WO2021002131A1 - 半導体膜、光電変換素子、イメージセンサおよび半導体膜の製造方法 - Google Patents

半導体膜、光電変換素子、イメージセンサおよび半導体膜の製造方法 Download PDF

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WO2021002131A1
WO2021002131A1 PCT/JP2020/021607 JP2020021607W WO2021002131A1 WO 2021002131 A1 WO2021002131 A1 WO 2021002131A1 JP 2020021607 W JP2020021607 W JP 2020021607W WO 2021002131 A1 WO2021002131 A1 WO 2021002131A1
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atom
semiconductor
semiconductor quantum
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French (fr)
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雅司 小野
真宏 高田
哲志 宮田
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Fujifilm Corp
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    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors
    • H10F39/18—Complementary metal-oxide-semiconductor [CMOS] image sensors; Photodiode array image sensors
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    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
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    • B82—NANOTECHNOLOGY
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Definitions

  • the present invention relates to a semiconductor film containing semiconductor quantum dots containing metal atoms, a photoelectric conversion element, an image sensor, and a method for manufacturing the semiconductor film.
  • silicon photodiode using a silicon wafer as a material for a photoelectric conversion layer has been used for a photodetector used in an image sensor or the like.
  • silicon photodiodes have low sensitivity in the infrared region with a wavelength of 900 nm or more.
  • InGaAs-based semiconductor materials known as near-infrared light receiving elements require extremely high-cost processes, such as needing epitaxial growth in order to achieve high quantum efficiency. , Not widespread.
  • Non-Patent Document 1 describes a solar cell device having a semiconductor film containing PbS quantum dots treated with ZnI 2 and 3-mercaptopropionic acid as a photoelectric conversion layer.
  • Non-Patent Document 1 When the present inventor examined the semiconductor film described in Non-Patent Document 1, it was found that this semiconductor film has a large variation in the external quantum efficiency in terms of plane. It was also found that there is room for further improvement in electrical conductivity, photocurrent value and external quantum efficiency.
  • an object of the present invention is a method for manufacturing a semiconductor film, a photoelectric conversion element, an image sensor, and a semiconductor film, which have high electrical conductivity, photocurrent value, and external quantum efficiency, and also have excellent in-plane uniformity of external quantum efficiency. Is to provide.
  • the ligand includes a first ligand which is an inorganic halide and a second ligand represented by any of the formulas (A) to (C).
  • X A1 and X A2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • L A1 represents a hydrocarbon group
  • the X A1 and X A2 is L A1, being separated one atom or two atoms, If other is carboxy groups while the thiol group of X A1 and X A2, X A1 and X A2 are separated one atom by L A1;
  • X B1 and X B2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group, respectively.
  • X B3 represents S, O or NH LB1 and LB2 each independently represent a hydrocarbon group.
  • X B1 and X B3 are L B1, it is separated one atom or two atoms, By X B2 and X B3 is L B2, it is separated one atom or two atoms;
  • X C1 to X C3 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • X C4 represents N LC1 to LC3 independently represent hydrocarbon groups, respectively.
  • X C1 and X C4 are separated one atom or two atoms
  • X C2 and X C4 is L C2
  • X C3 and X C4 by L C3 are separated one atom or two atoms.
  • ⁇ 2> The semiconductor film according to ⁇ 1>, wherein the semiconductor quantum dots contain Pb atoms.
  • ⁇ 3> The semiconductor film according to ⁇ 1> or ⁇ 2>, wherein the first ligand contains at least one selected from Group 12 elements and Group 13 elements.
  • ⁇ 4> The semiconductor film according to any one of ⁇ 1> to ⁇ 3>, wherein the first ligand contains a Zn atom.
  • ⁇ 5> The semiconductor film according to any one of ⁇ 1> to ⁇ 4>, wherein the first ligand contains an iodine atom.
  • the second ligand is thioglycolic acid, 2-aminoethanol, 2-aminoethanethiol, 2-mercaptoethanol, diethylenetriamine, tris (2-aminoethyl) amine, (aminomethyl) phosphonic acid and
  • the semiconductor film according to any one of ⁇ 1> to ⁇ 5> which is at least one selected from these derivatives.
  • ⁇ 7> The semiconductor film according to any one of ⁇ 1> to ⁇ 6>, which contains two or more of the first ligands.
  • ⁇ 8> The semiconductor film according to any one of ⁇ 1> to ⁇ 7>, which contains two or more of the second ligands.
  • ⁇ 9> The semiconductor film according to any one of ⁇ 1> to ⁇ 8>, further comprising a ligand other than the first ligand and the second ligand.
  • ⁇ 11> The photoelectric conversion element according to ⁇ 10>, which is a photodiode type photodetection element.
  • the image sensor according to ⁇ 12> which senses light having a wavelength of 900 nm to 1600 nm.
  • a ligand solution 1 containing a first ligand and a solvent, which are inorganic halides, and a formula (A) are applied to the film of the aggregate of semiconductor quantum dots formed by the step of forming the aggregate of semiconductor quantum dots.
  • the formula (A) To the ligand solution 2 containing the second ligand represented by any of (C) and the solvent, or the first ligand which is an inorganic halide, the formula (A).
  • the second ligand represented by any of (C) and the ligand solution 3 containing the solvent are applied, and the third ligand that coordinates with the semiconductor quantum dot is given to the third ligand.
  • L A1 represents a hydrocarbon group
  • the X A1 and X A2 is L A1, being separated one atom or two atoms, If other is carboxy groups while the thiol group of X A1 and X A2, X A1 and X A2 are separated one atom by L A1;
  • X B1 and X B2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group, respectively.
  • X B3 represents S, O or NH LB1 and LB2 each independently represent a hydrocarbon group.
  • X B1 and X B3 are L B1, it is separated one atom or two atoms, By X B2 and X B3 is L B2, it is separated one atom or two atoms;
  • X C1 to X C3 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • X C4 represents N LC1 to LC3 independently represent hydrocarbon groups, respectively.
  • X C1 and X C4 are L C1, are separated one atom or two atoms
  • X C2 and X C4 is L C2
  • X C3 and X C4 by L C3 are separated one atom or two atoms.
  • ⁇ 17> The method for producing a semiconductor film according to ⁇ 15>, wherein the aprotic solvent is at least one selected from acetonitrile and acetone.
  • a film of the semiconductor quantum dot aggregate having a thickness of 30 nm or more is formed.
  • the method for producing a semiconductor film according to any one of ⁇ 14> to ⁇ 17>, wherein the complex stability constant K1 of the second ligand with respect to the metal atom contained in the semiconductor quantum dot is 6 or more.
  • the complex stability constant K1 of the second ligand with respect to the metal atom contained in the semiconductor quantum dot is 8 or more.
  • the semiconductor quantum dot contains a Pb atom and contains a Pb atom.
  • a method for manufacturing a semiconductor film, a photoelectric conversion element, an image sensor, and a semiconductor film which have high electrical conductivity, photocurrent value, and external quantum efficiency, and also have excellent in-plane uniformity of external quantum efficiency. can do.
  • the contents of the present invention will be described in detail below.
  • "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the notation that does not describe substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the semiconductor film of the present invention is An aggregate of semiconductor quantum dots containing metal atoms and Containing ligands that coordinate to semiconductor quantum dots,
  • the ligand is characterized by containing a first ligand which is an inorganic halide and a second ligand represented by any of the formulas (A) to (C).
  • the semiconductor film of the present invention has high electrical conductivity, photocurrent value and external quantum efficiency, and is also excellent in in-plane uniformity of external quantum efficiency.
  • the detailed reason for obtaining such an effect is unknown, but it is presumed to be due to the following.
  • the metal atom of the semiconductor quantum dot is formed at the site of XA1 and XA2. It is presumed to be coordinated.
  • the ligand represented by the formula (B) (hereinafter, also referred to as the ligand (B))
  • the site of X B1 to X B3 is coordinated to the metal atom of the semiconductor quantum dot.
