Semiconductor nitride film material and preparation method thereof
By preparing Al1-xSixN1-yOy compound thin films, the problem that existing nitride thin films cannot simultaneously meet the requirements of insulation, high temperature resistance, wear resistance and hydrophobicity in complex environments has been solved, and high-performance thin film material applications have been realized.
Patent Information
- Application Number
- CN202511546182.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-28
- Publication Date
- 2026-01-23
AI Technical Summary
Existing nitride films are difficult to simultaneously meet the requirements of insulation, high temperature resistance, wear resistance and hydrophobicity in a variety of complex environments.
Using Al1-xSixN1-yOy compounds as thin film materials, thin films with excellent insulation, thermal stability, wear resistance and hydrophobicity were prepared by high-power pulsed magnetron sputtering on the substrate, controlling the Si and O contents within a specific range, and combining appropriate substrate heating and gas mixing ratio.
The prepared thin film material remains stable at 900℃~1200℃, with a resistivity greater than 2.5×1015Ωcm, a hardness of 15GPa~22GPa, and a surface free energy of less than 25mJ/m2, satisfying the comprehensive properties of insulation, high temperature resistance, wear resistance and hydrophobicity.
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Figure CN121381179A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of semiconductor thin film materials, and particularly relates to a semiconductor nitride thin film material and a preparation method thereof. BACKGROUND
[0002] Thin film materials play a crucial role as protective films in modern engineering technology, especially in the field of semiconductor devices that require high-performance protection, such as against high-temperature environments, electronic device protection, surface protection, and anti-fouling and corrosion resistance. Among them, thin film materials with insulation and high-temperature resistance gradually become one of the hotspots of advanced material research because they can meet the complex needs in extreme environments.
[0003] Nitride thin films have potential application value in the semiconductor field due to their own characteristics, such as: zirconium nitride (ZrN) has high hardness, good corrosion resistance, and certain high-temperature resistance, and has certain applications in the protection field; silicon nitride (Si3N4) has good chemical stability, high hardness, and high insulation resistance, and its oxidation resistance temperature can reach about 1200℃. However, in some special application scenarios with multiple complex environments, the protective film is required to meet the requirements of insulation, high-temperature resistance, wear resistance, and hydrophobicity at the same time, and the existing nitride thin film is difficult to meet this requirement.
[0004] Therefore, how to provide a nitride thin film that can stably have the comprehensive performance of insulation, high-temperature resistance, wear resistance, and hydrophobicity in multiple complex environments is a technical problem that needs to be solved at present. SUMMARY
[0005] In view of the above technical problems, the present application provides a semiconductor nitride thin film material and a preparation method thereof, which has excellent insulation, thermal stability, wear resistance, and hydrophobicity, and can meet the application requirements in multiple complex environments.
[0006] The present application provides a semiconductor nitride thin film material, the components of the thin film material include a compound with a chemical formula of Al 1- x Si x N 1-y O y , wherein , ; the compound is hexagonal, and the crystal space group is P63mc.
[0007] In some embodiments, the resistivity of the thin film material is greater than 2.5×10 15 Ω cm, which has a hexagonal wurtzite crystal form stable at 900-1200 DEG C, a hardness of 15-22 GPa, a contact angle with water greater than 111 DEG, and a surface free energy less than 25 mJ / m 2 The application further provides a preparation method of the semiconductor nitride thin film material. cleaning the substrate; sputtering the target material by high-power pulse magnetron sputtering in an argon and nitrogen mixed gas environment, to deposit compound Al 1-x Si x N 1-y O y , wherein, , to obtain the semiconductor nitride thin film material.
[0008] In some embodiments, the volume percentage of nitrogen in the argon and nitrogen mixed gas is 50-80%, and the rest is argon.
[0009] In some embodiments, the average power is 600-1000 W, the duty cycle is 7.5-15%, the frequency is 500-1000 Hz, and the sputtering gas pressure is 0.5-1.0 Pa during the high-power pulse magnetron sputtering.
[0010] In some embodiments, the substrate is additionally heated during the sputtering, and the heating temperature is 250 DEG C.
[0011] In some embodiments, the deposition time is 60-90 min.
[0012] In some embodiments, the thickness of the deposited thin film is 1100-1500 nm.
