WO2019009249A1 - 光電変換素子、光センサ、撮像素子、および、化合物 - Google Patents
光電変換素子、光センサ、撮像素子、および、化合物 Download PDFInfo
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- WO2019009249A1 WO2019009249A1 PCT/JP2018/025078 JP2018025078W WO2019009249A1 WO 2019009249 A1 WO2019009249 A1 WO 2019009249A1 JP 2018025078 W JP2018025078 W JP 2018025078W WO 2019009249 A1 WO2019009249 A1 WO 2019009249A1
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 125000004095 oxindolyl group Chemical class N1(C(CC2=CC=CC=C12)=O)* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000000059 patterning Methods 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
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000000206 photolithography Methods 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
- 229920000548 poly(silane) polymer Chemical class 0.000 description 1
- 229920000768 polyamine Chemical class 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 150000003217 pyrazoles Chemical class 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
- 125000001725 pyrenyl group Chemical group 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
- 150000003233 pyrroles Chemical class 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 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
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl 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
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005259 triarylamine group Chemical class 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical class CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
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- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
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- 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
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- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
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- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- 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 photoelectric conversion element having a photoelectric conversion film containing the following compound.
- Patent Document 2 discloses a semiconductor for a photoelectric conversion material, which is characterized in that it contains a dye as described below.
- Patent Document 3 discloses a semiconductor for a photoelectric conversion material characterized by containing the following heterocyclic compound.
- An object of the present invention is to provide a photoelectric conversion element having a photoelectric conversion film excellent in vapor deposition suitability and showing excellent photoelectric conversion efficiency even when the photoelectric conversion film is a thin film in view of the above-mentioned 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, wherein the photoelectric conversion film contains a compound represented by the formula (1) described later.
- Conversion element (2)
- the photoelectric conversion element as described in (1) whose compound represented by Formula (1) mentioned later is a compound represented by Formula (2) mentioned later.
- R b1 is an alkyl group, an aryl group, a heteroaryl group, a -CO-alkyl group, a -CO-aryl group, or an optionally substituted alkyl group, or
- the photoelectric conversion device according to (2) which represents a -CO-heteroaryl group.
- X 1 in Formula (2) described later represents an oxygen atom or a sulfur atom.
- the photoelectric conversion element as described in (6) in which Rc3 in Formula (3) mentioned later represents the aryl group or heteroaryl group which may have a substituent.
- the photoelectric conversion film further has an n-type organic semiconductor, and has a bulk heterostructure formed by mixing a compound represented by the formula (1) described later and the n-type organic semiconductor.
- An optical sensor comprising the photoelectric conversion device according to any one of (1) to (9).
- An imaging device comprising the photoelectric conversion device according to any one of (1) to (9).
- the present invention has a photoelectric conversion film which is excellent in vapor deposition aptitude, and it can provide the photoelectric conversion element which shows the outstanding photoelectric conversion efficiency, even when a photoelectric conversion film is a thin film. 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
- alkyl group means an 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.
- the bonding direction of the divalent group described in the present specification is not particularly limited.
- X 1 in formula (2) described later when X 1 in formula (2) described later is —NNCR b13 —, it is bonded to the R b3 side.
- an excellent thin film is a specific compound which does not have any of a carboxy group, a salt of a carboxy group, a phosphate group, a salt of a phosphate group, a sulfonate group, and a salt of a sulfonate group.
- salt is intended to be any of an alkali metal salt, an alkaline earth metal salt, an ammonium salt and a substituted ammonium salt.
- 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, it is possible to obtain a photoelectric conversion element having a photoelectric conversion film excellent in vapor deposition aptitude and exhibiting excellent photoelectric conversion efficiency at the time of thin film.
- the specific compound will be described in detail.
- the suitable conditions of the specific compound mentioned below are mentioned from the point which the photoelectric conversion efficiency at the time of a thin film is more excellent unless there is special mention.
- the substituents that the specific compound can have are each independently any of the substituents W described later.
- m represents an integer of 0 or more.
- m is preferably 0 to 4, more preferably 1 to 3, and still more preferably 1.
- Each of R a1 to R a7 independently represents a hydrogen atom or a substituent.
- the type of substituent is not particularly limited, and groups exemplified for the substituent W described later can be mentioned.
- R a1 to R a7 may be linked to each other to form a ring.
- R a1 and R a2 may be linked to each other to form a ring
- R a1 and R a7 may be linked to each other to form a ring
- R a3 and R a4 may be linked to each other to form a ring
- R a4 and R a5 are linked to each other to form a ring
- R a5 and R a6 may be linked to each other to form a ring
- R a3 and R a5 may be linked to each other to form a ring.
- R a3 and R a5 are linked to each other to form a ring
- m 0 is preferable.
- the plurality of R a2 's may be linked to each other to form a ring.
- the plurality of R a4 's may be linked to each other to form a ring.
- the R a4 that lie close to the most R a5 among the plurality present may R a4, and R a5 are preferably formed by connecting each other. That is, the ring formed by bonding the R a4 and R a5 to each other is condensed with the pyrrole ring group specified in the formula (1) to form a condensed ring structure (fused ring structure). preferable.
- Each of R a8 to R a15 independently represents a hydrogen atom or a substituent.
- R a1 in the case of not contributing to ring formation is an alkyl group, an aryl group, a heteroaryl group, a —CO-alkyl group, a —CO-aryl group, or a —CO-hetero group which may have a substituent.
- An aryl group is preferred.
- R a3 in the case of not contributing to ring formation is preferably an alkyl group, an aryl group, a heteroaryl group, or a non-aromatic heterocyclic group which may have a substituent, and an aryl group or a heteroaryl group. Groups are more preferred.
