WO2019098161A1 - 光電変換素子、光センサ、撮像素子、化合物 - Google Patents
光電変換素子、光センサ、撮像素子、化合物 Download PDFInfo
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- WO2019098161A1 WO2019098161A1 PCT/JP2018/041887 JP2018041887W WO2019098161A1 WO 2019098161 A1 WO2019098161 A1 WO 2019098161A1 JP 2018041887 W JP2018041887 W JP 2018041887W WO 2019098161 A1 WO2019098161 A1 WO 2019098161A1
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- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- LJDSOABMJSBRJV-UHFFFAOYSA-N indium;oxosilver Chemical compound [In].[Ag]=O LJDSOABMJSBRJV-UHFFFAOYSA-N 0.000 description 1
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- 125000001041 indolyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
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- 150000004986 phenylenediamines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- DNTVKOMHCDKATN-UHFFFAOYSA-N pyrazolidine-3,5-dione Chemical class O=C1CC(=O)NN1 DNTVKOMHCDKATN-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- PMJMHCXAGMRGBZ-UHFFFAOYSA-N subphthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(=N3)N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C3=N1 PMJMHCXAGMRGBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
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- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
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- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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- H10K30/84—Layers having high charge carrier mobility
- H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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- H10K85/211—Fullerenes, e.g. C60
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a photoelectric conversion element, an optical sensor, an imaging element, and a compound.
- solid-state imaging devices flat-type solid-state imaging devices are widely used, in which photodiodes (PDs) are two-dimensionally arrayed and signal charges generated in each PD are read out by a circuit.
- a color solid-state imaging device a structure in which a color filter for transmitting light of a specific wavelength is disposed on the light incident surface side of the planar solid-state imaging device is generally used.
- a color filter for transmitting blue (B: blue) light, green (G: green) light, and red (R: red) light is regularly arranged.
- B blue
- G green
- R red
- Patent Document 1 discloses a compound represented by the following formula as a material applied to a photoelectric conversion element (claim 1).
- An object of the present invention is to provide a photoelectric conversion element having excellent heat resistance in view of the above situation.
- Another object of the present invention is to provide an optical sensor and an imaging device including the photoelectric conversion device. Furthermore, this invention also makes it a subject to provide the compound applied to the said photoelectric conversion element.
- a photoelectric conversion element comprising a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, The photoelectric conversion element in which the said photoelectric conversion film contains an at least 1 sort (s) of compound selected from the group which consists of a compound represented by Formula (1) mentioned later, and a compound represented by Formula (2) mentioned later.
- the compound represented by Formula (1) described later is a compound represented by Formula (3) described later, and the compound represented by Formula (2) described later is a compound represented by Formula (4) described later
- R 1 may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent
- the photoelectric conversion film further contains an n-type organic semiconductor, At least one compound selected from the group consisting of a compound represented by the formula (1) described later and a compound represented by the formula (2) described later, and the n-type organic semiconductor
- An optical sensor comprising the photoelectric conversion device according to any one of [1] to [10].
- An imaging device comprising the photoelectric conversion device according to any one of [1] to [10].
- a photoelectric conversion element having excellent heat resistance can be provided. Further, according to the present invention, it is also possible to provide an optical sensor and an imaging device including the photoelectric conversion device. Furthermore, according to the present invention, it is possible to provide a compound to be applied to the photoelectric conversion device.
- a substituent for example, a substituent W described later
- a substituent W for example, a substituent W described later
- the expression "alkyl group” means an alkyl group (that is, a substituted or unsubstituted alkyl group) which may be substituted by a substituent (for example, the substituent W described later).
- a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
- each substituent when there are a plurality of substituents and linking groups etc. (hereinafter referred to as substituents etc.) represented by specific symbols, or when a plurality of substituents etc. are simultaneously defined, each substituent is It means that they may be the same as or different from each other. The same applies to the definition of the number of substituents and the like.
- the photoelectric conversion film comprises at least one selected from the group consisting of a compound represented by formula (1) described later and a compound represented by formula (2) described later
- a compound represented by formula (2) described later
- the point which uses the compound of a kind (Hereafter, these compounds are also generically called a "specific compound") is mentioned.
- the present inventors believe that the heat resistance of the photoelectric conversion element produced using the specific compound is improved because the specific compound has a rigid structure.
- FIG. 1 the cross-sectional schematic diagram of one Embodiment of the photoelectric conversion element of this invention is shown.
- the photoelectric conversion element 10a shown in FIG. 1A includes a conductive film (hereinafter also referred to as a lower electrode) 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and an upper electrode.
- a transparent conductive film (hereinafter also referred to as an upper electrode) 15 that functions is laminated in this order.
- FIG. 1B shows a configuration example of another photoelectric conversion element.
- FIGS. 1A and 1B has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on the lower electrode 11.
- the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1A and 1B may be appropriately changed according to the application and the characteristics.
- the photoelectric conversion element 10 a (or 10 b) light is preferably incident on the photoelectric conversion film 12 through the upper electrode 15.
- a voltage can be applied.
- the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes.
- the voltage to be applied is more preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 7 V / cm, and further preferably 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 6 V / cm.
- the voltage application method is preferably such that the electron blocking film 16A side is a cathode and the photoelectric conversion film 12 side is an anode in FIGS. 1A and 1B.
- the photoelectric conversion element 10a (or 10b) is used as an optical sensor, or when it is incorporated in an imaging element, a voltage can be applied by the same method.
- the photoelectric conversion element 10a (or 10b) can be suitably applied to an optical sensor application and an imaging element application, as described in detail later.
- FIG. 2 the cross-sectional schematic diagram of another embodiment of the photoelectric conversion element of this invention is shown.
- the photoelectric conversion element 200 shown in FIG. 2 is a hybrid photoelectric conversion element provided with an organic photoelectric conversion film 209 and an inorganic photoelectric conversion film 201.
- the organic photoelectric conversion film 209 contains the specific compound mentioned later.
- the inorganic photoelectric conversion film 201 has an n-type well 202, a p-type well 203, and an n-type well 204 on a p-type silicon substrate 205.
- Blue light is photoelectrically converted at the pn junction formed between the p-type well 203 and the n-type well 204 (pixel B), and is formed at the pn junction formed between the p-type well 203 and the n-type well 202 Red light is photoelectrically converted (R pixel).
- the conductivity types of the n-type well 202, the p-type well 203, and the n-type well 204 are not limited to these.
- a transparent insulating layer 207 is disposed on the inorganic photoelectric conversion film 201.
- a transparent pixel electrode 208 divided for each pixel is disposed on the insulating layer 207, and an organic photoelectric conversion film 209 that absorbs green light and performs photoelectric conversion is disposed on one pixel common to all pixels
- the electron blocking film 212 is disposed in a single sheet common to each pixel, the transparent common electrode 210 of a single sheet is disposed thereon, and the transparent protective film 211 is disposed in the uppermost layer It is done.
- the stacking order of the electron blocking film 212 and the organic photoelectric conversion film 209 may be reverse to that in FIG. 2, and the common electrode 210 may be arranged separately for each pixel.
- the organic photoelectric conversion film 209 constitutes G pixels that detect green light.
- the pixel electrode 208 is the same as the lower electrode 11 of the photoelectric conversion element 10 a shown in FIG. 1A.
- the common electrode 210 is the same as the upper electrode 15 of the photoelectric conversion element 10a shown in FIG. 1A.
- Blue light with a short wavelength is photoelectrically converted mainly at the shallow portion of the semiconductor substrate (inorganic photoelectric conversion film) 201 (near the pn junction formed between the p-type well 203 and the n-type well 204) to generate photocharges.
- Signal is output to the outside.
- the red light having a long wavelength is mainly photoelectrically converted at the deep portion of the semiconductor substrate (inorganic photoelectric conversion film) 201 (near the pn junction formed between the p-type well 203 and the n-type well 202) to generate photocharges.
- the signal is output to the outside.
- CMOS complementary metal oxide semiconductor
- CCD Charge Coupled Device
- MOS Metal-Oxide-Semiconductor
- the photoelectric conversion film 12 (or the organic photoelectric conversion film 209) is a film containing a specific compound as a photoelectric conversion material. By using this compound, a photoelectric conversion element having excellent heat resistance can be obtained.
- the specific compound will be described in detail.
- substituents that the specific compound may have each independently a group represented by Formula (C) described later (preferably a group represented by Formula (CX)) And the substituent W described later.
- alkyl group (including an alkyl group which may have a substituent) which the specific compound may have are each independently an alkyl group AL described later.
- aryl group (including an aryl group which may have a substituent) each independently include an aryl group AR described later, and a heteroaryl group (a heteroaryl which may have a substituent)
- examples of the group) include each independently a heteroaryl group HA described later.
- the photoelectric conversion film of the photoelectric conversion device of the present invention contains at least one compound selected from the group consisting of a compound represented by Formula (1) and a compound represented by Formula (2).
- R 1 and R 2 each independently represent a hydrogen atom or a substituent.
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent.
- An aryl group is preferred.
- R 1 is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
- the aryl group which may have or the heteroaryl group which may have a substituent is more preferable.
- R 2 is preferably a hydrogen atom.
- X 1 represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR a1- , -CR a2 R a3- , or -SiR a4 R a5- .
- R a1 to R a5 each independently represent a hydrogen atom or a substituent, and a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent
- the heteroaryl group which may have is preferable.
- X 1 is preferably a sulfur atom, an oxygen atom, or a selenium atom, more preferably a sulfur atom or an oxygen atom, and still more preferably a sulfur atom.
- R a6 represents a hydrogen atom or a substituent.
- R a 6 may be a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent
- a preferred heteroaryl group or a group represented by the formula (C) described later is preferable.
- L 1 represents a single bond, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NR a7- , -CR a8 R a9- , -SiR a10 R a11- , or -CO-.
- L 1 is preferably a single bond, an oxygen atom, -CR a8 R a9- , -SiR a10 R a11- or -CO-, and a single bond or -CR a8 R a9 -is more preferable.
- Each of R a7 to R a11 independently represents a hydrogen atom or a substituent.
- R a7 to R a11 are each independently a hydrogen atom, a halogen atom (preferably a fluorine atom), an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent
- the heteroaryl group which may have a group is preferable, and the alkyl group which may have a substituent is more preferable.
- the alkyl group which may have a substituent is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- R a8 and R a9 combine with each other to form a ring
- L 1 is —SiR a10 R a11 ⁇
- a10 and R a11 combine with each other to form a ring
- a ring formed by bonding R a8 and R a9 (or R a10 and R a11 ) to each other is, for example, a hydrocarbon ring which may have a substituent (preferably having a carbon number of 4 to 20).
- Is preferable and it may be a saturated hydrocarbon ring (preferably having a carbon number of 5 to 6) which may have a substituent or an aromatic hydrocarbon ring (which preferably has a carbon number of 6 to 18) which may have a substituent.
- a fluorene ring is more preferable.
- Z 1 and Z 2 are each independently a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR a12 -, - CR a13 R a14 -, - SiR a15 R a16 -, Or represents -CO-.
- Z 1 and Z 2 are each independently preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom.
- each of R a12 to R a16 independently represents a hydrogen atom or a substituent, and is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Or a heteroaryl group which may have a substituent is preferable.
- each of R a12 to R a18 independently represents a hydrogen atom or a substituent, and is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
- a heteroaryl group which may have a substituent is preferable, and a hydrogen atom is more preferable.
- B 1 represents, -CO-, oxygen atom, sulfur atom, selenium atom, tellurium atom, -NR a19 -, - CR a20 R a21 -, or, -SiR a22 R a23 - represents a.
- R a19 to R a23 each independently represent a hydrogen atom or a substituent, and a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent
- the heteroaryl group which may have is preferable.
- B 1 is preferably -CO-, an oxygen atom or a sulfur atom, and more preferably -CO-.
