JP2006086160A - Photoelectric conversion film, photoelectric conversion element and imaging element, and method of applying electric field to them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion film in which a half-value width of absorption is narrow, which is excellent in color reproduction and which further has a high photoelectric conversion efficiency and to provide a photoelectric conversion element and an imaging element (preferably a color image sensor), etc. <P>SOLUTION: The photoelectric conversion film includes at least one merocyanine dye. The photoelectric conversion element and the imaging element, and a method of applying an electric field to them are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photoelectric conversion film, a photoelectric conversion element having the photoelectric conversion film, a solid-state imaging element, and a method for applying an electric field to them.

  The photoelectric conversion film is widely used for, for example, an optical sensor, and is particularly preferably used as a solid-state imaging element (light-receiving element) of an imaging apparatus (solid-state imaging apparatus) such as a television camera. As a material of a photoelectric conversion film used as a solid-state imaging element of an imaging device, an inorganic material film such as a Si film or an a-Se film is mainly used.

  Conventional photoelectric conversion films using these inorganic material films do not have a steep wavelength dependence on the photoelectric conversion film characteristics. For this reason, an image pickup apparatus using a photoelectric conversion film has a three-plate structure including a prism that separates incident light into three primary colors of red, green, and blue, and three photoelectric conversion films that are arranged at the subsequent stage of the prism. Things have become mainstream.

  However, this three-plate type imaging device cannot avoid an increase in size and mass due to its structure.

  In order to reduce the size and weight of the image pickup apparatus, it is not necessary to provide a spectroscopic prism, and a single plate structure with one light receiving element is desired. For example, red, green, and blue filters are used for the single plate light receiving element. An image pickup device having a structure in which the structure is arranged is studied, and as a material of the photoelectric conversion film, there are various kinds and characteristics, and it is also considered to use an organic material having advantages such as a large degree of freedom of processing shape, Japanese Unexamined Patent Application Publication No. 2003-158254 discloses a photoelectric conversion film with improved photosensitivity (sensitivity) and a light receiving element using the photoelectric conversion film. In this document, an organic material is used as the p-type semiconductor and the n-type semiconductor. However, in the example of the publication, polymethylphenylsilane (PMPS) is used as the p-type organic material, and 8-hydroxyquinoline is used as the n-type organic material. Only an example in which 5.0 parts by mass of coumarin 6 as an organic dye is added to 100 parts by mass of the above PMPS using an aluminum complex (Alq3) is described. The description in the paragraph also describes that the organic dye is preferably used in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the p-type or n-type organic material constituting the photoelectric conversion film. Or there is no description of using as an n-type organic material.

Further, in order to realize a reduction in size and weight of the imaging apparatus, it is not necessary to provide a spectroscopic prism, and a low-resolution stacked photoelectric conversion film is disclosed as a single-plate structure having one light receiving element. It is described in the gazette. In this document, for example, a preferable stacked photoelectric conversion film absorbs light of a wavelength of any one of the three primary colors of light and a light of a wavelength of another color. It is described that a color image having high sensitivity and resolution can be obtained by laminating a photoelectric conversion film having a function of absorbing and a photoelectric conversion film having a function of absorbing the remaining light of one color. .
However, in the example of the publication, a coumarin 6 / polysilane film having photosensitivity in the entire blue region of 500 nm or less and a ZnPc / Alq3 film having an absorption region in the blue region together with the red region are used as the photoelectric conversion film. 6 / Only the photoelectric conversion film having photosensitivity only in the substantially red region centering on 600 to 700 nm is described due to the filter function of the polysilane film.

Japanese Patent Application Laid-Open No. 2003-332551 describes a stacked photoelectric conversion film similar to that described in Japanese Patent Application Laid-Open No. 2003-234460. However, Patent Documents 1 to 3 described above do not describe that the dye of the present invention gives preferable performance.
JP 2003-158254 A JP 2003-234460 A JP 2003-332551 A

  An object of the present invention is to provide a photoconductive film, a photoelectric conversion element, and an image pickup element (preferably a color image sensor) having a narrow half width of absorption and excellent color reproduction and high photoelectric conversion efficiency.

The present invention is solved by the following means.
(1) A photoelectric conversion film having an organic pn junction of an organic p-type semiconductor and an organic n-type semiconductor, comprising at least one merocyanine dye.
(2) The photoelectric conversion film according to (1), wherein the merocyanine dye according to (1) is represented by the following general formula (A).
Formula (A)

In formula (A), L ₁₀₈ , L ₁₀₉ , L ₁₁₀ and L ₁₁₁ each independently represent a methine group. p ₁₀₃ represents 0 or 1; q ₁₀₁ represents 0 or 1. n ₁₀₂ represents 0, 1, 2, 3 or 4. Z ₁₀₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. Z ₁₀₄ and Z ₁₀₄ ′ together with (N—R ₁₀₄ ) q ₁₀₁ represent an atomic group necessary for forming a ring or an acyclic acidic end group. However, Z ₁₀₃ and Z ₁₀₄ and Z ₁₀₄ ′ may be condensed or may have a substituent. M ₁₀₂ represents a charge balancing counter ion, m ₁₀₂ represents a number of 0 or more necessary for neutralizing the molecular charge. R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
(3) The photoelectric conversion film according to (1) or (2), wherein the merocyanine dye-containing layer has a thickness of 30 nm to 300 nm.
(4) A photoelectric conversion element comprising the photoelectric conversion film according to any one of (1) to (3) and a pair of electrodes sandwiching the photoelectric conversion film.
(5) An imaging device including the photoelectric conversion device according to (4).
(6) Two or more layers of the photoelectric conversion elements according to (4) are stacked. (5) An imaging element.
(7) The imaging element according to (6), wherein the photoelectric conversion element having two or more layers according to (6) includes three layers of a blue photoelectric conversion element, a green photoelectric conversion element, and a red photoelectric conversion element. .
(8) When the spectral absorption maximum values are λmax1, λmax2, and λmax3 in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), λmax1 is 400 nm to 500 nm and λmax2 is (5) The imaging device according to (7), wherein 500 nm to 600 nm and λmax3 are in the range of 600 nm to 700 nm.
(9) When the spectral sensitivity maximum values are Smax1, Smax2, and Smax3 in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), Smax1 is 400 nm to 500 nm, and Smax2 is The imaging device according to (7), wherein the imaging element is in a range of 500 nm to 600 nm and Smax3 is in a range of 600 nm to 700 nm.
(10) The interval between the shortest wavelength and the longest wavelength that indicates 50% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to (7) is 120 nm or less, respectively. (7) The imaging device according to (7).
(11) The interval between the shortest wavelength and the longest wavelength, which indicates 50% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), is 120 nm or less, respectively. (7) The imaging device according to (7).
(12) The interval between the shortest wavelength and the longest wavelength that indicates 80% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to (7) is 20 nm or more and 100 nm or less, respectively. (7) The imaging device according to (7).
(13) The interval between the shortest wavelength and the longest wavelength, which indicates 80% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), is 20 nm or more and 100 nm or less, respectively. (7) The imaging device according to (7).
(14) The interval between the shortest wavelength and the longest wavelength, which indicates 20% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), is 180 nm or less, respectively. (7) The imaging device according to (7).
(15) The interval between the shortest wavelength and the longest wavelength, which indicates 20% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), is 180 nm or less, respectively. (7) The imaging device according to (7).
(16) In the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7), the longest wavelengths indicating 50% of the spectral maximum absorption are 460 nm to 510 nm and 560 nm to 610 nm, respectively. 640 nm or more and 730 nm or less, The imaging device as described in (7) characterized by the above-mentioned.
(17) The longest wavelength showing 50% of the spectral maximum sensitivity in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element described in (7) is 460 nm to 510 nm and 560 nm to 610 nm, respectively. 640 nm or more and 730 nm or less, The imaging device as described in (7) characterized by the above-mentioned.
(18) A method of applying an electric field of 10 V / m or more and 1 × 10 ¹² V / m or less to the photoelectric conversion film, the photoelectric conversion element, or the imaging element according to (1) to (17).

