CN112034012B - MEMS gas sensor gas-sensitive unit and preparation method thereof - Google Patents
MEMS gas sensor gas-sensitive unit and preparation method thereof Download PDFInfo
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- CN112034012B CN112034012B CN202010427355.4A CN202010427355A CN112034012B CN 112034012 B CN112034012 B CN 112034012B CN 202010427355 A CN202010427355 A CN 202010427355A CN 112034012 B CN112034012 B CN 112034012B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/128—Microapparatus
Abstract
The application discloses a MEMS gas sensor gas-sensitive unit and a preparation method thereof, wherein the preparation method comprises the following steps: sequentially preparing a first metal electrode layer and an insulating layer from bottom to top on a substrate; preparing a second metal electrode layer with a first hole on the insulating layer; forming a second hole in the insulating layer in the area of the first hole projected on the insulating layer, and exposing the first metal electrode layer through the first hole and the second hole; covering the second metal electrode layer with a gas-sensitive material to form a gas-sensitive structure layer, so that the gas-sensitive material is communicated with the first metal electrode layer and the second metal electrode layer at the first hole and the second hole; and patterning the gas-sensitive structural layer, retaining the gas-sensitive materials retained in the first holes and the second holes, and removing the rest of the gas-sensitive materials of the gas-sensitive structural layer to complete the preparation of the gas-sensitive unit. The application can greatly reduce the total volume of the effective part of the gas-sensitive structure, and further can improve the sensitivity and response speed of the sensor.
Description
Technical Field
The invention belongs to the technical field of micro-motor manufacturing, and relates to a MEMS gas sensor gas-sensitive unit and a preparation method thereof.
Background
The gas sensor is an important component in the technical field of MEMS sensing, and under the constraint conditions of low power consumption, small size and low cost, the realization of high sensitivity and quick response capability to target gas is an important technical research and development direction of the MEMS gas sensor.
The main scheme for improving the sensitivity and the response speed of the MEMS gas sensor comprises the following steps:
1. The performance of the sensitive material is improved: the improvement of the gas-sensitive performance of the sensitive material is significant for improving the device-level performance, but is limited by the research of the field of MEMS gas-sensitive materials, the material with good environmental stability and gas-sensitive capability at present mainly comprises metal oxide and partial high molecular polymer, and the sensitivity, response speed and long-term stability of the material cannot be improved at the same time, and the indexes are often mutually limited.
2. Control of the operating environment of the gas sensor (typically device heating): the working environment of the gas sensor is controlled, so that the response capability of the gas-sensitive material to target gas can be effectively improved, the sensitivity and the response speed can be simultaneously improved, the current effective environmental control means mainly control the working temperature of the device, and the means all need additional facilities or components to realize specific functions, so that the complexity of the system is increased, and the improvement of the reliability of the sensor is not facilitated.
Disclosure of Invention
In order to solve the defects in the related art, the application provides the MEMS gas sensor gas-sensitive unit and the preparation method, the structure of the MEMS gas sensor gas-sensitive unit is improved, the improvement of the performance of the sensor is realized on the premise of not adding extra environmental control means in the current MEMS process frame, and the method is simple and easy to realize and does not bring complexity and power consumption improvement. The specific technical scheme is as follows:
In a first aspect, the present application provides a method for preparing a MEMS gas sensor gas-sensitive unit, the method comprising:
Sequentially preparing a first metal electrode layer and an insulating layer from bottom to top on a substrate;
Preparing a second metal electrode layer with a first hole on the insulating layer, wherein a superposition area exists among the first hole, the insulating layer and the first metal electrode layer in the projection direction;
forming a second hole in the insulating layer in a region of the insulating layer, where the first hole projects on the insulating layer, and exposing the first metal electrode layer through the first hole and the second hole;
Covering a gas-sensitive material on the second metal electrode layer to form a gas-sensitive structure layer, so that the gas-sensitive material is communicated with the first metal electrode layer and the second metal electrode layer at the first hole and the second hole;
And patterning the gas-sensitive structural layer, retaining the gas-sensitive materials retained in the first holes and the second holes, and removing the rest of the gas-sensitive materials of the gas-sensitive structural layer to complete the preparation of the gas-sensitive unit.
