JP4846372B2 - Microchemical chip and manufacturing method thereof - Google Patents

Description

  The present invention relates to a microchemical chip and a method for producing the same, and in particular, a microreactor (microfactory), an optical element, a bioreactor, which is formed based on a patterned substrate and performs a reaction / analysis in a minute amount. The present invention relates to a microchemical chip constituting a sensor, a DNA computer, a DNA memory, a biomolecule integrated device, and the like.

Conventionally, various proposals have been made for methods (μTAS, micro total analysis system) for performing reactions and analyzes in minute amounts (see, for example, Non-Patent Document 1 below).
Microchemical chips produced by such a method have been expected to be applied to chemical microdevices such as DNA analysis chips, laboratory-on-chips, microreactors (microfactories), and biosensors. There are a wide variety of applications in the fields of technology, medicine and agriculture.

  From such a background, it can be said that it is indispensable to carry out the reaction in a homogeneous system in order to carry out precise measurement in reaction and synthesis, etc., under conditions that do not cause a difference in concentration and temperature. The use of microchemical chips is desirable.

  Further, since the microchemical chip has a small circuit and a small amount of sample may be used, it is advantageous in terms of resource saving, low cost, and shortening of reaction time.

  As a conventional method for producing a microchemical chip, photolithography for semiconductor microfabrication is widely known. However, since this requires an expensive electron beam drawing apparatus, it has a problem of high cost. It was. There is also a problem that the size of the groove of the chip depends on the performance of the electron beam drawing apparatus.

This method using an electron beam drawing apparatus has an advantage that it is suitable for a mass production process using a mask, but is not suitable for free circuit design.
For this reason, there has been an increasing demand for a microchemical chip and a method for manufacturing the microchemical chip that achieve further resource saving and cost reduction.

In the microchemical chip, for example, a solution containing molecules such as DNA is used as a sample object.
DNA can form its own nanoscale structure by adjusting its base sequence, and it is expected to be applied to the production of molecular-sized electronic devices by performing various reactions using DNA as a framework. ing.

In the analysis or the like related to such DNA, it is necessary to make the side wall hydrophilic so that DNA does not adhere to the side wall of the flow path.
A technique using a hydrophilic resin using a partially esterified polymethacrylic acid as a material has been conventionally proposed (for example, see Patent Document 1 below). However, this is advantageous in terms of mass production because it uses injection molding or the like for the production of circuits, but there is a limit to the production accuracy and size, and a microchemical chip with a scale of several tens to hundreds of nanometers is required. It has a problem that it cannot be formed.

By the way, thermal lithography is known as a low-cost manufacturing method as compared with microfabrication using optical lithography. This is a technique that utilizes the fact that heat is applied to an endothermic layer (which plays the role of a light absorbing layer in the case of laser irradiation), and the characteristics of the portion to which heat is applied via the heat are changed.
Conventionally, a process for recording information by irradiating a laser beam and a method for producing an optical recording medium in which an unrecorded portion is removed by solution etching and a convex process is performed (for example, the following patents) are known. Reference 2).
For example, a mixture of zinc sulfide and silicon oxide is used as an endothermic material that is applied to an optical disk by forming pits smaller than the laser beam spot using thermal lithography technology. The technique to do is also proposed (for example, refer to Patent Documents 3 and 4 below).

A. Manz, et al., Sen. Actuators, B, 1, 244 (1990). JP 2003-159526 A JP 2005-158191 A JP 2005-71564 A JP 2005-100602 A

In the future, it is thought that it will be required to facilitate the fabrication of microchemical chips and further increase the precision, and this will expand the range of applications to various electronic devices including various microreactors and biosensors. ing.
Therefore, in the present invention, the fabrication of a microchemical chip having a structure on the order of nano to several hundreds of nanometers has been facilitated to achieve high accuracy.

In the present invention, a microchemical chip having a storage / conveying unit for storing and transporting a liquid or gaseous sample and a reaction unit for reacting the sample, which are formed by side walls on a support substrate, sidewalls state, and are not formed by etching resistance change material which changes its resistance to etching material by laser beam irradiation or thermal radiation, the etching resistance change material, zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, A microchemical chip comprising a mixture of any of aluminum nitride and silicon oxide is provided.