The photoconductive film, photoelectric conversion element, and imaging element of the present invention have a narrow half-width of absorption and excellent color reproduction, and further have the effect of high photoelectric conversion efficiency. However, in the BGR three-layer stacked solid-state imaging element, other than that Has the following characteristics.
Because of the three-layer structure, there is no moiré and no optical low-pass filter is required, so the resolution is high and there is no color blur. Further, signal processing is simple and no pseudo signal is generated. Furthermore, in the case of CMOS, pixel mixing is easy and partial reading is easy.
Since the aperture ratio is 100% and no microlens is required, there is no limitation on the exit pupil distance with respect to the imaging lens, and no shading. Therefore, it is suitable for a lens interchangeable camera, and in this case, the lens can be thinned.
Since there is no microlens, it is possible to seal the glass by filling the adhesive, reducing the package thickness, increasing the yield, and reducing the cost.
Because of the use of a merocyanine dye, high sensitivity is obtained, no IR filter is required, and flare is reduced.

  In the present invention, a merocyanine dye is used. These may be used as either a p-type organic dye or an n-type organic dye, but are preferably used as a p-type dye. As the merocyanine dye, any pigment may be used, but the case represented by the general formula (A) is preferable.

Details of these merocyanine dyes are described in the following dye literature.
[Dye literature]
FMHarmer, `` Heterocyclic Compounds-Cyanine Dyes and Related Compounds, '' John Wiley & Sons -New York, London, 1964, DMSturmer, "Heterocyclic Compounds-Special topics in cyclic chemistry", Chapter 18. , Pp. 482-515, John Wiley & Sons-New York, London, 1977, "Rodd's Chemistry of Carbon Compounds" 2nd.Ed.vol.IV, part B, 1977, Chapter 15, 369 from 422 pp., Elsevier Science Public Company, Inc. (Elsevier Science Publishing Company Inc.) published by, New York, and so on.

  Hereinafter, the merocyanine dye represented by formula (A) will be described in detail.

  In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. In addition, the substituent that can be used in the compound in the present invention may be any substituent.

When such a substituent is W, the substituent represented by W is not particularly limited, and examples thereof include halogen atoms, alkyl groups (cycloalkyl groups, bicycloalkyl groups, tricycloalkyl groups). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group) ), Ammonio group, acylamino group, aminocarbonyl group Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), other known Substituents are mentioned as examples.

  More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group)], an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted, aromatic or non-aromatic heterocycles) A monovalent group obtained by removing one hydrogen atom from a ring compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl and 2-thienyl. 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-pyridinio, 1-methyl-2-quinolinio A thione heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, iso Propoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4- t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy A group (preferably a substitution of 2 to 30 carbon atoms or Unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N- -Octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy) An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ), An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as amino, Tilamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), ammonio group (preferably ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, heterocyclic ring substituted ammonio group, for example, Trimethylammonio, triethylammonio, diphenylmethylammonio), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonylamino groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably carbon A substituted or unsubstituted aminocarbonylamino having a number of 1 to 30, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably having a carbon number) 2 to 30 substituted or unsubstituted alkoxycarbonylamino groups such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino groups (Preferably, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, N -N-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, Methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio) ), A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably carbon 0 or 30 substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N -Benzoylsulfamoyl, N- (N'-pheny Carbamoyl) sulfamoyl), sulfo groups, alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, Ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, 7 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyl group, a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl , Pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl Ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl), N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substitutions having 3 to 30 carbon atoms) Or an unsubstituted heterocyclic azo group such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), Phosphino group (preferably having 2 carbon atoms 30 substituted or unsubstituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl, Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxy Phosphinyloxy), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phospho group A silyl group (preferably having 3 to 30 substituted or unsubstituted silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino groups (preferably substituted or unsubstituted hydrazino groups having 0 to 30 carbon atoms such as trimethylhydrazino) , A ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido).

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or naphthalene. Ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, thian Ren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

Among the above substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents, -CONHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), or -SO ₂ NHSO ₂ - group (sulfonylsulfamoyl Group).
More specifically, an alkylcarbonylaminosulfonyl group (eg, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (eg, benzoylaminosulfonyl group), an alkylsulfonylaminocarbonyl group (eg, methylsulfonylaminocarbonyl), or arylsulfonyl An aminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

Z ₁₀₃ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, preferably a 5- or 6-membered nitrogen-containing heterocyclic ring. However, these may have a substituent on which a ring may be condensed. The ring may be either an aromatic ring or a non-aromatic ring, and may be either a hydrocarbon ring or a heterocyclic ring. An aromatic ring is preferred, and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring. Examples of the substituent include the aforementioned W.

  Specific examples of nitrogen-containing heterocycles include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole Nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, pyrroline nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4 -Quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, pyrazole nucleus, tetrazole nucleus, pyrimidine nucleus, and the like are preferable. Is the benzothiazole nucleus, benzoo Sazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus Or a 3-isoquinoline nucleus.

  These may be substituted or condensed with the above-described substituent represented by W and the ring. Preferred are an alkyl group, an aryl group, an aromatic heterocyclic group (preferably 5 members), an alkoxy group, a halogen atom, an aromatic ring condensation, a sulfo group, a carboxyl group, or a hydroxyl group.

Specific examples of the heterocyclic ring formed by Z ₁₀₃ is, Z ₁₁ of U.S. Patent No. 5,340,694 No. 23-24 _{column, Z 12, Z 13, Z} 14, and are mentioned as examples of Z ₁₆ The thing similar to what is there is mentioned.

Z ₁₀₃ is preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine) or a benzimidazole nucleus, more preferably a benzoxazole nucleus, a benzothiazole nucleus, Or a 3,3-dialkylindolenine nucleus, particularly preferably a benzoxazole nucleus or a benzothiazole nucleus. The substituent W on these nuclei is preferably a halogen atom, an aryl group, an aromatic heterocyclic group (preferably a 5-membered), or an aromatic ring condensation, particularly preferably a 5-membered aromatic heterocyclic group, or It is an aromatic ring condensation of two or more rings. The 5-membered aromatic heterocyclic group is preferably a furan ring, a thiophene ring, or a pyrrole ring, and the aromatic ring condensation of two or more rings is preferably a benzofuran ring condensation. Examples of these substituents or condensed rings include the aforementioned W. The substitution position is preferably the 5-position.

