阅读说明：本技术 具备三维纳米结构的具有固定相的微型分离器及其制造方法 (Micro separator with stationary phase having three-dimensional nanostructure and method for manufacturing the same ) 是由 全锡佑 沈煐晳 赵东辉 杰得·纳丁·昂 于 2019-10-02 设计创作，主要内容包括：所公开的一种用于气相色谱的微型分离器包括：基底基板,其具有沟槽；通道柱,其设置于所述沟槽内；和盖构件,其与所述基底基板结合且覆盖所述通道柱。所述通道柱包括固定相,所述固定相具有有序且三维地相互连接的孔。(A micro-separator for gas chromatography is disclosed comprising: a base substrate having a trench; a channel pillar disposed within the trench; and a cover member coupled with the base substrate and covering the channel pillars. The channel column includes a stationary phase having pores that are interconnected in an ordered and three-dimensional manner.)

1. A micro-separator for gas chromatography comprising:

a base substrate having a trench;

a channel pillar disposed within the trench; and

a cover member coupled with the base substrate and covering the channel pillars,

wherein the channel column comprises a stationary phase having pores that are interconnected in an ordered and three-dimensional manner.

2. The micro-separator for gas chromatography according to claim 1, wherein the base substrate comprises at least one selected from the group consisting of silicon, glass, quartz, sapphire, and polymers.

3. The micro-separator for gas chromatography according to claim 1, wherein the stationary phase comprises at least one selected from the group consisting of a polymer, a metal, and a ceramic.

4. The micro-separator for gas chromatography according to claim 1, wherein the stationary phase is disposed on a bottom surface of the groove and spaced apart from the cover member to define a gas flow path.

5. The micro-separator for gas chromatography according to claim 1, wherein the stationary phase comprises a lower stationary phase disposed on a bottom surface of the groove and an upper stationary phase bonded to a lower surface of the cover member, wherein at least a portion of the upper stationary phase is spaced apart from the lower stationary phase to define a gas flow path between the lower stationary phase and the upper stationary phase.

6. The micro-separator for gas chromatography according to claim 1, wherein the stationary phase completely fills the channel column.

7. The micro-separator for gas chromatography according to claim 1, wherein a bottom surface of the trench is concave and an upper surface of the stationary phase is recessed along the bottom surface of the trench.

8. A gas chromatography system comprising:

the micro-separator of any one of claims 1 to 7;

a preconcentrator providing the concentrated sample to the micro-separator; and

a sensor that detects the kind or component of the sample separated by the micro-separator.

9. A method of manufacturing a micro-separator for gas chromatography, the method comprising:

forming a photosensitive film in the groove of the base substrate;

exposing the photosensitive film by using a phase mask to provide light distributed three-dimensionally; and

and developing the exposed photosensitive film to form a polymer stationary phase of a three-dimensional nanostructure, wherein the three-dimensional nanostructure is provided with ordered and interconnected pores.

10. The manufacturing method of the micro-separator for gas chromatography according to claim 9, wherein the phase mask is provided on a lower surface of the base substrate.

11. The method of manufacturing a micro-separator for gas chromatography according to claim 9, wherein a photo-dielectric member is disposed on the photosensitive film, and the phase mask is disposed on the photo-dielectric member.

12. The method of manufacturing a micro-separator for gas chromatography according to claim 11, wherein at least a portion of the optical medium member is disposed in the groove, and the optical medium member comprises at least one selected from the group consisting of a lubricant for matching refractive index, glass, PDMS (polydimethylsiloxane), PUA (polyurethane acrylate), and PFPE (perfluoropolyether).

13. The method of manufacturing a micro-separator for gas chromatography according to claim 11, further comprising:

forming a surrogate stationary phase that fills at least a portion of the pores of the polymeric stationary phase and comprises a metal or a ceramic; and

removing the polymer stationary phase.

14. The method of manufacturing a micro-separator for gas chromatography according to claim 10, further comprising:

forming an upper stationary phase on a surface of the cover member, the upper stationary phase having a three-dimensional nanostructure with ordered and interconnected pores; and

combining the cover member with the base substrate such that the upper stationary phase is inserted into the groove of the base substrate.

Technical Field

The invention relates to a micro-separator for gas chromatography. More particularly, the present invention relates to a micro-separator provided with a stationary phase having a three-dimensional nanostructure for gas chromatography, and a method of manufacturing the same.

Background

Gas Chromatography (GC) is an analytical method in which a sample (analyte) is carried by a carrier Gas and passed through a column to separate mixed components into individual components. The GC system consists of a carrier gas, an inlet, a material separation column, an oven, a detector, and a data system, and the performance of the material separation column may be an important factor in determining the performance of the overall system.

In the material separation column, the chemical equilibrium, adsorption and distribution of the gaseous sample loaded with the carrier gas (mobile phase), which are different from those of the stationary phase, are caused by the difference in chemical properties between the gaseous sample and the stationary phase coated in the column, thereby generating a time difference in passing through the column. Thus, the material may be separated.

Generally, as the material separation column, a packed column or a capillary column is used. The packed column consists of an inert material, a solid support typically formed of a diatomaceous earth material, and a coated liquid stationary phase. Because the interior of the tube is completely filled, the packed column can have a relatively large diameter and a relatively short length, with an inner diameter of about 2 to 4 millimeters and a length of about 1.5 to 10 meters. Capillary columns can be divided into Wall Coated Open Tubular (WCOT) columns Coated with a liquid stationary phase and Porous Layer Open Tubular (PLOT) columns Coated with a solid Porous material with a thin film stationary phase on the inner Wall. Typical stationary phase materials for detecting a gaseous sample may include polysiloxane (PE-1, PE-5, etc.), polyethylene glycol (PE-Wax, FFAP (trade name)), Polydimethylsiloxane (PDMS), silica nanoparticles, and the like. In a capillary column, since the stationary phase is coated on the inner wall of the tube, it can have a narrower diameter (within 1 mm) and a longer length (several tens of meters) than a packed column to increase the probability of collision of gaseous samples.

The conventional GC system has advantages of superior reliability and superior separation efficiency compared to other separation systems. However, they have a large volume on the order of cubic meters due to a long column of several meters long, an oven for maintaining the proper temperature of the column, and a signal processing system. Therefore, they have inherent difficulties in their application to the accurate analysis of unknown samples collected at the scene of an event, such as explosives and drugs. In order to overcome the above problems, studies on u-Gas Chromatography (u-GC) using Micro Electro Mechanical Systems (MEMS) technology have recently been reported. For example, semi-packed columns with rectangular columnar arrays within a sputtering open-ended column have been shown to separate short hydrocarbons from natural gas (J.Visal et al, "silica sputtering as a novel collection stationary phase deposition for MEMS gas chromatography columns: feasibility and first separation", J.Chromatogr.A 1218, 3262-. As another example, separation of saturated and unsaturated hydrocarbon chains has been successfully performed using silica or graphite sputtered micro-columns with metal wires (temperature programming) (R. Haudebourg et al, "temperature programmed sputtered micro-mechanical gas chromatography columns: Rapid separation methods in oilfield applications," anal. chem.85,114-120,2013). Furthermore, the possibility of practical application of micro-GC was proposed by integrating ZIF-8-PVA cryogels (cryogels) into laser etched acrylic micro-separator columns for the separation of polycyclic aromatic hydrocarbons (C.Siritham et al, "preconcentrator-separator two-in-one in-line system for polycyclic aromatic hydrocarbon analysis", Talanta 167,573-582, 2017).

However, the material separators of the prior studies have a small reaction specific surface area with most gaseous samples, and non-uniform stacking occurs when silica nanoparticles or the like are used. As a result, due to material problems, deterioration of separation performance such as a peak having left-right asymmetry, peak broadening (peak broadening), tailing effect (tailing effect), and the like occurs. Therefore, they are hardly used in actual devices.

Patent documents:

(1) korean patent application No. 10-2015-0100209

Non-patent documents:

(1)Micromech.Microeng.2009,19,065032

(2)Micromech.Microeng.2017,27,035012

(3)Environ.Sci.Technol.2012,46,6065

(4)Chem.Commun.,2015,51,8920

(5)Anal.Chem.2013,85,114

(6)Anal.Chem.2018,90,13133

disclosure of Invention

It is an object of the present invention to provide a micro-separator for gas chromatography having a stationary phase with three-dimensional nanostructures by integrating three-dimensional nanostructures into a micro-column for a material separator and using it as the stationary phase, to overcome the inherent technical limitations of conventional gas chromatography systems.

It is another object of the present invention to provide a method of manufacturing a micro-separator for gas chromatography having a stationary phase with a three-dimensional nanostructure.

This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

According to an exemplary embodiment for achieving the object of the present invention, a micro-separator for gas chromatography comprises: a base substrate having a trench; a channel pillar disposed within the trench; and a cover member coupled with the base substrate and covering the channel pillars. The channel column includes a stationary phase having pores that are interconnected in an ordered and three-dimensional manner.

In an exemplary embodiment, the base substrate includes at least one selected from the group consisting of silicon, glass, quartz, sapphire, and a polymer.

In an exemplary embodiment, the stationary phase includes at least one selected from the group consisting of a polymer, a metal, and a ceramic.

In an exemplary embodiment, the stationary phase is disposed on a bottom surface of the groove and spaced apart from the cover member to define a gas flow path.

In an exemplary embodiment, the stationary phase includes a lower stationary phase disposed on a bottom surface of the groove and an upper stationary phase combined with a lower surface of the cover member. At least a portion of the upper stationary phase is spaced apart from the lower stationary phase to define a gas flow path between the lower stationary phase and the upper stationary phase.

In an exemplary embodiment, the stationary phase completely fills the channel column.

In an exemplary embodiment, a bottom surface of the groove is concave, and an upper surface of the stationary phase is recessed along the bottom surface of the groove.

According to an exemplary embodiment, a gas chromatography system comprises: a micro-separator; a preconcentrator providing the concentrated sample to the micro-separator; and a sensor that detects the kind or component of the sample separated by the micro-separator.

According to an exemplary embodiment, a method of fabricating a micro-separator for gas chromatography includes: forming a photosensitive film in the groove of the base substrate; exposing the photosensitive film by using a phase mask to provide light distributed three-dimensionally; and developing the exposed photosensitive film to form a polymer stationary phase of a three-dimensional nanostructure having pores that are ordered and interconnected.

In an exemplary embodiment, the phase mask is disposed on a lower surface of the base substrate.

In an exemplary embodiment, an optical medium member is disposed on the photosensitive film, and the phase mask is disposed on the optical medium member.

In an exemplary embodiment, at least a portion of the optical medium member is disposed in the groove, and the optical medium member includes at least one selected from the group consisting of a lubricant for matching refractive index, glass, PDMS (polydimethylsiloxane), PUA (polyurethane acrylate), and PFPE (perfluoropolyether).

In an exemplary embodiment, the method of manufacturing a micro-separator for gas chromatography further comprises: forming a surrogate stationary phase that fills at least a portion of the pores of the polymeric stationary phase and comprises a metal or a ceramic; and removing the polymeric stationary phase.

In an exemplary embodiment, the method of manufacturing a micro-separator for gas chromatography further comprises: forming an upper stationary phase on a surface of the cover member, the upper stationary phase having a three-dimensional nanostructure with ordered and interconnected pores; and combining the cover member with the base substrate such that the upper stationary phase is inserted into the groove of the base substrate.

According to the above-described embodiment of the present invention, the stationary phase of the micro-separator may have a three-dimensional network structure in which pores of a nanometer order are three-dimensionally connected to each other and periodically arranged. Thus, efficient mass transfer can be performed in the structure, and the surface area of the structure can be maximized. Therefore, the separation performance of the separator can be improved. Therefore, even if a shorter column is used, the separator can have performance equal to or greater than that of a conventional large-sized separator. Therefore, the separator can be miniaturized to a portable level. Can be implemented as a gas chromatography system that can be used in a variety of locations where fast feedback is required.

In addition, since the separator has a three-dimensional ordered porous structure suitable for surface reaction of the gaseous sample and the stationary phase, the number of adsorption/separation molecules can be increased by 10 to 1000 times due to an increase in specific surface area, as compared to conventional micro-sized ordered porous bodies. This can increase the detection limit by a factor of 10 to 100000. Thus, peak intensity, peak sharpness, and resolution may be increased when the separated sample may be detected by the sensor. In addition, since the length of the channel column is reduced, additional heating for inducing a surface reaction can be omitted, so that separation can be performed at a low temperature. Therefore, power consumption can be reduced, and the entire process for manufacturing the system can be simplified. Therefore, the method is advantageous in mass production.

In addition, selectivity to a sample and physical properties such as heat resistance can be increased by material substitution of the stationary phase.

Drawings

Fig. 1 is a plan view illustrating a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

Fig. 2 is a sectional view taken along line I-I' in fig. 1.

Fig. 3 to 6 are sectional views illustrating a method of manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

Fig. 7 is a perspective view illustrating a step for replacing a stationary phase material in a method for manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

Fig. 8 to 10 are sectional views illustrating a method of manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

Fig. 11 to 14 are sectional views illustrating a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

FIG. 15 is a top view illustrating a gas chromatography system according to an exemplary embodiment.

Fig. 16 shows a planar digital picture and a Scanning Electron Microscope (SEM) picture of a polymer stationary phase of a three-dimensional nanostructure according to example 1.

Fig. 17 is a graph showing the results of separation tests of example 1, example 2, and comparative example 1(Agilent J & W GC column).

Fig. 18 is a partial enlarged view showing a separation test result of example 1 at room temperature.

Detailed Description

Hereinafter, a micro-separator for gas chromatography and a method thereof according to embodiments will be described more fully with reference to the accompanying drawings, in which some embodiments are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, components, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, components, and/or groups thereof.

Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Fig. 1 is a plan view illustrating a micro-separator for gas chromatography according to an exemplary embodiment of the present invention. Fig. 2 is a sectional view taken along line I-I' in fig. 1.

Referring to fig. 1 and 2, a micro-separator 100 for gas chromatography according to the present invention includes a channel column 120. The channel pillars 120 may have various shapes and lengths according to the purpose, separation target, and the like of the micro-separator 100. For example, the channel post 120 may have a spiral shape, a radial shape, etc., as well as the saw tooth shape shown in fig. 1. For example, the length of the passage post 120 may be several centimeters to several tens of meters. In addition, the width of the channel pillar 120 may be 200 to 1000 micrometers, and the depth of the channel pillar 120 may be 100 to 500 micrometers.

The micro-separator 100 includes a base substrate 110. A groove may be formed along the surface of the base substrate 110 in order to form a space for the channel pillar 120. Both ends of the channel column 120 may be connected to an inlet 130 into which the gaseous sample is injected and an outlet 140 from which the separated gaseous sample is discharged, respectively.

