JPH03192690A - El display element - Google Patents
El display elementInfo
- Publication number
- JPH03192690A JPH03192690A JP1331579A JP33157989A JPH03192690A JP H03192690 A JPH03192690 A JP H03192690A JP 1331579 A JP1331579 A JP 1331579A JP 33157989 A JP33157989 A JP 33157989A JP H03192690 A JPH03192690 A JP H03192690A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- display element
- film
- transparent
- insulating layer
- 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.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 6
- 229910021332 silicide Inorganic materials 0.000 claims description 5
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims 1
- 229910000681 Silicon-tin Inorganic materials 0.000 claims 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 6
- 229910008479 TiSi2 Inorganic materials 0.000 abstract description 3
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 44
- 230000015556 catabolic process Effects 0.000 description 16
- 239000005083 Zinc sulfide Substances 0.000 description 10
- 229910052984 zinc sulfide Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- -1 zinc sulfide (ZnS) Chemical compound 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004299 TbF3 Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 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
- 238000009413 insulation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 210000001747 pupil Anatomy 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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、例えば計器類のバンクライト用の面光源等に
使用されるＢＬ（エレクトロミネッセンス）ディスプレ
イ素子に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a BL (electroluminescence) display element used, for example, as a surface light source for bank lights of instruments.
ＥＬディスプレイ素子は、硫化亜鉛（ＺｎＳ）等の蛍光
体に電界をかけたときに発光する現象を利用したもので
、自発光型の平面ディスプレイを構成するものとして注
目されている。EL display elements utilize the phenomenon of emitting light when an electric field is applied to a phosphor such as zinc sulfide (ZnS), and are attracting attention as a component of a self-luminous flat display.
このような従来のＥＬディスプレイ素子の一例を第３図
に示す。An example of such a conventional EL display element is shown in FIG.
図において、ガラス基板１上には、ＩＴＯ膜よりなる透
明電極１１．酸化タンタル（ＴａｚＯｓ）等よりなる第
１絶縁層膜２１１発光層４１．第２絶縁層膜２２が順次
積層形成してあり、さらにその上にＩＴＯ膜よりなる透
明電極１２が配設しである。In the figure, a transparent electrode 11 made of an ITO film is placed on a glass substrate 1. A first insulating layer film 211 made of tantalum oxide (TazOs) or the like; a light emitting layer 41; A second insulating layer 22 is sequentially laminated, and a transparent electrode 12 made of an ITO film is further disposed thereon.
Ｉ Ｔ Ｏ（Ｉｎｄｉｕｍ Ｔｉｎ ０ｘｉｄｅ）膜は
、酸化インジウム（ＩｎｚＯｉ）にすず（Ｓｎ）をドー
プした透明の導電膜で、低抵抗率であることから従来よ
り透明電極用として広く使用されている。An ITO (Indium Tin Oxide) film is a transparent conductive film made of indium oxide (InzOi) doped with tin (Sn), and has been widely used for transparent electrodes because of its low resistivity.
発光層４１としては、例えば、ＺｎＳを母材層とし、発
光中心としてマンガン（Ｍｎ）や三フフ化テルビウム（
ＴｂＦ３）を添加したものが使用される。ＥＬ全発光よ
る発光色はＺｎＳ中の添加物の種類によって決まり、例
えば発光中心としてＭｎを添加した場合にはオレンジ色
、ＴｂＦ：＋を添加した場合にはグリーンの発光が得ら
れる。The light-emitting layer 41 may be made of, for example, ZnS as a base material layer and manganese (Mn) or terbium trifluoride (as a light-emitting center).
TbF3) is used. The color of light emitted by total EL emission is determined by the type of additive in ZnS; for example, when Mn is added as a luminescent center, orange light is obtained, and when TbF:+ is added, green light is obtained.
しかしながら、上記構造のＥＬディスプレイ素子を製作
し、連続発光試験に供したところ、２００時間という比
較的短時間で絶縁破壊が生じ、発光効率ならびに耐久性
能面で大きな問題を有することが判明した。これは駆動
電圧が低い場合Ｇこしよそれほど重要ではないが、表示
面積の拡大等で駆動電圧を高くする必要が生じた場合に
は大きな問題となる。However, when an EL display element with the above structure was manufactured and subjected to a continuous light emission test, dielectric breakdown occurred in a relatively short time of 200 hours, and it was found that there were major problems in light emission efficiency and durability. This is not so important when the drive voltage is low, but it becomes a big problem when it becomes necessary to increase the drive voltage to increase the display area or the like.
また、近年、異なる発光色を示す発光層を複数積層して
、ＥＬディスプレイ素子をチューナプルカラー化するこ
とが提案されている（例えば、特開昭６０−２６４０９
６号公報、特開昭６０−２１６４９６号公報等）。In addition, in recent years, it has been proposed to make EL display elements tunable color by stacking a plurality of light emitting layers that emit light of different colors (for example, Japanese Patent Laid-Open No. 60-26409
6, JP-A-60-216496, etc.).
