TWI461302B - A hydrophobic layer, a method of making the same, a method for producing a hydrophobic layer, and a mold - Google Patents

Description

Hydrophobic layer, preparation method thereof, article with hydrophobic layer and mold manufacturing method

The invention relates to a hydrophobic layer, in particular to a hydrophobic layer which is excellent in chemical resistance and high temperature resistance.

The hydrophilicity or hydrophobicity of the article can be controlled by adjusting the roughness or surface energy of the surface of the article. For example, the Republic of China Certificate No. I334879 patent proposes a hydrophobic layer and a method for preparing the same, which can be formed on the surface of an article by a surface effect, and can exhibit a hydrophobic effect by an increase in surface roughness and a reduction in surface energy.

However, general articles are often processed by acid, alkali, organic solution or high-temperature process during processing, so a hydrophobic layer that is resistant to acids, alkalis, and organic solutions and can withstand high temperature heating is required. To enhance the stability of the hydrophobic layer in the production process or use of the article.

Accordingly, it is an object of the present invention to provide a hydrophobic layer which is excellent in hydrophobicity, has good resistance to acids, alkalis, and organic solutions, and can withstand high-temperature heating, and a method for producing the same.

Thus, the hydrophobic layer of the present invention is formed on the surface of a substrate. The method for preparing the hydrophobic layer comprises the steps of: (A) preparing a substrate; (B) generating a reaction gas, the main component of the reaction gas is a volatile alkyl decane molecule; (C) applying the reaction gas to the a surface of the substrate, and a plasma is applied to the corresponding reaction gas and the substrate; and (D) a hydrophobic layer is formed on the surface of the substrate.

Preferably, the material of the substrate is selected from the group consisting of semiconductor materials, glass, metals, plastics, rubber, high molecular polymers, ceramic materials, fiber materials, rocks, earth materials, cementitious materials, and coatings.

Preferably, in the step (B), the reaction gas is obtained by mixing a precursor gas and mixing with a volatile gas of a reaction solution, the precursor gas is nitrogen, and the main component of the reaction solution is a liquid alkyl decane molecule. .

Preferably, in step (C), the plasma is generated by a plasma unit; the plasma unit includes a cavity and a nozzle connected to the cavity; and the plasma is applied in the step (C) The fine step is: introducing a process gas for generating the plasma into the cavity, and applying a voltage to the nozzle, dissociating the process gas flowing in the nozzle to generate the plasma, and allowing the The plasma is discharged from the nozzle away from a nozzle of the cavity and applied to the reaction gas and the substrate.

On the other hand, the fine step of applying the plasma in the step (C) may also be: introducing a process gas and the reaction gas into the cavity, and applying a voltage to the nozzle to circulate in the nozzle. The process gas is dissociated from the reaction gas to produce the plasma, and the plasma and the reaction gas are led out from the nozzle away from a nozzle of the cavity and applied to the substrate.

Further, the process gas is dry clean air having a pressure of at least 5 kg/cm 2 .

Preferably, the nozzle is at a distance of 5 to 30 cm from the substrate.

Preferably, the hydrophobic layer consists essentially of helium and oxygen.

Preferably, the step (A) further applies a portion of the pattern covering the surface to the substrate; the hydrophobic layer formed in the step (D) covers the layer a pattern layer and a portion of the surface of the substrate not covered by the pattern layer; step (D) further comprising a step (E) of removing the pattern layer and a hydrophobic layer overlying the pattern layer to form a patterned hydrophobic layer Floor.

Further, the material of the pattern layer is a photosensitive photoresist; the step (E) is to remove the pattern layer by an organic solvent and simultaneously peel off the hydrophobic layer on the pattern layer.

Preferably, the hydrophobic layer has a thickness of from 300 nanometers to 500 micrometers.

Another object of the present invention is to provide an article using the aforementioned hydrophobic layer.

Thus, the article of the present invention having a hydrophobic layer comprises a substrate and a hydrophobic layer. The material of the substrate is selected from the group consisting of semiconductor materials, glass, metal, plastic, rubber, high molecular polymer, ceramic material, fiber material, rock, earth material, cement material and paint. The hydrophobic layer is made by the aforementioned production method.

