CN110635043A - Novel organic hole transport layer perovskite solar cell and preparation method thereof - Google Patents
Novel organic hole transport layer perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a novel organic hole transport layer perovskite solar cell, and the structure of a prepared solar cell device comprises the following steps from bottom to top: the device comprises a substrate, an anode, a hole transport layer, an optical active layer, an electron transport layer, a cathode modification layer and a cathode; the hole transport layer is prepared into organic small molecular monomer BTCV by adopting an organic chemical synthesis method, the organic small molecular monomer BTCV is dissolved in an organic solvent and then is coated on a glass substrate in a spinning mode, and the organic small molecular monomer BTCV is subjected to polymerization crosslinking reaction by adopting high-temperature annealing or ultraviolet lamp irradiation to form a net-shaped hole transport layer which is used for transporting holes and improve the photoelectric conversion efficiency of the cell, wherein the photoelectric conversion efficiency can reach 17.58%; the organic small-molecular monomer BTCV has the advantages of simple synthesis steps, low cost, high yield and stable property, can be commercially produced, and greatly reduces the cost of the perovskite solar cell. The organic hole transport material small molecule monomer BTCV can also be applied to the preparation of other photovoltaic devices.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a novel organic hole transport layer perovskite solar cell and a preparation method thereof.
Background
Solar cells based on organometallic halide perovskite materials (pero-SCs) are one of the most promising candidate materials for future energy power generation, and the process based on solution processing is simple, the photoelectric conversion efficiency is high, and the Photoelectric Conversion Efficiency (PCE) of the current organometallic halide perovskite solar cells is over 20%. The planar perovskite solar cell can realize solution processing at low temperature, and the low cost and the layer-by-layer processing technology are perfectly combined.
The structure of this type of battery device was at first: glass/Indium Tin Oxide (ITO)/PEDOT PSS/CH3NH3PbI3/C60Although the PEDOT: PSS is widely applied to organic electronic equipment as an interface layer, the performance of a device is influenced by the defects of acidity, easiness in water absorption and the like, and the prospect of the PEDOT: PSS in the industrialization of the planar perovskite solar cell is limited due to the high price of the PEDOT: PSS. Malinkiewicz et al adopt poly-TPD as a hole transport layer, and the high LUMO energy level (-2.4eV) can block the electron from being transported to the anode, however, some polymer hole transport materials are applied to the planar perovskite solar cell, the price cost of poly-TPD is expensive, and when the planar perovskite solar cell is prepared, the polymer hole transport layer positioned at the lower layer is required to resist the dissolution of a polar precursor solution, so that the search for a stable hole transport layer material is very important for preparing the planar perovskite solar cell.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a novel perovskite solar cell with an organic hole transport layer and a preparation method thereof, so that the cost of the planar perovskite solar cell is reduced, and the energy conversion efficiency of the cell is improved.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps:
step S1, cleaning and drying the glass substrate plated with the anode material, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step S2, depositing BTCV polymer on the pretreated substrate to form an organic hole transport layer;
s3, spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 90-110 ℃ to obtain a perovskite crystal film, namely a photoactive layer;
step S4, spin-coating a chlorobenzene solution of PCBM on the photoactive layer to form an electron transport layer;
step S5, spin-coating a methanol solution of PDINO on the electron transport layer to form a cathode modification layer;
and step S6, evaporating the cathode material to the cathode modification layer through thermal evaporation in vacuum to obtain the perovskite solar cell.
In the method for manufacturing the novel organic hole transport layer perovskite solar cell, preferably, the specific step of forming the organic hole transport layer in step S2 includes:
step s21, placing the organic small molecular monomer BTCV in N, N-dimethylformamide, fully stirring and dissolving to prepare a BTCV solution;
step s22, filtering the BTCV solution, spin-coating the BTCV solution on a spin coater for 30-60 seconds, and then curing to form a cross-linked reticular organic hole transport layer;
preferably, the concentration of the BTCV solution is 0.5-1.5mg mL-1；
Preferably, the thickness of the organic hole transport layer is 10-20 nm.
In the preparation method of the novel organic hole transport layer perovskite solar cell, preferably, in step s22, the curing treatment is annealing at 130-170 ℃ for 8-12min or ultraviolet lamp irradiation for 25-35min on a hot bench.
In the method for preparing the novel organic hole transport layer perovskite solar cell, preferably, the specific preparation method of the organic small molecule monomer BTCV comprises the following steps:
heating 2-bromocarbazole, 4-vinylbenzyl chloride and acetone to 60-90 ℃, adding sodium hydroxide and tetrabutylammonium hydrogen sulfate, stirring, filtering, spin-drying a solvent, and performing column chromatography to obtain white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 9- (4-vinylbenzyl) -2-bromocarbazole, 5 '-bis (trimethyltin) -2,2' -bithiophene, palladium tetratriphenylphosphine and freshly distilled toluene into a container, pumping gas for 2-4 times, heating to 110 ℃ and 130 ℃ in an argon atmosphere for reaction, cooling to room temperature after the reaction is finished, spin-drying the solvent, adding a saturated potassium fluoride solution, extracting by using dichloromethane, spin-drying the solvent, and carrying out column chromatography to obtain a yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely the organic small molecular monomer BTCV.
In the preparation method of the novel organic hole transport layer perovskite solar cell, the molar ratio of the 2-bromocarbazole to the 4-vinylbenzyl chloride is preferably 1:1.
