Anti-molten titanium-based composite target material, preparation method and application thereof

Abstract

The application belongs to the technical field of target materials, and discloses an anti-molten titanium-based composite target material and a preparation method and application thereof. Raw materials for preparing the titanium-based composite target material include metal oxides and titanium powder, wherein the metal oxides are selected from tantalum oxide and / or niobium oxide; and the mass ratio of the metal oxides to the titanium powder is (12-47):(53-88). The application uses specific metal oxides and titanium powder as main preparation raw materials, and the metal oxides have similar evaporation melting points with the titanium-based target material, so that the thermodynamic stability of the target material is ensured while the stable sublimation of the target material is not blocked. Meanwhile, a reinforcing agent is added as a low-chemical-activity additive, and the thermodynamic stability is improved in cooperation with the metal oxides, and the reinforcing agent does not react with the target material and does not affect the deposition and crystallization of the titanium-based thin film. The titanium-based composite target material of the application ensures the stability of the shape structure of the target material and improves the quality of the thin film under the premise of reducing the cost of the target material.

Description

Technical Field

[0001] This invention belongs to the field of target technology, specifically relating to an anti-molten titanium-based composite target, its preparation method, and its application. Background Technology

[0002] Transparent conductive film (TCO) glass is a functional material with a transparent conductive oxide film deposited on the glass surface. Currently, TCO faces the major challenge of indium shortage, while titanium-based films have become one of the candidates to replace indium-based films due to their low cost and non-toxicity and bio-friendly properties.

[0003] In coating processes such as plasma deposition (RPD) and magnetron sputtering (PVD), the target material is the most important factor determining the performance of the thin film. Since coating technology has certain requirements on the conductivity of the target material, metallic Ti targets can be used to replace traditional ceramic targets. However, due to the many phases of Ti and the very poor stability of Ti compounds, titanium-based targets are extremely prone to melting and nodulation under the harsh conditions of coating, which seriously limits the preparation and use of titanium-based thin films.

[0004] Therefore, developing a stable molten titanium-based metal target material is of great practical significance. Summary of the Invention

[0005] This invention aims to solve the target melting problem caused by the multiphase state of Ti element, and proposes a melt-resistant titanium-based composite target, its preparation method and application. The titanium-based composite target can ensure the stability of the target structure and improve the film quality while reducing the cost of the target.

[0006] The inventive concept of this invention is as follows: This invention uses specific metal oxides (such as tantalum oxide and / or niobium oxide) and titanium powder as the main raw materials. Utilizing the similar evaporation melting points of the metal oxides and titanium powder, the thermodynamic stability of the titanium-based target material is ensured while its stable sublimation is not hindered. During the coating process, the target material maintains a stable morphology, consuming layer by layer from the center. Simultaneously, a certain amount of reinforcing agents (such as silicon carbide, vanadium oxide, tungsten oxide, molybdenum oxide, titanium carbide, niobium carbide, aluminum nitride, zirconium diboride, and molybdenum disilicide) are added as low-chemically active additives. These additives, in conjunction with the metal oxides, enhance thermodynamic stability without chemically reacting with the target material, thus not affecting the deposition and crystallization of the titanium-based thin film. Therefore, the titanium-based composite target material of this invention can completely solve the target melting problem caused by the multiphase state of Ti, reducing target material costs while ensuring stability. It can be widely applied to various coating technologies, increasing production capacity, and improving film quality while ensuring the stability of the target material's structure.

[0007] To solve the above-mentioned technical problems, the first aspect of the present invention provides a titanium-based composite target material, wherein the raw materials for preparing the titanium-based composite target material include metal oxide and titanium powder, wherein the metal oxide is selected from tantalum oxide and / or niobium oxide; and the mass ratio of the metal oxide to the titanium powder is (12-47):(53-88).

[0008] Specifically, tantalum oxide and niobium oxide, under the thermal diffusion effect of sintering, can form "metal oxide-titanium" interstitial solid solutions and substitutional solid solutions, providing a suitable thermal stability range. During the coating process, this can improve the thermal stability and resistance to ion beam impact at the microscopic level. Simultaneously, the metal oxide and titanium powder have similar melting points, allowing the metal oxide to slowly evaporate and ionize simultaneously with the titanium, thus improving thermal stability without hindering the ionization process of the target material during coating.