- R a2 and R a4 to R a7 in the case of not contributing to ring formation are each independently a hydrogen atom or an alkyl group, an aryl group or a heteroaryl group which may have a substituent. Is preferred.
- A represents a ring containing at least 2 carbon atoms.
- the carbon atom in the carbonyl group in Formula (1) and the carbon atom adjacent to the carbon atom of a carbonyl group are intended, and all carbon atoms are atoms which constitute A. .
- the carbon number of A is preferably 3 to 30, more preferably 3 to 20, and still more preferably 3 to 15.
- the above carbon number is a number including two carbon atoms specified in the formula.
- A may have a hetero atom, and examples of the hetero atom 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, and a nitrogen atom A sulfur atom or an oxygen atom is preferred, and an oxygen atom is more preferred.
- A may have a substituent, and the substituent is preferably a halogen atom.
- the number of heteroatoms in A is preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 2.
- the number of hetero atoms is the number of oxygen atoms contained in the carbonyl group constituting A shown in the formula (1) and the number not containing the number of halogen atoms which A has as a substituent. .
- A may or may not show aromaticity.
- A may be a single ring structure or a condensed ring structure, but 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.
- the ring represented by A preferably has a group represented by the following formula (A1).
- * 1 represents the bonding position with the carbon atom in the carbonyl group which comprises A specifically shown in Formula (1)
- * 2 is carbonyl which comprises A specifically shown in Formula (1) It represents a bonding position to one other carbon atom different from the carbon atom in the group.
- L represents a single bond or -NR L- .
- R L represents a hydrogen atom or a substituent. Among them, R L is preferably an alkyl group, an aryl group or a heteroaryl group, and more preferably an alkyl group or an aryl group. L is preferably a single bond.
- R Y1 to R Y5 each independently represent a hydrogen atom or a substituent. Among them, R Y1 to R Y5 are each independently preferably an alkyl group, an aryl group or a heteroaryl group, and more preferably an alkyl group or an aryl group.
- R Y1 and R Y2 are preferably linked to each other to form a ring, and R Y1 and R Y2 are linked to each other to form a benzene ring Is more preferable.
- Z represents a single bond, -CO- or -S-, preferably -CO-.
- the ring formed by combining -LYZ- and two carbon atoms specified in the formula (1) is a 5-membered member.
- the combination which becomes a ring or 6 membered ring is preferable.
- the 5- or 6-membered ring may be condensed with a different ring (preferably a benzene ring) to form a condensed ring structure.
- the group represented by the formula (A1) is more preferably a group represented by the following formula (A2).
- a 1 and A 2 each independently represent a hydrogen atom or a substituent.
- a 1 and A 2 are preferably linked to each other to form a ring, and A 1 and A 2 are more preferably linked to each other to form a benzene ring.
- the above-mentioned benzene ring formed by A 1 and A 2 preferably further has a substituent.
- a substituent a halogen atom is preferable, and a chlorine atom or a fluorine atom is more preferable.
- the substituent which the benzene ring has to be formed by the A 1 and A 2 may be further formed a connection to ring.
- the substituents possessed by the above-mentioned benzene ring formed by A 1 and A 2 may be further linked to each other to form a benzene ring.
- the group represented by the formula (A1) is more preferably a group represented by the following formula (A3).
- each of A 3 to A 6 independently represents a hydrogen atom or a substituent.
- each of A 3 to A 6 is preferably independently a hydrogen atom or a halogen atom, and more preferably a hydrogen atom, a chlorine atom or a fluorine atom.
- a 3 and A 4 may be linked to each other to form a ring, and A 4 and A 5 may be linked to each other to form a ring, and A 5 and A 6 are linked to each other And may form a ring.
- the ring formed by linking A 3 and A 4 , A 4 and A 5 , and A 5 and A 6 to each other is preferably a benzene ring.
- a 4 and A 5 are bonded to each other to form a ring, the ring and A 4 and A 5 are formed by connecting together a benzene ring is preferred.
- a substituent may be further substituted on the ring formed by connecting A 4 and A 5 to each other.
- a merocyanine dye which is generally used as an acidic nucleus is preferable, and the following may be mentioned as specific examples thereof.
- (B) pyrazolinone nucleus for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1- (2-benzothiazolyl) -3-methyl- 2-pyrazolin-5-one and the like.
- (C) Isoxazolinone nucleus for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.
- (D) Oxindole nucleus For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
- (E) 2,4,6-trioxohexahydropyrimidine nucleus for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof and the like.
- 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).
- (F) 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.
- (J) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
- (K) Thiazolin-4-one nucleus for example, 4-thiazolinone, and 2-ethyl-4-thiazolinone and the like.
- (M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus for example, 2-thio-2,4-imidazolidinedione, and 3-ethyl-2-thio-2,4- Imidazolidinediones and the like.
- (N) Imidazolin-5-one nucleus for example, 2-propylmercapto-2-imidazolin-5-one and the like.
- (O) 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione, and 1,2-dimethyl-3,5-pyrazolidinedione.
- the specific compound does not have any of a carboxy group, a salt of a carboxy group, a phosphate group, a salt of a phosphate group, a sulfonic acid group, and a salt of a sulfonic acid group from the viewpoint of avoiding deterioration of vapor deposition suitability.
- groups and their salts from the viewpoint of avoiding the deterioration of the vapor deposition ability, monosulfate ester group, monophosphate ester group, phosphonic acid group, phosphinic acid group, boric acid group, and those groups It is preferred not to have any of the salts.
- the specific compound is preferably a compound represented by the following formula (2).
- m in the formula (1) represents 1 and R a4 and R a5 are connected to each other to form a ring.
- R b1 to R b5 each independently represent a hydrogen atom or a substituent.
- the type of substituent is not particularly limited, and groups exemplified for the substituent W described later can be mentioned.
