CN112635680B - Method for deeply doping hole dopant under low concentration through temperature induction - Google Patents

Method for deeply doping hole dopant under low concentration through temperature induction Download PDF

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CN112635680B
CN112635680B CN202110253052.XA CN202110253052A CN112635680B CN 112635680 B CN112635680 B CN 112635680B CN 202110253052 A CN202110253052 A CN 202110253052A CN 112635680 B CN112635680 B CN 112635680B
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transport layer
hole transport
tbapf
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spiro
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CN112635680A (en
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韩飞
王玲玲
范敏
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ENERGY RESEARCH INSTITUTE OF JIANGXI ACADEMY OF SCIENCES
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    • H—ELECTRICITY
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    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a method for deeply doping a temperature-induced hole dopant under low concentration, which comprises the following steps of: mixing hole transport layer material and TBAPF6Dissolving in dichloromethane to obtain hole transport layer material solution, and dissolving hole transport layer material solution TBAPF6The mass concentration of the perovskite thin film is 1-4 wt%, and a hole transport layer is prepared on the perovskite thin film by using corresponding spin coating parameters; and carrying out low-temperature heating treatment on the obtained n-i-p type perovskite solar cell, and then naturally cooling to room temperature. The invention adopts TBAPF6The low-concentration TBAPF-based low-temperature perovskite solar cell can be effectively improved by doping a hole transport layer material as a hole dopant and performing low-temperature heating treatment on the prepared perovskite solar cell6The photovoltaic performance and stability of the solar cell prepared by the doped hole transport layer material.

Description

Method for deeply doping hole dopant under low concentration through temperature induction
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a method for deeply doping a hole dopant under low concentration by temperature induction.
Background
In recent years, organic-inorganic hybrid perovskite solar cells are widely researched due to low cost, solution solubility and flexible processing, and the device efficiency of the organic-inorganic hybrid perovskite solar cells is dramatically improved. 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD) is the most used hole transport material in perovskite solar cells nowadays, and n-i-p type perovskite solar cells need to be doped with conventional hole dopants 4-tert-butylpyridine (tBP) and lithium bistrifluoromethanesulfonylimide (Li-TFSI), wherein the Li-TFSI can significantly improve the conductivity and hole mobility of a Spiro-OMeTAD thin film layer, but the introduction of Li-TFSI brings the following problems: (1) Li-TFSI is easy to deliquesce, so that the prepared Spiro-OMeTAD film has more holes, the decomposition of perovskite is accelerated, and the performance of the prepared device is reducedAnd stability; (2) Li-TFSI has low solubility in chlorobenzene, chloroform and other organic solvents, so that Li-TFSI is easy to gather in a Spiro-OMeTAD film, and the Spiro-OMeTAD is also easy to gather and crystallize to be unfavorable for hole transmission so as to influence the photoelectric property of a corresponding solar cell; (3) li+Can migrate from the hole transport layer to other layers of the perovskite solar cell, thereby affecting the stability of the device. The above problems all seriously affect the stability of the prepared solar cell, thereby limiting the further application of the perovskite solar cell, and therefore, how to solve the problems to realize the long-term stable storage and use of the perovskite solar cell is very important.
At present, the means for deeply doping the hole transport layer material mainly includes increasing the concentration of the hole dopant, oxidizing the hole transport layer material by air or oxidizing substances, mixing a plurality of hole dopants and the like, and how to obtain the deep doping effect under the condition of reducing the doping concentration is a direction worthy of research, but the prior art does not report the deep doping of the hole dopant of the temperature-induced low-concentration solar cell.
