CN109904319B - Preparation method of large-size perovskite flat crystal and perovskite layer and solar cell - Google Patents
Preparation method of large-size perovskite flat crystal and perovskite layer and solar cell Download PDFInfo
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Abstract
The invention discloses a preparation method of a perovskite layer, which comprises the following steps: 1) Preparing a first precursor solution, spin-coating the solution on a substrate to form a wet film, annealing and cooling; 2) Preparing a second precursor solution, dropwise adding the second precursor solution on the cooled substrate wet film by adopting a multi-drop coating method, and carrying out continuous heat treatment to obtain a perovskite layer; also provided is a method of manufacturing a solar cell, comprising the steps of: 1) Cleaning a conductive glass substrate, and preparing an electron transport layer on the substrate; 2) Preparing a perovskite layer on the electron transport layer; 3) Preparing a hole transport layer on the perovskite layer and preparing a metal electrode. The method provided by the invention increases the size of the perovskite crystal, the diameter of the crystal is mainly distributed in (1.4-2.8) mu m and can reach 5 mu m to the maximum, and the surface of the perovskite layer formed by the perovskite crystal is flat and has no pinholes, so that the Power Conversion Efficiency (PCE) and the long-term stability of the solar cell based on the perovskite crystal can be improved.
Description
Technical Field
The invention relates to a perovskite solar cell preparation technology, belongs to the field of electronic materials and devices, and particularly relates to a preparation method for forming a perovskite layer by using a large-size perovskite flat crystal and a solar cell thereof.
Background
Along with the consumption of energy, fossil fuels such as coal, oil and natural gas are widely used in life activities of people. Along with the continuous development of social economy and the continuous progress of human civilization, people have more and more great energy requirements. However, these energy sources are essentially non-renewable, and their limited reserves constitute an irreconcilable conflict with the unlimited needs of humans. Secondly, due to the increasing severity of the global warming phenomenon, various measures are taken for the emission of carbon dioxide in various countries of the world. The use of these energy sources also causes greenhouse effect, accelerates global warming, and poses a great challenge to the survival of human beings and other animals and plants. Therefore, the exploration of new energy is urgent, clean renewable energy is the key point, and solar energy is the preferred clean energy for human beings. Solar energy, which is a renewable energy source, is a radiation from the sun, and is directly converted into electric energy widely used by humans, and has been rapidly developed and widely used in recent years.
Perovskite solar cells have developed rapidly over the past 10 years due to their very prominent advantages. The manufacturing cost is low, the manufacturing process is simple, and a flexible and transparent battery can be prepared. Meanwhile, the band gap width is more appropriate, and the color of the battery can be controlled by changing the band gap width to prepare a color battery. The perovskite has a significantly increased absorption of green and blue light compared to silicon cells. And the crystallinity of the perovskite crystal is very high, the recombination degree of the current carrier is greatly reduced, the diffusion length of the current carrier is increased, the density of a trap state is reduced, and the perovskite solar cell can show excellent performance which is closely related to the characteristics. However, many problems still exist with perovskite solar cells, such as stability of the cell in a humid environment, lifetime of the cell, how to fabricate the cell in a large area, and the like. At present, the preparation process of the perovskite type solar cell mainly comprises methods such as solution spin coating, vacuum evaporation and the like, wherein the mature process is the solution spin coating method. The solution spin coating method is a process of directly coating a solution on the surface of a substrate and forming a film interface by utilizing high-speed rotation of a spin coater. The Power Conversion Efficiency (PCE) of solar cells fabricated using spin-coating processes reaches 22.1%. However, the perovskite solar cell power conversion efficiency is still not very high, and the stability under air humidity is also very poor, so that the spin coating process needs to be further optimized, so as to improve the performance of the perovskite solar cell.
In Chinese patent, "a method for improving perovskite crystallinity" (publication No. CN 106128954A) proves that DMSO (dimethyl sulfoxide) solution can be used for delaying the crystallization process, and then a high-quality perovskite thin film is formed. Meanwhile, a DMSO solution is also used in the annealing process, so that the stability problem under the environment of ambient temperature and humidity can be improved. However, the size of the crystals obtained is still not very clear, and it is reported that the crystal diameters are mainly distributed in the range of (0.5 to 1) μm, and the largest crystal diameter is close to 2 μm. This limited size is one of the disadvantages that limit the power conversion efficiency and the long-term moisture stability of the corresponding perovskite solar cell.
In the prior art, yanhong ZHao et al [ Journal of Power Sources 359 (2017): 147-156]A multi-drop coating approach is mentioned. When preparing the perovskite base layer, firstly, spin coating a first precursor solution on the substrate in a single-drop spin coating mode, wherein the rotation speed of a spin coater is 3000rpm, the rotation time is 30 seconds, and the first precursor solution comprises lead iodide (PbI) 2 ) Solution and DMSO solution, spin-coating with PbI 2 The substrate of the film was stored under vacuum for 20 minutes. Then in the formed PbI 2 The second precursor solution was applied drop-wise to the film, 1 drop every two seconds, one drop (2-12) after the spin coater was rotated at 4000rpm, dried at 150 ℃ for 10 minutes, and finally heat treated continuously at 120 ℃ for 40 minutes to form a perovskite layer. The reported distribution of the crystal diameters is mainly (0.4-2) Mum, the growth of the crystal diameter is limited, the improved interface is not particularly flat, the grain boundary still has pinholes, and the power conversion efficiency is limited.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a preparation method for forming a perovskite layer by using a large-size perovskite flat crystal and a solar cell.