Z ₁₀₄ , Z ₁₀₄ ′, and (N—R ₁₀₄ ) q ₁₀₁ each represent a group of atoms necessary to form a ring or an acyclic acidic end group. Here, any ring may be used, but a heterocyclic ring (preferably a 5- or 6-membered heterocyclic ring) is preferable, and an acidic nucleus is more preferable. Next, an acidic nucleus and an acyclic acidic terminal group will be described. The acidic nuclei and acyclic acidic end groups can take the form of the acidic nuclei and acyclic acidic end groups of any common merocyanine dye. In a preferred form, _Z104 is a thiocarbonyl group represented by-(C = S)-(including thioester group, thiocarbamoyl group, etc.), a carbonyl group represented by-(C = O)-(ester group, carbamoyl). A sulfonyl group (including a sulfonate group, a sulfamoyl group, etc.) represented by-(SO ₂ )-, a sulfinyl group represented by-(S═O)-, or a cyano group. And more preferably a thiocarbonyl group or a carbonyl group. Z ₁₀₄ ′ represents the remaining atomic group necessary to form an acidic nucleus and an acyclic acidic end group. In the case of forming an acyclic acidic terminal group, a thiocarbonyl group, a carbonyl group, a sulfonyl group, a sulfinyl group, a cyano group and the like are preferable. In addition, these acidic nuclei, or the carbonyl group or thiocarbonyl group forming the acyclic acidic terminal group, can be converted into the active methylene position of the active methylene compound that is the raw material of the acidic nucleus or the acyclic acidic terminal group. It is also possible to use a structure having exomethylene substituted with and a structure in which these are repeated. When an acidic nucleus is substituted with an acidic nucleus, a so-called trinuclear merocyanine, tetranuclear merocyanine, or the like is formed as a dye. What you have.
q ₁₀₁ is 0 or 1, but preferably 1.

  The acidic nuclei and acyclic acidic terminal groups mentioned here are, for example, “The Theory of the Photographic Process” edited by James, 4th edition, Macmillan Publishing Co., Ltd. 1977, pp. 197-200. Here, an acyclic acidic terminal group means an acidic or electron-accepting terminal group that does not form a ring. Acid nuclei and acyclic acidic end groups are specifically described in U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862. No. 4,002,480, No. 4,925,777, JP-A-3-167546, US Pat. No. 5,994,051, US Pat. No. 5,747,236, etc. Can be mentioned.

  The acidic nucleus is preferred when forming a heterocycle (preferably a 5- or 6-membered nitrogen-containing heterocycle) composed of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. More preferably, when forming a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms. Specifically, for example, the following nuclei can be mentioned.

  2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one, 2-thiooxazolidine -2,5-dione, 2-thiooxazoline-2,4-dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2, 4-dione, rhodanine, thiazolidine -2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxo Indazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo 3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, Chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] benzimidazole , Pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethine-2,3- Dihydrobenzo [d] thiophene-1, 1-dioxide nucleus.

  These acidic nuclei and acyclic acidic end groups may be condensed with a ring or may be substituted with a substituent (for example, the aforementioned W).

  Preferably as the acidic nucleus, hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2, 4-dione, thiazolidine-2, 4-dione, rhodanine, thiazolidine-2, 4- Dithione, barbituric acid, or 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, or 2-thiobarbituric acid Particularly preferred is 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, or barbituric acid, and most preferred is barbituric acid.

R ₁₀₃ and R ₁₀₄ are each independently a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, preferably an alkyl group, an aryl group, and a heterocyclic group. Specific examples of the alkyl group, aryl group, and heterocyclic group represented by R ₁₀₃ and R ₁₀₄ include, for example, preferably 1 to 18 carbon atoms, more preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. An unsubstituted alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), preferably 1 to 18, more preferably 1 to 7, particularly preferably 1 to 4. Substituted alkyl group {for example, an alkyl group substituted with the aforementioned W as a substituent. Preferably an aralkyl group (eg benzyl, 2-phenylethyl, 2- (4-biphenyl) ethyl, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 4-phosphobenzyl, 4-carboxybenzyl), unsaturated A hydrocarbon group (for example, an allyl group, a vinyl group, that is, a substituted alkyl group also includes an alkenyl group and an alkynyl group), a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), An alkyl group substituted with an acid group, a carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxy) Ethoxy) ethyl), aryloxyalkyl groups (eg 2-phenoxyethyl, 2- (4-biphenyloxy) ethyl, 2- (1-naphthoxy) ethyl, 2- (4-sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl), an alkoxycarbonylalkyl group (for example, Ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl groups (eg 3-phenoxycarbonylpropyl, 3-sulfophenoxycarbonylpropyl), acyloxyalkyl groups (eg 2-acetyloxyethyl), acylalkyl groups (eg 2-acetylethyl), a carbamoylalkyl group (for example, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (for example, N, N-dimethylsulfamoylmethyl), a sulfoalkyl group (for example, 2-sulfoethyl, 3 Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 3-phenyl-3-sulfopropyl, 4-phenyl- 4-sulfobutyl, 3- (2-pyridyl) -3-sulfopropyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), hetero Ring-substituted alkyl groups (for example 2- (pyrrolidin-2-one-1-yl) ethyl, 2- (2-pyridyl) ethyl, tetrahydrofurfuryl, 3-pyridiniopropyl), alkylsulfonylcarbamoylalkyl groups (for example methane Sulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (for example, Acetylcarbamoylmethyl group), acylsulfamoylalkyl group (for example, acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (for example, methanesulfonylsulfamoylmethyl group), ammonioalkyl group (for example, 3- (Trimethylammonio) propyl, 3-ammoniopropyl), aminoalkyl groups (eg, 3-aminopropyl, 3- (dimethylamino) propyl, 4- (methylamino) butyl), guanidinoalkyl groups (eg, 4-aminopropyl) Guanidinobutyl)}, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, substituted or unsubstituted aryl groups (examples of substituted aryl groups include substituent groups) As mentioned above, the aryl group substituted by the aforementioned W is exemplified. It is. Specific examples include phenyl, 1-naphthyl, p-methoxyphenyl, p-methylphenyl, p-chlorophenyl, biphenyl, 4-sulfophenyl, 4-sulfonaphthyl and the like. ), Preferably 1 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 4 to 8 carbon atoms, a substituted or unsubstituted heterocyclic group (the substituted heterocyclic group is exemplified as a substituent) Specific examples include heterocyclic groups substituted with the aforementioned W. Specifically, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2 -Thiazolyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl, 5-methyl-2-thienyl , 4-methoxy-2-pyridyl, 4-sulfo-2-pyridyl, etc.).
The above acid group will be described. An acid group is a group having a dissociable proton.
Specifically, for example, sulfo group, carboxyl group, sulfato group, —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group ( Sulfonylsulfamoyl groups), sulfonamido groups, sulfamoyl groups, phosphato groups, phosphono groups, boronic acid groups, phenolic hydroxyl groups, and the like, groups that can dissociate protons depending on their pka and surrounding pH. For example, a proton dissociable acidic group capable of dissociating 90% or more between pH 5-11 is preferable. More preferred are a sulfo group, a carboxyl group, a —CONHSO ₂ — group, a —CONHCO— group, and a —SO ₂ NHSO ₂ — group.

The substituent represented by R ₁₀₃ and R ₁₀₄ is preferably an unsubstituted alkyl group or a substituted alkyl group.

