CN108130517B - A kind of electrically conducting transparent WC crystalline film and preparation method thereof - Google Patents
A kind of electrically conducting transparent WC crystalline film and preparation method thereof Download PDFInfo
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- CN108130517B CN108130517B CN201711434847.0A CN201711434847A CN108130517B CN 108130517 B CN108130517 B CN 108130517B CN 201711434847 A CN201711434847 A CN 201711434847A CN 108130517 B CN108130517 B CN 108130517B
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- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- 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
- C23C14/0635—Carbides
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Abstract
The invention discloses a kind of electrically conducting transparent WC crystalline film, X-ray diffraction (001) peak of the WC film is highest peak, and film is along c-axis preferred orientation, single hexagonal phase structure；Crystalline state WC film transmission of visible light is higher than 89%, and resistivity is lower than 7.6 × 10–4Ωcm；The atomic percent of W:C in WC film is 50.1:49.9 ~ 50.7:49.3；The microhardness of electrically conducting transparent crystalline state WC film is higher than 23GPa.The invention also discloses the preparation methods of the film: using radio frequency magnetron sputtering method, using WC alloy as target, Ar-CH4For working gas；WC film is in Ar and CH4Plasma atmosphere in grow；Growth temperature is 450-550 °C；In growth course, the target speed of rotation is 30 revs/min, and the substrate speed of rotation is 40 revs/min.WC film produced by the present invention, it is a kind of function film for having both two aspect performance of electrically conducting transparent and hard alloy, using it as device prepared by functional layer, there are good wear-resisting and corrosion-resistance characteristics, the application of microelectronics and opto-electronic device in harsh environment can be expanded.
Description
Technical field
The invention belongs to carbide semiconductor technical field more particularly to a kind of electrically conducting transparent WC crystalline film and its preparations
Method.
Background technique
Tungsten carbide (WC) is a kind of typical cemented carbide material, is hexagonal simple structure, temperature of the six side WC until 3049K
It is all stable under degree.WC has very excellent physical and chemical properties, such as high rigidity, high abrasion, thermal stability and chemistry
Stability is good, and good in oxidation resistance, thermal expansion coefficient is low, and elasticity modulus is high, has a degree of plasticity, and WC is most of
The performance of Binder Phase infiltration is better than other carbide, and than other carbide good toughness.In addition, WC also has high-termal conductivity and height
Electric conductivity is conducive to cutting application.In view of above-mentioned advantage, WC as a kind of hard wear-resistant coating, be widely used in defence and military,
The military and civilians industrial circle such as aerospace, metallurgy, petrochemical industry, electric power, communications and transportation, water conservancy, ocean development becomes solution weight
Want the key technology of components wear-and corrosion-resistant and protection.Currently, the mainstream technology of preparing of WC hard alloy coating is thermal spraying side
Method, comprising: plasma spray coating, flame-spraying, electric arc spraying, detonation flame spraying and supersonic spray coating etc..
Other than as hard alloy application, it or a kind of microelectronic material can have wide WC in microelectronic field
Application prospect, such as diffusion barrier layer, transparent conductive film as microelectronic component.WC film has crystalline state and amorphous state two
Kind, compared with amorphous state WC, crystalline state WC is thermally conductive and conductive characteristic is significantly better than amorphous state WC, thus generally wants in practical applications
Seeking WC film is crystalline state.Currently, people focus primarily upon hard alloy field to the research and development of WC, and to WC micro-
The application study of electronic field is seldom.
Summary of the invention
Based on the Development Status of WC material, the present invention provides a kind of electrically conducting transparent WC to expand WC material application field
Crystalline film and preparation method thereof.The present invention uses magnetically controlled sputter method, develops electrically conducting transparent WC film, and propose one kind
The method of direct crystalline state growth prepares high performance electrically conducting transparent WC film, and prepared WC film not only has electrically conducting transparent
Photoelectric characteristic, and the characteristic with hard alloy can have huge application value in microelectronics and optoelectronic areas.
