CN107123741B - Phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell and manufacturing method thereof - Google Patents
Phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell and manufacturing method thereof Download PDFInfo
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- 239000001007 phthalocyanine dye Substances 0.000 claims abstract description 37
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- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
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- 229910015711 MoOx Inorganic materials 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 3
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- 239000005361 soda-lime glass Substances 0.000 claims description 3
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- 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
- Y02E10/549—Organic PV 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
- 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
Abstract
The invention relates to the technical field of inorganic perovskite CsPbBr3 thin film photovoltaic cells, in particular to a phthalocyanine dye sensitized CsPbBr3 thin film photovoltaic cell and a manufacturing method thereof. The phthalocyanine dye sensitized CsPbBr3 photovoltaic cell comprises a transparent conductive substrate, a hole transport layer, a CsPbBr3 thin film photosensitive layer, a dye sensitized layer, an electron transport layer, an electrode modification layer and a reflecting electrode. The invention can improve the energy conversion efficiency and the service life of the CsPbBr3 photovoltaic cell.
Description
Technical Field
the invention relates to the technical field of inorganic perovskite CsPbBr3 photovoltaic cells, in particular to a phthalocyanine dye sensitized CsPbBr3 photovoltaic cell and a manufacturing method thereof.
Background
energy crisis and environmental pollution are two prominent problems facing the development of the human society at present. The photovoltaic industry, which is centered on solar cells, directly converts solar energy into electrical energy, which is one of the cleanest energy sources available to human beings and is recognized as "green energy source". In recent years, the research heat of perovskite solar cells scraped from the solar field has attracted more and more attention of researchers, and such perovskite materials have excellent photoelectric properties, such as high quantum efficiency, large light absorption coefficient, long carrier migration distance, and the like, and also have solution processability. The perovskite does not show great application prospect in the solar field. The perovskite material commonly used at present is mainly organic-inorganic hybrid perovskite (CH3NH3PbX3), and a great problem of the material is that the material has poor thermal stability and is easy to decompose at high temperature. Inorganic perovskites CsPbBr3, which can withstand high temperatures above 200 ℃, can avoid this problem.
however, inorganic perovskite CsPbBr3 photovoltaic cells are not perfect. Currently, the CsPbBr3 battery has the following problems: (1) the research of the international CsPbBr3 battery is just started, and particularly, the defect of surface flatness of the prepared CsPbBr3 film has a large number of holes, and the existence of the holes can cause the direct contact of an electron transmission layer such as C60 and the like and a hole transmission layer, increase the recombination probability of electron holes, reduce the parallel resistance of the battery, and cause the overall reduction of characteristic parameters such as short-circuit current, filling factor, open-circuit voltage and the like of the battery, thereby reducing the efficiency of the battery. (2) The light absorption range of the CsPbBr3 is within the range of 300-520 nm, and the absorption is weak or almost no in the visible light range and near infrared region of 520-760 nm, so that the photocurrent and the energy conversion efficiency of the CsPbBr3 battery are greatly limited. (3) in addition, the CsPbBr3 battery has the problem that CsPbBr3 is sensitive to water oxygen, which affects the service life of the battery. Solving these problems is very urgent to improve the performance of CsPbBr3 batteries.
Disclosure of Invention
in order to solve the problems of CsPbBr3 photovoltaic cells in the background technology, the invention provides a phthalocyanine dye sensitized CsPbBr3 photovoltaic cell and a preparation method thereof, and the adopted technical scheme is as follows:
The invention provides a phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell which is characterized by comprising a transparent conductive substrate, a hole transport layer, a CsPbBr3 thin film photosensitive layer, a dye sensitized layer, an electron transport layer, an electrode modification layer and a reflecting electrode.
furthermore, the CsPbBr3 thin film photosensitive layer is a polycrystal of CsPbBr3 and is formed on the hole transport layer, the thickness of the CsPbBr3 thin film photosensitive layer is 100-300nm, and the surface root mean square roughness of the CsPbBr3 thin film photosensitive layer is 20-40 nm.
further, the dye sensitization layer is phthalocyanine, the dye sensitization layer is formed on the CsPbBr3 thin film photosensitive layer, and the dye sensitization layer is preferably SubPc, ClAlPc and SubNc, and the thickness of the dye sensitization layer is 10-20 nm.
further, the transparent conductive substrate is transparent glass such as quartz glass, silicate glass, high silica glass or soda-lime glass, etc., on which ITO grows, the ITO thickness is preferably 100-300nm, the light transmittance is greater than 85%, and the square resistance is less than 10 Ω.