Optionally, the preparing the first metal electrode layer and the insulating layer sequentially from bottom to top on the substrate includes:
Paving a first mask plate on the substrate, and forming a first metal electrode layer on the substrate after a sputtering-patterning-corrosion process;
and forming the insulating layer by film spreading on the first metal electrode layer.
Optionally, the preparing a second metal electrode layer with a first hole on the insulating layer includes:
and paving a second mask plate on the insulating layer, and forming a second metal electrode layer with the first hole on the insulating layer after a sputtering-patterning-corrosion process.
Optionally, the covering the second metal electrode layer with a gas-sensitive material to form a gas-sensitive structure layer includes:
And spin-coating the gas-sensitive material on the second metal electrode layer in a whole piece to form the gas-sensitive structure layer.
Optionally, the retaining the gas-sensitive material retained in the first hole and the second hole includes:
and retaining the gas sensitive material on the inner walls of the first hole and the second hole.
In a second aspect, the present application also provides a MEMS gas sensor gas sensing unit obtained using the method of preparation as provided in the first aspect and the various alternatives of the first aspect.
Optionally, the substrate is a surface oxide layer of a silicon oxide wafer, and the thickness of the substrate is the same as the original thickness of the surface oxide layer of the silicon oxide wafer.
Optionally, the thickness of the first metal electrode layer is 90nm-110nm, and the material of the first metal electrode layer is conductive metal material.
Optionally, the insulating layer is an insulating layer formed by directly forming a film on the first metal electrode layer in a whole piece, and the insulating layer is made of SiO2, si3N4 or Al2O3.
Optionally, the thickness of the second metal electrode layer is 90nm-110nm, and the material of the first metal electrode layer is conductive metal material.
Through the technical scheme, the application at least has the following beneficial effects:
The gas-sensitive unit is provided with a sandwich multilayer structure comprising two metal electrode layers and an intermediate insulating layer in the thickness direction, a second metal electrode layer (upper layer) is provided with holes, the insulating layer covered in the hole area is removed, and a gas-sensitive structure layer is prepared on the second insulating layer, so that the gas-sensitive film is communicated with the first metal electrode layer and the second metal electrode layer at the holes; because the effective part of the gas-sensitive structure layer is only distributed at the edge of the side wall in the depth direction of the opening, the scheme can greatly reduce the total volume of the effective part of the gas-sensitive structure, and meanwhile, the specific surface area of the effective part of the gas-sensitive structure layer which can interact with external gas is increased, so that the sensitivity and the response speed of the sensor can be improved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a method of fabricating a MEMS gas sensor gas-sensitive cell provided in one embodiment of the application;
FIG. 2A is a top view of a first metal electrode layer fabricated on a substrate provided in one embodiment of the application;
FIG. 2B is a top view of a first metal electrode layer fabricated on a substrate provided in another embodiment of the application;
FIG. 2C is a schematic diagram of FIG. 2A at section AA 'or FIG. 2B at section BB';
FIG. 3A is a top view of the second metal electrode layer laid on top of FIG. 2A;
Fig. 3B is a top view of the second metal electrode layer laid on top of fig. 2B;
FIG. 3C is a schematic view of FIG. 3A at section AA 'or FIG. 3B at section BB';
FIG. 4A is a top view of the insulating layer with a second hole formed through the first hole based on FIG. 3A;
FIG. 4B is a top view of the insulating layer with a second hole formed through the first hole based on FIG. 3B;
FIG. 4C is a schematic view of FIG. 4A at section AA 'or FIG. 4B at section BB';
FIG. 5A is a top view of the gas sensitive structural layer prepared on the basis of FIG. 4A;
FIG. 5B is a schematic view of the cross-section AA' after the gas sensitive material remaining in the first hole and the second hole after FIG. 5A is removed;
FIG. 5C is a schematic cross-sectional view of FIG. 5B continuing to remove the gas-sensitive material within the hole, leaving the gas-sensitive material only on the inner wall of the hole.