ところが、上記した絶縁層膜の耐圧低下現象は、このよ
うな積層型のＥＬディスプレイ素子において特に顕著で
あることが判明し、実用化に際し大きな障害となってい
る。However, it has been found that the above-mentioned phenomenon of reduction in breakdown voltage of the insulating layer film is particularly remarkable in such a laminated type EL display element, and has become a major obstacle to practical application.
本発明者らは、かかる点に鑑みて鋭意、研究したところ
、絶縁層膜の耐圧低下現象につき、次のごときメカニズ
ムを知見した。In view of the above, the present inventors conducted extensive research and discovered the following mechanism regarding the phenomenon of a decrease in breakdown voltage of an insulating layer film.
即ち、ＥＬディスプレイ素子の製造工程において、透明
電極を構成するＩＴＯ膜が部分的に還元されてその膜中
に部分的にＩｎ金属が存在し、この導電体であるＩｎが
絶縁層膜中に拡散し、このため絶縁層膜の耐圧低下現象
が生じることを突き止めた。That is, in the manufacturing process of EL display elements, the ITO film constituting the transparent electrode is partially reduced, and In metal is partially present in the film, and this conductive In is diffused into the insulating layer film. However, it was discovered that this caused a decrease in the withstand voltage of the insulating layer.
本発明は、かような知見に基づいて案出されたものであ
って、絶８ｉ層膜の電気耐圧が高く、高電圧駆動時にお
いても絶縁破壊が生しることがなｌ、＞ため、高信頼性
を有するＥＬディスプレイ素子を稈供することを目的と
するものである。The present invention was devised based on such knowledge, and the electrical breakdown voltage of the insulated 8i layer film is high, and dielectric breakdown does not occur even when driven at high voltage. The purpose is to provide an EL display element with high reliability.
本発明は、かかる目的を達成するため、少なくとも一方
をＩＴＯ膜で構成した一対の電極の間に、絶縁膜層を介
して発光層を配したＥＬディスプレイ素子において、一
対の電極のうちＩＴＯ膜で構成された電極と該電極側に
位置する絶縁層膜との間に透明なＩｎ捕捉層を配したと
いう技術的手段を採用したものである。In order to achieve this object, the present invention provides an EL display element in which a light emitting layer is disposed between a pair of electrodes, at least one of which is made of an ITO film, with an insulating film layer interposed therebetween. A technical measure is adopted in which a transparent In trapping layer is disposed between the constructed electrode and the insulating layer film located on the electrode side.
また、上記透明なＩｎ捕捉層は、Ｔｉ、Ｖ、Ｃｒ。Further, the transparent In trapping layer is made of Ti, V, or Cr.
Ｈｆ、Ｚｎ、Ｎｂ、Ｍｏ、Ｔａ、’ Ｗ、Ｐｔから選択
された高融点金属のシリサイド、または価電子制御され
た半導体、例えばｎ型半導体で構成することができる。It can be composed of a silicide of a high-melting point metal selected from Hf, Zn, Nb, Mo, Ta, 'W, and Pt, or a semiconductor with controlled valence electrons, such as an n-type semiconductor.
本発明によれば、ＩＴＯ膜で構成された電極中に存在す
るＩｎが絶縁層膜へ向けて拡散する過程で透明なＩｎ捕
捉層に捕捉され、従って絶縁層膜中への拡散が抑制され
ることになる。According to the present invention, In in the electrode made of an ITO film is captured by the transparent In trapping layer in the process of diffusing toward the insulating layer, and therefore diffusion into the insulating layer is suppressed. It turns out.
本発明においては、ＥＬディスプレイ素子における絶縁
Ｎ膜の電気耐圧を向上でき、このため高電圧駆動時にお
いても絶縁破壊を生じることがなく、従って信軌性の高
いＥＬディスプレイ素子を得ることができる。In the present invention, the electrical withstand voltage of the insulating N film in the EL display element can be improved, so that dielectric breakdown does not occur even when driven at a high voltage, and therefore an EL display element with high reliability can be obtained.
［実施例］
第１図には本発明のＥ Ｌディスプレイ素子の一実施例
を示す。図において、ガラス基板１上には光学的に透明
なＩＴＯ膜よりなる第１透明電極１よりなる光学的に透
明な第１絶縁層膜３１．Ｍｎが添加されたＺｎＳよりな
る発光Ｈ４１，Ｔａ２０５よりなる光学的に透明な第２
絶縁層膜３２．Ｔｉ５ｉｚよりなる光学的に透明な第２
Ｉｎ捕捉層２２、ＩＴＯ膜よりなる第２透明電極１２が
順次積層形成しである。[Example] FIG. 1 shows an example of the EL display element of the present invention. In the figure, an optically transparent first insulating layer film 31 made of a first transparent electrode 1 made of an optically transparent ITO film is disposed on a glass substrate 1. A light-emitting H41 made of Mn-doped ZnS, an optically transparent second made of Ta205
Insulating layer film 32. an optically transparent second layer made of Ti5iz;
An In trapping layer 22 and a second transparent electrode 12 made of an ITO film are sequentially laminated.
