WO2023184966A1 - 一种碳纳米管/银纳米线复合薄膜及其砷化镓基异质结太阳电池和制备方法 - Google Patents

一种碳纳米管/银纳米线复合薄膜及其砷化镓基异质结太阳电池和制备方法 Download PDF

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WO2023184966A1
WO2023184966A1 PCT/CN2022/128738 CN2022128738W WO2023184966A1 WO 2023184966 A1 WO2023184966 A1 WO 2023184966A1 CN 2022128738 W CN2022128738 W CN 2022128738W WO 2023184966 A1 WO2023184966 A1 WO 2023184966A1
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carbon nanotube
composite film
silver nanowire
nanowire composite
gallium arsenide
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PCT/CN2022/128738
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English (en)
French (fr)
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李国强
莫由天
张志杰
曾庆浩
邓曦
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华南理工大学
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    • H—ELECTRICITY
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/07—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the Schottky type
    • H—ELECTRICITY
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP

Definitions

  • the present invention relates to the technical field of solar cells, and more specifically, to a carbon nanotube/silver nanowire composite film, a gallium arsenide-based heterojunction solar cell and a preparation method thereof.
  • the prior art discloses a carbon nanotube/gallium arsenide heterojunction wide spectrum ultra-thin solar cell and its construction method, which includes: a lower electrode, an N-type gallium arsenide substrate, and a window with a window on the gallium arsenide substrate.
  • the insulating layer is a carbon nanotube film in direct contact with gallium arsenide located in the window of the insulating layer, and a patterned upper electrode is provided on the carbon nanotube film on the surface of the insulating layer.
  • This invention can simultaneously utilize the efficient absorption and conversion characteristics of photons of carbon nanotubes and gallium arsenide, and quickly separate and transport them through the formed heterojunction interface. On the one hand, it reduces the probability of photogenerated carrier recombination, and on the other hand The response spectrum of gallium arsenide is broadened.
  • the solar cell of this invention has the advantages of simple structure, simple process, lightness and thinness.
  • the present invention provides a carbon nanotube/silver nanowire composite film
  • the invention also provides a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell
  • the invention also provides a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell.
  • a carbon nanotube/silver nanowire composite film prepared by the following preparation method:
  • Step 1 Add the carbon nanotube powder to the sodium dodecylbenzene sulfonate solution, disperse and centrifuge to obtain a carbon nanotube suspension, and mix the carbon nanotube suspension with silver nanowires and water to obtain a diluted mixed solution.
  • the diluted mixture is subjected to vacuum filtration to obtain a carbon nanotube/silver nanowire composite film/filtration membrane;
  • Step 2 Place the carbon nanotube/silver nanowire composite film/filter membrane obtained in step 1 on a cleaned substrate, so that the carbon nanotubes/silver nanowire composite film/filter membrane in the carbon nanotube/silver nanowire composite film/filter membrane are The silver nanowire composite film is in contact with the surface of the substrate and pressed, and alcohol is added dropwise, and then vacuum filtration is performed, and then the filter membrane part of the carbon nanotube/silver nanowire composite film/filter membrane is removed. A carbon nanotube/silver nanowire composite film was obtained.
  • the mass fraction of the sodium dodecylbenzene sulfonate solution in step 1 is 0.1 to 1%, and the diluted mixture contains carbon nanoparticles with a concentration of 8 ⁇ 10 -4 to 1.65 ⁇ 10 -3 mg/mL. tube, containing silver nanowires at a concentration of 1.52 ⁇ 10 -6 to 1.52 ⁇ 10 -5 mg/mL.
  • the mass fraction of the sodium dodecyl benzene sulfonate solution in step 1 is 0.5%
  • the diluted mixture contains carbon nanotubes with a concentration of 1.27 ⁇ 10 -3 mg/mL, and a concentration of 7.58 ⁇ 10 - 6 mg/mL silver nanowires.
  • step 1 ultrasonic dispersion is performed, and the carbon nanotube suspension is obtained by centrifugation at a rotation speed of 1000 to 5000 rpm for 1 to 60 minutes.
  • step 1 is centrifuged at a rotation speed of 4000 rpm for 20 minutes to obtain the carbon nanotube suspension.
  • a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell includes the following parts from bottom to top: back electrode, gallium arsenide substrate, hole transport layer, insulating layer and front electrode,
  • the hole transport layer is a carbon nanotube/silver nanowire composite film prepared by the technology of the present invention. Its upper surface also has a light-receiving window, and the light-receiving window is spin-coated with a passivation layer.
  • a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell including the following steps:
  • Step 1 Prepare a back electrode on one side of the gallium arsenide substrate
  • Step 2 Add the carbon nanotube powder to the sodium dodecylbenzene sulfonate solution, disperse and centrifuge to obtain a carbon nanotube suspension, and mix the carbon nanotube suspension with silver nanowires and water to obtain a diluted mixed solution.
  • the diluted mixture is subjected to vacuum filtration to obtain a carbon nanotube/silver nanowire composite film/filtration membrane;
  • Step 3 Place the carbon nanotube/silver nanowire composite film/filter membrane obtained in step 2 on the other side of the gallium arsenide substrate described in step 1, so that the carbon nanotube/silver nanowire composite film/filter membrane
  • the carbon nanotube/silver nanowire composite film in the film is in contact and pressed with the other side of the gallium arsenide substrate, and alcohol is added dropwise, and then vacuum filtration is performed, and finally the carbon nanotube/silver nanowire composite film is removed From the filter membrane part of the thin film/filter membrane, a gallium arsenide substrate containing a carbon nanotube/silver nanowire composite thin film hole transport layer can be obtained;
  • Step 4 Perform photolithography and evaporation on the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film described in Step 3 to prepare an insulating layer, and prepare a front electrode on the surface of the insulating layer to make the carbon nanotube/silver nanowire composite film described in Step 3 A light-receiving window is formed on the surface of the hole transport layer of the tube/silver nanowire composite film;
  • Step 5 Spin-coat the passivation layer on the light-receiving window described in Step 4.
