A method for preparing a transparent conductive target material and a thin film circuit for copper electroplating process

Abstract

The present application relates to a method for preparing a transparent conductive target material and a thin film circuit for a copper electroplating process, including preparing an indium tin oxide, indium zinc oxide or indium tin zinc oxide target material and a corresponding silver-containing indium tin oxide, silver-containing indium zinc oxide or silver-containing indium tin zinc oxide target material by means of slurry injection molding and medium-high temperature sintering, and reducing the sintering temperature by adding silver oxide powder or pure silver powder to improve the density and conductivity of the target material; placing a glass substrate or an N-type silicon wafer that has completed the PECVD process, as well as the target material and the corresponding silver-containing target material into a vacuum sputtering machine, coating at room temperature to form an electroplated copper multilayer thin film structure, and performing a yellow light process and an etching process to form a copper metal grid line to complete the production of a thin film circuit. The present invention can realize the sputtering of the target material and the traditional transparent conductive film target material on the same sputtering machine, and can meet the performance requirements of copper electroplating metalization of heterojunction cells and heterojunction perovskite stacked cells.

Description

Technical Field

[0001] The present application relates to the technical field of preparation of film-coated oxide materials, and in particular to a method for preparing a transparent conductive target material and a thin film circuit for a copper electroplating process. Background Art

[0002] With the rapid development of society and science and technology, human beings have an increasingly urgent need for functional materials. New functional materials have become the key to the development of new technologies and emerging industries. With the development of display, touch screen, semiconductor, solar energy and other industries, a new functional material, transparent conducting oxide (TCO) film, has emerged and developed. The so-called transparent conductive film refers to a thin film material with a transmittance of more than 80% in the visible light range, high conductivity, and a specific resistance value of less than 1×10 -3 Ωcm. It is known that Au, Ag, Pt, Cu, Rh, Pd, Al, Cr and other metals have a certain degree of light transmittance when forming a 3-15nm thick film, and have been used in transparent thin film electrodes. However, these metal films absorb too much light, have low hardness and poor stability, so they gradually develop into transparent conductive film materials based on metal oxides. Such films have common optoelectronic properties such as wide bandgap, high light transmittance in the visible spectrum and low resistivity. They have broad application prospects in the fields of solar cells, flat panel displays, special function window coatings and other optoelectronic devices. Among them, ITO film has the most mature preparation technology and the most widely used. However, due to the high price of In2O3 in ITO film, the production cost is relatively high; non-indium oxide series materials such as tin oxide or zinc oxide have also been studied quite a lot in recent years, but at present, in the fields of LED, solar cells, displays and touch screens, the cost performance of these new conductive film materials cannot be compared with that of indium oxide series materials.

[0003] At present, the main methods for producing ITO films include vacuum evaporation process, chemical vapor deposition (CVD) process, pulsed laser deposition (PLD) process, and vacuum sputtering process. In order to achieve large-area uniformity and mass production, vacuum sputtering process is the first choice, so the quality and performance of the coating material used for thin film sputtering, that is, the target material, becomes very important. As the size of electronic components such as LCD TVs, touch screens, and thin-film solar cells becomes larger and larger, how to obtain ITO films with higher light transmittance and electrical properties is a top priority.

[0004] The target material is a parent material with a fixed shape used for sputtering coating. For oxide targets, the traditional production method is to use a hot pressing process or a cold isostatic pressing and sintering process. The material mixing uniformity is poor, and the stress distribution during the sintering process is uneven, making it difficult to produce high-density and large-sized oxide targets.

[0005] Among all solar cell technologies, the study of silicon-based heterojunction (HJT) solar cells is of great significance because it has the advantages of high conversion efficiency, simple structure, low process temperature, few process steps and low temperature coefficient. In the metallization process of heterojunction cells and heterojunction perovskite stacked cells, low-temperature silver paste or low-temperature silver-coated copper paste is often required. However, both low-temperature silver paste and low-temperature silver-coated copper paste have the problems of high price and low conductivity, and have high contact impedance with the transparent conductive film on the surface of heterojunction cells and heterojunction perovskite stacked cells, namely TCO film. In order to improve the electrical performance of metallization, reduce contact resistance, reduce the production cost of metallization, improve cell conversion efficiency and increase the output power of components, the non-silvering copper electroplating process has gradually received attention. Since the transparent conductive film material is a semiconductor with a resistance of 3×10 -4 ~4×10 -4 Ωcm, the electrical performance is not enough to directly electroplate the copper grid line. Therefore, it is usually necessary to first sputter a thin layer of aluminum or copper or other good conductors on the surface of the transparent conductive film as a seed layer. The thickness of the seed layer is usually less than <150nm, and the resistance is 4×10 -6 ~5×10 -6 Ωcm. Then, a thick copper grid line with a thickness greater than 5um is electroplated on the seed layer. At present, one of the disadvantages of sputtering pure copper as a seed layer is that pure copper is easily oxidized and has a large coefficient of thermal expansion and contraction, which can easily cause the film to fall off; secondly, since TCO coating requires heat treatment to obtain better electrical properties and transmittance, and pure copper coating is not suitable for heat treatment, sputtering TCO and sputtering pure copper are not suitable for operation on the same sputtering machine, and an additional vacuum sputtering machine is required, thereby increasing the cost of equipment investment. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a transparent conductive target material and a thin film circuit for a copper electroplating process, which can reduce the sintering temperature, improve the density and conductivity of the target material, and can achieve sputtering of a transparent conductive film layer containing silver particles. The target material and a traditional transparent conductive film target material are placed on the same sputtering machine for sputtering, which can meet the performance requirements of copper electroplating metallization of heterojunction batteries and heterojunction perovskite stacked batteries.

