WO2014092219A1

WO2014092219A1 - Method for manufacturing gas chromatography chip through multi-etching and method for manufacturing chip laminate

Info

Publication number: WO2014092219A1
Application number: PCT/KR2012/010902
Authority: WO
Inventors: 김상구; 임성민
Original assignee: 한국기초과학지원연구원
Priority date: 2012-12-13
Filing date: 2012-12-14
Publication date: 2014-06-19
Also published as: KR101401342B1

Abstract

The present invention relates to a method for manufacturing a gas chromatography chip through multi-etching and a method for manufacturing a chip laminate and, more specifically, to a gas chromatography chip obtained through multi-etching and a method for manufacturing a gas chromatography chip laminate by laminating the gas chromatography chip.

Description

Method for producing gas chromatography chip through multiple etching and method for manufacturing chip stack

The present invention relates to a method for producing a gas chromatography chip through multiple etching, and a method for manufacturing the chip laminate, and more particularly, to a gas chromatography chip obtained through multiple etching and a gas chromatography chip. A method for producing a gas chromatography chip laminate.

Chromatography relates to analytical techniques that precisely separate each component of a multicomponent mixture, from simple to very complex mixtures.

Chromatography can be classified into various types according to stationary phases and, in particular, mobile phases.

Chromatography may be classified into gas chromatography and liquid chromatography according to the type of the mobile phase. In the present invention, description of the liquid chromatography will be omitted.

In the gas chromatography technique, when a moving phase in which a mixture is dispersed is moved through a stationary phase, the mobile phase is changed according to a difference in attraction force or adsorption force to the stationary phase represented by each mixture included in the mobile phase. Taking advantage of the trailing features.

In other words, in the gas chromatography technique, the mixture to be separated is contained in the mobile phase.

The mixture components move through the stationary phase, where each component of the mixture separates while moving through the stationary phase.

In this case, gas chromatography is particularly characterized by high resolution even for simple, fast, highly sensitive, and thermally stable volatile materials.

Using chromatographic techniques, any mixture can be precisely separated by each component.

At this time, in the case of a gas chromatography chip that analyzes a very complex mixture, a difference in resolution occurs due to the total length of the microchannel, that is, the stationary phase, and the polarity formed in the microchannel (the stationary phase).

On the other hand, the gas chromatography chip conventionally manufactured used DRIE (Dry Reactive Ion Etching) technique.

Here, a method of carving a desired pattern on the substrate (wafer) will be described briefly.

In order to engrave a desired pattern on a substrate, (1) a substrate suitable for engraving a pattern is formed, a thin film is formed of a material suitable for etching on the substrate, and (2) a pattern to be etched on the substrate, that is, a blueprint is prepared. Next, (3) by using an etching (etching) equipment, it is possible to engrave the desired pattern by removing unnecessary portions of the thin film formed on the substrate as the pattern drawn in the schematic.

This pattern engraving can be roughly divided into a dry etching method and a wet etching method.

In the DRIE technique, an etching gas to react with a substrate (wafer) is brought into a plasma state, and the etching gas in the plasma state is collided with the substrate, thereby physically impacting the components forming the substrate and the etching gas. And a dry etching technique that etches a portion of the substrate as a result of a combined chemical reaction or the like.

This dry etching technique has been complicated and difficult to implement due to the complexity of the device.

On the other hand, the wet etching technique is a technique in which a liquid phase flows chemicals or chemicals to the substrate surface to remove unnecessary portions of the thin film formed on the substrate surface, and the implementation apparatus is relatively simple and inexpensive compared to the dry etching technique. There is an advantage.

The prior art related to the present invention is Republic of Korea Patent No. 10-0243995 (2000.02.01. Notification).

Therefore, an object of the present invention is to provide a method for producing a gas chromatography chip using a transparent substrate and using an inexpensive wet etching method.

At this time, since the gas chromatography chip of the present invention using a transparent substrate cannot obtain a microchannel of a desired depth through a single etching, it is preferable to perform multiple etching.

It is also an object of the present invention to effectively bond the substrates in a simple manner to provide a seal between the substrates.

The present invention also aims to control the polarity of the stationary phase formed in the microchannels on the substrate.

Moreover, an object of this invention is to provide the gas chromatography chip laminated body which laminated | stacked the gas chromatography chip obtained through multiple etching in multiple layers, as well as the manufacturing method of the single gas chromatography chip obtained through multiple etching.

The problem to be solved by the present invention is not limited to the problem (s) mentioned above, and other object (s) not mentioned will be clearly understood by those skilled in the art from the following description.

