JPH03110788A - Manufacture of membranous el element - Google Patents
Manufacture of membranous el elementInfo
- Publication number
- JPH03110788A JPH03110788A JP1248429A JP24842989A JPH03110788A JP H03110788 A JPH03110788 A JP H03110788A JP 1248429 A JP1248429 A JP 1248429A JP 24842989 A JP24842989 A JP 24842989A JP H03110788 A JPH03110788 A JP H03110788A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- emitting layer
- particles
- light
- zns
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 88
- 230000002159 abnormal effect Effects 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000010408 film Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract 2
- 238000010304 firing Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 230000003213 activating effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005566 electron beam evaporation Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 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、薄膜ＥＬ素子及びその製造法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a thin film EL device and a method for manufacturing the same.
（従来の技術）
従来、薄膜ＥＬ素子において、その発光層としては発光
性付活元素を含むＺｎＳ薄膜が一般に利用されている。(Prior Art) Conventionally, in thin film EL devices, a ZnS thin film containing a luminescent activating element has generally been used as the light emitting layer.
該ＺｎＳ薄膜は電子ビーム蒸着法。The ZnS thin film was formed by electron beam evaporation.
スパッタリング法等により成膜される。これらの成膜法
において、発光性付活元素が添加された２ｎｓ焼結体タ
ーゲットを蒸着源として用いる方法が一般的であるが、
ＺｎＳのみからなる焼結体り−ゲットと発光性付活剤と
を別個のターゲットとする二元蒸着法も行われている。The film is formed by a sputtering method or the like. In these film-forming methods, it is common to use a 2ns sintered target to which a luminescent activating element is added as a deposition source.
A binary vapor deposition method has also been carried out in which a sintered body target made only of ZnS and a luminescent activator are used as separate targets.
ＺｎＳを含むターゲットは、例えば、ＺｎＳ結晶粉末に
適宜発光性付活剤を混合した後、所定の形状に成型し、
得られた成型体を高温で焼成して得られる（特公昭５２
−１０３５８号公報参照）。A target containing ZnS can be prepared by, for example, mixing ZnS crystal powder with an appropriate luminescent activator and then molding it into a predetermined shape.
It is obtained by firing the obtained molded body at high temperature (Special Publication No. 52
(Refer to Publication No.-10358).
得られるターゲットは、ＺｎＳ結晶粒子からなる焼結体
である。焼成工程を経る方法によって得られるＺｎＳを
含むターゲットは、いずれもこのようなＺｎＳ結晶粒子
からなる焼結体である。The obtained target is a sintered body made of ZnS crystal particles. All targets containing ZnS obtained by a method that involves a firing process are sintered bodies made of such ZnS crystal particles.
このような従来のＺｎＳを含む焼結体ターゲットを構成
するＺｎＳ結晶粒子の平均粒子径（後記に定義する）は
１本発明者らの研究によれば、１゜２ μｍ未満、通常
０．８μｍ程度ある。According to research by the present inventors, the average particle diameter (defined below) of ZnS crystal grains constituting such a conventional sintered target containing ZnS is less than 1.2 μm, usually 0.8 μm. To some extent.
（発明が解決しようとする課題）
前記したような従来のＺｎＳを含む焼結体ターゲットを
蒸着源とする電子ビーム蒸着法、スパッタリング法等に
より発光層を形成して得られる薄膜ＥＬ素子は、比較的
低い電圧〔例えば、４ｍｍ角の画素を有する薄膜ＥＬ素
子で約７０ Ｖｒｖｓ（１ｋ Ｈｚ正弦波）〕で絶絶縁
環を起こす。(Problem to be Solved by the Invention) A thin film EL element obtained by forming a light-emitting layer by an electron beam evaporation method, a sputtering method, etc. using a conventional sintered body target containing ZnS as a deposition source as described above is compared to An insulating ring occurs at a relatively low voltage (for example, about 70 Vrvs (1 kHz sine wave) in a thin film EL element having a 4 mm square pixel).
この原因は、本発明者らが究明したところ、薄膜ＥＬ素
子に異常粒子が非常に多いことにあることがわかった。The cause of this was investigated by the present inventors, and it was found that there were a large number of abnormal particles in the thin film EL element.
また、この異常粒子が発光層の形成時に発光層に付着し
たものであることがわかった。It was also found that these abnormal particles were attached to the luminescent layer during formation of the luminescent layer.
このような異常粒子は、ＺｎＳが昇華性物質であり、加
熱しても溶融することがないため、蒸着時におけるチャ
ージアップ等による電気的斥力、熱的エネルギーによる
突沸等により、ターゲットを構成するＺｎＳ結晶粒子が
飛散し膜に付着することによって発生するものである。Since ZnS is a sublimable substance and does not melt even when heated, these abnormal particles are caused by electrical repulsion due to charge-up during vapor deposition, bumping due to thermal energy, etc., and the ZnS constituting the target This occurs when crystal particles scatter and adhere to the film.
絶縁破壊電圧が低い原因は、このような異常粒子の発光
層への付着だけでなく、付着した異常粒子の脱離による
発光層の欠陥（凹部）にもある。The cause of the low dielectric breakdown voltage is not only the adhesion of such abnormal particles to the light-emitting layer, but also defects (concavities) in the light-emitting layer due to detachment of the adhered abnormal particles.
上記の異常粒子及び凹部は、また、薄膜ＥＬ素子の作製
工程中１発光層への水蒸気等のガスの侵入、ウェットプ
ロセスでの液の浸透等による不良発生原因にもなる。The above-mentioned abnormal particles and recesses also cause defects due to the intrusion of gas such as water vapor into one light-emitting layer during the manufacturing process of the thin film EL element, the infiltration of liquid during the wet process, and the like.
