JPH0265092A - Manufacture of thin film el element - Google Patents
Manufacture of thin film el elementInfo
- Publication number
- JPH0265092A JPH0265092A JP63215522A JP21552288A JPH0265092A JP H0265092 A JPH0265092 A JP H0265092A JP 63215522 A JP63215522 A JP 63215522A JP 21552288 A JP21552288 A JP 21552288A JP H0265092 A JPH0265092 A JP H0265092A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- emitting layer
- target
- alkaline earth
- light emitting
- 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 38
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 6
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 11
- 229910052798 chalcogen Inorganic materials 0.000 abstract description 5
- 150000001787 chalcogens Chemical class 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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〕
本発明は表示デバイスなどに用いる薄膜ＥＬ素子に関す
るものである。更に詳しくは、良好なＥＬ発光特性を有
する発光層薄膜形成工程を含む薄膜ＥＬ素子の製造方怯
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thin film EL element used in display devices and the like. More specifically, the present invention relates to a method for manufacturing a thin film EL device including a step of forming a light emitting layer thin film having good EL emission characteristics.
薄膜ＥＬ素子の発光層材料はＺｎＳ：Ｍｎ、 ＺｎＳ：
Ｔｂ、 ＺｎＳ：ＳｍなどＺｎＳを母体とするものが多
いが、近年多色化のためにＣａＳ：Ｅｕ、 ＳｒＳ：Ｃ
ｓなどアルカリ土類カルコゲナイドを母体とし、希土類
で付活された発光層材料が注目されている。アルカリ土
類カルコゲナイドを母体とする発光層を有する薄膜ＥＬ
素子は、第２図に示すようにＺｎＳを母体とする薄膜Ｅ
Ｌ素子と同じくガラス基板８上に透明電極９、第一絶縁
体層１０．アルカリ土類カルコゲナイドを母体とする発
光層１１、第二絶縁体層１２、上部ＡＱ電極１３を順次
形成して製造され、このアルカリ土類カルコゲナイドを
母体とし希土類で付活された発光層薄膜は、 ＣａＳ：
ＥｕやＳｒＳ：Ｃｅ等の原料ペレットを電子ビームによ
り加熱し成膜する真空蒸着法やＣａＳ：ＥｕやＳｒＳ：
Ｃｅ等のターゲットを用いたスパッタ法によって成膜さ
れている。更に良好な薄膜を得るために、Ｓ雰囲気での
蒸着法や、Ｈ，Ｓを含むスパッタガスを用いるスパッタ
法も提案されている。The light emitting layer material of the thin film EL device is ZnS:Mn, ZnS:
Many materials are based on ZnS, such as Tb and ZnS:Sm, but in recent years, due to multicolorization, CaS:Eu, SrS:C
Luminescent layer materials based on alkaline earth chalcogenides such as s and activated with rare earth elements are attracting attention. Thin film EL with a light-emitting layer based on alkaline earth chalcogenide
The device is made of a thin film E whose matrix is ZnS, as shown in Fig. 2.
Similar to the L element, a transparent electrode 9 and a first insulating layer 10 are provided on a glass substrate 8. The light-emitting layer thin film made of alkaline earth chalcogenide as a base and activated with rare earth elements is manufactured by sequentially forming the light-emitting layer 11, the second insulator layer 12, and the upper AQ electrode 13, which has alkaline earth chalcogenide as the base, and is activated with rare earth elements. CaS:
Vacuum evaporation method in which raw material pellets such as Eu and SrS:Ce are heated with an electron beam to form a film, and CaS:Eu and SrS:
The film is formed by a sputtering method using a target such as Ce. In order to obtain even better thin films, a vapor deposition method in an S atmosphere and a sputtering method using a sputtering gas containing H and S have also been proposed.