In order to solve the above problems, a method of manufacturing a gas chromatography chip through multiple etching of the present invention, (A) preparing a top substrate and a lower substrate; (B) forming a micro channel pattern portion on opposite one or both surfaces of the upper substrate or the lower substrate; (C) etching the micro channel pattern portion three or more times to form a micro channel; (D) forming a gas supply connection on a surface opposite the substrate surface on which the micro channel pattern portion is formed; (E) forming a gas exhaust connection on an opposite surface of the substrate surface on which the micro channel pattern portion is formed or on an opposite surface of the opposite substrate on which the micro channel pattern portion is not formed; (F) applying a stationary phase on the inner surface of the substrate on which the micro channel pattern portion is formed by spin coating; And (G) manufacturing a gas chromatography chip by joining the coated surface of the substrate to which the stationary phase is coated with the opposite surface of the substrate to which the stationary phase is not applied, wherein the microchannel pattern unit has a circular cross section. A microchannel extending continuously from said gas supply connection to said gas discharge connection; The gas supply connection portion is formed in a tapered shape in which a gas supply port side is wide and its width is narrowed as it proceeds to the microchannel; One or more positioning markers are formed on opposite inner surfaces of the upper or lower substrate; A heat transfer part and a temperature control device for controlling the temperature of the substrate; The gas supply connection part and the gas discharge connection part are formed in an EDM method or a sandblast method; The temperature control device is characterized in that to prevent the loss of gas in the micro-channel formed on the substrate by performing a temperature control of the substrate and at the same time by applying a thermal pressure to the substrate.

Here, the material of the substrate is preferably one selected from a glass wafer, a quartz wafer, a polydimethylsiloxane wafer, a silicon wafer, a silicate wafer, a borosilicate wafer, and a fused silica wafer.

In addition, in the step (F), the stationary phase is PDMS, and in order to control the polarity of the microchannel, it is preferable to further include a step of coating one selected from silica gel, alumina, charcoal, molecular sieve, and porous polymer. Do.

In addition, the step (F) may further include a step of sealing the bonding surface of the substrate when the upper substrate and the lower substrate are bonded.

On the other hand, according to the present invention, the gas chromatography chip obtained through the method of manufacturing a gas chromatography chip through multiple etching, the gas supply connection of the preceding gas chromatography chip and the gas supply connection of the following gas chromatography chip to each other A method of manufacturing a gas chromatography chip stack that is connected to extend the length of the microchannel may be provided.

Here, the stationary phase further coated on the stationary phase of the gas chromatography chip may be different for each layer of the gas chromatography chip stack.

Specific details of other embodiments are included in the detailed description and the accompanying drawings.

Advantages and / or features of the present invention and methods for achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the invention is defined only by the scope of the claims.

Throughout the specification, the same reference numerals refer to the same components, it should be understood that the size, position, coupling relationship, etc. of each component constituting the invention may be exaggerated for clarity of the specification.

As mentioned above, according to the manufacturing method of the gas chromatography chip through the multiple etching of this invention, and the manufacturing method of the said chip laminated body, since it produces a gas chromatography chip by a wet etching method, it is economically advantageous.

In addition, according to the present invention, the gas chromatography chip obtained by the present invention is bonded and sealed by a simple and efficient method during substrate bonding.

Further, according to the present invention, the gas chromatography chip obtained by the present invention can adjust the polarity of the fixed phase coated on the microchannel.

Moreover, according to this invention, the gas chromatography chip laminated body which laminated | stacked the gas chromatography chip obtained by this invention in multiple layers can be provided.

1 is a flow chart schematically illustrating a method of manufacturing a gas chromatography chip through multiple etching according to a preferred embodiment of the present invention.

2 is a schematic plan view of a gas chromatography chip obtained through multiple etching, according to a preferred embodiment of the present invention.

3 is a table showing the etching depth of a substrate during multiple etching according to a preferred embodiment of the present invention.

FIG. 4A is a view showing the same flow path width of the gas inlet path of the gas supply connection portion of the gas chromatography chip according to the preferred embodiment of the present invention, and FIG. 4B is the present invention. According to the preferred embodiment of the present invention, the gas supply connection part of the gas chromatography chip obtained through the multiple etching is shown in the form, the width of the flow path of the gas inlet path of the gas supply connection is a diagram showing the tapered shape.

FIG. 5 is a partially enlarged view of a configuration of a gas supply connection of the gas chromatography chip, together with a schematic plan view of a gas chromatography chip obtained through multiple etching according to a preferred embodiment of the present invention.

FIG. 6 shows actual pictures of the gas supply connection, the micro channel, and the gas discharge connection of the gas chromatography chip obtained through multiple etching, and the gas supply connection and the gas discharge connection according to a preferred embodiment of the present invention. A diagram showing a state of a gas supply / discharge connector.

