WO2022138833A1 - 光電変換素子、撮像素子、光センサ、化合物 - Google Patents

光電変換素子、撮像素子、光センサ、化合物 Download PDF

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WO2022138833A1
WO2022138833A1 PCT/JP2021/047905 JP2021047905W WO2022138833A1 WO 2022138833 A1 WO2022138833 A1 WO 2022138833A1 JP 2021047905 W JP2021047905 W JP 2021047905W WO 2022138833 A1 WO2022138833 A1 WO 2022138833A1
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photoelectric conversion
atom
hydrogen atom
above formula
formula
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French (fr)
Japanese (ja)
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寛記 杉浦
征夫 谷
良 藤原
康智 米久田
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020237020618A priority Critical patent/KR102939978B1/ko
Priority to JP2022571627A priority patent/JP7709464B2/ja
Priority to CN202180085426.XA priority patent/CN116601156B/zh
Priority to EP21910972.5A priority patent/EP4269416B1/en
Publication of WO2022138833A1 publication Critical patent/WO2022138833A1/ja
Priority to US18/334,368 priority patent/US12479859B2/en
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    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a photoelectric conversion element, an image pickup element, an optical sensor, and a compound.
  • Patent Document 1 discloses the following organic semiconductor materials as materials related to the photoelectric field.
  • R is a predetermined alkyl group.
  • Ar 11 to Ar 14 are independent groups represented by any of the formulas (2) to (7) described later.
  • Ar 15 to Ar 16 are groups represented by any of the formulas (8) to (15) and the formulas (47) to (53), which will be described later, independently of each other, [1] or The photoelectric conversion element according to [2].
  • n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, n18 represents 1 or 2, and n18 represents 1 or 2.
  • Photoelectric conversion element [8] The photoelectric conversion element according to any one of [1] to [3], wherein n11 to n14 represent 0, n15 to n16 independently represent 0 or 1, n17 represents 2, and n18 represents 1.
  • the compound represented by the above formula (1) is a compound represented by any of the formulas (16) to (46) and the formulas (54) to (60), which will be described later, [1].
  • the photoelectric conversion element according to any one of [3].
  • the compound represented by the above formula (21) in which R is a hydrogen atom, Y 21 to Y 24 and Y 151 to Y 157 are ⁇ CR , and R is represented by the above formula (22).
  • the compounds represented by the above formula (1) are the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), the above formula (39), and the above formula (39).
  • Ar 15 to Ar 16 are each independently represented by any of the formulas (8) to (15) and the formulas (47) to (53), which will be described later, [21] or The compound according to [22].
  • n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.
  • the compound represented by the above formula (21) in which R is a hydrogen atom, Y 21 to Y 24 and Y 151 to Y 157 are ⁇ CR , and R is represented by the above formula (22).
  • Is a compound represented by the above formula (59) in which is a hydrogen atom, or a compound represented by the above formula (59) in which Y 531 to Y 539 are ⁇ CR and R is a hydrogen atom. 29].
  • the compounds represented by the above formula (1) are the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), the above formula (39), and the above formula (39).
  • the present invention it is possible to provide a photoelectric conversion element having excellent photoelectric conversion efficiency. Further, according to the present invention, it is possible to provide an image pickup device, an optical sensor, and a compound related to the photoelectric conversion element.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
  • the aromatic ring group may be a monocyclic type or a polycyclic type (for example, 2 to 6 ring type) unless otherwise specified.
  • the monocyclic aromatic ring group is an aromatic ring group having only one aromatic ring structure as a ring structure.
  • a polycyclic (for example, 2 to 6 ring type) aromatic ring group is an aromatic ring group in which a plurality of (for example, 2 to 6) aromatic ring structures are fused as a ring structure.
  • the number of ring-membered atoms of the aromatic ring group is preferably an integer of 5 to 15.
  • the aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the number of heteroatoms possessed as ring member atoms is, for example, 1 to 10.
  • 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.
  • the aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthrene ring group.
  • aromatic heterocyclic group examples include a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, and a triazine ring group (1,2,3-triazine ring group, 1,2,4-triazine ring group). , 1,3,5-triazine ring group, etc.), and tetradine ring group (1,2,4,5-tetrazine ring, etc.), quinoxaline ring group, pyrrol ring group, furan ring group, thiophene ring group, imidazole ring.
  • the aromatic ring constituting the aromatic ring group can be mentioned.
