JPH02135322A - Electrochromic display element - Google Patents
Electrochromic display elementInfo
- Publication number
- JPH02135322A JPH02135322A JP28975388A JP28975388A JPH02135322A JP H02135322 A JPH02135322 A JP H02135322A JP 28975388 A JP28975388 A JP 28975388A JP 28975388 A JP28975388 A JP 28975388A JP H02135322 A JPH02135322 A JP H02135322A
- Authority
- JP
- Japan
- Prior art keywords
- film
- electrochromic
- protective film
- thickness
- insulating protective
- 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
- 230000001681 protective effect Effects 0.000 claims abstract description 42
- 239000011521 glass Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエレクトロクロミック表示素子の改良に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to improvements in electrochromic display elements.
第1図にエレクトロクロミック表示素子の基本的なセル
構造の一例を示す。図中、1は透明ガラス板であり、こ
の透明ガラス板1の表面に透明導電膜からなる表示電極
2と絶縁保護膜3を複数個の表示セグメントからなる所
定のパターンにそれぞれ設けて表示極基板4が形成され
ている。この表示極基板4の絶縁保護膜3が形成されて
いない所定の表示セグメンI一部分の表示電極2上に酸
化タングステン(W○、)や酸化モリブデン(M o
O3)などからなるエレクトロクロミック膜5が3,0
00−10,000人の膜厚に設けられて表示極6が形
成されている。エレクトロクロミック膜5の膜厚が厚い
ほど着色濃度は濃くなるが消色時に消え残りが生じるた
めに、通常は5,000〜6゜000人が用いられる。FIG. 1 shows an example of the basic cell structure of an electrochromic display element. In the figure, 1 is a transparent glass plate, and display electrodes 2 made of transparent conductive films and insulating protective films 3 are provided on the surface of this transparent glass plate 1 in a predetermined pattern consisting of a plurality of display segments. 4 is formed. Tungsten oxide (W○, ) or molybdenum oxide (Mo
The electrochromic film 5 made of O3) etc.
The display electrode 6 is formed with a film thickness of 0.00 to 10,000. The thicker the electrochromic film 5 is, the higher the coloring density becomes, but since some residue remains when erasing the color, 5,000 to 6,000 people are usually used.
7は対向極基板であり、この対向極基板7の表面に対向
電極8を介して対向極物質層9が設けられて対向極10
が形成されている。そして、表示極基板4と対向極基板
7は合成樹脂やガラスなどからなるスペーサー11を介
してそれぞれの加工面を内側にして対向配置され、その
内部にプロピレンカーボネートやガンマブチロラクトン
などの有機溶媒に過塩素酸リチウムやホウフッ化リチウ
ムなどのリチウム塩を溶解させた電解液12が充満する
ように封入されている。7 is a counter electrode substrate, and a counter electrode material layer 9 is provided on the surface of this counter electrode substrate 7 with a counter electrode 8 interposed therebetween.
is formed. The display electrode substrate 4 and the counter electrode substrate 7 are arranged facing each other with their respective processed surfaces inward through a spacer 11 made of synthetic resin or glass, and are filled with an organic solvent such as propylene carbonate or gamma-butyrolactone inside. It is filled with an electrolytic solution 12 in which a lithium salt such as lithium chlorate or lithium borofluoride is dissolved.
上記の表示電極2はインジウム−スズ複合酸化物(IT
O)などの透明導電性材料からなり、真空蒸n法、スパ
ッタリング法などの既存の薄膜形成技術によって通常1
,000〜5,000人程度の厚さに形成される。表示
電極2と電解液12が接触すると素子の昧IJJ時にエ
レクトロクロミック膜だけでなく表示型へ2も電気化学
反応を起こし、表示電極2のみならず電解液12の劣化
の原因となる。それを防止するために表示電極2のhに
保護膜として二踵化ケイ素(SiO2)やフッ化マグネ
シウム(M g F、)などの絶縁保護膜3を3,00
0〜10.000人程度の厚さに設けている。The display electrode 2 is made of indium-tin composite oxide (IT
It is made of a transparent conductive material such as
It is formed to a thickness of about ,000 to 5,000 people. When the display electrode 2 and the electrolyte 12 come into contact, an electrochemical reaction occurs not only in the electrochromic film but also in the display mold 2 during IJJ of the device, causing deterioration of not only the display electrode 2 but also the electrolyte 12. To prevent this, an insulating protective film 3 such as silicon dioxide (SiO2) or magnesium fluoride (MgF) is applied to the display electrode 2 as a protective film.
