阅读说明：本技术 一种磁过滤阴极真空弧沉积导电碳膜的制备方法 (Preparation method of magnetic filtration cathode vacuum arc deposition conductive carbon film ) 是由 李谊 应世强 李文 于 2021-10-11 设计创作，主要内容包括：本发明提出了一种磁过滤阴极真空弧沉积导电碳膜的方法,包括以下步骤：首先将基片进行表面清洗预处理,然后在清洗后的基片上沉积过渡层,最后在过渡层表面沉积类石墨导电碳膜。通过本发明方法沉积的导电碳膜导电性高、结构致密,膜层与基片的结合力强。本发明提供的方法沉积面积大、效率高、绿色无污染,具有良好的应用前景。(The invention provides a method for depositing a conductive carbon film by magnetic filtration cathode vacuum arc, which comprises the following steps: firstly, the surface of a substrate is cleaned and pretreated, then a transition layer is deposited on the cleaned substrate, and finally a graphite-like conductive carbon film is deposited on the surface of the transition layer. The conductive carbon film deposited by the method has high conductivity, compact structure and strong bonding force between the film layer and the substrate. The method provided by the invention has the advantages of large deposition area, high efficiency, greenness, no pollution and good application prospect.)

1. A preparation method of a magnetic filtration cathode vacuum arc deposition conductive carbon film is characterized by comprising the following steps:

the first step, substrate pretreatment: carrying out ultrasonic cleaning and drying on the substrate, and then carrying out plasma cleaning on the surface of the substrate under the argon condition;

step two, depositing a transition layer: under the condition of working gas with certain pressure, the magnetic filtration cathode vacuum deposition technology is adopted to carry out transition layer deposition on the surface of the pretreated substrate;

step three, preparing a conductive carbon film: and under the condition of working gas with certain pressure, performing graphite-like carbon film deposition on the surface of the transition layer by adopting a magnetic filtration cathode vacuum deposition technology.

2. The method for preparing a magnetic filtration cathode vacuum arc deposition conductive carbon film as claimed in claim 1, wherein in the first step, the substrate pretreatment specifically comprises: sequentially putting the substrate into isopropanol, deionized water and absolute ethyl alcohol for ultrasonic cleaning, drying and fixing the substrate on a substrate hanger in a film deposition vacuum cavity; vacuumizing, opening a gas valve, introducing argon, and adjusting the pressure of the chamber; opening an ion source, adjusting the voltage and the duty ratio of the ion source, and cleaning the surface of the substrate by plasma;

in the second step, depositing the filter layer specifically comprises: introducing working gas into the film deposition vacuum cavity, adjusting the rotating speed of the substrate hanger, the gas flow, the chamber air pressure, the voltage and the duty ratio of a bias power supply, the voltage and the duty ratio of an ion source, opening an arc source, a lead-out source, an arc stabilizing source and a focusing source of the transition layer target, adjusting the deposition time, and performing transition layer deposition on the surface of the substrate after pretreatment and cleaning;

in the third step, the preparation of the conductive carbon film specifically comprises: and introducing working gas into the film deposition vacuum cavity, adjusting the rotating speed of the substrate hanger, the gas flow, the chamber gas pressure, the voltage and the duty ratio of the bias power supply, the voltage and the duty ratio of the ion source, opening the arc source, the extraction source, the arc stabilizing source and the focusing source corresponding to the graphite target, adjusting the deposition time, and depositing the graphite-like carbon film on the surface of the transition layer.

3. The method as claimed in claim 2, wherein the conductive carbon film is a graphite-like carbon film, wherein the graphite-like carbon film has a thickness of 2-5 μm and a sheet resistance of 12-30 Ω/□.

4. The method of claim 2, wherein the substrate is a silicon wafer, a glass sheet, a stainless steel sheet or a PET sheet.