  • the aromatic ring group is monovalent, examples of such an aromatic ring group include a group obtained by removing one hydrogen atom from the aromatic ring in the above-mentioned aromatic ring group.
  • the aromatic ring group in this case is a so-called aryl group or heteroaryl group.
  • examples of such an aromatic ring group include a group obtained by removing two hydrogen atoms from the aromatic ring in the above-mentioned aromatic ring group.
  • the aromatic ring group in this case is a so-called aryl group or heteroaryl group.
  • the aromatic ring group in this case is a so-called arylene group or heteroarylene group.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a heavy hydrogen atom (double hydrogen atom or the like).
  • the photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film is a compound represented by the formula (1) (hereinafter referred to as a compound). , Also referred to as "specific compound").
  • a compound represented by the formula (1)
  • specific compound also referred to as "specific compound”
  • the mechanism by which the photoelectric conversion element of the present invention can solve the above problems by adopting such a configuration is not always clear, but the present inventors speculate as follows. That is, the specific compound has a mother nucleus in which a nitrogen-containing five-membered ring having aromaticity is present at both ends, and the mother nucleus has predetermined substituents at both ends of the mother nucleus.
  • the mother nucleus has good crystallinity, and the types and arrangements of substituents that the mother nucleus can have are also limited to a range that does not inhibit the crystallinity of the specific compound.
  • the charge transportability between the compounds is good, and good charge transportability can be maintained even under a low voltage.
  • the photoelectric conversion element of the present invention has good photoelectric conversion efficiency (particularly, photoelectric conversion efficiency for light having a wavelength of 400 to 700 nm), and dark current is also suppressed.
  • the electric field strength dependence of the photoelectric conversion efficiency in the photoelectric conversion element is further suppressed, the photoelectric conversion efficiency is more excellent, and / or the dark current is further suppressed. The effect is better.
  • FIG. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10a shown in FIG. 1 includes a conductive film (hereinafter, also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and an upper electrode. It has a structure in which a functioning transparent conductive film (hereinafter, also referred to as an upper electrode) 15 is laminated in this order.
  • FIG. 2 shows a configuration example of another photoelectric conversion element.
  • FIGS. 1 and 2 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 laminated in this order on a 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. 1 and 2 may be appropriately changed depending on the application and characteristics.
  • the photoelectric conversion element 10a it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Further, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that 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. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 -4 to 1 ⁇ 10 7 V / cm, further preferably 1 ⁇ 10 -3 to 5 ⁇ 10 6 V / cm.
  • the voltage application method it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode in FIGS. 1 and 2.
  • a voltage can be applied by the same method.
  • the photoelectric conversion element 10a (or 10b) can be suitably applied to an image sensor application.
  • the photoelectric conversion film is a film containing a specific compound.
  • the specific compound will be described in detail.
  • X 11 and X 12 independently represent a sulfur atom or an oxygen atom, respectively. Of these, sulfur atoms are preferable for X 11 and X 12 .
  • Ar 11 to Ar 16 independently represent monocyclic, bicyclic, or tricyclic aromatic ring groups, respectively.
  • the aromatic ring group may have at least one group selected from the group consisting of a halogen atom (preferably a fluorine atom), a cyano group, and a trifluoromethyl group as a substituent.
  • the aromatic ring group does not have a substituent other than one or more groups selected from the group consisting of a halogen atom (preferably a fluorine atom), a cyano group, and a trifluoromethyl group.
  • the total number of the above-mentioned one or more groups represented by the above aromatic ring groups represented by Ar 11 to Ar 16 as substituents is, for example, 0 to 5 independently.
  • Ar 11 to Ar 14 are divalent aromatic ring groups.
  • Ar 15 to Ar 16 are monovalent aromatic ring groups.
  • the aromatic ring groups represented by Ar 11 to Ar 16 are nitrogen-containing aromatic ring groups each independently having one or more (for example, 1 to 3) nitrogen atoms as ring member atoms.
  • Ar 11 and Ar 12 have the same aromatic ring group
  • Ar 13 and Ar 14 preferably have the same aromatic ring group
  • Ar 15 and Ar 16 have the same aromatic ring group. It is also preferable.
  • each aromatic ring group is similar means that each aromatic ring group to be compared is a similar group, and each structure constituting those aromatic ring groups (heteroatoms and substituents that the aromatic ring group can have).
