KR20140143027A - Polycrystalline alloy having glass forming ability, method of fabricating the same, alloy target for sputtering and method of fabricating the same - Google Patents

Abstract

The purpose of the present invention is to provide a crystalline alloy with the ability to form glass and a manufacturing method thereof wherein the crystalline alloy is capable of having the ability to form glass, but also having a largely higher thermal stability when compared with an amorphous alloy. In addition, the other purpose of the present invention is to provide an alloy target to sputter and a manufacturing method thereof, wherein the alloy target to sputter is manufactured from the above crystalline alloy. According to an aspect of the present invention, the crystalline alloy with the ability to form glass is an alloy having the ability to form glass having at least four metal elements having an average crystal grain size in the range of 0.1-5 μm, and comprising: 5-20 at% of Al; 15-40 at% of at least one selected from the group consisting of Cu and Ni; 8 or less (larger than 0) at% of a sum of at least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti, Fe; and at least one selected from a group consisting of P and S, and the remnants of Zr.

Description

TECHNICAL FIELD The present invention relates to a crystalline alloy having amorphous forming ability, a method for producing the same, an alloy target for sputtering, and a method for fabricating the same.

The present invention relates to a crystalline alloy made of at least four metals having amorphous forming ability and having excellent thermal and mechanical stability, and a sputtering alloy target made of such a crystalline alloy.

The sputtering process refers to a technique of forming a thin film on the surface of a base material by colliding argon ions or the like with a negative voltage at high speed to release the target atoms and supplying the target atoms to the base material. Such a sputtering process is also used in the field of semiconductor manufacturing process, the manufacture of fine devices such as MEMS, as well as the coating formation for the improvement of wear resistance of various tools, molds, and automobile parts.

When the amorphous thin film or the nanocomposite thin film containing the amorphous phase is produced by sputtering, a target made of amorphous can be used. The amorphous target may be formed of a multi-metallic metal alloy having high amorphous forming ability, and the dissimilar metal elements separated from the amorphous target may form an alloy thin film having an amorphous phase on the surface of the base material.

However, such an amorphous target has an increased temperature due to the collision of ions in the sputtering process, and this temperature increase can change the structure near the surface of the target. That is, due to the characteristics of the thermally unstable amorphous phase, when the temperature of the target is increased, local crystallization can proceed on the surface of the target. This local crystallization can cause volume change and structural relaxation of the target, which can increase the target's brittleness and result in the target being easily destroyed during the sputtering process. If the target is destroyed during the process, it will cause a serious problem in the production of the product, so it is very important to secure a stable target that does not cause such destruction during the sputtering process.

It is an object of the present invention to solve the various problems including the above problems and to provide a crystalline alloy having an amorphous forming ability and a thermal stability remarkably superior to an amorphous state, and a method for producing the same. Another object of the present invention is to provide an alloy target for sputtering manufactured using the crystalline alloy and a method of manufacturing the same. However, these problems are exemplary and do not limit the scope of the present invention.

According to one aspect of the present invention, there is provided an amorphous alloy having an amorphous forming ability, the average grain size of the alloy being in a range of 0.1 탆 to 5 탆, wherein the alloy contains 5 atom% to 20 atom% ; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr, is provided.

In the crystalline alloy having amorphous forming ability, at least one or more selected from P and S may be from 30 ppm to 130 ppm.

In the crystalline alloy having amorphous forming ability, at least one or more selected from among P and S may be S of 10 ppm to 30 ppm.

In the crystalline alloy having amorphous forming ability, at least one or more selected from P and S may be 30 ppm to 130 ppm P and 10 ppm to 30 ppm S,

The critical casting thickness of the casting ribbon capable of obtaining an amorphous structure when casting the molten alloy of the alloy at a cooling rate in the range of 10 ⁴ K / sec to 10 ⁶ K / sec in the alloy having the amorphous forming ability ranges from 20 μm to 100 μm Lt; / RTI >

In the crystalline alloy having the amorphous forming ability, the average grain size of the crystalline alloy may be in the range of 0.3 탆 to 0.5 탆.

In the crystalline alloy having amorphous capability, the Al content is in the range of 6 to 13 atomic%, and at least one of Cu and Ni is in the range of 17 to 30 atomic%. The Cr, Mo, Si, Nb, Co, , Zn, V, Hf, Ag, Ti and Fe may be in a range of 5 atomic% or less (more than 0).

According to another aspect of the present invention, an alloy target for sputtering made of the above-described crystalline alloy can be provided.

According to still another aspect of the present invention, an amorphous alloy or a nanocrystalline alloy having an amorphous forming ability and comprising four metal elements or more is heated in a temperature range not lower than a crystallization start temperature of the amorphous alloy or a nanocrystalline alloy, Wherein the amorphous alloy or the nanocrystalline alloy contains Al in an amount of 5 atom% to 20 atom%; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr; a process for producing an amorphous forming crystalline alloy is provided.

In the method for producing a crystalline alloy having amorphous forming ability, at least one selected from P and S may be P of 30 ppm to 130 ppm.

In the method for producing a crystalline alloy having the amorphous forming ability, at least one or more selected from P and S may be S of 10 ppm to 30 ppm.

In the method for producing a crystalline alloy having amorphous ability, at least one selected from P and S may be 30 ppm to 130 ppm P and 10 ppm to 30 ppm S,

In the method for producing a crystalline alloy having the amorphous forming ability, the average size of the crystal grains can be controlled to be in the range of 0.3 탆 to 0.5 탆.

Wherein at least one of Cu and Ni is in a range of 17 to 30 atomic%, the Cr, Mo, Si, Nb, Co, Sn, In , Bi, Zn, V, Hf, Ag, Ti and Fe may be in a range of 5 atomic% or less (more than 0).

