CN109811303A - Nano-diamond film preparation method based on DLC film middle layer - Google Patents
Nano-diamond film preparation method based on DLC film middle layer Download PDFInfo
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Abstract
The invention discloses a kind of nano-diamond film preparation methods based on DLC film middle layer, are previously deposited one layer of DLC film on a monocrystaline silicon substrate as middle layer using ion beam composite intermediate frequency sputtering method；Microwave plasma (CVD) method is then utilized in DLC film middle layer, additional back bias voltage assistant depositing obtains nano-diamond film.The present invention generates the carbon source of high concentration using DLC film, increases the degree of supersaturation of carbon, to improve the Enhancing Nucleation Density of nano-diamond film；A large amount of atomic hydrogen is introduced during Bias-enhanced Nucleation, increases etching efficiency, to the crystallite dimension for reducing nano-diamond film, improves the Enhancing Nucleation Density of hetero-epitaxy nano-diamond film, and preparation high quality nano-diamond film has great significance.
Description
Technical field
The present invention relates to a kind of preparation processes of nano-diamond film, thin more particularly to a kind of composite nano-diamond
The preparation process of film is applied to inorganic non-metallic material manufacturing process technology field.
Background technique
Diamond is that have the characteristics such as excellent mechanics, electricity, calorifics and optics in the material of one, is such as had maximum
Young's modulus, highest thermal conductivity, highest forbidden bandwidth, minimum dielectric constant etc..These excellent physicochemical characteristics make
Diamond has broad application prospects in high-tech area.
Natural diamond content is rare, and artificial CVD method synthesis high quality, the diamond thin of large area are heavy as research
Point, and the extensive utilization of the hetero-epitaxy of diamond thin is mainly limited by lower Enhancing Nucleation Density.When directly untreated
Monocrystalline substrate on growing diamond membrane when, Enhancing Nucleation Density only has 104~105cm-2.Currently used raising forming core
Method has mechanical milling method, and ultrasonic seed-grain method, middle layer method and biased nucleation method etc. can significantly by pre-processed substrate
Enhancing Nucleation Density is improved, the nano-diamond film small to preparation crystallite dimension is of great significance.
Opposite middle layer method and biased nucleation method, mechanical milling method and ultrasonic seed-grain method are more bright to the raising of Enhancing Nucleation Density
It is aobvious, it can generally reach 1011cm-2, but also there is certain limitation.Mechanical milling method has apparent destruction to substrate, makes
It can not apply to prepare mems device and optical thin film.Ultrasonic seed-grain method is smaller to substrate destruction, but improves
The surface roughness of film makes it difficult to apply to prepare mems device and wear-resistant coating.When using middle layer method,
The material of selection is mostly iridium substrate, expensive.Biased nucleation is then not used to large area and prepares diamond thin.And it will be a variety of
The research for improving the preprocess method combined use of nano-diamond film Enhancing Nucleation Density is not yet mature.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Nano-diamond film preparation method based on DLC film middle layer, in conjunction with middle layer method and biased nucleation method, preparation
High-strength nano diamond thin uses the depositing diamond-like film conduct of ion beam composite intermediate frequency sputtering method on a variety of substrates
Middle layer, then uses MPCVD method, additional back bias voltage in diamond-like middle layer, and preparation is received
Rice diamond thin.It is used to improve the Enhancing Nucleation Density of nano-diamond film in conjunction with two kinds of preprocess methods, to prepare crystal grain ruler
Very little small nano-diamond film provides effective solution.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of nano-diamond film preparation method based on DLC film middle layer, includes the following steps:
A. substrate pre-treatment:
It places the substrate in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, at least clean 15 minutes, continue cycling through this
Cleaning process at least twice, the substrate cleaned up；Then with mass percent concentration not less than 40% hydrofluoric acid and
Deionized water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3, uses hydrofluoric acid dilutions
The substrate cleaned up is carried out corrosion treatment at least 90 seconds, the oxide impurity of substrate surface is removed, obtains pretreated