  • Etc. also mean that the positional relationship is the same with respect to the parent nucleus of the specific compound (partial structure enclosed in parentheses with n17 in the formula (1)).
  • Ar 11 to Ar 14 are groups represented by any of the formulas (2) to (7) independently.
  • * represents the coupling position.
  • the bond position (*) on the left side may be bonded to the mother nucleus side
  • the bond position (*) on the right side is the mother nucleus side. It may be bound to.
  • R in ⁇ CR represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.
  • the group represented by XN represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom ( -Se- ).
  • N in X N is an integer. That is, in the formulas (2) to (7), X 41 , X 51 , X 61 to X 62 , and X 71 are independently sulfur atoms (-S-) and oxygen atoms (-O-), respectively. , Or a selenium atom (-Se-), preferably a sulfur atom or an oxygen atom.
  • Ar 15 to Ar 16 are independently represented by any of the formulas (8) to (15) and the formulas (47) to (53). Is preferable.
  • N in Y N is an integer. That is, in the formulas (8) to (15) and the formulas (47) to (53), Y 81 to Y 85 , Y 91 to Y 97 , Y 101 to Y 103 , Y 111 to Y 115 , Y.
  • R in ⁇ CR represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.
  • Y 471 to Y 475 , Y 481 to Y 485 , Y 491 to Y 497 , Y 501 to Y 505 , Y 511 to Y 515 , Y 521 to Y 529 , and Y 531 to Y 539 , -CH is preferable.
  • the group represented by XN is a sulfur atom (-S-), an oxygen atom (-O-), or an oxygen atom (-O-). Represents a selenium atom (-Se-).
  • N in X N is an integer. That is, in the formulas (8) to (15) and the formulas (47) to (53), X 101 , X 111 , X 121 to X 122 , X 141 , X 151 , X 471 to X 472 , X.
  • X 481 to X 482 , X 491 , X 501 to X 502 , and X 511 to X 512 are independently sulfur atoms (-S-), oxygen atoms (-O-), or selenium atoms (-Se). -), And a sulfur atom or an oxygen atom is preferable.
  • n11 to n16 independently represent 0 or 1, respectively. It is preferable that n11 and n12 have the same value, n13 and n14 are preferably the same value, and n15 and n16 are preferably the same value.
  • n11 to n16 are 0, there is no group enclosed in parentheses with n11 to n16.
  • Ar 11 and Ar 15 are single-bonded in the formula (1).
  • n11 to n16 are all 0 and n17 is 1, the aromatic ring group represented by Ar 15 and Ar 16 is a tricyclic aromatic ring group.
  • n17 represents 1 or 2.
  • the mother nucleus of the specific compound has a structure in which two of the 4-ring or 5-ring aromatic ring groups are bonded by a single bond.
  • X 11 and X 12 existing outside the mother nucleus are the same atom.
  • X 11 and X 12 existing inside the mother nucleus are the same atom.
  • n18 represents 1 or 2.
  • Example A A combination in which n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.
  • Example B A combination in which n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.
  • Example C A combination in which n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.
  • Example D A combination in which n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.
  • Example E A combination in which n11 to n14 represent 0, n15 to n16 independently represent 0 or 1, n17 represents 2, and n18 represents 1.
  • the specific compound is a compound represented by any of the following formulas (16) to (46) and formulas (54) to (60) from the viewpoint that the effect of the present invention is more excellent. Is preferable.
  • N in Y N is an integer. That is, in equations (16) to (46), Y 21 to Y 24 , Y 41 to Y 42 , Y 51 to Y 54 , Y 61 to Y 62 , Y 71 , Y 81 to Y 85 , Y 91 to Y.
  • R in ⁇ CR represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.
  • Y 471 to Y 475 , Y 481 to Y 485 , Y 491 to Y 497 , Y 501 to Y 505 , Y 511 to Y 515 , Y 521 to Y 529 , and Y 531 to Y 539 , -CH is preferable.
  • X 11 and X 12 independently represent a sulfur atom (-S-) or an oxygen atom (-O-), respectively.
  • the groups represented by X N except X 11 to X 14 are sulfur atom (-S-), oxygen atom (-O-), or selenium atom (-Se). -) Is represented. "N" in X N is an integer.
  • X 471 , X 481 to X 482 , X 491 , X 501 to X 502 , and X 511 to X 512 are independently sulfur atoms (-S-), oxygen atoms (-O-), or oxygen atoms (-O-), respectively. It represents a selenium atom (-Se-), and a sulfur atom or an oxygen atom is preferable.
