CN104034758A - Integrated hydrogen sensor made from mixed graphene film, noble metal particles and metallic oxide materials and preparation method thereof - Google Patents
Integrated hydrogen sensor made from mixed graphene film, noble metal particles and metallic oxide materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an integrated hydrogen sensor made from mixed graphene film, noble metal particles and metallic oxide materials and a preparation method of the integrated hydrogen sensor. The sensor comprises a substrate, a heating electrode, a heat-conducting insulation layer and a detection electrode; the heating electrode is placed on the substrate; the heat-conducting insulation layer is placed between the heating electrode and the detection electrode and further the sensor further comprises a metallic oxide film deposited on the detection electrode, the noble metal particles deposited on the metallic oxide film, and the graphene film covers the metallic oxide film on which the noble metal particles are deposited. The noble metal particles covering the metallic oxide film are single atoms, wherein the covering rate is 0.05-100 percent, the particle size is 0.2-0.4 nanometers, and the noble metal particles are randomly and uniformly arranged. The metallic oxide film is 10 nanometers to 2 micrometers in thickness. The graphene film is 0.5-1.2 nanometers in thickness. By adopting the integrated hydrogen sensor provided by the invention, high-sensitivity and high-selectivity detection and monitoring for hydrogen can be simultaneously achieved.
Description
Technical field
The invention belongs to gas sensor field, be specifically related to integrated hydrogen sensor of a specific admixture graphene film, noble metal and metal oxide materials and preparation method thereof
.
Background technology
Hydrogen, due to advantages such as its burning efficiency are high, product is pollution-free, is called as three large new forms of energy together with sun power, nuclear energy.As a kind of new forms of energy, hydrogen is widely used in fields such as aviation, power; Meanwhile, hydrogen, as a kind of reducibility gas and carrier gas, in chemical industry, electronics, medical treatment, metal smelt, has very important using value in military and national defense field especially.But hydrogen molecule is very little, in the process of producing, store, transporting and using, easily leak.Because hydrogen is colourless, tasteless, explosive, and kindling point is only 585 ℃, in air, content, in 4% one 75% scopes, is met naked light and is blasted, thus in the use of hydrogen, must utilize high sensitivity hydrogen gas sensor to environment in the content of hydrogen detect and its leakage monitored.
Current hydrogen gas sensor mainly be take semiconductor material as main, and resistor-type semiconductor hydrogen gas sensor is mainly with SnO
2, ZnO, WO
3deng metal oxide, it is gas sensitive.Metal oxide is a kind of semiconductor material, when hydrogen is after metal oxide surface absorption, the oxonium ion of the electronics that hydrogen discharges as alms giver in chemisorbed layer is combined, cause carrier concentration in metal oxide semiconductor material to change, and then cause the resistance of material to change.Metal oxide semiconductor hydrogen sensor is by the variation of survey sensor resistance value, to obtain the content of hydrogen.Yet low to the general response sensitivity of reducibility gas based on metal-oxide gas transducer.Particularly importantly metal oxide sensor can be responsive to most of reducibility gas, therefore the selectivity that hydrogen is detected is poor.
The sensitivity that metal oxide hydrogen gas sensor is low can take the methods such as surface modification, doping to improve.By surperficial noble metal, adulterate to optimize air-sensitive performance and become the main method of improving gas sensitive susceptibility.When noble metal is evenly distributed on behind metal oxide materials surface, for reacting gas provides activated centre, not only reduce reaction activity, can increase electronics shifting to zinc paste in the concentration of adsorbed gas and intensified response process simultaneously, metal oxide crystal boundary potential barrier is reduced, electricity is led increase, has improved the sensitivity of material, has reduced the temperature of reaction of material and gas simultaneously.Yet, to the surface modification of metal oxide, be entrained in when having improved in all directions sensitive material to hydrogen and other gas sensitivities, still can not solve the selectivity that hydrogen is detected, need so new technology to contain optionally problem.
