Titanium-silicon target material as well as preparation method and application thereof
By using SPS process and Ti backing plate composite sintering, a high-density and highly uniform titanium-silicon sputtering target was prepared, which solved the problem of easy cracking of titanium-silicon sputtering target in traditional process and realized efficient production and high-quality titanium-silicon sputtering target application.
Patent Information
- Application Number
- CN202511608513.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-05
- Publication Date
- 2026-02-13
AI Technical Summary
Traditional titanium-silicon sputtering processes tend to form brittle titanium-silicon compounds at high silicon content, leading to increased sputtering hardness and brittleness, making the cladding difficult to remove and prone to cracking during PVD, which makes it difficult to meet the multifunctional requirements of high-end fields.
By employing the spark plasma sintering (SPS) process, rapid heating sintering under vacuum conditions through two heat preservation steps, combined with the Ti backplate composite sintering process, a high-density and highly uniform titanium-silicon target material is prepared, avoiding silicon segregation and crack formation.
It has enabled the efficient production of high-quality titanium-silicon sputtering targets, solving the problems of low density and uneven structure in traditional processes, and improving the yield and stability during use.
Smart Images
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Abstract
Description
Technical Field
[0001] This application relates to the technical field of PVD coating, specifically to a titanium-silicon target, its preparation method, and its application. Background Technology
[0002] Titanium-silicon targets are alloy targets composed of titanium (Ti) and silicon (Si) in a specific ratio. They are the core "raw material carrier" in physical vapor deposition (PVD, such as sputtering coating) processes. High-energy particles bombard the target surface, causing titanium-silicon atoms or ions to detach from the target and deposit onto a substrate (such as silicon wafers, metals, or glass), forming a titanium-silicon thin film with specific functions. Its properties are closely related to its composition and microstructure, making it an indispensable key material in high-end fields such as hard coatings, semiconductors, microelectronics, and new energy.
[0003] As a core raw material in the high-end coating field, titanium-silicon sputtering targets directly affect the quality and reliability of downstream devices, serving as a key support for the development of strategic emerging industries such as semiconductors, new energy, and optics. With domestic technological breakthroughs and increasing downstream demand, titanium-silicon sputtering targets are upgrading towards higher purity, larger sizes, and greater customization. Simultaneously, to meet the multifunctional needs of downstream applications, titanium-silicon sputtering targets are upgrading from "binary alloys" to "multi-element composites," that is, by introducing a third element (Me, such as B, Zr, W, Mo, etc.) to form TiSiMe composite sputtering targets. For example, introducing Zr can improve the high-temperature resistance of the sputtering target, adapting to the coating requirements of aero-engines; introducing B can reduce the thin film resistivity and optimize the performance of semiconductor interconnect layers.
[0004] Traditional titanium-silicon sputtering mainly employs hot isostatic pressing (HIP) technology. The process involves mixing titanium and silicon powders, encasing them in a metal sheath (such as stainless steel or titanium alloy), and holding the mixture at 900-1200℃ and 100-200MPa for 4-10 hours to densify the powder. While this process can produce sputtering targets with uniform microstructure and high density, and is suitable for large-size (diameter > 200mm) targets, it has significant drawbacks. When the silicon content is >30 at%, Ti and Si rapidly form numerous brittle titanium-silicon compounds (such as Ti5Si3 and TiSi2) during sintering, increasing the hardness and brittleness of the sputtering target. This makes it difficult to remove the sheath, and the increased brittleness also easily leads to cracking during cooling and sheath removal after HIP. In addition, when the Si content is greater than 30%, the greater brittleness makes it difficult to withstand the high power and cooling water pressure during the PVD process, which easily leads to the problem of target material cracking during use. Summary of the Invention
[0005] To address the aforementioned technical problems, this application provides a titanium-silicon target, its preparation method, and its application.