  • the ligand represented by the formula (C) (hereinafter, also referred to as the ligand (C))
  • the ligands are coordinated to the metal atoms of the semiconductor quantum dots at the sites X C1 to X C4 .
  • the ligand (A) the ligand (B) and the ligand (C) all have a plurality of sites coordinated with the metal atom of the semiconductor quantum dot in one molecule.
  • the ligand that coordinates the semiconductor quantum dot further contains the first ligand that is an inorganic halide, so that the gap in which the second ligand is not coordinated is included. It is presumed that the first ligand is coordinated, and that the surface defects of the semiconductor quantum dots can be reduced. Therefore, it is presumed that the electrical conductivity, the photocurrent value, the external quantum efficiency, and the in-plane uniformity of the external quantum efficiency could be improved.
  • the semiconductor film has an aggregate of semiconductor quantum dots containing metal atoms.
  • the aggregate of semiconductor quantum dots refers to a form in which a large number of semiconductor quantum dots (for example, 100 or more per 1 ⁇ m 2 ) are arranged close to each other.
  • specific resistance means a material is 10 -2 [Omega] cm or more 10 8 [Omega] cm or less.
  • Semiconductor quantum dots are semiconductor particles having metal atoms.
  • the metal atom also includes a metalloid atom represented by a Si atom.
  • the semiconductor quantum dot material constituting the semiconductor quantum dot include general semiconductor crystals [a) group IV semiconductors, b) group IV-IV, group III-V, or group semiconductor II-VI compound semiconductors, c) II. Nanoparticles (particles of 0.5 nm or more and less than 100 nm) of a compound semiconductor composed of a combination of three or more of Group, Group III, Group IV, Group V, and Group VI elements can be mentioned.
  • the semiconductor quantum dot preferably contains at least one metal atom selected from Pb atom, In atom, Ge atom, Si atom, Cd atom, Zn atom, Hg atom, Al atom, Sn atom and Ga atom. It is more preferable that it contains at least one metal atom selected from Pb atom, In atom, Ge atom and Si atom, and it is further preferable that it contains Pb atom because the effect of the present invention can be obtained more remarkably. preferable.
  • the semiconductor quantum dot material constituting the semiconductor quantum dot include PbS, PbSe, PbSeS, InN, InAs, Ge, InAs, InGaAs, CuInS, CuInSe, CuInGaSe, InSb, HgTe, HgCdTe, Ag2S, Ag2Se, Ag2Te.
  • semiconductor materials such as SnS, SnSe, SnTe, Si, and InP have a relatively narrow bandgap.
  • the semiconductor quantum dot preferably contains PbS or PbSe, and preferably contains PbS, because the absorption coefficient of light in the infrared region is large, the lifetime of photocurrent is long, and the carrier mobility is large. Is more preferable.
  • the semiconductor quantum dot may be a material having a core-shell structure in which the semiconductor quantum dot material is the core and the semiconductor quantum dot material is covered with a coating compound.
  • the coating compound include ZnS, ZnSe, ZnTe, ZnCdS, CdS, GaP and the like.
  • the band gap of the semiconductor quantum dots is preferably 0.5 eV to 2.0 eV.
  • the photodetector can be a photodetector capable of detecting light of various wavelengths depending on the application. it can. For example, it can be a photodetector capable of detecting light in the infrared region.
  • the upper limit of the band gap of the semiconductor quantum dots is preferably 1.9 eV or less, more preferably 1.8 eV or less, and even more preferably 1.5 eV or less.
  • the lower limit of the band gap of the semiconductor quantum dots is preferably 0.6 eV or more, and more preferably 0.7 eV or more.
  • the average particle size of the semiconductor quantum dots is preferably 2 nm to 15 nm.
  • the average particle size of the semiconductor quantum dots refers to the average particle size of 10 semiconductor quantum dots.
  • a transmission electron microscope may be used for measuring the particle size of the semiconductor quantum dots.
  • semiconductor quantum dots include particles of various sizes from several nm to several tens of nm.
  • semiconductor quantum dots if the average particle size of the semiconductor quantum dots is reduced to a size smaller than the Bohr radius of the internal electrons, a phenomenon occurs in which the band gap of the semiconductor quantum dots changes due to the quantum size effect.
  • the average particle size of the semiconductor quantum dots is 15 nm or less, it is easy to control the band gap by the quantum size effect.
  • the thickness of the semiconductor film is not particularly limited, but is preferably 10 nm to 600 nm, more preferably 50 nm to 600 nm, further preferably 100 nm to 600 nm, and even more preferably 150 nm from the viewpoint of obtaining high electrical conductivity. It is even more preferably about 600 nm.
  • the upper limit of the thickness is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 450 nm or less.
  • the semiconductor film contains a ligand that coordinates the semiconductor quantum dots.
  • the ligand includes a first ligand which is an inorganic halide and a second ligand represented by any of the formulas (A) to (C).
  • the semiconductor film may contain only one type of the first ligand, or may contain two or more types. Further, the semiconductor film may contain only one type of second ligand, or may contain two or more types.
  • the first ligand is an inorganic halide.
  • the halogen atom contained in the first ligand that is, the inorganic halide include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, which are iodine atoms because a high coordinating force can be easily obtained. Is preferable.
  • the first ligand that is, the inorganic halide, preferably contains at least one selected from Group 12 elements and Group 13 elements.
  • the first ligand is preferably a compound containing a metal atom selected from a Zn atom, an In atom and a Cd atom, and more preferably a compound containing a Zn atom.
  • the inorganic halide is preferably a salt of a metal atom and a halogen atom because it is easily ionized and easily coordinated with a semiconductor quantum dot.
  • the first ligand include zinc iodide, zinc bromide, zinc chloride, indium iodide, indium bromide, indium chloride, cadmium iodide, cadmium bromide, cadmium chloride, gallium iodide, and odor.
  • examples thereof include gallium bromide and gallium chloride, and zinc iodide is particularly preferable.
  • the inorganic halide may be coordinated on the surface of the semiconductor quantum dot in the film, or it may be dissociated into a halogen ion and an inorganic ion, and each of them may be a semiconductor quantum dot. It may be coordinated on the surface of.
  • zinc iodide zinc iodide may be coordinated on the surface of semiconductor quantum dots, or zinc iodide may be dissociated into iodine ions and zinc ions, respectively. May be coordinated to the surface of semiconductor quantum dots.
  • the second ligand is a ligand represented by any of the formulas (A) to (C).
  • the second ligand is preferably the ligand represented by the formula (A) because it is easy to increase the electric conductivity, the photocurrent value and the external quantum efficiency of the semiconductor film.
  • the ligand represented by the formula (A) is a compound having a relatively low molecular weight, and has sites that coordinate with the metal atoms of the semiconductor quantum dots at both ends. It is presumed that chelate coordination is easy, and that steric obstacles between semiconductor quantum dots can be made smaller.
  • X A1 and X A2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • L A1 represents a hydrocarbon group
  • the X A1 and X A2 is L A1, being separated one atom or two atoms, If other is carboxy groups while the thiol group of X A1 and X A2, X A1 and X A2 are separated one atom by L A1;
  • X B1 and X B2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group, respectively.
  • X B3 represents S, O or NH LB1 and LB2 each independently represent a hydrocarbon group.
  • X B1 and X B3 is L B1, it is separated one atom or two atoms
  • X B2 and X B3 is L B2, it is separated one atom or two atoms
  • X C1 to X C3 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • X C4 represents N LC1 to LC3 independently represent hydrocarbon groups, respectively.
  • X C1 and X C4 are separated one atom or two atoms
  • X C2 and X C4 is L C2
  • X C3 and X C4 by L C3 are separated one atom or two atoms.
  • the amino groups represented by X A1 , X A2 , X B1 , X B2 , X C1 , X C2 and X C3 are not limited to -NH 2 , but also include substituted amino groups and cyclic amino groups.
  • the substituted amino group include a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, an alkylarylamino group and the like.
  • -NH 2 a monoalkylamino group and a dialkylamino group are preferable, and -NH 2 is more preferable.
  • At least one of X A1 and X A2 is preferably a thiol group, an amino group, a hydroxy group or a carboxy group, and more preferably a thiol group.
