CN113979969B - Organic hole transport material, preparation method and application thereof, and perovskite solar cell - Google Patents
Organic hole transport material, preparation method and application thereof, and perovskite solar cell Download PDFInfo
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- CN113979969B CN113979969B CN202111176906.5A CN202111176906A CN113979969B CN 113979969 B CN113979969 B CN 113979969B CN 202111176906 A CN202111176906 A CN 202111176906A CN 113979969 B CN113979969 B CN 113979969B
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- hole transport
- transport material
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- organic hole
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- 239000000463 material Substances 0.000 title claims abstract description 92
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- 238000000576 coating method Methods 0.000 claims description 9
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 8
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
- C07F9/6539—Five-membered rings
- C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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Abstract
The invention provides an organic hole transport material, a preparation method and application thereof, and a perovskite solar cell. The chemical formula of the organic hole transport material is shown below:
ar is a triphenylamine derivative with semiconductor characteristics, and the energy level of the Ar is adjusted according to the electron donating and electron withdrawing characteristics of the Ar; r is R 3 The pi-conjugated fine tuning hole mobility and energy level are expanded for pi-interval conjugated aromatic systems, so that the distribution of electrons in molecules is more uniform, meanwhile, the molecules tend to be flattened, the stacking behavior of organic semiconductor molecules is effectively regulated, and the hole transmission capacity is further improved. R is R 4 Is an anchor group containing a hydrogen bond donor and is in chemical reaction or supermolecular interaction with the surface interface of an electrode material or the surface interface of a P-type semiconductor material. The hole transport material can be applied to perovskite solar cells to effectively enhance the carrier transport performance and interface contact stability of an electrode/perovskite interface or a P-type hole transport layer/perovskite interface.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an organic hole transport material, a preparation method and application thereof, and a perovskite solar cell.
Background
Organic-inorganic halide perovskite (OIHP) materials have been widely used in thin film transistors, lasers, bipolar transistors, light emitting diodes, flexible memory, and particularly solar cells, have received great attention in the optoelectronic field due to long carrier diffusion lengths, efficient bipolar charge transport, broad light absorption and large absorption coefficients, and have become one of the most popular active materials in the research topic. Metal halide Perovskite Solar Cells (PSCs) have attracted extensive attention in the scientific and industrial community over the past few years due to their great potential for interesting photophysical properties, high Power Conversion Efficiencies (PCEs) and low cost processing.
The interfacial properties between the perovskite light absorbing layer and the Hole Transporting Material (HTM) are strongly dependent on the HTM. Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) is the most commonly used HTM for p-i-n type PSCs. Typically, a thin layer of undoped PTAA is used as HTM. However, in some cases, due to its low hole mobility. Thus, PTAA is doped to provide high Photoelectric Conversion Efficiency (PCE) for PSCs, and the cost of PTAA is even higher (1980$/g), making it impossible to mass-produce PSCs. Therefore, the HTM with simple synthesis and purification, low cost and excellent performance is studied to have important significance for realizing commercialization of perovskite batteries.
Disclosure of Invention
In view of the above, the invention provides an organic hole transport material, a preparation method and application thereof, and a perovskite solar cell, so as to solve or partially solve the technical problems existing in the prior art.
In a first aspect, the present invention provides an organic hole transport material having the formula:
wherein Ar is
Any one of R 1 、R 2 Is hydrogen or an aromatic group or an alkyl group containing a heteroatom;
R 3 is that
Wherein n is a positive integer between 0 and 10;
R 4 is that
-(C n H 2n )PO 3 H 2 、-(C n H 2n )COOH、-(C n H 2n )SO 3 H 2 、-(C n H 2n )Si(OH) 3 ， -(C n H 2n )B(OH) 2 ，-(C n H 2n ) SH, wherein n is a positive integer between 0 and 5.
In a second aspect, the invention also provides a preparation method of the organic hole transport material.
In a third aspect, the invention also provides an application of the hole transport material in preparing perovskite solar cells and organic light-emitting diodes.
In a fourth aspect, the present invention also provides a perovskite solar cell, including a substrate, a hole transport layer, a perovskite layer, an electron transport layer, a hole blocking layer, and an electrode layer, which are sequentially stacked; the hole transport layer is prepared from the organic hole transport material.
In a fifth aspect, the invention also provides a preparation method of the perovskite solar cell.