[0006] In a first aspect, this application provides a method for preparing a titanium-silicon target material, comprising the following steps: uniformly mixing elemental powders, SPS sintering, and machining into a finished product; The SPS sintering process parameters are as follows: Hold at a first temperature of 700-800℃ for 3-5 minutes; then raise the temperature to a second temperature of 900-1200℃ and hold for 10-30 minutes; the entire sintering process is carried out under vacuum with a vacuum degree of 10. -1 -10 -3 Pa, with a pressure of 20-40 MPa, after sintering, the pressure is released and cooled to room temperature; The titanium-silicon target material is composed of the following components by atomic percentage: Ti 60-99 at%, Si 1-40 at%, Me 0-20; Me is selected from one or more metallic and non-metallic elements such as C, B, Zr, W, Co, Mo, Cr, Ta, Nb, V, and La.
[0007] The rapid sintering method for titanium-silicon targets provided in this application uses spark plasma sintering (SPS) to prepare titanium-silicon targets. The SPS process achieves rapid heating of the powder (heating rate can reach 100-500℃ / min) through Joule heating generated by pulsed current and plasma activation effect. The SPS sintering process sets two-stage holding times: the first stage holding time is 3-5 min, and the second stage holding time is 10-30 min, which can complete the sintering. Compared with the HIP process, the production cycle is shortened by more than 90%, and no metal casing is required. Graphite molds can be used directly, which greatly reduces costs.
[0008] Meanwhile, the rapid heating of SPS can suppress the excessive growth of titanium silicon compounds, reduce the brittleness of the target material, and effectively improve the yield of high silicon content (Si=30-40at%) targets, becoming a core technical path to solve the pain points of traditional processes.
[0009] In the SPS sintering process for preparing titanium-silicon targets, directly heating to 900-1200℃ and holding for a period of time results in silicon segregation in the prepared target. Through multiple experiments, the applicant discovered that holding the titanium-silicon alloy powder at a temperature step of 700-800℃ for a short time before heating to 900-1200℃ and holding for a period of time effectively prevents silicon segregation during SPS sintering and improves the compositional uniformity of the target. Simultaneously, setting two temperature steps allows for densification of the titanium-silicon alloy during sintering, effectively closing pores and further improving the density and density stability of the target.
[0010] Preferably, the titanium-silicon target material is composed of the following components by atomic percentage: Ti 60-70 at%, Si 30-40 at%, Me 0-20 at%; Me is selected from one or more of C, B, Zr, W, Co, Mo, Cr, Ta, Nb, V, and La.
[0011] Preferably, the process parameters for SPS sintering are as follows: holding at a first temperature of 720-780℃ and a pressure of 20-30MPa for 3-5 minutes; then raising the temperature to a second temperature of 1000-1100℃ and a pressure of 30-40MPa, holding for 15-25 minutes; the entire sintering process is carried out under vacuum, with a vacuum degree of 10. -1 -10 -3 Pa, after sintering, the pressure is released and cooled to room temperature.
[0012] Preferably, the process parameters for SPS sintering are as follows: holding at a first temperature of 730-770℃ and a pressure of 20-30MPa for 3-5 minutes; then raising the temperature to a second temperature of 1020-1080℃ and a pressure of 30-40MPa, holding for 15-25 minutes; the entire sintering process is carried out under vacuum, with a vacuum degree of 10. -1 -10 -3 Pa, after sintering, the pressure is released and cooled to room temperature.
[0013] In one specific implementation, the SPS sintering process parameters are as follows: a first temperature of 750℃ and a pressure of 25MPa are maintained for 4 minutes; then the temperature is raised to a second temperature of 1050℃ and a pressure of 35MPa, and maintained for 20 minutes; the entire sintering process is carried out under vacuum, with a vacuum degree of 10. -2 Pa, after sintering, the pressure is released and cooled to room temperature.
[0014] Preferably, the method for cooling to room temperature is as follows: cooling to a third temperature with the furnace and holding for 30-60 minutes, then air cooling to room temperature; the third temperature = the first temperature - (150℃-250℃).