  • Preferred combinations of X A1 and X A2, while the thiol group of X A1 and X A2, the other thiol group, an amino group, a combination is a hydroxy group or carboxy group, one amino group of X A1 and X A2 Then, a combination in which the other is a hydroxy group or a carboxy group can be mentioned.
  • one of X A1 and X A 2 is a thiol group, and the other is a thiol group, an amino group, or a hydroxy group because it has a high coordinating force on the surface of the quantum dot and it is easy to reduce surface defects.
  • a combination of carboxy groups is preferable.
  • X A1 is a group different from X A 2 . According to this aspect, it becomes easier to coordinate more firmly with respect to the semiconductor quantum dot, and the electric conductivity, the photocurrent value, the external quantum efficiency, and the in-plane uniformity of the external quantum efficiency can be further improved. Furthermore, it is easy to suppress the occurrence of film peeling.
  • At least one of X B1 and X B2 is preferably a thiol group, an amino group, or a hydroxy group, and more preferably an amino group.
  • X B3 represents S, O or NH, preferably O or NH, and more preferably NH.
  • At least one of X C1 to X C3 is preferably a thiol group, an amino group, or a hydroxy group, and more preferably an amino group.
  • the L A1, L B1, L B2 , L C1, hydrocarbon group L C2 and L C3 represents preferably an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
  • Specific examples of the hydrocarbon group include an alkylene group, an alkenylene group, and an ethynylene group.
  • alkylene group examples include a linear alkylene group, a branched alkylene group and a cyclic alkylene group, and a linear alkylene group or a branched alkylene group is preferable, and a linear alkylene group is more preferable.
  • alkenylene group examples include a linear alkenylene group, a branched alkenylene group and a cyclic alkenylene group, and a linear alkenylene group or a branched alkenylene group is preferable, and a linear alkenylene group is more preferable.
  • the alkylene group and the alkenylene group may further have a substituent.
  • the substituent is preferably a group having 1 or more and 10 or less atoms.
  • Preferred specific examples of the group having 1 to 10 atoms are an alkyl group having 1 to 3 carbon atoms [methyl group, ethyl group, propyl group and isopropyl group] and an alkenyl group having 2 to 3 carbon atoms [ethenyl group and propenyl group].
  • alkynyl group with 2 to 4 carbon atoms [ethynyl group, propynyl group, etc.], cyclopropyl group, alkoxy group with 1 to 2 carbon atoms [methoxy group and ethoxy group], acyl group with 2 to 3 carbon atoms [acetyl Group and propionyl group], alkoxycarbonyl group with 2-3 carbon atoms [methoxycarbonyl group and ethoxycarbonyl group], acyloxy group with 2 carbon atoms [acetyloxy group], acylamino group with 2 carbon atoms [acetylamino group], carbon Numbers 1 to 3 hydroxyalkyl groups [hydroxymethyl group, hydroxyethyl group, hydroxypropyl group], aldehyde group, hydroxy group, carboxy group, sulfo group, phospho group, carbamoyl group, cyano group, isocyanate group, thiol group, nitro Group, nitroxy group,
  • the X A1 and X A2 is L A1, being separated one atom or two atoms, when one of X A1 and X A2 is other carboxy group with a thiol group, X A1 and X A2 It is separated one atom by L A1.
  • the X C1 and X C4 is L C1, are separated one atom or two atoms, the X C2 and X C4 is L C2, are separated one atom or two atoms, X C3 and X C4 is the L C3, it is separated one atom or two atoms.
  • X A1 and X A2 by L A1, and are separated one atom or two atoms, the number is one or two atoms constituting the molecular chain of the shortest distance connecting the X A1 and X A2 Means that.
  • X A1 and X A2 are separated by two atoms.
  • the numbers added to the following structural formulas represent the order of the arrangement of atoms constituting the shortest distance molecular chain connecting X A1 and X A2 .
  • thioglycolic acid at site thiol group corresponding to X A1, at the site corresponding to the X A2 is a carboxyl group, a compound of structure part corresponding to L A1 is a methylene group (Compound with the following structure).
  • X A1 (thiol group) and X A2 (carboxy group) are separated by one atom by LA1 (methylene group).
  • X B1 and X B3 is L B1, that are separated one atom or two atoms
  • the X B2 and X B3 is L B2, that are separated one atom or two atoms
  • X C1 and X C4 is L C1 by, that are separated one atom or two atoms
  • the X C2 and X C4 is L C2
  • the X C3 and X C4 is L C3, 1 atom or two atoms apart
  • the second ligand examples include thioglycolic acid, 2-aminoethanol, 2-aminoethanethiol, 2-mercaptoethanol, glycolic acid, diethylenetriamine, tris (2-aminoethyl) amine, and 1-thioglycerol.
  • Dimercaprol ethylenediamine, ethyleneglycol, aminosulfonic acid, glycine, (aminomethyl) phosphonic acid, guanidine, diethanolamine, 2- (2-aminoethyl) aminoethanol, homoserine, cysteine, thioalic acid, malic acid, tartrate and Examples thereof include these derivatives.
  • thioglycolic acid 2-aminoethanol, 2-mercaptoethanol and 2-aminoethanethiol are preferable, and thioglycolic acid is more preferable, because the effects of the present invention can be obtained more remarkably.
  • the complex stability constant K1 of the second ligand with respect to the metal atom contained in the semiconductor quantum dot is preferably 6 or more, more preferably 8 or more, and further preferably 9 or more.
  • the complex stability constant K1 is 6 or more, the strength of the bond between the semiconductor quantum dot and the second ligand can be increased. Therefore, it is possible to suppress the peeling of the second ligand from the semiconductor quantum dot, and as a result, the electrical conductivity, the photocurrent value, the external quantum efficiency, the in-plane uniformity of the external quantum efficiency, etc. can be further improved. Can be done.
  • the complex stability constant K1 is a constant determined by the relationship between the ligand and the metal atom to be coordinated, and is represented by the following formula (b).
  • a plurality of ligands may be coordinated to one metal atom, but in the present invention, it is represented by the formula (b) when one ligand molecule is coordinated to one metal atom.
  • the complex stability constant K1 is defined as an index of the strength of coordination bonds.
  • the complex stability constant K1 between the ligand and the metal atom can be obtained by spectroscopy, magnetic resonance spectroscopy, potentiometry, solubility measurement, chromatography, calorimetry, freezing point measurement, vapor pressure measurement, relaxation measurement, and viscosity. There are measurement, surface tension measurement, etc.
  • Sc-Database ver. which summarizes the results from various methods and research institutes.
  • the complex stability constant K1 was determined by using 5.85 (Academic Software) (2010).
  • the complex stability constant K1 is Sc-Database ver. If it is not in 5.85, A. E. Martell and R.M. M. The values described in Critical Stability Constants by Smith are used.
  • a semiconductor quantum dot containing a Pb atom is used (more preferably PbS is used), and the complex stability constant K1 of the second ligand with respect to the Pb atom is preferably 6 or more, preferably 8 or more. Is more preferable, and 9 or more is further preferable.
  • the semiconductor film further contains a ligand other than the first ligand and the second ligand (hereinafter, also referred to as another ligand) as a ligand that coordinates with the semiconductor quantum dot. May be good.
  • ligands include ligands represented by any of the following formulas (D) to (F), 3-mercaptopropionic acid and the like.
  • X D1 and X D2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group, respectively.
  • L D1 represents a hydrocarbon group
  • X D1 and X D2 are separated by 3 to 10 atoms by L D1 ;
  • X E1 and X E2 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group, respectively.
  • X- E3 represents S, O or NH
  • LE1 and LE2 each independently represent a hydrocarbon group.
  • X E1 and X E3 are L E1, it is separated 3-10 atoms, By X E2 and X E3 is L E2, it is separated 1-10 atoms;
  • X F1 to X F3 independently represent a thiol group, an amino group, a hydroxy group, a carboxy group, a sulfo group, a phospho group or a phosphonic acid group.
