CN118042904A - Preparation method of tin oxide layer, perovskite battery, preparation method and power utilization device - Google Patents

Preparation method of tin oxide layer, perovskite battery, preparation method and power utilization device Download PDF

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CN118042904A
CN118042904A CN202410214193.4A CN202410214193A CN118042904A CN 118042904 A CN118042904 A CN 118042904A CN 202410214193 A CN202410214193 A CN 202410214193A CN 118042904 A CN118042904 A CN 118042904A
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layer
tin oxide
preparation
tin
oxide layer
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杨玉雯
曾海鹏
莫易
李明昊
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Trina Solar Co Ltd
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Trina Solar Co Ltd
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Abstract

The application discloses a preparation method of a tin oxide layer, a perovskite battery, a preparation method and an electric device, wherein the preparation method of the tin oxide layer comprises the following steps: placing a substrate on which a tin oxide layer is to be deposited in a reaction atmosphere, and forming a seed layer on the substrate by utilizing atomic layer deposition; preparing a tin oxide layer on the seed layer by utilizing reactive plasma deposition; the reaction atmosphere comprises cyclically alternating tin precursor sources and oxygen precursor sources. The dense seed layer is deposited by utilizing an atomic layer, and the tin oxide layer is grown by introducing a reaction plasma deposition auxiliary seed layer two-step method, so that the compactness and uniformity of a tin oxide film can be ensured, the deposition rate is improved, and the invasion of external water and oxygen to a battery and the decomposition and loss of materials in the battery are avoided. The tin oxide layer prepared by the method is arranged between the electron transport layer and the electrode layer, so that the damage of metal heat atoms to the electron transport layer during evaporation of the electrode layer is effectively prevented, and the stability of the battery is improved.

Description

Preparation method of tin oxide layer, perovskite battery, preparation method and power utilization device
Technical Field
The application relates to the field of photovoltaics, in particular to a preparation method of a tin oxide layer, a perovskite battery, a preparation method and an electric device.
Background
Organic-inorganic lead halide Perovskite Solar Cells (PSC) have become one of the most promising photovoltaic devices in thin film solar cell applications as a new generation of photovoltaic technology due to their excellent visible light capturing capability. Because of the remarkable photophysical properties of organic-inorganic halide perovskite materials, much research has been conducted on perovskite solar cells. Tin oxide (SnO 2) is commonly used as an Electron Transport Layer (ETL) in organic-inorganic lead halide perovskite solar cells because of its good light transmittance, good stability under uv irradiation, high electron mobility, and good processability at low temperatures. Meanwhile, snO 2 can be inserted between the electron transport layer and the electrode, quenching on the electron transport layer during evaporation of the electrode is reduced, damage to the electron transport layer during metal heat atom evaporation is prevented, damage to the perovskite light absorption layer by water oxygen in the external environment is prevented, and stability of the device is improved.
The traditional method generally prepares the SnO 2 layer by spin coating of nanoparticle colloidal dispersion, but the SnO 2 layer prepared by the method has rough surface, pinholes and cracks, is easy to generate leakage current, has lower carrier mobility, and causes poor performance of the battery.
Disclosure of Invention
Based on this, in order to further improve the compactness and uniformity of the tin oxide layer, it is necessary to provide a preparation method of the tin oxide layer, a perovskite battery, a preparation method and an electric device.
The specific technical scheme for solving the technical problems is as follows.
The application provides a preparation method of a tin oxide layer, which comprises the following steps:
placing a substrate on which a tin oxide layer is to be deposited in a reaction atmosphere, and forming a seed layer on the substrate by utilizing atomic layer deposition;
Preparing a tin oxide layer on the seed layer by utilizing reactive plasma deposition;
wherein the reaction atmosphere comprises a cyclic alternating introduction of a tin precursor source and an oxygen precursor source.
In one embodiment, the tin precursor source comprises tetra (dimethylamino) tin.
In one embodiment, the oxygen precursor source comprises one or more of water vapor, oxygen, hydrogen peroxide, and ozone.
