KR100560961B1 - Method of making reaction diffusion-bonded compound materials - Google Patents

Abstract

Disclosed is a method for preparing a compound diffusion reaction bonding structure. According to the present invention, two or more pieces of compound material are prepared to polish some or the entire surface. A thin film of metal, metalorganic or metal compound that can be incorporated or dissolved into the compound material upon thermal treatment on one or more abrasive surfaces to form a thin film of the composition. The heat treatment is performed with the pieces of the compound material facing each other with the surface where the composition thin film is formed to form a directly bonded interface without the presence of the second phase at the bonding interface.

Description

Method of making reaction diffusion-bonded compound materials

1 is a flow chart of a method of manufacturing a compound material reaction diffusion junction structure according to the present invention.

Figure 2a is a photograph of the sapphire reaction diffusion bonding structure bonded using an Al deposition film according to the present invention.

FIG. 2B is an enlarged photograph of a bonding interface in a sapphire reaction diffusion junction structure of FIG. 2A with a scanning electron microscope (SEM).

Figure 2c is a graph measuring the light transmittance of the bonding interface in the sapphire reaction diffusion bonding structure of Figure 2a.

3 is a photograph of a sapphire reaction diffusion bonding structure bonded using Al foil according to the present invention.

4A is a photograph of an alumina polycrystalline reaction diffusion bonding structure bonded using an Al deposition film according to the present invention.

FIG. 4B is an enlarged SEM photograph of the bonding interface of the alumina polycrystalline reaction diffusion bonding structure of FIG. 4A. FIG.

5A is a photograph of a MgO single crystal reaction diffusion junction structure bonded using an Mg deposited film according to the present invention.

FIG. 5B is an enlarged SEM photograph of the bonding interface of the MgO reaction diffusion bonding structure of FIG. 5A. FIG.

Figure 6 is a photograph of a ZnS polycrystalline reaction diffusion bonding structure bonded using a Zn deposited film according to the present invention.

7A is a photograph of a soda-lime glass reactive diffusion bonding structure bonded using an Al deposition film according to the present invention.

7B is an enlarged SEM photograph of the bonding interface of the soda-lime glass reaction diffusion structure of FIG. 7A.

Figure 8 is a cross-sectional SEM photograph of the AlN polycrystalline reaction diffusion bonding structure bonded using an Al deposition film according to the present invention.

9 is an enlarged SEM image of a bonding interface of a Si ₃ N ₄ polycrystalline reaction diffusion bonding structure bonded using a Si deposition film according to the present invention.

FIG. 10 is a cross-sectional SEM photograph of a SiC polycrystalline diffusion bonding structure bonded together using a Si deposited film according to the present invention. FIG.

FIG. 11 is a cross-sectional SEM photograph of a quartz glass reaction diffusion bonding structure bonded using a Si deposited film according to the present invention.

The present invention relates to a method of joining materials, and more particularly to a method of joining materials made of a compound, such as ceramics.

Looking at the manufacturing process of the urea components that are industrially used in various chemical, electronic, optical, or mechanical fields, manufacturing of a structure having a large size and a complicated shape is generally difficult, and various technologies are used. For example, casting, which melts the material, pours it into a mold and cools it to harden, casts the material into a powder form, presses it into a mold having a desired size and shape, and pressurizes or slurry into a mold such as gypsum. Forming process to transform the material of simple shape by using powder forming method, plastic deformation, etc., which is made into powder compact and then made into hard element parts through proper heat treatment. (forming operation), machining (machining) to machine the material to have the desired size and shape, and joining (joining) to connect the materials of simple shapes to each other to form large and complex element parts.

However, materials made of compounds, such as most ceramic materials, have very high melting temperatures or are very difficult to melt in the atmosphere, and have brittleness, making it difficult to cause plastic deformation. Therefore, it is difficult to manufacture the component parts having the desired size and complicated shape by the casting method and the molding method among the above-mentioned manufacturing methods, and it is difficult to use them in terms of economic efficiency. Thus, the powder casting method is generally adopted in the production of compound material element parts having such desired size and complex shape. However, this method can be applied to complex component parts having a relatively small size or relatively large structural element parts having a small aspect ratio, but having a large long / short ratio, a large complex shape, or The powder molding sintering method has the disadvantage that it cannot be used when it is undesirable in terms of the properties of the material (for example, the production of single crystal or amorphous material). In addition, the machining method is used only in limited fields due to the very weak mechanical strength of the powder compact, and the production cost by machining the hard material such as sintered ceramics has a large share of the production cost of the product. I have a problem.

Therefore, as far as possible, it is desirable to fabricate element parts of large size and complex shape by joining and connecting materials of simple shapes with sufficient bonding strength to each other. For this purpose, a so-called welding technique is applied to metal materials, but in a compound material such as ceramics, a very high temperature is required, or a change in the composition and crystal structure of the material due to thermal decomposition occurring during welding or the like due to thermal shock Due to breakage and the like, a method of locally heating by using a laser or an electron beam is only very limited. In addition, there are problems in economic aspects, such as the need for productivity and expensive equipment.

