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TW201140891A - Warelength converting member, optical elemant and manufacturing method for wavelength converting member - Google Patents

Warelength converting member, optical elemant and manufacturing method for wavelength converting member Download PDF

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Publication number
TW201140891A
TW201140891A TW100107659A TW100107659A TW201140891A TW 201140891 A TW201140891 A TW 201140891A TW 100107659 A TW100107659 A TW 100107659A TW 100107659 A TW100107659 A TW 100107659A TW 201140891 A TW201140891 A TW 201140891A
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Taiwan
Prior art keywords
glass
powder
inorganic phosphor
phosphor powder
wavelength conversion
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TW100107659A
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Chinese (zh)
Inventor
Yoshio Umayahara
Shunsuke Fujita
Masaru Iwao
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Nippon Electric Glass Co
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Publication of TW201140891A publication Critical patent/TW201140891A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7706—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/621—Chalcogenides
    • C09K11/625—Chalcogenides with alkaline earth metals

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Led Device Packages (AREA)
  • Luminescent Compositions (AREA)

Abstract

Provided is a wavelength converting member having high luminous efficiency, wherein the wavelength converting member comprises inorganic fluorescent powder dispersed in glass matrix. The wavelength comverting member comprises glass matrix, inorgamic fluorescent powder dispersed in the glass matrix, and a interlanyer with thickness of 0.01 to 5 μ m being set in the interface of inorgamic fluorescent powder and glass matrix, and comprising reation product of the inorgamic fluorescent powder and the glass matrix.