[0013] Compared with the prior art, the application has the following advantages and beneficial effects: 1. The semiconductor nitride thin film material provided by the application has a well-crystallized Al 1-x Si x N 1-y O y , a resistivity greater than 2.5*10 15 Ω cm, excellent insulation, a crystal form stable at 900-1200 DEG C, excellent thermal stability, a dense structure, a hardness of 15-22 GPa, a contact angle with water greater than 111 DEG, and a surface free energy less than 25 mJ / m 2, has excellent hydrophobicity, thus, as a kind of insulating high-temperature-resistant wear-resistant hydrophobic functional protective film material, it helps to promote the development of aerospace, new energy system, precision electronic component surface protection and other fields; 2、The semiconductor nitride thin film material provided by the present application limits the Si content and O content through x and y, and appropriate Si element doping can refine the crystal grains, form hard Si-N phase to improve hardness, but too high Si content will reduce the hydrophobicity of the thin film material due to the generation of hydrophilic groups (Si-OH) on the surface due to surface oxidation, and too high O content will generate low-density, brittle oxides (such as Al2O3, SiO2), weaken the crystal boundary combination and reduce the hardness, resulting in reduced wear resistance, therefore, limiting x and y in the range of 、 , the Si content and O content in the compound are moderate, so that the thin film material can have excellent insulation, thermal stability, wear resistance and hydrophobicity; 3、The preparation method of the semiconductor nitride thin film material provided by the present application is pollution-free, low in cost, simple and easy to operate, and short in thin film growth period, and the prepared thin film material can meet the requirements of insulation, high-temperature resistance, wear resistance and hydrophobicity at the same time, has good crystallization quality, dense and stable structure, smooth surface and strong adhesion. BRIEF DESCRIPTION OF DRAWINGS
[0014] Figure 1 It is a photo of the semiconductor nitride thin film material provided by the present application example 1; Figure 2 It is a photo of the semiconductor nitride thin film material provided by the present application example 5; Figure 3 It is a SEM graph of the thin film material provided by the present application example 1, example 3 and comparative example 1-4, wherein (a) corresponds to example 1, (b) corresponds to example 3, (c) corresponds to comparative example 1, (d) corresponds to comparative example 2, (e) corresponds to comparative example 3, and (f) corresponds to comparative example 4; Figure 4 It is the resistivity of the thin film material provided by the present application examples 1-5 and comparative examples 1-4; Figure 5 It is an XRD graph of the thin film material provided by the present application example 1 after high-temperature annealing; Figure 6 It is a hardness graph of the thin film material provided by the present application examples 1-5 and comparative examples 1-4; Figure 7Contact angle measurement results of the thin film material provided in the present application embodiments 1-5 and comparative examples 1-4, wherein (a) corresponds to embodiment 1, (b) corresponds to embodiment 2, (c) corresponds to embodiment 3, (d) corresponds to embodiment 4, (e) corresponds to embodiment 5, (f) corresponds to comparative example 1, (g) corresponds to comparative example 2, (h) corresponds to comparative example 3, (i) corresponds to comparative example 4. DETAILED DESCRIPTION
[0015] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.
[0016] The present application embodiment provides a semiconductor nitride thin film material, the components of the thin film material include a compound with a chemical formula of Al 1-x Si x N 1-y O y , wherein, , ; the compound is hexagonal, and the crystal space group is P63mc.
[0017] The semiconductor nitride thin film material has a well-crystallized Al 1-x Si x N 1-y O y , the resistivity is greater than 2.5×10 15 Ω cm, has excellent insulation, maintains a stable hexagonal wurtzite crystal form at 900℃-1200℃, has excellent thermal stability, has a densification structure, the hardness can reach 15GPa-22GPa, the contact angle with water is greater than 111°, the surface free energy is less than 25mJ / m 2 , has excellent hydrophobicity, thus, as an insulating high-temperature-resistant wear-resistant hydrophobic functional protective film material, it helps to promote the development of the fields of aerospace, new energy systems, and surface protection of precision electronic components. At the same time, in the semiconductor nitride thin film material, the Si content and the O content are limited by x and y, appropriate Si element doping can refine the crystal grains, form hard Si-N phase to improve the hardness, but too high Si content will generate hydrophilic groups (Si-OH) due to surface oxidation, reducing the hydrophobicity of the thin film material, and too high O content will generate low-density, brittle oxides (such as Al2O3, SiO2), weakening the crystal boundary combination and reducing the hardness, resulting in reduced wear resistance, thus, x and y are limited to , The Si content and O content in the compound can be moderate, so as to ensure that the thin film material has excellent insulation, thermal stability, wear resistance and hydrophobicity. It should be noted that when x and y are both 0, the thin film material component is AlN, which has a hexagonal wurtzite lattice, and when x and y are not 0, Si atoms can replace the positions of Al atoms, and O atoms replace the positions of N atoms, so as to form Al 1-x Si x N 1-y O y The solid solution still maintains a hexagonal system.
