JP4318536B2 - Red phosphor mainly composed of alkaline earth sulfide and method for producing the same - Google Patents
Red phosphor mainly composed of alkaline earth sulfide and method for producing the same Download PDFInfo
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- JP4318536B2 JP4318536B2 JP2003388816A JP2003388816A JP4318536B2 JP 4318536 B2 JP4318536 B2 JP 4318536B2 JP 2003388816 A JP2003388816 A JP 2003388816A JP 2003388816 A JP2003388816 A JP 2003388816A JP 4318536 B2 JP4318536 B2 JP 4318536B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- 229910052733 gallium Inorganic materials 0.000 claims description 23
- 229910052738 indium Inorganic materials 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- 239000011575 calcium Substances 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 claims description 13
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 229910052701 rubidium Inorganic materials 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Inorganic materials [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 description 13
- 238000005401 electroluminescence Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000005284 excitation Effects 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000005136 cathodoluminescence Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910016655 EuF 3 Inorganic materials 0.000 description 1
- 229910005269 GaF 3 Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
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Description
本発明は、アルカリ土類硫化物を主成分とする赤色蛍光体及びその製造方法に関し、詳しくはエレクトロルミネッセンセス(ＥＬ)、電界放射型ディスプレイ(ＦＥＤ)、プラズマディスプレイ(ＰＤＰ)等のディスプレイデバイスに用いられるアルカリ土類硫化物を主成分とする赤色蛍光体及びその製造方法に関する。 The present invention relates to a red phosphor mainly composed of an alkaline earth sulfide and a method for producing the same, and more particularly to a display such as an electroluminescence (EL), a field emission display (FED), or a plasma display (PDP). The present invention relates to a red phosphor mainly composed of alkaline earth sulfide used in a device and a method for producing the same.
蛍光体は、電子線又は紫外線により励起し発光する。このような蛍光体は、ディスプレイデバイスとして用いられている。パソコン用、ＴＶ用等の表示用ディスプレイにはカラー化が不可欠である。 The phosphor emits light when excited by an electron beam or ultraviolet rays. Such a phosphor is used as a display device. Colorization is indispensable for displays for personal computers and TVs.
カラー化に用いられる赤色、緑色、青色の３原色に発光する蛍光体として硫化物を主体とするものが信頼性、耐環境性に優れているが、要求特性である輝度、効率及び色純度のいずれかの点で満足するものではなく実用化の妨げとなっている。 The phosphors that emit light in the three primary colors of red, green, and blue used for colorization are mainly composed of sulfides, which are excellent in reliability and environmental resistance, but have the required characteristics of brightness, efficiency, and color purity. It is not satisfactory in any respect and hinders practical application.
加速電圧が１００Ｖ程度と低加速電圧のＥＬの用途においては、青緑色蛍光体としてＳｒＳ：Ｃｅ、緑色蛍光体としてＺｎＳ：Ｔｂ、また橙色蛍光体としてＺｎＳ：Ｍｎ等が知られている。 In EL applications where the acceleration voltage is as low as about 100 V, SrS: Ce is known as a blue-green phosphor, ZnS: Tb as a green phosphor, ZnS: Mn as an orange phosphor, and the like.
赤色蛍光体は、物理測光における発光強度が、緑色や橙色の蛍光体と同じであっても赤色は視感度が低いため、輝度が低い。従って、緑色や橙色の蛍光体と比べて効率が悪い。 The red phosphor has low luminance because red has low luminous sensitivity even if the emission intensity in physical photometry is the same as that of the green or orange phosphor. Therefore, the efficiency is lower than that of green and orange phosphors.
このため、従来においては、赤色蛍光体の特性を向上させる試みが多くなされている。例えば特許文献１(特開２００２−８０８４５号公報)及び特許文献２(特開２００３−４１２５０号公報)には、硫化カルシウムを母体中心とし、Ｅｕを発光中心、Ｍｎ，Ｌｉ，Ｃｅ，Ｇｄ等を増感剤とした赤色蛍光体が記載されている。 For this reason, conventionally, many attempts have been made to improve the characteristics of the red phosphor. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2002-80845) and Patent Document 2 (Japanese Patent Laid-Open No. 2003-41250), calcium sulfide is the center of the matrix, Eu is the emission center, Mn, Li, Ce, Gd, and the like. A red phosphor as a sensitizer is described.