Disclosure of Invention
The invention aims to provide a method for deeply doping a temperature-induced hole dopant at low concentration by adopting tetrabutylammonium hexafluorophosphate (TBAPF)6) 2,2',7,7' -tetrakis [ N, N-di (4-methoxyphenyl) amino as hole dopant for hole transport layer materials]Doping 9,9' -spirobifluorene (Spiro-OMeTAD), and heating the prepared perovskite solar cell at low temperature (less than or equal to 50 ℃), so that the low-concentration TBAPF (tert-butyl acrylate) can be effectively improved6The doped Spiro-OMeTAD hole transport layer material has the photovoltaic performance of the solar cell and improves the stability of the prepared perovskite thin film and the solar cell.
The invention is realized by the following technical scheme. A method for deeply doping a temperature-induced hole dopant at a low concentration is prepared by the following steps in sequence from bottom to top: the structure comprises FTO conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer and an Au n-i-p type perovskite solar cell structure; the manufacturing process of the hole transport layer comprises the following steps: selecting TBAPF6As hole dopingA hetero agent, a hole transport layer material and TBAPF6Dissolving in dichloromethane to obtain hole transport layer material solution containing TBAPF6The mass concentration of the perovskite thin film is 1-4 wt%, and a hole transport layer is prepared on the perovskite thin film by using corresponding spin coating parameters; and carrying out low-temperature heating treatment on the obtained n-i-p type perovskite solar cell, and then naturally cooling to room temperature.
More preferably, the low-temperature heat treatment temperature is 50 ℃.
More preferably, the low-temperature heat treatment time is 60 seconds.
Further preferably, the hole transport layer material is selected from Spiro-OMeTAD.
Further preferably, the content of Spiro-OMeTAD in the solution of the Spiro-OMeTAD hole transport layer per ml is 72.3 mg.
Further preferably, TBAPF is contained in the solution of the hole transport layer material6The mass concentration of (B) is 4 wt%.
The invention has the beneficial effects that: with the electrolyte tetrabutylammonium hexafluorophosphate (TBAPF)6) As hole dopant, hole transport layer material was doped, and Spiro-OMeTAD was dissolved using dichloromethane instead of chlorobenzene to promote TBAPF6The calcium titanate is uniformly dispersed in the Spiro-OMeTAD/dichloromethane, and effectively inhibits aggregation and crystallization of the Spiro-OMeTAD, so that the Spiro-OMeTAD completely covers the surface of the perovskite film to prevent water and oxygen in the air from damaging the perovskite layer; the prepared perovskite solar cell is subjected to low-temperature heating treatment, so that the ion migration in the Spiro-OMeTAD film is accelerated, the distribution state of holes and free electrons in the film is changed, the Spiro-OMeTAD oxidation reaction is promoted, and the low-concentration TBAPF (tert-butyl acrylate copolymer) is effectively improved6And the doped Spiro-OMeTAD hole transport layer material is used for preparing the photovoltaic performance of the solar cell. At the same time, TBA+PF, capable of forming covalent bond with lead iodide to passivate perovskite defects6 -Is easy to form hydrogen bond interaction with organic components MAI and FAI of perovskite so as to stabilize the escape of the organic components MAI and FAI and inhibit the yellow phase delta-FAPBI3The perovskite is formed, and the stability of the prepared perovskite thin film and the solar cell is obviously improved.
Drawings
FIG. 1 is a schematic diagram of perovskite solar cells prepared in comparative example 1 and example 1J-VCharacteristic curve.
FIG. 2 is a schematic diagram of perovskite solar cells prepared in comparative example 2 and example 2J-VCharacteristic curve.
FIG. 3 is a graph of perovskite solar cells prepared in comparative example 3 and example 3J-VCharacteristic curve.
FIG. 4 shows perovskite solar cells prepared in comparative example 4 and example 4J-VCharacteristic curve.
FIG. 5 is a view showing perovskite solar cells prepared in comparative example 5 and reference example 1J-VCharacteristic curve.
FIG. 6 is a view showing perovskite solar cells prepared in comparative example 6 and reference example 2J-VCharacteristic curve.
FIG. 7 shows perovskite solar cell fabricated in comparative example 7J-VCharacteristic curve.
