TW201641203A - Ceramic plating - Google Patents

Abstract

Composite member of material bonding, manufacturing method thereof and its application are disclosed. The present invention particularly relates to a transparent ceramic composite member of material bonding, manufacturing method of such ceramic composite member and its application. The composite member is made of two members fastened to each other. At least one member is an engineering ceramic. The members are fastened to each other without using bonding materials.

Description

Ceramic spraying

The present invention relates to a composite member for material joining, a method of manufacturing the same, and applications thereof. More particularly, the present invention relates to transparent ceramic composite members joined by materials, methods of making such ceramic composite members, and applications thereof.

The advantage of engineering ceramics over a variety of other materials is their greater chemical, thermal and/or mechanical stability. Therefore, it is advantageous to expand the application range of ceramics.

Especially in areas with strong corrosion, transparent ceramics are superior to transparent materials such as plastic or glass. Transparent ceramics are suitable for applications where corrosion is high due to their chemical, thermal and/or mechanical resistance.

However, engineering ceramics also have certain shortcomings. For example, in many cases, the fracture strength of thinner ceramic-substrates is insufficient. Transparent ceramics, for example, can be used as display panels for mobile electronic devices. However, it is difficult to achieve thickness and weight standards with ceramic disks because these standards must have a certain thickness in order to ensure sufficient breaking strength.

One solution to the above problems is to provide a ceramic-substrate composite or laminate whose ceramics can be ultra-thin and provide a functional surface. The substrate acts as a carrier for the ceramic and can perform more functions, such as providing the composite with sufficient breaking strength. However, the ceramic must be attached to the carrier material in a strong (preferably material bonded) manner.

Ceramic-substrate laminates joined by an adhesive layer are disclosed in the prior art. However, such an adhesive layer is particularly difficult to combine the extremely high strength of the entire laminate with the extremely strong interlayer adhesion.

In particular, in the field of optics, a composite of materials joined by an amorphous material such as glass is disclosed, and such a composite system is produced by sputtering two individual members. This operation establishes a connection between two members whose surface quality is excellent and whose surface shapes are shaped to each other. The corresponding surfaces on the members can be brought into close contact by abutting each other to establish a fixed connection for the two members. According to current theories, the force that sustains such a connection is the van der Waals force between the atoms or molecules of the two members.

The advantage of performing a spray coating is that it is not necessary to use a joining material such as an adhesive to join the components together. It is speculated that these components are mainly aggregated by adhesion. The bonding mechanism between the germanium wafer and the quartz wafer is based on a Si-O-Si bond formed at a high temperature (>100 ° C) (Gösele, Tong: Semiconductor wafer bonding, Annual Review of Materials Science 28 (1), 1998, 215-241). It is necessary to sufficiently hydrophilize the surface to form a Si-O-Si bond. A prerequisite for the robustness of the connection is a clean, very smooth and precisely mated surface.

DE 10 2011 012 835 A1 describes a method of joining glass to a crystalline ceramic by pretreatment in an oxygen low pressure plasma and heat treatment at at least 100 ° C under vacuum (<10 mbar). It is not necessary to carry out the coating process additionally (for example with SiO ₂ ). This can be achieved by applying a pressing force of 20 kPa to 5 MPa.

The object of the present invention is to provide an engineering ceramic and another component Fixed connection. Especially in the case of transparent ceramics, the connection of the invention does not adversely affect the transparency of the composite. The present invention provides composite members of ceramics and ceramics or ceramics and other materials, such as ceramics containing (cured) glass or ceramics containing plastic.

Only after the development of polycrystalline transparent ceramics (such as the polycrystalline transparent ceramic described in WO 2013/068418 A1, whose RIT value is >75% (thickness: 2 nm) at a wavelength of 600 nm), the present invention is the first to borrow A transparent material composite having at least one ceramic component is produced by sputtering. The transparency is measured

- Linear transmittance (RIT) and narrower aperture angles <0.5o

- Spot frequency

- Haze (turbidity)

To reliably quantify.

The solution of the present invention to achieve the above object is a composite member having the characteristics of a separate item. The preferred design is referred to the attached item. The method of the present invention for making a composite component of the present invention is defined by the features of the independent method request. Thus, the method of the present invention establishes a connection between a ceramic component and another component by sputtering. A preferred design of the method of the present invention is described in the accompanying method request.

According to a preferred embodiment of the invention, the two members are joined together directly, i.e., without the aid of an adhesive. A certain joint pressure is required for this purpose.

