CN115241386A - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

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CN115241386A
CN115241386A CN202210931159.XA CN202210931159A CN115241386A CN 115241386 A CN115241386 A CN 115241386A CN 202210931159 A CN202210931159 A CN 202210931159A CN 115241386 A CN115241386 A CN 115241386A
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perovskite
light absorption
solar cell
absorption layer
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张飞
吴鹏飞
王世荣
李祥高
刘红丽
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Tianjin University
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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Abstract

The invention provides a perovskite solar cell and a preparation method thereof, and belongs to the field of solar cells. Modified layer A' A of the invention n B n X 3n+1 The B in the light absorption layer comes from the light absorption layer, and the defects caused by the B metal ion clusters in the light absorption layer are eliminated. Resulting in A' A n B n X 3n+1 The ionic bond strengthens the interaction between the modification layer and the light absorption layer, further makes up the defects caused by vacancies and crystal boundaries in the light absorption layer, and improves the photoelectric conversion efficiency and the stability of the battery. In addition, the two-dimensional perovskite modification layer is prepared on the surface of the perovskite light absorption layer, on one hand, more favorable energy level arrangement can be formed, and the transfer of current carriers from the perovskite light absorption layer to the charge transfer layer is promoted, so that the reverse electron transfer and the current leakage loss are reduced, and the photoelectric conversion efficiency is improved; on the other hand, the method can also inhibit ion migration, and is beneficial to reducing the hysteresis effect and improving the stability.

Description

Perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
A perovskite solar cell is a solar cell using a perovskite-type organic metal halide semiconductor as a light absorbing material. The perovskite solar cell is a third-generation solar cell following a crystalline silicon solar cell and a thin-film solar cell, has the advantages of simple structure, high photoelectric conversion efficiency, low cost and the like, and is concerned by multiple countries all over the world.
At the present stage, perovskite solar cells still have certain technical defects, and due to the rapid growth and high-temperature annealing process of the perovskite solar cells, a large number of defects, such as a large number of grain boundaries and vacancy defects, can be formed at the interface between the perovskite light absorption layer and the corresponding transmission layer. The formation of defects may cause low photoelectric conversion efficiency and poor stability of the battery device. In order to improve the efficiency and stability of the cell device, the prior art generally adds an auxiliary agent to a perovskite precursor solution, adopts an encapsulation technology or uses a novel electron or hole transport layer material, but the photoelectric conversion efficiency and stability of the cell still need to be improved.
Disclosure of Invention
The invention aims to provide a perovskite solar cell and a preparation method thereof.
The invention provides a perovskite solar cell which comprises a conductive substrate, an electron transmission layer, a perovskite light absorption layer, a two-dimensional perovskite modification layer, a hole transmission layer and a metal electrode which are sequentially stacked;
the two-dimensional perovskite modification layer is prepared on the perovskite light absorption layer;
the chemical composition of the two-dimensional perovskite modification layer is A' A n B n X 3n+1 (ii) a Said A' comprises C 4 H 12 N + 、C 3 H 8 N + 、C 2 H 8 N + And CN 3 H 6 + One of (1); n is an integer of 1 to 10; a comprises CH 6 N + 、CH 5 N 2 + 、C 2 H 7 N 2 + And C 3 H 9 N + One of (1); what is needed isX is Cl - 、Br - And I - One or two of (a) and (b); b is a divalent metal ion; the B is derived from the perovskite light absorbing layer.
Preferably, said B comprises Ge 2+ 、Sn 2+ 、Pb 2+ 、Cu 2+ And Mn 2+ One kind of (1).
Preferably, the chemical composition of the perovskite light absorption layer is DBI 3 (ii) a D comprises CH 6 N + 、CH 5 N 2 + And Cs + One or more of (a).
Preferably, the chemical composition of the electron transport layer is an inorganic oxide electron transport material or an organic electron transport material.
Preferably, the inorganic oxide electron transport material comprises one of zinc oxide, tin dioxide, tungsten oxide and titanium dioxide; the organic electron transport material comprises [6,6]-phenyl radical C 71 Methyl butanoate, [6,6 ] n]-phenyl radical C 61 Methyl butyrate and organic fullerene materials.