According to still another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a plurality of amorphous alloys or nanocrystalline alloys having amorphous ability, And

The plurality of amorphous alloys or nanocrystalline alloys are thermally pressurized in a temperature range not lower than the crystallization start temperature of the amorphous alloy or the nanocrystalline alloy at a temperature not lower than the crystallization start temperature to produce a crystalline alloy having an average grain size in the range of 0.1 탆 to 5 탆 Wherein the amorphous alloy or the nanocrystalline alloy comprises 5 atom% to 20 atom% of Al; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr. The present invention also provides a method for producing an alloy target for sputtering.

In the above-described method for producing an alloy target for sputtering, at least one selected from among P and S may be P of 30 ppm to 130 ppm.

In the method for producing a crystalline alloy having the amorphous forming ability, at least one or more selected from P and S may be S of 10 ppm to 30 ppm.

In the method for producing a crystalline alloy having amorphous ability, at least one selected from P and S may be 30 ppm to 130 ppm P and 10 ppm to 30 ppm S,

At this time, the average size of the crystal grains may be in the range of 0.3 탆 to 0.5 탆.

In the above-described method for producing an alloy target for sputtering, the amorphous alloy or the nanocrystalline alloy may be an amorphous alloy ribbon or a nanocrystalline alloy ribbon.

In the method for manufacturing an alloy target for sputtering, the amorphous alloy ribbon or the nanocrystalline alloy ribbon may be prepared by preparing a molten metal in which the four metal elements or more are dissolved. Adding at least one selected from P and S to the molten metal; And injecting the molten metal having at least one selected from P and S added thereto into a rotating roll, by melt spinning.

According to the embodiments of the present invention, the thermal / mechanical stability of the target is greatly improved, and the target is not suddenly broken during the sputtering process, so that the sputtering process can be stably performed. In addition, since it has a very uniform microstructure, it has an effect of narrowing the compositional deviation between the target composition and the thin film composition due to the difference of the sputtering yield of the multi-component constituting the target, There is an effect that can be secured. Of course, the scope of the present invention is not limited by these effects.

1 is a graph illustrating the content of P and / or S in an amorphous formable alloy according to one embodiment of the present invention.
2A is a photograph of an amorphous alloy ribbon in the form of a foil according to an embodiment of the present invention, and 2b is a photograph of a laminate for manufacturing a target.
3A and 3B are photographs of an alloy target sintered after lamination of an amorphous alloy ribbon in the form of a foil according to an embodiment of the present invention.
4A is a photograph showing the microstructure before addition of P in an alloy target having a composition Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 .
4B is a photograph showing the microstructure of an alloy target having a composition Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 with P added thereto.
4C is a photograph showing the microstructure of an alloy target having a composition Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 with addition of S and P. FIG.
5 is a schematic view of a sputtering apparatus used for manufacturing a nanostructure composite thin film according to another embodiment of the present invention.
6A and 6B are SEM photographs of cross sections of thin films sputtered using an alloy target having the composition of Example P3 of Table 1 (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ).
FIG. 7 is a graph showing hardness and elastic modulus of a thin film formed by reactive sputtering using a nanocrystalline alloy target having various compositions according to another embodiment by a nanoindentation method. FIG.
FIGS. 8 and 9 are graphs showing the results of a friction test of a thin film deposited by a sputtering method using an alloy target according to another embodiment of the present invention. FIG.
10 and 11 are graphs showing the results of a friction test of a thin film formed by sputtering using an alloy target having the composition shown in Table 1 (Example P3).
12 is a graph illustrating an XRD analysis result of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention.
13 is a photograph of an EPMA analytical specimen analyzing a wear track of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention.
FIG. 14 shows the results of an EPMA analysis of a wear track of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention.
15A is a graph showing XPS analysis results of a specimen before a friction test of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention.
15B is a graph showing XPS analysis results of a specimen after a friction test of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Is provided to fully inform the user. Also, for convenience of explanation, the components may be exaggerated or reduced in size.

The crystalline alloy according to the present invention can be obtained by heating an amorphous alloy or a nanocrystalline alloy composed of four or more metal elements having glass forming ability in a temperature range not lower than the crystallization start temperature of the amorphous alloy or the nano- Can be implemented. In the case of such an amorphous alloy, crystallization takes place in the heating process, followed by grain growth. In the case of the nanocrystalline alloy, nanocrystalline growth occurs. At this time, the heating conditions are such that the average grain size of the alloy target ranges from 0.1 탆 to 5 탆, strictly 0.1 탆 to 1 탆, more strictly 0.1 탆 to 0.5 탆, more strictly 0.3 탆 to 0.5 탆 . ≪ / RTI >

In the present invention, the crystallization initiation temperature is a temperature at which an alloy in an amorphous state starts to crystallize, and has an inherent value according to a specific alloy composition. Therefore, the crystallization initiation temperature of the nanocrystalline alloy can be defined as the temperature at which the amorphous alloy having the same composition as the nanocrystalline alloy starts to crystallize.

Wherein the amorphous alloy has a substantially crystalline structure and the X-ray diffraction pattern shows a sharp peak at a specific Bragg angle and has a phase in which a broad peak is observed in a wide angle range, It can mean sieve. The nanocrystalline alloy may mean a metal alloy having an average grain size of less than 100 nm.

The amorphous formability means a relative measure indicating how much the alloy of a specific composition can be easily amorphized up to a certain cooling rate. Generally, in order to form an amorphous alloy through casting, a rapid cooling rate higher than a certain level is required. When the casting method is used with a relatively slow solidification rate (for example, a copper mold casting method), the amorphous forming composition range is reduced, The rapid solidification method such as melt spinning in which a molten alloy is dropped on a rotating copper roll to solidify it with a ribbon or a wire can achieve a maximized cooling rate of 10 ⁴ K / sec to 10 ⁶ K / sec or more to form amorphous The composition range that can be used is increased. Therefore, the evaluation of the degree of amorphous forming ability of a specific composition generally has a characteristic of representing a relative value depending on the cooling rate of a given rapid cooling process.

