CN110016650B - Method for regulating and controlling surface roughening rate of film in situ in large range - Google Patents

Method for regulating and controlling surface roughening rate of film in situ in large range Download PDF

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CN110016650B
CN110016650B CN201910239032.XA CN201910239032A CN110016650B CN 110016650 B CN110016650 B CN 110016650B CN 201910239032 A CN201910239032 A CN 201910239032A CN 110016650 B CN110016650 B CN 110016650B
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CN110016650A (en
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胡超权
蔡继泽
张侃
郑伟涛
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Jilin University
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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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/0641—Nitrides
    • 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
    • C23C14/0664—Carbonitrides
    • 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
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target

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Abstract

The invention relates to the field of film surface roughening rate, in particular to a method for regulating and controlling the film surface roughening rate in a large range in situ, which comprises a sample material, wherein the sample material is hafnium nitride, an amorphous layer is introduced by adopting a magnetron co-sputtering method in the preparation process, and the upslope diffusion is blocked by utilizing the amorphous coating effect so as to obtain a low roughening rate; the invention guides and practices the theory of atom diffusion increase, simplifies complex diffusion, only considers the uphill diffusion and the downhill diffusion which influence the coarsening rate of the surface, and provides a new method for controlling the surface growth on the atomic level. By introducing the amorphous layer, the probability ratio of the up-slope diffusion and the down-slope diffusion is greatly reduced by hindering the up-slope diffusion, so that an extremely low coarsening rate is obtained, and an ultra-smooth film is prepared; by introducing elements which are not wet with the parent material, the probability ratio of the diffusion from the upper slope to the lower slope is greatly improved by blocking the diffusion from the lower slope, so that the extremely high coarsening rate is obtained, and the ultra-coarse film is prepared.

