JPH0198266A - Photoelectric conversion element - Google Patents

Abstract

PURPOSE:To form a photoelectric converter element having a low cost, a large area and a high conversion efficiency by incorporating specific azo pigment in an optical active layer. CONSTITUTION:In a photoelectric converter element having an optical transmissible front electrode, an optical active layer and a back face electrode, the active layer contains azo pigment represented by a general formula formed of a specific formula I (where A represents coupler residue, and n represents integer numbers of 0 to 4). This layer may contain only the azo pigment, be dispersed in resin, or further contain an additive. In case of the dispersion in the resin, the pigment/resin ratio is suitably 10/0-1/4(wt. ratio). The thickness of the active layer is adequately 0.01-10mum, and the optimum thickness is preferably 0.05-3mum, though it is different according to the type of the pigment or the resin to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photoelectric conversion element (organic solar cell) using an organic leading conductor, and is applied to optical sensors, image sensors, etc.

[Prior Art] Many attempts have been made to produce photoelectric conversion elements using inorganic semiconductors. The goal is a) high conversion rate and b)
It is a low-priced photoelectric conversion element.

Single crystal S h polycrystal S is Cd55CdTe.

Attempts have been made to put GaAs, amorphous Si, etc. into practical use, but it is difficult to say that all of these satisfy the goal b).

In order to improve this drawback, attempts have been made in recent years to fabricate photoelectric conversion elements using organic semiconductors. Examples of the organic semiconductor layers used are as follows.

(a) Merocyanine dye layer coated with a spinner (JP-A-51-122389, JP-A-53-131782 and "Journal 9 of Applied Physics (J. Ap
pl, Phys, ) J 49.5982.1978) (
b) Laminated phthalocyanine vapor-deposited layer or electron donor layer such as obalene and electron acceptor layer such as pyrylium dye (JP-A-54-27787, JP-A-201872)
and R, O, Loutf'
y), “Journal of Akelide, Physics J, Appl.

Phys, ) J 52.5218.1981) (c)
Eutectic complex layer formed from pyrylium dye and polycarbonate (JP-A-54-27387) (d) Layer in which metal-free phthalocyanine is dispersed in a binder (JP-A-55-9)
497) (e) Laminated layer of n-type silicon and p-doped polyacetylene thin film (Japanese Patent Application Laid-Open No. 55-130182, JP-A No. 55-138879 and B. R. Weinberger (B. R., Wclnnbcrgcr) Applied Physics Letters (Appl, Phys, Lett) 88.555.
1981) (to) Vacuum-deposited merocyanine dye layer (
(Japanese Unexamined Patent Publication No. 58-35477) These methods include applying a solution in which these organic semiconductors are dissolved or dispersed in a medium onto a substrate, or vacuum-depositing them at low temperatures, and then providing another conductive layer thereon. Although a large-area product can be obtained at low cost, the conversion efficiency is too low to be of practical use.

[Purpose] The present invention has been made in order to solve the above-mentioned conventional drawbacks, and it is an inexpensive and easy-to-produce large-area photoelectric conversion layer using a layer in which an azo pigment is dispersed. The object of the present invention is to provide a photoelectric conversion element that is flexible and uses an organic material, has high conversion efficiency, and is more suited to the spectral distribution of sunlight and indoor light than conventional photoelectric conversion elements.

[Structure] The present invention has been made as a result of intensive research to achieve the above object.
In a photoelectric conversion element having a translucent front electrode, a photoactive layer, and a back electrode, the photoactive layer is composed of N [wherein A represents a coupler residue and n represents an integer from 0 to 4]. It has been found that the above object can be achieved by a photoelectric conversion element characterized by containing an azo pigment represented by the general formula.

The photoelectric conversion element of the present invention has a photoactive layer (1) containing an azo pigment.
) is sandwiched between two electrodes (front electrode, back electrode).

Since light enters from the front electrode side, the front electrode is transparent.

Both the front and back electrodes may be used alone, or may be provided with a support or a protective layer. 1st~
Examples of these are shown in FIG.