[0007] The technical solution adopted by the present invention is: a method for preparing a transparent conductive target material and a thin film circuit for a copper electroplating process, comprising the following steps:

[0008] S1: adding tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder to indium oxide powder, adding zirconium oxide balls, pure water and a dispersant, grinding and mixing them fully to form a slurry, pouring the ground slurry into a porous mold for drying to form an indium tin oxide low-density embryo, an indium zinc oxide low-density embryo or an indium tin zinc oxide low-density embryo;

[0009] S2: sintering the prepared indium tin oxide low-density embryo body, indium zinc oxide low-density embryo body or indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form an indium tin oxide high-density target material embryo body, indium zinc oxide high-density target material embryo body or indium tin zinc oxide high-density target material embryo body;

[0010] S3: bonding an indium tin oxide high-density target material embryo, an indium zinc oxide high-density target material embryo or an indium tin oxide zinc high-density target material embryo on a copper back plate with indium to form an indium tin oxide target, an indium zinc oxide target or an indium tin oxide zinc target for sputtering;

[0011] S4: adding tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder, and silver oxide powder or pure silver powder to indium oxide powder, and adding zirconium oxide balls, pure water and a dispersant to fully grind and mix to form a slurry, pouring the ground slurry into a porous mold for drying to form a silver-containing indium tin oxide low-density embryo body, a silver-containing indium zinc oxide low-density embryo body or a silver-containing indium tin oxide zinc low-density embryo body;

[0012] S5: sintering the prepared silver-containing indium tin oxide low-density embryo body, silver-containing indium zinc oxide low-density embryo body or silver-containing indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form a silver-containing indium tin oxide high-density target material embryo body, silver-containing indium zinc oxide high-density target material embryo body or silver-containing indium tin zinc oxide high-density target material embryo body;

[0013] S6: bonding a silver-containing indium tin oxide high-density target material embryo, a silver-containing indium zinc oxide high-density target material embryo, or a silver-containing indium tin oxide zinc high-density target material embryo on a copper back plate with indium to form a silver-containing indium tin oxide target, a silver-containing indium zinc oxide target, or a silver-containing indium tin oxide zinc target for sputtering;

[0014] S7: Place the glass substrate or the N-type silicon wafer that has completed the PECVD process, as well as the target material and the corresponding silver-containing target material into a vacuum sputtering machine, and perform coating at room temperature. Sputter a 50-150nm thick indium tin oxide film, an indium zinc oxide film or an indium tin zinc oxide film, and a 5-20nm thick silver-containing indium tin oxide film, a silver-containing indium zinc oxide film or a silver-containing indium tin zinc oxide film on the glass substrate or the N-type silicon wafer that has completed the PECVD process in sequence; perform a yellow light process on the surface of the silver-containing indium tin oxide film, the silver-containing indium zinc oxide film or the silver-containing indium tin zinc oxide film, and then electroplate a 5-20um thick pure copper film, and then perform an etching process to form a copper metal grid line, thereby completing the copper metallized multi-layer film production or HJT battery production.

[0015] Furthermore, when preparing the low-density indium tin oxide embryo in step S1, the weight percentage of the added tin oxide powder is 0.5-10wt%;

[0016] When making the low-density indium zinc oxide embryo, the weight percentage of zinc oxide powder added is 5 to 35 wt %;

[0017] When preparing the low-density indium tin zinc oxide embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, and the weight percentage of the added zinc oxide powder is 5-35wt%.

[0018] Furthermore, the grinding time in steps S1 and S4 is 16 to 72 hours.

[0019] Furthermore, in step S2, the sintering temperature when making the indium tin oxide high-density target material embryo is 1500-1600° C. The density of the obtained indium tin oxide high-density target material embryo is greater than 98%, and the resistance value is less than 3×10 -4 Ωcm;

[0020] The sintering temperature when making the indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is 1450-1550° C. The density of the prepared indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is greater than 97%, and the resistance value is less than 4×10 -4 Ωcm.

[0021] Furthermore, when preparing the silver-containing indium tin oxide low-density embryo in step S4, the weight percentage of the added tin oxide powder is 0.5-3wt%, and the weight percentage of the silver oxide powder or the pure silver powder is 0.5-5wt%;

[0022] When preparing the silver-containing indium zinc oxide low-density embryo, the weight percentage of zinc oxide powder added is 5-30wt%, and the weight percentage of silver oxide powder or pure silver powder is 0.5-5wt%;

[0023] When preparing the silver-containing indium tin zinc oxide low-density embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, the weight percentage of the added zinc oxide powder is 5-30wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%.

[0024] Furthermore, in the step S5, the sintering temperature when preparing the silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin oxide zinc high-density target material embryo body is 1350-1450° C. The density of the prepared silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin oxide zinc high-density target material embryo body is greater than 95%, and the resistance value is less than 3×10 -5 Ωcm.