The thickness is approximately 0 to 10,000 people.
絶縁保護膜3のパターン形成にはエツジ部をシャプに形
成できるフォトリソグラフィー法が通常用いられている
。しかし、エレクトロクロミック膜5と絶縁保護膜3と
の界面に間隙があると表示電極2と電解液12が接触し
てしまうという問題があった。この間隙をなくすために
種々の対策が講じられてきた。例えば、第2図(A)に
示すようにエレクトロクロミック膜19と重なりを生じ
ないように絶縁保護膜2oを連続して形成する(特開昭
52−38947)、第2図(B)に示すようにエレク
トロクロミック膜19上に一部絶縁保護膜20を重ねる
(特開昭52−28293)、第2図(C)に示すよう
に絶縁保護膜2o上に一部エレクトロクロミック膜19
を重ねるなどの方法が提案されている。しかし、これら
の方法はいずれも十分な効果が得られていなかった。す
なわち、特開昭52−38947で開示された方法では
マクロ的には絶縁保護膜20とエレクトロクロミック膜
19は連続しているように見えるが、両者の界面を電子
顕微鏡で詳細に観察すると0.1〜1μm程度の細い間
隙が生じたり、エレクトロクロミック膜19が絶縁保護
膜20の上にわずかに重なったりしており、再現性よく
絶縁保護膜2oとエレクトロクロミック膜19を連続的
に形成することは非常に蒋しい、わずかでも間隙があれ
ば、素子を数十刃口や数百ガロにわたってサイクル駆動
すると次第に劣化が進行してついには異常が発生する。For pattern formation of the insulating protective film 3, a photolithography method is usually used which allows sharp edges to be formed. However, if there is a gap at the interface between the electrochromic film 5 and the insulating protective film 3, there is a problem that the display electrode 2 and the electrolyte 12 come into contact with each other. Various measures have been taken to eliminate this gap. For example, as shown in FIG. 2(A), the insulating protective film 2o is formed continuously so as not to overlap with the electrochromic film 19 (Japanese Patent Application Laid-Open No. 52-38947), as shown in FIG. 2(B). As shown in FIG.
Methods have been proposed, such as overlapping. However, none of these methods were sufficiently effective. That is, in the method disclosed in Japanese Patent Application Laid-Open No. 52-38947, the insulating protective film 20 and the electrochromic film 19 appear to be continuous from a macroscopic perspective, but when the interface between the two is closely observed with an electron microscope, it is found that the insulating protective film 20 and the electrochromic film 19 are continuous. A narrow gap of about 1 to 1 μm may occur, or the electrochromic film 19 may slightly overlap the insulating protective film 20, and the insulating protective film 2o and the electrochromic film 19 should be continuously formed with good reproducibility. It is very flexible, and if there is even a slight gap, if the element is cycled over tens of blades or hundreds of gals, it will gradually deteriorate and eventually malfunction will occur.
第2図(B)の場合にはエレクトロクロミック膜19の
上に絶縁保護膜20が重なるため、絶縁保護膜20の下
になる部分のエレクトロクロミツク膜19は電解液と直
接接触しないために着消色反応が遅くなり1色ムラが生
じて表示品位が低下するという欠点がある。一方、第2
図(C)に示す絶縁保護膜20の上にエレクトロタロミ
ック膜19の端部を重ねる方法は、表示品位を低下させ
ることなくサイクル寿命を向上させることができ。In the case of FIG. 2(B), the insulating protective film 20 overlaps the electrochromic film 19, so the portion of the electrochromic film 19 below the insulating protective film 20 does not come into direct contact with the electrolytic solution. There is a drawback that the decoloring reaction is slow and one-color unevenness occurs, resulting in a decrease in display quality. On the other hand, the second
The method of overlapping the end portion of the electrothalomic film 19 on the insulating protective film 20 shown in FIG. 3(C) can improve the cycle life without deteriorating the display quality.
上記の3種類の方法の中で最も適当な方法である。This is the most suitable method among the above three methods.