Description

201140891 六、發明說明： 【發明所屬之技術領域】 本發明係關於作為白色LED(Light Emitting Diode) 等構成構件所使用之波長變換構件、使用其之光學元件及 波長變換構件之製造方法。 【先前技術】 近年來白色LED的開發相當盛行。白色LED是以例如 發出藍色或紫外激發光之LED及將無機螢光體粉末分散至 樹脂等基質中所形成之波長變換構件所構成。無機螢光體 粉末接受來自LED的激發光而發出與激發光相異波長之光 (榮光）。另一方面，來自LED的激發光中一部份沒有經過 波長變換而透過波長變換構件。混合這些光而得白色光。 白色LED特徵為與白熾燈及螢光燈相比其消費電量較 低且f命長。因此白色LED —直使用作為手機與數位相機 等的者光。今後作為取代白熾燈及螢光燈之次世代之光 源’白色LED在照明用途之應用令人期待。 白色LED依用途不同而越來越要求高亮度（High power) 、因此如以往在樹脂基質中分散無機螢光體粉末的方 因來自LED的熱造成樹脂基質變色，長時間使用會有 X下降之問題。此外將含有無機螢光體粉末的樹脂塗佈 ,LED上時，容易有產生厚度不—致，使配光性降低的情 形0 為了解决足些問題，已提出將無機螢光體粉末分散在 基質中使波長變換構件完全無機化的方法（例如參照 322846 3 201140891 專利文獻1及2)。依該方法可提升波長變換構件之耐熱性 及耐候性。具體來說在高溫環境下（例如15(TC、600小時） 或高溫高濕環境下（例如溫度85°C、濕度85%、2000小時） 長時間暴露，其白色LED發光特性幾乎沒有變化，或以太 陽光的紫外線長時間曝曬也幾乎沒有著色或劣化。再者因 其加工性優異，亦可抑制因厚度不一致所引起之配光性下 降。 [先前技術文獻] ‘[專利文獻] [專利文獻1]日本特開2005-11933號公報 [專利文獻2]曰本專利第4158〇12號公報 【發明内容】 (發明欲解決之課題） 將無機螢光體粉末分散在玻璃基質中所成之波長變換 構件，其與使用树知基質之波長變換構件相比較雖然長期 ( '安定性為優異，但過去將無機螢光體粉末分散在玻璃基質 中所成之波長遂換構件，因在無機螢光體粉末與玻璃基質 的界面中反射與散射而造成光損失很大。因此難以達到充 分尚的發光效率。另外在無機螢光體粉末與玻璃基質的界 面中之反射與散射，其原因為無機螢光體粉末與玻璃基質 的折射率差異。 因此本發明之課題係提供可得高發光效率之波長變換 構件，其為將無機螢光體粉末分散在玻璃基質中之波長變 換構件。 322846 4 201140891 (解決課題之手段） 本發明者們銳意檢討之結果，發現可由在玻璃基質與 無機榮光體氣末的界面形成特定的層以解決前述課題’從 而作為本發明提案。 即本發明之波長變換構件係具備：玻璃基質；分散在 玻璃基質中的無機螢光體粉末；以及設置在無機榮光體粉 末與玻璃基質的界面’由無機營光體粉末與玻璃基質之反 應生成物卿叙厚度為〇間層。 一般而言，在無機螢光體粉末分散在玻璃基質中所成（ 之波長變換構件中’無機螢光體粉末之折射率與玻璃基質 的折射率不同。例如相對於硼矽酸玻璃的折射率為L 5至 1. 6左右’ YAG螢光體粉末具有較硼矽酸玻璃高〇 2以上的 折射率（1. 83左右）。此等之無機螢光體粉末與玻璃基質之 折射率差大’使得激發光在無機螢光體粉末與玻璃基質的 界面被反射的比例變多。其結果為激發光無法有效率入射 至無機螢光體粉末中，使達到充分高之激發光的變換效率 為困難的。因此難以得到高發光效率的LED。 本發明中，波長變換構件中之無機螢光體粉末與玻璃 基質的界面，形成由兩者的反應物所成之中間層。因此可 以降低在無機螢光體粉末與玻璃基質的界面之反射率。即 該中間層具有無機螢光體粉末與玻璃基質之中間的折射 率，因玻璃基質中間層—無機螢光體粉末，折射率為連 續的變化，而可降低在玻璃基質與無機螢光體粉末的界面 的激發光反射。因此藉由使用本發明的波長變換構件，可 5 322846 201140891 提升LED的發光效率。例如將YAG螢光體分散在硼矽酸玻 璃中所成之波長變換構件的情況，由玻璃基質向無機螢光 體粉末之折射率漸漸提高，故不易發生在界面的反射。 另外，中間層的厚度過小或過大都無法如預期提升發 光效率。本發明中，中間層的厚度為0.01至5時，由 此可實現高發光效率。 波長變換構件較佳為以無機螢光體粉末與玻璃粉末的 燒結體所成者。 根據該構成，可容易地製作無機螢光體粉末均一分散 在玻璃基質中之波長變換構件。 無機螢光體粉末較佳為由氧化物、氮化物、氧氮化物、 硫化物、氧硫化物、稀土金屬硫化物、鋁醯氣及_磷醯氣 中選出之一種以上所成者。 關於本發明之光學元件，其具備關於上述發明之波長 變換構件。 關於本發明之波長變換構件的製造方法，其為用以製 造有關於上述本發明之波長變換構件的方法。關於本發明 之波長變換構件的製造方法為將含有無機螢光體粉末及玻 璃粉末之混合粉末，在較玻璃粉末之軟化點高65。匸的溫度 至較玻璃粉末之軟化點高loot：的溫度範圍燒成。 含有無機螢光體粉末及玻璃粉末之混合粉末，在較玻 璃粉末之軟化點高65°C的溫度至較玻璃粉末之軟化點高 100 C的溫度之較南的溫度燒成，使無機螢光體粉末與玻璃 粉末反應，無機螢光體粉末及玻璃之反應生成物所成的中 322846 6 201140891 - 間層可適宜的在兩者的界面形成。 【實施方式】 如第1圖所示，本實施形態之波長變換構件丨，其特 徵為在無機螢光體粉末2與玻璃基質3的界面形成由無機 螢光體粉末與玻璃粉末的反應生成物所成之中間芦4中 間層4的厚度為〇. 〇1至5//m，較佳為〇.〇1至士^^。若中 間層4的厚度未達O.Olem’則難有在無機螢光體粉末2 與玻璃基質3的界面中抑制激發光之反射的效果。另一方 面，若中間層4的厚度大於5//m，則在波長變換構件i中 之中間層4所佔的比例變高’而在波長變換構件1中之無 機榮光體粉末2所佔的比例降低。因此也會有使波長變換 構件1的變換效率變得過低的情形。因此使得使用波長變 換構件1之LED等發光元件的發光強度容易降低。 中間層4的厚度可如後述，可由調控波長變換構件i 製作時的熱處理溫度以調整。 無機螢光體粉末2 ’可舉出在紫外光或可見光之激發 光入射時，會發出較該激發光的波長更長波長的螢光者。 例如使用以可見光所成之激發光入射時，會發出相對於該 激發光的色相之補色的螢光之無機螢光體粉末，透過的激 發光與螢光之混合光可得白色光，因此可容易地獲得白色 LED元件°尤其是激發光為具有中心波長430nm至490nm 之光線’使用螢光為具有中心波長530nm至590nm的光線 的無機營光體粉末2可較容易獲得白色光，故為較佳。 使用之無機螢光體粉末2較佳的具體例可舉出例如 7 322846 201140891 YAG等之石榴石（garnet)系或由其他之氧化物、氮化物、 氧氮化物、硫化物、氧硫化物、稀土金屬硫化物、鋁酸鹽 氯化物及_磷酸鹽氯化物等所成者。 即使在上述無機螢光體粉末中，使用激發帶在波長 300nm至500nm且在380nm至780nm具有發光波峰者，尤 其是在藍色（440nm至480nra)、綠色（500nm至540nm)、黃 色（540nm至595nm)、紅色（600nm至700nm)具有發光波峰 者為佳。 若以波長在300nm至440nm之紫外光至近紫外光的激 發光照射會發出藍色發光的無機螢光體粉末可舉出 Sr5(P〇4)3Cl ： Eu2+> (Sr, Ba)MgAl.〇Oi7 ： Eu2+> (Sr, Ba)3MgSi2〇8: Eu2+等。 若以波長在300nm至440nm之紫外光至近紫外光的激 發光照射會發出綠色螢光的無機螢光體粉末可舉出[Technical Field] The present invention relates to a wavelength conversion member used as a constituent member such as a white LED (Light Emitting Diode), an optical element using the same, and a method of manufacturing a wavelength conversion member. [Prior Art] The development of white LEDs has become quite popular in recent years. The white LED is composed of, for example, an LED that emits blue or ultraviolet excitation light and a wavelength conversion member formed by dispersing an inorganic phosphor powder in a matrix such as a resin. The inorganic phosphor powder receives excitation light from the LED and emits light of a wavelength different from that of the excitation light (Glory). On the other hand, a part of the excitation light from the LED is transmitted through the wavelength conversion member without undergoing wavelength conversion. Mixing these lights gives white light. White LEDs are characterized by lower power consumption and longer life than incandescent and fluorescent lamps. Therefore, the white LED is used directly as a light source such as a mobile phone and a digital camera. In the future, as a light source for replacing the next generation of incandescent lamps and fluorescent lamps, the application of white LEDs in lighting applications is expected. White LEDs are increasingly required to have high power depending on the application. Therefore, if the inorganic phosphor powder is dispersed in the resin matrix, the resin matrix is discolored due to the heat from the LED, and X is lowered for a long time. problem. Further, when a resin containing an inorganic phosphor powder is applied, it is easy to cause a thickness unevenness in the case of an LED, and the light distribution property is lowered. In order to solve the above problems, it has been proposed to disperse the inorganic phosphor powder in a matrix. A method of completely inorganicizing the wavelength conversion member (for example, refer to 322846 3 201140891 Patent Documents 1 and 2). According to this method, the heat resistance and weather resistance of the wavelength converting member can be improved. Specifically, in a high temperature environment (for example, 15 (TC, 600 hours) or high temperature and high humidity environment (for example, temperature 85 ° C, humidity 85%, 2000 hours), the white LED light-emitting characteristics hardly change, or In the long-term exposure to the ultraviolet light of the sunlight, there is almost no coloration or deterioration. Further, the workability is excellent, and the decrease in the light distribution due to the inconsistency in thickness can be suppressed. [Prior Art Document] '[Patent Literature] [Patent Document 1 [Patent Document 2] Japanese Patent Publication No. 4158〇12 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) Wavelength conversion in which an inorganic phosphor powder is dispersed in a glass matrix A member which is compared with a wavelength conversion member using a tree-like substrate, although long-term (the stability is excellent, the wavelength of the inorganic phosphor powder dispersed in the glass matrix is changed in the past, due to the inorganic phosphor The reflection and scattering in the interface between the powder and the glass matrix cause a large loss of light, so it is difficult to achieve sufficient luminous efficiency. In addition, the boundary between the inorganic phosphor powder and the glass matrix The reflection and scattering in the surface are caused by the difference in refractive index between the inorganic phosphor powder and the glass substrate. Therefore, an object of the present invention is to provide a wavelength conversion member which can obtain high luminous efficiency, which is obtained by dispersing inorganic phosphor powder in The wavelength conversion member in the glass substrate. 322846 4 201140891 (Means for Solving the Problem) The inventors of the present invention have intensively reviewed the results and found that a specific layer can be formed at the interface between the glass substrate and the inorganic glare gas to solve the aforementioned problem. The present invention proposes a wavelength conversion member comprising: a glass substrate; an inorganic phosphor powder dispersed in a glass matrix; and an interface disposed between the inorganic glazing powder and the glass substrate, 'inorganic camp powder and glass The thickness of the reaction product of the matrix is the inter-turn layer. Generally, the refractive index of the inorganic phosphor powder and the refractive index of the glass matrix are formed in the wavelength conversion member in which the inorganic phosphor powder is dispersed in the glass matrix. The YAG phosphor powder has a refractive index of about 5 to about 1.6 with respect to the borosilicate glass. The refractive index of borosilicate glass is higher than 2 (about 1.83). The difference in refractive index between the inorganic phosphor powder and the glass matrix is such that the excitation light is at the interface between the inorganic phosphor powder and the glass matrix. As a result, the ratio of the reflection is increased. As a result, the excitation light is not efficiently incident on the inorganic phosphor powder, and it is difficult to achieve a sufficiently high conversion efficiency of the excitation light. Therefore, it is difficult to obtain an LED having high luminous efficiency. The interface between the inorganic phosphor powder and the glass substrate in the wavelength conversion member forms an intermediate layer formed by the reactants of the two. Therefore, the reflectance at the interface between the inorganic phosphor powder and the glass substrate can be reduced. The layer has a refractive index intermediate between the inorganic phosphor powder and the glass matrix, and the refractive index is continuously changed due to the glass matrix intermediate layer-inorganic phosphor powder, and the interface between the glass matrix and the inorganic phosphor powder can be lowered. Excitation light reflection. Therefore, by using the wavelength conversion member of the present invention, the luminous efficiency of the LED can be improved by 5 322846 201140891. For example, in the case of a wavelength converting member in which a YAG phosphor is dispersed in a borosilicate glass, the refractive index of the glass matrix to the inorganic phosphor powder gradually increases, so that reflection at the interface is less likely to occur. In addition, if the thickness of the intermediate layer is too small or too large, the light-emitting efficiency cannot be improved as expected. In the present invention, when the thickness of the intermediate layer is from 0.01 to 5, high luminous efficiency can be achieved. The wavelength converting member is preferably made of a sintered body of an inorganic phosphor powder and a glass powder. According to this configuration, the wavelength conversion member in which the inorganic phosphor powder is uniformly dispersed in the glass matrix can be easily produced. The inorganic phosphor powder is preferably one or more selected from the group consisting of oxides, nitrides, oxynitrides, sulfides, oxysulfides, rare earth metal sulfides, aluminum helium, and phosphine gas. The optical element of the present invention comprises the wavelength conversion member according to the above invention. The method for producing a wavelength converting member of the present invention is a method for producing the wavelength converting member of the present invention described above. The method for producing a wavelength conversion member according to the present invention is such that the mixed powder containing the inorganic phosphor powder and the glass powder is 65 higher than the softening point of the glass powder. The temperature of the crucible is burned to a temperature range higher than the softening point of the glass powder. The mixed powder containing the inorganic phosphor powder and the glass powder is fired at a temperature higher than the softening point of the glass powder by 65 ° C to a temperature higher than the softening point of the glass powder by 100 C to cause inorganic fluorescent The bulk powder is reacted with the glass powder, and the intermediate product of the inorganic phosphor powder and the glass is formed into a 322846 6 201140891 - interlayer which is suitably formed at the interface between the two. [Embodiment] As shown in Fig. 1, the wavelength conversion member 本 of the present embodiment is characterized in that a reaction product of inorganic phosphor powder and glass powder is formed at the interface between the inorganic phosphor powder 2 and the glass substrate 3. The intermediate layer 4 of the intermediate layer 4 has a thickness of 〇. 〇1 to 5//m, preferably 〇.〇1 to 士^^. If the thickness of the intermediate layer 4 is less than O.Olem', it is difficult to suppress the reflection of the excitation light at the interface between the inorganic phosphor powder 2 and the glass substrate 3. On the other hand, when the thickness of the intermediate layer 4 is more than 5/m, the proportion of the intermediate layer 4 in the wavelength conversion member i becomes high, and the inorganic glory powder 2 in the wavelength conversion member 1 occupies The ratio is reduced. Therefore, there is a case where the conversion efficiency of the wavelength conversion member 1 is too low. Therefore, the light-emitting intensity of the light-emitting element such as an LED using the wavelength conversion member 1 is easily lowered. The thickness of the intermediate layer 4 can be adjusted by adjusting the heat treatment temperature at the time of preparation of the wavelength conversion member i as will be described later. The inorganic phosphor powder 2' may be a phosphor which emits a wavelength longer than the wavelength of the excitation light when the excitation light of ultraviolet light or visible light is incident. For example, when an incident light that is made of visible light is incident, a fluorescent phosphor phosphor that emits a complementary color to the hue of the excitation light is emitted, and the mixed light of the transmitted excitation light and the fluorescent light can obtain white light. It is easy to obtain white LED elements. In particular, the excitation light is light having a center wavelength of 430 nm to 490 nm. Using inorganic phosphor powder 2 having fluorescence at a center wavelength of 530 nm to 590 nm can easily obtain white light, so good. Preferable specific examples of the inorganic phosphor powder 2 to be used include garnets such as 7 322846 201140891 YAG or other oxides, nitrides, oxynitrides, sulfides, oxysulfides, and the like. Rare earth metal sulfides, aluminate chlorides and _phosphate chlorides. Even in the above inorganic phosphor powder, the excitation band is used at a wavelength of 300 nm to 500 nm and has a luminescence peak at 380 nm to 780 nm, particularly in blue (440 nm to 480 nra), green (500 nm to 540 nm), yellow (540 nm to 595 nm) and red (600 nm to 700 nm) are preferred for luminescence peaks. The inorganic phosphor powder which emits blue light when irradiated with excitation light having a wavelength of from 300 nm to 440 nm to near-ultraviolet light may be Sr5(P〇4)3Cl: Eu2+>(Sr, Ba)MgAl. 〇Oi7 : Eu2+> (Sr, Ba)3MgSi2〇8: Eu2+ or the like. An inorganic phosphor powder which emits green fluorescence when irradiated with ultraviolet light having a wavelength of from 300 nm to 440 nm to near-ultraviolet light can be exemplified.