Substrate, it is spare as substrate；It is preferred that the substrate is silicon substrate, metal material substrate or composite substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put into for pretreated substrate in the step a, reach to vacuum degree not higher than 1.3*10-1Pa
When, ion beam cleaning is carried out to substrate, control Ar throughput is not less than 17sccm, and bias is not less than 1650V, and it is clear to carry out ion beam
Wash processing at least 15 minutes；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to not higher than 3.3*
10-1Pa, and Ti target is changed, mid frequency sputtering is carried out, control electric current is not less than 13A, and duty ratio is not less than 80%, and power is not less than
12kW, control Ar throughput are not less than 60sccm, and sputtering time is not less than 30 minutes, in deposition on substrate Ti film layer；In Ti
After the completion of film layer sputtering technology, start to continue depositing diamond-like film in Ti film layer, and control bias and be not less than
1600V, control Ar throughput are not less than 10sccm, and acetylene flow is not less than 80sccm, and control mid frequency sputtering power is not less than
1.5kW, sedimentation time are 1~3 hour, Ti/DLC multilayer film composite layer are prepared, to be previously deposited diamond-like on substrate
Film laminated layer forms compound substrate as middle layer preset between substrate and the nano-diamond film of subsequent preparation；So
After cool down, when vacuum room temperature is down to 130 DEG C or less, deflation vacuum breaker is carried out to vacuum chamber, then samples, is had
There is the compound substrate of DLC film middle layer；It is preferred that the thickness of prepared DLC film middle layer is not more than 1um；
C. microwave plasma CVD method is used, prepares nanometer in the compound substrate obtained in stepb
Diamond thin；Wherein the pressure in ion bombardment stage cavity is not less than 100Torr, and power is not less than 3.0kW, hydrogen flowing quantity
Not less than 500sccm, bombardment time at least 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, controls hydrogen flowing quantity
For 425~450sccm, methane flow is 50~75sccm, and bias is -100~-300V, and nucleated time is 15~60 minutes；?
In growth course, 460~475sccm of hydrogen flowing quantity, 25~40sccm of methane flow are controlled, growth time is 1~5 hour, is obtained
To nano-diamond film.It is preferred that the thickness of gained nano-diamond film is not more than 50nm.As currently preferred technology
Scheme, in the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is 425~450sccm, methane flow 50
~75sccm, bias are -200~-300V, and nucleated time is 15~30 minutes.It is preferred that the thickness of gained nano-diamond film
No more than 100nm.It is preferred that the Nano diamond crystallite dimension in gained nano-diamond film is 10~50nm.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the present invention combines middle layer method and biased nucleation method, in monocrystalline substrate heteroepitaxial growth nanometer Buddha's warrior attendant
Stone film, obtained nano-diamond film crystallite dimension is smaller, and Enhancing Nucleation Density is higher；
2. DLC film prepared by the present invention compared to monocrystalline substrate or other substrates have it is higher stick be
Number, reduces the re-evaporation effect of diamond nano seed crystal, and the high substrate of this concentration of carbon can be used as one layer of barrier and prevent
Carbon atom is conducive to improve second nucleation rate, to reduce nano-diamond film in the interior diffusion of substrate in nucleation process
Crystallite dimension；
3. the present invention generates the carbon source of high concentration using DLC film, increase the degree of supersaturation of carbon, to improve
The Enhancing Nucleation Density of nano-diamond film；A large amount of atomic hydrogen is introduced during Bias-enhanced Nucleation, increases etching efficiency, to reduction
The crystallite dimension of nano-diamond film improves the Enhancing Nucleation Density of hetero-epitaxy nano-diamond film, and preparation high quality
Nano-diamond film has great significance.
Detailed description of the invention
Fig. 1 is the nano-diamond film Raman light based on DLC film middle layer prepared by the embodiment of the present invention one
Spectrogram.
Fig. 2 is DLC film prepared by the embodiment of the present invention one and the nanogold based on DLC film middle layer
The comparison diagram of hard rock film surface appearance.
Fig. 3 is the nano-diamond film section shape based on DLC film middle layer prepared by the embodiment of the present invention one
Looks figure.
Fig. 4 is that the nano-diamond film XRD based on DLC film middle layer prepared by the embodiment of the present invention one spreads out
Penetrate figure.
The receiving based on DLC film middle layer that Fig. 5 is the embodiment of the present invention two, prepared by embodiment three, example IV
Rice diamond thin Raman spectrogram.