  • the carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell is obtained.
  • the carbon nanotube powder is first dissolved into the sodium dodecyl benzene sulfonate solution, dispersed, Centrifuge to obtain a uniformly dispersed carbon nanotube suspension, and then mix and dilute it with silver nanowires and water to obtain a uniformly dispersed diluted mixture to prepare a high-quality carbon nanotube/silver nanowire composite film, and transfer it to the
  • alcohol is added dropwise, and the volatilization of the alcohol is used to promote the carbon nanotube/silver nanowire composite film to be more closely combined with the gallium arsenide substrate.
  • the present invention prepares a carbon nanotube/silver nanowire composite film on a gallium arsenide substrate through vacuum filtration, which is not limited by the high temperature resistance of the substrate and can broaden the scope of the carbon nanotube/silver nanowire composite film. Application areas of thin films.
  • step one cleaning is required before and after preparing the back electrode on the gallium arsenide substrate.
  • the cleaning process is as follows: cleaning with acid, acetone, ethanol, and water in sequence, and then blowing dry with nitrogen.
  • the gallium arsenide substrate is ultrasonically pickled with a 10% HCl solution for 3 minutes, then ultrasonically cleaned with acetone, ethanol, and deionized water for 5 minutes, and dried with nitrogen. After evaporating the back electrode on the gallium arsenide substrate, repeat the above cleaning steps and blow dry with nitrogen again for later use.
  • the gallium arsenide substrate containing the back electrode is obtained through evaporation and annealing processes.
  • the mass fraction of the sodium dodecylbenzene sulfonate solution in step 2 is 0.1 to 1%, and the diluted mixture contains carbon nanoparticles with a concentration of 8 ⁇ 10 -4 to 1.65 ⁇ 10 -3 mg/mL. tube, containing silver nanowires at a concentration of 1.52 ⁇ 10 -6 to 1.52 ⁇ 10 -5 mg/mL.
  • the mass fraction of the sodium dodecyl benzene sulfonate solution in step 2 is 0.5%
  • the diluted mixture contains carbon nanotubes with a concentration of 1.27 ⁇ 10 -3 mg/mL, and a concentration of 7.58 ⁇ 10 - 6 mg/mL silver nanowires.
  • ultrasonic dispersion is performed, and the carbon nanotube suspension is obtained by centrifugation at a rotation speed of 1000 to 5000 rpm for 1 to 60 minutes.
  • step two centrifuge at a rotation speed of 4000 rpm for 20 minutes to obtain the carbon nanotube suspension.
  • the passivation layer in step five is Nafion
  • the spin coating process parameters are as follows: spin coating speed 2000-5000 rpm, spin coating time 10-60 s.
  • the passivation layer in step five is Nafion
  • the spin coating process parameters are as follows: spin coating speed 3500 rpm, spin coating time 40 s.
  • Nafion is used to make the passivation layer, which is beneficial to achieve penetration and wrapping of the carbon nanotube/silver nanowire composite film.
  • the carbon nanotube powder has a diameter of 1 to 2 nm and a length of 5 to 30 ⁇ m, and the silver nanowire has a diameter of 10 to 30 nm.
  • the back electrode is a single electrode selected from gold, silver, titanium, copper, nickel, platinum, tin antimony oxide or aluminum-doped zinc oxide or a composite electrode composed of two or more thereof.
  • the front electrode is a graphene electrode or a metal electrode
  • the metal electrode is any single electrode of gold, silver, titanium, copper, nickel, platinum, tin antimony oxide or aluminum-doped zinc oxide or is made of any one of them.
  • Composite electrodes composed of two or more types.
  • the front electrode in step 4 is graphene
  • the front electrode is obtained by wet transfer.
  • the specific implementation method is as follows: transfer PMMA/few-layer graphene to the surface of the insulating layer in step 4 by wet method, and pump it in an oven. After evaporating the water in a vacuum, use acetone to dissolve and remove PMMA, and then use isopropyl alcohol to clean the remaining acetone to prepare a graphene front electrode.
  • the front electrode in step 4 is any single electrode of gold, silver, titanium, copper, nickel, platinum, tin antimony oxide or aluminum doped zinc oxide or a composite electrode composed of two or more of them, through evaporation , prepared by annealing process.
  • the insulating layer is any one of ZnO, SiN x , SiO 2 or Al 2 O 3 .
  • the present invention prepares a carbon nanotube/silver nanowire composite film by means of suction filtration and film-making and applies it as a hole transport layer, which can greatly simplify the process and reduce the cost. It is not limited by the high temperature resistance of the substrate and broadens the scope of application. Application fields of carbon nanotube/silver nanowire composite films;
  • the present invention first prepares a carbon nanotube suspension through ultrasonic dispersion and centrifugation to disperse the carbon nanotube powder evenly, and then mixes and dilutes it with silver nanowires and water, which can effectively avoid agglomeration of the carbon nanotube powder.
  • the carbon nanotube/silver nanowire composite film prepared from the composite of carbon nanotubes serves as a hole transport layer and has high light transmittance. It can significantly reduce the resistance between film layers without sacrificing a large amount of light transmittance. , obtain high conductivity, accelerate the separation and transportation of carriers at the interface between carbon nanotubes and semiconductor light absorption layers, and improve the photoelectric conversion efficiency of the device;
  • a carbon nanotube/silver nanowire composite film with both high light transmittance and high electrical conductivity is combined with a gallium arsenide substrate with excellent direct band gap and wide bandgap properties to prepare a carbon nanotube/silver nanowire composite film.
  • /GaAs-based heterojunction solar cells compared with carbon nanotube/gallium arsenide-based heterojunction solar cells, have higher open circuit voltage and photoelectric conversion efficiency.
  • Figure 1 is a schematic structural diagram of a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell in Example 1, in which: 1. back electrode; 2. gallium arsenide substrate; 3. hole transport layer ; 4. Passivation layer; 5. Insulating layer; 6. Front electrode.
  • Figure 2 is an SEM image of the carbon nanotube/silver nanowire composite film in Step 3 of Example 1.