In one embodiment, the seed layer has a thickness of 15 a to 30 a.
In one embodiment, the temperature of the atomic layer deposition is 95 ℃ to 105 ℃, the pressure in a deposition chamber of the atomic layer deposition is 0.0048 Torr to 0.0052Torr, the gas flow rate of the tin precursor source is 200sccm to 500sccm each time, the time is 0.1s to 0.4s, and the gas flow rate of the oxygen precursor source is 400sccm to 600sccm each time, and the time is 0.1s to 0.4s each time.
In one embodiment, the conditions of the reactive plasma deposition include: the electron gun comprises 70-90 sccm of first glow gas, 20-40 sccm of second glow gas, the pressure in the reaction chamber is 0.3-0.7 Pa, the glow time is 40-90 s, and the working current is 15A-35A.
In one embodiment, the first glow gas and the second glow gas each independently comprise one or more of argon, neon, and helium.
In one embodiment, the method further comprises, after preparing the substrate with the seed layer and before performing the reactive plasma deposition: the pressure in the reaction chamber was pumped to 4.8X10 -6 Torr~5.2×10-6 Torr.
Further, the preparation method of the perovskite battery comprises the following steps:
Sequentially preparing a first carrier transmission layer, a perovskite layer, a second carrier transmission layer, a tin oxide layer and an electrode layer on a conductive substrate; wherein the tin oxide layer is prepared according to the preparation method.
In one embodiment, the first carrier transport layer is a hole transport layer and the second carrier transport layer is an electron transport layer.
The application also provides a perovskite battery which is prepared according to the preparation method.
Furthermore, the application also provides an electric device, and the power supply device comprises the perovskite battery.
The preparation method of the tin oxide layer provided by the application comprises the steps of depositing a compact seed layer by using an atomic layer, and then introducing a reactive plasma deposition technology to assist the seed layer to grow tin oxide in a two-step method, so that the compactness and uniformity of a tin oxide film can be ensured, the tin oxide deposition rate is improved, and invasion of external water and oxygen to a battery and decomposition and loss of materials inside the battery are effectively avoided.
The tin oxide layer prepared by the method is arranged between the electron transport layer and the electrode layer, and can effectively prevent the damage of metal heat atoms to the electron transport layer during evaporation of the electrode layer, thereby improving the stability of the battery device.
Drawings
Fig. 1 is a graph of current versus voltage for perovskite batteries produced in example 1 and example 2.
Detailed Description
The present application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. They are, of course, merely examples and are not intended to limit the application. Furthermore, the present application may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the application, the meaning of "plurality" is at least two, such as two, three, etc., unless explicitly defined otherwise. In the description of the present application, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
All percentages, fractions and ratios are calculated on the total mass of the composition of the application, unless otherwise indicated. All of the mass of the ingredients listed, unless otherwise indicated, are given to the active substance content and therefore they do not include solvents or by-products that may be included in commercially available materials. The term "mass percent" herein may be represented by the symbol "%".
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term "and/or" includes any and all combinations of the associated listed items.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
The terms "comprising," "including," "containing," "having," or other variations thereof herein are intended to cover a non-closed inclusion, without distinguishing between them. The term "comprising" means that other steps and ingredients may be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present application comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as additional or optional ingredients, components, steps, or limitations of any of the embodiments described herein. The terms "efficacy," "performance," "effect," "efficacy" are not differentiated herein.
The words "preferably," "more preferably," and the like in the present application refer to embodiments of the application that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the application.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The application provides a preparation method of a tin oxide layer, which comprises the following steps:
Placing a substrate on which a tin oxide layer is to be deposited in a reaction atmosphere, and forming a seed layer on the substrate by utilizing atomic layer deposition;
Preparing a tin oxide layer on the seed layer by utilizing reactive plasma deposition;
wherein the reaction atmosphere comprises cyclically and alternately introducing a tin precursor source and an oxygen precursor source.
In one specific example, the tin precursor source comprises tetra (dimethylamino) tin.