Preferably, the hole transport layer chemical composition comprises one of 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ], copper phthalocyanine, cuprous thiocyanate, poly (3-hexylthiophene), and nickel oxide.
Preferably, the thickness of the two-dimensional perovskite modification layer is 3-50 nm.
The invention also provides a preparation method of the perovskite solar cell in the scheme, which comprises the following steps:
coating the dispersion liquid of the corresponding composition substances of the electron transport layer on the conductive substrate, and performing first annealing to form the electron transport layer;
coating a perovskite light absorption layer precursor solution on the surface of the electron transport layer, and performing second annealing to form a perovskite light absorption layer;
coating an organic solution containing A' X and AX on the surface of the perovskite light absorption layer, and performing third annealing to form a two-dimensional perovskite modification layer; the molar ratio of A' X to AX is 1:1 to 10;
coating the dispersion liquid of the corresponding component of the hole transport layer on the surface of the two-dimensional perovskite modified layer to form the hole transport layer;
and evaporating raw materials of the metal electrode onto the hole transport layer to form the metal electrode, thereby obtaining the perovskite solar cell.
Preferably, the temperature of the third annealing is 60-120 ℃, and the heat preservation time is 1-30 min.
Preferably, the total solute concentration of the organic solution containing A' X and AX is 0.1 to 20mmol/L.
The invention provides a perovskite solar cell which comprises a conductive substrate, an electron transmission layer, a perovskite light absorption layer, a two-dimensional perovskite modification layer, a hole transmission layer and a metal electrode which are sequentially stacked; the two-dimensional perovskite modification layer is prepared on the perovskite light absorption layer; the chemical composition of the two-dimensional perovskite modification layer is A' A n B n X 3n+1 (ii) a Said A' comprises C 4 H 12 N + 、C 3 H 8 N + 、C 2 H 8 N + And CN 3 H 6 + One of (1); n is an integer of 1 to 10; a comprises CH 6 N + 、CH 5 N 2 + 、C 2 H 7 N 2 + And C 3 H 9 N + One of (a) and (b); x is Cl - 、Br - And I - One or two of them; b is a divalent metal ion; the B is derived from the perovskite light absorbing layer. In the invention, the two-dimensional perovskite modification layer A' A n B n X 3n+1 B in the perovskite light absorption layer is derived from the perovskite light absorption layer, and the defects caused by B metal ion clusters in the perovskite light absorption layer are eliminated. Resulting A' A n B n X 3n+1 Interaction between the two-dimensional perovskite modification layer and the perovskite light absorption layer is strengthened through ionic bonds, and defects caused by vacancies and grain boundaries in the perovskite light absorption layer are further overcome. Therefore, the two-dimensional perovskite modification layer prepared by the invention improves perovskite light absorptionInterface charge transmission between the layer and the electron transport layer/hole transport layer effectively improves the photoelectric conversion efficiency and stability of the perovskite solar cell. In addition, the two-dimensional perovskite modification layer is prepared on the surface of the perovskite light absorption layer, so that on one hand, more favorable energy level arrangement can be formed, and the transfer of current carriers from the perovskite light absorption layer to the charge transfer layer is promoted, thereby reducing the reverse electron transfer and current leakage loss, and improving the photoelectric conversion efficiency; on the other hand, the method can also inhibit ion migration, and is beneficial to reducing the hysteresis effect and improving the stability.
Drawings
FIG. 1 is a block diagram of a perovskite solar cell of the present invention;
fig. 2 is an SEM image of the perovskite layer solar cell of example 1;
FIG. 3 is a J-V performance curve for the perovskite layer solar cell of example 1 versus the perovskite layer solar cell of comparative example 1;
fig. 4 is a stability test result of the perovskite layer solar cell of example 2 and the perovskite layer solar cell of comparative example 1.