これらの赤色蛍光体は、発光の赤色純度に優れており、ＥＬ用デバイスとして期待が大きいが、低速電子励起では輝度が不充分であり、また化学的に不安定で、再現性が得にくいという問題がある。しかも、この蛍光体の製造に際しては、アルカリ土類系硫化物は酸化されやすく化学的に不安定であるため、原料であるＣａＳ，Ｅｕ２Ｓ３を有毒な硫化水素ガスや二硫化炭素ガス雰囲気や水素を含有する還元性雰囲気で焼成する必要があった。These red phosphors have excellent red purity of light emission, and are expected as EL devices, but they are insufficient in luminance by low-speed electron excitation, are chemically unstable, and are difficult to obtain reproducibility. There's a problem. Moreover, since alkaline earth sulfides are easily oxidized and chemically unstable during the production of this phosphor, the raw materials CaS and Eu 2 S 3 are toxic in hydrogen sulfide gas or carbon disulfide gas atmosphere. And firing in a reducing atmosphere containing hydrogen.
また、その他の赤色蛍光体として、Ｙ２Ｏ２Ｓ：Ｅｕからなる組成の赤色蛍光体、ＺｎＣｄＳ：Ａｇ，ＣｌやＺｎＣｄＳ：Ｍｎ等の組成からなる赤色蛍光体、ＺｎＳ：Ｍｎからなる組成の赤色蛍光体が提案されている。As other red phosphors, a red phosphor having a composition composed of Y 2 O 2 S: Eu, a red phosphor having a composition such as ZnCdS: Ag, Cl, ZnCdS: Mn, and a red having a composition composed of ZnS: Mn. Phosphors have been proposed.
Ｙ２Ｏ２Ｓ：Ｅｕからなる組成の蛍光体は、電子線励起で効率が高く、ブラウン管用の用途が期待されるが、色純度に劣り、低速電子励起では極端に輝度が低下する。A phosphor having a composition composed of Y 2 O 2 S: Eu is high in efficiency by electron beam excitation and is expected to be used for a cathode ray tube, but has poor color purity and extremely low luminance in low-speed electron excitation.
ＺｎＣｄＳ：Ａｇ，ＣｌやＺｎＣｄＳ：Ｍｎ等の組成からなる赤色蛍光体は、化学的に安定な材料であり、低加速電圧で発光するが、規制対象物質のＣｄを含むため、この蛍光体を用いたデバイスは将来的に販売できなくなる可能性が高い。 A red phosphor having a composition such as ZnCdS: Ag, Cl or ZnCdS: Mn is a chemically stable material and emits light at a low acceleration voltage. However, since it contains Cd as a regulated substance, this phosphor is used. There is a high possibility that the devices that were sold will not be sold in the future.
ＺｎＳ：Ｍｎからなる組成の赤色蛍光体は、ＥＬ用途としては輝度、効率が高いが、発光色が橙色であるためカラーフィルターを必要とする。 A red phosphor having a composition composed of ZnS: Mn has high luminance and efficiency for EL applications, but requires a color filter because the emission color is orange.
このように、低速電子励起で、特にＥＬ用途に用いられ、色純度のみならず輝度及び効率が良好な赤色蛍光体は得られていない。 As described above, a red phosphor having low luminance excitation and particularly good luminance and efficiency as well as color purity has not been obtained.
従って、本発明の目的は、低速電子励起においても、高い色純度と共に良好な輝度及び効率を有し、特にＥＬ用途に好適に用いられる赤色蛍光体、及びその安定的、かつ再現性の良好な製造方法を提供することにある。 Therefore, an object of the present invention is to provide a red phosphor having good luminance and efficiency with high color purity even in low-speed electron excitation, and particularly suitable for EL applications, and stable and reproducible. It is to provide a manufacturing method.
本発明者らは上記課題を解決すべく鋭意検討を行った結果、（Ｃａ，Ｓｒ）Ｓを母体中心(母体材料)、Ｅｕを発光中心とする赤色蛍光体において、Ａｌ，Ｇａ，Ｉｎから選ばれる少なくとも１種及び／又はＲｂとＦを増感剤として用いること、並びにその好適な製造方法によって、上記目的が達成し得ることを知見した。As a result of intensive studies to solve the above-mentioned problems, the present inventors selected Al, Ga, and In as a red phosphor having (Ca, Sr) S as the center of the matrix (matrix material) and Eu as the emission center. It has been found that the above object can be achieved by using at least one of the above and / or Rb and F as a sensitizer and a suitable production method thereof.