Fig. 6 is the nano-diamond film section shape based on DLC film middle layer prepared by the embodiment of the present invention two
Looks figure.
The receiving based on DLC film middle layer that Fig. 7 is the embodiment of the present invention two, prepared by embodiment three, example IV
Rice diamond thin XRD diffraction pattern.
Fig. 8 is the nano-diamond film section shape based on DLC film middle layer prepared by the embodiment of the present invention three
Looks figure.
Fig. 9 is the nano-diamond film section shape based on DLC film middle layer prepared by the embodiment of the present invention four
Looks figure.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one:
In the present embodiment, a kind of nano-diamond film preparation method based on DLC film middle layer, step
It is rapid as follows:
A. substrate pre-treatment:
Monocrystalline silicon substrate is placed in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, is persistently cleaned 15 minutes, is completed
Cleaning process, continues cycling through this cleaning process twice, the substrate cleaned up；Then it is with mass percent concentration
40% hydrofluoric acid and deionized water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3,
Corrosion treatment is carried out 90 seconds to the substrate cleaned up with hydrofluoric acid dilutions, the oxide for removing monocrystalline silicon substrate surface is miscellaneous
Matter obtains pretreated monocrystalline silicon substrate, spare as substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put by pretreated monocrystalline silicon substrate in the step a, reach 1.3*10 to vacuum degree-1Pa
When, ion beam cleaning is carried out to substrate, control Ar throughput is 17sccm, bias 1650V, carries out ion beam cleaning processing 15
Minute；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to 3.3*10-1Pa, and Ti target is changed, it carries out
Mid frequency sputtering, control electric current are 13A, and duty ratio 80%, power 12kW, control Ar throughput is 60sccm, sputtering time
It is 30 minutes, the depositing Ti film layer on monocrystalline silicon substrate；After the completion of Ti film layer sputtering technology, start in Ti film layer
Continuing depositing diamond-like film, and controlling bias is 1600V, control Ar throughput is 10sccm, and acetylene flow is 80sccm,
Control mid frequency sputtering power is 1.5kW, and sedimentation time is 3 hours, Ti/DLC multilayer film composite layer is prepared, thus pre- on substrate
First depositing diamond-like Film laminated layer forms compound substrate as middle layer；Then cool down, dropped to vacuum room temperature
When to 130 DEG C or less, deflation vacuum breaker is carried out to vacuum chamber, is then sampled, obtains that there is answering for DLC film middle layer
Close substrate；
C. microwave plasma CVD method is used, prepares nanometer in the compound substrate obtained in stepb
Diamond thin；Wherein the pressure in ion bombardment stage cavity is 100Torr, power 3.0kW, and hydrogen flowing quantity is
500sccm, bombardment time are 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is
450sccm, methane flow 50sccm, bias are -300V, and nucleated time is 15 minutes；During the growth process, hydrogen stream is controlled
460sccm, methane flow 40sccm are measured, growth time is 5 hours, obtains nano-diamond film.
Experimental test and analysis:
It is characterized using the nano-diamond film structure that Raman scattering prepares embodiment one, discovery film exists
Nano diamond characteristic peak is generated under the excitation of 632nm incidence wave, is located at 1320cm-1, show in diamond-like middle layer at
Function is prepared for nano-diamond film, as shown in Fig. 1 Raman spectrogram.
It is characterized using the nano-diamond film pattern that field emission scanning electron microscope prepares embodiment one, with
DLC film middle layer is compared, and nano-diamond film surface is finer and close, and cluster is less, as shown in Figure 2.Wherein Fig. 2 (a)
Figure is DLC film surface topography map prepared by the embodiment of the present invention one, and wherein Fig. 2 (b) figure is that the embodiment of the present invention one is made
The surface topography map of the standby nano-diamond film based on DLC film middle layer.
The nano-diamond film cross-section diagram prepared from embodiment one, fig. 3, it is shown that the diamond-like of preparation
Stone membrane middle layer (DLC) is with a thickness of 183nm, and nano-diamond film (ND) is with a thickness of 50nm.
It is characterized using the Nano diamond crystallite dimension that XRD diffraction prepares embodiment one, it is super with the prior art
The film of sound seed-grain method preparation compares discovery, under same sedimentary condition before film crystallite dimension be micron order, and utilize real
It applies the nano-diamond film crystallite dimension that example one is prepared based on DLC film middle layer and is calculated as nanoscale, and not
Greater than 20nm, as shown in Figure 4.
