CN105752967A - Preparation method of graphene conducting film - Google Patents
Preparation method of graphene conducting film Download PDFInfo
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- CN105752967A CN105752967A CN201610061583.8A CN201610061583A CN105752967A CN 105752967 A CN105752967 A CN 105752967A CN 201610061583 A CN201610061583 A CN 201610061583A CN 105752967 A CN105752967 A CN 105752967A
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Abstract
The invention relates to a preparation method of a graphene conducting film. The preparation method comprises the steps of preparing graphite oxide, assembling a graphene oxide film and reducing the graphene oxide film. Graphite powder forms graphite oxide under the effect of a strong oxidant; the graphite oxide is subjected to ultrasonic centrifugation to form a graphene oxide colloidal solution; then, electrolyte is dripped into the graphene oxide colloidal solution so that the graphene oxide colloidal solution generates flocculated sediments; meanwhile, a pretreated substrate with two-dimensional or three-dimensional structures and the graphene oxide complete the self-assembly process to obtain the graphene oxide film; finally, oxygen-containing functional groups in the graphene oxide film is removed by a heat treatment or chemical reduction method, so that the graphene conducting film is prepared. The preparation method of the graphene conducting film provided by the invention has the advantages that the step of transferring the prepared graphene onto a target substrate by a vapour deposition process is avoided; in addition, the graphene conducting film with the complicated two-dimensional or three-dimensional substrate structure can be prepared.
Description
Technical field
The present invention relates to technical field of semiconductor, the preparation method particularly relating to a kind of graphene conductive film.
Background technology
Graphene is that carbon atom is with sp2Hybrid orbital is the monolayer two dimensional crystal that honeycomb lattice is arranged to make up.Since within 2004, being found, the multiple excellent specific property of Graphene is also exploited gradually.The nano material that world that Graphene is known is thin, the hardest, its fracture strength is 42N/m2, Young's modulus reaches 7TPa, intensity up to 130GPa, when being same test more than 100 times of hardness of steel.Graphene has good light transmission, and the optical absorptivity of visible ray and infrared light is only 2.3%.Under room temperature, the electron mobility of Graphene is more than 15000cm2/ V s, resistivity is only 10-6Ω/cm, lower than copper and Yin Geng, it is the material that resistivity is minimum in the world at present, therefore Graphene can maintain significantly high electric conductivity.The connection between carbon atom within Graphene is very pliable and tough, when applying external force in Graphene, carbon atom face meeting flexural deformation so that carbon atom need not be rearranged to adapt to external force, thus keeping Stability Analysis of Structures, this stable lattice structure makes Graphene have good intensity and flexibility.Therefore, Graphene is excellent and the optics of uniqueness, electricity and mechanical characteristic have attracted the extensive concern of scientific circles and industrial quarters, be with a wide range of applications in fields such as photoelectric device, ultracapacitor, Flexible Displays, nanometer electronic device, intelligence sensor, biosensors.
At present, the Main Means preparing Graphene has mechanical phonograph recorder separation, oxidation-reduction method and chemical vapour deposition technique.Chemical vapour deposition technique is to utilize the hydrocarbon gas such as methane, ethylene to be at high temperature adsorbed on catalyst metals substrate surface the method for decomposition under metal catalytic effect, restructuring formation Graphene.Chemical vapour deposition technique can prepare the Graphene of larger area compared to mechanical separation and oxidation-reduction method, therefore suffers from the especially concern of scientist, but, chemical vapour deposition technique itself also has very big defect.General chemical vapour deposition technique carries out in high temperature furnace, and after growth terminates, the Graphene of growth is attached on catalyst metals completely, Graphene practical application prepared by this method will be also needed to an extra transfer step on device.Transfer typically requires at FeCl3Solution soaks more than ten hours to etch away catalyst metals substrate, then fish for by target substrate again, and Graphene is dried.Transfer process is time and effort consuming not only, and wayward, also can introduce exogenous impurity, even cause the destruction of Graphene, and these impurity and defect will directly affect the electrical properties of Graphene.Therefore it provides a kind of method that can directly form Graphene in target substrate is technical problem urgently to be resolved hurrily.
The preparation method that Chinese patent (publication No. is CN103778995A) discloses a kind of transparent graphene conductive film based on silicon dioxide substrates.The method includes preparing on the metallic substrate transparent graphene conductive film, to form the first substrate；Then on transparent graphene conductive film, preparing silicon dioxide substrates, finally etching away metal substrate, thus obtaining the transparent graphene conductive film based on silicon dioxide substrates.This patent avoids the Graphene transfer step being difficult in prior art, in that context it may be convenient to prepare the transparent graphene conductive film based on silicon dioxide substrates, can reduce cost simultaneously.But, the method still has the step of etching metal substrate, and etching metal substrate easily makes impurities left on transparent graphene conductive film, affects the character of graphene conductive film.
On the other hand, along with the development of science and technology and application demand, traditional planar graphene film can not meet requirement, is frequently encountered by the situation needing to cover graphene film at complicated three dimensional structure substrate surface.Current conventional techniques is to be directly transferred to two-dimensional graphene to have in the target substrate of three-dimensional surface structure, but, this method is difficult to accomplish to cover graphene film on the surface of three dimensional structure comprehensively.Additionally, planar graphene film is easily broken under the effect of external force or damages, and then cause that the various good characteristics of structure and graphene film are unstable.Therefore, exploitation one has the coplanar shape graphene film of flexible 3 D becomes problem demanding prompt solution, utilizes the device that Flexible graphene thin film makes to have the features such as collapsible, stretchable, lightweight, non-friable, is suitable for the development and application of flexible electronic.