  • Compounds, Y 41 to Y 42 and Y 111 to Y 115 are ⁇ CR , and R is a hydrogen atom.
  • the specific compound (particularly when used as an n-type material described later) has the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), and the above formula. It is preferably a compound represented by any of (39) and the above formula (42).
  • the molecular weight of the specific compound is not particularly limited, and is preferably 550 or more, more preferably 600 or more.
  • the molecular weight of the specific compound is preferably 1200 or less, more preferably 1000 or less.
  • the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur.
  • the molecular weight is 550 or more, the glass transition point of the vapor-film deposition film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
  • the specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor, an optical sensor, or a photovoltaic cell.
  • 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 agent material.
  • the maximum absorption wavelength of the specific compound is not particularly limited, and is preferably in the range of, for example, 300 to 550 nm, and more preferably in the range of 400 to 550 nm.
  • 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 such that the absorbance becomes 0.5 to 1.
  • solvent chloroform
  • the specific compound is not soluble in chloroform, the value measured using the specific compound in a film state after vapor deposition of the specific compound is used as the maximum absorption wavelength of the specific compound.
  • the maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and is preferably in the range of, for example, 300 to 700 nm, and more preferably in the range of 400 to 700 nm.
  • the specific compound can be used as a p-type material (material having excellent hole transportability) and as an n-type material (material having excellent electron transportability).
  • the specific compound When a specific compound is used as an n-type material, the specific compound preferably satisfies one or more of the following requirements.
  • Requirement 1 The specific compound has three or more fluorine atoms (preferably fluorine atoms existing as substituents of aromatic ring groups represented by Ar 11 to Ar 16 in the formula (1)) in the molecule (for example, 4). ⁇ 16).
  • Requirement 2 One or more (preferably 2 to 4) of Ar 11 to Ar 14 is a nitrogen-containing aromatic ring group containing a nitrogen atom as a ring member atom, and a fluorine atom or a cyano group (preferably) in the molecule.
  • the specific compound has a total of one or more (for example, 2 to 16) fluorine atoms existing as substituents of aromatic ring groups represented by Ar 11 to Ar 16 in the formula (1).
  • the specific compound is preferably a compound that does not satisfy any of the above requirements.
  • the ionization potential of the specific compound is preferably 5.0 to 6.0 eV.
  • the electron affinity of the specific compound is preferably 3.0 to 4.5 eV.
  • the value of the reciprocal of the LUMO value obtained by the calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian) as the electron affinity value (value multiplied by -1). ) Is used.
  • the specific compound contained in the photoelectric conversion film may be substantially only the specific compound used as the p-type material, or may be substantially only the specific compound used as the n-type material, and the specific compound used as the p-type material and n. It may be both of the specific compounds used as the mold material.
  • the fact that the specific compound contained in the photoelectric conversion film is substantially only the specific compound used as the p-type material means that all the specific compounds contained in the photoelectric conversion film include the specific compound used as the p-type material.
  • the fact that the specific compound contained in the photoelectric conversion film is substantially only the specific compound used as the n-type material means that the specific compound used as the n-type material is contained in all the specific compounds contained in the photoelectric conversion film.
  • the specific compound contained in the photoelectric conversion film is both the specific compound used as the p-type material and the specific compound used as the n-type material, the specific compound used as the p-type material and the n-type material in the photoelectric conversion film.
  • the photoelectric conversion film may contain only one type of the specific compound, may contain two types, or may contain three or more types.
  • the photoelectric conversion film contains substantially only one specific compound.
  • the film thickness in terms of a single layer / the total film film in terms of a single layer of all specific compounds ⁇ 100) is more than 90% by volume and 100% by volume or less (preferably 95 to 100% by volume, more preferably 99). ⁇ 100% by volume).
  • the above-mentioned one specific compound may be a specific compound used as a p-type material or a specific compound used as an n-type material.
  • the photoelectric conversion film contains two kinds of specific compounds
  • the photoelectric conversion film contains substantially only two kinds of specific compounds.
  • the total film thickness of each of the two specific compounds contained in the single layer equivalent / the total film thickness of all the specific compounds in terms of the single layer x 100) is more than 90% by volume and 100% by volume or less ( It means that it is preferably 95 to 100% by volume, more preferably 99 to 100% by volume).