The DLC film that embodiment one uses has higher sticking coefficient compared to monocrystalline substrate, reduces gold
The re-evaporation effect of hard rock nanometer seed crystal, and the high substrate of this concentration of carbon can be used as one layer of barrier and prevent carbon in nucleation process
Atom is conducive to improve second nucleation rate, to reduce the crystallite dimension of nano-diamond film in the interior diffusion of substrate.This reality
Nano-diamond film preparation method of the example based on DLC film middle layer is applied, is existed using ion beam composite intermediate frequency sputtering method
One layer of DLC film is previously deposited in monocrystalline substrate as middle layer；Then utilized in DLC film middle layer
Microwave plasma (CVD) method, additional back bias voltage assistant depositing obtain nano-diamond film.The present embodiment method utilizes
DLC film generates the carbon source of high concentration, increases the degree of supersaturation of carbon, to improve the forming core of nano-diamond film
Density；A large amount of atomic hydrogen is introduced during Bias-enhanced Nucleation, increases etching efficiency, to the crystal grain for reducing nano-diamond film
Size improves the Enhancing Nucleation Density of hetero-epitaxy nano-diamond film, and preparation high quality nano-diamond film has very greatly
Meaning.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of nano-diamond film preparation method based on DLC film middle layer, step
It is rapid as follows:
A. substrate pre-treatment:
Monocrystalline silicon substrate is placed in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, is persistently cleaned 15 minutes, is completed
Cleaning process, continues cycling through this cleaning process twice, the substrate cleaned up；Then it is with mass percent concentration
40% hydrofluoric acid and deionized water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3,
Corrosion treatment is carried out 90 seconds to the substrate cleaned up with hydrofluoric acid dilutions, the oxide for removing monocrystalline silicon substrate surface is miscellaneous
Matter obtains pretreated monocrystalline silicon substrate, spare as substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put by pretreated monocrystalline silicon substrate in the step a, reach 1.3*10 to vacuum degree-1Pa
When, ion beam cleaning is carried out to substrate, control Ar throughput is 17sccm, bias 1650V, carries out ion beam cleaning processing 15
Minute；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to 3.3*10-1Pa, and Ti target is changed, it carries out
Mid frequency sputtering, control electric current are 13A, and duty ratio 80%, power 12kW, control Ar throughput is 60sccm, sputtering time
It is 30 minutes, the depositing Ti film layer on monocrystalline silicon substrate；After the completion of Ti film layer sputtering technology, start in Ti film layer
Continuing depositing diamond-like film, and controlling bias is 1600V, control Ar throughput is 10sccm, and acetylene flow is 80sccm,
Control mid frequency sputtering power is 1.5kW, and sedimentation time is 3 hours, Ti/DLC multilayer film composite layer is prepared, thus pre- on substrate
First depositing diamond-like Film laminated layer forms compound substrate as middle layer；Then cool down, dropped to vacuum room temperature
When to 130 DEG C or less, deflation vacuum breaker is carried out to vacuum chamber, is then sampled, obtains that there is answering for DLC film middle layer
Close substrate；
C. microwave plasma CVD method is used, prepares nanometer in the compound substrate obtained in stepb
Diamond thin；Wherein the pressure in ion bombardment stage cavity is 100Torr, power 3.0kW, and hydrogen flowing quantity is
500sccm, bombardment time are 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is
450sccm, methane flow 50sccm, bias are -200V, and nucleated time is 30 minutes；During the growth process, hydrogen stream is controlled
460sccm, methane flow 40sccm are measured, growth time is 5 hours, obtains nano-diamond film.
Experimental test and analysis:
The present embodiment method reduces outer biasing in nano-diamond film forming core growth course compared with embodiment one
Pressure.
It is characterized using the nano-diamond film structure that Raman scattering prepares embodiment two, discovery film exists
Nano diamond characteristic peak is generated under the excitation of 632nm incidence wave, is located at 1332cm-1, show in diamond-like middle layer at
Function is prepared for nano-diamond film, as shown in Fig. 5 (A).