- a 1 represents a ring. More specifically, A 1 is a “carbon atom represented by CC ⁇ , which forms a vinylene group together with the carbon atom to which R 2 is bonded,” which is specified in formulas (1) and (2), and And a ring containing “—CO—” and “—B 1 —” bonded to this carbon atom. A preferred embodiment of A 1 will be described later.
- R 1 , R 2 and R a1 to R a23 may be bonded to each other to form a ring.
- the ring and Y 2 in R a6 and R a6 in Y 3 are bonded to each other to form a ring, for example, an aromatic ring (preferably aromatic ring of 5 to 6-membered ring, more preferably a furan ring) It is also preferable that the substituent of the above-mentioned aromatic ring further forms a ring (preferably a 5- to 6-membered aromatic ring, more preferably a thiophene ring).
- R 1 , R 2 and R a1 to R a23 may be bonded to each other to form a ring.
- R a6 of R a6 and Y 4 in the Y 3 are bonded to each other to form a ring, for example, an aromatic ring (preferably aromatic ring of 5 to 6-membered ring, more preferably a furan ring)
- the substituent of the above-mentioned aromatic ring further forms a ring (preferably a 5- to 6-membered aromatic ring, more preferably a thiophene ring).
- Equation (1) and the number of carbon atoms of A 1 in (2) is preferably from 3 to 30, more preferably from 3 to 20, more preferably 3 to 15.
- the above-mentioned carbon number is indicated in the formula “—CO—” “a carbon atom represented by ⁇ ⁇ ⁇ C ⁇ which forms a vinylene group with the carbon atom to which R 2 is bonded” and “-B 1- ”
- Is a number including the carbon atom of A 1 may have a hetero atom, and examples thereof include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
- a 1 may have a substituent, and a halogen atom (preferably a chlorine atom) is preferable as the above-mentioned substituent.
- the number of heteroatoms in A 1 is preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 2.
- the number of hetero atoms mentioned above includes the number of hetero atoms contained in "-CO-" and "-B 1- " specified in the formula, and the number of hetero atoms which the substituent of A 1 has. There is no number.
- a 1 may or may not show aromaticity.
- a 1 may be a single ring structure or a condensed ring structure, and is preferably a fused ring containing at least one of a 5-, 6-, or 5- and 6-membered ring.
- the number of rings forming the above-mentioned fused ring is preferably 1 to 4, and more preferably 1 to 3.
- a 1 is preferably a ring which is usually used as an acidic nucleus in merocyanine dyes, and specific examples thereof include the following rings.
- B 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof.
- Examples of the derivative include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, and 1,3- 1,3-Diaryls such as diphenyl, 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryls such as 1-ethyl-3-phenyl And 1,3-diheteroaryl such as 1,3-di (2-pyridyl).
- C 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof and the like.
- derivatives include 3-methylrhodane, 3-ethylrhodane such as 3-alkylrhodanine such as 3-ethylrhodane, 3-arylrhodanine, 3-arylrhodane such as 3-phenylrhodanine, and 3- (2) And 3-heteroaryl rhodanine such as -pyridyl) rhodanine and the like.
- 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazole dione) nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione .
- (E) Tiananaphthenone nucleus For example, 3 (2H) -Tiananaphthenone-1,1-dioxide and the like.
- (H) Thiazolin-4-one nucleus for example, 4-thiazolinone, and 2-ethyl-4-thiazolinone and the like.
- (K) 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione, and 1,2-dimethyl-3,5-pyrazolidinedione.
- (L) Indanone nucleus for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone .
- the compounds represented by the formulas (1) and (2) are preferably compounds represented by the following formulas (1X) and (2X), respectively.
- R 1 , R 2 , X 1 , Y 1 to Y 4 , Z 1 , Z 2 , L 1 and B 1 are each in the formulas (1) and (2) It is respectively synonymous with the group represented by the same symbol.
- R 1 , R 2 and R a1 to R a23 may be respectively bonded to each other to form a ring
- R 1 , R 2 and R a1 R a23 may be bonded to each other to form a ring. Examples of embodiments forming a ring are as described above.
- R c1 to R c3 are each independently a hydrogen atom or a substituent, and a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 4) is preferable.
- R c4 is a divalent substituent which forms a double bond with a carbon atom, and is preferably an oxygen atom or a sulfur atom.
- R c1 to R c4 may be bonded to each other to form a ring.
- R c1 and R c2 are preferably bonded to each other to form a ring, and the ring formed is a benzene ring which may have a substituent preferable.
- the substituents which the said benzene ring has may mutually couple
- R c1 and R c2 combine with each other to form a ring, and further R c1 It is also preferable that the ring formed by R c and R c2 and R c4 be bonded to each other to form another ring.
- Q 1 is, for example, a 1,8-naphthalenediyl group.
- the divalent linking group represented by Q 1 is preferably a divalent linking group represented by the following formula (D).
- R d1 to R d4 independently represents a hydrogen atom or a substituent, and a hydrogen atom or a halogen atom (preferably a chlorine atom) is preferable.
- R d1 and R d2 , R d2 and R d3 , and R d3 and R d4 may be bonded to each other to form a ring.
- Rd 2 and Rd 3 are preferably bonded to each other to form a ring.
- the ring formed in this manner and an aromatic ring is preferable, and a benzene ring which may have a substituent is more preferable.
- the compound represented by the formula (1) is preferably a compound represented by the formula (3), and the compound represented by the formula (2) is a compound represented by the formula (4) preferable.
- R 1 to R 6 each independently represent a hydrogen atom or a substituent.
- R 1 and R 2 of formula (3) and (4) has the same definition as R 1 and R 2 in the formula (1) and (2).
- R 3 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a formula (to be described later)
- the group represented by C) (preferably the group represented by formula (CX)) is preferred.
- R 4 to R 6 are preferably hydrogen atoms.
- X 1 represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR a1- , -CR a2 R a3- or -SiR a4 R a5- .
- Each of R a1 to R a5 independently represents a hydrogen atom or a substituent.
- X 1 and R a1 ⁇ R a5 of the formula (3) and (4) are respectively synonymous with X 1 and R a1 ⁇ R a5 in formula (1) and (2).
- L 1 represents a single bond, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NR a7- , -CR a8 R a9- , -SiR a10 R a11- , or -CO-.
- R a7 to R a11 independently represents a hydrogen atom or a substituent.
- L 1 and R a7 ⁇ R a11 of formula (3) and (4) are the same meaning as L 1 and R a7 ⁇ R a11 in the formula (1) and (2).
- Z 1 and Z 2 are each independently a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR a12 -, - CR a13 R a14 -, - SiR a15 R a16 -, Or represents -CO-.
- R a12 to R a18 independently represents a hydrogen atom or a substituent. Equation (3) and (4) Z 1, Z 2 during, and R a12 ⁇ R a18 is, Z 1, Z 2 in Formula (1) and (2), and, with R a12 ⁇ R a18, Each is synonymous.
- a 2 represents a ring. More specifically, A 2 is a “carbon atom represented by CC ⁇ which forms a vinylene group together with the carbon atom to which R 2 is bonded” which is clearly shown in the formulas (3) and (4) And a ring containing two “—CO—” adjacent to this carbon atom. It will be described later preferred form of A 2.
- R 1 to R 5 , R a1 to R a5 and R a7 to R a18 may be bonded to each other to form a ring.
- R 3 and R 4 are preferably bonded to each other to form a ring.
- the ring in which R 3 and R 4 are bonded to each other to form a ring is, for example, preferably an aromatic ring (preferably a 5- to 6-membered aromatic ring, more preferably a furan ring), and substitution of the above aromatic ring It is also preferred that the group further form a ring (preferably a 5- to 6-membered aromatic ring, more preferably a thiophene ring).
- R 1 to R 3 , R 5 , R 6 , R a1 to R a5 and R a7 to R a18 may be bonded to each other to form a ring.
- L 1 represents -NR a7- , -CR a8 R a9- , or -Si
- R 3 and R 6 are preferably bonded to each other to form a ring.
- the ring in which R 3 and R 6 are bonded to each other to form a ring is, for example, preferably an aromatic ring (preferably a 5- to 6-membered aromatic ring, more preferably a furan ring), and substitution of the above aromatic ring It is also preferred that the group further form a ring (preferably a 5- to 6-membered aromatic ring, more preferably a thiophene ring).
- a 2 in the formulas (3) and (4) described above corresponds to the case where B 1 represents —CO— in A 1 in the formulas (1) and (2).
- the compounds represented by the formulas (3) and (4) are preferably compounds represented by the following formulas (3X) and (4X), respectively.
- R 1 to R 6 , X 1 , Z 1 , Z 2 and L 1 are each independently a group represented by the same symbol in formulas (3) and (4) It is synonymous.
- R 1 to R 5 , R a1 to R a5 , and R a7 to R a18 may be bonded to each other to form a ring
- R 1 to R 3 , R 5 , R 6 , R a1 to R a5 , and R a7 to R a18 may be bonded to each other to form a ring. Examples of embodiments forming a ring are as described above.
- Q 1 is the same meaning as to Q 1 in the formula (1X) and (2X).
- the specific compound is preferably a compound represented by Formula (5).
- R 1 to R 5 each independently represent a hydrogen atom or a substituent.
- R 1 ⁇ R 5 in formula (5) has the same meaning as R 1 ⁇ R 5 in formula (3).
- X 51 represents a sulfur atom or an oxygen atom.
- X 51 is preferably a sulfur atom.
- L 51 represents a single bond or -CR a51 R a52- .
- Each of R a51 and R a52 independently represents a hydrogen atom or a substituent.
- R a51 and R a52 have the same meanings as R a8 and R a9 in formula (1).
- R a51 and R a52 may be bonded to each other to form a ring, and as an embodiment of forming a ring, an embodiment in which R a8 and R a9 are bonded to each other to form a ring can be mentioned similarly .
- Z 51 represents a sulfur atom or an oxygen atom.
- Z 51 is preferably a sulfur atom.
- L 51 is -CR a51 R a52-
- R a53 and R a54 independently represents a hydrogen atom or a substituent.
- R a53 and R a54 are respectively synonymous with R a17 and R a18 in Formula (1).
- a 2 represents a ring.
- a 2 in formula (5) has the same meaning as A 2 in the formula (3). It will be described later preferred form of A 2.
- R 1 to R 5 and R a51 to R a54 may be bonded to each other to form a ring.
- R 3 and R 4 are preferably bonded to each other to form a ring. Preferred forms of the ring in which R 3 and R 4 are bonded to each other to form a ring are as described above in the description of the formula (3).
- a 2 in the formula (5) is a “carbon atom represented by CC ⁇ which forms a vinylene group with a carbon atom to which R 2 is bonded” in the following formula (5X), two “—CO—” And “-Q 1- ” is preferably a ring formed jointly.
- the compound represented by the formula (5) is preferably a compound represented by the following formula (5X).
- R 1 to R 5 , X 51 , Z 51 and L 51 each have the same meaning as the group represented by the same symbol in the formula (5).
- R 1 to R 5 and R a51 to R a54 may be bonded to each other to form a ring. Examples of embodiments forming a ring are as described above.
- Q 1 is the same meaning as to Q 1 in the formula (1X) and (2X).
- the specific compound is more preferably a compound represented by Formula (6).
- R 1 to R 5 and R d1 to R d4 each independently represent a hydrogen atom or a substituent.
- R 1 ⁇ R 5 in the formula (6) has the same meaning as R 1 ⁇ R 5 in formula (3).
- R d1 ⁇ R d4 in the formula (6) has the same meaning as R d1 ⁇ R d4 in the formula (D).
- R 1 to R 5 and R d1 to R d4 may be combined with each other to form a ring.
- R 1 and R 5 , R 1 and R 4 , R 3 and R 4 , and R 2 and R 5 may be bonded to each other to form a ring.
- R 3 and R 4 are preferably bonded to each other to form a ring.
- the ring in which R 3 and R 4 are bonded to each other to form a ring is as described above in the description of Formula (3).
