TW201607768A - Method for fabricating a flexible glass thin film structure - Google Patents

Abstract

The present invention discloses a method for fabricating a flexible glass thin film structure, mainly comprising the steps of: providing a flexible substrate and depositing a sandwich thin film on the flexible substrate. Depositing of the sandwich thin film on the flexible substrate further comprises depositing a first organic thin film, depositing an inorganic thin film on the first organic thin film, and depositing a second organic thin film on the inorganic thin film. The first organic thin film and the second organic thin film both comprise elements of silicon, oxygen, carbon, hydrogen and fluorine and are a porous organosilica glass films. The method can fabricate a flexible glass thin film structure which exhibits good performances of transmittance, cooling capacity, hydrophobe and Mohs hardness.

Description

Process method for flexible glass film structure

The present invention relates to a method for fabricating a glass film structure, and more particularly to a process for fabricating a flexible glass film structure using chemical vapor deposition to prepare an organic film/inorganic film/organic film to form a sandwich film having a comparable Good light transmission, heat dissipation, hydrophobicity and Mohs hardness.

In recent years, various electronic products, such as mobile communication devices, tablets, or notebook computers, have become more and more abundant. For example, a touch panel is a type of panel that uses an inductive display device that receives a contact input signal. When touched on the graphic button on the screen, the on-screen tactile feedback system can drive various linkage devices according to a pre-programmed program, which can be used to replace the mechanical button panel and create a live sound and video effect through the display screen. Touch screens are used in a wide range of applications, from common cash machines to industrial touch computers. Because touch screens have an intimate and vivid human-machine interface, more and more smart display devices use touch screens.

The current touch electronic products are becoming more and more powerful, and the heat accumulated by the devices is gradually increasing. Typical touch electronic products usually use a glass or plastic substrate as the outer package structure. These two substrates usually cannot achieve good light transmittance, hydrophobicity and Mohs hardness at the same time. In the past, a glass film was applied to the surface of a glass or plastic substrate. However, the glass or plastic substrate coated with the glass film serves as an outer package structure, which causes the internal heat dissipation capability to be lowered, and the heat accumulated in the device cannot be quickly removed. Further, in order to increase the hardness of the glass film, cerium oxide (SiO ₂ ) is usually added to the glass film. However, the addition of the cerium oxide material makes the surface of the glass film hydrophilic, and the cerium oxide material deteriorates with time.

Further, the organic film which is a glass film at this stage is usually a film of a ruthenium-containing chemical containing hydrogen fluoride. The hydrofluoride-containing ruthenium chemical film uses tetraethoxysilane (TEOS) and silane (Silane) as a precursor material in a chemical vapor deposition (CVD) process. An additional fluorocarbon (C _n F _2n+2 ) or krypton fluoride (Si _n F _2n+2 ) gas is deposited as a source of fluorine. However, a process for the combination of the hydrofluoride-containing organic germanium chemical film and the ceria-containing (SiO ₂ )-containing glass film structure has not been disclosed.

In view of the above, it is necessary to propose a process method for fabricating a flexible glass film structure to solve the above problems of the glass or plastic substrate used in conventional electronic products.

The main object of the present invention is to provide a method for manufacturing a flexible glass film structure, which increases the heat dissipation efficiency and transmittance of the substrate through the stacking structure of the porous organic vermiculite glass film, and improves the flexibility by sandwiching the ruthenium dioxide film. The Mohs hardness of the film.

In order to achieve the above-mentioned main object, the present invention provides a method for fabricating a flexible glass film structure, which mainly comprises the steps of: providing a flexible substrate; and depositing a sandwich interlayer film stacked on the flexible substrate And having a stacked structure of a porous organic vermiculite glass film, wherein the sandwich interlayer film is subjected to a chemical vapor deposition (Chemical Vapor) The Deposition, CVD) process adjusts the deposition of an organic germanium precursor.