5. The method of claim 2, wherein the substrate is dried at a temperature of the first step60-100 ℃, and the vacuum degree of the evacuated cavity body is 1 multiplied by 10^-4The flow of the introduced argon is 10-20 sccm, and the pressure of the chamber after the argon is introduced is 0.03-0.08 Pa; the voltage of the ion source is set to be 300-800V, and the duty ratio is 20-80%.

6. The method of claim 2, wherein the target material of the transition layer is a titanium target or a chromium target.

7. The method of claim 2, wherein the transition layer has a thickness of 0.2-0.6 μm.

8. The method for preparing a conductive carbon film by magnetic filtration cathode vacuum arc deposition according to claim 2, wherein in the second step, the rotation speed of the substrate rack is 10 to 15r/min, the flow of the introduced argon is 40 to 150sccm, and the pressure of the chamber is 0.1 to 1 Pa; the bias power supply voltage is set to be 200-300V, and the duty ratio is set to be 30-40%; the voltage of the ion source is set to be 300-800V, and the duty ratio is 50-80%; the arc source current of the transition layer target is 60-90A, the extraction source current is 10-12A, and the arc stabilizing source current and the focusing source current are both 4A; the deposition time is 5-15 min.

9. The method for preparing a conductive carbon film by magnetic filtration cathode vacuum arc deposition according to claim 2, wherein in the third step, the rotation speed of the substrate hanger is 15 to 20r/min, the flow of the argon working gas is 150 to 200sccm, and the pressure in the chamber is 1 to 3 Pa; during carbon film deposition, the arc source current of the graphite target is 70-75A, the extraction source current is 10-15A, and the arc stabilizing source current and the focusing source current are both 4A; the voltage of the bias power supply is set to be 300-400V, and the duty ratio is 40-60%; the voltage of the ion source is set to be 550-650V, and the duty ratio is 70-90%; the deposition time is 100-300 min.

Technical Field

The invention relates to a preparation method of a magnetic filtration cathode vacuum arc deposition conductive carbon film, in particular to a preparation method of a magnetic filtration cathode vacuum arc deposition graphite-like conductive carbon film, and belongs to the technical field of thin film material preparation.

Background

It is known that cathode vacuum arc deposition is a thin film deposition method in which plasma generated by a vacuum arc power supply is led out to the surface of a substrate through a bias power supply and the like, and has the advantages of high ionization rate, low deposition temperature, high deposition rate, bonding force and the like. However, the film deposited by using the cathode vacuum arc still has the problems of larger particles, poorer compactness and the like. The magnetic filtering cathode vacuum arc deposition method is based on cathode vacuum arcOptimization of deposition improves the technology. The bending arc magnetic filter in the magnetic filtering cathode vacuum arc deposition technology can effectively filter large particles generated by cathode vacuum arc, and provides a completely ionized plasma source, so that the quality and uniformity of a film layer are improved. The existing magnetic filtration cathode vacuum arc deposition technology is mainly used for preparing sp³A hard diamond-like carbon film mainly having a hybrid bond. Sp in carbon film³The amount of the bond content directly determines the hardness of the diamond-like carbon film. In order to obtain high hardness carbon film coatings, researchers have long been working on optimizing magnetic filtration cathode vacuum arc deposition process parameters to obtain high sp³A diamond-like carbon film having a bond content. Except for sp³The diamond-like carbon film structure mainly based on sp2 bond hybridization is another important carbon film material, and has wide application prospect in the fields of electrochemical corrosion prevention and the like. However, studies on the preparation of graphite-like conductive carbon films by using a magnetic filtration cathode vacuum arc deposition technique have been rarely reported. In order to further expand the types of carbon film materials prepared by magnetic filtration cathode vacuum arc deposition, a technological method for preparing a graphite-like conductive carbon film by using a magnetic filtration cathode vacuum arc deposition technology needs to be developed urgently.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of a magnetic filtration cathode vacuum arc deposition conductive carbon film, which can realize the preparation of a graphite-like conductive carbon film with high compactness and high conductivity.

