CN113285034A - PVP (polyvinyl pyrrolidone) -doped zinc oxide film as well as preparation method and application thereof - Google Patents
PVP (polyvinyl pyrrolidone) -doped zinc oxide film as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a PVP (polyvinyl pyrrolidone) doped zinc oxide film as well as a preparation method and application thereof, belonging to the field of perovskite solar cell components. And the room temperature Hall mobility of electrons in the zinc oxide single crystal reaches up to 200cm2V‑1s‑1Much higher than titanium dioxide; on the other hand, the polymer material is added into the precursor solution to regulate and control the film performance of the zinc oxide nano material, so that a high-quality functional film can be obtained.
Description
Technical Field
The invention belongs to the field of perovskite solar cell components, and relates to a PVP (polyvinyl pyrrolidone) doped zinc oxide film, and a preparation method and application thereof.
Background
The basic structure of a perovskite solar cell generally comprises five functional layers, a transparent electrode, a hole transport layer, a perovskite active layer, an electron transport layer and a metal electrode layer, as shown in fig. 1. The electron transport layer at present most commonly comprises two types, one is a double-layer or multi-layer composite functional layer prepared by fullerene and derivatives thereof by a thermal evaporation method, and the other is high-temperature sintered TiO2And (3) a layer.
In the preparation process of the electron transport layer taking the fullerene and the derivatives thereof as main materials, the purification process of the fullerene and the derivatives thereof is more complicated, the production cost is higher, and the electron mobility is lower under the condition of low purity; for the preparation process of titanium dioxide used as an electron transport layer, a titanium dioxide functional layer is prepared by a precursor solution or gel and then a solution film-forming process combined with a high-temperature sintering process (400-. Therefore, it is necessary to develop a novel electron transport layer with high efficiency, low cost and easy processing.
Disclosure of Invention
In order to overcome the defects of complex preparation process and low electron mobility of an electron transport layer in the prior art, the invention aims to provide a PVP doped zinc oxide film and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of PVP dopes zinc oxide film, PVP dopes zinc oxide film and carries on the film forming process of solution by the precursor solution to get;
the precursor solution is a mixed solution of zinc oxide nano-particles and a conjugated polymer.
Preferably, the preparation method of the precursor solution comprises the following steps:
step 1) reacting zinc acetate with strong base to obtain zinc oxide nanoparticle gel;
step 2) dissolving zinc oxide nanoparticle gel in an organic solvent to obtain a zinc oxide solution;
and 3) dissolving the conjugated polymer in a zinc oxide solution to obtain a precursor solution.
Preferably, the zinc oxide nanoparticles are spherical, flaky, linear or rod-shaped;
the size of the zinc oxide nano-particles is 1-100 nm.
Preferably, the conjugated polymer is any one of PVP, PFN or PFNBr.
Preferably, the number average molecular weight of PVP is 1000-50000;
the number average molecular weight of PFN and PFNBr is 5000-50000.
Preferably, the concentration of the zinc acetate solution is in the range of 5-50 mg/ml.
Preferably, the strong base is potassium hydroxide or sodium hydroxide;
the concentration of the strong base is 1-50 mg/ml;
the organic solvent is one or more of acetone, chloroform, chlorobenzene, isopropanol, ethanol, methanol and dimethoxyethanol.
Preferably, the concentration of the zinc oxide solution is 0.1-50 mg/ml;
the concentration of the polyvinylpyrrolidone is 0.1-10 mg/ml.
The PVP doped zinc oxide film is prepared according to the preparation method of the PVP doped zinc oxide film, and the thickness of the PVP doped zinc oxide film is 20-80 nm.