Wherein, the reference numerals are as follows:
10. a substrate; 20. a first metal electrode layer; 30. an insulating layer; 31. a second hole; 40. a second metal electrode layer; 41. a first hole; 50. a gas sensitive structural layer.
Detailed Description
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the invention. Rather, they are merely examples of apparatus and methods consistent with aspects of the invention as detailed in the accompanying claims.
MEMS gas sensors are typically multi-layered structures comprising an electrode layer, an insulating layer, a gas sensitive structural layer, etc., and are limited by MEMS processing conditions, conventional MEMS gas sensor manufacturing processes typically produce patterned metal electrodes on the insulating layer, with the electrodes being divided into two or more groups, in the shape of comb teeth, and then produce the gas sensitive structural layer on the electrodes by a thin film or thick film process, but this step involves a relatively complex chemical process that is difficult to perform using conventional MEMS processes. Obviously, the structural design and the processing quality of the gas-sensitive structural layer have decisive influence on the performance level of the MEMS gas sensor, namely, the application provides a novel MEMS gas sensor gas-sensitive unit and a preparation process method thereof in a standard MEMS process frame, which are used for controllably reducing the absolute volume of the gas-sensitive structural layer and increasing the specific surface area of an effective part of the gas-sensitive structural layer which can interact with external gas under the constraint of the conventional process capability.
Fig. 1 is a method for preparing a MEMS gas sensor gas-sensitive unit according to an embodiment of the present application, the method comprising:
step 101, preparing a first metal electrode layer and an insulating layer on a substrate in sequence from bottom to top;
The substrate referred to herein may be a surface oxide layer of a silicon oxide wafer, the thickness of the substrate being the same as the original thickness of the surface oxide layer of the silicon oxide wafer.
When the first metal electrode layer and the insulating layer are sequentially prepared on the substrate from bottom to top, the method can comprise the following two steps:
s1, paving a first mask plate on a substrate, and forming a first metal electrode layer on the substrate after a sputtering-patterning-corrosion process;
The thickness of the first metal electrode layer may be 90nm to 110nm, for example, the thickness of the first metal electrode layer may be 90nm, 95nm, 100nm, 105nm, 110nm, etc., and the thickness thereof may be set according to actual needs. The material of the first metal electrode layer is a conductive metal material, such as gold, silver, aluminum, or the like, which is excellent in conductivity.
The first mask may be a mask with a regular shape or a mask with an irregular shape.
As shown in fig. 2A and 2B, fig. 2A and 2B show two different shapes of schematic diagrams of the first metal electrode layer prepared on the substrate, and fig. 2A and 2B show a schematic cross-sectional view of fig. 2C, in which the first metal electrode layer 20 is formed on the substrate 10.
S2, forming an insulating layer by film laying on the first metal electrode layer in a whole piece.
The insulating layer may be an insulating layer formed by directly forming a film on the first metal electrode layer 20 in a monolithic manner, and the insulating layer may be made of SiO2, si3N4, al2O3, or the like.
Step 102, preparing a second metal electrode layer with a first hole on an insulating layer, wherein a superposition area exists among the first hole, the insulating layer and the first metal electrode layer in the projection direction;
When the second metal electrode layer with the first hole is prepared on the insulating layer, the second mask plate is paved on the insulating layer, and the second metal electrode layer with the first hole is formed on the insulating layer after the sputtering, patterning and corrosion processes.
The second mask may be a mask of a regular shape or a mask of an irregular shape.
The first hole may be circular or non-circular.
As a schematic view of preparing a second metal electrode layer having a first hole on an insulating layer, see fig. 3A and 3B, fig. 3A and 3B show two different shapes of schematic views of preparing a second metal electrode layer 40 having a first hole 41 on an insulating layer 30, and fig. 3A and 3B are schematic cross-sectional views of fig. 3C, in which the second metal electrode layer 40 is formed on the insulating layer 30.
