WO2011062450A2 - 다성분 단일체의 스퍼터링 타겟 및 그 제조방법, 이를 이용한 다성분 합금계 나노구조 박막 제조방법 - Google Patents
다성분 단일체의 스퍼터링 타겟 및 그 제조방법, 이를 이용한 다성분 합금계 나노구조 박막 제조방법 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Definitions
- the present invention relates to a sputtering target of a multi-component monolithic body, a method for manufacturing the same, and a method for manufacturing a multi-component alloy-based nanostructure thin film using the same. More specifically, two kinds of metal elements having different reactivity with nitrogen, that is, a nitride forming metal Selective reactive sputtering using a monolithic target parent material containing elements and non-nitride-forming metal elements provides a variety of required characteristics such as high elasticity (low modulus) and low friction (low friction coefficient)
- the present invention relates to a sputtering target of a multi-component single body capable of forming a thin film capable of satisfying the same, and a method of manufacturing the same and a method of manufacturing a multi-component alloy nanostructure thin film using the same.
- nanoceramic-amorphous ceramics or nanoceramics obtained by applying a coating system having extremely low mutual immiscibility between the main components in the composition or combination of phases of the coating material obtained by plasma-based PVD or CVD processes. Attention has been focused on nanostructured coatings based on nanocomposite phase mixtures.
- ceramic nanostructured coating materials having a combination of (nano size ceramic crystals) and (amorphous ceramic phases) have been studied.
- the hardness is very high and the modulus of elasticity is also high with high hardness. This property is due to the intrinsic bonding style of covalent or ionic bonds that only ceramics have. These two high properties (hardness, modulus of elasticity) are theoretically very desirable for the use of cutting tool materials.
- substrates having low strength, low hardness and low elastic modulus such as low carbon steel, aluminum and magnesium alloys, may be used.
- substrates having low strength, low hardness and low elastic modulus such as low carbon steel, aluminum and magnesium alloys
- This problem is caused by the high modulus of elasticity of ceramic nano thin films.
- the hardness is high, the elastic modulus is high, and if the elastic modulus is high, the amount of elastic deformation until the coating material breaks is shortened.
- a material having a low hardness / low modulus of elasticity is used as a base material, when a local external deformation pressure is applied, a hard thin film of 10 ⁇ m or less is required as an egg shell effect to block the external force. This makes it practically difficult, and the base material is inevitable to local elastic / plastic deformation.
- the hard thin film when the hard thin film accumulates to some extent the elastic elastic / plastic deformation of the base material and does not allow the thin film to deform itself, the thin film is destroyed due to a mismatch of interfacial elastic properties between the base material and the coating material. Therefore, it is important to increase the hardness, but most of all, it is necessary to improve the elastic properties to have a low modulus of elasticity, and thus, the elastic strain of the thin film coated on the low hardness / low modulus matrix material. Increasing) may be a way to improve coating durability.
- the hardness of the oxide or nitride ceramic thin film used as the coating material is 1500 to 3000 Hv, and the carbide or boride system has a hardness of 2000 to 3000 Hv higher than this.
- These ceramic coatings are usually sputtering targets for transition metals (Ti, Zr, Mo, Cr, W, V, Al, etc.) that can react with reactive gases such as oxygen, nitrogen and carbonization gas to form high temperature ceramic compounds. It is used as an ash and is easily produced by a reactive PVD process using a mixed gas plasma of the reactive gas and argon gas.
- the ceramic hard thin film has a low hardness and low modulus of elasticity, and is used in a general tribo system field based on a material of low hardness and low elastic modulus.
- the ceramic hard thin film has a much lower substrate in terms of its elastic modulus. It is too high compared to the elastic modulus value of (eg, aluminum alloy 70 GPa, magnesium alloy 45 GPa, steel 200 GPa).
- the modulus of elasticity of most refractory ceramics is 400-700 GPa. Therefore, the ceramic hard thin film and the nanostructured thin film have a problem in durability due to the inconsistency of such elastic properties when using a low elastic modulus material as a base material. Accordingly, the ratio of hardness and elastic modulus (H / E) rather than hardness is used as a measure of coating durability, and this value shows the elastic strain to failure capability of the coating material to failure, This means the resilience and durability of the coating material.
- the thin film of the metal base is excellent in durability compared to the ceramic thin film because the difference in mechanical properties, in particular, the elastic properties with the metal base material is small as experienced in the case of Cr plating (electroplating). That is, the long elastic strain-to-failure that the ceramic does not have, and the ability to buffer plastic deformation is superior to the ceramic.
- Nano-structured thin film structure has the effect of simultaneously improving the hardness and durability of the metallic coating material by the Hall Pitch effect (Hall Pitch effect).
- the nanostructured technology of the metal thin film utilizes the quenching effect of the unique thin film composition method and vapor deposition method. That is, if the coating composition system is adjusted to have inherent mutual insolubility between the main elements constituting these thin films, and high plasma quenching rate conditions are used in the plasma PVD deposition, an alloy element of substitution or intrusion type is added. It is possible to supersaturate solid solution in the thin film base metal. The supersaturated solid solution can be formed into a nanocrystalline or amorphous phase by short range phase separation, thereby achieving nanostructured metal thin films.
- the coating system may include Cr-N and Mo-N in which nitrogen is dissolved.
- the high capacity of nitrogen in chromium is 4.3 at% at 1650-1700 ° C and negligibly small below 1000 ° C.
- the PVD Cr-N coating is carried out by controlling the nitrogen partial pressure, which is a reactive gas, to control the nitrogen content in the coating material to be less than the stoichiometric content of the ⁇ -Cr 2 N compound.
- the nitrogen partial pressure which is a reactive gas
- the structure of the thin film appears as a featureless structure in the columnar structure, thereby obtaining a Cr-N thin film of nanostructure by nitrogen element doping.
