CN116828943A - Method for improving crystallinity of perovskite solar cell - Google Patents
Method for improving crystallinity of perovskite solar cell Download PDFInfo
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- 239000002243 precursor Substances 0.000 claims abstract description 38
- RAJISUUPOAJLEQ-UHFFFAOYSA-N chloromethanamine Chemical compound NCCl RAJISUUPOAJLEQ-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 229910003437 indium oxide Inorganic materials 0.000 claims description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 9
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007788 liquid Substances 0.000 claims description 4
- RPNMGUBLKCLAEK-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfanyl-n,n-diethylethanamine;hydrochloride Chemical compound [Cl-].CC[NH+](CC)CCSC1=CC=C(Cl)C=C1 RPNMGUBLKCLAEK-UHFFFAOYSA-N 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
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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 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
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- 239000013078 crystal Substances 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 28
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 8
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a method for improving crystallinity of a perovskite solar cell, and belongs to the technical field of perovskite thin films. The method of the present invention comprises the steps of (1) forming an electron transport layer on a surface of a conductive substrate; (2) Coating a chloromethyl amine solution on the surface of the electron transport layer to form a chloromethyl amine film; (3) Coating a perovskite precursor solution on the surface of the chloromethyl amine film to form a perovskite wet film; (4) Placing the perovskite wet film in a wind collecting hood in solvent atmosphere, heating in stages, and annealing to form a perovskite film; (5) And sequentially forming a hole transport layer and an electrode layer on the surface of the perovskite film to obtain the perovskite solar cell with improved crystallinity. By adopting a chloromethyl amine pre-embedding mode, larger grain size can be obtained, thereby well solving the problem that excessive broken crystals are generated on the surface of the chloromethyl amine doped perovskite film.
Description
Technical Field
The invention belongs to the technical field of perovskite thin films, and particularly relates to a method for improving the crystallinity of a perovskite solar cell.
Background
The organic-inorganic hybrid perovskite solar cell is considered as a light absorbing material of the next generation of low-cost solar cells with the highest potential because of the excellent photoelectric properties of low cost, easy preparation, adjustable band gap and the like.
For preparing a high-quality perovskite film, the control of the formation process of perovskite crystal nuclei is critical, because the natural change process of perovskite is very rapid once the nucleation and growth of perovskite are started, and the perovskite is difficult to control, is unfavorable for the full coverage of the surface of the film, and is characterized by more film forming holes. The vertical crystallization of 3D perovskite can be promoted and the grain size thereof increased by solvent engineering, for example, by adding chloromethylamine to the perovskite precursor solution. However, the solvent can evaporate and disappear rapidly, the process window is small, and the control of the crystal size is not facilitated, so that the regulation means can improve the morphology of perovskite crystal grains, but the film formation is still rough and has holes.
On the other hand, roll-to-roll continuous production also places more stringent demands on the process of controlling crystallization. Accordingly, there is a need to provide a method that accommodates a roll-to-roll production process and that is effective in improving perovskite crystallization.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for improving the crystallinity of a perovskite solar cell. By adopting a mode of pre-burying the chloromethyl amine, larger grain size can be obtained by adjusting the dosage of the chloromethyl amine, thereby well solving the problem that excessive broken crystals are generated on the surface of the chloromethyl amine doped perovskite film.
The invention aims to provide a method for improving the crystallinity of a perovskite solar cell, which comprises the following steps,
(1) Forming an electron transport layer on the surface of the conductive substrate;
(2) Coating a chloromethyl amine solution on the surface of the electron transport layer to form a chloromethyl amine film; the concentration of the chloromethyl amine solution is 0.5mg/mL-6mg/mL;
(3) Coating a perovskite precursor solution on the surface of the chloromethyl amine film to form a perovskite wet film;
(4) Placing the perovskite wet film in a wind collecting hood in solvent atmosphere, heating in stages, and annealing to form a perovskite film; the heating treatment by stages is specifically divided into two stages, wherein the first stage is heating at 65-75 ℃ for 4-6 min; the second stage is heating at 100-150deg.C for 8-12 min;
(5) And sequentially forming a hole transport layer and an electrode layer on the surface of the perovskite film to obtain the perovskite solar cell with improved crystallinity.