[0018] The embodiment of the present application also provides a preparation method of the semiconductor nitride thin film material. S1, cleaning a substrate; S2, using Al or Al and Si as target materials, performing sputtering on the target materials in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method, so as to deposit a compound Al 1-x Si x N 1-y O y , wherein, , to obtain the semiconductor nitride thin film material.
[0019] The preparation method of the semiconductor nitride thin film material is pollution-free, low in cost, simple and easy to implement, and short in thin film growth period. Meanwhile, the thin film material prepared can meet the requirements of insulation, high-temperature resistance, wear resistance and hydrophobicity at the same time, has good crystallization quality, a dense and stable structure, a smooth surface and strong adhesion.
[0020] For step S1, it should be noted that the substrate includes but is not limited to single crystal silicon, ordinary glass, quartz glass, Au, Pt, ITO conductive glass, Al2O3, SiC, GaN and the like. It should also be noted that the specific steps of cleaning the substrate are as follows: (1) using anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol as cleaning liquids to clean the substrate in sequence, and the substrate is placed in an ultrasonic cleaner containing the cleaning liquid during each cleaning; (2) performing ion cleaning on the substrate in a pure argon gas environment, and the pressure during ion cleaning is greater than or equal to 1.0 Pa, the cleaning power is greater than 350 W, and the cleaning time is 10-15 min. Preferably, the pressure during ion cleaning is 1.0 Pa, the cleaning power is 380 W, and the cleaning time is 15 min.
[0021] For step S2, it should be noted that the high-power pulsed magnetron sputtering is a prior art, and the specific operation steps thereof are well known to those skilled in the art, which will not be described here.
[0022] Preferably, the volume percentage of nitrogen in the argon and nitrogen mixed gas is 50% to 80%, and the rest is argon. It should be noted that too low nitrogen content in the mixed gas will lead to an increase in the O content in the compound, resulting in a decrease in the hardness of the thin film material.
[0023] Preferably, when high-power pulse magnetron sputtering is performed, the average power is 600 W to 1000 W, the duty cycle is 7.5% to 15%, the frequency is 500 Hz to 1000 Hz, and the sputtering pressure is 0.5 Pa to 1.0 Pa. Using the above-mentioned preferred sputtering parameter range, the crystallinity of the nitride can be improved, a dense and uniform microstructure can be obtained, and a small surface roughness can be achieved, thereby obtaining an insulating, high-temperature-resistant, wear-resistant and hydrophobic thin film material. If the average power is too low, the sputtering energy will be low, leading to an increase in the O content in the compound, resulting in a decrease in the hardness of the thin film material. If the average power is too high, the sputtering energy will be high, leading to an increase in the Si content in the compound, resulting in a decrease in the hydrophobicity of the thin film material. If the duty cycle is too high, the Si content in the compound will increase, resulting in an increase in the hardness of the thin film material while a decrease in the hydrophobicity of the thin film material. It should be further noted that a purity of the target material of more than 99.995% is beneficial to ensure a low impurity content in the thin film material.
[0024] Preferably, the substrate is additionally heated during sputtering, and the heating temperature is 250°C. By additionally heating the substrate, the surface diffusion ability of atoms during deposition can be significantly improved, thereby reducing the defect density and improving the structural density and mechanical properties of the thin film.
[0025] Preferably, the deposition time is 60 min to 90 min, which is beneficial to obtain a thin film material with a suitable thickness.
