201202392 六、發明說明： 【發明所屬之技術領域】 本發明疋關於一種在螢光體（flu〇rescent substance) 粒子之表面具有被覆層之螢光體材料、及使用其之發光 裝置。 【先前技術】 目前在液晶電視之背光或次世代之照明方面，世人 是關注於LED燈上。若欲使LED燈發光成白色時，則必 須將LED元件本身之發光透射經塗布或摻雜入紅•藍· 綠等螢光體之透鏡而疊合來自螢光體之發光以獲得白色 。然而，螢光體卻有一旦暴露於水份、熱或紫外線，則 將會導致發光特性降低之缺點。因此，為針對此等外因 而加以保護，則有採取以金屬氧化物之被膜來塗布螢光 體粒子的情況。 〔先前技術文獻〕 專利文獻 專利文獻1 特願第2009-137727號 專利文獻2 特開第2008-29125 1號公報 【發明内容】 〔所欲解決之技術問題〕 塗布有各種方法，其中之一是溶膠-凝膠法（參閱專 利文獻1)。然而’在溶膠-凝膠法的情況，由於其係經在 螢光體粒子之表面形成前驅體膜後’在氧化之氣體環境 下加以熱處理以形成金屬氧化物之被膜，視螢光體之種 類而定，也會發生由於熱處理等之影響而造成特性降低 201202392 的情況。 卜其他之塗布方法也有一種是使用金屬氧化物 微粒來塗布營弁贈矣 蛍尤體表面之方法（參閱專利文獻2)。若根據 此方法，由於其係使用金屬氧化物微粒，不再需要在氧 化之轧體％境下之熱處理，因此不至於造成由於熱處理 所引起的特性降低之問題。然而，―般而言，在使用該 方法時，則如欲塗布螢光體粒子全部表面是有困難，若 2電子顯微鏡水準觀察時.，則可確認到螢光體之露出部 此外即使在乍看似已獲得均勻塗布的情況，卻有 水份或紫外線會從金屬氧化物微粒之界面透過而縮短耐 用期限之問題存在。 、 一本發明是有鑑於此等問題所達成者，其目的是提供 :種可提㈣水性或耐紫外光等特性、且可抑制由於愛 布所引起的特性劣化之登光體材料及發光裝置。 〔解決問題之技術方法〕 本發明 < 螢光體材料是具有帛光體粒+、 螢光體粒子之# & μβ /、被復 均粒徑為10 且被覆層是具有經積詹平 ’’、、nm以上40 nm以下之微粒的結構者。 本發明之發光裝置是含有本發明之 〔發明之功效〕 策尤體材枓者 有發明之勞光體材料’則由於構成為配備具 :積層千均粒徑為以上40㈣以 可抑制 > 、、資被覆螢光體粒子全部表面，同時 P制水份或紫外绩你傷# + w工妥 卜線仉微粒之界面透過的現象。因此， 了美南耐水性或耐紫外特 u t饤Γ王 J杈网由於時間經過 201202392 所引起的亮度維持率（luminance maintenance 外’由於構成為經積層微粒的結構，即使未灰 體粒子會劣化的溫度下之熱處理也可製造、3 熱處理而導致特性降低。因此，可抑制初期费 ，以獲得高的特性。因此，若使用根據本發明 材料的發光裝置是可獲得優越的特性，同時可 用期限化。 特別是若微粒之最大粒徑為50 nm以下時 穩定地被覆螢光體粒子，更進一步地提高耐水 外光等特性。 此外，若被覆層是具有微粒為朝厚度方向 子層以上的結構時，則可更有效地抑制水份或 透過，以提高耐水性或耐紫外光等特性。 更進一步，若被覆層之厚度為10nm以上 下時’則可獲得優越的耐水性、I同時可獲得 0 再加上，若被覆層是含有由稀土氧化物、 氧化鈦、氧化鋅、氧化紹、紀與紹之複合氧化 鎂及鋁與鎂之複合氧化物所組成的族群中之至 屬氧化物日寺，則可更進-步地提高耐水性或耐 特性。 並且，若被覆層是含有由紀（γ)、亂（Gd)、 鑭(La)所組成的族群中之至少一種元素之稀土 ，則可獲得更高的特性、且可抑制成本。 ratio) ° 此 i加在螢光 '防止由於 :度之降低 丨之螢光體 圖謀長耐 •，則可更 性或耐紫 積層三粒 紫外線之 且1 μηι以 南透過性 氧化鍅、 物、氧化 少一種金 紫外光等 鈽（Ce)及 氧化物時 201202392 【實施方式】 〔本發明之最佳實施方式〕 在下文中，則就本發明之實施形態參閱圖示詳細地 加以説明。 第1圖疋以模式展示有關本發明之一實施形態之螢 光體材料10者。該螢光體材料10是具有螢光體粒子Π 、與用於被覆螢光體粒子u之表面的被覆層12。 螢光體粒子1 1是包括：例如，BaMgAlie〇u : Eu、201202392 6. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a phosphor material having a coating layer on the surface of a fluent fluorescent substance particle, and a light-emitting device using the same. [Prior Art] At present, in the backlighting of LCD TVs or the lighting of the next generation, the world is concerned about LED lamps. If the LED lamp is to be illuminated in white, the light of the LED element itself must be transmitted through a lens coated or doped into a phosphor such as red, blue, or green to superimpose the light from the phosphor to obtain white. However, phosphors, once exposed to moisture, heat or ultraviolet light, will cause a reduction in luminescent properties. Therefore, in order to protect against such external factors, it is possible to coat the phosphor particles with a film of a metal oxide. [PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PRIOR ART Sol-gel method (see Patent Document 1). However, in the case of the sol-gel method, since it forms a precursor film on the surface of the phosphor particles, it is heat-treated in an oxidizing gas atmosphere to form a film of a metal oxide, depending on the type of the phosphor. However, there is also a case where the characteristic is lowered by 201202392 due to the influence of heat treatment or the like. One of the other coating methods is a method of coating the surface of a scorpion with a metal oxide fine particle (see Patent Document 2). According to this method, since the metal oxide fine particles are used, the heat treatment in the % of the oxidized rolling body is no longer required, so that the problem of deterioration in characteristics due to the heat treatment is not caused. However, in general, when this method is used, it is difficult to apply the entire surface of the phosphor particles. When the electron microscope is observed at a level of 2, the exposed portion of the phosphor can be confirmed even if it is in the crucible. It seems that the uniform coating has been obtained, but there is a problem that water or ultraviolet rays are transmitted from the interface of the metal oxide particles to shorten the durability period. The present invention has been made in view of the above problems, and an object thereof is to provide a light-emitting material and a light-emitting device capable of suppressing characteristics such as water or ultraviolet light resistance and suppressing deterioration of characteristics due to love cloth. . [Technical method for solving the problem] The present invention relates to a phosphor material having a phosphor particle +, a phosphor particle of # & μβ /, a complex average particle diameter of 10, and a coating layer having a product of Zhanping '', the structure of particles