CN116397220A

CN116397220A - Metal doped tin oxide film and preparation method and application thereof

Info

Publication number: CN116397220A
Application number: CN202310374848.XA
Authority: CN
Inventors: 陈瑞; 邵君
Original assignee: Wuxi Utmolight Technology Co Ltd
Current assignee: Wuxi Utmolight Technology Co Ltd
Priority date: 2023-04-10
Filing date: 2023-04-10
Publication date: 2023-07-07

Abstract

The invention provides a metal doped tin oxide film, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing metal salt, a tin source, an alkali source, a catalyst and a solvent to obtain a chemical water bath deposition solution; (2) Regulating the pH value of the chemical water bath deposition liquid, fully contacting the conductive surface of the substrate with the chemical water bath deposition liquid, controlling the temperature, and depositing a tin oxide layer on the conductive surface of the substrate; (3) And (3) annealing the substrate obtained in the step (2) to obtain the metal doped tin oxide film, wherein the metal doped tin oxide film prepared by the method has good compactness, can greatly improve conductivity and can realize continuous deposition.

Description

Metal doped tin oxide film and preparation method and application thereof

Technical Field

The invention belongs to the technical field of battery materials, and relates to a metal doped tin oxide film, a preparation method and application thereof.

Background

Solar cells can be classified into crystalline silicon cells, thin film cells, perovskite cells according to technical routes. For each technical route, the conversion efficiency determines the future development potential. Compared with the traditional crystal silicon, perovskite has three main core advantages: the photoelectric characteristic is very good, the raw materials are rich, the synthesis is easy, and the production process flow is short. This new technology, which was born in 2009, has achieved a laboratory certification cell efficiency of 25.7% in a short decade; under the background, the perovskite industrialization progress is obviously accelerated, and small test lines or pilot test lines are put into production by a plurality of enterprises.

Currently, two major factors that hinder the accelerated development of the industrialization process, namely large-area component efficiency and component stability. At the end of 2022, a complete set of stability authentication certificates are obtained by existing enterprises, but the authentication stability component efficiency is below 12%. Meanwhile, the efficiency of the battery is authenticated by a laboratory to be more than 25%, but the efficiency of the large-area assembly is always kept below 18%, and a certain gap still exists. In this context, increasing the efficiency of large area components is becoming a serious issue in the next perovskite development.

As is well known, most of high-efficiency batteries reported in the literature adopt an NIP structure, and the NIP structure has the advantages of simplicity in operation, clear process and the like; however, the problem faced by the NIP structure is high cost and poor stability, because most of the functional layers used are titanium oxide and Spiro, the titanium oxide needs high temperature annealing, the Spiro has high manufacturing cost, and at the same time, the titanium oxide has a photocatalytic effect and Li salt doped in the Spiro is easy to absorb water, resulting in poor stability. In view of this, it is imperative to change the functional layer.

The tin oxide has the advantages of low-temperature preparation, good light permeability, various processes and the like, and the existing method for preparing the tin oxide film comprises spin-coating a tin oxide aqueous solution and magnetron sputtering of tin oxide, wherein the coating aqueous solution has large-area limiting problems such as viscosity and uniformity; the magnetron sputtering tin oxide has low efficiency and high equipment manufacturing cost, but the direct water bath tin oxide deposition has the problems of thinner deposited film and better conductive performance, but has the problem of compactness, and if the deposited film is thicker, the film has poor conductivity, cannot consider compactness and conductivity, and greatly limits the application of the magnetron sputtering tin oxide in practice.

Disclosure of Invention

The invention aims to provide a metal doped tin oxide film, a preparation method and application thereof.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a method for preparing a metal-doped tin oxide film, the method comprising the steps of:

(1) Mixing metal salt, a tin source, an alkali source, a catalyst and a solvent to obtain a chemical water bath deposition solution;

(2) Regulating the pH value of the chemical water bath deposition liquid, fully contacting the conductive surface of the substrate with the chemical water bath deposition liquid, controlling the temperature, and depositing a tin oxide layer on the conductive surface of the substrate;

(3) And (3) annealing the substrate obtained in the step (2) to obtain the metal doped tin oxide film.

According to the preparation method of the metal doped tin oxide film, the film is doped with metal, so that the film is enabled to have certain thickness, the compactness is ensured, the conductivity is maintained, the balance point problem is solved, and meanwhile, the conductivity is greatly improved.