  According to a second aspect of the present invention, the side wall has a water contact angle of 40 ° or less and is made of the etching resistance changing material.

According to a third aspect of the present invention, in the microchemistry according to the first or second aspect, the reaction portion is formed with a porous portion made of the etching resistance changing material and having at least a part of a spherical shape. Provide chips.

According to a fourth aspect of the present invention, the side wall is formed of an etching resistance changing material whose resistance to an etching material is changed by laser light irradiation, and a laser beam is absorbed under the etching resistance changing material. The microchemical chip according to any one of claims 1 to 3, wherein a light absorption layer made of a material that generates heat is formed.

According to a fifth aspect of the present invention, there is provided the microchemical chip according to the fourth aspect , wherein the light absorption layer is made of a semiconductor or a metal.

According to a sixth aspect of the present invention, a microchemical chip having a storage / conveying section for storing and transporting a liquid or gaseous sample and a reaction section for reacting the sample, which are formed by side walls, is formed on a support substrate. A method of forming an etching resistance changing material comprising a mixture of zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, aluminum nitride and silicon oxide on the support substrate with respect to the formation of the side wall. And a step of irradiating a part or all of the support substrate on which the etching resistance changing material is formed with a laser beam or applying a heat treatment to change the etching resistance of the light irradiation portion or the heat treatment portion. And a step of performing an etching process by leaving a portion of the etching resistance changing material that has changed the etching resistance. To provide a manufacturing method of a microchemical chip.

In a seventh aspect of the present invention, the reaction unit includes a storage / conveying unit configured to store and transport a liquid or gaseous sample and a reaction unit configured to react with the sample, which are formed by side walls on the support substrate. And a microchemical chip manufacturing method in which a porous portion having at least a part of a spherical shape is formed of a predetermined etching resistance changing material, wherein the porous substrate is formed on the support substrate. A step of forming a fine particle arrangement layer in advance, and forming an etching resistance changing material made of a mixture of zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, aluminum nitride and silicon oxide on the fine particle arrangement layer Irradiating a part of or the entire region of the support substrate on which the etching resistance-changing material is formed, or applying a heat treatment to the light Microchemical having a morphism portion or step of changing the etching resistance of the thermal processing unit, and performing etching process by a part of changing the etching resistance is left out of the etching resistance change material, and removing the fine particles A method for manufacturing a chip is provided.

According to an eighth aspect of the present invention, there is provided the method for producing a microchemical chip according to the seventh aspect , wherein the step of removing a part of the etching resistance changing material and the step of removing the fine particles are performed simultaneously .

The invention according to claim 9 provides the method for producing a microchemical chip according to claim 7 or 8 , wherein the fine particles are made of a silicon oxide-containing material.

In the invention of claim 10, the step of forming the fine particle arrangement layer, a dispersion containing the fine particles, is coated on a supporting substrate, any of claims 7 to 9 was be done by evaporating the solvent A method for producing a microchemical chip according to claim 1 is provided.

In the invention of claim 11, in the step of removing the etching resistance change material, according to any one of claims 6 to 10, characterized in that the removal by a chemical reaction using an acid or alkali A method for manufacturing a microchemical chip is provided.

According to a twelfth aspect of the present invention, there is provided the method for producing a microchemical chip according to any one of the sixth to eleventh aspects, wherein the support substrate is made of resin or silicon alone .

According to the present invention, a high-precision microchemical chip was easily obtained by thermal lithography without using an exposure mask. In addition, it is possible to locally improve the resistance of the etching resistance change material after the laser irradiation or after the heat radiation to the chemical solution, so that reliable patterning can be performed, and an accurate microchemical chip is manufactured. did it.
According to the second aspect of the present invention, an accurate microchemical chip having a hydrophilic flow path side wall is provided.
According to the invention of claim 3, the hydrophilic surface area can be increased, and it can be used as a base for attaching biomolecules such as DNA.
According to the invention according to claim 4, more precisely microchemical chip thermogenic raw using light irradiation could be produced.
According to the invention of claim 5 , the light-heat conversion layer can be provided with high light / heat absorption efficiency.
According to the invention which concerns on Claim 6 , the simple manufacturing method of the microchemical chip using the material from which the etching tolerance with respect to a chemical | medical solution changes with laser beam irradiation or heat radiation was able to be provided.
According to the invention which concerns on Claim 7 , the manufacturing method of the microchemical chip which has a new effect in the location which makes a sample react can be provided. In addition, by removing the fine particles on the support substrate in the final step, the etching resistance changing material can be made to be a porous portion having at least a part of a spherical shape.

