CN107833970B - Surface modification method of perovskite film - Google Patents

Surface modification method of perovskite film Download PDF

Info

Publication number
CN107833970B
CN107833970B CN201710974249.6A CN201710974249A CN107833970B CN 107833970 B CN107833970 B CN 107833970B CN 201710974249 A CN201710974249 A CN 201710974249A CN 107833970 B CN107833970 B CN 107833970B
Authority
CN
China
Prior art keywords
thin film
perovskite thin
perovskite
surface modification
modification method
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.)
Active
Application number
CN201710974249.6A
Other languages
Chinese (zh)
Other versions
CN107833970A (en
Inventor
陈炜
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.)
Huazhong University of Science and Technology
Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Ezhou Institute of Industrial Technology Huazhong University of Science and Technology
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 Huazhong University of Science and Technology, Ezhou Institute of Industrial Technology Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201710974249.6A priority Critical patent/CN107833970B/en
Publication of CN107833970A publication Critical patent/CN107833970A/en
Application granted granted Critical
Publication of CN107833970B publication Critical patent/CN107833970B/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
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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
    • 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

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a surface modification method of a perovskite thin film, which comprises the following steps: (1) dissolving a surface modifier in an inert solvent, and preparing a surface modification solution with the concentration of 0.1-10 mg/ml, wherein the molecular structural formula of the surface modifier is as follows:
Figure DDA0001438195180000011
n is 1-8; (2) and spin-coating the surface modification solution on the surface of one side of the perovskite thin film, and drying at the temperature of 60-150 ℃. The surface modification is carried out on the upper surface of the perovskite thin film, so that the surface of the perovskite thin film is hydrophobic, the corrosion of moisture in the environment to the perovskite can be effectively shielded, the degradation speed of the perovskite thin film is greatly delayed, and the stability of the prepared perovskite solar cell is further effectively improved.