In the preparation method of the novel organic hole transport layer perovskite solar cell, the molar ratio of the 9- (4-vinylbenzyl) -2-bromocarbazole to the 5,5 '-bis (trimethyltin) -2,2' -bithiophene is preferably 2: 1.
In the method for manufacturing a novel organic hole transport layer perovskite solar cell as described above, preferably, in step S3, the method for manufacturing the perovskite precursor solution includes:
dissolving the donor A in an organic solvent, then adding the donor B, and stirring to obtain a perovskite precursor solution;
wherein the donor A is lead chloride, lead bromide, lead acetate, lead thiocyanate or lead iodide;
the donor B is methyl ammonium chloride, formamidine hydrochloride, methyl ammonium bromide, formamidine hydrobromide, methyl ammonium iodide or formamidine hydroiodide;
preferably, the organic solvent is dimethylformamide, dimethyl sulfoxide or γ -butyrolactone.
In the method for preparing the novel organic hole transport layer perovskite solar cell, the molar ratio of the donor A to the donor B is preferably 1: (1-5);
preferably, the total mass percentage of the donor A and the donor B in the organic solvent is 35-50 wt%.
A perovskite solar cell prepared by a preparation method of a novel organic hole transport layer perovskite solar cell.
Use of an organic hole transport layer for the preparation of a photovoltaic device; the organic hole transport layer is prepared by adopting the preparation method of the novel organic hole transport layer perovskite solar cell.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
according to the invention, the organic micromolecule monomer substance is subjected to a crosslinking reaction to form a net-shaped hole transport layer to replace the existing hole transport layer, so that the efficient planar perovskite solar cell is prepared, and the method mainly has the following excellent effects:
1. the performance of the perovskite solar cell is improved; the hole transport layer can well transport holes and block electrons, and reduces the occurrence probability of electron coupling or charge recombination at an interface, so that the open-circuit voltage, the short-circuit current density and the filling factor of the perovskite solar cell are improved, the photoelectric conversion efficiency of the perovskite solar cell is finally improved, and the photoelectric conversion efficiency of the planar heterojunction perovskite cell prepared by the preparation method disclosed by the invention reaches 17.58%.
2. The cost of the perovskite solar cell is reduced; the method prepares the solution of the organic micromolecular monomer BTCV, directly coats the solution on the anode substrate glass in a spinning way, and prepares the hole transport layer after crosslinking, so the method is simple to operate and can realize the preparation of large-area films.
Meanwhile, the organic small molecular monomer BTCV has the advantages of simple synthesis steps, low cost, high yield and stable property, can be commercially produced, and greatly reduces the cost of the perovskite solar cell.
Compared with the existing hole transport material, the perovskite solar cell prepared by using the organic small molecule monomer polymer material as the hole transport layer has better performance and lower cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
fig. 1 is a schematic structural view of a perovskite solar cell of example 1 of the present invention;
FIG. 2 is a flow diagram of the preparation of a perovskite solar cell according to an embodiment of the invention;
FIG. 3 is a molecular structural formula of a hole transport layer material BTCV according to an embodiment of the present invention;
FIG. 4 is a mass spectrum of BTCV as a hole transport layer material according to an embodiment of the present invention;
fig. 5 is a current density-voltage characteristic curve (positive and negative sweeps) of the perovskite solar cells prepared in inventive example 1 and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a novel perovskite solar cell with an organic hole transport layer, and provides a planar perovskite solar cell based on an organic cross-linking hole transport layer and a preparation method thereof, aiming at the defect that a hole transport material PEDOT (3, 4-ethylenedioxythiophene monomer-polystyrene sulfonate polymer) commonly used in the conventional planar perovskite solar cell is PSS (3, 4-ethylenedioxythiophene monomer-polystyrene sulfonate polymer), so that the cost of the planar perovskite solar cell is reduced, and the energy conversion efficiency of the cell is improved.
The solar cell device structure of the present invention comprises, from bottom to top: the device comprises a substrate, an anode, a hole transport layer, an optical active layer, an electron transport layer, a cathode modification layer and a cathode; the hole transport layer is made of organic hole transport layer material with the thickness of about 10-20nm, organic micromolecule monomer BTCV is prepared by an organic chemical synthesis method, the organic micromolecule monomer BTCV is dissolved in organic solvent and then is coated on a glass substrate in a spinning mode, polymerization crosslinking reaction is carried out on the organic micromolecule monomer BTCV by adopting high-temperature annealing or ultraviolet lamp irradiation, and a reticular hole transport layer is formed and used for blocking electrons, transporting holes, inhibiting the close contact between an anode and a light active layer, reducing the carrier recombination probability at an interface and further improving the photoelectric conversion efficiency of the battery. The organic small-molecule monomer BTCV has the advantages of simple synthesis steps, low cost, high yield and stable property, can be commercially produced, and greatly reduces the cost of the perovskite solar cell.
The organic hole transport material small molecule monomer BTCV prepared by the invention can also be applied to the preparation of other photovoltaic devices.
The invention provides a preparation method of a perovskite solar cell with a novel organic hole transport layer, which comprises the following steps:
a preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps:
and step S1, cleaning and drying the glass substrate plated with the anode material, and then carrying out ultraviolet cleaning treatment to obtain the pretreated substrate.
Preferably, the anode material is Indium Tin Oxide (ITO) or fluorine doped tin oxide (FTO) for collecting holes.
