CN104034763A - Noble metal doped particles and metallic oxide film integrated gas sensor and preparation method thereof - Google Patents
Noble metal doped particles and metallic oxide film integrated gas sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a noble metal doped particles and metallic oxide film integrated gas sensor and a preparation method thereof. The integrated gas sensor comprises a substrate, a heating electrode, a heat-conductive insulating layer, a detecting electrode and a metallic oxide film, wherein the heating electrode is prepared on the substrate, the heat-conductive insulating layer is arranged between the heating electrode and the detecting electrode, and the metallic oxide film is covered on the detecting electrode; the integrated gas sensor is characterized in that noble metal particles are deposited on the metallic oxide film, and the noble metal particles are monatomically covered on the metallic oxide film, the coverage degree of the noble metal particles is 0.05-10% of the surface area of the metallic oxide film and the particle size is 0.2-0.4nm. The integrated gas sensor can effectively improve the gas sensitivity and the gas stability of the metallic oxide film; the metallic oxide film doped with noble metal particles can achieve the sensitivity improved to 9.46 of the noble metal and metallic oxide film from 1.51 of the pure metallic oxide film when used for testing 200ppm ethyl alcohol gas; furthermorethe gas sensitivity reaction temperature of the metallic oxide film is only 150 DEG C.
Description
Technical field
The invention belongs to gas detection sensor field, be specifically related to a specific admixture noble metal and mix integrated gas sensors of particle and metal-oxide film and preparation method thereof.
Background technology
Along with development and the raising of national economy, in commercial production and daily life, a large amount of toxic and harmfuls has been discharged in the mankind's activity, and environment is gone from bad to worse, and has had a strong impact on the mankind's health.Meanwhile, the mankind also more and more come into one's own to the prevention awareness of toxic and harmful in environment.For example, the content of formaldehyde in domestic environment can cause chronic respiratory disease; The leakage of inflammable gas may cause blast and fire; The discharge of vehicle exhaust and organic burning cause serious haze, and the industry particularly toxic gas of chemical engineering industry discharge has all formed serious threat to the mankind's living environment.Because the gaseous species of various living environment and industrial environment discharge is also different, to gas (CO in these environment, H2, H2S, NOx, formaldehyde, ethanol, methane etc.) accurate detection is particularly important, so preparation has the key that the gas sensor of high sensitivity and fine selectivity is gas sensor design application.Meanwhile, in view of need to arrange that a large amount of gas sensors forms network various gas is measured in environment measuring and monitoring simultaneously, this requires gas sensor be able to work long hours, microminiaturized like this, low-power consumption, the development of array thin film gas sensor has become the developing direction of gas sensor product.
According to the difference of the gas sensitive of gas sensor and gas-sensitive property, can be divided into resistance-type metal oxide semiconductor films, non-resistance-type metal oxide semiconductor films, catalytic combustion type gas sensor, optical type gas sensor, quartz resonance gas sensor, electric chemical formula.Non-resistance-type metal oxide semiconductor films gas sensor mainly comprises metal-oxide-semiconductor field effect transistor type gas sensor and diode-type gas sensor etc., the principle of work of transistor-type gas sensor is that the gas being adsorbed between metal and interface changes the work function of semiconductor energy gap or metal, by the variation of semiconductor rectifier characteristic, judge the size of gas concentration, mainly for detection of reducibility gas, as hydrogen, methane etc.But due to its poor stability, for being used widely; Catalytic combustion type gas sensor is that the relation of the heat that produces in the chemical reaction that utilizes gas concentration and detected gas to carry out detects, owing to being combustion-type, this sensor is only responsive to inflammable gas, and low to the inflammable gas sensitivity of low concentration, catalyzer is comparatively serious to the intoxicating phenomenon of gas sensor; Optical type gas sensor mainly be take spectral absorption type as main, according to the molecular structure of different gaseous matters is different, concentration is different and the difference of energy distribution produces different absorption spectrums, according to the difference of spectrum, differentiate kind and the content of gas, mainly for detection of CO, CO