The front electrode and the back electrode are connected to an external circuit through lead wires, etc., and used for actual use.

The photoactive layer need not be a single layer; examples of two layers are shown in FIGS. 1-3(b), respectively. This photoactive layer (n) may be a layer that generates charges by light, similar to the photoactive layer (1), or may be a layer that efficiently transfers the charges generated in the photoactive layer (1). ) In the example shown in the figure, the photoactive layer (1) is drawn on the front electrode side, but of course the photoactive layer (II) may be on the front electrode side.
The photoactive layer (I) may also be a multilayer consisting of different azo pigments.

The present invention relates to the photoactive layer (1).

The photoactive layer (1) is a layer that generates holes and electrons when irradiated with light. This requires the presence of an electric field within the layer, either by applying an external voltage between the front and back electrodes, or by applying a voltage externally between the front or back electrodes (I). Due to the difference in Fermi level (or work function) between the layer i) and the layer i), heat carriers move, and this is achieved without an external voltage.

The photoactive layer (I) is a layer containing the following azo pigment as a main component.

The azo pigments are effective as photocarrier generating materials for electrophotographic photoreceptors, and we have found that these materials exhibit very good characteristics when applied as photoelectric conversion elements.

Here, a photoconversion element is one that generates an electromotive force or current, or both, when light is irradiated without applying an external voltage between the front and back electrodes in Figure 1, and that generates a large amount of electromotive force or current when an external voltage is applied. This is an element from which photocurrent can be extracted.

As mentioned above, this layer contains the following azo pigment.

The azo pigment may be alone, or it may be dispersed in a resin as described below, or it may further contain additives as described below.

In the case of dispersion with resin, the pigment/resin ratio is 101O to 114
(weight ratio) is appropriate, preferably 101O to 1/2. Charges are generally thought to move through the pigment, and the more resin there is, the more difficult it becomes to move the generated charges.

The additive is used to improve the transfer efficiency of charges generated in the photoactive layer (I) or to improve the efficiency of charge generation by light. Although additives can be expected to increase photocurrent, the opposite result often occurs, and an appropriate combination of pigments and additives is required.

The appropriate amount of the additive is 5 to 50% by weight based on the total weight of the resin.

The thickness of the photoactive layer is suitably 0.01 to 10 μm. The optimum film thickness varies depending on the type of azo pigment and resin used, but is preferably 0.05 to 3 μm.

If it is thin, the amount of light absorbed will be small, and the probability of pinholes occurring between the front and back electrodes will increase. When the thickness becomes thicker, the distance for one of the generated holes and electrons to reach the electrode becomes longer, increasing the probability that they will be deactivated on the way, and reducing efficiency.

For the aqueous layer, mix the above pigment with a resin additive if necessary in a suitable medium, grind the pigment using a method such as a ball mill to create a uniform slurry, or mix the pigment in a solvent such as an organic amine. They are formed by melting and applying these onto a back electrode or a back electrode on a support, or a front electrode on a support.

The photoactive layer formed for this purpose has a strong photosensitive region in the visible region and has a high release voltage (V
oe) and a high short circuit current (Jsc) as an organic material. The conversion efficiency (n) in this case is determined by the following formula: 77m tooXVOCXJ 5cXf f1n (P in : incident light energy, ff : fill factor).

The element of the present invention provides a high conversion effect for visible light as one using an organic material. This is due to the azo pigment of the present invention, which has a large quantum efficiency in the internal electric field formed at the junction, and is presumed to be able to obtain a large Jcs. Of course, even when an external voltage is applied, a large photocurrent can be extracted due to the above-mentioned high quantum efficiency, and therefore it is used as a photoelectric conversion element with excellent sensitivity.

For the front electrode layer and its support: Nialuminum, lead, zinc, tantalum, nickel, titanium, cobalt,
Translucent metals such as niobium, copper, Hastelloy C1 gold, platinum, silver, and palladium, and metal oxides such as tin oxide and ITO can be used as the front electrode, and glass and transparent plastic films can be used as the support. .

