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WO2018124390A1 - Cellule solaire de pérovskite utilisant une électrode de graphène, et son procédé de fabrication - Google Patents

Cellule solaire de pérovskite utilisant une électrode de graphène, et son procédé de fabrication Download PDF

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Publication number
WO2018124390A1
WO2018124390A1 PCT/KR2017/002415 KR2017002415W WO2018124390A1 WO 2018124390 A1 WO2018124390 A1 WO 2018124390A1 KR 2017002415 W KR2017002415 W KR 2017002415W WO 2018124390 A1 WO2018124390 A1 WO 2018124390A1
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graphene
electrode
solar cell
graphene electrode
transport layer
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Korean (ko)
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최석호
임상혁
허진혁
신동희
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Kyung Hee University
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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]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a perovskite solar cell using a graphene electrode and a method for manufacturing the same, and more particularly to a graphene-based perovskite solar cell that can control the work function while maintaining high electrical conductivity of graphene It is about.
  • the perovskite material is an AMX 3 structure (A, M is a cation, X is an anion) and is an organic / inorganic composite material having an ionic crystal and a direct band gap.
  • This material has high absorption coefficient, thin film, long charge diffusion distance, and high efficiency of solar cell.
  • the perovskite material has a great potential in terms of practical use because it can be manufactured in a low-cost, high-efficiency optoelectronic device can be a solution process.
  • the developed perovskite materials have low moisture and heat resistance and therefore require a passivation layer. It can be used as an ultra-thin solar cell and can be used as a next-generation flexible and mobile independent power source. However, in order to realize perovskite-based flexible solar cells, development of flexible electrodes that are flexible is essential. .
  • the present invention is expected to be able to manufacture high-efficiency graphene-based perovskite solar cells using a chemical doping method capable of adjusting the work function while maintaining high electrical conductivity of graphene. do.
  • the present invention is to provide a perovskite solar cell using a graphene transparent electrode whose characteristics are controlled by doping.
  • the present invention by using a p-type graphene electrode in the perovskite solar cell structure by adjusting the doping concentration, the perovskite using a graphene electrode that can increase the energy conversion efficiency of the perovskite solar cell To provide a skylight solar cell and a method of manufacturing the same.
  • the perovskite solar cell using a graphene electrode is a graphene electrode formed by applying an impurity solution on the surface of the graphene transferred on the substrate, holes deposited on the doped graphene electrode A transfer layer, a barrier layer formed of a metal oxide of a thin film having a predetermined thickness by coating a perovskite structure material on the hole transfer layer, an electron transfer layer formed on the barrier layer and the electron transfer layer An upper electrode formed on the layer.
  • the graphene electrode is formed by spin coating a p-type impurity solution on the graphene to dope the graphene transferred on the substrate, and the electrode characteristics are improved in proportion to the doping concentration of the p-type impurity solution. It features.
  • the graphene electrode is formed by the p-type impurity solution of gold chloride (Gold chloride, AuCl 3 ), the doping concentration may be controlled by the amount of powder of the gold chloride.
  • the p-type impurity solution may be formed of at least one of nitric acid (HNO 3 ), rhodium chloride (RhCl 3 ), and trifluoromethanesulfonic acid (TFSA) in addition to the gold chloride.
  • HNO 3 nitric acid
  • RhCl 3 rhodium chloride
  • TFSA trifluoromethanesulfonic acid
  • the graphene is manufactured by chemical vapor deposition (CVD), transferred onto the substrate, and then formed by removing poly (methyl methacrylate) (PMMA).
  • CVD chemical vapor deposition
  • PMMA poly (methyl methacrylate)
  • the hole transport layer may be formed by spin coating a methanol and a PEDOT: PSS solution on the doped graphene electrode and then evaporating the methanol.
  • the blocking layer may be formed by spin coating the perovskite structure material and dimethylformamide (N, N, dimethylformamide) solution on the hole transport layer.
  • the electron transport layer may be formed by spin coating a PCBM (Phenyl-C61-butyric acid methyl ester) and toluene solution, which are electron transport layers, on the blocking layer.
  • PCBM Phhenyl-C61-butyric acid methyl ester
  • toluene solution which are electron transport layers
  • the upper electrode may include at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), and an alloy thereof using a thermal evaporator on the electron transport layer. It can be formed of one material.
