CN111769197B - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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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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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Abstract
The invention provides a perovskite solar cell and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing a composite charge transport layer solution, spin-coating the solution on a substrate, and drying to form a composite charge transport layer; s2, preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the composite charge transport layer, and drying the perovskite precursor solution under the action of the composite charge transport layer to form a perovskite functional layer with a gradient band gap; s3, preparing a second charge transport layer solution, spin-coating the solution on the perovskite functional layer, and drying to form a second charge transport layer; and S4, placing the second charge transport layer on the mask, and conveying the mask into an evaporation bin for carrying out electrode evaporation to form a back electrode. Ions of the modified material can diffuse into the perovskite functional layer to enter perovskite lattices and participate in a crystallization process, so that gradient doping is formed, the perovskite functional layer with a gradient band gap is further obtained, and the effective utilization of the perovskite solar cell on spectra is increased.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell with specific gradient band gap and a preparation method thereof.
Background
The search for emerging energy sources to address the energy crisis and ecological disruption due to traditional fossil fuel usage is at hand. As a third generation solar cell, a perovskite solar cell is one of powerful competitors to replace a conventional silicon-based solar cell due to its excellent characteristics of simple preparation process, high energy conversion efficiency, and the like. Although the efficiency of perovskite solar cells is over 25%, the perovskite solar cells have poor stability, low open-circuit voltage, hysteresis effect of scanning, incomplete utilization of spectrum and other problems, and thus the perovskite solar cells have serious limitations on commercial application.
The charge transport layer plays a very important role in perovskite solar cells, however, the transport of photogenerated carriers is affected due to poor contact between the commonly used metal oxide charge transport layer and the perovskite functional layer. Meanwhile, due to the fact that the difference between the lattice constants of the metal oxide charge transport layer and the perovskite functional layer is too large, a large number of defects can be caused by lattice mismatch of a contact surface, interface recombination is further intensified, and adverse effects are caused to the stability of the perovskite solar cell device.
In order to solve the stability problem of perovskite solar cell devices, the method of modifying the metal oxide charge transport layer by alkali metal halide or alkali metal hydroxide is widely applied, and the importance of modifying the metal oxide charge transport layer is revealed by the improved efficiency and stability.
The band gap of the perovskite material determines the open-circuit voltage and the absorption spectrum thereof, however, the conventional perovskite functional layer with a single band gap is difficult to ensure the effective absorption and utilization of sunlight, which also limits the increase of the open-circuit voltage of the perovskite solar cell.
Cascading perovskite solar cells with solar cells of different band gaps is a common means to boost spectral absorption and open circuit voltage. However, the cascade solar cell has a complex preparation process, and the poor contact between each functional layer of the cascade solar cell brings unavoidable defects, and also has a problem of lattice mismatch, which further increases the carrier recombination between each functional layer, so that the performance of the whole device cannot reach the intended target, and at the same time, the stability of the whole device is adversely affected.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a perovskite solar cell and a preparation method thereof, wherein lattice mismatch of a contact surface of a perovskite functional layer and a metal oxide electron transport layer or a metal oxide hole transport layer is reduced by modifying the metal oxide electron transport layer or the metal oxide hole transport layer, defect state density is obviously reduced, carrier recombination of the contact surface is reduced, and gradient band gap is introduced into the perovskite functional layer through the modification layer, so that the absorption of the perovskite solar cell on a spectrum is improved, the defect state density of the contact surface and the perovskite functional layer is reduced, and further, the efficiency and the stability are improved.
In order to realize the purpose, the invention adopts the following specific technical scheme:
the invention provides a perovskite solar cell which comprises a substrate, a perovskite functional layer, a second charge transport layer and a back electrode which are sequentially prepared from bottom to top, and further comprises a composite charge transport layer which is prepared between the substrate and the perovskite functional layer and is used for enabling the perovskite functional layer to form a gradient band gap.
Preferably, the composite charge transport layer is one or two layers; when the composite charge transport layer is a layer, a metal oxide charge transport layer or a metal oxide hole transport layer is prepared by mixing a modification material and a metal oxide; when the composite charge transport layer is two layers, the composite charge transport layer is respectively a first charge transport layer and a modification layer which is prepared on the first charge transport layer, is in contact with the perovskite functional layer and is made of modification materials; and when the composite charge transport layer and the first charge transport layer are metal oxide charge transport layers, the second charge transport layer is a hole transport layer; when the composite charge transport layer and the first charge transport layer are metal oxide hole transport layers, the second charge transport layer is an electron transport layer.
Preferably, the modifying layer is a fluoride.
Preferably, the fluoride is cesium fluoride or rubidium fluoride.
Preferably, the perovskite functional layer has the general structural formula ABX 3 (ii) a Wherein A is CH 3 NH 3 + Or NH 2 CH＝NH 2 + B is Pb 2+ Or Sn 2+ X is Cl - 、Br - Or I - 。
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
s1, preparing a composite charge transport layer solution, spin-coating the solution on a substrate, and drying to form a composite charge transport layer;
s2, preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the composite charge transport layer, and drying the perovskite precursor solution under the action of the composite charge transport layer to form a perovskite functional layer with a gradient band gap;
s3, preparing a second charge transport layer solution, spin-coating the solution on the perovskite functional layer, and drying to form a second charge transport layer;
and S4, placing the second charge transport layer on the mask, and conveying the mask into an evaporation bin for carrying out electrode evaporation to form a back electrode.
