CN109896499B - Ceramic microstructure graphene gas sensor and manufacturing method thereof - Google Patents

Ceramic microstructure graphene gas sensor and manufacturing method thereof Download PDF

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CN109896499B
CN109896499B CN201910161174.9A CN201910161174A CN109896499B CN 109896499 B CN109896499 B CN 109896499B CN 201910161174 A CN201910161174 A CN 201910161174A CN 109896499 B CN109896499 B CN 109896499B
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graphene
ceramic
microstructure
sputtering
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CN109896499A (en
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杨永超
刘继江
刘玺
秦浩
王成杨
王洋洋
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CETC 49 Research Institute
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Abstract

The invention belongs to the technical field of sensors, and particularly relates to a ceramic microstructure graphene gas sensor and a manufacturing method thereof. The invention aims to solve the problems of difficult CVD growth and modification of graphene on ceramic heterogeneous materials and large structural size of a sensor. According to the invention, an MEMS (micro electro mechanical systems) process technology is adopted to manufacture a sensor heating resistor and a signal output electrode on a ceramic heterogeneous material substrate, a PVD (physical vapor deposition) technology is adopted to manufacture a seed layer for graphene growth on the substrate, a CVD (chemical vapor deposition) technology is adopted to realize the growth of graphene on the seed layer, a chemical modification means is adopted to realize the functional modification of graphite, and the preparation of the graphene gas sensor is completed. The sensor has the characteristics of high performance and small size, and is used for simultaneously detecting the concentration of various gases through the array integration of the sensing units.

Description

Ceramic microstructure graphene gas sensor and manufacturing method thereof
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a ceramic microstructure graphene gas sensor and a manufacturing method thereof.
Background
The trace amount of gas in the environment is harmful to the health and safety of human body, such as NO2、NH3、CO、H2S and the like. Therefore, trace gas in the environment needs to be detected in the environment, and the physical health and safety of personnel are guaranteed. Currently, the detection technology of gas concentration in the environment mainly includes a semiconductor type, an electrochemical type, a catalytic combustion type, a thermal conduction type, an optical type, and the like. Among them, the semiconductor gas sensor has been widely used due to its high sensitivity and fast response, and related products are introduced in the fields of industrial environment, air quality, and closed environment, for example, in the japan FIGARO corporation, the hennwer science and technology. But using a conventional sensorThe sensor designed by the material sensing system needs high-temperature operation, so that the power consumption is high, the response time is limited due to the fact that the sensitive material is prepared by adopting a thick film process, the problem of large volume is caused by the traditional manufacturing process, the design and the manufacture of miniaturization and integration of the sensor are difficult to realize, and the development of the sensor is limited.
Graphene has excellent gas-sensitive properties as a new generation material reinforcement. Researches show that the graphene gas-sensitive material can realize the ppb level rapid detection of gas, can effectively reduce the required working temperature of the sensitive material, and is the mainstream direction of the development of the sensitive material of the gas sensor. At present, the high-quality graphene growth technology mainly adopts a CVD method to grow on a copper or nickel-substrate, and how to realize heterogeneous growth of graphene on a ceramic substrate is difficult to develop a graphene gas sensor. In addition, with the development of the MEMS technology, the adoption of the MEMS technology to prepare the gas sensor can effectively reduce key technical indexes such as the size, the weight, the power consumption and the like of the existing sensor, and is a key development direction of a new-generation gas sensor.
Disclosure of Invention
The invention provides a ceramic microstructure graphene gas sensor and a manufacturing method thereof, aiming at solving the problems of difficult CVD growth and modification of graphene on the existing ceramic heterogeneous material and large structural size of the sensor.
The invention relates to a ceramic microstructure graphene gas sensor which comprises a ceramic substrate, a microstructure layer, a seed layer and a graphene sensitive layer;
the ceramic substrate is Al with a polished surface2O3A ceramic plate; the thickness of the ceramic substrate is 0.1-1 mm;
the microstructure layer is arranged on the surface of the ceramic substrate and comprises a heating resistor and a signal output electrode; the signal output electrode consists of two electrodes in the shape of separated fingers, and the two electrodes are arranged in a staggered manner and are not in contact with each other; the heating resistors are distributed in a snake shape at the gap of the signal output electrode and are not contacted with the signal output electrode; the thickness of the microstructure layer is 500-1500 nm; the resistance value of the heating resistor is 5-50 omega, and the number of electrode pairs of the signal output electrode is 3-10 pairs;
the seed layer is arranged at the gap between the heating resistor and the signal output electrode; the absolute value of the thickness difference between the seed layer and the microstructure layer is 50-300 nm;
the graphene sensitive layer covers the seed layer and is in contact communication with the heating resistor of the microstructure layer and the signal output electrode.
