Material surface modification method using multi-step dry surface treatment

Abstract

The present invention relates to a dry surface treatment method for modifying surface characteristics of materials by using a reactive gas and an ion beam in a vacuum state to treat the surfaces of various materials, namely, planar materials such as polymer films, ceramic substrates, glass substrates, and the like, or powder materials such as ceramic materials, carbon materials, and the like.

Description

Method for surface modification of materials by multi-stage dry surface treatment

[0001] The present invention relates to a dry surface treatment method for modifying the surface properties of a material by treating the surface of various materials, i.e., planar materials such as polymer films, ceramic substrates, and glass substrates, or powder materials such as ceramic materials and carbon materials, using a reactive gas and an ion beam in a vacuum state. The surface modification according to the present invention effectively controls the surface properties of the material to significantly reduce the contact angle, is easily dispersed in a solvent, and stably maintains the dispersion state, thereby maximizing heterogeneous bonding strength, dispersibility, or bonding strength with a base material, thereby enabling the production of products that were previously difficult to implement, and can be widely used in various application fields such as improving the performance of composites by using the surface-modified material as an additive.

[0002] The recent commercialization of 5G communications, the emergence of 6G communications, and the miniaturization of various electronic devices are accelerating the development of materials and components that minimize signal loss at ultra-high frequencies, improve heat dissipation, and reduce weight. For FCCL (Flexible Copper Clad Laminate) to support 5G / 6G communications, the inherent properties (permittivity and dielectric loss) of the insulator of the antenna circuit significantly impact signal loss. To minimize signal loss, lower permittivity and dielectric loss of the insulator are advantageous. Therefore, the development of materials with superior dielectric properties beyond PI (polyimide), which was primarily used in existing 4G communications, is necessary. While alternative materials such as LCP and MPI are being used to manufacture antennas, 6G communications will require communications in the ultra-high frequency range of 100 GHz. In this environment, fluororesin, a material with excellent low-k dielectric properties, will be required as an insulator. However, because of its unique molecular structure, fluororesin does not react well with other substances, making it difficult to secure high bonding strength between the conductive metal layer and the insulating layer required for manufacturing FCCL. To solve this problem, surface treatments such as ion beam, electron beam, and plasma are being used. For example, Heat Assisted Plasma treatment has been proposed as a method to improve the peel strength of fluororesin (PTFE; polytetrafluoroethylene) by modifying the surface using plasma. However, this method has problems such as quality deviation due to the use of multiple plasma torches in a large-area roll-to-roll process, and material deformation when using a thin film due to the high temperature process temperature.

[0003] In the semiconductor industry, the importance of packaging technology, a post-process for semiconductors, is growing. With the advancement of miniaturization and high-integration technologies, conventional resin substrates face limitations in implementing fine-pitch features due to low flatness and the problem of deformation caused by heat generation. Ceramic substrates, on the other hand, face challenges in responding to technological advancements due to their high resistance and permittivity. Therefore, there is active commercialization of glass substrates for high-performance packaging. These substrates offer minimal electrical loss even in the high-frequency range as an insulator, facilitate fine-pitch implementation with excellent flatness, and enable the production of large-area, thin substrates at low cost. However, even glass substrates lack the bonding strength with conductive metal layers, which can lead to reduced product durability and reliability due to factors such as thermal shock.

[0004] In the case of composites, research and development are continuously being conducted to improve the properties of the matrix by adding various powder materials, such as carbon nanotubes (CNTs), graphite, and boron nitride (BN), which selectively exhibit superior mechanical, electrical, chemical, and thermal properties depending on the intended application. However, most fillers have poor wettability, preventing effective mixing with the matrix. To compensate for this, methods such as wet chemical coating of the powder material or addition of dispersants are used. However, wet chemical coating and dispersant addition degrade the inherent properties of the material, and lead to environmental pollution due to wastewater generation and complex processes. Another method, dry surface treatment using plasma, has been proposed, but it suffers from poor reproducibility and the inability to sustain the surface treatment effect. Furthermore, fillers surface-treated in this way suffer from rapid deterioration of the mechanical properties of the composite due to re-agglomeration within the matrix when large amounts of filler are added.

[0005] In these diverse fields, issues such as material heterogeneity, dispersibility, and bonding strength with parent materials are issues that must be resolved in order to develop new products that can respond to industrial development.