- R b1 is preferably an alkyl group, an aryl group, a heteroaryl group, a -CO-alkyl group, a -CO-aryl group, or a -CO-heteroaryl group which may have a substituent
- a group or an aryl group is more preferable, and an alkyl group having 1 to 2 carbon atoms, a cyclohexyl group or a phenyl group is more preferable.
- the phenyl group preferably has an alkyl group (preferably a branched alkyl group having 3 to 5 carbon atoms) as a substituent.
- R b3 is preferably an alkyl group, an aryl group, a heteroaryl group, or a non-aromatic heterocyclic group (such as a piperidine ring group) which may have a substituent, and may have a substituent
- An aryl group or a heteroaryl group is more preferable, and a phenyl group, a naphthyl group, a thienyl group or a carbazole ring group which may have a substituent is more preferable.
- the aryl group or heteroaryl group represented by R b3 is an alkyl group (more preferably a linear or branched alkyl group having 1 to 5 carbon atoms) alkoxy group (more preferably a methoxy group) as a substituent Alternatively, it is also preferable to have an aryl group (more preferably a phenyl group). It is also preferable that the alkyl group, the alkoxy group and the aryl group as the above-mentioned substituent further have a substituent, and a halogen atom (more preferably a fluorine atom) is preferable as the substituent.
- Each of R b2 , R b4 and R b5 independently preferably represents a hydrogen atom or an alkyl group, an aryl group or a heteroaryl group which may have a substituent, and a hydrogen atom is more preferable. .
- R b6 to R b13 independently represents a hydrogen atom or a substituent.
- R b6 to R b13 each independently represent a hydrogen atom, or an alkyl group, an aryl group (such as a phenyl group) which may have a substituent, a heteroaryl group or a non-aromatic heterocyclic group
- R b2 and R b3 may be linked to each other to form a ring.
- X 1 represents And any one of R b6 to R b13 and R b3 may be linked to each other to form a ring.
- R b4 and R b5 are not linked to each other to form a ring.
- a in Formula (2) represents a ring containing at least 2 carbon atoms, and the preferred embodiment of A in Formula (2) and the preferred embodiment in A of Formula (1) are the same.
- the compound represented by the formula (2) has any of a carboxy group, a salt of a carboxy group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group I do not.
- the specific compound is more preferably a compound represented by the following formula (3).
- R c1 is an alkyl group, an aryl group, a heteroaryl group, a -CO-alkyl group, a -CO-aryl group, or a -CO-heteroaryl group which may have a substituent.
- an alkyl group or an aryl group is preferable, and an alkyl group having 1 to 2 carbon atoms, a cyclohexyl group or a phenyl group is more preferable.
- the phenyl group preferably has an alkyl group (preferably a branched alkyl group having 3 to 5 carbon atoms) as a substituent.
- R c2 to R c7 independently represents a hydrogen atom or a substituent.
- the type of substituent is not particularly limited, and groups exemplified for the substituent W described later can be mentioned.
- R c3 is preferably an alkyl group, an aryl group, a heteroaryl group, or a non-aromatic heterocyclic group (such as a piperidine ring group) which may have a substituent, and may have a substituent
- An aryl group or a heteroaryl group is more preferable, and a phenyl group, a naphthyl group, a thienyl group or a carbazole ring group which may have a substituent is more preferable.
- the aryl group or heteroaryl group represented by R c3 is an alkyl group (more preferably a linear or branched alkyl group having 1 to 5 carbon atoms) alkoxy group (more preferably a methoxy group) as a substituent Alternatively, it is also preferable to have an aryl group (more preferably a phenyl group). It is also preferable that the alkyl group, the alkoxy group and the aryl group as the above-mentioned substituent further have a substituent, and a halogen atom (more preferably a fluorine atom) is preferable as the substituent.
- R c2 and R c3 may be linked to each other to form a ring, and R c5 and R c6 may be linked to each other to form a ring.
- R c5 and R c6 be linked to each other to form a benzene ring. That is, it is preferable to form a group corresponding to the group represented by formula (A3).
- preferred embodiments of the group corresponding to the group represented by the above formula (A3) are the same as the preferred embodiments of the group represented by the formula (A3).
- the carbon atom to which R c5 specified in Formula (3) is bonded corresponds to a carbon atom adjacent to * 1 in Formula (A3).
- R c2 , R c4 and R c7 is independently preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom.
- X 2 represents an oxygen atom or a sulfur atom.
- R c4 and R c7 are not linked to each other to form a ring.
- the compound represented by the formula (3) is any of carboxy group, carboxy group salt, phosphoric acid group, phosphoric acid group salt, sulfonic acid group, and sulfonic acid group salt I do not.
- substituent W for example, a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group , Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxy Carbonyloxy, aryloxycarbonyloxy, amino (including anilino), ammonio, acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino
- 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 is a carboxy group, a salt of a carboxy group, a phosphate group, a salt of a phosphate group, a sulfonate group, and a salt of a sulfonate group. It has neither.
- the substituent W of the specific compound does not include a carboxy group, a salt of a carboxy group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.
- the carbon number of the alkyl group of the specific compound is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and 1 to 6 4 is more preferred.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group may be substituted by a substituent (for example, a substituent W).
- substituent W for example, a substituent W.
- 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 cyclohexyl group.
- the number of carbon atoms in the aryl group possessed by the specific compound is not particularly limited, but is preferably 6 to 30, more preferably 6 to 18, still more preferably 6 preferable.
- the aryl group may be a single ring structure or a condensed ring structure (fused ring structure) in which two or more rings are fused. Further, the aryl group may be substituted by a substituent (for example, a substituent W).
- aryl group examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group, methylphenyl group, dimethylphenyl group, biphenyl group, fluorenyl group and the like, and a phenyl group, a naphthyl group or Anthryl group is preferred.
