CN102849732B - Method for realizing double-surface asymmetric modification of single-layer graphene - Google Patents
Method for realizing double-surface asymmetric modification of single-layer graphene Download PDFInfo
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Abstract
The invention discloses a method for realizing the asymmetric covalent modification of single-layer graphene, which comprises the following steps: (1) preparing graphene on a substrate; (2) performing covalent chemical modification on the surface of the graphene to obtain single-surface modified graphene; (3) spin coating a PMMA (polymethyl methacrylate) solution on the surface of the single-surface modified graphene, baking the PMMA to form a thin polymer film, and then etching the substrate in a hydrofluoric acid water solution to separate the graphene from the substrate; (4) using the thin PMMA film as a protective base, and performing covalent chemical modification different from the method in the step (2) on the other side of the single-surface modified graphene to realize the double-surface asymmetric modification of the graphene; and (5) transferring the double-surface asymmetric modified graphene to the surface of another substrate, and removing the thin PMMA film to obtain the double-surface asymmetric modified graphene. By using the thin PMMA film as the operating medium, the method first realizes the double-surface asymmetric covalent modification of single-layer graphene, and is suitable for any graphene covalent modification method.
Description
Technical field
The present invention relates to a kind of method realizing the two-sided asymmetric modification of single-layer graphene.
Background technology
Graphene has stable Colloidal particles and excellent electricity, mechanical property, and its synthesis, character and application are the problems jointly paid close attention to of scientific circles and industrial community in recent years.As desirable two-dimensional atomic crystal, more than carrier mobility 2 orders of magnitude higher than traditional silicon material of Graphene, in addition its flexible and good light transmission, be subject to worldwide great attention as flexible transparent conductive film material on the one hand, the elementary material on the other hand as following nanometer electronic device has vast potential for future development.
Graphene comes from the essential characteristic of its zero band gap at one of the application institute facing challenges of devices field.Covalently chemical functionalized is a kind of effective ways that can realize Graphene band gap easy, on a large scale and open, and in addition, utilizes covalent modification can also design and synthesis graphite ene derivative, regulates and controls its optics, mechanics and surface properties simultaneously.Developed graphite alkene covalently chemical functionalized method within the scope of our times, such as hydrogenation, fluoridize, chlorination, diazonium salt addition and various cycloaddition reaction.Single-layer graphene is two-dimension plane structure, double side chemical modifies (modification group is dispersed in graphene sheet layer both sides uniformly) can obtain higher modification efficiency relative to one side modification, thus significantly promotes covalent modification to the ability of Graphene band engineering.The main stream approach realizing Graphene double measure at present utilizes the groove of substrate or the unsettled single-layer graphene of pore space structure, enables reactant realize two-sided reaction from the upper and lower both sides Graphene of attack simultaneously.Because the chemical environment of two side reactions is consistent, this method only can realize the double-sided symmetrical sex modification of single-layer graphene, and namely the modification group of both sides is identical up and down.
Summary of the invention
The object of this invention is to provide a kind of method realizing the two-sided asymmetric covalent modification of Graphene.
The method realizing the asymmetric covalent modification of Graphene using polymethylmethacrylate (PMMA) film as manipulation medium provided by the invention, comprises the steps:
1) on substrate, Graphene is prepared;
2) carry out covalently chemical functionalized at graphenic surface, under the protection of substrate, realize the one side chemically modified of Graphene;
3) PMMA solution is spin-coated to step 2) graphenic surface after the one side chemically modified that obtains, baking PMMA makes it to solidify to form polymeric film; Then etched substrate in hydrofluoric acid aqueous solution, the reactive force between release liners and Graphene, simultaneously realizes being separated of the Graphene after modifying and substrate with PMMA film for supporting;
4) using PMMA film as protectiveness substrate, continue the opposite side of Graphene after one side is modified and carry out and step 2) in the different secondary covalently chemical functionalized of covalently chemical functionalized method, realize the two-sided asymmetric modification of Graphene;
5) Graphene of two-sided asymmetric modification is transferred to another substrate surface, utilizes acetone steam to remove PMMA film, discharge the Graphene of asymmetric modification.