Emerging two-dimentional Graphene is one of the research that receives much attention in current numerous nano material and product object.Compare with traditional material, Graphene has the thickness of monoatomic layer, excellent mechanics, calorifics and electric property.Graphene not only can be used as the basic structural unit that builds other carbonaceous materials, can be used as again packing material and comes the advanced composite material (ACM) of processability excellence and desirable non-metallic catalyst carrier material simultaneously.Graphene has thickness, even aperture distribution, superelevation physical strength and the high thermal conductivity of atomic layer, is almost desirable gas film parting material.Because the physical size (< 0.2nm) of Graphene is less than the kinetic diameter of all conventional gas molecules, Graphene is but extensively thought that to gas and fluid molecule be completely impervious.
Summary of the invention
In order to improve sensitivity and the selectivity of hydrogen gas sensor simultaneously, the invention provides a kind of integrated hydrogen sensor and preparation method thereof, this sensor mixes Graphene, noble metal and metal oxide, the sensitivity that noble metal-metal oxide composite structure is used for improving hydrogen gas sensor; Utilize the aperture size of Graphene only to allow hydrogen to pass through graphene film aperture and react with sensitive material, utilize like this and cover the selectivity that Graphene improves hydrogen gas sensor.
To achieve these goals, the technological means that the present invention adopts is:
A kind of integrated hydrogen sensor, comprise substrate, heating electrode, heat conductive insulating layer, detecting electrode, heating electrode is positioned on substrate, heat conductive insulating layer is between heating electrode and detecting electrode, its characteristic is: also comprise the metal-oxide film being deposited on detecting electrode, metal-oxide film deposits noble metal on surface, and graphene film covers on the metal-oxide film that deposits noble metal.
Described noble metal is monatomic covering on metal-oxide film, and coverage is 0.05%-10%, and particle size is 0.2nm-0.4nm, evenly distributed at random.(percentage that the area that coverage covers metal-oxide film surface with noble metal accounts for metal-oxide film surface area recently represents)
Described metal-oxide film thickness is 10 nanometers to 2 micron.
Described graphene film thickness is extremely several atomic layers of individual layer, and thickness is in 0.5-1.2 nanometer.
Described noble metal is one or more in Au, Ag, Pt, Pd, Rh, Ru, Os, Ir.
Described metal-oxide film is made by transition metal oxide, non-transition metal oxides or composite oxide of metal.Described transition metal oxide is Cr
2o
3, γ-Fe
2o
3, WO
3, TiO
2, a kind of in NiO, MgO; Described non-transition metal oxides is SnO
2, ZnO, Mn
2o
3, Co
3o
4, CuO, SrO, In
2o
3, V
2o
3, GeO
2, Nb
2o
5, MoO
3, Ta
2o
5, CeO
2in a kind of; Composite oxide of metal is CeO
2-SnO
2, TiO
2-SnO
2, TiO
2-ZnO, Cu-ZnO, Sb
2o
3-SnO
2, Bi
2o
3-SnO
2, La
2o
3-SnO
2, CaO-La
2o
3, Ag-CuO-BaTiO
2, Cr
1.
8tiO
3, Pd-La
2o
3-SnO
2, Pd-La
2o
3-In
2o
3, ZnO-SnO
2, CuO-SnO
2, In-TiO
2, In
2o
3-SnO
2, Cd-SnO
2, Ga-ZnO and Li
2sO
4-CaSO
4-SiO
2in a kind of.
Indication electrode material of the present invention is metal: Pt, Pd, Ag, Au, Mo, Cu, Al, Cr etc.; (2) alloy: Ag-Pd, Ag-Pt, Mn-Cu, Fe-Al, Fe-Cr-Al, Ni-Cr, Ni-Cr-O, Ni-Cr-Cu-Al, Ni-Cr-Fe-Al, Ni-Cr-Be; (3) metal oxide: RuO
2, Sn-Sb-Al
2o
3, Sn-Sb-TiO
2, TiO
2; (4) carbon film: SiO
2-C, SiC; (5) metallic ceramics: Cr-SiO
2, Ti-SiO
2, Au-SiO, Au-SiO
2, NiCr-SiO
2, Ta-SiO
2; (6) compound substance: NiCr-TaN, NiCr-CrSi.Detecting electrode material mainly contains: (1) metal: Au, Pd, Pt, Ag, Cu, Al; (2) alloy: Ag-Pt, Ag-Pd, Ni-Cu; (3) metal oxide: RuO
2, TiO
2; (4) graphite material: C.