Preferably, the specific steps of step S1 include:
s110, preparing a first charge transport layer solution, spin-coating the solution on a substrate, and drying the solution to form a first charge transport layer;
s120, preparing a modification layer solution, spin-coating the modification layer solution on the first charge transport layer, and drying to form a modification layer, wherein the first charge transport layer and the modification layer form a composite charge transport layer;
alternatively, the specific steps of step S1 include:
s101, preparing a first charge transport layer solution and a modification layer solution, mixing the first charge transport layer solution and the modification layer solution, then spin-coating on a substrate, and drying to form the composite charge transport layer.
Preferably, the modifying layer solution is a cesium fluoride solution or a rubidium fluoride solution.
Preferably, S120 specifically includes the following steps:
s121, preparing a modification layer solution of 5-20 mg/mL;
s122, extracting 70-100 mu L of the modifying layer solution, and coating the modifying layer solution on the first charge transport layer by using a spin coater to obtain a flat modifying layer liquid film; wherein the rotating speed of the spin coater is 4000-6000rpm, the acceleration is 2000-3000rpm/s, and the coating time is 30-50 seconds;
s123, placing the liquid film of the modification layer on a heating table, heating for 15-30 minutes at the temperature of 100-150 ℃, and cooling to room temperature to obtain the modification layer.
Preferably, S2 specifically includes the following steps:
s201, adding 1.2-3mol/L MAPbI 3 Dissolving in GBL/DMSO solvent to obtain MAPbI 3 Perovskite solution, adding MAPbI 3 Heating and stirring the perovskite solution on a heating plate at 50-70 ℃ for 2-3 hours, and filtering to obtain a perovskite precursor solution;
s202, extracting 70-100 mu L of perovskite precursor solution, and coating the perovskite precursor solution on the first charge transport layer through a spin coater to obtain a flat perovskite liquid thin film; wherein the rotating speed of the spin coater is 4000-6000rpm, the acceleration is 2000-3000rpm/s, and the coating time is 40-60 seconds; and, in the coating process, rubidium ions or cesium ions in the modification layer are dissolved in the perovskite precursor solution;
s203, placing the perovskite liquid film on a heating plate, heating for 10-20 minutes at the temperature of 100-150 ℃, and cooling to room temperature to obtain a perovskite functional layer; wherein, rubidium ion or cesium ion in the modification layer is doped in the perovskite functional layer to change the band gap of the perovskite functional layer to form a gradient band gap.
The invention can obtain the following technical effects:
(1) By means of the method for modifying the charge transport layer, lattice mismatch of a contact surface of the metal oxide electron transport layer or the metal oxide hole transport layer and the perovskite function layer is reduced, defect state density is obviously reduced, and carrier recombination of the contact surface is reduced.
(2) Rubidium ions or cesium ions for modifying the metal oxide electron transport layer or the metal oxide hole transport layer can realize gradient diffusion in the perovskite functional layer, occupy the A site in the perovskite lattice structure and participate in the perovskite crystallization process, so that the perovskite solar cell with the gradient band gap is obtained, and the absorption and utilization of the perovskite device on the spectrum are enhanced.
(3) Fluorine ions in the modification layer and organic amine cations in the perovskite material form N-H \8230, F hydrogen bonds and uncoordinated lead ions form Pb-F bonds, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of the perovskite functional layer is reduced, and the high-quality perovskite crystal grains are obtained.
(4) The preparation method is simple, the perovskite solar cell with the gradient band gap can be prepared through a simple one-step method, and the perovskite solar cell has great advantages compared with the traditional laminated solar cell.
(5) In the preparation process, all materials are commercially produced and can be used without further treatment.
(6) The method has wide application range, and the perovskite solar cell with the gradient band gap can be realized by the method no matter the device is placed rightly or upside down.
Drawings
Fig. 1 is a schematic structural diagram of three perovskite solar cells according to one embodiment of the invention.
Fig. 2 is a schematic flow diagram of a corresponding overall fabrication method for three perovskite solar cells according to one embodiment of the invention.
FIG. 3 is a graph comparing the performance of perovskite solar cells according to one embodiment of the invention.