_{L 108, L 109, L 110} , and L ₁₁₁ each independently represents a methine group. The methine group represented by L _{108 to} L ₁₁₁ may have a substituent, and examples of the substituent include W described above. For example, a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (for example, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted carbon An aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 carbon atoms To 15, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), 1 to 15 carbon atoms, preferably carbon An alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms More preferably an amino group having 4 to 10 carbon atoms (for example, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. More preferably, it is an alkylthio group having 1 to 5 carbon atoms (for example, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (for example, phenylthio, p- Methylphenylthio) and the like. A ring may be formed with other methine groups, or a ring may be formed with Z ₁₀₃ , Z ₁₀₄ , Z _{104 ′} , R ₁₀₃ , R ₁₀₄ .

L ₁₀₈ and L ₁₀₉ are preferably an unsubstituted methine group.

n ₁₀₂ represents 0, 1, 2, 3 or 4. Preferred as n ₁₀₂ is 0, 1, 2, 3, more preferably 1, 2, particularly preferably 0 or 1,. When _n102 is 2 or more, the methine group is repeated but need not be the same.

p ₁₀₃ represents 0 or 1; Preferably it is 0.

_M102 is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (for example, p-toluenesulfonate ion, p- Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

m ₁₀₂ represents a number of 0 or more necessary for balancing the charge, a number of preferably 0-4, more preferably a number of 0 to 1, in the case of forming the salt in a molecule 0 It is.

  Next, specific examples of merocyanine dyes that are particularly preferably used in the present invention are shown below. Of course, the present invention is not limited to these.

[Definition of J-aggregate formation state of dye]
The dye of the present invention is preferably in a state in which a J aggregate is formed in the photoelectric conversion film. Here, the state in which the dye forms a J-aggregate is a state in which the absorption maximum value is shifted to the long wavelength side from the absorption maximum value indicated by the monomer solution without interaction between the dyes. Define that there is. The shift width is preferably 10 nm or more, more preferably 25 nm or more, particularly preferably 50 nm or more, and most preferably 75 nm or more. The upper limit of the shift width is not particularly limited, but is preferably 200 nm or less, and more preferably 150 nm or less. In general, it is known that when a dye forms a J-aggregate, the absorption maximum shifts to a longer wavelength side as compared with the monomer state. (The Theory of the Photographic Process, edited by TH James, 1977, Macmillan Publishing Co., Inc.) Therefore, the J meeting can be defined by the above definition.
The absorption maximum value exhibited by the dye solution in the monomer state means the absorption maximum value in a dimethylformamide (DMF) solution having a dye concentration = 1 × 10 ⁻⁵ mol / l. When the dye does not dissolve in DMF, chloroform, methylene chloride, dimethyl sulfoxide, or methanol may be used as a solvent.

Further, when the absorption width on the long wavelength side of the absorption of the J aggregate of the dye formed in the photoelectric conversion film is not more than twice the absorption width on the long wavelength side of the absorption exhibited by the dye solution in the above monomer state Is preferred. More preferably, it is 1.5 times or less, particularly preferably 1 time or less, and most preferably 0.5 times or less. Here, the absorption width on the long wavelength side represents the energy width between the absorption maximum wavelength and a wavelength that is longer than the absorption maximum wavelength and exhibits half the absorption maximum. In general, it is known that when a J aggregate is formed, the absorption width on the long wavelength side is smaller than that in the monomer state. However, in the photoelectric conversion film, when the dye does not form a J-aggregate, the non-uniform interaction between the dyes becomes strong, so the absorption becomes broad, and the absorption width on the long wavelength side of the dye solution in the monomer state The absorption width is more than twice as large as that of. Therefore, in the present invention, the above is defined as a preferable absorption width of the J aggregate.
As described above, the organic dye compound layer in which the J aggregates are formed may be partially included in the entire organic layer. Preferably, the proportion of the portion where the orientation is controlled with respect to the entire organic layer is 10% or more, more preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90%. Above, most preferably 100%.

  When the compound of the present invention forms a J-aggregate in the photoelectric conversion film, the photoelectric conversion efficiency is remarkably increased in addition to the advantage that the half width of absorption of the resulting photoelectric conversion film is narrow and the color reproducibility is excellent. Found it to be higher. Surprisingly, it has been found that the durability of the photoelectric conversion film is also significantly improved.

[Molecular weight]
We have found that the merocyanine dyes of the present invention have a preferred molecular weight range. The molecular weight is preferably 300 to 1200, more preferably 400 to 1000, and particularly preferably 500 to 800. When the molecular weight of the merocyanine dye of the present invention is in these ranges, in addition to the advantage that the film can be easily formed by vacuum deposition of the photoelectric conversion film, the photoelectric conversion efficiency of the obtained photoelectric conversion film is high and excellent, Furthermore, it has been found that the variation in the light absorption rate and the photoelectric conversion efficiency between the pixels of the image sensor is reduced.

[Providing hydrophobicity]
We have found that the merocyanine dyes of the present invention have a preferred hydrophilic / hydrophobic range. ClogP is preferably 2 or more and 10 or less, more preferably 3 or more and 8 or less, and particularly preferably 4 or more and 6 or less. When the hydrophilicity / hydrophobicity of the compound of the present invention is within these ranges, in addition to the advantage that the film can be easily formed by vacuum deposition or the like of the photoelectric conversion film, the photoelectric conversion efficiency of the obtained photoelectric conversion film is high and excellent. Furthermore, it has been found that the variation in the light absorption rate and the photoelectric conversion efficiency between the pixels of the image sensor is reduced. Moreover, when the hydrophilicity / hydrophobicity of the compound of this invention exists in these ranges, it discovered that durability of the film | membrane obtained, especially the durability under high-humidity conditions improved.

ClogP is used as a measure of the hydrophilicity / hydrophobicity of a compound.
Usually, hydrophilicity / hydrophobicity can be determined by the octanol / water partition coefficient (logP) of a compound. Specifically, it can be obtained by actual measurement by the flask-shaking method described in the following document (1).
Reference (1): Structure-activity relationship social gathering (representative) Ikuo Fujita, edited by Chemistry Special Issue 122 “Structure-activity relationship of drugs-Guidelines for drug design and mechanism of action research”, Nanedo, 1979, Chapter 2 Pages 43-203. In particular, Flask Shaking is described on pages 86-89.

Since the measurement may be difficult when logP is 3 or more, a model for calculating logP can be used in the present invention. In the present invention, logP (hereinafter referred to as ClogP) based on this calculated value is used. Can be defined using.
For the purpose of the present invention, the logP calculation value is calculated using Hansch-Leo's CLOGP program (Daylight Chemical Information Systems, USA) (version is algorithm = 4.01, fragment database = 17 (* 3)). If this software is not available, Applicants will provide their ClogP values for all specific compounds.
If multiple tautomers can be taken in the merocyanine dye of the present invention, ClogP can be calculated for each of these isomers, and if at least one of these values is within a particular range, the compound Is within the preferred range of the present invention. Further, when there is no molecular fragment in the database of the above program, ClogP can be obtained by supplementing the data by actual measurement of the hydrophilicity / hydrophobicity. The merocyanine dye of the present invention calculates ClogP based on the state at pH = 7.

〔potential〕
We have further found that the merocyanine dyes of the present invention have a preferred potential range. The oxidation potential is preferably 0.3 to 1.8 V (vs SCE), more preferably 0.5 to 1.5 V, and particularly preferably 0.8 to 1.3 V. The reduction potential is preferably -2 to -0.5 V (vs SCE), more preferably -1.6 to -0.8 V, and particularly preferably -1.4 to -1 V.
It has been found that when the potential of the merocyanine dye of the present invention is in these ranges, the durability of the photoelectric conversion film is improved in addition to the advantage that the photoelectric conversion efficiency of the obtained photoelectric conversion film is increased.