The nano-diamond film pattern that using field emission scanning electron microscope and XRD diffraction prepared by embodiment two and
Microstructure is characterized, and is compared and is found with film prepared by the ultrasonic seed-grain method of the prior art, under same sedimentary condition before
Film crystallite dimension be micron order, and the nano-diamond film crystalline substance for utilizing embodiment two prepare based on diamond-like middle layer
Particle size is nanoscale, and the DLC film middle layer (DLC) of preparation is with a thickness of 202nm；Nano-diamond film (ND) is thick
Degree is 36nm, as shown in Figure 6.The reduction of applying bias reduces corrasion of the atomic hydrogen to DLC middle layer, so that in DLC
Interbed thickness increases.Nano-diamond film crystallite dimension is calculated as nanoscale, and is not more than 17.8nm, such as Fig. 7 (A) institute
Show.DLC middle layer improves the carbon source concentration of film growth, increases the second nucleation rate of Nano diamond, leads to nanogold
Hard rock film crystal grain reduces.Nano-diamond film preparation method of the present embodiment based on DLC film middle layer utilizes
Ion beam composite intermediate frequency sputtering method is previously deposited one layer of DLC film as middle layer on a monocrystaline silicon substrate；Then in class
Microwave plasma (CVD) method is utilized in diamond thin middle layer, additional back bias voltage assistant depositing obtains Nano diamond
Film.The present embodiment method generates the carbon source of high concentration using DLC film, increases the degree of supersaturation of carbon, to improve
The Enhancing Nucleation Density of nano-diamond film；A large amount of atomic hydrogen is introduced during Bias-enhanced Nucleation, increases etching efficiency, to reduction
The crystallite dimension of nano-diamond film improves the Enhancing Nucleation Density of hetero-epitaxy nano-diamond film, and preparation high quality
Nano-diamond film has great significance.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of nano-diamond film preparation method based on DLC film middle layer, step
It is rapid as follows:
A. substrate pre-treatment:
Monocrystalline silicon substrate is placed in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, is persistently cleaned 15 minutes, is completed
Cleaning process, continues cycling through this cleaning process twice, the substrate cleaned up；Then it is with mass percent concentration
40% hydrofluoric acid and deionized water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3,
Corrosion treatment is carried out 90 seconds to the substrate cleaned up with hydrofluoric acid dilutions, the oxide for removing monocrystalline silicon substrate surface is miscellaneous
Matter obtains pretreated monocrystalline silicon substrate, spare as substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put by pretreated monocrystalline silicon substrate in the step a, reach 1.3*10 to vacuum degree-1Pa
When, ion beam cleaning is carried out to substrate, control Ar throughput is 17sccm, bias 1650V, carries out ion beam cleaning processing 15
Minute；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to 3.3*10-1Pa, and Ti target is changed, it carries out
Mid frequency sputtering, control electric current are 13A, and duty ratio 80%, power 12kW, control Ar throughput is 60sccm, sputtering time
It is 30 minutes, the depositing Ti film layer on monocrystalline silicon substrate；After the completion of Ti film layer sputtering technology, start in Ti film layer
Continuing depositing diamond-like film, and controlling bias is 1600V, control Ar throughput is 10sccm, and acetylene flow is 80sccm,
Control mid frequency sputtering power is 1.5kW, and sedimentation time is 1 hour, Ti/DLC multilayer film composite layer is prepared, thus pre- on substrate
First depositing diamond-like Film laminated layer forms compound substrate as middle layer；Then cool down, dropped to vacuum room temperature
When to 130 DEG C or less, deflation vacuum breaker is carried out to vacuum chamber, is then sampled, obtains that there is answering for DLC film middle layer
Close substrate；
C. microwave plasma CVD method is used, prepares nanometer in the compound substrate obtained in stepb
Diamond thin；Wherein the pressure in ion bombardment stage cavity is 100Torr, power 3.0kW, and hydrogen flowing quantity is
500sccm, bombardment time are 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is
450sccm, methane flow 50sccm, bias are -300V, and nucleated time is 30 minutes；During the growth process, hydrogen stream is controlled
460sccm, methane flow 40sccm are measured, growth time is 5 hours, obtains nano-diamond film.