  • Figure 3 is a current density-voltage curve of the carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell in Examples 1 to 5 and Comparative Examples 1 to 3.
  • the present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any form.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
  • a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell including the following steps:
  • Step 1 Ultrasonically clean the gallium arsenide substrate with acid, acetone, ethanol, and deionized water in sequence, and blow dry it with nitrogen. Then prepare a back electrode on one side of the gallium arsenide substrate through evaporation and annealing processes to obtain the back electrode. /GaAs substrate, then repeat the above cleaning steps, blow dry and set aside;
  • Step 2 Add carbon nanotube powder with a diameter of 1 to 2 nm and a length of 5 to 30 ⁇ m into a sodium dodecyl benzene sulfonate solution with a mass fraction of 0.1 to 1%, disperse it evenly through ultrasonic, and mix at 1000 to 5000 rpm. Centrifuge at high speed for 1 to 60 minutes, take the supernatant to obtain a carbon nanotube suspension, determine the concentration of the carbon nanotube suspension, and then mix the carbon nanotube suspension with silver nanowires with a diameter of 10nm to 30nm and deionized water.
  • a diluted mixture containing 8 ⁇ 10 -4 to 1.65 ⁇ 10 -3 mg/mL carbon nanotubes and 1.52 ⁇ 10 -6 to 1.52 ⁇ 10 -5 mg/mL silver nanowires was obtained, and then the diluted mixture was vacuumed Filter to obtain a carbon nanotube/silver nanowire composite film/filtration membrane;
  • Step three Place the carbon nanotube/silver nanowire composite film/filter membrane obtained in step two on the other side of the gallium arsenide substrate in step one, so that the carbon nanotube/silver nanowire composite film/filter membrane is
  • the carbon nanotube/silver nanowire composite film is in direct contact with the other side of the gallium arsenide substrate, and is pressed tightly with a glass slide.
  • alcohol is added dropwise, and placed in a closed space for vacuum filtration. After the alcohol is completely evaporated, take it out. And remove the filter part of the carbon nanotube/silver nanowire composite film/filter membrane to obtain a gallium arsenide substrate containing a hole transport layer of the carbon nanotube/silver nanowire composite film;
  • Step 4 Use any one of ZnO, SiN Insulating layer, and preparing a front electrode on the surface of the insulating layer to form a light-receiving window on the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film in step three;
  • Step 5 Spin-coat the Nafion passivation layer on the light-receiving window of Step 4 at a speed of 2000 to 5000 rpm. The spin coating lasts for 10 to 60 seconds.
  • the back electrode is any single electrode of gold, silver, titanium, copper, nickel, platinum, tin antimony oxide or aluminum-doped zinc oxide or a composite electrode composed of two or more thereof;
  • the front electrode is a graphene electrode or a metal electrode
  • the metal electrode is any single electrode or composed of two or more of gold, silver, titanium, copper, nickel, platinum, tin antimony oxide or aluminum-doped zinc oxide. composite electrode.
  • a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell including the following steps:
  • Step 1 Ultrasonically pickle the gallium arsenide substrate with a 10% HCl solution for 3 minutes, then ultrasonically clean it with acetone, ethanol and deionized water for 5 minutes. After blowing dry with nitrogen, the gallium arsenide substrate is placed on the gallium arsenide substrate. Prepare a gold back electrode on one side of the bottom through evaporation and annealing processes to obtain a gold back electrode/gallium arsenide substrate, then repeat the above cleaning steps, blow dry and set aside;
  • Step 2 Add 8.5 mg of carbon nanotube powder with a diameter of 1 nm and a length of 15 ⁇ m into 250 mL of a 0.5% sodium dodecyl benzene sulfonate solution, disperse evenly by ultrasonic, and centrifuge at 4000 rpm for 20 min to retain Supernatant to obtain a carbon nanotube suspension.
  • the diameter is 10 nm and the concentration is 0.05 mg/mL silver nanoparticle aqueous solution was added to 30 mL deionized water to obtain a diluted mixture containing 1.27 ⁇ 10 -3 mg/mL carbon nanotubes and 7.58 ⁇ 10 -6 mg/mL silver nanowires. Finally, the diluted mixture was vacuumed Filter to obtain a carbon nanotube/silver nanowire composite film/filtration membrane;
  • Step 3 Place the carbon nanotube/silver nanowire composite film/filter membrane on the other side of the gallium arsenide substrate in step 1, so that the carbon nanotube/silver nanowire composite film/filter membrane
  • the silver nanowire composite film is in direct contact with the other side of the gallium arsenide substrate and pressed tightly with a glass slide.
  • alcohol is added dropwise and placed in a closed space for vacuum filtration. After the alcohol is completely evaporated, the carbon nanowires are taken out and removed. From the filter membrane part of the tube/silver nanowire composite film/filter membrane, a gallium arsenide substrate containing a hole transport layer of the carbon nanotube/silver nanowire composite film can be obtained;
  • Step 4 Prepare an Al 2 O 3 insulation layer with a thickness of 100 nm on the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film in step 3 through photolithography and evaporation processes, and then add PMMA/few-layer graphene through a wet process Transfer to the surface of the Al 2 O 3 insulating layer, vacuum it in an oven to evaporate the water, use acetone to dissolve and remove PMMA, and then use isopropyl alcohol to clean the remaining acetone to prepare a graphene front electrode, so that the carbon nanotube/ There is a light-receiving window in the middle of the surface of the hole transport layer of the silver nanowire composite film;
  • Step 5 Spin-coat the Nafion passivation layer on the light-receiving window of Step 4 at a speed of 3500 rpm. The spin-coating lasts for 40 seconds.
  • Example 1 The structure of the carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell obtained in Example 1 is analyzed, as shown in Figure 1.
