CN112730534A - Carbon dioxide sensor for monitoring microbial growth and preparation method thereof - Google Patents
Carbon dioxide sensor for monitoring microbial growth and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 48
- 238000012544 monitoring process Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000000813 microbial effect Effects 0.000 title claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 81
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 75
- 244000005700 microbiome Species 0.000 claims abstract description 27
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- 239000010410 layer Substances 0.000 claims description 107
- 235000012431 wafers Nutrition 0.000 claims description 58
- 229920002873 Polyethylenimine Polymers 0.000 claims description 56
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000002687 intercalation Effects 0.000 claims description 8
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Abstract
本发明一种用于监控微生物生长的二氧化碳传感器及其制备方法，属于二氧化碳传感器及其制备方法技术领域；所要解决的技术问题为：提供一种用于监控微生物生长的二氧化碳传感器硬件结构的改进；解决上述技术问题采用的技术方案为：在蓝宝石衬底上外延生长n型氮化镓层，采用一系列电极制备工艺在氮化镓外延片上沉积Ti/Al/Pt/Au电极，后通过液相剥离黑磷以及对黑磷进行功能化改性制备BP‑PEI层，获得了高灵敏度、可实时操作的小型化二氧化碳气体传感器；本发明二氧化碳传感器性能稳定，对二氧化碳气敏性能良好且价格低廉，尺寸小，检测方式简单，同时具有一次性，无污染等优点；本发明应用于监控微生物生长。
The invention relates to a carbon dioxide sensor for monitoring the growth of microorganisms and a preparation method thereof, belonging to the technical field of carbon dioxide sensors and the preparation method thereof; the technical problem to be solved is: to provide an improvement in the hardware structure of the carbon dioxide sensor for monitoring the growth of microorganisms; The technical solution adopted to solve the above technical problems is: epitaxially growing an n-type gallium nitride layer on a sapphire substrate, using a series of electrode preparation processes to deposit Ti/Al/Pt/Au electrodes on the gallium nitride epitaxial wafer, and then passing the liquid phase The BP-PEI layer is prepared by stripping black phosphorus and functionally modifying the black phosphorus, thereby obtaining a miniaturized carbon dioxide gas sensor with high sensitivity and real-time operation; the carbon dioxide sensor of the invention has stable performance, good carbon dioxide gas sensing performance and low price. The size is small, the detection method is simple, and at the same time, it has the advantages of one-time use, no pollution, etc. The invention is applied to monitor the growth of microorganisms.
Description
Technical Field
The invention discloses a carbon dioxide sensor for monitoring microbial growth and a preparation method thereof, and belongs to the technical field of carbon dioxide sensors and preparation methods thereof.
Background
During the growth process of the microorganism, the microorganism continuously exchanges substances and energy with the outside, and the growth process can be monitored through the PH, the oxygen consumption rate and the carbon dioxide content of the microorganism incubator. The biological incubator is a long-term sealed device, the components and gas concentration of a culture medium are changed relative to the initial state, and the growth rate and metabolic products of microorganisms are changed under different gas environments. The requirement of monitoring the growth curve of microorganisms is very common nowadays, in order to monitor the growth condition of microorganisms, frequent detection of gas components is needed, and the detection of the concentration of carbon dioxide is also of great significance to the growth of microorganisms.
The traditional carbon dioxide sensor uses an infrared absorption detection technology, and the light intensity attenuation of infrared light after passing through the detected gas meets Lambert-Beer law. Therefore, the gas concentration can be measured by measuring the attenuation of infrared rays by gas, but the carbon dioxide sensor prepared based on the technology is expensive, the technology is immature, the later maintenance cost is high, the size is relatively large, the utilization rate is low, and the use of the carbon dioxide sensor is limited. Therefore, there is a need to develop a carbon dioxide sensor that is small in size and free of contamination.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to solve the technical problems that: an improvement in the hardware architecture of a carbon dioxide sensor for monitoring microbial growth is provided.
In order to solve the technical problems, the invention adopts the technical scheme that: a novel carbon dioxide sensor for monitoring the growth of microorganisms is a novel carbon dioxide sensor compounded by a gallium nitride-based material, novel two-dimensional material black phosphorus and branched polyethyleneimine, and specifically comprises an n-type gallium nitride thin layer growing on a sapphire substrate, wherein a Ti/Al/Pt/Au electrode layer is deposited on the n-type gallium nitride thin layer through magnetron sputtering, and the n-type gallium nitride thin layer is provided with a black phosphorus-branched polyethyleneimine thin layer.
