CN114394587A - Graphene PN junction semiconductor refrigerating sheet and preparation method thereof - Google Patents
Graphene PN junction semiconductor refrigerating sheet and preparation method thereof Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005057 refrigeration Methods 0.000 claims abstract description 43
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 26
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- 239000000919 ceramic Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011889 copper foil Substances 0.000 claims abstract description 17
- 239000002019 doping agent Substances 0.000 claims abstract description 10
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000011241 protective layer Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004519 grease Substances 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B21/00—Machines, plants or systems, using electric or magnetic effects
- F25B21/02—Machines, plants or systems, using electric or magnetic effects using Peltier effect; using Nernst-Ettinghausen effect
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Abstract
The invention relates to the technical field of semiconductor refrigeration, in particular to a graphene p-n junction semiconductor refrigeration sheet and a preparation method thereof, wherein the graphene p-n junction semiconductor refrigeration sheet is prepared by growing graphene on a copper foil by a CVD (chemical vapor deposition) method, doping the graphene in a p type and an n type respectively, and transferring a graphene pn junction to a ceramic flat semiconductor refrigeration element to obtain the graphene pn junction semiconductor refrigeration sheet; the method comprises the steps of preparing graphene by a CVD method, transferring the graphene on a copper foil, compounding a graphene p-n junction and a ceramic flat semiconductor refrigerating element, and bonding a graphene p-n junction semiconductor refrigerating sheet and a heat-conducting silicone sheet. The graphene pn junction semiconductor refrigerating sheet prepared by the method can quickly and uniformly dissipate heat, and the performance of the refrigerating sheet can be changed by adjusting the type of the doping agent. Compared with the traditional ceramic semiconductor refrigerating sheet, the graphene pn junction semiconductor refrigerating sheet prepared by the invention has more excellent refrigerating performance and has great application potential in the aspects of heat dissipation of electronic devices, refrigerating of protective clothing and the like.
Description
Technical Field
The invention relates to the technical field of carbon material preparation and semiconductor refrigeration, in particular to a graphene p-n junction semiconductor refrigeration sheet and a preparation method thereof.
Background
Graphene is a two-dimensional crystal of a single atomic layer whose carbon atoms are hybridized in an sp2 manner and sigma-bonds adjacent carbon atoms to form a regular hexagonal structure, with a C — C bond length of about 0.142 nm. At room temperature, the carrier mobility of graphene is 15000cm 2/(V · s), the thermal conductivity of single-layer graphene is 5300W/mK, and the theoretical Young modulus can reach 1.0 TPa, so that the graphene has ultrahigh charge transfer capacity, good electric and thermal conductivity and excellent mechanical properties, and has wide application prospects in the fields of heat dissipation materials, electronic devices, human-computer interaction and the like.
Chemical Vapor Deposition (CVD) is a commonly used method for preparing nanomaterials, in which carbon-containing compounds are decomposed by chemical reactions at relatively high temperatures, so that graphene self-assembles into a solid thin film on a substrate. The CVD method for preparing the common metal substrate of graphene roughly comprises four steps: (1) the carbon source gas is adsorbed on the surface of the metal catalyst and then is catalytically decomposed; (2) the decomposed carbon atoms are diffused on the surface of the metal and are partially dissolved into the metal; (3) the dissolved carbon is separated out on the surface of the metal; (4) the precipitated carbon nucleates and grows on the surface of the metal to form graphene.
Graphene has novel electrical, optical and optoelectronic properties due to its unique two-dimensional layered atomic crystal structure and dirac tapered electronic band structure. The p-n junction is the core structure of bipolar transistors and field effect transistors, and is the basis of modern electronic technology. The p-n junction in the graphene has an electron negative refractive index effect and a fractional quantum Hall effect, and in addition, the specific 'photoelectric and electric' effect can also realize high-efficiency photoelectric energy conversion based on a 'hot carrier' principle. The Peltier effect of the graphene p-n junction can be applied to the aspects of heat dissipation, quick refrigeration and the like, besides, the graphene p-n junction is expected to be applied to a very small photoelectric detector, the application prospect is very wide, and the chemical potential difference of the graphene p-n junction is improved by adjusting the dopant, so that the efficiency of the photoelectric detector can be improved.
