JP2715600B2 - Optical function element - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an optical functional device for converting a change in light intensity into a pulse current.

(Prior Art) The application of a photoelectric conversion element that converts the intensity of light to the intensity of current, voltage, etc., to an optical sensor or the like is being studied. Conventionally, inorganic materials such as CdS have been mainly used, and it has been studied to provide a desired sensitivity region by lamination with an organic dye. Porphyrins, phthalocyanines, and the like have been studied as organic material-based devices because they have photoelectric conversion ability and high quantum efficiency even when used alone.

In addition, when a cell in contact with a copper phthalocyanine vapor-deposited film and an aqueous electrolyte solution is irradiated with light or cut off, a pulse-like current is generated by Minami et al. (N. Minami et al.). (Ber. Bunsenges. Phys. Chem.) 1979, 83, 47
Reported on page 6.

(Problems to be Solved by the Invention) The conventional photoelectric conversion element shows a constant voltage and current response only when the light is continuously irradiated, and the electric signal intensity changes continuously depending on the light intensity. Therefore, if the light intensity is temporarily changed using a conventional photoelectric conversion element, and an attempt is made to configure an optical sensor that outputs the amount of change as a positive or negative signal, in addition to the photoelectric conversion element, the voltage rise after photoelectric conversion,
An electric external circuit such as a circuit for detecting a fall and a pulse generation circuit is required. Also, when measuring the amount of change in light intensity, it is necessary to take the difference between the photocurrent value before the change and the photocurrent value after the change.

On the other hand, according to Minami (N. Minami) et al., A configuration in which a pulse-like current is generated when light is irradiated or cut off is reported as described above. As a result of further detailed examination using a dye, it was found that the direction of a pulse-like current can be changed by appropriately combining an electron-donating substance and an electron-accepting substance in these films. Reached.

Means for Solving the Problems The present invention includes a three-component layer containing an electron-donating substance, a phthalocyanine dye and an electron-accepting substance, an electrolyte, and a second electrode laminated on a first electrode. The component layer and the second
The present invention relates to an optical functional device obtained by contacting the above electrode with the electrolyte.

The phthalocyanine dye may be any one that can be formed into a thin film and forms a liquid junction with an electrolyte solution. For example, 29H, 31H-phthalocyanine (metal-free phthalocyanine), zinc phthalocyanine, magnesium phthalocyanine, manganese phthalocyanine And metal phthalocyanines such as vanadyl phthalocyanine, copper phthalocyanine, iron phthalocyanine, and silicon phthalocyanine, and those in which four or less substituents (one or more in total) are bonded to each benzene ring in these phthalocyanine compounds. Examples of the substituent include an amino group, an alkylamino group, a dialkylamino group, a carboxyl group, an amide group, a hydroxyl group, an alkyl group, a fluoroalkyl group, an alkoxy group, a thioalkyl group, a sulfonic acid group, a sulfonamide group, a cyano group, and a trialkyl group. There are a silyl group and the like, and the carboxyl group and the sulfonic acid group may be in the form of a salt with sodium or the like. Illustrative phthalocyanine dyes having a substituent include tetraamino-29H, 31H-phthalocyanine, tetra-t-butyl copper phthalocyanine,
Examples include tetrakis (trimethylsilyl) copper phthalocyanine, tetrakis (trifluoromethyl) copper phthalocyanine, tetracarboxyl copper phthalocyanine tetrasodium salt, copper phthalocyanine tetrasulfonic acid tetrasodium salt, and the like.

The above phthalocyanine dyes may be dimers or multimers.

As the electron accepting substance or the electron donating substance, a transition metal complex represented by the following general formula (I), (II) or (III) is preferable, and a hydrophobic substance is particularly preferable. In the following, those in which m is 0 tend to be hydrophobic.