- the number of carbons in the heteroaryl group (monovalent aromatic heterocyclic group) of the specific compound is not particularly limited, but is preferably 3 to 30. And 3 to 18 are more preferable.
- the heteroaryl group may be substituted by a substituent (eg, a substituent W).
- Heteroaryl groups have heteroatoms in addition to carbon atoms and hydrogen atoms.
- hetero atom a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom are mentioned, for example, A sulfur atom, an oxygen atom, or a nitrogen atom is preferable.
- the number of heteroatoms in the heteroaryl group is not particularly limited, and is usually about 1 to 10, preferably 1 to 4, and 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.
- the heteroaryl group may be a single ring structure or a fused ring structure in which two or more rings are fused. In the case of a condensed ring structure, an aromatic hydrocarbon ring having no hetero atom (eg, a benzene ring) may be included.
- the heteroaryl group include pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthrizinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, quinazolyl group, pyridazinyl group, cinnolinyl group, phthalazinyl group, and the like.
- the molecular weight of the specific compound is not particularly limited, but is preferably 300 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 300 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 compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.
- 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 preferred.
- 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 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 photoelectric conversion film preferably has a bulk heterostructure formed by mixing the specific compound and an 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.
- a photoelectric conversion film is substantially comprised from a specific compound and an n-type organic semiconductor. To be substantially means that the total content of the specific compound and the n-type organic semiconductor is 95% by mass or more with respect to the total mass of the photoelectric conversion film.
- the n-type organic semiconductor contained in the photoelectric conversion film may be used singly or in combination of two or more.
- the photoelectric conversion film may further contain a p-type organic semiconductor.
- the p-type organic semiconductor include the following.
- the said p-type organic semiconductor intends p-type organic semiconductor other than a specific compound.
- the p-type organic semiconductor is a donor type organic semiconductor material (compound) and refers to an organic compound having a property of easily giving an electron. More specifically, the p-type organic semiconductor refers to an organic compound having a smaller ionization potential when used in contact with two organic compounds.
- Examples of p-type organic semiconductors include triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, carbazole compounds, polysilane compounds, thiophene compounds, cyanine compounds, oxonol Examples thereof include compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand.
- the p-type organic semiconductor one having an ionization potential smaller than that of the n-type organic semiconductor can be mentioned, and the organic dye exemplified as the n-type organic semiconductor can be used if this condition is satisfied.
- 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 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; Oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene, 4,4 ', 4''-tris (N- (3-methylphenyl) N-phenylamino ) Tri
- 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 for improving 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 outside 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.
- Compound (A-1) was prepared from 2-bromo-5-furaldehyde from Chem. Eur. J. It synthesize
- TFA trifluoroacetic acid
- a mixed solution obtained by adding Compound (A-4) (1.30 g, 5.43 mmol) and Compound (A-5) (1.12 g, 5.70 mmol) to acetic acid (40 mL) was prepared at 70 ° C. It was made to react for time. After cooling the mixed solution to room temperature, methanol (80 mL) was added to the mixed solution and stirred for 30 minutes to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to give a crude product. The obtained crude product was recrystallized from chlorobenzene (100 mL), and the solid obtained by recrystallization was washed with methanol to obtain Compound (D-1) (1.48 g, yield 65%).
- the compound (D-1) obtained was identified by 1 H NMR (Nuclear Magnetic Resonance) and MS (Mass Spectrometry).
- the 1 H NMR spectrum (400 MHz, CDCl 3 ) is shown in FIG. MS (ESI + ) m / z: 418.1 ([M + H] + )
- 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: 30 nm).
- the compound (R-1) as a p-type organic semiconductor and the fullerene (C 60 ) as an n-type organic semiconductor are each 100 nm in monolayer conversion on the electron blocking film 16A.
- the film was co-evaporated by vacuum evaporation so as to have a thickness of 100 nm to form a film, and a photoelectric conversion film 12 having a bulk heterostructure of 200 nm was formed.
- 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 was produced by the method similar to an element (A) except the film thickness of a photoelectric conversion film. Specifically, in a state where the temperature of the substrate is controlled to 25 ° C., vacuum is applied so that the compound (R-1) and the fullerene (C 60 ) become 50 nm and 50 nm in single layer conversion on the electron blocking film 16A. The film was co-deposited by vapor deposition to form a film, and a photoelectric conversion film 12 having a bulk heterostructure of 100 nm was formed. The obtained photoelectric conversion element is referred to as an element ( BR-1 ).
- Table 1 below shows the evaluation results of devices manufactured using each compound.
- the group represented by X 1 is an oxygen atom or a sulfur atom
- the group represented by X 1 is an oxygen atom or a sulfur atom
- the case where the group represented by X 1 is an oxygen atom or a sulfur atom is “presence”, and the case other than that is “none”.
- R c3 represents that the group represented by R c3 is an aryl group or a heteroaryl group. Indicate if there is.
- the case where the group represented by R c3 is an aryl group or a heteroaryl group is “presence”, and the case other than that is “none”.
- the compound which does not correspond to Formula (3) it was set as "-".
- the photoelectric conversion device of the present invention is a photoelectric conversion device having a photoelectric conversion film excellent in vapor deposition suitability and exhibiting excellent photoelectric conversion efficiency even when the photoelectric conversion film is a thin film.
- X 1 in the formula (2) is an oxygen atom or a sulfur atom, it has been confirmed that the photoelectric conversion element tends to exhibit the photoelectric conversion efficiency at the time of a better thin film (Example 20 and Other Examples and comparison).
- R b1 in the formula (2) is an alkyl group or an aryl group, it is confirmed that the photoelectric conversion element tends to exhibit better photoelectric conversion efficiency in thin film (Example 21 and Example 1). Comparison).