Step 103, forming a second hole in the insulating layer in the area where the first hole projects on the insulating layer, and exposing the first metal electrode layer through the first hole and the second hole;
the projections of the second hole and the first hole 41 overlap, the projection of the first hole 41 is larger than the projection of the second hole, or the projection of the first hole 41 is the same as the projection of the second hole.
The schematic diagrams of forming the second hole 31 in the region of the insulating layer 30 where the first hole 41 projects onto the insulating layer 30 are shown in fig. 4A and 4B, fig. 4A and 4B show two different shapes of schematic diagrams of forming the second hole 31 in the insulating layer 30, and the schematic cross-sectional diagrams of fig. 4A and 4B are shown in fig. 4C, where the second hole 31 is formed in the insulating layer 30 through the first hole 41.
104, Covering the second metal electrode layer with a gas-sensitive material to form a gas-sensitive structure layer, so that the gas-sensitive material is communicated with the first metal electrode layer and the second metal electrode layer at the first hole and the second hole;
When the second metal electrode layer 40 is covered with the gas-sensitive material to form the gas-sensitive structure layer, the gas-sensitive structure layer is formed by spin-coating the gas-sensitive material on the whole piece of the second metal electrode layer 40.
A schematic diagram of forming the gas-sensitive structure layer 50 by covering the second metal electrode layer 40 with a gas-sensitive material may be seen in fig. 5A, and fig. 5A shows a top view of the gas-sensitive structure layer 50 prepared on the basis of fig. 4A.
And 105, patterning the gas-sensitive structural layer, retaining the gas-sensitive materials retained in the first holes and the second holes, and removing the rest of the gas-sensitive materials of the gas-sensitive structural layer to complete the preparation of the gas-sensitive unit.
Please refer to fig. 5B, which is a schematic diagram of the cross section AA' after the remaining gas-sensitive material in the first hole 41 and the second hole 31 is removed after fig. 5A.
When the gas-sensitive materials reserved in the first holes and the second holes are reserved, only the gas-sensitive materials can be reserved on the inner walls of the first holes and the second holes, so that the total volume of the gas-sensitive structural layer is reduced, and the specific surface area is increased. As shown in fig. 5C, which is a schematic cross-sectional view of fig. 5B continuing to remove the gas-sensitive material in the hole, leaving the gas-sensitive material only on the inner wall of the hole.
In summary, according to the method for preparing the MEMS gas sensor gas-sensitive unit provided by the application, the obtained gas-sensitive unit has a sandwich multilayer structure comprising two metal electrode layers and an intermediate insulating layer in the thickness direction, the second metal electrode layer (upper layer) is provided with an opening, the insulating layer covered in the opening area is removed, and the gas-sensitive structure layer is prepared on the second insulating layer, so that the gas-sensitive film is communicated with the first metal electrode layer and the second metal electrode layer at the opening; because the effective part of the gas-sensitive structure layer is only distributed at the edge of the side wall in the depth direction of the opening, the scheme can greatly reduce the total volume of the effective part of the gas-sensitive structure, and meanwhile, the specific surface area of the effective part of the gas-sensitive structure layer which can interact with external gas is increased, so that the sensitivity and the response speed of the sensor can be improved.
In addition, the application also provides a MEMS gas sensor gas-sensitive unit which is obtained by adopting the preparation method shown in fig. 1, and the specific manufacturing process flow can be referred to the description of each step of fig. 1.
In practical implementation, the substrate may be a surface oxide layer of a silicon oxide wafer, and the thickness of the substrate is the same as the original thickness of the surface oxide layer of the silicon oxide wafer.
Alternatively, the thickness of the first metal electrode layer may be 90nm to 110nm, for example, the thickness of the first metal electrode layer may be 90nm, 95nm, 100nm, 105nm, 110nm, etc., and the thickness thereof may be set according to actual needs. The material of the first metal electrode layer is a conductive metal material, such as gold, silver, aluminum, or the like, which is excellent in conductivity.
Alternatively, the insulating layer may be an insulating layer formed by directly forming a film on the first metal electrode layer in a monolithic manner, and the insulating layer may be made of SiO2, si3N4, al2O3, or the like.
Similarly, the thickness of the second metal electrode layer may be 90nm to 110nm, for example, the thickness of the second metal electrode layer is 90nm, 95nm, 100nm, 105nm, 110nm, etc., and the thickness thereof may be set according to practical needs. The material of the second metal electrode layer is a conductive metal material, such as gold, silver, aluminum, or the like, which is excellent in conductivity.
In summary, the MEMS gas sensor gas-sensitive unit provided by the application has a sandwich multilayer structure including two metal electrode layers and an intermediate insulating layer in the thickness direction, wherein the second metal electrode layer (upper layer) is perforated, the insulating layer covered in the perforation area is removed, and the gas-sensitive structure layer is prepared on the second insulating layer, so that the gas-sensitive film is communicated with the first metal electrode layer and the second metal electrode layer at the perforation position; because the effective part of the gas-sensitive structure layer is only distributed at the edge of the side wall in the depth direction of the opening, the scheme can greatly reduce the total volume of the effective part of the gas-sensitive structure, and meanwhile, the specific surface area of the effective part of the gas-sensitive structure layer which can interact with external gas is increased, so that the sensitivity and the response speed of the sensor can be improved.
Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (9)
1. A method of manufacturing a MEMS gas sensor gas-sensitive cell, the method comprising:
sequentially preparing a first metal electrode layer and an insulating layer from bottom to top on a substrate;
Preparing a second metal electrode layer with a first hole on the insulating layer, wherein a superposition area exists among the first hole, the insulating layer and the first metal electrode layer in the projection direction;
forming a second hole in the insulating layer in a region of the insulating layer, where the first hole projects on the insulating layer, and exposing the first metal electrode layer through the first hole and the second hole;
Covering a gas-sensitive material on the second metal electrode layer to form a gas-sensitive structure layer, so that the gas-sensitive material is communicated with the first metal electrode layer and the second metal electrode layer at the first hole and the second hole;
And patterning the gas-sensitive structural layer, only retaining the gas-sensitive materials retained by the inner walls of the first holes and the second holes, and removing the rest of the gas-sensitive materials of the gas-sensitive structural layer to complete the preparation of the gas-sensitive unit.
2. The method of claim 1, wherein sequentially preparing the first metal electrode layer and the insulating layer on the substrate from bottom to top comprises:
Paving a first mask plate on the substrate, and forming a first metal electrode layer on the substrate after a sputtering-patterning-corrosion process;
and forming the insulating layer by film spreading on the first metal electrode layer.
3. The method of manufacturing according to claim 1, wherein the manufacturing of the second metal electrode layer having the first hole on the insulating layer includes:
and paving a second mask plate on the insulating layer, and forming a second metal electrode layer with the first hole on the insulating layer after a sputtering-patterning-corrosion process.
4. The method of manufacturing according to claim 1, wherein the covering the second metal electrode layer with a gas-sensitive material to form a gas-sensitive structure layer includes:
And spin-coating the gas-sensitive material on the second metal electrode layer in a whole piece to form the gas-sensitive structure layer.
5. A MEMS gas sensor cell, characterized in that it is obtained by a method of preparation according to any one of claims 1-4.
6. The gas sensing unit of claim 5, wherein the substrate is a surface oxide layer of a silicon oxide wafer, and wherein the thickness of the substrate is the same as the original thickness of the surface oxide layer of the silicon oxide wafer.
7. A gas sensitive unit according to claim 5, wherein the thickness of the first metal electrode layer is 90nm-110nm, and the material of the first metal electrode layer is a conductive metal material.
8. The gas sensor unit according to claim 5, wherein the insulating layer is an insulating layer formed by directly forming a film on the first metal electrode layer in a whole piece, and the insulating layer is made of SiO2, si3N4 or Al2O3.
9. A gas sensitive unit according to claim 5, wherein the thickness of the second metal electrode layer is 90nm-110nm, and the material of the first metal electrode layer is a conductive metal material.
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