LU501865B1 - An efficient inorganic hybrid perovskite ink and its application - Google Patents

An efficient inorganic hybrid perovskite ink and its application Download PDF

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LU501865B1
LU501865B1 LU501865A LU501865A LU501865B1 LU 501865 B1 LU501865 B1 LU 501865B1 LU 501865 A LU501865 A LU 501865A LU 501865 A LU501865 A LU 501865A LU 501865 B1 LU501865 B1 LU 501865B1
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perovskite
spin
transport layer
coating
film
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LU501865A
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French (fr)
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Chuanjia Jiao
Meihua Chen
Fuzhi Huang
Guijie Liang
Peng Zhou
Jiahao Cheng
Liu Liu
Zhicheng Zhong
Kemeng Song
Chengcai Shan
Wangnan Li
Shaojuan Lu
Jingyang Wang
Junbin Li
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Univ Hubei Arts & Science
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • H01L31/0256—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 characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • H01L31/0352—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 characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—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 characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K30/50—Photovoltaic [PV] devices

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Abstract

The present disclosure provides a perovskite ink and its application, and relates to the technical field of perovskite solar cells. The perovskite ink includes the following components: dimethylamine hydriodate, lead iodide, cesium iodide and mixed solvent, wherein the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, and a volume ratio of the 10 dimethylformamide to the dimethyl sulfoxide is 6.8-7.2:2.8-3.2. Through the selection of raw materials and the design of the mixed solvent ratio, the obtained perovskite ink can prepare CsPbI3 films at 160°C, and realize the low-temperature annealing of CsPbI3 film formation, and the obtained CsPbI3 film has good morphology, high grain boundary stability and low defect density, so that the CsPbI3 film has excellent temperature and humidity stability. In addition, the realization of low-temperature annealing makes the preparation of CsPbI3 film easier to operate, with low cost, which is beneficial to large-scale production.

Description

! LU501865
AN EFFICIENT INORGANIC HYBRID PEROVSKITE INK AND ITS
APPLICATION TECHNICAL FIELD
The present disclosure relates to the technical field of perovskite solar cells, in particular to an efficient inorganic hybrid perovskite ink and its application.
BACKGROUND
Energy shortage and environmental pollution are two major problems of the world today. The inexhaustible solar energy is an ideal renewable energy source. Third-generation solar cell technologies such as perovskite solar cells (PSCs) have the advantages of low cost, high efficiency, easy assembly, and flexibility. Since the application of perovskite materials to solar cells in 2009, the photoelectric conversion efficiency of perovskite solar cells has rapidly risen to more than 25%. However, since the existence of organic components makes perovskites thermally unstable, the use of inorganic materials instead of organic materials has become an effective method to improve the stability of perovskites.
Nowadays, Cs is mainly used to replace or partially replace the organic components in perovskites. All-inorganic cesium lead halide perovskite (CsPbX3, X=I, Br) films have high absorption coefficients, and their excellent thermal stability and charge mobility have attracted much attention. The black phase CsPbI; perovskite has excellent thermal stability as an all-inorganic perovskite with a band gap of about 1.7 eV, and is considered as one of the candidate materials for high-efficiency solar cells with potential applications in photovoltaics.
The process of preparing all-inorganic perovskite films is roughly divided into evaporation method and solution method (one-step spin-coating method, two-step spin-coating method, two-step dipping method, spraying/squeegee coating). The one-step spin-coating method is to first prepare perovskite ink (also called perovskite precursor solution), which is obtained by spin-coating and heating annealing, and this method is simple to operate. However, after spin-coating, the existing perovskite ink needs to be annealed at a high temperature of 200~220°C to promote the nucleation of the perovskite, so as to obtain the perovskite film.
However, high-temperature annealing results in high defect density and low grain boundary stability in perovskite films, which limit their applications.
2 LU501865
SUMMARY
The main objective of the present disclosure 1s to provide a perovskite ink and its application, aiming at solving the problems of high defect density and low grain boundary stability of the existing perovskite films.
