CN114464692A - Perovskite ink and application thereof - Google Patents
Perovskite ink and application thereof Download PDFInfo
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- CN114464692A CN114464692A CN202210076369.5A CN202210076369A CN114464692A CN 114464692 A CN114464692 A CN 114464692A CN 202210076369 A CN202210076369 A CN 202210076369A CN 114464692 A CN114464692 A CN 114464692A
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000137 annealing Methods 0.000 claims abstract description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012046 mixed solvent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims abstract description 15
- JMXLWMIFDJCGBV-UHFFFAOYSA-N n-methylmethanamine;hydroiodide Chemical compound [I-].C[NH2+]C JMXLWMIFDJCGBV-UHFFFAOYSA-N 0.000 claims abstract description 15
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims description 45
- 239000010409 thin film Substances 0.000 claims description 30
- 230000005525 hole transport Effects 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000007738 vacuum evaporation Methods 0.000 claims description 6
- 230000007547 defect Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 53
- 239000010408 film Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 26
- 239000011521 glass Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002207 thermal evaporation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 cesium lead halide Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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Abstract
The invention discloses perovskite ink and application thereof, and relates to the technical field of perovskite solar cells. Wherein the perovskite ink comprises the following components: the solvent comprises dimethylamine hydroiodide, lead iodide, cesium iodide and a mixed solvent, wherein the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, and the volume ratio of the dimethylformamide to the dimethyl sulfoxide is 6.8-7.2: 2.8 to 3.2. The invention can make the obtained perovskite ink into CsPbI at 160 ℃ by selecting raw materials and designing the proportion of mixed solvent3Film, realizes CsPbI3Low temperature annealing of film formation and the resulting CsPbI3The film has good appearance, high grain boundary stability and low defect density, thereby leading CsPbI to be3The temperature and humidity stability of the film is excellent; in addition, the implementation of low-temperature annealing enables CsPbI3Of filmsThe preparation is easier to operate, the cost is low, and the method is favorable for large-scale production.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to perovskite ink and application thereof.
Background
Energy shortage and environmental pollution are two major problems facing the world of human beings at present, and inexhaustible solar energy is ideal renewable energy. The third generation solar cell technologies such as Perovskite Solar Cells (PSCs) have the advantages of low cost, high efficiency, easiness in assembly, flexibility and the like. Since the application of perovskite materials to solar cells in 2009, the photoelectric conversion efficiency of perovskite solar cells has rapidly increased to over 25%, but the existence of organic components makes the perovskite thermally unstable, and the use of inorganic materials instead of organic materials is an effective method for improving the stability of perovskite.
At present, Cs is mainly used for replacing or partially replacing organic components in perovskite, wherein, the total inorganic cesium lead halide perovskite (CsPbX)3X ═ I, Br) films have a high absorption coefficient, and excellent thermal stability and charge mobility are of much interest. The CsPbI3 perovskite with black phase has excellent thermal stability as an all-inorganic perovskite, and has a band gap of about 17eV, which is considered as one of the candidate materials of high-efficiency solar cells (PSCs), has potential application value in the photovoltaic field.
The process for preparing the all-inorganic perovskite thin film is roughly divided into an evaporation method and a solution method (one-step spin coating method, two-step dipping method and spraying/blade coating method), wherein the one-step spin coating method is to prepare perovskite ink (also called perovskite precursor solution) firstly and prepare the all-inorganic perovskite thin film through spin coating and heating annealing, the method is simple to operate, but after the existing perovskite ink is spin coated, annealing is needed at the high temperature of 200-220 ℃ to promote perovskite nucleation so as to prepare the perovskite thin film, and the high-temperature annealing can cause the perovskite thin film to have high defect density and low grain boundary stability, so that the application of the all-inorganic perovskite thin film is limited.
Disclosure of Invention
The invention mainly aims to provide perovskite ink and application thereof, and aims to solve the problems of high defect density and low grain boundary stability of the conventional perovskite thin film.
In order to achieve the above object, the present invention provides a perovskite ink comprising the following components:
dimethylamine hydroiodide, lead iodide, cesium iodide and mixed solvent,
the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, wherein the volume ratio of the dimethylformamide to the dimethyl sulfoxide is (6.8-7.2): 2.8 to 3.2.
