JP2004099692A - Zinc oxide phosphor - Google Patents
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- JP2004099692A JP2004099692A JP2002261451A JP2002261451A JP2004099692A JP 2004099692 A JP2004099692 A JP 2004099692A JP 2002261451 A JP2002261451 A JP 2002261451A JP 2002261451 A JP2002261451 A JP 2002261451A JP 2004099692 A JP2004099692 A JP 2004099692A
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- DLISVLVFJRCVJM-UHFFFAOYSA-N zinc oxygen(2-) phosphane Chemical compound [O--].P.[Zn++] DLISVLVFJRCVJM-UHFFFAOYSA-N 0.000 title abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 137
- 239000011787 zinc oxide Substances 0.000 abstract description 70
- 238000010894 electron beam technology Methods 0.000 abstract description 22
- 238000010586 diagram Methods 0.000 abstract description 4
- 229960001296 zinc oxide Drugs 0.000 description 41
- 238000000295 emission spectrum Methods 0.000 description 17
- 239000011572 manganese Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012190 activator Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000608 laser ablation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 208000016169 Fish-eye disease Diseases 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 238000005136 cathodoluminescence Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical group [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
【課題】電子線に対して安定で、輝度の高い酸化亜鉛系蛍光体を提供する。
【解決手段】Ｙの濃度が８〜２５モル％、Ｔｂの濃度が３〜１０モル％であるＹとＴｂを共付活してなるＺｎＯ青色発光蛍光体、Ｇｅの濃度が２８〜３６モル％、Ｍｎの濃度が０．５〜５モル％であるＧｅとＭｎを共付活してなるＺｎＯ緑色発光蛍光体、およびＹの濃度が１０〜２０モル％、Ｅｕの濃度が０．２〜５モル％、Ｖの濃度が０．２〜８モル％であるＹとＥｕとＶを共付活してなるＺｎＯ赤色発光蛍光体。
【選択図】 なしAn object of the present invention is to provide a zinc oxide phosphor which is stable to an electron beam and has high luminance.
A ZnO blue light-emitting phosphor in which Y and Tb are co-activated with a Y concentration of 8 to 25 mol% and a Tb concentration of 3 to 10 mol%, and a Ge concentration of 28 to 36 mol%. , A ZnO green light-emitting phosphor obtained by co-activating Ge and Mn having a Mn concentration of 0.5 to 5 mol%, a Y concentration of 10 to 20 mol%, and an Eu concentration of 0.2 to 5 mol%. A ZnO red light-emitting phosphor obtained by co-activating Y, Eu and V having a mol% and a V concentration of 0.2 to 8 mol%.
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、蛍光体材料、即ち、電子線により適当な条件で励起された時に可視領域の波長の発光を行う材料に係わり、特に、酸化亜鉛を母体とする酸化亜鉛系の蛍光体に関するものである。
【０００２】
本発明に係る青色発光蛍光体は、蛍光表示管、フラットパネルディスプレイおよびカソード・レイ・チューブ（ＣＲＴ）などに好適に使用できる。特に、フラットパネルディスプレイの１種であるＦＥＤ（フィールドエミッションディスプレイ）用蛍光体として好適である。
【０００３】
【従来の技術】
インフォーメイション・テクノロジー（ＩＴ）の進展に伴い、ディスプレイは今後ますます重要性を増すとともに、その需要も増加が期待されている。