below 40 nm below nm. The illuminating device of the present invention is the same as the "effect of the invention" of the present invention. The lacquer material of the invention is composed of a device having a laminated average particle size of 40 or more (4) to suppress > It covers the entire surface of the phosphor particles, and at the same time, the phenomenon of P-water or UV-ray damage is transmitted through the interface of the particles. Therefore, the temperature-maintaining rate caused by the time-lapse of 201202392 (luminous maintenance) is the temperature at which the particles are degraded even if the particles are not formed by the structure of the laminated particles. The heat treatment can also be carried out, and the heat treatment can be carried out to cause a decrease in characteristics. Therefore, the initial cost can be suppressed to obtain high characteristics. Therefore, if the light-emitting device using the material according to the present invention is used, superior characteristics can be obtained, and the period can be shortened. In particular, when the maximum particle diameter of the fine particles is 50 nm or less, the phosphor particles are stably coated, and the characteristics such as water-resistant external light are further improved. Further, when the coating layer has a structure in which the fine particles are more than a sub-layer in the thickness direction, Further, water or permeation can be more effectively suppressed to improve water resistance or ultraviolet light resistance. Further, when the thickness of the coating layer is 10 nm or more, superior water resistance can be obtained, and I can obtain 0 at the same time. In addition, if the coating layer contains composite magnesium oxide containing rare earth oxide, titanium oxide, zinc oxide, oxidized Shao, Ji and Shao, In the group of oxides composed of magnesium and the oxides, it is possible to further improve the water resistance or the resistance characteristics. Further, if the coating layer contains the γ (γ), chaos (Gd), A rare earth of at least one element of the group consisting of lanthanum (La) can obtain higher characteristics and can suppress cost. ratio) ° This is added to the fluorescent 'preventing due to: a decrease in the amount of phosphor If you are able to resist the sputum (Ce) and oxides of the uranium oxide, the oxidized cesium (Ce) and the oxidized metal, etc. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Fig. 1 is a view showing a phosphor material 10 according to an embodiment of the present invention in a mode. The phosphor material 10 is a coating layer 12 having phosphor particles 与 and a surface for coating the phosphor particles u. The phosphor particles 11 include: for example, BaMgAlie〇u: Eu,
ZnS . Ag、Cl、BaAl2S4 : Eu 或 CaMgSi2〇6 : Eu 等之「藍 色系榮光體」；Zn2Si04 : Μη、（γ、Gd)B〇3 :几、ZnS :Cu、A1 或（Ba、Sr、Mg)〇 . aAl2〇3 : Mn 等之「綠色系 營光體」；（Y、Gd)B〇3 : Eu、y2〇2S : Eu 或 γρν〇4 : Eu 等之「紅色系螢光體」。基本上，螢光體粒子丨丨之粒徑 是並無特殊限制，但是平均粒徑較佳為約5 至2〇 、且粒徑儘可能為大小一致者，其係由於可穩定特性的 緣故。 被覆層12 {具有經在螢光體粒+ 表面積層平 均粒徑為40 nm以下之微粒12八的結構。藉此，則可實 質地被覆螢光體粒·^ n之表面整體，同時可抑制水份或 紫外線從微粒12A之界面透過的現象。此外，由於即使 未施加在螢光體粒子n t劣化的溫度下之熱處理也可 製造’並無由於熱處理而導致特性降低，因此可獲得高 的特性。另外，在本發明所謂的「被覆層12」是=覆螢 光體粒子11之表面整體，並非意謂也會排除空孔等缺陷 存在的情況者，而為實質地接近i00<%之被覆率的情況。 201202392 此外，微粒1 2 A之平的相你洛 十均粒徑為一次粒子之平均粒徑。 i粒1 2 A之平均粒和| 工更佳為例如3 0 n m以下，進_ 步更佳為25 nm以下。另冰 ’从粒1 2 A之平均粒徑較佳 為10nm以上、更佳為1 m以上。微粒1 2 A之平均粒徑 過小時，會發生粗大的_ 的一-人凝集粒子，變得難以均勻 覆螢光體粒子1 1的緣故。卜卜从 扪緣故。此外，微粒12Α之平均粒徑 佳為螢光體粒子11之平均彡 卞g粒徑的1/100以下至1/500以 下的程度，其係由於可更籍金认^ 文穩疋地形成被覆層1 2的緣故。ZnS . Ag, Cl, BaAl2S4 : Eu or CaMgSi2〇6 : Eu etc. "Blue glory"; Zn2Si04 : Μη, (γ, Gd) B〇3 : several, ZnS : Cu, A1 or (Ba, Sr ,M)).AlAl〇3: "Green luminescence" of Mn, etc.; (Y, Gd)B〇3: Eu, y2〇2S: Eu or γρν〇4: Eu, etc. "." Basically, the particle diameter of the phosphor particles is not particularly limited, but the average particle diameter is preferably about 5 to 2 Å, and the particle diameter is as large as possible, which is due to the stable characteristics. The coating layer 12 has a structure in which the particles 12 8 having an average particle diameter of 40 nm or less in the phosphor particle + surface area layer. Thereby, the entire surface of the phosphor particles can be substantially covered, and the phenomenon that water or ultraviolet rays are transmitted from the interface of the particles 12A can be suppressed. Further, since heat treatment can be performed even if heat treatment is not applied at a temperature at which the phosphor particles n t deteriorates, there is no deterioration in