CN108963007B - Graphene/silicon solar cell - Google Patents
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- CN108963007B CN108963007B CN201810752890.XA CN201810752890A CN108963007B CN 108963007 B CN108963007 B CN 108963007B CN 201810752890 A CN201810752890 A CN 201810752890A CN 108963007 B CN108963007 B CN 108963007B
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- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses a graphene/silicon solar cell which comprises a transparent electrode layer, wherein the transparent electrode is a graphene film, the thickness of the graphene film is not more than 20nm, graphene layers are crosslinked, and the crosslinking degree is 1-5%. The graphene film is prepared from graphene oxide through the steps of vacuum filtration film forming, chemical reduction, solid phase transfer, metal spraying, medium-temperature carbonization, chlorination, high-temperature graphitization and the like. The whole film is of a graphene structure, and a large number of interlayer cross-linked structures are arranged among the sheets. In contrast, the graphene film has high electron mobility and relatively low light transmittance, the solar energy absorption rate of silicon is increased through continuous reflection, and electron holes generated by the graphene film can be separated under the action of a built-in electric field, so that the light conversion efficiency is improved.
Description
Technical Field
The invention relates to a solar electrode, in particular to a graphene/silicon-based solar cell.
Background
With the increasing severity of environmental issues, environmental issues arising from the unregulated use of fossil energy sources are attracting increasing attention. People hope to find renewable and pollution-free new energy to replace heavily polluted fossil energy. Solar energy has been a concern of people as a source of the earth statement. The graphene/silicon solar cell is one of the applications, and is a heterojunction constructed by using different work functions of graphene (4.5eV) and silicon (4.31eV), and when sunlight irradiates the surfaces of the graphene/silicon solar cell and the silicon, valence electrons in the silicon absorb photon energy in incident light to perform transition, so that electron-hole pairs are formed. Under the action of a built-in electric field, electron-hole pairs are separated and can be transmitted to an external circuit through graphene and silicon, and conversion from solar energy to electric energy is achieved.
However, the conventional graphene/silicon solar cell uses single-layer graphene or few-layer mechanically-exfoliated graphene as a transparent conductive electrode, and has the following problems that firstly, the graphene is low in thickness and too low in light absorption rate; secondly, the single-layer graphene has many transfer defects and low electron mobility, and is not beneficial to the transmission of photoelectrons; third, few-layer graphene has too small an area to be suitable for large-scale preparation.
Therefore, the graphene film with high strength, high conductivity and high transparency is designed for overcoming various problems of the traditional graphene, the interface reflection is increased by increasing the thickness, and meanwhile, the graphene can absorb solar energy and increase the light conversion efficiency under the action of an internal electric field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a graphene/silicon solar cell.
The purpose of the invention is realized by the following technical scheme: a graphene/silicon solar cell is characterized by having a two-layer structure, wherein one layer is a silicon layer, the other layer is a graphene layer, and the graphene layer is attached to the silicon layer; the thickness of the graphene layer is not more than 20nm, the graphene layers are crosslinked, and the crosslinking degree is 1-5%. The preparation method comprises the following steps:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating the graphene oxide film from the bottom to the top at a high temperature of 80-100 ℃ for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step 3 to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal such as titanium, molybdenum or cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene film.
Further, the solid transfer agent is selected from the group consisting of paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, rosin, and other small molecule solid substances insoluble in water that can sublime or volatilize under certain conditions.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
Further, the chlorination treatment means: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
Further, the 2000 ℃ high temperature process temperature rise process is as follows: below 1500 ℃, 5-20 ℃ per minute; above 1500 ℃ and 2-5 ℃ per minute.