In order to achieve the above objective, the present disclosure provides a perovskite ink, including the following components: dimethylamine hydriodate, lead iodide, cesium iodide and mixed solvent, wherein the mixed solvent includes dimethylformamide and dimethyl sulfoxide, and a volume ratio of the dimethylformamide to the dimethyl sulfoxide is 6.8-7.2:2.8-3.2.
In an embodiment, in the perovskite ink, 75-77 mg of the dimethylamine hydriodate, 229-233 mg of the lead iodide and 128-131 mg of the cesium iodide are added to each 1 mL of the mixed solvent.
Based on the above objective, the present disclosure further provides a method for preparing an all-inorganic perovskite solar cell, including the following operations: providing an electron transport layer on a substrate; spin-coating the perovskite ink described above on the electron transport layer, and then annealing at 160-180°C for 25-35 min to obtain a perovskite film; providing a hole transport layer on the perovskite film; and providing a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
In an embodiment, the operation of providing an electron transport layer on a substrate includes: spin-coating n-butyl titanate solution on a surface of the substrate, annealing at 120-130°C for 4-6 min, and then annealing at room temperature for 25-35 min to obtain the electron transport layer provided on the substrate.
In an embodiment, a concentration of the n-butyl titanate solution is 0.14-0.16 mol/L; a spin-coating speed is 1800-2200 rpm, and a spin-coating time is 25-30 s.
3 LU501865
In an embodiment, the operation of spin-coating the perovskite ink on the electron transport layer, and then annealing at 160-180°C for 25-35 min to obtain a perovskite film includes: spin-coating the perovskite ink at 900-1200 rpm for 4-6 s, and then spin-coating the perovskite ink at 5800-6200 rpm for 28-33 s on the electron transport layer.
In an embodiment, the operation of providing a hole transport layer on the perovskite film includes: spin-coating P3HT solution on the perovskite film, and then annealing at 95-105°C for 2-4 min to obtain the hole transport layer.
In an embodiment, a concentration of the P3HT solution is 14-16 mg/mL; a spin-coating speed is 3800-4200 rpm, and a spin-coating time is 25-30 s.
In an embodiment, the operation of providing a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell includes: depositing Ag on the hole transport layer by vacuum evaporation to obtain the metal electrode layer.
In an embodiment, a thickness of the metal electrode layer is 80-100 nm; and/or a vacuum degree of the vacuum evaporation is 2.5x107 Pa.
In technical solutions of the present disclosure, the perovskite ink includes dimethylamine hydriodate, lead iodide, cesium iodide and mixed solvent. The mixed solvent includes dimethylformamide and dimethyl sulfoxide, and the volume ratio of the dimethylformamide to the dimethyl sulfoxide is 6.8-7.2: 2.8-3.2. Through the selection of raw materials and the design of the mixed solvent ratio, the obtained perovskite ink can prepare CsPbI; films at 160°C, and realize the low-temperature annealing of CsPbI; film formation, and the obtained
CsPbI; film has good morphology, high grain boundary stability and low defect density, so that the CsPbls film has excellent temperature and humidity stability. In addition, the realization of low-temperature annealing makes the preparation of CsPbI; film easier to operate, with low cost, which is beneficial to large-scale production.
4 LU501865
BRIEF DESCRIPTION OF THE DRAWINGS
In order to more clearly illustrate the embodiments of the present disclosure or the technical solutions in the prior art, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present disclosure, and for those of ordinary skill in the art, other related drawings can also be obtained from these drawings without creative effort.
FIG. 1 is SEM image of CsPbl; film prepared in Example 1 and Comparative Examples 1-3 of the present disclosure.
FIG. 2 is SEM image of CsPbl; film prepared in Example 1-2 and Comparative Example 4-6 of the present disclosure.
FIG. 3 is XRD image of CsPbl; film prepared in Example 1 and Comparative Examples 1-3 of the present disclosure.
FIG. 4 is a schematic diagram of humidity stability test results of CsPbls film prepared in
Example 1 and Comparative Examples 1-3 of the present disclosure.
FIG. 5 is a schematic diagram of humidity stability test results of all-inorganic perovskite solar cell prepared in Example 1 of the present disclosure.