In one embodiment of the present invention, in step (1), the conductive substrate is selected from fluorine doped tin oxide conductive substrate (FTO), tin doped indium oxide conductive substrate (ITO), titanium doped indium oxide conductive substrate (ITiO), cerium doped indium oxide conductive substrate (ICO), tungsten doped indium oxide conductive substrate (IWO), aluminum doped zinc oxide conductive substrate (AZO), or boron doped zinc oxide conductive substrate (BZO).
In one embodiment of the present invention, in the step (1), the conductive substrate is a pretreated conductive substrate, and the pretreatment is to sequentially wash with deionized water, ethanol, acetone, and isopropanol for 15min-20min each by an ultrasonic cleaner, and then perform UV-ozone treatment for 15min-20 min.
In one embodiment of the present invention, in step (1), the material of the electron transport layer is selected from the group consisting of TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness is 20nm-30nm.
In one embodiment of the present invention, in step (3), the perovskite precursor solution comprises a perovskite material and a solvent; the perovskite material is ABX 3 The perovskite type A is selected from one or more of methyl ammonium ion, formamidine ion, cesium ion and rubidium ion; b is selected from lead ions and/or tin ions; and X is one or more selected from iodide ions, bromide ions and chloride ions.
In one embodiment of the invention, the concentration of perovskite material in the perovskite precursor solution is in the range of 0.6mol/L to 1.4mol/L.
In one embodiment of the present invention, in step (3), the solvent is selected from one or more of 2-mercaptoethanol (2-ME), γ -butyrolactone (γ -GBL), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
Further, the solvent is prepared from N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to a volume ratio of 4:1, and mixing.
In one embodiment of the invention, in step (4), the operating speed of the perovskite wet film in the collection hood of the solvent atmosphere is 0.5m/min-1m/min; the air pressure of the air collecting cover is 0.2Mpa-1.2Mpa.
In one embodiment of the invention, in step (4), the solvent atmosphere employs a solvent that is consistent with the solvent in the perovskite precursor solution.
In one embodiment of the present invention, in step (4), the annealing is performed at 100 ℃ to 120 ℃ for 10min to 20min.
In one embodiment of the present invention, in the step (4), the perovskite thin film has a thickness of 500nm to 800nm.
In one embodiment of the present invention, in step (5), the material of the hole transport layer is selected from CuI, cuSCN, niO x One or more of PSS, spiro-OMeTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
In one embodiment of the invention, in step (5), the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) When the chloromethyl amine film is coated with the perovskite precursor solution, the perovskite precursor solution can partially permeate into the chloromethyl amine film, and a mixed interface layer can be formed between the perovskite precursor solution and the chloromethyl amine film, so that the concentration gradient distribution of the chloromethyl amine in the chloromethyl amine film-interface layer-perovskite wet film is beneficial to regulating and controlling the distribution of the chloromethyl amine in the direction vertical to a substrate, and the perovskite growth rate is regulated and controlled.
(2) According to the method, the volatilization process of the solvent is regulated and controlled after the solvent is in the air collecting cover of the solvent atmosphere, so that whether the perovskite concentration in the wet film reaches the critical supersaturation concentration of uniform nucleation is controlled, and the nucleation and grain growth processes are regulated.
(3) According to the method, the perovskite wet film is placed in the wind collecting cover of the solvent atmosphere, the atmospheric discharge rate is controlled, so that the air pressure of the wind collecting cover is larger than the saturated vapor pressure of the solvent in the wet film at the current temperature, the solvent in the wet film is not volatilized at this time, the pre-buried chloromethylamine partially permeates the perovskite wet film to form a concentration gradient, then the heating temperature in the space is raised, so that the air pressure of the wind collecting cover is lower than the saturated vapor pressure of the solvent of the wet film at the current heating temperature, the solvent in the wet film volatilizes, the perovskite precursor solution gradually reaches saturation, random nucleation occurs, the chloromethylamine fully participates in the vertical growth process of crystal nuclei in the process of slow volatilization of the solvent is controlled, and the prepared crystal grain size is large and the morphology is uniform.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a flow chart of the preparation of perovskite solar cell according to example 1 of the invention;
FIG. 2 is a block diagram of a perovskite solar cell of the invention; wherein, (a) is a structural diagram of the perovskite solar cell of example 1 and (b) is a structural diagram of the perovskite solar cell of comparative example 1;
FIG. 3 is an SEM characterization of perovskite thin film of example 1 according to the invention; wherein, (a) is a plan view and (b) is a cross-sectional view;
FIG. 4 is an SEM characterization of a perovskite thin film of comparative example 1 of the invention;
fig. 5 is an SEM characterization of the perovskite thin film of comparative example 2 of the invention.