Optionally, 75-77 mg of the dimethylamine hydroiodide, 229-233 mg of lead iodide and 128-131 mg of cesium iodide are added to 1mL of the mixed solvent in the perovskite ink.
Based on the above purpose, the present invention also provides a preparation method of an all-inorganic perovskite solar cell, which comprises the following steps:
s10, arranging an electron transport layer on the substrate;
s20, spin-coating the perovskite ink on the electron transport layer, and then annealing at 160-180 ℃ for 25-35 min to obtain a perovskite thin film;
s30, arranging a hole transport layer on the perovskite thin film;
and S40, arranging a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
Optionally, step S10 includes:
and spin-coating the n-butyl titanate solution on the surface of the substrate, annealing at 120-130 ℃ for 4-6 min, and then annealing at normal temperature for 25-35 min to obtain the electron transport layer arranged on the substrate.
Optionally, the concentration of the n-butyl titanate solution is 0.14-0.16 mol/L;
the spin coating speed of the spin coating is 1800-2200 rpm, and the spin coating time is 25-30 s.
Optionally, step S20 includes:
on the electron transmission layer, the perovskite ink is spin-coated for 4 to 6 seconds at 900 to 1200rpm, and then spin-coated for 28 to 33 seconds at 5800 to 6200 rpm.
Optionally, step S30 includes:
spin coating P on the perovskite thin film3And (4) annealing the HT solution at 95-105 ℃ for 2-4 min to obtain the hole transport layer.
Optionally, the P3The concentration of the HT solution is 14-16 mg/mL;
the spin coating speed is 3800-4200 rpm, and the spin coating time is 25-30 s.
Optionally, step S40 includes:
and depositing Ag on the hole transport layer in a vacuum evaporation mode to obtain a metal electrode layer.
Optionally, the thickness of the metal electrode layer is 80-100 nm; and/or the presence of a gas in the gas,
the vacuum degree of the vacuum evaporation is 2.5 multiplied by 10-5Pa。
According to the technical scheme provided by the invention, the perovskite ink is prepared from dimethyl amine hydroiodide, lead iodide, cesium iodide and a mixed solvent as raw materials, wherein the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, and the volume ratio of the dimethylformamide to the dimethyl sulfoxide is (6.8-7.2): 2.8-3.2, by selecting raw materials and designing the proportion of a mixed solventThe perovskite ink can prepare CsPbI at 160 DEG C3Film, realizes CsPbI3Low temperature annealing of film formation and the resulting CsPbI3The film has good appearance, high grain boundary stability and low defect density, thereby leading CsPbI to be3The temperature and humidity stability of the film is excellent; in addition, the implementation of low-temperature annealing enables CsPbI3The preparation of the film is easier to operate, the cost is low, and the large-scale production is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a CsPbI diagram showing that CsPbI is prepared according to example 1 of the present invention and comparative examples 1 to 33SEM image of the film;
FIG. 2 is a graph showing CsPbI prepared in examples 1 to 2 of the present invention and comparative examples 4 to 63SEM image of the film;
FIG. 3 is a CsPbI composition prepared in example 1 of the present invention and comparative examples 1 to 33XRD pattern of the film;
FIG. 4 is a CsPbI prepared in example 1 of the present invention and comparative examples 1 to 33The humidity stability test result of the film is shown schematically;
FIG. 5 is a schematic diagram of the humidity stability test results of the all-inorganic perovskite solar cell manufactured in example 1 of the present invention;
fig. 6 is a graph showing the photovoltaic characteristics test results of the all-inorganic perovskite solar cell manufactured in example 1 of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The one-step spin-coating method is to prepare perovskite ink (also called perovskite precursor solution) first, and prepare the perovskite ink through spin-coating and heating annealing, the method is simple to operate, but after the existing perovskite ink is spin-coated, the perovskite ink needs to be annealed at a high temperature of 200-220 ℃ to promote perovskite nucleation, so that a perovskite thin film is prepared, and the high-temperature annealing (200-220 ℃) can cause the following problems: 1. the crystallinity of the perovskite thin film is reduced, and the bonding compactness between a crystal boundary and the crystal boundary is influenced, so that the stability of the crystal boundary is reduced; 2. the perovskite thin film has high defect density; 3. high energy consumption and harsh preparation conditions, thereby leading to higher cost. Therefore, high temperature annealing results in low stability and high cost of the perovskite thin film, thereby limiting the application.