Description

Method for regulating and controlling surface roughening rate of film in situ in large range
Technical Field
The invention relates to the field of film surface roughening rate, in particular to a method for regulating and controlling the film surface roughening rate in an in-situ large range.
Background
With the rapid development of modern life science, physics and chemistry, more and more thin film materials with special surfaces are applied to the emerging technical fields of energy storage, superconduction, super surface, catalysis, biomedicine and the like. In these applications, control of the film surface morphology and roughness is critical. For example, in order to improve the durability and reliability of small and medium-sized moving mechanical parts in a micro-electro-mechanical system, the roughness of a durable protective film plated on a sliding pin needs to be at least in an ultra-smooth state below 1 nm; in order to reduce frictional resistance and to be able to adhere lubricating oil, the roughness of the gear surface needs to be in an intermediate state between 5 and 25 nm; in order to delay the formation of undesirable fibrous capsules around the implant, the surface roughness of the implant needs to reach at least a super-rough state of 30nm or more. In the conventional in-situ preparation method, a surface roughening phenomenon, i.e., a phenomenon that the roughness increases with the increase of the film thickness, is often observed, wherein the increasing speed of the surface roughness with the increase of the film thickness is the roughening rate. However, the conventional method has a coarsening rate in the middle region when most materials are prepared by controlling experimental parameters such as substrate bias, deposition temperature and gas flow, and the surface roughness of the thin film can not reach an ultra-smooth state nor an ultra-rough state when the film thickness is within a specified range, for example, the surface roughness ranges from 2 nm to 7nm when the film thickness is 1 μm. So that in order to achieve ultra-smooth and ultra-rough surfaces, only complex and expensive post-treatments, such as e-beam etching, chemical etching, etc., are relied upon at this stage. Therefore, the invention of a method for regulating and controlling the surface roughening rate of the film in situ in a large range is very important.
So far, the technical difficulty of in-situ regulation and control of the film surface roughening rate mainly focuses on two aspects: (1) the research on the microscopic factors of the coarsening rate of the surface of the film and the action rule thereof are not clear yet. Although researchers have paid great attention to the study of the microscopic mechanism of roughening the surface of thin films and have associated it with atomic diffusion, since atomic diffusion is random, complex and difficult to observe directly, the dependence of microscopic atomic diffusion on macroscopic surface roughening has not been explored well, and methods for precisely controlling surface roughness at the atomic level have not been proposed; (2) lack of reference-worthy related methods and techniques. The prior art discloses the law of influence of deposition conditions such as deposition temperature, substrate bias voltage and the like on the change of the coarsening rate of the surface of the film, but the conventional methods have different effects on different materials, are sometimes even opposite and have no good universality, and the conventional methods cannot regulate and control the coarsening rate to the state of preparing the ultra-smooth or ultra-rough film. How to further expand the surface roughening rate regulation range in situ by other methods based on these conventional methods has not been reported. Therefore, the method avoids the problem of complex diffusion caused by atom-increasing random walking, only considers the uphill diffusion and the downhill diffusion which have the largest influence on surface coarsening, obtains ultralow coarsening rate by introducing amorphous package to block the uphill diffusion, obtains general coarsening rate by regulating and controlling experimental parameters, and obtains ultrahigh coarsening rate by introducing nonwetting elements to block the downhill diffusion, thereby obtaining a large coarsening rate regulation and control range.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for regulating and controlling the surface roughening rate of a film in situ in a large range, which simplifies complex diffusion, only considers the uphill diffusion and downhill diffusion which have the greatest influence on surface roughening, obtains ultralow roughening rate by introducing amorphous coating to block the uphill diffusion, controls substrate bias voltage and deposition temperature to obtain general roughening rate, and introduces non-wetting elements to block the downhill diffusion to obtain ultrahigh roughening rate, thereby obtaining a large roughening rate regulation and control range.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for regulating and controlling the coarsening rate of the surface of a film in a large range in situ comprises a matrix material, wherein in the preparation process, an amorphous layer is introduced by adopting a magnetron co-sputtering method, and the uphill diffusion is blocked by utilizing the amorphous wrapping effect so as to obtain an ultralow coarsening rate; obtaining an intermediate roughening rate by controlling the substrate bias and deposition temperature during the preparation process; by doping elements which are not wetted with a parent material, the non-wetting property is utilized to block the downhill diffusion, so that the ultrahigh coarsening rate is obtained.
Preferably, hafnium nitride is used as the parent material, and the method comprises the following steps:
a. selecting a silicon wafer substrate as a substrate, ultrasonically cleaning the silicon wafer substrate by using acetone, absolute ethyl alcohol and distilled water in sequence, and drying by blowing after cleaning to obtain a target material for later use;
b. and in the deposition process, discharge gas is used, the working pressure is adjusted, the sputtering power of the pure hafnium target and the required target is controlled, sputtering is carried out according to the required conditions, and the film deposited on the substrate is obtained after the sputtering is finished.