The application of the PVP doped zinc oxide film in a perovskite solar cell comprises a transparent electrode layer, a hole transport layer, a perovskite active layer, an electron transport layer and a metal electrode layer from bottom to top in sequence, wherein the electron transport layer is the PVP doped zinc oxide film.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a PVP (polyvinyl pyrrolidone) doped zinc oxide film, wherein zinc oxide is a semiconductor material with similar conduction band energy level with titanium dioxide, and is different from a titanium dioxide layer needing high-temperature sintering in that the zinc oxide can be prepared into nano materials with different appearances, such as nano particles, nanospheres, nano sheets, nano rod arrays and the like, by a solution method under the low-temperature condition, and is easy to dope. And the room temperature Hall mobility of electrons in the zinc oxide single crystal reaches up to 200cm2V-1s-1Much higher than titanium dioxide; on the other hand, the polymer material is added into the precursor solution to regulate and control the film performance of the zinc oxide nano material, so that a high-quality functional film can be obtained.
Furthermore, polyvinylpyrrolidone (PVP) is a non-conjugated polymer with very good alcohol/water solubility, and the PVP can be used as a cathode buffer layer material in the field of organic solar cells to improve the performance of devices; in the field of perovskite solar cells, PVP can be used as a doping agent of a perovskite active layer to play a role similar to a surfactant, and aims to wrap perovskite grains, reduce the transition temperature of a perovskite cubic phase and further obtain a cubic phase stable at room temperature, so that the thermal stability of a perovskite layer is improved.
Drawings
FIG. 1 is a schematic diagram of a perovskite solar cell structure;
FIG. 2 is a schematic diagram of the chemical structure of a compound of the present invention; wherein (a) is PVP; (b) is PTAA; (c) is PFN; (d) is PFNBr;
FIG. 3 is an ultraviolet-visible absorption spectrum of the ZnO/PVP composite functional thin film;
FIG. 4 is a graph of cell density-voltage characteristics for perovskite cells of different thicknesses of the electron transport layer;
fig. 5 is a graph of cell density-voltage characteristics for perovskite cells with different ratios of PVP in the electron transport layer.
Wherein: 1-a transparent electrode layer; 2-a hole transport layer; a 3-perovskite active layer; 4-an electron transport layer; 5-metal electrode layer.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
example 1 (reference ratio)
Perovskite cells based on PC61BM and C60 as conventional electron transport layers were prepared.
Step 1) dissolving 2mg of PTAA in 1ml of toluene solvent under nitrogen atmosphere, stirring overnight at room temperature until the PTAA is completely dissolved to prepare a hole transport layer precursor solution with the concentration of 2 mg/ml;
step 2), cleaning the ITO glass with the pattern by the method, and carrying out UVO treatment for 15 minutes for later use;
step 3) taking 1290.8mg of PbI2And 445.2mg of MAI 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.
And 4) dissolving 12.5mg of PC61BM in 1ml of toluene solvent, and stirring at normal temperature overnight to obtain an electron transport layer precursor solution with the solution concentration of 12.5 mg/ml.
And 5) spin-coating the PTAA hole transport layer precursor solution obtained in the step (1) on the ITO glass obtained in the step (2), wherein the spin-coating speed is 6000rpm/min, the spin-coating time is 30 seconds, then annealing is carried out at 100 ℃ for 30 minutes, and the film thickness is about 30nm, so that the PEDOT/PSS hole transport layer is obtained.
And 6) spin-coating the perovskite precursor solution obtained in the step (3) on the PEDOT/PSS hole transport layer obtained in the step (5): 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; and finally, spin-coating at a high speed of 5000rpm/min for 11 seconds, and dripping 200 μ l of chlorobenzene (anti-solvent) in a dropwise manner, wherein the dripping of all the anti-solvent is required to be completed within 2 seconds, and the thickness of the perovskite light absorption layer is controlled to be about 500 nm.
And 7) annealing the wafer obtained in the step (6) at 75 ℃ for 2 minutes under the nitrogen protection environment, and then heating to 90 ℃ for annealing for 4 minutes.
Step 8) spin-coating the PC obtained in the step (4) on the chip obtained in the step (7)61And (3) spin coating the BM solution at 4000rpm/min for 3 seconds and 5000rpm/min for 30 seconds, wherein the film thickness is about 20 nm.