The preparation method of described a kind of integrated hydrogen sensor, comprises the steps:
1) clean substrate;
2) photoetching heating electrode pattern on substrate, then heating electrode is prepared in sputter;
3) adopt magnetron sputtering deposition, means of electron beam deposition or chemical vapor deposition, on heating electrode, prepare heat conductive insulating layer;
4) photoetching detecting electrode pattern adopts means of electron beam deposition or magnetron sputtering deposition detecting electrode on step 3) heat conductive insulating layer;
5) adopt membrane deposition method depositing metal oxide film on detecting electrode;
6) adopt vacuum deposition method depositing noble metal particle on metal-oxide film;
7) on sull, cover graphene film.
Described in step 5), membrane deposition method is any one in chemical spray pyrolysis method, chemical vapour deposition technique, sol-gal process, electrochemical deposition, magnetron sputtering method and pulsed laser deposition.
The preparation method of described a kind of integrated hydrogen sensor, concrete steps are as follows:
Heating electrode mainly contains: (1) metal: Pt, Pd, Ag, Au, Mo, Cu, Al, Cr etc.; (2) alloy: Ag-Pd, Ag-Pt, Mn-Cu, Fe-Al, Fe-Cr-Al, Ni-Cr, Ni-Cr-O, Ni-Cr-Cu-Al, Ni-Cr-Fe-Al, Ni-Cr-Be; (3) metal oxide: RuO
2, Sn-Sb-Al
2o
3, Sn-Sb-TiO
2, TiO
2; (4) carbon film: SiO
2-C, SiC; (5) metallic ceramics: Cr-SiO
2, Ti-SiO
2, Au-SiO, Au-SiO
2, NiCr-SiO
2, Ta-SiO
2; (6) compound substance: NiCr-TaN, NiCr-CrSi.
Detecting electrode material mainly contains: (1) metal: Au, Pd, Pt, Ag, Cu, Al; (2) alloy: Ag-Pt, Ag-Pd, Ni-Cu; (3) metal oxide: RuO
2, TiO
2; (4) graphite material: C.
The preparation of heating electrode:
(1) cleaning of substrate;
(2) photoetching heating electrode pattern, the process of photoetching is under the effect of illumination, and photoresist has absorbed light intensity, and makes photoresist that certain chemical change occur by chemical action, through the processing of the processes such as development, obtain the Micropicture structure being formed by stable residue photoresist again.Photoetching process generally comprises the techniques such as gluing, exposure, development, etching, can obtain needed heating electrode pattern by photoetching technique on substrate;
(3) physical deposition plating heating electrode, adopts magnetron sputtering plated electrode or electron beam deposition electrode;
(4) deposition materials peels off the formation with heating electrode;
(5) physics or chemogenic deposit heat conductive insulating layer: adopt magnetron sputtering, electron beam or chemical vapor deposition on heating electrode, to prepare heat conductive insulating layer;
(6) secondary photoetching and etching, secondary photoetching is that photoresist is blocked to heating electrode perform region, and photoresist is as mask, and heating electrode pin part photoresist is removed by acetone after photoetching development, again by ion beam etching, by the SiO of heating electrode pin top
2insulation course etching is removed;
The preparation of detecting electrode:
(1) photoetching detecting electrode pattern, adopts photoetching technique to prepare detecting electrode pattern;
(2) physical deposition detecting electrode, adopts magnetron sputtering deposition or electron beam deposition to prepare detecting electrode on heat conductive insulating layer.
(3) deposition materials peels off the formation with detecting electrode.Electrode production process is as Fig. 1.