characteristics due to heat treatment, so that high characteristics can be obtained. In addition, the "coating layer 12" in the present invention is the entire surface of the phosphor coated particles 11, and does not mean that defects such as voids are excluded, and the coverage ratio is substantially close to i00 <%. Case. 201202392 In addition, the flat phase of the particles 1 2 A is the average particle size of the primary particles. The average particle size of the i particles 1 2 A is preferably, for example, 3 0 n m or less, and more preferably 25 nm or less. Further, the average particle diameter of the ice from the particles 1 2 A is preferably 10 nm or more, more preferably 1 m or more. When the average particle diameter of the fine particles 1 2 A is too small, coarse-sized one-man aggregated particles are generated, and it becomes difficult to uniformly cover the phosphor particles 11 . Bu Bu from the sake of the sake. Further, the average particle diameter of the fine particles 12 is preferably from 1/100 or less to 1/500 or less of the average 彡卞g particle diameter of the phosphor particles 11, which is formed by the fact that the particles can be formed more stably. The reason for layer 1 2 .
微粒1 2 A之最大物彡①&从A ’二較佳為例如50 nm以下，其係 由於若存在著大於5〇 nm的私2 士 nm的粒子時，則容易造成螢光體 粒子11會露出之缺陷。料初 微粒1 2 A之最大粒徑更佳為例如 40nm以下，進一步更佳為3〇 nm以下。 此卜被覆層1 2較佳為具有微粒丨2 A為朝厚度方向 積層三粒子層以上的結構，其係由於可更有效地抑制水 伤或备、外線從微粒 1 2 A夕m τη- ^ 讯之界面透過的緣故。被覆層12 之厚度較佳為1 〇 nm以！ θ , ^ 以上且1 以下，其係由於若厚度 為薄時，則耐水性及而+整> & & , 汉了系外線性之功效將會變少而導致 螢光體粒子1 1劣化，芒/S麻* 力化右导度為厚時’則光透射性將會降 低而導致發光效率降低的緣故。 被覆層1 2較佳為含有由稀土氧化物、氧化鍅、氡化 欽、氧化鋅、氧化鋁、釔•鋁.石榴石 (ymiUm-aluminum_garnet)等之釔與鋁之複合氧化物氧 化鎂、及MgAhO4等之鋁與鎂之複合氧化物所組成的族 群中至少之一種金屬氧化物作為主成份。具體而言較 佳為在微粒1 2 A之至少一部份包括含有該金屬氧化物之 201202392 氧化 的緣 IL 、 物， 的緣 上混 不同 中含 ，但) 若其‘ 將會I 化為」 地抑I 。首: 於溶： 粒子 將漿' 加以： 必施 處理 一面 境是 物粒子，其係由於可接古# , j权π耐水性及耐势认， 故。其中，較佳為稀土 I '、光等特性 π怖土巩化物，更佳為 鈽及鑛所組成的族群中至小一- 由紀、 一種元素之 贫 特佳為丫2〇3，其係由於可庐得 虱 故。 功效且可抑制成本 被覆層12疋可為含有此等輩 力冗寻早獨一種、或含有 合。例如，可為含有I插笛儿兩種以 3百數種氧化物粒子混合、 的氧化物粒子積層成層狀者 佴狀考或在一個氧化物粒子 有數種氧化物。此外，；S q q u & Γ被覆層Μ也可含有其他成份 t其他成份之比例較伯_盍Λ，供曰Μ J平乂佳為〇· 1質量％以下，其係由於 to成份之比例一曰辦$，gil 1 + 、 一增夕，則光透射性及耐紫外線性 聲低的緣故。 弓外’雖然綠色系螢光體是由於紫外光所引起的劣 &仁疋若以Y2〇3形成被覆層12時，則可大幅度 Ν劣化’因此為較佳。 菱光體材料1 〇是例如可藉由如下所述方式來製造 ’製備將平均粒徑為40 nm以下之微粒12Α分散 漂所獲仔之漿體’其次’藉由在該漿體混合螢光體 11或在螢光體粒子11之流動層内喷霧漿體，以 ϋ塗布於螢光體粒子^之表面上。接著，將塗布層 乾燥以移除溶媒，以形成被覆層1 2。其時，雖可不 加…' 處理’但是較佳為在4 5 0。(：以下的溫度加以熱 ”係由於可一面防止螢光體粒子1 1之特性劣化、 提咼被覆層12之密著性的緣故。熱處理時之氣體環 可為大氣氣體環境，但是為防止由於熱處理時之氧 201202392 氣而導致特性劣化’因此較佳為可選擇氮氣氣體 氬氣氣體環境等之惰性氣體環境。此外，對於營 子11的漿體之塗布步驟及乾燥步驟較佳為重複 次以上，更佳為採取重複三次以上，其係由於藉 進行，則可確實地將微粒12A積層三粒子層以上 。但是’若為可積層三粒子層以上時，則塗布次 必特別地增加數次。 第2圖是展示使用該螢光體材料1 〇之發光』 之一構成例者。該發光裝置2〇是在基板21上配 元件22 ’且發光元件22則藉由形成在基板21上 23與線24而成電連接。此外，在發光元件22周 成例如反射框25，在發光元件22上則以覆蓋發 22之狀態而形成密封層26。密封層26是由例如 體材料1 0加以分散之樹脂所構成。 發光凡件22是使用例如會發出紫外光、藍色 綠色光之激發光者。螢光體材料丨〇則使用例如由 件22所發光之激發光而會發出紅色光者、會發出 者、會發出綠色光者、會發出黃色光者等中之一 需要而混合使用。 若根據如上所述本實施形態，由於構成為配 經積層平均粒徑為1〇nm以上4〇 nm以下之微粒 結構之被覆層12,可實質地被覆螢光體粒子η 表面，同時可抑制水份或紫外線從微粒1 2 Α之界 的現象。因此，可提高耐水性或耐紫外光等特性 提高由於時間經過所引起的亮度維持率。此外， 環境或 光體粒 進行兩 由重複 的緣故 數可不 (置20 備發光 之配線 圍則形 光元件 將螢光 光、或 發光元 藍色光 種或視 備具有 12A的 之全部 面透過 、且可 由於構 201202392 成為經積層微粒1 2 A的結構，即使未施力 11會劣化的溫度下之熱處理也可製造、可 理而導致特性之降低。因此，可抑制初期 以獲得高的特性。因此，若使用根據本發 料10之發光裝置，則可獲得優越的特性1 耐用期限化。 在螢光體 防止由於 亮度之降 明之螢光 同時可圖 特別是若微粒1 2 A之最 可更穩定地被覆螢光體粒子 或耐紫外光等特性。 大粒徑為 1 1，更進 5〇 nm以下時 步地提高耐 此外，若被覆層丨2是具有微粒為朝厚度方向積 粒子層以上的結構時，則可更有效地抑制水份或紫 之透過’以提高耐水性或耐紫外光等特性。 尺逗—步，若被覆層12之厚度為1〇 nm以上 以下時，則可獲得優越的耐水性、且同時可獲得 性。 又 —再加上，若被覆層12是含有由稀土氧化物、 氧化鈦、氧化鋅、氧化鋁、釔與鋁之複合氧化 化鎂及鋁與鎂之複合氧化物所組成的族群中之至 金屬氧化物時，則可争佳一人 、了更進一步地提向耐水性或耐 等特性。 雜 #破覆層1 2是含有由釔、釓、鈽及鑭 的族群中之至少__ 一種元素之稀土氧化物時，則可 商的特性、且可抑制成本。 、 粒子 熱處 低， 體材 謀長 ，則 水性 層三 外線 1 μιη 透過 化錯、氧 一種 外光 組成 得更 [實施例] 〔實施例1〕 -10- 201202392 準備經將平均粒徑為20 nm、最大粒徑 氧化記（Υ2 Ο3)之微粒1 2 A分散於溶媒所獲得 在該衆體混合平均粒徑為約1 〇 μ m之綠色系 11’然後在螢光體粒子11之表面上塗布製題 經塗布聚體之螢光體粒子1 1加以熱處理以傷 處理是在大氣中在300 °C下進行2小時、或 環境中在400°C下進行2小時。接著，就經 體粒子1 1，以相同的方式再重複進行一次漿 驟及乾燥步驟，以獲得螢光體材料10。 第3圖是展示所獲得螢光體材 SEM(Scanning Electron Microscope:掃描型 )照片之一實例者；第4圖是展示形成被覆層 螢光體粒子1 1之S E Μ照片之一實例者。此 是展示在所獲得螢光體材料 1〇之表 TEM(Transmission Electron Microscope:透 微鏡）照片之一實例者；而第6圖是經放大第 照片之一部份者。如第3圖及第5圖所示， 體材料10是在螢光體粒子11之表面整體已 12。此外，如第6圖所示，可知被覆層12 1 2 A在螢光體粒子1 1之表面均勻地積層三粒 結構。 接著，使用所獲得螢光體材料1 0來製造 示之發光裝置20。發光元件22是使用會發 〔比較例1 -1〕 為5 0 n m之 之漿體，並 螢光體粒子 。其次，將 -其乾燥。