KR101459700B1 - Method for heat treatment of amorphous alloy and method for manufacturing crystalline alloy - Google Patents

Abstract

An objective of the present invention is to provide a method for preparing a crystalline alloy having amorphous performance and having thermal stability superior to that of an amorphous alloy and a method for performing heat treatment for the amorphous alloy. According to one aspect of the present invention, provided is a method for preparing the crystalline alloy, which includes the steps of preparing multiple amorphous alloys or nano-crystalline alloys including metallic elements having amorphous performance; performing first heat treatment to maintain the amorphous alloys or the nano-crystalline alloys at a constant temperature ranging from a glass transition temperature (Tg) to a start temperature (Tx) of the amorphous alloy or the nano-crystalline alloy for a predetermined period of time; and performing second heat treatment for the amorphous alloys or the nano-crystalline alloys at a constant temperature within 0.7 times to 0.9 times higher than a melting temperature (Tm) of the amorphous alloy or the nano-crystalline alloy for a predetermined period of time.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of annealing an amorphous alloy,

The present invention relates to a method of annealing an amorphous alloy and a method of manufacturing a crystalline alloy, and more particularly, to a method of annealing an amorphous alloy containing a metal element having amorphous forming ability and a method of producing the 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, an amorphous alloy system having a capability of forming a bulk amorphous material having a sputtering target size that is used industrially has not been reported. To solve this problem, an amorphous powder is prepared, and then a high pressure of 600 MPa or more is applied. Technology is being tried.

On the other hand, even in a high-density amorphous target produced under high pressure, the temperature increases due to ion collision in the sputtering process, and the tissue near the surface of the target can be changed due to such temperature increase. 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.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an amorphous sintered body excellent in thermal stability, And to provide a method for producing a crystalline alloy which can be easily put to practical use. It is another object of the present invention to provide a method of sintering and / or heat treating an amorphous alloy and a method of manufacturing a plurality of amorphous alloys by sintering / bonding and high-crystalline alloy bulk material for producing the crystalline alloy. However, these problems are exemplary and do not limit the scope of the present invention.

According to an 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 containing a metal element having amorphous forming ability; A plurality of amorphous alloys or nanocrystalline alloys which are maintained at a constant temperature for a predetermined time under a predetermined pressure in a temperature range not lower than the glass transition temperature (Tg) of the amorphous alloy or the nanocrystalline alloy at the crystallization start temperature (Tx) 1 heat treatment step; And a plurality of amorphous alloys or nanocrystalline alloys which are maintained at a constant temperature for a predetermined time under a predetermined pressure in a temperature range from a crystallization start temperature (Tx) of the amorphous alloy or a nanocrystalline alloy to a melting temperature (Tm) And a second heat treatment step.

Wherein the plurality of amorphous alloys or nanocrystalline alloys are heated in a temperature range from a crystallization start temperature (Tx) to a melting temperature (Tm) of the amorphous alloy or a nanocrystalline alloy at a predetermined pressure for a predetermined time The second heat treatment step of maintaining the temperature at a constant temperature may be performed by heating the plurality of amorphous alloys or the nanocrystalline alloy at a constant temperature for a predetermined time at a temperature ranging from 0.7 to 0.9 times the melting temperature (Tm) of the amorphous alloy or the nanocrystalline alloy As shown in FIG.

The method of manufacturing the crystalline alloy may further include heating the plurality of amorphous alloys or the nanocrystalline alloy between the first heat treatment step and the second heat treatment step.

In the method for producing a crystalline alloy, the first heat treatment step may include controlling the porosity of the amorphous alloy or the nanocrystalline alloy to 1% or less.

In the method for producing a crystalline alloy, the second heat treatment may include controlling the porosity of the amorphous alloy or the nanocrystalline alloy to 0.1% or less.

In the method for producing a crystalline alloy, the second heat treatment step may include crystallizing the plurality of amorphous alloys or the nanocrystalline alloy so that an average grain size of the amorphous alloy is in a range of 0.1 탆 to 5 탆.

In the method for producing a crystalline alloy, the amorphous alloy or the nanocrystalline alloy may have at least one form selected from the group consisting of a foil, a powder, a block, and a rod.

In the method for producing a crystalline alloy, the amorphous alloy or the nanocrystalline alloy may contain at least one selected from 67 atom% to 78 atom% of Zr, 4 atom% to 13 atom% of at least one selected from Al and Co, May be composed of 15 atom% to 24 atom%.

In the method for producing a crystalline alloy, the base amorphous alloy or the nanocrystalline alloy may be composed of 5 atom% to 20 atom% of Al, 15 atom% to 40 atom% of at least one selected from Cu and Ni, and the balance Zr.

Wherein the amorphous alloy or the nanocrystalline alloy contains Al in an amount of 5 to 20 at%, at least one of Cu and Ni in an amount of 15 to 40 at%, Cr, Mo, Si, Nb, Co, Sn, At least one selected from the group consisting of In, Bi, Zn, V, Hf, Ag, Ti and Fe is 8 atomic% or less (more than 0) and the remainder is Zr.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing an amorphous alloy including a metal element having amorphous forming ability; A first heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time in a temperature range not lower than a glass transition temperature (Tg) of the amorphous alloy and a crystallization start temperature (Tx); And a second heat treatment step of maintaining the amorphous alloy at a constant temperature for a predetermined time under a predetermined pressure in a temperature range not lower than the crystallization start temperature (Tx) of the amorphous alloy and not higher than the melting temperature (Tm) Is provided.