[0026] Preferably, the thickness of the deposited thin film is 1100 nm to 1500 nm. Within the above-mentioned preferred thickness range, the thin film material prepared simultaneously satisfies the requirements of insulation, high-temperature resistance, wear resistance and hydrophobicity, which is beneficial to the subsequent application of the thin film.
[0027] In order to more clearly and specifically introduce the semiconductor nitride thin film material and the preparation method thereof provided by the embodiments of the present application, the following will be described in combination with specific embodiments.
[0028] Embodiment 1 (1) The single crystal silicon was used as the substrate, and anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol were used as the cleaning liquids to clean the substrate in sequence. During each cleaning, the substrate was placed in an ultrasonic cleaner containing the cleaning liquid and cleaned for 15 min. (2) The substrate was ion cleaned in a pure argon gas environment. During cleaning, the pressure was 1.0 Pa, the cleaning power was 380 W, and the cleaning time was 15 min. (3) using Al as the target material, the purity of the target material is 99.999%, and the target material is sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit a compound AlN on the substrate to obtain a thin film material; wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 70% (i.e., the argon flow is 30 sccm, and the nitrogen flow is 70 sccm); when the high-power pulsed magnetron sputtering is performed, the average power is 600 W, the duty cycle is 7.5%, the frequency is 1000 Hz, the gas pressure is kept at 0.8 Pa during the sputtering process, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 90 min. The thickness of the finally deposited thin film is 1050 nm, and the chemical formula of the compound constituting the thin film material is AlN, which belongs to the hexagonal system and has a crystal space group of P63mc, and the photograph is as shown in Figure 1 .
[0029] Example 2 (1) using single crystal silicon as the substrate, the substrate is sequentially cleaned with anhydrous ethanol, ultrapure water, acetone, and anhydrous ethanol as the cleaning liquid, and the substrate is placed in an ultrasonic cleaner containing the cleaning liquid for cleaning for 15 min each time; (2) the substrate is ion cleaned in a pure argon gas environment, and the pressure is 1.0 Pa, the cleaning power is 380 W, and the cleaning time is 15 min; (3) using Al and Si as the target materials, the purity of the target materials is 99.999%, and the target materials are sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit a compound Al 1-x Si x N 1-y O y on the substrate to obtain a thin film material; wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 60% (i.e., the argon flow is 40 sccm, and the nitrogen flow is 60 sccm); when the high-power pulsed magnetron sputtering is performed, the average power is 800 W, the duty cycle is 10%, the frequency is 800 Hz, the gas pressure is kept at 1.0 Pa during the sputtering process, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 75 min. The thickness of the finally deposited thin film is 1100 nm, and the chemical formula of the compound constituting the thin film material is Al 0.85 Si 0.15 N 0.976 O 0.024 , which belongs to the hexagonal system and has a crystal space group of P63mc.
[0030] Example 3 (1) using single crystal silicon as the substrate, using anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol as the cleaning liquid to clean the substrate in turn, and placing the substrate in an ultrasonic cleaner containing the cleaning liquid for 15 min each time; (2) performing ion cleaning on the substrate in a pure argon gas environment, wherein the pressure is 1.0 Pa, the cleaning power is 380 W, and the cleaning time is 15 min; (3) using Al and Si as the target material, the purity of the target material is 99.999%, and the target material is sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit compound Al 1-x Si x N 1-y O y on the substrate, thereby obtaining a thin film material; wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 50% (i.e., the argon flow is 50 sccm, and the nitrogen flow is 50 sccm); when the high-power pulsed magnetron sputtering is performed, the average power is 1000 W, the duty cycle is 15%, the frequency is 500 Hz, the gas pressure is kept at 0.5 Pa during the sputtering process, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 60 min. The thickness of the finally deposited thin film is 1500 nm, the chemical formula of the compound constituting the thin film material is Al 0.7 Si 0.3 N 0.95 O 0.05 , which belongs to the hexagonal system and the crystal space group is P63mc.