すなわち、本発明（１）は、下記一般式(１)で示される赤色蛍光体を提供するものである。
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｆ … … (１)
（但し、ＡはＡｌ，Ｇａ，Ｉｎから選択される少なくとも１種を表す）That is, the present invention (1) provides a red phosphor represented by the following general formula (1).
(Ca, Sr) S: Eu, A, F (1)
(However, A represents at least one selected from Al, Ga, and In)
また、本発明（２）は、下記式(２)で示される赤色蛍光体を提供するものである。
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ｒｂ，Ｆ … … (２)The present invention (2) provides a red phosphor represented by the following formula (2).
(Ca, Sr) S: Eu, Rb, F (2)
また、本発明（３）は、下記一般式(３)で示される赤色蛍光体を提供するものである。
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｒｂ，Ｆ … … (３)
（但し、Ａは上記一般式（１）と同じ）The present invention (3) provides a red phosphor represented by the following general formula (3).
(Ca, Sr) S: Eu, A, Rb, F (3)
(However, A is the same as the above general formula (1))
また、本発明（４）は、上記本発明（１）及び（３）において、Ａｌ，Ｇａ又はＩｎから選択される少なくとも１種を０．０１〜５モル％含有する上記赤色蛍光体を提供するものである。 Moreover, this invention (4) provides the said red fluorescent substance which contains 0.01-5 mol% of at least 1 sort (s) selected from Al, Ga, or In in the said invention (1) and (3). Is.
また、本発明（５）は、上記本発明（２）及び（３）において、Ｒｂを０．０１〜２モル％含有する上記赤色蛍光体を提供するものである。 The present invention (5) provides the red phosphor containing 0.01 to 2 mol% of Rb in the present inventions (2) and (3).
また、本発明（６）は、硫化カルシウム及び／又は硫化ストロンチウムとＡｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物とイオウとフッ化ユーロピウムを混合し、分級、成型した後、９００〜１１８０℃、１〜２４時間、不活性ガス雰囲気中で焼成することを特徴とする赤色蛍光体の製造方法を提供するものである。 In the invention (6), after mixing, classifying and molding calcium sulfide and / or strontium sulfide and at least one fluoride selected from Al, Ga or In, sulfur and europium fluoride, The present invention provides a method for producing a red phosphor, characterized by firing in an inert gas atmosphere at 1180 ° C. for 1 to 24 hours.
また、本発明（７）は、硫化カルシウム及び／又は硫化ストロンチウムとルビジウムの炭酸塩、フッ化物又は硫化物とイオウとフッ化ユーロピウムとを混合し、分級、成型した後、９００〜１１８０℃、１〜２４時間、不活性ガス雰囲気中で焼成することを特徴とする赤色蛍光体の製造方法を提供するものである。 In the present invention (7), calcium sulfide and / or strontium sulfide and rubidium carbonate, fluoride or sulfide, sulfur and europium fluoride are mixed, classified, molded, and then subjected to 900 to 1180 ° C., 1 The present invention provides a method for producing a red phosphor characterized by firing in an inert gas atmosphere for -24 hours.
また、本発明（８）は、硫化カルシウム及び／又は硫化ストロンチウムとＡｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物とルビジウムの炭酸塩、フッ化物又は硫化物とイオウとフッ化ユーロピウムを混合し、分級、成型した後、９００〜１１８０℃、１〜２４時間、不活性ガス雰囲気中で焼成することを特徴とする赤色蛍光体の製造方法を提供するものである。 Further, the present invention (8) includes calcium sulfide and / or strontium sulfide and at least one fluoride selected from Al, Ga or In, carbonate of rubidium, fluoride or sulfide, sulfur and europium fluoride. After mixing, classifying, and molding, a method for producing a red phosphor is provided, which is fired in an inert gas atmosphere at 900 to 1180 ° C. for 1 to 24 hours.
また、本発明（９）は、上記本発明（６）〜（８）において、上記フッ化ユーロピウムを０．１〜１０モル％添加する上記赤色蛍光体の製造方法を提供するものである。 Moreover, this invention (9) provides the manufacturing method of the said red fluorescent substance which adds 0.1-10 mol% of said europium fluoride in said invention (6)-(8).
また、本発明（１０）は、上記本発明（６）、（８）及び（９）において、上記Ａｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物をＡｌ，Ｇａ又はＩｎ換算で０．０１〜５モル％添加する上記赤色蛍光体の製造方法を提供するものである。 Further, the present invention (10) is the above-described present invention (6), (8) and (9), wherein at least one fluoride selected from Al, Ga or In is converted to 0 in terms of Al, Ga or In. The present invention provides a method for producing the red phosphor added in an amount of 0.01 to 5 mol%.