Summary of the invention
Deficiency for prior art, the preparation method that the invention provides a kind of graphene conductive film, described method includes the preparation of graphite oxide, the assembling of graphene oxide film and the reduction of graphene oxide film, by graphite powder being formed under strong oxidizer effect graphite oxide, and described graphite oxide is formed graphene oxide colloid solution after ultrasonic being centrifuged, electrolyte is dripped again so that the flocculation of described graphene oxide colloid solution deposits in described graphene oxide colloid solution, the substrate with two dimension or three dimensional structure good for pretreatment and described graphene oxide are completed self assembling process simultaneously and prepare described graphene oxide film, method finally by heat treatment or electronation removes the oxygen-containing functional group in described graphene oxide film, thus preparing described graphene conductive film.Preferably, described strong oxidizer is one or more in nitric acid, concentrated sulphuric acid, potassium permanganate, potassium dichromate, sodium hypochlorite, sodium nitrate and hydrogen peroxide, and described electrolyte is aqueous solution of nitric acid.
According to a preferred implementation, the described substrate with two dimension or three dimensional structure is metallic substrates, further, according to the material properties of described metallic substrates and required physical dimension select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode prepare described in there is the metallic substrates of two dimension or three dimensional structure.Preferably, described metallic substrates is at the bottom of cuprio, at the bottom of nickel substrate, aluminium substrate, titanio and the stainless steel-based end.
According to a preferred implementation, after the described metallic substrates with two dimension or three dimensional structure soaks 30～60min in one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution after sandblasting, again by described metallic substrates acetone, ethanol and deionized water ultrasonic cleaning 2～5min respectively, dry standby.
nullAccording to a preferred implementation，The described substrate with two dimension or three dimensional structure is flexible substrates，The described flexible substrates with two dimension or three dimensional structure is to prepare as follows: choose a metal material as the first substrate，And select photoetching according to the material properties of described first substrate and the physical dimension of required flexible substrates、Dry etching、Wet etching、Nano impression、Mask、Ion beam direct write、Self assembly or mechanical precision machined mode prepare first substrate with two dimension or three dimensional structure，Described first substrate with two dimension or three dimensional structure revolves the flexible polymer of one layer of 50～100 μ m-thick，And the first substrate being rotary with flexible polymer is placed in baking oven and is dried by described flexible polymer，Again the structure of described flexible polymer/the first substrate with two dimension or three dimensional structure is placed in metal etch solution and is fallen by described first substrate etching.Preferably, described flexible polymer is PDMS performed polymer, PET performed polymer, PP performed polymer, PE performed polymer, UV optic-solidified adhesive or PUA heat-curable glue.Preferably, described metal etch solution is one or more in ferric nitrate, Ammonium persulfate., copper chloride, sulphuric acid, chromic acid, hydrogen peroxide.
According to a preferred implementation, by the following method the described flexible substrates with two dimension or three dimensional structure is carried out pretreatment: after the described flexible substrates with two dimension or three dimensional structure is carried out sided corona treatment or chemical attack frosted process, be coated with adhensive membrane, and, described adhensive membrane is the one in thermosetting resin and thermoplastic resin, and the thickness of described adhensive membrane is 1～5 μm；Or the described flexible substrates with two dimension or three dimensional structure is inserted in plasma processor, adopts oxygen to process 40～80S when power is 30～100W；Dry standby after the flexible substrates deionized water described in pretreated with two dimension or three dimensional structure is cleaned.Preferably, described adhensive membrane is polyvinyl butyral resin or ethyl cellulose.
According to a preferred implementation, the preparation of described graphite oxide comprises the steps: to be placed in reactor by graphite powder, sodium nitrate and concentrated sulphuric acid, and at the temperature of 0～10 DEG C, dripping potassium permanganate while stirring, the time for adding of described potassium permanganate is 10～20min；In described reactor, pass into nitrogen and the temperature in described reactor is increased to 35 DEG C, continuing stirring 20～30min；In described reactor, add deionized water, the temperature in described reactor is increased to 85～95 DEG C simultaneously, continue stirring 35～45min；In described reactor, add hydrogen peroxide, then add deionized water and be diluted, be stirred simultaneously；After described reactor is naturally cooled to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide.
According to a preferred implementation, described graphite powder, described sodium nitrate, described concentrated sulphuric acid mass ratio be 1～4: 0.5～2: 40～100；The mass ratio of described graphite powder and described potassium permanganate is 1: 3；The mass ratio of described graphite powder and described deionized water is 1: 50～60, and, described deionized water adds in described reactor at twice；The mass ratio of described graphite powder and described hydrogen peroxide is 1: 15～20.
According to a preferred implementation, the assembling of described graphene oxide film comprises the steps: to add in reactor by described graphite oxide, and carrying out ultrasonic cleaning 40～60min by the amount that mass ratio is 1: 1500～2000 described deionized water of addition of described graphite oxide and deionized water, the turbid solution that described graphite oxide is formed through ultrasonic cleaning is centrifuged separating treatment 10～20min again；By being dissolved with the solution collection of graphene oxide and adding standing 30～60min after aqueous solution of nitric acid stirs after centrifugation, carry out after flocculation sediment process through aqueous solution of nitric acid, collect the graphene oxide of lower floor；By collect described graphene oxide be inverted in standby described in have in the substrate of two dimension or three dimensional structure, and make described graphene oxide formed liquid membranaceous, be placed in again after naturally drying in vacuum tank dry, obtain graphene oxide film；Or the described substrate with two dimension or three dimensional structure is dipped vertically in the described graphene oxide of collection and vertically there is the substrate of two dimension or three dimensional structure described in lift, make described graphene oxide transfer to described in have in the substrate of two dimension or three dimensional structure, naturally it is placed in vacuum tank after drying again dry, obtains graphene oxide film.
According to a preferred implementation, the reduction of described graphene oxide film comprises the steps: to put in tube furnace by described graphene oxide film, argon is passed into again after evacuation, repeatedly it is warming up to 800～1100 DEG C under an argon atmosphere after twice, and namely heat treatment 1～1.5h obtains graphene conductive film at such a temperature.