[0031] Example 4 (1) using single crystal silicon as the substrate, using anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol as the cleaning liquid to clean the substrate in turn, and placing the substrate in an ultrasonic cleaner containing the cleaning liquid for 15 min each time; (2) performing ion cleaning on the substrate in a pure argon gas environment, wherein the pressure is 1.0 Pa, the cleaning power is 380 W, and the cleaning time is 15 min; (3) using Al and Si as the target material, the purity of the target material is 99.999%, and the target material is sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit compound Al 1-x Si x N 1-y O y, wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 80% (i.e., the argon flow rate is 20 seem, and the nitrogen flow rate is 80 seem); during the high-power pulsed magnetron sputtering, the average power is 1000 W, the duty cycle is 15%, the frequency is 1000 Hz, the pressure during the sputtering process is kept at 0.5 Pa, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 90 min. The finally deposited film has a thickness of 1300 nm, and the compound constituting the film material has a chemical formula of Al 0.76 Si 0.24 N 0.997 O 0.003 , which belongs to a hexagonal system and has a crystal space group of P63mc.
[0032] Example 5 The difference from Example 1 is that a glass substrate is used. The compound constituting the film material deposited in this example also has a chemical formula of AlN, which belongs to a hexagonal system and has a crystal space group of P63mc, as shown in the photograph of Figure 2 .
[0033] Comparative Example 1 (1) The single crystal silicon substrate is cleaned with anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol in sequence, and each time the substrate is placed in an ultrasonic cleaner containing the cleaning liquid for 15 min; (2) The substrate is ion cleaned in a pure argon gas environment, and the pressure during the cleaning is 1.0 Pa, the cleaning power is 380 W, and the cleaning time is 15 min; (3) Al and Si are used as target materials, the purity of the target materials is 99.999%, and the target materials are sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit a compound Al 1-x Si x N 1-y O y on the substrate, wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 80% (i.e., the argon flow rate is 20 seem, and the nitrogen flow rate is 80 seem); during the high-power pulsed magnetron sputtering, the average power is 400 W, the duty cycle is 10%, the frequency is 1000 Hz, the pressure during the sputtering process is kept at 0.5 Pa, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 95 min. The finally deposited film has a thickness of 1100 nm, and the compound constituting the film material has a chemical formula of Al 0.95 Si 0.05 N 0.88 O 0.12, which belongs to hexagonal system and has crystal space group of P63mc.
[0034] Comparative Example 2 (1) The single crystal silicon was used as the substrate, and the substrate was sequentially cleaned with anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol as the cleaning liquid, and the substrate was placed in an ultrasonic cleaner containing the cleaning liquid for cleaning for 15 min each time; (2) The substrate was ion cleaned in a pure argon gas environment, and the pressure was 1.0 Pa, the cleaning power was 380 W, and the cleaning time was 15 min; (3) Al and Si were used as the target material, the purity of the target material was 99.999%, and the target material was sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit compound Al 1-x Si x N 1-y O y on the substrate, to obtain a thin film material; wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas was 80% (that is, the argon flow was 20 sccm, and the nitrogen flow was 80 sccm); when the high-power pulsed magnetron sputtering was performed, the average power was 1500 W, the duty cycle was 10%, the frequency was 1000 Hz, the gas pressure was kept at 0.5 Pa during the sputtering process, the substrate was additionally heated during the sputtering process, the heating temperature was 250°C, and the deposition time was 30 min. The finally deposited thin film had a thickness of 1400 nm, and the chemical formula of the compound constituting the thin film material was Al 0.61 Si 0.39 N 0.991 O 0.009 , which belongs to hexagonal system and has crystal space group of P63mc.
[0035] Comparative Example 3 (1) The single crystal silicon was used as the substrate, and the substrate was sequentially cleaned with anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol as the cleaning liquid, and the substrate was placed in an ultrasonic cleaner containing the cleaning liquid for cleaning for 15 min each time; (2) The substrate was ion cleaned in a pure argon gas environment, and the pressure was 1.0 Pa, the cleaning power was 380 W, and the cleaning time was 15 min; (3) Al and Si were used as the target material, the purity of the target material was 99.999%, and the target material was sputtered in an argon and nitrogen mixed gas environment by a high-power pulsed magnetron sputtering method to deposit compound Al 1-x Si x N 1-y O y, wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 70% (i.e., the argon flow rate is 30 sccm and the nitrogen flow rate is 70 sccm); during the high-power pulse magnetron sputtering, the average power is 600 W, the duty cycle is 20%, the frequency is 1000 Hz, the pressure during the sputtering process is kept at 0.8 Pa, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 90 min. The finally deposited film has a thickness of 1500 nm, and the chemical formula of the compound constituting the film material is Al 0.53 Si 0.47 N 0.988 O 0.012 , which belongs to the hexagonal system and has a crystal space group of P63mc.
