JP2006002043A - Fluorescent substance to be excited by vacuum ultraviolet rays, method for producing the same, and vacuum ultraviolet ray-excited light-emitting element - Google Patents
Fluorescent substance to be excited by vacuum ultraviolet rays, method for producing the same, and vacuum ultraviolet ray-excited light-emitting element Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000126 substance Substances 0.000 title abstract description 8
- 238000010304 firing Methods 0.000 claims abstract description 20
- 229910052788 barium Inorganic materials 0.000 claims abstract description 15
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 72
- 230000005284 excitation Effects 0.000 claims description 39
- 239000007858 starting material Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000006866 deterioration Effects 0.000 abstract description 24
- 238000012360 testing method Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910020068 MgAl Inorganic materials 0.000 description 4
- 229910006249 ZrSi Inorganic materials 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012494 forced degradation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は真空紫外線励起用蛍光体、その製造方法及び真空紫外線励起発光素子に関するものである。
更に詳しくは、真空紫外線によって励起されることにより青緑色の発光を示す真空紫外線励起用蛍光体であって、ペースト焼成による熱劣化及び真空紫外線照射による真空紫外線劣化が極めて少なく、それらに起因する発光強度の低下も極めて少ない紫外線励起用蛍光体、その製造方法及び蛍光体を使用した真空紫外線励起発光素子に関する。
The present invention relates to a phosphor for vacuum ultraviolet excitation, a method for producing the same, and a vacuum ultraviolet excitation light emitting device.
More specifically, it is a phosphor for vacuum ultraviolet light excitation that emits blue-green light when excited by vacuum ultraviolet light, and has extremely little heat deterioration due to paste firing and vacuum ultraviolet light deterioration due to vacuum ultraviolet irradiation, and light emission caused by them. The present invention relates to a phosphor for ultraviolet excitation, a method for producing the phosphor, and a vacuum ultraviolet excitation light-emitting device using the phosphor.
近年、Ar、Xe、He、Ne等の希ガスまたはそれらの混合ガス放電により放射される真空紫外線（一般には、波長190nm以下といわれている）によって、蛍光体を励起して発光させる真空紫外線励起発光素子の開発が盛んに行われている。
真空紫外線励起発光素子の例として希ガスランプがある。希ガスランプの管内にはHe−Xe、Ne−Xe等の希ガスが封入されており、その管の内面には真空紫外線励起用蛍光体からなる蛍光膜が形成されている。希ガスランプは水銀を使用しないため、環境保護の面からも注目されている。
In recent years, vacuum ultraviolet excitation that excites phosphors and emits light using vacuum ultraviolet rays (generally said to have a wavelength of 190 nm or less) emitted by rare gas such as Ar, Xe, He, Ne or mixed gas discharges thereof. Development of light-emitting elements is actively performed.
An example of a vacuum ultraviolet light-excited light emitting element is a rare gas lamp. A rare gas such as He-Xe or Ne-Xe is sealed in the tube of the rare gas lamp, and a fluorescent film made of a phosphor for vacuum ultraviolet ray excitation is formed on the inner surface of the tube. Since rare gas lamps do not use mercury, they are also attracting attention from the viewpoint of environmental protection.
希ガス放電により放射される真空紫外線によって励起される蛍光体には様々なものがある。例えば、青色蛍光体としては、BaMgAl10O17:Eu、青緑色蛍光体としては、(Ba,Sr)MgAl10O17:Eu,Mn、緑色蛍光体としては、Zn2SiO4:Mn、赤色蛍光体としては、(Y,Gd)BO3:Euが知られている。 There are various phosphors that are excited by vacuum ultraviolet rays emitted by a rare gas discharge. For example, BaMgAl 10 O 17 : Eu as a blue phosphor, (Ba, Sr) MgAl 10 O 17 : Eu, Mn as a blue green phosphor, Zn 2 SiO 4 : Mn, red as a green phosphor As the phosphor, (Y, Gd) BO 3 : Eu is known.
