CN113213774A

CN113213774A - Graphene glass and preparation method thereof

Info

Publication number: CN113213774A
Application number: CN202010069477.0A
Authority: CN
Inventors: 张艳锋; 周帆; 刘忠范
Original assignee: Peking University; Beijing Graphene Institute BGI
Current assignee: Peking University; Beijing Graphene Institute BGI
Priority date: 2020-01-21
Filing date: 2020-01-21
Publication date: 2021-08-06
Anticipated expiration: 2040-01-21
Also published as: CN113213774B

Abstract

The present disclosure provides a method for preparing graphene glass, comprising: providing a glass; carrying out physical vapor deposition on the surface of the glass to form a titanium intermediate layer; and carrying out chemical vapor deposition on the surface of the titanium intermediate layer to grow graphene, thus obtaining the graphene glass. According to the method, the extremely thin titanium interlayer is introduced between the glass substrate and the graphene, so that the binding force between the graphene and the glass is greatly improved, and the obtained graphene glass has the characteristics of low surface resistance, good uniformity, controllable graphene layer thickness, high graphene growth rate, long service life and the like, has good structural and performance stability, and is beneficial to promoting the development of practical application of the graphene glass in production and life, especially under certain extreme working conditions.

Description

Graphene glass and preparation method thereof

Technical Field

The disclosure relates to the technical field of composite materials, and particularly relates to graphene glass and a preparation method thereof.

Background

The graphene is a two-dimensional atomic crystal with a planar hexagonal honeycomb lattice structure and has a series of excellent characteristicsSuch as ultra high carrier mobility (up to 200,000 cm)²·V^-1·s^-1) Good light transmission (single-layer absorbance is a fine structure constant pi alpha and is-2.3%), excellent in-plane heat conductivity (the heat conductivity can reach-5300 W.m)^-1·K^-1) Extremely high mechanical strength and flexibility, surface hydrophobicity, good biocompatibility and the like. The excellent performances enable the graphene to have great application potential in the fields of electronic devices, photoelectric devices, energy storage and conversion, biomolecule detection and the like. The glass is an inorganic non-metallic amorphous material with long history and wide application, has the properties of extremely high hardness, good light transmittance, rigidity, insulation and the like, and can be used as a substrate material for supporting graphene. The graphene film is directly covered on the surface of the glass to form a novel composite material, namely graphene glass, so that the advantages of the two materials in performance can be complemented, and the obtained graphene glass composite material has the characteristics of transparency, transverse heat conduction, electric conduction, hydrophobicity, rigidity and the like, and is expected to be widely applied to the fields of transparent electric heating equipment, intelligent dimming windows, biomolecule detection, cell culture and the like.

At present, the preparation method of the graphene glass can be roughly divided into three types: coating methods, transfer methods, and CVD direct growth methods. The CVD direct growth method can obtain a graphene film with relatively high crystallization quality on the surface of the glass, simultaneously avoids a plurality of troubles caused by a transfer process due to direct growth, and has the advantages of low preparation cost, easiness in batch production, good controllability of graphene growth and the like, so that the method gradually becomes the most potential graphene glass preparation method.

However, since the interface interaction between graphene and the glass substrate is mainly weak van der waals interaction, the adhesion of graphene on the glass substrate is poor, and the graphene film is easily damaged by mechanical actions such as scratch and the like to cause material failure, which is not favorable for popularization and expansion of graphene glass application.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the present disclosure and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

A primary objective of the present disclosure is to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a method for preparing graphene glass and graphene prepared by the method, so as to solve the problem of poor adhesion of the existing graphene on a glass substrate.

In order to achieve the purpose, the following technical scheme is adopted in the disclosure:

the present disclosure provides a method for preparing graphene glass, comprising: providing a glass; carrying out physical vapor deposition on the surface of the glass to form a titanium intermediate layer; and carrying out chemical vapor deposition on the surface of the titanium intermediate layer to grow graphene, thus obtaining the graphene glass.