According to another embodiment of the present invention, the adhesion promoter may be plated on one or both members and the members may be sprayed together through the or the adhesion promoter. In particular, the present invention preferably employs a metal or metal oxide as an adhesion promoter, which can be plated on the respective members through different processes. It is especially preferred to use coating methods, especially PVD methods (such as sputtering, electron beam evaporation, Ion assisted deposition), CVD or sol-gel methods. The PVD method is particularly suitable because it enables the flatness required to perform the sputtering. The layer thickness is preferably from 1 nm to 10 μm. It is of course also possible to plate the layers onto the component by screen printing or pad printing or the like.

The metals can be implemented as a metal layer or an oxide layer. For example, when bonding is performed under oxidizing conditions (e.g., under an oxidizing atmosphere), the oxide layer is preferably produced during the bonding of the members.

Transparent Si and Ti are preferably used, and transparent SiO ₂ , TiO ₂ or ITO (indium tin oxide) is preferably used as an adhesion promoter. According to the invention, other metals or metal oxides, in particular transparent metals or metal oxides, are likewise suitable as adhesion promoters. For components that do not require transparency, it is of course also possible to use opaque metals or metal oxides. An alternative is to perform surface deuteration by pyrolytic deposition of a precursor. This solution coats the surface with SiO _{2 by} burning monodecane (SiH ₄ ). It is especially preferred to pre-clean the surface (eg by plasma cleaning).

For the spraying of the members, the flatness of the surface to be sprayed should be <10 μm, preferably <1 μm, and particularly preferably <100 nm.

According to the invention, the distance of the surface of the component to be joined is very small during the joining process, and according to a preferred embodiment of the invention, the surfaces of the components to be joined are brought into intimate contact, ie the distance of the surfaces is in accordance with the invention The middle is equal to zero, and the surface of the member to be joined is brought into contact as completely as possible. In order to ensure such close contact, the present invention particularly preferably employs the aforementioned surface flatness. According to another preferred embodiment of the invention, the surfaces awaiting connection are precisely matched to each other. In particular, when the members are sprayed without using an adhesion promoter, the accuracy of the fitting is particularly high.

According to the invention, it may be necessary to apply pressure and/or temperature after joining or during joining, depending on the material to be joined.

The preferred pressure of the present invention is between atmospheric pressure and 2000 MPa. For example, a large pressure can be generated by a gas pressure (argon, nitrogen, air) in a hot press (HIP).

A preferred temperature range for performing the joining process is between room temperature and below the melting/softening temperature of the member, which has a lower melting/softening temperature.

An advantage of implementing the joining process of the present invention in a HIP device is that temperature application and pressure application can be performed simultaneously, even under an atmosphere, as desired.

It can also be processed in vacuum furnaces, pressure sintering furnaces or other units that can be treated at pressure and/or temperature. Mechanical pressure components, such as presses, can also be used and heat treated in the furnace.

In order to shorten the processing time, the present invention can also be subjected to pressure and heat treatment by a rapid sintering process such as a FAST method (field assisted sintering process).

It is advantageous to perform cleaning on the surface to be joined, as appropriate, before spraying the components. According to the present invention, water, OH groups, hydrocarbons, and other substances on the surfaces can be removed by plasma etching, chemical cleaning, temperature adjustment in air, vacuum atmosphere or H ₂ atmosphere, or by ion beam etching.

According to a preferred embodiment of the invention, the coefficients of thermal expansion (WAK) of the components to be sprayed are matched to each other. In some instances, such as when the composite members made in accordance with the present invention need to be applied under thermal loading conditions (e.g., when used as furnace windows or fireplace windows), such WAKs are preferably as similar as possible.

However, in some applications of the composite member, the two members of the present invention preferably have different coefficients of thermal expansion. The present invention provides a composite member in which a member is composed of a material having a higher WAK, and compressive stress is generated in the other member. That is, for example, ceramics with lower WAK When the member is connected to the glass of the WAK, a compressive stress is generated in the surface of the ceramic, and the compressive stress may increase the breaking strength of the ceramic.

According to a particularly preferred embodiment of the invention, the fabricated composite member is part of a display of, for example, a mobile electronic device. In this case, the total thickness of the composite member is very small. Thus, the ceramic composite component consists of a thinner ceramic layer, for example bonded to a chemically cured glass or to a plastic. For such use, the ceramic layer or the ceramic member has a thickness of <50 mm, preferably <1 mm, more preferably <0.5 mm, and most preferably <0.1 mm.

The principle of the invention is to create a diffusion layer between the ceramic component and the component material to be sprayed. The material to be sprayed may also slightly penetrate the ceramic surface, and the grid in the contact layer may be adjusted.