In order to achieve the above object, the present invention provides a large-sized perovskite flat crystal, the diameter of the crystal is mainly distributed in (1.4-2.8) μm, and the maximum is 5 μm; the perovskite flat crystals are gathered together to form a perovskite layer, and the surface of the perovskite layer is flat and has no pinholes.
In addition, the invention also provides a perovskite layer formed by large-size perovskite flat crystals, and the preparation method of the perovskite layer comprises the following steps:
1) Preparing a first precursor solution, spin-coating the solution on a substrate to form a wet film, and annealing and cooling;
2) And preparing a second precursor solution, dropwise adding the second precursor solution on the cooled wet film of the substrate in a multi-drop coating mode assisted by the DMSO additive, and then carrying out continuous heat treatment to obtain the perovskite layer.
In the step 1), the first precursor solution is PbI 2 Dissolving the powder in a mixed solution of dimethyl formamide (DMF)/DMSO;
the DMF/DMSO mixing volume ratio is 9.5:0.5 of the PbI 2 The amount of powder added was 1.3M.
In the step 1), the first precursor solution is spin-coated at (1000-2000) rpm for (20-35) seconds and annealed at (50-100) deg.C for 1 minute to form PbI 2 And (3) a film.
In the step 2), the adopted second precursor solution comprises organic salts of formamidine iodine (FAI), methylamine bromide (MABr) and methylamine chloride (MACl), the solvent is isopropanol, the additive is DMSO solution, and the concentration of the DMSO solution in the second precursor solution is (0.1-30) mu L mL -1 ；
The molar ratio of the organic salts FAI, MABr and MACl is 1:0.15:0.25, and the dosage of the isopropanol is 1mL.
In the step 2), pbI is present 2 The substrate of the film was continuously rotated at (1000-2000) rpm for (20-35) s, and (40-60) μ L of the second precursor solution was taken, and the solution was dropped 1 time every (1-3) seconds and 4-6 times after the substrate started to rotate, to form a second layer of wet film.
In the step 2), the obtained second layer wet film is placed on a hot table in the ambient air with the humidity of 40-60% to carry out continuous heat treatment, the annealing process is in a dust-free and closed environment, the temperature of the hot table is (120-160) DEG C, and the perovskite layer is obtained after heating for (10-25) minutes.
In addition, the invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
1) Cleaning a conductive glass substrate, and preparing an electron transport layer on the substrate;
2) Preparing a perovskite layer on the electron transport layer;
3) Preparing a hole transport layer on the perovskite layer and preparing a metal electrode.
Finally, the invention provides a perovskite solar cell prepared by the method.
The principle of the invention is as follows:
the invention provides a multi-drop coating method assisted by a DMSO (dimethyl sulfoxide) additive to prepare a perovskite layer, and the method can be used for preparing a large-size perovskite flat crystal. The prepared solar cell is of a positive structure, and PbI is coated on the electron transmission layer 2 Precursor solution to form PbI 2 Annealing and cooling the film; secondly, coating the second precursor solution on PbI 2 And finally, forming a perovskite layer on the film through quasi-double-layer diffusion annealing. The invention improves the components on the basis of the original solution proportion, adds DMSO solution into the second precursor solution, and adopts a deposition method of a multi-drop coating to obtain a perovskite layer formed by large-size perovskite flat crystals. The invention adoptsDMSO additive assisted multi-drop coating method, DMSO solution is a common co-solvent for mesophase formation, so the present invention adds DMSO solution to the solution. In the annealing process, the forming time of the crystal is delayed, the crystal gradually grows, and the size gradually increases, so that the perovskite crystal with large size can be obtained. In addition, the crystal size can be further adjusted by means of multi-drop coating, and the interface is optimized. The invention strictly controls the dripping time, and the solution is dripped for 1-3 seconds at the same time interval. During the process of dispensing the solution, the small perovskite particles dissolve and deposit into the interstices between the large perovskite crystals, making the perovskite crystal boundaries more compact. In solution, the molecules at the surface of the perovskite particles are more mobile than the internal molecules due to fewer adjacent bonds, and the large perovskite particles contain more internal molecules and fewer surface molecules than the small perovskite particles, so more molecules are separated from the small perovskite particles surface and diffuse into the solution. As the concentration of free molecules in the solution increases, the free molecules will redeposit on the surface of the large perovskite particles. Therefore, through the multi-drop coating mode, the dissolution of small perovskite particles and the growth of large perovskite particles can be ensured, larger large-size perovskite flat crystals are generated, when the perovskite flat crystals are in an aggregation-integrated type, gaps among the perovskite crystals are formed through the coating mode, crystal boundaries are passivated, pin holes are reduced, the boundaries are combined more compactly, and the formed perovskite layer is smoother and smoother.