この方法でも、絶縁保護膜の膜厚が3,000人未満の
薄い場合には問題ないが、下の表示電極を十分に保護す
るためには通常5,000〜6,000人の膜厚が必要
であり、一方、前述したようにエレクトロクロミック膜
の厚みも消色時の消え残りの防止の観点から無制限に厚
くすることができない。そこで、このような場合には形
成した絶縁保護膜とエレクトロクロミック膜の界面を電
子顕微鏡でvA察すると第3図に示すように、後から蒸
着して絶縁保護膜24の上に端部を重ねたエレクトロク
ロミック膜23は段差の部分に凹みができてどうしても
一部膜厚の薄い部分が生じてしまう。これは、垂直に近
く高く切り立った段差のある膜の一部にこれと同程度の
膜厚に他の膜を蒸着する際には避けられない31である
6一方、エレクトロクロミック膜の端部にはエツジ効果
によって電流が集中するため、このように端部に膜厚の
薄い部分があると多数回のサイクル駆動によってエレク
トロクロミック膜の溶解が生じ1次第にその部分が薄く
なって、ついには表示電極と電解液が直接接触して劣化
が始まるという欠点があった。Even with this method, there is no problem if the insulating protective film is thin (less than 3,000 layers), but in order to sufficiently protect the display electrodes below, the film thickness is usually between 5,000 and 6,000 layers. On the other hand, as mentioned above, the thickness of the electrochromic film cannot be increased indefinitely from the viewpoint of preventing residual color from being left behind during erasing. Therefore, in such a case, when observing the interface between the formed insulating protective film and the electrochromic film using an electron microscope, it is found that the end portion is overlapped on the insulating protective film 24 by vapor deposition later, as shown in Figure 3. In the electrochromic film 23, depressions are formed at the step portions, and some portions of the film are inevitably thin. This is unavoidable when another film is deposited to a similar thickness on a part of a film with a nearly vertical step.31 On the other hand, on the edge of an electrochromic film, Since the current is concentrated due to the edge effect, if there is a thin part at the edge, the electrochromic film will melt due to multiple cycle driving1, and the part will gradually become thinner, and eventually the display electrode The drawback was that deterioration began due to direct contact between the electrolyte and the electrolyte.
この発明は、絶縁保護膜とエレクトロクロミック膜の界
面の形状を工夫することによって、長期のサイクル寿命
を有するエレクトロクロミック表示素子を目的とする。The object of the present invention is to provide an electrochromic display element that has a long cycle life by devising the shape of the interface between an insulating protective film and an electrochromic film.
本発明者らは、この目的達成のためにはエレクトロクロ
ミック膜の厚みの均一性の確保が必要であるとの知見の
もとに種々検討したところ、絶縁保護膜の端部形状が重
要な因子であることを見出した。すなわち、M!!、縁
保護膜の土にエレクトロクロミック膜を端部が重なるよ
うに蒸着する際に、絶縁保護膜の端部の形状が垂直に近
く高く切り立っている場合に、エレクトロクロミック膜
の一部の膜Jりが薄くなるということを見出した。この
原因は、蒸着の際に飛来したエレクトロクロミック物質
の粒子が絶縁保護膜の底部の陰になる部分に十分に回り
込まないためであることがわかった。The present inventors conducted various studies based on the knowledge that it is necessary to ensure the uniformity of the thickness of the electrochromic film in order to achieve this objective, and found that the shape of the edge of the insulating protective film is an important factor. I found that. In other words, M! ! When the electrochromic film is deposited on the soil of the edge protection film so that the edges overlap, if the edge of the insulation protection film is vertical and steep, some of the electrochromic film J It was found that the thickness becomes thinner. It has been found that the reason for this is that particles of the electrochromic substance that fly during vapor deposition do not sufficiently wrap around the shaded portion at the bottom of the insulating protective film.
本発明者らはこの事実に着目して鋭意検討の結果、エレ
クトロクロミック膜の厚みの均一性を確保するためには
、第4図(A)に示すようにMa保護膜の端部を適当な
形状に形成することによって、エレクトロクロミック物
質の蒸着粒子が回り込みやすいような形状にすればよい
ことを見出した。また、第4図(B)に示すように勾配
の角部を丸めたり、第4図(C)に示すように絶縁保護
膜の端部を階段状に形成しても同様の効果が得られるこ
とを見出した。The present inventors focused on this fact and as a result of intensive studies, in order to ensure the uniformity of the thickness of the electrochromic film, the ends of the Ma protective film should be appropriately shaped as shown in Figure 4 (A). It has been found that the shape can be formed so that the vapor-deposited particles of the electrochromic substance can easily wrap around it. Furthermore, the same effect can be obtained by rounding the corners of the slope as shown in FIG. 4(B) or by forming the edges of the insulating protective film into a stepped shape as shown in FIG. 4(C). I discovered that.