The invention provides a preparation method of a magnetic filtration cathode vacuum arc deposition conductive carbon film, which comprises the following steps:

the first step, substrate pretreatment: carrying out ultrasonic cleaning and drying on the substrate, and then carrying out plasma cleaning on the surface of the substrate under the argon condition;

step two, depositing a transition layer: under the condition of working gas with certain pressure, the magnetic filtration cathode vacuum deposition technology is adopted to carry out transition layer deposition on the surface of the pretreated substrate;

step three, preparing a conductive carbon film: and under the condition of working gas with certain pressure, performing graphite-like carbon film deposition on the surface of the transition layer by adopting a magnetic filtration cathode vacuum deposition technology.

The method comprises pretreating a substrate, depositing a transition layer on the surface of the substrate, and depositing a graphite-like conductive carbon film layer on the transition layer. The conductive carbon film deposited by the method has high conductivity, compact structure and strong bonding force between the film layer and the substrate. The method provided by the invention has the advantages of large deposition area, high efficiency, greenness, no pollution and good application prospect.

The technical scheme of the invention for further refining is as follows:

preferably, in the first step, the substrate pretreatment specifically includes: sequentially putting the substrate into isopropanol, deionized water and absolute ethyl alcohol for ultrasonic cleaning, drying and fixing the substrate on a substrate hanger in a film deposition vacuum cavity; vacuumizing, opening a gas valve, introducing argon, and adjusting the pressure of the chamber; opening an ion source, adjusting the voltage and the duty ratio of the ion source, and cleaning the surface of the substrate by plasma;

in the second step, depositing the filter layer specifically comprises: introducing argon working gas into the film deposition vacuum cavity, adjusting the rotating speed of the substrate hanger, the gas flow, the chamber air pressure, the voltage and the duty ratio of a bias power supply, the voltage and the duty ratio of an ion source, opening an arc source, a lead-out source, an arc stabilizing source and a focusing source of the transition layer target, adjusting the deposition time, and performing transition layer deposition on the surface of the substrate after pretreatment and cleaning;

in the third step, the preparation of the conductive carbon film specifically comprises: and introducing argon working gas into the film deposition vacuum cavity, adjusting the rotating speed of the substrate hanger, the gas flow, the chamber air pressure, the voltage and the duty ratio of the bias power supply, the voltage and the duty ratio of the ion source, opening the arc source, the extraction source, the arc stabilizing source and the focusing source corresponding to the graphite target, adjusting the deposition time, and depositing the graphite-like carbon film on the surface of the transition layer.

Preferably, the conductive carbon film is a graphite-like carbon film, wherein the thickness of the graphite-like carbon film is 2-5 μm, and the sheet resistance is 12-30 Ω/□.

Preferably, the substrate is a silicon wafer, a glass sheet, a stainless steel sheet or a PET sheet.

Preferably, in the first step, the drying temperature of the substrate is 60-100 ℃, and the vacuum degree of the vacuumized cavity body is 1 multiplied by 10^-4The flow of the introduced argon is 10-20 sccm, and the pressure of the chamber after the argon is introduced is 0.03-0.08 Pa; the voltage of the ion source is set to be 300-800V, and the duty ratio is 20-80%.

Preferably, the transition layer target is a titanium target or a chromium target.

Preferably, the thickness of the transition layer is 0.2-0.6 μm.

Preferably, in the second step, the rotating speed of the substrate hanger is 10-15 r/min, the flow of the introduced argon is 40-150 sccm, and the air pressure of the chamber is 0.1-1 Pa; the bias power supply voltage is set to be 200-300V, and the duty ratio is set to be 30-40%; the voltage of the ion source is set to be 300-800V, and the duty ratio is 50-80%; the arc source current of the transition layer target is 60-90A, the extraction source current is 10-12A, and the arc stabilizing source current and the focusing source current are both 4A; the deposition time is 5-15 min.