However, in order to achieve this goal, stable doping with high controllability and uniformity must be achieved on the premise of ensuring the quality of graphene, and the CVD method is currently one of the commonly used methods for controllably preparing graphene. Therefore, chemical doping is carried out after graphene is grown by a CVD method, the whole graphene p-n junction is transferred to the ceramic flat semiconductor refrigeration element and then is bonded with the heat-conducting silicone grease radiating fin, and the large chemical potential difference of the graphene p-n junction is realized by adjusting the type of the dopant, so that the graphene p-n junction has better heat dissipation and refrigeration performances.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to grow graphene by a CVD method and perform chemical doping on the graphene, so that the obtained graphene p-n junction can be compounded with a ceramic flat semiconductor refrigeration element for refrigeration and can also be used as a photoelectric detector and the like.
The purpose of the invention is realized by the following technical scheme:
a graphene p-n junction semiconductor refrigeration sheet and a preparation method thereof comprise the following steps:
growing graphene on a copper foil by using a CVD (chemical vapor deposition) method;
and step two, coating PMMA (polymethyl methacrylate) on the S end of the graphene grown by the CVD method for protection, and soaking the D end in HNO3 (63 wt%) solution. The HNO3 has strong oxidizing property and can break an sp2 bond of the graphene, carbon atoms at the edge or the defect of the graphene form sp3 hybridization, the graphene is subjected to oxidation reaction in nitric acid, oxygen radicals generated in the reaction process and C form hydroxyl or carboxyl, a sub-band is generated near a Fermi level, and effective p-type doping is further formed. P-type doping can also be formed by soaking in a solution of trifluoromethanesulfonic acid (CF 3SO 3H). Or in an air environment, the dipole moment of water molecules is adsorbed on the graphene to generate a local electrostatic field, so that charges in the graphene are partially transferred to the water molecules to generate p-type doping.
Removing PMMA at the S end of the prepared p-type doped graphene by using acetone;
step four, carrying out n-doping on the graphene by using a Polyethyleneimine (PEI), cesium fluoride (CsF) or O-MeO-DMBI solution, wherein when the graphene is doped by the PEI, hole conduction in the graphene is inhibited and electron conduction is reserved due to non-equilibrium carrier injection, so that n-type graphene is formed, and an in-plane p-n junction is further formed;
compounding the prepared graphene p-n junction with a ceramic flat semiconductor refrigeration element to obtain a graphene p-n junction semiconductor;
and sixthly, adding a layer of heat-conducting silicone grease sheet respectively above and below the prepared graphene p-n junction semiconductor refrigerating sheet so as to facilitate heat dissipation, and thus obtaining the graphene p-n junction semiconductor refrigerating sheet.
Preferably, the graphene grown by the CVD method in the second step is divided into a D terminal and an S terminal, and the S terminal is coated with PMMA as a protective layer.
Preferably, the dopant in the second step is HNO3 (63 wt%), and the D-end of the graphene on the copper foil is soaked in the HNO3 solution for 1-30 min.
Preferably, the graphene soaked with HNO3 is dried at room temperature, and after the sample is completely dried, acetone is used to dissolve PMMA at the S-terminal of the graphene.
Preferably, the dopant in the fourth step is Polyethyleneimine (PEI), and the uniform and air-stable n-type doped graphene is obtained by adjusting the work function through a laminated structure.
Preferably, the graphene in-plane p-n junction is transferred to the ceramic flat plate by a transfer method.
Preferably, the ceramic flat semiconductor refrigeration element consists of 4 refrigeration pieces and a pure aluminum piece, and the periphery of the aluminum piece is wrapped with a heat preservation and insulation material, so that the refrigeration loss is reduced.
Preferably, the heat-conducting silicone sheet and the heat radiating fins adopt fin structures, and the graphene p-n junction semiconductor refrigerating sheet is obtained by bonding an adhesive and a ceramic flat plate.
Compared with the prior art, the invention has the following beneficial effects:
the graphene p-n junction semiconductor refrigeration sheet prepared by the invention can realize larger chemical potential difference of the graphene p-n junction by adjusting the type of the dopant and the reaction time, and has more obvious heat dissipation and refrigeration effects.