勾配を形成する場合には、勾配を1700/1000(
仰角約60°)以下にすると膜厚の薄い部分が次第に解
消され、望ましくは1000/l。When forming a gradient, set the gradient to 1700/1000 (
When the elevation angle is set to about 60° or less, the thin part of the film is gradually eliminated, preferably 1000/l.
00(仰角約45°)以下、さらに望ましくは600/
1000(仰角約30°)以下にすると膜厚の薄い部分
はほぼなくなる。しかし、勾配をあまり小さくするとM
ai保護膜上のエレクトロクロミック膜の重なりが大き
くなってその部分の着消色反応が遅くなり表示品位が低
下する。膜厚との関係もあるが、勾配の下限は200/
1000、できれば300/1000以上が望ましい。00 (elevation angle approximately 45°) or less, more preferably 600/
When the angle is less than 1000 (elevation angle of about 30°), the thin part of the film almost disappears. However, if the slope is made too small, M
The overlap of the electrochromic film on the AI protective film becomes large, and the coloring/decoloring reaction in that area becomes slow, resulting in a decrease in display quality. Although it is related to the film thickness, the lower limit of the slope is 200/
1000, preferably 300/1000 or more.
また、第4図(C)のように絶縁保護膜の端部を階段状
に形成する場合は多段にすることが望ましいが、加工プ
ロセスが複雑になるので2〜3段が実用的である。その
場合、最下段があまり厚いと一段の場合と同じになり階
段状にする効果が低下するので、最下段の厚さは絶標保
護膜の全膜厚の2分の1以下でかつ3000Å以下が望
ましい。Further, when forming the end portion of the insulating protective film in a step-like manner as shown in FIG. 4(C), it is desirable to have multiple steps, but since the processing process becomes complicated, 2 to 3 steps is practical. In that case, if the bottom layer is too thick, it will be the same as in the case of one layer and the effect of making it step-like will be reduced, so the thickness of the bottom layer should be less than half of the total thickness of the absolute protective film and less than 3000 Å. is desirable.
以下1本発明にかかるエレクトロクロミック表示素子の
実施例について従来例と比較して説明する、
〔実施例〕
従来例
[50,+nm、横165nwn、厚さ1.1+nmの
透明ガラス板の表面に、表示電極となる厚さ2500人
のITO膜を真空蒸着法により設けて所定パターンに加
工形成した後、このIT○膜の全面に絶椋保護膜として
S i O,膜を厚さ5000人に真空蒸着法により設
けた。ついで1表示パターン部および引き出し電極部以
外の前記5in7膜上にフォトレジスト(東京応化製の
商品名0FPR−800)を2μmの膜厚に加工形成し
た。次に、前記基板のフォトレジストが載っていない部
分、すなわち表示セグメントおよび引き出し電極部のS
iO2膜を四フッ化炭素(CF4)ガスでエツチングし
、ついで酸素(O7)ガスでフォトレジストを後退させ
て第5図に示す端部形状に形成した。エツチング時間は
、CF、ガス:3分、02ガス:5分とし、また、エツ
チング温度は80℃とした。このときの端部の勾配は約
5000/1000 (仰角約80’)であった。この
表示極基板の引き出し電極部以外の全面に、02ガス圧
IXLO−’torr、基板温度150℃、成膜速度1
0人/秒の条件で、厚さ5000人のWO3膜を真空蒸
着し、リフトオフ法によって数字表示用の8字パターン
に形成して表示極とした。Below, an example of an electrochromic display element according to the present invention will be described in comparison with a conventional example. [Example] Conventional example After forming an ITO film with a thickness of 2,500 mm, which will become the display electrode, by vacuum evaporation and forming it into a predetermined pattern, a SiO film is deposited on the entire surface of this IT○ film as a protective film to a thickness of 5,000 mm. It was provided by a vapor deposition method. Next, a photoresist (product name: 0FPR-800 manufactured by Tokyo Ohka Co., Ltd.) was formed to a thickness of 2 μm on the 5 in 7 film except for the 1 display pattern area and the extraction electrode area. Next, S
The iO2 film was etched with carbon tetrafluoride (CF4) gas, and then the photoresist was retreated with oxygen (O7) gas to form the end shape shown in FIG. The etching time was 3 minutes for CF gas and 5 minutes for 02 gas, and the etching temperature was 80°C. The slope of the end at this time was approximately 5000/1000 (elevation angle approximately 80'). 02 gas pressure IXLO-'torr, substrate temperature 150°C, film formation rate 1
A WO3 film having a thickness of 5,000 layers was vacuum-deposited under conditions of 0 layers per second, and formed into an 8-figure pattern for displaying numbers using a lift-off method to form a display electrode.
