JPS6355685B2 - - Google Patents
Info
- Publication number
- JPS6355685B2 JPS6355685B2 JP55030298A JP3029880A JPS6355685B2 JP S6355685 B2 JPS6355685 B2 JP S6355685B2 JP 55030298 A JP55030298 A JP 55030298A JP 3029880 A JP3029880 A JP 3029880A JP S6355685 B2 JPS6355685 B2 JP S6355685B2
- Authority
- JP
- Japan
- Prior art keywords
- material layer
- electrochromic
- layer
- electrochromic material
- ion
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 23
- 238000009792 diffusion process Methods 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 description 20
- 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 7
- 229910001930 tungsten oxide Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 4
- -1 AgI Chemical compound 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IRDHJHLKOGRHJJ-UHFFFAOYSA-M iodosilver;rubidium Chemical compound [Rb].I[Ag] IRDHJHLKOGRHJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Description
【発明の詳細な説明】
本発明はエレクトロクロミツクを用いた表示素
子に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a display element using electrochromic technology.
エレクトロクロミツクを用いた表示体乃至表示
素子は一般に少なくとも一方は色調変化が目視或
いは機械的な光学判断ができるようになつてお
り、第１図に断面的に示す如く構成されている。
即ち一対の電極層１，１′を備えており、これら
両電極層１，１′間に酸化タングステンなどのエ
レクトロクロミツク材料層（電気発色性材料層）
２およびイオン導電性材料層３を介在させた構成
を採つている。しかして目視で使用する表示素子
では、ネサガラスで代表される透明導電性ガラス
が、その透明導電層を所要のセグメントや図形な
どにパターン化され一方の電極層１として用いら
れている。尚第１図において、４は電極層１を支
持するガラス基板を、５はスペーサをそれぞれ示
す。 Display bodies or display elements using electrochromic technology are generally designed so that the change in color tone can be determined visually or mechanically on at least one side, and is constructed as shown in cross section in FIG. 1.
That is, it has a pair of electrode layers 1 and 1', and an electrochromic material layer (electrochromic material layer) such as tungsten oxide is placed between these electrode layers 1 and 1'.
2 and an ion conductive material layer 3 are interposed therebetween. In a display element used for visual observation, a transparent conductive glass such as Nesa Glass is used as one electrode layer 1 by patterning its transparent conductive layer into desired segments or shapes. In FIG. 1, 4 indicates a glass substrate supporting the electrode layer 1, and 5 indicates a spacer.
上記構成の電気発色素子においてイオン導電性
材料層３を例えばAgI、RbAg4I5など銀塩、或い
はNaxWO3などナトリウム塩、またはSiO、
CaF2などの固体電解質で形成することも試みら
れている。この固体電解質を用いた場合には、液
密封止などを要しないため素子の組立、製造が簡
単になるという利点がある。しかし一方ではこの
種の固体電解質を用いて構成した表示発色素子に
おいては銀イオンのマイグレーシヨン或いはナト
リウムイオンのトラツプ作用によつて電極層１，
１′や電気発色性材料層２の劣化を起生するとい
う不都合さがある。 In the electrochromic element having the above structure, the ion conductive material layer 3 is made of a silver salt such as AgI, RbAg 4 I 5 , a sodium salt such as NaxWO 3 , or SiO,
Formation with solid electrolytes such as CaF2 has also been attempted. When this solid electrolyte is used, there is an advantage that assembly and manufacturing of the device are simplified because liquid-tight sealing and the like are not required. However, on the other hand, in display dye elements constructed using this type of solid electrolyte, the electrode layer 1,
There is a disadvantage that deterioration of the electrochromic material layer 1' and the electrochromic material layer 2 occurs.
従つて本発明は上述の如き欠点乃至問題点を除
去した電気発色素子を提供しようとするものであ
る。 Therefore, it is an object of the present invention to provide an electroluminescent element which eliminates the above-mentioned drawbacks and problems.
