CN106011779B - A method of preparing sulfur-doped graphene films - Google Patents
A method of preparing sulfur-doped graphene films Download PDFInfo
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- CN106011779B CN106011779B CN201610459139.1A CN201610459139A CN106011779B CN 106011779 B CN106011779 B CN 106011779B CN 201610459139 A CN201610459139 A CN 201610459139A CN 106011779 B CN106011779 B CN 106011779B
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
Sulfur-doped graphene films method is prepared the invention discloses a kind of, is related to New Two Dimensional field of nano material preparation.The present invention includes the following steps：Metal substrate and thianthrene are respectively placed in the mutually heat-insulated heating zone of chemical gas-phase deposition system reaction chamber；Under vacuum, mixed gas is passed through into reaction chamber；By heat preservation after metal substrate the high temperature anneal in the preparation temperature of graphene film, then heats thianthrene and be vaporized, and thianthrene gas is delivered to by metal substrate by mixed gas and is reacted, finally prepare sulfur-doped graphene films on the metallic substrate.Preparation process of the present invention is simple, cost is relatively low, it can be achieved that large-scale industrial production, raw material green pollution-free；The sulfur-doped graphene films number of plies, doping content, area is made in the present invention can be by controlling relevant parameter flexible modulation, to prepare with sulfur-doped graphene films of different nature, there is important value in terms of the practical applications such as basic scientific research field and sensor.
Description
Technical field
The present invention relates to New Two Dimensional field of nano material preparation, and in particular to one kind being based on chemical vapor deposition principle system
Standby large area sulfur-doped graphene films method.
Background technology
Machine is used from Univ Manchester UK An Deliehaimu in 2004 and Constantine Nuo Woxiao love professors
After tool stripping method prepares graphene, the more and more excellent specific properties of graphene are confirmed by laboratory.Research shows that graphene
Film has excellent electricity, optics and electrochemical properties, such as high carrier mobility, high light transmittance and specific surface
Product.Therefore, graphene film can be widely applied to the fields such as semiconductor, energy storage and sensing.
The conduction band and valence band of intrinsic graphene intersect at fermi level, its carrier is presented cutting edge aligned at fermi level
Dispersion relation, is a kind of zero gap semiconductor, and electrons and holes concentration is equal.Graphene film applied to semiconductor devices,
The impurity introduced in graphene film transfer process when the fields such as opto-electronic device and graphene film surface are in air
The small molecules such as the water and oxygen of absorption occur electric charge transfer and are adulterated from introducing p-type, this makes hole concentration be more than the concentration of electronics, this
The conductivity of graphene film can be improved, but band gap can not be opened.This makes the field effect transistor based on single-layer graphene film
The on-off ratio very little of pipe, or even can not accomplish current chopping, which greatly limits the applications of graphene.
Theoretical calculation shows that the instead type doping of non-metallic atom will be in graphene zero forbidden band of script for graphene-structured
Band structure in open band gap, while realize N-shaped or p-type doping, it means that the controllable preparation of doped graphene will have
Epochmaking meaning.
Currently, the nonmetal doping of graphene film is based on nitrogen atom doping graphene, research level and doping process
It is more mature.This is because nitrogen-atoms is located near carbon atom, its atom size is suitable with carbon atom, therefore is easy to be doped into
Enter in graphene.And be difficult to incorporate into graphene if the larger atom such as sulphur atom of atomic radius, technique realizes that difficulty is larger, is
One difficult point of graphene film doping vario-property research at present.The existing research about sulfur-doped graphene films technology of preparing
It is relatively fewer, mainly there are following two open reports：Gao Hui of Lanzhou University et al. is in number of patent application
201110095599.8《The preparation method of sulfur-doped graphene films》In report simple substance sulphur powder be dissolved in hexane as liquid
State carbon source and sulphur source prepare sulfur-doped graphene films on the metallic substrate using chemical vapour deposition technique.This method uses
Sulfur doping source need, by dissolution process, to increase preparation difficulty, while solvent hexane is inflammable and toxic as a kind of height
Liquid, have higher requirement to production equipment and environment.Shanghai Inst. of Microsystem and Information Technology, Chinese Academy of Sci
Liang Chen et al. is 201310080785.3 in number of patent application《A method of sulfur doping is carried out to graphene》Disclose one
Kind is passed through the method that sulphur source gas carries out sulfur doping to graphene film, and this method is a kind of post-processing doping to graphene,
It needs first to prepare graphene film and be doped again, this considerably increases the preparation flows of doped graphene film.Therefore, it seeks
A kind of low cost, environmental-friendly sulfur doping source are looked for, and preparation flow is simple, can accomplish that large area is controllable doped etc., be one
A to have project to be solved, this has epochmaking meaning to the scientific research of sulfur-doped graphene films and technical grade volume production.