- this shows excellent mechanical and chemical properties according to the microstructure difference.
- the hardness of this featureless structured thin film is up to 15 GPa higher than that of less saturated supersaturated ⁇ -Cr phase films (less than 12 GPa), which means that the nanostructures with increased nitrogen supersaturation solubility in the metallic matrix are It is known that hardness is raised by being accelerated.
- the featureless nanostructured thin films have a slightly lower hardness than the columnar ⁇ -Cr 2 N-phase thin films (20 to 25 GPa) containing nitrogen in stoichiometric amounts. As shown, it was superior to single ceramic ⁇ -Cr 2 N phase thin film.
- these nanostructured nitrogen-doped CrN films are dense structures with few defects and are dense and free from through-coating permeable defects that can become corrosion channels. Therefore, corrosion test results show that the chemical durability is increased.
- such a microstructured nanostructured or amorphous structured material or coating material is extremely small or no defects acting as a corrosion channel, because it is dense, it is possible to block the corrosion channel causing local rapid corrosion propagation, It is known that uniform and predictable sacrificial corrosion protection is possible on the surface.
- A. Leyland and A. Matthew proposed a more feasible and stable method of manufacturing nanostructured thin film and designing system of coating system. It is based on transition metal elements capable of reacting with nitrogen to form nitrides, which do not dissolve or have very low solubility in these nitride forming metal elements, and do not react at all or have a low propensity to nitrogen.
- a systematic coating system design method has been proposed to realize a more advanced nanostructure thin film by adding a so-called non-nitride forming element as a third alloying element together with nitrogen.
- elements which are the targets of nitride forming metal elements are group IVb-VIb elements (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) and IIIa / VIb (Al, Si).
- the non-nitride forming elements have 12 elements such as Mg, Ca, Sc, Ni, Cu, Y, Ag, In, Sn, La, Au, and Pb.
- Nitride-forming elements are all high melting point elements above 1000 ° C except Al element, and non-nitride forming element elements are the Sc, Y, Au, Ni and Cu elements. Except for all the low melting point characteristics are shown below 1000 °C.
- the coating system between the nitride forming base support element and the non-nitride forming additive element there may be various combinations of the coating system between the nitride forming base support element and the non-nitride forming additive element.
- the coating system combination should be selected as the non-dissolving or extremely low solubility. In order to have such a low solubility, it is necessary to select a combination of elements having a large difference in atomic radius between the supporting element and the added element by more than 14%, or different preferred crystallographic structures.
- Cr-N-Cu, Cr-N-Ag, Mo-N-Cu, Mo-N-Ag, Zr-N-Cu systems have been considered.
- substitutional alloying elements into the thin film can be a much more efficient method than relying on nitrogen, which is an invasive alloying element, in terms of nanostructure of the thin film, and addition of soft non-nitride forming elements that do not react with nitrogen.
- nitrogen which is an invasive alloying element, in terms of nanostructure of the thin film
- soft non-nitride forming elements that do not react with nitrogen.
- high H / E index is known to have the effect of improving the durability of the thin film.
- the addition of a soft metal enables the manufacture of a hard thin film having a low friction function.
- Mo-N-Cu is known as a thin film having low friction characteristics in addition to high hardness and high durability due to the generation of low melting point Mo-Cu-O low melting point oxide in a friction environment.
- the mechanism for producing low melting point / low friction oxides is that when two specific oxides with large differences in the unique ionic potential values of the respective oxides obtained through tribological chemistry are encountered, the binary complex oxidation mixture The low melting point characteristics are shown, and thus, a low friction film (tribo-film) of nano scale is formed on the friction surface of the thin film so that the thin film exhibits low friction characteristics.
- Low-melting double oxides systems known to have these characteristics are known to have various binary oxide systems in addition to MoO 3 -CuO.
- the nanostructure of the thin film is achieved through the addition of substitutional elements having low solubility with them to the nitride supportable base, and elements that form low melting binary oxides by chemical reaction during friction, This can be a very efficient way to make a feature versatile.
- an insoluble coating system composed of at least two elements except nitrogen elements is required.
- an element Mo, V, or element capable of forming low friction oxide through tribo-chemical reaction Co, Ag, Cu, Ni
- a new approach to the practically feasible multicomponent nanostructure thin film parent material composition and manufacturing method thereof is required.
- the present invention is to solve the problems described above, to ensure the chemical uniformity and film structure reproducibility of the insoluble alloy system consisting of nitride metal and non-nitride metal forming an efficient multi-component nanostructure thin film for various requirements It is an object of the present invention to provide a sputtering target of a multi-component monolith and a method for manufacturing the same, which can be formed in a single-component control system, and can realize a complex multi-component coating system.
- the present invention is a multi-component alloy-based nanostructure that can form a hard thin film that meets a variety of requirements, such as high hardness, high elasticity, low friction through selective reactive sputtering using the target It is an object to provide a method for producing a thin film.
- the sputtering target of the multi-component monolithic body of the present invention for achieving the above object has a low or low solubility in the nitride-forming metal element and the nitride-forming metal element which can react with nitrogen and form the nitride-containing metal element.
- a low amorphous nitride forming metal element comprising an amorphous or partially crystallized glass forming alloy system
- the nitride forming metal element is Ti, Zr, Hf, V, Nb, Ta, Cr, At least one element selected from Y, Mo, W, Al, Si, and the non-nitride-forming metal element is at least selected from Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, Pb It can be configured to include one element.
- the nitride-forming metal element is preferably contained in an atomic ratio of more than 40 at% and 80 at% or less. More preferably, the nitride-forming metal element is preferably contained in an atomic ratio of 60at% or more and 80at% or less.
- the sputtering target may include at least one low melting point oxide formable metal element selected from Mo, V, Co, Ag, Cu, Ni, Ti, and W, which may form low friction oxide through tribological chemical reaction. It may be.