This amorphous forming ability is dependent on the alloy composition and the cooling rate, and generally the cooling rate is inversely proportional to the casting thickness [(cooling rate) α (casting thickness) ^-2 ], so the critical thickness of the casting material The amorphous forming ability can be relatively quantified. For example, according to the copper mold casting method, the critical casting thickness of the casting material (in case of a stick-shaped casting) capable of obtaining an amorphous structure can be expressed as a diameter. As another example, when the ribbon is formed by melt spinning, it can be expressed as a critical thickness of the ribbon in which amorphous is formed.

In the present invention, an amorphous alloy having an amorphous forming ability means that an amorphous ribbon is obtained at a casting thickness in the range of 20 μm to 100 μm when the molten alloy is cast at a cooling rate in the range of 10 ⁴ K / sec to 10 ⁶ K / sec Means an alloy that can be formed.

The amorphous alloy according to the present invention is composed of four or more elements and has a difference in atomic radius between major elements of 12% or more and a negative heat of mixing between main elements. .

 The four or more metal elements having amorphous forming ability according to an embodiment of the present invention include Zr; Al and; Cu and Ni; At least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe; Can be. For example, a quaternary alloy of Zr, Al, Cr and Cu, a quaternary alloy of Zr, Al, Co and Cu, a quaternary alloy of Zr, Al, Sn and Cu, Or a quaternary alloy of Zr, Al, Co, NI, and Cu. Further, the alloy having amorphous forming ability according to an embodiment of the present invention further includes at least one selected from P and S.

Wherein the alloy comprises 5 atom% to 20 atom% of Al; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder Zr; The Al may have a range from 6 atom% to 13 atom%, and at least one selected from Cu and Ni may have a range from 17 atom% to 30 atom%, and the Cr, Mo, Si, Nb, The sum of at least one selected from Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe may be in a range of 5 atomic% or less (more than 0). Here, the alloy having amorphous forming ability according to an embodiment of the present invention may include 30 ppm to 130 ppm of P, as shown in Fig. Alternatively, the amorphous forming alloy according to an embodiment of the present invention may include 10 ppm to 30 ppm of S, as shown in Fig. Alternatively, the amorphous forming alloy according to one embodiment of the present invention may include 30 ppm to 130 ppm of P and 10 ppm to 30 ppm of S, as in Fig.

Such a crystalline alloy according to the present invention has excellent thermal stability compared to an amorphous alloy of the same composition. That is, in the case of an amorphous alloy, due to thermal instability, locally partial crystallization occurs due to heat energy transferred from the outside, and nanocrystals are locally formed. This local crystallization is weakened by the structural relaxation of the amorphous alloy and the fracture toughness is reduced.

However, alloys whose grain size is controlled through crystallization and / or grain growth from an amorphous alloy or a nanocrystalline alloy, such as a crystalline alloy according to the present invention, do not exhibit large changes in microstructure even when heat is externally applied, Of the amorphous alloy or the nanocrystalline alloy does not exhibit destruction due to thermal and mechanical instability.

Such a crystalline alloy according to the embodiments of the present invention can be successfully applied to fields requiring thermal stability, and can be applied to a sputtering target as an example.

Alternatively, an amorphous alloy target composed of a plurality of metal elements having amorphous forming ability may be used to form an amorphous thin film or a nanocomposite thin film through non-reactive sputtering or reactive sputtering. In the case of the sputtering target, the ions accelerated from the plasma during the process continuously collide with each other, so that the temperature of the sputtering target inevitably rises during the process. When the sputtering target is made of amorphous material, local crystallization at the target surface due to a rise in temperature may proceed during the sputtering process, and this local crystallization may increase the brittleness of the target, which may result in the target being easily broken during the sputtering process.

On the other hand, since the sputtering target made of the crystalline alloy according to the present invention has a microstructure in which crystal grains having a specific size range controlled by heat treatment are uniformly distributed, the thermal / mechanical stability is greatly improved and the temperature rise There is no change in the local organization, and therefore, there is no mechanical instability as described above. Therefore, in the case of the crystalline alloy target of the present invention, sputtering can be used to stably form an amorphous thin film or a nanocomposite thin film.

Hereinafter, a method of manufacturing an alloy target for sputtering using the crystalline alloy of the present invention will be described as an example.

The sputtering alloy made of the crystalline alloy of the present invention may be formed by casting the above-described amorphous alloy or nano-crystalline alloy to a size and shape similar to those of a sputtering target actually used. The amorphous alloy or nano- , And annealing to grow the crystal grains or the crystal grains, thereby producing a crystalline alloy target.

As another method, a plurality of amorphous alloys or nanocrystalline alloys may be prepared, and a plurality of amorphous alloys or nanocrystalline alloys may be thermally pressed to bond to each other to produce a sputtering target made of a crystalline alloy. Plastic deformation of an amorphous alloy or a nanocrystalline alloy may occur during the heat pressing.

Wherein the annealing or heat pressing is performed in a temperature range that is not lower than the crystallization start temperature of the amorphous alloy or the nanocrystalline alloy but lower than the melting temperature. The crystallization initiation temperature is defined as the temperature at which an alloy having a specific composition begins to transition from an amorphous state to a crystalline state.

The plurality of amorphous alloys or nanocrystalline alloys may be, for example, amorphous alloy powders or nanocrystalline alloy powders. The agglomerates of these alloy powders are pressed and sintered in a sintered metal mold and bonded to each other, whereby a shape and size approximate to an actual target can be produced. In this case, the pressure sintering is performed in a temperature range of the amorphous crystallization start temperature to the melting temperature lower than the amorphous crystallization start temperature in the composition of the alloy powder. During the heating process, the agglomerates of the amorphous alloy powder or the agglomerates of the nanocrystalline alloy powder are bonded to each other by diffusion to cause crystallization and / or grain growth. At this time, the time and / or temperature and the like are controlled so that the grain size in the crystallization or grain growth process has a specific range. Thus, the finally crystallized or grain-grown alloy has a grain size of less than 5 탆, for example in the range of 0.1 탆 to 5 탆, strictly in the range of 0.1 탆 to 1 탆, more strictly in the range of 0.1 탆 to 0.5 탆 , And more strictly, in the range of 0.3 탆 to 0.5 탆.

At this time, the amorphous alloy powder or the nanocrystalline alloy powder may be one produced by automizing. Specifically, a molten metal in which the aforementioned elements having amorphous forming ability are dissolved is prepared, and an inert gas such as argon gas is sprayed onto the molten metal while the molten metal is sprayed, thereby rapidly cooling the molten metal to form an alloy powder.

As another example, a plurality of amorphous alloys or nanocrystalline alloys may be amorphous alloy ribbons or nanocrystalline alloy ribbons. After a plurality of such ribbons are laminated, a target made of a crystalline alloy can be formed by thermocompression in a temperature range from a crystallization start temperature to a melting temperature lower than a crystallization start temperature in the composition of the alloy ribbon. In this case, the amorphous alloy ribbon laminate or the nanocrystalline alloy ribbon laminate undergoes crystallization and / or grain growth while bonding due to interdiffusion between the ribbons. Meanwhile, the lamination interface between the stacked alloy ribbons in this process can be extinguished by mutual diffusion.

At this time, the amorphous alloy ribbon or the nanocrystalline alloy ribbon may be one produced by a rapid solidification process such as melt spinning. Specifically, a molten metal in which the aforementioned elements having amorphous forming ability are dissolved is prepared, and the molten metal is put on a surface of a roll rotating at a high speed to rapidly solidify the amorphous alloy or nanocrystalline alloy in a ribbon shape.

As another example, a plurality of prepared amorphous alloys or nanocrystalline alloys may be amorphous alloy castings or nanocrystalline alloy castings. At this time, the amorphous alloy casting material or the nanocrystalline alloy casting material may have a rod shape or a plate shape. In this case, in the laminate in which a plurality of amorphous alloy casting materials are laminated or a nano-crystalline alloy casting material is laminated during the heat-pressurizing treatment, crystallization and / or grain growth is caused do. At this time, the interface between the alloy castings may be eliminated by mutual diffusion.

At this time, the amorphous alloy casting material or the nanocrystalline alloy casting material may be formed by using a suction method or a pressurizing method in which the molten metal is injected into a mold such as copper having high cooling ability by using a pressure difference between the inside and the outside of the mold ≪ / RTI > For example, in the case of a copper mold casting method, a molten metal having the aforementioned amorphous forming ability is prepared, and the molten metal is injected into the copper mold at a high speed through a nozzle by pressurizing or sucking the molten metal and rapidly solidified to form amorphous Alloy castings or nanocrystalline alloy castings can be produced.

In the case of alloy ribbons or alloy castings, the final crystallized alloy, like in the case of alloy powders, is adjusted such that the grain size of the alloy is in the range described above.

Meanwhile, the nano-structured composite thin film can be formed by sputtering using an alloy target according to the embodiments of the present invention. The nano-structured composite thin film may be a thin film having a fine grain size corresponding to a crystal grain size in the range of 5 nm to 30 nm, strictly in the range of 5 nm to 10 nm, and having a structure in which a nitride phase of a metal and at least one metal phase are mixed with each other have. Further, the nanostructured composite thin film formed by sputtering using the alloy target according to the embodiments of the present invention may further include at least one selected from P and S.

The nanostructured composite thin film exhibits a crystal structure of Zr nitride, and other metal elements including Al may be dissolved in the Zr nitride in the form of a nitride. Wherein the Zr nitride comprises ZrN. For example, in the case of Al, it can be employed in the ZrN by replacing a part of Zr of the crystal lattice of ZrN. In this case, the nitride containing Zr and Al may mean a solid solution of ZrN and AlN. In the nanostructured composite thin film, the nitride phase of the metal has a nanocrystalline structure consisting of nanocrystalline grains. On the other hand, in the embodiment of the present invention, Zr nitride is not limited to ZrN, Zr nitride as according to the flow reduction in the cant is, for example In accordance with the change of the process variable may be formed with a Zr ₂ N.

On the other hand, the metal phase may include a metal element having a lower nitride forming ability than a metal element constituting the nitride. In the nanostructured composite thin film, the nitride phase of the metal has a nanocrystalline structure consisting of nano-level crystal grains, while the metal phase can be traced to such a nanocrystalline system. For example, the metal phase is distributed in several atomic units and can exist in a form that does not form a special crystal structure. However, such a metal phase is not distributed intensively in a specific region but is uniformly distributed throughout the thin film. For example, the metal phase may include at least one selected from Cu and Ni. The nano-structured composite thin film may be formed by sputtering using an alloy target according to embodiments of the present invention. The nanostructure composite thin film may be formed of a material selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, And these elements may exist in a metal state due to a relatively low nitriding reaction. For example, they may exist in a boundary region of nanocrystalline grains or may exist with amorphous characteristics.

When a thin film is formed on a base material by non-reactive sputtering using a crystalline alloy target, the thin film may be an amorphous alloy thin film. Here, the non-reactive sputtering means sputtering in which sputtering is performed only with an inert gas, for example, Ar, without introducing a gas which is intrinsically reactive with the material constituting the crystalline alloy target into the sputtering apparatus. The crystalline alloy target has an amorphous ability to form and thus exhibits an amorphous alloy structure in a process in which a solid phase is formed at a high cooling rate such as sputtering. The amorphous alloy thin film formed at this time may have a composition approximate to the composition of the crystalline alloy target used for sputtering.

When a thin film is formed on the base material by reactive sputtering using the crystalline alloy target, the thin film may have a nanostructure composite thin film. For example, when sputtering is performed while introducing a gas containing nitrogen gas (N ₂ ) or nitrogen (N) as a reactive gas into the sputtering chamber, for example, a gas such as NH ₃ , Zr can form a ZrN or Zr N ₂ for Zr nitride, for example, by reaction with nitrogen, or other elements can be present in the solid solution, or the metal Zr nitride. At this time, the produced thin film may have a fine grain size of nano-scale, for example, 5 nm to 30 nm, further 5 nm to 10 nm.