Invention content
In order to which the disadvantages mentioned above and deficiency, the present invention that overcome the prior art provide a kind of sulfur doping of controllable preparation large area
The method of graphene film can prepare that large area, high quality, the number of plies are controllable, mix the present invention is based on chemical vapor deposition principle
The controllable sulfur-doped graphene films of miscellaneous content, preparation method of the present invention have low cost, and preparation process is simple, reproducible etc.
Feature.
The invention is realized by the following technical scheme：
A method of sulfur-doped graphene films are prepared, are included the following steps：
Step A：Metal substrate and thianthrene are respectively placed in the first heating zone of chemical gas-phase deposition system reaction chamber center
With the second heating zone center, second heating zone is located at first heating zone front end, and heat-insulated with the first heating zone；
Step B：Under vacuum, inert gas and hydrogen are passed through in the chemical gas-phase deposition system reaction chamber of step A
The mixed gas that gas is formed；
Step C：By controlling the first Heating Zone Temperature, the metal substrate is subjected to the high temperature anneal, is then kept the temperature
In the temperature for preparing graphene；
Step D：After metal substrate heat preservation in step C, thianthrene is heated by the second heating zone, is vaporized and passes through institute
It states mixed gas and thianthrene gas is delivered to metal substrate, thianthrene occurs high-temperature catalytic cracking reaction in metal substrate, reacted
Maintain negative pressure to improve film growth quality in journey；
Step E：The first Heating Zone Temperature and the second Heating Zone Temperature are down to room temperature to the end of reaction, finally in metal
Sulfur-doped graphene films are made in substrate surface.
In the preparation method of the present invention, metal substrate material can be copper, nickel or corronil, metal liner in the step A
Base thickness degree is 1~1000 micron, preferably 25 microns of thick copper foils；
The metal substrate is pre-processed, specially：It is 30% or so that metal substrate is used to mass fraction successively
Dilute hydrochloric acid or acetone, deionized water, absolute ethyl alcohol or isopropanol cleaning, each scavenging period be 1~10 minute, finally use nitrogen
Air-blowing is dry for use.
In the preparation method of the present invention, thianthrene (No. CAS in the step A：92-85-3) it is a kind of inexpensive, environment friend
Good sulfur doping source is used as single Solid Source in the present invention, can provide simultaneously needed for sulfur-doped graphene films preparation
Carbon source and sulphur source.
In the preparation method of the present invention, chemical gas-phase deposition system reaction chamber is true using mechanical pumping in the step B
Sky, the pressure after vacuumizing are 0.1~10Pa, preferably 1~5Pa.
Inert gas participates in reacting, make as protection gas, hydrogen as reducibility gas in mixed gas in the step B
It obtains thianthrene and cracks group of the formation containing sulphur atom and carbon atom in the reaction chamber of chemical gaseous phase deposition system, wherein inertia
Gas can be the mixed gas that argon gas, nitrogen or combinations thereof are formed, and the purity of hydrogen is preferably 99.999%；The indifferent gas
The flow for the mixed gas that body and hydrogen are formed is 1~1000sccm, preferably 300sccm；Preferably, the inert gas and
Hydrogen in the mixed gas that hydrogen is formed: inert gas=1: 5~15.