2, sulfur-containing oxide and oxides of nitrogen.Although this sensor is highly sensitive, because manufacturing cost is high, be not suitable for widespread use; The gas sensor of quartz resonance gas sensor is mainly comprised of quartz substrate, gold electrode and support three parts.On its electrode, scribble one deck gas sensitization film, when tested gas molecule is adsorbed on gas sensitization film, the mass penalty of sensitive membrane, thereby the resonance frequency of quartz vibrator is reduced, according to the concentration relationship of the variable quantity of resonance frequency and tested gas, gas concentration size can be judged, NH3, SO2, HCi, H2S, acetic acid steam etc. can be detected.But such sensor poor selectivity, industrialization also takes day; Galvanochemistry type gas sensor is the gas sensor that utilizes electrochemical properties, its principle is to make the interface of electrode and electrolyte solution keep constant potential electrolysis, by change, set current potential, selectively make gas generation redox reaction, thus can be quantitatively and the various gas of qualitative detection.Electrochemical sensor is mainly for detection of inflammable gas and toxic and harmful, as H
2s, CO, SO
2, Cl
2deng.But there are 2 limitations in electrochemical sensor, the one, the existence of interference gas also can produce and disturb the signal of electrolytic solution, causes to a certain extent the deviation of detection; The 2nd, the life-span of electrochemical gas sensor is shorter, because the life-span of its sensor probe generally only had about 2 years.
From the thirties in 20th century, metal-oxide film gas sensitive material obtains people's broad research.According to the difference of electronic structure, metal oxide gas sensitive is divided into transition metal oxide and non-transition metal oxide.Transition metal oxide mainly contains: Cr
2o
3, γ-Fe
2o
3, WO
3, TiO
2, NiO, MgO; Non-transition metal oxides mainly contains: 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
2.For metal oxide semiconductor material, from initial monobasic oxide (SnO2, ZnO), as gas sensitive, start, novel metal Composite Oxide Gassensing Materials is as CeO by now
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
2deng.These single oxides or multivariant oxide chemical composition, finishing, material lattice size and particle size and the structure and morphology etc. of material affect air-sensitive performance aspect obtained many new developments.When metal-oxide film is exposed in air, oxygen molecule is adsorbed on film surface, by catching the electronics of zinc oxide material inside, forms O
2 ?, O
2 2-, O
2ion, and form charge depletion layer (energy gap) at material surface, thus cause the resistance of material to increase.When reducibility gas is adsorbed on material surface, with ADSORPTION STATE oxonium ion generation series of chemical, finally transfer an electron to metal oxide materials inside, reduce the resistance value of body material, thereby obtained corresponding sensitivity.Yet the composition of metal and oxygen like this, for obtaining high gas sensitization degree, must be controlled metal oxide composition in technology of preparing in the inherent vice dependence metal oxide of metal oxide.
Also there is defect aspect long-time stability, selectivity, detected temperatures, humidity effect and sensitivity etc. in intrinsic metal oxide materials, for improving susceptibility and the selectivity of the gas of metal oxide materials, conventionally by surface doping noble metal, as Au, Ag, Pt, Pd, Rh, Ru, Os, Ir etc. optimize its air-sensitive performance, be the main method that improves gas sensor performance.When noble metal is evenly distributed on behind metal oxide materials surface, for reacting gas provides activated centre, reduce reaction activity.Noble metal promotes to decompose to the oxyhydrogen energy of absorption, make the electronics discharging in course of reaction constantly shift to metal oxide, metal oxide crystal boundary potential barrier is reduced, electricity is led increase, improve the sensitivity of material, reduced the temperature of reaction of material and gas simultaneously.Noble metal, at structure, crystalline form, surface coverage and the particle size of the very large dependence noble metal of the priming reaction of metal oxide surface, needs the new model preparation method that can regulate and control structure, crystalline form, surface coverage and particle size like this in precious metal material preparation.