SrAl2〇4 : Eu2+、SrGaA : Eu2+、SrBaSi〇4 : Eu2+、CdS : In、 CaS : Ce3+、Y3(A1，Gd)5〇12: Ce2+、Ca3Sc2Sh〇12: Ce3+、SrSiOn : Eu2+、ZnS ·· Al3+，Cu+、CaS: Sn2+、CaS: Sn2+, F、CaS〇4: Ce3+，Mn2+、 LiAl〇2: Mn2+、BaMgAl·— : Eu2+，Mn2+、ZnS:Cu+, Cl.、Ca3W〇6 : U ' Ca3Si〇4Cl2 ： Eu2+ ' Sro.2Bao.7Cl1.1AhO3.45 ： Ce3+, Mnz+ > Ba2MgSrAl2〇4 : Eu2+, SrGaA : Eu2+, SrBaSi〇4 : Eu2+, CdS : In, CaS : Ce3+, Y3(A1, Gd)5〇12: Ce2+, Ca3Sc2Sh〇12: Ce3+, SrSiOn: Eu2+, ZnS ··Al3+ , Cu+, CaS: Sn2+, CaS: Sn2+, F, CaS〇4: Ce3+, Mn2+, LiAl〇2: Mn2+, BaMgAl·— : Eu2+, Mn2+, ZnS: Cu+, Cl., Ca3W〇6: U 'Ca3Si〇 4Cl2 : Eu2+ ' Sro.2Bao.7Cl1.1AhO3.45 : Ce3+, Mnz+ > Ba2Mg

Si2〇?: Eu2+、Ba2Si〇4: Eu2+、Ba2Li2Si2〇7: Eu2+、ZnO : S、ZnO :Si2〇?: Eu2+, Ba2Si〇4: Eu2+, Ba2Li2Si2〇7: Eu2+, ZnO: S, ZnO:

Zn、Ca2Ba3(p〇4)3C1 : Eu2+、BaAl2〇4 : Eu2+等。 若以波長在44〇nm至48〇nm之藍色的激發光照射會發 出、綠色螢光的無機螢光體粉末可舉出SrAl2〇4 : Eu2+、Zn, Ca2Ba3(p〇4)3C1 : Eu2+, BaAl2〇4 : Eu2+, and the like. The inorganic phosphor powder which emits green fluorescent light by irradiation with blue light having a wavelength of from 44 Å to 48 Å may be SrAl 2 〇 4 : Eu 2+ ,

