CN115322121B - Organic hole transport material and perovskite solar cell prepared from same - Google Patents

Organic hole transport material and perovskite solar cell prepared from same Download PDF

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CN115322121B
CN115322121B CN202211087336.7A CN202211087336A CN115322121B CN 115322121 B CN115322121 B CN 115322121B CN 202211087336 A CN202211087336 A CN 202211087336A CN 115322121 B CN115322121 B CN 115322121B
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hole transport
layer
organic hole
transport layer
organic
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CN115322121A (en
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刘宗豪
陈炜
刘三万
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Huazhong University of Science and Technology
Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
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Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
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Abstract

The invention relates to an organic hole transport material and a perovskite solar cell prepared from the organic hole transport material, which have a strong anchoring effect on a substrate, can improve the photoelectric characteristic and mechanical property of a perovskite buried bottom interface and regulate and control the interface energy level, promote the hole transport efficiency from a perovskite layer to a hole transport layer, and solve the problems of insufficient stability of the cell interface and low hole transport efficiency in the prior art.

Description

Organic hole transport material and perovskite solar cell prepared from same
Technical Field
The invention belongs to the field of perovskite battery materials, and particularly relates to an organic hole transport material and a perovskite solar cell prepared from the organic hole transport material.
Background
The efficiency of perovskite solar cells has increased from the initial 3.8% to 25.5%, and despite significant breakthroughs in efficiency, long-term stability remains a major challenge for commercialization of perovskite solar cells because perovskite materials are commercially viable in oxygen, moisture, and additionAnd decompose under heat and light. Formamidine (FA) -based perovskite has higher thermal stability than Methylammonium (MA) -based perovskite, and the band gap is closer to the optimal band gap of a single-junction solar cell derived from the Shockley-Queisser limit, with higher theoretical efficiency. To date, FAPbI 3 Is a perovskite component that is now ubiquitous in almost all high efficiency perovskite solar cells, however, pure FAPbI 3 Is easily converted from a photoactive alpha phase to a photoactive delta phase at room temperature, and in order to stabilize the photoactive phase, a cation (Cs) having a small ionic radius is usually introduced + Or Rb + ) And halides (Br) - Or Cl - ) Mixed cationic halide perovskite is formed. In particular, in FA 1-X Cs X PbI y Br 3-y Perovskite solar cells based on (abbreviated as FACs) are ideal materials for commercialization of perovskite solar cells due to their excellent thermal stability and adjustable band gap.
To date, most high performance PSCs are based on N-i-p formal structures, the most commonly used hole transport layer being doped 2,2', 7' -tetrakis [ N, N-bis (p-methoxyphenyl) amino ] -9,9' -spirobifluorene (spiro-OMeTAD), however, the doped spiro-OMeTAD lacks sufficient stability, limiting long term stability of the device. In view of this, research into trans-perovskite solar cells employing a stable interfacial layer has received more attention, particularly, to the construction of trans-perovskite solar cells using a p-type semiconductor oxide as a hole transport layer, such as nickel oxide as a hole transport layer. However, perovskite solar cells based on nickel oxide suffer from lower open circuit voltage and lower efficiency compared to organic hole transport layers, and therefore improving the interface characteristics of perovskite and nickel oxide is of great importance to improve the performance of nickel oxide-based trans-structured perovskite solar cells. In the prior art, it is disclosed that An organic small molecular material is used as a hole transport layer to improve the interface performance of a nickel oxide-based trans-structure PSC, for example, molecules developed by Yang Wang et al have a D-Ac-An structure (as shown in formula a), organic molecules of the structure are similar to organic dyes of a D-A or D-pi-A structure in An n-type dye sensitized solar cell, an anchor group is generally positioned on An electron acceptor, an intramolecular electron transfer direction is from An electron donor to the electron acceptor and then to the anchor group, when the structure is used as An organic hole transport layer of a trans-structure perovskite solar cell, the anchor group tends to be adsorbed on a p-type semiconductor oxide, electrons flow to the p-type semiconductor oxide through the organic molecules, namely, the organic molecules/p-type semiconductor oxide interface hole transport direction is from the p-type semiconductor oxide to the organic molecules, and therefore, the problem that the organic transport molecule/p-type semiconductor oxide interface charge transport direction is not matched with the perovskite layer/p-type semiconductor oxide layer interface hole transport direction exists; al-Ashori et Al designed a molecule (formula c) with a single anchor modified electron donor carbazole, which still had the problems of insufficient anchoring effect on the nickel oxide substrate, mismatching of the organic molecular charge transport direction and the perovskite layer/nickel oxide interface hole transport direction, and in the molecular structure reported by Ece Aktas et Al (formula b), not only had the above-mentioned mismatching problem, but also, because two methoxy moieties at the top of carbazole compensate for polarization charges in the phosphate anchor, lower molecular dipole moment is formed at the interface, resulting in a certain reduction of the hole extraction rate of the interface.
Disclosure of Invention
The technical problems solved by the invention are as follows: an organic hole transport material and a perovskite solar cell are provided, which are used for solving the problems of insufficient interface stability and low hole efficiency of perovskite and a hole transport layer in the prior art.
The specific solution provided by the invention is as follows:
the invention provides an organic hole transport material, which is shown as a formula I or a formula II,
wherein, in each formula, R 1 Independently selected from carboxylic acid groups orOne of the phosphate groups; r is R 2 Each independently selected from one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzothienyl group, a substituted or substituted benzothiadiazolyl group; r is R 3 Each independently selected from electron withdrawing group substituted vinyl, electron withdrawing group substituted aryl, electron withdrawing group substituted thienyl, substituted or unsubstituted imide groups, said electron withdrawing group substitution including electron withdrawing group monosubstituted or electron withdrawing group polysubstituted.
On the basis of the above, the invention can be further improved as follows:
preferably, the electron withdrawing group is selected from the group consisting of a nitrile group, a substituted or unsubstituted imide group, and a substituted or unsubstituted imide group.
Preferably, the organic hole transport material is selected from one of the following structures:
the invention also provides a perovskite solar cell, comprising: a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, a perovskite active layer, and an organic hole transport layer disposed between the inorganic p-type semiconductor hole transport layer and the perovskite active layer, the organic hole transport layer comprising an organic hole transport material as described above;
alternatively, the organic hole transporting material comprises a transparent conductive oxide substrate, a perovskite active layer and an organic hole transporting layer arranged between the transparent conductive oxide substrate and the perovskite active layer, wherein the organic hole transporting layer comprises the organic hole transporting material.