Detailed Description
Therefore, the invention aims to solve the technical problems that the solvent volatilizes too fast and the crystallization process is difficult to control in the perovskite film preparation process in the prior art.
In order to solve the technical problems, the invention provides a method for improving the crystallinity of a perovskite solar cell. By adopting a mode of pre-burying the chloromethyl amine, larger grain size can be obtained by adjusting the dosage of the chloromethyl amine, thereby well solving the problem that excessive broken crystals are generated on the surface of the chloromethyl amine doped perovskite film.
The invention aims to provide a method for improving the crystallinity of a perovskite solar cell, which comprises the following steps,
(1) Forming an electron transport layer on the surface of the conductive substrate;
(2) Coating a chloromethyl amine solution on the surface of the electron transport layer to form a chloromethyl amine film; the concentration of the chloromethyl amine solution is 0.5mg/mL-6mg/mL;
(3) Coating a perovskite precursor solution on the surface of the chloromethyl amine film to form a perovskite wet film;
(4) Placing the perovskite wet film in a wind collecting hood in solvent atmosphere, heating in stages, and annealing to form a perovskite film; the heating treatment by stages is specifically divided into two stages, wherein the first stage is heating at 65-75 ℃ for 4-6 min; the second stage is heating at 100-150deg.C for 8-12 min;
(5) And sequentially forming a hole transport layer and an electrode layer on the surface of the perovskite film to obtain the perovskite solar cell with improved crystallinity.
In one embodiment of the present invention, in step (1), the conductive substrate is selected from fluorine doped tin oxide conductive substrate (FTO), tin doped indium oxide conductive substrate (ITO), titanium doped indium oxide conductive substrate (ITiO), cerium doped indium oxide conductive substrate (ICO), tungsten doped indium oxide conductive substrate (IWO), aluminum doped zinc oxide conductive substrate (AZO), or boron doped zinc oxide conductive substrate (BZO).
In one embodiment of the present invention, in the step (1), the conductive substrate is a pretreated conductive substrate, and the pretreatment is to sequentially wash with deionized water, ethanol, acetone, and isopropanol for 15min-20min each by an ultrasonic cleaner, and then perform UV-ozone treatment for 15min-20 min.
In one embodiment of the present invention, in step (1), the electron transportThe material of the layer is selected from TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness is 20nm-30nm.
In one embodiment of the present invention, in step (3), the perovskite precursor solution comprises a perovskite material and a solvent; the perovskite material is ABX 3 The perovskite type A is selected from one or more of methyl ammonium ion, formamidine ion, cesium ion and rubidium ion; b is selected from lead ions and/or tin ions; and X is one or more selected from iodide ions, bromide ions and chloride ions.
In one embodiment of the invention, the concentration of perovskite material in the perovskite precursor solution is in the range of 0.6mol/L to 1.4mol/L.
In one embodiment of the present invention, in step (3), the solvent is selected from one or more of 2-mercaptoethanol (2-ME), γ -butyrolactone (γ -GBL), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
Further, the solvent is prepared from N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to a volume ratio of 4:1, and mixing.
In one embodiment of the invention, in step (4), the operating speed of the perovskite wet film in the collection hood of the solvent atmosphere is 0.5m/min-1m/min; the air pressure of the air collecting cover is 0.2Mpa-1.2Mpa.
In one embodiment of the invention, in step (4), the solvent atmosphere employs a solvent that is consistent with the solvent in the perovskite precursor solution.
In one embodiment of the present invention, in the step (4), the atmosphere discharge rate is controlled to be 80m during the heat treatment 3 /min-120m 3 /min。
In one embodiment of the present invention, in step (4), the annealing is performed at 100 ℃ to 120 ℃ for 10min to 20min.
In one embodiment of the present invention, in the step (4), the perovskite thin film has a thickness of 500nm to 800nm.
In one embodiment of the present invention, in step (5), the material of the hole transport layer is selected from CuI、CuSCN、NiO x One or more of PSS, spiro-OMeTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
In one embodiment of the invention, in step (5), the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
In one embodiment of the invention, the primary function of both the conductive substrate and the electrode layer is to conduct away photo-generated current.
The principle of the invention is as follows: the pre-buried chloromethyl amine slowly releases during heating, on the one hand, when the Cl-diffusion part diffuses to the electron transport layer, the oxygen vacancies (V O ) Reduce interface defect, surface Cl - The enrichment of the 2D perovskite film has a promoting effect on carrier transmission; the non-diffused part grows along the surface of perovskite due to the existence of Pb-Cl precursor, and the MA is pre-buried at the bottom + Unstable PbI that enters the lattice to eliminate bottom residues 2 The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, when chloromethylamine diffuses into the perovskite thin film, MA is formed on the bottom of the perovskite thin film + Forming a perovskite with a wide band gap, forming FA in the upper half of the perovskite + The narrow bandgap perovskite, thereby creating a bandgap gradient inside the perovskite thin film, is manifested as an increase in cell efficiency.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Referring to fig. 1, a method for improving crystallinity of a perovskite solar cell specifically includes the following steps:
(1) Preparing MACl solution: MACl solid was weighed and dissolved in methanol to give a 4mg/mLMACl solution.
(2) Preparing a perovskite precursor solution:
1) Weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
2) Then weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
3) Then adding the equal volume of CsI solution into the mixed solution to obtain a perovskite precursor solution, wherein the system of the perovskite precursor is Cs 0.05 FA 0.95 PbI 3 The concentration was 0.8mol/L.
(3) And cleaning the substrate, namely cleaning the substrate by using an ITO conductive film of the PET substrate through an ultrasonic cleaner for 15min respectively by using ionized water, ethanol, acetone and isopropanol in sequence, and then performing UV-ozone treatment for 15 min.
(4) SnO is prepared 2 The deionized water dispersion liquid of (2) is coated on the ITO conductive film through a slit, and annealed at 150 ℃ for 25min to form an electron transport layer with the thickness of about 20nm-30nm.
(5) And (3) coating the MACl solution obtained in the step (1) on the electron transport layer by adopting a slit coating method, and drying and annealing at 80 ℃ for 10min to obtain the MACl film.
(6) Coating the perovskite precursor solution in the step (2) on the surface of the MACl film, placing the obtained perovskite wet film in a wind collecting hood in the solvent (same as the solvent of the perovskite precursor solution) atmosphere, setting the running speed of the wet film in the wind collecting hood to be 0.8m/min, setting the air pressure in the wind collecting hood to be 0.8Mpa, and controlling the air discharge rate to be 100m 3 Heating the wet film carrier in gradient at 70deg.C for 5min; heating at 150deg.C for 10min.
(7) And (3) annealing and drying the perovskite, and annealing for 15min at 110 ℃ to obtain the perovskite film with the thickness of 500-800 nm.
(8) A perovskite thin film is coated with a Spiro-MeOTAD layer with a thickness of 40nm-50nm as a hole transport layer.
(9) An 80nm to 100nm thick Ag electrode layer was vapor deposited on the hole transport layer to obtain a perovskite solar cell as shown in fig. 2 (a).
Comparative example 1
Basically, the embodiment 1 is different in that MACl pre-embedding is not performed, and specifically includes the following steps:
(1) Preparing a perovskite precursor solution containing MACl:
1) Weighing FAI and PbI 2 Dissolved in DMF and DMSO (volume ratio of 4:1)Stirring the mixed solution at 65 ℃ overnight to obtain a mixed solution;
2) Then weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
3) Then adding the equal volume of CsI solution into the mixed solution to obtain a perovskite precursor solution, wherein the system of the perovskite precursor is Cs 0.05 FA 0.95 PbI 3 The concentration is 0.8mol/L;
4) Adding a MACl solution to the perovskite precursor solution to obtain a perovskite precursor solution containing MACl, wherein the MACl solution is obtained by dissolving MACl solid in methanol solution.