FIG. 6 is a schematic diagram showing test results of photovoltaic characteristics of all-inorganic perovskite solar cell prepared in Example 1 of the present disclosure.
The realization of the objective, functional characteristics, and advantages of the present disclosure are further described with reference to the accompanying drawings.
DETAILED DESCRIPTION OF THE EMBODIMENTS
In order to make the objective, technical solution and advantage of the embodiments of the present disclosure clearer, the technical solutions in the embodiments of the present disclosure will be described clearly and completely below. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer’s indication are conventional products that can be purchased from the market.
Besides, the meaning of “and/or” appearing in the disclosure includes three parallel scenarios.
For example, “A and/or B” includes only A, or only B, or both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but
> LU501865 they must be based on the realization of those of ordinary skill in the art. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that such a combination of technical solutions does not exist, nor is it within the scope of the present disclosure. Based on the embodiments of the present disclosure, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present disclosure.
The one-step spin-coating method is to first prepare perovskite ink (also called perovskite precursor solution), which is obtained by spin-coating and heating annealing, and this method is simple to operate. However, after spin-coating, the existing perovskite ink needs to be annealed at a high temperature of 200-220°C to promote the nucleation of the perovskite, so as to obtain the perovskite film. However, high temperature annealing (200-220°C) will bring the following problems. 1. It is possible reduce the crystallinity of the perovskite film, affect the bonding density between the grain boundaries, thereby reducing the stability of the grain boundaries; 2. The defect density of perovskite films is high; 3. High energy consumption and harsh preparation conditions make the cost higher. Therefore, high temperature annealing results in low stability and high cost of perovskite films, which in turn limits their applications.
In view of this, the present disclosure provides a perovskite ink. In this embodiment, the perovskite ink includes the following components: dimethylamine hydriodate (DMAI), lead iodide (Pblz), cesium iodide (CsI) and mixed solvent. The mixed solvent includes dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and a volume ratio of DMF to
DMSO is 6.8-7.2:2.8-3.2, that is, the volume ratio can be 6.8:3.2, 6.9:3.1, 7:3, 7.1:2.9, 7.2:2.8, etc, preferably 7:3. When the volume ratio is within the above range, the perovskite ink can be annealed at a relatively low temperature (about 160°C) to form a perovskite film.
In technical solutions of the present disclosure, through the selection of raw materials and the design of the mixed solvent ratio, the obtained perovskite ink can prepare CsPbI; films at 160°C, and realize the low-temperature annealing of CsPbls film formation, and the obtained
CsPbI; film has good morphology, high grain boundary stability and low defect density, so that the CsPbI; film has excellent temperature and humidity stability. In addition, the realization of low-temperature annealing makes the preparation of CsPbI; film easier to
6 LU501865 operate, with low cost, which 1s beneficial to large-scale production.
In order to make the perovskite film formed by the perovskite ink have good morphology and high purity, in this example, 75-77 mg of the DMAI, 229-233 mg of Pbl; and 128-131 mg of
Csl are added to each 1 mL of the mixed solvent. Preferably, 76.56 mg of the DMAI, 230.5 mg of Pbl; and 129.93 mg of CsI are added to each 1 mL of the mixed solvent.
The preparation method of the perovskite ink is not limited in the present disclosure, as long as it is prepared from the above-mentioned raw materials and proportions. In one embodiment, the perovskite ink is prepared by the following operation: dissolving DMAI, Pbl; and Csl in a mixed solvent, and then fully shaking for 10-12 hours to obtain the perovskite ink.
Based on the above embodiment, the present disclosure further provides a method for preparing an all-inorganic perovskite solar cell, including the following operations:
Operation S10, providing an electron transport layer on a substrate.
The substrate is conductive glass FTO. It can be understood that the conductive glass FTO needs to be pretreated first, so that the electron transport layer can be better combined with the substrate, and the pretreatment can include steps such as cleaning, drying, and hydrophobic modification.
In an embodiment, the operation S10 includes: spin-coating n-butyl titanate solution on a surface of the substrate, annealing at 120-130°C for 4-6 min, and then annealing at room temperature for 25-35 min to obtain a TiO, electron transport layer provided on the substrate.