Description

Surface modification method of perovskite film
Technical Field
The invention relates to a solar cell preparation technology, in particular to a surface modification method of a perovskite thin film.
Background
With the increasing shortage of traditional energy and the increasing severity of global environmental problems, people are more and more urgent to develop and utilize new energy, especially to develop clean and renewable solar energy by utilizing photovoltaic technology. The traditional crystalline silicon solar cell has relatively high cost, and other novel solar cells such as a dye-sensitized cell and an organic solar cell have generally low equivalent rate and poor stability, so that a plurality of problems exist in the aspect of industrialization.
Since the first report in 2009, perovskite solar cells have received extensive attention from both academia and industry due to their ultra-low cost, solution-soluble fabrication processes. The energy conversion efficiency is rapidly improved to more than 20% from the initial 3.8%. With the continuous and deep research, the efficiency of the cell is probably more than that of the crystalline silicon solar cell which is developed and matured at present. Therefore, the method is considered to have extremely high application prospect in the aspect of industrialization.
The perovskite solar cell is divided into a mesoporous structure and a planar structure, and the planar structure is divided into a planar p-i-n structure and a planar n-i-p structure. For example, the basic structural composition of a planar p-i-n cell is "transparent conductive substrate/hole transport layer/perovskite layer/electron transport layer/metal electrode". During the use process of the perovskite solar cell, moisture in the air can permeate into the perovskite thin film, so that the perovskite material is subjected to dissolution denaturation or even phase decomposition, and the rapid performance attenuation of the device and the great reduction of the service life of the cell are caused. Therefore, it is necessary to modify the perovskite material, and the service life of the battery device is prolonged by improving the stability of the perovskite thin film, which is very important for enhancing the practical value of the perovskite solar battery.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a surface modification method of a perovskite thin film, and solves the problem of low device stability caused by degradation and denaturation of materials due to the fact that the surface of the perovskite thin film is easily corroded by moisture in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a surface modification method of a perovskite thin film, which is characterized by comprising the following steps:
(1) dissolving a surface modifier in an inert solvent, and preparing a surface modification solution with the concentration of 0.1-10 mg/ml, wherein the molecular structural formula of the surface modifier is as follows:
Figure BDA0001438195160000021
(2) and spin-coating the surface modification solution on the surface of one side of the perovskite thin film, and drying at the temperature of 60-150 ℃.
Preferably, the inert solvent is isopropanol, chlorobenzene or toluene.
Preferably, the step (2) further comprises annealing treatment at 60-150 ℃ for 1-60 minutes after drying.
Preferably, the drying temperature and the annealing treatment temperature are both 70-100 ℃, and the annealing treatment time is 5-10 minutes.
Preferably, the concentration of the surface modification solution is 1.0-3.0 mg/ml.
Preferably, the perovskite thin film has a molecular general formula of APbX3Wherein A comprises CH3NH3 +、CH(NH2)2 +、Cs+X comprises I-、Br-、Cl-At least one anion of (a).
Compared with the prior art, the surface modification method has the advantages that the surface modification is carried out on the upper surface of the perovskite thin film, so that the surface of the perovskite thin film is hydrophobic, the corrosion of moisture in the environment to the perovskite can be effectively shielded, the degradation speed of the perovskite thin film is greatly delayed, and the stability of the prepared perovskite solar cell is effectively improved.
Drawings
FIG. 1 is a wet angle measurement of an unmodified perovskite thin film;
FIG. 2 is a wetting angle measurement of the modified perovskite thin film of example 1;
FIG. 3 is a wetting angle measurement of the modified perovskite thin film of example 2;
FIG. 4 is a wetting angle measurement of the modified perovskite thin film of example 3;
FIG. 5 is a wetting angle measurement of the modified perovskite thin film of example 4;
FIG. 6 is a wetting angle measurement of the modified perovskite thin film of example 5;
FIG. 7 is an infrared spectrum of the perovskite thin film modified in examples 1 to 5;
FIG. 8 is a comparison graph of X-ray diffraction spectrum tests of the perovskite thin films modified and unmodified in the embodiments 1-5;
FIG. 9 is a comparative graph of light aging stability testing of perovskite solar cells of the present invention;
fig. 10 is a comparative graph of photocurrent-voltage curve testing for perovskite solar cells of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a surface modification method of a perovskite thin film, which is characterized by comprising the following steps:
(1) dissolving a surface modifier in an inert solvent, and preparing a surface modification solution with the concentration of 0.1-10 mg/ml, wherein the concentration of the surface modification solution is preferably 1.0-3.0 mg/ml; wherein, the molecular structural formula of the surface modifier is as follows:
Figure BDA0001438195160000031
(2) spin-coating the surface modification solution on the surface of one side of the perovskite thin film, drying at 60-150 ℃, and then carrying out annealing treatment, wherein the annealing treatment time is generally 1-60 minutes; wherein, the drying temperature and the annealing treatment temperature are preferably set to be 70-100 ℃, and the annealing treatment time is preferably 5-10 minutes.
In the embodiment, an inert solvent is adopted, specifically, isopropanol, chlorobenzene or toluene can be adopted, and the perovskite thin film cannot be dissolved, so that modified molecules cannot deeply penetrate into the perovskite thin film, that is, the good photoelectric property of the perovskite thin film as a whole cannot be damaged, and the photoelectric conversion efficiency cannot be reduced due to surface modification.
Wherein, the general formula of the perovskite thin film of the embodiment is APbX3Wherein A comprises CH3NH3 +、CH(NH2)2 +、Cs+X comprises I-、Br-、Cl-I.e., the perovskite thin film of the present embodiment is composed of at least one of the following components: CH (CH)3NH3PbI3、CH(NH2)2PbI3、CsPbI3、CH3NH3PbBr3、CH(NH2)2PbBr3、CsPbBr3、CH3NH3PbCl3、CH(NH2)2PbCl3、CsPbCl3。
When the perovskite solar cell is prepared, a hole blocking layer is arranged on an FTO substrate, a perovskite thin film is arranged on the hole blocking layer through a spin coating method, then the surface of the perovskite thin film is modified according to the method, the surface of the perovskite thin film to be modified is the surface of one side of the perovskite thin film opposite to an electron transport layer, after the surface is modified, the electron transport layer is spin-coated, and then a metal electrode is vapor-coated, so that the perovskite solar cell can be formed.
To illustrate the superiority of the surface modification method of this example, the following examples are carried out (wherein, the surface modifiers in examples 1 to 5 each adopt a molecular structure in which n in the above molecular structural formula corresponds to 1, 2, 3, 4, and 8):
example 1
The perovskite thin film of example 1 had a composition of CH3NH3PbI3The modification steps are as follows: dissolving surface modifier toluic acid in isopropanol to obtain surface modifying solution with concentration of 1.0mg/ml, and spin-coating the surface modifying solution on CH3NH3PbI3The upper surface of the perovskite thin film on the side opposite to the electron transport layer was dried at 100 ℃ and annealed for 5 minutes.
Example 2
The modification procedure of this example 2 was substantially the same as in example 1, except that the surface modifier was 4-dimethylaminobenzoic acid.
Example 3
The modification procedure of example 3 was substantially the same as in example 1, except that the surface modifier was 4-tert-butylbenzoic acid.
Example 4
The modification procedure of this example 4 was substantially the same as in example 1, except that the surface modifier was 4-n-pentylbenzoic acid.
Example 5
The modification procedure of this example 5 is substantially the same as in the examples, except that the surface modifier is 4-octylbenzoic acid.
As shown in fig. 1 to 6, fig. 1 is a test chart of the infiltration angle of an unmodified perovskite thin film, fig. 2 to 6 are test charts of the infiltration angle of a perovskite thin film modified by the surface modification method according to embodiments 1 to 5, and it can be seen by comparing fig. 2 to 6 with fig. 1 that the perovskite thin film modified in fig. 2 to 6 has a significantly larger infiltration angle than the unmodified perovskite thin film, which makes the surface of the perovskite thin film have stronger hydrophobic property after modification, thereby improving the water resistance and stability of the perovskite thin film, and is also beneficial to the stability of the prepared perovskite solar cell.
Fig. 7 is an infrared spectrum of the perovskite thin film modified in the embodiments 1 to 5, and it can be seen from fig. 7 that the surface modification method of the embodiment does not destroy the good photoelectric properties of the original perovskite thin film, and the photoelectric conversion efficiency of the prepared perovskite solar cell is not reduced after modification.
The perovskite thin films modified in the embodiments 1 to 5 are respectively aged for 24 hours under the conditions of high temperature of 40 ℃ and high humidity of 80 percent and are subjected to an X-ray diffraction spectrum test, then carrying out X-ray diffraction spectrum test on the unmodified perovskite thin film and the unmodified and aged perovskite thin film, as shown in FIG. 8, when the X-ray diffraction spectrum test was compared, it was found that, after the unmodified perovskite thin film was aged, a very obvious lead iodide diffraction peak appears at a diffraction angle of 12.6 degrees, which shows that the unmodified perovskite film has obvious material degradation after aging, the intensity of the lead iodide diffraction peak of the perovskite thin film subjected to the surface modification treatment is obviously weak, which shows that the content of PbI2 in the perovskite thin film subjected to the surface modification treatment is very low, and the perovskite thin film is only slightly degraded, so that the perovskite thin film subjected to the modification treatment in the embodiments 1-5 obviously has better stability.
The perovskite thin film modified in the embodiment 1-5 and the unmodified perovskite thin film are prepared to form a perovskite solar cell, and are prepared according to the following modes: the solar cell comprises a glass substrate, an FTO substrate, a hole layer, a perovskite thin film, a surface modification layer, an electron transmission layer and a silver electrode which are sequentially arranged from bottom to top to form the perovskite solar cell, wherein the hole layer is NiO, the perovskite thin film is CH3NH3PbI3, and the electron transmission layer is a fullerene derivative PCBM. Performing illumination aging stability test on the 6 groups of prepared perovskite solar cells, specifically, under the conditions that the perovskite solar cells are not packaged, the humidity is 30 percent and the temperature is 25 ℃, simulating solar illumination by a white light LED, wherein the light intensity is 100mW/cm2, and continuously detecting the maximum power point of the perovskite solar cells; as shown in fig. 9, the efficiency decay rate of the solar cell corresponding to the modified perovskite thin film in the embodiments 1 to 5 is significantly slower, that is, the stability of the solar cell corresponding to the modified perovskite thin film is significantly improved.
The photocurrent and voltage of the cell device of the 6 sets of perovskite solar cells prepared above are tested, the test comparison results are shown in fig. 10, it can be seen through comparison that the open-circuit voltage, the short-circuit current, the fill factor and the photoelectric conversion efficiency of the cell device of the perovskite solar cell prepared by the perovskite thin film subjected to surface modification in the embodiments 1-4 are all improved to a certain extent, whereas in the embodiment 5, the interface conductivity is not good due to the overlong carbon chain (n is 8) of the surface modifier 4-octylbenzoic acid, so that the interface charge transmission is influenced, and the prepared perovskite solar cell does not reach the ideal photoelectric conversion efficiency.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (6)

