JP4938999B2 - Method for forming conductive phosphor thin film and method for producing thin film phosphor substrate - Google Patents
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 92
- 239000010409 thin film Substances 0.000 title claims description 92
- 239000000758 substrate Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010408 film Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 15
- 150000002602 lanthanoids Chemical class 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910002367 SrTiO Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005566 electron beam evaporation Methods 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 1
- 230000001133 acceleration Effects 0.000 description 14
- 239000011701 zinc Substances 0.000 description 12
- 238000007740 vapor deposition Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 6
- 229910001940 europium oxide Inorganic materials 0.000 description 5
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000000918 Europium Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
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Description
本発明は、導電性蛍光体薄膜の形成方法及び薄膜蛍光体基板の作製方法に関する。 The present invention relates to a method for manufacturing a conductive phosphor thin film forming method and thin film phosphor board of.
近年、ディスプレイの分野においてはフラットパネルディスプレイの発展が著しく、大型フラットパネルディスプレイの有力候補として、フィールドエミッションディスプレイ(ＦＥＤ)が注目されている。このＦＥＤ用の蛍光体として、粉末蛍光体と比べて平坦性に優れている、超高精細ディスプレイ用蛍光体である薄膜蛍光体が知られている。しかしながら、今までに、ＦＥＤ用蛍光体として薄膜蛍光体の実用例は報告されていない。この原因は、この薄膜蛍光体から発光した光はガラスを通して外部に取り出されるが、ガラスとの界面での反射(屈折)のためにガラス前面から効率よく光を取り出すことができず、光の波動効果によるガラス端面からの光の散逸が大きくなって、輝度の減少、視野角の減少、消費電力の増大という問題が生じるためである。 In recent years, the development of flat panel displays has been remarkable in the field of displays, and field emission displays (FEDs) have attracted attention as leading candidates for large flat panel displays. As a phosphor for this FED, a thin film phosphor that is excellent in flatness as compared with a powder phosphor and is a phosphor for an ultra-high-definition display is known. However, no practical examples of thin film phosphors have been reported so far as phosphors for FED. The reason for this is that light emitted from this thin film phosphor is extracted outside through the glass, but light cannot be extracted efficiently from the front of the glass due to reflection (refraction) at the interface with the glass. This is because the dissipation of light from the glass end face due to the effect becomes large, causing problems such as a reduction in luminance, a reduction in viewing angle, and an increase in power consumption.
上述したような従来からの問題点を解決するための薄膜蛍光体基板が提案されている(例えば、特許文献１参照)。この場合の薄膜蛍光体基板は、透明基板、導電膜、蛍光体薄膜、及び低屈折率膜を有する４層構造からなる。この蛍光体薄膜は、導電性を持たない酸化物からなるものである。この蛍光体薄膜はまた、その膜厚が１μｍ以下であり、母材にランタノイド元素が付活されたものであって、電子ビーム蒸着法又はスパッタ法により作製されている。また、低屈折率膜を設け、蛍光体薄膜から発光した光が透明基板の端面から放出されるのを防ぎ、十分な光を基板正面から取り出すことができるようにしている。しかし、このように構成された薄膜蛍光体基板をＦＥＤに用いるのには次のような問題が発生する虞れがある。ＦＥＤでは、その構造から放出される電子が低加速電圧であるので、放出された電子が蛍光体薄膜を通過できずに、蛍光体薄膜表面にチャージアップしてしまい、十分な発光輝度が得られなくなるという虞れがある。
本発明の課題は、上記した従来技術の問題を解決することにあり、低加速電圧下においても蛍光体薄膜表面にチャージアップが起こることなく、十分な発光輝度が得られる導電性蛍光体薄膜の形成方法及び薄膜蛍光体基板の作製方法を提供することにある。 An object of the present invention is to solve the conventional above technical problems, low acceleration without charge-up occurs in the phosphor thin film surface even under voltage, sufficient conductivity phosphor thin film light-emitting luminance can be obtained and to provide a forming method and a manufacturing method of a thin film phosphor board of.