The perovskite layer prepared by the DMSO additive-assisted multi-drop coating method has the advantages that the perovskite crystal in the perovskite layer is larger in size and flatter in appearance, the perovskite layer is more compact and flatter in structure, the crystal boundary of the perovskite layer is flat and smooth, and the interface is free of pinholes, so that the recombination degree of photo-generated carriers is greatly reduced, the diffusion length of the carriers is increased, the density of trap states is reduced, charge transmission is facilitated, light absorption and conversion can be promoted, and the efficiency of the perovskite solar cell is improved.
The invention has the beneficial effects that:
1) The characterization shows that the mode of manufacturing the perovskite layer can obtain crystals with larger size after the continuous heat treatment process, simultaneously the crystal face of the perovskite layer is also perfect, the interface has no pin holes, and the maximum crystal size can reach 5 mu m. There is a lot of evidence that grain boundaries in polycrystalline perovskite thin films cause an increase in charge recombination due to the presence of defects in the crystals. Therefore, the DMSO additive and the multi-drop coating method can delay the crystal forming process, control the crystal size and form the large crystal perovskite film with smaller grain boundaries.
2) In addition, perovskite solar cells with increased crystallinity also exhibit better power conversion efficiency and stability. The planar perovskite solar cell with the perovskite layer formed on the basis of the large-size perovskite flat crystal has the power conversion efficiency remarkably improved to 20.63 percent (16.02 percent of the original perovskite solar cell). The unsealed perovskite solar cell device of large-size perovskite flat crystals is stored at room temperature under 40% of relative humidity, and still maintains 93% of the power conversion efficiency of the initial value after 500 hours.
Drawings
FIG. 1 is a schematic structural diagram of a perovskite solar cell manufactured according to the present invention.
FIG. 2 is a process diagram of the present invention for producing a perovskite layer using a DMSO additive assisted multi-drop coating method.
FIG. 3 is a graph showing current density-voltage (J-V) characteristics of four samples in example 1 of the present invention, and the cell area is 0.1cm 2 。
FIG. 4 is a graph comparing the long-term stability tests of the first and fourth samples in example 1 of the present invention;
FIG. 5 shows tin dioxide (SnO) deposited under different conditions according to example 1 of the present invention 2 ) A top view SEM image of a perovskite thin film on a substrate; (1) A film prepared using a DMSO additive assisted, multi-drop coating method for the first sample; (2) For the second sample, a film using a multi-drop coating method; (3) a third sample, a film containing a DMSO additive; (4) As a fourth sample, no DMSO additive was included and the multi-drop coating method was not used.
FIG. 6 shows deposition on SnO under different conditions in example 1 of the present invention 2 Cross-section SE of perovskite thin film on substrateM image; (1) For the first sample, a film prepared using a DMSO additive assisted, multi-drop coating method; (2) For the second sample, a film using a multi-drop coating method; (3) a third sample, a film containing a DMSO additive; (4) As a fourth sample, no DMSO additive was included and the multi-drop coating method was not used.
In the figure: 1. indium Tin Oxide (ITO) conductive glass layer, 2, snO 2 An electron transport layer, 3, a perovskite layer, 4, a hole transport layer, 5 and a metal gold electrode.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the detailed description herein of specific embodiments is intended to illustrate the invention and not to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention.
The invention provides a preparation method of a perovskite layer, which has strong operability and stable preparation process. The crystal growth size of the prepared battery device can be controlled, and the conversion efficiency of the solar battery is efficient and stable. The invention provides an effective process means for improving the performance of the perovskite solar cell and has wide application prospect.
The invention provides a solar cell prepared by the method, the structure of the solar cell is shown in figure 1, and the solar cell sequentially comprises an indium tin oxide conductive glass layer 1 and SnO from bottom to top 2 An electron transport layer 2, a perovskite layer 3, a hole transport layer 4 and a metallic gold electrode 5.