熱 在氮氣氣體 乾燥之螢光 體之塗布步 料 10 之 電子顯微鏡 12之前的 外，第5圖 面附近的 射型電子顯 5圖之TEM 可知該螢光 形成被覆層 是具有微粒 子層以上的 如第2圖所 出紫外光者 -11 - 201202392The largest substance 彡1& of the particles 1 2 A is preferably, for example, 50 nm or less from A '2, which is because the phosphor particles 11 are likely to be formed if there are particles of more than 5 nm in the range of 2 nm nm. Defects exposed. The maximum particle diameter of the primary particles 1 2 A is more preferably, for example, 40 nm or less, still more preferably 3 Å nm or less. The coating layer 12 preferably has a structure in which the fine particles 丨2 A is a three-particle layer or more laminated in the thickness direction, because the water damage or the external line can be more effectively suppressed from the particles 1 2 A m τη- ^ The reason for the interface of the news. The thickness of the coating layer 12 is preferably 1 〇 nm! θ , ^ or more and 1 or less, if the thickness is thin, the water resistance and the + >&&&&&&&<> Deterioration, awning/S hemp* When the right directivity is thick, the light transmittance will decrease and the luminous efficiency will decrease. The coating layer 12 preferably contains a composite oxide magnesia of cerium and aluminum such as rare earth oxide, cerium oxide, cerium oxide, zinc oxide, aluminum oxide, yttrium aluminum garnet (ymiUm-aluminum_garnet), and the like. At least one metal oxide of a group consisting of a composite oxide of aluminum and magnesium of MgAhO4 or the like is used as a main component. Specifically, it is preferable that at least a part of the microparticles 1 2 A include the 201202392 oxidized edge IL containing the metal oxide, and the inclusion of the edge is different, but if it is 'I will be Ground suppression I. First: Yurong: Particles Adding the pulp': It must be treated. The environment is a particle, which is recognized by the water resistance and resistance of the ancient _#. Among them, it is preferable that the rare earth I', the light and the like have a characteristic π-horror soil, and it is more preferable that the group consisting of the strontium and the ore is a small one - the Yuki, the poor of an element is 丫2〇3, which is due to Can be remembered. Efficacy and cost can be suppressed. The coating layer 12 can be used alone or in combination with such generations. For example, it may be a layered oxide layer containing two kinds of oxide particles mixed with two kinds of oxide particles, or a plurality of oxides in one oxide particle. In addition, S qqu & Γ coating layer can also contain other components t other components than the ratio of _ 盍Λ, for 曰Μ J Ping 乂 better 〇 · 1% by mass or less, due to the ratio of to components曰 $ , gil 1 + , 增 夕 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Outside the bow, although the green-based phosphor is inferior due to ultraviolet light, if the coating layer 12 is formed by Y2〇3, the deterioration can be greatly reduced, which is preferable. The rhombohedral material 1 〇 can be produced, for example, by preparing a slurry obtained by dispersing and floating a fine particle having an average particle diameter of 40 nm or less, followed by mixing fluorescent light in the slurry. The body 11 or the slurry is sprayed in the fluidized layer of the phosphor particles 11, and is applied onto the surface of the phosphor particles. Next, the coating layer is dried to remove the solvent to form a coating layer 12. In this case, although it is not necessary to 'process', it is preferably 4 50. (The following temperature is heated) because the properties of the phosphor particles 1 1 are prevented from deteriorating and the adhesion of the coating layer 12 is improved. The gas ring during the heat treatment may be an atmospheric gas atmosphere, but In the heat treatment, the oxygen 201202392 gas causes deterioration in characteristics. Therefore, it is preferable to select an inert gas atmosphere such as a nitrogen gas argon gas atmosphere, etc. Further, it is preferable to repeat the coating step and the drying step for the slurry of the camp 11 More preferably, it is repeated three times or more, and it is possible to reliably laminate the fine particles 12A with the three-particle layer or more by the borrowing. However, if it is a layer of the three-particle layer or more, the coating time is particularly increased several times. Fig. 2 is a view showing an example of a configuration in which the phosphor material 1 is used. The light-emitting device 2 is provided with an element 22' on the substrate 21, and the light-emitting element 22 is formed on the substrate 21 by 23 The wire 24 is electrically connected, and the light-emitting element 22 is formed, for example, as a reflection frame 25, and the light-emitting element 22 is formed to cover the hair 22 in a state in which the sealing layer 26 is formed. The sealing layer 26 is made of, for example, a body material. The material 10 is composed