The step 1 of the method)-2) in, described substrate is Si and SiO
2compound substrate (the i.e. Si/SiO of composition
2substrate), wherein, SiO
2substrate layer contacts with graphene sheet layer.Conventional SiO
2layer thickness is 300nm; Because Si layer is as supporting layer, its concrete thickness can be determined according to actual needs, and conventional Si substrate layer thickness is 600 μm.
Described Graphene specifically can be single-layer graphene.
The method that substrate prepared single-layer graphene be following method a) or b) in any one:
A) at Si and SiO
2single-layer graphene is prepared in the mode of mechanically peel in the compound substrate surface of composition;
Be specially: directly pipette the viscous surface of a certain amount of Kish graphite to scotch tape, the stripping utilizing the method for adhesive tape doubling repeatedly to realize Kish graphite is sprawled, and is transferred to Si and SiO
2the compound substrate surface of composition, obtains single-layer graphene.
B) Si and SiO is transferred to after chemical vapor deposition growth Graphene
2the compound substrate surface of composition;
Be specially: carry out chemical vapor deposition growth at copper foil surface (thickness is 25 μm) using methane as carbon source, single-layer graphene separated out on copper surface, then Graphene is transferred to Si/SiO
2on substrate.
Step 3) in, the weight-average molecular weight of PMMA is 950K, and liquid quality fraction is 4wt%; Spin coating rate selection 1000 ~ 3500r/min, preferred 2000r/min, spin-coating time is 45 ~ 60s; Storing temperature is set as 170 DEG C, and the time is 5 ~ 15min, preferred 10min.Hydrofluoric acid aqueous solution massfraction is 2wt%, and etching time is 5 ~ 15min.
Above-mentioned steps 2) and step 4) in, at the covalently chemical functionalized that graphenic surface carries out, existing Graphene covalently chemical functionalized method can be adopted as required to carry out the modification of different properties group.
As step 2) in, optical chlorinating reaction can be carried out at graphenic surface, obtain the Graphene that one side chlorination is modified.
Concrete modifying method is as follows: adopt nitrogen as carrier gas, chlorine to be passed into the photochemical reaction system of Graphene, and under the irradiation of UV-light, chlorine decomposes the chlorination reaction producing chlorine radical initiation Graphene; Wherein, ultraviolet source wave band is 250 ~ 450nm, and the illumination reaction time is 3 ~ 8min, light intensity 900mW/cm
2.
Step 4) in, after realizing being separated of Graphene and substrate, using PMMA film as protectiveness substrate, secondary covalently chemical functionalized is carried out on the surface exposed at Graphene, modifies or nitrophenylization is modified as phenylating.
Concrete modifying method is as follows:
A) phenylating of Graphene is modified: adopt benzoyl peroxide (BPO) molecule as initiator, produce benzene radical and be added to graphenic surface under laser radiation.
B) nitrophenylization of Graphene is modified: the diazonium salt molecule adopting p-nitrophenyl is initiator, carries out the diazonium salt addition reaction of Graphene in aqueous.
Step 5) in, substrate is Si and SiO
2the compound substrate of composition, the Graphene of wherein asymmetric modification and SiO
2layer fits tightly.
The present invention utilizes PMMA film to achieve the two-sided asymmetric modification of Graphene as manipulation medium.The method is applicable to any Graphene covalent modification means, can prepare graphite ene derivative structure.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet realizing the two-sided asymmetric covalent modification of single-layer graphene using PMMA film as manipulation medium.
Fig. 2 is that the Raman spectrum modified respectively by the upper and lower surface of single-layer graphene in chlorine and phenyl process changes and structural representation.
Fig. 3 is atomic force microscope images after the two-sided asymmetric modification chlorine of single-layer graphene and phenyl and elevation carrection.
Fig. 4 is the x-ray photoelectron power spectrum after the two-sided asymmetric modification chlorine of single-layer graphene and oil of mirbane.
Embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Provided by the invention using PMMA film as manipulation medium realize the schematic flow sheet of the two-sided asymmetric covalent modification of single-layer graphene as shown in Figure 1, wherein, numbering 1 is Si/SiO
2substrate, numbering 2 is single-layer graphene, the single-layer graphene that numbering 3 is modified for one side chlorination, numbering 4 is for handling medium-PMMA film, numbering 5 is the single-layer graphene of two-sided asymmetric modification, and numbering 6 is after removing PMMA, the single-layer graphene structure of asymmetric covalent modification.Wherein, steps A is the one side chlorination modification of substrate surface single-layer graphene; Step B is spin coating, baking PMMA film, and realizes being separated of chlorination Graphene and substrate with PMMA film in a solution of hydrofluoric acid for supporting, and step C is that phenylating/nitrophenylization of PMMA film surface Graphene is modified, and step D is the removal of PMMA.