In one specific example, the oxygen precursor source includes one or more of water vapor, oxygen, and ozone.
In one embodiment, the seed layer has a thickness of 15 a to 30 a.
Further, the thickness of the seed layer may be, but is not limited to, 15 a, 16a, 17 a, 18 a, 19 a, 20 a, 21a, 22 a, 23 a, 24 a, 25 a, 26 a, 27 a, 28 a, 29 a, or 30 a, preferably the seed layer is 20 a thick.
In one specific example, the atomic layer deposition temperature is 95-105 ℃, the atomic layer deposition pressure is 0.0048 Torr-0.0052 Torr, the gas flow rate of each time the tin-containing precursor source is 200 sccm~500 sccm, the time is 0.1 s-0.4 s, and the gas flow rate of each time the oxygen-containing precursor source is 400 sccm~600 sccm, the time is 0.1 s-0.4 s.
Specifically, the temperature of atomic layer deposition may be, but is not limited to, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, or 105 ℃. The gas flow rate per pass containing the tin precursor source may be, but is not limited to, 200 sccm, 250sccm, 300 sccm, 350 sccm, 450 sccm, or 500 sccm. A source of tin precursor is introduced with the carrier gas. The flow rate of the gas containing the oxygen precursor source may be, but is not limited to, 400 sccm, 420, 440, 460, 480, 500, 520, 540, 560, 580, or 600sccm per pass. The oxygen precursor source is introduced in a saturated vapor pressure diffusion manner or with a carrier gas. The carrier gas may be, but is not limited to, nitrogen.
It will be appreciated that the sample temperature and the deposition chamber temperature are maintained at 60 ℃ to 80 ℃ prior to atomic layer deposition, the time for starting to introduce the gas containing the tin precursor source after the temperature is raised to 95 ℃ to 105 ℃ is 0.1s to 0.4 s when the pressure in the deposition chamber is below 5 x 10 -3 Torr, the time for purging the gas containing the oxygen precursor source is 0.1s to 0.4 s after the purging gas is used for purging 10s to 20s, and the purging gas is used for purging 10s to 20s after the purging gas is used for purging the gas containing the oxygen precursor source, thus being a cycle of atomic layer deposition. Further, the purge gas is an inert gas, and in particular, the purge gas may be, but is not limited to, nitrogen.
In one specific example, the conditions of the reactive plasma deposition include: the electron gun contains 70-90 sccm of first glow gas, the reaction chamber contains 20-40 sccm of second glow gas, the pressure in the reaction chamber is 0.3-0.7 Pa, the glow time is 40-90 s, and the working current is 15A-35A.
Further, the pressure in the reaction chamber may be, but is not limited to, 0.3Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, or 0.7 Pa, the glow time may be, but is not limited to, 40 s, 50 s, 60 s, 70 s, 80 s, or 90 s, and the operating current may be, but is not limited to, 15A, 16A, 17A, 18A, 19A, 20A, 21A, 22A, 23A, 24A, 25A, 26A, 27A, 28A, 29A, 30A, 31A, 32A, 33A, 34A, or 35A.
In one specific example, the first glow gas and the second glow gas each independently comprise one or more of an inert gas such as argon, neon, and helium. Preferably, the first glow gas and the second glow gas are both argon.
In a specific example, after preparing the substrate with the seed layer and before performing the reactive plasma deposition, further comprises: the pressure in the reaction chamber was pumped to 4.8X10 -6 Torr~5.2×10-6 Torr.
Further, the preparation method of the perovskite battery comprises the following steps:
Sequentially preparing a first carrier transmission layer, a perovskite layer, a second carrier transmission layer, a tin oxide layer and an electrode layer on a conductive substrate; wherein the tin oxide layer is prepared according to the preparation method.
It is understood that the base on which the tin oxide layer is to be deposited is a base structure containing a conductive substrate, a first carrier transport layer, a perovskite layer, and a second carrier transport layer, which are stacked in this order.