The step of depositing the sandwich film comprises the steps of: depositing a first organic film to enhance adhesion between the sandwich film and the flexible substrate; depositing an inorganic film stacked on the first organic film Above, to enhance the hardness of the sandwich film; and depositing a second organic film stacked on the inorganic film to enhance the hydrophobicity of the surface of the sandwich film; wherein the first organic film and the The second organic film contains elements such as ruthenium, oxygen, carbon, hydrogen, and fluorine.

According to a feature of the invention, the deposited first organic film and the second organic film are composed of a hydrofluorofluorene oxide compound (Si _a O _b C _c H _d F _e ), a, b, c, d, e respectively represent the atomic percentage of each element, where a is between 10% and 30%, b is between 10% and 30%, c is between 10% and 30%, and d is between 10% and 30%, e Between 10% and 30%, and a+b+c+d+e=1.

According to a feature of the invention, the deposited first organic film has a thickness between 5 nm and 300 nm; and the deposited second organic film has a thickness between 5 nm and 300 nm.

According to a feature of the invention, the inorganic film is composed of cerium oxide (SiO ₂ ) having a film thickness of between 10 nm and 500 nm.

According to one feature of the present invention, the flexible substrate is composed of a material of polyethylene terephthalate (PET), polyimine (PI), polyvinyl chloride (PVC) and carbonate (PC).

According to one aspect of the present invention, the organic silicon-based precursor Silicon tetramethylammonium chloride, of the formula Si (CH _{3) 4.}

According to a feature of the invention, the chemical vapor deposition process is selected from the group consisting of plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), and electron cyclotron resonance. One of the processes of vapor deposition (ECRCVD) and inductively coupled plasma chemical vapor deposition (ICPCVD).

In summary, the manufacturing method of the flexible glass film structure of the present invention has the following effects:

1. A stacking structure of a porous organic vermiculite glass film can be deposited to exhibit good light transmittance and hydrophobicity.

2. Improve the Mohs hardness and heat dissipation capability of the flexible film by depositing the interlayer of the ruthenium dioxide film.

100‧‧‧Flexible glass membrane structure

110‧‧‧Flexible substrate

120‧‧‧ Sandwich laminated film

121‧‧‧First organic film

122‧‧‧Inorganic film

123‧‧‧Second organic film

200‧‧‧ Process flow of flexible glass membrane structure

210‧‧‧ Provide a flexible substrate

220‧‧‧Deposition of a sandwich film

310‧‧‧Deposition of a first organic film

320‧‧‧Deposition of an inorganic film

330‧‧‧Deposition of a second organic film

Fig. 1 is a view showing an embodiment of a flexible glass film structure in the present invention.

Fig. 2 is a view showing an embodiment of a process for producing a flexible glass film structure in the present invention.

Fig. 3 is a view showing an embodiment of the process for producing the sandwich interlayer film of the present invention.

While the invention may be embodied in various forms, the embodiments illustrated in the drawings It is not intended to limit the invention to the particular embodiments illustrated and/or described.

Referring now to Figure 1, an embodiment of a flexible glass film structure 100 of the present invention is shown. The flexible glass film structure 100 mainly comprises: a flexible substrate 110 and a sandwich interlayer film 120.

In an embodiment, the flexible substrate 110 is comprised of a substrate having flexible properties, such as a stainless steel metal or a transparent plastic flexible substrate. Preferably, the flexible substrate 110 is made of a transparent flexible substrate, and the transparent flexible substrate is one of the following materials selected from the group consisting of polyethylene terephthalate (PET) and poly. Polyimides (PI), polyvinyl chloride (PVC), carbonate (Polycarbonate, PC), and the like.