FIG. 8 shows perovskite solar cells prepared in comparative example 5 and example 4J-VCharacteristic curve.
Fig. 9 is a statistical plot of PCEs of perovskite solar cells prepared in comparative examples 1-6, examples 1-4, and reference examples 1-2.
FIG. 10 is glass/perovskite/(4 wt% TBAPF)6 + Spiro-OMeTAD) samples and glass/perovskite/(4 wt% TBAPF)6 + Spiro-OMeTAD) (low temperature heat treatment at 50 ℃) steady state fluorescence spectra of the samples.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The invention discloses a method for deeply doping a temperature-induced hole dopant under low concentration, which comprises the following steps of: FTO conductive glass, electron transport layer, perovskite light absorption layer, hole transport layer, Au, the concrete step is as follows:
step 1: cleaning the surface of the FTO conductive glass by sequentially adopting a detergent, deionized water, acetone and absolute ethyl alcohol, and drying the FTO conductive glass by using nitrogen for later use;
step 2: adding diisopropyl di (acetylacetonate) titanate into n-butanol, and stirring to uniformly mix to obtain a mixed solution A;
and step 3: spin-coating the mixed solution A on the surface of the FTO conductive glass cleaned in the step 1, and baking the FTO conductive glass at the temperature of 150 ℃ for 30 min to obtain compact TiO2A layer;
and 4, step 4: adding TiO into the mixture2Adding the slurry into absolute ethyl alcohol, and stirring to uniformly mix the slurry and the absolute ethyl alcohol to obtain a mixed solution B;
and 5: the dense TiO obtained in step 32Spin-coating the mixed solution B on the surface of the FTO conductive glass layer, baking at 125 ℃ for 10 min, and annealing at 500 ℃ for 60 min to obtain mesoporous TiO2A layer;
step 6: preparation of 1.1M FAxMA1-xPbI3(x = 0.8) solution (FA)+Is CH (NH)2)2 +, MA+Is CH3NH3 +) Using a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 3: 1, fully stirring to obtain a perovskite precursor solution; spreading the perovskite precursor solution on the FTO/TiO obtained in the step 52And (3) carrying out segmented spin coating on the surface of the substrate, wherein the segmented spin coating has the following process parameters: spin-coating at 1300 rpm for 10 s; and a second stage: spin-coating at a rotation speed of 5000 r/min for 30 s, dripping 200 μ L chlorobenzene antisolvent when the remaining 15 s of the second stage of spin-coating time, after the spin-coating is finished, heating at 50 ℃ for 15 s, and then heating and annealing at 100 ℃ for 60 min to obtain the perovskite thin film;
and 7: preparing a hole transport layer material solution: selecting TBAPF6As hole dopants, hole transport layer materials and TBAPF6Dissolving in dichloromethane to obtain hole transport layer material solution containing TBAPF6The mass concentration of (A) is 1-4 wt%; preparing a hole transport layer on the perovskite thin film by using corresponding spin coating parameters; the selected hole transport layer material is Spiro-OMeTAD; the content of Spiro-OMeTAD in the Spiro-OMeTAD hole transport layer solution per ml was 72.3 mg;
and 8: evaporating 60 nm Au on the surface of the hole transport layer obtained in the step 7 to form a counter electrode;
and step 9: heating the solar cell device at 50 deg.C for 60 s, and naturally cooling to room temperatureJ-VAnd (6) testing.