According to one embodiment of the present disclosure, the physical vapor deposition is performed by a magnetron sputtering method selected from one or more of a direct current magnetron sputtering method, a high power pulse magnetron sputtering method, a medium frequency magnetron sputtering method, a radio frequency magnetron sputtering method, and a reactive magnetron sputtering method, and/or a vacuum evaporation coating method selected from one or more of an electron beam evaporation coating method, a multi-arc ion coating method, and an ion beam evaporation coating method.

According to one embodiment of the present disclosure, a carbon source gas and a reducing gas are introduced into a chemical vapor deposition system to perform chemical vapor deposition, the carbon source is selected from one or more of methane, ethane, ethylene and acetylene, the flow rate of the carbon source gas is 3sccm to 10sccm, and the flow rate of the reducing gas is 5sccm to 10 sccm.

According to one embodiment of the present disclosure, the growth temperature of graphene is 600 ℃ to 700 ℃, and the vacuum degree in the chemical vapor deposition system is 1Pa to 10 Pa.

According to one embodiment of the disclosure, before the graphene grows, annealing treatment is performed on the glass after the titanium intermediate layer is formed, wherein the annealing treatment comprises a first annealing treatment and a second annealing treatment, the temperature of the first annealing treatment is 300-350 ℃, and the time is 1.5-2.5 h; the temperature of the second annealing treatment is 600-700 ℃, and the time is 0.5-2.5 h.

According to one embodiment of the present disclosure, the chemical vapor deposition adopts a plasma enhanced chemical vapor deposition method, and the chemical vapor deposition system comprises a reaction chamber, a radio frequency generation device and a three-temperature-zone tube furnace.

According to one embodiment of the present disclosure, the power of the radio frequency generating device is 200W to 400W.

According to one embodiment of the present disclosure, the three-temperature-zone tube furnace includes a first temperature zone, a second temperature zone, and a third temperature zone in this order along a carbon source gas passing direction, wherein glass on which a titanium intermediate layer is formed is placed at a boundary of the first temperature zone and the second temperature zone.

The present disclosure provides a graphene glass prepared by the above method, including: glass, titanium interlayers, and glass layers; the titanium intermediate layer is positioned on the surface of the glass, and the graphene layer is connected to the surface of the titanium intermediate layer in a covalent bond mode.

According to one embodiment of the present disclosure, the thickness of the titanium intermediate layer is 10nm to 20 nm.

According to one embodiment of the present disclosure, the glass is quartz glass, sapphire glass, or soda lime glass.

According to the technical scheme, the beneficial effects of the disclosure are as follows:

according to the preparation method of the graphene glass, the extremely thin titanium interlayer is introduced between the glass substrate and the graphene, and the strong bonding effect between the titanium and the graphene and between the titanium and the glass is utilized, so that the bonding force between the graphene and the glass substrate is greatly improved, the tolerance of the graphene on the glass substrate to destructive mechanical action (such as scratching, scratching and the like) is improved, the stability of the structure and the performance is improved, and the service life is prolonged; in addition, the extremely thin titanium interlayer is easily oxidized into colorless and transparent titanium dioxide in the air, so that the obtained graphene glass keeps high transmittance. Finally, compared with the method of directly growing graphene on a glass substrate, after the titanium intermediate layer is introduced, the growth speed of the graphene film is increased, the growth time is shortened, the surface resistance of the sample is reduced, and the growth uniformity is improved.

In a word, the graphene glass obtained by the method has the characteristics of low surface resistance, good uniformity, controllable graphene layer thickness, high graphene growth rate, long service life and the like, has good structural and performance stability, and is beneficial to promoting the practical application development of the graphene glass under extreme working conditions.

Drawings

The following drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the principles of the disclosure and not to limit the disclosure.