Further, the perovskite solar cell comprises a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, the organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged;
or comprises a transparent conductive oxide substrate, the organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged.
Further, the p-type semiconductor hole transport layer material is selected from one of nickel oxide, doped nickel oxide, cuprous thiocyanate or cuprous gallate.
Further, the perovskite active layer material is ABX 3 Wherein A is selected from the group consisting of methylamine, formamidine, cs + B is selected from Pb 2+ 、Sn 2+ One or two of X is selected from I - 、Br - 、Cl - One or more of the following.
Further, the electron transport layer material is selected from [6,6 ]]-phenyl-C71-butanoic acid methyl ester, C 60 Or C 60 One of the derivatives.
Further, the electrode layer is of a single-layer structure or a double-layer structure, the single-layer structure material is selected from one of silver, gold, copper, chromium, indium tin oxide, aluminum doped zinc oxide and tungsten doped indium oxide, and the double-layer structure is selected from one of bismuth-copper double-layer structure, bismuth-gold double-layer structure, bismuth-silver double-layer structure, chromium-copper double-layer structure, chromium-gold double-layer structure or chromium-silver double-layer structure.
Further, the preparation of the organic hole transport layer comprises the following steps:
dissolving the organic hole transport material in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, coating the organic hole transport material solution on the inorganic p-type semiconductor hole transport layer, and then annealing for 10-200 min at the annealing temperature of 20-200 ℃;
Or the organic hole transport material is dissolved in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, then the organic hole transport material solution is coated on the transparent conductive oxide substrate, and then annealing treatment is carried out for 10-200 min at the annealing temperature of 20-200 ℃.
Based on the technical scheme of the invention, the method has the following beneficial effects:
(1) The organic hole transport material has a strong anchoring effect on an inorganic p-type semiconductor bottom or a transparent conductive oxide substrate, can regulate and control the interface energy level of the inorganic p-type semiconductor (or regulate and control the interface energy level of the transparent conductive oxide), promotes the hole transport efficiency from a perovskite layer to a nickel oxide layer (or from the perovskite layer to the transparent conductive oxide substrate), and improves the photoelectric conversion efficiency of the battery.
(2) Based on the organic hole transport material, the charge transfer direction in the organic molecule is matched with the hole transport direction of the perovskite layer/p-type semiconductor oxide interface, so that the extraction speed of the interface carrier is accelerated, the interface non-radiative recombination is inhibited, and the problems of low hole extraction efficiency, low open circuit voltage, low efficiency and the like of the trans-perovskite solar cell can be effectively solved.
(3) Based on the perovskite solar cell, the organic molecule of the Y-shaped double-anchor electron donor structure is adopted to modify the inorganic p-type semiconductor hole transport layer substrate or directly modify the transparent conductive oxide substrate, on one hand, the double-anchor (carboxyl and phosphate) is subjected to stronger chemical bonding with the substrate, on the other hand, the double-anchor is positioned on two end points of the Y-shaped structure, and the Y-shaped distribution can further strengthen the anchoring of the double-anchor on the substrate; in addition, the An-D-L-Ac (anchor group-electron donor-linking group-electron acceptor) structure has stronger molecular dipole, and can further strengthen the charge action of the structure and a substrate such as nickel oxide, thereby improving the mechanical property of An interface and the stability of a battery interface; in addition, the double anchors are positioned on the donor structure to form An-D-L-Ac structure, so that the organic molecules are promoted to be axially inclined to be vertical to the surface of the substrate, the donor and the acceptor with the anchors at the two ends of the organic molecules are respectively contacted with the substrate and the perovskite layer, and the ordered and uniform-orientation arrangement can be carried out at the interface, so that the interface hole extraction rate is accelerated.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a schematic structural view of a perovskite solar cell according to one embodiment of the invention.
Fig. 2 is a schematic structural view of a perovskite solar cell according to another embodiment of the invention.
Fig. 3 is a Scanning Electron Microscope (SEM) cross-sectional view of device 1 in an embodiment of the invention.
Fig. 4 is a graph of current density versus voltage for devices 1-4 and comparative device 1 in an example of the present invention.
FIG. 5 is a steady state fluorescence spectrum of perovskite films modified and unmodified with organic hole transport materials of the present invention.
Fig. 6 is a time resolved photoluminescence spectrum of a perovskite film modified and unmodified with an organic hole transport material according to the invention.
Drawings
In the drawings, the components represented by the respective reference numerals are as follows:
1. a transparent conductive oxide substrate; 2. an inorganic p-type semiconductor hole transport layer; 3. an organic hole transport layer; a 4 perovskite active layer; 5. an electron transport layer; 6. a hole blocking layer; 7. an electrode layer.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Unless otherwise indicated, all materials used in the present invention are commercially available or may be prepared by known methods.
The invention provides an organic hole transport material, which is shown as a formula I or a formula II,
wherein in each formula, R 1 Each independently selected from one of a carboxylic acid group or a phosphoric acid group; r is R 2 Respectively and independently selectFrom one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted benzothienyl group, a substituted or substituted benzothiadiazolyl group; r is R 3 Each independently selected from electron withdrawing group substituted vinyl, electron withdrawing group substituted aryl, electron withdrawing group substituted thienyl, substituted or unsubstituted imide groups, said electron withdrawing group substitution including electron withdrawing group monosubstituted or electron withdrawing group polysubstituted.