FIG. 7 is a view showing actual gas analysis results of a gas chromatography chip obtained through multiple etching according to a preferred embodiment of the present invention. In the drawings, ECD detection results of chloroform and 4-bromofluorobenzene are shown.

Hereinafter, with reference to the accompanying drawings will be described embodiments of the present invention;

First, it should be understood that in the present invention, 'coating' and 'application', 'wafer' and 'substrate', and 'etching' and 'etching' are used in substantially equivalent meanings, respectively.

Hereinafter, a method of manufacturing a gas chromatography chip through multiple etching according to a preferred embodiment of the present invention will be described with reference to FIG. 1.

As can be seen from Figure 1, according to a preferred embodiment of the present invention, a method of manufacturing a gas chromatography chip through multiple etching, the substrate preparation step (S100), pattern forming step (S110), etching step (S120) , The stationary phase coating step (S130), and the substrate bonding step (S140).

Board Preparation

Substrate preparation step (S100), according to a preferred embodiment of the present invention, is a step of preparing a substrate for use in the method of manufacturing a gas chromatography chip through multiple etching.

Although the substrate is described later, the material is preferably one selected from glass wafers, quartz wafers, polydimethylsiloxane wafers, silicon wafers, silicate wafers, borosilicate wafers, and fused silica wafers, and most preferably borosilicate wafers. desirable.

In addition, the present substrate is preferably a standard 4 inch size, but if necessary, the size of the substrate may be different.

Here, the substrate is preferably separated into an upper substrate and a lower substrate.

Naturally, the thickness of the substrate is not limited otherwise.

In addition, it is preferable to form an Au / Cr deposited film in advance on the substrate to be used in the method of manufacturing a gas chromatography chip through multiple etching according to a preferred embodiment of the present invention.

The upper substrate or the lower substrate is not specified as the substrate on which the deposition film is to be formed.

Since this deposited film can withstand hydrofluoric acid, it can be useful for effective etching in the wet etching described later.

As the deposition equipment used to form the deposition film, an E-Beam Evaporator (Model: ei-5, manufacturer: ULVAC) was used, the thickness of the first deposited Cr film is about 200 ~ 300 Å, its The thickness of the Au film deposited thereon is preferably about 2000 GPa.

Pattern formation

The pattern forming step (S110) is a step of forming a pattern to be engrave on the prepared substrate.

The pattern referred to in this step S110 refers to a pattern similar to that shown in Fig. 2, and preferably, a pattern is formed in advance using a pattern forming program.

As a specific example of pattern formation, using a pattern forming program, a pattern similar to that shown in FIG. 2 is pre-formed, and then the pattern is printed on a blank master (Model Plotter Mask, manufactured by Barco). And a method of etching and etching the substrate 10 by using the blank master as a photo mask used for pattern production of the substrate 10 (FIG. 2) of the present invention.

In this case, a person having ordinary skill in the art may form a desired pattern on the substrate 10 by using a photo mask and a photoresist applied on the substrate 10. You will know well.

SU-8 50 (manufactured by Microchem, USA) may be used as the photoresist.

The SU-8 50 is a negative photoresist, and the coating thickness at this time may be adjusted to 40 to 100 m.

In addition, it is preferable that a position alignment marker as a use for facilitating position alignment at the time of etching of the substrate is also formed at the same time.

A more detailed pattern formation method is mentioned later.

etching

The etching step S120 is a step of etching the substrate in a predetermined pattern shape.

In the etching step (S120), it is preferable to only etch the pattern formed on the substrate.

In this case, the etching may be performed by using the photoresist PR and the wet etching method by using the photomask on which the desired pattern is formed.

In this etching step (S120), the wet etching is preferably repeated at least three times, until a desired etching depth, that is, about 50 μm comes out. This will be described later with reference to FIG. 3.

Stationary phase

The stationary phase coating step S130 is a step of applying a stationary phase, preferably polydimethylsiloxane (PDMS), to the surface of the substrate etched in the etching step (S120).

The PDMS was applied by spin coating using a spin coater as a material that is optically transparent, nonpolar, and non-flammable. A specific spin coating method will be described in more detail in the paragraphs of the following examples.

For reference, it should be noted that the substrate used in the present invention is also optically transparent.

In the present fixed phase application step (S130), in addition to the PDMS described above, a fixed phase having a different polarity may be further applied to the coating layer of the substrate, if necessary.

Examples of stationary phases having different polarities include silica gel, alumina, charcoal, molecular sieves, and porous polymers, and the polarity of the microchannels can be easily adjusted when these are applied as the stationary phase.

Board Bonding

Substrate bonding step S140 is the step of bonding the board | substrate which application | coating of the stationary phase is complete | finished.

At this time, it should be noted that the PDMS coated on either surface of the upper substrate or the lower substrate constituting the substrate not only performs the function of the stationary phase but also acts on the bonding of the substrate of the present invention.

Thus, the PDMS can simultaneously contribute to the role of the stationary phase in the microchannel and the sealing between the upper substrate and the lower substrate.

Alternatively, the PDMS may be coated on both surfaces of the upper substrate and the lower substrate.

Here, the PDMS is a spin using a spin coater, rather than using a method of coating the wall of the microchannel by bonding the upper substrate and the lower substrate, and then pressing-injecting one of the openings of the microchannel. It should be noted that the coating can be applied very simply.

Next, FIG. 2 is a schematic plan view of a gas chromatography chip obtained through multiple etching, according to a preferred embodiment of the present invention.

The gas chromatography chip may include a substrate 10 formed in a circular shape, a

position alignment marker

20 and 30 formed on one surface of the substrate 10, and a gas supply for supplying gas to the gas chromatography chip. The connection portion 40, the discharge connection portion 50 of the gas discharged from the gas chromatography chip, the micro channel 60, and the micro-channel to cover most of the plane of the substrate 10, starting at one side of the substrate 10. The channel 60 includes an extended micro channel pattern portion 70.

As described above, the substrate 10 may be separated into an upper substrate and a lower substrate, and the gas supply connection part 40, the gas discharge connection part 50, the micro channel 60, and the micro channel pattern part may be formed. Each of the 70 substrates may be formed on any one side of the upper substrate and the lower substrate.

Alternatively, these components may be formed on either side of the upper substrate and the lower substrate of the substrate 10 and the remaining portions may be formed on opposite opposing surfaces of the upper substrate and the lower substrate of the substrate 10. It may be.

As described above, the material of the substrate 10 is preferably one selected from a glass wafer, a quartz wafer, a polydimethylsiloxane wafer, a silicon wafer, a silicate wafer, a borosilicate wafer, and a fused silica wafer, and a borosilicate wafer Is most preferred.

In addition, the

alignment markers

20 and 30 are illustrated in the drawing on both sides of the substrate 10 to face each other with the micro channel pattern portion 70 therebetween on the substrate 10. The position of the

position alignment markers

20 and 30 is not limited thereto.

That is, the positions of forming the

alignment markers

20 and 30 may be formed on one surface of the substrate 10 or on one side and the other surface of the substrate 10, and may include at least one or more. have.

Accordingly, the alignment marker may be formed adjacent to one side of the substrate 10, or alternatively, only one side may be formed on one side of the substrate 10, and one side of the substrate 10 may be formed. After cutting, this cut surface can also be used as an auxiliary position alignment marker.

In the drawing, the gas supply connection part 40 is formed at one side of the upper end of the substrate 10, but the formation position may be any other position.

The gas supply connection part 40 is a part used when supplying a mixture gas as a mobile phase to a gas chromatography chip obtained in accordance with a preferred embodiment of the present invention.

The gas supply side connector 80, which will be described later, and the gas supply column 100 (above, see FIG. 6) are connected to the gas supply side of the gas supply connection portion 40, and the mobile phase is connected through the gas supply column 100. Gas is supplied. At this time, it is preferable that a gas supply side connector 80 (see FIG. 6) is provided between the substrate 10 and the gas supply column 100.

The gas supplied to the gas supply connection part 40 flows into the micro channel 60 formed continuously.

The micro channel 60 is a micro channel constituting the micro channel pattern part 70, and serves to continuously flow the gas of the mobile phase flowing from the gas supply connection part 40.

The microchannel pattern portion 70 preferably constitutes a pattern in advance by using a pattern forming program. As described above, the microchannel pattern portion 70 prints the pattern on the blank master, and the blank master is printed on the substrate 10 of the present invention. The substrate 10 is etched (etched) and formed by using as a photo mask used for the pattern production of ().

The width of the micro channel pattern portion 70 formed according to the preferred embodiment of the present invention was about 100 μm.

Therefore, it is obvious that the width of the microchannel 60 formed on the substrate 10 is also substantially the same width.

Meanwhile, the length of the micro channel 60 formed on the substrate 10 may be added or subtracted according to the pattern shape of the micro channel pattern part 70.

In addition, the gas discharge connecting portion 50 is formed in a direction opposite to the extending direction of the gas supply connecting portion 40 formed on one side of the upper end of the substrate 10, but this is not necessarily limited thereto.