現在、薄型のフラットパネルディスプレイ（ＦＰＤ）は液晶ディスプレイが中心であるが、プラズマディスプレイ（ＰＤＰ）、有機ＥＬディスプレイ、電界放出型ディスプレイ（（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ：ＦＥＤ）など、各種のＦＰＤが研究されている。
【０００４】
ＦＥＤはＣＲＴと同様にカソードルミネッセンスを基本原理とする発光型表示デバイスであるが、ＣＲＴが熱電子源を利用しているのに対して電界で電子を真空中に放出するコールドカソード（冷陰極）を電子源としている。今後、ＦＥＤが本格的ディスプレイとして市場に受け入れられるためにはカラー表示が必須であり、このためには高輝度かつ安定な３原色蛍光体が必要である。
【０００５】
現在、ＣＲＴに使用されている蛍光体としては、ＺｎＳ：Ａｇ（青色）、ＺｎＳ：Ｃｕ、Ａｌ（黄緑色）、Ｙ２Ｏ２Ｓ：Ｅｕ３＋（赤色）などがある。しかし、ＦＥＤ用蛍光体としてはより高輝度でかつ安定な蛍光体の開発が求められており、各種の発光蛍光体の研究が積極的に実施されている（例えば、特許文献１参照。）。
【０００６】
【特許文献１】
特開２００１−２１４１６１号公報
【０００７】
【発明が解決しようとする課題】
しかしながら、ＦＥＤ用の蛍光体として必要とされる重要な性質は、電子線照射に対して安定なことであるが、従来の硫化物系の蛍光体などは、電子線により蛍光体表面が分解、劣化し、硫化亜鉛が分解して発生した硫黄が真空中の残留ガス（殆どが水分）と反応して亜硫酸ガスとなって電子源表面に付着し電子放出特性が劣化するため、ＦＥＤ用蛍光体として適さないという問題がある。
【０００８】
本発明は、酸化物系の蛍光体、特に、酸化亜鉛を母体とする蛍光体（酸化亜鉛系蛍光体）が電子線照射に対して安定であることに着目して成されたもので、電子線に対して安定で、輝度の高い酸化亜鉛系蛍光体を提供することを課題としている。
また、本発明は、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系蛍光体を提供することを課題としている。
【０００９】
また、本発明は、電子線に対して安定で、輝度の高い酸化亜鉛系の青色発光蛍光体を提供することを課題としている。
また、本発明は、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系の青色発光蛍光体を提供することを課題としている。
【００１０】
また、本発明は、電子線に対して安定で、輝度の高い酸化亜鉛系の緑色発光蛍光体を提供することを課題としている。
また、本発明は、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系の緑色発光蛍光体を提供することを課題としている。
【００１１】
また、本発明は、電子線に対して安定で、輝度の高い酸化亜鉛系の赤色発光蛍光体を提供することを課題としている。
また、本発明は、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系の赤色発光蛍光体を提供することを課題としている。
【００１２】
【課題を解決するための手段】
本発明によれば、ＺｎＯにＹとＴｂを共付活して成ることを特徴とする青色発光蛍光体が提供される。
ここで、Ｙの濃度が８〜２５モル％であり、Ｔｂの濃度が３〜１０モル％であることが好ましい。
また、Ｙの濃度が１０〜２０モル％であり、Ｔｂの濃度が６〜９モル％であることが更に好ましい。
【００１３】
また、本発明によれば、ＺｎＯにＧｅとＭｎを共付活して成ることを特徴とする緑色発光蛍光体が提供される。
ここで、Ｇｅの濃度が２８〜３６モル％であり、Ｍｎの濃度が０．５〜５モル％であることが好ましい。
また、Ｇｅの濃度が３０〜３３モル％であり、Ｍｎの濃度が１〜３モル％であることが更に好ましい。
【００１４】
また、本発明によれば、ＺｎＯにＹとＥｕとＶを共付活して成ることを特徴とする赤色発光蛍光体が提供される。
ここで、Ｙの濃度が１０〜２０モル％であり、Ｅｕの濃度が０．２〜５モル％であり、Ｖの濃度が０．２〜８モル％であることが好ましい。
また、Ｙの濃度が１１〜１５モル％であり、Ｅｕの濃度が０．５〜２モル％であり、Ｖの濃度が０．５〜５モル％であることが更に好ましい。
【００１５】
【発明の実施の形態】
本発明者は、特にＦＥＤ用蛍光体として、電子線照射に安定で、低電圧で発光し、高輝度で寿命の長い酸化物系蛍光体の開発に鋭意努力した結果、驚くべきことに酸化亜鉛に各種の金属を付活した酸化亜鉛系蛍光体が優れた発色を示すことを見出し、本発明に到達した。
【００１６】
ＺｎＯ蛍光体（ＺｎＯ：Ｚｎ）は、低加速電子に対して優れた発光特性をもつ導電性緑色蛍光体として知られており、発光しきい値のアノード電圧、輝度などで優れている。しかしながらＺｎＯ蛍光体の欠点は緑色以外の発光が実現できていないことである。
ＺｎＯ蛍光体の発光は、もともと結晶中の酸素の欠損もしくは格子中に存在するＺｎによって形成される輻射遷移準位からの発光で、その中心波長は５０５ｎｍである。
【００１７】
ところが最近、ＺｎＯ−ＭｇＯ混合系蛍光体でＭｇ／Ｚｎ比を変えることにより、バンドギャップを３．３ｅＶ〜３．７ｅＶの範囲で制御できることが報告されＺｎＯ系の発光波長制御の可能性が示された。
我々はこれらの知見に基づき、酸化亜鉛を母体とする蛍光体である酸化亜鉛系蛍光体の研究を行い、ＺｎＯと各種の金属との組合せによる新規な蛍光体の開発に取組み本発明に到達した。即ち、本発明は、発光効率が良く、高輝度を示し、電子線照射に対し安定で新規なＺｎＯ系の各種の発光蛍光体を提供するが可能である。
【００１８】
本発明者は母体であるＺｎＯに各種の金属を付活してその蛍光を測定する研究を行っていたところ、特定の金属を付活剤として付活すると蛍光体が得られることを見出し鋭意研究を行い本発明に到達した。
具体的には、ＺｎＯにＹ（イットリウム）とＴｂ（トリビウム）を共付活すると青色発光蛍光体が得られることを見出した。即ち、ＺｎＯを母体とし、Ｙ及びＴｂを付活剤とする青色発光蛍光体を発明した。