A second heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time under a predetermined pressure in a temperature range not lower than a crystallization start temperature (Tx) of the amorphous alloy and a melting temperature (Tm) May include a heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time in a temperature range of 0.7 to 0.9 times the melting temperature (Tm) of the amorphous alloy.

According to the embodiments of the present invention, it is possible to realize a crystalline alloy which can heat-treat an amorphous alloy at a relatively low cost, heat treat a plurality of amorphous alloys simultaneously with sintering / bonding, and greatly improve thermal / mechanical stability. Of course, the scope of the present invention is not limited by these effects.

1 shows the results of investigation of the amorphous forming ability of Zr _63.9 Al ₁₀ Cu _26.1 copper mold sucking cast material (rod) according to the embodiment of the present invention by using X-ray diffraction.
Fig. 2 shows the results of DSC analysis showing the crystallization characteristics of a Zr _63.9 Al ₁₀ Cu _26.1 copper mold sucking cast material (rod) according to an embodiment of the present invention.
3 (a) to 3 (e) are _graphs showing the results of cracking occurrence test of the Zr _63.9 Al ₁₀ Cu _26.1 alloy casting rod (rod) according to the embodiment of the present invention with electron microscopy to be.
4 (a) to 4 (d) show the results of observing the microstructure of Example 3 and Comparative Examples 2 to 4. FIG.
5 (a) to 5 (d) are electron microscopic observations of the microstructure of an alloy target produced by combining an amorphous alloy rod, an amorphous alloy powder, a nanocrystalline alloy powder and an amorphous alloy ribbon, respectively.
6 (a) and 6 (b) show X-ray diffraction patterns of the amorphous powder produced by the atomization method and the nanocrystalline powder annealed at 600 ° C.
FIG. 7 is a photograph showing the result of measuring the hardness of an amorphous foil sintered body having the composition disclosed in some embodiments of the present invention according to Table 4; FIG.
Figure 8 shows the results of observing microstructure for an amorphous foil sintered body having the composition disclosed in some embodiments of the present invention according to Table 4.
Figure 9 shows the results of investigation of an amorphous foil having the composition disclosed in some embodiments of the present invention according to Table 4 using X-ray diffraction.
10A is a diagram illustrating a concept of implementing a crystalline alloy by sintering or heat-treating an amorphous alloy or a nanocrystalline alloy in a manufacturing method according to an embodiment of the present invention.
Fig. 10B is a photograph of the microstructure of the alloy observed at each step shown in Fig. 10A by an electron microscope.
11 is a result of observing the surface of a target after sputtering of a crystalline alloy target (Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 ) produced according to an embodiment of the present invention.
Figs. 12 (a) and 12 (b) are the results of observing the microstructure of the crystalline alloy target (Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 ) of FIG. 11 before sputtering and the surface of the target after sputtering.
Figs. 13A and 13B show the results of observing the target fracture occurred during the sputtering of the amorphous alloy target having the same composition as that of the crystalline alloy target of Fig. 11, and observing the fracture plane with an electron microscope.
14 (a) and 14 (b) show X-ray diffraction patterns of the amorphous alloy target before and after sputtering of the amorphous alloy target of FIG.
Figs. 15A and 15B show the results of observing the periphery of the indentation region of the amorphous alloy target of Fig. 13 after electron beam microscopic observation after the cracking test before and after the sputtering.
16 is a result of observing the surface of the target after sputtering of the cast alloy target having the same composition as that of the crystalline alloy target of Fig.
17A and 17B show the results of observing the microstructure of the cast alloyed target of FIG. 16 before sputtering and the surface of the target after sputtering.
18 is a result of observation of a cast alloyed alloy target broken during the solidification process.

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 is characterized in that an amorphous alloy or a nanocrystalline alloy composed of three or more metal elements having an amorphous glass forming ability is heated to a crystallization start temperature (Tx) of the amorphous alloy or a nanocrystalline alloy at a melting temperature (Tm) Lt; 0 > C. 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 comprising the crystalline alloy is in the range of 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 Mu] m to 0.5 [mu] m.

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 high 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 composition range of amorphous formation 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 maximum cooling rate of 10 ⁴ K / sec to 10 ⁶ K / sec or more, thereby forming amorphous The composition range that can be used is increased. Therefore, the evaluation of the degree of amorphous formability of a particular composition is generally characterized by a relative value depending on the cooling rate of a given rapid cooling process.

Since the amorphous forming ability depends on the alloy composition and the cooling rate, 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 formability means that an amorphous ribbon is obtained at a casting thickness in the range of 20 μm to 100 μm when casting the molten alloy 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 having the ability to form amorphous materials according to the present invention is composed of three 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. .

 An alloy composed of three or more metal elements having an amorphous forming ability according to an embodiment of the present invention includes Zr; Al and Co; And at least one selected from Cu and Ni. For example, a ternary alloy composed of Zr, Al, and Cu; A ternary alloy composed of Zr, Al, and Ni; A ternary alloy made of Zr, Co and Cu; A quaternary alloy consisting of Zr, Al, Cu and Ni; A quaternary alloy made of Zr, Al, Co and Cu, or a quaternary alloy made of Zr, Co, Cu and Ni.