Example 1
A preparation method of a solar cell specifically comprises the following steps:
1) Preparation of the substrate: taking ITO glass, shearing a sample with the thickness of 1cm multiplied by 1cm, sequentially washing the sample with a detergent, deionized water, acetone, isopropanol and ethanol for 20 minutes, ultrasonically cleaning and drying the sample, then carrying out UV-ozone cleaning treatment on an ITO substrate for 25 minutes to remove a surface oxide layer and oil stains, and then putting the ITO glass into a nitrogen glove box for drying for later use;
2) Preparing an electron transport layer: compounding SnO 2 Solution of SnO 2 Putting the colloid precursor solution into a reagent bottle, adding deionized water for dilution, and carrying out ultrasonic treatment for 30min to fully mix the solution. Adsorbing the cleaned ITO glass substrate on a spin coater, and dripping SnO 2 The solution was followed by spin coating. During spin coating, the rotation speed of a spin coater is 4000rpm, the rotation time is 30 seconds, then the substrate is transferred to a hot table, and annealing is carried out for 30 minutes at 150 ℃;
3) Preparing a perovskite layer:
(1) preparing a first precursor solution, and adding 1.3M PbI 2 The powder was dissolved in DMF/DMSO at a volume ratio of 9.5: and (3) oscillating the solution in the mixed solvent of 0.5 for 30min to obtain a mixed solution. Taking the first precursor solution, and dripping the first precursor solution into SnO 2 Spin-coating the compact layer by a spin coater to form a film, wherein the rotation speed of the spin coater is 1500rpm, the rotation time is 30 seconds, annealing is carried out on a hot table at 70 ℃ for 1 minute, and then the PbI-containing layer is subjected to annealing 2 Cooling the film substrate in a dust-free and closed environment to obtain PbI 2 A film;
(2) preparing a second precursor solution, and mixing organic salts FAI, MABr and MACl according to a molar ratio of 1:0.15:0.25, placing in a reagent bottle, adding 1mL of isopropanol, shaking for 30min to fully dissolve the organic salt, adding a DMSO solution into the solution, wherein the concentration of the DMSO solution in the second precursor solution is 25 muL mL -1 Oscillating for 30min again to obtain a second precursor solution, spin-coating the second precursor solution: in PbI 2 Spin-coating the solution on a film at the rotation speed of 1400rpm for 30 seconds, taking about 60 mu L of a second precursor solution, dropwise adding the solution at the interval of 1 second for 1 time and 5 times, transferring the obtained film into ambient air with the humidity of 40-60%, placing the film on a hot table for continuous heat treatment, and heating the film for 16 minutes at the temperature of 150 ℃ in a dust-free and closed environment in the annealing process to obtain a perovskite layer;
4) Preparing a hole transport layer: a2, 2', 7' -tetrakis- (dimethoxydiphenylamine) -spirofluorene (Spiro-OMeTAD) solution was prepared, 87.8mg of Spiro-OMeTAD powder was put into a reagent bottle, and 1mL of chlorobenzene, 19.5. Mu.L of bis (trifluoromethanesulfonyl) imide (Li-TFSI), 8. Mu.L of cobalt complex (FK 209) and 35.5. Mu.L of 4-tert-butylpyridine (TBP) were added in this order, followed by shaking for 30min to dissolve them sufficiently, thereby obtaining a mixed solution. Dripping single drops of spiro-OMeTAD solution on the perovskite layer obtained in the step 3), then carrying out spin coating, wherein the rotation speed of a spin coater is 4000rpm, the rotation time is 20 seconds, and then transferring the perovskite layer to a drying oven for drying and storing.
5) Preparing an electrode: and (5) evaporating a 100nm gold electrode by a vacuum coating machine.
Perovskite crystal size and solar cell performance analysis:
in the present invention, the first sample is a sample using a DMSO additive assisted multi-drop coating method; the second sample was a sample using a multi-drop coating method; the third sample is a sample containing DMSO additive; the fourth sample was a sample that contained no DMSO additive and also did not take the form of a multi-drop coating.
Comparison of crystal diameter size obtained in example 1: as shown in fig. 5 and 6, the top view and the cross-sectional SEM image of the sample crystal show the size of the crystal. The crystal diameter of the first sample is mainly distributed in (1.4-2.8) mu m, and the maximum diameter can reach 5 mu m; the crystal diameter of the second sample is mainly distributed in (0.75-1.6) mu m, and the maximum diameter can reach 2.4 mu m; the crystal diameter of the third sample is mainly distributed in (0.6-1.8) mu m, and the maximum diameter can reach 2 mu m; the crystal diameter of the fourth sample is mainly distributed in (0.2-0.8) mu m, and the maximum of the crystal diameter can reach 1.2 mu m. The main distribution means a distribution of 90% or more. We can see that the crystal diameter size is minimal when no DMSO additive is present and no multi-drop coating is used; when DMSO additive or multi-drop coating methods are used, there is an increase in the crystal diameter size, but the average maximum diameter does not exceed 2 μm; when the DMSO additive-assisted multi-drop coating method is adopted, the size of the crystals is larger, the diameter of a large part of the crystals is mainly distributed to exceed 2 mu m, and the maximum size can reach 5 mu m.
The performance of the solar cell obtained by the present invention is shown in fig. 3 and 4. Fig. 3 is a plot of current density versus voltage characteristics of the samples, and fig. 4 reflects the stability of the samples. The summary data is shown in table 1 below: the power conversion efficiency of the first sample is 20.63%, the stability of the device is greatly improved, and the efficiency is still more than 90% after 500 hours under the ambient humidity. The power conversion efficiency of the second sample is 18.09%, the power conversion efficiency of the second sample is reduced by 12% compared with that of the first sample, and the stability is reduced. The power conversion efficiency of the third sample is 19.73%, the power conversion efficiency of the third sample is reduced by 4% compared with that of the first sample, and the stability is reduced. The power conversion efficiency of the fourth sample is 16.02%, the power conversion efficiency of the fourth sample is reduced by 22% compared with that of the first sample, and the stability is poor.