- the nitride-forming metal element and the non-nitride-forming metal element may be selected to have a difference in atomic radius of at least 14% or different crystal structures, but this is not essential.
- the amorphous or nitride-forming metal element capable of forming a nitride by reacting with nitrogen and the non-nitride-forming metal element having low or low solubility for the nitride-forming metal element and does not react with nitrogen or low reactivity
- the nitride metal element comprises at least one element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Y, Mo, W, Al, Si
- the non-nitride-forming metal element includes at least one element selected from Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, and Pb.
- the sputtering target is manufactured by atomizing an alloy including a nitride forming metal element and a non-nitride forming metal element, and bulking the atomizing powder by heating and pressure sintering in a supercooled liquid section.
- an alloy including a nitride forming metal element and a non-nitride forming metal element
- bulking the atomizing powder by heating and pressure sintering in a supercooled liquid section.
- the sputtering target may be manufactured by bulking through the direct casting method of melting and rapid solidifying the nitride forming metal element and the non-nitride forming metal element, high frequency cold of the nitride forming metal element and the non-nitride forming metal element It may be prepared by crystallizing through rapid solidification at a relatively low cooling rate using induction-cold crucible and forming a bulk structure by forming a cast structure having microcrystals.
- the method for producing a multi-component alloy nanostructure thin film of the present invention is an amorphous or partially crystallized amorphous alloy of a nitride-forming metal element that reacts with nitrogen to form a nitride and a non-nitride-forming metal element that does not react with nitrogen.
- the target is formed, and the target is selectively reactive sputtered in a mixed gas atmosphere containing nitrogen and an inert gas to form a thin film on the surface of the base material.
- the nitride-forming metal elements include Ti, Zr, Hf, V, Nb, Ta, At least one element selected from Cr, Y, Mo, W, Al, Si, wherein the non-nitride-forming metal element is from Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, Pb It includes at least one element selected.
- the mixed gas for reactive sputtering may further include at least one reactive gas of oxygen and oxide gas, carbon and carbide gas.
- an amorphous buffer layer by non-reactive sputtering between the matrix and the thin film by reactive sputtering.
- the insoluble nitride-forming and non-nitride-forming metal element by using the insoluble nitride-forming and non-nitride-forming metal element, it is possible to manufacture a multi-component alloy-based sputtering target having a variety of properties, in the reactive sputtering process Stable and uniform nanostructure by preventing uniform element concentration in the thin film composition due to the sputtering difference between individual components in the target, and uniform nitrogen distribution for synthesizing and distributing the nanocrystalline phase in the thin film Thin films can be prepared.
- 1 and 2 show the microstructure of the powder sintered body and the shape of the powder less than 100 ⁇ m made of the parent material of the sputtering target according to the present invention.
- FIG 11 and 12 show backscattered electron (BSE) photographs of the reactive sputtering film surface of the example compositions.
- Figure 13 shows the fracture surface FE-SEM photographed on the coating formed on the silicon substrate.
- 16 and 17 are photographs of the TEM SAD pattern of the amorphous and subparallel regions shown.
- 20 to 22 are high resolution TEM images of the reactive sputtering thin film obtained according to the power amount of the non-reactive sputtering thin film and the direct current plasma power source.
- 29 shows a photograph taken by the FE-SEM of the fracture surface of the thick film deposited with a deposition time of 4 hours.
- FIG. 30 shows a measurement result of the thickness profile of each target element including nitrogen elements from the top surface of the thick film to the substrate portion using glow discharge optical emission spectroscopy (GDOES).
- GDOES glow discharge optical emission spectroscopy
- first and / or second may be used to describe various components, but the components are not limited to the terms. The terms are only for the purpose of distinguishing one component from other components, for example, without departing from the scope of the rights according to the inventive concept, the first component may be called a second component, and For example, the second component may also be referred to as a first component.
- the sputtering target of the present invention is a multi-component single alloyed target having an amorphous or partially crystallized structure including a nitride forming metal (active metal) and an amorphous nitride forming metal (soft metal).
- a nitride forming metal active metal
- an amorphous nitride forming metal soft metal
- multifunctional nanostructures including the use of sputtering processes for the formation of protective hard coatings, which have high frictional properties and low friction, on the surfaces of driving material parts or tool parts used in friction environments. It can be used to manufacture thin films.
- the multi-component sputtering target alloy composition may be based on a bulk amorphous alloy system having a glass forming ability (GFA) of 1 mm or more.
- GFA glass forming ability
- the bulk amorphous alloy refers to an alloy capable of amorphous casting of a thickness of 1 mm or more in academic terms.
- the sputtering target uses an amorphous structure having a bulk amorphous alloy of a multi-component target alloy composed of multi-component elements to form an amorphous structure through various methods including a rapid solidification manufacturing method such as a gas spray powder manufacturing process. It can be produced by a method of preparing an alloy powder having, and densifying the amorphous alloy powder by using the viscosity flow characteristics in the subcooled liquid temperature section of the bulk amorphous alloy.
- the active metal and the soft metal among the active metal and the soft metal having the mutual insoluble relationship in the target during the film formation through selective reactive sputtering in a mixed gas atmosphere of argon and nitrogen under reduced pressure react with nitrogen.
- the soft metal Participating in the film formation as a cured nitrogen compound, the soft metal itself participates in the film formation to form a multi-component multifunctional nanocomposite thin film in which two or more nitride phases and soft metal phases are composited to nano size. ([Active metal (AM)] N [Soft metal (SM)]).
- the sputtering target of the present invention can form a uniform nanostructure thin film without difference in sputtering yield between components by maximizing chemical homogeneity without component segregation.
- the present invention can vary the chemical complexity (target) of the target material to provide a method for implementing a high-density nanostructured thin film having a high structural complexity (complex) and dense atomic filling rate.