Fig. 1 is a flow chart of a process for preparing graphene glass according to an embodiment of the present disclosure;

FIG. 2 is a schematic diagram of chemical vapor deposition grown graphene according to an embodiment of the present disclosure;

FIG. 3 is a temperature-time line graph of the chemical vapor deposition growth process of example 1;

fig. 4 is a raman spectrum of the graphene glass of example 1 before and after the eraser test;

fig. 5 is a raman spectrum of the graphene glass of comparative example 1 before and after the eraser test;

FIG. 6 is an X-ray photoelectron spectroscopy analysis Ti 2p spectrum of the graphene glass of example 2;

fig. 7a and 7b are X-ray photoelectron spectroscopy analysis C1s spectrum and its partial enlarged view of graphene glass of example 2.

Wherein the reference numbers are as follows:

100: radio frequency generating device

200: three-temperature-zone tube furnace

201: first temperature zone

202: second temperature zone

203: third temperature zone

300: reaction chamber

400: glass with titanium interlayer

I: first annealing treatment period

II: second annealing treatment period

III: graphene growth period

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the present disclosure. The endpoints of the ranges and any values disclosed in the present disclosure are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

Referring to fig. 1, a flow chart of a process for preparing graphene glass according to an exemplary embodiment of the present disclosure is representatively illustrated. Fig. 2 shows a schematic diagram of chemical vapor deposition growth of graphene according to an embodiment of the present disclosure. The preparation method provided by the present disclosure is illustrated as being applied to the glass substrate growth of graphene. Those skilled in the art will readily appreciate that many modifications, additions, substitutions, deletions, or other changes may be made to the embodiments described below in order to apply the relevant designs of the present disclosure to other types of non-metallic substrates, such as silicon wafers and the like, while still remaining within the principles of the fabrication methods set forth in the present disclosure.

As shown in fig. 1, the method for preparing graphene glass of the present disclosure includes: providing a glass; carrying out physical vapor deposition on the surface of the glass to form a titanium intermediate layer; and carrying out chemical vapor deposition on the titanium intermediate layer to grow graphene, so as to obtain the graphene glass.

According to the disclosure, the existing graphene glass generally grows graphene on glass directly, however, since the interface interaction between the graphene and the glass substrate is mainly weak van der waals interaction, the adhesion of the graphene on the glass substrate is poor, so that the graphene film is easily damaged due to mechanical actions such as scratch and the like to cause material failure, which is not beneficial to popularization and expansion of application of the graphene glass. The inventors of the present disclosure found that by first forming a titanium metal interlayer on the glass before growing graphene, the performance of the graphene glass is greatly improved. On one hand, the metal titanium and the glass substrate have stronger binding force, and the graphene is chemically bonded to a certain extent when deposited on the surface of the titanium intermediate layer, namely, an extremely thin TiC transition layer is formed, so that the graphene and the titanium intermediate layer also have stronger binding force, and the graphene has stronger binding force with the glass through the carbon film; moreover, because a layer of compact oxide layer, namely colorless and transparent titanium dioxide, is easily formed on the surface of the metal titanium exposed in the air, the influence on the light transmittance of the graphene glass is reduced as much as possible when the bonding force between the graphene and the glass substrate is enhanced. Finally, compared with the method of directly growing graphene on a glass substrate, after the titanium intermediate layer is introduced, the growth speed of the graphene film is increased, the growth time is shortened, the surface resistance of the sample is reduced, and the growth uniformity is improved. The method is beneficial to improving the structural and performance stability of the graphene glass, prolonging the service life of the graphene glass, promoting the application and development of the graphene glass in daily scientific research, production, life and even some extreme working environments, and has important significance.

In some embodiments, the aforementioned glass includes, but is not limited to, high temperature resistant glass such as quartz glass, sapphire glass, etc., and can be extended to low softening point glass such as soda-lime glass, etc. at a suitable graphene growth temperature. Preferably, the glass is cleaned prior to use. For example: and (3) putting the glass into deionized water, acetone and isopropanol in sequence, ultrasonically cleaning for 10min, and blow-drying by using a nitrogen gun to obtain the glass with a clean surface.

