CN209797478U

CN209797478U - Chip structure of enricher

Info

Publication number: CN209797478U
Application number: CN201920133417.3U
Authority: CN
Inventors: 冯飞; 赵斌; 李昕欣
Original assignee: Shanghai Institute of Microsystem and Information Technology of CAS
Current assignee: Shanghai Institute of Microsystem and Information Technology of CAS
Priority date: 2019-01-25
Filing date: 2019-01-25
Publication date: 2019-12-17
Anticipated expiration: 2029-01-25

Abstract

The utility model provides an enricher chip structure, include: the substrate is provided with a groove structure; a plurality of microcolumn structures, adjacent microcolumn structures being arranged based on an open nest; a microfluidic port in communication with the groove structure; and the cover plate is formed on one side of the substrate, on which the groove structure is formed, and at least covers the groove structure. The utility model discloses a microcolumn structure array of the nested setting of design in the cavity that groove structure formed, can obtain big surface area, and make flow field evenly distributed, and prolong gas flow path route, and then improve adsorbing material's homogeneity, improve adsorbing gas's enrichment rate, in addition, through the mesoporous silica who builds a layer of high specific surface area at the cavity internal surface, like nanometer mesoporous silica, can greatly increase the interior surface area in the cavity, thereby further improve adsorbing material's bearing capacity, improve the enrichment rate of enricher chip structure.

Description

chip structure of enricher

Technical Field

The utility model belongs to the field of micro-electromechanical systems, especially relate to an enricher chip structure.

Background

Enrichment is an important analytical technique. The enricher is an important part in a gas analysis instrument (such as a gas chromatograph, an ion mobility spectrometer and a mass spectrometer), is usually arranged at the front end of the instrument, and has the main function of adsorbing a large amount of detected target gas components, namely enriching, then desorbing the target gas components in a very short time, and at the moment, the concentration of the target gas components is instantly amplified and is sent to the analysis instrument for detection. Generally speaking, the enricher can improve the detection capability of an analytical instrument by 1-3 orders of magnitude, and is particularly important when the concentration of target gas is relatively low, particularly lower than the detection threshold of the analytical instrument.

The traditional enricher is of a tubular structure, usually a metal pipe or a glass pipe, an adsorbing material is filled in the pipe, and a heating wire is wound outside the pipe. The traditional enricher has the advantages of high enrichment rate, large dead volume, large heat capacity, low temperature rise rate and large power consumption. Silicon-based Micro-enrichers based on MEMS (Micro-electro-mechanical systems) technology are receiving the attention of researchers due to the advantages of small dead volume, small heat capacity, rapid temperature rise, low power consumption, easy integration and the like. The silicon-based micro-concentrator structure can be divided into a single-channel type and a cavity type. The single-channel silicon-based micro-concentrator is simple in structure, but the pressure difference between the two ends of an inlet and an outlet of the silicon-based micro-concentrator is large due to the long length of the channel, the surface area of the silicon-based micro-concentrator is small due to the fact that a microstructure is not designed and manufactured in the channel, the existing cavity type structure can bring different airflow field distributions, and the further improvement of the enrichment rate can be limited due to the uneven airflow field distribution.

Therefore, how to provide an enricher chip structure and a preparation method thereof is necessary to solve the above problems in the prior art.

SUMMERY OF THE UTILITY MODEL

in view of the above shortcomings of the prior art, an object of the present invention is to provide an enricher chip structure and a method for manufacturing the same, which are used to solve the problems of non-uniform distribution of gas flow field and limited enrichment rate in the prior art.

To achieve the above and other related objects, the present invention provides a method for manufacturing an enricher chip structure, the method comprising the steps of:

providing a substrate, and preparing a groove structure in the substrate;

Preparing a plurality of micro-column structures in the substrate, wherein the micro-column structures are positioned in the groove structures and comprise a first extension part, a connecting part and a second extension part which are sequentially connected, the first extension part, the connecting part and the second extension part enclose a space area with an opening, and the adjacent micro-column structures are nested based on the opening;

Preparing at least two microfluidic ports in the substrate, the microfluidic ports being in communication with the groove structure; and

and providing a cover plate, and preparing the cover plate on one side of the substrate on which the groove structure is formed, wherein the cover plate at least covers the groove structure.

As an alternative of the utility model, prepare behind the apron, still include the step: and manufacturing a heating resistor and a temperature measuring resistor on at least one of one side of the cover plate far away from the substrate and one side of the substrate far away from the cover plate.

As an alternative of the utility model, the preparation heating resistor reaches the step of temperature measurement resistance includes: depositing a metal material layer on the surface of the structure where the heating resistor and the temperature measuring resistor are required to be formed, forming a graphical mask layer on the metal material layer, and etching the metal material layer based on the graphical mask layer to form the heating resistor and the temperature measuring resistor.