Regarding the back electrode and its support: Most metals can be used as the back electrode.

Glass or transparent plastic film is used as the support. ' Concerning the photoactive layer (n): This layer a) contains other charge-generating pigments to cover the low sensitive wavelength region of the azo pigment, or b) contains the photoactive layer (n).
) a layer forming a junction barrier between C) a photoactive layer (I
) is a layer that effectively transfers either holes or electrons generated in the process.

Of these, layer a) is formed by applying pigments such as phthalocyanine pigments, perylene pigments, aromatic polycyclic non-alcohol pigments, thioindigo pigments, and quinacridone pigments in the same manner as the photoactive layer (I).

The layer b) is formed by dispersing fine particles of zinc oxide, titanium oxide, cadmium sulfide, selenium crystals, lead oxide, etc. in an adhesive resin.

The layer C) is formed by mixing the additives of the photoactive layer (I), an electron donor described below as a hole transfer agent, and an electron acceptor as an electron transfer agent into a suitable resin. Ru.

The azo pigment used as an essential component of the photoactive layer of the present invention is represented by the general formula: Here, A represents a coupler residue, and n represents an integer from 0 to 4.

Couplers used in the production of the azo pigment represented by the above general formula include, for example, aromatic hydrocarbon compounds having a hydroxyl group such as phenols and naphthols, heterocyclic compounds having a hydroxyl group, and aromatic compounds having an amino group. group hydrocarbon compounds and heterocyclic compounds having an amide group, aromatic hydrocarbon compounds and heterocyclic compounds having an amino group and a hydroxyl group such as aminonaphthols, aliphatic or aromatic enolic ketone groups (active methylene groups) ), and preferably the coupler residue A has the following general formula (n), (m), (IV), (V), (Vl
), (■), (■), (IX), (X), (XI), (
It is represented by the general formula XII).

[In the above formulas (II), (m), (IV) and (V),
XS7121m and n represent the following, respectively.

] (R+ and R2 represent hydrogen or a substituted or unsubstituted alkyl group, and R3 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Yl: hydrogen, nitrogen, substituted or An unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfone group, a substituted or unsubstituted sulfamoyl group, or (R4 represents hydrogen, an alkyl group or a substituent thereof, a phenyl group or a substituent thereof, Y 2 is a hydrocarbon ring group or a substituent thereof, a polycyclic group or a substituent thereof, or/or a substituent thereof, a heterocyclic group or a substituent thereof, a styryl group or a substituent thereof, R6 is hydrogen, an alkyl group, represents a phenyl group or a substituted product thereof, or R5
and R may also form a ring together with the carbon atoms bonded thereto. ) Z: hydrocarbon ring or its substituted product, or heterocycle or its substituted product n: an integer of 1 or 2 m: an integer of 1 or 2] [In formulas (Vr) and (■), R7 is a substituted or unsubstituted represents a hydrocarbon group; is the same as ] [In the above formulas (IX) and (X), R9 represents hydrogen or a substituted or unsubstituted hydrocarbon group, and Ar2 represents a hydrocarbon ring group or a substituted product thereof. General (n), (
Examples of the hydrocarbon ring for Z in m), (rV) or (V) include a benzene ring and a naphthalene ring, and examples of the heterocycle include an indole ring, a carbazole ring, and a benzolane ring. Examples of the substituent in the second ring include halogen atoms such as chlorine atoms and bromine atoms, and alkoxy groups.

Examples of the hydrocarbon ring in Y2 or R5 include phenyl group, naphthyl group, anthryl group, pyrenyl group, etc.
Examples of the heterocyclic group include a pyridyl group, a thienyl group, a furyl group, an indolyl group, a benzofuranyl group, a carbazolyl group, and a dibenzofuranyl group.
Examples of the ring formed by combining R6 and R6 include a fluorene ring and the like.

