CN105842292B - A kind of pair of hydrogen sulfide carries out semiconductor and its preparation, use of room temperature gas sensitive detection - Google Patents
A kind of pair of hydrogen sulfide carries out semiconductor and its preparation, use of room temperature gas sensitive detection Download PDFInfo
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- CN105842292B CN105842292B CN201610192050.3A CN201610192050A CN105842292B CN 105842292 B CN105842292 B CN 105842292B CN 201610192050 A CN201610192050 A CN 201610192050A CN 105842292 B CN105842292 B CN 105842292B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0044—Specially adapted to detect a particular component for H2S, sulfides
Abstract
The invention discloses a kind of semiconductors that room temperature gas sensitive detection can be carried out to hydrogen sulfide, including MEMS substrate and the indium oxide porous array sensitive thin film for being attached to MEMS substrate surface, doped with gold nano grain in indium oxide porous array sensitive thin film, indium oxide porous array sensitive thin film surface modification has carbon coating gold nano grain；The number of plies of indium oxide porous array sensitive thin film is 1~30 layer, and bore dia is 1~3000nm, and overall thickness is 5~10000nm；Doping density of the gold nano grain in indium oxide porous array sensitive thin film is 0.1~200 μ g/cm2；Carbon coating gold nano grain is 0.1~100 μ g/cm in the modification density of indium oxide porous array sensitive thin film2.The invention also discloses the preparation methods of the above-mentioned semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide.The invention also discloses the application methods of the above-mentioned semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide.
Description
Technical field
The present invention relates to Semiconductor gas sensors detection field more particularly to a kind of room temperature gas sensitive detection can be carried out to hydrogen sulfide
Semiconductor and its preparation, use.
Background technique
Hydrogen sulfide is a kind of colourless, hypertoxic, highly acid gas, it is the violent in toxicity for being only second to cyanide, not only can be to gold
Belong to equipment and cause serious corrosion failure, also seriously threatens the life security of people.Low concentration is contacted to respiratory tract and eye
Local irritant effect is generated, when high concentration is more apparent to general action, shows as central nervous system symptom and asphyxia symptom.Sulphur
Although changing hydrogen has rotten egg smell, but cause olfactory nerves paralysis and unconsciously its taste when high concentration quickly, so when high-content
It is difficult to realize, people is easy to be poisoned and lead to death at this time.In recent years, hydrogen sulfide poisoning accident happens occasionally, in petroleum, chemical industry
Industry is also than more prominent.For life, property safety and the routine safety production for ensureing the people, reinforce the provisional monitor to hydrogen sulfide
And protection is particularly important.
Currently, most common sulfurated hydrogen detection technology is semiconductor transducer in the market.Traditional semiconductor transducer needs
It to work under certain hot conditions (generally at 300~600 DEG C), just be able to achieve the detection to object gas.But high temperature work
Make condition the problem is that: 1, sensor energy consumption is high (power consumption of single sensor is in 1W or so), limiting sensor it is small-sized
Change application, is also unsatisfactory for energy-efficient requirement；2, there is also security risks for detection of the hot operation to flammable explosive gas.In addition,
The interdigital spacing of conventional semiconductors sensor base is larger, is grade, causes the gas sensitive detection sensitivity of sensor lower.
Summary of the invention
Technical problems based on background technology can carry out room temperature gas sensitive detection to hydrogen sulfide the invention proposes a kind of
Semiconductor.
The invention solves another technical problem be MEMS substrate high activity gold nano grain and carbon coating Jenner
The preparation method of rice grain.
The invention solves another technical problem be MEMS substrate design, customization and use.
The invention solves another technical problem be gold nano grain doped indium oxide porous array sensitive thin film
Preparation method.
The invention solves another technical problem be that carbon coating gold nano particle modification indium oxide porous array is sensitive
The preparation method of film.
The invention solves another technical problem be to provide a kind of above-mentioned to distinguish by substrate, inside and surface of MEMS
The purposes of the indium oxide porous film material of doping and modification.