As an alternative of the present invention, the manner of preparing the cover plate on the substrate includes anodic bonding, wherein the cover plate includes a glass cover plate, the bonding temperature of the anodic bonding is between 200 ℃ and 450 ℃, and the bonding voltage is between 600V and 1400V.

As an alternative of the present invention, the shape of the groove structure includes any one of an oval shape and a structure with a square middle part and arc-shaped ends; the shape of the micro-column structure comprises any one of a U shape, a V shape and an irregular shape.

As an alternative of the present invention, the shape of the micro-pillar structure includes a U-shape, the opening of the U-shape constitutes the space region the opening, and adjacent the micro-pillar structure the opening is relatively set, and through adjacent the micro-pillar structure the first extension with the interpenetration setting of the second extension is realized the micro-pillar structure the nested setting.

as an alternative of the present invention, the preparation method further comprises the steps of: at least preparing a mesoporous silicon oxide layer on the surface of the micro-column structure.

As an alternative of the present invention, the preparation forms the groove structure the micro-pillar structure reaches the preparation after the micro-fluidic port the mesoporous silica layer, just the silica layer is formed in the groove structure internal surface and the surface of the micro-pillar structure.

As an alternative of the present invention, the step of preparing the mesoporous silica layer comprises:

1) Providing a containing device, and adding ethanol and ethyl orthosilicate into the containing device;

2) Adding concentrated hydrochloric acid into the accommodating device, and placing the accommodating device in an oil bath pan for stirring;

3) taking out the accommodating device, and adding water and concentrated hydrochloric acid into the accommodating device for stirring at room temperature;

4) Placing the accommodating device in an oil bath pan for stirring;

5) Taking out the accommodating device, and adding ethanol into the accommodating device for stirring at room temperature;

6) adding hexadecyl trimethyl ammonium bromide powder into the accommodating device, stirring at room temperature until the hexadecyl trimethyl ammonium bromide powder is dissolved, and continuing stirring;

7) taking a preset amount of the obtained liquid in the accommodating device, and adding ethanol for dilution to obtain an obtained liquid diluent;

8) Placing the substrate at least provided with the micro-column structure in the obtained liquid diluent, and pulling out the substrate based on a pulling method; and

9) And drying the pulled substrate, and roasting the dried substrate to prepare the mesoporous silicon oxide layer on at least the surface of the micro-column structure.

As an alternative of the present invention, the groove structure and the micro-pillar structure are prepared based on a patterned mask layer formed on the substrate, wherein the patterned mask layer is retained to step 9), and the patterned mask layer is removed after the drying and before the baking.

as an alternative of the utility model, the preparation of the mesoporous silica layer further comprises the following steps: and preparing an adsorption material layer on at least the surface of the mesoporous silicon oxide layer.

As an alternative of the present invention, the adsorbent material layer is prepared after the cover plate is prepared, wherein the adsorbent material layer is prepared in a manner including: and installing a capillary at the microfluidic port, and forming the adsorption material layer on the basis that the capillary is at least on the surface of the mesoporous silicon oxide layer.

As an alternative of the present invention, the layer of adsorbent material is prepared before the cover plate is prepared, wherein the manner of preparing the layer of adsorbent material comprises at least one of evaporation, sputtering, atomic layer deposition and molecular vapor deposition.

The utility model also provides an enricher chip structure, enricher chip structure includes:

The device comprises a substrate, wherein a groove structure is formed in the substrate;

The micro-column structures are formed on the substrate and located in the groove structures, each micro-column structure comprises a first extension part, a connecting part and a second extension part which are sequentially connected, a space area with an opening is defined by the first extension part, the connecting part and the second extension part, and the adjacent micro-column structures are nested based on the openings;

At least two microfluidic ports formed in the substrate and in communication with the groove structure; and

And the cover plate is formed on one side of the substrate on which the groove structure is formed and at least covers the groove structure.

as an alternative of the present invention, the concentrator chip structure further comprises a heating resistor and a temperature measuring resistor, wherein the heating resistor reaches the temperature measuring resistor is located the cover plate is kept away from one side of the substrate and the substrate is kept away from at least one of the one side of the cover plate.

As an alternative of the present invention, the first extension and the second extension form two side portions of the U-shaped micro-column structure, and the connection portion forms a bottom portion of the U-shaped micro-column structure, wherein the side portion has a rectangular shape, and the bottom portion has a semi-circular arc shape, wherein an outer diameter of the semi-circular arc shape is between 80 μm and 480 μm, an inner diameter of the semi-circular arc shape is between 35 μm and 560 μm, the inner diameter of the semi-circular arc shape is between 25 μm and 400 μm, and a length of the rectangular shape is between 80 μm and 480 μm; the distance between the adjacent micro-column structures is between 5 and 80 μm.