Further, the concentration of the n-butyl titanate solution is 0.14-0.16 mol/L, the spin-coating speed is 1800-2200 rpm (r/min), and the spin-coating time is 25-30 s.
In another embodiment, the operation S10 includes: spin-coating 0.15mol/L n-butyl titanate solution on the surface of conductive glass FTO, increasing to 2000rpm at a rate of 1000rpm, spin-coating for 26s, annealing at 125°C for Smin, and then annealing in air for 30min, cleaning by an ultraviolet ozone machine for 10 minutes to obtain a TiO; electron transport layer provided on the conductive glass FTO.
Operation S20, spin-coating the perovskite ink as described above on the electron transport
7 LU501865 layer, and then annealing at 160-180°C for 25-35 min to obtain a perovskite film.
When conventional perovskite inks are used, annealing at 200-220 °C is required to promote nucleation and form perovskite films. In this embodiment, since the above perovskite ink is used, a perovskite film with good morphology and excellent stability can be obtained only by annealing at 160-180°C. 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°C, so that the perovskite film not only has low defect density and energy consumption, but also has good stability and morphology. When the annealing temperature is 160°C, the annealing time is preferably 30 min.
In an embodiment, the operation S20 includes: spin-coating the perovskite ink at 900-1200 rpm for 4-6 s, and then spin-coating at 5800-6200 rpm for 28-33 s on the electron transport layer. In this way, the prepared perovskite film is more tightly bound to the electron transport layer, thereby making it more stable.
Operation S30, providing a hole transport layer on the perovskite film.
Specifically, the operation S30 includes: spin-coating PsHT solution on the perovskite film, and then annealing at 95-105°C for 2-4 min to obtain the hole transport layer. Further, a concentration of the P3HT solution is 14-16 mg/mL, a spin-coating speed is 3800-4200 rpm, and a spin-coating time is 25-30 s.
In another embodiment, the operation S30 includes: spin-coating the PsHT solution with a concentration of 15 mg/mL on the upper surface of the perovskite film, increasing to 4000 rpm at a rate of 2000 rpm, spin-coating for 26 s, and then annealing at 100 °C for 3 min to obtain the hole transport layer.
Operation S40, providing a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
In an embodiment, the operation S40 includes: depositing Ag on the hole transport layer by vacuum evaporation to obtain the metal electrode layer. A thickness of the metal electrode
8 LU501865 layer is 80-100 nm. In another embodiment, a vacuum degree of the vacuum evaporation is 2.5x10*Pa.
In another embodiment, the operation S40 includes: under the condition of a vacuum degree of 2.5x10°Pa, depositing Ag on the upper surface of the hole transport layer by thermal evaporation to obtain a metal electrode layer with a thickness of 90 nm.
The present disclosure designs the components and proportions of the perovskite ink and the process parameters for preparing the perovskite solar cell, such that the obtained all-inorganic perovskite solar cell devices have excellent humidity stability and temperature stability, the circuit voltage (Voc) is 0.94V, the short-circuit current density (Jsc) is 23.09 mA/cm”, the fill factor (FF) is 78.2%, and the photoelectric conversion efficiency is 14.84%.
The technical solutions of the present disclosure will be described in further detail below with reference to the specific embodiments and the accompanying drawings. It should be understood that the following embodiments are only used to explain the present disclosure and are not intended to limit the present disclosure.
Table 1 below lists the raw material formulations of the perovskite inks of Examples 1-4 and
Comparative Examples 1-3 (in the table, the units of DMAI, PblL and Csl are mg, and the units of DMF and DMSO are mL).