The bonding techniques developed to date have made it nearly impossible to make them into one large, single structure without losing the excellent optical, crystallographic, thermal, chemical, mechanical or electromagnetic properties of the individual compound material pieces. Bonding techniques developed to date include mechanical attachment, adhesive bonding, glazing, brazing, diffusion bonding, and fusion welding. They have proved inadequate for joining individual pieces of material together. For example, the joining of a piece of material by mechanical bonding is practically impossible to use in situations where the bond strength is so weak that a significant load is applied even at room temperature and even at room temperature. In addition, except for mechanical bonding, most of the above methods use a method of inserting various bonding materials, such as metal or silicon oxide, between the pieces of material to bond the pieces of material. The remaining intermediate bonding layer between the pieces differs greatly from the base material to be bonded in crystallographic, optical, thermal, chemical, electromagnetic and mechanical properties, which greatly reduces the light transmittance at the bonding interface. This can lead to significant changes in properties, including various properties (especially in the case of metal bonding layers), or failure to achieve a bond with a sufficiently satisfactory bond strength. In particular, when glass is melted at a relatively low temperature to increase light transmittance, the bonding strength is weak, and the thermal shock is weak due to a difference in thermal expansion coefficient. In order to compensate for this, when bonding using glass-ceramic or ceramic materials, the mechanical properties are improved, but there is a problem in that the optical properties are greatly reduced.

On the other hand, in the case of diffusion bonding, by applying a pressure at high temperature, plastic deformation or creep is generated at the joint surface, and the jointing surfaces are brought into perfect contact with each other to obtain a bonding force. In addition to the large amount of dislocations and their movement, they are very easy to perform diffusion bonding through plastic deformation at the bonding surface.However, in the case of ceramics, due to the inherent properties of the material, the dislocations are very small and furthermore, they are not easy to move, so they are fired even at high temperatures. Deformation is very difficult. As a result, direct diffusion bonding of ceramics is only successful in very small areas, and even in this case, the bond strength is well known to be far below the strength of the raw material. In addition, it requires a heat treatment condition at a high temperature and a high pressure near the melting temperature of the base material, and has a problem in that impurity removal and bonding must be performed under ultra-high vacuum in order to remove impurities adsorbed at the bonding interface. Moreover, this method is very sensitive to surface roughness, making it difficult to fabricate a bonded structure with sufficient bond strength in most compound materials. In addition, it is difficult to obtain sufficient bonding strength, such as cracking due to temperature gradient generated during melting and thermal stress generated during cooling. It is more difficult to apply to the junction of. In addition, there are many problems, such as the use of expensive special equipment and unsuitable for mass production.

An example of a monolithic and large compound material element component in one structure is a sapphire structure. Sapphire refers to a single crystal phase of alumina (Al ₂ O ₃ ), an oxide of aluminum, and is excellent in wear resistance, heat resistance, chemical resistance, thermal conductivity, and insulation, and is an electronic component for transmitting a wide wavelength from infrared to near ultraviolet It is applied to various places such as optical components and optical parts. In particular, sapphire not only has structural integrity, but also has sufficient thermal stability and high transmission of light in the visible, infrared and ultraviolet regions for use in various military applications. However, their application to these applications is severely limited by the difficulty of manufacturing large component parts.

Recently, to solve this problem, the surfaces of the sapphire pieces were coated with MgO vapor and contacted to face each other, and then heat-treated in a gas atmosphere containing hydrogen at about 1500 to 2000 ° C. for several hours, thereby having relatively good optical properties and bonding strength. It has been reported that sapphire structures can be made (US Patent No. 5942343). However, this method has a problem in that the coated MgO reacts with sapphire to form MgAl ₂ O ₄ spinel phase at the junction interface and still no direct contact bond is formed between the sapphires.

The technical problem to be solved by the present invention is to provide a method of chemically reacting pieces of individual compound materials (as well as single crystals or polycrystalline or amorphous materials) to form one large unitary structure bonded directly without the presence of an intermediate layer at the bonding interface. It is.

In order to achieve the above technical problem, in the method of manufacturing a compound material reaction diffusion structure according to the present invention, two or more pieces of compound material (including compound single crystal or polycrystal, solid solution monocrystalline or polycrystalline, and amorphous material) Preparing or polishing a part or entire surface thereof, and incorporating or dissolving it into the compound material upon conversion to a compound phase by chemical reaction with the surrounding gas atmosphere and / or the compound material upon heat treatment. A thin film of the composition by thinly inserting, applying, depositing, plating, or coating metals that can be solid solution, or metal organics or metal compounds or mixtures or solid solutions thereof containing the same in a molecular formula. To form. Then, in the atmosphere or vacuum, or a gas atmosphere containing an inert gas, hydrogen, or a constituent gas of the compound material in a state where the surface where the composition thin film is formed and the surface where the composition thin film is formed to face each other face to face. The high temperature heat treatment with or without pressing induces a chemical reaction of the composition at the bonding interface, thereby forming a material reactive bond in which the interface is chemically strongly bonded without the presence of the second phase. Also, if necessary, heat treatment in the above-described gas atmosphere may be further performed to improve the properties of the material.

According to a preferred embodiment, Li, Be, B, C, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Insert, slurry, or apply a thin film of a composition composed of one or more components selected from the group consisting of metals, metal organics, or metal compounds of Ac, Th, Pa, U, Np, Pu, Am, and Cm. By forming a very thin layer on the compound material to be bonded and heat-treated appropriately in contact with each other. At this time, by inserting or depositing, depositing, plating or coating the thin film of the composition sufficiently and heat-treating them, they are only present temporarily at the interface to promote mass transfer to form a strong bond, and then with the surrounding gas atmosphere and / or the compound material. The chemical reaction converts to form the same or different compound phase as the compound material and then allows the converted phase to be incorporated or solid solution into the compound material. As a result, it is possible to produce a reaction junction structure that is completely directly bonded between compound materials without the presence of a second phase at the bonding interface.

Thus, by the method according to the invention, individual pieces of compound material can be directly bonded by chemical reaction to form one large unitary structure. This not only has the structure almost the same mechanical, optical, electromagnetic, thermal, chemical and crystallographic properties as the individual pieces of compound material, but also maintains its structural integrity for use in the application of the material. It has enough characteristics.

