Preparation method and application of rose-like gold composite film with excellent mechanical properties

Abstract

The application belongs to the technical field of vacuum coating, and discloses a kind of rose-like gold composite film and its preparation method and application.The application utilizes intermediate frequency magnetron sputtering technology to deposit a primer layer on a substrate; then utilizes high-power pulse magnetron sputtering technology and intermediate frequency magnetron sputtering technology to deposit a transition layer and a surface layer on the primer layer in sequence by using a composite magnetron sputtering technology, to obtain a rose-like gold composite film of TiN / TiCN, wherein the primer layer is a pure Ti layer, the transition layer is a TiN layer, and the surface layer is a TiCN layer.The application combines intermediate frequency magnetron sputtering and high-power magnetron sputtering technology, integrates the advantages of the two processes, improves the defects of the two processes, has a wide range of applications, can be applied to most metal materials, and is green and environmentally friendly.The crystal lattices of the film layer prepared by the application cooperate well, the obtained rose-like gold composite film has excellent mechanical properties and film-substrate adhesion; and the atomic ratio is appropriate, and has the ideal color of rose-like gold.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of vacuum coating, and particularly relates to a preparation method and application of a rose-like gold composite film with excellent mechanical properties. BACKGROUND

[0002] TiN film in transition group binary nitride is famous for its high thermal stability, corrosion resistance, mechanical hardness and low resistivity, and is widely used in the fields of microelectronic industry, protective coating and tool coating, but with the development of society, people's pursuit of high-performance thin films is becoming stronger and stronger, and the addition of some metal or non-metal elements to TiN to form ternary nitride can effectively meet people's needs. The TiCN film obtained by adding C element not only has more excellent mechanical properties and friction properties, but also has a rose gold color, which makes it widely used in the field of decorative films.

[0003] TiCN film is usually prepared by physical vapor deposition (Physical Vapour Deposition, PVD) technology, but the traditional PVD film has loose structure and often has defects such as holes and pinholes, resulting in poor mechanical properties of the film and easy corrosion in corrosive medium. The magnetic control sputtering technology has the advantages of energy saving, safety, high precision and high quality, and general magnetic control sputtering technology such as intermediate frequency magnetic control sputtering can deposit a film with good mechanical properties.

[0004] However, the TiCN film prepared by the general magnetic control sputtering technology cannot meet the higher quality application requirements, and the demand for more excellent mechanical properties and more ideal color of the rose-like gold film layer in the field of decorative films also needs to be solved. The current popular high-power pulse magnetron sputtering technology (High-Power Impulse Magnetron Sputtering, HiPIMS) has low deposition efficiency, and the color of the TiCN film layer is unstable with gas flow change, and the general film layer structure also has the problem of low bonding force. SUMMARY

[0005] In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a preparation method of a rose-like gold composite film.

[0006] Another purpose of the present application is to provide a rose-like gold composite film prepared by the above method.

[0007] Still another purpose of the present application is to provide the application of the above rose-like gold composite film in the field of decorative films.

[0008] The purposes of the present application are achieved by the following schemes:

[0009] A method for preparing a rose gold-like composite film comprises the following steps: depositing a base layer on a substrate using medium frequency magnetron sputtering (MFMS); then sequentially depositing a transition layer and a surface layer on the base layer using a composite magnetron sputtering technique combining high power pulsed magnetron sputtering and medium frequency magnetron sputtering (HIPIMS+MFMS) to obtain a TiN / TiCN rose gold-like composite film, wherein the base layer is a pure Ti layer, the transition layer is a TiN layer, and the surface layer is a TiCN layer.

[0010] The preparation method of the rose gold-like composite film specifically comprises the following steps:

[0011] (1) Using a Ti target to deposit a base layer on the substrate by medium-frequency magnetron sputtering;

[0012] (2) Depositing the transition layer on the base layer by composite magnetron sputtering technology using a Ti target in N2;

[0013] (3) A Ti target was used on the transition layer to deposit a surface layer by composite magnetron sputtering technology in a mixed atmosphere of C2H2 and N2 to obtain a rose gold-like composite film of TiN / TiCN.