本発明は、このような問題点を解決するものであり、異
常粒子の付着又は付着粒子の脱離による凹部の少ない発
光層を有する薄膜ＥＬ素子及びその製造法を提供するも
のである。The present invention solves these problems and provides a thin film EL device having a light-emitting layer with fewer concavities caused by adhesion of abnormal particles or detachment of adhering particles, and a method for manufacturing the same.
（課題を解決するための手段）
本発明における薄膜ＥＬ素子は、透光性基材上に、透明
導電膜、発光層及び導電膜を順次積層し、これらの層間
のうち少なくとも一つの層間に絶縁層を形成してなる薄
膜ＥＬ素子において、上記発光層が異常粒子密度が１５
００個／ ｍ ｒｄ以下のものである。(Means for Solving the Problems) The thin film EL device of the present invention has a transparent conductive film, a light-emitting layer, and a conductive film sequentially laminated on a transparent base material, and an insulating layer is provided between at least one of these layers. In a thin film EL device formed by forming a layer, the light emitting layer has an abnormal particle density of 15
00 pieces/mrd or less.
異常粒子について説明する。第１図は、ガラス板上に作
製した発光層〔第１図（ａ）は後記比較例１で作製した
もの、第１図（ｂ）は後記実施例４で作成したもの〕を
透過法により撮影した光学顕微鏡写真（倍率１５０倍）
である、この写真で黒点として見えるのが発光層形成時
に付着した異常粒子又は該異常粒子が脱離してできた凹
部である。このような黒点は薄膜ＥＬ素子を構成する電
極及び絶縁層には観察されないので、上記の発光層の異
常粒子又は凹部に基づく黒点は、薄膜ＥＬ素子を作製後
、透明導電膜側から透過法により撮影する光学顕微鏡写
真又はアルムミウム等からなる背面電極（透明でないも
の）側から反射法により撮影する光学顕微鏡写真によっ
ても同様にｗｔ察することができる。黒点は発光層にほ
ぼ均一に分散している。これらが多いと、最終的に得ら
れる薄膜ＥＬ素子が比較的低い電圧で絶縁破壊を起す。The abnormal particles will be explained. Figure 1 shows a light-emitting layer produced on a glass plate [Figure 1 (a) was produced in Comparative Example 1 described later, and Figure 1 (b) was produced in Example 4 described later] by a transmission method. Optical micrograph taken (150x magnification)
What appears as black dots in this photograph are abnormal particles that adhered during the formation of the light emitting layer or recesses formed by the removal of the abnormal particles. Since such black spots are not observed on the electrodes and insulating layers that constitute the thin-film EL element, the black spots caused by abnormal particles or recesses in the light-emitting layer can be detected by a transmission method from the transparent conductive film side after fabricating the thin-film EL element. Similarly, wt can be detected by an optical microscope photograph taken or an optical microscope photograph taken by a reflection method from the back electrode (non-transparent) side made of aluminum or the like. The black spots are almost uniformly distributed in the light emitting layer. If there are too many of these, the thin film EL device finally obtained will suffer dielectric breakdown at a relatively low voltage.
異常粒子密度とは、■上記のような光学顕微鏡写真上に
５０ｍｍＸ５０ｍｍの正方形を異なった箇所に５箇所以
上区切り（一つの発光層又は一つの薄膜ＥＬ素子の異な
った箇所に光学顕微鏡写真を使用するのが好ましい）、
■これらの正方形内の黒点（異常粒子又は凹部）の個数
を数え、この個数からそれぞれ発光層（又は薄膜ＥＬ素
子）１ｍｒｒｒ（実寸）当りの黒点の個数を算出し、■
これらの値（単位：個／ ｍ ｒｄ ）を単純平均して
得られる値（単位：個／ ｍ ｒｄ ）である。Abnormal particle density is defined as: ■ On the optical microscope photograph shown above, divide 50 mm x 50 mm squares into five or more different locations (optical micrographs are used for different locations of one light-emitting layer or one thin film EL element) ),
■ Count the number of black dots (abnormal particles or recesses) within these squares, calculate the number of black dots per 1 mrrr (actual size) of the light emitting layer (or thin film EL element) from this number, and
This value (unit: number/m rd ) is obtained by simply averaging these values (unit: number/m rd ).
発光層の異常粒子密度が１５００個／ ｍ ｒｄ以下で
ある場合、薄膜ＥＬ素子は、従来よりも′絶縁破壊電圧
が著しく高くなる０発光層の異常粒子密度は、１２００
個／ ｍ ｒｒ？以下であるのが特に好ましい。When the abnormal particle density in the light emitting layer is 1500 particles/m rd or less, the thin film EL element has a significantly higher dielectric breakdown voltage than the conventional one.
pieces/mrr? The following is particularly preferred.
前記薄膜ＥＬ素子の各層について説明する。Each layer of the thin film EL element will be explained.
上記透光性基材としてはガラス板等が使用される。A glass plate or the like is used as the light-transmitting substrate.
透明導電膜は、ＳｎＯ，、Ｉｎ、Ｏ，、インジウムスズ
オキサイド（ＩＴＯ）等からなり、電子ビーム蒸着法、
抵抗加熱蒸着法、スパッタリング法。The transparent conductive film is made of SnO, In, O, indium tin oxide (ITO), etc., and is made by electron beam evaporation,
Resistance heating evaporation method, sputtering method.
