JP2001059979A - Optical device, driving method therefor and image pickup device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain stable light shielding degree in an optical device which applies the deposition/melting phenomenon of a substance such as silver to dimming. SOLUTION: In the optical device, the temperature of an electrolyte (silver salt solution) 63 is detected with a temperature detector 53, this temperature information is transmitted to a control means 55, which controls output electric current of a driving power source 51 in accordance with the temperature information, whereby the quantity and thickness of a deposited material are adjusted. Further, this optical device is applied to the converging of light quantity to constitute an image pickup device such as a CCD camera 70.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device for displaying numbers and characters or an XY matrix display, and a light transmittance or light reflection in a visible light region (wavelength: 400 to 700 nm). The present invention relates to an optical device suitable for being applied to an optical filter capable of controlling a rate, a driving method thereof, and an imaging device (camera system).

[0002]

2. Description of the Related Art Conventionally, an electrochromic display element (hereinafter, referred to as a digital clock) has been employed in a display device such as a digital timepiece.
Called "ECD". ) Is a non-luminous display device, which performs display using reflected light or transmitted light as a dimming element by an electrochemical operation, and therefore has the advantage of less fatigue even after long-time observation. Have
It has advantages such as relatively low driving voltage and low power consumption.

For example, as disclosed in JP-A-59-24879, an organic viologen molecule derivative which reversibly forms a colored / decolored state as a liquid type ECD is prepared by using an electrochromic material (EC material). ) Are known.

[0004] However, ECDs such as viologen molecule derivatives have a problem in that the response speed and the degree of shielding are insufficient. In addition, the light amount adjusting device needs to be able to control the light transmittance in the visible light region (wavelength: 400 to 700 nm).
The material did not provide sufficient properties.

[0005] Under such circumstances, the present inventor has previously described EC
As an optical device (electrochemical light control device) that can replace D, paying attention to a light control device using precipitation / dissolution of a metal salt,
An optical device was studied. As a result, an optical device having characteristics superior to those of the EC material in response speed and shielding degree could be obtained.

In such an optical device, various metal salts can be used for the electrolytic solution. In particular, a system using precipitation / dissolution of silver or silver-containing particles is not suitable from the viewpoint of optical characteristics. Are better. That is, when an electrolytic solution is prepared, the solution is in the visible light range (wavelength: 400 to 700 nm).
No silver salt (including silver complex) which does not show an absorption spectrum and can be shielded almost uniformly in the visible light region when light is shielded.
Reversible plating that causes precipitation / dissolution of particles from the substrate, that is, RED (Reversible Electro-Deposit
This silver salt has reversibility of precipitation / dissolution even by drive control.

On the other hand, with respect to the deposition of electrodeposits from a silver salt solution, a cyan-based solution has been conventionally used in a plating bath. However, since this cyan-based solution is highly toxic, the working environment is safe. It is preferable to use a non-cyanide-based silver salt in the present optical device in view of the properties and the problem of treating the waste liquid.

In such a situation, by using a reversible system for depositing / dissolving a metal from a metal salt on a transparent electrode of an optical device, that is, by using a reversible plating material R
By using the ED material, it is possible to provide an optical device such as an optical filter suitable for a non-light emitting visible light region with low power consumption.

FIG. 5 shows a cell structure of a conventional electrochemical light control device of this type.

As shown in FIGS. 5A and 6, a pair of transparent glass substrates 24 and 25 are arranged as display windows at regular intervals. As shown in FIG. 5A, an indium-tin oxide (ITO) obtained by doping indium oxide with tin is provided on the inner surface of each of the substrates 24 and 25.
Working electrodes 22 and 23 made of a Tin Oxide) film are provided facing each other, and an electrolytic solution 21 in which a metal salt is dissolved is sealed between the working electrodes 22 and 23 facing each other. 26 is
This is a counter electrode provided also as a spacer at the peripheral portion between the substrates 24 and 25, and the electrolyte 21 sealed thereby is sealed between the substrates 24 and 25.

In such an optical device, FIG.
As shown in the figure, the counter electrode 26 is used as an anode, and the working electrodes 22 and 23
When a DC driving voltage is applied for a predetermined time during this time, the metal ions dissolved in the electrolyte are converted into the following formula (1) by the following formula (1): M ^{n +} + ne ⁻ → M (1) (n is a natural number) Such an oxidation-reduction reaction occurs, and the working electrodes 22 and 23 on the cathode side are changed from transparent to light-shielded by the particles containing the deposited metal. FIG. 5B is a conceptual diagram showing the electrochemical action at this time.

The above-mentioned case will be specifically described in the case where a silver salt solution is used for the electrolyte 21. A silver plate is used for the counter electrode 26, and the silver salt solution is formed, for example, by adding silver bromide to dimethyl sulfoxide (DMSO). 5)
As shown in (B), the working electrode 2 is used as the counter electrode 26 as an anode.
The 2,23 as the cathode, a driving voltage of the DC predetermined time during which the silver ions at the cathode, the following equation (2) Ag + ⁺ e ^- occurs redox reaction such as → Ag (2), precipitation The working electrodes 22 and 23 on the cathode side are changed from transparent to light-shielded by the Ag particles.

As described above, by depositing metal particles on the working electrodes 22 and 23, a specific reflection color due to the deposited metal particles can be observed from the display window. The filtering effect of the electrodeposited film, that is, the transmittance (or degree of light blocking) of visible light changes with the magnitude of the voltage or the application time thereof. Alternatively, it can function as an optical filter.

On the other hand, when the cell is in a light-shielded state, when a DC voltage is applied between the counter electrode 26 and the working electrodes 22 and 23 in a direction opposite to that described above, metal particles are deposited thereon. The working electrodes 22 and 23 are now on the anode side, and a reaction represented by the following formula (3) M → M ^{n +} + ne ⁻ (3) occurs, and the metal particles deposited on the working electrodes 22 and 23 change from the colored state. Restore to a transparent state.

The case where a silver salt solution is used as the electrolytic solution 21 will be described again. When the cell is in a light-shielded state, the direction opposite to the above is set between the counter electrode 26 and the working electrodes 22 and 23. When a DC voltage is applied to the working electrode 22 comprising mainly particles of Ag thereon is precipitated, in turn becomes the anode side, the following equation (4) Ag → Ag ⁺ + ^e - made (4) reaction Occurs, the particles mainly containing Ag deposited on the working electrodes 22 and 23 are dissolved in the electrolytic solution 1, and the transparent state is restored from the light-shielded state.

FIGS. 7 and 8 show another conventional electrochemical light control device.

