CN108165952B - A kind of preparation method of translucency hard carbon nitride films - Google Patents
A kind of preparation method of translucency hard carbon nitride films Download PDFInfo
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- CN108165952B CN108165952B CN201711285578.6A CN201711285578A CN108165952B CN 108165952 B CN108165952 B CN 108165952B CN 201711285578 A CN201711285578 A CN 201711285578A CN 108165952 B CN108165952 B CN 108165952B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000000758 substrate Substances 0.000 claims abstract description 73
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 72
- 210000002381 plasma Anatomy 0.000 claims abstract description 60
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 56
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 24
- 239000012495 reaction gas Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000003851 corona treatment Methods 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 136
- 239000000126 substance Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004575 stone Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/347—Carbon nitride
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Abstract
The invention discloses a kind of preparation methods of translucency hard carbon nitride films, method includes the following steps: cleaning glass substrate；Using methane as reaction gas, using plasma enhances chemical vapour deposition technique and deposits one layer of amorphous carbon film in glass substrate surface；Using plasma enhances chemical vapour deposition technique and carries out ammonia plasmas processing to the amorphous carbon film that glass substrate surface deposits；Using methane and ammonia as reaction gas, using plasma enhances chemical vapour deposition technique and deposits one layer of carbon nitride films in ammonia plasmas treated amorphous carbon surface；The Low Temperature Heat Treatment carbon nitride films in high pure nitrogen atmosphere.This method adjusts stress in thin films using the method for Low Temperature Heat Treatment by nitrogen-atoms and hydrogen atom content in modification glass substrate surface chemical bond, optimization carbon nitride films and in nitrogen atmosphere, so that carbon nitride films be made to have good hardness and translucency.
Description
Technical field
The present invention relates to translucency hard technical field of film preparation, and in particular to a kind of translucency hard carbon nitride films
Preparation method.
Background technique
Carbon nitride films are because having the characteristics that high resiliency, high rigidity, low-friction coefficient, surface roughness are small and preferable
Chemical inertness and stability, wear-resistant protection coating and in terms of have good application.In addition, it also has
The physical properties such as good electricity, optics, calorifics, so it is in solar battery, luminescent material and high temperature semiconductors material etc.
Also there is preferable application in field.The present invention prepares a kind of translucency hard by plasma enhanced chemical vapor deposition technology
Carbon nitride films, this method provide chemistry by glow discharge mode under higher substrate temperature for growth carbon nitride films
The stronger carbon of activity, nitrogen groups, and make the carbon nitride films nitrogen content with higher and less hydrogen content of growth.This nitrogen
Changing C film has many advantages, such as that transmissivity is high, hardness is big, wear resistance is strong and is not easy deliquescence, photoelectron technical field can
It is used as a kind of antireflection protective film.
Summary of the invention
Object of the present invention is to provide a kind of translucency hard carbon nitride films and preparation method thereof in photoelectron technical field.
This method is made a living under higher substrate temperature by glow discharge mode by plasma enhanced chemical vapor deposition technology
Long carbon nitride films provide the stronger carbon of chemical activity, nitrogen groups, and make the carbon nitride films nitrogen content with higher of growth
With less hydrogen content.The present invention does buffer layer under higher underlayer temperature with amorphous carbon layer, and passes through ammonia glow discharge
Mode carries out corona treatment to amorphous carbon buffer layer, this method be conducive to high energy active particle migrate in substrate surface,
Diffusion and nucleation and reacting between activated carbon, nitrogen groups and substrate surface atom provide advantage, to improve nitrogen
Change C film growth quality.The carbon nitride films prepared in this way have that transmissivity is high, hardness is big, wear resistance is strong and
It is not easy the advantages that deliquescing, can be used as a kind of antireflection protective film use in optoelectronic areas.
A kind of preparation method of translucency hard carbon nitride films provided by the invention, comprising the following steps:
(1) glass substrate is cleaned；
(2) using high-purity methane as working gas, using plasma enhances chemical vapor deposition method in glass substrate table
Face deposits one layer of amorphous carbon film；
(3) using high-purity ammonia as working gas, using plasma enhances chemical vapor deposition method to glass substrate table
The amorphous carbon film in face carries out ammonia plasmas processing；
(4) using high-purity methane and high-purity ammonia as reaction gas, using plasma enhancing chemical vapor deposition method exists
Ammonia plasmas treated amorphous carbon film surface prepares one layer of carbon nitride films in step (3)；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.Described
The purity of high-purity methane is greater than 99.999%；The purity of high-purity ammonia is greater than 99.999%99.9995%；The height
The purity of pure nitrogen gas is greater than 99.999%.