It is proposed by the present invention it is a kind of the semiconductor of room temperature gas sensitive detection can be carried out to hydrogen sulfide, including MEMS substrate and be attached to
The indium oxide porous array sensitive thin film of MEMS substrate surface, doped with gold nano in indium oxide porous array sensitive thin film
Grain, indium oxide porous array sensitive thin film surface modification have carbon coating gold nano grain；Indium oxide porous array sensitive thin film
The number of plies is 1~30 layer, and bore dia is 1~3000nm, and overall thickness is 5~10000nm；Gold nano grain is in indium oxide porous array
Doping density in sensitive thin film is 0.1~200 μ g/cm2, the partial size of gold nano grain is 1~200nm；Carbon coating gold nano
Particle is 0.1~100 μ g/cm in the modification density of indium oxide porous array sensitive thin film2, the partial size of carbon coating gold nano grain
For 1~200nm.
MEMS substrate is MEMS (MEMS, Micro-Electro-Mechanical System), is in microelectronics
Grow up on the basis of technology (semiconductor processing technology), has merged photoetching, burn into film, LIGA, silicon micromachined, non-silicon
The high-tech electronic mechanical devices of the technologies production such as micro Process and precision machinery processing.
Preferably, gold nano grain is polycrystalline state gold nano grain.
Preferably, in carbon coating gold nano grain, carbon is monocrystalline or amorphous state, 1~30nm of carbon-coating thickness.
Preferably, the interdigital electrode spacing of MEMS substrate is 1~1000 μm, and interdigital logarithm is 1~100 pair, working region
Area is 100 μm2~1mm2。
Preferably, every layer of indium oxide porous array sensitive thin film is the orderly porous membrane of Hexagonal array.
The preparation method for the above-mentioned semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide that the present invention also proposes, including such as
Lower step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and solution cleans to obtain carbon coating gold nano grain；By carbon coating gold
Nano particle dispersion obtains carbon coating gold nano grain dispersion liquid in ethanol；
S3, gold nano grain is placed in indium oxide precursor solution, two-dimensional colloidal ball template is then moved into drift to its table
Then face is in the solution picked up colloidal spheres with MEMS substrate, drying, repetition is picked up and dried, then is made annealing treatment to obtain
MEMS substrate and the indium oxide porous array sensitive thin film for adulterating gold nano grain for being attached to MEMS substrate surface；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated, then by carbon coating gold nano grain dispersion in indium oxide porous array sensitive thin film surface, drying
Obtain that hydrogen sulfide can be carried out the semiconductor of room temperature gas sensitive detection.
Preferably, in S1, the wavelength of pulse laser is 100~2000nm, and repetition rate is 1~100Hz, and pulse width is
5~1000ns, laser energy are 10~240mJ/pulse.
Preferably, in S1, the spot diameter of pulse laser is 0.1~5.0mm.
Preferably, in S1, in mixed solution, the volume ratio of toluene and ethyl alcohol is (1:100)~(1:1).
Preferably, in S2, ultracentrifugal revolving speed is 1000~30000r/min, and the ultracentrifugal time is greater than 5min.
Preferably, in S2, solution cleaning carries out at least 1 time cleaning using deionized water, ethyl alcohol or acetone.
Preferably, in S3, the temperature of annealing is 300~600 DEG C, the time of annealing is 1~for 24 hours.
Preferably, in S4, the indium oxide of MEMS substrate and the doping gold nano grain for being attached to MEMS substrate surface is porous
Array sensitive thin film is heated to 20~300 DEG C.
The application method for the above-mentioned semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide that the present invention also proposes, detects work
Making temperature is 10~40 DEG C.
The beneficial effect of the present invention compared with the existing technology is:
1, the key of room temperature gas sensitive detection, which is the high-activity carbon cladding gold of indium oxide film surface modification, to be realized to hydrogen sulfide
Nano particle.Firstly, the nano particle of liquid laser ablation preparation has very high chemical activity, because of liquid laser ablation
The most unique feature of method maximum is to form the local plasmon body feathers brightness of high temperature and pressure, however this moment in solid liquid interface moment
The high temperature and pressure plasma plume brightness of formation is quenched in moment again, and this extreme non-equilibrium condition can be in prepared nanometer
Particle surface forms a large amount of chemical dangling bond, scission of link and vacancy, and generates number of drawbacks inside it.And these dangling bond scission of links,
The presence of vacancy and defect makes it have very high chemical activity, plays the role of effective catalyst in gas-sensitive reaction, can be with
Reaction is promoted to occur under lower operating temperature；Secondly, the surface coated carbon-coating of gold nano grain has good electric conductivity
Very low chemical potential energy, can more effective adsorbed target detection gas and transmission electronics.
