CN108516541B - CVD graphene dry transfer method - Google Patents
CVD graphene dry transfer method Download PDFInfo
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- CN108516541B CN108516541B CN201810320411.7A CN201810320411A CN108516541B CN 108516541 B CN108516541 B CN 108516541B CN 201810320411 A CN201810320411 A CN 201810320411A CN 108516541 B CN108516541 B CN 108516541B
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- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The invention discloses a CVD graphene dry transfer method, which comprises the steps of spin-coating PVP glue and PVA glue which are prepared on graphene/copper foil in sequence, and drying in an oven; taking out the obtained PVA/PVP/graphene/copper foil, stripping a PVA/PVP/graphene film, transferring the stripped film between two transparent glass slides, preheating, naturally stretching the film, immersing the film in warm absolute ethyl alcohol for 5s, taking out the film, adhering the film on a cleaned substrate, naturally airing the film, placing the film in water vapor at 75 ℃ for 10min, and placing the film in an oven for drying; and taking out the PVA/PVP/graphene/substrate, putting the PVA/PVP/substrate in deionized water at 75 ℃, cleaning the PVA/PVP colloid, washing the PVA/PVP colloid for 5 times by the deionized water, and drying the PVA/PVP colloid in an oven. The method has the advantages of less residual protective glue, no heavy metal residue, less residual organic solvent, less time consumption for transferring graphene, low cost, higher quality of transferred graphene and the like.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a CVD graphene dry transfer method.
Background
Graphene has been applied as a two-dimensional material with high electrical conductivity and high thermal conductivity in the lithium battery and solar energy industries, and since 14 years since the graphene was dissociated by the professor manchester university, nobel prize-god gomer, and the like in 2004, the research on graphene is fierce, and the preparation, electrical properties, optical properties, mechanical properties, modification and application of graphene have been widely agreed. With the development of the field of electronic photoelectric devices, graphene is applied to the photoelectric device as a transparent electrode as a two-dimensional material with high conductivity and high transmittance to a full spectrum, so that the photoelectric response rate of the device is greatly improved. There are many preparation methods of graphene, mainly including: separating out graphene by utilizing pyrolytic graphite; separating out carbon in the silicon carbide at high temperature; growing directly on the substrate using a chemical vapor deposition method, and the like. The graphene single crystal grown by the method has excellent quality, can meet the application on devices, and is popularized and mass-produced. However, the method for growing graphene is limited by a substrate, and at present, high-purity copper foil is generally used as the substrate, and after high-temperature cleaning, raw gas is introduced for growth. Therefore, the transfer process is indispensable for applying the prepared graphene thin film to a device. The traditional transfer method is graphene wet transfer, which is to uniformly mix PMMA (polymethyl methacrylate) glue, etch away copper foil by using an etchant (such as ferric trichloride, ammonium persulfate and the like), transfer graphene to the surface of a substrate after cleaning, and finally remove the glue. The graphene transferred by the method is good in quality, complete in structure and less in wrinkles. However, the process is complex, the etching time of the copper substrate is long, and the adhesion of the long-time etching to the graphene film and the PMMA glue is realizedThe adhesion has a large impact, resulting in the integrity of the graphene being affected during the etching of the copper foil. Furthermore, this method has its inherent disadvantages: 1. heavy metal impurity residues (e.g. Fe)3+、Cu2+Etc.); 2. the PMMA colloid remains; 3. the use of a large amount of organic solvent (e.g. acetone).
Disclosure of Invention
In order to solve the problems, the invention provides a graphene dry transfer method which is free of heavy metal residue, colloidal residue and little in organic pollution, and the method is very advantageous for using graphene as a transparent electrode and a heterojunction photoelectric device.
In order to achieve the purpose, the invention adopts the technical scheme that:
a CVD graphene dry transfer method comprises the following steps:
s1, preparing PVP (polyvinylpyrrolidone) and PVA (polyvinyl alcohol) colloid;
PVP glue: weighing 1g of PVP white powder, adding 1ml of deionized water, adding 2ml of NVP into the PVP white powder, finally adding absolute ethyl alcohol to 10ml, manually stirring until the absolute ethyl alcohol is completely dissolved, sealing and storing at low temperature (0-4 ℃);
PVA glue: weighing 1g of PVA white powder, adding 10ml of deionized water, placing on a magnetic stirrer, setting the temperature at 80 ℃, stirring for 1h until the PVA white powder is completely dissolved and is viscous and colloidal, sealing and storing at normal temperature;
s2, spin-coating colloid in sequence;
cutting graphene/copper foil with a required size, putting the graphene/copper foil on sealed deionized water, heating the graphene/copper foil in a water bath at 50 ℃ for 3 hours, taking out the graphene/copper foil, sequentially spin-coating the obtained PVP glue and PVA glue on the graphene surface, and drying the PVP glue and PVA glue in an oven;
s3, taking out the PVA/PVP/graphene/copper foil, stripping the PVA/PVP/graphene film, transferring the stripped film between two transparent glass slides, and preheating the film on a hot plate for 90S at 75 ℃ to naturally stretch the film;
s4 transfer graphene
Soaking the naturally stretched PVA/PVP/graphene film in absolute ethyl alcohol at 50 ℃ for 5s, taking out, adhering the film to the cleaned substrate, naturally airing, placing the film in water vapor at 75 ℃ for 10min, firmly adhering the film and the substrate, and placing the film in an oven for drying at the temperature of 110 ℃ for 10min to obtain the PVA/PVP/graphene/substrate;
s5, removing photoresist
Taking out the PVA/PVP/graphene/substrate, placing the PVA/PVP/graphene/substrate in deionized water at 75 ℃ for 10min-15min, removing PVA/PVP colloid, placing the PVA/PVP colloid in deionized water for cleaning for 5 times, and placing the PVA/PVP colloid in an oven for drying, wherein preferably, the temperature of the oven is 110 ℃, and the treatment time is 10 min.