As a specific example, the alloy may be composed of 0 atom% to 20 atom% of Al, 15 atom% to 40 atom% of at least one selected from Cu and Ni, and the balance of Zr. For example, the alloy may be composed of 40 atom% to 80 atom% of Zr, 5 atom% to 20 atom% of Al, and 15 atom% to 40 atom% of at least one selected from Cu and Ni.

In another specific example, the alloy may be composed of 67 atom% to 78 atom% of Zr, 4 atom% to 13 atom% of at least one selected from Al and Co, and at least 15 atom% to 24 Atomic%. For example, the alloy may be composed of 67 atom% to 78 atom% of Zr, 4 atom% to 12 atom% of Co, and 15 atom% to 24 atom% of at least one selected from Cu and Ni. Further, for example, the alloy may include at least one selected from the group consisting of 67 atom% to 78 atom% of Zr, 3 atom% to 10 atom% of Al, 2 atom% to 9 atom% of Co, 23 atomic%.

An alloy composed of three or more metal elements having amorphous forming ability according to another embodiment of the present invention may include Zr; Al and Co; Cu and Ni; M may be an alloy composed of M, M, and at least one selected from Cr, Mo, Si, Nb, Co, Sn, In, Bi, Zn, V, Hf, Ag, Ti and Fe. For example, a multi-element alloy composed of Zr, Al, Cu, and M; A multi-element alloy consisting of Zr, Al, Ni, and M; A multi-element alloy made of Zr, Al, Cu, Ni, and M; Or a multi-element alloy consisting of Zr, Al, Co, Cu, and M.

For example, the alloy may contain 0 atom% to 20 atom% of Al, 15 to 40 atom% of at least one of Cu and Ni, 9 atom% or less of M (more than 0) have. For example, the alloy may contain at least one element selected from the group consisting of Zr at 40 atom% to 80 atom%, Al at 0 atom% to 20 atom%, at least one element selected from Cu and Ni, 15 atom% to 40 atom% ). ≪ / RTI >

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 amorphous alloys or nanocrystalline alloys such as the crystalline alloys according to the present invention do not show large changes in microstructure even when heat is applied from the outside, 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.

An amorphous alloy target composed of a plurality of metal elements having amorphous ability to form an amorphous thin film or a nanocomposite thin film through sputtering and reactive sputtering may be used. 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.

Also, in the sputtering target produced by the casting method, i) the equilibrium solidification structure of the alloy system is very weak because it is composed of an intermetallic compound having a high brittleness, and ii) the grain size of the constitution is very large, .

On the other hand, the crystalline alloy according to the present invention has a microstructure in which crystal grains having a specific size range controlled by heat treatment have a uniformly distributed microstructure, so that the thermal / mechanical stability is greatly improved and the local temperature , And thus the mechanical instability as described above does not appear. 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 alloy for sputtering using the crystalline alloy of the present invention may be one casted in a size and shape similar to the sputtering target in which the amorphous alloy or the nanocrystalline alloy is actually used. The amorphous alloy or the nanocrystalline alloy thus cast may be heat- A crystalline alloy target can be produced by crystallizing or growing crystal grains through annealing.

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

At this time, the annealing or the heat pressing is performed at a temperature not higher than the glass transition temperature (Tg) of the amorphous alloy at the crystallization start temperature (Tx) or less and the sintering temperature is higher than the crystallization start temperature of the amorphous alloy or the nanocrystalline alloy Secondary sintering and grain growth are performed in the temperature range. 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, in the pressure sintering, the first sintering proceeds at a temperature equal to or higher than the glass transition temperature (Tg) of the amorphous alloy at the crystallization start temperature (Tx) or less, and at the temperature range not lower than the crystallization start temperature of the amorphous alloy or the nano- Secondary sintering and grain growth are performed. 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 size of the crystal grains 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 three or more metal 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, the amorphous alloy or the nanocrystalline alloy prepared in plurality may be an amorphous alloy ribbon and / or a nanocrystalline alloy ribbon in the form of a foil. After the plurality of such ribbons are laminated, the target can be formed by thermal pressurization in a temperature range from the crystallization start temperature to the melting temperature in the composition of the alloy ribbon. In this case, the amorphous alloy ribbon laminate and / or the nanocrystalline alloy ribbon laminate undergo crystallization and / or grain growth during 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 three or more metal 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, a molten metal in which three or more metal elements having amorphous forming ability are prepared is prepared by a copper mold casting method, 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.

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.

Crystallization of rod-shaped amorphous alloy castings (alloy rods)

FIG. 1 shows the results of X-ray diffraction analysis of the amorphous formation ability of a Zr-Al-Cu alloy rod according to an embodiment of the present invention. FIG. 2 shows crystallization characteristics according to the diameters of the Zr- DSC analysis results are shown. The compositions of Zr-Al-Cu were 63.9, 10, and 26.1 at%, respectively. This is expressed as Zr _63.9 Al ₁₀ Cu _26.1 (hereinafter, the composition of the alloy is expressed in this manner).

The Zr _63.9 Al ₁₀ Cu _26.1 alloy rod was prepared by dissolving an alloy button having the above composition by arc melting, followed by copper mold suction casting. The melting temperature (solid phase temperature) of the Zr _63.9 Al ₁₀ Cu _26.1 alloy rod was 913 ° C. Figs. 1 and 2 (a), 2 (b), 2 (c) and 2 (d) show alloy rods having diameters of 2 mm, 5 mm, 6 mm and 8 mm, respectively.