【００１９】
また、ＺｎＯにＧｅ（ゲルマニウム）とＭｎ（マンガン）を共付活すると緑色発光蛍光体が得られることを見出した。即ち、ＺｎＯを母体とし、Ｇｅ及びＭｎを付活剤とする緑色発光蛍光体を発明した。
さらに、ＺｎＯにＹとＥｕ（ユーロピウム）とＶ（バナジウム）を共付活すると赤色発光蛍光体が得られることを見出した。即ち、ＺｎＯを母体とし、Ｙ、Ｅｕ及びＶを付活剤とする赤色発光蛍光体を発明した。
【００２０】
ＺｎＯ／Ｙ／Ｔｂの３成分系蛍光体について詳述すると、蛍光体に占めるＹの濃度が８〜２５モル％であり、Ｔｂの濃度が３〜１０モル％の範囲が青色発光に好適である。更に好ましい範囲としては、Ｙの濃度が１０〜２０モル％であり、Ｔｂの濃度が６〜９モル％である。
この範囲をはずれると青色発光を示さなくなり、又発色強度が弱くなるため実用的に意味がなくなる。青色の発光波長は中心が４６０〜４９０ｎｍである。
【００２１】
ＺｎＯ／Ｇｅ／Ｍｎの３成分系蛍光体について詳述すると、蛍光体に占めるＧｅの濃度は２８〜３６モル％であり、Ｍｎの濃度は０．５〜５モル％の範囲が緑色発光に好適である。更に好ましい範囲としては、Ｇｅの濃度が３０〜３３モル％であり、Ｍｎの濃度が１〜３モル％である。
この範囲をはずれると緑色発光を示さなくなり、又発光強度が弱くなるため実用的に意味がなくなる。緑色の発光波長は中心が５３０〜５４０ｎｍである。
【００２２】
ＺｎＯ／Ｙ／Ｅｕ／Ｖの４成分系蛍光体について詳述すると、蛍光体に占めるＹの濃度が１０〜２０モル％であり、Ｅｕの濃度が０．２〜５モル％であり、Ｖの濃度が０．２〜８モル％の範囲が赤色発光に好適である。更に好ましい範囲としては、Ｙの濃度が１１〜１５モル％であり、Ｅｕの濃度が０．５〜２モル％であり、Ｖの濃度が０．５〜５モル％である。
この範囲をはずれると赤色発光を示さなくなり、又発光強度が弱くなるため実用的に意味がなくなる。
【００２３】
前記各蛍光体は、フラットパネルディスプレイ、カソードレイチューブなどに好適であり、特にＦＥＤには好適である。これらの蛍光体の製造法はどのような方法で行っても良いが、一般的な方法としてはゾルゲル法あるいはレーザーアブレーション法などが用いられる。そして、一定の条件下でアンニーリングして蛍光体を製造する。
【００２４】
以上の通り、本実施の形態によれば、電子線に対して安定で、輝度の高い酸化亜鉛系の蛍光体を提供することが可能になる。また、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系蛍光体を提供することが可能になる。
また、本実施の形態によれば、電子線に対して安定で、輝度の高い酸化亜鉛系の青色発光蛍光体、緑色発光蛍光体、または、赤色発光蛍光体を提供することが可能になる。また、本実施の形態によれば、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系の青色発光蛍光体、緑色発光蛍光体、または、赤色発光蛍光体を提供することが可能になる。
【００２５】
【実施例】
次に、本発明の実施例に係る酸化亜鉛系蛍光体の製造方法、発光特性について具体的に説明する。
〔実施例１〕
実施例１では、ゾルゲル法を用いて本実施例に係る酸化亜鉛系蛍光体を製造した。
即ち、先ず、２．３ｇ（０．０１１８モル）のＹＣｌ３と１．８ｇ（０．００６８モル）のＴｂＣｌ３を８０ｍｌの水に溶解した溶液に、５．３ｇ（０．０６５４モル）のＺｎＯを添加した。
【００２６】
十分に撹拌した後に水分を蒸発させ、生成した多孔性の固体を良くかき混ぜてルツボに入れた。ルツボを空気中９００℃で１２時間加熱した。得られた生成物が酸化亜鉛系蛍光体であり、白色の粉末であった。前記酸化亜鉛系蛍光体は１４モル％のＹと８モル％のＴｂを含んでいた。前記酸化亜鉛系蛍光体は青色発光蛍光体であり、その発光光の主波長は４７０〜４９５ｎｍ（青色）であった。本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性１０１として図１に示す。
【００２７】
［実施例２］
実施例２は、レーザーアブレーション法を用いて酸化亜鉛系蛍光体を製造した例であり、２つのセラミックターゲット（第１、第２のターゲット）にレーザーを照射して蒸発させた。
第１のターゲットはＺｎＯで、第２のターゲットは３５モル％のＴｂ２Ｏ３をドープしたＹ２Ｏ３よりなる。強力な５ＷのＫｒＦエキシマレーザーを用いて交互にターゲットを照射し、蒸発させた。蒸発した物質は、ターゲットから７０ｍｍ離れて配設すると共に５００℃に加熱した基板に堆積させた。
【００２８】
夫々のターゲット物質の堆積速度は予備的な計算で算出し、生成した堆積フィルム中のＹの濃度は１０モル％になるように調節した。実際に生成した堆積フィルムは、Ｙの濃度は１２モル％、Ｔｂの濃度が６モル％であることをＥＰＭＡ（電子線プローブ局所分析法）で確認した。６時間の堆積後、フィルムの厚さは１μｍであった。
【００２９】
得られたフィルムが酸化亜鉛蛍光体であり、フィルムは青色の蛍光を示した。前記酸化亜鉛系蛍光体は青色発光蛍光体であり、その発光光の主波長は４７０〜４９５ｎｍであった。
本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性１０２として図１に示す。発光スペクトル特性１０１と発光スペクトル特性１０２のスペクトル強度の違いは膜厚の差によるものである。
【００３０】
〔実施例３〕
実施例３では、ゾルゲル法を用いて本実施例に係る酸化亜鉛系蛍光体を製造した。
即ち、先ず、５．４ｇ（０．０６５モル）のＺｎＯと０．１６ｇ（０．００１２７モル）のＭｎＣｌ２を８０ｍｌの水に添加した溶液に、１．５１ｇ（０．０９７モル）のＧｅ（ＯＣ２Ｈ５）２を添加した。十分に撹拌後、溶液を室温にて２４時間保存してゲル化させた。ゲル状物を２００℃で１２時間乾燥させてルツボに入れた。ルツボを空気中で１１００℃で１２時間加熱した。
【００３１】