In this example, as shown in the sectional view of FIG.
On the inner surfaces of a pair of transparent glass substrates 4 and 5 constituting the cell,
Working electrodes 2a, 2b, 2 each comprising a pair of ITO films
c, 2d, 2e and 3a, 3b, 3c, 3d, 3e are provided to face each other. Counter electrodes 7a and 7b made of a metal plate such as a silver plate are provided on the outer peripheral portions of these outer working electrodes 2e and 3e. The substrates 4 and 5 are held and sealed at predetermined intervals by a spacer 6, and the electrolyte 1 is sealed between them.

As shown in the plan view of FIG. 8, the working electrode 2a
2e, 3a to 3e and the counter electrodes 7a, 7b are planar electrodes formed in concentric patterns. Each electrode 2a
, 3a, 2b and 3b, 2c and 3c, 2d and 3d, 2e and 3e, 7a and 7b are driving power sources 8a and 8b, respectively.
8c, 8d, 8e and 8f are wirings 9 made of thin chrome wires or the like.
a, 9b, 9c, 9d, 9e, 9f.

In this configuration, the working electrodes 2 opposed to each other
a and 3a, 2b and 3b, 2c and 3c, 2d and 3d, 2e
And 3e at predetermined potentials (V ₁ , V ₂ , V ₃ , V ₄ , V
_{Assume 5} . V ₆ is a reference potential at the counter electrodes 7a and 7b. By applying (1), metal particles can be precipitated from the electrolytic solution 1 on each electrode serving as a cathode, and can be shielded from light. The filter action of this deposited film, that is, the transmittance of visible light (or shading of light shielding) changes with the magnitude of the voltage or the application time.

Therefore, if V ₁ = V ₂ = V ₃ = V ₄ = V ₅ , light can be shielded uniformly over the entire area of the cell.
In addition, the degree of concentration can be uniformly changed according to the voltage or the application time. For example, | V ₁ |> |
If V ₂ |> | V ₃ |> | V ₄ |> | V ₅ |, the degree of light blocking decreases from the center to the periphery (in other words, the transmittance increases). Conversely, | V ₁ | <
If | V ₂ | <| V ₃ | <| V ₄ | <| V ₅ |, the transmittance decreases from the center to the periphery. This configuration is based on a CCD (Charge Coupled Device: Charge
It is useful as an optical (quantity) stop for a coupled device, and can reduce the size of the element, so that it can sufficiently cope with an improvement in the integration degree of the CCD.

[0021]

In the above-mentioned conventional electrochemical optical device, the form of metal deposition differs depending on the operating temperature, and the rate of metal deposition is particularly susceptible to temperature. That is, the deposition rate is higher when the temperature is higher than when the temperature is lower, and the thickness of the deposited film is higher when the temperature is higher at the same current density and for the same time.

In the above optical device, the degree of light shielding is changed depending on the thickness of the deposited film. Therefore, in order to obtain a desired degree of light shielding, temperature, current density and deposition time are affected. If the same deposition time is used for comparison, there is a problem that the light shielding degree of the optical device is greatly affected by the temperature and the current density, and the optical device is unstable.

For this reason, the conventional electrochemical optical device has a problem that the obtained optical characteristics are unstable due to the influence of the ambient temperature.

On the other hand, a mechanical light amount aperture has been used for adjusting the light amount of an image pickup device such as a CCD camera.
However, as the size of the CCD camera becomes smaller, the mechanical aperture of the mechanical light aperture becomes smaller as the aperture area becomes smaller. was there. Further, as the size of the CCD has been reduced, various problems have arisen, such as an image being blurred by the effect of light diffraction in the mechanical light amount aperture.

The present invention has been made in order to improve the above circumstances, and an object of the present invention is to provide an electrochemical optical device that utilizes a phenomenon of deposition / dissolution of a substance such as a metal for light control.
An optical device and a driving method thereof that provide a stable light blocking degree,
Another object of the present invention is to provide an image pickup apparatus which realizes downsizing of a system, prevention of blurring of an image, and the like by applying the optical device to light amount adjustment.

[0026]

That is, an optical device of the present invention comprises a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes, and performs an electrochemical dimming operation. Wherein a control means for adjusting a drive current value according to the temperature of the electrolytic solution is provided.

The driving method according to the present invention is characterized in that, in the above optical device, a driving current value is adjusted according to a temperature of the electrolytic solution.

Further, the optical device of the present invention comprises: a working electrode;
A heating / cooling unit that adjusts the temperature of the electrolytic solution and controls the heating / cooling unit in an optical device that includes a counter electrode and an electrolytic solution disposed in contact with these electrodes and performs electrochemical dimming. Control means is provided.

Further, the driving method of the present invention is characterized in that, in the above optical device, the temperature of the electrolytic solution is adjusted to a predetermined temperature, and a driving current is supplied to adjust the light.

Further, the image pickup apparatus according to the present invention is characterized in that the optical device is provided in the optical path for adjusting the amount of light.

According to the optical device and the driving method of the present invention,
In the optical device that performs electrochemical dimming, the drive current value is adjusted according to the temperature of the electrolytic solution, so that the average transmittance, that is, a stable light blocking degree can be obtained regardless of the temperature of the electrolytic solution. it can.

Further, according to the optical device and the driving method of the present invention, in the optical device for performing dimming electrochemically,
Since the electrolytic solution is adjusted to a predetermined temperature and the drive current is applied, a stable light blocking degree (average transmittance) can be obtained with little influence from the surrounding temperature.

Further, according to the image pickup apparatus of the present invention, the optical device attached thereto can adjust the light amount by applying an electric field to the electrolytic solution. The size of the optical path can be reduced to the size of the effective range of the optical path without the need for light, and the amount of light is controlled by the magnitude of the applied electric field to prevent diffraction and effectively prevent blurring of images. Can be.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The optical device according to the present invention may include a sensor for detecting the temperature of the electrolytic solution, and the temperature information may be input to a control circuit as the control means. preferable.

The working electrode used in the present invention is a transparent or translucent electrode, and in terms of transmittance, desirably 70% or more in the visible region.

The electrolyte used in the present invention is usually preferably a silver salt solution. Further, in consideration of the above-described effects on the environment and the like, it is preferable that the material be non-cyanide regardless of whether it is a silver salt solution.

Hereinafter, the present invention will be described more specifically based on preferred embodiments.

An optical device according to a preferred embodiment of the present invention comprises:
A pair of transparent or translucent substrates arranged opposite to each other,
At least one pair of working electrodes disposed so as to face the facing surfaces of these substrates, a counter electrode, comprising an electrolyte disposed in contact with the working electrode and the counter electrode, and a temperature detector for the electrolyte. And control means for controlling the drive current source based on the temperature information from the detector.