[0014] The material of the substrate in step (1) includes one of stainless steel, copper and its alloys, silver and its alloys.

[0015] The substrate in step (1) should be pre-treated before film sputtering, including at least one of degreasing, decontamination, and glow cleaning.

[0016] The atmosphere for depositing the bottom layer in step (1) is argon gas, and the gas flow rate is 150 to 300 sccm, preferably 180 to 250 sccm; the deposition time is 5 to 30 minutes.

[0017] The target current of the Ti target in step (1) is 10 to 50 A, preferably 25 to 45 A.

[0018] In step (2), the N2 gas flow rate is 150 to 220 sccm, preferably 160 to 210 sccm; and the deposition time is 10 to 50 minutes.

[0019] The Ti targets in step (2) are Ti target 1 and Ti target 2, wherein Ti target 1 is connected to a medium-frequency magnetron sputtering power supply, and Ti target 2 is connected to a high-power pulsed magnetron sputtering power supply; the current of Ti target 1 is 50 to 120 A, preferably 70 to 100 A; the current of Ti target 2 is 70 to 140 A, preferably 90 to 120 A; the currents of the Ti targets and Ti targets in step (3) are the same as those in step (2).

[0020] The gas flow of N2 is 2-50sccm, and the gas flow of C2H2 is 2-50sccm; preferably, the gas flow of N2 is 10-30sccm, and the gas flow of C2H2 is 8-40sccm; and the deposition time is 15-40min.

[0021] The TiN / TiCN rose-like gold composite film prepared by the method.

[0022] Application of the rose-like gold composite film in a decorative film.

[0023] The mechanism of the present application is as follows:

[0024] The present application adds a primer layer and a transition layer between the TiCN film layer and the substrate, so that the composite film has good adhesion with the substrate. Based on the cooperation between different film layers deposited by different process methods, the primer layer is deposited by using a medium frequency magnetron sputtering technology, the dense transition layer and surface layer are deposited by using a composite magnetron sputtering technology, the stress is generated between the lattices of different film layers, so that the obtained composite film has high hardness and good toughness, and the atomic ratio is good and has an ideal color of near rose gold.

[0025] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0026] The present application combines the medium frequency magnetron sputtering and high-power magnetron sputtering technologies, integrates the advantages of the two processes, improves the defects of the two processes, has a wide application range, and is suitable for most metal materials and is green and environmentally friendly.

[0027] The lattices of the film layers prepared by the present application cooperate well, and the obtained rose-like gold composite film has excellent mechanical properties, wherein the hardness is greater than 29GPa, the elastic modulus is greater than 280GPa, and the film-substrate adhesion is greater than 27N.

[0028] The obtained rose-like gold composite film has a proper atomic ratio and an ideal color of rose-like gold. Compared with the Lab value of the standard rose gold, the absolute value of Delta L is 22-23, the absolute value of Delta a is 4-5, and the absolute value of Delta b is 7-9. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 It is a structural schematic diagram of the rose-like gold composite film of the present application.

[0030] Figure 2 It is a nano-indentation loading-unloading curve diagram of the rose-like gold composite film prepared in Example 1 and the composite film prepared in Comparative Example 1.

[0031] Figure 3Nanoin denta tion load-unload curves of the rose-gold-like composite film prepared in Example 2 and the composite film prepared in Comparative Example 1.

[0032] Figure 4 Nanoin denta tion load-unload curves of the rose-gold-like composite film prepared in Example 3 and the composite film prepared in Comparative Example 1. DETAILED DESCRIPTION

[0033] The present application is described in further detail below with reference to examples and drawings, but the embodiments of the present application are not limited thereto. In the examples, the specific conditions not mentioned are performed according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not mentioned by the manufacturers, and are all conventional products that can be purchased on the market.

[0034] The reagents used in the examples are all conventional products that can be purchased on the market, unless otherwise specified.