The n-type gallium nitride thin layer is doped with 1 × 10 concentration18 cm-3-9×1018cm−3Of silicon (ii) is described.
The total thickness of the Ti/Al/Pt/Au electrode layers is 45nm-55nm, and the thickness of each electrode layer is 10nm-15 nm.
The black phosphorus-branched chain polyethyleneimine thin layer comprises a two-dimensional black phosphorus single layer and a plurality of layers of nano sheets, wherein the thickness of the two-dimensional black phosphorus single layer and the plurality of layers of nano sheets is 1nm-20nm, and the length of the two-dimensional black phosphorus single layer and the plurality of layers of nano sheets is 500nm-50 mu m.
The black phosphorus-branched polyethyleneimine thin layer is composed of black phosphorus powder and a polyethyleneimine solution, wherein the volume ratio of the black phosphorus powder to the polyethyleneimine solution is 3: 5.
a method of making a carbon dioxide sensor for monitoring microbial growth, comprising the steps of:
the method comprises the following steps: epitaxially growing a silicon-doped n-type gallium nitride epitaxial wafer on a sapphire substrate;
step two: depositing a SiO2 layer on the surface of the n-type gallium nitride epitaxial wafer by a PECVD method, throwing photoresist, placing a mask plate, and preparing an in-situ mask plate by utilizing exposure and development processes;
depositing a Ti/Al/Pt/Au electrode on the surface of the n-type gallium nitride epitaxial wafer by adopting a magnetron sputtering technology to form ohmic contact with the gallium nitride epitaxial wafer;
step three: taking single crystal black phosphorus as a raw material, and stripping the single crystal black phosphorus into a two-dimensional thin-layer black phosphorus single-layer and multi-layer micro nanosheet with the thickness of 1-20 nm by adopting a simple liquid phase stripping method;
stripping single crystal BP by using ultrasonic energy generated by a cell ultrasonic wall breaking machine, taking diethylene glycol dimethyl ether as an intercalation solvent to enable the single crystal BP to expand and delaminate, and generating a BP two-dimensional thin layer material;
step four: taking a two-dimensional thin layer BP sheet, adding the polyethyleneimine with mw =600 into deionized water, and uniformly mixing the polyethyleneimine with a magnetic stirrer;
performing electrostatic assembly on the surface of the two-dimensional thin layer BP through the branched chain PEI, functionalizing the surface of the two-dimensional thin layer BP and forming a covering layer;
step five: ultrasonically dispersing BP-PEI in an ethanol solution, then gently dripping the mixed solution between two electrodes, putting the mixed solution in a drying box to evaporate a solvent, and forming a stable film on the n-type gallium nitride epitaxial wafer to obtain the gas sensing device.
The first step is specifically as follows: epitaxially growing silicon-doped n-type gallium nitride epitaxial wafer on four-inch sapphire substrate by metal organic chemical vapor deposition method, wherein the thickness of the epitaxial wafer is 35 nm, and the silicon doping concentration is 1 × 1018 cm−3-9×1018cm −3。
And splitting the n-type gallium nitride epitaxial wafer with the prepared electrode in the second step to uniformly divide the four-inch n-type gallium nitride epitaxial wafer into 5mm multiplied by 5mm epitaxial wafers.
The third step is that the specific steps of manufacturing the two-dimensional thin-layer black phosphorus single-layer and multi-layer micro-nano sheet are as follows:
grinding high-quality blocky black phosphorus by using a mortar, taking black phosphorus crystal powder to disperse in a solution, and carrying out ultrasonic centrifugation on the mixed solution in an ice bath environment to obtain a stably-existing two-dimensional thin-layer black phosphorus suspension;
the ultrasonic energy generated by the cell ultrasonic wall breaking machine is utilized to strip the single crystal BP, diethylene glycol dimethyl ether is used as an intercalation solvent, the single crystal BP expands and delaminates, and a BP two-dimensional thin layer material is generated.
Compared with the prior art, the invention has the beneficial effects that: the novel gallium nitride-based carbon dioxide sensor provided by the invention has the advantages of high sensitivity, good selectivity, small size, capability of being controlled within 5mm multiplied by 5mm, low price, controllable cost within one unit, capability of avoiding cross contamination of microorganisms due to one-time use, wide application prospect in the field of biological medical treatment and the like, and is used for monitoring the growth condition of the microorganisms in a micro incubator.
