CN109368607A - Black phosphorus nanometer sheet and its preparation method and application - Google Patents
Black phosphorus nanometer sheet and its preparation method and application Download PDFInfo
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- CN109368607A CN109368607A CN201811359020.2A CN201811359020A CN109368607A CN 109368607 A CN109368607 A CN 109368607A CN 201811359020 A CN201811359020 A CN 201811359020A CN 109368607 A CN109368607 A CN 109368607A
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- black phosphorus
- nanometer sheet
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 268
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000005416 organic matter Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- -1 alternatively Substances 0.000 claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 238000002604 ultrasonography Methods 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 230000005669 field effect Effects 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 3
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims description 2
- QEPFXAUFVJBNEL-UHFFFAOYSA-N C(F)(F)F.C(C)N1C(N(C=C1)C)CC Chemical compound C(F)(F)F.C(C)N1C(N(C=C1)C)CC QEPFXAUFVJBNEL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000003487 electrochemical reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZIFRMAZAZSOSSD-UHFFFAOYSA-N 1,2-diethyl-3-methyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.C(C)N1C(N(C=C1)C)CC ZIFRMAZAZSOSSD-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- PFWZRULJVRDQJQ-UHFFFAOYSA-N 1-butyl-11h-benzo[a]carbazole Chemical compound C1=CC=C2NC3=C4C(CCCC)=CC=CC4=CC=C3C2=C1 PFWZRULJVRDQJQ-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical class [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
Abstract
The present invention relates to a kind of black phosphorus nanometer sheets and its preparation method and application.The preparation method of the black phosphorus nanometer sheet includes the following steps: that black phosphorus and anode are placed in electrolyte using black phosphorus as cathode, and to black phosphorus and anodal closure to be electrochemically reacted, obtain expansion black phosphorus, electrolyte is ionic liquid, alternatively, electrolyte is quaternary ammonium salt solution；Black phosphorus will be expanded and oil-dissolving solvent mixes and carries out ultrasonic removing, obtain removing slurry；The heterocycle organic matter hybrid reaction of slurry and sulfur-bearing and nitrogen will be removed, obtains black phosphorus nanometer sheet.The black phosphorus nanometer chip architecture of above method preparation is relatively stable and dispersed preferable.
Description
Technical field
The present invention relates to technical field of material chemistry, more particularly to a kind of black phosphorus nanometer sheet and its preparation method and application.
Background technique
Two-dimentional black phosphorus has both excellent carrier mobility (> 1000cm2Vs-1) and the relevant continuous bandgap structure of the number of plies
(0.3~2.1eV), and the black phosphorus of any number of plies all has direct energy level band gap, so that its application tool in field of photoelectric devices
There is advantageous structural advantage.However the research for being currently based on two-dimentional black phosphorus is concentrated on substantially using mechanical stripping method as core
Fundamental research, the property and application problem of many black phosphorus are still urgently to be resolved.Currently, structural stability and dispersibility poor are
Limit one of the core bottleneck problem of black phosphorus application.
Summary of the invention
Based on this, it is necessary to provide that a kind of structure is relatively stable and the preparation method of dispersed preferable black phosphorus nanometer sheet.
In addition, also providing a kind of black phosphorus nanometer sheet and application.
A kind of preparation method of black phosphorus nanometer sheet, includes the following steps:
Using black phosphorus as cathode, the black phosphorus and anode are placed in electrolyte, and logical to the black phosphorus and the anode
Electricity obtains expansion black phosphorus to be electrochemically reacted, and the electrolyte is ionic liquid, alternatively, the electrolyte is quaternary ammonium salt
Solution, the ionic liquid are selected from 1- ethyl-3-methylimidazole bromide, 1- ethyl-3-methylimidazole villaumite, 1- ethyl -3- first
Base iodonium imidazolide salts, 1- ethyl -2,3- methylimidazole fluoroform sulphonate, 1,2- diethyl -3- methylimidazole trifluoromethanesulfonic acid
Salt, 1,2- dimethyl -3- ethyl imidazol(e) bromide, 1,2- dimethyl -3- ethyl imidazol(e) villaumite and 1,-dimethyl -3- ethyl imidazol(e)
At least one of tetrafluoroborate；The solute of the quaternary ammonium salt solution is selected from 1- ethyl -3- methyl ammonium tetrafluoroborate, normal-butyl
At least one of tetrachloric acid's ammonium, normal-butyl ammonium tetrafluoroborate and normal-butyl tetrafluoro ammonium phosphate；
The expansion black phosphorus and oil-dissolving solvent are mixed and carry out ultrasonic removing, obtains removing slurry；And
By the heterocycle organic matter hybrid reaction of the removing slurry and sulfur-bearing and nitrogen, the black phosphorus nanometer sheet is obtained.