Wherein the reference numerals include: the electronic device comprises a substrate 1, a metal oxide electron transport layer 2, a modification layer 3, a perovskite functional layer 4, a hole transport layer 5, a back electrode 6, a substrate 1 ', a metal oxide hole transport layer 2', a modification layer 3 ', a perovskite functional layer 4', an electron transport layer 5 ', a back electrode 6', a substrate 11, a composite electron transport layer 12, a titanium ore functional layer 13, a hole transport layer 14 and a back electrode 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In order to solve the problem that poor contact between a metal oxide charge transmission layer and a perovskite functional layer of a traditional perovskite solar cell affects the transmission of photon-generated carriers; and the problems that due to the fact that the difference between the lattice constants of the metal oxide charge transport layer and the perovskite functional layer is too large, a large number of defects are caused due to lattice mismatch of a contact surface, interface recombination is further aggravated, and adverse effects are caused on the stability of a perovskite solar cell device are solved. The method for modifying the metal oxide charge transport layer and the perovskite functional layer by using the modifying material reduces lattice mismatch of the contact surface of the metal oxide charge transport layer and the perovskite functional layer due to overlarge lattice constant difference, and obviously reduces defect state density of the contact surface. Meanwhile, due to the excellent solubility of rubidium ions or cesium ions in the perovskite functional layer precursor solvent, rubidium ions or cesium ions can be dissolved in the precursor solution in the process of manufacturing the perovskite functional layer, spontaneously diffuse into the perovskite functional layer to form concentration gradient diffusion, occupy the position of A-site cations in perovskite to participate in the growth of perovskite grains, form the perovskite functional layer doped with rubidium ions or cesium ions, change the band gap of the perovskite functional layer, form the perovskite functional layer with gradient band gap, and accordingly improve the effective utilization of the perovskite functional layer on the spectrum. Meanwhile, fluorine ions in the modified material and organic amine cations in the perovskite material form N-H \8230, F hydrogen bonds and uncoordinated lead ions form Pb-F bonds, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of a perovskite functional layer is reduced, and the high-quality perovskite crystal grains are obtained.
The perovskite solar cell and the preparation method thereof provided by the embodiment of the invention are explained in detail below.
The perovskite solar cell provided by the invention comprises a substrate, a composite charge transport layer, a perovskite functional layer, a second charge transport layer and a back electrode which are sequentially prepared from bottom to top, wherein the composite charge transport layer is in contact with the perovskite functional layer, ions of the composite charge transport layer enter the perovskite functional layer to form concentration gradient diffusion, the band gap of the perovskite functional layer is changed, and the perovskite functional layer forms the composite charge transport layer with the gradient band gap.
The composite charge transport layer may be one layer or two separate layers. When the composite charge transport layer is a layer, the metal oxide charge transport layer or the metal oxide hole transport layer is prepared by mixing a modifying material and a metal oxide. When the composite charge transport layer is a metal oxide charge transport layer, the second charge transport layer is a hole transport layer; when the composite charge transport layer is a metal oxide hole transport layer, the second charge transport layer is an electron transport layer
When the composite charge transmission layer is two layers, the composite charge transmission layer is respectively a first charge transmission layer contacted with the substrate and a modification layer which is prepared on the first charge transmission layer, contacted with the perovskite functional layer and composed of modification materials, namely the modification layer is positioned between the first charge transmission layer and the perovskite functional layer, and the modification layer and the first charge transmission layer are independently prepared. When the first charge transport layer is a metal oxide charge transport layer, the second charge transport layer is a hole transport layer; when the first charge transport layer is a metal oxide hole transport layer, the second charge transport layer is an electron transport layer.
From the above, it can be seen that the perovskite solar cell with three structures is provided in the embodiments of the present invention, the positive perovskite solar cell is provided with the first charge transport layer as the metal oxide electron transport layer, the inverted perovskite solar cell is provided with the first charge transport layer as the metal oxide hole transport layer, and the novel perovskite solar cell is provided with the metal oxide electron transport layer and the modification layer which are mixed.
Fig. 1 shows the structure of three perovskite solar cells according to one embodiment of the invention.
As shown in fig. 1, (1) is a structure of an upright perovskite solar cell, (2) is a structure of an inverted perovskite solar cell, and (3) is a structure of a novel perovskite solar cell, which are explained below one by one.
(1) Positive perovskite solar cell
An upright perovskite solar cell comprising: the stacked substrate 1, the metal oxide electron transport layer 2, the modification layer 3, the perovskite functional layer 4, the hole transport layer 5 and the back electrode 6 are sequentially prepared from bottom to top.
The substrate 1 is a transparent conductive substrate, specifically a glass rigid substrate or a flexible substrate coated with ITO or FTO.
The metal oxide electron transport layer 2 is SnO 2 ZnO or TiO 2 The thickness is preferably 20 to 50nm.
The modification layer 3 is made of a modification material, and the modification material is fluoride, specifically cesium fluoride or rubidium fluoride.
The reason why the modified material selects the cesium fluoride or the rubidium fluoride is that the cesium fluoride or the rubidium fluoride has good solubility and can be dissolved in a perovskite precursor solution for preparing the perovskite functional layer 4, according to the calculation of a tolerance factor, rubidium ions or cesium ions can meet the tolerance factor, enter a perovskite lattice and participate in a crystallization process (the rubidium ions or the cesium ions occupy the position of an A-site cation in the perovskite and participate in the growth of perovskite grains), and form the perovskite functional layer 4 doped with cesium/rubidium ions, so that the band gap of the perovskite functional layer 4 is changed, the perovskite functional layer 4 with a gradient band gap is formed, and the effective utilization of the perovskite functional layer on a spectrum is finally improved.
Fluorine ions in the modified material and organic amine cations in the perovskite material form N-H \8230, F hydrogen bonds and uncoordinated lead ions form Pb-F bonds, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of a perovskite functional layer is reduced, and high-quality perovskite crystal grains are obtained.
Rubidium ions or cesium ions in the modified material can also reduce lattice dislocation caused by lattice mismatch of the contact surface of the metal oxide electron transmission layer 2 and the perovskite function layer 4, obviously reduce defect state density and reduce carrier recombination of the contact surface.
