An ico target material, a preparation method thereof and application thereof

Abstract

The application discloses an ICO target material and a preparation method and application thereof, and relates to the technical field of sputtering targets.The ICO target material comprises the following components in terms of molar percentage: Ce: 0.5-2.5%; Al: 0.05-0.2%; Si: 0.05-0.25%; and In: 97-99.5%. The application introduces Al and Si elements on the basis of the original Ce-doped ICO target material, and realizes the high-density performance of the ICO target material by regulating the dosages of the elements in the ICO target material.

Description

Technical Field

[0001] This invention relates to the field of sputtering target technology, and in particular to an ICO target, its preparation method, and its application. Background Technology

[0002] Indium cerium oxide (ICO) transparent conductive oxide (TCO) thin films have the dual advantages of excellent conductivity and light transmittance, as well as high electron mobility, and are regarded as important thin film materials for future heterojunctions, perovskite solar cells, and flexible transparent electronic devices.

[0003] TCO thin films based on ICO are crucial materials for future photovoltaic cells and represent a key area for breakthroughs that will drive future market development. This is because, on the one hand, compared to Sn... 4+ ion, Ce 4+ The effective radius of the ion (0.101 nm) and In 3+ The ions are closer (0.094 nm), and both have a coordination number of 6. Under the same doping concentration, Ce... 4+ Ion doping results in less microstrain. On the other hand, Ce doping can also reduce the density of intracrystalline oxygen vacancies and their grain boundary scattering for carrier transport; the lower carrier concentration also reduces the absorption of near-infrared free carriers. Therefore, developing a high-mobility, high-transmittance TCO thin film using ICO as a substrate not only meets future market demands but also provides important guidance for the research and development of TCO thin films.

[0004] However, existing ICO targets cannot achieve high density under normal pressure sintering conditions. This is partly due to Ce... 4+ The effective radius of the ion is greater than that of In. 3+ The presence of ions leads to low solid solubility of Ce in In₂O₃, and Ce during sintering... 4+ Ions have difficulty entering the In2O3 lattice. On the other hand, the transport of In2O3 and CeO2 during sintering mainly relies on diffusion, and the sintering driving force mainly relies on the surface tension of the powder. The driving force is relatively weak, and excessively high temperature will cause the volatilization of In2O3 and CeO2, which will seriously affect the density.

[0005] Therefore, there is an urgent need to develop a high-density ICO target to solve the above problems. Summary of the Invention

[0006] The first technical problem to be solved by this invention is:

[0007] An ICO target material is provided.

[0008] The second technical problem to be solved by this invention is:

[0009] A method for preparing the ICO target is provided.

[0010] The third technical problem to be solved by this invention is:

[0011] Application of the ICO target material.

[0012] The present invention also proposes a TCO thin film, comprising the aforementioned ICO target material.

[0013] To solve the first technical problem, the technical solution adopted by the present invention is as follows:

[0014] An ICO target material, by molar percentage, comprises the following components:

[0015] Ce: 0.5%–2.5%;

[0016] Al: 0.05%–0.2%;

[0017] Si: 0.05%–0.25%;

[0018] In: 97-99.5%.

[0019] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0020] This invention introduces Al and Si elements into the original Ce-doped ICO target material. By controlling the amount of each element in the ICO target material, the high-density performance of the ICO target material is achieved.

[0021] During the preparation process, cerium reacts with oxygen to form oxides, which helps stabilize the material's crystal structure and reduce lattice defects, thereby increasing the material's density. Furthermore, the presence of cerium can also increase the material's electrical conductivity.

[0022] Aluminum is present in relatively low amounts in ICO sputtering targets, but it can strengthen the material. The addition of aluminum can form solid solutions or precipitates, which helps to improve the hardness and strength of the material, thereby increasing its density.

[0023] Silicon has a low resistivity, and its addition to ICO targets can form silicon solid solutions or silicon compounds, which helps to reduce the resistivity of the material.