In the step (2), using plasma enhances glass substrate of the chemical vapour deposition technique in step (1)
Surface deposits one layer of amorphous carbon film, and technological parameter is: 300~400W of radio-frequency power, rf frequency 10-15MHz, substrate temperature
380~450 DEG C, 80~120Pa of chamber pressure, high-purity methane 60~90sccm of gas flow of degree is plated film time 15~25 seconds, thin
Film thickness is 5~12 nanometers.
In the step (2), using plasma enhances glass substrate of the chemical vapour deposition technique in step (1)
Surface deposits one layer of amorphous carbon film, and technological parameter is: radio-frequency power 350, rf frequency 13.56MHz, substrate temperature 400
DEG C, chamber pressure 100Pa, high-purity methane gas flow 75sccm, plated film time 20 seconds, film thickness was 9 nanometers.
In the step (3), high-purity ammonia plasmas is used by plasma enhanced chemical vapor deposition technology
The amorphous carbon film of glass substrate surface is handled, ammonia plasmas handles the technological parameter of glass substrate surface amorphous carbon film
It is: 200~300W of radio-frequency power, rf frequency 13.56MHz, 380~450 DEG C of substrate temperature, 100~160Pa of chamber pressure,
40~70sccm of high-purity ammonia gas flow, ammonia plasmas are handled the time 10~20 minutes.
In the step (3), high-purity ammonia plasmas is used by plasma enhanced chemical vapor deposition technology
The amorphous carbon film of glass substrate surface is handled, ammonia plasmas handles the technological parameter of glass substrate surface amorphous carbon film
It is: radio-frequency power 250W, rf frequency 12-15MHz, 400 DEG C of substrate temperature, chamber pressure 120Pa, high-purity ammonia gas flow
55sccm, ammonia plasmas are handled the time 15 minutes.
In the step (4), using plasma enhances the technique that chemical vapour deposition technique prepares carbon nitride films
Parameter is: 300~400W of radio-frequency power, rf frequency 12-15MHz, 380~450 DEG C of substrate temperature, chamber pressure 80~
120Pa, 50~80sccm of high-purity ammonia gas flow, high-purity methane 30~50sccm of gas flow, 50~80 points of plated film time
Clock, film thickness are 180~330 nanometers.
In the step (4), using plasma enhances the technique that chemical vapour deposition technique prepares carbon nitride films
Parameter is: radio-frequency power 350W, rf frequency 13.56MHz, 400 DEG C of substrate temperature, chamber pressure 100Pa, high-purity ammonia gas
Flow 70sccm, high-purity methane gas flow 40sccm, plated film time 60 minutes, film thickness was 260 nanometers.
In the step (5), low temperature is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere
The concrete technology of heat treatment is: it is passed through high pure nitrogen in quartzy annealing furnace before heating and is kept for 10-15 minutes, it then will preparation
The carbon nitride films of completion are placed in quartz boat and are pushed into quartzy annealing furnace, and carbon nitride films are in company with stone under nitrogen atmosphere protection
English annealing furnace is warming up to 450-500 DEG C together and is kept for 2-3 hour, later in company with quartzy annealing furnace under nitrogen atmosphere protection
Cooled to room temperature together.
This method by nitrogen-atoms and hydrogen atom content in modification glass substrate surface chemical bond, optimization carbon nitride films with
And stress in thin films is adjusted using the method for Low Temperature Heat Treatment in nitrogen atmosphere, so that it is good hard to have carbon nitride films
Degree and translucency.Relative to physical gas phase deposition technology and other chemical vapour deposition techniques is used, the present invention is in higher lining
Buffer layer is done with amorphous carbon layer at a temperature of bottom, and amorphous carbon buffer layer is carried out at plasma by ammonia glow discharge mode
Reason, this method are conducive to high energy active particle and migrate, spread and be nucleated in substrate surface and for activated carbon, nitrogen groups and base
Reaction between piece surface atom provides advantage, to improve carbon nitride films growth quality.