- R d1 and R d2 , R d2 and R d3 , and R d3 and R d4 respectively bond with each other to form a ring, and as such a ring formed in this way Preferred forms are as described above in the description of Formula (D).
- substituent W for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.), an alkyl group, an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group Group, heterocyclic group (may be referred to as heterocyclic group, including heteroaryl group), cyano group, hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino (including anilino), ammonio, acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sul
- a halogen atom a fluorine atom, a chlorine
- the substituent W may be further substituted by the substituent W.
- the alkyl group may be substituted with a halogen atom.
- the details of the substituent W are described in paragraph [0023] of JP-A-2007-234651.
- the specific compound preferably has a group represented by the following formula (C) (preferably a group represented by the formula (CX)) as a substituent.
- C formula (C)
- R 2, B 1, and, A 1 is, R 2, B 1 in the formula (1) and (2), and is synonymous with A 1.
- R 2, B 1, and, Q 1 is, R 2, B 1 in the formula (1X) and (2X), and has the same meaning as Q 1. * Represents a bonding position.
- the alkyl group AL preferably has, for example, 1 to 15 carbon atoms, more preferably 1 to 10, and still more preferably 1 to 6.
- the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, and cyclopentyl group.
- the alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these cyclic structures as a partial structure.
- the substituent which the alkyl group may have is not particularly limited, and examples thereof include the substituent W, and an aryl group (preferably having 6 to 18 carbon atoms, more preferably 6 carbon atoms), a heteroaryl group (preferably carbon)
- aryl group preferably having 6 to 18 carbon atoms, more preferably 6 carbon atoms
- heteroaryl group preferably carbon
- the number 5 to 18, preferably 5 to 6 carbon atoms, or a halogen atom preferably a fluorine atom or a chlorine atom
- aryl group AR examples include aryl groups having 6 to 18 carbon atoms.
- the aryl group may be monocyclic or polycyclic.
- a phenyl group, a naphthyl group, or an anthryl group is preferable, for example, and a phenyl group is more preferable.
- the substituent which the aryl group may have is not particularly limited, and examples thereof include a substituent W.
- the substituent an alkyl group (preferably having a carbon number of 1 to 10) which may further have a substituent is preferable, and a methyl group is more preferable.
- heteroaryl group HA examples include heteroaryl groups having a monocyclic or polycyclic ring structure containing a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom.
- the number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 3 to 18 and more preferably 3 to 5.
- the number of heteroatoms in the heteroaryl group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 4, and still more preferably 1 to 2.
- the number of ring members of the heteroaryl group is not particularly limited, but 3 to 8 is preferable, 5 to 7 is more preferable, and 5 to 6 is more preferable.
- heteroaryl group examples include furyl group, pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, quinazolyl group, pyridazinyl group, cinnolinyl group, phthalazinyl group.
- a specific compound does not contain any of an acidic group and its salt from the point which avoids aggravation of vapor deposition aptitude. It is because these groups may cause decomposition of the compound at the time of vapor deposition.
- the “acidic group” is a substituent having a dissociative proton and intends a substituent having a pKa of 11 or less.
- the pKa of the acidic group is as described in J.I. Phys. Chem. A 2011, 115, p. It is determined according to the "SMD / M05-2X / 6-31G *" method described in US Pat.
- the acidic group which shows acidity such as a carboxy group, a phosphonyl group, a phosphoryl group, a sulfo group, and a boric acid group, and the group which has these acidic groups are mentioned, for example.
- the molecular weight of the specific compound is not particularly limited, but is preferably 400 to 900. If the molecular weight is 900 or less, the deposition temperature does not increase, and decomposition of the compound hardly occurs. When the molecular weight is 400 or more, the glass transition point of the deposited film does not decrease, and the heat resistance of the photoelectric conversion element is improved.
- the specific compound is particularly useful as a material of a photoelectric conversion film used for an optical sensor, an imaging device, or a photovoltaic cell. Usually, the specific compound often functions as a p-type organic semiconductor in the photoelectric conversion film.
- the specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, pharmaceutical materials, and fluorescent diagnostic materials.
- the specific compound is a compound having an ionization potential of -5.0 to -6.0 eV in a single film in terms of the stability when used as a p-type organic semiconductor and the matching of the energy level with the n-type organic semiconductor Is preferred.
- the maximum absorption wavelength of the specific compound is preferably in the range of 450 to 600 nm and in the range of 480 to 600 nm in order to be applicable to the organic photoelectric conversion film 209 that absorbs green light and performs photoelectric conversion as described above. Is more preferable.
- the maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration at which the absorbance becomes 0.5 to 1.
- the specific compounds may be used alone or in combination of two or more.
- the photoelectric conversion film preferably contains an n-type organic semiconductor as a component other than the specific compound described above.
- the n-type organic semiconductor is an acceptor type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting an electron. More specifically, an n-type organic semiconductor refers to an organic compound having larger electron affinity when used in contact with two organic compounds.
- n-type organic semiconductor for example, fused aromatic carbocyclic compounds (for example, fullerene, naphthalene derivative, anthracene derivative, phenanthrene derivative, tetracene derivative, pyrene derivative, perylene derivative and fluoranthene derivative); nitrogen atom, oxygen atom, And 5- to 7-membered heterocyclic compounds having at least one sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, Phenanthroline, tetrazole, pyrazole, imidazole, and thiazole etc .; polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; and nitrogen-containing heterocyclization Metal complexes having an
- An organic dye may be used as the n-type organic semiconductor.
- the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.
- the n-type organic semiconductor is colorless or has an absorption maximum wavelength close to a specific compound and / or an absorption waveform.
- the absorption maximum wavelength of the n-type organic semiconductor is preferably 400 nm or less, or 500 to 600 nm.
- the n-type organic semiconductor may be used alone or in combination of two or more.
- the photoelectric conversion film preferably has a bulk heterostructure formed by mixing the specific compound and the n-type organic semiconductor.
- the bulk heterostructure is a layer in which the specific compound and the n-type organic semiconductor are mixed and dispersed in the photoelectric conversion film.
- the photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method.
- the bulk heterostructure is described in detail in, for example, paragraphs [0013] to [0014] of JP-A-2005-303266.
- the total content of the specific compound and the n-type organic semiconductor in the photoelectric conversion film is preferably 60 to 100% by mass with respect to the total mass of the photoelectric conversion film.
- the photoelectric conversion film may further contain other components.
- the kind of said other component is not specifically limited, For example, p-type organic semiconductor other than the specific compound mentioned above is mentioned.
- the compound illustrated as an electron donor compound mentioned later, and the electron accepting compound mentioned later for example And compounds exemplified as
- the total number of components substantially contained in the photoelectric conversion film is preferably 2 to 5, and more preferably 2 to 3.
- the photoelectric conversion film includes two types of specific compounds among the specific compounds exemplified in the upper part, each specific compound is separately counted one by one.
- the component which a photoelectric conversion film substantially contains means the component contained 1 mass% or more with respect to the photoelectric conversion film whole mass in a photoelectric conversion film.
- the photoelectric conversion film containing the specific compound is a non-light emitting film, and has a feature different from that of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
- OLED Organic Light Emitting Diode
- the nonluminous film is intended for a film having a light emission quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less.
- the photoelectric conversion film can be mainly formed by a dry film formation method.
- the dry film formation method include physical vapor deposition methods such as vapor deposition (in particular, vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), and plasma polymerization, etc. And CVD (Chemical Vapor Deposition).
- the vacuum evaporation method is preferable.
- manufacturing conditions such as a vacuum degree and vapor deposition temperature, can be set according to a conventional method.
- the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, still more preferably 50 to 500 nm, and particularly preferably 50 to 300 nm.
- the electrodes are made of a conductive material.
- the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected.
- Examples of materials constituting the upper electrode 15 include tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO Conductive metal oxides such as indium tin oxide (IZO) and metal thin films such as gold, silver, chromium and nickel; these metals and conductive metal oxides And polyaniline, polythiophene, and organic conductive materials such as polypyrrole, and the like. Among them, conductive metal oxides are preferable in terms of high conductivity and transparency.
- the sheet resistance is preferably 100 to 10000 ⁇ / ⁇ .
- the degree of freedom in the range of film thickness that can be made thin is large.
- the thickness of the upper electrode (transparent conductive film) 15 decreases, the amount of light absorbed decreases, and the light transmittance generally increases.
- An increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and the photoelectric conversion ability.
- the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm, in consideration of suppression of leakage current, increase in resistance of the thin film, and increase in transmittance as the film thickness decreases.
- the lower electrode 11 may be either transparent or non-transparent and reflect light.
- the material constituting the lower electrode 11 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO).
- Conductive metals such as gold), metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN) And mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
- the method for forming the electrode is not particularly limited, and can be appropriately selected according to the electrode material. Specifically, printing methods and wet methods such as coating methods; physical methods such as vacuum evaporation method, sputtering method and ion plating method; and chemical methods such as CVD and plasma CVD method , Etc.
- the material of the electrode is ITO, methods such as an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (sol-gel method etc.), and a dispersion of indium tin oxide can be mentioned.
- the photoelectric conversion element of the present invention has one or more kinds of intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
- the intermediate layer include a charge blocking film.
- the charge blocking film include an electron blocking film and a hole blocking film. Below, each film is explained in full detail.
- the electron blocking film contains an electron donating compound.
- low molecular weight materials such as N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) and 4,4'-bis [Aromatic diamine compounds such as N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD); Porphyrin compounds such as porphyrin, tetraphenylporphyrin copper, phthalocyanine, copper phthalocyanine, and titanium phthalocyanine oxide; [1 Benzothieno [3,2, b] [1] benzothiophene (BTBT), dinaphtho [2,3-b: 2 ′, 3′-f] thieno [3,2-b] thiophene (DNTT), benzo [1 , 2-b: 4,5-b '] dithiophene (BDT),
- TPD 4,4'-
- polymer material examples include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.
- polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.
- the electron blocking film may be composed of a plurality of films.
- the electron blocking film may be made of an inorganic material.
- the inorganic material has a dielectric constant larger than that of the organic material, when the inorganic material is used for the electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency is increased.
- an inorganic material that can be an electron blocking film for example, calcium oxide, chromium oxide, chromium copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper oxide, gallium oxide copper, strontium oxide copper, niobium oxide, molybdenum oxide, indium oxide Copper, indium silver oxide, iridium oxide and the like can be mentioned.
- Hole blocking film contains an electron accepting compound.
- the electron accepting compound oxadiazole derivatives such as 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7); anthraquinodimethane derivatives; diphenylquinone derivatives Vasocuproin, vasophenanthroline, and derivatives thereof; triazole compounds; tris (8-hydroxyquinolinate) aluminum complexes; bis (4-methyl-8-quinolinate) aluminum complexes; distyrylarylene derivatives; Etc. Further, compounds described in paragraphs [0056] to [0057] of JP-A-2006-100767 can be mentioned.
- the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film formation method and a wet film formation method.
- the dry film forming method includes a vapor deposition method and a sputtering method.
- the vapor deposition method may be any of physical vapor deposition (PVD) and chemical vapor deposition (CVD), preferably physical vapor deposition such as vacuum vapor deposition.
- Examples of the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method. From the viewpoint of precision patterning, the inkjet method is preferred.
- the thickness of the charge blocking film is preferably 3 to 200 nm, more preferably 5 to 100 nm, and still more preferably 5 to 30 nm.
- the photoelectric conversion element may further have a substrate.
- the type of substrate used is not particularly limited, and examples include semiconductor substrates, glass substrates, and plastic substrates.
- the position of the substrate is not particularly limited, in general, a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.
- the photoelectric conversion element may further have a sealing layer.
- the performance of the photoelectric conversion material may significantly deteriorate due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film can be formed of a dense metal oxide, metal nitride, or a metal nitride oxide ceramic that does not allow water molecules to permeate, or a sealing layer such as diamond-like carbon (DLC).