このような真空紫外線によって励起される蛍光体を使用した真空紫外線励起発光素子の製造においては、蛍光膜形成のために蛍光体と有機バインダーを混合して蛍光体ペーストをつくり、蛍光体ペーストを塗布した後、有機成分を除去するために焼成（ペースト焼成）を行っている。 In the manufacture of a vacuum ultraviolet light-emitting device using such a phosphor excited by vacuum ultraviolet light, a phosphor paste is prepared by mixing the phosphor and an organic binder to form a phosphor film, and the phosphor paste is applied. After that, firing (paste firing) is performed to remove organic components.
しかしながら、上記従来の真空紫外線励起用蛍光体には、次のような課題があった。
すなわち、真空紫外線によって励起される上記蛍光体のうち、アルミン酸塩蛍光体である青色蛍光体のBaMgAl10O17:Eu及び青緑色蛍光体の(Ba,Sr)MgAl10O17:Eu,Mnにおいては、ペースト焼成の工程を経ることによって熱劣化が起こり、発光強度が低下してしまう課題を有していた。
However, the conventional vacuum ultraviolet excitation phosphor has the following problems.
That is, among the phosphors excited by vacuum ultraviolet rays, the blue phosphor BaMgAl 10 O 17 : Eu and the blue-green phosphor (Ba, Sr) MgAl 10 O 17 : Eu, Mn are aluminate phosphors. However, there has been a problem that thermal degradation occurs due to the paste baking step, and the emission intensity decreases.
また、上記青色または青緑色に発光するアルミン酸塩蛍光体は、長時間にわたり真空紫外線の照射を受けると真空紫外線劣化が起こり、発光強度が低下してしまう。つまり、真空紫外線励起発光素子を駆動させた場合、経時的な発光強度の低下を起こすという課題を有していた。 The aluminate phosphor that emits blue or blue-green light is subject to vacuum ultraviolet light deterioration when irradiated with vacuum ultraviolet light for a long time, resulting in a decrease in emission intensity. That is, when the vacuum ultraviolet ray excitation light emitting element is driven, there is a problem that the light emission intensity decreases with time.
このようなことから、上記アルミン酸塩蛍光体に代わり、青色または青緑色に発光する真空紫外線励起用蛍光体であって、ペースト焼成による熱劣化を起こしにくく、しかも真空紫外線照射による真空紫外線劣化もない新たな真空紫外線励起用蛍光体の開発が強く望まれている。 For this reason, instead of the aluminate phosphor, it is a phosphor for vacuum ultraviolet excitation that emits blue or blue-green light. There is a strong demand for the development of a new phosphor for vacuum ultraviolet excitation.
本発明者は、このような状況下において種々の蛍光体を合成し、上記の諸課題を解決すべく鋭意研究を重ねた。その結果、Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素と、Si及びGeから選択される少なくとも１種類の元素を含有する蛍光体が、真空紫外線で効率よく青緑色に発光し、ペースト焼成による熱劣化が極めて少ないことを見出した。 Under such circumstances, the present inventors have synthesized various phosphors and conducted intensive studies to solve the above problems. As a result, it contains Eu as an activator, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, and at least one type selected from the group of Ti, Zr and Hf It has been found that a phosphor containing an element and at least one element selected from Si and Ge emits blue-green light efficiently with vacuum ultraviolet rays and has extremely little thermal deterioration due to paste firing.
また、Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素と、Si及びGeから選択される少なくとも１種類の元素を含有する蛍光体が、真空紫外線照射による真空紫外線劣化が極めて少なく、従ってそれらに起因する発光強度の低下が極めて少ないことを見出し、本発明を完成した。 Also, Eu as an activator, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, and at least one element selected from the group of Ti, Zr and Hf And a phosphor containing at least one element selected from Si and Ge is found to have very little deterioration in vacuum ultraviolet rays due to irradiation with vacuum ultraviolet rays. Was completed.