Detailed description of the invention
Film prepared by Fig. 1 embodiment 1 is in 300-900 nano waveband incident light transmittance curve figure
Specific embodiment
For the present invention is further explained, a kind of provided preparation method of translucency hard carbon nitride films, implements below
Case is not used in the limitation present invention to illustrate the present invention.
Embodiment 1:
A kind of preparation method of translucency hard carbon nitride films, method includes the following steps:
(1) glass substrate is cleaned；
(2) with high-purity methane (purity 99.999%) for working gas, using plasma enhances chemical vapor deposition
Technology deposits one layer of amorphous carbon film in glass substrate surface.Technological parameter is: radio-frequency power 350W, rf frequency
13.56MHz, 400 DEG C of substrate temperature, chamber pressure 100Pa, high-purity methane gas flow 75sccm, plated film time 20 seconds, film
With a thickness of 9 rans；
(3) with high-purity ammonia (purity 99.9995%) for working gas, using plasma enhances chemical vapor deposition
Technology carries out ammonia plasmas processing to the amorphous carbon film of glass substrate surface.Ammonia plasmas handles glass substrate table
The technological parameter of face amorphous carbon film is: radio-frequency power 250W, rf frequency 13.56MHz, 400 DEG C of substrate temperature, chamber pressure
120Pa, high-purity ammonia gas flow 55sccm, ammonia plasmas are handled the time 15 minutes；
(4) it is adopted with high-purity methane (purity 99.999%) and high-purity ammonia (purity 99.9995%) for reaction gas
With plasma enhanced chemical vapor deposition technology in step (3) ammonia plasmas treated amorphous carbon film surface system
Standby one layer of carbon nitride films.The technological parameter of carbon nitride films is: radio-frequency power 350W, rf frequency 13.56MHz, substrate temperature
400 DEG C, chamber pressure 100Pa, high-purity ammonia gas flow 70sccm, high-purity methane gas flow 40sccm of degree, plated film time
60 minutes, film thickness was 260 rans；
(5) Low Temperature Thermal is carried out to carbon nitride films prepared in step (4) in high pure nitrogen (99.999%) atmosphere
Processing.Specific heat treatment process is: high pure nitrogen (99.999%) is passed through before heating in quartzy annealing furnace and is kept for 12 minutes,
Then the carbon nitride films that preparation is completed are placed in quartz boat and are pushed into quartzy annealing furnace, the carbonitride under nitrogen atmosphere protection
Film is warming up to 480 DEG C in company with quartzy annealing furnace together and is kept for 2.5 hours, later in company with quartz under nitrogen atmosphere protection
Annealing furnace cooled to room temperature together.
The carbon nitride films prepared by above step are in 300-900 nano waveband transmittance graph as shown in Figure 1, film
Transmissivity is in 400-650 nano waveband up to 92%, and film hardness is up to 20GPa or so.
Embodiment 2:
A kind of preparation method of translucency hard carbon nitride films, method includes the following steps:
(1) glass substrate is cleaned；
(2) with high-purity methane (purity 99.999%) for working gas, using plasma enhances chemical vapor deposition
Technology deposits one layer of amorphous carbon film in glass substrate surface.Technological parameter is: radio-frequency power 300W, rf frequency
13.56MHz, 380 DEG C of substrate temperature, chamber pressure 120Pa, high-purity methane gas flow 90sccm, plated film time 15 seconds, film
With a thickness of 10 rans；
(3) with high-purity ammonia (purity 99.9995%) for working gas, using plasma enhances chemical vapor deposition
Technology carries out ammonia plasmas processing to the amorphous carbon film of glass substrate surface.Ammonia plasmas handles glass substrate table
The technological parameter of face amorphous carbon film is: radio-frequency power 200W, rf frequency 13.56MHz, 380 DEG C of substrate temperature, chamber pressure
100Pa, high-purity ammonia gas flow 70sccm, ammonia plasmas are handled the time 10 minutes；
(4) it is adopted with high-purity methane (purity 99.999%) and high-purity ammonia (purity 99.9995%) for reaction gas
With plasma enhanced chemical vapor deposition technology in step (3) ammonia plasmas treated amorphous carbon film surface system
Standby one layer of carbon nitride films.The technological parameter of carbon nitride films is: radio-frequency power 300W, rf frequency 13.56MHz, substrate temperature
380 DEG C, chamber pressure 80Pa, high-purity ammonia gas flow 60sccm, high-purity methane gas flow 30sccm of degree, plated film time 70
Minute, film thickness is 280 rans；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.Specific heat
Treatment process is: high pure nitrogen (99.999%) is passed through before heating in quartzy annealing furnace and is kept for 10 minutes, it then will preparation
The carbon nitride films of completion are placed in quartz boat and are pushed into quartzy annealing furnace, and carbon nitride films are in company with stone under nitrogen atmosphere protection
English annealing furnace is warming up to 450 DEG C together and is kept for 2 hours, later under nitrogen atmosphere protection in company with quartzy annealing furnace together from
So it is cooled to room temperature.