Substituents on the hydrocarbon ring group or heterocyclic group of Y2 or R5 or the ring formed by R5 and R6 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy groups, alkoxy groups such as butoxy groups, halogen atoms such as chlorine atoms and bromine atoms, dialkylamino groups such as dimethylamino groups and diethylamino groups, dialkylamino groups such as dibenzylamino groups, halomethyl groups such as trifluoromethyl groups, Examples include a nitro group, a cyano group, a carboxyl group, or an ester thereof, a hydroxyl group, and a sulfonic acid group such as -S 04 Na.

Examples of substituents for the phenyl group of R4 include halogen atoms such as chlorine atoms and bromine atoms.

Representative examples of the hydrocarbon group in R1 or R9 are:
Examples include alkyl groups such as a methyl group, ethyl group, propyl group, and butyl group, aralkyl groups such as benzyl group, aryl groups such as phenyl group, and substituted products thereof.

Substituents on the hydrocarbon group in R7 or R3 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy group,
Examples include alkoxy groups such as butoxy groups, halogen atoms such as chlorine atoms and bromine atoms, hydroxyl groups, and nitro groups.

Typical examples of the hydrocarbon ring group in Arl or Ar2 are phenyl group, naphthyl group, etc.
Substituents for these groups include alkyl groups such as methyl, ethyl, propyl, and butyl, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, nitro, chlorine, bromine, etc. Examples include halogen atoms, dialkylamino groups such as cyano groups, dimethylamino groups, and diethylamino groups.

Furthermore, among X, a hydroxyl group is particularly suitable.

Among the above coupler residues, preferred is the general formula <
m>, (Vl), (■), (■), (IX) and (X
), and among these, X in the general formula
is preferably a hydroxyl group. Also, among these, the general formula (
XI) A coupler residue represented by the formula (Y+ and 2 are the same as above) is preferred, and more preferably a coupler residue represented by the general formula (Z, Y2 and R2 are the same as above).

Furthermore, among the above-mentioned preferred coupler residues, the general formula (XI Xia) or (X I V) (Z, R2, R5
and R6 are the same as above, and examples of R10 include the substituents for Y2 above. ) is appropriate.

Specific examples of coupler residues are shown in structural formulas as follows.

No. A2NS Examples of resins for dispersing the azo pigment of the present invention include polyester resins, polycarbonate resins, polyamide resins, polyurethane resins, epoxy resins, alkyd resins,
Phenolic resin, melamine resin, acrylic resin, cellulose resin, vinyl acetate resin, vinyl chloride resin, vinylidene chloride resin, vinylidene fluoride resin, butyral resin,
Polyvinyl carbazole resin, polystyrene resin, polyimide resin, polyacrylonitrile resin, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, ethyl cellulose, etc. Can be mentioned.

Additives used in the present invention include metal oxides such as zinc oxide, titanium oxide, lead oxide, and alumina, as well as charge-donating substances and charge-accepting substances shown below.

As the charge donor, the following general formulas (1) to (11) are used.
Examples include the compounds shown below.