Step 9) moving the sheet prepared in the step 8 into a vacuum evaporation chamber, and vacuumizing until the vacuum degree is lower than 4 x 10-4After Pa, preparing an electron transport layer by a thermal evaporation deposition method; c60The evaporation rate is less than 0.05 angstrom/second, and the film thickness is 20 nm; the evaporation rate of BCP is less than 0.1 angstrom/second, and the film thickness is 9 nm.
Step 10) preparing the silver electrode from the sheet prepared in the step (9) by adopting a thermal evaporation deposition method, and controlling the vacuum degree to be lower than 4 x 10-4Pa, the evaporation rate is 1-2 angstroms/second, and the thickness of the silver electrode is 100nm, so that the perovskite battery device is prepared.
Example 2
And preparing the perovskite battery with the nano zinc oxide functional thin films with different thicknesses as the electron transmission layer.
The preparation of the transparent electrode layer 1, the hole transport layer 2, the perovskite active layer 3 and the metal electrode layer 5 was identical to the procedure described in example 1,
the electron transport layer 4 is produced by the following steps:
preparing a precursor solution: taking a 250ml round-bottom flask, weighing 3.55g of zinc acetate dihydrate, adding into 150ml of methanol solvent, heating and stirring until the zinc acetate dihydrate is completely dissolved, wherein the heating temperature is 60 ℃ (as shown in the figure, the temperature of the solution is controlled by a thermometer inserted into the three-neck flask), and the stirring speed is 350 rpm/min; (II) weighing 1.5g of potassium hydroxide, dissolving in 65ml of methanol, stirring at room temperature until the potassium hydroxide is completely dissolved, then quickly adding the solution into the solution (250ml of round-bottom flask) obtained in the step (I) through a dropping funnel, wherein the zinc acetate and the potassium hydroxide are subjected to chemical reaction under the heating and stirring conditions, the whole reaction process comprises three stages of changing a transparent solution into a white solution (generating the zinc hydroxide), then changing the solution into a semitransparent white or slightly blue solution (the reaction time is about 10-20 minutes), and finally changing the solution back into the white solution (sol consisting of ZnO nanoparticles, the reaction time is about 80-100 minutes), the zinc acetate and the potassium hydroxide react for about 2 hours, stopping heating, taking out the round-bottom flask from an oil bath, stopping stirring at the same time, and standing the solution for 2 hours to completely settle the prepared zinc oxide nanoparticles; (III) taking out supernatant in the solution after standing by using an injector, then adding 40-60ml of methanol into the flask, stirring for 10-15 minutes, standing until the upper layer of the solution becomes clear or standing overnight (>12 hours), taking out supernatant by using the injector (the steps can be repeated for 1-2 times), continuously adding 40-60ml of methanol into the flask, stirring for 10-15 times, transferring the solution into a centrifuge tube, centrifuging at 2000rpm until zinc oxide nanoparticles are separated from the solvent, and centrifuging for 10-15 minutes; (IV) pouring out supernatant in the centrifuge tube, taking out zinc oxide nanoparticles on the lower layer, weighing 5mg of the material, dissolving the material in 10ml of a mixed solvent of dimethoxyethanol and methanol, and stirring at normal temperature until the solution becomes clear and transparent, wherein the concentration of zinc oxide is 0.5mg/ml, and the volume ratio of dimethoxyethanol to methanol is 1: 1; and (V) weighing 5mg of PVP, dissolving in the zinc oxide solution obtained in the step (IV), and stirring at room temperature until the PVP is completely dissolved to obtain an electron transport layer precursor solution, wherein the PVP concentration is 0.5mg/ml, and the number average molecular weight is 5,000.
The precursor solution obtained in step (1) was added dropwise to the perovskite active layer 3 prepared as described in example 1, and an electron transport layer thin film was prepared by spin coating, the solution was filtered with a 0.45 μm filter head, the spin coating speed was 2000rpm/min, the spin coating time was 50 seconds, and the film thickness was 20 nm.