According to a preferred implementation, the preparation method of described graphene conductive film is as follows: be placed in reactor at 2: 1: 80 in mass ratio by graphite powder, sodium nitrate and concentrated sulphuric acid, and at the temperature of 10 DEG C, dripping the potassium permanganate of described graphite powder consumption 3 times while stirring, the time for adding of described potassium permanganate is 10min；In described reactor, pass into nitrogen again and by the temperature in described reactor to 35 DEG C, continue stirring 30min；In described reactor, add the deionized water of described graphite powder consumption 35 times again, the temperature in described reactor is increased to 90 DEG C simultaneously, continue stirring 40min；Adding the hydrogen peroxide of described graphite powder consumption 18 times again in described reactor, the deionized water adding described graphite powder consumption 20 times is diluted, and is stirred simultaneously；After described reactor is naturally cooled to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide.After one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution after there is after processed the metallic substrates sandblasting of two dimension or three dimensional structure soak 30min, by described, there is the metallic substrates acetone of two dimension or three dimensional structure, ethanol and deionized water ultrasonic cleaning 2min respectively again, and dry up with nitrogen standby；nullOr，Choose a metal material as the first substrate，And select photoetching according to the material properties of described first substrate and the physical dimension of required flexible substrates、Dry etching、Wet etching、Nano impression、Mask、Ion beam direct write、Self assembly or mechanical precision machined mode prepare first substrate with two dimension or three dimensional structure，Described first substrate with two dimension or three dimensional structure revolves the PDMS performed polymer of one layer of 50～100 μ m-thick、PET performed polymer、PP performed polymer、PE performed polymer、UV optic-solidified adhesive or PUA heat-curable glue，And described first substrate with two dimension or three dimensional structure is placed in baking oven by PDMS performed polymer、PET performed polymer、PP performed polymer、PE performed polymer、UV optic-solidified adhesive or PUA heat-curable glue are dried，Again the structure of described flexible polymer/the first substrate with two dimension or three dimensional structure is placed in metal etch solution and falls to prepare the flexible substrates with two dimension or three dimensional structure by described first substrate etching，It is coated with adhensive membrane after the described flexible substrates with two dimension or three dimensional structure is carried out sided corona treatment or chemical attack frosted process，The thickness of described adhensive membrane is 1～5 μm，Or the described flexible substrates with two dimension or three dimensional structure is inserted in plasma processor，Adopt oxygen，40～80S is processed so that the described flexible substrates with two dimension or three dimensional structure is carried out pretreatment when power is 30～100W，After the flexible substrates deionized water described in pretreated with two dimension or three dimensional structure is cleaned standby；Being added in reactor by described graphite oxide, and add deionized water ultrasonic cleaning 60min by the amount that mass ratio is 1: 2000 of described graphite oxide and described deionized water, the turbid solution formed through ultrasonic cleaning is centrifuged separating treatment 10min again；By being dissolved with the solution collection of graphene oxide and adding standing 30min after aqueous solution of nitric acid stirs after centrifugation, carry out after flocculation sediment process through aqueous solution of nitric acid, collect the graphene oxide of lower floor；Described graphene oxide is inverted in the standby substrate with two dimension or three dimensional structure, and it is membranaceous to make described graphene oxide form liquid, be placed in vacuum tank after naturally drying again dry, obtain graphene oxide film；Or the described substrate with two dimension or three dimensional structure is dipped vertically in the described graphene oxide of collection and vertically there is the substrate of two dimension or three dimensional structure described in lift, make described graphene oxide transfer to described in have in the substrate of two dimension or three dimensional structure, naturally it is placed in vacuum tank after drying again dry, obtains graphene oxide film；Described graphene oxide film is put in tube furnace, after evacuation, passes into argon again, be repeatedly warming up to 900～1100 DEG C according to the speed of 5～10 DEG C/min under an argon atmosphere after twice, and namely heat treatment 1～1.5h obtains graphene film at such a temperature.
The preparation method of a kind of graphene conductive film provided by the invention at least has the advantage that
(1) present invention can be implemented in target substrate is directly formed graphene conductive film, it is to avoid the graphene conductive film prepared is transferred to the problem causing graphene conductive film hydraulic performance decline in target substrate.
(2) present invention can according to the application of graphene conductive film, choose metallic substrates or flexible substrates, the substrate of two dimension or three dimensional structure can also be prepared according to the application demand of graphene conductive film, considerably increase the range of application of graphene conductive film.
(3) by the metallic substrates or flexible substrates with two dimension or three dimensional structure are carried out pretreatment, substrate is made to have excellent adhesiveness, the caking property of graphene conductive film and substrate can be increased, it is to avoid cover suprabasil graphene conductive film and produce defect.
Accompanying drawing explanation
Fig. 1 is the sectional view processing three-dimensional substrates according to one embodiment of present invention；
Fig. 2 is that the three-dimensional substrates of Fig. 1 is at the view processing in step with later；
Fig. 3 is that the three-dimensional substrates of Fig. 2 is at the view processing in step with later；
Fig. 4 is that the three-dimensional substrates of Fig. 3 is at the view processing in step with later；
Fig. 5 is that the three-dimensional substrates of Fig. 4 is at the view processing in step with later；
Fig. 6 is that the three-dimensional substrates of Fig. 5 is at the view processing in step with later；
Fig. 7 is that the three-dimensional substrates of Fig. 6 is at the view processing in step with later；
Fig. 8 is that the three-dimensional substrates of Fig. 7 is at the view processing in step with later.
Reference numerals list
10: substrate 101: the first pattern 102: the second pattern
20: the first screen layer 30: the first mask layer 40: the second mask layers
50: the second pattern masks 60: planar film 70: secondary shielding layer
80: the first pattern masks 601: raised design
Detailed description of the invention
It is described in detail below in conjunction with embodiment and accompanying drawing.
The preparation method that the invention provides a kind of graphene conductive film, the method includes the reduction of the preparation of graphite oxide, the assembling of graphene oxide film and graphene oxide film.First, graphite powder forms graphite oxide under strong oxidizer effect.Secondly, graphite oxide forms graphene oxide colloid solution after ultrasonic being centrifuged, and drips electrolyte and can make graphene oxide colloid solution flocculation deposition in graphene oxide colloid solution.Again, the substrate with two dimension or three dimensional structure good for pretreatment and graphene oxide are completed self assembling process and prepare graphene oxide film.Finally, remove the oxygen-containing functional group in graphene oxide film by the method for heat treatment or electronation, thus preparing graphene conductive film.