- Imaging devices similar to those shown in FIG. 3 were produced. That is, after depositing amorphous TiN 30 nm on a CMOS substrate by sputtering, it is patterned by photolithography so that one pixel exists on each of the photodiodes (PD) on the CMOS substrate, to form a lower electrode. After the film formation of the electron blocking material, an imaging device was produced in the same manner as the devices (A) or (B D-1 ) to (B D-24 ) or (B R-1 ).
- 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、光電変換膜の薄膜化を進めた場合(例えば、光電変換膜を100nmとした場合)でも良好な光電変換効率を維持できることが求められている。
本発明者は、特許文献1で開示されている化合物(例えば、上述した化合物)を用いて光電変換素子を作製し、光電変換膜が薄膜である場合の光電変換効率(以下「薄膜時の光電変換効率」ともいう)について検討したところ、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、本発明者は、特許文献2および3について検討したところ、両文献に開示されている化合物の構造によっては、蒸着法を用いて光電変換膜を製造することが困難であることを知見した。
なお、以下、蒸着法を用いた場合における光電変換膜の製造適性を「蒸着適性」ともいう。
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。
(2) 後述する式(1)で表される化合物が、後述する式(2)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(2)中の、Rb1が、置換基を有していてもよい、アルキル基、アリール基、ヘテロアリール基、-CO-アルキル基、-CO-アリール基、または、-CO-ヘテロアリール基を表す、(2)に記載の光電変換素子。
(4) 後述する式(2)中の、X1が、酸素原子、硫黄原子、-NRb6-、または、-CRb11=CRb12-を表す、(2)または(3)に記載の光電変換素子。
(5) 後述する式(2)中の、X1が、酸素原子または硫黄原子を表す、(2)~(4)のいずれかに記載の光電変換素子。
(6) 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る、(1)~(5)のいずれかに記載の光電変換素子。
(7) 後述する式(3)中のRc3が、置換基を有していてもよい、アリール基またはヘテロアリール基を表す、(6)に記載の光電変換素子。
(8) 上記光電変換膜が、さらにn型有機半導体を含み、後述する式(1)で表される化合物と上記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)~(7)のいずれかに記載の光電変換素子。
(9) 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)~(8)のいずれかに記載の光電変換素子。
(10) (1)~(9)のいずれかに記載の光電変換素子を有する、光センサ。
(11) (1)~(9)のいずれかに記載の光電変換素子を有する、撮像素子。
(12) 後述する式(2)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。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。
本明細書において表記される二価の基の結合方向は特に制限されず、例えば、後述する式(2)中のX1が-N=CRb13-である場合、Rb3側に結合している位置を*1、ピロール環基の側に結合している位置を*2とすると、X1は*1-N=CRb13-*2であってもよく、*1-CRb13=N-*2であってもよい。
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(以後、「特定化合物」ともいう)を使用している点が挙げられる。
また、本発明者らは、所定の酸性の基およびその塩の存在が化合物の蒸着適性に悪影響を与える傾向があることを知見した。より具体的には、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない特定化合物であれば、優れた薄膜時の光電変換効率と共に、優れた蒸着適性も維持できることを見出した。
なお、本明細書において「塩」は、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、および、置換アンモニウム塩のいずれかを意図する。
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の電圧を印加することが好ましい。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ことが好ましい。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、これらに限るものではない。
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、蒸着適性に優れる光電変換膜を有し、優れた薄膜時の光電変換効率を示す、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。
なお、以下で言及される特定化合物の好適な条件は、特筆無き限り、薄膜時の光電変換効率がより優れる点から言及される。
また、特筆無き限り、特定化合物が有し得る置換基は、それぞれ独立に、後述する置換基Wのいずれかであるのが好ましい。
なお、本明細書において、式(1)中、Ra7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(1)はそのいずれをも含む。つまり、上記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は、いずれも式(1)で表される化合物に含まれる。
後述する式(2)におけるRb5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も同様である。
例としては、Ra1とRa2とは互いに連結して環を形成していてもよく、Ra1とRa7とは互いに連結して環を形成していてもよく、Ra2とRa3とは互いに連結して環を形成していてもよく、Ra3とRa4とは互いに連結して環を形成していてもよく、Ra4とRa5とは互いに連結して環を形成していてもよく、Ra5とRa6とは互いに連結して環を形成していてもよく、Ra3とRa5とは互いに連結して環を形成していてもよい。Ra3とRa5とは互いに連結して環を形成する場合、m=0が好ましい。
なお、Ra2が複数存在する場合、複数存在するRa2同士が、互いに連結して環を形成していてもよい。
Ra4が複数存在する場合、複数存在するRa4同士が、互いに連結して環を形成していてもよい。
また、上記Ra4とRa5とが互いに結合して形成する基は、酸素原子、硫黄原子、セレン原子、-NRa8-、-CRa9Ra10-、-SiRa11Ra12-、-CRa13=CRa14-、-N=CRa15-、または、-N=N-が好ましく、酸素原子または硫黄原子がより好ましい。なお、Ra8~Ra15は、それぞれ独立に、水素原子または置換基を表す。