In the general formulas (I) and (II), Z is an atom or an atomic group selected from O, S, NR (R is hydrogen or an alkyl group) and may be different at each position, and X and X 'are hydrogen, Alkyl group, substituted alkyl group, halogen group, alkoxy group, alkyloxycarbonyl group, carboxyl group, alkylamino group, quaternary alkyl ammonium group,
Selected from a nitro group or a cyano group, X and X 'may be the same, n is an integer of 1 to 4, m is an integer of +2 to -2,
A represents one or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by m, and M represents a transition metal ion (provided that m is 0) Does not have A).

In the general formula (III), Z ′ is selected from S and NR (R is hydrogen or an alkyl group) and may be different at each position, and Y is hydrogen, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group and Selected from a cyano group, which may be different at each position, m is an integer of +2 to -2, and A is one or more having the number of charges necessary to neutralize the charge defined by m. An anion or one or more cations and M represent a transition metal ion (however, when m is 0, A is not present).

These compounds are described, for example, in JAMcleve
rty) et al., Progress in Organic Chemistry (P
rog.Inorg.Chem.) 10, 49 (1968), SCH Schrauzer et al., Accounts of Chemical Research (Acc.Chem.Res.) 2, 72 (1969), Inorganic Synthesis (Inorg) .Syn.) Volume 10, page 2 summarizes the synthesis method and characteristics in detail. Under normal conditions, it can be stably isolated from -2 anions in the zero-valent state in air, and its charge state is It differs depending on the type of the central metal ion and the type of the ligand. Various oxidation states have been confirmed in all or a part of the range from divalent anions to divalent cations in these compounds, and it is known that some of them can be stably isolated in different oxidation states. Have been.

Examples of the transition metal complex include a cobalt bis (dithiomaleonitrile) complex, a manganese bis (dithiomaleonitrile) complex, an iron bis (dithiomaleonitrile) complex, a copper bis (dithiomaleonitrile) complex, and a nickel bis (dithiomaleonitrile) complex. , Platinum bis (dithiomaleonitrile) complex, palladium bis (dithiomaleonitrile) complex, nickel bis (toluene-3,4-dithiolate) complex, nickel bis (octadecylbenzene-3,4
-Dithiolate) complex, platinum bis (toluene-3,4-dithiolate) complex, copper bis (toluene-3,4-dithiolate) complex, nickel bis (benzene-4-dimethylamino-1,2-dithiolate) complex, nickel bis ( Benzene-4-dioctadecylamino-1,2-dithiolate) complex, nickeles bis (benzene-3,4,5,6-tetrabromo-1,2-dithiolate) complex, nickel bis (1,2
-Dithionaphthalene) complex, platinum bis (1,2-dithionaphthalene) complex, nickel bis (dithiostyribene) complex, platinum bis (dithiostyribene) complex, palladium bis (dithiostyribene) complex, nickel bis (p-chlorodithiostyribene) complex, Nickel bis (p-methoxydithiostyribene) complex, nickel bis (p-octadecyloxydithiostyribene) complex, nickel bis (p
-Octadecyloxycarbonyldithiostyriben) complex, nickelsbis (p-carboxysidithiostyriben) complex, nickel bis (p-dimethylaminodithiostyriben) complex, nickel bis (p-trimethylammonium dithiostyriben) tetraio Dyed, nickel bis (p-dioctadecylaminodithiostyriben)
Complex, nickel bis (1,2-phenylene diimine) complex, platinum bis (1,2-phenylene diimine) complex, palladium bis (1,2-phenylene diimine) complex, nickel bis (4-chloro-1 , 2-Phenylenediimine) complex, nickel bis (3,4-dichloro-1,2-phenylenedimine) complex, nickel bis (4-alkyl-1,2-phenylenedimine) complex, nickel bis (diimino) Maleonitrile) complex, platinum bis (diiminomaleonitrile) complex, palladium (diiminomaleonitrile) complex, nickel bis [bis (trifluoromethyl) ethylene 1,2-dithiate] complex, platinum bis [bis (trifluoromethyl) Ethylene-1,2-dithiate] complex, palladium bis [bis (trifluoromethyl) ethylene-1,
2-dithiate] complex. In the general formulas (I) to (III), when m is not 0, an appropriate A, for example, quaternary ammonium such as tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion, dimethyldioctadecylammonium ion, etc. Ion, sodium ion, cation such as alkali ion such as potassium ion, ClO ₄
^-, BF ₄ ^-, containing one or more anions such as halogen ions. Such a transition metal complex may be an electron-accepting substance or an electron-donating substance. The oxidation-reduction potential and oxidation state of a substance selected from the complex, and a substance (one or more) selected from the complex (Preferably two or more) and a phthalocyanine-based dye and the arrangement of these substances determine whether they function as an electron-accepting substance or an electron-donating substance. For example, nickel bis (dithiomaleonitrile) dianion, which is used in the form of dimethyldioctadecyl ammonium salt or other salts, and nickel bis (orthophenylsamine)
The complex is typically used as an electron donating substance, and the nickel dithiostyriben complex functions as both an electron accepting substance and an electron donating substance, but is preferably used as an electron accepting substance.