According to a preferred implementation, the preparation method of graphene conductive film is as follows.It is be placed in reactor at 2: 1: 80 in mass ratio by graphite powder, sodium nitrate and concentrated sulphuric acid.Dripping the potassium permanganate of graphite powder consumption 3 times at the temperature of 10 DEG C while stirring, the time for adding of potassium permanganate is 10min.In reactor, pass into nitrogen and by the temperature in reactor to 35 DEG C, continue stirring 30min.In reactor, add the deionized water of graphite powder consumption 35 times, the temperature in reactor is increased to 90 DEG C simultaneously, continue stirring 40min.Adding the hydrogen peroxide of graphite powder consumption 18 times in reactor, the deionized water adding graphite powder consumption 20 times is diluted, and is stirred simultaneously.After reactor is naturally cooled to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide.After one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution after there is after processed the metallic substrates sandblasting of two dimension or three dimensional structure soak 30min, to there is the metallic substrates acetone of two dimension or three dimensional structure, ethanol and deionized water ultrasonic cleaning 2min respectively again, and dry up with nitrogen standby.Or, choose a metal material as the first substrate, and select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode to prepare first substrate with two dimension or three dimensional structure according to the material properties of the first substrate and the physical dimension of required flexible substrates.First substrate with two dimension or three dimensional structure revolves the PDMS performed polymer of one layer of 50～100 μ m-thick, PET performed polymer, PP performed polymer, PE performed polymer, UV optic-solidified adhesive or PUA heat-curable glue.First substrate with two dimension or three dimensional structure is placed in baking oven PDMS performed polymer, PET performed polymer, PP performed polymer, PE performed polymer, UV optic-solidified adhesive or PUA heat-curable glue are dried.The structure with flexible polymer/the first substrate of two dimension or three dimensional structure is placed in metal etch solution and falls to prepare the flexible substrates with two dimension or three dimensional structure by the first substrate etching.It is coated with adhensive membrane after the flexible substrates with two dimension or three dimensional structure is carried out sided corona treatment or chemical attack frosted process.The thickness of adhensive membrane is 1～5 μm.Or the flexible substrates with two dimension or three dimensional structure is inserted in plasma processor, adopts oxygen to process 40～80S when power is 30～100W so that the flexible substrates with two dimension or three dimensional structure is carried out pretreatment.By standby after the pretreated flexible substrates deionized water cleaning with two dimension or three dimensional structure.Graphite oxide is added in reactor, and adds deionized water ultrasonic cleaning 60min by the amount that mass ratio is 1: 2000 of graphite oxide and deionized water.The turbid solution formed through ultrasonic cleaning is centrifuged separating treatment 10min again.The solution collection of graphene oxide will be dissolved with and add standing 30min after aqueous solution of nitric acid stirs after centrifugation.Carry out after flocculation sediment process through aqueous solution of nitric acid, collect the graphene oxide of lower floor.Graphene oxide is inverted in the standby substrate with two dimension or three dimensional structure, and it is membranaceous to make graphene oxide form liquid, be placed in vacuum tank after naturally drying again dry, obtain graphene oxide film.Or the substrate with two dimension or three dimensional structure is dipped vertically in the graphene oxide of collection and vertically lifts the substrate with two dimension or three dimensional structure, graphene oxide is made to transfer in the substrate with two dimension or three dimensional structure, naturally it is placed in vacuum tank after drying again dry, obtains graphene oxide film.Graphene oxide film is put in tube furnace, after evacuation, pass into argon again, be repeatedly warming up to 900～1100 DEG C according to the speed of 5～10 DEG C/min under an argon atmosphere after twice, and namely heat treatment 1～1.5h obtains graphene film at such a temperature.
Preparation method provided by the invention can realize directly being formed graphene conductive film in target substrate, avoid and the graphene conductive film prepared is transferred to the problem causing graphene conductive film hydraulic performance decline in target substrate, simultaneously, the substrate of the graphene conductive film of the present invention can be metallic substrates or flexible substrates, may also be two dimension substrate or three-dimensional substrates, graphene conductive film prepared by the present invention can be applied, it is also possible in the micro-nano device of development of new in multiple fields such as photoelectric device, MEMS, intelligent sensing, electronic skin.
Embodiment 1
Preparation for graphite oxide.
The preparation of graphite oxide carries out in four-hole boiling flask, is respectively provided with nitrogen tube, addition funnel, agitator and water circulating condensing pipe on four-hole boiling flask top.The preparation of graphite oxide specifically includes following steps:
S1: be 1～4: 0.5～2: 40～100 weigh graphite powder, sodium nitrate and concentrated sulphuric acid in mass ratio, addition funnel be sequentially added in four-hole boiling flask.Preferably, the consumption of graphite powder is 3.0g, and the consumption of sodium nitrate is 1.5g, and the consumption of concentrated sulphuric acid is 65mL.
S2: four-hole boiling flask is placed on the beaker filling mixture of ice and water, turn on agitator, it is stirred 3～5min, makes the solution mix homogeneously in four-hole boiling flask.When temperature in four-hole boiling flask drops to below 10 DEG C, add potassium permanganate while stirring, and continue stirring 10min.Preferably, the consumption of potassium permanganate is 9.0g.
S3: transferred to by four-hole boiling flask in oil bath cylinder, opens nitrogen tube input nitrogen.Preferably, the input speed of nitrogen is 20cm3/min.Simultaneously open water circulating condensing pipe and electric controller successively, makes the temperature in four-hole boiling flask be increased to 35 DEG C, and continues stirring 30min.
S4: being added deionized water by addition funnel in four-hole boiling flask, add while stirring, in four-hole boiling flask, solution becomes glassy yellow.Preferably, the addition of deionized water is 100mL.While continuing to unlatching electric controller, make the temperature of four-hole boiling flask be increased to 90 DEG C, and continue stirring 40min.