[0024] Indium is a surplus element in ICO targets, and its content is affected by the content of other elements. The addition of indium can adjust the crystal structure and microstructure of the material, helping to optimize its performance. Specific indium contents can lead to the formation of specific crystalline or precipitated phases, thereby affecting the material's density and resistivity.

[0025] Furthermore, within the aforementioned dosage range, the interaction between cerium, aluminum, silicon, and indium can also form specific crystal structures:

[0026] The combined action of Ce, Si, and Al forms the Ce-Si-Al phase. In this phase, Ce forms a solid solution or intermetallic compound with Si and Al, exhibiting good electrical conductivity and stability. The formation of the Ce-Si-Al phase optimizes the crystal structure of the material, reduces lattice defects, and thus increases the material's density. Simultaneously, the good electrical conductivity of the Ce-Si-Al phase reduces the material's resistivity.

[0027] The interaction of Ce and In forms the CeIn3 phase. CeIn3 is an intermetallic compound with good electrical conductivity.

[0028] The interaction between Ce and Si forms the Ce3Si5 phase. Ce3Si5 is a metallic silicon compound with good electrical conductivity and stability. The formation of the Ce3Si5 phase can increase the density of the material because the interaction between Ce and Si helps reduce lattice defects. Furthermore, the good electrical conductivity of the Ce3Si5 phase also reduces the resistivity of the material.

[0029] According to one embodiment of the present invention, the ICO target material, by molar percentage, comprises the following components:

[0030] Ce: 1.85%–2.5%;

[0031] Al: 0.1%–0.2%;

[0032] Si: 0.05%–0.25%;

[0033] In: 97-98%.

[0034] To solve the second technical problem, the technical solution adopted by the present invention is as follows:

[0035] A method for preparing the ICO target material includes the following steps:

[0036] S1 mixes a compound containing Ce, Al, Si and In in a solvent and then ball-mills it to obtain a mixed slurry;

[0037] S2 involves placing the mixed slurry in a sealed container and degassing it under vacuum to obtain the treated slurry;

[0038] S3 allows the slurry to flow into the mold, and the air pressure is adjusted to 0.2MPa~0.5MPa. After holding the pressure and letting it stand, it is dried to obtain the molded blank.

[0039] S4 sinters the formed green blank to obtain the ICO target material.

[0040] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0041] This invention, through doping with dopants, combined with improved slurry casting technology and specific control of the slurry casting process, enables the preparation of ICO targets that not only maintain extremely low resistivity but also significantly improve sintering density, solving the problem of achieving dense sintering under normal pressure conditions.

[0042] In step S3, appropriate molding pressure facilitates more complete filling of the slurry in the mold and promotes the removal of moisture and other organic substances, resulting in a green body with lower porosity and higher density. If the molding pressure is too low, the green body will not achieve maximum densification, affecting the sintering densification process; if the molding pressure is too high, defects similar to delamination will occur.

[0043] The ICO target material prepared by this invention has a relative density of up to 99.93% and a resistivity of down to 0.428 mΩ·cm, which greatly improves the sintering density while ensuring low resistivity.

[0044] According to one embodiment of the present invention, in step S1, the ball milling is a two-step ball milling. After mixing the components in the solvent, the first step of ball milling is performed for 21 to 40 hours, and then the dispersant is added and the second step of ball milling is performed.

[0045] According to one embodiment of the present invention, the second ball milling time is 2 to 3 hours.

[0046] According to one embodiment of the present invention, the dispersant comprises polyacrylic acid.

[0047] According to one embodiment of the present invention, in step S2, the vacuum degassing time is 5 to 6 minutes.

[0048] According to one embodiment of the present invention, in step S2, during the vacuum degassing process, the pressure in the sealed container is -0.1MPa to -0.2MPa.

[0049] According to one embodiment of the present invention, step S3 further includes the following step: using an air pressure of 0.2MPa to 0.7MPa to make the slurry flow into the mold.