また、本発明（１１）は、上記本発明（７）〜（９）において、上記ルビジウムの炭酸塩、フッ化物又は硫化物をルビジウム換算で０．１〜２モル％添加する上記赤色蛍光体の製造方法を提供するものである。 Further, the present invention (11) is the red phosphor according to the present invention (7) to (9), wherein the rubidium carbonate, fluoride or sulfide is added in an amount of 0.1 to 2 mol% in terms of rubidium. A manufacturing method is provided.
本発明に係る赤色蛍光体は、低速電子励起においても、高い色純度と共に良好な輝度及び効率を有することから、ディスプレイデバイス、特にＥＬ用途に好適に用いられる。また、本発明に係る製造方法によって、硫化水素ガス、二硫化炭素等の有毒な雰囲気を採用することなしに、再現性よく、化学的に安定な上記赤色蛍光体が得られる。 Since the red phosphor according to the present invention has good luminance and efficiency as well as high color purity even in low-speed electron excitation, it is suitably used for display devices, particularly EL applications. In addition, the production method according to the present invention can provide the above-described red phosphor with high reproducibility and chemical stability without employing a toxic atmosphere such as hydrogen sulfide gas or carbon disulfide.
以下、本発明に係る赤色蛍光体について詳述する。
本発明に係る赤色蛍光体は、下記一般式(１)、下記式(２)及び下記一般式(３)で示される。
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｆ … … (１)
（但し、ＡはＡｌ，Ｇａ，Ｉｎから選択される少なくとも１種を表す）
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ｒｂ，Ｆ … … (２)
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｒｂ，Ｆ … … (３)
（但し、Ａは上記と同じ）Hereinafter, the red phosphor according to the present invention will be described in detail.
The red phosphor according to the present invention is represented by the following general formula (1), the following formula (2), and the following general formula (3).
(Ca, Sr) S: Eu, A, F (1)
(However, A represents at least one selected from Al, Ga, and In)
(Ca, Sr) S: Eu, Rb, F (2)
(Ca, Sr) S: Eu, A, Rb, F (3)
(However, A is the same as above)
本発明に係る赤色蛍光体は、硫化カルシウム及び／又は硫化ストロンチウムを母体中心(母体材料)とし、ユーロピウムを発光中心とする。 The red phosphor according to the present invention has calcium sulfide and / or strontium sulfide as a base center (base material) and europium as a luminescent center.
母体中心である（Ｃａ１−ｘＳｒｘ）Ｓで示される上記硫化カルシウム及び／又は硫化ストロンチウムの含有割合であるｘ（０≦ｘ≦１）を調整することによって、発光波長を任意に制御することが可能となる。すなわち、ＣａＳ：Ｅｕの極大発光波長は６５０ｎｍであり、ＳｒＳ：Ｅｕの極大発光波長は５９０ｎｍであり、カルシウムとストロンチウムの含有割合を調整することによって、上記発光波長の間で発光波長を任意に制御することができる。このことは、Ａｌ，Ｒｂ等の増感剤を含有する場合においても同様である。The emission wavelength is arbitrarily controlled by adjusting x (0 ≦ x ≦ 1), which is the content ratio of the calcium sulfide and / or strontium sulfide represented by (Ca 1-x Sr x ) S which is the base of the matrix. It becomes possible. That is, the maximum emission wavelength of CaS: Eu is 650 nm, the maximum emission wavelength of SrS: Eu is 590 nm, and the emission wavelength is arbitrarily controlled between the emission wavelengths by adjusting the content ratio of calcium and strontium. can do. The same applies to the case of containing a sensitizer such as Al or Rb.
本発明に係る赤色蛍光体は、Ａｌ，Ｇａ，Ｉｎから選ばれる少なくとも１種(Ａ)及び／又はＲｂを増感剤（電荷補償剤）とする。これらの増感剤は、電子線励起効率の向上を目的とするものであり、母体中心に導電性を付与する。 The red phosphor according to the present invention uses at least one (A) and / or Rb selected from Al, Ga and In as a sensitizer (charge compensator). These sensitizers are intended to improve the electron beam excitation efficiency, and impart conductivity to the center of the matrix.