And b, the refrigeration performance of the graphene p-n junction semiconductor prepared by the invention is superior to that of the traditional ceramic flat semiconductor, and the graphene p-n junction semiconductor can better play a role in heat conduction and refrigeration.
compared with other methods, the method for preparing the refrigerating sheet has the characteristics of controllable operation and uniform and stable product in the CVD method, and the chemical doping method has the advantages of simplicity and convenience in operation, adjustability, low cost and the like.
Drawings
Fig. 1 is a schematic structural diagram of a graphene PN junction semiconductor refrigeration sheet disclosed by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The invention discloses a graphene PN junction semiconductor refrigerating sheet which comprises a ceramic substrate 2, wherein a graphene PN junction 1 is arranged on the upper portion of the ceramic substrate 2, the graphene PN junction 1 comprises an S end 11 and a D end 12 which are adjacently arranged at the left and right, graphene at the S end 11 is P-type doped graphene, and graphene at the D end 12 is N-type doped graphene. The ceramic substrate 2 comprises an aluminum sheet and 4 refrigerating sheets, and the surface of the aluminum sheet is coated with a heat-insulating material. And the upper part of the graphene PN junction 1 and the lower part of the ceramic substrate 2 are both provided with heat conduction silicone grease 3.
Example 1
The graphene p-n junction semiconductor refrigeration sheet and the preparation method thereof comprise the following steps:
growing graphene on a copper foil by a CVD method:
a chemical vapor deposition system (cold wall CVD) is adopted, the equipment is firstly pumped to a low-pressure state, argon is introduced to prevent gas pollution in the operation process, a copper foil processed in advance is used as a substrate, then methane is introduced to grow graphene at a high temperature, the temperature rise process is carried out in a gradient temperature rise mode, and the total temperature is maintained at 1050 ℃.
And step two, coating PMMA on one end of the copper foil graphene prepared in the step one, which is 5 multiplied by 5 cm2, as a protective layer, and immersing the other end, which is not coated with PMMA, in 2.5 cm of HNO3 solution (63 wt%) for 5min or forming p-type doping.
Removing PMMA, and carrying out n-type doping on graphene:
and soaking the graphene in acetone for 30min to replace the new solution, repeating the operation for three times to remove PMMA, and using Polyethyleneimine (PEI) as a doping agent to adjust the work function of all graphene through a laminated structure to obtain uniform and stable n-type doped graphene.
And step four, removing the copper substrate of the prepared in-plane graphene p-n junction by using an ammonium persulfate solution with the concentration of 3%, drying the copper substrate, and firmly adhering the graphene p-n junction to the ceramic flat semiconductor refrigeration element by using a double faced adhesive tape to obtain the graphene p-n junction semiconductor.
And step five, respectively adhering a layer of heat-conducting silicone grease on the upper surface and the lower surface of the prepared graphene p-n junction semiconductor refrigerating sheet to obtain the graphene p-n junction semiconductor refrigerating sheet.
Example 2
A graphene p-n junction semiconductor refrigeration sheet and a preparation method thereof comprise the following steps:
growing graphene on a copper foil by a CVD method:
a chemical vapor deposition system (cold wall CVD) is adopted, the equipment is firstly pumped to a low-pressure state, argon is introduced to prevent gas pollution in the operation process, a copper foil processed in advance is used as a substrate, then methane is introduced to grow graphene at a high temperature, the temperature rise process is carried out in a gradient temperature rise mode, and the total temperature is maintained at 1050 ℃.
And step two, coating PMMA on one end of the copper foil graphene prepared in the step one, which is 5 multiplied by 5 cm2, as a protective layer, and immersing the other end, which is not coated with PMMA, in trifluoromethanesulfonic acid (CF 3SO3H) solution for 15min to form p-type doping.
Removing PMMA, and carrying out n-type doping on graphene:
the method comprises the steps of soaking the graphene in acetone for 30min to replace a new solution, repeating the operation for three times to remove PMMA, using cesium fluoride (CsF) as a doping agent, treating all graphene through a full solution, and manufacturing the graphene under any condition without a vacuum process, wherein the sheet resistance and the light transmittance of the graphene can be modified through a water-containing process.
And step four, removing the copper substrate of the prepared in-plane graphene p-n junction by using an ammonium persulfate solution with the concentration of 3%, drying the copper substrate, and firmly adhering the graphene p-n junction to the ceramic flat semiconductor refrigeration element by using a double faced adhesive tape to obtain the graphene p-n junction semiconductor.