Preferably, the metal salt in step (1) comprises any one or a combination of at least two of zinc salt, iron salt, titanium salt or niobium salt;

preferably, the tin source comprises any one or a combination of at least two of stannous chloride, stannous sulfate or stannous nitrate;

preferably, the alkali source comprises any one or a combination of at least two of urea, ammonia or thiourea;

preferably, the catalyst comprises any one or a combination of at least two of thioglycollic acid, carbonic acid, acetic acid or nitrous acid;

preferably, the molar ratio of the metal salt to the tin source is (0.2 to 0.4): 1, for example: 0.2:1, 0.25:1, 0.3:1, 0.35:1, or 0.4:1, etc.

Preferably, the solvent comprises water.

Preferably, the concentration of tin in the chemical water bath deposition solution is 0.01-0.03 mol/L, for example: 0.01mol/L, 0.012mol/L, 0.02mol/L, 0.025mol/L, 0.03mol/L, etc.

In the method, a tin source and an alkali source have the main functions of finally forming tin oxide; the main function of the catalyst is to slow down the reaction; the main function of water is to dissolve tin source, alkali source and catalyst as dispersing agent to form clear precursor liquid; the metal salt plays a role in improving conductivity by metal doping, and ensures sufficient mobility and conductivity even if the film thickness is increased.

Preferably, the substrate of step (2) comprises FTO conductive glass.

Preferably, the substrate is subjected to a wet treatment and then to an ultraviolet ozone treatment.

Preferably, the wetting treatment comprises ultrasonic cleaning of the substrate sequentially by industrial cleaning agent, deionized water and ethanol until the surface wettability is good, so that a uniform water film can be formed.

Preferably, the substrate is subjected to a drying treatment after being subjected to the wetting treatment.

Preferably, the time of the ultraviolet ozone treatment is 10 to 20 minutes, for example: 10min, 12min, 15min, 18min or 20min, etc.

Preferably, the pH in step (2) is from 1 to 3, e.g. 1, 1.5, 2, 2.5 or 3, etc.

Preferably, the temperature in step (2) is 70-100 ℃, for example: 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, or the like, preferably 90-95 ℃.

Preferably, the substrate is placed parallel to the chemical bath deposition liquid level or at a different angle in the chemical bath deposition liquid, preferably the substrate is placed parallel to the chemical bath deposition liquid level.

Preferably, when the substrate is placed in the chemical water bath deposition solution at different angles, the back surface is attached with the isolation adhesive tape.

The existing water bath tin oxide deposition method is to vertically place the substrate, so that the problem is that continuous production is not realized. The invention changes the vertical placement commonly used at present into the horizontal placement, and the FTO surface is downward, thus being beneficial to grabbing of a mechanical arm and being capable of realizing continuous deposition.

The deposition process is carried out in a water tank at 70-100 ℃ under normal pressure.

Preferably, the time of deposition is 5 to 10 minutes, for example: 5min, 6min, 7min, 8min, 9min or 10min, etc.

According to the invention, hydrochloric acid is added into the precursor liquid, the pH value is regulated, a chemical water bath deposition liquid is obtained, the conductive surface of the conductive glass is suspended downwards above the deposition liquid, the conductive surface is fully contacted with the solution, the temperature in water bath is controlled, tin oxide nano particles grow on a substrate to form a film, and a tin oxide film layer is not deposited on the back surface of the conductive glass, so that single-sided film coating is realized; the pH value of the hydrochloric acid in the deposition solution is adjusted to slow down the reaction.

Preferably, the annealing treatment in step (3) is performed at a temperature of 180 to 200 ℃, for example: 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃ and the like.

Preferably, the annealing treatment is performed for 0.5 to 1 hour, for example: 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, etc.

The large particles generated by the deposition reaction do not meet the requirements, and are washed by pure water, so that a layer of compact tin oxide film is obtained, and then the tin oxide film with good crystallinity is generated by annealing.

In a second aspect, the present invention provides a metal-doped tin oxide film produced by the method of the first aspect.

In a third aspect, the present invention provides a perovskite assembly comprising a metal doped tin oxide film as described in the second aspect.

Preferably, the perovskite assembly further comprises a transparent electrode, a hole transport layer and a metal electrode.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the preparation method of the metal doped tin oxide film, through metal doping, the film is enabled to have a certain thickness, the compactness is ensured, and meanwhile, the conductivity can be maintained. This not only solves the balance point problem, but also has the advantage that the conductivity is greatly improved.

(2) The existing water bath tin oxide deposition method is to vertically place the substrate, so that the problem is that continuous production is not realized. The vertical placement commonly used at present is changed into horizontal placement, and the FTO surface is downward, so that the grabbing of a mechanical arm is facilitated, and continuous deposition can be realized.