Hereinafter, the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to the following examples.
[Example 1]
A schematic diagram of the microchemical chip of the present invention is shown in FIG.
In the example described below, the microchemical chip plays a role as a microreactor by attaching a microvalve or the like.
In a microchemical chip 10 shown in FIG. 1, a reagent introduction part 2, a flow path 3, a reaction part (sensor part) 4, a reservoir 5, and a microvalve 6 are formed on a resin support substrate 1.

FIG. 2 shows an enlarged schematic view of the main part of the microchemical chip of FIG.
The flow path 3 is formed by the side wall 7, and the side wall 7 can be formed of, for example, a mixture of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ), and exhibits hydrophilicity. To do.
Each flow path 3 is formed with a microvalve 6 made of a hydrogel that has a responsiveness to pH and expands and contracts due to this change. By the operation of the microvalve 6, the reagent introduction unit 2, the reaction chamber 4, and the reservoir 5 shown in FIG. 1 can be appropriately selected. Here, in FIG. 1, the reagent introduction unit 2, the flow path 3, and the reservoir 5 have a function of storing or transporting the reagent and are collectively referred to as a storage / transport unit.

A method for manufacturing the microchemical chip 10 shown in FIG. 1 will be specifically described with reference to FIGS.
First, Ge is formed as a light absorption layer 9 on a support substrate 1 made of silicon using a sputtering apparatus, and then a mixture of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ) (composition molar ratio 8: 2). ) And a thin film 8 (film thickness: 200 nm) made of an etching resistance changing material whose etching resistance is changed by laser beam irradiation described later (FIG. 3A).

Using a laser irradiation device, the light emitted from the blue semiconductor laser (wavelength 405 nm) is reduced by a lens (NA 0.85), and finally the sample introduction point 2 and the flow path 3 in FIG. Laser beam irradiation was continuously or pulsed on the formation portion of the side wall 7 to be formed (FIG. 3B).
Thereafter, the supporting substrate was immersed in a hydrofluoric acid (hydrofluoric acid) solution (about 2 wt%) for several tens of seconds, washed with pure water, and dried.
The portions irradiated with the laser beam remained after etching, and they became side walls to form the flow path 3 (FIG. 3 (c)). In this way, the basic skeleton of the microchemical chip was formed.

Thereafter, a predetermined micro valve (symbol 6 in FIG. 1) was installed.
Further, a predetermined resin substrate was disposed as the protective material 20 and bonded through heat treatment and subsequent cooling treatment (FIG. 3D).
A predetermined adhesive was put in a place where the flow path 3 did not need to be formed, and was reinforced.

According to the present invention, the microchemical chip 10 shown in FIG. 1 can be manufactured with high accuracy by a simple manufacturing method by thermal lithography using laser light.
Specifically, as described with reference to FIGS. 3A to 3D, the light absorption layer 9 made of Ge absorbs the laser beam and is formed thereon, an etching resistance change material layer, that is, A mixture of zinc sulfide and silicon oxide absorbs heat.
Thus, by forming the light absorption layer 9 in the lower layer, the heat absorption in the upper layer is performed in a narrow region, and a fine pattern can be formed.
More specifically, the thin film 8 made of the above-described material is more resistant to etching with hydrofluoric acid at the location irradiated with the laser. The mixture of portions not irradiated with the laser beam is removed by etching with hydrofluoric acid.
When etching with a hydrofluoric acid solution, only the portion of the mixture that has been heated to about 500 ° C. or more remains in the portion irradiated with laser light, and the other portions are removed by etching. Yes.
In order to utilize the properties as described above, the thin film 8 is a mixture containing silicon oxide, and a material that can be patterned by a difference in etching characteristics between the heat absorbing portion and other portions. is required.