That is, in the figure, the gas supply connection part 40 and the gas discharge connection part 60 are respectively shown in the shape of "┑" and "┎", but the gas supply connection part 40 and the gas discharge connection part, respectively. 50 may be formed to face each other like the shape of "┎" and "┑".

In addition, although the gas supply connection part 40 and the gas discharge connection part 50 may be formed by gathering on one surface of the board | substrate 10, in the upper side and the lower side of the board | substrate 10, or the right side and the left side, respectively, It may be formed spaced apart.

Alternatively, one of the gas supply connection part 40 and the gas discharge connection part 50 is formed on one surface of the substrate 10 and the other is formed on the opposite surface of any one side of the substrate 10. May be

The gas exhaust connection portion 50 is a portion where gas as a mobile phase supplied to a gas chromatography chip obtained in accordance with a preferred embodiment of the present invention is discharged.

The gas discharge side connector 90 and the gas discharge column 110 (see FIG. 6), which will be described later, are connected to the gas discharge side of the gas discharge connection unit 50, and the gas discharge side connector 90 and the gas are connected to each other. The mobile phase gas is discharged through the discharge column 110.

The gas discharged to the gas discharge connection unit 50 may be discharged to the outside, alternatively, when the gas chromatography chip stack is configured by stacking the gas chromatography chip, through the gas discharge column 110, It may be supplied to a gas supply connection (not shown) of another gas chromatography chip adjacent or remote.

That is, the gas discharged from the gas discharge side connector provided in the gas discharge connection portion of the preceding gas chromatography chip can be continuously supplied to the gas supply side connector provided in the gas supply connection portion of the following gas chromatography chip.

In the gas chromatography technique, temperature control of the entire apparatus is very important. In particular, in order to analyze the mixture with high resolution, it is necessary to precisely control the temperature of the substrate 10 and the microchannels 60 formed in the substrate 10. have.

To this end, although not shown in the drawings, the

alignment markers

20 and 30, the gas supply connection part 40, the gas discharge connection part 50, and the micro channel 60 and the micro channel pattern formed on the substrate 10 are formed. A heat transfer part may be further formed at portions except the portion 70.

Alternatively, the heat transfer part (not shown) heats the gas supply connection part 40, the gas discharge connection part 50, and the entirety of the micro channel 60 and the micro channel pattern part 70 formed on the substrate 10. It may be formed to be.

In this case, the heat transfer unit is further preferably provided with a temperature control device (not shown).

In the case of the gas chromatography chip according to the present invention, the temperature control device can control the temperature of the gas chromatography chip at high speed and precisely.

In this case, a peltier device may be used for the heat transfer part in consideration of the small size of the substrate 10.

As can be seen in FIG. 3, when the etching was performed once, the depth of the microchannel 60 was about 17 μm to 20 μm (average depth: 18 μm). The depth of 60 deepens to about 42 micrometers-57 micrometers (average depth: 50 micrometers).

The depth of the microchannel 50 formed in the preferred embodiment of the present invention was 50 μm.

In the gas supply flow path shown in FIG. 4A, the flow path itself is formed in parallel, and in the gas supply flow path shown in FIG. It can be seen that a flow path is formed that is widest and narrows toward the right side.

In the present invention, the reason why the shape of the gas inlet path of the gas supply connection part is formed in a tapered shape is that the microchannel 60 of the substrate 10 is formed when a parallel flow path is formed as shown in FIG. This is because the amount of gas that flows through the exhaust gas to the gas exhaust connection part 50 of the substrate 10 is too small.

In FIG. 4B, the gas supply port side is formed to have a width of about 500 μm, and the gas supply port side is reduced to a width of about 100 μm to a starting point of the microchannel pattern part 70, that is, a point where the microchannel 60 starts. It was formed in a tapered shape.

The specific shape is demonstrated with reference to FIG.

As can be seen in Figure 5, according to a preferred embodiment of the present invention, the width of the flow path in the vicinity of the gas supply port 42 formed in the gas supply connection portion 40 of the gas chromatography chip is about 500 ㎛, Since the width | variety of the flow path far from the gas supply port 42 is formed in about 100 micrometers, they comprise the taper-shaped channel part 44. As shown in FIG.

6, in the gas chromatography chip according to the preferred embodiment of the present invention, the gas supply side connector 80 is provided at the gas supply port 42 of the gas supply connection part 40 formed at one side of the substrate 10. It can be seen that the gas discharge side connector 90 is installed at the gas discharge port (not shown) of the gas discharge connection unit 50 formed on the other side of the substrate 10.

In a preferred embodiment of the present invention, as the gas supply side connector 80 and the gas outlet side connector 90, Nanoport Assembly (R) (manufactured by Upchurch Scientific, USA) was used, and the material of these connectors was PEEK (polyether). ether ketone), which satisfies the desired heat resistance condition (mp = 340 ° C.), and no gas leakage from the inside of the substrate 10 occurred even when the gas chromatography chip was subjected to high pressure.

Finally, FIG. 7 is a view showing actual gas analysis results of a gas chromatography chip obtained through multiple etching according to a preferred embodiment of the present invention, in which the ECD detection results of chloroform and 4-bromofluorobenzene are shown. It is shown.

In order to obtain the graph of FIG. 7, as a sample for analysis, 9 µl of chloroform and 1 µl of 4-bromofluorobenzene were mixed, and then hexane was added to add 1/200 of chloroform. Diluted in proportions.

As an analytical instrument, a μECD detector (Model: HP 6890, manufacturer: Agilent, country of manufacture: USA) was used.

In addition, analysis conditions are as follows.

Gas supply temperature: 300 ℃

Carrier Gas: He

Pressure: 1.30 MPa

Split ratio: 50: 1

Feed amount: 1 μl

Used column: Micro fab column (2 m x 0.10 mm ID x 0.1 μm)

Temperature gradient: 40 ℃ (2 min) → 10 ℃ / min → 120 ℃ (10 min)

Detector temperature: 300 ℃

As can be seen in FIG. 7, the first peak of the graph is clearly shown as chloroform, and the second peak of the graph is clearly shown as 4-bromofluorobenzene.

Next, a method of manufacturing a gas chromatography chip and a laminate thereof according to a preferred embodiment of the present invention will be described.

In this regard, since it has been described with reference to FIG. 1, it is to be understood that the description may be omitted or the descriptions thereof will be omitted.

First, a substrate consisting of an upper substrate and a lower substrate is prepared.

At this time, the material of the substrate is preferably one selected from a glass wafer, a quartz wafer, a polydimethylsiloxane wafer, a silicon wafer, a silicate wafer, a borosilicate wafer, and a fused silica wafer, and most preferably a borosilicate wafer.

As described above, a photoresist PR and a wet etching method are applied to the borosilicate wafer using a mask on which a desired pattern is formed to form a microchannel pattern portion having a width of about 100 μm.

The width of the microchannels in the mask was 0.1 mm, the diameter of the gas supply and gas outlet connections was 0.5 mm, and the length of the entire microchannel was 6054 mm.

As described above, the wet etching at this time is preferably repeated at least three times or more until a desired etching depth, that is, about 50 μm, is obtained.

Here, the microchannel 60 or the microchannel pattern portion 70 may be formed on one side of one of the upper and lower substrates constituting the substrate 10 or the surfaces of both sides of the upper and lower substrates facing each other. It can be formed on.

In addition, since the etching is repeated with reference to the

alignment markers

20 and 30 formed on the substrate 10 as described above, the microchannel 60 and the microchannel pattern portion 70 having a desired pattern have a constant depth and width. Can be etched precisely and in engagement with each other.

As a result, the cross section of the microchannel 60 obtained can be circular.

Using the above technique, as described above, since the masking layer or other special equipment required in the existing DRIE technique is not required, the microchannel pattern portion 70 is formed on the substrate 10 in a simple manner inexpensively. can do.

Next, polydimethylsiloxane (PDMS) is applied as a stationary phase and as an application for bonding / sealing the upper substrate and the lower substrate.

At this time, PDMS was applied by spin coating using a spin coater as a material having optically transparent, non-polar and non-flammable characteristics.

The spin coater had a rotation speed of about 4000 to 8000 RPM and a rotation duration of about 1 second during the spin coating.

In addition, in order to lower the viscosity of PDMS, it was diluted with toluene at a ratio of 1: 1 or 1: 2 (v / v), and thus, the coating height of PDMS was also suppressed to the maximum level.

According to the exemplary embodiment of the present invention, spin coating is performed only on one surface of the upper substrate or the lower substrate constituting the substrate 10, and both substrates of the upper substrate and the lower substrate are bonded without applying to the other surface. In the oven, it heated at the temperature of 70 degreeC for about 1 hour, and bonded together completely.

At this time, the PDMS is preferably coated on either side of the upper substrate or the lower substrate constituting the substrate, alternatively may be coated on both sides.

This coated PDMS not only performs the function of the stationary phase but can also be used directly for the bonding of silicate wafers, thereby simultaneously contributing to the flow of gas in the microchannel 60 and the sealing between the substrate 10.

That is, the PDMS is a technically difficult method of forming a gas chromatography chip and then applying pressure injection to either the gas supply connection 40 or the gas discharge connection 50 to coat the wall of the microchannel 60. Rather, it can be produced by a simple coating method using a spin coater, it can be seen that it is very economical.

Here, as described above, if necessary, a fixed phase having a different polarity may be further applied to the coating layer of the substrate 10.

Examples of stationary phases having different polarities may include silica gel, alumina, charcoal, molecular sieves, and porous polymers, and the polarities of the microchannels 60 may be easily adjusted when they are applied as a stationary phase.

In addition, the stationary phases having different polarities may be applied to either the upper substrate or the lower substrate of the substrate 10, or may be applied to the entire microchannel 60.

Furthermore, when forming a gas chromatography chip laminated body, the same stationary phase may be apply | coated to each gas chromatography chip, and a different stationary phase may be apply | coated to each gas chromatography chip.

As described above, the chip fabrication in the preferred embodiment of the present invention uses a wet etching technique, unlike in the conventional dry etching technique (DRIE), so that a spin coater having a low cost and simple structure can be used to simplify the process. Yet economically effective.

According to a preferred embodiment of the present invention, the specifications of the substrate 10 used in the gas chromatography chip are as follows.

Substrate Size: 4 inches

Size of gas supply port: 500 ㎛

Size of gas outlet: 500 μm

Micro channel width: 100 μm

Substrate Material: Borosilicate Wafer

Here, it should be noted that the size of the gas supply port is 500 μm, the width of the micro channel is 100 μm, and thus the flow path from the gas supply port to the micro channel is tapered.

Next, a method of forming a gas supply port 42 formed at the gas supply connection part 40 of the gas chromatography chip and a gas discharge port (not shown) formed at the gas discharge connection part 50 according to a preferred embodiment of the present invention. Explain.

First, the gas supply port and the gas discharge port can be accurately implemented even by sand blasting (sand blasting), but the sand blasting method is very inefficient in order to produce a small amount, according to a preferred embodiment of the present invention, The gas outlet was fabricated using an electrical EDM (Electrical Discharge Machining) technique.

At this time, 5 M KOH solution was made, and then the gas chromatography chip of the present invention was completely immersed in the KOH solution (8 mm or more), and 40 V / 3 A current was flowed.

As needed, the electrode for electric discharge machining, a solution, etc. were changed suitably.

The gas supply port and the gas outlet may be simultaneously formed on one side of the gas chromatography chip, one of them may be formed on one side, and the other may be formed on the other side.

The former has the advantage of convenient operation, and the latter can be very advantageous when forming gas chromatography chip laminates.

Next, a column for supplying the gas mixture to be analyzed was connected to the gas chromatography chip obtained according to the preferred embodiment of the present invention.

To this end, as shown in FIG. 6, the gas supply side connector 80 is installed at the gas supply port 42 of the gas supply connection part 40 formed at one side of the gas chromatography chip according to the preferred embodiment of the present invention. The gas discharge side connector 90 was installed at the gas discharge port (not shown) of the gas discharge connection unit 50 formed on the other side of the chip.

The gas supply side connector 80 and the gas discharge side connector 90 may be connected to a gas supply column 100 and a gas discharge column 110 that are in charge of supplying gas from the outside, respectively.

The gas supply column 100 is a column for fluidly supplying a gas including a gas of a mobile phase and a mixture to be analyzed, and a gas discharge column 110 discharges the gas to the outside or the gas chromatography chip stack. In this case, the column is connected to the gas supply connection of another gas chromatography chip.

In addition, since application | coating of PDMS, bonding of a board | substrate, vapor deposition of Au / Cr, etc. were mentioned above, description is abbreviate | omitted.

In addition, the analysis performance of the gas chromatography chip according to the preferred embodiment of the present invention manufactured as described above has also been described with reference to FIG. 7.

Here, in order to measure the analytical performance of the gas chromatography chip obtained by the method of manufacturing the gas chromatography chip through the multiple etching of the present invention, and the method of manufacturing the chip laminate, the detection is connected to the gas chromatography chip. Devices may be further included, such as a flame ionization detector (FID), an electron capture detector (ECD), and a mass spectrometer.

ECD is mainly useful for the detection of compounds containing halogen elements (eg, F, Cl, Br, I), mainly for the detection of pesticides, PCBs, N ₂ O gas and the like. FID is mainly used for the analysis of organic compounds such as HC, TCE, PCE and the like.

In addition, in the gas chromatography chip obtained in accordance with the preferred embodiment of the present invention, as described above, a heat transfer part may be further formed for temperature control.

The heat transfer part may be formed in a region where an accessory of the gas chromatography chip is not formed, or may be formed to heat the entire gas chromatography chip.

Moreover, as mentioned above, it is preferable that the temperature control apparatus is further provided in the said heat transfer part.