  • the forming of the graphene electrode may include spin coating a p-type impurity solution on the graphene to form the graphene electrode to dope the graphene transferred on the substrate, and a doping concentration of the p-type impurity solution. It may be characterized in that to improve the electrode characteristics of the graphene electrode in proportion to.
  • the graphene electrode is formed by the p-type impurity solution, which is gold chloride (AuCl 3 ), and the doping concentration may be controlled by the amount of powder of the gold chloride.
  • the hole transport layer after spin-coating methanol and PEDOT: PSS solution on the doped graphene electrode, the hole transport layer may be deposited by evaporating the methanol.
  • the forming of the blocking layer may include spin-coating the perovskite structure material and dimethylformamide (N, N, dimethylformamide) solution on the hole transport layer to form the blocking layer of perovskite structure material. Can be formed.
  • the electron transport layer which is an electron transfer layer, may be formed by spin coating a PCBM (Phenyl-C61-butyric acid methyl ester) and toluene solution on the blocking layer.
  • PCBM Phhenyl-C61-butyric acid methyl ester
  • the forming of the upper electrode may include silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), and these using a thermal evaporator on the electron transport layer.
  • the upper electrode may be formed of at least one material of an alloy.
  • the embodiment of the present invention by controlling the doping concentration by using a p-type graphene electrode in the perovskite solar cell structure, it is possible to increase the energy conversion efficiency of the perovskite solar cell.
  • FIG. 1 illustrates a structure example of a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • FIG. 2 illustrates an example of transferring graphene onto a substrate according to an embodiment of the present invention.
  • 3A and 3B illustrate an example of manufacturing doped graphene according to an embodiment of the present invention.
  • Figure 4 shows the experimental results for the doping degree of gold chloride according to an embodiment of the present invention.
  • 5a to 5g show the results of experiments on the surface roughness and the formation of nanoparticles at different doping concentrations according to an embodiment of the present invention.
  • Figure 6 shows the experimental results for the graphene sheet resistance at different doping concentrations according to an embodiment of the present invention.
  • Figure 7 shows the experimental results for the permeability of graphene at different doping concentrations according to an embodiment of the present invention.
  • Figure 9 shows the experimental results for the work function at different doping concentrations according to an embodiment of the present invention.
  • 10A and 10B illustrate experimental results of graphene field effect transistors at different doping concentrations according to an exemplary embodiment of the present invention.
  • FIG. 11 illustrates a scanning electron microscope image of a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • 12A and 12B illustrate evaluation results of characteristics of a perovskite solar cell using a graphene electrode according to an exemplary embodiment of the present invention.
  • Figure 13 shows the experimental results for the external quantum efficiency of the perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • FIG. 14A and 14B illustrate graphs of measurement results of diffusion coefficients and carrier decay times at different doping concentrations and calculation examples of diffusion distances according to embodiments of the present invention.
  • 15A to 15F illustrate evaluation results of characteristics of a perovskite solar cell using graphene electrodes at different doping concentrations according to an embodiment of the present invention.
  • FIG. 16 shows the results of measuring the stability of the current for the perovskite solar cell using a gold chloride-doped graphene electrode according to an embodiment of the present invention.
  • FIG. 17 is a flowchart illustrating a method of manufacturing a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • an embodiment As used herein, “an embodiment”, “an example”, “side”, “an example”, etc., should be construed that any aspect or design described is better or advantageous than other aspects or designs. It is not.
  • the term 'or' means inclusive or 'inclusive or' rather than 'exclusive or'.
  • the expression 'x uses a or b' means any one of natural inclusive permutations.
  • FIG. 1 illustrates a structure example of a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • the perovskite solar cell 100 using the graphene electrode according to the embodiment of the present invention is formed including a graphene transparent electrode whose characteristics are controlled by doping.
  • the perovskite solar cell 100 using a graphene electrode is a graphene electrode 110, a hole transport layer 120, a blocking layer 130, an electron transport layer 140 ), And an upper electrode 150.
  • the graphene electrode 110 is formed by applying an impurity solution to the graphene surface transferred on the substrate.