Therefore, the DMSO additive-assisted multi-drop coating method has great influence on the crystal size of the perovskite layer, so that the crystal size can be enlarged, the interface is improved, and the power conversion efficiency is improved. However, when the mode of the invention is adopted and the DMSO additive assisted multi-drop coating method is adopted, the crystal size is further improved, the interface is smooth and has no pinholes, the charge recombination can be reduced, the power conversion efficiency of the device is improved, and the stability of the device is improved.
The results of the performance tests of the various samples of example 1 are shown in Table 1 below.
Table 1 results of performance tests of various samples in example 1
Example 2
A preparation method for forming a perovskite layer by perovskite flat crystals specifically comprises the following steps:
1) Preparation of the substrate: firstly, taking ITO glass, shearing a sample with the thickness of 1cm multiplied by 1cm, sequentially washing the ITO glass for 20 minutes by using a detergent, deionized water, acetone, isopropanol and ethanol, ultrasonically cleaning and drying the ITO glass, then cleaning the ITO glass substrate for 25 minutes by using UV-ozone to remove an oxide layer and oil stains on the surface of the ITO glass, and then putting the ITO glass into a nitrogen glove box for drying for later use;
2) Preparing a perovskite layer:
(1) preparing a first precursor solution, and adding 1.3M PbI 2 The powder was dissolved in DMF/DMSO at a volume ratio of 9.5: oscillating for 30min in 0.5 mixed solvent to obtain first precursor solution, and dripping the first precursor solution into SnO 2 Spin-coating the compact layer by a spin coater to form a film, wherein the rotation speed of the spin coater is 1000rpm, the rotation time is 20 seconds, annealing is carried out on a hot table at 50 ℃ for 1 minute, and then the PbI-containing layer is subjected to annealing 2 Cooling the film substrate in a dust-free and closed environment to obtain PbI 2 A film;
(2) preparing a second precursor solution, and mixing organic salts FAI, MABr and MACl according to a molar ratio of 1:0.15:0.25, placing the mixture in a reagent bottle, adding 1mL of isopropanol, shaking for 30min to fully dissolve the organic salt, adding a DMSO solution into the solution, wherein the concentration of the DMSO solution in the second precursor solution is 15 μ L mL -1 And oscillating again for 30min to obtain a mixed solution, spin-coating a second precursor solution: in PbI 2 Spin-coating the solution on a film at a rotation speed of 1200rpm for 35 seconds, taking about 40 mu L of a second precursor solution, dropwise adding the solution at intervals of 3 seconds for 1 time and 4 times, transferring the obtained film into ambient air (40-60% humidity), and placing the film on a hot bench for continuous heat treatment, wherein the film is in a dust-free and closed environment in the annealing process, the temperature of the hot bench is 160 ℃, and the perovskite layer is obtained after heating for 10 minutes.
In the invention, the fifth sample is a sample adopting a traditional single-drop coating, the solution is directly dropped on the substrate, and then the film is prepared by spin coating; and the sixth sample is a sample adopting a DMSO additive-assisted multi-drop coating method, and after the substrate is rotated, the solution is dripped on the substrate dropwise, and 4 drops are formed in total, so that the film is formed finally.
Comparative analysis of crystal size: the fifth sample has crystal diameters mainly distributed in (0.8-1.65) μm; the sixth sample had a crystal diameter distribution of mainly (1.0-2.2) μm.
In this embodiment, the fifth sample adopts a conventional single-drop spin coating manner, and the SEM characterization chart shows that the crystal size is mainly distributed at (0.8-1.65) μm, the interface of the perovskite layer is not flat, the existence of pinholes between crystals affects the power conversion efficiency of the device, and the stability also affects the device. In the sixth sample, the DMSO additive assisted multi-drop coating method is adopted, and the crystal diameter is mainly distributed in the range of (0.8-1.65) mu m, and the formed perovskite layer interface is relatively flat and has almost no pinholes. Therefore, the multi-drop coating method assisted by the DMSO additive can delay the crystal growth time, so that the crystal forming time is longer, the dissolution of small crystals is accompanied with the formation of large crystals, crystals with larger size are obtained, and a smoother grain boundary can be obtained by the method.