  • a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell including the following steps:
  • Step 1 Ultrasonically pickle the gallium arsenide substrate with a sulfuric acid solution with a mass fraction of 10% for 3 minutes. Ultrasonically clean the gallium arsenide substrate with acetone, ethanol and deionized water for 5 minutes. After drying with nitrogen, place the gallium arsenide substrate on the gallium arsenide substrate. Prepare a silver back electrode on one side of the bottom through evaporation and annealing processes to obtain a silver back electrode/gallium arsenide substrate. Then repeat the above cleaning steps and blow dry for later use;
  • Step 2 Add 8.5 mg of carbon nanotubes with a diameter of 2 nm and a length of 5 ⁇ m into 250 mL of a 1% sodium dodecyl benzene sulfonate solution, disperse evenly by ultrasonic, and centrifuge at 1000 rpm for 60 min. Keep the supernatant. Clear liquid to obtain a carbon nanotube suspension. Determine the concentration of the carbon nanotube suspension to be 0.014 mg/mL. Measure 3 mL of the 0.014 mg/mL carbon nanotube suspension and 10 ⁇ L of silver nanowires. The diameter is 30 nm and the concentration is 0.05 mg.
  • Step 3 Place the carbon nanotube/silver nanowire composite film/filter membrane on the other side of the gallium arsenide substrate in step 1, so that the carbon nanotube/silver nanowire composite film/filter membrane
  • the silver nanowire composite film is in direct contact with the other side of the gallium arsenide substrate and pressed tightly with a glass slide.
  • alcohol is added dropwise and placed in a closed space for vacuum filtration. After the alcohol is completely evaporated, the carbon nanowires are taken out and removed. From the filter membrane part of the tube/silver nanowire composite film/filter membrane, a gallium arsenide substrate containing a hole transport layer of the carbon nanotube/silver nanowire composite film can be obtained;
  • Step 4 Prepare a ZnO insulating layer with a thickness of 100 nm on the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film in step 3 through photolithography and evaporation processes, and then prepare copper on the surface of the ZnO insulating layer through evaporation and annealing processes
  • the front electrode allows the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film in step 3 to retain a light-receiving window;
  • Step 5 Spin-coat the Nafion passivation layer on the light-receiving window of Step 4 at a speed of 2000 rpm. The spin-coating lasts for 60 seconds.
  • a method for preparing a carbon nanotube/silver nanowire composite film/gallium arsenide-based heterojunction solar cell including the following steps:
  • Step 1 Ultrasonically pickle the gallium arsenide substrate with a 10% HCl solution for 3 minutes, ultrasonically clean it with acetone, ethanol and deionized water for 5 minutes, and blow dry it with nitrogen. Prepare a gold back electrode on one side of the bottom through evaporation and annealing processes to obtain a gold back electrode/gallium arsenide substrate, then repeat the above cleaning steps, blow dry and set aside;
  • Step 2 Add 8.5 mg of carbon nanotube powder with a diameter of 1 nm and a length of 30 ⁇ m into 250 mL of a 0.1% sodium dodecyl benzene sulfonate solution, disperse it evenly by ultrasonic, and centrifuge at 5000 rpm for 1 min. Keep the supernatant. Clear liquid to obtain a carbon nanotube suspension. Measure 3 mL of the 0.014 mg/mL carbon nanotube suspension and 1 ⁇ L of the silver nanowire aqueous solution with a diameter of 15 nm and a concentration of 0.05 mg/mL.
  • Step 3 Place the carbon nanotube/silver nanowire composite film/filter membrane on the other side of the gallium arsenide substrate in step 1, so that the carbon nanotube/silver nanowire composite film/filter membrane
  • the silver nanowire composite film is in direct contact with the other side of the gallium arsenide substrate and pressed tightly with a glass slide.
  • alcohol is added dropwise and placed in a closed space for vacuum filtration. After the alcohol is completely evaporated, the carbon nanowires are taken out and removed. From the filter membrane part of the tube/silver nanowire composite film/filter membrane, a gallium arsenide substrate containing a hole transport layer of the carbon nanotube/silver nanowire composite film can be obtained;
  • Step 4 Prepare a 100nm-thick SiN Prepare a silver front electrode so that the surface of the hole transport layer of the carbon nanotube/silver nanowire composite film in step 3 retains a light-receiving window;
  • Step 5 Spin-coat the Nafion passivation layer on the light-receiving window of Step 4 at a rotation speed of 5000 rpm. The spin-coating lasts for 10 seconds.
  • Example 4 The preparation conditions of Example 4 are basically the same as those of Example 1, except that the concentration of carbon nanotubes in the mixed solution in step two is controlled to 8 ⁇ 10 -4 mg/mL.
  • Example 5 The preparation conditions of Example 5 are basically the same as those of Example 1, except that the concentration of carbon nanotubes in the mixed solution in step two is controlled to be 1.65 ⁇ 10 -3 mg/mL.
  • Comparative Example 1 The preparation conditions of Comparative Example 1 are basically the same as those of Example 1, except that a carbon nanotube film is used as the hole transport layer.
  • Comparative Examples 2 to 3 are similar to Example 1, except that the concentration of carbon nanotubes in the diluted mixture in step 2 is controlled to: 4.5 ⁇ 10 -4 mg/mL and 2 ⁇ 10 -3 mg/mL. .
  • the carbon nanotubes and silver nanowires in the carbon nanotube/silver nanowire composite film are interconnected and distributed relatively uniformly.
  • the solar cells obtained through Technical Examples 1 to 5 of the present invention have higher open circuit voltage, and the photoelectric conversion rate is significantly improved. Rising from 2.47% to 6.77%, 4.93%, 4.41%, 3.60%, 4.22%.
  • Comparative Examples 2 to 3 illustrate that the concentration of carbon nanotubes in the diluted mixture in step 2 is one of the important conditions affecting product performance.