SrGa2S4 : Eu2+、SrBaSiCh : Eu2+、CdS : In、CaS : Ce3+、 8 322846 201140891 Y3(Al，Gd)5〇12 : Ce2+、Ca3Sc2Si3〇12 : Ce3+、SrSiOn : Eu2+等。 若以波長在300nm至440nm之紫外光至近紫外光的激 發光照射會發出黃色螢光的無機螢光體粉末可舉出ZnS:SrGa2S4: Eu2+, SrBaSiCh: Eu2+, CdS: In, CaS: Ce3+, 8 322846 201140891 Y3(Al, Gd) 5〇12 : Ce2+, Ca3Sc2Si3〇12: Ce3+, SrSiOn: Eu2+, and the like. The inorganic phosphor powder which emits yellow fluorescence by irradiation with ultraviolet light having a wavelength of from 300 nm to 440 nm to near-ultraviolet light may be ZnS:

Eu2+、Ba5(P0〇3Cl : U、Sr3W〇6 : U、CaGa2S4 : Eu2+、SrS〇4 : Eu2+，Mn2+、ZnS : P、ZnS : P3—，Cl_、ZnS : Mn2+等。 若以波長在440nm至480nm之藍色的激發光照射會發 出黃色螢光的無機螢光體粉末可舉出Y3(Al，Gd)5〇12 : Ce2+、 Ba5(P〇4)3Cl : U、CaGa2S4 : Eu2+、Sr2Si〇4 : Eu2+等。 若以波長在300nm至440nm之紫外光至近紫外光的激 發光照射會發出紅色螢光的無機螢光體粉末可舉出CaS: Yb2，C1、Gd3Ga4〇i2 : Cr3+、CaGa2S4 : Mn2+、Na(Mg，Mn)2LiSi4 Oi〇F2 : Mn、ZnS: Sn2+、Y3Al5〇i2: Cr3+、SrB8〇i3: Sm2+、MgSr3Si2〇8: Eu2+，Mn2+、a -SrO · 3B2〇3 : Sm2+、ZnS-CdS、ZnSe : Cu+，Cl、 ZnGa2S4 : Mn2+、ZnO : Bi3+、BaS : Au，K、ZnS : Pb2+、ZnS : Sn2+，Li+、ZnS : Pb，Cu、CaTi〇3 : Pr3+、CaTi〇3 : Eu3+、Y2〇3 : Eu3+、（Y、Gd)2〇3: Eu3+、CaS: Pb2+，Mn2+、YP〇4: Eu3+、Ca2MgSi2〇7: Eu2+，Mn2+、Y (P、V) 〇4: Eu3+、Y2〇2S: Eu3+、Sr A14〇7: Eu3+、CaY A1 〇4: Eu3+、La〇2S : Eu3+、LiW2〇8: Eu3+，Sm3+、（Sr，Ca，Ba，Mg)ie(P〇4)6 Cl2 : Eu2+，Mn2+、Ba3MgSi2〇8 : Eu2+、Mn2+等。 若以波長在440nm至480nm之藍色的激發光照射會發 出紅色螢光的無機螢光體粉末可舉出ZnS: Mn2+，Te2+、 Mg2Ti〇4 : Mn4+、K2SiF6 : Mn4+、SrS : Eu2+、CaS : Eu2+、Naw K0.42EU0.i2TiSi4〇n' Na1.23Ko.42Euo.12TiSi5〇i3 · Eu3+ ' CdS： In, Te ' CaAlSiN3 : Eu2+、CaSiNs: Eu2+、（Ca，Sr)2Si5N8: Eu2+、Eu2W2〇7 9 322846 201140891 等。 、另外為了使激發光與發光的波長區域相合，亦可使用 光粉末混合。例如以紫外光區域的激發光照 射可付白色光的情形’只要將發出藍色、綠色、黃色、紅 色的無機螢光體粉末混合使用即可。Eu2+, Ba5(P0〇3Cl: U, Sr3W〇6: U, CaGa2S4: Eu2+, SrS〇4: Eu2+, Mn2+, ZnS: P, ZnS: P3—, Cl_, ZnS: Mn2+, etc. If the wavelength is 440 nm to An inorganic phosphor powder which emits yellow fluorescence by excitation light of 480 nm blue may be Y3(Al,Gd)5〇12 : Ce2+, Ba5(P〇4)3Cl:U, CaGa2S4: Eu2+, Sr2Si〇 4: Eu2+, etc. If the inorganic phosphor powder which emits red fluorescence by irradiation with ultraviolet light of a wavelength of 300 nm to 440 nm to near-ultraviolet light is exemplified by CaS: Yb2, C1, Gd3Ga4〇i2: Cr3+, CaGa2S4: Mn2+, Na(Mg,Mn)2LiSi4 Oi〇F2 : Mn, ZnS: Sn2+, Y3Al5〇i2: Cr3+, SrB8〇i3: Sm2+, MgSr3Si2〇8: Eu2+, Mn2+, a-SrO · 3B2〇3 : Sm2+, ZnS -CdS, ZnSe: Cu+, Cl, ZnGa2S4: Mn2+, ZnO: Bi3+, BaS: Au, K, ZnS: Pb2+, ZnS: Sn2+, Li+, ZnS: Pb, Cu, CaTi〇3: Pr3+, CaTi〇3: Eu3+ , Y2〇3 : Eu3+, (Y, Gd)2〇3: Eu3+, CaS: Pb2+, Mn2+, YP〇4: Eu3+, Ca2MgSi2〇7: Eu2+, Mn2+, Y (P, V) 〇4: Eu3+, Y2 〇2S: Eu3+, Sr A14〇7: Eu3+, CaY A1 〇4: Eu3+, La〇2S: Eu3+ LiW2〇8: Eu3+, Sm3+, (Sr, Ca, Ba, Mg)ie(P〇4)6 Cl2: Eu2+, Mn2+, Ba3MgSi2〇8: Eu2+, Mn2+, etc. If the wavelength is between 440nm and 480nm blue The inorganic phosphor powder which emits red fluorescence by excitation light can be exemplified by ZnS: Mn2+, Te2+, Mg2Ti〇4: Mn4+, K2SiF6: Mn4+, SrS: Eu2+, CaS: Eu2+, Naw K0.42EU0.i2TiSi4〇n' Na1.23Ko.42Euo.12TiSi5〇i3 · Eu3+ 'CdS: In, Te ' CaAlSiN3 : Eu2+, CaSiNs: Eu2+, (Ca, Sr)2Si5N8: Eu2+, Eu2W2〇7 9 322846 201140891 and the like. Further, in order to make the excitation light coincide with the wavelength region of the light emission, it is also possible to use light powder mixing. For example, in the case where the white light is emitted by the excitation light in the ultraviolet light region, the inorganic phosphor powder emitting blue, green, yellow or red may be used in combination.