In one of the embodiments, it is described to the black phosphorus and the anodal closure to be electrochemically reacted the step of
Are as follows: the voltage of 1V~10V is applied to be electrochemically reacted to the black phosphorus and the anode.
In one of the embodiments, it is described to the black phosphorus and the anodal closure to be electrochemically reacted the step of
Are as follows: applying density to the black phosphorus and the anode is 1mA/cm2~100mA/cm2Electric current to be electrochemically reacted.
It is described in one of the embodiments, that the expansion black phosphorus and oil-dissolving solvent are mixed to the step for carrying out ultrasonic removing
Further include the steps that isolating and purifying the expansion black phosphorus before rapid, described the step of isolating and purifying includes: described in removal
The anode in reaction system, then the reaction system is centrifuged, filter residue is obtained, the filter residue is cleaned, obtains
The expansion black phosphorus of purifying.
The step to the black phosphorus and the anodal closure to be electrochemically reacted in one of the embodiments,
Suddenly, it is described the expansion black phosphorus and oil-dissolving solvent are mixed the step of carrying out ultrasound removing and it is described by the removing slurry and
The step of heterocycle organic matter hybrid reaction of sulfur-bearing and nitrogen, is carried out under conditions of air.
The molar ratio of the expansion black phosphorus and the sulfur-bearing and the heterocycle organic matter of nitrogen is in one of the embodiments,
0.1:1~10:1.
The oil-dissolving solvent is selected from n,N-Dimethylformamide, dimethyl sulfoxide, N- first in one of the embodiments,
At least one of base pyrrolidones and tetrahydrofuran；And/or the concentration of the solute of the quaternary ammonium salt solution be 0.05g/mL~
10g/mL；And/or the solvent of the quaternary ammonium salt solution is selected from n,N-Dimethylformamide, dimethyl sulfoxide, N- crassitude
One of ketone and tetrahydrofuran.
The anode is selected from one of platinum, graphite carbon rod and graphene paper in one of the embodiments,.
The black phosphorus nanometer sheet that the preparation method of above-mentioned black phosphorus nanometer sheet is prepared.
Above-mentioned black phosphorus nanometer sheet is preparing the application in field effect transistor.
The preparation method of above-mentioned black phosphorus nanometer sheet by will by using black phosphorus as cathode, and with above-mentioned ionic liquid or on
Stating quaternary ammonium salt solution is electrolyte, is electrochemically reacted with anodal closure, so that expanded graphite is obtained, by that will expand black phosphorus
It is mixed with oil-dissolving solvent and carries out ultrasonic removing, obtained removing slurry, the heterocycle organic matter for removing slurry and sulfur-bearing and nitrogen is mixed
Reaction is closed, so that the black phosphorus nanometer sheet of ion salt covalent modification is obtained, the experiment proved that, the black phosphorus nanometer chip architecture is relatively stable
And dispersibility is preferably.
Detailed description of the invention
Fig. 1 is Raman (Raman) spectrogram for the black phosphorus nanometer sheet that embodiment 1 is prepared；
Fig. 2 is transmission (TEM) electron microscope for the black phosphorus nanometer sheet that embodiment 1 is prepared；
Fig. 3 is the electron diffraction diagram that Fig. 1 corresponds to constituency；
Fig. 4 is the enlarged drawing that Fig. 2 amplifies 1000 times；
Fig. 5 is the histogram of the hole mobility for the field effect transistor that the black phosphorus nanometer sheet of embodiment 1 is prepared.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to herein
Described embodiment.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more saturating
It is thorough comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
The preparation method of the black phosphorus nanometer sheet of one embodiment, includes the following steps:
Step S110: using black phosphorus as cathode, black phosphorus and anode being placed in electrolyte, and to black phosphorus and anodal closure with
It is electrochemically reacted, obtains expansion black phosphorus.