本発明は、上記課題を解決するために、蛍光体薄膜に導電性を付与することにより、低加速電圧下においても蛍光体薄膜表面にチャージアップが起こることなく、十分な発光輝度を得ることができるようしたものである。 In order to solve the above-mentioned problems, the present invention can obtain sufficient light emission luminance by imparting conductivity to a phosphor thin film without causing charge-up on the surface of the phosphor thin film even under a low acceleration voltage. It is something that can be done.
本発明の導電性蛍光体薄膜の形成方法は、Ｙ ２ Ｏ ３ 、Ｇｄ ２ Ｏ ３ 、ＺｎＧａ ２ Ｏ ４ 及びＳｒＴｉＯ ３ から選ばれた少なくとも一種の酸化物からなる母材酸化物と、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、及びルテチウムから選ばれた少なくとも一種のランタノイド元素からなる付活材と、導電性酸化物となり得るＺｎ、Ｉｎ、Ｓｎ、Ｃｒ、Ｍｏ、Ｏｓ、Ｒｅ、Ｎｂ、Ｖ、Ｗ、Ｓｍ、Ｉｒ、Ｒｕ、Ｎｄ、Ｌａ、及びＴｉから選ばれた少なくとも１種の金属とを多元蒸着し、次いでこの多元蒸着したものを大気中で焼成することにより導電性蛍光体薄膜を形成することを特徴とする。この場合、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、及びルテチウムから選ばれた少なくとも一種のランタノイド元素からなる付活材で付活されたＹ ２ Ｏ ３ 、Ｇｄ ２ Ｏ ３ 、ＺｎＧａ ２ Ｏ ４ 及びＳｒＴｉＯ ３ から選ばれた少なくとも一種の酸化物からなる母材酸化物と、導電性酸化物となり得るＺｎ、Ｉｎ、Ｓｎ、Ｃｒ、Ｍｏ、Ｏｓ、Ｒｅ、Ｎｂ、Ｖ、Ｗ、Ｓｍ、Ｉｒ、Ｒｕ、Ｎｄ、Ｌａ、及びＴｉから選ばれた少なくとも１種の金属とを多元蒸着し、次いでこの多元蒸着したものを大気中で焼成することにより導電性蛍光体薄膜を形成しても良い。 The method for forming a conductive phosphor thin film of the present invention includes a base material oxide composed of at least one oxide selected from Y 2 O 3 , Gd 2 O 3 , ZnGa 2 O 4 and SrTiO 3 , lanthanum, and cerium. , An active material made of at least one lanthanoid element selected from praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, and Zn, In that can be a conductive oxide , Sn, Cr, Mo, Os, Re, Nb, V, W, Sm, Ir, Ru, Nd, La, and at least one metal selected from Ti, and then this multi-source deposition A conductive phosphor thin film is formed by baking the material in the air . In this case, lanthanum, cerium, praseodymium, neodymium, samarium, was activated europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and activated with material made of at least one lanthanide element selected from lutetium A base oxide composed of at least one oxide selected from Y 2 O 3 , Gd 2 O 3 , ZnGa 2 O 4 and SrTiO 3; and Zn, In, Sn, Cr, Mo, which can be a conductive oxide , Multi- source deposition of at least one metal selected from Os, Re, Nb, V, W, Sm, Ir, Ru, Nd, La, and Ti, and then firing the multi- source deposition in the air A conductive phosphor thin film may be formed by the above.
本発明の薄膜蛍光体基板の作製方法は、透明基板上に導電膜を形成し、この導電膜上に上記導電性蛍光体薄膜の形成方法を用いて導電性蛍光体薄膜を形成して、３層構造の薄膜蛍光体基板を作製することを特徴とする。 The method for producing a thin film phosphor substrate of the present invention comprises forming a conductive phosphor film on a transparent substrate, forming a conductive phosphor thin film on the conductive film using the method for forming a conductive phosphor thin film, and 3 A thin-film phosphor substrate having a layer structure is produced.