璃土質3的功成為使無機螢光體粉末2安定維持之 媒質另外·依玻壤基質3的玻璃組成會使波長變換構件 1的色調不同或造成與無機螢光體粉末2反應性的差別， 故考慮這些條，而選擇所使用玻璃基質3的玻璃組成為較 佳。再者’決定適合於玻璃基f 3的玻璃組成的無機螢光 體粉末2的添加量與波長變換構件的厚度也很重要。 玻璃基質3可使用例如Si〇2_B2〇3_R〇系玻璃（R代表 Mg、Ca、Sr、Ba)、Si〇2-B2〇3-R’ 2〇 系玻璃（R，代表 Li、Na、 K)、Si〇2-B2〇3-Alz〇3 系玻璃、si〇2_B2〇3—Zn0 系玻璃、Zn〇_B2〇3 系玻璃、SnO-P2〇s系玻璃。可依目的之特性不同適當的選擇 這些玻璃。例如欲以低溫燒成時，可選擇軟化點低的 ΖηΟ-Β2〇3系玻璃、SnO-P2〇5系玻璃，欲提升波長變換構件i 的耐候性時，可選擇Si〇2-B2〇3-RO系玻璃、Si〇2-B2〇3-R，2〇 系玻璃、Si〇2-B2〇3_Al2〇3 系玻璃、Si〇2-B2〇3-ZnO 系玻璃。 使用Si〇2-B2〇3-RO系玻璃作為玻璃時，以莫耳％計，較 佳使用含有Si〇2為30至80%、B2〇3為1至30%、MgO為〇 至 10%、CaO 為 0 至 30%、SrO 為 0 至 20%、BaO 為 0 至 40%、 MgO+CaO+SrO+BaO 為 5 至 45%、Al2〇3 為 0 至 10%及 ZnO 為 〇 至10%之玻璃。 10 322846 201140891 另外除了上述成分以外’為使玻璃熔融性提升且降低 玻璃軟化點以易於低溫燒成’可添加合計量最多5%之 Li〇2、Na〇2及IGO。其他如，為使玻璃熔融性提升，可添加 最多5%之Ρ2〇5 ;為提升玻璃的化學耐久性，可添加個別添 加量最多 15%之 Ta2〇5、Ti〇2、Nb2〇5、Gd2〇3、La2〇3。 使用Si〇2_B2〇3-R 2〇糸玻璃作為所用玻璃時，以莫耳％ 計，較佳使用含有Si〇2為30至80%、B2〇3為1至55%、Li2〇 為 0 至 20%、Na2〇 為 0 至 25%、K2〇 為 0 至 25%、Li2〇+Na2〇+K2〇 為5至35%、AI2O3為0至10%及ZnO為〇至1〇%之玻璃。 另外除了上述成分以外’為提升玻璃的熔融性，可添 加合計量最多5%之MgO、CaO、SrO及baO。其他，如為使 玻璃熔融性提升，可添加最多5%之P2〇5 ;為提升玻璃的化 學耐久性，可添加個別添加量最多15%之Ta2〇5、TiH Gd2〇3、La2〇3。 使用Si〇2_B2〇3-Al2〇3系玻璃作為玻璃時，以莫耳％計， 較佳使用含有Si〇2為30至70%、β2〇3為15至55%、Ah〇3 為 15 至 55%、Li2〇 為 0 至 10%、Na2〇 為 〇 至 、κ2〇 為 〇 至 10%、MgO 為 0 至 10%、CaO 為 0 至 1〇%、sr〇 為 〇 至 1〇% 及BaO為0至10%之玻璃。 另外除了上述成分以外’為提升玻璃的溶融性，可添 加最多5%之Pz〇5 ;為提升玻璃的化學耐久性，可添加個別 添加量最多 15%之 Ta2〇5、Ti 〇2、Nb2〇5、Gd2〇3、LaeCh。 使用SiCh-BzOa-ZnO系玻璃作為玻璃時，以莫耳％計， 較佳使用含有Si〇2為5至50%、B2O3為15至55%、ZnO為 322846 11 201140891 30 至 80%、Li2〇 為 0 至 10%、Na2〇 為 0 至 10%、K2O 為 0 至 10%、MgO 為 〇 至 10%、CaO 為 0 至 10%、SrO 為 0 至 10% 及BaO為0至10%之玻璃。 另外除了上述成分以外，為提升玻璃的化學耐久性， 可添加最多5%之AI2O3;為提升玻璃的化學耐久性’可添加 個別添加量最多 15%之 Ta2〇s、Ti〇2、Nb2〇s、Gd2〇3、La2〇3。 使用Zn〇-B2〇3系玻璃作為玻璃時，以莫耳％計，較佳使 用含有 ZnO 為 30 至 80%、B2〇3 為 20 至 70%、Si〇2 為 0 至 5°/〇、 LhO 為 0 至 10%、Na2〇 為 0 至 10°/。、K2〇 為 0 至 10%、MgO 為0至10%、CaO為0至10%、SrO為0至10%及BaO為0 至10%之玻璃。 另外除了上述成分以外，為提升玻璃的化學耐久性， 可添加最多5%之Al2〇3;為提升玻璃的化學财久性，可添加 個別添加量最多 15%之 Ta2〇s、Ti〇2、Nb2〇5、Gd2〇3、La2〇3。 使用Sn〇-P2〇5系玻璃作為玻璃時，以莫耳％計，較佳使 用含有SnO為35至8OVP2O5為5至40%、B2〇3為0至30%、 Al2〇3 為 〇 至 10%、Si〇2 為 0 至 1〇%、Li2〇 為 〇 至 1〇%、Na2〇 為 0 至 10%、K2〇 為 0 至 10%、Mg〇 為 〇 至 1〇%、CaO 為 〇 至 10%、SrO為0至10%、BaO為〇至1〇%之玻璃。 另外除了上述成分以外，為提升耐候性，可添加合計 量最多 10%之 ZnO、Ta2〇5、Ti〇2、Nb2〇5、Gd2〇3、La2〇3。 另外，為降低軟化點且使玻璃安定化，Sn〇/P2〇5(莫耳 比）較佳為0. 9至16的範圍。若Sn〇/P2〇5小於〇. 9則軟化 點會上升，使低溫燒成變得困難，無機螢光體粉末容易劣 322846 12 201140891 • 化。此外，耐候性也有明顯降低的傾向。另一方面若Sn〇/p2〇5 大於16，則玻璃中起因於Sn的失透明物析出使玻璃的 透光率有下降的傾向，結果難以獲得具有高發光效率的波 長變換構件l〇SnO/P2〇5更佳的範圍為5至1〇，又更佳 圍為2至5。 本實施形態的波長變換構件！較佳為由含有益機勞光 體粉末與玻璃粉末的混合粉末之燒結體所成者。因在此产 況下無機螢光體粉末可容易且均一地分散在玻璃基質中。月 玻璃粉末的平均粒徑^較佳為〇.1_至1叫m，更 佳為1 至50/ζιη。若玻璃粉末的平均粒徑^過小，則燒 成時會有氣泡的產生量過多情形。波長變換構件i中含^ 斗多氣泡成為光散射的原因而使發光效率有下降的傾向。 氣孔率較佳在2%以下，更佳在1%以下。另一方面，若平均 粒徑D5。過大，則會使波長變換構件i中之無機螢光體粉末 2難以均一地分散，結果使波長變換構件丨的發光效率 下降的傾向。 波長變換構件1的發光效率（lm/w)會隨分散在玻璃其 質3中的無機螢光體粉末2的種類、含有量與發光色變ς 構件1的厚度有所變化。欲提高波長變換構件丨的發光效 率時，可以較薄的厚度使激發光與螢光的透光率提高，以 增多無機螢光體粉末2的含量使變換之光量增加亦可。然 而，無機螢光體粉末2的含量過多時，則難以獲得緻密= 構造而使氣孔率有增大的傾向。結果會有激發光難以有效 率的照射到無機螢光體粉末、波長變換構件丨的機械強度 322846 13 201140891The work of the glazing material 3 serves as a medium for maintaining the inorganic phosphor powder 2 in a stable manner. Further, the glass composition of the SiORP matrix 3 causes a difference in the color tone of the wavelength conversion member 1 or a difference in reactivity with the inorganic phosphor powder 2, Therefore, considering these strips, it is preferable to select the glass composition of the glass substrate 3 to be used. Further, it is also important to determine the amount of the inorganic phosphor powder 2 suitable for the glass composition of the glass base f 3 and the thickness of the wavelength converting member. As the glass substrate 3, for example, Si〇2_B2〇3_R lanthanum glass (R represents Mg, Ca, Sr, Ba), Si〇2-B2〇3-R' 2 lanthanide glass (R, represents Li, Na, K) can be used. , Si〇2-B2〇3-Alz〇3-based glass, si〇2_B2〇3-—Zn0-based glass, Zn〇_B2〇3-based glass, and SnO-P2〇s-based glass. These glasses can be appropriately selected depending on the characteristics of the purpose. For example, when firing at a low temperature, ΖηΟ-Β2〇3 glass and SnO-P2〇5 glass having a low softening point can be selected, and when the weather resistance of the wavelength conversion member i is to be improved, Si〇2-B2〇3 can be selected. -RO-based glass, Si〇2-B2〇3-R, 2-lanthanum-based glass, Si〇2-B2〇3_Al2〇3-based glass, and Si〇2-B2〇3-ZnO-based glass. When Si〇2-B2〇3-RO glass is used as the glass, it is preferable to use 30% to 80% of Si〇2, 1 to 30% of B2〇3, and 10% to 10% of MgO. , CaO is 0 to 30%, SrO is 0 to 20%, BaO is 0 to 40%, MgO+CaO+SrO+BaO is 5 to 45%, Al2〇3 is 0 to 10%, and ZnO is 〇 to 10%. Glass. 10 322846 201140891 In addition to the above-mentioned components, it is possible to add Li〇2, Na〇2 and IGO in a total amount of 5% in order to increase the glass meltability and lower the glass softening point to facilitate low-temperature firing. For example, in order to improve the glass meltability, it is possible to add up to 5% of Ρ2〇5; to improve the chemical durability of the glass, it is possible to add Ta2〇5, Ti〇2, Nb2〇5, Gd2 with an individual addition amount of up to 15%. 〇3, La2〇3. When Si〇2_B2〇3-R 2〇糸 glass is used as the glass to be used, it is preferable to use 30% to 80% of Si〇2, 1 to 55% of B2〇3, and 0 to 1% of Li2〇 in terms of mol%. 20%, Na2〇 is 0 to 25%, K2〇 is 0 to 25%, Li2〇+Na2〇+K2〇 is 5 to 35%, AI2O3 is 0 to 10%, and ZnO is 〇 to 1%%. Further, in addition to the above components, in order to improve the meltability of the glass, MgO, CaO, SrO, and baO may be added in a total amount of 5%. In addition, in order to improve the glass meltability, up to 5% of P2〇5 may be added; in order to improve the chemical durability of the glass, Ta2〇5, TiH Gd2〇3, and La2〇3 may be added in an amount of up to 15%. When Si〇2_B2〇3-Al2〇3 series glass is used as the glass, it is preferable to use 30% to 70% of Si〇2, 15 to 55% of β2〇3, and 15 to 55% of Ah〇3 in terms of mole %. 55%, Li2〇 is 0 to 10%, Na2〇 is 〇, κ2〇 is 〇 to 10%, MgO is 0 to 10%, CaO is 0 to 1〇%, sr〇 is 〇 to 1〇%, and BaO It is 0 to 10% glass. In addition to the above ingredients, in order to improve the solubility of the glass, up to 5% of Pz〇5 can be added. To improve the chemical durability of the glass, Ta2〇5, Ti〇2, Nb2〇 can be added up to 15% individually. 5. Gd2〇3, LaeCh. When using SiCh-BzOa-ZnO-based glass as the glass, it is preferable to use 5 to 50% of Si〇2, 15 to 55% of B2O3, and 322846 11 201140891 30 to 80% of Li2〇 in terms of mole %. Glass of 0 to 10%, Na2〇 is 0 to 10%, K2O is 0 to 10%, MgO is 〇 to 10%, CaO is 0 to 10%, SrO is 0 to 10%, and BaO is 0 to 10%. . In addition to the above ingredients, in order to improve the chemical durability of the glass, up to 5% of AI2O3 can be added; to improve the chemical durability of the glass, it is possible to add up to 15% of the individual addition amount of Ta2〇s, Ti〇2, Nb2〇s , Gd2〇3, La2〇3. When Zn〇-B2〇3 based glass is used as the glass, it is preferable to use 30% to 80% of ZnO, 20 to 70% of B2〇3, and 0 to 5°/〇 of Si〇2 in terms of mol%. LhO is 0 to 10%, and Na2〇 is 0 to 10°/. , K2 〇 is 0 to 10%, MgO is 0 to 10%, CaO is 0 to 10%, SrO is 0 to 10%, and BaO is 0 to 10% glass. In addition to the above ingredients, in order to improve the chemical durability of the glass, up to 5% of Al2〇3 can be added; in order to improve the chemical durability of the glass, Ta2〇s, Ti〇2, which can be added up to 15% individually, can be added. Nb2〇5, Gd2〇3, La2〇3. When Sn Sn-P 2 〇 5 series glass is used as the glass, it is preferably used in a molar percentage of 35 to 8 OVP 2 O 5 of 5 to 40%, B 2 〇 3 is 0 to 30%, and Al 2 〇 3 is 〇 to 10 in terms of mole %. %, Si〇2 is 0 to 1〇%, Li2〇 is 〇 to 1〇%, Na2〇 is 0 to 10%, K2〇 is 0 to 10%, Mg〇 is 〇 to 1〇%, and CaO is 〇 to 10%, SrO is 0 to 10%, and BaO is 〇 to 1% by weight of glass. Further, in addition to the above components, in order to improve the weather resistance, ZnO, Ta2〇5, Ti〇2, Nb2〇5, Gd2〇3, and La2〇3 may be added in a total amount of up to 10%. 5至范围内。 In addition, in order to reduce the softening point and the glass is stabilized, Sn 〇 / P2 〇 5 (mole ratio) is preferably in the range of 0.9 to 16. If Sn〇/P2〇5 is less than 〇. 9, the softening point will rise, making it difficult to burn at a low temperature, and the inorganic phosphor powder is easily inferior. 322846 12 201140891 • In addition, weather resistance also tends to decrease significantly. On the other hand, when Sn 〇 / p2 〇 5 is larger than 16, the light-transmitting property of the glass due to the precipitation of the opaque substance due to Sn tends to decrease, and as a result, it is difficult to obtain the wavelength conversion member l〇SnO/ having high luminous efficiency. A better range of P2 〇 5 is 5 to 1 〇, and a better range is 2 to 5. The wavelength conversion member of this embodiment! Preferably, it is composed of a sintered body containing a mixed powder of a machine powder and a glass powder. In this case, the inorganic phosphor powder can be easily and uniformly dispersed in the glass matrix. The average particle diameter of the glass powder is preferably 〇.1_ to 1 is m, more preferably 1 to 50/ζιη. If the average particle diameter of the glass powder is too small, the amount of generation of bubbles may be excessive at the time of firing. In the wavelength conversion member i, the multi-bubbles are caused by light scattering, and the luminous efficiency tends to decrease. The porosity is preferably 2% or less, more preferably 1% or less. On the other hand, if the average particle diameter is D5. If it is too large, the inorganic phosphor powder 2 in the wavelength conversion member i is difficult to be uniformly dispersed, and as a result, the luminous efficiency of the wavelength conversion member 倾向 tends to decrease. The luminous efficiency (lm/w) of the wavelength converting member 1 varies depending on the type and content of the inorganic phosphor powder 2 dispersed in the glass material 3 and the thickness of the luminescent color changing member 1. When the luminous efficiency of the wavelength converting member 丨 is to be increased, the light transmittance of the excitation light and the fluorescent light can be increased with a thin thickness, and the amount of the inorganic phosphor powder 2 can be increased to increase the amount of converted light. However, when the content of the inorganic phosphor powder 2 is too large, it is difficult to obtain a dense structure and an increase in porosity. As a result, there is a possibility that the excitation light is hardly irradiated to the inorganic phosphor powder and the mechanical strength of the wavelength conversion member 322846 13 201140891