As an alternative of the present invention, the concentrator chip structure further comprises a mesoporous silica layer, wherein the mesoporous silica layer is at least located on the surface of the micro-pillar structure.

As above, the utility model discloses an enricher chip architecture, through the microcolumn structure array of the nested setting of design in the cavity that groove structure formed, can obtain big surface area, and make flow field evenly distributed, and prolong the gas flow path route, and then improve adsorbing material's homogeneity, improve adsorbing gas's enrichment rate, in addition, through the mesoporous silica of a layer of high specific surface area of building at the cavity internal surface, like nanometer mesoporous silica, can greatly increase the internal surface area in the cavity, thereby further improve adsorbing material's bearing capacity, improve enricher chip architecture's enrichment rate.

Drawings

FIG. 1 is a schematic structural diagram of a silicon-based micro-concentrator chip (a) based on mesoporous silica according to the present invention; (b) the structural schematic diagram of the nested U-shaped micro-column array is distributed in the cavity; (c) nesting structural parameters of the U-shaped microcolumn units; (d) gas flow path distribution schematic.

FIGS. 2-8 are schematic diagrams of the main steps for preparing a silicon-based micro-concentrator chip based on mesoporous silica according to the first embodiment,

Fig. 2 is a schematic diagram illustrating the formation of a patterned mask layer.

Fig. 3 is a schematic diagram illustrating the formation of a groove structure and a micro-pillar structure.

Fig. 4 is a schematic view showing the formation of a mesoporous silica layer.

Fig. 5 is a schematic diagram of removing the remaining patterned mask layer.

Fig. 6 shows a schematic view of forming a cover plate.

Fig. 7 is a schematic structural diagram illustrating the formation of a metal material layer and a patterned mask layer.

FIG. 8 is a schematic diagram of a structure for forming a heating resistor and a temperature measuring resistor.

FIG. 9 is a schematic plan view showing the shapes of the heating resistor and the temperature measuring resistor.

FIG. 10(a) SEM of the structure of a silicon-based preconcentrator chip; (b) scanning electron microscope photo of mesoporous silica coated on the inner surface of the cavity of the silicon-based micro concentrator.

FIGS. 11-12 are schematic diagrams of the main steps for preparing a silicon-based micro-concentrator chip based on mesoporous silica according to example two,

fig. 11 is a schematic diagram illustrating the formation of the adsorbent material layer.

Fig. 12 is a schematic view showing the formation of a cover plate.

Description of the element reference numerals

100 substrate

101 groove structure

102 micro-column structure

102a first extension part

102b connecting part

102c second extension part

103 microfluidic port

104 patterned mask layer

105 mesoporous silica layer

106 cover plate

107 metal material layer

108 patterned mask layer

109 heating resistor

110 temperature measuring resistor

111 layer of adsorbent material

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The present invention can also be implemented or applied through other different specific embodiments, and various details in the present specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

please refer to fig. 1 to 12. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention in a schematic manner, and only the components related to the present invention are shown in the drawings rather than being drawn according to the number, shape and size of the components in actual implementation, and the form, quantity and proportion of the components in actual implementation may be changed at will, and the layout of the components may be more complicated.

The first embodiment is as follows:

As shown in fig. 1-9, the utility model provides a preparation method of enricher chip structure, the preparation method comprises the following steps:

providing a substrate 100, and preparing a groove structure 101 in the substrate 100;

Preparing a plurality of micro-pillar structures 102 in the substrate 100, wherein the micro-pillar structures 102 are located in the groove structures 101, the micro-pillar structures 102 include a first extension portion 102a, a connection portion 102b and a second extension portion 102c which are connected in sequence, the first extension portion 102a, the connection portion 102b and the second extension portion 102c enclose a space region with an opening, and adjacent micro-pillar structures 102 are nested based on the opening;

preparing at least two microfluidic ports 103 in the substrate 100, the microfluidic ports 103 being in communication with the groove structure 101; and

a cover plate 106 is provided, and the cover plate 106 is prepared on the side of the substrate 100 where the groove structure 101 is formed, and the cover plate 106 at least covers the groove structure 101.

the following will describe in detail the preparation of the concentrator chip structure of the present invention with reference to the accompanying drawings, wherein the steps and sequences of the above preparation method can be combined or interchanged according to the actual process.

first, in an example, a substrate 100 is provided, wherein the substrate 100 is used for forming a subsequent chip structure based on the substrate, and may be a silicon substrate 100, and the like, and the silicon substrate 100 is selected in this example, but not limited thereto.

