CN112133835A - Perovskite precursor solution and method for preparing perovskite solar cell by using same - Google Patents

Perovskite precursor solution and method for preparing perovskite solar cell by using same Download PDF

Info

Publication number
CN112133835A
CN112133835A CN201910551479.0A CN201910551479A CN112133835A CN 112133835 A CN112133835 A CN 112133835A CN 201910551479 A CN201910551479 A CN 201910551479A CN 112133835 A CN112133835 A CN 112133835A
Authority
CN
China
Prior art keywords
perovskite
precursor solution
perovskite precursor
preparing
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.)
Pending
Application number
CN201910551479.0A
Other languages
Chinese (zh)
Inventor
朱瑞敏
唐泽国
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.)
Beijing Hongtai Innovation Technology Co ltd
Original Assignee
Beijing Hongtai Innovation Technology Co ltd
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 Beijing Hongtai Innovation Technology Co ltd filed Critical Beijing Hongtai Innovation Technology Co ltd
Priority to CN201910551479.0A priority Critical patent/CN112133835A/en
Publication of CN112133835A publication Critical patent/CN112133835A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • 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
    • 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

Landscapes

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

Abstract

The invention discloses a perovskite precursor solution which comprises a perovskite precursor material, a solvent and an additive, wherein the additive comprises a mercapto compound. The invention also discloses a method for preparing the perovskite solar cell, which comprises the following steps: preparing a substrate; preparing a first carrier transport layer on the substrate; coating the perovskite precursor solution on the first carrier transport layer to obtain a perovskite absorption layer; preparing a second carrier transport layer on the perovskite absorption layer; and preparing a back electrode.

Description

Perovskite precursor solution and method for preparing perovskite solar cell by using same
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite precursor solution and a method for preparing a perovskite solar cell by using the perovskite precursor solution.
Background
Perovskite thin-film solar cells are the most promising solar cells due to the advantages of high photoelectric conversion efficiency, low cost, simple manufacture and the like. The quality and uniformity of the perovskite thin film directly determine the efficiency of the cell. The perovskite thin film with few defects and high crystallinity is more beneficial to the efficient conversion of solar energy into electric energy by the cell, so the preparation of the high-quality perovskite thin film becomes the key of the cell preparation.
The current preparation method of perovskite thin films is generally a solution method. The one-step solution method is to dissolve all the perovskite precursor materials in a solvent, and then use an anti-solvent such as chlorobenzene, ether, etc. to assist the perovskite film formation. The two-step solution process is generally first preparedPbX of a certain thickness2And then dropwise adding the organic amine halide salt solution. The perovskite solar cell prepared by the solution method is also the advantage of low-cost mass production of the perovskite solar cell technology.
However, in the preparation of perovskite solar cells by a solution method, perovskite thin film deposition is subjected to nucleation, crystallization and crystal growth processes, and controllable growth of perovskite thin films cannot be achieved at present. How to prepare the perovskite thin film with large grain size and low defect density is the key for preparing the high-efficiency perovskite solar cell and is an extremely important research and development subject of the perovskite solar cell.
Disclosure of Invention
In order to solve the technical problems, the invention provides a perovskite precursor solution and a method for preparing a perovskite solar cell by using the perovskite precursor solution, so that a perovskite thin film with higher quality is obtained, and the perovskite solar cell with excellent performance is obtained.
The perovskite precursor solution provided by the invention comprises a perovskite precursor material, a solvent and an additive, wherein the additive comprises a mercapto compound.
Further, the mercapto compound is mercaptoethanol or mercaptoacetic acid.
Further, the content of the mercapto compound is 1-5% of the perovskite precursor solution by volume.
Further, the perovskite precursor material comprises an organic amine halide salt and PbX2Wherein X is halogen. In one embodiment, the organoamine halide salt is selected from formamidinehalide, methylamine halide, or a combination thereof.
Further, the perovskite precursor material is APbX3Materials of structure (la) wherein a is an organic cation, preferably, a is HN ═ CHNH3 +、CH3NH3 +、Cs+、Rb+Or a combination thereof; x is halogen.
The invention also provides a method for preparing a perovskite solar cell, comprising:
preparing a substrate;
preparing a first carrier transport layer on the substrate;
coating the perovskite precursor solution according to any one of claims 1 to 8 on the first carrier transport layer to obtain a perovskite absorption layer;
preparing a second carrier transport layer on the perovskite absorption layer;
and preparing a back electrode.
Further, the perovskite absorption layer is prepared by a one-step solution method, which comprises the steps of completely dissolving a perovskite precursor material, adding a mercapto compound, and spin-coating the mercapto compound on the first carrier transport layer;
further, the perovskite absorption layer is prepared by a two-step solution method, which comprises the steps of firstly preparing a solution containing PbX2And an additive is coated on the first carrier transport layer, and then an organic amine halide salt solution is coated.
By adopting the perovskite precursor solution and the method for preparing the perovskite solar cell, the film forming speed of the perovskite film is reduced, the growth time of the perovskite film is prolonged, the growth of crystal grains of the perovskite film is facilitated, and the defect density is reduced, so that the perovskite film with higher quality is obtained.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic diagram of one embodiment of a perovskite absorber layer prepared using a one-step process;
FIG. 2 is a schematic diagram of one embodiment of a perovskite absorber layer prepared using a two-step process;
FIG. 3 is a schematic diagram of one embodiment of a perovskite solar cell fabricated using the method of the present invention;
FIG. 4 is a comparative scanning electron micrograph of a perovskite active layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The perovskite thin film solar cell generally comprises functional thin films of a transparent substrate, a transparent conductive film, a carrier transmission layer, a perovskite absorption layer, a metal electrode and the like. The quality and uniformity of the perovskite thin film directly determine the efficiency of the cell. The perovskite thin film with few defects and high crystallinity is more beneficial to the efficient conversion of solar energy into electric energy by the cell, so the preparation of the high-quality perovskite thin film becomes the key of the cell preparation.
The invention provides a perovskite precursor solution for preparing a perovskite absorption layer. The perovskite precursor solution comprises a perovskite precursor material, a solvent and an additive, wherein the additive comprises a mercapto compound.
The perovskite precursor material of the invention refers to a raw material used for preparing the perovskite absorption layer.
In one embodiment, the perovskite precursor material for use in the present invention is APbX3A material of structure wherein a is a monovalent organic or inorganic cation. Preferably, a is HN ═ CHNH3 +(FA)、CH3NH3 +(MA)、Cs+、Rb+Or a combination thereof. X is halogen, preferably halogen includes Cl, Br and I.
In one embodimentIn the formula, the perovskite precursor material comprises organic amine halide salt and PbX2And X is halogen. Preferably, the organoamine halide salt is selected from formamidinehalide, methylamine halide, or a combination thereof.
The solvent of the perovskite precursor solution of the invention is a solvent capable of dissolving the precursor material. In one embodiment, the solvent comprises Dimethylformamide (DMF), Dimethyl Sulfoxide (DSMO), gamma-butyrolactone, or a combination thereof.
The perovskite precursor solution of the invention also contains an additive which is a mercapto compound. The mercapto compound used in the present invention refers to a mercapto group-containing compound.
In one embodiment, the additive of the present invention is selected from mercaptoethanol (. beta. -ME) or thioglycolic acid (MAA). The invention adopts mercaptoethanol or mercaptoacetic acid as an additive of the perovskite precursor solution to regulate and control the growth process of the perovskite film. The sulfur in the beta-ME or MAA contains lone-pair electrons and can provide electrons to the empty orbit of lead to form a chelating intermediate product, thereby reducing the film forming speed of the perovskite film, prolonging the growth time of the perovskite film, being beneficial to the growth of crystal grains of the perovskite film and reducing the defect density, and further obtaining the perovskite film with higher quality.
The content of the mercapto compound in the perovskite precursor solution is 1-5% of the perovskite precursor solution by volume.
In another aspect, the present invention provides a method for preparing a perovskite solar cell using the perovskite precursor solution of the first aspect of the present invention, comprising:
preparing a substrate;
preparing a first carrier transport layer on the substrate;
preparing a perovskite absorption layer on the first carrier transmission layer by adopting the perovskite precursor solution;
preparing a second carrier transport layer on the perovskite absorption layer;
and preparing a back electrode.
The perovskite absorption layer is prepared by a solution method.
One-step solution method: and completely coating the precursor solution on the carrier transport layer, and then annealing to obtain the perovskite absorption layer. FIG. 1 is a schematic diagram of one embodiment of a perovskite absorber layer prepared using a one-step process.
Two-step solution process: firstly, the material contains PbX2And the solution of the additive is coated on the carrier transport layer, and then the organic amine halide salt solution is coated or dripped on the carrier transport layer to obtain the perovskite absorption layer. FIG. 2 is a schematic diagram of one embodiment of a two-step process for producing a perovskite absorber layer.
The other layers of the perovskite solar cell are prepared using any preparation method known in the art. Fig. 3 is a schematic diagram of an embodiment of a perovskite solar cell fabricated by the method of the present invention, comprising in order from bottom to top:
a substrate 1, which may be glass or a transparent polymer;
the transparent conductive oxide film 2 can be fluorine-doped tin oxide (FTO), Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO) and the like;
carrier transport layers 3, 5, the carrier transport layers including electron transport layers or hole transport layers. The electron transport layer can be titanium dioxide (TiO)2) Tin dioxide (SnO)2) Wide bandgap semiconductors such as zinc oxide (ZnO), or organic materials such as fullerene derivatives (PCBM); the hole transport layer can be a Spiro-OMeTAD (2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group)]-9, 9' -spirobifluorene) (formal structure) or PEDOT: PSS, NiOx(trans structure);
perovskite absorption layer 4, which may be MAPbI3、FAPbI3、(FAPbI3)x(MAPbCl3)1-x(x-0-1), and the like;
the metal back electrode 6 can be formed by evaporating a metal film (Au or Ag) as an electrode by an evaporation method.
The technical solution of the present invention is further understood by the specific preparation method below:
example 1
Layer 1 of example 1 was a poly (terephthalic acid) (PET) substrate, layer 2 was FTO, and layer 3 was SnO2Electronic deviceThe transport layer, layer 4, is a perovskite photoactive layer (FAPBI)3)0.95(MAPbBr3)0.05 Layer 5 is a spiro-OMeTAD hole transport layer and layer 6 is 80nm gold as the anode. The preparation method specifically comprises the following steps:
s1, carrying out ultraviolet/ozone treatment on the surface of poly (terephthalic acid) (PET)/FTO, and then spin-coating a layer of SnO with the mass fraction of 2.5% on the FTO2Carrying out thermal annealing on the nano particle dispersion liquid for 30min at 150 ℃ after the spin coating is finished to obtain a 1 st layer to a 3 rd layer;
s2, mixing 889mg FAPBI3,33mg MAPbBr3And 33mg of MACl were dissolved in 900. mu.l of DMF and 100. mu.l of DMSO, then 10. mu.l of beta-ME was added, stirred until completely dissolved, filtered through a microporous membrane, spin-coated, and then annealed at 130 ℃ for 30 min.
S3, spin coating a Spiro-OMeTAD solution on the perovskite layer: Spiro-OMeTAD was dissolved in chlorobenzene at a concentration of 50mg/ml, to which small amounts of Li-TFSI and tBP were added as additives, at a spin speed of 5000 rpm. And standing in dry air for more than 48h after the spin coating to form an electron blocking layer with the thickness of about 100 nm.
S4, continuously evaporating a layer of Au with the thickness of about 80nm on the 1 st layer to the 5 th layer, and limiting the area covered by the Au through a mask plate to ensure that the area of an effective area is 1cm2。
Example 2.
Example 1 was repeated with the same procedure except that 10 μ l of MAA was added to the perovskite precursor solution in said step S2.
Comparative example 1.
Example 1 was repeated with the same procedure except that in said step S2, no additive was added.
Example 3.
Example 1 was repeated with the same procedure except that in said step S2, the perovskite layer was prepared by a two-step process of spin-coating 1.2M PbI with a suitable amount of β -ME2The solution was annealed at 70 ℃ for 10s and then spin-coated on PbI with a solution of FAI, MABr, MACl and (80: 6:6 by mass) in isopropanol2Annealing the film at 150 deg.C for 10 min.
Example 4.
Example 3 was repeated with the same steps except that in said step S2, the same amount of MAA was used instead of β -ME.
Comparative example 2.
Example 3 was repeated with the same procedure except that in said step S2, no additive was added.
And (3) morphology analysis:
FIG. 4 is a scanning electron micrograph of a perovskite active layer: (a) comparative example 1(b) example 1
It can be seen that the grain size of the perovskite thin film in example 1 is significantly larger than that of comparative example 1, and the perovskite thin film in example 1 is more dense and smooth. The reason is that after the beta-ME is added, the beta-ME can neutralize Pb in the solution2+Coordination, forming a chelated intermediate product, slowing the crystallization process of the perovskite, thereby facilitating the growth of perovskite grains.
The battery performance is as follows:
the light intensity is 100mW/cm2The current-voltage curves of the cells of the examples and comparative examples were measured under AM 1.5 white light irradiation to obtain a parameter short-circuit current density (J)sc) Open circuit voltage (V)oc) Conversion efficiency (Eff) and Fill Factor (FF). The test results are shown in Table 1.
TABLE 1 table of performance parameters of batteries in examples and comparative examples
Figure BDA0002105593720000071
Comparing examples 1 and 2 with comparative example 1, the open-circuit voltage, the current density and the fill factor of the cell in the solar cell prepared in example 1 are all significantly improved, thus resulting in the increase of the cell efficiency from 18.22% to 19.42%; the open-circuit voltage of the solar cell prepared in the embodiment 2 is almost unchanged, the short-circuit current density and the filling factor are greatly improved, and the cell efficiency is improved to 19.65%; likewise, comparing examples 3 and 4 with comparative example 2, the open-circuit voltage and the current density of the cell in the solar cell prepared in example 3 were significantly improved, and the cell efficiency was improved from 18.81% to 19.15%; the cell fill factor in the solar cell prepared in example 4 was slightly increased, while the short-circuit current density and the open-circuit voltage were greatly increased, so the cell efficiency was increased to 20.36%. The beta-ME or MAA coordinates with lead ions in the perovskite precursor solution, so that the film forming speed of the perovskite film is reduced, the growth time of the perovskite film is prolonged, the growth of crystal grains of the perovskite film is facilitated, the defect density is reduced, and the perovskite film with higher quality is obtained.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

1. A perovskite precursor solution, characterized in that the perovskite precursor solution comprises a perovskite precursor material, a solvent and an additive, the additive comprising a mercapto compound.
2. The perovskite precursor solution of claim 1, wherein the mercapto compound is mercaptoethanol or mercaptoacetic acid.
3. The perovskite precursor solution according to claim 1, wherein the mercapto compound is present in an amount of 1-5% by volume of the perovskite precursor solution.
4. The perovskite precursor solution of claim 1, wherein the solvent is DMF, DMSO, gamma-butyrolactone, or a combination thereof.
5. The perovskite precursor solution of any one of claims 1 to 4, wherein the perovskite precursor material comprises an organoamine halide salt and PbX2And X is halogen.
6. The perovskite precursor solution of claim 5, wherein the organoamine halide salt is selected from formamidinehalide, methylamine halide, or a combination thereof.
7. The perovskite precursor solution of any one of claims 1 to 4, wherein the perovskite precursor material is APbX3A material of structure wherein a is an organic or inorganic monovalent cation and X is a halogen.
8. The perovskite precursor solution of claim 7, wherein A is HN ═ CHNH3 +、CH3NH3 +、Cs+、Rb+Or a combination thereof.
9. A method for fabricating a perovskite solar cell, comprising:
preparing a substrate;
preparing a first carrier transport layer on the substrate;
coating the perovskite precursor solution according to any one of claims 1 to 8 on the first carrier transport layer to obtain a perovskite absorption layer;
preparing a second carrier transport layer on the perovskite absorption layer;
and preparing a back electrode.
10. The method according to claim 9, wherein the perovskite absorption layer is prepared by a one-step solution method comprising dissolving all of the perovskite precursor material and adding a mercapto compound, which is spin-coated on the first carrier transport layer.
11. The method of claim 9, wherein the perovskite absorber layer is prepared by a two-step solution process comprising first incorporating PbX2And additives are coated on the second layerA carrier transport layer is then coated with an organoamine halide salt solution.
CN201910551479.0A 2019-06-24 2019-06-24 Perovskite precursor solution and method for preparing perovskite solar cell by using same Pending CN112133835A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910551479.0A CN112133835A (en) 2019-06-24 2019-06-24 Perovskite precursor solution and method for preparing perovskite solar cell by using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910551479.0A CN112133835A (en) 2019-06-24 2019-06-24 Perovskite precursor solution and method for preparing perovskite solar cell by using same

Publications (1)

Publication Number Publication Date
CN112133835A true CN112133835A (en) 2020-12-25

Family

ID=73850040

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910551479.0A Pending CN112133835A (en) 2019-06-24 2019-06-24 Perovskite precursor solution and method for preparing perovskite solar cell by using same

Country Status (1)

Country Link
CN (1) CN112133835A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864330A (en) * 2021-01-26 2021-05-28 南方科技大学 Perovskite precursor solution and preparation method and application thereof
CN114220922A (en) * 2021-11-18 2022-03-22 华中科技大学 Method for thermally evaporating perovskite material through in-situ passivation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112864330A (en) * 2021-01-26 2021-05-28 南方科技大学 Perovskite precursor solution and preparation method and application thereof
CN114220922A (en) * 2021-11-18 2022-03-22 华中科技大学 Method for thermally evaporating perovskite material through in-situ passivation

Similar Documents

Publication Publication Date Title
Mahmud et al. Low temperature processed ZnO thin film as electron transport layer for efficient perovskite solar cells
CN109904318B (en) Perovskite thin film preparation method based on anti-solution bath and solar cell
CN109148644B (en) Gradient annealing and anti-solvent-based all-inorganic perovskite battery and preparation method thereof
CN109216557B (en) Based on citric acid/SnO2Perovskite solar cell of electron transport layer and preparation method thereof
US20210166885A1 (en) Method for preparing inorganic perovskite battery based on synergistic effect of gradient annealing and antisolvent, and prepared inorganic perovskite battery
CN108598268B (en) Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition
CN108899420A (en) The preparation method and perovskite solar cell device of perovskite thin film
CN109728169B (en) Perovskite solar cell doped with functional additive and preparation method thereof
CN108807680B (en) Perovskite solar cell
CN105870341A (en) Method for improving growth quality of perovskite crystal and solar cell device
CN110729403B (en) Preparation method and application of high-quality organic-inorganic hybrid perovskite film
Zong et al. Highly stable hole-conductor-free perovskite solar cells based upon ammonium chloride and a carbon electrode
CN108281552A (en) A kind of perovskite solar cell and preparation method thereof with energy band gradient
CN111092157A (en) Preparation method of efficient and stable perovskite solar cell
Duan et al. Surface modification of SnO2 blocking layers for hysteresis elimination of MAPbI3 photovoltaics
CN105810831A (en) Lead-tin hybrid perovskite thin film, and preparation method and application therefor
Jiang et al. Efficiency enhancement of perovskite solar cells by fabricating as-prepared film before sequential spin-coating procedure
Wang et al. Effective control of the length of ZnO-TiO2 nanorod arrays as electron transport layer of perovskite solar cells with enhanced performance
CN115020596A (en) Double-layer electron transport layer, perovskite solar cell with double-layer electron transport layer, and preparation method and application of perovskite solar cell
CN112133835A (en) Perovskite precursor solution and method for preparing perovskite solar cell by using same
CN110635050B (en) Method for preparing high-quality perovskite thin film with assistance of pressure
CN114883493A (en) Solar cell based on three-dimensional/two-dimensional perovskite and preparation method thereof
Runa et al. Highly reproducible perovskite solar cells based on solution coating from mixed solvents
CN107845729B (en) Perovskite solar cell and preparation method thereof
CN113972323A (en) Sodium thiocyanate-doped efficient and stable perovskite solar cell and preparation method thereof

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