S5: added hydrogen peroxide by addition funnel in four-hole boiling flask, be stirred simultaneously, then add deionized water and be diluted.Preferably, the addition of hydrogen peroxide is 50mL, and the addition of deionized water is 60mL.
S6: close electric controller, agitator, water circulating condensing pipe and nitrogen tube, make the mixed solution in four-hole boiling flask naturally cool to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide.
Graphite issues biochemical reaction in strong oxidizer effect and generates graphite oxide, and reaction equation is as follows:
Embodiment 2
There is the metallic substrates of two dimension or three dimensional structure for preparation.
The two-dimensional structure of metallic substrates is random two-dimensional planar structure.The three dimensional structure of metallic substrates includes but not limited to convex configuration, concave structure, pore space structure, curved-surface structure, optical grating construction, optical waveguide structure, photon crystal structure and fishing net shaped structure.The two dimension of metallic substrates or three dimensional structure are of a size of nanoscale, micron order or macro-scale.The preparation of the metallic substrates with two dimension or three dimensional structure specifically includes following steps:
S1: choose a metal material as substrate, and metallic substrates is processed into two dimension or three dimensional structure.Preferably, metallic substrates be at the bottom of cuprio, at the bottom of nickel substrate, aluminium substrate, titanio, the stainless steel-based end or other alloy substrates.Material properties and required physical dimension according to metallic substrates select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode to be processed as two dimension or three dimensional structure.Specifically, the method that can adopt wet etching will be processed as required two dimension or three dimensional structure at the bottom of cuprio, it is possible to adopt nano impression, the method for mask will prepare into required three dimensional structure at the bottom of cuprio.The method preparation that can adopt precise electrotyping has the nickel substrate of three dimensional structure.
The two dimension of S2:S1 gained or the metallic substrates of three dimensional structure soak 40min after sandblasting in one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution.Preferably, the granularity after metallic substrates sandblasting is 100～200 orders.Preferably, when metallic substrates is the titanium alloy-based end, the solution chosen is the aqueous solution of 2wt% sodium hydroxide, 2wt% hydrogen peroxide.When metallic substrates is the stainless steel-based end, the solution chosen is 10wt% phosphoric acid, 10wt% salt aqueous acid.
S3: by the metallic substrates of the two dimension after immersion or three dimensional structure again with acetone, ethanol and deionized water ultrasonic cleaning 2～5min respectively, dry standby.
Embodiment 3
For preparation, there is the three-dimensional substrates protruding patterning below.
Fig. 8 illustrates that the present embodiment has the sectional view of the three-dimensional substrates protruding patterning.As shown in Figure 8, the base material of three-dimensional substrates is metallic substrates.Preferably, metallic substrates is at the bottom of cuprio, at the bottom of nickel substrate, aluminium substrate, titanio and the stainless steel-based end.It is formed with the first pattern 101 and the second pattern 102 on the substrate 10.Wherein, the first pattern 101 is for repeating area of the pattern, and the second pattern 102 is pattern interruptive area.According to a preferred implementation, three-dimensional substrates as shown in Figure 8 is formed as follows:
As it is shown in figure 1, set gradually the first mask layer 30 and the second mask layer 40 again on the first screen layer 20 after arranging the first screen layer 20 by the mode of rotation on the substrate 10, and the second pattern mask 50 is set on the second mask layer 40.Preferably, the first screen layer 20 is rotation carbon.The thickness of the first screen layer 20 is 50～500 angstroms.The material of the first mask layer 30 and the second mask layer 40 is rich in silicon, oxygen, nitrogen compound, and thickness is 50～500 angstroms, and, the first mask layer 30 and the second mask layer 40 also include antireflection figure layer.Second pattern mask 50 is identical with the size of the second pattern 102, and, the second pattern mask 50 also includes photoresist.
As in figure 2 it is shown, by using the second pattern mask 50 to be removed by second pattern mask 50 again after making the second mask layer 40 patterning.Concrete, the second area of the pattern in the second mask layer 40 is covered by the second pattern mask 50, and makes the first area of the pattern reveal.By this step, the second mask layer 40 can be made to form the second pattern mask at the second area of the pattern.
As shown in Figure 3, on planar film 60, secondary shielding layer 70 and the first pattern mask 80 is set gradually again after second mask layer 40 of the first mask layer 30 and patterning forms a layer plane film 60, further, the thickness of planar film 60 is more than the thickness of the second mask layer 40 of patterning.Preferably, by the mode thickness of deposition 50～2500 angstroms on the second mask layer 40 of the first mask layer 30 and patterning revolved, then again by the material planarization of rotation to form planar film 60.The thickness of secondary shielding layer 70 is 50～500 angstroms, and secondary shielding layer 70 has anti-reflection function.First pattern mask 80 includes photoresist.The size of the first pattern mask 80 is identical with the first pattern 101.
As shown in Figure 4, by using the first pattern mask 80 to be removed by first pattern mask 80 again after making secondary shielding layer 70 patterning.Pattern on secondary shielding layer 70 is for repeating area of the pattern.Preferably, the first pattern mask 80 is etched secondary shielding layer 70 so that secondary shielding layer 70 patterns as module.
As it is shown in figure 5, by using the secondary shielding layer 70 of patterning as module etched plane film 60 and to make the secondary shielding layer 70 that planar film 60 will be patterned into after forming repeat patterns region again remove.The thickness of the planar film 60 of patterning is more than the thickness of the second mask layer 40 of patterning.The planar film 60 of patterning comprises relevant to the second mask layer 40 of picture a pair raised design 601.Preferably, raised design 601 two edges each extending to exceed the second mask layer 40 of picture therein, as shown in Figure 5；Or raised design 601 one of them extend to more than the edge of the second mask layer 40 of picture；Or raised design 601 two edges all not extending to exceed the second mask layer 40 of picture therein.