One example is an optical device as shown in FIG. 1A (the description of the installation of the reference electrode is omitted). That is, in the optical device of the embodiment shown in FIG. 1A, glass substrates 60 and 61 are arranged as display windows so as to face each other with a spacer 62 interposed therebetween, and an inner surface of these glass substrates 60 and 61 is provided with a working electrode 54 made of ITO. The counter electrodes 52 are arranged to face each other. A silver salt solution 63 is sealed between the glass substrates 60 and 61 and the spacer 62 as an electrolytic solution.

A driving power source 51 is connected between the counter electrode 52 and the working electrode 54. The drive power supply 51 is composed of a known power supply circuit, and is controlled according to the temperature of the electrolyte as described later.

On the other hand, a control means (control circuit) 55, a temperature detector 53, and a control means (control circuit) 55 are connected between the drive power supply 51 and the drive power supply 51. One end is in contact with the silver salt solution 63 through the spacer 62.

In the above-described configuration, the temperature detector 53 is required to have a function of transmitting the temperature information of the electrolytic solution to the control means 55. In general, the temperature detector 53 can transmit the temperature change of the electrolytic solution to the control means 55 in the form of an electric signal. Those such as thermistors are preferred.

As shown in the drawing, the probe 53a of the temperature detector 53 is preferably disposed in such a manner that the tip thereof is in contact with the electrolytic solution in order to more accurately know the temperature of the electrolytic solution. No need. For example, the probe 53
If a has a problem such as corrosion resistance, the tip of the probe 53a may be fixed to a portion of the device near the electrolytic solution, for example, inside the spacer 62. Even in this case, practically, almost no problem occurs.

As for the material of the probe 53a,
Generally, stainless steel (SUS304) having good corrosion resistance is sufficient. However, when higher corrosion resistance is required under special or special circumstances, a more chemically stable material such as gold or platinum may be used instead of stainless steel. Alternatively, the surface of a stainless steel material or another metal material may be coated with these noble metals or other materials having high chemical stability.

The temperature information detected by the temperature detector 53 is transmitted to the control means 55. This control means 55
Is to adjust the output current of the drive power supply 51 based on this temperature information, whereby the amount of metal deposited on the working electrode 54 (or the amount of dissolved metal) can be adjusted. As a practical control means 55 suitable for such purpose, for example, a PID control device can be mentioned.

In another preferred embodiment of the present invention, a pair of transparent or translucent substrates arranged opposite to each other, and at least a pair of functional units arranged opposite to the opposing surfaces of these substrates are provided. An electrode, a counter electrode, and an electrolytic solution disposed in contact with the working electrode and the counter electrode, and a temperature detector for the electrolytic solution, and control of the temperature of the electrolytic solution based on temperature information from the detector. And temperature control means for performing the following.

As an example, an optical device as shown in FIG. 1B can be cited.
The description of the installation of the reference electrode is omitted). Configuration of optical cell, drive power supply 51, temperature detector 53, and probe 53a
Is similar to that of FIG. 1A. 1A is different from FIG. 1A in that, for example, a heating / cooling switching type heating / cooling means 59 provided with a thermostat or the like for changing the temperature of the optical cell based on the temperature information from the temperature detector 53;
Temperature control means 57 for controlling this.

The temperature information detected by the temperature detector 53 is transmitted to the temperature control means 57. This temperature control means 57
Can control the heating / cooling means 59 based on this temperature information and maintain the optical cell at a predetermined temperature. This makes it possible to adjust the amount of metal deposited (or the amount of dissolved metal) and the thickness of the metal deposited on the working electrode 54 almost without being affected by the ambient temperature.

For forming the transparent electrode used as the working electrode 54 in the optical device of the present invention, ITO or tin oxide is used. Although the constituent element ratio of indium and tin is arbitrary, it is preferable that In / Sn be 0 to 9.

The above-mentioned various transparent electrodes are formed by using a metal or an oxide thereof as a target and applying an AC voltage to a DC voltage, an AC voltage, or a DC voltage under reduced pressure or normal pressure to oxidize the metal or the oxide thereof. Sputtering method for forming a thin film of an object, vapor deposition method for melting and evaporating a metal or its oxide to form a film, vaporizing a gas containing a desired metal, and applying an AC voltage to a DC voltage, an AC voltage, or a DC voltage. Is applied to chemically activate and form a film containing a desired metal on an object, and various vapor deposition methods such as a chemical vapor deposition method (CVD) are preferably used.

As a target used in the sputtering, a single crystal or a polycrystal of a compound containing a film forming component element is used. The composition of the film can be controlled by the element composition ratio in the target. For example, in the case of a polycrystalline material in which tin oxide is mixed into ITO, the composition of the film can be controlled by changing the amount of tin oxide to be mixed.

For the purpose of reducing the resistance value of the film, the target may be a material in which different elements such as fluorine and antimony are mixed in a small amount.

At the time of film formation by sputtering, the temperature in the reaction tank is appropriately adjusted. Since the critical temperature between the crystallinity and the amorphousness of the film at the time of film formation also depends on the In / Sn ratio in the film, the temperature is adjusted to an appropriate temperature according to a desired In / Sn ratio. It is desirable to do.

The sputtering method is preferably performed by degassing the inside of the reaction tank once and introducing mainly argon as an inert gas into the tank. Depending on the specifications of various physical properties such as the sheet resistance of the film to be formed, a slight amount of oxygen may be mixed as needed.

Further, if the transparent electrode is chemically or physically modified, the deposition potential of the electrodeposit on the transparent electrode is lowered, the deposition of the electrodeposit is facilitated, and the transparent electrode or the solution itself is electrically received. Damage can be reduced.

As a chemical modification method in this case, it is preferable to perform a surface treatment (chemical plating) of the transparent electrode with palladium or the like by a two-liquid treatment method of a tin solution and a palladium solution. That is, as a surface activation treatment of the transparent electrode with palladium, the activity on the surface of the ITO electrode is increased by depositing palladium nuclei on a single substrate of the transparent conductive film.

In this case, as the tin solution, tin chloride (Sn
Cl ₂ ) 0.10 to 1.0 g in a concentration of 0.010 to 0.1
Palladium chloride (PdCl ₂ ) 0.10 to 0% dissolved in 1 liter of HCl.
1.0 g of a concentration of 0.010 to 0.10% and 1 liter of HC
1 can be used.

Further, as a physical modification method, a method of depositing a metal or the like which is nobler than the metal contained in the electrodeposit on the transparent electrode can be adopted.

Next, the counter electrode 52 is made of a metal different from the metal contained in the deposit, and the deposited metal can be deposited and dissolved thereon. For example, when an electrolyte containing a silver salt is used, platinum, gold, and a metal having a smaller ionization tendency than silver, such as palladium, may be used to deposit an electrodeposit containing silver thereon. It is possible.