[In the formula, R1 represents a methyl group, ethyl group, 2-hydroxyethyl group, or 2-chloroethyl group, R2 represents a methyl group, ethyl group, benzyl group, or phenyl group, and R3
represents hydrogen, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a dialkylamino group, or a nitro group. [wherein Ar represents a naphthalene ring, an anthracene ring, a styryl group, a substituent thereof, a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group. CO[In the formula, RI represents an alkyl group, a benzyl group, or a phenyl group, and R2 represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a carbon number 1
~3 represents an alkoxy group, dialkylamino group, dialkylamino group, or diarylamino group, and n is 1 to
represents an integer of 4, and when n is 2 or more, R2 may be the same or different. R3 represents hydrogen or a methoxy group. [In the formula, R1 represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group, or a heterocyclic group, and R2, R
3 may be the same or different and represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a chloralkyl group, a substituted or unsubstituted aralkyl group, and R2 and R3 are bonded to each other, and nitrogen may form a heterocycle containing R4 may be the same or different and represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen. ] [In the formula, R represents hydrogen or a halogen atom, and Ar is a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group [In the formula, R1 is hydrogen, halogen, cyano group, carbon number 1] ~4 alkoxy group or an alkyl group having 1 to 4 carbon atoms, Ar represents , R2 represents an alkyl group having 1 to 4 carbon atoms, R3 is hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, carbon Number 1
~4 represents an alkoxy group or dialkylamino group,
n is 1 or 2, and when n is 2, R3 may be the same or different, R4 and R5 are hydrogen, and have 1 to 1 carbon atoms.
4 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted benzyl group. [In the formula, R is a carbazolyl group, pyridyl group, thienyl group, indolyl group, furyl group, or a substituted or unsubstituted phenyl group, styryl group, naphthyl group or anthryl group, and these substituents are dialkylamino selected from the group consisting of a group, an alkyl group, an alkoxy group, a carboxy group, or an ester thereof, a halogen atom, a cyano group, an aralkylamino group, an N-alkyl-N aralkylamino group, an amino group, a nitro group, and an acetylamino group. represents a group. [In the formula, RI represents a lower alkyl group or a benzyl group, and R2 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group, or an amino group substituted with a lower alkyl group or a benzyl group. , and n represents an integer of 1 or 2. [In the formula, Rl represents a hydrogen atom, an alkyl group, an alkyl group, an alkoxy group, or a halogen atom, and R2 and R3
represents an alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, sR4 represents a hydrogen atom or a substituted or unsubstituted phenyl group, and A represents a phenyl group or a naphthyl group.] child, alkyl group or substituted or unsubstituted phenyl group,
A represents a 9-anthryl group or a substituted or unsubstituted N-alkylcarbazolyl group, where R2 is a monohydrogen atom,
Alkyl group, alkoxy group, halogen (however, R3 and R4 are alkyl group, substituted or unsubstituted aralkyl group,
Represents a substituted or unsubstituted aryl group, R3 and R4
may form a ring), m is an integer of 0.1.2 or 3, and when m is 2 or more, R2 may be the same or different. ] [In the formula, R1, R2 and R3 represent hydrogen, a lower alkyl group, a lower alkoxy group, a dialkylamino group or a halogen atom, and n represents 0 or 1. ] Examples of the compound represented by the general formula (1) include 9-ethylcarbazole-3-aldehyde, 1-methyl-1-phenylhydrazone, 9-ethylcarbazol-3-aldehyde 1-benzyl-1-phenylhydrazone, 9 -ethylcarbazole-3-aldehyde 1,1-diphenylhydrazone and the like.

Examples of the compound represented by general formula (2) include 4-diethylaminostyrene-β-aldehyde t-methyl-1-
Examples include phenylhydrazone, 4-methoxynaphthalene-1-aldehyde l-benzyl-1-phenylhydrazone, and the like.

Examples of the compound represented by the general formula (3) include 4-methoxybenzaldehyde 1-methyl-1-phenylhydrazone, 2.4-dimethoxybenzaldehyde 1-benzyl-1-phenylhydrazone, and 4-diethylaminobenzaldehyde 1.1- Diphenylhydrazone, 4-methoxybenzaldehyde 1-benzyl-1-(4-methoxy)phenylhydrazone, 4-diphenylaminobenzaldehyde l-benzyl-1-phenylhydrazone, 4
-dibenzylaminobenzaldehyde-1,1-diphenylhydradosine and the like.

The compound represented by general formula (4) includes, for example, 1.1-
Bis(4-dibenzylaminophenyl)propane, tris(4-diethylaminophenyl)methane, 1,1-bis(4-dibenzylaminophenyl)propane, 2,2
-dimethyl-4,4'-bis(diethylamino)-triphenylmethane and the like.

The compound represented by general formula (5) includes, for example, 9-(4
-diethylaminostyryl)anthracene, 9-bromo-10-(4-diethylaminostyryl)anthracene, and the like.

The compound represented by general formula (6) includes, for example, 9-(4
-dimethylaminobenzylidene)fluorene, 3-(9
-fluorenonedene)-9-ethylcarbazole and the like.