希土類で付活したアルカリ土類カルコゲナイドは、カラ
ーＥＬ発光層材料として期待されるが、ＺｎＳを母体に
した発光層材料に比べ高品位な薄膜を得ることが非常に
難しく、良好な薄膜ＥＬ素子の発光特性を得ることが困
難である。アルカリ土類カルコゲナイドのペレットを電
子ビーム加熱する真空蒸着法では、形成した発光層薄膜
のカルコゲン抜けが発生し、化学量論比組成からずれる
ことにより結晶性が著しく悪くなる。また、酸素によっ
て一部化学量論比組成のずれが補われ、アルカリ土類酸
化物が生成されることにより発光特性が劣化する。Ｓの
雰囲気蒸着法では、上記カルコゲン抜けや酸化物の生成
をある程度抑えることが可能であり、結晶性や発光特性
の改善がみられるが、Ｓ雰囲気の制御性が悪く、蒸着法
としては１０″″４〜１Ｏ−３ｔｏｒｒと真空度を著し
く悪くしなければならない。更に、真空蒸着法ではｓｏ
ｏ’ ｃ以上の高い基板温度が必要である。−カスバッ
タ法による成膜では、Ｈ２ＳやＨ２Ｓｅを含んだスパッ
タガスを用いることでカルコゲン抜けの少ない高品位な
薄膜を４００℃以下の温度で形成することができるが、
有毒なガスの殆どが成膜室外に排出されるため、有毒排
出ガスの処理工程が必要である。Alkaline earth chalcogenides activated with rare earth elements are expected to be used as color EL light-emitting layer materials, but it is extremely difficult to obtain high-quality thin films compared to light-emitting layer materials based on ZnS, and it is difficult to obtain good thin-film EL devices. It is difficult to obtain luminescent properties. In the vacuum evaporation method in which alkaline earth chalcogenide pellets are heated with electron beams, chalcogen loss occurs in the formed light-emitting layer thin film, which deviates from the stoichiometric composition, resulting in significantly poor crystallinity. In addition, the deviation in stoichiometric composition is partially compensated for by oxygen, and alkaline earth oxides are generated, thereby degrading the luminescent properties. In the S atmosphere vapor deposition method, it is possible to suppress the chalcogen loss and the formation of oxides to some extent, and improvements in crystallinity and luminescent properties are observed, but the controllability of the S atmosphere is poor, and the vapor deposition method is limited to 10" ``The degree of vacuum must be significantly reduced to 4 to 1 O-3 torr. Furthermore, in the vacuum evaporation method, so
A high substrate temperature of oc or higher is required. - In film formation by the castbatter method, a high-quality thin film with less chalcogen loss can be formed at a temperature of 400°C or lower by using a sputtering gas containing H2S or H2Se.
Since most of the toxic gases are exhausted outside the deposition chamber, a process for treating the toxic exhaust gases is necessary.
本発明の目的は多量の有毒ガスを排出することなしに４
００’ Ｃ以下の基板温度で高品位な発光層薄膜を形成
することが可能な、アルカリ土類カルコゲナイドを母体
とした発光層を有する薄膜ＥＬ素子の製造方怯を提供す
ることにある。The object of the present invention is to
It is an object of the present invention to provide a method for manufacturing a thin film EL device having a light emitting layer based on alkaline earth chalcogenide, which can form a high quality thin light emitting layer at a substrate temperature of 00'C or less.
上記目的を達成するため、本発明の薄膜ＥＬ素子の製造
方怯は、アルカリ土類カルコゲナイドを母体とし、Ｃｅ
やＥｕ等の希土類又はＭｎで付活された蛍光体薄膜を発
光層とする薄膜ＥＬ素子の製造方怯において、付活剤及
び化学量論比組成の母体材料に過剰のＳｓ又はＴｅを含
むターゲットを用い、スパッタ法によって発光層薄膜を
形成する工程を含むものである。In order to achieve the above object, the manufacturing method of the thin film EL device of the present invention uses alkaline earth chalcogenide as a matrix and Ce
In the method of manufacturing a thin film EL device using a phosphor thin film activated with a rare earth element such as Eu or Mn as a light emitting layer, a target containing an excess of Ss or Te in the activator and the host material with a stoichiometric composition is used. The method includes a step of forming a light emitting layer thin film by sputtering using a method of manufacturing.
希土類で付活されたアルカリ土類カルコゲナイドをター
ゲットとし、 ＡｒやＮｅなどの希ガスをスパッタガス
として用い、発光層薄膜を成膜する際、化学量論比組成
のアルカリ土類カルコゲナイドに過剰のＳｓ又はＴｅを
加えたターゲットを用いてスパッタ成膜することにより
、 Ｓｓ又はＴｏを加えないときに発生したカルコゲン
抜けが、ターゲットより過剰のＳｅ又はＴｅが供給され
るため大幅に抑制され、化学量論比組成が補償された高
品位な薄膜を得ることができ、ひいては良好な発光特性
を有する薄膜ＥＬ素子を得ることができる。この際、有
毒ガスは殆ど排出されない。When forming a light-emitting layer thin film by targeting alkaline earth chalcogenide activated with rare earth elements and using a rare gas such as Ar or Ne as a sputtering gas, an excess of Ss is added to the alkaline earth chalcogenide having a stoichiometric composition. Alternatively, by sputtering film formation using a target to which Te is added, the chalcogen loss that occurs when Ss or To is not added is greatly suppressed because excess Se or Te is supplied from the target, and the stoichiometry is maintained. A high-quality thin film with a compensated specific composition can be obtained, and a thin film EL element with good light emission characteristics can be obtained. At this time, almost no toxic gas is emitted.