次に、上記構造のＥＬディスプレイ素子の製造方法の一
例を説明する。Next, an example of a method for manufacturing an EL display element having the above structure will be described.
まず、ガラス基板１上に、第１透明電極１１を成膜した
。蒸着材料としては、酸化インジウム（Ｉｎｚ（）＋）
粉末にすず（Ｓｎ）を加えて混合し、ペレット状に成形
したものを用い、成膜装置としては、電子ビーム蒸着装
置を用いた。具体的には、基板１の温度を２００°Ｃに
保持したまま蒸着装置内を５Ｘ１０−３Ｐａまで排気し
、蒸着レートが１．０〜３．０人／ ｓ ｅ ｃの範囲
となるようビーム電力を調整した。First, the first transparent electrode 11 was formed on the glass substrate 1. As a vapor deposition material, indium oxide (Inz()+)
The powder was mixed with tin (Sn) and formed into pellets, and an electron beam evaporation device was used as the film forming device. Specifically, the inside of the evaporation apparatus was evacuated to 5X10-3 Pa while maintaining the temperature of the substrate 1 at 200°C, and the beam power was adjusted so that the evaporation rate was in the range of 1.0 to 3.0 persons/sec. adjusted.
第１透明電極１１の上面には、チタンシリサイド（Ｔｉ
Ｓｉ２）よりなる第１１ｎ捕捉Ｊ！ｆ２１をスパッタ装
置により形成した。具体的には、基板１の温度を１５０
°Ｃに保持してスパッタ装置内を５Ｘ１０−’Ｐａまで
排気後、装置内にＡｒガスを導入して、１．４ＫＷの高
周波電力のもと約５分間スパッタし、第１透明電極１１
の上面に第１１ｎ捕捉層２１をなすＴ ｉ Ｓ ｉ ｚ
の膜を堆積した。堆積膜の組成はターゲットのＴｉとＳ
ｉの比を変化する“ことで制御した。このようにして得
られた第１１ｎ捕捉１ｉ２１の抵抗値はＴｉＳｉ、膜の
固有抵抗値（１０μΩ・ＣＴ１１）から予想される値と
比較して１桁程度高い値を示すが、後述の熱処理にょっ
て抵抗値は減少する。The upper surface of the first transparent electrode 11 is made of titanium silicide (Ti).
The 11nth acquisition J! f21 was formed using a sputtering device. Specifically, the temperature of the substrate 1 was set to 150°C.
After maintaining the temperature at °C and evacuating the inside of the sputtering apparatus to 5X10-'Pa, Ar gas was introduced into the apparatus, and sputtering was performed for about 5 minutes under a high frequency power of 1.4KW.
The 11nth trapping layer 21 is formed on the upper surface of T i S i z
film was deposited. The composition of the deposited film is the target Ti and S.
The resistance value of the 11n-th capture 1i21 obtained in this way is one order of magnitude higher than the value expected from the specific resistance value (10 μΩ・CT11) of the TiSi film. Although the resistance value is relatively high, the resistance value decreases by heat treatment, which will be described later.
次に、第１１ｎ捕捉層２１の上面には、Ｔ ａ 、０゜
よりなる第１絶縁層膜３１をスパッタにより形成する。Next, on the upper surface of the 11n trapping layer 21, a first insulating layer film 31 having a T a of 0° is formed by sputtering.
具体的には基板１の温度を２００°Ｃに保持し、スパッ
タ装置内を１． ＯＰ ａに維持し、装置内にＡｒとＯ
Ｚの混合ガスを導入（２０００ｃｃ／ｍｉｎ ）し、Ｉ
ＫＷの高周波電力で堆積速度２人／ ｓ ｅ ｃの条件
で行った。Specifically, the temperature of the substrate 1 is maintained at 200°C, and the inside of the sputtering apparatus is heated to 1. Maintain at OP a, with Ar and O inside the device.
Introduce the mixed gas of Z (2000cc/min),
The deposition was performed using KW high frequency power at a deposition rate of 2 persons/sec.
この第１絶縁Ｊ’Ｗ３１上には、ＺｎＳを母材層とし、
発光中心としてＭｎを添加した発光層４１をＷ着により
形成した。具体的には、基板１の温度を１２０ ’Ｃニ
保持し、装置内を５Ｘ１０−’Ｐａ以上に維持し、堆積
速度１．０〜３．０人／ ｓ ｅ ｃの条件で電子ビー
ム蒸着を行った。On this first insulation J'W31, ZnS is used as a base material layer,
A light emitting layer 41 doped with Mn as a light emitting center was formed by W deposition. Specifically, the temperature of the substrate 1 was maintained at 120'C, the inside of the apparatus was maintained at 5X10-'Pa or more, and electron beam evaporation was performed at a deposition rate of 1.0 to 3.0 persons/sec. went.