Table 1 Raw material formulations
Tow [wm [a [ow [wo
Compe aT | so | 305 | 1% | 09 | or
Compe Fame? | Tso | 205 | Tw | 05 | 03
Ce a | 06] A
Example 1
9 LU501865 (1) Preparation of perovskite ink: DMAI, PbL, and CsI were dissolved in a mixed solvent, and then fully shaken for 11 h to obtain a perovskite ink. (2) 0.15 mol/L n-butyl titanate solution was spin-coated on the surface of conductive glass
FTO, increased to 2000 rpm at a rate of 1000 rpm, spin-coated for 26 s, annealed at 125°C for 5 min, then annealed in air for 30 min, and finally cleaned by an ultraviolet ozone machine for min to obtain a TiO; electron transport layer provided on the conductive glass FTO. (3) On the upper surface of the electron transport layer, the above perovskite ink was first spin-coated at 1000 rpm for 5 s, and then spin-coated at 6000 rpm for 30 s, then annealed at 160°C for 30 min on a hot stage, and finally cooled to room temperature to obtain the treated 10 CsPbI; film. (4) The PsHT solution with a concentration of 15 mg/mL was spin-coated on the upper surface of the CsPbI; film, increased to 4000 rpm at a rate of 2000 rpm, spin-coated for 26 s, and then annealed at 100°C for 3 min to obtain a hole transport layer. (5) Under the condition of vacuum degree of 2.5x10°Pa, Ag was deposited on the upper surface of the hole transport layer by thermal evaporation, a metal electrode layer with a thickness of 90 nm was obtained, and finally an all-inorganic perovskite solar cell was obtained.
Example 2
The rest of the steps are the same as in Example 1, except that the annealing temperature in step (3) is replaced with 180°C.
Example 3 (1) Preparation of perovskite ink: DMAI, PblL and CsI were dissolved in a mixed solvent, and then fully shaken for 10 h to obtain a perovskite ink. (2) 0.14 mol/L n-butyl titanate solution was spin-coated on the surface of conductive glass
FTO, increased to 2200 rpm at a rate of 1000 rpm, spin-coated for 25 s, annealed at 125°C for 6 min, then annealed in air for 25 min, and finally cleaned by an ultraviolet ozone machine for 10 min to obtain a TiO; electron transport layer provided on the conductive glass FTO. (3) On the upper surface of the electron transport layer, the above perovskite ink was first spin-coated at 900 rpm for 6 s, and then spin-coated at 5800 rpm for 33 s, then annealed at 170°C for 25 min on a hot stage, and finally cooled to room temperature to obtain the treated
CsPbI; film.
10 LU501865 (4) The PsHT solution with a concentration of 14 mg/mL was spin-coated on the upper surface of the CsPbI; film, increased to 3800 rpm at a rate of 2000 rpm, spin-coated for 30 s, and then annealed at 105°C for 2 min to obtain a hole transport layer. (5) Under the condition of vacuum degree of 2.5x10°Pa, Ag was deposited on the upper surface of the hole transport layer by thermal evaporation, a metal electrode layer with a thickness of 100 nm was obtained, and finally an all-inorganic perovskite solar cell was obtained.
Example 4 (1) Preparation of perovskite ink: DMAI, Pbl and CsI were dissolved in a mixed solvent, and then fully shaken for 12 h to obtain a perovskite ink. (2) 0.16 mol/L n-butyl titanate solution was spin-coated on the surface of conductive glass
FTO, increased to 1800 rpm at a rate of 1000 rpm, spin-coated for 30 s, annealed at 130°C for 4 min, then annealed in air for 35 min, and finally cleaned by an ultraviolet ozone machine for 10 min to obtain a TiO; electron transport layer provided on the conductive glass FTO. (3) On the upper surface of the electron transport layer, the above perovskite ink was first spin-coated at 1200 rpm for 4 s, and then spin-coated at 6200 rpm for 28 s, then annealed at 165°C for 35 min on a hot stage, and finally cooled to room temperature to obtain the treated
CsPbI; film. (4) The PsHT solution with a concentration of 16 mg/mL was spin-coated on the upper surface of the CsPbI; film, increased to 4200 rpm at a rate of 2000 rpm, spin-coated for 25 s, and then annealed at 95°C for 4 min to obtain a hole transport layer. (5) Under the condition of vacuum degree of 2.5x10°Pa, Ag was deposited on the upper surface of the hole transport layer by thermal evaporation, a metal electrode layer with a thickness of 80 nm was obtained, and finally an all-inorganic perovskite solar cell was obtained.
Comparative Example 1
The rest of the steps are the same as in Example 1, except that the formula of the perovskite ink is replaced with the formula shown in Comparative Example 1 in Table 1 (that is, in the mixed solvent, DMF: DMSO=9: 1).