Example 1
Step 1: cleaning the surface of the FTO conductive glass by sequentially adopting a detergent, deionized water, acetone and absolute ethyl alcohol, and drying the FTO conductive glass by using nitrogen for later use;
step 2: adding diisopropyl di (acetylacetonate) titanate into n-butanol, and stirring to uniformly mix to obtain a mixed solution A;
and step 3: spin-coating the mixed solution A on the surface of the FTO conductive glass cleaned in the step 1, and baking the FTO conductive glass at the temperature of 150 ℃ for 30 min to obtain compact TiO2A layer;
and 4, step 4: adding TiO into the mixture2Adding the slurry into absolute ethyl alcohol, and stirring to uniformly mix the slurry and the absolute ethyl alcohol to obtain a mixed solution B;
and 5: the dense TiO obtained in step 32Spin-coating the mixed solution B on the surface of the FTO conductive glass layer, baking at 125 ℃ for 10 min, and annealing at 500 ℃ for 60 min to obtain mesoporous TiO2A layer;
step 6: preparation of 1.1M FAxMA1-xPbI3(x = 0.8) solution, wherein, FA+Is CH (NH)2)2 +, MA+Is CH3NH3 +Using a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 3: 1, fully stirring to obtain a perovskite precursor solution; spreading the perovskite precursor solution on the FTO/TiO obtained in the step 52And (3) carrying out segmented spin coating on the surface of the substrate, wherein the segmented spin coating has the following process parameters: spin-coating at 1300 rpm for 10 s; and a second stage: spin-coating at a rotation speed of 5000 r/min for 30 s, dripping 200 μ L chlorobenzene antisolvent when the remaining 15 s of the second stage of spin-coating time, after the spin-coating is finished, heating at 50 ℃ for 15 s, and then heating and annealing at 100 ℃ for 60 min to obtain the perovskite thin film;
and 7: a72.3 mg/mL solution of Spiro-OMeTAD in methylene chloride was prepared containing 72.3 mg of Spiro-OMeTAD, 1 wt% TBAPF6And 1 mL of dichloromethane, and then sufficiently stirring to obtain a Spiro-OMeTAD solution; spreading a Spiro-OMeTAD solution on the surface of the perovskite, then spin-coating for 30 s at the rotating speed of 3000 r/min, and naturally airing after the spin-coating is finished to obtain a Spiro-OMeTAD film on the perovskite substrate;
and 8: evaporating 60 nm Au on the surface of the hole transport layer obtained in the step 7 to form a counter electrode;
and step 9: heating the solar cell device at 50 deg.C for 60 s, and naturally cooling to room temperatureJ-VAnd (6) testing.
Example 2
Steps 1-6, step 8 and step 9 were the same as in example 1 except that TBAPF in step 76The mass concentration of (B) is 2 wt%.
Example 3
Steps 1-6, step 8 and step 9 were the same as in example 1 except that TBAPF in step 76The mass concentration of (B) is 3 wt%.
Example 4
Steps 1-6, step 8 and step 9 were the same as in example 1 except that TBAPF in step 76The mass concentration of (B) is 4 wt%.
Reference example 1
Steps 1-6, step 8 and step 9 were the same as in example 1 except that TBAPF in step 76The mass concentration of (B) is 6 wt%.
Reference example 2
Steps 1-6, step 8 and step 9 were the same as in example 1 except that TBAPF in step 76The mass concentration of (B) is 8 wt%.