一方、樅45mm、横160n+m、厚さ1.lnmの
透明ガラス板からなる対向極基板の全面に、厚さ400
0人のITO膜からなる対向電極を真空蒸着法により形
成し、この上に活性炭素繊維クロス(クラレ社製の商品
名CH−20)をカーボンペースト(他力社製の商品名
PR−10)を介して貼り合わせ、180°Cで2時間
加熱処理することにより対向極物質層を形成して対向極
とした。そして、上記の周基板をWO3膜と対向極物質
層とが向かい合う形で、かつ両者の間に二酸化チタン(
TiO2)粉末とポリテトラフルオロエチレン粉末との
混合物のシー1〜状形成物(住人電気工業製の商品名ボ
アフロン)からなる背景材を介在させ、さらに周辺部に
厚さ1mmのポリエステル樹脂製の方形環状スペーサー
を介在させて対向配置し、エポキシ樹脂系接着剤にて接
着封止した後、スペーサーの一部に開けた電解液注入孔
から内部にプロピレンカーボネートに1mol/lの過
塩素酸リチウムを溶解させ、かつ0.1重量%の純水を
添加してなる電解成約6mlを注入し、注入孔をエポキ
シ樹脂系接着剤にて接着封止した。ついで、リード端子
の取り付けと銀ペースト塗布による導電層の形成を行い
、第1図に示すエレクトロクロミック表示素子を作製し
た。On the other hand, fir 45mm, width 160n+m, thickness 1. A layer with a thickness of 400 nm is placed on the entire surface of the counter electrode substrate made of a transparent glass plate of 1 nm.
A counter electrode made of an ITO film was formed by vacuum evaporation, and activated carbon fiber cloth (trade name CH-20, manufactured by Kuraray Co., Ltd.) was applied on top of the counter electrode (trade name PR-10, manufactured by Taikisha Co., Ltd.). A counter electrode material layer was formed by bonding the electrodes together through a heat treatment at 180° C. for 2 hours, thereby forming a counter electrode. Then, the above-mentioned peripheral substrate was placed in such a manner that the WO3 film and the counter electrode material layer faced each other, and titanium dioxide (
A background material made of a mixture of TiO2) powder and polytetrafluoroethylene powder (trade name Boaflon, manufactured by Judenki Kogyo Co., Ltd.) is interposed, and a rectangular shape made of polyester resin with a thickness of 1 mm is placed around the periphery. After placing them facing each other with an annular spacer in between and sealing with epoxy resin adhesive, 1 mol/l of lithium perchlorate is dissolved in propylene carbonate through an electrolyte injection hole made in a part of the spacer. 6 ml of electrolytic solution prepared by adding 0.1% by weight of pure water was injected, and the injection hole was adhesively sealed with an epoxy resin adhesive. Next, lead terminals were attached and a conductive layer was formed by applying silver paste, thereby producing the electrochromic display element shown in FIG. 1.
実施例 1
従来例における5in2膜のエツチング時間を、CF4
ガス:3分(第6図(A)→(B))、02ガス=5分
(第6図(B)→(C))、CF4ガス:4分(第6図
(C)→(D))、02ガス=8分(第6図(D)→(
E))とした以外は従来例と同様にしてエレクトロクロ
ミック表示素子を作製した、実施例1で作製した基板を
電子顕微鏡で観察したところSiO2膜の端部は第6図
(E)に示すような形状になった。Example 1 The etching time of the 5in2 film in the conventional example was changed to CF4
Gas: 3 minutes (Fig. 6 (A) → (B)), 02 gas = 5 minutes (Fig. 6 (B) → (C)), CF4 gas: 4 minutes (Fig. 6 (C) → (D) )), 02 gas = 8 minutes (Figure 6 (D) → (
An electrochromic display element was manufactured in the same manner as in the conventional example except for E)). When the substrate manufactured in Example 1 was observed with an electron microscope, the edges of the SiO2 film were found as shown in Figure 6 (E). It became a shape.