[0009] In some embodiments of the present invention, the mass ratio of the metal oxide to the titanium powder is (15-35):(65-85). Preferably, the mass ratio of the metal oxide to the titanium powder is (17-32):(68-83).

[0010] In some embodiments of the present invention, the particle size of the metal oxide is 1-5 μm and the purity is ≥99.99%.

[0011] In some embodiments of the present invention, the titanium powder has a particle size of 1-5 μm and a purity of ≥99.99%.

[0012] In some embodiments of the present invention, the raw materials for preparing the titanium-based composite target material further include at least one of a reinforcing agent, a dispersant, and a binder.

[0013] In some embodiments of the present invention, the reinforcing agent is selected from at least one of silicon carbide, vanadium oxide, tungsten oxide, molybdenum oxide, titanium carbide, niobium carbide, aluminum nitride, zirconium diboride, and molybdenum disilicide.

[0014] Specifically, these reinforcing agents possess excellent thermodynamic stability and extremely low chemical activity. While providing the target material with good resistance to melting, they do not react strongly with the target material itself, thus avoiding target poisoning caused by changes in target composition due to ion beam ionization. Therefore, using these materials as reinforcing agents is beneficial for further enhancing the thermal shock resistance of the target material. Simultaneously, the reinforcing agents form a continuous physical network at the mesoscopic level, permeating the "metal oxide-titanium" target material, exhibiting a significant skeletal effect, ensuring that the evaporation and ionization process of the target material proceeds in an orderly and stable manner.

[0015] In some embodiments of the present invention, the reinforcing agent has a particle size of 500 nm-5 μm and a purity of ≥99.99%. The silicon carbide can be silicon carbide powder or silicon carbide whiskers; the silicon carbide powder has a particle size of 500 nm-5 μm, and the silicon carbide whiskers have a diameter of 0.1-0.5 μm, a length of 5-20 μm, and a strength of 7-10 GPa.

[0016] In some embodiments of the present invention, the amount of the reinforcing agent is 0.5-20% of the total mass of the metal oxide and titanium powder; preferably, the amount of the reinforcing agent is 10-15% of the total mass of the metal oxide and titanium powder.

[0017] In some embodiments of the present invention, the dispersant is selected from at least one of polyvinylpyrrolidone (PVP), ammonium polyacrylate (PAA-NH4), polymethacrylic acid (PMAA), polyethyleneimine (PEI), and polyacrylamide (PAM).

[0018] In some embodiments of the present invention, the amount of the dispersant is 0.1-5% of the total mass of the metal oxide and titanium powder; preferably, the amount of the dispersant is 0.5-2% of the total mass of the metal oxide and titanium powder.

[0019] In some embodiments of the present invention, the adhesive is selected from at least one of polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyacrylonitrile (PAN), acrylic emulsion, and emulsion-type styrene-butadiene rubber (SBR).

[0020] In some embodiments of the present invention, the amount of adhesive used is 1-10% of the total mass of the metal oxide and titanium powder; preferably, the amount of adhesive used is 1-3% of the total mass of the metal oxide and titanium powder.

[0021] A second aspect of the present invention provides a method for preparing the above-mentioned titanium-based composite target, comprising the following steps: (1) Take the raw materials for preparing the titanium-based composite target material, perform wet ball milling and spray granulation to obtain mixed powder; (2) The mixed powder is pressed into shape to obtain a target blank; (3) After dehydrating and degreasing the target blank, it is sintered to obtain the titanium-based composite target.

[0022] In some embodiments of the present invention, step (1) includes the following steps in the preparation process of the mixed powder: Metal oxides and titanium powder are ball-milled in a solvent to obtain a slurry; after drying, grinding and sieving, a mixed powder is obtained; then the mixed powder is spray-granulated to obtain the mixed powder body.

[0023] In some embodiments of the present invention, step (1) includes the following steps in the preparation process of the mixed powder: Metal oxide, titanium powder, and dispersant are added to a solvent containing a reinforcing agent and ball-milled once to obtain slurry A; then a binder is added to slurry A and ball-milled a second time to obtain slurry B; then slurry B is dried, ground, and sieved to obtain a mixed powder; finally, the mixed powder is spray-granulated to obtain the mixed powder body.