As shown in Figure 6, the second mask layer 40 that will be patterned into and the planar film 60 of patterning, as composite module, adopt the method for etching to make the first mask layer 30 pattern.Preferably, raised design 601 trimming at the second mask layer 40 edge of picture and/or shearing will be exceeded so that the edge of raised design 601 is concordant with the edge of the second mask layer 40 of patterning before patterning the first mask layer 30.As shown in Figure 7 and Figure 8, the first mask layer 30 that will be patterned into, as module, is continuing with lithographic method and makes the first screen layer 20 and substrate 10 pattern.Preferably, it is also possible to mix mask by ion implantation technique or diffusion and make first mask layer the 30, first screen layer 20 and substrate 10 pattern.
The forming method of the three-dimensional substrates that the present embodiment provides only need to change the structure of mask, adopts method similar to the above, can form the 3-dimensional metal substrate of various structures.The method that the present embodiment provides, when forming the substrate of three dimensional structure, has various structures and will not destroy the advantage of base material structure.
Embodiment 4
There is the flexible substrates of two dimension or three dimensional structure for preparation.
The two-dimensional structure of flexible substrates is random two-dimensional planar structure.The three dimensional structure of flexible substrates includes but not limited to convex configuration, concave structure, pore space structure, curved-surface structure, optical grating construction, optical waveguide structure, photon crystal structure and fishing net shaped structure.The two dimension of flexible substrates or three dimensional structure are of a size of nanoscale, micron order or macro-scale.The preparation of the flexible substrates with two dimension or three dimensional structure specifically includes following steps:
S1: choose a metal material as the first substrate, and the first substrate is processed into two dimension or three dimensional structure.Preferably, the first substrate be at the bottom of cuprio, at the bottom of nickel substrate, aluminium substrate, titanio, the stainless steel-based end or other alloy substrates.Material properties and the physical dimension of required flexible substrates according to the first substrate select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode to be processed as two dimension or three dimensional structure.Specifically, the method that can adopt wet etching will be processed as required two dimension or three dimensional structure at the bottom of cuprio, it is possible to adopt nano impression, the method for mask will prepare into required three dimensional structure at the bottom of cuprio.The method preparation that can adopt precise electrotyping has the nickel substrate of three dimensional structure.Specifically, the three dimensional structure of the first substrate can adopt the method described in embodiment 3 to prepare.
S2: revolve the flexible polymer of one layer of 50～100 μ m-thick in the two dimension of S1 gained or the first substrate of three dimensional structure.Preferably, flexible polymer is PDMS performed polymer, PET performed polymer, PP performed polymer, PE performed polymer, UV optic-solidified adhesive or PUA heat-curable glue.The first substrate being rotary with flexible polymer is placed in baking oven and dries, obtain the structure of flexible polymer/the first substrate.Preferably, the temperature of baking oven is 80 DEG C.It is placed in metal etch solution to fall the first substrate etching by the structure of flexible polymer/the first substrate with two dimension or three dimensional structure after drying, to prepare the flexible substrates with two dimension or three dimensional structure.Preferably, the rotary rpm revolving flexible polymer on the first substrate is 100～1000r/min.The thickness of the flexible polymer of rotation is nanoscale or micron order.Preferably, described metal etch solution is one or more in ferric nitrate, Ammonium persulfate., copper chloride, sulphuric acid, chromic acid, hydrogen peroxide.It is highly preferred that metal etch solution is ferric nitrate or Ammonium persulfate..
S3: the S2 flexible substrates with two dimension or three dimensional structure prepared is carried out surface preparation.One of method carrying out surface preparation is to be coated with adhensive membrane after the flexible substrates with two dimension or three dimensional structure carries out sided corona treatment or chemical attack frosted process.Preferably, adhensive membrane is the one in thermosetting resin and thermoplastic resin.It is highly preferred that adhensive membrane is polyvinyl butyral resin or ethyl cellulose.Flexible substrates is carried out sided corona treatment or chemical attack frosted processes, it is possible to improve the adhesive force on flexible substrates surface.In order to obtain enough adhesions, the thickness of adhensive membrane is 1～5 μm.Graphene oxide film can more firm with flexible substrates must be connected by adhensive membrane, it is possible to avoids covering suprabasil graphene conductive film and produces defect.
The method carrying out surface preparation two is insert in plasma processor by the flexible substrates with two dimension or three dimensional structure, adopts oxygen to process 40～80S when power is 30～100W.Preferably, flexible substrates processes 60S when power is 50W.Plasma treatment mainly removes the impurity on flexible substrates surface, to improve the adhesion of flexible substrates and graphene oxide film.
S4: dry standby after the flexible substrates deionized water of the two dimension after carrying out surface preparation or three dimensional structure is cleaned.
Embodiment 5
It is reduced to example with the assembling of graphene oxide film and graphene oxide film.
On the basis of embodiment 1 and embodiment 2 or continue the preparation method of the graphene conductive film to the present invention on the basis of embodiment 1 and embodiment 3 and illustrate.
The assembling of graphene oxide film specifically includes following steps:
S1: the graphite oxide that embodiment 1 prepares is added in beaker, and in beaker, add deionized water, beaker is placed in the supersonic cleaning machine that power is 150W and carries out supersound process 60min, form turbid solution.Preferably, the addition of graphite oxide is 0.1g, and the addition of deionized water is 200mL.
S2: the turbid solution in beaker is poured in centrifuge tube, is centrifuged separating treatment 10min.Preferably, the rotating speed of centrifuge is 5000r/min.After being performing centrifugal separation on, the more graphite oxide of the number of plies is stayed bottom centrifuge tube, and relatively thin graphene oxide solution is dissolved in deionized water.Preferably, the number of plies of relatively thin graphene oxide is 1～100 layer.
S3: the solution collection of graphene oxide will be dissolved with in beaker, and add salpeter solution and be stirred, then stand 30min.Preferably, the concentration of aqueous solution of nitric acid is 5mol/L, and addition is 1mL.After adding aqueous solution of nitric acid, having obvious flocculent deposit to precipitate out, after precipitation, liquid is divided into upper and lower two-layer, and upper strata is liquid, and lower floor is linen graphene oxide, is collected by the graphene oxide of lower floor.