得られた生成物が酸化亜鉛系蛍光体であり、白色の粉末であった。前記酸化亜鉛系蛍光体は３３モル％のＧｅと１．３モル％のＭｎを含んでいた。前記酸化亜鉛系蛍光体は緑色発光蛍光体であり、その発光光の主波長は５３７ｎｍ（緑）であった。本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性２０１として図２に示す。
【００３２】
［実施例４］
実施例４は、レーザーアブレーション法を用いて酸化亜鉛系蛍光体を製造した例であり、２つのセラミックターゲット（第１、第２のターゲット）にレーザーを照射して蒸発させた。
第１のターゲットは３モル％のＭｎ２Ｏ３をドープしたＺｎＯで、第２のターゲットはＧｅＯ２よりなる。強力な５ＷのＫｒＦエキシマレーザーを用いて交互にターゲットを照射し、蒸発させた。蒸発した物質は各ターゲットから７０ｍｍ離れると共に５００℃に加熱した基板に堆積させた。
【００３３】
夫々のターゲット物質の堆積速度は予備的な計算で算出し、生成した堆積フィルム中のＧｅの濃度は３０モル％になるように調節した。実際に生成した堆積フィルムはＧｅの濃度は３０モル％、Ｍｎの濃度が２モル％であることをＥＰＭＡ（電子線プローブ局所分析法）で確認した。６時間の堆積後、フィルムの厚さは１μｍであった。フィルムは空気中で３時間、７００℃でアニールした。
【００３４】
得られたフィルムが酸化亜鉛蛍光体であり、フィルムは緑色の蛍光を示した。前記酸化亜鉛系蛍光体は緑色発光蛍光体であり、その発光光の主波長は５４０ｎｍであった。
本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性２０２として図２に示す。発光スペクトル特性２０１と発光スペクトル特性２０２のスペクトル強度の違いは膜厚の差によるものである。
【００３５】
〔実施例５〕
実施例５では、ゾルゲル法を用いて本実施例に係る酸化亜鉛系蛍光体を製造した。
即ち、先ず、０．６３ｇ（０．００３２モル）のＹＣｌ３と０．０５６ｇ（０．０００２モル）のＥｕＣｌ３を８０ｍｌの水に溶解した溶液に１．８ｇ（０．０２２２モル）のＺｎＯと０．０２５ｇ（０．０００２モル）のＮＨ４ＶＯ３を添加した。十分に撹拌後、過剰の水を蒸発させ、生成した多孔質の固体をよく混合した後ルツボに入れた。ルツボを空気中で９００℃で、１２時間加熱した。
【００３６】
得られた生成物が酸化亜鉛系蛍光体であり、白色の粉末であった。前記酸化亜鉛系蛍光体は１２モル％のＹと０．８モル％のＥｕと０．８モル％のＶを含んでいた。前記酸化亜鉛系蛍光体は赤色発光蛍光体である、その発光光の主波長は６１８ｎｍ（赤色）であった。本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性３０１として図３に示す。
【００３７】
［実施例６］
実施例６は、レーザーアブレーション法を用いて酸化亜鉛系蛍光体を製造した例であり、２つのセラミックターゲット（第１、第２のターゲット）にレーザーを照射して蒸発させた。
第１のターゲットは０．６モル％のＶ２Ｏ５をドープしたＺｎＯで、第２のターゲットは１３モル％のＥｕ２Ｏ３をドープしたＹ２Ｏ３よりなる。強力な５ＷのＫｒＦエキシマレーザーを用いて交互にターゲットを照射し、蒸発させた。蒸発した物質は各ターゲットから７０ｍｍ離れると共に５００℃に加熱した基板に堆積させた。
【００３８】
夫々のターゲット物質の堆積速度は予備的な計算で算出し、生成した堆積フィルム中のＹの濃度は１２モル％になるように調節した。実際に生成した堆積フィルムはＹの濃度は１４モル％、Ｅｕの濃度が１．５モル％、Ｖの濃度が０．５モル％であることをＥＰＭＡ（電子線プローブ局所分析法）で確認した。６時間の堆積後、フィルムの厚さは１μｍであった。フィルムは空気中で３時間、７００℃でアニールした。
【００３９】
得られたフィルムが酸化亜鉛蛍光体であり、フィルムは赤色の蛍光を示した。前記酸化亜鉛系蛍光体は赤色発光蛍光体であり、その発光光の主波長は６２０ｎｍであった。
本実施例に係る蛍光体の発光スペクトルを、発光スペクトル特性３０２として図３に示す。発光スペクトル特性３０１と発光スペクトル特性３０２のスペクトル強度の違いは膜厚の差によるものである。
【００４０】
【発明の効果】
本発明によれば、電子線に対して安定で、輝度の高い酸化亜鉛系蛍光体を提供することが可能になる。また、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系蛍光体を提供することが可能になる。
また、本発明によれば、電子線に対して安定で、輝度の高い酸化亜鉛系の青色発光蛍光体、緑色発光蛍光体、または、赤色発光蛍光体を提供することが可能になる。
また、本発明によれば、電子線に対して安定で、輝度が高く、ＦＥＤに好適な酸化亜鉛系の青色発光蛍光体、緑色発光蛍光体、または、赤色発光蛍光体を提供することが可能になる。
【図面の簡単な説明】
【図１】本発明の実施例に係る青色発光蛍光体の発光スペクトル特性を示す図である。
【図２】本発明の実施例に係る緑色発光蛍光体の発光スペクトル特性を示す図である。
【図３】本発明の実施例に係る赤色発光蛍光体の発光スペクトル特性を示す図である。
【符号の説明】
１０１、１０２、２０１、２０２、３０１、３０２・・・発光スペクトル特性[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a phosphor material, that is, a material that emits light of a wavelength in the visible region when excited under an appropriate condition by an electron beam, and more particularly to a zinc oxide-based phosphor having zinc oxide as a base material. is there.