If the counter electrode 52 has a laminated structure, the first layer is made of platinum, palladium or gold, and an electrodeposit containing silver is deposited on the surface thereof, the potential of the electrode can be stabilized. It becomes possible.

In other words, if a metal or metal oxide which shows a nobleer potential than silver and smoothly promotes the precipitation / dissolution reaction of silver is used on the outermost surface of the counter electrode 52, the counter electrode 52 is stable and can be used at the time of driving. Polarization (polarization potential) can be suppressed to a small value, and not only reduction in power consumption but also suppression of side reactions can be realized.

However, a platinum group metal such as platinum or palladium or a thin film of gold has low adhesion to an insulating substrate such as glass. Therefore, when the above metal is formed on an insulating substrate such as glass, a layer containing platinum, palladium, or gold is used as the first layer, and between the first layer and the insulating substrate,
Metals such as titanium, chromium, and tungsten, and metal oxides such as ITO and tin oxide that are good conductors and have good film
It is good to interpose as a layer.

That is, as a process, the first layer may be formed after forming the second layer on the insulating substrate. in this case,
Depending on the conditions, the second layer may become chemically unstable with respect to the electrolytic solution or may cause a side reaction with the electrolytic solution. It is desirable to have a structure that covers the layer.

The first or second layer can be formed by a vapor deposition method such as a vapor deposition method or a sputtering method, or a plating method.

That is, the metal or metal oxide of the first layer or the second layer is formed by vapor deposition of the metal or metal oxide under reduced pressure to form a film on a predetermined surface, or by using a metal or metal oxide as a target. As under reduced pressure or normal pressure, DC voltage,
A sputtering method or the like in which a desired metal or metal oxide is formed on a predetermined surface by applying an AC voltage or a DC voltage to an AC voltage and applying the applied voltage is preferably used. The vapor deposition method includes a method of vaporizing a metal or metal oxide by resistance heating in a high vacuum, a method of vaporizing the target metal or metal oxide by irradiating an electron beam (EB), and the like. Either technique does not change the effect of the present invention.

When platinum, palladium, gold or the like is formed on an insulating substrate made of silicon dioxide or the like, the second layer can be arbitrarily inserted because the adhesion between the two is good.

The formation of a metal layer of platinum, palladium, gold, or the like can be performed by a method other than the vapor deposition method. For example, these metals are formed into a predetermined shape in advance,
This molded product may be embedded or fitted in a corresponding recess on the substrate surface. Such a method also has an advantage that the molded product can be fixed to the concave portion using an adhesive as appropriate, so that it can be easily arranged on the substrate.

However, as shown in FIG.
Since the corner of the shape often has a sharp corner in shape,
An electric field concentration occurs there, and therefore, an inert particulate electrodeposit A is easily deposited on the counter electrode 52. This inert particle A
Floating in the electrolytic solution 63, the transparency of the optical device may be reduced, or the electrodes may be short-circuited.

Therefore, a vapor phase film forming method is usually used for forming the metal layer. In the vapor deposition method, the entire electrode can be formed in a thin film shape, so that a sharp edge (corner) hardly occurs at the edge.

Since platinum, palladium, and gold are metals nobler than silver, the natural potential generated when immersed is higher than silver. For example, the standard electrode potential in an aqueous solution at 25 ° C. is 1.188 V vs. platinum. NHE, palladium at 0.915 V vs. NHE, gold is 1.50 V vs. NHE. The standard electrode potential of silver is 0.7991 Vvs. Since it is NHE (all refer to the Chemical Handbook), platinum has a noble potential of 0.389 V with respect to silver, palladium has a noble potential of 0.116 V, and gold has a noble potential of 0.7 V. Show. Also, dimethyl sulfoxide (DMSO) / acetonitrile (AN) =
Even in a non-aqueous solvent having a mixing ratio of 55/45, it can be confirmed that the relative potential of platinum, palladium or gold with respect to silver shows a noble potential close to the potential in an aqueous solution.

Even if these metals are used as the counter electrode 52 as they are, there is no problem in exhibiting the performance of the optical device at all. However, in order to lower the polarization value of the counter electrode when the optical device is driven, it is necessary to use the above metal. It is preferable to previously form a layer of a more dissimilar metal element thereon. For example, when a silver salt solution is used, if a layer containing silver is formed on platinum, palladium, or gold, the potential shown when this electrode is immersed in the solution should be approximately the same as silver. Can be
The counter electrode 52 having excellent reversibility in the deposition / dissolution reaction of the electrodeposit can be obtained.

The layer of the different metal element can be formed by the vapor deposition method or electrolytic plating described above, and the characteristics as the counter electrode are not changed by either method.

Further, the counter electrode 52 can be constituted by a mixture layer containing conductive particles. The conductive particles are made of at least one carbon material, and a binder for binding the conductive particles is selected from the group consisting of natural rubber, cellulose, phenol, urethane, and epoxy. It is preferable to be made of at least one kind of resin material.

Examples of the carbon material used for the conductive particles include graphite (graphite), graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), carbon black, and activated carbon.

The graphitizable carbon is 2800-30.
A non-graphitizable carbon is a carbon material that does not graphitize even when heat-treated at about 3000 ° C.

The graphitizable carbon can be obtained, for example, by depositing coal or pitch in a nitrogen stream at a rate of 1 to 20 ° C./min.
It is produced by baking under the conditions of about 0 to 1300 ° C and a holding time at the ultimate temperature of about 0 to 5 hours. The pitch is
Distillation (vacuum distillation, atmospheric distillation, steam distillation, etc.) by tars, asphalt, etc. obtained by high-temperature pyrolysis of coal tar, ethylene bottom oil, crude oil, etc., thermal polycondensation, extraction,
Examples thereof include those obtained by an operation such as chemical polycondensation, and pitches or the like generated during wood carbonization.

The graphitizable carbon can be obtained by carbonizing a high molecular compound material such as polyvinyl chloride resin, polyvinyl acetate, polyvinyl butyrate, and 3,5-dimethylphenol resin in a nitrogen stream at 300 to 700 ° C. After that, it is also produced by firing under the same conditions as above.

Further, the graphitizable carbon is naphthalene,
Condensed polycyclic hydrocarbon compounds such as phenanthrene, anthracene, triphenylene, pyrene, perylene, pentaphen, and pentacene and derivatives thereof (for example, carboxylic acids, carboxylic anhydrides, carboxylic imides, etc.), and mixtures of the above compounds And condensed heterocyclic compounds such as acenaphthylene, indole, isoindole, quinoline, isoquinoline, quinoxaline, phthalazine, carbazole, acridine, phenazine, phenanthridine, and derivatives thereof, as described above, even when carbonized and calcined.