- the present invention can provide a nano-composite coating thin film having a low friction high hardness properties of the mixed active metal nitride (AMeN) and soft metal (SMe) as a single target through a selective reactive sputtering process, a systematic low friction in the future It is possible to provide a new coating method that can be applied to the development of high hardness nano thin film design and film formation technology.
- AeN mixed active metal nitride
- SMe soft metal
- Table 1 shows the physical properties of the sputtering and reactive sputtering thin film according to the amorphous alloy composition as a sputtering target parent material according to the present invention, Examples 1 to 16 and Comparative Example 1 to the sputtering target of the present invention To 3 are indicated. In the following description, each example refers to those listed in Table 1.
- the alloy used as the target parent material includes a nitride forming element such as Zr, Al, Ti, Nb, Cr, Mo, Fe, etc., in an atomic% ratio of more than 40% and up to 80% or less, 1 mm
- a nitride forming element such as Zr, Al, Ti, Nb, Cr, Mo, Fe, etc.
- An alloy composed of a composition ratio having the above amorphous forming ability was used.
- the composition of these alloys consists of a nitride forming element (active metal) and a non-nitride forming element (soft metal).
- the multicomponent raw material mixtures measured at the above composition ratio of the alloy were alloyed and melted by a vacuum arc melting apparatus to form an alloy ingot.
- the alloy ingot was re-dissolved through a high frequency heating apparatus by argon gas atomization, and then sprayed with the same gas in an argon inert atmosphere to obtain an amorphous powder.
- the resulting amorphous powder was classified into a powder of 100 ⁇ m or less using a 150 mesh screen device.
- the powder of less than 100 ⁇ m is charged into the graphite mold with the internal diameter of 3 inch graphite mold in consideration of the theoretical specific gravity of each alloy composition, and the amount of sintered body is 6mm.
- the powder densification process resulted in a bulk spherical target with a diameter of 76.2 mm and a thickness of 6 mm.
- the sintering pressure applied to the powder and the molding mold during pulse energization sintering was 40 to 70 MPa.
- the powder sintered body has a dense microstructure with a spherical amorphous powder deformed with a relative density of 99% or more, and a powder particle boundary, which is an interface between powders, is a typical amorphous powder obtained by densifying the amorphous powder by plastic deformation in a supercooled liquid section. It shows a cosmetic tissue.
- the powder temperature inside the molding mold which is reached when heated by powder conduction resistance heating, tends to concentrate current at the center of the powder in the mold in the case of conductive powder such as amorphous metal. And the temperature is distributed low in the powder outer diameter direction.
- the temperature sensor K type thermocouple, this study
- the sintering temperature during energizing pressurization is difficult to directly contact with the powder, and only the mold temperature is measured as it is located at the center of the outer wall thickness of the mold, which is a low temperature region Therefore, it is inevitable to predict the temperature of the powder indirectly. Therefore, the difficulty of accurate sintering temperature and time control can contribute to this partial crystallization. If necessary, it may be possible to manufacture bulk powder compacts that maintain the amorphous structure of the powder by improving the temperature cycles and improving the temperature measurement method accurately and efficiently according to the subcooled liquid temperature range of each alloy.
- This amorphous or partially crystallized glass forming alloy powder sintered body was used as a sputtering target parent material, and it was used as a normal, non-reactive sputtering and reactive sputtering using direct current magnetron plasma power supply.
- a thin film was obtained through the sputtering process.
- the deposition condition is 70mm between target and substrate surface
- chamber pressure is 5mTorr
- argon gas flow rate is 36 sccm
- distance between target and substrate surface is 50mm.
- the gas flow rate was 30 sccm
- the reactive nitrogen gas was 6 sccm
- the argon / nitrogen gas flow rate ratio was 5: 1.
- the substrate was not heated by a separate heating device.
- the hardness and elastic modulus of the thin film were measured by the nano-indentation method, and the structure and crystallinity of the thin film were confirmed by X-ray diffractometer, FE-SEM, HR-TEM.
- FIGS. 3 and 4 show SEM and backscattered electron (BSE) photographs of the target surface of the ion etched area after sputtering Example 3.
- BSE backscattered electron
- the surface of the target is very flat, meaning that sputtering takes place uniformly.
- the back-scattered electron photograph of the same region shows that the inside of the grain boundary surface is seen, which shows the same structure as the sintered body structure photograph of Figs. Therefore, in the case of this sintered body, there was no appearance of a new phase in the sputtering process other than the amorphous phase, and it proves that a uniform sputtering yield occurred throughout the target surface without the difference in the sputtering depth between the grain boundary and the particles.
- 3 to 10 show the crystallinity of thin films deposited by alloys No. 2, 3, 5, 12, 14, and 15 of the composition, sintered sputtering target and non-reactive sputtering and reactive sputtering processes. The result analyzed by the line diffractometer is shown. Table 2 below shows the diffuse bragg angle of the reactive sputtering thin film according to the composition of the embodiment.
- the amorphous alloy powders are all amorphous. All of the non-reactive sputtering thin films using argon inert gas were also amorphous.
- the position of the broadened bragg peak (2 ⁇ value) is similar to that of the corresponding amorphous powder of the parent material. That is, the position of the breg pick of the amorphous powder varies slightly depending on the composition of the alloy, and the position of the diffuse breg pick of the amorphous thin film of the non-reactive sputtering thin film corresponding to the alloy material is the same as that of the corresponding parent material powder. This means that the composition and structure of the amorphous alloy, which is the parent material, are almost congruent transfer into the thin film through the non-reactive sputtering process.
- thin films deposited by RF magnetron non-reactive sputtering using crystallized Zr 52 Ti 6 Al 11 Cu 21 Ni 13 amorphous glass-forming alloy target parent material are similar to the parent material composition.