Preferably, the discharge gas is a mixed gas of nitrogen and argon or a mixed gas of oxygen and argon, wherein N is contained in the mixed gas of nitrogen and argon2/(Ar+N2) Is 3.8%, and O is contained in the mixed gas of oxygen and argon2/(O2+ Ar) flow ratio was 20%.
Preferably, the desired target is selected from carbon, silver, tungsten and gold targets.
Preferably, the working pressure in the step b is kept at 0.8Pa, and the RF power applied to the hafnium target is 130-170W.
Preferably, the temperature of the substrate in the required conditions of the step b is not heated, the rotation speed of the sample is 5r/min, the bias voltage of the substrate ranges from-10 v to-240 v, and the deposition time ranges from 5min to 80 min.
The invention provides a method for regulating and controlling the surface roughening rate of a film in situ in a large range for the first time, and the creativity of the method is that the theory of atom-increasing diffusion is guided to practice, and only the uphill diffusion and the downhill diffusion which influence the surface roughening rate are considered. The inventors have found that surface roughening is primarily a competitive proportional relationship between up and down atomic diffusion: v isRK δ, where νRIs the coarsening rate and δ is the effective diffusion direction. We have hindered the ramp-up diffusion by introducing an amorphous layer to greatly reduce delta, so that delta<<1 in turn, extremely low vRAnd the ultra-smooth film can be prepared. By introducing an element which is not wettable with a parent material, the delta is greatly improved by blocking downhill diffusion, so that the delta>>1 to obtain a very high vRAnd the ultra-rough film can be prepared.
Compared with the prior art, the invention has the beneficial effects that: the method for regulating and controlling the coarsening rate in the in-situ large range has simple process and high efficiency, can prepare films with various surface roughness in the in-situ mode, controls the film thickness to be 1-4 mu m, and is widely suitable for various coating applications with requirements on rough surfaces.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a graph of the coarsening rate obtained in example 1 using hafnium nitride as a matrix;
FIG. 2 is a surface topography map of the hafnium nitride precursor obtained in example 1;
FIG. 3 shows the coarsening rate and roughness data obtained in example 1 using hafnium nitride as the matrix.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for regulating and controlling the coarsening rate of the surface of a film in a large range in situ comprises a parent material, wherein the parent material is hafnium nitride, a carbonitride amorphous layer is introduced by adopting a magnetron co-sputtering method in the preparation process, and the uphill diffusion is blocked by utilizing the amorphous wrapping effect so as to obtain a low coarsening rate; by doping silver element which is not wetted with the parent material, the non-wetting property is utilized to block the downhill diffusion so as to obtain high coarsening speed.
Specifically, the method comprises the following steps:
a. selecting a silicon wafer substrate as a substrate, ultrasonically cleaning the silicon wafer substrate by using acetone, absolute ethyl alcohol and distilled water in sequence, and drying by blowing after cleaning to obtain a target material for later use;
b. and in the deposition process, discharge gas is used, the working pressure is adjusted, the sputtering power of the pure hafnium target and the required target is controlled, sputtering is carried out according to the required conditions, and the film deposited on the substrate is obtained after the sputtering is finished.
The discharge gas is a mixed gas of nitrogen and argon, and N is contained in the mixed gas of nitrogen and argon2/(Ar+N2) The flow rate of (3) to (8).
The required targets are silver targets and carbon targets.
In step b the working pressure is maintained at 0.8Pa and the RF power applied to the hafnium target is 150W. Substrate temperature: heating is not carried out; sample rotation rate: 5r/min, the deposition time is respectively selected to be 10min, 40min and 80min, and the substrate bias voltage is sequentially selected to be-10 v, -40v, -160v and-240 v when a pure HfN sample is prepared. In addition, a pure HfN sample was prepared with a substrate temperature of 400 ℃ and a substrate bias of-40 v, and other conditions were unchanged. CN/HfN multilayer films with ultra-low roughening rates were prepared using pure hafnium targets and pure carbon targets. In the magnetron sputtering deposition process, the direct current power applied to the carbon target is 200W, the substrate pressure is-40 v, and other conditions are unchanged. In addition, Ag doped HfN films with ultra-high roughening rates were prepared by co-sputtering hafnium and silver targets. During deposition, the RF power applied to the silver target was 30W, the substrate pressure was maintained at-40 v, and other conditions were unchanged. The surface roughness and film thickness of each film were characterized by AFM and profilometer, respectively, and then the slope of the RMS-d line was calculated to obtain the roughening rate (FIG. 3).
Example 2:
a method for regulating and controlling the coarsening rate of the surface of a film in a large range in situ comprises a parent material, wherein the parent material is hafnium nitride, a carbonitride amorphous layer is introduced by adopting a magnetron co-sputtering method in the preparation process, and the uphill diffusion is blocked by utilizing the amorphous wrapping effect so as to obtain a low coarsening rate; by doping gold elements which are not wetted with the parent material, the non-wetting property is utilized to block the downhill diffusion so as to obtain high coarsening speed.
Specifically, the method comprises the following steps:
a. selecting a silicon wafer substrate as a substrate, ultrasonically cleaning the silicon wafer substrate by using acetone, absolute ethyl alcohol and distilled water in sequence, and drying by blowing after cleaning to obtain a target material for later use;