  • X F4 represents N and LF1 to LF3 independently represent hydrocarbon groups, respectively.
  • X F1 and X F4 are separated by 3 to 10 atoms by L F1 .
  • X F2 and X F4 is L F2, being separated 1-10 atoms, X F3 and X F4 are separated by 1 to 10 atoms by L F3 .
  • the second ligand is the total mass of the second ligand and the other ligand. It is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Further, even if it does not contain any of the ligand represented by the above formula (D), the ligand represented by the above formula (E), and the ligand represented by the above formula (F). Good.
  • the method for producing a semiconductor film of the present invention is A semiconductor quantum dot containing a metal atom, a first ligand which is a ligand coordinated to the semiconductor quantum dot and is an inorganic halide, and a second ligand represented by any of the formulas (A) to (C).
  • the ligand solution 1 containing the first ligand and the solvent which are inorganic halides and the formula (A) to A second ligand represented by any of (C) and a ligand solution 2 containing a solvent are added, or a first ligand which is an inorganic halide, formulas (A) to A ligand solution 3 containing the second ligand and the solvent represented by any of (C) is applied, and the third ligand coordinated to the semiconductor quantum dot is assigned to the first ligand.
  • the semiconductor quantum dot aggregate forming step and the ligand exchange step may be alternately repeated a plurality of times. Further, a rinsing step of bringing the rinsing liquid into contact with the film of the aggregate of semiconductor quantum dots to rinse the film may be further included.
  • a film of an aggregate of semiconductor quantum dots is formed on the substrate by applying a semiconductor quantum dot dispersion liquid on the substrate in the step of forming the aggregate of semiconductor quantum dots.
  • the semiconductor quantum dots are dispersed in the solvent by the third ligand, the semiconductor quantum dots are unlikely to be in the form of aggregated bulk. Therefore, by applying the semiconductor quantum dot dispersion liquid on the substrate, the aggregate of semiconductor quantum dots can be configured such that each semiconductor quantum dot is arranged.
  • a ligand exchange takes place between the child and the first and second ligands. Therefore, it is considered that the semiconductor quantum dots are easily brought close to each other.
  • the proximity of the semiconductor quantum dots enhances the electrical conductivity of the aggregate of the semiconductor quantum dots, so that a semiconductor film having a high photocurrent value and high external quantum efficiency can be obtained.
  • a semiconductor quantum dot containing a metal atom, a third ligand coordinating to the semiconductor quantum dot, and a semiconductor quantum dot dispersion liquid containing a solvent are applied onto a substrate to make a semiconductor. It forms a film of aggregates of quantum dots.
  • the semiconductor quantum dot dispersion liquid may be applied to the surface of the substrate or may be applied to another layer provided on the substrate. Examples of the other layer provided on the substrate include an adhesive layer for improving the adhesion between the substrate and the aggregate of semiconductor quantum dots, a transparent conductive layer, and the like.
  • the semiconductor quantum dot dispersion liquid contains a semiconductor quantum dot having a metal atom, a third ligand, and a solvent.
  • the semiconductor quantum dot dispersion liquid may further contain other components as long as the effects of the present invention are not impaired.
  • the details of the semiconductor quantum dots containing the metal atoms contained in the semiconductor quantum dot dispersion liquid are as described above, and the preferred embodiment is also the same.
  • the content of the semiconductor quantum dots in the semiconductor quantum dot dispersion is preferably 1 mg / mL to 500 mg / mL, more preferably 10 mg / mL to 200 mg / mL, and 20 mg / mL to 100 mg / mL. It is more preferable to have.
  • the content of the semiconductor quantum dots in the semiconductor quantum dot dispersion liquid is 1 mg / mL or more, the density of the semiconductor quantum dots on the substrate becomes high, and a good film can be easily obtained.
  • the film thickness obtained by applying the semiconductor quantum dot dispersion liquid once is less likely to increase. Therefore, in the ligand exchange step of the next step, the ligand exchange of the third ligand coordinating with the semiconductor quantum dots existing in the film can be sufficiently performed.
  • the third ligand contained in the semiconductor quantum dot dispersion liquid acts as a ligand for coordinating the semiconductor quantum dots and has a molecular structure that easily causes steric hindrance, and the semiconductor quantum dots are dispersed in the solvent. Those that also serve as a dispersant are preferable.
  • the third ligand is preferably a ligand having at least 6 or more carbon atoms in the main chain from the viewpoint of improving the dispersibility of the semiconductor quantum dots, and has a coordination in which the main chain has 10 or more carbon atoms. It is more preferable to be a child.
  • the third ligand may be either a saturated compound or an unsaturated compound. Specific examples of the third ligand include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, erucic acid, oleylamine, dodecylamine, dodecanethiol, 1,2-hexadecanethiol.
  • the third ligand is preferably one that does not easily remain in the film after the formation of the semiconductor film. Specifically, it is preferable that the molecular weight is small.
  • the third ligand is preferably oleic acid or oleylamine from the viewpoint that the semiconductor quantum dots have dispersion stability and are unlikely to remain on the semiconductor film.
  • the content of the third ligand in the semiconductor quantum dot dispersion is preferably 0.1 mmol / L to 500 mmol / L, preferably 0.5 mmol / L to the total volume of the semiconductor quantum dot dispersion. More preferably, it is 100 mmol / L.
  • the solvent contained in the semiconductor quantum dot dispersion is not particularly limited, but it is preferably a solvent that is difficult to dissolve the semiconductor quantum dots and easily dissolves the third ligand.
  • an organic solvent is preferable. Specific examples include alkanes [n-hexane, n-octane, etc.], benzene, toluene, and the like.
  • the solvent contained in the semiconductor quantum dot dispersion liquid may be only one type or a mixed solvent in which two or more types are mixed.
  • the solvent contained in the semiconductor quantum dot dispersion is preferably a solvent that does not easily remain in the formed semiconductor film. If the solvent has a relatively low boiling point, the content of residual organic matter can be suppressed when the semiconductor film is finally obtained. Further, as the solvent, a solvent having good wettability to the substrate is preferable. For example, when a semiconductor quantum dot dispersion is applied on a glass substrate, the solvent is preferably an alkane such as hexane or octane.
  • the content of the solvent in the semiconductor quantum dot dispersion is preferably 50% by mass to 99% by mass, more preferably 70% by mass to 99% by mass, based on the total mass of the semiconductor quantum dot dispersion. It is more preferably 90% by mass to 98% by mass.
  • the semiconductor quantum dot dispersion liquid is applied on the substrate.
  • the shape, structure, size, etc. of the substrate are not particularly limited and can be appropriately selected according to the purpose.
  • the structure of the substrate may be a single layer structure or a laminated structure.
  • a substrate composed of glass, an inorganic material such as YSZ (Yttria-Stabilized Zirconia; yttria-stabilized zirconium), a resin, a resin composite material, or the like can be used.
  • electrodes, an insulating film and the like may be formed on the substrate. In that case, the semiconductor quantum dot dispersion liquid is applied on the electrodes and the insulating film on the substrate.
  • the method of applying the semiconductor quantum dot dispersion liquid on the substrate is not particularly limited. Examples thereof include a spin coating method, a dip method, an inkjet method, a dispenser method, a screen printing method, a letterpress printing method, an intaglio printing method, and a spray coating method.
  • the film thickness of the semiconductor quantum dot aggregate formed by the semiconductor quantum dot aggregate forming step is preferably 3 nm or more, more preferably 10 nm or more, and more preferably 30 nm or more.
  • the upper limit is preferably 200 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • Ligand exchange process In the ligand exchange step, the ligand solution 1 containing the first ligand and the solvent and the second ligand solution 1 and the second A ligand solution 2 containing a ligand and a solvent is added, or a ligand solution 3 containing a first ligand, a second ligand and a solvent is added to obtain a semiconductor quantum dot. The third ligand coordinated with is exchanged for the first ligand and the second ligand.
  • the complex stability constant K1 of the second ligand with respect to the metal atom contained in the semiconductor quantum dot is preferably 6 or more, more preferably 8 or more, and further preferably 9 or more.