[0006] In the past, there were efforts to modify the surface of polymer films by directly blowing a reactive gas separately onto the film surface and irradiating the surface with energetic ion particles. However, this method has the problem that it is difficult to efficiently form functional groups because the functional groups formed by the reactive gas can be removed by continuous irradiation with the Ar ion beam by separately supplying the reactive gas and performing surface treatment during Ar ion beam treatment. In addition, when surface treating a large-area material with a width of 1 m or more, there is a problem in that there is a limit to uniformly treating the entire surface of the large-area material due to the density gradient of the reactive gas depending on the distance from the injection site of the reactive gas.

[0007] The present invention aims to provide a surface modification method that can solve the above problems through effective surface treatment by a dry process. The present invention aims to provide a dry surface treatment method that can solve problems in terms of uniformity, durability, environmental pollution, reproducibility, sustainability, etc. of conventional chemical or physical methods in a surface treatment method that modifies the surface properties of materials by treating the surfaces of various materials, i.e., planar materials such as polymer films, ceramic substrates, and glass substrates, or powder materials such as ceramic materials and carbon materials, using a dry process using a reactive gas and an ion beam in a vacuum state, and at the same time effectively controls the surface properties of the material to significantly reduce the contact angle, and maximize the heterogeneous bonding strength, dispersibility, and bonding strength with the base material by easily dispersing in a solvent and stably maintaining the dispersion state.

[0008] The purpose of the present invention is not limited to what has been described above, and other purposes not described above will be clearly understood by those skilled in the art from the following description.

[0009] The present invention relates to a dry surface treatment method for a material that modifies the surface of the material using an ion beam in a vacuum chamber.

[0010] A step of performing primary surface treatment on the surface of a material by supplying a reactive gas by ionizing it using an ion beam; and

[0011] It includes a step of performing n-th (n is an integer from 2 to 10) surface treatment on a first surface-treated material by ionizing and supplying a reactive gas using an ion beam.

[0012] A method for dry surface treatment of a material is provided, wherein the nth surface treatment is performed by making the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam the same as compared to the first surface treatment, or by changing at least one selected from the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam.

[0013] The vacuum level of the vacuum chamber is preferably 5x10 -5 -5x10 -6 It could be torr.

[0014] The above material may be a polymer film, a ceramic substrate, a glass substrate, a ceramic powder or a carbon powder.

[0015] The present invention has the effect of providing a surface treatment method applicable to the surface of various materials, that is, a surface material such as a polymer film, a ceramic substrate, a glass substrate, or a powder material such as a ceramic material or a carbon material, by dry-treating the surface of the material to modify the surface properties of the material.

[0016] The present invention relates to a dry surface treatment method for modifying the surface of a material in a vacuum chamber, wherein a process of injecting a specific type of reactive gas into a vacuum chamber via an ion beam and irradiating a specific amount of ion beams with specific energy onto the surface of the material is performed in two or more multi-stage steps while changing the conditions step by step, thereby controlling the surface properties of the material, thereby solving problems such as non-uniformity, lack of durability, environmental pollution, lack of reproducibility, and lack of sustainability of conventional chemical or physical methods, and at the same time effectively controlling the surface properties of the material to significantly reduce the contact angle, and to maximize the material's heterogeneous bonding strength, dispersibility, and bonding strength with a base material by easily dispersing in a solvent and stably maintaining the dispersion state.

[0017] This enables the production of products that were previously difficult to implement, and has the effect of being widely used in various application fields, such as improving the performance of composite materials by using surface-modified materials as additives.

[0018] Figure 1 shows the XPS measurement results for a surface-treated PTFE film.

[0019] Figure 2 shows the contact angle measurement results for distilled water on a surface-treated PTFE film.

[0020] Figure 3 shows the contact angle measurement results for distilled water on a surface-treated MPI film.

[0021] Figure 4 shows the contact angle measurement results for distilled water on a surface-treated PI film.

[0022] Figure 5 shows the dispersion state of surface-treated BN filler in distilled water.

[0023] Figure 6 shows the dispersion state of the surface-treated MWCNT material in distilled water.

[0024] Figure 7 is a graph showing the average transmittance in the visible light band immediately after dispersion, 30 seconds later, and 180 seconds later for a surface-treated MWCNT material.

[0025] The present invention will be described in detail below. However, it is not limited to the following description, and each component may be modified or selectively mixed as needed. Therefore, it should be understood that all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention are included.

[0026] The present invention relates to a dry surface treatment method for a material that modifies the surface of the material using an ion beam in a vacuum chamber.

[0027] A step of performing primary surface treatment on the surface of a material by supplying a reactive gas by ionizing it using an ion beam; and

[0028] It includes a step of performing n-th (n is an integer from 2 to 10) surface treatment on a first surface-treated material by ionizing and supplying a reactive gas using an ion beam.

