TWI783112B - β-Sialon phosphor, manufacturing method thereof, and light-emitting device - Google Patents
β-Sialon phosphor, manufacturing method thereof, and light-emitting device Download PDFInfo
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Abstract
一種β型賽隆螢光體，係於將Al-Kα線用作激發X射線源的X射線光電子分光光譜中，在將結合能為103.5eV時的光電子強度設為X、將結合能為102.0eV時的光電子強度設為Y時，滿足2.5>Y/X。 A β-sialon phosphor based on X-ray photoelectron spectroscopy using Al-Kα ray as an excitation X-ray source, when the photoelectron intensity when the binding energy is 103.5eV is set as X, and the binding energy is 102.0 When the photoelectron intensity at eV is Y, 2.5>Y/X is satisfied.
Description
本發明係有關β型賽隆螢光體及其製造方法、以及發光裝置。 The present invention relates to a β-sialon phosphor, a method for producing the same, and a light-emitting device.
組合發出一次光的發光元件及吸收一次光並發出二次光的螢光體而成的發光裝置，係以可期待低耗電力化、小型化、高輝度且廣範圍的色再現性之次世代的發光裝置受到矚目，且研究開發正盛行。例如，有提案一種發光裝置，係透過組合發出藍色到紫色的短波長的可視光之發光元件與螢光體，且利用發光元件的發光與藉螢光體經波長轉換後的光之混色而獲得白色光(專利文獻1)。 A light-emitting device that combines a light-emitting element that emits primary light and a phosphor that absorbs primary light and emits secondary light is a next-generation device that can expect low power consumption, miniaturization, high luminance, and wide-range color reproducibility. The light-emitting device of is attracting attention, and research and development are flourishing. For example, there is a proposal for a light-emitting device that combines a light-emitting element that emits blue to purple short-wavelength visible light and a phosphor, and utilizes the color mixing of the light emitted by the light-emitting element and the wavelength-converted light of the phosphor. White light is obtained (Patent Document 1).
近年來，就液晶顯示器的背光、照明、平板顯示器等之發光裝置來說，係被要求高輝度化，而發光裝置的高輸出化亦伴隨著進展著。由於發光裝置的高輸出化與發熱量之增加有關聯，因此發光強度隨著螢光體溫度的上升而降低，會導致發光裝置的可靠性降低。因此，追求耐久性(尤指耐熱性)優異的螢光體，使得由結晶構造穩定的β型賽隆螢光體所代表的氮化物或氮氧化物的螢光體受到矚目。 In recent years, light-emitting devices such as backlights of liquid crystal displays, lighting, and flat panel displays have been required to have higher luminance, and higher output of light-emitting devices has also been progressing. Since higher output of a light emitting device is related to an increase in heat generation, the luminous intensity decreases as the temperature of the phosphor increases, resulting in a decrease in the reliability of the light emitting device. Therefore, phosphors excellent in durability (especially heat resistance) are sought, and nitride or oxynitride phosphors, represented by β-sialon phosphors with stable crystal structures, are attracting attention.
在β型賽隆螢光體的製造方法方面，已知有將氮化矽、氮化鋁及像氧化銪般的光學活性元素化合物以既定的莫耳比混合，並以2000℃左右的溫度進行燒結，在將所獲得之燒結物粉碎之後，對粉末狀的燒結物進行酸處理之方法(專利文獻2)。又，亦知悉在原料之燒結後，進行在氮氣環境下之熱處理及在稀有氣體環境下之熱處理的方法(專利文獻3)。 In the production method of β-sialon phosphor, it is known to mix silicon nitride, aluminum nitride and an optically active element compound such as europium oxide at a predetermined molar ratio, and carry out the process at a temperature of about 2000°C. Sintering is a method of pulverizing the obtained sintered product and then subjecting the powdered sintered product to an acid treatment (Patent Document 2). Also, a method of performing heat treatment in a nitrogen atmosphere and a heat treatment in a rare gas atmosphere after sintering of raw materials is known (Patent Document 3).
[專利文獻1]日本專利第4769132號公報 [Patent Document 1] Japanese Patent No. 4769132
[專利文獻2]日本專利第4210761號公報 [Patent Document 2] Japanese Patent No. 4210761
[專利文獻3]日本專利第5508817號公報 [Patent Document 3] Japanese Patent No. 5508817
然而，藉由如專利文獻2及3那樣的公知方法所製造的β型賽隆螢光體在維持原樣的狀態下，耐久性(尤指耐熱性)並不充分，當將此β型賽隆螢光體使用於發光裝置時，有可靠性降低的問題。 However, the durability (especially heat resistance) of the β-sialon phosphor produced by the known methods such as Patent Documents 2 and 3 is not sufficient in the state as it is, and when this β-sialon When phosphors are used in light-emitting devices, there is a problem of lowering reliability.
本發明係為解決上述問題而研創者，目的在於提供一種能製造可靠性高的發光裝置之β型賽隆螢光體及其製造方法。 The present invention is developed to solve the above problems, and aims to provide a β-sialon phosphor capable of manufacturing a highly reliable light-emitting device and a manufacturing method thereof.
又，本發明之目的在於提供一種可靠性高的發光裝置。 Another object of the present invention is to provide a highly reliable light emitting device.
本案發明者們，在進行了用以解決上述問題的專心研究之結果，發現透過將β型賽隆螢光體在特定的條件下熱處理而進行表面改質，能獲得在賦予可靠性高的發光裝置之耐久性(尤指耐熱性)上優異的β型賽隆螢光體，乃至完成本發明。 The inventors of the present invention, as a result of intensive research to solve the above problems, found that by heat-treating the β-sialon phosphor under specific conditions to modify the surface, it is possible to obtain highly reliable luminescence. A β-sialon phosphor excellent in device durability (especially heat resistance) led to the completion of the present invention.
又，本發明者們經將具有上述特性的β型賽隆螢光體進行X射線光電子分光分析之結果，發現在將Al-Kα線用作激發X射線源的X射線光電子分光光譜中，特定的2個位置的結合能(binding energy)中的光電子強度(Counts/s)之比是在特定的範圍，乃至完成本發明。 Furthermore, the inventors of the present invention, as a result of X-ray photoelectron spectroscopy analysis of the β-Sialon phosphor having the above-mentioned characteristics, found that in X-ray photoelectron spectroscopy using Al-Kα rays as excitation X-ray sources, specific The ratio of the photoelectron intensity (Counts/s) in the binding energy (binding energy) of the two positions is within a specific range, leading to the completion of the present invention.
亦即，本發明之實施形態的β型賽隆螢光體為，於將Al-Kα線用作激發X射線源的X射線光電子分光光譜中，在將結合能為103.5eV時的光電子強度設為X、將結合能為102.0eV時的光電子強度設為Y時，滿足2.5>Y/X。 That is, in the β-Sialon phosphor according to the embodiment of the present invention, in the X-ray photoelectron spectroscopy using Al-Kα rays as the excitation X-ray source, the photoelectron intensity when the binding energy is 103.5 eV is set to be When X is X and the photoelectron intensity when the binding energy is 102.0 eV is Y, 2.5>Y/X is satisfied.
又，本發明之實施形態的發光裝置係包含上述的β型賽隆螢光體。 Also, a light-emitting device according to an embodiment of the present invention includes the above-mentioned β-sialon phosphor.
再者，本發明之實施形態的β型賽隆螢光體的製造方法為，在水相對於β型賽隆螢光體及水的合計質量為0.5質量%以上的共存狀態，以150℃以上的溫度對β型賽隆螢光體進行熱處理。 Furthermore, in the method for producing a β-Sialon phosphor according to an embodiment of the present invention, in a state where water coexists at 0.5% by mass or more with respect to the total mass of the β-Sialon phosphor and water, the temperature is 150° C. or higher. The temperature of the β-sialon phosphor is heat-treated.
依據本發明，可提供能製造可靠性高的發光裝置之β型賽隆螢光體及其製造方法。 According to the present invention, it is possible to provide a β-sialon phosphor capable of manufacturing a highly reliable light-emitting device and a method for manufacturing the same.
又，依據本發明，能提供可靠性高的發光裝置。 Also, according to the present invention, a highly reliable light emitting device can be provided.
圖1係實施例1及比較例1的β型賽隆螢光體的X射線光電子分光光譜。 FIG. 1 is the X-ray photoelectron spectroscopy spectra of the β-sialon phosphors of Example 1 and Comparative Example 1. FIG.
圖2係實施例1及比較例1~2的β型賽隆螢光體的經FT-IR所測定的庫貝卡-孟克函數(Kubelka-Munk Function)的值(KM值)的光譜。 Fig. 2 is a spectrum of the Kubelka-Munk function value (KM value) measured by FT-IR of the β-Sialon phosphors of Example 1 and Comparative Examples 1-2.
以下，針對本發明的β型賽隆螢光體及其製造方法、以及發光裝置的實施形態作詳細說明。但本發明未受以下的實施形態所限定，可在不悖離其要旨之範圍下將構成要素變形並予以具體化。又，藉由以下的實施形態所揭示之複數個構成要素的適宜組合，可形成各種發明。例如，亦可從實施形態所示的全構成要素去除幾個構成要素。再者，亦可適宜地組合不同的實施形態的構成要素。 Hereinafter, embodiments of the β-Sialon phosphor of the present invention, its manufacturing method, and light-emitting device will be described in detail. However, the present invention is not limited to the following embodiments, and constituent elements can be modified and embodied within a range not departing from the gist. In addition, various inventions can be formed by appropriate combinations of a plurality of constituent elements disclosed in the following embodiments. For example, some constituent elements may be removed from all the constituent elements shown in the embodiment. In addition, components of different embodiments may be combined appropriately.
本說明書中的「β型賽隆螢光體」，係指在β型氮化矽(Si3N4)的Si位置有Al部分置換且N位置有O部分置換而成的固溶體，且能以通式：Si6-zAlzOzN8-z表示。式中，z係0~4.2。又，β型賽隆螢光體係在紫外光到可視光的寬廣波長區域被激發而發出綠色光。 "β-Sialon phosphor" in this specification refers to a solid solution in which the Si position of β-type silicon nitride (Si 3 N 4 ) is partially substituted by Al and the N position is partially substituted by O, and It can be represented by the general formula: Si 6-z Al z O z N 8-z . In the formula, z is 0~4.2. Also, the β-sialon fluorescent system is excited in a broad wavelength range from ultraviolet light to visible light to emit green light.