以下本発明を詳細に説明すると、本発明は遷移
金属酸化物系の電気発色性材料層およびこの電気
発色性材料層に接するイオン導電性材料層とを具
備して成る電気発色素子において、前記イオン導
電性材料層に接する電気発色性材料層の表面が結
晶質化し、イオンの拡散制御層化されていること
を特徴とする電気発色素子である。 To explain the present invention in detail below, the present invention provides an electrochromic element comprising a transition metal oxide electrochromic material layer and an ion conductive material layer in contact with the electrochromic material layer. The electrochromic element is characterized in that the surface of the electrochromic material layer in contact with the conductive material layer is crystallized to form an ion diffusion control layer.
第２図はこのような本発明に係る電気発色素子
の構成例を断面的に示したもので、例えば次の如
く容易に製造できる。先ずネサガラス板を用意
し、透明導電性膜を所望の電極層をなすようパタ
ーン化した後、このパターン化した透明導電性膜
上１に厚さ0.3μの酸化タングステン（WO3）層２
を蒸着形成する。次いでレーザー光などのエネル
ギー線を上記酸化タングステン層２の表面に照射
することにより、酸化タングステン膜２の表面は
加熱され、表面を深さ0.05μ程度にわたりイオン
の拡散を制御しうる結晶質化層２′ならしめる。 FIG. 2 shows a cross-sectional view of an example of the structure of the electroluminescent element according to the present invention, which can be easily manufactured, for example, as follows. First, a Nesa glass plate is prepared, a transparent conductive film is patterned to form a desired electrode layer, and then a 0.3μ thick tungsten oxide (WO 3 ) layer 2 is placed on the patterned transparent conductive film 1.
Formed by vapor deposition. Next, by irradiating the surface of the tungsten oxide layer 2 with an energy beam such as a laser beam, the surface of the tungsten oxide film 2 is heated, and a crystallized layer is formed over the surface to a depth of about 0.05μ that can control the diffusion of ions. Make it 2'.
尚エネルギー線としてレーザー光を用いる場合
には、その光源としてルビーレーザー（波長
0.694μ）、Na−YAGレーザー（波長1.06μ）など
のＱスイツチパルスレーザーを用い、照射条件は
パルス巾、20〜50nsec、パワ密度107〜108W／
cm2、照射パルス数、１〜10の範囲にそれぞれ選択
すればよい。 In addition, when using laser light as an energy beam, the light source is a ruby laser (wavelength
A Q-switch pulse laser such as a Na-YAG laser (wavelength 1.06μ) or Na-YAG laser (wavelength 1.06μ) was used, and the irradiation conditions were a pulse width of 20 to 50 nsec, and a power density of 10 7 to 10 8 W/.
cm 2 and the number of irradiation pulses may be selected in the range of 1 to 10.
しかる後例えばスパツタ法によつてイオン導電
性膜として厚さ0.15μ程度の窒化リチウム膜３を
上記の、レーザー光照射を行ない、結晶質化した
酸化タングステン層２′上に形成する。 Thereafter, a lithium nitride film 3 having a thickness of about 0.15 μm is formed as an ion-conductive film on the crystallized tungsten oxide layer 2' by laser beam irradiation, for example, by sputtering.
次に上記窒化リチウム膜３上に対向する一方の
電極層１′として白金層を蒸着形成してから空隙
領域を例えばエポキシ樹脂６にて封止することに
より第２図示構成の電気発色素子が得られる。 Next, a platinum layer is formed on the lithium nitride film 3 by vapor deposition as one of the opposing electrode layers 1', and the gap region is sealed with, for example, an epoxy resin 6, thereby obtaining an electroluminescent element having the structure shown in the second figure. It will be done.
本発明においてイオン拡散抑制膜たる結晶質酸
化タングステン層２′を設けるにあたつては、上
記Ｑスイツチパルスレーザー光源の他アルゴンレ
ーザー、炭酸ガスレーザーなどのパワ密度
106W／cm2以下の連続発振レーザーも用い得るし、
さらに他のエネルギー線としてはフラツシユラン
プ、電子線なども使用しうる。 In the present invention, in providing the crystalline tungsten oxide layer 2' which is an ion diffusion suppressing film, in addition to the above-mentioned Q-switch pulse laser light source, the power density of an argon laser, a carbon dioxide laser, etc.