Comparative example 1
Step 1: cleaning the surface of the FTO conductive glass by sequentially adopting a detergent, deionized water, acetone and absolute ethyl alcohol, and drying the FTO conductive glass by using nitrogen for later use;
step 2: adding diisopropyl di (acetylacetonate) titanate into n-butanol, and stirring to uniformly mix to obtain a mixed solution A;
and step 3: spin-coating the mixed solution A on the surface of the FTO conductive glass cleaned in the step 1, and baking the FTO conductive glass at the temperature of 150 ℃ for 30 min to obtain compact TiO2A layer;
and 4, step 4: adding TiO into the mixture2Adding the slurry into absolute ethyl alcohol, and stirring to uniformly mix the slurry and the absolute ethyl alcohol to obtain a mixed solution B;
and 5: the dense TiO obtained in step 32Spin-coating the mixed solution B on the surface of the FTO conductive glass layer, baking at 125 ℃ for 10 min, and annealing at 500 ℃ for 60 min to obtain mesoporous TiO2A layer;
step 6: preparation of 1.1M FAxMA1-xPbI3(x = 0.8) solution (wherein, FA+Is CH (NH)2)2 +, MA+Is CH3NH3 +) Using a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 3: 1, fully stirring to obtain a perovskite precursor solution; spreading the perovskite precursor solution on the FTO/TiO obtained in the step 52And (3) carrying out segmented spin coating on the surface of the substrate, wherein the segmented spin coating has the following process parameters: spin-coating at 1300 rpm for 10 s; and a second stage: spin-coating at a rotation speed of 5000 r/min for 30 s, dripping 200 μ L chlorobenzene antisolvent when the remaining 15 s of the second stage of spin-coating time, after the spin-coating is finished, heating at 50 ℃ for 15 s, and then heating and annealing at 100 ℃ for 60 min to obtain the perovskite thin film;
and 7: a72.3 mg/mL solution of Spiro-OMeTAD in methylene chloride was prepared containing 72.3 mg of Spiro-OMeTAD, 1 wt% TBAPF6And 1 mL of dichloromethane, and then sufficiently stirring to obtain a Spiro-OMeTAD solution; spreading a Spiro-OMeTAD solution on the surface of the perovskite, then spin-coating for 30 s at the rotating speed of 3000 r/min, and naturally airing after the spin-coating is finished to obtain a Spiro-OMeTAD film on the perovskite substrate;
and 8: evaporating 60 nm Au on the surface of the hole transport layer obtained in the step 7 to form a counter electrode;
and step 9: without any treatment, directly carrying outJ-VAnd (6) testing.
Comparative example 2
Steps 1-6, step 8 and step 9 were the same as in comparative example 1 except that TBAPF in step 76The mass concentration of (B) is 2 wt%.
Comparative example 3
Steps 1-6, step 8 and step 9 were the same as in comparative example 1 except that TBAPF in step 76The mass concentration of (B) is 3 wt%.
Comparative example 4
Steps 1-6, step 8 and step 9 were the same as in comparative example 1 except that TBAPF in step 76The mass concentration of (B) is 4 wt%.
Comparative example 5
Steps 1-6, step 8 and step 9 were the same as in comparative example 1 except that TBAPF in step 76The mass concentration of (B) is 6 wt%.
Comparative example 6
Steps 1-6, step 8 and step 9 were the same as in comparative example 1 except that TBAPF in step 76The mass concentration of (B) is 8 wt%.
Comparative example 7
In contrast to comparative example 1, step 7 was: preparing 72.3 mg/mL of a Spiro-OMeTAD/dichloromethane solution containing 72.3 mg of Spiro-OMeTAD and 1 mL of dichloromethane, and then stirring thoroughly; and (3) spreading a Spiro-OMeTAD solution on the surface of the perovskite, spin-coating at the rotating speed of 3000 r/min for 30 s, and naturally airing after the spin-coating is finished to obtain the Spiro-OMeTAD hole transport layer thin film on the perovskite substrate.
The perovskite solar cells obtained in the examples and comparative examples were tested and analyzed for performance:
FIG. 1 is a schematic diagram of perovskite solar cells prepared in comparative example 1 and example 1J-VA characteristic curve; FIG. 2 is a schematic diagram of perovskite solar cells prepared in comparative example 2 and example 2J-VA characteristic curve; FIG. 3 is a graph of perovskite solar cells prepared in comparative example 3 and example 3J-VA characteristic curve; FIG. 4 shows perovskite solar cells prepared in comparative example 4 and example 4J-VA characteristic curve; FIG. 5 is a view showing perovskite solar cells prepared in comparative example 5 and reference example 1J-VA characteristic curve; FIG. 6 is a view showing perovskite solar cells prepared in comparative example 6 and reference example 2J-VA characteristic curve; FIG. 7 shows perovskite solar cell fabricated in comparative example 7J-VCharacteristic curve. As can be derived from FIGS. 1-7, at TBAPF6Has a mass concentration of 1 to 4 wt% low temperature heating helps to enhance the PCE of the prepared perovskite solar cell. At high TBAPF concentrations6Under the doping condition (mass concentration is 6-8 wt%), low-temperature heating treatment does not contribute to improving PCE of the prepared perovskite solar cell.