ＣＶ Ｄ （Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏ
ｓｉｔｉｏｎ）法、プラズマＣＶＤ法等によって形成さ
れる。CVD (Chemical Vapor Depot)
It is formed by a plasma CVD method or the like.
発光層は、前記の特徴を有するものであるが。The light-emitting layer has the characteristics described above.
発光性付活元素が添加（ドープ）されているＺｎＳ等の
螢光体からなる。It is made of a phosphor such as ZnS to which a luminescent activating element is added (doped).
もう一つの導電膜は、透明導電膜と同様のものでもよく
、アルミニウム、クロム、金等の金属からなるものであ
ってもよい。The other conductive film may be the same as the transparent conductive film, or may be made of a metal such as aluminum, chromium, or gold.
前記絶縁層は、Ｔａ、Ｏ，、Ｙ、Ｏ，、ＳｉＯ，。The insulating layer is made of Ta, O, Y, O, SiO.
ＡＱ、Ｏ，、Ｓｉ、Ｎ４．ＡＱＮ、５ｒＴｉＯ，等から
なり、これらの層を２層以上積層して＃＠縁層としても
よい、これらの層の形成方法は、透明導電膜の形成方法
と同様である。AQ,O,,Si,N4. It is made of AQN, 5rTiO, etc., and two or more of these layers may be laminated to form a #@edge layer. The method of forming these layers is the same as the method of forming a transparent conductive film.
前記薄膜ＥＬ素子において、絶縁層は、前記透明導電膜
と前記発光層の間に及び／又は前記発光層と前記導電膜
の間に積層される。以下、前記透明導電膜と前記発光層
の間の絶縁層を第１の＃＠縁層と及び前記発光層と前記
導電膜の間を第２の絶縁層と言う。In the thin film EL device, an insulating layer is laminated between the transparent conductive film and the light emitting layer and/or between the light emitting layer and the conductive film. Hereinafter, the insulating layer between the transparent conductive film and the light emitting layer will be referred to as a first #@edge layer, and the layer between the light emitting layer and the conductive film will be referred to as a second insulating layer.
このような薄膜ＥＬ素子は、透明導電膜、第１の絶縁層
９発光層、第２の絶縁層及び導電膜（背面電極）を、こ
の順序で、基材上に順次形成して作成される。ただし、
第１及び第２のＭ縁層のうちどちらか一つはなくてもよ
い、また、発光層を形成後前記と同様の絶縁層を積１し
、さらに発光層を形成してもよい、これらの工程中発光
層の形成後真空下又はＡｒ、Ｎ、等の不活性ガス雰囲気
下に２００〜６５０℃の範囲で加熱処理してもよい。Such a thin film EL element is created by sequentially forming a transparent conductive film, a first insulating layer 9, a light-emitting layer, a second insulating layer, and a conductive film (back electrode) on a base material in this order. . however,
Either one of the first and second M edge layers may be omitted, or an insulating layer similar to the above may be laminated after forming the light emitting layer, and then a light emitting layer may be formed. After the formation of the light-emitting layer during the process, heat treatment may be performed at a temperature in the range of 200 to 650° C. under vacuum or in an atmosphere of an inert gas such as Ar or N.
前記薄膜ＥＬ素子を図面を用いて説明する。第２図は前
記薄膜ＥＬ素子の一例を示す断面図であり、基板１の上
に透明導電膜（透明電極）２．第１の絶縁層３２発光層
４．第２の絶縁／Ｗ５及びもう一つの導電膜（背面電極
）６をこの順に積層して作製したものである。The thin film EL device will be explained with reference to the drawings. FIG. 2 is a sectional view showing an example of the thin film EL element, in which a transparent conductive film (transparent electrode) 2. First insulating layer 32 light emitting layer 4. It was produced by laminating the second insulator/W5 and another conductive film (back electrode) 6 in this order.
前記発光層は、好ましくは、ＺｎＳ焼結体からなり、該
焼結体を構成するＺｎＳ結晶粒子の平均粒子径が１．２
μｍ以上であるターゲットを用いる真空蒸着法によっ
て形成される。これにより。The light-emitting layer is preferably made of a ZnS sintered body, and the average particle diameter of ZnS crystal particles constituting the sintered body is 1.2.
It is formed by a vacuum evaporation method using a target having a diameter of μm or more. Due to this.
異常粒子密度が約１２００個／ｍイ以下の発光層を形成
することができる。上記ＺｎＳ結晶粒子の平均粒子径が
１．５μｍ以上であると上記異常粒子密度を約１２００
個／ ｍ ｒ＆以下にすることができる。A light-emitting layer having an abnormal particle density of about 1200 particles/m2 or less can be formed. When the average particle diameter of the ZnS crystal particles is 1.5 μm or more, the abnormal particle density is about 1200 μm or more.
It can be less than pcs/m r&.
上記ターゲットは、ＺｎＳを母体物質とするものであり
、発光性付活元素が添加（ドープ）されているものでも
よい６発光性付活元素としては、Ｍｎ、Ｔｍ、Ｓｍ等が
あり、Ｚｎに対して０．００１〜１０モル％添加されて
いるのが好ましい。The above target has ZnS as a host material, and may be doped with a luminescent activating element. 6 Luminescent activating elements include Mn, Tm, Sm, etc. It is preferable that the amount is 0.001 to 10 mol %.
ＺｎＳ結晶粒子の平均粒子径は次のようにして測定され
る。The average particle diameter of ZnS crystal particles is measured as follows.