[0036] Comparative Example 4 (1) The single crystal silicon substrate was cleaned with anhydrous ethanol, ultrapure water, acetone and anhydrous ethanol in sequence, and each time the substrate was placed in an ultrasonic cleaner containing the cleaning liquid for cleaning for 15 min; (2) The substrate was ion cleaned in a pure argon gas environment, and during the cleaning, the pressure was 1.0 Pa, the cleaning power was 380 W, and the cleaning time was 15 min; (3) Al and Si were used as target materials with a purity of 99.999%, and the target materials were sputtered by high-power pulse magnetron sputtering in an argon and nitrogen mixed gas environment to deposit the compound Al 1-x Si x N 1-y O y on the substrate; wherein the volume percentage of nitrogen in the argon and nitrogen mixed gas is 20% (i.e., the argon flow rate is 80 sccm and the nitrogen flow rate is 20 sccm); during the high-power pulse magnetron sputtering, the average power is 1000 W, the duty cycle is 15%, the frequency is 1000 Hz, the pressure during the sputtering process is kept at 1.2 Pa, the substrate is additionally heated during the sputtering process, the heating temperature is 250°C, and the deposition time is 75 min. The finally deposited film has a thickness of 1200 nm, and the chemical formula of the compound constituting the film material is Al 0.993 Si 0.007 N 0.82 O 0.18 , which belongs to the hexagonal system and has a crystal space group of P63mc.
[0037] Performance Test (1) Morphology characterization The cross sections of the film materials prepared in Example 1, Example 3 and Comparative Examples 1-4 were characterized by SEM, and the results are shown in Figure 3As shown. By Figure 3 It can be seen that the thin film materials prepared in Examples 1 and 3 have a dense structure, while the thin film materials prepared in Comparative Examples 1-4 have a loose structure.
[0038] (2) Insulation performance test The resistivity of the thin film materials prepared in Examples 1-5 and Comparative Examples 1-4 was measured using a high-resistivity meter (Keithley 6517B), and the results are as follows: Figure 4 As shown. By Figure 4 As can be seen, the resistivity of the thin film materials prepared in Examples 1-5 is all around 2.5 × 10⁻⁶. 15 Ω The resistivity of the thin film material prepared in Examples 1-5 is significantly higher than that in Comparative Examples 1-2 and 4, indicating that the thin film materials prepared in Examples 1-5 have excellent insulation properties; the resistivity of the thin film material prepared in Comparative Example 3 is 2.86 × 10⁻⁶ cm⁻¹. 15 Ω cm, which also has good insulation properties.
[0039] (3) High temperature resistance test The thin film materials prepared in Examples 1-5 were subjected to air annealing for more than 30 minutes in a high-temperature annealing furnace within the temperature range of 500℃ to 1200℃, and then XRD tests were performed. The tests revealed that the XRD patterns of the thin film materials prepared in Examples 1-5 after high-temperature annealing were basically the same. Taking Example 1 as an example, the XRD pattern of the thin film material prepared in Example 1 after high-temperature annealing is shown below. Figure 5 As shown. By Figure 5 It can be seen that the thin film material prepared in Example 1 still retains a stable crystal orientation after high-temperature annealing at 900℃~1200℃, indicating that the thin film material prepared in Example 1 has excellent thermal stability and high-temperature resistance.
[0040] (4) Wear resistance test The hardness of the thin film materials prepared in Examples 1-5 and Comparative Examples 1-4 was measured using nanoindentation technology, and the results are as follows: Figure 6 As shown. By Figure 6As can be seen, the hardness of the thin film materials prepared in Examples 1-5 were 15.948 GPa, 18.456 GPa, 21.576 GPa, 19.327 GPa, and 15.284 GPa, respectively, while the hardness of Comparative Examples 1-4 were 9.471 GPa, 19.374 GPa, 20.413 GPa, and 7.524 GPa, respectively. This indicates that the hardness of the thin film materials prepared in Examples 1-5 can reach 15 GPa~22 GPa, exhibiting excellent wear resistance. The thin film materials prepared in Comparative Examples 1 and 4 had higher O content, which affected the material hardness, while the thin film materials prepared in Comparative Examples 2 and 3 had higher Si content, thus also exhibiting higher hardness.
