CN111769197A - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

Info

Publication number
CN111769197A
CN111769197A CN202010691446.9A CN202010691446A CN111769197A CN 111769197 A CN111769197 A CN 111769197A CN 202010691446 A CN202010691446 A CN 202010691446A CN 111769197 A CN111769197 A CN 111769197A
Authority
CN
China
Prior art keywords
transport layer
perovskite
charge transport
layer
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010691446.9A
Other languages
Chinese (zh)
Other versions
CN111769197B (en
Inventor
段羽
王锦涛
崔义乾
陈琛
王振宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202010691446.9A priority Critical patent/CN111769197B/en
Publication of CN111769197A publication Critical patent/CN111769197A/en
Application granted granted Critical
Publication of CN111769197B publication Critical patent/CN111769197B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

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 plate, and sending the mask plate 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

Perovskite solar cell and preparation method thereof
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 caused by scanning, incomplete utilization of spectrum and the like, and the commercial application is severely limited.
Charge transport layers have 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 layers 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 increase 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 expected target, and also has an adverse effect on the stability of the whole device.
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 metal oxide electron transport layer or a metal oxide hole transport layer and a perovskite functional layer is reduced by modifying the metal oxide electron transport layer or the metal oxide hole transport layer, the defect state density is obviously reduced, the carrier recombination of the contact surface is reduced, and a 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 achieve 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 structural general formula of the perovskite functional layer is ABX3(ii) a Wherein A is CH3NH3 +Or NH2CH＝NH2 +B is Pb2+Or Sn2+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 plate, and sending the mask plate into an evaporation bin for carrying out electrode evaporation to form a back electrode.
Preferably, the specific step of step S1 includes:
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, drying the first charge transport layer solution to form a modification layer, and forming a composite charge transport layer by the first charge transport layer and the modification layer;
alternatively, the specific step of step S1 includes:
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 rotation speed of the spin coating instrument 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 MAPbI3Dissolving in GBL/DMSO solvent to obtain MAPbI3Perovskite solution, adding MAPbI3Heating 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 rotation speed of the spin coating instrument 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, the perovskite functional layer is doped with rubidium ions or cesium ions in the modification layer so as 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 can form N-H … F hydrogen bonds with organic amine cations in the perovskite material and form 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 function layer is reduced, and the high-quality perovskite crystal grains can be 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 below 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 are not to be construed as limiting 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 can form N-H … F hydrogen bonds with organic amine cations in the perovskite material and form 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 a perovskite functional layer is reduced, and the high-quality perovskite crystal grains can be 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, the structure of the positive perovskite solar cell, the structure of the inverted perovskite solar cell, and the structure of the novel perovskite solar cell are explained below one by one.
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 SnO2ZnO or TiO2The thickness is preferably 20 to 50 nm.
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.
And fluorine ions in the modified material can form N-H … F hydrogen bonds with organic amine cations in the perovskite material and form 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 a perovskite functional layer is reduced, and the high-quality perovskite crystal grains can be obtained.
The rubidium ions or the 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 ABX3A is CH3NH3 +Or NH2CH＝NH2 +(ii) a B is Pb2+Or Sn2+(ii) a X is Cl-、Br-Or I-The thickness is preferably 250-700 nm.
The hole transport layer 5 is Spiro-OMeTAD or PTAA, and its thickness is preferably 20-40 nm.
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 80-100 nm.
② an inverted perovskite solar cell
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' is referenced to the substrate 1 of the positive perovskite solar cell.
The metal oxide hole transport layer 2' is NiOxThe thickness is preferably 20 to 50 nm.
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 the 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 referenced to 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 on the substrate, and drying to form the composite charge transport layer.
When the front perovskite solar cell is prepared, 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 includes the steps of:
s110', preparing a metal oxide hole transport layer solution, spin-coating the solution on a 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, step S1 specifically includes the following steps:
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.
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 plate, and sending the mask plate 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. SnO2Colloidal solution (15 wt%) and ultrapure water in proportion (SnO)2The volume ratio of the colloidal solution to the ultrapure water is 1: 6) mixing, shaking the obtained solution for 5min, filtering with 0.22 μm filter head, and collecting 25 μ L SnO2The 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 5mg/mL cesium fluoride solution, shaking uniformly, and filtering by a 0.22-micrometer filter head to obtain a modification layer solution; and (3) extracting 70 mu L of modification layer solution, uniformly coating the solution on the metal oxide electron transmission layer by using a spin coater to obtain a flat modification 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 modification layer liquid film on a heating table, heating at 100 ℃ for 15 minutes to form a cesium fluoride modification layer, and the step is carried out in an indoor environment.
d. Adding 1.2mol/L MAPbI3Dissolving in GBL/DMSO solvent to obtain MAPbI3Heating and stirring the perovskite solution on a hot plate at 50 ℃ for 2 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 MAPbI3And 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 4000rpm, the acceleration is 2000rpm/s, the coating time is 40 seconds, the perovskite liquid film is placed on a hot plate at 100 ℃ to be heated for 10 minutes, and then the perovskite liquid film is taken down from the hot plate and cooled to room temperature to form the perovskite functional layer.
In a preferred embodiment of the present invention, 150-.
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 can form N-H … F hydrogen bonds with organic amine cations in the perovskite functional layer and form 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 perovskite crystal grains with high quality are 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 0.09cm2The mask is sent into an evaporation chamber to evaporate a back electrode, the material of the back electrode is Ag, the pressure of the evaporation chamber is 5 × 10-4Pa, 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 depositionxA hole transport layer that is a metal oxide.
Specifically, 0.2mol of Ni (NO) was prepared3)2·6H2O and 0.2M C6H12N4The 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/cm2The 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 NiOxAnd (3) a layer. After cooling, the mixture was subjected to UVO-Zone treatment for 15 minutes to obtain NiOxA 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 coaterxAnd 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 MAPbI3Dissolving in GBL/DMSO solvent to obtain MAPbI3Heating 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 MAPbI3And 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-.
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 can form N-H … F hydrogen bonds with organic amine cations in the perovskite functional layer and form 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 can be 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 μm to obtain an electron transport layer solution, extracting 70 μ 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 spin coater has the rotation speed of 6000rpm, the acceleration of 3000rpm/s and the coating time of 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 0.09cm2The mask is sent into an evaporation chamber to evaporate a back electrode, the material of the back electrode is Ag, the pressure of the evaporation chamber is 5 × 10-4Pa, 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 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 novel perovskite solar cell prepared 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) SnO2Colloidal solution (15 wt%) and ultrapure water in proportion (SnO)2The volume ratio of the colloidal solution to the ultrapure water is 1: 6) and mixing, adding 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 MAPbI3Dissolving in GBL/DMSO solvent to obtain MAPbI3Heating 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 MAPbI3And 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-.
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 can form N-H … F hydrogen bonds, and the fluorine ions and the organic amine cations in the perovskite functional layer can 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 can be 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 0.09cm2The mask is sent into an evaporation chamber to evaporate a back electrode, the material of the back electrode is Ag, the pressure of the evaporation chamber is 5 × 10-4Pa, 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/cm2, 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/cm2, 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 is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, 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 (10)