As described above, in the conventional method of joining materials using a metal bonding material, for example, the loss of light transmittance due to the presence of a metal bonding layer between the materials after bonding and the coefficient of thermal expansion between the metal bonding layer and the base material and mechanical Due to the difference in properties, it was impossible to obtain high bond strength. However, as in the present invention, a metal (for example, Mg in the case of MgO single crystal) or a metal element (for example, MgO single crystal in the case of MgO single crystal) forming a compound material (base metal) to be bonded is formed. Al, etc.) are formed very thinly on the site to be bonded, for example, about 0.001 to 500 µm, preferably about 1 to 10 µm, and then heat-treated at their melting temperature (including partial melting degree) or more. Is present as an intermediate layer which promotes mass transfer between the bonding interfaces, at the same time part of the evaporation and part of the atomic diffusion into the base material, wherein the constituent gas of the compound material or The compounding of atoms that are incorporated into or dissolved into the compound material through chemical reaction with the compound material As a result, in the late stage of bonding, the metal bonding layer disappears, and as a result, reaction bonding between the compound materials is formed. Thus, using this method, it is possible to form a junction structure in which the crystallographic, thermal, mechanical, chemical and electromagnetic properties are almost equivalent to the compound material.

In this way, the present invention not only overcomes the shortcomings and difficulties of the existing technologies, but also provides many advantages, such as allowing the bonded structures made according to the present invention to have better thermal, mechanical, chemical and electromagnetic properties. Have

Specific details of other embodiments are included in the detailed description and drawings.

Hereinafter, with reference to the accompanying drawings will be described in detail a method of manufacturing a compound material reaction diffusion junction structure according to the present invention. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms, and only the embodiments make the disclosure of the present invention complete, and the scope of the invention to those skilled in the art. It is provided for the purpose of full disclosure, and the invention is only defined by the scope of the claims. In particular, in the description of the present invention, the term crystal is used to refer to both pure crystals or solid solutions or complexes thereof, and also refers to both single crystals and polycrystals. Although the specification describes a case where the crystal pieces and the crystal pieces are bonded, the present invention can be used by those skilled in the art to bond crystals and their solid solution (or complex) crystals or solid solution (or complex) crystals. It will be appreciated. It will also be appreciated that the present invention can also be used to join amorphous and crystalline or amorphous materials.

Example

1 is a flow chart of a method of manufacturing a compound material reaction diffusion junction structure according to the present invention.

Referring to FIG. 1, in step 10, a part or entire surface of a piece of two or more compound materials, including compound single crystals or polycrystals, solid solution single crystals or polycrystals, and amorphous materials, are all polished, lapping or polishing. do. The crystals in the fragment of the compound material may be obtained by cutting the prepared crystal or its solid solution or composite crystal into the desired crystallographic direction, size and shape.

Next, upon heat treatment on at least one side of the piece of material polished in step 20, it can be incorporated into or solid solution into the base material by being converted into the compound phase by chemical reaction with the ambient gas atmosphere and / or the base material. Various metals or metal organics or metal compounds or mixtures or solid solutions thereof containing the same in a molecular formula are thinly inserted, coated, deposited, plated or coated to form a thin film of the composition. At this time, the composition thin film is made into a thin thin film (foil), inserted into, or formed into a slurry in which fine powder of nm size is dispersed, or applied by spin coating, a sol-gel method, and sputtering. ), Chemical vapor deposition (CVD), organometallic CVD (MOCVD), laser ablation, pulsed laser deposition, reactive evaporation, resistive vacuum deposition Deposition, plating or coating may be performed using one or more methods selected from the group consisting of evaporation, electrolytic or electroless plating.

Common to all compound materials, various metals that can be converted into a compound by chemical reaction and incorporated into or solid-solution into a base material by heat treatment include Li, Be, B, C, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, Fr, Ra, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, Np, Pu, Am, Cm and the like. Such metals may be used in the form of metals themselves, organics of these metals, or compounds. In addition, the compounds are borides, carbides, nitrides, nitrides, oxides, fluorides, silicides, phosphides, sulfides, chlorides of metal elements. chloride, germanide, arsenide, selenide, bromide, telluride, iodide or intermetallic compounds and these Solid solution compounds of the liver.

With continued reference to FIG. 1, in accordance with step 30, the base material pieces are assembled into a desired structure by facing the surface on which the composition thin film is formed and the surface on which the composition thin film is not formed, or the surface where the composition thin film is formed, and then in the air or in vacuum or inert. High temperature heat treatment in a gas atmosphere containing gas, hydrogen or a constituent gas of the compound material. At this time, heat treatment may be performed in a pressurized or non-pressurized state. The heat treatment is performed for about 1 minute to 10 hours at a temperature between the melting temperature (including partial meltness) and the evaporation temperature of the thin film composition. In the case of pressurization, a pressure between 0 and 100 MPa, preferably between 0 and 30 MPa, is used. The heat treatment herein may include all kinds of heat treatments such as radiant heating, inductive heating, microwave heating, ultrasonic heating, and the like. The composition thin film formed on the substrate polishing surface temporarily exists as a medium for promoting mass transfer at the interface during this heat treatment step, and then partially or entirely inside the substrate is converted into a compound phase by chemical reaction with the surrounding gas atmosphere or the substrate. Infiltrate in the way of incorporation or employment. Therefore, finally, the bonding and bonding between the compound materials at the interface can be made to have almost the same mechanical, thermal, chemical and electromagnetic properties, and the coefficient of thermal expansion as the base compound of the same thickness can be made of excellent bonding structure. The bonding interface is chemically tightly bonded to form one large structure that is mechanically / structurally integrity and integrated structurally, thermally, chemically, and electromagnetically. Here, it is preferable that the joining interface forms a direct joining interface without the second phase. The absence of a second phase is meant to include the presence of an amount below the measurement limit. However, since a very thin composition thin film is formed, even if the second phase is present, the shape will be in the form of precipitation or segregation, but not a uniform film of the second phase.