Next, the groove structure 101, the micro-pillar structure 102, and the micro-fluidic port 103 are prepared on the substrate 100, wherein the three structures may be formed by etching/etching based on the same mask layer in the same process, or may be formed by etching separately or in pairs, and in an example, the three structures are selected to be etched and formed at the same time.

as an example, the process of etch formation includes: a patterned mask layer 104, which may be photoresist, silicon oxide, silicon nitride, or the like, is formed on the substrate 100, and a desired pattern is formed thereon, and the groove structure 101, the micro-pillar structure 102, and the micro-fluidic port 103 are formed based on the patterned mask layer 104. The number of the microfluidic ports 103 can be selected according to actual requirements, and in one example, two microfluidic ports are selected and respectively arranged at two opposite ends of the groove structure 101, so that a capillary column can be sealed to provide a gas passage with the outside.

Specifically, the micro-pillar structure 102 includes a first extension 102a, a connection portion 102b and a second extension 102c connected in sequence, the first extension 102a, the connection portion 102b and the second extension 102c enclose a space region with an opening, the nesting of the adjacent micro-pillar structures 102 is performed based on the nesting of the openings, that is, the adjacent micro-pillar structures 102 are nested with each other, and may be interspersed in an interpolation manner, for example, in a case of a reference micro-pillar structure 102, the second extension 102c of the micro-pillar structure 102 on the left side thereof may be inserted into the space region of the reference micro-pillar structure 102 from the opening of the reference micro-pillar structure 102, and the first extension 102a of the micro-pillar structure 102 on the right side thereof is inserted into the space region of the reference micro-pillar structure 102 from the opening of the reference micro-pillar structure 102, to achieve a nested arrangement.

As an example, the shape of the groove structure 101 includes any one of an oval shape and a structure with a square middle part and arc-shaped ends;

The shape of the micro-pillar structure 102 includes any one of a U-shape, a V-shape, and an irregular shape, as an example.

Specifically, the groove structure 101 and the cover plate 106 covering the groove structure form a cavity to form a cavity of the silicon-based micro-concentrator, wherein, in an example, from a top view, the middle of the cavity is rectangular, and two ends of the cavity are two arcs, preferably two semi-circles, and in addition, the cavity can also be designed to be oval according to needs, and the round or oval structure ensures that the cavity structure is streamlined, thereby being beneficial to the uniform distribution of a flow field. The shape of the micro-pillar structure 102 in a plan view includes any one of a U shape, a V shape, and an irregular shape, for example, a U-shaped cavity constitutes the space region, but the first extension portion 102a, the connection portion 102b, and the second extension portion 102c may be irregular structures, and the space region having the opening may be formed.

As an example, the shape of the micro-pillar structure 102 includes a U shape, an opening of the U shape constitutes the opening of the space region, the openings of the adjacent micro-pillar structures 102 are oppositely disposed, and the nested arrangement of the micro-pillar structures 102 is realized by interposing the first extension portion 102a and the second extension portion 102c of the adjacent micro-pillar structures 102.

As an example, the first extension portion 102a and the second extension portion 102c form two side portions of the U-shaped micro-cylinder structure 102, and the connection portion 102b forms a bottom portion of the U-shaped micro-cylinder structure 102, wherein the side portions have a rectangular shape, and the bottom portion has a semicircular arc shape, wherein an outer diameter of the semicircular arc shape is between 80 μm and 480 μm, and an inner diameter of the semicircular arc shape is between 20 μm and 400 μm; the width of the rectangle is between 5 and 80 mu m, and the length of the rectangle is between 80 and 480 mu m; the spacing between adjacent micro-pillar structures 102 is between 5 μm and 80 μm. The distance between adjacent micro-pillar structures 102 refers to a distance between opposite sides of two micro-pillar structures 102 after being inserted in the adjacent micro-pillar structures 102 that are inserted, for example, a distance between two opposite surfaces of a first extension portion 102a of one micro-pillar structure 102 and a second extension portion 102c of the adjacent micro-pillar structure 102.

specifically, in an example, the micro-cylinder structure 102 is disposed in a U shape, and a cross section (top view) of the U-shaped micro-cylinder structure is as shown in fig. 1(c), and is formed by a semicircular arc and two rectangles connected with the semicircular arc, wherein an outer diameter of the semicircular arc is 280 micrometers, an inner diameter of the semicircular arc is 200 micrometers, a width of the rectangle is 40 micrometers, and a length of the rectangle is 280 micrometers; the U-shaped microcolumns are nested with each other (fig. 1(b) - (c)) and distributed in a regularly arranged array, and the distance between every two adjacent U-shaped microcolumns is 40 micrometers; the dimensions of the structures described above may be scaled up or down as desired. On one hand, the nested U-shaped micro-column array has the advantages that due to the uniform distribution of the micro-columns, gas can uniformly flow in the gaps of the U-shaped micro-columns (the gas flow path is shown in figure 1(d)), the length of the gas flow path is increased, so that the contact probability of the gas and the enriched material on the surface of the micro-columns is increased, and the factors can further improve the enrichment rate of the chip.