勾配は約600/1000であった。The slope was approximately 600/1000.
実施例 2 従来例における5in2膜のエツチング時間を。Example 2 Etching time for 5in2 film in conventional example.
CF、ガス:5分、02ガス:10分、CF4ガス:1
.5分、02ガス=8分とした以外は従来例と同様にし
てエレクトロクロミック表示素子を作製した。実施例2
ではSin、膜の端部形状は第7図に示すように2段の
階段状となった。下段の厚さは約2500人であった。CF, gas: 5 minutes, 02 gas: 10 minutes, CF4 gas: 1
.. An electrochromic display element was produced in the same manner as in the conventional example except that the heating time was 5 minutes and the 02 gas was 8 minutes. Example 2
In the case of Sin, the end shape of the film had a two-step staircase shape as shown in FIG. The thickness of the lower tier was about 2,500 people.
以上のようにして作製した3種類のエレクトロクロミッ
ク表示素子を第8図に示すようなタイムチャートで、4
5℃の一定温度で、着色印加電圧ニー1.OV、着色電
圧印加時間二0.8秒、休止時間=58秒、消色印加電
圧:+1.2V、消色電圧印加時間=1.2秒の条件で
サイクル寿命試験を行った。このモードはデジタル時計
の分針の変化を模したものである。The three types of electrochromic display elements produced as described above are shown in the time chart shown in Figure 8.
At a constant temperature of 5°C, coloring applied voltage knee 1. A cycle life test was conducted under the following conditions: OV, coloring voltage application time: 20.8 seconds, pause time = 58 seconds, decoloring applied voltage: +1.2V, and decoloring voltage application time = 1.2 seconds. This mode mimics the movement of the minute hand on a digital clock.
その結果、従来例の素子は26万回で断線が生じて表示
異常が発生したが、実施例1および実施例2の素子はい
ずれも40万回以上サイクル駆動しても異常は発生しな
かった。なおここでいう断線とは、WO1膜の端部が溶
解したために表示セグメントのエツジに沿って下地のI
TO膜が電解液と接触し、電気化学反応を起こしてIT
O膜が霧出して該表示セグメントとリード電極部の導通
が失われる現象である。したがって、断線が生じた表示
セグメントは応答を示さなくなり、表示素子としては致
命的な異常となる。As a result, the conventional element broke after 260,000 cycles and displayed an abnormal display, but the elements of Examples 1 and 2 did not exhibit any abnormality even after being cycled more than 400,000 times. . Note that the disconnection mentioned here is due to the melting of the edge of the WO1 film, causing the underlying I to break along the edge of the display segment.
The TO film comes into contact with the electrolyte, causing an electrochemical reaction and
This is a phenomenon in which the O film oozes out and conduction between the display segment and the lead electrode portion is lost. Therefore, the display segment in which the disconnection occurs no longer shows any response, which is a fatal abnormality for the display element.
以上説明したように1本発明ではエレクトロクロミック
膜と接する絶縁保護膜の端部形状に着目し、エレクトロ
クロミック物質の蒸着粒子が回り込みやすいような形状
に絶縁保護膜を加工形成することによって、エレクトロ
クロミック表示素子のサイクル寿命を大幅に向上させる
ことができた。As explained above, in the present invention, we focus on the shape of the end of the insulating protective film in contact with the electrochromic film, and process and form the insulating protective film in a shape that allows the deposited particles of the electrochromic substance to easily wrap around. It was possible to significantly improve the cycle life of the display element.
なお、実施例ではガスを用いたドライエツチング法を採
用しているが、酸等を用いるウェットエツチング法を採
用しても良い。In the embodiment, a dry etching method using a gas is employed, but a wet etching method using an acid or the like may also be employed.
