Imaging element, method of manufacturing imaging element, and imaging device

• US 10,672,837 B2
• Filed: 05/16/2017
• Issued: 06/02/2020
• Est. Priority Date: 06/02/2016
• Status: Active Grant

• Current Assignee: Sony Corporation (Sony Group Corp.)
• Original Assignee: Sony Corporation (Sony Group Corp.)
• Inventors: Kobayashi, Hajime, Tokita, Yuichi
• Primary Examiner(s): Shook, Daniel P
• Application Number:
  US16/302,743
• Publication Number:
  US 20190296086A1
• Time in Patent Office: 1,113 Days
• CPC Class Codes: H01L 21/3205 Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers manufacture of electrodes H01L21/28
• CPC Class Codes: H01L 21/768 Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
• CPC Class Codes: H01L 23/522 including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
• CPC Class Codes: H01L 27/146 Imager structures
• CPC Class Codes: H01L 27/14612 involving a transistor
• CPC Class Codes: H01L 27/14638 Structures specially adapted for transferring the charges across the imager perpendicular to the imaging plane
• CPC Class Codes: H01L 27/1464 Back illuminated imager structures
• CPC Class Codes: H01L 27/14645 Colour imagers
• CPC Class Codes: H01L 27/14667 Colour imagers
• CPC Class Codes: H01L 31/10 characterised by potential barriers, e.g. phototransistors
• CPC Class Codes: H04N 25/79 Arrangements of circuitry being divided between different or multiple substrates, chips or circuit boards, e.g. stacked image sensors
• CPC Class Codes: H10K 19/20 comprising components having an active region that includes an inorganic semiconductor
• CPC Class Codes: H10K 30/30 comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• CPC Class Codes: H10K 39/32 Organic image sensors
• CPC Class Codes: H10K 71/40 Thermal treatment, e.g. annealing in the presence of a solvent vapour
• CPC Class Codes: H10K 85/211 Fullerenes, e.g. C60
• CPC Class Codes: H10K 85/215 comprising substituents, e.g. PCBM
• CPC Class Codes: H10K 85/311 Phthalocyanine
• CPC Class Codes: H10K 85/623 containing five rings, e.g. pentacene
• CPC Class Codes: H10K 85/6572 comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
• CPC Class Codes: H10K 85/6576 : comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
• CPC Class Codes: Y02E 10/549 : Organic PV cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

An imaging element according to an embodiment of the present disclosure includes: a first electrode and a second electrode facing each other; and a photoelectric conversion layer including a p-type semiconductor and an n-type semiconductor, and provided between the first electrode and the second electrode, in which the photoelectric conversion layer has an exciton charge separation rate of 1×10¹⁰ s⁻¹ to 1×10¹⁶ s⁻¹ both inclusive in a p-n junction surface formed by the p-type semiconductor and the n-type semiconductor.

Claims

1. An imaging element, comprising:

a first electrode;

a second electrode that faces the first electrode; and

a photoelectric conversion layer between the first electrode and the second electrode, wherein

the photoelectric conversion layer comprises a p-type semiconductor, an n-type semiconductor, and a p-n junction surface between the p-type semiconductor and the n-type semiconductor,

the p-type semiconductor and the n-type semiconductor have controlled molecular orientations, and

the p-n junction surface includes a specific combination of a first crystal plane of the p-type semiconductor and a second crystal plane of the n-type semiconductor based on the controlled molecular orientations, such that the photoelectric conversion layer has an exciton charge separation rate of 1×

10¹⁰ s<sup>−

1</sup> to 1×

10¹⁶ s<sup>−

1</sup>, both inclusive in the p-n junction surface.

2. The imaging element according to claim 1, wherein one of the p-type semiconductor or the n-type semiconductor is one of quinacridone or a quinacridone derivative.

3. The imaging element according to claim 1, wherein one of the p-type semiconductor or the n-type semiconductor is one of chlorinated boron subphthalocyanine or a chlorinated boron subphthalocyanine derivative.

4. The imaging element according to claim 1, wherein one of the p-type semiconductor or the n-type semiconductor is one of pentacene or a pentacene derivative.

5. The imaging element according to claim 1, wherein one of the p-type semiconductor or the n-type semiconductor is one of benzothienobenzothiophene or a benzothienobenzothiophene derivative.

6. The imaging element according to claim 1, wherein one of the p-type semiconductor or the n-type semiconductor is one of fullerene or a fullerene derivative.