[0024] In some embodiments of the present invention, the reinforcing agent is an acid-modified reinforcing agent, and the acid used for acid washing is concentrated nitric acid with a concentration of 65-75 wt%.

[0025] In some embodiments of the present invention, the acid-washing modification process includes the following steps: first, the reinforcing agent is soaked in concentrated nitric acid for 1-6 hours, dispersed by magnetic stirring at a rotation speed of 300-800 rpm; then, it is washed with deionized water until neutral, vacuum dried for 6-12 hours, and sieved through a 30-50 mesh to obtain a reinforcing agent with a powder particle size ≤500 μm; then, it is ultrasonically dispersed in deionized water for 5-30 minutes at a frequency of 60-120 kHz; thus, the acid-washing modified reinforcing agent is obtained.

[0026] Specifically, concentrated nitric acid is used for pickling. On the one hand, the strong oxidizing and dissolving properties of concentrated nitric acid remove metal impurities and surface contaminants from the surface of the reinforcing agent. On the other hand, the strong oxidizing properties of concentrated nitric acid will graft -OH groups onto the surface of the reinforcing agent, improving its surface hydrophilicity and surface energy, which is beneficial to the subsequent ball milling and mixing processes.

[0027] In some embodiments of the present invention, the solvent is selected from deionized water or anhydrous ethanol, and the amount of the solvent used is 40-80 wt% of the total amount of material.

[0028] In some embodiments of the present invention, in step (1), the ball milling speed is 200-600 r / min and the ball milling time is 6-12 hours.

[0029] In some embodiments of the present invention, in step (1), the spray granulation is carried out in a spray granulator, wherein the process parameters of the spray granulator include: rotation speed 4000-6000 r / min, inlet air temperature 180-200℃, and outlet air temperature 50-100℃.

[0030] In some embodiments of the present invention, in step (1), the particle size of the mixed powder is such that it passes through a 100-200 mesh sieve and the particle size is ≤150μm.

[0031] In some embodiments of the present invention, in step (2), the pressing pressure is 50-200 MPa and the pressing time is 5-30 minutes.

[0032] In some embodiments of the present invention, in step (3), the dehydration temperature is 130-300°C, the dehydration time is 2-4 hours, and the heating rate is 0.5-1°C / min.

[0033] In some embodiments of the present invention, in step (3), the degreasing temperature is 310-460°C, the degreasing time is 2-4 hours, and the heating rate is 0.5-1°C / min.

[0034] In some embodiments of the present invention, in step (3), the sintering temperature is 950-1400℃, the sintering time is 3-8 hours, and the heating rate is 2-10℃ / min.

[0035] In some embodiments of the present invention, the sintering atmosphere is an inert atmosphere.

[0036] A third aspect of the present invention provides a titanium-based thin film, which is formed by coating the above-mentioned titanium-based composite target material.

[0037] In some embodiments of the present invention, the titanium-based thin film is a titanium oxide thin film.

[0038] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages: (1) This invention uses specific metal oxides (such as tantalum oxide and / or niobium oxide) and titanium powder as the main raw materials. Through the thermal diffusion of the metal oxides during sintering, interstitial solid solutions and substitutional solid solutions of "metal oxide-titanium" are formed, providing a suitable thermal stability range. This improves the thermal stability and resistance to ion beam impact of the target material at the microscopic level during the coating process. At the same time, due to their similar melting points, the metal oxides will slowly evaporate and ionize with the titanium, thereby improving thermal stability without hindering the ionization process of the target material during coating.

[0039] (2) To further enhance the thermal shock resistance of the target material, specific reinforcing agents (such as silicon carbide, vanadium oxide, tungsten oxide, molybdenum oxide, titanium carbide, niobium carbide, aluminum nitride, zirconium diboride, and molybdenum disilicide) are introduced into the target material of the present invention. These agents utilize their excellent thermodynamic stability and extremely low chemical activity to provide the target material with good resistance to melting, and will not produce strong chemical reactions with the target material itself, thus avoiding target poisoning caused by changes in the target material composition due to ion beam ionization. Simultaneously, the reinforcing agents form a continuous physical network that permeates the "metal oxide-titanium" target material, exhibiting a significant skeletal effect, ensuring that the evaporation and ionization process of the target material proceeds in an orderly and stable manner.