The compound represented by general formula (7) includes, for example, 1.2-
Bis(4-diethylaminostyryl)benzene, ■, 2
-bis(2,4-dimethythoxystyryl)benzene.

Examples of the compound represented by the general formula (8) include 3-styryl-9-ethylcarbazole and 3-(4-methoxystyryl)-9-ethylcarbazole.

Examples of the compound represented by the general formula (9) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1-(4-diphenylaminostyryl)naphthalene, 1-(4- diethylaminostyryl) naphthalene, etc.

Examples of the compound represented by the general formula (IO) include 4-diphenylamino-α-phenylstilbene and 4'-methylphenylamino-α-phenylstilbene.

The compound represented by general formula (11) includes, for example, 1-phenyl-3-(4-diethylaminostyryl)-5-(
4-diethylaminophenyl)pyrazoline, 1-phenyl-3-(4-dimethylaminostyryl)-5-(4-
dimethylaminophenyl) pyrazoline, etc.

Other charge-donating substances include, for example, 2.5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole, 2.5-bis[4-(4-diethylaminostyryl)phenyl]-1 , 3,4-oxadiazole, 2-(9-ethylcarbazolyl-3-)-5
-(4-diethylaminophenyl) -1,3,4-
Oxadiazole compounds such as oxadiazole, 2-
Vinyl-4-(2-chlorophenyl)-5-(4-
Examples include low molecular weight compounds such as oxazole compounds such as diethylaminophenyl)oxazole and 2-(4-diethylaminophenyl)-4-phenyloxazole. Further, polymeric compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, pyrene formaldehyde resin, and ethylcarbazole formaldehyde resin can also be used.

“ Gradual receptor substances include, for example, chloranil,
Bromoanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4.7-trinitro-9-fluorenone, 2,4.5.7-tetranitro-9-fluorenone, 2,4,5.7-titranitroxanthone, 2
．． 4.81-Linitrothioxanthone, 2゜6.8-trinitro-4H-indeno[1,2-b]thiophen-4-one, 1.3.7-)Linitrodibenzothiophene-5,5-dioxide and so on.

Next, structural examples of the photoelectric transformable element of the present invention will be explained with reference to the schematic diagrams shown in FIGS. 1 to 3. Figure b shows an example in which a second photoactive layer is added to supplement the photoactive layer shown in figure a.

In the figure, ■ is a translucent front electrode, 2 is a photoactive layer (I),
3 is a photoactive layer (II), 4 is a back electrode, 5 is a front electrode support, and 6 is a back electrode support. It should be understood that these structures can be varied in various ways depending on the application.

Examples are shown below to further specifically explain the present invention, but the present invention is not limited thereto.

Example 1 1 g of an azo pigment having the following structure, 5 g of a 5% cyclohexanone solution of butyral resin (XYHL manufactured by UCC), and 19 g of cyclohexanone were ball-milled for 3 days, then diluted with 5 g of the above butyral solution, and applied at 5 vt%. A liquid was prepared.

This coating solution is indium-doped tin oxide (hereinafter referred to as I).
A glass substrate provided with
After pulling up the substrate at a speed of 2 seconds, it was heat-dried at 90°C, and the I
A pigment dispersion film was provided on the TO substrate.

On top of this, translucent aluminum was vacuum-deposited so that the transmittance at 560 nm was about 8%, and then a thin copper wire was connected to the ITO and aluminum using silver paste.

For this sample, 860nIIl was applied to the aluminum electrode side.
While irradiating monochromatic light of
A ramp wave swept at mv/sec was applied to measure the current-voltage characteristics. The result was Voc-0,95VJsc-13nA/cd1'f'-0,20.

The photoelectric conversion efficiency (η') of this device at 680 nm, corrected for the transmittance of the electrodes, was o, 17%.

Example 2 680Il except that the azo pigment of Example 1 was changed to the following.
lffi monochromatic light is incident on this sample, CPin'-1
, 36 μw/cJ), and the photoelectric conversion characteristics were measured in the same manner as in Example 1, and the following results were obtained.