Example 3
And preparing the perovskite battery with the nano zinc oxide functional thin films with different thicknesses as the electron transmission layer.
The concentration of zinc oxide nanoparticles in the electron transport layer precursor solution in example 2 was changed to 1mg/ml, the other steps were not changed, and the film thickness was 30 nm.
Example 4
And preparing the perovskite battery with the nano zinc oxide functional thin films with different thicknesses as the electron transmission layer.
The concentration of zinc oxide nanoparticles in the electron transport layer precursor solution in example 2 was changed to 2mg/ml, and the thickness of the film was 50nm without changing other steps.
Example 5
And preparing the perovskite battery with the nano zinc oxide functional thin films with different thicknesses as the electron transmission layer.
The concentration of zinc oxide nanoparticles in the electron transport layer precursor solution in example 2 was changed to 5mg/ml, and the thickness of the film was 80nm without changing the other steps.
Example 6
The nanometer zinc oxide functional thin films with different PVP proportions are used for preparing perovskite batteries of an electron transmission layer.
The concentration of PVP in the precursor solution of the electron transport layer in example 3 was changed to 1mg/ml, the other steps were not changed, and the film thickness was 50 nm.
Example 7
The nanometer zinc oxide functional thin films with different PVP proportions are used for preparing perovskite batteries of an electron transmission layer.
The concentration of PVP in the precursor solution of the electron transport layer in example 3 was changed to 2mg/ml, the other steps were not changed, and the film thickness was 50 nm.
Example 8
The nanometer zinc oxide functional thin films with different PVP proportions are used for preparing perovskite batteries of an electron transmission layer.
The concentration of PVP in the precursor solution of the electron transport layer in example 3 was changed to 5mg/ml, the other steps were not changed, and the film thickness was 50 nm.
Example 9
Preparing the zinc oxide nano-particle and PVP mixed functional film.
The electron transport layer precursor solution obtained in example 2 was prepared on a quartz plate by spin coating to obtain a thin film having a thickness of 50 nm.
When the film obtained in example 9 is subjected to absorption spectrum test, as shown in fig. 3, it can be seen that the main absorption peak of the mixed film of zinc oxide and poly (vinyl pyrrolidone) is located in the ultraviolet region, and the absorption band edge is near 420nm, which indicates that the composite functional film does not affect the light absorption of the perovskite active layer in the cell in the visible light and near infrared regions when acting as a hole transport layer.
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 performance parameters and current density-voltage curves of the batteries tested are shown in table 1 and fig. 4 and 5, respectively.
Table 1 perovskite solar cell performance parameter table prepared according to different embodiments
Performance test data for perovskite solar cells prepared according to different examples show that: when the thickness of the ZnO/PVP composite functional film is in a certain range (20-80nm), the cell adopting the hole transport layer shows the photoelectric conversion efficiency equivalent to that of a reference cell; meanwhile, when the composite functional film is prepared, the open-circuit voltage is slightly increased along with the increase of the PVP concentration (0.5-5mg/ml), the corresponding current value is slightly reduced, and the photoelectric conversion efficiency of the cell is not greatly changed.
In conclusion, the PVP doped zinc oxide film provided by the invention can be applied to the field of high-efficiency perovskite solar cells. The preparation method of the PVP doped zinc oxide film provided by the invention has the advantages of room temperature operation, simple and easy precursor solution preparation, solution processing and the like. The preparation method of the PVP doped zinc oxide film provided by the invention has great advantages in the aspects of large-scale preparation, simplified process, cost control, flexible device preparation and the like of perovskite solar cells.
In the above examples, the reaction conditions of zinc acetate and strong base were as follows: heating and stirring, wherein the heating temperature is within the range of 30-70 ℃; the stirring speed is within the range of 200-2,000 rpm. And centrifuging after heating and stirring, wherein the centrifuging speed is 2000-20000 revolutions per minute.