For example, Mg or Mg alloy is deposited on the MgO single crystal polishing surface, and then subjected to an oxygen atmosphere heat treatment at a temperature higher than the melting temperature of the composition. The composition then initially melts over the interface between the MgO single crystal pieces to form a very thin Mg liquid film and acts as a medium to facilitate mass transfer between the MgO single crystal interfaces. Over time, however, the molten Mg is partially evaporated and the remainder diffuses and penetrates into the MgO single crystal, forming an oxide as a rapid reaction with dissolved oxygen dissolved in the component gas (here oxygen gas) present in the heat treatment atmosphere, forming an oxide. To be incorporated or employed. As a result, a second phase having a different crystal structure does not exist at the interface between the MgO single crystals and an epitaxial bonding interface having a light transparency composed of MgO alone can be obtained.

Similarly, Al or an Al alloy is deposited on the sapphire polishing surface, followed by an oxygen atmosphere heat treatment at a higher temperature than the melting temperature of the composition. Then, it is initially melted on the interface between the sapphire pieces to form a very thin Al liquid film, which acts as a medium for facilitating mass transfer between the sapphire interfaces. Over time, however, the molten Al is partially evaporated and the remainder diffuses and penetrates into the sapphire crystals, forming or oxides into the sapphire crystals, forming oxides by rapid reaction with dissolved oxygen dissolved in oxygen gas present in the heat treatment atmosphere. . As a result, the second phase having a different crystal structure does not exist at the interface between the sapphire crystals, and the epitaxial bonding interface having the light transparency composed of only sapphire can be obtained.

Particularly important in this process is that the composition thin film completely undergoes phase transition during the bonding process. For this purpose, control of the appropriate gas atmosphere is important, but thickness control of the composition thin film is most important. Because the phase transition of the composition thin film between the base metals is a process involving gas diffusion and chemical reactions, the thicker the thickness of the composition thin film, the more time is required for the complete phase transition to become uneconomical or unreacted interlayer composition. This is because it may remain. And if the thickness is too thin, it is difficult to obtain the desired bonding strength. Therefore, the thickness of the composition thin film should be appropriately determined. According to a preferred embodiment of the present invention, the thickness of the composition thin film is about 0.001 ~ 500㎛. More preferably, it is about 1-10 micrometers.

Meanwhile, the heat treatment for bonding may be performed while applying an electric field. Compound materials form compounds by covalent or ionic bonding, and most of them have ionic bonding properties. Therefore, when an electric field is applied from the outside, the cations and anions constituting the ion-bonding compound are subjected to electrostatic forces in opposite directions by the applied electric field, and as a result, ions are moved by the electric field in the solid. -migration) will occur. This facilitates the bonding of materials. For example, when two materials to be bonded are contacted and heat treated, when a voltage is applied to each surface, positive ions move from the positive voltage side toward the bonding interface. The negative ions move toward the junction interface from the side where the negative voltage is applied. As a result of the action of the electrostatic force, the supply of cations and anions to the bonding interface is made from the base material, which causes the effect of achieving more complete interface contact and bonding as they recombine and precipitate at the bonding interface.

In the case of applying the electric field, a voltage of 0 to 5 KV may be applied in consideration of the electrical conductivity and thickness of the material to be bonded during the heat treatment. Preferably, a voltage of 0 to 0.5 KV is applied. For example, when bonding Al ₂ O ₃ , MgO, and quartz glass, a voltage of 0.3 KV is applied, and when bonding AlN, Si ₃ N ₄ , SiC, and soda-lime glass, a voltage of 0.1 KV is applied.

When the composition thin film formed on the polishing surface of the compound material to be bonded has a higher melting temperature than the base material, or it is difficult to apply the joining process according to the present invention due to thermal decomposition or phase transition during high temperature heat treatment, these are replaced with the base material. Low temperatures (compositions) in the atmosphere or in vacuum, or in an atmosphere containing inert gas, hydrogen, or compound constituent gases in order to pre-change into phases that can be melted at low temperatures or to cause their pyrolysis or phase transition; Heat treatment at low temperature below the melting or pyrolysis temperature of the thin film).

Next, as an optional step, a heat treatment in a compound component gas atmosphere may be further performed in step 40 to improve the properties of the bonding interface. For example, in the case of MgO and sapphire junction, it can implement in oxygen atmosphere. Further heat treatment may induce oxidation and diffusion of a composition (metal or oxide) that may remain at the bonding interface, and may be changed into a bonding interface of, for example, MgO single crystal only, having more excellent interfacial properties and stronger bonding strength. have. The heat treatment in the oxygen atmosphere is performed at 500 to 2000 ° C. for 5 minutes to 10 hours, for example.

More detailed information about the present invention will be described through the following specific experimental examples, and details not described herein will be omitted because it can be inferred technically by those skilled in the art. In addition, the following experimental examples are not intended to limit the present invention. Below is an experimental example of a method for producing a reaction diffusion junction structure such as sapphire single crystal according to the present invention, in addition to various modifications are possible. For example, it can be bonded between monocrystalline or polycrystalline and amorphous materials of different compositions and different crystal structures.

Experimental Example 1 (Sapphire Bonding-1)

Sapphire was cut to the desired crystallographic orientation, size and shape, and then the cross section was polished sequentially using 6 μm diamond abrasive from 1 μm diamond abrasive. In this experiment, sapphire was cut into a 5 mm thick disk. Pure Al (99.99%, Institute of High Purity Chemistry, Japan) was deposited to a thickness of 2 to 4 μm using a vacuum evaporator on surface polished sapphire.