Referring to FIG. 1, broad peaks typically observed in an amorphous phase are observed in a range of 5 mm or less in diameter, but crystalline peaks are observed in a range of 6 mm or more. Observation of the alloy rod with diameters of 6 mm and 8 mm by electron microscope revealed that the average grain size of the main grains was very fine nanocrystalline structure of 100 nm or less.

In general, the cooling rate of the mold casting method such as the copper mold suction casting method has a lower cooling rate than that of the melt spinning method, and thus the alloy has the amorphous forming ability defined in the present invention. Further, it can be understood that the alloy composition can be an amorphous alloy having a thickness or diameter of 5 mm or less when the copper mold suction casting method is used.

Referring to FIG. 2, although an exothermic peak corresponding to the crystallization behavior was observed at an elevated temperature up to an alloy rod diameter of 6 mm, no exothermic peak was observed at 8 mm. From this, it can be seen that, in the case of 6 mm, amorphous phase is present in a part together with the nanocrystalline structure. It can be seen that the glass transition temperatures (Tg) are 404.4 ° C, 400.9 ° C and 391.3 ° C, respectively, when the diameters are 2mm, 5mm and 6mm, respectively.

Table 1 shows hardness and cracking occurrence according to the annealing temperature of Zr _63.9 Al ₁₀ Cu _26.1 alloy rod having a diameter of 2 mm and Zr _63.9 Al ₁₀ Cu _26.1 alloy rod having an 8 mm diameter. The hardness was measured at 1 Kgf load, and the presence or absence of cracks was determined by observing the indentation marks under a 5 Kgf load with an electron microscope. The annealing was performed in a hot vacuum furnace and the annealing time was 30 minutes at all temperatures.

[Table 1]

As shown in Table 1, the hardness value of the alloy rod having a diameter of 2 mm and the alloy rod having a diameter of 8 mm increased as the annealing temperature was increased below 600 ° C., but decreased again at a temperature exceeding 600 ° C. On the other hand, the alloy rod having a diameter of 2 mm did not crack at 700 ° C and 800 ° C, and the alloy rod having a diameter of 8 mm did not crack at 800 ° C.

3 (a) to 3 (d) show the results of observing the indentation periphery when the alloy rod having a diameter of 2 mm was annealed at 600 ° C, 800 ° C, and 900 ° C, respectively, Shows an observation result of annealing an alloy rod having a diameter of 8 mm at 800 ° C.

3 (a) to 3 (c), when a crack occurs (FIG. 3 (a)), the average grain size (hereinafter referred to as crystal grain) is smaller than 0.1 탆 in a nanocrystalline structure (FIG. 3 (b) and FIG. 3 (c)), crystal grains having a size ranging from 0.1 μm to about 1 μm were uniformly distributed. When the crystal grains exceeded 5 mu m (Fig. 3 (d)), a crack occurred. 3 (e), it was confirmed that cracks did not occur even in the case of an alloy rod having nanocrystalline grains having a diameter of 8 mm when the microstructure similar to that of FIG. 3 (c) was exhibited.

From this, it can be seen that when the amorphous alloy rod is annealed and partially crystallized or crystallized with a nanostructure having nanocrystalline grains, the brittleness increases with increasing hardness. This increase in brittleness is attributed to the relaxation of the structure and the change in the free volume of the amorphous originally generated by precipitation of nanocrystalline grains in the amorphous matrix.

However, even if the amorphous alloy is completely crystallized, when the grain size is in the range of 0.1 탆 to 5 탆, the phenomenon of the increase in the brittleness due to the relaxation of the structure and the precipitation of the nanocrystalline does not occur and the fracture toughness is remarkably improved .

Table 2 shows the amorphous characteristics when annealed at 800 DEG C of an alloy casting material (2 mm diameter rod, 0.5 mm thick plate) containing various amorphous or amorphous phases in addition to the above alloy composition (Example 1 of Table 2) The results for crack occurrence are summarized (annealed at 700 ° C for Example 2 and Comparative Example 1). Tg, Tx and Tm in Table 2 indicate the glass transition temperature, the crystallization start temperature and the melting temperature (solid phase temperature), respectively. The grain size was measured by measuring the grain diameter of the metal of KS D0205.

[Table 2]

Fig. 4 (a) shows the result of observing the microstructure after the crack generation test by the indenter of Example 3 as an example. Figs. 4 (b) to 4 (d) show the results of observing the microstructure after the crack occurrence test of Comparative Examples 2 to 4. Cracks were observed in the case of the specimen not including Al in the alloy (Comparative Example 1) and the specimen in which the annealing temperature was higher than the melting point (Comparative Example 2). Also in the case of the example (Comparative Example 4) in which the composition of Cu was less than 15 atomic% and the composition of M (that is, Co) was 8 weight% or more, cracks were also observed. On the other hand, when a different kind of metal other than Zr, Al, Cu and Ni was added, cracking was observed when the composition of Al was 20 atomic% or more (Comparative Example 3).

Further analysis and observation results on the embodiments disclosed in Table 2 are the same as those of the analysis and observation described in Korean Patent Application No. 10-2011-0129888 filed by the inventors of the present application. Referring to Table 2, the alloys of Examples 2 to 30 exhibited a very similar microstructure to the alloys of Example 1 after annealing, and no cracks were observed in the cracking test.