S4: the graphene oxide of collection is inverted in embodiment 2 or in the metallic substrates with two dimension or three dimensional structure prepared by embodiment 3 or flexible substrates so that it is trickling naturally, forms liquid membranaceous, naturally dry.It is placed in vacuum drying oven is dried being equipped with the membranaceous substrate of liquid.Preferably, baking temperature is 50 DEG C, and vacuum is 5Pa, and drying time is 24h.Brown color product after drying is graphene oxide film.
Or, S4 may be used without following manner and realizes:
The metallic substrates with two dimension or three dimensional structure or the flexible substrates prepare embodiment 2 or embodiment 3 are dipped vertically in the graphene oxide of collection, then vertically lift metallic substrates or flexible substrates, make graphene oxide transfer in metallic substrates or flexible substrates.Again the metallic substrates or flexible substrates that are attached with graphene oxide are placed in vacuum drying oven to be dried.Preferably, the speed that metallic substrates or flexible substrates are dipped vertically into and vertically lift is 0.1～1mm/min.Metallic substrates or flexible substrates make graphene oxide be attached to substrate surface by the mode being dipped vertically into and vertically lift, and immerse and lift the graphene oxide film once obtaining monolayer, immerse and lift the graphene oxide film obtaining bilayer twice, by that analogy.
According to a preferred implementation, the present invention adopts heat-treating methods to carry out oxidation graphene film.Specifically, prepared graphene oxide film is put in quartz boat, put in the quartz ampoule in tube furnace together, closed quartz tube.Evacuation, then passes to argon, twice repeatedly, finally intensification heat treatment 1.5h under an argon atmosphere.Preferably, temperature is warming up to 1100 DEG C according to the speed of 5 DEG C/min.Graphene oxide film is reduced to graphene conductive film under argon shield.
It should be noted that; above-mentioned specific embodiment is illustrative of; those skilled in the art can find out various solution under the inspiration of the disclosure of invention, and these solutions also belong to disclosure of the invention scope and fall within protection scope of the present invention.It will be understood by those skilled in the art that description of the present invention and accompanying drawing thereof be illustrative are not constitute limitations on claims.Protection scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. the preparation method of a graphene conductive film, described method includes the preparation of graphite oxide, the assembling of graphene oxide film and the reduction of graphene oxide film, it is characterized in that, by graphite powder being formed under strong oxidizer effect graphite oxide, and described graphite oxide is formed graphene oxide colloid solution after ultrasonic being centrifuged, electrolyte is dripped again so that the flocculation of described graphene oxide colloid solution deposits in described graphene oxide colloid solution, the substrate with two dimension or three dimensional structure good for pretreatment and described graphene oxide are completed self assembling process simultaneously and prepare described graphene oxide film, method finally by heat treatment or electronation removes the oxygen-containing functional group in described graphene oxide film, thus preparing described graphene conductive film.
2. the preparation method of graphene conductive film as claimed in claim 1, it is characterized in that, the described substrate with two dimension or three dimensional structure is metallic substrates, further, according to the material properties of described metallic substrates and required physical dimension select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode prepare described in there is the metallic substrates of two dimension or three dimensional structure.
3. the preparation method of graphene conductive film as claimed in claim 2, it is characterized in that, after the described metallic substrates with two dimension or three dimensional structure soaks 30～60min in one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution after sandblasting, again by described metallic substrates acetone, ethanol and deionized water ultrasonic cleaning 2～5min respectively, dry standby.
4. the preparation method of graphene conductive film as claimed in claim 1, it is characterised in that described in have the substrate of two dimension or three dimensional structure be flexible substrates, described in have the flexible substrates of two dimension or three dimensional structure be prepare as follows:
Choose a metal material as the first substrate, and select photoetching, dry etching, wet etching, nano impression, mask, ion beam direct write, self assembly or mechanical precision machined mode to prepare first substrate with two dimension or three dimensional structure according to the material properties of described first substrate and the physical dimension of required flexible substrates
Described first substrate with two dimension or three dimensional structure revolves the flexible polymer of one layer of 50～100 μ m-thick, and the first substrate being rotary with flexible polymer is placed in baking oven and is dried by described flexible polymer, then the structure of described flexible polymer/the first substrate with two dimension or three dimensional structure is placed in metal etch solution and is fallen by described first substrate etching.
5. the preparation method of graphene conductive film as claimed in claim 4, it is characterised in that by the following method the described flexible substrates with two dimension or three dimensional structure is carried out pretreatment:
It is coated with adhensive membrane after the described flexible substrates with two dimension or three dimensional structure is carried out sided corona treatment or chemical attack frosted process, and, described adhensive membrane is the one in thermosetting resin and thermoplastic resin, and the thickness of described adhensive membrane is 1～5 μm；Or
The described flexible substrates with two dimension or three dimensional structure is inserted in plasma processor, adopts oxygen to process 40～80S when power is 30～100W；
Dry standby after the flexible substrates deionized water described in pretreated with two dimension or three dimensional structure is cleaned.
6. the preparation method of the graphene conductive film as described in claim 3 or 5, it is characterised in that the preparation of described graphite oxide comprises the steps:
Graphite powder, sodium nitrate and concentrated sulphuric acid being placed in reactor, and drip potassium permanganate at the temperature of 0～10 DEG C while stirring, the time for adding of described potassium permanganate is 10～20min；
In described reactor, pass into nitrogen and the temperature in described reactor is increased to 35 DEG C, continuing stirring 20～30min；
In described reactor, add deionized water, the temperature in described reactor is increased to 85～95 DEG C simultaneously, continue stirring 35～45min；
In described reactor, add hydrogen peroxide, then add deionized water and be diluted, be stirred simultaneously；
After described reactor is naturally cooled to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide.
7. the preparation method of graphene conductive film as claimed in claim 6, it is characterised in that
Described graphite powder, described sodium nitrate, described concentrated sulphuric acid mass ratio be 1～4: 0.5～2: 40～100；
The mass ratio of described graphite powder and described potassium permanganate is 1: 3；
The mass ratio of described graphite powder and described deionized water is 1: 50～60, and, described deionized water adds in described reactor at twice；
The mass ratio of described graphite powder and described hydrogen peroxide is 1: 15～20.