Experimental test and analysis:
The present embodiment method reduces sedimentation time in DLC middle layer preparation process compared with embodiment one.
It is characterized using the nano-diamond film structure that Raman scattering prepares embodiment three, discovery film exists
Nano diamond characteristic peak is generated under the excitation of 632nm incidence wave, is located at 1332cm-1, show in diamond-like middle layer at
Function is prepared for nano-diamond film, as shown in Fig. 5 (B).
The nano-diamond film pattern using field emission scanning electron microscope and XRD diffraction prepared by embodiment three into
Row characterization is compared with film prepared by the ultrasonic seed-grain method of the prior art and is found, under same sedimentary condition before film crystal grain
Having a size of micron order, and the nano-diamond film crystallite dimension prepared using embodiment three based on diamond-like middle layer is to receive
Meter level, the nano-diamond film (ND) of preparation is with a thickness of 65nm, as shown in Figure 8.Reduce in DLC middle layer preparation process
Growth time reduces DLC intermediate layer thickness.In nano-diamond film growth course, the corrasion of atomic hydrogen makes
DLC middle layer is reformed completely into the nucleation point of Nano diamond, and nano-diamond film thickness is caused to increase.Nano diamond
Film crystallite dimension is calculated as nanoscale, and is not more than 40nm, as shown in Fig. 7 (B).Since DLC middle layer is by atomic hydrogen
Etching completely reduces the carbon source concentration of film growth, nano-diamond film crystal grain is caused to become larger.The present embodiment is based on eka-gold
The nano-diamond film preparation method of hard rock membrane middle layer, on a monocrystaline silicon substrate using ion beam composite intermediate frequency sputtering method
One layer of DLC film is previously deposited as middle layer；Microwave plasma is then utilized in DLC film middle layer
Vapour deposition process, additional back bias voltage assistant depositing obtain nano-diamond film.The present embodiment method utilizes DLC film
The carbon source for generating high concentration, increases the degree of supersaturation of carbon, to improve the Enhancing Nucleation Density of nano-diamond film；In bias shape
A large amount of atomic hydrogen is introduced in nuclear process, increases etching efficiency, to the crystallite dimension for reducing nano-diamond film, is improved heterogeneous
The Enhancing Nucleation Density of extension nano-diamond film, and preparation high quality nano-diamond film have great significance.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of nano-diamond film preparation method based on DLC film middle layer, step
It is rapid as follows:
A. substrate pre-treatment:
Monocrystalline silicon substrate is placed in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, is persistently cleaned 15 minutes, is completed
Cleaning process, continues cycling through this cleaning process twice, the substrate cleaned up；Then it is with mass percent concentration
40% hydrofluoric acid and deionized water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3,
Corrosion treatment is carried out 90 seconds to the substrate cleaned up with hydrofluoric acid dilutions, the oxide for removing monocrystalline silicon substrate surface is miscellaneous
Matter obtains pretreated monocrystalline silicon substrate, spare as substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put by pretreated monocrystalline silicon substrate in the step a, reach 1.3*10 to vacuum degree-1Pa
When, ion beam cleaning is carried out to substrate, control Ar throughput is 17sccm, bias 1650V, carries out ion beam cleaning processing 15
Minute；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to 3.3*10-1Pa, and Ti target is changed, it carries out
Mid frequency sputtering, control electric current are 13A, and duty ratio 80%, power 12kW, control Ar throughput is 60sccm, sputtering time
It is 30 minutes, the depositing Ti film layer on monocrystalline silicon substrate；After the completion of Ti film layer sputtering technology, start in Ti film layer
Continuing depositing diamond-like film, and controlling bias is 1600V, control Ar throughput is 10sccm, and acetylene flow is 80sccm,
Control mid frequency sputtering power is 1.5kW, and sedimentation time is 3 hours, Ti/DLC multilayer film composite layer is prepared, thus pre- on substrate
First depositing diamond-like Film laminated layer forms compound substrate as middle layer；Then cool down, dropped to vacuum room temperature
When to 130 DEG C or less, deflation vacuum breaker is carried out to vacuum chamber, is then sampled, obtains that there is answering for DLC film middle layer
Close substrate；
C. microwave plasma CVD method is used, prepares nanometer in the compound substrate obtained in stepb
Diamond thin；Wherein the pressure in ion bombardment stage cavity is 100Torr, power 3.0kW, and hydrogen flowing quantity is
500sccm, bombardment time are 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is
425sccm, methane flow 75sccm, bias are -100V, and nucleated time is 60 minutes；During the growth process, hydrogen stream is controlled
475sccm, methane flow 25sccm are measured, growth time is 1 hour, obtains nano-diamond film.