The sandwich interlayer film 120 is deposited on the flexible substrate 110 and includes a first organic film 121, an inorganic film 122, and a second organic film 123. The first organic film 121 is used to enhance the adhesion between the sandwich film 120 and the flexible substrate 110. The inorganic film 122 is stacked on the first organic film 121 to enhance the sandwich layer. The hardness of the film 120; and the second organic film 123 are stacked on the inorganic film 122 to enhance the hydrophobicity of the surface of the sandwich film 120. The first organic film 121 and the second organic film 123 both contain elements such as germanium, oxygen, carbon, hydrogen, fluorine and the like.

With reference to Fig. 1 and with reference to Fig. 2, an embodiment of a process for fabricating a flexible glass film structure of the present invention will be described. Referring to Fig. 3, there is illustrated an embodiment of the process for the sandwich interlayer film of the present invention.

In the process flow 200 of the flexible glass film structure, the following steps are included: Step 210: providing a flexible substrate; and Step 220: depositing a sandwich interlayer film.

In step 210, the flexible substrate 110 is placed in a plasma generation reaction system. The plasma generation reaction system may be any vacuum coating system capable of providing the flexible substrate 110, preferably using a chemical vapor deposition process system, such as plasma enhancement. Plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), electron cyclotron resonance chemical vapor deposition (ECRCVD) Or Inductive Coupled Plasma Chemical Vapor Deposition (ICPCVD) chemical vapor deposition.

In step 220, the step of depositing the sandwich film is performed by a chemical vapor deposition (CVD) process to adjust the deposition of an organic germanium precursor.

Wherein, the chemical vapor deposition process is applied to the process of the present invention as follows: a gas or gas phase source material is introduced into the reaction chamber, and the source material diffuses through the boundary layer and contacts the surface of the substrate to be coated on the substrate surface in an adsorption manner. on. The adsorbed source material then moves over the surface of the substrate and begins a chemical reaction on the surface of the substrate. Finally, the solid product forms crystal nuclei on the surface of the substrate, and the nuclei grow into islands, which are then combined into a continuous film.

The chemical vapor deposition system of the present invention adjusts the parameters of the process by the RF power and the temperature of the reaction system. In a preferred embodiment, the chemical vapor deposition system has a radio frequency power between 10 W and 2000 W in the process, and the temperature of the plasma generation reaction system is between 30 ° C and 300 ° C when the substrate is placed. between. The chemical vapor deposition process is an Inductive Coupled Plasma (ICP) chemical vapor deposition process.

In step 220, the step of depositing the sandwich interlayer film further comprises the following process steps: step 310: depositing a first organic film; step 320: depositing an inorganic film; Step 330: depositing a second organic film.

In step 310, the deposited first organic film 121 is composed of a hydrofluoromethoxy hydride compound (Si _a O _b C _c H _d F _e ), and a, b, c, d, and e respectively represent each element. The atomic percentage. Where a is between 10% and 30%, b is between 10% and 30%, c is between 10% and 30%, d is between 10% and 30%, and e is between 10% and 30%, and a+ b+c+d+e=1. The first organic film 121 is used to enhance the adhesion between the sandwich film 120 and the flexible substrate 110. Preferably, a is between 10% and 30%, b is between 10% and 20%, c is between 10% and 20%, d is between 15% and 20%, and e is between 15% and 25%, and a+b+c+d+e=1. That is, the first organic thin film 121 is a material rich in elements such as carbon, hydrogen, fluorine, etc., and can form a porous organic vermiculite glass film.

In step 320, the deposited inorganic thin film 122 is composed of cerium oxide (SiO ₂ ) or cerium oxynitride (SiON), and has a thickness of 10 nm to 500 nm, and has quite good hardness characteristics. Preferably, the inorganic thin film 122 is composed of cerium oxide (SiO ₂ ). The first organic thin film 121 composed of cerium oxide is solid at normal temperature and pressure, and the thin film constitutes a bond (Si-O). The bond energy of the sandwich film 120 can be increased by a high hardness and has a relatively good toughness, so that the sandwich film 120 can have a Mohs hardness of 8H. Preferably, the thickness of the inorganic thin film 122 is between 20 nm and 50 nm, and the sandwich interlayer film 120 has a Mohs hardness of 9H. The increase in hardness can improve the scratch and abrasion resistance of the flexible glass film structure 100. The surface of the flexible glass film structure 100 has a hardness of 9H, which is higher than ordinary polyethylene terephthalate (PET). The substrate film is three times stronger. Even sharp objects such as keys and knives do not scratch the surface of the flexible glass film structure 100.