  For the thin film 8, a change in etching resistance due to light and heat radiation is controlled by appropriately mixing silicon oxide and other materials (zinc sulfide in this embodiment) or adjusting the mixing ratio. Can do.

In addition, the light absorption layer 9 is preferably formed of a metal or a semiconductor because heat absorption efficiency is improved.
When hydrofluoric acid is used in the etching process, a material that does not exhibit a chemical reaction with hydrofluoric acid is selected for the support substrate 1 and the protective material 20.

Further, the wall surface of the side wall 7 preferably has a water contact angle of 40 ° or less. Further, by making it show hydrophilicity, molecules adhere to the side wall 7 during DNA analysis, for example. Therefore, there will be no problems that hinder transportation.
By setting the water contact angle of the side wall surface to 40 ° or less, adhesion of molecules of the analysis material to the side wall can be effectively prevented.

Moreover, the adhesion effect of the said analysis material can be heightened by forming the predetermined | prescribed protective film used as a hydrophilic group with respect to the wall surface of a side wall.
A sample having a long hydrophilicity retention period is less likely to cause the above-described adhesion failure, and detection of a target substance in the reaction unit 4 shown in FIG. 1 can be obtained with high sensitivity.

In the above-described pattern production according to the present invention, the flow path 3 can be formed on a scale with a width of about several tens of nanometers, as in the fine processing using X-ray lithography.
Furthermore, according to the present invention, the inclination angle of the pattern of the side wall 7 can be formed steeper than a pattern by general fine processing, and the height can be increased to a scale of several hundred nm.
In addition, the laser light irradiation apparatus may be used depending on the intended use of the microchemical chip, and a microchemical chip having a precise structure can be manufactured at a low cost by an extremely simple process.
When laser beam irradiation is performed, automatic drawing on the scale of several tens to several hundreds of nanometers can be performed with high control by programming the irradiation position distribution.

[Example 2]
A schematic view of another example of the microchemical chip of the present invention is shown in FIGS.
4A shows a schematic top view, and FIG. 4B shows a schematic cross-sectional view.
In this example, the microchemical chip serves as a microreactor.
In the microchemical chip 30 of FIG. 4, a mixture of silicon oxide and zinc oxide (composition molar ratio 8: 2) is formed in the reaction chamber 4 formed by the side wall 7 so as to cover the hemispherical or spherical voids. That is, a porous portion 11 is formed which forms a part of a spherical shape made of an etching resistance changing material.

  As shown in FIG. 4, in the microchemical chip 30, a porous portion 11 made of a mixture of silicon oxide and zinc oxide is partially formed on the support substrate 1, and this porous portion 11 has a diameter of A spherical or hemispherical outer portion of about 40 nm is formed of a mixture of silicon oxide and zinc oxide, and has a projection shape when they are connected.

Next, a method for producing the microchemical chip 30 of FIG. 4 will be described with reference to FIGS.
First, the support substrate 1 made of silicon was immersed in a colloidal solution containing silica fine particles having a diameter of about 40 nm, and pulled up at a constant speed, so that the silica fine particles were two-dimensionally arranged in a single layer on the support substrate 1. Thereafter, a thin film (film thickness: 40 nm) made of a mixture (molar ratio 8: 2) of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ) is formed on the surface of the support substrate using a sputtering apparatus.

This will be described in detail below.
FIG. 5A is a schematic cross-sectional view of a state in which a two-dimensional array structure of silica fine particles 12 is formed on the support substrate 1.
FIG. 5B shows a schematic cross-sectional view of a state in which a thin film 13 made of a mixture of silicon oxide and zinc oxide is formed on a two-dimensional array structure of silica fine particles 12.
Strictly speaking, the thin film 13 is formed so as to cover the fine particles 12, but is simplified in the drawing.
Sputtering is performed, and then the support substrate is fixed to a predetermined laser irradiation apparatus, and a blue semiconductor laser (wavelength: 405 nm, condensing with a NA 0.85 lens) is used, as shown in FIG. As described above, the laser beam was irradiated continuously or in a pulsed manner at a specific location (in the figure, reference numeral 14 represents a laser beam irradiation unit).
Thereafter, each supporting substrate was immersed in a hydrofluoric acid solution (about 2 wt%) for several tens of seconds, then washed with pure water and subjected to a drying treatment.
As described above, a support substrate on which the porous portion 11 was formed was produced, leaving only the laser irradiation portion 14 of a mixture of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ) (FIG. 5D). ).
The mixture of silicon oxide and zinc oxide and silica fine particles in the laser non-irradiated portion are removed by reaction with hydrofluoric acid.