And step five, respectively adhering a layer of heat-conducting silicone grease on the upper surface and the lower surface of the prepared graphene p-n junction semiconductor refrigerating sheet to obtain the graphene p-n junction semiconductor refrigerating sheet.
Example 3
A graphene p-n junction semiconductor refrigeration sheet and a preparation method thereof comprise the following steps:
growing graphene on a copper foil by a CVD method:
a chemical vapor deposition system (cold wall CVD) is adopted, the equipment is firstly pumped to a low-pressure state, argon is introduced to prevent gas pollution in the operation process, a copper foil processed in advance is used as a substrate, then methane is introduced to grow graphene at a high temperature, the temperature rise process is carried out in a gradient temperature rise mode, and the total temperature is maintained at 1050 ℃.
And step two, coating PMMA (polymethyl methacrylate) on one end of the copper foil graphene prepared in the step one and having the thickness of 5 multiplied by 5 cm2 as a protective layer, wherein small molecules are easily adsorbed on the surface of the graphene, and in an air environment, the dipole moment of water molecules is adsorbed on the graphene to generate a local electrostatic field, so that charges in the graphene are partially transferred to the water molecules, and the p-type doping is generated within 150 min.
Removing PMMA, and carrying out n-type doping on graphene:
the organic compound is soaked in acetone for 30min to replace a new solution, the operation is repeated for three times to remove PMMA, and a solution of a molecule of 2- (2-methoxyphenyl) -1, 3-dimethyl-2, 3-dihydro-1H-benzimidazole, namely an O-MeO-DMBI solution (the concentration is 0.1 mg/mL) is used, so that the organic compound not only has a stronger electron-donating group, but also can be conjugated with the surface of graphene through a benzene ring, and thus the graphene has obvious n-type doping.
And step four, removing the copper substrate of the prepared in-plane graphene p-n junction by using an ammonium persulfate solution with the concentration of 3%, drying the copper substrate, and firmly adhering the graphene p-n junction to the ceramic flat semiconductor refrigeration element by using a double faced adhesive tape to obtain the graphene p-n junction semiconductor.
And step five, respectively adhering a layer of heat-conducting silicone grease on the upper surface and the lower surface of the prepared graphene p-n junction semiconductor refrigerating sheet to obtain the graphene p-n junction semiconductor refrigerating sheet.
Experimental example 4
A testing method of a graphene p-n junction semiconductor refrigerating sheet comprises the following steps:
the method comprises the steps of firstly, respectively testing the refrigeration effect of the three graphene p-n junction semiconductor refrigeration sheets, and then, comparing and testing the refrigeration effect of the ceramic flat semiconductor refrigeration element. The semiconductor refrigerating sheet is a heat transfer tool, and as long as the temperature of the hot end (cooled object) is higher than a certain temperature, the semiconductor refrigerator starts to work, so that the temperatures of the cold end and the hot end are gradually equalized, and the refrigerating effect is achieved. The heat release power is calculated according to the formula: q = pi · I = a · Tc · I, where pi = a · Tc,
in the formula: q-exothermic or endothermic Power;
pi-the proportionality coefficient, called the peltier coefficient;
i-operating current;
a-thermoelectric power ratio;
tc-cold junction temperature.
Experiment 1: the refrigeration effect of the device is verified under the condition that the ambient temperature is 25 ℃. When the direct current enters the N-P type couple pair, the right end of the couple pair absorbs heat to form a cold end which is connected with a transparent cold chamber; the left end releases heat to form a hot end which is connected with a heat radiation water tank. The Peltier effect can be conveniently and visually observed with obvious effect by matching a thermometer and a millivoltmeter, and the test result is shown in Table 1.