The components to be sprayed are joined together in a materially bonded manner to form a chemical reaction zone.

The present inventors have unexpectedly discovered that the transparent composite member of the present invention can be produced by sputtering without interfering intermediate layers.

- RIT>60%, preferably >70%, especially better >75%

- Spot frequency <10%, preferably <3%, especially preferably <1%

- Haze <10%, preferably 5%, especially preferably <2%. By using higher requirements in terms of flatness (<10 μm, preferably <1 μm, especially <100 nm) and roughness (<20 nm, preferably <10 nm, especially <1 nm), it is possible to prevent, for example, surface voids. In the case of scattered light or an interferogram.

These bonding pairs can produce a more suitable joint connection with a RIT value of >80% when using a thinner solution (thickness <1.5 mm, preferably <0.75 mm, especially <0.3 mm) because of the transparent The degree increases as the thickness decreases. The reason for this is that when the ceramic composition is thin, the originally extremely low defect density (porosity < 100 ppm) is further lowered, and the light passes through the member almost unimpeded. In addition, the geometric requirements are also reduced because the glass components and ceramic components can be deformed and can be softly pressed together. To do this, it is necessary to apply a certain joint pressure.

The thinner ceramic components have a polycrystalline structure, preferably magnesium aluminate spinel (MgAl ₂ O ₄ ) or polycrystalline corundum (α-Al ₂ O ₃ ).

When the hard ceramic is thin enough, it can be made soft: the bending stiffness is proportional to the third power of the thickness, so the thinner component embodiment significantly reduces the stiffness. This is particularly evident in the case where the ceramic thickness is <300 μm, preferably <200 μm, and particularly preferably <100 μm.

In particular, the present invention describes the following aspects:

‧ A composite member consisting of a fixed connection of two members, at least one of which is an engineered ceramic, and wherein the members are joined in a manner that does not employ a joining material.

‧ A composite member according to the previous point, wherein the two members are joined in a materially joined manner in a manner to form a chemical reaction zone.

The composite member according to any one of the preceding claims, wherein the one member is an engineering ceramic selected from the group consisting of ceramics, selected from a second engineering ceramic, selected from a transparent material, selected from the group consisting of glass, preferably selected from the group consisting of The alkali aluminum bismuth glass is preferably selected from the group consisting of alkali-containing aluminum bismuth glass whose near surface layer is pre-tensioned by a certain pressure, selected from cured glass or selected from plastic.

The composite member according to any one of the preceding claims, wherein the engineering ceramic has a polycrystalline structure.

The composite member according to any one of the preceding claims, characterized in that the engineering ceramic is a polycrystalline transparent engineering ceramic.

The composite member according to any one of the preceding claims, wherein the engineering ceramic is a polycrystalline transparent engineering ceramic, preferably magnesium aluminum spinel (MgAl ₂ O ₄ ) or polycrystalline corundum (α-Al ₂ O ₃ ) .

The composite member of any of the preceding claims, wherein the composite member is transparent.

The composite member according to any one of the preceding claims, wherein the composite member is transparent and has a RIT > 60%, preferably > 70%, particularly preferably > 75%, and a spot frequency < 10%, preferably < 3%, especially Preferably <1%, Haze (hazeness) <10%, preferably 5%, especially preferably <2%.

A method of manufacturing a composite member according to any one or more of the preceding claims, wherein the two members, at least one of which is an engineered ceramic, are joined together by sputtering without using a joining material.

</ RTI> The method of any of the preceding claims, wherein the two members, at least one of which is an engineered ceramic, are joined together by a joining pressure without using a joining material.

The method of any of the preceding claims, wherein an adhesion promoter is plated on the surface of one or both members and the members are sprayed together through the or the adhesion promoter.

</ RTI> A method according to any one of the preceding claims, wherein a metal or metal oxide is used as an adhesion promoter.

The method of any of the preceding claims, wherein the coating is applied by a coating method, in particular a PVD method (such as sputtering, electron beam evaporation, ion assisted deposition), CVD or sol-gel method. Adhesive.

The method of any of the preceding claims, wherein the adhesion promoter is plated with a layer thickness of from 1 nm to 10 μm.

‧ The method according to any one of the preceding claims, wherein transparent Si and Ti are used, and transparent SiO ₂ , TiO ₂ or ITO (indium tin oxide) is particularly preferably used as an adhesion promoter.

</ RTI> A method according to any one of the preceding claims, wherein surface deuteration is carried out by pyrolytic deposition of a precursor.

The method of any of the preceding claims, wherein the surface is coated with SiO _{2 by} burning monodecane (SiH ₄ ).