On the other hand, non-graphitizable carbon is produced by, for example, carbonizing and calcining a furan resin made of a homopolymer or copolymer of furfuryl alcohol or furfural under the same conditions as in the case of graphitizable carbon.

This non-graphitizable carbon is obtained from an organic material in which a functional group containing oxygen is introduced into a petroleum pitch having a specific H / C atomic ratio (for example, 0.6 to 0.8) (so-called oxygen crosslinking). Is also generated. For example, a non-graphitizable carbon material is H
Organic polymer compounds such as phenolic resin, acrylic resin, vinyl halide resin, polyimide resin, polyamide imide resin, polyamide resin, conjugated resin, cellulose and derivatives thereof having a / C atomic ratio of 0.6 to 0.8; , Naphthalene, phenanthrene, anthracene, triphenylene, pyrene, perylene, pentaphene, pentacene, and other condensed polycyclic hydrocarbon compounds and derivatives thereof (for example, carboxylic acids, carboxylic anhydrides, carboxylic imides, and the like); Various pitches based on a mixture of compounds, acenaphthylene, indole, isoindole, quinoline, isoquinoline, quinoxaline, phthalazine, carbazole, acridine, phenazine, phenazine, fused heterocyclic compounds and derivatives thereof, similar to the above Carbonized under conditions Is generated by fine fired.

The graphitizable carbon and the non-graphitizable carbon described above can also be produced by adding a phosphorus compound to the starting material or precursor and then performing the same carbonization and firing as described above.

When the conductive particles used for forming the counter electrode 52 are made of graphite, for example, a graphitizable carbon may be used as a precursor in addition to natural graphite at 2000 ° C.
Artificial graphite obtained by heat treatment at the above high temperature can be used.

In the table below, graphite, soft carbon,
The properties of hard carbon and activated carbon are shown in the following table in comparison.

[Table 1]

In forming the counter electrode 52, the binder used by mixing with the above-described conductive particles may be one having resistance to an electrolytic solution. For example, a natural rubber-based, cellulose-based, phenol-based, urethane-based or epoxy-based binder may be used. A system resin can be used. The mixing ratio of the binder to the conductive particles is preferably in the range of about 80:20 to about 99: 1 by weight, and more preferably in the range of about 90:10 to about 99: 1. If the mixing ratio is less than 80:20, the strength of the resulting film may be too weak. On the other hand, if the mixing ratio is more than 99: 1, the conductive particles may be relatively small and may be required. Conductivity may not be obtained.

The counter electrode 52 is preferably composed of conductive particles mainly composed of a carbon material and the binder, but a part of the counter electrode 52 may be formed of a mixture thereof.

It is preferable that the conductive particles constituting the mixture of the conductive particles and the binder contain at least one carbon material, but other components such as silver,
Metals such as copper and nickel or alloys or compounds thereof may be contained alone or in a mixed state.
In particular, when a silver salt solution is used for the electrolyte, silver particles in particular,
This is preferable because it has the effect of stabilizing the potential of the counter electrode 52.

As described above, when the counter electrode 52 is made of a material in which conductive particles are contained in a binder, it is possible to realize a reduction in cost, an improvement in transmittance, and prevention of a short circuit between electrodes. However, it is thought to be caused by the drive voltage of the optical device.In the configuration of the counter electrode in which the conductive particles are contained in the binder, the metal in the electrolytic solution is taken into the counter electrode 54 during driving, and the immersion potential of the metal is reduced. In order to show a different electric potential or to make the counter electrode 52 chemically unstable (metal dissolved in the electrolytic solution precipitates and the composition of the counter electrode 54 changes),
Drive control may become difficult.

However, when the metal such as the silver particles is formed as a part of the counter electrode 52, the potential of the electrode is stabilized.

In particular, when a silver salt solution is used for the electrolytic solution 1,
When the potential of the counter electrode 52 is positively or negatively different from the potential of the silver electrode by 50 mV or more, it is effective to use silver as the silver particles and mix silver particles in the electrode. If the counter electrode 52 is different from the silver potential by | 50 mV | or more, precipitation and dissolution of silver are unlikely to occur. Therefore, by using the silver film-forming layer, the potential of the electrode is made equal to that of the silver electrode, or silver is deposited.
The potential can easily be set to cause dissolution.

In this case, the silver particles are added in an amount of 0.1 to the component composed of the conductive particles other than the silver particles and the binder.
It is desirable that the additive is added in a weight ratio of 01 to 100 times from the viewpoint of stabilization of the potential of the counter electrode 52 and ease of preparing the mixture, and the addition amount is further preferably 0.05 to 10 times. Good.

Specifically, the silver particles have a solid content of 0.01 to 100 times (more preferably 0.05 to 10 times) the solid content of the paste comprising the conductive particles other than the silver particles and the binder.
Is preferably added in a weight ratio of

The particle size of the conductive particles is preferably from several μm to several tens μm. If the particle size is too small or too large, the conductive particles are uniformly dispersed in the binder. And the electrical resistance of the film may be too high.

As a current collector constituting the third layer as a base layer of the counter electrode 52, a material having electron conductivity and being electrochemically stable is used. Representative examples of the current collector material that can be used for the electrolytic solution used in the present invention include at least one metal material selected from Group 4A, 6A, 8 and 1B of the periodic table, and a metal material thereof. Alloys or metal oxides such as ITO can be used.

Further, in the counter electrode using a conductive particle layer such as a carbon paste, a polymer layer may be interposed between the conductive particle layer and the current collector in order to increase the adhesion. . Such a polymer layer is preferably made of a conductive polymer in order to smoothly transfer charges from the current collector to the conductive particle layer. Various methods such as an electrochemical polymerization method, a casting method, and a vapor deposition method are used for forming such a conductive polymer layer, and among them, the electrochemical polymerization method is preferable.

In the electrochemical polymerization method, an object to be formed is immersed in a solution containing monomer molecules, and the current is passed through the object to polymerize the monomer molecules, and a conductive polymer film is formed on the surface of the object to be formed. Is a method of forming

Examples of the type of the conductive polymer formed by the electropolymerization include polyaniline using aniline as a monomer, polypyrrole using pyrrole as a monomer, and polythiophene using thiophene as a monomer.

Further, since aniline, pyrrole, thiophene, and the like are easily chemically modified, various derivatives are present, and a derivative polymer is accordingly present. For example, in polyaniline, the derivatives N-alkylaniline, N, N
Polymers such as -dimethylaniline, 1-aminopyrene and σ-phenylenediamine; polymers such as N-methylpyrrole as derivatives of polypyrrole; and alkyl groups, alkoxyl groups and allyl groups at positions 3 and 4 of thiophene in polythiophene. There is a polythiophene derivative substituted with

The synthesis of a polymer by the electrochemical polymerization method is preferably performed by a dedicated cell 46 as shown in FIG. In order to carry out the polymerization, it is preferable to provide a cock 44 capable of introducing an inert gas in order to remove oxygen from the air if possible. Usually, a polymer obtained by polymerizing a polymer is used as the positive electrode 48,
An appropriate electrode material is used for the negative electrode 47. In the figure, an ammeter 42 is connected in series to the anode side with respect to a power supply 41, and a voltmeter 43 is connected in parallel.