  • the substrate may be at least one of a glass substrate, a plastic substrate, and a flexible substrate
  • the flexible substrate may be polyethylene glycol (polyethylenterephthalate, PET), polyethylene naphtalate (PEN), and polydimethylsiloxane (PDMS). It may be at least one of).
  • the graphene electrode 110 is formed by spin coating a p-type impurity solution on the graphene to dope the graphene transferred on the substrate, and the electrode characteristics may be improved in proportion to the doping concentration of the p-type impurity solution. .
  • the graphene electrode 110 is formed by a p-type impurity solution of gold chloride (Gold chloride, AuCl 3 ), the doping concentration may be controlled by the amount of powder of gold chloride.
  • gold chloride Gold chloride, AuCl 3
  • the p-type impurity solution may be formed of at least one of nitric acid (HNO 3 ), rhodium chloride (RhCl 3 ), and trifluoromethanesulfonic acid (TFSA) in addition to gold chloride.
  • HNO 3 nitric acid
  • RhCl 3 rhodium chloride
  • TFSA trifluoromethanesulfonic acid
  • the graphene is manufactured by chemical vapor deposition (CVD), transferred onto the substrate, and then formed by removing poly (methyl methacrylate) (PMMA).
  • CVD chemical vapor deposition
  • PMMA poly (methyl methacrylate)
  • the graphene electrode 110 may be formed by growing graphene directly on the substrate or transferring the grown graphene onto the substrate. At this time, the method for growing graphene is not particularly limited.
  • the graphene electrode 110 formed by the chemical vapor deposition (CVD) method may have a hydrophobic surface.
  • the hole transport layer 120 is deposited on the doped graphene electrode.
  • the hole transport layer 120 may be formed by spin-coating methanol and a PEDOT: PSS solution on the doped graphene electrode 110 and then evaporating methanol.
  • the hole transport layer 120 may be formed to have a uniform thickness and composition through a solution process by applying a template material on the graphene electrode 110 surface.
  • the hole transport layer 120 may be a hole transport layer, and may include an inorganic oxide thin film.
  • the inorganic oxide thin film is a p-type inorganic oxide such as tungsten oxide (WO 3 ), molybdenum trioxide (MoO 3 ), vanadium oxide (Vanadium (V) oxide, V 2 O 5 ), nickel oxide (Nio), or the like. It may be formed.
  • the hole transport layer 120 may include a PEDOT: PSS thin film formed on the inorganic oxide thin film, and the inorganic oxide thin film and the PEDOT: PSS thin film may function together as a hole transport layer.
  • the blocking layer 130 is formed of a thin metal oxide having a predetermined thickness by applying a perovskite structure material on the hole transport layer.
  • the blocking layer 130 may be formed by spin-coating a perovskite structure material and a dimethylformamide (N, N, dimethylformamide) solution on the hole transport layer 120.
  • the blocking layer 130 is a metal oxide, in addition to titanium dioxide (TiO 2 ), zirconium, titanium, tin, zinc, zinc oxide, zirconium dioxide (ZrO 2 ), tantalum oxide (Ta 2 O 3 ) It may be formed of a metal oxide in the form of a thin film, such as magnesium oxide (Magnesium oxide, MgO), hafnium (IV) oxide, HfO 2 .
  • the electron transport layer 140 is formed on the blocking layer 130.
  • the electron transport layer 140 may be formed by spin coating a PCBM (Phenyl-C61-butyric acid methyl ester) and toluene solution on the blocking layer 130.
  • PCBM Phhenyl-C61-butyric acid methyl ester
  • the electron transport layer 140 may be an electron transport layer, and may include an inorganic oxide thin film.
  • the inorganic oxide thin film may be formed of an n-type inorganic oxide such as titanium dioxide (TiO 2 ), zinc oxide (ZnO), or the like.
  • the inorganic oxide precursor may be titanium bisammonium lactatodihydroxide (TiBALDH, [CH 3 CH (O) CO 2 NH 4 ] 2 Ti (OH). 2 ) and the like can be used.
  • the upper electrode 150 is formed on the electron transport layer 140.
  • the upper electrode 150 may be formed of silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt), and the like by using a thermal evaporator on the electron transport layer 140. It may be formed of at least one material of the alloy.