  • the film thickness in terms of a single layer / the film thickness of the specific compound B in terms of a single layer) is preferably 10/90 to 90/10, more preferably 40/60 to 60/40, and 47/53 to 53 /. 47 is more preferred.
  • both of the two kinds of specific compounds may be specific compounds used as p-type materials, or both may be specific compounds used as n-type materials. It is also preferable that one is a specific compound used as a p-type material and the other is a specific compound used as an n-type material.
  • the content of the specific compound in the photoelectric conversion film is more preferably 20 to 60% by volume, further preferably 25 to 40% by volume.
  • the content of the specific compound in the photoelectric conversion film is more preferably 40 to 80% by volume, further preferably 60 to 75% by volume.
  • the photoelectric conversion film contains a dye as a component other than the above-mentioned specific compound.
  • the dye is preferably an organic dye.
  • the above-mentioned dyes include, for example, cyanine dye, styryl pigment, hemicyanine pigment, merocyanine pigment (including zero methine merocyanine (simple merocyanine)), rodacyanine pigment, allopolar pigment, oxonol pigment, hemioxonor pigment, squalium pigment, croconium pigment, and azamethine.
  • the content of the dye with respect to the total content of the specific compound and the dye in the photoelectric conversion film (film thickness in terms of single layer of dye / (film thickness in terms of single layer of specific compound + single dye)
  • the film thickness) ⁇ 100)) in terms of layers is preferably 15 to 75% by volume, more preferably 20 to 65% by volume, and even more preferably 25 to 60% by volume.
  • the dye may be used alone or in combination of two or more.
  • the photoelectric conversion film contains an n-type semiconductor material as a component other than the above-mentioned specific compound and dye.
  • the photoelectric conversion film contains a specific compound used as a p-type material, it is preferable to include an n-type semiconductor material, and when the specific compound contained in the photoelectric conversion film is only a specific compound used as a p-type material, photoelectric is used.
  • the conversion film contains an n-type semiconductor material, and when the photoelectric conversion film contains only one specific compound and the above-mentioned one specific compound is a specific compound used as a p-type material, the photoelectric conversion film is used. More preferably contains an n-type semiconductor material.
  • the n-type semiconductor material is an acceptor-type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons. More specifically, the n-type semiconductor material is preferably an organic compound having a higher electron affinity than the specific compound when used in contact with the above-mentioned specific compound. Further, the n-type semiconductor material is preferably an organic compound having a higher electron affinity than the dye when used in contact with the above-mentioned dye.
  • the electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.
  • the n-type semiconductor material is, for example, fullerene selected from the group consisting of fullerene and its derivatives, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and , Fluolanthene derivative); 5- to 7-membered heterocyclic compound having at least one nitrogen atom, oxygen atom, and sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxalin, quinazoline, phthalazine).
  • fullerene selected from the group consisting of fullerene and its derivatives, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene
  • Examples thereof include styrylallylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silol compounds; and the compounds described in paragraphs [0056] to [0057] of JP-A-2006-100677.
  • the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  • fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  • the fullerene include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, and mixed fullerene.
  • the fullerene derivative include compounds in which a substituent is added to the above fullerene.
  • the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group.
  • the fullerene derivative the compound described in JP-A-2007-123707 is preferable.
  • the n-type semiconductor material may be used alone or in combination of two or more.
  • the total thickness of the semiconductor materials) ⁇ 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume.
  • the fullerenes may be used alone or in combination of two or more.
  • the molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
  • the photoelectric conversion film is substantially composed of only a specific compound, a dye, and an n-type semiconductor material.
  • the fact that the photoelectric conversion film is substantially composed of only the specific compound, the dye, and the n-type semiconductor material means that the total content of the specific compound, the dye, and the n-type semiconductor material is 95 with respect to the total mass of the photoelectric conversion film. It means that it is ⁇ 100% by mass.
  • the photoelectric conversion film contains a p-type semiconductor material as a component other than the above-mentioned specific compound and dye.
  • the photoelectric conversion film contains a specific compound used as an n-type material
  • the conversion film contains a p-type semiconductor material, and when the photoelectric conversion film contains only one specific compound and the above-mentioned one specific compound is a specific compound used as an n-type material, the photoelectric conversion film is used.