of a resin dispersed. The light-emitting element 22 is, for example, an excitation light that emits ultraviolet light or blue-green light, and the phosphor material is used, for example, by the excitation light emitted by the member 22. If one of the red light is emitted, the light is emitted, the green light is emitted, and the yellow light is emitted, it is mixed and used. According to the present embodiment, the average particle size of the laminated layer is 1〇. The coating layer 12 of the fine particle structure of nm or more and 4 μm or less can substantially cover the surface of the phosphor particles η and suppress the phenomenon of moisture or ultraviolet rays from the boundary of the particles 1 2 , thereby improving water resistance or resistance. The characteristics such as ultraviolet light increase the brightness retention rate due to the passage of time. In addition, the environment or the photo-particles may be repeated for two reasons (the wiring of the light-emitting layer is surrounded by the light-emitting element, or the illuminating element) The light source of the blue light or the surface having 12A is transparent, and the structure of the layered particles 1 2 A can be formed by the structure of the 201202392, and the heat treatment is performed even at a temperature at which the force 11 is not deteriorated. Manufacturing and arbitrage result in a decrease in characteristics. Therefore, it is possible to suppress the initial stage to obtain high characteristics. Therefore, if the light-emitting device according to the present invention 10 is used, superior characteristics can be obtained, and durability can be obtained. Since the brightness of the fluorescent light is reduced, the particles can be more stably coated with the phosphor particles or the ultraviolet light resistance. The large particle size is 1 1, and the time is 5 or less. In addition, when the coating layer 丨2 has a structure in which the fine particles are formed in the thickness direction or more, it is possible to more effectively suppress the penetration of water or purple to improve the properties such as water resistance or ultraviolet light resistance. In the case of the step, if the thickness of the coating layer 12 is 1 〇 nm or more, superior water resistance and simultaneous availability can be obtained. Further, if the coating layer 12 is composed of a rare earth oxide, titanium oxide, zinc oxide, aluminum oxide, composite magnesium oxide of cerium and aluminum, and a composite oxide of aluminum and magnesium, the metal When the oxide is used, it can be better for one person, and further improve the water resistance or resistance. When the #11-cladding layer 1 2 is a rare earth oxide containing at least one element of the group of lanthanum, cerium, lanthanum and cerium, the properties are negotiable and the cost can be suppressed. The particle heat is low, and the body material is long. The outer layer of the water layer is 1 μιη through the error, and the oxygen is an external light. [Examples] [Example 1] -10- 201202392 Preparation The average particle size is 20 The fine particles 1 2 A of nm and the maximum particle size oxidation (Υ2 Ο3) are dispersed in a solvent to obtain a green system 11' having a mixed average particle diameter of about 1 μm in the body and then on the surface of the phosphor particles 11. The coating problem was subjected to heat treatment by coating the polymer-containing phosphor particles 1 1 to be carried out in the air at 300 ° C for 2 hours or in the environment at 400 ° C for 2 hours. Next, the slurry and drying steps are repeated one by one in the same manner as the particles 1 1 to obtain the phosphor material 10. Fig. 3 is a view showing an example of a SEM (Scanning Electron Microscope) photograph of the obtained fluorescent material; and Fig. 4 is a view showing an example of a S E Μ photograph of the coated phosphor particles 1 1 . This is an example of a TEM (Transmission Electron Microscope) photograph showing the obtained phosphor material; and Fig. 6 is a part of the enlarged photograph. As shown in Figs. 3 and 5, the bulk material 10 is 12 on the entire surface of the phosphor particles 11. Further, as shown in Fig. 6, it is understood that the coating layer 12 1 2 A uniformly has a three-layer structure on the surface of the phosphor particles 1 1 . Next, the obtained light-emitting device 20 is manufactured using the obtained phosphor material 10. The light-emitting element 22 was a slurry obtained by using a growth method [Comparative Example 1-1] of 50 nm, and phosphor particles. Second, it will - dry. It is known that before the electron microscope 12 of the coating material 10 of the fluorescent material which is dried by the nitrogen gas, the TEM of the image of the electron beam 5 in the vicinity of the fifth surface shows that the fluorescent coating layer has a particle layer or more. The ultraviolet light produced in Figure 2 - 11 - 201202392