The preparation of metal-oxide film:
Utilize membrane deposition method as chemical spray pyrolysis method, chemical vapour deposition technique, sol-gal process, electrochemical deposition, magnetron sputtering method, electron beam evaporation, laser physics sedimentation, on detecting electrode, deposit the metal-oxide film of tens nanometer to two microns (10nm-2 μ m) thickness.
The vacuum moulding machine of noble metal on metal-oxide film surface:
Utilize vacuum deposition method as: magnetron sputtering, laser physics deposition, chemical vapor deposition, depositing noble metal particle on metal-oxide film (particle or reticulate texture).
Beneficial effect: the present invention proposes integrated hydrogen sensor of a specific admixture graphene film, noble metal and metal oxide materials and preparation method thereof
,the sensitivity that noble metal-metal oxide composite structure is used for improving hydrogen gas sensor.Utilize Graphene aperture size, large molecule is blocked in outside film, and the characteristic that little molecule can pass through improves the selectivity of hydrogen gas sensor, and hydrogen gas sensor provided by the invention can be realized simultaneously and detecting and monitoring high sensitivity and high selectivity.
The present invention is applied to gas sensor at Graphene and has obvious originality aspect preparing.Inventor finds to cause introducing regular texture defect Graphene aperture to increase and the electricity environment passivation to aperture by selected molecule, incredible, particularly separated to the selection of hydrogen thereby the graphene film that reduces coulomb repulsion power shows.The dependence of the sensor selectivity that the present invention breaks traditions to material, utilizes the aperture size of Graphene only to allow hydrogen to pass through, and graphene film reacts with sensitive material, and the sensor that covers like this Graphene has improved the selectivity to hydrogen greatly.
Be different from current Graphene and in sensor application, mainly utilize the gas absorption characteristic of grapheme material itself and the principle of resistance variations, the present invention utilizes the big or small selectivity in Graphene aperture to see through small size gas molecule and stops principle that large scale gas molecule arrives at sensitive material to solve in gas test an optionally difficult problem.The invention solves susceptibility and the selective problems of the hydrogen detection of long-term puzzlement.Utilize hydrogen gas sensor of the present invention can in many gaseous environments, select to detect the hydrogen of 20ppm.
The invention provides the method that a pervasive solution gas-selectively detects.Although the present invention is particularly suitable for the high selectivity of small size gas molecule, detect, yet the principle of utilizing pore size selectivity to see through gas molecule can extend to the selection of other gas molecules, detect.As long as there is different sizes in these gas molecules, the particularly detection of the selective gas in the environment that only has two kinds or a few gas to exist.
Accompanying drawing explanation
Fig. 1: heating electrode and detecting electrode preparation flow figure;
Fig. 2: vacuum deposition methods noble metal structural drawing;
Fig. 3: hydrogen gas sensor structural drawing;
Fig. 4: the sensitivity test result of hydrogen gas sensor to gas with various; Wherein: 1-substrate; 2-heating electrode, 3-heat conductive insulating layer, 4-detecting electrode, 5-sull, 6-noble metal; 7-graphene film.
Embodiment
Following examples be take Graphene-precious metal palladium particle-zinc paste (Gra-Pd-ZnO) film-type integrated hydrogen sensor as example detailed description its preparation method and effect, other noble metal character are similar with it, do not do explanation one by one, this embodiment object is for a better understanding of the present invention, can not be as the restriction to content of the present invention.
Embodiment 1
Preparation Gra-Pd-ZnO film-type hydrogen gas sensor, concrete steps are as follows:
The preparation of detecting electrode-heating electrode substrate
(1) substrate cleans: to SiO
2-Si substrate adopts acetone, ethanol, and deionized water is successively to SiO
2-Si substrate carries out ultrasonic cleaning 5 minutes, and then nitrogen dries up, standby.
(2) photoetching heating electrode pattern: photoresist adopts the positive glue of the auspicious red RZJ-304 in Suzhou, first the substrate cleaning is carried out to photoresist spin coating, the slow-speed of revolution is 500rpm, rotational time is 5s, high rotating speed 4000rpm, rotational time is 20s, follow front baking 2min at 100 ℃, then ABM litho machine is installed to mask plate corresponding to heating electrode, 9s exposes, light intensity is 15mw/cm2, development 11s after exposure, at 100 ℃, firmly dry again 5min, firmly dried cooling, can carry out development treatment, developer solution is the auspicious red RZX-3038 positivity developer solution in Suzhou, development time is 9S.After developing, use washed with de-ionized water substrate, nitrogen dries up standby.