In order to achieve the above object of the invention, the present invention adopts the following technical scheme:
The present invention provides a kind of electrically conducting transparent WC crystalline film, the WC film is crystalline film, X-ray diffraction
(001) peak is highest peak, and film is along c-axis preferred orientation, single hexagonal phase structure；Crystalline state WC film transmission of visible light is higher than
89%, resistivity is lower than 7.6 × 10–4Ωcm；The atomic percent of W:C in WC film is 50.1:49.9 ~ 50.7:49.3；Thoroughly
The microhardness of bright conductive crystalline WC film is higher than 23GPa.
The present invention also provides a kind of preparation methods of electrically conducting transparent WC crystalline film: radio frequency magnetron sputtering method is used,
Using high-purity WC alloy as target, Ar-CH4For working gas；It is preceding by Ar plasma bombardment using using quartz as substrate
Reason；When reaction chamber is evacuated to background vacuum higher than 1 × 10–4After Pa, it is passed through Ar-CH4Mixed gas, gas pressure intensity in deposition process
It is maintained at 1.0 Pa, CH in mixed gas4Content (with pressure gage) is 6%；WC film is in Ar and CH4Plasma atmosphere in it is raw
It is long；Growth temperature is 450-550 °C；In growth course, the target speed of rotation be 30 revs/min, the substrate speed of rotation be 40 turns/
Minute.
In above-mentioned preparation method, quartz substrate is only to enumerate, and other substrates can be selected in actual operation.
Above-mentioned technological parameter is that inventor establishes through test of many times, stringent and accurate control is needed, in the reality of inventor
If exceeding the range of above-mentioned technological parameter in testing, satisfactory electrically conducting transparent WC crystalline film can not be made.
The beneficial effects of the present invention are:
1) electrically conducting transparent WC crystalline film of the invention, the atomic percent of W:C is 50.1:49.9 ~ 50.7:49.3, non-
Very close to the stoichiometric ratio of the 1:1 in WC, and X-ray diffraction (001) peak is highest peak, and film is along c-axis preferred orientation, the WC
Film has excellent crystalline quality, can have high performance index.
2) electrically conducting transparent WC crystalline film transmission of visible light of the invention is higher than 89%, and resistivity is lower than 7.6 × 10–4Ω
Cm is had excellent performance, and can be led in many microelectronics such as light emitting diode, solar battery, transparence display, integrated circuit and photoelectron
It is applied in domain.
3) electrically conducting transparent crystalline state WC film of the invention, microhardness are higher than 23GPa, are that one kind has both electrically conducting transparent and hard
The function film of two aspect performance of matter alloy has good using electrically conducting transparent crystalline state WC film as device prepared by functional layer
Wear-resisting and corrosion-resistance characteristics, so as to expand the application of microelectronics and opto-electronic device in harsh environment.
4) magnetically controlled sputter method of the present invention is widely used in each industrial circle, has lower depositing temperature
With higher deposition rate, it is formed by film densification, and thickness is controllable, magnetically controlled sputter method technological parameter controllability is strong, can
Realize the Effective Regulation of electrically conducting transparent WC crystalline film structure and photoelectric properties.
5) preparation method simple process provided by the present invention, low manufacture cost are easily operated, it can be achieved that large-scale application
And industrialization.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) curve of electrically conducting transparent WC crystalline film made from embodiment 1.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and the specific embodiments.
Embodiment 1:
Using radio frequency magnetron sputtering method, using high-purity WC alloy as target, Ar-CH4For working gas；It is lining with quartz
Bottom is handled using preceding by Ar plasma bombardment；When reaction chamber is evacuated to background vacuum higher than 1 × 10–4After Pa, it is passed through Ar-
CH4Mixed gas, gas pressure intensity is maintained at 1.0 Pa, CH in mixed gas in deposition process4Content (with pressure gage) is 6%；WC
Film is in Ar and CH4Plasma atmosphere in grow；Growth temperature is 500 °C；In growth course, the target speed of rotation is 30
Rev/min, the substrate speed of rotation is 40 revs/min.