[0029] A method for dry surface treatment of a material is provided, wherein the nth surface treatment is performed by making the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam the same as compared to the first surface treatment, or by changing at least one selected from the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam.

[0030] The above material may be a polymer film, a ceramic substrate, a glass substrate, a ceramic powder or a carbon powder.

[0031] The present invention provides a multi-stage dry surface treatment method that can be used in a wide range of applications by performing a process of ionizing a specific type of reactive gas using an ion beam in a vacuum chamber according to the characteristics of the material and irradiating the surface of the material in two or more stages, and effectively controlling the characteristics of the material surface through changes in the process conditions, thereby improving the heterogeneous bonding strength, dispersibility, or bonding strength with a base material of the material.

[0032] Specifically, the reactive gas of the present invention is characterized in that it is used by ionizing using an active gas or an inert gas using a linear or circular ion beam.

[0033] The vacuum level of the above vacuum chamber is preferably 5x10 -5 -5x10 -6 It could be torr.

[0034] The above active gas or inert gas may be any one of O2, N2, H2 or Ar gas, and it is characterized in that two or more types may be mixed and performed.

[0035] The voltage input from the linear or circular ion beam is 0.5 to 3.0 kV, and the amount of ion beam is 1x10 14 ~5x10 18 ions / cm 2 It is characterized by being performed within the range of , and when the voltage and amount of the ion beam are within the above range, the material can be processed to have the desired properties such as a clean effect, hydrophilicity, bonding strength, and nanostructure formation without damage to the material.

[0036] In one embodiment, the present invention can perform surface treatment using Ar as a reactive gas in the first stage, and from the second stage onwards, using at least one selected from the group consisting of O2, N2, H2 and Ar as a reactive gas, or at least one selected from the group consisting of O2, N2 and H2. In this way, when Ar gas is used as a reactive gas in the first stage, the molecular weight is large and the ionization efficiency is high, so that the effect of forming dangling bonds on the material surface or removing functional groups of polymers is maximized, and when an active gas (nitrogen, hydrogen, oxygen, etc.) is treated in the n-th stage, the above-mentioned position is replaced, so that hydrophilicity can be improved. In other words, if the n-th stage treatment using an active gas is well controlled, the user's desired results can be obtained through hydrophilicity, adhesiveness, nanostructure formation, etc.

[0037] The present invention determines the surface treatment conditions and the number of surface treatment orders by considering the properties to be obtained through the material after n-th (n is 2 or more) surface treatment, for example, when only hydrophilicity is desired, when strong adhesion with other polymer materials is desired, when adhesion with heterogeneous materials (metals, polymers, etc.) is desired, etc.

[0038] The present invention can perform pretreatment prior to dry surface treatment on a material. This pretreatment may be heat treatment. An example of pretreatment is heat treatment using an infrared heater at a temperature of 120-180°C for 2-30 minutes. This method uses infrared radiation to heat the target material, removing internal gases and contaminants, thereby minimizing defects in subsequent processes. Furthermore, for crystalline polymers (e.g., PTFE, PEEK), it has the advantage of smoothing the surface shape.

[0039] Below, the surface treatment method for each material is described in detail.

[0040] Surface modification of polymers

[0041] In the present invention, when the material is a polymer, surface modification of the polymer can be achieved by performing surface treatment by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam for each surface treatment from the first to nth times for the polymer material, or by repeatedly performing surface treatment under the same conditions from the second to nth times by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam after the first surface treatment, or by performing surface treatment by additionally changing the conditions after the third time and repeating the treatment up to the nth time.

[0042] The polymer surface modification status was confirmed by measuring the contact angle with distilled water. A smaller contact angle indicates increased hydrophilicity of the polymer surface, which enhances adhesion to other polar substances.

[0043] The polymer material may be at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyimide (PI), modified polyimide (MPI), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyoxymethylene (POM), perfluoroalkoxy alkane (PFA), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), and polymethyl methacrylate (PMMA), but is not limited thereto.

[0044] The above 1st-nth surface treatment is characterized in that it is performed by ionizing a reactive gas of an active gas or an inert gas using a linear ion beam. n may be 3 or more.

[0045] The reactive gas for the above first surface treatment may be any one of O2, N2, H2 or Ar gases, and it is characterized in that two or more types may be mixed to perform the treatment. The first surface treatment gas is preferably Ar.

[0046] The reactive gas for the above 2nd to nth surface treatment may be any one of O2, N2 or H2 gas, and it is characterized in that two or more types may be mixed and performed.

