TW554547B - Light emitting diode, optical semiconductor device, epoxy resin composition suited for optical semiconductor device, and method for manufacturing the same - Google Patents

Light emitting diode, optical semiconductor device, epoxy resin composition suited for optical semiconductor device, and method for manufacturing the same Download PDF

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Publication number
TW554547B
TW554547B TW091101139A TW91101139A TW554547B TW 554547 B TW554547 B TW 554547B TW 091101139 A TW091101139 A TW 091101139A TW 91101139 A TW91101139 A TW 91101139A TW 554547 B TW554547 B TW 554547B
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Taiwan
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light
fluorescent substance
resin
emitting diode
aforementioned
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TW091101139A
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Chinese (zh)
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Kensho Sakano
Kazuhiko Sakai
Yuji Okada
Toshihiko Umezu
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Nichia Corp
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    • H01L24/93—Batch processes
    • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
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    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch
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    • H01L2224/732—Location after the connecting process
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    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909—Post-treatment of the connector or wire bonding area
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Abstract

A light emitting diode comprising an LED chip having a light emitting layer made of a nitride compound semiconductor and a light transmitting resin that includes a fluorescent material which absorbs at least a part of light emitted by the LED chip and emits light of a different wavelength, wherein the fluorescent material includes a fluorescent particles of small particle size and a fluorescent particles of large particle size, the fluorescent particles of large particle size being distributed in the vicinity of the LED chip in the light transmitting resin to form a wavelength converting layer, the fluorescent particles of small particle size being distributed on the outside of the wavelength converting layer in the light transmitting resin.

Description

554547554547

技術領域 本發明係關於一種可利用於液晶之背燈、全彩顯示器、 開關内照明、照明用光源、各種指示器或交通信號燈等主 要係表面安裝型的發光二極體等之光半導體元件與其製造 方法、及、適用於其發光二極體之耐光性及可撓性優的透 明性環氧樹脂組合物。 背景技術 今日，藍色光為可呈高輝度-發光之半導體發光元件即利 用氮化物半導體（InxGayAll xyN、、（^以”之 LED晶片已被開發。利用氮化物半導體之發光元件係與利 用其他之GaAs、AlInGaP等材料且發出紅色至黃綠色之發 光元件比較，乃擁有輸出高且很少受溫度引起之色偏移 等，但，至今有在具有綠色以上波長之長波區域很難得到 咼輸出之傾向。另外，在此LED晶片上配置一可吸收從 led晶片放出之藍色光的一部份而黃色可發光之螢光物質 即YAG : Ce螢光體等，而白色系可發光之發光二極體亦本 案申請人開發，申請（國際公開編號WO 98/5078號）。 此發光二極體係無關於例如1晶片2端子構造之比較簡單 的構成，而介由凸透鏡輸出白色光（其係來自電氣連接於導 線電極之LED晶片的光、與、被覆LED晶片之透光性樹脂 中所含有的YAG : Ce等螢光物質的光之混色光）。 又，此發光二極體係調節螢光物質之使用量，以將從發 光二極禮所放出之混色光調整成略帶藍之白色至略帶黃之 白色等的任意色。進而，認為添加顏料亦可得到例如黃色 -4 - 本纸張尺度適用中國國家標準(CNS) Α4规格(210X297公釐) V ίBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-emitting semiconductor element, such as a surface-mounted light-emitting diode, which is mainly used for liquid crystal backlights, full-color displays, in-switch lighting, lighting sources, various indicators, or traffic lights, and the like. A production method and a transparent epoxy resin composition suitable for the light-emitting diode having excellent light resistance and flexibility. 2. Description of the Related Art Today, blue light is a semiconductor light-emitting element that can exhibit high luminance-luminescence, that is, an LED wafer using nitride semiconductors (InxGayAll xyN,, ^) has been developed. Light-emitting elements using nitride semiconductors and other GaAs, AlInGaP and other materials that emit red to yellow-green light-emitting elements have high output and are rarely affected by temperature-induced color shifts. However, it has been difficult to obtain chirp output in long-wavelength regions with wavelengths above green. In addition, on this LED chip, a fluorescent substance that can absorb part of the blue light emitted from the LED chip and emit yellow light, that is, YAG: Ce phosphor, etc., and white is a light-emitting diode that can emit light. Developed and applied by the applicant of this case (International Publication No. WO 98/5078). This light-emitting diode system does not have a relatively simple structure such as a 1-chip, 2-terminal structure, and outputs white light through a convex lens (which is derived from electrical Mixed color light of the light of the LED chip connected to the lead electrode and the light of fluorescent materials such as YAG: Ce contained in the translucent resin covering the LED chip) In addition, this light-emitting diode system adjusts the amount of fluorescent substance used to adjust the mixed-color light emitted from the light-emitting diode to any color such as a slightly blue white to a slightly yellow white. Further, it is considered that a pigment is added You can also get, for example, yellow -4-This paper size applies to China National Standard (CNS) Α4 (210X297 mm) V ί

裝 訂Binding

554547 A7 B7 五、發明説明（2 光或紅色光。 然而，求取發光二極體之廣泛利用領域以及可發出高輝 度之發光二極體。 又，在近年中，係廣泛使用晶片型之發光二極體，作為 開關内照明、全色顯示器、液晶背光等之光源。晶片型之 發光二極體的構成，係使用一種具有可收藏發光元件晶片 之凹部的封裝體，於該封裝體之凹部電氣連接發光元件晶 片，並包覆發光元件晶片之方_式形成透光性樹脂而封住。 另外，因今日之光半導體技術的快速進步，光半導體元 件之高輸出力化及短波長化，例如，在使用氮化物半導體 之發光二極體中，藉由構成發光層之組成的元素而可在主 發光學約365 nm至650 nm之任意發光锋發光，即使以550 nm以下之可見光（具體上近紫外線至藍綠色光等）於氮化物 半導體之發光層利用多重量子井構造亦可發出5 mw以上之 高輸出力。此高輸出力產生新的問題。亦即，可發出或接 受如此高能量光之光半導體元件中，光引起之模鋒樹脂的 劣化對策，或，藉熱緩和發生於模鋒樹脂與光半導體晶片 之間的應力乃成為特別重要的課題。 在特開平2000-196151號公報中，係揭示以脂環式環氧樹 脂作為主體之模鑄樹脂以取代一般雙酚型環氧樹脂。以脂 環式環氧樹脂作為主體而以酸甜使之硬化的環氧樹脂组合 物’係於主骨架幾乎不含成為光劣化原因之碳-碳間的雙 鍵，故，長時間之光照射後模鑄樹脂之劣化亦很少，又， 比較可撓性優，故，熱應力亦很難造成半導體晶片之損 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) A7 B7 554547 五、發明説明（3 ) 傷。 但，在半導體晶片直接安裝於基板表面之表面安裝型元 件（ = SMD 型、SMD ; Surface Mounted Device)中，必須使 模鑄樹脂形成薄膜，故無法使用酸酐硬化系之環氧樹脂。 亦即’表面士裝型元件之模鋒樹脂一般必須形成約1 mm以 下之薄膜，故，所塗布之環氧樹脂混合液與外氣的接觸面 積很廣。但，酸酐硬化劑係揮發性、吸濕性很高，而且， 以酸酐硬化劑而進行硬化必須5〜2 0小時之比較長時間， 故，硬化中酸酐硬化劑乃引起吸濕或揮發，環氧樹脂之硬 化不正常地進行。引起硬化不良之環氧樹脂係無法發揮樹 脂原來之性能，而大幅降低耐光性或耐熱性。 因此’必須為如表面安裝型元件之薄膜塗布的用途，並 非酸酐硬化劑，一般乃使用芳香族硫鑌鹽等之陽離子硬化 劑。陽離子硬化劑因揮發性低，與環氧樹脂之混合液塗布 於薄膜時，亦可進行良好的硬化。 但’陽離子硬化劑因原本易吸收藍色以下之短波長光， 故’受陽離子硬化劑而硬化之環氧樹脂係照射短波長光易 引起黃變。因此，要將被陽離子硬化劑所硬化之環氧樹脂 組合物使用於一可發出或接受藍色以下之短波長光的光半 導體元件乃很難。又，由陽離子硬化劑引起之硬化反應幾 乎只藉％乳基間之開環反應來進行，所得到之環氧樹脂組 合物係具有醚鍵比較規則排列之3次元網目狀構造，且可撓 性低。因此，使用一受陽離子硬化劑硬化之環氧樹脂作為 光半導體元件的模鑄樹脂情形下，光半導體元件之加熱、 -6 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 裝 訂554547 A7 B7 V. Description of the invention (2 light or red light. However, to find the field of wide application of light-emitting diodes and light-emitting diodes that can emit high brightness. Also, in recent years, wafer-type light-emitting diodes have been widely used. A diode is used as a light source for lighting inside a switch, a full-color display, a liquid crystal backlight, etc. The structure of a wafer-type light emitting diode uses a package having a recess for storing a light-emitting element wafer, and the recess of the package is used. The light-emitting element wafer is electrically connected, and the light-emitting element wafer is covered to form a light-transmitting resin and sealed. In addition, due to the rapid progress of today's optical semiconductor technology, the optical semiconductor element has a higher output force and a shorter wavelength. For example, in a light-emitting diode using a nitride semiconductor, the element constituting the light-emitting layer can emit light at any light emission front of about 365 nm to 650 nm, even in visible light below 550 nm (specifically Near-ultraviolet to blue-green light, etc.) The light emitting layer of the nitride semiconductor can also emit a high output force of more than 5 mw using a multiple quantum well structure. This high power New problems arise with force. That is, in light semiconductor devices that emit or receive such high-energy light, countermeasures against the degradation of the die resin caused by light, or by using heat to relax the die resin that occurs between the die resin and the optical semiconductor wafer. Stress is a particularly important issue. In Japanese Patent Application Laid-Open No. 2000-196151, it is disclosed that an alicyclic epoxy resin is used as a main body to replace a general bisphenol epoxy resin. An alicyclic epoxy resin is used. As the main body, the epoxy resin composition that is hardened by sweetness and acidity is mainly composed of a carbon-carbon double bond that causes photodegradation in the main skeleton. Therefore, the degradation of the mold resin after long-term light irradiation Rarely, moreover, it is more flexible, so it is difficult to cause damage to the semiconductor wafer due to thermal stress. -5- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 554547 5. Description of the invention (3) Injury. However, in a surface-mount component (= SMD type, SMD; Surface Mounted Device) in which a semiconductor wafer is directly mounted on a substrate surface, it is necessary to form a mold resin to form a thin film, so acid anhydride cannot be used. Chemical epoxy resin. That is, the mold resin of the surface-mounted component must generally form a film of less than about 1 mm, so the contact area of the applied epoxy resin mixture with outside air is wide. However, The acid anhydride hardener is highly volatile and hygroscopic, and it takes a long time of 5 to 20 hours to harden with the acid anhydride hardener. Therefore, the acid anhydride hardener causes moisture absorption or volatilization during curing. Hardening does not proceed normally. Epoxy resins that cause poor hardening do not exhibit the original properties of the resin and significantly reduce light or heat resistance. Therefore, they must be used for film coating of surface-mounted components, not acid anhydride hardeners. Generally, a cationic hardener such as an aromatic thiosulfate salt is used. Since the cationic hardener has low volatility, it can also harden well when the mixed solution with epoxy resin is applied to the film. However, since the 'cationic hardener' originally absorbs short-wavelength light below blue, the epoxy resin which is hardened by the cationic hardener is liable to cause yellowing due to short-wavelength light. Therefore, it is difficult to use an epoxy resin composition hardened by a cationic hardener in an optical semiconductor element that can emit or receive short-wavelength light below blue. In addition, the hardening reaction caused by the cationic hardener proceeds almost exclusively by the ring-opening reaction between% milk groups. The obtained epoxy resin composition has a three-dimensional mesh structure with a relatively regular arrangement of ether bonds, and is flexible. low. Therefore, in the case of using an epoxy resin hardened by a cationic hardener as the molding resin of the optical semiconductor element, the heating of the optical semiconductor element, -6-this paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ) Staple

554547 A7 ___ B7 五、發明説明（4 ) 冷卻時在光半導體晶片與模鑄樹脂之間會產生很大的應 力，易造成光半導體晶片之龜裂或導線斷裂。 為改善一使用陽離子硬化劑而硬化之環氧樹脂組合物的 可撓性，亦可於硬化之環氧樹脂中混合單縮水甘油基醚、 多元醇縮水甘油基醚、3級羧酸單縮水甘油基醚等之低分子 量的反應性稀釋劑。但，此等反應性稀釋劑之混合為避免 環氧樹脂之硬化，必須增加陽離子硬化劑之使用量，使環 氧樹脂組合物之黃變問題更惡化。 發明之揭示 本發明係為滿足對於上述氮化物半導體系之發光二極體 的各種要求而構成的，目的在於如下·· 弟1，本發明之目的在於提供一種發光特性更優異之色變 換型發光二極體。 第2 ’本發明之目的在於提供一種量產性優之發光二極體 的製造方法。 第3 ’本發明之目的在於提供一種以陽離子硬化劑進行硬 化，同時並很難引起黃變，且，可撓性優之環氧樹脂組合 物’藉由將如此之環氧樹脂組合物利用於模鋒樹脂，可提 供耐光性及耐熱性優之發光二極體。 為達成上述目的，本發明之第1發光二極體係具備··發光 層由氮化物系化合物半導體所構成的LED晶片、及、含有 一種可吸收自該LED晶片之光的至少一部分而發出不同波 長光之勞光物質的透光性樹脂；其特徵在於： 前述螢光物質係含有小粒徑螢光物質與大粒徑勞光物 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐)554547 A7 ___ B7 V. Description of the invention (4) During cooling, a great stress will be generated between the optical semiconductor wafer and the molding resin, which may easily cause cracks or wire breaks in the optical semiconductor wafer. In order to improve the flexibility of an epoxy resin composition hardened by using a cationic hardener, a monoglycidyl ether, a polyhydric alcohol glycidyl ether, and a tertiary carboxylic acid monoglycidyl can be mixed in the hardened epoxy resin Low molecular weight reactive diluent such as ether. However, in order to prevent the epoxy resin from being hardened by mixing these reactive diluents, it is necessary to increase the amount of the cationic hardener to worsen the yellowing problem of the epoxy resin composition. DISCLOSURE OF THE INVENTION The present invention is constituted to satisfy various requirements for the above-mentioned nitride semiconductor light-emitting diodes. The purpose is as follows: Brother 1. The object of the present invention is to provide a color-converting light-emitting device having more excellent light emitting characteristics Diode. The second object of the present invention is to provide a method for manufacturing a light-emitting diode having excellent mass productivity. The third object of the present invention is to provide an epoxy resin composition that is hardened with a cationic hardener and hardly causes yellowing, and has excellent flexibility. Mould resin provides light emitting diodes with excellent light and heat resistance. In order to achieve the above object, the first light-emitting diode system of the present invention includes an LED wafer having a light-emitting layer composed of a nitride-based compound semiconductor, and emitting a different wavelength by including at least a portion of light that can be absorbed by the LED wafer. The light-transmitting resin of the light-emitting material is characterized in that the aforementioned fluorescent material contains a small-sized fluorescent material and a large-sized fluorescent material. (Centimeter)

554547 A7 B7 五、發明説明（5 ) 質，前述大粒徑螢光物質係在前述透光性樹脂中分布於 LED晶片附近而形成色變換層，前述小粒徑螢光物質係在 前述透光性樹脂中分布於前述色變換層的外側。 在如此所構成之第1發光二極體中，由大粒徑螢光物質所 構成之色變換層可有效地使之色變換，且，藉由分散於其 外側之小粒徑螢光物質可抑制色不均。 又，在本發明之第1發光二極體中，前述大粒徑螢光物質 其粒徑宜調整至10 /zm〜60 //jn?藉此，可使前述大粒徑勞 光物質比較粗地分布於前述透光性樹脂中之LED晶片附 近，可有效發揮波長變換功能。 又，本發明之第1發光二極體中，前述小粒徑螢光物質其 粒徑宜調整至0·2 //m〜1·5 /zm，藉此，可防止小粒徑榮光 物質之凝集，且，可有效發揮光的散亂功能，故可更有效 抑制色不均。 進一步，前述大粒徑螢光物質之頻度譜♦粒徑值宜設定 於前述小粒徑螢光物質之頻度譜峰粒徑值的2 0〜9 0倍，藉 此，可提高光之取出效率。 又，本發明之第2發光二極體係具備··發光層由半導體所 構成之發光元件、及、含有一種可吸收自該發光元件之光 的至少一部分而發出不同波長光的螢光物質之透光性樹 脂；前述螢光物質在體積基準粒度分布曲線中，具有加算 值0·01 vol%〜10 vol%間斜率為0之平坦區域β因此，可得 到以高輝度輸出之高發光二極體。 又，本發明之第2發光二極體中，螢光物質係包括：以前 -8 - 本紙張尺度適用中國國家標準(CNS) Α4規格(210X 297公釐) 裝 訂554547 A7 B7 5. Description of the invention (5) The above-mentioned large particle size fluorescent substance is distributed near the LED chip in the light-transmitting resin to form a color conversion layer, and the small particle size fluorescent substance is light-transmitting. The resin is distributed outside the color conversion layer. In the first light-emitting diode thus constituted, a color conversion layer composed of a large-diameter fluorescent substance can effectively perform color conversion, and a small-particle-size fluorescent substance dispersed on the outside thereof can be used for color conversion. Suppresses color unevenness. Moreover, in the first light-emitting diode of the present invention, the particle size of the fluorescent material with a large particle size should be adjusted to 10 / zm ~ 60 // jn? By doing so, the material with a large particle size can be made relatively coarse. It is distributed in the vicinity of the LED chip in the light-transmitting resin and can effectively perform the wavelength conversion function. Furthermore, in the first light-emitting diode of the present invention, the particle size of the aforementioned small particle size fluorescent substance should be adjusted to 0 · 2 //m~1.5·zm, thereby preventing the small particle size glory substance from being prevented. Aggregation and the light scattering function can be effectively performed, so color unevenness can be suppressed more effectively. Further, the frequency spectrum of the aforementioned large-sized fluorescent substance ♦ The particle size value should be set to 20 to 90 times the peak particle diameter value of the frequency spectrum of the aforementioned small-sized fluorescent substance, thereby improving the extraction efficiency of light . The second light-emitting diode system of the present invention includes a light-emitting element composed of a semiconductor having a light-emitting layer, and a transparent substance containing a fluorescent substance capable of absorbing at least a part of light from the light-emitting element and emitting light of a different wavelength. Photoresin; the above-mentioned fluorescent substance has a flat area β with a slope of 0 in the volume-based particle size distribution curve of the added value. Therefore, a high light-emitting diode with a high luminance output can be obtained. . Moreover, in the second light-emitting diode of the present invention, the fluorescent substance system includes the following: -8-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) binding

554547 A7 ^____ B7_ 五、發明説明（6 ) 述平坦區域為界之小粒徑螢光物質及大粒徑螢光物質，前 述大粒徑螢光物質之頻度譜峰粒徑值宜為小粒徑勞光物質 之頻度譜峰粒徑值的2〇〜90倍，如此一來，可得到光取出 效率更良好之發光二極體。 又’在本發明之第1與第2發光二極體中，螢光物質之中 心粒徑宜為1 5 // m〜5 0 // m，藉此，可提高發光效率並得到 輝度雨之發光二極禮。又，可抑制一種形成對光學特性有 影響之傾向並密集凝集之凝集體。 在本發明之第1與第2發光二極體中，中心粒徑之頻度值 若為20〜50%之範圍，可減少粒徑之參差不齊，藉此可抑 制色不均，得到具有良好對此之發光。 進一步’在本發明之第1與第2發光二極體中，若於前述 透光性樹脂中含有螢光物質以及擴散劑，更可抑制色不均 並得到均一的發光，故佳。 又’在本發明之第1與第2發光二極體中，由前述透光性 樹脂所構成之發光面宜具有曲面。藉此而發光元件之光從 前述透光性樹脂朝外部取出時，在前述透光性樹脂與外部 之空氣層的界面光會擴散，藉由使用大粒徑螢光物質可抑 制易產生之色不均。可提高在發光面之光的取出效率，並 更高輸出力地發光。 又，本發明之第3發光二極體係具備：封裝體，其係包括 構成正負電極之一對金屬薄板以被絕緣樹脂電氣分離之方 式接合而構成的金屬底、及、為形成收藏部於前述金屬底 之一個面的周圍被接合的側壁部；設於前述收藏部之lEd I纸張尺度適用巾g Η家鮮(CNS) Α4規格(210 X 297公釐)554547 A7 ^ ____ B7_ V. Description of the invention (6) The flat area is a boundary of the small particle size fluorescent material and the large particle size fluorescent material. The frequency spectrum peak particle size value of the large particle size fluorescent material should be small particles. The diameter of the peak value of the frequency spectrum of the light-emitting substance is 20 to 90 times, so that a light-emitting diode with better light extraction efficiency can be obtained. Furthermore, in the first and second light-emitting diodes of the present invention, the central particle diameter of the fluorescent substance should preferably be 1 5 // m to 5 0 // m, thereby improving the luminous efficiency and obtaining the luminance rain. Glowing Dipole. In addition, it is possible to suppress the formation of agglomerates that tend to affect the optical characteristics and are densely aggregated. In the first and second light-emitting diodes of the present invention, if the frequency value of the center particle diameter is in the range of 20 to 50%, the variation in particle diameter can be reduced, thereby suppressing color unevenness and obtaining good results. It glowed. Furthermore, in the first and second light-emitting diodes of the present invention, if the light-transmitting resin contains a fluorescent substance and a diffusing agent, color unevenness can be suppressed and uniform light emission can be obtained. Further, in the first and second light-emitting diodes of the present invention, the light-emitting surface made of the light-transmitting resin preferably has a curved surface. As a result, when light from the light-emitting element is taken out from the translucent resin to the outside, light is diffused at the interface between the translucent resin and the outer air layer, and a color that is easily generated can be suppressed by using a large-diameter fluorescent substance Uneven. It is possible to improve the extraction efficiency of light on the light emitting surface and emit light with higher output. The third light-emitting diode system of the present invention includes a package including a metal base configured by joining a pair of metal thin plates constituting one of the positive and negative electrodes to be electrically separated by an insulating resin, and a storage portion for forming a storage portion. Side wall portion joined around one side of the metal bottom; lEd I paper size applicable towels set in the aforementioned storage section g Η 家 鲜 (CNS) Α4 size (210 X 297 mm)

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554547 A7 ___B7 五、發明説明（7 ) 晶片、及、以封住前述led晶片之方式充填於前述收藏部 之透光性樹脂；其特徵在於： 前述透光性樹脂係從前述收藏部於其周圍之側壁部上面 連續而形成，其透光性樹脂之上面為平坦且與前述金屬底 略平行，且，前述透光性樹脂之外周側面在於與前述封裝 體之外周側面略同一面β 藉如此所構成之第3發光二極體，可提供信賴性及量產性 優之發光二極體。又，前述透光性樹脂乃從前述收藏部於 其周圍之側壁的上面連績而形成，故，發光面廣而成為發 光二極體之上面全體，可實現良好的指向特性。 又，於前述透光性樹脂亦可含有填充劑，其中一種可含 有能吸收來自發光元件之光的一部分而發出不同波長光之 螢光物質。 含有螢光物質時，易產生色不均，但，若形成本發明之 構成’可得到良好的發光面，可抑制色不均。 又，螢光物質之中心粒徑宜為15 〜5〇 ，更宜為 20 /zm〜50 #m。若使用如此之粒徑範圍的螢光物質，可 有效發揮螢光物質之波長變換功能，且，切片步驟可良好 地實施且可提高良率。 本發明之發光一極體的製造方法，係用以製造前述第3發 光二極體之方法，其特徵在於具備如下步驟： 第1步驟：使分別對應於前述收藏部之複數貫通孔分成群 組所形成的絕緣基板、與、對應於前述各貫通孔而具有被 前述絕緣樹脂分離之部分的金屬基板接合，以製作由複數 •10· 本紙張尺度適用巾S S家標準(CNS) A4規格(21G X 297公釐) ' - 554547 A7 B7 五、發明説明（8 封裝體集合體所構成的封裝體組件； 第2步驟：於被前述貫通孔所形成之各封裝體的收藏部安 裝LED晶片； 第3步驟·對應於如述各群組而使用—形成1個開口部的 掩模，而藉孔版印刷於前述絕緣性基板之上面與貫通孔内 塗布前述透光性樹脂而使之硬化； 第4步驟：將形成前述透光性樹脂之封裝體組件分割成各 封裝體。 _ 藉此，可以量產性良好地形成一厚度一定且具有平滑發 光面及端面之發光二極體。 又在本發明之製造方法中，前述孔版印刷宜反覆進行 減壓及加壓。藉此可極簡單地脫去氣泡等，可製造特性參 差不齊更少且發光不均或色不均很少之發光二極體。 尤其，透光性樹脂中含有無機物即填充劑時，混合中有 氣泡易進入之傾向。又，光之路程長會變長，且各種填充 劑間、及此等與透光性樹脂之比重差異而易產生色不均， 但，可藉本發明之製造方法抑制色不均。可得到一種所製 造之各發光一極體間的色參差不齊很少且信賴性高之發光 二極體。 Λ 本案發明之環氧樹脂組合物其特徵在於包含··脂環式環 氧樹脂65重量％以上所構成之環氧樹脂、相對於前述 樹脂之環氧當量為〇·〇〇5〜1 ·5莫耳以通式（1)所示之酸酐或 以通式（2)所示之二幾酸、 -11 - ^紙張尺度適用中® ®家標準(CNS) Α4規格(21GX297公釐y554547 A7 ___B7 V. Description of the invention (7) The wafer and the translucent resin filled in the storage section by sealing the LED chip; characterized in that: the translucent resin is from the storage section around the storage section; The upper surface of the side wall portion is formed continuously, and the upper surface of the translucent resin is flat and slightly parallel to the metal bottom, and the outer peripheral surface of the translucent resin is slightly the same as the outer peripheral surface of the package β. The third light-emitting diode is configured to provide a light-emitting diode with excellent reliability and mass productivity. In addition, since the light-transmitting resin is formed successively from the upper surface of the side wall of the storage portion, the light-emitting surface is wide to form the entire upper surface of the light-emitting diode, and good directional characteristics can be achieved. Further, the translucent resin may contain a filler, and one of them may contain a fluorescent substance capable of absorbing a part of the light from the light emitting element and emitting light of a different wavelength. When a fluorescent substance is contained, color unevenness easily occurs. However, if the constitution of the present invention is formed, a good light emitting surface can be obtained, and color unevenness can be suppressed. The central particle diameter of the fluorescent substance is preferably 15 to 50, and more preferably 20 / zm to 50 #m. If a fluorescent substance having such a particle size range is used, the wavelength conversion function of the fluorescent substance can be effectively exerted, and the slicing step can be performed well and the yield can be improved. The manufacturing method of the light-emitting monopole of the present invention is a method for manufacturing the third light-emitting diode, and is characterized by having the following steps: Step 1: Grouping a plurality of through-holes respectively corresponding to the storage section into groups The formed insulating substrate is bonded to a metal substrate corresponding to each of the through holes and having a portion separated by the insulating resin, so as to produce a plurality of • 10 · This paper size is applicable to SS Home Standard (CNS) A4 specifications (21G X 297 mm) '-554547 A7 B7 V. Description of the invention (8 Package assembly composed of package assembly; Step 2: Install the LED chip in the storage part of each package formed by the aforementioned through hole; 3 steps · Use corresponding to each group as described above—form a mask with one opening, and apply stencil printing on the top of the insulating substrate and apply the light-transmitting resin in the through-hole to harden it; Section 4 Step: Divide the package body forming the light-transmitting resin into individual packages. _ By this, a light-emitting diode with a constant thickness and a smooth light-emitting surface and an end surface can be formed with good mass productivity. In the manufacturing method of the present invention, the aforementioned stencil printing should be repeatedly depressurized and pressurized. Thereby, bubbles and the like can be removed very easily, and there can be less uneven production characteristics and uneven light emission or color unevenness. Very few light-emitting diodes. In particular, when the translucent resin contains an inorganic substance, that is, a filler, there is a tendency for bubbles to enter easily during mixing. In addition, the distance of light will be longer, and various fillers, and so on The difference in specific gravity from the light-transmitting resin is likely to cause color unevenness, but the color unevenness can be suppressed by the manufacturing method of the present invention. It is possible to obtain a reliable and reliable color unevenness among the light-emitting monopoles produced. High-emission light-emitting diode. Λ The epoxy resin composition of the present invention is characterized in that it contains an epoxy resin composed of 65% by weight or more of an alicyclic epoxy resin, and has an epoxy equivalent to the aforementioned resin. · 〇〇5 ～ 1 · 5 moles Anhydride represented by the general formula (1) or bis-acid represented by the general formula (2), -11-^ Applicable paper standards ® ® Home Standard (CNS) Α4 Specifications (21GX297 mm)

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554547 A7 _____ B7 五、發明説明（9 ) 0554547 A7 _____ B7 V. Description of the invention (9) 0

0 HOOC-R2-COOH (2) (式中，R!為碳數0〜12之環式或脂肪族烷基或芳基、心為 碳數0〜12之烷基或芳基）、與、相對於前述環氧樹脂之環 氧基當量為0.0001〜0.01莫耳的陽離子硬化劑。 本發明之環氧樹脂組合物係形成一種脂環式環氧樹脂與 酸酐或二羧酸（以下、酸酐等）反應而具有某種聚合度之交 聯寡聚物，故，以習知之1/10至1/1〇〇之量的陽離子硬化 劑可完全地硬化。因此，可抑制陽離子硬化劑引起之短波 長光吸收，可防止所得到之環氧樹脂组合物的黃變。又， 本發明之環氧樹脂組合物係不僅具有因環氧基開環反應所 產生之醚鍵，亦具有脂環式環氧樹脂與酸酐等之交聯結合 反應所產生之酯鍵，並具有環氧樹脂間不規則連結之3次元 綱目構造。因此，即使不使用反應性稀釋劑亦具有高的可 撓性，使用於光半導體元件之模鑄樹脂時，可使光半導體 晶片與模鑄樹脂之間的熱應力緩和，而防止龜裂或導線斷 裂等之問題。 環氧樹脂组合物之可撓性係比例於環氧樹脂與酸奸等反 應所得到的交聯寡聚物的分子量。亦即，交聯寡聚物中之 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 554547 A70 HOOC-R2-COOH (2) (where R! Is a cyclic or aliphatic alkyl or aryl group having 0 to 12 carbon atoms, and the heart is an alkyl or aryl group having 0 to 12 carbon atoms), and, A cationic hardener having an epoxy equivalent of 0.0001 to 0.01 mol relative to the aforementioned epoxy resin. The epoxy resin composition of the present invention forms a cross-linked oligomer having a certain degree of polymerization by reacting an alicyclic epoxy resin with an acid anhydride or a dicarboxylic acid (hereinafter, an acid anhydride, etc.). The cationic hardener in an amount of 10 to 1/100 can be completely hardened. Therefore, short-wavelength light absorption by the cationic hardener can be suppressed, and yellowing of the obtained epoxy resin composition can be prevented. In addition, the epoxy resin composition of the present invention has not only an ether bond generated by an epoxy ring-opening reaction, but also an ester bond generated by a cross-linking reaction between an alicyclic epoxy resin and an acid anhydride, and the like. Three-dimensional structure of irregular connection between epoxy resins. Therefore, even without the use of a reactive diluent, it has high flexibility. When used in the molding resin of optical semiconductor devices, the thermal stress between the optical semiconductor wafer and the molding resin can be relaxed, and cracks or wires can be prevented. Problems such as fracture. The flexibility of the epoxy resin composition is proportional to the molecular weight of the cross-linked oligomer obtained by the reaction of the epoxy resin and acid. That is, -12 in the cross-linked oligomer is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 554547 A7