The preparation process of the zinc oxide electron transport layer selects a spin coating method, a scraper coating method and a slit extrusion coating method. The spin coating method adopts a bench spin coater to rotate and coat the film, and the coating speed is preferably 1000-. The blade coating method adopts a flat plate type coating machine to coat the film, and preferably, the coating speed is 0.02-1m/min (meter/minute), and the coating width is 0.2-5 cm. The slot coating method adopts a roll-to-roll coater to carry out a coating process on the surface of the flexible conductive substrate, preferably the solution supply speed is 5-500 microliter/min, the coating speed is 0.2-2m/min, the coating temperature is 25-100 ℃, the coating width is 0.2-5 cm, and the slot width is 10-50 microns.
The perovskite solar cell comprises a transparent electrode layer 1, a hole transport layer 2, a perovskite active layer 3, an electron transport layer 4 and a metal electrode layer 5, wherein the transparent electrode layer 1 contains a substrate material.
The substrate material is hard high-transparency glass or flexible organic plastic, and preferably, the substrate material is high-transparency glass, flexible PET (polyethylene terephthalate), flexible PC (polycarbonate), flexible PI (polyimide) or the like.
The transparent electrode layer 1 comprises Indium Tin Oxide (ITO), Fluorine Tin Oxide (FTO), Aluminum Zinc Oxide (AZO) or tungsten-doped indium tin oxide (WTO) and the like, the light transmittance of the transparent electrode layer in a visible light region range is greater than 80%, and the surface resistance of the transparent electrode layer is less than 15 ohms.
The hole transport layer 2 is made of one or more of materials such as poly 3, 4-ethylenedioxythiophene (PEDOT), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA, the molecular structure of which is shown in the attached figure 2 of the specification), doped 2,2', 7,7' -tetrabromo-9, 9' -spirobi, tri (4-iodobenzene) amine (Spiro-OMeTAD) and conjugated polymers (such as poly (3-hexylthiophene), P3 HT). The hole transport layer material is PEDOT PSS or PTAA.
The material of the perovskite active layer 3 is ABX3A compound of the formula (I), wherein A is selected from K+、Rb+、Cs+、CH3NH3 +Or CH (NH)2)2 +B is Pb2+X is Cl-、Br-、I-Or SCN-. The thickness of the perovskite active layer 3 is 100-1000 nm.
The electron transport layer 4 is the zinc oxide functional layer.
The metal electrode layer 5 is one or a composite electrode of two or more selected from gold, copper, silver, aluminum and conductive carbon material electrodes.
The polymer includes, but is not limited to, a pyrrolidone-based polymer material, or a conjugated polymer material having high electron mobility such as PFN { poly [3,3'- (7,7' -dimethyl-9 ', 9' -dioctyl-9H, 9'H- [2,2' -bifluorene ] -9, 9-diyl) bis (N, N-dimethylpropane-1-amine) ] }, PFNBr { poly [3,3'- (7,7' -dimethyl-9 ', 9' -dioctyl-9H, 9'H- [2,2' -bifluorene ] -9, 9-diyl) bis (N-ethyl-N, N-dimethylpropane-1-amine) bromide ] }, and the like.
The substrate cleaning means that the substrate material covering the transparent conductive electrode is ultrasonically cleaned twice by sequentially using a surfactant, deionized water, acetone and isopropanol for 10-15 minutes each time, then dried in air or dried by using nitrogen, and treated by ultraviolet ozone (UVO) for 10-20 minutes for later use.
When the hole transport layer 2 is selected from PTAA, the preparation method of PTAA precursor solution is as follows: dissolving a certain amount of PTAA in toluene solvent, and stirring overnight at room temperature until the solution is completely dissolved, wherein the solution concentration is 0.5-8 mg/ml. The hole transport layer is prepared by a spin coating method with the spin coating speed of 2000-8000rpm/min, and the spin-coated film is annealed at 70-150 ℃ for 20-80 minutes under the protection of inert gas.