[0002]
The blue light emitting phosphor according to the present invention can be suitably used for a fluorescent display tube, a flat panel display, a cathode ray tube (CRT), and the like. In particular, it is suitable as a phosphor for FED (field emission display), which is a kind of flat panel display.
[0003]
[Prior art]
With the development of information technology (IT), displays are becoming increasingly important in the future, and demand for them is expected to increase.
Currently, thin flat panel displays (FPDs) are mainly liquid crystal displays, but various types of FPDs such as plasma displays (PDPs), organic EL displays, and field emission displays ((Field Emission Display): FED) have been studied. I have.
[0004]
The FED is a light-emitting display device based on cathodoluminescence, similar to a CRT, but a cold cathode (cold cathode) that emits electrons into a vacuum by an electric field while a CRT uses a thermionic electron source. Is the electron source. In the future, color display is indispensable in order for the FED to be accepted as a full-scale display in the market, and a high-luminance and stable three-primary-color phosphor is required for this.
[0005]
Currently, phosphors used in CRTs include ZnS: Ag (blue), ZnS: Cu, Al (yellow-green), and Y 2 O 2 S: Eu 3+ (red). However, there is a demand for the development of a phosphor having higher luminance and stability as a phosphor for FED, and various kinds of light-emitting phosphors have been actively researched (for example, see Patent Document 1).
[0006]
[Patent Document 1]
JP 2001-214161 A
[Problems to be solved by the invention]
However, an important property required as a phosphor for FED is that it is stable against electron beam irradiation, but the phosphor surface of a conventional sulfide-based phosphor and the like is decomposed by an electron beam. The sulfur produced by the decomposition and decomposition of zinc sulfide reacts with the residual gas (mostly water) in vacuum to form sulfurous acid gas, which adheres to the electron source surface and deteriorates the electron emission characteristics. There is a problem that is not suitable as.
[0008]
The present invention focuses on the fact that oxide-based phosphors, particularly phosphors based on zinc oxide (zinc oxide-based phosphors), are stable against electron beam irradiation. It is an object of the present invention to provide a zinc oxide-based phosphor that is stable to light and has high luminance.
Another object of the present invention is to provide a zinc oxide-based phosphor that is stable to electron beams, has high luminance, and is suitable for FEDs.
[0009]
It is another object of the present invention to provide a zinc oxide-based blue light-emitting phosphor that is stable to an electron beam and has high luminance.
Another object of the present invention is to provide a zinc-oxide-based blue light-emitting phosphor that is stable to electron beams, has high luminance, and is suitable for FEDs.
[0010]
Another object of the present invention is to provide a zinc oxide-based green light-emitting phosphor that is stable to an electron beam and has high luminance.
Another object of the present invention is to provide a zinc oxide-based green light-emitting phosphor that is stable to electron beams, has high luminance, and is suitable for FEDs.
[0011]
Another object of the present invention is to provide a zinc oxide-based red light-emitting phosphor that is stable to an electron beam and has high luminance.
Another object of the present invention is to provide a zinc oxide-based red light-emitting phosphor that is stable to an electron beam, has high luminance, and is suitable for an FED.
[0012]
[Means for Solving the Problems]
According to the present invention, there is provided a blue light-emitting phosphor characterized in that ZnO is co-activated with Y and Tb.
Here, it is preferable that the concentration of Y is 8 to 25 mol% and the concentration of Tb is 3 to 10 mol%.
More preferably, the concentration of Y is 10 to 20 mol%, and the concentration of Tb is 6 to 9 mol%.
[0013]
Further, according to the present invention, there is provided a green light-emitting phosphor characterized in that Ge and Mn are co-activated with ZnO.
Here, it is preferable that the concentration of Ge is 28 to 36 mol% and the concentration of Mn is 0.5 to 5 mol%.
More preferably, the concentration of Ge is 30 to 33 mol%, and the concentration of Mn is 1 to 3 mol%.
[0014]
Further, according to the present invention, there is provided a red light-emitting phosphor characterized in that Y, Eu and V are co-activated with ZnO.
Here, it is preferable that the concentration of Y is 10 to 20 mol%, the concentration of Eu is 0.2 to 5 mol%, and the concentration of V is 0.2 to 8 mol%.
More preferably, the concentration of Y is 11 to 15 mol%, the concentration of Eu is 0.5 to 2 mol%, and the concentration of V is 0.5 to 5 mol%.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
The present inventors have made intensive efforts to develop an oxide-based phosphor which is stable to electron beam irradiation, emits light at a low voltage, has high luminance, and has a long life. Have found that zinc oxide-based phosphors activated with various metals exhibit excellent color development, and have reached the present invention.
[0016]
A ZnO phosphor (ZnO: Zn) is known as a conductive green phosphor having excellent emission characteristics with respect to low-acceleration electrons, and has excellent emission threshold anode voltage, luminance, and the like. However, a disadvantage of the ZnO phosphor is that emission of light other than green cannot be realized.
The light emission of the ZnO phosphor is light emission from a radiation transition level formed by oxygen deficiency in the crystal originally or Zn existing in the lattice, and its central wavelength is 505 nm.
[0017]
However, recently, it has been reported that the band gap can be controlled in the range of 3.3 eV to 3.7 eV by changing the Mg / Zn ratio of the ZnO-MgO mixed phosphor, and the possibility of controlling the emission wavelength of the ZnO-based phosphor has been shown. Was.
Based on these findings, we conducted research on zinc oxide-based phosphors, which are phosphors based on zinc oxide, and worked on the development of new phosphors by combining ZnO with various metals, and reached the present invention. . That is, the present invention can provide a variety of novel ZnO-based phosphors that exhibit good luminous efficiency, exhibit high luminance, and are stable to electron beam irradiation.
[0018]
The present inventor has been conducting research on activating various metals on ZnO, which is a base material, and measuring the fluorescence, and has found that a phosphor can be obtained by activating a specific metal as an activator. And arrived at the present invention.
Specifically, it has been found that a blue light-emitting phosphor can be obtained when Y (yttrium) and Tb (tribium) are co-activated with ZnO. That is, a blue light emitting phosphor using ZnO as a base material and Y and Tb as activators was invented.
[0019]
Further, they have found that a green light-emitting phosphor can be obtained by co-activating Ge (germanium) and Mn (manganese) with ZnO. That is, the inventors have invented a green light-emitting phosphor using ZnO as a base and Ge and Mn as activators.
Further, they have found that a red-emitting phosphor can be obtained when Y, Eu (europium) and V (vanadium) are co-activated on ZnO. That is, the inventors have invented a red light-emitting phosphor using ZnO as a base and Y, Eu and V as activators.
[0020]
The ZnO / Y / Tb ternary phosphor is described in detail. The concentration of Y in the phosphor is 8 to 25 mol%, and the concentration of Tb in the range of 3 to 10 mol% is suitable for blue light emission. . More preferably, the concentration of Y is 10 to 20 mol% and the concentration of Tb is 6 to 9 mol%.
If the ratio is out of this range, blue light is not emitted, and the color intensity is weakened, so that it is practically meaningless. The emission wavelength of blue light has a center of 460 to 490 nm.
[0021]
The ternary phosphor of ZnO / Ge / Mn will be described in detail. The concentration of Ge in the phosphor is 28 to 36 mol%, and the concentration of Mn in the range of 0.5 to 5 mol% is suitable for green light emission. It is. More preferably, the concentration of Ge is 30 to 33 mol%, and the concentration of Mn is 1 to 3 mol%.
Outside of this range, green light emission will not be exhibited, and the light emission intensity will be weak, which is practically meaningless. The emission wavelength of green light has a center of 530 to 540 nm.
[0022]
The ZnO / Y / Eu / V four-component phosphor is described in detail. The concentration of Y in the phosphor is 10 to 20 mol%, the concentration of Eu is 0.2 to 5 mol%, and A concentration in the range of 0.2 to 8 mol% is suitable for red light emission. More preferably, the concentration of Y is 11 to 15 mol%, the concentration of Eu is 0.5 to 2 mol%, and the concentration of V is 0.5 to 5 mol%.
Outside of this range, red light emission will not be exhibited, and the light emission intensity will be weak, which is practically meaningless.
[0023]
Each of the phosphors is suitable for a flat panel display, a cathode ray tube, and the like, and is particularly suitable for an FED. These phosphors may be produced by any method, but a general method such as a sol-gel method or a laser ablation method is used. Then, annealing is performed under certain conditions to produce a phosphor.
[0024]
As described above, according to the present embodiment, it is possible to provide a zinc oxide-based phosphor that is stable to an electron beam and has high luminance. Further, it is possible to provide a zinc oxide-based phosphor which is stable to an electron beam, has high luminance, and is suitable for an FED.
Further, according to the present embodiment, it is possible to provide a zinc oxide-based blue light-emitting phosphor, a green light-emitting phosphor, or a red light-emitting phosphor that is stable to an electron beam and has high luminance. Further, according to the present embodiment, it is possible to provide a zinc oxide-based blue light-emitting phosphor, a green light-emitting phosphor, or a red light-emitting phosphor that is stable to an electron beam, has high luminance, and is suitable for an FED. Becomes possible.
[0025]
【Example】
Next, a method for producing a zinc oxide-based phosphor according to an example of the present invention and light emission characteristics will be specifically described.
[Example 1]
In Example 1, the zinc oxide-based phosphor according to the present example was manufactured using the sol-gel method.
First, 5.3 g (0.0654 mol) of ZnO was added to a solution of 2.3 g (0.0118 mol) of YCl 3 and 1.8 g (0.0068 mol) of TbCl 3 in 80 ml of water. Was added.
[0026]
After sufficient stirring, the water was evaporated and the resulting porous solid was mixed well and placed in a crucible. The crucible was heated in air at 900 ° C. for 12 hours. The obtained product was a zinc oxide-based phosphor and was a white powder. The zinc oxide-based phosphor contained 14 mol% of Y and 8 mol% of Tb. The zinc oxide-based phosphor was a blue light-emitting phosphor, and the main wavelength of the emitted light was 470 to 495 nm (blue). The emission spectrum of the phosphor according to this example is shown in FIG.
[0027]
[Example 2]
Example 2 is an example in which a zinc oxide-based phosphor was manufactured by using a laser ablation method. Two ceramic targets (first and second targets) were irradiated with a laser and evaporated.
The first target is ZnO, and the second target is Y 2 O 3 doped with 35 mol% of Tb 2 O 3 . The target was irradiated alternately with a powerful 5 W KrF excimer laser and evaporated. The evaporated material was deposited on a substrate placed at a distance of 70 mm from the target and heated to 500 ° C.
[0028]
The deposition rate of each target material was calculated by preliminary calculation, and the concentration of Y in the formed deposited film was adjusted to be 10 mol%. The deposited film actually produced was confirmed by EPMA (Electron Beam Probe Local Analysis) to have a Y concentration of 12 mol% and a Tb concentration of 6 mol%. After 6 hours of deposition, the film thickness was 1 μm.
[0029]
The obtained film was a zinc oxide phosphor, and the film showed blue fluorescence. The zinc oxide-based phosphor was a blue light-emitting phosphor, and the main wavelength of the emitted light was 470 to 495 nm.
The emission spectrum of the phosphor according to this example is shown in FIG. The difference between the spectral intensities of the emission spectrum characteristic 101 and the emission spectrum characteristic 102 is due to the difference in film thickness.
[0030]
[Example 3]
In Example 3, the zinc oxide-based phosphor according to this example was manufactured using the sol-gel method.
That is, first, 1.51 g (0.097 mol) of Ge (0.097 mol) was added to a solution obtained by adding 5.4 g (0.065 mol) of ZnO and 0.16 g (0.00127 mol) of MnCl 2 to 80 ml of water. was added OC 2 H 5) 2. After thorough stirring, the solution was stored at room temperature for 24 hours to gel. The gel was dried at 200 ° C. for 12 hours and placed in a crucible. The crucible was heated at 1100 ° C. in air for 12 hours.
[0031]
The obtained product was a zinc oxide-based phosphor and was a white powder. The zinc oxide-based phosphor contained 33 mol% of Ge and 1.3 mol% of Mn. The zinc oxide-based phosphor was a green light-emitting phosphor, and the main wavelength of the emitted light was 537 nm (green). The emission spectrum of the phosphor according to this example is shown in FIG.
[0032]
[Example 4]
Example 4 is an example in which a zinc oxide-based phosphor was manufactured by using a laser ablation method, and two ceramic targets (first and second targets) were irradiated with a laser and evaporated.
The first target is ZnO doped with 3 mol% of Mn 2 O 3 , and the second target is made of GeO 2 . The target was irradiated alternately with a powerful 5 W KrF excimer laser and evaporated. The evaporated material was deposited on a substrate heated to 500 ° C. at a distance of 70 mm from each target.
[0033]
The deposition rate of each target material was calculated by preliminary calculation, and the concentration of Ge in the formed deposited film was adjusted to be 30 mol%. The deposited film actually formed was confirmed by EPMA (Electron Beam Probe Local Analysis) to have a Ge concentration of 30 mol% and a Mn concentration of 2 mol%. After 6 hours of deposition, the film thickness was 1 μm. The film was annealed at 700 ° C. for 3 hours in air.
[0034]
The resulting film was a zinc oxide phosphor and the film exhibited green fluorescence. The zinc oxide-based phosphor was a green light-emitting phosphor, and the main wavelength of the emitted light was 540 nm.
The emission spectrum of the phosphor according to this example is shown in FIG. The difference between the spectral intensities of the
[0035]
[Example 5]
In Example 5, the zinc oxide-based phosphor according to this example was manufactured using the sol-gel method.
That is, first, 1.8 g (0.0222 mol) of ZnO was added to a solution obtained by dissolving 0.63 g (0.0032 mol) of YCl 3 and 0.056 g (0.0002 mol) of EuCl 3 in 80 ml of water. 0.025 g (0.0002 mol) of NH 4 VO 3 was added. After sufficient stirring, excess water was evaporated and the resulting porous solid was mixed well and placed in a crucible. The crucible was heated at 900 ° C. in air for 12 hours.