The preparation method of the ceramic microstructure graphene gas sensor specifically comprises the following steps:
firstly, cleaning a ceramic substrate: boiling and cleaning the ceramic substrate for 30-60 min at the temperature of 60-100 ℃ by using the mixed solution, and then washing and spin-drying the ceramic substrate by using deionized water by using a spin dryer; the mixed solution is an aqueous solution of concentrated sulfuric acid and potassium dichromate, wherein the ratio of concentrated sulfuric acid: potassium dichromate: (0.8-1.2) g of (15-25) mL of water;
secondly, preparing a microstructure layer: sequentially carrying out metal film sputtering, heat treatment, photoetching and etching on the ceramic substrate prepared in the step one to form a microstructure layer containing a heating resistor and a signal output electrode; the thickness of the microstructure layer is 500-1500 nm;
thirdly, seed layer preparation: preparing a seed layer on the surface of the ceramic substrate at the gap of the microstructure layer by adopting a PVD (physical vapor deposition) technology; preparation of NiAl by controlling technological parameters2O4-xFilm or CuAl2O4-xPerforming photoresist removing treatment on the film to show a microstructure, annealing the ceramic substrate in a reducing atmosphere, and forming Ni or Cu clusters on the surface;
fourthly, preparing a graphene sensitive layer: and (4) growing graphene on the seed layer prepared in the third step by adopting a CVD (chemical vapor deposition) technology, and performing functional modification on the completely grown graphene layer to form the ceramic microstructure graphene gas sensor.
The invention has the beneficial effects that:
the graphene gas sensor is simple in structure and small in size, and different types of gases are detected by functionally modifying graphene. The graphene gas sensor is designed and manufactured based on MEMS technology, the manufacturing process is mature, the mass production of the sensor is easy to realize, and the miniaturization and integration design and manufacturing of the sensor are easy to realize.
Drawings
FIG. 1 is a schematic diagram of a structure in which layers of a ceramic microstructure graphene gas sensor are separated;
FIG. 2 is a front view of a plurality of ceramic microstructure graphene gas sensor arrays arranged;
FIG. 3 is a performance test curve of a nano-silver graphene functionalized modified gas sensor;
fig. 4 is a linearity curve of the nano-silver graphene functionalized modified gas sensor.
Detailed Description
The first embodiment is as follows: with reference to fig. 1 and fig. 2, a ceramic microstructure graphene gas sensor according to this embodiment includes a ceramic substrate 1, a microstructure layer 2, a seed layer 3, and a graphene sensitive layer 4;
the ceramic substrate 1 is Al with a polished surface2O3A ceramic plate; the thickness of the ceramic substrate 1 is controlled to be 0.1-1 mm;
the microstructure layer 2 is arranged on the surface of the ceramic substrate 1, and the microstructure layer 2 comprises a heating resistor 2-1 and a signal output electrode 2-2; the signal output electrode 2-2 consists of two electrodes in the shape of separated fingers, and the two electrodes are arranged in a staggered manner and are not in contact with each other; the heating resistors 2-1 are distributed in a snake shape at the gap of the signal output electrode 2-2 and are not contacted with the signal output electrode 2-2; the thickness of the microstructure layer 2 is controlled to be 500-1500 nm; the resistance value of the heating resistor 2-1 is controlled to be 5-50 omega, and the number of electrode pairs of the signal output electrode 2-2 is controlled to be 3-10 pairs;
the seed layer 3 is arranged at the gap between the heating resistor 2-1 and the signal output electrode 2-2; the absolute value of the thickness difference between the seed layer 3 and the microstructure layer 2 is controlled to be 50-300 nm;
the graphene sensitive layer 4 covers the seed layer 3 and is in contact communication with the heating resistor 2-1 and the signal output electrode 2-2 in the microstructure layer 2.