As an example, the manner of preparing the cover plate 106 on the substrate 100 includes anodic bonding, wherein the cover plate 106 includes a glass cover plate 106, the bonding temperature of the anodic bonding is between 200 ℃ and 450 ℃, and the bonding voltage is between 600V and 1400V.

specifically, the utility model discloses an it still forms in the preparation of concentrator chip structure apron 106, apron 106 includes glass apron 106, and in an example, the selection is two glass pieces of throwing, and is further, will apron 106 prepare in the substrate 100 mode can be the mode of bonding, also can be other modes known in the art, in an example, the selection is the mode of anodic bonding, the bonding temperature of anodic bonding selects 300 ℃, and bonding voltage selects 1000V, in addition, apron 106 covers at least groove structure 101 is in order to form the cavity of concentrator, in an example, apron 106 still covers microfluidic port 103, further can cover whole substrate 100.

As an example, after the cover plate 106 is prepared, the method further includes the steps of: a heating resistor 109 and a temperature measuring resistor 110 are fabricated on at least one of a side of the cover plate 106 away from the substrate 100 and a side of the substrate 100 away from the cover plate 106.

as an example, the steps of preparing the heating resistor 109 and the temperature measuring resistor 110 include: depositing a metal material layer 107 on the surface of the structure where the heating resistor 109 and the temperature measuring resistor 110 need to be formed, forming a patterned mask layer 108 on the metal material layer 107, and etching the metal material layer 107 based on the patterned mask layer 108 to form the heating resistor 109 and the temperature measuring resistor 110.

specifically, the utility model discloses an among the enricher structure, can heat it through the mode that external setting heating device to can carry out the release of enrichment gas, in an example, can be through setting up above-mentioned heating is carried out to heating resistor 109's mode, in further optional example, can also be setting when heating resistor 109, set up temperature measurement resistor 110 to effectively carry out gaseous release, temperature measurement resistor 110 is preferred to be set up heating resistor 109 with one side, in an example, heating resistor 109 sets up temperature measurement resistor 110's periphery, promptly heating resistor 109 encircles temperature measurement resistor 110 sets up.

In an example, the heating resistor 109 and the temperature measuring resistor 110 are disposed on a side of the cover plate 106 away from the substrate 100, and the heating resistor 109 and the temperature measuring resistor 110 are also disposed on a side of the substrate 100 away from the cover plate 106, and in an example, the heating resistor 109 and the temperature measuring resistor 110 may be formed by depositing a metal material layer 107 (such as Ti/Pt, etc.) on the substrate 100 and the cover plate 106, spin-coating a mask layer (such as photoresist) and patterning, and etching/corroding the metal layer.

In addition, in an example, dicing may be performed after the heating resistor 109 and the temperature measuring resistor 110 are formed, so as to obtain a silicon-based micro-concentrator chip.

As an example, the preparation method further comprises the steps of: at least the surface of the micro-pillar structure 102 is prepared with a mesoporous silica layer 105.

specifically, in an example, the step of preparing the mesoporous silica layer 105 at least on the surface of the micro-pillar structure 102 may be nano mesoporous silica, in an optional example, the mesoporous silica layer 105 is formed on the inner surface of the groove structure 101 and the surface of the micro-pillar structure 102, based on a mesoporous silica nano construction technology, a thin layer of mesoporous silica with a high specific surface area is prepared on the inner surface of the silicon-based micro concentrator cavity, and finally, the mesoporous silica is coated with an adsorbing material, so that the mesoporous silica thin film can bear more adsorbing material than the original silicon surface.

As an example, the mesoporous silicon oxide layer 105 is prepared after the groove structure 101, the micro-pillar structure 102 and the micro-fluidic port 103 are prepared.

Specifically, in an example, the mesoporous silicon oxide layer 105 is prepared after the groove structure 101, the micro-pillar structure 102 and the microfluidic port 103 are prepared, and in an example, the above structure is formed based on the patterned mask layer, and the remaining patterned mask layer is included after the structure is prepared, so as to protect a bonding surface in a subsequent process.

As an example, the step of preparing the mesoporous silica layer 105 includes:

4) Placing the accommodating device in an oil bath pan for stirring;

8) placing the substrate 100 on which at least the micro-pillar structure 102 is formed in the obtained liquid diluent, and pulling out the substrate 100 based on a czochralski method; and

9) Drying the pulled substrate 100, and baking the dried substrate 100 to prepare the mesoporous silicon oxide layer 105 on at least the surface of the micro-pillar structure 102.

As an example, the groove structure 101 and the micro-pillar structure 102 are prepared based on a patterned mask layer formed on the substrate 100, wherein the patterned mask layer is remained in step 9), and is removed after the drying and before the baking.

Specifically, the accommodating device may be a flask, and in an example, a nano mesoporous silicon oxide layer 105 is formed inside a microchannel on the silicon substrate 100 with the micro-cavity and the micro-fluidic port 103 fabricated thereon by using a non-aqueous synthesis method of solvent Evaporation Induced Self-Assembly (EISA), where the process is as follows: (a) adding 50mL of ethanol and 50mL of TEOS into a 500mL flask, adding 4.14mL of water and 1 mu L of concentrated hydrochloric acid into the flask, putting the flask into an oil bath kettle at 60 ℃, and stirring for 30 min; (b) taking out the flask, adding 16.6mL of water and 76 mu L of concentrated hydrochloric acid, and stirring at room temperature for 15 min; (c) placing the flask into an oil bath kettle at 50 ℃ and stirring for 15 min; (d) taking the flask out of the oil bath pan, adding 250mL of ethanol, and stirring at room temperature; (e) adding 8.36g of CTAB powder into the flask, stirring at room temperature until CTAB is completely dissolved, and continuing stirring for 1 h; (f) 20mL of the resulting solution was diluted with 0-200mL of ethanol. (g) A mask is manufactured on the bonding surface of the silicon substrate 100 on which the micro-channel and the microfluidic port 103 have been manufactured, and the mask can be a patterned mask layer remained in a previous process for manufacturing a structure such as the micro-pillar structure 102, and then the silicon substrate 100 is immersed in a solution, and the silicon substrate 100 is pulled out at a rate of 5-15mL/min by a czochralski method. (h) The silicon substrate 100 was placed in a drying tower to be dried for three days, and the mask was removed. (i) The silicon substrate 100 is placed into a furnace for baking, and the baking conditions are as follows: the temperature of the calcining furnace is raised to 550 ℃ at the temperature rise rate of 1 ℃/min, the furnace temperature of 550 ℃ is kept for 360min, and then the furnace is naturally cooled.

as an example, the preparation of the mesoporous silica layer 105 further includes the following steps: an adsorption material layer 111 is prepared on at least the surface of the mesoporous silica layer 105.

specifically, in an example, the method further includes the following steps after the mesoporous silicon oxide layer 105 is prepared: an adsorption material layer 111 is prepared on at least the surface of the mesoporous silica layer 105. In an example, the adsorption material layer 111 may be formed on the mesoporous silica layer 105 on the inner surface of the groove structure 101, and also formed on the surface of the mesoporous silica layer 105 on the surface of the micro-pillar structure 102.

As an example, the adsorption material layer 111 is prepared after the cover plate 106 is prepared, wherein the adsorption material layer 111 is prepared by: a capillary is installed at the microfluidic port 103, and the adsorption material layer 111 is formed on the basis that the capillary is at least on the surface of the mesoporous silica layer 105.

Specifically, in this example, after the cover plate 106 is prepared, in another optional example, after the heating electrode and the temperature measuring resistor 110 are prepared and formed, and after the silicon-based preconcentrator chip is obtained by dicing, a capillary is installed at the microfluidic port 103, the port is sealed with glue, and finally, an adsorbing material (such as Tenax-TA) is coated in the cavity of the silicon-based preconcentrator chip through the installed capillary.

In addition, as shown in fig. 1, referring to fig. 2-10, the present invention further provides an enricher chip structure, comprising:

A substrate 100, and a groove structure 101 is formed in the substrate 100;

a plurality of micro-pillar structures 102 formed on the substrate 100 and located in the groove structure 101, wherein each micro-pillar structure 102 includes a first extension 102a, a connection portion 102b, and a second extension 102c connected in sequence, the first extension 102a, the connection portion 102b, and the second extension 102c enclose a space region with an opening, and adjacent micro-pillar structures 102 are nested based on the opening;

At least two microfluidic ports 103 formed in the substrate 100 and communicating with the groove structure 101; and

And a cover plate 106 formed on one side of the substrate 100 where the groove structure 101 is formed, and at least covering the groove structure 101.

specifically, the substrate 100 is used for forming a subsequent chip structure based on the substrate, and may be a silicon substrate 100, and the substrate is selected as the silicon substrate 100 in this example, but is not limited thereto. The number of the microfluidic ports 103 can be selected according to actual requirements, and in one example, two microfluidic ports are selected and respectively arranged at two opposite ends of the groove structure 101, so that a capillary column can be sealed and connected to provide a gas passage with the outside.