XRD, X-ray energy spectrum (EDX), UV-Vis spectrophotometry spectrum, Hall and micro- hard are carried out to WC film obtained
Degree test, test result are as follows: such as the XRD diagram that attached drawing 1 is WC film made from the embodiment, there are three diffraction maximums, it is right respectively
(001), (100) and (101) peak of WC, the diffraction maximum without other phases are answered, resulting WC film is single hexagonal phase structure,
In (001) peak be highest peak, film is along c-axis preferred orientation；The visible light that subordinate list 1 gives WC film made from each embodiment is saturating
The numerical value of rate, resistivity, constituent content and microhardness is penetrated, WC film transmission of visible light 89.6% made from the present embodiment, electricity
Resistance rate 7.1 × 10–4The atomic percent of Ω cm, the W:C in film are 50.4:49.6, microhardness 24GPa.
Embodiment 2:
Using radio frequency magnetron sputtering method, using high-purity WC alloy as target, Ar-CH4For working gas；It is lining with quartz
Bottom is handled using preceding by Ar plasma bombardment；When reaction chamber is evacuated to background vacuum higher than 1 × 10–4After Pa, it is passed through Ar-
CH4Mixed gas, gas pressure intensity is maintained at 1.0 Pa, CH in mixed gas in deposition process4Content (with pressure gage) is 6%；WC
Film is in Ar and CH4Plasma atmosphere in grow；Growth temperature is 450 °C；In growth course, the target speed of rotation is 30
Rev/min, the substrate speed of rotation is 40 revs/min.
XRD, X-ray energy spectrum (EDX), UV-Vis spectrophotometry spectrum, Hall and micro- hard are carried out to WC film obtained
Degree test, test result are as follows: WC film made from the embodiment is crystalline film, has single hexagonal phase structure, and X-ray is spread out
Penetrating (001) peak is highest peak, and film is along c-axis preferred orientation；Table 1 gives the visible transmission of WC film made from each embodiment
Rate, resistivity, constituent content and microhardness numerical value, the WC film transmission of visible light 90% obtained of the present embodiment, resistance
Rate 7.6 × 10–4The atomic percent of Ω cm, the W:C in film are 50.1:49.9, microhardness 25GPa.
Embodiment 3:
Using radio frequency magnetron sputtering method, using high-purity WC alloy as target, Ar-CH4For working gas；It is lining with quartz
Bottom is handled using preceding by Ar plasma bombardment；When reaction chamber is evacuated to background vacuum higher than 1 × 10–4After Pa, it is passed through Ar-
CH4Mixed gas, gas pressure intensity is maintained at 1.0 Pa, CH in mixed gas in deposition process4Content (with pressure gage) is 6%；WC
Film is in Ar and CH4Plasma atmosphere in grow；Growth temperature is 550 °C；In growth course, the target speed of rotation is 30
Rev/min, the substrate speed of rotation is 40 revs/min.
XRD, X-ray energy spectrum (EDX), UV-Vis spectrophotometry spectrum, Hall and micro- hard are carried out to WC film obtained
Degree test, test result are as follows: WC film made from the embodiment is crystalline film, has single hexagonal phase structure, and X-ray is spread out
Penetrating (001) peak is highest peak, and film is along c-axis preferred orientation；Table 1 gives the visible transmission of WC film made from each embodiment
Rate, resistivity, constituent content and microhardness numerical value, WC film transmission of visible light 89% made from the present embodiment, resistivity
6.9×10–4The atomic percent of Ω cm, the W:C in film are 50.7:49.3, microhardness 23GPa.