The ceramic substrate of the present embodiment plays a role of supporting and insulating.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the heating resistor 2-1 is Au or Pt; the signal output electrode 2-2 is Au or Pt. The rest is the same as the first embodiment.
The heating resistor of the embodiment provides required temperature for the sensor, and the signal output electrode is used for outputting a sensor signal.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the seed layer 3 is NiAl prepared by adopting a PVD technology2O4-xFilm or CuAl2O4-xA film; the PVD technology adopts a corresponding ceramic target material to carry out radio frequency magnetron sputtering or adopts an alloy target material to carry out direct current reactive magnetron sputtering; the purity of the ceramic target material is NiAl with 99.99 percent2O4Target or CuAl2O4A target; the Cu-Al alloy target or the Ni-Al alloy target with the purity of the alloy target material of 99.99 percent is described. The others are the same as in the first or second embodiment.
NiAl produced by the present embodiment2O4-xOr CuAl2O4-xAnnealing the film in a reducing atmosphere to realize Ni+2Or Cu+2The ions are reduced and transferred to the surface to form Ni or Cu clusters, and catalytic active sites are provided for graphene growth.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the graphene is prepared by adopting a CVD (chemical vapor deposition) technology, and the grown graphene is subjected to functional modification. The rest is the same as one of the first to third embodiments.
According to the embodiment, the specific perception of different gases is realized by functionally modifying the growing graphene.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the functional modification comprises organic molecule, functional group, metal or compound modification. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the preparation method of the ceramic microstructure graphene gas sensor comprises the following steps:
firstly, cleaning a ceramic substrate: boiling and cleaning the ceramic substrate for 30-60 min at the temperature of 60-100 ℃ by using the mixed solution, and then washing and spin-drying the ceramic substrate by using deionized water by using a spin dryer; the mixed solution is an aqueous solution of concentrated sulfuric acid and potassium dichromate, wherein the ratio of concentrated sulfuric acid: potassium dichromate: (0.8-1.2) g of (15-25) mL of water;
secondly, preparing a microstructure layer: sequentially carrying out metal film sputtering, heat treatment, photoetching and etching on the ceramic substrate prepared in the step one to form a microstructure layer containing a heating resistor and a signal output electrode; the thickness of the microstructure layer is controlled to be 500-1500 nm;
thirdly, seed layer preparation: preparing a seed layer on the surface of the ceramic substrate at the gap of the microstructure layer by adopting a PVD (physical vapor deposition) technology; preparation of NiAl by controlling technological parameters2O4-xFilm or CuAl2O4-xPerforming photoresist removing treatment on the film to show a microstructure, annealing the ceramic substrate in a reducing atmosphere, and forming Ni or Cu clusters on the surface;
fourthly, preparing a graphene sensitive layer: and (4) growing graphene on the seed layer prepared in the third step by adopting a CVD (chemical vapor deposition) technology, and performing functional modification on the completely grown graphene layer to form the ceramic microstructure graphene gas sensor.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the preparation of the microstructure layer in the second step is carried out according to the following steps:
sputtering a metal film: a magnetron sputtering deposition system is adopted, and the thickness of the metal film is controlled to be 500-1500 nm by controlling process parameters; selecting a gold or platinum target with 99.99 percent of target material, and controlling the sputtering power to be 200-1000 w; the sputtering time is controlled to be 30-70 min; the sputtering gas is Ar; controlling the sputtering pressure to be 0.5-2 Pa;
heat treatment: carrying out heat treatment on the metal film sputtered in the step I at the temperature of 800-1200 ℃ by adopting a ceramic sintering furnace, and controlling the constant temperature time to be 1-3 h;