The conductive substrate is generally transparent, i.e., the conductive substrate is a transparent conductive oxide substrate, each of which, independently, may include, but is not limited to, one or more of Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tungsten doped indium oxide (IWO), and aluminum doped zinc oxide (AZO).
It will be appreciated that the perovskite layer material has the chemical formula ABX 3, wherein a is a monovalent cation, specifically a includes, but is not limited to, one or more of cesium ions (Cs +), rubidium ions (Rb +), methylammonium ions (CH 3NH3,MA+), and formamidine ions (CH 2(NH2)2 +,FA+); b is a divalent cation including, but not limited to, one or more of lead ion (Pb 2+), copper ion (Cu 2+), zinc ion (Zn 2+), gallium ion (Ga 2+), tin ion (Sn 2+), and calcium ion (Ca 2+); x monovalent anions including, but not limited to, one or more of iodine (I -), bromine (Br -), chlorine (Cl -), fluorine (F -), and thiocyanate ions (SCN -).
In one specific example, the first carrier transport layer is a hole transport layer and the second carrier transport layer is an electron transport layer.
The material of the electron transport layer comprises one or two of fullerene and fullerene derivative. Specifically, the fullerene contains one or both of C60 and C70; the fullerene derivative may include, but is not limited to, isopropyl [6,6] -phenyl-C61-butyrate (PCBM).
The material of the hole transport layer comprises self-assembled single molecular material, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Sprio-OMeTAD), polyethylene Terephthalate (PTAA), polymer of 3-hexylthiophene (P3 HT), mixed conductor poly (3, 4-ethylenedioxythiophene) poly (styrene sulfonate) (PEDOT: PSS), 2', 7' -tetrakis (di-P-tolylamino) Spiro-9, 9' -bifluorene (Spiro-TTB), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-P-benzoquinone (F4-TCNQ), 2' - (perfluoronaphthalene-2, 6-dimethylene) dipropyldinitrile (F6 TCNNQ), and nickel oxide (NiO x). Further, the self-assembled monomolecular material may include, but is not limited to, one or more of [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid (Me-4 PACz), [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid (2 PACz), [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid (MeO-2 PACz), [4- (7H-dibenzocarbazol-7-yl) butyl ] phosphonic acid (4 PADCB), poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) layer, and 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline (TAPC).
Further, the electrode layer includes one or two layers of a metal layer and a transparent conductive oxide layer.
In particular, the metal layer may be, but is not limited to, one or both of a metal silver layer and a metal copper layer, and the transparent conductive oxide in the electrode layer may be, but is not limited to, one or more of Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tungsten doped indium oxide (IWO), and aluminum doped zinc oxide (AZO).
The application also provides a perovskite battery which is prepared according to the preparation method.
Furthermore, the application also provides an electric device, and the power supply device comprises the perovskite battery.
The preparation method of the tin oxide layer provided by the application comprises the steps of depositing a compact seed layer by using an atomic layer, and then introducing an RPD technology to assist the growth of the seed layer, so that the compactness and uniformity of a tin oxide film can be ensured, the invasion of external water and oxygen and the decomposition and loss of internal materials are effectively avoided, and the deposition rate is also improved.
The tin oxide layer prepared by the method is arranged between the electron transport layer and the electrode layer, and can effectively prevent the damage of metal heat atoms to the electron transport layer during evaporation of the electrode layer, thereby improving the stability of the device.
Specific examples are provided below to illustrate in further detail the method of preparing the tin oxide layer and perovskite battery. The raw materials according to the following embodiments may be commercially available unless otherwise specified.