私奸等擁有的幾基之中，與環氧樹脂或後述之助觸媒反應 而轉化成醋之比率愈高，所得到之環氧樹脂組合物的可捷 性愈良好。認為㈣轉化進行乃很難引起薄膜在硬化之際 的酸奸等揮發。交聯寡聚物中之_等擁有㈣基之酿轉 率為1 0 /。以上，更苴為7 〇 %以上。酯轉化率可以反應溫 度與時間來調節。 匕又，本|明之環氧樹脂㉞合物的優點，係脂環式環氧樹 月曰與酸酐或二羧酸反應而得到交聯寡聚物後，可使前述交 聯寡聚物使與陽離子硬化劑之混合物硬化。亦即，使脂環 j環氧樹脂與酸酐等預先在適當的反應容器中反應而形成 交聯寡聚物，若使其交聯寡聚物與陽離子硬化劑之混合液 模鑄於光半導體元件的基板上，即使模鑄成薄膜狀時亦可 防止硬化反應中酸酐揮發。又，交聯寡聚物與陽離子硬化 劑 < 混合液的黏度可藉酸酐等之添加量或酯轉化率而自由 調節，故可很容易設定適於處理之黏度。又，交聯寡聚物 與陽離子硬化劑之混合液因已進行某種度聚合，故黏度很 少隨時間變化，適用期（p〇t Hfe)亦長。 進一步’將本發明之環氧樹脂組合物使用於光半導體元 件之模鑄樹脂時，亦可適當混合填充劑、螢光劑粒子、著 色劑粒子等功能粒子，但，交聯寡聚物與陽離子硬化劑之 混合液為比較高黏度，此等功能粒子之分散性佳。因此， 很少的粒子含量可顯現所希望的功能，並降低功能粒子之 光散亂、遮蔽等引起的光半導體元件之發光或受光損失。 用於本發明環氧樹脂組合物之脂環式環氧樹脂，係宜使 -13 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)Among the several bases possessed by gangsters, the higher the ratio of reaction with epoxy resin or a catalyst to be described later to convert to vinegar, the better the flexibility of the obtained epoxy resin composition. It is considered that the conversion of tritium is difficult to cause the film to volatilize when it is hardened. In the cross-linked oligomers, the conversion rate of the fluorene group with a fluorenyl group is 10 /. The above is more than 70%. Ester conversion can be adjusted by reaction temperature and time. The advantages of the epoxy resin compound of this invention are that the alicyclic epoxy resin is reacted with an acid anhydride or a dicarboxylic acid to obtain a crosslinked oligomer. A mixture of cationic hardeners hardens. That is, an alicyclic j epoxy resin and an acid anhydride are reacted in advance in an appropriate reaction container to form a crosslinked oligomer, and if a mixed solution of the crosslinked oligomer and a cationic hardener is molded into an optical semiconductor device, On the substrate, the acid anhydride can be prevented from volatilizing during the curing reaction even when it is molded into a thin film. In addition, the viscosity of the mixed solution of the cross-linked oligomer and the cationic hardener < can be freely adjusted by the addition amount of the acid anhydride or the like, or the ester conversion rate, so it is easy to set a viscosity suitable for processing. In addition, since the mixed solution of the cross-linked oligomer and the cationic hardener has been polymerized to a certain degree, the viscosity rarely changes with time, and the pot life (pot Hfe) is also long. Furthermore, when the epoxy resin composition of the present invention is used for a die-cast resin of an optical semiconductor device, functional particles such as fillers, fluorescer particles, and colorant particles may be appropriately mixed, but the crosslinked oligomer and cation The mixture of hardeners has a relatively high viscosity, and the dispersibility of these functional particles is good. Therefore, a small amount of particles can exhibit a desired function and reduce the light emission or light loss of an optical semiconductor device caused by light scattering, shielding, and the like of the functional particles. The alicyclic epoxy resin used in the epoxy resin composition of the present invention is preferably -13-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

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二翁奸齡-& l 4 、虱化雙酚A二縮水甘油基醚、 很難引起光劣化…可得到二此♦脂環式環氧樹脂， 物。 了仵到可撓性優之環氧樹脂组合 ;不贫月環氧樹脂組合物之陽離子硬化 香族硫鐳鹽、芳香族重且使用7 贫秩里氮知、芳香碘鑌鹽、芳香族磁苗 等。此等陽離子硬化劑係硬化、余步 Λ 分硬化。 以㈤係硬化速度快，且可以少量得則 '又本發明之環氧樹脂組合物進一步宜相對於酸酐或二 破酸含有G.1〜5.G當量之多價醇或其聚縮合體。多價醇可使 用如乙二醇、二甘醇、三乙二醇、三乙二醇、丙二醇、 1，心丁二醇、i，6-己二醇等。藉由添加此等多元醇或其聚 縮合體，可進-步提昇所得到之環氧樹脂組合物之可挽 性。 又，本發明之光半導體元件係具備：至少一對之導線電 極、電氣連接於前述導線電極之光半導體晶片、及、封住 則述光半導體晶片之模鑄樹脂；其特徵在於模鑄樹脂乃由 本發明之％乳樹脂組合物所構成的。藉此，可得到一種光 半導體元件’其係模鑄樹脂黃變所引起之發光或受光效率 的降低很少，又，熱循環引起之晶片損傷或導線斷裂不易 發生。 尤其’本發明之光半導體元件係於形成導線電極之基板 表面接合前述光半導體晶片而成之表面安裝型，又，光半 導體晶片具有一由至少含有In與Ga之氮化物半導禮所構成 -14 - 本紙張尺度適用中菌酉家標準(CNS) A4規格(210X 297公釐）Diwon's age-& l 4, liceated bisphenol A diglycidyl ether, it is difficult to cause photodegradation ... can be obtained alicyclic epoxy resin. It has an epoxy resin combination with excellent flexibility; a cationic hardening aromatic sulfur radium salt of a non-depleted epoxy resin composition, aromatic heavy and using 7 depleted nitrogen, aromatic iodonium salt, aromatic magnetic Miao and so on. These cationic hardeners are hardened, and the remaining steps are hardened. The saccharide hardening speed is fast and can be obtained in a small amount. Furthermore, the epoxy resin composition of the present invention further preferably contains G.1 to 5.G equivalent of polyvalent alcohol or polycondensate thereof with respect to acid anhydride or dibasic acid. Polyvalent alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, triethylene glycol, propylene glycol, 1, butanediol, i, 6-hexanediol, and the like can be used. By adding these polyols or their polycondensates, the affordability of the obtained epoxy resin composition can be further improved. The optical semiconductor element of the present invention includes at least one pair of lead electrodes, an optical semiconductor wafer electrically connected to the lead electrodes, and a molding resin sealing the optical semiconductor wafer; the molding resin is characterized in that: It is composed of the% milk resin composition of the present invention. Thereby, it is possible to obtain an optical semiconductor element 'which has little reduction in light emission or light receiving efficiency caused by yellowing of the mold resin, and further, wafer damage or wire breakage due to thermal cycling is unlikely to occur. In particular, 'the optical semiconductor element of the present invention is a surface mount type formed by bonding the aforementioned optical semiconductor wafer to the surface of a substrate on which a wire electrode is formed, and the optical semiconductor wafer has a semiconducting nitride containing at least In and Ga- 14-The size of this paper is applicable to CNS A4 (210X 297mm)

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圖面之簡單說明 圖1係本發明實施形態i之SMD型發光二極體的模式斷面 圖。 圖2A係表示實施形態1之螢光物質的體積基準分布曲線 (相對於粒徑之加算值）圖。 圖2 B係表示實施形態1之螢光物質的體積基準分布曲線 (相對於粒徑之頻度值）圖。 圖3 A係在實施形態1之製造方法中，使用於孔版印刷之 掩模的模式平面圖。 圖3B係使圖3A之掩模的一部分擴散而表示的模式平面 圖。 圖4A〜4D係實施形態1之製造方法中的孔版印刷步驟 圖。 圖5係實施形態1之製造方法中，進行孔版印刷而使透光 性樹脂硬化後之封裝體組件的一部分斷面圖。 圖6係本發明實施形態2之SMD型發光二極體的模式斷面 圖。 圖7 A、7 B係表示實施例5之發光二極體的透光性樹脂， 其形成步驟之斷面圖。 圖8係本發明實施例1之SMD型發光二極體的模式斷面 圖0 圖9 A係表示比較例1之螢光物質的體積基準分布曲線（相 對於粒徑之加算值）圖。 圖9B係表示比較例1之螢光物質的體積基準分布曲線（相 -16· 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)Brief Description of the Drawings Fig. 1 is a schematic sectional view of an SMD type light emitting diode according to Embodiment i of the present invention. FIG. 2A is a graph showing a volume-based distribution curve (added value with respect to a particle size) of a fluorescent substance in Embodiment 1. FIG. FIG. 2B is a graph showing a volume reference distribution curve (frequency value with respect to a particle size) of the fluorescent substance of Embodiment 1. FIG. Fig. 3A is a schematic plan view of a mask used for stencil printing in the manufacturing method of the first embodiment. Fig. 3B is a schematic plan view showing a part of the mask of Fig. 3A diffused. Figs. 4A to 4D are stencil printing steps in the manufacturing method of the first embodiment. Fig. 5 is a cross-sectional view of a part of a package component after the stencil printing is performed to harden a light-transmitting resin in the manufacturing method of the first embodiment. Fig. 6 is a schematic sectional view of an SMD type light emitting diode according to a second embodiment of the present invention. 7A and 7B are cross-sectional views showing the light-transmitting resin of the light-emitting diode of Example 5 and the forming steps thereof. Fig. 8 is a schematic sectional view of an SMD-type light emitting diode according to Example 1 of the present invention. Fig. 0 Fig. 9 A is a graph showing a volume reference distribution curve (added value with respect to particle size) of the fluorescent substance of Comparative Example 1. Fig. 9B shows the volume-based distribution curve of the fluorescent substance in Comparative Example 1 (phase -16 · This paper size is in accordance with China National Standard (CNS) A4 specification (210X297 mm)

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對於粒徑之頻度值）圖。 圖10A係本發明實施例9之燈光型發光二極體的模式斷面 圖〇 圖10B係圖l〇A之點線圓部分的擴大圖。 圖11A係表示有關環氧樹脂組合物而耐光性試驗前之全 光線穿透率圖。 圖11 B係表示有關環氧樹脂組合物而耐光性試驗後之全 光線穿透率圖。 _ 圖12A係表示有關環氧樹脂組合物而耐熱試驗前之全光 線穿透率圖。 圖1 2 B係表tjt有關環乳樹脂組合物而耐熱試驗後之全光 線穿透率圖。 圖1 3係將環氧樹脂組合物用於模鋒樹脂之發光二極體， 其常溫壽命試驗中之輸出強度變化圖。 圖1 4係將環乳樹脂組合物用於模轉樹脂之發光二極禮， 其高溫高濕壽命試驗中之輸出強度變化圖。 圖1 5係表示環氧樹脂組合物之黏度隨時間變化圖。 用以實施發明之最佳形態 以下’一面參照圖面一面說明有關本發明實施形態。 實施形態1 本發明之形態1的發光二極體如圖1所示，係於封裝體中 發光二極體晶片（LED晶片）5被透光性樹脂8封住所形成之 表面安裝型（SMD型）的發光二極體。在本實施形態1之發光 二極體中，封裝體係由金屬基底2與側壁部1所構成的，側 -17- 本纸張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)For frequency values of particle size). FIG. 10A is a schematic cross-sectional view of a light-emitting light-emitting diode according to Embodiment 9 of the present invention. FIG. 10B is an enlarged view of a dotted circle portion of FIG. 10A. Fig. 11A is a graph showing the total light transmittance of the epoxy resin composition before the light resistance test. Fig. 11B is a graph showing the total light transmittance of the epoxy resin composition after a light resistance test. Fig. 12A is a graph showing the total light transmittance of the epoxy resin composition before the heat resistance test. Fig. 12 B is a graph showing the total light transmittance of the cycloemulsion resin composition after heat resistance test in Table tjt. Fig. 13 is a graph showing the change in output intensity during the life-temperature test of a light-emitting diode using an epoxy resin composition as a mold resin. Fig. 14 is a graph showing the change of output intensity in a high temperature and high humidity life test of a light emitting diode using a cycloemulsion resin composition for a mold transfer resin. Fig. 15 is a graph showing the change in viscosity of the epoxy resin composition with time. Best Mode for Carrying Out the Invention Embodiments of the present invention will be described below with reference to the drawings. Embodiment 1 As shown in FIG. 1, a light-emitting diode according to a first embodiment of the present invention is a surface-mount type (SMD type) formed by sealing a light-emitting diode chip (LED chip) 5 in a package with a transparent resin 8 ) Light-emitting diode. In the light-emitting diode of the first embodiment, the packaging system is composed of a metal substrate 2 and a side wall portion 1, and the side is -17- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)

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554547 A7 B7 五、發明説明（ 壁部1係為構成收藏部la，接合於金屬基底2之一者的面之 周圍。LED晶片5係於封裝體之收藏部la被模黏合而藉引線 接合形成特定配線後，以透光性樹脂8 (例如LED晶片上之 厚約1 mm)封住。 此處，本實施形態1之發光二極體中，係使用本案特有之 環氧樹脂作為封住樹脂8，在封住樹脂8中係藉發光二極禮 (LED)晶片所發出之、光變換成波長不同的光而輸出之勞光 物質（螢光體粒子）被分散，具有如以下之特徵。 第1，透光性之封住樹脂8係^脂環式環氧樹脂與酸奸或二 幾酸反應而形成交聯寡聚物，使用一可以少量陽離子硬化 劑硬化之環氧樹脂组合物，俾提昇耐光性及耐熱性。 第2，使分散於透光性樹脂之螢光物質（色變換材料）的粒 度分布形成本案特有的分布，可大幅改善發光輸出及發光 輝度。 以下，詳細說明有關本實施形態1之發光二極體的構成。 <封裝體> 在本實施形態中，封装體之金屬基底2係構成正端子之金 屬薄板2a與構成負端子之金屬薄板2b以絕緣性樹脂4接 合’並分別藉焊線7連接於LED晶片5之正電極5a與負電極 5b。 此處，在本實施形態1中，LED晶片5係於一者之金屬薄 板2b上被模黏合樹脂6模黏合。但，在本發明中，led晶 片5亦可於另一者之金屬薄板2a上模黏合，亦可跨越金屬 薄板2a與金屬薄板2b而被模黏合❶ < LED晶片5 > ..... . ...... * 18 * 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 554547 A7 B7 五、發明説明（彳6 ) 本實施形態1之發光二極體係藉螢光物質使來自LED晶片 5之光的一部分或全部進行波長變換之方式構成的，故， LED晶片5係使用一種可發出激發其螢光物質之發光波長的 光者。在本發明中，如此之LED晶片5可使用一種利用 ZnSe系、或GaN系等各種半導體所構成者，但，在本發明 中，係使用一種LED晶片5，其乃利用可有效激發螢光物質 之短波長光可發光的氮化物半導體（InxAlyGai x yN、〇 $ X、OSY、X + Y^l)。此LED晶片 5 具有i^GahWOcxq) 作為發光層’藉其混晶度而可使發光波長在約365 nm至650 nm任意改變。LED晶片5之構造可舉例：具有MIS接合、 PIN接合或pn接合等之均質構造、異質構造或雙異質構造 者，在本發明中可使用任一者，但，宜採用可得到更高輝 度之雙異質構造。又，藉構成發光層（活性層）之半導體組 成或其混晶度而可選擇各種發光波長。又，亦可形成一在 活性層含有產生量子效果之薄膜所構成的單一量子井構造 或多重量子井構造。 使用氮化物半導體之LED晶片5時，於基板係可使用藍寶 石、尖晶石、SiC、Si、ZnQ等材料，但為量產性佳地形成 結晶性良好的氮化物半導體，宜使用藍寶石基板。在此藍 寶石基板上可使用MOCVD法等形成氮化物半導體。此時， 在藍寶石基板上宜形成GaN、AIN、GaAIN等之緩衝層而於 其上使具有pn接合之氮化物半導體層成長。 具有一使用氮化物半導體之pn接合的LED晶片例，可舉 出：於藍寶石基板上形成緩衝層，於其緩衝層上使η型氮化 •19- i紙張尺度適用中國囷家標準(CNS) A4規格(210 X 297公釐） " 裝 訂554547 A7 B7 V. Description of the invention (Wall part 1 is to form the storage part la, which is bonded around the surface of one of the metal substrates 2. The LED chip 5 is formed by wire bonding to the storage part la of the package by die bonding. After the wiring is specified, it is sealed with a translucent resin 8 (for example, a thickness of about 1 mm on the LED chip). Here, the light-emitting diode of the first embodiment uses an epoxy resin unique to the case as the sealing resin. 8. In the sealing resin 8, the light-emitting substances (fluorescent particles) emitted by the light-emitting diode (LED) wafer and converted into light with different wavelengths are dispersed, and have the following characteristics. First, the translucent sealing resin 8 series alicyclic epoxy resin reacts with acid or dipic acid to form a crosslinked oligomer. An epoxy resin composition that can be hardened with a small amount of cationic hardener is used.俾 Improve light resistance and heat resistance. Second, the particle size distribution of the fluorescent substance (color conversion material) dispersed in the light-transmitting resin is formed into a unique distribution in this case, which can greatly improve the light emission output and light emission brightness. The details will be described below. Issue of the first embodiment Structure of the diode. ≪ Package > In this embodiment, the metal base 2 of the package is a metal thin plate 2a constituting a positive terminal and a metal thin plate 2b constituting a negative terminal are joined by an insulating resin 4 and borrowed separately. The bonding wire 7 is connected to the positive electrode 5a and the negative electrode 5b of the LED chip 5. Here, in the first embodiment, the LED chip 5 is bonded to the metal thin plate 2b by a mold bonding resin 6 mold. In the present invention, the LED chip 5 may also be die-bonded on the other metal sheet 2a, or may be die-bonded across the metal sheet 2a and the metal sheet 2b. ≪ LED chip 5 > ..... ..... * 18 * This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554547 A7 B7 V. Description of the invention (彳 6) The light-emitting diode system of this embodiment 1 uses fluorescent light The substance is constructed by converting a part or all of the light from the LED chip 5. Therefore, the LED chip 5 uses a light emitting wavelength that excites its fluorescent substance. In the present invention, such an LED As the wafer 5, a variety of semiconductor devices such as ZnSe-based or GaN-based semiconductors can be used. Successful, but in the present invention, an LED chip 5 is used, which is a nitride semiconductor (InxAlyGai x yN, 〇 $ X, OSY, X + Y) that can emit light using short-wavelength light that can effectively excite a fluorescent substance. ^ l). This LED chip 5 has i ^ GahWOcxq) as the light-emitting layer. By its mixed crystallinity, the light-emitting wavelength can be arbitrarily changed from about 365 nm to 650 nm. Examples of the structure of the LED chip 5 include those having a homogeneous structure, a heterostructure, or a double heterostructure, such as a MIS junction, a PIN junction, or a pn junction. Any of them can be used in the present invention. Double heterostructure. In addition, depending on the semiconductor composition or mixed crystallinity constituting the light-emitting layer (active layer), various light-emitting wavelengths can be selected. Alternatively, a single quantum well structure or a multiple quantum well structure composed of a thin film that generates a quantum effect in the active layer may be formed. When a nitride semiconductor LED wafer 5 is used, sapphire, spinel, SiC, Si, ZnQ and other materials can be used as the substrate. However, in order to form a nitride semiconductor with good crystallinity with good mass productivity, a sapphire substrate is suitable. A nitride semiconductor can be formed on this sapphire substrate using a MOCVD method or the like. At this time, it is preferable to form a buffer layer such as GaN, AIN, GaAIN, etc. on the sapphire substrate and grow a nitride semiconductor layer having a pn junction thereon. An example of an LED wafer having a pn junction using a nitride semiconductor is to form a buffer layer on a sapphire substrate, and make the n-type nitride on the buffer layer. The 19-i paper size is applicable to the Chinese Standard (CNS). A4 size (210 X 297 mm) " Binding

554547 A7 ------- -B7 五、發明說明（17 ) 嫁形成之第1接觸層，以11型氮化鋁/鎵所形成之第1覆蓋 層、以氮化銦/鎵所形成之活性層、以p型氮化鋁/鎵所形成 <第2覆蓋層、以p型氮化鎵所形成之第2接觸層依序積層 而形成之雙異質構造的LED晶片。 氮化物半導體係以不摻雜雜質之狀態顯示η型導電性， 但’為形成所希望之η型氮化物半導體，宜適當導入Si、 Ge、Se、Te、C等作為η型摻雜物，為形成p型氮化物半導 體’係摻雜ρ型摻雜物即Zn、_Mg、Be、Ca、Sr、Ba等。 又’氮化物半導體只摻混p型摻雜物很難p型化，故p型摻 雜物導入後’宜藉爐進行加熱或電漿照射等使之低電阻 化。如此地依序形成特定之氮化物半導體層後，於特定位 置形成電極之晶圓切成晶片狀，可製作一使用氮化物半導 體之LED晶片5。 在本實施形態1之發光二極體中，使白色系之光發光時， 考慮與來自螢光物質之發光波長的補色關係或透光性樹脂 的劣化防止等，LED晶片5之發光波長宜設定於400 nm以上 530 nm以下’更宜設定於420 nm以上490 nm以下。為提高 LED晶片本身之發光效率且提昇螢光物質激發所引起的發 光效率，進一步宜將LED晶片5半導體之發光波長設定於 450 nm以上475 nm以下。又，在本發明中藉由選擇勞光體 之種類，亦可適用一發出比4〇〇 nm還短之紫外線區域波長 的光之LED晶片。 使用藍寶石或尖晶石等絕緣性基板之氛化物半導體lED 晶片’係為於半導體表面側形成p型及η型用之電極，蝕刻 -20- 本纸張尺度適用中國國家標準(CNS) Α4規格(210X 297公釐） 554547 A7 __— _B7_ 五、發明説明（Μ ) P型半導體而使η型半導體露出，分別於p型半導體層及^型 半導體層使用濺鍍法或真空蒸鍍法等而形成特定形狀之各 電極。從半導體側取出光時，形成於ρ型半導體層之全面的 電極，係作為由金屬薄膜所構成之透光性電極。 <螢光物質> 螢光物質之比重達到硬化前之液狀樹脂的數倍。又，熱 硬化性樹脂當加熱硬化時，黏度會大幅降低。因此，以含 有螢光物質之液狀樹脂覆蓋LED晶片並進行熱硬化，樹脂 中之螢光物質的幾乎全部有密集集結於LED晶片周邊而沉 澱之傾向。 如此密集集結而沉澱之螢光物質係疊合而沉澱於led晶 片5之周邊，故，可有效率地吸收來自LED晶片之光乃只限 於在LED晶片表面附近之螢光物質。因此，多數之螢光物 質係不充分發揮波長之變換功能，反之，遮蔽其他螢光物 質經過波長變換之光而僅作用於使光之能量衰減。其結 果，引起發光二極體之發光輸出的降低。 因此，本發明中係使用一種於全部螢光物質發揮波長變 換功能並可呈最大限活用之具有特定粒度分布的螢光物 質，謀求發光二極體之輸出提昇。 具體上，用於本實施形態1之發光二極體的螢光物質係包 括大粒徑螢光物質8 1之集合體（第1分布）與小粒徑螢光物 質82的集合體（第2分布）’第1分布與第2分布之間係存在 於螢光物質幾乎不存在之區域。本發明中，藉由使用如此 分布之螢光物質，可防止一對光學特性有不良影響之凝集 -21 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) ' " 554547 A7 B7 五、發明説明（19 ) 體的形成，且，防止發光色之色不均。圖2八、23中，顯 示在本實施形態1中所使用之螢光物質的體積基準黏度分布 曲線。圖2A表示各粒徑中之加算分布，圖2B係表示在各 粒徑之頻度分布。 如圖2A所示般，本發明所使用之螢光物質係於體積基準 分布曲線中，具有加算值001 v〇l〇/0〜10 v〇l%之間斜率為 零之平坦區域。此平坦區域係位於上述第1分布與第2分布 之間，螢光物質幾乎未分布之i立徑範圍（區域）。 此處，在本實施形態1中，小粒徑螢光物質8 2之含量為螢 光物質全體之〇.〇1 vol%〜1〇 vol%，大粒徑螢光物質81之 含量為螢光物質全體之9 0 vol %以上。在本發明中，更佳 之小粒徑螢光物質的含量為〇·〇1 v〇l%〜5 vol%。如此，使 小粒徑螢光物質成為少量，可防止色不均，同時並以不遮 蔽來自LED晶片及大粒徑螢光物質之光的方式可配置於樹 脂中。 又，大粒徑螢光物質8 1之頻度波峰粒徑值宜設定成小粒 徑螢光物質82之頻度波峰值的20倍〜90倍。如此，藉由增 大粒徑差，在發光二極體中，以各別螢光物質呈最大限活 用各別作用（小粒徑螢光物質8 2主要為散射功能，大粒徑螢 光物質8 1主要為波長變換功能）之方式進行配置。 亦即’小粒徑勞光物質8 2係光變換效率低，但，可反射 擴散光，藉此可防止發光色之色不均。因此，小粒徑螢光 物質宜在透光性樹脂中並非沉澱於LED晶片周邊而分散。 在本發明所使用之小粒徑螢光物質係調整成極少量且與 •22- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)554547 A7 ------- -B7 V. Description of the invention (17) The first contact layer formed by marrying, the first cover layer formed by 11-type aluminum nitride / gallium, and the indium nitride / gallium A double heterostructure LED wafer formed by sequentially stacking an active layer, a second cover layer formed of p-type aluminum nitride / gallium, and a second contact layer formed of p-type gallium nitride. Nitride semiconductors exhibit n-type conductivity in a state where they are not doped with impurities. However, in order to form a desired n-type nitride semiconductor, Si, Ge, Se, Te, C, etc. should be appropriately introduced as n-type dopants. To form a p-type nitride semiconductor, a doped p-type dopant, that is, Zn, _Mg, Be, Ca, Sr, Ba, etc. It is difficult to p-type a nitride semiconductor only by mixing a p-type dopant. Therefore, after the p-type dopant is introduced, it is preferable to reduce the resistance by heating it with a furnace or plasma irradiation. After the specific nitride semiconductor layer is sequentially formed in this way, the wafer on which electrodes are formed at specific positions is cut into a wafer shape, and an LED wafer 5 using a nitride semiconductor can be manufactured. In the light-emitting diode of the first embodiment, when the white light is emitted, it is desirable to set the light-emitting wavelength of the LED chip 5 in consideration of the complementary color relationship with the light-emitting wavelength from the fluorescent substance or the prevention of deterioration of the translucent resin. Above 400 nm and below 530 nm 'is more preferably set above 420 nm and below 490 nm. In order to improve the luminous efficiency of the LED chip itself and the luminous efficiency caused by the excitation of the fluorescent substance, it is further suitable to set the luminous wavelength of the semiconductor of the LED chip 5 to 450 nm to 475 nm. In addition, in the present invention, by selecting the type of the laborer, an LED chip that emits light having a wavelength in the ultraviolet region shorter than 400 nm can also be applied. Affinity semiconductor lED wafers using insulating substrates such as sapphire or spinel are used to form p-type and η-type electrodes on the surface of the semiconductor, and are etched -20- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 554547 A7 __— _B7_ V. Description of the invention (M) P-type semiconductor and n-type semiconductor are exposed, and the p-type semiconductor layer and the ^ -type semiconductor layer are sputtered or vacuum deposited, etc. Each electrode is formed into a specific shape. When light is taken out from the semiconductor side, the entire electrode formed on the p-type semiconductor layer serves as a light-transmitting electrode composed of a metal thin film. < Fluorescent substance > The specific gravity of the fluorescent substance is several times that of the liquid resin before curing. In addition, the viscosity of a thermosetting resin is greatly reduced when it is cured by heating. Therefore, the LED chip is covered with a liquid resin containing a fluorescent substance and is thermally hardened. Almost all of the fluorescent substance in the resin tends to be densely concentrated around the LED chip and precipitate. Such densely packed and precipitated fluorescent substances are superimposed and deposited on the periphery of the LED chip 5. Therefore, the efficient absorption of light from the LED chip is limited to the fluorescent substance near the surface of the LED chip. Therefore, most fluorescent substances do not fully perform the wavelength conversion function. On the contrary, they shield the other fluorescent substances from the wavelength-converted light and only act to attenuate the energy of the light. As a result, the light-emitting output of the light-emitting diode is reduced. Therefore, in the present invention, a fluorescent substance having a specific particle size distribution that exhibits a wavelength conversion function for all fluorescent substances and can be used to the maximum extent is used to improve the output of a light emitting diode. Specifically, the fluorescent substance used in the light-emitting diode of the first embodiment includes an aggregate (first distribution) of a large-size fluorescent substance 81 and an aggregate (small-size fluorescent substance 82) (second Distribution) 'The first distribution and the second distribution exist in a region where fluorescent substances hardly exist. In the present invention, by using the fluorescent substance thus distributed, it is possible to prevent agglomeration of a pair of optical characteristics having an adverse effect. -21-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) '" 554547 A7 B7 V. Description of the invention (19) The formation of the body and the prevention of uneven color of the luminous color. Figures 28 and 23 show the volume-based viscosity distribution curve of the fluorescent substance used in the first embodiment. Fig. 2A shows the added distribution of each particle diameter, and Fig. 2B shows the frequency distribution of each particle diameter. As shown in FIG. 2A, the fluorescent substance used in the present invention is in a volume-based distribution curve, and has a flat region with a slope of zero between an added value of 001 v0l0 / 0 to 10 v0l%. This flat area is located between the first distribution and the second distribution, and the vertical diameter range (area) where the fluorescent substance is hardly distributed. Here, in the first embodiment, the content of the fluorescent material 82 with a small particle size is 0.001 vol% to 10 vol% of the entire fluorescent material, and the content of the fluorescent material 81 with a large particle size is fluorescent. More than 90 vol% of all substances. In the present invention, it is more preferable that the content of the fluorescent material having a small particle diameter is from 0.001 to 5 vol%. In this way, a small amount of the fluorescent material with a small particle diameter can be prevented, and color unevenness can be prevented. At the same time, it can be arranged in the resin so as not to shield the light from the LED chip and the large particle fluorescent material. In addition, the frequency peak particle size value of the large-size fluorescent substance 81 is preferably set to 20 to 90 times the frequency peak value of the small-size fluorescent substance 82. In this way, by increasing the particle size difference, in the light-emitting diode, the individual fluorescent materials are used to the maximum limit and the individual functions are used (the small-particle fluorescent material 8 2 is mainly a scattering function, and the large-particle fluorescent material is used. 8 1 is mainly configured by the wavelength conversion function). In other words, the 'small-grained gloss material 8 2 series has low light conversion efficiency, but can reflect diffused light, thereby preventing color unevenness of the emitted color. Therefore, it is desirable that the small-sized fluorescent substance is dispersed in the translucent resin instead of being deposited on the periphery of the LED chip. The small particle size fluorescent substance used in the present invention is adjusted to a very small amount and is in accordance with the standard of China National Standard (CNS) A4 (210 X 297 mm).