1. The novel two-dimensional material adopted by the invention has ultrathin thickness of single-layer and multi-layer black phosphorus nanometer thin layers, high carrier migration rate and short response recovery time, and improves the sensitivity and the response recovery time of the carbon dioxide gas sensor.
2. When the n-type gallium nitride and the p-type black phosphorus are contacted, a p-n-type heterojunction is formed due to Van der Waals interaction, electron transfer occurs between the n-type gallium nitride and the p-type black phosphorus due to the fact that the Fermi level of the n-type gallium nitride is higher than that of the p-type black phosphorus, and when the Fermi levels of the n-type gallium nitride and the p-type black phosphorus are consistent, a p-n heterojunction structure is formed at the interface of the n-type gallium nitride and the p-type black phosphorus, so that the width of a surface electron depletion layer or a hole accumulation layer is increased, and the sensitivity of the sensor is improved.
3. The gallium nitride-based material adopted by the invention has stable performance and is relatively insensitive to temperature, and meanwhile, the stripped black phosphorus thin layer generates lattice defects due to P-P bond fracture, and a stable BP-PEI thin layer is formed by non-covalent assembly of branched polyethyleneimine. By combining the two aspects, the carbon dioxide sensor has relatively stable performance and good gas-sensitive performance to carbon dioxide.
4. The gallium nitride epitaxial wafer has good biocompatibility and environmental friendliness, and provides an excellent material for a gas sensor used in the field of microorganisms.
5. The lattice constant of the gallium nitride plane used by the invention is similar to that of the black phosphorus armchair direction, and good lattice matching degree lays a foundation for the formation of P-N heterojunction.
6. The carbon dioxide sensor prepared by the invention has the characteristics of low price, small size, simple detection mode, disposable use, no pollution and the like.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of the preparation of BP-PEI layers according to the present invention.
FIG. 2 is a flow chart of the preparation of the GaN-BP-PEI novel carbon dioxide sensor of the invention.
Fig. 3 is a schematic connection diagram of the novel carbon dioxide sensor test system of the present invention.
Detailed Description
As shown in fig. 1 to 3, the novel carbon dioxide sensor for monitoring the growth of microorganisms, which is compounded by gallium nitride-based materials, novel two-dimensional materials of black phosphorus and branched polyethyleneimine, specifically comprises an n-type gallium nitride thin layer grown on a sapphire substrate, wherein a Ti/Al/Pt/Au electrode layer is deposited on the n-type gallium nitride thin layer by magnetron sputtering, and the black phosphorus-branched polyethyleneimine thin layer is arranged on the n-type gallium nitride thin layer.
The n-type gallium nitride thin layer is doped with 1 × 10 concentration18 cm-3-9×1018cm−3Of silicon (ii) is described.
The total thickness of the Ti/Al/Pt/Au electrode layers is 45nm-55nm, and the thickness of each electrode layer is 10nm-15 nm.
The black phosphorus-branched chain polyethyleneimine thin layer comprises a two-dimensional black phosphorus single layer and a plurality of layers of nano sheets, wherein the thickness of the two-dimensional black phosphorus single layer and the plurality of layers of nano sheets is 1nm-20nm, and the length of the two-dimensional black phosphorus single layer and the plurality of layers of nano sheets is 500nm-50 mu m.
The black phosphorus-branched polyethyleneimine thin layer is composed of black phosphorus powder and a polyethyleneimine solution, wherein the volume ratio of the black phosphorus powder to the polyethyleneimine solution is 3: 5.