Detailed Description
The invention provides a perovskite solar cell which comprises a conductive substrate, an electron transmission layer, a perovskite light absorption layer, a two-dimensional perovskite modification layer, a hole transmission layer and a metal electrode which are sequentially stacked;
the two-dimensional perovskite modification layer is prepared on the perovskite light absorption layer;
the chemical composition of the two-dimensional perovskite modification layer is A' A n B n X 3n+1 (ii) a Said A' comprises C 4 H 12 N + 、C 3 H 8 N + 、C 2 H 8 N + And CN 3 H 6 + One of (1); n is an integer of 1 to 10; a comprises CH 6 N + 、CH 5 N 2 + 、C 2 H 7 N 2 + And C 3 H 9 N + One of (a) and (b); x is Cl - 、Br - And I - One or two of (a) and (b); b isIs a divalent metal ion; the B is derived from the perovskite light absorbing layer.
The perovskite solar cell provided by the invention comprises a conductive substrate. In the present invention, the thickness of the conductive substrate is preferably 0.5 to 2.5cm, more preferably 1 to 2cm, and further preferably 1.5 to 1.8cm. In the present invention, the conductive substrate preferably comprises fluorine-doped tin dioxide conductive glass or indium tin oxide transparent conductive film glass.
The perovskite solar cell provided by the invention comprises an electron transport layer attached to the surface of a conductive substrate. In the present invention, the thickness of the electron transport layer is preferably 20 to 200nm, more preferably 50 to 150nm, and still more preferably 70 to 100nm. In the present invention, the chemical composition of the electron transport layer is preferably an inorganic oxide electron transport material or an organic electron transport material; the inorganic oxide electron transport material preferably comprises one of zinc oxide, tin dioxide, tungsten oxide and titanium dioxide; the organic electron transport material preferably comprises [6,6]-phenyl radical C 71 Methyl butanoate, [6,6 ] n]-phenyl radical C 61 Methyl butyrate and organic fullerene materials.
The perovskite solar cell provided by the invention comprises a perovskite light absorption layer attached to the surface of an electron transport layer. In the present invention, the thickness of the perovskite light absorption layer is preferably 300 to 800nm, more preferably 400 to 600nm, and still more preferably 450 to 500nm. In the present invention, the chemical composition of the perovskite light absorption layer is preferably DBI 3 (ii) a Said D preferably comprises CH 6 N + 、CH 5 N 2 + And Cs + One or more of; b is a divalent metal ion; the divalent metal ion preferably comprises Ge 2+ 、Sn 2 + 、Pb 2+ 、Cu 2+ And Mn 2+ One kind of (1). In an embodiment of the invention, the chemical composition of the perovskite light absorbing layer is in particular CH 5 N 2 PbI 3 。
The perovskite solar cell provided by the invention comprises a two-dimensional perovskite modification layer attached to the surface of a perovskite light absorption layer. In the present invention, the two-dimensional perovskite repairThe thickness of the decorative layer is preferably 3 to 50nm, more preferably 10 to 40nm, and still more preferably 20 to 30nm. In the invention, the two-dimensional perovskite modification layer is prepared in situ on the perovskite light absorption layer; the chemical composition of the two-dimensional perovskite modification layer is A' A n B n X 3n+1 (ii) a Said A' comprises C 4 H 12 N + 、C 3 H 8 N + 、C 2 H 8 N + And CN 3 H 6 + One of (1); n is an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 4 to 6. The B is derived from the perovskite light absorbing layer. In an embodiment of the invention, the chemical composition of the two-dimensional perovskite modification layer is specifically CN 3 H 6 (CH 6 N) 2 Pb 2 I 7 。
The invention relates to a two-dimensional perovskite modification layer A' A n B n X 3n+1 B in the perovskite light absorption layer is derived from the perovskite light absorption layer, and the defects caused by B metal ion clusters in the perovskite light absorption layer are eliminated. Resulting in A' A n B n X 3n+1 Interaction between the two-dimensional perovskite modification layer and the perovskite light absorption layer is strengthened through ionic bonds, and defects caused by vacancies and grain boundaries in the perovskite light absorption layer are further overcome. Therefore, the two-dimensional perovskite modification layer prepared by the invention improves the interface charge transmission between the perovskite light absorption layer and the electron transmission layer/hole transmission layer, and effectively improves the photoelectric conversion efficiency and stability of the perovskite solar cell. In addition, the two-dimensional perovskite modification layer is prepared on the surface of the perovskite light absorption layer, on one hand, more favorable energy level arrangement can be formed, and the transfer of current carriers from the perovskite light absorption layer to the charge transfer layer is promoted, so that the reverse electron transfer and the current leakage loss are reduced, and the photoelectric conversion efficiency is improved; on the other hand, the method can also inhibit ion migration, and is favorable for reducing photocurrent delay and improving stability.