A continuous wave laser of 10 6 W/cm 2 or less can also be used,
Furthermore, as other energy beams, a flash lamp, an electron beam, etc. can be used.
本発明において、イオン導電膜は上記窒化リチ
ウムなどリチウムイオン、沃化銀、沃化ルビジウ
ム銀などの銀イオン或いはβ−アルミナなどナト
リウムイオンを用い構成し得る。イオン導電性膜
の形成は蒸着法、スパツタ法もしくはイオンプレ
ーテイング法によつて行ない得る。またイオン導
電性濃３の厚さは0.05〜1μ好ましくは0.1〜0.3μ程
度の範囲に、イオン拡散抑制膜たる結晶質酸化タ
ングステン層２′の厚さは0.01〜0.1μ程度の範囲
にそれぞれ選択するのが好ましい。さらにこれら
の両膜２′，３についてみると、その比抵抗が電
気発消色の応答性に影響をおよぼすことから、イ
オン拡散抑制膜２′の比抵抗はイオン導電膜３の
５〜10000倍通常５〜50倍程度に選択することが
好ましい。 In the present invention, the ion conductive film may be constructed using lithium ions such as the above-mentioned lithium nitride, silver ions such as silver iodide and rubidium silver iodide, or sodium ions such as β-alumina. The ion conductive film can be formed by vapor deposition, sputtering or ion plating. In addition, the thickness of the ion conductive layer 3 is selected to be in the range of 0.05 to 1 μm, preferably 0.1 to 0.3 μm, and the thickness of the crystalline tungsten oxide layer 2', which is the ion diffusion suppressing film, is selected to be in the range of approximately 0.01 to 0.1 μm. It is preferable to do so. Furthermore, looking at both of these films 2' and 3, the specific resistance of the ion diffusion suppressing film 2' is 5 to 10,000 times that of the ion conductive film 3, since its specific resistance affects the responsiveness of electrochromic/decolorizing. Usually, it is preferable to select about 5 to 50 times.
次に本発明に係る電気発色素子の特性例につい
て示すと、前記第２図構成の電気発色素子の透明
電極１と対向電極１′との間に直流1.5Vを印加し
たところ150ｍsecで濃青色像が得られた。また電
源を切り放置したところ10分後でも濃青色像が維
持されており、逆電圧を印加すると100ｍsecで濃
青色像が消失した。さらに、印加電圧1.2Vの矩
形波にて１Hzの周波数で駆動しても、両電極１，
１′および電気発色性材料層２の劣化は認められ
ず且つコントラスト比12対１で２×107回の駆動
にも耐えすぐれた安定性を示した。一方電気発色
性材料層に結晶質化層を設けない比較例の電気発
色素子の場合には104回の駆動で電気発色材料層
の劣化がみられた。 Next, an example of the characteristics of the electroluminescent element according to the present invention will be described. When a DC voltage of 1.5 V was applied between the transparent electrode 1 and the counter electrode 1' of the electroluminescent element having the structure shown in FIG. was gotten. Furthermore, when the power was turned off and left as it was, the dark blue image was maintained even after 10 minutes, and when a reverse voltage was applied, the dark blue image disappeared in 100 msec. Furthermore, even if driven at a frequency of 1Hz with a rectangular wave with an applied voltage of 1.2V, both electrodes 1,
No deterioration was observed in the electrochromic material layer 1' and the electrochromic material layer 2, and the contrast ratio was 12:1, showing excellent stability even after driving 2×10 7 times. On the other hand, in the case of the electrochromic element of the comparative example in which the crystallized layer was not provided in the electrochromic material layer, deterioration of the electrochromic material layer was observed after 10 4 times of driving.