粉砕したターゲットの電子顕微鏡写真（倍率約５ｏｏｏ
倍）を取る。この電子Ｍ微鏡写真の中で輪郭が明確な粒
子だけに着目し、その輪郭で囲まれる面積を算出し、つ
いで、算出された面積に相当する円の直径（以下、１円
相当径」という）を算出する。このようにして、２００
〜４００個の粒子について円相光径を算出し、これらの
平均値を、ＺｎＳ結晶粒子の平均粒子径とする０個々の
粒子の面積は、粒子の輪郭を座標入出力装置（デジタイ
ザー）を用いてコンピュータに入力し、その輪郭で囲ま
れる面積を算出させることによって行うことができる。Electron micrograph of the crushed target (magnification approximately 5ooo)
times). Focusing only on particles with clear outlines in this electron micrograph, we calculate the area surrounded by the outline, and then calculate the diameter of a circle corresponding to the calculated area (hereinafter referred to as 1-yen equivalent diameter). ) is calculated. In this way, 200
The circular phase diameter is calculated for ~400 particles, and the average value of these is taken as the average particle diameter of the ZnS crystal particles.The area of each particle is calculated by using the coordinate input/output device (digitizer) of the particle outline. This can be done by inputting it into a computer and having it calculate the area surrounded by the contour.
粉砕したターゲットの電子顕微鏡写真（倍率５０００倍
）の例を第３図に示す、また、第４図に、第３図に示す
電子顕微鏡写真において、面積を算出する粒子の輪郭を
第３図と同一縮尺で示す。Figure 3 shows an example of an electron micrograph (5000x magnification) of a crushed target, and Figure 4 shows the contours of the particles whose area is to be calculated in the electron microscope photograph shown in Figure 3. Shown at the same scale.
前記ターゲットは、次のようにして製造することができ
る。The target can be manufactured as follows.
■平均粒子径が１．２ μｍ未満又は１．５ μｍ未満
のＺｎＳ結晶粉末を成型体となし、これを焼成して結晶
を成長させ、平均粒子径が１．２ μｍ以上又は１．５
μｍ以上のＺｎＳ結晶粒子からなる焼結体を形成する
方法。■ A ZnS crystal powder with an average particle size of less than 1.2 μm or less than 1.5 μm is made into a molded body, which is fired to grow crystals, and the average particle size is 1.2 μm or more or 1.5 μm or more.
A method for forming a sintered body consisting of ZnS crystal particles of μm or more.
一般に入手可能なＺｎＳ結晶粉末は、前記の定義による
平均粒子径が、１．２ μｍ未満、通常０．８ μｍ前
後のものであるが、これを焼成することにより、結晶を
成長させることができる。Generally available ZnS crystal powder has an average particle size as defined above of less than 1.2 μm, usually around 0.8 μm, and by firing it, crystals can be grown. .
原料であるＺｎＳ結晶粉末の成型体は、該ＺｎＳ結晶粉
末のみ又はこれと発光性付活剤の混合物を成形用治具等
を用いてプレス機等により１円筒形、円板形等に成型す
ることによって製造できる。A molded body of ZnS crystal powder, which is a raw material, is formed by molding the ZnS crystal powder alone or a mixture of it and a luminescent activator into a cylindrical shape, a disk shape, etc. using a press machine etc. using a molding jig etc. It can be manufactured by
この場合、成型しやすいように少量の水、ポロビニルア
ルコール等を加えてもよい。上記発光性付活剤としては
、ＭｎＳＯ４、ＭｎＯ，、ＭｎＳ、ＭｎＣＱ、、ＴｂＦ
、、Ｔｍ、８３等があり、得られるターゲット中に発光
性付活元素がＺｎに対して０．００１ 〜１０モル％に
含まれるように使用されるのが好ましい。In this case, a small amount of water, polovinyl alcohol, etc. may be added to facilitate molding. Examples of the luminescent activator include MnSO4, MnO, MnS, MnCQ, TbF.
.
このような成型体は、ついで、焼成され、焼結体とされ
る。この場合、雰囲気はＡｒガス等の不活性ガス雰囲気
でもよいが、Ｈ，Ｓ ガス等の硫化性ガスを含む硫化
性雰囲気が好ましい。硫化性雰囲気中には硫化性ガスが
５０〜１００容量％含まれるのが好ましい、硫化性雰囲
気に含まれていてもよい他のガスとしては、上記不活性
ガス等がある。焼成温度は５００〜１２００℃が好まし
く、焼成時間は２〜２０時間が好ましい。Such a molded body is then fired to form a sintered body. In this case, the atmosphere may be an inert gas atmosphere such as Ar gas, but preferably a sulfiding atmosphere containing sulfiding gas such as H or S gas. It is preferable that the sulfiding atmosphere contains 50 to 100% by volume of the sulfiding gas.Other gases that may be included in the sulfiding atmosphere include the above-mentioned inert gases. The firing temperature is preferably 500 to 1200°C, and the firing time is preferably 2 to 20 hours.
■ＺｎＯ，ＺｎＣ０，又はＺ ｎ Ｓ Ｏ，を成型体と
なし、これを焼成して平均粒子径が１．２ μｍ以上、
好ましくは１．５ μｍ以上のＺｎＳ結晶粒子からなる
焼結体を形成する方法。■Mold ZnO, ZnC0, or ZnS O, and sinter it to form a molded body with an average particle size of 1.2 μm or more.
A method of forming a sintered body comprising ZnS crystal particles preferably having a size of 1.5 μm or more.