本實施形態的β型賽隆螢光體為，於將Al-Kα線用作激發X射線源的X射線光電子分光光譜中，在將結合能為103.5eV時的光電子強度設為X、將結合能為102.0eV時的光電子強度設為Y時，滿足2.5>Y/X。當 2.5≦Y/X時，因為β型賽隆螢光體的耐久性未充分提升，所以無法獲得可靠性高的發光裝置。 In the β-sialon phosphor of this embodiment, in the X-ray photoelectron spectroscopy using Al-Kα rays as an excitation X-ray source, the photoelectron intensity at the time of binding energy of 103.5 eV is X, and the binding energy is 103.5 eV. When the photoelectron intensity at 102.0 eV is Y, 2.5>Y/X is satisfied. when When 2.5≦Y/X, since the durability of the β-sialon phosphor is not sufficiently improved, a highly reliable light-emitting device cannot be obtained.
此處，X射線光電子分光光譜係可由各光電子強度的結合能之值特定官能基等。結合能為103.5eV時的光電子強度係表示Si-N鍵，而在結合能為102.0eV時的光電子強度係表示Si-O鍵的存在。 Here, X-ray photoelectron spectroscopy can specify functional groups and the like based on the value of the binding energy of each photoelectron intensity. The photoelectron intensity at the binding energy of 103.5 eV indicates the Si-N bond, and the photoelectron intensity at the binding energy of 102.0 eV indicates the presence of the Si-O bond.
這可認為是在滿足2.5>Y/X時，因為Si-O鍵相對於Si-N鍵之比例變高，所以β型賽隆螢光體的表面水解而充分形成氧化層(亦即，表面改質被充分進行)。當在β型賽隆螢光體的表面充分形成氧化層時，進一步的水解受到抑制。其結果，在發光裝置中的β型賽隆螢光體的溫度上升之際，由於銨離子等之離子性物質的產生受到抑制，故發光裝置的可靠性提升。 This can be considered to be that when 2.5>Y/X is satisfied, because the ratio of Si-O bonds to Si-N bonds becomes higher, the surface of the β-sialon phosphor is hydrolyzed to fully form an oxide layer (that is, the surface modification is fully carried out). When the oxide layer is sufficiently formed on the surface of the β-Sialon phosphor, further hydrolysis is suppressed. As a result, when the temperature of the β-sialon phosphor in the light-emitting device rises, the generation of ionic substances such as ammonium ions is suppressed, thereby improving the reliability of the light-emitting device.
X射線光電子分光光譜，係可藉由X射線光電子分光分析(XPS)而獲得。其測定條件如下。 X-ray photoelectron spectroscopy can be obtained by X-ray photoelectron spectroscopy (XPS). The measurement conditions are as follows.
測定裝置：X射線光電子分光分析裝置(ULVAC-PHI,Inc.製PHI5000VersaProbeII) Measuring device: X-ray photoelectron spectroscopic analysis device (PHI5000VersaProbeII manufactured by ULVAC-PHI, Inc.)
輸出：15kV-50W Output: 15kV-50W
測定區域：200μmΦ Measuring area: 200μmΦ
通能(Pass energy)：187eV Pass energy: 187eV
步距：50ms Step distance: 50ms
本實施形態的β型賽隆螢光體較佳為，於使用了FT-IR的庫貝卡-孟克(Kubelka-Munk：以下，有時簡稱為「K-M」)函數的值(KM值)的光譜中，在將波數為3650cm-1時的KM值設為A、將波數為2600cm-1時的KM 值設為D時，滿足0.15<A/D。 The β-sialon phosphor of this embodiment is preferably the value (KM value) of the Kubelka-Munk (Kubelka-Munk: hereinafter, sometimes abbreviated as "KM") function using FT-IR. In the spectrum of , 0.15<A/D is satisfied when the KM value at a wave number of 3650 cm −1 is A and the KM value at a wave number of 2600 cm −1 is D.
此處，本說明書中「庫貝卡-孟克函數的值」，係指將物質的反射率轉換成作為物質固有的吸收指標之值的函數，且可透過吸光係數除以散射係數(吸光係數/散射係數)而獲得。 Here, the "value of the Kubekka-Munck function" in this specification refers to a function that converts the reflectance of a substance into a value that is an index of absorption inherent in the substance, and can be divided by the light absorption coefficient by the scattering coefficient (absorption coefficient /scattering coefficient) is obtained.
使用了FT-IR的庫貝卡-孟克函數的值(KM值)的光譜係可由波數之值特定官能基等。波數為3650cm-1時的KM值係表示Si-OH鍵，波數為2600cm-1時的KM值係表示源自於β型賽隆螢光體的構造之峰值。 The spectrum using the value of the Kubekar-Munck function (KM value) of FT-IR can specify a functional group or the like from the value of the wave number. The KM value at the wave number of 3650 cm -1 represents the Si-OH bond, and the KM value at the wave number of 2600 cm -1 represents the peak derived from the structure of the β-sialon phosphor.
可認為是在滿足0.15<A/D時，因為β型賽隆螢光體的構造所佔的Si-OH鍵之比例變高，所以β型賽隆螢光體的表面水解而充分形成氧化層(亦即，表面改質被充分進行)。因此，β型賽隆螢光體進一步的水解受抑制的結果，在發光裝置中的β型賽隆螢光體的溫度上升之際，變得難以產生銨離子等之離子性物質，使發光裝置的可靠性提升。 It can be considered that when 0.15<A/D is satisfied, since the structure of the β-sialon phosphor occupies a higher ratio of Si-OH bonds, the surface of the β-sialon phosphor is hydrolyzed to form an oxide layer sufficiently (That is, surface modification is sufficiently performed). Therefore, as a result of suppressing further hydrolysis of the β-Sialon phosphor, when the temperature of the β-Sialon phosphor in the light-emitting device rises, it becomes difficult to generate ionic substances such as ammonium ions, and the light-emitting device reliability improvement.
庫貝卡-孟克函數的值(KM值)的光譜係可藉由傅立葉轉換紅外線吸收分析(FT-IR)而獲得。測定係使用PerkinElmer Japan Co.,Ltd.製Spectrum One來進行。測定試樣係只要不將β型賽隆螢光體稀釋下予以顆粒(pellet)化即可。 The spectrum of the Kubekar-Munck function value (KM value) can be obtained by Fourier transform infrared absorption analysis (FT-IR). The measurement was performed using Spectrum One manufactured by PerkinElmer Japan Co., Ltd. The measurement sample may be pelletized without diluting the β-Sialon phosphor.
本實施形態的β型賽隆螢光體較佳為，於使用了FT-IR的庫貝卡-孟克函數的值(KM值)的光譜中，在將波數為3650cm-1時的KM值設為A、將波數為3400cm-1時的KM值設為B時，滿足0.2<A/B。 The β - Sialon phosphor of the present embodiment is preferably KM at a wave number of 3650 cm When the value is A and the KM value at a wavenumber of 3400 cm −1 is B, 0.2<A/B is satisfied.
此處，波數為3400cm-1時的KM值係表示吸附水的O-H鍵。 Here, the KM value when the wave number is 3400 cm -1 represents the OH bond of adsorbed water.
可認為是在滿足0.2<A/B時，因為相較於吸附水的O-H鍵，氧化層的Si-OH鍵之比例變高，所以β型賽隆螢光體的表面水解而充分形成氧化層。因此，在發光裝置中的β型賽隆螢光體的溫度上升之際，變得難以產生銨離子等之離子性物質，使發光裝置的可靠性提升。 It can be considered that when 0.2<A/B is satisfied, since the ratio of Si-OH bonds in the oxide layer becomes higher than that of O-H bonds that absorb water, the surface of the β-Sialon phosphor is hydrolyzed to form an oxide layer sufficiently . Therefore, when the temperature of the β-sialon phosphor in the light-emitting device rises, it becomes difficult to generate ionic substances such as ammonium ions, and the reliability of the light-emitting device is improved.
本實施形態的β型賽隆螢光體較佳為，於使用了FT-IR的庫貝卡-孟克函數的值(KM值)的光譜中，在將波數為3200cm-1時的KM值設為C、將波數為3400cm-1時的KM值設為B時，滿足0.7<C/B。 The β - sialon phosphor of the present embodiment is preferably KM at a wave number of 3200 cm When the value is C and the KM value at a wave number of 3400 cm −1 is B, 0.7<C/B is satisfied.
此處，波數為3200cm-1時的KM值係表示氧化層的Al-OH鍵。 Here, the KM value at a wave number of 3200 cm -1 represents the Al-OH bond of the oxide layer.
可認為是在滿足0.7<C/B時，相較於吸附水的O-H鍵，氧化層的Al-OH鍵的比例變高，故而β型賽隆螢光體的表面水解而充分形成氧化層。因此，在發光裝置中的β型賽隆螢光體的溫度上升之際，變得難以產生銨離子等之離子性物質，使發光裝置的可靠性提升。 It is considered that when 0.7<C/B is satisfied, the ratio of Al-OH bonds in the oxide layer becomes higher than that of O-H bonds that absorb water, so that the surface of the β-Sialon phosphor is hydrolyzed to sufficiently form an oxide layer. Therefore, when the temperature of the β-sialon phosphor in the light-emitting device rises, it becomes difficult to generate ionic substances such as ammonium ions, and the reliability of the light-emitting device is improved.
具有上述特徵的本實施形態的β型賽隆螢光體，係可在水相對於β型賽隆螢光體及水的合計質量為0.5質量%以上的共存狀態，藉由以150℃以上的溫度對β型賽隆螢光體進行熱處理而製造。當共存水量小於0.5質量%或加熱溫度小於150℃時，β型賽隆螢光體的表面水解變不充分，未充分形成氧化層。 The β-sialon phosphor of the present embodiment having the above-mentioned characteristics can coexist in a state where water is 0.5% by mass or more with respect to the total mass of the β-sialon phosphor and water. Manufactured by heat-treating β-Sialon phosphors. When the amount of coexisting water is less than 0.5% by mass or the heating temperature is less than 150° C., the surface hydrolysis of the β-sialon phosphor becomes insufficient, and the oxide layer is not sufficiently formed.
在作成以水相對於β型賽隆螢光體及水的合 計質量為0.5質量%以上的共存狀態之方法方面並未特別限定，例如，在混合β型賽隆螢光體與水之後，只要將混合物(含水量0.5質量%以上)設為密閉狀態即可。 In making a combination of water relative to β-sialon phosphor and water There are no particular limitations on the method of coexisting at 0.5% by mass or more. For example, after mixing the β-sialon phosphor and water, the mixture (with a water content of 0.5% by mass or more) should be airtight. .
熱處理時的壓力條件雖未特別限定，但較佳為在0.05MPa以上的錶壓(gauge pressure)下進行熱處理。透過在上述的壓力條件下進行熱處理，可有效率地進行β型賽隆螢光體的表面之水解。作為用以在此種壓力條件下進行熱處理的方法，未特別限定，例如，只要使用密閉容器且在密閉狀態下能進行加熱處理即可。 The pressure conditions during the heat treatment are not particularly limited, but it is preferable to perform the heat treatment at a gauge pressure of 0.05 MPa or higher. By performing heat treatment under the above-mentioned pressure conditions, the hydrolysis of the surface of the β-sialon phosphor can be efficiently performed. It does not specifically limit as a method for heat-processing under such pressure conditions, For example, what is necessary is just to use an airtight container and to be able to heat-process in a sealed state.
作為上述的熱處理前的β型賽隆螢光體，未特別限定，只要是藉由公知的方法所獲得者即可。具體言之，上述的熱處理前的β型賽隆螢光體係可藉由燒結包含有氮化矽、氮化鋁、像氧化銪的光學活性元素化合物之混合原料粉末，且將所獲得之燒結物粉碎而獲得。此外，上述的熱處理前的β型賽隆螢光體亦可視需要進行酸處理、在非活性環境下進行熱處理。又，作為上述的熱處理前的β型賽隆螢光體，亦可使用市售品。 The above-mentioned β-Sialon phosphor before heat treatment is not particularly limited, as long as it is obtained by a known method. Specifically, the above-mentioned β-sialon fluorescent system before heat treatment can be obtained by sintering mixed raw material powders containing silicon nitride, aluminum nitride, and optically active element compounds such as europium oxide, and the obtained sintered product Obtained by crushing. In addition, the above-mentioned β-sialon phosphor before heat treatment may also be acid-treated or heat-treated in an inactive environment as needed. In addition, commercially available items can also be used as the above-mentioned β-sialon phosphor before heat treatment.
在進行上述的熱處理之後，亦能在大氣中，以100℃以上，較佳為以100~600℃進一步熱處理。透過進行進一步的熱處理，因為可除去β型賽隆螢光體的吸附水及結晶水，故發光裝置的可靠性提升。 After the above-mentioned heat treatment, it can also be further heat-treated in the atmosphere at 100°C or higher, preferably at 100-600°C. Through further heat treatment, since the adsorption water and crystal water of the β-Sialon phosphor can be removed, the reliability of the light-emitting device is improved.
照這樣所獲得之本實施形態的β型賽隆螢光體，由於在發光裝置內的溫度上升之際，難以產生銨離子等之離子性物質，所以對使用在發光裝置是有用的。 The β-Sialon phosphor of the present embodiment thus obtained is useful for use in a light-emitting device because it is less likely to generate ionic substances such as ammonium ions when the temperature inside the light-emitting device rises.
本實施形態的發光裝置係包含上述的β型賽 隆螢光體。在此發光裝置中，β型賽隆螢光體通常被用作發光構件。發光構件係可藉由將β型賽隆螢光體與密封材料(例如，聚矽氧樹脂)混合進行硬化而獲得。發光構件也可含有除了β型賽隆螢光體之外的螢光體。 The light-emitting device of the present embodiment includes the above-mentioned β-type LED Long phosphor. In this light emitting device, a β-sialon phosphor is generally used as a light emitting member. The light emitting member can be obtained by mixing β-sialon phosphor with a sealing material (for example, silicone resin) and hardening. The light-emitting member may contain phosphors other than the β-sialon phosphor.
又，本實施形態的發光裝置可包含各種發光元件。在發光元件方面，雖未特別限定，但較佳為發出波長240~480nm之光的紫外線LED或藍色LED，更佳為發出波長440~470nm之光的藍色LED。例如，藉由上述的β型賽隆螢光體與紫外線LED或藍色LED組合，可獲得白色發光裝置(白色LED)。 In addition, the light emitting device of this embodiment may include various light emitting elements. The light-emitting element is not particularly limited, but is preferably an ultraviolet LED or a blue LED that emits light with a wavelength of 240-480 nm, and more preferably a blue LED that emits light with a wavelength of 440-470 nm. For example, a white light-emitting device (white LED) can be obtained by combining the above-mentioned β-sialon phosphor with an ultraviolet LED or a blue LED.
具有上述特徵的本實施形態的發光裝置由於含有在發光裝置內的溫度上升之際難以產生銨離子等之離子性物質的β型賽隆螢光體，故可靠性高。 The light-emitting device according to the present embodiment having the above characteristics has high reliability because it contains a β-sialon phosphor that hardly generates ionic substances such as ammonium ions when the temperature inside the light-emitting device rises.