FIG. 8 shows perovskite solar cells prepared in comparative example 5 and example 4J-VA characteristic curve; at TBAPF6Is better than TBAPF through low-temperature heating under the doping condition that the mass concentration is 4 wt percent6With a mass concentration of 6 wt% of PCE under doping conditions. It is shown that at low concentrations of doping, low temperature heating helps to raise the PCE of perovskite solar cells.
FIG. 9 is a PCE histogram of perovskite solar cells prepared in comparative examples 1-6, examples 1-4 and reference examples 1-2; table 1 shows the photovoltaic performance of the perovskite solar cells prepared in comparative examples 1 to 7, examples 1 to 4 and reference examples 1 to 2.
TABLE 1 photovoltaic Performance of perovskite solar cells
Figure 806249DEST_PATH_IMAGE001
In comparative examples 1-6, based on 6 wt% TBAPF6The optimum device performance of the doped Spiro-OMeTAD hole transport layer thin film assembled perovskite solar cell is 17.31%, and 1 wt%, 2 wt%, 3 wt%, 4 wt% and 8 wt% TBAPF6The optimal PCEs for doped Spiro-omtad hole transport layer thin film assembled perovskite solar cells are 11.54%, 14.74%, 16.39%, 16.68%, and 15.53%, respectively; in examples 1-4 and reference examples 1-2, based on 4 wt% of TBAPF6The optimum device performance of the doped Spiro-OMeTAD hole transport layer thin film assembled perovskite solar cell (50 ℃ low temperature heat treatment for 60 s) is 18.05%, and TBAPF of 1 wt%, 2 wt%, 3 wt%, 6 wt% and 8 wt%6The optimal PCEs of the perovskite solar cell assembled by the doped Spiro-OMeTAD hole transport layer thin film (low-temperature heat treatment at 50 ℃ for 60 s) are 15.08%, 16.47%, 16.90%, 16.71% and 15.15% respectively; TABLE 1 Performance data for perovskite solar cells taken together with TBAPF6Increase of doping concentrationAdditionally, the performance of the device is improved firstly and then reduced, and the performance is reduced to 6 wt% of TBAPF6The perovskite solar cell performance under the doping concentration reaches the optimum, and 1-8 wt% of TBAPF is subjected to low-temperature heating treatment6Doped Spiro-OMeTAD hole transport layer thin film assembled perovskite solar cell is subjected to low temperature heat treatment at 50 ℃ for 60 s and performance test is carried out, based on TBAPF of 4 wt%6Performance of perovskite solar cells with doping concentration (V oc = 1.09 V, J sc = 21.79 mA cm-2FF = 0.76, PCE = 18.05%) to an optimum, even better, than the optimum performance of the device of reference example 1 (V oc = 1.07 V, J sc = 21.69 mA cm-2FF = 0.72 and PCE = 16.71%), which is because the low-temperature heating treatment can accelerate the ion migration inside the Spiro-OMeTAD thin film and change the distribution state of holes and free electrons inside the film, promote the oxidation of Spiro-OMeTAD, improve the conductivity and hole mobility of the Spiro-OMeTAD hole transport layer thin film, reduce the parallel resistance of the device, improve the FF of the device, and finally greatly improve the device performance.