a method of making a carbon dioxide sensor for monitoring microbial growth, comprising the steps of:
the method comprises the following steps: epitaxially growing a silicon-doped n-type gallium nitride epitaxial wafer on a sapphire substrate;
step two: depositing a SiO2 layer on the surface of the n-type gallium nitride epitaxial wafer by a PECVD method, throwing photoresist, placing a mask plate, and preparing an in-situ mask plate by utilizing exposure and development processes;
depositing a Ti/Al/Pt/Au electrode on the surface of the n-type gallium nitride epitaxial wafer by adopting a magnetron sputtering technology to form ohmic contact with the gallium nitride epitaxial wafer;
step three: taking single crystal black phosphorus as a raw material, and stripping the single crystal black phosphorus into a two-dimensional thin-layer black phosphorus single-layer and multi-layer micro nanosheet with the thickness of 1-20 nm by adopting a simple liquid phase stripping method;
stripping single crystal BP by using ultrasonic energy generated by a cell ultrasonic wall breaking machine, taking diethylene glycol dimethyl ether as an intercalation solvent to enable the single crystal BP to expand and delaminate, and generating a BP two-dimensional thin layer material;
step four: taking a two-dimensional thin layer BP sheet, adding the polyethyleneimine with mw =600 into deionized water, and uniformly mixing the polyethyleneimine with a magnetic stirrer;
performing electrostatic assembly on the surface of the two-dimensional thin layer BP through the branched chain PEI, functionalizing the surface of the two-dimensional thin layer BP and forming a covering layer;
step five: ultrasonically dispersing BP-PEI in an ethanol solution, then gently dripping the mixed solution between two electrodes, putting the mixed solution in a drying box to evaporate a solvent, and forming a stable film on the n-type gallium nitride epitaxial wafer to obtain the gas sensing device.
The first step is specifically as follows: epitaxially growing silicon-doped n-type gallium nitride epitaxial wafer on four-inch sapphire substrate by metal organic chemical vapor deposition method, wherein the thickness of the epitaxial wafer is 35 nm, and the silicon doping concentration is 1 × 1018 cm−3-9×1018cm −3。
And splitting the n-type gallium nitride epitaxial wafer with the prepared electrode in the second step to uniformly divide the four-inch n-type gallium nitride epitaxial wafer into 5mm multiplied by 5mm epitaxial wafers.
The third step is that the specific steps of manufacturing the two-dimensional thin-layer black phosphorus single-layer and multi-layer micro-nano sheet are as follows:
grinding high-quality blocky black phosphorus by using a mortar, taking black phosphorus crystal powder to disperse in a solution, and carrying out ultrasonic centrifugation on the mixed solution in an ice bath environment to obtain a stably-existing two-dimensional thin-layer black phosphorus suspension;
the ultrasonic energy generated by the cell ultrasonic wall breaking machine is utilized to strip the single crystal BP, diethylene glycol dimethyl ether is used as an intercalation solvent, the single crystal BP expands and delaminates, and a BP two-dimensional thin layer material is generated.
The invention overcomes the defects of the existing carbon dioxide sensor, provides a novel carbon dioxide sensor for monitoring the growth of microorganisms, and solves the problems of high cost, high maintenance cost and large sensor size of the existing traditional infrared carbon dioxide sensor.
The invention provides a novel carbon dioxide sensor compounded by gallium nitride (GaN) -based materials, novel two-dimensional materials of Black Phosphorus (BP) and branched Polyethyleneimine (PEI), which comprises an n-type gallium nitride thin layer grown on a sapphire substrate, a Ti/Al/Pt/Au electrode deposited by magnetron sputtering and a BP-PEI thin layer formed by functional treatment.
The thickness of the two-dimensional black phosphorus single-layer and multi-layer micro-nano sheets is within the range of 1-20 nm, and the length of the two-dimensional black phosphorus single-layer and multi-layer micro-nano sheets is within the range of 500nm-50 mu m.
The concentration of n-type gallium nitride doped silicon is 1 x 1018 cm-3-9×1018 cm−3。
The thickness of the Ti/Al/Pt/Au electrode is 45-55 nm.
And the BP-PEI thin layer improves the selectivity of the carbon dioxide gas sensor.
The volume ratio of the black phosphorus powder to the polyethyleneimine solution is 3: 5.
the preparation method comprises the following specific steps:
s1: epitaxially growing a silicon-doped n-GaN epitaxial wafer on a four-inch sapphire substrate by Metal Organic Chemical Vapor Deposition (MOCVD) method, wherein the thickness of the silicon-doped n-GaN epitaxial wafer is 35 nm, and the silicon doping concentration is 1 multiplied by 1018 cm−3-9×1018 cm −3。
S2: depositing a 30nm SiO2 layer on the surface of the gallium nitride epitaxial wafer by PECVD, throwing photoresist, placing a mask plate, preparing an in-situ mask plate by utilizing a series of processes such as exposure, development and the like, and depositing a Ti/Al/Pt/Au electrode on the gallium nitride epitaxial wafer by adopting a magnetron sputtering technology to form ohmic contact with the gallium nitride epitaxial wafer so as to realize good electrical performance. And then splitting the gallium nitride epitaxial wafer with the prepared electrode to uniformly divide the four-inch gallium nitride epitaxial wafer into 5mm multiplied by 5mm epitaxial wafers.
S3: taking single crystal black phosphorus as a raw material, stripping the single crystal black phosphorus into two-dimensional thin-layer black phosphorus single-layer and multi-layer micro-nanosheets with the thickness of 1-20 nm by adopting a simple liquid phase stripping method, specifically, grinding high-quality blocky black phosphorus by using a mortar, taking black phosphorus crystal powder to disperse in a solution, and ultrasonically centrifuging the mixed solution in an ice bath environment to obtain a stably existing two-dimensional thin-layer black phosphorus turbid liquid. The ultrasonic energy generated by the cell ultrasonic wall breaking machine is utilized to strip the single crystal BP, diethylene glycol dimethyl ether is used as an intercalation solvent, the single crystal BP expands and delaminates, and a BP two-dimensional thin layer material is generated.
S4: a two-dimensional thin layer BP sheet was taken, and mw =600(Sigma-Aldrich) Polyethyleneimine (PEI) was added to deionized water and mixed homogeneously using a magnetic stirrer. And (3) generating a large number of lattice defects at the edge of the stripped BP nanosheet due to the breakage of phosphorus-phosphorus bonds, and then, carrying out electrostatic assembly on the surface of the two-dimensional thin layer BP through the branched chain PEI to functionalize the surface of the two-dimensional thin layer BP and form a covering layer (BP-PEI) so as to keep the stability of the BP thin layer.
S5: ultrasonically dispersing BP-PEI in an ethanol solution, then gently dripping the mixed solution between two electrodes, putting the mixed solution in a drying box to evaporate a solvent so as to form a stable film on a gallium nitride epitaxial wafer, and obtaining the gas sensing device.
In the first step, n-type gallium nitride is epitaxially grown on the substrate by MOCVD method, the thickness is 35 nm, and the n-type doping concentration is 7 multiplied by 1018 cm-3。
The distance between the Ti/Al/Pt/Au electrodes was 2 mm.
Grinding the block black phosphorus by using a mortar, stripping the single crystal BP by using ultrasonic energy generated by a cell ultrasonic wall breaking machine, taking diethylene glycol dimethyl ether as an intercalation solvent, placing in an ice bath, expanding and layering the single crystal BP, and generating a BP two-dimensional thin layer material.
In the fourth step, the black phosphorus nanosheets and the branched polyethyleneimine are uniformly mixed by using a magnetic stirrer, and the polyethyleneimine plays a role in protecting the black phosphorus surface, so that the stability of the gas-sensitive material is improved.
The carbon dioxide and the amido in the BP-PEI thin film material are subjected to chemical reaction to further cause the change of the electric signal of the sensor, and the concentration of the carbon dioxide gas can be measured through the change of the electric signal.
The size of the prepared gas sensing device is 5mm multiplied by 5 mm.
FIG. 2 is a method for manufacturing the novel carbon dioxide sensor for monitoring the growth of microorganisms according to the present invention, and the manufacturing method is further illustrated by the following specific examples.
Example 1
S1: epitaxially growing a silicon-doped n-GaN epitaxial wafer on a four-inch sapphire substrate by Metal Organic Chemical Vapor Deposition (MOCVD), wherein the thickness of a gallium nitride layer is 35 nm, and the silicon doping concentration is 1 multiplied by 1018cm-3-9×1018cm-3。
S2: depositing SiO 30nm on the surface of the gallium nitride epitaxial wafer by PECVD2And after photoresist is thrown, a mask is placed, an in-situ mask is prepared by a series of processes such as exposure, development and the like, and a Ti/Al/Pt/Au electrode is deposited on the gallium nitride epitaxial wafer by adopting a magnetron sputtering technology so as to form ohmic contact with the gallium nitride epitaxial wafer, thereby realizing good electrical performance. And then splitting the gallium nitride epitaxial wafer with the prepared electrode to uniformly divide the four-inch gallium nitride epitaxial wafer into 5mm multiplied by 5mm epitaxial wafers.