And then, plating the titanium intermediate layer on the cleaned glass by a Physical Vapor Deposition (PVD) method, wherein the PVD method adopts a magnetron sputtering method and/or a vacuum evaporation plating method, the magnetron sputtering method is selected from one or more of a direct-current magnetron sputtering method, a high-power pulse magnetron sputtering method, a medium-frequency magnetron sputtering method, a radio-frequency magnetron sputtering method and a reactive magnetron sputtering method, and the vacuum evaporation plating method is selected from one or more of an electron beam evaporation plating method, a multi-arc ion plating method and an ion beam evaporation plating method. Taking the magnetron sputtering method as an example, the coating process parameters can be as follows: the DC power is 20W, the working pressure is 0.5Pa, and the deposition time is about 3 min. The present disclosure is not limited thereto and the above deposition methods and parameters may be adjusted according to actual needs. The thickness of the titanium intermediate layer is generally 10nm to 20nm, for example, 10nm, 12nm, 15nm, 18nm, 20nm, etc. But should not be too thick or too thin, too thick will result in too low a transmittance of the final sample and too high a cost; due to the limitation of coating precision, if the titanium intermediate layer is too thin, firstly, the layer thickness may be greatly different from an ideal value (coating time may be only a few seconds, which is difficult to control and has a large error), and secondly, the condition of uneven coating may occur, for example, some places have a film layer, and some places do not have a film layer; or some titanium intermediate layers are thicker or thinner, which finally influences the growth uniformity and controllability of the graphene.

After a titanium intermediate layer is deposited on a glass substrate, chemical vapor deposition is carried out in a chemical vapor deposition system to grow graphene. As shown in fig. 2, the chemical vapor deposition system is a plasma chemical vapor deposition (PECVD) system, and includes a radio frequency generation device 100, a three-temperature-zone tube furnace 200, and a reaction chamber 300, wherein the three-temperature-zone tube furnace 200 includes a first temperature zone 201, a second temperature zone 202, and a third temperature zone 203. The edge of an ordinary tube furnace can dissipate heat, and the position close to the edge in the furnace can be lower than a set temperature, so that the actual temperature of part of the area is different from the set temperature when graphene grows. The invention adopts the three-temperature-zone tube furnace, the total length of the three temperature zones is longer than that of the common tube furnace and is set to be the same temperature, so that the length of a constant-temperature zone, namely a zone with the actual temperature consistent with the set temperature, is increased, which is beneficial to improving the growth uniformity of a substrate with larger size, for example, a sample (such as a strip sample) with larger size along the airflow direction, and if the temperature at each position is inconsistent, the growth non-uniformity can be further increased.

Before the reaction starts, the glass 400 after the formation of the titanium intermediate layer is placed in the reaction chamber 300. Preferably, the pre-reacted substrate is placed at the boundary between the first two temperature zones of the three-temperature-zone tube furnace 200, i.e. the first temperature zone 201 and the second temperature zone 202, where the plasma concentration is higher and is located in the constant temperature zone range of the three-temperature-zone tube furnace 200, so that the graphene near the substrate can be ensured to have relatively higher carbon source concentration and more uniform temperature distribution in the growth process.

Next, the reaction system is evacuated to maintain the system vacuum at 1Pa to 10Pa, for example, 5 Pa. Then, a reducing gas such as hydrogen is introduced from the gas inlet end of the reaction chamber 300 to create a reducing atmosphere. The flow rate of the reducing gas in this case ranges from 30sccm to 60sccm, for example, 50sccm, but the present disclosure is not limited thereto. The reaction chamber is then warmed. The glass 400 with the titanium interlayer formed is firstly annealed, and the annealing treatment comprises a first annealing treatment and a second annealing treatment, wherein the temperature of the first annealing treatment is 300-350 ℃, for example 300 ℃, and the first annealing time is 1.5-2.5 h, for example 1.5h, 1.8h, 2h, 2.5h and the like. The agglomeration of the titanium intermediate layer in the high-temperature graphene growth process can be reduced through the first annealing treatment, and the fluctuation of the surface of the substrate is reduced, so that the growth quality of graphene is improved. After the first annealing treatment is finished, the second annealing treatment can be further carried out for about 0.5h to 2.5h, such as 0.5h, 0.8h, 1.2h, 2h, 2.5h and the like at the temperature of 600 ℃ to 700 ℃. The temperature of the growth system can be stabilized through the second annealing treatment, the temperature in the growth region is ensured to be uniform, and the surface of the growth substrate can be further cleaned.