[0050] According to one embodiment of the present invention, in step S3, the pressure holding and settling time is 5 to 10 hours. A reasonable pressure holding and settling time is crucial. On the one hand, if the pressure is not transmitted to the required depth during the grouting process, and the pressure is removed too early, it is difficult to remove moisture and other organic matter, resulting in insufficient density of the obtained green body. On the other hand, excessively long pressure holding time will cause large residual stress in the green body, leading to cracking of the molded body and the target material during drying or sintering.

[0051] Different slurries with different compositions exhibit varying degrees of affinity for water and organic matter. For instance, Al oxides are more hydrophilic than Si. Therefore, when the proportion of Al oxides is higher, the molding pressure and holding time can be appropriately increased, and vice versa.

[0052] According to one embodiment of the present invention, in step S3, the drying time is 8 to 10 hours. Drying removes moisture from the green blank, resulting in a green blank with higher density.

[0053] According to one embodiment of the present invention, the mold, both the upper and lower molds, are made of plaster.

[0054] According to one embodiment of the present invention, the lower mold of the mold has a groove with a diameter of 110-120 mm.

[0055] According to one embodiment of the present invention, the lower mold of the mold has a height of 12-13 mm.

[0056] According to one embodiment of the present invention, in step S4, the sintering is a three-step sintering process, wherein the temperature of the first step sintering is 1600℃~1700℃, the temperature of the second step sintering is 1450℃~1550℃, and the temperature of the third step sintering is 1100℃~1250℃.

[0057] According to one embodiment of the present invention, in step S4, the heating rate in the three-step sintering is 3-5°C / min.

[0058] According to one embodiment of the present invention, the second and third sintering steps further include the following step: introducing oxygen at a rate of 20–35 L / min and a pressure of 3.0–3.5 kg / cm². 2 .

[0059] According to one embodiment of the present invention, the second and third sintering processes further include a heat preservation step, wherein the heat preservation time ratio of the second and third sintering processes is 5-8:3-5.

[0060] According to one embodiment of the present invention, the first sintering process does not include a heat preservation step.

[0061] According to one embodiment of the present invention, step S4 further includes the following steps: machining and surface polishing and bonding the prepared ICO target material to obtain the finished target material.

[0062] Another aspect of the present invention provides a TCO thin film, comprising the ICO target material as described in the first aspect embodiment above. Since this application employs all the technical solutions of the aforementioned ICO target material, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments.

[0063] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Detailed Implementation

[0064] In the description of this invention, the use of terms such as "first," "second," etc., is for the purpose of distinguishing technical features only and should not be construed as indicating or implying relative importance, or implicitly indicating the number of technical features indicated, or implicitly indicating the order of the technical features indicated.

[0065] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0066] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of the present invention.

[0067] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0068] Example 1

[0069] An ICO target material, by molar percentage, comprises the following components:

[0070] Ce: 1%;

[0071] Al: 0.08%;

[0072] Si: 0.05%;

[0073] In: 98.87%.

[0074] The method for preparing the above-mentioned ICO target material includes the following steps:

[0075] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 20 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 2 hours to obtain a mixed slurry.

[0076] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0077] S3 uses an air compressor with an air pressure of 0.2MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.4MPa, and the pressure is maintained for 8 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9 hours to obtain the molded green blank.

[0078] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1450℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1100℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 20 L / min and a pressure of 3.0 kg / cm². 2 The target material semi-finished product is obtained;

[0079] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0080] A TCO thin film comprising the aforementioned ICO target material.

[0081] Example 2

[0082] An ICO target material, by molar percentage, comprises the following components:

[0083] Ce: 1.5%;

[0084] Al: 0.15%;

[0085] Si: 0.10%;

[0086] In: 98.25%.

[0087] The method for preparing the above-mentioned ICO target material includes the following steps:

[0088] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 38 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0089] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0090] S3 uses an air compressor with an air pressure of 0.5MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.5MPa, and the pressure is maintained for 10 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the shaped green blank.

[0091] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 8 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 5 hours. During the second and third sintering steps, oxygen is introduced at a rate of 20 L / min and a pressure of 3.5 kg / cm². 2 The target material semi-finished product is obtained;

[0092] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0093] A TCO thin film comprising the aforementioned ICO target material.

[0094] Example 3

[0095] An ICO target material, by molar percentage, comprises the following components:

[0096] Ce: 2.5%;

[0097] Al: 0.05%;

[0098] Si: 0.03%;

[0099] In: 97.42%.

[0100] The method for preparing the above-mentioned ICO target material includes the following steps:

[0101] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball-milled for 40 hours. Then, polyacrylic acid dispersant was added and ball-milled for another 2 hours to obtain a mixed slurry.

[0102] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0103] S3 uses an air compressor with an air pressure of 0.6MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.2MPa, and the pressure is maintained for 8 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8.5 hours to obtain the molded green blank.

[0104] S4 sintersects the formed green body in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 4 hours. Oxygen is introduced during the second and third sintering steps at a rate of 35 L / min and a pressure of 3.0 kg / cm². 2 The target material semi-finished product is obtained;

[0105] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0106] A TCO thin film comprising the aforementioned ICO target material.

[0107] Example 4

[0108] An ICO target material, by molar percentage, comprises the following components:

[0109] Ce: 0.5%;

[0110] Al: 0.15%;

[0111] Si: 0.15%;

[0112] In: 99.20%.

[0113] The method for preparing the above-mentioned ICO target material includes the following steps:

[0114] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0115] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0116] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the shaped green blank.

[0117] S4 sintersects the formed green body in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 4 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.5 kg / cm². 2 The target material semi-finished product is obtained;

[0118] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0119] A TCO thin film comprising the aforementioned ICO target material.

[0120] Example 5

[0121] An ICO target material, by molar percentage, comprises the following components:

[0122] Ce: 2%;

[0123] Al: 0.2%;

[0124] Si: 0.25%;

[0125] In: 97.55%.

[0126] The method for preparing the above-mentioned ICO target material includes the following steps:

[0127] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball-milled for 40 hours. Then, polyacrylic acid dispersant was added and ball-milled for another 2 hours to obtain a mixed slurry.

[0128] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0129] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 6.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the molded green blank.

[0130] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.0 kg / cm².2 The target material semi-finished product is obtained;

[0131] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0132] A TCO thin film comprising the aforementioned ICO target material.

[0133] Example 6

[0134] An ICO target material, by molar percentage, comprises the following components:

[0135] Ce: 2.5%;

[0136] Al: 0.15%;

[0137] Si: 0.1%;

[0138] In: 97.25%.

[0139] The method for preparing the above-mentioned ICO target material includes the following steps:

[0140] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 38 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 2 hours to obtain a mixed slurry.

[0141] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0142] S3 uses an air compressor with an air pressure range of 0.5MPa to allow the slurry to flow slowly into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.5MPa, and the pressure is maintained for 9 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 10 hours to obtain the molded green blank.

[0143] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.3 kg / cm². 2 The target material semi-finished product is obtained;

[0144] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0145] A TCO thin film comprising the aforementioned ICO target material.

[0146] Example 7

[0147] An ICO target material, by molar percentage, comprises the following components:

[0148] Ce: 1.85%;

[0149] Al: 0.1%;

[0150] Si: 0.05%;

[0151] In: 98.00%.

[0152] The method for preparing the above-mentioned ICO target material includes the following steps:

[0153] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 39 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0154] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0155] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.2MPa, and the pressure is maintained for 9.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8 hours to obtain the molded green blank.

[0156] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 4 hours. Oxygen is introduced during the second and third sintering steps at a rate of 35 L / min and a pressure of 3.4 kg / cm². 2 The target material semi-finished product is obtained;

[0157] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0158] A TCO thin film comprising the aforementioned ICO target material.

[0159] Example 8

[0160] An ICO target material, by molar percentage, comprises the following components:

[0161] Ce: 2.5%;

[0162] Al: 0.15%;

[0163] Si: 0.25%;

[0164] In: 97.10%.

[0165] The method for preparing the above-mentioned ICO target material includes the following steps:

[0166] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 39 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0167] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0168] S3 uses an air compressor with an air pressure of 0.6MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 6.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the molded green blank.

