TWI540042B - Metallic glass-ceramics multilayer film and method for fabricating the same - Google Patents

Description

Metal glass-ceramic composite multilayer film and manufacturing method thereof

The invention relates to a metal glass-ceramic composite multilayer film and a manufacturing method thereof, in particular to a metal glass-ceramic composite multilayer film with excellent mechanical properties.

A metallic glass, also known as an amorphous alloy, refers to the arrangement of atoms in a metal that lacks long-range order, but is arranged in a short-range order or even a disorder. In 1960, W.Klement (Jr.), Willens and Duwez first observed the world's first metallic glass material Au ₇₅ Si ₂₅ alloy. As the research on metallic glass increases, the excellent atomic arrangement of metallic glass imparts excellent engineering properties such as thermal stability, good corrosion resistance, high tensile strength and high elastic energy, so The improved development of metallic glass materials is also continuing and is expected to expand its commercial use. In recent years, the composition and content of the elements in the metallic glass film have become wider, and there is an opportunity to mass production in a large area, making the research of metallic glass more popular.

However, just like other conventional metal glass blocks, metal The lack of ductility of the glass film in the absence of metallic materials leads to poor fracture toughness of the metallic glass, which would limit the applicability of the metallic glass. In order to solve the above problems, the application field of metallic glass has been expanded, and many research teams have attempted to embed a metal thin film, such as copper or nickel, into a metallic glass film to form a metallic glass-metal multilayer composite film. Compared with conventional metal glass, the metal glass-metal multilayer composite film has improved in mechanical properties such as hardness or strain tolerance, but there is still much room for improvement.

As for the development of multilayer nanofilm technology, it has been quite a long time. Historically, in the prior art, physical vapor deposition, chemical vapor deposition, electroplating, or chemical methods have been used to coat several to hundreds of layers of different materials on the surface of a material, of which a single layer of film The thickness is approximately several nanometers to hundreds of nanometers, and the total thickness of the multilayer film can range from several hundred nanometers to several micrometers. The total grain boundary of the multilayer nano film is very large, and when one film is a crystalline material and the other layer is an amorphous material, since the amorphous material can effectively limit the crystal growth of the crystalline material, the crystal is made The effect of grain refinement and strengthening is more remarkable.

Adjust the multilayer nano film material according to the desired effect Composition, which can make mechanical properties (such as strength, toughness, and wear resistance), electrical properties, optical properties (such as light absorption, linearity and nonlinearity of light), and magnetic properties (such as super) of multilayer nanofilm materials. The paramagnetic effect, the gas sensing property, and the like can be adjusted in accordance with the demand, and can be flexibly applied to various fields. Applications of multilayer nanofilms include semiconductor industry, optoelectronics, magnetics, X-ray mirrors, infrared laser industry, and wear-resistant, high-strength protection Coating, machining and other purposes.

The main object of the present invention is to provide a metal glass-ceramic composite multilayer film. In particular, the present invention firstly inserts a ceramic material into a metal glass film to form a metal glass-ceramic composite multilayer film, and confirms the metal glass-ceramic composite of the present invention. The multilayer film has excellent mechanical properties compared to conventional metal glass. The present invention also provides a method of producing a metal glass-ceramic composite multilayer film.

To achieve the above object, the present invention provides a metallic glass-ceramic composite multilayer film comprising a plurality of metallic glass layers and a plurality of ceramic layers, wherein the ceramic layers are sandwiched between adjacent metallic glass layers.

Each of the above metallic glass layers covers all of the amorphizable alloy systems without particular limitation. Specifically, each of the metallic glass layers is independently an amorphous alloy, and includes one or more selected from the group consisting of Zr, Cu, Ni, Al, and Si, wherein the content of Zr is 30 at .%~65 at.%, Cu content is 30 at.%~65 at.%, Ni content is 0 at.%~25 at.%, and Al content is 0 at.%~25 at.%, The content of Si is 0 at.%~25 at.% (in the present specification, the sum of all elements is taken as the atomic percentage 100 at.% (at.% is the abbreviation of Atom%, which is an abbreviation of atomic percentage). For example, the amorphous alloy in this case may be Zr _a Cu _b Ni _c Al _d Si _{100-(a+b+c+d)} , wherein a is 30~65, b is 30~65, c is 0~ 25, d is 0~25.

Further, the ceramic layer in the metallic glass-ceramic composite multilayer film of the present invention is not particularly limited, and materials of different structures and compositions are included, and in the present invention, a ceramic layer of high hardness such as carbide or a hard ceramic layer formed of a diboride such as TiC _x , NbC _x , ZrC _x , WC _x , SiC _x , NbB _2y , TaB _2z , or TiB _2z , and wherein 0.49<x<1.2, 1.78<2y<3.16, 1.84 <2z<2.92.