In view of this, the present invention proposes a perovskite ink, which in this embodiment comprises the following components: dimethylamine hydroiodide (DMAI), lead iodide (PbI)2) The cesium iodide (CsI) and the mixed solvent are prepared, wherein the mixed solvent comprises Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and the volume ratio of the DMF to the DMSO is 6.8-7.2: 2.8 to 3.2, that is, a volume ratio of 6.8:3.2, 6.9:3.1, 7:3, 7.1:2.9, 7.2:2.8, etc., preferably 7:3, and when the volume ratio is within the above range, the perovskite ink is preparedWater can be annealed at a lower temperature (about 160 ℃) to form a perovskite thin film.
In the technical scheme provided by the invention, the CsPbI can be prepared from the obtained perovskite ink at 160 ℃ by selecting raw materials and designing the proportion of a mixed solvent3Film, realizes CsPbI3Low temperature annealing of film formation and the resulting CsPbI3The film has good appearance, high grain boundary stability and low defect density, thereby leading CsPbI to be3The temperature and humidity stability of the film is excellent; in addition, the implementation of low-temperature annealing enables CsPbI3The preparation of the film is easier to operate, the cost is low, and the large-scale production is facilitated.
In order to ensure good morphology and high purity of the perovskite thin film formed by the perovskite ink, in the embodiment, 75-77 mg of DMAI and 229-233 mg of PbI are added into every 1mL of the mixed solvent2And 128-131 mg CsI. Preferably, 76.56mg of the DMAI and 230.5mg of PbI are added to 1mL of the mixed solvent2And 129.93mg of CsI.
The perovskite ink is prepared by the above raw materials and the above compounding ratio without any limitation. In one embodiment, the perovskite ink is prepared by: DMAI and PbI are mixed2And dissolving the CsI and the mixed solvent, and then fully oscillating for 10-12 h to obtain the perovskite ink.
On the basis of the above embodiment, the present invention further provides a method for manufacturing an all-inorganic perovskite solar cell, which in one embodiment includes the following steps:
step S10, an electron transport layer is disposed on the substrate.
Wherein, the substrate is conductive glass FTO. It is understood that the conductive glass FTO needs to be pretreated to make the electron transport layer be better bonded to the substrate, and the pretreatment may include steps of cleaning, drying, hydrophobic modification, and the like.
In one embodiment, step S10 includes: spin coating n-butyl titanate solution on the surface of a substrate, annealing at 120-130 ℃ for 4-6 min, and then annealing at normal temperature for 25-35 min to obtain TiO arranged on the substrate2An electron transport layer. Furthermore, the concentration of the n-butyl titanate solution is 0.14-0.16 mol/L, the spin coating speed of the spin coating is 1800-2200 rpm (r/min), and the spin coating time is 25-30 s.
In a preferred embodiment, step S10 includes: spin coating 0.15mol/L n-butyl titanate solution on the surface of the conductive glass FTO, raising the speed to 2000rpm at the speed of 1000rpm, spin coating 26s, annealing at 125 ℃ for 5min, then annealing in the air for 30min, and finally cleaning for 10min by an ultraviolet ozone machine to obtain TiO arranged on the conductive glass FTO2An electron transport layer.
S20, spin-coating the perovskite ink on the electron transmission layer, and then annealing at 160-180 ℃ for 25-35 min to obtain a perovskite thin film;
when the conventional perovskite ink is adopted, annealing at 200-220 ℃ is needed to promote nucleation, so that the perovskite thin film is formed. In the embodiment, the perovskite ink is adopted, and the perovskite thin film with good appearance and excellent stability can be obtained only by annealing at 160-180 ℃. The higher the annealing temperature, the higher the defect density and the higher the energy consumption, therefore, in this embodiment, the annealing temperature is preferably 160 ℃, so that the perovskite thin film not only has low defect density and energy consumption, but also has good stability and morphology. When the annealing temperature is 160 ℃, the annealing time is preferably 30 min.