- DLC diamond-like carbon
- the above-mentioned deterioration can be prevented by covering and sealing.
- materials may be selected and manufactured according to the description in paragraphs [0210] to [0215] of JP-A-2011-082508.
- Optical sensor As a use of a photoelectric conversion element, although a photovoltaic cell and an optical sensor are mentioned, for example, it is preferred to use a photoelectric conversion element of the present invention as an optical sensor. As an optical sensor, you may use by the said photoelectric conversion element independent, and may be used as a line sensor which distribute
- the photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a driving unit such as a scanner in a line sensor, and the two-dimensional sensor converts optical image information into an optical signal as an imaging module.
- the system functions as an imaging element by forming an image on a sensor and converting it into an electric signal.
- An image pickup element is an element for converting light information of an image into an electric signal, and a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). And the electric signal can be sequentially output to the outside of the imaging device for each pixel. Therefore, one photoelectric conversion element and one or more transistors are provided per pixel.
- FIG. 3 is a schematic cross-sectional view showing a schematic configuration of an imaging device for describing an embodiment of the present invention.
- the imaging device is mounted on an imaging device such as a digital camera and a digital video camera, an electronic endoscope, and an imaging module such as a cellular phone.
- This imaging device has a plurality of photoelectric conversion devices configured as shown in FIG. 1A, and a circuit board on which a readout circuit for reading out a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion device is formed.
- a plurality of photoelectric conversion elements are arranged in one dimension or two dimensions on the same plane above the circuit board.
- the imaging device 100 illustrated in FIG. 3 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and an opposite electrode.
- CF Color Filter
- the pixel electrode 104 has the same function as the lower electrode 11 of the photoelectric conversion element 10a shown in FIG. 1A.
- the counter electrode 108 has the same function as the upper electrode 15 of the photoelectric conversion element 10 a shown in FIG. 1A.
- the photoelectric conversion film 107 has the same configuration as the layer provided between the lower electrode 11 and the upper electrode 15 of the photoelectric conversion element 10 a shown in FIG. 1A.
- the substrate 101 is a glass substrate or a semiconductor substrate such as Si.
- An insulating layer 102 is formed on the substrate 101.
- a plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.
- the photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.
- the counter electrode 108 is one electrode provided on the photoelectric conversion film 107 and common to all the photoelectric conversion elements.
- the counter electrode 108 is formed on the connection electrode 103 disposed outside the photoelectric conversion film 107 and is electrically connected to the connection electrode 103.
- connection portion 106 is embedded in the insulating layer 102 and is a plug for electrically connecting the connection electrode 103 and the counter electrode voltage supply portion 115.
- the counter electrode voltage supply unit 115 is formed on the substrate 101, and applies a predetermined voltage to the counter electrode 108 through the connection portion 106 and the connection electrode 103.
- the power supply voltage is boosted by a charge pump or other booster circuit to supply the predetermined voltage.
- the readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104.
- the readout circuit 116 is configured of, for example, a CCD, a CMOS circuit, or a TFT (Thin Film Transistor) circuit, and is shielded by a light shielding layer (not shown) disposed in the insulating layer 102.
- the readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection portion 105.
- the buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108.
- the sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109.
- the color filter 111 is formed on the sealing layer 110 so as to face each pixel electrode 104.
- the partition wall 112 is provided between the color filters 111 and is used to improve the light transmittance of the color filter 111.
- the light shielding layer 113 is formed on the sealing layer 110 except the area where the color filter 111 and the partition wall 112 are provided, and prevents light from entering the photoelectric conversion film 107 formed in areas other than the effective pixel area. Do.
- the protective layer 114 is formed on the color filter 111, the partition wall 112, and the light shielding layer 113, and protects the entire imaging element 100.
- the imaging device 100 when light is incident, the light is incident on the photoelectric conversion film 107, and a charge is generated here. Holes among the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the imaging element 100 by the readout circuit 116.
- the method of manufacturing the imaging device 100 is as follows.
- the connection portions 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed on the circuit substrate on which the counter electrode voltage supply portion 115 and the readout circuit 116 are formed.
- the plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in, for example, a square lattice.
- the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum evaporation method.
- the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum, for example, by sputtering.
- the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum evaporation method.
- the protective layer 114 is formed, and the imaging device 100 is completed.
- the invention also includes the invention of compounds.
- the compound of the present invention is the same as the compound represented by the above-mentioned formula (5).
- the compound (A-2) was added to N, N-dimethylformamide (DMF) (57 mL) and stirred, to which N-bromosuccinimide (NBS) (3.27 g, 18.4 mmol) was added.
- NBS N-bromosuccinimide
- the solution thus obtained was allowed to react at room temperature (23 ⁇ 3 ° C.) for 1 hour, then water (100 mL) and ethyl acetate (100 mL) were added for phase separation, and the organic phase was separated.
- the organic phase was washed with saturated brine, magnesium sulfate was added, and the filtrate was concentrated to give a crude product.
- the obtained crude product was purified by silica gel column chromatography (eluent: 20% ethyl acetate / hexane) to obtain a compound (A-3) (5.31 g, yield 75%).