[0025] Furthermore, in the steps S1 and S4, the ratio of the added zirconia balls, pure water and dispersant is: 68wt% of zirconia balls, 30wt% of pure water and 2wt% of dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid.

[0026] Furthermore, the specific method of step S7 is: the background pressure of the sputtering chamber is pumped down to 0.7×10 -5 ~0.9×10 -5 torr, argon is used as the working gas, and argon is introduced through a throttle valve to control the working pressure of the sputtering chamber to 1×10 -3 ~3×10 -3 torr, the glass substrate or the N-type silicon wafer after the PECVD process is not heated;

[0027] On a glass substrate or an N-type silicon wafer that has completed the PECVD process, a 50-150nm thick indium tin oxide film, an indium zinc oxide film or an indium tin zinc oxide film and a 5-20nm thick silver-containing indium tin oxide film, a silver-containing indium zinc oxide film or a silver-containing indium tin zinc oxide film are sequentially sputtered, and the transmittance of the double-layer film is greater than 80%; the surface of the silver-containing indium tin oxide film, the silver-containing indium zinc oxide film or the silver-containing indium tin zinc oxide film is subjected to a yellow light process, and then a 5-20um thick pure copper film is electroplated, and then an etching process is performed to form a copper metal grid line, thereby completing the copper metallized multi-layer film production or HJT battery production.

[0028] Furthermore, the resistance value of the copper metal grid line obtained in step S7 is less than 5×10 -6 Ωcm, tension greater than 1.5N / cm 2 .

[0029] The beneficial effects of the present invention are:

[0030] (1) By adding silver oxide powder Ag2O or pure silver powder with a particle diameter of less than 1 μm to indium tin oxide, indium zinc oxide or indium tin zinc oxide materials, the sintering temperature is reduced to 1350-1450°C, the density and conductivity of the target material are increased, and the target material density is greater than 95% and the resistance is less than 6×10 -5 Ωcm; and make relevant coating materials by slip casting and medium-high temperature sintering to improve the uniformity of coating materials;

[0031] (2) In the vacuum magnetron sputtering process, when room temperature coating is used to make a transparent conductive film, the flatness of the film can be improved and the damage to the original coated layer can be reduced. After heat treatment, silver particles dispersed on the oxide substrate are precipitated, which is helpful for the subsequent copper electroplating. A composite transparent conductive layer with high light transmittance and high conductivity is formed by the transparent conductive film and the silver particle-containing transparent conductive film, which can take into account the dual functions of transparent conductivity and serving as a copper electroplating seed layer;

[0032] (3) When sputtering a transparent conductive film layer containing silver particles, the target material and the traditional transparent conductive film target material can be placed on the same sputtering machine for sputtering. The process is continuous and will not significantly increase the equipment cost. It is suitable for large-scale mass production and can effectively meet the performance requirements of copper electroplating metallization of heterojunction batteries and heterojunction perovskite stacked batteries. DETAILED DESCRIPTION

[0033] In order to more clearly understand the above-mentioned purpose, features and advantages of the present invention, the present invention is further described in detail below in conjunction with specific embodiments. In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and therefore, the present invention is not limited to the limitations of the specific embodiments disclosed below.

[0034] The embodiment of the present invention provides a method for preparing a transparent conductive target material and a thin film circuit for a copper electroplating process, comprising the following steps:

[0035] S1: Add tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder to indium oxide powder, add zirconium oxide balls, pure water and dispersant, grind and mix thoroughly to form a slurry. The ratio of the added zirconium oxide balls, pure water and dispersant is: 68wt% zirconium oxide balls, 30wt% pure water and 2wt% dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid, and the grinding time is 16 to 72h. The ground slurry is poured into a porous mold with a diameter of 300mm for drying. After 24 hours of drying, the mold is removed to form an indium tin oxide low-density embryo, an indium zinc oxide low-density embryo or an indium tin zinc oxide low-density embryo;

[0036] When making the low-density indium tin oxide embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%;

[0037] When making the low-density indium zinc oxide embryo, the weight percentage of the added zinc oxide powder is 5 to 35 wt %;

[0038] When preparing the low-density indium tin zinc oxide embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, and the weight percentage of the added zinc oxide powder is 5-35wt%.

[0039] S2: sintering the prepared indium tin oxide low-density embryo body, indium zinc oxide low-density embryo body or indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form an indium tin oxide high-density target embryo body, indium zinc oxide high-density target embryo body or indium tin zinc oxide high-density target embryo body with a diameter of 200 mm and a thickness of 6 mm;

[0040] The sintering temperature when making the indium tin oxide high-density target material embryo is 1500-1600°C; the density of the prepared indium tin oxide high-density target material embryo is greater than 98%, and the resistance value is less than 3×10 -4 Ωcm;

[0041] The sintering temperature when making the indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is 1450-1550° C. The density of the prepared indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is greater than 97%, and the resistance value is less than 4×10 -4 Ωcm.

[0042] S3: Bonding an indium tin oxide high-density target body, an indium zinc oxide high-density target body or an indium tin zinc oxide high-density target body on a copper back plate with indium to form a transparent conductive oxide target for sputtering, i.e., an indium tin oxide target, an indium zinc oxide target or an indium tin zinc oxide target.