Step S2, depositing BTCV polymer on the pretreated substrate to form an organic hole transport layer. Preferably, the organic hole transport layer has a thickness of 10-20nm (such as 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20 nm).
Preferably, the specific step of forming the organic hole transport layer in step S2 includes:
step s21, placing the organic small molecular monomer BTCV in N, N-dimethylformamide, fully stirring and dissolving to prepare a BTCV solution; preferably, the concentration of the BTCV solution is 0.5-1.5mg mL-1(e.g., 0.6mg mL)-1、0.7mg mL-1、0.8mg mL-1、0.9mg mL-1、1.0mg mL-1、1.1mg mL-1、1.2mg mL-1、1.3mg mL-1、1.4mg mL-1)；
Step s22, filtering the BTCV solution, spin-coating the BTCV solution on a spin coater for 30 to 60 seconds, and then carrying out curing treatment to form a cross-linked reticular organic hole transport layer; in step s22, the curing treatment is annealing at 130-170 deg.C (such as 135 deg.C, 138 deg.C, 140 deg.C, 145 deg.C, 148 deg.C, 150 deg.C, 155 deg.C, 158 deg.C, 160 deg.C, 165 deg.C, 168 deg.C) for 8-12min (such as 9min, 10min, 11min, 12min) or irradiating with ultraviolet lamp for 25-35min (such as 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34 min);
preferably, the specific preparation method of the organic small molecule monomer BTCV comprises the following steps:
heating 2-bromocarbazole, 4-vinylbenzyl chloride and acetone to 60-90 deg.C (such as 62 deg.C, 64 deg.C, 66 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 74 deg.C, 76 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 84 deg.C, 86 deg.C, 88 deg.C, 90 deg.C), adding sodium hydroxide and tetrabutylammonium hydrogen sulfate, stirring, filtering, spin-drying solvent, and performing column chromatography to obtain white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 9- (4-vinylbenzyl) -2-bromocarbazole, 5 '-bis (trimethyltin) -2,2' -bithiophene, palladium tetratriphenylphosphine and freshly distilled toluene into a container, pumping air for 2-4 times, heating to 110-130 ℃ (such as 112 ℃, 114 ℃, 116 ℃, 118 ℃, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃ and 130 ℃) in an argon atmosphere for reaction, cooling to room temperature after the reaction is finished, spin-drying the solvent, adding a saturated potassium fluoride solution, extracting by using dichloromethane, spin-drying the solvent, and performing column chromatography to obtain a yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely an organic small molecular monomer BTCV.
Newly distilled toluene means that common toluene is distilled before being used, and no water and no impurities are ensured.
Preferably, the molar ratio of 2-bromocarbazole to 4-vinylbenzyl chloride is 1:1.
Preferably, the molar ratio of 9- (4-vinylbenzyl) -2-bromocarbazole to 5,5 '-bis (trimethyltin) -2,2' -bithiophene is 2: 1.
Step S3, spin-coating perovskite precursor solution (CH) on the organic hole transport layer3NH3PbI3) Adding chlorobenzene solvent, continuously spin-coating, and annealing at 90-110 deg.C (such as 92 deg.C, 94 deg.C, 96 deg.C, 98 deg.C, 100 deg.C, 102 deg.C, 104 deg.C, 106 deg.C, 108 deg.C, and 110 deg.C) to obtain perovskite crystal film, i.e. photoactive layer;
preferably, in step S3, the method for preparing the perovskite precursor solution includes:
dissolving the donor A in an organic solvent, then adding the donor B, and stirring to obtain a perovskite precursor solution;
wherein, the donor A is lead chloride, lead bromide, lead acetate, lead thiocyanate or lead iodide;
the donor B is methyl ammonium chloride, formamidine hydrochloride, methyl ammonium bromide, formamidine hydrobromide, methyl ammonium iodide or formamidine hydroiodide;
preferably, the organic solvent is dimethylformamide, dimethyl sulfoxide or γ -butyrolactone.
Preferably, the molar ratio of donor a to donor B is 1: (1-5) (e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1: 5);
preferably, the total mass percentage content of the donor a and the donor B in the organic solvent is 35 to 50 wt% (such as 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%).
Step S4, spin-coating a chlorobenzene solution of PCBM ([6,6] -phenyl-C61-methyl butyrate) on the photoactive layer to form an electron transport layer;
step S5, spin-coating a methanol solution of PDINO (perylene diimide derivative) on the electron transport layer to form a cathode modification layer;
and step S6, evaporating the cathode material to the cathode modification layer through thermal evaporation in vacuum to obtain the perovskite solar cell.
Preferably, the cathode material is metallic aluminum (Al) or silver (Ag).
The materials, reagents and the like used in the examples and comparative examples were all commercially available products.
Example 1
As shown in fig. 1 and fig. 2, the method for manufacturing a novel organic hole transport layer perovskite solar cell provided in this embodiment includes the following steps:
and step S1, ultrasonically washing the anode glass substrate sputtered with Indium Tin Oxide (ITO) for 2 times by using liquid detergent, deionized water, acetone and isopropanol in sequence, wherein each time is 10-15 min, and drying by using nitrogen after the cleaning is finished. And (3) putting the blow-dried ITO glass substrate into ultraviolet cleaning surface treatment equipment for treatment for 20min to obtain a pretreated substrate.
And step S2, depositing a BTCV polymer with the thickness of 20nm on the pretreated substrate to form an organic hole transport layer, wherein the specific steps mainly comprise two steps.