また、本発明の薄膜蛍光体基板の作製方法は、透明基板上に上記導電性蛍光体薄膜の形成方法を用いて導電性蛍光体薄膜を形成し、その後この導電性蛍光体薄膜上に導電膜を形成して、３層構造の薄膜蛍光体基板を作製することを特徴とする。
The method for producing a thin film phosphor substrate according to the present invention comprises forming a conductive phosphor thin film on a transparent substrate by using the method for forming a conductive phosphor thin film, and then forming a conductive film on the conductive phosphor thin film. To form a thin film phosphor substrate having a three-layer structure.
本発明によれば、扱いやすい複数の酸化物を用いる同時蒸着により成膜し、導電性の付与された蛍光体薄膜を提供できると共に、この薄膜を用いた薄膜蛍光体基板を提供できるので、導電性を付与していない蛍光体薄膜の場合と比べて、蛍光体薄膜表面にチャージアップが起こることもなく、低加速電圧でも顕著な発光輝度が得られ、さらに蛍光体基板の長寿命化を図ることが可能になるという効果を奏する。 According to the present invention, it is possible to provide a phosphor thin film provided with conductivity by simultaneous vapor deposition using a plurality of easy-to-handle oxides, and to provide a thin film phosphor substrate using this thin film. Compared with a phosphor thin film that has not been imparted with the property, the surface of the phosphor thin film is not charged up, a remarkable light emission luminance is obtained even at a low acceleration voltage, and the life of the phosphor substrate is further extended. There is an effect that it becomes possible.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明によれば、導電性蛍光体薄膜は、上記したように、例えば、母材酸化物、付活材としてのランタノイド元素及び薄膜形成時に導電性酸化物となり得る物質を多元蒸着して成膜し、次いで大気中で焼成することにより形成される。また、本発明によれば、透明基板、導電膜(好ましくは透明導電膜)、及び上記導電性蛍光体薄膜を有する３層構造からなる薄膜蛍光体基板は、例えば、透明基板上に導電膜を形成し、この導電膜上に、母材酸化物と付活材としてのランタノイド元素と導電性酸化物となり得る物質とを電子ビーム蒸着法又はスパッタ法により多元蒸着し、次いで焼成することにより導電性蛍光体薄膜を形成して作製される。この場合、成膜プロセスは、電子ビーム蒸着法又はスパッタ法に加えてガス中蒸着法による同時蒸着により実施することも可能である。 According to the present invention, as described above, the conductive phosphor thin film is formed by, for example, multi-source vapor deposition of a base material oxide, a lanthanoid element as an activator, and a material that can become a conductive oxide when forming the thin film. And then fired in air. Further, according to the present invention, a thin film phosphor substrate having a three-layer structure having a transparent substrate, a conductive film (preferably a transparent conductive film), and the conductive phosphor thin film has a conductive film on a transparent substrate, for example. A conductive oxide is formed on the conductive film by subjecting the base material oxide, the lanthanoid element as the activator, and a substance that can become a conductive oxide to multi-source deposition by electron beam evaporation or sputtering, and then firing. It is produced by forming a phosphor thin film. In this case, the film formation process can be performed by simultaneous vapor deposition by gas vapor deposition in addition to electron beam vapor deposition or sputtering.