Preferably, the step S2 specifically includes the following steps:
s21, cutting graphene/copper foil with a required size, putting the graphene/copper foil into sealed deionized water, heating for 3 hours in a water bath at 50 ℃, taking out, spin-coating the obtained PVP glue on the graphene surface through a glue homogenizing machine, and setting parameters of the glue homogenizing machine as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 2000 revolutions per minute for 30s, the glue is homogenized for 2 times, and after the glue is homogenized, the glue is transferred to a hot plate for drying, the temperature of the hot plate is 75 ℃, and the time is 90 s;
s22, spin-coating the dried PVP glue with the PVA glue obtained through a spin coater, wherein the parameters of the spin coater are as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 4000 revolutions per minute for 30s, the glue is homogenized for 1 time, and after the glue is homogenized, the glue is transferred to an oven to be dried, the temperature of the oven is 110 ℃, and the time is 15 min.
The invention has the following beneficial effects:
the method has the advantages of less residual protective glue, no heavy metal residue, less residual organic solvent, less time consumption for transferring graphene, low cost, higher quality of transferred graphene and the like, has more prospect compared with the traditional wet transfer, and has good promotion effect and greater attraction for the preparation and application industries of graphene.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, an embodiment of the present invention provides a CVD graphene dry transfer method, including the following steps:
s1, preparing PVP (polyvinylpyrrolidone) and PVA (polyvinyl alcohol) colloid;
PVP glue: weighing 1g of PVP white powder, adding 1ml of deionized water, adding 2ml of NVP into the PVP white powder, finally adding absolute ethyl alcohol to 10ml, manually stirring until the absolute ethyl alcohol is completely dissolved, sealing and storing at low temperature (0-4 ℃);
PVA glue: weighing 1g of PVA white powder, adding 10ml of deionized water, placing on a magnetic stirrer, setting the temperature at 80 ℃, stirring for 1h until the PVA white powder is completely dissolved and is viscous and colloidal, sealing and storing at normal temperature;
s2, spin-coating colloid in sequence;
s21, cutting graphene/copper foil with a required size, putting the graphene/copper foil into sealed deionized water, heating for 3 hours in a water bath at 50 ℃, taking out, spin-coating the obtained PVP glue on the graphene surface through a glue homogenizing machine, and setting parameters of the glue homogenizing machine as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 2000 revolutions per minute for 30s, the glue is homogenized for 2 times, and after the glue is homogenized, the glue is transferred to a hot plate for drying, the temperature of the hot plate is 75 ℃, and the time is 90 s;
s22, spin-coating the dried PVP glue with the PVA glue obtained through a spin coater, wherein the parameters of the spin coater are as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 4000 revolutions per minute for 30s, the glue is homogenized for 1 time, and after the glue is homogenized, the glue is transferred to an oven to be dried, the temperature of the oven is 110 ℃, and the time is 15 min.
S3, taking out the PVA/PVP/graphene/copper foil, stripping the PVA/PVP/graphene film, transferring the stripped film between two transparent glass slides, and preheating the film on a hot plate for 90S at 75 ℃ to naturally stretch the film;
s4 transfer graphene
Soaking the naturally stretched PVA/PVP/graphene film in absolute ethyl alcohol at 50 ℃ for 5s, taking out, adhering the film to the cleaned substrate, naturally airing, placing the film in water vapor at 75 ℃ for 10min, firmly adhering the film and the substrate, and placing the film in an oven for drying at the temperature of 110 ℃ for 10min to obtain the PVA/PVP/graphene/substrate;
s5, removing photoresist
Taking out the PVA/PVP/graphene/substrate, placing the PVA/PVP/graphene/substrate in deionized water at 75 ℃ for 10-15 min, removing PVA/PVP colloid, placing the PVA/PVP colloid in deionized water for cleaning for 5 times, and placing the PVA/PVP colloid in an oven for drying.
