JPH0371594A - Manufacture of fluorescent thin film - Google Patents
Manufacture of fluorescent thin filmInfo
- Publication number
- JPH0371594A JPH0371594A JP1207531A JP20753189A JPH0371594A JP H0371594 A JPH0371594 A JP H0371594A JP 1207531 A JP1207531 A JP 1207531A JP 20753189 A JP20753189 A JP 20753189A JP H0371594 A JPH0371594 A JP H0371594A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- reducing atmosphere
- film
- transparent electrode
- oxide transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010408 film Substances 0.000 claims abstract description 24
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000000137 annealing Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- -1 alkaline earth metal sulfides Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052923 celestite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、蛍光体薄膜製造方法に係るもので。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a phosphor thin film.
特にＥＬ素子の蛍光体薄膜製造方法の改良に関するもの
である。In particular, the present invention relates to improvements in methods for manufacturing phosphor thin films for EL devices.
［発明の概要］
本発明は、アルカリ土類硫化物蛍光体薄膜の製造におい
て、薄膜を還元性雰囲気中にて熱処理しても、酸化物透
明電極が還元を受けないようにしたものである。[Summary of the Invention] According to the present invention, in the production of an alkaline earth sulfide phosphor thin film, an oxide transparent electrode is prevented from being reduced even if the thin film is heat-treated in a reducing atmosphere.
［従来の技術］
近時、ＩＬａ−ＶＩｂ族化合物、特にアルカリ土類金属
の硫化物であるＳｒＳ、ＣａＳを蛍光膜として用いる薄
膜ＥＬ素子が、フルカラー薄ＷＡＥＬパネルを実現しう
る重要な材料として注目されている。[Prior Art] Recently, thin-film EL devices using ILa-VIb group compounds, especially SrS and CaS, which are alkaline earth metal sulfides, as fluorescent films have attracted attention as important materials that can realize full-color thin WAEL panels. has been done.
ことに、従来のＺｎＳ 系蛍光膜では実現できなかった
高輝度の青色ＥＬが実現できる可能性があるため、近年
、盛んに検討されつつある。ここで、フルカラー化に必
要な三原色（赤、緑、青）のそれぞれの現在の技術水準
をＺｎＳ 系材料および硫化アルカリ土類金属材料につ
いて、以下に述べる６１）緑色ＥＬ
ＺｎＳ ： ＴｂＦ、は色純度に優れ、かつ高輝度のも
のが得られており、すでに実用レベルに達している。特
にスパッター法で作成したものは高輝度のものが得られ
ており、約１３７Ｃｄ／ｆｆ１（６０胞）程度である。In particular, it has been actively studied in recent years because it has the potential to realize high-brightness blue EL, which was not possible with conventional ZnS-based fluorescent films. Here, the current technological level of each of the three primary colors (red, green, and blue) necessary for full color production is described below for ZnS-based materials and alkaline earth metal sulfide materials.61) Green EL ZnS: TbF, color purity It has excellent brightness and high brightness, and has already reached a practical level. In particular, those produced by the sputtering method have high brightness, about 137 Cd/ff1 (60 cells).
２）赤色ＥＬ
ＺｎＳ：Ｓｍ系では、ＳｌをＳ ｍ Ｆ ｚ ＨＳ ｍ
ｌ ＣＱ ｚ ｗＳｍＰの形で導入する方法がそれぞれ
試みられており、ＳｍＣＱ、のものが最も色純度が優れ
ている。2) In the red EL ZnS:Sm system, change Sl to S m F z HS m
Various methods have been tried to introduce it in the form of l CQ z wSmP, and SmCQ has the best color purity.
輝度は約１２Ｃｄ／耐（６０１（ｚ）程度で、 これは
実用レベルに達するには最低で２倍、望ましくは４倍程
度の向上が更に必要な値である。The luminance is about 12 Cd/distance (601(z)), which is a value that needs to be further improved by at least two times, preferably about four times, to reach a practical level.
ＣａＳ：Ｅｕ系も色純度は優れている。輝度はＥＢ蒸着
法で作成したもので、約１０Ｃｄ／ｍ（６０Ｈｚ）、ス
パッター法のものは実用レベルの最低線にごく近づいて
いる。The CaS:Eu system also has excellent color purity. The brightness was approximately 10 Cd/m (60 Hz) for those created using the EB evaporation method, and the brightness for those created using the sputtering method was very close to the lowest practical level.