上記成形体は、前記酸化物、炭酸塩若しくは硫酸塩をそ
のまま又はこれらのうち一種と発光性付活剤を混合し、
前記■の方法と同様にして製造することができる。この
成型体において前記酸化物。The above-mentioned molded body contains the above-mentioned oxide, carbonate or sulfate as is or one of them is mixed with a luminescent activator,
It can be produced in the same manner as the method (2) above. In this molded body, the oxide.
炭酸塩又は硫酸塩は強く凝集しているのが好ましい。Preferably, the carbonate or sulfate is highly agglomerated.
このような成型体は、次いで焼成される。この場合、雰
囲気はＨ，Ｓ ガス等の硫化性ガスを含む硫化性雰囲気
とされる。この雰囲気は、Ａｒガス等の不活性ガスが混
合されていてもよいが、硫化性ガスが５０〜１００容量
％であるのが好ましい。Such a molded body is then fired. In this case, the atmosphere is a sulfiding atmosphere containing sulfiding gases such as H and S gases. This atmosphere may be mixed with an inert gas such as Ar gas, but preferably contains 50 to 100% by volume of sulfidic gas.
また、焼成温度は５００〜１２００℃が好ましく、焼成
時間は１〜１０時間が好ましい。この焼成により、酸素
がイオウと置き換わり（硫化反応し）目的のＺｎＳ結晶
粒子からなる焼結体が得られる。この場合、酸素がいく
らか残存していてもよく、母体物質全体の組成がＺ ｎ
５ｘＯｙ （ただし、ｘ＋ｙはほぼ１であり、かつＯ
≦ｙ≦０．２である）であればよい、酸素が残存してい
る場合、ＺｎＳに酸素が固溶しているか又はさらに一部
のＺｎが酸化されている。このような組成は、雰囲気組
成、焼成温度、焼成時間等を制御して行なうことができ
る。上記硫化反応により、酸素がどの程度残存している
かは、Ｘ線回折法、オージェ電子分光法、燃焼法等によ
り確認することができる。Further, the firing temperature is preferably 500 to 1200°C, and the firing time is preferably 1 to 10 hours. By this firing, oxygen is replaced with sulfur (sulfurization reaction occurs), and a desired sintered body consisting of ZnS crystal particles is obtained. In this case, some oxygen may remain and the overall composition of the host material is Z n
5xOy (However, x+y is approximately 1, and O
≦y≦0.2). If oxygen remains, oxygen is solidly dissolved in ZnS, or some Zn is oxidized. Such a composition can be achieved by controlling the atmosphere composition, firing temperature, firing time, etc. The amount of oxygen remaining due to the sulfidation reaction can be confirmed by X-ray diffraction, Auger electron spectroscopy, combustion method, etc.
このような方法によると結晶粒子径の大きなＺｎｓ結晶
粒子を比較的簡単に得ることができる。According to such a method, Zns crystal particles having a large crystal particle size can be obtained relatively easily.
■発光性付活元素が添加されていてもよいＺｎＳ （母
体物質）を酸素ガスを含む雰囲気下に加熱処理して前記
ＺｎＳｘＯｙ組成（ただし、Ｏくｙ≦０．２）のターゲ
ットを製造する方法。■A method of manufacturing a target having the above-mentioned ZnSxOy composition (Oxy≦0.2) by heat-treating ZnS (base material) to which a luminescent activating element may be added in an atmosphere containing oxygen gas. .
発光性付活元素が添加されている場合、その量は母体物
質に対して０．００１〜１０モル％が好ましい。また、
酸素ガスを含む雰囲気とは、酸素を０゜１容量％以上含
むものが好ましく、他にＡ ｒ ｓ Ｎ２等の不活性ガ
スを含んでいてもよく、空気を使用してもよい、加熱温
度は、５００〜１２００℃が好ましい、前記したＺｎＳ
ｘＯｙ組成は前記と同様に制御し、確認することができ
る。When a luminescent activating element is added, the amount thereof is preferably 0.001 to 10 mol % based on the base material. Also,
The atmosphere containing oxygen gas preferably contains at least 0.1% by volume of oxygen, and may also contain an inert gas such as Ars N2, or may use air.The heating temperature is , preferably 500 to 1200°C, the above-mentioned ZnS
The xOy composition can be controlled and confirmed in the same manner as described above.
母体物質がＺｎＳｘＯｙ組成で表される場合、ｙは０．
０２〜０．２が好ましく、この組成の母体物質を含むタ
ーゲットを用いて形成される発光層を含む薄膜ＥＬ素子
は１発光輝度が向上する。When the parent material is represented by a ZnSxOy composition, y is 0.
02 to 0.2 is preferable, and a thin film EL element including a light-emitting layer formed using a target containing a host material having this composition improves luminance by 1.
前記ターゲットを用いる発光層の形成方法としては電子
ビーム蒸着法、スパッタリング法等の真空蒸着法が利用
できる。蒸着時の基板温度は１５０〜３００℃が好まし
い。As a method for forming the light emitting layer using the target, vacuum evaporation methods such as electron beam evaporation method and sputtering method can be used. The substrate temperature during vapor deposition is preferably 150 to 300°C.
（実施例） 以下、本発明の実施例を示す。(Example) Examples of the present invention will be shown below.