第1図はエレクトロクロミック表示素子の基本的な素子
構造の一例を示す断面構造図、第2図は従来例を説明す
るための要部断面構造図、第3図は従来例の構造を詳細
に説明するための要部断面構造図、第4図は本発明にか
かる実施例を説明するための要部断面構造図、第5図は
従来例を説明するための要部断面構造図、第6図は実施
例1を説明するための要部断面構造図、第7図は実施例
2を説明するための要部断面構造図、第8図はサイクル
寿命試験のタイムチャートである。
1.17.21.25.29.33.37・・・・・透
明ガラス板、 2.18.22.26.30.34.3
8・・・・・・表示電極、3.20.24゜28.31
.35.39・・・・・・絶縁保護膜、 4・・・・・
・表示極基板、 5.19.23.27・・・・エレク
トロクロミック膜、 6・・・・・・表示極、7・・
・・・・対向極基板、 8・・・・・・対向電極、 9
・・・・・・対向極物質層、 10・・・・・・対向
極、 11・・・・・・スペーサー、 12・・・・
・・電解液、 13表示極り一ド端子、 14・・・
・・・対向極リード端子、 15・・・・・・導電層、
16・・・・・・背景材。
32.36.40・・・・・・フォトし・シスト特許出
願人 日立マクセル株式会社
代表者 永 井 厚
第 1
図
第2図
(,4)
q
CB)
1−一一透B月ブ丁うスイ及
2−一一表示電イ係
3−−一 傘巴永ふイ呆盲負膜
4−−−1衣示恐基仄
、5−−−一エレクトロクロミック膜
6−−−表示才函
クーー一対向イ壺基板
8−一−ヌ寸向七配径
q−−一苅向イセ電質層
7の一対向極
77−−−スペーサー
7z−m−電解液
13−−一衣示逢す−ドj高子
74−m一対向極り一ド塙各
7、f−−一導電眉
76一−〜片景肘
17−−−透明力゛ラス仮
18−一一六示電極
/d
79−一一エレクトロクロミ、り膜
zO−−一粕絽促謹謀
第3図
茨示電急
一絶録促護撲
第5
図
Zヲー−一虐明n゛ラスオ反
3θ−−一衣示電う
3ノー〜−余A縁イ矛謹月莫
32−一−フオトレンスト
第
図
(A)
災示電糧
一デまElぞヒき(イjキシLtH臭
第
1問
33−一一透明刀゛ラス板 35
34−−−ラヲビ示唱砕らオ) 36舶外保
護膜
フォトレシスト
第
図
(C)
(ρ)
第
図
38−一一表示電鈴
4θ
一7オトレソスト
第
図
(E−)
第
図
体止時間
消色電圧印加時間
看色電圧印加時間Fig. 1 is a cross-sectional structure diagram showing an example of the basic element structure of an electrochromic display element, Fig. 2 is a cross-sectional structure diagram of main parts to explain a conventional example, and Fig. 3 shows the structure of the conventional example in detail. FIG. 4 is a sectional view of the main part for explaining the embodiment of the present invention; FIG. 5 is a sectional view of the main part for explaining the conventional example; FIG. 6 is a sectional view of the main part for explaining the conventional example; FIG. 7 is a cross-sectional view of the main part for explaining Example 1, FIG. 7 is a cross-sectional view of main part for explaining Example 2, and FIG. 8 is a time chart of the cycle life test. 1.17.21.25.29.33.37...Transparent glass plate, 2.18.22.26.30.34.3
8...Display electrode, 3.20.24°28.31
.. 35.39...Insulating protective film, 4...
・Display electrode substrate, 5.19.23.27... Electrochromic film, 6... Display electrode, 7...
...Counter electrode substrate, 8...Counter electrode, 9
...Counter electrode material layer, 10...Counter electrode, 11...Spacer, 12...
...Electrolyte, 13 display terminal, 14...
... Opposite electrode lead terminal, 15 ... Conductive layer,
16...Background material. 32.36.40...Photography/Sist Patent Applicant Hitachi Maxell Co., Ltd. Representative Atsushi Nagai 1 Figure 2 (,4) q CB) 1-11 Toru B Monthly Button Sui and 2-11 Display phone section 3--1 Umbrella, blind negative film 4--1 Display base, 5--1 Electrochromic film 6--Display box One opposing electrode 77 of the electrolyte layer 7 in one direction - Electrolyte 13 - Doj Takako 74-m 1 Opposite pole 1 Dohanawa each 7, f--1 Conductive eyebrow 76-1--One view elbow 17--Transparent force glass temporary 18-116 Indicating electrode/d 79- 11 Electrochromi, Rime ZO--Ichikasuke promotion 3rd figure Ibarashi Denkyu Ikzetsuroku promotion 5th figure 3 No ~ - I'm sorry for my relationship with you Lath plate 35 34-----Rawobi display broken o) 36 External protective film photoresist diagram (C) (ρ) Figure 38-11 Display bell 4θ 17 Otresist diagram (E-) Figure body stop Time Decoloring voltage application time Coloring voltage application time
Claims (6)
該透明導電膜の表面に部分的にパターン化されて形成さ
れたエレクトロクロミック膜と、該エレクトロクロミッ
ク膜が形成されていない上記透明導電膜の表面に少なく
とも3,000Åの膜厚に形成された絶縁保護膜とを有
するエレクトロクロミック表示素子において、前記エレ
クトロクロミック膜が前記絶縁保護膜と接する付近の膜
厚が中央部の膜厚とほぼ同等以上であることを特徴とす
るエレクトロクロミック表示素子。(1) A transparent conductive film formed on the surface of a transparent glass plate,
an electrochromic film partially patterned and formed on the surface of the transparent conductive film; and an insulating film having a thickness of at least 3,000 Å formed on the surface of the transparent conductive film on which the electrochromic film is not formed. 1. An electrochromic display element having a protective film, wherein the thickness of the electrochromic film in the vicinity where the electrochromic film contacts the insulating protective film is approximately equal to or greater than the thickness of the central part.