以下，使用實施例及比較例更具體說明本發明，但本發明只要未悖離其要旨，則不受下述實施例所限定。 Hereinafter, although an Example and a comparative example are used and this invention is demonstrated more concretely, this invention is not limited to the following Example unless it deviates from the summary.
將β型賽隆螢光體(Denka Co.,Ltd.製GR-SW529B)95質量%與離子交換水5質量%混合。其次，在將混合物20g放入內側有鐵弗龍(註冊商標)為襯底的SUS316製容器(50cc)之後，於密閉狀態，以溫度200℃進行168小時的熱處理。熱處理時的容器內的錶壓經測定後為1.62MPa。其次，在對熱處理後的β型賽隆螢光體一邊澆 離子交換水一邊使之通過尼龍篩(網眼150μm)後，使用孔徑10μm以下的濾紙過濾。在將過濾物以離子交換水3L洗淨並再度進行過濾之後，透過在80℃下乾燥25小時，獲得實施例1的β型賽隆螢光體。 95% by mass of β-sialon phosphor (GR-SW529B manufactured by Denka Co., Ltd.) and 5% by mass of ion-exchanged water were mixed. Next, after putting 20 g of the mixture into a SUS316 container (50 cc) with a Teflon (registered trademark) substrate inside, heat treatment was performed at a temperature of 200° C. for 168 hours in a sealed state. The measured gauge pressure in the container during the heat treatment was 1.62 MPa. Secondly, while pouring the heat-treated β-sialon phosphor After passing the ion-exchanged water through a nylon mesh (mesh 150 μm), it was filtered using filter paper with a pore diameter of 10 μm or less. The filtrate was washed with 3 L of ion-exchanged water, filtered again, and dried at 80° C. for 25 hours to obtain the β-Sialon phosphor of Example 1.
除了以200℃進行48小時熱處理之外，同實施例1的條件下進行處理，藉以獲得實施例2的β型賽隆螢光體。此外，熱處理時的容器內的錶壓經測定後為1.62MPa。 Except for the heat treatment at 200° C. for 48 hours, the treatment was carried out under the same conditions as in Example 1, so as to obtain the β-sialon phosphor of Example 2. In addition, the gauge pressure in the container during the heat treatment was measured to be 1.62 MPa.
將實施例2的β型賽隆螢光體於大氣中，於大氣壓以150℃進一步進行5小時熱處理，藉以獲得實施例3的β型賽隆螢光體。 The β-Sialon phosphor of Example 2 was further heat-treated at 150° C. for 5 hours in the air at atmospheric pressure, so as to obtain the β-Sialon phosphor of Example 3.
將實施例2的β型賽隆螢光體於大氣中，於大氣壓以80℃進一步進行5小時熱處理，藉以獲得實施例4的β型賽隆螢光體。 The β-Sialon phosphor of Example 2 was further heat-treated at 80° C. for 5 hours in the air at atmospheric pressure, thereby obtaining the β-Sialon phosphor of Example 4.
除了以150℃進行48小時熱處理之外，同實施例1的條件下進行處理，藉以獲得實施例5的β型賽隆螢光體。此外，熱處理時的錶壓經測定後為0.52MPa。 Except for the heat treatment at 150° C. for 48 hours, the treatment was carried out under the same conditions as in Example 1, so as to obtain the β-sialon phosphor of Example 5. In addition, the gauge pressure during the heat treatment was measured to be 0.52 MPa.
除了混合β型賽隆螢光體(Denka Co.,Ltd.製GR-SW529B)99.5質量%與離子交換水0.5質量%之外，同實施例2的條件下進行處理，藉以獲得實施例6的β型賽隆螢光體。此外，熱處理時的錶壓經測定後為0.68MPa。 Except mixing 99.5% by mass of β-sialon phosphor (GR-SW529B manufactured by Denka Co., Ltd.) and 0.5% by mass of ion-exchanged water, the same conditions as in Example 2 were used to obtain Example 6. β-sialon phosphor. In addition, the gauge pressure during the heat treatment was measured to be 0.68 MPa.
將熱處理前的β型賽隆螢光體(Denka Co.,Ltd.製GR-SW529B)設為比較例1。 A β-sialon phosphor (GR-SW529B manufactured by Denka Co., Ltd.) before heat treatment was used as Comparative Example 1.
將β型賽隆螢光體(Denka Co.,Ltd.製GR-SW529B)於大氣中，以大氣壓、200℃進行168小時熱處理。其次，在對熱處理後的β型賽隆螢光體一邊澆離子交換水一邊使之通過尼龍篩(網眼150μm)後，使用孔徑10μm以下的濾紙過濾。在將過濾物以離子交換水3L洗淨並再度進行過濾之後，透過在80℃下乾燥25小時，獲得比較例2的β型賽隆螢光體。 A β-sialon phosphor (GR-SW529B manufactured by Denka Co., Ltd.) was heat-treated at 200° C. for 168 hours at atmospheric pressure in the air. Next, after pouring ion-exchanged water over the heat-treated β-Sialon phosphor, it was passed through a nylon mesh (mesh 150 μm), and then filtered using filter paper with a pore diameter of 10 μm or less. The filtrate was washed with 3 L of ion-exchanged water, filtered again, and dried at 80° C. for 25 hours to obtain the β-Sialon phosphor of Comparative Example 2.