本発明で用いる母材酸化物としては、例えば、Ｙ２Ｏ３、Ｇｄ２Ｏ３、ＺｎＧａ２Ｏ４、及びＳｒＴｉＯ３等から選ばれた少なくとも一種の酸化物を挙げることができる。付活材としてのランタノイド元素は、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、及びルテチウムから選ばれた少なくとも一種であれば良い。また、導電性酸化物となり得る物質としては、大気中焼成により導電性酸化物を生成し得る金属、例えば、Ｚｎ、Ｉｎ、Ｓｎ、Ｃｒ、Ｍｏ、Ｏｓ、Ｒｅ、Ｎｂ、Ｖ、Ｗ、Ｓｍ、Ｉｒ、Ｒｕ、Ｎｄ、Ｌａ、及びＴｉから選ばれた少なくとも１種の金属を挙げることができる。 Examples of the base material oxide used in the present invention include at least one oxide selected from Y 2 O 3 , Gd 2 O 3 , ZnGa 2 O 4 , SrTiO 3 and the like. The lanthanoid element as the activator may be at least one selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, as a substance that can be a conductive oxide, a metal that can generate a conductive oxide by firing in the atmosphere, for example, Zn, In, Sn, Cr, Mo, Os, Re, Nb, V, W, Sm, Mention may be made of at least one metal selected from Ir, Ru, Nd, La and Ti.
スパッタ法で多元蒸着としての成膜プロセスを実施する場合には、そのスパッタリングターゲットとして、母材酸化物、付活材の酸化物及び導電性酸化物となり得る物質の酸化物のそれぞれで構成されたターゲットを用いれば良い。電子ビーム蒸着法及びガス中蒸着法の場合も、これらの母材酸化物、付活材の酸化物及び導電性酸化物となり得る物質の酸化物のそれぞれを構成し得る材料を用いれば良く、例えば、上記した材料を用いる。なお、上記酸化物の代わりに金属単体を用いて成膜しても良く、成膜後、焼成を行うため、最終的には酸化物となる。 When performing a film forming process as multi-source deposition by sputtering, each of the sputtering targets is composed of a base material oxide, an oxide of an activator, and an oxide of a substance that can be a conductive oxide. A target may be used. In the case of the electron beam vapor deposition method and the gas vapor deposition method, a material that can constitute each of the base material oxide, the oxide of the activator, and the oxide of the substance that can be a conductive oxide may be used. The materials described above are used. Note that a film may be formed using a single metal instead of the above oxide, and after the film formation, firing is performed, so that the oxide is finally formed.
上記成膜プロセスをスパッタリング法で行う場合、例えば、公知のＲＦスパッタリング法を用い、ターゲットとして、酸化ランタノイドからなるターゲットと、母材酸化物からなるターゲットと、導電性酸化物からなるターゲットとを同時に用いてスパッタ成膜して前駆体を得、この前駆体を大気中所定の温度で焼成することにより、所望の導電性蛍光体薄膜を形成することができる。同時スパッタリングは、例えば、母材酸化物のスパッタターゲットの表面にそれより径の小さな酸化ランタノイドのスパッタターゲットと導電性酸化物のターゲットとを好ましくは複数個乗せたターゲット配置形状で同時にスパッタを行えば良い。このターゲット形状は、特に制限はなく、所望の目的を達成できるようなものであれば良い。 When performing the film formation process by a sputtering method, for example, using a known RF sputtering method, a target made of a lanthanoid oxide, a target made of a base material oxide, and a target made of a conductive oxide are simultaneously used. The precursor is formed by sputtering to obtain a precursor, and the precursor is fired at a predetermined temperature in the atmosphere, whereby a desired conductive phosphor thin film can be formed. Co-sputtering is performed, for example, by performing sputtering simultaneously in a target arrangement shape in which a plurality of lanthanoid oxide sputtering targets having a smaller diameter and a conductive oxide target are preferably placed on the surface of a base oxide sputtering target. good. The target shape is not particularly limited as long as it can achieve a desired purpose.
また、電子ビーム蒸着法の場合は、導電性蛍光体薄膜の各成分元素を蒸発源とし、個々の蒸発源からの分子状の成分元素を基板上で反応させて所望の薄膜を形成しても良い。 In the case of the electron beam evaporation method, each component element of the conductive phosphor thin film is used as an evaporation source, and a molecular component element from each evaporation source is reacted on the substrate to form a desired thin film. good.
