CN113979969A - 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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- CN113979969A CN113979969A CN202111176906.5A CN202111176906A CN113979969A CN 113979969 A CN113979969 A CN 113979969A CN 202111176906 A CN202111176906 A CN 202111176906A CN 113979969 A CN113979969 A CN 113979969A
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- Prior art keywords
- hole transport
- transport material
- compound
- organic hole
- organic
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- 239000000463 material Substances 0.000 title claims abstract description 110
- 230000005525 hole transport Effects 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 107
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- 239000000758 substrate Substances 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002243 precursor Substances 0.000 claims description 13
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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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- 239000004332 silver Substances 0.000 claims description 7
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- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 6
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- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
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- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
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- -1 hexafluorophosphate Chemical compound 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
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Images
Classifications
-
- 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 as follows:
organic cavities of the inventionA transport material, Ar is a triphenylamine derivative with semiconductor characteristics, and the energy level of Ar is adjusted according to the electron donating and electron withdrawing characteristics of Ar; r3The organic semiconductor material is a pi-spaced conjugated aromatic system, expands pi-conjugated fine-tuning hole mobility and energy level, makes the distribution of electrons in molecules more uniform, and simultaneously, the molecules tend to be planar, so that the stacking behavior of organic semiconductor molecules is effectively regulated and controlled, and further the hole transmission capability is improved. R4The anchoring group containing hydrogen bond donor acceptor can produce chemical reaction or supermolecular interaction with the surface interface of electrode material or P-type semiconductor material. When the hole transport material is applied to the perovskite solar cell, the carrier transport performance and interface contact stability of an electrode/perovskite interface or a P-type hole transport layer/perovskite interface can be effectively enhanced.
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 memories, and especially solar cells due to their long carrier diffusion length, efficient bipolar charge transport, broad light absorption and large absorption coefficient, making them of great interest in the field of optoelectronics and have become one of the most popular active materials in the subject of this study. Metal halide Perovskite Solar Cells (PSCs) have attracted considerable attention in the scientific and industrial sectors over the last few years due to their interesting photophysical properties, high Power Conversion Efficiencies (PCEs) and great potential for low cost processing.
The interfacial properties between the perovskite light absorbing layer and the Hole Transport Material (HTM) are heavily 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 needs to be doped to provide high Photoelectric Conversion Efficiency (PCE) for PSCs, and PTAA is even more costly (1980$/g), making it impossible to mass-produce PSCs. Therefore, research on the HTM with simple synthesis and purification, low cost and excellent performance has important significance for realizing commercialization of the perovskite battery.
Disclosure of Invention
In view of the above, the invention provides an organic hole transport material, a preparation method and an application thereof, and a perovskite solar cell, so as to solve or partially solve the technical problems 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, R1、R2Is hydrogen, or is an aromatic group or an alkyl group containing hetero atoms;
R3is composed of
Any one of the above, wherein n is a positive integer between 0 and 10;
R4is composed of
-(CnH2n)PO3H2、-(CnH2n)COOH、-(CnH2n)SO3H2、-(CnH2n)Si(OH)3， -(CnH2n)B(OH)2，-(CnH2n) Any one of 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 preparation of perovskite solar cells and organic light emitting diodes.