Compared with the traditional wet transfer process, the method has the characteristics of simple process, no heavy metal impurity residue, less colloid residue, less organic pollution and the like, and the graphene transferred by the dry transfer method can better approach the intrinsic performance of the graphene in the aspects of electricity, mechanics, optics and the like, thereby having great value in the aspects of preparing photoelectric devices and energy storage materials. On one hand, the process uses water-soluble protective glue, the chemical performance of the water-soluble protective glue can be kept stable in the transferring process, no reaction can be caused with graphene, the protective glue can be better removed by using deionized water with the constant temperature of 75 ℃ in the glue removing process, and after glue removing, the glue residue on a sample is less, and the performance of a graphene device cannot be influenced; on the other hand, before graphene is transferred by using the method, the graphene/copper foil needs to be subjected to oxidation treatment, so that a copper oxide isolation layer is generated between the graphene and the substrate copper foil, the stress between the graphene and the copper foil is reduced, and the graphene can be more fully stripped. In addition, in the process of transferring graphene, the PVP/PVA/graphene film which is stripped off is subjected to preheating treatment, so that the film which is just stripped off can be naturally leveled, and then the film is immersed into warm absolute ethyl alcohol to be combined with a target substrate, and the step is crucial to the quality of the transferred graphene.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. A CVD graphene dry transfer method is characterized by comprising the following steps:
s1, preparing PVP (polyvinylpyrrolidone) and PVA (polyvinyl alcohol) colloid;
PVP glue: weighing 1g of PVP white powder, adding 1ml of deionized water, adding 2ml of NVP into the PVP white powder, finally adding absolute ethyl alcohol to 10ml, manually stirring until the absolute ethyl alcohol is completely dissolved, sealing, and storing at the low temperature of 0-4 ℃;
PVA glue: weighing 1g of PVA white powder, adding 10ml of deionized water, placing on a magnetic stirrer, setting the temperature at 80 ℃, stirring for 1h until the PVA white powder is completely dissolved and is viscous and colloidal, sealing and storing at normal temperature;
s2, spin-coating colloid in sequence;
cutting graphene/copper foil with a required size, putting the graphene/copper foil on sealed deionized water, heating the graphene/copper foil in a water bath at 50 ℃ for 3 hours, taking out the graphene/copper foil, sequentially spin-coating the obtained PVP glue and PVA glue on the graphene surface, and drying the PVP glue and PVA glue in an oven;
s3, taking out the PVA/PVP/graphene/copper foil, stripping the PVA/PVP/graphene film, transferring the stripped film between two transparent glass slides, and preheating the film on a hot plate for 90S at 75 ℃ to naturally stretch the film;
s4 transfer graphene
Soaking the naturally stretched PVA/PVP/graphene film in absolute ethyl alcohol at 50 ℃ for 5s, taking out, adhering the film to the cleaned substrate, naturally airing, placing the film in water vapor at 75 ℃ for 10min, firmly adhering the film and the substrate, and placing the film in an oven for drying at the temperature of 110 ℃ for 10min to obtain the PVA/PVP/graphene/substrate;
s5, removing photoresist
Taking out the PVA/PVP/graphene/substrate, placing the PVA/PVP/graphene/substrate in deionized water at 75 ℃ for 10-15 min, removing PVA/PVP colloid, placing the PVA/PVP colloid in deionized water for cleaning for 5 times, placing the PVA/PVP colloid in an oven, and drying the PVA/PVP colloid.
2. The CVD graphene dry transfer method according to claim 1, wherein the step S2 specifically comprises the following steps:
s21, cutting graphene/copper foil with a required size, putting the graphene/copper foil into sealed deionized water, heating for 3 hours in a water bath at 50 ℃, taking out, spin-coating the obtained PVP glue on the graphene surface through a glue homogenizing machine, and setting parameters of the glue homogenizing machine as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 2000 revolutions per minute for 30s, the glue is homogenized for 2 times, and after the glue is homogenized, the glue is transferred to a hot plate for drying, the temperature of the hot plate is 75 ℃, and the time is 90 s;
s22, spin-coating the dried PVP glue with the PVA glue obtained through a spin coater, wherein the parameters of the spin coater are as follows: the low speed is 1000 revolutions per minute for 6s, the high speed is 4000 revolutions per minute for 30s, the glue is homogenized for 1 time, and after the glue is homogenized, the glue is transferred to an oven to be dried, the temperature of the oven is 110 ℃, and the time is 15 min.
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| CN109516454A (en) * | 2018-12-14 | 2019-03-26 | 清华大学 | A kind of graphene transfer method |
| GR1009757B (en) * | 2018-12-31 | 2020-06-01 | Ιδρυμα Τεχνολογιας Ερευνας/Ινστιτουτο Επιστημων Χημικης Μηχανικης (Ιτε/Ιεχμη) | Protection of artworks with bi-dimensional materials such as graphene |
| CN114195142B (en) * | 2020-09-17 | 2023-05-26 | 香港城市大学深圳研究院 | Graphene transfer method for stripping polymer support material based on alcohol solvent |
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| US8753468B2 (en) * | 2009-08-27 | 2014-06-17 | The United States Of America, As Represented By The Secretary Of The Navy | Method for the reduction of graphene film thickness and the removal and transfer of epitaxial graphene films from SiC substrates |
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