[0035] Example 1

[0036] 1. Pretreatment

[0037] The stainless steel substrate was placed in deionized water and ethanol, respectively, for ultrasonic cleaning for oil and dirt removal, and then was placed in a vacuum furnace for glow cleaning.

[0038] 2. Preparation of rose-gold-like composite film

[0039] (1) The protective gas Ar was introduced, the Ar flow rate was controlled to be 200 sccm, the intermediate frequency magnetron sputtering power was turned on, the Ti target current was adjusted to be 40 A, and a Ti layer was deposited on the substrate for 15 min;

[0040] (2) The reaction gas N2 was introduced, the N2 flow rate was controlled to be 195 sccm, the high-power pulse magnetron sputtering power was turned on, the Ti target 1 was connected to the intermediate frequency magnetron sputtering power, and the Ti target 2 was connected to the high-power pulse magnetron sputtering power; the Ti target 1 current was maintained to be 100 A, the Ti target 2 current was 120 A, and a TiN layer was deposited on the Ti layer for 30 min;

[0041] (3) The N2 flow rate was adjusted to be 20 sccm, the reaction gas C2H2 was introduced, the C2H2 flow rate was 10 sccm, a TiCN layer was deposited on the TiN layer for 25 min, and a rose-gold-like TiN / TiCN film was obtained.

[0042] Example 2

[0043] 1. Pretreatment

[0044] The stainless steel substrate was placed in deionized water and ethanol, respectively, for ultrasonic cleaning for oil and dirt removal, and then was placed in a vacuum furnace for glow cleaning.

[0045] 2. Preparation of rose-gold-like composite film

[0046] (1) Introduce the protective gas Ar, control the Ar flow rate to be 200 sccm, turn on the intermediate frequency magnetron sputtering power supply, adjust the Ti target current to be 40 A, and deposit a Ti layer on the substrate for 15 min;

[0047] (2) Introduce the reaction gas N2, control the N2 flow rate to be 200 sccm, turn on the high-power pulse magnetron sputtering power supply, wherein the Ti target 1 is connected to the intermediate frequency magnetron sputtering power supply, and the Ti target 2 is connected to the high-power pulse magnetron sputtering power supply; keep the Ti target 1 current to be 100 A, and the Ti target 2 current to be 120 A, and deposit a TiN layer on the Ti layer for 30 min;

[0048] (3) Adjust the N2 flow rate to be 20 sccm, introduce the reaction gas C2H2, the C2H2 gas flow rate is 10 sccm, deposit a TiCN layer on the TiN layer for 25 min, and obtain a TiN / TiCN film with a rose gold color.

[0049] Example 3

[0050] 1. Pretreatment

[0051] The stainless steel substrate is placed in deionized water and ethanol for ultrasonic cleaning for oil and dirt removal treatment, and then placed in a vacuum furnace for glow cleaning.

[0052] 2. Preparation of a rose gold composite film

[0053] (1) Introduce the protective gas Ar, control the Ar flow rate to be 200 sccm, turn on the intermediate frequency magnetron sputtering power supply, adjust the Ti target current to be 40 A, and deposit a Ti layer on the substrate for 15 min;

[0054] (2) Introduce the reaction gas N2, control the N2 flow rate to be 205 sccm, turn on the high-power pulse magnetron sputtering power supply, wherein the Ti target 1 is connected to the intermediate frequency magnetron sputtering power supply, and the Ti target 2 is connected to the high-power pulse magnetron sputtering power supply; keep the Ti target 1 current to be 100 A, and the Ti target 2 current to be 120 A, and deposit a TiN layer on the Ti layer for 30 min;

[0055] (3) Adjust the N2 flow rate to be 20 sccm, introduce the reaction gas C2H2, the C2H2 gas flow rate is 10 sccm, deposit a TiCN layer on the TiN layer for 25 min, and obtain a TiN / TiCN film with a rose gold color.

[0056] Comparative Example 1

[0057] 1. Pretreatment

[0058] The stainless steel substrate is placed in deionized water and ethanol for ultrasonic cleaning for oil and dirt removal treatment, and then placed in a vacuum furnace for glow cleaning.