The perovskite solar cell provided by the invention comprises a hole transport layer attached to the surface of a two-dimensional perovskite modification layer. In the present invention, the thickness of the hole transport layer is preferably 5 to 200nm, more preferably 50 to 150nm, and still more preferably 60 to 120nm. In the present invention, the hole transport layer chemical composition preferably includes one of 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ], copper phthalocyanine, cuprous thiocyanate, poly (3-hexylthiophene), and nickel oxide. The hole transport layer preferably also comprises 4-tert-butylpyridine and lithium bistrifluoromethanesulfonylimide. The 4-tert-butylpyridine and lithium bis (trifluoromethanesulfonylimide) can improve the hole transport rate of the hole transport layer. In an embodiment of the present invention, the chemical composition of the hole transport layer is 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 4-tert-butylpyridine, and lithium bistrifluoromethanesulfonylimide.
The perovskite solar cell provided by the invention comprises a metal electrode attached to the surface of a hole transport layer. In the present invention, the thickness of the metal electrode is preferably 50 to 200nm, more preferably 80 to 180nm, and still more preferably 100 to 150nm. The metal electrode preferably includes one of Al, ag, cu, and Au. In an embodiment of the present invention, the metal electrode is Au.
The perovskite solar cell disclosed by the invention has a structure shown in detail in a figure 1, and comprises a conductive substrate, an electron transmission layer, a perovskite light absorption layer, a two-dimensional perovskite modification layer, a hole transmission layer and a metal electrode which are sequentially stacked.
The invention provides a preparation method of the perovskite solar cell in the scheme, which comprises the following steps:
coating the dispersion liquid of the corresponding composition substances of the electron transport layer on the conductive substrate, and performing first annealing to form the electron transport layer;
coating a perovskite light absorption layer precursor solution on the surface of the electron transport layer, and performing second annealing to form a perovskite light absorption layer;
coating an organic solution containing A' X and AX on the surface of the perovskite light absorption layer, and performing third annealing to form a two-dimensional perovskite modification layer; the molar ratio of A' X to AX is 1:1 to 10;
coating the dispersion liquid of the corresponding component of the hole transport layer on the surface of the two-dimensional perovskite modified layer to form the hole transport layer;
and evaporating the raw material of the metal electrode onto the hole transport layer to form the metal electrode, thereby obtaining the perovskite solar cell.
The invention coats the dispersion liquid of the corresponding composition substance of the electron transport layer on the conductive substrate, and carries out the first annealing to form the electron transport layer. In the present invention, the method for preparing the dispersion of the constituent substances of the electron transport layer preferably includes: and dispersing the corresponding component substances of the electron transport layer in the first dispersing agent. The first dispersing agent preferably comprises one of deionized water, ethanol, methanol and butanol, and the content of the components corresponding to the electron transport layer in the dispersion liquid of the components corresponding to the electron transport layer is preferably 1-5 wt%, and more preferably 2-4 wt%. The dispersion is not particularly limited in the present invention, and the dispersion may be uniform by a method known to those skilled in the art. In the present invention, the coating is preferably spin coating, the spin coating is preferably performed at a rotation speed of 2000 to 5000rpm/min, more preferably 3000 to 4500rpm/min, further preferably 3500 to 4000rpm/min, and the time is preferably 30s. The spin coating is preferably carried out in air. In the present invention, the temperature of the first annealing is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, further preferably 150 to 160 ℃, and the time is preferably 10 to 90min, more preferably 30 to 80min, further preferably 50 to 60min. The first annealing is preferably performed in air. And removing the first dispersant remained in the spin coating process through first annealing to form a compact electron transport layer.