As semiconductor material, the technology of preparing of its film has had a variety of so far, mainly comprises the preparation method of Physical, chemical method and crossing domain.In scientific research now, mainly contain chemical spray pyrolysis method, chemical vapour deposition technique, magnetron sputtering method, sol-gal process and pulsed laser deposition.First chemical spray pyrolysis method packs precursor solution in reaction chamber into, logical pressurized air, under certain pressure, adopt ultrasonic atomization method to make solution atomization, the solution of last atomization arrives reaction chamber and high temperature substrate contact, on its surface of substrate, there is cracking reaction and generate sull, because atomized drop process of thermal decomposition in reacting furnace is subject to the combined action of a lot of parameters, very complicated, the growth pattern of its film is difficult for accurately being controlled, thereby has affected the quality of film; Chemical vapour deposition technique is by oxide precursor high-temperature evaporation, then by carrier gas, is delivered in the substrate of reaction chamber, finally by physisorption and chemical reaction, forms sull in substrate.Although chemical vapor deposition oxide is easily prepared, mode of deposition is also easy to control, and the metallorganics in course of reaction can become small solid particle, and these solid microparticles enter the quality that has affected film in sull; Magnetron sputtering method refers in high vacuum, fills with inert gas (conventional Ar gas), under the effect of direct current or high-frequency and high-voltage electric field, makes Ar atomic ionization produce glow discharge, forms high-octane Ar
+bombardment of ion beam oxide target material surface, does not have chemical change directly to obtain sull.Although magnetron sputtering method can obtain fine and close sull, target utilization is not high, generally lower than 40%, and plasma unstable; Sol-gel process is that to take metal organic or inorganic compound solution be raw material, the submicron order ultra micron colloidal sol that shows dispersion flows in the solution generating through hydrolysis, condensation reaction, again it is combined with ultra micron, forms extexine curing gel, then make the method for oxidation through bakingout process.Although sol-gel process is applicable to industrialization large area, produce, have following shortcoming: (1) raw materials used great majority are organic compounds, and cost is higher, and the time of processing procedure is longer, often reach 1-2 month; (2) goods easily ftracture, and this is because amount of liquid in gel is large, produce to shrink to cause when dry; (3) if burn till perfect not, can residual pore in goods and OH root or C, the latter makes goods band black.
The preparation of nano noble metal particles is at present divided into chemical method and Physical.Chemical method has oxidation-reduction method, electrochemical process, sol-gel method etc.The I of noble metal prepared by chemical method reaches several nanometers, simple to operate, easy to control.But the noble metal obtaining be difficult for to shift and assembling, and easily comprise impurity, assemble.Physical mainly contains laser ablation, vacuum evaporation etc., and its nano particle purity of preparing is higher.The special noble metal of preparing for laser deposition, its sharp light intensity can be controlled particle size, concentration and the distribution of noble metal neatly.Laser deposition is easy to preparation table surface-active agent and the faint nano particle being connected of precious metal surface, makes the particle being fixed can not change significantly its how much and electronics proterties.
Pulsed laser deposition (Pulsed Laser Deposition PLD) is called again laser ablation (Pulsed Laser Ablation PLA), is a kind of physical vacuum deposition technique.The physical principle of PLD is LASER HEATING evaporation target phenomenon.First the high-energy photon pulse that laser instrument produces by focus lamp after bombardment be placed in the target in vacuum chamber, several evaporation and sputters that produce surfacings to tens nanometer layer under instantaneous heating target material surface.The surfacing of eruption forms has the plasma (the target molecule of electronics, ion, little quality) compared with kinetic energy.In plasma diffusion, to the process of substrate, the target molecule of the follow-up medium and small quality of the broken plasma of laser irradiation forms the plasma only consisting of electronics, ion uniformly.These plasma diffusion are to high temperature substrate, thus formation metal-oxide film.
The advantage of pulsed laser deposition is to realize the synchronous transfer of target composition on substrate, like this by realizing the accurate control of metal oxide gas sense film composition to the control of metal oxide target.For the deposition of noble metal, for noble metal structure, crystalline form, surface coverage and particle size, can control by controlling energy, frequency and the monopulse number of times of laser pulse accurately.For the deposition of noble metal, the concentration that accurate noble metal structures, crystalline form, surface coverage and particle size can be controlled noble metal by frequency and the number of times of gating pulse, noble metal-metal oxide sensor structure is as Fig. 3.