  Various methods can be used to measure the reduction potential and the oxidation potential. Preferably, the reduction potential and the oxidation potential are measured by phase discrimination type second harmonic AC polarography, and an accurate value can be obtained. The method of measuring the potential by the above-described phase discrimination type second harmonic alternating current polarography is described in Journal of Imaging Science, Volume 30, Page 27 (1986). Yes.

〔fluorescence〕
We have further found that the merocyanine dyes of the present invention have a preferred fluorescence quantum yield and fluorescence lifetime range. The fluorescence quantum yield is preferably 0.1 to 1, more preferably 0.5 to 1, and particularly preferably 0.8 to 1. The fluorescence lifetime is preferably 10 ps or more, more preferably 40 ps or more, and particularly preferably 160 ps or more. There is no particular upper limit, but it is preferably 1 ms or less.
When the fluorescence quantum yield and fluorescence lifetime of the merocyanine dye of the present invention are in these ranges, in addition to the advantage that the photoelectric conversion efficiency of the obtained photoelectric conversion film is increased, the durability of the photoelectric conversion film is improved. I found it.

  The fluorescence quantum yield can be measured by the method described in JP-A-63-138341. The method is described below. The fluorescence quantum yield in the dye film can be measured by basically the same method as in the case of the luminescence quantum yield of the solution. , 10-diphenylanthracene, etc.), and relative measurement comparing the incident light intensity and the light emission intensity of the sample under a fixed optical arrangement. This relative measurement method is described in, for example, C. A. Parker and W. T. Rees, Analyst, 1960, vol. 85, page 587. The fluorescence quantum yield in the present invention may be either a solution state or a film state value, but is preferably a value in the film state.

  The fluorescence lifetime of the merocyanine dye of the present invention can be measured by the method described by Tadaaki Tani, Takeshi Suzumoto, Klaus Kemnitz, Keitaro Yoshihara, The Journal of Physical Chemistry, 1992, 96, 2778.

[Absorption wavelength regulation]
We have further found that the merocyanine dyes of the present invention have a preferred spectral absorption wavelength and spectral sensitivity range.
In the present invention, a BGR photoelectric conversion film with good color reproduction, that is, a photoelectric conversion element in which three layers of a blue photoelectric conversion film, a green photoelectric conversion film, and a red photoelectric conversion film are stacked can be preferably used. Each photoelectric conversion film preferably has the following spectral absorption and / or spectral sensitivity characteristics.
When the spectral absorption maximum values are λmax1, λmax2, and λmax3 in the order of BGR, and the spectral sensitivity maximum values are Smax1, Smax2, and Smax3 in the order of BGR, λmax1 and Smax1 are preferably 400 nm to 500 nm, and more preferably 420 nm or more It is a case where it exists in the range of 430 nm or more and 470 nm or less especially preferably. λmax2 and Smax2 are preferably in the range of 500 nm to 600 nm, more preferably 520 nm to 580 nm, and particularly preferably 530 nm to 570 nm. λmax3 and Smax3 are preferably 600 nm to 700 nm, more preferably 620 nm to 680 nm, and particularly preferably 630 nm to 670 nm.

Further, when the photoelectric conversion film of the present invention has a laminated structure of three or more layers, the shortest wavelength and the longest wavelength exhibiting 50% of the spectral maximum absorption of λmax1,2,3 and the spectral maximum sensitivity of Smax1,2,3, respectively. The wavelength interval is preferably 120 nm or less, more preferably 100 nm or less, particularly preferably 80 nm or less, and most preferably 70 nm or less.
Further, the interval between the shortest wavelength and the longest wavelength that shows 80% of the spectral maximum absorption of λmax1,2,3 and the spectral maximum sensitivity of Smax1,2,3 is preferably 20 nm or more, preferably 100 nm or less, more preferably Is 80 nm or less, particularly preferably 50 nm or less.
Further, the interval between the shortest wavelength and the longest wavelength that shows 20% of the spectral maximum absorption of λmax1,2,3 and the spectral maximum sensitivity of Smax1,2,3 is preferably 180 nm or less, more preferably 150 nm or less, and particularly preferably Is 120 nm or less, most preferably 100 nm or less.
In addition, on the long wave side of λmax1,2,3 and Smax1,2,3, the longest wavelength showing the spectral absorption of λmax1,2,3 and the spectral absorption of 50% of the spectral maximum of Smax1,2,3 is λmax1 and Smax1 are preferably 460 nm to 510 nm, λmax2 and Smax2 are preferably 560 nm to 610 nm, and λmax3 and Smax3 are preferably 640 nm to 730 nm.
When the spectral absorption wavelength and spectral sensitivity range of the compound of the present invention are within these ranges, the color reproducibility of the color image obtained by the imaging device can be improved.

[Angle definition of spectral absorption transition dipole moment of dye compounds]
We have further found that there is a preferred range for the angle formed by the spectral absorption transition dipole moment of the dye compound of the present invention and the electrode plane of the photoelectric conversion element.
The angle formed by the spectral absorption transition dipole moment of the dye compound of the present invention and the electrode plane of the photoelectric conversion element is preferably 60 ° or less, more preferably 50 ° or less, further preferably 40 ° or less, and more preferably 30. It is at most 0 °, more preferably at most 15 °, further preferably at most 5 °, particularly preferably at most 2 °, most preferably at 0 °.
When the angle between the spectral absorption transition dipole moment of the compound of the present invention and the electrode plane of the photoelectric conversion element is in these ranges, the photoelectric conversion efficiency of the obtained photoelectric conversion film is remarkably increased, and surprisingly It has been found that the light absorption rate is also significantly improved.

Conventionally, little attention has been paid to the orientation of the organic photoelectric conversion element in the film. The transition dipole moment of the dye molecule is in the long axis direction of the particle, and when the dye in the photoelectric conversion film forms an angle with the electrode plane of the photoelectric conversion element, the transition dipole moment of the dye and the electrode plane of the photoelectric conversion element Is at an angle.
In the present invention, in order to improve the mobility of excitons and carriers in the dye generated by photoexcitation, the angle formed by the transition dipole moment of the dye and the electrode plane is an important parameter. It has been found that the photoelectric conversion efficiency is increased. When reviewing conventional organic photoelectric conversion elements from this viewpoint, it has become clear that there is no system in which the angle between the transition dipole moment of the dye and the electrode plane is nearly parallel, which is insufficient.
Furthermore, since light enters the photoelectric conversion element perpendicularly, the vibration plane of the electric field of the incident light is parallel to the photoelectric conversion element surface, that is, parallel to the electrode plane of the photoelectric conversion element. When the transition dipole moment of the dye and the electrode plane of the photoelectric conversion element are parallel to each other, it is clear that the light absorption efficiency is increased because it coincides with the electric field vibration plane of the incident light.