Preferably, step S20 includes: on the electron transmission layer, the perovskite ink is spin-coated for 4-6 s at 900-1200 rpm, and then spin-coated for 28-33 s at 5800-6200 rpm. Therefore, the prepared perovskite thin film is more tightly combined with the electron transport layer, so that the stability of the perovskite thin film is better.
And step S30, arranging a hole transport layer on the perovskite thin film.
Specifically, P is spin-coated on the perovskite thin film3And (4) annealing the HT solution at 95-105 ℃ for 2-4 min to obtain the hole transport layer. Further, said P3The concentration of the HT solution is 14-16 mg/mL, the spin coating speed of the spin coating is 3800-4200 rpm, and the spin coating time is 25-30 s.
In a preferred embodiment, step S30 includesComprises the following steps: p with a concentration of 15mg/mL3And (3) spin-coating HT solution on the upper surface of the perovskite thin film, raising the speed to 4000rpm at the speed of 2000rpm, spin-coating for 26s, and then annealing at 100 ℃ for 3min to obtain the hole transport layer.
And step S40, arranging a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
Preferably, Ag is deposited on the hole transport layer in a vacuum evaporation mode to obtain the metal electrode layer. Wherein the thickness of the metal electrode layer is 80-100 nm. In another embodiment, the vacuum degree of vacuum evaporation is 2.5 × 10-5Pa。
In a more preferred embodiment, step S40 includes: under vacuum degree of 2.5X 10-5And depositing Ag on the upper surface of the hole transport layer in a thermal evaporation mode under the condition of Pa to obtain a metal electrode layer with the thickness of 90 nm.
According to the invention, through the design of the components and the proportion of the perovskite ink and the process parameters for preparing the perovskite solar cell, the prepared all-inorganic perovskite solar cell device has excellent humidity stability and temperature stability, the circuit voltage (Voc) is 0.94V, and the short-circuit current density (Jsc) reaches 23.09mA/cm2The Fill Factor (FF) reaches 78.2%, and the photoelectric conversion efficiency reaches 14.84%.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Table 1 below lists the raw material formulations of the perovskite inks of examples 1 to 4, and comparative examples 1 to 3 (DMAI, PbI in the Table)2And CsI in mg, DMF and DMSO in mL).
Table 1 raw material formulation
Example 1
(1) Preparing perovskite ink: DMAI and PbI are mixed2And CsI is dissolved in the mixed solvent, and then the mixed solvent is fully shaken for 11h to obtain the perovskite ink.
(2) Spin coating 0.15mol/L n-butyl titanate solution on the surface of the conductive glass FTO, raising the speed to 2000rpm at the speed of 1000rpm, spin coating 26s, annealing at 125 ℃ for 5min, then annealing in the air for 30min, and finally cleaning for 10min by an ultraviolet ozone machine to obtain TiO arranged on the conductive glass FTO2An electron transport layer.
(3) Spin-coating the perovskite ink at 1000rpm for 5s, then spin-coating the perovskite ink at 6000rpm for 30s on the upper surface of the electron transport layer, then placing the perovskite ink on a hot bench, annealing the perovskite ink at 160 ℃ for 30min, and finally cooling the perovskite ink to room temperature to obtain CsPbI after interface treatment3A film.
(4) P with a concentration of 15mg/mL3HT solution is coated on the CsPbI in a spinning way3The upper surface of the film was raised to 4000rpm at a rate of 2000rpm, spin-coated for 26 seconds, and then annealed at 100 ℃ for 3min to obtain a hole transport layer.
(5) Under vacuum degree of 2.5X 10-5And depositing Ag on the upper surface of the hole transport layer in a thermal evaporation mode under the condition of Pa to obtain a metal electrode layer with the thickness of 90nm, and finally obtaining the all-inorganic perovskite solar cell.
Example 2
The procedure was the same as in example 1 except that the annealing temperature in step (3) was changed to 180 ℃.
Example 3
(1) Preparing perovskite ink: DMAI and PbI are mixed2And CsI is dissolved in the mixed solvent, and then the mixed solvent is fully vibrated for 10h to obtain the perovskite ink.
