CN107285289B - Black phosphorus crystal, preparation method and application with high photoelectric respone rate - Google Patents
Black phosphorus crystal, preparation method and application with high photoelectric respone rate Download PDFInfo
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- CN107285289B CN107285289B CN201610202569.5A CN201610202569A CN107285289B CN 107285289 B CN107285289 B CN 107285289B CN 201610202569 A CN201610202569 A CN 201610202569A CN 107285289 B CN107285289 B CN 107285289B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000013078 crystal Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 28
- 239000004065 semiconductor Substances 0.000 claims description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 19
- 229910052711 selenium Inorganic materials 0.000 claims description 19
- 239000011669 selenium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052785 arsenic Inorganic materials 0.000 claims description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000003708 ampul Substances 0.000 description 14
- 239000010453 quartz Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000005566 electron beam evaporation Methods 0.000 description 5
- 230000005669 field effect Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- -1 CN104310326A Chemical compound 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Light Receiving Elements (AREA)
Abstract
The invention discloses a kind of black phosphorus crystal, preparation method and applications with high photoelectric respone rate.The black phosphorus crystal with high photoelectric respone rate is monocrystalline, and space group Cmca (no.64), cell parameter is Interlamellar spacingPreparation method includes: to be placed in the growth predecessor comprising red phosphorus, mineralizer and doped chemical in the sealed reaction vessel that inner cavity is vacuum environment, and successively heated to the reaction vessel, keep the temperature, cool down, so that growth forms the black phosphorus crystal.The carrier type and carrier concentration of black phosphorus crystal provided by the invention are adjustable, in the case where being not necessarily to subsequent modification, show high photoelectric respone rate, preparation method is simple simultaneously, it is at low cost, pollution is small, yield is high, product good crystallinity, uniform doping, have wide application prospects in field of optoelectronic devices.
Description
Technical field
The present invention relates to a kind of photoelectric materials, are doped with high photoelectric respone rate, semiconductor type more particularly to one kind
Adjustable black phosphorus crystal and the preparation method and application thereof, such as preparing the application in photodetector.
Background technique
Black phosphorus is a kind of New Two Dimensional atomic crystal material, has high carrier mobility (~1000cm2/ Vs) and switch
Than (> 105) and the excellent properties such as tunable direct band gap (0.3-2eV), compensate for zero band gap, the transition metal of graphene
The too low performance deficiency of chalkogenide (TMDs) carrier mobility is another semiconductor technology and the industry of allowing after graphene
The two-dimensional material that boundary feels inspired, especially in photoelectron device, such as: high-performance optical detector, optical waveguide, mode-locked laser,
Huge potentiality are shown in terms of the development and application of modulator, polarizer etc..
Currently, the research and development of black phosphorus and its technology of preparing focus mostly on intrinsic black phosphorus (such as CN104310326A,
CN105133009A).However, intrinsic black phosphorus is contacted with metal electrode has higher Schottky barrier, it is suppressed that photoproduction current-carrying
The transmission of son is unfavorable for the performance of opto-electronic device so that photoelectric respone rate is relatively low.
In addition, corresponding to the conventional semiconductor materials such as silicon, GaAs, the semiconductor type of the multiplicity such as intrinsic, p-type, N-shaped and
Tunable hole, electron concentration are materials in the necessary condition of the semiconductor components and devices application and development such as opto-electronic device.And work as
Preceding black phosphorus shows as p-type electric-conducting more, N-shaped lacks, and carrier concentration can not regulate and control.
Summary of the invention
It is adjustable with bloom with high photoelectric respone rate, semiconductor type that the main purpose of the present invention is to provide a kind of
The black phosphorus crystal and the preparation method and application thereof of electroresponse rate, to solve the above problems.