In the preparation method of the present invention, it is specially to the high temperature anneal of metal substrate in the step C：By metal liner
Bottom is heated to 900~1100 DEG C, keeps the temperature 5~120 minutes, preferably 1000~1050 DEG C, 20~30 DEG C/min of heating rate,
Heat preservation 10~30 minutes；Then metal substrate is cooled down to the temperature for preparing graphene film, it is described to prepare graphene film
Temperature be 500~1000 DEG C, preferably 750~850 DEG C；To be lowered to being carried out at heat preservation after the temperature for preparing graphene film
Reason, to be reacted.
In the preparation method of the present invention, thianthrene is heated without using the first heating zone of reaction chamber in the step D, but
It is heated using the second heating zone of heating tape heating or reaction chamber, the second heating zone of the reaction chamber is reacted with described
First heating zone of chamber is mutually heat-insulated, to ensure not influence the temperature of other side；The heating temperature of thianthrene is 90~200
DEG C, preferably 130~150 DEG C, 10~20 DEG C/min of heating rate；
The chemical gas-phase deposition system reaction chamber need to maintain negative pressure 1~1 × 105Between pa；The present invention is using logical
It crosses mechanical pump and takes reaction chamber away hydrogen and inert gas to provide the growth quality that negative pressure achievees the purpose that raising film.
In the preparation method of the present invention, metal substrate temperature and thianthrene temperature are made by wind cooling temperature lowering in the step E
It is down to room temperature, it is preferable that rate of temperature fall is about 50 DEG C/min.
In the preparation method of the present invention, generally the sulfur-doped graphene films of catalytic growth need to be shifted first on the metallic substrate
To carry out subsequent applications on to target substrate, therefore, the preparation method further includes by sulfur-doped graphene films from metal
Substrate desquamation, the step of being transferred to target substrate；It specifically includes：The polymethyl methacrylate rotation of ethyl lactate will be dissolved in
(PMMA) it is applied to graphene film surface, it is with ferric chloride aqueous solutions, ammonium persulfate aqueous solution or dilute hydrochloric acid that metal substrate is rotten
Eating away is transferred to target substrate after cleaning the composite membrane that PMMA and graphene are formed with deionized water, finally uses acetone, benzene first
Ether or ethyl lactate remove PMMA.
Compared with prior art, the invention has the advantages that：
1, the number of plies for the sulfur-doped graphene films that the present invention prepares can realize single layer extremely by regulating and controlling the amount of thianthrene
Ten is several layers of, and different layers of sulfur-doped graphene films have the property such as different mechanical strength and electric conductivity and light transmittance
Matter has important value in terms of the practical applications such as basic scientific research field and sensor.
2, sulfur doping content is up to 3.46%, and sulfur doping graphite in the sulfur-doped graphene films that the present invention prepares
The doping content of alkene film can realize a wide range of adjust by controlling the ratio of mixed gas.
3, the present invention can prepare the sulfur-doped graphene films of large area, high quality, and sulfur-doped graphene films are made
Area can be adjusted flexibly according to the area of metal substrate, repeated experiment proves that preparation method of the present invention can stablize realization
The preparation of wafer scale sulfur-doped graphene films.
4, preparation process of the present invention is simple controllable, strong operability and manufacturing cost are relatively low, it can be achieved that large-scale industry
Production, raw material green pollution-free are more suitable for promoting, apply.
Description of the drawings
Fig. 1 is the chemical vapor deposition unit schematic diagram that the present invention prepares sulfur-doped graphene films；
Fig. 2 is the transmission electron microscope figure of sulfur-doped graphene films prepared by the embodiment of the present invention, and figure (a) is to implement
The transmission electron microscope figure of sulfur-doped graphene films prepared by example 1, figure (b) are sulfur doping graphene prepared by embodiment 2
The transmission electron microscope figure of film；
Fig. 3 is the distribution diagram of element of sulfur-doped graphene films prepared by the embodiment of the present invention, and figure (c) is distributed for carbon
Figure, figure (d) are element sulphur distribution map；
Fig. 4 is the x-ray photoelectron spectroscopy of sulfur-doped graphene films prepared by the embodiment of the present invention, and figure (e) is carbon member
Plain open score, figure (f) are element sulphur open score；
Fig. 5 is the Raman spectrum of sulfur-doped graphene films prepared by the embodiment of the present invention.
