JPS62203133A - Optical modulating element - Google Patents
Optical modulating elementInfo
- Publication number
- JPS62203133A JPS62203133A JP61043946A JP4394686A JPS62203133A JP S62203133 A JPS62203133 A JP S62203133A JP 61043946 A JP61043946 A JP 61043946A JP 4394686 A JP4394686 A JP 4394686A JP S62203133 A JPS62203133 A JP S62203133A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- coloring
- electrochromic
- coloring layer
- cathode side
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- 238000004040 coloring Methods 0.000 claims abstract description 55
- 230000007935 neutral effect Effects 0.000 claims abstract description 18
- 238000000862 absorption spectrum Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract 3
- 230000003595 spectral effect Effects 0.000 abstract 3
- 239000004020 conductor Substances 0.000 abstract 2
- 238000010030 laminating Methods 0.000 abstract 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 Gap Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 229940090961 chromium dioxide Drugs 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride 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
- 230000001590 oxidative effect Effects 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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素子、特にその着色時の
吸収スペクトル特性が可視光域においてニュートラルで
あり、光学変調素子として応用できるエレクトロクロミ
ック素子に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrochromic device, and particularly to an electrochromic device whose absorption spectrum characteristics when colored are neutral in the visible light range and which can be applied as an optical modulation device. be.
［従来の技術］
全固体型エレクトロクロミック素子の一般的な２つの構
造例を第１図（Ａ）、 （Ｂ）に示す。[Prior Art] Two general structural examples of all-solid-state electrochromic devices are shown in FIGS. 1(A) and 1(B).
ｉ１図（Ａ）に示すエレクトロクロミック素子は、透明
な基板１の上に、透明導電体膜よりなる第１電極２、陽
極側発色層である酸化発色性のエレクトロクコミック層
３、誘電体膜からなる絶縁層４、導電体膜よりなる第２
電極５を順次積層してなるものである。また、第１図（
Ｂ）に示すエレクトロクロミンク素子は、第１図（Ａ）
に示す構造における絶縁層４と第２電極５との間に、更
に陰極側発色層である還元発色性の第２のエレクトロク
ロミック層６を積層したものである。The electrochromic element shown in Fig. i1 (A) has a first electrode 2 made of a transparent conductive film on a transparent substrate 1, an oxidative color-forming electrochromic layer 3 which is an anode side color-forming layer, and a dielectric film. an insulating layer 4 made of
It is formed by sequentially stacking electrodes 5. Also, Figure 1 (
The electrochromic device shown in B) is shown in Figure 1 (A).
Between the insulating layer 4 and the second electrode 5 in the structure shown in FIG. 1, a second electrochromic layer 6 with reduction coloring property, which is a coloring layer on the cathode side, is further laminated.
基板１は一般にガラス板によって形成されるが、これは
ガラス板に限らず、プラスティック板またはアクリル板
等の無色透明な板ならば良く、また、その位置に関して
も、第１電極２の下に限らず第２電極５の上にあっても
よいし、目的に応じて（例えば保護カバーとするなどの
目的で）両面に設けてもよい。The substrate 1 is generally formed of a glass plate, but it is not limited to a glass plate, and any colorless and transparent plate such as a plastic plate or an acrylic plate may be used. It may be provided first on the second electrode 5, or may be provided on both sides depending on the purpose (for example, for the purpose of serving as a protective cover).
第１電極２は、ＩＴＯ膜（Ｉｎ２０３中に５ｎ０２を混
入したもの）やＮＥＳＡ （ネサ）膜（５ｎ０２）など
の透明導電膜で構成される。第２電極５も透明電極とす
れば透明型の素子ができる。The first electrode 2 is made of a transparent conductive film such as an ITO film (In203 mixed with 5n02) or a NESA film (5n02). If the second electrode 5 is also a transparent electrode, a transparent element can be obtained.
酸化発色性の第１エレクトロクロミック層３をなす物質
としては、Ｖ２Ｏ３、ＷＯｚ 、 Ｃｕ２Ｏ，Ｎｉｐ、
ＳｎＯ。The substances forming the first electrochromic layer 3 with oxidation coloring property include V2O3, WOz, Cu2O, Nip,
SnO.