  • the method of forming the upper electrode 150 is not particularly limited.
  • the upper electrode 150 when the graphene electrode 110 is an anode, the upper electrode 150 may function as a cathode, and in this case, the upper electrode 150 may be a metal having a low work function. It may be formed of aluminum (Al).
  • the upper electrode 150 when the graphene electrode 110 is a cathode, the upper electrode 150 may function as an anode, in which case the upper electrode 150 is a metal having a high work function. Phosphorus silver (Ag) may be formed.
  • graphene electrode doped with gold chloride (AuCl 3 ) has a large work function, so the perovskite structure is manufactured based on the pin structure.
  • PEDOT PSS was deposited to fabricate a hole transport layer on undoped or doped graphene electrodes.
  • a spin coating method which is a coating method in which the prepared solution is dropped on the graphene electrode and rotated at high speed to spread thinly, was used.
  • PCBM Phenyl-C61-butyric acid methyl ester
  • an aluminum (Al) electrode was formed on an electron transport layer (PCBM / MAPbI 3 / PEDOT: PSS / Graphene / Glass) using a thermal evaporator to form an upper electrode.
  • FIG. 2 illustrates an example of transferring graphene onto a substrate according to an embodiment of the present invention.
  • the substrate may be a glass substrate, but may be any one of a flexible substrate and a plastic substrate.
  • graphene is manufactured by chemical vapor deposition (CVD), and a sheet of graphene is supported by poly (methyl methacrylate) (PMMA), floated in deionized water, and then transferred onto a substrate.
  • CVD chemical vapor deposition
  • PMMA poly (methyl methacrylate)
  • the transferred graphene may be dried in air, and then formed on a hot plate and further dried at about 180 ° C. for 2 hours. Thereafter, after removing PMMA using acetone, it may be naturally dried.
  • 3A and 3B illustrate an example of manufacturing doped graphene according to an embodiment of the present invention.
  • Figure 3a shows an example of the doping concentration according to the mixing of nitromethane (Nitro methane) and gold chloride (Gold chloride, AuCl 3 ),
  • Figure 3b to form a graphene electrode on the graphene / substrate An example is shown.
  • the graphene electrode of the perovskite solar cell using the graphene electrode according to the embodiment of the present invention is formed by a doping solution doped on the graphene surface transferred on the substrate.
  • the doping solution may be used gold chloride for the production of p-type graphene.
  • the doping solution according to the mixing of nitromethane and gold chloride may exhibit different doping concentrations depending on the amount of powder of gold chloride.
  • the doping concentration of the doping solution was adjusted to 1mM to 10mM by the amount of gold chloride powder, and after doping to uniformly coat the gold chloride, heat treatment was performed at 100 ° C. for 10 minutes using rapid heat treatment.
  • a doping solution 310 which is a p-type impurity solution is coated on a graphene / substrate, and spin-coated to form a doped graphene electrode.
  • Robesky solar cells can be fabricated.
  • the doping solution 310 may be any one of solutions showing different doping concentrations according to the amount of gold chloride powder prepared in FIG. 3A.
  • the doping solution 310 is applied onto the graphene / substrate, followed by spin coating for 1 minute at about 2500 rpm. Thereafter, annealing of the p-type impurity solution / graphene / substrate 330 to which the P-type impurity solution is applied is performed to form a graphene electrode 350 using the doped graphene as an electrode. Can be.
  • Figure 4 shows the experimental results for the doping degree of gold chloride according to an embodiment of the present invention.
  • FIG. 4 shows a graph of experimental results obtained by applying X-ray photoelectron spectroscopy to a gold chloride-doped graphene electrode.
  • XPS intensity (XPS Intensity) according to binding energy (eV) in gold chloride-doped graphene electrode (AuCl 3 doped graphene) and undoped graphene electrode (Pristine graphene) You can check.
  • the gold (Au) and chlorine (Cl) elements are observed only on the graphene electrode doped with gold chloride.
  • the p-type impurity solution of gold chloride (AuCl 3 ) is graphene. It can be seen that it is well doped on the electrode.
  • 5a to 5g show the results of experiments on the surface roughness and the formation of nanoparticles at different doping concentrations according to an embodiment of the present invention.