（本発明の目的）
本発明の目的は、真空紫外線によって励起されることにより青緑色の発光を示す真空紫外線励起用蛍光体であって、ペースト焼成による発光強度の低下、すなわち熱劣化が極めて少ない真空紫外線励起用蛍光体、その製造方法及び蛍光体を使用した真空紫外線励起発光素子を提供することである。
(Object of the present invention)
An object of the present invention is a vacuum ultraviolet excitation phosphor that emits blue-green light when excited by vacuum ultraviolet radiation, and has a reduced emission intensity due to paste firing, i.e., extremely low thermal degradation. The manufacturing method and the vacuum ultraviolet-excited light emitting device using the phosphor are provided.
本発明の他の目的は、同じく青緑色の発光を示す真空紫外線励起用蛍光体であって、真空紫外線照射による発光強度の低下、すなわち真空紫外線劣化が極めて少ない真空紫外線励起用蛍光体、その製造方法及び蛍光体を使用した真空紫外線励起発光素子を提供することである。 Another object of the present invention is a vacuum ultraviolet excitation phosphor that also exhibits blue-green light emission, and its emission intensity is reduced by irradiation with vacuum ultraviolet rays, that is, a vacuum ultraviolet excitation phosphor that has very little vacuum ultraviolet deterioration, and its production. The present invention provides a vacuum ultraviolet light-emitting device using a method and a phosphor.
上記課題を解決するために本発明が講じた手段は次のとおりである。
第１の発明にあっては、
Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素と、Si及びGeから選択される少なくとも１種類の元素をそれぞれ含有することを特徴とする、
真空紫外線励起用蛍光体である。
Means taken by the present invention to solve the above problems are as follows.
In the first invention,
Eu as an activator, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, and at least one element selected from the group of Ti, Zr and Hf; Each containing at least one element selected from Si and Ge,
This is a vacuum ultraviolet excitation phosphor.
第２の発明にあっては、
Lx-aMyNzOx+2y+2z:Eua（ただし、式中、LはBa、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素を表し、MはTi、Zr、及びHfの群から選択される少なくとも１種類の元素を表し、NはSi及びGeから選択される少なくとも１種類の元素を表し、xは0.5≦x≦1.5、yは0.5≦y≦1.5、zは2≦z≦4、aは0.001≦a≦0.5の条件を満たす数である）により表される化合物を含むことを特徴とする、
真空紫外線励起用蛍光体である。
In the second invention,
L xa M y N z O x + 2y + 2z : Eu a (wherein L represents at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, M is Ti, Zr represents at least one element selected from the group of Hf, N represents at least one element selected from Si and Ge, x is 0.5 ≦ x ≦ 1.5, and y is 0.5 ≦ y ≦ 1.5. , Z is a number represented by 2 ≦ z ≦ 4, a is a number satisfying the condition of 0.001 ≦ a ≦ 0.5),
This is a vacuum ultraviolet excitation phosphor.
第３の発明にあっては、
真空紫外線励起用蛍光体の製造方法であって、出発原料として、Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素と、Si及びGeから選択される少なくとも１種類の元素とを含み、還元雰囲気中で焼成することを特徴とする、
真空紫外線励起用蛍光体の製造方法である。
In the third invention,
A method for producing a phosphor for vacuum ultraviolet excitation, comprising Eu as an activator as a starting material, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, Ti, Including at least one element selected from the group of Zr and Hf and at least one element selected from Si and Ge, and firing in a reducing atmosphere,
This is a method for producing a vacuum ultraviolet excitation phosphor.
第４の発明にあっては、
真空紫外線励起用蛍光体の製造方法であって、出発原料として、Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素と、Si及びGeから選択される少なくとも１種類の元素とを含み、フッ化物、塩化物または硼化物から選ばれた１種類または２種類以上の存在下で焼成することを特徴とする、
真空紫外線励起用蛍光体の製造方法である。
In the fourth invention,
A method for producing a phosphor for vacuum ultraviolet excitation, comprising Eu as an activator as a starting material, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, Ti, One or two selected from fluoride, chloride or boride, including at least one element selected from the group of Zr and Hf and at least one element selected from Si and Ge It is characterized by firing in the presence of the above,
This is a method for producing a vacuum ultraviolet excitation phosphor.
第５の発明にあっては、
第１または第２の発明に係る真空紫外線励起用蛍光体を使用することを特徴とする、
真空紫外線励起発光素子である。
In the fifth invention,
Using the phosphor for vacuum ultraviolet ray excitation according to the first or second invention,
It is a vacuum ultraviolet ray excited light emitting element.
（作用）
本発明に係る真空紫外線励起用蛍光体は、Euを付活剤として含有し、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素と、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素とSi及びGeから選択される少なくとも１種類の元素をそれぞれ含有することを特徴とする蛍光体であり、真空紫外線を吸収し、青緑の光を高効率で放射するものである。
(Function)
The phosphor for vacuum ultraviolet excitation according to the present invention contains Eu as an activator, and includes at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, and Ti, Zr and Hf. It is a phosphor characterized by containing at least one element selected from the group and at least one element selected from Si and Ge, and absorbs vacuum ultraviolet rays, making blue-green light highly efficient It radiates at.
本発明に係る真空紫外線励起用蛍光体を製造するためには、Ba、Sr及びCaの群から選択される少なくとも１種類のアルカリ土類金属元素、Ti、Zr、及びHfの群から選択される少なくとも１種類の元素、Si及びGeから選択される少なくとも１種類の元素及びEu元素のそれぞれの炭酸塩、硝酸塩、酸化物、水酸化物等を、前記各元素の構成比が所望の化学組成になるように秤量し、十分に混合し蛍光体原料を調整する。そして、原料粉体をアルミナるつぼ等の耐熱容器に充填し焼成することで製造することができる。 In order to manufacture the phosphor for vacuum ultraviolet ray excitation according to the present invention, it is selected from the group of at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, Ti, Zr and Hf. At least one kind of element, at least one kind of element selected from Si and Ge, and each element of Eu element, such as carbonate, nitrate, oxide, hydroxide, etc., the composition ratio of each element to the desired chemical composition Weigh so that the mixture is sufficiently mixed to prepare the phosphor material. And it can manufacture by filling raw material powder into heat-resistant containers, such as an alumina crucible, and baking.
焼成の際には、酸化雰囲気下において１回またはそれ以上の焼成を行ってもよいが、最終的には、還元雰囲気下で、例えば1000〜1600℃の温度において焼成を行うことが好ましい。
また、紫外線励起用蛍光体を製造するときの出発原料中に反応促進剤として、フッ化物、塩化物または硼化物から選ばれた１種類または２種類以上を混合し、その存在下で焼成を行うことが好ましい。
At the time of firing, one or more firings may be performed in an oxidizing atmosphere, but it is finally preferable to perform firing at a temperature of, for example, 1000 to 1600 ° C. in a reducing atmosphere.
In addition, one or two or more kinds selected from fluoride, chloride or boride are mixed as a reaction accelerator in a starting material when producing a phosphor for ultraviolet excitation, and firing is performed in the presence thereof. It is preferable.
このようにして得られた本発明に係る真空紫外線励起用蛍光体は、希ガスランプやその他の真空紫外線励起発光素子に使用されているアルミン酸塩蛍光体に比べて、ペースト焼成工程を経ても発光強度の低下はほとんど認められず、熱劣化が極めて少なかった。 The thus obtained phosphor for vacuum ultraviolet excitation according to the present invention can be obtained through a paste firing step as compared with the aluminate phosphor used in rare gas lamps and other vacuum ultraviolet excitation light emitting devices. Little decrease in emission intensity was observed, and thermal degradation was extremely small.
また、本発明に係る真空紫外線励起用蛍光体は、真空紫外線照射による発光強度の低下もほとんど認められず、真空紫外線劣化は極めて少なかった。これにより、蛍光体としての寿命が大幅に長くなった。 In addition, the phosphor for vacuum ultraviolet excitation according to the present invention showed almost no decrease in emission intensity due to vacuum ultraviolet irradiation, and extremely little deterioration in vacuum ultraviolet. Thereby, the lifetime as a fluorescent substance was prolonged significantly.
（ａ）本発明によれば、真空紫外線によって励起されると青緑色の光を効率的に発光し、ペースト焼成工程を経ても発光強度の低下はほとんど認められず、熱劣化が極めて少ない真空紫外線励起用蛍光体およびその製造方法を提供することができる。 (A) According to the present invention, when excited by vacuum ultraviolet light, blue-green light is efficiently emitted, and even after the paste firing step, almost no decrease in light emission intensity is observed, and vacuum ultraviolet light has very little thermal deterioration. An excitation phosphor and a method for manufacturing the same can be provided.
（ｂ）本発明によれば、同じく青緑色の光を効率的に発光し、真空紫外線照射による発光強度の低下はほとんど認められず、真空紫外線劣化が極めて少ない真空紫外線励起用蛍光体およびその製造方法を提供することができる。 (B) According to the present invention, a phosphor for exciting a vacuum ultraviolet ray and its production, which also efficiently emits blue-green light, hardly shows a decrease in emission intensity due to irradiation with vacuum ultraviolet rays, and has very little vacuum ultraviolet ray deterioration. A method can be provided.
（ｃ）本発明に係る真空紫外線励起用蛍光体を希ガスランプやその他の真空紫外線発光素子の蛍光体膜として適用することにより、長寿命の真空紫外線励起発光素子が実現できる。 (C) By applying the vacuum ultraviolet excitation phosphor according to the present invention as a phosphor film of a rare gas lamp or other vacuum ultraviolet light emitting elements, a long-life vacuum ultraviolet excitation light emitting element can be realized.
本発明を実施例によりさらに詳しく説明する。なお、本発明は以下の実施例に限定されるものではない。 The present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.
Ba0.98ZrSi3O9:Eu0.02を合成するにあたって、出発原料として炭酸バリウムBaCO3、酸化ジルコニウムZrO2、酸化珪素SiO2、酸化ユーロピウムEu2O3を用いた。用いた出発原料はいずれも純度99%以上である。これらの出発原料を、モル比がBaCO3：ZrO2：SiO2：Eu2O3=0.98：1：3：0.01となるように配合した。 In synthesizing Ba 0.98 ZrSi 3 O 9 : Eu 0.02 , barium carbonate BaCO 3 , zirconium oxide ZrO 2 , silicon oxide SiO 2 , and europium oxide Eu 2 O 3 were used as starting materials. The starting materials used have a purity of 99% or more. These starting materials were blended so that the molar ratio was BaCO 3 : ZrO 2 : SiO 2 : Eu 2 O 3 = 0.98: 1: 3: 0.01.
さらに、反応促進剤としてフッ化物であるフッ化アルミニウムAlF3を添加し、めのう乳鉢を用いて混合した。得られた混合粉体をアルミナるつぼに充填し、窒素−水素混合ガス（水素含有量は5体積％）中にて1450℃で5時間焼成し、室温まで徐冷した。得られた試料を粉砕後、粉末X線回折測定を行ったところ、BaZrSi3O9の組成の相が生成していることが分かった。 Furthermore, aluminum fluoride AlF 3 which is a fluoride was added as a reaction accelerator and mixed using an agate mortar. The obtained mixed powder was filled in an alumina crucible, fired at 1450 ° C. for 5 hours in a nitrogen-hydrogen mixed gas (hydrogen content: 5% by volume), and gradually cooled to room temperature. After the obtained sample was pulverized and subjected to powder X-ray diffraction measurement, it was found that a phase having a composition of BaZrSi 3 O 9 was formed.
得られた蛍光体Ba0.98ZrSi3O9:Eu0.02に対して、分光蛍光光度計（FP-777W、日本分光製）を用いて、254nmの紫外線による発光スペクトルを測定した。
図１に実施例１の発光スペクトルを示した。この蛍光体は、波長477nmをピークとする青緑色の発光を示した。
With respect to the obtained phosphor Ba 0.98 ZrSi 3 O 9 : Eu 0.02 , an emission spectrum by ultraviolet rays at 254 nm was measured using a spectrofluorometer (FP-777W, manufactured by JASCO Corporation).
The emission spectrum of Example 1 is shown in FIG. This phosphor exhibited blue-green light emission with a peak at a wavelength of 477 nm.