In a fourth aspect, the invention further provides a perovskite solar cell, which comprises 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 further 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 organic hole transport material of the present invention, and benzo [ c ]][1,2,5]Thiadiazole is used as a center, Ar is a triphenylamine derivative with semiconductor characteristics, and the triphenylamine derivative and the perovskite component generate Lewis acid-base interaction, and the energy level of the triphenylamine derivative is adjusted according to the electron donating and electron withdrawing characteristics of the triphenylamine derivative; r3The organic semiconductor material is a pi conjugated aromatic system, the stacking behavior of organic semiconductor molecules is regulated and controlled, and further the hole transmission capability is improved, and the pi conjugated system is usually easy to synthesize and shows excellent optical and electrochemical properties. In addition, their structure can be easily adjusted to adjust their optical, electrochemical properties and thermal stability. R4An anchoring group containing a hydrogen bond donor acceptor, and chemically reacting or supramolecular interacting with an electrode or a P-type semiconductor substrate. The hole transport material is simple to synthesize, low in cost, good in stability and strong in 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. In organic light emitting diodes and solar energyThe method has high application value in the photoelectric field such as batteries 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 obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural view of a perovskite solar cell of the present invention;
FIG. 2 shows a first compound1H NMR spectrum;
FIG. 3 shows a first compound13C NMR spectrum;
FIG. 4 shows a second compound1H NMR spectrum;
FIG. 5 shows a fourth compound1H NMR spectrum;
FIG. 6 shows a fifth compound1H NMR spectrum;
FIG. 7 shows a fifth compound13C NMR spectrum;
FIG. 8 shows a sixth compound1H NMR spectrum;
FIG. 9 is a drawing of Compound P11H NMR spectrum;
FIG. 10 shows Compound P113C NMR spectrum;
FIG. 11 is a HRMS spectrum of Compound P1;
FIG. 12 is a drawing of Compound P21H NMR spectrum;
FIG. 13 preparation of Compound P213C NMR spectrum;
figure 14 HRMS spectrum of compound P2;
FIG. 15 is a drawing of Compound P31H NMR spectrum;
FIG. 16 of Compound P313C NMR spectrum;
figure 17 HRMS spectrum of compound P3;
FIG. 18 is a drawing of Compound P41H NMR spectrum;
FIG. 19 HRMS spectrum of Compound P4;
FIG. 20 is a chart of UV-VIS absorption spectra of organic hole transporting materials P1-P4 in tetrahydrofuran;
FIG. 21 is MAPbI3The film is coated on the ultraviolet-visible absorption spectrogram of ITO, P1-P4 and PTAA in a spinning mode;
FIG. 22 is a plot of cyclic voltammograms of organic hole transport materials P1-P4 in dichloromethane;
FIG. 23 is a graph showing energy levels of perovskite solar cells according to examples 11 to 14;
FIG. 24 is a thermogravimetric analysis of the organic hole transporting materials P1-P4;
FIG. 25 is a positive-negative sweep J-V plot of perovskite solar cells prepared in examples 11-14.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides an organic hole transport material, and the chemical formula of the organic hole transport material is as follows:
wherein Ar is
Any one of, R1、R2Is hydrogen, or is an aromatic group or an alkyl group containing hetero atoms; r3Is composed of
Any one of the above, wherein n is a positive integer between 0 and 10; r4Is composed of
-(CnH2n)PO3H2、-(CnH2n) COOH、-(CnH2n)SO3H2、-(CnH2n)Si(OH)3，-(CnH2n)B(OH)2，-(CnH2n) SH, and the like, wherein n is a positive integer between 0 and 5.
In particular, R1、R2Can be aromatic group or alkyl group containing heteroatom such as oxygen, nitrogen, fluorine, sulfur, phosphorus, chlorine, selenium, arsenic, bromine, iodine, etc., such as:
-OCnH2n+1、-SCnH2n+1any one of-H, wherein n is a positive integer between 1 and 5; r is as defined above4Is a reactive anchoring group capable of chemical reaction or supramolecular interaction with hydrogen bond donor or acceptor groups at the surface interface of the electrode or inorganic semiconductor.
In some embodiments, the hole transport material has the formula:
r is
-PO3H2Any one of the above.