The step of in one of the embodiments, to black phosphorus and anodal closure to be electrochemically reacted are as follows: to black phosphorus and
Anode applies the voltage of 1V~10V to be electrochemically reacted.Too low voltage (being less than 1V) is although can be anti-with drive response
Answer rate too slow；Voltage is too high (being greater than 10V), and reaction dissolvent can decompose under the electric field and go bad.
In another embodiment, the step of to black phosphorus and anodal closure to be electrochemically reacted are as follows: to cathode and sun
It is 1mA/cm that pole, which applies density,2~100mA/cm2Electric current to be electrochemically reacted.Too low current density (is less than 1mA/
cm2) under, detachment rate is too slow；Current density is excessive (to be greater than 100mA/cm2), react too fast, removing incomplete material may
It falls off from electrode and peeling effect is undesirable.
Specifically, electrolyte is ionic liquid or quaternary ammonium salt solution；More specifically, ionic liquid is selected from 1- ethyl -3- first
Base imidazoles bromide, 1- ethyl-3-methylimidazole villaumite, 1- ethyl-3-methylimidazole salt compounded of iodine, 1- ethyl -2,3- methylimidazole
Fluoroform sulphonate, 1,2- diethyl -3- methylimidazole fluoroform sulphonate, 1,2- dimethyl -3- ethyl imidazol(e) bromide, 1,2-
Dimethyl -3- ethyl imidazol(e) villaumite and 1, at least one of-dimethyl -3- ethyl imidazol(e) tetrafluoroborate；Quaternary ammonium salt solution
Solute be selected from 1- ethyl -3- methyl ammonium tetrafluoroborate, normal-butyl tetrachloric acid ammonium, normal-butyl ammonium tetrafluoroborate and normal-butyl tetrafluoro
At least one of ammonium phosphate.
Specifically, the concentration of the solute of quaternary ammonium salt solution is 0.05g/mL~10g/mL.The solvent of quaternary ammonium salt solution is selected from
In N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP) and tetrahydrofuran (THF)
It is at least one.
Specifically, anode is selected from one of platinum, graphite carbon rod and graphene paper.Wherein, platinum is platinum filament or platinized platinum.
Step S120: expansion black phosphorus and oil-dissolving solvent being mixed and carry out ultrasonic removing, obtain removing slurry.
Specifically, the mass volume ratio for expanding black phosphorus and oil-based solvent is 1mg:1000mL~10mg:1mL, proportion stripping
Preferable from effect, excessively ultrasonic peeling effect is poor for black phosphorus, and the very few reduction production efficiency of black phosphorus is low.Power when ultrasound removing is 5W
~50W, splitting time are 5 minutes~60 minutes.
It specifically, further include black to expanding before expansion black phosphorus and oil-dissolving solvent being mixed the step of carrying out ultrasound removing
The step of phosphorus is isolated and purified, wherein the step of isolating and purifying includes: the anode removed in reaction system, then by reactant
System is centrifuged, and obtains filter residue, cleans filter residue, the expansion black phosphorus purified.Wherein, in the step of cleaning filter residue, make
Filter residue is cleaned with organic solvent；Organic solvent is selected from N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N- methyl
At least one of pyrrolidones (NMP) and tetrahydrofuran (THF).
Specifically, oil-dissolving solvent is selected from n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N- methyl pyrrole
At least one of pyrrolidone (NMP) and tetrahydrofuran (THF).More specifically, oil-dissolving solvent with cleaning filter residue it is organic molten
Agent is identical, is conducive to material analysis, while being also convenient for experimental implementation.It is appreciated that oil-dissolving solvent and cleans the organic of filter residue
Solvent can also be different.
Step S130: the heterocycle organic matter hybrid reaction of slurry and sulfur-bearing and nitrogen will be removed, obtains black phosphorus nanometer sheet.
It is the black phosphorus nanometer sheet of ion salt covalent modification by the black phosphorus nanometer sheet that step S130 is obtained.Specifically, it will shell
The heterocycle organic matter hybrid reaction step of syneresis material and sulfur-bearing and nitrogen are as follows: slurry and sulfur-bearing and nitrogen will be removed at normal temperatures and pressures
Heterocycle organic matter is stirred to react.Further, the time being stirred to react is 2 hours~10 hours.
Specifically, the molar ratio of the heterocycle organic matter of expansion black phosphorus and sulfur-bearing and nitrogen is 0.1:1~10:1.
Specifically, the heterocycle organic matter of sulfur-bearing and nitrogen be selected from 1,3- bis- (2,4,6- trimethylphenyl) chlorination benzothiazole,
One of N- methyl-N- sulfonic acid butyl benzo carbazole and N- methyl-N- carboxylic acid ethyl's benzo carbazole.
Specifically, step S110, step S120 and step S130 is carried out under conditions of air.
The preparation method of above-mentioned black phosphorus nanometer sheet by will by using black phosphorus as cathode, and with above-mentioned ionic liquid or on
Stating quaternary ammonium salt solution is electrolyte, is electrochemically reacted with anodal closure, to obtain expanded graphite, lead to will expansion black phosphorus and
Oil-dissolving solvent mixing carries out ultrasonic removing, obtains removing slurry, and removing slurry is mixed with the heterocycle organic matter of sulfur-bearing and nitrogen
Reaction, to obtain the black phosphorus nanometer sheet of ion salt covalent modification, the experiment proved that, the black phosphorus nanometer chip architecture it is relatively stable and
It is dispersed preferable.
The black phosphorus nanometer sheet that the preparation method of the black phosphorus nanometer sheet of one embodiment is prepared, the black phosphorus nanometer chip architecture
It is relatively stable and dispersed preferable.
Application in above-mentioned black phosphorus nanometer sheet scene effect transistor.Since above-mentioned black phosphorus nanometer sheet has excellent dispersion
Property and structural stability feature, be conducive to the high speed migration in its hole under electric field action, it is therefore, it is brilliant using scene effect
It can make field effect transistor that there is highly sensitive photoresponse ability in body pipe.
The following are specific embodiment part, (following embodiment unless otherwise specified, does not then contain and removes inevitable impurity
Other components not yet explicitly pointed out in addition.):
1~embodiment of embodiment 3
The preparation process of the black phosphorus nanometer sheet of the present embodiment 1~3 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 1, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using DMF, obtains expansion black phosphorus.
(2) according to table 1, under air conditions, expansion black phosphorus and DMF that mass volume ratio is M:A are blended in the function of 25W
Ultrasound removing 10 minutes under rate, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 1
Object is stirred to react 6 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 1
Molar ratio.
Table 1
Embodiment 4 and embodiment 5
The preparation process of the black phosphorus nanometer sheet of the present embodiment 4 and 5 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 1, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using DMSO, obtains expansion black phosphorus.
(2) according to table 1, under air conditions, expansion black phosphorus and DMSO that mass volume ratio is M:A are blended in the function of 5W
Ultrasound removing 60 minutes under rate, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 1
Object is stirred to react 10 hours, obtains black phosphorus nanometer sheet.
Embodiment 6 and embodiment 7
The preparation process of the black phosphorus nanometer sheet of embodiment 6 and embodiment 7 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 1, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using NMP, obtains expansion black phosphorus.
(2) according to table 1, under air conditions, expansion black phosphorus and NMP that mass volume ratio is M:A are blended in the function of 50W
Ultrasound removing 5 minutes under rate, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 1
Object is stirred to react 2 hours, obtains black phosphorus nanometer sheet.
8~embodiment of embodiment 9
The preparation process of the black phosphorus nanometer sheet of embodiment 8~9 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 1, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using THF, obtains expansion black phosphorus.
(2) according to table 1, under air conditions, expansion black phosphorus and THF that mass volume ratio is M:A are blended in the function of 30W
Ultrasound removing 20 minutes under rate, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 1
Object is stirred to react 8 hours, obtains black phosphorus nanometer sheet.
Embodiment 10
The preparation process of the black phosphorus nanometer sheet of embodiment 10 is roughly the same with embodiment 3, and difference is, the difference of voltage,
The voltage of embodiment 10 is 12V.