For achieving the above object, the present invention provides the following technical scheme that
The embodiment of the invention provides a kind of black phosphorus crystals with high photoelectric respone rate, are monocrystalline, space group
Cmca (no.64), cell parameter areInterlamellar spacing
Further, the XRD characteristic spectrum of the black phosphorus crystal includes 52 peaks θ: 17.1 °, 26.6 °, and 34.4 °, 40.2 °,
52.5°。
Further, the black phosphorus crystal is semiconductor, and semiconductor type is p-type or N-shaped, and band gap is 0.1~2.5eV,
On-off ratio is 103~106, carrier mobility is 10~3000cm2/ Vs, preferably 100~3000cm2/Vs。
Further, the doped chemical in the black phosphorus crystal is comprising in phosphorus, boron, carbon, sodium, magnesium, sulphur, potassium, arsenic element
Any one or two or more combinations.
Further, the photoresponse rate of the black phosphorus crystal is greater than 1A/W.
The embodiment of the invention also provides a kind of preparation methods of black phosphorus crystal with high photoelectric respone rate comprising:
Growth predecessor is provided, the growth predecessor includes that mass ratio is (100~600): (10~100): (0.1~
10) red phosphorus, mineralizer and doped chemical；
By it is described growth predecessor be placed in inner cavity be vacuum environment sealed reaction vessel in, and to the reaction vessel according to
It is secondary to be heated, kept the temperature, cooled down, to grow to form the black phosphorus crystal with high photoelectric respone rate.
Further, the doped chemical include selenium, sulphur, carbon, boron, arsenic, sodium, magnesium, in potassium element any one or two
Kind or more combination.
The embodiment of the invention provides a kind of photodetectors, and it includes the black phosphorus with high photoelectric respone rate is brilliant
Body, photoresponse rate are greater than 1A/W.
Further, the photodetector includes the film separated from the black phosphorus crystal, the film
With a thickness of 1~20nm.
Compared with prior art, the invention has the advantages that the doping black phosphorus preparation method provided is without high temperature and pressure etc.
Harsh conditions, yield is high, at low cost, pollution is small, and the good crystallinity of the prepared black phosphorus crystal with high photoelectric respone rate is mixed
Miscellaneous uniform, semiconductor type and carrier concentration are adjustable, and in the case where not needing subsequent modification, can be directly from institute
It states black phosphorus crystal and separates two-dimensional film material supplied materials and prepare photodetector, method is simple, high yield rate, and shows high
Response rate be particularly advantageous for black phosphorus much higher than existing based on intrinsic black phosphorus and its constructed, hetero-junctions photodetector and exist
The popularization and application of the field of optoelectronic devices such as photodetection.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the photo of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 2 is the Raman spectrometer test curve figure of selenium doping in embodiment 1；
Fig. 3 is the transmission electron microscope photo and selective electron diffraction figure of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 4 is the lattice fringe figure of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 5 is the XRD diagram of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 6 a- Fig. 6 b is the phosphorus and selenium element distribution map of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 7 is the P elements XPS map of black phosphorus crystal in the embodiment of the present invention 1；
Fig. 8 is the selenium element XPS map of black phosphorus crystal in the embodiment of the present invention 1.
Specific embodiment
A kind of black phosphorus crystal with high photoelectric respone rate that the one aspect of the embodiment of the present invention provides, is monocrystalline,
Space group Cmca (no.64), cell parameter areInterlamellar spacing
A kind of black phosphorus crystal with high photoelectric respone rate that the other side of the embodiment of the present invention provides, preparation side
Method includes:
Growth predecessor is provided, the growth predecessor includes that mass ratio is (100~600): (10~100): (0.1~
10) red phosphorus, mineralizer and doped chemical；
By it is described growth predecessor be placed in inner cavity be vacuum environment sealed reaction vessel in, and to the reaction vessel into
Row heating first rises to 600~850 DEG C from room temperature in 1~3 hour, and keeps the temperature 1~3 hour, drops in 1~24 hour later
To 450~550 DEG C, and 1~12 hour is kept the temperature, 100~200 DEG C is cooled in 1~4 hour thereafter, then at 1~3 hour
It is inside cooled to room temperature, ultimately forms the black phosphorus crystal with high photoelectric respone rate, the black phosphorus crystal is monocrystalline, space group
Cmca (no.64), cell parameter areInterlamellar spacing
Further, the XRD characteristic spectrum of the black phosphorus crystal includes 52 peaks θ: 17.1 °, 26.6 °, and 34.4 °, 40.2 °,
52.5°。
Further, the black phosphorus crystal is semiconductor, and semiconductor type is that p-type or N-shaped are adjustable, band gap 0.1~
Adjustable within the scope of 2.5eV, on-off ratio is 103~106Adjustable in range, carrier mobility is in 10~3000cm2Within the scope of/Vs
It is adjustable, preferably 100~3000cm2/Vs。
Further, the doped chemical in the black phosphorus crystal is comprising in phosphorus, boron, carbon, sodium, magnesium, sulphur, potassium, arsenic element
Any one or two or more combinations, and it is without being limited thereto.