③ photoetching: coating the ceramic substrate subjected to the heat treatment in the second step with photoresist by using a coater, controlling the thickness of the photoresist to be 0.2-1 mu m, and coating the photoresist by using a hot plate machinePre-baking the ceramic substrate of the photoresist for 150-200 s at 80-120 ℃, and exposing the substrate on a mask plate by using a photoetching machine, wherein the exposure time is controlled to be 15-30 s, and the exposure intensity is controlled to be (50-80) multiplied by 100 mu w/cm2(ii) a Developing the ceramic substrate in a developing solution for 20-50 s, and hardening the film for 10-30 min at 80-120 ℃ by adopting a hot plate machine; and etching the substrate by adopting an ion beam etching machine, controlling the etching time to be 50-70 min, and cleaning and aligning the shape of the microstructure after etching to finish the preparation of the microstructure layer. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the sixth or seventh embodiment is different from the sixth or seventh embodiment in that: the preparation of the seed layer in the third step is specifically carried out according to the following steps:
firstly, carrying out NiAl by a magnetron sputtering deposition system2O4-xFilm or CuAl2O4-xFilm sputtering: by using NiAl2O4Or CuAl2O4Performing radio frequency magnetron sputtering on the ceramic target, wherein the sputtering technological parameters are as follows: controlling the sputtering power to be 200-500 w; the sputtering time is controlled to be 40-80 min; the sputtering gas is Ar; controlling the sputtering pressure to be 0.5-2 Pa;
removing the photoresist: carrying out photoresist removal treatment on the substrate by using acetone and ethanol solution, cleaning the photoresist to show a microstructure layer, and controlling the photoresist removal time to be 5-10 min;
annealing: placing the substrate in H2Annealing in an Ar reducing atmosphere, wherein the annealing temperature is controlled to be 800-1100 ℃, and the constant temperature time is controlled to be 0.5-2 h. The rest is the same as the sixth or seventh embodiment.
The specific implementation method nine: this embodiment differs from one of the sixth to eighth embodiments in that: the preparation of the seed layer in the third step is specifically carried out according to the following steps:
firstly, carrying out NiAl by a magnetron sputtering deposition system2O4-xFilm or CuAl2O4-xFilm sputtering: performing direct-current reactive magnetron sputtering by adopting a Cu-Al alloy or Ni-Al alloy target material, wherein the sputtering technological parameters are as follows: controlling the sputtering power to be 200-500 w; the sputtering time is controlled to be 40-80 min; the sputtering gas is Ar; the reaction gas is O2(ii) a The sputtering pressure is controlled to be 0.5-2 Pa, O2Controlling the partial pressure to be 50-70%;
removing the photoresist: carrying out photoresist removal treatment on the substrate by using acetone and ethanol solution, cleaning the photoresist to show a microstructure layer, and controlling the photoresist removal time to be 5-10 min;
annealing: placing the substrate in H2Annealing in an Ar reducing atmosphere, wherein the annealing temperature is controlled to be 800-1100 ℃, and the constant temperature time is controlled to be 0.5-2 h. The rest is the same as in one of the sixth to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the sixth to ninth embodiments in that: the preparation of the graphene sensitive layer in the fourth step is specifically carried out according to the following steps:
growing graphene: growing graphene by Chemical Vapor Deposition (CVD) system using CH4Or C2H4As a carbon source, H2As carrier gas, the growth temperature is controlled at 800-1100 ℃;
functional modification: preparing a nano gold, nano silver, a nano metal oxide or an organic matter solution, controlling the concentration within the range of 0.05-2 mg/mL, sucking the modification solution by using a micropipettor, dripping the trace solution at the growing graphene, and drying at the temperature of 50-200 ℃ to finish the functional modification of the graphene and finish the preparation of the graphene sensitive layer. The others are the same as in one of the sixth to ninth embodiments.