Embodiment 1, two-sided asymmetric covalent modification is carried out to single-layer graphene
1) at Si/SiO
2(Si layer thickness is 600 μm to substrate, SiO
2substrate layer is 300nm) surface adopts the mode of mechanically peel to prepare single-layer graphene, and wherein Fig. 2 (a) is the Raman spectrogram of substrate surface single-layer graphene.
2) carry out optical chlorinating reaction on single-layer graphene surface, under the protection of substrate, realize the chlorination of Graphene one side modify.Concrete implementation step is:
Adopt dilute hydrochloric acid (9mol/L) and manganese dioxide powder (5g) at 60 DEG C, react obtained chlorine, nitrogen is adopted as carrier gas, new preparing chlorine gas to be passed into the photochemical reaction system of Graphene, under the irradiation of UV-light, chlorine decomposes the chlorination reaction producing chlorine radical initiation Graphene.Wherein, ultraviolet source wave band is 250 ~ 450nm, and the illumination reaction time is 3 ~ 8min, light intensity 900mW/cm
2.Wherein Fig. 2 (b) is the Raman spectrogram after the chlorination of Graphene one side is modified, and as seen from the figure, the carbon atom of sp3 configuration has appearred in graphenic surface, proves the formation of carbon-chlorine covalent linkage.
3) at the graphenic surface spin coating PMMA solution that one side chlorination is modified, rotating speed 2000r/min, spin-coating time 1min; Storing temperature selects 170 DEG C, and the time is 10min.Sample after spin coating is soaked in 5 ~ 15min in hydrofluoric acid aqueous solution (2%wt), utilizes hf etching SiO
2layer realizes being separated of substrate and chlorination Graphene.
4) with PMMA film for protectiveness substrate, the opposite side grapheme modified in chlorination carries out phenylating modification, obtains the single-layer graphene of two-sided asymmetric covalent modification.Concrete implementation step is:
Sample is placed in the aqueous isopropanol of benzoyl peroxide (BPO), concentration selects 0.5mmol/L, and soak time is 30min.Taking-up carries out phenylating reaction under being placed on laser, and optical maser wavelength is 514nm, light intensity 0.5mW, and irradiation time is set as 0.7s.Because laser facula size is only 1 ~ 2 μm, thus need to adopt the mode of laser scanning to obtain the Graphene of the asymmetric modification of large area two-side.After reaction terminates, be soaked in by sample in aqueous isopropanol and remove remaining BPO molecule, soak time is 1h.
5) Graphene of two-sided asymmetric modification is transferred to Si/SiO
2compound substrate surface, utilizes acetone steam to remove PMMA film.Wherein, Fig. 2 (c) is the Raman spectrogram of two-sided asymmetric covalent modification Graphene, and as seen from the figure, the atom ratio of sp3 configuration increases further, proves that benzene radical is added to graphenic surface.
Fig. 3 is Si/SiO
2the atomic force microscope images (height phase) of the single-layer graphene of the compound substrate two-sided asymmetric modification in surface, measures the single-layer graphene height after obtaining asymmetric modification at 1.6nm.
Embodiment 2, two-sided asymmetric covalent modification is carried out to single-layer graphene
1) carry out chemical vapor deposition growth at copper foil surface, single-layer graphene is separated out on copper surface, Graphene is transferred to another sheet Si/SiO
2on substrate.Wherein, annealing temperature is 1000 DEG C, and growing environment is low pressure environment (500mTorr), and carbon source adopts methane, and growth atmosphere is methane 35sccm/ hydrogen 2sccm.
2)-3) step is with embodiment 1.
4) with PMMA film for protectiveness substrate, the opposite side grapheme modified in chlorination carries out nitrophenyl modification, obtains the single-layer graphene of two-sided asymmetric covalent modification.Concrete implementation step is:
Sample is placed in the p-nitrophenyl diazonium salt solution that concentration is 20mmol/L, temperature controls at 40 DEG C, reaction times 1-2h.After reaction terminates, be soaked in by sample in deionized water and remove remaining diazonium salt molecule, soak time is 2 hours.