Further, the XPS map of the black phosphorus crystal includes at least one of following characteristics peak: phosphorus 129~
132eV, 189~194eV of boron, 283~286eV of carbon, 1064~1080eV of sodium, 1233~1237eV of magnesium, 160~172eV of sulphur, potassium
290~300eV, 40~50eV of arsenic.
Further, the photoresponse rate of the black phosphorus crystal is greater than 1A/W.
The other side of the embodiment of the present invention also provides a kind of preparation side of black phosphorus crystal with high photoelectric respone rate
Method comprising:
Growth predecessor is provided, the growth predecessor includes that mass ratio is (100~600): (10~100): (0.1~
10) red phosphorus, mineralizer and doped chemical；
By it is described growth predecessor be placed in inner cavity be vacuum environment sealed reaction vessel in, and to the reaction vessel according to
It is secondary to be heated, kept the temperature, cooled down, to grow to form the black phosphorus crystal with high photoelectric respone rate.
In some more preferred embodiments, the preparation method includes: to being equipped with the growth predecessor
The reaction vessel heated, first rise to 600~850 DEG C from room temperature in 1~3 hour, and keep the temperature 1~3 hour, later
It is down to 450~550 DEG C in 1~24 hour, and keeps the temperature 1~12 hour, is cooled to 100~200 DEG C in 1~4 hour thereafter,
Then it is cooled to room temperature in 1~3 hour, ultimately forms the black phosphorus crystal.
Further, the mineralizer include tin, it is gold, gold-tin alloy, stannic iodide, silver, copper, any in magnesium gun-metal
A combination of one or more, but not limited to this.
Further, the doped chemical include selenium, sulphur, carbon, boron, arsenic, sodium, magnesium, in potassium element any one or two
Kind or more combination.
In a more specific case study on implementation, the preparation method includes: that the predecessor is mounted in quartz ampoule,
It again by quartz ampoule vacuum sealing tube, and lies in a horizontal plane in tube furnace and heats, until growth forms the black phosphorus crystal.
The embodiment of the invention also provides the black phosphorus crystals with high photoelectric respone rate by aforementioned any method preparation.
The another aspect of the embodiment of the present invention additionally provides the purposes of the black phosphorus crystal with high photoelectric respone rate,
Such as preparing the purposes in photoelectric device.
For example, the embodiment of the invention provides a kind of photodetector, it includes described with high photoelectric respone rate
Black phosphorus crystal, photoresponse rate are greater than 1A/W.
More preferred, the photodetector includes the film separated from the black phosphorus crystal, the film
With a thickness of 1~20nm.
Further, the film is distributed on substrate, and the film is equipped with electrode.
Further, the electrode includes the electrodes such as chrome gold, titanium/gold, ni au, platinum/gold, but not limited to this.
Further, the substrate includes low-resistance silicon substrate, but not limited to this.
Further, the photodetector includes field effect transistor.
The embodiment of the invention provides a kind of production methods of photodetector comprising: from the black phosphorus crystal
The black phosphorus film with a thickness of 1~20nm is separated, and is transferred on silicon substrate, electron beam exposure or electron beam evaporation plating are then passed through
Method depositing electrode on the black phosphorus film.
For a further understanding of the present invention, below in conjunction with several examples and drawings, the present invention is described in detail.