３）青色ＥＬ
ＺｎＳＨＴｍ系のものは占くから検討されているが５色
純度はよいものの、輝度は０．１４Ｃｄ／ｍ（６０Ｈｚ
）と実用にはほど遠い。3) Blue EL ZnSHTm type is being considered for fortune-telling, but although the five-color purity is good, the luminance is 0.14Cd/m (60Hz
) and is far from practical.
ＳｒＳ ＨＣｅ系は色純度に問題があるものの（青緑色
）、輝度については、約４０ Ｃｄ／ボ（６０Ｈ７）が
実現されており、実用レベルを越えている。ただ、ＴＶ
映像のような応用には、色フィルターを通すことが必要
で、輝度は約１０分の１に低下する（約４Ｃｄ／ボ、６
０亀）ａ したがって、この場合には、実用レベルに達
するには、少なくとも２倍、望ましくは５倍程度の輝度
の向上が必要となる。しかし、もしも、この輝度向上が
実現できれば、一つの蛍光膜で青と緑の２原色を出せる
可能性がある。Although the SrS HCe system has a problem with color purity (blue-green color), a luminance of approximately 40 Cd/bo (60H7) has been achieved, which exceeds the practical level. However, TV
For applications such as video, it is necessary to pass through a color filter, which reduces the brightness by about a tenth (approximately 4 Cd/vo, 6
Therefore, in this case, in order to reach a practical level, it is necessary to improve the brightness by at least two times, preferably about five times. However, if this improvement in brightness could be achieved, it would be possible to produce two primary colors, blue and green, with a single fluorescent film.
したがって、赤色および青色ＥＬについては、Ｈａ −
ＶＩ ｂ族化合物の蛍光体を中心に一般の輝度向」二が
必要である。更に、これらのＩＩａ−ＶＩｈ族化合物蛍
光体の問題点である輝度の不安定性や劣化の問題に関す
る有効な解決策を見出す努力も同時に並行して進める必
要がある。Therefore, for red and blue ELs, Ha −
A general brightness direction is required mainly for phosphors of group VIb compounds. Furthermore, it is necessary to simultaneously proceed with efforts to find an effective solution to the problems of luminance instability and deterioration that are problems of these IIa-VIh group compound phosphors.
［発明が解決しようとする課題］
青色発光材料の最も有力な候補となっている上記ＳｒＳ
は、 かなり酸化され易い。乾燥雰囲気中においても、
水分または二酸化炭素の作用により分解すると云われて
いる。[Problem to be solved by the invention] The above-mentioned SrS is the most promising candidate for a blue light emitting material.
is quite easily oxidized. Even in a dry atmosphere,
It is said to be decomposed by the action of moisture or carbon dioxide.
このように、一般にアルカリ土類硫化物を使用した蛍光
膜は、大気中にて極めて不安定である。As described above, fluorescent films using alkaline earth sulfides are generally extremely unstable in the atmosphere.
特に蒸着に用いる前記ＳｒＳ のペレソトそのものが、
ＳｒＳ が酸化されてできた５ｒＳＯ，をかなり大量
に混入している可能性があるため、このペレッ１−を使
用して薄膜を作成すると、ＳｒＳＯ４の配向膜、もしく
は、これの混入した膜が得られ、ＥＬ素子としての特性
を大幅に劣化させる原因となる。In particular, the SrS material itself used for vapor deposition is
There is a possibility that a large amount of 5rSO, which is formed by oxidation of SrS, is mixed in, so if a thin film is made using this pellet, an oriented film of SrSO4 or a film mixed with this may be obtained. This causes a significant deterioration of the characteristics of the EL element.
これより、５ｒＳＯ，の混入の少ないＳ ｒ Ｓ 薄膜
を作成することが、ＥＬ特性を向上させるうえで極めて
重要である。この問題について、本発明者は、 ＥＬ特
性を劣化させる原因となっている５ｒＳＯ，の如き酸化
物の混入をできるだけ低減させる方法として、成膜後の
薄膜を還元性雰囲気中にて熱処理を施す蛍光体薄膜製造
方法を提案した。From this, it is extremely important to create a S r S thin film with less 5rSO, in order to improve the EL characteristics. Regarding this problem, the present inventor proposed a method for reducing as much as possible the contamination of oxides such as 5rSO, which cause deterioration of EL characteristics, by heat-treating the thin film after it has been formed in a reducing atmosphere. A method for producing body thin film was proposed.