Comparative Example 2
Il LU501865
The rest of the steps are the same as in Example 1, except that the formula of the perovskite ink is replaced with the formula shown in Comparative Example 2 in Table 1 (that is, in the mixed solvent, DMF: DMSO=8: 2).
Comparative Example 3
The rest of the steps are the same as in Example 1, except that the formula of the perovskite ink is replaced with the formula shown in Comparative Example 3 in Table 1 (that is, in the mixed solvent, DMF: DMSO=6: 4).
Comparative Example 4
The rest of the steps are the same as in Example 1, except that the annealing temperature of step (3) is replaced with 200°C.
Comparative Example 5
The rest of the steps are the same as in Example 1, except that the annealing temperature of step (3) is replaced with 220°C.
Comparative Example 6
The rest of the steps are the same as in Example 1, except that the annealing temperature of step (3) is replaced with 140°C.
The CsPbI; films and all-inorganic perovskite solar cells prepared in the above examples and comparative examples were tested as follows. (1) SEM characterization 1. The CsPbI; films prepared in step (3) in Example 1 and Comparative Examples 1-3 were observed under a scanning electron microscope (SEM). The results are shown in FIG. 1.
As can be seen from FIG. 1, compared with Comparative Examples 1-3, the CsPbI; film prepared in Example 1 has more plump and dense grains and no obvious holes, which indicates that the present disclosure makes the obtained CsPbls film with good appearance through the design of the solvent ratio in the mixed solvent. 2. The CsPbl; films prepared in step (3) in Examples 1-2 and Comparative Examples 4-6
12 LU501865 were observed under a scanning electron microscope (SEM). The results are shown in FIG. 2.
As can be seen from FIG. 2, the CsPbI; films prepared in Example 1 and Example 2 have uniform perovskite grains and dense grain boundaries. The CsPbI; films prepared in
Comparative Example 4 and Comparative Example 5 have high surface roughness and high defect density. The CsPbI; film prepared in Comparative Example 6 has no nucleation and has obvious pores. That is, the morphology of the CsPbl; film prepared in the comparative example is generally worse than that of the example, indicating that the present disclosure makes the morphology of the prepared CsPbls film better by designing the annealing temperature.
In addition, compared with Example 1, the grain boundary bonding density of Example 2 is slightly worse than that of Example 1 due to the relatively high temperature. (2) XRD test
The CsPbI; films obtained in step (3) in Example 1 and Comparative Examples 1-3 were subjected to X-ray diffraction, and the results are shown in FIG. 3.
As can be seen from FIG. 3, compared with the CsPbl; film prepared in Comparative
Examples 1-3, the characteristic peaks (110) and (220) of the perovskite in Example 1 are significantly increased, indicating that through the design of the solvent ratio in the mixed solvent, the obtained CsPbls film has more full grain nucleation and significantly reduced grain boundary defect state compensation, which is beneficial to the transport of carrier charges and thus improves the photoelectric conversion efficiency of photovoltaic cells. (3) Humidity stability test
The humidity stability test (RH65%, 25°C) of the CsPbl; films prepared in step (3) in
Example 1 and Comparative Examples 1-3, the results are shown in FIG. 4. 6:4, 8:2, 9:1, 7:3 in FIG. 4 refer to the volume ratio of DMF to DMSO. The all-inorganic perovskite solar cell finally obtained in Example 1 was tested for humidity stability (RH65%, 25°C), and four parallel experiments were set up, and the results are shown in FIG. 5.
As can be seen from FIG. 4, the aging corrosion degree of the CsPbI; film prepared in
Example 1 (DMF:DMSO=7:3) is relatively small, while the CsPbl; films prepared in
Comparative Examples 1-3 have been completely aged and corroded, indicating that the
CsPbI; films prepared in the embodiments of the present disclosure have better temperature
13 LU501865 stability. In addition, the CsPbI; film after humidity test for 24h was made into a solar cell, compared with Comparative Examples 1-3, the battery devices prepared in the examples have lower internal resistance, and through testing it was found that the battery devices prepared in the examples can still work normally.