[0036]
The obtained product was a zinc oxide-based phosphor and was a white powder. The zinc oxide phosphor contained 12 mol% of Y, 0.8 mol% of Eu, and 0.8 mol% of V. The zinc oxide-based phosphor was a red light-emitting phosphor, and the main wavelength of the emitted light was 618 nm (red). FIG. 3 shows an emission spectrum of the phosphor according to this example as an
[0037]
[Example 6]
Example 6 is an example in which a zinc oxide-based phosphor was manufactured by using a laser ablation method. Two ceramic targets (first and second targets) were irradiated with a laser and evaporated.
The first target is made of ZnO doped with 0.6 mol% of V 2 O 5 , and the second target is made of Y 2 O 3 doped with 13 mol% of Eu 2 O 3 . The target was irradiated alternately with a powerful 5 W KrF excimer laser and evaporated. The evaporated material was deposited on a substrate heated to 500 ° C. at a distance of 70 mm from each target.
[0038]
The deposition rate of each target material was calculated by preliminary calculation, and the concentration of Y in the formed deposited film was adjusted to be 12 mol%. It was confirmed by EPMA (Electron Beam Probe Local Analysis) that the actually formed deposited film had a Y concentration of 14 mol%, an Eu concentration of 1.5 mol%, and a V concentration of 0.5 mol%. . After 6 hours of deposition, the film thickness was 1 μm. The film was annealed at 700 ° C. for 3 hours in air.
[0039]
The obtained film was a zinc oxide phosphor, and the film showed red fluorescence. The zinc oxide-based phosphor was a red light-emitting phosphor, and the main wavelength of the emitted light was 620 nm.
The emission spectrum of the phosphor according to this example is shown in FIG. The difference between the spectral intensities of the emission spectrum characteristic 301 and the emission spectrum characteristic 302 is due to the difference in film thickness.
[0040]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, it becomes stable with respect to an electron beam, and it becomes possible to provide a zinc oxide type fluorescent substance with high brightness. Further, it is possible to provide a zinc oxide-based phosphor which is stable to an electron beam, has high luminance, and is suitable for an FED.
Further, according to the present invention, it is possible to provide a zinc oxide-based blue light-emitting phosphor, a green light-emitting phosphor, or a red light-emitting phosphor that is stable to an electron beam and has high luminance.
Further, according to the present invention, it is possible to provide a zinc oxide-based blue light-emitting phosphor, a green light-emitting phosphor, or a red light-emitting phosphor that is stable to an electron beam, has high luminance, and is suitable for an FED. become.
[Brief description of the drawings]
FIG. 1 is a diagram showing emission spectrum characteristics of a blue light emitting phosphor according to an example of the present invention.
FIG. 2 is a diagram showing emission spectrum characteristics of a green light emitting phosphor according to an example of the present invention.
FIG. 3 is a diagram showing an emission spectrum characteristic of a red light emitting phosphor according to an example of the present invention.
[Explanation of symbols]
101, 102, 201, 202, 301, 302 ... emission spectrum characteristics
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002261451A JP2004099692A (en) | 2002-09-06 | 2002-09-06 | Zinc oxide phosphor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002261451A JP2004099692A (en) | 2002-09-06 | 2002-09-06 | Zinc oxide phosphor |
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| JP2004099692A true JP2004099692A (en) | 2004-04-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088085A1 (en) * | 2007-01-19 | 2008-07-24 | Toyota Jidosha Kabushiki Kaisha | Powdery phosphor and process for producing the same, and light emitting device, display device and fluorescent lamp containing powdery phosphor |
| JP2009191178A (en) * | 2008-02-14 | 2009-08-27 | Ulvac Japan Ltd | Method of manufacturing oxide phosphor |
| CN102796521A (en) * | 2011-05-23 | 2012-11-28 | 吉林师范大学 | Preparation method for ZnO nanoparticles with high luminescent property |
| CN102812105A (en) * | 2010-05-25 | 2012-12-05 | 海洋王照明科技股份有限公司 | Fluorescent Materials Used In Field Emission And Preparation Methods Thereof |
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2002
- 2002-09-06 JP JP2002261451A patent/JP2004099692A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008088085A1 (en) * | 2007-01-19 | 2008-07-24 | Toyota Jidosha Kabushiki Kaisha | Powdery phosphor and process for producing the same, and light emitting device, display device and fluorescent lamp containing powdery phosphor |
| JP2008174665A (en) * | 2007-01-19 | 2008-07-31 | Toyota Motor Corp | Powder phosphor and method for manufacturing the same, and light emitting device, display device and fluorescent lamp having powder phosphor |
| US8197713B2 (en) | 2007-01-19 | 2012-06-12 | Toyota Jidosha Kabushiki Kaisha | Fluorescent powder, process for producing the same, and light emitting device, display device, and fluorescent lamp containing fluorescent powder |
| JP2009191178A (en) * | 2008-02-14 | 2009-08-27 | Ulvac Japan Ltd | Method of manufacturing oxide phosphor |
| CN102812105A (en) * | 2010-05-25 | 2012-12-05 | 海洋王照明科技股份有限公司 | Fluorescent Materials Used In Field Emission And Preparation Methods Thereof |
| EP2578661A4 (en) * | 2010-05-25 | 2015-02-25 | Oceans King Lighting Science | Fluorescent materials used in field emission and preparation methods thereof |
| CN102796521A (en) * | 2011-05-23 | 2012-11-28 | 吉林师范大学 | Preparation method for ZnO nanoparticles with high luminescent property |
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