Preparation of organic small molecule monomer BTCV
Step s21, adding 0.588g (2.4mmol) of 2-bromocarbazole, 0.364g (2.4mmol) of 4-vinylbenzyl chloride and 20ml of acetone into a 100ml two-mouth bottle, heating to 75 ℃, adding 0.110g (2.8mmol) of sodium hydroxide and 0.02g (0.0589mmol) of tetrabutylammonium hydrogen sulfate, stirring for 4h, filtering, spin-drying the solvent, and performing column chromatography to obtain 0.5g (1.38mmol) of white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 0.5g (1.38mmol) of 9- (4-vinylbenzyl) -2-bromocarbazole, 0.0339g (0.690mmol) of 5,5 '-bis (trimethyltin) -2,2' -bithiophene, 0.05g (0.04mmol) of palladium tetratriphenylphosphine and 50ml of freshly distilled toluene into a two-neck flask, pumping gas for 3 times, heating to 130 ℃ under argon atmosphere, reacting for 12 hours, cooling to room temperature after the reaction is finished, spin-drying the solvent, adding a saturated potassium fluoride solution, extracting with dichloromethane (30 ml. times.3), namely using 30ml of dichloromethane for each extraction, extracting for 3 times, carrying out column chromatography after the solvent is spin-dried, obtaining yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, 0.11g (0.151mmol), namely organic small molecular monomer BTCV, wherein the molecular structural formula of the organic small molecular monomer BTCV is shown in figure 3, the mass spectrum of BTCV is shown in FIG. 4.
The synthetic route of the small molecular monomer BTCV is as follows:
cross-linking reaction of BTCV polymers
Step s22, placing organic small molecular monomer BTCV in N, N-Dimethylformamide (DMF), fully stirring and dissolving to prepare 1mg mL-1The BTCV solution of (1);
and step s23, filtering the BTCV solution through a 0.45-micron filter head, spin-coating for 60 seconds at the rotation speed of 4000r/min on a spin coater, and then annealing for 10min at 150 ℃ on a hot bench to perform a crosslinking reaction to form a crosslinked reticular organic hole transport layer with the thickness of 20 nm.
Step S3, PbI2And CH3NH3I, according to a molar ratio of 1:2 in N, N-Dimethylformamide (DMF) solution, PbI in the solution2And CH3NH3I total mass fraction is 40 wt%, stirring at room temperature to prepare perovskite precursor solution (CH)3NH3PbI3). Spin coating perovskite on organic hole transport layer at 5000r/min rotation speedAnd (3) dripping an anti-solvent chlorobenzene solvent when the precursor solution rotates for 4.5s to promote rapid crystallization of the perovskite layer, transferring the perovskite layer into the air, and carrying out thermal annealing treatment at 100 ℃ for 10min to obtain a black perovskite layer with the thickness of 300nm, namely the black perovskite layer is the photoactive layer.
Step S4, spin coating concentration on the photoactive layer to be 20mg mL-1PCBM ([6,6]]phenyl-C61-methyl butyrate) was spin-coated on the above perovskite layer at a rotation speed of 1500r/min for 30-60s to obtain an electron transport layer having a thickness of 20 nm.
Step S5, 1mg mL-1The methanol solution of PDINO (perylene diimide derivative) is spin-coated on the perovskite layer covered with PCBM for 30-60s at the rotating speed of 3000r/min to obtain a cathode modification layer with the thickness of 15 nm.
Step S6, finally 5 × 10-5And (3) carrying out vacuum evaporation on Al with the thickness of 100nm under Pa to obtain the perovskite solar cell.
As shown in FIG. 1, the device structure obtained in the embodiment of the invention is ITO/BTCV/CH3NH3PbI3The performance of the device tested by/PCBM/PDINO/Al is shown in figure 5, and under the optimal condition, the thickness of the material is 100mW cm-2The open-circuit voltage under the irradiation of the simulated sunlight is 1.00V, and the short-circuit current is 21.70mA cm-2The fill factor was 81%, and the photoelectric conversion efficiency was 17.58%.
Example 2
The preparation method of the novel organic hole transport layer perovskite solar cell provided by the embodiment comprises the following steps:
and step S1, ultrasonically washing the anode glass substrate sputtered with Indium Tin Oxide (ITO) for 2 times by using liquid detergent, deionized water, acetone and isopropanol in sequence, wherein each time is 10-15 min, and drying by using nitrogen after the cleaning is finished. And (3) putting the blow-dried ITO glass substrate into ultraviolet cleaning surface treatment equipment for treatment for 20min to obtain a pretreated substrate.
And step S2, depositing a BTCV polymer with the thickness of 10nm on the pretreated substrate to form an organic hole transport layer, wherein the specific steps mainly comprise two steps.