Observe the solution of hole transport layer material as configured due to TBAPF6Compatibility with Spiro-OMeTAD, TBAPF6Can be uniformly distributed in the Spiro-OMeTAD/dichloromethane, and can accelerate the progress of the Spiro-OMeTAD oxidation reaction, so that the color of the Spiro-OMeTAD/dichloromethane solution is changed along with TBAPF6The increase in doping concentration goes from light yellow to light pink to pink and finally to dark red (according to literature reports, red is a sign of the oxidation of Spiro-OMeTAD, and the shade of red represents the degree of oxidation). In addition, methylene dichloride is used for replacing chlorobenzene to dissolve the Spiro-OMeTAD, aggregation and crystallization of the Spiro-OMeTAD can be effectively inhibited, the Spiro-OMeTAD film completely covers the surface of the perovskite film to prevent water and oxygen in the air from damaging a perovskite layer, and the stability of the device is improved on the basis of remarkably improving the conductivity of the Spiro-OMeTAD film and the performance of a hole transport layer. General Table 1, TBAPF6The photovoltaic performance of the perovskite solar cell assembled by the doped Spiro-OMeTAD hole transport layer thin film is obviously improved for three reasons: (1) TBAPF6Doped SpThe ultraviolet-visible absorption spectrum of iro-OMeTAD/dichloromethane has a strong absorption peak near 525 nm, which is favorable for improving the performance of corresponding devicesJ sc ；（2）TBAPF6After doping, the conductivity of the film of the Spiro-OMeTAD hole transport layer is obviously improved, and the FF of a corresponding device is further improved; (3) TBAPF6The doped Spiro-OMeTAD has a lower HOMO energy level, so that the perovskite thin film in the solar cell can rapidly collect photogenerated holes under low energy loss, and the performance of a corresponding device is improvedV oc 。
FIG. 10 is glass/perovskite/(4 wt% TBAPF)6 + Spiro-OMeTAD) samples and glass/perovskite/(4 wt% TBAPF)6 + Spiro-OMeTAD) (low temperature heat treatment at 50 ℃) steady state fluorescence spectra of the samples; in general FAxMA1- xPbI3Perovskite is extremely easy to form yellow phase delta-FAPBI3Perovskite with a large number of defects, low temperature heat treatment can promote TBA+Formation of covalent bonds with lead iodide to passivate perovskite defects, as shown in FIG. 10, PF6 -Forming hydrogen bond action (blue shift of steady-state fluorescence spectrum after low-temperature heating treatment) with MAI and FAI to stabilize the escape of the organic components of the perovskite and inhibit yellow phase delta-FAPBI3And perovskite is formed, and the stability of the prepared perovskite thin film and the solar cell is improved.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A method for deeply doping a temperature-induced hole dopant at a low concentration is characterized by preparing an n-i-p type perovskite solar cell structure which sequentially comprises FTO conductive glass, an electron transport layer, a perovskite light absorption layer, a hole transport layer and Au from bottom to top; the preparation process of the hole transport layer is characterized by comprising the following steps: selecting TBAPF6As hole dopants, hole transport layer materials and TBAPF6Dissolving in dichloromethane to obtain hole transport layer material solutionTBAPF in solution of liquid, hole transport layer material6The mass concentration of the perovskite thin film is 1-4 wt%, and a hole transport layer is prepared on the perovskite thin film by using corresponding spin coating parameters; the obtained n-i-p type perovskite solar cell is subjected to low-temperature heating treatment and then naturally cooled to room temperature.
2. The method of claim 1, wherein the low temperature heat treatment temperature is 50 ℃.
3. The method of claim 2, wherein the low temperature heat treatment time is 60 s.
4. The method of claim 1, wherein the hole transport layer is selected from the group consisting of Spiro-OMeTAD.
5. The method of claim 4, wherein the amount of Spiro-OMeTAD in the solution of Spiro-OMeTAD hole transport layer is 72.3 mg per ml.
6. The method of claim 1, wherein the hole transport layer material is TBAPF in solution6The mass concentration of (B) is 4 wt%.
