CN115028602A - Star-shaped molecule for hole transport layer and preparation method and application thereof - Google Patents
Star-shaped molecule for hole transport layer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a star-shaped molecule for a hole transport layer, and a preparation method and application thereof. The star-shaped molecule provided by the invention has a branched structure, the tail end of the molecule is a triphenylamine molecule with an angular conical conformation, the central core of the molecule, namely triphenylamine and benzothiadiazole, are connected through a carbon-carbon triple bond, and a benzothiadiazole unit in the molecule is provided with a substituent group; the star-shaped molecule has the characteristics of high hole mobility and easy solution processing, can be applied to perovskite solar cells, and effectively improves the luminous efficiency of the cells.
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Description
Technical Field
The invention relates to the technical field of electron transport materials, in particular to a star-shaped molecule for a hole transport layer and a preparation method and application thereof.
Background
In addition to the solution processability of perovskite layers, the solution processability of other functional layers such as carrier transport layers (hole and electron transport layers) and even transparent and metallic electrodes is a very important direction of research for the production process of perovskite solar cells.
The p-i-n perovskite solar cell hole transport layer is generally selected from PEDOT, PSS, PTAA, NiOx and the like. The PEDOT, PSS and PTAA can be prepared by a solution processing method, on one hand, the PEDOT, PSS are acid solutions, the prepared film can damage transparent electrode layers such as FTO and ITO layers to a certain extent, and in addition, the PEDOT, PSS film also has the defect of easy water absorption, so the long-term stability of the perovskite solar cell is seriously influenced; on the other hand, PTAA is a conjugated polymer, which is expensive to produce, and its inherent properties make its purification difficult; thirdly, the NiOx film is generally prepared by a magnetron sputtering method, so that the requirement on equipment and a target material is high, and the cost is high.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a star-shaped molecule for a hole transport layer, and a preparation method and an application thereof, wherein the star-shaped molecule is applied to a perovskite solar cell as a hole transport layer, and can effectively improve the light emitting efficiency of the cell.
In order to achieve the above purpose, the present invention provides a star-shaped molecule for a hole transport layer, which has a structure shown in formula I:
wherein R is 1 Selected from substituted or unsubstituted C3-C16 alkyl, or R 1 is-XR 2 ；
X is any one of the elements in the main group VI;
R 2 selected from substituted or unsubstituted C3-C16 alkyl.
The star-shaped molecule provided by the invention takes Triphenylamine (TPA) as a donor and benzothiadiazole (1, 2, 5-benzothiazoles, BDT) as a receptor, and the Triphenylamine and the BDT are connected through a carbon-carbon three-bond to form the star-shaped molecule with a large pi conjugated system, wherein the tail end of the molecule is also TPA; wherein, the central TPA core and the BDT unit connected with the central TPA core through a triple bond can ensure certain planar performance of molecules; in addition, a larger pi conjugated system can be constructed by the TPA, the carbon-carbon triple bond and the BDT unit, and the combined action of the TPA, the carbon-carbon triple bond and the BDT unit can ensure that the star-shaped molecule has higher hole mobility. The TPA group at the tail end of the molecule has a pyramid conformation structure, which is beneficial to the injection and transmission of the hole of the molecule. Meanwhile, alkyl branched chains are introduced into the BDT units by the molecules, so that the solubility of the molecules, namely the solution processability, can be improved; furthermore, the molecule introduces alkoxy, alkylthio or alkylseleno branched chains on BDT, which can further expand a pi conjugated system and simultaneously improve the solution processability of the molecule, and has the following advantages: 1. the sizes of oxygen atoms, sulfur atoms and selenium atoms are larger, the delocalization of outer layer lone pair electrons is better, and a pi conjugated system is easier to construct with aromatic molecules, so that the hole mobility of the molecules is improved; 2. larger size atoms (oxygen, sulfur, selenium) can optimize the spatial configuration of molecules, molecules in the film prepared by the solution method tend to be amorphous, and the film with high quality can be obtained in the solution processing process. Finally, the star-shaped molecule has the characteristics of high hole mobility and easy solution processing, and can be used as a high-efficiency hole transport layer material to be applied to perovskite solar cells.