The transition dipole moment of the dye compound of the present invention can be determined, for example, by the following method. Experimental Physics Lecture 14, Kinoshita Yoshio edited by Kyoritsu Publishing Co., Ltd., 1986, measured the reflection spectrum of photoelectric conversion element using a 45-degree reflection optical system and an ultraviolet-visible spectrometer with a polarizer. To do. The reflection intensity (Ig (ν)) of light of p-polarized light and s-polarized light is measured in the range of 200 nm before and after the absorption wavelength of the dye. Further, the reflection intensity Iq (ν) of quartz as a standard material is measured by the same method. The refractive index n of quartz is obtained for each wave number (cm ^-1 ) by the following formula,
n ² = 1 + 1.2409 × 10 ¹⁰ / (106359 ² −ν ² )
From this, the reflectance (Rq (ν)) of quartz is
Rq (ν) = | (n−1) / (n + 1) | ²
The reflectance (Rg (ν)) of the photoelectric conversion element is
Rg (ν) = Rq (ν) × Ig (ν) / Iq (ν)
It can be obtained more. The above reflectance measurement is performed for both p-polarized light and s-polarized light, and the absorption spectrum for the p-polarized component and s-polarized component of the total absorption of the photoelectric conversion element by performing the Kramers-Kronig conversion (hereinafter referred to as KK conversion) on the reflected spectrum Ap (ν) and As (ν) can be obtained. The KK conversion is described in 4th edition, Experimental Chemistry Lecture 7 Spectroscopy II, Hiroo Iguchi, Maruzen Co., Ltd., 1992, P320. By performing the above measurement with an element obtained by removing only the dye compound of the present invention from the photoelectric conversion element, absorption spectra A1p (ν) and A1s ( ν) can be obtained in the same manner. The absorption spectrum of the dye alone is
p polarization component A2p (ν) = Ap (ν) − A1p (ν)
s polarization component A2s (ν) = As (ν) − A1s (ν)
You can ask. From these measurements, the angle between the electrode plane and the transition dipole moment of the dye is θ2ps (ν) = tan ^-1 (A2p (ν) / A2s (ν) − 1 / √2)
It becomes. In the present invention, the angle formed by the electrode plane and the transition dipole moment of the dye is defined as θ2ps (ν) at the absorption maximum wavelength of the dye.

Alternatively, A2p (ν) and A2s (ν) can be obtained by integrating Ap (ν) and As (ν) with the wavelength change component of the first derivative with respect to wavelength. The angle between the electrode plane and the transition dipole moment of the dye can also be obtained in the same manner as described above using A2p (ν) and A2s (ν).
θ2ps (ν) = tan ⁻¹ (A12p (ν) / A12s (ν) − 1 / √2)
It becomes.

[Electron transporting materials]
In the photoelectric conversion film of the present invention, the organic material (n-type compound) having an electron transporting property preferably has an ionization potential larger than 6.0 eV, and may be represented by the following general formula (X). I found it preferable.
Formula (X) L- (A) m
(In the formula, A represents a heterocyclic group in which two or more aromatic heterocycles are condensed, and the heterocyclic group represented by A may be the same or different. M represents an integer of 2 or more. L Represents a linking group.)
Details and preferred ranges of these organic materials having electron transport properties are described in detail in Japanese Patent Application No. 2004-082002.
It has been found that when these electron transporting organic materials are used, the photoelectric conversion efficiency of the obtained photoelectric conversion film is remarkably increased.
[General requirements]
In the present invention, it is preferable to use a photoelectric conversion element having at least two or more photoelectric conversion films, more preferably three or four layers, and particularly preferably three layers.

  In the present invention, these photoelectric conversion elements can be particularly preferably used as an imaging element.

  Moreover, in this invention, the case where a voltage is applied to these photoelectric conversion films, photoelectric conversion elements, and image sensors is preferable.

  The photoelectric conversion element in the present invention is preferably a case where a p-type semiconductor layer and an n-type semiconductor layer have a photoelectric conversion film having a stacked structure between a pair of electrodes. Preferably, at least one of the p-type and n-type semiconductors contains an organic compound, and more preferably, both the p-type and n-type semiconductors contain an organic compound.

[Apply voltage]
When a voltage is applied to the photoelectric conversion film of the present invention, it is preferable in terms of improving the photoelectric conversion efficiency. The applied voltage may be any voltage, but the required voltage varies depending on the film thickness of the photoelectric conversion film. That is, the photoelectric conversion efficiency improves as the electric field applied to the photoelectric conversion film increases, but the applied electric field increases as the film thickness of the photoelectric conversion film decreases even at the same applied voltage. Therefore, when the photoelectric conversion film is thin, the applied voltage may be relatively small. The electric field applied to the photoelectric conversion film is preferably 10 V / m or more, more preferably 1 × 10 ³ V / m or more, more preferably 1 × 10 ⁵ V / m or more, and particularly preferably 1 × 10 ⁶ V / m. m or more, most preferably 1 × 10 ⁷ V / m or more. The upper limit is not particularly since current even in a dark place when the electric field too added flows undesirable, 1 × preferably 10 ¹² V / m or less, preferably more 1 × 10 ⁹ V / m or less.

[Organic pn compound]
Any organic p-type semiconductor (compound) and organic n-type semiconductor (compound) may be used. In the case of using at least one compound (organic dye, preferably the merocyanine dye of the present invention) that has absorption in the visible and infrared regions, but preferably has absorption in the visible region. It is. Furthermore, a colorless p-type compound and an n-type compound may be used, and an organic dye (preferably the merocyanine dye of the present invention) may be added thereto.
In the case of a three-layer structure of p-type layer / bulk heterojunction layer / n-type layer, the p-type or n-type semiconductor (compound) on the incident light side is preferably colorless.

  The organic p-type semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound. For example, triphenylamines, benzidines, pyrazolines, styrylamines, hydrazones, triphenylmethanes, carbazoles, polysilanes, thiophenes, phthalocyanines, polyamines, and the like can be used. Not limited to this, as described above, any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor.

  Organic n-type semiconductors (compounds) are acceptor organic semiconductors (compounds), which are mainly represented by electron-transporting organic compounds and refer to organic compounds that easily accept electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound. For example, perylene derivatives, oxadiazole derivatives, triazole derivatives, triazines, quinoxalines, phenanthrolines, fullerenes, aluminum quinolines, and the like can be used. Note that the present invention is not limited thereto, and as described above, any organic compound having an electron affinity higher than that of the organic compound used as the donor organic compound may be used as the acceptor organic semiconductor.

  As a p-type organic dye or an n-type organic dye, a dye that can be used in combination with the merocyanine dye of the present invention, or another dye for a photoelectric conversion film, preferably a coumarin dye, an anthraquinone dye, a triphenylmethane dye, an azo dye Azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye, quinacridone dye, quinophthalone Examples thereof include dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes.

The layer containing these organic compounds is formed by a dry film formation method or a wet film formation method. Specific examples of the dry film forming method include a physical vapor deposition method such as a vacuum deposition method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization. As the wet film forming method, a casting method, a spin coating method, a dipping method, an LB method, or the like is used.
In the case of using a polymer compound as at least one of the p-type semiconductor (compound) or the n-type semiconductor (compound), it is preferable to form the film by a wet film forming method that is easy to create. When a dry film formation method such as vapor deposition is used, it is difficult to use a polymer because it may be decomposed, and an oligomer thereof can be preferably used instead. On the other hand, when a low molecule is used, it is preferable to form a film by a dry film forming method such as co-evaporation.