(2) And cleaning the substrate, namely cleaning the substrate by using an ITO conductive film of the PET substrate through an ultrasonic cleaner for 15min respectively by using ionized water, ethanol, acetone and isopropanol in sequence, and then performing UV-ozone treatment for 15 min.
(3) SnO is prepared 2 The deionized water dispersion liquid of (2) is coated on the ITO conductive film through a slit, and annealed at 150 ℃ for 25min to form an electron transport layer with the thickness of about 20nm-30nm.
(4) Coating the perovskite precursor solution containing MACl in the step (1) on the surface of an electron transport layer, placing the obtained perovskite wet film in a wind collecting hood in the solvent (same as the solvent of the perovskite precursor solution) atmosphere, setting the running speed of the wet film in the wind collecting hood to be 0.8m/min, setting the air pressure in the wind collecting hood to be 0.8Mpa, and controlling the discharge rate of the atmosphere to be 100m 3 Heating the wet film carrier in gradient at 70deg.C for 5min; heating at 150deg.C for 10min.
(5) And (3) annealing and drying the perovskite, and annealing for 15min at 110 ℃ to obtain the perovskite film with the thickness of 500-800 nm.
(6) A perovskite thin film is coated with a Spiro-MeOTAD layer with a thickness of 40nm-50nm as a hole transport layer.
(7) An 80nm to 100nm thick Ag electrode layer was vapor deposited on the hole transport layer to obtain a perovskite solar cell as shown in fig. 2 (b).
Comparative example 2
The method is basically the same as the embodiment 1, and is characterized in that no MACl pre-burying step is adopted, and the method specifically comprises the following steps:
(1) Preparing a perovskite precursor solution:
1) Weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
2) Then weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
3) Then adding the equal volume of CsI solution into the mixed solution to obtain a perovskite precursor solution, wherein the system of the perovskite precursor is Cs 0.05 FA 0.95 PbI 3 The concentration was 0.8mol/L.
(2) And cleaning the substrate, namely cleaning the substrate by using an ITO conductive film of the PET substrate through an ultrasonic cleaner for 15min respectively by using ionized water, ethanol, acetone and isopropanol in sequence, and then performing UV-ozone treatment for 15 min.
(3) SnO is prepared 2 The deionized water dispersion liquid of (2) is coated on the ITO conductive film through a slit, and annealed at 150 ℃ for 25min to form an electron transport layer with the thickness of about 20nm-30nm.
(4) Coating the perovskite precursor solution in the step (2) on the surface of the electron transport layer, placing the obtained perovskite wet film in a wind collecting hood in the solvent (same as the solvent of the perovskite precursor solution) atmosphere, setting the running speed of the wet film in the wind collecting hood to be 0.8m/min, setting the air pressure in the wind collecting hood to be 0.8Mpa, and controlling the air discharge rate to be 100m 3 Heating the wet film carrier in gradient at 70deg.C for 5min; heating at 150deg.C for 10min.
(5) And (3) annealing and drying the perovskite, and annealing for 15min at 110 ℃ to obtain the perovskite film with the thickness of 500-800 nm.
(6) A perovskite thin film is coated with a Spiro-MeOTAD layer with a thickness of 40nm-50nm as a hole transport layer.
(7) Evaporating and plating the Ag electrode layer with the thickness of 80nm-100nm on the hole transport layer to obtain the perovskite solar cell.