The Al-deposited surfaces were faced and then heat-treated in a vacuum sintering furnace or a hot press sintering furnace (Hot Press). The heat treatment was performed under pressure of 0-30 MPa for 30 minutes to 2 hours at 1000 to 1850 ° C. in an Ar atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. At this time, a gas containing vacuum, hydrogen, or oxygen may be used instead of the Ar heat treatment atmosphere. In addition, if necessary, in order to increase the light transmittance, the secondary heat treatment was performed at 1000 to 2000 ° C. for 30 minutes to 10 hours in an oxygen-containing atmosphere.

2A is a photograph of a sapphire reaction diffusion bonding structure bonded using an Al deposition film according to the experimental example. As can be seen here, when Al is deposited, it can be observed that a high quality uniform sapphire bonded structure with high light transmittance and high bonding strength is formed. The surface is blurry because light reflections occur on the surface because the surfaces of the bonded specimens are not polished.

FIG. 2B is an enlarged photograph of the sapphire reaction diffusion junction structure junction interface of FIG. 2A observed with a scanning electron microscope (SEM). FIG. As can be seen in FIG. 2B, no metal or oxide phase (ie, second phase) of any kind was observed at the junction interface, as described above, all of the deposited Al was melt-evaporated / diffused- during the heat treatment. It means that the sapphire crystal was changed through oxidation-incorporation / employment. As a result, as shown in FIG. 2C, which is a result of measuring the light transmittance of the bonded specimen, the bonded specimen (indicated by the solid line) has a high light comparable to the light transmittance of the sapphire single crystal (indicated by the dotted line) of the same thickness. The transmission characteristics are shown.

This result is not only Al as a composition thin film, but also Al alloy, Mg, Cr, Ti, Fe, V, Si, Ca, Co, Cu, Ag, Bi, Cd, Ce, Ga, Hf, K, La, Mn, Na , Nb, Nd, Ni, Pb, Sc, Sm, Sn, Sr, Ta, U, Y, Zn, Zr, Li and alloys thereof were also obtained.

Experimental Example 2 (Sapphire Bonding-2)

Experiment was carried out under the same conditions as in Experiment 1. However, instead of depositing and joining Al on the polished surface, an Al foil having a thickness of about 18 µm was inserted between the two polished surfaces. Heat treatment was carried out in a vacuum sintering furnace or a high temperature pressurization sintering furnace. Heat treatment was performed under pressure of 0-30 MPa for 30 minutes to 2 hours at 600 to 1850 ° C. in an Ar atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC.

3 is a photograph of the sapphire reaction diffusion bonding structure bonded using Al foil according to the experimental example. As can be seen here, it can be observed that a high quality uniform sapphire reaction diffusion junction structure is formed.

Experimental Example 3 (Polycrystalline Al ₂ O ₃  join)

In order to bond the polycrystalline alumina specimen, Al ₂ O ₃ powder (AKP-50, Sumitomo, Japan) was hot-pressed at 1400 ° C. to prepare a sintered specimen made of a polycrystalline body, and then polished the surface thereof and deposited Al thereon. . The Al was deposited to face the polished surface and heat treatment was performed under the same conditions as in Experimental Example 1.

Specifically, Al was deposited only on one side of the alumina to face the other alumina which did not deposit Al, and then heat-treated in a vacuum sintering furnace or a high temperature pressurization sintering furnace. The heat treatment was performed under pressure of 0-30 MPa for 30 minutes to 2 hours at 1000 to 1850 ° C. in an Ar atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. The heat treatment atmosphere was an atmosphere or a gas containing vacuum, hydrogen, or oxygen in addition to Ar.

4A is a photograph of an alumina polycrystalline reaction diffusion bonding structure bonded using an Al deposition film according to the experimental example. FIG. 4B is an enlarged SEM photograph of the bonding interface of the alumina polycrystalline reaction diffusion structure of FIG. 4A. FIG. As can be seen here, when Al is deposited, it can be observed that there is no second phase of any kind at the interface and a high quality homogeneous alumina reaction diffusion junction structure is formed. This means that the Al deposited as described above was transformed into Al ₂ O ₃ crystals through melt-evaporation / diffusion-oxidation-incorporation / employment during heat treatment.

The junction of alumina is Al, Mg, Cr, Ti, Fe, V, Si, Ca, Co, Cu, Ag, Bi, Cd, Ce, Ga, Hf, K, La, Mn, Na, Nb as in the sapphire junction. , Nd, Ni, Pb, Sc, Sm, Sn, Sr, Ta, U, Y, Zn, Zr, Li and alloys thereof can be used.

Experimental Example 4 (Single Crystal MgO Junction)

MgO single crystals were cut into 5 mm thick rectangles, and their cross-sections were sequentially polished from 6 µm diamond abrasive to 1 µm diamond abrasive, and then pure Mg (99.99%) was added to the surface polished MgO single crystal using a vacuum evaporator. Deposited to a thickness of 5 μm.

The MgO single crystal with Mg deposited on one side and the MgO single crystal with no MB deposited on each side were heat-treated in a vacuum sintering furnace or a high-temperature pressurization sintering furnace. The heat treatment was performed at 500 to 1850 ° C. under an Ar atmosphere while giving a pressure of 0 to 30 MPa for 30 minutes to 2 hours. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. When the second heat treatment was performed for 5 minutes to 10 hours at 500 ~ 2000 ℃ it was confirmed that the light transmittance can be increased. The heat treatment conditions play a very important role in the formation of the highly transparent MgO single crystal reaction surface because the phase change and diffusion and the oxidation, incorporation or solid solution of the deposited Mg thin film layer are very sensitive to the heat treatment conditions. .