1. A surface modification method of a perovskite thin film is characterized by comprising the following steps:
(1) dissolving a surface modifier in an inert solvent, and preparing a surface modification solution with the concentration of 0.1-10 mg/ml, wherein the molecular structural formula of the surface modifier is as follows:
Figure FDA0001438195150000011
(2) and spin-coating the surface modification solution on the surface of one side of the perovskite thin film, and drying at the temperature of 60-150 ℃.
2. The surface modification method for the perovskite thin film as claimed in claim 1, wherein the inert solvent is isopropanol, chlorobenzene or toluene.
3. The surface modification method of the perovskite thin film as claimed in claim 1 or 2, wherein the step (2) further comprises annealing at 60 to 150 ℃ for 1 to 60 minutes after drying.
4. The surface modification method for a perovskite thin film as claimed in claim 3, wherein the drying temperature and the annealing treatment temperature are both 70 to 100 ℃, and the annealing treatment time is 5 to 10 minutes.
5. The surface modification method for a perovskite thin film as claimed in claim 4, wherein the concentration of the surface modification solution is 1.0 to 3.0 mg/ml.
6. The method for surface modification of a perovskite thin film as claimed in claim 1, wherein the perovskite thin film has a molecular formula of APbX3Wherein A comprises CH3NH3 +、CH(NH2)2 +、Cs+X comprises I-、Br-、Cl-At least one anion of (a).
CN201710974249.6A 2017-10-19 2017-10-19 Surface modification method of perovskite film Active CN107833970B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710974249.6A CN107833970B (en) 2017-10-19 2017-10-19 Surface modification method of perovskite film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710974249.6A CN107833970B (en) 2017-10-19 2017-10-19 Surface modification method of perovskite film