  • the p-type semiconductor material is a donor organic semiconductor material (compound), and refers to an organic compound having a property of easily donating electrons. More specifically, the p-type semiconductor material is preferably an organic compound having better hole transportability than the specified combination in the photoelectric conversion film, and more preferably an organic compound having better hole transportability than any of the specific compound and the dye. ..
  • the hole transport property (hole carrier mobility) of a compound can be evaluated by using, for example, the Time-of-Flitht method (range time method, TOF method) or a field effect transistor element.
  • the hole carrier mobility of the p-type semiconductor material is preferably 10 -4 cm 2 / V ⁇ s or more, more preferably 10 -3 cm 2 / V ⁇ s or more, and 10 -2 cm 2 or more. It is more preferably / V ⁇ s or more.
  • the upper limit of the hole carrier mobility is not particularly limited, but is preferably 10 cm 2 / V ⁇ s or less, for example, from the viewpoint of suppressing the flow of a small amount of current without light irradiation.
  • the p-type semiconductor material preferably has a smaller ionization potential than the specific compound in the photoelectric conversion film, and more preferably has a smaller ionization potential than any of the specific compound and the dye.
  • the p-type semiconductor material is, for example, a triarylamine compound (for example, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD), 4,4.
  • TPD triarylamine
  • '-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD) the compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP-A-2011-176259.
  • Tribal charcoal Ring compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivative
  • the p-type semiconductor material is a compound represented by the formula (p1), a compound represented by the formula (p2), a compound represented by the formula (p3), a compound represented by the formula (p4), or a compound represented by the formula (p4).
  • the compound represented by the formula (p5) is also preferable.
  • the two Rs present are independently hydrogen atoms or substituents (alkyl group, alkoxy group, halogen atom, alkylthio group, (hetero) arylthio group, alkylamino group. , (Hetero) arylamino group, (hetero) aryl group, etc. These groups may further have a substituent if possible.
  • the (hetero) aryl group further has a substituent. It may be an arylaryl group (that is, a biaryl group; at least one of the aryl groups constituting this group may be a heteroaryl group).
  • R a group represented by R in the formula (IX) of WO2019-081416 is also preferable.
  • X and Y independently represent -CR 22-, sulfur atom ( -S-), oxygen atom (-O-), -NR 2- , or -SiR 22- , respectively .
  • R 2 may have a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group or a trifluoromethyl group), an aryl group which may have a substituent, or a substituent.
  • the two or more R 2s representing a heteroaryl group may be the same or different.
  • Ar represents an aromatic ring group (preferably a benzene ring group).
  • the p-type semiconductor material is preferably a compound represented by the formula (p1).
  • the n-type semiconductor material may be used alone or in combination of two or more.
  • the photoelectric conversion film is substantially composed of only a specific compound, a dye, and a p-type semiconductor material.
  • the fact that the photoelectric conversion film is substantially composed of only the specific compound, the dye, and the p-type semiconductor material means that the total content of the specific compound, the dye, and the p-type semiconductor material is 95 with respect to the total mass of the photoelectric conversion film. It means that it is ⁇ 100% by mass.
  • the photoelectric conversion film is substantially composed of only a specific compound, a dye, an n-type semiconductor material, and a p-type semiconductor material.
  • the fact that the photoelectric conversion film is substantially composed of only a specific compound, a dye, an n-type semiconductor material, and a p-type semiconductor material means that the specific compound, the dye, and the n-type semiconductor material are used with respect to the total mass of the photoelectric conversion film. It means that the total content of the p-type semiconductor material is 95 to 100% by mass.
  • the photoelectric conversion film is preferably a mixed layer formed in a state where the specific compound and the dye are mixed.
  • the photoelectric conversion film contains an n-type semiconductor material and / or a p-type semiconductor material
  • the photoelectric conversion film is formed in a state where a specific compound and an n-type semiconductor material and / or a p-type semiconductor material are mixed. It is preferably a mixed layer.
  • the photoelectric conversion film contains a dye and an n-type semiconductor material and / or a p-type semiconductor material
  • the photoelectric conversion film is in a state where a specific compound, a dye, an n-type semiconductor material and / or a p-type semiconductor material are mixed. It is preferably a mixed layer to be formed.
  • a mixed layer is a layer in which two or more kinds of materials are mixed in a single layer.
  • the photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
  • the non-luminescent film is intended to be a film having a emission quantum efficiency of 1% or less, and the emission quantum efficiency is preferably 0.5% or less, more preferably 0.1% or less.