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, and 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.
2. The perovskite solar cell of claim 1, wherein the composite charge transport layer is one or two layers; wherein the content of the first and second substances,
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.
3. The perovskite solar cell of claim 2, wherein the modifying material is fluoride.
4. The perovskite solar cell of claim 3, wherein the fluoride is cesium fluoride or rubidium fluoride.
5. The perovskite solar cell of claim 1, wherein the perovskite functional layer has the general structural formula ABX3(ii) a Wherein A is CH3NH3 +Or NH2CH＝NH2 +B is Pb2+Or Sn2+X is Cl-、Br-Or I-。
6. 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;
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 a mask, and sending the mask into an evaporation bin for electrode evaporation to form a back electrode.
7. The method for preparing a perovskite solar cell as claimed in claim 6, wherein the step S1 comprises the following steps:
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 the first charge transport layer solution to form a modification layer, wherein the first charge transport layer and the modification layer form the composite charge transport layer;
alternatively, the specific step of step S1 includes:
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.
8. The method for preparing a perovskite solar cell as claimed in claim 7, wherein the modifying layer solution is a cesium fluoride solution or a rubidium fluoride solution.
9. The method for preparing a perovskite solar cell according to claim 7, wherein the step S120 comprises 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 rotation speed of the spin coating instrument 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.
10. The method for producing a perovskite solar cell as claimed in claim 6, wherein S2 comprises the following steps:
s201, adding 1.2-3mol/L MAPbI3Dissolving in GBL/DMSO solvent to obtain MAPbI3Perovskite solution, adding said MAPbI3Heating 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 first charge transport layer through a spin coater to obtain a flat perovskite liquid thin film; wherein the rotation speed of the spin coating instrument 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 at the temperature of 100-150 ℃ for 10-20 minutes, 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.
CN202010691446.9A 2020-07-17 2020-07-17 Perovskite solar cell and preparation method thereof Active CN111769197B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010691446.9A CN111769197B (en) 2020-07-17 2020-07-17 Perovskite solar cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010691446.9A CN111769197B (en) 2020-07-17 2020-07-17 Perovskite solar cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111769197A true CN111769197A (en) 2020-10-13
CN111769197B CN111769197B (en) 2022-10-21