Preparation of organic small molecule monomer BTCV
Step s21, adding 0.588g (2.4mmol) of 2-bromocarbazole, 0.364g (2.4mmol) of 4-vinylbenzyl chloride and 20ml of acetone into a 100ml two-mouth bottle, heating to 75 ℃, adding 0.110g (2.8mmol) of sodium hydroxide and 0.02g (0.0589mmol) of tetrabutylammonium hydrogen sulfate, stirring for 4h, filtering, spin-drying the solvent, and performing column chromatography to obtain 0.5g (1.38mmol) of white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 0.5g (1.38mmol) of 9- (4-vinylbenzyl) -2-bromocarbazole, 0.0339g (0.690mmol) of 5,5 '-bis (trimethyltin) -2,2' -bithiophene, 0.05g (0.04mmol) of tetrakistriphenylphosphine palladium and 50ml of freshly distilled toluene into a two-neck bottle, extracting with air for 3 times, heating to 130 deg.C under argon atmosphere, reacting for 12h, cooling to room temperature after reaction, spin-drying solvent, adding saturated potassium fluoride solution, extracting with dichloromethane (30ml × 3), namely, 30ml of dichloromethane is used for extraction for 3 times, the solvent is dried by spinning, and then column chromatography is carried out, so as to obtain 0.11g (0.151mmol) of yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely organic small molecular monomer BTCV, which is shown in figure 3.
Cross-linking reaction of BTCV polymers
Step s22, placing organic small molecular monomer BTCV in N, N-Dimethylformamide (DMF), fully stirring and dissolving to prepare 1mg mL-1The BTCV solution of (1);
and step s23, filtering the BTCV solution by a 0.45-micron filter head, spin-coating the BTCV solution on a spin coater at 4000r/min for 30 seconds, and irradiating the BTCV solution under an ultraviolet lamp for 30min to perform a crosslinking reaction to form a crosslinked reticular organic hole transport layer with the thickness of 10 nm.
Step S3, PbI2And CH3NH3I, according to a molar ratio of 1:1 is dissolved in N, N-Dimethylformamide (DMF), PbI is dissolved in the solution2And CH3NH3I total mass fraction is 40 wt%, stirring at room temperature to prepare perovskite precursor solution (CH)3NH3PbI3). Spin-coating perovskite precursor solution on the organic hole transport layer at the rotation speed of 5000r/min, then dripping anti-solvent chlorobenzene solvent when rotating for 4.5s to promote rapid crystallization of the perovskite layer, then transferring the perovskite layer into the air, and carrying out thermal annealing treatment at 100 ℃ for 10min to obtain the perovskite/titanium composite materialTo a black perovskite layer with a thickness of 300nm, i.e. a photoactive layer.
Step S4, the concentration is 20mg mL-1PCBM ([6,6]]phenyl-C61-methyl butyrate) was spin-coated on the above perovskite layer at a rotation speed of 1500r/min for 30-60s to obtain an electron transport layer having a thickness of 20 nm.
Step S5, 1mg mL-1The methanol solution of PDINO (perylene diimide derivative) is spin-coated on the perovskite layer covered with PCBM for 30-60s at the rotating speed of 3000r/min to obtain a cathode modification layer with the thickness of 15 nm.
Step S6, finally 5 × 10-5And (3) evaporating Al with the thickness of 100nm in vacuum below Pa to serve as a metal electrode to obtain the perovskite solar cell.
The device structure obtained by the embodiment of the invention is ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, and the performance of the device is tested under the optimal condition of 100mW cm-2The open-circuit voltage under the irradiation of the simulated sunlight is 1.00V, and the short-circuit current is 21.39mA cm-2The fill factor was 79.95% and the photoelectric conversion efficiency was 17.10%.
Example 3
The preparation method of the novel organic hole transport layer perovskite solar cell provided by the embodiment comprises the following steps:
and step S1, ultrasonically washing the anode glass substrate sputtered with Indium Tin Oxide (ITO) for 2 times by using liquid detergent, deionized water, acetone and isopropanol in sequence, wherein each time is 10-15 min, and drying by using nitrogen after the cleaning is finished. And (3) putting the blow-dried ITO glass substrate into ultraviolet cleaning surface treatment equipment for treatment for 20min to obtain a pretreated substrate.
And step S2, depositing a BTCV polymer with the thickness of 15nm on the pretreated substrate to form an organic hole transport layer, wherein the specific steps mainly comprise two steps.
Preparation of organic small molecule monomer BTCV
Step s21, adding 0.588g (2.4mmol) of 2-bromocarbazole, 0.364g (2.4mmol) of 4-vinylbenzyl chloride and 20ml of acetone into a 100ml two-mouth bottle, heating to 60 ℃, adding 0.110g (2.8mmol) of sodium hydroxide and 0.02g (0.0589mmol) of tetrabutylammonium hydrogen sulfate, stirring for 4h, filtering, spin-drying the solvent, and performing column chromatography to obtain 0.5g (1.38mmol) of white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 0.5g (1.38mmol) of 9- (4-vinylbenzyl) -2-bromocarbazole, 0.0308g (0.627mmol) of 5,5 '-bis (trimethyltin) -2,2' -bithiophene, 0.05g (0.04mmol) of tetrakistriphenylphosphine palladium and 30ml of freshly distilled toluene into a two-mouth bottle, extracting with air for 3 times, heating to 120 deg.C under argon atmosphere, reacting for 12h, cooling to room temperature after reaction, spin-drying solvent, adding saturated potassium fluoride solution, extracting with dichloromethane (30ml × 3), namely, 30ml of dichloromethane is used for extraction for 3 times, the solvent is dried by spinning, and then column chromatography is carried out, so as to obtain 0.11g (0.151mmol) of yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely organic small molecular monomer BTCV, which is shown in figure 3.