- the photoelectric conversion element of the form of FIG. 1A was produced using the obtained compound. That is, the photoelectric conversion element to be evaluated in this example includes the lower electrode 11, the electron blocking film 16A, the photoelectric conversion film 12, and the upper electrode 15. Specifically, amorphous ITO is deposited on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and the following compound (EB-1) is vacuum-deposited on the lower electrode 11 The film was formed by vapor deposition to form an electron blocking film 16A (thickness: 10 nm).
- the compound (D-1) as a p-type organic semiconductor and the fullerene (C 60 ) as an n-type organic semiconductor are each 100 nm in single layer conversion on the electron blocking film 16A.
- the film was co-evaporated by vacuum evaporation so as to have a thickness of 100 nm, thereby forming a photoelectric conversion film 12 having a bulk heterostructure of 200 nm.
- amorphous ITO was formed into a film on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
- an aluminum oxide (Al 2 O 3 ) layer is formed thereon by an ALCVD (Atomic Layer Chemical Vapor Deposition) method, and the photoelectric conversion element is formed.
- ALCVD Atomic Layer Chemical Vapor Deposition
- the photoelectric conversion element of the present invention is excellent in heat resistance. Moreover, in the specific compound, when the group corresponding to R 1 in the formulas (1) and (2) is an aryl group which may have a substituent, the heat resistance of the photoelectric conversion element is more excellent confirmed.
- Photoelectric conversion element 11 Conductive film (lower electrode) 12 photoelectric conversion film 15 transparent conductive film (upper electrode) 16A electron blocking film 16B hole blocking film 100 pixel separation type imaging device 101 substrate 102 insulating layer 103 connection electrode 104 pixel electrode (lower electrode) 105 connection portion 106 connection portion 107 photoelectric conversion film 108 counter electrode (upper electrode) 109 buffer layer 110 sealing layer 111 color filter (CF) 112 partition wall 113 light shielding layer 114 protective layer 115 counter electrode voltage supply unit 116 readout circuit 200 photoelectric conversion element (hybrid type photoelectric conversion element) 201 inorganic photoelectric conversion film 202 n-type well 203 p-type well 204 n-type well 205 p-type silicon substrate 207 insulating layer 208 pixel electrode 209 organic photoelectric conversion film 210 common electrode 211 protective film 212 electron blocking film
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Abstract
Description
カラー固体撮像素子を実現するには、平面型固体撮像素子の光入射面側に、特定の波長の光を透過するカラーフィルタを配した構造が一般的である。現在、2次元的に配列した各PD上に、青色(B:blue)光、緑色(G:green)光、および、赤色(R:red)光を透過するカラーフィルタを規則的に配した単板式固体撮像素子がよく知られている。しかし、この単板式固体撮像素子においては、カラーフィルタを透過しなかった光が利用されず光利用効率が悪い。
これらの欠点を解決するため、近年、有機光電変換膜を信号読み出し用基板上に配置した構造を有する光電変換素子の開発が進んでいる。
例えば、光電変換素子においては、優れた耐熱性が求められている。
本発明者は、特許文献1に具体的に開示されている化合物を用いて光電変換素子を作製し、得られた光電変換素子の耐熱性を評価したところ、その特性は必ずしも昨今求められるレベルに達しておらず、さらなる向上が必要であることを見出した。
また、本発明は、上記光電変換素子を含む光センサおよび撮像素子を提供することも課題とする。さらに、本発明は、上記光電変換素子に適用される化合物を提供することも課題とする。
導電性膜、光電変換膜、および、透明導電性膜をこの順で有する光電変換素子であって、
上記光電変換膜が、後述する式(1)で表される化合物および後述する式(2)で表される化合物からなる群から選択される少なくとも1種の化合物を含む、光電変換素子。
〔2〕
後述する式(1)で表される化合物が後述する式(3)で表される化合物であり、後述する式(2)で表される化合物が後述する式(4)で表される化合物である、〔1〕に記載の光電変換素子。
〔3〕
後述する式(1)~(4)中、L1が、単結合または-CRa8Ra9-を表す、〔1〕または〔2〕に記載の光電変換素子。
〔4〕
後述する式(1)~(4)中、X1が、硫黄原子、酸素原子、または、セレン原子を表す、〔1〕~〔3〕のいずれかに記載の光電変換素子。
〔5〕
上記光電変換膜が、後述する式(5)で表される化合物を含む、〔1〕~〔4〕のいずれかに記載の光電変換素子。
〔6〕
後述する式(5)で表される化合物が、後述する式(6)で表される化合物である、〔5〕に記載の光電変換素子。
〔7〕
後述する式(1)~(6)中、R1が、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基を表す、〔1〕~〔6〕のいずれかに記載の光電変換素子。
〔8〕
後述する式(1)で表される化合物および後述する式(2)で表される化合物の分子量が、400~900である、〔1〕~〔7〕のいずれかに記載の光電変換素子。
〔9〕
上記光電変換膜が、さらにn型有機半導体を含み、
上記光電変換膜が、後述する式(1)で表される化合物および後述する式(2)で表される化合物からなる群から選択される少なくとも1種の化合物と、上記n型有機半導体とが混合された状態で形成するバルクへテロ構造を有する、〔1〕~〔8〕のいずれかに記載の光電変換素子。
〔10〕
上記導電性膜と上記透明導電性膜の間に、上記光電変換膜の他に1種以上の中間層を有する、〔1〕~〔9〕のいずれかに記載の光電変換素子。
〔11〕
〔1〕~〔10〕のいずれかに記載の光電変換素子を有する、光センサ。
〔12〕
〔1〕~〔10〕のいずれかに記載の光電変換素子を有する、撮像素子。
〔13〕
後述する式(5)で表される化合物。
また、本発明によれば、上記光電変換素子を含む光センサおよび撮像素子を提供することもできる。さらに、本発明によれば、上記光電変換素子に適用される化合物を提供することもできる。
なお、本明細書において、置換または無置換を明記していない置換基等については、目的とする効果を損なわない範囲で、その基にさらに置換基(例えば、後述する置換基W)が置換していてもよいし、置換していなくてもよい。例えば、「アルキル基」という表記は、置換基(例えば、後述する置換基W)が置換していてもよいアルキル基(つまり、置換または無置換のアルキル基)を意味する。
また、本明細書において、「~」を用いて表される数値範囲は、「~」前後に記載される数値を下限値および上限値として含む範囲を意味する。
従来技術と比較した本発明の特徴点としては、光電変換膜に、後述する式(1)で表される化合物および後述する式(2)で表される化合物からなる群から選択される少なくとも1種の化合物(以後、これらの化合物を総称して「特定化合物」ともいう)を使用している点が挙げられる。
本発明者らは、特定化合物が剛直な構造を有しているため、特定化合物を用いて作製された光電変換素子の耐熱性が向上したと考えている。
図1Aに示す光電変換素子10aは、下部電極として機能する導電性膜(以下、下部電極とも記す)11と、電子ブロッキング膜16Aと、後述する特定化合物を含む光電変換膜12と、上部電極として機能する透明導電性膜(以下、上部電極とも記す)15とがこの順に積層された構成を有する。
図1Bに別の光電変換素子の構成例を示す。図1Bに示す光電変換素子10bは、下部電極11上に、電子ブロッキング膜16Aと、光電変換膜12と、正孔ブロッキング膜16Bと、上部電極15とがこの順に積層された構成を有する。なお、図1Aおよび図1B中の電子ブロッキング膜16A、光電変換膜12、および、正孔ブロッキング膜16Bの積層順は、用途および特性に応じて、適宜変更してもよい。
また、光電変換素子10a(または10b)を使用する場合には、電圧を印加できる。この場合、下部電極11と上部電極15とが一対の電極をなし、この一対の電極間に、1×10-5~1×107V/cmの電圧を印加するのが好ましい。性能および消費電力の点から、印加される電圧としては、1×10-4~1×107V/cmがより好ましく、1×10-3~5×106V/cmがさらに好ましい。
なお、電圧印加方法については、図1Aおよび図1Bにおいて、電子ブロッキング膜16A側が陰極となり、光電変換膜12側が陽極となるように印加するのが好ましい。光電変換素子10a(または10b)を光センサとして使用した場合、また、撮像素子に組み込んだ場合も、同様の方法により電圧を印加できる。
後段で、詳述するように、光電変換素子10a(または10b)は光センサ用途および撮像素子用途に好適に適用できる。
図2に示される光電変換素子200は、有機光電変換膜209と無機光電変換膜201とを備えるハイブリッド型の光電変換素子である。なお、有機光電変換膜209は、後述する特定化合物を含む。
無機光電変換膜201は、p型シリコン基板205上に、n型ウェル202、p型ウェル203、および、n型ウェル204を有する。
p型ウェル203とn型ウェル204との間に形成されるpn接合にて青色光が光電変換され(B画素)、p型ウェル203とn型ウェル202との間に形成されるpn接合にて赤色光が光電変換される(R画素)。なお、n型ウェル202、p型ウェル203、および、n型ウェル204の導電型は、これらに限らない。
絶縁層207の上には、画素毎に区分けした透明な画素電極208が配置され、その上に、緑色光を吸収して光電変換する有機光電変換膜209が各画素共通に一枚構成で配置され、その上に、電子ブロッキング膜212が各画素共通に一枚構成で配置され、その上に、一枚構成の透明な共通電極210が配置され、最上層に、透明な保護膜211が配置されている。電子ブロッキング膜212と有機光電変換膜209との積層順は図2とは逆であってもよく、共通電極210は、画素毎に区分けして配置されてもよい。
有機光電変換膜209は、緑色光を検出するG画素を構成する。
<特定化合物>
光電変換膜12(または有機光電変換膜209)は、光電変換材料として特定化合物を含む膜である。この化合物を使用することにより、優れた耐熱性を有する光電変換素子が得られる。
以下、特定化合物について詳述する。
式(2)においても同様で、式(2)中、R2が結合する炭素原子とそれに隣接する炭素原子とで構成されるC=C二重結合に基づいて区別され得る幾何異性体について、式(2)はそのいずれをも含む。
また、特筆無き限り、特定化合物が有し得るアルキル基(置換基を有していてもよいアルキル基を含む)の例としては、それぞれ独立に、後述するアルキル基ALが挙げられる。アリール基(置換基を有していてもよいアリール基を含む)の例としては、それぞれ独立に、後述するアリール基ARが挙げられ、ヘテロアリール基(置換基を有していてもよいヘテロアリール基を含む)の例としては、それぞれ独立に、後述するヘテロアリール基HAが挙げられる。
R1およびR2は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましい。
中でも、R1は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましく、置換基を有していてもよいアリール基または置換基を有していてもよいヘテロアリール基がより好ましい。
R2は、水素原子が好ましい。
Ra1~Ra5は、それぞれ独立に、水素原子または置換基を表し、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましい。
中でも、X1は、硫黄原子、酸素原子、または、セレン原子が好ましく、硫黄原子または酸素原子がより好ましく、硫黄原子がさらに好ましい。
Ra6は、水素原子または置換基を表す。
中でも、Y1~Y2およびY4は、それぞれ独立に、-CH=または窒素原子が好ましく、-CH=がより好ましい。
Y3は、-CRa6=が好ましい。
Y3が-CRa6=である場合、Ra6は、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、または、後述する式(C)で表される基(好ましくは式(CX)で表される基)が好ましい。
中でも、L1は、単結合、酸素原子、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-が好ましく、単結合または-CRa8Ra9-がより好ましい。
Ra7~Ra11は、それぞれ独立に、水素原子または置換基を表す。
Ra7~Ra11は、それぞれ独立に、水素原子、ハロゲン原子(好ましくはフッ素原子)、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましく、置換基を有していてもよいアルキル基がより好ましい。
上記置換基を有していてもよいアルキル基は、炭素数1~4の直鎖状または分岐鎖状のアルキル基が好ましく、メチル基がより好ましい。