本発明製造方怯による形成膜は、アルカリ土類カルコゲ
ナイドとして硫化物をターゲット中に使用したとしても
Ｓｓ又はＴｏを含む混晶となるが、これによる発光特性
の低下は通常の場合あまりない。The film formed by the production method of the present invention becomes a mixed crystal containing Ss or To even if sulfide is used as the alkaline earth chalcogenide in the target, but the luminescent properties usually do not deteriorate much due to this.
但し、母体材料の混晶化が容認されない材料系の場合に
は、本発明の製造方怯は適さない＊ Ｓｅ、 Ｔｅの代
りに過剰のＳを加えたターゲットを用いてスパッタ成膜
した場合、Ｓの蒸気圧が非常に高いために一回のスパッ
タ中にターゲットの加熱によってターゲット中に含まれ
るＳが大幅に減少し、再現性に難点がある。However, in the case of a material system that does not allow mixed crystallization of the base material, the manufacturing method of the present invention is not suitable. Since the vapor pressure of S is very high, the S contained in the target is significantly reduced by heating the target during one sputtering process, which poses a problem in reproducibility.
以下、Ｅｕで付活されたＣａＳにＳｅを過剰に加えたタ
ーゲットを用いてスパッタ成膜した発光層を有する薄膜
ＥＬ素子を例にして詳細を説明する。第２図に示すよう
にガラス基板８上に透明電極９を形成し、ＡＱ、０．か
らなる第一絶縁体層１ｏを３０００人形成した。その後
、第１図に示す成膜装置を用いて成膜した。第１図はス
パッタガスボンベ６を接続した真空槽３内にターゲット
５と基板２とを向き合せに設置し、基板２を基板ヒータ
１で加熱し、ターゲット５を冷却器４で冷却して保持さ
せたものである。７は流量調節器である。ターゲット５
にはＥｕを０．２＋＋ｏ１％含むＣａＳ（６０ｗｔ、％
）とＳｏ（４０ｗｔ、％）を混合し、これを加圧成形し
たものを用い、基板温度３５０’ ＣでＡｒガスをスパ
ッタガスにして高周波スパッタリングにより基板２に発
光層薄膜１１を７０００人形成した。その後ＡＩ２．０
．からなる第二絶縁体層１２を３０００人形成し、更に
上部ＡＱ電極１３を成膜して、薄膜ＥＬ素子を構成した
。また比較のために、Ｓｓを混合せずＥｕを０．２＋＋
＋ｏ１％含むＣａＳを加圧成形してターゲット５として
用い、発光層を形成した素子も作製した。Ｓｅを含むタ
ーゲットを用いて形成した発光層を組成分析及びＸ線結
晶構造解析を行ったところ、形成膜はＣａＳとＣａＳｅ
の混晶となっており、Ｎ ａ ＣＱ構造を有する。また
この発光層は、Ｓｅを含まないターゲットを用いて形成
した発光層薄膜に比べ、回折線の半値幅Δ２θが半分以
下に減少し、回折線の強度も増加しており結晶性が大幅
に改善されていた。この二つのＥＬ素子の輝度−電圧発
光特性を測定したところ、第３図に示すように本発明に
よるεｌ、素子は従来技術により作製した素子に比べ、
立ち上がりも良好で輝度も約４倍向上していた。Hereinafter, details will be explained by taking as an example a thin film EL element having a light emitting layer formed by sputtering using a target in which Se is added in excess to CaS activated with Eu. As shown in FIG. 2, a transparent electrode 9 is formed on a glass substrate 8, and the AQ is 0. 3000 people formed the first insulator layer 1o consisting of the following. Thereafter, a film was formed using the film forming apparatus shown in FIG. In FIG. 1, a target 5 and a substrate 2 are placed facing each other in a vacuum chamber 3 connected to a sputtering gas cylinder 6, and the substrate 2 is heated by a substrate heater 1, and the target 5 is cooled and held by a cooler 4. It is something that 7 is a flow rate regulator. target 5
contains CaS (60 wt, %
) and So (40 wt, %) were mixed and pressure molded, and a light emitting layer thin film 11 was formed on the substrate 2 by high frequency sputtering at a substrate temperature of 350'C using Ar gas as a sputtering gas. . After that AI2.0
．． A second insulator layer 12 was formed by 3000 people, and an upper AQ electrode 13 was further formed to form a thin film EL element. For comparison, 0.2++ of Eu was added without mixing Ss.