Table 1:
the direct current of 1-3A is respectively introduced to the graphene p-n junction semiconductor refrigeration sheet, the temperature of the transparent cold chamber and the temperature of the heat dissipation water tank are recorded every 1min through the thermometer, and the experimental results show that after the direct current of 1A is introduced, the temperature of the heat dissipation water tank of the embodiment 1-3 is higher than the room temperature, and the temperature is higher along with the time. Meanwhile, as the current rises to 2A or 3A, the rate of temperature rise in the radiator tank is faster. The cold chamber is the opposite, and the temperature in the cold chamber is lower than the room temperature after the current is applied, and continues to decrease with the passage of time. The larger the current is introduced, the more obvious the refrigeration effect is. From the above results, it can be seen that the refrigeration effect of example 3 is the best, and the longer the current is, the higher the current is, the more obvious the refrigeration and heat dissipation effects are.
Experiment 2: setting 4 thermocouples at equal intervals from the center to the edge of the aluminum sheet, compounding the graphene p-n junction semiconductor refrigeration sheet with the aluminum sheet, setting a specific temperature for the graphene p-n junction semiconductor refrigeration sheet, measuring the temperature gradient distribution of the aluminum sheet, and obtaining a test result shown in table 2. The result shows that no temperature gradient exists on the surface of the aluminum sheet, which is caused by the temperature of the secondary homogenization molding surface of the heat-conducting silicone grease layer and the aluminum sheet layer on the Peltier refrigerating sheet.
Table 2:
known from the above table, when applying different temperatures to the aluminum sheet, because the special two-dimensional structure of graphite alkene PN junction semiconductor, can be with the heat diffusion in the face rapidly, the data demonstration of surveying through 4 thermocouples on the aluminum sheet, the difference in temperature control everywhere on the aluminum sheet is within 0.5 ℃, can prove that graphite alkene PN junction semiconductor has good homothermal effect from this for aluminum sheet temperature everywhere all has good homogeneity, graphite alkene PN junction semiconductor refrigeration piece has better homothermal effect, there is not temperature gradient's distribution in the dull and stereotyped face.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Graphene PN junction semiconductor refrigeration piece, its characterized in that includes ceramic substrate, ceramic substrate upper portion is equipped with graphene PN junction, graphene PN junction is including controlling adjacent S end and the D end that sets up, the graphene of S end is P type doping graphene, the graphene of D end is N type doping graphene.
2. The graphene PN junction semiconductor refrigeration sheet according to claim 1, wherein: the ceramic substrate comprises an aluminum sheet and a refrigerating sheet, and the surface of the aluminum sheet is coated with a heat insulating material.
3. The graphene PN junction semiconductor refrigeration sheet according to claim 1, wherein: and the upper part of the graphene PN junction and the lower part of the ceramic substrate are both provided with heat-conducting silicone grease.
4. A preparation method of a graphene PN junction semiconductor refrigerating sheet is characterized by comprising the following steps:
1) growing graphene on the copper foil by using a CVD (chemical vapor deposition) method;
2) arranging the graphene into an S end and a D end, coating a protective layer at the S end, and forming effective p-type doped graphene at the D end;
3) removing the protective layer at the S end;
4) carrying out n-type doping on the sample obtained in the step 3 by using an n-type dopant to form n-type doped graphene, and further obtaining an in-plane graphene PN junction;
5) and after removing the copper foil substrate, compounding the prepared graphene pn junction with a ceramic substrate to obtain the graphene pn junction semiconductor.
5. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: in the step 2, the p-type doping is formed by soaking the D terminal in 63wt% HNO3 solution, or in trifluoromethanesulfonic acid (CF 3SO3H) solution, or in a manner that local electrostatic field is generated by adsorbing the D terminal on the graphene by using the dipole moment of water molecules in an air environment; preferably, the D end is soaked in an HNO3 solution with the mass fraction of 63wt% to prepare the p-type doped graphene.
6. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: in step 2, the step of coating the protective layer at the S end comprises the following specific steps: the copper foil grown with graphene obtained by CVD is cut into a predetermined size, and a protective layer is coated on the S-end of the graphene with PMMA.
7. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: and 3, soaking in acetone to remove the PMMA protective layer on the surface of the S end.
8. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: and repeating the step 3 for 2-3 times.
9. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: and 5, removing the copper foil substrate of the in-plane graphene pn junction by using an ammonium persulfate solution with the concentration of 3%.
10. The preparation method of the graphene PN junction semiconductor chilling plate according to claim 4, characterized by comprising the following steps: the n-type dopant used in the step 4 is selected from one of polyethyleneimine, cesium fluoride and O-MeO-DMBI solution.
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