Drawings

FIG. 1 is a schematic structural diagram of a perovskite assembly according to the present invention, a 1-metal electrode, a 2-hole transport layer, a 3-PVSK layer, a 4-ETL layer SnO ₂ 5-FTO conductive glass.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Example 1

The embodiment provides a metal doped tin oxide film, and the preparation method of the metal doped tin oxide film comprises the following steps:

(1) Selecting area size of 30×30cm ² The FTO conductive glass is subjected to P1 scribing, the cutting resistance is in the hundred megaohms level within the range of 6-7mm of the width of the subcell, and the substrate is subjected to ultrasonic cleaning sequentially by industrial cleaning agent, deionized water and ethanol until the surface wettability is good, so that a uniform water film can be formed. Drying with compressed air, and treating with ultraviolet ozone for 15min; zinc acetate and stannous chloride are added into water according to the mol ratio of 0.3:1 and urea and thioglycollic acid to be stirred and dissolved to prepare chemical water bath deposition liquid, wherein the concentration of tin in the chemical water bath deposition liquid is 0.012mol/L;

(2) Adding hydrochloric acid to adjust the pH of the chemical water bath deposition solution to 1.6, placing the conductive surface of the substrate in parallel in the chemical water bath deposition solution, completely contacting the conductive surface with the solution, controlling the water bath temperature to 90 ℃, and depositing a tin oxide layer on the conductive surface of the substrate for 8min;

(3) And (3) annealing the substrate obtained in the step (2) for 45min at the temperature of 190 ℃ to obtain the metal doped tin oxide film.

Example 2

(1) Selecting area size of 30×30cm ² The FTO conductive glass is subjected to P1 scribing, the cutting resistance is in the hundred megaohms level within the range of 6-7mm of the width of the subcell, and the substrate is subjected to ultrasonic cleaning sequentially by industrial cleaning agent, deionized water and ethanol until the surface wettability is good, so that a uniform water film can be formed. Drying with compressed air, adhering adhesive tape on the back of glass, and treating with ultraviolet ozone for 16min; adding ferric chloride and stannous nitrate into water according to a molar ratio of 0.32:1, stirring and dissolving the ferric chloride and the stannous nitrate and the ammonia water and the nitrous acid to prepare a chemical water bath deposition solution, wherein the concentration of the stannum in the chemical water bath deposition solution is 0.015mol/L;

(2) Adding hydrochloric acid to adjust the pH of the chemical water bath deposition solution to 2, placing the conductive surface of the substrate in parallel in the chemical water bath deposition solution, completely contacting the conductive surface with the solution, controlling the water bath temperature to 95 ℃, and depositing a tin oxide layer on the conductive surface of the substrate for 10min;

(3) And (3) annealing the substrate obtained in the step (2) for 50min at 185 ℃ to obtain the metal doped tin oxide film.

Example 3

This example differs from example 1 only in that the molar ratio of zinc acetate to stannous chloride in step (1) is 0.1:1, and other conditions and parameters are exactly the same as in example 1.

Example 4

This example differs from example 1 only in that the molar ratio of zinc acetate to stannous chloride in step (1) is 0.5:1, and other conditions and parameters are exactly the same as in example 1.

Example 5

This example differs from example 1 only in that the concentration of tin in the chemical bath deposition solution in step (1) is 0.005mol/L, and other conditions and parameters are exactly the same as in example 1.

Example 6

This example differs from example 1 only in that the concentration of tin in the chemical bath deposition solution in step (1) is 0.05mol/L, and other conditions and parameters are exactly the same as those in example 1.

Example 7

This example differs from example 1 only in that the deposition temperature in step (2) is 70 ℃, the other conditions and parameters being exactly the same as in example 1.

Example 8

This example differs from example 1 only in that the deposition temperature in step (2) is 100 ℃, and other conditions and parameters are exactly the same as in example 1.

Example 9

This example differs from example 1 only in that the pH in step (2) is 3, and other conditions and parameters are exactly the same as in example 1.

Comparative example 1

This comparative example differs from example 1 only in that no metal is doped, and other conditions and parameters are exactly the same as example 1.