造。得到燒結體後，可依其必要進行研削、研磨、再壓等 加工成所求的形狀。 容易下降等問題產生的情況。另一 2的含量過少時，則難以得 預備成形的方法並無特別限制，可採用沖壓成形法、 射出成刑法、片狀成形法（Sheet forming)、押出成形法 (Extrusion)等方法。 玻璃粉末與無機螢光體粉末之混合粉末的燒成溫度， 較佳為在比玻璃粉末之軟化點高6 5 °C的溫度至比玻璃粉末 之軟化點高100°C的溫度之溫度範圍内，更佳為在比玻璃 粉末之軟化點高70°C的溫度至比玻璃粉末之軟化點高 90°C的溫度之溫度範圍内。燒成溫度低於比玻璃粉末之軟 化點高65°C的溫度時，無機螢光體粉末與玻璃的界面之中 間層的厚度會過薄，在界面的反射無法減少，結果使發光 效率有降低的傾向。另一方面，若燒成溫度高於比玻璃粉 末之軟化點高l〇〇°C的溫度，玻璃與無機螢光體粉末的反 應過度進行，使無機螢光體粉末含有率下降，造成變換效 率降低，結果使得發光強度容易下降° 另外，可對無機螢光體粉末與玻璃粉末之混合粉末實 施粉碎處理，藉由機械力化學效應（mechanochemical 14 322846 201140891 effect)在無機螢光體財表面形成與玻璃之反應生成物 (中間層）。 如第2圖所示’波長變換構件1與例如LED晶片等的 光源5組合作為白色LED等光學元件6使用。此時波長變 換構件1可直接接著在光源5上，亦可接著於圍繞光源5 之涵相上使用。另外，在板狀體之波長變換構件下方設置 複數個LED晶片’可利用作為具備發光機能與擴散機能之 面發光元件。 (實施例） 以下基於實施例以說明本發明，但本發明並不只限定 於此等之實施例。 表1表示本發明的實施例（N〇. 2、5、8)及比較例⑺。· 1 、 3 、 4 、 6 、 7 、 9) ° [表 1 ]_Made. After the sintered body is obtained, it can be processed into a desired shape by grinding, polishing, repressing, or the like as necessary. It is easy to drop and other problems arise. When the content of the other two is too small, the method for preparing the preliminary molding is not particularly limited, and a method such as a press forming method, an injection molding method, a sheet forming method, or an extrusion method may be employed. The baking temperature of the mixed powder of the glass powder and the inorganic phosphor powder is preferably in a temperature range from a temperature of 6 5 ° C higher than the softening point of the glass powder to a temperature 100 ° C higher than the softening point of the glass powder. More preferably, it is in a temperature range of 70 ° C higher than the softening point of the glass powder to a temperature 90 ° C higher than the softening point of the glass powder. When the baking temperature is lower than the temperature higher than the softening point of the glass powder by 65 ° C, the thickness of the intermediate layer at the interface between the inorganic phosphor powder and the glass is too thin, and the reflection at the interface cannot be reduced, and as a result, the luminous efficiency is lowered. Propensity. On the other hand, if the firing temperature is higher than the softening point of the glass powder by 10 ° C, the reaction between the glass and the inorganic phosphor powder is excessively performed, so that the inorganic phosphor powder content is lowered, resulting in conversion efficiency. As a result, the luminescence intensity is easily lowered. In addition, the mixed powder of the inorganic phosphor powder and the glass powder can be pulverized by the mechanical force chemical effect (mechanochemical 14 322846 201140891 effect) on the surface of the inorganic phosphor body. The reaction product of glass (intermediate layer). As shown in Fig. 2, the wavelength converting member 1 is used in combination with a light source 5 such as an LED chip as an optical element 6 such as a white LED. At this time, the wavelength converting member 1 can be directly applied to the light source 5, or can be used next to the culvert surrounding the light source 5. Further, a plurality of LED chips are provided under the wavelength conversion member of the plate-like body, and can be used as a surface light-emitting element having a light-emitting function and a diffusion function. (Examples) Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples. Table 1 shows examples (N〇. 2, 5, 8) and Comparative Example (7) of the present invention. · 1, 3, 4, 6, 7, 9) ° [Table 1]_