[0015] Preferably, the method for cooling to room temperature is as follows: cool with the furnace to a third temperature and hold for 40-50 minutes, then air cool to room temperature; the third temperature = the first temperature - (170℃ - 220℃).
[0016] In one specific implementation, the method for cooling to room temperature is as follows: cooling to a third temperature with the furnace and holding for 45 minutes, then air cooling to room temperature; the third temperature = the first temperature - 200°C.
[0017] During the preparation of the target material, the cooling method has a certain impact on the quality of the target material. If it is cooled directly in the furnace, or if the furnace cooling temperature is too high or too low, the finished titanium-silicon target material is prone to defects such as internal cracks and poor density uniformity. Through experiments, the applicant found that cooling the target material in the furnace to the aforementioned third temperature and holding it for 30-60 minutes, followed by air cooling to room temperature, can avoid the formation of micro-cracks inside the target material and improve density uniformity.
[0018] Preferably, when the Si atom content of the titanium silicon target material is >30%, the method further includes the following steps: using a Ti backplate composite sintering process, after the elemental powders are mixed evenly, they are placed on the Ti target material backplate, so that the powder and the backplate are integrated during the SPS sintering process.
[0019] To address the increased brittleness caused by Si content >30%, this application employs a Ti-backplate composite sintering process for TiSi targets with Si content >30%. A Ti backplate is pre-placed in the mold, followed by the loading of powder. During sintering, the powder and backplate bond together. This structure effectively solves the cracking problem of single-layer high-silicon, low-titanium targets during use.
[0020] Secondly, this application provides a titanium-silicon target material, which is prepared using the above-described preparation method.
[0021] Preferably, the relative density of the titanium-silicon target is 99.5-99.9%.
[0022] Thirdly, this application provides the application of the aforementioned titanium-silicon sputtering target in PVD coating.
[0023] In summary, the technical solution of this application has the following effects: This application overcomes the problems of low target density and poor microstructure uniformity in the conventional hot isostatic pressing process for preparing titanium-silicon targets, and provides a novel preparation method for titanium-silicon targets that can be mass-produced, has high production efficiency, and stable target quality.
[0024] This application employs powder metallurgy technology, using SPS discharge plasma sintering with two combined heat preservation steps for sintering, to prepare titanium-silicon targets with excellent properties such as high density, uniform structure, and no segregation. Attached Figure Description
[0025] Figure 1 The images show a top view (a) and a side view (b) of the titanium-silicon target material in Example 1. Detailed Implementation
[0026] The present application will be further described in detail below with reference to embodiments, comparative examples and performance test results. These embodiments should not be construed as limiting the scope of protection claimed in this application. Example
[0027] Examples 1-7 Examples 1-7 provide a titanium-silicon target and its preparation method, respectively.
[0028] The difference between Examples 1-7 is that the process parameters for SPS sintering are different, as shown in Table 1.
[0029] The specific preparation methods of the titanium-silicon targets in Examples 1-7 are shown below.
[0030] (1) Uniform mixing of elemental powders: Titanium powder and silicon powder are weighed according to the atomic percentage of "Ti=65at%, Si=35at%" and then mixed uniformly in a three-dimensional mixer to obtain titanium-silicon alloy powder; wherein, the purity of titanium powder is 99.8wt% and the particle size is -250 mesh; the purity of silicon powder is 99.8wt% and the particle size is -300 mesh.
[0031] Place the Ti target backplate at the bottom of the graphite mold; uniformly fill the graphite mold containing the Ti target backplate with the mixed titanium-silicon alloy powder.
[0032] (2) SPS sintering: The graphite mold is placed in an SPS discharge plasma sintering furnace, and then heated to the first temperature at the first heating rate according to the process parameters shown in Table 1, and held at that temperature; then heated to the second temperature at the second heating rate, and held at that temperature; the entire sintering process is evacuated to a vacuum degree of 10. -2 The pressure is 20-40 MPa. After sintering, the pressure is released and the furnace is cooled to the third temperature and held. Then it is air-cooled to room temperature to obtain titanium silicon intermediate billet.