本発明の導電性蛍光体薄膜は、母材酸化物にランタノイド元素が付活され、更に導電性酸化物が分散されたものであり、その組成をａｔｍ％で表示すれば、一般に、ランタノイド元素の酸化物として、０．１〜１０ａｔｍ％程度、好ましくは２〜５ａｔｍ％であり、導電性酸化物となり得る物質として、１〜４０ａｔｍ％程度、好ましくは１〜５ａｔｍ％であり、残部は母材酸化物である。この範囲内の組成を有する導電性蛍光体薄膜であれば電子線による所望の発光を示す。 In the conductive phosphor thin film of the present invention, the lanthanoid element is activated in the base material oxide, and the conductive oxide is further dispersed. If the composition is expressed in atm%, generally the lanthanoid element The oxide is about 0.1 to 10 atm%, preferably 2 to 5 atm%, and the substance that can be a conductive oxide is about 1 to 40 atm%, preferably 1 to 5 atm%, and the balance is base material oxidation. It is a thing. A conductive phosphor thin film having a composition within this range exhibits desired light emission by an electron beam.
なお、焼成後に得られた導電性蛍光体薄膜は、例えば、[Ａ(１−ｘ)Ｂｘ]２Ｏ３Ｃｙ(式中、Ａは母材金属、Ｂはランタノイド元素、Ｃは導電性酸化物を形成し得る金属、０＜ｘ＜０．０５、０＜ｙ＜０．１である)の組成になっていると思われる。 The conductive phosphor thin film obtained after firing is, for example, [A (1-x) B x ] 2 O 3 Cy (where A is a base metal, B is a lanthanoid element, and C is conductive) It is considered that the composition of the metal capable of forming an oxide, 0 <x <0.05, 0 <y <0.1).
この透明基板としては、特に制限されるものではなく、例えばガラス基板、ＩＴＯ膜からなる基板、ＺｎＯ膜からなる基板等を挙げることができる。 The transparent substrate is not particularly limited, and examples thereof include a glass substrate, a substrate made of an ITO film, and a substrate made of a ZnO film.
本発明によれば、上記した多元蒸着の後に大気中で焼成して導電性蛍光体薄膜を形成するが、その際の焼成温度は、基板の耐熱温度以下であることが必要である。例えば、通常のガラス基板を用いた場合、その耐熱温度である５００℃程度であれば、所望の薄膜を生成できる。 According to the present invention, the conductive phosphor thin film is formed by firing in the air after the above-described multi-source deposition, and the firing temperature at that time needs to be equal to or lower than the heat resistant temperature of the substrate. For example, when a normal glass substrate is used, a desired thin film can be generated as long as the heat resistant temperature is about 500 ° C.
本発明では、大気中で、母材酸化物と付活材としてのランタノイド元素と導電性酸化物となり得る物質とを用いて同時に成膜処理しているので、母材酸化物内に均等に付活材が分散し、焼成時に結晶性が上昇すると共に、導電性酸化物となり得る物質も同時に成膜処理しているので、母材酸化物中に均等に分散し、得られた導電性蛍光体薄膜の発光輝度が高くなる上、蛍光体表面でのチャージアップも抑制され得る。この場合、母材酸化物に予めランタノイド元素を付活したものを用いて導電性酸化物となり得る物質と共に多元蒸着しても、同様の結果が得られる。 In the present invention, since film formation is simultaneously performed in the atmosphere using a base material oxide, a lanthanoid element as an activator, and a substance that can become a conductive oxide, the film is applied evenly in the base material oxide. Since the active material is dispersed, the crystallinity is increased during firing, and a substance that can become a conductive oxide is simultaneously formed into a film, so that the conductive phosphor obtained is uniformly dispersed in the base material oxide. The light emission brightness of the thin film is increased, and charge-up on the phosphor surface can be suppressed. In this case, the same result can be obtained even when multi-source deposition is performed together with a material that can be a conductive oxide using a lanthanoid element previously activated on a base material oxide.