</ RTI> The method of any one of the preceding claims, wherein the surface of the surface to be coated is <10 μm, preferably <1 μm, and more preferably <100 nm.

The method of any of the preceding claims, wherein the surfaces of the waiting connection are precisely matched to each other.

</ RTI> A method according to any one of the preceding claims, wherein pressure and/or temperature is applied after the joining is completed or during the joining process.

The method of any of the preceding claims, wherein the applied pressure is between atmospheric pressure and 2000 MPa.

The method of any of the preceding claims, wherein the pressure is applied by a gas pressure (argon, nitrogen, air) in a hot press (HIP).

The method of any of the preceding claims, wherein the bonding process is carried out at a temperature ranging between room temperature and below the melting/softening temperature of the member, which has a lower melting/softening temperature.

The method according to any one of the preceding claims, wherein, in order to shorten the processing time, the pressure and heat treatment are carried out by a rapid sintering process such as a FAST method (field assisted sintering process).

The method of any of the preceding claims, wherein the surface to be joined is cleaned prior to spraying the components.

</ RTI> The method according to any one of the preceding claims, wherein, prior to spraying the components, plasma etching, chemical cleaning, temperature adjustment in air, vacuum atmosphere or H ₂ atmosphere, or ion beam etching Remove the harmful substances on the surface waiting to be joined.

The method of any of the preceding claims, wherein the coefficient of thermal expansion (WAK) of the member to be sprayed is matched to each other.

The method of any of the preceding claims, wherein the coefficient of thermal expansion (WAK) of the member to be sprayed is as similar as possible.

The method of any of the preceding claims, wherein the one member is constructed of a material having a higher WAK to create compressive stress in the other member.

The invention also relates to the use of the composite member of the invention or the composite member made in accordance with the invention, for example as part of a display for a mobile electronic device or as a furnace window or a fireplace window.

The invention is described below in connection with a number of examples, which are not intended to limit the invention.

Example 1:

Two square spinel tiles having a polished surface (r _a < 20 nm, preferably r _a < 10 nm, particularly preferably r _a < 4 nm) are pretreated with a chemical agent and a plasma cleaner. In a clean room environment, the surfaces are brought into contact, aligned with one another at room temperature and heat treated in a thermal homogenizer at a pressure equal to >500 bar, preferably >1000 bar, and particularly preferably >1500 bar. The desired temperature is > 1200 ° C, preferably > 1350 ° C, and more preferably > 1500 ° C. After the end of the heat treatment, the joining of the materials is established by a plurality of diffusion processes, thereby realizing a transparent composite member having a RIT value of >75%.

Example 2:

An alkali-containing aluminum-bismuth glass which is pre-tensioned by a certain pressure layer is sprayed with a transparent spinel ceramic. The dimensions of the square specimens are 10 mm x 10 mm. The glass has a thickness of 1 mm and a ceramic thickness of 500 μm. The flatness is <5 μm and the roughness is less than 1 nm. The beveled edges of the two joint faces achieve precise orientation prior to the heat treatment. The joint faces are pre-cleaned. The spinel ceramic is provided with a thin SiO ₂ layer which is treated by a chemical agent such as nitric acid and an aqueous NH ₄ OH:H ₂ O ₂ solution at a higher temperature of >80 ° C. Hydrophilic. After the orientation of the samples is completed, heat treatment is performed in a high vacuum furnace at a temperature of 200 to 400 °C. After the end of the heat treatment, the joining of the materials is established, thereby realizing a transparent composite member with a RIT value of >75%.

Example 3:

An alkali-containing aluminum-bismuth glass which is pre-tensioned by a certain pressure layer is sprayed with a transparent spinel ceramic. The dimensions of the square specimens are 10 mm x 10 mm. The glass has a thickness of 1 mm and a ceramic thickness of 200 μm. Flatness <500 nm, roughness less than 1 nm. The beveled edges of the two joint faces achieve precise orientation prior to the heat treatment. The joints are plasma cleaned, uncoated and hydrophilic. After the orientation of the samples is completed, heat treatment is performed in a high vacuum furnace at a temperature of 200 to 400 °C. After the end of the heat treatment, the joining of the materials is established, thereby realizing a transparent composite member with a RIT value of >75%.

Claims (31)

A composite member consisting of a fixed connection of two members, at least one of which is an engineering ceramic, and wherein the members are joined in a manner that does not employ a joining material. A composite member according to the first aspect of the invention, characterized in that the two members are joined in a materially joined manner in such a manner as to form a chemical reaction zone. The composite member according to claim 1 or 2, wherein the one member is an engineering ceramic, the other member is selected from the group consisting of ceramics, selected from the second engineering ceramics, selected from transparent materials, and selected from the group consisting of glass. Preferably, it is selected from the group consisting of alkali-containing aluminum-bismuth glass, and is preferably selected from the group consisting of alkali-containing aluminum-bismuth glass whose front surface layer is pre-tensioned by a certain pressure, selected from cured glass or selected from plastic. A composite member according to any one of the preceding claims, characterized in that the engineering ceramic has a polycrystalline structure. A composite member according to any one of the preceding claims, characterized in that the engineering ceramic is a polycrystalline transparent engineering ceramic. The composite member according to any one of the preceding claims, wherein the engineering ceramic is a polycrystalline transparent engineering ceramic, preferably magnesium aluminum spinel (MgAl ₂ O ₄ ) or polycrystalline corundum (α-Al). ₂ O ₃ ). A composite member according to any one of the preceding claims, characterized in that the composite member is transparent. A composite member according to any one of the preceding claims, wherein the composite member is transparent and has a RIT > 60%, preferably > 70%, particularly preferably > 75%, and a spot frequency < 10%, preferably < 3%, especially preferably <1%, Haze (turbidity) <10%, preferably 5%, especially preferably <2%. A method of manufacturing a composite member according to any one or more of the preceding claims, It is characterized in that two members, at least one of which is an engineering ceramic, are joined together by sputtering without using a joining material. The method of claim 9, wherein the two members, at least one of which is an engineering ceramic, are joined together by a joining pressure without using a joining material. A method of claim 9 or 10, wherein an adhesion promoter is plated on the surface of one or both members and the members are sprayed together through the or the adhesion promoter. A method according to any one of the preceding claims, characterized in that a metal or metal oxide is used as an adhesion promoter. A method according to any one of the preceding claims, characterized in that it is plated by a coating method, in particular a PVD method (such as sputtering, electron beam evaporation, ion assisted deposition), CVD or sol-gel method. Cover these adhesion promoters. A method according to any one of the preceding claims, characterized in that the adhesion promoters are plated with a layer thickness of from 1 nm to 10 μm. The method according to any one of the preceding claims, characterized in that transparent Si and Ti are used, and transparent SiO ₂ , TiO ₂ or ITO (indium tin oxide) is particularly preferably used as an adhesion promoter. A method according to any one of the preceding claims, characterized in that the surface deuteration is carried out by pyrolytically depositing a ruthenium precursor. A method according to any one of the preceding claims, characterized in that the surface is coated with SiO _{2 by} burning monodecane (SiH ₄ ). A method according to any one of the preceding claims, characterized in that the waiting for spraying member The flatness of the surface is <10 μm, preferably <1 μm, and particularly preferably <100 nm. A method according to any one of the preceding claims, characterized in that the surfaces of the waiting connection are precisely matched to one another. A method according to any one of the preceding claims, characterized in that the pressure and/or temperature is applied after the joining is completed or during the joining. A method according to any one of the preceding claims, wherein the applied pressure is between atmospheric pressure and 2000 MPa. A method according to any one of the preceding claims, characterized in that the pressure is applied by means of air pressure (argon, nitrogen, air) in a hot press (HIP). A method according to any one of the preceding claims, wherein the bonding process is carried out at a temperature ranging from room temperature to below the melting/softening temperature of the member, which has a lower melting temperature/softening temperature. A method according to any one of the preceding claims, characterized in that, in order to shorten the processing time, the pressure and heat treatment are carried out by a rapid sintering process such as a FAST method (field assisted sintering process). A method according to any one of the preceding claims, characterized in that the surface to be joined is cleaned before the components are sprayed. A method according to any one of the preceding claims, characterized in that before the spraying of the members, plasma etching, chemical cleaning, temperature adjustment in air, vacuum atmosphere or H ₂ atmosphere, or through Ion beam etching removes harmful substances on the surface that is awaiting bonding. A method according to any one of the preceding claims, characterized in that the waiting for spraying The coefficients of thermal expansion (WAK) of the members match each other. A method according to any one of the preceding claims, characterized in that the coefficient of thermal expansion (WAK) of the member to be sprayed is as similar as possible. A method according to any one of the preceding claims, wherein the member is constructed of a material having a higher WAK to create a compressive stress in the other member. An application of a composite member according to any one of claims 1 to 9 or a composite member made according to any of the method claims, as part of a display such as a mobile electronic device. A composite member according to any one of claims 1 to 9 or a composite member made according to any one of the method claims, for use as a furnace window or a fireplace window.