[0169] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 30 L / min and a pressure of 3.2 kg / cm². 2 The target material semi-finished product is obtained;

[0170] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0171] A TCO thin film comprising the aforementioned ICO target material.

[0172] Example 9

[0173] An ICO target material, by molar percentage, comprises the following components:

[0174] Ce: 2%;

[0175] Al: 0.2%;

[0176] Si: 0.25%;

[0177] In: 97.55%.

[0178] The method for preparing the above-mentioned ICO target material includes the following steps:

[0179] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 38 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 2 hours to obtain a mixed slurry.

[0180] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0181] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 6.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the molded green blank.

[0182] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 6 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 5 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.0 kg / cm². 2 The target material semi-finished product is obtained;

[0183] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0184] A TCO thin film comprising the aforementioned ICO target material.

[0185] Example 10

[0186] An ICO target material, by molar percentage, comprises the following components:

[0187] Ce: 2%;

[0188] Al: 0.2%;

[0189] Si: 0.2%;

[0190] In: 97.60%.

[0191] The method for preparing the above-mentioned ICO target material includes the following steps:

[0192] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0193] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0194] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 6.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 9.5 hours to obtain the molded green blank.

[0195] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1550℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.3 kg / cm². 2 The target material semi-finished product is obtained;

[0196] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0197] A TCO thin film comprising the aforementioned ICO target material.

[0198] Comparative Example 1

[0199] An ICO target material, by molar percentage, comprises the following components:

[0200] Ce: 0.5%;

[0201] In: 99.50%.

[0202] The method for preparing the above-mentioned ICO target material includes the following steps:

[0203] S1 In2O3 powder and CeO2 powder were added to deionized water according to the dosage and ball milled for 38 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0204] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0205] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.2MPa, and the pressure is maintained for 5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8 hours to obtain the molded green blank.

[0206] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1200℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.3 kg / cm². 2 The target material semi-finished product is obtained;

[0207] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0208] A TCO thin film comprising the aforementioned ICO target material.

[0209] Comparative Example 2

[0210] An ICO target material, by molar percentage, comprises the following components:

[0211] Ce: 2.5%;

[0212] In: 97.50%.

[0213] The method for preparing the above-mentioned ICO target material includes the following steps:

[0214] S1 In2O3 powder and CeO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0215] S2 places the mixed slurry in a sealed tank and maintains it at -0.25MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0216] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.5MPa, and the pressure is maintained for 10 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 10 hours to obtain the molded green blank.

[0217] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1450℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 25 L / min and a pressure of 3.4 kg / cm². 2 The target material semi-finished product is obtained;

[0218] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0219] A TCO thin film comprising the aforementioned ICO target material.

[0220] Comparative Example 3

[0221] An ICO target material, by molar percentage, comprises the following components:

[0222] Ce: 0.5%;

[0223] In: 99.50%.

[0224] The method for preparing the above-mentioned ICO target material includes the following steps:

[0225] S1 In2O3 powder and CeO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0226] S2 spray-granulates the ball-milled slurry to obtain a specific surface area of ​​10m². 2 / g~22m 2 / g of spherical particles;

[0227] S3 molds the above spherical particles, vacuum-packs the blank after molding, and then immerses it in a hydraulic cylinder for cold isostatic pressing at 220MPa for 15 minutes.

[0228] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 6 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 5 hours. During the second and third sintering steps, oxygen is introduced at a rate of 35 L / min and a pressure of 3.5 kg / cm². 2 The target material semi-finished product is obtained;

[0229] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0230] A TCO thin film comprising the aforementioned ICO target material.

[0231] Comparative Example 4

[0232] An ICO target material, by molar percentage, comprises the following components:

[0233] Ce: 0.5%;

[0234] Al: 0.15%;

[0235] Si: 0.15%;

[0236] In: 99.20%.