When the metal oxide electron transport layer 2 and the modification layer 3 are prepared, a metal oxide electron transport layer solution and a modification layer solution are separately prepared and separately formed into a film.
The structural general formula of the perovskite functional layer 4 is ABX 3 A is CH 3 NH 3 + Or NH 2 CH＝NH 2 + (ii) a B is Pb 2+ Or Sn 2+ (ii) a X is Cl - 、Br - Or I - The thickness is preferably 250 to 700nm.
The hole transport layer 5 is Spiro-OMeTAD or PTAA, and its thickness is preferably 20-40nm.
The back electrode 6 is a metal electrode or a carbon electrode, the metal electrode can be a silver electrode, a gold electrode, an aluminum electrode, etc., and the thickness of the back electrode 6 is preferably 80-100nm.
(2) For inverted perovskite solar cells
An inverted perovskite solar cell comprising: a substrate 1 ', a metal oxide hole transport layer 2', a modification layer 3 ', a perovskite functional layer 4', an electron transport layer 5 'and a back electrode 6'.
The substrate 1' refers to the substrate 1 of an upright perovskite solar cell.
The metal oxide hole transport layer 2' is NiO x The thickness is preferably 20 to 50nm.
The modification layer 3 ' refers to the modification layer 3 of the positive perovskite solar cell, the modification layer 3 ' is also made of cesium fluoride or rubidium fluoride modification material, and the modification effect on the perovskite functional layer 4 ' can be obtained in the same way. Rubidium ions or cesium ions in the modified material can also reduce lattice dislocation caused by lattice mismatch of a contact surface of the metal oxide hole transport layer 2' and the perovskite functional layer 4, obviously reduce defect state density and reduce carrier recombination of the contact surface.
The perovskite functional layer 4' is referred to as the perovskite functional layer 4 of the positive perovskite solar cell.
The electron transport layer 5' is PCBM, C60 or BCP, preferably 20-40nm thick.
The back electrode 6' is referenced to the back electrode 6 of the positive perovskite solar cell.
(3) Novel perovskite solar cell
The novel perovskite solar cell is formed by improving an upright perovskite solar cell or an inverted perovskite solar cell and is divided into two cases.
When novel perovskite solar cell improved by just putting perovskite solar cell and come, unite two into one metal oxide electron transport layer 2 and modification layer 3 and form compound charge transport layer, when preparing compound charge transport layer, mix modification layer solution and metal oxide electron transport layer solution together, form compound charge transport layer after the drying.
When the novel perovskite solar cell is improved by an inverted perovskite solar cell, the metal oxide hole transport layer 2 'and the modification layer 3' are combined into a whole to form a composite charge transport layer, when the composite charge transport layer is prepared, a modification layer solution and a metal oxide electron transport layer solution are mixed together, and the composite charge transport layer is formed after drying.
The structures of the three perovskite solar cells provided by the embodiment of the invention are explained in detail, and the invention also provides preparation methods of the three perovskite solar cells corresponding to the three perovskite solar cells.
The corresponding overall preparation method of the three perovskite solar cells comprises the following steps:
as shown in fig. 2, the overall preparation method for three perovskite solar cells provided by the embodiment of the present invention includes the following steps:
s1, preparing a composite charge transport layer solution, spin-coating the solution on a substrate, and drying to form a composite charge transport layer.
When preparing the front perovskite solar cell, the step S1 specifically includes the following steps:
s110, preparing a metal oxide charge transport layer solution, spin-coating on the substrate, and drying to form the metal oxide charge transport layer.
S120, preparing a modification layer solution, spin-coating the modification layer solution on the metal oxide charge transport layer, and drying to form the modification layer.
The metal oxide charge transport layer and the modification layer form a composite charge transport layer.
When preparing an inverted perovskite solar cell, step S1 specifically comprises the steps of:
s110', preparing a metal oxide hole transport layer solution, spin-coating on the substrate, and drying to form the metal oxide hole transport layer.
S120', preparing a modification layer solution, spin-coating the modification layer solution on the metal oxide hole transport layer, and drying to form the modification layer.
The metal oxide hole transport layer and the modification layer form a composite charge transport layer.
When preparing a novel perovskite solar cell, the step S1 specifically comprises the steps of:
s101, preparing a first charge transport layer solution and a modification layer solution, mixing the first charge transport layer solution and the modification layer solution, then spin-coating on a substrate, and drying to form the composite charge transport layer.
The first charge transport layer solution is a metal oxide charge transport layer solution or a metal oxide hole transport layer solution.
S2, preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the composite charge transport layer, and drying the perovskite precursor solution under the action of the composite charge transport layer to form the perovskite functional layer with the gradient band gap.
And S3, preparing a second charge transport layer solution, spin-coating the solution on the perovskite functional layer, and drying to form a second charge transport layer.
And S4, placing the second charge transport layer on the mask, and conveying the mask into an evaporation bin for carrying out electrode evaporation to form a back electrode.
The flow of the preparation method of the inverted perovskite solar cell, the inverted perovskite solar cell and the novel perovskite solar cell is described in detail by three specific examples.