7. The imaging element according to claim 1, wherein the photoelectric conversion layer includes at least two of quinacridone, a quinacridone derivative, chlorinated boron subphthalocyanine, a chlorinated boron subphthalocyanine derivative, pentacene, a pentacene derivative, benzothienobenzothiophene, a benzothienobenzothiophene derivative, fullerene, and a fullerene derivative.

8. The imaging element according to claim 1, wherein

the photoelectric conversion layer includes one of quinacridone or a quinacridone derivative as the p-type semiconductor, and one of chlorinated boron subphthalocyanine or a chlorinated boron subphthalocyanine derivative as the n-type semiconductor, and

the p-n junction surface includes a combination of a crystal plane of the quinacridone or the quinacridone derivative and a crystal plane of the chlorinated boron subphthalocyanine or the chlorinated boron subphthalocyanine derivative.

9. The imaging element according to claim 1, further comprising:

an organic photoelectric converter that comprises at least one photoelectric conversion layer including the photoelectric conversion layer, and

at least one inorganic photoelectric converter, wherein

the organic photoelectric converter and the at least one inorganic photoelectric converter are stacked,

the at least one inorganic photoelectric converter is configured to;

execute photoelectric conversion in a different wavelength range from the organic photoelectric converter.

10. The imaging element according to claim 9, wherein

the at least one inorganic photoelectric converter is embedded in a semiconductor substrate, and

the organic photoelectric converter is on a side on which a first surface of the semiconductor substrate is located.

11. The imaging element according to claim 10, further comprising a multilayer wiring layer on a side on which a second surface of the semiconductor substrate is located.

12. The imaging element according to claim 10, wherein

the organic photoelectric converter is configured to execute photoelectric conversion of green light,

a first inorganic photoelectric converter is configured to execute photoelectric conversion of blue light, and

a second inorganic photoelectric converter is configured to execute photoelectric conversion of red light,

the organic photoelectric converter, the first inorganic photoelectric converter, and the second inorganic photoelectric converter are stacked inside the semiconductor substrate.

13. The imaging element according to claim 1, wherein the specific combination of the first crystal plane and the second crystal plane comprises one of a (100) plane-a (001)A plane, the (100) plane-a (001)B plane, a (010) plane-a (010) plane, the (010) plane-the (001)A plane, the (010) plane-the (001)B plane, a (001) plane-the (001)A plane, or the (001) plane-the (001)B plane.

14. A method of manufacturing an imaging element, the method comprising:

forming a first electrode;

forming a photoelectric conversion layer on the first electrode; and

forming a second electrode on the photoelectric conversion layer, wherein

the photoelectric conversion layer comprises a p-type semiconductor, an n-type semiconductor, and a p-n junction surface between the p-type semiconductor and the n-type semiconductor,

the p-type semiconductor and the n-type semiconductor have controlled molecular orientations, and

the p-n junction surface includes a specific combination of a first crystal plane of the p-type semiconductor and a second crystal plane of the n-type semiconductor based on the controlled molecular orientations, such that the photoelectric conversion layer has an exciton charge separation rate of 1×

10¹⁰ s<sup>−

1</sup> to 1×

10¹⁶ s<sup>−

1</sup>, both inclusive in the p-n junction surface.

15. The method according to claim 14, further comprising subjecting the photoelectric conversion layer to a heat treatment.

16. The method of manufacturing the imaging element according to claim 14, further comprising subjecting the photoelectric conversion layer to a pressurization treatment.

17. The method of manufacturing the imaging element according to claim 14, further comprising subjecting the photoelectric conversion layer to a heat treatment and a pressurization treatment.

18. An imaging device, comprising:

a plurality of pixels, wherein each pixel of the plurality of pixels includes at least one imaging element, the at least one imaging element comprising;

a first electrode;

a second electrode that faces the first electrode; and

a photoelectric conversion layer between the first electrode and the second electrode, wherein

the photoelectric conversion layer comprises a p-type semiconductor, an n-type semiconductor, and a p-n junction surface between the p-type semiconductor and the n-type semiconductor,

the p-type semiconductor and the n-type semiconductor have controlled molecular orientations, and

the p-n junction surface includes a specific combination of a first crystal plane of the p-type semiconductor and a second crystal plane of the n-type semiconductor based on the controlled molecular orientations, such that the photoelectric conversion layer has an exciton charge separation rate of 1×

10¹⁰ s<sup>−

1</sup> to 1×

10¹⁶ s<sup>−

1</sup>, both inclusive in the p-n junction surface.