In the metal glass-ceramic composite multilayer film of the present invention, The thickness of the metallic glass layer and the ceramic layer are independently 5 to 500 nm, preferably 15 to 100 nm, and among them, 20 nm is optimal. Further, in the metallic glass-ceramic composite multilayer film of the present invention, the metallic glass layer and the ceramic layer may have the same or different thicknesses.

In addition, the present invention also provides a metal glass-ceramic composite A method of manufacturing a multilayer film comprising: (a) providing a substrate; (b) forming a metallic glass layer on a substrate; (c) forming a ceramic layer on the metallic glass layer; and (d) repeating the step (b) And (c) to form a multilayer film.

The above substrate which can be used in the present invention is not particularly limited, and is In the invention, for example, a crucible wafer, stainless steel, tungsten carbide, or sapphire can be used as the substrate.

As for the metallic glass layer, as described above, all alloy systems capable of amorphizing are covered without particular limitation. Each of the metallic glass layers is independently an amorphous alloy, and includes one or more selected from the group consisting of Zr, Cu, Ni, Al, and Si, wherein the content of Zr is 30 at.% to 65. The content of at.% and Cu is 30 at.%~65 at.%, the content of Ni is 0 at.%~25 at.%, the content of Al is 0 at.%~25 at.%, and the content of Si is 0 at.%~25 at.% (In this specification, the sum of all elements is taken as the atomic percentage of 100 at.% (at.% is the abbreviation of Atom%, which is an abbreviation of atomic percentage). Specifically, for example, The amorphous alloy of the present invention may be Zr _a Cu _b Ni _c Al _d Si _{100-(a+b+c+d)} , wherein a is 30-65, b is 30-65, c is 0-25, d is 0~25.

Further, the ceramic layer in the method for producing a metallic glass-ceramic composite multilayer film of the present invention is also not particularly limited, and materials of different structures and compositions are included, and in the present invention, a ceramic layer of high hardness is preferable, for example. The carbide or diboride is a hard ceramic layer formed of, for example, TiC _x , NbC _x , ZrC _x , WC _x , SiC _x , NbB _2y , TaB _2z , or TiB _2z , and wherein 0.49<x<1.2, 1.78<2y <3.16, 1.84<2z<2.92.

The invention of the metal glass-ceramic composite multilayer film of the invention In the manufacturing method, the metal glass layer and the ceramic layer are formed to have a thickness of 5 to 500 nm, preferably 15 to 100 nm, respectively, and wherein 20 nm is optimal.

The invention relates to the metal glass-ceramic composite multilayer film of the invention In the method, the method for forming the steps (b) and (c) is not particularly limited, but is preferably produced by magnetron sputtering, and steps (b) and (c) are repeated to form a multilayer film. .

In the present invention, the metal obtained by the above method and composition The glass-ceramic composite multilayer film has the following advantages: first, mechanical properties such as hardness, strength and film adhesion of the metallic glass-ceramic composite multilayer film of the present invention compared to the conventional metallic glass film and the metallic glass-metal multilayer composite film Both of them are significantly improved. Secondly, by appropriately controlling the stacking period of the metallic glass layer and the ceramic layer, the breaking behavior is not easily transmitted to the inside of the material, so the fracture toughness of the metallic glass-ceramic composite multilayer film of the present invention can be significantly improved. Even surpassing the general ductile material; thirdly, the range of optional single-layer materials of the present invention covers a wide range, so the metal glass-ceramic of the present invention The ceramic composite multilayer film can be produced in various combinations according to requirements, and accordingly, the metal glass-ceramic composite multilayer film of the invention improves the mechanical properties of the conventional metal glass and obtains excellent effects, thereby expanding the metallic glass. Application area.

1‧‧‧Metal glass-ceramic composite multilayer film

11‧‧‧metal glass layer

12‧‧‧Ceramic layer

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of a metallic glass-ceramic composite multilayer film of the present invention.

Figure 2 is a photograph of the metallic glass-ceramic composite multilayer film of the present invention under a scanning electron microscope.

3 is a graph showing the hardness test results of the metallic glass-ceramic composite multilayer film of Examples 1 to 4 of the present invention and the metallic glass single-layer film of Comparative Example 1.

4 is a graph showing the adhesion test results of the metallic glass-ceramic composite multilayer film of Examples 1 to 4 of the present invention and the metallic glass single-layer film of Comparative Example 1.

Preferred embodiments of the invention are described in detail below. Those skilled in the art can readily understand the objects, advantages, and advantages of the present invention through the disclosure of the present disclosure. In addition, the present invention may be embodied or applied by other different embodiments without departing from the spirit and scope of the invention.