また、L1が、-CRa8Ra9-である場合、Ra8とRa9とが互いに結合して環を形成するのも好ましく、L1が、-SiRa10Ra11-である場合、Ra10とRa11とが互いに結合して環を形成するのも好ましい。ここで、Ra8とRa9(またはRa10とRa11)とが互いに結合して形成される環は、例えば、置換基を有していてもよい炭化水素環(好ましくは炭素数4~20)が好ましく、置換基を有していてもよい飽和炭化水素環(好ましくは炭素数5~6)または置換基を有していてもよい芳香族炭化水素環(好ましくは炭素数6~18。例えば、フルオレン環)がより好ましい。
この場合、中でも、Z1およびZ2は、それぞれ独立に、硫黄原子または酸素原子が好ましく、硫黄原子がより好ましい。
また、この場合、Ra12~Ra16は、それぞれ独立に、水素原子または置換基を表し、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましい。
この場合、中でも、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、または、-CRa17=CRa18-が好ましく、硫黄原子または-CRa17=CRa18-がより好ましい。
また、この場合、Ra12~Ra18は、それぞれ独立に、水素原子または置換基を表し、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましく、水素原子がより好ましい。
Ra19~Ra23は、それぞれ独立に、水素原子または置換基を表し、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基が好ましい。
中でも、B1は、-CO-、酸素原子、または、硫黄原子が好ましく、-CO-がより好ましい。
より具体的には、A1は、式(1)および(2)中に明示される、「R2が結合する炭素原子と共にビニレン基を形成する、=C<で表される炭素原子」ならびに、この炭素原子と結合する「-CO-」および「-B1-」を含む環である。
A1の好ましい形態については後述する。
具体的には、例えば、Y1が-CRa6=を表す場合におけるY1中のRa6とR1、Y1が-CRa6=を表す場合におけるY1中のRa6とR2、Y2が-CRa6=を表す場合におけるY2中のRa6とR1、Y2およびY3が-CRa6=を表す場合におけるY2中のRa6とY3中のRa6、Z1が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表しY3が-CRa6=を表す場合におけるZ1中のRa12~Ra18とY3中のRa6、Z1が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表しL1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表す場合におけるZ1中のRa12~Ra18とL1中のRa7~Ra11、L1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表しX1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるL1中のRa7~Ra11とX1中のRa1~Ra5、X1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるX1中のRa1~Ra5とR2、および、B1が-NRa19-、-CRa20Ra21-、または、-SiRa22Ra23-を表す場合におけるB1中のRa19~Ra23とR2とは、それぞれ互いに結合して環を形成していてもよい。
中でも、Y2およびY3が-CRa6=を表す場合においてY2中のRa6とY3中のRa6とが互いに結合して環を形成するのが好ましい。Y2中のRa6とY3中のRa6とが互いに結合して環を形成される環としては、例えば、芳香環(好ましくは5~6員環の芳香環、より好ましくはフラン環)が好ましく、上記芳香環の置換基がさらに環(好ましくは5~6員環の芳香環、より好ましくはチオフェン環)を形成しているのも好ましい。
具体的には、例えば、Y1が-CRa6=を表す場合におけるY1中のRa6とR1、Y1が-CRa6=を表す場合におけるY1中のRa6とR2、Z2が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表す場合におけるZ2中のRa12~Ra18とR1、Z2が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表しY3が-CRa6=を表す場合におけるZ2中のRa12~Ra18とY3中のRa6、Y3およびY4が-CRa6=を表す場合におけるY3中のRa6とY4中のRa6、Y4が-CRa6=を表しL1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表す場合におけるY4中のRa6とL1中のRa7~Ra11、L1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表しX1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるL1中のRa7~Ra11とX1中のRa1~Ra5、X1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるX1中のRa1~Ra5とR2、および、B1が-NRa19-、-CRa20Ra21-、または、-SiRa22Ra23-を表す場合におけるB1中のRa19~Ra23とR2とは、それぞれ互いに結合して環を形成していてもよい。
中でも、Y3およびY4が-CRa6=を表す場合においてY3中のRa6とY4中のRa6とが互いに結合して環を形成するのが好ましい。Y3中のRa6とY4中のRa6とが互いに結合して環を形成される環としては、例えば、芳香環(好ましくは5~6員環の芳香環、より好ましくはフラン環)が好ましく、上記芳香環の置換基がさらに環(好ましくは5~6員環の芳香環、より好ましくはチオフェン環)を形成しているのも好ましい。
A1は、ヘテロ原子を有していてもよく、例えば、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、および、ホウ素原子等が挙げられ、窒素原子、硫黄原子、または、酸素原子が好ましく、酸素原子がより好ましい。
A1は置換基を有していてもよく、上記置換基としてはハロゲン原子(好ましくは塩素原子)が好ましい。
A1中のヘテロ原子の数は、0~10が好ましく、0~5がより好ましく、0~2がさらに好ましい。なお、上記ヘテロ原子の数は、式中に明示される「-CO-」および「-B1-」に含まれるヘテロ原子の数、ならびに、A1の置換基が有するヘテロ原子の数を含まない数である。
A1は、芳香族性を示してもよく、示さなくてもよい。
A1は、単環構造でもよく、縮環構造でもよいが、5員環、6員環、または、5員環および6員環の少なくともいずれかを含む縮合環であるのが好ましい。上記縮合環を形成する環の数は、1~4が好ましく、1~3がより好ましい。
(a)1,3-ジカルボニル核:例えば、1,3-インダンジオン核、1,3-シクロヘキサンジオン、5,5-ジメチル-1,3-シクロヘキサンジオン、および、1,3-ジオキサン-4,6-ジオン等。
(b)2,4,6-トリオキソヘキサヒドロピリミジン核:例えば、バルビツール酸または2-チオバルビツール酸およびその誘導体等。誘導体としては、例えば、1-メチル、1-エチル等の1-アルキル体、1,3-ジメチル、1,3-ジエチル、1,3-ジブチル等の1,3-ジアルキル体、1,3-ジフェニル、1,3-ジ(p-クロロフェニル)、1,3-ジ(p-エトキシカルボニルフェニル)等の1,3-ジアリール体、1-エチル-3-フェニル等の1-アルキル-1-アリール体、および、1,3-ジ(2―ピリジル)等の1,3-ジヘテロアリール体等が挙げられる。
(c)2-チオ-2,4-チアゾリジンジオン核:例えば、ローダニンおよびその誘導体等。誘導体としては、例えば、3-メチルローダニン、3-エチルローダニン、3-アリルローダニン等の3-アルキルローダニン、3-フェニルローダニン等の3-アリールローダニン、および、3-(2-ピリジル)ローダニン等の3-ヘテロアリールローダニン等が挙げられる。
(d)2-チオ-2,4-オキサゾリジンジオン(2-チオ-2,4-(3H,5H)-オキサゾールジオン)核:例えば、3-エチル-2-チオ-2,4-オキサゾリジンジオン等。
(e)チアナフテノン核:例えば、3(2H)-チアナフテノン-1,1-ジオキサイド等。
(f)2-チオ-2,5-チアゾリジンジオン核:例えば、3-エチル-2-チオ-2,5-チアゾリジンジオン等。
(g)2,4-チアゾリジンジオン核:例えば、2,4-チアゾリジンジオン、3-エチル-2,4-チアゾリジンジオン、および、3-フェニル-2,4-チアゾリジンジオン等。
(h)チアゾリン-4-オン核:例えば、4-チアゾリノン、および、2-エチル-4-チアゾリノン等。
(i)2,4-イミダゾリジンジオン(ヒダントイン)核:例えば、2,4-イミダゾリジンジオン、および、3-エチル-2,4-イミダゾリジンジオン等。
(j)2-チオ-2,4-イミダゾリジンジオン(2-チオヒダントイン)核:例えば、2-チオ-2,4-イミダゾリジンジオン、および、3-エチル-2-チオ-2,4-イミダゾリジンジオン等。
(k)3,5-ピラゾリジンジオン核:例えば、1,2-ジフェニル-3,5-ピラゾリジンジオン、および、1,2-ジメチル-3,5-ピラゾリジンジオン等。
(l)インダノン核:例えば、1-インダノン、3-フェニル-1-インダノン、3-メチル-1-インダノン、3,3-ジフェニル-1-インダノン、および、3,3-ジメチル-1-インダノン等。
(m)ベンゾフラン-3-(2H)-オン核:例えば、ベンゾフラン-3-(2H)-オン等。
(n)2,2-ジヒドロフェナレン-1,3-ジオン核等。
言い換えると、式(1)および(2)で表される化合物は、それぞれ、下記式(1X)および(2X)で表される化合物であるのが好ましい。
式(1X)中、R1、R2、および、Ra1~Ra23は、それぞれ互いに結合して環を形成してもよく、式(2X)中、R1、R2、および、Ra1~Ra23は、それぞれ互いに結合して環を形成してもよい。
環を形成する態様の例は上述の通りである。
Rc1~Rc3は、それぞれ独立に、水素原子または置換基であり、水素原子またはアルキル基(好ましくは炭素数1~4)が好ましい。
Rc4は、炭素原子と二重結合を形成する2価の置換基であり、酸素原子または硫黄原子が好ましい。
中でも、Q1は、-CRc1=CRc2-であるのが好ましい。
例えば、-CRc1=CRc2-において、Rc1とRc2とは、互いに結合して環を形成するのが好ましく、形成される環としては、置換基を有していてもよいベンゼン環が好ましい。また、上記ベンゼン環が有する置換基同士が互いに結合してさらに環を形成していてもよい。
また、-CRc1=CRc2-と-C(=Rc4)-とが、隣り合って存在している場合、Rc1とRc2とが互いに結合して環を形成し、さらに、Rc1とRc2とで形成された環とRc4とが互いに結合して別の環を形成しているのも好ましい。この場合のQ1は、例えば、1,8-ナフタレンジイル基である。
Rd1とRd2、Rd2とRd3、および、Rd3とRd4とは、それぞれ互いに結合して環を形成していてもよい。中でも、Rd2とRd3とが、互いに結合して環を形成するのが好ましい。このようにして形成される環に特に制限はなく、芳香環が好ましく、置換基を有していてもよいベンゼン環がより好ましい。
式(3)および(4)中のR1およびR2は、式(1)および(2)中のR1およびR2と同義である。
R3は、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、または、後述する式(C)で表される基(好ましくは式(CX)で表される基)が好ましい。
R4~R6は、水素原子が好ましい。
Ra1~Ra5は、それぞれ独立に、水素原子または置換基を表す。
式(3)および(4)中のX1およびRa1~Ra5は、式(1)および(2)中のX1およびRa1~Ra5とそれぞれ同義である。
Ra7~Ra11は、それぞれ独立に、水素原子または置換基を表す。
式(3)および(4)中のL1およびRa7~Ra11は、式(1)および(2)中のL1およびRa7~Ra11とそれぞれ同義である。
L1が酸素原子、硫黄原子、セレン原子、テルル原子、-NRa7-、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-の場合、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、-CO-、または、-CRa17=CRa18-を表す。
Ra12~Ra18は、それぞれ独立に、水素原子または置換基を表す。
式(3)および(4)中のZ1、Z2、および、Ra12~Ra18は、式(1)および(2)中のZ1、Z2、および、Ra12~Ra18と、それぞれ同義である。
より具体的には、A2は、式(3)および(4)中に明示される、「R2が結合する炭素原子と共にビニレン基を形成する、=C<で表される炭素原子」および、この炭素原子と隣接する2個の「-CO-」を含む環である。
A2の好ましい形態については後述する。
具体的には、例えば、R1とR5、R1とR4、R3とR4、R2とR5、Z1が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表す場合におけるZ1中のRa12~Ra18とR3、Z1が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表しL1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表す場合におけるZ1中のRa12~Ra18とL1中のRa7~Ra11、L1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表しX1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるL1中のRa7~Ra11とX1中のRa1~Ra5、および、X1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるX1中のRa1~Ra5とR2とは、それぞれ互いに結合して環を形成していてもよい。
中でも、R3とR4とが互いに結合して環を形成するのが好ましい。R3とR4とが互いに結合して環を形成される環としては、例えば、芳香環(好ましくは5~6員環の芳香環、より好ましくはフラン環)が好ましく、上記芳香環の置換基がさらに環(好ましくは5~6員環の芳香環、より好ましくはチオフェン環)を形成しているのも好ましい。
具体的には、例えば、R1とR5、R2とR5、R3とR6、Z2が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表す場合におけるZ2中のRa12~Ra18とR1、Z2が-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CRa17=CRa18-を表す場合におけるZ2中のRa12~Ra18とR3、L1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表しX1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるL1中のRa7~Ra11とR6、L1が-NRa7-、-CRa8Ra9-、または、-SiRa10Ra11-を表しX1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるL1中のRa7~Ra11とX1中のRa1~Ra5、および、X1が-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す場合におけるX1中のRa1~Ra5とR2とは、それぞれ互いに結合して環を形成していてもよい。
中でも、R3とR6とが互いに結合して環を形成するのが好ましい。R3とR6とが互いに結合して環を形成される環としては、例えば、芳香環(好ましくは5~6員環の芳香環、より好ましくはフラン環)が好ましく、上記芳香環の置換基がさらに環(好ましくは5~6員環の芳香環、より好ましくはチオフェン環)を形成しているのも好ましい。