[0047] The input voltage of the above linear ion beam is 0.5 to 2.0 kV, and the amount of ion beam is 1x10 14 ~5x10 17 ions / cm 2 When performed within the range of , the hydrophilicity of the polymer surface increases without damaging the surface of the polymer material, and the adhesion to other polar substances is enhanced.

[0048] Surface modification of ceramic substrates

[0049] In the present invention, when the material is a ceramic substrate, surface modification of the ceramic substrate can be achieved by surface treating the ceramic substrate material in a vacuum state by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam in each order from the first to the nth order, or by performing surface treatment by repeatedly performing surface treatment under the same conditions as the first surface treatment up to the nth order after the first surface treatment. n can be 3 or more.

[0050] The surface modification status of the ceramic substrate was confirmed by measuring the contact angle with distilled water. A smaller contact angle indicates increased hydrophilicity of the ceramic substrate surface, which enhances adhesion to other polar substances.

[0051] The above ceramic substrate may be made of one or more materials selected from the group consisting of boron nitride (BN), alumina (Al2O3), aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), magnesia (MgO), silica (SiO2), tungsten carbide (WC), titanium carbide (TiC), tantalum carbide (TaC), titanium nitride (TiN), and zirconia (ZrO2), but is not limited thereto.

[0052] The above 1st to nth surface treatments are characterized in that they are performed using a linear ion beam with an active gas or an inert gas as a reactive gas.

[0053] The reactive gas of the above first surface treatment may be any one of O2, N2, H2 or Ar gas, and it is characterized in that it may be performed by mixing two or more types.

[0054] The reactive gas for the above 2nd to nth surface treatment may be any one of O2, N2, H2 or Ar gas, and it is characterized in that it may be performed by mixing two or more types.

[0055] The voltage input from the above linear ion beam is 0.5 to 3.0 kV, and the amount of ion beam is 1x10 14 ~5x10 18 ions / cm 2 It is characterized by being carried out within the scope of .

[0056] When the input voltage and amount of the ion beam are as described above, dangling bonds are created, improving the reactivity between the ceramic substrate and other materials.

[0057] Surface modification of glass

[0058] In the present invention, when the material is a glass substrate, surface modification of the glass substrate can be achieved by surface treating the glass material by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam in each order from the first to the nth order in a vacuum state, or by repeatedly performing surface treatment under the same conditions as the first surface treatment from the first surface treatment to the nth order.

[0059] The modification status of the glass surface was confirmed by measuring the contact angle with distilled water. A smaller contact angle indicates increased hydrophilicity of the polymer surface, which enhances adhesion to other polar substances.

[0060] The above glass substrate material may include oxide-based glass such as silicate, borosilicate, and phosphate, and is characterized by not being limited by differences in the composition of metal oxides such as Al, Ca, Mg, Na, K, Pb, B, Ba, Ce, Fe, and Zn.

[0061] The above 1st to nth surface treatments are characterized in that they are performed by ionizing using a linear ion beam with an active gas or an inert gas as a reactive gas.

[0062] The reactive gas of the above first surface treatment may be any one of O2, N2, H2 or Ar gas, and it is characterized in that it may be performed by mixing two or more types.

[0063] The reactive gas for the above 2nd to nth surface treatment may be any one of N2, H2 or Ar gas, and it is characterized in that two or more types may be mixed and performed.

[0064] The voltage input from the above linear ion beam is 0.5 to 3.0 kV, and the amount of ion beam is 1x10 14 ~5x10 18 ions / cm 2It is characterized by being carried out within the scope of .

[0065] In one embodiment, the nth order may be 3 or more.

[0066] Surface modification of powder materials

[0067] When the material of the present invention is ceramic powder or carbon powder, surface modification of the powder material can be achieved by surface treating the powder material by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam in each order from the first to the nth order in a vacuum state, or by surface treating the powder material by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam after the first surface treatment and repeatedly performing surface treatment under the same conditions from the second to the nth order.

[0068] Unlike surface materials, powder materials can be made using a container that holds the powder and a stirring device that moves the powder within the container so that the ion beam can be evenly irradiated onto the powder surface.

[0069] The surface modification status of the powder material was confirmed through dispersibility in polar solvents. The dispersion rate of the surface-modified material in the solvent compared to the untreated powder material was visually observed, and the dispersion stability was measured using a UV-Vis spectrophotometer.