Cross-linking reaction of BTCV polymers
Step s22, placing organic small molecule monomer BTCV in N, N-Dimethylformamide (DMF), fully stirring and dissolving to prepare 0.8mg mL-1The BTCV solution of (1);
and step s23, filtering the BTCV solution through a 0.45-micron filter head, spin-coating the BTCV solution on a spin coater at 4000r/min for 45 seconds, and annealing the BTCV solution on a hot table at 160 ℃ for 12min to perform a crosslinking reaction to form a crosslinked reticular organic hole transport layer with the thickness of 15 nm.
Step S3, mixing lead acetate and methyl ammonium iodide in a molar ratio of 1:3 dissolving in gamma-butyrolactone solution, PbI in the solution2And CH3NH3I total mass fraction is 50 wt%, stirring at room temperature to prepare perovskite precursor solution (CH)3NH3PbI3). Spin-coating perovskite precursor solution on the organic hole transport layer at the rotating speed of 5000r/min, then dripping anti-solvent chlorobenzene solvent when rotating for 4.5s to promote rapid crystallization of the perovskite layer, then transferring the perovskite layer into the air, and carrying out thermal annealing treatment at 90 ℃ for 10min to obtain a black perovskite layer with the thickness of 300nm, namely the black perovskite layer is the photoactive layer.
Step S4, spin coating concentration on the photoactive layer to be 20mg mL-1PCBM ([6,6]]-phenyl-C61-butyric acid methyl ester) at 1500r/minSpin-coating on the perovskite layer at high speed for 30-60s to obtain an electron transport layer with a thickness of 20 nm.
Step S5, 1mg mL-1The methanol solution of PDINO (perylene diimide derivative) is spin-coated on the perovskite layer covered with PCBM for 30-60s at the rotating speed of 3000r/min to obtain a cathode modification layer with the thickness of 15 nm.
Step S6, finally 5 × 10-5And (3) performing vacuum evaporation on Ag with the thickness of 100nm below Pa to obtain the perovskite solar cell as a metal electrode.
The device structure obtained by the embodiment of the invention is ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Ag, testing the performance of the device under the optimal condition of 100mW cm-2The open-circuit voltage under the irradiation of the simulated sunlight is 1.01V, and the short-circuit current is 20.84mA cm-2The fill factor was 78.13% and the photoelectric conversion efficiency was 16.44%.
Example 4
The preparation method of the novel organic hole transport layer perovskite solar cell provided by the embodiment comprises the following steps:
and step S1, ultrasonically washing the anode glass substrate sputtered with the fluorine-doped tin oxide FTO for 2 times by using liquid detergent, deionized water, acetone and isopropanol in sequence, wherein each time is 10-15 min, and drying by using nitrogen after the cleaning is finished. And (4) placing the blow-dried FTO glass substrate into ultraviolet cleaning surface treatment equipment for treatment for 20min to obtain a pretreated substrate.
And step S2, depositing a BTCV polymer with the thickness of 18nm on the pretreated substrate to form an organic hole transport layer, wherein the specific steps mainly comprise two steps.
Preparation of organic small molecule monomer BTCV
Step s21, adding 0.588g (2.4mmol) of 2-bromocarbazole, 0.364g (2.4mmol) of 4-vinylbenzyl chloride and 20ml of acetone into a 100ml two-mouth bottle, heating to 75 ℃, adding 0.110g (2.8mmol) of sodium hydroxide and 0.02g (0.0589mmol) of tetrabutylammonium hydrogen sulfate, stirring for 4h, filtering, spin-drying the solvent, and performing column chromatography to obtain 0.5g (1.38mmol) of white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 0.5g (1.38mmol) of 9- (4-vinylbenzyl) -2-bromocarbazole, 0.0308g (0.627mmol) of 5,5 '-bis (trimethyltin) -2,2' -bithiophene, 0.05g (0.04mmol) of tetrakistriphenylphosphine palladium and 30ml of freshly distilled toluene into a two-mouth bottle, extracting with air for 3 times, heating to 120 deg.C under argon atmosphere, reacting for 12h, cooling to room temperature after reaction, spin-drying solvent, adding saturated potassium fluoride solution, extracting with dichloromethane (30ml × 3), namely, 30ml of dichloromethane is used for extraction for 3 times, the solvent is dried by spinning, and then column chromatography is carried out, so as to obtain 0.11g (0.151mmol) of yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely organic small molecular monomer BTCV, which is shown in figure 3.
Cross-linking reaction of BTCV polymers
Step s22, placing organic small molecular monomer BTCV in N, N-Dimethylformamide (DMF), fully stirring and dissolving to prepare 1.5mg mL-1The BTCV solution of (1);
and step s23, filtering the BTCV solution by a 0.45-micron filter head, spin-coating the BTCV solution on a spin coater at 4000r/min for 55 seconds, and irradiating the BTCV solution under an ultraviolet lamp for 25min to perform a crosslinking reaction to form a crosslinked reticular organic hole transport layer with the thickness of 18 nm.
Step S3, mixing lead chloride and formamidine hydroiodide in a molar ratio of 1:1 dissolving in dimethyl sulfoxide solution, PbI in the solution2And CH3NH3I total mass fraction is 50 wt%, stirring at room temperature to prepare perovskite precursor solution (CH)3NH3PbI3). Spin-coating perovskite precursor solution on the organic hole transport layer at the rotating speed of 5000r/min, then dripping anti-solvent chlorobenzene solvent when rotating for 4.5s to promote rapid crystallization of the perovskite layer, then transferring the perovskite layer into the air, and carrying out thermal annealing treatment at 100 ℃ for 10min to obtain a black perovskite layer with the thickness of 300nm, namely the black perovskite layer is the photoactive layer.