[0059] 2. Preparation of composite film

[0060] (1) The protective gas Ar was introduced at a flow rate of 200 sccm, the intermediate frequency magnetron sputtering power was turned on, the Ti target current was adjusted to 40 A, and a Ti layer was deposited on the substrate for 15 min;

[0061] (2) The reaction gas N2 was introduced at a flow rate of 195 sccm, the Ti target current was maintained at 100 A, and a TiN layer was deposited on the Ti layer for 30 min;

[0062] (3) The reaction gas C2H2 was introduced at a flow rate of 10 sccm, a TiCN layer was deposited on the TiN layer for 25 min, and a TiN / TiCN film was obtained.

[0063] Comparative Example 2

[0064] 1. Pretreatment

[0065] The stainless steel substrate was ultrasonically cleaned in deionized water and ethanol respectively for oil and dirt removal, and then placed in a vacuum furnace for glow cleaning.

[0066] 2. Preparation of composite film

[0067] (1) The protective gas Ar was introduced at a flow rate of 200 sccm, the intermediate frequency magnetron sputtering power was turned on, the Ti target current was adjusted to 40 A, and a Ti layer was deposited on the substrate for 15 min;

[0068] (2) The reaction gas N2 was introduced at a flow rate of 195 sccm, the Ti target current was maintained at 100 A, and a TiN layer was deposited on the Ti layer for 30 min;

[0069] (3) The intermediate frequency magnetron sputtering power was turned off, the high-power pulsed magnetron sputtering power was turned on, the Ti target current was maintained at 120 A, the reaction gas C2H2 was introduced at a flow rate of 10 sccm, the N2 flow rate was adjusted to 20 sccm, a TiCN layer was deposited on the TiN layer for 25 min, and a TiN / TiCN film was obtained.

[0070] Product effect test

[0071] 1. Mechanical property test: The mechanical properties of the films prepared in the above examples and comparative examples were tested by using a TTX-NHT3 nanoindenter of Austria Anton Paar. The load force was set to 5 mN, the loading rate was 5 mN / min, and the microhardness and elastic modulus of different samples were measured in turn. The mechanical properties of the composite film were reflected by the hardness and elastic modulus. The hardness represents the ability of the metal surface to resist deformation or rupture within a small volume, and the elastic modulus indicates the rigidity of the film layer. The greater the elastic modulus, the more difficult it is to occur elastic deformation.

[0072] The results are shown in Table 1, combined with Figures 2 to 4 The hardness of Examples 1-3 is significantly greater than that of Comparative Example 1, and the elastic modulus is also improved, indicating that the mechanical properties of the rose gold TiN / TiCN composite film prepared by the method of the application are significantly improved.

[0073] Table 1 Nanoindentation test results of each example and comparative example

[0074] Hardness / GPa Elastic Modulus / Gpa Example 1 35.36 346.17 Example 2 29.28 286.34 Example 3 33.38 292.94 Comparative Example 1 17.32 220.59 Comparative Example 2 28.54 288.92

[0075] 2. Color test: The color of the film prepared in each of the above examples and comparative examples was analyzed using a CM-700d spectrophotometer from Konica Minolta, Japan. The sample was measured 3 times and the average value was taken, and the brightness difference (ΔL), red-green color difference (Δa), and yellow-blue color difference (Δb) were obtained.

[0076] The color difference was calculated by ΔE = (ΔL 2 + Δa 2 + Δb 2 ) 1 / 2 The results are shown in Table 2. Compared with the Lab values of standard rose gold, it can be seen that the brightness difference, red-green color difference, and yellow-blue color difference of Examples 1-3 are significantly reduced compared with Comparative Examples 1-2, and the color difference value is also significantly reduced, indicating that the film layer prepared by the method of the application is closer to rose gold.

