Black Phosphorus Crystal Having High Photoelectric Response Rate, Two-Dimensional Black Phosphorus PN Junction, and Preparation Method and Use Thereof

• US 20190055668A1
• Filed: 12/28/2016
• Published: 02/21/2019
• Est. Priority Date: 04/01/2016
• Status: Active Grant

• Current Assignee: Suzhou Institute of Nano-Tech and Nano-Bionics
• Original Assignee: Suzhou Institute of Nano-Tech and Nano-Bionics Chinese Academy of Sciences
• Inventors: Zhang, Kai, Zhang, Yuegang, Xu, Yijun
• Granted Patent: US 10,640,884 B2
• Time in Patent Office: Days
• CPC Class Codes: C01B 25/02 Preparation of phosphorus
• CPC Class Codes: C01P 2002/01 depicted by a TEM-image
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C30B 23/00 Single-crystal growth by condensing evaporated or sublimed materials
• CPC Class Codes: C30B 29/02 Elements
• CPC Class Codes: C30B 9/04 by cooling of the solution
• CPC Class Codes: H01L 21/02521 Materials
• CPC Class Codes: H01L 29/12 characterised by the materials of which they are formed
• CPC Class Codes: H01L 29/24 including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22 including organic materials H10K99/00
• CPC Class Codes: H01L 29/861 Diodes
• CPC Class Codes: H01L 29/8611 Planar PN junction diodes
• CPC Class Codes: H01L 31/0264 Inorganic materials
• CPC Class Codes: H01L 31/032 including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
• CPC Class Codes: H01L 31/036 characterised by their crystalline structure or particular orientation of the crystalline planes
• CPC Class Codes: H01L 31/09 Devices sensitive to infrared, visible or ultraviolet radiation H01L31/101 takes precedence
• CPC Class Codes: H01L 31/1013 devices sensitive to two or more wavelengths, e.g. multi-spectrum radiation detection devices
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H10K 30/00 : Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation integrated devices or assemblies of multiple devices H10K39/00, H10K65/00; electrolytic light-sensitive devices H01G9/20
• CPC Class Codes: H10K 30/50 : Photovoltaic [PV] devices
• CPC Class Codes: Y02E 10/50 : Photovoltaic [PV] energy
• CPC Class Codes: Y02E 10/547 : Monocrystalline silicon PV cells

Abstract

A black phosphorus crystal having a high photoelectric response rate, a two-dimensional black phosphorus PN junction, and preparation method and use thereof. The black phosphorus crystal having a high photoelectric response rate is a single crystal with a spatial point group Cmca (No. 64), cell parameters a=3.2-3.4 Å, b=10.4-10.6 Å, c=4.3-4.5 Å, and an interlayer spacing of 4-6 Å, and is characterized by a high photoelectric response rate, an adjustable semiconductor type, and the like. Its preparation method is simple with a mild condition, a high yield, a low cost, and less pollution. The two-dimensional black phosphorus PN junction comprises a two-dimensional black phosphorus film, a first area of the film forming an n-type semiconductor by n-type doping, a second area of the film is maintained as a p-type semiconductor, and the first area is adjacent to the second area, to enable the n-type semiconductor to be combined with the p-type semiconductor to form the PN junction. The two-dimensional black phosphorus PN junction has properties, such as a unidirectional conductivity, or a special photovoltaic effect. The preparation method is simple, and efficient with a good repeatability, and is compatible with a conventional semiconductor technology. The black phosphorus crystal and the two-dimensional black phosphorus PN junction according to the disclosure have extensive application prospects in photoelectric and electronic fields.