[0043] S4: Add tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder, and silver oxide powder or pure silver powder to indium oxide powder, and add zirconium oxide balls, pure water and dispersant to fully grind and mix to form a slurry. The particle diameter of the added silver oxide powder or pure silver powder is less than 1um; the ratio of the added zirconium oxide balls, pure water and dispersant is: 68wt% zirconium oxide balls, 30wt% pure water and 2wt% dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid, and the grinding time is 16 to 72h. The ground slurry is poured into a porous mold with a diameter of 300mm for drying. After 24 hours of drying, the mold is demolded to form a low-density indium tin oxide embryo containing silver, a low-density indium zinc oxide embryo containing silver or a low-density indium tin zinc oxide embryo containing silver;

[0044] When preparing the silver-containing indium tin oxide low-density embryo, the weight percentage of the added tin oxide powder is 0.5-3wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%;

[0045] When preparing the silver-containing indium zinc oxide low-density embryo, the weight percentage of the added zinc oxide powder is 5-30wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%;

[0046] When preparing the silver-containing indium tin zinc oxide low-density embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, the weight percentage of the added zinc oxide powder is 5-30wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%.

[0047] S5: sintering the prepared silver-containing indium tin oxide low-density embryo body, silver-containing indium zinc oxide low-density embryo body or silver-containing indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form a silver-containing indium tin oxide high-density target embryo body, silver-containing indium zinc oxide high-density target embryo body or silver-containing indium tin zinc oxide high-density target embryo body with a diameter of 200 mm and a thickness of 6 mm;

[0048] The sintering temperature when preparing the silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin zinc oxide high-density target material embryo body is 1350-1450° C. The density of the prepared silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin zinc oxide high-density target material embryo body is greater than 95%, and the resistance value is less than 3×10 -5 Ωcm.

[0049] S6: Bonding a silver-containing indium tin oxide high-density target material embryo, a silver-containing indium zinc oxide high-density target material embryo or a silver-containing indium tin oxide zinc high-density target material embryo on a copper back plate with indium to form a silver-containing indium tin oxide target, a silver-containing indium zinc oxide target or a silver-containing indium tin oxide zinc target for sputtering.

[0050] S7: Place the glass substrate or N-type silicon wafer that has completed the PECVD process, as well as the target material and the corresponding silver-containing target material into a vacuum sputtering machine, and perform coating at room temperature. The background pressure of the sputtering chamber is pumped down to 0.7×10 -5 ~0.9×10 -5 torr, argon is used as the working gas, and argon is introduced through a throttle valve to control the working pressure of the sputtering chamber to 1×10 -3 ~3×10 -3 torr, the glass substrate or the N-type silicon wafer after the PECVD process is not heated;

[0051] On a glass substrate or an N-type silicon wafer that has completed a PECVD process, a 50-150nm thick indium tin oxide film, an indium zinc oxide film or an indium tin zinc oxide film and a 5-20nm thick silver-containing indium tin oxide film, a silver-containing indium zinc oxide film or a silver-containing indium tin zinc oxide film are sequentially sputtered, and the transmittance of the double-layer film is greater than 80%; the surface of the silver-containing indium tin oxide film, the silver-containing indium zinc oxide film or the silver-containing indium tin zinc oxide film is subjected to a yellow light process, and then a 5-20um thick pure copper film is electroplated, and then an etching process is performed to form a copper metal grid line, and the copper metallized multi-layer film production or HJT battery production is completed. The resistance value of the prepared copper metal grid line is less than 5×10 -6 Ωcm, tension greater than 1.5N / cm 2 .

[0052] The properties of the film prepared by the embodiment of the present invention are described below by means of specific examples:

[0053] Example 1

[0054] S1: Add 0.5wt% of tin oxide powder SnO2 to indium oxide powder In2O3, add zirconium oxide balls, pure water and dispersant, grind and mix thoroughly to form slurry. The ratio of the added zirconium oxide balls, pure water and dispersant is: 68wt% of zirconium oxide balls, 30wt% of pure water and 2wt% of dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid, and the grinding time is 48h. The ground slurry is poured into a porous mold with a diameter of 300mm for drying. After 24 hours of drying, the mold is removed to form a low-density indium tin oxide embryo.

[0055] S2: The prepared low-density indium tin oxide embryo body is sintered at a sintering temperature of 1550° C. After sintering, it is cut and surface ground to form a high-density indium tin oxide target embryo body with a diameter of 200 mm and a thickness of 6 mm.

[0056] S3: The indium tin oxide high-density target material embryo is fixed on the copper back plate with indium to form an indium tin oxide target material for sputtering.

[0057] S4: Add 0.5wt% of tin oxide powder SnO2 and 0.5wt% of silver oxide powder Ag2O to indium oxide powder In2O3, and add zirconium oxide balls, pure water and dispersant to fully grind and mix to form a slurry. The ratio of the added zirconium oxide balls, pure water and dispersant is: 68wt% of zirconium oxide balls, 30wt% of pure water and 2wt% of dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid, and the grinding time is 48h. The ground slurry is poured into a porous mold with a diameter of 300mm for drying. After 24 hours of drying, the mold is removed to form a low-density embryo containing silver indium tin oxide.