On the other hand, the inventors of the present application found that the alloys of the additional embodiments disclosed in Table 3 exhibited microstructures very similar to those of the alloy of Example 1 after annealing, and no cracks were observed in the cracking test.

[Table 3]

Example 31, Example 33, Example 34, Example 36, Example 37, Example 38, Example 39, Example 40, Example 41, Example 42, Example 43, Referring to Example 44 and Example 45, an alloy consisting of 3 or more metal elements having amorphous forming ability according to an embodiment of the present invention is made of 67 atom% to 78 atom% of Zr, at least one selected from Al and Co is 4 At least one selected from atomic% to 13 atomic%, Cu and Ni may be composed of 15 atomic% to 24 atomic%.

For example, referring to Examples 42, 43, 44, and 45, an alloy composed of three or more metal elements having amorphous forming ability according to an embodiment of the present invention does not contain Al, Zr of 67 atom% to 78 atom%, Co 4 atom% to 12 atom%, Cu and Ni of 15 atom% to 24 atom%.

In addition, referring to Examples 31, 34, 36, 37, 38, 39, and 40, amorphous forming ability 3 according to an embodiment of the present invention The alloy consisting of the above metal elements does not contain Ni and contains 67 atom% to 78 atom% of Zr, 3 atom% to 10 atom% of Al, 2 atom% to 9 atom% of Co, 17 atom% 23 atomic%.

With respect to the composition of the alloy and the details thereof with reference to Tables 2 and 3, reference may be had to the patent application Nos. 10-2011-0129888 and 10-2013-0065244 already filed by the present inventors.

Fabrication of Alloy Targets Using Multiple Amorphous Alloy Bars

In Table 4, a plurality of 3 mm diameter amorphous alloy rods having the alloy composition (Zr _63.9 Al ₁₀ Cu _26.1 ) of Example 1 were prepared and laminated in a graphite mold, followed by heat pressurization in an electrification pressure sintering apparatus, The results of observing hardness and crack occurrence according to bonding temperature are shown. Here, the bonding temperature means the contact temperature of the graphite mold. In addition,? Tx in Table 4 means a temperature selected from the temperature interval between the glass transition temperature and the crystallization start temperature, that is, the subcooled liquid temperature interval.

[Table 4]

Referring to Table 4, when the bonding temperatures were 700 ° C. and 800 ° C. as in the results shown in Table 1, cracks did not occur. As a result of observation with an electron microscope, crystal grains having a grain size of 1 μm or less were uniformly distributed. FIG. 5 (a) shows the result of observation of the microstructure of an alloy target bonded at 800 ° C. by an electron microscope.

Manufacture of Alloy Target Using Amorphous Alloy Powder or Nanocrystalline Alloy Powder

Table 5 shows an alloy target prepared by preparing an alloy having the same composition (Zr _63.9 Al ₁₀ Cu _26.1 ) as that of Example 1 in powder form, laminating it in a graphite mold, and pressurizing and sintering with an electrification pressure sintering apparatus. And hardness and crack occurrence according to the results.

At this time, the alloy powders were prepared by atomization method. Specifically, the alloying buttons were prepared by dissolving alloy by the arc melting method in accordance with the composition ratio of Zr, Al and Cu, and the alloy buttons were reused by high frequency After the melt, the molten alloy was sprayed with argon gas. The alloy powder thus prepared exhibited an amorphous phase and the X-ray diffraction results of the alloy powder are shown in FIG. 6 (a).

The amorphous alloy powder thus prepared was sintered in a graphite mold to produce an alloy target, or the amorphous alloy powder thus prepared was annealed at 600 ° C in a high-vacuum furnace to produce a nanocrystalline alloy powder, which was then sintered to be a target . FIG. 6 (b) shows the results of X-ray diffraction after annealing the amorphous alloy powder.

[Table 5]

In the case of the alloy target prepared by sintering the amorphous alloy powder, cracks were not generated at 700 ° C and 800 ° C, and in the case of the alloy target obtained by sintering the nanocrystalline alloy powder, Cracks did not occur. As a result of observation with an electron microscope, all of the alloy targets without cracks exhibited a crystalline structure in which crystal grains of 1 mu m or less were uniformly distributed. FIGS. 5 (b) and 5 (c) show electron micrographs of the microstructure of an alloy target obtained by sintering amorphous alloy powder and nanocrystalline alloy powder at 800 ° C., respectively.

Manufacture of alloy targets using amorphous alloy ribbon

In Table 6, amorphous alloys having the same composition (Zr _63.9 Al ₁₀ Cu _26.1 ) as in Experimental Example 1 were prepared in the form of a ribbon, a plurality of alloy ribbons were laminated in a graphite mold, and pressed and sintered In one alloy target, the results of observing the hardness and the occurrence of cracks according to the pressing temperature are shown.

[Table 6]

Referring to Table 6, when the sintering temperature was 800 ° C, cracks did not occur, and as a result of observation with an electron microscope, as in the results of the above Examples, (Fig. 1). At this time, the amorphous alloy ribbon was produced by the melt spinning method. Specifically, a molten alloy was produced by an arc melting method in accordance with the composition ratio of Zr, Al and Cu, and then the alloy was cast on a copper roll having a diameter of 600 mm, The molten metal was injected through a nozzle and rapidly solidified. At this time, the thickness of the amorphous alloy ribbon was 70 mu m.

The process for producing a sputtering target using an amorphous foil has the following advantageous advantages over the process for producing a sputtering target by using the above amorphous alloy rod or amorphous powder.

First, amorphous ribbons have i) relatively low sintering and bonding properties due to a low oxygen content, and ii) amorphous powders have an initial filling rate of about 60%, whereas amorphous foils have an initial filling rate of about 85% or more Iii) amorphous powder is not easy to obtain uniformity of thickness in a large-area target, whereas amorphous foil has an advantageous effect that the thickness uniformity after sintering is comparatively excellent even in a large area have.

Referring to FIGS. 7 and 8, it was confirmed that no cracking was observed in the crack generation test for the amorphous foil sintered body having the composition disclosed in some embodiments of the present invention according to Table 3, and the microstructure was observed with an electron microscope As a result of the observation, it was confirmed that crystal grains having a grain size of 1 탆 or less had a crystalline structure uniformly distributed.

Referring to FIG. 9, X-ray diffraction analysis of an amorphous foil having the composition disclosed in some embodiments of the present invention according to Table 3 confirmed that broad peaks typically observed in the amorphous phase were observed.

10A is a view illustrating a concept of implementing a crystalline alloy by applying heat treatment to an amorphous alloy and / or a nanocrystalline alloy in a manufacturing method according to an embodiment of the present invention, and FIG. 10B is a cross- The microstructure of the alloy is observed with an electron microscope.

First, referring to FIG. 10A, a sintering process and / or a heat treatment process of an amorphous alloy or a nanocrystalline alloy includes preparing a plurality of amorphous alloys or nanocrystalline alloys containing a metal element having amorphous forming ability; The temperature of the amorphous alloy or the nanocrystalline alloy in the temperature range of the glass transition temperature (Tg) of the amorphous alloy or the nanocrystalline alloy is not more than the crystallization start temperature (Tx) (that is, the temperature range of the supercooled liquid phase region A first heat treatment step (1 & cir &) for maintaining a constant temperature for a predetermined time under a constant pressure, for example, a pressure of several tens MPa to several hundred MPa; And the plurality of amorphous alloys or nanocrystalline alloys are heated at a temperature ranging from 0.7 to 0.9 times the melting temperature (Tm) of the amorphous alloy or the nanocrystalline alloy under a constant pressure, for example, at a pressure of tens of MPa to several hundred MPa , And a second heat treatment step (4 & cir &) for maintaining a constant temperature for a predetermined time.

According to one embodiment of the present invention, the sintering and / or heat treatment is carried out at very high pressures such as 600 MPa, as in the prior art, under the pressure of tens of MPa to several hundred MPa, Similarly, since sintering and / or heat treatment can be performed under a pressure of 20 MPa, there is an advantageous effect of not using high-pressure equipment. The present inventors have found that sintering and / or heat treatment is possible even when the first heat treatment step and / or the second heat treatment step are performed under a pressure ranging from 10 MPa to 50 MPa.

The first heat treatment step (1) includes controlling the porosity of the amorphous alloy or the nanocrystalline alloy to 1% or less. Wherein the second heat treatment step (④ zone) includes a step in which a plurality of the amorphous layer-to-layer interfaces of the plurality of amorphous alloys or the nanocrystalline alloy are controlled to have a porosity of 0.1% or less, Crystallized so that the amorphous alloy or the nanocrystalline alloy has an average grain size in the range of 0.1 mu m to 5 mu m.

Meanwhile, the sintering and / or heat treatment of the amorphous alloy or the nanocrystalline alloy may include heating the plurality of amorphous alloys or the nanocrystalline alloy between the first heat treatment step and the second heat treatment step (zone 2, zone 3); . The first heating temperature zone (2) includes a temperature range immediately above the crystallization starting temperature (Tx) of the amorphous alloy or the nanocrystalline alloy. The second heating temperature zone (3) includes an amorphous alloy or a nanocrystalline alloy Is carried out in a temperature range of 0.6 times or less of the melting temperature (Tm).

In summary, the sintering and / or heat treatment of the amorphous alloy or the nanocrystalline alloy described above can be carried out in the temperature range of 0.7 _Tm or more and 0.9 _Tm or less ( _Tm is the melting temperature of the amorphous alloy) Lt; RTI ID = 0.0 > shrinkage < / RTI > By the primary shrinkage, the amorphous state of the sintered body is realized to be 1% or less, and the crystalline state is realized in which the porosity of the sintered body is 0.1% or less due to the secondary shrinkage. The multistage sintering and / or heat treatment process can be applied not only to the amorphous foil described above but also to amorphous solid (amorphous powder, nanocrystalline powder, amorphous rod, amorphous foil) having any arbitrary shape.

According to the present invention, the amorphous alloy can be heat-treated at a relatively low cost, or the plurality of amorphous alloys can be heat-treated at the same time as the sintering / bonding, and the thermal / mechanical stability can be greatly improved.

Meanwhile, the annealing method of the amorphous alloy according to one embodiment of the present invention is not limited to the specific composition of the amorphous alloy, and may be applied to an amorphous alloy having an arbitrary composition.