次に、この発光層４１の上にＴ ａ ２０ ｓよりなる
第２絶縁層膜３２．ＴｉＳｉ、よりなる第２Ｉｎ捕捉層
２２を、各々第１絶縁層膜３１．第１１ｎ捕捉層２１と
同一の方法で形成する。Next, on this light emitting layer 41, a second insulating layer film 32 made of T a 20 s is formed. A second In trapping layer 22 made of TiSi and a first insulating layer 31 . It is formed by the same method as the 11n-th trapping layer 21.
以上の各層１１，２１．３１，４１，３２．２２をガラ
ス基板１上に形成後、５Ｘ１０−’Ｐａの真空中、３０
０〜５５０°Ｃで熱処理を行った。この熱処理により、
発光層４１の結晶性を向上させ、発光輝度が上がる。After forming each of the above layers 11, 21.31, 41, 32.22 on the glass substrate 1, 30
Heat treatment was performed at 0 to 550°C. With this heat treatment,
The crystallinity of the light-emitting layer 41 is improved, and the luminance of light emission is increased.
この熱処理後に、ＩＴＯＩＩｉよりなる第２透明電極１
２を、先の第１透明電極１１と同一の方法により、第２
Ｉｎ捕捉ＪＷ２２の上に形成した。各々の膜厚は、第１
．第２透明電極１１．１２が３０００人、第１．第２１
ｎ捕捉層２１．２２が３゜０人、第１．第２絶縁層膜３
１．３２が６０００人２発光層４１が６０００人である
。After this heat treatment, the second transparent electrode 1 made of ITOIIi
2 to the second transparent electrode 11 using the same method as the first transparent electrode 11 described above.
It was formed on In-trapping JW22. Each film thickness is the first
．． The second transparent electrode 11.12 is 3000 people, the first transparent electrode 11.12 is 3000 people. 21st
n trapping layer 21.22 is 3°0 people, 1st. Second insulating layer film 3
1.32 is 6000 people and 2 light emitting layer 41 is 6000 people.
このようにして得たＥＬディスプレイ素子を、連続発光
試験に供したところ（交流印加電圧１８０■）、５００
時間経過後も絶縁破壊は認められず、絶縁破壊に対し良
好な性能を有することがわかった。When the EL display element thus obtained was subjected to a continuous light emission test (AC applied voltage 180μ), 500μ
No dielectric breakdown was observed even after the passage of time, indicating that it had good performance against dielectric breakdown.
第２図は本発明の他の実施例を示す。本実施例で瞳、上
記第１実施例の構造上にさらに第２の発光層を積層した
積層型のＥＬディスプレイ素子としである。FIG. 2 shows another embodiment of the invention. In this example, the pupil is a layered EL display element in which a second light emitting layer is further laminated on the structure of the first example.
図において、中間電極となる第２透明電極１２（ＩＴＯ
膜）上にはＴｉＳｉ２よりなる第３１ｎ捕捉層２３およ
びＴ ａ ｚ Ｏｓよりなる第３絶縁層膜３３が先の実
施例と同一の方法でスバ・ツタにより形成してあり、そ
の上に第２発光層４２が先の実施例と同一の方法で形成
しである。第２発光層４２は、ＺｎＳを母材層とし、発
光中心としてＴ ｂ Ｆ ｘを添加したものでグリーン
発光する。In the figure, a second transparent electrode 12 (ITO
A 31n-th trapping layer 23 made of TiSi2 and a third insulating layer 33 made of T az Os are formed on the same method as in the previous embodiment, and a second The light emitting layer 42 is formed by the same method as in the previous embodiment. The second light emitting layer 42 has ZnS as a base material layer and T b F x is added as a light emitting center, and emits green light.
第２発光層４２上には、Ｔ ａ ２０ ｓよりなる第４
絶縁層膜３４を介してＡＮ金属よりなる上部電極５が蒸
着により形成しである。第３．第４絶縁層膜３３，３４
．第２発光層４２の膜厚はいずれも６０００人であり、
Ｉｎ捕捉層２３．２４は５００人、上部電極５は１００
０人である。On the second light emitting layer 42, there is a fourth layer made of T a 20 s.
An upper electrode 5 made of AN metal is formed by vapor deposition with an insulating layer 34 interposed therebetween. Third. Fourth insulating layer film 33, 34
．． The thickness of the second light emitting layer 42 is 6000 in each case,
500 people for the In trapping layers 23 and 24, 100 people for the upper electrode 5
There are 0 people.
上記構造のＥＬディスプレイ素子において、第１の発光
層４１．または第２発光層４２に電圧を印加することに
より、それぞれオレンジ、グリーンの発光色が得られ、
さらに第１．第２発光層４１．４２を同時に発光させる
ことにより、これらの混色であるイエローの発光色が得
られるので、これらを組合わせることによりマルチカラ
ー化力く可能となる。In the EL display element having the above structure, the first light emitting layer 41. Alternatively, by applying a voltage to the second light emitting layer 42, orange and green light emission colors can be obtained, respectively.
Furthermore, the first. By causing the second light emitting layers 41 and 42 to emit light at the same time, a yellow light emitting color, which is a mixture of these colors, can be obtained, so by combining these colors, it becomes possible to create a multicolor display.
