CN109306455B - Iron-doped amorphous carbon film and preparation method thereof - Google Patents
Iron-doped amorphous carbon film and preparation method thereof Download PDFInfo
- Publication number
- CN109306455B CN109306455B CN201811241590.1A CN201811241590A CN109306455B CN 109306455 B CN109306455 B CN 109306455B CN 201811241590 A CN201811241590 A CN 201811241590A CN 109306455 B CN109306455 B CN 109306455B
- Authority
- CN
- China
- Prior art keywords
- iron
- evaporation
- amorphous carbon
- carbon film
- doped amorphous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to an iron-doped amorphous carbon film and a preparation method thereof, wherein the preparation method comprises the following steps: (1) pretreatment: grinding and polishing an iron sheet serving as a substrate material, cleaning, drying, adhering the iron sheet to a sample rack of a vacuum chamber, and connecting an electrode by taking a carbon wire as an evaporation source; (2) preparation before plating: vacuumizing the vacuum chamber and adjusting the target base distance; (3) evaporation: and (3) regulating the evaporation resistance current to carry out evaporation under the condition of inert gas, and depositing a layer of carbon film on the surface of the iron sheet to prepare the iron-doped amorphous carbon film. Compared with the prior art, the iron-doped amorphous carbon film prepared by the vacuum evaporation method mainly comprises two valence states of graphitized carbon sp2 and diamond carbon sp3, the closer the iron substrate is, the higher the graphitization degree is, the preparation method is simple, the film forming speed is high, and the efficiency is high.
Description
Technical Field
The invention relates to a carbon film, in particular to an iron-doped amorphous carbon film and a preparation method thereof.
Background
The amorphous carbon film is a metastable state disordered long-range amorphous material containing sp3 and sp2 bonds, has the excellent characteristics of diamond and graphite, has the characteristics of high hardness and high elastic modulus, low friction coefficient, excellent wear resistance, good chemical inertness, biocompatibility and the like, and has wide application prospect in the fields of machinery, electronics, optics, biomedicine, aerospace and the like.
In recent years, different elements or nanoparticles such as Au, N, Ni, and ZnO are doped into an amorphous carbon thin film to prepare a functional carbon-based composite thin film having good electrical, optical, magnetic, and photocatalytic properties, which is of interest to researchers. However, the research on the iron/amorphous carbon interaction mechanism in the generation process of the phenomenon still has many difficulties and few researches, and the amorphous carbon film has low bonding force with the metal substrate and is easy to generate film peeling, thereby limiting the wider application of the amorphous carbon film.
Generally, the amorphous carbon film is classified into a diamond-like amorphous carbon film and a graphite-like amorphous carbon film according to the relative concentration ratio of sp3 to sp2 bonds in the amorphous carbon film. In the former, the relative concentration of sp3 bonded carbon is high, a disordered network structure is formed, and the mechanical property of the carbon film is influenced; the sp2 bond carbon has high relative concentration and is gathered into a graphite-like domain in the form of a six-atom ring, so that the dielectric property and the like of the carbon film are influenced. Therefore, the relative concentration ratio of sp3 bonded carbon to sp2 bonded carbon in the amorphous carbon film is closely related to the performance of the amorphous carbon film.
Common film preparation technologies include vacuum evaporation, sputtering, laser pulse deposition, molecular beam epitaxy, metal organic chemical vapor deposition, hot filament chemical vapor deposition, plasma enhanced chemical vapor deposition and the like, and film preparation technologies such as magnetron sputtering or plasma vapor deposition and the like, and the film preparation technologies have the disadvantages of complex equipment system, difficult operation, unstable film performance and high cost.
Disclosure of Invention
The present invention is directed to overcome the above-mentioned drawbacks of the prior art and to provide an iron-doped amorphous carbon thin film and a method for preparing the same.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing an iron-doped amorphous carbon film comprises the following steps:
(1) pretreatment: grinding and polishing an iron sheet serving as a substrate material, cleaning, drying, adhering the iron sheet to a sample rack of a vacuum chamber, and connecting an electrode by taking a carbon wire as an evaporation source;
(2) preparation before plating: vacuumizing the vacuum chamber and adjusting the target base distance;
(3) evaporation: and (3) regulating the evaporation resistance current to carry out evaporation under the condition of inert gas, and depositing a layer of carbon film on the surface of the iron sheet to prepare the iron-doped amorphous carbon film.
Preferably, in the step (1): the purity of the iron piece is 99.99%, the size is 10mm multiplied by 3mm, and the purity of the carbon wire is 99.99%.
Preferably, in the step (1): cleaning by ultrasonic cleaning with acetone and anhydrous ethanol for 15-30min, removing oil stain on surface, and blowing with nitrogen or argon.