Of course, the amorphous alloy or the nanocrystalline alloy having various compositions as described above can be subjected to the heat treatment so as to undergo such two-step shrinkage. For example, the amorphous alloy or the nanocrystalline alloy may contain 67 atom% to 78 atom% of Zr, 4 atom% to 13 atom% of at least one selected from Al and Co, and at least 15 atoms selected from Cu and Ni % To 24 atomic%. As another example, the amorphous alloy or the nanocrystalline alloy may be composed of 5 atom% to 20 atom% of Al, 15 atom% to 40 atom% of at least one selected from Cu and Ni, and the balance Zr. As another example, the amorphous alloy or the nanocrystalline alloy may contain Al in an amount of 5 to 20 atomic%, at least one of Cu and Ni in 15 to 40 atomic%, Cr, Mo, Si, Nb, The sum of at least one selected from Bi, Zn, V, Hf, Ag, Ti, and Fe is 8 atomic% or less (more than 0) and the balance is Zr. Further details regarding the composition of the amorphous alloy or the nanocrystalline alloy can be found in the patent application Nos. 10-2011-0129888 and 10-2013-0065244 already filed by the present inventors.

Referring to FIG. 10B, a plurality of amorphous alloys can be sintered in the superplastic section through the first heat treatment step (region (1)) to achieve a sintered density of 99% or more. However, the cohesive force due to mutual diffusion between the foil and the powder particles may be deteriorated. Generally, a high load of 700 MPa or more is required in order to secure sintering and bonding force in the superplastic section by using amorphous powder, resulting in a disadvantage that the manufacturing cost is greatly increased. The inventors of the present invention have found that by introducing a two-step heat treatment process of the first heat treatment step (the first zone) and the second heat treatment step (the fourth zone), crystal grains control technology is obtained through the superplasticity and crystallization behavior of the amorphous alloy, There is provided a process for producing a crystalline alloy having heat resistance. On the other hand, cracks occurred in the alloys after passing through the first heating step (the zone 2) and the second heating step (the third zone), which are the middle stages of the heat treatment process, due to the mutual diffusion between the amorphous alloys in powder or foil form It is understood that the bonding force is still low.

Sputtering Properties of Crystalline Alloy Targets, Amorphous Alloy Targets and Cast Alloy Targets

FIG. 11 shows the results of observing the surface of a crystalline alloy target (Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 ) prepared by sintering amorphous alloy powder at 800 ° C. in an actual sputtering apparatus and applying 300 W DC plasma power Is shown. Fig. 12 (a) shows the microstructure of the pre-sputtering alloy, and Fig. 12 (b) shows the result of observing the surface of the target after sputtering.

Referring to FIGS. 11, 12A and 12B, it can be seen that the crystalline alloy target has a very smooth surface even after sputtering, and a large change in alloy structure is not observed before and after sputtering . From this, it can be seen that the crystalline alloy target according to the embodiment of the present invention exhibits excellent thermal / mechanical stability that does not show changes in alloy structure even when the temperature is raised during sputtering.

On the other hand, FIG. 13 (a) shows a case where sputtering is carried out under the same conditions using an amorphous alloy target obtained by sintering an amorphous alloy powder of the same composition (Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 ) FIG. 13 (b) shows the result of observing the fracture plane with an electron microscope.

13 (a) and 13 (b), it can be seen that the amorphous alloy target may be broken during the sputtering process. When the aspect of the fracture surface is observed, the surface of the amorphous alloy target shows a flat brittle fracture appearance . From this, it can be seen that the fracture path was broken by the fracture path passing through the inside of the particle, not at the interface of the powder particle.

14A and 14B show X-ray diffraction patterns of an amorphous alloy target before and after sputtering, and it can be seen from the X-ray diffraction results that the amorphous phase before sputtering partially crystallized during the sputtering process.

15A and 15B show a photograph of the periphery of the indenter after the crack generation test (vertical load: 1 kgf) of the alloy target before and after the sputtering of the target having an amorphous phase by an electron microscope. In the case of the amorphous alloy target, the brittleness due to the precipitation of the nanocrystalline during the sputtering process is increased, and thus cracks are generated in the crack generation test as shown in FIG. 15 (b).

From this, it can be seen that the amorphous alloy target may have local thermal crystallization due to the poor thermal stability due to the temperature rise during sputtering, and the brittleness of the target may be increased by the local crystallization to cause destruction of the target during the sputtering process Can be confirmed.

16 shows the result of observing the surface of an alloy target prepared by a general casting method with the same composition (Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 ) as an actual comparative example in a case where a sputtering apparatus is actually mounted and a 300 W DC plasma power source is applied Respectively. Fig. 17 (a) shows the microstructure of the sputtering alloy, and Fig. 17 (b) shows the result of observing the surface of the target after sputtering.

16 and 17 (a) and 17 (b), it can be seen that the sputtered surface of the cast alloyed target is uneven and very rough compared to the crystalline alloy target of the present invention (see FIG. 11) This is considered to be because the microstructure of the cast alloyed target is coarse and non-uniform and the sputtering on the surface thereof occurs unevenly.

As shown in FIG. 17 (a), the cast alloyed alloy target shows uneven microstructure in which coarse phases of various sizes and shapes having different compositions such as main phase structure or dendritic phase phase in the solidification process are mixed. The sputtered surface due to the nonuniformity of the microstructure is also formed non-uniformly as shown in Fig. 17 (b).