Example 1
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 100 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 70s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Example 2
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, adopting H 2 O as an oxygen precursor source, carrying out a process after the temperature is raised to 100 ℃ after the pressure of a deposition chamber reaches below 5X 10 -3 Torr, enabling the tin precursor source to enter a reaction chamber along with nitrogen pulse, wherein the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the excessive oxygen precursor source and reaction byproducts, wherein the flushing gas is nitrogen, the gas flow is 2500sccm, and the thickness of one cycle growth of an ALD system is about 1A. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 60 s and the working current to 30A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 1
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of the hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mL of Li-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s was spin-coated onto ITO glass at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of DMF and DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
The substrate is placed in a vacuum coating machine, a C60 film with the thickness of 30nm is evaporated on a perovskite layer to be used as an electron transmission layer under the vacuum degree of 8 multiplied by 10 -4 Pa, and the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of electrode layers
And placing the prepared substrate in a vacuum evaporation chamber, and evaporating 100nm Ag on the electron transport layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 2
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s was spin-coated on ITO glass at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of DMF and DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30: 30s were spin-coated onto the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6: 6 s, followed by heating at 100deg.C on a heating station for 15: 15 min.
4. Preparation of an electron transport layer
The substrate is placed in a vacuum coating machine, a C60 film with the thickness of 30nm is evaporated on a perovskite layer to be used as an electron transmission layer under the vacuum degree of 8 multiplied by 10 -4 Pa, and the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of RPD-SnO 2 layer
Before the RPD system is used, the chamber air pressure is pumped to 4.8X10 -6-5.2×10-6 Torr, ar of 85 sccm and 35 sccm are respectively introduced into the electron gun and the chamber as glow gas, the chamber air pressure is maintained at 0.4-0.6 Pa, the glow time is set to 60s and the working current is set to 35A, and an RPD-SnO 2 layer with a certain thickness is obtained on the electron transport layer.
6. Preparation of electrode layers
And placing the prepared substrate in a vacuum evaporation chamber, and evaporating 100 nm of Ag on the RPD-SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 3
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 layers
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 100 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500 sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 150 cycles, an ALD-SnO 2 layer with a thickness of about 20nm a is obtained.
6. Preparation of electrode layers
And placing the prepared substrate in a vacuum evaporation chamber, and evaporating 100 nm of Ag on the RPD-SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 4
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2. 1.2 mol/L, spin-coating 30 s on the hole transport layer at a speed of 5000 r/min, and dropping 300 μl of ethyl acetate antisolvent at 6 th s, followed by heating 15: 15 min on a heating stage at 100deg.C.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, adopting H 2 O as an oxygen precursor source, carrying out a process after the temperature is raised to 100 ℃ after the pressure of a deposition chamber reaches below 5X 10 -3 Torr, enabling the tin precursor source to enter a reaction chamber along with nitrogen pulse, wherein the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the excessive oxygen precursor source and reaction byproducts, wherein the flushing gas is nitrogen, the gas flow is 2500sccm, and the thickness of one cycle growth of an ALD system is about 1A. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 30s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 5
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 100 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 100 s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 6
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 100 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 200 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500 sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 70s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 7
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 100 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500 sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 70s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 8
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated onto the hole transport layer at 5000 r/min, 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, and then heated on a 100 ℃ heating station for 15 min.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 90 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500 sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 70s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
Comparative example 9
1. Ultrasonically cleaning ITO conductive glass with deionized water, acetone and isopropanol respectively for 15 min in sequence, and finally drying in a drying oven at 75 ℃ for later use; and (3) putting the dried ITO glass substrate into an ultraviolet ozone machine for treatment of 5 min, and removing organic impurities on the surface of the ITO glass substrate.
2. Preparation of hole transport layer
70 Mg/mL of a hole transport layer precursor (72.3 mg Spiro-OMeTAD) was dissolved in 1 mL chlorobenzene solution, 29.0 μl of triphenylbismuth TPB solution and 17.5 μl of lithium bis (trifluoromethylsulfonyl) imide Li-TFSI solution (520 mg/mLLi-TFSI acetonitrile solution) were then added dropwise to the solution, and 30 s were spin-coated on ITO at 2000 r/min.
3. Preparation of perovskite layer
0.4610 G PbI 2 and 0.1589 g CH 3NH3 I were weighed and dissolved in a mixed solution of N, N-dimethylformamide DMF and dimethyl sulfoxide DMSO (volume ratio 4:1) to prepare a perovskite precursor solution of 1.2 mol/L. 30 s was spin-coated on the hole transport layer at 5000 r/min, and 300 μl of ethyl acetate antisolvent was added dropwise to 6 th s, followed by heating 15 min on a 100 ℃ heating stage.