本発明に係る赤色蛍光体において、上記一般式(１)及び（３）におけるアルミニウム族元素であるＡｌ，Ｇａ，Ｉｎから選択される少なくとも１種（Ａ）の含有量は、好ましくは０．０１〜５モル％である。上記Ａ成分の含有量が０．０１モル％未満ではこの成分の含有効果がなく、５モル％を超えると輝度が低下するだけでなく焼結体にクラックが生じる。さらに上記一般式（１）においては、上記Ａ成分のさらに好ましい含有量は１〜２モル％であり、上記一般式（３）においては、上記Ａ成分の好ましい含有量は０．５〜２モル％である。 In the red phosphor according to the present invention, the content of at least one (A) selected from Al, Ga and In which are aluminum group elements in the general formulas (1) and (3) is preferably 0.01. ~ 5 mol%. If the content of the component A is less than 0.01 mol%, the effect of containing this component is not obtained, and if it exceeds 5 mol%, not only the luminance is lowered but also cracks are generated in the sintered body. Further, in the general formula (1), the more preferable content of the component A is 1 to 2 mol%. In the general formula (3), the preferable content of the component A is 0.5 to 2 mol. %.
本発明に係る赤色蛍光体において、上記式(２)及び一般式（３）におけるＲｂの含有量は、好ましくは０．０１〜２モル％である。上記Ｒｂの含有量が０．０１モル％未満ではこの成分の含有効果がなく、２モル％を超えると３価のユーロピウムが生成し、著しく輝度が低下する。さらに上記式（２）においては、上記Ｒｂのさらに好ましい含有量は０．５〜１．５モル％であり、最適値は１モル％であり、上記化学式（３）においては、上記Ｒｂの好ましい含有量は０．５〜１モル％である。 In the red phosphor according to the present invention, the content of Rb in the above formula (2) and general formula (3) is preferably 0.01 to 2 mol%. If the content of Rb is less than 0.01 mol%, the effect of containing this component is not present, and if it exceeds 2 mol%, trivalent europium is produced, and the luminance is remarkably lowered. Further, in the above formula (2), the more preferable content of Rb is 0.5 to 1.5 mol%, and the optimum value is 1 mol%. In the above chemical formula (3), the above Rb is preferable. Content is 0.5-1 mol%.
また、上記一般式(１)、上記式(２)及び上記一般式(３)で示される本発明に係る赤色蛍光体において、Ｆの含有量は、６モル％以下とすることが望ましい。 In the red phosphor according to the present invention represented by the above general formula (1), the above formula (2), and the above general formula (3), the content of F is preferably 6 mol% or less.
次に、本発明に係る赤色蛍光体の好ましい製造方法の一例を説明する。図１に本発明の製造方法のフロー図を示す。 Next, an example of a preferable method for producing the red phosphor according to the present invention will be described. FIG. 1 shows a flowchart of the manufacturing method of the present invention.
本発明の製造方法では、下記（Ｉ）〜（III）を原料とする。
（Ｉ）硫化カルシウム及び／又は硫化ストロンチウムとＡｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物とイオウとフッ化ユーロピウム
(II) 硫化カルシウム及び／又は硫化ストロンチウムとルビジウムの炭酸塩、フッ化物又は硫化物とイオウとフッ化ユーロピウム
(III) 硫化カルシウム及び／又は硫化ストロンチウムとＡｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物とルビジウムの炭酸塩、フッ化物又は硫化物とイオウとフッ化ユーロピウムIn the production method of the present invention, the following (I) to (III) are used as raw materials.
(I) Calcium sulfide and / or strontium sulfide and at least one fluoride selected from Al, Ga or In, sulfur and europium fluoride
(II) Calcium sulfide and / or strontium sulfide and rubidium carbonate, fluoride or sulfide and sulfur and europium fluoride
(III) At least one fluoride and rubidium carbonate selected from calcium sulfide and / or strontium sulfide and Al, Ga or In, fluoride or sulfide and sulfur and europium fluoride
上記原料（Ｉ）〜（III）のように、フッ化ユーロピウムを用いることによって、硫化カルシウム及び／又は硫化ストロンチウムからなる母体中心へのユーロピウムの固溶が容易に起こる。フッ化ユーロピウムは０．５〜１．５モル％添加することが望ましく、最適値は１モル％である。 By using europium fluoride as in the above raw materials (I) to (III), solid solution of europium easily occurs at the center of the matrix composed of calcium sulfide and / or strontium sulfide. It is desirable to add 0.5 to 1.5 mol% of europium fluoride, and the optimum value is 1 mol%.