本発明では、透明基板又は導電膜上に直接導電性蛍光体薄膜を形成でき、かつ、その膜厚制御も比較的容易に行える。例えば、膜厚が１μｍ以下(例えば、１００〜５００ｎｍ程度)の薄膜を形成することもでき、このような膜厚を有する導電性蛍光体薄膜で本発明の目的を達成することができる。 In the present invention, the conductive phosphor thin film can be directly formed on the transparent substrate or the conductive film, and the film thickness can be controlled relatively easily. For example, a thin film having a thickness of 1 μm or less (for example, about 100 to 500 nm) can be formed, and the object of the present invention can be achieved with a conductive phosphor thin film having such a thickness.
これに対して、従来のように、蛍光体薄膜を作製する時にスパッタ法やＥＢ蒸着法を用いて母材酸化物と付活材とを交互に積層させるだけでは、焼成時に付活材が母材酸化物の内部に十分に分散しないので、主に母材酸化物と付活材との界面のみが発光してしまい、発光輝度が低くなる。 On the other hand, as in the prior art, when the phosphor thin film is produced, the activator is used as the base material during firing only by alternately laminating the base material oxide and the activator using the sputtering method or the EB vapor deposition method. Since it is not sufficiently dispersed inside the material oxide, mainly only the interface between the base material oxide and the activator emits light, and the light emission luminance is lowered.
以下に、本発明について実施例を挙げて詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
本発明に従ってＹ２Ｏ３：Ｅｕ Ｚｎからなる導電性蛍光体薄膜を形成した。 In accordance with the present invention Y 2 O 3 : Eu A conductive phosphor thin film made of Zn was formed.
まず、酸化イットリウムターゲットと酸化ユーロピウムターゲットとＺｎＯターゲットとを用いて、通常の条件でガラス基板に対して同時にスパッタ成膜した。そして、得られた前駆体の形成された基板を電気炉に入れ、大気中５００℃で焼成した。この場合、５００℃まで３０分で上昇させ、そのまま６０分間保持した。その後、自然放冷で室温まで下げ、処理された基板を取り出した。また、比較のために、上記方法に準じて、酸化イットリウムターゲットと酸化ユーロピウムターゲットとを用い、導電性を付与していない蛍光体薄膜を作製した。かくして得られた薄膜の組成は、導電性蛍光体薄膜の場合、Ｅｕ：２ａｔｍ％、Ｚｎ：５ａｔｍ％、残部Ｙ２Ｏ３であり、導電性を付与していない蛍光体薄膜の場合、Ｅｕ：２ａｔｍ％、残部Ｙ２Ｏ３であった。また、得られた薄膜の膜厚は、それぞれ、約４００ｎｍであった。 First, using a yttrium oxide target, a europium oxide target, and a ZnO target, a sputter film was simultaneously formed on a glass substrate under normal conditions. And the board | substrate with which the obtained precursor was formed was put into the electric furnace, and it baked at 500 degreeC in air | atmosphere. In this case, the temperature was raised to 500 ° C. in 30 minutes and held for 60 minutes. Thereafter, the substrate was naturally cooled to room temperature, and the treated substrate was taken out. For comparison, a phosphor thin film not imparted with conductivity was produced using an yttrium oxide target and a europium oxide target in accordance with the above method. The composition of the thin film thus obtained is Eu: 2 atm%, Zn: 5 atm% and the balance Y 2 O 3 in the case of the conductive phosphor thin film, and Eu: It was 2 atm% and the balance was Y 2 O 3 . Moreover, the film thickness of the obtained thin film was about 400 nm, respectively.