環の形成に寄与しない場合のRa3は、置換基を有していてもよい、アルキル基、アリール基、ヘテロアリール基、または、非芳香族ヘテロ環基が好ましく、アリール基、または、ヘテロアリール基がより好ましい。
また、環の形成に寄与しない場合のRa2およびRa4~Ra7は、それぞれ独立に、水素原子、または、置換基を有していてもよい、アルキル基、アリール基、もしくは、ヘテロアリール基が好ましい。
Aは、ヘテロ原子を有していてもよく、ヘテロ原子は、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。
Aは置換基を有していてもよく、置換基としてはハロゲン原子が好ましい。
A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(1)中に明示されるAを構成するカルボニル基に含まれる酸素原子の数、および、Aが置換基として有するハロゲン原子の数を含まない数である。
Aは、芳香族性を示してもよく、示さなくてもよい。
A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。
RLは、水素原子または置換基を表す。中でも、RLは、アルキル基、アリール基、または、ヘテロアリール基が好ましく、アルキル基またはアリール基が好ましい。
Lは、単結合が好ましい。
RY1~RY5は、それぞれ独立に、水素原子または置換基を表す。中でも、RY1~RY5は、それぞれ独立に、アルキル基、アリール基、または、ヘテロアリール基が好ましく、アルキル基またはアリール基がより好ましい。
また、Yが-CRY1=CRY2-を表す場合、RY1とRY2とは互いに連結して環を形成するのが好ましく、RY1とRY2とは互いに連結してベンゼン環を形成するのがより好ましい。
A1とA2とは互いに連結して環を形成するのが好ましく、A1とA2とは互いに連結してベンゼン環を形成するのがより好ましい。
A1とA2とで形成される上記ベンゼン環は、さらに置換基を有しているのも好ましい。置換基としては、ハロゲン原子が好ましく、塩素原子またはフッ素原子がより好ましい。
また、A1とA2とで形成される上記ベンゼン環が有する置換基が、さらに互いに連結して環を形成していてもよい。例としては、A1とA2とで形成される上記ベンゼン環が有する置換基が、さらに互いに連結してベンゼン環を形成していてもよい。
A3とA4とは互いに連結して環を形成していてもよく、A4とA5とは互いに連結して環を形成していてもよく、A5とA6とは互いに連結して環を形成していてもよい。A3とA4、A4とA5、および、A5とA6とが、それぞれ互いに連結して形成する環はベンゼン環が好ましい。
中でも、A4とA5とが互いに連結して環を形成するのが好ましく、A4とA5とが互いに連結して形成される環はベンゼン環が好ましい。
なお、A4とA5とが互いに連結して形成される環には、さらに置換基が置換していてもよい。
(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)ピラゾリノン核:例えば、1-フェニル-2-ピラゾリン-5-オン、3-メチル-1-フェニル-2-ピラゾリン-5-オン、および、1-(2-ベンゾチアゾリル)-3-メチル-2-ピラゾリン-5-オン等。
(c)イソオキサゾリノン核:例えば、3-フェニル-2-イソオキサゾリン-5-オン、および、3-メチル-2-イソオキサゾリン-5-オン等。
(d)オキシインドール核:例えば、1-アルキル-2,3-ジヒドロ-2-オキシインドール等。
(e)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。
(f)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。
(g)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。
(h)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。
(i)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。
(j)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。
(k)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。
(l)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。
(m)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。
(n)イミダゾリン-5-オン核:例えば、2-プロピルメルカプト-2-イミダゾリン-5-オン等。
(o)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。
(p)ベンゾチオフェン-3(2H)-オン核:例えば、ベンゾチオフェン-3(2H)-オン、オキソベンゾチオフェン-3(2H)-オン、および、ジオキソベンゾチオフェンー3(2H)-オン等。
(q)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。
(r)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。
(s)2,2-ジヒドロフェナレン-1,3-ジオン核等。
また、上述の基およびその塩以外にも、蒸着適性の悪化を回避する点から、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、これらの基の塩のいずれも有さないことが好ましい。
特定化合物は、下記式(2)で表される化合物であるのが好ましい。
なお、下記式(2)は、式(1)中のmが1を表し、Ra4とRa5とが互いに連結して環を形成している場合に相当する。
なお、上記フェニル基は、置換基としてアルキル基(好ましくは炭素数3~5の分岐鎖状アルキル基)を有しているのも好ましい。
Rb3で表されるアリール基またはヘテロアリール基は、置換基としてアルキル基(より好ましくは炭素数1~5の直鎖状または分岐鎖状のアルキル基)アルコキシ基(より好ましくはメトキシ基)、または、アリール基(より好ましくはフェニル基)を有しているのも好ましい。上記置換基としての、アルキル基、アルコキシ基、および、アリール基がさらに置換基を有しているのも好ましく、その置換基としてはハロゲン原子(より好ましくはフッ素原子)が好ましい。
中でも、X1は、酸素原子、硫黄原子、-NRb6-、または、-CRb11=CRb12-が好ましく、酸素原子または硫黄原子がより好ましい。
また、X1が、-NRb6-、-CRb7Rb8-、-SiRb9Rb10-、-CRb11=CRb12-、または、-N=CRb13-を表す場合、X1が表す基が有するRb6~Rb13のいずれか1つと、Rb3とは、互いに連結して環を形成していてもよい。
特定化合物は、下記式(3)で表される化合物であるのがより好ましい。
なお、上記フェニル基は、置換基としてアルキル基(好ましくは炭素数3~5の分岐鎖状アルキル基)を有しているのも好ましい。
Rc3で表されるアリール基またはヘテロアリール基は、置換基としてアルキル基(より好ましくは炭素数1~5の直鎖状または分岐鎖状のアルキル基)アルコキシ基(より好ましくはメトキシ基)、または、アリール基(より好ましくはフェニル基)を有しているのも好ましい。上記置換基としての、アルキル基、アルコキシ基、および、アリール基がさらに置換基を有しているのも好ましく、その置換基としてはハロゲン原子(より好ましくはフッ素原子)が好ましい。
中でも、Rc5とRc6とが互いに連結してベンゼン環を形成しているのが好ましい。つまり、式(A3)で表される基に相当する基を形成するのが好ましい。この場合、上記式(A3)で表される基に相当する基の好適な態様は、式(A3)で表される基の好適な態様と同様である。なお、この場合、式(3)中に明示されるRc5が結合している炭素原子が、式(A3)中の*1と隣接する炭素原子に相当する。