The hole transport layer is formed on the transparent conductive substrate, the hole transport layer comprises but is not limited to graphene, PEDOT PSS, PTAA, polyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE and PEI, and the thickness of the hole transport layer is preferably 10-50 nm.
further, the phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell is characterized in that the electron transport layer is formed on the dye-sensitized layer, the electron transport layer includes but is not limited to C60, C70 and PCBM, and the thickness of the electron transport layer is preferably 20-50 nm.
Further, the electrode modification layer is one of BCP, Bphen, Alq3 and TPBI, and the preferable thickness is 5-10 nm.
Further, the reflective electrode is formed on the electrode modification layer, the reflective electrode includes but is not limited to Al, Au, Ag, and the preferred thickness of the reflective electrode is 100-.
as another aspect of the present invention, there is provided a method for manufacturing a phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell, characterized in that the preparation of the device comprises, in order, the steps of:
(1) cleaning a transparent conductive substrate;
(2) forming a hole transport layer on a transparent conductive substrate;
(3) forming a CsPbBr3 thin film photosensitive layer on the hole transport layer;
(4) Forming a dye-sensitized layer on the CsPbBr3 thin film photosensitive layer;
(5) forming an electron transport layer on the dye-sensitized layer;
(6) forming an electrode modification layer on the electron transport layer;
(7) and forming a reflecting electrode on the electrode modification layer.
Further, the manufacturing method of the phthalocyanine dye sensitized CsPbBr3 photovoltaic cell is characterized in that the step of forming the CsPbBr3 thin film photosensitive layer on the hole transport layer comprises the following steps:
(1) synthesizing CsPbBr3 polycrystal;
(2) preparing a CsPbBr3 precursor solution, wherein the concentration of the CsPbBr3 precursor solution is 0.5M, the solute of the CsPbBr3 precursor solution is synthesized CsPbBr3 polycrystal, and the solvent is dimethyl sulfoxide;
(3) Spin coating CsPbBr3 precursor solution on the hole transport layer;
(4) Annealing on a heating plate, evaporating the solvent to obtain the CsPbBr3 film photosensitive layer, wherein the annealing temperature is 90-200 ℃, and the annealing time is 10-30 minutes.
Further, the manufacturing method of the phthalocyanine dye sensitized CsPbBr3 photovoltaic cell is characterized in that the method for synthesizing the CsPbBr3 polycrystal comprises the following steps:
(1) dissolving 3.65g of PbBr2 in 15ml of HBr solution with the mass fraction of 48% to obtain solution A;
(2) Taking 2.13g of CsBr, and putting the solution in 5ml of deionized water to obtain a solution B;
(3) fully mixing the solution A and the solution B to obtain an orange solute;
(4) The obtained orange solute was washed with absolute ethanol and then vacuum-dried to obtain CsPbBr3 polymorph.
further, the manufacturing method of the phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell is characterized in that the step of forming a dye-sensitized layer on the CsPbBr3 thin film photosensitive layer comprises the following steps:
(1) loading the substrate with the CsPbBr3 film photosensitive layer into an ultrahigh vacuum coating system and loading the required phthalocyanine dye material;
(2) vacuumizing the ultrahigh vacuum coating system until the vacuum degree is less than 5 multiplied by 10 -4 Pa;
(3) The phthalocyanine dye is deposited on the CsPbBr3 film photosensitive layer by adopting a vacuum thermal evaporation method.
Compared with the prior art, the invention has the beneficial effects that: the defect of surface flatness of the CsPbBr3 film is improved, the phthalocyanine dye layer can fill holes on the surface of the CsPbBr3 film, direct contact between an electron transport layer and a hole transport layer is avoided, the recombination probability of electron holes is reduced, the parallel resistance of the battery is increased, the short-circuit current, the filling factor and the open-circuit voltage of the battery are improved, and finally the energy conversion efficiency of the battery is improved. (2) Increasing the photoresponse range of the cell; the phthalocyanine dye layer has good light absorption in a visible light range, and photogenerated excitons generated after the phthalocyanine dye layer absorbs light can be decomposed at an interface of the electron transport layer to form photogenerated current, so that the absorption of the cell can be enhanced by introducing the phthalocyanine dye layer, and the energy conversion efficiency of the cell is finally improved. (3) Improving the life of the battery; the phthalocyanine dye has good protection effect on the CsPbBr3 film layer of the battery due to chemical property temperature under the conditions of air and most of chemical solvents, and the service life of the battery is prolonged.
drawings
Fig. 1 is a phthalocyanine dye sensitized CsPbBr3 photovoltaic cell of the present invention;
FIG. 2 is a surface topography of a CsPbBr3 thin film photosensitive layer according to the present invention;
FIG. 3 is an absorption spectrum of a CsPbBr3 thin film photosensitive layer of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention provides a technical solution:
A phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell is characterized by comprising a transparent conductive substrate, a hole transport layer, a CsPbBr3 thin film photosensitive layer, a dye sensitized layer, an electron transport layer, an electrode modification layer and a reflecting electrode;
furthermore, the CsPbBr3 film photosensitive layer is polycrystal of CsPbBr3 and is formed on the hole transport layer, the thickness of the CsPbBr3 film photosensitive layer is 100-300nm, and the surface root mean square roughness of the CsPbBr3 film photosensitive layer is 20-40 nm;
Further, the dye sensitization layer is phthalocyanine, the dye sensitization layer is formed on the CsPbBr3 thin film photosensitive layer, and the dye sensitization layer is preferably SubPc, ClAlPc and SubNc, and the thickness of the dye sensitization layer is 10-20 nm.
further, the transparent conductive substrate is transparent glass such as quartz glass, silicate glass, high silica glass or soda-lime glass, etc., on which ITO grows, the ITO thickness is preferably 100-300nm, the light transmittance is greater than 85%, and the square resistance is less than 10 Ω.
The hole transport layer is formed on the transparent conductive substrate, the hole transport layer comprises but is not limited to graphene, PEDOT PSS, PTAA, polyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE and PEI, and the thickness of the hole transport layer is preferably 10-50 nm.
Further, the electron transport layer is formed on the dye sensitizing layer, the electron transport layer includes but is not limited to C60, C70, PCBM, the thickness of the electron transport layer is preferably 20-50 nm.
Further, the electrode modification layer is formed on the electron transport layer, the electrode modification layer is one of BCP, Bphen, Alq3 and TPBI, and the preferable thickness is 5-10 nm.
further, the reflective electrode is formed on the electrode modification layer, the reflective electrode includes but is not limited to Al, Au, Ag, and the preferred thickness of the reflective electrode is 100-.
a manufacturing method of a phthalocyanine dye sensitized CsPbBr3 photovoltaic cell is characterized in that the preparation of a device sequentially comprises the following steps:
(1) Cleaning a transparent conductive substrate;
(2) forming a hole transport layer on a transparent conductive substrate;
(3) Forming a CsPbBr3 thin film photosensitive layer on the hole transport layer; the method comprises the following steps:
A. Synthesizing CsPbBr3 polycrystal; dissolving 3.65g of PbBr2 in 15ml of HBr solution with the mass fraction of 48% to obtain solution A; taking 2.13g of CsBr, and putting the solution in 5ml of deionized water to obtain a solution B; fully mixing the solution A and the solution B to obtain an orange solute; washing the obtained orange solute with absolute ethyl alcohol, and then drying in vacuum to obtain CsPbBr3 polycrystal;
B. preparing a CsPbBr3 precursor solution, wherein the concentration of the CsPbBr3 precursor solution is 0.5M, the solute of the CsPbBr3 precursor solution is synthesized CsPbBr3 polycrystal, and the solvent is dimethyl sulfoxide;
C. Spin coating CsPbBr3 precursor solution on the hole transport layer;
D. Annealing on a heating plate, and evaporating a solvent to obtain a CsPbBr3 film photosensitive layer, wherein the annealing temperature is 90-200 ℃;
(4) forming a dye-sensitized layer on the CsPbBr3 thin film photosensitive layer; the method comprises the following steps:
A. loading the substrate with the CsPbBr3 film photosensitive layer into an ultrahigh vacuum coating system and loading the required phthalocyanine dye material;
B. Vacuumizing the ultrahigh vacuum coating system until the vacuum degree is less than 5 multiplied by 10 -4 Pa;
C. Depositing phthalocyanine dye on the CsPbBr3 film photosensitive layer by adopting a vacuum thermal evaporation method;
(5) Forming an electron transport layer on the dye-sensitized layer;
(6) Forming an electrode modification layer on the electron transport layer;
(7) A reflective electrode is formed on the electrode transfer layer.