Experimental test and analysis:
The present embodiment method increases the carbon source concentration in nano-diamond film nucleation process compared with embodiment one,
Reduce carbon source concentration and applying bias in nano-diamond film growth course.
It is characterized using the nano-diamond film structure that Raman scattering prepares embodiment three, discovery film exists
Nano diamond characteristic peak is generated under the excitation of 632nm incidence wave, is located at 1332cm-1, show in diamond-like middle layer at
Function is prepared for nano-diamond film, and the reduction of applying bias is so that atomic hydrogen etches insufficient, the Nano diamond of preparation
Film contains more amorphous phase, reduces film quality, shows 1332cm-1And 1480cm-1Peak broadens, such as Fig. 5 (C) institute
Show.
The nano-diamond film pattern using field emission scanning electron microscope and XRD diffraction prepared by example IV into
Row characterization is compared with film prepared by the ultrasonic seed-grain method of the prior art and is found, under same sedimentary condition before film crystal grain
Having a size of micron order, and the nano-diamond film crystallite dimension prepared using example IV based on diamond-like middle layer is to receive
Meter level, the DLC film middle layer (DLC) of preparation is with a thickness of 240nm；Nano-diamond film (ND) is with a thickness of 48nm, such as
Shown in Fig. 9.In Nano diamond growth course, the reduction of applying bias reduces atomic hydrogen and makees to the etching of DLC middle layer
With DLC middle layer is thicker；The reduction of carbon source concentration leads to the reduction of nano-diamond film growth rate, and thickness is reduced.Nanogold
Hard rock film crystallite dimension is calculated as nanoscale, and is not more than 12.7nm, as shown in Fig. 7 (C).Nano-diamond film shape
In nuclear process, the raising of carbon source concentration increases the second nucleation rate of Nano diamond, reduces the crystal grain ruler of Nano diamond
It is very little.Nano-diamond film preparation method of the present embodiment based on DLC film middle layer, utilizes ion beam composite intermediate frequency
Sputtering method is previously deposited one layer of DLC film as middle layer on a monocrystaline silicon substrate；Then among DLC film
Microwave plasma (CVD) method is utilized on layer, additional back bias voltage assistant depositing obtains nano-diamond film.The present embodiment
Method generates the carbon source of high concentration using DLC film, increases the degree of supersaturation of carbon, so that it is thin to improve Nano diamond
The Enhancing Nucleation Density of film；A large amount of atomic hydrogen is introduced during Bias-enhanced Nucleation, increases etching efficiency, and to reducing, Nano diamond is thin
The crystallite dimension of film, the Enhancing Nucleation Density of raising hetero-epitaxy nano-diamond film, and preparation high quality Nano diamond are thin
Film has great significance.
The above embodiment of the present invention combines middle layer method and biased nucleation method, in monocrystalline substrate heteroepitaxial growth
Nano-diamond film, obtained nano-diamond film crystallite dimension is smaller, and Enhancing Nucleation Density is higher.It is prepared in the above embodiments
DLC film has higher sticking coefficient compared to monocrystalline substrate or other substrates, reduces diamond nano seed crystal
Re-evaporation effect, and the high substrate of this concentration of carbon can be used as one layer of barrier and prevent in nucleation process carbon atom in substrate
Interior diffusion is conducive to improve second nucleation rate, to reduce the crystallite dimension of nano-diamond film.Gained Nano diamond is thin
Nano diamond crystallite dimension in film is 10~50nm, and diamond thin crystallite dimension is calculated as nanoscale.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the present invention is based on the technical principles and hair of the nano-diamond film preparation method of DLC film middle layer
Bright design, belongs to protection scope of the present invention.