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、アルキル基(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を含む)、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)、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)、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。
ただし、上述の通り、蒸着適性の悪化を回避する点から、特定化合物は、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない。そのため、本明細書において、特定化合物が有する置換基Wとしては、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩を含まない。
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、シクロへキシル基等が挙げられる。
アリール基としては、例えば、フェニル基、ナフチル基、アントリル基、ピレニル基、フェナントレニル基、メチルフェニル基、ジメチルフェニル基、ビフェニル基、および、フルオレニル基等が挙げられ、フェニル基、ナフチル基、または、アントリル基が好ましい。
ヘテロアリール基は、炭素原子、および、水素原子以外にヘテロ原子を有する。ヘテロ原子としては、例えば、硫黄原子、酸素原子、窒素原子、セレン原子、テルル原子、リン原子、ケイ素原子、および、ホウ素原子が挙げられ、硫黄原子、酸素原子、または、窒素原子が好ましい。
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、通常、1~10程度であり、1~4が好ましく、1~2がより好ましい。
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。なお、ヘテロアリール基は、単環構造であっても、2つ以上の環が縮環した縮環構造であってもよい。縮環構造の場合、ヘテロ原子を有さない芳香族炭化水素環(例えば、ベンゼン環)が含まれていてもよい。
ヘテロアリール基としては、例えば、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、フリル基、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。
なお、下記で示す構造式は、化合物を式(1)(または式(2))に当てはめた場合において、Ra7(またはRb5)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。
下記例示中、「Me」はメチル基を表し、「TMS」はトリメチルシリル基を表す。
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。
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。
なお、光電変換膜は、実質的に、特定化合物とn型有機半導体から構成されることが好ましい。実質的とは、光電変換膜全質量に対して、特定化合物およびn型有機半導体の合計含有量が95質量%以上であることを意図する。
また、光電変換膜は、特定化合物及びn型有機半導体に加えて、さらにp型有機半導体を含んでいてもよい。p型有機半導体としては、例えば、下記に示すものが挙げられる。
なお、特定化合物をp型有機半導体として使用する場合は、上記p型有機半導体は、特定化合物以外のp型有機半導体を意図する。
p型有機半導体とは、ドナー性有機半導体材料(化合物)であり、電子を供与しやすい性質がある有機化合物をいう。さらに詳しくは、p型有機半導体とは、2つの有機化合物を接触させて用いたときにイオン化ポテンシャルの小さい方の有機化合物をいう。
p型有機半導体(特定化合物以外のp型有機半導体)としては、例えば、トリアリールアミン化合物、ベンジジン化合物、ピラゾリン化合物、スチリルアミン化合物、ヒドラゾン化合物、カルバゾール化合物、ポリシラン化合物、チオフェン化合物、シアニン化合物、オキソノール化合物、ポリアミン化合物、インドール化合物、ピロール化合物、ピラゾール化合物、ポリアリーレン化合物、縮合芳香族炭素環化合物、及び、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。
p型有機半導体としては、n型有機半導体よりもイオン化ポテンシャルが小さいものが挙げられ、この条件を満たせば、n型有機半導体として例示した有機色素を使用し得る。
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ことが好ましい。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ことも好ましい。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(光電変換効率および応答性等)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;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ことが好ましい。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。
化合物(D-1)は、以下のスキームに従って、合成した。
なお下記において、「Et」はエチル基を表し、「Ac」はアセチル基を表す。
得られた化合物(D-1)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:418.1([M+H]+)
また化合物(D-3)、(D-4)、および、(D-6)の1H NMRスペクトル(400MHz、CDCl3)を図5~7に示す。
なお、得られた化合物(D-1)~(D-24)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、Ra7またはRb5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。
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:30nm)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(R-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(A)とする。
(化合物(R-1)を用いた例)
光電変換膜の膜厚以外は、素子(A)と同様の方法で光電変換素子を作製した。
具体的には、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上に化合物(R-1)とフラーレン(C60)とをそれぞれ単層換算で50nm、50nmとなるように真空蒸着法により共蒸着して成膜し、100nmのバルクヘテロ構造を有する光電変換膜12を形成した。
得られた光電変換素子を、素子(BR-1)とする。
化合物(R-1)を、それぞれ、化合物(D-1)~(D-24)または(R-2)~(R-3)に変更した以外は、素子(BR-1)と同様の方法で光電変換素子の作製を試みた。
化合物(D-1)~(D-24)を用いて得られた光電変換素子を、それぞれ、素子(BD-1)~(BD-24)とする。
一方で、化合物(R-2)~(R-3)を用いた場合は、化合物(R-2)~(R-3)を蒸着できなかった。