As an example, the first extension portion 102a and the second extension portion 102c form two side portions of the U-shaped micro-cylinder structure 102, and the connection portion 102b forms a bottom portion of the U-shaped micro-cylinder structure 102, wherein the side portions have a rectangular shape, and the bottom portion has a semicircular arc shape, wherein an outer diameter of the semicircular arc shape is between 35 μm and 560 μm, and an inner diameter of the semicircular arc shape is between 25 μm and 400 μm; the width of the rectangle is between 5 and 80 mu m, and the length of the rectangle is between 80 and 480 mu m; the spacing between adjacent micro-pillar structures 102 is between 5 μm and 80 μm. The distance between adjacent micro-pillar structures 102 refers to a distance between opposite sides of two micro-pillar structures 102 after being inserted in the adjacent micro-pillar structures 102 that are inserted, for example, a distance between two opposite surfaces of a first extension portion 102a of one micro-pillar structure 102 and a second extension portion 102c of the adjacent micro-pillar structure 102.

Specifically, in an example, the micro-pillar structure 102 is disposed in a U shape, and a cross section (top view) of the U-shaped micro-pillar 11 is as shown in fig. 1(c), and is formed by a semicircular arc and two rectangles connected with the semicircular arc, wherein an outer diameter of the semicircular arc is 280 micrometers, an inner diameter of the semicircular arc is 200 micrometers, a width of the rectangle is 40 micrometers, and a length of the rectangle is 280 micrometers; the U-shaped microcolumns are nested with each other (fig. 1(b) - (c)) and distributed in a regularly arranged array, and the distance between every two adjacent U-shaped microcolumns is 40 micrometers; the dimensions of the structures described above may be scaled up or down as desired. On one hand, the nested U-shaped micro-column array has the advantages that due to the uniform distribution of the micro-columns, gas can uniformly flow in the gaps of the U-shaped micro-columns (shown in figure 1(d)), so that the coating uniformity of the adsorption material and the uniform adsorption of the gas in the whole cavity can be improved; on the other hand, compared with other micro-column structures 102, the nested U-shaped micro-columns increase the surface area and thus increase the carrying area of the adsorbing material, and the gas flow path bends back and forth along the gaps of the U-shaped micro-column array (fig. 1(d)), increasing the length of the gas flow path and thus increasing the contact probability of the gas and the enriched material on the surface of the micro-column, which all further increase the enrichment rate of the chip.

Specifically, the utility model discloses an it still forms in the preparation of concentrator chip structure apron 106, apron 106 includes glass apron 106, in an example, selects for two glass pieces of throwing, in addition, apron 106 covers at least groove structure 101 is in order to form the cavity of concentrator, in an example, apron 106 still covers micro-fluidic port 103, further can cover wholly substrate 100.

As an example, the concentrator chip structure further comprises a heating resistor 109 and a temperature measuring resistor 110, wherein the heating resistor 109 and the temperature measuring resistor 110 are located on at least one of a side of the cover plate 106 away from the substrate 100 and a side of the substrate 100 away from the cover plate 106.

specifically, the utility model discloses an among the enricher structure, can heat it through the mode that external setting heating device to can carry out the release of enrichment gas, in an example, can be through setting up above-mentioned heating is carried out to heating resistor 109's mode, in further optional example, can also be setting when heating resistor 109, set up temperature measurement resistor 110 to effectively carry out gaseous release, temperature measurement resistor 110 is preferred to be set up heating resistor 109 with one side, in an example, heating resistor 109 sets up temperature measurement resistor 110's periphery, promptly heating resistor 109 encircles temperature measurement resistor 110 sets up. In one example, the heating resistor 109 and the temperature measuring resistor 110 are disposed on a side of the cover plate 106 away from the substrate 100, and the heating resistor 109 and the temperature measuring resistor 110 are also disposed on a side of the substrate 100 away from the cover plate 106, in one example, the heating resistor 109 and the temperature measuring resistor 110 may be a metal material, such as Ti/Pt.

As an example, the concentrator chip structure further comprises a mesoporous silica layer 105, wherein the mesoporous silica layer 105 is at least located on the surface of the micro-pillar structure 102.

specifically, in an example, the mesoporous silica layer 105 may be a nano mesoporous silica, and in an optional example, the mesoporous silica layer 105 is formed on the inner surface of the groove structure 101 and the surface of the micro-pillar structure 102, based on a mesoporous silica nano construction technology, a thin layer of mesoporous silica with a high specific surface area is prepared on the inner surface of the silicon-based micro-concentrator cavity, and finally, the adsorbing material is coated on the mesoporous silica, so that the mesoporous silica film can carry more adsorbing material than the original silicon surface.