After the electron transport layer is formed, the perovskite light absorption layer precursor solution is coated on the surface of the electron transport layer, and second annealing is carried out to form the perovskite light absorption layer. In the present invention, the perovskite light-absorbing layer precursor solution preferably includes a BI-containing solution 2 And an organic solution containing DI and CH 6 Organic solution of NCl. In the present invention, the BI (bismuth-containing compound) 2 The method of preparing the organic solution of (2) preferably comprises subjecting the BI 2 First mixing with a first organic solvent to obtain the BI 2 The organic solution of (2). The first mixing is preferably carried out in a glove box. The first mixing is not particularly limited in the present invention, and the first mixing may be uniformly mixed by a scheme well known to those skilled in the art. The compound contains BI 2 BI in organic solution of (2) 2 The concentration of (B) is preferably 0.5 to 2mol/L, more preferably 1.3 to 1.8mol/L, and still more preferably 1.4 to 1.6mol/L. The first organic solvent preferably comprises a mixed solution of DMF and DMSO, and the volume ratio of DMF to DMSO is preferably 9:0.1 to 2, more preferably 9.5 to 1.5, and still more preferably 9. In the present invention, the compound containing DI and CH 6 The process for the preparation of the organic solution of NCl preferably comprises reacting DI and CH 6 Second mixing NCl with a second organic solvent to obtain the composition containing DI and CH 6 Organic solution of NCl. In the present invention, the compound containing DI and CH 6 Organic solution of NCl with DI and CH 6 The total concentration of NCl is preferably 0.1 to 1mol/L, more preferably 0.5 to 0.7mol/L. In the present invention, the DI and CH 6 The molar ratio of NCl is preferably 4. CH (CH) 6 NCl can promote the formation of the perovskite light absorption layer and improve the quality of the perovskite light absorption layer film. In the present invention, the second organic solvent is preferably one of isopropyl alcohol, ethanol, methanol, dichloromethane, chloroform, butanol, tetrahydrofuran, and acetone. In the present invention, the coating is preferably spin coating, the spin coating is preferably performed at a rotation speed of 1000 to 3000rpm/min, more preferably 1200 to 2500rpm/min, even more preferably 1500 to 2000rpm/min, and the time is preferably 10 to 60 seconds, more preferably 20 to 50 seconds, and even more preferably 30 to 40 seconds. The spin coating is preferably carried out in a glove box.
According to the invention, the step of coating the perovskite light absorption layer precursor solution on the surface of the electron transport layer, and the second annealing preferably comprises the following steps: will contain BI 2 Is applied to the surface of the electron transport layer and a second' anneal is performed to form a BI 2 A layer; mixing DI and CH 6 Organic solution of NCl applied to the BI 2 And performing second annealing after the layer is formed to obtain the perovskite light absorption layer. In the present invention, the temperature of the second' annealing is preferably 60 to 90 ℃, more preferably 70 to 80 ℃, and the time is preferably 0.5 to 3min, more preferablyPreferably 1 to 2min. The temperature of the second "anneal is preferably 140 to 160 deg.C, more preferably 145 to 150 deg.C, and the time is preferably 5 to 15min, more preferably 8 to 12min. The second' anneal is preferably performed in a glove box. The second "anneal is preferably performed in air, where traces of water have a promoting effect on the crystallization of the perovskite light absorbing layer. Removing the residual first organic solvent of the spin-coating process in the second annealing process to make the BI 2 Attached to the surface of the electron transport layer, and in a subsequent second annealing process, BI 2 Reacting with DI to form DBI 3 I.e. the perovskite light absorbing layer.
After the perovskite light absorption layer is formed, the perovskite light absorption layer is coated with an organic solution containing A' X and AX, and then the surface of the perovskite light absorption layer is subjected to third annealing to form a two-dimensional perovskite modification layer. In the present invention, the method for preparing the organic solution containing a ' X and AX preferably comprises performing a third mixing of a ' X and AX with a third organic solvent to obtain the organic solution containing a ' X and AX. The third mixing is preferably carried out in a glove box. The third mixing is not particularly limited in the present invention, and the third mixing may be uniformly mixed by a scheme well known to those skilled in the art. In the present invention, the molar ratio of a' X and AX is 1:1 to 10, preferably 1. In the present invention, the third organic solvent is preferably one or more of methanol, isopropanol, acetone, tetrahydrofuran, dichloromethane, chloroform, ethanol and butanol. The total concentration of A 'X and AX in the organic solution containing A' X and AX is preferably 0.1 to 20mmol/L, more preferably 5 to 15mmol/L, and further preferably 10 to 12mmol/L. In the invention, the coating mode is preferably spin coating, the rotating speed of the spin coating is preferably 4000rpm/min, and the time is preferably 30s. The spin coating is preferably carried out in a glove box. The temperature of the third annealing is preferably 60 to 120 ℃, more preferably 70 to 100 ℃, further preferably 80 to 90 ℃, and the time is preferably 1 to 30min, more preferably 5 to 25min, further preferably 10 to 15min. The third anneal is preferably performed in a glove box filled with argon. Reacting A' X and AX with the B metal ion cluster on the surface of the perovskite light absorption layer at a third annealing temperature to generate A’A n B n X 3n+1 And removing residual solvent in the two-dimensional perovskite modification layer.
After the two-dimensional perovskite modification layer is formed, the dispersion liquid of the substances corresponding to the hole transport layer is coated on the surface of the two-dimensional perovskite modification layer to form the hole transport layer. The method for producing the dispersion of the hole transport layer-corresponding constituent substance of the present invention preferably disperses the hole transport layer-corresponding constituent substance in the second dispersant. The second dispersant preferably comprises one or more of toluene, chlorobenzene, and xylene. When the corresponding constituent materials of the hole transport layer are 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 '-spirobifluorene, 4-t-butylpyridine and lithium bistrifluoromethanesulfonylimide, the content of the 2,2',7 '-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene in the dispersion of the corresponding constituent materials of the hole transport layer is preferably 60 to 100mg/mL, more preferably 72.3 to 80mg/mL, the content of the 4-t-butylpyridine is preferably 20 to 30mg/mL, more preferably 25 to 28.8. Mu.L/mL, and the content of the lithium bistrifluoromethanesulfonylimide is preferably 20 to 40mg/mL, more preferably 30.8 to 35mg/mL. The dispersion is not particularly limited in the present invention, and the dispersion may be uniform by a method known to those skilled in the art. In the invention, the coating mode is preferably spin coating, the rotating speed of the spin coating is preferably 4000rpm/min, and the time is preferably 30s. The spin coating is preferably carried out in a glove box. In the present invention, the solvent in the dispersion liquid includes one of toluene, chlorobenzene, and xylene.
After the hole transport layer is formed, evaporating raw materials of the metal electrode onto the hole transport layer to form the metal electrode, and obtaining the perovskite solar cell. In the present invention, the degree of vacuum of the vapor deposition is preferably less than 1 × 10 -3 pa, speed is preferably
Figure BDA0003781507320000081
More preferably
Figure BDA0003781507320000082
Further preferably
Figure BDA0003781507320000083
For further illustration of the present invention, the perovskite solar cell and the preparation method thereof provided by the present invention are described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