  • the complex stability constant K1 is 6 or more, the ligand exchange between the third ligand and the second ligand can be performed quickly, and the ligand is formed by the semiconductor quantum dot aggregate forming step. Even if the film thickness of the aggregate of semiconductor quantum dots is large, ligand exchange can be sufficiently performed up to the bottom side of the film. For this reason, normally, the semiconductor quantum dot aggregate forming step and the ligand exchange step are alternately repeated a plurality of times to form a semiconductor film having a desired thickness, but the film thickness formed per cycle is large.
  • the ligand exchange can be sufficiently performed up to the bottom of the film, the tact time in producing a semiconductor film having a desired film thickness can be shortened. Further, when the complex stability constant K1 is 6 or more, the second ligand can be firmly coordinated to the semiconductor quantum dot, and the electric conductivity, photocurrent value, external quantum efficiency, and external of the semiconductor film can be obtained. In-plane uniformity of quantum efficiency can be further improved.
  • the second ligand is a complex stability constant K1 for a metal atom contained in the semiconductor quantum dots. Is preferably 6 or more, more preferably 8 or more, and even more preferably 9 or more. Further, when a semiconductor quantum dot containing a Pb atom is used (more preferably PbS is used), the second ligand has a complex stability constant K1 with respect to the Pb atom of 6 or more. It is preferable that the amount is 8 or more, and more preferably 9 or more.
  • the first ligand content contained in the ligand solution 1 and the ligand solution 3 is preferably 1 mmol / L to 500 mmol / L, and more preferably 5 mmol / L to 100 mmol / L. It is more preferably 10 mmol / L to 50 mmol / L.
  • the content of the second ligand contained in the ligand solution 2 and the ligand solution 3 is preferably 0.001 v / v% to 5 v / v%, preferably 0.002 v / v% to 1 v /. It is more preferably v%, and even more preferably 0.005 v / v% to 0.1 v / v%.
  • the solvent contained in the ligand solution 1, the ligand solution 2 and the ligand solution 3 is preferably selected as appropriate according to the type of the ligand contained in each ligand solution, and each ligand is preferably selected. It is preferable that the solvent is easy to dissolve. Further, the solvent contained in the ligand solution is preferably an organic solvent having a high dielectric constant. Specific examples include ethanol, acetone, methanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, butanol, propanol and the like. Further, the solvent contained in the ligand solution is preferably a solvent that does not easily remain in the formed semiconductor film.
  • the solvent contained in the ligand solution is preferably one that does not mix with the solvent contained in the semiconductor quantum dot dispersion liquid.
  • the solvent contained in the ligand solution is preferably a polar solvent such as methanol or acetone. ..
  • the solvent content in the ligand solution is the balance obtained by subtracting the ligand content from the total mass of the ligand solution.
  • the method of applying the ligand solution to the aggregate of semiconductor quantum dots is the same as the method of applying the semiconductor quantum dot dispersion liquid on the substrate, and the preferred embodiment is also the same.
  • the method for producing a semiconductor film of the present invention may include a rinsing step in which a rinsing solution is brought into contact with a film of a semiconductor quantum dot aggregate to rinse the film.
  • a rinsing step By having the rinsing step, it is possible to remove the excess ligand contained in the film and the ligand desorbed from the semiconductor quantum dots. In addition, the remaining solvent and other impurities can be removed.
  • a solvent contained in the semiconductor quantum dot dispersion liquid or a ligand solution can be used, but an excess ligand contained in the film or a ligand desorbed from the semiconductor quantum dots is used.
  • the boiling point of the rinsing solution is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and even more preferably 90 ° C. or lower, because it can be easily removed after film formation.
  • the boiling point of the rinsing solution is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and even more preferably 50 ° C. or higher, because unnecessary concentration during the operation can be avoided. From the above, the boiling point of the rinse solution is preferably 50 to 90 ° C.
  • aprotic solvent examples include acetonitrile, acetone, dimethylformamide, and dimethyl sulfoxide, and acetonitrile and acetone are preferable because they have a low boiling point and do not easily remain in the membrane.
  • the rinsing solution may be poured onto the film of the semiconductor quantum dot aggregate, or the film of the semiconductor quantum dot aggregate may be immersed in the rinse solution. Further, the rinsing step may be performed after the semiconductor quantum dot aggregate forming step or after the ligand exchange step. Further, it may be performed after repeating the set of the semiconductor quantum dot aggregate forming step and the ligand exchange step.
  • the amount of metal impurities in the solvent used in the semiconductor quantum dot aggregate forming step, the ligand exchange step, and the rinsing step is small, and the metal content is, for example, 10 mass ppb (parts per parts) or less.
  • a solvent at the mass ppt (parts per parts) level may be used, and such a solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures), and the isomer may contain only one kind or a plurality of kinds of isomers.
  • the method for producing a semiconductor film of the present invention may include a drying step.
  • the drying step may be a dispersion solution drying step of drying and removing the solvent remaining on the film of the semiconductor quantum dot aggregate after the semiconductor quantum dot aggregate forming step, or after the ligand exchange step.
  • the solution drying step of drying the ligand solution may be performed. Further, it may be a comprehensive step performed after repeating the set of the semiconductor quantum dot aggregate forming step and the ligand exchange step.
  • a semiconductor film is formed on the substrate by going through each of the steps described above.
  • the obtained semiconductor film has high electrical conductivity, photocurrent value and external quantum efficiency, and is also excellent in in-plane uniformity of external quantum efficiency.
  • the photoelectric conversion element of the present invention includes the above-mentioned semiconductor film of the present invention. More preferably, the semiconductor film of the present invention is included as the photoelectric conversion layer.
  • the thickness of the semiconductor film of the present invention in the photoelectric conversion element is preferably 10 nm to 600 nm, more preferably 50 nm to 600 nm, further preferably 100 nm to 600 nm, and further preferably 150 nm to 600 nm. preferable.
  • the upper limit of the thickness is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 450 nm or less.
  • Examples of the type of photoelectric conversion element include a photodetection element such as a sensor and a photovoltaic element such as a solar cell.
  • the semiconductor film of the present invention is excellent in in-plane uniformity of external quantum efficiency, it is particularly effective when used as a photodetector. That is, in a photodetection device, if there is a large variation in the external quantum efficiency in the plane, it may cause noise, and in the case of an image sensor, for example, it may cause deterioration of the quality of the acquired image, and the function as a sensor is functioning. Easy to drop. For this reason, photodetectors are particularly required to have high in-plane uniformity of external quantum efficiency.
  • Examples of the type of photodetector include a photoconductor type photodetector and a photodiode type photodetector. Of these, a photodiode-type photodetector is preferable because a high signal-to-noise ratio (SN ratio) can be easily obtained.
  • SN ratio signal-to-noise ratio
  • the photoelectric conversion element of the present invention can be used as an optical detection element for detecting light having a wavelength in the infrared region. It is preferably used. That is, the photoelectric conversion element of the present invention is preferably used as an infrared light detection element.
  • the light having a wavelength in the infrared region is preferably light having a wavelength exceeding 700 nm, more preferably light having a wavelength of 800 nm or more, and further preferably light having a wavelength of 900 nm or more. Further, the light having a wavelength in the infrared region is preferably light having a wavelength of 2000 nm or less, and more preferably light having a wavelength of 1600 nm or less.
  • the photoelectric conversion element may be a photodetector that simultaneously detects light having a wavelength in the infrared region and light having a wavelength in the visible region (preferably light having a wavelength in the range of 400 to 700 nm).
  • FIG. 1 shows an embodiment of a photodiode-type photodetector.
  • the arrows in the figure represent the incident light on the photodetector.
  • the photodetection element 1 shown in FIG. 1 includes a lower electrode 12, an upper electrode 11 facing the lower electrode 12, and a photoelectric conversion layer 13 provided between the lower electrode 12 and the upper electrode 11.
  • the photodetection element 1 shown in FIG. 1 is used by injecting light from above the upper electrode 11.
  • the photoelectric conversion layer 13 is composed of the above-mentioned semiconductor film of the present invention.