8. the preparation method of the graphene conductive film as described in claim 3 or 5, it is characterised in that the assembling of described graphene oxide film comprises the steps:
Described graphite oxide is added in reactor, and carrying out ultrasonic cleaning 40～60min by the amount that mass ratio is 1: 1500～2000 described deionized water of addition of described graphite oxide and deionized water, the turbid solution that described graphite oxide is formed through ultrasonic cleaning is centrifuged separating treatment 10～20min again；
By being dissolved with the solution collection of graphene oxide and adding standing 30～60min after aqueous solution of nitric acid stirs after centrifugation, carry out after flocculation sediment process through aqueous solution of nitric acid, collect the graphene oxide of lower floor；
By collect described graphene oxide be inverted in standby described in have in the substrate of two dimension or three dimensional structure, and make described graphene oxide formed liquid membranaceous, be placed in again after naturally drying in vacuum tank dry, obtain graphene oxide film；Or
The described substrate with two dimension or three dimensional structure is dipped vertically in the described graphene oxide of collection and vertically there is the substrate of two dimension or three dimensional structure described in lift, make described graphene oxide transfer to described in have in the substrate of two dimension or three dimensional structure, naturally it is placed in vacuum tank after drying again dry, obtains graphene oxide film.
9. the preparation method of the graphene conductive film as described in claim 3 or 5, it is characterised in that the reduction of described graphene oxide film comprises the steps:
Described graphene oxide film is put in tube furnace, after evacuation, passes into argon again, be repeatedly warming up to 800～1100 DEG C under an argon atmosphere after twice, and namely heat treatment 1～1.5h obtains graphene conductive film at such a temperature.
10. the preparation method of graphene conductive film as claimed in claim 1, it is characterised in that the preparation method of described graphene conductive film is as follows:
Being be placed in reactor at 2: 1: 80 in mass ratio by graphite powder, sodium nitrate and concentrated sulphuric acid, and drip the potassium permanganate of described graphite powder consumption 3 times at the temperature of 10 DEG C while stirring, the time for adding of described potassium permanganate is 10min；In described reactor, pass into nitrogen again and by the temperature in described reactor to 35 DEG C, continue stirring 30min；In described reactor, add the deionized water of described graphite powder consumption 35 times again, the temperature in described reactor is increased to 90 DEG C simultaneously, continue stirring 40min；In described reactor, add the hydrogen peroxide of described graphite powder consumption 18 times again, and the deionized water adding described graphite powder consumption 20 times is diluted, and is stirred simultaneously；After described reactor is naturally cooled to 25 DEG C, use deionized water wash product, and be dried, obtain graphite oxide；
After one or both solution in sodium hydroxide solution, hydrogenperoxide steam generator, phosphoric acid solution and hydrochloric acid solution after there is after processed the metallic substrates sandblasting of two dimension or three dimensional structure soak 30min, by described, there is the metallic substrates acetone of two dimension or three dimensional structure, ethanol and deionized water ultrasonic cleaning 2min respectively again, and dry up with nitrogen standby；nullOr，Choose a metal material as the first substrate，And select photoetching according to the material properties of described first substrate and the physical dimension of required flexible substrates、Dry etching、Wet etching、Nano impression、Mask、Ion beam direct write、Self assembly or mechanical precision machined mode prepare first substrate with two dimension or three dimensional structure，Described first substrate with two dimension or three dimensional structure revolves the PDMS performed polymer of one layer of 50～100 μ m-thick、PET performed polymer、PP performed polymer、PE performed polymer、UV optic-solidified adhesive or PUA heat-curable glue，And described first substrate with two dimension or three dimensional structure is placed in baking oven by PDMS performed polymer、PET performed polymer、PP performed polymer、PE performed polymer、UV optic-solidified adhesive or PUA heat-curable glue are dried，Again the structure of described flexible polymer/the first substrate with two dimension or three dimensional structure is placed in metal etch solution and falls to prepare the flexible substrates with two dimension or three dimensional structure by described first substrate etching，It is coated with adhensive membrane after the described flexible substrates with two dimension or three dimensional structure is carried out sided corona treatment or chemical attack frosted process，The thickness of described adhensive membrane is 1～5 μm，Or the described flexible substrates with two dimension or three dimensional structure is inserted in plasma processor，Oxygen is adopted to process 40～80S when power is 30～100W so that the described flexible substrates with two dimension or three dimensional structure is carried out pretreatment，After the flexible substrates deionized water described in pretreated with two dimension or three dimensional structure is cleaned standby；Being added in reactor by described graphite oxide, and add deionized water ultrasonic cleaning 60min by the amount that mass ratio is 1: 2000 of described graphite oxide and described deionized water, the turbid solution formed through ultrasonic cleaning is centrifuged separating treatment 10min again；By being dissolved with the solution collection of graphene oxide and adding standing 30min after aqueous solution of nitric acid stirs after centrifugation, carry out after flocculation sediment process through aqueous solution of nitric acid, collect the graphene oxide of lower floor；Described graphene oxide is inverted in the standby substrate with two dimension or three dimensional structure, and it is membranaceous to make described graphene oxide form liquid, be placed in vacuum tank after naturally drying again dry, obtain graphene oxide film；Or the described substrate with two dimension or three dimensional structure is dipped vertically in the described graphene oxide of collection and vertically there is the substrate of two dimension or three dimensional structure described in lift, make described graphene oxide transfer to described in have in the substrate of two dimension or three dimensional structure, naturally it is placed in vacuum tank after drying again dry, obtains graphene oxide film；
Described graphene oxide film is put in tube furnace, after evacuation, passes into argon again, be repeatedly warming up to 900～1100 DEG C according to the speed of 5～10 DEG C/min under an argon atmosphere after twice, and namely heat treatment 1～1.5h obtains graphene film at such a temperature.
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