Claims (6)
1. a kind of nano-diamond film preparation method based on DLC film middle layer, which is characterized in that including as follows
Step:
A. substrate pre-treatment:
It places the substrate in acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic, at least clean 15 minutes, continue cycling through this cleaning
Process at least twice, the substrate cleaned up；Then with mass percent concentration not less than 40% hydrofluoric acid and go from
Sub- water prepares hydrofluoric acid dilutions according to the ratio that hydrofluoric acid and deionized water volume ratio are 1:3, with hydrofluoric acid dilutions to clear
The substrate of wash clean carries out corrosion treatment at least 90 seconds, removes the oxide impurity of substrate surface, obtains pretreated substrate,
It is spare as substrate；
B. the preparation of DLC film middle layer:
Vacuum chamber will be put into for pretreated substrate in the step a, reach to vacuum degree not higher than 1.3*10-1It is right when Pa
Substrate carries out ion beam cleaning, and control Ar throughput is not less than 17sccm, and bias is not less than 1650V, carries out at ion beam cleaning
Reason at least 15 minutes；Then ion beam composite intermediate frequency sputtering method is used, is continued to vacuum chamber to not higher than 3.3*10- 1Pa, and Ti target is changed, mid frequency sputtering is carried out, control electric current is not less than 13A, and duty ratio is not less than 80%, and power is not less than 12kW,
It controls Ar throughput and is not less than 60sccm, sputtering time is not less than 30 minutes, in deposition on substrate Ti film layer；In Ti film layer
After the completion of sputtering technology, start to continue depositing diamond-like film in Ti film layer, and controls bias not less than 1600V, control
Ar throughput processed is not less than 10sccm, and acetylene flow is not less than 80sccm, and control mid frequency sputtering power is not less than 1.5kW, deposition
Time is 1~3 hour, prepares Ti/DLC multilayer film composite layer, so that DLC film composite layer is previously deposited on substrate,
As middle layer, compound substrate is formed；Then cool down, when vacuum room temperature is down to 130 DEG C or less, vacuum chamber is carried out
Deflation vacuum breaker, then samples, and obtains the compound substrate with DLC film middle layer；
C. microwave plasma CVD method is used, prepares nanometer Buddha's warrior attendant in the compound substrate obtained in stepb
Stone film；Wherein the pressure in ion bombardment stage cavity is not less than 100Torr, and power is not less than 3.0kW, and hydrogen flowing quantity is not low
In 500sccm, bombardment time at least 10 minutes；In the biased nucleation stage, pressure is constant in holding chamber, and control hydrogen flowing quantity is
425~450sccm, methane flow are 50~75sccm, and bias is -100~-300V, and nucleated time is 15~60 minutes；In life
In growth process, 460~475sccm of hydrogen flowing quantity, 25~40sccm of methane flow are controlled, growth time is 1~5 hour, is obtained
Nano-diamond film.
2. according to claim 1 based on the nano-diamond film preparation method of DLC film middle layer, feature
Be: in the step b, the thickness of prepared DLC film middle layer is not more than 1um.
3. according to claim 1 based on the nano-diamond film preparation method of DLC film middle layer, feature
Be: in the step c, the thickness of gained nano-diamond film is not more than 100nm.
4. according to claim 1 based on the nano-diamond film preparation method of DLC film middle layer, feature
Be: in the step c, the Nano diamond crystallite dimension in gained nano-diamond film is 10~50nm.
5. according to claim 1 based on the nano-diamond film preparation method of DLC film middle layer, feature
Be: in the step c, in the biased nucleation stage, pressure is constant in holding chamber, control hydrogen flowing quantity be 425~
450sccm, methane flow are 50~75sccm, and bias is -200~-300V, and nucleated time is 15~30 minutes.
6. according to claim 1 based on the nano-diamond film preparation method of DLC film middle layer, feature
Be: in the step a, the substrate is silicon substrate, metal material substrate or composite substrate.
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| CN113445023A (en) * | 2021-05-10 | 2021-09-28 | 广东工业大学 | Diamond product and preparation method and application thereof |
| CN113621926A (en) * | 2021-08-13 | 2021-11-09 | 中国计量科学研究院 | Low-stress diamond-like wear-resistant coating and preparation method thereof |
| CN114196936A (en) * | 2021-12-13 | 2022-03-18 | 昆山汇创杰纳米科技有限公司 | Novel preparation process for preparing DLC coating by ion beam method |
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