  • the refractive index of the photoelectric conversion layer 13 with respect to light of the target wavelength detected by the photodetector is preferably 2.0 to 3.0, more preferably 2.1 to 2.8, and 2.2. It is more preferably about 2.7. According to this aspect, when the photodetector is configured as a photodiode, it becomes easy to realize a high light absorption rate, that is, a high external quantum efficiency.
  • the thickness of the photoelectric conversion layer 13 is preferably 10 nm to 600 nm, more preferably 50 nm to 600 nm, further preferably 100 nm to 600 nm, and even more preferably 150 nm to 600 nm.
  • the upper limit of the thickness is preferably 550 nm or less, more preferably 500 nm or less, and even more preferably 450 nm or less.
  • the wavelength ⁇ and the optical path length L ⁇ satisfy such a relationship, the light (incident light) incident from the upper electrode 11 side is reflected by the surface of the lower electrode 12 in the photoelectric conversion layer 13. It is possible to align the phase with the light (reflected light), and as a result, the light is strengthened by the optical interference effect, and higher external quantum efficiency can be obtained.
  • ⁇ is the wavelength of the target light to be detected by the photodetector.
  • L ⁇ is the optical path length of light having a wavelength ⁇ from the surface 12a on the photoelectric conversion layer 13 side of the lower electrode 12 to the surface 13a on the upper electrode side of the photoelectric conversion layer 13.
  • m is an integer greater than or equal to 0.
  • M is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and particularly preferably 0 or 1.
  • the optical path length means the product of the physical thickness of the substance through which light is transmitted and the refractive index.
  • the photoelectric conversion layer 13 when the thickness of the photoelectric conversion layer is d 1 and the refractive index of the photoelectric conversion layer with respect to the wavelength ⁇ 1 is N 1 , the wavelength ⁇ 1 transmitted through the photoelectric conversion layer 13 The optical path length of light is N 1 ⁇ d 1 .
  • the photoelectric conversion layer 13 is composed of two or more laminated films, or when an intermediate layer described later is present between the photoelectric conversion layer 13 and the lower electrode 12, the integrated value of the optical path length of each layer is calculated.
  • the optical path length L ⁇ when the photoelectric conversion layer 13 is composed of two or more laminated films, or when an intermediate layer described later is present between the photoelectric conversion layer 13 and the lower electrode 12, the integrated value of the optical path length of each layer is calculated.
  • the optical path length L ⁇ when the photoelectric conversion layer 13 is composed of two or more laminated films, or when an intermediate layer described later is present between the photoelectric
  • the upper electrode 11 is preferably a transparent electrode formed of a conductive material that is substantially transparent to the wavelength of the target light detected by the photodetector.
  • substantially transparent means that the light transmittance is 50% or more, preferably 60% or more, and particularly preferably 80% or more.
  • the material of the upper electrode 11 include a conductive metal oxide. Specific examples include tin oxide, zinc oxide, indium oxide, indium tungsten oxide, indium zinc oxide (IZO), indium tin oxide (ITO), and fluorine-doped tin oxide (fluorine-topped). Tin oxide: FTO) and the like.
  • the film thickness of the upper electrode 11 is not particularly limited, and is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, and particularly preferably 0.01 ⁇ m to 1 ⁇ m.
  • the thickness of each layer can be measured by observing the cross section of the light detection element 1 using a scanning electron microscope (SEM) or the like.
  • Examples of the material forming the lower electrode 12 include metals such as platinum, gold, nickel, copper, silver, indium, ruthenium, palladium, rhodium, iridium, osnium, and aluminum, the above-mentioned conductive metal oxides, carbon materials, and the like. Examples include conductive polymers.
  • the carbon material may be any material having conductivity, and examples thereof include fullerenes, carbon nanotubes, graphite, graphene and the like.
  • the lower electrode 12 a thin film of metal or a conductive metal oxide (including a thin film formed by vapor deposition), or a glass substrate or a plastic substrate having this thin film is preferable.
  • a glass substrate or the plastic substrate glass having a thin film of gold or platinum or glass on which platinum is vapor-deposited is preferable.
  • the film thickness of the lower electrode 12 is not particularly limited, and is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.01 ⁇ m to 10 ⁇ m, and particularly preferably 0.01 ⁇ m to 1 ⁇ m.
  • a transparent substrate may be arranged on the surface of the upper electrode 11 on the light incident side (the surface opposite to the photoelectric conversion layer 13 side).
  • Examples of the type of transparent substrate include a glass substrate, a resin substrate, and a ceramic substrate.
  • an intermediate layer may be provided between the photoelectric conversion layer 13 and the lower electrode 12 and / or between the photoelectric conversion layer 13 and the upper electrode 11.
  • the intermediate layer include a blocking layer, an electron transport layer, and a hole transport layer.
  • a preferred embodiment includes a mode in which the hole transport layer is provided between the photoelectric conversion layer 13 and the lower electrode 12 and between the photoelectric conversion layer 13 and the upper electrode 11. It is possible that one of the photoelectric conversion layer 13 and the lower electrode 12 and one of the photoelectric conversion layer 13 and the upper electrode 11 has an electron transport layer and the other has a hole transport layer. preferable.
  • the hole transport layer and the electron transport layer may be a single-layer film or a laminated film having two or more layers.
  • the blocking layer is a layer having a function of preventing reverse current.
  • the blocking layer is also called a short circuit prevention layer.
  • Examples of the material forming the blocking layer include silicon oxide, magnesium oxide, aluminum oxide, calcium carbonate, cesium carbonate, polyvinyl alcohol, polyurethane, titanium oxide, tin oxide, zinc oxide, niobium oxide, tungsten oxide and the like.
  • the blocking layer may be a single-layer film or a laminated film having two or more layers.
  • the electron transport layer is a layer having a function of transporting electrons generated in the photoelectric conversion layer 13 to the upper electrode 11 or the lower electrode 12.
  • the electron transport layer is also called a hole block layer.
  • the electron transport layer is formed of an electron transport material capable of exerting this function. Examples of the electron transporting material include fullerene compounds such as [6,6] -Phenyl-C61-Butyric Acid Metyl Ester (PC 61 BM), perylene compounds such as perylene tetracarboxydiimide, tetracyanoquinodimethane, titanium oxide, and tin oxide.
  • the electron transport layer may be a single-layer film or a laminated film having two or more layers.
  • the hole transport layer is a layer having a function of transporting holes generated in the photoelectric conversion layer 13 to the upper electrode 11 or the lower electrode 12.
  • the hole transport layer is also called an electron block layer.
  • the hole transport layer is formed of a hole transport material capable of exerting this function.
  • the organic hole transport material or the like described in paragraph Nos. 0209 to 0212 of JP-A-2001-291534 can also be used.
  • semiconductor quantum dots can also be used as the hole transport material.
  • Examples of the semiconductor quantum dot material constituting the semiconductor quantum dot include general semiconductor crystals [a) group IV semiconductors, b) group IV-IV, group III-V, or group II-VI compound semiconductors, c) II.
  • Examples thereof include semiconductor materials having a relatively narrow bandgap.
  • a ligand may be coordinated on the surface of the semiconductor quantum dot.
  • the photoelectric conversion device of the present invention includes the above-mentioned photoelectric conversion element of the present invention. Since the photoelectric conversion element of the present invention has excellent sensitivity to light having a wavelength in the infrared region, it can be particularly preferably used as an infrared image sensor.
  • the configuration of the image sensor is not particularly limited as long as it includes the photoelectric conversion element of the present invention and functions as an image sensor.
  • the image sensor may include an infrared transmission filter layer.
  • the infrared transmission filter layer preferably has low light transmittance in the visible wavelength band, and more preferably has an average transmittance of light in the wavelength range of 400 nm to 650 nm of 10% or less. It is more preferably 5.5% or less, and particularly preferably 5% or less.
  • Examples of the infrared transmission filter layer include those composed of a resin film containing a coloring material.
  • Examples of the coloring material include chromatic color materials such as red color material, green color material, blue color material, yellow color material, purple color material, and orange color material, and black color material.