Prussian blue, an iron-sulfur cluster compound, a nickel bis (deuroquinone) complex, tetrathiofulvalene, in combination with such a transition metal complex or as at least one of an electron donating substance and an electron accepting substance.
Tetracyanoquinodimethane, polypyrrole, polythiophene, polyalkylpyrrole, polyalkylthiophene, polyisothianaphthene and the like may be used.

In addition, ferrocene, N-alkylcarbazole, and the like can be used as the electron donating substance, and viologen, quinone, and the like can be used as the electron accepting substance.

It is preferable that the electron donor substance and the electron accepting substance can be formed into a film.

The electron donating substance, the phthalocyanine dye and the electron accepting substance are laminated in this order or in the reverse order to form a three-component layer. Methods for forming each layer into a film include vacuum evaporation, MBE (molecular beam epitaxy), ion plating, sputtering, plasma polymerization, and other dry processes, spin coating, casting, spreading on water, and electrolytic weighting. There are a legal process and an anodizing response wet process. The ternary layer is laminated on the first electrode, and the layer in contact with the first electrode may be a layer of an electron donating substance or a layer of an electron accepting substance. The thickness of each layer is determined as appropriate,
Angstroms or less is preferred.

The first electrode and the second electrode may be translucent electrodes or non-translucent electrodes. ITO as the translucent electrode
Electrode (indium tin oxide electrode), transparent gold electrode,
Examples thereof include an aluminum transparent electrode, which is formed on a suitable substrate by a vacuum evaporation method, a sputtering method, or the like. As the substrate, a light-transmitting substrate such as a glass plate is used.
Examples of the non-translucent electrode include gold, silver, copper, nickel and other metal electrodes. A platinum electrode is particularly preferable, and may be formed on an appropriate substrate.

Examples of the electrolyte include lithium perchlorate, sodium perchlorate, sodium chloride, lithium chloride, lithium iodide and the like. The electrolyte may be used as an electrolyte by dissolving it in a solvent such as water, methanol, ethanol, acetonitrile, methylene chloride, and propylene carbonate.Polymethyl methacrylate, polystyrene, polyvinyl alcohol,
It may be dispersed in a binder polymer such as polyethylene terephthalate and polyvinyl chloride and a gelling agent such as agar, agarose and juran gum and used as a solid film. As the binder of the solid film, a cured product of a curable composition including a combination of polyvinyl alcohol and glutaraldehyde, a combination of a reactive unsaturated monomer such as acrylonitrile and a radical polymerization initiator such as benzoyl peroxide, and the like may be used. .

In addition, polyethylene oxide,
Auxiliary polymers such as polypropylene oxide, polyethylene imine, polyepichlorohydrin, and polyethylene succinate are preferably included to increase the conductivity of the solid film. Further, the auxiliary polymer may be dissolved in the electrolytic solution.