A2の好ましい態様としては、式(1)および(2)中のB1が-CO-を表す場合におけるA1の好ましい態様が同様に挙げられる。
つまり、式(3)および(4)中のA2は、下記式(3X)および(4X)中の「R2が結合する炭素原子と共にビニレン基を形成する、=C<で表される炭素原子」、2つの「-CO-」、および、「-Q1-」とが共同して形成される環であるのが好ましい。
言い換えると、式(3)および(4)で表される化合物は、それぞれ、下記式(3X)および(4X)で表される化合物であるのが好ましい。
式(3X)中、R1~R5、Ra1~Ra5、および、Ra7~Ra18は、それぞれ互いに結合して環を形成していてもよく、式(4X)中、R1~R3、R5、R6、Ra1~Ra5、および、Ra7~Ra18は、それぞれ互いに結合して環を形成していてもよい。
環を形成する態様の例は上述の通りである。
Q1は、式(1X)および(2X)中のQ1と同義である。
式(5)中のR1~R5は、式(3)中のR1~R5と同義である。
X51は、硫黄原子が好ましい。
Ra51およびRa52は、それぞれ独立に、水素原子または置換基を表す。
Ra51およびRa52は、式(1)中のRa8およびRa9とそれぞれ同義である。
Ra51とRa52とは、互いに結合して環を形成していてもよく、環を形成する態様としては、Ra8とRa9とが互いに結合して環を形成する態様が同様に挙げられる。
この場合、Z51は、硫黄原子が好ましい。
L51が-CRa51Ra52-の場合、Z51は、硫黄原子、酸素原子、または、-CRa53=CRa54-を表す。
この場合、Z51は、硫黄原子または-CRa53=CRa54-が好ましい。
Ra53およびRa54は、それぞれ独立に、水素原子または置換基を表す。
Ra53およびRa54は、式(1)中のRa17およびRa18とそれぞれ同義である。
式(5)中のA2は、式(3)中のA2と同義である。
A2の好ましい形態については後述する。
具体的には、例えば、R1とR5、R1とR4、R3とR4、R2とR5、Z51が-CRa53=CRa54-を表す場合におけるZ51中のRa53~Ra54とR3、および、Z51が-CRa53=CRa54-を表しL51が-CRa51Ra52-を表す場合におけるZ51中のRa53~Ra54とL51中のRa51~Ra52とは、それぞれ互いに結合して環を形成していてもよい。
中でも、R3とR4とが互いに結合して環を形成するのが好ましい。R3とR4とが互いに結合して環を形成される環として好ましい形態は式(3)の説明において上述した通りである。
言い換えると、式(5)で表される化合物は、下記式(5X)で表される化合物であるのが好ましい。
式(5X)中、R1~R5およびRa51~Ra54は、それぞれ互いに結合して環を形成していてもよい。
環を形成する態様の例は上述の通りである。
Q1は、式(1X)および(2X)中のQ1と同義である。
式(6)中のR1~R5は、式(3)中のR1~R5と同義である。
式(6)中のRd1~Rd4は、式(D)中のRd1~Rd4と同義である。
具体的には、例えば、R1とR5、R1とR4、R3とR4、および、R2とR5とは、それぞれ互いに結合して環を形成していてもよい。
中でも、R3とR4とが互いに結合して環を形成するのが好ましい。R3とR4とが互いに結合して環を形成される環は式(3)の説明において上述した通りである。
本明細書における置換基Wについて記載する。
置換基Wとしては、例えば、ハロゲン原子(フッ素原子、塩素原子、臭素原子、および、ヨウ素原子等)、アルキル基、アルケニル基(シクロアルケニル基、および、ビシクロアルケニル基を含む)、アルキニル基、アリール基、複素環基(ヘテロ環基といってもよい。ヘテロアリール基を含む)、シアノ基、ヒドロキシ基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基(アニリノ基を含む)、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルまたはアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキルまたはアリールスルフィニル基、アルキルまたはアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリールまたはヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、ボロン酸基(-B(OH)2)、スルホ基、カルボキシ基、リン酸基、ホスホニル基、ホスホリル基、モノ硫酸エステル基、モノリン酸エステル基、ホスホン酸基、ホスフィン酸基、ホウ酸基、および、その他の公知の置換基が挙げられる。
また、置換基Wは、さらに置換基Wで置換されていてもよい。例えば、アルキル基にハロゲン原子が置換していてもよい。
なお、置換基Wの詳細については、特開2007-234651号公報の段落[0023]に記載される。
式(C)中、R2、B1、および、A1は、式(1)および(2)中のR2、B1、および、A1と同義である。*は、結合位置を表す。
式(CX)中、R2、B1、および、Q1は、式(1X)および(2X)中のR2、B1、および、Q1と同義である。*は、結合位置を表す。
なお、式(C)および(CX)中、R2が結合する炭素原子とそれに隣接する炭素原子とで構成されるC=C二重結合に基づいて区別され得る幾何異性体について、式(C)および(CX)は、それぞれ、そのいずれをも含む。
アルキル基ALとしては、例えば、炭素数1~15が好ましく、1~10がより好ましく、1~6がさらに好ましい。アルキル基としては、直鎖状、分岐鎖状、および、環状のいずれであってもよい。
アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、t-ブチル基、n-ヘキシル基、および、シクロペンチル基等が挙げられる。
また、アルキル基は、例えば、シクロアルキル基、ビシクロアルキル基、および、トリシクロアルキル基であってもよく、これらの環状構造を部分構造として有していてもよい。
アルキル基が有し得る置換基としては特に制限されないが、例えば、置換基Wが挙げられ、アリール基(好ましくは炭素数6~18、より好ましくは炭素数6)、ヘテロアリール基(好ましくは炭素数5~18、より好ましくは炭素数5~6)、または、ハロゲン原子(好ましくはフッ素原子または塩素原子)が好ましい。
アリール基ARとしては、例えば、炭素数6~18のアリール基が挙げられる。
アリール基は、単環式であっても、多環式であってもよい。
アリール基としては、例えば、フェニル基、ナフチル基、または、アントリル基が好ましく、フェニル基がより好ましい。
アリール基が有し得る置換基としては特に制限されないが、例えば、置換基Wが挙げられる。中でも、置換基としては、さらに置換基を有していてもよいアルキル基(好ましくは炭素数1~10)が好ましく、メチル基がより好ましい。
ヘテロアリール基HAとしては、硫黄原子、酸素原子、または窒素原子等のヘテロ原子を含む、単環式または多環式の環構造を有するヘテロアリール基が挙げられる。
上記ヘテロアリール基中の炭素数は特に制限されないが、3~18が好ましく、3~5がより好ましい。
ヘテロアリール基が有するヘテロ原子の数は特に制限されず、1~10が好ましく、1~4がより好ましく、1~2がさらに好ましい。
ヘテロアリール基の環員数は特に制限されないが、3~8が好ましく、5~7がより好ましく、5~6がさらに好ましい。
上記ヘテロアリール基としては、フリル基、ピリジル基、キノリル基、イソキノリル基、アクリジニル基、フェナントリジニル基、プテリジニル基、ピラジニル基、キノキサリニル基、ピリミジニル基、キナゾリル基、ピリダジニル基、シンノリニル基、フタラジニル基、トリアジニル基、オキサゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、イミダゾリル基、ベンゾイミダゾリル基、ピラゾリル基、インダゾリル基、イソオキサゾリル基、ベンゾイソオキサゾリル基、イソチアゾリル基、ベンゾイソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、ベンゾフリル基、チエニル基、ベンゾチエニル基、ジベンゾフリル基、ジベンゾチエニル基、ピロリル基、インドリル基、イミダゾピリジニル基、および、カルバゾリル基等が挙げられる。
ヘテロアリール基が有し得る置換基としては特に制限されないが、例えば、置換基Wが挙げられる。
なお、本明細書中、「酸性基」とは、解離性のプロトンを有する置換基であり、pKaが11以下の置換基を意図する。酸性基のpKaは、J.Phys.Chem.A2011,115,p.6641-6645に記載の「SMD/M05-2X/6-31G*」方法に従って求められる。酸性基としては、例えば、カルボキシ基、ホスホニル基、ホスホリル基、スルホ基、および、ホウ酸基等の酸性を示す酸基、並びに、これらの酸基を有する基が挙げられる。
なお、上記極大吸収波長は、特定化合物の吸収スペクトルを吸光度が0.5~1になる程度の濃度に調整して溶液状態(溶剤:クロロホルム)で測定した値である。
特定化合物は1種単独で使用してもよく、2種以上を併用してもよい。
光電変換膜は、上述した特定化合物以外の他の成分として、n型有機半導体を含むのが好ましい。
n型有機半導体は、アクセプタ性有機半導体材料(化合物)であり、電子を受容しやすい性質がある有機化合物をいう。さらに詳しくは、n型有機半導体は、2つの有機化合物を接触させて用いた場合に電子親和力の大きい方の有機化合物をいう。
n型有機半導体としては、例えば、縮合芳香族炭素環化合物(例えば、フラーレン、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ピレン誘導体、ペリレン誘導体、および、フルオランテン誘導体);窒素原子、酸素原子、および、硫黄原子の少なくとも1つを有する5~7員環のヘテロ環化合物(例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、キノリン、キノキサリン、キナゾリン、フタラジン、シンノリン、イソキノリン、プテリジン、アクリジン、フェナジン、フェナントロリン、テトラゾール、ピラゾール、イミダゾール、および、チアゾール等);ポリアリーレン化合物;フルオレン化合物;シクロペンタジエン化合物;シリル化合物;ならびに、含窒素ヘテロ環化合物を配位子として有する金属錯体等が挙げられる。
n型有機半導体は1種単独で使用してもよく、2種以上を併用してもよい。
なお、光電変換膜中、特定化合物およびn型有機半導体の合計含有量は、光電変換膜全質量に対して、60~100質量%が好ましい。
また、光電変換膜に含まれる成分としては、上述した特定化合物および上段で例示したn型有機半導体の他に、例えば、後述する電子供与性化合物として例示する化合物、および、後述する電子受容性化合物として例示する化合物が挙げられる。
ここで、上記成分の数の合計を計算する場合、同一分類に含まれる成分であっても、異なる化合物であればそれぞれ1種として計上する。例えば、光電変換膜が、上段で例示した特定化合物のうちの2種類の特定化合物を含む場合、それぞれの特定化合物は別個に1種ずつ計上する。
ただし、特定化合物中、R2で表される基が結合する炭素原子とそれに隣接する炭素原子とで構成されるC=C二重結合に基づいて区別されるシス体とトランス体とについては、それぞれ別個の成分としては計上しない。
また、光電変換膜が実質的に含む成分とは、光電変換膜中において、光電変換膜全質量に対し1質量%以上含まれる成分を意図する。
光電変換膜は、主に、乾式成膜法により成膜できる。乾式成膜法の具体例としては、蒸着法(特に、真空蒸着法)、スパッタ法、イオンプレーティング法、および、MBE(Molecular Beam Epitaxy)法等の物理気相成長法、ならびに、プラズマ重合等のCVD(Chemical Vapor Deposition)法が挙げられる。中でも、真空蒸着法が好ましい。真空蒸着法により光電変換膜を成膜する場合、真空度および蒸着温度等の製造条件は常法に従って設定できる。
電極(上部電極(透明導電性膜)15と下部電極(導電性膜)11)は、導電性材料から構成される。導電性材料としては、金属、合金、金属酸化物、電気伝導性化合物、および、これらの混合物等が挙げられる。
上部電極15から光が入射されるため、上部電極15は検知したい光に対し透明であるのが好ましい。上部電極15を構成する材料としては、例えば、アンチモンまたはフッ素等をドープした酸化錫(ATO:Antimony Tin Oxide、FTO:Fluorine doped Tin Oxide)、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO:Indium Tin Oxide)、および、酸化亜鉛インジウム(IZO:Indium zinc oxide)等の導電性金属酸化物;金、銀、クロム、および、ニッケル等の金属薄膜;これらの金属と導電性金属酸化物との混合物または積層物;ならびに、ポリアニリン、ポリチオフェン、および、ポリピロール等の有機導電性材料、等が挙げられる。中でも、高導電性、および、透明性等の点から、導電性金属酸化物が好ましい。
電極の材料がITOの場合、電子ビーム法、スパッタ法、抵抗加熱蒸着法、化学反応法(ゾル-ゲル法等)、および、酸化インジウムスズの分散物の塗布等の方法が挙げられる。
本発明の光電変換素子は、導電性膜と透明導電性膜の間に、光電変換膜の他に1種以上の中間層を有しているのも好ましい。上記中間層としては、電荷ブロッキング膜が挙げられる。光電変換素子がこの膜を有することにより、得られる光電変換素子の特性(暗電流の抑制性等)がより優れる。電荷ブロッキング膜としては、電子ブロッキング膜と正孔ブロッキング膜とが挙げられる。以下に、それぞれの膜について詳述する。
電子ブロッキング膜は、電子供与性化合物を含む。具体的には、低分子材料では、N,N’-ビス(3-メチルフェニル)-(1,1’-ビフェニル)-4,4’-ジアミン(TPD)、および、4,4’-ビス[N-(ナフチル)-N-フェニル-アミノ]ビフェニル(α-NPD)等の芳香族ジアミン化合物;ポルフィリン、テトラフェニルポルフィリン銅、フタロシアニン、銅フタロシアニン、および、チタニウムフタロシアニンオキサイド等のポルフィリン化合物;[1]ベンゾチエノ[3,2,b][1]ベンゾチオフェン(BTBT)、ジナフト[2,3-b:2´,3´-f]チエノ[3,2-b]チオフェン(DNTT)、ベンゾ[1,2-b:4,5-b´]ジチオフェン(BDT)等のチエノアセン化合物、テトラセン、ペンタセン、および、ルブレン等のアセン化合物、クリセン、および、フェナントレン等のフェナセン化合物;ならびに、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、スチルベン誘導体、ピラゾリン誘導体、テトラヒドロイミダゾール、ポリアリールアルカン、ブタジエン、4,4’,4’’-トリス(N-(3-メチルフェニル)N-フェニルアミノ)トリフェニルアミン(m-MTDATA)、トリアゾール誘導体、オキサジザゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、および、シラザン誘導体等が挙げられる。高分子材料としては、フェニレンビニレン、フルオレン、カルバゾール、インドール、ピレン、ピロール、ピコリン、チオフェン、アセチレン、および、ジアセチレン等の重合体、ならびに、その誘導体が挙げられる。また、特許第6047109号の段落[0044]~[0051]に記載の化合物、特許第5597450号の段落[0049]~[0063]に記載の化合物、特開2011-225544号公報の段落[0119]~[0158]に記載の化合物、および、特開2012-94660号公報の段落[0086]~[0090]に記載の化合物等が挙げられる。