Still another object of the present invention is to provide a method of producing a mold which is produced in accordance with a water repellent layer.

Thus, the method for fabricating the mold of the present invention comprises the steps of: (A) preparing a hydrophobic layer which is formed by the above-mentioned manufacturing method; and (B) forming a metal layer on the surface of the hydrophobic layer by electroforming. The metal layer is attached to the surface of the hydrophobic layer to completely conform to the corresponding surface of the hydrophobic layer; and (C) the metal layer is separated.

Preferably, step (B) comprises the following fine steps: (B1) covering a metal starting layer on the surface of the hydrophobic layer by physical vapor deposition or metallization; and (B2) by electrochemical deposition Starting layer of the metal The metal layer is formed thereon.

The effect of the invention is that the hydrophobic layer formed by the plasma treatment of the volatile alkyl decane molecules has excellent hydrophobicity, chemical resistance and temperature resistance, and enhances the stability of the hydrophobic layer during the manufacturing process of the article. And improve its durability. In addition, the mold made by the hydrophobic layer can transfer the rough surface topography of the hydrophobic layer to a curable plastic material to enhance the hydrophobicity of the plastic material.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments of the accompanying drawings.

1 to 2 show a preferred embodiment of the hydrophobic layer 12 of the present invention and a method of fabricating the same.

Step S1: Prepare an item 1, which may be a mobile phone, an integrated circuit chip, a glass bottle, etc., but is not limited thereto. The article 1 has a substrate 11 made of a semiconductor material, glass, metal, plastic, rubber, polymer, ceramic material, fiber material, rock (such as marble, granite), earth material ( Groups of bricks, tiles, clay, cementitious materials (such as cement, concrete, asphalt, and gypsum) and coatings (such as paints and varnishes).

The substrate 11 may be surface cleaned as needed before performing the next step. For example, if the material of the substrate 11 is 矽, unclean substances such as organic substances, oxides, and metal ions on the surface of the substrate 11 can be removed by RCA (Radio Corporation of America) cleaning technology. But the above substrate The cleaning step of 11 is not a necessary step.

Step S2: generating a reaction gas 3 in which a main component is a volatile alkyl decane molecule. The reaction gas 3 is formed by introducing a precursor gas and mixing it with a volatile gas of a reaction solution. Here, the precursor gas is nitrogen, and the main component of the reaction solution is a liquid alkyl decane molecule.

Specifically, the reaction solution containing the liquid alkyl decane molecule is contained in a closed container (not shown), and nitrogen gas is introduced into the closed container, and the volatilized gaseous alkyl decane molecule is mixed with nitrogen gas to be used. To form the reaction gas 3 of the hydrophobic layer 12.

It should be particularly noted that the precursor gas used in the present embodiment is nitrogen gas, but not limited thereto, and may be a gas such as argon gas or atmosphere, as long as it does not chemically react with the gaseous alkyl decane molecule.

Step S3: applying the reactive gas 3 to a surface of the substrate 11 through an air guiding tube 22, and applying a plasma 5 corresponding to the contact of the reactive gas 3 with the substrate 11, thereby dissociating and modifying the reactive gas 3 A film is deposited on the surface of the substrate 11 to form a hydrophobic layer 12.

Here, the plasma 5 is produced by a plasma unit 21. The plasma unit 21 includes a cavity 211 and a nozzle 212 connected to the cavity 211. After a process gas 4 for generating the plasma 5 is introduced into the cavity 211, a voltage is applied to the nozzle 212 to dissociate the process gas 4 flowing through the nozzle 212 to generate a plasma 5, which is sprayed from the plasma 5 The tube 212 is led away from a nozzle 213 of the cavity 211 and applied to the contact of the reaction gas 3 with the substrate 11.

In the above process, the process gas 4 is a dry clean air (CDA) having a pressure of at least 5 kg/cm 2 , and the nozzle 212 is The distance of the substrate 11 is 5 to 30 cm, and specific values are determined as needed.

It should be particularly noted that the above-mentioned reaction gas 3 can also be directly introduced into the cavity 211 of the plasma unit 21, mixed with the process gas 4, and then dissociated by high voltage to generate the plasma 5, and a hydrophobic layer 12 is formed on the surface of the substrate 11.