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Abstract

本发明属于太阳电池的领域，公开了一种碳纳米管/银纳米线复合薄膜及其砷化镓基异质结太阳电池和制备方法。该太阳电池自下而上包含背面电极、砷化镓衬底、空穴传输层、绝缘层和正面电极，所述空穴传输层为碳纳米管/银纳米线复合薄膜，其上表面还具有受光窗口，所述受光窗口旋涂上钝化层。本发明的太阳电池，使用碳纳米管/银纳米线复合薄膜作为空穴传输层，可极大地简化工序和降低成本的同时，又不受衬底耐高温性能的局限，拓宽了应用领域，且同时具备高透光性与高电导性，显著降低太阳电池的串联电阻，加快碳纳米管与半导体光吸收层界面的载流子的分离和运输，使太阳电池获得更高的开路电压及更好的光伏性能，提高光电转化效率。

Description

一种碳纳米管/银纳米线复合薄膜及其砷化镓基异质结太阳电池和制备方法 技术领域
本发明涉及太阳电池的技术领域，更具体地，涉及一种碳纳米管/银纳米线复合薄膜及其砷化镓基异质结太阳电池和制备方法。
背景技术
太阳电池技术的开发，极大地缓解了化石能源的消耗，有利于人类文明的延续。硅基太阳电池作为最成熟的技术之一，凭借其来源丰富，工艺成熟等优势在民用领域得到广泛的应用。材料的持续发展使得太阳电池器件种类逐渐丰富，包括钙钛矿太阳电池、有机太阳电池、薄膜太阳电池等。其中以砷化镓为代表的III-Ⅴ族半导体化合物作为电池材料引起了广泛的重视，这得益于其较大的禁带宽度，可与太阳光谱形成较好的匹配，同时其优异的耐高温性和抗高能粒子辐照性能使得其可应用为聚光电池和太空电池。即便砷化镓基太阳电池理论光电转换效率较高，但其制备技术及其高昂成本严重限制了推广应用。目前，针对多结III-Ⅴ族半导体太阳电池制备中存在的外延层间晶格失配严重和工艺复杂等难题，人们提出采用碳材料、聚合物、无机化合物等异质材料作为载流子传输层，实现高性能异质结太阳电池的制备。
现有技术公开了一种碳纳米管/砷化镓异质结宽光谱超薄太阳能电池及其构筑方法，其包括：下电极、N型砷化镓基底，位于砷化镓基底上带窗口的绝缘层，位于绝缘层窗口内与砷化镓直接接触的碳纳米管薄膜，设置在绝缘层表面碳纳米管薄膜上的图形化上电极。该发明可以同时利用碳纳米管与砷化镓对光子的高效吸收与转换特性，并通过所形成的异质结界面快速分离、输运，一方面降低了光生载流子复合几率，另一方面拓宽了砷化镓的响应光谱。该发明的太阳电池具有结构简单、工艺简便、轻薄等优点。
发明内容
本发明为克服上述现有技术所述的砷化镓基异质结太阳电池的电阻较大，光电转换效率较低等问题，提供一种碳纳米管/银纳米线复合薄膜；
同时，本发明还提供一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池；
同时，本发明还提供一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法。
为解决上述技术问题，本发明的技术方案如下：
一种碳纳米管/银纳米线复合薄膜，由以下制备方法制备得到：
步骤1，将碳纳米管粉末加入十二烷基苯磺酸钠溶液中，分散、离心得到碳纳米管悬浮液，将所述碳纳米管悬浮液和银纳米线、水混合得到稀释混合液，将所述稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤2，将步骤1得到的碳纳米管/银纳米线复合薄膜/滤膜置于清洗干净的衬底上，使所述碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与所述衬底表面接触压紧，并滴加酒精，再进行真空抽滤，然后去除所述碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到碳纳米管/银纳米线复合薄膜。
优选地，步骤1所述十二烷基苯磺酸钠溶液质量分数为0.1～1％，所述稀释混合液中含有浓度为8×10 -4～1.65×10 -3mg/mL的碳纳米管，浓度为1.52×10 -6～1.52×10 -5mg/mL的银纳米线。
进一步优选地，步骤1的十二烷基苯磺酸钠溶液质量分数为0.5％，所述稀释混合液中含有浓度为1.27×10 -3mg/mL的碳纳米管，浓度为7.58×10 -6mg/mL的银纳米线。
优选地，步骤1进行超声分散，并在1000～5000rpm的转速下离心1～60min得到所述碳纳米管悬浮液。
进一步优选地，步骤1在4000rpm的转速下离心20min得到所述碳纳米管悬浮液。
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池，自下到上包括以下部分：背面电极、砷化镓衬底、空穴传输层、绝缘层和正面电极，所述空穴传输层为本发明技术制备得到的碳纳米管/银纳米线复合薄膜，其上表面还具有受光窗口，所述受光窗口旋涂上钝化层。
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，包 括以下步骤：
步骤一，在砷化镓衬底的其中一面制备背面电极；
步骤二，将碳纳米管粉末加入十二烷基苯磺酸钠溶液中，分散、离心得到碳纳米管悬浮液，将所述碳纳米管悬浮液和银纳米线、水混合得到稀释混合液，将所述稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤三，将步骤二得到的碳纳米管/银纳米线复合薄膜/滤膜置于步骤一所述砷化镓衬底的另一面上，使所述碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与所述砷化镓衬底的另一面接触压紧，并滴加酒精，再进行真空抽滤，最后去除所述碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
步骤四，在步骤三所述碳纳米管/银纳米线复合薄膜空穴传输层表面进行光刻、蒸镀制备绝缘层，并在所述绝缘层表面制备正面电极，使步骤三所述碳纳米管/银纳米线复合薄膜空穴传输层表面形成受光窗口；
步骤五，在步骤四所述受光窗口上进行钝化层的旋涂。
通过以上工艺步骤，获得所述碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池。
本发明在制备碳纳米管/银纳米线复合薄膜/滤膜时，考虑到碳纳米管粉末难以分散的缺陷，先将碳纳米管粉末溶入十二烷基苯磺酸钠溶液中，分散、离心得到分散均匀的碳纳米管悬浮液，再与银纳米线、水混合稀释，能得到分散均匀的稀释混合液，以制备获得高质量的碳纳米管/银纳米线复合薄膜，并且在转移所述碳纳米管/银纳米线复合薄膜时，滴加了酒精，利用酒精的挥发促使碳纳米管/银纳米线复合薄膜与砷化镓衬底的结合更加紧密。