Specific embodiment
Invention is further explained with reference to embodiments：
Embodiment 1：
Step A：The copper foil that by thickness be 25 microns, area is 10 centimetres of 10 cm x is successively 30% with mass fraction
Dilute hydrochloric acid, deionized water, absolute ethyl alcohol are respectively washed, and each scavenging period is 5 minutes, is finally dried up with nitrogen；Such as Fig. 1 institutes
Show, the copper foil after cleaning is placed in the central warm area of chemical gas-phase deposition system reaction chamber, the chemical gas-phase deposition system
The central warm area of reaction chamber weighs 200mg thianthrenes and is put in and set in sample boat, will set sample boat and be placed in described as the first heating zone
One heating zone front end, and it is heat-insulated with the first heating zone, it sets sample boat and is heated using heating tape, the heating tape is as the second heating
Area；
Step B：The pressure of chemical gas-phase deposition system reaction chamber is evacuated to by 5Pa using mechanical pump, is then led to thereto
Enter the mixed gas that inert gas and hydrogen are formed, wherein the ratio of argon gas and hydrogen is 14: 1, and mixed gas total flow is
300sccm, and it is 300Pa to maintain reaction chamber pressure；
Step C：Reaction chamber center warm area i.e. the first Heating Zone Temperature is risen to 1000 DEG C, heating rate is 25 DEG C/minute
Clock, heat preservation cool the temperature to 800 DEG C after 30 minutes, then keep the temperature in 800 DEG C；
Step D：After copper foil heat preservation in step C, heating tape i.e. the second Heating Zone Temperature is risen to 140 DEG C, and be maintained at
The temperature, heating rate are 10 DEG C/min, and heating is so that thianthrene gasifies, and is delivered to thianthrene gas by the mixed gas
Copper foil makes it that catalytic cracking reaction occur on copper foil, keeps negative pressure to improve film growth quality in reaction process；
Step E：To the end of reaction, stop all heating, copper foil temperature and thianthrene temperature is equal by air-cooled mode
It is quickly down to room temperature, mixed gas is closed, sulfur-doped graphene films finally is made in copper foil surface.
The transmission electron microscope figure that (a) is sulfur-doped graphene films manufactured in the present embodiment is schemed in Fig. 2, schemes interior scale
For 2nm, micro-zone analysis can be seen that the typical light and dark striped in graphene film edge, fringe spacing 0.38nm are
Typical graphene layer spacing.By Fig. 2 it can also be seen that about 10 layers of the thickness of sulfur-doped graphene films made from the embodiment
Left and right.
Fig. 3 is sulfur-doped graphene films distribution diagram of element manufactured in the present embodiment, wherein figure (c) is distributed for carbon
Figure, figure (d) are element sulphur distribution map；It can be seen from the figure that element sulphur is evenly distributed, it was demonstrated that sulphur prepared by the present embodiment method
Doped graphene film has good doping characteristic.
Embodiment 2：
Step A：The copper foil that by thickness be 25 microns, area is 10 centimetres of 10 cm x is successively 30% with mass fraction
Dilute hydrochloric acid, deionized water, absolute ethyl alcohol are respectively washed, and each scavenging period is 5 minutes, is finally dried up with nitrogen；Such as Fig. 1 institutes
Show, the copper foil after cleaning is placed in the central warm area of chemical gas-phase deposition system reaction chamber, the chemical gas-phase deposition system
The central warm area of reaction chamber weighs 100mg thianthrenes and is put in and set in sample boat, will set sample boat and be placed in described as the first heating zone
One heating zone front end, and it is heat-insulated with the first heating zone, it sets sample boat and is heated using heating tape, the heating tape is as the second heating
Area；
Step B：The pressure of chemical gas-phase deposition system reaction chamber is evacuated to by 5Pa using mechanical pump, is then led to thereto
Enter the mixed gas that inert gas and hydrogen are formed, wherein the ratio of argon gas and hydrogen is 14: 1, and mixed gas total flow is
300sccm, and it is 300Pa to maintain reaction chamber pressure；
Step C：Reaction chamber center warm area i.e. the first Heating Zone Temperature is risen to 1020 DEG C, heating rate is 25 DEG C/minute
Clock, heat preservation cool the temperature to 750 DEG C after 30 minutes, then keep the temperature in 750 DEG C；
Step D：After copper foil heat preservation in step C, heating tape i.e. the second Heating Zone Temperature is risen to 140 DEG C, and be maintained at
The temperature, heating rate are 10 DEG C/min, and heating makes thianthrene gasify, and thianthrene gas is delivered to copper by the mixed gas
Foil makes it that catalytic cracking reaction occur on copper foil, keeps negative pressure to improve film growth quality in reaction process；
Step E：To the end of reaction, stop all heating, copper foil temperature and thianthrene temperature is equal by air-cooled mode
It is quickly down to room temperature, mixed gas is closed, sulfur-doped graphene films finally is made in copper foil surface.