7. The method according to claim 1, wherein the method comprises the following steps:
step 1: cleaning the surface of the FTO conductive glass by sequentially adopting a detergent, deionized water, acetone and absolute ethyl alcohol, and drying the FTO conductive glass by using nitrogen for later use;
step 2: adding diisopropyl di (acetylacetonate) titanate into n-butanol, and stirring to uniformly mix to obtain a mixed solution A;
and step 3: spin-coating the mixed solution A on the surface of the FTO conductive glass cleaned in the step 1, and baking the FTO conductive glass at the temperature of 150 ℃ for 30 min to obtain compact TiO2A layer;
and 4, step 4: adding TiO into the mixture2Adding the slurry into absolute ethyl alcohol, and stirring to uniformly mix the slurry and the absolute ethyl alcohol to obtain a mixed solution B;
and 5: the dense TiO obtained in step 32Spin-coating the mixed solution B on the surface of the FTO conductive glass layer, baking at 125 ℃ for 10 min, and annealing at 500 ℃ for 60 min to obtain mesoporous TiO2A layer;
step 6: preparation of 1.1M FAxMA1-xPbI3Solution, FA+Is CH (NH)2)2 +, MA+Is CH3NH3 +Using a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 3: 1, fully stirring to obtain a perovskite precursor solution; spreading the perovskite precursor solution on the FTO/TiO obtained in the step 52And (3) carrying out segmented spin coating on the surface of the substrate, wherein the segmented spin coating has the following process parameters: spin-coating at 1300 rpm for 10 s; and a second stage: spin-coating at a rotation speed of 5000 r/min for 30 s, dripping 200 μ L chlorobenzene antisolvent when the remaining 15 s of the second stage of spin-coating time, after the spin-coating is finished, heating at 50 ℃ for 15 s, and then heating and annealing at 100 ℃ for 60 min to obtain the perovskite thin film;
and 7: preparing a hole transport layer material solution: selecting TBAPF6As hole dopants, hole transport layer materials and TBAPF6Dissolving in dichloromethane to obtain hole transport layer material solution containing TBAPF6The mass concentration of (A) is 1-4 wt%; preparing a hole transport layer on the perovskite thin film by using corresponding spin coating parameters; the selected hole transport layer material is Spiro-OMeTAD; the content of Spiro-OMeTAD in the Spiro-OMeTAD hole transport layer solution per ml was 72.3 mg;
and 8: evaporating 60 nm Au on the surface of the hole transport layer obtained in the step 7 to form a counter electrode;
and step 9: and (3) heating the obtained perovskite solar cell device at the low temperature of 50 ℃ for 60 s, and naturally cooling to room temperature.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040011178A (en) * 2002-07-29 2004-02-05 학교법인고려중앙학원 π-conjugated polymer nano-tube, nano-wier and method for preparing the same
CN101454922A (en) * 2006-05-30 2009-06-10 巴伦西亚大学 Charge injection layer for electro-optical devices
CN103236501A (en) * 2013-03-13 2013-08-07 华中科技大学 Metal-halide-doped organic hole transporting layer, and preparation method and application thereof
CN111799381A (en) * 2020-09-10 2020-10-20 江西省科学院能源研究所 Preparation method of perovskite solar cell based on phosphorus-containing hole dopant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040011178A (en) * 2002-07-29 2004-02-05 학교법인고려중앙학원 π-conjugated polymer nano-tube, nano-wier and method for preparing the same
CN101454922A (en) * 2006-05-30 2009-06-10 巴伦西亚大学 Charge injection layer for electro-optical devices
CN103236501A (en) * 2013-03-13 2013-08-07 华中科技大学 Metal-halide-doped organic hole transporting layer, and preparation method and application thereof
CN111799381A (en) * 2020-09-10 2020-10-20 江西省科学院能源研究所 Preparation method of perovskite solar cell based on phosphorus-containing hole dopant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Surface charge-transfer doping for highly efficient perovskite solar cells";Shaobing Xiong 等;《Nano Energy》;20201016;第79卷;全文 *

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