(2) Spin coating 0.14mol/L n-butyl titanate solution on the surface of the conductive glass FTO, raising the speed to 2200rpm at the speed of 1000rpm, spin coating for 25s, annealing at 120 ℃ for 6min, then annealing in the air for 25min, and finally cleaning for 10min by an ultraviolet ozone machine to obtain TiO arranged on the conductive glass FTO2An electron transport layer.
(3) Spin coating the perovskite ink at 900rpm for 6s, then spin coating the perovskite ink at 5800rpm for 33s on the upper surface of the electron transmission layer, then placing the perovskite ink on a hot bench, annealing the perovskite ink at 170 ℃ for 25min, and finally cooling the perovskite ink to room temperature to obtain CsPbI after interface treatment3A film.
(4) P with a concentration of 14mg/mL3HT solution is coated on the CsPbI in a spinning way3The upper surface of the film was raised to 3800rpm at a rate of 2000rpm, spin-coated for 30 seconds, and then annealed at 105 ℃ for 2min to obtain a hole transport layer.
(5) Under vacuum degree of 2.5X 10-5And depositing Ag on the upper surface of the hole transport layer in a thermal evaporation mode under the Pa condition to obtain a metal electrode layer with the thickness of 100nm, and finally obtaining the all-inorganic perovskite solar cell.
Example 4
(1) Preparing perovskite ink: DMAI and PbI are mixed2And CsI are dissolved in the mixed solvent, and then the mixed solvent is fully vibrated for 12h to obtain the perovskite ink.
(2) Spin coating 0.16mol/L n-butyl titanate solution on the surface of the conductive glass FTO, raising the speed to 1800rpm at the speed of 1000rpm, spin coating for 30s, annealing at 130 ℃ for 4min, then annealing in the air for 35min, and finally cleaning for 10min by an ultraviolet ozone machine to obtain TiO arranged on the conductive glass FTO2An electron transport layer.
(3) Spin-coating the perovskite ink at 1200rpm for 4s, then spin-coating the perovskite ink at 6200rpm for 28s on the upper surface of the electron transport layer, then placing the perovskite ink on a hot table, annealing the perovskite ink at 165 ℃ for 35min, and finally cooling the perovskite ink to room temperature to obtain CsPbI after interface treatment3A film.
(4) P with the concentration of 16mg/mL3HT solution is coated on the CsPbI in a spinning way3The upper surface of the film was raised to 4200rpm at a rate of 2000rpm, spin-coated for 25 seconds, and then annealed at 95 ℃ for 4min to obtain a hole transport layer.
(5) Under vacuum degree of 2.5X 10-5Depositing Ag on the upper surface of the hole transport layer by adopting a thermal evaporation mode under the condition of Pa to obtain a metal electrode layer with the thickness of 80nm, and finally obtaining the all-inorganic perovskiteA solar cell.
Comparative example 1
The procedure was the same as in example 1 except that the formulation of the perovskite ink was replaced with the formulation shown in comparative example 1 in table 1 (i.e., in mixed solvent, DMF: DMSO ═ 9: 1).
Comparative example 2
The procedure was the same as in example 1 except that the formulation of the perovskite ink was replaced with the formulation shown in comparative example 2 in table 1 (i.e., in mixed solvent, DMF: DMSO ═ 8: 2).
Comparative example 3
The procedure was the same as in example 1 except that the formulation of the perovskite ink was replaced with the formulation shown in comparative example 3 in table 1 (i.e., in mixed solvent, DMF: DMSO ═ 6: 4).
Comparative example 4
The procedure was the same as in example 1 except that the annealing temperature in step (3) was changed to 200 ℃.
Comparative example 5
The procedure was the same as in example 1 except that the annealing temperature in step (3) was changed to 220 ℃.
Comparative example 6
The procedure was the same as in example 1 except that the annealing temperature in step (3) was replaced with 140 ℃.
CsPbI prepared by each of the above examples and comparative examples3The thin film, as well as the all-inorganic perovskite solar cell, were tested as follows.
(one) SEM characterization
1. CsPbI prepared in step (3) of example 1 and comparative examples 1 to 33The film was observed under a Scanning Electron Microscope (SEM), and the results are shown in FIG. 1.