Example 3
A method for preparing a perovskite layer formed of flat perovskite crystals, comprising the steps of:
1) Preparation of the substrate: taking ITO glass, shearing a sample with the thickness of 1cm multiplied by 1cm, sequentially washing the sample with a detergent, deionized water, acetone, isopropanol and ethanol for 20 minutes, ultrasonically cleaning and drying the sample, then carrying out UV-ozone cleaning treatment on an ITO substrate for 25 minutes to remove a surface oxide layer and oil stains, and then putting the ITO glass into a nitrogen glove box for drying for later use;
2) Preparing a perovskite layer:
(1) preparing a first precursor solution, and adding 1.3M PbI 2 The powder was dissolved in DMF/DMSO at a volume ratio of 9.5:0.5, oscillating for 30min to obtain a mixed solution, taking the first precursor solution, and dripping the first precursor solution into SnO 2 Spin-coating the compact layer by a spin coater to form a film, wherein the rotation speed of the spin coater is 2000rpm, the rotation time is 35 seconds, annealing is carried out on a hot platform at 50 ℃ for 1 minute, and then the PbI is contained 2 Cooling the film substrate in a dust-free and closed environment to obtain PbI 2 A film;
(2) preparing a second precursor solution, and mixing organic salts FAI, MABr and MACl according to a molar ratio of 1:0.15:0.25, placing in a reagent bottle, adding 1mL of isopropanol, shaking for 30min to fully dissolve the organic salt, adding a DMSO solution into the solution, wherein the concentration of the DMSO solution in the second precursor solution is 28 μ L mL -1 Then the mixture is oscillated again for 30min,to obtain a mixed solution, spin coating the second precursor solution: in PbI 2 Spin-coating the solution on a film at the rotation speed of 1800rpm for 25 seconds, dropwise adding about 50 mu L of a second precursor solution at an interval of 2 seconds for 1 time and 5 times, transferring the obtained film into 40-60% humidity ambient air, and placing the film on a hot bench for continuous heat treatment, wherein the film is in a dust-free and closed environment in the annealing process, the temperature of the hot bench is 130 ℃, and the perovskite layer is obtained after heating for 25 minutes.
In the invention, the seventh sample is a sample adopting a traditional single-drop coating, the solution is directly dropped on the substrate, and then the film is prepared by spin coating; the eighth sample is a sample of a multi-drop coating method assisted by a DMSO additive, and after the substrate is rotated, the solution is dropped on the substrate drop by drop, and 5 drops are formed in total, and finally the film is formed.
Comparative analysis of crystal size: the seventh sample had crystal diameters mainly distributed in the range of (1.1 to 1.8) μm; the eighth sample had a crystal diameter distribution mainly in the range of (1.3-2.65) μm.
In this embodiment, a seventh sample adopts a conventional single drop spin coating manner, and SEM characterization charts show that the crystal size, the crystal diameter mainly distributed in (1.1-1.8) μm, the interface of the perovskite layer is not flat, pinholes exist between crystals, the power conversion efficiency of the device is affected, and the stability is also affected. In the eighth sample, the DMSO additive-assisted multi-drop coating method is adopted, and the crystal diameters are mainly distributed in the range of (1.3-2.65) mu m, so that the formed perovskite layer interface is relatively flat and almost no pin holes exist. Therefore, the multi-drop coating method assisted by the DMSO additive can delay the crystal growth time, so that the crystal forming time is longer, the dissolution of small crystals is accompanied with the formation of large crystals, crystals with larger size are obtained, and a smoother grain boundary can be obtained by the method.
Example 4
A method for producing a perovskite layer formed of flat perovskite crystals, comprising the steps of:
1) Preparation of the substrate: taking ITO glass, shearing a sample with the thickness of 1cm multiplied by 1cm, sequentially washing the sample with a detergent, deionized water, acetone, isopropanol and ethanol for 20 minutes, ultrasonically cleaning and drying the sample, then carrying out UV-ozone cleaning treatment on an ITO substrate for 25 minutes to remove a surface oxide layer and oil stains, and then putting the ITO glass into a nitrogen glove box for drying for later use;
2) Preparing a perovskite layer:
(1) preparing a first precursor solution, and adding 1.3M PbI 2 The powder was dissolved in DMF/DMSO at a volume ratio of 9.5:0.5, oscillating for 30min to obtain a mixed solution, taking the first precursor solution, and dripping the first precursor solution into SnO 2 Spin-coating the compact layer by a spin coater to form a film, wherein the rotation speed of the spin coater is 1600rpm, the rotation time is 25 seconds, annealing is carried out on a hot table at 100 ℃ for 1 minute, and then the PbI-containing layer is subjected to annealing 2 Cooling the film substrate in a dust-free and closed environment to obtain PbI 2 A film;
(2) preparing a second precursor solution, and mixing organic salts FAI, MABr and MACl according to a molar ratio of 1:0.15:0.25, placing the mixture in a reagent bottle, adding 1mL of isopropanol, shaking for 30min to fully dissolve the organic salt, adding a DMSO solution into the solution, wherein the concentration of the DMSO solution in the second precursor solution is 20 μ L mL -1 And oscillating again for 30min to obtain a mixed solution, spin-coating a second precursor solution: in PbI 2 Spin-coating the solution on a film at the rotation speed of 1000rpm of a spin coater for 20 seconds, taking about 60 mu L of a second precursor solution, dropwise adding the solution at the interval of 2 seconds for 1 time and 6 times, transferring the obtained film into ambient air (40-60% humidity), placing the film on a hot table for continuous heat treatment, and heating the film for 25 minutes at the temperature of 120 ℃ in a dust-free and closed environment in the annealing process to obtain a perovskite layer.