The nanostructured composite thin films according to the embodiments of the present invention exhibit very fine nanocrystalline grains while being mixed with Zr nitride having a high hardness and a metal alloy having a relatively low elastic modulus within the thin film, The difference in elastic modulus between the first and second elastic members is not large. In particular, it exhibits a remarkably improved low friction characteristic as compared with the conventional one, which will be described later.

In order to further improve the properties of the base material coated with the nanostructured composite thin film, a buffer layer may be further formed between the bottom of the nanostructured composite thin film, that is, between the base material and the nanostructured composite thin film. At this time, the buffer layer can function as an adhesion layer for further improving the adhesion of the nanostructure composite thin film to the base material, for example. As another example, the buffer layer may be a stress relaxation layer to relax the stress between the base material and the nanostructured composite thin film, and as another example, it may be a corrosion resistant layer for improving corrosion resistance. However, the present invention is not limited thereto, and refers to a layer that can be interposed between the nano-structured composite thin film and the parent material in terms of the structure of the thin film.

As such a buffer layer, an amorphous alloy thin film formed using the above-described crystalline alloy target may be used. Specifically, in the step of coating the base material by sputtering after mounting the crystalline alloy target in the sputtering chamber, in the first step, an amorphous alloy thin film is formed on the base material by a non-reactive sputtering process to a predetermined thickness, The nanostructure composite thin film can be formed by performing sputtering while introducing nitrogen gas. In this case, the buffer layer and the nano-structured composite thin film can be formed in-situ by using the same crystalline alloy target. However, the present invention is not limited thereto. The amorphous alloy thin film and the nano-structured composite thin film, which are the buffer layer, may be formed using nanocrystalline targets having different compositions, or may be formed separately in separate chambers .

As another example of the buffer layer, a metal layer using another different target, for example, a Cr layer using a Cr target or a Ti layer using a Ti target, may be used. As another example, a double layer in which a Ti layer and an amorphous alloy thin film layer are sequentially laminated from the surface of the above-described metal base material, or a double layer in which a Cr layer and an amorphous alloy thin film layer are sequentially laminated.

Hereinafter, embodiments are provided to facilitate understanding of the present invention. It should be understood, however, that the following examples are for the purpose of promoting understanding of the present invention, but the present invention is not limited by the following examples.

Manufacture of sputtering target

Table 1 summarizes the composition of the various embodiments, the amount of additive material, the method of injection, and the like for the aforementioned amorphous alloy capable of containing at least one selected from P and S.

Since the glass forming ability (GFA) depends on the alloy composition and the cooling rate, and the cooling rate is inversely proportional to the casting thickness (cooling rate)? (Casting thickness) ^-2 , the casting material which can obtain amorphous By evaluating the critical thickness, amorphous forming ability can be relatively quantified. For example, when the ribbon is formed by melt spinning, it can be expressed as a critical thickness of the ribbon in which amorphous is formed. Referring to Table 1, the amorphous formability is relatively higher in Example P5 (composition Zr _65.6 Al ₁₀ Co ₃ Cu _21.4 ) than in Example P2 (composition Zr _64.6 Al _7.1 Cr _2.2 Cu _26.1 ).

Examples P2 to P11 include at least one selected from Cu and Ni; At least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe; Al; P; And Zr; wherein the crystalline alloy includes P by adding 49.2 ppm to 109.6 ppm of gypsum as the amorphous alloy having amorphous capability. Haman Indong is used as an anode which is a supply source of Cu ions in the process of manufacturing printed circuit boards. P is added in the range of 400ppm to 650ppm for improving plating properties. In the case of Hamain copper alloys, all of the Cu corresponding to the alloy target composition was used as a crucible.

[Table 1]

In the examples disclosed in Table 1, the BCUP-2 or Hamindo-type alloy is exemplified as the P-doped parent alloy, but the technical idea of the present invention is not limited thereto, and the P- Of brazing filler metal.

[Table 2]

In addition, the P-doped parent alloy may include a commercial Cu alloy, such as tantalum, which uses P to remove oxygen in Cu and may ultimately contain from 40 ppm to 400 ppm of residual P have. The P-doped parent alloy may also include BCUP-2, which is a brazing filler metal consisting of 92.8% Cu and 7.2% P. Since BCUP-2 has a high content of phosphorus, BCUP-2 was added after calculating the target composition as the parent alloy concept, and the remaining Cu used high-purity oxygen-free copper.

On the other hand, in Table 1, Examples SP1 to SP2 show that at least one selected from Cu and Ni; At least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe; Al; P; S; And Zr; wherein S is added to the alloy by introducing Cu ₂ S, and P is added to the alloy by introducing the sintered alloy, so that the crystalline alloy includes P and S, respectively. In particular, the S-doped parent alloy may be a Cu-S parent alloy such as copper (I) sulfide, for example, Cu ₂ S powder may be used.

Meanwhile, Table 3 summarizes the ICP (Inductively Coupled Plasma) analysis of the sputtering target composition to which P and / or S is added.

[Table 3]

ICP analysis refers to a method of performing spectroscopic analysis by mixing a sample in a discharge plasma of a non-polarity generated by flowing a high-frequency current through a high-frequency oscillator of several kW to several tens kW to a coil in an inert gas flow. The objects analyzed in Table 3 include the amorphous foil produced by making the alloy ingot in the arc melting furnace and using the rapid solidification method.

Taking the example P3 shown in Table 1 and Table 3 as an example, 80 ppm of Ham's copper was injected into a molten metal in which 12 atom% of Al, 3 atom% of Co, 20.6 atom% of Cu and 64.4 atom% of Zr were dissolved As a result of ICP analysis of the formed alloy, it can be seen that the amount of P contained in the actually formed alloy is only 49.2 ppm.

According to the ICP analysis performed in this manner, it was confirmed that the amorphous alloy having an amorphous forming ability according to an embodiment of the present invention contains 30 ppm to 130 ppm of P, as shown in FIG. Alternatively, it has been confirmed that the amorphous forming alloy according to one embodiment of the present invention includes 30 ppm to 130 ppm of P and 10 ppm to 30 ppm of S, as in Fig.

FIGS. 2A and 2B are photographs of an amorphous alloy ribbon and a laminate in the form of foil according to an embodiment of the present invention. FIG. 3A and FIG. 3B are cross-sectional views of the amorphous alloy ribbon in the form of a foil according to an embodiment of the present invention These are photos of the sintered alloy target.

First, as shown in FIGS. 2A and 2B, an amorphous alloy foil having a composition (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ) according to Example P3 of Table 1, that is, an amorphous alloy ribbon was produced. This amorphous alloy ribbon contains 49.2 ppm of phosphorus in the state where at least three metal elements (64.4 atomic percent of Zr, 12 atomic percent of Al, 3 atomic percent of Co, and 20.6 atomic percent of Cu) having amorphous forming ability are dissolved A ribbon-shaped amorphous alloy (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ) was prepared by providing a molten metal with a crucible at high speed on a rotating roll surface to perform rapid solidification such as melt spinning . The foil, which is an amorphous alloy, has a thickness of 50 탆 to 150 탆 and is produced in a vacuum atmosphere.

3A and 3B, the ribbon-shaped amorphous alloy (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ) was laminated and sintered at a temperature of 800 ° C. for 30 minutes to obtain a crystalline alloy having the composition according to Example P3 Target. Such sintering is carried out in a temperature range above the crystallization start temperature of the amorphous alloy and below the melting temperature. During the heating process, the layers of the amorphous alloy ribbon are bonded to each other by diffusion and crystallization occurs. At this time, the time and / or temperature and the like are controlled so that the size of the crystal grains has a specific range.

The alloy target implemented in this way may be at least one selected from Cu and Ni, for example, as in Examples P2 to P11 of Table 1; At least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe; Al; P; And Zr; and as another example, as in Examples SP1 to SP2 of Table 1, at least one selected from Cu and Ni; At least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe; Al; P; S; And Zr; < / RTI >

Referring to Figs. 4A to 4C, the microstructure of a crystalline alloy target implemented in this manner will be described. As a specific example, a photograph of a structure of an alloy target having a composition (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ) according to the embodiment of Table 1 is shown in FIG. 4A. FIG. 4A is a _{graph of} a Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 alloy 4B is a photograph showing the microstructure of Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 alloy (Example P3 in Table 1) to which P is added, and FIG. 4C is a photograph showing the microstructure of Zr _{64.4 12} is a photograph showing the microstructure of an Al ₁₂ Co ₃ Cu _20.6 alloy (Example SP1 in Table 1).

Looking at such microstructures, the finally crystallized alloy is characterized in that the grain size of the alloy is less than 5 탆, for example in the range of 0.1 탆 to 5 탆, strictly in the range of 0.1 탆 to 1 탆, more strictly 0.1 탆 to 0.5 Lt; RTI ID = 0.0 > um, < / RTI > It has an effect of narrowing the compositional deviation between the target composition and the thin film composition due to the difference in the sputtering yield of the multi-component constituting the target, and it is possible to secure the compositional uniformity according to the thickness of the thin film There is an effect that can be done.

Further, it was confirmed that cracks were not generated even when a load of 5000 g was applied to the alloy target according to the present embodiments. The thermal / mechanical stability of the target was greatly improved, and the target suddenly appeared during the sputtering process So that the sputtering process can be stably performed.

Fabrication of amorphous or nanostructured composite thin films

A thin film was formed by a sputtering method using a crystalline alloy target produced by the above method. In sputtering, both non-reactive sputtering for forming a metal thin film in an Ar atmosphere and reactive sputtering for forming a thin film including a nitride film in an Ar and N ₂ mixed atmosphere were performed.

5 shows a schematic view of a magnetron sputtering equipment 100 used for sputtering. The distance between the target 102 and the substrate holder 103 in the chamber 101 was adjusted in the range of 50 to 80 mm. During the process, the chamber pressure was maintained at 5 mTorr and the total flow rate of the input gas was set at 36 sccm. In the case of film formation by non-reactive sputtering, only Ar was introduced through the gas line 106. In the case of reactive sputtering, nitrogen gas was introduced at a rate of 3 to 5 sccm through the gas line 107, and Ar was introduced through the gas line 106 at the remaining flow rate.

Power of 200 to 450 W was applied to the target 102 through the power supply device 104, and the substrate 103 was not heated by a separate heating device. The substrate holder 103 is connected to a pulse supply device 105 capable of applying a DC pulse to the substrate for plasma cleaning of the substrate surface before the sputtering process. High-speed steel and silicon wafers were used as substrates.

For evaluation of the obtained thin films, the hardness and elastic modulus of the thin films were measured by the nanoindentation method, and the structure and crystallinity of the thin films were confirmed by X - ray diffraction analysis. In order to observe the microstructure, SEM (scanning electron microscopy) and electron probe X-ray microanalysis (EPMA) were used.

Table 4 shows the sputtering conditions and the method of forming the nanostructure composite thin film according to another embodiment of the present invention.

[Table 4]

FIGS. 6A and 6B are SEM images of cross-sections of a nanostructure composite thin film according to another embodiment of the present invention. FIG. Specifically, FIGS. 6A and 6B are cross-sectional views of a thin film sputtered using an alloy target having a composition (Zr _64.4 Al ₁₂ Co ₃ Cu _20.6 ) of Example P3 in Table 1.

Table 5 shows the results of EPMA analysis of thin films deposited by non-reactive sputtering using alloy targets having compositions of Examples P5 and P8 of Table 1. [ The substrate on which the thin film was formed was a silicon wafer, the distance between the target and the substrate was 5 cm, the process pressure was 5 mTorr, and the buffer layer in the thin film was formed in an argon atmosphere with a power of 200 W for 10 minutes. Under a nitrogen atmosphere of argon and 4sccm at a power of 300 W for 35 minutes.