Figure 5a is a photograph of the MgO single crystal reaction diffusion junction structure bonded using an Mg deposition film according to the experimental example. 5B is an enlarged photograph of the MgO reaction diffusion junction structure bonding interface of FIG. 5A. As can be seen here, when Mg is deposited, it can be observed that there is no second phase of any kind at the interface, and a high quality uniform MgO single crystal junction structure having high light transmittance and high bonding strength is formed. This means that the Mg deposited as described above has been changed into MgO single crystal while undergoing melt-evaporation / diffusion-oxidation-incorporation / employment during the heat treatment.

In particular, these results are not only when using Mg, but also Mg alloys, Li, Be, Na, Al, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag , In, Sn, Sb, Te, La, Tl, Pb, Bi, Ce, Si, Cr, Mn, Fe, Co, Ni, Y, Yb, Sc, V, Er, Zr, Nb and alloys thereof Even when I could get.

Experimental Example 5 (polycrystalline ZnS junction)

The cross section of the disk-shaped ZnS polycrystal was polished using an abrasive of 1 mu m, and then pure Zn (99.99%) was deposited to a thickness of 2 to 5 mu m using a vacuum evaporator on the surface polished ZnS poly crystal.

The two ZnS polycrystalline specimens faced each other to face Zn-deposited surfaces, and were heat treated using a vacuum sintering furnace or a high temperature pressurizing sintering furnace. The heat treatment was performed under pressure of 0 to 10 MPa for 30 minutes to 2 hours at 500 to 1000 ° C. in an Ar atmosphere. The temperature increase rate was 10 degreeC per minute. In order to improve properties, the secondary heat treatment may be performed at 500 to 1000 ° C. for 5 minutes to 10 hours in an atmosphere containing component gas.

FIG. 6 is a photograph of a ZnS polycrystalline reaction diffusion bonding structure bonded using a Zn deposited film according to the experimental example. As can be seen here, when Zn is deposited, it can be observed that there is no kind of second phase at the interface and a high quality uniform ZnS polycrystalline junction structure with high bonding force is formed. This means that the Zn deposited as described above has been changed to ZnS polycrystal during all the heat treatment through melt-evaporation / diffusion-sulphide-incorporation / employment.

In addition to Zn, ZnS can be bonded to Li, Be, Na, Mg, Al, K, Ca, Ti, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag, In, Sn, Sb, Te, It was confirmed that La, Tl, Pb, Bi, Ce, Si, Cr, Mn, Fe, Co, Ni, Y, Zr and their alloys could be used.

Experimental Example 6 (amorphous soda-lime glass junction)

Pure Al (99.99%, Institute of High Purity Chemistry, Japan) was deposited to a thickness of 2 to 5 μm using a vacuum evaporator on a rectangular soda-lime glass cross section. One side was faced with a soda-lime glass specimen having an Al deposition film and a soda-lime glass specimen without a deposition film, and then heat-treated in a vacuum sintering furnace or a high temperature pressurization furnace. The heat treatment was performed at 400 to 700 ° C. under an Ar atmosphere while giving a pressure of 0 to 10 MPa for 30 minutes to 2 hours. The temperature increase rate was 10 degreeC per minute. At this time, if necessary, the heat treatment atmosphere may be air or vacuum, or a gas containing an inert gas, hydrogen, or a soda-lime glass material component gas, or the like. Also, if necessary, secondary heat treatment may be performed at 400 to 700 ° C. for 5 minutes to 10 hours in an atmosphere containing soda-lime glass component gas to improve properties.

7A is a photograph of a soda-lime glass reaction diffusion bonding structure bonded using an Al deposition film according to the experimental example. 7B is an enlarged SEM photograph of the bonding interface of the soda-lime glass reaction diffusion structure of FIG. 7A. As can be seen here, when Al is deposited, it can be observed that there is no kind of second phase at the interface and a high quality uniform soda-lime glass joint structure is formed with high bonding force. This means that the deposited Al was incorporated into the soda-lime glass through evaporation / diffusion-oxidation-incorporation / employment as described above.

On the other hand, when bonding soda-lime glass, in addition to Al, Li, Be, Na, Mg, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag, In, It was confirmed that Sn, Sb, Te, La, Tl, Pb, Bi, Ce, Si, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb and their alloys can be used.

Experimental Example 7 (polycrystalline AlN junction)

In order to bond the polycrystalline aluminum nitride (AlN) specimen, an AlN sintered specimen prepared by high temperature pressurization was prepared. Then, the surfaces of the polycrystalline AlN pieces were polished sequentially using 6 μm diamond abrasive to 1 μm diamond abrasive, and pure Al (99.99%, High Purity Chemical Research Institute, Japan) was applied to the surface polished polycrystalline AlN using a vacuum evaporator. It was deposited to a thickness of 2 ~ 4㎛.

The Al-deposited and non-deposited surfaces faced each other and then heat-treated in a vacuum sintering furnace or a high-temperature pressurization sintering furnace. The heat treatment was performed while applying a pressure of 0 to 30 MPa and a voltage of 0 to 0.5 KV for 30 minutes to 2 hours at 1000 to 1850 ° C. in a nitrogen atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. At this time, if necessary, the heat treatment atmosphere may be a vacuum or an inert gas, hydrogen, or a gas containing oxygen. In addition, if necessary, the secondary heat treatment may be performed at 1000 to 2000 ° C. for 30 minutes to 10 hours in an atmosphere containing nitrogen.

FIG. 8 is a cross-sectional SEM photograph of an AlN polycrystalline diffusion bonding structure bonded using an Al deposition film according to this experimental example. As can be seen here, it can be observed that there is no second phase of any kind at the interface and a high quality uniform AlN reaction diffusion junction structure is formed. This means that the Al deposited as described above was transformed into AlN crystals during the heat treatment through melt-evaporation / diffusion-nitridation-incorporation / employment.