Test example 1
The perovskite thin films prepared in example 1 and comparative examples 1 to 2 were subjected to a Scanning Electron Microscope (SEM), and the results are shown in fig. 3 to 5. From FIGS. 3-5, it can be seen that the size of the perovskite grains of the MACl buried bottom is significantly increased, and is uniform and flat, no holes are formed, and through-crystal formation is observed; as a comparative example, when MACl is added into the perovskite precursor solution or no MACl is added into the perovskite precursor solution, the perovskite film has obvious holes, the perovskite crystal morphology is poor, and although the perovskite crystal grains added with MACl grow larger than the comparative example without MACl, the broken crystal is more and the crystal grain size is smaller. The method is characterized in that the embedded MACl is partially dissolved from the bottom of the perovskite wet film to the surface of the wet film to form a concentration gradient distribution state, particularly in the perovskite film annealing process, the MACl at the bottom of the perovskite film is heated and then diffuses to the surface of the film, the MACl continuously diffused to the surface of the film properly slows down the grain growth process through forming a perovskite intermediate phase, so that the grains grow into a larger size, however, the MACl directly added into a precursor solution can be subjected to higher volatility, so that the surface of the perovskite wet film is nucleated and crystallized preferentially, and more broken crystals are formed.
Test example 2
The perovskite solar cells prepared in example 1 and comparative example 1 were tested for performances such as open circuit voltage, short circuit current, fill factor, photoelectric conversion efficiency, and the like.
Table 1 shows the relevant properties of the finally measured perovskite solar cell:
TABLE 1
From table 1 it can be seen that there is a significant improvement in MACl-buried device performance. This is mainly due to the large grain size and high crystallinity of perovskite films in MACl-buried devices, which reduce defects and increase carrier mobility.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A method for improving crystallinity of perovskite solar cell is characterized by comprising the following steps,
(1) Forming an electron transport layer on the surface of the conductive substrate;
(2) Coating a chloromethyl amine solution on the surface of the electron transport layer to form a chloromethyl amine film; the concentration of the chloromethyl amine solution is 0.5mg/mL-6mg/mL;
(3) Coating a perovskite precursor solution on the surface of the chloromethyl amine film to form a perovskite wet film;
(4) Placing the perovskite wet film in a wind collecting hood in solvent atmosphere, heating in stages, and annealing to form a perovskite film; the heating treatment by stages is specifically divided into two stages, wherein the first stage is heating at 65-75 ℃ for 4-6 min; the second stage is heating at 100-150deg.C for 8-12 min;
(5) And sequentially forming a hole transport layer and an electrode layer on the surface of the perovskite film to obtain the perovskite solar cell with improved crystallinity.
2. The method of claim 1, wherein in step (1), the conductive substrate is selected from fluorine-doped tin oxide conductive substrate, tin-doped indium oxide conductive substrate, titanium-doped indium oxide conductive substrate, cerium-doped indium oxide conductive substrate, tungsten-doped indium oxide conductive substrate, aluminum-doped zinc oxide conductive substrate, or boron-doped zinc oxide conductive substrate.
3. The method of claim 1, wherein in step (1), the electron transport layer is made of a material selected from the group consisting of TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness is 20nm-30nm.
4. The method of claim 1, wherein in step (3), the perovskite precursor is dissolvedThe liquid contains perovskite material and solvent; the perovskite material is ABX 3 The perovskite type A is selected from one or more of methyl ammonium ion, formamidine ion, cesium ion and rubidium ion; b is selected from lead ions and/or tin ions; and X is one or more selected from iodide ions, bromide ions and chloride ions.
5. The method for improving the crystallinity of a perovskite solar cell according to claim 1, wherein in step (4), the operation speed of the perovskite wet film in the collecting hood of the solvent atmosphere is 0.5m/min to 1m/min; the air pressure of the air collecting cover is 0.2Mpa-1.2Mpa.
6. The method of claim 1, wherein in step (4), the solvent atmosphere employs a solvent that is consistent with the solvent in the perovskite precursor solution.
7. The method of claim 1, wherein in step (4), the annealing is performed at 100 ℃ to 120 ℃ for 10min to 20min.
8. The method for improving the crystallinity of a perovskite solar cell according to claim 1, wherein in step (4), the thickness of the perovskite thin film is 500nm to 800nm.
9. The method of claim 1, wherein in step (5), the hole transport layer is made of a material selected from CuI, cuSCN, niO x One or more of PSS, spiro-OMeTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
10. The method of claim 1, wherein in step (5), the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
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