Step S4: The hydrophobic layer 12 is formed on the surface of the substrate 11 via the step S3. The thickness of the hydrophobic layer 12 is determined by the time during which the reactive gas 3 and the plasma 5 are applied, and the thickness is preferably from 300 nm to 500 μm, but not limited thereto.

Refer to Table 1 for the characteristic test results of the hydrophobic layer 12. As can be seen from Table 1, the hydrophobic layer 12 is mainly composed of niobium and oxygen, and the surface roughness and the hydrophobic group thereof effectively increase the hydrophobicity, and are high in acid, alkali, organic solution and high. After the temperature treatment, it still has excellent hydrophobicity, and the surface hydrophobicity of the substrate 11 can be improved.

Refer to Figure 3. For example, the article 1 can be an integrated circuit chip including a package case 13 and a plurality of pins 14. Generally, the integrated circuit chip is fixed to a circuit board by soldering (not shown). During the solder reflow heating process, the surface tension of the solder at the bottom end of the pin 14 is reduced, and by capillary phenomenon. As the pin 14 climbs up to the package casing 13, the solder risks damage the package casing 13, which is a phenomenon of "climbing". If the hydrophobic layer 12 is separately formed between the bottom end of the pin 14 and the package case 13 by the foregoing method, since the hydrophobic layer 12 has high temperature resistance and the solder cannot adhere to the surface of the hydrophobic layer 12, Avoid soldering during the heating process of solder reflow to improve process yield.

Refer to Figure 4. In addition, item 1 can also be a mobile phone. The hydrophobic layer 12 is formed on the surface of the mobile phone, and its hydrophobicity enhances the waterproofness of the mobile phone and keeps it clean.

It should be particularly noted that the above-described integrated circuit chip and mobile phone are for illustrative purposes only, and the application field of the hydrophobic layer 12 cannot be limited thereto, as long as the material of the substrate 11 of the article 1 is matched to the hydrophobic layer 12.

1 , 5 and 6 are referred to. The difference between the second preferred embodiment of the present invention and the first preferred embodiment is that the hydrophobic layer 12 is further defined by a semiconductor technology, and the details are as follows.

Step F1: Referring to FIG. 5a, a part of the surface of the substrate 11 is covered by the photolithography to cover the surface. Pattern layer 15. Here, the material of the pattern layer 15 is a photosensitive photoresist.

Step F2: Referring to FIG. 5b, a portion of the surface of the pattern layer 15 and the substrate 11 not covered by the pattern layer 15 is covered with a hydrophobic layer 12 by the method of producing the hydrophobic layer 12 as described above.

Step F3: The pattern layer 15 is removed by an organic solvent and the hydrophobic layer 12 on the pattern layer 15 is simultaneously peeled off. Here, the organic solvent is acetone, but it is not limited thereto as long as the pattern layer 15 can be removed.

Step F4: Referring to Figure 5c, a patterned hydrophobic layer 12 of a particular shape is defined by the pattern layer 15.

As described above, the hydrophobic layer 12 having good chemical resistance and temperature resistance can be produced according to the steps S1 to S3, and the patterned hydrophobic layer 12 can be further formed by the semiconductor process technology from the steps F1 to F4, and the hydrophobic layer 12 is enhanced. The scope of application.

In addition, referring to Figs. 7 to 9, since the hydrophobic layer 12 has a rough surface (Fig. 7) to enhance its hydrophobicity, the present invention also provides a mold 6 for replicating the surface topography of the hydrophobic layer 12. By embossing the surface of the mold 6 on a curable plastic material (such as polydimethyl siloxane, PDMS), the surface topography of the hydrophobic layer 12 can be transferred to the surface of the plastic material to enhance the plasticity. The hydrophobicity of the material.

The following is the step of making the mold 6.

Step M1: Referring to FIG. 9a, a hydrophobic layer 12 is prepared by the aforementioned steps S1 to S3 or steps F1 to F4.

Step M2: Forming a mold 6 on the surface of the hydrophobic layer 12 (Fig. 9b).

This step is based on precision electroforming (Electroforming) With 6. Specifically, a layer of a metal seed layer is first coated on the surface 121 of the hydrophobic layer 12 by physical vapor deposition techniques (eg, evaporation techniques or sputtering techniques) or other metallization techniques. For example, the metal starting layer may be a double-layer metal such as chromium/copper or titanium/copper, but is not limited thereto.

Next, a thick metal layer is deposited on the metal starting layer by Electrochemical Deposition to form the mold 6. The material of the mold 6 may be nickel, nickel cobalt alloy or copper, but not limited thereto.

In the process of electrochemical deposition, the mold 6 is formed by gradually depositing metal from the surface 121 of the hydrophobic layer 12, so that the surface 61 of the mold 6 is complementary in appearance to the surface 121 of the hydrophobic layer 12, and the transfer function can be performed.

Step M3: The mold 6 is separated from the surface 121 of the hydrophobic layer 12 to produce a mold 6 (Fig. 9c).

After the surface 61 of the mold 6 is embossed and solidified on the surface of the plastic material, the surface of the plastic material forms a topography complementary to the surface 61 of the mold 6. The effect of this method is equivalent to the appearance of the surface 121 of the hydrophobic layer 12. Transfer to the surface of the plastic material to increase the hydrophobicity of the plastic material by increasing the surface roughness.

In summary, the hydrophobic layer 12 formed by treating the alkyl decane molecules in a volatile state by the plasma 5 has excellent hydrophobicity, chemical resistance and high temperature tolerance, and can enhance the hydrophobic layer 12 in various articles. The stability of the manufacturing process of 1 and enhance its durability. In addition, since the hydrophobic layer 12 has excellent chemical resistance, it can be patterned by semiconductor technology. The hydrophobic layer 12 is used to enhance its application range. Furthermore, the mold 6 produced by the hydrophobic layer 12 can transfer the rough surface topography of the hydrophobic layer 12 to the surface of the curable plastic material, thereby further enhancing the hydrophobicity of the plastic material.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

1‧‧‧ Items

11‧‧‧Substrate

12‧‧‧hydrophobic layer

121‧‧‧ surface

13‧‧‧Packing

14‧‧‧ pins

15‧‧‧pattern layer

21‧‧‧Plastic unit

211‧‧‧ cavity

212‧‧‧ nozzle

213‧‧‧ mouth

22‧‧‧ air duct

3‧‧‧Reactive gas

4‧‧‧Process Gas

5‧‧‧ Plasma

6‧‧‧Mold

61‧‧‧ surface

S1~S4‧‧‧ Process steps

F1~F4‧‧‧ process steps

M1~M3‧‧‧ process steps

1 is a schematic view showing a preferred embodiment of a method for fabricating a hydrophobic layer of the present invention; FIG. 2 is a flow chart for fabricating the hydrophobic layer; FIG. 3 and FIG. 4 are schematic diagrams of application of the hydrophobic layer; Schematic diagram of the patterned hydrophobic layer; FIG. 6 is a flow chart for fabricating the patterned hydrophobic layer; FIG. 7 is an electrical display of the hydrophobic layer; FIG. 8 is a flow chart for fabricating a mold from the hydrophobic layer; A schematic of the mold.

S1~S4‧‧‧ Process steps

Claims (20)

A method for preparing a hydrophobic layer comprises the steps of: (A) preparing a substrate; (B) generating a reactive gas, the main component of which is a volatile alkyl decane molecule; (C) applying the reactive gas and Plasma is applied to a surface of the substrate; and (D) forms a hydrophobic layer on the surface of the substrate. The method for producing a water repellent layer according to claim 1, wherein the material of the substrate is selected from the group consisting of semiconductor materials, glass, metal, plastic, rubber, high molecular polymer, ceramic material, fiber material, rock, and soil. A group of materials, cementitious materials, and coatings. The method for producing a water-repellent layer according to the first aspect of the invention, wherein the reaction gas is obtained by mixing a precursor gas and mixing with a volatile gas of a reaction solution in the step (B), wherein the precursor gas is Nitrogen, the main component of the reaction solution is a liquid alkyl decane molecule. The method for fabricating a hydrophobic layer according to claim 1, wherein the plasma is produced by a plasma unit in the step (C); the plasma unit includes a cavity and a cavity connected thereto a nozzle; the step (C) of the reaction gas and the plasma are respectively applied to the corresponding surface of the substrate, and the fine step of applying the plasma is: introducing a process gas for generating the plasma The cavity is applied with a voltage to the nozzle to dissociate the process gas flowing in the nozzle to generate the plasma, and the plasma is discharged from the nozzle away from a nozzle of the cavity. The reaction gas and the substrate. The method for producing a water repellent layer according to claim 4, wherein the process gas is dry clean air having a pressure of at least 5 kg/cm 2 . The method for producing a water repellent layer according to claim 4, wherein the nozzle has a distance from the substrate of 5 to 30 cm. The method for fabricating a hydrophobic layer according to claim 1, wherein the plasma is produced by a plasma unit in the step (C); the plasma unit includes a cavity and a cavity connected thereto a nozzle; the fine step of applying the plasma in the step (C) is: introducing a process gas and the reaction gas into the cavity, and applying a voltage to the nozzle to make the flow in the nozzle The process gas is dissociated from the reaction gas to produce the plasma, and the plasma and the reaction gas are discharged from the nozzle away from a nozzle of the cavity to be applied to the substrate. The method for producing a water repellent layer according to claim 7, wherein the process gas is dry clean air having a pressure of at least 5 kg/cm 2 . The method for producing a water repellent layer according to claim 7, wherein the distance between the nozzle and the substrate ranges from 5 to 30 cm. The method for producing a water repellent layer according to claim 1, wherein the hydrophobic layer is mainly composed of ruthenium and oxygen. The method for producing a water repellent layer according to claim 1, wherein the step (A) further applies a portion of the pattern layer covering the surface to the substrate; the hydrophobic layer formed in the step (D) Covering the pattern layer and a portion of the surface of the substrate not covered by the pattern layer; step (D) further comprising a step (E) of removing the pattern layer and covering the pattern layer The hydrophobic layer forms a patterned hydrophobic layer. The method for fabricating a hydrophobic layer according to claim 11, wherein the material of the pattern layer is a photosensitive photoresist; and the step (E) is to remove the pattern layer by an organic solvent and simultaneously peel off the pattern layer. The hydrophobic layer. The method for producing a water repellent layer according to claim 1, wherein the hydrophobic layer has a thickness of from 300 nm to 500 μm. A hydrophobic layer formed on a surface of a substrate prepared by the method of any one of claims 1 to 13. An article having a hydrophobic layer comprising a substrate; and a hydrophobic layer formed on the surface of the substrate, wherein the hydrophobic layer is produced by the method of any one of claims 1 to 13. The article having a water repellent layer according to claim 15, wherein the substrate is a metal pin of an integrated circuit chip, and the hydrophobic layer is formed between the bottom end and the top end of the metal pin. . An article having a hydrophobic layer comprising a substrate; and a hydrophobic layer formed on the surface of the substrate by a plasma treatment of a reactive gas applied to the surface of the substrate, the main component of the reactive gas being in a volatilized state An alkyl decane molecule having a main component of ruthenium and oxygen and having a thickness of from 300 nm to 500 μm. The article having a water repellent layer according to claim 17, wherein the material of the substrate is selected from the group consisting of semiconductor materials, glass, metal, plastic, and rubber. A group of glues, polymers, ceramic materials, fiber materials, rock, earth materials, cementitious materials, and coatings. A method for fabricating a mold comprising the steps of: (A) preparing a water repellent layer prepared by the method of any one of claims 1 to 13; (B) by electroforming The surface of the hydrophobic layer forms a metal layer, the metal layer is attached to the surface of the hydrophobic layer to completely conform to the corresponding surface of the hydrophobic layer; and (C) the metal layer is separated to form the mold. The method for manufacturing a mold according to claim 19, wherein the step (B) comprises the following fine steps: (B1) covering a metal starting layer in the hydrophobic layer by a physical vapor deposition technique or a metal plating technique And (B2) forming the metal layer on the metal starting layer by an electrochemical deposition technique.