Solvent 4 deoxygenated by blowing inert gas
In 9, when a monomer to be polymerized is dissolved at an appropriate concentration and an appropriate voltage is applied between both electrodes, a desired polymer is formed on the positive electrode 48.

For example, when aniline is electrochemically polymerized, aniline is added to an aqueous solution (pH <2) of hydrochloric acid, sulfuric acid, perchloric acid, tetrafluoroboric acid or the like for about 0.2 to 1 m.
When ol / l is dissolved and ITO is used as a positive electrode and silver is used as a reference electrode to oxidize by applying a constant potential or a constant current of 0.7 to 1.0 V, polyaniline is formed on the ITO on the film.

When electrochemically polymerizing pyrrole, for example, acetonitrile is used as a solvent, the concentration of pyrrole is set to 0.05 to 0.1 mol / l, ITO is used as a positive electrode, platinum is used as a negative electrode, and about 3 When a voltage of .5V is applied,
Polypyrrole forms on the ITO.

Further, when electrochemically polymerizing thiophene, benzonitrile, tetrahydrofuran, methylene chloride and the like are often used as a solvent in addition to acetonitrile, and platinum, nickel, graphite and the like can be used for a negative electrode. When voltage is applied using the positive electrode as ITO, polythiophene is formed on the ITO.

Normally, in order to carry out electrochemical polymerization, an electrolyte is dissolved in order to supply a sufficient current value. For example, in the electrochemical polymerization of polyaniline, acidity is adjusted to about pH 1 by adding hydrochloric acid or the like. When electrochemical polymerization of polypyrrole or polythiophene is performed, bromide contained in the electrolytic solution used in the optical device of the present invention is used. In addition to silver salts such as silver, lithium salts such as lithium iodide and lithium perchlorate are used as the electrolyte. In such electrochemical polymerization, an anion of the electrolyte is taken in as a dopant at the same time as the polymerization, so that a polymer film having high conductivity is obtained.

The conditions for carrying out the electrochemical polymerization vary depending on the type of the monomer, the solvent and the driving method. In order to obtain a good film, for example, in the case of polymerization of polyaniline at a constant current, 3
mA / cm ² or less, more preferably 0.5 mA / cm ² .

In electrochemical polymerization, copolymerization may or may not be possible in some cases. For example, copolymerization of pyrrole and thiophene is not possible because the oxidation potentials of the two monomers are different, but derivatives such as 2,2'-thienylpyrrole and 2,5-di (2-thienyl) -pyrrole can be used as monomers. Then, since the oxidation potential becomes close, it is possible to synthesize an alternating copolymer of thiophene and pyrrole in the ratio of 1: 1 or 2: 1.

In this way, a preferable counter electrode can be obtained by forming a second layer by performing electrochemical polymerization on the counter electrode portion, and further applying or printing a layer containing conductive particles as the first layer thereon.

The thickness of the first layer is several μm to several tens μm, the thickness of the second layer is 50 to 500 nm, and the thickness of the third layer is 100 μm.
It is good to be ~ 400 nm. The third layer is provided on an insulating substrate (thickness is, for example, about 1 mm) such as glass or fiber reinforced plastic (FRP), and may be made of ITO, copper, silver, gold, platinum, SUS, or the like.

As described above, if the counter electrode 52 has a laminated structure of the mixture layer of the conductive particles and the binder, the polymer layer, and the layer of the base current collector, it is possible to form the counter electrode 52 by a metal plate such as a silver plate as in the related art. An optical device having stable characteristics can be formed without causing the particles of the precipitate to float as compared with the case where the method is performed.

The provision of the reference electrode is effective for stably controlling the working electrode and the counter electrode. In other words, the reference electrode can control the potential of the working electrode and the counter electrode in the electrolytic solution with high precision, and if the external power supply is controlled by a limiter or the like so that the potential difference between the working electrode and the counter electrode is kept within a predetermined range, the operation can be performed. Excessive polarization of the electrode or the counter electrode can be prevented, and deterioration of the optical device can be suppressed.

As the reference electrode, a material having the same material composition as that of the counter electrode can be used. That is, a mixture of conductive particles such as a carbon material and a binder is applied or printed on a current collector such as a transition metal such as platinum or an oxide such as ITO, or an electrode is formed on a transition metal such as platinum or a surface thereof. A material obtained by depositing an electrodeposited metal (for example, silver) can be used for the reference electrode. However, since the reference electrode does not actively perform the precipitation / dissolution reaction of the metal such as silver as the counter electrode, the amount of the metal such as silver to be supported on the mixture of the carbon material and the binder is smaller than that of the counter electrode. Good.

As the metal used for the current collector of the reference electrode, tantalum, niobium or the like can be used in addition to the metal used for the counter electrode 52 and the like. Tantalum and niobium are not used because their specific resistances are higher than those of the others, and the counter electrode is not used because the polarization is large.However, the reference electrode receives only a small current to monitor the potential, and the potential of the reference electrode is Since they hardly change, these metals can also be used as current collectors for the reference electrode.

Next, as a silver salt solution suitably used for the electrolytic solution 63, a solution in which silver halide such as silver bromide, silver chloride, silver iodide or the like is dissolved in water or a non-aqueous solvent can be mentioned. .
At this time, dimethyl sulfoxide (D
MSO), dimethylformamide (DMF), diethylformamide (DEF), N, N-dimethylacetamide (DMAA), N-methylpropionamide (MP
A), N-methylpyrrolidone (MP), propylene carbonate (PC), acetonitrile (AN), 2-methoxyethanol (MEOH), 2-ethoxyethanol (EEOH) and the like can be used.

The concentration of silver halide in the silver salt solution is preferably from 0.03 to 2.0 mol / l.
More preferably, it is 0.05 to 2.0 mol / l.

In order to drive the optical device of this embodiment, light is shielded by depositing an electrodeposit mainly containing a metal dissolved in the electrolytic solution 63 on the surface of the working electrode 54, thereby shielding the light. Light is transmitted by dissolving the precipitate.

At this time, in order to deposit an electrodeposit on the working electrode 54, the working electrode 54 is polarized so as to serve as a cathode, and a current is supplied in the reduction direction so that electrons are supplied from a power supply. Good.