Voc-0,98V Jsc-5,7nA/cshff'-0,14 η゛kaku0.057% Example 3 A sample was prepared in the same manner as in Example except that the azo pigment in Example 1 was changed to the following. Created.

BOOsm monochromatic light is incident on this sample, and CPin'-
When the photoelectric conversion characteristics were determined at n1 in the same manner as in Example 1, the following results were obtained.

Voc=1. OV Jsc-1,3nA/cshff-0,21 η″-o, otg% Example 4 Example 1 except that the azo pigment in Example 1 was changed to the following.
A sample was prepared in the same manner.

Monochromatic light of 600I was incident on this sample, and (Pin'-1
, 5 μw/cd), and the photoelectric conversion characteristics were measured in the same manner as in Example 1, and the following results were obtained.

Voc=0.119V Jsc-5,4nA/cd ff-0,22 η''-0,07% Example 5 Example 1 except that the azo pigment of Example 1 was changed to the following.
A sample was prepared in the same manner.

561) Monochromatic light of nrA is incident on this sample, and (Pln
When the photoelectric conversion efficiency was measured in the same manner as in Example 1, the following results were obtained.

Voc-0,92V Jsc-1,9nA/cd ff-0,21 η--0,023% Example 6 Example 1 except that the azo pigment in Example 1 was changed to the following.
A sample was prepared in the same manner.

Monochromatic light of 640 μ is incident on this sample, and (Pin'-1
, 4 μw/cJ), and the photoelectric conversion efficiency was measured in the same manner as in Example 1, and the following results were obtained.

Woe-0,88V Jdc-8,3nA/c sirr-0,20 η ゛ -0,08% Example 7 Example 1 except that the azo pigment of Example 1 was changed to the following.
A sample was prepared in the same manner.

Monochromatic light of 640 m was incident on this sample, and (P1n'-1
, 4 μW/cd), and the photoelectric conversion efficiency was measured in the same manner as in Example 1, and the following results were obtained.

Voc=0.97V Jsc-2,3nA/cJ ff-0,23 Cou-0,037% Example 8 680m5 except that the azo pigment of Example 1 was changed to the following.
+ monochromatic light is incident on this sample, (Pln'-t, aμ
w/cj), and the photoelectric conversion efficiency was measured in the same manner as in Example 1, and the following results were obtained.

Voc-0,93V Jsc-3,9nA/cd fr-0,23 η--0.084% Example 9 Example 1 except that the azo pigment in Example 1 was changed to the following.
A sample was prepared in the same manner.

Monochromatic light of B[1OiI11 is incident on this sample, and (Pl
When the photoelectric conversion rate was measured in the same manner as in Example 1, the following results were obtained.

Voc-0,8AV Jsc-7,OnA/c rf-0,20 η=-0,69% Example 10 Example 1 except that the azo pigment in Example 1 was changed to the following.
A sample was prepared in the same manner.

Monochromatic light of 700μ is incident on this sample, and (Pin'-1
When the photoelectric conversion efficiency was measured in the same manner as in Example 1, the following results were obtained.

voe-[1,94V Jsc-1,8nA/c+# rfso 0.22 η=-0,029% [Effect] As described above, according to the present invention, the liquid in which the azo pigment is dispersed can be simply Since a photoactive layer can be produced by coating, a photoelectric conversion element with a large area can be produced at low cost. Also,
A photoelectric conversion element having high conversion efficiency over all visible light can be created. Furthermore, a photoelectric conversion element well suited to the solar spectrum can be provided.

[Brief explanation of the drawing]

FIGS. 1a to 3 are schematic diagrams showing cross sections of the photoelectric conversion element of the present invention. ■...Transparent front electrode, 2...Photoactive layer (I)
3... Photoactive layer (n), 4... Back electrode 5... Front electrode support, 6... Back electrode support.

Claims (1)

[Claims] The photoactive layer is an azo pigment represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents a coupler residue, and n represents an integer from 0 to 4] A photoelectric conversion element characterized by comprising: