CN109896499A - A kind of ceramic microstructures graphene gas sensor and its manufacturing method - Google Patents

A kind of ceramic microstructures graphene gas sensor and its manufacturing method Download PDF

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CN109896499A
CN109896499A CN201910161174.9A CN201910161174A CN109896499A CN 109896499 A CN109896499 A CN 109896499A CN 201910161174 A CN201910161174 A CN 201910161174A CN 109896499 A CN109896499 A CN 109896499A
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graphene
ceramic
sputtering
gas sensor
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CN109896499B (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

A kind of ceramic microstructures graphene gas sensor and its manufacturing method, the invention belongs to sensor technical fields, and in particular to a kind of ceramic microstructures graphene gas sensor and its manufacturing method.The present invention is to solve the problems, such as that graphene CVD growth on ceramic foreign material, modification are difficult and sensor structure size is big.The present invention makes sensor adding thermal resistance and signal output electrode in ceramic foreign material base using MEMS technology technology, the seed layer of graphene growth is made on substrate of PVD technique, the growth of graphene on the seed layer is realized with CVD technology, the functional modification to graphite is realized with chemical modification techniques, completes the preparation of graphene gas sensor.Sensor of the invention has the characteristics that performance is high, size is small, integrates for multiple gases concentration while detecting by the array of sensing unit.

Description

A kind of ceramic microstructures graphene gas sensor and its manufacturing method
Technical field
The invention belongs to sensor technical fields, and in particular to a kind of ceramic microstructures graphene gas sensor and its system Make method.
Background technique
Micro gas endangers the healthy and safe generation of human body in environment, such as NO2、NH3、CO、H2S etc..Therefore, environment In need to detect minimum gas in environment, the health and safety of support personnel.Currently, gas concentration in environment Detection technique mainly includes semiconductor-type, electric chemical formula, catalytic combustion type, heat-conducted, optical profile type etc..Wherein, semi-conductor gas Sensor has the characteristics that high sensitivity, fast have been obtained of response are widely applied, such as FIGARO company, Japan, the bright section in Henan Skill etc. is proposed relative technological products for fields such as industrial environment, air quality, closed environments.But using traditional sensitive material The sensor of System Design needs hot operation to cause power consumption larger, sensitive material using thick-film technique preparation cause the response time by Limit, conventional fabrication processes lead to there is a problem of that volume is big, it is difficult to realize sensor miniaturization, integrated design and manufacture, limit The development of sensor is made.
Graphene has excellent air-sensitive performance as Material reinforcement body of new generation.Studies have shown that graphene gas sensitive The quickly detection of ppb grades of gas may be implemented, can effectively reduce operating temperature needed for sensitive material, be gas sensor sensitive material The main flow direction of development.Currently, high-quality graphene growing technology mainly uses CVD method to grow on copper or nickel-substrate, such as What realizes that the Heteroepitaxy of graphene is the where the shoe pinches of graphene gas sensor exploitation on a ceramic substrate.In addition, with The development of MEMS technology technology, preparing gas sensor using MEMS technology technology can effectively reduce existing size sensor, again The key technical index such as amount, power consumption are gas sensor prior development directions of new generation.
Summary of the invention
The present invention is to solve graphene CVD growth on existing ceramic foreign material, modification difficulty and sensor structure The big problem of size, and a kind of ceramic microstructures graphene gas sensor and its manufacturing method are provided.
A kind of ceramic microstructures graphene gas sensor of the present invention includes ceramic bases, microstructured layers, seed layer and stone Black alkene sensitive layer;
The ceramic bases are the Al of surface polishing2O3Potsherd;The ceramic bases with a thickness of 0.1~1mm;
The microstructured layers are arranged on ceramic bases surface, and the microstructured layers include adding thermal resistance and signal output electricity Pole;Signal output electrode is formed by two in the electrode for separating finger-shaped, and two electrodes are interlaced to be arranged and be not in contact with each other;Add It the serpentine-like gap location for being distributed in signal output electrode of thermal resistance and is not in contact with each other with signal output electrode;The microstructured layers With a thickness of 500~1500nm;Adding thermal resistance resistance value is 5~50 Ω, and the electrode logarithm of signal output electrode is 3~10 pairs;
The gap location of adding thermal resistance and signal output electrode is arranged in the seed layer;The thickness of seed layer and microstructured layers The absolute value of difference is 50~300nm;
Graphene sensitive layer covers seed layer, and contacts connection with adding thermal resistance in microstructured layers and signal output electrode.
A kind of preparation method of ceramic microstructures graphene gas sensor specifically includes the following steps:
One, ceramic substrate cleans: selecting mixed solution to boil ceramic substrate under conditions of temperature is 60~100 DEG C clear After washing 30~60min, deionized water flushing, drying are carried out to ceramic substrate using dryer;The mixed solution is the concentrated sulfuric acid With the aqueous solution of potassium bichromate, the wherein concentrated sulfuric acid: potassium bichromate: water=(0.8~1.2) g:(15~25) mL:(15~25) mL;
Two, prepared by microstructured layers: ceramic substrate is made in step 1 and successively carries out metal film sputtering, heat treatment, photoetching, quarter Erosion formation includes the microstructured layers of adding thermal resistance and signal output electrode;Microstructured layers with a thickness of 500~1500nm;
Three, prepared by seed layer: preparing seed layer in the ceramic substrate surface of microstructured layers gap location using PVD technique; It controls technological parameter and prepares NiAl2O4-xFilm or CuAl2O4-xFilm, and processing of removing photoresist is carried out, micro-structure is shown, it will be ceramic Substrate is annealed under reducing atmosphere, forms Ni or Cu cluster on surface;
Four, prepared by graphene sensitive layer: graphene growth is carried out in the seed layer made from step 3 using CVD technology, And complete graphene layer will be grown and carry out functional modification, form ceramic microstructures graphene gas sensor.
Beneficial effects of the present invention:
Graphene gas sensor configuration of the invention is simple, size is small, real by carrying out functional modification to graphene Existing variety classes gas detection.Graphene gas sensor of the present invention is based on MEMS technology Technology design and to manufacture, Manufacturing process is mature, is easily achieved the mass production of sensor, the miniaturization of sensor easy to accomplish, Integration Design system Make.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that a kind of each leafing of ceramic microstructures graphene gas sensor is scattered;
Fig. 2 is the main view of multiple ceramic microstructures graphene gas sensor arrays arrangement;
Fig. 3 is that nano silver graphene functionalized modifies gas sensor performance test curve;
Fig. 4 is that nano silver graphene functionalized modifies gas sensor linearity curve.
Specific embodiment
Specific embodiment 1: illustrating in conjunction with Fig. 1 and Fig. 2, a kind of ceramic microstructures graphene gas of present embodiment is passed Sensor includes ceramic bases 1, microstructured layers 2, seed layer 3 and graphene sensitive layer 4;
The ceramic bases 1 are the Al of surface polishing2O3Potsherd;The thickness control of the ceramic bases 1 0.1~ 1mm;
The microstructured layers 2 are arranged on 1 surface of ceramic bases, and the microstructured layers 2 include adding thermal resistance 2-1 and signal Output electrode 2-2;Signal output electrode 2-2 is formed by two in the electrode for separating finger-shaped, two interlaced settings of electrode And it is not in contact with each other;The serpentine-like gap location for being distributed in signal output electrode 2-2 of adding thermal resistance 2-1 and with signal output electrode 2-2 It is not in contact with each other;The thickness control of the microstructured layers 2 is in 500~1500nm;The control of adding thermal resistance 2-1 resistance value is in 5~50 Ω, letter The electrode logarithm majorzation of number output electrode 2-2 is at 3~10 pairs;
The gap location of adding thermal resistance 2-1 and signal output electrode 2-2 is arranged in the seed layer 3;Seed layer 3 and micro-structure The absolute value of the thickness difference of layer 2 is controlled in 50~300nm;
Graphene sensitive layer 4 cover seed layer 3, and with adding thermal resistance 2-1 in microstructured layers 2 and signal output electrode 2-2 Contact connection.
The ceramic bases of present embodiment play support and insulating effect.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: the adding thermal resistance 2-1 is Au Or Pt;The signal output electrode 2-2 is Au or Pt.Other are same as the specific embodiment one.
Present embodiment adding thermal resistance provides required temperature for sensor, and signal output electrode is defeated for sensor signal Out.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: the seed layer 3 is to adopt The NiAl prepared with PVD technique2O4-xFilm or CuAl2O4-xFilm;The PVD technique is penetrated using corresponding ceramic target Frequency magnetron sputtering carries out direct current reaction magnetron sputtering using alloy target material;The ceramic target purity is 99.99% NiAl2O4Target or CuAl2O4Target;Described is the Cu-Al alloys target or Ni-Al alloys target that alloy target material purity is 99.99%.Its He is the same as one or two specific embodiments.
The NiAl of present embodiment preparation2O4-xOr CuAl2O4-xFilm is annealed under reducing atmosphere, realizes Ni+2Or Cu+2From Son, which is restored and migrated to surface, forms Ni or Cu cluster, provides active site for graphene growth.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: the graphene It is prepared using CVD technology, and functional modification is carried out to the graphene of growth.One of other and specific embodiment one to three phase Together.
Present embodiment is realized specifically sexy to variety classes gas by carrying out functional modification to the graphene of growth Know.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: the functionalization Modification includes organic molecule, functional group, metal or compound-modified.Other are identical as one of specific embodiment one to four.
Specific embodiment 6: a kind of preparation method of ceramic microstructures graphene gas sensor of present embodiment is specific The following steps are included:
One, ceramic substrate cleans: selecting mixed solution to boil ceramic substrate under conditions of temperature is 60~100 DEG C clear After washing 30~60min, deionized water flushing, drying are carried out to ceramic substrate using dryer;The mixed solution is the concentrated sulfuric acid With the aqueous solution of potassium bichromate, the wherein concentrated sulfuric acid: potassium bichromate: water=(0.8~1.2) g:(15~25) mL:(15~25) mL;
Two, prepared by microstructured layers: ceramic substrate is made in step 1 and successively carries out metal film sputtering, heat treatment, photoetching, quarter Erosion formation includes the microstructured layers of adding thermal resistance and signal output electrode;The thickness control of microstructured layers is in 500~1500nm;
Three, prepared by seed layer: preparing seed layer in the ceramic substrate surface of microstructured layers gap location using PVD technique; It controls technological parameter and prepares NiAl2O4-xFilm or CuAl2O4-xFilm, and processing of removing photoresist is carried out, micro-structure is shown, it will be ceramic Substrate is annealed under reducing atmosphere, forms Ni or Cu cluster on surface;
Four, prepared by graphene sensitive layer: graphene growth is carried out in the seed layer made from step 3 using CVD technology, And complete graphene layer will be grown and carry out functional modification, form ceramic microstructures graphene gas sensor.
Specific embodiment 7: present embodiment is unlike specific embodiment six: microstructured layers system in step 2 It is standby specifically to sequentially include the following steps:
1. metal film sputters: using magnetron sputtering depositing system, by controlling technological parameter, thickness of metal film control is made to exist 500~1500nm;The gold or platinum target that target selection is 99.99%, sputtering power are controlled in 200~1000w;Sputtering time control In 30~70min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. heat treatment: being carried out the metal film that 1. step sputters under conditions of 800~1200 DEG C using ceramic sintering furnace Heat treatment, constant temperature time are controlled in 1~3h;
3. photoetching: the ceramic substrate after the heat treatment of 2. step being carried out to the coating of photoresist with glue spreader, photoresist is thick Degree control at 0.2~1 μm, using hot plate machine will coat the ceramic substrate of photoresist under conditions of 80~120 DEG C front baking 150~ 200s is exposed substrate in mask plate using litho machine, time for exposure control in 15~30s, exposure intensity control (50~ 80)×100μw/cm2;Ceramic substrate is put into developer solution and is developed, developing time is controlled in 20~50s, is existed using hot plate machine 10~30min of post bake under conditions of 80~120 DEG C;Substrate etching is carried out using ion bean etcher, etch period is controlled 50 After etched, neat, completion microstructured layers preparation is cleaned to microstructure aspects by~70min.Other and six phase of specific embodiment Together.
Specific embodiment 8: present embodiment is unlike specific embodiment six or seven: seed layer in step 3 Preparation specifically sequentially includes the following steps:
1. magnetron sputtering depositing system carries out NiAl2O4-xFilm or CuAl2O4-xThin film sputtering: NiAl is used2O4Or CuAl2O4Ceramic target carries out rf magnetron sputtering, splash-proofing sputtering process parameter are as follows: sputtering power is controlled in 200~500w;When sputtering Between control in 40~80min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. removing photoresist: carrying out processing of removing photoresist to substrate with acetone, ethanol solution, photoresist is cleaned up, micro- knot is shown Structure layer, time control of removing photoresist is in 5~10min;
3. annealing: by substrate in H2It anneals under/Ar reducing atmosphere, annealing temperature control is at 800~1100 DEG C, constant temperature time Control is in 0.5~2h.Other are identical as specific embodiment six or seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment six to eight: being planted in step 3 Sublayer preparation specifically sequentially includes the following steps:
1. magnetron sputtering depositing system carries out NiAl2O4-xFilm or CuAl2O4-xThin film sputtering: using Cu-Al alloy or Ni-Al alloy target material carries out direct current reaction magnetron sputtering, splash-proofing sputtering process parameter are as follows: sputtering power is controlled in 200~500w;Sputtering Time controls in 40~80min;Sputter gas is Ar;Reaction gas is O2;Sputtering pressure is controlled in 0.5~2Pa, O2Partial pressure control System is 50~70%;
2. removing photoresist: carrying out processing of removing photoresist to substrate with acetone, ethanol solution, photoresist is cleaned up, micro- knot is shown Structure layer, time control of removing photoresist is in 5~10min;
3. annealing: by substrate in H2It anneals under/Ar reducing atmosphere, annealing temperature control is at 800~1100 DEG C, constant temperature time Control is in 0.5~2h.Other are identical as one of specific embodiment six to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment six to nine: stone in step 4 Black alkene sensitive layer preparation specifically sequentially includes the following steps:
1. graphene growth: carrying out graphene growth using chemical gas-phase deposition system, utilize CH4Or C2H4As carbon source, H2As carrier gas, growth temperature is controlled at 800~1100 DEG C;
2. functional modification: configuration nanogold, nano silver, nano-metal-oxide or organic solution, concentration control exist Within the scope of 0.05~2mg/mL, modification solution is sucked using micropipettor and micro solution of dripping at the graphene of growth, It is dried under conditions of 50~200 DEG C, completes graphene functionalized modification, complete the preparation of graphene sensitive layer.Other with it is specific One of embodiment six to nine is identical.
Specific embodiment 11: unlike one of present embodiment and specific embodiment six to ten: the micro- knot of ceramics In the preparation process of structure graphene gas sensor, multiple constitutional repeating units are prepared on a ceramic substrate, to different structures Unit carries out different graphene functionalized modifications, realizes the array, integrated of ceramic microstructures graphene gas sensor Preparation.Other are identical as one of specific embodiment six to ten.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of ceramic microstructures graphene gas sensor specifically includes the following steps:
One, ceramic substrate cleans: selecting mixed solution to boil ceramic substrate under conditions of temperature is 60~100 DEG C clear After washing 30~60min, deionized water flushing, drying are carried out to ceramic substrate using dryer;The mixed solution is the concentrated sulfuric acid With the aqueous solution of potassium bichromate, the wherein concentrated sulfuric acid: potassium bichromate: water=(0.8~1.2) g:(15~25) mL:(15~25) mL;
Two, prepared by microstructured layers: 1. metal film sputters: using magnetron sputtering depositing system, by controlling technological parameter, makes Thickness of metal film is controlled in 500~1500nm;The gold or platinum target that target selection is 99.99%, sputtering power control 200~ 1000w;Sputtering time is controlled in 30~70min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. heat treatment: being carried out the metal film that 1. step sputters under conditions of 800~1200 DEG C using ceramic sintering furnace Heat treatment, constant temperature time are controlled in 1~3h;
3. photoetching: the ceramic substrate after the heat treatment of 2. step being carried out to the coating of photoresist with glue spreader, photoresist is thick Degree control at 0.2~1 μm, using hot plate machine will coat the ceramic substrate of photoresist under conditions of 80~120 DEG C front baking 150~ 200s is exposed substrate in mask plate using litho machine, time for exposure control in 15~30s, exposure intensity control (50~ 80)×100μw/cm2;Ceramic substrate is put into developer solution and is developed, developing time control is in 20~50s, using hot plate machine, 10~30min of post bake under conditions of 80~120 DEG C;Substrate etching is carried out using ion bean etcher, etch period is controlled 50 After etched, neat, completion microstructured layers preparation is cleaned to microstructure aspects by~70min;Formation includes adding thermal resistance and letter The microstructured layers of number output electrode;The thickness control of microstructured layers is in 500~1500nm;
Three, prepared by seed layer: 1. magnetron sputtering depositing system carries out NiAl2O4-xFilm or CuAl2O4-xThin film sputtering: it adopts Use NiAl2O4Or CuAl2O4Ceramic target carries out rf magnetron sputtering, splash-proofing sputtering process parameter are as follows: sputtering power control 200~ 500w;Sputtering time is controlled in 40~80min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. removing photoresist: carrying out processing of removing photoresist to substrate with acetone, ethanol solution, photoresist is cleaned up, micro- knot is shown Structure layer, time control of removing photoresist is in 5~10min;
3. annealing: by substrate in H2It anneals under/Ar reducing atmosphere, annealing temperature control is at 800~1100 DEG C, constant temperature time Control is in 0.5~2h;
Four, prepared by graphene sensitive layer: 1. graphene growth: graphene growth is carried out using chemical gas-phase deposition system, Utilize CH4Or C2H4As carbon source, H2As carrier gas, growth temperature is controlled at 800~1100 DEG C;
2. functional modification: configuration nanogold, nano silver, nano-metal-oxide or organic solution, concentration control exist Within the scope of 0.05~2mg/mL, modification solution is sucked using micropipettor and micro solution of dripping at the graphene of growth, It is dried under conditions of 50~200 DEG C, completes graphene functionalized modification, completed the preparation of graphene sensitive layer, it is micro- to form ceramics Structure graphite alkene gas sensor.
The grapheme modified gas sensor of nano silver is tested for the property, as shown in Figure 3 and Figure 4, the sensor is to NO2 Gas shows excellent air-sensitive performance, can realize at room temperature to NO2Gas detection, the test linearity reach 0.9851。
This method is based on MEMS technology technology, including film is grown, photoetching, etching etc..By control graphene in ceramics The growth of substrate and special sex modification realize that the array of the preparation of variety classes gas sensor and sensor is integrated.This embodiment party The manufacturing method of formula has the features such as simple process, technology maturation, can be mass, and obtained sensor is stablized with performance etc. Advantage.It can be applied to trace gas detection in the environment such as closed environment, atmospheric environment, underground pipe gallery.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims Variation is included within the present invention.

Claims (10)

1. a kind of ceramic microstructures graphene gas sensor, which is characterized in that ceramic microstructures graphene gas sensor packet Include ceramic bases (1), microstructured layers (2), seed layer (3) and graphene sensitive layer (4);
The ceramic bases (1) are the Al of surface polishing2O3Potsherd;The thickness control of the ceramic bases (1) 0.1~ 1mm;
The microstructured layers (2) are arranged on ceramic bases (1) surface, the microstructured layers (2) include adding thermal resistance (2-1) and Signal output electrode (2-2);Signal output electrode (2-2) is formed by two in the electrode for separating finger-shaped, and two electrodes are mutual It is staggered and is not in contact with each other;The serpentine-like gap location for being distributed in signal output electrode (2-2) of adding thermal resistance (2-1) and and signal Output electrode (2-2) is not in contact with each other;The thickness control of the microstructured layers (2) is in 500~1500nm;Adding thermal resistance (2-1) resistance Value control is in 5~50 Ω, and the electrode logarithm majorzation of signal output electrode (2-2) is at 3~10 pairs;
Gap location of seed layer (3) setting in adding thermal resistance (2-1) and signal output electrode (2-2);Seed layer (3) with it is micro- The absolute value of the thickness difference of structure sheaf (2) is controlled in 50~300nm;
Graphene sensitive layer (4) cover seed layer (3), and with adding thermal resistance (2-1) and signal output electrode in microstructured layers (2) (2-2) contact connection.
2. a kind of ceramic microstructures graphene gas sensor according to claim 1, which is characterized in that the heating electricity Hindering (2-1) is Au or Pt;The signal output electrode (2-2) is Au or Pt.
3. a kind of ceramic microstructures graphene gas sensor according to claim 1, which is characterized in that the seed layer (3) NiAl to be prepared using PVD technique2O4-xFilm or CuAl2O4-xFilm;The PVD technique is using corresponding ceramic target It carries out rf magnetron sputtering or direct current reaction magnetron sputtering is carried out using alloy target material;The ceramic target purity is 99.99% NiAl2O4Target or CuAl2O4Target;Described is the Cu-Al alloys target or Ni-Al alloys target that alloy target material purity is 99.99%.
4. a kind of ceramic microstructures graphene gas sensor according to claim 3, which is characterized in that the graphene It is prepared using CVD technology, and functional modification is carried out to the graphene of growth.
5. a kind of ceramic microstructures graphene gas sensor according to claim 1, which is characterized in that the functionalization Modification includes organic molecule, functional group, metal or compound-modified.
6. a kind of preparation method of ceramic microstructures graphene gas sensor as described in claim 1, which is characterized in that should Method specifically includes the following steps:
One, ceramic substrate cleans: mixed solution being selected to boil cleaning 30 under conditions of temperature is 60~100 DEG C to ceramic substrate After~60min, deionized water flushing, drying are carried out to ceramic substrate using dryer;The mixed solution is the concentrated sulfuric acid and again The aqueous solution of potassium chromate, the wherein concentrated sulfuric acid: potassium bichromate: water=(0.8~1.2) g:(15~25) mL:(15~25) mL;
Two, prepared by microstructured layers: ceramic substrate is made in step 1 and successively carries out metal film sputtering, heat treatment, photoetching, etching shape At the microstructured layers for including adding thermal resistance and signal output electrode;The thickness control of microstructured layers is in 500~1500nm;
Three, prepared by seed layer: preparing seed layer in the ceramic substrate surface of microstructured layers gap location using PVD technique;Control Technological parameter prepares NiAl2O4-xFilm or CuAl2O4-xFilm, and processing of removing photoresist is carried out, micro-structure is shown, by ceramic substrate It anneals under reducing atmosphere, forms Ni or Cu cluster on surface;
Four, prepared by graphene sensitive layer: graphene growth is carried out in the seed layer made from step 3 using CVD technology, and will It grows complete graphene layer and carries out functional modification, form ceramic microstructures graphene gas sensor.
7. a kind of ceramic microstructures graphene gas sensor according to claim 6, which is characterized in that micro- in step 2 Structure sheaf preparation specifically sequentially includes the following steps:
1. metal film sputters: using magnetron sputtering depositing system, by controlling technological parameter, make thickness of metal film control 500 ~1500nm;The gold or platinum target that target selection is 99.99%, sputtering power are controlled in 200~1000w;Sputtering time control exists 30~70min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. heat treatment: the metal film that 1. step sputters being carried out hot place under conditions of 800~1200 DEG C using ceramic sintering furnace Reason, constant temperature time are controlled in 1~3h;
3. photoetching: the ceramic substrate after the heat treatment of 2. step is carried out to the coating of photoresist, photoresist thickness control with glue spreader System at 0.2~1 μm, using hot plate machine will coat the ceramic substrate of photoresist under conditions of 80~120 DEG C front baking 150~ 200s is exposed substrate in mask plate using litho machine, time for exposure control in 15~30s, exposure intensity control (50~ 80)×100μw/cm2;Ceramic substrate is put into developer solution and is developed, developing time is controlled in 20~50s, is existed using hot plate machine 10~30min of post bake under conditions of 80~120 DEG C;Substrate etching is carried out using ion bean etcher, etch period is controlled 50 After etched, neat, completion microstructured layers preparation is cleaned to microstructure aspects by~70min.
8. a kind of ceramic microstructures graphene gas sensor according to claim 6, which is characterized in that planted in step 3 Sublayer preparation specifically sequentially includes the following steps:
1. magnetron sputtering depositing system carries out NiAl2O4-xFilm or CuAl2O4-xThin film sputtering: NiAl is used2O4Or CuAl2O4Pottery Porcelain target carries out rf magnetron sputtering, splash-proofing sputtering process parameter are as follows: sputtering power is controlled in 200~500w;Sputtering time control exists 40~80min;Sputter gas is Ar;Sputtering pressure is controlled in 0.5~2Pa;
2. removing photoresist: processing of removing photoresist is carried out to substrate with acetone, ethanol solution, photoresist is cleaned up, microstructured layers are shown, Time control remove photoresist in 5~10min;
3. annealing: by substrate in H2It anneals under/Ar reducing atmosphere, at 800~1100 DEG C, constant temperature time is controlled for annealing temperature control In 0.5~2h.
9. a kind of ceramic microstructures graphene gas sensor according to claim 6, which is characterized in that planted in step 3 Sublayer preparation specifically sequentially includes the following steps:
1. magnetron sputtering depositing system carries out NiAl2O4-xFilm or CuAl2O4-xThin film sputtering: Cu-Al alloy or Ni-Al are used Alloy target material carries out direct current reaction magnetron sputtering, splash-proofing sputtering process parameter are as follows: sputtering power is controlled in 200~500w;Sputtering time Control is in 40~80min;Sputter gas is Ar;Reaction gas is O2;Sputtering pressure is controlled in 0.5~2Pa, O2Partial pressure control exists 50~70%;
2. removing photoresist: processing of removing photoresist is carried out to substrate with acetone, ethanol solution, photoresist is cleaned up, microstructured layers are shown, Time control remove photoresist in 5~10min;
3. annealing: by substrate in H2It anneals under/Ar reducing atmosphere, at 800~1100 DEG C, constant temperature time is controlled for annealing temperature control In 0.5~2h.
10. a kind of ceramic microstructures graphene gas sensor according to claim 6, which is characterized in that in step 4 The preparation of graphene sensitive layer specifically sequentially includes the following steps:
1. graphene growth: carrying out graphene growth using chemical gas-phase deposition system, utilize CH4Or C2H4As carbon source, H2Make For carrier gas, growth temperature is controlled at 800~1100 DEG C;
2. functional modification: configuration nanogold, nano silver, nano-metal-oxide or organic solution, concentration are controlled 0.05 Within the scope of~2mg/mL, modification solution is sucked using micropipettor and micro solution of dripping at the graphene of growth, 50 It is dried under conditions of~200 DEG C, completes graphene functionalized modification, complete the preparation of graphene sensitive layer.
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