b. and in the deposition process, discharge gas is used, the working pressure is adjusted, the sputtering power of the pure hafnium target and the required target is controlled, sputtering is carried out according to the required conditions, and the film deposited on the substrate is obtained after the sputtering is finished.
The discharge gas is a mixed gas of nitrogen and argon, and N is contained in the mixed gas of nitrogen and argon2/(Ar+N2) The flow rate of (3) to (8). Required targetTungsten targets and gold targets are selected. In step b the working pressure is maintained at 0.8Pa and the RF power applied to the hafnium target is 150W. Substrate temperature: heating is not carried out; sample rotation rate: 5r/min, the deposition time is respectively selected to be 10min, 40min and 80min, and the substrate bias voltage is sequentially selected to be-10 v, -40v, -160v and-240 v when a pure HfN sample is prepared. A CN/HfN multilayer film was prepared by using a pure hafnium target and a pure carbon target. In the magnetron sputtering deposition process, the direct current power applied to the carbon target is 200W, the substrate pressure is-40 v, and other conditions are unchanged. In addition, Au doped HfN films were prepared by co-sputtering hafnium and gold targets. During deposition, the RF power applied to the gold target was 30W, the substrate pressure was maintained at-40 v, and other conditions were unchanged.
Example 3:
a method for regulating and controlling the coarsening rate of the surface of a film in a large range in situ comprises a parent material, a sample material is hafnium oxide, a tungsten oxide amorphous layer is introduced by adopting a magnetron co-sputtering method in the preparation process, and the upward slope diffusion is blocked by utilizing the amorphous wrapping effect so as to obtain a low coarsening rate; by doping gold elements which are not wetted with the parent material, the non-wetting property is utilized to block the downhill diffusion so as to obtain high coarsening speed.
Specifically, the method comprises the following steps:
a. selecting a silicon wafer substrate as a substrate, ultrasonically cleaning the silicon wafer substrate by using acetone, absolute ethyl alcohol and distilled water in sequence, and drying by blowing after cleaning to obtain a target material for later use;
b. and in the deposition process, discharge gas is used, the working pressure is adjusted, the sputtering power of the pure hafnium target and the required target is controlled, sputtering is carried out according to the required conditions, and the film deposited on the substrate is obtained after the sputtering is finished.
In the deposition process, the discharge gas is a mixed gas of oxygen and argon, and O in the mixed gas of oxygen and argon2/(O2+ Ar) flow ratio was 20%. Working pressure was maintained at 1.0Pa, RF power applied to Hf target: 150W; substrate temperature: heating is not carried out; sample rotation rate: 5 r/min. Preparation of pure HfO2The substrate bias voltage was selected to be-10 v, -40v, -80v, and-160 v in sequence when sampling. The deposition time is 5min, 10min, 20min and 40min respectively. By usingPreparation of pure hafnium target and pure tungsten target WO3/HfO2A multilayer film. In the magnetron sputtering deposition process, the RF power applied to the tungsten target is 120W, the substrate pressure is-40 v, and other conditions are unchanged. Preparation of Au-doped HfO by co-sputtering hafnium and gold targets2And (3) a membrane. During deposition, the RF power applied to the gold target was 30W, the substrate pressure was maintained at-40 v, and other conditions were unchanged.
According to the method for regulating and controlling the surface roughening rate of the film in the large range in situ, the amorphous layer is introduced, and the amorphous coating effect is utilized to block the uphill diffusion so as to obtain a low roughening rate; by doping elements which are not wettable with the parent material, the non-wettability is utilized to block the downhill diffusion so as to obtain high coarsening rate.
In the above method, hafnium nitride was taken as an example to demonstrate the wide range of control of the coarsening rate. An ultra-low coarsening rate is obtained by introducing a carbon-nitrogen amorphous layer for hindering the uphill diffusion; an ultra-high coarsening rate is obtained by retarding the downhill diffusion by introducing silver particles that are non-wetting with the matrix material.
The invention simulates the change rule between the size and the roughness of the bulge on the surface of the film through simulation software and quantifies the probability of the uphill diffusion and the downhill diffusion by combining the prior knowledge. And then, by contrasting the relation between the experiment and the simulation one by one, starting from the micro mechanism of the coarsening rate, finding that the factor mainly influencing the coarsening rate of the surface of the film is the probability ratio of the diffusion of the atoms ascending slope and the diffusion of the atoms descending slope. By hindering the uphill diffusion, such as by introducing an amorphous layer, a very small roughening rate can be obtained; by hindering the downhill diffusion, e.g. by introducing elements that are non-wetting with the matrix, several large coarsening rates can be obtained.
In addition, the theory of atom diffusion is increased to guide practice, the complex diffusion is simplified, only the uphill diffusion and the downhill diffusion which influence the coarsening rate of the surface are considered, and a new method for controlling the surface growth on the atomic level is provided. By introducing the amorphous layer, the probability ratio of the up-slope diffusion to the down-slope diffusion is greatly reduced by hindering the up-slope diffusion, so that the extremely low coarsening rate is obtained, and the ultra-smooth film is prepared. By introducing elements which are not wet with the parent material, the probability ratio of the diffusion from the upper slope to the lower slope is greatly improved by blocking the diffusion from the lower slope, so that the extremely high coarsening rate is obtained, and the ultra-coarse film is prepared.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.