実施例１〜５及び比較例１
（１）ターゲットの作製
高純度ＺｎＯ粉末（前記で定義した平均粒子径が０．５
μｍのもの）１６．２７４ｇ と高純度ＭｎＳＯ４
・Ｈ２０粉末０．２４２ ｇ （ＭｎはＺｎ原子に対
して０．７２ｍｏ１％）とを乾式で均一に混合し、得ら
れた混合物を成型治具に入れて円筒の高さ方向に約２０
ｋｇ／ａ＃の圧力を加え高さ２０ｍｍ、直径２０ｍｍの
円筒形に成型した。次に、この成型体を石英製のボート
に入れてＨ，Ｓ ガスを流した石英管中で焼成（硫化
・焼結）した、焼成温度１０００℃、上記のガスの流量
２００ｃｃ／分とし、焼成時間は下記衣１に示すように
した。Examples 1 to 5 and Comparative Example 1 (1) Preparation of target High purity ZnO powder (average particle diameter as defined above is 0.5
μm) 16.274g and high purity MnSO4
- 0.242 g of H20 powder (Mn is 0.72 mo1% with respect to Zn atoms) is mixed uniformly in a dry method, and the resulting mixture is put into a molding jig and molded about 20 g in the height direction of the cylinder.
A pressure of kg/a# was applied to mold it into a cylindrical shape with a height of 20 mm and a diameter of 20 mm. Next, this molded body was placed in a quartz boat and fired (sulfurized and sintered) in a quartz tube through which H, S gas was flowed. The time was as shown in Clothing 1 below.
得られたターゲットついて前記した方法で該ターゲット
を構成する結晶粒子の平均粒子径を求めた。この結果を
、円相当径を求めた粒子数とともに表１に示す。The average particle diameter of the crystal grains constituting the obtained target was determined by the method described above. The results are shown in Table 1 along with the number of particles for which the equivalent circle diameter was determined.
（２）薄膜ＥＬ素子の作成 次に、第２図に示すような薄膜ＥＬ素子を作製した。(2) Creation of thin film EL device Next, a thin film EL device as shown in FIG. 2 was fabricated.
基材１としてのホウケイ酸ガラス板（３４ｍ角。Borosilicate glass plate (34m square) as base material 1.
厚さ１．１＋ａ）上にＩＴＯ膜をスパッタリング法で形
成し、これをエツチングして透明導電膜２としてのスト
ライプ状１．ＴＯ透明電極（厚さ２００ｎｍ、電極幅４
．０ａｓ）を形成した。この上に第１の絶縁層３として
Ｓｉ、Ｎ４をプラズマＣＶＤ法で２２０ｎｍの厚さに成
膜した。An ITO film with a thickness of 1.1+a) is formed on the film by sputtering, and this is etched to form a striped pattern 1.1 as the transparent conductive film 2. TO transparent electrode (thickness 200 nm, electrode width 4
．． 0as) was formed. On top of this, a first insulating layer 3 of Si and N4 was formed to a thickness of 220 nm by plasma CVD.
さらに、この上に、上記で得たターゲットを用いて電子
ビーム蒸着法により発光層４を成膜した。Furthermore, a light emitting layer 4 was formed thereon by electron beam evaporation using the target obtained above.
このときの条件は、基板温度２００℃、成膜速度６０ｎ
ｍ／分とし、発光層は６００ｎｍの厚さにした。The conditions at this time were a substrate temperature of 200°C and a film formation rate of 60n.
m/min, and the luminescent layer had a thickness of 600 nm.
ついで、第２の絶縁層５を第１の絶縁層３と同様にして
作成した。最後にアルミニウム膜をスパッタリング法で
形成し、エツチングして背面電極６としてのストライプ
状アルミニウム電極（厚さ２００ｎｍ、電極幅４．０
ｍｍ）を形成して薄膜ＥＬ素子を得た。この薄膜ＥＬ素
子は４ｍｍ角の画素を５個有するものであり、同時に、
基材１上に７〜８個の素子を作製した。Next, the second insulating layer 5 was created in the same manner as the first insulating layer 3. Finally, an aluminum film is formed by sputtering and etched to form a striped aluminum electrode (thickness: 200 nm, electrode width: 4.0 nm) as the back electrode 6.
mm) to obtain a thin film EL device. This thin film EL element has five pixels of 4 mm square, and at the same time,
Seven to eight elements were fabricated on the base material 1.
この素子を用い、絶縁破壊電圧を（印加電圧：１ｋＨｚ
正弦波）求めた。これらの結果を表１に示す。Using this element, the dielectric breakdown voltage (applied voltage: 1kHz
sine wave) was obtained. These results are shown in Table 1.
また、前記で作製したターゲットを用いて、ガラス板上
に直接、上記薄膜ＥＬ素子の発光層形成法と同じ条件で
発光層を形成し、前述した方法によって異常粒子密度（
５箇所の平均値）を測定した。この結果を表１に示す。Further, using the target prepared above, a light emitting layer was formed directly on a glass plate under the same conditions as the light emitting layer formation method of the thin film EL element described above, and the abnormal particle density was
The average value of 5 points) was measured. The results are shown in Table 1.
なお、実施例１〜６で作製したターゲットにはＸ線回折
法で調べたところ、ＺｎＯ結晶に基づくピークはなく、
比較例１で得られたターゲットにはにＺｎＯ結晶に基づ
くピークが極くわずか検出された。In addition, when the targets prepared in Examples 1 to 6 were examined by X-ray diffraction, there were no peaks based on ZnO crystals.
In the target obtained in Comparative Example 1, very few peaks due to ZnO crystals were detected.