SnO 2 Dispersing in deionized water to obtain SnO 2 The dispersion liquid with the content of 2.5Wt% is coated on a conductive substrate FTO in the air in a spinning way, and then first annealing is carried out for 30min at the temperature of 150 ℃ to form an electron transmission layer with the thickness of 150 nm; the spin coating speed is 4000rpm/min, and the time is 30s;
using PbI in glove box 2 Dissolving the mixture in an organic solvent (the organic solvent is a mixed solvent of DMF and DMSO, the volume ratio of DMF to DMSO is 9 2 A layer; mixing CH with a molar ratio of 4 5 N 2 I and CH 6 NCl is dissolved in isopropanol to obtain an organic solution with the total concentration of 0.6 mol/L; the organic solution was spin coated (spin speed 2000rpm/min, time 30 s) onto PbI in a glove box 2 Performing a second 'annealing' in air at 150 deg.C for 15min to form CH with thickness of 400nm 5 N 2 PbI 3 A perovskite light-absorbing layer;
in a glove box, CN in a molar ratio of 1 3 H 6 I and CH 6 NI was dissolved in isopropanol to give CN at a total concentration of 5mmol/L 3 H 6 I and CH 6 An organic solution of NI; the organic solution was spin coated on the CH in a glove box (speed of spin coating 4000rpm/min, time 30 s) 5 N 2 PbI 3 Performing a third annealing on the perovskite light absorption layer at 100 deg.C for 5min in a glove box filled with argon gas to form chemical composition CN 3 H 6 (CH 6 N) 2 Pb 2 I 7 A two-dimensional perovskite modification layer with the thickness of 5 nm;
dispersing 2,2', 7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene by chlorobenzene, doping 4-tert-butylpyridine and lithium bistrifluoromethanesulfonylimide to obtain a dispersion liquid of a substance corresponding to a hole transport layer. The content of 2,2', 7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene in the dispersion liquid was 72.3mg/mL, the content of 4-tert-butylpyridine was 28.8. Mu.L/mL, and the content of lithium bistrifluoromethanesulfonylimide was 30.8mg/mL. Spin-coating the obtained dispersion on a two-dimensional perovskite modification layer in a glove box (the rotating speed is 4000rpm/min, and the time is 30 s) to form a hole transport layer with the thickness of 150 nm;
under vacuum degree of 6.5X 10 -4 pa under the conditions of
Figure BDA0003781507320000091
And evaporating the metal electrode Au at the speed of (1) to form a metal electrode with the thickness of 100nm on the hole transport layer to obtain the perovskite solar cell.
SEM analysis of the perovskite light-absorbing layer and the modified layer prepared in example 1 was performed, and the results are shown in fig. 2. As can be seen from fig. 2, the surface morphology of the perovskite light absorption layer of the present embodiment has a large grain size of about 1 μm, no obvious voids, the grain boundary is passivated by the two-dimensional perovskite modification layer, and the two-dimensional perovskite modification layer is distributed obviously. The result shows that the passivated perovskite light absorption layer has few defects and low film roughness.
Example 2
The only differences from example 1 are: CN is contained when preparing two-dimensional perovskite modification layer 3 H 6 I and CH 6 The total concentration of the organic solution of NI was 10mmol/L.
Example 3
The only difference from example 1 is: CN is contained when preparing two-dimensional perovskite modification layer 3 H 6 I and CH 6 The total concentration of the organic solution of NI was 15mmol/L.
Example 4
The only difference from example 1 is: preparation of IICN is contained in the perovskite modification layer 3 H 6 I and CH 6 The total concentration of the organic solution of NI was 20mmol/L.
Comparative example 1
The only difference from example 1 is: a two-dimensional perovskite modification layer is not prepared.
At AM1.5G,100mW/cm 2 The J-V performance curves of the perovskite solar cells of example 1 and comparative example 1 were obtained using a solar simulator under test conditions, as shown in fig. 3 and in table 1.
TABLE 1 blank conditions and J-V parameters of passivated perovskite solar cell devices
Voc(V) Jsc(mA·cm -2 ) FF PCE(％)
Comparative example 1 1.14 24.65 0.78 21.9
Example 1 1.16 24.70 0.81 23.2
As can be seen from FIG. 3 and Table 1, the short-circuit current of the perovskite solar cell of the comparative example was 24.65mA/cm 2 The open circuit voltage was 1.14V, the fill factor was 0.78, and the energy conversion efficiency was 21.9%. While the short-circuit current of the perovskite solar cell of example 1 was increased to 24.7mA/cm 2 The open-circuit voltage is increased to 1.16V, the filling factor is increased to 0.81, and the energy conversion efficiency is increased to 23.2%.