Family

ID=72728526

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010691446.9A Active CN111769197B (en) 2020-07-17 2020-07-17 Perovskite solar cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111769197B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864327A (en) * 2021-02-23 2021-05-28 无锡极电光能科技有限公司 Perovskite solar cell and preparation method thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102810639A (en) * 2011-05-30 2012-12-05 海洋王照明科技股份有限公司 Parallel polymer solar cell and preparation method thereof
KR101571528B1 (en) * 2014-07-01 2015-11-25 한국화학연구원 Perovskite solar cell improving photoelectric conversion efficiency and the manufacturing method thereof
CN105826477A (en) * 2016-05-12 2016-08-03 东莞市联洲知识产权运营管理有限公司 High-performance perovskite solar cell and preparation method for same
CN105870329A (en) * 2016-04-12 2016-08-17 中国科学院长春光学精密机械与物理研究所 Preparation method for water-soluble rubidium fluoride inverted-structure polymer solar cell
CN106972104A (en) * 2017-06-08 2017-07-21 安阳师范学院 A kind of perovskite solar cell preparation method of alkali metal fluoride doping
CN108258128A (en) * 2018-01-17 2018-07-06 杭州纤纳光电科技有限公司 A kind of perovskite solar cell with interface-modifying layer and preparation method thereof
CN109360889A (en) * 2018-07-28 2019-02-19 西安交通大学 A kind of perovskite solar battery of high fill factor and preparation method thereof
CN109686843A (en) * 2018-11-30 2019-04-26 苏州协鑫纳米科技有限公司 Perovskite solar battery and preparation method thereof
CN110416416A (en) * 2019-06-26 2019-11-05 西交利物浦大学 A kind of fluorine and rubidium adulterated with Ca and Ti ore solar battery and preparation method
CN110518125A (en) * 2019-08-01 2019-11-29 北京科技大学 A kind of preparation method of cation doping perovskite solar battery
CN111223990A (en) * 2019-11-29 2020-06-02 西南石油大学 Inverted perovskite solar cell containing alkali metal halide hole modification layer and preparation method