また、重水素ランプを励起光源として、真空紫外線領域から紫外線領域にかけての領域において励起スペクトルを測定した。
図２に実施例１の励起スペクトルを示した。この蛍光体は、紫外線領域よりも真空紫外線領域で強く発光し、波長147nmのXe共鳴線、波長172nmのXe分子線の両方に対して強い発光を示すことが分かった。
The excitation spectrum was measured in the region from the vacuum ultraviolet region to the ultraviolet region using a deuterium lamp as the excitation light source.
FIG. 2 shows the excitation spectrum of Example 1. This phosphor was found to emit more strongly in the vacuum ultraviolet region than in the ultraviolet region, and showed strong emission for both the Xe resonance line having a wavelength of 147 nm and the Xe molecular beam having a wavelength of 172 nm.
（熱劣化試験）
得られた蛍光体Ba0.98ZrSi3O9:Eu0.02と有機バインダーを混合してペーストを作成し、大気雰囲気中500℃で30分間焼成し、内製のマイクロ波発振Xe真空紫外線発生装置を用いて147nmの真空紫外線でペースト焼成前後の発光強度を比較した。
(Thermal degradation test)
The obtained phosphor Ba 0.98 ZrSi 3 O 9 : Eu 0.02 and an organic binder were mixed to prepare a paste, which was baked at 500 ° C. for 30 minutes in an air atmosphere, using an in-house microwave oscillation Xe vacuum ultraviolet generator. The emission intensity before and after paste firing was compared using vacuum ultraviolet rays of 147 nm.
表１は実施例１の蛍光体と、後述する比較例１の蛍光体の熱劣化試験結果である。
ペースト焼成前の蛍光体の発光強度を100%とすると、実施例１の蛍光体はペースト焼成後の発光強度が100%となっており、ペースト焼成による発光強度の低下は見られず、熱劣化は認められなかった。
Table 1 shows the thermal deterioration test results of the phosphor of Example 1 and the phosphor of Comparative Example 1 described later.
Assuming that the emission intensity of the phosphor before baking the paste is 100%, the emission intensity of the phosphor of Example 1 after baking the paste is 100%. Was not recognized.
（真空紫外線劣化試験）
ペースト焼成した蛍光体Ba0.98ZrSi3O9:Eu0.02を、内製の真空紫外線照射強制劣化試験装置を用いて20時間の真空紫外線劣化試験を実施した。この真空紫外線照射強制劣化試験装置は、石英管にHe（99体積%）−Xe（1体積%）混合ガスを導入して石英管両端に設けた電極に電圧を印加し、放電させることによって147nmのXe共鳴線及び172nmのXe分子線を発生させ、それらを試験試料に照射させるものである。
(Vacuum UV degradation test)
The paste fired phosphor Ba 0.98 ZrSi 3 O 9 : Eu 0.02 was subjected to a vacuum ultraviolet ray deterioration test for 20 hours using an in-house vacuum ultraviolet ray irradiation forced deterioration test apparatus. This vacuum ultraviolet ray irradiation forced degradation test apparatus introduces a He (99% by volume) -Xe (1% by volume) mixed gas into a quartz tube, applies a voltage to electrodes provided at both ends of the quartz tube, and discharges them to 147 nm. Xe resonance line and 172 nm Xe molecular beam are generated to irradiate the test sample.
強制劣化試験前後の蛍光体を、前述のマイクロ波発振Xe真空紫外線発生装置で強制劣化試験前の蛍光体の発光強度を100%として発光強度を比較した。
図３に実施例１の蛍光体の真空紫外線劣化試験結果を示した。真空紫外線劣化試験後の発光強度は試験前とほとんど変わらず、真空紫外線劣化はほとんど認められなかった。
The phosphors before and after the forced deterioration test were compared with each other using the above-described microwave oscillation Xe vacuum ultraviolet ray generator with the emission intensity of the phosphor before the forced deterioration test as 100%.
FIG. 3 shows the results of the vacuum ultraviolet ray degradation test of the phosphor of Example 1. The emission intensity after the vacuum ultraviolet ray deterioration test was almost the same as that before the test, and almost no vacuum ultraviolet ray deterioration was observed.