The transmission electron microscope figure that (b) is sulfur-doped graphene films manufactured in the present embodiment is schemed in Fig. 2, schemes interior scale
For 2nm, micro-zone analysis can be seen that the typical light and dark striped in graphene film edge, fringe spacing 0.38nm are
Typical graphene layer spacing.By figure (b) it can also be seen that the embodiment made from sulfur-doped graphene films thickness be 4~
It 5 layers, can be effective by the total amount and preparation temperature that regulate and control thianthrene compared to sulfur-doped graphene films prepared by embodiment 1
Regulation and control sulfur-doped graphene films the number of plies.
Fig. 4 is the x-ray photoelectron spectroscopy of sulfur-doped graphene films made from the present embodiment, wherein figure (e) is carbon member
Plain open score, figure (f) are element sulphur open score；As shown in Figure 4, the spectral peak signal of element sulphur is very strong, and mainly in the form of sulphur carbon key
In the presence of, carbon open score and element sulphur open score are quantitatively calculated known to sulfur doping content be up to 3.47%, it was demonstrated that the present embodiment system
The sulfur-doped graphene films obtained have good doping characteristic.
Embodiment 3：
Step A：The copper foil that by thickness be 25 microns, area is 20 centimetres of 50 cm x is successively 30% with mass fraction
Dilute hydrochloric acid, deionized water, absolute ethyl alcohol are respectively washed, and each scavenging period is 5 minutes, is finally dried up with nitrogen；Such as Fig. 1 institutes
Show, the copper foil after cleaning is placed in the central warm area of chemical gas-phase deposition system reaction chamber, the chemical gas-phase deposition system
The central warm area of reaction chamber weighs 100mg thianthrenes and is put in and set in sample boat, will set sample boat and be placed in described as the first heating zone
One heating zone front end, and it is heat-insulated with the first heating zone, it sets sample boat and is heated using heating tape, the heating tape is as the second heating
Area；
Step B：The pressure of chemical gas-phase deposition system reaction chamber is evacuated to by 5Pa using mechanical pump, is then led to thereto
Enter the mixed gas that inert gas and hydrogen are formed, wherein the ratio of argon gas and hydrogen is 5: 1, and mixed gas total flow is
300sccm, and it is 5 × 10 to maintain reaction chamber pressure4Pa；
Step C：Reaction chamber center warm area i.e. the first Heating Zone Temperature is risen to 1020 DEG C, heating rate is 25 DEG C/minute
Clock, heat preservation cool the temperature to 800 DEG C after 30 minutes, then keep the temperature in 800 DEG C；
Step D：After copper foil heat preservation in step C, heating tape i.e. the second Heating Zone Temperature is risen to 150 DEG C, and be maintained at
The temperature, heating rate are 10 DEG C/min, and heating makes thianthrene gasify, and thianthrene gas is delivered to copper by the mixed gas
Foil makes it that catalytic cracking reaction occur on copper foil, keeps negative pressure to improve film growth quality in reaction process；
Step E：To the end of reaction, stop all heating, copper foil temperature and thianthrene temperature is equal by air-cooled mode
It is quickly down to room temperature, mixed gas is closed, sulfur-doped graphene films finally is made in copper foil surface.