  • the color material contained in the infrared transmission filter layer is preferably a combination of two or more kinds of chromatic color materials to form black, or preferably contains a black color material.
  • Examples of the combination of chromatic color materials in the case of forming black by combining two or more kinds of chromatic color materials include the following aspects (C1) to (C7).
  • (C1) An embodiment containing a red color material and a blue color material.
  • C2 An embodiment containing a red color material, a blue color material, and a yellow color material.
  • C3 An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material.
  • C4 An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material.
  • C5 An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material.
  • C6 An embodiment containing a red color material, a blue color material, and a green color material.
  • C7 An embodiment containing a yellow color material and a purple color material.
  • the chromatic color material may be a pigment or a dye. Pigments and dyes may be included.
  • the black color material is preferably an organic black color material.
  • examples of the organic black color material include a bisbenzofuranone compound, an azomethine compound, a perylene compound, and an azo compound.
  • the infrared transmission filter layer may further contain an infrared absorber.
  • infrared absorbers include pyrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonor compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, and azomethine compounds.
  • examples thereof include compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal boroides.
  • the spectral characteristics of the infrared transmission filter layer can be appropriately selected according to the application of the image sensor.
  • a filter layer satisfying any of the following spectral characteristics (1) to (5) can be mentioned.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • a filter layer in which the minimum value of the transmittance in the wavelength range of 1000 nm to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 1100 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength range is 1400 nm to 1500 nm.
  • the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 nm to 1300 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength range is 1600 nm to 2000 nm.
  • infrared transmission filters Japanese Patent Application Laid-Open No. 2013-077009, Japanese Patent Application Laid-Open No. 2014-130173, Japanese Patent Application Laid-Open No. 2014-130338, International Publication No. 2015/166779, International Publication No. 2016/178346, International Publication No.
  • infrared transmission filter two or more filters may be used in combination, or a dual bandpass filter that transmits two or more specific wavelength regions with one filter may be used.
  • the image sensor of the present invention may include an infrared shielding filter for the purpose of improving various performances such as noise reduction.
  • the infrared shielding filter include, for example, International Publication No. 2016/186050, International Publication No. 2016/035695, Japanese Patent No. 6248945, International Publication No. 2019/021767, Japanese Patent Application Laid-Open No. 2017-06793, Patent. Examples thereof include the filters described in Japanese Patent Application Laid-Open No. 6506529.
  • the image sensor of the present invention may include a dielectric multilayer film.
  • the dielectric multilayer film include those in which a plurality of layers of a dielectric thin film having a high refractive index (high refractive index material layer) and a dielectric thin film having a low refractive index (low refractive index material layer) are alternately laminated.
  • the number of laminated dielectric thin films in the dielectric multilayer film is not particularly limited, but is preferably 2 to 100 layers, more preferably 4 to 60 layers, and even more preferably 6 to 40 layers.
  • As the material used for forming the high refractive index material layer a material having a refractive index of 1.7 to 2.5 is preferable.
  • Specific examples include Sb 2 O 3 , Sb 2 S 3 , Bi 2 O 3 , CeO 2 , CeF 3 , HfO 2 , La 2 O 3 , Nd 2 O 3 , Pr 6 O 11 , Sc 2 O 3 , SiO. , Ta 2 O 5 , TiO 2 , TlCl, Y 2 O 3 , ZnSe, ZnS, ZrO 2, and the like.
  • a material having a refractive index of 1.2 to 1.6 is preferable.
  • the method for forming the dielectric multilayer film is not particularly limited, and for example, an ion plating method, a vacuum deposition method such as an ion beam, a physical vapor deposition method (PVD method) such as sputtering, or a chemical vapor deposition method. (CVD method) and the like.
  • each of the high refractive index material layer and the low refractive index material layer is preferably 0.1 ⁇ to 0.5 ⁇ when the wavelength of the light to be blocked is ⁇ (nm).
  • the dielectric multilayer film for example, the films described in JP-A-2014-130344 and JP-A-2018-010296 can be used.
  • the dielectric multilayer film preferably has a transmission wavelength band in the infrared region (preferably a wavelength region having a wavelength of more than 700 nm, more preferably a wavelength region having a wavelength of more than 800 nm, and further preferably a wavelength region having a wavelength of more than 900 nm).
  • the maximum transmittance in the transmission wavelength band is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the maximum transmittance in the light-shielding wavelength band is preferably 20% or less, more preferably 10% or less, and further preferably 5% or less.
  • the average transmittance in the transmission wavelength band is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • the wavelength range of the transmission wavelength band, when the center wavelength lambda t1 wavelengths showing a maximum transmittance is preferably the central wavelength lambda t1 ⁇ 100 nm, more preferably the central wavelength lambda t1 ⁇ 75 nm, It is more preferable that the center wavelength is ⁇ t1 ⁇ 50 nm.
  • the dielectric multilayer film may have only one transmission wavelength band (preferably, a transmission wavelength band having a maximum transmittance of 90% or more), or may have a plurality of transmission wavelength bands.
  • the image sensor of the present invention may include a color separation filter layer.
  • the color separation filter layer include a filter layer including colored pixels.
  • Examples of the types of colored pixels include red pixels, green pixels, blue pixels, yellow pixels, cyan pixels, magenta pixels, and the like.
  • the color separation filter layer may include two or more colored pixels, or may have only one color. It can be appropriately selected according to the application and purpose. For example, the filter described in International Publication No. 2019/039172 can be used.
  • the colored pixels of each color may be adjacent to each other, and a partition wall may be provided between the colored pixels.
  • the material of the partition wall is not particularly limited. Examples thereof include organic materials such as siloxane resin and fluororesin, and inorganic particles such as silica particles.
  • the partition wall may be made of a metal such as tungsten or aluminum.
  • the image sensor of the present invention includes an infrared transmission filter layer and a color separation layer
  • the color separation layer is provided on an optical path different from the infrared transmission filter layer. It is also preferable that the infrared transmission filter layer and the color separation layer are arranged two-dimensionally. The fact that the infrared transmission filter layer and the color separation layer are arranged two-dimensionally means that at least a part of both is present on the same plane.
  • the image sensor of the present invention may include an intermediate layer such as a flattening layer, a base layer, and an adhesion layer, an antireflection film, and a lens.
  • an antireflection film for example, a film prepared from the composition described in International Publication No. 2019/017280 can be used.
  • the lens for example, the structure described in International Publication No. 2018/092600 can be used.
  • the image sensor of the present invention can be preferably used as an infrared image sensor. Further, the image sensor of the present invention can be preferably used as a sensor for sensing light having a wavelength of 900 nm to 2000 nm, and more preferably as a sensor for sensing light having a wavelength of 900 nm to 1600 nm.
  • Comparative Example 1 22.5 mL of oleic acid, 2 mmol of lead oxide and 19 mL of octadecene were measured in a flask and heated at 110 ° C. under vacuum for 90 minutes to obtain a precursor solution. Then, the temperature of the solution was adjusted to 95 ° C., and the system was put into a nitrogen flow state. Then 1 mmol of hexamethyldisiratene was injected with 5 mL of octadecene. Immediately after the injection, the flask was naturally cooled, and when the temperature reached 30 ° C., 12 mL of hexane was added and the solution was recovered.
  • test piece 1 As a substrate, a substrate having 65 pairs of comb-shaped platinum electrodes shown in FIG. 2 was prepared on quartz glass. As the comb-shaped platinum electrode, a comb-shaped electrode manufactured by BAS (model number 012126, electrode spacing 5 ⁇ m) was used.
  • a dispersion of PbS quantum dots was dropped onto the substrate and spin-coated at 2500 rpm to form a PbS quantum dot aggregate film (step 1).
  • a first ligand solution which is a methanol solution (concentration 25 mmol / L) of the specific ligand 1 shown in the table below and a specific coordination described in the table below.
  • the second ligand solution which is the methanol solution (concentration 0.01 v / v%) of the child 2
  • the mixture was allowed to stand for 10 seconds and spin-dried at 2500 rpm for 10 seconds.