Embodiment 11
The preparation process of the black phosphorus nanometer sheet of embodiment 11 is roughly the same with embodiment 2, and difference is, the difference of voltage,
The voltage of embodiment 11 is 0.8V.
12~embodiment of embodiment 14
The preparation process of the black phosphorus nanometer sheet of embodiment 12~14 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 2, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using DMF, obtains expansion black phosphorus.
(2) according to table 2, under air conditions, expansion black phosphorus and DMF that mass volume ratio is M:A are mixed, and in 25W
Power under ultrasound removing 10 minutes, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 2
Object is stirred to react 6 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 2
Molar ratio.
Table 2
Embodiment 15 and embodiment 16
The preparation process of the black phosphorus nanometer sheet of the present embodiment 15 and 16 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 2, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using DMSO, obtains expansion black phosphorus.
(2) according to table 2, under air conditions, expansion black phosphorus and DMSO that mass volume ratio is M:A are mixed, and in 50W
Power under ultrasound removing 5 minutes, obtain removing slurry.Wherein, M:A is the quality for expanding black phosphorus and oil-dissolving solvent in table 2
Volume ratio.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 2
Object is stirred to react 10 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 2
Molar ratio.
Embodiment 17 and embodiment 18
The preparation process of the black phosphorus nanometer sheet of embodiment 17 and embodiment 18 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 2, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using NMP, obtains expansion black phosphorus.
(2) according to table 2, under air conditions, expansion black phosphorus and NMP that mass volume ratio is M:A are mixed, and 5W's
Ultrasound removing 60 minutes under power, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 2
Object is stirred to react 2 hours, obtains black phosphorus nanometer sheet.
19~embodiment of embodiment 20
The preparation process of the black phosphorus nanometer sheet of embodiment 19~20 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 2, black phosphorus and anode are placed in electrolyte, and right
Black phosphorus and anode apply certain voltage to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system into
Row centrifuge separation, obtains filter residue, cleans filter residue using THF, obtains expansion black phosphorus.
(2) according to table 2, under air conditions, expansion black phosphorus and THF that mass volume ratio is M:A are mixed, and in 20W
Power under ultrasound removing 40 minutes, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 2
Object is stirred to react 8 hours, obtains black phosphorus nanometer sheet.
Embodiment 21
The preparation process substantially phase of the black phosphorus nanometer sheet of the preparation process and embodiment 12 of the black phosphorus nanometer sheet of the present embodiment
Together, difference is, the concentration of the solute of electrolyte is 11g/mL.
Embodiment 22 and embodiment 23
The preparation process of the black phosphorus nanometer sheet of embodiment 22 and embodiment 23 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 3, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using DMF, obtain expansion black phosphorus.
(2) according to table 3, expansion black phosphorus and DMF that mass volume ratio is M:A are mixed, and the ultrasound stripping under the power of 25W
From 10 minutes, removing slurry is obtained.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 3
Object is stirred to react 4 hours, obtains black phosphorus nanometer sheet.Wherein, M:N is that the heterocycle for expanding black phosphorus and sulfur-bearing and nitrogen has in table 3
The molar ratio of machine object.
Table 3
Embodiment 24 and embodiment 25
The preparation process of the black phosphorus nanometer sheet of the present embodiment 24 and embodiment 25 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 3, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using DMSO, obtain expansion black phosphorus.
(2) according to table 3, under air conditions, black phosphorus will will be expanded for M:A according to mass volume ratio and DMSO is mixed, and
Ultrasound removing 20 minutes under the power of 30W, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 3
Object is stirred to react 10 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 3
Molar ratio.
Embodiment 26 and embodiment 27
The preparation process of the black phosphorus nanometer sheet of embodiment 26 and embodiment 27 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 3, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using NMP, obtain expansion black phosphorus.
(2) according to table 3, under air conditions, expansion black phosphorus and NMP that mass volume ratio is M:A are mixed, and 5W's
Ultrasound removing 60 minutes under power, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 3
Object is stirred to react 2 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 3
Molar ratio.
Embodiment 28 and embodiment 29
The preparation process of the black phosphorus nanometer sheet of embodiment 28 and embodiment 29 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 3, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using THF, obtain expansion black phosphorus.