Fig. 5 is the Raman spectrum of sulfur-doped graphene films made from the present embodiment, it can be seen that it is thin with graphene
Typical three characteristic peaks of film, are the peaks D, the peaks G and the peaks 2D respectively, and the appearance at the peaks G ' further shows that element sulphur is mixed with graphite
Alkene；It can be seen that sulfur-doped graphene films prepared by the present embodiment method have preferably from the relative intensity ratio at the peaks 2D and the peaks G
Crystal quality.
Embodiment 4：
Step A：The nickel substrate that by thickness be 10 microns, area is 20 centimetres of 50 cm x is successively 30% with mass fraction
Dilute hydrochloric acid, deionized water, absolute ethyl alcohol be respectively washed, each scavenging period is 5 minutes, is finally dried up with nitrogen；Such as Fig. 1 institutes
Show, the nickel substrate after cleaning is placed in the central warm area of chemical gas-phase deposition system reaction chamber, the chemical vapor deposition system
Unite reaction chamber central warm area as the first heating zone, weigh 500mg thianthrenes and be put in and set in sample boat, will set sample boat be placed in it is described
First heating zone front end, and it is heat-insulated with the first heating zone, it sets sample boat and is heated using heating tape, the heating tape is as the second heating
Area；
Step B：The pressure of chemical gas-phase deposition system reaction chamber is evacuated to by 5Pa using mechanical pump, is then led to thereto
Enter the mixed gas that inert gas and hydrogen are formed, wherein the ratio of argon gas and hydrogen is 10: 1, and mixed gas total flow is
10sccm, and it is 10Pa to maintain reaction chamber pressure；
Step C：Reaction chamber center warm area i.e. the first Heating Zone Temperature is risen to 900 DEG C, heating rate is 15 DEG C/minute
Clock, heat preservation cool the temperature to 500 DEG C after 90 minutes, then keep the temperature in 500 DEG C；
Step D：After nickel substrate heat preservation in step C, heating tape i.e. the second Heating Zone Temperature is risen to 100 DEG C, and keep
In the temperature, heating rate is 8 DEG C/min, and heating makes thianthrene gasify, and is delivered to thianthrene gas by the mixed gas
Metal substrate makes it that catalytic cracking reaction occur in nickel substrate, keeps negative pressure to improve film growth quality in reaction process；
Step E：To the end of reaction, stops all heating, nickel substrate temperature and thianthrene temperature are passed through into air-cooled mode
It is quickly down to room temperature, closes mixed gas, sulfur-doped graphene films finally are made in Ni-based bottom surface.
Embodiment 5：
Step A：The cupro-nickel substrate that by thickness be 100 microns, area is 20 centimetres of 50 cm x is successively with mass fraction
30% dilute hydrochloric acid, deionized water, absolute ethyl alcohol are respectively washed, and each scavenging period is 5 minutes, is finally dried up with nitrogen；Such as
Shown in Fig. 1, the cupro-nickel substrate after cleaning is placed in the central warm area of chemical gas-phase deposition system reaction chamber, the chemical gaseous phase
The central warm area of depositing system reaction chamber weighs 500mg thianthrenes and is put in and set in sample boat, will set sample boat and set as the first heating zone
In first heating zone front end, and it is heat-insulated with the first heating zone, it sets sample boat and is heated using heating tape, the heating tape is as
Two heating zones；
Step B：The pressure of chemical gas-phase deposition system reaction chamber is evacuated to by 5Pa using mechanical pump, is then led to thereto
Enter the mixed gas that inert gas and hydrogen are formed, wherein the ratio of argon gas, nitrogen and hydrogen is 5: 5: 1, and mixed gas always flows
Amount is 900sccm, and it is 1 × 10 to maintain reaction chamber pressure5Pa；
Step C：Reaction chamber center warm area i.e. the first Heating Zone Temperature is risen to 1100 DEG C, heating rate is 30 DEG C/minute
Clock, heat preservation cool the temperature to 900 DEG C, then keep the temperature in 900 DEG C after forty minutes；
Step D：After cupro-nickel substrate heat preservation in step C, heating tape i.e. the second Heating Zone Temperature is risen to 200 DEG C, and protect
It holds in the temperature, heating rate is 20 DEG C/min, and heating makes thianthrene gasify, and is conveyed thianthrene gas by the mixed gas
To metal substrate, make it that catalytic cracking reaction occur in cupro-nickel substrate, negative pressure is kept in reaction process to improve film growth