Thereafter, a thin film 8 (thickness 200 nm) made of a mixture of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ) (composition molar ratio 8: 2) was further formed using a sputtering apparatus (FIG. 5E). .
Subsequently, the support substrate is fixed to the laser beam irradiation device, and the light emitted from the blue semiconductor laser (wavelength 405 nm) is reduced by the lens (NA 0.85) to form the flow path 3 and the reaction chamber 4. Laser beam irradiation was performed continuously or in a pulsed manner on the portion to be the side wall 7 (FIG. 5F).
Thereafter, it was immersed in a hydrofluoric acid solution (about 2 wt%) for several tens of seconds, washed with pure water, and dried.
The portion irradiated with the laser light has improved etching resistance and remains after the etching process, and the remaining portion becomes the side surface 7 of the flow path (FIG. 5G).
As described above, the basic skeleton of the microchemical chip of the present invention is formed.
Thereafter, the microvalve 6 shown in FIG. 1 is installed at a predetermined position of the flow path 3.
Further, a resin substrate was placed on the upper portion as the protective material 20, and after the heat treatment, it was bonded by quenching (FIG. 5 (h)).
If necessary, an adhesive was put in a place that does not become a flow path to strengthen the fixation.

The microchemical chip 30 shown in FIGS. 4A and 4B can be accurately manufactured by a simple manufacturing method by thermal lithography using laser light.
In this example as well, as in the manufacturing process shown in FIG. 3, a light absorption layer 9 made of a Ge layer is formed as a lower layer to absorb laser light, and a mixture of zinc sulfide and silicon oxide formed on the upper layer is formed. When the thin film is made to absorb heat, heat is absorbed in a narrow region, which is advantageous for forming a fine pattern.
The etching resistance to hydrofluoric acid is enhanced in the thin film made of the above mixture only at the portion irradiated with the laser beam. The mixture at the laser unirradiated portion is removed by etching with hydrofluoric acid.
In the etching with a hydrofluoric acid solution, a phenomenon is used in which only a mixture portion having a high temperature of about 500 ° C. or more remains in the portions irradiated with laser, and the other portions are removed by etching.
Such a phenomenon can be used by applying a mixture containing silicon oxide and performing patterning by utilizing the difference in etching characteristics between the heat absorbing portion and other portions.

Further, by appropriately mixing silicon oxide and other materials (in this embodiment, zinc sulfide) and adjusting the mixing ratio, the etching resistance can be changed and controlled by light and heat radiation.
Further, the light absorption layer 9 shown in FIG. 3 formed in the lower layer is preferably a metal or semiconductor because it has excellent light / heat absorption efficiency.

In the microchemical chip 30 shown in FIG. 4, the porous part 11 is formed in the reaction part 4.
In this microchemical chip 30, it was confirmed that DNA was attached only to the porous portion 11 when a solution containing aminosilane single molecule was passed through the reaction portion 4 and then a solution containing DNA was passed.

The porous portion 11 has a water contact angle of 40 ° or less, is hydrophilic, and passes through a solution containing an aminosilane single molecule and a DNA-containing solution in order as described above. Amino-modified DNA can be formed only in the mass part 11.
Biomolecules have molecular recognition ability, catalytic ability, self-healing function, etc., and various applications are possible by hybridization and the like.

Selective array fixation on a biomolecule pattern is useful for producing biomolecule integrated devices such as DNA computers, memories, and nanomachines.
By providing the porous part 11 as in the microchemical chip 30 of the present invention, a highly functional reaction part is formed, and it can also serve as a foundation for hybridization.