Example 1
The preparation method of the positive perovskite solar cell comprises the following steps:
a. an FTO glass substrate of 2.5 multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning by detergent, deionized water, acetone and ethanol for 15 minutes, is dried by nitrogen, and is subjected to UVO-zone treatment for 15 minutes to serve as a transparent conductive substrate.
b. SnO 2 Colloidal solution (15 wt%) and ultrapure water in proportion (SnO) 2 The volume ratio of the colloidal solution to the ultrapure water =1: 6) Mixing, shaking the obtained solution for 5min, filtering with 0.22 μm filter head, collecting 25 μ L SnO 2 The solution is uniformly coated on a transparent conductive substrate by a spin coater to obtain a flat metal oxide electron transport layer liquid film, the spin coating speed of the spin coater is 5000rpm, the acceleration is 2500rpm/s, the coating time is 30 seconds, the obtained metal oxide electron transport layer liquid film is placed on a heating table at 150 ℃ to be heated for 30 minutes, and after cooling, UVO-Zone treatment is carried out for 15 minutes to form a metal oxide electron transport layer.
c. Preparing a cesium fluoride solution of 5mg/mL, shaking uniformly by shaking, and filtering by a filter head of 0.22 mu m to obtain a modification layer solution; extracting 70 mu L of the modifying layer solution, uniformly coating the modifying layer solution on the metal oxide electron transmission layer by using a spin coater to obtain a flat modifying layer liquid film, wherein the rotation speed of the spin coater is 4000rpm, the acceleration is 2000rpm/s, the coating time is 30 seconds, then placing the modifying layer liquid film on a heating table, heating the modifying layer liquid film at 100 ℃ for 15 minutes to form a cesium fluoride modifying layer, and the step is carried out in an indoor environment.
d. 1.2mol/L of MAPbI 3 Dissolving in GBL/DMSO solvent to obtain MAPbI 3 Heating and stirring the perovskite solution on a hot plate at 50 ℃ for 2 hours, filtering the perovskite solution through a filter head of 0.22 mu m to obtain a perovskite precursor solution, and extracting 70 mu L of MAPbI 3 The perovskite solution is evenly coated on the modification layer through a spin coater to obtain a flat perovskite liquid film, the rotation speed of the spin coater is 4000rpm, the acceleration is 2000rpm/s, the coating time is 40 seconds, the perovskite liquid film is placed on a hot plate at the temperature of 100 ℃ to be heated for 10 minutes, then the perovskite liquid film is taken down from the hot plate and is cooled to the room temperature, and a perovskite functional layer is formed.
In a preferred embodiment of the present invention, 150-200 μ L of chlorobenzene is dropped onto the perovskite liquid thin film about 30-35 seconds after the spin coating process, and chlorobenzene is used as an anti-solvent to induce perovskite crystallization.
In the coating process of the spin coating instrument, cesium ions in the cesium fluoride modification layer are dissolved in a perovskite precursor solution, so that the cesium ions spontaneously diffuse into the perovskite functional layer to form concentration gradient diffusion, occupy the position of A-site cations in perovskite to participate in the growth of perovskite grains, form the perovskite functional layer doped with the cesium ions, change the band gap of the perovskite functional layer, form the perovskite functional layer with gradient band gap, and further improve the effective utilization of the perovskite functional layer on the spectrum.
Meanwhile, fluorine ions in the cesium fluoride modification layer and organic amine cations in the perovskite functional layer form N-H \8230, F hydrogen bonds and Pb-F bonds with uncoordinated lead ions, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of the perovskite functional layer is reduced, and the high-quality perovskite crystal grains are favorably obtained.
e. Dissolving 20mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for more than 2 hours, filtering by using a filter tip with the diameter of 0.22 mu m to obtain a hole transport layer solution, pumping 70 mu L of the hole transport layer solution, uniformly coating the hole transport layer solution on a modification layer by using a spin coater to obtain a flat liquid film of the hole transport layer, wherein the rotation speed of the spin coater is 4000rpm, the acceleration is 2000rpm/s, the coating time is 20 seconds, and waiting for the solvent to volatilize or heat at normal temperature to form the hole transport layer.
f. Placing the hole transport layer on a mask plate with an effective area of 0.09cm 2 The mask plate is fed into an evaporation chamber for evaporation coating of a back electrode, the material of the back electrode is Ag, the pressure of the evaporation chamber is 5 multiplied by 10 -4 Pa, the thickness of the back electrode is 80-100nm, the evaporation rate is 2A/s, and after the evaporation of the back electrode is finished, the evaporation bin is cooled after 10 minutes, and the perovskite solar cell is taken out by inflating.
Example 2
The preparation method of the inverted perovskite solar cell comprises the following steps:
A. an FTO glass substrate of 2.5 multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning by detergent, deionized water, acetone and ethanol for 15 minutes, is dried by nitrogen, and is subjected to UVO-zone treatment for 15 minutes to serve as a transparent conductive substrate.