S3: taking single crystal black phosphorus as a raw material, stripping the single crystal black phosphorus into a two-dimensional black phosphorus thin layer with the thickness of 1-20 nm by adopting a simple liquid phase stripping method, specifically, grinding high-quality blocky black phosphorus by using a mortar, and mixing black phosphorus crystal powder and diethylene glycol dimethyl ether in a ratio of 2: 5, and placing the mixed solution in an ice bath environment for ultrasonic treatment for 3 hours at an amplitude of 60 percent. And (3) setting the revolution number to be 2000 rpm-1, and centrifuging for 0.5 h to obtain a two-dimensional thin-layer black phosphorus suspension which stably exists.
S4: a thin layer of 3mg two-dimensional BP was taken, then mw =600(Sigma-Aldrich) of 5 mg Polyethyleneimine (PEI) was added to 50 ml deionized water and mixed homogeneously using a magnetic stirrer. And (3) generating a large number of lattice defects at the edge of the stripped BP flake due to the breakage of phosphorus-phosphorus bonds, and then carrying out electrostatic assembly on the surface of the two-dimensional thin layer BP through the branched chain PEI to functionalize the surface of the two-dimensional thin layer BP and form a covering layer (BP-PEI) so as to ensure the stability of the BP nanosheet.
S5: ultrasonically dispersing a proper amount of BP-PEI in 1.0 mL of ethanol, then dripping the mixed solution on a gallium nitride epitaxial wafer by using a dropper, placing the gallium nitride epitaxial wafer in a 60 ℃ oven for drying for 5 h to evaporate the solvent, and forming a stable BP-PEI thin film on the gallium nitride epitaxial wafer to obtain the gas sensing device.
S6: the sensor is arranged at an operation opening of the microorganism incubator, a core device of the sensor is connected with a control system, and the control system is connected with a computer. The system is debugged and data is processed by the control system, and the gas test result is output on a display of the computer end.
Example 2
S1: epitaxially growing an n-type gallium nitride layer on the sapphire substrate by metal organic chemical vapor deposition, wherein the thickness of the gallium nitride layer is 35 nm, and the silicon doping concentration is 1 multiplied by 1018cm−3- 9×1018cm−3。
S2: depositing SiO 30nm on the surface of the gallium nitride epitaxial wafer by PECVD2And after photoresist is thrown, a mask plate is placed, and a series of processes such as exposure, development and the like are carried out to prepare an in-situ mask plate, and a Ti/Al/Pt/Au electrode is deposited on the gallium nitride epitaxial wafer by adopting a magnetron sputtering technology so as to form ohmic contact with the gallium nitride epitaxial wafer, thereby realizing good electrical performance. And then splitting the gallium nitride epitaxial wafer with the prepared electrode to uniformly divide the four-inch gallium nitride epitaxial wafer into 5mm multiplied by 5mm epitaxial wafers.
S3: stripping black phosphorus slices from massive black phosphorus by adopting a liquid phase, grinding the black phosphorus slices by using a mortar, placing the black phosphorus slices and diethylene glycol dimethyl ether into powder, and mixing the black phosphorus powder and the diethylene glycol dimethyl ether in a ratio of 2: 5, carrying out ultrasonic treatment on the mixed solution in an ice bath for 3.5 h, and setting the rotating speed of a centrifugal machine to be 2500 r min-1 and the centrifugal time to be 0.3 h to obtain the stable large-area two-dimensional thin-layer black phosphorus material.
S4: 3mg of two-dimensional BP sheet was taken. Then, mw =600(Sigma-Aldrich) of 5 mg Polyethyleneimine (PEI) was added to 50 ml deionized water, and mixed uniformly using a magnetic stirrer.
S5: ultrasonically dispersing a proper amount of BP-PEI in 1.0 mL of ethanol, spin-coating the mixed solution on a gallium nitride epitaxial wafer, drying the gallium nitride epitaxial wafer in a 70 ℃ oven for 4 h to evaporate a solvent to form a stable BP-PEI film on the gallium nitride epitaxial wafer, and preparing the carbon dioxide gas sensor.
S6: the sensor is arranged at an operation opening of the microorganism incubator, a core device of the sensor is connected with a control system, and the control system is connected with a computer. And debugging and data processing of the system are carried out through the control system, and a test result is output on a display of the computer end.
It should be noted that, regarding the specific structure of the present invention, the connection relationship between the modules adopted in the present invention is determined and can be realized, except for the specific description in the embodiment, the specific connection relationship can bring the corresponding technical effect, and the technical problem proposed by the present invention is solved on the premise of not depending on the execution of the corresponding software program.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
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