The invention has the beneficial effects that: according to the invention, firstly, an ultrathin graphene film is obtained in a solid transfer mode, so that a foundation is laid for the high resistance of a device; further, the surface wrinkles of the graphene film are increased through slow heating (1 ℃/min), and the area of the graphene film in a unit space is expanded; and then heating at a speed of 10 ℃/min and placing at 2000 ℃ to remove most of atomic defects in the graphene, but not recovering the stacking structure in the graphene. Further sputtering metal particles on the surface of the ultrathin graphene film, and reacting the metal particles with the graphene at high temperature to form metal carbide; then the metal carbide forms metal chloride under the action of chlorine and escapes, meanwhile, the carbon structure is converted to the diamond structure, the strength (reaching 7-20GPa) and the thermal stability of the film are greatly improved, the graphene film structure is recovered to a great extent by high-temperature treatment at 2000 ℃, but the interlayer cross-linking structure is not influenced and an AB accumulation structure is not formed. The battery has the advantages that transparency is guaranteed, meanwhile, the electric conductivity and the mechanical bearing performance are guaranteed, and the battery can endure various environmental problems and external interference in the using process. In contrast, graphene has higher electron mobility, which is beneficial to electron transport; the thickness is relatively high, so that the light absorption rate of the graphene is improved; meanwhile, interface reflection is increased, and meanwhile, the graphene can absorb solar energy, so that the light conversion efficiency is increased under the action of an internal electric field; in addition, compared with few-layer graphene, the thin film prepared by the method is large in size and higher in operability.
Drawings
Fig. 1 is a raman spectrum of a non-crosslinked graphene film after treatment at 2000 degrees celsius.
Fig. 2 is a raman spectrum of the cross-linked graphene film after 2000 degrees celsius treatment.
Fig. 3 is a transmission spectrum of a non-crosslinked graphene film at 2000 degrees celsius treatment.
Fig. 4 is a transmission spectrum of a cross-linked graphene film processed at 2000 degrees celsius.
Fig. 5 is a graph of tensile strength testing of a cross-linked graphene film at 2000 degrees celsius treatment.
Fig. 6 is a schematic structural diagram of a graphene/silicon solar cell.
Detailed Description
Example 1:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene membrane in a closed container, and fumigating the graphene oxide membrane from the bottom to the top for 1h at a high temperature of 80 ℃.
(3) And uniformly coating the melted solid transfer agent camphor on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, slowly cooling at room temperature, and separating the film from the substrate.
(4) And slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 40 ℃ to obtain the independent self-supported graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 28.6% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 1200 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 0.5% for heating treatment for 4 h.
(7) And (3) carrying out 2000-degree high-temperature treatment on the chlorinated graphene film, wherein the temperature rise process in the 2000-degree high-temperature process is as follows: below 1500 ℃ and 20 ℃ per minute; above 1500 ℃, 5 ℃ per minute; graphene films with a thickness of 19nm were obtained.
Comparing FIGS. 1 and 2, the graphene film having a plurality of crosslinked structures has a stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 4.8%, as measured by the ID/IG area ratio; in fig. 3 and 4, the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. Fig. 5 shows that the strength of the prepared graphene film is 9 GPa.
(8) And 7, flatly paving the graphene film obtained in the step 7 on a silicon substrate. Taking the surface of graphene as a light receiving surface to obtain a first solar cell of the invention; constructing single-layer graphene on the same silicon substrate by using a polymer assisted transfer method to obtain a solar cell II; compared with a battery II, the photoelectric conversion efficiency of the solar battery I is improved by 102%, and after the graphene battery I is used for 8760h, the photoelectric conversion efficiency of the solar battery is kept above 97% of the original photoelectric conversion efficiency.
Example 2:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a film by taking the PC film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 0.1 h.
(3) And uniformly coating the melted solid transfer agent naphthalene on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 80 ℃ to obtain the independent self-supporting graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 18.4% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 800 degrees celsius, so that the titanium nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 10% for heating treatment for 0.1 h.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 5 ℃ per minute; above 1500 ℃, 2 ℃ per minute; keeping the temperature at 2000 ℃ for 1 h; obtaining the graphene film with the thickness of 18 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 1.1% as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The strength of the prepared graphene film is 7 GPa.
(8) And 7, flatly paving the graphene film obtained in the step 7 on a silicon substrate. Taking the surface of graphene as a light receiving surface to obtain a first solar cell of the invention; constructing single-layer graphene on the same silicon substrate by using a polymer assisted transfer method to obtain a solar cell II; compared with a battery II, the photoelectric conversion efficiency of the solar battery I is improved by 97%, and the photoelectric conversion efficiency of the graphene battery I is kept above 96% of the original photoelectric conversion efficiency after the graphene battery I is used for 8760 h.
Example 3:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 1ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene in a closed container, and fumigating at high temperature of 90 ℃ for 0.5h from the bottom to the top.
