Preparation method of amorphous superlattice alloys

Abstract: Preparation method of amorphous superlattice alloys consisting of lamellae based on periodic change in the composition by continuous conventional sputtering during periodic change in the positions of substrates relative to a target or targets.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a preparation method of amorphous superlattice alloys applicable to a variety for fields such as materials with specific magnetic and chemical properties. 2. Description of the Prior Art The formation of atomic lamellar structure in which each layer consists of different pure elements has been known, and the method for preparation of amorphous alloys by sputtering is also known. However, a method of forming an amorphous superlattice based on the repetition of two amorphous layers of different compositions is not known. The method of forming a superlattice by alternating sputtering of two kinds of metals or alloys is well known. Instead of alternating sputtering of two kinds of metals or alloys, preparation of the amorphous superlattice alloys by continuous conventional sputtering has not been performed. However, there has been a strong demand for development of a new method to form new superlattice alloys, that is, preparation of the amorphous superlattice alloys by continuous conventional sputtering. SUMMARY OF THE INVENTION It is an objective of the present invention to provide a continuous method for production of an amorphous superlattice alloy consisting of lamellae based on periodic change in the composition by sputtering. The objective of the invention is achieved by the present invention: (1) A method of preparation by sputtering of an amorphous suberlattice alloy consisting of lamellae based on period changes in the composition, said method comprising the steps of providing a target consisting of metal or alloy pieces placed on or embedded in an erosion region of another metal or alloy disk, continuously sputtering the target onto substrates, said substrates being located in a plane extending parallel to a target face, and periodically changing the position of the substrates relative to the target by rotating the substrates in said plane around a first axis extending normal to the center of the substrates and orbiting the substrates in said plane around a second axis parallel to the first axis and spaced therefrom, so that, when the substrates come to the position right above the target by virtue of the revolution around the second axis, the first axis of the substrates is on a line extending normal to the center of the face of the target. (2.) A method of preparation by sputtering of an amorphous superlattice alloy consisting of lamellae based on a periodic change in the composition, said method comprising the steps of providing multiple targets, each consisting of metal or metal alloy pieces placed on or embedded in erosion regions of another metal or alloy disk, said targets being obliquely inclined towards one another in a sputtering apparatus, normals from the centers of each of said targets intersecting at a point, continuously sputtering the targets onto the substrates, said substrates being located in one plane, and periodically changing the position of the substrates relative to the multiple targets by rotating the substrates in said plane on a first axis extending normally to the center of the substrates and also orbiting the substrates in said plane around a second axis extending parallel to the first axis and spaced therefrom, so that, when the substrates come right above the obliquely inclined targets by virtue of their revolution around the second axis, the first axis of the substrates lies on said point of intersection of the normal of each of the targets. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 show examples of apparatuses used in methods of preparing an amorphous superlattice alloy according to the present invention. Fig. 3 shows an example of a target assembly. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention aims to provide a continuous method for production of an amorphous superlattice alloy consisting of a lamellae based on periodic change in the composition by sputtering. It is generally known that an alloy has a crystalline structure in the solid state. However, an alloy having a specific composition becomes amorphous by prevention of the formation of a long-range order structure during solidification through, for example, rapid solidification from the liquid state, sputter deposition or plating under specific conditions; or by destruction of the long-range order structure of the solid alloy through ion implantation which is also effective for supersaturation with necessary elements. The amorphous alloy thus formed is a homogeneous single phase supersaturated solid solution containing sufficient amounts of various alloying elements beneficial in providing specific characteristics, such as high corrosion resistance, high mechanical strength and high toughness. The present inventors carried out a series of researches paying attention to the preparation methods and outstanding properties of amorphous alloys. They found that amorphous alloys consisting of metals having high melting points and metals having low melting points can be prepared by a sputter deposition method which does not require mixing of metallic elements by melting. Furthermore, the present inventors found that an amorphous superlattice alloy consisting of lamellae based on a periodic change in the composition can be prepared by periodically changing the substrate position relative to the target for sputtering. The method of the present invention has been accomplished on the basis of this finding. Sputtering is generally performed by using a sintered or alloyed crystalline target of multiple phases whose average composition is the same as the amorphous alloy to be prepared. Sputtering is also carried out by using a target consisting of a metal sheet of one of the constituents in the amorphous alloy to be prepared and other metal constituents placed on the metal sheet. The present invention was performed by improvements of these methods as follows: As shown in FIG.3, targets 4 (or 5) consist of metal or alloy pieces B (or D) placed on or embedded in the erosion region of another metal or alloy disc A (or C). An example of the apparatus is shown in FIG. 1. The positions of the substrates 2 which are rotated on a first axis 7, which is parallel to a second or central axis 1 relative to a target 3 are periodically changed by orbiting of the substrates 2 around the second axis 1 different from the normal of the center of the target 3 in a sputtering chamber 6. Sputtering by this procedure enables the formation of an amorphous alloy consisting of A (or C) and B (or D) in which the concentrations of A (or C) and B (or D) change periodically. The apparatus shown in FIG. 2 can also be used. For instance a target 4 consists of metals or alloys A and B which constitutes the amorphous alloy, and another target 5 consists of metals or alloys C and D which also constitute the amorphous alloy. These two targets 4 and 5 are installed obliquely in the sputtering chamber 6, in such a way that the intersection of the normals to the centers of these two targets is on the orbit of the center or axis 7 of the substrates 2 revolving around a central axis 1 of the sputtering chamber 6. The positions of the substrates 2 relative to the intersection of the normals to the centers of these two targets 4 and 5 are periodically changed by the rotation and orbiting of the substrates 2. Sputtering by this procedure enables the formation of an amorphous alloy consisting of A, B, C and D in which the concentrations of A, B, C and D change periodically. The average composition of the amorphous alloy can easily be changed by changing, for instance, the area of B placed on A. The invention is now illustrated by the following examples: Example 1 The targets consisted of 4 Ta discs of 20 mm diameter and 1 mm thickness placed symmetrically on an Al disc of 100 mm diameter and 6 mm thickness so as to place the center of Ta discs on a concentric circle of 58 mm diameter on the surface of the Al disc. The sputtering apparatus shown in FIG. 1 was used. Substrates were an Al disc and two glasses which were rotated or orbited with the rate of 6.26 sec/ revolution around the central axis of the sputtering chamber. Sputtering was carried out at the power of 240-200 watts under purified Ar stream of 5 ml/min at a vacuum of 2 x 10⁻⁴ Torr. X-ray diffraction of the sputter deposit thus prepared revealed the formation of an amorphous alloy. Electron probe microanalysis showed that the amorphous alloys consisted of Al-22 at% Ta alloy. After slicing the alloy by a ultra-microtome, the cross section of the alloy was observed by a transmission electron microscope. The electron microscopy revealed that the alloy is an amorphous superlattice alloy consisting of the repetition of 3 nm thick lamellae. Example 2 As shown in Table 1, targets used were composed of different numbers of various discs placed on the same Al disc as described in Example 1. Sputtering was carried out similarly to Example 1. X-ray diffraction of the sputter deposits thus prepared revealed the formation of amorphous alloys. The number of the discs placed on the Al disc, the cycle of revolution of the substrates, the average composition of the amorphous superlattice alloy formed and the thickness of each lamella are shown in Table 1. Composition and Periodicity of Amorphous Superlattice Alloys Metal disc on Al No. of discs on Al Revolution cycle of substrate (Sec/rev.) Average composition of amorphous alloy (at %) Thickness of lamella (nm) Ta 4 12.5 22 5.8 Ta 4 25.0 22 10.6 Ta 6 12.5 38 4.1 Mo 3 12.5 19 7.2 Mo 6 12.5 49 5.5 Nb 4 6.26 20 3.2 Nb 4 12.5 20 6.1 Nb 4 25.0 20 11.3 Nb 7 12.5 58 4.5 W 4 12.5 15 6.5 W 6 12.5 45 5.1 In these two examples, the apparatus shown in FIG. 1 was used. Similar amorphous superlattice alloys are also produced by using the apparatus shown in FIG. 2.