- thin films can be formed amorphous.
- the results in this example also can be said to show similar results to the previous studies reported.
- the result of forming the amorphous thin film is not necessarily due to the high ability to form amorphous, which is a characteristic of the target parent material.
- an amorphous alloy having an amorphous forming ability of 1 mm or more is sufficient forming conditions to form an amorphous phase at a cooling rate of 10 3 C / sec or more. Therefore, the fast cooling rate condition of the sputtering deposition process far surpasses the critical cooling rate of such amorphous alloys, and the synergistic effect is obtained when an alloy having an amorphous forming ability, that is, an alloy having a tendency to become non-equilibrium rather than equilibrium, is used as a target parent material. It is contemplated that the amorphous thin film can be formed more easily. After all, this means that in the synthesis of the amorphous thin film by sputtering using an alloy having an amorphous forming ability as the target parent material, the structure and configuration of the target need not necessarily be amorphous.
- the reactive sputtering thin film shows nanocrystalline.
- These XRD results show that the cause of crystallization is not related to the general amorphous crystallization behavior due to the formation of intermetallic compounds by the reaction between the components of the target parent material.
- the specific crystallization can be judged to be caused only by nitriding reactions of nitride-forming elements such as nitrogen (Zr,) and titanium (Ti), which are the main elements of the parent material alloy, with nitrogen, which is a reactive gas element. Can be.
- the nanoscale crystal is present in the thin film.
- 11 and 12 show backscattered electron photographs of the surface of the reactive sputtering thin film of the example composition using FE-SEM. No segregation of micro units was observed on the surface of the deposited nitride thin film, and it can be seen that a uniform coating layer was formed over the entire surface.
- FIG. 13 shows a fracture surface FE-SEM photograph of a coating film formed on a silicon substrate.
- an amorphous thin film was formed on the substrate by a non-reactive sputtering process (target / substrate distance: 7cm, power: 250W, deposition time 10 minutes), followed by reactive sputtering (target / substrate distance: 5cm) by adding nitrogen gas. , power: 300 W, deposition time: 20 minutes).
- the amorphous alloy composition used was Example 5 (Zr 63 Al 7.5 Mo 5 V 2 Ni 6 Cu 12.5 Ag 5 ).
- the fracture patterns of the reactive sputtering layer and the non-reactive sputtering layer are in sharp contrast.
- the amorphous thin film layer exhibits the same pattern as the vein-like pattern or striation-like pattern destruction by shear band propagation, which is an inherent failure mode of the parent material bulk amorphous, whereas the reactive sputtering layer has a high hardness and brittle fracture. It shows an aspect. This shows that the structure and mechanical properties of the two layers have very different differences.
- a deposited sample was prepared for high resolution transmission electron analysis. Deposition conditions reduced the non-reactive and reactive deposition times by one half to reduce the total thickness of the hybrid thin film layer by half the size of the SEM fracture surface observation specimen, and other deposition conditions were performed in the same manner. The samples were fabricated into TEM specimens through mechanical polishing and ion milling.
- each interface shows no cracks or voids as observed in the fracture SEM image, and shows a continuous flat interface.
- the amorphous layer shows a uniform concentration without showing a difference in overall contrast
- the reactive sputtering layer shows that there are stain-shaped phases that are discontinuously lined in the direction of growth of the thin film. Can be.
- these contrast-rich phases appear to form a lattice pattern in high-magnification photographs, they appear to be nanocrystals with a size of 5-20 nm.
- the non-reactive sputtering region shows a diffuse or broad halo electron diffraction pattern
- the reactive region shows nanoscale crystallinity from faint points.
- the non-regular atomic arrangement of the non-reactive sputtering layer can be confirmed by the overall amorphous structure, and the atomic arrangement is continuously extended to some regions within the reactive reactive sputtering layer.
- nanocrystals in the sputtering layer are surrounded by an amorphous matrix and each crystal shows a fully percolated structure in which almost amorphous phases present in nanoscale as discontinuously isolated forms are present.
- the amorphous thin film made by the non-reactive sputtering process has a low hardness of 10 GPa or less, whereas in the case of the reactive sputtered thin film by incorporation into the reactive nitrogen gas, nitride formation
- the hardness varies from 15 to 27 GPa.
- the cause is caused by nitrogen reactant forming elements in the parent material and nitrogen gas elements having inter-reactivity with them during sputter deposition.
- the reaction may be attributed to the Hall Pitch effect due to the grain refinement through the formation of a nano hard phase in the amorphous matrix and the formation of a microstructure into a nanostructure.
- the thin film of reactive sputtering shows high modulus of elasticity of 200 GPa or more due to the increase in hardness and the incorporation of nano nitrogen compounds.
- the low elastic modulus 164 ⁇ 268GPa
- the fraction of soft metals which are non-nitride generating elements having insoluble relation to these nitride forming elements, is contained in the target by 20 to 60%.
- a high H / E index 0.1 is exhibited by nanocompositing the amorphous metal phase and the hard ceramic nitride phase having low modulus in the hard thin film.
- 20 to 22 are high resolution TEM images of the reactive sputtering thin film obtained according to the power amount of the non-reactive sputtering thin film and the direct current plasma power source.
- the distance between the target surface and the substrate surface is 70mm and the power is 250W.
- the distance is 50mm and 8: 1 argon / nitrogen mixed gas ratio is deposited under the conditions of 250W and 350W.
- the composition used was an alloy of composition 3 (Zr 62.5 Al 10 Mo 5 Cu 22.5 ) in the example composition of Table 1.
- amorphous tissues with irregular atomic arrangements are shown, whereas in the case of reactive sputtering, regions where atomic arrangements are regular are observed.
- the size and dispersion state of nano-arranged regions in which atoms are regularly arranged can be seen that the crystal phase becomes finer and the fraction of crystal phase increases further when the power of DC power is increased to 350W.