B. Preparation of NiO by electrochemical deposition x A hole transport layer that is a metal oxide.
Specifically, 0.2mol of Ni (NO) was disposed 3 ) 2 ·6H 2 O and 0.2M C 6 H 12 N 4 The aqueous solution of (a) was prepared using a simple two-electrode system, with the cathode being a transparent conductive substrate and the anode being Pt-coated glass of the same area as the transparent conductive substrate. The output of the electrochemical workstation is 0.12mA/cm 2 The deposition time was 60 seconds. Then the obtained sample is dried in the air and put into a muffle furnace to be heated for 2 hours at 300 ℃ in Ar gas flow to obtain NiO x And (3) a layer. After cooling, the mixture was subjected to UVO-Zone treatment for 15 minutes to obtain NiO x A hole transport layer.
C. Preparing 20mg/mL rubidium fluoride solution, shaking uniformly, filtering with a 0.22 mu m filter head to obtain a modification layer solution, extracting 70 mu L of the modification layer solution, and uniformly coating the modification layer solution on NiO by a spin coater x And obtaining a flat liquid film of the modification layer on the hole transport layer, wherein the rotating speed of a spin coater is 6000rpm, the acceleration is 3000rpm/s, the coating time is 50 seconds, then placing the liquid film of the modification layer on a heating table, heating at 150 ℃ for 30 minutes to form the rubidium fluoride modification layer, and the step is carried out in an indoor environment.
D. Adding 3mol/L MAPbI 3 Dissolving in GBL/DMSO solvent to obtain MAPbI 3 Heating and stirring the perovskite solution on a hot plate at 70 ℃ for 3 hours, filtering the perovskite solution through a filter head with the diameter of 0.22 mu m to obtain a perovskite precursor solution, and extracting 70 mu L of MAPbI 3 And uniformly coating the perovskite solution on the modification layer through a spin coater to obtain a flat perovskite liquid film, wherein the rotation speed of the spin coater is 6000rpm, the acceleration is 3000rpm/s, the coating time is 60 seconds, the perovskite liquid film is placed on a hot plate at the temperature of 150 ℃ to be heated for 20 minutes, and then the perovskite liquid film is taken down from the hot plate and cooled to room temperature to form a perovskite functional layer.
In a preferred embodiment of the present invention, 150-200 μ L of chlorobenzene is dropped onto the perovskite liquid thin film about 30-35 seconds after the spin coating process, and chlorobenzene is used as an anti-solvent to induce perovskite crystallization.
In the coating process of the spin coating instrument, rubidium ions in the rubidium fluoride modification layer are dissolved in a perovskite precursor solution, so that the rubidium ions are spontaneously diffused into the perovskite functional layer to form concentration gradient diffusion, the position of A-site cations in perovskite is occupied to participate in the growth of perovskite grains, the rubidium ion-doped perovskite functional layer is formed, the band gap of the perovskite functional layer is changed, the gradient band gap perovskite functional layer is formed, and the effective utilization of the perovskite functional layer on the spectrum is improved.
Meanwhile, fluorine ions in the rubidium fluoride modification layer and organic amine cations in the perovskite functional layer form N-H \8230, F hydrogen bonds and Pb-F bonds with uncoordinated lead ions, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of the perovskite functional layer is reduced, and the high-quality perovskite crystal grains are favorably obtained.
E. Dissolving 20mg of PCBM in 1mL of chlorobenzene, stirring for more than 2 hours, filtering by using a filter head with the thickness of 0.22 mu m to obtain an electron transport layer solution, pumping 70 mu L of the electron transport layer solution, uniformly coating the electron transport layer solution on a perovskite functional layer by using a spin coater to obtain a flat liquid film of the electron transport layer, wherein the rotation speed of the spin coater is 6000rpm, the acceleration is 3000rpm/s, the coating time is 40 seconds, and waiting for solvent volatilization or heating at normal temperature to form the electron transport layer.
F. The electron transmission layer is arranged on a mask plate, and the effective area of the mask plate is 0.09cm 2 The mask is fed into a vapor deposition chamber for vapor deposition of a back electrode, the material of the back electrode is Ag, the pressure of the vapor deposition chamber is 5 multiplied by 10 -4 Pa, the thickness of the back electrode is 80-100nm, the evaporation rate is 2A/s, and after the evaporation of the back electrode is finished, the evaporation cabin is cooled after 10 minutes, and the perovskite solar cell is taken out by inflating.
Example 3
The preparation method of the novel perovskite solar cell is characterized in that a modification material is directly doped into a metal oxide electron transport layer of an upright perovskite solar cell or a metal oxide hole transport layer of an inverted perovskite solar cell, the preparation of the novel perovskite solar cell by doping the metal oxide electron transport layer of the upright perovskite solar cell is taken as an example for explanation, and the novel perovskite solar cell prepared by doping the metal oxide hole transport layer of the inverted perovskite solar cell can be obtained in the same way.
The preparation method of the novel perovskite solar cell comprises the following steps:
(1) An FTO glass substrate of 2.5 multiplied by 2.5cm is sequentially subjected to ultrasonic cleaning by detergent, deionized water, acetone and ethanol for 15 minutes, is dried by nitrogen, and is subjected to UVO-zone treatment for 15 minutes to serve as a transparent conductive substrate.
(2) SnO 2 Colloidal solution (15 wt%) and ultrapure water in proportion (SnO) 2 The volume ratio of the colloidal solution to the ultrapure water =1: 6) And mixing, adding the weighed cesium fluoride into the prepared solution, shaking the obtained solution for 5min, and filtering by using a filter head with the diameter of 0.22 mu m to obtain the composite charge transport layer solution.