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554547 A7 B7 五、發明説明（2〇 ) 大粒徑螢光物質之粒徑分開的很小粒徑，藉此，可得到在 透光性樹脂中小粒徑螢光物質良好地分散之發光二極體。 小粒徑螢光物質82之粒徑宜為0.2 /zm〜1·5 之範圍。藉 此，可抑制各小粒徑螢光物質凝集且可有效發揮光之散亂 功能。又，具有前述範圍之粒徑的小粒徑螢光物質82在未 硬化之透光性樹脂中幾乎未沉殿，故，可與大粒徑勞光物 質8 1分離而配置。亦即，由大粒徑螢光物質8丨與小粒徑榮 光物質82所構成之本發明螢光物質，係於被覆LED晶片5 之透光性樹脂中，大粒徑螢光物質8 1存在於LED晶片5之 接近部分，在其外側小粒徑螢光物質82幾乎均一分散而存 在。在如此所分散之螢光物質中，大粒徑螢光物質8丨係以 使來自LED晶片5之光波長變換的方式作用，其外側之小粒 徑螢光物質82係藉其反射功能防止發光色之色不均的方式 作用。 又，於前述小粒徑螢光物質82與大粒徑螢光物質81之間 亦可含有頻度波奪之中粒徑螢光物質。為波長變換之光要 全部被大粒徑螢光物質吸收而變換乃很困難《大粒徑勞光 物質8 1係被表面積大的成分、粒徑大的螢光物質所反射之 光仍存在。因此，使大粒徑螢光物質8 1與比大粒徑勞光物 質8 1粒徑還小且比小粒徑螢光物質8 2還大的中粒徑勞光物 質共存，且不斷被大粒徑螢光物質8 1吸收之光，係使之被 前述中粒徑螢光物質吸收且色變換。如此，藉由有效地使 於大粒徑螢光物質之表面完全被反射且來自LED晶片之光 進行色變換，可以最小限之螢光物質含量得到所希望之色 -23- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 一---^554547 A7 B7 V. Description of the invention (20) The particle diameter of the large-size fluorescent substance is separated to a very small particle diameter, thereby obtaining a light-emitting diode in which the small-size fluorescent substance is well dispersed in the translucent resin. body. The particle diameter of the small particle fluorescent substance 82 is preferably in the range of 0.2 / zm to 1.5. This suppresses the aggregation of fluorescent materials with small particle diameters, and effectively exerts the light scattering function. In addition, since the small-particle-size fluorescent substance 82 having the particle diameter in the aforementioned range is hardly settled in the non-hardened light-transmitting resin, it can be arranged separately from the large-particle-type polished substance 81. That is, the fluorescent substance of the present invention, which is composed of a large particle size fluorescent substance 8 丨 and a small particle size glory substance 82, is a light-transmitting resin covering the LED chip 5, and a large particle size fluorescent substance 81 exists. In the near portion of the LED wafer 5, a small-particle-size fluorescent substance 82 is almost uniformly dispersed on the outer side and exists. Among the fluorescent substances dispersed in this way, the large-sized fluorescent substance 8 is used to convert the wavelength of light from the LED chip 5, and the small-sized fluorescent substance 82 on the outer side prevents light emission by its reflection function. The color uneven effect works. Further, a medium-sized fluorescent substance having a frequency of pulsation may be contained between the small-sized fluorescent substance 82 and the large-sized fluorescent substance 81. It is difficult for wavelength-converted light to be absorbed by a large-sized fluorescent substance and converted. "Large-sized light-emitting substance 81 is still reflected by components with large surface areas and large-sized fluorescent substances. Therefore, the large-sized fluorescent substance 81 and the medium-sized fluorescent substance having a smaller particle size than the large-sized fluorescent substance 81 and the larger-sized small-sized fluorescent substance 8 2 coexist, and are continuously being enlarged. The light absorbed by the particle size fluorescent substance 81 is absorbed by the aforementioned medium particle size fluorescent substance and undergoes color conversion. In this way, by effectively reflecting the surface of the large-size fluorescent substance completely and performing color conversion of the light from the LED chip, the desired color can be obtained with the minimum fluorescent substance content. National Standard (CNS) A4 Specification (210 X 297 mm) One --- ^

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554547 A7 _______ B7 五：：發明説明（21 ) 調，並提高輝度。前述中粒徑螢光物質係前述大粒徑螢光 物質81之0.3倍〜0.9倍，更佳係具有〇·5倍〜〇·8倍之中心粒 徑，藉此，可有效地吸收於前述大粒徑螢光物質的表面被 反射之光應進行色變換。 一般，螢光物質係粒徑愈大光變換效率愈高。本發明之 發光二極體係進一步設定成如後述大粒徑螢光物質8丨之粒 度分布’以免於LED晶片5之周邊互相重叠之方式配置大粒 徑螢光物質8 1，使來自LED晶片5之光有效率地被全部之 大粒徑螢光物質8 1吸收並使光變換。 亦即，本發明之螢光物質中，具有大粒徑之大粒徑螢光 物質81 ,係如圖4A，4B所示般分布，故於樹脂中互相重 疊、緻达、凝集者幾乎無，並具有較佳之間隔而沉殿。因此， 從LED晶片5所發出之光，並非只有接近LED晶片5之大粒 徑螢光物質81，而可將光導入全部之大粒徑螢光物質81。 藉此，可使更多之螢光物質幫助變換，提高各螢光物質之 光吸收率及變換效率。 亦即，使用粒徑未適當管理之習知螢光物質，而為得到 所希望之光，必須於樹脂中含有大量之螢光物質，因螢光 物質層會變厚且互相重疊，無助於光變換之螢光物質的比 例會增加，藉由不使其光變換之螢光物質，光會被遮蔽之 傾向。因此，習知者係取出效率差，且無法得到高輝度。 然而，如本發明般，若使用其平均粒徑與粒度分布被管理 之大粒徑螢光物質81 ,前述大粒徑螢光物質81會密集重疊 而沉激之機率很低，可比習知更粗地使大粒徑螢光物質81554547 A7 _______ B7 Five: Description of the invention (21) Tune and increase the brightness. The medium particle size fluorescent substance is 0.3 to 0.9 times the size of the large particle size fluorescent substance 81, and more preferably has a center particle size of 0.5 to 0.8 times, thereby effectively absorbing the aforementioned particle size. The light reflected on the surface of the large-size fluorescent substance should undergo color conversion. Generally, the larger the particle size of the fluorescent substance system, the higher the light conversion efficiency. The light-emitting diode system of the present invention is further set to a particle size distribution of the large-sized fluorescent substance 8 丨 as described later, so that the large-sized fluorescent substance 81 is arranged so that the periphery of the LED chip 5 does not overlap with each other, so that the LED chip 5 The light is efficiently absorbed and converted by all the large-particle-size fluorescent substances 81. That is, among the fluorescent substances of the present invention, the large-particle-size fluorescent substance 81 having a large particle diameter is distributed as shown in FIGS. 4A and 4B, so there is almost no overlap, reach, and agglutination in the resin. And has a better interval while sinking. Therefore, the light emitted from the LED chip 5 is not only the large-diameter fluorescent substance 81 close to the LED chip 5, but light can be introduced into the entire large-particle fluorescent substance 81. In this way, more fluorescent substances can help the conversion, and the light absorption rate and conversion efficiency of each fluorescent substance can be improved. That is, a conventional fluorescent substance whose particle diameter is not appropriately controlled is used, and in order to obtain the desired light, a large amount of fluorescent substance must be contained in the resin, because the fluorescent substance layers will become thick and overlap each other, which is not helpful The proportion of light-transmitting fluorescent substances will increase, and the light-transmitting fluorescent substances will tend to be shielded. Therefore, the conventional system has poor extraction efficiency and cannot obtain high luminance. However, as in the present invention, if a large particle size fluorescent substance 81 whose average particle size and particle size distribution are controlled is used, the probability that the large particle size fluorescent substance 81 will overlap and become very low is much higher than conventional. Roughly make large particle size fluorescent substance 81

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五、發明説明（22 ) 分散，從各螢光物質至發光面之距離亦可比較短，故，傲 換後之光不會被樹脂吸收而直接維持南輝度並有效率地取 出於外部。 以上乃設定本發明之大粒徑螢光物質8丨分布之基本邦、 法。 “ 如此，在本發明中，係使用由大粒徑螢光物質8丨與小粒 從螢先物質8 2所構成的螢光物質，進一步使朝外部之光取 出效率、光吸收效率、光變換效率提昇，故，以良好的間 隔將大粒徑螢光物質8 1配置於LED晶片5之周邊而成為色 變換層，俾得到一可高光度及高輸出之發光二極體。 於本發明所使用之大粒徑螢光物質8 1的粒徑，為使朝外 部之光取出效率、光吸收效率、光變換效率提昇，宜設定 於10 /zm〜60 之範圍，更宜設定於1〇 em〜5〇 之範 圍’最佳係設定於15 〜30 具有比1〇 還小且 比前述小粒徑螢光物質82還大的粒徑之螢光物質，係易形 成凝集體，在液狀樹脂中成為密集而沉澱，故減少光之穿 透效率。具有比15私m還小且比前述小粒徑螢光物質82還 大的粒徑之螢光物質，係比15 以上者更易形成凝集 體，若製造步驟上之管理不足，在液狀樹脂中會變成密集 而沉澱，故有減少光之穿透效率之虞。 又，大粒徑螢光物質之粒度整齊一致較佳，藉此，更可 有效防止大粒徑螢光物質密集沉澱。大粒徑螢光物質之粒 度分布的標準偏差，係無特別分級，可設定於較佳之範圍 即0·3以下。藉進一步分級，亦可設定於〇15以下（本發明 ____-25- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公€ 554547 A7V. Description of the invention (22) Dispersion, the distance from each fluorescent substance to the light-emitting surface can also be relatively short, so the light after the replacement will not be absorbed by the resin, and the south brightness will be directly maintained and efficiently taken from the outside. The above is the basic method for setting the distribution of the large-sized fluorescent substance 8 in the present invention. “In this way, in the present invention, a fluorescent substance composed of a large-sized fluorescent substance 8 丨 and a small particle from the fluorescent substance 8 2 is used to further improve the light extraction efficiency, light absorption efficiency, and light conversion efficiency to the outside. It is improved, therefore, the large-diameter fluorescent substance 81 is arranged around the LED chip 5 at a good interval to become a color conversion layer, and a light-emitting diode capable of high luminosity and high output is obtained. Used in the present invention The particle size of the large-size fluorescent substance 81 is preferably set to a range of 10 / zm ~ 60, and more preferably 10em ~, in order to improve the light extraction efficiency, light absorption efficiency, and light conversion efficiency toward the outside. The range of 50 ′ is optimally set to 15 to 30. The fluorescent substance having a particle diameter smaller than 10 and larger than the aforementioned small-sized fluorescent substance 82 is easy to form agglomerates, and is in a liquid resin. It becomes dense and precipitates, so it reduces the light penetration efficiency. Fluorescent substances with a particle size smaller than 15 μm and larger than the aforementioned small-sized fluorescent substance 82 are more likely to form aggregates than 15 or more. If the management of the manufacturing steps is insufficient, it will become It is dense and precipitated, so there is a risk of reducing the penetration efficiency of light. In addition, the particle size of the large-size fluorescent substance is better and uniform, which can effectively prevent the dense-grained fluorescent substance from being densely precipitated. The standard deviation of the particle size distribution of light substances has no special classification, and can be set to a better range, that is, less than 0 · 3. By further classification, it can also be set to less than 015 (the present invention ____- 25- This paper scale is applicable to China National Standard (CNS) Α4 size (210 X 297 public € 554 547 A7

人等經確認藉分級可製作標準偏差〇 ·丨3 5之大粒徑螢光物 質）。 在本發明中，係藉由使用如此之大粒徑螢光物質，可抑 制螢光物質遮蔽光並提昇發光二極體之輸出。又，在本發 明所使用之大粒徑螢光物質的材料，係宜光之吸收率及變 換效率高且激發波長幅寬廣。 如此，使一具有光學優異之特徵（所謂光之吸收率及變換 效率高且激發波長幅寬廣的特-徵）的大粒徑螢光物質8丨於全 螢光物質中含有90 vol%以上，可使LED晶片之主波長周邊 的光良好地變換而發出波長相異之光，亦可提昇發光二極 體之量產性。 如此，本發明之發光二極體係藉由使用上述之螢光物 質’以分離配置成：分散於遠離樹脂中之LED晶片5的部分 且由小粒徑螢光物質82所構成之具有光擴散功能的層； 及’於LED晶片5之周邊具有良好間隔而沉澱且由大粒徑螢 光物質8 1所構成之色變換層。藉此而若依本發明，可得到 一種可無色不均且均一地發出高輸出且高光度之光的發光 二極體。 此處’在本發明中，螢光物質之粒徑係以體積基準粒度 分布曲線所得到之值來表示。又，體積基準粒度分布曲線 係依雷射繞射、散射法來測定螢光物質之粒度分布而得 到。具體上，在氣溫25°C、濕度70%之環境下，使螢光物 質分散於濃度為〇·〇5%之六偏磷酸鈉水溶液，藉雷射繞射 式粒度分布測定裝置（SALD-2000A)，在粒徑範圍〇.〇3 -26- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)It has been confirmed by humans and others that a large particle size fluorescent material with a standard deviation of σ · 35 can be produced by classification). In the present invention, by using such a large-diameter fluorescent substance, it is possible to suppress the fluorescent substance from blocking light and improve the output of the light-emitting diode. In addition, a material having a large particle size for a fluorescent substance used in the present invention is preferable because it has high absorption and conversion efficiency of light and a wide excitation wavelength. In this way, a large-particle-size fluorescent substance 8 having excellent optical characteristics (the so-called characteristic of high light absorption and conversion efficiency and wide excitation wavelength range) is contained in the entire fluorescent substance at 90 vol% or more. The light around the main wavelength of the LED chip can be converted well to emit light with different wavelengths, and the mass production of the light emitting diode can be improved. In this way, the light-emitting diode system of the present invention is separated and configured by using the above-mentioned fluorescent substance 'to be dispersed in a portion far from the LED chip 5 in the resin and composed of a small-diameter fluorescent substance 82 having a light-diffusing function. And a color conversion layer composed of a fluorescent material 81 having a large particle diameter and deposited at a good interval around the periphery of the LED chip 5. Therefore, according to the present invention, a light-emitting diode capable of emitting light with high output and high luminosity uniformly and colorlessly can be obtained. Here, in the present invention, the particle size of the fluorescent substance is represented by a value obtained by a volume-based particle size distribution curve. The volume-based particle size distribution curve is obtained by measuring the particle size distribution of a fluorescent substance by laser diffraction and scattering methods. Specifically, the fluorescent substance is dispersed in a sodium hexametaphosphate aqueous solution having a concentration of 0.05% under an environment of an air temperature of 25 ° C and a humidity of 70%, and a laser diffraction particle size distribution measuring device (SALD-2000A) is used. ), In the range of particle size 0.03 -26- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)

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〜700 之範圍進行測定而得到者。 在本發明中，所謂螢光物質之中心粒徑在前述體積基準 粒度分布曲線中加算值為5〇 v〇1%時之粒徑值，宜為丨5 〜50 範圍。又，宜含有具此中心粒徑值之螢光物質為 頻度向者’頻度值宜為20%〜50%。如此，藉由使用粒徑 <參差不齊很小的螢光物質，可得到一種色不均被抑制且 具有良好對比色之發光二極體。 亦即，大粒徑螢光物質8丨與粒徑比此還小之螢光物質比 較而有易造成發光二極體之色不均的傾向，但，在大粒徑 螢光物質8 1中若粒徑之參差不齊很小，會比參差不齊大者 更可改善色不均。 在本發明之發光二極體中，螢光物質宜使用一種可激發 從一以氮化物系半導體作為發光層之半導體j^ED晶片所發 出之光而發光的鈽，以此鈽所賦活之釔/鋁氧化物系螢光物 負作為基礎者。 具體之允/鋁氧化物系螢光物質可舉例：YAl〇3 : c e、 Y3A15012 : Ce(YAG : Ce)或 y4ai2〇9 : Ce ,進一步為此等 之混合物等。於Y/A1氧化物系螢光物質中亦可含有Ba、Measured in the range of ~ 700. In the present invention, the particle diameter value of the so-called center particle diameter of the fluorescent substance when the added value in the aforementioned volume-based particle size distribution curve is 50 v0%, and preferably in the range of 5 to 50. In addition, it is desirable to include a fluorescent substance having such a central particle size value as a frequency direction 'frequency value is preferably 20% to 50%. In this way, by using a fluorescent substance having a small particle diameter < unevenness, a light emitting diode with suppressed color unevenness and a good contrast color can be obtained. That is, the large particle size fluorescent substance 8 丨 tends to cause color unevenness of the light emitting diode compared with the fluorescent material having a smaller particle size. However, in the large particle size fluorescent substance 81, If the variation in particle size is small, the color unevenness can be improved more than the variation in particle size. In the light-emitting diode of the present invention, the fluorescent substance is preferably a kind of yttrium which can excite light emitted from a semiconductor j ^ ED wafer having a nitride-based semiconductor as a light-emitting layer, and the yttrium activated by this ytterbium / Aluminum oxide-based fluorescent materials as the basis. Specific allowable / aluminum oxide-based fluorescent materials can be exemplified by YAlO3: ce, Y3A15012: Ce (YAG: Ce) or y4ai2O9: Ce, and further mixtures thereof. Y / A1 oxide fluorescent materials may also contain Ba,

Sr、Mg、Ca、zn之至少一種。又，含有si而可抑制結晶 成長之反應，並整齊螢光物質之粒子。 在本說明書中，被Ce賦活之釔/鋁氧化物系螢光物質係特 別廣義解釋者，含有以下之螢光物質。 (1)在釔/鋁氧化物系螢光物質中，釔之一部分或全體乃 被至：/種選自Lu、Sc、La、Gd及Sm之元素所取代的螢At least one of Sr, Mg, Ca, and zn. In addition, it contains si, which suppresses the reaction of crystal growth and neatly aligns the particles of the fluorescent substance. In this specification, the yttrium / aluminum oxide-based fluorescent substance activated by Ce is particularly interpreted broadly and includes the following fluorescent substances. (1) In the yttrium / aluminum oxide-based fluorescent substance, a part or the whole of yttrium is replaced by:

554547 A7 B7 五 發明説明（25 ) 光物質。 (2) 在釔/鋁氧化物系螢光物質中，鋁之一部分或全部乃 被至少一種選自Ba、Tl、Ga、In之元素所取代的勞光物 (3) 在釔/鋁氧化物系螢光物質中，釔之一部分或全部乃 被至少一種選自Lu、Sc、La、Gd、及Sm之元素所取代、 且、銘之一部分或全體乃被至少一種選自Ba、Tl、Ga、 In之元素所取代的螢光物質。-. 更詳而言之，係以通式（YzGdi.z)3Al5〇i2 : Ce(但，〇<ζ$ 1)所示之光激發光螢光體或以通式（RehSmahRe’sOu ·· Ce (但，0Sa<l、OSbSl、Re係至少一種選自 Y、Gd、 La、Sc，Re1係至少一種選自A1、Ga、In)所示之光激發 光螢光體。 此螢光物質係因石榴石構造，對熱、光及水分感應很 強，可使激發光譜之波辛在450 nm附近，發光波峰亦在5 80 nm附近，擁有至700 nm可拉出一條尾線之發光光譜。 又，光激發光螢光體係於結晶中含有Gd(Cadmium)，可 提高460 nm以上之長波長域的激發發光效率。藉Cd之含量 增加，發光波峰波長會移動至長波長，全體之發光波長亦 偏移至長波長側。亦即，必須為紅色很強之發光色時，可 以增多Cd之置換量來達成。另外，Cd增加同時並且藍色光 引起之光激發光的發光輝度有下降之傾向。進一步，可依 照所希望而加入Ce，亦可含有Tb、Cu、Ag、Au、Fe、 Cr、Nd、Dy、Co、Ni、Ti、Eu 等。 -28 - 本紙張尺度適用中國國家標準(CNS) A4規格(210x 297公釐)554547 A7 B7 V. Description of the invention (25) Light matter. (2) In the yttrium / aluminum oxide-based fluorescent substance, a part or all of aluminum is replaced by at least one element selected from Ba, Tl, Ga, and In. (3) In the yttrium / aluminum oxide In the fluorescent materials, a part or all of yttrium is replaced by at least one element selected from Lu, Sc, La, Gd, and Sm, and a part or all of yttrium is replaced by at least one selected from Ba, Tl, Ga The fluorescent substance replaced by the element of In. -. More specifically, it is a light-excitation photoluminescent phosphor represented by the general formula (YzGdi.z) 3Al50〇i2: Ce (but, 〇 < ζ $ 1) or a general formula (RehSmahRe'sOu · Ce (however, 0Sa < l, OSbSl, Re is at least one selected from the group consisting of Y, Gd, La, and Sc, and Re1 is at least one selected from the group consisting of A1, Ga, and In.). Due to the garnet structure, the material is highly sensitive to heat, light and moisture, which can make the wave spectrum of the excitation spectrum near 450 nm and the light emission peak near 5 80 nm. It has a tail light emission up to 700 nm. In addition, the photo-excitation fluorescence system contains Gd (Cadmium) in the crystal, which can increase the excitation luminous efficiency in the long wavelength range above 460 nm. By increasing the content of Cd, the wavelength of the luminous peak will move to a long wavelength, and the whole The emission wavelength is also shifted to the long wavelength side. That is, when it is necessary to have a strong red emission color, the amount of Cd replacement can be increased to achieve it. In addition, the Cd increases and the luminous brightness of the photoexcitation light caused by blue light decreases. Furthermore, Ce may be added as desired, and Tb, Cu, Ag, Au, and Fe may be added. Cr, Nd, Dy, Co, Ni, Ti, Eu, etc. -28-- This paper scales applicable Chinese National Standard (CNS) A4 size (210x 297 mm)

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554547 A7 _____ B7 五、發明説明（26 ) 而且’擁有石梢石構造之釔/鋁/石榴石系螢光體之組成 中’以Ga取代A1之一部分，發光波長會偏移至短波長側。 又，以Gd取代組成之γ的一部分，發光波長會偏移至長波 長側。 以Gd取代γ之一部分時，對Gd之取代成為1成以下， 且，苴使C e之含有（取代）形成於〇 〇3〜^對〇 d之取代為 2成以下，則綠色成分為變大，紅色成分會變少，但，增加 Ce又含量可補充紅色成分，不會使輝度降低，可得到所希 望之色調。若形成如此之組成，溫度特性會變良好，可提 昇發光二極體之信賴性。又，若使用一調整成具有很多紅 色成分般的光激發光螢光體，能製作一種可使橙色等之中 間色的發光二極體。 如此之光激發光螢光體係可如下般製作。首先，使用氧 化物、或在高溫下容易變成氧化物之化合物作為γ、G d、 及Ce之原料，將此等以化學計量比充分混合而得到原 料或，將Y、Cd、Ce之稀土族元素以化學計量比溶解於 酸之溶解液，使其以存酸共沉澱，再燒成所得到之共沉氧 化物，將此共沉氧化物與氧化鋁混合而得到混合原料。於 其中再適量混合氟化鋇或氟化鋁等之氟化物作為助熔劑而 填塞於坩鍋中，在空氣中、135〇〜145〇t之溫度範圍燒成 2 5 j時而彳于到燒成品，其次，將燒成品於水中進行球研 磨’而洗淨、分離、乾燥、最後通過篩而得到。 在本發明之發光二極體中，如此之光激發光螢光體，係 亦可混合一被2種以上之鈽賦活的釔/鋁/石榴石等螢光體或 _ __-29· 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 554547 A7 — __ —_B7 五、發明説明（—2〇 — 其他之榮光體。 藉由混合從Y朝Gd之置換量相異之二種類的釔/鋁/石榴 石系螢光體，可很容易實現成為所希望之色調的光。尤 其，若以前述置換量很多之螢光物質作為上述大粒徑螢光 物質，以前述置換量很少或零之螢光物質作為上述中粒徑 螢光物質，則可同時實現演色性及輝度之提昇。 (透光性樹脂） 透光性樹脂8係使相對於環氧當量為〇 〇〇5〜15莫耳之酸 酐或二羧酸對6 5重量％以上由脂環式環氧樹脂所構成的環 氧樹脂而成為交聯寡聚物，於其交聯寡聚物中混合少量之 陽離子硬化劑（有關環氧當量為〇·〇〇〇〇5〜〇 〇〇3莫耳，宜為 0.0001〜0.01莫耳）的溶液，塗布於一收藏有氮化物半導體 LED晶片5之收藏部1 a的内部後，進行加熱硬化以形成。 如此所形成之透光性樹脂8因吸收藍色光之陽離子硬化劑 的含量為習知之1 /1 〇至1 /1 〇〇的量，故樹脂之黃變幾乎不 成問題。因此，以可藍色發光之氮化物半導體LED晶片5的 發光及螢光物質所波長變換的光，可高效率地輸出至外 部。又，透光性樹脂8因具有比較高的可能性，故，可缓和 透光性樹脂8與LED晶片5之熱膨脹係數相異而產生的應 力，而防止於氮化物半導體LED晶片5之龜裂發生，或引線 7之切斷的不良。 以下，詳細說明有關一用於透光性樹脂8之環氧樹脂組合 物的組成。 構成透光性樹脂8之環氧樹脂組合物係以脂環式環氧樹脂 •30- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 554547 A7554547 A7 _____ B7 V. Description of the invention (26) Moreover, in the composition of yttrium / aluminum / garnet-based phosphor with stone-stone structure, replacing part of A1 with Ga, the emission wavelength will shift to the short wavelength side. In addition, when Gd is substituted for a part of the composition γ, the emission wavelength is shifted to the long wavelength side. When Gd is substituted for a part of γ, the substitution of Gd becomes 10% or less, and if the content (substitution) of Ce is formed to 〇03 ~ ^ The substitution of 〇d is 20% or less, the green component is changed. Larger, the red component will be reduced, but increasing the Ce content can supplement the red component without reducing the brightness, and can obtain the desired hue. If such a composition is formed, the temperature characteristics will be improved, and the reliability of the light emitting diode can be improved. In addition, if a light-excited phosphor adjusted to have a lot of red components is used, a light-emitting diode capable of producing intermediate colors such as orange can be produced. Such a light-excitation fluorescence system can be produced as follows. First, an oxide or a compound that easily becomes an oxide at a high temperature is used as a raw material of γ, G d, and Ce, and these are sufficiently mixed at a stoichiometric ratio to obtain a raw material or a rare earth group of Y, Cd, and Ce The elements are dissolved in the acid solution with a stoichiometric ratio, co-precipitated with the stored acid, and the co-precipitated oxide obtained is fired, and the co-precipitated oxide is mixed with alumina to obtain a mixed raw material. A suitable amount of fluoride, such as barium fluoride or aluminum fluoride, is filled in the crucible as a flux, and it is burned in the air at a temperature range of 135 to 1450 t for 2 5 j. The finished product is then ball-milled in water, washed, separated, dried, and finally obtained by sieving. In the light-emitting diode of the present invention, such a light-excitation light-emitting phosphor can also be mixed with a phosphor such as yttrium / aluminum / garnet activated by two or more kinds of thorium or _ __- 29 · This paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 554547 A7 — __ — — B7 V. Description of the invention (—20— Other glory bodies. Two types with different displacements from Y to Gd by mixing The yttrium / aluminum / garnet-based phosphors can easily achieve light with a desired hue. In particular, if a fluorescent substance with a large amount of the aforementioned substitution is used as the fluorescent material with a large particle size, the amount of the substitution is very With less or zero fluorescent substances as the above-mentioned medium-sized fluorescent substances, the color rendering and brightness can be improved at the same time. (Translucent resin) The translucent resin 8 series has an epoxy equivalent of 0.05 ~ 15 moles of anhydride or dicarboxylic acid to 65% by weight or more of epoxy resin composed of alicyclic epoxy resin to become a crosslinked oligomer, and a small amount of cation hardening is mixed in the crosslinked oligomer Agent (relevant epoxy equivalent is from 0.005 to 5 0.0001 ~ 0.01 mol) solution, coated on the inside of a storage portion 1a containing a nitride semiconductor LED chip 5, and then heat-hardened to form it. The light-transmitting resin 8 formed in this way absorbs blue light cations The content of the hardener is a conventional amount of 1/1/10 to 1 / 10.00, so the yellowing of the resin is hardly a problem. Therefore, the light emitting and fluorescent substances of the nitride semiconductor LED chip 5 which can emit blue light are used. The wavelength-converted light can be efficiently output to the outside. Since the translucent resin 8 has a relatively high possibility, the stress caused by the difference in thermal expansion coefficient between the translucent resin 8 and the LED chip 5 can be reduced. In order to prevent the occurrence of cracks in the nitride semiconductor LED chip 5 or the defect of cutting of the lead wire 7, the composition of an epoxy resin composition for a light-transmitting resin 8 will be described in detail below. The epoxy resin composition of Resin 8 is alicyclic epoxy resin. 30- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 554547 A7

作為主成分之環氧樹脂、與 劑作為必要成分，進—步…：戈—灰酸％離子硬化 其聚縮合物所構成之助觸媒等=，亦可含有由多元醇或 (環氧樹脂） 性樹脂8必須維持高透光性，故，使用於本發明之環 乳树月g，係謂環式環氧樹脂占有全環氧樹脂成分（=只除 去硬化劑等之環氧樹脂的全量)中之65重量％以上較佳係 90重量％以上的方式，極力減少成為著色成分之芳香族成 分、尤其酚衍生物的含量。脂環式環氧樹脂可混合環己缔 環氧化物衍生物、氧化雙酚A二縮水甘油基醚、六氫酞酸 二縮水甘油基酯等單獨或2種以上而使用之。尤其，以3,4-環氧基環己基甲基-3，，4·環氧基環己基羧酸酯為代表之環 己晞環氧化物衍生物為主體，依需要而混合六氫酞酸二縮 水甘油基酯、或、由氫化雙酚A二縮水甘油基醚等之環己 烷衍生物與環氧氣丙烷所構成的環氧樹脂。又，亦可依需 要而混合由雙酚A二縮水甘油基醚所構成之液狀或固形的 環氧樹脂等。 (酸酐或二羧酸） 於酸酐或二羧酸中係可使用以下之通式（1)所示之酸酐或 以通式（2)所示之二羧酸。The epoxy resin as the main component and the adjuvant as the essential components, further ...: Ge-gray acid% ion hardens its polycondensation catalyst, etc., and may also contain polyol or (epoxy resin) ) The resin 8 must maintain high light transmittance. Therefore, the cyclic epoxy resin used in the present invention means that the cyclic epoxy resin occupies the entire epoxy resin component (= the total amount of the epoxy resin except only the hardener is removed). The content of 65% by weight or more is preferably 90% by weight or more, and the content of an aromatic component, particularly a phenol derivative, which is a coloring component is minimized. The alicyclic epoxy resin may be used singly or in combination of cyclohexyl epoxide derivative, oxidized bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, and the like. In particular, cyclohexyl epoxide derivatives represented by 3,4-epoxycyclohexylmethyl-3,4,4-epoxycyclohexyl carboxylate are mainly used, and hexahydrophthalic acid is mixed as required. An epoxy resin composed of a diglycidyl ester or a cyclohexane derivative such as a hydrogenated bisphenol A diglycidyl ether and an epoxy propane. Further, a liquid or solid epoxy resin composed of bisphenol A diglycidyl ether may be mixed as necessary. (Acid anhydride or dicarboxylic acid) Among the acid anhydride or dicarboxylic acid, an acid anhydride represented by the following general formula (1) or a dicarboxylic acid represented by the general formula (2) can be used.