No. 1 2 3 4 5 6 7 8 9 玻 璃 玻璃組成（mol%) 軟化點rc) 65Si〇2-5Bz〇3'30BaO 820 lOSi )2-30Β：〇3-ί 530 OZnO 60Sn 0-20P2〇a-2 350 OB^ 螢 光 體 種類 粒子直徑(D50)(/im) YAG 20 CaCa2S ‘ 15 SnSiO ‘ 25 玻璃：螢光體（質量《) 90 ： l〇 90 ： 10 90 ： 10 中ft 發ί! (溫度(°C) 750 890 950 530 600 650 350 420 460 1層厚度(//m) - 1 8 一 2 10 一 0.2 12 ό 效率（lm/W) 16 25 18 8 15 10 15 24 17 首先’以表1所示玻璃組成之方式秤量並混合玻璃原 料’將此混合物放置白金坩堝中以900至1400°C、一小時 使之熔融玻璃化。將熔融玻璃成形為薄膜狀，將所得之薄 15 322846 201140891 膜狀玻璃以球磨機粉碎後通過325網眼之篩以分級，而獲 得平均粒徑Dso為30之玻璃粉末。測定所得之粉末的軟 化點。使用微電腦視差熱分析儀測定，所得曲線之第四反 曲點的値即為軟化點。平均粒徑])5〇為將坡璃粉末分散在水 中’使用雷射散射粒徑分佈儀測定之。 接著，將玻璃粉末與無機螢光體粉末以表丨所示調配 比方式混合之，關具加㈣形製作為直徑lem的圓柱狀 預備成形體。將此預備成形體以表丨所示燒成溫度燒成得 到燒結體。對燒結體施以研磨處理，加工為直徑8咖、厚 度0.3mm的圓盤狀。測定所得之波長變換構件中，玻璃基 質與無機螢錢粉末的界面所形成之中間層的厚度與發光 ^。結果如表1所示。另外在試料Νο. 1、4、7 ^確認 有中間層。 反應生成層的厚度以SEM-EPMA測定。另外由該測定可 在中間層檢測出無機螢光體粉末與玻璃粉末所含^元素。 因此可轉定中Ρ⑽為由無機螢光體粉末與 生成物所成。 冬ι汉應 波長變換構件的發光特性以下述方式評價之。由藍色 ，激發各樣品，將樣品前方所發出的光在積分球内測定 付到其發光圖譜。從所得之發光圖譜計算出發光效率。 從表1明顯看出，本發明實施例之試料Νο·2、5、8之 f長變換構件，其因反應層厚度在請至5”的範圍内， 相較與比較例之波長變換構件（試料N。· 1、3、4、6、7、 9) ’其發光效率良好。 322846 16 201140891 【圖式簡單說明】 第1圖為關於本發明一實施形態之波長變換構件的示 意性的擴大截面圖。 第2圖為關於本發明一實施形態之光學元件的示意性 的側面圖。 【主要元件符號說明】 1 波長變換構件 2 無機螢光體粉末 3 玻璃基質 4 中間層 5 光源 6 光學元件 17 322846No. 1 2 3 4 5 6 7 8 9 Glass composition (mol%) Softening point rc) 65Si〇2-5Bz〇3'30BaO 820 lOSi )2-30Β:〇3-ί 530 OZnO 60Sn 0-20P2〇a -2 350 OB^ Phosphor type Particle diameter (D50)(/im) YAG 20 CaCa2S ' 15 SnSiO ' 25 Glass: Phosphor (Quality) 90 : l〇90 : 10 90 : 10 ft ί! (Temperature (°C) 750 890 950 530 600 650 350 420 460 1 layer thickness (//m) - 1 8 1 2 10 1 0.2 12 ό Efficiency (lm/W) 16 25 18 8 15 10 15 24 17 First ' The glass raw material was weighed and mixed in the manner of the glass composition shown in Table 1. The mixture was placed in a platinum crucible and melted and vitrified at 900 to 1400 ° C for one hour. The molten glass was formed into a film shape, and the resulting thin film was obtained. 322846 201140891 The membranous glass was pulverized by a ball mill and sieved through a 325 mesh sieve to obtain a glass powder having an average particle diameter Dso of 30. The softening point of the obtained powder was measured, and the obtained curve was measured using a microcomputer parallax thermal analyzer. The enthalpy of the four recurve points is the softening point. The average particle size]) 5 〇 is to disperse the slag powder in water 'Using laser scattering Determination of the size distribution analyzer. Next, the glass powder and the inorganic phosphor powder were mixed in a mixing ratio as shown in Table ,, and the cylindrical shape-prepared body having a diameter lem was formed by the addition of (4). This preliminary molded body was fired at a firing temperature shown in Table 得 to obtain a sintered body. The sintered body was subjected to a grinding treatment and processed into a disk shape having a diameter of 8 coffee and a thickness of 0.3 mm. The thickness and luminescence of the intermediate layer formed at the interface between the glass substrate and the inorganic rock powder were measured in the wavelength conversion member obtained. The results are shown in Table 1. In addition, in the sample Νο. 1, 4, 7 ^ confirmed that there is an intermediate layer. The thickness of the reaction-generating layer was measured by SEM-EPMA. Further, in this measurement, the element contained in the inorganic phosphor powder and the glass powder can be detected in the intermediate layer. Therefore, the intermediate iridium (10) can be converted from the inorganic phosphor powder and the product. The luminous characteristics of the wavelength conversion member of Dongmu Han should be evaluated in the following manner. Each sample is excited by blue, and the light emitted in front of the sample is measured in the integrating sphere and paid to its luminescence spectrum. The luminous efficiency was calculated from the obtained luminescence spectrum. It is apparent from Table 1 that the length conversion members of the samples Νο. 2, 5, and 8 of the examples of the present invention are in the range of 5" due to the thickness of the reaction layer, compared with the wavelength conversion member of the comparative example ( Sample N.·1, 3, 4, 6, 7, 9) 'The luminous efficiency is good. 322846 16 201140891 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic enlarged view of a wavelength conversion member according to an embodiment of the present invention Fig. 2 is a schematic side view showing an optical element according to an embodiment of the present invention. [Description of main element symbols] 1 wavelength conversion member 2 inorganic phosphor powder 3 glass substrate 4 intermediate layer 5 light source 6 optical element 17 322846

Claims (1)

201140891 七、申請專利範圍： 1. 一種波長變換構件，其具備： 玻璃基質； 無機螢光體粉末，分散在前述玻璃基質中，以及 中間層，設置在前述無機螢光體粉末與前述玻璃基 質的界面，由前述無機螢光體粉末及前述玻璃基質之反 應生成物所構成之厚度為O.Olym至5/zm。 2. 如申請專利範圍第1項所述之波長變換構件，其為前述 ("：, 無機榮光體粉末與玻璃粉末之燒結體所成。 3·如申請專利範圍第1項或第2項所述之波長變換構件， 其中’前述無機螢光體粉末為由氧化物、氮化物、氧氛 化物、硫化物、氧硫化物、稀土金屬硫化物、鋁醯氣及 鹵磷醯氣中選出一種以上所成。 4. /種光學元件，其具備申請專利範圍第1至3項中任一 頊所述之波長變換構件。 5. /種波長變換構件之製造方法，其為用以製造申請專利 / , 範圜第1至3項中任一項所述之波長變換構件的方法， 真將含有前述無機螢光體粉末及玻璃粉木之混合粉 本，在較前述玻璃粉末之軟化點高65t的溫度至較前 述破璃粉末之軟化點高l〇(TC的溫度範圍燒成。 322846 1201140891 VII. Patent application scope: 1. A wavelength conversion member comprising: a glass substrate; an inorganic phosphor powder dispersed in the glass matrix, and an intermediate layer disposed on the inorganic phosphor powder and the glass substrate The thickness of the interface between the inorganic phosphor powder and the reaction product of the glass substrate is from O.Olym to 5/zm. 2. The wavelength conversion member according to claim 1, which is the above (": sintered body of inorganic glory powder and glass powder. 3. If the scope of claim 1 or 2 The wavelength conversion member, wherein the 'inorganic phosphor powder is one selected from the group consisting of an oxide, a nitride, an oxygenate, a sulfide, an oxysulfide, a rare earth metal sulfide, an aluminum germanium gas, and a hafnium germanium gas. The above-mentioned optical element includes the wavelength conversion member according to any one of claims 1 to 3. 5. A method for manufacturing a wavelength conversion member, which is used for manufacturing a patent application The method of the wavelength conversion member according to any one of the items 1 to 3, which comprises a mixed powder of the inorganic phosphor powder and the glass powder, which is 65 t higher than the softening point of the glass powder. The temperature is higher than the softening point of the aforementioned glass powder by 1 〇 (the temperature range of TC is fired. 322846 1
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