  • the photoelectric conversion film can be formed mainly by a dry film forming method.
  • the dry film forming method includes, for example, a vapor deposition method (particularly, a vacuum vapor deposition method), a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE (Molecular Beam Epitaxy) method, and a CVD method such as plasma polymerization. (Chemical Vapor Deposition) method can be mentioned. Of these, the vacuum vapor deposition method is preferable.
  • the manufacturing conditions such as the degree of vacuum and the 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, further preferably 50 to 500 nm, and particularly preferably 50 to 400 nm.
  • the electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) 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, it is preferable that the upper electrode 15 is transparent to the light to be detected.
  • the material constituting the upper electrode 15 is, for example, antimony or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine topped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Conductive metal oxides such as Indium Tin Oxide) and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; these metals and conductive metal oxides. Examples thereof include mixtures or laminates; organic conductive materials such as polyaniline, polythiophene and polypyrrole; and carbon materials such as graphene and carbon nanotubes. Of these, conductive metal oxides are preferable from the viewpoint of high conductivity and transparency.
  • the sheet resistance may be, for example, 100 to 10000 ⁇ / ⁇ .
  • the degree of freedom in the range of film thickness that can be thinned is large.
  • Increasing the light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
  • the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
  • the lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use.
  • the material constituting the lower electrode 11 is, for example, antimony or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium oxide tin (ITO), and indium zinc oxide (IZO).
  • Conductive metal oxides such as gold, silver, chromium, nickel, titanium, tungsten, and metals such as aluminum, oxides of these metals or conductive compounds such as nitrides (as an example, titanium nitride (TiN)). ); Mixtures or laminates of these metals and conductive metal oxides; Organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes. Be done.
  • the method for forming the electrode is not particularly limited and can be appropriately selected depending on the electrode material. Specifically, a wet method such as a printing method and a coating method; a physical method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method; and a chemical method such as CVD and plasma CVD method. , Etc. can be mentioned.
  • the electrode material is ITO, examples thereof include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a method of applying a dispersion of indium tin oxide.
  • the photoelectric conversion element of the present invention has one or more 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.
  • the electron blocking film is a donor organic semiconductor material (compound), and for example, the p-type organic semiconductor as described above can be used.
  • One type of p-type organic semiconductor may be used alone, or two or more types may be used.
  • the p-type organic semiconductor used in the electron blocking film a compound having a smaller ionization potential than the n-type semiconductor material can be mentioned, and if this condition is satisfied, the dye as described above can also be used.
  • a polymer material can also be used as the electron blocking film.
  • the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrrole, 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.
  • Inorganic materials that can be electron blocking films include, for example, calcium oxide, chromium oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium oxide copper, niobium oxide, molybdenum oxide, and indium copper oxide. , Indium silver oxide, and iridium oxide.
  • the hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type semiconductor material or the like can be used.
  • the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method.
  • the dry film forming method include a vapor deposition method and a sputtering method.
  • the vapor deposition method may be any of a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable.
  • 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 preferable.
  • the thickness of the charge blocking film is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.
  • the photoelectric conversion element may further have a substrate.
  • the type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the position of the substrate is not particularly limited, and usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
  • the photoelectric conversion element may further have a sealing layer.
  • the performance of the photoelectric conversion material may be significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is coated with a dense metal oxide, metal nitride, ceramics such as metal nitride, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon) that does not allow water molecules to permeate.
  • DLC Diamond-like Carbon
  • the photoelectric conversion element is an element that converts the optical information of an image into an electric signal. Normally, a plurality of photoelectric conversion elements are arranged in a matrix on the same plane, and each photoelectric conversion element (pixel) has an optical signal. Is converted into an electric signal, and the electric signal can be sequentially output to the outside of the image sensor for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
  • the image pickup element is mounted on a digital camera, an image pickup element such as a digital video camera, an electronic endoscope, and an image pickup module such as a mobile phone.
  • the photoelectric conversion element of the present invention is also preferably used for an optical sensor having the photoelectric conversion element of the present invention.
  • the optical sensor may be used by the photoelectric conversion element alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion elements are arranged in a plane.
  • the present invention also relates to compounds.
  • the compound of the present invention is the same as the above-mentioned specific compound (compound represented by the formula (1)), and the preferred conditions are also the same.
  • N-type semiconductor material Fullerene C60 was used as an n-type semiconductor material used for evaluation in the production of a photoelectric conversion element described later.