(1)(1)

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本紙張尺度適用中國國家標準(CMS) A4规格(210X297公爱） 554547 A7 B7 五、發明説明（29 ) HOOC——R2——COOH (2) 式中’ 1^表示碳數0〜12之環式或脂肪族烷基或芳基' r2 表示碳數0〜12之烷基或芳基。酸酐可使用如：丙酸酐、無 水琥拍酸、1,2 -環己烷二羧酸酐、3 -甲基-1，2 -環己烷二羧 酸奸、4 -甲基-1，2-環己烷二羧酸酐、無水酞酸、4,4，·雙 無水缺酸、六氫無水酞酸、甲基六氫無水酞酸、三烷基四 氲播水自太酸、氫化甲基鋼吉酸酐等。又，二幾酸可使用 如：4,4’ -雙苯基二羧酸、2,2，-雙苯基二羧酸、草酸、琥 珀酸、己二酸、1,6 -己烷二羧酸、丨，；^環己烷二羧酸、 1，3-環己烷二羧酸、〗，4-環己烷二羧酸、卜酞酸、m•酞 酸、P -目太酸等。 於環氧樹脂中混合酸酐或二羧酸而形成交聯寡聚物後， 於交聯寡聚物中混合陽離子硬化劑而硬化時，宜相對於環 氧基當量以0.005〜0·5莫耳之比例混合酸酐或二羧酸，更宜 以0·01〜0.2莫耳之比例混合。另外，於環氧樹脂中同時混 合酸奸或二羧酸與陽離子硬化劑而使之硬化時，宜相對於 環氧基當量以〇·〇〇5〜1.5莫耳之比例混合酸酐或二羧酸，更 宜以0.1〜0.8莫耳之比例混合。 (陽離子硬化劑） 於陽離子硬化劑可使用芳香族硫鑌鹽、芳香族重氣錯、 芳香族碘鑌鹽、芳香族硒等。芳香族硫鏘鹽係藉熱及/或 360 nm以下之紫外線進行分解，產生陽離子。例如，三苯 基硫鑌六氟化銻鹽、三苯基硫鑌六氟化磷鹽等。尤其，= -32-This paper size applies the Chinese National Standard (CMS) A4 specification (210X297 public love) 554547 A7 B7 V. Description of the invention (29) HOOC——R2——COOH (2) where '1 ^ represents the ring of carbon number 0 ~ 12 Formula or aliphatic alkyl or aryl 'r2 represents an alkyl or aryl group having 0 to 12 carbon atoms. The acid anhydride can be used such as: propionic anhydride, anhydrous succinic acid, 1,2-cyclohexanedicarboxylic anhydride, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2- Cyclohexanedicarboxylic anhydride, anhydrous phthalic acid, 4,4, · dihydroanhydrous acid, hexahydroanhydrophthalic acid, methylhexahydroanhydrophthalic acid, trialkyltetrahydrosulfuric acid, hydrogenated methyl steel Glycolic anhydride, etc. In addition, dikidic acid can be used, for example: 4,4'-bisphenyldicarboxylic acid, 2,2, -bisphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid, 1,6-hexanedicarboxylic acid Acid, 丨, ^ cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, phthalic acid, m-phthalic acid, P-phthalic acid, etc. . When an acid anhydride or a dicarboxylic acid is mixed with an epoxy resin to form a crosslinked oligomer, and a cationic hardener is mixed with the crosslinked oligomer to harden it, it is preferable that the epoxy equivalent is 0.005 to 0.5 mole. Mix acid anhydride or dicarboxylic acid in a ratio, and more preferably mix in a ratio of 0.01 to 0.2 mole. In addition, when an acid or a dicarboxylic acid and a cationic hardener are mixed together in an epoxy resin to harden it, it is preferable to mix an acid anhydride or a dicarboxylic acid with a ratio of 0.05 to 1.5 moles relative to the epoxy equivalent. , More preferably mixed in a ratio of 0.1 to 0.8 mol. (Cationic hardener) As the cationic hardener, aromatic thiosulfonium salt, aromatic heavy gas, aromatic iodonium salt, aromatic selenium, and the like can be used. Aromatic thiosulfonium salts are decomposed by heat and / or UV below 360 nm to generate cations. For example, triphenylthiosulfonium hexafluoride salt, triphenylthiosulfonium hexafluoride salt, and the like. In particular, = -32-

554547 A7 B7554547 A7 B7

五、發明説明（3〇 ) 苯基硫錯六氟化銻鹽係硬化速度快，即使以少量調配亦可 充分硬化。陽離子硬化劑係相對於還氧基當量使用 0.00005〜0.003莫耳，宜使用〇 〇〇〇1〜〇 〇1莫耳，更宜為 0.0002〜0.005 莫耳。 (助觸媒） 使用來作為助觸媒之多元醇可使用如乙二醇、二甘醇、 二甲二醇、三乙二醇、丙二醇、丨’扣丁二醇、1>6•己二醇 等。又，亦可使用縮合聚合此等多元醇中之一種或二種以 上的聚縮合體。多元醇或此等之聚縮合體係相對於酸奸或 二羧酸為0.1〜5.0當量，更宜使用〇 2〜3 〇當量。 又，使用於透光性樹脂等之環氧樹脂組合物，係含有上 述各組成以外之成分亦無妨。例如於透光性樹脂8中，亦可 含有填充劑10。又，除填充劑外，亦可含有擴散劑、著色 劑等之各種功能。 其次’說明有關透光性樹脂8之形成方法的詳細。 透光性樹脂8之形成有如下方法：（i)於環氧樹脂中同時 混合酸酐等與陽離子硬化劑之溶液進行塗布、硬化；（^) 使酸奸等與j衣乳樹脂反應而交聯寡聚物後，於其交聯寡聚 物中混合陽離子硬化劑的溶液進行塗布、硬化。例如，使 ，光性樹脂8形成500 /zm以下時，以（ii)之方法為佳。藉由 採由（Π)之方法，可防止當呈薄膜狀塗布透光性樹脂8而硬 化時<酸酐等的揮發，又，所塗布之溶液的黏度調整很容 易，適用期亦變長，故作業性變佳。 以下，詳細說明有關（ii)之方法。V. Description of the invention (30) Phenylthiomalon antimony hexafluoride hardening speed is fast, and it can be fully hardened even with a small amount of preparation. The cationic hardener is 0.00005 to 0.003 moles, preferably 0.0001 to 0.005 moles, and more preferably 0.0002 to 0.005 moles, relative to the oxo equivalent. (Auxiliary catalyst) The polyhydric alcohol used as the auxiliary catalyst can be used such as ethylene glycol, diethylene glycol, dimethyl glycol, triethylene glycol, propylene glycol, butanediol, 1 > 6 Alcohol and so on. Alternatively, a polycondensate obtained by condensation polymerization of one or more of these polyols may be used. Polyols or these polycondensation systems are 0.1 to 5.0 equivalents relative to acid or dicarboxylic acid, and more preferably 2 to 3 equivalents. The epoxy resin composition used in a light-transmitting resin or the like may contain components other than the above-mentioned components. For example, the translucent resin 8 may contain a filler 10. In addition to the filler, various functions such as a diffusing agent and a coloring agent may be contained. Next, the method of forming the translucent resin 8 will be described in detail. The formation of the translucent resin 8 includes the following methods: (i) coating and curing a solution of an acid anhydride and a cationic hardener in an epoxy resin at the same time; (^) reacting the acid and the like with the j-coat milk resin and crosslinking After the oligomer, a solution of a cationic hardener is mixed with the crosslinked oligomer to apply and harden. For example, when the photoresist 8 is made to be 500 / zm or less, the method (ii) is preferred. By adopting the method (Π), the volatilization of < anhydride, etc., can be prevented when the light-transmitting resin 8 is applied as a thin film and hardened. In addition, the viscosity of the applied solution can be easily adjusted and the pot life can be extended. Therefore, workability becomes better. The method of (ii) will be described in detail below.

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554547 A7 B7 先’在適當的反應容器中，使65重量％以上由脂環式 &氧樹脂所構成的環氧樹脂，與相對於環氧基當量為 0·005〜〇·5莫耳，宜為〇〇1〜〇2〇莫耳之酸酐或二羧酸反應 而开> 成又聯寡聚物。當使用多元醇或其聚縮合體作為助觸 ^時，係與酸酐或二羧酸同時地混合於環氧樹脂中。環氧 樹月曰與酸酐或二羧酸之反應，係宜在氧化等之副反應很難 發生之至溫下進行。酸酐之情形下的反應時間約為1〜36〇 小時，二羧酸之情形下的反應時間約為小時。為促 進酸酐之開環反應而縮短反應時間，亦可加熱至50〜15〇eC (較佳係60〜12(TC)。 其次，調整一溶液，其係於所得到之交聯寡聚物中混合 相對於5衣氧當量為0·00005〜0·〇3莫耳，宜為ooooi〜〇〇1 莫耳之陽離子硬化劑。然後，將混合溶液充填於一收藏著 氮化物半導體LED晶片5的收藏部1 a之内部後，藉加熱進行 硬化而形成透光性樹脂8。混合溶液係在8〇〜i〇〇(>c下加熱 2〜4小時而約次硬化，在14〇〜15〇t下加熱^小時而第] 次硬化。 又更具體的製造方法如後述。 如上述般最後所得到之環氧樹脂組合物的可撓性，係比 例於中間所得到之交聯寡聚物的分子量。亦即，酸酐或二 羧酸之羧基中，與環氧樹脂或助觸媒反應而轉化成醋之比 2愈高，所得到之環氧樹脂組合物的可撓性愈良好。又， 交聯寡聚物與陽離子硬化劑之混合液的黏度，係依存於交 聯寡聚物之分子量，故藉由調節酸酐等之添加量或酯轉化554547 A7 B7 Firstly, in an appropriate reaction vessel, 65% by weight or more of an epoxy resin composed of an alicyclic & oxygen resin and an epoxy equivalent of 0.005 to 0.5 moles, It is preferred to react with 0.001 to 002 mole of anhydride or dicarboxylic acid to form a double-linked oligomer. When a polyhydric alcohol or a polycondensate thereof is used as a catalyst, it is simultaneously mixed with an acid anhydride or a dicarboxylic acid in an epoxy resin. The reaction of epoxy resin with acid anhydride or dicarboxylic acid is preferably carried out at a temperature where side reactions such as oxidation are difficult to occur. The reaction time in the case of an acid anhydride is about 1 to 36 hours, and the reaction time in the case of a dicarboxylic acid is about 1 hour. In order to accelerate the ring-opening reaction of the acid anhydride and shorten the reaction time, it can also be heated to 50 ~ 15eC (preferably 60 ~ 12 (TC). Secondly, a solution is adjusted to be in the obtained crosslinked oligomer It is mixed with a cationic hardener having an oxygen equivalent of 0 · 00005 ~ 0 · 〇3 moles, preferably ooooi ~ 001 moles. Then, the mixed solution is filled in a nitride semiconductor LED chip 5 containing After the inside of the storage section 1 a, it is hardened by heating to form a light-transmitting resin 8. The mixed solution is heated at 80 to 100 (> c for 2 to 4 hours to harden for about one time, and is 14 to 15 Heating for ^ hours at 〇t for the first time]. A more specific manufacturing method will be described later. The flexibility of the epoxy resin composition finally obtained as described above is proportional to the crosslinked oligomer obtained in the middle. That is, the higher the ratio of the carboxylic acid anhydride or dicarboxylic acid carboxyl group to the reaction with an epoxy resin or a catalyst to convert to vinegar, the higher the flexibility of the obtained epoxy resin composition. The viscosity of the mixed solution of crosslinked oligomer and cationic hardener depends on the viscosity of the crosslinked oligomer. Molecular weight, so by adjusting the amount of acid anhydride added or ester conversion

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554547 A7 _ B7 五、發明説明（32 ) 率而可自由地調節黏度。 〈實施形態1之製造方法&gt; 其次，說明有關本實施形態1之發光二極體的製造方法。 本製造方法係一種使實施形態1之表面安裝型的發光二極 體安定且量產性佳地進行製造之方法。 在本製造方法中，至以透光性樹脂被覆LED晶片5之步 驟，係為使複數之封裝體一概處理，使用複數之封裝體集 合而成的封裝體組件。此封裝體組件係形成一對應於各封 裝體的收藏部1 a的複數貫通孔101 a之絕緣性基板1 〇 1與金 屬基底板102接合而製成的。 此處，絕緣性基板101係例如由厚為〇·〇6 mm〜2.0 mm之 树脂積層品等所構成的’形成貫通於厚度方向之複數貫通 孔101a。貫通孔l〇la之橫斷面形狀可為橢圓，亦可為圓形 或方形。亦即，本發明係不被貫通孔1 〇 1 a之橫斷面形狀所 限定，可從各種形狀之中任意地選定。又，在貫通孔1〇u 中’宜以貫通孔l〇la之開口徑從絕緣基板之一面（與金屬薄 板所接合之面）_另外一面而變大的方式，使貫通孔之側面 傾斜。如此若使貫通孔丨〇丨a之側面傾斜，從LEd晶片朝貫 通孔之側面所射出的光於側面反射而朝上方輸出，故，可 效率佳地從發光二極體取出一從LED晶片5所射出之光。 又’金屬基底板102被切斷成一個一個之封裝體時，於各 封裝體中以金屬薄板2a與金屬薄板2b藉絕緣性樹脂4電氣 分離的方式，分別對應於各貫通孔而形成分離溝，其分離 溝中充填絕緣性樹脂4。 -35- 554547 A7 B7 五 發明説明（33 ) 在各封裝體部分中，在貫通孔101a内露出金屬薄板2&amp;之 一部分、絕緣性樹脂4、及金屬薄板2 b之一部分。 進而，在封裝體組件中進一步相對於後述掩模112之1個 的開口部113而複數封裝體被分组配置。 &lt;LED晶片之安裝&gt; 在如上述所構成之封裝體組件的各貫通孔（收藏部）之特 定位置使用模黏合樹脂而使LED晶片5進行模黏合，藉引線 黏合進行特定的配線（圖5)。_ . 於各貫通孔之内側係露出金屬薄板2a與金屬薄板2b， LED晶片5接著於負電極之金屬薄板2b上，其LED晶片5之 p側電極5 a及η側電極5 b係藉引線7分別連接於金屬薄板2 a 及金屬薄板2b。 &lt;第1步驟：孔版印刷&gt; 其次，封住構件即透光性樹脂（本發明之環氧樹脂組合物） 8係於腔室内藉孔版印刷進行塗布。圖3 A係本實施形態1之 製造方法的孔版印刷所使用之掩模112的平面圖。於掩模 112如圖3 A所示，形成複數之開口部113，各開口部113之 位置及大小係相對於1個開口部113，歸納成1群組之複數 封裝體對應般設定（圖3B)。如此本發明所使用之掩模係不 只於各貫通孔内設置透光性樹脂，亦於周圍之絕緣性基板 101上形成樹脂層的方式進行設計。在本實施形態之製造方 法中，使用如此之掩模112而進行孔版印刷，於絕緣基板之 貫通孔101a内及絕緣性基板101上以硬化後表面呈平滑面之 方式而可形成透光性樹脂。 -36- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)554547 A7 _ B7 V. Description of the invention (32) The viscosity can be adjusted freely. <Manufacturing method of the first embodiment> Next, a manufacturing method of the light emitting diode of the first embodiment will be described. This manufacturing method is a method for manufacturing the surface-mount type light emitting diode of the first embodiment in a stable and mass-productive manner. In this manufacturing method, the step of covering the LED chip 5 with a light-transmitting resin is a package assembly in which a plurality of packages are integrated in order to treat the plurality of packages collectively. This package assembly is formed by joining an insulating substrate 101 having a plurality of through-holes 101a corresponding to the storage portion 1a of each package and a metal base plate 102. Here, the insulating substrate 101 is formed of, for example, a plurality of through-holes 101a formed through a resin laminate having a thickness of 0.06 mm to 2.0 mm and penetrating in the thickness direction. The cross-sectional shape of the through hole 10a may be elliptical, circular, or square. That is, the present invention is not limited to the cross-sectional shape of the through-hole 10a and can be arbitrarily selected from various shapes. In the through-hole 10u, it is preferable that the side surface of the through-hole is inclined so that the opening diameter of the through-hole 10la becomes larger from one surface of the insulating substrate (the surface to which the thin metal plate is joined) _the other surface. In this way, if the side of the through-hole 丨 〇 丨 a is inclined, the light emitted from the LEd chip toward the side of the through-hole is reflected on the side and output upward. Therefore, it is possible to efficiently take out the light-emitting diode from the LED chip 5 The emitted light. When the metal base plate 102 is cut into individual packages, the metal sheets 2a and the metal sheets 2b are electrically separated by the insulating resin 4 in each package to form separate trenches corresponding to the respective through holes. The insulation groove 4 is filled in the separation trench. -35- 554547 A7 B7 V. Description of the Invention (33) In each package part, a part of the metal sheet 2 &, an insulating resin 4, and a part of the metal sheet 2b are exposed in the through hole 101a. Furthermore, a plurality of packages are arranged in groups in the package assembly with respect to the opening 113 of one of the masks 112 described later. &lt; Installation of LED chip &gt; Using a mold bonding resin to mold the LED chip 5 at a specific position of each of the through-holes (storage portions) of the package assembly configured as described above, the LED chip 5 is mold-bonded, and specific wiring is performed by wire bonding (Figure 5). _. The metal sheet 2 a and the metal sheet 2 b are exposed on the inside of each through hole, and the LED chip 5 is next to the metal sheet 2 b of the negative electrode. The p-side electrode 5 a and the η-side electrode 5 b of the LED chip 5 are lead wires. 7 are connected to the metal sheet 2 a and the metal sheet 2 b, respectively. &lt; 1st step: stencil printing &gt; Next, the light-transmitting resin (epoxy resin composition of the present invention) 8 which is a sealing member is coated by stencil printing in a chamber. Fig. 3A is a plan view of a mask 112 used for stencil printing according to the manufacturing method of the first embodiment. As shown in FIG. 3A, a plurality of openings 113 are formed on the mask 112. The positions and sizes of the openings 113 are set corresponding to the plurality of packages grouped into one group relative to one opening 113 (FIG. 3B). ). In this way, the mask used in the present invention is not only provided with a light-transmitting resin in each of the through holes, but also is designed to form a resin layer on the surrounding insulating substrate 101. In the manufacturing method of this embodiment, stencil printing is performed using such a mask 112, and a light-transmitting resin can be formed in the through-hole 101a of the insulating substrate and on the insulating substrate 101 so that the cured surface becomes smooth. . -36- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

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線 554547 A7 B7 五、發明説明（34 ) 亦即，在本製造方法中，如圖5所示般，除去一很難使開 口部113的周邊部分之透光性樹脂形成平坦的部分，而配置 被分群之複數封裝體，於配置複數封裝體之部分以一定的 厚度且表面呈平坦之方式形成透光性樹脂，俾抑制在封裝 體間之透光性樹脂層厚度的參差不齊且謀求各封裝體之透 光性樹脂表面的平坦化。 如此，對於複數之發光二極體一度形成透光性樹脂後， 於圖5所示之虚線部分切斷而-分離以形成各別之發光二極 體。藉此，可在發光二極體間不產生大小或色參差不齊之 方式良率佳地形成一具有均一膜厚之發光二極體。又，以 調整掩模之板厚可任意地變更一形成於前述絕緣性基板上 之透光性樹脂膜厚。 其次，在各開口部113中，具體地說明方法之一例，其係 於配置複數封裝體之部分以一定的厚度且表面呈平坦之方 式形成透光性樹脂。 (步驟1) 首先，將一貫通孔10 la朝掩模112側之封裝體組件10〇吸 引至昇降台117上（圖4A)，使台117上昇而對準封裝體組件 100與掩模112位置，而接觸掩模112的下面（圖4B)。藉 此’以矯正封裝體組件之翹曲的狀態可使封裝體組件1〇〇接 觸掩模112。如此，藉矯正封裝體組件100之翹曲，可於封 裝體組件100上之一面形成均一的膜厚透光性樹脂。亦即， 若於封裝體基板翹曲直接形成封住構件，在所形成之各個 發光二極體間會產生厚度參差不齊且良率會惡化。 -37· ¥纸張尺度適用中@ S家標準(CNS) A4規格(210X297公釐) 一 554547 A7 _ B7 五、發明説明（35 ) 含有螢光物質之透光性樹脂，如圖4A所示，在大氣壓下 配置於掩模112之開口部外之端。以此狀態減壓而進行脫 泡。減壓宜設定於100 Pa〜400 Pa之範圍，若為此範圍，可 有效地取出樹脂内部所含有的氣泡。在使用上述封裝體組 件100與掩模112之本實施形態中，可使用比較高黏度者作 為透光性樹脂。 如本實施形態1般，使螢光物質含於透光性樹脂而使用 時，具有特大之粒徑的螢光物質在液狀樹脂中之沉澱速率 會很快，故，宜使用一具有在保持分散均一性上之黏度的 樹脂。然而，黏度愈高之樹脂脫泡愈困難，製造良率有下 降之虞。於是，本發明係首先在進行孔版印刷之前步驟而 一度進行減壓而脫泡，其後，採用反覆加壓及減壓同時並 進行孔版印刷之方法，俾不使製造良率降低並可使用高黏 度的透光性樹脂。藉此目的在於當使用大粒徑之螢光物質 時，可改善易造成之色參差不齊，並可使用高的黏度樹 月旨。又，即使使用高黏度的樹脂時，亦可良率佳地製造發 光二極體。 若於透光性樹脂中直接混合氣泡而被封住，因氣泡使來 自LED晶片之光或螢光物質之發光反射折射，故色不均或 輝度不均明顯被觀測到。因此，形成一含有螢光物質之透 光性樹脂時’如本貫施形態般反覆減壓及加壓乃極有效， 有抑制色不均或輝度不均之顯著效果。又，若於透光性樹 脂中含有氣泡，其乃原因所在而有透光性樹脂之剝離、引 係接著部分之剝離、引線斷裂等產生時，信賴性會降低。 •38- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 554547 A7 _B7 五、發明説明（36 ) 因此，藉本方法防止氣泡，就提高信賴性上亦極有效。 (步驟2) 其次在減壓下，進行第1往返之往壓擠掃瞄（圖4C)。此 時所使用之往愿擠用刮刀114 ’如圖4 C所示，相對於掩模 112之垂直方向朝動作方向傾斜，藉空壓使刮刀U4押抵掩 模112而動作’使樹脂8流入掩模112之開口部113 ^往壓擠 掃瞄因在減壓下進行，昇降台117之吸引作用不構成意義， 但，因物理上使昇降台117押抵掩模112，故不會造成封裝 體組件100與掩模112之偏移。 (步驟3) 其次，加壓至大氣壓，加壓完了後，第1往返之返壓擠乃 與往壓擠掃瞄逆方向進行（圖4D)。往壓擠用刮刀U5係相 對於掩模112之垂直線朝動作方向比往壓擠用刮刀114更大 傾斜且比往壓擠掃瞄時更強的空壓進行動作。如此，藉很 強的壓力增大返壓播用刮刀115與掩模112之接觸面積而再 充填透光性樹脂，可有效率地除去充填於開口部丨丨3内之樹 脂表面出現的氣泡，並加精加工封住構件之表面呈平滑的 面0 (步驟4) 步驟2與步驟3同樣做法，而反覆減壓及加愿使之脫泡同 時並進行數次往返壓擠，於開口部113内以均一膜厚充填樹 脂。 (步驟5) 以此狀態（使掩模112接觸封裝體組件100之狀態）使透光 -39· 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) — '&quot;&quot;&quot;&quot; 554547 A7 B7 五、發明説明（37 ) 性樹脂硬化，而於硬化後除去掩模，在配置著LED晶片之 貫通孔内及絕緣性基板上面所一體成形之透光性樹脂的上 面形成大致與封裝體底面平行且平滑的面。 藉由使用如此孔版印刷之封住樹脂形成方法，即使在硬 化前亦可使用比較高黏度之透光性樹脂。因此，如當使用 黏度低之樹脂時，在樹脂中螢光物質不會自由沉澱或浮 游。是故，可比較良好地維持螢光物質之混合狀態。又， 在成形時，透光性樹脂會溶解而成為液體而存在之時間係 數分至數十秒，與藉黏合方法流入貫通孔内而熱硬化形成 之數小時比較而可非常縮短。進而，因至固化之時間亦可 極縮短，故可避免在led晶片上螢光物質重疊而沉澱之狀 態。 亦即，若依本實施形態1之製造方法，因可使用黏度高的 透光性樹脂，故於透光性樹脂中含有螢光物質後，可防止 至充填於基板上之間的樹脂與螢光物質的分離。藉此，可 抑制在發光二極體間之螢光物質含量的參差不齊，同一製 造批内、及製造批間之、色參差不齊很少的發光二極體的 製造成為可能。又，可提昇製造良率。 又，在充填於各貫通孔後至硬化之間，亦可避免大粒徑 螢光物質密集沉澱於LED晶片之表面附近，並能有效發揮 各大粒徑螢光物質之光變換功能。又，可將小粒徑螢光物 質均一配置於大粒徑螢光物質之外側的透光性樹脂中，藉 此，可防止發光二極體之色不均。 尤其形成一含有YAG : Ce螢光體作為螢光物質之可白色 -40- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 裝 訂Line 554547 A7 B7 V. Description of the Invention (34) That is, in this manufacturing method, as shown in FIG. 5, a portion where it is difficult to form the transparent resin in the peripheral portion of the opening portion 113 is removed and arranged. The plurality of packaged bodies are grouped to form a light-transmitting resin with a certain thickness and a flat surface at a portion where the plurality of package bodies are arranged, so as to suppress variations in the thickness of the light-transmitting resin layer between the packages and seek for various Planarize the transparent resin surface of the package. In this way, after a plurality of light-emitting diodes were formed into a light-transmitting resin at one time, they were cut and separated at the dotted line portion shown in FIG. 5 to form individual light-emitting diodes. Thereby, a light-emitting diode having a uniform film thickness can be formed with good yield in such a manner that no size or color unevenness occurs between the light-emitting diodes. The thickness of the transparent resin film formed on the insulating substrate can be arbitrarily changed by adjusting the thickness of the mask. Next, an example of a method is specifically described in each of the openings 113, in which a portion where a plurality of packages are arranged is formed with a light-transmitting resin having a constant thickness and a flat surface. (Step 1) First, a package assembly 100 passing through a through hole 10a toward the mask 112 side is attracted to the lifting table 117 (FIG. 4A), and the table 117 is raised to align the package assembly 100 and the mask 112. While contacting the underside of the mask 112 (FIG. 4B). With this, the package body 100 can be brought into contact with the mask 112 to correct the warped state of the package body component. In this way, by correcting the warpage of the package body assembly 100, a uniform film thickness translucent resin can be formed on one surface of the package body assembly 100. That is, if the sealing member is directly formed by warping the package substrate, uneven thicknesses will occur between the formed light emitting diodes and the yield will deteriorate. -37 · ¥ Paper size applicable @ S 家 standard (CNS) A4 size (210X297 mm) 554547 A7 _ B7 V. Description of the invention (35) Translucent resin containing fluorescent substances, as shown in Figure 4A Is disposed at an end outside the opening of the mask 112 under atmospheric pressure. Degassing was performed under reduced pressure in this state. The decompression should be set in the range of 100 Pa to 400 Pa. If the pressure is within this range, bubbles contained in the resin can be effectively taken out. In this embodiment using the package assembly 100 and the mask 112 described above, a relatively high viscosity can be used as the translucent resin. As in the first embodiment, when a fluorescent substance is contained in a translucent resin and used, the precipitation rate of the fluorescent substance with an extremely large particle diameter in the liquid resin will be fast. Therefore, it is desirable to use a Resin with uniform viscosity. However, the higher the viscosity of the resin, the more difficult it is to defoam, and the manufacturing yield may decrease. Therefore, the present invention first decompresses and defoams once before performing the step of stencil printing, and then uses the method of repeated pressure and decompression to perform stencil printing simultaneously, which does not reduce the manufacturing yield and can use high Viscosity transparent resin. The purpose is to improve the color unevenness that can easily be caused when using a fluorescent material with a large particle size, and to use a high viscosity tree. In addition, even when a resin having a high viscosity is used, a light emitting diode can be produced with a good yield. If air bubbles are directly mixed in the light-transmitting resin and sealed, the air bubbles reflect the light from the LED chip or the luminescence of the fluorescent substance and reflect and refract, so that color unevenness or uneven luminance are clearly observed. Therefore, when a light-transmitting resin containing a fluorescent substance is formed, it is extremely effective to repeatedly depressurize and pressurize as in the conventional embodiment, and it has a significant effect of suppressing color unevenness and uneven brightness. In addition, if air bubbles are contained in the translucent resin, it is because the peeling of the translucent resin, the peeling of the lead-in portion, the lead breakage, etc. are caused because of the cause, and the reliability is lowered. • 38- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554547 A7 _B7 V. Description of the invention (36) Therefore, preventing air bubbles by this method is also very effective in improving reliability. (Step 2) Next, under the reduced pressure, the first round-trip squeezing scan is performed (FIG. 4C). As shown in FIG. 4C, the wishing squeezing blade 114 used at this time is inclined with respect to the vertical direction of the mask 112 toward the operation direction, and the doctor blade U4 is pressed against the mask 112 by air pressure to operate and the resin 8 flows The opening 113 of the mask 112 is pressed under reduced pressure, and the attraction of the lifting platform 117 is not meaningful. However, because the lifting platform 117 is physically pressed against the mask 112, it does not cause packaging. Offset of the body assembly 100 from the mask 112. (Step 3) Next, pressurize to the atmospheric pressure. After the pressurization is completed, the first back-and-forth back-pressing is performed in the opposite direction to the forward-scanning scan (Fig. 4D). The squeezing squeegee U5 is a pneumatic line with a larger vertical direction with respect to the mask 112 than the squeezing squeegee 114, and operates at a higher air pressure than when squeezing and scanning. In this way, by applying a strong pressure to increase the contact area between the back-pressure spreading blade 115 and the mask 112, and then filling the transparent resin, the bubbles appearing on the surface of the resin filled in the openings 3 can be efficiently removed. And the surface of the component is finished with a smooth surface 0 (step 4) Step 2 is the same as step 3, and it is repeatedly decompressed and degassed at the same time and pressed back and forth several times at the opening 113 The resin is filled with a uniform film thickness. (Step 5) In this state (the state where the mask 112 is in contact with the package assembly 100), the light is transmitted. -39 · This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) — '&quot; &quot; &quot; &quot; 554547 A7 B7 V. Description of the invention (37) The hardening resin is cured, and the mask is removed after hardening, and formed on the transparent resin integrally formed in the through hole where the LED chip is arranged and on the insulating substrate. A surface that is substantially parallel and smooth to the bottom surface of the package. By using such a sealing resin forming method for stencil printing, a relatively high-viscosity translucent resin can be used even before hardening. Therefore, when a resin with a low viscosity is used, the fluorescent substance does not freely precipitate or float in the resin. Therefore, the mixed state of the fluorescent substances can be maintained relatively well. In addition, the time period during which the translucent resin dissolves and becomes a liquid during molding is from a few minutes to several tens of seconds, which can be extremely shortened compared with the hours during which the resin is hardened by flowing into the through-hole by a bonding method. Furthermore, since the time until curing can be extremely shortened, it is possible to avoid a state where the fluorescent substances are superimposed on the LED chip and precipitated. That is, according to the manufacturing method of the first embodiment, since a translucent resin having a high viscosity can be used, after the fluorescent substance is contained in the translucent resin, it is possible to prevent the resin and the fluorescent material from filling the substrate. Separation of light matter. This makes it possible to suppress variations in the content of fluorescent substances between the light-emitting diodes, and it is possible to manufacture light-emitting diodes with little color variation within the same manufacturing lot and between manufacturing lots. In addition, manufacturing yield can be improved. In addition, after filling the through-holes to hardening, it is also possible to prevent large-size fluorescent materials from being densely deposited near the surface of the LED chip, and to effectively exert the light conversion function of the large-size fluorescent materials. In addition, it is possible to uniformly arrange the fluorescent material with a small particle size in the light-transmitting resin on the outside of the fluorescent material with a large particle size, thereby preventing color unevenness of the light emitting diode. In particular, it forms a white color that contains YAG: Ce phosphor as a fluorescent substance. -40- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) binding