[Bulk heterojunction structure]
In the present invention, a p-type semiconductor layer and an n-type semiconductor layer are provided between a pair of electrodes, and at least one of the p-type semiconductor and the n-type semiconductor is an organic semiconductor, and these semiconductor layers It is preferable to contain a photoelectric conversion film (photosensitive layer) having a bulk heterojunction structure layer containing the p-type semiconductor and the n-type semiconductor as an intermediate layer. In such a case, in the photoelectric conversion film, by incorporating a bulk heterojunction structure in the organic layer, the disadvantage that the carrier diffusion length of the organic layer is short can be compensated, and the photoelectric conversion efficiency can be improved.
The bulk heterojunction structure is described in detail in Japanese Patent Application No. 2004-080639.

[Tandem structure]
In the present invention, a photoelectric conversion film (photosensitive layer) having a structure having two or more repeating structures (tandem structures) of a pn junction layer formed of a p-type semiconductor layer and an n-type semiconductor layer between a pair of electrodes ) Is preferable, and more preferably, a thin layer of a conductive material is inserted between the repetitive structures. The number of repeating structures (tandem structures) of the pn junction layer may be any number, but is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and particularly preferably 2 in order to increase the photoelectric conversion efficiency. Or 3, most preferably 3. Silver or gold is preferable as the conductive material, and silver is most preferable.
In the present invention, the semiconductor having a tandem structure may be an inorganic material, but is preferably an organic semiconductor, and more preferably an organic dye.
The tandem structure is described in detail in Japanese Patent Application No. 2004-079930.

(Orientation regulation)
The present invention relates to an imaging device having a photoelectric conversion film having a p-type semiconductor layer, an n-type semiconductor layer (preferably a mixed / dispersed (bulk heterojunction structure) layer) between a pair of electrodes, and the p-type semiconductor and n Preferred is a photoelectric conversion film characterized by containing an organic compound whose orientation is controlled in at least one of the type semiconductors, and more preferably, the orientation is controlled by both the p-type semiconductor and the n-type semiconductor (possible N) when an organic compound is included.
As the organic compound used in the organic layer of the photoelectric conversion film, one having π-conjugated electrons is preferably used, but this π-electron plane is not perpendicular to the substrate (electrode substrate) but oriented at an angle close to parallel. The better it is. The angle with respect to the substrate is preferably 0 ° or more and 80 ° or less, more preferably 0 ° or more and 60 ° or less, further preferably 0 ° or more and 40 ° or less, and further preferably 0 ° or more and 20 ° or less. Particularly preferably, it is 0 ° or more and 10 ° or less, and most preferably 0 ° (that is, parallel to the substrate).
As described above, the organic compound layer whose orientation is controlled may be partially included in the entire organic layer, but preferably the proportion of the portion whose orientation is controlled with respect to the entire organic layer is 10% or more. More preferably, it is 30% or more, more preferably 50% or more, further preferably 70% or more, particularly preferably 90% or more, and most preferably 100%.
Such a state compensates for the shortcoming of the short carrier diffusion length of the organic layer by controlling the orientation of the organic compound in the organic layer in the photoconductive film, and improves the photoelectric conversion efficiency.

In the case where the orientation of the organic compound of the present invention is controlled, it is more preferable that the heterojunction plane (for example, the pn junction plane) is not parallel to the substrate. It is more preferable that the heterojunction plane is oriented not at a parallel to the substrate (electrode substrate) but at an angle close to the vertical. The angle with respect to the substrate is preferably 10 ° or more and 90 ° or less, more preferably 30 ° or more and 90 ° or less, further preferably 50 ° or more and 90 ° or less, and further preferably 70 ° or more and 90 ° or less. Particularly preferably, it is 80 ° or more and 90 ° or less, and most preferably 90 ° (that is, perpendicular to the substrate).
The organic compound layer whose heterojunction surface is controlled as described above may be partially included in the entire organic layer. Preferably, the proportion of the portion where the orientation is controlled with respect to the entire organic layer is 10% or more, more preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90%. Above, most preferably 100%. In such a case, the area of the heterojunction surface in the organic layer increases, the amount of carriers of electrons, holes, electron-hole pairs, etc. generated at the interface increases, and the photoelectric conversion efficiency can be improved.
In the above-described photoconductive film (photoelectric conversion film) in which the orientation of both the heterojunction plane and the π-electron plane of the organic compound is controlled, it is possible to improve the photoelectric conversion efficiency.
These states are described in detail in Japanese Patent Application No. 2004-079931.

[Thickness regulation of organic dye layer]
When the photoelectric conversion film of the present invention is used as a color image sensor (image sensor), the light absorption rate of each of the organic dye layers of the B, G, and R layers is preferably 50% or more, more preferably 70% or more, and particularly preferably. Is preferably 90% (absorbance = 1) or more, most preferably 99% or more in order to improve the photoelectric conversion efficiency and to improve color separation without passing excess light through the lower layer. Therefore, in terms of light absorption, the larger the thickness of the organic dye layer is, the more preferable, but considering the ratio that does not contribute to charge separation, the thickness of the organic dye layer in the present invention is preferably 30 nm to 300 nm, more preferably 50 nm. ˜150 nm, particularly preferably 80 nm to 130 nm.
[About BGR spectroscopy]
In the present invention, a BGR photoelectric conversion film with good color reproduction, that is, a photoelectric conversion element in which three layers of a blue photoelectric conversion film, a green photoelectric conversion film, and a red photoelectric conversion film are stacked can be preferably used.
Each photoelectric conversion film preferably has, for example, the above-described spectral absorption and / or spectral sensitivity characteristics.

[Laminated structure]
In the present invention, it is preferable to use a photoelectric conversion element in which at least two photoelectric conversion films are laminated. There are no particular limitations on the multilayer imaging device, and any of those used in this field can be applied. However, a BGR three-layer structure is preferable, and a preferred example of the BGR multilayer structure is shown in FIG.
Next, the solid-state imaging device according to the present invention has, for example, a photoelectric conversion film as shown in this embodiment. In the solid-state imaging device as shown in FIG. 1, a stacked photoelectric conversion film is provided on the scanning circuit unit. The scanning circuit unit can appropriately adopt a configuration in which a MOS transistor is formed on a semiconductor substrate for each pixel unit, or a configuration having a CCD as an image sensor.
For example, in the case of a solid-state imaging device using a MOS transistor, charges are generated in the photoelectric conversion film by incident light transmitted through the electrodes, and the charges are generated by an electric field generated between the electrodes by applying a voltage to the electrodes. It travels to the electrode through the photoelectric conversion film, and further moves to the charge storage part of the MOS transistor, and charges are stored in the charge storage part. The charge accumulated in the charge accumulation unit moves to the charge readout unit by switching of the MOS transistor, and is further output as an electric signal. Thereby, a full-color image signal is input to the solid-state imaging device including the signal processing unit.
As these laminated image pickup devices, solid color image pickup devices represented by FIG. 2 of JP-A-58-103165, FIG. 2 of JP-A-58-103166, and the like can also be applied.

  The method described in JP-A-2002-83946 (see FIGS. 7 to 23 and paragraph numbers 0026 to 0038 of the same publication) can be applied to the manufacturing process of the above-described multilayer image sensor, preferably a three-layer image sensor.

[Example]
Examples and embodiments are described below.