Claims

1. A black phosphorus crystal having a high photoelectric response rate, the black phosphorus crystal being a single crystal with a spatial point group Cmca (No. 64), cell parameters a=3.2-3.4 Å

, b=10.4-10.6 Å

, c=4.3-4.5 Å

, and an interlayer spacing of 4-6 Å

, a characteristic XRD pattern of the black phosphorus crystal comprises 5 2θ

peaks;

17.1°

, 26.6°

, 34.4°

, 40.2°

, and 52.5°

, a doped element within the black phosphorus crystal comprises any one or a combination of two or more of phosphorus, boron, carbon, sodium, magnesium, sulfur, potassium, arsenic, stibium, bismuth, selenium, tellurium, ferrum, nickel, fluorine, chlorine, bromine, or hydrogen, and an XPS spectrum of the black phosphorus crystal comprises at least one of following characteristic peaks;

phosphorus 129-132 eV, boron 189-194 eV, carbon 283-286 eV, sodium 1064-1080 eV, magnesium 1290-1320 eV, sulfur 160-172 eV, potassium 290-300 eV, arsenic 40-50 eV, stibium 32-36 eV, bismuth 156-160 eV, selenium 53-58 eV, tellurium 567-590 eV, ferrum 718-723 eV, nickel 850-855 eV, fluorine 682-690 eV, chlorine 194-202 eV, or bromine 66-70 eV.

3. The black phosphorus crystal having a high photoelectric response rate according to claim 1, wherein the black phosphorus crystal is a semiconductor, the semiconductor is a p-type or n-type having a band gap of 0.1-2.5 eV, a switching ratio of 103-106, and a carrier mobility of 10-30000 cm²/Vs, preferably 100-3000 cm²/Vs, while a photoresponse rate of the black phosphorus crystal is more than 1 NW.

11. Use of the black phosphorus crystal having a high photoelectric response rate according to claim 1 in the preparation of a photoelectric device.

12. A photoelectric device, comprising the black phosphorus crystal having a high photoelectric response rate according to claim 1, a photoresponse rate of the black phosphorus crystal being more than 1 NW.

13. The photoelectric detector according to claim 12, comprising a film stripped from the black phosphorus crystal, and a thickness of the film is 1-20 nm.

2. (canceled)

4-6. -6. (canceled)

7. A preparation method of a black phosphorus crystal having a high photoelectric response rate, comprising:

providing a growth precursor, the growth precursor comprising red phosphorus, a mineralizer, and a doped element at a mass ratio of (100-600);

(10-100);

(0.1-10), wherein the doped element comprises any one or a combination of two or more of selenium, sulfur, carbon, boron, arsenic, sodium, magnesium, potassium, stibium, bismuth, selenium, tellurium, ferrum, nickel, fluorine, chlorine, bromine, or hydrogen; and

placing the growth precursor in a sealed reactor having an inner chamber in a vacuum environment, and successively heating the reactor accommodating the growth precursor first by heating from room temperature to 600-850°

C. within 1-3 hours, and thermostatically controlling for 1-3 hours, then by cooling to 450-550°

C. within 1-24 hours, and thermostatically controlling for 1-12 hours, then by cooling to 100-200°

C. within 1-4 hours, and then by cooling to room temperature within 1-3 hours, and finally forming the black phosphorus crystal having a high photoelectric response rate.

9. The preparation method according to claim 7, wherein the mineralizer comprises any one or a combination of two or more of stannum, gold, gold-stannum alloy, stannic iodide, argentum, copper, or magnesium-stannum-copper alloy.

8. (canceled)

10. (canceled)

14. A two-dimensional black phosphorus PN junction, comprising a two-dimensional black phosphorus film, a first area of the black phosphorus film forming an n-type semiconductor by n-type doping, a second area of the black phosphorus film being maintained as a p-type semiconductor, the first area being adjacent to the second area, to enable the n-type semiconductor to be combined with the p-type semiconductor to form the PN junction.

15. The two-dimensional black phosphorus PN junction according to claim 14, wherein a thickness of the black phosphorus film is 0.5-100 nm;

and/or, the black phosphorus film is obtained through stripping from a black phosphorus crystal at least by a micromechanical stripping method or a liquid phase stripping method.