表１
焼成温度及び試験結果
１）測定粒子数は、平均粒子径を算出するために、円相
当径を測定したＺｎＳ結晶粒子の個数である。Table 1 Firing temperature and test results 1) The number of measured particles is the number of ZnS crystal particles whose equivalent circle diameter was measured in order to calculate the average particle diameter.
２）絶縁破壊電圧は、同一条件で作成した薄膜ＥＬ素子
のいくつかについての平均値とバラツキ（上限と下限）
を示し、測定個数はこのときに絶縁破壊電圧を測定した
薄膜ＥＬ素子の個数である。2) Dielectric breakdown voltage is the average value and variation (upper and lower limits) for several thin film EL devices created under the same conditions.
is the number of thin film EL elements whose dielectric breakdown voltage was measured at this time.
前記実施例１〜５及び比較例１におけるターゲットを構
成するＺｎＳ結晶粒子の平均粒子径と発光層の異常粒子
密度の関係をを示すグラフを第５図に示す。FIG. 5 is a graph showing the relationship between the average particle diameter of the ZnS crystal particles constituting the target in Examples 1 to 5 and Comparative Example 1 and the abnormal particle density in the light emitting layer.
実施例７
ターゲットの作製において、高純度
ＭｎＳＯ４・Ｈ，Ｏ粉末を用いないこと以外は、実施例
３に準じてターゲットを作製した。このターゲットを構
成するＺｎＳ結晶粒子の平均粒子径は２．２ μｍ〔測
定粒子数：２５２）であった。Example 7 A target was manufactured according to Example 3, except that high-purity MnSO4.H,O powder was not used. The average particle diameter of the ZnS crystal particles constituting this target was 2.2 μm (number of measured particles: 252).
ついで、発光層形成の蒸着源としてこのターゲット及び
Ｍ ｎ Ｃｌ ２粉末を用いること以外は、実施例４に
準じて薄膜ＥＬ素子を作製し絶縁破壊電圧を測定した。Next, a thin film EL device was produced according to Example 4, except that this target and M n Cl 2 powder were used as a vapor deposition source for forming a light emitting layer, and the dielectric breakdown voltage was measured.
さらに実施例４と同様にして異常粒子密度を測定した。Furthermore, the abnormal particle density was measured in the same manner as in Example 4.
これらの結果、絶縁破壊電圧は２６０±２５Ｖｒｍｓ（
測定個数＝５３、異常粒子密度は１０５０個／ ｍ ｒ
ｄであった。As a result, the breakdown voltage was 260±25Vrms (
Number of particles measured = 53, abnormal particle density 1050 particles/m r
It was d.
実施例８
高純度ＺｎＳ粉末（前記で定義した平均粒子径が０．８
μｍのもの）にＺｎに対してＭｎが１．０モル％になる
ようにＭ ｎ ＣＱ 、を乾式で均一に混合し、得られ
た混合物を０．５ トン／ａｌの圧力で実施例１と同様
に成型した０次に、この成型体を石英製のボートに入れ
てＨ，Ｓガスを流した石英管中で焼成した。焼成温度１
０００℃、上記のガスの流量２００ｃｃ／分とし、焼成
時間は５時間とした。得られたターゲットを構成するＺ
ｎＳ結晶粒子の平均粒子径は２．１ μｍ［測定粒子数
：２００）であった。Example 8 High purity ZnS powder (average particle size defined above is 0.8
M n CQ was mixed uniformly in a dry process so that the Mn content was 1.0 mol % with respect to Zn, and the resulting mixture was mixed with Example 1 at a pressure of 0.5 ton/al. This molded body was molded in the same manner, and then placed in a quartz boat and fired in a quartz tube through which H and S gases were flowed. Firing temperature 1
000° C., the flow rate of the above gas was 200 cc/min, and the firing time was 5 hours. Z constituting the obtained target
The average particle diameter of the nS crystal particles was 2.1 μm [number of measured particles: 200].
ついで１発光層形成の蒸着源としてこのターゲットを用
いること以外は、実施例１に準じて薄膜ＥＬ素子を作製
し絶縁破壊電圧を測定した。さらに実施例１と同様にし
て異常粒子密度を測定した。Next, a thin film EL device was prepared according to Example 1 except that this target was used as a vapor deposition source for forming one light emitting layer, and the dielectric breakdown voltage was measured. Furthermore, the abnormal particle density was measured in the same manner as in Example 1.
これらの結果、絶縁破壊電圧は２４０±２０Ｖｒｍｓ（
測定個数ニア〕、異常粒子密度は１２５０個／ｍｍ２で
あった。As a result, the breakdown voltage was 240±20Vrms (
The number of measured particles was near], and the abnormal particle density was 1250 particles/mm2.
実施例９
なお、実施例３で得られたターゲットを空気中６００℃
で３０分間熱処理し、ターゲットに酸素を拡散させた。Example 9 The target obtained in Example 3 was heated at 600°C in air.
The target was heat-treated for 30 minutes to diffuse oxygen into the target.