(2) according to table 3, under air conditions, expansion black phosphorus and THF that mass volume ratio is M:A are mixed, and in 50W
Power under ultrasound removing 5 minutes, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 3
Object is stirred to react 8 hours, obtains black phosphorus nanometer sheet.
Embodiment 30
The preparation process substantially phase of the black phosphorus nanometer sheet of the preparation process and embodiment 23 of the black phosphorus nanometer sheet of embodiment 30
Together, difference is, the current density of embodiment 30 is 0.8mA/cm2。
Embodiment 31
The preparation process substantially phase of the black phosphorus nanometer sheet of the preparation process and embodiment 24 of the black phosphorus nanometer sheet of embodiment 31
Together, difference is, the current density of embodiment 31 is 105mA/cm2。
Embodiment 32 and embodiment 33
The preparation process of the black phosphorus nanometer sheet of embodiment 32 and embodiment 33 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 4, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using DMF, obtain expansion black phosphorus.
(2) according to table 4, under air conditions, expansion black phosphorus and DMF that mass volume ratio is M:A are mixed, and in 25W
Power under ultrasound removing 10 minutes, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 4
Object is stirred to react 4 hours, obtains black phosphorus nanometer sheet.Wherein, M:N is that the heterocycle for expanding black phosphorus and sulfur-bearing and nitrogen has in table 4
The molar ratio of machine object.
Table 4
Embodiment 34 and embodiment 35
The preparation process of the black phosphorus nanometer sheet of the present embodiment 34 and embodiment 35 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 4, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using DMSO, obtain expansion black phosphorus.
(2) according to table 4, under air conditions, black phosphorus will will be expanded for M:A according to mass volume ratio and DMSO is mixed, and
Ultrasound removing 30 minutes under the power of 25W, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 4
Object is stirred to react 10 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 4
Molar ratio.
Embodiment 36 and embodiment 37
The preparation process of the black phosphorus nanometer sheet of embodiment 36 and embodiment 37 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 4, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using NMP, obtain expansion black phosphorus.
(2) according to table 4, expansion black phosphorus and NMP that mass volume ratio is M:A are mixed, and the ultrasound stripping under the power of 25W
From 15 minutes, removing slurry is obtained.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 4
Object is stirred to react 2 hours, obtains black phosphorus nanometer sheet.M:N is the heterocycle organic matter for expanding black phosphorus and sulfur-bearing and nitrogen in table 4
Molar ratio.
Embodiment 38 and embodiment 39
The preparation process of the black phosphorus nanometer sheet of embodiment 38 and embodiment 39 is as follows:
(1) in the condition of air, using black phosphorus as cathode, according to table 4, black phosphorus and anode are placed in electrolyte, and to black
Phosphorus and anode apply the electric current of certain density to be electrochemically reacted, and obtain reaction system, take anode away, then by reaction system
It is centrifuged, obtains filter residue, clean filter residue using THF, obtain expansion black phosphorus.
(2) according to table 4, under air conditions, expansion black phosphorus and THF that mass volume ratio is M:A are mixed, and in 25W
Power under ultrasound removing 12 minutes, obtain removing slurry.
(3) at normal temperatures and pressures that the heterocycle for removing slurry and sulfur-bearing and nitrogen is organic under conditions of air according to table 4
Object is stirred to react 8 hours, obtains black phosphorus nanometer sheet.
Embodiment 40
The preparation process of the black phosphorus nanometer sheet of the present embodiment is roughly the same with embodiment 35, and difference is, expansion black phosphorus with
The molar ratio M:N of the heterocycle organic matter of sulfur-bearing and nitrogen is difference, and the M:N of the present embodiment is 11:1.
Comparative example 1
Comparative example 1 is the two-dimentional black phosphorus of traditional direct ultrasound removing.