Performance test:

according to perovskite component Cs _0.3 FA _0.7 PbI _0.6 Br _0.4 Is proportional to CsI, FAI, pbI ₂ 、PbBr ₂ Preparing a precursor solution, wherein the solvent is DMF: NMP volume ratio=8:1 mixed solution, precursor solution concentration 1.3M, the precursor solution is applied to the metal doped tin oxide films prepared in the examples and the comparative examples, a Slot-die method is adopted to prepare a perovskite film, the prepared perovskite film is annealed in an oven at 120 ℃ for 40min, nickel oxide powder synthesized by hydrothermal synthesis is uniformly dispersed in isopropanol, then film coating is carried out in an ultrasonic spraying mode, after spraying is completed, low-temperature annealing at 80 ℃ is carried out, P2 scribing is carried out on the component, and 5 x 10 is carried out ^-6 Under the mbar condition, a Cr+Ag electrode is subjected to vacuum evaporation, P3 scribing and edge cleaning are carried out, and then a perovskite assembly is obtained, the structural schematic diagram of the perovskite assembly is shown in figure 1, the efficiency of the perovskite assembly is tested, and the result is shown in table 1:

TABLE 1

As can be seen from table 1, the conversion efficiency of the perovskite cell prepared by the metal doped tin oxide thin film of the invention can reach more than 23%, and the increase of the film thickness by properly increasing the metal zinc doping ratio, the pH, the temperature and the extension time does not affect the performance, which indicates that the tolerance of the zinc doped film thickness is also increased.

As can be seen from comparison of examples 1 and 3-4, in the preparation process of the metal doped tin oxide film, the mole ratio of the metal salt to the tin source influences the performance, the mole ratio of the metal salt to the tin source is controlled to be 0.2-0.3:1, the effect is good, if the doping amount of the metal salt is too low, the conductivity cannot be optimized, and if the doping amount of the metal salt is too high, znO is likely to be formed to be dominant, and the film performance is poor.

As can be seen from comparison of examples 1 and examples 5-6, in the preparation process of the metal doped tin oxide film, the concentration of tin in the chemical bath deposition liquid can influence the performance of the metal doped tin oxide film, the concentration of tin in the chemical bath deposition liquid is controlled to be 0.01-0.03 mol/L, the effect is good, if the concentration of tin in the chemical bath deposition liquid is too low, the film is not fully covered, electric leakage can be caused, and if the concentration of tin in the chemical bath deposition liquid is too high, the film deposition rate is too fast, the film is too thick, and the conductivity is poor.

As can be seen from comparison of examples 1 and examples 7-8, in the preparation process of the metal doped tin oxide film, the temperature of tin oxide deposition can influence the performance of the metal doped tin oxide film, the temperature of tin oxide deposition is controlled to be 90-95 ℃, the effect is good, if the temperature of tin oxide deposition is too low, the deposition rate is slow, the film is thinner, and if the temperature of tin oxide deposition is too high, water is easy to boil, so that the film deposition is not facilitated.

As can be seen from the comparison of examples 1 and 9, too high a pH may result in too fast tin oxide deposition, too large a particle size of the deposited tin oxide, and may result in a change in the valence state of the tin, yielding other species.

By comparing the embodiment 1 with the comparative example 1, the invention ensures the compactness of the film with certain thickness and maintains the conductivity through metal doping, thus not only solving the problem of balance points, but also greatly improving the conductivity.

The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims

1. The preparation method of the metal doped tin oxide film is characterized by comprising the following steps of:

2. The method of claim 1, wherein the metal salt of step (1) comprises any one or a combination of at least two of zinc, iron, titanium, or niobium salts;

preferably, the molar ratio of the metal salt to the tin source is (0.1-0.5): 1;

preferably, the solvent comprises water.

3. The method according to claim 1, wherein the concentration of tin in the chemical bath deposition solution in the step (1) is 0.01 to 0.03mol/L.

4. The method of manufacturing of claim 1, wherein the substrate of step (2) comprises FTO conductive glass.

5. The method of claim 1, wherein the pH in step (2) is 1 to 3;

preferably, the temperature is 70-100 ℃, preferably 90-95 ℃;

preferably, the substrate is placed parallel to the chemical bath deposition liquid level or placed in the chemical bath deposition liquid at a different angle, preferably the substrate is placed parallel to the chemical bath deposition liquid level;

6. The method of claim 1, wherein the time of the deposition in step (2) is 5 to 10 minutes.

7. The method of claim 1, wherein the annealing treatment in step (3) is performed at a temperature of 150 to 200 ℃;

preferably, the annealing treatment is performed for 0.5 to 1 hour.

8. A metal-doped tin oxide film, characterized in that the metal-doped tin oxide film is produced by the method according to any one of claims 1 to 7.

9. A perovskite assembly comprising the metal doped tin oxide thin film of claim 8.

10. The perovskite assembly of claim 9, further comprising a transparent electrode, a hole transport layer, and a metal electrode.