Preferably, in the step (2): preheating the substrate material to make the temperature of the iron sheet reach 150-200 ℃.
Preferably, in the step (2): the vacuum degree in the vacuum chamber is more than 5 multiplied by 10-3Pa。
Preferably, in the step (2): the target base distance, i.e. the distance between the substrate material and the evaporation source, is 50-60 mm.
Preferably, in the step (2): when the vacuum is pumped, the iron sheet is firstly shielded by the baffle plate, and the iron sheet is removed after the vacuum degree is reached.
Preferably, the process conditions for vapor deposition in step (3) are as follows: the inert gas is argon, the flow rate is 0.1-0.5mL/min, the carbon wire is preheated for 20-30s, the evaporation current is 40-50A, the deposition time is 10-20min, the carbon wire is fused, and the evaporation is finished.
Preferably, in the step (3): the sample holder is kept rotating to keep the uniformity of evaporation in the evaporation process, and the rotating speed is 10-15 rpm.
The quality of the prepared carbon film is influenced by the surface property of the substrate material, the temperature, the evaporation rate, the vacuum degree and other factors of the substrate material during evaporation. The deposition needs to be finished under a higher vacuum degree, the vacuum degree is too low, molecules or atoms of an evaporation source collide with a large amount of gas molecules, so that the prepared carbon film is polluted, even oxide and the like are formed, and the purity of the carbon film is reduced; the evaporation rate is determined by the applied current, if the current is too high, the evaporation rate is too fast, and a uniform continuous film is difficult to form, otherwise, the deposited particles are too large, the valence state of the components is not uniformly distributed, and the flatness of the surface of the film is poor; the target base distance has a great influence on the thickness uniformity of the coating.
Compared with the prior art, the carbon element at the interface of the iron-doped amorphous carbon prepared by the invention mainly exists in the forms of amorphous carbon and an iron-carbon compound, wherein the amorphous carbon film mainly consists of two valence states of graphitized carbon sp2 and diamond carbon sp3, and the closer to the substrate, the higher the graphitization degree. The preparation method is simple, the deposition efficiency is high, and the prepared iron-doped amorphous carbon film is compact.
Drawings
Fig. 1 is an XRD pattern of an iron-doped amorphous carbon thin film prepared according to the present invention;
FIG. 2 is an XPS plot of the etching time of 600s for an Fe-doped amorphous carbon film prepared in accordance with the present invention;
FIG. 3 is an XPS plot of the etching time of 660s for an Fe-doped amorphous carbon film prepared according to the present invention;
FIG. 4 is an XPS plot of the etching time of 720s for an Fe-doped amorphous carbon film prepared in accordance with the present invention;
FIG. 5 is an XPS plot of 780s etching time for an Fe-doped amorphous carbon film prepared according to the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Adopting a laboratory vacuum evaporator, wherein a substrate material is high-purity iron (99.99%), the size is 10mm multiplied by 3mm, carrying out mirror polishing treatment, carrying out ultrasonic cleaning in absolute ethyl alcohol and acetone for 20min before use, then carrying out blow-drying by argon, and then adhering the sample to a sample rack in a vacuum chamber, wherein the sample rack autorotates in the evaporation process to keep the uniformity of a film, and the rotating speed is 15 rpm; the evaporation source is a high-purity carbon wire (99.99%), and two ends of the evaporation source are connected with a clamp and an electrode; adjusting target base distance before vapor deposition, i.e. adjusting the distance between the substrate material and the evaporation source to 50mm, protecting the substrate with an evaporation source baffle, and vacuumizing to a vacuum degree of more than 5 × 10-3Pa, removing the baffle; during vapor deposition, argon is introduced, the flow rate is 0.5mL/min, and the carbon wire is preheated for 30 s; adjusting the evaporation current to 40A, and performing carbon film evaporation; and after 20min of deposition, fusing the carbon wire, and finishing evaporation.
Example 2
Adopting a laboratory vacuum evaporator, wherein a substrate material is high-purity iron (99.99%), the size is 10mm multiplied by 3mm, carrying out mirror polishing treatment, carrying out ultrasonic cleaning in absolute ethyl alcohol and acetone for 15min before use, then carrying out blow-drying by argon, and then adhering the sample to a sample rack in a vacuum chamber, wherein the sample rack autorotates in the evaporation process to keep the uniformity of a film, and the rotating speed is 15 rpm; the evaporation source is a high-purity carbon wire (99.99%), and two ends of the evaporation source are connected with a clamp and an electrode; adjusting target base distance, namely adjusting the distance between the substrate material and the evaporation source to 55mm, protecting the substrate with an evaporation source baffle plate, and vacuumizing until the vacuum degree is more than 5 multiplied by 10-3Pa, removing the baffle; during vapor deposition, argon is introducedGas with the flow rate of 0.5mL/min and carbon wire preheating for 30 s; adjusting the evaporation current to 45A, and performing carbon film evaporation; and after 15min of deposition, fusing the carbon wire, and finishing evaporation.
The prepared iron-doped amorphous carbon film is subjected to XRD test, and an X-ray diffraction pattern of the invention is shown in figure 1, and as can be seen from the pattern, the carbon component consists of carbon and iron-carbon compounds.
XPS detection is performed on the prepared amorphous carbon film, and accompanying figures 2-5 show C1s spectrograms with etching time of 600s, 660s, 720s and 780s along the direction from the surface of the amorphous carbon film to an iron-carbon interface, and the etching depth is 162nm, 178nm, 194nm and 210nm respectively. From the fitting result of the C1s spectrogram, it can be known that the relative concentration ratio of sp2/sp3 hybridized bonds is gradually increased along the direction from the surface of the amorphous carbon film to the iron-carbon interface, the graphitization degree is increased, and the content of Fe-C compounds is gradually increased.
According to experimental results, the amorphous carbon film prepared by the vacuum evaporation method has the advantages that the relative concentration ratio of sp2/sp3 hybridized bonds is gradually increased along the direction from the surface of the amorphous carbon film to an iron-carbon interface, the graphitization degree is increased, and the content of Fe-C compounds is gradually increased.
Example 3
Adopting a laboratory vacuum evaporator, wherein a substrate material is high-purity iron (99.99%), the size is 10mm multiplied by 3mm, carrying out mirror polishing treatment, carrying out ultrasonic cleaning in absolute ethyl alcohol and acetone for 30min before use, then carrying out blow-drying by argon, and then adhering to a sample rack in a vacuum chamber, wherein the sample rack autorotates in the evaporation process to keep the uniformity of a film, and the rotating speed is 13 rpm; the evaporation source is a high-purity carbon wire (99.99%), and two ends of the evaporation source are connected with a clamp and an electrode; before evaporation, the target base distance is adjusted, i.e. the distance between the substrate material and the evaporation source is adjusted to 60mm, the substrate is protected by an evaporation source baffle plate, and the substrate is vacuumized until the vacuum degree is more than 5 multiplied by 10-3Pa, removing the baffle; during vapor deposition, argon is introduced, the flow rate is 0.1mL/min, and the carbon wire is preheated for 20 s; adjusting the evaporation current to 50A, and performing carbon film evaporation; and after deposition for 10min, fusing the carbon wire, and finishing evaporation.
Example 4
The vacuum evaporator for laboratory is adopted, and the base material isHigh-purity iron (99.99 percent) with the size of 10mm multiplied by 3mm is subjected to mirror polishing treatment, the high-purity iron is sequentially subjected to ultrasonic cleaning in absolute ethyl alcohol and acetone for 15min before use, then is dried by argon and then is adhered to a sample rack in a vacuum chamber, the sample rack rotates automatically in the evaporation process to keep the uniformity of a film, and the rotating speed is 10 rpm; the evaporation source is a high-purity carbon wire (99.99%), and two ends of the evaporation source are connected with a clamp and an electrode; before evaporation, the target base distance is adjusted, i.e. the distance between the substrate material and the evaporation source is adjusted to 60mm, the substrate is protected by an evaporation source baffle plate, and the substrate is vacuumized until the vacuum degree is more than 5 multiplied by 10-3Pa, removing the baffle; during vapor deposition, argon is introduced, the flow rate is 0.3mL/min, and the carbon wire is preheated for 25 s; adjusting the evaporation current to 50A, and performing carbon film evaporation; and after deposition for 10min, fusing the carbon wire, and finishing evaporation.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A preparation method of an iron-doped amorphous carbon film is characterized by comprising the following steps:
(1) pretreatment: grinding and polishing an iron sheet serving as a substrate material, cleaning, drying, adhering the iron sheet to a sample rack of a vacuum chamber, and connecting an electrode by taking a carbon wire as an evaporation source;
(2) preparation before plating: vacuumizing the vacuum chamber and adjusting the target base distance;
(3) evaporation: regulating the evaporation resistance current to carry out evaporation under the condition of inert gas, and depositing a layer of carbon film on the surface of the iron sheet to prepare an iron-doped amorphous carbon film;
in the step (2): the vacuum degree in the vacuum chamber is more than 5 multiplied by 10-3Pa；
In the step (2): the target base distance, namely the distance between the substrate material and the evaporation source is 50-60 mm;
the evaporation process conditions in the step (3) are as follows: the inert gas is argon, the flow rate is 0.1-0.5mL/min, the carbon wire is preheated for 20-30s, the evaporation current is 40-50A, and the deposition time is 10-20 min.
2. The method for preparing an iron-doped amorphous carbon thin film according to claim 1, wherein in the step (1): the purity of the iron piece is 99.99%, the size is 10mm multiplied by 3mm, and the purity of the carbon wire is 99.99%.
3. The method for preparing an iron-doped amorphous carbon thin film according to claim 1, wherein in the step (1): cleaning by ultrasonic cleaning with acetone and anhydrous ethanol for 15-30min, and blowing with nitrogen or argon.
4. The method of claim 1, wherein in the step (2): when the vacuum pumping is carried out, the iron sheet is firstly shielded by the baffle plate, and after the vacuum degree is reached, the iron sheet is removed.
5. The method of claim 1, wherein in step (3): the sample holder is kept rotating in the evaporation process, and the rotating speed is 10-15 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241590.1A CN109306455B (en) | 2018-10-24 | 2018-10-24 | Iron-doped amorphous carbon film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811241590.1A CN109306455B (en) | 2018-10-24 | 2018-10-24 | Iron-doped amorphous carbon film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109306455A CN109306455A (en) | 2019-02-05 |
| CN109306455B true CN109306455B (en) | 2020-04-28 |
Family
ID=65225578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811241590.1A Active CN109306455B (en) | 2018-10-24 | 2018-10-24 | Iron-doped amorphous carbon film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109306455B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005083144A1 (en) * | 2004-02-27 | 2005-09-09 | Japan Science And Technology Agency | Carbonaceous thin film, process for producing the same and member utilizing the thin film |
| CN101550530B (en) * | 2009-04-03 | 2010-11-10 | 清华大学 | Preparation iron doped carbon membrane material with white light photoconductive effect by pulse laser deposition method |
| CN101777590B (en) * | 2010-01-15 | 2011-08-17 | 清华大学 | Heterogenous junction film material with white light photovoltaic effect and preparation method thereof |
| DE102010062114B4 (en) * | 2010-11-29 | 2014-12-11 | Federal-Mogul Burscheid Gmbh | Sliding element, in particular piston ring, with a coating |
| CN104513955A (en) * | 2013-09-26 | 2015-04-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nitrogen-doped porous carbon film and product thereof |
-
2018
- 2018-10-24 CN CN201811241590.1A patent/CN109306455B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109306455A (en) | 2019-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5308661A (en) | Pretreatment process for forming a smooth surface diamond film on a carbon-coated substrate | |
| CN100560793C (en) | A kind of method for preparing nano composite diamond coating | |
| JP4755262B2 (en) | Method for producing diamond-like carbon film | |
| US8597731B2 (en) | Method for applying a diamond layer onto a graphite substrate | |
| CN108385066B (en) | Preparation method of hydrogen-free metal doped diamond-like coating and product thereof | |
| Alawajji et al. | Electrical properties of multilayer (DLC-TiC) films produced by pulsed laser deposition | |
| Imai et al. | Hydrogen-free fluorinated DLC films with high hardness prepared by using T-shape filtered arc deposition system | |
| CN109722642A (en) | Equipped with diamond/graphene the compound lubricating film workpiece and preparation method thereof | |
| Boeira et al. | Influence of base pressure prior to deposition on the adhesion behaviour of carbon thin films on steel | |
| US5824367A (en) | Method for the deposition of diamond film on an electroless-plated nickel layer | |
| CN109306455B (en) | Iron-doped amorphous carbon film and preparation method thereof | |
| CN114703452B (en) | CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof | |
| CN113621926A (en) | Low-stress diamond-like wear-resistant coating and preparation method thereof | |
| JP6142562B2 (en) | Super water-repellent material manufacturing method and super water-repellent material | |
| JP2003082458A (en) | Apparatus and method for forming amorphous carbon film | |
| CN108441825A (en) | Doping metals diamond-like coating preparation method and its product | |
| US8491964B1 (en) | Diamond nucleation using polyethene | |
| CN111041430A (en) | Production process of high-temperature-resistant diamond-like carbon film layer | |
| KR20150004664A (en) | Pre-processes for diamond film coating and diamond film coating method using the same | |
| JP5360603B2 (en) | Method for producing amorphous carbon-coated member | |
| KR20190122601A (en) | Equipment and Method for Doped Coating Using Filtered Cathodic Vacuum Arc | |
| Zhong et al. | Large‐Area Synthesis of Carbon Nanofibers by Low‐Power Microwave Plasma‐Assisted CVD | |
| Ali et al. | Role of surface pre-treatment in the CVD of diamond films on copper | |
| JP2005533171A (en) | Amorphous hydrogenated carbon membrane | |
| JP3718876B2 (en) | Ultra-hard film-coated member and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |