# US 12,120,894 B2 · Semiconductor film and method of producing the same, photoelectric conversion element, solid-state imaging element and electronic apparatus

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- Number: US 12,120,894 B2
- Document ID: US12120894B2
- Status: Granted
- Kind: B2
- Application number: 18/355,218
- Filed: 2023-07-19
- Published: 2023-11-09
- Granted: 2024-10-15
- Earliest claimed: 2016-07-20
- Assignees: Sony Group Corporation
- Applicants: Sony Group Corporation
- Inventors: Syuuiti Takizawa; Michinori Shiomi
- Web page: https://patentgrep.com/patent/US12120894B2

## CPC

- H10F 39/199: {Back-illuminated image sensors}
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- B82Y 15/00: Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
- B82Y 40/00: Manufacture or treatment of nanostructures
- H10F 39/182: {Colour image sensors}
- H10F 39/1825: {Multicolour image sensors having stacked structure, e.g. NPN, NPNPN or multiple quantum well [MQW] structures}
- H10K 19/20: comprising components having an active region that includes an inorganic semiconductor
- H10K 30/35: comprising inorganic nanostructures, e.g. CdSe nanoparticles
- H10K 39/32: Organic image sensors
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

To provide a semiconductor film capable of realizing further enhancement of photoelectric conversion efficiency. The semiconductor film includes semiconductor nanoparticles and a compound represented by the following general formula (1), in which the compound represented by the general formula (1) is coordinated to the semiconductor nanoparticles. (In the general formula (1), X represents —SH, —COOH, —NH2, —PO(OH)2, or —SO2(OH), A1 represents —S, —COO, —PO(OH)O, or —SO2(O), and n is an integer of 1 to 3. B1 represents Li, Na, or K.)

## Claims

### Claim 1

A semiconductor film obtained by coating a substrate with a dispersion containing semiconductor nanoparticles and a compound represented by general formula (2):
(in the general formula (2), X represents —SH, —COOH, —NH2, —PO(OH)2, or —SO2(OH), A1 represents —S, —COO, —PO(OH)O, or —SO2(O), and n represents an integer of 1 to 3, B2 represents an imidazolium compound, a pyridinium compound, a phosphonium compound, an ammonium compound, or a sulfonium compound),
wherein the compound represented by the general formula (2) is coordinated to the semiconductor nanoparticles.

### Claim 2 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles selectively absorb at least light in a visible region.

### Claim 3 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles selectively absorb at least light in an infrared region.

### Claim 4 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles include at least one of TiO2, ZnO, WOs, NIO, MoO3, CuO, Ga2O3, SrTiO3, SnO2, InSnOx, Nb2O3, MnO2, V2O3, CrO, CuInSe2, CuInS2, AgInS2, Si, PbS, PbSe, PbTe, CdS, CdSe, CdTe, Fe2O3, GaAs, GaP, InP, InAs, Ge, In2S3, Bi2S3, ZnSe, ZnTe, or ZnS.

### Claim 5 (depends on 1)

The semiconductor film according to claim 1, wherein a particle diameter of the semiconductor nanoparticle is 2 to 20 nm.

### Claim 6 (depends on 1)

The semiconductor film according to claim 1, wherein a shape of the semiconductor nanoparticle is a sphere, an ellipsoid, or a triangular prism.

### Claim 7 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles for red light include PbSe, CdTe, PbS, Si, PbTe, CdSe, CuInSe2, CuInS2, AgInS2, MnO2, V2O3, CrO, GaAs, Fe2O3, InP, InAs, Ge, Bi2S3 or CuO.

### Claim 8 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles for green light include CdS, GaP or ZnTe.

### Claim 9 (depends on 1)

The semiconductor film according to claim 1, wherein the semiconductor nanoparticles for blue light include WO3, ZnSe or In2S3.

### Claim 10

A photoelectric conversion element, comprising:
a semiconductor film obtained by coating a substrate with a dispersion containing semiconductor nanoparticles and a compound represented by general formula (2):
(in the general formula (2), X represents —SH, —COOH, —NH2, —PO(OH)2, or —SO2(OH), A1 represents —S, —COO, —PO(OH)O, or —SO2(O), and n represents an integer of 1 to 3, B2 represents an imidazolium compound, a pyridinium compound, a phosphonium compound, an ammonium compound, or a sulfonium compound),
wherein the compound represented by the general formula (2) is coordinated to the semiconductor nanoparticles;
a first electrode; and
a second electrode which are disposed to face each other,
wherein the semiconductor film is disposed between the first electrode and the second electrode.

### Claim 11 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the first electrode includes a light-transmitting conductive material such as ITO and the second electrode includes a conductive material such as Au, Ag, Cu or Al.

### Claim 12 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles selectively absorb at least light in a visible region.

### Claim 13 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles selectively absorb at least light in an infrared region.

### Claim 14 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles include at least one of TiO2, ZnO, WO3, NiO, MoO3, CuO, Ga2O3, SrTiO3, SnO2, InSnOx, Nb2O3, MnO2, V2O3, CrO, CuInSe2, CuInS2, AgInS2, Si, PbS, PbSe, PbTe, CdS, CdSe, CdTe, Fe2O3, GaAs, GaP, InP, InAs, Ge, In2S3, Bi2S3, ZnSe, ZnTe, or ZnS.

### Claim 15 (depends on 10)

The photoelectric conversion element according to claim 10, wherein a particle diameter of the semiconductor nanoparticle is 2 to 20 nm.

### Claim 16 (depends on 10)

The photoelectric conversion element according to claim 10, wherein a shape of the semiconductor nanoparticle is a sphere, an ellipsoid, or a triangular prism.

### Claim 17 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles for red light include PbSe, CdTe, PbS, Si, PbTe, CdSe, CuInSe2, CuInS2, AgInS2, MnO2, V2O3, CrO, GaAs, Fe2O3, InP, InAs, Ge, Bi2S3 or CuO.

### Claim 18 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles for green light include CdS, GaP or ZnTe.

### Claim 19 (depends on 10)

The photoelectric conversion element according to claim 10, wherein the semiconductor nanoparticles for blue light include WO3, ZnSe or In2S3.

### Claim 20

A method of producing a semiconductor film, the method comprising:
coating a substrate with a dispersion containing semiconductor nanoparticles and a compound represented by the following general formula (2):
(in the general formula (2), X represents —SH, —COOH, —NH2, —PO(OH)2, or —SO2(OH), A1 represents —S, —COO, —PO(OH)O, or —SO2(O), and n represents an integer of 1 to 3, B2 represents an imidazolium compound, a pyridinium compound, a phosphonium compound, an ammonium compound, or a sulfonium compound),
wherein the compound represented by the general formula (2) is coordinated to the semiconductor nanoparticles.