2, indium oxide itself is a kind of good Semiconductor gas sensors material, the indium oxide film of micro-/micro-nano structure porous array
Then have many advantages, such as sensitivity is higher, response speed faster.
3, the traditional sensors of opposite grade electrode spacing, the MEMS substrate of micron order interdigital electrode spacing greatly reduce
The resistance of sensitive membrane, improves the detection sensitivity of entire circuit.
4, the gold nano grain adulterated inside indium oxide sensitive membrane can prevent indium oxide crystal grain from growing up, cracking, to mention
The air-sensitive stability and service life of high entire sensitive membrane.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure of the semiconductor proposed by the present invention that room temperature gas sensitive detection can be carried out to hydrogen sulfide.
Fig. 2 is the electron-microscope scanning figure of present invention gained indium oxide porous array sensitive thin film.
Fig. 3 is the Electronic Speculum transmission plot of present invention gained carbon coating gold nano grain.
Fig. 4 is the semiconductor progress hydrogen sulfide gas sensitive detection knot that present invention gained can carry out room temperature gas sensitive detection to hydrogen sulfide
Fruit.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
It is proposed by the present invention it is a kind of the semiconductor of room temperature gas sensitive detection can be carried out to hydrogen sulfide, including MEMS substrate and be attached to
The indium oxide porous array sensitive thin film of MEMS substrate surface, doped with gold nano in indium oxide porous array sensitive thin film
Grain, indium oxide porous array sensitive thin film surface modification have carbon coating gold nano grain；Indium oxide porous array sensitive thin film
The number of plies is 1~30 layer, and bore dia is 1~3000nm, and overall thickness is 5~10000nm；Gold nano grain is in indium oxide porous array
Doping density in sensitive thin film is 0.1~200 μ g/cm2, the partial size of gold nano grain is 1~200nm；Carbon coating gold nano
Particle is 0.1~100 μ g/cm in the modification density of indium oxide porous array sensitive thin film2, the partial size of carbon coating gold nano grain
For 1~200nm.
A kind of preparation method of semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide proposed by the present invention, including it is as follows
Step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and solution cleans to obtain carbon coating gold nano grain；By carbon coating gold
Nano particle dispersion obtains carbon coating gold nano grain dispersion liquid in ethanol；
S3, gold nano grain is placed in indium oxide precursor solution, two-dimensional colloidal ball template is then moved into drift to its table
Then face is in the solution picked up colloidal spheres with MEMS substrate, drying, repetition is picked up and dried, then is made annealing treatment to obtain
MEMS substrate and the indium oxide porous array sensitive thin film for adulterating gold nano grain for being attached to MEMS substrate surface；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated, then by carbon coating gold nano grain dispersion in indium oxide porous array sensitive thin film surface, drying
Obtain that hydrogen sulfide can be carried out the semiconductor of room temperature gas sensitive detection.
Embodiment 2
A kind of preparation method of semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide proposed by the present invention, including it is as follows
Step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol, and the volume ratio of toluene and ethyl alcohol is 1:10；The wavelength of pulse laser is
532nm, repetition rate 5Hz, pulse width 5ns, laser energy 40mJ/pulse, spot diameter 1mm；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and carries out cleaning 2 times using ethyl alcohol and obtains carbon coating gold nano
Grain；The dispersion of carbon coating gold nano grain is obtained into carbon coating gold nano grain dispersion liquid in ethanol；Ultracentrifugal revolving speed is
12000r/min, ultracentrifugal time are 30min；
S3, gold nano grain is placed in indium oxide precursor solution, then by the polystyrene colloid ball of diameter 500nm
Two-dimensional colloidal ball template is made by the method being coated with, two-dimensional colloidal ball template is moved and is floated to indium oxide precursor solution surface,
Then colloidal spheres are picked up in the solution with MEMS substrate, is dried, then made annealing treatment to obtain MEMS substrate and be attached to MEMS
The indium oxide porous array sensitive thin film of the doping gold nano grain of substrate surface, the temperature of annealing are 300 DEG C, at annealing
The time of reason is 2h；Wherein the interdigital electrode spacing of MEMS substrate is 10 μm, and interdigital logarithm is 4 pairs, and work area is
10000μm2；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated to 100 DEG C, then does carbon coating gold nano grain dispersion on indium oxide porous array sensitive thin film surface
The dry semiconductor for obtaining that hydrogen sulfide can be carried out room temperature gas sensitive detection.