In the invention, the ninth sample is a sample adopting a traditional single-drop coating, the solution is directly dropped on the substrate, and then the spin coating is carried out to prepare a film; the tenth sample is a sample of a multi-drop coating method assisted by a DMSO additive, and after the substrate is rotated, the solution is dropped on the substrate drop by drop, and 6 drops are formed in total, and finally the film is formed.
Comparative analysis of crystal size: the ninth sample had crystal diameters mainly distributed (1.1-1.75) μm; the tenth sample had a crystal diameter distribution mainly in (1.25-2.6) μm.
In this embodiment, the ninth sample adopts a conventional single-drop spin coating manner, and the SEM characterization chart shows that the crystal size is mainly distributed in (1.1-1.75) μm, the interface of the perovskite layer is not flat, the existence of pinholes between crystals affects the power conversion efficiency of the device, and the stability also affects the device. In the tenth sample, the DMSO additive-assisted multi-drop coating method is adopted, and the crystal diameters are mainly distributed in the range of (1.25-2.6) mu m, so that the formed perovskite layer interface is relatively flat and almost no pin holes exist. Therefore, the DMSO additive-assisted multi-drop coating method can delay the crystal growth time, so that the crystal forming time is longer, the dissolution of small crystals is accompanied with the formation of large crystals, crystals with larger size are obtained, and a smoother grain boundary can be obtained through the method.
Example 5
A preparation method of a perovskite layer formed by perovskite flat crystals comprises the following steps:
1) Preparation of the substrate: taking ITO glass, shearing a sample with the thickness of 1cm multiplied by 1cm, sequentially washing the sample with a detergent, deionized water, acetone, isopropanol and ethanol for 20 minutes, ultrasonically cleaning and drying the sample, then carrying out UV-ozone cleaning treatment on an ITO substrate for 25 minutes to remove a surface oxide layer and oil stains, and then putting the ITO glass into a nitrogen glove box for drying for later use;
2) Preparing a perovskite layer:
(1) preparing a first precursor solution, and adding 1.3M PbI 2 The powder was dissolved in DMF/DMSO at a volume ratio of 9.5: oscillating for 30min in 0.5 mixed solvent to obtain mixed solution, taking the first precursor solution, and dripping into SnO 2 Spin-coating the compact layer by a spin coater to form a film, wherein the rotation speed of the spin coater is 1800rpm, the rotation time is 25 seconds, annealing is carried out on a hot table at 70 ℃ for 1 minute, and then the PbI is contained 2 Cooling the film substrate in a dust-free and closed environment to obtain PbI 2 A film;
(2) preparing a second precursor solution, and mixing organic salts FAI, MABr and MACl according to a molar ratio of 1:0.15:0.25, placing in a reagent bottle, adding 1mL of isopropanol, shaking for 30min to fully dissolve the organic salt, adding DMSO solution into the solution, dissolving the DMSO solution in the second precursorThe concentration of the solution is 25 mu L mL -1 And oscillating for 30min again to obtain a mixed solution, and spin-coating a second precursor solution: in PbI 2 Spin-coating the solution on a film at a spin coater speed of 1600rpm for 30 seconds, taking about 50 mu L of a second precursor solution, dropwise adding the solution at an interval of 1 second for 1 time and 5 times, transferring the obtained film into ambient air (40-60% humidity), and placing the film on a hot table for continuous heat treatment at a dust-free and closed environment in the annealing process, wherein the temperature of the hot table is 140 ℃, and heating for 20 minutes to obtain a perovskite layer.
In the invention, the eleventh sample is a sample adopting a DMSO additive-assisted multi-drop coating method, after a substrate is rotated, the solution is dripped on the substrate drop by drop, 5 drops are formed in total, finally, a film is formed, a trace amount of DMSO solution is added into the second precursor solution, and the concentration of the DMSO solution in the second precursor solution is 0.1 mu L mL -1 (ii) a The twelfth sample is a sample adopting a multi-drop coating method, after the substrate is rotated, the solution is dropped on the substrate drop by drop, 5 drops are formed in total, finally, the film is formed, a trace amount of DMSO solution is added into the second precursor solution, and the concentration of the DMSO solution in the second precursor solution is 25 mu L mL -1 。
Comparative analysis of crystal size: the eleventh sample had a crystal diameter mainly distributed in (0.85-1.65) μm; the twelfth sample had a crystal diameter distribution mainly in the range of (1.3-2.4) μm.
In this example, the eleventh sample is coated by multiple drops, the second precursor solution contains a trace amount of DMSO solution, and it can be seen from the SEM characterization chart that the crystal size is mainly distributed in (0.85-1.65) μm, the interface of the formed perovskite layer is not flat, and there are pinholes, thus the power conversion efficiency of the device is affected. The twelfth sample also adopts a multi-drop coating method assisted by a DMSO additive, and the diameters of crystals are mainly distributed in the range of (1.3-2.4) mu m, the interface of a perovskite layer is relatively flat, the crystal size is relatively large, almost no pin holes exist among crystals, and the influence on the power conversion efficiency and the stability of the device is realized. Therefore, the DMSO additive-assisted multi-drop coating method can delay the crystal growth time, so that the crystal forming time is longer, the dissolution of small crystals is accompanied with the formation of large crystals, crystals with larger size are obtained, and a smoother grain boundary can be obtained through the method. When the crystals are too rapidly formed in the almost DMSO-free solution, the resulting crystals are small in size, and therefore, the gaps between the crystals increase, and the grain boundaries are not very flat.
The results of the property tests of the various samples in the above examples are shown in table 2 below.
Table 2 results of performance tests of various samples in examples
The data in table 2 above show that the interface size of the planar perovskite solar cell is increased, and the formation of the perovskite layer by the large-size perovskite flat crystal is promoted by the DMSO additive assisted multi-drop coating method. As can be seen from the first example, the advantages of the multi-drop coating method assisted by the DMSO additive are more obvious by comparing the way of adding the DMSO solution and the multi-drop coating. It can be seen from the first sample that the crystal diameters are mainly distributed at (1.4-2.8) μm and can reach a maximum of 5 μm, whereas the maximum diameter can reach only 2.4 μm in comparison with the other three samples in example 1. Examples 2, 3 and 4 show that the crystal size can be increased and the grain boundary is flat and has no pinholes compared with the traditional single-drop coating mode because the mode of controlling the multi-drop coating, such as the amount of the solution to be dropped, the annealing time, the number of the solution drops and the like, can influence the crystal size. Therefore, the DMSO additive-assisted multi-drop coating method has great advantages, the size of the crystal can be increased, the interface can be optimized, and the large-size perovskite flat crystal can be obtained.
The invention provides a preparation method for forming a perovskite layer by using large-size perovskite flat crystals and a solar cell, which improve the interface size of a planar perovskite solar cell and promote the large-size perovskite flat crystals to form the perovskite layer by using a multi-drop coating method assisted by a DMSO (dimethyl sulfoxide) additive. The interface is optimized, the crystal forming time is delayed, the dissolution of small crystals is accompanied with the formation of large crystals, and large-size perovskite crystals are induced to form a perovskite layer. Meanwhile, the crystal boundary is reduced, so that the defect state is reduced, the crystallinity is high, and the high light absorption and low carrier recombination rate are realized. It shows that the conversion efficiency of the solar cell can be improved by strictly controlling the concentration of the DMSO solution and controlling the process method of the multi-drop coating, and the corresponding power conversion efficiency is remarkably improved to 20.63% from the original 16.02%. More importantly, even the perovskite solar cell without encapsulation showed excellent stability, maintaining 93% of the initial efficiency after 500 hours in air at 40% humidity, whereas the original device only decreased by about 65% within 256 hours of survival. Therefore, this result provides a promising approach for preparing perovskite layers of large-sized perovskite flat crystals and high-performance stable perovskite solar cells.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (4)
1. The preparation method of the perovskite layer is characterized by comprising the following steps:
1) 1.3M PbI is added 2 Dissolving the powder in a mixed volume ratio of 9.5:0.5 of DMF/DMSO mixed solution, preparing a first precursor solution, spin-coating the solution on a substrate to form a wet film, annealing and cooling;
2) The method comprises the following steps of: 0.15:0.25 organic salts FAI, MABr and MACl, 1mL isopropanol as solvent, DMSO as additive, the DMSO solution in the second precursor solution at a concentration of (0.1-30) μ L mL -1 Preparing a second precursor solution having PbI 2 Continuously rotating the substrate of the film at (1000-2000) rpm for (20-35) s, and taking (40-60) microliter of the second precursor solutionAnd dropwise adding the solution after the substrate starts to rotate, dripping for 1 time every (1-3) seconds and dripping for 4-6 times to form a second layer of wet film, placing the second layer of wet film on a hot table in the environment air with the humidity of 40-60% for continuous heat treatment, keeping the second layer of wet film in a dust-free and closed environment in the annealing process, wherein the temperature of the hot table is (120-160) DEG C, and heating for 10-25 minutes to obtain the perovskite layer.
2. The method of claim 1, wherein the first precursor solution is spin-coated at (1000-2000) rpm for (20-35) seconds and annealed at (50-100) deg.C for 1 minute to form PbI in step 1) 2 And (3) a membrane.
3. A preparation method of a perovskite solar cell is characterized by comprising the following steps:
1) Cleaning a conductive glass substrate, and preparing an electron transport layer on the substrate;
2) Preparing a perovskite layer on the electron transport layer by the method of any one of claims 1-2;
3) Preparing a hole transport layer on the perovskite layer and preparing a metal electrode.
4. A perovskite solar cell prepared by the method of claim 3 having a power conversion efficiency of 20.63%.
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