Therefore, in the case of the gas chromatography chip according to the present invention, since the temperature of the gas chromatography chip can be controlled at high speed and precisely by the temperature control device, the temperature control is immediate compared to the conventional gas chromatography technique. Because it is effectively controlled, very sharp peaks can be obtained in the analysis of gas mixtures.

In this case, in consideration of the small size of the gas chromatography chip, the heat transfer unit may use a peltier device.

In addition, the heat transfer part not only regulates the temperature of the gas chromatography chip, but also serves to prevent gas loss in the microchannel by applying thermal pressure to the junction between the upper substrate and the lower substrate constituting the gas chromatography chip.

This is because the heat applied to the gas chromatography chip enhances the adhesion of the PDMS applied between the upper substrate and the lower substrate.

While specific embodiments of the present invention have been described so far, various modifications are possible without departing from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below, but also by the equivalents of the claims.

As described above, the present invention has been described by way of limited embodiments and drawings, but the present invention is not limited to the above-described embodiments, which can be variously modified and modified by those skilled in the art to which the present invention pertains. Modifications are possible.

Accordingly, the spirit of the present invention should be understood only by the claims set forth below, and all equivalent or equivalent modifications thereof will belong to the scope of the present invention.

According to the method for producing a gas chromatography chip through the multiple etching of the present invention, and the method for producing the chip laminate, it is economically advantageous because the gas chromatography chip is produced by the wet etching method.

S100: Substrate Preparation Step

S110: pattern forming step

S120: etching step

S130: stationary phase application step

S140: Substrate Bonding Step

10: substrate

20, 30: position alignment marker

40: gas supply connection

42: gas supply port

44: tapered channel portion

50: gas exhaust connection

60: microchannel

70: microchannel pattern portion

80: gas supply side connector

90: gas discharge connector

100: gas supply column

110: gas discharge column

Claims

(A) preparing an upper substrate and a lower substrate;

(B) forming a micro channel pattern portion on opposite one or both surfaces of the upper substrate or the lower substrate;

(C) etching the micro channel pattern portion three or more times to form a micro channel;

(D) forming a gas supply connection on a surface opposite the substrate surface on which the micro channel pattern portion is formed;

(E) forming a gas exhaust connection on an opposite surface of the substrate surface on which the micro channel pattern portion is formed or on an opposite surface of the opposite substrate on which the micro channel pattern portion is not formed;

(F) applying a stationary phase on the inner surface of the substrate on which the micro channel pattern portion is formed by spin coating; And

(G) manufacturing a gas chromatography chip by bonding the application surface of the substrate on which the stationary phase has been applied with the opposite surface of the substrate on which the stationary phase is not applied;

The micro channel pattern portion is formed in a micro channel having a circular cross section and extending continuously from the gas supply connection portion to the gas discharge connection portion;

The gas supply connection portion is formed in a tapered shape in which a gas supply port side is wide and its width is narrowed as it proceeds to the microchannel;

One or more positioning markers are formed on opposite inner surfaces of the upper or lower substrate;

A heat transfer part and a temperature control device for controlling the temperature of the substrate;

The gas supply connection part and the gas discharge connection part are formed in an EDM method or a sandblast method;

The temperature control device is characterized in that to prevent the loss of gas in the micro-channel formed in the substrate by applying a thermal pressure to the substrate while performing the temperature control of the substrate,

Method for producing a gas chromatography chip through multiple etching.
The method of claim 1,

The material of the substrate,

Characterized in that the glass wafer, quartz wafer, polydimethylsiloxane wafer, silicon wafer, silicate wafer, borosilicate wafer and fused silica wafer,

Method for producing a gas chromatography chip through multiple etching.
The method of claim 2,

In the step (F), the stationary phase is PDMS,

To control the polarity of the micro-channel, further comprising the step of further coating one selected from silica gel, alumina, charcoal, molecular sieve, and porous polymer,

Method for producing a gas chromatography chip through multiple etching.
The method of claim 3, wherein

In the step (F), when the upper substrate and the lower substrate is bonded, the fixed phase further comprises the step of sealing (sealing) the bonding surface of the substrate,

Method for producing a gas chromatography chip through multiple etching.
A gas chromatography chip obtained through a method for producing a gas chromatography chip through multiple etching according to any one of claims 1 to 4,

Characterized in that the length of the microchannel is extended by connecting the gas outlet connection of the preceding gas chromatography chip with the gas supply connection of the following gas chromatography chip.

Method for producing a gas chromatography chip laminate.
The method of claim 5,

The stationary phase further coated on the stationary phase may be different for each layer of the gas chromatography chip stack,

Method for producing a gas chromatography chip laminate.