The concrete implementation mode eleven: this embodiment differs from one of the sixth to tenth embodiments in that: in the preparation process of the ceramic microstructure graphene gas sensor, a plurality of repeated structural units are prepared on a ceramic substrate, different graphene functional modifications are carried out on different structural units, and the array and integration preparation of the ceramic microstructure graphene gas sensor is realized. The others are the same as in one of the sixth to tenth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the ceramic microstructure graphene gas sensor specifically comprises the following steps:
firstly, cleaning a ceramic substrate: boiling and cleaning the ceramic substrate for 30-60 min at the temperature of 60-100 ℃ by using the mixed solution, and then washing and spin-drying the ceramic substrate by using deionized water by using a spin dryer; the mixed solution is an aqueous solution of concentrated sulfuric acid and potassium dichromate, wherein the ratio of concentrated sulfuric acid: potassium dichromate: (0.8-1.2) g of (15-25) mL of water;
secondly, preparing a microstructure layer: sputtering a metal film: a magnetron sputtering deposition system is adopted, and the thickness of the metal film is controlled to be 500-1500 nm by controlling process parameters; selecting a gold or platinum target with 99.99 percent of target material, and controlling the sputtering power to be 200-1000 w; the sputtering time is controlled to be 30-70 min; the sputtering gas is Ar; controlling the sputtering pressure to be 0.5-2 Pa;
heat treatment: carrying out heat treatment on the metal film sputtered in the step I at the temperature of 800-1200 ℃ by adopting a ceramic sintering furnace, and controlling the constant temperature time to be 1-3 h;
③ photoetching: coating the ceramic substrate subjected to heat treatment in the second step with photoresist by using a coater, controlling the thickness of the photoresist to be 0.2-1 mu m, prebaking the ceramic substrate coated with the photoresist for 150-200 s at 80-120 ℃ by using a hot plate machine, exposing the substrate on a mask plate by using the coater, controlling the exposure time to be 15-30 s, and controlling the exposure intensity to be (50-80) multiplied by 100 mu w/cm2(ii) a Developing the ceramic substrate in a developing solution for 20-50 s, and hardening the film for 10-30 min at 80-120 ℃ by adopting a hot plate machine; etching the substrate by using an ion beam etching machine, controlling the etching time to be 50-70 min, and cleaning and aligning the shape of the microstructure after etching to finish the preparation of the microstructure layer; forming a microstructure layer containing a heating resistor and a signal output electrode; the thickness of the microstructure layer is controlled to be 500-1500 nm;
thirdly, seed layer preparation: firstly, carrying out NiAl by a magnetron sputtering deposition system2O4-xFilm or CuAl2O4-xFilm sputtering: by using NiAl2O4Or CuAl2O4Performing radio frequency magnetron sputtering on the ceramic target, wherein the sputtering technological parameters are as follows: controlling the sputtering power to be 200-500 w; the sputtering time is controlled to be 40-80 min; the sputtering gas is Ar; sputtering pressure controlUnder 0.5-2 Pa;
removing the photoresist: carrying out photoresist removal treatment on the substrate by using acetone and ethanol solution, cleaning the photoresist to show a microstructure layer, and controlling the photoresist removal time to be 5-10 min;
annealing: placing the substrate in H2Annealing in an Ar reducing atmosphere, controlling the annealing temperature to be 800-1100 ℃ and the constant temperature time to be 0.5-2 h;
fourthly, preparing a graphene sensitive layer: growing graphene: growing graphene by Chemical Vapor Deposition (CVD) system using CH4Or C2H4As a carbon source, H2As carrier gas, the growth temperature is controlled at 800-1100 ℃;
functional modification: preparing a nano gold, nano silver, a nano metal oxide or an organic matter solution, controlling the concentration within the range of 0.05-2 mg/mL, sucking the modification solution by using a micropipettor, dripping the trace solution at the growing graphene, drying at the temperature of 50-200 ℃, completing the functional modification of the graphene, completing the preparation of the graphene sensitive layer, and forming the ceramic microstructure graphene gas sensor.
The nano-silver modified graphene gas sensor is subjected to performance test, and as shown in fig. 3 and 4, the sensor is used for testing NO2The gas shows excellent gas-sensitive performance, and NO can be realized at room temperature2And (5) detecting the gas, wherein the test linearity reaches 0.9851.
The method is based on MEMS technology, and comprises film growth, photoetching, etching and the like. The preparation of different gas sensors and the array integration of the sensors are realized by controlling the growth and specific modification of graphene on a ceramic substrate. The manufacturing method of the embodiment has the characteristics of simple process, mature technology, capability of batch production and the like, and the obtained sensor has the advantages of stable performance and the like. The method can be applied to trace gas detection in the environments such as closed environment, atmospheric environment, underground pipe gallery and the like.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. The ceramic microstructure graphene gas sensor is characterized by comprising a ceramic substrate (1), a microstructure layer (2), a seed layer (3) and a graphene sensitive layer (4);
the ceramic substrate (1) is Al with polished surface2O3A ceramic plate; the thickness of the ceramic substrate (1) is controlled to be 0.1-1 mm;
the microstructure layer (2) is arranged on the surface of the ceramic substrate (1), and the microstructure layer (2) comprises a heating resistor (2-1) and a signal output electrode (2-2); the signal output electrode (2-2) consists of two electrodes in the shape of separated fingers, and the two electrodes are arranged in a staggered manner and are not in contact with each other; the heating resistors (2-1) are distributed in a snake shape at the gap of the signal output electrode (2-2) and are not contacted with the signal output electrode (2-2); the thickness of the microstructure layer (2) is controlled to be 500-1500 nm; the resistance value of the heating resistor (2-1) is controlled to be 5-50 omega, and the number of electrode pairs of the signal output electrode (2-2) is controlled to be 3-10 pairs;
the seed layer (3) is arranged at the gap between the heating resistor (2-1) and the signal output electrode (2-2); the absolute value of the thickness difference between the seed layer (3) and the microstructure layer (2) is controlled to be 50-300 nm;
the graphene sensitive layer (4) covers the seed layer (3) and is in contact communication with the heating resistor (2-1) and the signal output electrode (2-2) in the microstructure layer (2).
2. The ceramic microstructure graphene gas sensor according to claim 1, wherein the heating resistor (2-1) is Au or Pt; the signal output electrode (2-2) is Au or Pt.
3. The ceramic microstructured graphene gas of claim 1The sensor is characterized in that the seed layer (3) is NiAl prepared by adopting a PVD technology2O4-xFilm or CuAl2O4-xA film; the PVD technology adopts a corresponding ceramic target material to carry out radio frequency magnetron sputtering or adopts an alloy target material to carry out direct current reactive magnetron sputtering; the ceramic target material is NiAl with the purity of 99.99 percent2O4Target or CuAl2O4A target; the alloy target is a Cu-Al alloy target or a Ni-Al alloy target with the purity of 99.99 percent.
4. The ceramic microstructure graphene gas sensor according to claim 3, wherein the graphene is prepared by a CVD technology, and the grown graphene is subjected to functional modification.
5. The ceramic microstructured graphene gas sensor according to claim 4, wherein the functionalized modification comprises a functional group, a metal or a compound modification.
6. The method for preparing a ceramic microstructure graphene gas sensor according to claim 1, wherein the method specifically comprises the following steps:
firstly, cleaning a ceramic substrate: boiling and cleaning the ceramic substrate for 30-60 min at the temperature of 60-100 ℃ by using the mixed solution, and then washing and spin-drying the ceramic substrate by using deionized water by using a spin dryer; the mixed solution is an aqueous solution of concentrated sulfuric acid and potassium dichromate, wherein the ratio of concentrated sulfuric acid: potassium dichromate: (0.8-1.2) g of (15-25) mL of water;
secondly, preparing a microstructure layer: sequentially carrying out metal film sputtering, heat treatment, photoetching and etching on the ceramic substrate prepared in the step one to form a microstructure layer containing a heating resistor and a signal output electrode; the thickness of the microstructure layer is controlled to be 500-1500 nm;
thirdly, seed layer preparation: preparing a seed layer on the surface of the ceramic substrate at the gap of the microstructure layer by adopting a PVD (physical vapor deposition) technology; preparation of NiAl by controlling technological parameters2O4-xFilm or CuAl2O4-xPerforming photoresist removing treatment on the film to show a microstructure, annealing the ceramic substrate in a reducing atmosphere, and forming Ni or Cu clusters on the surface;
fourthly, preparing a graphene sensitive layer: and (4) growing graphene on the seed layer prepared in the third step by adopting a CVD (chemical vapor deposition) technology, and performing functional modification on the completely grown graphene layer to form the ceramic microstructure graphene gas sensor.