[0040] (3) This invention improves the density of the target material by controlling the particle size of the raw materials, thus avoiding cracking of the target material during sintering due to uneven particle size, improving the quality of the target material, and saving process costs. At the same time, by regulating the sintering temperature regime, the highly concentrated internal stress phenomenon of the target material during sintering is reduced, thereby avoiding melting, collapse, or nodule formation during coating. The target material does not melt at 800℃, and the quality retention rate can reach 97.667-98.623%. Attached Figure Description

[0041] Figure 1 This is the phase diagram of Ti-O.

[0042] Figure 2 Images showing the coating process of titanium-based target materials prepared in Comparative Example 7 and Example 1; Figure 3 Images of the titanium-based target materials prepared in Comparative Example 7 and Example 1 after coating.

[0043] Figure 4 SEM images of the titanium-based target coating areas prepared in Comparative Example 7 and Example 1.

[0044] Figure 5 The differential scanning calorimetry spectrum of the mixed powder prepared in Example 1. Detailed Implementation

[0045] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0046] Example 1 A titanium-based composite target material is prepared from raw materials including Ta2O5, Ti powder, AlN, PVP and PEG-2000, wherein the mass ratio of Ta2O5 to Ti powder is 20:80, and the amounts of AlN, PVP and PEG-2000 are 10%, 1% and 1% of the total mass of Ta2O5 and Ti powder, respectively; the average particle size of Ta2O5, Ti powder and AlN is 1μm and the purity is ≥99.99%.

[0047] The preparation method of the above-mentioned titanium-based composite target includes the following steps: (1) Place AlN in a container and soak it in concentrated nitric acid (68wt%) for 6 hours, and disperse it by magnetic stirring at a speed of 500 rpm. Then wash it with deionized water until neutral, vacuum dry it for 8 hours, and sieve it through a 30-mesh sieve to obtain an acid-modified AlN reinforcing agent with a particle size ≤500μm. Then pour the acid-modified AlN reinforcing agent into deionized water and ultrasonically disperse it for 10 minutes at a frequency of 100kHz to obtain a pretreated solution.

[0048] (2) Add Ta2O5, Ti and PVP to the pretreatment solution obtained in step (1) and ball mill. Set the ball mill speed to 300 r / min and ball mill for 6 hours. Take out the slurry. Add PEG-2000 and continue ball milling for 2 hours to obtain a mixed slurry. Then dry and grind the obtained mixed slurry and sieve it through an 80-mesh sieve to obtain a mixed powder with a particle size ≤200 μm. Then use a spray granulator to granulate the mixed powder. The process parameters of the spray granulator are: speed 4500 r / min, inlet air temperature 175℃, outlet air temperature 75℃, and sieve it through a 100-mesh sieve to obtain a mixed powder with a particle size ≤150 micrometers.

[0049] (3) The mixed powder obtained in step (2) is placed into a cylindrical mold with a diameter of 25 mm and pressed into shape by a hydraulic press. The molding pressure is 100 MPa and the molding time is 10 minutes to obtain a cylindrical target blank with a diameter of 25 mm and a height of 30 mm.

[0050] (4) The target blank obtained in step (3) is placed in a high-temperature sintering furnace for dehydration, degreasing and sintering. Pure argon gas is introduced throughout the process. The temperature regime is as follows: first, the temperature is raised to 200°C at a heating rate of 1°C / min and held for 2 hours. Then, the temperature is raised to 350°C at the same heating rate and held for 2 hours to complete dehydration and degreasing. Then, the temperature is raised to 1200°C at a heating rate of 2°C / min and held for 3 hours to perform atmospheric pressure sintering to obtain the titanium-based composite target of this embodiment.

[0051] Example 2 A titanium-based composite target material is prepared from raw materials including Ta2O5, Nb2O5, Ti powder, TiC, PVP, and PVA, wherein the mass ratio of Ta2O5, Nb2O5, and Ti powder is 10:10:80, and the amounts of TiC, PVP, and PVA are 10%, 1%, and 1% of the total mass of Ta2O5, Nb2O5, and Ti powder, respectively; the average particle size of Ta2O5, Nb2O5, Ti powder, and TiC is 1 μm, and the purity is ≥99.99%.