The unevenness of the composition of the thin film produced by the sputtering may be poor due to the unevenness of the casting alloyed target. Also, there may be a marked difference between the composition of the target and the composition of the thin film formed through sputtering, and the thin film characteristics such as the composition of the thin film may be adversely affected as the sputtering proceeds. Furthermore, particles may be generated from the target during sputtering, causing contamination of the sputtering chamber.

In addition, when casting a multi-element alloy, various intermetallic compounds having high brittleness can be formed, so that a brittle fracture of the target may occur during the process of casting or casting the target. Illustratively, FIG. 18 shows that a 3-inch grade cast alloy material target having a composition of Zr _63.9 Al ₁₀ Cu _26.1 is cracked during natural solidification after arc melting in a water-cooled copper hose and is broken.

On the other hand, the crystalline alloy target according to the present invention has a microstructure in which fine grains are uniformly distributed, and thereby, the uniformity of sputtering occurs on the target surface, so that the composition of the thin film is uniform and the composition of the thin film approximates to the target composition Can be obtained. Unlike the casting alloyed target, the generation of particles can be remarkably improved.

Table 7 shows the compositions of thin films prepared by sputtering a crystalline alloy target with a Zr _62.5 Al ₁₀ Mo ₅ Cu _22.5 composition and a cast alloy alloy target. At this time, a DC voltage of 200 W was applied to the sputtering target, and the chamber pressure was 5 mTorr. The thickness of the deposited thin film was 10 μm and the composition was analyzed by EPMA.

Referring to Table 7, it can be seen that the composition of the thin film is closer to the target composition than that of the cast target.

 [Table 7]

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 (13)

Preparing a plurality of amorphous alloys or nanocrystalline alloys containing metal elements having amorphous forming ability;
A first heat treatment step of keeping the plurality of amorphous alloys or nanocrystalline alloys at a constant temperature for a predetermined time in a temperature range of a glass transition temperature (Tg) of the amorphous alloy or a nanocrystalline alloy to a crystallization start temperature (Tx) or lower; And
A second heat treatment step of keeping the plurality of amorphous alloys or nanocrystalline alloys at a constant temperature in a range of a crystallization starting temperature (Tx) of the amorphous alloy or a nanocrystalline alloy to a melting temperature (Tm) or less;
≪ / RTI > The method according to claim 1,
A second heat treatment step of keeping the plurality of amorphous alloys or nanocrystalline alloys at a constant temperature for a predetermined time in a temperature range not lower than a crystallization start temperature (Tx) of the amorphous alloy or a nanocrystalline alloy at a melting temperature (Tm)
And a heat treatment step of keeping the plurality of amorphous alloys or nanocrystalline alloys at a constant temperature for a predetermined time in a temperature range of 0.7 to 0.9 times the melting temperature (Tm) of the amorphous alloy or the nanocrystalline alloy, ≪ / RTI >

The method according to claim 1,
Wherein the first heat treatment step or the second heat treatment step is performed under a pressure ranging from 10 MPa to 50 MPa. The method according to claim 1,
And heating the plurality of amorphous alloys or nanocrystalline alloys between the first heat treatment step and the second heat treatment step. The method according to claim 1,
Wherein the first heat treatment step comprises controlling the porosity between the plurality of amorphous alloys or the nanocrystalline alloy to 1% or less. The method according to claim 1,
Wherein the second heat treatment step comprises controlling the porosity between a plurality of the amorphous alloys or the nanocrystalline alloy to 0.1% or less. The method according to claim 1,
Wherein the second annealing step comprises crystallizing the plurality of amorphous alloys or nanocrystalline alloys such that the average grain size of the amorphous alloy or nanocrystalline alloy is in the range of 0.1 mu m to 5 mu m. The method according to claim 1,
Wherein the amorphous alloy or the nanocrystalline alloy has at least one shape selected from the group consisting of a foil, a powder, a block, and a rod. The method according to claim 1,
Wherein the amorphous alloy or the nano-crystalline alloy contains at least 67 atom% to 78 atom% of Zr, 4 at% to 13 at% of at least one selected from Al and Co, and at least 15 atom% to 24 atoms %, ≪ / RTI > The method according to claim 1,
Wherein 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, and the balance Zr. The method according to claim 1,
Wherein the amorphous alloy or the nanocrystalline alloy contains Al in an amount of 5 to 20 atomic%, at least one of Cu and Ni in an amount of 15 to 40 atomic%, Cr, Mo, Si, Nb, Co, Sn, In, , At least one selected from among Hf, Ag, Ti and Fe is not more than 8 atomic% (more than 0), and the remainder is Zr. Preparing an amorphous alloy including a metal element having an amorphous forming ability;
A first heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time in a temperature range not lower than a glass transition temperature (Tg) of the amorphous alloy and a crystallization start temperature (Tx); And
A second heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time in a temperature range from a crystallization start temperature (Tx) to a melting temperature (Tm) of the amorphous alloy;
Of the amorphous alloy. 13. The method of claim 12,
The second heat treatment step of keeping the amorphous alloy at a constant temperature for a predetermined time in a temperature range from a crystallization starting temperature (Tx) of the amorphous alloy to a melting temperature (Tm) or lower of the amorphous alloy may be performed by heating the amorphous alloy to a melting temperature Tm) at a constant temperature for a predetermined time in a temperature range of 0.7 to 0.9 times the temperature of the amorphous alloy.

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