Completion is just prepared by a kind of translucency hard carbon nitride films of above step, film transmission is received in 400-650
VHF band is up to 90%, and film hardness is up to 15GPa or so.
Embodiment 3:
A kind of preparation method of translucency hard carbon nitride films, method includes the following steps:
(1) glass substrate is cleaned；
(2) with high-purity methane (purity 99.999%) for working gas, using plasma enhances chemical vapor deposition
Technology deposits one layer of amorphous carbon film in glass substrate surface.Technological parameter is: radio-frequency power 400W, rf frequency
13.56MHz, 450 DEG C of substrate temperature, chamber pressure 80Pa, high-purity methane gas flow 60sccm, plated film time 25 seconds, film
With a thickness of 12 rans；
(3) with high-purity ammonia (purity 99.9995%) for working gas, using plasma enhances chemical vapor deposition
Technology carries out ammonia plasmas processing to the amorphous carbon film of glass substrate surface.Ammonia plasmas handles glass substrate table
The technological parameter of face amorphous carbon film is: radio-frequency power 300W, rf frequency 13.56MHz, 450 DEG C of substrate temperature, chamber pressure
140Pa, high-purity ammonia gas flow 40sccm, ammonia plasmas are handled the time 20 minutes；
(4) it is adopted with high-purity methane (purity 99.999%) and high-purity ammonia (purity 99.9995%) for reaction gas
With plasma enhanced chemical vapor deposition technology in step (3) ammonia plasmas treated amorphous carbon film surface system
Standby one layer of carbon nitride films.The technological parameter of carbon nitride films is: radio-frequency power 400W, rf frequency 13.56MHz, substrate temperature
450 DEG C, chamber pressure 120Pa, high-purity ammonia gas flow 80sccm, high-purity methane gas flow 50sccm of degree, plated film time
50 minutes, film thickness was 180 rans；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.Specific heat
Treatment process is: high pure nitrogen (99.999%) is passed through before heating in quartzy annealing furnace and is kept for 15 minutes, it then will preparation
The carbon nitride films of completion are placed in quartz boat and are pushed into quartzy annealing furnace, and carbon nitride films are in company with stone under nitrogen atmosphere protection
English annealing furnace is warming up to 500 DEG C together and is kept for 3 hours, later under nitrogen atmosphere protection in company with quartzy annealing furnace together from
So it is cooled to room temperature.
Completion is just prepared by a kind of translucency hard carbon nitride films of above step, film transmission is received in 400-650
VHF band is up to 91%, and film hardness is up to 18GPa or so.
Embodiment 4:
A kind of preparation method of translucency hard carbon nitride films, method includes the following steps:
(1) glass substrate is cleaned；
(2) with high-purity methane (purity 99.999%) for working gas, using plasma enhances chemical vapor deposition
Technology deposits one layer of amorphous carbon film in glass substrate surface.Technological parameter is: radio-frequency power 370W, rf frequency
13.56MHz, 420 DEG C of substrate temperature, chamber pressure 90Pa, high-purity methane gas flow 80sccm, plated film time 15 seconds, film
With a thickness of 7 rans；
(3) with high-purity ammonia (purity 99.9995%) for working gas, using plasma enhances chemical vapor deposition
Technology carries out ammonia plasmas processing to the amorphous carbon film of glass substrate surface.Ammonia plasmas handles glass substrate table
The technological parameter of face amorphous carbon film is: radio-frequency power 220W, rf frequency 13.56MHz, 420 DEG C of substrate temperature, chamber pressure
160Pa, high-purity ammonia gas flow 60sccm, ammonia plasmas are handled the time 17 minutes；
(4) it is adopted with high-purity methane (purity 99.999%) and high-purity ammonia (purity 99.9995%) for reaction gas
With plasma enhanced chemical vapor deposition technology in step (3) ammonia plasmas treated amorphous carbon film surface system
Standby one layer of carbon nitride films.The technological parameter of carbon nitride films is: radio-frequency power 370W, rf frequency 13.56MHz, substrate temperature
420 DEG C, chamber pressure 90Pa, high-purity ammonia gas flow 50sccm, high-purity methane gas flow 30sccm of degree, plated film time 80
Minute, film thickness is 330 rans；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.Specific heat
Treatment process is: high pure nitrogen (99.999%) is passed through before heating in quartzy annealing furnace and is kept for 13 minutes, it then will preparation
The carbon nitride films of completion are placed in quartz boat and are pushed into quartzy annealing furnace, and carbon nitride films are in company with stone under nitrogen atmosphere protection
English annealing furnace is warming up to 470 DEG C together and is kept for 2 hours, later under nitrogen atmosphere protection in company with quartzy annealing furnace together from
So it is cooled to room temperature.