[0052] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0053] Example 3 A titanium-based composite target material is prepared from raw materials including Nb2O5, Ti powder, PAA-NH4 and PEG-2000, wherein the mass ratio of Nb2O5 to Ti powder is 30:70, the amounts of PAA-NH4 and PEG-2000 are 1% and 1% of the total mass of Nb2O5 and Ti powder, respectively; the average particle size of Nb2O5 and Ti powder is 1 μm, and the purity is ≥99.99%.

[0054] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0055] Example 4 A titanium-based composite target material is prepared from raw materials including Nb2O5, Ti powder, SiC, TiC, PMAA, and PVB, wherein the mass ratio of Nb2O5 to Ti powder is 20:80, and the amounts of SiC, TiC, PMAA, and PVB are 5%, 5%, 1%, and 1% of the total mass of Nb2O5 and Ti powder, respectively; the average particle size of Nb2O5, Ti powder, SiC, and TiC is 1 μm, and the purity is ≥99.99%.

[0056] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0057] Example 5 A titanium-based composite target material is prepared from raw materials including Ta2O5, Ti powder, V2O5, WO3, PEI and PAN, wherein the mass ratio of Ta2O5 to Ti powder is 15:85, and the amounts of V2O5, WO3, PEI and PAN are 3%, 7%, 1% and 1% of the total mass of Ta2O5 and Ti powder, respectively; the average particle size of Ta2O5, Ti powder, V2O5 and WO3 is 1 μm, and the purity is ≥99.99%.

[0058] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0059] Example 6 A titanium-based composite target material is prepared from raw materials including Ta2O5, Ti powder, MoO3, and PEG-2000, wherein the mass ratio of Ta2O5 to Ti powder is 25:75, and the amounts of MoO3 and PEG-2000 are 10% and 1% of the total mass of Ta2O5 and Ti powder, respectively; the average particle size of Ta2O5, Ti powder, and MoO3 is 1 μm, and the purity is ≥99.99%.

[0060] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0061] Example 7 A titanium-based composite target material is prepared from raw materials including Nb2O5, Ti powder, NbC, and PMAA, wherein the mass ratio of Nb2O5 to Ti powder is 27:73, and the amounts of NbC and PMAA are 10% and 1% of the total mass of Nb2O5 and Ti powder, respectively; the average particle size of Nb2O5, Ti powder, and NbC is 1 μm, and the purity is ≥99.99%.

[0062] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0063] Example 8 A titanium-based composite target material is prepared from raw materials including Ta2O5, Ti powder, MoSi2, and MoO3, wherein the mass ratio of Ta2O5 to Ti powder is 32:68, and the amounts of MoSi2 and MoO3 are 6% and 4% of the total mass of Ta2O5 and Ti powder, respectively; the average particle size of Ta2O5, Ti powder, MoSi2, and MoO3 are all 1 μm, and the purity is ≥99.99%.

[0064] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0065] Example 9 A titanium-based composite target material is prepared from Nb2O5 and Ti powder, wherein the mass ratio of Nb2O5 to Ti powder is 35:65; the average particle size of Nb2O5 and Ti powder is 1 μm and the purity is ≥99.99%.

[0066] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0067] Example 10 A titanium-based composite target material is prepared from raw materials including Ta2O5, Nb2O5, and Ti powder, wherein the mass ratio of Ta2O5, Nb2O5, and Ti powder is 20:20:60; the average particle size of Ta2O5, Nb2O5, and Ti powder is 1 μm, and the purity is ≥99.99%.

[0068] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials such as metal oxide, dispersant, binder and reinforcing agent were changed to obtain the titanium-based composite target of this example.

[0069] Comparative Example 1 A titanium-based composite target material is prepared from Ti powder, ZrB2, PVP and PEG-2000, wherein the amounts of ZrB2, PVP and PEG-2000 are 30%, 1% and 1% of the mass of Ti powder, respectively; the average particle size of Ti powder and ZrB2 is 1 μm and the purity is ≥99.99%.

[0070] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0071] Comparative Example 2 A titanium-based composite target material is prepared from Ti powder, MoSi2, PVP and PEG-2000, wherein the amounts of MoSi2, PVP and PEG-2000 are 15%, 1% and 1% of the mass of Ti powder, respectively; the average particle size of Ti powder and MoSi2 is 1 μm and the purity is ≥99.99%.