  • methanol is dropped onto the PbS quantum dot aggregate film as a rinsing solution, and spin-drying is performed at 2500 rpm for 20 seconds to change the ligand coordinated to the PbS quantum dot from oleic acid to a specific ligand.
  • the ligand was exchanged for 1 and the specific ligand 2 (step 2).
  • a semiconductor film was formed to a thickness of 180 nm to prepare a test piece 1. The thickness of the PbS quantum dot aggregate film formed per cycle was about 18 nm.
  • test piece 2 A titanium oxide film was formed on a 1-inch (25.4 mm) fluorine-doped tin oxide film-coated quartz glass substrate by 50 nm sputtering. Next, the dispersion liquid of PbS quantum dots was dropped onto the titanium oxide film formed on the substrate and spin-coated at 2500 rpm to form a PbS quantum dot aggregate film (step 1). Next, on the PbS quantum dot aggregate film, a first ligand solution which is a methanol solution (concentration 25 mmol / L) of the specific ligand 1 shown in the table below and a specific coordination described in the table below.
  • a first ligand solution which is a methanol solution (concentration 25 mmol / L) of the specific ligand 1 shown in the table below and a specific coordination described in the table below.
  • a second ligand solution which is a methanol solution of child 2 (concentration: 0.01 v / v%), was added dropwise, and then the mixture was allowed to stand for 10 seconds and spin-dried at 2500 rpm for 10 seconds.
  • methanol was dropped onto the PbS quantum dot aggregate membrane as a rinsing solution, and spin-drying was performed at 2500 rpm for 20 seconds to change the ligand coordinated to the PbS quantum dot from oleic acid to a specific ligand.
  • the ligand was exchanged for 1 and the specific ligand 2 (step 2).
  • the photoelectric conversion layer was formed with a thickness of 180 nm.
  • the thickness of the PbS quantum dot aggregate film formed per cycle was about 18 nm.
  • molybdenum oxide is continuously vapor-deposited at 50 nm and gold at 100 nm via a metal mask in which three patterns of openings having an area of 0.16 cm 2 are formed on the photoelectric conversion layer to form three element portions.
  • a test piece 2 which was formed and was a photodiode type photodetector was produced.
  • the electric conductivity and the photocurrent value of the semiconductor film were measured using a semiconductor parameter analyzer (C4156, manufactured by Agilent). That is, with regard to the electric conductivity, the electric conductivity of the semiconductor film was measured by applying + 5 V to the electrode without irradiating the test body 1 with light and acquiring a current value.
  • the photocurrent value was evaluated by measuring the photocurrent value in a state where the test piece 1 was irradiated with monochrome light having a wavelength of 1550 nm (irradiation intensity 40 ⁇ W / cm 2 ).
  • a monochrome light source system MLS-1510 manufactured by Asahi Spectroscopy Co., Ltd. was used for light irradiation.
  • the external quantum efficiency and its in-plane uniformity were evaluated using the prepared test piece 2. That is, the external quantum efficiency (EQE) when the test body 2 was irradiated with monochrome light (irradiation intensity 40 ⁇ W / cm 2 ) having a wavelength of 1550 nm while a reverse voltage of 2 V was applied was measured. For the external quantum efficiency (EQE), the number of electrons generated by light irradiation was calculated by subtracting the current value in the non-irradiated state from the current value in the irradiated state.
  • the value of external quantum efficiency (EQE) was obtained by dividing the number of electrons generated by light irradiation by the number of photons of the irradiated light.
  • the value of the external quantum efficiency (EQE) in the table was taken as the average value of the three element parts of the test body 2.
  • the value of the thing-the value of the thing with the lowest external quantum efficiency) was calculated, and the in-plane uniformity (in-plane uniformity of the external quantum efficiency) was evaluated. The smaller the value of ⁇ EQE, the better the in-plane uniformity.
  • the ligand described in the column of specific ligand 1 in the above table corresponds to the first ligand in the present invention.
  • thioglycolic acid, 2-aminoethanol, 2-aminoethanethiol, 2-mercaptoethanol, diethylenetriamine, tris (2-aminoethyl) Amines and (aminomethyl) phosphonic acids correspond to the second ligand in the present invention.
  • Example 14 as the first ligand solution, a methanol solution in which ZnI 2 was mixed at a concentration of 12.5 mmol / L and CdCl 2 was mixed at a concentration of 12.5 mmol / L was used. Further, in Example 15, as the second ligand solution, a methanol solution in which thioglycolic acid was mixed at a concentration of 0.005 v / v% and 2-aminoethanol was mixed at a concentration of 0.005 v / v% was used.
  • Example 16 a second ligand solution in which thioglycolic acid was mixed at a concentration of 0.008 v / v% and 3-mercaptopropionic acid was mixed at a concentration of 0.002 v / v% was used. Further, in Comparative Example 2, the ligand exchange was performed using only the first ligand solution. Further, in Comparative Example 3, the ligand exchange was performed using only the second ligand solution.
  • Comparative Example 1 was an example in which 3-mercaptopropionic acid was used instead of the second ligand, but the in-plane uniformity was inferior.
  • Comparative Example 2 contains only the first ligand in the present invention as the ligand, but it is presumed that the proximity of the distance between the semiconductor quantum dots is insufficient, and the photocurrent value and the external quantum are not sufficient. The efficiency was low.
  • Comparative Example 3 contained only the first ligand in the present invention as the ligand, but the external quantum efficiency was low. It is presumed that this is because there are many surface defects of the semiconductor dots.
  • Example 17 In the preparation of the test body 1 and the test body 2, the test body 1 and the test body 2 were prepared in the same manner as in Example 3 except that the type of the rinsing solution used in the step 2 was changed from methanol to acetonitrile.
  • the electric conductivity was 1.4 ⁇ 10-2.
  • the photocurrent value was 4.8 ⁇ 10-5 A
  • the external quantum efficiency (EQE) was 49.5%
  • the in-plane uniformity ( ⁇ EQE) was 1.4%. All of the electric conductivity, the photocurrent value, the external quantum efficiency, and the in-plane uniformity thereof were improved as compared with Example 3.
  • Examples 18 and 19 A dispersion of PbS quantum dots having a concentration of 80 mg / mL was used, and a methanol solution (concentration of 25 mmol / L) of the specific ligand 1 (ZnI 2 ) shown in the table below was used as the first ligand solution.
  • a semiconductor film which is an exchanged PbS quantum dot aggregate film, was formed to a thickness of about 180 nm to prepare a test body 1 and a test body 2.
  • the thickness of the PbS quantum dot aggregate film formed per cycle was about 37 nm.
  • the complex stability constant K1 of thioglycolic acid with respect to the Pb atom was 8.5, and the complex stability constant K1 of 2-mercaptoethanol with respect to the Pb atom was 6.7.
  • the values of these complex stability constants K1 are described in Sc-Database ver. Obtained using 5.85 (Academic Software) (2010).
  • Example 19 using thioglycolic acid (complex stability constant K1 for Pb is 8.5), 2-mercaptoethanol (complex stability constant K1 for Pb is 6.7). ) was superior to that of Example 18 in terms of electrical conductivity, photocurrent value, external quantum efficiency, and in-plane uniformity.
  • Example 20> In step 2, the same as in Example 1 except that a methanol solution containing 0.01 v / v% of thioglycolic acid and 25 mmol / L of ZnI 2 was added dropwise as a ligand solution onto the PbS quantum dot aggregate film. Test bodies 1 and 2 were prepared. When the electric conductivity, the photocurrent value, the external quantum efficiency and the in-plane uniformity were evaluated using the obtained test bodies 1 and 2, the performance was the same as that of Example 1.
  • an image sensor was prepared by a known method together with an optical filter prepared according to the methods described in International Publication No. 2016/186050 and International Publication No. 2016/190162, and solidified. By incorporating it into an image sensor, an image sensor having good visible and infrared imaging performance can be obtained.
  • the same effect can be obtained by changing the semiconductor quantum dots of the photoelectric conversion layer to PbSe quantum dots.

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