In some embodiments, the organic hole transport material has a chemical formula as shown in any one of P1-P4:
based on the same inventive concept, the embodiment of the present application further provides a preparation method of the organic hole transport material with the chemical formula shown as P1-P4, specifically, the preparation method of the organic hole transport material with the chemical formula of P1 comprises the following steps:
s11, reacting 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole and (4- (diphenylamino) phenyl) boric acid under an alkaline condition to obtain a first compound; s12, reacting the first compound with 5-aldehyde-2-thiopheneboronic acid under the protection of inert gas under the alkaline condition to obtain a second compound; s13, reacting the second compound with cyanoacetic acid under the protection of inert gas to obtain the organic hole transport material with the chemical formula of P1;
the preparation method of the organic hole transport material with the chemical formula of P2 comprises the following steps:
s21, reacting the first compound with 4-formylphenylboronic acid under the protection of inert gas under the alkaline condition to obtain a third compound; s22, reacting the third compound with cyanoacetic acid under the protection of inert gas to obtain the organic hole transport material with the chemical formula of P2;
the preparation method of the organic hole transport material with the chemical formula of P3 comprises the following steps:
s31, under the protection of inert gas, reacting the first compound with diethyl phosphinate under alkaline conditions 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 the organic hole transport material with the chemical formula of P3;
the preparation method of the organic hole transport material with the chemical formula of P4 comprises the following steps:
s41, under the protection of inert gas, reacting 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole and 4-boric acid ester-4 ',4' -dimethoxytriphenylamine under an 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, under the protection of inert gas, the sixth compound and trimethyl bromosilane are subjected to hydrolysis reaction, and the organic hole transport material with the chemical formula of P4 is obtained.
Specifically, the structural formula of the first compound is
The second compound has a structural formula of
The third compound has the structural formula
The fourth compound has the structural formula
The fifth compound has the structural formula
The sixth compound has the structural formula
Specifically, in some embodiments, in step S11, the molar ratio of 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole to 4-boronate-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 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 h, the alkali used in the reaction is potassium carbonate, the catalyst is tetrakis (triphenylphosphine) palladium, and the solvent is toluene.
In the step 12, the molar ratio of the first compound to the 5-aldehyde-2-thiopheneboronic acid is 1:, the reaction temperature is 85-120 ℃, the reaction time is 5-24 hours, the alkali is potassium carbonate, the catalyst is tetrakis (triphenylphosphine) palladium, and the solvent is tetrahydrofuran.
In the step 21, the molar ratio of the first compound to the 4-formylphenylboronic acid is 1 (1.2-3), the reaction temperature is 85-120 ℃, the reaction time is 5-24 h, the alkali is potassium carbonate, and the catalyst is tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) And the solvent is tetrahydrofuran.
In the step S31, the molar ratio of the first compound to diethyl phosphite is 1 (2-5), the reaction temperature is 85-120 ℃, the reaction time is 5-24 h, the base is triethylamine, the catalyst is tetrakis (triphenylphosphine) palladium, and the solvent is toluene.
In the step S42, the molar ratio of the fifth compound to diethyl phosphite is 1 (2-5), the reaction temperature is 85-120 ℃, the reaction time is 5-24 h, the base is triethylamine, the catalyst is tetrakis (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 base is piperidine, and the solvent is acetic acid.
In the step S32, the molar ratio of the fourth compound to the trimethylbromosilane is 1 (4-5), the reaction temperature is 20-25, the reaction time is 6-12 hours, and the solvent is dichloromethane.
In the step S43, the molar ratio of the sixth compound to the trimethylbromosilane 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 the application of the organic hole transport material in the preparation of 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 prepared from the organic hole transport material described above.
In some embodiments, the material of the electron transport layer 4 is [6,6] -phenyl-C61-methyl butyrate, the material of the hole blocking layer 5 is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and the material of the electrode layer 6 is 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 specifically formulated as: 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 organic hole transport material solution is coated on the substrate, and the hole transport layer is prepared by: 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 carried out at 80-120 ℃ for 8-12 min after the spin-coating is finished.
In some embodiments, the perovskite precursor solution (i.e., MAPbI) in step S33Solution) is prepared by the following steps: 722.08mg of lead iodide and 238.50mg of iodomethylamine solid were dissolved in 1mL of N, N-Dimethylformamide (DMF),stirring at normal temperature until the components are completely dissolved; coating the perovskite precursor solution on the hole transport layer by using a spin coating method, wherein the specific spin coating method comprises the following steps: and spin-coating at a speed of 1000r/min for 10s in a nitrogen glove box, then spin-coating at a speed of 5000r/min for 30s, dropwise adding 125 mu L of ethyl acetate onto the hole transport layer during the second spin-coating for 15s, and annealing at 100 ℃ for 40min after the spin-coating is finished to obtain the perovskite layer.
In some embodiments, the step S4 of preparing the electron transport layer specifically includes: dissolving 20mg of [6,6] -phenyl-C61-methyl butyrate (PCBM) in 1mL of chlorobenzene, and stirring at normal temperature until the PCBM is completely dissolved to obtain a [6,6] -phenyl-C61-methyl butyrate solution; the [6,6] -phenyl-C61-butyric acid methyl ester solution was further spin-coated on the perovskite layer at 3000r/min for 60s in a nitrogen glove box.
In some embodiments, a solution of the hole blocking layer material is prepared 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 solution is completely dissolved to obtain a 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) solution; in a nitrogen glove box, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) solution is spin-coated on the electron transport layer at 5000r/min for 35 s.
In some embodiments, the step S6 of preparing the electrode layer on the electron transport layer specifically includes: the electrode layer is prepared by adopting a vacuum coating method, which comprises the following steps: in a vacuum coating apparatus, the vacuum degree is pumped to 3 × 10-4And (3) evaporating a silver electrode at about Pa to finally form the silver electrode with the thickness of 100 nm.
In some embodiments, the substrate is ITO conductive glass.
The following further describes the preparation method and application of the organic hole transport material of the present application with specific examples.
Example 1
The synthesis method of the first compound comprises the following steps:
to a 150mL dry three-neck round bottom flask was added 1470mg of 4, 7-dibromobenzo [ c ]][1,2,5]Thiadiazole, 950mg of (4- (diphenylamino) phenyl) boronic acid, 116mg of Pd (PPh)3)42760mg of K2CO3And 70mL of toluene, deoxygenated for 15min, and stored under N2Heating, stirring and refluxing overnight at 85-120 ℃ under the atmosphere. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (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 the first compound as an orange solid in 60% yield (457 mg).
Of a first compound1The H NMR spectrum is shown in FIG. 2:1H NMR(400MHz,DMSO-d6)：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 compound13The C NMR spectrum is shown in FIG. 3:13C NMR(400MHz,DMSO-d6)：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 as follows:
example 2
The synthesis method of the second compound comprises the following steps:
to a 100mL three-necked round bottom flask was added 300mg of the first compound, 140mg of 5-carboxaldehyde-2-thiopheneboronic acid, 37.5mg of Pd (PPh)3)4448.5mg of K2CO3And 30mL of tetrahydrofuran, deoxygenated for 15min under N2Heating, stirring and refluxing at 85-120 ℃ under atmosphere overnight. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (5) drying. After evaporation of the solvent, the residue is purified by column chromatography (silica gel, petroleum ether: dichloromethane)Alkane-1: 1 as eluent) to give the second compound as a red solid in 65% yield (205 mg).
Of a second compound1The H NMR spectrum is shown in FIG. 4:1H NMR(400MHz,DMSO-d6)：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 as follows:
example 3
The synthesis method of the third compound comprises the following steps:
to a 100mL three-necked round bottom flask were added 300mg of the first compound, 127mg of 4-formylphenylboronic acid, 37.5mg of Pd (PPh)3)4448.5mg of K2CO3And 30mL of toluene, deoxygenated for 15min under N2Heating, stirring and refluxing at 85-120 ℃ under atmosphere overnight. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (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 as follows:
example 4
The synthesis method of the fourth compound comprises the following steps:
into a 100mL three-necked round bottom flask was added 924mg of the first compound, 415mg of diethyl phosphite, 115.5mg of Pd (PPh)3)48mL of threeEthylamine and 30mL of toluene, deoxygenated for 15min under N2Heating, stirring and refluxing at 85-120 ℃ under atmosphere overnight. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (5) drying. After evaporation of the solvent, the residue was purified by column chromatography (silica gel, CH)2Cl2: ethyl acetate 100:1 as eluent) to give the fourth compound as an orange-yellow solid in 86% yield (890 mg).
Of a fourth compound1The H NMR spectrum is shown in FIG. 5:1H NMR(400MHz,DMSO-d6)：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 as follows:
example 5
A method of synthesizing a fifth compound:
to a 150mL dry three-neck 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)41380mg of K2CO3And 80mL of toluene, deoxygenated for 15min, and stored under N2Heating, stirring and refluxing overnight at 85-120 ℃ under the atmosphere. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (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 the fifth compound as a dark red solid in 65% yield (1360 mg).
Of a fifth compound1The H NMR spectrum is shown in FIG. 6：1H NMR(400MHz,DMSO-d6)：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 compound13The C NMR spectrum is shown in FIG. 7:13C NMR(400MHz,DMSO-d6)：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 scheme for the synthesis of the fifth compound is shown below:
example 6
A method of synthesizing a sixth compound:
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)48mL of triethylamine and 30mL of toluene, deoxygenated for 15min under N2Heating, stirring and refluxing at 85-120 ℃ under atmosphere overnight. After cooling to room temperature, the reaction mixture was spin-dried under reduced pressure using CH2Cl2Repeatedly extracting for 3-4 times, and collecting the organic phase in a conical flask. The combined organic layers were passed over anhydrous Na2SO4And (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 the sixth compound as a dark red solid in 75% yield (865 mg).
Of the sixth Compound1The H NMR spectrum is shown in FIG. 8:1H NMR(400MHz,DMSO-d6)：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 as follows:
example 7
A method of preparing an organic hole transport material having the formula P1:
to a 50mL round bottom flask was added 122mg of the second compound, 95mg cyanoacetic acid, 21.3mg piperidine and 15mL acetic acid. In N2The reaction mixture was heated at reflux (85 ℃ C. -120 ℃ C.) under an atmosphere overnight. When the reaction was complete, the acetic acid was spin-dried under reduced pressure, the piperidine was washed with water and the product was extracted with dichloromethane. Collecting the organic layer, and adding anhydrous Na2SO4Dried 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 black red solid.
Of compound P11The H NMR spectrum is shown in FIG. 9:1H NMR(400MHz,DMSO-d6)：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).
of compound P113The C NMR spectrum is shown in FIG. 10:13C NMR(400MHz,DMSO-d6)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 figure 11: HRMS (ESI) M/z [ M ]]+Calcd for C32H20N4O2S2:555.0948。
The synthesis scheme of the organic hole transport material with the chemical formula of P1 is as follows:
example 8
A method of preparing an organic hole transport material having the formula P2:
to a 50mL round bottom flask was added 120mg of the third compound, 95mgCyanoacetic acid, 21.3mg piperidine and 15mL acetic acid. In N2The reaction mixture was heated at reflux (85 ℃ C. -120 ℃ C.) under an atmosphere overnight. When the reaction was complete, the acetic acid was spin-dried under reduced pressure, the piperidine was washed with water and the product was extracted with dichloromethane. Collecting the organic layer, and adding anhydrous Na2SO4Dried 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.
Of compound P21The H NMR spectrum is shown in FIG. 12:1H NMR(400MHz,DMSO-d6)：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).
of compound P213The C NMR spectrum is shown in FIG. 13:13C NMR(400MHz,DMSO-d6)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 figure 14: HRMS (ESI) M/z [ M ]]+Calcd for C34H22N4O2S:549.1384。
The synthesis scheme of the organic hole transport material with the chemical formula of P2 is as follows:
example 9
A method of preparing an organic hole transport material having the formula P3:
a50 mL round-bottom flask was charged with 515mg of the fourth compound and dissolved in 20mL of dichloromethane. 3mL of trimethylbromosilane was slowly added dropwise with a syringe and reacted 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. Collecting the organic layer, and adding anhydrous Na2SO4Drying and rotary evaporation under reduced pressure gave compound P3(365mg, 80%) as a pale orange solid.
Of compound P31The H NMR spectrum is shown in FIG. 15:1H NMR(400MHz,CDCl3)：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).
of compound P313The C NMR spectrum is shown in FIG. 16:13C NMR(400MHz,DMSO-d6)：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 figure 17: HRMS (ESI) M/z [ M ]]+Calcd for C24H18N3O3PS:458.0726。
The synthesis scheme of the organic hole transport material with the chemical formula of P3 is as follows:
example 10
A method of preparing an organic hole transport material having the formula P4:
to a 50mL round-bottomed flask was added 575mg of the sixth compound and dissolved in 20mL of methylene chloride. 3mL of trimethylbromosilane was slowly added dropwise with a syringe and reacted 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. Collecting the organic layer, and adding anhydrous Na2SO4Drying and rotary evaporation under reduced pressure gave compound P4(410mg, 79%) as a black red solid.
Of compound P41The H NMR spectrum is shown in FIG. 18:1H 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 figure 19: HRMS (ESI) M/z [ M ]]+Calcd for C26H22N3O5PS:518.0935。
The synthesis scheme of the organic hole transport material with the chemical formula of 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 and respectively ultrasonically cleaning the ITO conductive glass for 15min by using deionized water, acetone and isopropanol, and finally drying the ITO conductive glass in a drying oven at 75 ℃ for later use; putting 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 embodiment 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, dripping 30uL of organic hole transport material solution on the processed ITO glass, spin-coating for 30S at the rotating speed of 5000rpm, and placing the ITO glass in S1 on a hot bench for heating and annealing 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 iodomethylamine solid are completely dissolved to obtain a perovskite precursor solution;
s5, in a nitrogen glove box, dropwise adding 30uL of perovskite precursor solution onto ITO conductive glass forming a hole transport layer, spin-coating at 1000rpm for 10S, then spin-coating at 5000rpm for 30S, rapidly dropwise adding 125uL of ethyl acetate during the process for 25S, and then placing the ITO glass on a heating table to heat and anneal 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, taking 30uL of 6, 6-phenyl-C61-methyl butyrate solution to form ITO conductive glass with a perovskite layer, and spin-coating 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 at 5000rpm for 35S to form a hole blocking layer;
s9, transferring the ITO conductive glass with the hole barrier layer, the PCBM electron transport layer, the perovskite layer and the hole transport layer into a vacuum coating instrument, and pumping the ITO conductive glass to a vacuum degree of 3 multiplied by 10-4And (4) evaporating a silver electrode at Pa to form a silver electrode with the thickness of 100nm, thus obtaining the electrode layer.
Example 12
The embodiment of the application provides a preparation method of a perovskite solar cell, which is the same as the embodiment 11, and is different from the embodiment 11 in that the organic hole transport material used is P2.
Example 13
The embodiment of the application provides a preparation method of a perovskite solar cell, which is the same as the embodiment 11, and is different from the embodiment 11 in that the organic hole transport material used is P3.
Example 14
The embodiment of the application provides a preparation method of a perovskite solar cell, which is the same as the embodiment 11, and is different from the embodiment 11 in that the organic hole transport material used is P4.
Performance testing
The organic hole transport materials synthesized in examples 7-10 and having chemical formulas of P1-P4 were tested for ultraviolet physical properties and electrochemical properties, and the test methods were as follows:
(1) ultraviolet-visible absorption spectrum
Testing by using an ultraviolet visible near infrared spectrophotometer (SolidSpec-3700); organic hole transport materials with chemical formulas of P1-P4 are respectively prepared into 1.0 multiplied by 10–5M in tetrahydrofuran, and their UV-visible absorption spectra were determined. UV-visible absorption spectra (1.0X 10) of P1-P4 in tetrahydrofuran–5M) is shown in fig. 20.
As can be seen from FIG. 20, the organic hole transporting materials P1 and P2 both have three absorption peaks in the region of 300 to 600nm, whereas P4 and P4 have only two absorptions in the region of 300 to 600nmPeaks, P1 and P2 have a weak absorption peak at 350 to 410nm more than P4 and P4. The absorption band from 300 to 330nm originates from the electronic transition of triphenylamine, and the absorption band from 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-P4max) 580, 535, 509 and 574nm, respectively, according to the band gap Eg＝1240/λmaxTo obtain E of P1 to P4g2.14, 2.32, 2.44 and 2.16eV, respectively.
Spin coating perovskite precursor solution on ITO substrate to form MAPbI3A film; organic hole transport materials with chemical formulas of P1-P4 and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA) is respectively coated on the ITO substrate in a spinning way, and then perovskite precursor solution is respectively coated on the P1-P4 and the PTAA in a spinning way to form different MAPbI3A film; testing of different MAPbI Using SolidSpec-3700 ultraviolet-visible near-infrared Spectrophotometer3The absorbance of the film is shown in FIG. 21.
Wherein in FIG. 21, Perovskite represents MAPbI formed by spin coating a Perovskite precursor solution directly on an ITO substrate3A film; PTAA/Perovskite indicates MAPbI formed by spin coating PTAA onto ITO substrate, followed by spin coating Perovskite precursor solution3A film; similarly, P1-P4/Perovskite respectively indicate that P1-P4 are firstly spin-coated on an ITO substrate, and then MAPbI formed by spin-coating a Perovskite precursor solution3And (3) a membrane.
In fig. 21, the absorption ranges from visible light to near infrared region. The initial absorption wavelength (λ onset ≈ 780nm) corresponds to MAPbI3The band gap of (a). Compared with spin coating on ITO and PTAA, the perovskite thin film spin coated on the organic hole transport materials P1-P4 has higher absorbance, can reduce the absorption loss of incident photons, and is an advantageous property for an ideal HTM.
(2) Electrochemical properties
Cyclic voltammetric measurements were performed using an electrochemical workstation (Zahner Zennium) with 0.1M tetra-n-butylammonium hexafluorophosphate (Bu)4NPF6) Carried out as supporting electrolyte in dichloromethane. 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)Liquid). And using a ferrocene/ferrocene redox couple (Fc/Fc)+) As a reference for all measurements, the scan rate was 50 mV/s. Cyclic voltammograms of organic hole-transporting materials P1-P4 in dichloromethane (1.0X 10)–4M) is shown in fig. 22. The P1-P4 all have a pair of redox peaks, and the cyclic voltammograms of the two are highly reversible, which shows that the two are excellent in electrochemical stability.
(3) Energy level of organic hole transport material
By the formula HOMO ═ 5.1 (E)ox-E1/2(Fc/Fc+)) The HOMO orbital levels of P1-P4 can be obtained by eV calculation. Band gap delta E by UV-visible absorption spectroscopygAnd HOMO energy level obtained from cyclic voltammetry curve by applying formula LUMO ═ HOMO + Δ EgThe LUMO energy level can be calculated and the results are shown in table 1:
table 1 energy level data table for hole transport materials
| HTM | λmax,abs/nm | Eox(eV) | HOMO(eV) | LOMO(eV) | Egap(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 calculated to be-5.31, -5.31 eV, -5.28 and-5.02 eV respectively, and the ratio of the HOMO energy levels to the HOMO energy levels is MAPbI3Is high (-5.45 eV), the hole transfer can be promoted. The energy levels of the perovskite solar cells in examples 11 to 14 are shown in fig. 23, ITO is conductive glass, perovskite is a perovskite layer, and PCBM represents an electron transport layer.
(4) Thermal analysis
The test condition of the thermogravimetric analysis (NETZSCH STA 449F 3 Jupiter) is N2And (3) the atmosphere is kept, the temperature rise interval is 30-600 ℃, and the temperature rise rate is 10.0K/min. The results of thermogravimetric analysis of the organic hole transporting materials P1-P4 are shown in FIG. 24. Decomposition temperature (T)d) Temperature, defined as 5% weight loss, from FIG. 24As can be seen, Tds of P1 to P4 are 321.5 ℃, 180.0 ℃, 285.5 ℃ and 270.0 ℃, respectively, and the results show that the thermal stability of P2 is poor, the thermal stability of the two materials P3 and P4 is relatively good, and the thermal stability of P1 is best.
The perovskite solar cells prepared in examples 11-14 were tested and the current density-voltage curves (J-V currents) of the devices were determined by AM 1.5G (100mW cm) provided by a Source Meter (Keithley 2400) in a solar simulator (ABET Sun 3000)–2) Obtained under illumination, and the battery area is 0.08cm2The light intensity before the test is corrected by a standard silicon battery, the scanning speed is 10mV/s, and the scanning direction is positive and negative scanning.
The forward and reverse sweep J-V curves of the perovskite solar cells prepared in examples 11 to 14 (the materials of the corresponding hole transport layers are respectively P1 to P4) are shown in fig. 25, the photovoltaic parameters are shown in table 2, and the cell efficiency based on P1 is the highest (19.95%), and the cell based on P3 (18.82%), P2 (17.92%) and P4 (17.00%).
Table 2-photovoltaic parameters of perovskite solar cells prepared in different examples
The result shows that the hole transport material synthesized by the invention and taking benzo [ c ] [1,2,5] thiadiazole as the core has higher photoelectric conversion efficiency when being applied to the perovskite solar cell and has good application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An organic hole transport material, wherein the hole transport material has the formula:
wherein Ar is
Any one of, R1、R2Is hydrogen, or is an aromatic group or an alkyl group containing hetero atoms;
R3is composed of
Any one of the above, wherein n is a positive integer between 0 and 10;
R4is composed of
-(CnH2n)PO3H2、-(CnH2n)COOH、-(CnH2n)SO3H2、-(CnH2n)Si(OH)3，-(CnH2n)B(OH)2，-(CnH2n) Any one of SH, wherein n is a positive integer between 0 and 5.
2. The organic hole transport material of claim 1, wherein the hole transport material has the formula:
wherein Ar is
Any one of (a);
r is
-PO3H2Any one of (1) to (2)And (4) seed preparation.
3. The organic hole transport material according to claim 2, wherein the organic hole transport material has a chemical formula of any one of P1 to P4:
4. a method for preparing the organic hole transport material according to claim 3, wherein the method for preparing the organic hole transport material of formula P1 comprises the steps of:
reacting 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole and (4- (diphenylamino) phenyl) boric acid under an alkaline condition to obtain a first compound;
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;
under the protection of inert gas, reacting the second compound with cyanoacetic acid to obtain the organic hole transport material with the chemical formula of P1;
the preparation method of the organic hole transport material with the chemical formula of P2 comprises the following steps:
under the protection of inert gas, reacting the first compound with 4-formylphenylboronic acid under alkaline conditions to obtain a third compound;
reacting the third compound with cyanoacetic acid under the protection of inert gas to obtain an organic hole transport material with a chemical formula of P2;
the preparation method of the organic hole transport material with the chemical formula of P3 comprises the following steps:
under the protection of inert gas, reacting the first compound with diethyl phosphinate under alkaline conditions to obtain a fourth compound;
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 of P3;
the preparation method of the organic hole transport material with the chemical formula of P4 comprises the following steps:
under the protection of inert gas, 4, 7-dibromobenzo [ c ] [1,2,5] thiadiazole and 4-boric acid ester-4 ',4' -dimethoxy triphenylamine react under the alkaline condition to obtain a fifth compound;
under the protection of inert gas, reacting the fifth compound with diethyl phosphonite under alkaline conditions to obtain a sixth compound;
and (3) under the protection of inert gas, carrying out hydrolysis reaction on the sixth compound and trimethyl bromosilane to obtain the organic hole transport material with the chemical formula of P4.
5. Use of an organic hole transport material according to any of claims 1 to 3 for the preparation of perovskite solar cells and organic light emitting diodes.
6. 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 as claimed in any one of claims 1 to 3.
7. The perovskite solar cell according to claim 6, wherein the electron transport layer is [6,6] -phenyl-C61-methyl butyrate, the hole blocking layer is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and the electrode layer is silver.
8. A method of manufacturing a perovskite solar cell as claimed in claims 6 to 7, 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;
and preparing an electrode layer on the electron transport layer.
9. The method for preparing a perovskite solar cell as claimed in claim 8, wherein the preparation of the organic hole transport material solution is specifically: 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.
10. The method for preparing a perovskite solar cell as claimed in claim 9, wherein the organic hole transport material solution is coated on the substrate to prepare a hole transport layer, in particular: 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 carried out at 80-120 ℃ for 8-12 min after the spin-coating is finished.
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