上記具体例から明らかのようにイオン導電性材
料層（膜）と接する電気発色性材料層の表面を特
にレーザー光照射などによつて結晶質電気発色性
材料層化しイオンの拡散を制御しうるようにした
本発明に係る固体形電気発色素子においては、イ
オン導電性膜、例えば窒化リチウム膜３からこれ
に接する酸化タングステンなどの電気発色性材料
層２へのイオンの拡散が結晶質化した電気発色性
材料層２′により制御、抑制されるので、所要の
発消色機能が維持発揮されると共に、応答性も改
善されさらにコントラストも向上し、常に良好な
表示機能を示す。 As is clear from the above specific example, the surface of the electrochromic material layer in contact with the ion conductive material layer (film) is formed into a crystalline electrochromic material layer by irradiation with laser light, etc., so that the diffusion of ions can be controlled. In the solid-state electrochromic element according to the present invention, diffusion of ions from the ion-conductive film, for example, the lithium nitride film 3 to the electrochromic material layer 2, such as tungsten oxide, in contact with the ion-conductive film causes crystallized electrochromic formation. Since the coloring material layer 2' is controlled and suppressed, the required coloring/decoloring function is maintained and exhibited, the responsiveness is improved, and the contrast is also improved, so that a good display function is always exhibited.
加えて、イオンの拡散を制御、抑制する層とし
て、電気発色性材料層を蒸着条件を変えて、既に
蒸着形成されて電気発色性材料層の上に重畳蒸着
し形成する場合に較べ、レーザー光照射などによ
つて電気発色性材料層表面を結晶質化してイオン
の拡散を制御せしめる本発明に係る電気発色素子
によれば、蒸着条件に伴なうばらつき、イオン拡
散の制御などの不安定さが回避され、安定した表
示性能を常に発揮でき、且つ製造工程も大幅に短
縮、簡単化され得る。 In addition, as a layer for controlling and suppressing the diffusion of ions, the electrochromic material layer can be formed by changing the deposition conditions and being superimposed on the electrochromic material layer that has already been deposited. According to the electrochromic element of the present invention, which controls the diffusion of ions by crystallizing the surface of the electrochromic material layer by irradiation or the like, there are problems such as variations in deposition conditions and instability in controlling ion diffusion. is avoided, stable display performance can always be exhibited, and the manufacturing process can be significantly shortened and simplified.
かくして本発明の電気発色素子は製造の容易
さ、固体形であることにともなう取扱い易さなど
と相俟つて実用上多くの利点をもたらすものと言
える。 Thus, it can be said that the electroluminescent element of the present invention provides many practical advantages, including ease of manufacture and ease of handling due to its solid state.
第１図は従来知られている電気発色素子の構成
例を示す断面図、第２図は本発明に係る電気発色
素子の構成例を示す断面図である。
１……透明電極層、１′……対向電極層、２…
…電気発色性材料層、３……電解液、２′……結
晶質電気発色性材料層（イオン拡散抑制膜）、３
……イオン導電性膜、４……ガラス基板、５……
スペーサ、６……封止樹脂。
FIG. 1 is a sectional view showing an example of the structure of a conventionally known electroluminescent element, and FIG. 2 is a sectional view showing an example of the structure of an electroluminescent element according to the present invention. 1...Transparent electrode layer, 1'...Counter electrode layer, 2...
...Electrochromic material layer, 3... Electrolyte, 2'... Crystalline electrochromic material layer (ion diffusion suppressing film), 3
...Ion conductive film, 4...Glass substrate, 5...
Spacer, 6... Sealing resin.
Claims (1)
の電気発色性材料層に接するイオン導電性材料層
とを具備して成る電気発色素子において、前記イ
オン導電性材料層に接する電気発色性材料層面が
結晶質化しイオン拡散制御層化されていることを
特徴とする電気発色素子。1. In an electrochromic element comprising an electrochromic material layer of a transition metal oxide and an ionically conductive material layer in contact with the electrochromic material layer, the surface of the electrochromic material layer in contact with the ionically conductive material layer is An electroluminescent element characterized by being crystallized and layered to control ion diffusion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029880A JPS56126825A (en) | 1980-03-12 | 1980-03-12 | Electrochromic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029880A JPS56126825A (en) | 1980-03-12 | 1980-03-12 | Electrochromic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56126825A JPS56126825A (en) | 1981-10-05 |
| JPS6355685B2 true JPS6355685B2 (en) | 1988-11-04 |
Family
ID=12299825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3029880A Granted JPS56126825A (en) | 1980-03-12 | 1980-03-12 | Electrochromic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56126825A (en) |
-
1980
- 1980-03-12 JP JP3029880A patent/JPS56126825A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56126825A (en) | 1981-10-05 |
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