しかしながら、通常、ＥＬ素子起して使用する透明電極
はＩＴＯ（酸化インジウム！！ｌ）のように、酸化物で
ある。However, the transparent electrode used in EL devices is usually an oxide such as ITO (indium oxide!!l).
このような酸化物の透明電極を還元性雰囲気中にて熱処
理すると、還元されるため、その透明度を失うことにな
る。とくに、ＩＴＯの場合、実際に５５０℃、３０分の
熱処理を行った場合、還元されるが、金属のインジウム
や錫は融点が低いため蒸発してしまい、後に島状の残留
物が残り、これは導電性を示さなくなる。そのため還元
性ＩＩ囲気中においても、透明電極が還元を受番づない
ようにする必要がある。When a transparent electrode made of such an oxide is heat-treated in a reducing atmosphere, it is reduced and loses its transparency. In particular, in the case of ITO, when it is actually heat treated at 550°C for 30 minutes, it is reduced, but metals such as indium and tin have low melting points and evaporate, leaving behind island-shaped residues. no longer exhibits conductivity. Therefore, it is necessary to prevent the transparent electrode from undergoing reduction even in a reducing II atmosphere.
［発明の目的コ
本発明は、−上記問題に鑑みてなされたものであって、
アルカリ土類硫化物蛍光体薄膜の製造において、薄膜を
還元性雰囲気中にて熱処理しても、酸化物透明電極が還
元を受けないようにした蛍光体薄膜製造方法を提供する
ものである。[Object of the Invention] The present invention has been made in view of the above problems, and
The present invention provides a method for producing an alkaline earth sulfide phosphor thin film in which an oxide transparent electrode is not reduced even when the thin film is heat-treated in a reducing atmosphere.
［課題を解決するための手段］
本発明は、アルカリ土類硫化物蛍光体薄膜を形成する薄
膜製造方法において、前記薄膜形成後、露出する酸化物
透明電極部位を、導電性を有するとともに還元性雰囲気
にて影響されない保護膜で被覆し、その後に還元性雰囲
気中にて熱処理を施すことを特徴としているものである
。[Means for Solving the Problems] The present invention provides a thin film manufacturing method for forming an alkaline earth sulfide phosphor thin film. It is characterized in that it is coated with a protective film that is not affected by the atmosphere, and then heat-treated in a reducing atmosphere.
［作用］
上記製造方法によれば、露出する酸化物透明電極部位は
保護膜で被覆されているので、還元性雰囲気中での熱処
理を受けても、還元されることはない。[Function] According to the above manufacturing method, since the exposed oxide transparent electrode portion is covered with a protective film, it will not be reduced even if it is subjected to heat treatment in a reducing atmosphere.
［実施例］
第１図は１本発明方法によって製造するＥＬ素子構造を
示し、第２図は従来のＥＬの基本的な素子構造を示すも
のである。両図面において、同一または類似する部材に
は同じ符号が付されている。[Example] FIG. 1 shows the structure of an EL device manufactured by the method of the present invention, and FIG. 2 shows the basic structure of a conventional EL device. Identical or similar parts are given the same reference numerals in both figures.
即ち、１はガラス基板、２はＩＴＯの透明電極、３は第
１絶縁層、４は蛍光層、５は第２絶縁層、６はＡＱによ
る背面電極であり、第１図で符号７で示したものは、露
出する透明電極部位を被覆している保護膜である。この
保護膜７にはＡＱその他の金属膜のような、導電性を有
するとともに還元性雰囲気にて影響されない材料が用い
られている。That is, 1 is a glass substrate, 2 is an ITO transparent electrode, 3 is a first insulating layer, 4 is a fluorescent layer, 5 is a second insulating layer, and 6 is a back electrode made of AQ, which is indicated by the reference numeral 7 in FIG. The other thing is a protective film that covers the exposed transparent electrode parts. This protective film 7 is made of a material such as AQ or other metal film that has conductivity and is not affected by a reducing atmosphere.
ここで、第２図に示した従来のＥＬ素子の作成工程を下
記に述べる。Here, the manufacturing process of the conventional EL element shown in FIG. 2 will be described below.
■）ガラス基板面にＩＴＯをエツチングし、パターンを
形成する。(2) Etching ITO on the glass substrate surface to form a pattern.
２）第Ｉ絶縁層を形成する。2) Form a first insulating layer.
３）蛍光体薄膜を形成する。必要に応じてアニール処理
を行う。3) Form a phosphor thin film. Annealing is performed as necessary.
４）第２絶縁層を形成する。4) Form a second insulating layer.