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102810639A (en) * 2011-05-30 2012-12-05 海洋王照明科技股份有限公司 Parallel polymer solar cell and preparation method thereof
KR101571528B1 (en) * 2014-07-01 2015-11-25 한국화학연구원 Perovskite solar cell improving photoelectric conversion efficiency and the manufacturing method thereof
CN105870329A (en) * 2016-04-12 2016-08-17 中国科学院长春光学精密机械与物理研究所 Preparation method for water-soluble rubidium fluoride inverted-structure polymer solar cell
CN105826477A (en) * 2016-05-12 2016-08-03 东莞市联洲知识产权运营管理有限公司 High-performance perovskite solar cell and preparation method for same
CN106972104A (en) * 2017-06-08 2017-07-21 安阳师范学院 A kind of perovskite solar cell preparation method of alkali metal fluoride doping
CN108258128A (en) * 2018-01-17 2018-07-06 杭州纤纳光电科技有限公司 A kind of perovskite solar cell with interface-modifying layer and preparation method thereof
CN109360889A (en) * 2018-07-28 2019-02-19 西安交通大学 A kind of perovskite solar battery of high fill factor and preparation method thereof
CN109686843A (en) * 2018-11-30 2019-04-26 苏州协鑫纳米科技有限公司 Perovskite solar battery and preparation method thereof
CN110416416A (en) * 2019-06-26 2019-11-05 西交利物浦大学 A kind of fluorine and rubidium adulterated with Ca and Ti ore solar battery and preparation method
CN110518125A (en) * 2019-08-01 2019-11-29 北京科技大学 A kind of preparation method of cation doping perovskite solar battery
CN111223990A (en) * 2019-11-29 2020-06-02 西南石油大学 Inverted perovskite solar cell containing alkali metal halide hole modification layer and preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHEN, EC等: "Interfacial Energy Level Tuning for Efficient and Thermostable CsPbI2Br Perovskite Solar Cells", 《ADVANCED SCIENCE》 *
XIA, JX等: "Vertical Phase Separated Cesium Fluoride Doping Organic Electron Transport Layer: A Facile and Efficient "Bridge" Linked Heterojunction for Perovskite Solar Cells", 《ADVANCED FUNCTIONAL MATERIALS》 *
YI, XH等: "Incorporating CsF into the PbI2 Film for Stable Mixed Cation-Halide Perovskite Solar Cells", 《ADVANCED ENERGY MATERIALS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864327A (en) * 2021-02-23 2021-05-28 无锡极电光能科技有限公司 Perovskite solar cell and preparation method thereof

Also Published As

Publication number Publication date
CN111769197B (en) 2022-10-21

Similar Documents

Publication Publication Date Title
CN110350089B (en) Bi2O2S-modified SnO2Perovskite solar cell of electron transport layer and preparation method
CN111223990A (en) Inverted perovskite solar cell containing alkali metal halide hole modification layer and preparation method
CN106025085A (en) Perovskite solar cell based on Spiro-OMeTAD/CuxS composite hole transport layer and preparation method thereof
CN111092160B (en) Method for passivating lower interface of perovskite solar cell with inverse structure
CN108389969B (en) Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell
CN109728169B (en) Perovskite solar cell doped with functional additive and preparation method thereof
CN109755394B (en) Method for preparing perovskite solar cell by applying air knife coating
CN110335945B (en) Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof
CN112490363B (en) Preparation method of perovskite solar cell based on magnetron sputtering zinc oxide/tin dioxide double electron transmission layer
CN101728092A (en) Semiconductor electrode, manufacturing method thereof and solar cell having semiconductor electrode
CN114678472A (en) FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same
CN114914362A (en) Preparation method of efficient and stable titanium ore solar cell
CN113097388B (en) Perovskite battery based on composite electron transport layer and preparation method thereof
CN108767112B (en) BiI with different hole transport layers3Solar cell and preparation method thereof
CN111769197B (en) Perovskite solar cell and preparation method thereof
CN116801652A (en) Crystalline silicon perovskite laminated solar cell and preparation method thereof
CN113394343B (en) Back-incident p-i-n structure perovskite solar cell and preparation method thereof
CN114420853A (en) Method for modifying self-assembled hole transport layer by alkali metal acetate
CN115666191A (en) Method for improving stability of perovskite solar cell device
CN114284437A (en) SnO modified by ammonium salt2Method for preparing efficient perovskite solar cell by using electron transport layer
CN114520288A (en) Preparation method of crystalline silicoperovskite laminated solar cell
CN110246969B (en) Preparation method of perovskite solar cell with pyridine modified tin oxide compact layer
CN113363394A (en) Perovskite battery preparation method
CN114937743B (en) Organic/inorganic perovskite solar cell based on formamidino and preparation method thereof
CN220307715U (en) Perovskite solar cell with double light absorption layer structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant