KR101226624B1 - Method for manufacturing glass substrate of hydrophilic/hydrophobic patterning - Google Patents

Abstract

The present invention is to produce a water-repellent / hydrophilic patterning substrate on a glass substrate by using the LPD method, the water-repellent surface is made by the surface modification using a FAS ZnO thin film having a rough surface, the hydrophilic surface is irradiated with ultraviolet rays FAS Was made by removing it. Hexagonal ZnO rod was grown vertically on the glass substrate coated with ZnO seed layer by LPD method. As deposition time increased, the diameter and thickness of ZnO rod increased. The surface structure, thickness, crystal structure, transmittance and contact angle of the prepared ZnO thin films were measured using FE-SEM, XRD, UV-vis and contact angle meter. The hydrophilic ZnO thin film having a contact angle of 20 ° to 30 ° was changed to a surface having a contact angle of 145 ° to 161 ° by FAS surface treatment. The prepared water repellent surface was patterned by irradiating ultraviolet rays using a shadow mask having a dot size of 300 μm and 3 mm. Finally, the water-repellent surface irradiated with ultraviolet rays turned into a hydrophilic surface.

Hydrophilic, water-repellent, patterning

Description

METHOD FOR MANUFACTURING GLASS SUBSTRATE OF HYDROPHILIC / HYDROPHOBIC PATTERNING}

The present invention relates to a method for producing a water / hydrophilic patterned substrate on a glass substrate using the LPD method.

Bio-biochips are of great importance as the demand for medical welfare in society increases due to the aging of the population, but low sensitivity, reproducibility, and stability of biomolecules must be solved.

In order to solve the problems of the prior art, an object of the present invention is to manufacture a hydrophilic / water-repellent patterned glass substrate which can be easily immobilized with biomolecules by using it as a substrate material for a biochip.

In order to achieve the above object, the present invention cleans and hydrophilizes a substrate, forms a ZnO thin film on top of the substrate, and performs a FAS treatment on the surface of the Zno thin film to cover a shadow mask and irradiate ultraviolet rays to pattern the pattern. Provided is a manufacturing method for producing a water repellent patterned glass substrate.

In addition, the present invention provides a hydrophilic / water repellent patterned glass substrate having a ZnO thin film by FAS treatment and covering a shadow mask on the thin film and irradiating with ultraviolet rays, the portions irradiated by ultraviolet rays exhibit hydrophilicity, and the non-irradiated portions exhibit water repellency. .

The present invention can produce a hydrophilic / water-repellent patterned glass substrate, and when used as a substrate material for biochips, has the effect of easily and selectively immobilizing biomolecules to more clearly analyze the results.

BRIEF DESCRIPTION OF THE DRAWINGS The above objects, features and advantages will become more apparent through the following examples in conjunction with the accompanying drawings. Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Bio-biochips are of great importance as the demand for medical welfare in society increases due to the aging of the population, but low sensitivity, reproducibility, and stability of biomolecules must be solved. Substrate materials for biochips that need to measure a lot of information quickly with a small amount of sample include a substrate coated with slide glass, silicon, nylon, organic polymers (PMMA, PC, Teflon), Pt or Au. In addition, in order to selectively immobilize biomolecules exhibiting hydrophilic properties, a substrate is used by modifying a hydrophilic or water repellent surface. In order to manufacture a super water-repellent thin film, as can be seen in the lotus leaf structure, a process of first forming a rough surface having an uneven structure on the surface of the substrate and a process of modifying the surface using a compound having a low surface energy is used. Required. SiO ₂ , TiO ₂ , and ZnO thin films are widely used as a film having a rough surface of nanostructures necessary for producing a super water-repellent film. In particular, ZnO is applied to gas sensors, catalytic varistors, electrophotographic photosensitizers, and fluorescent displays because it has properties such as semiconductivity, piezoelectricity, fluorescence, and photoconductivity. These characteristics are more excellent when ZnO has nano size. . ZnO thin films are manufactured by electrochemical deposition, suputtering, sol-gel, chemical vapor deposition, and pulsed-laser deposition.

In order to hydrophobically modify the surface of the uneven structure, fluorine or silicon compounds are widely used, and among them, fluoroalkyltrimethoxysilane (FAS, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ , which has a very low surface energy (~ 8 mJ / m ₂ ) Si (OCH ₃ ) ₃ ,) is widely used. In the present invention, the microstructure and optical properties of ZnO rods grown by deposition time were measured by using liquid phase deposition (LPD), a solution process method, in order to manufacture a water / hydrophilic patterned substrate. After that, the contact angle characteristics of the prepared thin film were confirmed. The prepared superhydrophobic thin film was covered with a shadow mask and irradiated with ultraviolet rays to prepare a water / hydrophilic patterned substrate.

In order to coat the ZnO seed layer on the glass substrate, the molar ratio of zinc acetate dehydrate (Zn (CH ₃ COO) _{2 ·} 2H ₂ O, Wako), monoethanolamine (MEA, Wako), 2-methoxyehanol (Wako) was 0.02: 0.02: 0.51. After mixing with stirring for 2 hours at 60 ℃ to prepare a solution. For cleaning and hydrophilic treatment of the glass substrate before coating, the substrate was immersed in KOH (1.0 wt.%) Solution and distilled water and sonicated for 5 minutes. A glass substrate was deposited on the prepared coating solution, and dip coating was performed at a pulling speed of 1.0 mm / s. The coated glass substrate was dried at room temperature, dried at 90 ° C. for 1 hour, and finally heat treated at 400 ° C. for 1 hour. A wurtzite-type ZnO film was prepared on the seed layer by LPD method, and zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ 6H ₂ O was mixed with H ₂ O (95 ml) and NaOH _{( aq )} (25%, 5 ml) in a mixed solvent. ): ammonium chloride (NH ₄ Cl): urea (Co (NH ₂ ) ₂ ) = 1: 2: 1: A coating solution was prepared by mixing in a molar ratio. The glass substrate coated with the Seed layer was kept soaked in an aqueous ZnO coating solution at 90 ° C. for 1 to 2.5 hours. Then, the coated substrate was cleaned using distilled water. As a water repellent solution for preparing a super water-repellent ZnO thin film, 2.0 wt.% Of fluoroalkyltrimethoxysilane (FAS) was added to hexane. A glass substrate coated with a ZnO thin film was deposited on the water repellent solution and left at room temperature for 20 minutes. The super water-repellent ZnO thin film prepared for water repellent / hydrophilic patterning was covered with a shadow mask (dot size: 300㎛, 3.0mm) and irradiated with UV light (20W, 352nm) for 2 hours. The water repellent part was removed.

A field emission scanning electron microscope (FE-SEM, JSM 6700, JEOL) was used to confirm the surface microstructure and thickness of the prepared thin film. The crystal structure of ZnO was analyzed by X-ray diffraction (XRD, KFX-987228). -SE, Mac Science). The transmittance of the thin film was measured using a UV-Vis spectrophotometer (V-570, JASCO), and a contact angle meter (Easy Drop, KRUSS) was used to check the water contact angle on the thin film surface.

1 shows the microstructure of a ZnO film having a hexagonal rod shape grown on the surface of a glass substrate in an ZnO aqueous solution by LPD method. The prepared ZnO rods were grown in the vertical direction and the rod diameter was increased from about 50 nm to 300 nm as the deposition time increased. Figure 2 shows the change in thickness of the thin film grown with the change of deposition time. As the deposition time was increased to 1.0h, 1.5h, 2.0h, 2.5h, the thickness of the prepared thin film was grown to about 0.225, 1.434, 2.250, 3.010 μm.

3 is an XRD pattern of a thin film grown by depositing a seed layer coated glass substrate in a ZnO aqueous solution for 2.5 hours. The prepared thin film was confirmed to be hexagonal wurtzite-type ZnO having a (002) strong diffraction peak. Figure 4 shows the transmittance of the ZnO thin film prepared according to the deposition time. The thin film prepared by immersion in an aqueous solution of ZnO for 1 hour has a transmittance of about 89% in the visible region. As shown in (a) and (a) of FIG. 1, a thin film having a diameter of about 50 nm and a thickness of about 225 nm has almost no decrease in transmittance in the visible region, but the deposition time is increased to 1.5 hours. As a result, it was found that the transmittance significantly decreased with the growth of the ZnO rod size and the film thickness. In addition, the ZnO-coated glass substrate having UV blocking properties, as shown in the drawing, the film prepared by immersion for more than 1.5 hours showed excellent UV blocking properties. The water contact angle of ZnO rod-coated glass substrates prepared by deposition for 1.0 to 2.5 hours showed hydrophilic surface characteristics with contact angles of about 20 ° to 30 ° and decreased slightly with increasing deposition time. Showed a tendency.

This is because, as confirmed in FIG. 1, as the deposition time increases, the area of contact with water increases as the diameter of the grown ZnO rod increases. The ZnO thin film prepared above was immersed in a water repellent FAS solution to water repellent treatment. The thin film water-repelled by FAS solution showed a high contact angle of about 161 ° to 145 ° as shown in FIG. In particular, the ZnO thin film prepared by immersion for 1 hour, 1.5 hours showed a super water-repellent property of more than 155 °.

6 is an image showing the contact angle before and after the FAS treatment for the ZnO thin film prepared by immersion for 1 hour. The contact angle after FAS treatment improved from 30 ° to 161 °. In order to manufacture a water repellent / hydrophilic patterned substrate, a shadow mask was placed on a super water-repellent ZnO thin film manufactured by FAS and irradiated with UV. ZnO, which has a photocatalytic property of decomposing organic matter, decomposes the water repellent of the UV-irradiated portion, and the portion is changed to a surface showing hydrophilic property in water repellency.