In the semiconductor that the present embodiment obtains, the doping density of gold nano grain is 1 μ g/cm2, carbon coating gold nano grain
Modification density be 1 μ g/cm2。
Embodiment 3
A kind of preparation method of semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide proposed by the present invention, including it is as follows
Step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol, and the volume ratio of toluene and ethyl alcohol is 1:5；The wavelength of pulse laser is
1064nm, repetition rate 10Hz, pulse width 10ns, laser energy 80mJ/pulse, spot diameter 1.5mm；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and carries out cleaning 3 times using ethyl alcohol and obtains carbon coating gold nano
Grain；The dispersion of carbon coating gold nano grain is obtained into carbon coating gold nano grain dispersion liquid in ethanol；Ultracentrifugal revolving speed is
11000r/min, ultracentrifugal time are 40min；
S3, gold nano grain is placed in indium oxide precursor solution, then by the polystyrene colloid of diameter 1000nm
Ball passes through the method being coated with and two-dimensional colloidal ball template is made, and two-dimensional colloidal ball template is moved drift to indium oxide precursor solution table
Then face is in the solution picked up colloidal spheres with MEMS substrate, drying repeats and picks up and dry 1 time, then made annealing treatment
It obtains MEMS substrate and is attached to the indium oxide porous array sensitive thin film of the doping gold nano grain of MEMS substrate surface, at annealing
The temperature of reason is 400 DEG C, and the time of annealing is 4h；Wherein the interdigital electrode spacing of MEMS substrate is 15 μm, interdigital logarithm
It is 6 pairs, work area is 22500 μm2；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated to 150 DEG C, then does carbon coating gold nano grain dispersion on indium oxide porous array sensitive thin film surface
The dry semiconductor for obtaining that hydrogen sulfide can be carried out room temperature gas sensitive detection.
In the semiconductor that the present embodiment obtains, the doping density of gold nano grain is 2 μ g/cm2, carbon coating gold nano grain
Modification density be 2 μ g/cm2。
Embodiment 4
A kind of preparation method of semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide proposed by the present invention, including it is as follows
Step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol, and the volume ratio of toluene and ethyl alcohol is 1:2.5；The wavelength of pulse laser is
266nm, repetition rate 20Hz, pulse width 15ns, laser energy 100mJ/pulse, spot diameter 2.0mm；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and carries out cleaning 3 times using ethyl alcohol and obtains carbon coating gold nano
Grain；The dispersion of carbon coating gold nano grain is obtained into carbon coating gold nano grain dispersion liquid in ethanol；Ultracentrifugal revolving speed is
13000r/min, ultracentrifugal time are 30min；
S3, gold nano grain is placed in indium oxide precursor solution, then by the polystyrene colloid ball of diameter 200nm
Two-dimensional colloidal ball template is made by the method being coated with, two-dimensional colloidal ball template is moved and is floated to indium oxide precursor solution surface,
Then colloidal spheres are picked up in the solution with MEMS substrate, dries, repeats and pick up and dry 2 times, then make annealing treatment
To the indium oxide porous array sensitive thin film of MEMS substrate and the doping gold nano grain for being attached to MEMS substrate surface, annealing
Temperature be 400 DEG C, time of annealing is 6h；Wherein the interdigital electrode spacing of MEMS substrate is 15 μm, and interdigital logarithm is 8
Right, work area is 40000 μm2；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated to 200 DEG C, then does carbon coating gold nano grain dispersion on indium oxide porous array sensitive thin film surface
The dry semiconductor for obtaining that hydrogen sulfide can be carried out room temperature gas sensitive detection.