また、上記原料（Ｉ）及び（III）のように、Ａｌ，Ｇａ又はＩｎから選択される少なくとも１種のフッ化物を用いることによって、これらフッ化物は焼成温度範囲で溶融するため、フラックス効果により焼結が促進される。これらのフッ化物はＡｌ，Ｇａ又はＩｎ換算で０．０１〜５モル％添加されることが望ましい。さらに上記原料（Ｉ）においては、これらのフッ化物のさらに好ましい添加量はＡｌ，Ｇａ又はＩｎ換算で１〜２モル％であり、上記原料（III）においては、これらのフッ化物のさらに好ましい添加量はＡｌ，Ｇａ又はＩｎ換算で０．５〜２モル％である。 In addition, by using at least one fluoride selected from Al, Ga or In as in the raw materials (I) and (III), these fluorides are melted in the firing temperature range. Sintering is promoted. These fluorides are preferably added in an amount of 0.01 to 5 mol% in terms of Al, Ga or In. Further, in the raw material (I), a more preferable addition amount of these fluorides is 1 to 2 mol% in terms of Al, Ga or In, and in the raw material (III), a more preferable addition of these fluorides. The amount is 0.5 to 2 mol% in terms of Al, Ga or In.
上記原料(II)及び(III)において、Ｒｂの炭酸塩、フッ化物又は硫化物の添加量はＲｂ換算で０．０１〜２モル％であることが望ましい。上記原料（II）においては、上記Ｒｂの炭酸塩、フッ化物又は硫化物のさらに好ましい添加量はＲｂ換算で０．５〜１．５モル％であり、最適値は１モル％であり、上記原料（III）においては、上記Ｒｂの炭酸塩、フッ化物又は硫化物の好ましい添加量はＲｂ換算で０．５〜１モル％である。 In the raw materials (II) and (III), the amount of Rb carbonate, fluoride or sulfide added is preferably 0.01 to 2 mol% in terms of Rb. In the raw material (II), the more preferable addition amount of the carbonate, fluoride or sulfide of Rb is 0.5 to 1.5 mol% in terms of Rb, and the optimum value is 1 mol%. In the raw material (III), a preferable addition amount of the carbonate, fluoride or sulfide of Rb is 0.5 to 1 mol% in terms of Rb.
これらの原料(Ｉ)〜(III)を用いることによって、反応時間を大幅に短縮でき、アルゴンガス等の不活性ガス雰囲気による焼成でも酸化を抑制することができる。 By using these raw materials (I) to (III), the reaction time can be greatly shortened, and oxidation can be suppressed even by firing in an inert gas atmosphere such as argon gas.
本発明に係る製造方法では、図１に示されるように、上記原料(Ｉ)〜(III)を混合する。混合は例えばφ３ｍｍのジルコニアボールをメディアに用いてペイントシェーカーやボールミル等で９０分程度なされる。 In the manufacturing method according to the present invention, as shown in FIG. 1, the raw materials (I) to (III) are mixed. For example, the mixing is performed for about 90 minutes with a paint shaker or a ball mill using zirconia balls having a diameter of 3 mm as media.
次いで、１００μｍ以下に分級し、さらにφ２０ｍｍ、約６２０ｋｇ／ｃｍ２の条件で成型する。Next, it is classified to 100 μm or less, and further molded under the conditions of φ20 mm and about 620 kg / cm 2 .
さらに、９００〜１１８０℃、１〜２４時間、不活性ガス雰囲気中で焼成する。焼成温度が９００℃未満では焼結体の密度が低く、機械的強度が不十分であり、１１８０℃を超える高温では原料に低融点物質を用いるため飛散し、組成制御が困難になる。また、焼成時間が１時間未満では物質特性に再現性が得られにくく、２４時間を超えると物質飛散の増加による組成変動の問題が生じる。 Further, it is fired in an inert gas atmosphere at 900 to 1180 ° C. for 1 to 24 hours. If the firing temperature is less than 900 ° C., the density of the sintered body is low and the mechanical strength is insufficient. If the firing temperature is higher than 1180 ° C., a low melting point material is used as a raw material, so that the composition control becomes difficult. In addition, if the firing time is less than 1 hour, it is difficult to obtain reproducibility of the material characteristics, and if it exceeds 24 hours, there is a problem of composition variation due to an increase in material scattering.
不活性ガス雰囲気としては、アルゴンガス雰囲気、窒素ガス雰囲気等が挙げられるが、特にアルゴンガス雰囲気が好ましく用いられる。 Examples of the inert gas atmosphere include an argon gas atmosphere and a nitrogen gas atmosphere, and an argon gas atmosphere is particularly preferably used.