4. Preparation of an electron transport layer
And placing the substrate with the hole transport layer into a vacuum coating machine, and evaporating a C60 film with the thickness of 30nm on a perovskite layer to serve as an electron transport layer under the vacuum degree of 8 multiplied by 10 -4 Pa, wherein the evaporation rate is 0.1-0.15 nm/s.
5. Preparation of ALD-SnO 2 seed layer
SnO 2 seed layer was deposited on the electron transport layer using an atomic layer deposition ALD system: the method comprises the steps of adopting tetra (dimethylamino) tin as a tin precursor source, keeping the temperature of a sample and a chamber at 65 ℃, taking H 2 O as an oxygen precursor source, after the pressure of a deposition chamber reaches below 5 multiplied by 10 -3 Torr, raising the temperature to 110 ℃, carrying out a process, wherein the tin precursor source enters a reaction chamber along with nitrogen pulse, the nitrogen flow is 400 sccm, the exposure time of the tin precursor source is 0.4 seconds, the flushing time is 20 seconds, the oxygen precursor source enters the reaction chamber along with nitrogen pulse, the nitrogen flow is 600 sccm, the exposure time of the oxygen precursor source is 0.4 seconds, the flushing time is 20 seconds, after the reaction of the oxygen precursor source and the tin precursor source is completed, introducing flushing gas to purge the redundant oxygen precursor source and reaction byproducts, the flushing gas is nitrogen, the gas flow is 2500 sccm, and the ALD system has a cycle growth thickness of about 1a cycle. After 20 cycles, a dense ALD-SnO 2 seed layer was obtained.
6. Preparation of RPD-SnO 2 layer
And (3) using a Reactive Plasma Deposition (RPD) system, adopting a tin target with the purity of 99.999% as a target material, pumping the chamber to the air pressure of 4.8X10 -6-5.2×10-6 Torr before starting, respectively introducing Ar of 80 sccm and 30 sccm into an electron gun and the chamber as glow gas, maintaining the chamber air pressure at 0.4-0.6 Pa, setting the glow time to 70s and the working current to 20A, and obtaining the RPD-SnO 2 layer with a certain thickness.
7. Preparation of electrode layers
The prepared substrate is placed in a vacuum evaporation chamber, and 100nm of Ag is evaporated on the SnO 2 layer under the condition that the vacuum degree of the chamber is below 10 -5 Pa.
As shown in fig. 1, the current-voltage graphs of the perovskite batteries prepared in example 1 and example 2, different modulation parameters were used, which had a significant effect on the device performance, and specific performance parameters are shown in table 1. From table 1, it is seen that the perovskite battery of comparative example 1, in which the tin oxide layer was not prepared, had the lowest device efficiency, i.e., the worst battery performance, and SnO 2 had good electron mobility and a suitable band structure. Whereas example 1 and example 2 contained perovskite cells having tin oxide layers prepared using the two-step method of the present application, the device efficiency was superior to that of the perovskite cells of comparative example 2 using only the tin oxide layer prepared by reactive plasma deposition. The tin oxide layer prepared by the two-step method has high density and uniformity, is suitable for perovskite batteries, and is beneficial to further improving the performance of the perovskite batteries. The perovskite cell performance of examples 1 and 2 comprising the tin oxide layer prepared using the two-step process of the present application was slightly lower than the perovskite cell performance of comparative example 3 using only atomic layer deposition of the tin oxide layer prepared. However, the preparation time of the SnO 2 layer is greatly shortened, the preparation time of the SnO 2 layer in the perovskite battery of comparative example 3 is about 1.2h, the preparation time of the SnO 2 layer in the perovskite batteries of example 1 and example 2 is about 0.5h, and the tin oxide layer prepared by the two-step method has good industrialized prospect.