On the indium tin oxide thin film (hereinafter referred to as ITO), a 50 nm-thick (Dye: A-1) layer of the present invention was formed by vacuum deposition, and then (material 1) by vacuum deposition. A photoconductive element A can be obtained by forming a 50 nm thick layer and further forming a 20 nm thick translucent gold electrode by vacuum deposition. The same photoconductive element B is used except that copper phthalocyanine is used instead of (pigment: A-1) of the photoelectric conversion element A. In addition, the image pick-up element which divided these photoconductive films A and B into pixels is set as image pick-up elements A and B, respectively.
The absorption maximum wavelength of the photoelectric conversion film of the photoelectric conversion element A is 615 nm, and the half width of absorption is 80 nm. On the other hand, the absorption maximum wavelength of the photoelectric conversion film of the photoelectric conversion element B is 610 nm, and the half width of absorption is 205 nm.
The optical response current of the image sensor A is 1.4 times that of the image sensor B.
Further, by applying a reverse bias of a voltage of 5v between the electrodes (a positive voltage is applied to the gold electrode), that is, by applying an electric field of 5 × 10 ⁷ V / m, the photoresponse current of the image sensor A does not apply a voltage. In contrast to the case of 2.6 times, the photoresponse current of the comparative image pickup element B is only 1.9 times that of the case where no voltage is applied.
The same result can be obtained even if the order of lamination of (dye: A-1) or copper phthalocyanine and (material 1) is reversed. In this case, the polarity of voltage application is reversed.
As described above, the image sensor made of the photoelectric conversion film containing the dye of the present invention has a higher photoresponse current and higher sensitivity as the image sensor than the image sensor made of the photoelectric conversion film not containing the dye of the present invention. Moreover, when a voltage is applied, the sensitivity becomes remarkably high.

The same elements of the present invention except for the compounds used in the image sensor described in Example 1 were changed as follows, and showed excellent performance as in Example 1.
Elements of the present invention (photoelectric conversion element C, imaging element C):
(Dye: A-1) is changed to (Dye: A-2) of the present invention. The maximum absorption wavelength of the photoelectric conversion film of the photoelectric conversion element C is 557 nm, and the half width of absorption is 71 nm.

The same elements of the present invention except for the compounds used in the image sensor described in Example 1 were changed as follows, and showed excellent performance as in Example 1.
Elements of the present invention (photoelectric conversion element D, imaging element D):
(Dye: A-1) is changed to (Dye: A-3) of the present invention. The maximum absorption wavelength of the photoelectric conversion film of the photoelectric conversion element C is 457 nm, and the half width of absorption is 70 nm.

  In the imaging device shown in FIG. 1 in which the imaging device of Example 3 is a B layer, the imaging device of 2 is the G layer, the imaging device of 1 is the R layer, and the three imaging layers are laminated, each layer has an excellent optical response compared It shows current and is highly sensitive, and has excellent color reproducibility as a color image sensor.

It is a cross-sectional schematic diagram for 1 pixel of the photoelectric conversion film laminated | stacked image pick-up element of BGR 3 layer lamination by this invention.

Explanation of symbols

1 P-well layers 2, 4, 6 High-concentration impurity regions 3, 5, 7 MOS circuit 8 Gate insulating films 9, 10 Insulating films 11, 14, 16, 19, 21, 24, Transparent electrode films 12, 17, 22, Electrodes 13, 18, 23 Photoelectric conversion films 10, 15, 20, 25 Transparent insulating film 26 Light shielding film 50 Semiconductor substrate

Claims (18)

  A photoelectric conversion film having an organic pn junction of an organic p-type semiconductor and an organic n-type semiconductor, comprising at least one merocyanine dye. 2. The photoelectric conversion film according to claim 1, wherein the merocyanine dye according to claim 1 is represented by the following general formula (A).
Formula (A)

In formula (A), L ₁₀₈ , L ₁₀₉ , L ₁₁₀ and L ₁₁₁ each independently represent a methine group. p ₁₀₃ represents 0 or 1; q ₁₀₁ represents 0 or 1. n ₁₀₂ represents 0, 1, 2, 3 or 4. Z ₁₀₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. Z ₁₀₄ and Z ₁₀₄ ′ together with (N—R ₁₀₄ ) q ₁₀₁ represent an atomic group necessary for forming a ring or an acyclic acidic end group. However, Z ₁₀₃ and Z ₁₀₄ and Z ₁₀₄ ′ may be condensed or may have a substituent. M ₁₀₂ represents a charge balancing counter ion, m ₁₀₂ represents a number of 0 or more necessary for neutralizing the molecular charge. R ₁₀₃ and R ₁₀₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.   The photoelectric conversion film according to claim 1 or 2, wherein the merocyanine dye-containing layer has a thickness of 30 nm to 300 nm.   A photoelectric conversion element comprising the photoelectric conversion film according to claim 1 and a pair of electrodes sandwiching the photoelectric conversion film.   An imaging device comprising the photoelectric conversion device according to claim 4.   The image pickup device according to claim 4, wherein two or more layers of the photoelectric conversion device according to claim 4 are laminated.   7. The imaging element according to claim 6, wherein the photoelectric conversion element having two or more layers according to claim 6 includes three layers of a blue photoelectric conversion element, a green photoelectric conversion element, and a red photoelectric conversion element.   When the spectral absorption maximum values are λmax1, λmax2, and λmax3 in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7, λmax1 is 400 nm to 500 nm and λmax2 is 500 nm to 600 nm. The imaging element according to claim 7, wherein λmax3 is in the range of 600 nm to 700 nm.   When the spectral sensitivity maximum values are Smax1, Smax2, and Smax3 in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7, Smax1 is 400 nm to 500 nm and Smax2 is 500 nm to 600 nm. The image sensor according to claim 7, wherein Smax3 is in a range of 600 nm to 700 nm.   The distance between the shortest wavelength and the longest wavelength that indicates 50% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 is 120 nm or less, respectively. The imaging device according to claim 7.   The distance between the shortest wavelength and the longest wavelength that indicates 50% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 is 120 nm or less, respectively. The imaging device according to claim 7.   The interval between the shortest wavelength and the longest wavelength, which indicates 80% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7, is 20 nm or more and 100 nm or less, respectively. The imaging device according to claim 7.   The interval between the shortest wavelength and the longest wavelength, which indicates 80% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7, is 20 nm or more and 100 nm or less, respectively. The imaging device according to claim 7.   The distance between the shortest wavelength and the longest wavelength indicating 20% of the spectral maximum absorption of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 is 180 nm or less, respectively. The imaging device according to claim 7.   The distance between the shortest wavelength and the longest wavelength indicating 20% of the spectral maximum sensitivity of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 is 180 nm or less, respectively. The imaging device according to claim 7.   The longest wavelengths showing 50% of the spectral maximum absorption in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 are 460 nm to 510 nm, 560 nm to 610 nm, and 640 nm, respectively. The imaging device according to claim 7, wherein the imaging device is 730 nm or less.   The longest wavelengths showing 50% of the spectral maximum sensitivity in the order of the blue photoelectric conversion element, the green photoelectric conversion element, and the red photoelectric conversion element according to claim 7 are 460 nm to 510 nm, 560 nm to 610 nm, and 640 nm, respectively. The imaging device according to claim 7, wherein the imaging device is 730 nm or less. A method of applying an electric field of 10 V / m or more and 1 × 10 ¹² V / m or less to the photoelectric conversion film, the photoelectric conversion element, or the imaging element according to claim 1.

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