Step S4, spin coating concentration on the photoactive layer to be 20mg mL-1PCBM ([6,6]]phenyl-C61-methyl butyrate) was spin-coated on the above perovskite layer at a rotation speed of 1500r/min for 30-60s to obtain an electron transport layer having a thickness of 20 nm.
Step S5, 1mg mL-1In methanol of PDINO (perylene diimide derivative)And (3) spin-coating 30-60s on the perovskite layer covered with the PCBM at the rotating speed of 3000r/min to obtain a cathode modification layer with the thickness of 15 nm.
Step S6, finally 5 × 10-5And (3) performing vacuum evaporation on Ag with the thickness of 100nm below Pa to obtain the perovskite solar cell as a metal electrode.
The device structure obtained by the embodiment of the invention is FTO/BTCV/CH3NH3PbI3PCBM/PDINO/Ag, testing the performance of the device under the optimal condition of 100mW cm-2The open-circuit voltage under the irradiation of the simulated sunlight is 1.00V, and the short-circuit current is 20.51mA cm-2The fill factor was 80.05%, and the photoelectric conversion efficiency was 16.42%.
Example 5
The difference between this embodiment and embodiment 1 is that, in step s23, after the BTCV solution is filtered by a filter, spin-coated on a spin coater, and then annealed at 130 ℃ for 12min on a hot stage, so that a cross-linking reaction occurs, and a cross-linked mesh-shaped organic hole transport layer is formed.
The perovskite solar cell prepared in the embodiment has the structure of FTO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, the perovskite cell of this example was tested for performance at 100mW cm-2The open-circuit voltage is 1.00V and the short-circuit current is 21.03mA cm under the irradiation of the simulated sunlight-2The fill factor was 79.21% and the photoelectric conversion efficiency was 16.66%.
Comparative example 1
The present comparative example differs from example 1 in that in step S2, the organic hole transport layer used was PEDOT: the PSS solution, other steps and methods are the same as those of example 1, and are not repeated herein.
The perovskite solar cell prepared in the comparative example has a structure of ITO/PEDOT: PSS/CH3NH3PbI3The perovskite cells of the comparative example were subjected to performance test using/PCBM/PDINO/Al, and the test results are shown in FIG. 5 at 100 mW/cm-2The J-V curve is measured under the irradiation of simulated sunlight, and the open-circuit voltage is 0.91V, and the short-circuit current is 19.77mA cm-2The fill factor was 77.03%, and the photoelectric conversion efficiency was 13.86%.
Comparative example 2
This comparative example differs from example 1 in that the small organic molecule monomer BTCV was formulated to 0.5mg mL in step s22-1The other steps and methods of the BTCV solution are the same as those of example 1, and are not repeated herein.
The perovskite solar cell prepared in the comparative example has the structure of ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, the perovskite cell of this comparative example was subjected to a performance test at 100mW cm-2The J-V curve is measured under the irradiation of the simulated sunlight, and the open-circuit voltage is 1.00V, and the short-circuit current is 18.28mA cm-2The fill factor was 70.64%, and the photoelectric conversion efficiency was 12.91%.
Comparative example 3
The difference between this comparative example and example 1 is that the BTCV solution is spin-coated in step s23 and then annealed at 100 ℃ for 10min on a hot stage, and the other steps and methods are the same as example 1 and are not repeated herein.
The perovskite solar cell prepared in the comparative example has the structure of ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, the perovskite cell of this comparative example was subjected to a performance test at 100mW cm-2The J-V curve is measured under the irradiation of the simulated sunlight, and the open-circuit voltage is 1.00V, and the short-circuit current is 20.33mA cm-2The fill factor was 75.87%, and the photoelectric conversion efficiency was 15.42%.
Comparative example 4
The difference between this comparative example and example 1 is that in the preparation of organic small molecule monomer BTCV, 1.176g (4.8mmol) of 2-bromocarbazole, 0.364g (2.4mmol) of 4-vinylbenzyl chloride, 0.110g (2.8mmol) of sodium hydroxide and 0.02g (0.0589mmol) of tetrabutylammonium hydrogen sulfate are added in step s21, and the other steps are the same as in example 1 and are not repeated herein.
The perovskite solar cell prepared in the comparative example has the structure of ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, the perovskite cell of this comparative example was subjected toPerformance test at 100mW cm-2The J-V curve is measured under the irradiation of the simulated sunlight, and the open-circuit voltage is 0.824V, and the short-circuit current is 16.33mA cm-2The packing factor was 60.85%, and the photoelectric conversion efficiency was 8.188%.
Comparative example 5
The present comparative example differs from example 1 in that PbI is added in step S32And CH3NH3I, according to a molar ratio of 2:1 is dissolved in N, N-Dimethylformamide (DMF), PbI is dissolved in the solution2And CH3NH3I total mass fraction is 40 wt%, stirring at room temperature to prepare perovskite precursor solution (CH)3NH3PbI3) The other steps and methods are the same as those in embodiment 1, and are not described herein again.
The perovskite solar cell prepared in the comparative example has the structure of ITO/BTCV/CH3NH3PbI3PCBM/PDINO/Al, the perovskite cell of this comparative example was subjected to a performance test at 100mW cm-2The J-V curve is measured under the irradiation of the simulated sunlight, and the open-circuit voltage is 0.800V, and the short-circuit current is 17.28mA cm-2The packing factor was 65.21%, and the photoelectric conversion efficiency was 9.014%.