上記の第２図の構造のＥＬディスプレイ素子においても
絶縁破壊に対し良好な性能が得られ、第１実施例と同一
の連続発光試験に供したところ、５００時間経過後も絶
縁破壊は認められなかった。The EL display element with the structure shown in Figure 2 above also exhibited good performance against dielectric breakdown, and when subjected to the same continuous light emission test as in the first example, no dielectric breakdown was observed even after 500 hours had elapsed. Ta.
次に、比較のため、第３図、第４図に示す従来構造のＥ
Ｌディスプレイ素子を作製した。なお、図中、第１図、
第２図と同一符号は同一の構成を示す。これらは、それ
ぞれ上記第１実施例（第１図）および第２実施例（第２
図）からＩｎ捕捉層２１．２２，２３．２４を省いた構
造となっている点が異なるのみで、他の構造は各実施例
と同一であり、製法も同一である。Next, for comparison, the E of the conventional structure shown in Figs. 3 and 4 is shown.
An L display element was manufactured. In addition, in the figure, Figure 1,
The same reference numerals as in FIG. 2 indicate the same configurations. These are the above-mentioned first embodiment (Fig. 1) and second embodiment (second embodiment), respectively.
The only difference is that the In trapping layers 21, 22, 23, 24 are omitted from the structure shown in FIG.
これらを第１実施例と同一の連続発光試験に供したとこ
ろ、第３図の構造では２００時間で絶縁破壊が生じ、第
４図の構造では４０時間で絶縁破壊が生じた。When these were subjected to the same continuous light emission test as in the first example, dielectric breakdown occurred in the structure shown in FIG. 3 after 200 hours, and dielectric breakdown occurred in the structure shown in FIG. 4 after 40 hours.
このＩＴＯによる絶縁破壊を調べるため、第５図のよう
に、ガラス基板１上にＩＴＯ電極５を設け、その上にＴ
ａ 、０５絶縁層膜３をスパッタ法で成膜した試料を
作製してＡＥＳ分析（オージェ電子分光分析）を行った
。試料は側端面を５°に斜め研磨し、深さ方向の元素の
分布がわかるようにした。結果を第６図に示す。In order to investigate the dielectric breakdown caused by this ITO, as shown in FIG.
A, AES analysis (Auger electron spectroscopy) was performed on a sample in which the 05 insulating layer film 3 was formed by sputtering. The side end surfaces of the samples were polished at an angle of 5° so that the distribution of elements in the depth direction could be seen. The results are shown in Figure 6.
また、成膜後、３５０°Ｃで熱処理したもの、５５０”
Ｃで熱処理したものにつき、同様の分析を行ない、結果
をそれぞれ第７図、第８図に示した。Also, after film formation, heat treated at 350°C, 550"
A similar analysis was carried out on those heat-treated with C, and the results are shown in FIGS. 7 and 8, respectively.
各図に明らかなように、熱処理によりＴａとＩｎのオー
バーラツプが大きくなっており、Ｉｎが絶８ｉ層３を構
成するＴ ａ ｚ Ｏｓ中に浸入していく様子がよくわ
かる。また、熱処理温度を高くするごとでさらにその傾
向が増加している。As is clear from each figure, the overlap between Ta and In increases due to the heat treatment, and it can be clearly seen that In penetrates into the T az Os constituting the 8i layer 3. Furthermore, this tendency increases as the heat treatment temperature increases.
Ｉｎは導電体であるため、絶縁層膜３中へＩｎが拡散す
ると絶縁層膜の電気耐圧は低くなり、これが原因となっ
て絶縁破壊が生じると考えられる。Since In is a conductor, when In diffuses into the insulating layer 3, the electric withstand voltage of the insulating layer decreases, and this is considered to be the cause of dielectric breakdown.
このＩｎの絶縁層膜中への拡散は、ＩＴＯ膜の上層の絶
縁ｉ膜の成膜時に、例えばスバ・ツタのようにプラズマ
を利用する方法を用いるため、Ｉｎｚ０３が還元されて
部分的にＩｎ金属となって存在するからで、このＩｎ金
属が熱処理の過程で拡散するためではないかと考えられ
ている。This diffusion of In into the insulating layer film is caused by the reduction of Inz03 and partial In because a method using plasma is used, for example, as in Suba-Ivy, when forming the insulating i film on the ITO film. It is thought that this is because In metal exists as a metal, and this In metal diffuses during the heat treatment process.