[0058] S5: Sintering the prepared silver-containing indium tin oxide low-density embryo body at a sintering temperature of 1400° C. After sintering, cutting and surface grinding are performed to form a silver-containing indium tin oxide high-density target embryo body with a diameter of 200 mm and a thickness of 6 mm.

[0059] S6: The silver-containing indium tin oxide high-density target material embryo is fixed on the copper back plate with indium bonding to form a silver-containing indium tin oxide target material for sputtering.

[0060] S7: Place the glass substrate, indium tin oxide target and silver-containing indium tin oxide target into a vacuum sputtering machine and perform coating at room temperature. Pump the background pressure of the sputtering chamber to 0.7×10 -5 ~0.9×10 -5 torr, argon was used as the working gas, and argon was introduced through a throttle valve to control the working pressure of the sputtering chamber to 2×10 -3torr, the glass substrate is not heated;

[0061] A pulsed DC power supply is used to sputter a 100nm thick indium tin oxide film and a 15nm thick silver-containing indium tin oxide film on a glass substrate. The surface of the silver-containing indium tin oxide film is subjected to a yellow light process, and then a 15um thick pure copper film is electroplated to form a Glass / ITO / ITAgO / Cu multilayer film structure. Then, after an etching process, copper metal grid lines are formed on the surface to complete the production of thin-film copper circuits. A visible spectrometer is used for transmittance measurement, and a four-point probe resistance tester is used for conductivity measurement.

[0062] Example 2

[0063] The preparation method of Example 2 is basically the same as that of Example 1, except that in Example 2, when preparing the low-density indium tin oxide embryo in step S1, 5wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 2wt% of tin oxide powder SnO2 and 1wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0064] Example 3

[0065] The preparation method of Example 3 is basically the same as that of Example 1, except that in Example 3, when preparing the low-density indium tin oxide embryo in step S1, 10wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 3wt% of tin oxide powder SnO2 and 2.5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0066] Example 4

[0067] The preparation method of Example 4 is basically the same as that of Example 1, except that in Example 4, when preparing the low-density indium tin oxide embryo in step S1, 10wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 3wt% of tin oxide powder SnO2 and 5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0068] Example 5

[0069] The preparation method of Example 5 is basically the same as that of Example 1, except that in Example 5, an indium zinc oxide low-density embryo is prepared in step S1, and 5wt% of zinc oxide powder ZnO is added when preparing the indium zinc oxide low-density embryo; the sintering temperature of step S2 is adjusted to 1470°C; in step S4, a silver-containing indium zinc oxide low-density embryo is prepared, and 5wt% of zinc oxide powder ZnO and 0.5wt% of silver oxide powder Ag2O are added when preparing the silver-containing indium zinc oxide low-density embryo; in step S7, a glass substrate, an indium zinc oxide target and a silver-containing indium zinc oxide target are placed in a vacuum sputtering machine, and the formed electroplated copper multilayer thin film structure is a Glass / IZO / IZAgO / Cu multilayer thin film structure, and the remaining steps are the same.

[0070] Example 6

[0071] The preparation method of Example 6 is basically the same as that of Example 5, except that in Example 6, when preparing the indium zinc oxide low-density embryo in step S1, 20wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 20wt% of zinc oxide powder ZnO and 1wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0072] Example 7

[0073] The preparation method of Example 7 is basically the same as that of Example 5, except that in Example 7, when preparing the indium zinc oxide low-density embryo in step S1, 30wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 30wt% of zinc oxide powder ZnO and 2.5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0074] Example 8

[0075] The preparation method of Example 8 is basically the same as that of Example 5, except that in Example 8, when preparing the indium zinc oxide low-density embryo in step S1, 30wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 30wt% of zinc oxide powder ZnO and 5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0076] Example 9

[0077] The preparation method of Example 9 is basically the same as that of Example 1, except that in Example 9, a low-density indium tin zinc oxide embryo is prepared in step S1, and when preparing the low-density indium tin zinc oxide embryo, 0.5wt% of tin oxide powder SnO2 and 5wt% of zinc oxide powder ZnO are added; the sintering temperature of step S2 is adjusted to 1470°C; in step S4, a silver-containing indium tin zinc oxide low-density embryo is prepared, and when preparing the silver-containing indium tin zinc oxide low-density embryo, 0.5wt% of tin oxide powder SnO2, 5wt% of zinc oxide powder ZnO and 0.5wt% of silver oxide powder Ag2O are added; in step S7, a glass substrate, an indium tin zinc oxide target and a silver-containing indium tin zinc oxide target are placed in a vacuum sputtering machine, and the formed electroplated copper multilayer thin film structure is a Glass / ITZO / ITZAgO / Cu multilayer thin film structure, and the remaining steps are the same.

[0078] Example 10

[0079] The preparation method of Example 10 is basically the same as that of Example 9, except that in Example 10, when preparing the indium tin zinc oxide low-density embryo body in step S1, 5wt% of tin oxide powder SnO2 and 20wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo body in step S4, 5wt% of tin oxide powder SnO2, 20wt% of zinc oxide powder ZnO and 1wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0080] Embodiment 11

[0081] The preparation method of Example 11 is basically the same as that of Example 9, except that in Example 11, when preparing the indium tin zinc oxide low-density embryo body in step S1, 10wt% of tin oxide powder SnO2 and 30wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo body in step S4, 10wt% of tin oxide powder SnO2, 30wt% of zinc oxide powder ZnO and 2.5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0082] Example 12

[0083] The preparation method of Example 12 is basically the same as that of Example 9, except that in Example 12, when preparing the indium tin zinc oxide low-density embryo in step S1, 10wt% of tin oxide powder SnO2 and 30wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo in step S4, 10wt% of tin oxide powder SnO2, 30wt% of zinc oxide powder ZnO and 5wt% of silver oxide powder Ag2O are added, and the remaining steps are the same.

[0084] Embodiment 13

[0085] The preparation method of Example 13 is basically the same as that of Example 1, except that in Example 13, when preparing the low-density indium tin oxide embryo in step S1, 0.5wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 0.5wt% of tin oxide powder SnO2 and 0.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0086] Embodiment 14

[0087] The preparation method of Example 14 is basically the same as that of Example 1, except that in Example 14, when preparing the low-density indium tin oxide embryo in step S1, 5wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 2wt% of tin oxide powder SnO2 and 1wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0088] Embodiment 15

[0089] The preparation method of Example 15 is basically the same as that of Example 1, except that in Example 15, when preparing the low-density indium tin oxide embryo in step S1, 10wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 3wt% of tin oxide powder SnO2 and 2.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0090] Example 16

[0091] The preparation method of Example 16 is basically the same as that of Example 1, except that in Example 16, when preparing the low-density indium tin oxide embryo in step S1, 10wt% of tin oxide powder SnO2 is added; when preparing the silver-containing indium tin oxide low-density embryo in step S4, 3wt% of tin oxide powder SnO2 and 5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0092] Embodiment 17

[0093] The preparation method of Example 17 is basically the same as that of Example 5, except that in Example 17, when preparing the indium zinc oxide low-density embryo in step S1, 5wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 5wt% of zinc oxide powder ZnO and 0.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0094] Embodiment 18

[0095] The preparation method of Example 18 is basically the same as that of Example 5, except that in Example 18, when preparing the indium zinc oxide low-density embryo in step S1, 20wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 20wt% of zinc oxide powder ZnO and 1wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0096] Embodiment 19

[0097] The preparation method of Example 19 is basically the same as that of Example 5, except that in Example 19, when preparing the indium zinc oxide low-density embryo in step S1, 30wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 30wt% of zinc oxide powder ZnO and 2.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0098] Embodiment 20

[0099] The preparation method of Example 20 is basically the same as that of Example 5, except that in Example 20, when preparing the indium zinc oxide low-density embryo in step S1, 35wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 35wt% of zinc oxide powder ZnO and 5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0100] Embodiment 21

[0101] The preparation method of Example 21 is basically the same as that of Example 9, except that in Example 21, when preparing the indium tin zinc oxide low-density embryo in step S1, 0.5wt% of tin oxide powder SnO2 and 5wt% of zinc oxide powder ZnO are added; in step S4, when preparing the silver-containing indium tin zinc oxide low-density embryo, 0.5wt% of tin oxide powder SnO2, 5wt% of zinc oxide powder ZnO and 0.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0102] Embodiment 22

[0103] The preparation method of Example 22 is basically the same as that of Example 9, except that in Example 22, when preparing the indium tin zinc oxide low-density embryo in step S1, 5wt% of tin oxide powder SnO2 and 20wt% of zinc oxide powder ZnO are added; in step S4, when preparing the silver-containing indium tin zinc oxide low-density embryo, 5wt% of tin oxide powder SnO2, 20wt% of zinc oxide powder ZnO and 1wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0104] Embodiment 23

[0105] The preparation method of Example 23 is basically the same as that of Example 9, except that in Example 23, when preparing the indium tin zinc oxide low-density embryo in step S1, 10wt% of tin oxide powder SnO2 and 30wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo in step S4, 10wt% of tin oxide powder SnO2, 30wt% of zinc oxide powder ZnO and 2.5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0106] Embodiment 24

[0107] The preparation method of Example 24 is basically the same as that of Example 9, except that in Example 24, when preparing the indium tin zinc oxide low-density embryo in step S1, 10wt% of tin oxide powder SnO2 and 30wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo in step S4, 10wt% of tin oxide powder SnO2, 30wt% of zinc oxide powder ZnO and 5wt% of pure silver powder Ag are added, and the remaining steps are the same.

[0108] Embodiment 25

[0109] The preparation method of Example 25 is basically the same as that of Example 12, except that in Example 25, when preparing the indium tin zinc oxide low-density embryo in step S1, 10wt% of tin oxide powder SnO2 and 30wt% of zinc oxide powder ZnO are added; when preparing the silver-containing indium tin zinc oxide low-density embryo in step S4, 10wt% of tin oxide powder SnO2, 30wt% of zinc oxide powder ZnO and 5wt% of silver oxide powder Ag2O are added; in step S7, the N-type silicon wafer, indium tin zinc oxide target and silver-containing indium tin zinc oxide target for completing the PECVD process are placed in the vacuum sputtering machine, and the formed electroplated copper multilayer thin film structure is a HJT / ITZO / ITZAgO / Cu multilayer thin film structure, and the remaining steps are the same.

[0110] Embodiment 26

[0111] The preparation method of Example 26 is basically the same as that of Example 8, except that in Example 26, when preparing the indium zinc oxide low-density embryo in step S1, 30wt% of zinc oxide powder ZnO is added; when preparing the silver-containing indium zinc oxide low-density embryo in step S4, 30wt% of zinc oxide powder ZnO and 5wt% of silver oxide powder Ag2O are added; in step S7, the N-type silicon wafer, indium zinc oxide target and silver-containing indium zinc oxide target for completing the PECVD process are placed in the vacuum sputtering machine, and the formed electroplated copper multilayer thin film structure is a HJT / IZO / IZAgO / Cu multilayer thin film structure, and the remaining steps are the same.

[0112] Embodiment 27

[0113] The preparation method of Example 27 is basically the same as that of Example 4, except that in Example 27, when preparing the low-density indium tin oxide embryo in step S1, 3wt% of tin oxide powder SnO2 is added; when preparing the low-density indium tin oxide embryo containing silver in step S4, 3wt% of tin oxide powder SnO2 and 5wt% of silver oxide powder Ag2O are added; in step S7, the N-type silicon wafer, indium tin oxide target and silver-containing indium tin oxide target for completing the PECVD process are placed in the vacuum sputtering machine, and the formed electroplated copper multilayer thin film structure is a HJT / ITO / ITAgO / Cu multilayer thin film structure, and the remaining steps are the same.

[0114] Comparative Example 1

[0115] Add 10wt% tin oxide to indium oxide, use cold isostatic molding and 1600℃ high temperature sintering to make a blank, and then process and fix it into indium tin oxide target. Put the glass substrate and indium tin oxide target into a vacuum sputtering machine, and use the vacuum exhaust system to pump the sputtering chamber background pressure to 0.7×10 -5 ~0.9×10 -5 torr, argon was used as the working gas and introduced through the throttle valve to control the working pressure of the sputtering chamber to 2×10 -3 torr, the glass substrate is not heated. Then, a 100nm thick indium tin oxide film is sputtered on the glass substrate with a pulsed DC power supply, and then a 15um thick pure copper film is electroplated to form a layer structure of Glass / ITO / Cu. The transmittance is measured using a visible spectrometer, and the conductivity is measured using a four-point probe resistance tester. The results show that the electroplated copper cannot cover the ITO coating.

[0116] Comparative Example 2

[0117] The preparation method of Comparative Example 2 is basically the same as that of Comparative Example 1, except that in Comparative Example 2, the N-type silicon wafer and indium tin oxide target that have completed the PECVD process are placed in a vacuum sputtering machine for coating to form a HJT / ITO / Cu layer film structure. This structure is subjected to a yellow light process and an etching process to form a copper metal grid line, and then the battery efficiency is measured. The results show that the electroplated copper cannot be successfully covered on the ITO coating.

[0118] The properties of the films obtained in the embodiments and comparative examples are shown in Table 1:

[0119] Table 1 Properties of the films obtained in the examples and comparative examples

[0120]

[0121]

[0122]

[0123]

[0124] From the results in Table 1, it can be seen that the silver-containing indium tin oxide target, silver-containing indium zinc oxide target or silver-containing indium tin zinc oxide target prepared by the slip casting method used in the embodiment of the present invention has a lower resistivity, and the copper electroplating can be coated on the multilayer film structure prepared by vacuum sputtering. And through appropriate thickness control, it can have a better film tension, meeting the requirements of the metallization circuit performance for heterojunction batteries or heterojunction perovskite stacked batteries.

[0125] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a thin film circuit, characterized in that: The steps include: S1: adding tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder to indium oxide powder, adding zirconium oxide balls, pure water and a dispersant, grinding and mixing them fully to form a slurry, pouring the ground slurry into a porous mold for drying to form an indium tin oxide low-density embryo, an indium zinc oxide low-density embryo or an indium tin zinc oxide low-density embryo; S2: sintering the prepared indium tin oxide low-density embryo body, indium zinc oxide low-density embryo body or indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form an indium tin oxide high-density target material embryo body, indium zinc oxide high-density target material embryo body or indium tin zinc oxide high-density target material embryo body; S3: bonding an indium tin oxide high-density target material embryo, an indium zinc oxide high-density target material embryo or an indium tin oxide zinc high-density target material embryo on a copper back plate with indium to form an indium tin oxide target, an indium zinc oxide target or an indium tin oxide zinc target for sputtering; S4: adding tin oxide powder, zinc oxide powder or tin oxide powder and zinc oxide powder, and silver oxide powder or pure silver powder to indium oxide powder, and adding zirconium oxide balls, pure water and a dispersant to fully grind and mix to form a slurry, pouring the ground slurry into a porous mold for drying to form a silver-containing indium tin oxide low-density embryo body, a silver-containing indium zinc oxide low-density embryo body or a silver-containing indium tin oxide zinc low-density embryo body; S5: sintering the prepared silver-containing indium tin oxide low-density embryo body, silver-containing indium zinc oxide low-density embryo body or silver-containing indium tin zinc oxide low-density embryo body, and cutting and surface grinding after sintering to form a silver-containing indium tin oxide high-density target material embryo body, silver-containing indium zinc oxide high-density target material embryo body or silver-containing indium tin zinc oxide high-density target material embryo body; S6: bonding a silver-containing indium tin oxide high-density target material embryo, a silver-containing indium zinc oxide high-density target material embryo, or a silver-containing indium tin oxide zinc high-density target material embryo on a copper back plate with indium to form a silver-containing indium tin oxide target, a silver-containing indium zinc oxide target, or a silver-containing indium tin oxide zinc target for sputtering; S7: Place the glass substrate or the N-type silicon wafer that has completed the PECVD process, as well as the target material and the corresponding silver-containing target material into a vacuum sputtering machine, and perform coating at room temperature. Sputter a 50-150nm thick indium tin oxide film, an indium zinc oxide film or an indium tin zinc oxide film, and a 5-20nm thick silver-containing indium tin oxide film, a silver-containing indium zinc oxide film or a silver-containing indium tin zinc oxide film on the glass substrate or the N-type silicon wafer that has completed the PECVD process in sequence; perform a yellow light process on the surface of the silver-containing indium tin oxide film, the silver-containing indium zinc oxide film or the silver-containing indium tin zinc oxide film, and then electroplate a 5-20µm thick pure copper film, and then perform an etching process to form a copper metal grid line to complete the thin film circuit production.

2. The method for preparing a thin film circuit according to claim 1, characterized in that: When preparing the low-density indium tin oxide embryo in step S1, the weight percentage of the added tin oxide powder is 0.5-10wt%; When making the low-density indium zinc oxide embryo, the weight percentage of zinc oxide powder added is 5-35wt%; When preparing the low-density indium tin zinc oxide embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, and the weight percentage of the added zinc oxide powder is 5-35wt%.

3. The method for preparing a thin film circuit according to claim 1, characterized in that: The grinding time in steps S1 and S4 is 16 to 72 hours.

4. The method for preparing a thin film circuit according to claim 1, characterized in that: In step S2, the sintering temperature when making the indium tin oxide high-density target material embryo is 1500-1600° C. The density of the obtained indium tin oxide high-density target material embryo is greater than 98%, and the resistivity is less than 3×10 -4 Ωcm; The sintering temperature when making the indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is 1450-1550°C; the density of the prepared indium zinc oxide high-density target material embryo body or the indium tin zinc oxide high-density target material embryo body is greater than 97%, and the resistivity is less than 4×10 -4 Ωcm.

5. The method for preparing a thin film circuit according to claim 1, characterized in that: When preparing the silver-containing indium tin oxide low-density embryo in step S4, the weight percentage of the added tin oxide powder is 0.5-3wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%; When preparing the silver-containing indium zinc oxide low-density embryo, the weight percentage of zinc oxide powder added is 5-30wt%, and the weight percentage of silver oxide powder or pure silver powder is 0.5-5wt%; When preparing the silver-containing indium tin zinc oxide low-density embryo, the weight percentage of the added tin oxide powder is 0.5-10wt%, the weight percentage of the added zinc oxide powder is 5-30wt%, and the weight percentage of the silver oxide powder or pure silver powder is 0.5-5wt%.

6. The method for preparing a thin film circuit according to claim 1, characterized in that: In the step S5, the sintering temperature when preparing the silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin oxide zinc high-density target material embryo body is 1350-1450° C. The density of the prepared silver-containing indium tin oxide high-density target material embryo body, the silver-containing indium zinc oxide high-density target material embryo body or the silver-containing indium tin oxide zinc high-density target material embryo body is greater than 95%, and the resistivity is less than 3×10 -5 Ωcm.

7. The method for preparing a thin film circuit according to claim 1, characterized in that: In the steps S1 and S4, the ratio of the added zirconium oxide balls, pure water and dispersant is: 68wt% of zirconium oxide balls, 30wt% of pure water and 2wt% of dispersant; the dispersant is a sodium salt aqueous solution of polyacrylic acid.

8. The method for preparing a thin film circuit according to claim 1, characterized in that: The specific method of step S7 is: the background pressure of the sputtering chamber is pumped down to 0.7×10 -5 ~0.9×10 -5 torr, argon is used as the working gas, and argon is introduced through a throttle valve to control the working pressure of the sputtering chamber to 1×10 -3 ~3×10 -3 torr, the glass substrate or the N-type silicon wafer after the PECVD process is not heated; On a glass substrate or an N-type silicon wafer that has completed the PECVD process, a 50-150nm thick indium tin oxide film, an indium zinc oxide film or an indium tin zinc oxide film and a 5-20nm thick silver-containing indium tin oxide film, a silver-containing indium zinc oxide film or a silver-containing indium tin zinc oxide film are sequentially sputtered, and the transmittance of the double-layer film is greater than 80%; the surface of the silver-containing indium tin oxide film, the silver-containing indium zinc oxide film or the silver-containing indium tin zinc oxide film is subjected to a yellow light process, and then a 5-20µm thick pure copper film is electroplated, and then an etching process is performed to form a copper metal grid line to complete the thin film circuit production.

9. The method for preparing a thin film circuit according to claim 1, characterized in that: The resistivity of the copper metal grid line obtained in step S7 is less than 5×10 -6 Ωcm.

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