When AlN is bonded, Li, Be, Na, Mg, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag, In, Sn, Sb, Te , La, Tl, Pb, Bi, Ce, Si, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo and alloys thereof can be used.

Experimental Example 8 (Polycrystalline Si ₃ N ₄  join)

In order to bond polycrystalline silicon nitride (Si ₃ N ₄ ) specimens, Si ₃ N ₄ sintered specimens prepared by high-temperature pressurization were prepared. Then, the surfaces of the polycrystalline Si ₃ N ₄ pieces were polished sequentially using 6 μm diamond abrasive to 1 μm diamond abrasive, and then pure Si was 2 to 4 μm using the vacuum evaporator on the surface polished polycrystalline Si ₃ N ₄ . Was deposited to a thickness of.

The surface on which the Si deposition film was formed and the surface on which the Si deposition film was not faced were heat-treated in a vacuum sintering furnace or a high temperature pressurization sintering furnace. The heat treatment was performed while applying a pressure of 0 to 30 MPa and a voltage of 0 to 0.5 KV for 30 minutes to 2 hours at 1400 to 1850 ° C. in a nitrogen atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. At this time, if necessary, the heat treatment atmosphere may be a vacuum or an inert gas, hydrogen, or a gas containing oxygen. In addition, if necessary, the secondary heat treatment may be performed at 1000 to 2000 ° C. for 30 minutes to 10 hours in an atmosphere containing nitrogen.

9 is a photograph of a Si ₃ N ₄ polycrystalline reaction diffusion bonding structure bonded using a Si deposited film according to the experimental example. Here, no metal or second phase of any kind is observed at the junction interface and a good, uniform Si ₃ N ₄ reactive junction structure is formed, which, as described above, is all melt-diffused- during the heat treatment of the deposited Si. Through the nitriding-incorporation / employment, it means that the Si ₃ N ₄ crystal has been changed.

When bonding polycrystalline Si ₃ N ₄ , not only Si, but also Li, Be, Na, Mg, Al, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag , In, Sn, Sb, Te, La, Tl, Pb, Bi, Ce, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Sc, V, Tc, Ru, Rh, Hf, Ta , W, Re, Os, Ir, Tl, Po, Fr, Ra, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U , Np, Pu and their alloys can be used.

Experimental Example 9 (Polycrystalline SiC Junction)

In order to bond polycrystalline silicon carbide (SiC) specimens, SiC sintered specimens prepared by high-temperature autoclaving were prepared, and the surfaces thereof were polished, and then Si was deposited thereon. The specimen was prepared by facing Si on the polished surface and heat-treating for 2 hours under a methane (CH ₄ ) atmosphere at 1600 ° C. while applying a pressure of 0˜30 MPa.

Specifically, the surface of the polycrystalline SiC piece was polished sequentially using 6 μm diamond abrasive to 1 μm diamond abrasive, and then pure Si was deposited on the surface polished polycrystalline SiC using a vacuum evaporator to a thickness of 2 to 4 μm.

The Si-deposited and non-deposited surfaces were faced and then heat-treated in a vacuum sintering furnace or a high temperature pressurized sintering furnace. The heat treatment was performed while applying a pressure of 0 to 30 MPa and a voltage of 0 to 0.5 KV for 30 minutes to 2 hours at 1400 to 1850 ° C. in a methane atmosphere. The temperature increase rate was 10 degreeC per minute up to 1500 degreeC, and it was 5 degreeC per minute above 1500 degreeC. At this time, if necessary, the heat treatment atmosphere may be a vacuum or an inert gas, hydrogen, or a gas containing carbon. If necessary, the secondary heat treatment may be performed at 1000 to 2000 ° C. for 30 minutes to 10 hours in an atmosphere containing carbon.

FIG. 10 is a SEM photograph of a SiC polycrystalline diffusion bonding structure bonded using a Si deposition film according to the experimental example. As can be seen, it can be observed that there is no second phase of any kind at the interface and a high quality homogeneous SiC reactive junction structure is formed. This means that as described above, all of the deposited Si was converted into SiC crystals through melt-diffusion-carbonization-incorporation / employment during the heat treatment.

When SiC is bonded, similar to Si ₃ N ₄ , in addition to Si, Li, Be, Na, Mg, Al, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr, Ag , In, Sn, Sb, Te, La, Tl, Pb, Bi, Ce, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Sc, V, Tc, Ru, Rh, Hf, Ta , W, Re, Os, Ir, Tl, Po, Fr, Ra, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U , Np, Pu and their alloys can be used.

Experimental Example 10 (Amorphous Quartz Glass Bonding)

Pure Si was deposited to a thickness of 2 to 5 μm using a vacuum evaporator on rectangular quartz glass pieces. The specimens were prepared by facing the surface on which Si was deposited and heat-treated in a vacuum sintering furnace or a high temperature pressurization sintering furnace. The heat treatment was performed while applying a pressure of 0 to 10 MPa and a voltage of 0 to 0.5 KV for 30 minutes to 2 hours at 800 to 1500 ° C. in an oxygen atmosphere. The temperature increase rate was 10 degreeC per minute. At this time, if necessary, the heat treatment atmosphere may be air or vacuum, or a gas containing an inert gas, hydrogen, or a quartz glass material component gas. Also, if necessary, the secondary heat treatment may be performed at 500 to 1500 ° C. for 5 minutes to 10 hours in an atmosphere containing quartz glass component gas to improve properties.

FIG. 11 is an SEM photograph of a quartz glass reaction diffusion bonding structure bonded using a Si deposition film according to the experimental example. As can be seen here, when Si is deposited, it can be observed that there is no second phase of any kind at the interface and a high quality uniform quartz glass bonded structure with high bonding strength is formed. This means that the Si deposited as described above was incorporated into the quartz glass through diffusion-oxidation-incorporation / employment during the heat treatment.