これに対し、第１図の第１実施例のごとく、第１透明電
極１１と第１絶８ｉＮ膜３１との間、および第２透明電
極１２と第２絶縁層膜３２との間に、各々第１．第２１
ｎ捕捉層２１．２２（厚さ３００人、Ｔｉ５ｉｚ）を形
成した試料を用いてＡＥＳ分析を行った結果を第９図に
示す。第９図から明らかなように、５５０°Ｃ熱処理後
もＩｎの絶縁層膜中への拡散は見られない。このように
、ＩＴＯ膜よりなる透明電極−絶縁層膜間にＩｎ捕捉層
を設けることにより、絶縁破壊を防止できる。On the other hand, as in the first embodiment shown in FIG. 1st. 21st
FIG. 9 shows the results of an AES analysis performed using a sample in which an n-trapping layer 21.22 (thickness: 300 layers, Ti5iz) was formed. As is clear from FIG. 9, no diffusion of In into the insulating layer film was observed even after the heat treatment at 550°C. In this way, by providing the In trapping layer between the transparent electrode made of the ITO film and the insulating layer film, dielectric breakdown can be prevented.
ところで、上記の実施例は透明なＩｎ捕捉層として、高
融点金属のシリサイド即ちＴｉ５ｉｚにより構成したが
、微結晶炭化ケイ素等の価電子制御された半導体によっ
てＩｎ捕捉層を構成することができる。炭化ケイ素より
なる薄膜は、例えばシラ゛ン（ＳｉＨ４）とメタン（Ｃ
Ｈ，）との混合ガスを高周波放電などにより分解するこ
とで得られるが、混合ガス中にジボラン（Ｂ２Ｈ１）や
ホスフィン（ＰＨ３）を添加すればそれぞれＰ型。By the way, in the above embodiment, the transparent In trapping layer is made of high melting point metal silicide, that is, Ti5iz, but the In trapping layer can be made of a semiconductor whose valence electrons are controlled, such as microcrystalline silicon carbide. A thin film made of silicon carbide is made of, for example, silane (SiH4) and methane (C
It can be obtained by decomposing a mixed gas with H, ) by high frequency discharge, etc., but if diborane (B2H1) or phosphine (PH3) is added to the mixed gas, each becomes P type.
ｎ型の半導体膜が得られる。さらに，ＳｉｘＧｅｉＨ４
とＣＨ，の混合比によって１．７ｅｖ 〜２．７ｅｖ程
度まで光学的禁制帯幅を制御することができる。ところ
で、本発明のＥＬディスプレイ素子で用いている透明電
極（ＩＴＯ）、発光層（ＺｎＳ）はｎ型半導体であるが
、各層の光学的禁制帯幅は異なるため、電荷がトンネリ
ングによって発光層中に導入されるためには大きな電圧
を印加する必要がある。An n-type semiconductor film is obtained. Furthermore, SixGeiH4
The optical forbidden band width can be controlled to about 1.7ev to 2.7ev by adjusting the mixing ratio of CH and CH. By the way, the transparent electrode (ITO) and the light-emitting layer (ZnS) used in the EL display element of the present invention are n-type semiconductors, but since the optical forbidden band width of each layer is different, charges may be tunneled into the light-emitting layer. In order to be introduced, it is necessary to apply a large voltage.
そこで、前述した方法によって価電子制御した炭化ケイ
素半導体膜をＩｎ捕捉層に用いることで、発光層への電
荷注入効率が大幅に改善される。Therefore, by using a silicon carbide semiconductor film whose valence electrons are controlled by the method described above as an In trapping layer, the efficiency of charge injection into the light emitting layer is significantly improved.
即ち、光学的禁制帯幅を透明電極（ＩＴＯ）と発光層（
ＺｎＳ）との中間に設定するため、例えば５ｉ）（４と
ＣＨ４のガス流量比を１：２とし、２、７ ｅ ｖとし
た。また、活性化エネルギも同様で、ＩＴＯとＺｎＳの
中間に位置するようにＳｉＣ成膜時にＰＨ，を５ｉＨａ
とＣＨ，の総流量に対して流量比で１％添加した。この
方法により、光学的禁制帯幅２．７ｅｖ、活性化エネル
ギ０．４ｅｖのｎ型炭化ケイ素膜を得、緩衝層に応用し
た。その結果、しきい値電圧が約４０Ｖ低下し８ｏ■と
なり、輝度も２３００ｃｄ／ｒｒｆから２７００ｃｄ／
ｒｄまで大幅に向上（緑色発光）し、従って電荷の注入
効率が改善されていることがわかる。なお、不純物を添
加しない半導体またはＰ型半導体は障壁となるので、電
荷の注入効率を改善する効果は期待できない。In other words, the optical forbidden band width is determined by the distance between the transparent electrode (ITO) and the light emitting layer (
For example, 5i) (the gas flow ratio of 4 and CH4 was set to 1:2, and the activation energy was set to 2,7 e v. When forming the SiC film, the pH was adjusted to 5iHa so that the
and CH, were added at a flow rate ratio of 1% to the total flow rate. By this method, an n-type silicon carbide film with an optical forbidden band width of 2.7 ev and an activation energy of 0.4 ev was obtained and applied to a buffer layer. As a result, the threshold voltage decreased by about 40V to 8o■, and the brightness also increased from 2300cd/rrf to 2700cd/rrf.
It can be seen that the charge injection efficiency is significantly improved to rd (green light emission), and therefore the charge injection efficiency is improved. Note that since a semiconductor to which no impurity is added or a P-type semiconductor acts as a barrier, no effect of improving charge injection efficiency can be expected.