example one
A phthalocyanine dye sensitized CsPbBr3 photovoltaic cell and a manufacturing method thereof are disclosed, the device structure is from bottom to top Glass/ITO/PEDOT PSS/CsPbBr 3/SubPc/C60/Bphen/Al.
Providing an ITO glass substrate, wherein the thickness of ITO is preferably 100-300nm, the light transmittance is more than 85%, and the square resistance is less than 10 omega, and manufacturing the CsPbBr3 photovoltaic cell according to the following steps:
(1) Cleaning a transparent conductive substrate: ultrasonically cleaning a transparent conductive substrate for 20 minutes by adopting acetone, isopropanol and deionized water in sequence, and irradiating the transparent conductive substrate for twenty minutes by using an ultraviolet lamp after drying the transparent conductive substrate by using nitrogen;
(2) forming a hole transport layer on a transparent conductive substrate: PSS is taken as a hole transport layer, the PEDOT is deposited on an ITO transparent conductive substrate by a spin coating method at the rotation speed of 4000 rpm for 40s, and then annealing treatment is carried out on a heating plate at the temperature of 120 ℃ for 30 minutes;
(3) Forming a CsPbBr3 thin film photosensitive layer on the hole transport layer, and preparing the CsPbBr3 thin film photosensitive layer according to the following steps:
A. synthesizing CsPbBr3 polycrystal; dissolving 3.65g of PbBr2 in 15ml of HBr solution with the mass fraction of 48% to obtain solution A; taking 2.13g of CsBr, and putting the solution in 5ml of deionized water to obtain a solution B; fully mixing the solution A and the solution B to obtain an orange solute; washing the obtained orange solute with absolute ethyl alcohol, and then drying in vacuum to obtain CsPbBr3 polycrystal;
B. preparing a CsPbBr3 precursor solution, wherein the concentration of the CsPbBr3 precursor solution is 0.5M, the solute of the CsPbBr3 precursor solution is synthesized CsPbBr3 polycrystal, and the solvent is dimethyl sulfoxide;
C. spin coating a CsPbBr3 precursor solution on the hole transport layer: the rotating coating rotating speed is 2000 rpms, and the time is 30 s;
D. Annealing on a heating plate: evaporating the solvent to obtain a CsPbBr3 film photosensitive layer, wherein the annealing temperature is 90 ℃, and the annealing time is 30 minutes;
(4) forming a dye-sensitized layer on the CsPbBr3 thin film photosensitive layer, the dye-sensitized layer being prepared by the following steps:
A. loading the substrate with the CsPbBr3 film photosensitive layer into an ultrahigh vacuum coating system and loading the substrate with the required phthalocyanine dye material SubPc;
B. vacuumizing the ultrahigh vacuum coating system until the vacuum degree is less than 5 multiplied by 10 -4 Pa;
C. Depositing phthalocyanine dye on the CsPbBr3 film photosensitive layer by adopting a vacuum thermal evaporation method, wherein the deposition rate is 0.02 nm/s, the deposition rate is monitored by a quartz crystal oscillator plate, and the deposition thickness is 10 nm;
(5) forming an electron transport layer on the dye-sensitized layer: growing a layer of 40nm C60 as an electron transport layer by a thermal evaporation method;
(6) forming an electrode modification layer on the electron transport layer: growing a 5 nm Bphen electrode modification layer by a thermal evaporation method;
(7) forming a reflective electrode on the electrode transport layer: and growing a layer of Al with the thickness of 100 nm as a reflecting electrode by a thermal evaporation or magnetron sputtering method.