554547 A7 五、發明説明（38 發光的發光二極體時，比透光性樹脂，螢光物質之比重還 大’有密集沉澱之傾向，但，即使此情形下，亦可避免大 粒徑螢光物質81密集沉澱於LED晶片5之表面附近等，並 可使色溫度均一的發光二極體安定而製造。 其次，詳細說明有關切片步驟。如上述做法而形成（硬化） 透光性樹脂後，如以下般進行切片而分割成各個發光二極 &lt;第2步驟：切片步驟&gt; _ (切片步驟1) 首先，使樹脂硬化後，將封裝體組件100之透光性樹脂側 接著於切片薄片。如上述般，封裝體組件1〇〇與切片薄片之 接著面係實質上由同一材料所構成且平滑的平面，故接著 強度可很強。藉此，可防止切片時之晶片飛出或切片偏 差’可良率佳地切成各個發光二極體。 相對於此，使用一具有對應於封裝體組件之各個貫通孔 的開口部之掩模，而進行樹脂之充填及硬化後，所充填之 樹脂會熱收縮而於貫通孔部分陷沒，與切片薄片接觸之面 係只成為除貫通孔上之絕緣性基板上面，密著性會降低。 又，使用一具有對應於各個貫通孔之開口部的掩模而大量 充填樹脂量再使之硬化，樹脂的上面比所切片之部分即絕 緣性基板上面還更高，與切片薄片之接著面只成為樹脂上 面，此情形下，封裝體組件與切片薄片之接著強度會變得 極弱，而產生切片偏差。如此，若封裝體組件與切片薄片 之固定不安定而直接進行切片，會造成晶片之飛出或切片554547 A7 V. Description of the invention (38 When emitting light-emitting diodes, the proportion of fluorescent substances is greater than that of translucent resins. 'There is a tendency for dense precipitation, but even in this case, large-size fluorescent lamps can be avoided. The light substance 81 is densely deposited on the surface of the LED chip 5 or the like, and the light emitting diode having a uniform color temperature can be stably manufactured. Next, the slicing step will be described in detail. After the light-transmitting resin is formed (hardened) as described above, Slicing is performed as follows to divide into light emitting diodes <2nd step: slicing step> _ (slicing step 1) First, after curing the resin, the transparent resin side of the package body assembly 100 is bonded to the slicing Sheet. As mentioned above, the bonding surface of the package body 100 and the dicing sheet is substantially a flat surface made of the same material, so the bonding strength can be very strong. This can prevent the wafer from flying out during slicing or The slice deviation can be cut into individual light-emitting diodes with good yield. In contrast, a mask having openings corresponding to the respective through-holes of the package component is used to fill the resin and After the resinization, the filled resin will shrink thermally and sink in the through-hole portion, and the surface in contact with the slicing sheet will only become the top surface of the insulating substrate except the through-hole, and the adhesion will be reduced. The masks at the openings of the respective through holes are filled with a large amount of resin and hardened. The upper surface of the resin is higher than the sliced portion, that is, the upper surface of the insulating substrate, and the bonding surface with the slice sheet is only the upper surface of the resin. In this case, , The bonding strength between the package component and the slicing sheet will become very weak, and the slicing deviation will occur. In this way, if the package component and the slicing sheet are unstable and directly sliced, it will cause the wafer to fly out or slice.

554547 A7 B7 五、發明説明（39 ) ~-- 偏差。又，所得到之發光二極禮之切口有時亦會產生毛邊 等的不艮狀況。毛邊在後步驟之安裝過程等有龜裂之虞， 若前述毛邊邵分条裂很深，濕氣會從外部混入至封住構件 内，發光二極體之信賴性會降低，或，成為内部之金屬部 分被氧化而變色等不良原因。 &lt;步驟2 &gt; 將步驟1密著性良好地固定於切片薄片之封裝體組件，從 封裝體組件底面側藉切片刀各別切斷（沿圖5之虛線切斷）。 所渭切片刀係以黏著為中心而使粒徑很小的鑽石粒體集結 於周圍而構成者。如此構成之鑽石刀係當切割封裝體組件 時於粒體之間亦填塞發光二極體之切削的一部分即金屬破 片。因此在第1步驟中，若於封住構件即透光性樹脂中含有 很硬的填充劑，所填塞之金屬會被前述填充劑刮出，而可 良好地進行切片步驟，故佳。若使用粒徑特大的填充劑， 上述之作用效果會變大。在本實施形態1中係使用粒徑很大 的大粒徑螢光物質作為填充劑，且，其大粒徑螢光物質因 具有高的硬度，故上述之作用效果會變大。 以上製造方法所製作之發光二極體中，係透光性樹脂於 絕緣基板的上面與絕緣基板的貫通孔内一體形成，且，透 光性樹脂的上面乃與封裝體底面約平行，且透光性樹脂之 外周側面係與前述封裝體的外周側面在約同一面上。如 此，發光二極體之上面全部形成之透光性樹脂，可使發光 面變寬並提昇輸出。又，藉絕緣基板上之透光性樹脂，可 得到一來自LED晶片之光藉外部擴散且具有良好指向特向 广 ,______—____- 42 -________ 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 554547 A7 B7 五、發明説明（40 ) 之發光二極體。又，於前述絕緣基板上之透光性樹脂含有 填充劑時，藉其填充劑進一步可得到其作用增大且具有較 佳發光特性之發光二極體。554547 A7 B7 V. Description of the invention (39) ~-Deviation. In addition, the obtained luminous bipolar incision may cause incomplete conditions such as burrs. There may be cracks in the installation process of the burr in the subsequent steps. If the burr is split deeply, moisture will be mixed into the sealing member from the outside, and the reliability of the light emitting diode will be reduced, or it will become internal. The metal part is oxidized and discolored. &lt; Step 2 &gt; Fix the package components of Step 1 with good adhesion to the slicing sheet, and cut each of them from the bottom side of the package component with a dicing knife (cut along the dotted line in Fig. 5). The slicing knife is composed of the diamond granules with a small particle size centered around the adhesion. The diamond knife thus constituted is a metal fragment that is part of the cutting of the light-emitting diodes when the package body is cut between the particles. Therefore, in the first step, if a hard filler is contained in the light-transmitting resin that is a sealing member, the stuffed metal will be scraped off by the filler, and the slicing step can be performed well. When a filler having an extremely large particle diameter is used, the above-mentioned effects are increased. In the first embodiment, a large-particle-size fluorescent substance having a large particle diameter is used as a filler, and the large-particle-size fluorescent substance has a high hardness, so that the above-mentioned effect is increased. In the light-emitting diode produced by the above manufacturing method, the light-transmitting resin is integrally formed on the upper surface of the insulating substrate and the through hole of the insulating substrate, and the upper surface of the transparent resin is approximately parallel to the bottom surface of the package and transparent. The outer peripheral side surface of the optical resin is approximately the same surface as the outer peripheral side surface of the package. In this way, the light-transmitting resin formed on the entire surface of the light-emitting diode can widen the light-emitting surface and improve the output. In addition, by using the light-transmitting resin on the insulating substrate, a light from the LED chip can be diffused from the outside and has a good directivity and wide orientation. ______—____- 42 -________ This paper standard applies to China National Standard (CNS) A4 (210X 297 mm) 554547 A7 B7 V. Light-emitting diode of invention description (40). When the light-transmitting resin on the insulating substrate contains a filler, a light-emitting diode having an enhanced effect and excellent light-emitting characteristics can be obtained by using the filler.

裝 訂Binding

如以上詳細說明般，本發明之實施形態的發光二極體， 係使用一種螢光物質，其被分級成具有各別之粒徑分布區 域分開成小粒徑螢光物質及大粒徑螢光物質，以此等之作 用可呈最大限活用之方式配置，俾能提昇光度及發光輸 出。小粒徑螢光物質係以全螢-光物質之〇.〇1 V〇l%〜1〇 ν〇1〇/。 之範圍分散於透光性樹脂中的狀態被硬化，可良好地使光 散射並得到均一的發光。又，大粒徑螢光物質係以可充分 發揮高的發光效率之狀態調整成可配置於led晶片周邊之 粒徑範圍，俾能充分發揮原來作用即波長變換作用。又， 以本實施形態所使用之大粒徑螢光物質具有很寬廣的激發 波長’故亦可對應於電流引起之LED晶片波長移位或封裝 體小型化所引起之色度降低等，可形成信賴性及量產性優 異之發光二極體。 又，藉本實施形態之發光二極體的製造方法，可量產性 佳地製造發光特性安定之發光二極體。又，即使量產步驟 達長時間時，最初所製造之發光二極體、與、最後所製造 之發光二極體間之發光參差不齊可成為極小。進一步，因 可減低在發光二極體内之發光不均，故可提昇良率。 在本實施形態1所說明之本發明透光性樹脂，係以陽離子 硬化劑使環氧樹脂與酸肝或二幾酸之交聯寡聚物硬化， 故，可提供一種很少黃變且可撓性優之環氧樹脂組合物。As described in detail above, the light-emitting diode according to the embodiment of the present invention uses a fluorescent substance that is classified into regions having separate particle size distributions and divided into small-sized fluorescent substances and large-sized fluorescent substances. Substances can be configured in such a way that they can be used in the most limited way, and can not improve luminosity and luminous output. The small particle size fluorescent substance is from 0.01% to 100% of the total fluorescent-fluorescent substance. When the range is dispersed in the light-transmitting resin, the state is hardened, and light can be scattered well and uniform light can be obtained. In addition, the large-particle-size fluorescent substance is adjusted to a range of particle diameters that can be arranged around the LED chip in a state that can sufficiently exhibit high luminous efficiency, so that the original function, that is, the wavelength conversion function can be fully exerted. In addition, since the large particle size fluorescent substance used in this embodiment has a wide excitation wavelength, it can also correspond to the wavelength shift of the LED chip caused by the current or the reduction in chromaticity caused by the miniaturization of the package. Light-emitting diode with excellent reliability and mass productivity. In addition, by the method of manufacturing a light-emitting diode of this embodiment, a light-emitting diode with stable light-emitting characteristics can be manufactured with good mass productivity. In addition, even when the mass production process takes a long time, uneven light emission between the light-emitting diodes manufactured first and the light-emitting diodes manufactured last can be extremely small. Furthermore, since the uneven light emission in the light emitting diode can be reduced, the yield can be improved. The light-transmitting resin of the present invention described in this embodiment 1 hardens the crosslinked oligomer of the epoxy resin and the acidic liver or dipic acid with a cationic hardener. Therefore, it can provide a little yellowing Flexible epoxy resin composition.

554547 A7 -----B7 五、發明説明（41 ) T ’依本發明所得到之環氧樹脂組合物係以調整對於環氧 树脂之酸肝或二幾酸的添加量或其等之酯轉化率，可自由 地調節黏度，且適用期亦長，故作業性亦優。 實施形態2554547 A7 ----- B7 V. Description of the invention (41) T 'The epoxy resin composition obtained in accordance with the present invention is used to adjust the amount of acid or hepatic acid added to the epoxy resin or its ester Conversion rate, the viscosity can be adjusted freely, and the pot life is long, so the workability is also excellent. Embodiment 2

圖ό係本發明實施形態2之smd型發光二極體的模式斷面 圖。本實施形態2之發光二極體係使LED晶片5配置於具有 一對引線電極12a、12b之玻璃環氧基板12上；該LED晶片 5係於藍寶石基本上介由GadAh dN(〇sdg丨）所構成之緩衝 層而形成由氮化物半導體（AlxGayInzN 1、OSzS 1、x + y + z=1)所構成之…接合。led晶片5至 少具有氮化物半導體層所構成之發光層 。設於此LED晶片5 I一者的面側之正負各電極，係電氣連接於一對導線電極 1 2 a、1 2 b與各別導電性引線7。 繼而，在實施形態2之發光二極體中，係使與實施形態夏 同樣的螢光物質分散於透光性樹脂丨8中。 亦即，分散於透光性樹脂18中之螢光物質，係包括大粒 徑螢光物質8 1與小粒徑螢光物質8 2 ,在發光二極體中對全 部之大粒徑螢光物質81使波長變換作用發揮至最大限，謀 求發光二極體之輸出提昇，同時並以小粒徑螢光物質82防 止色不均。 在本實施形態之發光二極體中，透光性樹脂丨8係宜使用 在實施形態1所說明的環氧樹脂。 然而’在實施形態2中並非於封裝體中充填樹脂，而於基 板上模铸樹脂者，故，亦可使用適用於其製造方法之其他 _ -44- 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐） 554547 A7 ____B7 五、發明説明（43 ) 施形態1同樣之大粒徑螢光物質8 1與小粒徑螢光物質8 2， 故可形成一能有效率變換紫外線之色變換層，得到高輝度 之發光二極體。尤其，使用複數種類之螢光體而混色發光 時’宜藉小粒徑螢光物質之散射作用有效果地抑制色不 均。 混合此等異種之螢光物質而形成1層之色變換薄膜層時， 各螢光物質之中心粒徑及形狀宜類似。藉此而從各種螢光 物質所發出之光被良地混合，可抑制色不均。 在本實施形態3中，係亦可形成各螢光物質作為各別之色 變換層。使各螢光物質之色變換層作為多重層而配置時， 考慮各別之螢光物質的紫外光穿透率，而於led晶片上依 序積層紅色螢光物質層、綠色螢光物質層、及藍色螢光物 質層，則可於全部的層有效率地吸收紫外線，故佳。進一 步，以在色變換多重層中從下層至上層而各層中之螢光物 免的粒徑會變小之方式’使各勞光物質之中心粒徑形成藍 色螢光物質 &gt; 綠色螢光物質 &gt; 紅色螢光物質，則可至最上層 良好地透過紫外線同時並於色變換多重層中可不洩漏紫外 線而吸收，故佳。 其他，亦可以成為條紋狀、格子狀、或三角形之方式使 各色變換層配置於LED晶片上。此時，亦可在含有相異之 榮光體的不同層之間設置間隔而配置，若如此一來，混色 性變成良好。另外，若以全部被覆led晶片周圍之方式配 置色變換層，可抑制紫外線被封住樹脂等之外部吸收，故 佳。 __-46· 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 554547 A7 ___ B7 五、發明説明（44 ) 實施形態4 本發明實施形態4係有關適於發光二極體之螢光物質的製 造方法’為一種可防止發光色之色度偏差，並防止帶紅色 成分之減少的螢光物質合成方法。 就螢光物質之合成法，化學計量上混合螢光物質之各原 料，於混合原料中添加硼酸作為助熔劑而燒成之方法已揭 示於特開昭48-4985號公報中。又，在特開昭61_36〇38號 公報中已揭示一種在化學計量上混合各原料之混合原料中 添加氟化鋇作為助熔劑，使粒子成長的方法。 但，為促進粒子成長，若使用一於硼酸中添加氟化鋇者 作為助溶劑而形成螢光物質，則照射激發光所得到之發光 色的色度會產生偏差，紅色成分會減少。 因此，在本實施形態4中，燒成一由含有混合原料與氟化 鋇之助熔劑所構成的混合物時，於前述混合物中添加液體 而進行燒成，俾抑制螢光物質之色度變動。此作用係於燒 成時藉添加液體，混合原料間會變密，反應性會提昇，可 得到一種材質均一且粒子形狀整齊之螢光物質。又，藉燒 成時進行押壓，可進一步提高效果。 又，所添加之液體量愈增加，粒子形狀之整齊愈佳，可 抑制色度之變動。液體量相對於混合原料宜為5 wt%〜2〇〇 ’ 更宜為 10 wt%〜70 wt%，最宜為 5〇 wt%〜7〇 wt%。 就螢光物質之原料，若加於一作用成為賦活劑之Ce並含有 Fe，上述效果可提高。 又，在本實施形態4之勞光物質的製造方法中，係宜以如 L_ -47- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 554547 A7 B7FIG. 6 is a schematic sectional view of an smd-type light emitting diode according to the second embodiment of the present invention. In the light emitting diode system of the second embodiment, the LED chip 5 is arranged on a glass epoxy substrate 12 having a pair of lead electrodes 12a and 12b. The LED chip 5 is basically sapphire via GadAh dN (〇sdg 丨) The buffer layer is formed to form a junction made of a nitride semiconductor (AlxGayInzN 1, OSzS 1, x + y + z = 1). The LED chip 5 has at least a light emitting layer composed of a nitride semiconductor layer. The positive and negative electrodes provided on the surface side of one of the LED chips 5 I are electrically connected to a pair of lead electrodes 1 2 a and 1 2 b and respective conductive leads 7. Further, in the light-emitting diode of Embodiment 2, the same fluorescent substance as that of Embodiment Xia is dispersed in a light-transmitting resin. That is, the fluorescent substance dispersed in the light-transmitting resin 18 includes a large-sized fluorescent substance 81 and a small-sized fluorescent substance 8 2, and all the large-sized fluorescent substances are emitted in the light-emitting diode. The substance 81 maximizes the wavelength conversion effect, seeks to improve the output of the light-emitting diode, and prevents the color unevenness of the fluorescent substance 82 with a small particle size. In the light-emitting diode of this embodiment, the light-transmitting resin 8 is preferably the epoxy resin described in the first embodiment. However, in the second embodiment, the resin is not filled in the package, but the resin is molded on the substrate. Therefore, other methods suitable for its manufacturing method can be used. ) A4 specification (210X297 mm) 554547 A7 ____B7 V. Description of the invention (43) Application mode 1 Same large particle size fluorescent substance 8 1 and small particle size fluorescent substance 8 2 so it can form an ultraviolet light which can efficiently convert The color conversion layer obtains a high-luminance light-emitting diode. In particular, when a plurality of types of phosphors are used for mixed color emission, it is desirable to effectively suppress color unevenness by the scattering effect of a small-sized fluorescent substance. When these heterogeneous fluorescent substances are mixed to form a single color conversion film layer, the center particle diameter and shape of each fluorescent substance should be similar. As a result, light emitted from various fluorescent materials is well mixed, and color unevenness can be suppressed. In the third embodiment, each fluorescent substance may be formed as a separate color conversion layer. When the color conversion layer of each fluorescent substance is arranged as multiple layers, the ultraviolet light transmittance of each fluorescent substance is considered, and a red fluorescent substance layer, a green fluorescent substance layer, and And the blue fluorescent substance layer is preferable because it can efficiently absorb ultraviolet rays in all the layers. Further, in the color conversion multi-layer, from the lower layer to the upper layer, the particle size of the fluorescent substance in each layer becomes smaller, so that the central particle size of each light-emitting substance becomes a blue fluorescent substance &gt; green fluorescent Substance &gt; A red fluorescent substance is preferred because it can transmit ultraviolet rays to the uppermost layer at the same time and absorb them in the color conversion multiple layers without leaking ultraviolet rays. Alternatively, each color conversion layer may be arranged on the LED wafer in a stripe, lattice, or triangle manner. At this time, it is also possible to arrange and arrange the gaps between different layers containing different glare bodies. If so, the color mixing property becomes good. If the color conversion layer is disposed so as to completely cover the periphery of the LED chip, it is preferable to suppress external absorption of ultraviolet rays by the sealing resin or the like. __- 46 · This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 554547 A7 ___ B7 V. Description of the invention (44) Embodiment 4 The fourth embodiment of the present invention relates to a light-emitting diode suitable for light-emitting diodes. A method for producing a fluorescent substance is a method for synthesizing a fluorescent substance that can prevent the chromaticity deviation of the luminous color and prevent the reduction of reddish components. Regarding the method for synthesizing a fluorescent substance, a method of stoichiometrically mixing each raw material of the fluorescent substance and adding a boric acid as a flux to the mixed raw material and firing is disclosed in Japanese Patent Application Laid-Open No. 48-4985. Further, Japanese Patent Application Laid-Open No. 61-36〇38 has disclosed a method for adding particles of barium fluoride as a flux to a mixed raw material for stoichiometrically mixing the raw materials to grow particles. However, in order to promote particle growth, if a fluorescent substance is formed by using barium fluoride added to boric acid as a co-solvent, the chromaticity of the luminous color obtained by irradiating the excitation light will vary, and the red component will decrease. Therefore, in the fourth embodiment, when a mixture composed of a flux containing a mixed raw material and barium fluoride is fired, a liquid is added to the mixture to perform the firing, thereby suppressing the color change of the fluorescent substance. This effect is that by adding liquid during firing, the mixed raw materials will become denser and the reactivity will be improved, and a fluorescent material with uniform material and uniform particle shape can be obtained. In addition, the effect can be further enhanced by pressing when firing. In addition, the more the amount of liquid added, the better the shape of the particles, and the change in chromaticity can be suppressed. The amount of liquid relative to the mixed raw material is preferably 5 wt% to 200 ', more preferably 10 wt% to 70 wt%, and most preferably 50 wt% to 70 wt%. As for the raw material of the fluorescent substance, if the Ce is added as an activating agent and Fe is contained, the above effects can be improved. In addition, in the manufacturing method of the polished material of the fourth embodiment, it is preferable to apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to the paper size of L_ -47- 554547 A7 B7

下之二階段進行燒成，即由混合著螢光物質原料之混合原 料與助熔劑所構成的混合物在大氣中或弱還原氣氛中進行 之第一燒成步驟；及，在還原氣氛中進行之第二燒成步 此處在本發明中，所谓弱還原氣氛係在從混合原料形 成所希望的螢光物質之反應過程中，設定成至少含有必須 的氧量之弱還原氣氛，藉由進行第一燒成步驟至在此弱還 原氣氛中所希望之螢光物質的構造形成結束，可防止勞光 物質變黑且防止光之吸收效率劣化。又，在第二燒成步驟 中之還原氣氛中，係謂比弱還原氣氛還強之還原氣氛。 若如此地以二階段進行燒成，可得到激發波長之吸收效 率高的螢光物質《藉此，例如適用於發光二極體時，為得 到所希望之色調，可減少必須的螢光物質量，得到光取出 效率高的發光二極體。 變形例1 (透光性樹脂） 在實施形態1中係使用特定之環氧樹脂作為較佳例，但在 本發明中，亦可混合其他之樹脂或玻璃與實施形態1所說明 之螢光物質而使用，以構成發光二極體。 其時，適用來作為透光性樹脂之具體材料，可舉例··其 他種類之環氧樹脂（含氮環氧樹脂等）、丙締酸樹脂、矽酮 等之耐候性優的透明樹脂或玻璃等。於此等樹脂等亦可含 有由大粒徑螢光物質及小粒徑螢光物質所構成的螢光物 質’亦可構成高輸出的發光二極體。又，於透光性樹脂中 _ -48- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)The next two stages are firing, that is, the first firing step of a mixture composed of a mixed raw material mixed with a fluorescent material raw material and a flux in the atmosphere or a weak reducing atmosphere; and, Second firing step Here in the present invention, the so-called weak reducing atmosphere is a weak reducing atmosphere containing at least a necessary amount of oxygen during a reaction process for forming a desired fluorescent substance from a mixed raw material. From the firing step to the end of the formation of the desired fluorescent substance in this weakly reducing atmosphere, it is possible to prevent the light-emitting substance from becoming black and to prevent the light absorption efficiency from being deteriorated. The reducing atmosphere in the second firing step is a reducing atmosphere that is stronger than a weak reducing atmosphere. If it is fired in two steps in this way, a fluorescent substance with a high absorption efficiency at the excitation wavelength can be obtained. Therefore, when it is applied to, for example, a light-emitting diode, the required fluorescent substance mass can be reduced to reduce the mass To obtain a light emitting diode with high light extraction efficiency. Modification 1 (transparent resin) In the first embodiment, a specific epoxy resin is used as a preferred example. However, in the present invention, other resins or glasses may be mixed with the fluorescent substance described in the first embodiment. Instead, it is used to form a light emitting diode. At this time, it is suitable as a specific material for the light-transmitting resin, and examples include other types of epoxy resins (nitrogen-containing epoxy resins), acrylic resins, silicones, and other transparent resins or glasses having excellent weather resistance Wait. These resins and the like may contain a fluorescent substance composed of a large particle size fluorescent substance and a small particle size fluorescent substance ', and may also constitute a high-output light-emitting diode. In translucent resin _ -48- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm)

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554547 A7 ___ B7 五、發明説明（46 ) 亦可含有前述螢光物質以及顏料。 又，為提高透光性樹脂之耐候性，亦可於透光性樹脂中 添加紫外線吸收劑，進一步，亦可於透光性樹脂中添加氧 化防止劑、或有機羧酸鋅、酸酐、鋅螯合化合物等。 變形例2 (擴散劑） 進一步，於|發明中，在透光性樹脂中亦可加於螢光物 質而含有擴散劑。具體之擴散劑可適當地使用鈦酸鋇、氧 化鈦、氧化鋁、氧化矽、碳酸鈣等。又，亦可使用蜜胺樹 脂、CTU鳥糞胺樹脂、苯並烏糞胺樹脂等之有機擴散劑。 若如此一來，可構成一具有良好指向特向之發光二極 體。 此處在本說明書中所謂擴散劑係指中心粒徑為1 nm以上5 以下者。1 以上5 以下之擴散劑係使來自LED晶 片及螢光物質之光良好地散射，藉由使用大粒徑螢光物質 可抑制易產生的色不均，故佳。又，藉由擴散劑之使用， 可縮小發光光譜之半幅值，並得到色純度高之發光二極 體。 另外，1 nm以上1 以下之擴散劑係對於來自LED晶片 之光的干涉效果低之反面，不會使光度下降而可提高樹脂 黏度。若利用此，藉黏合等於封裝體之凹部内充填樹脂 時，可在注射器内略均一地使樹脂中之螢光物質分散並維 持其狀態，即使使用比較難處理之大粒徑螢光物質時，亦 可良率佳地進行生產。如此在本發明中之擴散劑係依粒徑 -49- ΐ紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) ： &quot; 554547 A7554547 A7 ___ B7 V. Description of the invention (46) It may also contain the aforementioned fluorescent substances and pigments. In addition, in order to improve the weatherability of the translucent resin, an ultraviolet absorber may be added to the translucent resin, and further, an anti-oxidant, or organic zinc carboxylic acid, acid anhydride, and zinc chelate may be added to the translucent resin. Compounds and so on. Modification 2 (diffusing agent) Further, in the invention, a diffusing agent may be added to a fluorescent material in a translucent resin. Specific diffusing agents include barium titanate, titanium oxide, aluminum oxide, silicon oxide, calcium carbonate, and the like. In addition, organic diffusing agents such as melamine resin, CTU guanoamine resin, and benzocinamine resin can also be used. If so, a light-emitting diode with good directivity can be constructed. The term "diffusing agent" as used herein refers to one having a central particle diameter of 1 nm to 5 nm. A diffusing agent of 1 to 5 can scatter light from LED wafers and fluorescent substances well, and it is preferable to use a large-diameter fluorescent substance to suppress color unevenness that easily occurs. In addition, the use of a diffusing agent can reduce the half-amplitude of the light emission spectrum and obtain a light emitting diode with high color purity. In addition, the diffusing agent with a wavelength of 1 nm or more is the opposite side of the low interference effect on the light from the LED chip, and it does not decrease the luminosity and can increase the resin viscosity. If this is used, when the resin is filled in the concave portion of the package by bonding, the fluorescent substance in the resin can be dispersed and maintained in a uniform state in the syringe, even when using a large-size fluorescent substance that is difficult to handle, Production can also be performed with good yield. The diffusing agent in the present invention is based on the particle size -49--The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm): &quot; 554547 A7

範圍而作用相異，可§£合使用方法而選擇或組合而使用。 變形例3 (填充劑） 進一步，在本發明中，亦可於透光性樹脂中加於螢光物 質而含有填充劑。具體的材料係與擴散劑相同，但，擴散 州與中〜粒徑乃相異，在本說明書中填充劑乃指中心粒徑 為jetn以上100 以下者。若於透光性樹脂中含有如此 粒徑之填充劑，藉光散射作用可改善發光二極體之色度參 差不齊，尚且，可提高透光性樹脂之耐熱衝擊性。因此， 即使在咼溫下之使用，亦可防止LED晶片與封裝體等電極 電氣連接之引線斷掉或前述LED晶片之底面與封裝體之凹 部底面的_等。藉此，可提供_種信賴性高的發光二極 體。進一步可調整樹脂之流動性成長時間一定，可於所希 望之處塗布特定量的透光性樹脂，並可良率佳地進行量 產。 又，填充劑罝具有與螢光物質類似之粒徑及/或形狀。此 處在本說明書中所謂類似的粒徑係指各粒子的各個中心粒 徑之差為2 0 %以下的情形，所謂類似之形狀係指表示與各 粒徑之真圓的似近程度之圓形度（圓形度=等於粒子之投影 面積的真圓的周圍長度/粒子之投影的周圍長度），其值之 差為20%以下的情形。藉由使用如此之填充劑，螢光物質 與填充劑會互相作用，在樹脂中可良好地分散螢光物質， 並抑制色不均。進一步，螢光物質及填充劑其中心粒徑均 為15 〜50 ’更宜為20 〜5〇 #πι，藉由如此地調 -50- 本纸張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐) 554547 A7 B7 五、發明説明（48 ) 整粒徑，可於各粒子間設有較佳的間隔而配置。因此可確 保光之取出路徑，並能抑制填充劑混入造成之光度降低同 時並能改善指向特性。又，若於透光性樹脂中含有如此之 粒徑範圍的螢光物質及填充劑，並以孔版印刷法形成透光 性樹脂，在硬化透光性樹脂後之切片步驟中切片刮刀之填 塞可產生所往返之修整效果，並提高量產性。 在切片步驟中，為得到良好的修整效果，宜含有大粒徑 者作為填充劑，若於透光性樹脂、中含有中心粒徑為15 〜50 ，宜20 /zm〜50 /zm之填充劑，可有效地使切片刮 刀之填塞返往，得到優異之修整效果。 變形例4 (發光面） 在本發明中，接觸發光二極體之發光面的透光性樹脂表 面可為曲面。尤其，實施形態2所示並於基板上模鑄樹脂之 型的發光二極體中，藉封裝體之側壁無法於上方使光反 射，故宜以透光性樹脂之表面作為曲面而實現所希望的指 向特向。 如此之曲面即發光面係藉由一使用對應於各個發光二極 體而分別形成開口部的掩模3 9(圖7 A)，以孔版印刷形成一 必須之物質被分散的透光性樹脂來實現的。圖7A、圖7B 中模式地表7F其樣式。如此所形成之透光性樹脂的表面， 一般係樹5曰被熱硬化後’成為曲面，但可對應於掩模3 9之 材質及構造、樹脂的充填量而形成特定的形狀。藉此方 法，可使發光二極體量產性佳地進行製造。又，即使含有 ______-51 - 本紙張尺度適财a S家標準(CNS) Α4規格(21G X 297公爱)' 裝 訂The scope and effect are different, and they can be selected or combined according to the usage method. Modification 3 (Filler) Further, in the present invention, a fluorescent substance may be added to the translucent resin to contain a filler. The specific material is the same as the diffusing agent, but the diffusion state is different from the medium to particle size. In this specification, the filler refers to the one having a central particle size of at least jetn and at most 100. If a filler having such a particle size is contained in the light-transmitting resin, the light-scattering effect can improve the unevenness of the color of the light-emitting diode, and the heat-impact resistance of the light-transmitting resin can be improved. Therefore, even when used at high temperatures, it is possible to prevent the leads of the electrical connection between the LED chip and the package body from being broken or the bottom surface of the aforementioned LED chip and the bottom surface of the concave portion of the package body. This makes it possible to provide a variety of highly reliable light-emitting diodes. Further, the resin can be adjusted to have a certain fluidity growth time, and a certain amount of light-transmitting resin can be applied at a desired place, and mass production can be performed with good yield. The filler 罝 has a particle size and / or shape similar to that of a fluorescent substance. Herein, in this specification, the similar particle size refers to a case where the difference between the central particle sizes of the particles is 20% or less, and the similar shape refers to a circle representing a degree of closeness to the true circle of each particle size. When the degree of circularity (roundness = peripheral length of a true circle equal to the projected area of particles / peripheral length of a projected particle), the difference between the values is 20% or less. By using such a filler, the fluorescent substance and the filler interact with each other, the fluorescent substance can be well dispersed in the resin, and color unevenness is suppressed. Further, the central particle diameter of the fluorescent substance and the filler is 15 to 50 ′, and more preferably 20 to 5〇 # πι. By adjusting in this way, -50- This paper size applies the Chinese National Standard (CNS) Α4 specification ( 210 X 297 mm) 554547 A7 B7 V. Description of the invention (48) The particle size can be adjusted by setting a better interval between each particle. Therefore, it is possible to ensure the light extraction path, and to suppress the decrease in luminosity caused by the mixing of fillers, and to improve the directivity characteristics. In addition, if the translucent resin contains a fluorescent substance and a filler in such a particle size range, and the translucent resin is formed by a stencil printing method, the slicing blade can be filled in the slicing step after the translucent resin is cured. Produces the trimming effect of round trips and improves mass productivity. In the slicing step, in order to obtain a good dressing effect, those with large particle diameters should be used as fillers. If the light-transmitting resin contains a central particle diameter of 15 to 50, a filler of 20 / zm to 50 / zm is preferred. , Can effectively make the filling of the slicing blade back, get excellent trimming effect. Modification 4 (Light-emitting surface) In the present invention, the light-transmitting resin surface that contacts the light-emitting surface of the light-emitting diode may be a curved surface. In particular, in the light-emitting diode of the type shown in the second embodiment and the resin is molded on the substrate, the side of the package cannot reflect light from above. Therefore, the surface of the transparent resin should be used as a curved surface to achieve the desired result. Pointing special. Such a curved surface, that is, a light emitting surface, is formed by using a mask 39 (FIG. 7A) in which openings corresponding to the respective light emitting diodes are respectively formed by stencil printing to form a translucent resin in which necessary substances are dispersed. Realized. The pattern 7F in FIG. 7A and FIG. 7B has a pattern. The surface of the light-transmitting resin formed in this way is generally a curved surface after being heat-cured, but it can be formed into a specific shape in accordance with the material and structure of the mask 39 and the filling amount of the resin. By this method, light-emitting diodes can be manufactured with high productivity. In addition, even if it contains ______- 51-this paper is suitable for a family standard (CNS) Α4 size (21G X 297 public love) 'binding

554547554547

一具有粒徑之大粒徑螢光物質與小粒徑螢光物質的本發明 之發光二極體經長時間而進行量產時，其步驟最初所製作 足發光二極體與最後所製作之發光二極體之間的發光參差 不齊可縮減至極小，提昇良率。 進一步’使用矽酮作為掩模39的材料，可降低成本，尚 且藉碎酮與透光性樹脂之熱膨脹差等，可形成一具有所希 望曲面之發光面。 變形例5 在本實施形態1等中，LED晶片與封裝體係藉引線連接， 但本發明不限於此，亦可以使用導電性構件而將LED晶片 倒裝於黏合於封裝體之收藏部1&amp;的方式，取出自LED晶片 之基板側所輸出的光。 亦即，封裝體如圖1所示般係絕緣分離部4位於收藏部 la(貫通孔）内，於其兩側露出金屬薄板2a、2b，故只要跨 於絕緣分離部4而載置LED晶片，分別連接LED晶片之正負 電極，連接於金屬薄板2a、2b即可。 變形例6 又’在上述實施形態及變形例之發光二極體，係形成 SMD型發光二極體，但本發明不限於此。 例如，在實施形態1所說明之螢光物質及/或環氧樹脂係 可利用於顯示器、8段型或砲彈型等各種型態之發光二極 gal» 體0 亦即’若利用實施形態1所說明之螢光物質，可得到高輸 出之發光二極體，若利用實施形態丨所說明之環氧樹脂，可 -52- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)When the light-emitting diode of the present invention has a large-diameter fluorescent material and a small-diameter fluorescent material with a particle diameter and is mass-produced over a long period of time, the steps are first to produce a foot-emitting diode and finally to produce the light-emitting diode. The uneven light emission between the light emitting diodes can be reduced to a minimum, and the yield is improved. Further, the use of silicone as the material of the mask 39 can reduce the cost, and furthermore, a light emitting surface having a desired curved surface can be formed by the difference in thermal expansion between the broken ketone and the light-transmitting resin. Modification 5 In the first embodiment and the like, the LED chip and the packaging system are connected by leads, but the present invention is not limited to this, and the LED chip may be flip-chip mounted on the storage portion 1 &amp; Method, taking out the light output from the substrate side of the LED wafer. That is, as shown in FIG. 1, the package is such that the insulation separation portion 4 is located in the storage portion la (through-hole), and the thin metal plates 2 a and 2 b are exposed on both sides thereof. Therefore, the LED chip needs to be placed across the insulation separation portion 4. It can be connected to the positive and negative electrodes of the LED chip and the thin metal plates 2a and 2b respectively. Modification 6 In the light-emitting diodes of the above embodiments and modifications, SMD-type light-emitting diodes are formed, but the present invention is not limited to this. For example, the fluorescent substance and / or epoxy resin described in the first embodiment can be used in various types of light-emitting diode gals, such as a display, an 8-segment type, or a cannonball type. The fluorescent materials described can obtain high-output light-emitting diodes. If the epoxy resin described in the embodiment 丨 is used, it can be -52- This paper size applies to China National Standard (CNS) A4 (210 X 297) (Centimeter)

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554547 A7 B7 五、發明説明（5〇 ) 提供信賴性高的發光二極體。 在本實施形態1中所說明之透光性樹脂不僅用於發光二極 體等之發光元件，亦可適用於光二極體等之受光元件。 實施例 以下，說明有關本發明之實施例。又，本發明不限於以 下所示之實施例。 實施例1 製作圖8之斷面圖所示的SMD型發光二極體作為本發明之 發光二極體，就LED晶片5，乃使用一具有由InGaN所構成 之發光層且主發光波峰為470 nm的LED晶片。在本實施例1 之發光二極體中，封裝體係由基底部分與側壁部分以一體 成形之樹脂成形體24所構成。導線電極22a、22b係*** 成形於樹脂24之基底部份。LED晶片係利用MOCVD法而 形成的。具體上係於反應室内安裝已洗淨之藍寶石基板， 反應氣體乃使用TMG(三甲基）氣體、TMI (三甲基銦）氣 體、TMA(三甲基鋁）氣體、氨氣體及作為載體氣體之氫 氣、進一步使用矽烷氣體及環戊二鎂作為雜質氣體而進行 成膜。 就LED晶片之層構成乃於藍寶石基板上依序形成如下之 層： 低溫緩衝層即AlGaN層、 用以使結晶性提昇之未摻雜GaN(厚約15000A)、 形成電極之η型接觸層即Si摻雜的GaN層（厚約21650A)、 用以提昇結晶性之未摻雜的GaN層（厚約3000A)、 •53· 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 554547 A7 B7 五、發明説明（51 ) 以未摻雜之GaN(厚約50A)與Si摻雜的GaN(厚約300A) 超格子所構成之多層膜（η型覆蓋層）、 用以提昇發光層結晶性之未摻雜GaN(厚約4 0 Α)與未摻雜 InGaN(厚約20A)的超格子所構成之多層膜、 由未摻雜GaN(厚約250A)與InGaN(厚約30A)所構成之多 重量子井構造的發光層、 由摻雜Mg之InGaN(厚約25A)與摻雜Mg之GaAIN(厚約 4 0A)的超格子所構成之多層膜、.及、 p型接觸層即摻雜Mg之GaN層（厚約1200A)。 如此一來而形成複數氮化物半導體層之半導體晶圓部分 被蝕刻而使η型接觸層之一部分露出。繼而，於所露出之p 型及η型接觸層上分別利用濺鍍法而形成^型及ρ型之電極 後，分割成各個LED晶片而製作可發出藍色光之LED晶 將如以上所製作之LED晶片藉模黏合樹脂6模黏合於一導 線電極22a、22b於樹脂24 —體成形所構成之成形體封裝 體凹部，分別使用35从m之金屬引線7而將LED晶片之各電 極與各導線電極22 a、22b引線黏合、電氣連接。 在本實施形態1係製作以G d取代約2成Y且中心粒徑為 21.429 #111之（丫0.8〇(10.2)2.965八15〇12:〇60.035 而使用來作為螢 光物質。前述螢光物質係包括大粒徑螢光物質與小粒徑螢 光物質’具有圖2A、2B所示之體積基準粒度分布。在體 積基準分布曲線中，斜率為〇之平坦區域係加算值4.6 vol%、且粒徑範圍1.371 〜8·379 。亦即，全螢光物 -54· 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公羡) 一 554547 A7 B7 五、發明説明（52 ) ' 質中之4·6 v〇l%係由具有比1.371 /zm還小粒徑之小粒徑螢 光物質所構成，其餘95.6 vol%係由具有比8.379 //m還大粒 徑之大粒徑螢光物質所構成。為具有如此之分布，依沉澱 法所分級之螢光物質的中心粒徑為2丨·4 ,在前述中心粒 徑之頻度值為29.12%。又，小粒徑螢光物質之頻度波峰粒 徑直為0.613 ，大粒徑螢光物質之頻度波峰粒徑值為 22.908 //m。又，在本實施形態1中，大粒徑螢光物質之粒 度分布中的標準偏差為0.295。_ 為得到在CIE之色度表呈x、y = (〇 33、〇·33)之光，以重 量比為16 : 100之方式混合所調整之螢光物質與透光性樹 脂。將如此所得到之含螢光物質環氧樹脂藉澆灌充填於一 LED晶片以金屬線連接於一對導線電極之封裝體凹部内， 使之硬化而形成發光二極體。 藉由如此成形，可得到一擁有高輝度及高輸出而能發光 白光之發光二極體。 比較例1 為了比較，除了使用體積基準分布曲線如圖9A、9B之粒 度分布範圍很廣的勞光物質，且，中心粒徑為6 · 3 15 // m即 (Y〇.8Gd〇.2)2.965Al5〇i2: Ce〇.〇35螢光體以外，其餘與實施例1 相同做法，而製作一成為同樣色度點之發光二極體。若測 定此比較例之發光二極體的光度及輸出，比實施例1之發光 二極體，光度約降低3 5 %，輸出約降低2 5 %。藉此，可知 本發明之發光二極體即使在白色系等色純度低的長波長側 亦可呈高輝度發光。 ____ _-55·__ 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐） 裝 訂554547 A7 B7 5. Description of the invention (50) Provide a highly reliable light-emitting diode. The translucent resin described in the first embodiment is applicable not only to light-emitting elements such as light-emitting diodes but also to light-receiving elements such as light-emitting diodes. Examples Hereinafter, examples of the present invention will be described. The present invention is not limited to the embodiments shown below. Example 1 An SMD light-emitting diode shown in the cross-sectional view of FIG. 8 was produced as the light-emitting diode of the present invention. For the LED chip 5, a light-emitting layer made of InGaN was used and the main light-emitting peak was 470. nm LED chip. In the light-emitting diode of the first embodiment, the packaging system is composed of a resin molded body 24 formed integrally with the base portion and the side wall portion. The lead electrodes 22a and 22b are inserted into a base portion formed on the resin 24. LED wafers are formed using the MOCVD method. Specifically, the cleaned sapphire substrate is installed in the reaction chamber. The reaction gas is TMG (trimethyl) gas, TMI (trimethylindium) gas, TMA (trimethylaluminum) gas, ammonia gas, and carrier gas. The film was formed using hydrogen, silane gas, and cyclopentamagnesium as impurity gases. With regard to the layer structure of the LED wafer, the following layers are sequentially formed on the sapphire substrate: a low-temperature buffer layer, namely, an AlGaN layer, undoped GaN (about 15000A thick) for improving crystallinity, and an n-type contact layer for forming an electrode, namely Si-doped GaN layer (approximately 21650A thick), undoped GaN layer (approximately 3000A thick) to improve crystallinity, • 53 · This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) ) 554547 A7 B7 V. Description of the invention (51) Multilayer film (n-type cover layer) composed of undoped GaN (about 50A thick) and Si-doped GaN (about 300A thick) superlattice, used to improve A multilayer film composed of a superlattice of crystalline non-doped GaN (thickness about 40 A) and undoped InGaN (thickness of about 20 A). The non-doped GaN (thickness of about 250 A) and InGaN (thickness of about 250 A) 30A) light emitting layer with multiple quantum well structure, multilayer film consisting of Mg-doped InGaN (about 25A thick) and Mg-doped GaAIN (about 40A thick) superlattice, and p-type The contact layer is a Mg-doped GaN layer (about 1200A thick). In this way, a portion of the semiconductor wafer forming the plurality of nitride semiconductor layers is etched to expose a portion of the n-type contact layer. Then, ^ -type and ρ-type electrodes are formed on the exposed p-type and η-type contact layers by sputtering, respectively, and then divided into individual LED chips to produce LED crystals that can emit blue light as described above. The LED chip is bonded to a lead electrode 22a, 22b and a resin 24 by forming a mold package. The concave portion of the molded package body is formed by resin molding. The electrodes of the LED chip and each lead are connected by using metal leads 7 of 35 m in length. The electrodes 22 a and 22 b are bonded and electrically connected. In the first embodiment, G is used to replace about 20% of Y with a central particle size of 21.429 # 111 (Ya 0.80 (10.2) 2.965 8 1512: 060.035) and used as a fluorescent substance. The substance system includes a large-size fluorescent substance and a small-size fluorescent substance 'having a volume-based particle size distribution shown in FIGS. 2A and 2B. In the volume-based distribution curve, a flat area with a slope of 0 is an added value of 4.6 vol%, And the particle size range is 1.371 to 8.379. That is, full-fluorescein-54 · This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public envy) 554547 A7 B7 V. Description of the invention (52) '4.6 vol% of the mass is composed of a fluorescent material with a small particle diameter smaller than 1.371 / zm, and the remaining 95.6 vol% is composed of a particle with a larger particle diameter than 8.379 // m The particle size is composed of fluorescent substances. In order to have such a distribution, the center particle diameter of the fluorescent substance classified according to the precipitation method is 2 丨 · 4, and the frequency value of the center particle diameter is 29.12%. Also, the small particle diameter The frequency peak particle size of the fluorescent substance is 0.613, and the frequency peak particle size of the large particle fluorescent substance is 22.908 // m. In the first embodiment, the standard deviation in the particle size distribution of the large-particle-size fluorescent substance is 0.295. _ In order to obtain light in the CIE chromaticity table, x, y = (〇33, 〇 · 33), weight The adjusted fluorescent substance and light-transmitting resin are mixed in a ratio of 16: 100. The fluorescent substance-containing epoxy resin thus obtained is filled in an LED chip by pouring and is connected to a pair of wire electrodes by metal wires. The light-emitting diode is hardened in the body recess to form a light-emitting diode. By forming in this manner, a light-emitting diode having high luminance and high output and capable of emitting white light can be obtained. Comparative Example 1 For comparison, in addition to using a volume-based distribution curve As shown in Figures 9A and 9B, the material has a wide range of particle size distribution, and the center particle diameter is 6 · 3 15 // m, that is (Y〇.8Gd〇.2) 2.965Al5〇i2: Ce〇.〇35 fluorescent Except for the light body, the rest is the same as in Example 1, and a light-emitting diode with the same chromaticity point is produced. If the light-emitting diode and the output of the light-emitting diode of this comparative example are measured, it is better than that of Example 1 , The luminosity is reduced by about 35%, and the output is reduced by about 25%. Bright light-emitting diodes can emit high luminance even on long-wavelength sides with low color purity, such as white. ____ _-55 · __ This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) binding

554547 A7 B7 五、發明説明（53 ) 又，使用於本比較例之螢光物質的粒度分布中的標準偏 差為0.365。 實施例2 就實施例2係使用經如下分級之螢光物質，即螢光物質之 組成比為（丫〇.995〇(1。.()。5)2.750八15〇12:〇6〇25〇，加算值為〇〇77 vol%且在1.371 //m〜8.379 //m之粒徑範圍具有平坦區域， 前述螢光物質之中心粒徑為25.626 Am、前述中心粒徑中之 頻度值為24.812%、小粒徑勞·光物質之頻度波學粒後值為 0 · 6 1 3 y m，大粒徑螢光物質之頻度波峰粒徑值為2 8 · 〇 j 2 Vm ;除此之外，其餘與實施例1相同，而製作一成為同樣 色度點的發光二極體。若測定實施例2之發光二極體的光度 及輸出，比實施例1之發光二極體，光度約提高1 8 〇/〇 ,輸出 約提南1 0 % ^藉實施例2之發光二極體，可提供比實施例1 更高輝度之發光二極體。 在本實施例2中，大粒徑螢光物質之粒度分布中的標準偏 差為0.259。 實施例3 以重量比為100 : 50之方式混合環氧樹脂、與、作為擴散 劑而中心粒徑為2.5 //m之Si02，然後，在含有其擴散劑之 環氧樹脂中混合與實施例i之螢光物質同樣的螢光物質，其 以外，係與實施例1同樣做法，而製作一成為與實施例i同 樣色度點的發光二極體。此實施例3之發光二極體係得到與 實施例1同樣的輝度及輸出，又，比實施例1更可抑制色不 均且得到良好的色調。 _____ -56- 本紙τ國Η冢標準(CNS) Α;規格(21GX 297涵 &quot; 一554547 A7 B7 5. Description of the invention (53) In addition, the standard deviation in the particle size distribution of the fluorescent substance used in this comparative example is 0.365. Example 2 For Example 2, a fluorescent substance that is classified as follows is used, that is, the composition ratio of the fluorescent substance is (y 0.9995 (1 .. (). 5) 2.750 eight 15012: 〇06.025 〇, the added value is 〇77 vol% and has a flat area in the range of 1.371 //m~8.379 // m particle size, the center particle diameter of the fluorescent substance is 25.626 Am, and the frequency value in the center particle diameter is 24.812%, the frequency of small particle size light and light matter after wave particle value is 0 · 6 1 3 ym, the frequency of the large size fluorescent substance peak value is 2 8 · 〇j 2 Vm; The rest is the same as in Example 1, and a light-emitting diode with the same chromaticity point is produced. If the light-emitting diode and the output of the light-emitting diode of Example 2 are measured, the luminosity is improved compared to the light-emitting diode of Example 1. 1 8 〇 / 〇, the output is about 10%. ^ By using the light-emitting diode of Example 2, it can provide a light-emitting diode with higher brightness than that of Example 1. In this Example 2, a large particle size fluorescent The standard deviation in the particle size distribution of the light substance is 0.259. Example 3 The epoxy resin was mixed with a weight ratio of 100: 50, and the center particle diameter was used as a diffusing agent. 2.5 // m of Si02, and then mixed the same fluorescent substance as the fluorescent substance of Example i in the epoxy resin containing the diffusing agent, except that the same procedure as in Example 1 was performed, and the first The light-emitting diode with the same chromaticity point in Example i. The light-emitting diode system of Example 3 obtained the same brightness and output as in Example 1, and it could suppress color unevenness and obtain a good hue than Example 1. _____ -56- This paper τ National Standard (CNS) Α; Specifications (21GX 297) &quot; 1

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554547 A7 B7 五、發明説明（54 ) 實施例4 如圖6所示，電氣連接於基板上之led晶片上，使用模具 而配置含有螢光物質之透光性樹脂，除此之外，其餘與實 施例1同樣做法，而製作一成為同樣色度點之發光二極體。 可得到具有平滑發光面之發光二極體，並得到與實施例j同 樣的特性。 實施例5 如圖7·Α、7B所示，於電·氣連接LED晶片5之基板32 上’藉由使用一由矽酮所構成之掩模3 9的孔版印刷法，形 成一含螢光物質之透光性樹脂，使之硬化，除此之外，其 餘與實施例1同樣做法，製作一成為同樣色度點的發光二極 體。可得到此發光面具有曲面之發光二極體，並得到比實 施例1更均一的發光。 又’於基板3 2係對應於各LED晶片分別設有正電極 32a 、 32b 〇 實施例6 以重量比100 : 5 0之方式混合環氧樹脂、與、作為擴散劑 而中心粒徑為2.5 之Si02，然後，混合與實施例2同樣之 螢光物質，進一步，使用一作為填充劑而中心粒徑為6 之Si〇2相對於前述環氧樹脂量含有70 wt%者作為透光性樹 脂。將此透光性樹脂藉由孔版印刷法與實施例5同樣做法充 填於一 LED晶片以金屬線連接於一對導線電極且具有壁面 之框體的凹部内，以85 eCX3小時，進一步以140 °C X 4小 時硬化，而製作一成為與實施例1同樣色度點之發光二極 __157-：___ 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公复） 554547 A7 B7 五、發明説明（55 ) 體。此實施例6之發光二極體係進一步壽命會提高，可得到 具有均一發光之發光二極體。 實施例7 使用與實施例2相同的螢光物質，並且使用具有與前述螢 光物質相同之粒徑且中心粒徑為約25 /zm之以〇2作為填充 劑，除此以外，其餘與實施例3相同做法而形成發光二極 體。藉此，光度可比實施例3提高1 0 %。 實施例8 使用與實施例2相同之螢光物質，並且使用前述勞光物質 與圓形度之差為1 0%且中心粒徑為約25 μιη之Si02作為填充 劑，除此之外，其餘與實施例6同樣做法，而形成發光二極 體。藉此光度可比實施例6提高10%。 實施例9 如圖10A及其部分擴大圖即圖10B所示，將LED晶片5 (與實施例1同樣者）以環氧樹脂42模黏合於一施予光澤鍍 膜之銅製安裝引線42a的杯狀部後，將LED晶片5之各電極 與安裝引線42a及第二引線42b分別使用直徑為30 之引 線7而進行引線黏合。其次，以可得到在ciE之色度表呈 X、y = (0.33、0·33)之光的方式，與實施例2同樣的螢光物 質與透光性樹脂即環氧樹脂混合成重量比為5 : 1 〇〇者注入 於前述安裝引線的杯狀内後，以15〇°C之溫度硬化1小時， 形成含有螢光物質之塗覆部48。進一步從發光觀測面觀看 而呈圓狀般，以透光性環氧樹脂形成砲彈型透鏡49 ^如此 一來所得到之燈泡型發光二極體係具有與實施例1相同的效 -58 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)554547 A7 B7 V. Description of the Invention (54) Example 4 As shown in FIG. 6, the LED chip on the substrate is electrically connected, and a light-transmitting resin containing a fluorescent substance is arranged using a mold. In the same manner as in Example 1, a light-emitting diode having the same chromaticity point was produced. A light-emitting diode having a smooth light-emitting surface was obtained, and the same characteristics as in Example j were obtained. Example 5 As shown in FIGS. 7A and 7B, on a substrate 32 electrically and pneumatically connected to the LED chip 5, a fluorescein was formed by a stencil printing method using a mask 39 made of silicone. A light-transmitting resin made of a substance was hardened, and the rest was the same as in Example 1 to produce a light-emitting diode having the same chromaticity point. A light-emitting diode having a curved surface on this light-emitting surface was obtained, and more uniform light emission was obtained than in Example 1. The substrate 3 2 is provided with positive electrodes 32a and 32b corresponding to each LED chip. Example 6 An epoxy resin was mixed in a weight ratio of 100: 50, and a central particle diameter of 2.5 was used as a diffusing agent. Then, Si02 was mixed with the same fluorescent substance as in Example 2. Furthermore, SiO2 having a center particle diameter of 6 as a filler and containing 70 wt% of the epoxy resin was used as a translucent resin. This translucent resin was filled into a recess of a frame body having a wall surface connected to a pair of lead electrodes with a metal wire by a stencil printing method in the same manner as in Example 5. The temperature was 85 eCX for 3 hours, and further 140 °. CX is hardened in 4 hours, and a light-emitting diode with the same chromaticity point as in Example 1 is produced. __157-: ___ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public copy) 554547 A7 B7 V. Description of the invention (55) body. The life of the light emitting diode system of this Example 6 will be further improved, and a light emitting diode having uniform light emission can be obtained. Example 7 The same fluorescent substance as in Example 2 was used, and a filler having the same particle diameter as the foregoing fluorescent substance and a central particle diameter of about 25 / zm was used as the filler. The light emitting diode was formed in the same manner as in Example 3. As a result, the luminosity can be increased by 10% compared with the third embodiment. Example 8 The same fluorescent substance as in Example 2 was used, and Si02, which was a 10% difference between circularity and circularity, and had a central particle diameter of about 25 μm, was used as a filler. A light-emitting diode was formed in the same manner as in Example 6. As a result, the luminosity can be increased by 10% compared to Example 6. Example 9 As shown in FIG. 10A and an enlarged view of a part thereof, that is, as shown in FIG. 10B, the LED chip 5 (the same as in Example 1) was bonded to a cup-shaped copper mounting lead 42a with a glossy coating by epoxy resin 42 mold. Each electrode of the LED chip 5 is bonded to the mounting lead 42a and the second lead 42b using a lead 7 having a diameter of 30, respectively. Next, in order to obtain a light having X, y = (0.33, 0.33) in the chromaticity table of ciE, the same fluorescent material as in Example 2 was mixed with the translucent resin, ie, the epoxy resin, in a weight ratio. A person having a size of 5: 100 was injected into the cup shape of the mounting lead, and then cured at a temperature of 150 ° C for one hour to form a coating portion 48 containing a fluorescent substance. When viewed further from the light-emitting observation surface, the light-emitting diode system has the same effect as that of Example 1 when it is formed into a circular shape with a light-transmitting epoxy resin. 49 ^ Applicable to China National Standard (CNS) A4 (210X297 mm)

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554547 A7 B7 五、發明説明（56 ) 果。 實施例1 0 與實施例2相同之螢光物質、透光性樹脂即環氧樹脂、作 為填充劑之前述螢光物質與圓形度之差為丨〇 %且中心粒徑 為約25 /im之Si02的重量比呈1〇〇 ·· 1〇 : 35之方式進行混 合，再注入安裝引線之杯狀内，除此之外，其餘與實施例9 同樣做法而形成燈泡型發光二極體，則可得到比實施例9更 高輝度且均一的發光。 實施例1 1 在一***形成引線電極之樹脂封裝體的凹部内配置與實 施例1同樣的LED晶片，使透光性樹脂即矽酮樹脂、與實施 例1同樣的螢光物質、由中心粒徑為約1 3 # m之 γ2.965Α15012 : Ce0.035所構成的螢光物質、中心粒徑為約0.5 &quot;m之Si02以重量比為1〇〇 : 〇·69 : 〇·5 : 1〇之方式進行混 合，製作一將此混合溶液充填於前述凹部内之發光二極 體，則具有與實施例1同樣的效果，進一步可得到演色性優 且輝度高之發光二極體。 實施例1 2 將透光性樹脂即矽酮樹脂、中心粒徑約為3〇 # m之 (YojGduh.^AlsOu : Ce0.035、與實施例2同樣的螢光物 質、中心粒徑約為〇·5 之Si〇2以重量比為1〇〇 : 〇·69 : 0·5 : 10之方式進行混合，再將此混合溶液充填於前述凹部 内’除此之外’其餘與實施例11相同做法而形成發光二極 體，則具有與實施例2相同的效果，進一步可得到演色性優 -59- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐)554547 A7 B7 V. Description of the invention (56) Fruit. Example 10 The same fluorescent substance as in Example 2, an epoxy resin that is a translucent resin, the aforementioned fluorescent substance as a filler, and the difference between the circularity and the central particle diameter were about 25 / im. The weight ratio of Si02 is mixed in a way of 100 ·· 10: 35, and then injected into the cup shape of the mounting lead. The rest is the same as in Example 9 to form a light bulb type light emitting diode. Then, a higher luminance and uniform light emission can be obtained than in Example 9. Example 1 1 An LED chip similar to that of Example 1 was placed in a recessed portion of a resin package into which a lead electrode was formed, and a silicone resin, which is a light-transmitting resin, and a fluorescent substance similar to that of Example 1 were composed of a central particle. Fluorescent substance consisting of γ2.965A15012: Ce0.035 with a diameter of about 1 3 # m and a central particle size of about 0.5 &quot; m of Si02 in a weight ratio of 100: 〇69: 〇0.5: 1 The method of mixing with 〇 to produce a light-emitting diode in which the mixed solution is filled in the recessed portion has the same effect as in Example 1, and a light-emitting diode with excellent color rendering and high luminance can be obtained. Example 1 2 A silicone resin, which is a light-transmitting resin, has a central particle diameter of about 30 μm (YojGduh. ^ AlsOu: Ce0.035), and the same fluorescent substance as in Example 2 has a central particle diameter of about 0. Si5 in 5 is mixed in a weight ratio of 100: 0 · 69: 0 · 5: 10, and the mixed solution is filled in the recessed portion except that the rest is the same as in Example 11. The method of forming a light-emitting diode has the same effect as in Example 2, and can further obtain excellent color rendering. -59- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

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554547 A7 B7 五、發明説明（57 ) 且輝度高的發光二極體。 實施例1 3 本實施例1 3係有關實施形態1之製造方法的實施例。 在本實施例13中，係製造如圖1所示之表面安裝型的發光 二極體。 在本實施例1 3中，LED晶片5係使用氮化物半導體LED晶 片作為發光層，而該氮化物半導體LED晶片乃具有單色性 發光波峰為可見光即475 nm之InwGawN半導體作為發光 層。更具體地，LED晶片5係於已洗淨之藍寶石基板上使 TMG(三甲基鎵）氣體、TMI(三甲基銦）氣體、氮氣及摻雜 氣體與載體氣體一起流動，再以MOCVD法形成氮化物半導 體而製作成的。此時，藉由切換SiH4與Cp2Mg作為摻雜氣 體而形成一成為η型氮化物半導體或p型氮化物半導體之 層。 LED晶片5之元件構造係於藍寶石基板上依序積層如下： 由在低溫下成長之GaN所構成的緩衝層、 未摻雜之氮化物半導體即η型GaN層、 形成η電極之Si摻雜的GaN層（η型接觸層）、 未摻雜之氮化物半導體即η型GaN層、 成為阻隔層之GaN層、構成電井層之InGaN層、以成為阻 隔層之GaN作為1組，被GaN層挾住之InGaN層進行5層積 層之多重量子井構造的發光層、 已摻雜Mg之AlGaN層（p型覆蓋層）、 已摻雜Mg之GaN層（p型接觸層）。 -60- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 554547 、發明説明（ 又，P型半導體係成膜後在400 以上進行回火。 積層後，藉蝕刻於藍寶石基板上之氮化物半導體側的同 一面側使15型11型之各接觸層表面露出。於接觸層上使用濺 鍍法而分別形成正負電極。又，於？型氮化物半導體上之全 面係形成金屬薄膜作為透光性電極後，在透光性電極之一 邵分形成台座電極。在完成之半導體晶圓拉出划線後，藉 外力進行分割。藉此製作發光元件即LED晶片。 使如以上般製作之LED晶片-藉環氧樹脂模黏合於實施形 態1所說明之封裝體組件的各貫通孔内，再使LED晶片之各 电極、金屬薄板2a、2b分別以金屬線引線黏合，取得電氣 導通。 又’螢光物質係如以上方法進行製作。 首先，使Y、Gd、Ce之稀土族元素之化學計量比溶解於 酸，此溶解液以草酸共沉澱。再燒成此所得到之共沉氧化 物與氧化鋁進行混合而得到混合原料。於其中混合氟化鋇 作為助熔劑而填塞於坩堝内，在空氣中、14〇〇χ：之溫度燒 成3小時而得到燒成品。其燒成品於水中以球研磨進行粉 碎’洗淨、分離、乾燥後，最後通過篩而形成中心粒徑為 22#111之（丫0 995〇(10.005)2.750八15〇12:〇60.250 勞光物質〇 對於一含有中心粒徑為〇·3 //m之Si〇2 2〇 wt〇/〇的環氧樹 月9 ’進一步使前述螢光物質17 wt%、中心粒徑1 〇 v m之 Si〇2 70 wt%混合分散而成之脂環式環氧樹脂組合物（黏度 8000 mPa *s)，利用來作為封住構件。 在本實施例1 3中，係使用由不銹鋼所構成且模厚為1 〇〇 _一__ -61 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 裝 訂 線 554547 A7 _____Β7 五、發明説明（59 ) 之掩模112。掩模設計係與在實施形態丨所說明之圖3相 同。於如此之掩模112，貫通孔之開口侧朝向掩模112側而 使配置著LED晶片之封裝體組件被基板昇降台載置而吸 引’使之接觸掩模112。 於掩模112之端塗布前述透光性樹脂印刷必須的特定量， 減壓至330 Pa。減壓完了後，相對於掩模112之垂直線而朝 動作方向傾斜30度之刮刀14 ,對其施予0·10 MPa&lt;印壓空 氣壓再進行第1次往返的往壓擠。其次，在真空室内加壓至 20000 Pa。加壓完後，相對於掩模112之垂直線而朝往壓擠 相反方向之動作方向傾斜3 5度的刮刀1 5，對其施予〇· 12 MPa之印壓空氣壓而進行第！次之返壓擠。此往返壓擠進行 2次往返。' 然後’使基板昇降台下降，封裝體组件從掩模112拉離。 其後’使透光性樹脂在8 5 °C下以3小時暫時硬化，其次在 140 C下以4小時二次硬化。如此一來而涵蓋前述貫通孔上 與其兩端之絕緣基板上面可形成表面平滑的透光性樹脂。 再者’於薄膜厚為150 /zm且其黏層為20 之紫外線硬 化型切片黏著片上，使封裝體組件之透光性樹脂側對向於 黏著層而進行接著。從封裝體組件之底面側使用切片刀， 為分割成各個發光二極體，切眼深入至前述封裝體組件及 切片黏著片的100 Am之深度。最後從薄膜側照射紫外線而 使黏著層硬化，分割成各發光二極體。製作500個如此所得 到之表面安裝型（SMD型）的發光二極體，測定無參差不齊 後’不同發光二極體間之色度參差不齊很少。又，在各發 -62· 本纸張尺度適用中國國家標準(CNS) A4規格(21〇χ297公釐) 554547 A7554547 A7 B7 V. Description of the invention (57) A light emitting diode with high luminance. Example 1 3 This example 1 3 is an example related to the manufacturing method of the first embodiment. In the thirteenth embodiment, a surface-mount type light emitting diode shown in Fig. 1 is manufactured. In this embodiment, the LED wafer 5 uses a nitride semiconductor LED wafer as the light-emitting layer, and the nitride semiconductor LED wafer has a monochromatic InwGawN semiconductor whose emission peak is visible light, that is, 475 nm, as the light-emitting layer. More specifically, the LED chip 5 is made by flowing a TMG (trimethylgallium) gas, a TMI (trimethylindium) gas, a nitrogen gas, and a doping gas together with a carrier gas on a cleaned sapphire substrate, followed by MOCVD. It is made by forming a nitride semiconductor. At this time, a layer which becomes an n-type nitride semiconductor or a p-type nitride semiconductor is formed by switching SiH4 and Cp2Mg as the doping gas. The element structure of the LED wafer 5 is sequentially laminated on the sapphire substrate as follows: a buffer layer composed of GaN grown at a low temperature, an undoped nitride semiconductor, which is an n-type GaN layer, and an Si-doped Si-doped GaN layer (n-type contact layer), n-type GaN layer that is undoped nitride semiconductor, GaN layer that acts as a barrier layer, InGaN layer that forms an electric well layer, and GaN that acts as a barrier layer as a group. The clamped InGaN layer is a five-layer light emitting layer of a multiple quantum well structure, a Mg-doped AlGaN layer (p-type cladding layer), and a Mg-doped GaN layer (p-type contact layer). -60- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 554547, invention description (also, P-type semiconductor system is tempered above 400 after film formation. After lamination, it is etched by sapphire On the same surface side of the nitride semiconductor side on the substrate, the surface of each contact layer of type 15 and type 11 is exposed. Positive and negative electrodes are respectively formed on the contact layer by sputtering. Also, a comprehensive system is formed on? -Type nitride semiconductor. After the metal thin film is used as a light-transmissive electrode, a pedestal electrode is formed on one of the light-transmissive electrodes. After the finished semiconductor wafer is drawn and scribed, it is divided by external force. Thereby, a light-emitting element, namely an LED wafer, is produced. The LED chip manufactured as described above is bonded to each through hole of the package component described in Embodiment 1 by an epoxy resin mold, and then each electrode of the LED chip and the metal sheets 2a and 2b are bonded with metal wire leads, respectively. Electrical continuity was obtained. The fluorescent substance was produced as described above. First, the stoichiometric ratio of the rare earth elements of Y, Gd, and Ce was dissolved in the acid, and the solution was co-precipitated with oxalic acid. The coprecipitated oxide thus obtained is mixed with alumina to obtain a mixed raw material. Barium fluoride is mixed therein as a flux and packed in a crucible, and fired in the air at a temperature of 1400 × 3 for 3 hours. The fired product is obtained. The fired product is pulverized by ball milling in water, washed, separated, dried, and finally passed through a sieve to form a core particle size of 22 # 111 (γ0 995〇 (10.005) 2.750 and 815012: 〇60.250 Fluorescent substance 〇 For an epoxy tree containing Si 3 2 / m 2 0 wt 0/0 with a central particle diameter of 9 ′ further make the foregoing fluorescent substance 17 wt%, the central particle diameter 1 A cycloaliphatic epoxy resin composition (viscosity 8000 mPa * s) obtained by mixing and dispersing 70 wt% of Sivm of 〇vm, and used as a sealing member. In Examples 13 and 13, stainless steel was used. Composition and die thickness is 1 〇〇_ 一 __ -61-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) gutter 554547 A7 _____B7 5. Mask 112 of the description of the invention (59). The mask design is the same as that shown in FIG. 3 described in the embodiment 丨 For such a mask 112, The opening side of the hole faces the side of the mask 112, and the package assembly on which the LED chip is arranged is attracted by being placed on the substrate lifter, so as to be brought into contact with the mask 112. The end of the mask 112 is coated with the transparent resin necessary for printing The pressure is reduced to 330 Pa by a specific amount. After the pressure reduction is completed, the scraper blade 14 which is inclined by 30 degrees with respect to the vertical line of the mask 112 toward the operation direction is given a pressure of 0 · 10 MPa &lt; pressed air pressure and then subjected to the first step. Squeeze back and forth twice. Second, pressurize to 20,000 Pa in a vacuum chamber. After pressurizing, the scraper blade 15 inclined at 35 degrees with respect to the vertical direction of the mask 112 toward the opposite direction of the squeezing action is applied to the printing air pressure of 0. 12 MPa. Next, it is squeezed back. This round-trip squeezing is performed twice. 'Then' the substrate lift table is lowered, and the package assembly is pulled away from the mask 112. Thereafter, the light-transmitting resin was temporarily hardened at 85 ° C for 3 hours, and then was secondarily hardened at 140C for 4 hours. In this way, a transparent light-transmitting resin with a smooth surface can be formed on the above-mentioned through hole and on the upper surface of the insulating substrate at both ends thereof. Furthermore, on a UV-hardened dicing adhesive sheet having a film thickness of 150 / zm and an adhesive layer of 20, the transparent resin side of the package component is faced to the adhesive layer and adhered. Use a dicing knife from the bottom side of the package component to cut into light emitting diodes, and cut into the aforementioned package component and slice adhesive sheet to a depth of 100 Am. Finally, the adhesive layer is hardened by irradiating ultraviolet rays from the film side and divided into individual light-emitting diodes. 500 surface-mount (SMD-type) light-emitting diodes obtained in this way were produced, and after measuring no unevenness, there was little variation in chromaticity between different light-emitting diodes. Also, in each issue -62 · This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 554547 A7

光二極體中無外觀上之發光不均。 比較例 使用以1個開口部對應於封裝體組件之一個貫通孔的 所形成之掩模，除此以外，其餘與實施例13相同而製作; 光二極體。所得到之發光二極體的上面充填之透光性樹脂 會洩漏至兩端的基板上面。此發光二極體係黏著於切片用 黏著片而進行切片時，各發光二極體會七零八落。 又，若觀測所得到之發光二極體，與實施例丨比較而於其 上面側會產生毛邊。安裝所得到之發光二極體500個而研究 色溫度&lt;製造參差不齊。其結果，與比較例之發光二極體 的色度圖上之面積而實施例13之發光二極體，色溫度之製 造參差不齊約小2成左右。 實施例1 4 就實施例1 4，於無添加含有交聯寡聚物之一液硬化性環 氧樹脂中，使前述螢光物質15 wt%、中心粒徑為1〇 Si〇2 40 wt%混合分散而成之脂環式環氧樹脂組合物（黏度 15000 mPa·^，利用來作為封住構件的材料，除此以外， 其餘與實施例13相同而製作表面安裝型的發光二極體。本 實施例14之發光二極體係比實施例13更可提高光度及輸 出，且可大幅改善信賴性。 實施例1 5 在實施例1 5中，係以相同於實施例丨3之方法製作γ被g d 取代約2成且中心粒徑為21.429 /zm之（Y0.8Gd0.2)2.965A150i2 :Ceo.035作為螢光物質。其螢光物質係由大粒徑螢光物質 -63- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)There is no uneven light emission in the photodiode. Comparative Example A photodiode was fabricated in the same manner as in Example 13 except that a mask formed with one opening corresponding to one through hole of the package component was used. The light-transmitting resin filled on the obtained light-emitting diode will leak onto the substrate on both ends. When this light-emitting diode system is adhered to the slicing adhesive sheet for slicing, each light-emitting diode experiences a spatter. In addition, if the obtained light-emitting diode is observed, a burr may be generated on the upper side of the light-emitting diode as compared with the embodiment. The obtained 500 light-emitting diodes were installed and studied. The color temperature &lt; As a result, the variation in the color temperature of the light-emitting diode of Example 13 was about 20% smaller than the area on the chromaticity diagram of the light-emitting diode of Comparative Example. Example 14 As for Example 14, in a liquid-hardenable epoxy resin containing no cross-linked oligomer, the fluorescent substance was 15 wt% and the center particle diameter was 10 Si0 2 40 wt%. An alicyclic epoxy resin composition (viscosity 15000 mPa · ^) obtained by mixing and dispersing was used as a material for a sealing member, and otherwise, a surface-mount type light emitting diode was produced in the same manner as in Example 13. The light-emitting diode system of Example 14 can improve the luminosity and output more than Example 13, and can greatly improve the reliability. Example 1 5 In Example 15, it is made in the same way as in Example 3 (Y0.8Gd0.2) 2.965A150i2: Ceo.035, which is replaced by gd and has a core particle size of 21.429 / zm, is a fluorescent substance. The fluorescent substance consists of a large-sized fluorescent substance-63- Standards apply to China National Standard (CNS) A4 (210 X 297 mm)

裝 訂Binding

554547 A7 -----— B7 五、發明説明（62 ) 黃色變色成藍色（pH7.6)之點作為中和點，從中 KOH水溶液里求取未進行醋轉化之幾基量。 (樹脂A :比較例） 於300 ml之四口燒瓶中，加入作為脂環式環氧樹脂之環 己埽環氧化物衍生物即3,‘環氧基環己烷羧酸3，，4、環氧 基環己基甲基256 g( 1.95 e.eq)、及、作為陽離子硬化劑之 芳香族硫鑌鹽（陰離子種係六氟化銻）即苯甲基硫鑌鹽係觸 媒六氟化銻酸苯甲基甲基p_羥基苯基硫鏘〇 6 g，攪拌〇·5小 時後，在85°C下加熱3小時，進一步於14〇t下加熱4小時 而使之硬化。 (樹脂B :比較例） 於樹脂Al成分中，進一步加入作為反應性稀釋劑之丙二 醇單縮水甘油基醚7.68 g(相對於環氧樹脂為3 wt%),攪捽 0.5小時後，在85°C下加熱3小時，進一步在14〇χ：下加熱4 小時而使之硬化。 (樹脂C :本發明） 於300 ml之四口燒瓶中，加入作為脂環式環氧樹脂之 3,4-環氧基環己烷羧酸3^_環氧基環己基甲基256 §(195 e.eq)、作為酸肝之4-甲基六氫無水酞酸/六氫無水酞酸 = 70/30之混合物104.29 gW.i^MO·1 m〇i)、作為助觸媒之 乙二醇2.56 g(4.12xl0·2 mol)、作為陽離子硬化劑之苯甲 基硫鑌鹽系觸媒即六氟化銻酸苯甲基甲基p -羥基苯基硫鑌 〇·6 g ’揽掉0.5小時後，測定羧基之酯轉化率，為〇 %。測 定後，在85 °C下加熱3小時，進一步於i4〇«c下加熱4小時 -65- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 554547554547 A7 ------ B7 V. Description of the invention (62) The point where the yellow color changes to blue (pH7.6) is used as the neutralization point, and the basic amount of vinegar conversion is obtained from the KOH aqueous solution. (Resin A: Comparative Example) A 300 ml four-necked flask was charged with 3, 'epoxycyclohexanecarboxylic acid, which is cyclohexyl epoxide derivative, which is an alicyclic epoxy resin. Epoxy cyclohexylmethyl 256 g (1.95 e.eq), and aromatic thiosulfonium salt (anionic species antimony hexafluoride) as a cationic hardener, namely benzylthiosulfonium salt catalyst hexafluoride The antimony benzylmethyl p-hydroxyphenylthiocarbamate (6 g) was stirred for 0.5 hours, and then heated at 85 ° C. for 3 hours, and further heated at 14 0 t for 4 hours to harden it. (Resin B: Comparative Example) To the resin Al component, 7.68 g of propylene glycol monoglycidyl ether (3 wt% relative to the epoxy resin) was further added as a reactive diluent, and stirred for 0.5 hours at 85 ° It was hardened by heating at C for 3 hours, and further heating at 14 ×: for 4 hours. (Resin C: the present invention) In a 300 ml four-necked flask, 3,4-epoxycyclohexanecarboxylic acid 3 ^ _epoxycyclohexylmethyl 256 as an alicyclic epoxy resin was added § ( 195 e.eq), 4-methylhexahydroanhydrophthalic acid / hexahydroanhydrophthalic acid = 70/30 as a mixture of acid and liver 104.29 gW.i ^ MO · 1 m〇i), B as a catalyst 2.56 g of diol (4.12 x 10 · 2 mol), benzyl thiosulfonium salt catalyst as a cationic hardener, benzyl antimony hexafluoride, benzyl methyl p-hydroxyphenylthio, 0.6 g After 0.5 hour, the ester conversion of the carboxyl group was measured and found to be 0%. After measurement, heat at 85 ° C for 3 hours, and further heat at i4〇 «c for 4 hours -65- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 554547

而使之硬化。 (樹脂D ·本發明） 在300 ml之四口燒瓶中，加入作為脂環式環氧樹脂之 3,4-環氧基環己烷羧酸3，，4、環氧基環己基甲基256 8(195 e.eq)、作為酸酐之4-甲基六氫無水酞酸/六氫無水酞酸 = 70/3 0之混合物9·57 g(5.69xl〇·2 m〇1)、作為助觸媒之乙 一醇1.77 g(2.85xl0 2 m〇i),以加熱套徐緩昇溫在 9 0〜lOOt下加熱16小時。徐冷至室溫後，加入作為陽離子 硬化劑之苯甲基硫鑌鹽系觸媒即六氟化銻酸苯甲基甲基卜 包基麥基硫鏘0 · 6 g ’攪拌〇 · 5小時後，測定幾基之酿轉化 率，為90.6%。測定後，在85艽下加熱3小時，進一步於 14〇t：下加熱4小時而使之硬化。 (樹脂E :本發明） 除了加入脂環式環乳樹脂即3，4 -環氧基環己燒幾酸3，，4 · _ 環氧基環己基甲基256 g( 1.95 e.eq)、酸酐即4 -甲基六氫無 水S太酸/穴風供水S太酸= 70/30之混合物15.95 g(9.48x10·2 mol)、助觸媒即乙二醇2·95 g(4.75xl0·2 m〇l)、陽離子硬 化劑即苯甲基硫鑌鹽系觸媒，六氟化銻酸苯甲基〒基p _幾 基苯基硫鐳0.6 g，其餘均與樹脂D相同而製作成環氧樹脂 組合物。羧基之酯轉化率為94.2%。 (樹脂F :本發明） 除加入脂環式環氧樹脂即3，4 -環氧基環己燒羧酸3，，4，·環 氧基環己基甲基256 g( 1.95 e.eq)、酸酐即4-曱基六氫無水 S太酸/六氫無水g太酸= 70/30之混合物。25.52 $(1.52^10.1 •66- 本紙張尺度適用中國國家標準(CNS) A4规格(210X297公釐) 554547 A7 B7 五、發明説明（64 ) mol)、助觸媒即乙二醇4.72 g(7.60x10·2 mol)、陽離子硬 化劑即苯甲基硫鑌鹽系觸媒六氟化銻酸苯甲基甲基？·幾基 苯基硫鑌0.6 g，其餘均與樹脂D相同而製作成環氧樹脂組 合物。羧基之酯轉化率為92.4%。 2·可撓性評估 使用環氧樹脂组合物A至F而製作圖1所示之構造的發光 二極體，藉由進行液相衝擊試驗評估樹脂之可撓性。 又，用於此評估之發光二極·體係於環氧樹脂組合物中不 混合螢光物質。 液相衝擊試驗係以對-40 °C之液相的1分鐘浸潰、及對 100°C之液相的1分鐘浸潰作為1循環，進行500〜25〇〇循環 後’研究Led晶片之龜裂發生或引線打開所產生之動作不 良發生率（試驗個數1〇〇個）。 評估結果表示於表1中。只以陽離子硬化劑使脂環式環氧 樹脂硬化之樹脂A ’係自試驗初期即發生龜裂之動作不 良’ 1000次循環後’動作不良率為1〇〇%。加入反應性稀釋 劑而改善可撓性之樹脂B係在2500循環後發生7 %之動作不 良。另外，本發明之樹脂C、D、E、F係任一者均在25〇〇 循環後之動作不良為4%以下，尤其，進行酯轉化之樹脂 D、E、F係動作不良為〇%。本案發明之環氧樹脂組合物係 比習知以反應性稀釋劑改善可撓性之環氧樹脂還更具優異 可撓性。 -67- 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 554547 A7 B7 五、發明説明（65 ) [表1] 動作不良發生率 動作不良 原因 500 循環 1000 循環 1500 循環 2000 循環 2500 循環 樹脂A :比較例 39% 100% 100% 100% 100% 龜裂 樹脂B :比較例 0% 0% 1% 4% 7% 龜裂 樹脂C :實施例 1% 1% 3% 3% 4% 龜裂 樹脂D :實施例 0% 0% 0% 0% 0% 樹脂E :實施例 0% 0% 0% 0% 0% _ 樹脂F :實施例 0% 0% 0% 0% 0%And harden it. (Resin D · The present invention) In a 300 ml four-necked flask, 3,4-epoxycyclohexanecarboxylic acid 3,4, epoxycyclohexylmethyl 256 as an alicyclic epoxy resin was added. 8 (195 e.eq), 4-methylhexahydroanhydrophthalic acid / hexahydroanhydrophthalic acid = 70/3 0 as an anhydride 9.57 g (5.69xl0 · 2 m〇1), as an aid The catalyst was 1.77 g of ethylene glycol (2.85 x 10 2 m0i), which was slowly heated with a heating jacket and heated at 90 to 100 t for 16 hours. After cooling to room temperature, a benzylthiosulfonium salt catalyst, which is a cationic hardener, was added, benzyl antimony hexafluorate, benzylmethylbuthyl methythionine, 0.6 g, and stirred for 0.5 hours. After that, the conversion rate of Jijijiu was measured and found to be 90.6%. After the measurement, it was heated at 85 ° F for 3 hours, and further heated at 140 ° C for 4 hours to harden. (Resin E: the present invention) In addition to the addition of alicyclic cycloemulsion resin, which is 3,4-epoxycyclohexylacetic acid 3,4,4-epoxycyclohexylmethyl 256 g (1.95 e.eq), Anhydride is 4-methylhexahydroanhydrous S too acid / anaerobic water supply S too acid = 70/30 mixture 15.95 g (9.48x10 · 2 mol), the catalyst is ethylene glycol 2.95 g (4.75xl0 · 2 mol), a benzylthiosulfonium salt-based catalyst, a cationic hardener, benzylsulfanyl hexafluoride antimony p_ several phenylphenylsulfanium 0.6 g, and the rest are the same as resin D Epoxy resin composition. The carboxyl ester conversion was 94.2%. (Resin F: the present invention) In addition to adding alicyclic epoxy resin, which is 3,4-epoxycyclohexyl carboxylic acid 3,4, · epoxycyclohexylmethyl 256 g (1.95 e.eq), The anhydride is a mixture of 4-fluorenylhexahydroanhydrous S too acid / hexahydroanhydrous g too acid = 70/30. 25.52 $ (1.52 ^ 10.1 • 66- This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) 554547 A7 B7 V. Description of the invention (64) mol), the catalyst is ethylene glycol 4.72 g (7.60 x10 · 2 mol), cation hardener, benzyl thiosulfonium salt catalyst benzyl hexafluoroantimonate? -0.6 g of a few phenyl sulfanil, and the rest were the same as resin D to prepare an epoxy resin composition. The carboxyl ester conversion was 92.4%. 2. Flexibility Evaluation Using the epoxy resin compositions A to F, light-emitting diodes having the structure shown in FIG. 1 were produced, and the flexibility of the resin was evaluated by performing a liquid phase impact test. In addition, the light-emitting diode · system used for this evaluation was not mixed with a fluorescent substance in the epoxy resin composition. The liquid phase impact test uses 1 minute immersion in a liquid phase at -40 ° C and 1 minute immersion in a liquid phase at 100 ° C as one cycle. Incidence of cracking or lead failure (100 trials). The evaluation results are shown in Table 1. Resin A ', which hardens the alicyclic epoxy resin with only a cationic hardener, has a defective operation that has cracked since the beginning of the test. After 1000 cycles, the defective operation rate is 100%. Resin B, which added a reactive diluent to improve flexibility, had 7% poor operation after 2500 cycles. In addition, any of the resins C, D, E, and F of the present invention had a malfunction of 4% or less after 25,000 cycles, and in particular, resins D, E, and F of an ester conversion had malfunction of 0% . The epoxy resin composition of the present invention is more flexible than conventional epoxy resins which are improved in flexibility with a reactive diluent. -67- This paper size applies Chinese National Standard (CNS) A4 (210X297mm) 554547 A7 B7 V. Description of the invention (65) [Table 1] Occurrence rate of poor movements Reasons for poor movements 500 cycles 1000 cycles 1500 cycles 2000 cycles 2500 Recycled resin A: Comparative example 39% 100% 100% 100% 100% Cracked resin B: Comparative example 0% 0% 1% 4% 7% Cracked resin C: Example 1% 1% 3% 3% 4 % Cracked resin D: Example 0% 0% 0% 0% 0% Resin E: Example 0% 0% 0% 0% 0% _ Resin F: Example 0% 0% 0% 0% 0% 0%

裝 3·耐光性（黃變）評估 訂Equipment 3 · Evaluation of light resistance (yellowing)