[0072] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0073] Comparative Example 3 A titanium-based composite target material, the raw materials for which are prepared include Ti powder, SiC fiber, PVP and PEG-2000, wherein: SiC w The amounts of PVP and PEG-2000 used are 1%, 1%, and 1% of the Ti powder mass, respectively; the average particle size of the Ti powder is 1 μm, and the purity is ≥99.99%; the SiC fibers have a diameter of 0.1-0.5 μm, a length of 5-20 μm, and a strength of 7-10 GPa. Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0074] Comparative Example 4 A titanium-based composite target material is prepared from raw materials including Nb2O5, Ti powder, ZrB2, PVP, and PEG-2000, wherein the mass ratio of Nb2O5 to Ti powder is 5:95, and the amounts of ZrB2, PVP, and PEG-2000 are 1%, 1%, and 1% of the total mass of Nb2O5 and Ti powder, respectively; the average particle size of Nb2O5 and Ti powder is 1 μm, and the purity is ≥99.99%.

[0075] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0076] Comparative Example 5 A titanium-based composite target material is prepared from raw materials including Ta2O3, Nb2O5, Ti powder, SiC powder, PVP, and PEG-2000, wherein the mass ratio of Ta2O3, Nb2O5, and Ti powder is 1:1:98, and the amounts of SiC powder, PVP, and PEG-2000 are 1%, 1%, and 1% of the total mass of Ta2O3, Nb2O5, and Ti powder, respectively; the average particle size of Ta2O3, Nb2O5, Ti powder, and SiC powder is 1 μm, and the purity is ≥99.99%.

[0077] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0078] Comparative Example 6 A titanium-based composite target material is prepared from Nb2O5, Ti powder, PVP, and PEG-2000, wherein the mass ratio of Nb2O5 to Ti powder is 10:90, and the amounts of PVP and PEG-2000 are 1% and 1% of the total mass of Nb2O5 and Ti powder, respectively; the average particle size of Nb2O5 and Ti powder is 1 μm, and the purity is ≥99.99%.

[0079] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based composite target of this comparative example.

[0080] Comparative Example 7 A titanium-based composite target material is prepared from Ti powder, PVP and PEG-2000, wherein the amounts of PVP and PEG-2000 are 1% and 1% of the mass of Ti powder, respectively; the average particle size of Ti powder is 1 μm and the purity is ≥99.99%.

[0081] Referring to the preparation method of the titanium-based composite target in Example 1, the types and amounts of raw materials of metal oxide and reinforcing agent were changed to obtain the titanium-based target of this comparative example.

[0082] Performance testing The target samples prepared in Examples 1-4 and Comparative Examples 1-7 were coated by reactive plasma deposition, with a distance of 511 mm between the target and the substrate. The melting status and target mass retention rate at 800 °C were recorded. The results are shown in Table 1. The melting severity level of the target was: severe melting > melting > no melting.

[0083] Table 1:

[0084] Table 1 shows that with the combined effect of a certain amount of metal oxide and reinforcing agent, the target material can achieve complete non-melting. However, when the added metal oxide or reinforcing agent is insufficient, the target material begins to melt. With only a small amount or no metal oxide or reinforcing agent added, severe melting occurs, forming a molten pool on the substrate. This demonstrates that specific metal oxides and reinforcing agents can significantly improve the thermal stability and resistance to ion beam impact of the target material. Under the thermal diffusion effect of sintering, the metal oxide forms interstitial and substitutional solid solutions of "metal oxide-titanium" at the microscopic level. During sublimation, a small amount of Ti is deposited on the film, resulting in an extremely low consumption rate. This provides a certain degree of support to the target material without hindering the sublimation deposition process. The reinforcing agent possesses extremely low chemical activity and excellent thermal stability. At the mesoscopic level, the reinforcing agent forms a continuous physical network, filling the "metal oxide-titanium" target material and exhibiting a significant skeletal effect. Under the combined action of these two materials, the target material can be stably consumed without melting.

[0085] Figure 1 The Ti-O binary phase diagram shows that Ti possesses multiple phase states, resulting in poor stability. It undergoes an α→β phase transition at 882℃ and transforms into a liquid state above 1670℃. Therefore, titanium sputtering targets are highly susceptible to melting and collapse during the coating process.