referring to fig. 2, the CsPbBr3 film has a large defect in surface flatness, and a large number of holes exist on the surface, and the existence of the holes can cause direct contact between an electron transport layer such as C60 and a hole transport layer, increase the recombination probability of electron holes, reduce the parallel resistance of the battery, and cause overall reduction of characteristic parameters such as short-circuit current, fill factor, and open-circuit voltage of the battery, thereby reducing the efficiency of the battery. The phthalocyanine layers such as SubPc can fill holes on the surface of the CsPbBr3 film, so that the direct contact between the electron transport layer and the hole transport layer is avoided, the recombination probability of electron holes is reduced, the parallel resistance of the battery is increased, the short-circuit current, the filling factor and the open-circuit voltage of the battery are improved, and the energy conversion efficiency of the battery is finally improved.
Referring to fig. 3, the light absorption range of CsPbBr3 is within 300-520 nm, and the absorption is weak or no at 520-760 nm in the visible light range and near infrared region, which greatly limits the photocurrent and cell efficiency of CsPbBr3 cell. The phthalocyanine dye layer has good light absorption in a visible light range, and photogenerated excitons generated after the phthalocyanine dye layer absorbs light can be decomposed at an interface of the electron transport layer to form photogenerated current, so that the absorption of the cell can be enhanced by introducing the phthalocyanine dye layer, and the energy conversion efficiency of the cell is finally improved. The SubPc phthalocyanine dye with the wavelength of 10nm is introduced to be used as a photosensitive layer of the cell, and the SubPc has better absorption at 520-600 nm, so that the light responsivity of the cell from 520 nm to 600 nm can be greatly enhanced, and the efficiency of the cell is improved.
In addition, the CsPbBr3 battery has the problem that CsPbBr3 is sensitive to water, and the service life of the battery is influenced. Due to the chemical property and temperature of phthalocyanine dyes such as SubPc under the conditions of air and most of less chemical solvents, the film layer of the CsPbBr3 of the battery can be well protected, and the service life of the battery is prolonged.
through comparison tests, the short-circuit current density of the phthalocyanine dye sensitized CsPbBr3 photovoltaic cell adopting SubPc as the dye sensitization layer is 4.3 mA/cm 2, the open-circuit voltage is 1.32V, the filling factor is 0.45, the energy conversion efficiency is 2.55%, compared with the CsPbBr3 photovoltaic cell without the dye sensitization layer, the short-circuit current density of the photovoltaic cell is 2.3mA/cm2, the open-circuit voltage is 1.12V, the filling factor is 0.34, and the energy conversion efficiency is 0.87%.
example two
A phthalocyanine dye sensitized CsPbBr3 photovoltaic cell and a manufacturing method thereof are disclosed, the device structure is from bottom to top Glass/ITO/PEDOT PSS/CsPbBr 3/ClAlPc/PCBM/BCP/Ag.