而且，本发明通过真空抽滤的方式在砷化镓衬底上制备碳纳米管/银纳米线复合薄膜，不受衬底耐高温性能的局限，可以拓宽所述碳纳米管/银纳米线复合薄膜的应用领域。
优选地，步骤一在所述砷化镓衬底上制备背面电极前后都需要进行清洗，所述清洗工艺如下：依次用酸、丙酮、乙醇、水进行清洗，后用氮气吹干。
进一步优选地，步骤一用质量分数为10％的HCl溶液将所述砷化镓衬底超声酸洗3min，然后依次用丙酮、乙醇、去离子水超声清洗5min，并用氮气吹干，待所述砷化镓衬底蒸镀上背面电极后，重复上述清洗步骤，再次用氮气吹干备用。
优选地，步骤一通过蒸镀、退火工艺获得含有背面电极的砷化镓衬底。
优选地，步骤二所述十二烷基苯磺酸钠溶液质量分数为0.1～1％，所述稀释混合液中含有浓度为8×10 -4～1.65×10 -3mg/mL的碳纳米管，浓度为1.52×10 -6～1.52×10 -5mg/mL的银纳米线。
进一步优选地，步骤二的十二烷基苯磺酸钠溶液质量分数为0.5％，所述稀释混合液中含有浓度为1.27×10 -3mg/mL的碳纳米管，浓度为7.58×10 -6mg/mL的银纳米线。
优选地，步骤二进行超声分散，并在1000～5000rpm的转速下离心1～60min得到所述碳纳米管悬浮液。
进一步优选地，步骤二在4000rpm的转速下离心20min得到所述碳纳米管悬浮液。
优选地，步骤五的钝化层为Nafion，旋涂工艺参数如下：旋涂转速2000～5000rpm，旋涂时间10～60s。
进一步优选地，步骤五的钝化层为Nafion，旋涂工艺参数如下：旋涂转速3500rpm，旋涂时间为40s。
Nafion作为高分子聚合物，用于制作钝化层，有利于实现对碳纳米管/银纳米线复合薄膜的渗透包裹。
优选地，所述碳纳米管粉末直径为1～2nm，长度为5～30μm，所述银纳米线直径为10～30nm。
优选地，所述背面电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极。
优选地，所述正面电极为石墨烯电极或金属电极，所述金属电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极。
当步骤四所述正面电极为石墨烯时，通过湿法转移获得正面电极，具体实施方法如下：将PMMA/少层石墨烯通过湿法转移至步骤四所述绝缘层表面，并于烘箱中抽真空使水分挥发后，使用丙酮溶解并去除PMMA，再用异丙醇清洗残留的丙酮，制备得到石墨烯正面电极。
当步骤四所述正面电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极时，通过蒸镀、退火工 艺制备获得。
优选地，所述绝缘层为ZnO、SiN x、SiO 2或Al 2O 3中的任意一种。
与现有技术相比，本发明技术方案的有益效果是：
本发明通过抽滤制膜的手段制备碳纳米管/银纳米线复合薄膜应用为空穴传输层，可极大地简化工序和降低成本的同时，又不受衬底耐高温性能的局限，拓宽了碳纳米管/银纳米线复合薄膜的应用领域；
本发明先通过超声分散、离心制备碳纳米管悬浮液，使碳纳米管粉末分散均匀，再与银纳米线、水混合稀释，能有效避免碳纳米管粉末出现结块现象，由银纳米线与碳纳米管复合制备得到的碳纳米管/银纳米线复合薄膜，作为空穴传输层，具备高透光性，可在不大量牺牲光透过率的前提下，大幅度降低薄膜层间的电阻，获得高电导性能，加快碳纳米管与半导体光吸收层界面载流子的分离和运输，提高器件光电转换效率；
同时具备高透光性和高电导性的碳纳米管/银纳米线复合薄膜结合具有直接带隙、宽禁带优异特性的砷化镓衬底，制备得到的碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池，相较于碳纳米管/砷化镓基异质结太阳电池，具有更高的开路电压及光电转换效率。
附图说明
图1为实施例1碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的结构示意图，其中：1、背面电极；2、砷化镓衬底；3、空穴传输层；4、钝化层；5、绝缘层；6、正面电极。
图2为实施例1步骤三碳纳米管/银纳米线复合薄膜的SEM图。
图3为实施例1～5和对比例1～3中碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的电流密度-电压曲线图。
具体实施方式
下面结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，以下实施例所用试剂和材料均为市购。
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，包括以下步骤：
步骤一，依次用酸、丙酮、乙醇、去离子水超声清洗砷化镓衬底，并用氮气吹干后，在砷化镓衬底的其中一面通过蒸镀、退火工艺制备背面电极，得到背面电极/砷化镓衬底，然后重复上述的清洗步骤，吹干备用；
步骤二，将直径为1～2nm，长度为5～30μm的碳纳米管粉末加入质量分数为0.1～1％的十二烷基苯磺酸钠溶液中，通过超声分散均匀，于1000～5000rpm的转速下离心1～60min，取上清液，得到碳纳米管悬浮液，确定碳纳米管悬浮液的浓度，再将碳纳米管悬浮液和直径为10nm～30nm的银纳米线、去离子水混合得到含有8×10 -4～1.65×10 -3mg/mL碳纳米管和1.52×10 -6～1.52×10 -5mg/mL银纳米线的稀释混合液，然后将稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤三，将步骤二得到的碳纳米管/银纳米线复合薄膜/滤膜置于步骤一的砷化镓衬底的另一面上，使碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与砷化镓衬底的另一面直接接触，并用载玻片压紧，然后滴加酒精，放入密闭空间中进行真空抽滤，待酒精完全挥发后，取出并去除碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
步骤四，以ZnO、SiN x、SiO 2或Al 2O 3中的任意一种作为绝缘层材料，在步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面进行光刻、蒸镀制备绝缘层，并在绝缘层表面制备正面电极，使步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面形成受光窗口；
步骤五，以2000～5000rpm的转速在步骤四受光窗口旋涂Nafion钝化层，旋涂持续10s～60s。
通过以上工艺步骤，最终获得碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池。
具体地，背面电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极；