Publications (2)

Publication Number Publication Date
CN107833970A CN107833970A (en) 2018-03-23
CN107833970B true CN107833970B (en) 2020-04-28

Family

ID=61648314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710974249.6A Active CN107833970B (en) 2017-10-19 2017-10-19 Surface modification method of perovskite film

Country Status (1)

Country Link
CN (1) CN107833970B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461635B (en) * 2018-04-11 2019-09-13 北京大学 A kind of method and its application of boron compound surface modification perovskite thin film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560207A (en) * 2013-11-20 2014-02-05 电子科技大学 Organic thin-film solar cell and preparation method thereof
CN105470397A (en) * 2015-11-24 2016-04-06 华东理工大学 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency
CN106531888A (en) * 2016-08-04 2017-03-22 南京工业大学 Porphyrin derivative used for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell
WO2017160955A1 (en) * 2016-03-15 2017-09-21 Nutech Ventures Insulating tunneling contact for efficient and stable perovskite solar cells
CN107221601A (en) * 2017-06-30 2017-09-29 华中科技大学鄂州工业技术研究院 The preparation method and application of interface-modifying layer based on nickel protoxide hole transmission layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560207A (en) * 2013-11-20 2014-02-05 电子科技大学 Organic thin-film solar cell and preparation method thereof
CN105470397A (en) * 2015-11-24 2016-04-06 华东理工大学 Preparation method of organic and inorganic hybrid perovskite film possessing high moisture stability and photoelectric conversion efficiency
WO2017160955A1 (en) * 2016-03-15 2017-09-21 Nutech Ventures Insulating tunneling contact for efficient and stable perovskite solar cells
CN106531888A (en) * 2016-08-04 2017-03-22 南京工业大学 Porphyrin derivative used for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell
CN107221601A (en) * 2017-06-30 2017-09-29 华中科技大学鄂州工业技术研究院 The preparation method and application of interface-modifying layer based on nickel protoxide hole transmission layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Efficient perovskite solar cells via simple interfacial modification toward a mesoporous TiO2 electron transportation layer;L. F. Zhu等;《 RSC Advances》;20160831;第6卷(第85期);第82283页第1栏第2段-第82287页第1栏第1段 *

Also Published As

Publication number Publication date
CN107833970A (en) 2018-03-23

Similar Documents

Publication Publication Date Title
CN108389967B (en) Light absorption layer material of solar cell, wide-band-gap perovskite solar cell and preparation method thereof
KR101571528B1 (en) Perovskite solar cell improving photoelectric conversion efficiency and the manufacturing method thereof
CN105470399A (en) Perovskite solar cell based on undoped organic hole transport layer and preparation method
CN103296211B (en) Heterojunction solar battery device of organic-two dimensional crystal-inorganic hybridization and preparation method thereof
CN112563422B (en) Maleimido undecanoic acid modification-based high-stability perovskite solar cell and preparation method thereof
CN105140404A (en) Bulk heterojunction organic thin-film solar cell and preparation method thereof
CN113193123A (en) Double-interface-layer-modified efficient perovskite solar cell and preparation method thereof
CN106410037A (en) Small organic molecule donor material based double-junction solar cell device and preparation method thereof
CN109942800B (en) Zwitterion conjugated polyelectrolyte interface material with amino acid group
CN109216554B (en) Perovskite solar cell with P3 HT/graphene as hole transport layer and preparation method thereof
CN110649165A (en) Perovskite battery with tetraphenylbiphenyldiamine derivative as hole transport material
CN107833970B (en) Surface modification method of perovskite film
CN108682740A (en) Perovskite battery and preparation method thereof
CN109851571B (en) Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material
CN109378388B (en) Efficient ternary organic solar cell and preparation method thereof
CN108807696B (en) Method for improving interface modification of organic solar cell
CN112885967B (en) Double-layer organic solar cell based on delayed fluorescent material and preparation method
KR101454397B1 (en) The method of Dye-sensitized solar cells employing cobalt-complex-based electrolyte
CN110190192B (en) Preparation method of trans-organic-inorganic hybrid perovskite solar cell
CN112993165A (en) Biocompatible perovskite battery component, precursor liquid and preparation method thereof
CN116247116B (en) 2-amino-5-bromobenzamide material passivated inorganic perovskite-based solar cell and preparation method thereof
CN116230799B (en) 3-amino-5-bromopyridine-2-carboxamide material passivated inorganic perovskite-based solar cell and preparation method thereof
CN220476238U (en) Surface passivation perovskite solar cell
CN220422354U (en) Perovskite battery prepared from high-efficiency modifier 1-propyl-3-methylimidazole bromide
CN110911567B (en) Sulfonate micromolecule material used for organic solar cell cathode interface modification layer

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