Table 1
| Transmission of visible light | Resistivity | W:C atomic percent | Microhardness | |
| Embodiment 1 | 89.6% | 7.1×10–4Ωcm | 50.4:49.6 | 24GPa |
| Embodiment 2 | 90% | 7.6×10–4Ωcm | 50.1:49.9 | 25GPa |
| Embodiment 3 | 89% | 6.9×10–4Ωcm | 50.7:49.3 | 23GPa |
Claims (3)
1. a kind of electrically conducting transparent WC crystalline film, it is characterised in that: X-ray diffraction (001) peak of the WC crystalline film is most
Qiang Feng, film is along c-axis preferred orientation, single hexagonal phase structure；The atomic percent of W:C in the WC film is 50.1:
49.9~50.7:49.3；The transmission of visible light of the WC crystalline film is higher than 89%, and resistivity is lower than 7.6 × 10–4Ω cm is shown
Microhardness is higher than 23GPa.
2. the method for preparing electrically conducting transparent WC crystalline film described in claim 1, using radio frequency magnetron sputtering method, feature exists
In including the following steps:
Using WC alloy as target, Ar-CH4For working gas；Substrate is handled using preceding by Ar plasma bombardment；Work as reaction chamber
Background vacuum is evacuated to higher than 1 × 10–4After Pa, it is passed through Ar-CH4Mixed gas, gas pressure intensity is maintained at 1.0 in deposition process
Pa；With pressure gage, CH in mixed gas4Content is 6%；The WC crystalline film is in Ar and CH4Plasma atmosphere in grow；
Growth temperature is 450-550 °C；In growth course, the target speed of rotation is 30 revs/min, and the substrate speed of rotation is 40 revs/min
Clock.
3. a kind of preparation method of electrically conducting transparent WC crystalline film as claimed in claim 2, it is characterised in that: substrate is quartz.
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| CN201711434847.0A CN108130517B (en) | 2017-12-26 | 2017-12-26 | A kind of electrically conducting transparent WC crystalline film and preparation method thereof |
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| CN201711434847.0A CN108130517B (en) | 2017-12-26 | 2017-12-26 | A kind of electrically conducting transparent WC crystalline film and preparation method thereof |
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| CN108130517B true CN108130517B (en) | 2019-10-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144277A (en) * | 1995-08-25 | 1997-03-05 | 东芝图格莱株式会社 | Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy |
| KR20050000219A (en) * | 2003-06-23 | 2005-01-03 | 학교법인 인하학원 | Method for preparing tungsten carbide layer for replacing electroplating of chromium |
| CN101497985A (en) * | 2009-02-19 | 2009-08-05 | 吉林大学 | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof |
-
2017
- 2017-12-26 CN CN201711434847.0A patent/CN108130517B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144277A (en) * | 1995-08-25 | 1997-03-05 | 东芝图格莱株式会社 | Plate-crystalline tungsten carbide-containing hard alloy, composition for forming plate-crystalline tungsten carbide and process for preparing said hard alloy |
| KR20050000219A (en) * | 2003-06-23 | 2005-01-03 | 학교법인 인하학원 | Method for preparing tungsten carbide layer for replacing electroplating of chromium |
| CN101497985A (en) * | 2009-02-19 | 2009-08-05 | 吉林大学 | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Effects of carbon incorporation in tungsten carbide films deposited by r.f.magnetron sputtering: single layers and multilayers;C. Rinco´n 等;《SURFACE&COATINGS TECHNOLOGY》;20031231;第163-164卷;386-391 * |
| Optical emission spectroscopy study of r.f. magnetron sputtering discharge used for multilayers thin film deposition;G. Zambrano 等;《SURFACE&COATINGS TECHNOLOGY》;20031231;第172卷;144-149 * |
| 磁控溅射法制备碳化钨薄膜的研究及应用进展;郑华均 等;《浙江化工》;20051231;第36卷(第1期);33-36 * |
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