除了以100℃進行48小時熱處理之外，同實施例1的條件下進行處理，藉以獲得比較例3的β型賽隆螢光體。此外，熱處理時的錶壓經測定後為0.13MPa。 Except for the heat treatment at 100° C. for 48 hours, the treatment was carried out under the same conditions as in Example 1, so as to obtain the β-sialon phosphor of Comparative Example 3. In addition, the gauge pressure during the heat treatment was measured to be 0.13 MPa.
除了以50℃進行48小時熱處理之外，同實施例1的條件下進行處理，藉以獲得比較例4的β型賽隆螢光體。此外，熱處理時的錶壓經測定後為0.02MPa。 Except for the heat treatment at 50° C. for 48 hours, the treatment was carried out under the same conditions as in Example 1, so as to obtain the β-sialon phosphor of Comparative Example 4. In addition, the gauge pressure during the heat treatment was measured to be 0.02 MPa.
除了β型賽隆螢光體(Denka Co.,Ltd.製GR-SW529B)不與水混合且使用了β型賽隆螢光體20g之外，同實施例2的條件下進行處理，藉以獲得比較例5的β型賽隆螢光體。此外，熱處理時的錶壓經測定後為0.06MPa。 Except that the β-sialon phosphor (GR-SW529B manufactured by Denka Co., Ltd.) was not mixed with water and 20 g of the β-sialon phosphor was used, it was treated under the same conditions as in Example 2 to obtain β-Sialon phosphor of Comparative Example 5. In addition, the gauge pressure during the heat treatment was measured to be 0.06 MPa.
上述的實施例及比較例中的熱處理條件彙整於表1。 Table 1 summarizes the heat treatment conditions in the above-mentioned examples and comparative examples.
針對在上述的實施例及比較例獲得之β型賽隆螢光體，進行了X射線光電子分光分析，傅立葉轉換紅外線吸收分析及可靠性評估。 X-ray photoelectron spectroscopy analysis, Fourier transform infrared absorption analysis and reliability evaluation were performed on the β-sialon phosphors obtained in the above-mentioned examples and comparative examples.
X射線光電子分光分析及傅立葉轉換紅外線吸收分析，係以上述的條件進行了測定。又，可靠性評估係按下述方式進行。 X-ray photoelectron spectroscopy and Fourier transform infrared absorption analysis were measured under the above-mentioned conditions. In addition, the reliability evaluation was performed as follows.
將在實施例及比較例獲得之β型賽隆螢光體2.5g及聚矽氧樹脂(Dow Corning Toray Co.,Ltd.製OE6656)47.5g以自轉公轉型的混合機(THINKY股份有限公司製AWATORI RENTARO(註冊商標)ARE-310)混合。其次，在凹型的封裝本體的底部配置發光元件(LED)並與基板上的電極連結(wire bonding)之後，以覆蓋發光元件的方式，使混合物從微注射器(micro syringe)注入，以150℃使之硬化。之後，透過以110℃進行10小時的後硬化(post cure)並密封，作成LED封裝。發光元件使用了發光峰值波長為448nm且大小為1.0mm×0.5mm者。 2.5 g of the β-sialon phosphor obtained in Examples and Comparative Examples and 47.5 g of polysiloxane resin (OE6656 manufactured by Dow Corning Toray Co., Ltd.) were used in a rotary-revolving type mixer (manufactured by THINKY Co., Ltd. AWATORI RENTARO (registered trademark) ARE-310) was mixed. Next, after disposing the light-emitting element (LED) at the bottom of the concave package body and connecting to the electrode on the substrate (wire bonding), the mixture is injected from a micro syringe (micro syringe) in such a way as to cover the light-emitting element, and heated at 150°C. of hardening. Thereafter, after performing post cure at 110° C. for 10 hours and sealing, an LED package was fabricated. As the light-emitting element, one with an emission peak wavelength of 448 nm and a size of 1.0 mm×0.5 mm was used.
其次，在將直流穩壓電源連接的LED封裝放入85℃、85%RH的恆溫恆濕槽且以90mA通電使之點亮的狀態進行1000小時的曝露。測定曝露前後的LED封裝的全光束，算出曝露後的LED封裝的全光束保持率。若全光束保持率為93%以上，則能判定為可靠性高。 Next, exposure was performed for 1000 hours in a state where the LED package connected to the DC stabilized power supply was placed in a constant temperature and humidity chamber at 85° C. and 85% RH, and turned on at 90 mA. The total luminous flux of the LED package before and after exposure was measured, and the total luminous flux retention rate of the exposed LED package was calculated. When the full beam retention rate is 93% or more, it can be judged that the reliability is high.
將上述的各評估結果顯示在表2。 Table 2 shows each of the above evaluation results.
此處，針對X射線光電子分光分析及傅立葉轉換紅外線吸收分析的結果，作為代表例，將實施例1及比較例1的β型賽隆螢光體的X射線光電子分光光譜顯示於圖1。又，將實施例1及比較例1~2的β型賽隆螢光體的庫貝卡-孟克函數的值(KM值)的光譜顯示於圖2。 Here, the X-ray photoelectron spectroscopy spectra of the β-Sialon phosphors of Example 1 and Comparative Example 1 are shown in FIG. 1 as representative examples of the results of X-ray photoelectron spectroscopy and Fourier transform infrared absorption analysis. Moreover, the spectrum of the Kubecart-Munck function value (KM value) of the β-Sialon phosphors of Example 1 and Comparative Examples 1 to 2 is shown in FIG. 2 .
如表2所示，實施例1~6的β型賽隆螢光體係2.5>Y/X，可獲得全光束保持率為93%以上的可靠性高的LED封裝。 As shown in Table 2, the β-sialon fluorescent system 2.5>Y/X of Examples 1-6 can obtain a highly reliable LED package with a full beam retention rate of over 93%.
相對地，比較例1的β型賽隆螢光體因為未進行熱處理，所以表面未充分形成氧化層，成為2.5≦Y/X(Si-O鍵相對於Si-N鍵之比例變低)。其結果，可認為是此β型賽隆螢光體在溫度上升之際產生銨離子等之離子性物質，LED封裝的全光束保持率(可靠性)降低。 In contrast, the β-Sialon phosphor of Comparative Example 1 was not subjected to heat treatment, so the oxide layer was not sufficiently formed on the surface, and it was 2.5≦Y/X (the ratio of Si-O bond to Si-N bond was low). As a result, it is considered that the β-sialon phosphor generates ionic substances such as ammonium ions when the temperature rises, and the total light beam retention (reliability) of the LED package decreases.
比較例2的β型賽隆螢光體因為是在大氣中進行了熱處理，所以表面的水解未被充分進行。又，比較例3及4的β型賽隆螢光體因為熱處理溫度過低，所以表面的水解未被充分進行。再者，比較例5的β型賽隆螢光體，在熱處理之際，因為未設成水相對於β型賽隆螢光體及水的合計質量為0.5質量%以上的共存狀態，所以表面的水解未被充分進行。因此，可認為是此等β型賽隆螢光體係表面未充分形成氧化層，成為2.5≦Y/X(Si-O鍵相對於Si-N鍵之比例變低)，LED封裝的全光束保持率(可靠性)降低。 Since the β-Sialon phosphor of Comparative Example 2 was heat-treated in the air, the hydrolysis of the surface did not proceed sufficiently. In addition, in the β-Sialon phosphors of Comparative Examples 3 and 4, since the heat treatment temperature was too low, the hydrolysis of the surface did not proceed sufficiently. Furthermore, the β-Sialon phosphor of Comparative Example 5 did not coexist in a state where water was 0.5% by mass or more relative to the total mass of the β-Sialon phosphor and water at the time of heat treatment, so the surface The hydrolysis is not fully carried out. Therefore, it can be considered that the oxide layer is not sufficiently formed on the surface of these β-sialon fluorescent systems, and becomes 2.5≦Y/X (the ratio of Si-O bonds to Si-N bonds becomes lower), and the full beam of the LED package remains Rate (reliability) decreases.
又，經比較實施例2與實施例3，透過在熱處理之後，於大氣中以100℃以上的溫度進一步熱處理，使LED封裝的全光束保持率(可靠性)提升。這可認為是因為透過進一步的熱處理而除去了β型賽隆螢光體的吸附水。經實際觀察庫貝卡-孟克函數的值(KM值)的光譜後，表示吸附水的O-H鍵之KM值B降低，A/B、C/B的值上升。 In addition, by comparing Example 2 and Example 3, after the heat treatment, further heat treatment at a temperature above 100° C. in the atmosphere improves the total beam retention (reliability) of the LED package. This is considered to be because the adsorbed water of the β-Sialon phosphor was removed by further heat treatment. After actually observing the spectrum of the Kubekka-Munck function value (KM value), it shows that the KM value B of the O-H bond of adsorbed water decreases, and the values of A/B and C/B increase.
即便是進行進一步的熱處理之情況，在如實施例4般熱處理溫度小於100℃時，未充分獲得LED封裝的全光束保持率(可靠性)的提升效果。 Even when further heat treatment is performed, when the heat treatment temperature is lower than 100° C. as in Example 4, the effect of improving the total light beam retention (reliability) of the LED package is not sufficiently obtained.
從以上結果可知，依據本發明，可提供能製造可靠性高的發光裝置之β型賽隆螢光體及其製造方法。又，依據本發明，能提供可靠性高的發光裝置。 From the above results, according to the present invention, it is possible to provide a β-sialon phosphor capable of manufacturing a highly reliable light-emitting device and a method for manufacturing the same. Also, according to the present invention, a highly reliable light emitting device can be provided.
本發明的β型賽隆螢光體，係可使用於白色 發光裝置，有色發光裝置等之各式各樣的發光裝置。作為白色發光裝置，可舉出液晶顯示器、液晶面板的背光、照明裝置、信號裝置、影像顯示裝置等。又，本發明的β型賽隆螢光體及發光裝置亦可作為投影機用途來使用。 The β-sialon phosphor of the present invention can be used in white Various light-emitting devices such as light-emitting devices and colored light-emitting devices. Examples of white light-emitting devices include liquid crystal displays, backlights for liquid crystal panels, lighting devices, signaling devices, video display devices, and the like. In addition, the β-sialon phosphor and light-emitting device of the present invention can also be used as a projector.
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