It is understood, however, that those skilled in the art can use for reference the content of this specification, it is suitably modified realization of process parameters.Especially
It should be pointed out that all similar substitutions and modifications are apparent to those skilled in the art, they are all regarded
To be included in the present invention.Application of the invention is described by preferred embodiment, and related personnel can obviously not take off
From being modified in the content of present invention, spirit and scope to application as described herein or appropriate changes and combinations, to realize and answer
Use the technology of the present invention.
Embodiment 1: the present embodiment is related to a kind of preparation method of selenium doping black phosphorus crystal, comprising:
Predecessor red phosphorus, tin, copper, selenium are pressed into (550~600): (10~20): (20~40): the quality of (0.1~0.5)
Than being fitted into quartz ampoule, and by quartz ampoule vacuum sealing tube.Quartz ampoule level is then placed on heat growth in tube furnace,
Detailed process includes: to rise to 850 DEG C from room temperature in 3 hours, and keep the temperature 1 hour, is down to 450 DEG C in 24 hours later, and protect
Temperature 6 hours, 100 DEG C are cooled to thereafter in 3 hours, then room temperature is cooled in 1 hour, finally obtains black phosphorus crystal.Its
A kind of photo of middle typical black phosphorus crystal product sees Fig. 1, and Raman spectrum sees Fig. 2, therefore can verify that the crystal is
Selenium adulterates black phosphorus.The transmission electron microscope results that Fig. 3 is selenium doping black phosphorus crystal are please referred to again, illustration is selective electron diffraction figure,
Show that selenium doping black phosphorus crystal has high crystallographic.The lattice fringe figure that Fig. 4 is selenium doping black phosphorus crystal is separately please referred to,
Spacing of the atomic distance in the direction x and y is 0.166 and 0.220 nanometer respectively.Its XRD characteristic spectrum includes 52 peaks θ: 17.1 °,
26.6 °, 34.4 °, 40.2 °, 52.5 ° (refering to Fig. 5).Selenium element the selenium doping black phosphorus crystal in be distributed more uniformly (refering to
Fig. 6 a- Fig. 6 b), in addition, XPS map demonstrate in selenium doping black phosphorus crystal comprising P elements and selenium element (refering to Fig. 7 and
8).And the other black phosphorus crystal products obtained to the present embodiment characterize, and similar test result also can be obtained.
Further, on the basis of typical case's selenium of the present embodiment adulterates black phosphorus crystal, two-dimentional black phosphorus half can also be prepared
Conductor photodetector, specific method include:
Black phosphorus film (about 1~20 nanometer thick) is transferred on low-resistance silicon substrate using the method for micromechanics removing, then
It deposited chrome gold electrode (about 10/90 nanometer thick) with the method for electron beam exposure, electron beam evaporation plating, be prepared for field effect transistor
Pipe.Electrical testing shows that the device performance is excellent, and electrode and the contact of black phosphorus channel are good, and it is P-type semiconductor that selenium, which adulterates black phosphorus,
On-off ratio is 103Above and up to 106, hole mobility averagely about 561cm2/ Vs (reaches as high as about 3000cm2/ Vs), electricity
Transport factor averagely about 51cm2/Vs.Meanwhile being also tested for the photoelectric properties of selenium doped black phosphorescence electric explorer, photoelectric respone
Rate averagely about 15.33*103MA/W, much higher than the photodetector based on intrinsic black phosphorus and hetero-junctions.
And according to preceding method, to the photodetector of the other black phosphorus crystal products building obtained using the present embodiment into
Similar test result also can be obtained in row performance test.
Embodiment 2: the present embodiment is related to a kind of preparation method of sulfur doping black phosphorus crystal, comprising:
Predecessor red phosphorus, tin, stannic iodide, sulphur are pressed into (100~150): (60~80): (30~40): the matter of (0.1~2)
Amount ratio is fitted into quartz ampoule, and by quartz ampoule vacuum sealing tube.Quartz ampoule level is then placed on heat growth in tube furnace,
Detailed process includes: to rise to 600 DEG C from room temperature in 1 hour, and keep the temperature 3 hours, is down to 500 DEG C in 12 hours later, and
Heat preservation 12 hours, 150 DEG C are cooled to thereafter in 1 hour, is then cooled to room temperature in 2 hours, ultimately forms the black phosphorus
Crystal.Finally obtain black phosphorus crystal, sulfur doping amount averagely about 0.2wt% therein.
On the basis of aforementioned sulfur doping black phosphorus crystal, two-dimentional black phosphorus semiconductor photo detector can be prepared.Specific side
Method is as follows: black phosphorus film (about 10 nanometers thick) being transferred on low-resistance silicon substrate with the method that micromechanics is removed, then uses electronics
Beam exposes, the method for electron beam evaporation plating deposited chrome gold electrode (10/90 nanometer), is prepared for field effect transistor.Electrical testing
Show that device performance is excellent, electrode and the contact of black phosphorus channel are good, and sulfur doping black phosphorus is n-type semiconductor, and on-off ratio is 103
Above and up to 106, hole mobility averagely about 283cm2/ Vs, electron mobility averagely about 673cm2/Vs.Meanwhile it also testing
The photoelectric properties of sulfur doping black phosphorus photodetector, photoelectric respone rate averagely about 1.65*103MA/W, much higher than based on pure
The photodetector of black phosphorus and hetero-junctions.
Embodiment 3: the present embodiment is related to a kind of preparation method of magnesium doping black phosphorus crystal, comprising:
Predecessor red phosphorus, gold-tin alloy, tin, magnesium are pressed into (550~600): (50~70): (25~35): the matter of (7~10)
Amount ratio is fitted into quartz ampoule, and by quartz ampoule vacuum sealing tube.Quartz ampoule level is then placed on heat growth in tube furnace,
Detailed process includes: to rise to 750 DEG C from room temperature in 2 hours, and keep the temperature 2 hours, is down to 550 DEG C in 24 hours later, and
Heat preservation 1 hour, 200 DEG C are cooled to thereafter in 4 hours, is then cooled to room temperature in 3 hours, and it is flat to finally obtain doped amount of magnesium
The black phosphorus crystal of about 0.6wt%.
On the basis of aforementioned magnesium adulterates black phosphorus crystal, two-dimentional black phosphorus semiconductor photo detector can be prepared.Specific side
Method is as follows: black phosphorus film (about 14 nanometers thick) being transferred on low-resistance silicon substrate with the method that micromechanics is removed, then uses electronics
Beam exposes, the method for electron beam evaporation plating deposited chrome gold electrode (10/90 nanometer), is prepared for field effect transistor.Electrical testing
Show that device performance is excellent, electrode and the contact of black phosphorus channel are good, and it is P-type semiconductor that magnesium, which adulterates black phosphorus, and on-off ratio is 103
Above and up to 106, hole mobility averagely about 2896cm2/ Vs, electron mobility averagely about 26cm2/Vs.Meanwhile it also testing
The photoelectric properties of magnesium doped black phosphorescence electric explorer, photoelectric respone rate averagely about 2.16*103MA/W, much higher than intrinsic black
Phosphorus and heterojunction photoelectric detector.
Embodiment 4: the present embodiment is related to a kind of preparation method of arsenic doping black phosphorus crystal, comprising:
Predecessor red phosphorus, tin, gold, arsenic are pressed into (300~350): (30~40): (15~20): the mass ratio dress of (3~5)
Enter in quartz ampoule, and by quartz ampoule vacuum sealing tube.Quartz ampoule level is then placed on heat growth in tube furnace, specific mistake
Journey includes: to rise to 700 DEG C from room temperature in 2 hours, and keep the temperature 3 hours, is down to 500 DEG C in 10 hours later, and it is small to keep the temperature 3
When, 100 DEG C are cooled in 4 hours thereafter, is then cooled to room temperature in 3 hours, finally obtains arsenic doping amount averagely about
The black phosphorus crystal of 1wt%.