The electrolyte is preferably used in an amount of 10 to 50% by weight in the solid film, and is dissolved in the electrolyte at a saturation concentration or less.

Next, a method for manufacturing an optical functional device according to the present invention will be described.

A three-component layer is formed and laminated on the first electrode as described above. When the electrolyte is used as a solid film containing a binder polymer, a solution obtained by dissolving the electrolyte and the binder polymer and, if necessary, the auxiliary polymer in a suitable solvent is applied to the second electrode and dried to form a solid. It is preferable that a film is formed, and thereafter, the solid film is laminated on the three-component layer so as to be in contact therewith. In this case, at least one electrode, particularly the first electrode, is preferably a light-transmitting electrode, and is preferably formed on a light-transmitting substrate. Forming a first electrode and a second electrode on the same substrate;
After covering the first electrode with the three-component layer, it is preferable to apply a solution containing the same electrolyte and binder polymer as described above on the three-component layer and the second electrode, and then to form a solid film by drying. A suitable substrate may be laminated on the solid film in order to protect the substrate. In this case, the first electrode and the substrate on which the first electrode is formed are preferably light-transmitting, and only the protection substrate may be light-transmitting. When a curable composition is used as the binder, a curing reaction is performed during the coating and drying.

When the electrolyte is used as a solid film containing a gelling agent,
An optical functional device can be produced in the same manner as in the case of the solid film containing the binder polymer described above, but in this case, the solid film is formed of the electrolyte and the gelling agent and, if necessary, the auxiliary polymer as described above. After adding to a solvent and heating to form a uniform solution, it can be formed by coating or pouring and cooling. When applying and pouring, an appropriate frame can be used.

When an electrolytic polymer film is used as the electrolyte, an optical functional device can be produced in the same manner as in the case of the solid film containing the binder polymer described above. In this case, electrolytic polymerization is performed instead of the above-mentioned coating and drying. Will be

When an electrolyte is used as an electrolyte, a three-component layer laminated on a first electrode formed on an appropriate substrate and a second electrode are used so that the second electrode faces the three-component layer. May be immersed in the electrolyte. Alternatively, a first electrode and a second electrode may be formed over the same substrate, and the first electrode covered with a three-component layer may be immersed in an electrolytic solution. In these cases, it is preferable that the first electrode be translucent.

In the above, the first electrode is kept out of direct contact with the electrolyte. Each electrode can be connected to a potentiostat or the like to measure a current value. In this case, a reference electrode such as a saturated calomel electrode or a silver-silver chloride electrode can be appropriately connected. When a solid electrolyte or an electrolytic polymerized membrane is used, the electrolyte and the reference electrode can be connected using a salt bridge.

 The present invention will be described with reference to the drawings.

FIG. 1 is a sectional view showing an example of an optical functional device used in the present invention. A film in which a first electrode film 2 is formed on a first substrate 1, and a three-component layer 3 is formed on the first electrode film 1, has a three-component layer 3 in contact with a solid film (electrolyte layer) 4 and a second electrode 5. Are laminated so that the second substrate 6 formed on the surface thereof contacts the second electrode film 5 with the solid film (electrolyte layer) 4. Further, a salt bridge 7 for connecting a third electrode (reference electrode).
Are connected to a solid membrane (electrolyte layer) 5. The third electrode (reference electrode) and the salt bridge are not always necessary.
When the electrolyte is used in the form of an electrolytic solution, the structure can be basically the same as described above. In this case, the first substrate formed on an appropriate substrate is used.
What is necessary is just to immerse the electrode in which the three-component layer is laminated on the electrode and the second electrode in the electrolytic solution so that it faces the three-component layer. A structure in which a three-component layer is laminated on a first electrode formed on an appropriate substrate can be configured so that the electrolyte is brought into contact only with the three-component layer without being immersed in the electrolyte.