As can be seen from FIG. 5, after the all-inorganic perovskite solar cell prepared in the embodiment of the present disclosure was placed under the conditions of RH65% and 25°C for 24 hours, the morphology was basically unchanged. After testing, it was found that the all-inorganic perovskite solar cell device can still work normally, indicating that the solar cell prepared by the present disclosure has excellent humidity stability. (4) Photovoltaic characteristic test
The photovoltaic characteristics of the all-inorganic perovskite solar cell prepared in Example 1 were tested, and the results are shown in FIG. 6. It can be seen from FIG. 6 that the circuit voltage (Voc) of the all-inorganic perovskite solar cell is 0.94V, the short-circuit current density (Jsc) reaches 23.09 mA/cm?, the 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. Therefore, their morphology and performance are also similar to those of
Example 1, which will not be repeated herein.
In conclusion, the perovskite ink provided by the present disclosure can prepare the CsPbls film at 160°C, realizes the low-temperature annealing of the CsPbl; film formation, and the obtained CsPbI; film has good morphology and excellent humidity stability. In addition, through the design of the preparation method of the all-inorganic perovskite solar cell, the obtained solar cell has excellent humidity stability and good photovoltaic properties.
The above are only some embodiments of the present disclosure, and do not limit the scope of the present disclosure thereto. Under the inventive concept of the present disclosure, equivalent structural transformations made according to the description and drawings of the present disclosure, or direct/indirect application in other related technical fields are included in the scope of the present disclosure.

Claims (10)

14 LU501865 CLAIMS
1. À perovskite ink, comprising the following components: dimethylamine hydriodate, lead iodide, cesium iodide and mixed solvent, wherein the mixed solvent comprises dimethylformamide and dimethyl sulfoxide, and a volume ratio of the dimethylformamide to the dimethyl sulfoxide is 6.8-7.2:2.8-3.2.
2. The perovskite ink of claim 1, wherein in the perovskite ink, 75-77 mg of the dimethylamine hydriodate, 229-233 mg of the lead iodide and 128-131 mg of the cesium 1odide are added to each 1 mL of the mixed solvent.
3. A method for preparing an all-inorganic perovskite solar cell, comprising the following operations: providing an electron transport layer on a substrate; spin-coating the perovskite ink according to claim 1 or 2 on the electron transport layer, and then annealing at 160-180°C for 25-35 min to obtain a perovskite film; providing a hole transport layer on the perovskite film; and providing a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell.
4. The method of claim 3, wherein the operation of providing an electron transport layer on a substrate comprises: spin-coating n-butyl titanate solution on a surface of the substrate, annealing at 120-130°C for 4-6 min, and then annealing at room temperature for 25-35 min to obtain the electron transport layer provided on the substrate.
5. The method of claim 4, wherein a concentration of the n-butyl titanate solution is
0.14-0.16 mol/L; a spin-coating speed is 1800-2200 rpm, and a spin-coating time is 25-30 s.
6. The method of claim 3, wherein the operation of spin-coating the perovskite ink on the electron transport layer, and then annealing at 160-180°C for 25-35 min to obtain a perovskite film comprises:
15 LU501865 spin-coating the perovskite ink at 900-1200 rpm for 4-6 s, and then spin-coating the perovskite ink at 5800-6200 rpm for 28-33 s on the electron transport layer.
7. The method of claim 3, wherein the operation of providing a hole transport layer on the perovskite film comprises: spin-coating P3HT solution on the perovskite film, and then annealing at 95-105°C for 2-4 min to obtain the hole transport layer.
8. The method of claim 7, wherein a concentration of the PsHT solution is 14-16 mg/mL; a spin-coating speed is 3800-4200 rpm, and a spin-coating time is 25-30 s.
9. The method of claim 3, wherein the operation of providing a metal electrode layer on the hole transport layer to obtain the all-inorganic perovskite solar cell comprises: depositing Ag on the hole transport layer by vacuum evaporation to obtain the metal electrode layer.
10. The method of claim 9, wherein a thickness of the metal electrode layer is 80-100 nm; and/or a vacuum degree of the vacuum evaporation is 2.5x107 Pa.
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