And then keeping the temperature unchanged, reducing the flow of the reducing gas, such as hydrogen, starting a carbon source, and after the pressure in the pipeline is stable, starting a radio frequency generation device and setting the power to be 200-400W to perform PECVD growth of graphene. Generally, it also includes the introduction of a certain amount of carrier gas, such as argon, etc. Wherein the carbon source may be one or more of methane, ethane, ethylene, and acetylene, to which the present disclosure is not limited. The flow rate of the carbon source gas is 3sccm to 10sccm, and the flow rate of the reducing gas is 5sccm to 10 sccm. In the present disclosure, the reaction temperature, the reaction time, and the gas flow rate may be adjusted as needed. It mainly follows the following principles: in the graphene growth process, if the mass flow ratio of the hydrogen to the carbon source is kept unchanged, the growth quality of the graphene is improved along with the increase of the growth temperature; the thickness and the growth quality of graphene obtained by growth on the surface of the substrate can be regulated and controlled by regulating and controlling growth parameters such as growth time, carbon-hydrogen ratio (mass flow ratio of carbon source to hydrogen) and the like; with the increase of the carbon-hydrogen ratio, the growth speed of the graphene is reduced, the time required for growing the graphene with the same thickness is increased, and meanwhile, the growth quality of the graphene is also improved; with the increase of the growth time, the layer thickness of the graphene is gradually increased, and meanwhile, the growth quality of the graphene is improved.

After the growth of the graphene is finished, a radio frequency power supply, a carbon source and a heating switch of the three-temperature-zone tube furnace are closed, meanwhile, the introduction of hydrogen is kept, and a reacted sample is naturally cooled to room temperature in a hydrogen atmosphere so as to prevent the generated graphene from being oxidized at high temperature. And (3) after the furnace body is completely cooled, introducing argon gas of about 1000sccm, and taking out the sample after the pressure in the tube is restored to the atmospheric pressure to obtain the graphene glass disclosed by the invention.

In a word, the preparation method of the graphene glass disclosed by the invention is simple and low in cost, and the prepared graphene glass has the characteristics of lower surface resistance, good uniformity, controllable graphene layer thickness, high graphene growth rate and the like. Based on the advantages, the method is beneficial to improving the structural and performance stability of the graphene glass, prolonging the service life of the graphene glass, and promoting the development of the practical application of the graphene glass in production and life, especially under certain extreme working conditions.

The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby. Unless otherwise specified, reagents, materials and the like used in the present disclosure are commercially available.

Example 1

This example is provided to illustrate the preparation method of the graphene glass of the present disclosure.

1) Taking quartz glass, putting the quartz glass in deionized water, acetone and isopropanol in sequence, ultrasonically cleaning for 10min, and blow-drying by using a nitrogen gun to obtain the quartz glass with a clean surface.

2) And (3) placing the cleaned quartz glass in a magnetron sputtering device for film coating treatment so as to deposit a titanium intermediate layer with the thickness of 10nm on the surface of the quartz glass. Wherein the coating process parameters are as follows: the DC power is 20W, the working pressure is 0.5Pa, and the deposition time is about 3 min.

3) Then, the quartz glass on which the titanium intermediate layer was formed was subjected to chemical vapor deposition to grow graphene using the apparatus shown in fig. 2.