Providing any ITO glass substrate, wherein the thickness of ITO is preferably 100-300nm, the light transmittance is more than 85%, and the square resistance is less than 10 omega, and preparing the CsPbBr3 photovoltaic cell according to the following steps:
(1) cleaning a transparent conductive substrate: the same as the first embodiment;
(2) forming a hole transport layer on a transparent conductive substrate: the same as the first embodiment;
(3) forming a CsPbBr3 thin film photosensitive layer on the hole transport layer, and preparing the CsPbBr3 thin film photosensitive layer according to the following steps:
A. Synthesizing CsPbBr3 polycrystal, which is the same as the first embodiment;
B. Preparing a CsPbBr3 precursor solution in the same way as in the first embodiment;
C. spin coating a CsPbBr3 precursor solution on the hole transport layer: the rotary coating speed is 4000 rpms, and the time is 50 s;
D. Annealing on a heating plate: evaporating the solvent to obtain a CsPbBr3 film photosensitive layer, wherein the annealing temperature is 200 ℃, and the annealing time is 10 minutes;
(4) forming a dye-sensitized layer on the CsPbBr3 thin film photosensitive layer, the dye-sensitized layer being prepared by the following steps:
A. loading the substrate with the CsPbBr3 film photosensitive layer into an ultrahigh vacuum coating system, and loading the substrate with the required phthalocyanine dye material ClAlPc;
B. Vacuumizing the ultrahigh vacuum coating system until the vacuum degree is less than 5 multiplied by 10 -4 Pa;
C. depositing phthalocyanine dye on the CsPbBr3 film photosensitive layer by adopting a vacuum thermal evaporation method, wherein the deposition rate is 0.05 nm/s, the deposition rate is monitored by a quartz crystal vibrating piece, and the deposition thickness is 20 nm;
(5) forming an electron transport layer on the dye-sensitized layer: growing a PCBM layer as an electron transport layer by a spin coating method;
(6) forming an electrode modification layer on the electron transport layer: growing a 10nm BCP electrode modification layer by a thermal evaporation method;
(7) forming a reflective electrode on the electrode transport layer: and growing a layer of Ag with the thickness of 200 nm as a reflecting electrode by a thermal evaporation or magnetron sputtering method.
the beneficial effects are as described in the first embodiment, specifically: (1) the ClAlPc phthalocyanine sensitizing layer can fill the holes on the surface of the CsPbBr3 film; (2) the ClAlPc phthalocyanine dye sensitized layer can enhance the absorption of the cell in the range of 520-900 nm, thereby improving the cell efficiency; (3) the sensitized layer of the ClAlPc phthalocyanine dye can protect the CsPbBr3 film and prolong the service life of the battery. The test results show that the efficiency and the service life of the battery are improved by more than one time.
The working and implementation principle of the present invention is briefly described below. The invention introduces a phthalocyanine sensitizing layer to improve the efficiency and the service life of the CsPbBr3 photovoltaic cell, and is based on the following reasons: (1) the binding energy of the exciton of the perovskite material is very small, and the exciton binding energy is reported to be less than 0.1 eV, so that the photogenerated exciton formed in the CsPbBr3 perovskite can be automatically dissociated into free electron and hole to a great extent without diffusing to the interface of the photogenerated exciton and an electron transmission layer, and even if a phthalocyanine dye sensitization layer is introduced, the decomposition of the exciton and the formation of photocurrent in the CsPbBr3 photosensitive layer are not hindered; (2) the phthalocyanine dye material has good bipolar transmission performance, namely photo-generated electrons formed in the CsPbBr3 photosensitive layer can be transmitted to the electron transmission layer through the sensitizing layer and are finally collected by the electrode, and the transmission and collection of charges in the original device are not influenced by the introduction of the dye sensitizing layer. (3) The surface roughness of the CsPbBr3 film photosensitive layer is large, and more holes exist. Even if a sensitizing layer with a certain thickness, such as 20nm, is introduced, the contact between the CsPbBr3 layer and the electron transport layer cannot be completely isolated, or the actual distance between the CsPbBr3 layer and the electron transport layer is smaller than the thickness of the sensitizing layer, so that the possibility of decomposition of excitons in CsPbBr3 at the interface between the excitons and the electron transport layer is improved, the electron transport distance is shortened, and the collection of photo-generated electrons formed in CsPbBr3 is facilitated.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. a phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell is characterized by comprising a transparent conductive substrate, a hole transport layer, a CsPbBr3 thin film photosensitive layer, a dye sensitized layer, an electron transport layer, an electrode modification layer and a reflecting electrode; the dye sensitization layer is phthalocyanine dye, the dye sensitization layer is one of SubPc, ClAlPc and SubNc, the dye sensitization layer is formed on the CsPbBr3 film photosensitive layer, the thickness is 10-20nm, the CsPbBr3 film photosensitive layer is polycrystal of CsPbBr3, and the dye sensitization layer is formed on the hole transmission layer; the thickness of the CsPbBr3 film photosensitive layer is 100-300nm, the surface root mean square roughness of the CsPbBr3 film photosensitive layer is 20-40nm, and the electron transport layer is formed on the dye sensitization layer; the electron transport layer is one of C60, C70 and PCBM, and the thickness of the electron transport layer is 20-50 nm.