When the optical functional device of the present invention is irradiated with light having a wavelength at which the phthalocyanine dye absorbs, a pulsed current flows in response to a change in light intensity. At this time, the direction of the pulse current can be measured by measuring the current value to detect a change in the light intensity of the irradiation light, and the optical function element is used as an optical switch using such current characteristics. You can also.

The irradiation light may include light having a wavelength at which the phthalocyanine dye absorbs, and may be monochromatic light or polychromatic light, or may include light having a wavelength not absorbed by the phthalocyanine dye. The method of irradiating light is not particularly limited, and any method may be used as long as light can reach the three-component layer, particularly the phthalocyanine dye. The light may be emitted directly from a light source, or may be emitted after being condensed by an optical system such as a lens.

(Operation) The optical functional device of the present invention exhibits current conversion characteristics as shown in FIG. That is, a pulse as shown in FIG. 2 (a) is applied to the optical functional device of the present invention (the three-component layer in which an electron donating substance, a phthalocyanine dye and an electron accepting substance are laminated in this order from the first electrode side). Irradiation of light (input light) produces a current corresponding to that shown in FIG. 2 (b). That is, when the light intensity increases rapidly, a cathodic current response is temporarily generated correspondingly, and when the light intensity is rapidly reduced, a anodic current is temporarily generated correspondingly. 4 shows a current response. After such a current response, if the intensity of the input light is constant, the photocurrent immediately decreases. In the optical functional device of the present invention, the three-component layer is formed of a receptive substance,
When the phthalocyanine dye and the electron donating substance are laminated in this order, there is a current response opposite to the above.

As described above, the optical functional element of the present invention can change the directionality of the pulse current corresponding to the change in the light intensity applied to the three-component layer by changing the configuration of the three-component layer.

(Example) Hereinafter, the present invention will be described with reference to examples.

Example 1 On a 26 mm × 76 mm glass plate, a nickel bis (orthophenylenediamine) complex was formed into an ITO transparent electrode by a vacuum evaporation method, and the peripheral portion of the ITO film was removed by etching with a width of 3 mm.
Then, a nickel bis (orthophenylenediamine) complex, which is an electron donating substance, was added to the mixture at 5 × 10 ⁻⁵ torr at 280 ° C.
Vacuum-deposited to cover the entire ITO film to a thickness of about 600 Å with zinc phthalocyanine at 2 × 10 ^-5 torr, 39
Vacuum deposited at 0 ° C. to a thickness of about 800 Å, and then nickel-bis (dithiostyriben) complex, an electron accepting substance, at 4 × 10 ^-5 torr and vacuum deposited at 240 ° C. to a thickness of about 600 Å. A component layer was formed. However,
Each layer was formed by masking the electrode extraction portion from the ITO transparent electrode.

Next, an electrolytic solution consisting of a 0.1 M LiClO ₄ aqueous solution was placed in a transparent glass container, and the ITO transparent glass electrode, the platinum electrode (second electrode), and the reference electrode, which were formed by laminating the zinc phthalocyanine thin film prepared above, were saturated. The calomel electrode was immersed. The zinc phthalocyanine thin film and the platinum electrode (second electrode) were opposed to each other, and each electrode was connected to a potentiostat. The electrolyte was previously degassed for 10 minutes with argon gas.

The ternary layer was tested by irradiating 620 nm light, the maximum absorption wavelength of zinc phthalocyanine, through an ITO transparent electrode.
The intensity of the irradiated light was sequentially switched between 0 and 6.7 μW. As a result, a current value as shown in FIG. 3 was measured. That is, a cathodic pulse current flows at the moment of irradiating light (on time in FIG. 3), and the moment of stopping light (off time in FIG. 3).
An anodic pulse current flowed through. In addition, after using a halogen lamp as a light source and making monochromatic light through a monochromator, the light was condensed and irradiated by an optical system.