(3) And uniformly coating the molten solid transfer agent sulfur on the surface of the reduced graphene oxide film by using a method such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 120 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 15.9% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(6) The graphene film sputtered with the metal is chlorinated at 1000 degrees celsius, allowing the cobalt nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 5% for heating treatment for 1 h.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃ and 10 ℃ per minute; above 1500 ℃, 3 ℃ per minute; keeping the temperature at 2000 ℃ for 0.5 h; obtaining the graphene film with the thickness of 14 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 1.9%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The strength of the prepared graphene film is 11 GPa.
(8) And 7, flatly paving the graphene film obtained in the step 7 on a silicon substrate. Taking the surface of graphene as a light receiving surface to obtain a first solar cell of the invention; constructing single-layer graphene on the same silicon substrate by using a polymer assisted transfer method to obtain a solar cell II; compared with a battery II, the photoelectric conversion efficiency of the solar battery I is improved by 109%, and the photoelectric conversion efficiency of the graphene battery I is kept above 94% of the original photoelectric conversion efficiency after the graphene battery I is used for 8760 h.
Example 4:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 3ug/mL, and performing suction filtration to form a membrane by taking a hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 0.2 h.
(3) And uniformly coating the melted solid transfer agent paraffin on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 200 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 25.4% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(6) The graphene film sputtered with the metal is chlorinated at 1100 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 2% for heating treatment for 2 hours.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 12 ℃ per minute; above 1500 ℃, 4 ℃ per minute; and keeping the temperature at 2000 ℃ for 1h to obtain the 13 nm-thick graphene film.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 2.2%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The strength of the prepared graphene film is 10 GPa.
(8) And 7, flatly paving the graphene film obtained in the step 7 on a silicon substrate. Taking the surface of graphene as a light receiving surface to obtain a first solar cell of the invention; constructing single-layer graphene on the same silicon substrate by using a polymer assisted transfer method to obtain a solar cell II; compared with a battery II, the photoelectric conversion efficiency of the solar battery I is improved by 99%, and the photoelectric conversion efficiency of the graphene battery I is kept above 97% of the original photoelectric conversion efficiency after the graphene battery I is used for 8760 h.
Example 5:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene membrane in a closed container, and fumigating at high temperature of 80 ℃ HI from the bottom to the top for 0.8 h.
(3) And uniformly coating the melted solid transfer agent norbornene on the surface of the reduced graphene oxide film by using methods such as evaporation, tape casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the obtained graphene film supported by the solid transfer agent at 60 ℃ under 2 atmospheric pressures to obtain the independent self-supported graphene film.
(5) And spraying a layer of metal molybdenum on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 22.8% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 800 degrees celsius, so that the molybdenum nanoparticles escape as chlorides. The method specifically comprises the following steps: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with chlorine content of 6% for heating treatment for 3 h.
(7) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 7 ℃ per minute; and (3) preserving heat for 1h at the temperature of more than 1500 ℃, 2 ℃ per minute and 2000 ℃, so as to obtain the graphene film with the thickness of 11 nm.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 3.7% as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The strength of the prepared graphene film is 9 GPa.
(8) And 7, flatly paving the graphene film obtained in the step 7 on a silicon substrate. Taking the surface of graphene as a light receiving surface to obtain a first solar cell of the invention; constructing single-layer graphene on the same silicon substrate by using a polymer assisted transfer method to obtain a solar cell II; compared with a battery II, the photoelectric conversion efficiency of the solar battery I is improved by 103%, and the photoelectric conversion efficiency of the graphene battery I is kept above 97% of the original photoelectric conversion efficiency after the graphene battery I is used for 8760 h.
Claims (4)
1. A graphene/silicon solar cell is characterized by having a two-layer structure, wherein one layer is a silicon layer, the other layer is a graphene layer, and the graphene layer is attached to the silicon layer; the thickness of the graphene layers is not more than 20nm, the graphene layers are crosslinked, and the degree of crosslinking is 1-5%; preparing the graphene layer by:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10 mug/mL, and filtering to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating the graphene oxide film from the bottom to the top at a high temperature of 80-100 ℃ for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step (3) to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal titanium, molybdenum or cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene layer.
2. The graphene/silicon solar cell of claim 1, wherein the solid transfer agent is selected from the group consisting of paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, and rosin.
3. The graphene/silicon solar cell according to claim 1, wherein the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
4. The graphene/silicon solar cell of claim 1, wherein the chlorination treatment is: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
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