Quality；
Step E：To the end of reaction, stops all heating, cupro-nickel base reservoir temperature and thianthrene temperature are passed through into air-cooled side
Formula is quickly down to room temperature, closes mixed gas, and sulfur-doped graphene films finally are made in cupro-nickel substrate surface.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of method preparing sulfur-doped graphene films, which is characterized in that include the following steps：
Step A：Metal substrate and thianthrene are respectively placed in chemical gas-phase deposition system reaction chamber the first heating zone center and
Two heating zones center, second heating zone are located at first heating zone front end, and heat-insulated with the first heating zone；
Step B：Under vacuum, inert gas and hydrogen shape are passed through in the chemical gas-phase deposition system reaction chamber of step A
At mixed gas；
Step C：By controlling the first Heating Zone Temperature, the metal substrate is subjected to the high temperature anneal, is then kept the temperature in system
The temperature of standby graphene；
Step D：After metal substrate heat preservation in step C, thianthrene is heated by the second heating zone, is vaporized and by described mixed
It closes gas and thianthrene gas is delivered to metal substrate, thianthrene is in metal substrate generation high-temperature catalytic cracking reaction, reaction process
Maintain negative pressure to improve film growth quality；
Step E：To the end of reaction, metal substrate temperature and thianthrene temperature are down to room temperature, stops mixed gas and is passed through, finally
Sulfur-doped graphene films are made in metal substrate surface.
2. a kind of method preparing sulfur-doped graphene films according to claim 1, which is characterized in that the step C
Specially：Metal substrate is heated to 900~1100 DEG C by the first heating zone, keeps the temperature 5~120 minutes, then it is down to 500~
It 1000 DEG C and keeps the temperature.
3. a kind of method preparing sulfur-doped graphene films according to claim 1, which is characterized in that the step D
Middle maintenance negative pressure is specially：By take the mixed gas that the inert gas and hydrogen are formed away with maintain pressure 1~1 ×
105Between Pa.
4. a kind of method preparing sulfur-doped graphene films according to claim 1, which is characterized in that the step E
In by wind cooling temperature lowering so that metal substrate temperature and thianthrene temperature are down to room temperature, rate of temperature fall is 40~60 DEG C/min.
5. a kind of method preparing sulfur-doped graphene films according to claim 1, which is characterized in that further include by sulphur
Doped graphene film is removed from metal substrate, the step of being transferred to target substrate；The poly- of ethyl lactate will be specially dissolved in
Methyl methacrylate is spun on graphene film surface, with liquor ferri trichloridi, ammonium persulfate solution or dilute hydrochloric acid by metal
Substrate etching falls, and mesh is transferred to after then cleaning the composite membrane that polymethyl methacrylate and graphene are formed with deionized water
Substrate is marked, acetone, methyl phenyl ethers anisole is finally used to remove polymethyl methacrylate.
6. a kind of method preparing sulfur-doped graphene films according to any one of claim 1 to 5, feature exist
In metal substrate material is copper, nickel or corronil in the step A, and metal substrate thickness is 1~1000 micron.
7. a kind of method preparing sulfur-doped graphene films according to any one of claim 1 to 5, feature exist
In inert gas is the mixed gas that argon gas, nitrogen or combinations thereof are formed in the step B.
8. a kind of method preparing sulfur-doped graphene films according to any one of claim 1 to 5, feature exist
In the flow for the mixed gas that inert gas and hydrogen are formed in the step B is 1~1000sccm.
9. a kind of method preparing sulfur-doped graphene films according to any one of claim 1 to 5, feature exist
In hydrogen in the mixed gas that inert gas and hydrogen are formed in the step B: inert gas=1: 5~15.
10. a kind of method preparing sulfur-doped graphene films according to any one of claim 1 to 5, feature exist
In the temperature of the second heating zone is 90~200 DEG C in the step D.
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| CN105236762A (en) * | 2015-09-17 | 2016-01-13 | 电子科技大学 | Chemical vapor deposition preparation method for vertically-arranged hafnium disulfide nano-sheet |
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