17. The two-dimensional black phosphorus PN junction according to claim 14, wherein the two-dimensional black phosphorus PN junction has a unidirectional conductivity and/or a photovoltaic property, and parameters characterizing the photovoltaic property include:

a short circuit current of the two-dimensional black phosphorus PN junction being 1-200 nA, its open circuit voltage being 1-500 mV, and its maximum output power being 1-100 nW.

31. Use of the two-dimensional black phosphorus PN junction according to claim 14 in the preparation of an electronic device or photoelectric device, wherein the electronic device or photoelectronic device comprises a rectifier diode, a detector diode, a switching diode, a voltage regulator diode, an avalanche diode, a semiconductor laser diode, a semiconductor light emitting diode, a photoelectric detector, a solar cell, or a bipolar transistor.

16. (canceled)

18. A two-dimensional black phosphorus PN junction, comprising a two-dimensional black phosphorus film, at least a local surface area of the phosphorus black film being coated with a film having a charge transfer doping property;

the black phosphorus film forming an n-type semiconductor by doping at least at a junction interface of the black phosphorus film and the film having a charge transfer doping property;

the black phosphorus film further comprising black phosphorus as a p-type semiconductor; and

the n-type semiconductor being combined with the p-type semiconductor to form the PN junction, while the two-dimensional black phosphorus PN junction has a unidirectional conductivity and/or a photovoltaic property, and parameters characterizing the photovoltaic property include;

a short circuit current of the two-dimensional black phosphorus PN junction being 1-200 nA, its open circuit voltage being 1-500 mV, and its maximum output power being 1-100 nW.

19. The two-dimensional black phosphorus PN junction according to claim 18, wherein a thickness of the black phosphorus film is 0.5-100 nm;

and/or the black phosphorus film is obtained through stripping from a black phosphorus crystal at least by a micromechanical stripping method or a liquid phase stripping method; and

/or a thickness of the film having a charge transfer property is 5-2000 nm; and

/or materials of the film having a charge transfer doping property comprise 2,3,5,6-tetrafluoro-7,7′

,8,8′

-tetracyanoquinodimethane, 1,5-naphthalenediamine, 9,10-dimethylanthracene, 9,10-dibromoanthracene, tetrasodium 1,3,6,8-pyrenetetrasulfonate (C₁₆H₆Na₄O₁₂S₄), Si_xN_y, or Cs_mCO_n, wherein x;

y=1;

(0.5-2), and m;

n=1;

(0.1-2).

20-23. -23. (canceled)

24. A preparation method of a two-dimensional black phosphorus PN junction, comprising:

providing a two-dimensional black phosphorus film; and

forming an n-type semiconductor by n-type doping on a local area of the black phosphorus film, enabling other local area of the black phosphorus film to be maintained as a p-type semiconductor, and enabling the n-type semiconductor to be combined with the p-type semiconductor to form the PN junction.

25. The preparation method according to claim 24, comprising:

depositing a film having a charge transfer doping property in a local surface area of the black phosphorus film at least by a physical and/or chemical deposition method, to enable the local area of the black phosphorus film to form the n-type semiconductor by n-type doping.

27. The preparation method according to claim 24, wherein a thickness of the black phosphorus film is 0.5-100 nm;

and/or the black phosphorus film is obtained through stripping from a black phosphorus crystal at least by a micromechanical stripping method or a liquid phase stripping method; and

/or a thickness of the film having a charge transfer property is 5-2000 nm and/or materials of the film having a charge transfer doping property comprise 2,3,5,6-tetrafluoro-7,7′

,8,8′

-tetracyanoquinodimethane, 1,5-naphthalenediamine, 9,10-dimethylanthracene, 9,10-dibromoanthracene, tetrasodium 1,3,6,8-pyrenetetronate (C₁₆H₆Na₄O₁₂S₄), Si_xN_y, or Cs_mCO_n (x;

y=1;

(0.5-2), m;

n=1;

(0.1-2)).

26. (canceled)

28-30. -30. (canceled)

32. (canceled)