電子ブロッキング膜は、無機材料で構成されていてもよい。一般的に、無機材料は有機材料よりも誘電率が大きいため、無機材料を電子ブロッキング膜に用いた場合に、光電変換膜に電圧が多くかかるようになり、光電変換効率が高くなる。電子ブロッキング膜となりうる無機材料としては、例えば、酸化カルシウム、酸化クロム、酸化クロム銅、酸化マンガン、酸化コバルト、酸化ニッケル、酸化銅、酸化ガリウム銅、酸化ストロンチウム銅、酸化ニオブ、酸化モリブデン、酸化インジウム銅、酸化インジウム銀、および、酸化イリジウム等が挙げられる。
正孔ブロッキング膜は、電子受容性化合物を含む。
電子受容性化合物としては、1,3-ビス(4-tert-ブチルフェニル-1,3,4-オキサジアゾリル)フェニレン(OXD-7)等のオキサジアゾール誘導体;アントラキノジメタン誘導体;ジフェニルキノン誘導体;バソクプロイン、バソフェナントロリン、および、これらの誘導体;トリアゾール化合物;トリス(8-ヒドロキシキノリナート)アルミニウム錯体;ビス(4-メチル-8-キノリナート)アルミニウム錯体;ジスチリルアリーレン誘導体;ならびに、シロール化合物、等が挙げられる。また、特開2006-100767号公報の段落[0056]~[0057]に記載の化合物等が挙げられる。
光電変換素子は、さらに基板を有していてもよい。使用される基板の種類は特に制限されず、半導体基板、ガラス基板、および、プラスチック基板が挙げられる。
なお、基板の位置は特に制限されないが、通常、基板上に導電性膜、光電変換膜、および、透明導電性膜をこの順で積層する。
光電変換素子は、さらに封止層を有していてもよい。光電変換材料は水分子等の劣化因子の存在で顕著にその性能が劣化してしまうことがある。そこで、水分子を浸透させない緻密な金属酸化物、金属窒化物、もしくは、金属窒化酸化物等のセラミクス、または、ダイヤモンド状炭素(DLC:Diamond-like Carbon)等の封止層で光電変換膜全体を被覆して封止することで、上記劣化を防止できる。
なお、封止層としては、特開2011-082508号公報の段落[0210]~[0215]に記載に従って、材料の選択および製造を行ってもよい。
光電変換素子の用途として、例えば、光電池および光センサが挙げられるが、本発明の光電変換素子は光センサとして用いるのが好ましい。光センサとしては、上記光電変換素子単独で用いてもよいし、上記光電変換素子を直線状に配したラインセンサ、または、平面上に配した2次元センサとして用いてもよい。本発明の光電変換素子は、ラインセンサでは、スキャナー等の様に光学系および駆動部を用いて光画像情報を電気信号に変換し、2次元センサでは、撮像モジュールのように光画像情報を光学系でセンサ上に結像させ電気信号に変換することで撮像素子として機能する。
次に、光電変換素子10aを備えた撮像素子の構成例を説明する。
なお、以下に説明する構成例において、すでに説明した部材等と同等な構成、または、作用を有する部材等については、図中に同一符号または相当符号を付すことにより、説明を簡略化または省略する。
撮像素子とは画像の光情報を電気信号に変換する素子であり、複数の光電変換素子が同一平面状でマトリクス上に配置されており、それぞれの光電変換素子(画素)において光信号を電気信号に変換し、その電気信号を画素ごとに逐次撮像素子外に出力できるものをいう。そのために、画素ひとつあたり、一つの光電変換素子、一つ以上のトランジスタから構成される。
図3は、本発明の一実施形態を説明するための撮像素子の概略構成を示す断面模式図である。この撮像素子は、デジタルカメラおよびデジタルビデオカメラ等の撮像装置、電子内視鏡、ならびに、携帯電話機等の撮像モジュール等に搭載される。
この撮像素子は、図1Aに示したような構成の複数の光電変換素子と、各光電変換素子の光電変換膜で発生した電荷に応じた信号を読み出す読み出し回路が形成された回路基板とを有し、回路基板上方の同一面上に、複数の光電変換素子が一次元状または二次元状に配列された構成となっている。
対向電極電圧供給部115と読み出し回路116が形成された回路基板上に、接続部105および106、複数の接続電極103、複数の画素電極104、ならびに、絶縁層102を形成する。複数の画素電極104は、絶縁層102の表面に例えば正方格子状に配置する。
本発明は化合物の発明も含む。本発明の化合物とは、上述した式(5)で表される化合物と同一である。
<化合物(D-4)の合成>
化合物(D-4)は、以下のスキームに従って、合成した。
得られた化合物(D-4)は1H NMR(Nuclear Magnetic Resonance)およびMS(Mass Spectrometry)により同定した。
1H NMRスペクトル(400MHz,CDCl3)を図4に示す。
MS(ESI+)m/z:621.3([M+H]+)
化合物(D-13)は、以下のスキームに従って、合成した。
得られた化合物(D-13)はNMR(Nuclear Magnetic Resonance)、MS(Mass Spectrometry)により同定した。
1H NMRスペクトル(400MHz,CDCl3)を図5に示す。
MS(ESI+)m/z:548.2([M+H]+)
上記化合物(D-13)の合成方法を参照して、さらに化合物(D-12)、(D-14)、および、(D-15)を合成した。
以下に、得られた化合物(D-1)~(D-15)、および、比較化合物(R-1)~(R-2)の構造を示す。なお、得られた化合物(D-1)~(D-15)について下記で示す構造式は、化合物を式(1)または(2)に当てはめた場合において、R2が結合する炭素原子とそれに隣接する炭素原子とで構成されるC=C二重結合に相当する基に基づいて区別され得るシス体とトランス体とのいずれをも含むことを意図する。
<光電変換素子の作製(素子(A))>
得られた化合物を用いて図1Aの形態の光電変換素子を作製した。つまり、本実施例で評価する光電変換素子は、下部電極11、電子ブロッキング膜16A、光電変換膜12、および、上部電極15からなる。
具体的には、ガラス基板上に、アモルファス性ITOをスパッタ法により成膜して、下部電極11(厚み:30nm)を形成し、さらに、下部電極11上に下記化合物(EB-1)を真空蒸着法により成膜して、電子ブロッキング膜16A(厚み:10nm)を形成した。
さらに、基板の温度を25℃に制御した状態で、電子ブロッキング膜16A上にp型有機半導体として化合物(D-1)とn型有機半導体としてフラーレン(C60)とをそれぞれ単層換算で100nm、100nmとなるように真空蒸着法により共蒸着して成膜し、200nmのバルクヘテロ構造を有する光電変換膜12を形成した。
さらに、光電変換膜12上に、アモルファス性ITOをスパッタ法により成膜して、上部電極15(透明導電性膜)(厚み:10nm)を形成した。上部電極15上に、真空蒸着法により封止層としてSiO膜を形成した後、その上にALCVD(Atomic Layer Chemical Vapor Deposition)法により酸化アルミニウム(Al2O3)層を形成し、光電変換素子を作製した。
得られた光電変換素子を、素子(AD-1)とする。
また、化合物(R-2)を用いて光電変換素子の作製を試みたところ、電子ブロッキング膜16A上に化合物(R-2)を蒸着できず、光電変換素子を作製できなかった。
得られた各光電変換素子の駆動の確認をした。各光電変換素子に1.0×105V/cmの電界強度となるように電圧を印加した。その後、上部電極(透明導電性膜)側から光を照射して540nmでの光電変換効率(外部量子効率)を測定したところ、化合物(D-1)~(D-15)および(R-1)を用いて作製した素子(A)はいずれも60%以上の光電変換効率を示し、光電変換素子として十分な外部量子効率を有することを確認した。外部量子効率は、オプテル製定エネルギー量子効率測定装置を用いて測定した。照射した光量は50μW/cm2であった。
得られた各素子(A)をホットプレート上で160℃、1時間加熱した後に、吸収極大波長での光電変換効率が60%になるように電圧をかけ、その電圧での暗電流を測定した。加熱前の同様の測定での暗電流を1として、加熱後の暗電流の相対値で、光電変換素子の耐熱性の評価を行った。
暗電流の測定値は小さいほど好ましい。
相対値が1.5未満である場合をA、1.5以上2.0未満である場合をB、2.0以上である場合をCとした。結果を表に示す。なお、実用上、B以上が好ましく、Aがより好ましい。
また、特定化合物において、式(1)および(2)中のR1に相当する基が、置換基を有していてもよいアリール基である場合、より光電変換素子の耐熱性が優れることが確認された。
上述の<光電変換素子の耐熱性の評価>を実施した後の素子(AD-1)~(AD-15)を用いて、図3に示す形態と同様の撮像素子をそれぞれ作製したところ、撮像素子の性能に問題はなかった。
11 導電性膜(下部電極)
12 光電変換膜
15 透明導電性膜(上部電極)
16A 電子ブロッキング膜
16B 正孔ブロッキング膜
100 画素分離型撮像素子
101 基板
102 絶縁層
103 接続電極
104 画素電極(下部電極)
105 接続部
106 接続部
107 光電変換膜
108 対向電極(上部電極)
109 緩衝層
110 封止層
111 カラーフィルタ(CF)
112 隔壁
113 遮光層
114 保護層
115 対向電極電圧供給部
116 読み出し回路
200 光電変換素子(ハイブリッド型の光電変換素子)
201 無機光電変換膜
202 n型ウェル
203 p型ウェル
204 n型ウェル
205 p型シリコン基板
207 絶縁層
208 画素電極
209 有機光電変換膜
210 共通電極
211 保護膜
212 電子ブロッキング膜
Claims (13)
- 導電性膜、光電変換膜、および、透明導電性膜をこの順で有する光電変換素子であって、
前記光電変換膜が、式(1)で表される化合物および式(2)で表される化合物からなる群から選択される少なくとも1種の化合物を含む、光電変換素子。
式(1)および(2)中、R1およびR2は、それぞれ独立に、水素原子または置換基を表す。
X1は、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す。
Y1~Y4は、それぞれ独立に、-CRa6=または窒素原子を表す。
L1は、単結合、酸素原子、硫黄原子、セレン原子、テルル原子、-NRa7-、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-を表す。
L1が単結合の場合、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CO-を表す。
L1が酸素原子、硫黄原子、セレン原子、テルル原子、-NRa7-、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-の場合、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、-CO-、または、-CRa17=CRa18-を表す。
B1は、-CO-、酸素原子、硫黄原子、セレン原子、テルル原子、-NRa19-、-CRa20Ra21-、または、-SiRa22Ra23-を表す。
Ra1~Ra23は、それぞれ独立に、水素原子または置換基を表す。
A1は、環を表す。
式(1)中、R1、R2、および、Ra1~Ra23は、それぞれ互いに結合して環を形成してもよい。
式(2)中、R1、R2、および、Ra1~Ra23は、それぞれ互いに結合して環を形成してもよい。 - 前記式(1)で表される化合物が式(3)で表される化合物であり、前記式(2)で表される化合物が式(4)で表される化合物である、請求項1に記載の光電変換素子。
式(3)および(4)中、R1~R6は、それぞれ独立に、水素原子または置換基を表す。
X1は、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa1-、-CRa2Ra3-、または、-SiRa4Ra5-を表す。
L1は、単結合、酸素原子、硫黄原子、セレン原子、テルル原子、-NRa7-、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-を表す。
L1が単結合の場合、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、または、-CO-を表す。
L1が酸素原子、硫黄原子、セレン原子、テルル原子、-NRa7-、-CRa8Ra9-、-SiRa10Ra11-、または、-CO-の場合、Z1およびZ2は、それぞれ独立に、硫黄原子、酸素原子、セレン原子、テルル原子、-NRa12-、-CRa13Ra14-、-SiRa15Ra16-、-CO-、または、-CRa17=CRa18-を表す。
Ra1~Ra5およびRa7~Ra18は、それぞれ独立に、水素原子または置換基を表す。
A2は環を表す。
式(3)中、R1~R5、Ra1~Ra5、および、Ra7~Ra18は、それぞれ互いに結合して環を形成していてもよい。
式(4)中、R1~R3、R5、R6、Ra1~Ra5、および、Ra7~Ra18は、それぞれ互いに結合して環を形成していてもよい。 - L1が、単結合または-CRa8Ra9-を表す、請求項1または2に記載の光電変換素子。
- X1が、硫黄原子、酸素原子、または、セレン原子を表す、請求項1~3のいずれか1項に記載の光電変換素子。
- 前記光電変換膜が、式(5)で表される化合物を含む、請求項1~4のいずれか1項に記載の光電変換素子。
式(5)中、R1~R5は、それぞれ独立に、水素原子または置換基を表す。
X51は、硫黄原子または酸素原子を表す。
L51は、単結合または-CRa51Ra52-を表す。
L51が単結合の場合、Z51は、硫黄原子または酸素原子を表す。
L51が-CRa51Ra52-の場合、Z51は、硫黄原子、酸素原子、または、-CRa53=CRa54-を表す。
Ra51~Ra54は、それぞれ独立に、水素原子または置換基を表す。
A2は環を表す。
R1~R5およびRa51~Ra54は、それぞれ互いに結合して環を形成していてもよい。 - R1が、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、または、置換基を有していてもよいヘテロアリール基を表す、請求項1~6のいずれか1項に記載の光電変換素子。
- 前記式(1)で表される化合物および前記式(2)で表される化合物の分子量が、400~900である、請求項1~7のいずれか1項に記載の光電変換素子。
- 前記光電変換膜が、さらにn型有機半導体を含み、
前記光電変換膜が、前記式(1)で表される化合物および前記式(2)で表される化合物からなる群から選択される少なくとも1種の化合物と、前記n型有機半導体とが混合された状態で形成するバルクへテロ構造を有する、請求項1~8のいずれか1項に記載の光電変換素子。 - 前記導電性膜と前記透明導電性膜の間に、前記光電変換膜の他に1種以上の中間層を有する、請求項1~9のいずれか1項に記載の光電変換素子。
- 請求項1~10のいずれか1項に記載の光電変換素子を有する、光センサ。
- 請求項1~10のいずれか1項に記載の光電変換素子を有する、撮像素子。
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WO2021221108A1 (ja) | 2020-04-30 | 2021-11-04 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、化合物 |
WO2022014721A1 (ja) | 2020-07-17 | 2022-01-20 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、及び化合物 |
WO2022138833A1 (ja) | 2020-12-24 | 2022-06-30 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、化合物 |
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