裝置。 形成被覆層而直接用作為螢光 實施例1相同的方式製造發光 〔比較例1-2〕 在經將釔鹽溶解於溶媒所獲Device. The coating layer was formed and luminescence was directly produced in the same manner as in Example 1 of Comparative Example 1 [Comparative Example 1-2] obtained by dissolving cerium salt in a solvent.
所獲得之溶液混合螢光體粒 於螢光體粒子1 1之表面，並加以乾 氣氣體環境中在5 0 0 °c下加以燒成2 1 1是使用與實施例1相同者。第7圖 體材料之表面附近的TEM照片之一 中’以1 11所示部份是螢光體粒子， 臈。如第7圖所示 而以1 12所示部份則為被覆層。另外，在螢光體粒子i i 及破覆層1 12之上&自色部份則為在分析時所使用的碳 對於該螢光體材料，被覆層1 12雖 已形成在螢光體粒子U1之表面整體，但是卻並未觀察 到微粒之積層結構。對於該螢光體材料是也以與實施例 1相同的方式製造發光裝置。 (劣化試驗） 就貫施例1及比較例1 -1、1 _ 2之各發光裝置2 〇進 行發光试驗，以調查亮度之經時變化。第8圖是展示實 知例1與比較例1 -1、1 - 2之結果加以比較。在第§圖中 ’縱軸是假設未形成被覆層的比較例1 _丨之初期亮度為 1〇〇%時之相對的亮度維持率。另外’關於實施例i，在 t氣中在300X：下進行熱處理2小時者、與在氮氣氣體 每境中在4001下進行2小時者是獲得相同的結果。 如第8圖所示’若根據被覆層12為具有微粒丨2 a -12- 201202392 之積層結構的實施例 w為可大幅度地抑制由乂並未形成被覆層之比較例 ，在比較W-2，雖：::：間所引起的亮度降低。此外 ，但是相對於可：： 間所引起的亮度維持率為高 、觀察到初期.亮度之降低，若根據f絲& 1則可大幅地抑制初期古…欠 右根據實轭例 體粒子"之表面是以降低。亦即’得知若螢光 12 , ^ , ^具有微粒UA之積層結構的被覆層 彳可提高由於時間經侧 可抑制初期亮度之降低，藉此可獲得高的 特性。 〔實施例2-1至2_4、比較例w〕 除了變化微粒12A之平均粒徑及最大粒徑以外，其 餘則以與實施例1相同的方式製造螢光體材料10及發光 裝置20。在’施例2_ i是使用平均粒徑為μ⑽，最大 粒徑為50 nm，在實施例2_2是使用平均粒徑為3〇㈣， 最大粒徑為50 nm，在實施例2 3是使用平均粒徑為25 nm，最大粒徑為5〇 nm，在實施例2 4是使用平均粒徑 為20 nm，最大粒徑為4〇 nm，在比較例2_丨則使用平均 粒徑為50 nm，最大粒徑為8〇 nm之微粒12A。就所獲 知發光裝置20以與實施例丨相同的方式進行發光試驗， 以調查党度之經時變化。將所獲得之結果與實施例1及 比車又例1 -1、1 - 2之結果一起展示於表在表1中，所 謂的「2000小時後之亮度維持率」是意謂假設並未形成 被覆層的比較例1 -1之初期亮度為1 〇 〇 %時之相對值。 201202392 [表1] 平均粒徑 (nm) 最大粒徑 (nm) 塗布步驟 (次數/次） 2000小時後之 亮度維持率 (%) 評估 實施例2-1 40 50 2 80 〇 實施例2-2 30 50 2 80 〇 實施例2-3 25 50 2 81 〇 實施例1 20 50 2 82 〇 實施例2-4 20 40 2 85 〇 比較例1-1 — — 0 30 X 比較例1-2 — — 2 58 Δ 比較例2-1 50 80 2 61 Δ 〇：（亮度維持率）80%以上50至79%'χ_·低於49%。 如表1所示，若微粒12Α之平均粒徑為4〇 nm以下 時，則可獲得良好結果。亦即，得知若設定微粒丨2A之 平均粒徑為40 nm以下時，則可獲得高的特性。此外， 若微粒12A之最大粒徑為5〇 nm以下時，則可獲得良好 、。果亦即，得知若設定微粒1 2A之最大粒徑為5〇 nm 以下時，則可獲得高的特性。 〔實施例3〕 除了僅貫施一次漿體之塗布步驟及乾燥步驟以外， :餘則以與實施例j相同的方式製造螢光體 2置2。。以職觀察所獲得登光體材料丨。之二 =認到在營光體粒子表面整體已形成被覆。果 的情況。此外，被覆声 又饭復層1 -粒子層至三粒曰疋地具有微粒1 2 A是以农 所獲得榮光體材料；〇::積層的結構1 9圖是展3 抖1 〇之表面附近之TEM照片。此外， -14- 201202392The obtained solution was mixed with the phosphor particles on the surface of the phosphor particles 1 1 and fired at 50 ° C in a dry gas atmosphere. The same as in Example 1 was used. Fig. 7 One of the TEM photographs near the surface of the bulk material is a phosphor particle, 臈. As shown in Fig. 7, the portion indicated by 1 12 is the coating layer. Further, on the phosphor particles ii and the fracture layer 12, the & self-color portion is the carbon used in the analysis. For the phosphor material, the coating layer 12 is formed on the phosphor particles. The surface of U1 is entirely intact, but the laminated structure of the particles is not observed. A light-emitting device was also produced in the same manner as in Example 1 for the phosphor material. (Deterioration test) Each of the light-emitting devices 2 of the first embodiment and the comparative examples 1 -1 and 1 - 2 was subjected to a light-emission test to investigate the temporal change in luminance. Fig. 8 is a comparison showing the results of the example 1 and the comparative examples 1-1 and 1-2. In the § diagram, the vertical axis represents the relative luminance maintenance ratio when the initial luminance of Comparative Example 1 _ 未 without forming a coating layer is 1 〇〇 %. Further, regarding Example i, the heat treatment was carried out at 300X: for 2 hours in t gas, and the same result was obtained for 2 hours at 4001 in a nitrogen gas atmosphere. As shown in Fig. 8, the example w of the laminated structure having the fine particles 丨2 a -12 to 201202392 according to the coating layer 12 is a comparative example in which the coating layer is not formed by the ruthenium, and the comparison is performed. 