また、第１実施例と同一の連続発光試験を行ったところ
、５００時間経過後も絶縁破壊は認められず、先の実施
例のＴｉＳ２よりなるＩｎ捕捉層と同様、Ｉｎの絶縁層
膜への拡散を防止する効果が認められた。In addition, when the same continuous light emission test as in the first example was conducted, no dielectric breakdown was observed even after 500 hours had passed, and similar to the In trapping layer made of TiS2 in the previous example, the In insulating layer film was The effect of preventing the spread was recognized.
本発明は上記の実施例に限らず、次のごとく、種々の変
形が可能である。The present invention is not limited to the above-described embodiments, but can be modified in various ways as described below.
（１） Ｉ ｎ捕捉層２１，２２．２３はＴｉ５ｉｚの
他に“ＶＳ ｉ２．Ｔａ Ｓ ｉ２．Ｈｆ Ｓ
ｉｚ、 Ｚ ｒ Ｓ Ｌ。(1) In addition to Ti5iz, the In trapping layers 21, 22, and 23 include “VS i2.Ta Si2.Hf S
iz, Z r S L.
ＮｂＳ ｉｚ、ＣｒＳ ｉｚ、ＭｏＳ ｔｚ、Ｐ ｔＳ
ｉｚのいわゆる高融点金属のシリサイドにより構成す
ることができる。また、Ｉｎ捕捉層２１，２２．２３は
価電子制御された半導体により構成しているが、その半
導体は５ｉ）（Ｃ＋−ｘの他に，ＳｉｘＧｅｉ、５ｉ）
（Ｇｅ＋５ｉｘＳｎ＋−ｘであってもよい。また、価電
子制御された半導体はＩｎの捕捉という観点からすれば
ｎ型の他にＰ型でもよい。NbS iz, CrS iz, MoS tz, P tS
It can be composed of silicide of a so-called high melting point metal. In addition, the In trapping layers 21, 22, and 23 are made of a valence-controlled semiconductor, and the semiconductor is 5i) (in addition to C+-x, SixGei, 5i)
(Ge+5ixSn+-x may be used. Also, from the viewpoint of trapping In, the valence electron-controlled semiconductor may be of P type instead of n type.
（２）絶縁層膜３１．３２，３３．３４はＴ ａ ２０
５で構成したが、Ａｆ、０．，ＳｉｘＧｅ ｉ３Ｎ、、
ＰｂＴ ｉ Ｏ３て構成してもよい。(2) Insulating layer films 31, 32, 33, 34 are T a 20
5, but Af, 0. ,SixGe i3N,,
It may also be composed of PbT i O3.
（３）発光層４１はＺｎＳにＭｎを添加したもので構成
したが、ＺｎＳにＳｍ、Ｔｍ等の希土類金属イオンを添
加したもので構成してもよい。(3) Although the light emitting layer 41 is made of ZnS added with Mn, it may be made of ZnS added with rare earth metal ions such as Sm and Tm.
（４）発光層は１層、２層の他に３層以上とすることで
、例えばＲＧＢ等の発光層を重ねることでフルカラー化
が可能となる。(4) By using three or more light-emitting layers in addition to one or two layers, it is possible to achieve full color, for example, by stacking RGB light-emitting layers.
（５）高融点金属のシリサイドにより構成されたＩｎ捕
捉層と、価電子制御された半導体により構成されたＩｎ
捕捉層を重層してもよい。この場合、絶縁層膜側に前者
のＩｎ捕捉層を、透明電極側に後者のＩｎ捕捉層を配す
るとよい。(5) In trapping layer made of high melting point metal silicide and In made of semiconductor with controlled valence electrons
Acquisition layers may be overlaid. In this case, it is preferable to arrange the former In trapping layer on the insulating layer side and the latter In trapping layer on the transparent electrode side.
（６）価電子制御された半導体により構成されたＩｎ捕
捉層は複層としてもよい。例えば、透明電極側に、光学
的禁制帯幅が大きく活性化エネルギーの小さい層を形成
し、絶縁層膜側に向けて段階的に光学的禁制帯幅を小さ
く活性化エネルギーを大きくした層を順次積層するよう
にしてもよい。この構成により、透明電極と絶縁層膜と
の間の物性値を連続的なものにでき、発光層への電荷の
注入効率が更に改善できる。(6) The In trapping layer made of a semiconductor whose valence electrons are controlled may be a multilayer. For example, a layer with a large optical band gap and low activation energy is formed on the transparent electrode side, and layers with a small optical band gap and high activation energy are sequentially formed toward the insulating layer side. They may be laminated. With this configuration, the physical property values between the transparent electrode and the insulating layer can be made continuous, and the efficiency of charge injection into the light emitting layer can be further improved.