FIG. 7A is an optical microscope image of a sample patterned by placing a mask having a dot size of 300 μm on a ZnO-coated substrate prepared by immersion for 2 hours. When water was dropped on the water-repellent / hydrophilic patterned substrate, only water where the FAS was decomposed by ZnO was found to show the water-repellent and hydrophilic regions. FIG. 7B is an image of a substrate manufactured by using a mask having a 3 mm dot size of a super water-repellent substrate having a high transmittance prepared by immersion for 1 hour. As can be seen from the figure, the water droplets on the substrate are selectively buried only in the hydrophilic part, and it shows a high transmittance in which the letters under the glass substrate are clearly visible. If these water-repellent / hydrophilic patterned substrates are used as substrate materials for biochips, the results can be analyzed much more clearly by easily and selectively immobilizing biomolecules.

 A water-repellent / hydrophilic patterned substrate coated with ZnO rods was prepared using a solution process method. The ZnO thin film prepared by coating a ZnO seed layer on a glass substrate and then depositing the substrate in an aqueous ZnO solution by LPD method exhibited a wurtzite-type ZnO crystal structure having a 002 diffraction peak, and the deposition time was 2.5 at 1 hour. It was confirmed that the diameter of the prepared ZnO rod increases with time, from about 50 nm to 300 nm, and the thickness of the film increases from 225 nm to 3.01 μm. Thin films treated with FAS were converted from a hydrophilic surface of 20 ° to 30 ° to a 145 ° to 161 ° water repellent surface. In particular, ZnO rod-coated glass substrate prepared by immersion for 1 hour showed high transmittance of 89% in visible light and super water-repellent contact angle of 161 °. The water-repellent / hydrophilic substrate prepared by placing a shadow mask on the substrate and irradiating ultraviolet rays and removing the water repellent of the portion irradiated with ultraviolet rays by using the photocatalytic properties of ZnO was clearly patterned to a dot size of 300 μm and 3 mm.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. Will be clear to those who have knowledge of.

1 is an FE-SEM image of a ZnO thin film according to deposition time in an aqueous solution.

2 is a cross-sectional image of a ZnO thin film according to the deposition time in an aqueous solution.

3 is a diagram showing an XRD pattern of a ZnO thin film grown for 2 hours of deposition time.

4 is a diagram showing a transmission spectrum of a ZnO thin film according to deposition time in an aqueous solution.

5 is a view showing the contact angle of the ZnO thin film before and after the FAS treatment.

6 is a droplet image before and after the FAS treatment for the ZnO thin film prepared by immersion for 1 hour.

7 is a hydrophilic / water repellent patterned image of a ZnO thin film grown using a shadow mask.

8 is a view showing a transparent super water-repellent superhydrophilic patterning process.

Claims (9)

Cleaning and hydrophilizing the substrate Forming a ZnO thin film on top of the substrate After the ZnO thin film was immersed in the FAS solution for 1 to 1.5 hours and subjected to FAS treatment cover the shadow mask and irradiate with UV The ZnO thin film is formed by coating a ZnO seed layer on the substrate, and then coating the substrate on which the seed layer is formed with a mixed solvent of H ₂ O (95 ml) and NaOH _(aq) (25%, 5 ml) in zinc nitrate hexahydrate (Zn). (NO ₃ ) ₂ 6H ₂ O): ammonium chloride (NH ₄ Cl): urea (Co (NH ₂ ) ₂ ) = 1: 2: Mixing in a molar ratio of 1: 1 to form by immersion in the coating solution Method for producing hydrophilic / water repellent patterned glass substrate. The method of claim 1, Cleaning and hydrophilic treatment of the substrate After dip coating the substrate in a mixed solution of KOH solution and distilled water, and then sequentially dried at room temperature, 90 ℃ and heat treated at 400 ℃ Method for producing hydrophilic / water repellent patterned glass substrate. delete The method of claim 1, wherein the seed layer Mix zinc acetate dehydrate (Zn (CH ₃ COO) _{2 ·} 2H ₂ O, Wako), monoethanolamine (MEA, Wako), 2-methoxyehanol (Wako) at molar ratio of 0.02: 0.02: 0.51, and then stir at 60 ℃ for 2 hours. Formed by immersing the substrate in a solution Method for producing hydrophilic / water repellent patterned glass substrate. The method of claim 1, The FAS process, Hexane is added to the FAS solution to form a water repellent solution, and the substrate on which the ZnO thin film is formed is deposited on the water repellent solution. Method for producing hydrophilic / water repellent patterned glass substrate. The method of claim 1, Dot size of the shadow mask is 300㎛, 3.0mm Method for producing hydrophilic / water repellent patterned glass substrate. The method of claim 1, The transmittance of the ZnO thin film is As the deposition time increases, the thickness of the ZnO thin film increases, The transmittance decreases in the visible region by increasing the thickness. Method for producing hydrophilic / water repellent patterned glass substrate. The method of claim 1, The transmittance of the ZnO thin film is As the deposition time increases from 1 hour to 2.5 hours, the thickness of the ZnO thin film increases, The transmittance decreases at a wavelength of 380 nm to 780 nm in the visible region by increasing the thickness of the ZnO thin film. Method for producing hydrophilic / water repellent patterned glass substrate. A hydrophilic / water repellent patterning part produced by the manufacturing method of any one of claims 1, 2 and 4 to 8, irradiated with ultraviolet light, exhibits hydrophilicity, and non-irradiated part exhibits water repellency. Glass substrate.

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