On the other hand, in order to dissolve the electrodeposit on the surface of the working electrode 54, the working electrode 54 is polarized so as to function as an anode, and a current is applied in the oxidation direction so as to send electrons to a power source. do it.

The reduction current required for depositing an electrodeposit at a predetermined light-shielding degree during a certain period of time differs depending on the temperature. That is, since the deposition rate of the electrodeposits increases as the temperature rises, the reduction current value for achieving a predetermined light-shielding degree in a certain time can be small. Conversely, if the temperature is low, the deposition rate of the deposits is slow, so to achieve the same degree of light shielding under the same conditions,
A large reduction current value is required. And the same thing,
This also applies to the oxidation current value required to dissolve the deposited electrodeposit.

The value of the reduction current or the value of the oxidation current differs depending on the type and quality of the transparent conductive film constituting the working electrode 54, the configuration of the electrolytic solution, and the like. Therefore, it is important to control the current according to each case flexibly.

Next, the optical device 7 according to the present invention described above.
6 (for example, having an electrode pattern as shown in FIG. 8)
An image pickup apparatus according to the present invention will be exemplified for an embodiment incorporated in a CD (Charge Coupled Device) camera.

In the CCD camera 70 shown in FIG. 2, a first group lens 71, a second group lens (for zoom) 72, a third group lens 73, a fourth group lens (for focus) 74, and an optical axis indicated by a chain line. CCD packages 75 are disposed in this order at appropriate intervals, and the CCD package 75 contains an infrared cut filter 75a, a liquid crystal optical low-pass filter system 75b, and a CCD image pickup device 75c. Between the second group lens 72 and the third group lens 73,
The optical device 76 according to the present invention described above near the third lens group 73 is mounted on the same optical path for light amount adjustment (light amount stop). Note that the fourth group lens 74 for focusing is
A linear motor 77 is provided so as to be movable between the third lens group 73 and the CCD package 75 along the optical path. The second lens group 72 for zooming includes a first lens group 71 and an optical device 76 along the optical path. It is arranged so that it can move between.

According to this embodiment, the second group lens 72
The optical device 76 according to the present invention set between the lens unit and the third lens group 73 can adjust the light amount by applying an electric field as described above, so that it is fundamentally different from the conventional mechanical light amount stop mechanism. Since a mechanical configuration for driving the aperture is not required, the size of the system can be reduced, and the size can be reduced substantially to the size of the effective range of the optical path. Therefore, the size of the CCD camera can be reduced. In addition, since the amount of light can be appropriately controlled depending on the magnitude of the voltage applied to the patterned electrodes, the conventional phenomenon of diffraction can be prevented, a sufficient amount of light can be made incident on the image sensor, and blurring of the image can be eliminated.

[0122]

Next, specific examples of the present invention will be described in comparison with comparative examples.

Example 1 The optical device shown in FIG.
In addition, the present invention is applied to an optical filter (electrochemical light control element) substantially similar to that described with reference to FIG.

In this embodiment, as shown in the figure, a pair of transparent electrodes (for example, glass substrates) 4 and 5 constituting a cell are arranged at regular intervals, and
Each pair of working electrodes 2a, 2b, 2c, 2d, 2e and 3
a, 3b, 3c, 3d, and 3e are provided facing each other. The substrates 4 and 5 are held at a predetermined interval by a spacer 6, between which the silver salt solution 1 is sealed.

Then, outside the cell, as shown in FIG. 1A, the working electrodes 2a to 2e and 3a to 3e and the counter electrode 1
Constant current source 51 for supplying an electric current between the power supply 7a and 17b
And a control device 55 for controlling the constant current source 51 and a temperature detector 53 for detecting the temperature of the electrolytic solution of the cell.

In this embodiment, the working electrodes 2a to 2a
e and counter electrodes 17a and 17b and reference electrodes 27a and 27b are provided on the outer peripheral portion of 3e to 3e. These counter electrodes 17a and 17b are formed by forming an ITO film on the substrates 4 and 5 by sputtering to a thickness of about 200 nm to form a current collector layer. The working electrodes 2a to 2e and 3a
3e and the planar shapes of the counter electrodes 17a and 17b are substantially the same as those shown in FIG. Reference electrodes 27a, 2
As described above, 7b is effective for stably driving and controlling the optical device, but is not used here for driving and controlling because it does not relate to the essence of the present invention.

Through the manufacturing steps using various vapor deposition methods, the substrates 4 and 5 having the desired patterning are obtained.
As shown in FIG. 2, the working electrodes 2a to 2e and 3a to 3e and the counter electrodes 17a and 17b are arranged so as to face each other, and the two substrates 4 are interposed via a spacer 6 having a probe (not shown) of the temperature detector 53. 5 were bonded together, the silver salt solution 1 was sealed therein, and an electric circuit provided with necessary control means 55 was formed.

Silver salt solution 1 contains 500 mM of silver bromide and 750 mM of sodium iodide in dimethyl sulfoxide (DM
SO) / dimethylacetamide (DMAA) = 50/5
One dissolved in a mixed solvent of 0 was used.

When the temperature of the electrolytic solution was 22 ° C., 40 ° C., and 60 ° C., the current value was controlled by the control device to be 6 mA, 4 mA, and 3 mA. At this time, the average transmittance of light when silver was deposited for 2 seconds was measured. The results are shown in the table below.

[0130]

[Table 2]

According to this, the average transmittance was reduced to almost 20% even under various temperature conditions, and was considerably stable. When an oxidation current having the same value as described above is applied for 2 seconds, the deposited silver film is dissolved, and the transmittance becomes 1
It recovered to 00%.

(Embodiment 2) In this embodiment, FIG.
1B is installed in a heating / cooling means 59 having a built-in thermostat as shown in FIG. 1B.
It was adjusted to become. Among them, 3
When a current of mA was applied, it was observed that the average transmittance was always about 20% regardless of the ambient temperature.

From these results, it is apparent that, according to the present invention, a stable average transmittance can be realized by supplying a reduction current and an oxidation current according to the temperature, and an optical device having excellent characteristics can be provided. It is.

In the above embodiment, the problem of electric field concentration can be solved as follows. In other words, when the pastes 17a and 17b are formed by applying a paste-like material or the like, the corners of the edges of the counter-electrode are rounded due to the fluidity and surface tension of the paste-like material, and the counter electrode having substantially no corner 17a and 17b are formed. Therefore, the concentration of the electric field as described with reference to FIG. 9 is reduced, and as a result, the particles of the precipitate from the electrolytic solution 1 do not become larger. That is, the phenomenon that the particles of the precipitate float in the electrolytic solution to lower the transparency when the working electrode is decolored or short-circuit between the electrodes is prevented beforehand.

Although the present invention has been described with reference to the preferred embodiments and examples, these can be variously modified based on the technical concept of the present invention.