The invention designs a Y-type double-anchor (An) -electron donor (linker, L) -acceptor (Ac) (double-anchor-electron donor-linker-electron acceptor structure, an-D-L-Ac) organic micromolecule hole transport material, wherein each anchor is carboxyl or phosphate, and the electron donor is diphenylamine or carbazole. The Y-type double-anchor-based organic small molecule can be used as An organic hole transport layer material of a trans-perovskite solar cell, the electron transport direction in the Y-type double-anchor-based organic small molecule is from An-D-L-Ac (An- & gtAc), the Y-type double-anchor-based organic small molecule can be adsorbed on the surface of a p-type inorganic semiconductor oxide inorganic film through An anchor, and at the moment, the electron transport direction of An organic hole transport layer/p-type semiconductor oxide interface is as follows: from the p-type semiconductor oxide to the electron donor D attached to the anchor An, from the donor D to the acceptor Ac, and then to the perovskite active layer. Therefore, the hole transport direction in the small organic molecule and the hole transport direction of the interface of the organic hole transport layer and the p-type semiconductor oxide are matched with each other. In the prior art, D-L-Ac-An type dye molecules are mostly used as organic hole transport materials, the dye is adsorbed on the surface of a p-type inorganic semiconductor oxide film by virtue of An anchor group, and the electron transfer direction in the molecule is from An electron donor to An electron acceptor, but the acceptor is connected with the anchor group and is adsorbed on the surface of nickel oxide by virtue of the anchor group, so that electrons tend to flow from the dye molecules to the surface of nickel oxide, namely holes tend to flow from the surface of the p-type inorganic semiconductor oxide to the organic hole transport molecules, and therefore, the problem that the internal charge transport direction of the organic molecules/the hole transport direction of the interface of the p-type inorganic semiconductor and the hole transport direction of the interface of a perovskite layer/the interface of the p-type inorganic semiconductor oxide are not matched exists, and the internal charge transport of a battery is unfavorable. Based on the organic hole transport material, the organic intramolecular charge transfer direction is matched with the perovskite layer/p-type semiconductor oxide interface hole transport direction, so that the problems of low hole extraction efficiency, low open circuit voltage, low efficiency and the like of the trans-perovskite solar cell can be effectively solved.
Preferably, the electron withdrawing group is selected from the group consisting of a nitrile group, a substituted or unsubstituted imide group, and a substituted or unsubstituted imide group. When the electron withdrawing group is the substituent, the hole transport efficiency from the perovskite layer to the nickel oxide layer can be remarkably improved, and the efficiency of the trans-nickel oxide perovskite solar cell is improved.
Preferably, the organic hole transport material is selected from one of the following structures:
the organic small molecules with the structure have excellent hole transport efficiency and better efficiency.
The invention also provides a perovskite solar cell, comprising: a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, a perovskite active layer, and an organic hole transport layer disposed between the inorganic p-type semiconductor hole transport layer and the perovskite active layer, the organic hole transport layer comprising an organic hole transport material as described above;
alternatively, a transparent conductive oxide substrate, a perovskite active layer, and an organic hole transport layer disposed between the transparent conductive oxide substrate and the perovskite active layer, the organic hole transport layer comprising an organic hole transport material as described above.
As shown in fig. 1, the perovskite solar cell according to the embodiment of the invention comprises a transparent conductive oxide substrate 1, an inorganic p-type semiconductor hole transport layer 2, an organic hole transport layer 3, a perovskite active layer 4, an electron transport layer 5, a hole blocking layer 6 and an electrode layer 7 which are sequentially arranged;
Alternatively, the organic light-emitting device comprises a transparent conductive oxide substrate 1, the organic hole transport layer 3, a perovskite active layer 4, an electron transport layer 5, a hole blocking layer 6 and an electrode layer 7 which are sequentially arranged.
Preferably, the p-type semiconductor hole transport layer material is selected from one of nickel oxide, doped nickel oxide, cuprous thiocyanate or cuprous gallate.
Preferably, when the material is nickel oxide material or doped nickel oxide material, the p-type semiconductor hole transport layer is prepared by magnetron sputtering a nickel oxide target on a transparent conductive oxide substrate, or spraying a pyrolytic nickel oxide precursor solution on the transparent conductive oxide substrate, and sintering the nickel oxide target coated with the nickel oxide precursor at high temperature, or spin-coating nickel oxide nano ink on the transparent conductive oxide substrate.
Based on the perovskite solar cell, the organic molecule modified inorganic p-type semiconductor hole transport layer with the Y-shaped double-anchor electron donor structure is adopted, for example, in a nickel oxide-based trans-perovskite cell, the double-anchor group has chemical bonding action with a nickel oxide base, and the anchoring of the double-anchor group on a nickel oxide base can be further enhanced due to the fact that the double-anchor group is positioned on two end points of the Y-shaped structure; in addition, the structure with An-D-L-Ac has stronger molecular dipole, and can further strengthen the charge effect of the structure with substrates such as nickel oxide and the like, thereby improving the mechanical property of the interface and the stability of the battery interface; the anchor group is positioned on the donor structure to form An-D-L-Ac structure, so that the axial trend of the organic molecule is promoted to be vertical to the surface of nickel oxide, the donor and the acceptor with the anchor groups at the two ends of the organic molecule are respectively contacted with the p-type semiconductor oxide and the perovskite layer, and the ordered and uniform orientation arrangement can be carried out at the interface, thereby accelerating the interface hole extraction rate and finally obtaining the high-efficiency stable trans-nickel oxide perovskite solar cell.
Preferably, when the material is cuprous thiocyanate or cuprous gallate, the p-type semiconductor hole transport layer is prepared by spin-coating the nanomaterial and then sintering at high temperature.
Based on the perovskite solar cell provided by the embodiment of the invention, the perovskite active layer material is ABX 3 Wherein A is selected from the group consisting of methylamine, formamidine, cs + B is selected from Pb 2+ 、Sn 2+ One or two of X is selected from I - 、Br - 、Cl - One or more of the following.
According to the perovskite solar cell provided by the embodiment of the invention, the electron transport layer material is selected from [6,6 ]]-phenyl-C71-butanoic acid methyl ester, C 60 Or C 60 One of the derivatives.
According to the perovskite solar cell provided by the embodiment of the invention, the electrode layer is of a single-layer structure or a double-layer structure, the single-layer structure material is selected from one of silver, gold, copper, chromium, indium tin oxide, aluminum-doped zinc oxide and tungsten-doped indium oxide, and the double-layer structure is selected from one of bismuth-copper double-layer structure, bismuth-gold double-layer structure, bismuth-silver double-layer structure, chromium-copper double-layer structure, chromium-gold double-layer structure or chromium-silver double-layer structure.
According to the perovskite solar cell provided by the embodiment of the invention, the preparation of the organic hole transport layer comprises the following steps:
Dissolving the organic hole transport material in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, coating the organic hole transport material solution on the inorganic p-type semiconductor hole transport layer, and then annealing for 10-200 min at the annealing temperature of 20-200 ℃;
or the organic hole transport material is dissolved in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, then the organic hole transport material solution is coated on the transparent conductive oxide substrate, and then annealing treatment is carried out for 10-200 min at the annealing temperature of 20-200 ℃.
Preferably, the coating mode is selected from one of spin coating, knife coating, spray coating, slot coating or immersion.
Preferably, the organic solvent is selected from one of ethanol, acetone or toluene.
Preferably, the organic solvent is absolute ethanol.
Preferably, the transparent conductive oxide substrate is selected from one of Indium Tin Oxide (ITO) or fluorine doped tin oxide conductive glass (FTO).
Example 1: preparation of TPA-CA
As shown in the reaction formula A, the specific preparation method comprises the following steps:
(1) The raw material of the tert-butyl 4-aminobenzoate, the raw material of the tert-butyl 4-bromobenzoate and the catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain a structure shown in a formula a, wherein, the structure is formed by tert-butyl 4-aminobenzoate, tert-butyl 4-bromobenzoate and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) The structure shown in the formula a, p-bromobenzaldehyde and a catalyst Pd (OAc) 2 Alkali K 2 CO 3 Reacting in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12h to obtain a structure shown in a formula b, wherein the structure shown in the formula a, p-bromobenzaldehyde and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(3) After the structure shown in the formula b and triethylamine are dissolved in acetonitrile, malononitrile is added, and the reaction is carried out for 2 hours at 90 ℃ in a nitrogen atmosphere, so that the structure shown in the formula c is obtained.
(4) Dissolving the structure shown in the formula c in dichloromethane, adding trifluoroacetic acid, and hydrolyzing at room temperature to obtain the structure shown in the formula d.
Example 2: preparation of TPA-PA
The procedure of example 1 was repeated except that the starting material, tert-butyl 4-aminobenzoate and tert-butyl 4-bromobenzoate, were replaced with diethyl (4-amino-phenyl) -phosphate and diethyl 4-bromophenyl phosphate, respectively.
Example 3: preparation of PACz-CE
As shown in the reaction formula B, the specific preparation method comprises the following steps:
(1) The catalyst Pd (OAc) was first introduced 2 Alkali potassium acetate (AcOK), 1' -bis (diphenylphosphine) ferrocene (DPPF) and triethylamine (Et) 3 N) in dry Tetrahydrofuran (THF), stirring under reflux for 15 min under nitrogen, wherein catalyst Pd (OAc) 2 The molar ratio of basic potassium acetate AcOK, 1' -bis (diphenylphosphine) ferrocene (DPPF) was 2.12:9.2:4.24.
(2) The mixture was cooled to room temperature, and 3,6 dibromocarbazole and diethyl phosphite (HPO (OEt) were added to the solution 2 ) And 50mL of dry THF, and the mixture was refluxed with stirring for 16 hours to give the compound represented by formula f.
(3) The substance shown in the formula f, p-bromobenzaldehyde and a catalyst Pd (OAc) 2 And base K 2 CO 3 Reacting in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain a substance shown in a formula g, wherein the substance shown in a formula f, p-bromobenzaldehyde and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(4) After dissolving a structure shown in a formula g and triethylamine in acetonitrile, adding malononitrile, and reacting for 2 hours at 90 ℃ under a nitrogen atmosphere to obtain the structure shown in the formula h, wherein the molar ratio of a substance shown in the formula g to malononitrile is 1:3.
(5) Formula h was dissolved in anhydrous 1, 4-dioxane under argon atmosphere and bromotrimethylsilane (BrSi (CH) 3 ) 3 ) Reverse, oppositeStirring should be carried out at 25℃for 22 hours, after which methanol is added to the mixture at room temperature and stirring is continued for 3 hours to give the structure of formula i, wherein the molar ratio of formula h to bromotrimethylsilane is 1.55:15.59.
Example 4: preparation of CACz-CE
The CACz-CE was prepared as in example 3, except that the raw material HPO (OEt) was used 2 Replaced with tert-butyl formate.
Example 5: preparation of TPA-PR
(1) Structure a, 1, 4-dibromobenzene, catalyst Pd (OAc) 2 Alkali K 2 CO 3 In a mixed solvent of phenyl ether and toluene, reacting for 12h at 110 ℃ to obtain an intermediate a1, wherein the structure shown in the formula a, p-bromobenzaldehyde and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) Intermediate a1, N-dimethyl-3, 4,9, 10-perylenetetracarboxylic diimide and catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain an intermediate product a2, wherein N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide, the intermediate product a1 and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(3) Intermediate a2 was dissolved in dichloromethane, trifluoroacetic acid was added and hydrolyzed at room temperature to give TPA-PR.
Example 6: preparation of PACz-Th-In
As shown in reaction D, the specific preparation method comprises the following steps:
(1) With substance f, 3-bromothiophene-2-carbaldehyde, catalyst Pd (OAc) 2 And base K 2 CO 3 Reacting in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain a substance shown in a formula j, wherein the substance shown in the formula f, 3-bromothiophene-2-formaldehyde and Pd (OAc) 2 And K 2 CO 3 The molar ratio of phenyl ether to toluene is 20:24:35:0.6;
(2) Compound j (400 mg,1 mmol) and 1-hexyl-2, 3-trimethyl-3H-indole (293 mg,1.2 mmol) were added to CH 3 In CN (30 mL), piperidine was refluxed for 12h.
(4) The solvent was then removed by rotary evaporation and the residue was purified by chromatography (silica gel, dichloromethane: methanol=10:1 v/v) to give substance k.
(5) Formula k was dissolved in anhydrous 1, 4-dioxane and bromotrimethylsilane (BrSi (CH) 3 ) 3 ) The reaction was stirred at 25℃for 22 hours, then methanol was added to the mixture at room temperature and stirring was continued for 3 hours to give the formula PACz-Th-In wherein the molar ratio of formula k to bromotrimethylsilane was 1.55:15.59.
Wherein the starting material 1-hexyl-2, 3-trimethyl-3H-indole is prepared as shown in reaction D, 2, 3-trimethyl-3H-indole (15.91 g,100 mmol) and 1-bromohexane (19.7 g,120 mmol) are dissolved in acetonitrile (100 mL) and refluxed under nitrogen for 12H, the solvent is evaporated, and the crude product is washed three times with diethyl ether to give 1-hexyl-2, 3-trimethyl-3H-indole.
Example 7: preparation of CA-TPA-NaT
(1) As shown in reaction scheme E, the starting material (4-amino-phenyl) -phosphoric acid diethyl ester, 4-bromophenyl phosphoric acid diethyl ester, catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain an intermediate product n, wherein (4-amino-phenyl) -diethyl phosphate, diethyl 4-bromophenyl phosphate and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) The intermediate product N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide and the catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain an intermediate product a3, wherein N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide, N and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(3) Intermediate a4 was dissolved in dichloromethane and trifluoroacetic acid was added and hydrolyzed at room temperature to give TPA-PR.
Example 8: preparation of PACz-NaT
(1) The structure f, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide and the catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain an intermediate product a5, wherein N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide, f and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) Intermediate a5 was dissolved in dichloromethane and trifluoroacetic acid was added and hydrolyzed at room temperature to give TPA-PR.
Example 9: preparation of CA-TPA-Dt
(1) As shown in reaction scheme F, starting from substance b (60 mg,0.06 mmol), 1, 3-diethyl-2-thiobarbituric acid (110 mg,0.55 mmol), dissolved in dry CHCl 3 To (5 ml) was added pyridine (0.2 ml), and after stirring at room temperature for 12 hours under Ar atmosphere, the reaction was stopped by adding water, followed by CHCl 3 And (5) extracting. The combined organic phases are washed with water and dried over anhydrous sodium sulfate, the solvent is evaporated under reduced pressure and the residue is purified by column chromatography: by ethanol/CHCl 3 (1:30, v/v) as solvent, and subjecting to chromatography on silica gel to give L.
(2) Dissolving the structure shown in the formula L in dichloromethane, adding trifluoroacetic acid, and hydrolyzing at room temperature to obtain CA-TPA-Dt.
Example 10: preparation of PA-DPA-Fl-CE
(1) 2, 7-dibromo-9, 9-dihexyl-9H-fluorene is dissolved in DMF and tetrahydrofuran in the presence of n-BuLi, stirred and reacted for 1H at minus 78 ℃ and then stirred for 2H at normal temperature to obtain a substance m;
(2) The structure shown in formula n in example 5, substance m (wherein R is hexyl), and catalyst Pd (OAc) 2 Alkali K 2 CO 3 Reacting for 12h at 110 ℃ in a mixed solvent of phenyl ether and toluene to obtain an intermediate a6, wherein the structure shown in a formula n, m and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(4) After the intermediate product a6 and triethylamine are dissolved in acetonitrile, malononitrile is added, and the mixture is reacted for 2 hours at 90 ℃ under the nitrogen atmosphere to obtain an intermediate product a7.
(5) Intermediate a7 was dissolved in dichloromethane, trifluoroacetic acid was added and hydrolyzed at room temperature to give PA-DPA-Fl-CE.
Example 11: preparation of CACz-Ds
(1) The synthesis steps from f to g are carried out by taking the substance 2f and 1, 4-dibromobenzene as raw materials, and the substance O is obtained.
(2) Into a 100ml round flask were charged substances O (0.40 g,0.76 mmol), pinacol biborate (0.213 g,0.84 mmol), K 2 OAc (0.17 g,1.73 mmol) and PdCl 2 (dppf) (0.019 g,3 mol%) was used as a catalyst under nitrogen. After addition of dry DMF (5 mL), the mixture was heated to 80℃for 18h. The volatile components were removed in vacuo and the residue extracted with dichloromethane. The organic extracts were collected and dried over magnesium sulfate. After filtration, the filtrate was drained. The crude product was further purified by alumina column chromatography using hexane/DCM (4:1 by volume) as eluent to give material P.
(3) To a 100ml round flask was added substance 1 (0.10 g,0.19 mmol), substance P (0.12 g, 0.21) under nitrogen as K 2 CO 3 (0.052g，0.38mmol)、PPh 3 (2.50 mg,5 mol%) and Pd (PPh 3) 4 (0.01 g,5 mol%) as catalyst. To the mixture were added dry toluene (5 ml) and ethanol (1 ml). The mixture was heated to 80℃and reacted for 24 hours. The volatile components were removed in vacuo, the residue extracted with dichloromethane and washed with aqueous ammonium chloride. The organic extracts were collected and dried over magnesium sulfate. The filtrate was then drained. The crude product was further purified by column chromatography on silica gel using EA/MeOH (volume ratio 10:1) as eluent, giving product as green powder material Q.
(4) The structure shown in the substance Q is dissolved in methylene dichloride, trifluoroacetic acid is added, and CACz-Ds is obtained through hydrolysis at room temperature.
Wherein, the synthesis steps of the substance 1 are as follows:
as shown in reaction scheme G, first, 5-bromo-2, 3-trimethyl-3H-indole (1 a,1.7G,0.07 mol) nitrogen was charged into a 100ml two-necked flask. Acetonitrile (5 ml) was then added as solvent. To the solution was added ethyl iodide (2.8 mL) and the mixture was heated to reflux for 40 hours. The residue was triturated with diethyl ether and the resulting powder was washed with diethyl ether and dried under vacuum to give brown solid 1b.
To a 250ml two-necked round flask was added 2, 3-trimethyl-3H-indole (1 c,5.03g,32 mmol) nitrogen and acetonitrile (25 ml) as a solvent. To the solution was added ethyl iodide (8.0 mL) and the solution was refluxed for 40h, volatile components were removed in vacuo, and the solid formed was washed with diethyl ether. The product was an orange solid 1d.
1d (2.96 g,17 mmol), the squaric acid derivative (1 e,6.73g,21 mmol) and ethanol (20 ml) were added as solvents to a 100ml round flask. After triethylamine (2.8 ml,20 mmol) was added, the solution was heated to reflux for 15 min. The crude product was further purified by column chromatography on silica gel using methylene chloride/EA (volume ratio 9:1) as eluent. The product was orange solid 1f.
1f (0.50 g,1.6 mmol), 40% sodium hydroxide (0.35 ml) and ethanol (5 ml) were added as solvents to a 50ml round flask. The solution was heated to reflux for 30 minutes and then cooled to room temperature. During this time, some orange solid formed. Orange product 1g was collected by filtration and used without further purification.
1g (0.35 g,1.2 mmol), 1b (0.49 g,1.2 mmol), toluene (5 ml) and n-butanol (5 ml) were added to a 50ml round flask, refluxed for 20h, the solvent was removed in vacuo, and the crude product was further purified by silica gel column chromatography using methanol/EA (1:9 volume ratio) as eluent. The product was brown powdery substance 1.
Example 12: preparation of PACz-Cz-NaP
(1) Substance f in example 4, substance m in example 10 (wherein R is methyl), catalyst Pd (OAc) 2 Alkali K 2 CO 3 In a mixed solvent of phenyl ether and toluene, reacting for 12h at 110 ℃ to obtain an intermediate a8, wherein the structure shown in a formula n, m and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) After the intermediate product a8 and triethylamine are dissolved in acetonitrile, malononitrile is added, and the mixture is reacted for 2 hours at 90 ℃ under the nitrogen atmosphere to obtain an intermediate product a9.
(3) Intermediate a9 was dissolved in dichloromethane and trifluoroacetic acid was added and hydrolyzed at room temperature to give PACz-Cz-NaP.
Example 13: preparation of CA-DPA-Tp-CE
The synthesis procedure was the same as in example 1 except that p-bromobenzaldehyde was replaced with 5- (7-bromobenzo [1,2,5] thiadiazol-4-yl) thiophene-2-carbaldehyde to give CA-DPA-Tp-CE.
Example 14: preparation of CACz-Bz-CE
The synthesis procedure was the same as in example 3 except that p-bromobenzaldehyde was replaced with 7-bromo-4-aldehydebenzo [1,2,5] thiadiazole to give CACz-Bz-CE.
Example 15: preparation of CA-DPA-Th-CE
The synthesis procedure was the same as in example 1 except that p-bromobenzaldehyde was replaced with 2-bromo-4-aldehyde thiazole to give CA-DPA-Th-CE.
Example 16: preparation of CA-DPA-Bz-CE
The synthesis procedure was as in example 1, except that p-bromobenzaldehyde was replaced with 7-bromo-4-aldehydobenzo [1,2,5] thiadiazole.
Example 17: preparation of CA-DPA-Bz-NaT
(1) The material a, 4, 7-dibromo-2, 1, 3-benzothiadiazole and catalyst Pd (OAc) of example 1 were reacted 2 Alkali K 2 CO 3 In a mixed solvent of phenyl ether and toluene, reacting for 12h at 110 ℃ to obtain an intermediate product b1, wherein the substances a, 4, 7-dibromo-2, 1, 3-benzothiadiazole and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) Intermediate b1, N-dimethyl-3, 4,9, 10-perylenetetracarboxylic diimide and catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and toluene at 110 ℃ for 12 hours to obtain an intermediate product b2, wherein N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide, the intermediate product b1 and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(3) Intermediate b2 is dissolved in dichloromethane, trifluoroacetic acid is added, and the CA-DPA-Bz-NaT is obtained through hydrolysis at room temperature.
Example 18: preparation of PACz-Bz-NaT
(1) F, 4, 7-dibromo-2, 1, 3-benzothiadiazole and catalyst Pd (OAc) in example 3 2 Alkali K 2 CO 3 In a mixed solvent of phenyl ether and toluene, reacting for 12h at 110 ℃ to obtain an intermediate product b3, wherein the substances a, 4, 7-dibromo-2, 1, 3-benzothiadiazole and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(2) Intermediate b3, N-dimethyl-3, 4,9, 10-perylenetetracarboxylic diimide and catalyst Pd (OAc) 2 And a base in a mixed solvent of phenyl ether and tolueneReacting for 12h at 110 ℃ to obtain an intermediate product b4, wherein N, N-dimethyl-3, 4,9, 10-perylene tetracarboxylic diimide, the intermediate product b3 and Pd (OAc) 2 And K 2 CO 3 The molar ratio of (2) is 20:24:35:0.6.
(3) Intermediate b4 was dissolved in dichloromethane and trifluoroacetic acid was added and hydrolyzed at room temperature to give PACz-Bz-NaT.
Device 1 (NiMgLiO/TPA-CA)
A perovskite solar cell comprises a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged, wherein the transparent conductive oxide substrate is FTO glass, the inorganic p-type semiconductor hole transport layer is NiMgLiO, the organic hole transport layer is TPA-CA, and the perovskite active layer is (Cs 0.15 FA 0.85 )Pb(I 0.95 Br 0.05 ) 3 The electron transport layer material is [6,6 ]]-phenyl-C71-butyric acid isopropyl ester, the hole blocking layer material is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), the electrode layer material is silver, wherein the p-type semiconductor hole transport layer, the organic hole transport layer, the perovskite active layer, the electron transport layer, the hole blocking layer and the electrode layer are respectively 20nm, 5nm, 450nm, 30nm, 3nm and 80nm thick.
The preparation process of the NiMgLiO hole transport layer is as follows: adding magnesium acetate tetrahydrate and lithium acetate into a mixed solution of nickel acetylacetonate, acetonitrile and ethanol, and mixing to obtain a NiMgLiO precursor solution, wherein the volume ratio of acetonitrile to ethanol in the NiMgLiO precursor solution is 95:5, the molar atomic ratio of Ni to Mg to Li is 80:15:5, and the total metal ion concentration is 0.02M; the NiMgLiO precursor solution was sprayed onto the transparent conductive oxide substrate and annealed at 570 ℃ for 30 minutes.
Wherein, the preparation process of the organic hole transport layer is as follows: and dissolving the organic hole transport material in ethanol to prepare an ethanol solution of the organic hole transport material with the concentration of 0.5mg/mL, coating the ethanol solution on the NiMgLiO hole transport layer, and annealing for 200min at the annealing temperature of 120 ℃ to obtain the organic hole transport layer.
Device 2 (NiMgLiO/TPA-PA)
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was TPA-PA.
Device 3 (NiMgLiO/TPA-PR)
A perovskite solar cell, identical to that of device 1, differs only in that the organic hole transport layer material is TPA-PR.
Device 4 (NiMgLiO/CACz-CE)
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material is CACz-CE.
Device 5 (NiMgLiO/PACz-CE)
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was PACz-CE.
Device 6 (NiMgLiO/PACz-Th-In)
A perovskite solar cell is identical to device 1 except that the organic hole transport layer material is PACz-Th-In.
Devices 7-9
Perovskite solar cell is identical to device 1 except that the concentration of organic hole transporting material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 7, device 8 and device 9, respectively.
Devices 10-12
Perovskite solar cell is the same as device 2 except that the concentration of organic hole transport material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 10, device 11 and device 12, respectively.
Devices 13-15
Perovskite solar cell is the same as device 3 except that the concentration of organic hole transport material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 13, device 14 and device 15, respectively.
Devices 16-18
Perovskite solar cell is the same as device 4 except that the concentration of organic hole transport material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 16, device 17 and device 18, respectively.
Devices 19-21
: perovskite solar cell is the same as device 5 except that the concentration of organic hole transport material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 19, device 20 and device 21, respectively.
Devices 22-24
: perovskite solar cell is identical to device 6 except that the concentration of organic hole transporting material in the ethanol solution is 0.01mg/L, 0.4mg/L and 20mg/L, respectively, corresponding to device 22, device 23 and device 24, respectively.
Device 25
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-TPA-NaT.
Device 26
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was PACz-NaT.
Device 27
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-TPA-Dt.
Device 28
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material is PA-DPA-Fl-CE.
Device 29
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material is CACz-Ds.
Device 30
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was PACz-Cz-NaP.
Device 31
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-DPA-Tp-CE.
Device 32
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material is CACz-Bz-CE.
Device 33
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-DPA-Th-CE.
Device 34
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-DPA-Bz-CE.
Device 35
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was CA-DPA-Bz-NaT.
Device 36
A perovskite solar cell, identical to that of device 1, except that the organic hole transport layer material was PACz-Bz-NaT.
Device 37
The same as device 1 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was directly coated on the transparent conductive oxide substrate.
Device 38
The same as device 2 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was directly coated on the transparent conductive oxide substrate.
Device 39
The same as device 3 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was coated directly onto the transparent conductive oxide substrate.
Device 40
The same as device 34 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was directly coated on the transparent conductive oxide substrate.
Device 41
The same as device 5 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was directly coated on the transparent conductive oxide substrate.
Device 42
The same as device 6 except that no NiMgLiO hole transport layer was included, the ethanol solution of the organic hole transport material was directly coated on the transparent conductive oxide substrate.
Device 43
A perovskite solar cell comprises a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged, wherein the transparent conductive oxide substrate is ITO glass, the inorganic p-type semiconductor hole transport layer is made of nickel oxide, the organic hole transport layer is made of TPA-PA, and the perovskite active layer is made of MAPbI 3 The electron transport layer material is C 60 The hole blocking layer is made of BCP, the electrode layer is made of copper, and the p-type semiconductor hole transport layer, the organic hole transport layer, the perovskite active layer, the electron transport layer, the hole blocking layer and the electrode layer are respectively 40nm, 20nm, 500nm, 60nm, 10nm and 100nm thick.
The preparation process of the nickel oxide hole transport layer comprises the following steps: placing the ITO glass subjected to ultraviolet treatment into a cavity of a magnetron sputtering instrument, sputtering a nickel oxide target material by magnetron sputtering with the magnetron power of 290W and the magnetron sputtering time of 10 minutes, taking out a sample, placing the sample into a heat table at 300 ℃, and annealing in air for 20 minutes.
Wherein, the preparation process of the organic hole transport layer is as follows: and dissolving the organic hole transport material in acetone to prepare an acetone solution of the organic hole transport material with the concentration of 16mg/mL, coating the nickel oxide hole transport layer with the ethanol solution, and then annealing for 30min at the annealing temperature of 150 ℃ to obtain the organic hole transport layer.
Device 44
A perovskite solar cell comprises a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged, wherein the transparent conductive oxide substrate is FTO glass, the inorganic p-type semiconductor hole transport layer is made of cuprous thiocyanate, the organic hole transport layer is PACz-NaT, and the perovskite active layer is made of FAPbI 3 The electron transport layer material is C 60 The hole blocking layer is made of BCP, and the electrode layer is of a bismuth-copper double-layer structure, wherein the thicknesses of the p-type semiconductor hole transport layer, the organic hole transport layer, the perovskite active layer, the electron transport layer, the hole blocking layer and the electrode layer are respectively 10nm, 3nm, 400nm, 12nm, 2nm and 200nm.
The preparation process of the cuprous thiocyanate hole transport layer comprises the following steps: spin-coating copper thiocyanate/diethyl sulfide solution (solution concentration is 35 mg/mL) on ITO glass subjected to ultraviolet treatment, annealing at 100 ℃ for 10 minutes,
wherein, the preparation process of the organic hole transport layer is as follows: and dissolving the organic hole transport material in toluene to prepare toluene solution of the organic hole transport material with the concentration of 0.01mg/mL, coating ethanol solution on the cuprous thiocyanate hole transport layer, and annealing for 30min at the annealing temperature of 150 ℃ to obtain the organic hole transport layer.
Comparative example device 1
The same as device 1 except that no organic hole transport layer was coated between the NiMgLiO hole transport layer and the perovskite active layer.
Device structure characterization and performance testing
1) Structural characterization:
SEM characterization was performed on the interface of the perovskite battery device 1 prepared by the device 1, and as shown in fig. 3, it can be seen that the organic hole transport layer 1 on the surface of the NiMgLiO hole transport layer is dense and regular, and each layer in the perovskite solar cell is tightly stacked.
2) Battery performance test
2.1 testing the cell performance of device 1 (NiMgLiO/TPA-CA), device 2 (NiMgLiO/TPA-PA), device 3 (NiMgLiO/TPA-PR), device 4 (NiMgLiO/CACz-CE), device 5 (NiMgLiO/PACz-CE), device 6 (NiMgLiO/PACz-Th-In) and comparative example device 1 (original) to obtain the current density versus voltage (J-V) characteristic curves (test conditions: AM1.5G,100 mW/cm) of the perovskite cells shown In FIG. 4 2 Effective area is 0.09cm 2 ) Compared with the comparative example device 1, the battery performance of the Y-type double-anchor modified donor-acceptor small organic molecule modified nickel oxide-based perovskite devices 1-6 is remarkably improved.
2.2 cell performance tests were performed on devices 7-32 and comparative example device 1, and the results are shown in Table 1.
Table 1: cell performance parameter table for devices 7-42 and comparative example device 1
As shown in table 7, after the modification of the nickel oxide base by using the Y-type double-anchor modified donor-acceptor type organic small molecule as the hole transport layer, the performance of the nickel oxide base perovskite solar cell can be remarkably improved, and the cell efficiency can be improved; the trans perovskite batteries obtained by directly modifying the transparent conductive oxide substrate by directly taking the Y-type double-anchor modified donor-acceptor type small organic molecules as the hole transport layer have excellent battery performance, for example, the photoelectric conversion efficiency of the perovskite battery (the device 37) taking TPA-CA molecules as the hole transport layer and the photoelectric conversion efficiency of the perovskite battery (the device 7-9) taking TPA-CA molecules as the nickel oxide base are obviously superior to that of the nickel oxide base perovskite battery (the comparative example device 1) in battery performance parameters of the device 7, the device 8, the device 9, the device 37 and the comparative example device 1.
3) Steady state fluorescence (PL) and Time Resolved Photoluminescence (TRPL) tests
The Y-type double-anchor-group modified donor-acceptor type organic hole transport material can effectively passivate contact defects of perovskite and nickel oxide interfaces, and In order to evaluate passivation defect effects, a NiMgLiO layer, an organic hole transport layer (materials are respectively TPA-CA, TPA-PA, TPA-PR, CACz-CE, PACz-Th-In) and a perovskite active layer (Cs) are sequentially arranged on an ITO transparent conductive substrate according to the method In the device 1 0.15 FA 0.85 )Pb(I 0.95 Br 0.05 ) 3 The control group was sequentially provided with a NiMgLiO layer and a perovskite active layer on an ITO substrate, labeled as original films, and then steady state fluorescence (PL) and Time Resolved Photoluminescence (TRPL) tests were performed on 7 samples, respectively, as shown In fig. 5 and 6. The steady-state PL luminous intensity of the perovskite film of the organic molecules modified by TPA-CA, TPA-PA, TPA-PR, CACz-CE, PACz-CE and PACz-Th-In is obviously lower than that of a standard sample, and the result shows that the Y-type double-anchor modified donor-acceptor type organic hole transport molecule accelerates the extraction speed of interface carriers at a nickel oxide/perovskite interface, thereby inhibiting interface non-radiative recombination, improving the performance of the device, especially the open circuit voltage (V OC ). The TRPL results of perovskite thin films show a bi-exponential decay characteristic with fast decay, which may be related to non-radiative recombination due to perovskite surface charge trapping defects, and slow decay, which represents radiative recombination of free carriers in the body, as shown in table 8, fitting with bi-exponential decay functions, according to the following formula:
y＝A 1 exp(-t/τ 1 )+A 2 exp(-t/τ 2 )+y 0
here τ 1 And τ 2 Respectively fast decay and slow decay lifetimes, average carrier lifetime (τ ave ) The method is obtained according to the following formula:
as shown In Table 8, the original film had a carrier lifetime of 8.88ns, a carrier lifetime of 5.12ns, a carrier lifetime of 4.58ns, a carrier lifetime of 7.16ns, a carrier lifetime of 6.74ns NiMgLiO/PACz-CA, a carrier lifetime of 5.94ns, and a carrier lifetime of 7.11ns, which indicates that the contact defect at the interface can be effectively reduced after modification with Y-type double-anchor modified donor-acceptor type organic hole transport molecules, the hole extraction speed is increased, and non-radiative recombination of perovskite and nickel oxide interface is suppressed.
Table 8: TRPL data fitting parameters for perovskite membranes
Although embodiments of the present invention have been described in detail above, one of ordinary skill in the art will appreciate that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.

Claims (7)

1. An organic hole transport material selected from one of the following structures:
2. a perovskite solar cell, comprising: a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, a perovskite active layer, and an organic hole transport layer disposed between the inorganic p-type semiconductor hole transport layer and the perovskite active layer, the organic hole transport layer comprising the organic hole transport material of claim 1;
alternatively, comprising a transparent conductive oxide substrate, a perovskite active layer, and an organic hole transport layer disposed between the transparent conductive oxide substrate and perovskite active layer, the organic hole transport layer comprising the organic hole transport material of claim 1;
the p-type semiconductor hole transport layer material is selected from one of nickel oxide, niMgLiO and cuprous thiocyanate.
3. The perovskite solar cell according to claim 2, wherein the perovskite solar cell comprises a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, the organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer, which are disposed in that order;
Or comprises a transparent conductive oxide substrate, the organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially arranged.
4. The perovskite solar cell of claim 2, wherein the perovskite active layer material is ABX 3 Wherein A is selected from the group consisting of methylamine, formamidine, cs + B is selected from Pb 2+ 、Sn 2+ One or two of X is selected from I - 、Br - 、Cl - One or more of the following.
5. A perovskite solar cell according to claim 3, characterized in that the electron transport layer material is selected from [6,6]-phenyl-C71-butanoic acid methyl ester, C 60 Or C 60 One of the derivatives.
6. A perovskite solar cell according to claim 3, wherein the electrode layer has a single layer structure or a double layer structure, the single layer structure material is selected from one of silver, gold, copper, chromium, indium tin oxide, aluminum doped zinc oxide, and tungsten doped indium oxide, and the double layer structure is selected from one of bismuth copper double layer structure, bismuth gold double layer structure, bismuth silver double layer structure, chromium copper double layer structure, chromium gold double layer structure, or chromium silver double layer structure.
7. The perovskite solar cell according to any one of claims 2 to 6, wherein the preparation of the organic hole transport layer comprises the steps of:
Dissolving the organic hole transport material in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, coating the organic hole transport material solution on the inorganic p-type semiconductor hole transport layer, and then annealing for 10-200 min at the annealing temperature of 20-200 ℃;
or the organic hole transport material is dissolved in an organic solvent to prepare an organic hole transport material solution with the concentration of 0.01-20 mg/mL, then the organic hole transport material solution is coated on the transparent conductive oxide substrate, and then annealing treatment is carried out for 10-200 min at the annealing temperature of 20-200 ℃.
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