（比較例１）
比較例１として、アルミン酸塩蛍光体であるβ−アルミナ型構造の蛍光体BaMgAl10O17:Euを合成した。合成にあたっては、出発原料として炭酸バリウムBaCO3、水酸化マグネシウムMg(OH)2、酸化アルミニウムAl2O3、酸化ユーロピウムEu2O3を用いた。用いた出発原料はいずれも純度99%以上である。
(Comparative Example 1)
As Comparative Example 1, a phosphor BaMgAl 10 O 17 : Eu having a β-alumina structure, which is an aluminate phosphor, was synthesized. In the synthesis, barium carbonate BaCO 3 , magnesium hydroxide Mg (OH) 2 , aluminum oxide Al 2 O 3 , and europium oxide Eu 2 O 3 were used as starting materials. The starting materials used have a purity of 99% or more.
これらの出発原料を、モル比がBaCO3：Mg(OH)2：Al2O3：Eu2O3=0.9：1：5：0.05となるように配合した。さらに反応促進剤としてフッ化物であるフッ化アルミニウムAlF3を添加し、めのう乳鉢を用いて混合した。得られた混合粉体をアルミナるつぼに充填し、窒素−水素混合ガス（水素含有量は5体積%）中にて1450℃で5時間焼成し、室温まで徐冷した。得られた試料を粉砕し、組成がBa0.9MgAl10O17:Eu0.1の青色蛍光体を得た。 These starting materials were blended so that the molar ratio was BaCO 3 : Mg (OH) 2 : Al 2 O 3 : Eu 2 O 3 = 0.9: 1: 5: 0.05. Furthermore, aluminum fluoride AlF 3 which is a fluoride was added as a reaction accelerator and mixed using an agate mortar. The obtained mixed powder was filled into an alumina crucible, fired at 1450 ° C. for 5 hours in a nitrogen-hydrogen mixed gas (hydrogen content: 5% by volume), and gradually cooled to room temperature. The obtained sample was pulverized to obtain a blue phosphor having a composition of Ba 0.9 MgAl 10 O 17 : Eu 0.1 .
この蛍光体Ba0.9MgAl10O17:Eu0.1をペースト化し、大気雰囲気中において500℃で30分焼成した後、ペースト焼成前後での発光強度を比較した。
表１にその結果を示した。ペースト焼成後の蛍光体ではペースト焼成前の粉体の91%となり、発光強度が9%低下した。
This phosphor Ba 0.9 MgAl 10 O 17 : Eu 0.1 was made into a paste, fired at 500 ° C. for 30 minutes in the air atmosphere, and the emission intensity before and after firing the paste was compared.
Table 1 shows the results. The phosphor after paste firing was 91% of the powder before paste firing, and the emission intensity was reduced by 9%.
更に、前述の真空紫外線照射強制劣化試験装置を用いて劣化試験を実施し、劣化前後での発光強度を前述のマイクロ波発振真空紫外線発生装置を用いて比較した。
図３に比較例１の蛍光体の真空紫外線劣化試験結果を示した。劣化試験後の発光強度は劣化試験前を100%としたときの28%となり、大幅に低下した。
Further, a deterioration test was performed using the aforementioned vacuum ultraviolet irradiation forced deterioration test apparatus, and the emission intensity before and after the deterioration was compared using the above microwave oscillation vacuum ultraviolet generator.
FIG. 3 shows the results of the vacuum ultraviolet ray degradation test of the phosphor of Comparative Example 1. The light emission intensity after the deterioration test was 28% when the pre-deterioration test was taken as 100%, which was a significant decrease.
なお、本明細書で使用している用語と表現は、あくまで説明上のものであって限定的なものではなく、上記用語、表現と等価の用語、表現を除外するものではない。また、本発明は図示されている実施の形態に限定されるものではなく、技術思想の範囲内において種々の変形が可能である。 Note that the terms and expressions used in the present specification are merely explanatory and not restrictive, and do not exclude terms and expressions equivalent to the above terms and expressions. The present invention is not limited to the illustrated embodiment, and various modifications can be made within the scope of the technical idea.