For example, the electrode patterns shown in FIG. 3 are not limited to concentric circles. Further, the drive control according to the case of the electrolytic solution is not limited to the above-described electrodeposition, but can be, of course, performed during the dissolution. The drive control waveform is constant according to the temperature,
It may be changed continuously or stepwise.

The optical device of the present invention can be applied not only to the above-mentioned transmission type, but also to a reflection type, and to other known filter materials (for example, organic electrochromic materials,
Liquid crystal, an electroluminescent material, etc.).

Further, the optical device of the present invention includes various optical systems, such as an optical diaphragm of a CCD, for example, an electrophotographic copying machine,
It can be widely applied to light quantity adjustment of optical communication equipment and the like. Further, the optical device of the present invention can be applied to various image display elements for displaying characters and images, in addition to the optical filters.

[0139]

The optical device of the present invention is provided with a control device capable of adjusting the value of the current to be supplied according to the temperature of the electrolytic solution. An average transmittance can be realized.

Further, since the optical device of the present invention is provided with a temperature control device for adjusting the temperature of the electrolytic solution to a predetermined temperature, a stable transmittance can be obtained with the same amount of electricity, and the influence of the ambient temperature can be reduced. An optical device that does not receive light can be realized.

Further, in the driving method of the present invention, a stable average transmittance can be realized irrespective of the temperature by adjusting the value of the current to be supplied according to the temperature in the element.

Further, according to the imaging apparatus of the present invention, since the above-described optical device capable of adjusting the light amount by applying an electric field is applied to a light amount diaphragm, a large-scale mechanical configuration is required unlike a conventional mechanical light amount diaphragm. Instead, the size can be reduced substantially to the effective range of the optical path, and furthermore, the amount of light can be controlled by the magnitude of the applied electric field to prevent diffraction and effectively prevent image blurring.

[Brief description of the drawings]

FIG. 1A is a structural diagram of an optical device of an electrochemical dimming type according to an embodiment of the present invention.

FIG. 1B is a block diagram of an electrochemical dimming type optical device according to another embodiment of the present invention.

FIG. 2 is a longitudinal sectional view of an image pickup apparatus in which the optical device according to the embodiment of the present invention is applied to a light amount stop of a CCD camera.

FIG. 3 is a cross-sectional view of the same kind of optical device (an electric system is omitted) according to another embodiment of the present invention.

FIG. 4 is a schematic configuration diagram of an electrochemical polymerization apparatus.

5A and 5B show a configuration of a conventional optical device, in which FIG. 5A is a cross-sectional view and FIG.

FIG. 6 is a perspective view of the same.

FIG. 7 is a cross-sectional view of another example of the same type of conventional optical device.

FIG. 8 is a plan view of the same.

FIG. 9 is a conceptual diagram showing a precipitation / growth / dropout phenomenon of silver particles in a conventional optical device using a silver plate as a counter electrode.

[Explanation of symbols]

1, 21, 63: silver salt solution, 2a to 2e, 3a to 3e,
22, 23, 54 ... working electrode, 4, 5, 24, 25, 6
0, 61: transparent substrate, 6, 26, 62: spacer, 17
a, 17b, 52 ... counter electrode, 27a, 27b ... reference electrode,
51: drive power supply, 53: temperature detector, 53a: probe, 55: control means, 57: temperature control means, 70: CC
D camera, 71 ... 1 group lens, 72 ... 2 group lens, 73
... 3 group lens, 74 ... 4 group lens, 75 ... CCD package, 75c ... CCD image pickup device, 76 ... Electrochemical optical device

Claims (24)

[Claims] 1. An optical device which comprises a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes and performs electrochemical dimming. Characterized by having a control means for adjusting the
Optical device. 2. The optical device according to claim 1, further comprising a sensor for detecting a temperature of the electrolytic solution, wherein the temperature information is input to a control circuit serving as the control unit. 3. The working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region.
An optical device according to claim 1. 4. The method according to claim 1, wherein the electrolyte is a silver salt solution.
An optical device according to claim 1. 5. A driving method for an optical device, comprising a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes, wherein the optical device performs electrochemical dimming according to the temperature of the electrolytic solution. A method for driving an optical device, comprising: adjusting a drive current value. 6. The method of driving an optical device according to claim 5, wherein the temperature of the electrolytic solution is detected, and the temperature information is input to a control circuit of the driving current. 7. The working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region.
The driving method of the optical device according to 1. 8. The method according to claim 5, wherein the electrolyte is a silver salt solution.
The driving method of the optical device according to 1. 9. An optical device which comprises a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes, and performs electrochemical dimming, and is driven in accordance with the temperature of the electrolytic solution. An image pickup apparatus, wherein an optical device provided with a control unit for adjusting a current value is provided in a light path for light quantity adjustment. 10. The imaging device according to claim 9, further comprising a sensor for detecting a temperature of the electrolytic solution, wherein the temperature information is input to a control circuit as the control unit. 11. The imaging device according to claim 9, wherein the working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region. 12. The imaging device according to claim 9, wherein the electrolyte is a silver salt solution. 13. A heating and cooling means for adjusting the temperature of an electrolytic solution in an optical device for electrochemically controlling light, comprising a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes. An optical device, comprising: a control unit that controls the heating and cooling unit. 14. The optical device according to claim 13, further comprising a sensor for detecting a temperature of the electrolytic solution, wherein the temperature information is input to the control unit. 15. The optical device according to claim 13, wherein the working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region. 16. The optical device according to claim 13, wherein the electrolyte is a silver salt solution. 17. A driving method for an optical device, comprising a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes, wherein the temperature of the electrolytic solution is controlled to a predetermined value. A method for driving an optical device, comprising adjusting to a temperature. 18. The method according to claim 1, wherein the temperature of the electrolytic solution is detected, and the temperature information is inputted to a temperature control means of the electrolytic solution.
8. The driving method of the optical device according to 7. 19. The method for driving an optical device according to claim 17, wherein the working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region. 20. The method according to claim 17, wherein the electrolytic solution is a silver salt solution. 21. An optical device for performing electrochemical dimming, comprising a working electrode, a counter electrode, and an electrolytic solution disposed in contact with these electrodes, wherein the heating device adjusts the temperature of the electrolytic solution. An imaging apparatus, comprising: an optical device provided with a cooling unit and a control unit for controlling the heating / cooling unit, for adjusting a light amount in an optical path. 22. The imaging device according to claim 21, further comprising a sensor for detecting a temperature of the electrolytic solution, wherein the temperature information is input to the control unit. 23. The imaging device according to claim 21, wherein the working electrode is a transparent or translucent electrode having a transmittance of 70% or more in a visible region. 24. The imaging device according to claim 21, wherein the electrolytic solution is a silver salt solution.