Example 2 The same procedure as in Example 1 was carried out except that the stacking order of the nickel-bis (orthophenylenediamine) complex as the electron-donating substance and the nickel-bis (dithiostyriben) complex as the electron-accepting substance in the three-component layer was changed. It carried out according to Example 1. As a result, a current response as shown in FIG. 4 was obtained. In other words, an anodic pulse current flows at the moment of irradiating light (on time in FIG. 4),
At the moment when the light was cut off (at the time of off in FIG. 4), a cathodic pulse current flowed.

Example 3 ITO formed by vacuum evaporation on a 26 × 30 mm glass substrate
Etch the film to make the first electrode of 10mm x 20mm and 5mm x 26m
m second electrode was formed, and a three-component layer was formed according to Example 1 so as to cover only the first electrode. The formation of the three-component layer was performed by masking the electrode lead-out portion of the first electrode, the second electrode, and the periphery thereof.

Then, water containing 1M lithium perchlorate and 1% by weight of agarose is heated to 100 ° C. to form a uniform solution. Then, the ternary layer and the second electrode are covered except for the electrode take-out part. It was applied to the entire glass substrate and cooled to form a solid electrolyte layer. Thereafter, a glass plate was placed for protection of the solid electrolyte layer. The glass plate used was partially missing for connecting a salt bridge and extracting an electrode. The salt bridge was connected to the electrolyte, and a reference electrode was connected ahead of it. Each electrode was connected to a potentiostat.

When light irradiation was performed in the same manner as in Example 1, a pulse-like current flowed when the light intensity changed abruptly, and the same result as in Example 1 was obtained.

(Effect of the Invention) The optical functional device according to the present invention generates a pulse current corresponding to a change in light intensity, which can be used for detecting a change in light intensity and for an optical switch.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of an optical functional device according to the present invention, FIG. 2 is a graph showing a light pulse and a corresponding current response, and FIG. 3 is a light beam of Example 1 when the irradiation light intensity is changed. FIG. 4 is a graph showing the current response of the functional element and FIG. 4 is a graph showing the current response of the optical functional element of Example 1 when the intensity of the irradiation light is changed. DESCRIPTION OF SYMBOLS 1 ... first substrate 2 ... first electrode 3 ... ternary layer 4 ... solid film (electrolyte layer) 5 ... second electrode 6 ... second substrate 7 …… Shiobashi

Continuing on the front page (72) Inventor, Toshinori Tachaina, 48, Wadai, Tsukuba, Ibaraki Prefecture, Hitachi Chemical Co., Ltd., Tsukuba Development Laboratory Co., Ltd. (56) References JP-A-62-165647 (JP, A) JP-A-62-65385 (JP, A) JP-A-57-182979 (JP, A)

Claims (1)

(57) [Claims] 1. A ternary layer containing an electron donating substance, a phthalocyanine dye and an electron accepting substance, an electrolyte, and a second electrode laminated on a first electrode, wherein the ternary layer is vacuum deposited. A film formed by a method, wherein the three-component layer and the second electrode are brought into contact with the electrolyte, and at least one of the electron donating substance and the electron accepting substance has the following general formula: An optical functional device selected from the transition metal complexes represented by formula (I), formula (II) or formula (III). In the general formulas (I) and (II), Z is O, S, NR (R
Is an atom or atomic group selected from hydrogen or an alkyl group) and may be different at each position, and X and X ′ are hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an alkoxy group, an alkyloxycarbonyl group, a carboxyl group, Group, alkylamino group, quaternary alkylammonium group,
Selected from a nitro group or a cyano group, X and X 'may be the same, n is an integer of 1 to 4, m is an integer of +2 to -2,
A represents one or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by m, and M represents a transition metal ion (provided that when m is 0, A represents Does not exist). In the general formula (III), Z 'is selected from S and NR (R is hydrogen or an alkyl group) and may be different at each position, and Y is hydrogen, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group. And m may be different at each position, m is an integer of +2 to -2, A is one or more anions having the number of charges necessary to neutralize the charge defined by m Alternatively, one or more cations and M represent a transition metal ion (however, when m is 0, A does not exist).