As shown in FIG. 1, the metallic glass-ceramic composite multilayer film 1 comprises a plurality of metallic glass layers 11 and a plurality of ceramic layers 12, wherein the ceramic layers 12 are sandwiched between adjacent metallic glass layers 11. 2 is a metal glass-ceramic composite multilayer film of the present invention under a scanning electron microscope a picture in which the darker color is a crystalline ceramic layer; the lighter one is an amorphous metallic glass layer, and hereinafter, the metallic glass-ceramic composite multilayer film of the present invention will be shown by way of specific examples and for its mechanical properties (hardness, Adhesion) was tested.

Example 1

At normal temperature, the ambient vacuum value is first drawn between 2x10 ^-7 and 5x10 ^-6 torr, and then multilayer film stacking is performed. First, argon gas was introduced as a sputtering gas, and a mass flow controller was used to control the mass flow rate of argon gas between 5 and 50 sccm. A germanium wafer, stainless steel, tungsten carbide, or sapphire may be used as the substrate. However, in the present embodiment, a germanium wafer is used as a substrate, and then argon gas as a sputtering gas is decomposed into a cation by a low temperature plasma, and bombarded. The surface of the amorphous metal glass target forms an amorphous metallic glass layer having a thickness of 15 nm. The above-mentioned amorphous alloy system includes one or more groups selected from the group consisting of Zr, Cu, Ni, Al, and Si, and the total of all the elements is calculated as an atomic percentage of 100 at.%, wherein the content of Zr is 30 at. %~65 at.%, Cu content is 30 at.%~65 at.%, Ni content is 0 at.%~25 at.%, Al content is 0 at.%~25 at.%, Si The content is 0 at.%~25 at.% (at.% is the abbreviation of Atom%, which is an abbreviation of atomic percentage). Specifically, for example, the amorphous alloy of the present invention may be Zr _a Cu _b Ni _c Al _d Si _{100-(a+b+c+d)} , wherein a is 30-65, b is 30-65, c-system 0 to 25 and d are 0 to 25, and in the present embodiment, Zr ₅₃ Cu ₃₀ Ni ₈ Al ₈ Si _{1 is} used as the amorphous metallic glass layer.

Next, TiB ₂ diboride ceramic was used as a target. The metal atoms on the target leave the surface of the target due to plasma bombardment and are sprayed onto the first metallic glass layer to form a first hard ceramic layer having a thickness of 15 nm. Then, a second metallic glass layer having a thickness of 15 nm is deposited on the hard ceramic layer as described above, and the metal glass-ceramic composite multilayer film having a total thickness of one micron is formed by continuously repeating the above steps.

Example 2

In the embodiment 2, except that the metallic glass layer and the hard ceramic layer are each stacked at a thickness of 20 nm to form a metallic glass-ceramic composite multilayer film having a total thickness of one micrometer, the metallic glass layer and the hard ceramic layer. Both were deposited by magnetron sputtering as in Example 1.

Example 3

In the third embodiment, except that the metallic glass layer and the hard ceramic layer are each stacked at a thickness of 50 nm to form a metallic glass-ceramic composite multilayer film having a total thickness of one micrometer, the metallic glass layer and the hard ceramic layer. Both were deposited by magnetron sputtering as in Example 1.

Example 4

In the third embodiment, except that the metallic glass layer and the hard ceramic layer are each stacked at a thickness of 100 nm to form a metallic glass-ceramic composite multilayer film having a total thickness of one micrometer, the metallic glass layer and the hard ceramic layer. Both were deposited by magnetron sputtering as in Example 1.

Comparative example 1

In Comparative Example 1, except that the hard ceramic layer was not formed on the first metallic glass layer, the first metallic glass layer was prepared in the same manner as in Example 1 to form a ZrCuNiAl single-layer film.

Experimental Example 1: Hardness performance

The nanoindentation measurement technique is currently the most common tool for measuring the microscopic plasticity and elastic behavior of materials at the nanometer scale. Here is a brief introduction: through the bottom of the pneumatic balance stage, the nano indentation can effectively overcome the external environment interference during the indentation process, and accurately detect the force and displacement during the recording of the indentation. The nano indentation system uses a very small load and a very sharp needle to select the range of the extremely micro-area, and obtains the hardness (H) and the Young's coefficient value (E) by continuous loading and unloading processes. The load is 5 micronewtons (5 mN).

Since the metallic glass-ceramic composite multilayer film of the present invention improves the mechanical properties of the conventional metallic glass film, the hardness performance is one of the test indexes of the mechanical properties. Here, the metal glass-ceramic composite multilayer film (ZrCuNiAl/TiB ₂ multilayer film) obtained in the above Examples 1 to 4, and the metallic glass (ZrCuNiAl single layer film) obtained in Comparative Example 1 were used using a nanoindentation apparatus. Hardness performance was tested.