Summary of the invention
The present invention is in order to improve the performance of metal-oxide film sensor, improve the sensitivity of metal-oxide film sensor, provide a specific admixture noble metal to mix the integrated gas sensors of particle and metal-oxide film, application semiconductor technology is prepared miniature interdigital electrode and heating electrode, adopt pulsed laser deposition at metal oxide surface doped precious metal particle, by gating pulse frequency and the accurate concentration of controlling noble metal of time, changing mode of deposition avoids noble metal to enter the inner impurity that forms of metal oxide, prevent that noble metal is oxidized to metal oxide containing precious metals simultaneously.
The technical solution used in the present invention is:
Mix noble metal and mix the integrated gas sensors of particle and metal-oxide film, comprise substrate, heating electrode, heat conductive insulating layer, detecting electrode, metal-oxide film, heating electrode preparation is on substrate, heat conductive insulating layer is between heating electrode and detecting electrode, metal-oxide film covers on detecting electrode, on metal-oxide film, deposit noble metal, noble metal is monatomic covering on sull, coverage (noble metal covers the number percent that area on metal-oxide film accounts for metal-oxide film surface area) is 0.05%-10%, particle size is 0.2nm-0.4nm, evenly distributed at random.
Described noble metal is one or more in Au, Ag, Pt, Pd, Rh, Ru, Os, Ir.
Metal-oxide film thickness is 20-2000nm, has the growth of high c-axle orientation.
Described noble metal coverage is preferably 0.5% of metal-oxide film surface area, and particle size is preferably 0.27nm
Describedly mix the preparation method that noble metal is mixed the integrated gas sensors of particle and metal-oxide film, comprise the steps:
1) cleaning of substrate;
2) photoetching heating electrode pattern;
3) physical deposition plating heating electrode, adopts magnetron sputtering plated electrode or electron beam deposition electrode;
4) physical deposition heat conductive insulating layer, adopts magnetron sputtering deposition or electron beam deposition on heating electrode, to prepare heat conductive insulating layer; 5) secondary photoetching and etching;
6) photoetching detecting electrode pattern, adopts photoetching technique to prepare detecting electrode pattern;
7) physical deposition detecting electrode, adopts magnetron sputtering deposition or electron beam deposition on insulation course, to prepare detecting electrode;
8) pulsed laser deposition is prepared metal oxide nano film, and depositing temperature is 200 ~ 600 ℃, and it is 0 ~ 50Pa that oxygen is pressed, and pulse energy is 100 ~ 700mJ, and pulsed frequency is 1 ~ 100Hz, and sedimentation time is 1 ~ 180min.
9) pulsed laser deposition noble metal modifying metallic oxide film, depositing temperature is 25 ~ 600 ℃, and it is 0 ~ 10Pa that oxygen is pressed, and pulse energy is 200 ~ 500mJ, and pulsed frequency is 1 ~ 10Hz, sedimentation time is 1 ~ 60s.
In the present invention, heating electrode can be: (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: 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 process of electrode is: the cleaning of (1) 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, by photoetching technique at SiO
2on-Si substrate, can obtain needed heating electrode pattern; (3) physical deposition plating heating electrode, adopts magnetron sputtering plated electrode or electron beam deposition electrode; (4) physical deposition heat conductive insulating layer, adopts magnetron sputtering deposition or electron beam deposition on heating electrode, to prepare heat conductive insulating layer; (5) 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; (6) photoetching detecting electrode pattern, adopts photoetching technique to prepare detecting electrode pattern; (7) physical deposition detecting electrode, adopts magnetron sputtering deposition or electron beam deposition on insulation course, to prepare detecting electrode.Electrode production process is as Fig. 1.
Pulsed laser deposition is prepared metal oxide nano film
Utilize PLD method depositing metal oxide film on electrode.Optimizing on the basis of deposition parameter, obtain the adjustable metal-oxide film for high sensitivity gas sensor of high-quality and composition.As shown in Figure 3.