For example, the base substrate 110 may include silicon, glass, quartz, sapphire, polymer, metal, and the like. For example, the polymer may include PMMA (polymethyl methacrylate), PET (polyethylene terephthalate), PC (polycarbonate), PI (polyimide), PA (polyamide), PP (polypropylene), and the like.

The channel column 120 includes a stationary phase 122. In an exemplary embodiment, the micro-separator 100 may be of the capillary column type. The channel column 120 having the capillary column type may have an empty space in which the stationary phase 122 is not disposed, and the empty space may be defined as a gas flow path 124.

In an exemplary embodiment, the stationary phase 122 may have a three-dimensional porous nanostructure. Preferably, the stationary phase 122 may have pores that are interconnected in an ordered and three-dimensional manner. The stationary phase 122 may comprise various materials, such as metals, ceramics, semiconductors, organic compounds, and the like. For example, the stationary phase 122 may include cerium oxide (CeO)₂) Alumina (Al)₂O₃) Titanium oxide (TiO)₂) Zirconium oxide (ZrO)₂) Zinc oxide (ZnO), titanium nitride (TiN), or combinations thereof. In another exemplary embodiment, the stationary phase 122 may include gold, silver, platinum, palladium, ruthenium, rhodium, iridium, vanadium, nickel, cobalt, copper, tungsten, molybdenum, manganese, aluminum, iron, or combinations thereof. For example, the polymer may include epoxy, acrylic, phenolic, and the like, which may be crosslinked. However, the stationary phase material usable in the present invention is not limited thereto, and various materials may be used according to the separation target and the like.

In an exemplary embodiment, the micro-separator 100 may further include a cover member 150 coupled to the base substrate 110 and covering the channel post 129.

In an exemplary embodiment, the micro-separator 100 may further include a heating member 152. The heating member 152 may include a metal having high thermal conductivity, such as copper, aluminum, nickel, silver, and the like. For example, the heating member 152 may adjust or maintain the temperature in the channel column 120 by joule heating.

In an exemplary embodiment, the heating member 152 may be combined with the upper surface of the cover member 150. However, the exemplary embodiments of the present invention are not limited thereto. The heating member 152 may be combined with the lower surface of the cover member 150, or combined with the lower surface or the side surface of the base substrate 110. Further, the heating member 152 may be omitted.

In one exemplary embodiment, the stationary phase 122 may have a three-dimensional network structure in which pores of a nanometer order are three-dimensionally connected to each other and periodically arranged. Thus, efficient mass transfer can be performed in the structure, and the surface area of the structure can be maximized. Therefore, the separation performance of the separator can be improved. Therefore, even if a shorter column is used, the separator can have performance equal to or greater than that of a conventional large-sized separator. Therefore, the separator can be miniaturized to a portable level.

In addition, since the separator has a three-dimensional ordered porous structure suitable for surface reaction of the gaseous sample and the stationary phase, the number of adsorption/separation molecules can be increased by 10 to 1000 times due to an increase in specific surface area, as compared to conventional micro-sized ordered porous bodies. This can increase the detection limit by a factor of 10 to 100000. Thus, peak intensity, peak sharpness, and resolution may be increased when the separated sample may be detected by the sensor. In addition, since the length of the channel column is reduced, additional heating for inducing a surface reaction can be omitted, so that separation can be performed at a low temperature. Therefore, power consumption can be reduced, and the entire process for manufacturing the system can be simplified. Therefore, the method is advantageous in mass production.

Fig. 3 to 6 are sectional views illustrating a method of manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention. Fig. 7 is a perspective view illustrating a step for replacing a stationary phase material in a method for manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

To form the stationary phase having the three-dimensional nanostructure according to the exemplary embodiments of the present invention, various methods such as self-assembly, interference lithography, stereolithography, holographic lithography, direct ink writing, 3D printing, etc. may be used. The disclosures of korean patent application nos. 2018-0041150 and 2016-0116160 and korean patent nos. 1391730, 1400363, 1358988, 19119906 and 1902382 are incorporated herein by reference to explain methods of forming a stationary phase having a three-dimensional nanostructure.

Hereinafter, an exemplary embodiment using proximity-field nano-patterning (PnP) will be explained.

Referring to fig. 3, a photosensitive film 128 is formed in the groove of the base substrate 110. The trench may be formed by various methods. For example, Deep Reactive Ion Etching (DRIE), LIGA (Lithographie, Galvano-forming, and Abforming, lithography and Vanoforming), and the like.

The photosensitive film 128 may be formed, for example, by soft-baking the photosensitive composition at a temperature ranging from about 50 ℃ to about 100 ℃ after disposing the photosensitive composition in the groove. The baking time may be appropriately adjusted, and may be, for example, about 5 minutes to 3 hours.

For example, the photosensitive composition for forming the photosensitive film 128 may include an organic-inorganic hybrid material that is crosslinkable in response to light, a hydrogel, a phenol resin, an epoxy resin, and the like. In particular, examples of photosensitive compositions can include photoresists, such as the SU-9 series, KMPR series, ma-N1400 series, supplied by MicroChem, and the like.

Various methods may be used to provide the photosensitive composition in the trench. In view of the width of the channel, a method of flowing the photosensitive composition through a micropipette or syringe may be preferably used.

Referring to fig. 4 and 5, a PnP process is performed to form the polymeric stationary phase 122 a. In an exemplary embodiment, the phase mask 170 may contact the lower surface of the base substrate 110, and then the three-dimensionally distributed light may be irradiated onto the photosensitive film 128 through the phase mask 170 and the base substrate 110.

In the PnP process, the photosensitive film 128 may be patterned, for example, by using a periodic three-dimensional distribution of light generated by interference of light through a phase mask including an elastomer material. For example, when the flexible elastomer-based phase mask 170 having the concavo-convex grid structure on the surface thereof may contact the base substrate 110, the phase mask 170 may spontaneously adhere (e.g., conformal-contact) to the base substrate 110 due to van der waals forces.

When laser light having a wavelength range similar to the grating period of the phase mask 170 is irradiated onto the surface of the phase mask 170, a three-dimensional distribution of light may be formed by a Talbot effect. When a negative photoresist is used, crosslinking may occur at a strongly light-irradiated portion of the photoresist due to constructive interference of light, and other weakly light-irradiated portions of the photoresist may be dissolved and removed in a developing process due to insufficient exposure. After the final drying process, a porous polymer material may be obtained, which may contain periodic three-dimensional structures of several hundred nanometers (nm) to several micrometers (μm), depending on the wavelength of the laser and the design of the phase mask.

In an exemplary embodiment, the aperture and periodicity of the polymer stationary phase 122a may be adjusted by controlling the pattern period of the phase mask 170 and the wavelength of incident light in the PnP process.

For example, the phase mask 170 used in the PnP process may include PDMS (polydimethylsiloxane), PUA (polyurethane acrylate), PEPE (perfluorpolyether), and the like.

For example, an i-line (365 nm) light source may be used for exposure, and the exposure dose energy may be 10 to 30mJ/cm²Depending on the thickness of the exposed layer.

For example, the exposed photosensitive film 128 may be baked at a temperature in a range of about 50 ℃ to about 100 ℃. The baking time may be appropriately adjusted, and may be, for example, about 5 minutes to 3 hours.

For example, when the photosensitive film 128 includes a negative photoresist, the exposed portions of the photosensitive film 128 may remain, while the unexposed portions thereof may be removed by a developing solution. As a result, a polymeric stationary phase 122a including three-dimensional nanopores may be formed.

Examples of the developer may include, for example, PGMEA (propylene glycol monomethyl ether acetate), ethyl lactate, diacetone alcohol, TMAH (tetramethylammonium hydroxide), a Su-8 developer, and the like. In addition, rinsing with an alcohol such as ethanol, isopropanol, or the like may also be performed.

In an exemplary embodiment, the polymeric stationary phase 122a may have a three-dimensional network structure in which nanoscale pores in the range of about 1 nanometer to about 2000 nanometers are three-dimensionally interconnected and arranged to have a periodicity.

In an exemplary embodiment, the polymeric stationary phase 122a may be used as a stationary phase for separation. However, the polymeric stationary phase 122a may be used as a template for material substitution. For example, referring to fig. 6 and 7, at least a portion of the pores of the polymeric stationary phase 122a may be filled to form the surrogate stationary phase 122b, and then the polymeric stationary phase 122a may be removed, so that the surrogate stationary phase 122b may have pores corresponding to the polymeric stationary phase 122 a.

The surrogate stationary phase 122b may include various materials according to purposes. For example, the surrogate stationary phase 122b can include a ceramic or a metal. For example, the ceramic may include cerium oxide (CeO)₂) Alumina (Al)₂O₃) Titanium oxide (TiO)₂) Zirconium oxide (ZrO)₂) Zinc oxide (ZnO), and titanium nitride (TiN), or combinations thereof. The metal may include gold, silver, platinum, palladium, ruthenium, rhodium, iridium, vanadium, nickel, cobalt, copper, tungsten, molybdenum, manganese, aluminum, iron, or combinations thereof.

The surrogate stationary phase 122b can be formed by various methods. For example, the surrogate stationary phase 122b may be formed by chemical vapor deposition, atomic layer deposition, electroplating, electroless plate, metal-infiltrated (metal-infiltrated) or the like.

In an exemplary embodiment, the surrogate stationary phase 122b can include a ceramic such as alumina and can be formed by atomic layer deposition. For example, zinc diethyl, H, etc. can be used₂O, ammonia, tetrakis (dimethylamido) titanium (IV) (tetrakis (dimethylamido) titanium, TDMAT), Trimethylaluminum (TMA), and the like. However, examples of the present inventionThe exemplary embodiment is not limited thereto, and various precursors known to be suitable for the target material may be used. For example, atomic layer deposition may be repeatedly performed at 40 to 100 ℃ for 100 to 1000 cycles depending on the desired thickness. The stationary phase having a three-dimensional nanostructure including a ceramic may have high stability against heat and temperature changes.

In an exemplary embodiment, the surrogate stationary phase 122b may completely fill the pores of the polymeric stationary phase 122a to have the inverse shape of the polymeric stationary phase 122 a. However, exemplary embodiments are not limited thereto, and the substitute stationary phase 122b may be coated on the inner wall of the pores of the polymer stationary phase 122a in a thin film shape, thereby forming a nanoshell structure.

The polymer stationary phase 122a serving as a template may be removed by heat treatment, ultrasonic treatment using an organic solvent, plasma etching, wet etching, or the like. For example, the temperature in the heat treatment may be increased by 1 to 5 ℃/minute, and the heat treatment may be performed at 200 to 600 ℃ for at least 10 minutes to remove the polymeric stationary phase 122 a. When the rate of raising the temperature is too high, the polymeric stationary phase 122a may deform, thereby causing damage to the three-dimensional structure of the surrogate stationary phase 122 b.

In one exemplary embodiment, the reaction activating material may be further provided on the surface of the polymeric stationary phase 122a or the surrogate stationary phase 122 b. A reaction activating material may be provided to increase reactivity or absorbability to a target sample, thereby improving separation performance. For example, the reaction activating material may be coated on the surfaces of the polymer stationary phase 122a and the substitute stationary phase 122b by a solution method.

Various materials may be used for the reaction activating material depending on the detection target. For example, as shown in the following chemical formula 1-1, when the detection object is a substance (for example, cocaine, heroin, morphine, methamphetamine, ecstasy, ketamine, etc.) containing a functional group of a hydrogen bond acceptor (indicated by a dotted line), a material containing a functional group of a hydrogen bond donor as shown in the following chemical formula 1-2 may be used as the reaction activating material.

[ chemical formula 1-1]

[ chemical formulas 1-2]

Further, when the detection object is a material (e.g., LSD, hemp, morphine, etc.) containing a functional group of a charge transfer donor (shown by a dotted line) shown in the following chemical formula 2-1, a material containing a functional group of a charge transfer acceptor shown in the following chemical formula 2-2 may be used as the reaction activating material.

[ chemical formula 2-1]

[ chemical formula 2-2]

Various known materials containing a functional group shown in the above chemical formula 1-2 or 2-2 can be used as the reaction activating material.

After the polymer stationary phase 122a or the substitute stationary phase 122b is formed, the cover member 150 is bonded on the base substrate 110.

The cover member 150 may include the same or similar material as the base substrate 110, such as silicon, glass, quartz, sapphire, polymer, metal, and the like. The base substrate 110 and the cover member 150 may be bonded to each other by a known wafer bonding method such as anodic bonding, crystal bonding, melting, adhesive, or the like. In an exemplary embodiment, the base substrate 110 may include silicon, and the cover member 150 may include glass.

Fig. 8 to 10 are sectional views illustrating a method of manufacturing a micro-separator for gas chromatography according to an exemplary embodiment of the present invention.

Referring to fig. 8, the optical medium member 160 may be disposed on the photosensitive film 128 disposed in the groove. In the PnP process, the optical medium member 160 may efficiently transmit light to the photosensitive film 128.

As described above, the upper surface of the photosensitive film 128 is lower than the upper surface of the base substrate 110, so that an empty space where the stationary phase is not disposed may be formed in the channel column having the capillary type. In this case, even if the phase mask is closely attached to the base substrate 110, a gap may be generated between the photosensitive film 128 and the phase mask. Therefore, the uniformity of patterning may be deteriorated. Further, although the PnP process is performed using exposure through the lower surface in fig. 4, when a member having low transparency, such as a metal film or a heating member 152, is disposed on the rear surface of the base substrate 110 as shown in fig. 8, it is difficult to use exposure through the lower surface.

In an exemplary embodiment, in order to overcome the limitation of the patterning failure and the post-transmissive exposure, the optical medium member 160 may be disposed between the phase mask and the photosensitive film 128, so that the patterning may be uniformly performed. In addition, the uniformity of patterning can be further optimized by light reflection of the metal thin film disposed thereunder.

In an exemplary embodiment, the optical media member 160 may include a polymer film including a polymer. Preferably, the optical medium member 160 may include the same polymer as the phase mask, and may include, for example, PDMS (polydimethylsiloxane), PUA (polyurethane acrylate), PFPE (perfluoropolyether), and the like. To form the optical media member 160, a polymer composition including a polymer or monomer composition may be coated on the photosensitive film 128 and then may be dried or cured.

In another exemplary embodiment, the optical media member 160 may include glass. For example, the optical media member 160 may include protrusions corresponding to the grooves, and the protrusions may be aligned to be inserted into the grooves. Since the refractive index of glass (1.46 or more) is greater than that of PDMS (refractive index: 1.45), the optical medium member 160 may have a refractive index more similar to that of the photosensitive film 128 (refractive index: e.g., 1.65 to 1.7, and 1.67 of Su-8 (trade name)). Therefore, light distributed three-dimensionally can be transmitted to the photosensitive film 128 more efficiently than the case of using PDMS. Preferably, soda lime glass having a refractive index greater than that of general glass may be used for the optical medium member 160.

In another exemplary embodiment, the optical medium member 160 may include a lubricant for matching refractive index. The lubricant for matching the refractive index may be a liquid mixture, and may be provided to fill the groove.

Referring to fig. 9, a PnP process is performed to form a polymer stationary phase 122 a. In an exemplary embodiment, the phase mask 170 may contact the upper surface of the optical medium member 160, and then the three-dimensionally distributed light may be irradiated onto the photosensitive film 128 through the phase mask 170 and the optical medium member 160 to form the polymer stationary phase 122 a.

In an exemplary embodiment, the stationary phase of the micro-separator of the present invention may not be formed in the groove of the base substrate but formed on the cover member. For example, referring to fig. 10, after the stationary phase 126 having the three-dimensional nanostructure is formed in a pattern on the surface of the cover member 150, the cover member 150 may be combined with the base substrate 110 such that the stationary phase 126 is inserted into the groove of the base substrate 110.

Referring to fig. 11, the stationary phase 126 may be combined with a lower surface of the cover member 150, and the gas flow path 124 may be defined between the stationary phase 126 and a bottom surface of the groove.

Fig. 12 and 13 illustrate exemplary embodiments for increasing the contact area between the stationary phase and the sample in the channel column.

Referring to fig. 12, the lower stationary phase 122 is disposed on the bottom surface of the groove of the base substrate 110. The upper stationary phase 126 is disposed on a lower surface of the cover member 150. A gas flow path 124 is defined between the lower stationary phase 122 and the upper stationary phase 126.

Referring to fig. 13, the groove of the base substrate 110 may have a concave cross-section. For example, the grooves may have a semi-circular or triangular cross-section.

When the wettability of the base substrate 110 by the photosensitive composition is increased by the above-described structure (for example, a hydrophilic solvent may be used), the lower stationary phase 12 formed in the groove may have a relatively conformal shape to have a concave upper surface, thereby increasing a contact area with the sample. In addition, the upper stationary phase 126 may be further disposed on a lower surface of the cover member 150, so that the gas flow path 124 may be defined between the lower stationary phase 122 and the upper stationary phase 126.

A micro-separator including a stationary phase having three-dimensional nanostructures according to an exemplary embodiment may be used for a capillary column type including a gas flow path as described above. However, the exemplary embodiments are not limited thereto, and may be used for a packed column type.

For example, referring to fig. 14, the micro-separator includes a channel column 120 disposed in a groove of the base substrate 110, and the channel column 120 may be completely filled with the stationary phase. For example, after forming the lower stationary phase 122 on the bottom surface of the groove of the base substrate 110, the upper stationary phase 126 formed on the surface of the cover member 150, as shown in fig. 10, may be inserted into the groove to obtain the channel column 120 completely filled with the stationary phase. When the PnP process is used to form a stationary phase having a three-dimensional nanostructure, it may be difficult to form a stationary phase that completely fills the trench due to light absorption by the photoresist. According to an exemplary embodiment, the lower stationary phase 122 formed in the groove of the base substrate 110 may be assembled with the upper stationary phase 126 formed on the surface of the cover member 150, so that a stationary phase having a sufficient thickness to fill the groove may be obtained.

Further, the stationary phase having a three-dimensional nanostructure includes pores that are connected to each other in order and three-dimensionally. Therefore, even in the packed column type, the sample is easily moved.

FIG. 15 is a top view illustrating a gas chromatography system according to an exemplary embodiment.

Referring to FIG. 15, a gas chromatography system according to an exemplary embodiment includes a preconcentrator, a micro-separator, and a sensor. The preconcentrator may concentrate the gaseous sample to provide a concentrated sample to the micro-separator. The micro-separator may separate the sample into a plurality of components and may provide the components to the sensor in sequence. The sensor may detect the type and composition of the components provided by the micro-separator.

The micro-separator 100 includes a channel column 120 to separate gaseous samples. The micro-separator 100 includes a base substrate 110, and a groove is formed along a surface of the base substrate 110 to form a space for the channel pillar 120. Both ends of the channel column 120 may be connected to an inlet 130 into which the gaseous sample is injected, and an outlet 140 from which the separated gaseous sample is discharged, respectively. Since the micro-separator 100 has substantially the same configuration as the above-described exemplary embodiment, a more detailed explanation will be omitted.

The pre-concentrator includes a base substrate 210 having a trench. The trough may include a concentrator 212, an inlet 220, and an outlet 230. The three-dimensional porous nanostructure is disposed in concentrator 212. The three-dimensional porous nanostructure includes pores that are connected to each other in an ordered and three-dimensional manner. The three-dimensional porous nanostructures may comprise a variety of materials, such as metals, ceramics, semiconductors, low molecular weight organic compounds, polymers, and the like.

The gaseous sample is injected through inlet 220 and then transferred to concentrator 212. In an exemplary embodiment, the gaseous sample may be injected with a suitable carrier gas. The gaseous sample concentrated by absorption and separation in concentrator 212 may be provided to inlet 130 of the micro-separator through outlet 230. The outlet 230 of the preconcentrator may be connected to the inlet 130 of the micro-separator by connecting the column 10 using a tube or the like.

In another exemplary embodiment, the micro-separator and the pre-concentrator may be disposed in the same substrate. In this case, the grooves formed on the substrate may be used as connection posts instead of the additional tubes. If desired, the stationary phase of the micro-separator and the three-dimensional porous nanostructure of the concentrator 212 may be formed in the same process.

The three-dimensional porous nanostructure of the concentrator 212 may be formed by the same method as the stationary phase of the micro-separator, for example, by the PnP process or the like. Because the three-dimensional nanostructure has a three-dimensionally connected network structure, the three-dimensional nanostructure can ensure uniform and rapid heat transfer and has small weight and high porosity. Therefore, since the three-dimensional nanostructure can heat the sample with low energy and uniformly heat the sample in a short time, the gaseous sample can be discharged with high density in a short time. As a result, the preconcentrator may have optimized concentration performance. In addition, the three-dimensional nanostructures may minimize their backpressure.

For example, the sensor 300 may include a photo ionization detection sensor, a flame ionization detection sensor, an electrochemical sensor, a colorimetric sensor, a surface acoustic wave sensor, or the like, which measures a change in voltage due to electrons dissociated in response to ultraviolet rays applied thereto.

The gas chromatography system according to the exemplary embodiment can be miniaturized to be applied to portable devices that can be used for on-site inspection due to the inclusion of the preconcentrator and the micro-separator including the three-dimensional nanostructure. In addition, materials may be detected that conventional sensor systems may not accurately identify, such as certain drugs, explosives, volatile organic compounds, etc. that are too low in composition in air due to low vapor pressure at room temperature.

Hereinafter, the effects of the present invention will be described with reference to specific embodiments and experiments.

Example 1

After a photoresist composition (trade name: SU-82, manufactured by MicroChem) was run in a groove formed in a glass substrate, it was heated on a hot plate at 50 ℃ to 100 ℃ for 60 minutes. After that, a phase mask formed of PDMS and having a periodic concavo-convex structure was disposed to contact the lower surface of the glass substrate. The phase mask includes holes arranged in a rectangular shape at a pitch of 600 nm. Using about 20mJ/cm²The exposure process is performed with an i-line (365 nm) light source.

Thereafter, the exposed photosensitive film is heated at 50 to 100 ℃ for 10 minutes, and then developed to form a stationary phase of a three-dimensional nanostructure.

Example 2

The glass substrate on which the polymer stationary phase of the three-dimensional nanostructure is formed is placed in a reaction chamber. An atomic layer deposition process was performed at about 80 ℃ using trimethylaluminum as the aluminum precursor. (at 10)^-3Is carried out under a pressure of Torr700 cycles).

Thereafter, after the temperature of the chamber was increased to about 500 ℃ at a rate of 3 ℃/min, heat treatment was performed in an air atmosphere to remove the polymer stationary phase, thereby obtaining three-dimensional nanostructured alumina (Al) in the trenches₂O₃) A stationary phase.

Fig. 16 shows a planar digital picture and a Scanning Electron Microscope (SEM) picture of a polymer stationary phase of a three-dimensional nanostructure according to example 1.

Referring to fig. 16, it can be seen that in the grooves of the glass substrate according to example 1, a three-dimensional nanostructured polymer stationary phase having ordered pores is formed.

Fig. 17 is a graph showing the results of separation tests of example 1, example 2, and comparative example 1(Agilent J & W GC column). Fig. 18 is a partial enlarged view showing a separation test result of example 1 at room temperature. In the experiment, methanol was used as a solvent gas, and a FID sensor was used.

Referring to FIGS. 17 and 18, comparative example 1 did not show separation performance at either room temperature (25 ℃) or high temperature (95 ℃), whereas example 1(3D SU-8) using a polymer stationary phase was able to show separation performance, and example 2(3D Al) using an alumina stationary phase₂O₃) Can exhibit separation performance (occurrence of peak separation) at high temperature. Therefore, it can be noted that according to the exemplary embodiment of the present invention, a low-component sample can be separated in a channel column having a short length (3 cm), and the apparatus and optimized performance of the gas chromatography of the present invention can be expected.

The foregoing is illustrative of embodiments and is not to be construed as limiting thereof. Although a few embodiments have been described, those skilled in the art will readily appreciate that many modifications are possible in the embodiments without materially departing from the novel teachings and advantages of the present inventive concept. Accordingly, all such modifications are intended to be included within the scope of the inventive concept as defined in the claims. Therefore, it is to be understood that the foregoing is illustrative of various embodiments and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed embodiments, as well as other embodiments, are intended to be included within the scope of the appended claims.

The micro-separator according to the exemplary embodiment may be used to detect various gaseous samples, such as drugs, volatile organic compounds, explosive compounds, and the like. For example, the micro-separator may be coupled with a sensor for use in a Portable multi-component gaseous sample detection sensor System, which may be used in a Portable micro-gas chromatography System (Portable μ -GC System), enabling real-time detection of multiple components at various incident sites, such as crimes, terrorist attacks, etc.