(3) Uniformly coating 25 mu L of composite charge transport layer solution on a transparent conductive substrate by a spin coater to obtain a flat liquid film of the metal oxide electron transport layer, wherein the spin coating speed of the spin coater is 5000rpm, the acceleration is 2500rpm/s, the coating time is 40 seconds, placing the obtained liquid film of the metal oxide electron transport layer on a heating table at 125 ℃ for heating for 20 minutes, cooling, and carrying out UVO-Zone treatment for 15 minutes to form the composite charge transport layer.
(4) 2.5mol/L of MAPbI 3 Dissolving in GBL/DMSO solvent to obtain MAPbI 3 Heating and stirring the perovskite solution on a hot plate at 60 ℃ for 2.5 hours, filtering the perovskite solution through a filter head with the diameter of 0.22 mu m to obtain a perovskite precursor solution, and extracting 70 mu L of MAPbI 3 And uniformly coating the perovskite solution on the composite charge transport layer through a spin coater to obtain a flat perovskite liquid film, wherein the rotation speed of the spin coater is 5000rpm, the acceleration is 2500rpm/s, the coating time is 50 seconds, the perovskite liquid film is placed on a hot plate at 125 ℃ to be heated for 15 minutes, then the perovskite liquid film is taken down from the hot plate and cooled to room temperature, and a perovskite functional layer is formed.
In a preferred embodiment of the present invention, 150-200 μ L of chlorobenzene is dropped onto the perovskite liquid thin film about 30-35 seconds after the spin coating process, and chlorobenzene is used as an anti-solvent to induce perovskite crystallization.
In the coating process of the spin coating instrument, cesium ions in the composite charge transport layer are dissolved in a perovskite precursor solution, so that the cesium ions spontaneously diffuse into the perovskite functional layer to form concentration gradient diffusion, occupy the position of A-site cations in perovskite to participate in the growth of perovskite grains, form the perovskite functional layer doped with the cesium ions, change the band gap of the perovskite functional layer, form the perovskite functional layer with gradient band gap, and further improve the effective utilization of the perovskite functional layer on the spectrum.
Meanwhile, fluorine ions in the composite charge transport layer and organic amine cations in the perovskite functional layer form N-H \8230, F hydrogen bonds and Pb-F bonds with uncoordinated lead ions, so that the loss of the organic amine ions in the annealing process is remarkably reduced, the growth speed of crystal grains is delayed, the defect state density of the perovskite functional layer is reduced, and the high-quality perovskite crystal grains are obtained.
(5) Dissolving 20mg of Spiro-OMeTAD in 1mL of chlorobenzene, stirring for more than 2 hours, filtering by using a filter tip with the diameter of 0.22 mu m to obtain a hole transport layer solution, pumping 70 mu L of the hole transport layer solution, uniformly coating the hole transport layer solution on a modification layer by using a spin coater to obtain a flat liquid film of the hole transport layer, wherein the rotation speed of the spin coater is 5000rpm, the acceleration is 2500rpm/s, the coating time is 30 seconds, and waiting for the solvent to volatilize or heat at normal temperature to form the hole transport layer.
(6) Placing the hole transport layer on a mask plate with an effective area of 0.09cm 2 The mask is fed into a vapor deposition chamber for vapor deposition of a back electrode, the material of the back electrode is Ag, the pressure of the vapor deposition chamber is 5 multiplied by 10 -4 Pa, the thickness of the back electrode is 80-100nm, the evaporation rate is 2A/s, and after the evaporation of the back electrode is finished, the evaporation bin is cooled after 10 minutes, and the perovskite solar cell is taken out by inflating.
Tests on the perovskite solar cells of the three embodiments show that the unmodified perovskite solar cell device has an open-circuit voltage of 1.08V, a short-circuit current of 23.09mA/cm & lt 2 & gt, a filling factor of 69% and a final device efficiency of 17.38%; the open-circuit voltage of the modified perovskite solar cell device is 1.13V, the short-circuit current is 23.77mA/cm & lt 2 & gt, the filling factor is 73%, and the final device efficiency is 19.71%. As can be seen from fig. 2, the open circuit voltage of the modified perovskite solar cell device is significantly increased. At the same time, the low defect state density also reverses the increase in fill factor due to the reduction in dislocations of the charge transport layer and the perovskite functional layer.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
The above embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. The perovskite solar cell comprises a substrate, a perovskite functional layer, a second charge transport layer and a back electrode which are sequentially prepared from bottom to top, wherein the structural general formula of the perovskite functional layer is ABX 3 (ii) a Wherein A is CH 3 NH 3 + Or NH 2 CH=NH 2 + B is Pb 2 + X is Cl - 、Br - Or I - The perovskite-based composite charge transport layer is characterized by further comprising a composite charge transport layer which is prepared between the substrate and the perovskite functional layer and is used for enabling the perovskite functional layer to form a gradient band gap; the composite charge transport layer comprises a modification material, and the modification material is cesium fluoride or rubidium fluoride; wherein, the fluorinion and the organic amine cation in the perovskite material form N-H \8230, the F hydrogen bond and the uncoordinated lead ion form Pb-F bond; cesium ions or rubidium ions spontaneously diffuse into the perovskite functional layer to form concentration gradient diffusion, occupy the position of A-site cations in the perovskite to participate in the growth of perovskite grains, and form the perovskite functional layer doped with rubidium ions or cesium ions so as to change the band gap of the perovskite functional layer and form the perovskite functional layer with gradient band gap.