[0077] Table 2 Color test results of each example and comparative example

[0078] L a b Delta E Standard Rose Gold 87.7 8.32 18.57 / Example 1 65.18 12.53 27.23 24.49 Example 2 64.43 12.55 26.41 24.92 Example 3 65.29 12.55 26.41 24.54 Comparative Example 1 63.85 12.79 25.55 25.24 Comparative Example 2 43.36 18.37 5.32 47.36

[0079] 3. Adhesion test: The adhesion between the composite film prepared in each of the above examples and comparative examples and the substrate was analyzed using a MFT-4000 scratch tester from Lanzhou Zhongke Kaitai Technology Co., Ltd. The scratch length was set to 5 mm, the test load was 50 N, and the loading rate was 50 N / min. The adhesion of the film layer was determined by observing the friction coefficient and friction force curve and the optical morphology change of the scratch. By observing the optical morphology change of the scratch, when a large number of silver-white metallic luster appears inside the scratch, and the raised phenomenon around the scratch intensifies, it means that the film layer is peeled off, in addition, the sudden change of the friction coefficient and friction force curve can determine the adhesion of the film layer.

[0080] The results are shown in Table 3. It can be seen that the adhesion of Examples 1-3 is significantly greater than that of Comparative Examples 1-2, indicating that the adhesion of the rose gold TiN / TiCN film prepared by the method of the application is significantly improved.

[0081] Table 3 Adhesion test results of each example and comparative example

[0082] Bond Strength / N Example 1 28.99 Example 2 27.33 Example 3 28.69 Comparative Example 1 16.58 Comparative Example 2 21.27

[0083] The above embodiments are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any changes, modifications, substitutions, combinations, simplifications, etc. made without departing from the spirit and principles of the present application should be equivalent replacement manners and should be included in the protection scope of the present application.

Claims

1. A method for preparing a rose gold-like composite film, characterized in that: The following steps are involved: A base layer is deposited on a substrate using medium-frequency magnetron sputtering technology. A transition layer and a surface layer are then sequentially deposited on the base layer using a composite magnetron sputtering technology combining high-power pulsed magnetron sputtering technology and medium-frequency magnetron sputtering technology, thereby obtaining a TiN / TiCN rose gold-like composite film, wherein the base layer is a pure Ti layer, the transition layer is a TiN layer, and the surface layer is a TiCN layer. The specific steps include: (1) Using a Ti target to deposit a base layer on the substrate by medium-frequency magnetron sputtering; (2) Depositing the transition layer on the base layer using a Ti target in N2 by composite magnetron sputtering technology; (3) Using a Ti target on the transition layer, a surface layer was deposited by composite magnetron sputtering technology in C2H2 and N2 to obtain a rose gold-like composite film of TiN / TiCN; In step (2), the N2 gas flow rate is 160-210 sccm; the deposition time is 10-50 min; The Ti targets in step (2) are Ti target 1 and Ti target 2, wherein Ti target 1 is connected to a medium-frequency magnetron sputtering power supply, and Ti target 2 is connected to a high-power pulsed magnetron sputtering power supply; the current of Ti target 1 is 70-100 A; the current of Ti target 2 is 90-120 A; The Ti target and the current of the Ti target in step (3) are the same as those in step (2); In step (3), the gas flow rate of N2 is 10-30 sccm, and the gas flow rate of C2H2 is 8-40 sccm; the deposition time is 15-40 min.

2. The method for preparing the rose gold-like composite film according to claim 1, wherein: The material of the substrate in step (1) includes one of stainless steel, copper and its alloys, silver and its alloys; The substrate in step (1) should be pre-treated before film sputtering, including at least one of degreasing, decontamination, and glow cleaning.

3. The method for preparing the rose gold-like composite film according to claim 1, wherein: The atmosphere for depositing the base layer in step (1) is argon gas with a gas flow rate of 180-250 sccm; the deposition time is 5-30 min.

4. The method for preparing the rose gold-like composite film according to claim 1, wherein: The target current of the Ti target in step (1) is 25~45A.

5. The rose gold-like TiN / TiCN composite film prepared by the method according to any one of claims 1 to 4.

6. Use of the rose gold-like composite film according to claim 5 in decorative films.

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