(3) preparation of heating electrode: select the JGP560 type magnetron sputtering plating instrument of Chinese Academy of Sciences's Shenyang scientific instrument development, first by instrument vacuum breaker, the substrate with electrode pattern is installed, plated electrode target Ni is installed
20cr
80, closed hatch door, closing baffle plate, is evacuated to 1.5 * 10
-3when Pa is following, passing into Ar airshed is 25sccm, and it is 1.7Pa that build-up of luminance pressure is set, and keeps the pressure of 0.5Pa constant during build-up of luminance, and it is 28w(electric current 0.1A that sputtering power is set, voltage 280v), the time of sputter is 4min.After sputter is complete, close slide valve, stop plumage brightness, stop vacuumizing, pour nitrogen vacuum breaker, take out sample, put into the ultrasonic 1min of acetone soln, remove photoresist, obtain heating electrode.Heating electrode substrate is rinsed well with deionized water, and nitrogen dries up standby.
(4) physical deposition heat conductive insulating layer: select electron beam deposition insulation course SiO
2, heating electrode substrate is put into electron beam deposition chamber sample and drag, SiO is installed
2particle target, closes hatch door, is evacuated to 5 * 10
-4when Pa is following, unlocking electronic rifle power supply, regulates speed stream 250mA, after stablizing, opens baffle plate, opens film thickness gauge simultaneously, and rate of sedimentation is 2A/s, deposition SiO
2thickness is 200nm, after deposition finishes, closes speed stream, closes slide valve, stops vacuumizing cooling rear taking-up sample.
(5) secondary photoetching and etching: secondary photoetching is that photoresist is blocked to heating electrode perform region, and heating electrode pin part photoresist is eliminated, photoresist is as mask, then by ion beam etching, by the SiO of heating electrode pin top
2insulation course etching is removed.Photoresist adopts the positive glue of the auspicious red RZJ-304 in Suzhou, first the substrate that has plated insulation course is carried out to photoresist spin coating, the slow-speed of revolution is 500rpm, rotational time is 5s, high rotating speed 4000rpm, rotational time is 20s, and then front baking 2min at 100 ℃, then installs mask plate corresponding to secondary photoetching to ABM litho machine, 9s exposes, light intensity is 15mw/cm2, development 11s after exposure, then at 100 ℃, firmly dry 5min, firmly dried cooling, can carry out development treatment, developer solution is the auspicious red RZX-3038 positivity developer solution in Suzhou, and development time is 9S.After developing, use washed with de-ionized water substrate, nitrogen dries up standby; Etching adopts ion bean etcher, and the substrate after photoresist mask is installed, and is evacuated to 4.5 * 10
-4when Pa is following, pass into etching gas Ar gas 3.0sccm, regulating ion beam incident angle is 60 °, ion speed stream 100mA, plate voltage 400v, electronics speed stream 70mA, cathode current 13A, in and electric current 11A, anode current 1.2A, anode voltage 55V, etching time 45s.After etching completes, treat that sample stage temperature is increased to more than 15 ℃, can take out sample.
(6) photoetching detecting electrode pattern: photoresist adopts the positive glue of the auspicious red RZJ-304 in Suzhou, first the substrate after etching is carried out to photoresist spin coating, the slow-speed of revolution is 500rpm, rotational time is 5s, high rotating speed 4000rpm, rotational time is 20s, follow front baking 2min at 100 ℃, the mask plate of then ABM litho machine installation and measuring electrode pair being answered, 9s exposes, light intensity is 15mw/cm2, development 11s after exposure, at 100 ℃, firmly dry again 5min, firmly dried cooling, can carry out development treatment, developer solution is the auspicious red RZX-3038 positivity developer solution in Suzhou, development time is 9S.After developing, use washed with de-ionized water substrate, nitrogen dries up standby.