In the semiconductor that the present embodiment obtains, the doping density of gold nano grain is 3 μ g/cm2, carbon coating gold nano grain
Modification density be 3 μ g/cm2。
Embodiment 5
A kind of preparation method of semiconductor that room temperature gas sensitive detection can be carried out to hydrogen sulfide proposed by the present invention, including it is as follows
Step:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid through pulsed laser irradiation
Solution；Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid through pulsed laser irradiation
Solution, wherein mixed solution includes toluene and ethyl alcohol, and the volume ratio of toluene and ethyl alcohol is 1:2；The wavelength of pulse laser is
355nm, repetition rate 10Hz, pulse width 20ns, laser energy 120mJ/pulse, spot diameter 0.5mm；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold
Nanoparticle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and carries out cleaning 4 times using ethyl alcohol and obtains carbon coating gold nano
Grain；The dispersion of carbon coating gold nano grain is obtained into carbon coating gold nano grain dispersion liquid in ethanol；Ultracentrifugal revolving speed is
13000r/min, ultracentrifugal time are 40min；
S3, gold nano grain is placed in indium oxide precursor solution, then by the polystyrene colloid of diameter 2000nm
Ball passes through the method being coated with and two-dimensional colloidal ball template is made, and two-dimensional colloidal ball template is moved drift to indium oxide precursor solution table
Then face is in the solution picked up colloidal spheres with MEMS substrate, drying repeats and picks up and dry repeatedly, then carries out at annealing
Reason obtains MEMS substrate and is attached to the indium oxide porous array sensitive thin film of the doping gold nano grain of MEMS substrate surface, annealing
The temperature of processing is 400 DEG C, and the time of annealing is 12h；Wherein the interdigital electrode spacing of MEMS substrate is 12 μm, interdigital right
Number is 10 pairs, and work area is 22500 μm2；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitivity it is thin
Film is heated to 180 DEG C, then does carbon coating gold nano grain dispersion on indium oxide porous array sensitive thin film surface
The dry semiconductor for obtaining that hydrogen sulfide can be carried out room temperature gas sensitive detection.
In the semiconductor that the present embodiment obtains, the doping density of gold nano grain is 3 μ g/cm2, carbon coating gold nano grain
Modification density be 3 μ g/cm2。
The semiconductor that can carry out room temperature gas sensitive detection obtained by the present invention to hydrogen sulfide is subjected to electron-microscope scanning, result is as schemed
Shown in 1.The present invention is prepared for uniformly and the fine and close porous battle array of indium oxide in the interdigital electrode of MEMS substrate as seen from Figure 1
Column sensitive thin film.
Indium oxide porous array sensitive thin film obtained by the present invention is subjected to electron-microscope scanning, result is as shown in Figure 2.By Fig. 2
It can be seen that gold nano grain of the inside of indium oxide porous array sensitive thin film doped with high activity, indium oxide porous array are quick
The surface modification of sense film has carbon coating gold nano grain.
Carbon coating gold nano grain obtained by the present invention is subjected to Electronic Speculum transmission, result is as shown in Figure 3.It can be seen by Fig. 3
Out carbon coating gold nano grain using Jin Weihe, using carbon as the core-shell structure of shell.
The present invention is used for the room temperature detection to hydrogen sulfide gas, under 20 DEG C of environment of room temperature, the unheated condition of product
Under, when purpose product shown in FIG. 1 is respectively placed in 2~5ppm hydrogen sulfide atmosphere, measured air-sensitive response results such as Fig. 3
It is shown.The present invention shows good air-sensitive respective performances to hydrogen sulfide gas at normal temperature as seen from Figure 3.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (13)
1. a kind of semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide, which is characterized in that including MEMS substrate and be attached to
The indium oxide porous array sensitive thin film of MEMS substrate surface, doped with gold nano in indium oxide porous array sensitive thin film
Grain, indium oxide porous array sensitive thin film surface modification have carbon coating gold nano grain；Indium oxide porous array sensitive thin film
The number of plies is 1~30 layer, and bore dia is 1~3000nm, and overall thickness is 5~10000nm；Gold nano grain is in indium oxide porous array
Doping density in sensitive thin film is 0.1~200 μ g/cm2, the partial size of gold nano grain is 1~200nm；Carbon coating gold nano
Particle is 0.1~100 μ g/cm in the modification density of indium oxide porous array sensitive thin film2, the partial size of carbon coating gold nano grain
For 1~200nm；
Every layer of indium oxide porous array sensitive thin film is the orderly porous membrane of Hexagonal array.
2. the semiconductor of room temperature gas sensitive detection can be carried out to hydrogen sulfide according to claim 1, which is characterized in that gold nano
Grain is polycrystalline state gold nano grain.
3. the semiconductor of room temperature gas sensitive detection can be carried out to hydrogen sulfide according to claim 1, which is characterized in that carbon coating gold
In nano particle, carbon is monocrystalline or amorphous state, 1~30nm of carbon-coating thickness.