Wherein R is 1 The alkyl group is preferably a substituted or unsubstituted C3-C16 alkyl group, more preferably a substituted or unsubstituted C6-C10 alkyl group, and still more preferably a n-hexyl group, 2-ethylhexyl group, n-octyl group, 3-ethyloctyl group or n-decyl group.
The R is 1 May also be-XR 2 。
Wherein X is any one of the elements of main group VI, preferably oxygen, sulfur or selenium.
R 2 The alkyl group is preferably a substituted or unsubstituted C3-C16 alkyl group, more preferably a substituted or unsubstituted C6-C10 alkyl group, and still more preferably a n-hexyl group, 2-ethylhexyl group, n-octyl group, 3-ethyloctyl group or n-decyl group. R is as defined above 2 The substituent(s) in (1) is preferably halogen, cyano, hydroxyl, amino, or the like.
The star-shaped molecule can be well dissolved in chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, methanol and other conventional solvents, so that a film can be prepared through solution processing and is applied to a hole transport layer of a perovskite solar cell.
The invention provides a preparation method of the star-shaped molecule for the hole transport layer, which comprises the following steps:
1) reacting the compound a with the compound b to obtain a compound c;
2) compounds c and R 1 MgBr is reacted to obtain a compound d;
3) reacting the compound d with the compound e to obtain a compound shown as a formula I;
wherein R is 1 、X、R 2 The same scope is defined above, and is not described herein.
Y is halogen, specifically F, Cl or Br.
In the above preparation method, R in the substitution reaction can be replaced 1 Different attack groups of MgBr realize different R 1 And (4) introducing a group.
In some embodiments of the present invention, the reaction scheme of the above preparation method is as follows:
as shown in the reaction scheme, the products I and II can be prepared by one-step reaction of a monomer 1 and a monomer 2 or a monomer 1 and a monomer 3.
Preferably, the monomer 1 is prepared by the following reaction: the tri (4-iodobenzene) amine (triiodotriphenylamine) reacts with trimethylsilyl acetylene, and the trimethylsilyl is removed by tetrabutyl ammonium fluoride to obtain the tri (4-ethynylbenzene) amine.
Specifically, the preparation process of the monomer 1 comprises the following steps: reacting tri (4-iodobenzene) amine and trimethylsilyl acetylene at normal temperature in the presence of bis (triphenylphosphine) palladium chloride and cuprous iodide as catalysts and triethylamine and tetrahydrofuran to obtain a trimethylsilyl ethynyl substituent of triphenylamine; then, the trimethylsilyl group is removed by using tetrabutylammonium fluoride to obtain the tri (4-ethynyl benzene) amine.
Preferably, the monomer 2 or the monomer 3 is prepared by the following reaction: firstly, carrying out iodination reaction on 4, 7-dibromo-benzothiadiazole to obtain 4, 7-dibromo-6-iodobenzothiadiazole; second, the action of 4-diphenylaminobenzaldehyde on potassium tert-butoxide and triphenylmethyl phosphorus iodide4-diphenylamino styrene is obtained; thirdly, 4-diphenylamino styrene and 4, 6, 7-tribromobenzothiadiazole react to obtain 4- (6, 7-dibromobenzothiadiazole) -ethenyl- (4-diphenylamino benzene); in the fourth step, the bromine at the 6-position of the product of the third step is substituted by an alkyl group (R) 1 ) Or alkoxy, alkylthio, alkylseleno (X-R) 2 ) Substitution gives monomer 2 or monomer 3.
Specifically, the preparation process of the monomer 2 and the monomer 3 comprises the following steps: 1) carrying out bromination reaction on the 4, 7-dibromo-benzothiadiazole under the action of magnesium dichloride (2, 2, 6, 6-tetramethylpiperidine) lithium salt (TMPMgCl ∙ LiCl) to obtain 4, 6, 7-tribromobenzothiadiazole; 2) 4-diphenylamino benzaldehyde is subjected to combined action of potassium tert-butoxide and triphenyl methyl phosphorus iodide to obtain 4-diphenylamino styrene; 3) 4-diphenylamino styrene and 4, 6, 7-tribromobenzothiadiazole react to obtain 4- (6, 7-dibromobenzothiadiazole) -vinyl- (4-diphenylamino benzene); 4) with alkyl (R) 1 ) Or alkoxy, alkylthio, alkylseleno (X-R) 2 ) Attack bromine on 6-position in 4- (6, 7-dibromo benzothiadiazole) -ethenyl- (4-diphenylamino benzene) to generate substitution reaction, and obtain corresponding monomer 2 or monomer 3.
Then, the monomer 1 and the monomer 2, or the monomer 1 and the monomer 3 react under the combined action of tetrakis (triphenylphosphine) palladium and cuprous iodide to obtain the star-shaped molecule with the structure shown in the formula I or the formula II, wherein the reaction solvent is preferably triethylamine and tetrahydrofuran.
In the synthetic route, different main group VI elements and substituent groups R in the final product 1 、R 2 This can be achieved by replacing the attack group of the bromine substitution reaction at the 6-position in monomer 2 and monomer 3.
The tri (4-iodobenzene) amine, the trimethylsilylacetylene, the 4, 7-dibromobenzothiadiazole, the 4-diphenylamine benzaldehyde and the like as raw materials and related catalysts and solvents are commercial products and can be directly purchased.
The invention provides the application of the star-shaped molecule which can be used for the hole transport layer or the star-shaped molecule which can be used for the hole transport layer and is prepared by the preparation method in the preparation of the hole transport layer.
The invention also provides a hole transport layer, which comprises the star-shaped molecule capable of being used for the hole transport layer or the star-shaped molecule capable of being used for the hole transport layer prepared by the preparation method, wherein the star-shaped molecule forms a thin film layer by a solution processing method.
The invention has no special limitation on the solution, and can be a solution prepared by dissolving the star-shaped molecule provided by the invention in a conventional solvent; the conventional solvent is preferably one or more of chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, methanol and the like, namely the solution processing method adopts a solution comprising the following steps: chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, methanol, and the like.
The solution processing method includes, but is not limited to, one or more of a spin coating film forming method, a blade coating method, a slot extrusion coating method, a wire bar coating method, roll-to-roll printing and the like, and more preferably, one or more of a spin coating film forming method, a slot extrusion coating method and a wire bar coating method is used.
The thickness of the thin film layer is preferably 10-100 nm, and more preferably 20-60 nm.
The preparation process parameters of the spin coating film are preferably as follows: the compound of the formula I is dissolved in a solvent, the concentration of the solution is preferably 0.2 mg/ml-10 mg/ml, the spin coating speed is preferably 1000 rpm/min-8000 rmp/min, and the obtained film thickness is preferably 10-100 nm, and more preferably 20-60 nm. The solvent is preferably one or more of chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, methanol, and the like, and more preferably chlorobenzene.
The preparation process parameters of the wire rod coating film are preferably as follows: the compound of the formula I is dissolved in a solvent, the concentration of the solution is preferably 0.2 mg/ml-10 mg/ml, the coating speed is preferably 5-40 mm/s, the gap between a wire rod and a substrate is preferably 20-500 mu m, and the obtained film thickness is preferably 10-100 nm, more preferably 20-60 nm. The solvent is preferably one or more of chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, methanol, and the like, and more preferably methanol.
The invention provides a perovskite solar cell which comprises the hole transport layer.
Compared with the prior art, the star-shaped molecule for the hole transport layer provided by the invention has a structure shown in a formula I. The star-shaped molecule provided by the invention has a branched structure, the tail end of the molecule is a triphenylamine molecule with an angular cone conformation, the central core of the molecule, namely triphenylamine and benzothiadiazole, are connected through a carbon-carbon triple bond, and a benzothiadiazole unit in the molecule is provided with a substituent group; the star-shaped molecule has the characteristics of high hole mobility and easy solution processing, can be applied to perovskite solar cells, and effectively improves the luminous efficiency of the cells.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of monomer 1 prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2, 4, 6, 7-tribromobenzothiadiazole prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 4-diphenylaminostyrene prepared in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of 4- (6, 7-dibromobenzothiadiazole) -vinylene- (4-diphenylanilinobenzene) prepared in example 1;
FIG. 5 is a nuclear magnetic hydrogen spectrum of monomer 2 prepared in example 1;
FIG. 6 is a nuclear magnetic hydrogen spectrum of the star molecule prepared in example 1;
FIG. 7 is a nuclear magnetic hydrogen spectrum of a star-shaped molecule prepared in example 2;
FIG. 8 is a nuclear magnetic hydrogen spectrum of a star-shaped molecule prepared in example 3;
FIG. 9 is a nuclear magnetic hydrogen spectrum of a star-shaped molecule prepared in example 4;
FIG. 10 is a nuclear magnetic hydrogen spectrum of a star-shaped molecule prepared in example 5;
FIG. 11 is a schematic diagram of the perovskite solar cell prepared by the present invention.
Detailed Description
In order to further illustrate the present invention, the star-shaped molecules for hole transport layers and the preparation method and application thereof provided by the present invention are described in detail below with reference to the examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The practice of the present invention may employ conventional techniques and assays for organic synthesis within the skill of the art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. Temperatures used in the following examples o C represents that the pressure is at or near atmospheric pressure. All solvents were purchased as HPLC grade. Unless otherwise indicated, all reagents were obtained commercially.
Example 1
1. The synthesis of monomer 1 is as follows:
the synthesis steps are as follows:
1) adding 10mmol of tri (4-iodobenzene) amine, 1mmol of bis triphenylphosphine palladium chloride and 1mmol of cuprous iodide into a schlenk bottle which is dried in advance; 2) argon is filled and washed for three times, then 80ml of tetrahydrofuran and 40mmol of trimethylsilyl acetylene are added, and finally 20ml of triethylamine is added by an injector; 3) after stirring the mixture for 15 hours, it was diluted with ether and quenched with a small piece of silica; 4) transferring the crude product after the solvent is removed by reduced pressure distillation into a round-bottom flask, and then adding 40ml of dichloromethane for dissolution; 5) cooling to 0 deg.C (ice water bath), and slowly adding 30mmol of tetrabutylammonium fluoride (30 ml of 1mol/ml tetrahydrofuran solution) via syringe; 6) the reaction mixture was stirred at 0 ℃ for 2 hours; 7) the product was purified by column chromatography on silica gel eluting with pentane and dichloromethane (volume ratio 9: 1).
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 1.
2. The synthesis of 4, 6, 7-tribromobenzothiadiazole is carried out by the following synthetic route:
the synthesis steps are as follows:
1) under the protection of argon and at the temperature of 0 ℃ (ice water bath), 10mmol of 4, 7-dibromobenzothiadiazole is dissolved in 40ml of tetrahydrofuran, and then 7.5mmol of magnesium dichloride (2, 2, 6, 6-tetramethylpiperidine) lithium salt solution (TMPMgCl ∙ LiCl, 15ml of 0.5mol/L tetrahydrofuran solution) is slowly added dropwise, wherein the whole dropwise adding time is 15 minutes; 2) controlling the temperature at 0 ℃, stirring the reaction mixture for 3 hours, slowly dropwise adding 15mmol of 1, 2-dibromo-tetrachloroethane (15 ml of 1mol/L tetrahydrofuran solution), controlling the temperature to slowly rise to 25 ℃ while dropwise adding the solution, and controlling the time of dropwise adding the solution and rising the temperature to be about 30 minutes; 3) adding 40ml of saturated ammonium chloride to quench the reaction; 4) the aqueous layer in the post-reaction mixture was extracted with dichloromethane (three times 60ml each); 5) the organic layers were combined and dried over magnesium sulfate, followed by distillation under reduced pressure to remove the remaining solvent; 6) the crude product was purified by flash chromatography to give the product as eluent pentane and ether (vol =100: 1).
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 2.
3. The synthesis of 4-diphenylamino styrene comprises the following synthetic route:
the synthesis steps are as follows:
1) under argon atmosphere, 30g of 4-diphenylaminobenzaldehyde (about 110mmol) was dissolved in 45ml of tetrahydrofuran, followed by addition of 20g of potassium tert-butoxide (about 165 mmol) and 65g of triphenylmethylphosphonium iodide (about 165 mmol); 2) the mixture was stirred at room temperature under argon for 4.5 hours; 3) the reacted mixture was poured into 20ml of a mixed solvent of dichloromethane and deionized water (volume ratio 1: 1) quenching; 4) extraction with dichloromethane three times (40 ml each), combining the organic phases and rotary evaporation to remove the solvent; 5) purifying the residual reaction product by silica gel column chromatography, wherein the eluent is n-hexane; 6) the eluted solution was subjected to rotary evaporation to remove the solvent, and then methylene chloride and methanol (volume ratio 1: 20) the obtained precipitate is the product.
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 3.
4. The synthesis of 4- (6, 7-dibromo benzothiadiazole) -vinyl- (4-diphenylamino benzene) has the following synthetic route:
the synthesis steps are as follows: 1) 12mmol of 4-diphenylaminostyrene, 12mmol of 4, 6, 7-tribromobenzothiadiazole, 0.22mmol of palladium acetate [ Pd (OAc) 2 ]12mmol of sodium acetate and 1.95 mmol of tetrabutylammonium bromide are dissolved together in 80ml of N, N-Dimethylformamide (DMF); 2) heating to 100 ℃, stirring and reacting for 24 hours, and then adding 150ml of deionized water to quench the reaction; 3) the reacted mixture was filtered and the resulting precipitate was washed with deionized water, then dissolved in dichloromethane and dried over magnesium sulfate; 4) removing residual solvent by vacuum evaporation, and purifying by silica gel column chromatography to obtain product, wherein the eluent is mixed solvent of petroleum ether and dichloromethane (volume ratio is 3: 1).
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 4.
5. The 6-position bromine on the 4- (6, 7-dibromo benzothiadiazole) -vinyl- (4-diphenylaniline) has the following synthesis route:
the synthesis steps are as follows: 1) under the protection of inert gas argon, 0.36mmol of 1, 3-bis (diphenylphosphinopropane) nickel dichloride [ Ni (dpp) Cl 2 ]36mmol of 4- (6, 7-dibromobenzothiadiazole) -vinylene- (4-diphenylanilinobenzene) were added together to 80ml of Tetrahydrofuran (THF); 2) the Grignard reagent (MgBrC) was added dropwise at 0 deg.C 6 H 13 1.5mol, about 12 ml); 3) after the dropwise addition reaction was completed, the mixture was refluxed overnightSlowly quenching with hydrochloric acid, then washing twice with water, extracting twice with diethyl ether, rotatably evaporating the residual solvent to dryness, and drying in vacuum to obtain the product, namely the monomer 2.
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 5.
6. The synthesis of star-shaped molecule is as follows:
the synthesis steps are as follows: 1) 1.7 mmol of the monomer 1, 5.6mmol of the monomer 2, 0.085mmol (5% molar ratio) of palladium bistriphenylphosphine chloride and 0.085mmol of cuprous iodide were added together to a mixed solvent of 80ml of Triethylamine (TEA) and 80ml of tetrahydrofuran; 2) the mixture was heated to reflux and maintained at reflux for 5.5 hours, then allowed to cool to room temperature; 3) removing residual solvent by reduced pressure distillation, and purifying by silica gel column chromatography to obtain product, wherein the eluent is mixed solvent of petroleum ether and dichloromethane (volume ratio is 4: 1).
The nuclear magnetic hydrogen spectrum of the prepared product is shown in figure 6.
Example 2
N-hexyl (C) in the fifth step's reagent of the synthetic route of example 1 6 H 13 ) By changing to n-octyl (C) 8 H 17 ) The rest is unchanged, and the final product is as follows:
the nuclear magnetic hydrogen spectrum is shown in FIG. 7.
Example 3
N-hexyl (C) in the fifth step's reagent of the synthetic route of example 1 6 H 13 ) By changing to 2-ethylhexyl (CH) 3 CH 2 C 6 H 12 ) The remainder was unchanged, and the final product was as follows:
the nuclear magnetic hydrogen spectrum is shown in FIG. 8.
Example 4
N-hexyl (C) in the fifth step Grignard reagent of the synthetic route of example 1 6 H 13 ) By change to n-hexyloxy (C) 6 H 13 O), the rest being unchanged, the final product obtained is as follows:
the nuclear magnetic hydrogen spectrum is shown in FIG. 9.
Example 5
N-hexyl (C) in the fifth step's reagent of the synthetic route of example 1 6 H 13 ) Replacement of n-hexylthio (C) 6 H 13 S), the rest is unchanged, and the final obtained product is as follows:
the nuclear magnetic hydrogen spectrum is shown in FIG. 10.
Comparative example 1
Preparation of perovskite solar cell based on NiOx as hole transport layer
(1) Ultrasonically cleaning the FTO glass with the pattern by using deionized water, acetone and ethanol in sequence, and then carrying out UVO treatment for 15 minutes for later use;
(2) preparing NiO with the thickness of 25nm by the treated FTO glass through a magnetron sputtering process x A hole transport layer;
(3) covering NiO x Placing the FTO glass of the hole transport layer into a high-temperature oven, annealing for 30 minutes at 300 ℃, and taking out for later use after cooling;
(4) 1290.8mg of PbI are taken 2 And 445.2mg of MAI dissolved in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO is 4: 1), stirring at normal temperature overnight to obtain a perovskite precursor solution, wherein the total concentration of solute in the solution is 1.4 mol/ml;
(5) NiO obtained in step (3) x And (3) coating the perovskite precursor solution obtained in the step (4) on a hole transport layer in a spinning mode: the whole spin coating process is divided into three steps, firstly spin coating for 3 seconds at 4000 rpm/min; then spin-coating at 5000rpm/min for 30 seconds; finally, 200 mul of chlorobenzene (anti-solvent) is dripped when the high-speed spin coating is carried out for 11 seconds at 5000rpm/min, all the anti-solvent is dripped within 2 seconds, and the thickness of the perovskite active layer is controlled to be about 500 nm;
(6) annealing the wafer obtained in the step (5) in an oven at 130 ℃ for 20 minutes, cooling and taking out;
(7) moving the sheet prepared in the step (6) into a vacuum evaporation chamber, and vacuumizing until the vacuum degree is lower than 4 x 10 -4 After Pa, preparing an electron transmission layer and a modification layer by a thermal evaporation deposition method; c 60 The evaporation rate is less than 0.05 angstrom/second, and the thickness of the film is 40 nm; the BCP evaporation rate is less than 0.1 angstrom/second, and the film thickness is 6 nm;
(8) preparing the gold electrode by the sheet prepared in the step (7) by adopting a thermal evaporation deposition method, and controlling the vacuum degree to be lower than 4 x 10 -4 Pa, the initial evaporation rate is 0.2 nm/second, meanwhile, the real-time film thickness is monitored through an online film thickness testing device, after the film thickness is larger than 10nm, the evaporation rate is adjusted to be 1.5 nm/second, after the film thickness is larger than 20nm, the evaporation rate is adjusted to be 4 nm/second, and the final thickness of a gold electrode is 100nm, so that the perovskite solar cell device is prepared.
Device application example 1
The preparation of the NiOx hole transport layer by the magnetron sputtering process in step (2) in comparative example 1 was changed to the preparation by the solution spin coating method, and the preparation procedure was as follows: the product obtained in example 1 was dissolved in chlorobenzene at a solution concentration of 8mg/ml, a spin-coating speed of 6500rpm/min to give a film thickness of 20nm, and the remaining steps were as in comparative example 1.
FIG. 11 is a schematic view of the perovskite solar cell structure prepared by the present invention, 1-transparent electrode layer; 2-a hole transport layer; a 3-perovskite active layer; 4-an electron transport layer; 5-a modification layer; 6-metal electrodes.
Device application example 2
The spin coating speed in the device application example 1 was changed to 4000rpm/min, and the film thickness was controlled to 40nm, which is the same as in the device application example 1.
Device application example 3
The preparation of the hole transport layer thin film by the spin-coating method in the device application example 1 is changed into the preparation by a wire rod coating method, and the preparation process comprises the following steps: the product obtained in example 1 was dissolved in chlorobenzene at a solution concentration of 8mg/ml, a coating speed of 10mm/s, a gap of 70 μm between a wire bar and a substrate, and the obtained film had a thickness of 20nm, and the remaining steps were the same as in device application example 1.
Device application example 4
Perovskite solar cell preparation of hole transport layer based on the product solution method prepared in example 2, wherein a hole transport layer thin film was prepared by spin coating, as described in device application example 1, and the resulting film thickness was 20 nm.
Device application example 5
Perovskite solar cell preparation for hole transport layer preparation based on the product solution method prepared in example 3, wherein a hole transport layer thin film was prepared by spin coating, as described in device application example 1, to a film thickness of 20 nm.
Device application example 6
Perovskite solar cell preparation of hole transport layer based on the product solution method prepared in example 4, wherein a hole transport layer thin film was prepared by spin coating, as described in device application example 1, and the resulting film thickness was 20 nm.
Device application example 7
Perovskite solar cell preparation of hole transport layer based on the product solution method prepared in example 5, wherein a hole transport layer thin film was prepared by spin coating, as described in device application example 1, and the resulting film thickness was 20 nm.
Performance detection
And (3) testing the battery performance: the perovskite solar cell prepared in the above example was subjected to a standard solar light intensity (AM1.5G, 100 mW/cm) using a solar simulator (xenon lamp as a light source) 2 ) Tests were performed using silicon diodes (with KG9 visible filter) calibrated in the national renewable energy laboratory. The corresponding test results are shown in table 1.
Table 1 perovskite solar cell performance parameter table prepared according to different embodiments
As can be seen from the battery performance test data, the hole transport layer prepared by the star-shaped molecule provided by the invention can be used for perovskite solar cells. Compared with a perovskite cell using NiOx as a hole transport layer prepared by a magnetron sputtering method, star-shaped molecules can be used for preparing the hole transport layer by a solution processing method, and meanwhile, the perovskite solar cell with the hole transport layer shows better performance parameters, and the preparation process is simplified.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A star-shaped molecule which can be used for a hole transport layer has a structure shown in a formula I:
wherein R is 1 Selected from substituted or unsubstituted C3-C16 alkyl, or R 1 is-XR 2 ；
X is any one of the elements in the main group VI;
R 2 selected from substituted or unsubstituted C3-C16 alkyl.
2. The star-shaped molecule for a hole transport layer according to claim 1, wherein R is 1 Selected from substituted or unsubstituted C6-C10 alkyl;
x is oxygen, sulfur or selenium;
R 2 selected from substituted or unsubstituted C6-C10 alkyl.
3. The star-shaped molecule for a hole transport layer according to claim 2, wherein R is 1 Selected from n-hexyl, 2-ethylhexyl, n-octyl, 3-ethyloctyl or n-decyl;
x is oxygen, sulfur or selenium;
R 2 selected from n-hexyl, 2-ethylhexyl, n-octyl, 3-ethyloctyl or n-decyl.