A device in which a light emitting layer was formed was also fabricated by pressure molding CaS containing 1% +O and using it as the target 5. Composition analysis and X-ray crystal structure analysis of the light-emitting layer formed using a target containing Se revealed that the formed film was composed of CaS and CaSe.
It is a mixed crystal with an N a CQ structure. In addition, compared to a thin light emitting layer formed using a target that does not contain Se, this light emitting layer has a half width Δ2θ of the diffraction line reduced to more than half, the intensity of the diffraction line has increased, and the crystallinity has been significantly improved. It had been. When the luminance-voltage emission characteristics of these two EL devices were measured, as shown in FIG.
The start-up was also good, and the brightness was about 4 times higher.
さらに、Ｃｅで付活されたＳｒＳにＳｅを過剰に加えた
ターゲットを用いた場合や、 Ｓｅに換えてＴｅを用い
た場合でも同様な効果があった。Furthermore, similar effects were obtained when using a target in which Se was added in excess to SrS activated with Ce, or when Te was used instead of Se.
以上説明したように、本発明の薄膜ＥＬ素子の製造方怯
によれば、希土類で付活されたアルカリ土類硫化物にＳ
ｅ又はＴｏを混合したターゲットを用いて発光層薄膜を
スパッタ成膜することにより、Ｈ２Ｓのような特殊な有
毒ガスをスパッタガスに用いることなく、より容易に低
い基板温度で良好な発光特性を有する薄膜ＥＬ素子を得
ることができる効果を有するものである。As explained above, according to the manufacturing method of the thin film EL device of the present invention, S
By sputtering a light-emitting layer thin film using a target mixed with e or To, it is possible to easily achieve good light-emitting characteristics at a low substrate temperature without using a special toxic gas such as H2S as a sputtering gas. This has the effect that a thin film EL element can be obtained.
尚、本実施例では粉末を混合して作製したターゲットを
使用したが、例えばＣａＳ ： Ｅｕの成形ターゲット
の上にＳｅの小片を配置したいわゆる複合型ターゲット
としてもよい。In this embodiment, a target prepared by mixing powders was used, but a so-called composite target in which small pieces of Se are placed on a molded target of CaS:Eu, for example, may also be used.
第１図は本発明の薄膜ＥＬ素子の発光層の形成が可能な
成膜装置の略示図、第２図は薄膜ＥＬ素子の断面図、第
３図は本発明により作製した素子と従来技術により作製
した素子の輝度−電圧発光特性図である。FIG. 1 is a schematic diagram of a film forming apparatus capable of forming the light-emitting layer of the thin film EL device of the present invention, FIG. 2 is a cross-sectional view of the thin film EL device, and FIG. 3 is a diagram showing the device manufactured according to the present invention and the prior art. FIG. 3 is a luminance-voltage emission characteristic diagram of an element manufactured by the method.
Claims (1)
Ｅｕ等の希土類又はＭｎで付活された蛍光体薄膜を発光
層とする薄膜ＥＬ素子の製造方怯において、付活剤及び
化学量論比組成の母体材料に過剰のＳｅ又はＴｅを含む
ターゲットを用い、スパッタ法によって発光層薄膜を形
成する工程を含むことを特徴とする薄膜ＥＬ素子の製造
方怯．(1) In the method of manufacturing a thin film EL device having an alkaline earth chalcogenide matrix and a phosphor thin film activated with a rare earth element such as Ce or Eu or Mn as a light emitting layer, the activator and stoichiometric composition A method for manufacturing a thin film EL device, characterized in that it includes a step of forming a light emitting layer thin film by sputtering using a target containing excess Se or Te as a base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215522A JPH0265092A (en) | 1988-08-29 | 1988-08-29 | Manufacture of thin film el element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63215522A JPH0265092A (en) | 1988-08-29 | 1988-08-29 | Manufacture of thin film el element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0265092A true JPH0265092A (en) | 1990-03-05 |
Family
ID=16673812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63215522A Pending JPH0265092A (en) | 1988-08-29 | 1988-08-29 | Manufacture of thin film el element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0265092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087621A (en) * | 1989-04-18 | 1992-02-11 | Laboratorios Del Dr. Esteve | Substituted azetidinylisothiazolopyridone derivatives, their preparation and their application as medicinal products |
-
1988
- 1988-08-29 JP JP63215522A patent/JPH0265092A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5087621A (en) * | 1989-04-18 | 1992-02-11 | Laboratorios Del Dr. Esteve | Substituted azetidinylisothiazolopyridone derivatives, their preparation and their application as medicinal products |
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