上記本発明に係る赤色蛍光体は、例えば、電解放射型ディスプレイ、プラズマディスプレイ、エレクトロルミネッセンス等のディスプレイデバイスの用途に使用されるほか、４６０ｎｍ前後に強い励起スペクトルを有することから青色ＬＥＤ励起用蛍光体の用途に適用でき、特にエレクトロルミネッセンスのディスプレイデバイスとして期待される。また、本発明に係る赤色蛍光体の製造方法によって、上記本発明に係る赤色蛍光体を再現性よく、かつ化学的に安全に製造することができる。 The red phosphor according to the present invention is used for, for example, display devices such as an electrolytic emission display, a plasma display, and electroluminescence, and has a strong excitation spectrum around 460 nm. In particular, it is expected as an electroluminescence display device. Moreover, the red phosphor according to the present invention can be produced with good reproducibility and chemically safely by the method for producing a red phosphor according to the present invention.
以下に実施例を示すが、本発明はこれらに限定されて解釈されるものではない。 Examples are shown below, but the present invention is not construed as being limited thereto.
以下、実施例１〜実施例１０を比較例１と対比して説明する。原料としてＣａＳ、ＡｌＦ３、ＧａＦ３、Ｒｂ２ＣＯ３、Ｓ及びＥｕＦ３を各々用い、表１の組成となるように秤量し、φ３ｍｍのジルコニアボールをメディアに用いてペイントシェーカーで９０分混合した。Hereinafter, Examples 1 to 10 will be described in comparison with Comparative Example 1. Using CaS, AlF 3 , GaF 3 , Rb 2 CO 3 , S and EuF 3 as raw materials, each was weighed to have the composition shown in Table 1, and mixed for 90 minutes with a paint shaker using φ3 mm zirconia balls as media. .
次いで、１００μｍ以下に分級し、さらにφ２０ｍｍ、約６２０ｋｇ／ｃｍ２の条件で成型した。さらに、１０５０℃、１２時間、アルゴンガス雰囲気中で焼成し、赤色蛍光体を得た。Subsequently, it classified to 100 micrometers or less, and also shape | molded on the conditions of (phi) 20mm and about 620 kg / cm < 2 >. Further, it was baked in an argon gas atmosphere at 1050 ° C. for 12 hours to obtain a red phosphor.
得られた赤色蛍光体の極大発光波長とカソードルミネッセンス（ＣＬ）相対強度を表１に示す。また、実施例１〜３、５〜６及び比較例１のカソードルミネッセンス（ＣＬ）相対強度とＡｌ又はＲｂの含有量の関係を図２に示す。また、実施例１、３及び比較例１の波長とカソードルミネッセンス（ＣＬ）相対強度の関係を図３に示す。 Table 1 shows the maximum emission wavelength and cathodoluminescence (CL) relative intensity of the obtained red phosphor. Moreover, the relationship of the cathode luminescence (CL) relative intensity | strength of Examples 1-3, 5-6, and the comparative example 1 and content of Al or Rb is shown in FIG. FIG. 3 shows the relationship between the wavelengths of Examples 1 and 3 and Comparative Example 1 and the relative intensity of cathodoluminescence (CL).
表１及び図２に示されるように、実施例１〜４の赤色蛍光体は、比較例１に比してカソードルミネッセンス相対強度を３００％以上向上させることができ、実施例５及び６の赤色蛍光体は、比較例１に比してカソードルミネッセンス相対強度を２０〜３０％向上させることができる。さらに、表１に示されるように、実施例７〜１０の赤色蛍光体は、比較例１に比してカソードルミネッセンス相対強度を２０〜６０％程度向上させることができる。 As shown in Table 1 and FIG. 2, the red phosphors of Examples 1 to 4 can improve the relative intensity of cathodoluminescence by 300% or more compared to Comparative Example 1, and the red phosphors of Examples 5 and 6 The phosphor can improve the relative intensity of cathodoluminescence by 20 to 30% compared to Comparative Example 1. Furthermore, as shown in Table 1, the red phosphors of Examples 7 to 10 can improve the cathode luminescence relative intensity by about 20 to 60% as compared with Comparative Example 1.
また、表１及び図３に示されるように、実施例１及び３は、比較例１に比して、同一波長（６５０ｎｍ近傍）において、３００％以上のカソードルミネッセンス相対強度を有する。 As shown in Table 1 and FIG. 3, Examples 1 and 3 have a cathode luminescence relative intensity of 300% or more at the same wavelength (near 650 nm) as compared with Comparative Example 1.
［試験例１］
（Ｃａ１−ｘＳｒｘ）Ｓ：Ｅｕ，Ｆ（０≦ｘ≦１）で示される赤色蛍光体のカルシウムとストロンチウムの混合割合を変えてフォトルミネッセンス特性を評価した。その結果を図４に示す。 [Test Example 1]
Photoluminescence characteristics were evaluated by changing the mixing ratio of calcium and strontium of the red phosphor represented by (Ca 1-x Sr x ) S: Eu , F (0 ≦ x ≦ 1). The result is shown in FIG.
図４の結果から、ＣａＳ：Ｅｕ，Ｆの極大発光波長は６５０ｎｍであり、ＳｒＳ：Ｅｕ，Ｆの極大発光波長は５９０ｎｍであり、カルシウムとストロンチウムの量を調整することによって、上記発光波長の間で発光波長を任意に制御することが判る。From the results of FIG. 4, the maximum emission wavelength of CaS: Eu , F is 650 nm, the maximum emission wavelength of SrS: Eu , F is 590 nm, and the above emission wavelengths can be adjusted by adjusting the amounts of calcium and strontium. It can be seen that the emission wavelength is arbitrarily controlled.
［試験例２］
（Ｃａ１−ｘＳｒｘ）Ｓ：Ｅｕ，Ｆ（０≦ｘ≦１）で示される赤色蛍光体と（Ｃａ１− ｘＳｒｘ）Ｓ：Ｅｕ，Ａｌ，Ｆ（０≦ｘ≦１）で示される赤色蛍光体の極大発光波長を比較した。結果を図５に示す。 [Test Example 2]
(Ca 1−x Sr x ) S: Eu , F (0 ≦ x ≦ 1) and (Ca 1− x Sr x ) S: Eu, Al , F (0 ≦ x ≦ 1) The maximum emission wavelengths of the red phosphors shown were compared. The results are shown in FIG.
図５の結果から、増感剤であるアルミニウムの含有の有無に拘わらず、極大発光波長に変化はなかった。From the results shown in FIG. 5, the maximum emission wavelength did not change regardless of the presence or absence of aluminum as a sensitizer.
本発明に係る赤色蛍光体及びその製造方法は、電解放射型ディスプレイ、プラズマディスプレイ、エレクトロルミネッセンス等のディスプレイデバイスの用途に使用できるほか、青色ＬＥＤ励起用蛍光体等の用途に適用でき、特にエレクトロルミネッセンスのディスプレイデバイスの用途に好適に用いることができる。 The red phosphor and the manufacturing method thereof according to the present invention can be applied to uses of display devices such as electrolytic emission displays, plasma displays, and electroluminescence, and can also be applied to uses such as phosphors for exciting blue LEDs, and in particular, electroluminescence. It can use suitably for the use of the display device of this.
Claims (11)
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｆ … … (１)
（但し、ＡはＡｌ，Ｇａ，Ｉｎから選択される少なくとも１種を表す） A red phosphor represented by the following general formula (1).
(Ca, Sr) S: Eu, A, F (1)
(However, A represents at least one selected from Al, Ga, and In)
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ｒｂ，Ｆ … … (２) A red phosphor represented by the following formula (2).
(Ca, Sr) S: Eu, Rb, F (2)
（Ｃａ，Ｓｒ）Ｓ：Ｅｕ，Ａ，Ｒｂ，Ｆ … … (３)
（但し、ＡはＡｌ，Ｇａ，Ｉｎから選択される少なくとも１種を表す） A red phosphor represented by the following general formula (3).
(Ca, Sr) S: Eu, A, Rb, F (3)
(However, A represents at least one selected from Al, Ga, and In)
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| US8278816B2 (en) | 2004-09-30 | 2012-10-02 | Global Tungsten & Powders Corp. | High CRI electroluminescent lamp |
| JP4879567B2 (en) * | 2005-11-25 | 2012-02-22 | 電気化学工業株式会社 | Method for producing sialon phosphor and lighting apparatus using phosphor obtained thereby |
| WO2008102518A1 (en) * | 2007-02-19 | 2008-08-28 | Mitsui Mining & Smelting Co., Ltd. | Red phosphor, red light emitting element or device, and white light emitting element or device |
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| CN104471025B (en) | 2012-10-23 | 2016-04-20 | 三井金属矿业株式会社 | Fluor, LED luminous element and light supply apparatus |
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