JPS59154425A - Entirely solid electrochromic element - Google Patents

Abstract

PURPOSE:To develop color of high density at a high response speed by using manganese hydroxide as the material of an electrochromic layer as a color developing layer at the anode side. CONSTITUTION:The 1st electrode 2 made of a transparent electric conductor film, an electrochromic layer 3 as a color developing layer at the anode side, an insulating layer 4 made of a dielectric film, and the 2nd electrode 5 made of an electric conductor film are successively laminated on a transparent substrate 1 to obtain an entirely solid electrochromic element. The 2nd electrochromic layer 6 as a color developing layer at the cathode side may be further laminated. At this time, the electrochromic layer 3 is made of manganese hydroxide [Mn(OH)2]. The manganese hydroxide film is formed by reactive ion plating in an atmosphere of steam or a mixture of steam with gaseous O2 using manganese or manganese oxide as an evaporating material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochromic element that utilizes a trochromic phenomenon.

Electrochromic phenomenon refers to the phenomenon in which substances change color due to redox reactions when voltage is applied. Electrochemically quenching dye elements that utilize such electrochromic phenomena, that is, electrochromic elements, can be applied to, for example, numeric display elements, X-Y matrix display elements, optical shutters, aperture mechanisms, etc. Although they can be classified by material into liquid type and solid type, the present invention particularly relates to an all-solid type electrochromic element.

Two construction examples of all-integrated electrochromic elements utilizing electrochromic phenomena are shown in FIGS. 1 and 2.

The electrochromic element shown in FIG. 1 consists of a transparent substrate 1, a first electrode 2 made of a transparent conductive film, an electrochromic layer 3 which is a coloring layer on the anode side, an insulating layer 4 made of a dielectric film, and a conductive layer 4. It is made by sequentially laminating second electrodes 5 made of body membranes.

Furthermore, the electrochromic element shown in FIG.
In the figure, between the insulating layer 4 and the second electrode 5 in the mustard structure,
Further, a second electrochromic layer 6, which is a coloring layer on the cathode side, is laminated.

In the above structure, the substrate 1 is generally formed of a glass plate, but this is not limited to a glass plate, and may be a transparent left plate such as a nolastic plate or an acrylic plate. It may also be placed above the second electrode 5 instead of under the first electrode 2, or it may be provided on both sides depending on the purpose (for example, as a counterfeit cover, etc.). Good too. However, depending on these cases, it is necessary to use a transparent conductive film for the second electrode 5, or to use transparent conductive films for both the electrodes and the electrodes on both sides. If both electrodes are made of transparent heavy metal, the element can be used as a transparent type. As such a transparent conductive film, an ITO film (containing about 5% of tin oxide SnO2 in indium oxide In2O3), a NESA film, etc. are used.

In the above structure, the electrochromic layer 3, which is the coloring layer on the anode side, has conventionally been made of chromium ternide (Cr203),
It is formed from irizoum hydroxide (Ir(OH)2.) and nickel hydroxide (N1(OH)2)@.

The insulating layer 4 made of dielectric material is made of norcon dioxide (Zr02
), silicon oxide (810), silicon dioxide (5i0
2), oxides such as tantalum pentoxide (Ta205), or lithium fluoride (T, IF'),
It is formed using a fluoride such as magnesium fluoride (MgF2). , 1. Electrochromic 6, which is the coloring layer on the cathode side, is made of tungsten dioxide (W
O2), tungsten trioxide (WO3), molybdenum dioxide (MoO2), molybdenum trioxide, Zoden (Mo0a
), 1 cum of panaso pentoxide (■2o5), etc.

In an all-solid-state electrochromic element with such a structure, by applying Vr and electricity LL between the first electrode 2 and the second electrode 5, an electrochemical reaction occurs, resulting in coloring and decoloring. It is generally believed that this coloring υday1' is caused by the formation of bronze by double injection of cations and electrons into the electrochromic layer 6.For example, as an electrochromic material, WO3ff1
When #l-j exists, an oxidation-reduction reaction represented by the following formula (]) occurs, resulting in coloration.

WO3+xH+xe ;= HxWO3(],)(1
) Tungsten Bronze) IxIVO3' according to the formula
7jh is formed and colored, but if the applied voltage is reversed at this point, the color becomes decolored. In the reaction of formula (1), in an all-solid-state electrochromic device, protons (I+) are supplied by an insulating layer inside the device and the device is colored.

, in the above-mentioned electrochromic device, conventionally,
The electrochromic layer 3, which is a coloring layer on the anode side, is formed by adding a reactive substance such as irizoum hydroxide (Ir(OH)2), nickel hydroxide (N1(OR)2), etc. to a reactive gas or an anodic oxide film method. It is formed by

The present invention provides such an electrochromic device in which the electrochromic layer, which is the coloring layer on the anode side, is made of a completely new material different from conventional ones.
It is an object of the present invention to provide an all-solid-state electrochromic device that can achieve response speed and color density that are superior to those of conventional cathode-side color development and fading methods.

The all-solid-state electrochromic cable according to the present invention is characterized by a first electrode composed of a conductive film, an electrochromic layer which is a coloring layer on the anode side, and a dielectric film, as shown in Fig. 1. An insulating layer made of In an all-solid-state electrochromic element in which a second electrochromic layer, which is a coloring layer on the cathode side, is further laminated, the electrochromic layer, which is a coloring layer on the anode side, is made of manganese hydroxide (Mll (
OH) 2) It consists in composing. This manganese hydroxide film can be formed by reactive ion silating.
304) and H20 vapor or) as the atmosphere.
The desired electrochromic layer thickness can be obtained by adding 120% steam and O2 gas.

FIG. 3 shows an example of a reactive ion routing apparatus used to manufacture an all-solid-state electrochromic device according to the present invention. In the figure, 1° is the main body of the reactive ion blating device, 11 is the diffusion pump, and 12 is the electron gun (
xy B gun), 13 is umbrella (board holder), 14 is D
Apply C bias -j, 61. ) C, -' ia
” Ma +, 15 is high 1i5.l 774, :y i Jl/ (RF coil), 1 (3 is n2o: i, [H supplying air 20 steam i, 'ξ', + 11':' ,
, 17ba0. Gas'fi: IJ'G #1f-3-ru gas+W 7, 18'',. Lbi 1 is knee 1.
゛Gal valve, 20 is innumerable (wood, ′:,, I□678 bodies) Henn 1, zu.

ㅅ+', 'J l゛xi li(-)1gu-j 'M
i, '-i: tL: Yode J~shi, kutrochromisoku 2 (, -1" %: Made '51゜su4゛2 王 (te, " is the l-missing]not↓ri).

First, draw the usual drawer r + A: 'j'\ on board 1.
Part sum/Yobiri -H, + fjC', , I, I1 noe/, - Self-1,'fli□4tl:□, 2 is formed, and this 3 i"J'!+: 11 In the device shown in the figure, set T7.I, as shown in 2().
゛ (I~l11) 翛 or child's i □'i・2 conversion'j
:'l'('~'1.nO.

Mn022Mn203+Mn, 0. ) using '#', H2
0Bm air 1,1; S":; When the 02 gas is introduced, the 02 gas is introduced and the raw ion radiation can be reacted.
! , : (from 1- [obtained 1 collection 1Li 1l 5re 1' 2 fake layers, δelect "4ri 1 comic layer, 3 above C)
17th F'i: i4t 2 on form/JI;:zu/S)
・Next (to C-this 1
, (・This insulating Ji・; 4 is formed, and then the insulating material r′ 4 o , J= It? 2nd, 1, □■・Hi 45
(as shown in FIG. 1), or in the case of an electrochromic element), or an electro, chromic, or chromic layer 6 of Europe 1tj, Al1 coloring 1"Ffi is added to -h of the insulation 1c'44. Tracing the sky,
271) (forming 1EX- of I-゛・5 ( y)
Figure 2 shows the work l/cutoroku "J mink element-J:no" 7
).

The present invention +2-twist appendix-1) (ξ's shade if< (il
Quizo's electro-chromic material with i1 shot extinguisher 4 only and Jl.
It can be done by changing the lifespan.

J) The following describes examples of the present invention.

The sentence is l, I',! /li l Light, Fu, Ko, 0.8 +, -m power゛゛las Corn
ing 7059 ) group +i u1 above(・, -1:+knee j toyasu drawer +,l(< 1ili and ri-ps
W, Cwo・1.11. f CITOP3,L
') Seiru 2. ! ,'17', i, 4・li 29
1 form jL', L,;
2 j:y, p〈21;! 3 (Soldier = ili1 color IF
'l Elek (・I Fukuromitsu 4 layers: shape 3) &
L/ko.