(7) physical deposition detecting electrode: select electron beam deposition detecting electrode Al, the substrate that has plated insulation course is put into electron beam deposition chamber sample and drag, Al particle target is installed, close hatch door, be evacuated to 5 * 10
-4when Pa is following, unlocking electronic rifle power supply, regulates speed stream 250mA, after stablizing, opens baffle plate, opens film thickness gauge simultaneously, and rate of sedimentation is 2A/s, and depositing Al thickness is 80nm, after deposition finishes, closes speed stream, closes slide valve, stops vacuumizing cooling rear taking-up sample.Put into the ultrasonic 1min of acetone soln, remove photoresist, obtain detecting electrode.Heating electrode substrate is rinsed well with deionized water, and nitrogen dries up standby.
Pulsed laser deposition (PLD) ZnO film
(1) target and electrode base sheet are installed: PLD deposit cavity is opened, ZnO target is arranged on to position No. 1, Pd target is arranged on position (instrument model: PLD-450B type Gas Sensor Films Deposited by Pulsed Laser Deposition system) No. 2, electrode base sheet is fixed on sample carrier, regulating target holder and substrate spacing is 56mm, closes hatch door and air release.
(2) setting of mode of deposition in vacuum chamber: after substrate and target install, first cavity is vacuumized to processing, first open mechanical pump and be evacuated to below 20Pa, be then extracted into 10 with molecular pump
-3below Pa; Chamber pressure reaches after deposition requirement, can arrange the temperature of ZnO film deposition, and be 500 ℃; After temperature stabilization, pass into oxygen, passing into of oxygen can prevent that ZnO film oxygen defect is too much, but oxygen is pressed the too high crystalline quality that can affect again film, and while finding that according to research oxygen is pressed as 10Pa, ZnO film crystalline quality is best.
(3) setting of laser parameter: regulate target rotating speed and sample stage rotating speed, open two dimensional laser scanning device, closing baffle plate, open laser power supply, after stable, laser energy is adjusted to 200mJ, frequency is 5Hz, first target is carried out to pre-sputtering 5min, sedimentation time is set as 27min, and the metal-oxide film of this time deposition is about 200nm thickness; After above parameter sets, operation laser (RUN+EXE), then opens baffle plate electrode base sheet is started to plated film.
Pulsed laser deposition Pd particle
(1) setting of mode of deposition in vacuum chamber: close oxygen and pass into after metal-oxide film has deposited, continue to vacuumize; Deng depositing temperature, be reduced to 50 ℃ when following, target is underpined to the target into Pd, holding chamber internal pressure is 5 * 10
-14below Pa.
(2) setting of laser parameter: regulate target rotating speed and sample stage rotating speed, open two dimensional laser scanning device, closing baffle plate, open laser power supply, after stable, laser energy is adjusted to 400mJ, frequency is 1Hz, first target is carried out to pre-sputtering 1min, it is pulse 10 times that the noble metal loading time is set as 10S(), the noble metal concentration of this time deposition is the highest to metal-oxide film sensitivity; After above parameter sets, operation laser (RUN+EXE), then opens baffle plate metal-oxide film is carried out to noble metal deposition.
Transfer and the covering of graphene film on Pd-ZnO hydrogen gas sensor film
(1) the PMMA/ single-layer graphene/organic polymer layer that business can be purchased is put into deionized water, dissolve away the organic polymer of lower floor, then use target substrate (Pd-ZnO thin film sensor) to be pulled out, single-layer graphene is covered in colorimetric sensor films, room temperature is dried 30min;
(2) after naturally drying, sensor is put into the dry 30min of thermostatic drying chamber, 75 ℃ of baking temperatures, after drying, take out to put it in 30 ℃ of water-bath acetone solns and soak 30min, it is in order to remove the PMMA(polymethylmethacrylate above Graphene that acetone soaks), taking-up is dried, and the hydrogen gas sensor metal-oxide film thickness obtaining is 200nm; Graphene film thickness is 0.8nm; Noble metal coverage is that 0.5%, Pd particle diameter is 0.27nm, evenly distributed at random.