該透明導電膜の表面に部分的にパターン化されて形成さ
れたエレクトロクロミック膜と、該エレクトロクロミッ
ク膜が形成されていない上記透明導電膜の表面に少なく
とも3,000Åの膜厚に形成された絶縁保護膜とを有
するエレクトロクロミック表示素子において、前記絶縁
保護膜の前記エレクトロクロミック膜と接する端部に勾
配を設けたことを特徴とするエレクトロクロミック表示
素子。(2) a transparent conductive film formed on the surface of a transparent glass plate;
an electrochromic film partially patterned and formed on the surface of the transparent conductive film; and an insulating film having a thickness of at least 3,000 Å formed on the surface of the transparent conductive film on which the electrochromic film is not formed. An electrochromic display element having a protective film, characterized in that an end portion of the insulating protective film in contact with the electrochromic film is provided with a slope.
1000/1000の範囲にあることを特徴とする請求
項(2)記載のエレクトロクロミック表示素子。(3) The electrochromic display element according to claim (2), wherein the slope of the edge of the insulating protective film is in the range of 300/1000 to 1000/1000.
形成されていることを特徴とする請求項(2)または(
3)記載のエレクトロクロミック表示素子。(4) Claim (2) or (4) characterized in that the slope corner of the sloped insulating protective film is formed in an arc shape.
3) The electrochromic display element described above.
該透明導電膜の表面に部分的にパターン化されて形成さ
れたエレクトロクロミック膜と、該エレクトロクロミッ
ク膜が形成されていない上記透明導電膜の表面に少なく
とも3,000Åの膜厚に形成された絶縁保護膜とを有
するエレクトロクロミック表示素子において、前記絶縁
保護膜の前記エレクトロクロミック膜と接する端部が階
段状に形成されていることを特徴とするエレクトロクロ
ミック表示素子。(5) a transparent conductive film formed on the surface of a transparent glass plate;
an electrochromic film partially patterned and formed on the surface of the transparent conductive film; and an insulating film having a thickness of at least 3,000 Å formed on the surface of the transparent conductive film on which the electrochromic film is not formed. An electrochromic display element having a protective film, characterized in that an end portion of the insulating protective film in contact with the electrochromic film is formed in a stepped shape.
、絶縁保護膜の全膜厚の2分の1以下でかつ3,000
Å以下であることを特徴とする請求項(5)記載のエレ
クトロクロミック表示素子。(6) The thickness of the bottom step of the stepped portion at the end of the insulating protective film is 1/2 or less of the total thickness of the insulating protective film and 3,000 yen
6. The electrochromic display element according to claim 5, wherein the electrochromic display element has a thickness of Å or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28975388A JPH02135322A (en) | 1988-11-16 | 1988-11-16 | Electrochromic display element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28975388A JPH02135322A (en) | 1988-11-16 | 1988-11-16 | Electrochromic display element |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02135322A true JPH02135322A (en) | 1990-05-24 |
Family
ID=17747315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28975388A Pending JPH02135322A (en) | 1988-11-16 | 1988-11-16 | Electrochromic display element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02135322A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7858983B2 (en) | 2003-07-31 | 2010-12-28 | Satoshi Morita | Electrochromic display with current drive circuit |
-
1988
- 1988-11-16 JP JP28975388A patent/JPH02135322A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7858983B2 (en) | 2003-07-31 | 2010-12-28 | Satoshi Morita | Electrochromic display with current drive circuit |
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