上記の方法で得られた導電性を付与したＹ２Ｏ３：Ｅｕ Ｚｎ蛍光体薄膜及び導電性を付与していないＹ２Ｏ３：Ｅｕ蛍光体薄膜のそれぞれに対して、加速電圧３ｋＶまでの電子線を照射した時に得られる輝度を電流密度２．５ｍＡ／ｃｍ２で測定した。その結果を、図１に、加速電圧(ｋＶ)に対する輝度(ｃｄ／ｍ２)の変化として示す。図１から明らかなように、導電性を付与したサンプルの方が高輝度を示していることが分かる。従って、本実施例で得られた導電性を付与した蛍光体薄膜は、低加速電圧でも高輝度を示し、かつ、チャージアップもなかったため、ＦＥＤ等において十分使用に耐え得ることが分かる。 Y imparted with conductivity obtained by the above method2O3: Eu Zn phosphor thin film and Y not imparting conductivity2O3: The luminance obtained when each of the Eu phosphor thin films is irradiated with an electron beam up to an acceleration voltage of 3 kV is a current density of 2.5 mA / cm.2Measured with The result is shown in FIG. 1 as luminance (cd / m) with respect to acceleration voltage (kV).2). As is clear from FIG. 1, it can be seen that the sample provided with conductivity exhibits higher luminance. Therefore, it can be seen that the phosphor thin film imparted with conductivity obtained in this example exhibits high luminance even at a low acceleration voltage and has no charge-up, so that it can sufficiently be used in an FED or the like.
実施例１と同様の手法で作製したＹ２Ｏ３：Ｅｕ Ｚｎ蛍光体薄膜とＹ２Ｏ３：Ｅｕ蛍光体薄膜とを用いて、スタート輝度を１１０ｃｄ／ｍ２とした時の加速電圧３ｋＶの電子線の照射による寿命測定を行った。その結果を、図２に、時間(分)に対する輝度(ｃｄ／ｍ２)の変化として示す。図２から明らかなように、導電性を付与していないサンプルは、蛍光体表面のチャージアップにより発光輝度が時間と共に減少しているが、導電性を付与することにより、２０分程度で輝度の減少が治まり安定状態になった。つまり寿命が長くなったと言える。 Y 2 O 3 : Eu produced by the same method as in Example 1 Using a Zn phosphor thin film and a Y 2 O 3 : Eu phosphor thin film, lifetime measurement was performed by irradiation with an electron beam with an acceleration voltage of 3 kV when the start luminance was 110 cd / m 2 . The result is shown in FIG. 2 as a change in luminance (cd / m 2 ) with respect to time (minutes). As is clear from FIG. 2, in the sample not imparted with conductivity, the light emission luminance decreased with time due to the charge-up of the phosphor surface. The decrease has subsided and has become stable. In other words, it can be said that the lifetime has been extended.
実施例１及び２から、導電性を付与することで輝度が上昇するだけでなく、帯電の抑制効果も同時に得られるため、低加速電圧でも十分な発光輝度が得られ、ＦＥＤ等のように電子が低加速電圧で放出されるディスプレイ分野で蛍光体として有用である。 From Examples 1 and 2, not only the luminance is increased by imparting conductivity, but also the effect of suppressing charging is obtained at the same time. Therefore, sufficient emission luminance can be obtained even at a low acceleration voltage, and electrons such as FED can be obtained. Is useful as a phosphor in the field of displays in which is emitted at low acceleration voltages.
上記実施例では、酸化イットリウムと酸化ユーロピウムと酸化亜鉛とを用いて蛍光体薄膜を作製したが、その他の上記した酸化物も用いても同様な結果が得られる。 In the above embodiment, the phosphor thin film was prepared using yttrium oxide, europium oxide, and zinc oxide. However, similar results can be obtained by using other oxides described above.
本発明に従って、電子ビーム蒸着法によりＹ２Ｏ３：Ｅｕ Ｚｎ導電性蛍光体薄膜を形成した。 In accordance with the present invention, Y 2 O 3 : Eu by electron beam evaporation. A Zn conductive phosphor thin film was formed.