In addition, when laser light irradiation is performed, automatic drawing on the scale of several tens to several hundreds of nanometers can be performed with high control by programming the irradiation position distribution of the laser light.
Unlike photolithography, a mask is not necessarily required, and the circuit pattern can be easily changed according to the chip.
The pattern can also be designed by changing the size of the fine particles.
The shape after etching can also be controlled from the ratio between the particle size of the fine particles and the thickness of the mixture of zinc sulfide and silicon oxide.

Example 3
FIG. 6 shows a schematic top view of another example of the microchemical chip of the present invention.
In FIG. 6, the protective material formed on the uppermost layer is omitted.
In the microchemical chip 40, a reagent introduction part (not shown), a flow path 3, and a reaction part (sensor part) 4 are formed on a resin support substrate 1.
The side wall 7 of the channel 3 is made of a mixture of zinc sulfide (ZnS) and silicon oxide (SiO ₂ ) (composition molar ratio 9: 1), has a water contact angle of 40 ° or less, and exhibits hydrophilicity. And
The manufacturing method of the microchemical chip 40 can be the same as in the first embodiment. However, it is assumed that the irradiation position distribution is controlled and the program is drawn so as to form the flow path having the shape of FIG.
The composition molar ratio of the mixture of zinc sulfide and silicon oxide was 9: 1 compared to 8: 2 in Example 1. Even if the composition ratio was changed, a fine flow path pattern could be formed with high accuracy.

Example 4
FIG. 7 shows a schematic cross-sectional view of another example of the microchemical chip of the present invention.
This configuration is almost the same as the configuration of the microchemical chip in Example 2 described above.
In the microchemical chip 50 of FIG. 7, a reagent introduction part (not shown), a flow path 3, and a reaction part (sensor part) 4 are formed on a resin support substrate 1.
The side wall 7 forming the flow path 3 is made of a mixture (composition molar ratio 8: 2) of zinc oxide (ZnO) and silicon oxide (SiO ₂ ), and the contact angle with water is 40 ° or less. It shall show hydrophilicity.
The manufacturing method can be the same as in Example 2 described above, but a layer made of AgInSbTe of the light absorption layer 9 is formed as the lower layer of the side wall.
In Example 2, the Ge layer was used as the light absorption layer, but it was confirmed that the excellent effect as the light absorption layer was exhibited also in this example.
Moreover, the sputtering time of zinc oxide and silicon oxide was made relatively short, and the film thickness of the deposited film was made thin.
As a result, the structure of the porous part 3 finally produced after the etching was almost hemispherical.

The present invention is not limited to the first to fourth embodiments described above, and can be applied within a range that does not depart from the gist of the present invention.
For example, as a material for forming the light absorption layer 9, a III-V group compound semiconductor or the like can be applied in addition to Ge.
Further, as a material to be included in silicon oxide as a material for forming the sidewall 7, zinc oxide, aluminum oxide, silicon nitride, aluminum nitride, or the like can be applied in addition to zinc sulfide.
The diameter of the fine particles 12 shown in FIG. 5 and the film thickness of the thin film used to form the porous portion 11 are appropriately adjusted, and the patterning shape can be various shapes such as a hemispherical shape and a cylindrical shape. Can be selected.
In addition, when forming the sidewall, in addition to the method of irradiating with laser light, a method of locally applying heat can be applied, and a thermal lithography technique can be used. However, the method of irradiating with laser light is preferable because it can increase the accuracy.
In the manufacturing process diagram shown in FIG. 5, the number of layers of the fine particles 12 formed on the support substrate 1 is not limited to a single layer, and may be a plurality of layers.
About the magnitude | size of the microparticles | fine-particles 12, it is desirable from viewpoints, such as preparation accuracy, that it is the same particle size.
As the kind of the fine particles 12, in addition to amorphous silica which can be removed by etching with hydrofluoric acid, polystyrene which can be removed by heat or toluene can be applied.
In addition to microreactors (microfactories), applications of microchemical chips are diverse, including optical elements, biosensors, DNA computers, DNA memories, and biomolecule integrated devices.

1 shows a schematic perspective view of a microchemical chip of the present invention. The schematic of the principal part of a microchemical chip is shown. (A)-(d) The manufacturing process figure of the microchemical chip of this invention is shown. (A) A schematic top view of another example of the microchemical chip of the present invention is shown. (B) A schematic cross-sectional view of another example of the microchemical chip of the present invention is shown. (A)-(h) The manufacturing process figure of another example of the microchemical chip of this invention is shown. The schematic top view of another example of the microchemical chip of the present invention is shown. The schematic sectional drawing of the other example of the microchemical chip of this invention is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support substrate 2 Reagent introduction part 3 Flow path 4 Reaction part 5 Reservoir 6 Micro valve 7 Side wall 8 Thin film 9 Light absorption layer 10 Micro chemical chip 11 Porous part 12 Fine particle 13 Thin film 20 Protective material 30 Micro chemical chip 40 Micro chemical chip 50 Micro chemical chip

Claims (12)

A microchemical chip having a storage / conveying unit for storing and transporting a liquid or gaseous sample and a reaction unit for reacting the sample, which are formed by side walls on a support substrate,
The sidewalls state, and are not formed by etching resistance change material which changes its resistance to etching materials by irradiation or thermal radiation laser beam,
The microchemical chip according to claim 1, wherein the etching resistance changing material is made of a mixture of zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, aluminum nitride and silicon oxide .   2. The microchemical chip according to claim 1, wherein the side wall has a water contact angle of 40 ° or less and is formed of the etching resistance changing material. 3. The microchemical chip according to claim 1, wherein the reaction part is formed with a porous part made of the etching resistance changing material and having at least a part of a spherical shape. 4. The side wall is formed of an etching resistance changing material whose resistance to an etching material changes by laser light irradiation,
4. The microchemical chip according to claim 1, wherein a light absorption layer made of a material that absorbs laser light and generates heat is formed below the etching resistance changing material. 5. The microchemical chip according to claim 4, wherein the light absorption layer is a semiconductor or a metal. A method for producing a microchemical chip, comprising a storage / conveying part for storing and transporting a liquid or gaseous sample, and a reaction part for reacting the sample, formed by side walls on a support substrate,
Regarding the formation of the side wall,
On the support substrate, a step of forming an etching resistance changing material made of a mixture of zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, aluminum nitride, and silicon oxide , and
A step of irradiating a part of or the entire region of the support substrate on which the etching resistance changing material is formed, or applying a heat treatment to change the etching resistance of the light irradiation portion or the heat treatment portion;
And a step of performing an etching process by leaving a portion of the etching resistance changing material in which the etching resistance has been changed. A support substrate has a storage / conveying unit for storing and transporting a liquid or gaseous sample and a reaction unit for reacting the sample, which are formed by side walls, and a predetermined etching resistance changing material in the reaction unit. A microchemical chip manufacturing method in which a porous portion having at least a part of a spherical shape is formed,
Regarding the formation of the porous part,
Forming a fine particle arrangement layer in advance on the support substrate;
A step of forming an etching resistance changing material made of a mixture of any of zinc oxide, zinc sulfide, aluminum oxide, silicon nitride, aluminum nitride and silicon oxide on the fine particle array layer;
A step of irradiating a part of or the entire region of the support substrate on which the etching resistance changing material is formed, or applying a heat treatment to change the etching resistance of the light irradiation portion or the heat treatment portion;
A step of performing an etching process by leaving a portion of the etching resistance changing material that has changed the etching resistance ; and
And a step of removing the fine particles . 8. The method of manufacturing a microchemical chip according to claim 7 , wherein the step of removing a part of the etching resistance changing material and the step of removing the fine particles are simultaneously performed. The method for producing a microchemical chip according to claim 7 or 8 , wherein the fine particles are made of a silicon oxide-containing material. The step of forming the fine particle arrangement layer, a dispersion containing the fine particles, and coated on a support substrate, according to any one of claims 7 to 9, characterized in that by evaporation of the solvent Manufacturing method of microchemical chip. The method for producing a microchemical chip according to any one of claims 6 to 10 , wherein in the step of removing the etching resistance changing material, removal by a chemical reaction using acid or alkali is performed. The method for producing a microchemical chip according to any one of claims 6 to 11 , wherein the support substrate is made of resin or silicon alone .

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