具体地，正面电极为石墨烯电极或金属电极，金属电极为金、银、钛、铜、 镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极。
实施例1
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，包括以下步骤：
步骤一，用质量分数为10％的HCl溶液对砷化镓衬底进行超声酸洗3min，并依次用丙酮、乙醇和去离子水进行超声清洗5min，用氮气吹干后，在砷化镓衬底的其中一面通过蒸镀、退火工艺制备金背面电极，得到金背面电极/砷化镓衬底，然后重复上述的清洗步骤，吹干备用；
步骤二，将8.5mg直径为1nm，长度为15μm碳纳米管粉末加入250mL质量分数为0.5％的十二烷基苯磺酸钠溶液中，通过超声分散均匀，于4000rpm的转速下离心20min，保留上清液，得到碳纳米管悬浮液，测定碳纳米管悬浮液的浓度为0.014mg/mL，量取3mL的0.014mg/mL碳纳米管悬浮液及5μL银纳米线直径为10nm，浓度为0.05mg/mL的银纳米水溶液加入30mL去离子水中得到含有1.27×10 -3mg/mL碳纳米管和7.58×10 -6mg/mL银纳米线的稀释混合液，最后将稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤三，将碳纳米管/银纳米线复合薄膜/滤膜置于步骤一的砷化镓衬底的另一面上，使碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与砷化镓衬底的另一面直接接触，并用载玻片压紧，然后滴加酒精，放入密闭空间中进行真空抽滤，待酒精完全挥发后，取出并去除碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
步骤四，在步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面通过光刻、蒸镀工艺制备厚度为100nm的Al 2O 3绝缘层，再将PMMA/少层石墨烯通过湿法转移至Al 2O 3绝缘层表面，并于烘箱中抽真空使水分挥发后，使用丙酮溶解并去除PMMA，再用异丙醇清洗残留的丙酮，制备得到石墨烯正面电极，使碳纳米管/银纳米线复合薄膜空穴传输层表面中间保留有受光窗口；
步骤五，以3500rpm的转速在步骤四的受光窗口旋涂Nafion钝化层，旋涂持续40s。
通过以上工艺步骤，获得碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池。
分析实施例1所得碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的结构，如图1所示。
用扫描电子显微镜对实施例1步骤三的碳纳米管/银纳米线复合薄膜进行表征，结果如图2所示。
实施例2
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，包括以下步骤：
步骤一，用质量分数为10％的硫酸溶液对砷化镓衬底进行超声酸洗3min，并依次用丙酮、乙醇和去离子水进行超声清洗5min，用氮气吹干后，在砷化镓衬底的其中一面通过蒸镀、退火工艺制备银背面电极，得到银背面电极/砷化镓衬底，然后重复上述的清洗步骤，吹干备用；
步骤二，将8.5mg直径为2nm，长度为5μm碳纳米管加入250mL质量分数为1％的十二烷基苯磺酸钠溶液中，通过超声分散均匀，于1000rpm的转速下离心60min，保留上清液，得到碳纳米管悬浮液，测定碳纳米管悬浮液的浓度为0.014mg/mL，量取3mL的0.014mg/mL碳纳米管悬浮液及10μL银纳米线直径为30nm，浓度为0.05mg/mL银纳米水溶液加入30mL去离子水中得到含有1.27×10 -3mg/mL的碳纳米管和1.52×10 -5mg/mL银纳米线的稀释混合液，最后将稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤三，将碳纳米管/银纳米线复合薄膜/滤膜置于步骤一的砷化镓衬底的另一面上，使碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与砷化镓衬底的另一面直接接触，并用载玻片压紧，然后滴加酒精，放入密闭空间中进行真空抽滤，待酒精完全挥发后，取出并去除碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
步骤四，在步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面通过光刻、蒸镀工艺制备厚度为100nm的ZnO绝缘层，再在ZnO绝缘层表面通过蒸镀、退火工艺制备铜正面电极，使步骤三碳纳米管/银纳米线复合薄膜空穴传输层表 面保留有受光窗口；
步骤五，以2000rpm的转速在步骤四的受光窗口旋涂Nafion钝化层，旋涂持续60s。
通过以上工艺步骤，获得碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池。
实施例3
一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，包括以下步骤：
步骤一，用质量分数为10％的HCl溶液对砷化镓衬底进行超声酸洗3min，并依次用丙酮、乙醇和去离子水进行超声清洗5min，并用氮气吹干后，在砷化镓衬底的其中一面通过蒸镀、退火工艺制备金背面电极，得到金背面电极/砷化镓衬底，然后重复上述的清洗步骤，吹干备用；
步骤二，将8.5mg直径为1nm，长度为30μm碳纳米管粉末加入250mL质量分数为0.1％十二烷基苯磺酸钠溶液中，通过超声分散均匀，于5000rpm的转速下离心1min，保留上清液，得到碳纳米管悬浮液，量取3mL的0.014mg/mL碳纳米管悬浮液及1μL银纳米线直径为15nm，浓度为0.05mg/mL银纳米水溶液加入30mL去离子水中得到含有1.27×10 -3mg/mL的碳纳米管和1.52×10 -6mg/mL的银纳米线的稀释混合液，最后将稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
步骤三，将碳纳米管/银纳米线复合薄膜/滤膜置于步骤一的砷化镓衬底的另一面上，使碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与砷化镓衬底的另一面直接接触，并用载玻片压紧，然后滴加酒精，放入密闭空间中进行真空抽滤，待酒精完全挥发后，取出并去除碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
步骤四，在步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面通过光刻、蒸镀工艺制备厚度为100nm的SiN x绝缘层，再在SiN x绝缘层表面通过蒸镀、退火工艺制备银正面电极，使步骤三碳纳米管/银纳米线复合薄膜空穴传输层表面保留有受光窗口；
步骤五，以5000rpm的转速在步骤四的受光窗口旋涂Nafion钝化层，旋涂持续10s。
通过以上工艺步骤，获得碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池。
实施例4
实施例4与实施例1制备条件基本相同，不同之处在于，控制步骤二混合溶液中碳纳米管浓度为8×10 -4mg/mL。
实施例5
实施例5与实施例1制备条件基本相同，不同之处在于，控制步骤二混合溶液中碳纳米管浓度为1.65×10 -3mg/mL。
对比例1
对比例1与实施例1制备条件基本相同，不同之处在于，用碳纳米管薄膜作为空穴传输层。
对比例2～3
对比例2～3与实施例1制备条件相似，不同之处在于，分别控制步骤二稀释混合液中碳纳米管的浓度为：4.5×10 -4mg/mL和2×10 -3mg/mL。
对实施例1～5和对比例1～3所得太阳电池进行电学性能测试，测试结果见表1与图3。
表1实施例1～5和对比例1～3所得太阳电池的电学性能测试结果
Figure PCTCN2022128738-appb-000001
Figure PCTCN2022128738-appb-000002
由图2可知，碳纳米管/银纳米线复合薄膜中碳纳米管与银纳米线交叉互联，分布较为均匀。
结合图3与表1可知：
通过本发明技术实施例1～5得到的太阳电池相对对比例1用碳纳米管薄膜作为空穴传输层获得的太阳电池，具有更高的开路电压，光电转换化率都有了显著的提高，从2.47％上升到6.77％、4.93％、4.41％、3.60％、4.22％。
对比例2～3则说明了步骤二稀释混合液中碳纳米管的浓度是影响产品性能的重要条件之一。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种碳纳米管/银纳米线复合薄膜，其特征在于，由以下制备方法制备得到：
    步骤1，将碳纳米管粉末加入十二烷基苯磺酸钠溶液中，分散、离心得到碳纳米管悬浮液，将所述碳纳米管悬浮液和银纳米线、水混合得到稀释混合液，将所述稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
    步骤2，将步骤1得到的碳纳米管/银纳米线复合薄膜/滤膜置于清洗干净的衬底上，使所述碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与所述衬底表面接触压紧，并滴加酒精，再进行真空抽滤，然后去除所述碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到碳纳米管/银纳米线复合薄膜。
  2. 根据权利要求1所述碳纳米管/银纳米线复合薄膜，其特征在于，
    步骤1所述十二烷基苯磺酸钠溶液质量分数为0.1～1％，所述稀释混合液中含有浓度为8×10 -4～1.65×10 -3mg/mL的碳纳米管，浓度为1.52×10 -6～1.52×10 -5mg/mL的银纳米线。
  3. 根据权利要求2所述碳纳米管/银纳米线复合薄膜，其特征在于，步骤1的十二烷基苯磺酸钠溶液质量分数为0.5％，所述稀释混合液中含有浓度为1.27×10 -3mg/mL的碳纳米管，浓度为7.58×10 -6mg/mL的银纳米线。
  4. 根据权利要求1所述碳纳米管/银纳米线复合薄膜，其特征在于，步骤1进行超声分散，并在1000～5000rpm的转速下离心1～60min得到所述碳纳米管悬浮液。
  5. 一种碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池，其特征在于，自下到上包括以下部分：背面电极、砷化镓衬底、空穴传输层、绝缘层和正面电极，所述空穴传输层为权利要求1～4任意一项所述碳纳米管/银纳米线复合薄膜，其上表面还具有受光窗口，所述受光窗口旋涂上钝化层。
  6. 根据权利要求5所述碳纳米管/银纳米线复合薄膜/砷化镓异质结太阳电池，其特征在于，所述将碳纳米管粉末直径为1～2nm，长度为5～30μm，所述银纳米线直径为10nm～30nm。
  7. 根据权利要求5所述碳纳米管/银纳米线复合薄膜/砷化镓异质结太阳电池，其特征在于，所述背面电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌 中的任意一种单一电极或由其中两种以上组成的复合电极；所述正面电极为石墨烯电极或金属电极，所述金属电极为金、银、钛、铜、镍、铂、氧化锡锑或铝掺氧化锌中的任意一种单一电极或由其中两种以上组成的复合电极。
  8. 权利要求5～7任意一项所述碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，其特征在于，包括以下步骤：
    步骤一，在砷化镓衬底的其中一面制备背面电极；
    步骤二，将碳纳米管粉末加入十二烷基苯磺酸钠溶液中，分散、离心得到碳纳米管悬浮液，将所述碳纳米管悬浮液和银纳米线、水混合得到稀释混合液，将所述稀释混合液进行真空抽滤得到碳纳米管/银纳米线复合薄膜/滤膜；
    步骤三，将步骤二得到的碳纳米管/银纳米线复合薄膜/滤膜置于步骤一所述砷化镓衬底的另一面上，使所述碳纳米管/银纳米线复合薄膜/滤膜中的碳纳米管/银纳米线复合薄膜与所述砷化镓衬底的另一面接触压紧，并滴加酒精，再进行真空抽滤，然后去除所述碳纳米管/银纳米线复合薄膜/滤膜中的滤膜部分，即可得到含有碳纳米管/银纳米线复合薄膜空穴传输层的砷化镓衬底；
    步骤四，在步骤三所述碳纳米管/银纳米线复合薄膜空穴传输层表面进行光刻、蒸镀制备绝缘层，并在所述绝缘层表面制备正面电极，使步骤三所述碳纳米管/银纳米线复合薄膜空穴传输层表面形成受光窗口；
    步骤五，在步骤四所述受光窗口上进行钝化层的旋涂。
  9. 根据权利要求8所述碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，其特征在于，步骤五所述钝化层为Nafion，旋涂工艺参数如下：旋涂转速2000～5000rpm，优选3500rpm，旋涂时间10～60s，优选40s。
  10. 根据权利要求8所述碳纳米管/银纳米线复合薄膜/砷化镓基异质结太阳电池的制备方法，其特征在于，步骤四的绝缘层为ZnO、SiN x、SiO 2或Al 2O 3中的任意一种。
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