ＰｂＯ，Ｃｅ２Ｏ３，Ｔｉｅ、 Ｃａ２Ｏ，Ａｇ２Ｏ
，Ｈｇ２０． Ｔｂ２Ｏ３゜Ｓｉｎ、 Ｔａｇ、
Ｆｅｄ、 Ｏｓ’、 Ａｕ２０３． ＭＯＯ４
，Ｃｒｙ、 ＣｄＯ。PbO, Ce2O3, Tie, Ca2O, Ag2O
, Hg20. Tb2O3゜Sin, Tag,
Fed, Os', Au203. MOO4
, Cry, CdO.
Ｉｒ２０３ ＋ ＭｎＯ，ＶＯ２＋ Ｃａｏなどが挙げ
られる。Examples include Ir203 + MnO and VO2+ Cao.
絶縁層４をなす物質としては、酸化チタン、酸化ジルコ
ニウム、酸化ハフニウム、五酸化タンタル、二酸化ケイ
素、酸化ゲルマニウム、カルコゲニドガラス、塩化ナト
リウム、塩化カリウム、フッ化マグネシウム、フッ化カ
ルシウム、ポリ塩化ビニル、ポリスチレン、ポリビニル
アルコール、ポリエステル、セルロース等多くの物質が
使用可能である。Materials forming the insulating layer 4 include titanium oxide, zirconium oxide, hafnium oxide, tantalum pentoxide, silicon dioxide, germanium oxide, chalcogenide glass, sodium chloride, potassium chloride, magnesium fluoride, calcium fluoride, polyvinyl chloride, and polystyrene. , polyvinyl alcohol, polyester, cellulose, and many other materials can be used.
還元発色性の第２エレクトロクロミック層６ヲナス物質
トシテハ、ＷＯ３，Ｖ２Ｏ５，Ｇａｐ、 ＭｎＯｘ。Reduction color-forming second electrochromic layer 6 materials include WO3, V2O5, Gap, MnOx.
５ｎＯｚ、 ＩｒＯ＋、 Ｎｂ２Ｏ５，ＶＯ３，ＴｅＯ
２，ＣｄＯ，Ｃｒ２（ｈ。5nOz, IrO+, Nb2O5, VO3, TeO
2, CdO, Cr2 (h.
ＭｎＯ２，Ｔａ２０５． Ｃｏ２Ｏ３，Ｒｅ０７． Ａ
ｕ２０３． Ｆｅ２Ｏ３゜５ｂ２０５ 、 ＴｉＯ２，
ＣｅＯ２、５ｂ２０３ 、 ＡｇＯなどが挙げられる。MnO2, Ta205. Co2O3, Re07. A
u203. Fe2O3゜5b205, TiO2,
Examples include CeO2, 5b203, AgO, and the like.
この様な構成のエレクトロクロミック素子は、電極２．
５間に電圧を印加することにより電気化学的反応が誘起
され、着色、消色を行なう。An electrochromic element having such a configuration has electrodes 2.
By applying a voltage between 5 and 5, an electrochemical reaction is induced, resulting in coloring and decoloring.
例えば、第２図において、酸化発色層３をＩｒＯｘ、
Ｗｉ元発色層６をＷＯ３で構成し、酸化発色層３側をプ
ラス・（÷）、還元発色層６側をマイナス（−）に印加
すると、ＩｒＯｘ及びＷＯ３はそれぞれ、ＩｒＯｘ＋
７Ｈ２０ａｄ＋ Ｉｒ０ｘ（ＯＨ）ｙ＋ ｙＨ°＋
ｙｅ−Ｗ０３＋ ｖＨ◆＋、ｙｅ−＋ ＨｙＷＯ３
（但し、Ｈ２０ａ ｄは素子中に含まれる吸着水を示す
、）
なる反応により、着色種Ｉｒ０ｘ（ＯＨ）ｙ、 ＨｙＷ
Ｏ３が生成して発色し、電界を逆転することにより上式
と逆の反応が起こり消色するものと考えられる。For example, in FIG. 2, the oxidized coloring layer 3 is IrOx,
When the Wi source coloring layer 6 is composed of WO3 and a positive voltage (÷) is applied to the oxidized coloring layer 3 side and a negative voltage (-) is applied to the reduced coloring layer 6 side, IrOx and WO3 respectively become IrOx+.
7H20ad+ Ir0x(OH)y+ yH°+
ye-W03+ vH◆+, ye-+ HyWO3
(However, H20a d indicates adsorbed water contained in the element.) Due to the following reaction, colored species Ir0x(OH)y, HyW
It is thought that O3 is generated and develops color, and by reversing the electric field, a reaction opposite to the above equation occurs and the color disappears.
この発消色反応において、絶縁層６は、Ｈ２０ａ ｄの
供給源であると同時に着色種の再結合による逆反応を防
ぐこと、換言すればイオンの導通と電子のブロッキング
を行なうという働きを有する。In this coloring/decoloring reaction, the insulating layer 6 functions as a source of H20ad and at the same time prevents a reverse reaction due to recombination of colored species, in other words, conducts ions and blocks electrons.
［発明が解決しようとする問題点］
上記のような従来構成において、陽極側発色層（酸化発
色性物質）としてはＩｒ、旧、 Ｇｏ等の水酸化物に代
表されるように、着色時の吸収スペクトルがニュートラ
ル（グレー）なものが存在するが、陰極側発色層（還元
発色性物質）については着色時の吸収スペクトルがニュ
ートラルである物質が現在に至るまで発見されていない
。エレクトロクロミック素子全体としては陰極側と陽極
側の相乗スペクトルとなるため、吸収スペクトルはニュ
ートラル、でなく、そのためニュートラル性が必要とさ
れる光学変調素子、例えばライトパルプ、ＮＯフィルタ
ー等への応用ができないという問題がある。[Problems to be Solved by the Invention] In the conventional configuration as described above, the coloring layer (oxidation coloring material) on the anode side is typified by hydroxides such as Ir, old, Go, etc. Although there are materials with a neutral (gray) absorption spectrum, no material has been discovered to date that has a neutral absorption spectrum when colored in the cathode side coloring layer (reduction coloring material). Since the electrochromic element as a whole has a synergistic spectrum between the cathode side and the anode side, the absorption spectrum is not neutral, and therefore cannot be applied to optical modulation elements that require neutrality, such as light pulp and NO filters. There is a problem.
本発明は上述従来技術の問題を解決し、ニュートラルな
吸収スペクトル特性を有するエレクトロクロミック素子
を実現することによって、従来の光学変調素子では困難
であった変調の可変性を有し、例えば可変ＮＤフィルタ
ーのような可変光学変調素子を提供することを目的とす
る。The present invention solves the above-mentioned problems of the prior art and realizes an electrochromic element having neutral absorption spectrum characteristics, thereby achieving modulation variability that is difficult to achieve with conventional optical modulation elements, such as a variable ND filter. The purpose of the present invention is to provide a variable optical modulation element.
［問題点を解決するための手段および作用］本発明によ
れば、導電体膜よりなる第１電極と、陽極側発色層であ
るエレクトロクロミック層と、誘電体膜からなる絶縁層
と、導電体膜よりなる第２電極を順次積層し、あるいは
上記の絶縁層と第２電極の間にさらに陰極側発色層であ
る第２のエレクトロクロミック層を積層してなる全固体
型エレクトロクコミック素子であって、上記陽極側発色
層としてニュートラルな吸収スペクトル特性を持つエレ
クトロクロミック物質を用い、または更に上記陰極側発
色層として、非発色化処理するか、陰極側発色層の還元
発色性物質の代わりに酸化還元を可逆的に行なう非発色
物質を用いた陽極側単極発色型のエレクトロクロミック
素子による、可視光域でニュートラルな吸収スペクトル
特性を有することを特徴とする光学変調素子が提供され
る。[Means and effects for solving the problems] According to the present invention, a first electrode made of a conductive film, an electrochromic layer which is an anode side coloring layer, an insulating layer made of a dielectric film, and a conductive film are provided. This is an all-solid-state electrochromic device in which a second electrode consisting of a film is sequentially laminated, or a second electrochromic layer, which is a coloring layer on the cathode side, is further laminated between the above-mentioned insulating layer and the second electrode. In this case, an electrochromic substance with neutral absorption spectrum characteristics is used as the coloring layer on the anode side, or a non-coloring treatment is used as the coloring layer on the cathode side, or an oxidized substance is used in place of the reduced coloring material in the coloring layer on the cathode side. Provided is an optical modulation element characterized by having neutral absorption spectrum characteristics in the visible light region, which is formed by an anode-side unipolar color-forming electrochromic element using a non-color-forming substance that performs reversible reduction.