Claims: A method of preparation by sputtering of an amorphous superlattice alloy consisting of lamellae based on periodic changes in the composition, said method comprising the steps of providing a target (3) consisting of metal or alloy pieces placed on or embedded in an erosion region of another metal or alloy disk, continuously sputtering the target onto substrates, said substrates (2) being located in a plane extending parallel to a target face, and periodically changing the position of the substrates relative to the target by rotating the substrates in said plane around a first axis (7) extending normal to the center of the substrates (2) and orbiting the substrates in said plane around a second axis (1) parallel to the first axis and spaced therefrom, so that, when the substrates come to the position right above the target by virtue of the revolution around the second axis (1), the first axis (7) of the substrates (2) is on a line extending normal to the center of the face of the target. A method of preparation by sputtering of an amorphous superlattice alloy consisting of lamellae based on a periodic change in the composition, said method comprising the steps of providing multiple targets (4, 5), each consisting of metal or metal alloy pieces placed on or embedded in erosion regions of another metal or alloy disk, said targets being obliquely inclined towards one another in a sputtering apparatus, normals from the centers of each of said targets intersecting at a point, continuously sputtering the targets onto substrates (2), said substrates (2) being located in one plane, and periodically changing the position of the substrates relative to the multiple targets by rotating the substrates in said plane on a first axis (7) extending normally to the center of the substrates and also orbiting the substrates in said plane around a second axis (1) extending parallel to the first axis and spaced therefrom, so that, when the substrates (2) come right above the obliquely inclined targets by virtue of their revolution around the second axis (1), the first axis (7) of the substrates (2) lies on said point of intersection of the normal of each of the targets.

Inventors: ASAMI KATSUHIKO, HASHIMOTO KOJI, KAWASHIMA ASAHI, YOSHIOKA HIDEAKI, ASAMI, KATSUHIKO, HASHIMOTO, KOJI, KAWASHIMA, ASAHI, YOSHIOKA, HIDEAKI
Applicants: HASHIMOTO KOJI, YKK CORP, HASHIMOTO, KOJI, YKK CORPORATION
Application year: 1989
Main classification: C23C14
IPC codes: C23C14