Example two:

In addition, as shown in FIGS. 11-12, referring to FIGS. 1-10, the present invention provides another method for manufacturing an enricher chip structure, the difference from the first embodiment is that the formation sequence and manner of the adsorbing material layer 111 are different, in this embodiment, the adsorbent material layer 111 is prepared prior to preparing the cover plate 106, wherein the manner of preparing the adsorption material layer 111 includes at least one of evaporation, sputtering, atomic layer deposition and molecular vapor deposition, that is, after the mesoporous silica layer 105 is formed, an adsorption material layer 111 (such as alumina or the like) is deposited (such as evaporation, sputtering, atomic layer deposition, molecular vapor deposition), in an example, when forming the micro-pillar structure 102 or the like based on a patterned mask layer, the patterned mask layer is removed after forming the adsorption material layer 111. Then, carrying out anodic bonding on the surface of the silicon substrate 100 with the microcavity and the glass cover plate 106 (double-polished glass sheet), wherein the bonding temperature is 200-; ) Depositing a metal layer (such as Ti/Pt and the like) on the silicon substrate 100 and the glass substrate 100, spin-coating a mask layer (such as photoresist) and patterning; etching/corroding the metal layer to obtain a heating resistor 109 and a temperature measuring resistor 110, scribing to obtain a silicon-based micro-concentrator chip, installing a capillary tube at the microfluidic port 103, and sealing the port with glue to complete the manufacturing of the silicon-based micro-concentrator chip, wherein other processes and structures can refer to the first embodiment.

To sum up, the utility model provides an enricher chip structure and preparation method, the preparation includes: providing a substrate, and preparing a groove structure in the substrate; preparing a plurality of micro-column structures in the substrate, wherein the micro-column structures are positioned in the groove structures and comprise a first extension part, a connecting part and a second extension part which are sequentially connected, the first extension part, the connecting part and the second extension part enclose a space area with an opening, and the adjacent micro-column structures are nested based on the opening; preparing at least two microfluidic ports in the substrate, the microfluidic ports being in communication with the groove structure; and providing a cover plate, and preparing the cover plate on one side of the substrate on which the groove structure is formed, wherein the cover plate at least covers the groove structure. The utility model discloses an enricher chip architecture and preparation method thereof, through the microcolumn structure array of the nested setting of design in the cavity that groove structure formed, can obtain big surface area, and make flow field evenly distributed, and prolong the gas flow path route, and then improve the homogeneity of adsorption material, improve the enrichment rate of adsorption gas, in addition, through the mesoporous silica of building a layer of high specific surface area at the cavity internal surface, like nanometer mesoporous silica, can greatly increase the internal surface area in the cavity, thereby further improve the bearing rate of adsorption material, improve the enrichment rate of enricher chip architecture. Therefore, the utility model effectively overcomes various defects in the prior art and has high industrial utilization value.

The above embodiments are merely illustrative of the principles and effects of the present invention, and are not to be construed as limiting the invention. Modifications and variations can be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims

1. an concentrator chip architecture, comprising:

2. the concentrator chip architecture of claim 1, further comprising a heating resistor and a temperature measuring resistor, wherein the heating resistor and the temperature measuring resistor are located on at least one of a side of the cover plate away from the substrate and a side of the substrate away from the cover plate.

3. The concentrator chip structure of claim 1, wherein the shape of the groove structure comprises any one of an oval shape and a structure with a square middle and arc ends; the shape of the micro-column structure comprises any one of a U shape and a V shape.

4. The concentrator chip structure of claim 1, wherein the shape of the micropillar structure comprises a U-shape, the opening of the U-shape constitutes the opening of the spatial region, and the openings of adjacent micropillar structures are oppositely disposed, and the nested arrangement of the micropillar structures is achieved by an interspersed arrangement of the first and second extensions of adjacent micropillar structures.

5. The concentrator chip structure of claim 4, wherein the first and second extensions form two sides of the U-shaped micro-pillar structure, and the connecting portion forms a bottom of the U-shaped micro-pillar structure, wherein the sides comprise a rectangle shape and the bottom comprises a semi-circular arc shape, wherein the semi-circular arc shape has an outer diameter of between 35 μ ι η -560 μ ι η and an inner diameter of between 25 μ ι η -400 μ ι η; the width of the rectangle is between 5 and 80 mu m, and the length of the rectangle is between 80 and 480 mu m; the distance between the adjacent micro-column structures is between 5 and 80 μm.

6. The concentrator chip structure of any one of claims 1-5, further comprising a mesoporous silica layer at least on a surface of the microcolumn structure.