- the amorphous and crystalline regions are clearly distinguished and the two phases are similar in size.
- the amorphous region decreases more rapidly than in the case of 250W, and the crystalline region occupies most of it.
- the increase of the crystallization region does not proceed through the growth of crystals due to the long-term diffusion of elemental elements, and the fraction of amorphous regions decreases and the fraction of crystallization regions increases by short-range diffusion of less than 5 nm. It is shown.
- Zr and N atoms which lead crystallization, are difficult to diffuse in the long range, which is a characteristic of the atomic arrangement of the amorphous base phase, which is an interphase region located between nanocrystals, that is, atoms of each other.
- the nitrogen atom which is a reactive gaseous element and the element having the smallest atomic size among the thin film elements, is easily supersaturated on an amorphous substrate having a high atomic filling efficiency through a sputtering process having a fast cooling rate of 10 -8 C / sec. Condensation occurs, and the amorphous matrix phase with the addition of nitrogen added elements has a smaller free volume value. This lowers the result of the higher atomic filling rate, and the longer and longer the diffusion of nitrogen atoms for the nitriding reaction becomes more difficult.
- FIGS. 20 to 22 show SAD pattern analysis results of the thin film observed in FIGS. 20 to 22.
- the typical diffuse halo pattern of the amorphous structure is seen, and in the case of reactive sputtering, it is seen that the crystallization by nitriding reaction occurs as a distinct ring pattern. It was also confirmed that the ZrN ring pattern was clearly observed as the power of the DC power source increased to 350W.
- a thick film was grown to a thickness of 10 ⁇ m or more through a reactive sputtering process using a multi-component target parent material of Example 3 (Zr 62.5 Al 10 Mo 5 Cu 22.5 ).
- the underlayer of the thick film was made into an amorphous thin film through non-reactive sputtering using the same target.
- 29 shows a photograph taken by the FE-SEM of the fracture surface of the thick film deposited with a deposition time of 4 hours.
- the surface hardness of the thick film was 20GPa which was somewhat lower than the hardness of the thin film (22GPa).
- the depth profile of each target element including nitrogen elements from the top surface of the thick film to the substrate was measured by using glow discharge optical emission spectroscopy (GDOES), and the results are shown in FIG. 30. .
- GDOES glow discharge optical emission spectroscopy
- the surface of the thick film showed high concentration of nitrogen element and low concentration of target element up to about 3 ⁇ m depth. Then, as the depth deepens, that is, the elements of the first layer formed show a relatively stable and uniform concentration distribution of each element. Zr and Al, which form nitrogen compounds, are very small in proportion to their depth, but the concentration tends to increase continuously, and the concentration of nitrogen is inversely lowered. This is due to the increase in deposition temperature with long exposure to ion collision in the process of forming a thick film having a thickness of 10 or more, and is not a phenomenon that occurs when forming a thin film having a thickness of 10 ⁇ m or less.
- each element has a flat and steady state concentration profile depending on the thickness of the film.
- the average nitrogen concentration in this homogeneous zone is around 32 at%.
- the discontinuous concentration profile shows a sharp drop in the concentration of nitrogen elements and a sharp increase in the concentrations of other components, and at this point, the amorphous intermediate layer begins as a base layer and the reactive sputtering layer ends. It can be seen that it is a point.
- the nitrogen element is very low in the intermediate layer compared with the nitride layer, but is not negligible in the level of 7-8 at%.
- this region is an intermediate buffer layer formed by non-reactive sputtering, it contains some nitrogen, which also exposes the film to the ion collision process for a long time of 4 hours for the deposition time to grow to a thick film thickness. As a result, it is very likely that nitrogen has diffused into the non-nitride layer due to the increase in temperature.
- Table 3 shows the results analyzed by EPMA to investigate the quantitative composition ratios of the raw material powder, the sintered sputtering target, the non-reactive thin film and the reactive thin film layer.
- the raw material powder and the target showed an error range of less than 1 at% with the initial alloy composition, and the non-reactive sputtering film showed a composition almost similar to the powder / target composition.
- nitrogen is contained at 38 at% level, thereby lowering the atomic fraction of the target element.
- the results of detecting only four target component sources without detecting nitrogen elements are shown in parentheses. It can be seen that the atomic ratio between the target components shows a slight difference from the components of the target raw material.
- the composition of the reactive sputtering film using the single target of the multicomponent amorphous forming alloy system is almost similar to that of the multicomponent target alloy composition and shows a uniform concentration distribution.
- the sputtering target of the present invention can form a uniform nanostructure thin film without difference in sputtering yield between components by maximizing chemical homogeneity without component segregation.
- the present invention can vary the chemical complexity (target) of the target material to provide a method for implementing a high-density nanostructured thin film having a high structural complexity (complex) and dense atomic filling rate.
- the present invention can provide a nano-composite coating thin film having a low friction high hardness properties of the mixed active metal nitride (AMeN) and soft metal (SMe) as a single target through a selective reactive sputtering process, a systematic low friction in the future It is possible to provide a new coating method that can be applied to the development of high hardness nano thin film design and film formation technology.
- AeN mixed active metal nitride
- SMe soft metal
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Abstract
Description
실시/비교No. | 타겟물질 | 스퍼터링 박막 | 반응성 스퍼터링 박막 | |||||||
화학조성 (at%) | 질화물형성원소분율(%) | 소결재구성상 | 경도(GPa) | 탄성계수(GPa) | 박막구성상 | 경도(GPa) | 탄성계수(GPa) | 박막구성상 | H/E | |
실시예1 | Zr55Al20Ti5Ni10Cu10 | 80.0 | 결정+비정질 | 6.5 | 110.7 | 비정질 | 26.0 | 256.3 | nc-ZrN+비정질 | 0.10 |
실시예2 | Zr62.5Al10Fe5Cu22.5 | 77.5 | 비정질 | 6.7 | 113.8 | 비정질 | 23.1 | 251.5 | nc-ZrN+비정질 | 0.09 |
실시예3 | Zr62.5Al10Mo5Cu22.5 | 77.5 | 비정질 | 7.0 | 119.0 | 비정질 | 22.6 | 237.5 | nc-ZrN+비정질 | 0.10 |
실시예4 | Zr58.5Al9Mo10Ni9Cu13.5 | 77.5 | 결정+비정질 | 6.2 | 114.5 | 비정질 | 25.9 | 261.7 | nc-ZrN+비정질 | 0.10 |
실시예5 | Zr63Al7.5Mo4V2Ni6Cu12.5Ag5 | 76.5 | 결정+비정질 | 6.0 | 102.1 | 비정질 | 26.8 | 260.3 | nc-ZrN+비정질 | 0.10 |
실시예6 | Zr61.8Al9.5Cr5Ni9.5Cu14.2 | 76.3 | 결정+비정질 | 6.3 | 107.1 | 비정질 | 25.6 | 247.8 | nc-ZrN+비정질 | 0.10 |
실시예7 | Zr55Al20Ni25 | 75.0 | 결정+비정질 | 6.0 | 109.2 | 비정질 | 25.7 | 251.6 | nc-ZrN+비정질 | 0.10 |
실시예8 | Zr65Al10Co10Cu15 | 75.0 | 결정+비정질 | 6.1 | 110.7 | 비정질 | 25.1 | 253.5 | nc-ZrN+비정질 | 0.10 |
실시예9 | Zr61Al7.5Ti2Nb2Ni10Cu12.5Ag5 | 72.5 | 비정질 | 6.1 | 114.7 | 비정질 | 25.3 | 268.5 | nc-ZrN+비정질 | 0.09 |
실시예10 | Zr65Al7.5Ni10Cu17.5 | 72.5 | 비정질 | 6.4 | 120.9 | 비정질 | 29.3 | 256.9 | nc-ZrN+비정질 | 0.11 |
실시예11 | Zr57Al10Nb5Ni12.6Cu15.4 | 72.0 | 비정질 | 6.5 | 118.7 | 비정질 | 22.3 | 230.1 | nc-ZrN+비정질 | 0.10 |
실시예12 | Zr55Al10Ni5Cu30 | 65.0 | 비정질 | 7.2 | 124.5 | 비정질 | 23.1 | 243.3 | nc-ZrN+비정질 | 0.10 |
실시예13 | Zr50.7Al12.3Ni9Cu28 | 63.0 | 비정질 | 7.3 | 128.7 | 비정질 | 20.7 | 222.0 | nc-ZrN+비정질 | 0.09 |
실시예14 | Zr50Ti16Ni19Cu15 | 66.0 | 결정+비정질 | 6.7 | 121.4 | 비정질 | 23.6 | 231.5 | nc-ZrN+비정질 | 0.10 |
실시예15 | Ti45Zr5Ni5Cu45 | 50.0 | 결정+비정질 | 7.4 | 133.7 | 비정질 | 19.8 | 198.7 | nc-ZrN+비정질 | 0.10 |
실시예16 | Ti34Zr11Ni8Cu47 | 45.0 | 결정+비정질 | 7.5 | 132.1 | 비정질 | 15.7 | 164.2 | nc-TiN+비정질 | 0.09 |
비교예1 | Zr22Ti18Ni6Cu54 | 40.0 | 결정+비정질 | 7.9 | 137 | 비정질 | 11.8 | 191.1 | nc-TiN+비정질 | 0.06 |
비교예2 | Ti | 100 | 결정+비정질 | - | - | - | 26.7 | 435.3 | TiN 결정질 | 0.06 |
비교예3 | Zr | 100 | 결정+비정질 | - | - | - | 25.0 | 328.1 | ZrN 결정질 | 0.076 |
면지수 | Reference | XRD 분석결과 | ||||||
실시예 2번 조성 | 실시예 3번 조성 | 실시예 5번 조성 | 실시예 12번 조성 | 실시예 14번 조성 | 실시예 15번 조성 | |||
ZrN | TiN | ZrN | ZrN | ZrN | ZrN | ZrN | TiN | |
111 | 33.918 | 36.730 | 34.29 | 34.09 | 34.53 | 33.97 | 34.16 | 36.66 |
200 | 39.362 | 42.669 | 39.85 | 39.61 | 39.93 | 39.73 | 39.44 | 42.94 |
220 | 56.885 | 61.929 | 57.53 | 56.33 | 57.45 | 57.33 | 57.16 | 61.56 |
311 | 67.914 | 74.215 | 68.77 | 68.63 | 68.97 | 68.17 | 67.92 | 74.06 |
222 | 71.380 | 78.121 | - | 72.01 | 71.95 | 71.97 | - | - |
Nominal alloy composition | Sample | Element concentration (at%) | ||||
Zr | Cu | Al | Mo | N | ||
Zr62.5Al10Mo5Cu22.5 | Gas atomized powder | 62.89 | 21.67 | 10.26 | 4.18 | - |
Sintered target | 63.11 | 22.58 | 10.02 | 4.29 | - | |
Non-reactive sputtering film | Power:250W | 62.94 | 22.57 | 10.24 | 4.24 | - |
Reactivesputtering film가스비 8:1 | 250W | 34.66(57.98) | 12.84(21.83) | 8.42(14.13) | 3.61(6.06) | 40.48(-) |
300W | 38.45(62.39) | 12.28(19.97) | 7.30(11.73) | 3.64(5.90) | 38.32(-) | |
350W | 38.70(61.95) | 12.75(20.39) | 7.13(11.59) | 3.78(5.07) | 37.65(-) |
Claims (19)
- 질화물형성 금속원소 및 상기 질화물형성 금속원소에 대한 고용도가 없거나 낮고 질소와 반응하지 않거나 반응성이 낮은 비질화물형성 금속원소의 비정질 또는 부분결정화된 비정질형성 합금계를 포함하며,상기 질화물형성 금속원소는 Ti, Zr, Hf, V, Nb, Ta, Cr, Y, Mo, W, Al, Si로부터 선택된 적어도 하나의 원소를 포함하고,상기 비질화물형성 금속원소는 Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, Pb로부터 선택된 적어도 하나의 원소를 포함하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟.
- 제1항에 있어서,상기 질화물형성 금속원소를 40at% 초과 및 80at% 이하의 원자비율로 포함하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟.
- 제2항에 있어서,상기 질화물형성 금속원소를 60at% 이상 및 80at% 이하의 원자비율로 포함하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟.
- 제1항 내지 제3항 중 어느 한 항에 있어서,마찰화학반응을 통해 저마찰 산화물을 형성할 수 있는 Mo, V, Co, Ag, Cu, Ni, Ti, W로부터 선택된 적어도 하나의 저융점 산화물형성 가능 금속원소를 포함하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟.
- 제1항 내지 제3항 중 어느 한 항에 있어서,상기 질화물형성 금속원소와 비질화물형성 금속원소는 상호 간의 원자반경의 차이가 14% 이상이거나 결정구조가 상이한 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟.
- 질화물형성 금속원소 및 상기 질화물형성 금속원소에 대한 고용도가 없거나 낮고 질소와 반응하지 않거나 반응성이 낮은 비질화물형성 금속원소를 비정질 또는 부분결정화된 비정질형성 합금계로 형성하며,상기 질화물형성 금속원소는 Ti, Zr, Hf, V, Nb, Ta, Cr, Y, Mo, W, Al, Si로부터 선택된 적어도 하나의 원소를 포함하고, 상기 비질화물형성 금속원소는 Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, Pb로부터 선택된 적어도 하나의 원소를 포함하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제6항에 있어서,상기 질화물형성 금속원소를 40at% 초과 및 80at% 이하의 원자비율로 함유되도록 하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제7항에 있어서,상기 질화물형성 금속원소를 60at% 이상 및 80at% 이하의 원자비율로 함유되도록 하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제6항 내지 제8항 중 어느 한 항에 있어서,마찰화학반응을 통해 저마찰 산화물의 형성이 가능한 Mo, V, Co, Ag, Cu, Ni로부터 선택된 적어도 하나의 산화물형성 금속원소를 함유되도록 하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제6항 내지 제8항 중 어느 한 항에 있어서,상기 질화물형성 금속원소와 비질화물형성 금속원소를 포함하는 합금을 아토마이징하고, 아토마이징 분말을 과냉액체구간에서 가열 및 가압 소결하여 벌크화하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제6항 내지 제8항 중 어느 한 항에 있어서,상기 질화물형성 금속원소와 비질화물형성 금속원소를 용융 및 급속응고시키는 직접 주조방법을 통해 벌크화하는 것을 특징으로 하는 다성분 단일체의 스퍼터링 타겟 제조방법.
- 제6항 내지 제8항 중 어느 한 항에 있어서,상기 질화물형성 금속원소와 비질화물 형성 금속원소를 고주파 콜드 크루시블(induction-cold crucible)을 이용한 급속응고를 통해 결정화하고 미세결정을 갖는 주조조직으로 만들어 벌크화하는 것을 특징으로 하는 다성분 단일체의 스프터링 타겟 제조방법.
- 질화물형성 금속원소 및 질소와 반응하지 않는 비질화물형성 금속원소를 비정질 또는 부분결정화된 비정질형성 합금계의 타겟으로 만들고,상기 타겟을 질소 및 불활성기체를 포함하는 혼합기체 분위기에서 선택적 반응성 스퍼터링하여 기지재의 표면에 박막을 형성하며,상기 질화물형성 금속원소는 Ti, Zr, Hf, V, Nb, Ta, Cr, Y, Mo, W, Al, Si로부터 선택된 적어도 하나의 원소를 포함하고, 상기 비질화물형성 금속원소는 Mg, Ca, Sc, Ni, Cu, Ag, In, Sn, La, Au, Pb로부터 선택된 적어도 하나의 원소를 포함하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제13항에 있어서,상기 타겟에 질화물형성 금속원소가 40at% 초과 및 80at% 이하의 원자비율로 함유되도록 하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제14항에 있어서,상기 타겟에 질화물형성 금속원소가 60at% 이상 및 80at% 이하의 원자비율로 함유되도록 하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제13항 내지 제15항 중 어느 한 항에 있어서,상기 반응성 스퍼터링을 위한 혼합기체는 산소 및 산화물 기체, 탄소 및 탄화물 기체 중 적어도 하나의 반응성 기체를 더 포함하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제13항 내지 제15항 중 어느 한 항에 있어서,상기 타겟에 마찰화학반응을 통해 저마찰 산화물의 형성이 가능한 Mo, V, Co, Ag, Cu, Ni로부터 선택된 적어도 하나의 산화물형성 금속원소가 함유되도록 하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제13항 내지 제15항 중 어느 한 항에 있어서,상기 타겟은 질화물형성 금속원소와 비질화물형성 금속원소를 아토마이징하고, 아토마이징 분말을 과냉액체구간에서 가열 및 가압 소결하여 벌크화하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
- 제13항 내지 제15항 중 어느 한 항에 있어서,상기 기지재와 반응성 스퍼터링에 의한 박막의 사이에 비반응성 스퍼터링에 의한 비정질의 버퍼층을 형성하는 것을 특징으로 하는 다성분 합금계 나노구조 박막 제조방법.
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