As can be seen from FIG. 1, CsPbI prepared in example 13Compared with the comparative examples 1 to 3, the crystal grains of the film are fuller and more compact without obvious holes, which shows that the CsPbI prepared by the invention is designed by the proportion of the solvent in the mixed solvent3The film has good appearance.
2. CsPbI prepared in step (3) of examples 1-2 and comparative examples 4-63The film was observed under a Scanning Electron Microscope (SEM)The results are shown in FIG. 2.
As can be seen from FIG. 2, CsPbI prepared in example 1 and example 23The perovskite crystal grain size is uniform, and the grain boundary bonding is compact; CsPbI prepared in comparative examples 4 and 53The film had high surface roughness and high defect density, and CsPbI prepared in comparative example 63The film had no nucleation and had significant porosity. That is, CsPbI prepared in comparative example3The appearance of the film is generally worse than that of the embodiment, which shows that the invention enables the prepared CsPbI to be in accordance with the design of annealing temperature3The film has good appearance.
In addition, in example 2, since the temperature is relatively high compared to example 1, the grain boundary bonding density is inferior to that in example 1.
(II) XRD test
CsPbI prepared in step (3) of example 1 and comparative examples 1 to 33The film was subjected to X-ray diffraction, and the results are shown in FIG. 3.
As can be seen from FIG. 3, CsPbI prepared in example 13Compared with comparative examples 1-3, the characteristic peaks (110) and (220) of the perovskite of the thin film are obviously improved, which shows that the CsPbI prepared by the method is designed by the proportion of the solvent in the mixed solvent3The crystal grain nucleation of the film is fuller, the defect state of the crystal boundary is compensated and obviously reduced, and the transmission of the charge of the current carrier is facilitated, so that the photoelectric conversion efficiency of the photovoltaic cell is improved.
(III) humidity stability test
CsPbI prepared in step (3) of example 1 and comparative examples 1 to 33The results of the film humidity stability test (RH 65%, 25 ℃) are shown in FIG. 4, where 6:4, 8:2, 9:1, and 7:3 in FIG. 4 refer to the volume ratio of DMF to DMSO. The finally obtained all-inorganic perovskite solar cell of example 1 was subjected to a humidity stability test (RH 65%, 25 ℃), and 4 parallel experiments were performed, and the results are shown in fig. 5.
As can be seen from fig. 4, CsPbI prepared in example 1 (DMF: DMSO ═ 7:3)3The film had a lower degree of aged corrosion than that of comparative examples 1 to 3, in which CsPbI was produced3The film had been fully aged and corroded, demonstrating that the inventive examples were madeCsPbI of (2)3The temperature stability of the film is better. In addition, CsPbI after 24h of humidity test3The thin film is made into a solar cell, the internal resistance of the cell device prepared in the example is lower than that of the cell devices prepared in the comparative examples 1 to 3, and the cell device prepared in the example can still work normally through tests.
As can be seen from fig. 5, after the all-inorganic perovskite solar cell manufactured in the embodiment of the present invention is placed under conditions of RH 65% and 25 ℃ for 24 hours, the morphology of the all-inorganic perovskite solar cell is substantially unchanged, and after a test, it is found that the all-inorganic perovskite solar cell device can still normally operate, which indicates that the humidity stability of the solar cell manufactured in the present invention is excellent.
(IV) photovoltaic Property testing
The all-inorganic perovskite solar cell prepared in example 1 was subjected to a photovoltaic characteristic test, and the result thereof is shown in fig. 6. As can be seen from FIG. 6, the circuit voltage (Voc) of the all-inorganic perovskite solar cell was 0.94V, and the short-circuit current density (Jsc) reached 23.09mA/cm2The Fill Factor (FF) reaches 78.2%, and the photoelectric conversion efficiency reaches 14.84%.
It should be noted that the preparation principles of examples 3 and 4 are similar to those of example 1, and therefore the morphology and performance are also similar to those of example 1, which is not described herein again.