On the basis of aforementioned arsenic doping black phosphorus crystal, two-dimentional black phosphorus semiconductor photo detector can be prepared.Specific side
Method is as follows: black phosphorus film (16 nanometers) being transferred on low-resistance silicon substrate with the method that micromechanics is removed, is then exposed with electron beam
Light, electron beam evaporation plating method deposited chrome gold electrode (10/90 nanometer), be prepared for field effect transistor.Electrical testing shows
Device performance is excellent, and electrode and the contact of black phosphorus channel are good, and arsenic doping black phosphorus is P-type semiconductor, and on-off ratio is 103More than
And up to 106, hole mobility averagely about 526cm2/ Vs, electron mobility averagely about 56cm2/Vs.Meanwhile it being also tested for arsenic and mixing
The photoelectric properties of miscellaneous black phosphorus photodetector, photoelectric respone rate averagely about 4.96*103MA/W, much higher than based on intrinsic black phosphorus
And the photodetector of hetero-junctions.
Finally it should also be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (12)
1. a kind of black phosphorus crystal with high photoelectric respone rate, it is characterised in that its preparation method includes:
There is provided growth predecessor, it is described growth predecessor include mass ratio be (100 ~ 600): (10 ~ 100): (0.1 ~ 10) it is red
Phosphorus, mineralizer and doped chemical；
The growth predecessor is placed in the sealed reaction vessel that inner cavity is vacuum environment, and the reaction vessel is added
Heat first rises to 600 ~ 850 DEG C from room temperature in 1 ~ 3 hour, and keeps the temperature 1 ~ 3 hour, is down to 450 ~ 550 in 1 ~ 24 hour later
DEG C, and 1 ~ 12 hour is kept the temperature, 100 ~ 200 DEG C are cooled in 1 ~ 4 hour thereafter, room temperature is then cooled in 1 ~ 3 hour, most
For end form at the black phosphorus crystal with high photoelectric respone rate, the black phosphorus crystal is monocrystalline, space group Cmca (no. 64), structure cell
Parameter is a=3.2 ~ 3.4, b=10.4 ~ 10.6, c=4.3 ~ 4.5, interlamellar spacing 4 ~ 6.
2. the black phosphorus crystal according to claim 1 with high photoelectric respone rate, it is characterised in that: the black phosphorus crystal
XRD characteristic spectrum includes 52 peaks θ: 17.1 °, 26.6 °, 34.4 °, 40.2 °, 52.5 °.
3. the black phosphorus crystal according to claim 1 with high photoelectric respone rate, it is characterised in that: the black phosphorus crystal is
Semiconductor, semiconductor type are p-type or N-shaped, and band gap is 0.1 ~ 2.5eV, on-off ratio 103~106, carrier mobility be 10 ~
3000cm2/Vs。
4. the black phosphorus crystal according to claim 1 with high photoelectric respone rate, it is characterised in that: the black phosphorus crystal
Carrier mobility is 100 ~ 3000cm2/Vs。
5. the black phosphorus crystal according to claim 1 with high photoelectric respone rate, it is characterised in that: the doped chemical packet
Phosphorous, boron, carbon, sodium, magnesium, sulphur, potassium, any one or two or more combinations in arsenic element, correspondingly, the black phosphorus crystal
XPS map include at least one of following characteristics peak: 129 ~ 132 eV of phosphorus, 189 ~ 194 eV of boron, carbon 283 ~ 286
EV, 1064 ~ 1080 eV of sodium, 1233 ~ 1237 eV of magnesium, 160 ~ 172 eV of sulphur, 290 ~ 300 eV of potassium, 40 ~ 50 eV of arsenic.
6. the black phosphorus crystal according to claim 1 with high photoelectric respone rate, it is characterised in that: the black phosphorus crystal
Photoresponse rate is greater than 1 A/W.
7. a kind of preparation method of the black phosphorus crystal with high photoelectric respone rate, characterized by comprising:
There is provided growth predecessor, it is described growth predecessor include mass ratio be (100 ~ 600): (10 ~ 100): (0.1 ~ 10) it is red
Phosphorus, mineralizer and doped chemical；
The growth predecessor is placed in the sealed reaction vessel that inner cavity is vacuum environment, and to being equipped with the growth forerunner
The reaction vessel of object is heated, and first rises to 600 ~ 850 DEG C from room temperature in 1 ~ 3 hour, and keep the temperature 1 ~ 3 hour, later
It is down to 450 ~ 550 DEG C in 1 ~ 24 hour, and keeps the temperature 1 ~ 12 hour, is cooled to 100 ~ 200 DEG C in 1 ~ 4 hour thereafter, then
Be cooled to room temperature in 1 ~ 3 hour, ultimately form the black phosphorus crystal with high photoelectric respone rate to the reaction vessel according to
It is secondary to be heated, kept the temperature, cooled down, to grow to form the black phosphorus crystal with high photoelectric respone rate.
8. preparation method according to claim 7, it is characterised in that: the mineralizer includes tin, gold, gold-tin alloy, iodine
Change tin, silver, copper, any one or two or more combinations in magnesium gun-metal.
9. preparation method according to claim 7, it is characterised in that: the doped chemical include selenium, sulphur, carbon, boron, arsenic,
Sodium, magnesium, any one or two or more combinations in potassium element.
10. the black phosphorus crystal with high photoelectric respone rate prepared by any one of claim 7-9 the method.
11. a kind of photodetector, it is characterised in that brilliant comprising the black phosphorus described in any one of claim 10 with high photoelectric respone rate
Body, photoresponse rate are greater than 1A/W.
12. photodetector according to claim 11, it is characterised in that include what is separated from the black phosphorus crystal
Film, the film with a thickness of 1 ~ 20 nm.
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| CN201610202569.5A CN107285289B (en) | 2016-04-01 | 2016-04-01 | Black phosphorus crystal, preparation method and application with high photoelectric respone rate |
| PCT/CN2016/112646 WO2017166878A1 (en) | 2016-04-01 | 2016-12-28 | Black phosphorus crystal with high photoelectric response rate, two-dimensional black phosphorus pn junction, and preparation method therefor and application thereof |
| JP2018551438A JP6810753B2 (en) | 2016-04-01 | 2016-12-28 | Black phosphorus crystal and its manufacturing method, photoelectric detector, two-dimensional black phosphorus PN junction and its manufacturing method and use |
| US16/090,087 US10640884B2 (en) | 2016-04-01 | 2016-12-28 | Black phosphorus crystal having high photoelectric response rate, two-dimensional black phosphorus PN junction, and preparation method and use thereof |
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| CN108059137B (en) * | 2017-12-04 | 2020-09-08 | 中国科学院电工研究所 | Preparation method of black phosphorus nano material |
| CN108538707B (en) * | 2018-03-05 | 2020-04-24 | 南京航空航天大学 | Preparation method of two-dimensional black phosphorus crystal |
| CN108550640B (en) * | 2018-04-17 | 2020-02-28 | 张晗 | Cadmium telluride nanocrystalline composite broadband black phosphorus photoelectric detector and preparation method thereof |
| CN109913942A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A kind of method that vapor transportation method prepares black phosphorus and adulterates black phosphorus monocrystalline |
| CN112110429B (en) * | 2019-06-21 | 2021-11-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method and application of black phosphorus nanosheet |
| CN110729410B (en) * | 2019-10-31 | 2022-06-21 | 京东方科技集团股份有限公司 | Organic light emitting diode, display panel and manufacturing method |
| CN111334780A (en) * | 2020-03-02 | 2020-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus film, preparation method and application thereof |
| CN111470485B (en) * | 2020-04-22 | 2022-08-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gold phosphide nanosheet and controllable preparation method and application thereof |
| CN114038902B (en) * | 2021-12-01 | 2022-07-01 | 上海镓芯科技有限公司 | Transient voltage suppression diode of thin film type semiconductor |
| CN114293146A (en) * | 2022-03-07 | 2022-04-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus and preparation method and application thereof |
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