As shown in FIG. 3, it can be clearly observed that when the hard ceramic layer is placed in the metallic glass layer, and the nano periodic thickness is appropriately controlled (stacking period, if the pushing period is n, it represents the metallic glass-ceramic composite multilayer film of the present invention. (ZrCuNiAl/TiB ₂ multilayer film) was extruded at a thickness of n/n nm, and it was found that the hardness of the metallic glass was greatly improved from the original 4.5 GPa. Among them, it is most desirable to laminate the multilayer film in a manner of individual thicknesses of 20/20 nm, in which case the hardness of the film can be pulled up to about 16 GPa.

Experimental Example 2: Adhesion performance

The metal glass-ceramic composite multilayer film (ZrCuNiAl/TiB ₂ multilayer film) obtained in Examples 1 to 4 and the metal glass (ZrCuNiAl single layer film) obtained in Comparative Example 1 were measured by a nano scratching apparatus to investigate The adhesion of some films. Here, the adhesion test refers to the use of a lateral force to act on the film to produce scratches, and to observe how much force the film will automatically peel off from the substrate.

As shown in FIG. 4, the adhesion of the film is also improved by the placement of the hard ceramic and appropriately controlling the thickness of the nanometer cycle. For example, when the metallic glass-ceramic composite multilayer film (ZrCuNiAl/TiB ₂ multilayer film) of the present invention is stacked with a thickness of 20/20 nm, the adhesion is about 650 mN, and Comparative Example 1 The adhesion of the obtained metallic glass (ZrCuNiAl single-layer film) was more than twice as high as that of 300 mN.

It is apparent from the foregoing experimental examples that the metallic glass-ceramic composite multilayer film of the present invention exhibits improved mechanical properties such as hardness and adhesion as compared with a conventional metallic glass which does not include a ceramic layer. In particular, when the stacking period of the metallic glass layer and the ceramic layer is appropriately controlled, for example, when the individual thicknesses are 20/20 nm, the hardness or the adhesion is remarkably improved.

The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.

1‧‧‧Metal glass-ceramic composite multilayer film

11‧‧‧metal glass layer

12‧‧‧Ceramic layer

Claims (13)

A metal glass-ceramic composite multilayer film comprising: a plurality of metal glass layers; and a plurality of ceramic layers sandwiched between adjacent metal glass layers, wherein each of the metal glass layers is independently a non- a crystalline alloy comprising one or more selected from the group consisting of Zr, Cu, Ni, Al, and Si, wherein the content of Zr is 30 at.% to 65 at.%, and the content of Cu is 30 at.% to 65 at. The content of % and Ni is 0at.%~25at.%, the content of Al is 0at.%~25at.%, and the content of Si is 0at.%~25at.%. The metallic glass/ceramic composite multilayer film according to claim 1, wherein the ceramic layer is composed of TiC _x , NbC _x , ZrC _x , WC _x , SiC _x , NbB _2y , TaB _2z , or TiB _2z Formed, and 0.49 < x < 1.2, 1.78 < 2y < 3.16, 1.84 < 2z < 2.92. The metallic glass/ceramic composite multilayer film according to claim 1, wherein the metallic glass layer has a thickness of 5 to 500 nm. The metallic glass/ceramic composite multilayer film according to claim 1, wherein the ceramic layer has a thickness of 5 to 500 nm. The metallic glass/ceramic composite multilayer film of claim 1, wherein the metallic glass layer and the ceramic layer may have the same or different thicknesses. A method for manufacturing a metal glass-ceramic composite multilayer film, comprising: (a) providing a substrate; (b) forming a metallic glass layer on a substrate; (c) forming a ceramic layer on the metallic glass layer; and (d) repeating steps (b), (c) to form a multilayer film. The method for manufacturing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the substrate is a wafer, a stainless steel, a tungsten carbide, or a sapphire. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein each of the metallic glass layers is independently an amorphous alloy, and one or more selected from the group consisting of Zr, Cu, A group consisting of Ni, Al, and Si, wherein the content of Zr is 30 at.% to 65 at.%, the content of Cu is 30 at.% to 65 at.%, and the content of Ni is 0 at.% to 25 at.%, Al. The content is 0at.%~25at.%, and the content of Si is 0at.%~25at.%. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the ceramic layer is composed of TiC _x , NbC _x , ZrC _x , WC _x , SiC _x , NbB _2y , TaB _2z , Or TiB _2z is formed, and 0.49 < x < 1.2, 1.78 < 2y < 3.16, 1.84 < 2z < 2.92. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the metallic glass layer has a thickness of 5 to 500 nm. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the ceramic layer has a thickness of 5 to 500 nm. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the metallic glass layer and the ceramic layer may have the same or different thicknesses. The method for producing a metallic glass/ceramic composite multilayer film according to claim 6, wherein the steps (b) and (c) are obtained by a magnetron sputtering method.