7. The method for preparing a ceramic microstructure graphene gas sensor according to claim 6, wherein the preparation of the microstructure layer in the second step is specifically carried out according to the following steps:
sputtering a metal film: a magnetron sputtering deposition system is adopted, and the thickness of the metal film is controlled to be 500-1500 nm by controlling process parameters; selecting a gold or platinum target with 99.99 percent of target material, and controlling the sputtering power to be 200-1000 w; the sputtering time is controlled to be 30-70 min; the sputtering gas is Ar; controlling the sputtering pressure to be 0.5-2 Pa;
heat treatment: carrying out heat treatment on the metal film sputtered in the step I at the temperature of 800-1200 ℃ by adopting a ceramic sintering furnace, and controlling the constant temperature time to be 1-3 h;
③ photoetching: coating the ceramic substrate subjected to heat treatment in the second step with photoresist by using a coater, controlling the thickness of the photoresist to be 0.2-1 mu m, prebaking the ceramic substrate coated with the photoresist for 150-200 s at 80-120 ℃ by using a hot plate machine, exposing the substrate on a mask plate by using the coater, controlling the exposure time to be 15-30 s, and controlling the exposure intensity to be (50-80) multiplied by 100 mu w/cm2(ii) a Developing the ceramic substrate in a developing solution for 20-50 s, and hardening the film for 10-30 min at 80-120 ℃ by adopting a hot plate machine; and etching the substrate by using an ion beam etching machine, controlling the etching time to be 50-70 min, and cleaning the shape of the microstructure after etching to finish the preparation of the microstructure layer.
8. The method for preparing the ceramic microstructure graphene gas sensor according to claim 6, wherein the preparation of the seed layer in the third step is specifically carried out according to the following steps:
firstly, carrying out NiAl by a magnetron sputtering deposition system2O4-xFilm or CuAl2O4-xFilm sputtering: by using NiAl2O4Or CuAl2O4Performing radio frequency magnetron sputtering on the ceramic target, wherein the sputtering technological parameters are as follows: controlling the sputtering power to be 200-500 w; the sputtering time is controlled to be 40-80 min; the sputtering gas is Ar; controlling the sputtering pressure to be 0.5-2 Pa;
removing the photoresist: carrying out photoresist removal treatment on the substrate by using acetone and ethanol solution, cleaning the photoresist to show a microstructure layer, and controlling the photoresist removal time to be 5-10 min;
annealing: placing the substrate in H2Annealing in an Ar reducing atmosphere, wherein the annealing temperature is controlled to be 800-1100 ℃, and the constant temperature time is controlled to be 0.5-2 h.
9. The method for preparing the ceramic microstructure graphene gas sensor according to claim 6, wherein the preparation of the seed layer in the third step is specifically carried out according to the following steps:
firstly, carrying out NiAl by a magnetron sputtering deposition system2O4-xFilm or CuAl2O4-xFilm sputtering: performing direct-current reactive magnetron sputtering by adopting a Cu-Al alloy or Ni-Al alloy target material, wherein the sputtering technological parameters are as follows: controlling the sputtering power to be 200-500 w; the sputtering time is controlled to be 40-80 min; the sputtering gas is Ar; the reaction gas is O2(ii) a The sputtering pressure is controlled to be 0.5-2 Pa, O2Controlling the partial pressure to be 50-70%;
removing the photoresist: carrying out photoresist removal treatment on the substrate by using acetone and ethanol solution, cleaning the photoresist to show a microstructure layer, and controlling the photoresist removal time to be 5-10 min;
annealing: placing the substrate in H2Annealing in an Ar reducing atmosphere, wherein the annealing temperature is controlled to be 800-1100 ℃, and the constant temperature time is controlled to be 0.5-2 h.
10. The method for preparing the ceramic microstructure graphene gas sensor according to claim 6, wherein the preparation of the graphene sensitive layer in the fourth step is specifically carried out according to the following steps:
growing graphene: growing graphene by Chemical Vapor Deposition (CVD) system using CH4Or C2H4As a carbon source, H2As carrier gas, the growth temperature is controlled at 800-1100 ℃;
functional modification: preparing a nano gold, nano silver, a nano metal oxide or an organic matter solution, controlling the concentration within the range of 0.05-2 mg/mL, sucking the modification solution by using a micropipettor, dripping the trace solution at the growing graphene, and drying at the temperature of 50-200 ℃ to finish the functional modification of the graphene and finish the preparation of the graphene sensitive layer.
CN201910161174.9A 2019-03-04 2019-03-04 Ceramic microstructure graphene gas sensor and manufacturing method thereof Expired - Fee Related CN109896499B (en)

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