作製した素子(A)、(BD-1)~(BD-24)、および、(BR-1)について、それぞれ、2.0×105V/cmの電界強度になるように電圧を印加し、光電変換効率の最大値を測定した。
素子(A)の光電変換効率の最大値を1として、それに対する他の各素子の光電変換効率の最大値を、相対値で評価した。素子の光電変換効率の相対値が1.1以上の場合を「A」、1.0以上1.1未満の場合を「B」、1.0未満の場合を「C」とした。
結果を表1に示す。実用上、「A」または「B」が好ましく、「A」がより好ましい。
表1中、「X1」の欄は、化合物(D-1)~(D-24)を式(2)に当てはめた場合において、X1で表される基が酸素原子または硫黄原子であるかを示す。X1で表される基が酸素原子または硫黄原子である場合を「有」、そうでない場合を「無」とする。
表1中、「Rb1」の欄は、化合物(D-1)~(D-24)を式(2)に当てはめた場合において、Rb1で表される基がアルキル基またはアリール基であるかを示す。Rb1で表される基がアルキル基またはアリール基である場合を「有」、そうでない場合を「無」とする。
表1中、「式(A2)」の欄は、化合物(D-1)~(D-24)を式(2)に当てはめた場合における、式(A2)で表される基の有無を示す。
表1中、「Rc3」の欄は、化合物(D-1)~(D-24)を式(3)に当てはめた場合において、Rc3で表される基がアリール基またはヘテロアリール基であるかを示す。Rc3で表される基がアリール基またはヘテロアリール基である場合を「有」、そうでない場合を「無」とする。なお、式(3)に当てはまらない化合物については「-」とした。
式(2)においてX1が、酸素原子または硫黄原子である場合、光電変換素子は、より優れた薄膜時の光電変換効率を示す傾向が確認された(実施例20と、他の実施例との比較)。
式(2)におけるRb1が、アルキル基またはアリール基である場合、光電変換素子は、より優れた薄膜時の光電変換効率を示す傾向が確認された(実施例21と、実施例1との比較)。
式(2)で表される化合物が、式(A2)で表される基を有する場合、光電変換素子は、より優れた薄膜時の光電変換効率を示す傾向が確認された(実施例6~8と、他の実施例との比較)。
式(3)におけるRc3が、アリール基またはヘテロアリール基である場合、光電変換素子は、より優れた薄膜時の光電変換効率を示す傾向が確認された(実施例14、15、および、23と、他の実施例との比較)。
化合物(D-1)~(D-24)および(R-1)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。
つまり、CMOS基板上に、アモルファス性TiN 30nmをスパッタ法により成膜後、フォトリソグラフィーによりCMOS基板上のフォトダイオード(PD)の上にそれぞれ1つずつ画素が存在するようにパターニングして下部電極とし、電子ブロッキング材料の成膜以降は素子(A)または(BD-1)~(BD-24)もしくは(BR-1)と同様にして撮像素子を作製した。得られた撮像素子で、光電変換膜が薄膜である場合の光電変換効率の評価も同様に行い、表1と同様な結果を得た。このことから、本発明の光電変換素子は、撮像素子においても優れた性能を示すことが分かった。
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 (12)
- 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)で表される化合物を含む、光電変換素子。
Ra1~Ra7は、それぞれ独立に、水素原子または置換基を表す。
Ra1~Ra7は、互いに連結して環を形成していてもよい。
Ra2が複数存在する場合、複数存在するRa2同士が、互いに連結して環を形成していてもよい。
Ra4が複数存在する場合、複数存在するRa4同士が、互いに連結して環を形成していてもよい。
Aは、少なくとも2つの炭素原子を含む環を表す。
ただし、式(1)で表される化合物は、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない。 - 前記式(1)で表される化合物が、式(2)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。
X1は、酸素原子、硫黄原子、セレン原子、-NRb6-、-CRb7Rb8-、-SiRb9Rb10-、-CRb11=CRb12-、-N=CRb13-、または、-N=N-を表す。
Rb6~Rb13は、それぞれ独立に、水素原子または置換基を表す。
Rb2とRb3とは、互いに連結して環を形成していてもよい。
X1が、-NRb6-、-CRb7Rb8-、-SiRb9Rb10-、-CRb11=CRb12-、または、-N=CRb13-を表す場合、X1が表す基が有するRb6~Rb13のいずれか1つと、Rb3とは、互いに連結して環を形成していてもよい。
Aは、少なくとも2つの炭素原子を含む環を表す。
ただし、式(2)で表される化合物は、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない。 - Rb1が、置換基を有していてもよい、アルキル基、アリール基、ヘテロアリール基、-CO-アルキル基、-CO-アリール基、または、-CO-ヘテロアリール基を表す、請求項2に記載の光電変換素子。
- X1が、酸素原子、硫黄原子、-NRb6-、または、-CRb11=CRb12-を表す、請求項2または3に記載の光電変換素子。
- X1が、酸素原子または硫黄原子を表す、請求項2~4のいずれか1項に記載の光電変換素子。
- 前記式(1)で表される化合物が、式(3)で表される化合物である、請求項1~5のいずれか1項に記載の光電変換素子。
Rc2~Rc7は、それぞれ独立に、水素原子または置換基を表す。
X2は、酸素原子または硫黄原子を表す。
Rc2とRc3とは、互いに連結して環を形成していてもよい。
Rc5とRc6とは、互いに連結して環を形成していてもよい。
ただし、式(3)で表される化合物は、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない。 - Rc3が、置換基を有していてもよい、アリール基またはヘテロアリール基を表す、請求項6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、前記式(1)で表される化合物と前記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1~7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1~8のいずれか1項に記載の光電変換素子。
- 請求項1~9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1~9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。
- 式(2)で表される、化合物。
X1は、酸素原子、硫黄原子、セレン原子、-NRb6-、-CRb7Rb8-、-SiRb9Rb10-、-CRb11=CRb12-、-N=CRb13-、または、-N=N-を表す。
Rb6~Rb13は、それぞれ独立に、水素原子または置換基を表す。
Rb2とRb3とは、互いに連結して環を形成していてもよい。
X1が、-NRb6-、-CRb7Rb8-、-SiRb9Rb10-、-CRb11=CRb12-、または、-N=CRb13-を表す場合、X1が表す基が有するRb6~Rb13のいずれか1つと、Rb3とは、互いに連結して環を形成していてもよい。
Aは、少なくとも2つの炭素原子を含む環を表す。
ただし、式(2)で表される化合物は、カルボキシ基、カルボキシ基の塩、リン酸基、リン酸基の塩、スルホン酸基、および、スルホン酸基の塩のいずれも有さない。
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