Test:
Fig. 1 is that Raman (Raman) spectrogram for the black phosphorus nanometer sheet that embodiment 1 is prepared (is swashed when test using 523nm
Radiant), in figure bulk, IL, 2L, 3L, 4L and 5L respectively indicate after unstripped block black phosphorus, removing have a layer thickness,
The black phosphorus nanometer sheet of two layers of thickness, threeply degree, four thickness degree and five thickness degree.Si is that Raman spectrum is used when testing in figure
Substrate, obtained stripping nano sheet material, which must load to generate, plays the role of support in the silicon base of interference.In Fig. 1
It can be seen that the black phosphorus nanometer sheet that experiment obtains from single layer to multilayer, is located at 361.2cm in figure-1、439.5cm-1And 468.6cm-1
Three typical raman characteristic peaks correspond to three phonon modes in black phosphorus structure: the outer A of planeg 1, B in plane2gAnd Ag 2This three
Kind lattice vibration mode illustrates that the black phosphorus nanometer sheet that removing obtains has high crystallinity, and crystallinity is preferable.
Fig. 2 is transmission (TEM) electron microscope for the black phosphorus nanometer sheet that embodiment 1 is prepared, and illustrates the black phosphorus material of preparation
It is a nanometer chip architecture.Fig. 3 is the electron diffraction diagram that Fig. 2 corresponds to constituency, and clearly spot illustrates the monocrystalline state of material, further
The black phosphorus nanometer sheet for illustrating that removing obtains is highly crystalline.Fig. 4 is the enlarged drawing that Fig. 2 amplifies 1000 times, can from figure
Black phosphorus nanometer sheet has clearly lattice fringe and interplanar distance out, and without visible lattice defect, stable structure, and black phosphorus is received
(021) of rice piece and the interplanar distance of (041) two crystal face are respectivelyWith
The black phosphorus nanometer sheet of 2~embodiment of embodiment 40 has similar with the black phosphorus nanometer sheet that embodiment 1 is prepared
Raman spectrogram, electron diffraction diagram and transmission electron microscope picture, details are not described herein, wherein the black phosphorus nanometer sheet of Examples 1 to 40
Crystallization situation and stable structure situation are shown in Table 5.
Dispersibility test: the black phosphorus nanometer sheet for respectively preparing Examples 1 to 40 is 10mg:40mL according to mass volume ratio
Ultrasound is dispersed in methyl pyrrolidone for 0.5 hour, respectively obtains dispersion liquid and the comparison of the black phosphorus nanometer sheet of Examples 1 to 40
Then the dispersion liquid of the two-dimentional black phosphorus of example 1 stands 12 hours, then whether directly observation bottom has precipitating, if bottom does not occur
The dispersibility that precipitating has had.Wherein, traditional two-dimentional black phosphorus of the black phosphorus nanometer sheet of Examples 1 to 40 and comparative example 1
It is dispersed as shown in table 5.
Hole mobility test: the two dimension of the dispersion liquid of the black phosphorus nanometer sheet of above-described embodiment 1~40 and comparative example 1 is black
The dispersion liquid of phosphorus is spun to SiO2It is about 300 nanometers thick in/Si substrate, and copper mesh is covered above, counter electrode is that Cr/Au is thin
Film (wherein, Cr layers with a thickness of 3nm, Au layers with a thickness of 50nm), is fabricated to field effect transistor, by Examples 1 to 40 respectively
The corresponding field effect transistor of the two-dimentional black phosphorus of black phosphorus nanometer sheet and comparative example 1 is connected on 4200 semiconductor analysis instrument of Keithly
Test the hole mobility of each field effect transistor.Wherein, Fig. 5 is the corresponding field effect transistor of black phosphorus nanometer sheet of embodiment 1
The histogram of the hole mobility of pipe, is computed, and the mean void mobility of the field effect transistor of embodiment 1 is 60cm2·V-1·s-1, wherein the black phosphorus nanometer sheet of embodiment 2~40 and traditional corresponding field effect transistor of two-dimentional black phosphorus of comparative example 1
The mean void mobility of pipe is as shown in table 5.
Wherein, the yield of the black phosphorus nanometer sheet of Examples 1 to 40 is also recorded in table 5.
Table 5
As can be seen from Table 5, the black phosphorus nanometer sheet of Examples 1 to 40 has high crystallinity, and has than comparative example 1
The good dispersibility of two-dimentional black phosphorus, and the mean void of the corresponding field effect transistor of black phosphorus nanometer sheet of Examples 1 to 40 is moved
Shifting rate is at least 20cm2·V-1·s-1, mean void mobility with higher.