2, although the brightness caused by :::: is reduced. In addition, the brightness maintenance rate is high with respect to::, and the initial brightness is lowered. If the f-wire & 1 is used, the initial period can be greatly suppressed. The surface is reduced. That is, it is known that if the fluorescent layer 12, ^, ^ has a coating structure of a laminated structure of fine particles UA, the decrease in the initial luminance can be suppressed by the time passage side, whereby high characteristics can be obtained. [Examples 2-1 to 2_4, Comparative Example w] The phosphor material 10 and the light-emitting device 20 were produced in the same manner as in Example 1 except that the average particle diameter and the maximum particle diameter of the fine particles 12A were changed. In 'Example 2_i, the average particle size is μ (10), the maximum particle size is 50 nm, and in Example 2_2, the average particle size is 3 〇 (4), and the maximum particle size is 50 nm. In Example 2, 3 is the average. The particle size is 25 nm and the maximum particle size is 5 〇 nm. In Example 24, the average particle size is 20 nm and the maximum particle size is 4 〇 nm. In Comparative Example 2 丨, the average particle size is 50 nm. The particles 12A having a maximum particle diameter of 8 〇 nm. The luminescence test was carried out in the same manner as in Example 就 in order to investigate the change over time of the party. The results obtained are shown in Table 1 together with the results of Example 1 and the vehicle examples 1-1 and 1-2. The so-called "brightness maintenance rate after 2000 hours" means that the assumption is not formed. The relative value of the initial brightness of Comparative Example 1-1 of the coating layer was 1%. 201202392 [Table 1] Average particle diameter (nm) Maximum particle diameter (nm) Coating step (number of times/time) Brightness maintenance rate after 2000 hours (%) Evaluation Example 2-1 40 50 2 80 Example 2-2 30 50 2 80 〇Example 2-3 25 50 2 81 〇Example 1 20 50 2 82 〇Example 2-4 20 40 2 85 〇Comparative Example 1-1 — — 0 30 X Comparative Example 1-2 — — 2 58 Δ Comparative Example 2-1 50 80 2 61 Δ 〇: (Brightness maintenance ratio) 80% or more 50 to 79% 'χ_· below 49%. As shown in Table 1, when the average particle diameter of the fine particles 12 为 was 4 〇 nm or less, good results were obtained. That is, it has been found that when the average particle diameter of the fine particles A2A is set to 40 nm or less, high characteristics can be obtained. Further, when the maximum particle diameter of the fine particles 12A is 5 〇 nm or less, good results can be obtained. That is, it is found that when the maximum particle diameter of the fine particles 1 2A is set to 5 〇 nm or less, high characteristics can be obtained. [Example 3] A phosphor 2 was produced in the same manner as in Example j except that the application step and the drying step of the slurry were carried out only once. . Obtained material obtained by the employment observation. The second = recognize that the entire surface of the campsite particles has formed a coating. The situation. In addition, the sound and the layer of the layer 1 to the particle layer to the third layer have the particle 1 2 A to obtain the glory material from the farm; 〇:: the structure of the layer 1 is shown near the surface of the exhibition 3 TEM photo. In addition, -14- 201202392
焭度維持率卻比實施例1為低。其係由於微粒ι2Α之積 層數為少而導致水份或紫外線從微粒12A之界面透過的 情況。亦即，得知若微粒12A是在厚度方向積層三粒子 層以上時’則可獲得更高的特性。 (實施例4，比較例4) 除了使微粒1 2 A之平均粒徑變化至小粒徑側，及隨 之所致之最大粒徑的變化外，其餘則以與實施例丨相同 的方式製造螢光體材料10及發光裝置2〇。實施例4係 使用平均粒徑為1 5nm、最大粒徑為4〇nm ;比較例4係 使用平均粒徑為8nm、最大粒徑為30nm的微粒12A^就 所獲得發光裝置20以與實施例i相同的方式進行發光試 -15- 201202392 驗，以調查亮度之經時變化。將所獲得之結果與實施例 1及比較例1-1之結果一起展示於表3。在表3中，所謂 的「2000小時後之亮度維持率」是意謂並未形成被覆層 的比較例1 -1之初期亮度為1 00%時之相對值。 Γ主The twist maintenance rate is lower than that of the first embodiment. This is because the number of layers of the particles ι2 为 is small, and moisture or ultraviolet rays are transmitted from the interface of the particles 12A. In other words, it is found that when the fine particles 12A are laminated on the three-particle layer or more in the thickness direction, higher characteristics can be obtained. (Example 4, Comparative Example 4) The same procedure as in Example 丨 was carried out except that the average particle diameter of the fine particles 1 2 A was changed to the small particle diameter side and the change in the maximum particle diameter caused therewith. The phosphor material 10 and the light-emitting device 2 are. In Example 4, the average particle diameter was 15 nm and the maximum particle diameter was 4 〇 nm. In Comparative Example 4, the luminescent device 20 was obtained using the fine particles 12A having an average particle diameter of 8 nm and a maximum particle diameter of 30 nm. I performed the luminescence test -15-201202392 in the same way to investigate the change in brightness over time. The results obtained are shown in Table 3 together with the results of Example 1 and Comparative Example 1-1. In Table 3, the "brightness retention rate after 2000 hours" means a relative value when the initial luminance of Comparative Example 1-1 in which the coating layer was not formed was 100%. Γ主