The low photoelectric conversion efficiency of the solar cell is caused by PbI2There is a large amount of residue, no CH is generated3NH3PbI3It cannot absorb light energy; PbI2The insulating material is an insulator, which hinders the transfer of charges, increases the resistance, and finally reduces the photoelectric conversion efficiency of the solar cell.
In summary, the following steps: the invention relates to a perovskite solar cell based on an organic cross-linked hole transport layer, which comprises the following components in structure from bottom to top: the hole transport layer can well reduce the occurrence probability of electronic coupling or charge recombination at an interface, the photoelectric conversion efficiency of the planar heterojunction perovskite battery prepared by the method reaches 17.58%, the performance of the perovskite solar battery is improved, and the planar heterojunction perovskite solar battery can be used for photoelectric conversion.
Meanwhile, the organic small molecular monomer BTCV has the advantages of simple synthesis steps, low cost, high yield and stable property, can be commercially produced, and greatly reduces the cost of the perovskite solar cell.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a novel organic hole transport layer perovskite solar cell is characterized by comprising the following steps:
step S1, cleaning and drying the glass substrate plated with the anode material, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step S2, depositing BTCV polymer on the pretreated substrate to form an organic hole transport layer;
s3, spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 90-110 ℃ to obtain a perovskite crystal film, namely a photoactive layer;
step S4, spin-coating a chlorobenzene solution of PCBM on the photoactive layer to form an electron transport layer;
step S5, spin-coating a methanol solution of PDINO on the electron transport layer to form a cathode modification layer;
and step S6, evaporating the cathode material to the cathode modification layer through thermal evaporation in vacuum to obtain the perovskite solar cell.
2. The method for preparing a novel organic hole transport layer perovskite solar cell as claimed in claim 1, wherein the step of forming the organic hole transport layer in step S2 comprises the following steps:
step s21, placing the organic small molecular monomer BTCV in N, N-dimethylformamide, fully stirring and dissolving to prepare a BTCV solution;
step s22, filtering the BTCV solution, spin-coating the BTCV solution on a spin coater for 30-60 seconds, and then curing to form a cross-linked reticular organic hole transport layer;
preferably, the concentration of the BTCV solution is 0.5-1.5mg mL-1；
Preferably, the thickness of the organic hole transport layer is 10-20 nm.
3. The method according to claim 2, wherein in step s22, the curing treatment is annealing at 130-170 ℃ for 8-12min or irradiation with an ultraviolet lamp for 25-35 min.
4. The preparation method of the novel organic hole transport layer perovskite solar cell as claimed in claim 2, wherein the specific preparation method of the organic small molecule monomer BTCV comprises the following steps:
heating 2-bromocarbazole, 4-vinylbenzyl chloride and acetone to 60-90 ℃, adding sodium hydroxide and tetrabutylammonium hydrogen sulfate, stirring, filtering, spin-drying a solvent, and performing column chromatography to obtain white solid 9- (4-vinylbenzyl) -2-bromocarbazole;
adding 9- (4-vinylbenzyl) -2-bromocarbazole, 5 '-bis (trimethyltin) -2,2' -bithiophene, palladium tetratriphenylphosphine and newly evaporated toluene into a container, pumping gas for 2-4 times, heating to 110 ℃ and 130 ℃ in an argon atmosphere for reaction, cooling to room temperature after the reaction is finished, spin-drying the solvent, adding a saturated potassium fluoride solution, extracting by using dichloromethane, and performing column chromatography after spin-drying the solvent to obtain a yellow solid 5,5 '-bis [9- (4-vinylbenzyl) -2-carbazolyl ] -2,2' -bithiophene, namely the organic small molecular monomer BTCV.
5. The method of preparing a novel organic hole transport layer perovskite solar cell according to claim 4, wherein the molar ratio of the 2-bromocarbazole to the 4-vinylbenzyl chloride is 1:1.
6. The method of claim 4, wherein the molar ratio of 9- (4-vinylbenzyl) -2-bromocarbazole to 5,5 '-bis (trimethyltin) -2,2' -bithiophene is 2: 1.
7. The method of manufacturing a novel organic hole transport layer perovskite solar cell as claimed in claim 1, wherein in step S3, the method of manufacturing the perovskite precursor solution comprises:
dissolving the donor A in an organic solvent, then adding the donor B, and stirring to obtain a perovskite precursor solution;
wherein the donor A is lead chloride, lead bromide, lead acetate, lead thiocyanate or lead iodide;
the donor B is methyl ammonium chloride, formamidine hydrochloride, methyl ammonium bromide, formamidine hydrobromide, methyl ammonium iodide or formamidine hydroiodide;
preferably, the organic solvent is dimethylformamide, dimethyl sulfoxide or γ -butyrolactone.
8. The method of fabricating the novel organic hole transport layer perovskite solar cell of claim 7, wherein the molar ratio of the donor A to the donor B is 1: (1-5);
preferably, the total mass percentage of the donor A and the donor B in the organic solvent is 35-50 wt%.
9. The perovskite solar cell prepared by the preparation method of the novel organic hole transport layer perovskite solar cell as claimed in any one of claims 1 to 8.
10. Use of an organic hole transport layer for the preparation of a photovoltaic device; the organic hole transport layer is prepared by adopting the preparation method of the novel organic hole transport layer perovskite solar cell as claimed in any one of claims 1 to 6.
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