4. any one of -3 semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide according to claim 1, which is characterized in that
The interdigital electrode spacing of MEMS substrate is 1~1000 μm, and interdigital logarithm is 1~100 pair, and work area is 100 μm2~
1mm2。
5. a kind of preparation side for the semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide as described in claim any one of 1-4
Method, which comprises the steps of:
S1, gold target material is placed in the deionized water of stirring, obtains gold nano-particle colloid solution through pulsed laser irradiation；
Gold target material is placed in the mixed solution of stirring, obtains carbon coating gold nano-particle colloid solution through pulsed laser irradiation,
Wherein mixed solution includes toluene and ethyl alcohol；
S2, gold nano-particle colloid solution is carried out to high speed centrifugation, separation of solid and liquid obtains gold nano grain；By carbon coating gold nano
Particle colloid solution carries out high speed centrifugation, is separated by solid-liquid separation, and solution cleans to obtain carbon coating gold nano grain；By carbon coating gold nano
Particle dispersion obtains carbon coating gold nano grain dispersion liquid in ethanol；
S3, gold nano grain is placed in indium oxide precursor solution, then by two-dimensional colloidal ball template shifting drift to its surface, so
Colloidal spheres are picked up in the solution with MEMS substrate afterwards, are dried, repetition is picked up and dried, then is made annealing treatment to obtain MEMS base
Bottom and the indium oxide porous array sensitive thin film for adulterating gold nano grain for being attached to MEMS substrate surface；
S4, by MEMS substrate and be attached to MEMS substrate surface doping gold nano grain indium oxide porous array sensitive thin film into
Carbon coating gold nano grain dispersion, is then dried to obtain by row heating on indium oxide porous array sensitive thin film surface
The semiconductor of room temperature gas sensitive detection can be carried out to hydrogen sulfide.
6. can carry out the preparation method of the semiconductor of room temperature gas sensitive detection to hydrogen sulfide according to claim 5, feature exists
In in S1, the wavelength of pulse laser is 100~2000nm, and repetition rate is 1~100Hz, and pulse width is 5~1000ns, is swashed
Light energy is 10~240mJ/pulse.
7. can carry out the preparation method of the semiconductor of room temperature gas sensitive detection to hydrogen sulfide according to claim 5, feature exists
In in S1, the spot diameter of pulse laser is 0.1~5.0mm.
8. can carry out the preparation method of the semiconductor of room temperature gas sensitive detection to hydrogen sulfide according to claim 5, feature exists
In in S1, in mixed solution, the volume ratio of toluene and ethyl alcohol is (1:100)~(1:1).
9. according to the preparation method of any one of the claim 5-8 semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide,
It is characterized in that, ultracentrifugal revolving speed is 1000~30000r/min in S2, the ultracentrifugal time is greater than 5min.
10. according to the preparation method of any one of the claim 5-8 semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide,
It is characterized in that, solution cleaning carries out at least 1 time cleaning using deionized water, ethyl alcohol or acetone in S2.
11. according to the preparation method of any one of the claim 5-8 semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide,
It is characterized in that, in S3, the temperature of annealing is 300~600 DEG C, the time of annealing is 1~for 24 hours.
12. according to the preparation method of any one of the claim 5-8 semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide,
It is characterized in that, in S4, by the indium oxide porous array of MEMS substrate and the doping gold nano grain for being attached to MEMS substrate surface
Sensitive thin film is heated to 20~300 DEG C.
13. a kind of user for the semiconductor that can carry out room temperature gas sensitive detection to hydrogen sulfide as described in claim any one of 1-4
Method, which is characterized in that detection operating temperature is 10~40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610192050.3A CN105842292B (en) | 2016-03-28 | 2016-03-28 | A kind of pair of hydrogen sulfide carries out semiconductor and its preparation, use of room temperature gas sensitive detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610192050.3A CN105842292B (en) | 2016-03-28 | 2016-03-28 | A kind of pair of hydrogen sulfide carries out semiconductor and its preparation, use of room temperature gas sensitive detection |
Publications (2)
| Publication Number | Publication Date |
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| CN108802107B (en) * | 2017-05-02 | 2021-02-09 | 中国石油化工股份有限公司 | Method for measuring concentration of hydrogen sulfide based on resistance |
| CN109668937A (en) * | 2018-12-13 | 2019-04-23 | 大连理工大学 | A kind of the composite nano fiber ammonia gas sensor and its preparation process of amorphous carbon-graphene-cobaltosic oxide package structure |
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