2. The perovskite solar cell of claim 1, wherein the composite charge transport layer is one or two layers; wherein,
when the composite charge transport layer is a layer, a metal oxide electron transport layer or a metal oxide hole transport layer is prepared by mixing a modification material and a metal oxide; when the composite charge transport layer is two layers, the composite charge transport layer is respectively a first charge transport layer and a modification layer which is prepared on the first charge transport layer, is in contact with the perovskite functional layer and is made of modification materials;
when the composite charge transport layer and the first charge transport layer are metal oxide electron transport layers, the second charge transport layer is a metal oxide hole transport layer; when the composite charge transport layer and the first charge transport layer are metal oxide hole transport layers, the second charge transport layer is a metal oxide electron transport layer.
3. A preparation method of a perovskite solar cell is characterized by comprising the following steps:
s1, preparing a composite charge transport layer solution, spin-coating the solution on a substrate, and drying to form a composite charge transport layer; the composite charge transport layer solution comprises a modification layer solution, and the modification layer solution is a cesium fluoride solution or a rubidium fluoride solution; wherein, the fluorinion and the organic amine cation in the perovskite material form N-H \8230, the F hydrogen bond and the uncoordinated lead ion form Pb-F bond; cesium ions or rubidium ions spontaneously diffuse into the perovskite functional layer to form concentration gradient diffusion, occupy the position of A-site cations in the perovskite to participate in the growth of perovskite grains, and form the perovskite functional layer doped with rubidium ions or cesium ions so as to change the band gap of the perovskite functional layer and form the perovskite functional layer with gradient band gap;
s2, preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the composite charge transport layer, and drying the perovskite precursor solution under the action of a modification layer solution of the composite charge transport layer to form a perovskite functional layer with a gradient band gap; the structural general formula of the perovskite functional layer is ABX 3 (ii) a Wherein A is CH 3 NH 3 + Or NH 2 CH=NH 2 + B is Pb 2+ X is Cl - 、Br - Or I - ；
S3, preparing a second charge transport layer solution, spin-coating the solution on the perovskite functional layer, and drying to form a second charge transport layer;
and S4, placing a mask on the second charge transport layer, and feeding the mask into an evaporation bin for electrode evaporation to form a back electrode.
4. The method for preparing a perovskite solar cell according to claim 3, wherein the specific steps of step S1 comprise:
s110, preparing a first charge transport layer solution, spin-coating the solution on a substrate, and drying the solution to form a first charge transport layer;
s120, preparing a modification layer solution, spin-coating the modification layer solution on the first charge transport layer, and drying to form a modification layer, wherein the first charge transport layer and the modification layer form the composite charge transport layer;
alternatively, the specific steps of step S1 include:
s101, preparing a first charge transport layer solution and a modification layer solution, mixing the first charge transport layer solution and the modification layer solution, then spin-coating on the substrate, and drying to form the composite charge transport layer.
5. The method for manufacturing a perovskite solar cell according to claim 4, characterized in that the step S120 specifically comprises the steps of:
s121, preparing a modification layer solution of 5-20 mg/mL;
s122, extracting 70-100 mu L of the modifying layer solution, and coating the modifying layer solution on the first charge transport layer through a spin coater to obtain a flat modifying layer liquid film; wherein the rotating speed of the spin coater is 4000-6000rpm, the acceleration is 2000-3000rpm/s, and the coating time is 30-50 seconds;
s123, placing the liquid film of the modification layer on a heating table, heating for 15-30 minutes at the temperature of 100-150 ℃, and cooling to room temperature to obtain the modification layer.
6. The method for manufacturing a perovskite solar cell according to claim 3, characterized in that the step S2 comprises in particular the steps of:
s201, adding 1.2-3mol/L MAPbI 3 Dissolving in GBL/DMSO solvent to obtain MAPbI 3 Perovskite solution, adding said MAPbI 3 Heating and stirring the perovskite solution on a heating plate at the temperature of 50-70 ℃ for 2-3 hours, and filtering to obtain the perovskite precursor solution;
s202, extracting 70-100 mu L of perovskite precursor solution, and coating the perovskite precursor solution on the composite charge transport layer through a spin coater to obtain a flat perovskite liquid thin film; wherein the rotating speed of the spin coater is 4000-6000rpm, the acceleration is 2000-3000rpm/s, and the coating time is 40-60 seconds; and, in the coating process, rubidium ions or cesium ions in the modification layer are dissolved in the perovskite precursor solution;
s203, placing the perovskite liquid film on a heating plate, heating for 10-20 minutes at the temperature of 100-150 ℃, and cooling to room temperature to obtain the perovskite functional layer; and rubidium ions or cesium ions in the modification layer are doped in the perovskite functional layer so as to change the band gap of the perovskite functional layer to form a gradient band gap.
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