[0086] Figure 2 Comparative Example 7 ( Figure 2 a) and Example 1 ( Figure 2 b) Images of the prepared target material during the coating process show that the 100% Ti target material prepared in Comparative Example 7 underwent severe melting and collapse during the coating process; while the composite target material prepared in Example 1 can maintain the original cylindrical blank shape, and the upper end gradually sublimates and ionizes without melting and collapse, ensuring the smooth progress of the coating process.

[0087] Figure 3 Comparative Example 7 ( Figure 3 a) and Example 1 ( Figure 3b) Images of the titanium-based target after coating show that after being subjected to high temperature and high energy impact from the ion beam in the coating chamber, the 100% Ti target prepared in Comparative Example 7 could no longer maintain its complete shape, and the whole thing collapsed and rotted; while the composite target prepared in Example 1 only showed the separation of the coating at the upper end, and the lower end still maintained the cylindrical shape of the blank, and had good resistance to melting.

[0088] Figure 4 Comparative Example 7 ( Figure 4 a) and Example 1 ( Figure 4 b) SEM images of the titanium-based target coating area. From the microscopic morphology, the 100% Ti target coating area prepared in Comparative Example 7 reflects the morphology of the target after liquid / semi-liquid cooling formed by the high temperature and high energy impact of the ion beam. This indicates that the 100% Ti target has undergone severe melting during the coating process, so it is unable to support the target shape. In contrast, the composite target coating area prepared in Example 1 forms a rough physical mesh-like surface, and many large grains can still be seen. Some of these grains sublimate normally under the high temperature and high energy impact of the ion beam, while others bond together to form a skeleton supporting the target. Therefore, the melting phenomenon of the target is greatly reduced, and the melting phenomenon is basically not visible.

[0089] Figure 5 The differential calorimetry spectrum of the mixed powder prepared in Example 1 shows that there are two endothermic peaks in the mixed powder, which are in the temperature ranges of 200-260℃ and 310-360℃ respectively. That is, the degreasing step is held in these two temperature ranges, which allows the organic matter to volatilize better.

[0090] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A titanium-based composite target material, characterized by, The raw materials for preparing the titanium-based composite target include metal oxide and titanium powder, wherein the metal oxide is selected from tantalum oxide and / or niobium oxide; the mass ratio of the metal oxide to the titanium powder is (12-47):(53-88).

2. The titanium-based composite target material according to claim 1, characterized in that, The raw materials for preparing the titanium-based composite target also include at least one of a reinforcing agent, a dispersant, and a binder.

3. The titanium-based composite target material according to claim 2, characterized in that, The reinforcing agent is selected from at least one of silicon carbide, vanadium oxide, tungsten oxide, molybdenum oxide, titanium carbide, niobium carbide, aluminum nitride, zirconium diboride, and molybdenum disilicide. The amount of the reinforcing agent is 0.5-20% of the total mass of the metal oxide and titanium powder.

4. The titanium-based composite target material according to claim 2, characterized in that, The dispersant is selected from at least one of polyvinylpyrrolidone, ammonium polyacrylate, polymethacrylic acid, polyethyleneimine, and polyacrylamide, and the amount of the dispersant is 0.1-5% of the total mass of the metal oxide and titanium powder.

5. The titanium-based composite target material according to claim 2, characterized in that, The adhesive is selected from at least one of polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, acrylic emulsion, and emulsion-type styrene-butadiene rubber, and the amount of the adhesive is 1-10% of the total mass of the metal oxide and titanium powder.

6. A method for preparing a titanium-based composite target as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Take the raw materials for preparing the titanium-based composite target material, perform wet ball milling and spray granulation to obtain mixed powder; (2) The mixed powder is pressed into shape to obtain a target blank; (3) After dehydrating and degreasing the target blank, it is sintered to obtain the titanium-based composite target.

7. The method for preparing the titanium-based composite target according to claim 6, characterized in that, The pressing pressure is 50-200 MPa, and the pressing time is 5-30 minutes.

8. The method for preparing the titanium-based composite target according to claim 6, characterized in that, The dehydration temperature is 130-300℃, and the dehydration time is 2-4 hours; and / or, the degreasing temperature is 310-460℃, and the degreasing time is 2-4 hours.

9. The method for preparing the titanium-based composite target according to claim 6, characterized in that, The sintering temperature is 950-1400℃, and the sintering time is 3-8 hours.

10. A titanium thin film, characterized in that, It is formed by coating with the titanium-based composite target material as described in any one of claims 1-5.

Images