By regulating the glow time of the RPD-SnO 2 layer in the tin oxide layer prepared by the two-step method, the glow time is set to be 30s in comparative example 4 and 100s in comparative example 5, and the result shows that the glow time is set to be 70s under the condition that the working current is 20A in example 1, the device performance is optimal, the glow time influences the thickness of the film, the thickness is optimal under the condition of example 1, and the film has optimal optical and electrical properties.
The precursor pulse flow rate of the SnO 2 seed layer prepared by ALD is regulated, the precursor pulse flow rate of the comparative example 6 is set to 200sccm, the low flow rate can cause incomplete reaction, the precursor pulse of the comparative example 7 is set to 600sccm, and the reaction amount is too large at the high flow rate, which is also unfavorable for the performance of the device.
By controlling the deposition temperature of the ALD process for preparing the SnO 2 seed layer, the deposition temperature of comparative example 8 was 90 ℃, and the results show that when the temperature is too low, the precursor may not react completely with the substrate, reducing the growth rate. Comparative example 9 has a deposition temperature of 110 c and as a result shows that too high a temperature may exacerbate the precursor desorption from the substrate surface, reducing the growth rate and degrading device performance.
TABLE 1
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely illustrate several embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that those skilled in the art, based on the technical solutions provided by the present application, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.

Claims (12)

1. The preparation method of the tin oxide layer is characterized by comprising the following steps of:
placing a substrate on which a tin oxide layer is to be deposited in a reaction atmosphere, and forming a seed layer on the substrate by utilizing atomic layer deposition;
Preparing a tin oxide layer on the seed layer by utilizing reactive plasma deposition;
Wherein the reaction atmosphere comprises cyclically and alternately introducing a tin precursor source and an oxygen precursor source.
2. The method of preparing a tin oxide layer according to claim 1, wherein the tin precursor source comprises tetra (dimethylamino) tin.
3. The method of claim 1, wherein the oxygen precursor source comprises one or more of water vapor, oxygen, hydrogen peroxide, and ozone.
4. The method of claim 1, wherein the seed layer has a thickness of 15 a to 30 a.
5. The method of manufacturing a tin oxide layer according to claim 1, wherein the atomic layer deposition temperature is 95 ℃ to 105 ℃, the pressure in the deposition chamber of the atomic layer deposition is 0.0048Torr to 0.0052Torr, the gas flow rate of the tin precursor source is 300 sccm~500 sccm s to 0.4s each time, the gas flow rate of the oxygen precursor source is 400sccm to 600 sccm each time, and the time is 0.1s to 0.4s each time.
6. The method of preparing a tin oxide layer according to claim 1, wherein the conditions of the reactive plasma deposition include: the electron gun comprises 70-90 sccm of first glow gas, 20-40 sccm of second glow gas, the pressure in the reaction chamber is 0.3-0.7 Pa, the glow time is 40-90 s, and the working current is 15A-35A.
7. The method of preparing a tin oxide layer according to claim 6, wherein the first glow gas and the second glow gas each independently comprise one or more of argon, neon, and helium.
8. The method of any one of claims 1 to 7, further comprising, after preparing the substrate with the seed layer and before performing the reactive plasma deposition: the pressure in the reaction chamber was pumped to 4.8X10 -6Torr~5.2×10-6 Torr.
9. A method of preparing a perovskite battery, comprising the steps of:
sequentially preparing a first carrier transmission layer, a perovskite layer, a second carrier transmission layer, a tin oxide layer and an electrode layer on a conductive substrate; wherein the tin oxide layer is prepared according to the preparation method of any one of claims 1 to 8.
10. The method of claim 9, wherein the first carrier transport layer is a hole transport layer and the second carrier transport layer is an electron transport layer.
11. A perovskite battery, characterized by being produced according to the production method as claimed in claim 9 or 10.
12. An electrical device, characterized in that its power supply means comprise a perovskite battery according to claim 11.
CN202410214193.4A 2024-02-27 2024-02-27 Preparation method of tin oxide layer, perovskite battery, preparation method and power utilization device Pending CN118042904A (en)

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