  • FIGS. 5A to 5F show graphs of experimental results of atomic force microscope (AFM) images and nanoparticle height profiles according to the doping concentration of gold chloride (AuCl 3 ), and FIG. 5g shows an experimental result graph of surface roughness values according to the doping concentration of gold chloride (AuCl 3 ).
  • AFM atomic force microscope
  • FIG. 5A shows experimental results of AFM images and nanoparticle height for graphene / substrate including undoped graphene electrodes (Pristine graphene).
  • FIG. 5B shows experimental results of AFM images and nanoparticle height for graphene / substrate comprising 1 mM gold chloride doped graphene electrode
  • FIG. 5C includes graphene electrode doped with 2.5 mM gold chloride. The experimental results of the AFM image and nanoparticle height for the graphene / substrate.
  • FIG. 5D shows experimental results of AFM images and nanoparticle height for graphene / substrate comprising 5 mM gold chloride doped graphene electrode
  • FIG. 5E includes 7.5 mM gold chloride doped graphene electrode.
  • AFM images of the graphene / substrate and the experimental results of the nanoparticle height is shown
  • Figure 5f is an experiment of the AFM image and nanoparticle height for the graphene / substrate containing a graphene electrode doped with 10 mM gold chloride The results are shown.
  • gold (Au) nanoparticles are formed by doping with gold chloride. This may be understood that the reduction potential of graphene (0.22eV) is higher than that of gold chloride ions (1.0eV).
  • the roughness value Rq of the graphene / substrate surface increases as the doping concentration n D of the doping solution increases depending on the amount of powder of gold chloride.
  • Figure 6 shows the experimental results for the graphene sheet resistance at different doping concentrations according to an embodiment of the present invention.
  • FIG. 6 shows graphene on a graphene / substrate according to undoped graphene electrodes (Pristine) and graphene electrodes doped with gold chloride doped with 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively. A graph of the sheet resistance measurement results is shown.
  • the sheet resistance of the graphene electrode gradually decreases as the doping concentration n D of the doping solution increases depending on the amount of powder of gold chloride.
  • the sheet resistance of the single layer graphene transferred onto the substrate was observed to be about 890 ohm / sq on average, and as the doping concentration of gold chloride (AuCl 3 ) increased from 1 mM to 10 mM, the sheet resistance of the graphene electrode. It can be seen that gradually decreases from ⁇ 890ohm / sq to ⁇ 70ohm / sq. This means that as the doping concentration increases, the characteristics of the graphene electrode are improved.
  • Figure 7 shows the experimental results for the permeability of graphene at different doping concentrations according to an embodiment of the present invention.
  • FIG. 7 shows the transmission spectrum of graphene according to the undoped graphene electrode (0 mM) and the graphene electrode doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively. .
  • the transmittance at 550 nm is reduced from about 9% to 89.2% by about 8%. You can see that it is very insignificant.
  • FIG. 8 shows DC conductivity and optical conductivity characteristics through the following [Formula 1] to confirm whether the transparent conductive electrode including the graphene electrode doped with gold chloride (AuCl 3 ) can be used industrially. The graph of the experimental result confirmed is shown.
  • T means transmittance
  • Rs means sheet resistance
  • Z0 means free space impedance
  • Means optical conductivity Means DC conductivity.
  • the value of DC conductivity / optical conductivity must be at least 35 (the straight line in FIG. 8 graph means minimum value).
  • Figure 9 shows the experimental results for the work function at different doping concentrations according to an embodiment of the present invention.
  • FIG. 9 illustrates a work function measured by applying a Kelvin probe to each of the undoped graphene electrodes (Pristine) and graphene electrodes doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM, and 10 mM, respectively.
  • the graph shows the measurement result of (Work function).
  • 10A and 10B illustrate experimental results of graphene field effect transistors at different doping concentrations according to an exemplary embodiment of the present invention.
  • FIG. 10A shows the current-voltage of a graphene field effect transistor according to an undoped graphene electrode (0 mM) and graphene electrodes doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively.
  • the resultant graphs of the curves and diplock points and mobility are shown
  • FIG. 10B shows the resultant graphs of the mobility of electrons and holes of the graphene electrodes calculated from the I SD -V G curves.