The preparation of the perovskite active layer 3 comprises two parts of precursor liquid preparation and thin film deposition: the precursor solution is prepared by selecting Methyl Ammonium Iodide (MAI) and lead iodide (PbI2) according to the weight ratio of 1:1 is dissolved in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), the concentration of the solution is 0.5-5mol/ml, and the volume ratio of the two solvents of the DMF and the DMSO is (0.2-5): 1; the film deposition is carried out by any one of the conventional solution film forming methods such as spin coating, wire bar coating, blade coating, slit extrusion coating, screen printing, gravure printing, relief printing and the like.
The perovskite active layer 3 is prepared by a gel coating method, and the high-efficiency perovskite light absorption layer is prepared by an anti-solvent method, and the method can be divided into three steps: (I) dropping the precursor on the surface of the hole transport layer; (II) starting spin coating to prepare a film, and dripping an anti-solvent in the spin coating process to obtain a high-efficiency perovskite light absorption layer; and (III) annealing. The spin coating preparation of the light absorption layer is divided into two stages, wherein the first stage is a slow stage, the preferred spin coating speed is 1000-; the second stage is a high speed stage, preferably with a spin speed of 4000-. Wherein, the anti-solvent is chlorobenzene, the volume of the solvent is 100-200 mul, and the anti-solvent is dripped 20 seconds before the spin coating is stopped. The anti-solvent addition is typically completed within 2 seconds.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a PVP doped zinc oxide film is characterized in that the PVP doped zinc oxide film is obtained by a solution film forming process of a precursor solution;
the precursor solution is a mixed solution of zinc oxide nano-particles and a conjugated polymer.
2. The method of claim 1, wherein the precursor solution comprises:
step 1) reacting zinc acetate with strong base to obtain zinc oxide nanoparticle gel;
step 2) dissolving zinc oxide nanoparticle gel in an organic solvent to obtain a zinc oxide solution;
and 3) dissolving the conjugated polymer in a zinc oxide solution to obtain a precursor solution.
3. The method of claim 1, wherein the zinc oxide nanoparticles are spherical, lamellar, linear or rod-shaped;
the size of the zinc oxide nano-particles is 1-100 nm.
4. The method of claim 1, wherein the conjugated polymer is any one of PVP, PFN or PFNBr.
5. The method for preparing a PVP doped zinc oxide film according to claim 4, wherein the number average molecular weight of PVP is 1000-50000;
the number average molecular weight of PFN and PFNBr is 5000-50000.
6. The method of claim 2, wherein the zinc acetate solution has a concentration in the range of 5-50 mg/ml.
7. The method of claim 2, wherein the strong base is potassium hydroxide or sodium hydroxide;
the concentration of the strong base is 1-50 mg/ml;
the organic solvent is one or more of acetone, chloroform, chlorobenzene, isopropanol, ethanol, methanol and dimethoxyethanol.
8. The method for preparing a PVP doped zinc oxide film according to claim 2, wherein the concentration of the zinc oxide solution is 0.1-50 mg/ml;
the concentration of the polyvinylpyrrolidone is 0.1-10 mg/ml.
9. The PVP doped zinc oxide film prepared by the preparation method of the PVP doped zinc oxide film according to any one of claims 1 to 8, wherein the thickness of the PVP doped zinc oxide film is 20-80 nm.
10. The use of the PVP-doped zinc oxide thin film according to claim 9 in a perovskite solar cell, wherein the perovskite solar cell comprises, from bottom to top, a transparent electrode layer (1), a hole transport layer (2), a perovskite active layer (3), an electron transport layer (4) and a metal electrode layer (5), and wherein the electron transport layer (4) is the PVP-doped zinc oxide thin film.
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| WO2021005520A1 (en) * | 2019-07-11 | 2021-01-14 | Eni S.P.A. | Process for producing inverted polymer photovoltaic cells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114203917A (en) * | 2021-12-16 | 2022-03-18 | 华能新能源股份有限公司 | Conductive electrode and preparation method and application thereof |
| CN114203917B (en) * | 2021-12-16 | 2023-12-19 | 华能新能源股份有限公司 | Conductive electrode and preparation method and application thereof |
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