〇_ (亮度維持率）8〇%以上、，△ : 50至79% :低於49% 如表3所不，將微粒丨2 A之平均粒徑設定為】 的實施例4 ’可獲得與實施例1同樣良好的結果。相對 於此’微粒12A之平均粒徑設定為8nm的比較例4，亮 度維持率隨著時間而有顯著的降低。也就是說，可以知 道若微粒12Λ之平均粒徑設定為1 〇nm以上，較佳為 15nm以上，則可得到高性能。 為了驗證此等原因，就於實施例4及比較例4所得 之螢光體材料1 〇係使用SEM來進行觀察。圖丨丨為實施 例4之螢光體材料i 〇的SEM相片之一例圖1 2為比較 例4之螢光體材料的SEM相片之一例。如第丨丨圖及第 12圖所示，可發現相對於實施例4 一樣被覆微粒， 比較例4則未均—地被覆微粒12A，而是所見的微粒12A 的凝集體之粗大的二次凝集粒子進行附著。即，可想而 201202392 知’微粒1 2 A之平均粒徑過小時，被覆螢光體粒子1 1之 前，微粒1 2 A彼此間將會產生異常的二次凝集，而變得 難以均勻地被覆螢光體粒子1 1。 如上所述’雖然以實施形態例示說明本發明，但是 本發明並不受限於如上所述實施形態’尚可作各種變化 。例如，如上所述實施形態則說明經形成具有在螢光體 粒子1 1之表面積層微粒1 2 A的結構之被覆層1 2者，在 不至於對螢光體粒子11造成不良影響下當可更進一步 形成含有其他物質之層。 〔產業上之利用可能性〕 可使用於LED等之發光裝置。 【圖式簡單說明】 第1圖是展示本發明之一實施形態之螢光體材料示 思模式圖。 第2圖是展示使用第1圖之螢光體材料之發光裝置 構成圖。 第3圖是實施例1.之螢光體材料之SEM照片。 第4圖是在實施例1所使用的螢光體粒子之SEM照 片。 第5圖是實施例1之螢光體材料之TEM照片。 第6圖是第5圖之螢光體材料之放大照片。 第7圖是比較例1 _2之螢光體材料之TEM照片。 第8圖是展示實施例丨及比較例1 _丨、丨_2之亮度維 持率特性圖。 第9圖是貫施例3之螢光體材料之TEM照片。 -17- 201202392 第1 0圖是展示實施例3之亮度維持率特性圖。 第1 1圖是實施例4之螢光體材料之SEM照片。 第1 2圖是比較例4之螢光體材料之SEM照片。 【主要元件符號說明】 10 螢光體材料 11 螢光體粒子 12 被覆層 12Α 微粒 20 發光裝置 21 基板 22 發光元件 23 配線 24 線 25 反射框 2 6 密封層 -18 -〇_ (brightness maintenance ratio) 8〇% or more, Δ: 50 to 79%: less than 49% As shown in Table 3, Example 4 in which the average particle diameter of the fine particles A2 A is set to be ' Example 1 gave similarly good results. In Comparative Example 4 in which the average particle diameter of the fine particles 12A was set to 8 nm, the luminance maintenance ratio was remarkably lowered with time. In other words, it is understood that when the average particle diameter of the fine particles 12 is set to 1 〇 nm or more, preferably 15 nm or more, high performance can be obtained. In order to verify these reasons, the phosphor material 1 obtained in Example 4 and Comparative Example 4 was observed by SEM. Fig. 1 is an example of an SEM photograph of the phosphor material i 实施 of Example 4. Fig. 1 2 is an example of an SEM photograph of the phosphor material of Comparative Example 4. As shown in the first and fourth figures, it was found that the particles were coated as in Example 4, and in Comparative Example 4, the particles 12A were not uniformly coated, but the coarse secondary agglomeration of the aggregate of the particles 12A was observed. The particles are attached. In other words, it is known that 201202392 knows that the average particle diameter of the particles 1 2 A is too small, and before the phosphor particles 11 are coated, abnormal secondary agglomeration occurs between the particles 1 2 A, and it becomes difficult to uniformly coat them. Phosphor particles 1 1. As described above, the present invention has been described by way of embodiments, but the present invention is not limited to the embodiments described above. For example, the embodiment described above explains that the coating layer 12 having the structure of the surface layer layer particles 1 2 A having the surface area of the phosphor particles 11 is not adversely affected by the phosphor particles 11. Further forming a layer containing other substances. [Industrial Applicability] It can be used for a light-emitting device such as an LED. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a phosphor material according to an embodiment of the present invention. Fig. 2 is a view showing the configuration of a light-emitting device using the phosphor material of Fig. 1. Figure 3 is a SEM photograph of the phosphor material of Example 1. Fig. 4 is an SEM photograph of the phosphor particles used in Example 1. Fig. 5 is a TEM photograph of the phosphor material of Example 1. Figure 6 is an enlarged photograph of the phosphor material of Figure 5. Fig. 7 is a TEM photograph of the phosphor material of Comparative Example 1 _2. Fig. 8 is a graph showing the luminance maintenance ratio characteristics of Example 丨 and Comparative Example 1 _丨 and 丨_2. Figure 9 is a TEM photograph of the phosphor material of Example 3. -17-201202392 Fig. 1 is a graph showing the luminance maintenance rate characteristic of the third embodiment. Fig. 1 is a SEM photograph of the phosphor material of Example 4. Fig. 1 is a SEM photograph of the phosphor material of Comparative Example 4. [Explanation of main components] 10 Phosphor material 11 Phosphor particles 12 Coating 12 Α Particles 20 Light-emitting device 21 Substrate 22 Light-emitting element 23 Wiring 24 Line 25 Reflecting frame 2 6 Sealing layer -18 -