上記したように、本発明においては前述第１図（Ｂ）の
従来構成中でニュートラルな吸収スペクトル特性の得ら
れていない陰極側発色層６を非発色化処理するか、陰極
側発色層６の還元発色性物質の代わりに酸化還元反応を
可逆的に行ない且つ両状態において非着色である物質（
非着色酸化還元物質）を使用し、陰極側は陽極側反応の
反応補償のみを行なうものとする。As described above, in the present invention, the color forming layer 6 on the cathode side, which does not have a neutral absorption spectrum characteristic in the conventional structure shown in FIG. Substances that perform redox reactions reversibly and are non-colored in both states (instead of reduction color-forming substances)
A non-colored redox substance) is used, and the cathode side only compensates for the reaction on the anode side.
陰極側発色層を非発色化処理する手段としては、例えば
アモルファス状態にあるＥＣ物質を微結晶化または多結
晶化し、可視域で着色する特性を除去すればよい、具体
的には成膜時の蒸着速成低下、基板加熱、または成膜後
の熱アニール等が考えられる。As a means for non-coloring the cathode side coloring layer, for example, the EC substance in an amorphous state may be microcrystalized or polycrystalized to remove the characteristic of coloring in the visible range. Possible causes include a decrease in deposition rate, substrate heating, or thermal annealing after film formation.
また、非着色酸化還元物質を用いる場合、このような物
質の例としては、二酸化クロム、熱処理した酸化タング
ステン等が挙げられる。Further, when a non-colored redox substance is used, examples of such a substance include chromium dioxide, heat-treated tungsten oxide, and the like.
また、陽極側発色層３はニュートラルな吸収スペクトル
特性を持つ酸化発色性物質、例えばＩｒ。The coloring layer 3 on the anode side is made of an oxidized coloring material having neutral absorption spectrum characteristics, such as Ir.
旧、 Ｃｏの酸化物または水酸化物等が用いられる。Previously, Co oxides or hydroxides were used.
このような構成により、ニュートラルな吸光スペクトル
特性を持つ単極発色型エレクトロクロミック素子が実現
され、可変光学変調素子への応用が可能と・なる０例え
ば本発明による可変ＮＤフィルターをカメラの光学系に
組み込めば、従来のような撮影時にＮＯフィルターを着
脱する煩わしさを伴なわずに、高感度フィルム使用時の
絞り開放側またはシャッタースピード低速側等の撮影領
域拡大などの新しい機能をカメラに持たせることができ
る。このような場合、可変ＮＯフィルターは光学系のど
こに位置してもよく１例えば第２図のようにレンズ曲面
状に形成することも可能である。With such a configuration, a monopolar color-forming electrochromic device with neutral absorption spectrum characteristics is realized, and it becomes possible to apply it to a variable optical modulation device.For example, the variable ND filter according to the present invention can be used in a camera optical system. By incorporating it, the camera can be equipped with new functions, such as expanding the shooting range when using high-sensitivity film, such as opening the aperture or slowing down the shutter speed, without the hassle of attaching and detaching the NO filter during shooting. be able to. In such a case, the variable NO filter may be located anywhere in the optical system; for example, it may be formed in the shape of a curved lens surface as shown in FIG.
第２図において、７はカメラレンズ部、１２はミラー、
１３はフィルム面、８．１０はレンズ、９は絞りユニッ
トである。この例ではレンズ１０上にエレクトロクロミ
ック可変ＮＤフィルター１１が形成される。In Fig. 2, 7 is a camera lens section, 12 is a mirror,
13 is a film surface, 8.10 is a lens, and 9 is an aperture unit. In this example, an electrochromic variable ND filter 11 is formed on the lens 10.
［実施例］
本発明の光学変調素子を可変ＮＯフィルターに応用した
場合の実施例を第３図により説明する。[Example] An example in which the optical modulation element of the present invention is applied to a variable NO filter will be described with reference to FIG.