[0041] (5) Hydrophobicity test The contact angles of the thin film materials prepared in Examples 1-5 and Comparative Examples 1-4 with water at room temperature were measured using a contact angle meter, and the results are as follows: Figure 7 As shown. By Figure 7 As can be seen, the contact angles between the thin film materials prepared in Examples 1-5 and water are 113.1°, 118°, 119.1°, 123.6°, and 111.3°, respectively, while the contact angles between the thin film materials prepared in Comparative Examples 1-4 and water are 92.6°, 76.2°, 71.7°, and 110.1°, respectively. The surface free energy of the thin film materials prepared in Examples 1-5, calculated using the Owens-Wendt model (two-liquid method), is 24.9 mJ / m². 2 24.7 mJ / m 2 24.2 mJ / m 2 24.6 mJ / m 2 and 24.8 mJ / m 2 The surface free energies of the thin film materials prepared in Comparative Examples 1-4 were 31.75 mJ / m², respectively. 2 37.9mJ / m 2 38.2mJ / m 2 and 28.8 mJ / m 2 This indicates that the contact angles between the thin film materials prepared in Examples 1-5 and water are all greater than 111°, significantly higher than those in Comparative Examples 1-4, and the surface free energies of the thin film materials prepared in Examples 1-5 are all less than 25 mJ / m. 2 The Si content was significantly lower than that of Comparative Examples 1-4, indicating that the thin film materials prepared in Examples 1-5 have excellent hydrophobicity. It should be noted that the thin film materials prepared in Comparative Examples 2 and 3 had higher Si content, which improved the hardness, but significantly reduced the hydrophobicity of both.
Claims
1. A semiconductor nitride thin film material, characterized by, The components of the thin film material include compounds of the formula Al 1-x Si x N 1- y O y wherein, , The compound is hexagonal, with crystal space group P63mc.
2. The semiconductor nitride thin film material of claim 1, wherein, The resistivity of the thin film material is greater than 2.5*10 15 Ω cm, which maintains a stable hexagonal wurtzite crystal form at 900℃~1200℃, the hardness is 15GPa~22GPa, the contact angle with water is greater than 111°, and the surface free energy is less than 25mJ / m 2 .
3. A method of producing a semiconductor nitride thin film material, characterized by, The method comprises the following steps: cleaning the substrate; Deposition of compound Al 1-x Si x N 1-y O y wherein, 、 semiconductor nitride thin film material.
4. The method of claim 3, wherein the semiconductor nitride thin film material is prepared by a method comprising: the volume percentage of nitrogen in the mixed gas of argon and nitrogen is 50-80%, and the rest is argon.
5. The method of claim 3, wherein the semiconductor nitride thin film material is formed by a process selected from the group consisting of plasma enhanced chemical vapor deposition, plasma enhanced atomic layer deposition, and plasma enhanced molecular layer deposition. During the high-power pulse magnetron sputtering, the average power is 600-1000 W, the duty cycle is 7.5-15%, the frequency is 500-1000 Hz, and the sputtering pressure is 0.5-1.0 Pa.
6. The method of claim 3, wherein the semiconductor nitride thin film material is formed by a process selected from the group consisting of plasma enhanced chemical vapor deposition, plasma enhanced atomic layer deposition, and plasma enhanced molecular layer deposition. The substrate is additionally heated during the sputtering process, and the heating temperature is 250 DEG C.
7. The method of claim 3, wherein the semiconductor nitride thin film material is formed by a plasma enhanced chemical vapor deposition process. The deposition time is 60-90 min.
8. The method of claim 3, wherein the semiconductor nitride thin film material is formed by a process selected from the group consisting of plasma enhanced chemical vapor deposition, plasma enhanced atomic layer deposition, and plasma enhanced molecular layer deposition. The thickness of the deposited film is 1100-1500 nm.