[0237] The method for preparing the above-mentioned ICO target material includes the following steps:

[0238] S1 In2O3 powder, CeO2 powder, Al2O3 and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0239] S2 spray-granulates the ball-milled slurry to obtain a specific surface area of ​​10m². 2 / g~22m 2 / g of spherical particles;

[0240] S3 molds the above spherical particles, vacuum-packs the blank after molding, and then immerses it in a hydraulic cylinder for cold isostatic pressing at 220MPa for 15 minutes.

[0241] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1450℃ at a rate of 3℃ / min and holding for 8 hours. The third step involves cooling to 1100℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 28 L / min and a pressure of 3.5 kg / cm². 2 The target material semi-finished product is obtained;

[0242] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0243] A TCO thin film comprising the aforementioned ICO target material.

[0244] Comparative Example 5

[0245] An ICO target material, by molar percentage, comprises the following components:

[0246] Ce: 0.5%;

[0247] Al: 0.05%;

[0248] In: 99.45%.

[0249] The method for preparing the above-mentioned ICO target material includes the following steps:

[0250] S1 In2O3 powder, CeO2 powder and Al2O3 were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0251] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0252] S3 uses an air compressor with an air pressure of 0.6MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.2MPa, and the pressure is maintained for 6.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8 hours to obtain the shaped green blank.

[0253] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 6 hours. The third step involves cooling to 1100℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 28 L / min and a pressure of 3.0 kg / cm². 2 The target material semi-finished product is obtained;

[0254] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0255] A TCO thin film comprising the aforementioned ICO target material.

[0256] Comparative Example 6

[0257] An ICO target material, by molar percentage, comprises the following components:

[0258] Ce: 0.5%;

[0259] Si: 0.05%;

[0260] In: 99.45%.

[0261] The method for preparing the above-mentioned ICO target material includes the following steps:

[0262] S1 In2O3 powder, CeO2 powder and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0263] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0264] S3 uses an air compressor with an air pressure of 0.7MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 9 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8.5 hours to obtain the shaped green blank.

[0265] S4 sintersects the formed green blank in three steps. The first step involves heating to 1600℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1450℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1100℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 30 L / min and a pressure of 3.0 kg / cm². 2 The target material semi-finished product is obtained;

[0266] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0267] A TCO thin film comprising the aforementioned ICO target material.

[0268] Comparative Example 7

[0269] In step S4 of Example 7, the highest sintering temperature is 1580°C.

[0270] An ICO target material, by molar percentage, comprises the following components:

[0271] Ce: 1.85%;

[0272] Al: 0.10%;

[0273] Si: 0.05%;

[0274] In: 98.00%.

[0275] The method for preparing the above-mentioned ICO target material includes the following steps:

[0276] S1 In2O3 powder, CeO2 powder and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0277] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0278] S3 uses an air compressor with an air pressure of 0.6MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 9.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8.5 hours to obtain the molded green blank.

[0279] S4 sintersects the formed green blank in three steps. The first step involves heating to 1580℃ at a rate of 3℃ / min and holding for 0 hours. The second step involves cooling to 1500℃ at a rate of 3℃ / min and holding for 5 hours. The third step involves cooling to 1250℃ at a rate of 3℃ / min and holding for 3 hours. During the second and third sintering steps, oxygen is introduced at a rate of 30 L / min and a pressure of 3.5 kg / cm². 2 The target material semi-finished product is obtained;

[0280] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0281] A TCO thin film comprising the aforementioned ICO target material.

[0282] Comparative Example 8

[0283] In step S4 of Comparative Example 8, oxygen is not introduced during the second and third sintering steps.

[0284] An ICO target material, by molar percentage, comprises the following components:

[0285] Ce: 1.80%;

[0286] Al: 0.10%;

[0287] Si: 0.05%;

[0288] In: 98.05%.

[0289] The method for preparing the above-mentioned ICO target material includes the following steps:

[0290] S1 In2O3 powder, CeO2 powder and SiO2 powder were added to deionized water according to the dosage and ball milled for 40 hours. Then, polyacrylic acid dispersant was added and ball milling was continued for 3 hours to obtain a mixed slurry.

[0291] S2 places the mixed slurry in a sealed tank and maintains it at -0.2MPa for 5 minutes to perform vacuum degassing, thereby obtaining the treated slurry;

[0292] S3 uses an air compressor with an air pressure of 0.6MPa to slowly flow the slurry into the mold. After the mold is completely filled, the slurry outlet is closed, the air pressure is adjusted to 0.3MPa, and the pressure is maintained for 9.5 hours. After the pressure is maintained, the green blank is placed in an oven to dry for 8.5 hours to obtain the molded green blank.

[0293] S4 sinters the formed blank. The sintering is divided into three steps. The first step of sintering is to heat up to 1600℃ at 3℃ / min and hold for 0h. The second step of sintering is to cool down to 1500℃ at 3℃ / min and hold for 5h. The third step of sintering is to cool down to 1250℃ at 3℃ / min and hold for 3h. During the second and third steps of sintering, no oxygen is introduced to obtain the target material semi-finished product.

[0294] S5 performs machining, surface polishing, and bonding of the target material semi-finished product to obtain the ICO target material.

[0295] A TCO thin film comprising the aforementioned ICO target material.

[0296] The component dosages and molding conditions of Examples 1-10 and Comparative Examples 1-8 were statistically analyzed to obtain Table 1.

[0297] Table 1

[0298]

[0299] Performance testing:

[0300] The molded blanks and ICO targets prepared in Examples 1-10 and Comparative Examples 1-6 were subjected to the following tests, and the test results are shown in Table 2.

[0301] 1) The resistivity of the target material was tested using the four-point probe method.

[0302] 2) The density of the green blank and the target material was tested using Archimedes' principle.

[0303] The measurement of the green body density involved the following steps: To avoid contact between the dried green body and water, the surface of the green body was polished and coated with a layer of liquid paraffin before testing. The weight of the green body after polishing (m1) and the mass after coating with paraffin (m2) were recorded. After measurement, the green body was directly immersed in pure water, and the weight was recorded as m3. The water temperature was recorded using a thermometer, and the density of the water (ρ1) was recorded according to the relationship between water temperature and density. The density of the paraffin was calculated as 0.91 g / cm³. 2 Calculation. Based on this, the actual density ρ2 of the green body can be obtained:

[0304]

[0305] The target density measurement involved: grinding the surface of the sintered target and recording its weight (m4); then immersing the target directly in pure water and recording its weight (m5). The water temperature was recorded using a thermometer, and the water density (ρ1) was recorded by referring to a table showing the relationship between water temperature and density. Based on this, the actual density (ρ3) of the target could be obtained.

[0306]

[0307] Relative density calculation method: Relative density = (actual density ÷ theoretical density) × 100%.

[0308] Table 2

[0309]

[0310]

[0311] As can be seen from Table 2:

[0312] Comparative Examples 1-4 show that the density of the billet obtained by slip casting is higher than that obtained by wet isostatic pressing, and the density of the green billet gradually increases with increasing pressure and holding time. Analysis of Example 2 and Comparative Example 2 shows that when the pressure reaches 0.5 MPa and the holding time exceeds 10 hours, cracks appear in the sintered targets. This may be due to excessive pressure and prolonged holding time, leading to internal dark cracks within the billet and causing sintering cracking.

[0313] In summary, appropriate molding pressure facilitates more complete filling of the slurry in the mold and promotes the removal of moisture and other organic substances, resulting in a green body with lower porosity and higher density. If the molding pressure is too low, the green body will not achieve maximum densification, affecting the sintering densification process; if the molding pressure is too high, defects similar to delamination will occur.

[0314] The appropriate holding time under pressure is crucial. On the one hand, if the pressure is not transmitted to the required depth during the grouting process and is removed too early, it will be difficult to remove moisture and other organic matter, resulting in insufficient density of the green body. On the other hand, excessive holding time will cause large residual stress in the green body, leading to cracking of the molded body and the target material during drying or sintering, thus failing to meet the sputtering conditions. Target material density and resistivity are positively correlated; therefore, the molding pressure and holding time directly affect the resistivity.

[0315] Analysis of Comparative Examples 1-3, 5-6, and Example 1 shows that the incorporation of Al and Si significantly improves the density of the sintered target material, and the density gradually increases with the increase of Al and Si content. However, Examples 9-10 show that when the Al and Si content reaches 2.5%, the density decreases and cannot meet the sputtering requirements.

[0316] Analysis of Comparative Example 4 and Example 4 shows that both the target materials prepared by isostatic pressing and slip casting can meet the coating requirements. However, under the same composition conditions, the target material prepared by slip casting is superior to that prepared by isostatic pressing in terms of both raw blank density and sintered body density, indicating that slip casting has obvious advantages.

[0317] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. An ICO target material, characterized by: In: 98.87%, Ce: 1.00%, Al: 0.08%, Si: 0.05%; or, In: 98.25%, Ce: 1.50%, Al: 0.15%, Si: 0.10%; or, In: 97.42%, Ce: 2.50%, Al: 0.05%, Si: 0.03%; or, In: 99.20%, Ce: 0.50%, Al: 0.15%, Si: 0.15%; or, In: 97.25%, Ce: 2.50%, Al: 0.15%, Si: 0.10%; or, In: 98.00%, Ce: 1.85%, Al: 0.10%, Si: 0.05%; or, In: 97.10%, Ce: 2.50%, Al: 0.15%, Si: 0.25%; The combined action of Ce, Si and Al forms a Ce-Si-Al phase; the combined action of Ce and In forms a CeIn3 phase; and the combined action of Ce and Si forms a Ce3Si5 phase. The preparation method of the ICO target material has the following steps: S1: mixing compounds containing Ce, Al, Si and In in a solvent, ball milling to obtain a mixed slurry; S2: placing the mixed slurry in a sealed container, vacuum defoaming to obtain a treated slurry; S3: flowing the treated slurry into a mold, adjusting the air pressure to 0.2 MPa-0.5 MPa, and after pressure holding and standing, performing drying treatment to obtain a formed green body; S4: sintering the formed green body to obtain the ICO target material; In step S4, the sintering is three-step sintering, the first-step sintering temperature is 1600-1700 °C, the second-step sintering temperature is 1450-1550 °C, and the third-step sintering temperature is 1100-1250 °C. The preparation method has the following steps: The second step sintering and the third step sintering further comprise the following steps: oxygen is introduced at a speed of 20-35 L / min and a pressure of 3.0-3.5 kg / cm 2 .

2. A method of making an ICO target as claimed in claim 1, characterized by: S1: mixing compounds containing Ce, Al, Si and In in a solvent, ball milling to obtain a mixed slurry; S2: placing the mixed slurry in a sealed container, vacuum defoaming to obtain a treated slurry; S3: flowing the treated slurry into a mold, adjusting the air pressure to 0.2 MPa-0.5 MPa, and after pressure holding and standing, performing drying treatment to obtain a formed green body; S4: sintering the formed green body to obtain the ICO target material.

3. The method according to claim 2, characterized in that in step S2, during the vacuum defoaming process, the pressure in the sealed container is -0.1 MPa--0.2 MPa. The treated slurry is flowed into the mold under an air pressure of 0.2-0.7 MPa.

4. The method according to claim 2, characterized in that step S3 further comprises the steps of:

5. The method according to claim 2, characterized in that in step S3, the pressure holding and standing time is 5-10 h.

6. The method according to claim 2, characterized in that in step S4, the sintering is three-step sintering, the first-step sintering temperature is 1600-1700 °C, the second-step sintering temperature is 1450-1550 °C, and the third-step sintering temperature is 1100-1250 °C. ​ 7. The method according to claim 6, characterized in that the second sintering step and the third sintering step further comprise the following steps: Pass in oxygen, the passing in speed is 20~35 L / min, the pressure is 3.0~3.5 kg / cm 2 .

8. The method according to claim 6, characterized in that the second sintering and the third sintering are further comprised of a holding step, and the time ratio of the holding step of the second sintering to the third sintering is 5-8:3-5.

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