[0033] (3) Machining into finished product: According to the finished product drawings, the titanium-silicon intermediate billet is machined to obtain the titanium-silicon target product; the target diameter D = 162 mm, and the thickness = 12 mm. The top view (a) and side view (b) of the prepared titanium-silicon target are shown below. Figure 1 As shown.
[0034] Table 1. Process parameters for SPS sintering in Examples 1-7 Examples 8-10 Examples 8-10 respectively provide a titanium-silicon target and its preparation method.
[0035] The difference between the above embodiments and Embodiment 1 is that the methods for cooling to room temperature are different, as detailed below.
[0036] In Example 8: The furnace was cooled to room temperature.
[0037] In Example 9: the furnace was cooled to a third temperature of 650°C (third temperature = first temperature - 100°C), held for 45 minutes, and then air-cooled to room temperature.
[0038] In Example 10: the furnace was cooled to a third temperature of 450°C (third temperature = first temperature - 300°C), held for 45 minutes, and then air-cooled to room temperature.
[0039] All other process parameters in the above embodiments are the same as those in Embodiment 1.
[0040] Comparative Example Comparative Example 1 Comparative Example 1 provides a titanium-silicon target and its preparation method.
[0041] The difference between Comparative Example 1 and Example 1 is that hot isostatic pressing sintering process is used instead of SPS sintering, as shown below.
[0042] The hot isostatic pressing method involves holding the target at 1000℃ and 150MPa for 4 hours. Results showed that after cooling and removing the cladding, cracks and uneven Si distribution were observed in the microstructure.
[0043] In Comparative Example 1, all other process parameters were the same as in Example 1.
[0044] Comparative Examples 2-6 Comparative Examples 2-6 each provide a titanium-silicon target and its preparation method.
[0045] The difference between the above comparative example and Example 1 is that the process parameters for SPS sintering are different, as shown in Table 2.
[0046] Table 2. Process parameters for SPS sintering in Comparative Examples 2-6 All other process parameters in the above comparative examples are the same as those in Example 1.
[0047] Performance testing Appearance: Observe the surface of the finished titanium-silicon target material for any segregation issues.
[0048] Relative density: The measured density was determined using the Archimedes displacement method. The relative density is equal to the measured density divided by the theoretical density. Here, the theoretical density of the titanium-silicon target is calculated using the elemental powder mixing method. Using the preparation methods provided in the examples or comparative examples, three titanium-silicon targets were prepared in parallel. The relative density of the titanium-silicon targets was measured, and the stability of the relative density was evaluated.
[0049] Si content: The Si content in the titanium-silicon sputtering target was detected by ICP method. Three random samples were taken from the titanium-silicon sputtering target, and the Si content was measured to evaluate the uniformity of Si content.
[0050] Test results are shown in Table 3.
[0051] Table 3 Performance test results of titanium-silicon sputtering materials in the examples and comparative examples. As shown in Table 3 above, the test results indicate that in Comparative Example 1, the titanium-silicon target material prepared using the hot isostatic pressing (HIP) sintering process cracked during the cooling process. In Comparative Example 2, the SPS sintering process at 1050℃ was used directly. In Comparative Examples 3-4, the first sintering temperature was too low or too high, and in Comparative Examples 5-6, the second sintering time was too short or too long. These results in poor density stability and uniformity of Si content in the prepared titanium-silicon target materials, leading to poor overall microstructure uniformity.
[0052] In contrast, the SPS sintering process technology used in this application embodiment, which involves "holding at a first temperature of 700-800℃ for 3-5 minutes, then raising the temperature to a second temperature of 900-1200℃ and holding for 10-30 minutes", produces titanium-silicon targets that do not crack and have excellent properties such as high relative density and uniform structure without segregation.
[0053] By comparing the test results of Examples 1-7, it can be seen that by controlling the temperature of the first sintering in the SPS sintering process to 720-780℃, the temperature of the second sintering to 1000-1100℃, and the time of the second sintering to 15-25min, the performance of the target material can be further improved.
[0054] Comparing the test results of Examples 1 and 8-10, it can be seen that the cooling method has a certain impact on the quality of the target material. If the target material is cooled directly in the furnace, or if the furnace cooling temperature is too high or too low, the resulting titanium-silicon target material is prone to defects with poor uniformity. Through experiments, the applicant found that using furnace cooling to the third temperature, controlling the third temperature to be equal to the first temperature - (170℃ - 220℃) and holding it at that temperature, followed by air cooling to room temperature, can further improve the compositional and density uniformity of the finished titanium-silicon target material. Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.
Claims
1. A method for preparing a titanium-silicon target, characterized in that, Includes the following steps: The elemental powders are mixed evenly, sintered using SPS, and machined into finished products. The SPS sintering process parameters are as follows: Hold at a first temperature of 700-800℃ for 3-5 minutes; then raise the temperature to a second temperature of 900-1200℃ and hold for 10-30 minutes; the entire sintering process is carried out under vacuum with a vacuum degree of 10. -1 -10 -3 Pa, with a pressure of 20-40 MPa, after sintering, the pressure is released and cooled to room temperature; The titanium-silicon target material is composed of the following components by atomic percentage: Ti 60-99 at%, Si 1-40 at%, Me 0-20; Me is selected from one or more of the following metals and non-metals: C, B, Zr, W, Co, Mo, Cr, Ta, Nb, V, La, etc.
2. The method for preparing the titanium-silicon target according to claim 1, characterized in that, The titanium-silicon target material is composed of the following components by atomic percentage: Ti 60-70 at%, Si 30-40 at%, Me 0-20 at%; Me is selected from one or more of the following metals and non-metals: C, B, Zr, W, Co, Mo, Cr, Ta, Nb, V, La, etc.
3. The method for preparing the titanium-silicon target according to claim 1, characterized in that, The SPS sintering process parameters are as follows: Under a first temperature of 720-780℃ and a pressure of 20-30MPa, hold for 3-5 minutes; then raise the temperature to a second temperature of 1000-1100℃ and a pressure of 30-40MPa, hold for 15-25 minutes; the entire sintering process is carried out under vacuum, with a vacuum degree of 10. -1 -10 -3 Pa, after sintering, the pressure is released and cooled to room temperature.
4. The method for preparing the titanium-silicon target according to claim 3, characterized in that, The SPS sintering process parameters are as follows: Under a first temperature of 730-770℃ and a pressure of 20-30MPa, hold for 3-5 minutes; then raise the temperature to a second temperature of 1020-1080℃ and a pressure of 30-40MPa, hold for 15-25 minutes; the entire sintering process is carried out under vacuum, with a vacuum degree of 10. -1 -10 -3 Pa, after sintering, the pressure is released and cooled to room temperature.
5. The method for preparing the titanium-silicon target according to claim 1, characterized in that, The method for cooling to room temperature is as follows: cool with the furnace to the third temperature and hold for 30-60 minutes, then air cool to room temperature; the third temperature = the first temperature - (150℃-250℃).
6. The method for preparing the titanium-silicon target according to claim 1, characterized in that, The method for cooling to room temperature is as follows: cool with the furnace to the third temperature and hold for 40-50 minutes, then air cool to room temperature; the third temperature = the first temperature - (170℃ - 220℃).
7. The method for preparing the titanium-silicon target according to claim 6, characterized in that, When the Si atom content of the titanium silicon target material is >30%, the following steps are also included: using a Ti backplate composite sintering process, after the elemental powder is mixed evenly, it is placed on the Ti target material backplate, so that the powder and the backplate are integrated during the SPS sintering process.
8. A titanium-silicon target material, characterized in that, It is prepared using the preparation method according to any one of claims 1-7.
9. The titanium-silicon sputtering target according to claim 8, characterized in that, The relative density of the titanium-silicon target is 99.5-99.9%. The application of the titanium-silicon sputtering target as described in any one of claims 8-9 in PVD coating.