Completion is just prepared by a kind of translucency hard carbon nitride films of above step, film transmission is received in 400-650
VHF band is up to 90%, and film hardness is up to 14GPa or so.
Embodiment 5:
A kind of preparation method of translucency hard carbon nitride films, method includes the following steps:
(1) glass substrate is cleaned；
(2) with high-purity methane (purity 99.999%) for working gas, using plasma enhances chemical vapor deposition
Technology deposits one layer of amorphous carbon film in glass substrate surface.Technological parameter is: radio-frequency power 300W, rf frequency
13.56MHz, 380 DEG C of substrate temperature, chamber pressure 80Pa, high-purity methane gas flow 65sccm, plated film time 17 seconds, film
With a thickness of 5 rans；
(3) with high-purity ammonia (purity 99.9995%) for working gas, using plasma enhances chemical vapor deposition
Technology carries out ammonia plasmas processing to the amorphous carbon film of glass substrate surface.Ammonia plasmas handles glass substrate table
The technological parameter of face amorphous carbon film is: radio-frequency power 270W, rf frequency 13.56MHz, 380 DEG C of substrate temperature, chamber pressure
150Pa, high-purity ammonia gas flow 65sccm, ammonia plasmas are handled the time 13 minutes；
(4) it is adopted with high-purity methane (purity 99.999%) and high-purity ammonia (purity 99.9995%) for reaction gas
With plasma enhanced chemical vapor deposition technology in step (3) ammonia plasmas treated amorphous carbon film surface system
Standby one layer of carbon nitride films.The technological parameter of carbon nitride films is: radio-frequency power 330W, rf frequency 13.56MHz, substrate temperature
380 DEG C, chamber pressure 110Pa, high-purity ammonia gas flow 75sccm, high-purity methane gas flow 50sccm of degree, plated film time
65 minutes, film thickness was 240 rans；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.Specific heat
Treatment process is: high pure nitrogen (99.999%) is passed through before heating in quartzy annealing furnace and is kept for 15 minutes, it then will preparation
The carbon nitride films of completion are placed in quartz boat and are pushed into quartzy annealing furnace, and carbon nitride films are in company with stone under nitrogen atmosphere protection
English annealing furnace is warming up to 460 DEG C together and is kept for 3 hours, later under nitrogen atmosphere protection in company with quartzy annealing furnace together from
So it is cooled to room temperature.
Completion is just prepared by a kind of translucency hard carbon nitride films of above step, film transmission is received in 400-650
VHF band is up to 91%, and film hardness is up to 15GPa or so.
The above be present pre-ferred embodiments, but the present invention should not be limited to it is interior disclosed in the embodiment
Hold.So all do not depart from the lower equivalent or modification completed of spirit disclosed in this invention, the scope of protection of the invention is both fallen within.
Claims (8)
1. a kind of preparation method of translucency hard carbon nitride films, which is characterized in that this method includes the following steps:
(1) glass substrate is cleaned；
(2) using high-purity methane as working gas, it is heavy in glass substrate surface that using plasma enhances chemical vapor deposition method
One layer of amorphous carbon film of product, technological parameter is: 300~400W of radio-frequency power, rf frequency 10-15MHz, substrate temperature 380
~450 DEG C, 80~120Pa of chamber pressure, high-purity methane 60~90sccm of gas flow, plated film time 15~25 seconds, film is thick
Degree is 5~12 nanometers；
(3) using high-purity ammonia as working gas, using plasma enhances chemical vapor deposition method to glass substrate surface
Amorphous carbon film carries out ammonia plasmas processing, and ammonia plasmas handles the technique ginseng of glass substrate surface amorphous carbon film
Number is: 200~300W of radio-frequency power, rf frequency 13.56MHz, 380~450 DEG C of substrate temperature, chamber pressure 100~
160Pa, 40~70sccm of high-purity ammonia gas flow, ammonia plasmas are handled the time 10~20 minutes；
(4) using high-purity methane and high-purity ammonia as reaction gas, using plasma enhances chemical vapor deposition method in step
(3) ammonia plasmas treated amorphous carbon film surface prepares one layer of carbon nitride films in；
(5) Low Temperature Heat Treatment is carried out to carbon nitride films prepared in step (4) in high pure nitrogen atmosphere.
2. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that the high-purity methane
Purity be greater than 99.999%；The purity of high-purity ammonia is greater than 99.9995%；The purity of the high pure nitrogen is greater than
99.999%。
3. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (2), use
The glass substrate surface of plasma enhanced chemical vapor deposition technology in step (1) deposits one layer of amorphous carbon film, work
Skill parameter is: radio-frequency power 350, rf frequency 13.56MHz, 400 DEG C of substrate temperature, chamber pressure 100Pa, high-purity methane gas
Body flow 75sccm, plated film time 20 seconds, film thickness was 9 nanometers.
4. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (3), pass through
Plasma enhanced chemical vapor deposition technology uses the amorphous carbon film of high-purity ammonia corona treatment glass substrate surface,
The technological parameter of ammonia plasmas processing glass substrate surface amorphous carbon film is: radio-frequency power 250W, rf frequency 12-
15MHz, 400 DEG C of substrate temperature, chamber pressure 120Pa, high-purity ammonia gas flow 55sccm, ammonia plasmas handles the time
15 minutes.
5. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (4), use
The technological parameter that plasma enhanced chemical vapor deposition technology prepares carbon nitride films is: 300~400W of radio-frequency power, radio frequency
Frequency 12-15MHz, 380~450 DEG C of substrate temperature, 80~120Pa of chamber pressure, 50~80sccm of high-purity ammonia gas flow,
High-purity methane 30~50sccm of gas flow, plated film time 50~80 minutes, film thickness was 180~330 nanometers.
6. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (4), use
The technological parameter that plasma enhanced chemical vapor deposition technology prepares carbon nitride films is: radio-frequency power 350W, rf frequency
13.56MHz, 400 DEG C of substrate temperature, chamber pressure 100Pa, high-purity ammonia gas flow 70sccm, high-purity methane gas flow
40sccm, plated film time 60 minutes, film thickness was 260 nanometers.
7. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (5), in height
The concrete technology for carrying out Low Temperature Heat Treatment to carbon nitride films prepared in step (4) in pure nitrogen gas atmosphere is: before heating
It is passed through high pure nitrogen in quartzy annealing furnace and is kept for 10-15 minutes, the carbon nitride films that preparation is completed then are placed in quartz boat
Interior and be pushed into quartzy annealing furnace, carbon nitride films are warming up to 450-500 in company with quartzy annealing furnace together under nitrogen atmosphere protection
DEG C and kept for 2-3 hour, later in company with quartzy annealing furnace together cooled to room temperature under nitrogen atmosphere protection.
8. the preparation method of translucency hard carbon nitride films described in claim 1, which is characterized in that in step (5), in height
The concrete technology for carrying out Low Temperature Heat Treatment to carbon nitride films prepared in step (4) in pure nitrogen gas atmosphere is: before heating
It is passed through high pure nitrogen in quartzy annealing furnace and is kept for 12 minutes, is then placed in the carbon nitride films that preparation is completed in quartz boat simultaneously
It is pushed into quartzy annealing furnace, carbon nitride films are warming up to 480 DEG C in company with quartzy annealing furnace together and keep under nitrogen atmosphere protection
2.5 hours, later in company with quartzy annealing furnace together cooled to room temperature under nitrogen atmosphere protection.
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Application publication date: 20180615 Assignee: Henan Chaomei Building Materials Co.,Ltd. Assignor: CHINA THREE GORGES University Contract record no.: X2024980000728 Denomination of invention: A preparation method for transparent hard carbon nitride thin films Granted publication date: 20191108 License type: Common License Record date: 20240116 |