4. The method for preparing the star-shaped molecule used for the hole transport layer according to any one of claims 1 to 3, comprising the steps of:
1) reacting the compound a with the compound b to obtain a compound c;
2) compounds c and R 1 MgBr is reacted to obtain a compound d;
3) reacting the compound d with the compound e to obtain a compound shown as a formula I;
wherein R is 1 Selected from substituted or unsubstituted C3-C16 alkyl, or R 1 is-XR 2 ；
X is any one of the elements in the VI main group;
R 2 selected from substituted or unsubstituted C3-C16 alkyl;
y is halogen.
5. Use of the star-shaped molecule for a hole transport layer according to any one of claims 1 to 3 or the star-shaped molecule for a hole transport layer prepared by the preparation method according to claim 4 in the preparation of a hole transport layer.
6. A hole transport layer, comprising the star-shaped molecule for a hole transport layer according to any one of claims 1 to 3 or the star-shaped molecule for a hole transport layer prepared by the preparation method according to claim 4, wherein the star-shaped molecule is formed into a thin film layer by a solution processing method.
7. The hole transport layer of claim 6, wherein the solution processing method comprises: one or more of a spin-on film-forming method, a blade coating method, a slit extrusion coating method, a wire bar coating method, and a roll-to-roll printing.
8. The hole transport layer according to claim 6, wherein the solution processing method uses a solution comprising: chlorobenzene, dichlorobenzene, toluene, xylene, chloroform, tetrahydrofuran and methanol.
9. The hole transport layer of claim 6, wherein the thin film layer has a thickness of 10 to 100 nm.
10. A perovskite solar cell, comprising the hole transport layer according to any one of claims 6 to 9.
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| PCT/CN2023/082965 WO2024031993A1 (en) | 2022-08-09 | 2023-03-22 | Star-shaped molecule capable of being used for hole transport layer, preparation method therefor, and use thereof |
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| CN101492428A (en) * | 2008-01-23 | 2009-07-29 | 中国科学院化学研究所 | Star numerator acceptor material with triphenylamine as core, preparation method and application thereof |
| KR20160050223A (en) * | 2014-10-29 | 2016-05-11 | 경상대학교산학협력단 | Benzothiadiazole derivatives and Solar cell device using this material |
| CN111205245A (en) * | 2020-01-10 | 2020-05-29 | 南方科技大学 | Hole transport material and preparation method and application thereof |
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| CN101348537B (en) * | 2008-08-18 | 2010-09-15 | 苏州大学 | Triphenyl amine-naphthalin multi-branched molecule having two-photon polymerization initiation characteristic |
| CN103073541B (en) * | 2013-01-07 | 2015-08-19 | 中国科学院宁波材料技术与工程研究所 | Triphenylamine star-shaped material, its preparation method and purposes that electron-withdrawing group is modified |
| CN115028602B (en) * | 2022-08-09 | 2022-11-15 | 中国华能集团清洁能源技术研究院有限公司 | Star-shaped molecule capable of being used for hole transport layer and preparation method and application thereof |
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| CN101492428A (en) * | 2008-01-23 | 2009-07-29 | 中国科学院化学研究所 | Star numerator acceptor material with triphenylamine as core, preparation method and application thereof |
| KR20160050223A (en) * | 2014-10-29 | 2016-05-11 | 경상대학교산학협력단 | Benzothiadiazole derivatives and Solar cell device using this material |
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| CHANG HE, ET AL.: "Improving the efficiency of solution processable organic photovoltaic devices by a star-shaped molecular geometry", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
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| WO2024031993A1 (en) * | 2022-08-09 | 2024-02-15 | 中国华能集团清洁能源技术研究院有限公司 | Star-shaped molecule capable of being used for hole transport layer, preparation method therefor, and use thereof |
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