５）背面電極を形成する。5) Form a back electrode.
これに対し、本発明方法を示す第１図において、最も特
徴的な点は、第１絶縁膜を形成するに先立ち、露出する
可能性のある透明電極部位を、前記保護膜７で被覆して
おき、第１絶縁膜および蛍光膜を形成したあと、蛍光膜
の特性を改良する目的で、本素子を水素などの還元性雰
囲気中にてアニール処理を行う工程において、還元ガス
にさらさないようにしたものである。以下に本発明方法
によるＥＬ素子の作成方法を述べる。On the other hand, in FIG. 1 showing the method of the present invention, the most characteristic point is that, prior to forming the first insulating film, the transparent electrode portion that may be exposed is covered with the protective film 7. After forming the first insulating film and fluorescent film, the device is annealed in a reducing atmosphere such as hydrogen in order to improve the characteristics of the fluorescent film, so that it is not exposed to reducing gas. This is what I did. A method for producing an EL element using the method of the present invention will be described below.
１〉ガラス基板面にＩＴＯをエツチングし、パターンを
形成する。1> Etch ITO on the glass substrate surface to form a pattern.
２）還元性雰囲気中にて露出する可能性のある透明電極
部位にＡＱ等の金属による保護膜を形成する。2) A protective film made of a metal such as AQ is formed on a transparent electrode portion that may be exposed in a reducing atmosphere.
３）第１絶縁膜を形成ｉる。3) Form a first insulating film.
４）蛍光体薄膜を形成する。4) Form a phosphor thin film.
５）還元性雰囲気中にて薄膜をアニールする。5) Anneal the thin film in a reducing atmosphere.
６）第２絶縁層を形成する。6) Form a second insulating layer.
７）背面電極を形成する。7) Form a back electrode.
［発明の効果］
以上に述べたように、本発明によれば、アルカリ土類硫
化物蛍光体薄膜を形成する薄膜の製造において、ＩＴＯ
等の透明電極を還元させることなく、水素などの還元性
雰囲気中にて、蛍光体薄膜をアニールすることができ、
その特性を大幅に改善することを可能とした点で、顕著
な効果がある。[Effects of the Invention] As described above, according to the present invention, in the production of a thin film forming an alkaline earth sulfide phosphor thin film, ITO
The phosphor thin film can be annealed in a reducing atmosphere such as hydrogen without reducing the transparent electrode, such as
It has a remarkable effect in that it makes it possible to significantly improve its characteristics.
第１図は本発明によって製造したＥＬ素子の要部の断面
図、第２図は従来法によって製造したＥＬ素子の要部の
断面図である。
１・・・・・・・・・ガラス基板、２・・・・・・・・
・透明電極、３・・・・・・・・・第１絶縁層、４・・
・・・・・・・蛍光層、５・・・・・・・・・第２絶縁
層、６・・・・・・・・・背面電極、７・・・・・・・
・・保護層。
第１図
第２図FIG. 1 is a sectional view of a main part of an EL device manufactured by the present invention, and FIG. 2 is a sectional view of a main part of an EL device manufactured by a conventional method. 1...Glass substrate, 2...
・Transparent electrode, 3...First insulating layer, 4...
...... Fluorescent layer, 5... Second insulating layer, 6... Back electrode, 7...
...Protective layer. Figure 1 Figure 2
Claims (1)
法において、前記薄膜形成後、露出する酸化物透明電極
部位を、導電性を有するとともに還元性雰囲気にて影響
されない保護膜で被覆し、その後に還元性雰囲気中にて
熱処理を施すことを特徴とする蛍光体薄膜製造方法。In a thin film manufacturing method for forming an alkaline earth sulfide phosphor thin film, after forming the thin film, the exposed oxide transparent electrode portion is covered with a protective film that is conductive and unaffected by a reducing atmosphere, and then A method for producing a phosphor thin film characterized by performing heat treatment in a reducing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1207531A JPH0371594A (en) | 1989-08-09 | 1989-08-09 | Manufacture of fluorescent thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1207531A JPH0371594A (en) | 1989-08-09 | 1989-08-09 | Manufacture of fluorescent thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0371594A true JPH0371594A (en) | 1991-03-27 |
Family
ID=16541267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1207531A Pending JPH0371594A (en) | 1989-08-09 | 1989-08-09 | Manufacture of fluorescent thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0371594A (en) |
-
1989
- 1989-08-09 JP JP1207531A patent/JPH0371594A/en active Pending
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