使用環氧樹脂組合物B、F而進行耐光性試驗。製作3 Ο X 30X3 mm之試片，在120°C之溫度條件下照射氙燈100小 時，研究燈照射前後之全光線穿透率的變化。穿透率測定 係使用分光測色計（村上色彩研究所製）。測定結果表示於 圖11A及圖11B。圖11A表示照射前之全光線穿透率，圖 1 1 B係照射後之全光線穿透率。習知之環氧樹脂組合物即 添加有反應性稀釋劑之樹脂B，從初期短波長區域之穿透 率會下降而變成黃色，依耐光性試驗而短波長區域之穿透 率會進一步下降而黃變更明顯進行。 另外，本發明之環氧樹脂組合物即樹脂F係於初期亦或耐 光性試驗後均看不出變色。 4.对熱性評估 -68- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐） 554547 A7 B7 五、發明説明（66 ) 使用環氧樹脂組合物A、B、F而進行耐光性試驗。製作 3 0 X 3 0 X 3 mm之試片，在120 °C之烘箱中加熱500小時， 研究加熱前後之全光線穿透率的變化。穿透率測定係使用 分光測色計（村上色彩研究所製），測定結果表示於圖12A 及圖12B。囷12A係表示照射前之全光線穿透率，圖12B 係表示照射後之全光、線穿透率。 習知之環氧樹脂組合物即添加有陽離子硬化劑之樹脂A係 具有與本發明之環氧樹脂組合物即樹脂F同等的穿透率， 但’依耐熱性試驗而短波長區域的穿透率會下降而變黃。 又，添加有反應性稀釋劑之樹脂B係從初期短波長區域的 穿透率會下降而成為黃色，依耐熱性試驗而短波長區域的 穿透率會進一步下降而明顯變黃。 另外，本發明之環氧樹脂組合物即樹脂F係在初期未變 色’比受耐熱性試驗會進行變黃之樹脂B顯示更良好的耐 熱性。 5 .LED通電壽命評估 使用環氧樹脂组合物B及F而製作圖1所示構造之發光二 極禮，進行在室溫（25。〇與高溫高濕（85 °C、85%)中之通 電壽命試驗（電流值1 〇 m A)。囷1 3及圖1 4係分別研究在室 溫及高溫高濕之通電壽命中的LED相對輸出值P。〇/〇(以初期 作為100¼之輸出的相對值）之變化圖形。如圖13及囷14所 示般，本發明之環氧樹脂組合物F係比習知環氧樹脂組合物 B更少在壽命中之led輸出的降低。 6 ·適用期評估The light resistance test was performed using epoxy resin compositions B and F. A 3 〇 X 30X3 mm test piece was made, and the xenon lamp was irradiated at a temperature of 120 ° C for 100 hours. The change of the total light transmittance before and after the irradiation of the lamp was studied. The transmittance was measured using a spectrophotometer (manufactured by Murakami Color Research Institute). The measurement results are shown in Figs. 11A and 11B. FIG. 11A shows the total light transmittance before irradiation, and FIG. 11B shows the total light transmittance after irradiation. The conventional epoxy resin composition, that is, resin B to which a reactive diluent is added, has a decrease in transmittance from the initial short-wavelength region to yellow, and the transmittance in the short-wavelength region further decreases and yellow due to light resistance tests The change is apparent. In addition, the resin F, which is the epoxy resin composition of the present invention, shows no discoloration at the initial stage or after the light resistance test. 4. Evaluation of thermal properties-68- This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 554547 A7 B7 V. Description of the invention (66) Lightfastness using epoxy resin compositions A, B, and F test. A 30 X 3 0 X 3 mm test piece was made and heated in an oven at 120 ° C for 500 hours to study the change in total light transmittance before and after heating. The transmittance was measured using a spectrophotometer (manufactured by Murakami Color Research Institute). The measurement results are shown in Figs. 12A and 12B.囷 12A is the total light transmittance before irradiation, and Figure 12B is the total light and linear transmittance after irradiation. The conventional epoxy resin composition, that is, the resin A to which a cationic hardener is added, has the same transmittance as that of the resin F, which is the epoxy resin composition of the present invention, but the transmittance in the short wavelength region is determined by the heat resistance test. Will fall and turn yellow. Further, the resin B to which the reactive diluent is added decreases in transmittance from the initial short-wavelength region to yellow, and the transmittance in the short-wavelength region further decreases and yellows significantly depending on the heat resistance test. In addition, Resin F, which is the epoxy resin composition of the present invention, has no discoloration at the initial stage ', and shows better heat resistance than Resin B, which undergoes yellowing when subjected to a heat resistance test. 5. Evaluation of LED power-on life Using the epoxy resin compositions B and F, a light-emitting diode having the structure shown in FIG. 1 was produced and subjected to room temperature (25.0 and high temperature and high humidity (85 ° C, 85%)). Power-on life test (current value 10 m A). 囷 13 and Figure 14 respectively study the relative output value P of LED in the power-on life at room temperature and high temperature and humidity. 〇 / 〇 (The initial output is 100¼ output Figure 13 and Figure 14 show that the epoxy resin composition F of the present invention has less reduction in the LED output during life than the conventional epoxy resin composition B. 6 · Period Evaluation

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554547 A7 ____B7 五、發明説明（67 ) 使用環氧樹脂組合物B及F ’研究在5(rc下之黏度隨時間 變化。評估結果表示於圖15中。習知之環氧樹脂組合物B 之適用期約25小時，但，本發明之環氧樹脂組合物F之適 用期約4 0小時。 實施例1 7 製作圖1所示之表面安裝型的發光二極體作為實施例17。 此實施例17之發光二極體中係於透光性樹脂混合螢光物 質。LED晶片5係使用一具有-單色性發光波峰為可見光即 475 nm之Ino^Gao.sN半導體的氮化物半導體元件作為發光 層。亦即，在本實施例1 7中，LED晶片係使用與實施例！ 3 相同者。 又，封裝體亦使用與實施例1 3相同者。 又，螢光物質亦使用與實施例1 3相同者。 製作脂環式環氧樹脂組合物（黏度15000 mPa · s)作為透 光性樹脂，該組合物係相對於上述樹脂F而混合分散前述勞 光物質15 wt%、中心粒徑10 之Si02 40 wt%。 以下，同於實施例13之做法而製作發光二極體500個。 測定如此方法所得到之發光二極體500個之參差不齊後， 在發光二極體間之色度參差不齊很小，在各發光二極體中 外觀上並無發光不均已獲得確認。又，與使用樹脂A時比 較可更大幅地提昇信賴性。 比較例 使用樹脂A，且使用一相對於絕緣性基板1個之貫通孔而 形成1個開口部的掩模來進行製作，除此以外，其餘與實施 -70- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 554547 A7 B7 五、發明説明（邱） 例1 7同樣方法而製作發光二極體，則看到發光不均，無法 得到均一的發光。又，信賴性比實施例丨7更降低。 實施例1 8 使用與實施例15相同者作為螢光物質，並於15 wt%樹脂 下中含有螢光物質，除此以外，其餘與實施例丨7相同做法 而製作發光二極體。此實施例1 8之發光二極體係可得到與 實施例1同樣的效果，同時並可得到比實施例丨7更高輝度 的發光二極體。 以下之實施例係有關螢光物質合成之實施例。 實施例19(在還原氣氛中藉2段燒成合成螢光物質） 以下之實施例係有關適用於發光二極體之螢光物質的製 造方法。' 在實施例1 9之方法中，係首先於調整成所希望之螢光物 質的組成之混合材料中混合助溶劑而填入掛禍中，在弱還 原氣氛中以1400°C〜1600°C燒成6〜8小時，進一步於還原氣 氣中以1400 °C〜1600艺燒成6〜8小時，粉碎所得到之燒成 品，通過200網目的篩而形成螢光物質。 如此，當形成螢光物質時，使用混合原料與助熔劑所構 成之混合物以二階段（即在弱還原氣氛中進行之第一燒成步 驟、及、在還原氣氛中進行之第二燒成步驟）進行燒成，俾 可得到激發波長之吸收效率高的螢光物質。藉此，例如， 適用於圖1所示之發光二極體時，為得到所希望之色調，可 減少必需之螢光物質量，並得到光取出效率高的發光二極 體。 -71 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)554547 A7 ____B7 V. Description of the invention (67) The use of epoxy resin compositions B and F 'to study the viscosity change over time at 5 (rc. The evaluation results are shown in Figure 15. The application of the conventional epoxy resin composition B The period is about 25 hours, but the useful life of the epoxy resin composition F of the present invention is about 40 hours. Example 17 A surface-mount type light-emitting diode shown in FIG. 1 is produced as Example 17. This example The light-emitting diode of 17 is composed of a translucent resin mixed with a fluorescent substance. The LED chip 5 uses a nitride semiconductor element having an Ino ^ Gao.sN semiconductor with a monochromatic emission peak that is visible light, that is, 475 nm. That is, in this Example 17, the LED chip is the same as that in Example! 3, and the package is also the same as that in Example 13 and 3. The fluorescent substance is also used as in Example 1. 3 is the same. An alicyclic epoxy resin composition (viscosity 15000 mPa · s) is prepared as a light-transmitting resin, and the composition is a mixture of 15 wt% of the above-mentioned matte substance and a center particle diameter of 10 with respect to the resin F. 40% by weight of Si02. Hereinafter, the same as in Example 13 500 light-emitting diodes were produced in this way. After measuring the unevenness of the 500 light-emitting diodes obtained in this way, the chromaticity unevenness between the light-emitting diodes was small, and in each light-emitting diode No uneven light emission has been confirmed in appearance. Reliability can be improved significantly compared to when resin A is used. In the comparative example, resin A was used, and one through hole was formed with respect to one insulating substrate. The masks at the openings are made. Except for this, the rest are implemented. -70- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 554547 A7 B7 V. Description of invention (Qiu) Example 1 7 When a light-emitting diode was produced in the same manner, uneven light emission was observed, and uniform light emission could not be obtained. Moreover, the reliability was lower than that of Example 丨 Example 1. 8 The same as Example 15 was used as a fluorescent substance. In addition, a fluorescent substance is contained in 15 wt% of the resin, except that the light-emitting diode is produced in the same manner as in Example 1.7. The light-emitting diode system of Example 18 can be obtained in the same manner as in Example 1. Effect, and available at the same time A light emitting diode with higher brightness than Example 丨 7. The following examples are examples of the synthesis of fluorescent substances. Example 19 (2 steps of firing in a reducing atmosphere to synthesize fluorescent substances) The following examples It relates to a method for producing a fluorescent substance suitable for a light-emitting diode. 'In the method of Example 19, first, a co-solvent was mixed in a mixed material adjusted to the composition of a desired fluorescent substance, and then the mixture was filled. In the disaster, firing in a weak reducing atmosphere at 1400 ° C ~ 1600 ° C for 6 ~ 8 hours, and further firing in a reducing gas at 1400 ° C ~ 1600 ° C for 6 ~ 8 hours, crushing the obtained fired product, Pass through a 200 mesh screen to form a fluorescent substance. Thus, when a fluorescent substance is formed, a mixture composed of a mixed raw material and a flux is used in two stages (i.e., the first firing step performed in a weak reducing atmosphere, and the second firing step performed in a reducing atmosphere). ) By firing, fluorene can obtain a fluorescent substance with high absorption efficiency at the excitation wavelength. Thus, for example, when it is applied to the light-emitting diode shown in FIG. 1, in order to obtain a desired hue, the mass of the necessary fluorescent substance can be reduced, and a light-emitting diode with high light extraction efficiency can be obtained. -71-This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)

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Claims (1)

554547 修正補充 第091101139號專利申請案 中文申請專利範圍替換本02年8月） A8 B8 C8 P年8 ή?554547 Amendment Supplement No. 091101139 Patent Application Chinese Patent Application Replacement (August 2002) 1.種發光一極體，係具備··發光層由氮化物系化合物半 導體所構成之LED晶片，及，含有螢光物質之透光性樹 月曰’而该螢光物質係可吸收來自該LED晶片之光的至少 一部分而發出不同波長的光；其特徵在於： *前述螢光物質係含有小粒徑螢光物質與大粒徑螢光物 员，㈤逑大粒徑螢光物質係於前述透光性樹脂中分布於 釣这LED曰曰片附近而形成色變換層，前述小粒徑營光物 質係於前述透光性樹脂中分布在前述色變換層的外侧。 2·根據申請專利範圍第1項之發光二極體，其中前述大粒 仅勞光物質其粒徑係被調整1 〇 # m〜6 〇 # m的範圍。 3·根據申請專利範圍第丨項之發光二極體，其中前述小粒 徑螢光物質其粒徑係被調整至〇·2 #m〜15 的範圍。 4·根據申請專利範圍第1項之發光二極體，其中前述大粒 徑螢光物質之頻度波峰粒徑值係設定於前述小粒徑螢光 物質的頻度波峰粒徑值之2 〇倍〜9 〇倍範圍。 5·=種發光二極體，係具備：發光層由氮化物系化合物半 導體所構成之LED晶片、及含有螢光物質之透光性樹 脂，而孩螢光物質係可吸收來自該LED晶片之光的至少 一部分而發出不同波長之光；其特徵在於： 前述螢光物質係在體積基準粒度分布曲線中，具有加 算值0·01 v〇l%〜10 vol%之間斜率為〇之平坦區域。 6·根據申請專利範圍第5項之發光二極體，其中前述螢光 物質係包括以前述平坦區域作為界限之小粒徑螢光物質 及大粒徑螢光物質，前述大粒徑螢光物質之頻度波峰1 O:\76\76326-920808 DOC 5 ^ 冬狀氣尺度通用中國國家標A4規格(21〇Χ297公愛） 554547 A8 B8 C81. A light-emitting monopolar body comprising: an LED chip whose light-emitting layer is composed of a nitride-based compound semiconductor, and a light-transmitting tree containing a fluorescent substance, and the fluorescent substance can absorb the light from the At least a part of the light from the LED chip emits light with different wavelengths; it is characterized by: * The aforementioned fluorescent substance contains a small-sized fluorescent substance and a large-sized fluorescent substance, and the large-sized fluorescent substance is based on The light-transmitting resin is distributed in the vicinity of the LED chip to form a color conversion layer, and the small particle size light-emitting substance is distributed in the light-transmitting resin outside the color conversion layer. 2. The light-emitting diode according to item 1 of the scope of the patent application, in which the above-mentioned large particles only have a light-emitting substance whose particle size is adjusted to a range of 1 〇 # m to 6 〇 # m. 3. The light-emitting diode according to item 丨 of the scope of patent application, wherein the particle size of the aforementioned small-particle-size fluorescent substance is adjusted to a range of 0.2 to 15 m. 4. The light-emitting diode according to item 1 of the scope of the patent application, wherein the frequency peak particle size value of the aforementioned large particle size fluorescent substance is set to be 200 times of the frequency peak particle size value of the aforementioned small particle size fluorescent substance ~ 90 fold range. 5 · = light-emitting diodes, which include: an LED wafer whose light-emitting layer is composed of a nitride-based compound semiconductor, and a translucent resin containing a fluorescent substance, and the fluorescent substance can absorb the light from the LED chip. At least a part of the light emits light of different wavelengths, and is characterized in that: the aforementioned fluorescent substance has a flat area with a slope between 0 and 01 v0l% to 10 vol% in the volume-based particle size distribution curve with an added value of 0 . 6. The light-emitting diode according to item 5 of the scope of patent application, wherein the aforementioned fluorescent substance includes a small-sized fluorescent substance and a large-sized fluorescent substance with the aforementioned flat region as a boundary, and the aforementioned large-sized fluorescent substance Frequency peak 1 O: \ 76 \ 76326-920808 DOC 5 ^ Winter-like gas scale General Chinese national standard A4 specification (21〇 × 297 public love) 554547 A8 B8 C8 申請專利範圍 〜修正I 補充 么值為前述小 〜9 〇倍。 粒徑螢光物質 &lt;頻度波峰粒徑值的20倍 7·根據申請專利範圍第山項中任一項 &quot;1C勞光物質之中心粒徑為15之範：。’、 • 2申，專利範圍第7項之發光二極體，其中前述中心 权頻度值為2 〇 %〜5 〇 %的範圍。 9. 根據申請專利範圍第項之發光二極 光性樹脂除含有前《絲料，又含有擴散劑 10. 根據中請專利範圍第…項之發光二極體，其中前述赶 光性樹脂之發光面具有曲線。 11· 一種發光二極體，係具備如下者， 封裝體，其係包括：構成正負電極之靖金屬薄板以由 絕緣樹脂電氣分離之方式被接合而形成的金屬基底、及 為形成收藏部而接合於前述金屬基底之一側面的周圍之 側壁部； 設於前述收藏部之led晶片； 以封住前述LED晶片之方式充填於前述收藏部之透光 性樹脂；其特徵在於： 前述透光性樹脂係從前述收藏部連續形成於其周圍之 側壁部的上面，其透光性樹脂的上面係平坦且大致與前 述金屬基底平行，且前述透光性樹脂之外周側面係位於 大致與前述封裝體之外周侧面同一平面上。 12·根據申請專利範圍第&quot;項之發光二極體，其中前述透光 性樹脂係含有填充劑。 -2 - 裝 玎 線 O:\76\76326-920808 DOC 5 表鍈張瓦度適用中國國家標準(CNS) A4規格(210 X 297公釐)Scope of patent application ~ Correction I Supplement The value is ~ 90 times smaller than the aforementioned value. Particle size Fluorescent substance &lt; 20 times the frequency peak particle size value 7 · According to any of the items in the scope of the patent application &quot; 1C, the center particle diameter of the light-emitting substance is in the range of 15 :. ', • 2 applications, the light-emitting diode of the seventh item of the patent scope, wherein the aforementioned center-weighted frequency value ranges from 20% to 50%. 9. According to the scope of the patent application, the light-emitting diode resin in addition to the former "silk material, but also contains a diffusing agent. 10. According to the patent scope of the invention, the light-emitting diode, in which the light-emitting surface of the light-emitting resin With curves. 11. A light-emitting diode comprising the following: a package comprising a metal substrate formed by joining positive and negative electrode thin metal plates electrically insulated from an insulating resin, and joining to form a storage portion A side wall around one side of the metal substrate; a led chip provided in the storage section; a light-transmitting resin filled in the storage section so as to seal the LED chip; the light-transmitting resin is characterized in that: The upper portion of the transparent resin is formed continuously on the upper side of the surrounding side wall portion, the upper surface of the light-transmitting resin is flat and substantially parallel to the metal substrate, and the outer peripheral side of the light-transmitting resin is located substantially on the side of the package. The outer peripheral sides are on the same plane. 12. The light-emitting diode according to item &quot; in the scope of the patent application, wherein the light-transmitting resin contains a filler. -2-Installation line O: \ 76 \ 76326-920808 DOC 5 Table wattage is applicable to China National Standard (CNS) A4 (210 X 297 mm) 利範圍第12項之發光二極體，其中前述填充 :‘、3有—種可吸收來自前述LED晶片之光的一部分並 可發出不同波長之螢光物質。 i4m專利範圍第i3項之發光二極體，其中前述螢光 ^ 心粒徑係設定於1 5 〜50 之範圍。 5·^種發光二極體之製造方法，係用以製造中請專利範圍 罘11項足發光二極體的方法，其特徵在於具 驟： 第1步驟·係使分別對應於前述收藏部之複數貫通孔分 j所形成的絕緣基4£、與對應於前述各貫通孔而具有被 可述絕緣樹脂分離之部分的金屬基底板進行接合，俾製 作由複數封裝體之集合體所構成的封裝體組件； 第2步驟：於依前述貫通孔所形成之各封裝體的收藏部 安裝LED晶片； 第3步驟：係使用一對應於前述各組而形成丨個開口部 足掩模，再藉孔版印刷於前述絕緣性基板的上面與前述 貫通孔内塗佈前述透光性樹脂並使之硬化； 第4步驟：係使形成有前述透光性樹脂之封裝體組件分 割成各個封裝體。 16.根據申請專利範圍第丨5項之發光二極體的製造方法，其 中前述孔版印刷係反覆進行減壓及加壓。 17·根據申請專利範圍第1 5或丨6項之發光二極體的製造方 法，其中前述透光性樹脂含有填充劑。 18. —種環氧樹脂組合物，係含有：6 5重量％以上由脂環式 -3- O:\76\76326-920808.DOC 5 泰展張尺度適用中國國家標準(CNS) A4規格(210 X 297公董) 中 A BCD il^l 每氧樹脂所構成之環氧樹脂、相 乳當量為〇.，〜M莫耳以通式(1)所=氧樹脂之環 (2)所示之二羧酸： 不又酸奸或以通式The light-emitting diode of the twelfth item, wherein the aforementioned filling: ‘, 3 has—a kind of fluorescent substance that can absorb a part of the light from the LED chip and emit different wavelengths. The illuminating diode of the i4m patent range item i3, wherein the aforementioned fluorescent particle diameter is set in the range of 15 to 50. 5. · A kind of light-emitting diode manufacturing method, which is a method for manufacturing 11 foot-emitting light-emitting diodes in the scope of patent application, which is characterized by the following steps: The first step is to correspond to the aforementioned collection department The insulating base formed by the plurality of through-holes j is bonded to a metal base plate corresponding to each of the through-holes and having a portion separated by an insulating resin, to produce a package composed of an assembly of a plurality of packages. Step 2: Install the LED chip in the storage part of each package formed by the aforementioned through-holes; Step 3: Use an opening foot mask corresponding to each of the aforementioned groups, and then borrow the hole plate The transparent resin is printed on the upper surface of the insulating substrate and coated in the through hole to harden it. The fourth step is to divide the package component formed with the transparent resin into individual packages. 16. The method of manufacturing a light-emitting diode according to item 5 of the scope of the patent application, wherein the aforementioned stencil printing is repeatedly decompressed and pressurized. 17. The method for manufacturing a light-emitting diode according to item 15 or item 6 of the scope of patent application, wherein the translucent resin contains a filler. 18. An epoxy resin composition containing more than 65% by weight of alicyclic -3- O: \ 76 \ 76326-920808.DOC 5 Thai expansion scales are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297), the epoxy resin and phase emulsion equivalent of A BCD il ^ l per oxyresin are 0.1, and ~ M mole is represented by the ring (2) of oxyresin represented by the general formula (1) Dicarboxylic acid: not sour or general formula HOOC-r2—-c〇〇H 0) (2) ’中’ R 1為碳數〇〜1 2之環式4月匕脱、A t、甘 為碳數0〜12&gt;斤甘、— 无基或芳基，I 氧备旦A 0 0 、凡土或方基），相對於前述環氧樹脂的環 田里為0·0001〜〇.〇1莫耳之陽離子硬化劑。 19.:C:範圍第18項之環氧樹脂組合物，其中前述 :%切氧樹脂為至少一種選自環己缔環氧化物衍生 氫化雙驗A二縮水甘油基_、六紐酸：縮水 酉旨。 ’田 .f據申睛專利範圍第1 8項之環氧樹脂組合物，其中前逑 陽離子硬化劑為選自芳香族硫鏘鹽、芳香族重氮鑕鹽^ 芳香族碘鑌鹽、芳香族硒鹽之至少一種。 21·根據申請專利範圍第18項之環氧樹脂組合物，其中相對 於岫述酸酐或二羧酸含有〇1〜5 〇當量之多元醇或其縉 體。 22·根據申請專利範圍第21項之環氧樹脂組合物，其中前迷 -4- O:\76\76326-920808.DOC £ '卜冰奴尺攻適用令國A4規格(21GX297公tT 554547HOOC-r2—-c〇〇H 0) (2) 'Medium' R 1 is a ring-shaped April dagger with carbon number of 0 ~ 12, At and Gan are carbon number of 0 ~ 12 &gt; Jingan,-None Cation or aryl group, I-Oxyl-Dandan (A 0 0, earthen or square)), a cationic hardener of 0.0001 to 0.001 mole relative to the aforementioned epoxy resin. 19 .: C: The epoxy resin composition of the range of item 18, wherein the aforementioned:% oxygen-cutting resin is at least one selected from cyclohexyl epoxide-derived hydrogenated double test A diglycidyl, hexanoic acid: shrink Intent. 'Tian.f According to claim 18, the epoxy resin composition of the patent scope, wherein the proton cation hardener is selected from the group consisting of aromatic thiosulfonium salt, aromatic diazonium sulfonium salt ^ aromatic iodonium salt, aromatic At least one kind of selenium salt. 21. The epoxy resin composition according to item 18 of the scope of application for a patent, which contains 0.01 to 50 equivalents of a polyhydric alcohol or an isomer thereof with respect to the anhydride or dicarboxylic acid described above. 22. The epoxy resin composition according to item 21 of the scope of application for patents, in which the former fan -4- O: \ 76 \ 76326-920808.DOC £ 'Bubingu rule applicable to A4 specifications (21GX297 male tT 554547 夕兀醇係選自乙二醇、二甘醇、三甲撐二醇、三乙二 醇、丙二醇、14-丁二醇、1,6-己二醇之至少一種。 23. —種環氧樹脂組合物之製造方法，其係製造申請專利範 圍第1 8項之環氧樹脂組合物的方法，其特徵在於： —使則述環氧樹脂與前述酸酐或二羧酸反應而得到交聯 寡聚物後’在前述交聯寡聚物中混合陽離子硬化劑。 24. —種光導體元件，係具備：至少一對之導線電極、電氣 連前述導線電極之光半導體晶片、及封住前述光^ 導骨豆晶片之模鑄樹脂；其特徵在於： 、則述模鑄樹脂係由申請專利範圍第18〜22項中任一項 &lt;環氧樹脂組合物所構成。 、 25·根據中請專利範圍第24項之光半導體元件，其中前述光 半導to件係於形成前述導線電極之基板表面接合前述 半導體晶片的表面安裝型。 26·根據巾請專利範圍第24項之光半導體元件，纟中前述光 半導體晶片係具有由至少含有111與(3&amp;之氮化物半導體所 構成之發光層，主發光波峰為5 5 〇 以下之發光二 體。 一 v 、種螢光物質足製造方法，其係混合原料與助熔劑而燒 成以製造螢光物質者，其特徵在於： 則述燒成步驟係包括在第1還原氣氛中進行燒成之第工 燒f步，與在第2還原氣氛中進行燒成之第2燒成步驟， 1述第1還原氣氛係較前述第2還原氣氛為弱之還原性 氣氛。 O:\76\76326-920808.DOC5 - -5 554547 iki&quot; rr 補充I A8 B8 ____D8 、申請專利範園 28.«中請專利範圍第27項之螢光物質的製造方法，其中 W述助熔劑係由氟化鋁所構成。 據中請專利範圍第27項之榮光物質的製造方法，其中 前述助熔劑係包含氟化鋇與硼酸。 據申請專利範圍第29項之螢光物質的製造方法，其中 前述助熔劑進一步含有液體。 •種螢光物質之製造方法，其係混合原料與助熔劑而進 行燒成以製造螢光物質者，其特徵在於·· 利述助溶劑係含有氟化鋇與硼酸與液體。 32·根據申請專利範圍第3 0項之螢光物質的製造方法，其中 前述液體為水。 •根據申凊專利範圍第2 7〜3 2項中任一項之勞光物質的製 造方法，其中前述原料係由Y2〇3、Gd2〇3、A1203及Ce〇2 所構成。 °^6\76326-92i »2〇8〇8.D〇C 5 - 6 - 一 、α尺〜適同中國國家標準(CNS) A4規格(210 x 297公褒）The alcohol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, 14-butanediol, and 1,6-hexanediol. 23. —A method for manufacturing an epoxy resin composition, which is a method for manufacturing an epoxy resin composition according to item 18 of the scope of patent application, which is characterized by: —using the epoxy resin and the aforementioned acid anhydride or dicarboxylic acid After the reaction to obtain a crosslinked oligomer, a cationic hardener is mixed with the crosslinked oligomer. 24. A light-conducting element comprising: at least one pair of lead electrodes, an optical semiconductor wafer electrically connected to the lead electrodes, and a molding resin encapsulating the aforementioned light-guided bean chip; characterized in that: The die-cast resin is composed of any one of the patent application scope items 18 to 22 &lt; epoxy resin composition. 25. The optical semiconductor device according to item 24 of the patent application, wherein the optical semiconducting element is a surface mount type in which the semiconductor wafer is bonded to the surface of the substrate on which the lead electrode is formed. 26. According to the optical semiconductor device of the 24th patent scope, the aforementioned optical semiconductor wafer has a light emitting layer composed of a nitride semiconductor containing at least 111 and (3 &amp;), and the main emission peak is 5 5 0 or less. Luminescent body. A v. A method for producing a fluorescent substance, which is a method of firing a mixture of raw materials and a flux to produce a fluorescent substance, which is characterized in that the firing step includes performing in a first reducing atmosphere. The first firing step of firing and the second firing step of firing in a second reducing atmosphere. The first reducing atmosphere described above is a weaker reducing atmosphere than the aforementioned second reducing atmosphere. O: \ 76 \ 76326-920808.DOC5--5 554547 iki &quot; rr Supplement I A8 B8 ____D8, Patent Application Park 28. «Chinese Patent Application No. 27 for the production of fluorescent substances, wherein the flux is described by fluorination It is composed of aluminum. According to the patent, the method of manufacturing a glorious substance according to item 27, wherein the foregoing flux includes barium fluoride and boric acid. According to the method of manufacturing a fluorescent substance, item 29, wherein the foregoing flux Enter Steps contain liquids. • A method for producing a fluorescent substance, which is prepared by mixing raw materials and a flux and firing to produce a fluorescent substance, which is characterized in that the co-solvent system contains barium fluoride, boric acid, and a liquid. 32. The method for producing a fluorescent substance according to item 30 of the scope of the patent application, wherein the aforementioned liquid is water. • The method for producing the phosphorescent material according to any one of scopes 27 to 32 of the patent application scope, wherein The aforementioned raw materials are composed of Y203, Gd203, A1203, and CeO2. ° ^ 6 \ 76326-92i »2〇8〇8.D〇C 5-6-I. α ~ Applicable to China Standard (CNS) A4 size (210 x 297 cm)
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Publication number Priority date Publication date Assignee Title
US7278756B2 (en) 2003-11-14 2007-10-09 Hon Hai Precision Industry Co., Ltd. Light-emitting diode and backlight system using the same
US8558446B2 (en) 2005-02-18 2013-10-15 Nichia Corporation Light emitting device provided with lens for controlling light distribution characteristic
TWI467809B (en) * 2011-12-29 2015-01-01 Advanced Optoelectronic Tech Method for manufacturing semiconductor package and structure thereof
TWI495169B (en) * 2011-06-14 2015-08-01 Nitto Denko Corp Encapsulating sheet and optical semiconductor element device

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7278756B2 (en) 2003-11-14 2007-10-09 Hon Hai Precision Industry Co., Ltd. Light-emitting diode and backlight system using the same
US8558446B2 (en) 2005-02-18 2013-10-15 Nichia Corporation Light emitting device provided with lens for controlling light distribution characteristic
TWI419375B (en) * 2005-02-18 2013-12-11 Nichia Corp Light emitting device provided with lens for controlling light distribution characteristic
US8836210B2 (en) 2005-02-18 2014-09-16 Nichia Corporation Light emitting device provided with lens for controlling light distribution characteristic
US9093619B2 (en) 2005-02-18 2015-07-28 Nichia Corporation Light emitting device provided with lens for controlling light distribution characteristic
TWI495169B (en) * 2011-06-14 2015-08-01 Nitto Denko Corp Encapsulating sheet and optical semiconductor element device
TWI467809B (en) * 2011-12-29 2015-01-01 Advanced Optoelectronic Tech Method for manufacturing semiconductor package and structure thereof

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