Claims (5)
真空紫外線励起用蛍光体。 Eu as an activator, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, and at least one element selected from the group of Ti, Zr and Hf; Each containing at least one element selected from Si and Ge,
Vacuum ultraviolet excitation phosphor.
真空紫外線励起用蛍光体。 L xa M y N z O x + 2y + 2z : Eu a (wherein L represents at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, M is Ti, Zr represents at least one element selected from the group of Hf, N represents at least one element selected from Si and Ge, x is 0.5 ≦ x ≦ 1.5, and y is 0.5 ≦ y ≦ 1.5. , Z is a number represented by 2 ≦ z ≦ 4, a is a number satisfying the condition of 0.001 ≦ a ≦ 0.5),
Vacuum ultraviolet excitation phosphor.
真空紫外線励起用蛍光体の製造方法。 A method for producing a phosphor for vacuum ultraviolet excitation, comprising Eu as an activator as a starting material, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, Ti, Including at least one element selected from the group of Zr and Hf and at least one element selected from Si and Ge, and firing in a reducing atmosphere,
A method for producing a phosphor for vacuum ultraviolet excitation.
真空紫外線励起用蛍光体の製造方法。 A method for producing a phosphor for vacuum ultraviolet excitation, comprising Eu as an activator as a starting material, at least one alkaline earth metal element selected from the group of Ba, Sr and Ca, Ti, One or two selected from fluoride, chloride or boride, including at least one element selected from the group of Zr and Hf and at least one element selected from Si and Ge It is characterized by firing in the presence of the above,
A method for producing a phosphor for vacuum ultraviolet excitation.
真空紫外線励起発光素子。 The phosphor for vacuum ultraviolet ray excitation according to claim 1 or 2 is used,
Vacuum ultraviolet excitation light emitting element.
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| WO2008018578A1 (en) * | 2006-08-10 | 2008-02-14 | Sumitomo Chemical Company, Limited | Phosphor, phosphor paste containing the same, and light-emitting device |
| WO2008111438A1 (en) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | Phosphor for ultraviolet excited light-emitting device, phosphor paste, and ultraviolet excited light-emitting device |
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| WO2014006755A1 (en) * | 2012-07-06 | 2014-01-09 | 住友金属鉱山株式会社 | Silicate phosphor and process for manufacturing same |
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| WO2008018576A1 (en) * | 2006-08-10 | 2008-02-14 | Sumitomo Chemical Company, Limited | Phosphor, phosphor paste containing the same, and light-emitting device |
| WO2008018578A1 (en) * | 2006-08-10 | 2008-02-14 | Sumitomo Chemical Company, Limited | Phosphor, phosphor paste containing the same, and light-emitting device |
| WO2008111438A1 (en) * | 2007-03-09 | 2008-09-18 | Sumitomo Chemical Company, Limited | Phosphor for ultraviolet excited light-emitting device, phosphor paste, and ultraviolet excited light-emitting device |
| JP2008222766A (en) * | 2007-03-09 | 2008-09-25 | Sumitomo Chemical Co Ltd | Phosphor for UV-excited light emitting device |
| JP2012144689A (en) * | 2010-12-24 | 2012-08-02 | Sumitomo Metal Mining Co Ltd | Silicate phosphor and method for producing the same |
| CN104271705A (en) * | 2012-04-24 | 2015-01-07 | 默克专利有限公司 | Silicate phosphors |
| JP2015520783A (en) * | 2012-04-24 | 2015-07-23 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Silicate phosphor |
| US9657222B2 (en) | 2012-04-24 | 2017-05-23 | Merck Patent Gmbh | Silicate phosphors |
| WO2014006755A1 (en) * | 2012-07-06 | 2014-01-09 | 住友金属鉱山株式会社 | Silicate phosphor and process for manufacturing same |
| US10144869B2 (en) | 2012-07-06 | 2018-12-04 | Sumitomo Metal Mining Co., Ltd. | Silicate phosphor and method for producing the same |
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