  • P-type semiconductor material The p-type semiconductor material shown below was used as a p-type semiconductor material used for evaluation in the production of a photoelectric conversion element described later.
  • test X a photoelectric conversion film is prepared and evaluated using a specific compound, an n-type semiconductor material and a dye
  • test Y a photoelectric conversion film is prepared using two specific compounds and a dye. Evaluation was performed
  • Test Z a photoelectric conversion film was prepared using a specific compound, a p-type semiconductor material, and a dye, and the evaluation was performed.
  • the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.
  • amorphous ITO is formed on a glass substrate by a sputtering method to form a lower electrode 11 (thickness: 30 nm), and the following compound (C-1) is further vacuumed on the lower electrode 11.
  • a film was formed by a heat vapor deposition method to form an electron blocking film 16A (thickness: 30 nm).
  • each component shown in each Example or Comparative Example shown in the table below was co-deposited to form a photoelectric conversion film 12 as a mixed layer.
  • the ratio of the vapor deposition rate of each component was adjusted so that the film thickness of each component in the photoelectric conversion film in terms of a single layer was the ratio shown in the "component ratio" column in the table.
  • the following compound (C-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
  • Amorphous ITO was formed on the hole blocking film 16B 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 on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method.
  • ALCVD Atomic Layer Chemical Vapor Deposition
  • a photoelectric conversion element of a comparative example was manufactured.
  • the compounds (1-1) to (1-36) show the properties as a p-type semiconductor.
  • the dark current of each of the obtained photoelectric conversion elements was measured by the following method. A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so as to have an electric field strength of 2.5 ⁇ 105 V / cm, and the current value (dark current) in a dark place was measured. Next, similarly, a voltage is applied so as to have an electric field strength of 7.5 ⁇ 10 4 V / cm, and the current value (dark current) in a dark place is measured. The ratio was calculated and evaluated according to the following criteria.
  • Relative ratio of dark current (dark current of 2.5 ⁇ 10 5 V / cm) / (dark current of 7.5 ⁇ 10 4 V / cm)
  • E Relative ratio of dark current is 3.5 or more
  • Relative ratio (Integral value of photoelectric conversion efficiency of the photoelectric conversion element to be evaluated at 400 to 700 nm) / (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1 at 400 to 700 nm)
  • C Relative ratio of integrated values of photoelectric conversion efficiency is 1. .0 or more and less than 1.2
  • Relative ratio of integrated values of photoelectric conversion efficiency is less than 0.8
  • the photoelectric conversion efficiency ratio was calculated from the following formula using the integrated value of the photoelectric conversion efficiency at 400 to 700 nm measured at each electric field strength, and the electric field strength dependence of the photoelectric conversion efficiency was evaluated according to the following criteria.
  • Photoelectric conversion efficiency ratio (Integral value of photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so as to have an electric field strength of 7.5 ⁇ 10 4 V / cm) / (photoelectric conversion element to be evaluated) (Integral value of photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so as to have an electric field strength of 2.5 ⁇ 10 5 V / cm)
  • Photoelectric conversion efficiency ratio is less than 0.6
  • the compounds represented by the above formula (16) in which Y 41 to Y 42 and Y 81 to Y 85 are -CR and R is a hydrogen atom, Y 41 to Y 42 and Y 111 to Y 115 are- .
  • R is a hydrogen atom.
  • the dark current of each of the obtained photoelectric conversion elements was measured by the following method. A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so as to have an electric field strength of 2.5 ⁇ 105 V / cm, and the current value (dark current) in a dark place was measured. As a result, it was confirmed that the dark current was 50 nA / cm 2 or less in any of the photoelectric conversion elements, and the dark current was sufficiently low.
  • Photoelectric conversion efficiency ratio (Integral value of photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so as to have an electric field strength of 2.0 ⁇ 105 V / cm) / (photoelectric conversion element to be evaluated) (Integral value of photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so as to have an electric field strength of 2.5 ⁇ 10 5 V / cm)
  • the group represented by 8 it was confirmed that the effect of the present invention is more excellent (Examples 2-3, 2-7, 2-9, 2-10, 2-12 to 2-17). See results etc.).

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WO2025204395A1 (ja) * 2024-03-25 2025-10-02 富士フイルム株式会社 組成物、光電変換素子、撮像素子、光センサ、撮像素子の製造方法

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