When joining quartz glass, in addition to Si, similar to soda-lime glass, Li, Be, Na, Mg, Al, K, Ca, Ti, Zn, Cs, Ba, B, Cu, Ga, Ge, Se, Rb, Sr , Ag, In, Sn, Sb, Te, La, Tl, Pb, Bi, Ce, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb and their alloys may be used.

As described above, according to the present invention, the lowering of the bonding strength, which is a problem with the conventional compound material bonding, and the decrease of the electromagnetic properties such as the decrease of the light transmittance due to the second phase existing at the interface mainly in the form of metal, and the base material and the surfactant Degradation of bond strength and degradation due to the difference in thermal expansion coefficient between two phases, and deterioration of chemical and thermal properties can be solved. Therefore, if the reaction diffusion junction structure of the compound material is manufactured by the above method, it can be easily and inexpensively manufactured in large quantities.

As mentioned above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the technical spirit of the present invention. It is obvious.

As described above, the method of manufacturing a compound material reaction diffusion joint structure according to the present invention is due to the low bonding strength, which is the biggest weakness of the conventional method of manufacturing the material bonding structure, and the presence of the second phase in the metal phase in the bonding interface. Compound materials can be strongly bonded without deterioration and degradation of bonding strength due to various thermal, chemical and electromagnetic properties and the difference in coefficient of thermal expansion with the base material, and bonding through general thin film and heat treatment process without expensive special device The formation of a directly bonded interface without a second phase at the interface allows for low cost and low cost of crystal structures or composites or solid solution crystals or amorphous materials with good thermal, chemical and electromagnetic properties and high mechanical bonding strength. Can be produced in large quantities.

In addition, the method for producing a reaction diffusion bonded structure of the compound material according to the present invention can be applied to other types of material bonding. In particular, when used as a semiconductor substrate can be bonded to the substrate to further increase the possibility of application of the crystal substrate, small natural crystal pieces can be bonded to make a very large jewelry crystals.

Claims (13)

(a) preparing two or more pieces of the compound material to polish the surface of the pieces of the compound material; (b) at least one of a metal, a metal organic material, and a metal compound which can be incorporated into the compound material during the heat treatment is applied on at least one polishing surface by applying, applying, depositing, plating, and coating any one of the following methods: Forming a; And (c) forming a directly bonded interface without a second phase at a bonded interface by heat-treating the pieces of the compound material facing each other with the composition thin film formed therebetween. Method of manufacturing the bonded structure. The compound material reaction of claim 1, wherein in the heat treatment step, the composition thin film is incorporated into the compound material while being converted into a compound phase by a chemical reaction with at least one of an ambient atmosphere gas and the compound material. Diffusion Bonded Structure Manufacturing Method. The method of claim 1, wherein after step (c) Further heat-treating in any one of an atmosphere, a vacuum and a gas atmosphere, wherein the gas atmosphere is an atmosphere comprising any one of an inert gas, hydrogen, and a constituent gas of the compound material. Diffusion Bonded Structure Manufacturing Method. The method of claim 3, wherein the additional heat treatment is performed for 1 minute to 10 hours between room temperature and the melting temperature of the compound material. The method of claim 1, wherein in the step (b), at least one of the metal and the metal organic material is applied by any one method of inserting, applying, depositing, plating, and coating. Heat treating below the melting temperature of the composition thin film in any one of atmospheric, vacuum and gaseous atmospheres to achieve a more uniform bonding, wherein the gaseous atmosphere is an inert gas, hydrogen and components of the compound material. Method for producing a compound material reaction diffusion junction structure, characterized in that the atmosphere containing any one of the gases. The method of claim 1, wherein the heat treatment while applying an electric field in step (c). The method of claim 1, wherein the heat treatment is performed while applying pressure in the step (c). The method of claim 1, wherein in step (c), the heat treatment is performed while applying a pressure of 0 to 100 MPa. The method of claim 1, wherein the heat treatment of step (c) is carried out in any one of an atmosphere, a vacuum, and a gas atmosphere, wherein the gas atmosphere includes any one of an inert gas, hydrogen, and a constituent gas of the compound material. Method for producing a compound material reaction diffusion junction structure, characterized in that. The method of claim 1, wherein the heat treatment of step (c) is performed for about 1 minute to 10 hours at a temperature between the melting temperature and the evaporation temperature of the thin film of the composition. The method of claim 1, wherein the thickness of the composition thin film is about 0.001 to 500 μm. The method of claim 1, wherein the heat treatment of step (c) (c-1) heating at a temperature higher than the melting temperature of the thin film of the composition to form a thin liquid film on the interface between the pieces of the compound material to facilitate mass transfer between the compound material pieces; And (c-2) the compound while chemically reacting at least one of the dissolved component gas and the compound material dissolved in the component gas of the compound material present in the heat treatment atmosphere with the metal element in the liquid film to form a compound And incorporating it into the piece of material. (a) preparing any one of at least two single crystals and solid solution single crystal pieces thereof, and polishing the surface of the single crystal pieces; (b) inserting, applying, depositing, plating and coating at least one of a component metal of a single crystal, an organic material containing the component metal in a molecular formula, and an oxide of the component metal on a surface of at least one of about 0.001 to 500 µm Applying to any one of the methods to form a composition thin film; And (c) about 1 minute to 10 hours at a temperature between the melting temperature and the evaporation temperature of the composition thin film in any one of air, vacuum and gas atmospheres with the single crystal pieces facing each other with the surface on which the composition thin film is formed. Forming a direct bonding interface without thermal treatment by presence of a second phase at the bonding interface, Wherein said gas atmosphere is an atmosphere comprising one of an inert gas, hydrogen, and said single crystal component gas.

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