Specifically, after the growth device is connected and sealed, the system is vacuumized to 5Pa, a 50sccm hydrogen cleaning pipeline is opened, a reducing atmosphere is built inside the pipeline, and then a temperature control program is started. Fig. 3 shows a temperature-time line graph of the chemical vapor deposition growth process of example 1. As shown in fig. 3, first, before the temperature is raised to 700 ℃ of the graphene growth temperature, the titanium-plated quartz glass substrate needs to be subjected to a first annealing treatment at 300 ℃, wherein the first annealing treatment period I is 120min, and then, after the furnace temperature is raised to 700 ℃, the sample is subjected to a second annealing treatment at the temperature, wherein the second annealing treatment period II is 120 min. And then, keeping the temperature unchanged, regulating the mass flow of the hydrogen to 10sccm, starting 5sccm of methane as a carbon source, starting a power supply of the radio frequency generation device after the pressure in the pipeline is stable, and setting the radio frequency power to 300W to grow the graphene, wherein the growth period III of the graphene is 1 h.

And after the growth is finished, closing the radio frequency power supply, the methane gas flow and the furnace body heating switch, and naturally cooling the sample obtained by the growth to room temperature in a hydrogen atmosphere of 10 sccm. And after the furnace body is completely cooled, introducing argon of 1000sccm, and taking out the sample after the pressure in the tube is restored to the atmospheric pressure.

Example 2

Graphene glass was prepared by the method of example 1, except that the flow rate of carbon source methane was 3sccm and the growth time was 40min, to obtain graphene glass with a titanium interlayer.

Comparative example 1

Graphene glass was prepared using the method of example 1, except that step 2) was not performed, resulting in graphene glass without a titanium interlayer.

Test example 1

The test example is used to characterize the interfacial bonding force of the graphene glasses of example 1 and comparative example 1.

The graphene glasses of example 1 and comparative example 1 were subjected to a rubber wiping experiment. The test method comprises the steps of wiping the surfaces of the graphene glass samples in the embodiment 1 and the comparative example 1 back and forth 10 times respectively with the same force by using a 4B rubber, and measuring the surface resistance, the light transmittance and the Raman (Raman) signals of the samples to be tested before and after wiping. Wherein table 1 below shows the sheet resistance and the light transmittance of the graphene glasses of example 1 and comparative example 1 before and after the eraser test, respectively; fig. 4 shows raman spectra of the graphene glass of example 1 before and after the rubber wiping experiment; fig. 5 shows raman spectra of the graphene glass of comparative example 1 before and after the rubber wiping experiment.

TABLE 1

Analysis shows that the Raman signal of the graphene glass with the titanium interlayer does not change significantly before and after wiping, and compared with that before wiping, the sample I after wiping_2D/I_GThe value is reduced, and the surface resistance and the transmittance are slightly increased, which shows that the structure and the performance of the graphene layer on the surface of the quartz glass after the titanium-plated interlayer is plated do not change obviously before and after wiping; the Raman signal of the graphene glass in the comparative example 1 is greatly changed before and after wiping, compared with that before wiping, the signal intensity of the graphene relative to the substrate after wiping of the sample is obviously weakened, the 2D peak almost disappears, and I_D/I_GThe value increases significantly, the transmittance increases by a large margin (-16.2%), while the sheet resistance increases significantly (the sample after wiping is non-conductive), indicating that the graphene layer on the surface of the quartz glass is severely damaged during wiping. The qualitative experiment shows that the introduction of the titanium intermediate layer is beneficial to the improvement of the binding force between the graphene and the glass substrate.

Test example 2

The test example is used for representing the interface bonding condition of the graphene glass.