  • drain-source current (I SD ) and gate voltage (A BG ) curves of all samples show the conduction characteristics of electrons and holes around the dilock point as is generally observed.
  • the I SD ⁇ V G curve is symmetrical in the field effect transistor (FET) of the initial state graphene (0mM). However, it can be seen that the asymmetry changes as the doping concentration (n D ) gradually increases.
  • the dirac point moves as the doping concentration n D of the doping solution increases depending on the amount of powder of gold chloride.
  • the position of the diplock point shifts toward the positive gate voltage in the I SD -V G curve.
  • the dilock point may be found to be about 60V when the doping concentration is at most 10 mM.
  • FIG. 10B illustrates a graph of mobility of electrons and holes of graphene calculated by Equation 2 below from the I SD -V G curve of FIG. 10A.
  • the electron mobility is reduced from approximately 3,000 to 550 cm 2 / Vs as the doping concentration (n D ) of the doping solution increases depending on the amount of powder of gold chloride You can see that.
  • the hole mobility (Hole) can be seen that the decrease is small from 2200 to 1600cm 2 / Vs as the doping concentration increases.
  • FIG. 11 illustrates a scanning electron microscope image of a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • FIG. 11 is a graphene electrode (Graphene) is formed on the substrate (Glass), a hole transport layer (PEDOT: PSS) is formed on the graphene electrode (Graphene), the blocking on the hole transport layer
  • a layer MAbI 3 , a perovskite structure material
  • PCBM electron transport layer
  • Al electrode upper electrode
  • a ⁇ 60-nm upper electrode Al electrode
  • a ⁇ 50-nm electron transport layer PCBM
  • a ⁇ 380nm blocking layer MAbI 3
  • a ⁇ 40nm hole transport layer PEDOT
  • 12A and 12B illustrate evaluation results of characteristics of a perovskite solar cell using a graphene electrode according to an exemplary embodiment of the present invention.
  • FIG. 12A illustrates a graph of evaluation of characteristics of a perovskite solar cell using an undoped graphene electrode (Pristine), and FIG. 12B illustrates a perovskite using a graphene electrode doped with 7.5 mM gold chloride. It shows the characteristic evaluation graph of the sky solar cell.
  • Primary undoped graphene electrode
  • FIG. 12B illustrates a perovskite using a graphene electrode doped with 7.5 mM gold chloride. It shows the characteristic evaluation graph of the sky solar cell.
  • the reason for this is, firstly, the result of the conductivity improvement of the graphene electrode, and secondly, the work function increases as the doping concentration of the doping solution increases depending on the amount of gold chloride powder.
  • the Fermi level of graphene can be placed further down the diplock point, and thus the holes can be moved more easily in the hole transport layer PEDOT: PSS. It can be seen that.
  • Figure 13 shows the experimental results for the external quantum efficiency of the perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • FIG. 13 shows measurement results of external quantum efficiency (EQE) according to undoped graphene electrodes (Pristine) and graphene electrodes doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively. The graph is shown.
  • EQE external quantum efficiency
  • FIG. 14A and 14B illustrate graphs of measurement results of diffusion coefficients and carrier decay times at different doping concentrations and calculation examples of diffusion distances according to embodiments of the present invention.
  • FIG. 14A shows a graph of measurement results of diffusion coefficients between undoped graphene electrodes (0 mM) and graphene electrodes doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively.
  • FIG. 14B shows a graph of measurement results of carrier decay time according to undoped graphene electrodes (0 mM) and graphene electrodes doped with gold chloride of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM, respectively.
  • 15A to 15F illustrate evaluation results of characteristics of a perovskite solar cell using graphene electrodes at different doping concentrations according to an embodiment of the present invention.
  • FIGS. 15A to 15F illustrate graphene electrodes according to doping concentrations of undoped graphene electrodes (Pristine, 0 mM) and doping concentrations of 1 mM, 2.5 mM, 5 mM, 7.5 mM and 10 mM gold chloride (AuCl3).
  • the graph shows the results of measuring 24 perovskite solar cells, respectively.
  • the measurement result of 24 perovskite solar cells according to the undoped graphene electrode (0 mM) shows 10.24 ⁇ 1.29%.
  • FIG. 16 shows the results of measuring the stability of the current for the perovskite solar cell using a gold chloride-doped graphene electrode according to an embodiment of the present invention.
  • FIG. 16 illustrates a graph showing the results of measuring the stability of the current for a perovskite solar cell using a graphene electrode doped with 7.5 mM gold chloride (AuCl 3 ).
  • FIG. 16 is a graph of a measurement result of a perovskite solar cell using a graphene electrode doped with 7.5 mM gold chloride while the encapsulation environment is maintained at 50% humidity without applying encapsulation technology. It is shown.
  • the perovskite solar cell using a graphene electrode doped with 7.5mM gold chloride can be seen that the current density hardly changes even after 100 hours of light irradiation.
  • the perovskite solar cell using the graphene electrode according to the embodiment of the present invention exhibits excellent stability characteristics, and the graphene electrode can be applied to the flexible device based on these results. It can be applied to various optoelectronic devices.
  • FIG. 17 is a flowchart illustrating a method of manufacturing a perovskite solar cell using a graphene electrode according to an embodiment of the present invention.
  • a graphene electrode is formed by spin coating a p-type impurity solution on the graphene to dope the transferred graphene on the substrate, and the electrode characteristics of the graphene electrode are proportional to the doping concentration of the p-type impurity solution. It may be a step of improving.
  • the graphene electrode is formed by a p-type impurity solution of gold chloride (AuCl 3 ), and the doping concentration may be controlled by the amount of powder of gold chloride.
  • step 1730 a hole transport layer is deposited on the doped graphene electrode.
  • Step 1730 may be a step of spin-coating methanol and a PEDOT: PSS solution on the doped graphene electrode, and then evaporating methanol to deposit a hole transport layer.
  • a perovskite structure material is coated on the hole transport layer to form a barrier layer of a thin metal oxide layer.
  • Step 1740 may be a step of forming the blocking layer of the perovskite structure material by spin coating a perovskite structure material and dimethylformamide (N, N, dimethylformamide) solution on the hole transport layer.
  • dimethylformamide N, N, dimethylformamide
  • an electron transport layer is formed on the blocking layer.
  • Step 1750 may be a step of forming a electron transfer layer, which is an electron transfer layer, by spin-coating a phenyl-C61-butyric acid methyl ester (PCBM) and toluene solution on a single layer.
  • PCBM phenyl-C61-butyric acid methyl ester
  • an upper electrode is formed on the electron transport layer.
  • Step 1760 is performed on at least one of silver (Ag), gold (Au), copper (Cu), aluminum (Al), platinum (Pt) and alloys thereof using a thermal evaporator on the electron transport layer. It may be a step of forming an upper electrode from a material.

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Abstract

La présente invention concerne : une cellule solaire de pérovskite utilisant une électrode de graphène, permettant de réguler une fonction de travail tout en maintenant une conductivité électrique élevée du graphène ; et son procédé de fabrication. Une électrode de graphène de type p est utilisée dans une structure de cellule solaire de pérovskite et sa concentration de dopage est régulée, et ainsi l'efficacité de conversion d'énergie de la cellule solaire de pérovskite peut être augmentée.
PCT/KR2017/002415 2016-12-26 2017-03-07 Cellule solaire de pérovskite utilisant une électrode de graphène, et son procédé de fabrication Ceased WO2018124390A1 (fr)

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CN114684819A (zh) * 2022-03-31 2022-07-01 华中科技大学 钙钛矿型氧化物及其制备方法和在制备一氧化碳的应用
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CN110148673A (zh) * 2019-04-28 2019-08-20 南京邮电大学 一种改性pedot:pss、制备方法和石墨烯基钙钛矿量子点发光二极管的制备方法
CN114868268A (zh) * 2019-09-25 2022-08-05 剑桥企业有限公司 钙钛矿半导体器件
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CN114684819A (zh) * 2022-03-31 2022-07-01 华中科技大学 钙钛矿型氧化物及其制备方法和在制备一氧化碳的应用
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CN116718730A (zh) * 2023-06-09 2023-09-08 华东理工大学 一种一体式自供能气体传感器件平台

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