2. the phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell according to claim 1, wherein the transparent conductive substrate is a transparent glass such as quartz glass, silicate glass, high silica glass or soda-lime glass on which ITO has been grown, the ITO thickness is 100-300nm, the light transmittance is greater than 85%, and the sheet resistance is less than 10 Ω.
3. the phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell according to claim 1, wherein said hole transport layer is formed on a transparent conductive substrate; the hole transport layer comprises but is not limited to graphene, PEDOT PSS, PTAA, polyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE and PEI, and the thickness of the hole transport layer is 10-50 nm.
4. the phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell according to claim 1, wherein the electrode modification layer is one of BCP, Bphen, Alq3, TPBI, and the thickness of the electrode modification layer is 5-10 nm.
5. The phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell according to claim 1, wherein said reflective electrode is formed on an electrode modification layer; the reflective electrode includes but is not limited to Al, Au, Ag, and the thickness of the reflective electrode is 100-1000 nm.
6. a manufacturing method of a phthalocyanine dye sensitized CsPbBr3 photovoltaic cell is characterized in that the preparation of a device sequentially comprises the following steps:
(1) cleaning a transparent conductive substrate;
(2) Forming a hole transport layer on a transparent conductive substrate;
(3) Forming a CsPbBr3 thin film photoactive layer on the hole transport layer, the forming of the CsPbBr3 thin film photoactive layer comprising the steps of: s1 Synthesis of CsPbBr3 polymorph: dissolving 3.65g of PbBr2 in 15ml of HBr solution with the mass fraction of 48% to obtain solution A; taking 2.13g of CsBr, and putting the solution in 5ml of deionized water to obtain a solution B; fully mixing the solution A and the solution B to obtain an orange solute; washing the obtained orange solute with absolute ethyl alcohol, and then drying in vacuum to obtain CsPbBr3 polycrystal; s2 is prepared into CsPbBr3 precursor solution, the concentration of the CsPbBr3 precursor solution is 0.5M, the solute of the CsPbBr3 precursor solution is synthesized CsPbBr3 polycrystal, and the solvent is dimethyl sulfoxide; s3 spin coating CsPbBr3 precursor solution on the hole transport layer; annealing on a s4 heating plate, evaporating a solvent to obtain a CsPbBr3 film photosensitive layer, wherein the annealing temperature is 90-200 ℃, and the annealing time is 10-30 minutes;
(4) forming a dye sensitization layer on the CsPbBr3 thin film photosensitive layer, wherein the dye sensitization layer is one of SubPc, ClAlPc and SubNc;
(5) forming an electron transport layer on the dye-sensitized layer;
(6) forming an electrode modification layer on the electron transport layer;
(7) and forming a reflecting electrode on the electrode modification layer.
7. the method of fabricating a phthalocyanine dye-sensitized CsPbBr3 photovoltaic cell according to claim 6, wherein the forming of the dye-sensitized layer comprises the steps of:
(1) loading the substrate with the CsPbBr3 film photosensitive layer into an ultrahigh vacuum coating system and loading the required phthalocyanine dye material;
(2) vacuumizing the ultrahigh vacuum coating system until the vacuum degree is less than 5 multiplied by 10 -4 Pa;
(3) The phthalocyanine dye is deposited on the CsPbBr3 film photosensitive layer by adopting a vacuum thermal evaporation method.
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| CN105742508A (en) * | 2016-04-12 | 2016-07-06 | 上海大学 | Preparation method for perovskite solar cell with tetramino zinc phthalocyanine organic hole transmission layer |
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Denomination of invention: A CsPbBr3 photovoltaic cell sensitized with phthalocyanine dye and its manufacturing method Effective date of registration: 20231211 Granted publication date: 20191210 Pledgee: Agricultural Bank of China Limited by Share Ltd. Tiantai County branch Pledgor: Zhou Xiaoyin Registration number: Y2023330002995 |