Alpha-phase tungsten-molybdenum alloy film and preparation method thereof

Abstract

The invention discloses a preparation method of an alpha-phase tungsten-molybdenum alloy film, which comprises the following specific steps: step 1, simultaneously depositing a WxMo1-x alloy layer on a substrate by a magnetron sputtering method, and x is more than or equal to 0.2 and less than or equal to 0.8; and 2, annealing is conducted, specifically, after deposition of the WxMo1-x alloy layer is finished, annealing treatment is conducted on the sample. The invention further discloses the alpha-phase tungsten-molybdenum alloy film prepared through the method, and the tungsten-molybdenum alloy film is in an alpha phase and has good thermal stability.

Description

Technical Field

[0001] The invention belongs to the technical field of tungsten-molybdenum alloy film materials, and in particular relates to an alpha-phase tungsten-molybdenum alloy film, and also relates to a preparation method of the alpha-phase tungsten-molybdenum alloy film. Background Art

[0002] Tungsten-molybdenum alloy is an important high-temperature material with excellent high-temperature strength, oxidation resistance and wear resistance, as well as good corrosion resistance. Therefore, it is widely used in aerospace, national defense and high-temperature industrial fields. With the development of miniaturization of devices, the demand for high-quality tungsten-molybdenum alloy films is more urgent. In addition, to meet the needs of different fields, the ratio of tungsten and molybdenum in the alloy needs to be adjusted and the performance optimized. Due to the complex phase structure of tungsten, there are alpha phase and beta phase. Beta phase tungsten is a metastable phase with poor thermal stability. It will transform into alpha phase tungsten at a certain film thickness and temperature. Therefore, high-quality alpha phase and adjustable composition tungsten-molybdenum alloy is more valuable for application. Summary of the invention

[0003] The first object of the present invention is to provide a method for preparing an alpha-phase tungsten-molybdenum alloy film. The present invention forms a film by co-sputtering tungsten and molybdenum and performs vacuum annealing to achieve the preparation of the alpha-phase tungsten-molybdenum alloy film.

[0004] A second object of the present invention is to provide an alpha-phase tungsten-molybdenum alloy film, which is in the alpha phase and has good thermal stability.

[0005] The first technical solution adopted by the present invention is a method for preparing an alpha phase tungsten-molybdenum alloy film, and the specific steps are as follows: Step 1: Deposit W on the substrate simultaneously by magnetron sputtering x Mo 1-x Alloy layer, where 0.2≤x≤0.8; Step 2: Annealing: x Mo 1-x After the alloy layer deposition is completed, the sample is annealed.

[0006] The present invention is also characterized in that: In step 1, the substrate is a Si substrate, SiO 2 Substrate or Si substrate with pre-printed pattern.

[0007] In step 1, W in the alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 18 sccm-36 sccm.

[0008] In step 1, a magnetron sputtering system is used to simultaneously deposit W and Mo on the substrate; the sputtering power of the W target is 20W-60W, and the sputtering power of the Mo target is 13W-60W; the sputtering time is 128s-300s.

[0009] The substrate rotation speed in the magnetron sputtering system is 5rpm-20rpm.

[0010] In step 2, the annealing temperature is 500°C-700°C, In step 2, the annealing time is 0.5h-2h.

[0011] The second technical solution adopted by the present invention is that the alpha phase tungsten-molybdenum alloy film is prepared by the above method.

[0012] The beneficial effects of the present invention are: Since the stress accumulation of the beta-phase tungsten-molybdenum alloy will be significantly increased under high temperature conditions, resulting in an increase in its thermodynamic instability, the tungsten-molybdenum alloy structure is reorganized and transformed into a stable alpha-phase tungsten-molybdenum alloy through the method of the present invention, and the prepared alpha-phase tungsten-molybdenum alloy film has good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic diagram of the structure of the alpha phase tungsten-molybdenum alloy film of the present invention; Figure 2 The [W 0.8 Mo 0.2 ] XRD of alloy thin films; Figure 3 The [W 0.6 Mo 0.4 ] XRD of alloy thin films; Figure 4 The [W 0.5 Mo 0.5 ] XRD of alloy thin films; Figure 5 The [W 0.4 Mo 0.6 ] XRD of alloy thin films; Figure 6 The [W 0.2 Mo 0.8 ] XRD of alloy thin films; Figure 7 The [W 0.5 Mo 0.5 ] XRD of alloy thin films; Figure 8 The [W 0.5 Mo 0.5 ]XRD of alloy thin films.

[0014] In the figure, 1. substrate, 2. W x Mo 1-x Alloy layer. DETAILED DESCRIPTION

[0015] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0016] The present invention provides a method for preparing an alpha phase tungsten-molybdenum alloy film, and the specific steps are as follows: Step 1: Deposit W on substrate 1 by magnetron sputtering x Mo 1-x Alloy layer 2, wherein 0.2≤x≤0.8; In step 1, substrate 1 is a Si substrate, SiO 2 Substrate or Si substrate with pre-printed pattern.

[0017] In step 1, W in the alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 18 sccm-36 sccm.

[0018] In step 1, a magnetron sputtering system is used to simultaneously deposit W and Mo on a substrate; the sputtering power of the W target is 20W-60W, and the sputtering power of the Mo target is 13W-60W; The splashing time is 128s-300s.

[0019] The substrate rotation speed in the magnetron sputtering system is 5rpm-20rpm.

[0020] Step 2: Annealing: x Mo 1-x After the alloy layer 2 is deposited, the sample is annealed.

[0021] In step 2, the annealing temperature is 500°C-700°C, In step 2, the annealing time is 0.5h-2h.

[0022] The present invention also provides an alpha phase tungsten-molybdenum alloy film, such as Figure 1 As shown, including W set from top to bottom x Mo 1-x The alloy layer 2 and the substrate 1 are prepared by the above method.

[0023] The specifications of the instruments used in all the following examples are as follows: Magnetron sputtering system: Brand: Kurt J.Lesker, Model: PVD 75 Proline.

[0024] Vacuum annealing furnace: brand: Dongfang Chenjing, model: high temperature magnetic field heating furnace.

[0025] Multifunctional X-ray diffractometer: brand: Japan Rigaku, model: Smartlab SE.

[0026] Embodiment 1: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 80% and the content of Mo is 20% according to the atomic number percentage. W and Mo are deposited on the substrate 1 (the substrate 1 is a Si substrate) by DC magnetron sputtering to obtain W. x Mo 1-x Alloy layer 2.

[0027] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 18 sccm.

[0028] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate. In this embodiment, the sputtering power of the W target was 60 W, and the sputtering power of the Mo target was 13 W. The sputtering time was 300 s, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0029] After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at 600°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 80%, and the Mo content was 20%.

[0030] XRD was used to measure the crystal structure of the samples. Figure 2 As shown, the sample annealed at 600 °C exhibits a W-Mo alloy with an alpha phase structure.

[0031] Embodiment 2: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 60% and the content of Mo is 40% according to the atomic number percentage. W and Mo are deposited on the substrate 1 (the substrate 1 is a Si substrate) by DC magnetron sputtering to obtain W. x Mo 1-x Alloy layer 2.

[0032] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 36 sccm.

[0033] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate; in this embodiment, the sputtering power of the W target was 60 W, and the sputtering power of the Mo target was 19 W. The sputtering time was 226 s, the sputtering gas pressure was 23 sccm, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0034] After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at 600°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 60%, and the Mo content was 40%.

[0035] XRD was used to measure the crystal structure of the samples. Figure 3 As shown, the sample annealed at 600 °C exhibits a W-Mo alloy with an alpha phase structure.

[0036] Embodiment 3: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 50% and the content of Mo is 50% according to the atomic number percentage. W and Mo are deposited on the substrate 1 (the substrate 1 is a Si substrate) by DC magnetron sputtering to obtain W. x Mo 1-x Alloy layer 2.

[0037] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 30 sccm.

[0038] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate; in this embodiment, the sputtering power of the W target was 60 W, and the sputtering power of the Mo target was 40 W. The sputtering time was 158 s, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0039] After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at 600°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 50%, and the Mo content was 50%.

[0040] XRD was used to measure the crystal structure of the samples. Figure 4 As shown, the sample annealed at 600 °C exhibits a W-Mo alloy with an alpha phase structure.

[0041] Embodiment 4: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 40% and the content of Mo is 60% according to the atomic number percentage. W and Mo are deposited on the substrate 1 (the substrate 1 is a Si substrate) by DC magnetron sputtering to obtain W. x Mo 1-x Alloy layer 2.

[0042] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 25 sccm.

[0043] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate; in this embodiment, the sputtering power of the W target was 65 W, and the sputtering power of the Mo target was 60 W. The sputtering time was 128 s, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0044] After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at 600°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 40%, and the Mo content was 60%.

[0045] XRD was used to measure the crystal structure of the samples. Figure 5 As shown, the sample annealed at 600 °C exhibits a W-Mo alloy with an alpha phase structure.

[0046] Embodiment 5: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 20% and the content of Mo is 80% according to the atomic number percentage. W and Mo are deposited on the substrate 1 (the substrate 1 is a Si substrate) by DC magnetron sputtering to obtain W. x Mo 1-x Alloy layer 2.

[0047] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 20 sccm.

[0048] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate. In this embodiment, the sputtering power of the W target was 20 W, and the sputtering power of the Mo target was 60 W. The sputtering time was 172 s, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0049] After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at 600°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 20%, and the Mo content was 80%.

[0050] XRD was used to measure the crystal structure of the samples. Figure 6 As shown, the sample annealed at 600 °C exhibits a W-Mo alloy with an alpha phase structure.

[0051] Embodiment 6: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 50%, and the content of Mo is 50% according to the atomic number percentage. The DC magnetron sputtering method is used to simultaneously deposit the W on the substrate 1 (the substrate 1 is SiO 2 W and Mo are deposited on the substrate to obtain W x Mo 1-x Alloy layer 2.

[0052] In this embodiment, the sputtering power of the W target is 60 W, and the sputtering power of the Mo target is 40 W. The sputtering time is 158 s, and the substrate rotation speed of the magnetron sputtering system is 10 rpm.

[0053] W in alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 19 sccm. The magnetron sputtering system is used to deposit W and Mo on the substrate at the same time; After deposition, the sample was placed in a vacuum annealing furnace for non-in-situ annealing at a temperature of 500°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 50%, and the Mo content was 50%.

[0054] XRD was used to measure the crystal structure of the samples. Figure 7 As shown, the sample annealed at 500 °C exhibits a W-Mo alloy with an alpha phase structure.

[0055] Embodiment 7: Method for preparing tungsten-molybdenum alloy film having alpha phase, W x Mo 1-x In the alloy layer 2, the content of W is 50%, and the content of Mo is 50% according to the atomic number percentage. The DC magnetron sputtering method is used to simultaneously deposit the W on the substrate 1 (the substrate 1 is SiO 2 W and Mo are deposited on the substrate to obtain W x Mo 1-x Alloy layer 2.

[0056] W in alpha phase tungsten-molybdenum alloy filmx Mo 1-x The alloy layer 2 is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 33 sccm.

[0057] A magnetron sputtering system was used to simultaneously deposit W and Mo on the substrate; in this embodiment, the sputtering power of the W target was 60 W, and the sputtering power of the Mo target was 40 W. The sputtering time was 158 s, and the substrate rotation speed of the magnetron sputtering system was 10 rpm.

[0058] After deposition, the sample was placed in a vacuum annealing furnace for ex-situ annealing at 700°C for 1 h. The thickness of the alloy layer was 16 nm, the W content was 50%, and the Mo content was 50%.

[0059] XRD was used to measure the crystal structure of the samples. Figure 8 As shown, the sample annealed at 700 °C exhibits a W-Mo alloy with an alpha phase structure.

Claims

1. A method for preparing an alpha phase tungsten-molybdenum alloy film, characterized in that: The specific steps are as follows: Step 1: Deposit W on substrate (1) by magnetron sputtering x Mo 1-x Alloy layer (2), wherein 0.2≤x≤0.8; Step 2: Annealing: x Mo 1-x After the alloy layer (2) is deposited, the sample is annealed.

2. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 1, characterized in that: In step 1, the substrate (1) is a Si substrate, a SiO2 substrate or a Si substrate with a pre-printed pattern.

3. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 2, characterized in that: In step 1, W in the alpha phase tungsten-molybdenum alloy film x Mo 1-x The alloy layer (2) is deposited by a magnetron sputtering system, the sputtering atmosphere is argon, and the argon flow rate is 18 sccm-36 sccm.

4. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 2, characterized in that: In step 1, a magnetron sputtering system is used to simultaneously deposit W and Mo on the substrate (1); the sputtering power of the W target is 20W-65W, and the sputtering power of the Mo target is 13W-60W; the sputtering time is 128s-300s.

5. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 3, characterized in that: The substrate rotation speed in the magnetron sputtering system is 5rpm-20rpm.

6. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 1, characterized in that: In step 2, the annealing temperature is 500°C-700°C.

7. The method for preparing an alpha-phase tungsten-molybdenum alloy thin film according to claim 1, characterized in that: In step 2, the annealing time is 0.5h-2h.

8. Alpha phase tungsten-molybdenum alloy film, characterized in that: The method is prepared by any one of claims 1 to 7.

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