In conclusion, the perovskite ink provided by the invention can be used for preparing CsPbI at 160 DEG C3Film, realizes CsPbI3Low temperature annealing of film formation and the resulting CsPbI3The film has good appearance and excellent humidity stability; in addition, through the design of the preparation method of the all-inorganic perovskite solar cell, the obtained solar cell is excellent in humidity stability and good in photovoltaic characteristics.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A perovskite ink comprising the following components:
dimethylamine hydroiodide, lead iodide, cesium iodide and mixed solvent,
the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, and the volume ratio of the dimethylformamide to the dimethyl sulfoxide is (6.8-7.2): 2.8 to 3.2.
2. The perovskite ink as claimed in claim 1, wherein 75 to 77mg of the dimethylamine hydroiodide, 229 to 233mg of lead iodide and 128 to 131mg of cesium iodide are added to 1mL of the mixed solvent.
3. A preparation method of an all-inorganic perovskite solar cell is characterized by comprising the following steps:
s10, arranging an electron transport layer on the substrate;
s20, spin-coating the perovskite ink as described in claim 1 or 2 on the electron transport layer, and then annealing at 160-180 ℃ for 25-35 min to obtain a perovskite thin film;
s30, arranging a hole transport layer on the perovskite thin film;
and S40, arranging a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
4. The method for producing an all-inorganic perovskite solar cell as claimed in claim 3, wherein the step S10 comprises:
and spin-coating the n-butyl titanate solution on the surface of the substrate, annealing at 120-130 ℃ for 4-6 min, and then annealing at normal temperature for 25-35 min to obtain the electron transport layer arranged on the substrate.
5. The method for preparing the all-inorganic perovskite solar cell according to claim 4, wherein the concentration of the n-butyl titanate solution is 0.14-0.16 mol/L;
the spin coating speed of the spin coating is 1800-2200 rpm, and the spin coating time is 25-30 s.
6. The method for producing an all-inorganic perovskite solar cell as claimed in claim 3, wherein the step S20 comprises:
on the electron transmission layer, the perovskite ink is spin-coated for 4-6 s at 900-1200 rpm, and then spin-coated for 28-33 s at 5800-6200 rpm.
7. The method for producing an all-inorganic perovskite solar cell as claimed in claim 3, wherein the step S30 comprises:
spin coating P on the perovskite thin film3And (4) annealing the HT solution at 95-105 ℃ for 2-4 min to obtain the hole transport layer.
8. The method of making an all-inorganic perovskite solar cell of claim 7, wherein the P is3The concentration of the HT solution is 14-16 mg/mL;
the spin coating speed is 3800-4200 rpm, and the spin coating time is 25-30 s.
9. The method for producing an all-inorganic perovskite solar cell as claimed in claim 3, wherein the step S40 comprises:
and depositing Ag on the hole transport layer in a vacuum evaporation mode to obtain a metal electrode layer.
10. The method for preparing an all-inorganic perovskite solar cell according to claim 9, wherein the thickness of the metal electrode layer is 80-100 nm; and/or the presence of a gas in the gas,
the vacuum degree of the vacuum evaporation is 2.5 multiplied by 10-5Pa。
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| LU501865A LU501865B1 (en) | 2022-01-21 | 2022-04-20 | An efficient inorganic hybrid perovskite ink and its application |
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| CN109360895B (en) * | 2018-09-20 | 2022-10-04 | 上海科技大学 | Perovskite material, preparation method and solar cell device thereof |
| US11390533B2 (en) * | 2018-12-14 | 2022-07-19 | Alliance For Sustainable Energy, Llc | Compositions for solution processing of perovskites and methods of making the same |
| US10930494B2 (en) * | 2019-04-09 | 2021-02-23 | Swift Solar Inc. | Vapor phase transport system and method for depositing perovskite semiconductors |
| CN110518128B (en) * | 2019-08-26 | 2023-05-19 | 陕西师范大学 | ACI type two-dimensional perovskite solar cell and preparation method thereof |
| CN112968134B (en) * | 2021-02-03 | 2024-04-23 | 陕西师范大学 | Perovskite solar cell with fused salt assisted crystallization and preparation method thereof |
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| CN104201284A (en) * | 2014-08-29 | 2014-12-10 | 国家纳米科学中心 | Integrated solar battery based on perovskite solar battery and bulk heterojunction solar battery and preparation method thereof |
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