Preferably, in the third step, the rotating speed of the substrate hanger is 15-20 r/min, the flow of the argon working gas is 150-200 sccm, and the air pressure of the chamber is 1-3 Pa; during carbon film deposition, the arc source current of the graphite target is 70-75A, the extraction source current is 10-15A, and the arc stabilizing source current and the focusing source current are both 4A; the voltage of the bias power supply is set to be 300-400V, and the duty ratio is 40-60%; the voltage of the ion source is set to be 550-650V, and the duty ratio is 70-90%; the deposition time is 100-300 min.

Compared with the prior art, the invention has the following advantages and innovations: (1) the magnetic filtration cathode vacuum arc deposition technology is used for depositing the graphite-like conductive film, so that the preparation of the high-compactness and high-conductivity graphite-like conductive carbon film is realized; (2) the deposition area is large, the efficiency is high, and the large-scale production can be realized; (3) the method has the advantages of no generation of harmful substances, no discharge of waste gas and waste water, no pollution, safety and reliability in the implementation process.

Drawings

Fig. 1 is an SEM image of a graphite-like carbon film produced in the present invention.

Fig. 2 is a Raman chart of the graphite-like carbon film prepared in the present invention.

Detailed Description

The technical scheme of the invention is further explained in detail by combining the attached drawings: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection authority of the present invention is not limited to the following embodiments.

Example 1

(1) Substrate pretreatment: sequentially putting the glass substrate into isopropanol, deionized water and absolute ethyl alcohol for ultrasonic cleaning, cleaning for 10 minutes each time, drying at 100 ℃, and fixing on a rotatable substrate hanger in an equipment chamber; vacuum-pumping to 1 × 10^-4Pa, opening a gas valve, introducing argon with the flow of 10sccm, and controlling the pressure of the chamber to be 0.06 Pa; the ion source was turned on, the ion source voltage was set to 500V, and the duty cycle was 50%. And carrying out plasma cleaning on the surface of the glass substrate for 20min to remove impurities on the surface of the substrate.

(2) Depositing a titanium transition layer: argon is used as working gas, the air inflow of the argon is set to be 80sccm, the air pressure of a chamber is set to be 0.5Pa, the rotating speed of a substrate hanger is adjusted to be 15r/min, a titanium target power supply is turned on, an arc source current is set to be 75A, a source current is led out to be 10A, and arc stabilizing source and focusing source currents are 4A; the voltage of the bias power supply is set to be 200V, and the duty ratio is 30%; the voltage of the ion source is set to be 500V, and the duty ratio is 60 percent; and (3) carrying out titanium transition layer deposition on the surface of the substrate after pretreatment and cleaning, wherein the deposition time is 10 min.

(3) Depositing a graphite-like carbon film: argon is used as working gas, the air inflow of the argon is set to be 150sccm, the air pressure of a chamber is set to be 1.0Pa, the rotating speed of a substrate hanger is adjusted to be 20r/min, a graphite target power supply is turned on, arc source current is set to be 75A, source current is led out to be 10A, arc stabilizing source and focusing source current are set to be 4A, the voltage of a bias power supply is set to be 300V, the duty ratio is 40%, the voltage of an ion source is set to be 600V, the duty ratio is 80%, graphite-like carbon film deposition is carried out on the surface of a transition layer, and the deposition time is 120 min.

The detection shows that the thickness of the transition layer is 0.2-0.6 μm, the thickness of the graphite-like carbon film is 2-5 μm, and the sheet resistance is 12-30 Ω/□. Paired systemScanning by an electron microscope and measuring by Raman spectroscopy to obtain SEM images and Raman images of the prepared graphite-like carbon film (see figures 1 and 2). As can be seen from fig. 1, the graphite-like carbon film is composed of tightly bonded carbon particles; as can be seen from FIG. 2, the relative intensity ratio of the D peak and the G peak in the Raman chart of the graphite-like carbon film is (