CN108622865A - A kind of method of chemoproection black phosphorus - Google Patents

A kind of method of chemoproection black phosphorus Download PDF

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Publication number
CN108622865A
CN108622865A CN201710163991.9A CN201710163991A CN108622865A CN 108622865 A CN108622865 A CN 108622865A CN 201710163991 A CN201710163991 A CN 201710163991A CN 108622865 A CN108622865 A CN 108622865A
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black phosphorus
chemoproection
acetone
solution
boric acid
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CN201710163991.9A
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CN108622865B (en
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刘晶
范双青
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Tianjin University
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Tianjin University
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    • 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
    • C01B25/003—Phosphorus
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention provides a kind of method of chemoproection black phosphorus, includes the following steps：Sheet black phosphorus is immersed in 20 25 DEG C of immersions of room temperature in modification solution, the solute molar ratio of the modification solution is (1 50)：4 R, 2,2,6,6 tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon of (1 50), solvent is the mixed solution of the acetone and water of acetone or isometric ratio, after impregnating 5 10h, takes out sample, organic solvent washing, drying.The beneficial effects of the invention are as follows：For this method without being operated under the conditions of anhydrous and oxygen-free, operating process is simple, and this method will not have an adverse effect to the photoelectric property of black phosphorus, will not destroy black phosphorus crystal structure, not increase its surface roughness after black phosphorus chemoproection.

Description

A kind of method of chemoproection black phosphorus
Technical field
The invention belongs to field of photoelectric technology, more particularly, to a kind of method of chemoproection black phosphorus.
Background technology
Two-dimensional material, such as graphene, black phosphorus, transient metal sulfide, due to its special nature and in nanoelectronic Potential application greatly paid close attention to.Wherein, graphene, molybdenum disulfide, as representative two-dimensional material in flexibility Electronics, photodetector, electro-catalysis, the application fields such as gas sensing are widely studied.But graphene lacks band gap and seriously makes About its application in logic semiconductor, and the low electron mobility of molybdenum disulfide influences its electrical properties.Therefore it finds new Two semi-conducting materials of type seem particularly urgent.
Black phosphorus is as layered semiconductor material, with its larger on-off ratio, higher carrier mobility, accurate one-dimensional exciton Characteristic, adjustable direct band gap, by domestic and international extensive concern.However black phosphorus is easily aoxidized in air, it is serious to restrict It is studied and practical application.Although the method for available physical encapsulation protects black phosphorus, also constrain simultaneously black phosphorus device into one Step processing, and protecting effect is nor very ideal.Therefore there is an urgent need for a kind of method of chemoproection black phosphorus, black phosphorus is avoided to be aoxidized While, keep its excellent photoelectric property.
Invention content
In order to overcome the problems, such as that black phosphorus is easily aoxidized, the present invention provides a kind of methods of new chemoproection black phosphorus.
The technical scheme is that：A kind of method of chemoproection black phosphorus of the present invention, includes the following steps：
Sheet black phosphorus is immersed in modification solution and is in 20-25 DEG C of immersion of room temperature, the solute molar ratio of the modification solution (1-50)：The 4-R-2 of (1-50), 2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon, solvent are acetone or wait The acetone of volume ratio and the mixed solution of water after immersion, take out sample, organic solvent washing, drying.
Preferably, the sheet black phosphorus is by mechanically pulling off by blocky black phosphorus or ultrasound, the methods of mechanical agitation are decomposed and At.
Preferably, the soaking time is 6h-7h.
Preferably, the washing solution uses acetone or IPA (isopropanol).
Preferably, the drying operation is completed using nitrogen gun purging.
Preferably, 4-R-2 in the modification solution, 2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon Molar ratio is 1：1.
Preferably, the solute in the modification solution is 10mmol 4-R-2,2,6,6- tetramethyl piperidine oxides and three Phenyl tetrafluoro boric acid carbon, solvent are 1mL acetone and 1mL deionized waters.
Another aspect of the present invention further includes the black phosphorus protected through the above method, and the black phosphorus after protection is being placed 100 days Afterwards, lattice structure does not change, and roughness is without significant change.
Another aspect of the present invention further includes a kind of application for modifying solution on protection black phosphorus, the modification solution Solute is that molar ratio is (1-50)：The 4-R-2 of (1-50), 2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon, Solvent is the mixed solution of the acetone of isometric ratio or the acetone and water of isometric ratio.
Preferably, 4-R-2 in the modification solution, 2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon Molar ratio is 1：1.
The invention has the advantages and positive effects that：
1, this method can both be protected single black phosphorus device, can also realize the change of high-volume black phosphorus in the solution Learn protection.
2, for this method without being operated under the conditions of anhydrous and oxygen-free, operating process is simple, and stream can be completed without professional Journey.
3, this method will not have an adverse effect to the photoelectric property of black phosphorus, will not destroy black phosphorus crystal structure.
4, its surface roughness is not increased after black phosphorus chemoproection.
Description of the drawings
Fig. 1 is that 0day (a), 100day (b) atomic force microscope are placed in black phosphorus air of the embodiment 1 after chemoproection Figure.
Fig. 2 is that 0day (a), 100day (b) atomic force microscope are placed in black phosphorus air of the embodiment 1 without chemoproection Figure.
Fig. 3 be embodiment 1 through (a) before chemoproection, after (b) black phosphorus Raman spectrum curve graph.
Fig. 4 is the atom of the 120th day (b) after being placed on the 0th day (a) under air environment after 2 black phosphorus of embodiment is modified and protecting Force microscope figure, and without modification black phosphorus in air expose the 0th day (c) and the 4th day (d) atomic force microscopy diagram.
Fig. 5 is the Raman of the 120th day (b) after being placed on the 0th day (a) under air environment after 2 black phosphorus of embodiment is modified and protecting Spectral curve.
Fig. 6 is embodiment 2 to be exposed the black phosphorus Raman light of the 0th day (a) and the 4th day (b) without modification black phosphorus and sets a song to music in air Line chart.
Specific implementation mode
It elaborates below in conjunction with the accompanying drawings to the present invention.
2,2,6,6- tetramethyl piperidine oxides are bought in Tianjin Heowns Biochemical Technology Co., Ltd., triphenyl tetrafluoro boron Sour carbon purchase is in uncommon love (Shanghai) the chemical conversion industry Development Co., Ltd of ladder.
Embodiment 1
(1) a small amount of blocky black phosphorus is placed on blue light adhesive tape, folded adhesive tape several times, will by dimethyl silicone polymer Sheet black phosphorus is transferred in Si/SiO2 substrates.
(2) 2,2,6,6- tetramethyl piperidine oxides (3.1mg, 2mmol), triphenyl tetrafluoro boric acid are added in brown bottle Carbon (6.6mg, 2mmol) and 1mL acetone, 1mL deionized waters, concussion make it dissolve.Sheet black phosphorus obtained by the above method is soaked Enter in solvent bottle, in soaking at room temperature 7h.
(3) substrate is pressed from both sides out with tweezers, dries up to obtain the black phosphorus of chemoproection through isopropanol washing, nitrogen gun.
It after thinned, has to organic solvent such as acetone, IPA etc. is rinsed well, and otherwise solvent volatilizees, and causes solute dense Spending moment becomes larger, and solute can rest on surface, to destroy black phosphorus surface.A large amount of solutes can also be agglomerated by obtaining black phosphorus surface, no Preferably remove.
Atomic force microscope uses Dimension Icon (Bruker, German), from Fig. 1-2 as can be seen that through chemistry Black phosphorus after protection is placed 100 days, and roughness does not have significant change from 0.609nm to 0.616nm, and without the black of protection Phosphorus is only placed one day, and roughness becomes 6.26nm from 0.257nm, illustrates that the present invention plays a very good protection to black phosphorus. Fig. 3 is to be located at 359cm through the forward and backward black phosphorus Raman spectrogram of chemoproection-1、436cm-1And 463cm-1Raman peaks difference The Ag of corresponding black phosphorus1、B2gAnd Ag2Peak, illustrating chemoproection, there is no destroy black phosphorus lattice structure.It draws after placing 100 days Graceful spectrum peak intensity does not have significant change, further illustrates the present invention and plays a very good protection to black phosphorus.
Embodiment 2
1) a small amount of blocky black phosphorus is placed on blue light adhesive tape, folded adhesive tape several times, by dimethyl silicone polymer, by piece Shape black phosphorus is transferred in Si/SiO2 substrates.
(2) 2,2,6,6- tetramethyl piperidine oxides (15.5mg, 10mmol), triphenyl tetrafluoro boron are added in brown bottle Sour carbon (33mg, 10mmol) and 1mL acetone, 1mL deionized waters, concussion make it dissolve.By sheet black phosphorus obtained by the above method It immerses in solvent bottle, in soaking at room temperature 7h.
(3) substrate is pressed from both sides out with tweezers, dries up to obtain the black phosphorus of chemoproection through isopropanol washing, nitrogen gun.
Fig. 5 is 10mM carbonium ions (triphenyl tetrafluoro boric acid carbon) and 10mMTEMPO (2,2,6,6- tetramethyl piperidines oxidations Object) water acetone soln to black phosphorus modify after, the aerial passivation effect of black phosphorus.
It is placed under air environment in the 0th day atomic force microscopy diagram such as Fig. 4 shown in a after black phosphorus modification, after black phosphorus modification It is placed under air environment in the 120th day atomic force microscopy diagram such as Fig. 4 shown in b, thickness is 3.2nm, no significant change.Figure 5 be their Raman spectrum respectively.Two curve co-insides, it is seen that the black phosphorus of modification is stablized under air environment.
It is exposed in air without modification black phosphorus in the 0th day atomic force microscopy diagram such as Fig. 4 shown in c, thickness 5.1nm, It is exposed in air without modification black phosphorus in the 4th day atomic force microscopy diagram such as Fig. 4 shown in d, thickness 4.1nm, it can be seen that, In air, surface is aoxidized unmodified black phosphorus, and thickness is lower, as shown in the Raman spectrogram of Fig. 6, it is seen that unmodified is black After phosphorus exposes 4 days in air, raman scattering intensity reduces, and thickness is lower, and surface is aoxidized.
One embodiment of the present invention has been described in detail above, but the content be only the present invention preferable implementation Example should not be construed as limiting the practical range of the present invention.It is all according to all the changes and improvements made by the present patent application range Deng should all still fall within the scope of the patent of the present invention.

Claims (10)

1. a kind of method of chemoproection black phosphorus, it is characterised in that：Include the following steps：Sheet black phosphorus is immersed in modification solution In 20-25 DEG C of immersion of room temperature, the solute molar ratio for modifying solution is (1-50)：The 4-R-2,2,6,6- tetramethyls of (1-50) Piperidine oxide and triphenyl tetrafluoro boric acid carbon, solvent are the mixed solution of the acetone and water of acetone or isometric ratio, impregnate 5- After 10h, sample, organic solvent washing, drying are taken out.
2. a kind of method of chemoproection black phosphorus according to claim 1, it is characterised in that：The sheet black phosphorus is by bulk Black phosphorus is by mechanically pulling off or ultrasound, the methods of mechanical agitation are decomposed.
3. a kind of method of chemoproection black phosphorus according to claim 1, it is characterised in that：The soaking time is 6- 7h。
4. according to claim 1, it is characterised in that：The washing solution uses acetone or isopropanol.
5. a kind of method of chemoproection black phosphorus according to claim 1, it is characterised in that：The drying operation uses nitrogen Air gun purging is completed.
6. a kind of method of chemoproection black phosphorus according to claim 1, it is characterised in that：4-R- in the modification solution 2,2,6,6- tetramethyl piperidine oxides and the molar ratio of triphenyl tetrafluoro boric acid carbon are 1：1.
7. a kind of method of chemoproection black phosphorus according to claim 1, it is characterised in that：It is molten in the modification solution Matter is 10mmol 4-R-2,2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon, and solvent is 1mL acetone and 1mL Deionized water.
8. the black phosphorus protected by any one of claim 1-7 methods, it is characterised in that：Black phosphorus after protection is placing 100 After it, lattice structure does not change, and roughness is without significant change.
9. a kind of application of modification solution on protection black phosphorus, it is (1-50) that the solute of the modification solution, which is molar ratio,：(1- 50) 4-R-2,2,6,6- tetramethyl piperidine oxides and triphenyl tetrafluoro boric acid carbon, solvent are the acetone and water of isometric ratio Mixed solution or acetone soln.
10. a kind of application of the modification solution according to claim 9 on protection black phosphorus, it is characterised in that：The modification 4-R-2,2,6,6- tetramethyl piperidine oxides and the molar ratio of triphenyl tetrafluoro boric acid carbon are 1 in solution：1.
CN201710163991.9A 2017-03-17 2017-03-17 Method for chemically protecting black phosphorus Expired - Fee Related CN108622865B (en)

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Cited By (1)

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CN109825800A (en) * 2019-01-03 2019-05-31 南京大学 A kind of method of polymer protection arsenic alkene nanometer sheet

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