The conditions are l-I20 3.0>,]-I0
4 people in 'Torr i, 02 gas f5. OX1
0'Torr V and deposition rate's, : ], O
X/sac toshi/ko. rg r=-, t is 100OX/"ζ. This two (', L/di IA l-11 chromic 3・bow; 3 is water 1 child moka ~ n 7) n (Mn
It consists of (OFo 2 ) 7 (.

On top of this loop, an insulator layer 4 is formed using the -1, "L air vaporization) method.
I added an X. At this time, the vacuum +i- is 2. OX10”
Torr, the steaming speed is 8X/sec, -). Furthermore, on top of these films, a semi-transparent conductive Au film was attached as the second electrode 5 for 300 minutes.

This all-solid-state electrochromic ζ-element was manufactured by applying a voltage of 2.2 V between the first and second electrodes to drive it. 0 at 0
．． By the time I got there, it was already 900 tons.

Example 2 11ν 0.8 nm glass (Corning 705
On the substrates 1 and 1- of 9), a first layer made of an ITO film with an appropriate lead-out voltage (-1 area and ~1 inch area) is placed on the substrate 1, 1-.
Form the electrode 2, and steam it once (M,
Using reactive ionone 0-laying method, 1L5 (;M
An electrochromic layer 3 with i-law color development*-i was formed.

Sea j2, ■-I20 steam as column A'1; 3. OX
10 Torr and set the steam foil speed to 1.0
i/sec, 1'0, 1', ji, 11000X. This elect 11 blackberry layer 3 was composed of water and manganese (Mn (OH) 2 ). On this film, 3oooX of Ta 205 JN was applied as an insulator layer 4 using vacuum evaporation method V (Yomitsu), and further on this film, a cathode side coloring layer (Z) was applied as an electrochromic layer 6. , add a layer of WO3 to 4000 ζ
. The degree of vacuum at this time is 2, OX 1 (1”Torr,
The deposition rates were 8×/see and 1××/scc, respectively. Furthermore, on top of these ribs, a semi-transparent conductive Au film with a thickness of 30°C was placed as a second tM, KM5.

The all-solid-state electronic device manufactured in this way was driven by applying a voltage of 2.2 V for 1'l between the first and second electrodes, and the color density was Δ0 ( )
By the time I got to 03, I was 700171See/r
, <+Example 3 Glass with thickness I6 till (Corning 7059
) glue, (on top of the ITO film 1, an appropriate extraction potential H and 1) (y i ~ 1).
The electrode 2 is shaped like J, and the vapor first material is manganese oxide (Mn).
An electrochromic layer 3, which is a coloring layer on the anode side, was formed on the first electrode 2 by the bending and bending routing method.

The conditions are H20 vapor at 3.0 x 10'To
The electrochromic layer 3 was made of manquinone hydroxide (Mn(OH)2). On top of this film, a layer of Ta 20 s was deposited as an insulator layer 4 to a thickness of 300 s using a vacuum evaporation method.
Added a z.

The degree of vacuum at this time was 2.0 X 10-5 Torr, and the deposition rate was 8 X/Sec. Furthermore, on top of these films, a semi-transparent conductive Au film with a thickness of 300 mm is applied as the second electrode 5.
λ I heard it.

When the all-solid-state electrochromic device manufactured in this way was driven by applying a voltage of 22 V between the broom 1 and the second electrode, the coloring density reached 950 m56c until it reached 0.3 at ΔO9O. .

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views showing two examples of all-solid-state electrochromic devices according to the present invention, and FIG. 3 shows a reactive ion silating apparatus used to manufacture the devices of the present invention. Schematic diagram. 1...Substrate, 2. ...first electrode, 3...
Electrochromic layer, 4...1. corner edge layer,
5... 2nd i step ((, 6... Electrocomic layer, 10... Main body of reactive ion blating device, 1
1... Diffusion Honda, 12... Electron gun (EB gun), 1: U... Umbrella (substrate holder), 14 - DC bias source, 15... Kosho e': 2 ill (RF' coil) , 16・
・H20 steam supply or 5r, x7...o2 is Sufj? 18.19...Needle valve, 20.Substrate (object to be deposited).

Claims (1)

[Scope of Claims] 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 sequentially laminated, Alternatively, a second color forming layer on the cathode side is further provided between the above insulating layer and the second electrode.
electrochromi. All-solid-state electrochromium made of laminated layers. Elen), which is the coloring layer on the anode side of the element. Risukko is an all-solid-state electrochromic product whose chromic layer is made of manganese hydroxide.