このターゲットの中のＳ及びＯを燃焼法で分析した結果
ＺｎＳｘＯｙで規定されるＸ及びｙがｘ＝０．８．ｙ＝
０．１であった。このターゲットを形成する結晶素子の
平均粒子径は、２．２μｍであり、実施例３で得られた
ターゲットと実質的に変わらない、このターゲットを用
いて実施例３と同様にして薄膜ＥＬ素子を作成しその印
加電圧−発光特性を測定した。その結果、しきい電圧よ
り３０Ｖ高い電圧での発光輝度は１ｋＨｚ正弦波関動で
３５００ｃｄ／耐あり、この輝度は酸化処理していない
実施例３で得た薄膜ＥＬ素子の輝度の１．５倍あった。As a result of analyzing the S and O in this target using the combustion method, it was found that X and y defined by ZnSxOy were x=0.8. y=
It was 0.1. The average particle diameter of the crystal element forming this target is 2.2 μm, which is substantially the same as the target obtained in Example 3. Using this target, a thin film EL element was fabricated in the same manner as in Example 3. The applied voltage-emission characteristics were measured. As a result, the emission brightness at a voltage 30V higher than the threshold voltage was 3500 cd/withstand with a 1kHz sine wave, and this brightness was 1.5 times the brightness of the thin film EL element obtained in Example 3 without oxidation treatment. there were.
また、ここで得られた薄膜ＥＬ素子について、発光層の
異常粒子密度は１０３０個／ｌ１ｍ１２及び結像破壊電
圧は２６０±２５ Ｖｒｍｓ （測定個数７）であり、
実施例３と実質的に変わらない。In addition, regarding the thin film EL device obtained here, the abnormal particle density in the light emitting layer was 1030 particles/l1m12 and the imaging breakdown voltage was 260 ± 25 Vrms (measured number of particles 7),
There is no substantial difference from Example 3.
（発明の効果）
請求項１〜２に係る又は請求項３〜５の方法によって得
られる薄膜ＥＬ素子において、その発光層への付着粒子
（異常粒子）が少なく、結果として、該薄膜ＥＬ素子は
絶縁破壊電圧が高く、良好なものである。請求項５の方
法によって得られる薄膜ＥＬ素子は発光輝度も優れる。(Effect of the invention) In the thin film EL device according to claims 1 to 2 or obtained by the method of claims 3 to 5, there are few particles (abnormal particles) attached to the light emitting layer, and as a result, the thin film EL device has The dielectric breakdown voltage is high and good. The thin film EL device obtained by the method of claim 5 also has excellent luminance.
第１図は発光層の光学顕微鏡写真、第２図は本発明の薄
膜ＥＬ素子の一例を示す断面図、第３図は本発明のター
ゲットの粉砕物の電子顕微鏡写真。FIG. 1 is an optical micrograph of a light-emitting layer, FIG. 2 is a cross-sectional view showing an example of the thin film EL element of the present invention, and FIG. 3 is an electron micrograph of a crushed target of the present invention.
Claims (5)
順次積層し、これらの層間のうち少なくとも一つの層間
に絶縁層を形成してなる薄膜ＥＬ素子において、上記発
光層の異常粒子密度が１５００個／ｍｍ＾２以下である
薄膜ＥＬ素子．1. In a thin film EL device in which a transparent conductive film, a light-emitting layer, and a conductive film are sequentially laminated on a light-transmitting base material, and an insulating layer is formed between at least one of these layers, abnormal particles in the light-emitting layer A thin film EL device with a density of 1500 pieces/mm^2 or less.
である請求項１記載の薄膜ＥＬ素子。2. 2. The thin film EL device according to claim 1, wherein the density of abnormal particles in the light emitting layer is 1200 particles/mm^2 or less.
順次積層し、これらの層間のうち少なくとも一つの層間
に絶縁層を形成する薄膜ＥＬ素子の製造法において、上
記発光層を、ＺｎＳ焼結体からなり、該焼結体を構成す
るＺｎＳ結晶粒子の平均粒子径が１．２μｍ以上である
ターゲットを用いる真空蒸着法によって形成することを
特徴とする薄膜ＥＬ素子の製造法。3. In a method for manufacturing a thin film EL device, in which a transparent conductive film, a light-emitting layer, and a conductive film are sequentially laminated on a light-transmitting base material, and an insulating layer is formed between at least one of these layers, the light-emitting layer is 1. A method for manufacturing a thin film EL element, comprising forming a thin film EL element by a vacuum evaporation method using a target made of a ZnS sintered body and in which the average particle size of ZnS crystal grains constituting the sintered body is 1.2 μm or more.
ｎＳ結晶粒子の平均粒子径が１．５μｍ以上のものであ
る請求項３記載の薄膜ＥＬ素子の製造法。4. The target according to claim 3 comprises Z
4. The method for manufacturing a thin film EL device according to claim 3, wherein the nS crystal particles have an average particle diameter of 1.5 μm or more.
ｙ（ただし、ｘ＋ｙはほぼ１であり、０≦ｙ≦０．２で
ある）で表される組成を有するものである請求項３又は
請求項４記載の薄膜ＥＬ素子の製造法。5. The target is ZnS_xO_
5. The method of manufacturing a thin film EL device according to claim 3, wherein the thin film EL device has a composition represented by y (where x+y is approximately 1 and 0≦y≦0.2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1248429A JPH03110788A (en) | 1989-09-25 | 1989-09-25 | Manufacture of membranous el element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1248429A JPH03110788A (en) | 1989-09-25 | 1989-09-25 | Manufacture of membranous el element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03110788A true JPH03110788A (en) | 1991-05-10 |
Family
ID=17177994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1248429A Pending JPH03110788A (en) | 1989-09-25 | 1989-09-25 | Manufacture of membranous el element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03110788A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6803729B2 (en) | 2001-11-27 | 2004-10-12 | Nippon Seiki Co., Ltd. | Drive circuit for organic EL device |
-
1989
- 1989-09-25 JP JP1248429A patent/JPH03110788A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6803729B2 (en) | 2001-11-27 | 2004-10-12 | Nippon Seiki Co., Ltd. | Drive circuit for organic EL device |
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