The second organic-based thin film 123 in step 330, the deposited silicon hydrogen fluorine formed alumoxane compound _{(Si a O b C c H} d F e), a, b, c, d, e represent each element The atomic percentage. Where a is between 10% and 30%, b is between 10% and 30%, c is between 10% and 30%, d is between 10% and 30%, and e is between 10% and 30%, and a+ b+c+d+e=1. The second organic film 123 is stacked on the inorganic film 122 to enhance the hydrophobicity of the surface of the sandwich film 120. Preferably, a is between 10% and 30%, b is between 10% and 20%, c is between 10% and 20%, d is between 15% and 20%, and e is between 15% and 25%, and a+b+c+d+e=1. That is, the first organic thin film 121 is a material rich in elements such as carbon, hydrogen, fluorine, etc., and can form a porous organic vermiculite glass film.

In step 220, each process of depositing the sandwich film 120 is performed, including the step 310: depositing a first organic film; and step 320: depositing an inorganic film. In step 310, step 320 and step 330, the process of depositing the layers of the film in the sandwich film 120 is grown through a chemical vapor deposition process. By adjusting the type of the organic germanium precursor used, the first organic film 121 and the second organic film 123 deposited by the chemical vapor deposition process will form a porous structure, which can be used to improve the sandwich interlayer film 120. Thermal performance and hydrophobic properties.

In step 220, the method includes the following steps: depositing a first organic thin film; and step 320: depositing an inorganic thin film; and before step 330, first passing a carrier gas into the plasma generating reaction system, and the carrier gas is used to carry the organic germanium. Precursor.

The carrier gas may be selected from one of a reducing gas participating in the reaction and a passive gas not participating in the reaction. When the carrier gas is a reducing gas participating in the reaction, it is selected from one of decane vapor, oxygen, air and hydrogen; when the carrier gas is a passive gas that does not participate in the reaction, it is selected from nitrogen and helium. One with argon.

In one embodiment, the organic ruthenium precursor is a methyl decane, particularly tetramethyl decane, having the chemical formula Si(CH ₃ ) ₄ . In another embodiment, the functional group of the fluorocarbon-containing functional group in the organic ruthenium precursor has a chemical formula of CxHyFz, an x system of between 5 and 20, and a z series of between 3 and 15. More specifically, the fluorocarbon-containing cerium oxide compound precursor is composed of R ₁ Si(OR ₂ )(OR ₃ )(OR ₄ ), Tridecafluoro-1,1,2,2-tetrahydrooctyl-triethoxysilane (TDF-TEOS). And Trimethoxy(3,3,3-trifluoropropyl)silane, wherein R _{1 is one} of a fluorinated alkyl group, a fluorinated alkenyl group, a fluorinated alkynyl group and a fluorinated aromatic group, R ₂ , R ₃ and R ₄ is one of an alkyl group, a fluorinated alkyl group, a fluorinated aromatic group, a fluorinated alkenyl group

In a preferred embodiment, in step 310, step 320, and step 330, the organic germanium precursor is heated at a temperature between 50 ° C and 100 ° C when the carrier gas is introduced to cause the organic germanium precursor. The material has a more stable vapor pressure, and the gas flow rate of the carrier gas is between 0.1 sccm and 10000 sccm, which can be used to effectively reduce the water vapor permeability, and the saturated vapor pressure system of the organic germanium precursor is between 30 torr. Between 80torr. The time to pass the carrier gas is between 0.5 hours and 1.5 hours.

After the completion of step 330, a heat treatment can be further performed. In this step, the organic germanium precursor is converted into the first organic thin film 121 and the second organic thin film 123 having a porous organic vermiculite glass structure by heat treatment, and the first organic thin film 121 and the second organic thin film 123 are eliminated. The stress.

The heat treatment comprises increasing the temperature of the organic germanium precursor or supplying the precursor with an additional energy. The additional energy may be from a magnetic field or other source of light, such as an infrared or laser system additionally incorporated in the plasma generation reaction system. The temperature of the heat treatment is heated to Between 100 ° C and 350 ° C, with a brief conversion time.

In a preferred embodiment, the sandwich interlayer film is grown by an inductively coupled plasma chemical vapor deposition process using an organic germanium precursor of tetramethyl decane and a chemical formula of Si(CH ₃ ) ₄ . Oxygen and nitrogen are used as process gases.

Moisture or moisture in the atmosphere can easily cause deterioration of some materials that like water. The inorganic thin film 122 in the sandwich interlayer film 120 is composed of cerium oxide (SiO ₂ ). Ceria materials have quite superior physical and chemical properties and are often used in a variety of chemical compositions. However, the surface of a pure cerium oxide chemical composition likes to adsorb water. As time goes on, the cerium oxide material will deteriorate. This is due to the fact that the ruthenium dioxide-based compound has a chemically reactive position (functional group) which is a hydrophilic (hydrophilic) hydrogen-oxygen bond. The surface functional group itself is a functional group that prefers water (hydrophilic). Therefore, when it is exposed to air for atmospheric drying, the cerium oxide-based compound is broken due to the large surface tension shrinkage, resulting in a shortened material life. Therefore, in the present invention, the second organic film 123 is stacked on the inorganic film 122 to enhance the hydrophobicity of the surface of the sandwich film 120.

The hydrophobic nature is primarily assessed by the size of the contact angle. The greater the contact angle of the substance with the water droplet, the higher the hydrophobicity; the smaller the contact angle of the substance with the water droplet, the higher the hydrophilicity. In addition, the surface tension between gas and solid is called Surface Free Energy; when the surface free energy is larger, the liquid (droplet) capacity that the surface energy can adsorb is larger, and the liquid adsorption area is also higher. Large, resulting in a smaller surface contact angle. That is, the second organic film 123 reduces the surface free energy of the sandwich film 120. The surface of the sandwich film 120 has a hydrophobic angle greater than 110 degrees. Preferably, the hydrophobic angle of the surface of the sandwich film 120 The degree is between 110 degrees and 160 degrees. The surface is treated with a hydrophobic coating to make fingerprints and oils less likely to adhere to the surface of the flexible glass film structure 100, making it easier to wipe and clean, while also providing ultra-smooth touch sensitivity.

The thickness of the first organic film 121 and the second organic film 122 of the invention are both between 5 nm and 300 nm, so the flexible glass film structure 100 has a relatively good transmittance, and the transmittance is 70. % to 95%. Preferably, the thickness of the first organic film 121 and the second organic film 122 are between 5 nm and 30 nm, and the thickness of the inorganic film 122 is between 10 nm and 50 nm. More preferably, the thickness of the first organic film 121 and the second organic film 122 are between 5 nm and 15 nm, and the thickness of the inorganic film 122 is between 10 nm and 30 nm. Therefore, the flexible glass film structure 100 has a relatively good transmittance and a transmittance of 80% to 95%.

In a specific embodiment, the first organic film and the second organic film are composed of a hydrofluoromethoxy siloxane compound (Si _a O _b C _c H _d F _e ), a, b, c, d, e Represents the atomic percentage of each element. a between 10% and 30%, b between 10% and 20%, c between 10% and 20%, d between 15% and 20%, e between 15% and 25%, and a+b+ c+d+e=1. The thickness of the first organic film is between 10 nm and 12 nm. The thickness of the second organic film is between 10 nm and 12 nm. The inorganic thin film was composed of cerium oxide (SiO ₂ ) and had a film thickness of 50 nm. The flexible substrate is composed of polyethylene terephthalate (PET).

The flexible glass film structure has a transmittance of 75% to 85%: a Mohs hardness of 8H; and the surface has a hydrophobic angle of 110 degrees to 130 degrees.

In summary, the process method of the flexible glass film structure of the present invention has the following effects:

1. Through the stacking structure of depositing porous organic vermiculite glass film, it exhibits good light transmittance and hydrophobicity.

2. Improve the Mohs hardness and heat dissipation capability of the flexible film by depositing the interlayer of the ruthenium dioxide film.

While the present invention has been described in its preferred embodiments, it is not intended to limit the scope of the invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. As explained above, various modifications and variations can be made without departing from the spirit of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

200‧‧‧ Process flow of flexible glass membrane structure

210‧‧‧ Provide a flexible substrate

220‧‧‧Deposition of a sandwich film

Claims (10)

A method for fabricating a flexible glass film structure, the method comprising the steps of: providing a flexible substrate; and depositing a sandwich interlayer film stacked on the flexible substrate and having a porous organic vermiculite glass film a stacked structure, wherein the sandwich interlayer film is deposited by a chemical vapor deposition (CVD) process to adjust an organic germanium precursor; wherein depositing the sandwich interlayer film comprises the steps of: depositing a first organic thin film, For enhancing the adhesion between the sandwich interlayer film and the flexible substrate; depositing an inorganic film stacked on the first organic film to enhance the hardness of the sandwich film; and depositing a second organic The film is stacked on the inorganic film to enhance the hydrophobicity of the surface of the sandwich film; wherein the first organic film and the second organic film both contain elements such as germanium, oxygen, carbon, hydrogen, fluorine and the like. The routing method of one of the first item of the scope of patent flexible glass film structure, wherein the first organic film and the second organic thin-film silicon fluorine hydrogen siloxane compound _{(Si a O b C c H} d F _e ), a, b, c, d, e respectively represent the atomic percentage of each element, where a is between 10% and 30%, b is between 10% and 30%, and c is between 10% and 30%. %, d is between 10% and 30%, e is between 10% and 30%, and a+b+c+d+e=1. The method for fabricating a flexible glass film structure according to claim 1, wherein the first organic film deposited has a thickness of between 5 nm and 300 nm. The method of fabricating a flexible glass film structure according to claim 1, wherein the second organic film deposited has a thickness of between 5 nm and 300 nm. The method for manufacturing a flexible glass film structure according to claim 1, wherein the inorganic film deposited is composed of cerium oxide (SiO ₂ ), and the film thickness thereof is between 10 nm and 500 nm. between. The method for manufacturing a flexible glass film structure according to claim 1, wherein the flexible substrate is polyethylene terephthalate (PET), polyimine (PI), polychlorinated It is composed of one material of ethylene (PVC) and carbonate (PC). The process for producing a flexible glass film structure according to claim 1, wherein the organic ruthenium precursor is tetramethyl decane and the chemical formula is Si(CH ₃ ) ₄ . The method for manufacturing a flexible glass film structure according to claim 7, wherein the chemical vapor deposition process is selected from the group consisting of plasma enhanced chemical vapor deposition, low pressure chemical vapor deposition, and electron cyclotron resonance chemistry. One of the vapor deposition and inductively coupled plasma chemical vapor deposition processes. The method of manufacturing a flexible glass film structure according to claim 1, wherein the flexible glass film structure has a Mohs hardness of 8H. The method of manufacturing a flexible glass film structure according to claim 1, wherein the surface of the sandwich film has a hydrophobic angle of more than 110 degrees.