Compared with the prior art, the organic hole transport material, the preparation method thereof and the perovskite solar cell have the following beneficial effects:
(1) The invention is thatIn (c) is a benzo [ c ]][1,2,5]Thiadiazole is taken as a center, ar is a triphenylamine derivative with semiconductor characteristics, and the Ar and a perovskite component generate Lewis acid-base interaction, and the energy level of the Ar is adjusted according to electron donating and electron withdrawing characteristics of the Ar; r is R 3 The pi conjugated aromatic system regulates the stacking behavior of organic semiconductor molecules so as to improve the hole transport capacity, and is generally easy to synthesize and has excellent optical and electrochemical properties. In addition, their structure can be easily adjusted to adjust their optical, electrochemical properties and thermal stability. R is R 4 Is an anchor group containing a hydrogen bond donor and is in chemical reaction or supermolecular interaction with an electrode or a P-type semiconductor substrate. The hole transport material has the advantages of simple synthesis, low cost, good stability and strong hole transport capacity, and can effectively enhance the carrier transport performance and interface contact stability of an electrode/perovskite interface or a P-type hole transport layer/perovskite interface when being applied to a perovskite solar cell. Has higher application value in the photoelectric fields of organic light emitting diodes, solar cells and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a schematic diagram of the structure of a perovskite solar cell of the present invention;
FIG. 2 is a first compound 1 H NMR spectrum;
FIG. 3 shows a first compound 13 C NMR spectrum;
FIG. 4 is a second compound 1 H NMR spectrum;
FIG. 5 is a fourth compound 1 H NMR spectrum;
FIG. 6 is a fifth compound 1 H NMR spectrum;
FIG. 7 is a fifth compound 13 C NMR spectrum;
FIG. 8 is a sixth compound 1 H NMR spectrum;
FIG. 9 is a diagram of Compound P1 1 H NMR spectrum;
FIG. 10 is a diagram of Compound P1 13 C NMR spectrum;
FIG. 11 is an HRMS spectra of Compound P1;
FIG. 12 is a diagram of Compound P2 1 H NMR spectrum;
FIG. 13 Compound P2 13 C NMR spectrum;
FIG. 14 HRMS spectra of Compound P2;
FIG. 15 is a diagram of Compound P3 1 H NMR spectrum;
FIG. 16 Compound P3 13 C NMR spectrum;
FIG. 17 HRMS spectra of Compound P3;
FIG. 18 is a diagram of Compound P4 1 H NMR spectrum;
FIG. 19 HRMS spectra of Compound P4;
FIG. 20 is an ultraviolet-visible absorption spectrum of organic hole transport materials P1 to P4 in tetrahydrofuran;
FIG. 21 shows MAPbI 3 The film is spin-coated on ultraviolet-visible absorption spectrograms of ITO, P1-P4 and PTAA;
FIG. 22 is a cyclic voltammogram of organic hole transport materials P1-P4 in methylene chloride;
fig. 23 is an energy level diagram of the perovskite solar cell in examples 11 to 14;
FIG. 24 is a thermogravimetric analysis of the hole transport materials P1 to P4;
fig. 25 is a graph of the positive and negative sweep J-V curves of perovskite solar cells prepared in examples 11 to 14.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the application provides an organic hole transport material, the chemical formula of which is shown as follows:
wherein Ar is
Any one of R 1 、R 2 Is hydrogen or an aromatic group or an alkyl group containing a heteroatom; r is R 3 Is that
Wherein n is a positive integer between 0 and 10; r is R 4 Is->
-(C n H 2n )PO 3 H 2 、-(C n H 2n ) COOH、-(C n H 2n )SO 3 H 2 、-(C n H 2n )Si(OH) 3 ，-(C n H 2n )B(OH) 2 ，-(C n H 2n ) SH, etc., wherein n is a positive integer of 0 to 5.
Specifically, R is 1 、R 2 May be an aromatic group or an alkyl group containing heteroatoms such as oxygen, nitrogen, fluorine, sulfur, phosphorus, chlorine, selenium, arsenic, bromine, iodine, etc., such as:
-OC n H 2n+1 、-SC n H 2n+1 any one of (1) -H, wherein n is positive between 1 and 5An integer; r is as described above 4 Is an active anchoring group capable of chemically reacting or supermolecular interactions with hydrogen bond donor or acceptor groups of the electrode or inorganic semiconductor surface interface.
In some embodiments, the hole transport material has the formula:
r is
-PO 3 H 2 Any one of them.
In some embodiments, the organic hole transport material has the formula shown in any one of P1-P4:
based on the same inventive concept, the embodiment of the application also provides a preparation method of the organic hole transport material with the chemical formulas shown as P1-P4, specifically, the preparation method of the organic hole transport material with the chemical formula P1 comprises the following steps:
s11, reacting 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole with (4- (diphenylamino) phenyl) boric acid under alkaline conditions to obtain a first compound; s12, under the protection of inert gas, reacting the first compound with 5-aldehyde-2-thiopheneboronic acid under an alkaline condition to obtain a second compound; s13, under the protection of inert gas, reacting the second compound with cyanoacetic acid to obtain an organic hole transport material with a chemical formula P1;
the preparation method of the organic hole transport material with the chemical formula P2 comprises the following steps:
s21, under the protection of inert gas, reacting the first compound with 4-formylphenyl boric acid under an alkaline condition to obtain a third compound; s22, under the protection of inert gas, reacting a third compound with cyanoacetic acid to obtain an organic hole transport material with a chemical formula P2;
the preparation method of the organic hole transport material with the chemical formula P3 comprises the following steps:
s31, under the protection of inert gas, reacting the first compound with diethyl phosphinate under an alkaline condition to obtain a fourth compound; s32, under the protection of inert gas, carrying out hydrolysis reaction on the fourth compound and trimethyl bromosilane to obtain an organic hole transport material with a chemical formula P3;
the preparation method of the organic hole transport material of the chemical formula P4 comprises the following steps:
s41, under the protection of inert gas, reacting 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole with 4-borate-4 ',4' -dimethoxy triphenylamine under the alkaline condition to obtain a fifth compound; s42, under the protection of inert gas, reacting the fifth compound with diethyl phosphinate under an alkaline condition to obtain a sixth compound; s43, carrying out hydrolysis reaction on the sixth compound and trimethyl bromosilane under the protection of inert gas to obtain the organic hole transport material with the chemical formula P4.
Specifically, the first compound has the structural formula of
The structural formula of the second compound is
The structural formula of the third compound is +.>
The structural formula of the fourth compound is +.>
The structural formula of the fifth compound is
The structural formula of the sixth compound is +.>
Specifically, in some embodiments, in step S11, the molar ratio of 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole to 4-borate-4 ',4' -dimethoxytriphenylamine is (1.5-3): 1, the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the base used in the reaction is potassium carbonate, the catalyst is tetrakis (triphenylphosphine) palladium, and the solvent is toluene.
In the step S41, the molar ratio of the 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole to the 4-borate-4 ',4' -dimethoxy triphenylamine is (1.5-3): 1, the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the alkali used in the reaction is potassium carbonate, the catalyst is tetra (triphenylphosphine) palladium, and the solvent is toluene.
In the step 12, the molar ratio of the first compound to the 5-aldehyde-2-thiophene boric acid is 1, the reaction temperature is 85-120 ℃, the reaction time is 5-24 h, the alkali is potassium carbonate, the catalyst is tetra (triphenylphosphine) palladium, and the solvent is tetrahydrofuran.
In the step 21, the mole ratio of the first compound to the 4-formylphenyl boric acid is 1 (1.2-3), the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the alkali is potassium carbonate, the catalyst is tetra (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) The solvent is tetrahydrofuran.
In the step S31, the mole ratio of the first compound to the diethyl phosphite is 1 (2-5), the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the alkali is triethylamine, the catalyst is tetra (triphenylphosphine) palladium, and the solvent is toluene.
In the step S42, the molar ratio of the fifth compound to the diethyl phosphite is 1 (2-5), the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the base is triethylamine, the catalyst is tetra (triphenylphosphine) palladium, and the solvent is toluene.
In the step S13, the molar ratio of the second compound to the cyanoacetic acid is 1 (4-5), the reaction temperature is 85-120 ℃, the reaction time is 5-16 h, the alkali is piperidine, and the solvent is acetic acid.
In the step S22, the molar ratio of the third compound to the cyanoacetic acid is 1 (4-5), the reaction temperature is 85-120 ℃, the reaction time is 5-16 h, the alkali is piperidine, and the solvent is acetic acid.
In the step S32, the mole ratio of the fourth compound to the trimethyl bromosilane is 1 (4-5), the reaction temperature is 20-25, the reaction time is 6-12 h, and the solvent is methylene dichloride.
In the step S43, the mol ratio of the sixth compound to the trimethyl bromosilane is 1 (4-5), the reaction temperature is 20-25, the reaction time is 6-12 h, and the solvent is dichloromethane.
The inert gas in the reaction step is nitrogen or argon.
Based on the same inventive concept, the embodiment of the application also provides application of the organic hole transport material in preparing perovskite solar cells and organic light-emitting diodes.
Based on the same inventive concept, the embodiment of the present application further provides a perovskite solar cell, as shown in fig. 1, including a substrate 1, a hole transport layer 2, a perovskite layer 3, an electron transport layer 4, a hole blocking layer 5, and an electrode layer 6, which are sequentially stacked; the hole transport layer 2 is made of the organic hole transport material described above.
In some embodiments, the electron transport layer 4 is made of methyl [6,6] -phenyl-C61-butyrate, the hole blocking layer 5 is made of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and the electrode layer 6 is made of silver.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the perovskite solar cell, which comprises the following steps:
s1, providing a substrate;
s2, preparing an organic hole transport material solution, and coating the organic hole transport material solution on a substrate to prepare a hole transport layer;
s3, preparing a perovskite precursor solution, and coating the perovskite precursor solution on the hole transport layer to prepare a perovskite layer;
s4, preparing an electron transport material solution, and coating the electron transport material solution on the perovskite layer to prepare an electron transport layer;
s5, preparing a hole blocking layer material solution and coating the hole blocking layer material solution on the electron transport layer;
and S6, preparing an electrode layer on the electron transport layer.
In some embodiments, the organic hole transport material solution is formulated specifically as: and dissolving the organic hole transport material in chlorobenzene, and stirring and dissolving to obtain the organic hole transport material, wherein the mass-volume ratio of the organic hole transport material to the chlorobenzene is 2mg (1-3) mL.
In some embodiments, the hole transport layer is prepared by coating an organic hole transport material solution on a substrate, specifically: and spin-coating the organic hole transport material solution on the substrate by using a spin-coating method, wherein the spin-coating speed is 5000-6000 r/min, the spin-coating time is 30-60 s, and annealing is performed for 8-12 min at 80-120 ℃ after the spin-coating is completed.
In some embodiments, the perovskite precursor solution (i.e., MAPbI 3 Solution) is prepared by the following steps: 722.08mg lead iodide and 238.50mg of iodomethylamine solid are dissolved in 1mL of N, N-Dimethylformamide (DMF), and stirred at normal temperature until the solid is completely dissolved; the perovskite precursor solution is coated on the hole transport layer by a spin coating method, and the specific spin coating method is as follows: spin-coating for 10s at a speed of 1000r/min in a nitrogen glove box, spin-coating for 30s at a speed of 5000r/min, and dripping 125 mu L of ethyl acetate onto the hole transport layer in the second spin-coating for 15s, and annealing at 100 ℃ for 40min after spin-coating is completed to obtain the perovskite layer.
In some embodiments, the preparing an electron transport layer in step S4 is specifically: 20mg of [6,6] -phenyl-C61-methyl butyrate (PCBM) was dissolved in 1mL of chlorobenzene, and stirred at room temperature until completely dissolved, yielding a solution of [6,6] -phenyl-C61-methyl butyrate; in a nitrogen glove box, the [6,6] -phenyl-C61-methyl butyrate solution was spin-coated on the perovskite layer at 3000r/min for 60s.
In some embodiments, a hole blocking layer material solution is formulated and coated on the electron transport layer in step S5, specifically: dissolving 0.5mg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) in 1mL of isopropanol, and stirring at normal temperature until the 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) is completely dissolved to obtain a 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) solution; 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) solution is spin-coated on the electron transport layer at 5000r/min in a nitrogen glove box, and the spin-coating time is 35s.
In some embodiments, the preparing an electrode layer on the electron transport layer in step S6 is specifically: the electrode layer is prepared by adopting a vacuum coating method, and specifically comprises the following steps: in the vacuum coating apparatus, the vacuum degree is pumped to 3X 10 -4 And evaporating a silver electrode when Pa is about, and finally forming the silver electrode with the thickness of 100 nm.
In some embodiments, the substrate is ITO conductive glass.
The preparation method and application of the organic hole transport material of the present application are further described in the following specific examples.
Example 1
The synthesis method of the first compound comprises the following steps:
1470mg of 4, 7-dibromobenzo [ c ] are charged to a 150mL dry three-necked round bottom flask][1,2,5]Thiadiazole, 950mg of (4- (diphenylamino) phenyl) boronic acid, 116mg of Pd (PPh) 3 ) 4 2760mg of K 2 CO 3 And 70mL toluene deoxygenated for 15min and under N 2 Heating, stirring and refluxing at 85-120 ℃ under the atmosphere for overnight. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, petroleum ether: dichloromethane=3:1 as eluent) to give an orange solid as the first compound in 60% yield (457 mg).
Of a first compound 1 The H NMR spectrum is shown in fig. 2: 1 H NMR(400MHz,DMSO-d 6 )：δ8.09(d,J＝7.7 Hz,1H),7.90(d,J＝8.7Hz,2H),7.74(d,J＝7.7Hz,1H),7.36(dd,J＝8.4,7.2Hz,4H),7.15–6.99(m,8H).
of a first compound 13 The C NMR spectrum is shown in FIG. 3: 13 C NMR(400MHz,DMSO-d 6 )：δ153.66,152.90,148.18,147.25,133.10,132.89,130.64,130.16,128.09,125.04,124.13,122.59,111.89.
the synthetic scheme for the first compound is shown below:
example 2
The synthesis method of the second compound comprises the following steps:
into a 100mL three-necked round bottom flask was charged 300mg of the first compound, 140mg of 5-aldehyde-2-thiopheneboronic acid, 37.5mg of Pd (PPh) 3 ) 4 448.5mg of K 2 CO 3 And 30mL tetrahydrofuran, deoxygenated for 15min, at N 2 Heating, stirring and refluxing overnight at 85-120 ℃ under the atmosphere. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, petroleum ether: dichloromethane=1:1 as eluent) to give a red solid as the second compound in 65% yield (205 mg).
Of a second compound 1 The H NMR spectrum is shown in fig. 4: 1 H NMR(400MHz,DMSO-d 6 )：δ 10.00(s,1H),8.24(d,J＝4.1Hz,1H),8.08(d,J＝7.5Hz,1H),7.95–7.86(m,3H),7.77(d,J＝7.5Hz,1H),7.40–7.28(m,4H ),7.26–7.18(m,6H),7.12(dd,J＝7.3,1.2Hz,2H)。
the synthetic scheme for the second compound is shown below:
example 3
The synthesis method of the third compound comprises the following steps:
into a 100mL three-necked round bottom flask was charged 300mg of the first compound, 127mg of 4-formylphenylboronic acid, 37.5mg of Pd (PPh) 3 ) 4 448.5mg of K 2 CO 3 And 30mL toluene, deoxygenated for 15min, at N 2 Under the atmosphereHeating, stirring and refluxing at 85-120 ℃ for overnight. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, petroleum ether: dichloromethane=1:1 as eluent) to give compound 3 as an orange solid in 62% yield (192 mg).
The synthetic scheme for the third compound is shown below:
example 4
The synthesis method of the fourth compound comprises the following steps:
to a 100mL three-necked round bottom flask was added 924mg of the first compound, 415mg of diethyl phosphite, 115.5mg of Pd (PPh 3 ) 4 8mL of triethylamine and 30mL of toluene, deoxygenated for 15min, at N 2 Heating, stirring and refluxing overnight at 85-120 ℃ under the atmosphere. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, CH 2 Cl 2 : ethyl acetate=100:1 as eluent) to give an orange-yellow solid as fourth compound in 86% (890 mg).
Of a fourth compound 1 The H NMR spectrum is shown in fig. 5: 1 H NMR(400MHz,DMSO-d 6 )：δ8.23(dd,J＝15.7,7.2 Hz,1H),7.97(d,J＝8.7Hz,2H),7.93(dd,J＝7.3,3.0Hz,1H),7.38(dd,J＝8.3,7.3Hz,4H),7.17–7.07(m,8H),4.20–4.11( m,3H),1.26(t,J＝7.1Hz,6H).
the synthetic scheme for the fourth compound is shown below:
example 5
The synthesis method of the fifth compound comprises the following steps:
to a 150mL dry three-necked round bottom flask was added 1764mg of 4, 7-dibromobenzo [ c ]][1,2,5]Thiadiazole, 1724mg of 4-borate-4 ',4' -dimethoxytriphenylamine, 231mg of Pd (PPh) 3 ) 4 1380mg of K 2 CO 3 And 80mL toluene deoxygenated for 15min and under N 2 Heating, stirring and refluxing at 85-120 ℃ under the atmosphere for overnight. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, petroleum ether: dichloromethane=1:1 as eluent) to give a dark red solid as the fifth compound in 65% yield (1360 mg).
Of a fifth compound 1 The H NMR spectrum is shown in fig. 6: 1 H NMR(400MHz,DMSO-d 6 )：δ8.06(d,J＝7.7Hz,1H),7.82 (d,J＝8.8Hz,2H),7.68(d,J＝7.7Hz,1H),7.11(d,J＝8.9Hz,4H),6.95(d,J＝9.0Hz,4H),6.87(d,J＝ 8.8Hz,2H)。
of a fifth compound 13 The C NMR spectrum is shown in FIG. 7: 13 C NMR(400MHz,DMSO-d 6 )：δ156.57,153.68,152.95, 149.31,140.05,133.10,130.37,127.61,118.81,115.51,111.28,55.73。
the synthetic scheme for the fifth compound is shown below:
example 6
The synthesis method of the sixth compound comprises the following steps:
to a 100mL three-necked round bottom flask was added 1044mg of the fifth compound, 415mg of diethyl phosphite, 115.5mg of Pd (PPh) 3 ) 4 8mL of triethylamine and 30mL of toluene, deoxygenated for 15min, at N 2 Atmosphere ofHeating and stirring at 85-120 deg.c for refluxing overnight. After cooling to room temperature, the reaction mixture was dried under reduced pressure to dryness, and the reaction solvent was dried over CH 2 Cl 2 Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were dried over anhydrous Na 2 SO 4 And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, dichloromethane: ethyl acetate=30:1 as eluent) to give a dark red solid as the sixth compound in 75% yield (865 mg).
Of the sixth compound 1 The H NMR spectrum is shown in fig. 8: 1 H NMR(400MHz,DMSO-d 6 )：1H NMR(400MHz,DMSO-d6) δ8.20(dd,J＝15.6,7.3Hz,1H),7.90(d,J＝8.9Hz,2H),7.67–7.62(m,2H),7.14(d,J＝8.9Hz,4H),6.97 (d,J＝9.0Hz,4H),6.88(d,J＝8.9Hz,2H),4.14(ddd,J＝10.1,8.4,7.0Hz,3H),1.25(t,J＝7.0Hz,6H).
the synthetic scheme for the sixth compound is shown below:
example 7
The preparation method of the organic hole transport material shown in the chemical formula P1 comprises the following steps:
to a 50mL round bottom flask was added 122mg of the second compound, 95mg of cyanoacetic acid, 21.3mg of piperidine and 15mL acetic acid. At N 2 The reaction mixture was heated at reflux (85 ℃ C. To 120 ℃ C.) under an atmosphere overnight. After the reaction was completed, acetic acid was dried by spin-drying under reduced pressure, piperidine was washed with water, and the product was extracted with dichloromethane. The organic layer was collected with anhydrous Na 2 SO 4 Dried and evaporated under reduced pressure. The remaining crude product was purified by column chromatography (silica gel, dichloromethane: methanol: acetic acid=20:1:0.1 as eluent) to give compound P1 (107 mg, 77%) as a dark red solid.
Compound P1 1 The H NMR spectrum is shown in fig. 9: 1 H NMR(400MHz,DMSO-d 6 )：8.32(d,J＝7.6Hz,1H),8.27(d, J＝4.1Hz,1H),8.08(d,J＝4.2Hz,1H),7.97(d,J＝8.8Hz,2H),7.91(d,J＝7.7Hz,1H),7.37(dd,J＝8.7, 7.1Hz,4H),7.15–7.06(m,8H).
compound P1 13 The C NMR spectrum is shown in FIG. 10: 13 C NMR(400MHz,DMSO-d 6 )δ164.0,153.4,152.3,148.3, 147.9,147.2,140.3,137.1,133.7,130.8,130.2,130.1,128.4,128.2,127.5,125.2,124.2,123.7,122.3.
the HRMS spectrum of compound P1 is shown in fig. 11: HRMS (ESI) M/z: [ M ]]+Calcd for C 32 H 20 N 4 O 2 S 2 :555.0948。
The synthetic flow of the organic hole transport material with the chemical formula shown as P1 is as follows:
example 8
The preparation method of the organic hole transport material with the chemical formula shown as P2 comprises the following steps:
to a 50mL round bottom flask was added 120mg of the third compound, 95mg of cyanoacetic acid, 21.3mg of piperidine and 15mL acetic acid. At N 2 The reaction mixture was heated at reflux (85 ℃ C. To 120 ℃ C.) under an atmosphere overnight. After the reaction was completed, acetic acid was dried by spin-drying under reduced pressure, piperidine was washed with water, and the product was extracted with dichloromethane. The organic layer was collected with anhydrous Na 2 SO 4 Dried and evaporated under reduced pressure. The remaining crude product was purified by column chromatography (silica gel, dichloromethane: methanol: acetic acid=20:1:0.1 as eluent) to give compound P2 (98 mg, 71%) as a dark orange solid.