X-ray photoelectron spectroscopy (XPS) analysis was performed on the graphene glass of example 2, and fig. 6 is an X-ray photoelectron spectroscopy analysis Ti 2p spectrum of the graphene glass of example 2; fig. 7a is a graph of X-ray photoelectron spectroscopy analysis C1s of the graphene glass of example 2, and fig. 7b is a partially enlarged view of a circled area in fig. 7 a. The characteristic peaks at 455.6eV and 457.6eV shown in fig. 6 and at 282.3eV shown in fig. 7a and 7b all show the presence of Ti-C chemical bonds, indicating that a certain amount of Ti-C chemical bonds are formed between the titanium layer and the graphene layer during the growth of graphene. The bond energy of the chemical bond is much larger than the van der waals interaction energy, and the result of the test example 1 shows that the bonding force between the graphene and the glass substrate is remarkably improved by the Ti-C chemical bond formed by introducing the titanium.

In conclusion, the ultra-thin titanium interlayer is introduced between the glass substrate and the graphene, and the stronger bonding effect between the titanium and the graphene and between the titanium and the glass is utilized, so that the bonding force between the graphene and the glass substrate is greatly improved, and the higher light transmittance can be kept. The obtained graphene glass has the characteristics of low surface resistance, good uniformity, controllable graphene layer thickness, high graphene growth rate, long service life and the like, and has good industrial application prospects.

It should be noted by those skilled in the art that the described embodiments of the present disclosure are merely exemplary, and that various other substitutions, alterations, and modifications may be made within the scope of the present disclosure. Accordingly, the present disclosure is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. A preparation method of graphene glass is characterized by comprising the following steps:

providing a glass;

carrying out physical vapor deposition on the surface of the glass to form a titanium intermediate layer; and

and carrying out chemical vapor deposition on the surface of the titanium intermediate layer to grow graphene, thus obtaining the graphene glass.

2. The method according to claim 1, wherein the physical vapor deposition is performed by a magnetron sputtering method selected from one or more of a direct current magnetron sputtering method, a high power pulse magnetron sputtering method, a medium frequency magnetron sputtering method, a radio frequency magnetron sputtering method, and a reactive magnetron sputtering method, and/or a vacuum evaporation coating method selected from one or more of an electron beam evaporation coating method, a multi-arc ion coating method, and an ion beam evaporation coating method.

3. The method according to claim 1, wherein the chemical vapor deposition is performed by introducing a carbon source gas and a reducing gas into a chemical vapor deposition system, wherein the carbon source is selected from one or more of methane, ethane, ethylene and acetylene, the carbon source gas has a flow rate of 3sccm to 10sccm, and the reducing gas has a flow rate of 5sccm to 10 sccm.

4. The preparation method according to claim 3, wherein the growth temperature of the graphene is 600 ℃ to 700 ℃, and the degree of vacuum in the chemical vapor deposition system is 1Pa to 10 Pa.

5. The preparation method according to claim 1, wherein before the graphene grows, annealing treatment is carried out on the glass after the titanium intermediate layer is formed, wherein the annealing treatment comprises a first annealing treatment and a second annealing treatment, the temperature of the first annealing treatment is 300-350 ℃, and the time is 1.5-2.5 h; the temperature of the second annealing treatment is 600-700 ℃, and the time is 0.5-2.5 h.

6. The preparation method according to claim 1, wherein the chemical vapor deposition adopts a plasma enhanced chemical vapor deposition method, and the chemical vapor deposition system comprises a reaction chamber, a radio frequency generation device and a three-temperature-zone tube furnace.

7. The method according to claim 6, wherein the power of the RF generator is 200W to 400W.

8. The production method according to claim 6, wherein the three-temperature-zone tube furnace comprises a first temperature zone, a second temperature zone and a third temperature zone in this order along the carbon source gas passage direction, wherein the glass after the titanium intermediate layer is formed is placed at the boundary between the first temperature zone and the second temperature zone.

9. A graphene glass prepared by the method of any one of claims 1 to 8, comprising:

glass;

a titanium interlayer located on the glass surface; and

and the graphene layer is connected to the surface of the titanium intermediate layer through a covalent bond.

10. The graphene glass according to claim 9, wherein the titanium interlayer has a thickness of 10nm to 20 nm.