Wherein, the black phosphorus nanometer of Examples 1 to 9,12~20,22~29 and 32~39 not only has preferable dispersibility,
And black phosphorus nanometer sheet of the mean void mobility than embodiment 10,11,21,30,31 and 40 is high.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of black phosphorus nanometer sheet, which comprises the steps of:
Using black phosphorus as cathode, the black phosphorus and anode are placed in electrolyte, and to the black phosphorus and the anodal closure with
It being electrochemically reacted, obtains expansion black phosphorus, the electrolyte is ionic liquid, alternatively, the electrolyte is quaternary ammonium salt solution,
The ionic liquid is selected from 1- ethyl-3-methylimidazole bromide, 1- ethyl-3-methylimidazole villaumite, 1- ethyl-3-methylimidazole
Salt compounded of iodine, 1- ethyl -2,3- methylimidazole fluoroform sulphonate, 1,2- diethyl -3- methylimidazole fluoroform sulphonate, 1,2-
Dimethyl -3- ethyl imidazol(e) bromide, 1,2- dimethyl -3- ethyl imidazol(e) villaumite and 1,-dimethyl -3- ethyl imidazol(e) tetrafluoro boric acid
At least one of salt；The solute of the quaternary ammonium salt solution is selected from 1- ethyl -3- methyl ammonium tetrafluoroborate, normal-butyl tetrachloric acid
At least one of ammonium, normal-butyl ammonium tetrafluoroborate and normal-butyl tetrafluoro ammonium phosphate；
The expansion black phosphorus and oil-dissolving solvent are mixed and carry out ultrasonic removing, obtains removing slurry；And
By the heterocycle organic matter hybrid reaction of the removing slurry and sulfur-bearing and nitrogen, the black phosphorus nanometer sheet is obtained.
2. the preparation method of black phosphorus nanometer sheet according to claim 1, which is characterized in that described to the black phosphorus and described
The step of anodal closure is to be electrochemically reacted are as follows: the voltage of 1V~10V is applied to carry out to the black phosphorus and the anode
Electrochemical reaction.
3. the preparation method of black phosphorus nanometer sheet according to claim 1, which is characterized in that described to the black phosphorus and described
The step of anodal closure is to be electrochemically reacted are as follows: applying density to the black phosphorus and the anode is 1mA/cm2~
100mA/cm2Electric current to be electrochemically reacted.
4. the preparation method of black phosphorus nanometer sheet according to claim 1, which is characterized in that it is described by the expansion black phosphorus and
Oil-dissolving solvent mixing carries out further including the steps that isolating and purifying the expansion black phosphorus before the step of ultrasound removing, institute
Stating the step of isolating and purifying includes: the anode in the removal reaction system, then the reaction system is carried out centrifugation point
From, filter residue is obtained, the filter residue is cleaned, the expansion black phosphorus purified.
5. the preparation method of black phosphorus nanometer sheet according to claim 1, which is characterized in that described to the black phosphorus and described
The step of anodal closure is to be electrochemically reacted, described mix the expansion black phosphorus and oil-dissolving solvent carry out ultrasonic removing
The step of and it is described by the step of heterocycle organic matter hybrid reaction of the removing slurry and sulfur-bearing and nitrogen be item in air
It is carried out under part.
6. the preparation method of described in any item black phosphorus nanometer sheets according to claim 1~5, which is characterized in that the expansion is black
The molar ratio of the heterocycle organic matter of phosphorus and the sulfur-bearing and nitrogen is 0.1:1~10:1.
7. the preparation method of described in any item black phosphorus nanometer sheets according to claim 1~5, which is characterized in that the oil-soluble
Solvent is selected from least one of N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone and tetrahydrofuran；And/
Or, the concentration of the solute of the quaternary ammonium salt solution is 0.05g/mL~10g/mL；And/or the solvent choosing of the quaternary ammonium salt solution
From one of N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone and tetrahydrofuran.
8. the preparation method of described in any item black phosphorus nanometer sheets according to claim 1~5, which is characterized in that the anode choosing
From one of platinum, graphite carbon rod and graphene paper.
9. the black phosphorus nanometer sheet that the preparation method of black phosphorus nanometer sheet according to any one of claims 1 to 8 is prepared.
10. black phosphorus nanometer sheet as claimed in claim 9 is preparing the application in field effect transistor.
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