EPMA analysis of the nitride film revealed that the nitrogen content of about 32 ~ 36% was observed, indicating that there was a mutual reaction between the nitrogen introduced during the process and the target (shown in the first row in each composition). In addition, the chemical composition of the remaining elements except for nitrogen was observed. As a result, it was confirmed that the alloy component of the thin film approximated to the alloy component of the target, and the alloy component of the target was uniformly transferred to the thin film (shown in the second row in each composition). However, the phosphorus content was not measured because it was contained in ppm units which can not be measured by EPMA analysis.

[Table 5]

FIG. 7 shows the hardness and the elastic modulus measured by the nanoindentation method for thin films formed by reactive sputtering using a crystalline alloy target having various compositions. Referring to FIG. 7, all of the nanostructured composite thin films showed a hardness value of about 25 GPa or more, which is comparable to that of the high hardness ceramic material. From this, it can be understood that the nanostructure composite thin film of the present invention can realize high hardness.

Table 6 shows a friction test method for evaluating the friction characteristics of the thin film formed by the sputtering method using the alloy target according to the embodiments of the present invention with respect to the base oil.

[Table 6]

Table 7 shows the friction test conditions and results of the thin film deposited by the sputtering method using the alloy targets (Examples P3 and SP1 in Table 1) according to one embodiment of the present invention, FIG. 3 is a graph showing a result of a friction test of a thin film formed by a sputtering method using an alloy target according to an embodiment of the present invention. FIG. Under the friction test conditions, the test temperature was 90 ° C, the oil used was 5W30, and the test time was 15 minutes per load. According to this, it was confirmed that when P is added, the friction coefficient of the thin film formed by the sputtering method using the alloy target according to the embodiment of the present invention is remarkably reduced.

[Table 7]

Generally, in many cases, excellent lubricating properties are required in driving parts, sliding parts, or various tools of various mechanical devices. In order to improve the lubrication characteristics, a technique of forming a thin film having low friction characteristics on the surface of the base material can be applied. For example, energy consumption may occur due to friction between various parts generated during driving of an automobile engine. When the friction between these driving parts is reduced, the consumption of the automobile fuel is reduced, and the fuel efficiency can be improved. Since the thin film having such a low friction property must withstand a severe friction environment, it is required to have a hardness not less than a certain level of hardness, adhesion to the base material, and high resistance to an oxidizing atmosphere. As the thin film having such low friction characteristics, a nitride having a high hardness, a ceramic material based on a carbide, a diamond like carbon (DLC), or the like can be used and applied by physical vapor deposition, chemical vapor deposition, plasma spray coating, .

However, the conventional ceramic-based thin film exhibits a high hardness of about 2000 Hv or more, but exhibits a high difference in elastic modulus with a metal material such as steel, aluminum, and magnesium used as a base material. For example, most of the high melting point ceramic materials have a modulus of elasticity of 400 to 700 GPa compared to about 70 GPa for aluminum alloy, about 45 GPa for magnesium alloy and about 200 GPa for steel, Lt; / RTI > And also exhibits a high coefficient of friction for application to important drive members such as automotive engines. On the other hand, in the case of the DLC film, the friction reduction effect is not large in the boundary lubrication environment, and graphitization (sp ³ → sp ² ) progresses due to abrasion under the boundary lubrication environment accompanied by the temperature rise due to the solid- This can result in serious wear of the membrane and may not be compatible with additives such as friction modifiers added in the lubricating oil, such as, for example, organic molybdenum compounds (MoDTC, Molybdenum dialkyldithiocarbamate), which reduces the additive efficiency, There is a possibility that a problem of promoting the reaction may occur.

However, the thin film formed by the sputtering method using the alloy target according to an embodiment of the present invention has a low friction characteristic with high hardness and adhesion while exhibiting much lower friction coefficient than the conventional thin film. Particularly, the thin film formed by the sputtering method using the alloy target according to an embodiment of the present invention includes at least one of P and S, whereby the coefficient of friction is remarkably low, while the high hardness and adhesion And a low friction characteristic.

Recently, the content of S, P, Cl, etc. as an additive to the oil has been regulated as an additive in the existing oil to improve the wear and friction characteristics of the engine part. As a result, severe abrasion and fusion It is required to develop a coating material capable of improving the friction characteristics in the environmentally friendly 5W30 base engine oil to which the friction modifier is not added. As a result, in an embodiment of the present invention It is expected that the thin film formed by the sputtering method using the alloy target according to the present invention can meet this demand.

Table 8 shows the friction test conditions and results of the thin film formed by the sputtering method using the alloy target having the composition shown in Table 1, and Figs. 10 and 11 show the results of the friction test conditions and the results of the alloy target having the composition (Example P3) Which is a graph showing a result of a friction test of a thin film formed by a sputtering method. The test temperature was 90 ° C under the friction test conditions. The oil used was environmentally friendly base engine oil 5W30 and the test time was 15 minutes per load.

According to this, it is confirmed that the addition of P and / or S significantly decreases the coefficient of friction of the thin film formed by the sputtering method using the alloy target according to one embodiment of the present invention, as compared with the case of using the DLC low friction thin film there was. In particular, referring to FIG. 11, when the load is 50 N, the friction coefficient is significantly lower than that of the bare plate even when the DLC low friction thin film is coated. However, when the load is 100 N, And it is confirmed that there is a limit to realize low friction characteristics by the DLC thin film. On the contrary, it was confirmed that the thin film formed by the sputtering method using the alloy target according to the embodiment of the present invention significantly reduced the friction coefficient even when the load was 50N as well as 100N, as compared with the case where the bare plate or DLC coating was applied there was.

[Table 8]

12 is a graph illustrating an XRD analysis result of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention. Under the sputtering conditions, the substrate was a high-speed steel, and the distance between the substrate and the target was 5 cm, the process pressure was 5 mTorr, and the buffer layer in the thin film was formed under an argon atmosphere at a power of 200 W for 7 minutes. Of argon and 4 sccm of nitrogen at a power of 300 W for 25 minutes. On the other hand, the composition of the alloy target corresponds to the example P3 in Table 1. According to this, the intensity of the peak of the (200) face increases with the addition of P. Further, the half value width increases with the addition of P, which means that the structure of the nanostructure composite thin film becomes finer.