まず、酸化イットリウムのＥＢターゲットを第１の坩堝に入れ、第１の電源を用いて、また、酸化ユーロピウムのＥＢターゲットを第２の坩堝に入れ、第２の電源を用いて、また、ＺｎＯのＥＢターゲットを第３の坩堝に入れ、第３の電源を用いて、同時に蒸着操作を行って成膜した。その後、得られた前駆体の形成された基板を電気炉に入れ、大気中５００℃で焼成した。この場合、５００℃まで３０分で上昇させ、そのまま６０分間保持した。その後、自然放冷で室温まで下げ、処理された基板を取り出した。また、比較のために、上記方法に準じて、酸化イットリウムのＥＢターゲットと酸化ユーロピウムのＥＢターゲットとを用い、導電性を付与していない蛍光体薄膜を作製した。かくして得られた薄膜の組成は、導電性蛍光体薄膜の場合、Ｅｕ：２ａｔｍ％、Ｚｎ：５ａｔｍ％、残部Ｙ２Ｏ３であり、導電性を付与していない蛍光体薄膜の場合、Ｅｕ：２ａｔｍ％、残部Ｙ２Ｏ３であった。また、得られた薄膜の膜厚は、それぞれ、約４００ｎｍであった。 First, an yttrium oxide EB target is placed in a first crucible and using a first power source, a europium oxide EB target is placed in a second crucible and a second power source is used, and ZnO The EB target was placed in a third crucible, and a film was formed by simultaneously performing a vapor deposition operation using a third power source. Thereafter, the obtained substrate on which the precursor was formed was placed in an electric furnace and baked at 500 ° C. in the atmosphere. In this case, the temperature was raised to 500 ° C. in 30 minutes and held for 60 minutes. Thereafter, the substrate was naturally cooled to room temperature, and the treated substrate was taken out. For comparison, a phosphor thin film not imparted with conductivity was prepared using an yttrium oxide EB target and a europium oxide EB target in accordance with the above method. The composition of the thin film thus obtained is Eu: 2 atm%, Zn: 5 atm% and the balance Y 2 O 3 in the case of the conductive phosphor thin film, and Eu: It was 2 atm% and the balance was Y 2 O 3 . Moreover, the film thickness of the obtained thin film was about 400 nm, respectively.
上記の方法で得られた導電性を付与したＹ２Ｏ３：Ｅｕ Ｚｎ蛍光体薄膜及び導電性を付与していないＹ２Ｏ３：Ｅｕ蛍光体薄膜のそれぞれに対して、加速電圧３ｋＶまでの電子線を照射した時に得られる輝度を実施例１と同様に測定した。その結果、導電性を付与したサンプルの方が導電性を付与しないサンプルより高輝度を示した。本実施例で得られた導電性を付与した蛍光体薄膜は、低加速電圧でも高輝度を示し、かつ、チャージアップもなかったため、ＦＥＤ等において十分使用に耐え得ることが分かる。 Y 2 O 3 : Eu provided with conductivity obtained by the above method The luminance obtained when an electron beam up to an acceleration voltage of 3 kV was irradiated to each of the Zn phosphor thin film and the Y 2 O 3 : Eu phosphor thin film not imparted with conductivity was measured in the same manner as in Example 1. . As a result, the sample imparted with conductivity showed higher luminance than the sample not imparted with conductivity. It can be seen that the phosphor thin film imparted with conductivity obtained in this example exhibits high luminance even at a low acceleration voltage and has no charge-up, so that it can sufficiently be used in an FED or the like.
本発明によれば、低加速電圧でも十分に発光輝度が得られ、長寿命化を図ることが可能な蛍光体薄膜を提供できるので、この薄膜を用いた蛍光体基板はＦＥＤや高精細ＣＲＴのディスプレイ等の分野で利用可能である。 According to the present invention, it is possible to provide a phosphor thin film that can obtain sufficient emission luminance even at a low acceleration voltage and can have a long life. Therefore, a phosphor substrate using this thin film can be used for FED and high-definition CRT. It can be used in fields such as displays.
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