Claims (1)

1. A method for regulating and controlling the coarsening rate of the surface of a film in situ in a large range is characterized in that: the method comprises the steps that a mother material is selected from hafnium nitride, a carbonitride amorphous layer is introduced by adopting a magnetron co-sputtering method in the preparation process, the uphill diffusion is hindered by the amorphous wrapping effect, so that the low coarsening rate is obtained, and the intermediate coarsening rate is obtained by controlling the substrate bias voltage and the deposition temperature in the preparation process of a pure hafnium target sample; by doping silver or gold elements which are not wetted with a parent material, the non-wetting property is utilized to block the downhill diffusion so as to obtain a high coarsening rate;
specifically, the method comprises the following steps:
a. selecting a silicon wafer substrate as a substrate, ultrasonically cleaning the silicon wafer substrate by using acetone, absolute ethyl alcohol and distilled water in sequence, and drying by blowing after cleaning to obtain a target material for later use;
b. using discharge gas in the deposition process, adjusting the working pressure, controlling the sputtering power of a pure hafnium target and a required target, sputtering according to required conditions, and obtaining a film deposited on the substrate after sputtering is finished;
the discharge gas is a mixed gas of nitrogen and argon, and N is contained in the mixed gas of nitrogen and argon2/(Ar+N2) 3.8% of the flow rate;
the required target is any one of a silver target, a gold target and a carbon target;
in step b, the working pressure is kept at 0.8Pa, and the RF power applied to the hafnium target is 150W; substrate temperature: heating is not carried out; sample rotation rate: 5r/min, the deposition time is respectively selected to be 10min, 40min and 80min, and the substrate bias voltage is sequentially selected to be-10 v, -40v, -160v and-240 v when a pure HfN sample is prepared; in addition, a pure HfN sample with the substrate temperature of 400 ℃ and the substrate bias voltage of-40 v is prepared, and other conditions are unchanged; preparing a CN/HfN multilayer film with an ultra-low coarsening rate by using a pure hafnium target and a pure carbon target; in the magnetron sputtering deposition process, the direct current power applied to the carbon target is 200W, the substrate pressure is-40 v, and other conditions are unchanged; in addition, an Ag or Au doped HfN film with an ultra-high coarsening rate is prepared by co-sputtering hafnium and a silver target or a gold target; during deposition, the RF power applied to the silver or gold target was 30W, the substrate pressure was maintained at-40 v, and other conditions were unchanged.
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JP2000169960A (en) * 1998-12-04 2000-06-20 Japan Energy Corp Sputtering target for forming optical disk recording film
CN1730716A (en) * 2005-08-23 2006-02-08 浙江大学 Novel metallic film preparation technology on liquid phase substrate surface
EP2123789A1 (en) * 2008-05-15 2009-11-25 Eifeler Werkzeuge GmbH A method of producing hard coatings

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1255553A (en) * 1998-11-26 2000-06-07 武汉大学 Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process
JP2000169960A (en) * 1998-12-04 2000-06-20 Japan Energy Corp Sputtering target for forming optical disk recording film
CN1730716A (en) * 2005-08-23 2006-02-08 浙江大学 Novel metallic film preparation technology on liquid phase substrate surface
EP2123789A1 (en) * 2008-05-15 2009-11-25 Eifeler Werkzeuge GmbH A method of producing hard coatings

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