The CGS-1TP dynamic air-distributing air-sensitive detection system that adopts Beijing Ai Lite to produce, sensitivity adopts Ra/Rg to represent, and institute's gas distribution is 500ppm, and sensor heating-up temperature is 100 ℃.The results are shown in Figure 4, prepared Graphene-Pd-ZnO hydrogen gas sensor, it is 2.63 to the sensitivity of hydrogen, to ethanol, CO, acetone, methane gas all do not show sensitivity, only hydrogen is had to selectivity.
Claims (9)
1. an integrated hydrogen sensor, comprise substrate, heating electrode, heat conductive insulating layer and detecting electrode, heating electrode is positioned on substrate, heat conductive insulating layer is between heating electrode and detecting electrode, its characteristic is: also comprise the metal-oxide film being deposited on detecting electrode, metal-oxide film deposits noble metal on surface, and graphene film covers on the metal-oxide film that deposits noble metal.
2. a kind of integrated hydrogen sensor according to claim 1, is characterized in that: described noble metal is monatomic covering on metal-oxide film, and coverage is 0.05%-10%, and particle size is 0.2nm-0.4nm, evenly distributed at random.
3. a kind of integrated hydrogen sensor according to claim 1, is characterized in that: described metal-oxide film thickness is 10nm-2 μ m.
4. a kind of integrated hydrogen sensor according to claim 1, is characterized in that: described graphene film thickness 0.5-1.2nm.
5. a kind of integrated hydrogen sensor according to claim 1, is characterized in that: described noble metal is at least one in Au, Ag, Pt, Pd, Rh, Ru, Os, Ir.
6. a kind of integrated hydrogen sensor according to claim 1, is characterized in that: described metal-oxide film is made by transition metal oxide, non-transition metal oxides or composite oxide of metal.
7. a kind of integrated hydrogen sensor according to claim 6, is characterized in that: described transition metal oxide is Cr
2o
3, γ-Fe
2o
3, WO
3, TiO
2, a kind of in NiO; Described non-transition metal oxides is SnO
2, ZnO, MgO, Mn
2o
3, Co
3o
4, CuO, SrO, In
2o
3, V
2o
3, GeO
2, Nb
2o
5, MoO
3, Ta
2o
5, CeO
2in a kind of; Composite oxide of metal is CeO
2-SnO
2, TiO
2-SnO
2, TiO
2-ZnO, Cu-ZnO, Sb
2o
3-SnO
2, Bi
2o
3-SnO
2, La
2o
3-SnO
2, CaO-La
2o
3, Ag-CuO-BaTiO
2, Cr
1.
8tiO
3, Pd-La
2o
3-SnO
2, Pd-La
2o
3-In
2o
3, ZnO-SnO
2, CuO-SnO
2, In-TiO
2, In
2o
3-SnO
2, Cd-SnO
2, Ga-ZnO and Li
2sO
4-CaSO
4-SiO
2in a kind of.
8. the preparation method of integrated hydrogen sensor described in any one in claim 1 ~ 7, is characterized in that comprising the steps:
1) clean substrate;
2) photoetching heating electrode pattern on substrate, then sputter or electron beam deposition are prepared heating electrode;
3) adopt magnetron sputtering deposition method, means of electron beam deposition or chemical vapor deposition, on heating electrode, prepare heat conductive insulating layer;
4) photoetching detecting electrode pattern adopts sputter or means of electron beam deposition deposition detecting electrode on step 3) heat conductive insulating layer;
5) adopt membrane deposition method depositing metal oxide film on detecting electrode;
6) adopt vacuum deposition method depositing noble metal particle on metal-oxide film;
7) on metal-oxide film, cover graphene film.
9. the preparation method of integrated hydrogen sensor according to claim 8, is characterized in that: described in step 5), membrane deposition method is any one in chemical spray pyrolysis method, chemical vapour deposition technique, sol-gal process, electrochemical deposition, magnetron sputtering method and pulsed laser deposition.
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