第１図は本発明の第１実施例を示すＥＬディスプレイ素
子の全体断面図、第２図は本発明の第２実施例を示すＥ
Ｌディスプレイ素子の全体断面図、第３図および第４図
は従来のＢＬディスプレイ素子の全体断面図、第５図は
従来のＥＬディスプレイ素子におけるＩｎの拡散状態を
調べるための試料の部分断面図、第６〜第８図は従来の
ＥＬディスプレイ素子におけるＩｎの拡散状態を示す図
、第９図は本発明のＥＬディスプレイ素子におけるＩｎ
の拡散状態を示す図である。
１・・・ガラス基板、１１．１２・・・第１．第２透明
電極、２１，２２．２３・・・第１．第２．第３１ｎ捕
捉層、３１，３２，３３．３４・・・第１．第２゜第３
．第４絶縁層膜、４１．４２・・・第１．第２発光層。FIG. 1 is an overall sectional view of an EL display element showing a first embodiment of the present invention, and FIG. 2 is an E display element showing a second embodiment of the present invention.
3 and 4 are overall sectional views of a conventional BL display element, and FIG. 5 is a partial sectional view of a sample for investigating the diffusion state of In in a conventional EL display element. 6 to 8 are diagrams showing the diffusion state of In in the conventional EL display element, and FIG. 9 is a diagram showing the diffusion state of In in the EL display element of the present invention.
It is a figure showing the diffusion state of. 1... Glass substrate, 11.12... 1st. 2nd transparent electrode, 21, 22, 23... 1st. Second. 31nth trapping layer, 31, 32, 33, 34... 1st. 2nd゜3rd
．． Fourth insulating layer film, 41.42...1st. Second light emitting layer.
Claims (6)
の間に、絶緑層膜を介して発光層を配したＥＬデイスプ
レイ素子において、 前記一対の電極のうち前記ＩＴＯ膜で構成された電極と
該電極側に位置する前記絶縁層膜との間に透明なＩｎ捕
捉層を配したことを特徴とするＥＬデイスプレイ素子。(1) In an EL display element in which a light-emitting layer is arranged between a pair of electrodes, at least one of which is made of an ITO film, with a never-green layer interposed therebetween, the electrode of the pair of electrodes is made of an ITO film, An EL display element characterized in that a transparent In trapping layer is disposed between the insulating layer film located on the electrode side.
で構成されていることを特徴とする請求項（１）記載の
ＥＬデイスプレイ素子。(2) The EL display element according to claim 1, wherein the transparent In trapping layer is made of silicide of a high-melting point metal.
，Ｎｂ，Ｍｏ，Ｔａ，Ｗ，Ｐｔから選択されることを特
徴とする請求項（２）記載のＥＬデイスプレイ素子。(3) The high melting point metal is Ti, V, Cr, Hf, Zr
, Nb, Mo, Ta, W, and Pt.
体で構成されていることを特徴とする請求項（１）記載
のＥＬデイスプレイ素子。(4) The EL display element according to claim (1), wherein the transparent In trapping layer is made of a semiconductor whose valence electrons are controlled.
シリコンカーボン），Ｓｉ＿ｘＧｅ＿１＿−＿ｘ（シリ
コンゲルマニウム），Ｓｉ＿ｘＳｎ＿１＿−＿ｘ（シリ
コンすず）から選択されることを特徴とする請求項（４
）記載のＥＬデイスプレイ素子。(5) The semiconductor is Si, Si_xC_t_-_x(
Claim (4) characterized in that the silicone is selected from silicon carbon), Si_xGe_1_-_x (silicon germanium), and Si_xSn_1_-_x (silicon tin).
).The EL display element described in ).
ことを特徴とする請求項（４）記載のＥＬデイスプレイ
素子。(6) The EL display element according to claim 4, wherein the valence electron-controlled semiconductor is an n-type semiconductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1331579A JPH0760741B2 (en) | 1989-12-21 | 1989-12-21 | EL display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1331579A JPH0760741B2 (en) | 1989-12-21 | 1989-12-21 | EL display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03192690A true JPH03192690A (en) | 1991-08-22 |
| JPH0760741B2 JPH0760741B2 (en) | 1995-06-28 |
Family
ID=18245233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1331579A Expired - Lifetime JPH0760741B2 (en) | 1989-12-21 | 1989-12-21 | EL display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0760741B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5726953A (en) * | 1995-04-07 | 1998-03-10 | Metro-Mark, Incorporated | Electroluminescent lamp with buried indiciae and method for making same |
| KR100354823B1 (en) * | 1999-09-10 | 2002-10-04 | 전자부품연구원 | Eld using a transparent isolate layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389698U (en) * | 1986-12-01 | 1988-06-10 |
-
1989
- 1989-12-21 JP JP1331579A patent/JPH0760741B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389698U (en) * | 1986-12-01 | 1988-06-10 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5726953A (en) * | 1995-04-07 | 1998-03-10 | Metro-Mark, Incorporated | Electroluminescent lamp with buried indiciae and method for making same |
| KR100354823B1 (en) * | 1999-09-10 | 2002-10-04 | 전자부품연구원 | Eld using a transparent isolate layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0760741B2 (en) | 1995-06-28 |
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