13 is a photograph of an EPMA analysis specimen for analyzing a wear track of a nanostructure composite thin film sputtered using an alloy target according to another embodiment of the present invention. According to this, when the wear track area is enlarged, it is made up of the wear track w1 and the unaffected area w2. The composition of the analytical specimen corresponds to Example P3 of Table 1, and the coating condition was an argon atmosphere for 10 minutes in the buffer layer, and a power of 300 W in a nitrogen atmosphere of 4 sccm for 35 minutes. Table 9 and FIG. 14 summarize the analysis results of the EPMA. High concentrations of phosphorus and oxygen were detected in the abrasion marks after the friction test, and phosphorus and oxygen components were not detected in the areas without abrasion. Therefore, it was confirmed that the phosphorous component distributed in the coating layer formed the tribo film containing the phosphorus component of the alloy target component of the present invention under the boundary lubrication condition in the friction test.

. FIG. 15A is a graph showing the XPS analysis results of the specimen before the friction test, and FIG. 15B is a graph showing the XPS analysis results of the specimen after the friction test. XPS analysis showed that the compounds such as ZrN, Cu and CuO were the same but AlPO4 compounds were observed to increase significantly in the abrasion. Therefore, it has been confirmed in the present invention that the phosphorus component added for low friction implementation can form a tribo film for a low friction implementation.

[Table 9]

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (21)

As the alloy having an amorphous forming ability and being composed of four metal elements or more,
The average grain size of the alloy is in the range of 0.1 탆 to 5 탆,
The alloy contains 5 atom% to 20 atom% of Al; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr. The crystalline alloy according to claim 1, wherein at least one of P and S is P of 30 ppm to 130 ppm. The crystalline alloy according to claim 1, wherein at least one of P and S is 10 ppm to 30 ppm S, and has amorphous ability. The method of claim 1, wherein at least one of P and S is selected from the group consisting of 30 ppm to 130 ppm of P; And 10 ppm to 30 ppm of S; an amorphous alloy. The casting method of claim 1, wherein the alloy has a critical casting thickness of 20 to 100 占 퐉, wherein the casting ribbon capable of obtaining an amorphous structure when casting the molten alloy at a cooling rate in the range of 10 ⁴ K / sec to 10 ⁶ K / Crystalline amorphous alloy. ≪ Desc / Clms Page number 24 > The crystalline alloy according to claim 1, wherein the average grain size of the alloy is in the range of 0.3 탆 to 0.5 탆. The method of claim 1, wherein the Al content is in the range of 6 to 13 atomic%, the at least one of Cu and Ni is in the range of 17 to 30 atomic%, the Cr, Mo, Si, Nb, Co, Sn, In, V, Hf, Ag, Ti, and Fe in an amount of 5 atomic% or less (more than 0). The alloy target for sputtering according to any one of claims 1 to 7, which is made of a crystalline alloy having an amorphous forming ability. An amorphous alloy or a nanocrystalline alloy having an amorphous forming ability and having a quadruple metal element or more is heated in a temperature range not lower than a crystallization starting temperature of the amorphous alloy or a nanocrystalline alloy to a range of 0.1 to 5 μm So that,
The amorphous alloy or the nanocrystalline alloy contains 5 atom% to 20 atom% of Al; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr. 10. The method for producing a crystalline alloy according to claim 9, wherein at least one of P and S is P of 30 ppm to 130 ppm. 10. The method for producing a crystalline alloy according to claim 9, wherein at least one of P and S is S of 10 ppm to 30 ppm. The method of claim 9, wherein at least one of P and S is selected from the group consisting of 30 ppm to 130 ppm of P; And 10 ppm to 30 ppm of S; wherein the amorphous alloy has an amorphous forming ability. 11. The method according to claim 9, wherein the Al content is in the range of 6 to 13 atomic%, the content of at least one of Cu and Ni is in the range of 17 to 30 at%, the Cr, Mo, Si, Nb, Co, Sn, In, V, Hf, Ag, Ti and Fe is not more than 5 atomic% (more than 0). 10. The method for producing an amorphous alloy according to claim 9, wherein an average size of the crystal grains is controlled to be in the range of 0.3 mu m to 0.5 mu m. Preparing a plurality of amorphous alloys or nanocrystalline alloys having at least four metal elements and having amorphous forming ability; And
The plurality of amorphous alloys or nanocrystalline alloys are thermally pressurized in a temperature range not lower than the crystallization start temperature of the amorphous alloy or the nanocrystalline alloy at a temperature not lower than the crystallization start temperature to produce a crystalline alloy having an average grain size in the range of 0.1 탆 to 5 탆 step; / RTI >
The amorphous alloy or the nanocrystalline alloy contains 5 atom% to 20 atom% of Al; 15 atom% to 40 atom% of at least one selected from Cu and Ni; At least one selected from the group consisting of Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe is not more than 8 atomic% P and S; And the remainder being Zr. 16. The method according to claim 15, wherein at least one of P and S is P of 30 ppm to 130 ppm. 16. The method according to claim 15, wherein at least one of P and S is S of 10 ppm to 30 ppm. 16. The method of claim 15, wherein at least one selected from P and S comprises 30 ppm to 130 ppm of P; And 10 ppm to 30 ppm of S; 15. The method according to claim 15, wherein an average size of the crystal grains is in the range of 0.3 mu m to 0.5 mu m. 15. The method according to claim 15, wherein the amorphous alloy or the nanocrystalline alloy is an amorphous alloy ribbon or a nanocrystalline alloy. 21. The method of claim 20, wherein the amorphous alloy ribbon or nanocrystalline alloy ribbon comprises:
Preparing a molten metal in which the four metal elements or more are dissolved;
Adding at least one selected from P and S to the molten metal; And
Adding the at least one selected from P and S to the rotating roll;
Wherein the sputtering target is produced by melt spinning.

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