Compound P2 1 The H NMR spectrum is shown in fig. 12: 1 H NMR(400MHz,DMSO-d 6 )：δ 8.36–8.19(m,3H),8.15(d,J＝8.3Hz,2H),8.07(d,J＝7.4Hz,1H),7.96(dd,J＝12.3,7.9Hz,3H),7.37(t,J＝7.7 Hz,4H),7.12(d,J＝7.8Hz,8H).
compound P2 13 The C NMR spectrum is shown in FIG. 13: 13 C NMR(400MHz,DMSO-d 6 )δ172.5,163.8,154.0,153.7, 153.6,148.1,147.3,141.5,133.3,131.6,131.3,130.7,130.5,130.3,130.2,130.1,129.7,127.6,125.1,124.1, 122.5,116.7,104.3.
the HRMS spectrum of compound P2 is shown in fig. 14: HRMS (ESI) M/z: [ M ]]+Calcd for C 34 H 22 N 4 O 2 S:549.1384。
The synthetic flow of the organic hole transport material with the chemical formula shown as P2 is as follows:
example 9
The preparation method of the organic hole transport material with the chemical formula shown as P3 comprises the following steps:
to a 50mL round bottom flask was added 515mg of the fourth compound, 20mL of dichloromethane to dissolve. 3mL of trimethylbromosilane was slowly added dropwise by means of a syringe, and the reaction was carried out at room temperature for 12 hours. When the reaction was complete, it was washed with a large amount of water and the product was extracted with dichloromethane. The organic layer was collected with anhydrous Na 2 SO 4 Dried and evaporated under reduced pressure to give compound P3 (365 mg, 80%) as a pale orange solid.
Compound P3 1 The H NMR spectrum is shown in fig. 15: 1 H NMR(400MHz,CDCl 3 )：δ7.67(dd,J＝12.1,7.5Hz,1H), 7.54(d,J＝7.4Hz,2H),7.49–7.41(m,1H),7.21(t,J＝7.7Hz,4H),7.13–6.95(m,8H).
compound P3 13 The C NMR spectrum is shown in FIG. 16: 13 C NMR(400MHz,DMSO-d 6 )：δ148.24,147.24,132.51, 131.98,131.89,130.78,130.15,129.27,129.15,125.04,124.12,122.50.
the HRMS spectrum of compound P3 is shown in fig. 17: HRMS (ESI) M/z: [ M ]]+Calcd for C 24 H 18 N 3 O 3 PS:458.0726。
The synthetic flow of the organic hole transport material with the chemical formula shown as P3 is as follows:
example 10
The preparation method of the organic hole transport material with the chemical formula shown as P4 comprises the following steps:
to a 50mL round bottom flask was added 575mg of the sixth compound, 20mL of dichloromethane to dissolve. 3mL of trimethylbromosilane was slowly added dropwise by means of a syringe, and the reaction was carried out at room temperature for 12 hours. When the reaction was complete, it was washed with a large amount of water and the product was extracted with dichloromethane. The organic layer was collected with anhydrous Na 2 SO 4 Dried and rotary distilled under reduced pressure to give compound P4 (410 mg, 79%) as a black-red solid.
Compound P4 1 The H NMR spectrum is shown in fig. 18: 1 H NMR(400MHz,Chloroform-d)：1H NMR(400MHz, Chloroform-d)δ7.79–7.39(m,4H),6.81(s,10H),3.78(s,6H).
the HRMS spectrum of compound P4 is shown in fig. 19: HRMS (ESI) M/z: [ M ]]+Calcd for C 26 H 22 N 3 O 5 PS:518.0935。
The synthetic flow of the organic hole transport material with the chemical formula shown as P4 is as follows:
example 11
The embodiment of the application provides a preparation method of a perovskite solar cell, which comprises the following steps:
s1, sequentially ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol for 15min respectively, and finally drying in a drying oven at 75 ℃ for later use; placing the dried ITO glass substrate into an ultraviolet ozone machine for treatment for 5min, removing organic impurities on the surface of the ITO glass substrate, and optimizing the surface wettability of the ITO glass substrate;
s2, dissolving 1mg of the organic hole transport material P1 prepared in the example 7 in 2mL of chlorobenzene, and stirring at normal temperature until the organic hole transport material P1 is completely dissolved to obtain an organic hole transport material solution;
s3, taking 30uL of organic hole transport material solution, dripping the solution on the treated ITO glass, spin-coating the solution for 30S at a rotation speed of 5000rpm, and heating and annealing the ITO glass in the S1 on a hot table at 100 ℃ for 10min to form a hole transport layer;
s4, dissolving 722.08mg of lead iodide and 238.50mg of iodomethylamine solid in 1mL of N, N-Dimethylformamide (DMF), and stirring at normal temperature until the lead iodide and the 238.50mg of iodomethylamine solid are completely dissolved to obtain a perovskite precursor solution;
s5, in a nitrogen glove box, dripping 30uL of perovskite precursor solution onto ITO conductive glass for forming a hole transport layer, spin-coating at 1000rpm for 10S, spin-coating at 5000rpm for 30S, rapidly dripping 125uL of ethyl acetate in the process for 25S, and then heating and annealing the ITO glass on a hot table at 100 ℃ for 40min to form a perovskite layer;
s6, dissolving 20mg of methane fullerene phenyl-C61-butyric acid-methyl ester (PCBM) in 1mL of chlorobenzene, and stirring at normal temperature to obtain a [6,6] -phenyl-C61-butyric acid methyl ester solution;
s7, spin-coating 30uL of [6,6] -phenyl-C61-methyl butyrate solution on ITO conductive glass with a perovskite layer formed by the solution at 3000rpm for 60S to form an electron transport layer;
s7, dissolving 0.5mg of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) in 1mL of isopropanol, and stirring at normal temperature to obtain a hole blocking layer solution;
s8, dripping 40uL of hole blocking layer solution above the electron transport layer, and spin-coating for 35S at 5000rpm to form a hole blocking layer;
s9, transferring the ITO conductive glass with the hole blocking layer, the PCBM electron transport layer, the perovskite layer and the hole transport layer into a vacuum coating instrument, and pumping the vacuum degree to 3 multiplied by 10 -4 Evaporating silver electrode during Pa to form 100nm thick silver electrode to obtain electrode layer.
Example 12
The embodiment of the application provides a method for preparing a perovskite solar cell, which is similar to embodiment 11, and is different from embodiment 11 in that the organic hole transport material is P2.
Example 13
The embodiment of the application provides a method for preparing a perovskite solar cell, which is similar to embodiment 11, and is different from embodiment 11 in that the organic hole transport material is P3.
Example 14
The embodiment of the application provides a method for preparing a perovskite solar cell, which is similar to embodiment 11, and is different from embodiment 11 in that the organic hole transport material is P4.
Performance testing
The organic hole transport materials of the chemical formulas P1 to P4 synthesized in examples 7 to 10 were subjected to ultraviolet light physical property and electrochemical performance tests, and the test methods are as follows:
(1) Ultraviolet-visible absorption spectrum
Testing with ultraviolet visible near infrared spectrophotometer (SolidSpec-3700); organic hole transport materials with chemical formulas as P1-P4 are respectively prepared into 1.0X10 –5 Samples of M in tetrahydrofuran were measured for their uv-vis absorption spectra. Ultraviolet-visible absorption spectra of P1 to P4 in tetrahydrofuran (1.0X10) –5 M) is shown in fig. 20.
As can be seen from fig. 20, the organic hole transport materials P1 and P2 each have three absorption peaks in the region of 300 to 600nm, whereas P4 and P4 have only two absorption peaks in the region of 300 to 600nm, and P1 and P2 have one more weak absorption peak at 350 to 410nm compared to P4 and P4. The absorption band 300 to 330nm originates from the electron transition of triphenylamine and the absorption band 330 to 600nm originates from the pi-pi transition of the whole molecule. At the same time, the wavelength (lambda) of the maximum absorption edge of P1 to P4 max ) 580, 535, 509 and 574nm, respectively, according to band gap E g ＝1240/λ max Obtaining E of P1 to P4 g 2.14, 2.32, 2.44 and 2.16eV, respectively.
Spin-coating perovskite precursor solution on ITO substrate to form MAPbI 3 A membrane; organic hole-transporting materials of the formula P1-P4 and poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA) spin-coating on ITO substrate, and then spin-coating perovskite precursor solution on P1-P4 and PTAA to form different MAPbI 3 A membrane; testing different MAPbI Using SolidSpec-3700 ultraviolet visible near infrared Spectrophotometer 3 The absorbance of the film was shown in FIG. 21.
In FIG. 21, perovskite represents MAPbI formed by spin coating a Perovskite precursor solution directly onto an ITO substrate 3 A membrane;PTAA/Perovski means that PTAA is spin-coated onto an ITO substrate and then the spin-coated Perovskite precursor solution is used to form MAPbI 3 A membrane; the same applies to P1-P4/Perovskite, which respectively represent MAPbI formed by spin-coating P1-P4 on an ITO substrate and then spin-coating a Perovskite precursor solution 3 And (3) a film.
In fig. 21, the absorption ranges from visible light up to the near infrared region. The initial absorption wavelength (λonset. Apprxeq.780 nm) corresponds to MAPbI 3 Is a band gap of (c). Compared with the spin coating on ITO and PTAA, the perovskite thin films spin-coated on the organic hole transport materials P1-P4 have higher absorbance, can reduce the absorption loss of incident photons, and is a favorable property for ideal HTM.
(2) Electrochemical Properties
Cyclic voltammetry was performed using an electrochemical workstation (Zahner zenium) with 0.1M tetra-n-butyl ammonium hexafluorophosphate (Bu 4 NPF 6 ) In methylene chloride as a supporting electrolyte. The working electrode is a platinum wire electrode; the counter electrode is a platinum sheet electrode; the reference electrode is a silver electrode (saturated potassium chloride solution). And using a ferrocene/ferrocene redox pair (Fc/Fc + ) As a reference for all measurements, the scan rate was 50mV/s. Cyclic voltammograms (1.0X10) of organic hole transport materials P1 to P4 in methylene chloride –4 M) is shown in fig. 22. P1 to P4 each have a pair of redox peaks, and the cyclic voltammograms of both are highly reversible, indicating their excellent electrochemical stability.
(3) Energy level of organic hole transport material
By the formula homo= -5.1 (E ox -E 1/2(Fc/Fc+) ) The HOMO orbital levels for P1-P4 can be obtained by eV calculation. Band gap ΔE by ultraviolet-visible absorption spectroscopy g And the HOMO energy level from the cyclic voltammogram, using the formula lumo=homo+Δe g LUMO energy levels can be calculated and the results are shown in table 1:
TABLE 1 energy level data sheet of hole transport materials
| HTM | λ max,abs /nm | E ox (eV) | HOMO(eV) | LOMO(eV) | E gap (eV) |
| P1 | 582 | 0.789 | -5.31 | -3.17 | 2.14 |
| P2 | 536 | 0.794 | -5.31 | -2.99 | 2.32 |
| P3 | 511 | 0.757 | -5.28 | -2.96 | 2.44 |
| P4 | 574 | 0.495 | -5.02 | -2.86 | 2.16 |
The HOMO energy levels of P1-P4 are respectively-5.31, -5.31eV, -5.28 and-5.02 eV, compared with MAPbI 3 Is high (-5.45 eV) and can promote hole transfer. The energy levels of perovskite solar cells in examples 11 to 14 are shown in fig. 23, in which ITO is conductive glass, perovskie is perovskite layer, and PCBM is electron transport layer.
(4) Thermal analysis
The test condition of thermogravimetric analysis (NETZSCH STA 449F 3 Jupiter) is N 2 The atmosphere and the temperature rise interval are 30-600 ℃, and the temperature rise rate is 10.0K/min. The results of thermogravimetric analysis of the organic hole transport materials P1 to P4 are shown in fig. 24. Decomposition temperature (T) d ) Defined as the temperature at 5% weight loss, it can be seen from FIG. 24 that Td of P1-P4 are 321.5 ℃, 180.0 ℃, 285.5 ℃ and 270.0 ℃ respectively, and the results indicate that P2 has poor thermal stability, P3 and P4 are relatively good in thermal stability, and P1 has the best thermal stability.
The perovskite solar cells prepared in examples 11 to 14 were tested and the current density-voltage curve (J-V curves) of the device was measured by the AM 1.5G (100 mW cm) provided by the source table (Keithley 2400) in the solar simulator (ABET Sun 3000) –2 ) Obtained under illumination, the cell area is 0.08cm 2 The light intensity before test is corrected by a standard silicon cell, the scanning speed is 10mV/s, and the scanning direction is positive and negative scanning.
The positive and negative sweep J-V curves of the perovskite solar cells (P1 to P4 for the hole transport layers respectively) prepared in examples 11 to 14 are shown in fig. 25, the photovoltaic parameters are shown in table 2, the highest cell efficiency (19.95%) based on P1, followed by cells based on P3 (18.82%), P2 (17.92%) and P4 (17.00%).
TABLE 2 photovoltaic parameters of perovskite solar cells prepared in different examples
In conclusion, the results show that the hole transport material synthesized by the invention and taking benzo [ c ] [1,2,5] thiadiazole as a core has higher photoelectric conversion efficiency when applied to a perovskite solar cell, and has good application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. An organic hole transport material is characterized in that the chemical formula of the organic hole transport material is shown as any one of P3 to P4:
2. a method for producing an organic hole transporting material according to claim 1, wherein,
the preparation method of the organic hole transport material of the chemical formula P3 comprises the following steps:
under the protection of inert gas, reacting the first compound with diethyl phosphinate under an alkaline condition to obtain a fourth compound;
under the protection of inert gas, carrying out hydrolysis reaction on a fourth compound and trimethyl bromosilane to obtain an organic hole transport material with a chemical formula P3;
the preparation method of the organic hole transport material of the chemical formula P4 comprises the following steps:
under the protection of inert gas, 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole and 4-borate-4 ',4' -dimethoxy triphenylamine react under the alkaline condition to obtain a fifth compound;
under the protection of inert gas, reacting a fifth compound with diethyl phosphinate under an alkaline condition to obtain a sixth compound;
under the protection of inert gas, carrying out hydrolysis reaction on a sixth compound and trimethyl bromosilane to obtain an organic hole transport material with a chemical formula P4;
the structural formula of the first compound is
The structural formula of the fourth compound is
The structural formula of the fifth compound is
/>
The structural formula of the sixth compound is
3. Use of the organic hole transport material of claim 1 for the preparation of perovskite solar cells and organic light emitting diodes.
4. The perovskite solar cell is characterized by comprising a substrate, a hole transport layer, a perovskite layer, an electron transport layer, a hole blocking layer and an electrode layer which are sequentially stacked; the hole transport layer is prepared from the organic hole transport material of claim 1.
5. The perovskite solar cell according to claim 4, wherein the electron transport layer is made of [6,6] -phenyl-C61-methyl butyrate, the hole blocking layer is made of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and the electrode layer is made of silver.
6. A method of manufacturing a perovskite solar cell as claimed in any one of claims 4 to 5, comprising the steps of:
providing a substrate;
preparing an organic hole transport material solution, and coating the organic hole transport material solution on a substrate to prepare a hole transport layer;
preparing a perovskite precursor solution, and coating the perovskite precursor solution on the hole transport layer to prepare a perovskite layer;
preparing an electron transport material solution and coating the electron transport material solution on a perovskite layer to prepare an electron transport layer;
preparing a hole blocking layer solution and coating the hole blocking layer solution on an electron transport layer;
an electrode layer is prepared on the electron transport layer.
7. The method for manufacturing a perovskite solar cell according to claim 6, wherein the organic hole transport material solution is prepared specifically as follows: and dissolving the organic hole transport material in chlorobenzene, and stirring and dissolving to obtain the organic hole transport material, wherein the mass-volume ratio of the organic hole transport material to the chlorobenzene is 2mg (1-3) mL.
8. The method for preparing a perovskite solar cell according to claim 7, wherein the organic hole transport material solution is coated on a substrate, and the preparation of the hole transport layer is specifically: and spin-coating the organic hole transport material solution on the substrate by using a spin-coating method, wherein the spin-coating speed is 5000-6000 r/min, the spin-coating time is 30-60 s, and annealing is performed for 8-12 min at 80-120 ℃ after the spin-coating is completed.
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