Stability tests were performed on the perovskite solar cells of example 2 and comparative example 1: the photoelectric conversion efficiency was measured every 24 hours for the first 200 hours and every 168 hours after 200 hours in an air-dry dark environment. The stability test results are shown in fig. 4. As can be seen from fig. 4, the perovskite solar cell of example 1 maintained the photoelectric conversion efficiency of 82% after 1440 hours, whereas the perovskite solar cell of comparative example 1 had a photoelectric conversion efficiency that decayed to 59% of the initial value. The stability test result shows that the stability of the passivated perovskite solar cell is improved due to the reduction of defects of the perovskite light absorption layer.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. A perovskite solar cell is characterized by comprising a conductive substrate, an electron transmission layer, a perovskite light absorption layer, a two-dimensional perovskite modification layer, a hole transmission layer and a metal electrode which are sequentially stacked;
the two-dimensional perovskite modification layer is prepared on the perovskite light absorption layer;
the chemical composition of the two-dimensional perovskite modification layer is A' A n B n X 3n+1 (ii) a Said A' comprises C 4 H 12 N + 、C 3 H 8 N + 、C 2 H 8 N + And CN 3 H 6 + One of (1); n is an integer of 1 to 10; a comprises CH 6 N + 、CH 5 N 2 + 、C 2 H 7 N 2 + And C 3 H 9 N + One of (1); x is Cl - 、Br - And I - One or two of them; b is a divalent metal ion; the B is derived from the perovskite light absorbing layer.
2. The perovskite solar cell of claim 1, wherein the B comprises Ge 2+ 、Sn 2+ 、Pb 2+ 、Cu 2 + And Mn 2+ To (3) is provided.
3. The perovskite solar cell of claim 1 or 2, wherein the chemical composition of the perovskite light absorbing layer is DBI 3 (ii) a D comprises CH 6 N + 、CH 5 N 2 + And Cs + One or more of (a).
4. The perovskite solar cell of claim 1, wherein the chemical composition of the electron transport layer is an inorganic oxide electron transport material or an organic electron transport material.
5. The perovskite solar cell of claim 4, wherein the inorganic oxide electron transport material comprises one of zinc oxide, tin dioxide, tungsten oxide, and titanium dioxide; the organic electron transport material comprises [6,6]-phenyl radical C 71 Methyl butanoate, [6,6 ] n]-phenyl radical C 61 Methyl butyrate and organic fullerene materials.
6. The perovskite solar cell of claim 1, wherein the hole transport layer chemical composition comprises one of 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ], copper phthalocyanine, cuprous thiocyanate, poly (3-hexylthiophene), and nickel oxide.
7. The perovskite solar cell of claim 1, wherein the thickness of the two-dimensional perovskite modification layer is from 3 to 50nm.
8. A method of manufacturing a perovskite solar cell as claimed in any one of claims 1 to 7, comprising the steps of:
coating the dispersion liquid of the corresponding composition substances of the electron transport layer on the conductive substrate, and performing first annealing to form the electron transport layer;
coating a perovskite light absorption layer precursor solution on the surface of the electron transport layer, and performing second annealing to form a perovskite light absorption layer;
coating an organic solution containing A' X and AX on the surface of the perovskite light absorption layer, and performing third annealing to form a two-dimensional perovskite modification layer; the molar ratio of A' X to AX is 1:1 to 10;
coating the dispersion liquid of the corresponding component of the hole transport layer on the surface of the two-dimensional perovskite modified layer to form a hole transport layer;
and evaporating raw materials of the metal electrode onto the hole transport layer to form the metal electrode, thereby obtaining the perovskite solar cell.
9. The preparation method according to claim 7, wherein the temperature of the third annealing is 60 to 120 ℃ and the holding time is 1 to 30min.
10. The method according to claim 7, wherein the organic solution containing A' X and AX has a total solute concentration of 0.1 to 20mmol/L.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115666197A (en) * 2022-12-13 2023-01-31 无锡众能光储科技有限公司 Flexible solar cell with high mechanical stability and preparation method
CN115835743A (en) * 2022-12-16 2023-03-21 杭纳半导体装备(杭州)有限公司 Perovskite light absorption layer preparation method, solar cell and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115666197A (en) * 2022-12-13 2023-01-31 无锡众能光储科技有限公司 Flexible solar cell with high mechanical stability and preparation method
CN115835743A (en) * 2022-12-16 2023-03-21 杭纳半导体装备(杭州)有限公司 Perovskite light absorption layer preparation method, solar cell and preparation method thereof
CN115835743B (en) * 2022-12-16 2024-01-23 杭纳半导体装备(杭州)有限公司 Perovskite light absorption layer preparation method, solar cell and preparation method thereof

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