5) Graphene of two-sided asymmetric covalent modification is transferred to Si/SiO
2compound substrate surface, utilizes acetone steam to remove PMMA film.Wherein, Fig. 4 is Si/SiO
2the x-ray photoelectron energy spectrogram of single-layer graphene after the two-sided asymmetric modification on compound substrate surface, as seen from the figure, the graphenic surface of asymmetric modification, simultaneously containing chlorine element and nitrogen element, proves that chlorine and nitrophenyl are added to graphenic surface simultaneously.
Claims (3)
1. realize a method for the two-sided asymmetric covalent modification of Graphene, comprise the steps:
1) on substrate, Graphene is prepared;
2) carry out covalently chemical functionalized at graphenic surface, obtain the Graphene that one side is modified;
3) polymethyl methacrylate solution is spin-coated to step 2) graphenic surface that the one side that obtains is modified, toasts described polymethylmethacrylate and makes it to solidify to form polymethyl methacrylate film; Then etched substrate in hydrofluoric acid aqueous solution, makes Graphene and substrate separation;
4) using polymethyl methacrylate film as protectiveness substrate, continue the opposite side of Graphene after modifying one side to carry out and step 2) in the different secondary covalently chemical functionalized of covalently chemical functionalized method, realize the two-sided asymmetric covalent modification of Graphene;
5) Graphene of two-sided asymmetric covalent modification is transferred to another substrate surface, removing polymethyl methacrylate film, obtains the Graphene of two-sided asymmetric covalent modification;
Step 1) described in substrate be Si and SiO
2the compound substrate of composition, wherein, SiO
2substrate layer contacts with described graphene sheet layer; Described Graphene is single-layer graphene;
Step 3) described in the weight-average molecular weight of polymethylmethacrylate be 950K; The massfraction of described polymethyl methacrylate solution is 4%, and spin coating speed is 1000 ~ 3500r/min, and the time is 45 ~ 60s; The temperature of described baking is 170 DEG C, and the time is 5 ~ 15min;
Step 3) described in the massfraction of hydrofluoric acid solution be 2%, etching time is 5 ~ 15min;
Step 5) in the Graphene of two-sided asymmetric covalent modification is transferred to Si/SiO
2substrate surface, Graphene and SiO
2substrate layer contacts;
Step 5) described in polymethyl methacrylate film adopt acetone steam removing.
2. method according to claim 1, is characterized in that: step 2) described in covalently chemical functionalized be chlorination modify; Concrete modifying method is as follows: adopt nitrogen as carrier gas, chlorine to be passed into the photochemical reaction system of Graphene, and under the irradiation of UV-light, chlorine decomposes the chlorination reaction producing chlorine radical initiation Graphene; Wherein, the light source wave band of described UV-light is 250 ~ 450nm, and irradiation time is 3 ~ 8min, and the light intensity of UV-light is 900mW/cm
2.
3. method according to claim 1, is characterized in that: step 4) in, described secondary covalently chemical functionalized is that Graphene phenylating is modified or nitrophenylization is modified;
The method that described Graphene phenylating is modified is as follows: adopt benzoyl peroxide molecule as initiator, produce benzene radical and be added to graphenic surface under laser radiation;
The method that described Graphene nitrophenylization is modified is as follows: the diazonium salt molecule adopting p-nitrophenyl is initiator, carries out the diazonium salt addition reaction of Graphene in aqueous.
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| EP3936476A1 (en) * | 2020-07-08 | 2022-01-12 | Valstybinis Moksliniu Tyrimu Institutas Fiziniu Ir Technologijos Mokslu Centras | Method of polymethylmethacrylate (pmma) removal from a graphene surface by photoexposure |
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| US11479466B2 (en) * | 2014-08-08 | 2022-10-25 | Olanrewaju W. Tanimola | Methods for synthesis of graphene derivatives and functional materials from asphaltenes |
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| EP3936476A1 (en) * | 2020-07-08 | 2022-01-12 | Valstybinis Moksliniu Tyrimu Institutas Fiziniu Ir Technologijos Mokslu Centras | Method of polymethylmethacrylate (pmma) removal from a graphene surface by photoexposure |
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