１５はフィルム供給室、１６はフィルム巻き取り室、１
７がフィルム面である。フィルム面１７の近傍に設置さ
れた本発明によるエレクトロクロミック可変ＮＯフィル
ター１４は、数十〜数百のマス目に分割されている。15 is a film supply chamber, 16 is a film winding chamber, 1
7 is the film surface. The electrochromic variable NO filter 14 according to the present invention installed near the film surface 17 is divided into several tens to hundreds of squares.
本例のような可変ＮＤフィルターは、例えば多分割測光
による各エリアの測光情報に応じてマス目単位で露光補
正を行なうことができ１部分的な露光オーバ一部を修正
することも可能となる。尚、このような場合フィルム面
と補正板（可変ＮＯフィルター）の距離は散乱効果によ
ってマスの境界の影響がなくなる程度に離れている必要
がある。A variable ND filter like the one in this example can perform exposure correction in units of squares according to the photometric information of each area using multi-segment photometry, and it is also possible to correct partial overexposure. . In this case, the distance between the film surface and the correction plate (variable NO filter) needs to be far enough to eliminate the influence of the mass boundaries due to the scattering effect.
このようなエレクトロクロミック多分割露光補正板は第
４図に示すようにラボにおけるプリント時の露光補正に
も応用できる。Such an electrochromic multi-segment exposure correction plate can also be applied to exposure correction during printing in a laboratory, as shown in FIG.
［発明の効果］
以上説明したように、両極発色型の構成を持つエレクト
ロクロミック素子の陰極側発色層を■非発色化するか、
または■それを酸化還元反応を可逆的に行ない且つ両状
態において非発色である物質で代替することによって、
ニュートラルな吸光スペクトル特性を持つエレクトロク
ロミック素子が実現でき、従来の光学変調素子では困難
であった変調の可変性を有する可変光学変調素子、例え
ば可変ＮＯフィルター等を提供できるようになる。[Effects of the Invention] As explained above, the coloring layer on the cathode side of an electrochromic element having a bipolar coloring type structure can be made non-coloring, or
or ■ by replacing it with a substance that reversibly undergoes redox reactions and does not develop color in both states,
An electrochromic element with neutral absorption spectrum characteristics can be realized, and a variable optical modulation element, such as a variable NO filter, etc., can be provided that has modulation variability, which has been difficult to achieve with conventional optical modulation elements.
第１図は従来型エレクトロクロミック素子の構成図で、
第１図（Ａ）は単極発色型、第１図（Ｂ）は両極発色型
である。第２図は本発明によるエレクトロクロミック可
変ＮＤフィルターをレンズ上に形成した場合のカメラ光
学系である。第３図、第４図は本発明によるエレクトロ
クロミック多分割可変ＮＤフィルターを利用した露光補
正パネルへの応用例で、第３図はフィルム露光時補正、
第４図はプリント焼付時露光補正である。
ｌ二基板
２：第１電極
３：陽極側発色層（酸化発色性）
４：絶縁層
５：第２電極
６：ｌｌｉ極側発色層（還元発色性）
７：カメラレンズ部
８：レンズ
９：絞りユニット
１０：レンズ
１１：エレクトロクロミンク可変Ｎｉｌフィルター１２
：ミラー
１３：フィルム面
１４：エレクトロクロミック可変ＮＤフィルター１５：
フィルム供給室
１Ｂ＝フィルム巻き取り室
１７：フィルム面Figure 1 shows the configuration of a conventional electrochromic device.
FIG. 1(A) shows a monopolar coloring type, and FIG. 1(B) shows a bipolar coloring type. FIG. 2 shows a camera optical system in which an electrochromic variable ND filter according to the present invention is formed on a lens. Figures 3 and 4 show an example of application to an exposure compensation panel using the electrochromic multi-division variable ND filter according to the present invention, and Figure 3 shows film exposure compensation,
FIG. 4 shows exposure correction during print printing. l2 substrate 2: first electrode 3: anode side coloring layer (oxidation coloring) 4: insulating layer 5: second electrode 6: lli pole side coloring layer (reduction coloring) 7: camera lens section 8: lens 9: Aperture unit 10: Lens 11: Electrochromic variable Nil filter 12
: Mirror 13: Film surface 14: Electrochromic variable ND filter 15:
Film supply chamber 1B = Film winding chamber 17: Film surface
Claims (3)
るエレクトロクロミック層と、誘電体膜からなる絶縁層
と、導電体膜よりなる第２電極を順次積層し、あるいは
上記の絶縁層と第２電極の間にさらに陰極側発色層であ
る第２のエレクトロクロミック層を積層してなる全固体
型エレクトロクロミック素子であって、上記陽極側発色
層としてニュートラルな吸収スペクトル特性を持つエレ
クトロクロミック物質を用い、または更に上記陰極側発
色層を非発色化処理するか、陰極側発色層の還元発色性
物質の代わりに酸化還元を可逆的に行なう非発色物質を
用いた陽極側単極発色型のエレクトロクロミック素子に
よる、可視光域でニュートラルな吸収スペクトル特性を
有することを特徴とする光学変調素子。(1) A first electrode made of a conductive film, an electrochromic layer as an anode side coloring layer, an insulating layer made of a dielectric film, and a second electrode made of a conductive film are laminated in sequence, or This is an all-solid-state electrochromic device in which a second electrochromic layer, which is a coloring layer on the cathode side, is further laminated between the layer and the second electrode, and the coloring layer on the anode side is an electrochromic layer with neutral absorption spectrum characteristics. Unipolar coloring on the anode side using a chromic substance, or further treating the coloring layer on the cathode side to make it non-coloring, or using a non-coloring substance that reversibly performs redox in place of the reduction coloring substance in the coloring layer on the cathode side. An optical modulation element characterized by having neutral absorption spectrum characteristics in the visible light region, which is made of a type electrochromic element.
ペクトル特性を有するＩｒ、ＮｉまたはＣｏの酸化物で
ある特許請求の範囲第１項記載の光学変調素子。(2) The optical modulation element according to claim 1, wherein the coloring layer on the anode side is an oxide of Ir, Ni, or Co having neutral absorption spectrum characteristics in the visible light region.
ペクトル特性を有するＩｒ、ＮｉまたはＣｏの水酸化物
である特許請求の範囲第１項記載の光学変調素子。(3) The optical modulation element according to claim 1, wherein the coloring layer on the anode side is a hydroxide of Ir, Ni, or Co having neutral absorption spectrum characteristics in the visible light region.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61043946A JPS62203133A (en) | 1986-03-03 | 1986-03-03 | Optical modulating element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61043946A JPS62203133A (en) | 1986-03-03 | 1986-03-03 | Optical modulating element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62203133A true JPS62203133A (en) | 1987-09-07 |
Family
ID=12677871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61043946A Pending JPS62203133A (en) | 1986-03-03 | 1986-03-03 | Optical modulating element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62203133A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020531871A (en) * | 2017-08-31 | 2020-11-05 | 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． | Exposure equipment, exposure method and photolithography method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578524A (en) * | 1980-06-19 | 1982-01-16 | Nippon Kogaku Kk <Nikon> | Electrochromic display element |
| JPS6128930A (en) * | 1984-07-20 | 1986-02-08 | Canon Inc | Driving method of electrochromic element |
| JPS62115128A (en) * | 1985-11-14 | 1987-05-26 | Toyoda Gosei Co Ltd | Production of whole solid-state type electrochromic element |
-
1986
- 1986-03-03 JP JP61043946A patent/JPS62203133A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578524A (en) * | 1980-06-19 | 1982-01-16 | Nippon Kogaku Kk <Nikon> | Electrochromic display element |
| JPS6128930A (en) * | 1984-07-20 | 1986-02-08 | Canon Inc | Driving method of electrochromic element |
| JPS62115128A (en) * | 1985-11-14 | 1987-05-26 | Toyoda Gosei Co Ltd | Production of whole solid-state type electrochromic element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020531871A (en) * | 2017-08-31 | 2020-11-05 | 京東方科技集團股▲ふん▼有限公司Ｂｏｅ Ｔｅｃｈｎｏｌｏｇｙ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． | Exposure equipment, exposure method and photolithography method |
| US11294288B2 (en) | 2017-08-31 | 2022-04-05 | Boe Technology Group Co., Ltd. | Exposure device, exposure method and photolithography method |
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