[0070] The above powder material may include, but is not limited to, one or more selected from the group consisting of carbon nanotubes (CNT), graphite, graphene, boron nitride (BN), alumina (Al2O3), aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), magnesia (MgO), silica (SiO2), tungsten carbide (WC), titanium carbide (TiC), tantalum carbide (TaC), titanium nitride (TiN), and zirconia (ZrO2).

[0071] The above 1st to nth surface treatments are characterized in that they are performed using a circular or linear ion beam with an active gas or an inert gas as a reactive gas.

[0072] The reactive gas of the above first surface treatment may be any one of O2, N2, H2 or Ar gas, and it is characterized in that it may be performed by mixing two or more types.

[0073] The reactive gas for the above 2nd to nth surface treatment may be any one of O2, N2 or H2 gas, and it is characterized in that two or more types may be mixed and performed.

[0074] The voltage input from the above ion beam is 0.5 to 2.0 kV, and the amount of ion beam is 1x10 14 ~5x10 17 ions / cm 2 It is characterized by being carried out within the scope of .

[0075] In one embodiment, n may be 2 or more.

[0076] The present invention is described below with reference to examples, but the scope of the present invention is not limited by the examples.

[0077] <Example 1> Surface treatment of PTFE film

[0078] For a PTFE film with a thickness of 150 μm, heat treatment was performed at 150°C for 5 minutes using an infrared heater. Then, a linear ion beam was used to ionize the reactive gas Ar gas and treat it on the surface of the film. At this time, the amount of the ion beam was 5×10 15 ions / cm 2 The first surface treatment was performed with N2 gas as a reactive gas and ionized with an ion beam, with the amount of ion beam being 5×10 15 ions / cm 2The second and third surface treatments were performed. The input voltage was 1.0 kV for both the first surface treatment and the second and third surface treatments. Fig. 1 shows the XPS results according to the number of surface treatments. When untreated, the chemical bond of the PTFE surface is confirmed by the peak of CF or C-F2 bond at 292 eV, but after the first surface treatment, the 292 eV peak is lowered and a 285 eV peak is formed. After the second surface treatment, the 292 eV peak is lowered further and the 285 eV peak is further increased, and after the third surface treatment, the 292 eV peak almost disappears and the 285 eV peak is mainly formed. In other words, as the number of surface treatments increases, the CF and C-F2 bonds decrease and C-C, C-O, and C-N bonds are formed, which improves the bonding strength with the metal material.

[0079] <Example 2> PTFE film surface treatment

[0080] For a PTFE film with a thickness of 150 μm, heat treatment was performed at 150°C for 5 minutes using an infrared heater. Then, a linear ion beam was used to ionize Ar gas, a reactive gas, on the surface of the film with an ion beam dose of 5×10 15 ions / cm 2 The first surface treatment was performed with O2 gas as the ion beam and reactive gas, and the amount of the ion beam was 5×10 15 ions / cm 2The second and third surface treatments were performed. The input voltage was 1.0 kV for both the first surface treatment and the second and third surface treatments. Figure 2 shows the contact angle measurement results according to the number of surface treatments. The contact angle of the untreated (control) was 94.8°, the first surface treatment was 64.8°, and the first, second, and third surface treatments were 37.5°. As the number of surface treatments increases, the contact angle gradually decreases, which can be seen as an increase in hydrophilicity. The increase in hydrophilicity is because the surface energy of the film increases, which further increases the reactivity with other substances, resulting in an increase in adhesion.

[0081] <Example 3> Confirmation of surface modification effect according to the number of MPI film surface treatments

[0082] In order to confirm the surface modification effect according to the first, second, and nth surface treatments according to one embodiment of the present invention, untreated, first surface treated, first, second, and third surface treated groups were set for the modified polyimide (MPI) film of Company A. The surface treatment conditions for each order for the experimental group were an input voltage of 1.0 kV, first Ar gas, and an ion beam amount of 5x10 15 ions / cm 2 , secondary N2 gas, ion beam amount 5x10 15 ions / cm 2 , tertiary N2 gas, ion beam amount 5x10 15 ions / cm 2 Surface treatment was performed.

[0083] <Example 4> Confirmation of surface modification effect according to the number of MPI film surface treatments

[0084] In order to confirm the surface modification effect according to the first, second, and nth surface treatments, the degree of hydrophilicity was confirmed by measuring the contact angle after surface treatment on the MPI film of Company B. The surface treatment conditions for each stage for the experimental group were as follows: input voltage 1.0 kV, first Ar gas, and ion beam amount 5x10 15 ions / cm2 , 5x10 of the secondary O2 gas ion beam 15 ions / cm 2 , 5x10 of the third O2 gas ion beam 15 ions / cm 2 Surface treatment, 4th O2 gas ion beam amount 5x10 15 ions / cm 2 The surface was treated with water, and the fluid used for contact angle measurement was distilled water, and the measurement results are shown in Fig. 3. The contact angle of the untreated control group was 72.0°, the first surface treatment was 59.5°, and the contact angle was 7.8° for the first, second, third, and fourth surface treatments. As the number of surface treatments increased, the contact angle gradually decreased, which can be seen as an increase in hydrophilicity. The increase in hydrophilicity can be obtained by increasing the film surface energy, which further increases the reactivity with other substances, resulting in an increase in adhesion.

[0085] <Example 5> Confirmation of surface modification effect according to the number of PI film surface treatments

[0086] In order to confirm the surface modification effect according to the first, second, and nth surface treatments, the degree of hydrophilicity was confirmed by measuring the contact angle after surface treatment on the PI film of Company C. The surface treatment conditions for each stage for the experimental group were an input voltage of 1.0 kV and a first Ar gas ion beam dose of 5x10 15 ions / cm 2 , 5x10 of the secondary O2 gas ion beam 15 ions / cm 2 , 5x10 of the third O2 gas ion beam 15 ions / cm 2 The surface treatment was performed, and the fluid used for contact angle measurement was distilled water, and the measurement results are shown in Fig. 4.

[0087] Referring to Figure 4, the untreated contact angle is 64.4°, the first surface treatment is 43.2°, and the first, second, and third surface treatments are 12.4°. As the number of surface treatments increases, the contact angle gradually decreases, which can be seen as an increase in hydrophilicity. The increase in hydrophilicity can be achieved by increasing the film surface energy, which further increases the reactivity with other substances, resulting in an increase in adhesion.

[0088] <Example 6> Surface treatment for AlN substrate

[0089] For a 635㎛ AlN substrate, a linear ion beam was used to surface-treat the substrate surface with Ar gas as the ion beam gas, while changing the input voltage, ion beam dose, and surface treatment order. Table 1 shows the contact angle results according to the surface treatment conditions. When untreated, the contact angle of the AlN substrate was 55-60°, but when observing the change in contact angle according to the input voltage, ion beam dose, and surface treatment order, it was confirmed that the contact angle decreased as the input voltage, ion beam dose, and surface treatment order increased. This can be seen as an increase in hydrophilicity, and the surface energy of the ceramic substrate increases, which improves the reactivity with other substances, resulting in improved adhesion.

[0090] Untreated condition 1 Condition 2 Condition 3 Condition 4 Condition 5 Condition 6 Input voltage (kV) 2.0 2.0 2.5 2.5 3.0 3.0 Amount of ion beam (dose / cm) 2 )1E+143E+141E+155E+151E+162E+16Number of surface treatments5 times10 times5 times10 times5 times10 timesContact angle(°)55-6045-4832-3539-4326-2833-3423-26

[0091] <Example 7> Surface treatment for borosilicate glass substrate

[0092] For a 500㎛ borosilicate glass substrate, surface treatment was performed on the surface of the substrate using a linear ion beam by changing the reaction gas and surface treatment order. Table 2 shows the contact angle results according to the surface treatment conditions. When untreated, the contact angle of the borosilicate glass substrate was 38.8°, while when Ar gas, input voltage 3.0 kV, and ion beam amount 5x10 17 ions / cm 2 When the first surface treatment was performed, the contact angle decreased to 17.2°, indicating that hydrophilicity increased. To confirm the effect of multi-stage surface treatment, Ar gas, input voltage 3.0 kV, and ion beam dose 5x10 17 ions / cm 2 The second to fifth surface treatments were performed. After the second surface treatment, the contact angle was 13.7°, after the third surface treatment, the contact angle was 9.3°, after the fourth surface treatment, the contact angle was 6.4°, and after the fifth surface treatment, the contact angle was 3-4°, indicating complete hydrophilicity. There was no change in the contact angle when the sixth surface treatment was performed. This can be seen as maximum surface modification achieved with the fifth surface treatment.

[0093] Surface treatment conditions Contact angle Gas ion beam input voltage Ion beam control group X38.8°1st Ar3kV5X10 17 ions / cm 2 17.2°2nd Ar3kV5X10 17 ions / cm 2 13.7°3rdAr3kV5X10 17 ions / cm 2 9.3°4thAr3kV5X10 17 ions / cm 2 6.4°5thAr3kV5X10 17 ions / cm 2 3~4°

[0094] <Example 8> Surface treatment for BN filler

[0095] For plate-shaped boron nitride (BN) fillers with particle sizes of 10-20 μm, surface treatment was performed using a reactive gas and an ion beam. The reactive gas, Ar gas, was ionized using a circular ion beam, and the input voltage was 1 kV and the ion beam dose was 4.5 × 10 14 ions / cm 2 The first surface treatment was performed to form micro-defects on the BN filler surface. Then, O2 gas was used as a reactive gas, with an input voltage of 1 kV and an ion beam dose of 5x10 16 ions / cm 2 The secondary surface treatment was performed to form oxygen functional groups on the surface of the BN filler. After the secondary surface treatment, 3 g of the surface-treated BN filler was added to 50 ml of distilled water, a polar solvent, to check the dispersibility. The results are shown in Fig. 5. Referring to Fig. 5, the control group is an untreated BN filler, and the experimental group is a BN filler that was subjected to a secondary surface treatment. When added to a polar solvent, the BN filler in the control group exhibited hydrophobicity and did not mix, but in the experimental group, the hydrophilicity of the BN filler surface was improved, allowing it to be easily dispersed in a polar solvent.

[0096] <Example 9> Surface treatment for CNTs

[0097] Surface treatment was performed on LG Chemical multi-walled carbon nanotubes (MWCNT (BT1001M)) with an average diameter of 10 nm, an average length of 16 μm, and a specific surface area of ​​250 m2 using a reactive gas and ion beam. The reactive gas, Ar gas, was ionized using a circular ion beam at an input voltage of 0.5 kV and an ion beam dose of 4.5 × 10 14 ions / cm 2 The first surface treatment was performed to form micro-defects on the MWCNT surface. Then, O2 gas was used as a reactive gas, with an input voltage of 1 kV and an ion beam dose of 7x10 16 ions / cm 2The secondary surface treatment was performed to form oxygen functional groups on the MWCNT surface. After the secondary surface treatment, 0.1 g of the surface-treated MWCNT was added to 40 ml of distilled water, a polar solvent, and stirred at 300 rpm for 5 minutes to check the dispersibility. The results are shown in Fig. 6. Referring to Fig. 6, the dispersion status of MWCNTs in distilled water can be seen immediately after stirring, after 30 seconds, and after 180 seconds for the untreated MWCNTs on the left, which is the control group, and the secondary surface-treated MWCNTs on the right, which is the experimental group. In the case of the untreated MWCNTs, most of them precipitated after 180 seconds, but the secondary surface-treated MWCNTs were confirmed to be stably and well dispersed. In order to quantitatively confirm the dispersion stability of MWCNTs in distilled water, 3 ml was taken from the MWCNT mixture of the control and experimental groups and analyzed using a UV-Visible Spectrophotometer (Model: U3900) from HITACHI.

[0098] Figure 7 is a graph showing the average transmittance in the visible light band immediately after dispersion, 30 seconds later, and 180 seconds later. Immediately after dispersion, the transmittance between the control and experimental groups differed by only about 2%, but the difference in transmittance increased rapidly over time, reaching a transmittance difference of more than three times after 180 seconds. This confirms that the hydrophilicity of the secondary surface-treated MWCNTs was enhanced when added to a polar solvent, allowing for stable and easy dispersion in the polar solvent.

[0099] The present invention relates to a dry surface treatment method for modifying the surface properties of a material by treating the surface of various materials, i.e., planar materials such as polymer films, ceramic substrates, and glass substrates, or powder materials such as ceramic materials and carbon materials, using a reactive gas and an ion beam in a vacuum state. The surface modification according to the present invention effectively controls the surface properties of the material to significantly reduce the contact angle, is easily dispersed in a solvent, and stably maintains the dispersion state, thereby maximizing heterogeneous bonding strength, dispersibility, or bonding strength with a base material, thereby enabling the production of products that were previously difficult to implement, and can be widely used in various application fields such as improving the performance of composites by using the surface-modified material as an additive.

Claims

1. A dry surface treatment method for modifying the surface of a material using an ion beam in a vacuum chamber. A step of performing primary surface treatment on the surface of a material by supplying a reactive gas by ionizing it using an ion beam; and It includes a step of performing n-th (n is an integer from 2 to 10) surface treatment on a first surface-treated material by ionizing and supplying a reactive gas using an ion beam. A dry surface treatment method for a material, which is performed by making the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam the same as those of the first surface treatment when performing the above n-th surface treatment, or by changing at least one selected from the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam.

2. A dry surface treatment method for a material according to claim 1, characterized in that the material is a polymer film, a ceramic substrate, a glass substrate, a ceramic powder, or a carbon powder.

3. A dry surface treatment method for a material according to claim 1, wherein the material is a polymer film, and when performing surface treatments from the 1st to the nth time, the surface treatment is performed by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam for each time, or after the 1st surface treatment, the surface treatment is repeatedly performed under the same conditions from the 2nd to the nth time by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam.

4. A dry surface treatment method for a material, characterized in that, in claim 3, the first surface treatment is performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases, and the second to n-th surface treatments are performed using at least one reactive gas selected from the group consisting of N2, H2, and O2 gases.

5. In claim 3, the input voltage of the ion beam is in the range of 0.5 to 2.0 kV, or the amount of the ion beam is 1x10 14 ~5x10 17 ions / cm 2 A method for dry surface treatment of a material, characterized in that it is performed within the range of .

6. A method for dry surface treatment of a material according to claim 3, characterized in that the polymer material comprises at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyimide (PI), modified polyimide (MPI), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyoxymethylene (POM), perfluoroalkoxy alkane (PFA), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), and polymethyl methacrylate (PMMA).

7. A dry surface treatment method for a material according to claim 1, characterized in that the material is a ceramic substrate, and the surface is treated by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam for each order from the 1st to the nth order in a vacuum state, or the surface treatment is repeatedly performed under the same conditions as the 1st surface treatment for the nth order after the 1st surface treatment.

8. A dry surface treatment method for a material according to claim 7, characterized in that the first surface treatment is performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases, and the second to n-th surface treatments are performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases.

9. In claim 7, the input voltage of the ion beam is in the range of 0.5 to 3.0 kV, or the amount of the ion beam is 1x10 14 ~5x10 18 ions / cm 2 A method for dry surface treatment of a material, characterized in that it is performed within the range of .

10. A method for dry surface treatment of a material, characterized in that in claim 7, the ceramic substrate is made of at least one material selected from the group consisting of boron nitride (BN), alumina (Al2O3), aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), magnesia (MgO), silica (SiO2), tungsten carbide (WC), titanium carbide (TiC), tantalum carbide (TaC), titanium nitride (TiN), and zirconia (ZrO2).

11. A dry surface treatment method for a material according to claim 1, wherein the material is a glass substrate, and the surface is treated by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam for each order from the 1st to the nth order in a vacuum state, or repeating surface treatment under the same conditions as the 1st surface treatment for the nth order after the 1st surface treatment.

12. A dry surface treatment method for a material according to claim 11, characterized in that the first surface treatment is performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases, and the second to n-th surface treatments are performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases.

13. In claim 11, the input voltage of the ion beam is in the range of 0.5 to 3.0 kV, or the amount of the ion beam is 1x10 14 ~5x10 18 ions / cm 2 A method for dry surface treatment of a material, characterized in that it is performed within the range of .

14. A method for dry surface treatment of a material according to claim 11, characterized in that the glass substrate material comprises at least one selected from the group consisting of silicate, borosilicate, and phosphate glasses.

15. A dry surface treatment method for a material according to claim 1, wherein the material is ceramic powder or carbon powder, and the surface treatment is performed by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam in each order from the first to the nth order in a vacuum state, or after the first surface treatment, the surface treatment is repeatedly performed under the same conditions from the second to the nth order by changing at least one of the type of reactive gas, the input voltage of the ion beam, and the amount of the ion beam.

16. A dry surface treatment method for a material according to claim 15, characterized in that the first surface treatment is performed using at least one reactive gas selected from the group consisting of N2, H2, O2, and Ar gases, and the second to n (3≤n≤8) surface treatments are performed using at least one reactive gas selected from the group consisting of N2, H2, and O2 gases.

17. In claim 15, the input voltage of the ion beam is in the range of 0.5 to 2.0 kV, or the amount of the ion beam is 1x10 14 ~5x10 17 ions / cm 2 A method for dry surface treatment of a material, characterized in that it is performed within the range of .

18. A method for dry surface treatment of a material, characterized in that in claim 15, the material comprises at least one selected from the group consisting of carbon nanotubes (CNT), graphite, graphene, boron nitride (BN), alumina (Al2O3), aluminum nitride (AlN), silicon nitride (Si3N4), silicon carbide (SiC), magnesia (MgO), silica (SiO2), tungsten carbide (WC), titanium carbide (TiC), tantalum carbide (TaC), titanium nitride (TiN), and zirconia (ZrO2).

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