Pulsed laser deposition noble metal modifying metallic oxide film surface
When noble metal is evenly distributed on behind metal oxide materials surface, for reacting gas provides activated centre, not only reduce reaction activity, can concentration be increased adsorbed gas simultaneously, take zinc paste metal-oxide film as example, noble metal provides abundant activated centre at zinc oxide surface, and absorption hydrogen-oxygen also promotes to decompose:
2 noble metals+H2 → 2 noble metal-H (1)
2 noble metals+O2 → 2 noble metal-O (2)
Hydrogen after decomposition and oxygen move on to zinc oxide surface following reaction occur:
Oad+e-→O-ad?（3）
2Had+Oad→H2O+e-?（4）
Along with the carrying out of reaction, electronics is constantly shifted to zinc paste, and metal oxide crystal boundary potential barrier is reduced, and electricity is led increase, has improved the sensitivity of material, has reduced the temperature of reaction of material and gas simultaneously.
Utilize pulsed laser deposition (PLD) noble metal at metal oxide surface, improve the air-sensitive performance of oxide.Optimizing on the basis of deposition parameter, obtaining high-quality, good uniformity, concentration is adjustable for optimizing the noble metal of metal-oxide film air-sensitive performance.As shown in Figure 4.
beneficial effect
The present invention has obvious originality at precious metal doping metal-oxide film gas sensitive aspect preparing.Aspect prepared by material, pulsed laser deposition metal-oxide film can accurately be controlled film thickness and improve film quality; The pulsed laser deposition of noble metal can accurately be controlled noble metal concentration makes it reach film sensitivity peak, simultaneously in high vacuum, under cryogenic conditions, noble metal is not easy oxidized and has guaranteed that noble metal only modifies at metal oxide surface, the surface catalysis effect of at utmost bringing into play noble metal, prevents causing of other defect.The present invention can effectively improve metal-oxide film gas sensitivity and stability, by doped precious metal particle, and test 200ppm alcohol gas, sensitivity (S=Ra/Rg) is brought up to 9.46 of noble metal-metal oxide by 1.51 of pure metal oxides; Meanwhile, the gas-sensitive reaction temperature of metal-oxide film only needs 150 ℃, has greatly reduced power consumption.By pulsed laser deposition, prepare the invention of noble metal-metal-oxide film, the sensor of acquisition has ethanol highly sensitive, and low-power consumption advantage makes pulsed laser deposition become one of excellent process of preparing air-sensitive film.
The noble metal that mixes of described PLD deposition is mixed the advantage of the integrated gas sensors of particle and metal-oxide film and is: (1) PLD prepares metal-oxide film and can accurately control metal-oxide film thickness and improve the oxygen defect in metal-oxide film, the metal oxide gas sensitive good stability of preparation.(2) by after PLD depositing noble metal particle is on metal-oxide film, due to the catalytic action of noble metal, this sensor has high sensitivity and low-power consumption feature.
The noble metal of doping low concentration of our research can reduce below temperature of reaction to 100 ℃, and ethanol is had to high sensitivity and selectivity.
Accompanying drawing explanation
Fig. 1: heating electrode and detecting electrode preparation flow figure;
Fig. 2: vacuum deposition methods noble metal structural drawing;
Fig. 3: sull gas sensor configuration figure;
Fig. 4: noble metal-metal-oxide film gas sensor configuration figure;
Fig. 5: different precious metal concentration doping sensitivity experiment results;
1-substrate; 2-heating electrode, 3-heat conductive insulating layer, 4-detecting electrode, 5-sull, 6-noble metal, 7-laser beam, 8-noble metal target material, 9-plasma.
Embodiment
It is example that following examples be take the integrated gas sensors that mixes Pd particle and ZnO film, illustrate its preparation method, other noble metals Au, Ag, Pt, Rh, Ru, Os, Ir and Pd graininess matter are similar, be applicable to same preparation method, the gas sensor character obtaining is similar, below does not elaborate.
Embodiment 1: preparation Pd-ZnO film gas sensor
the first step, the preparation of detecting electrode-heating electrode substrate
(1) substrate cleans: to SiO
2the Si substrate that material covers 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.
second step ZnO Prepared by Pulsed Laser Deposition
(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.The 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 pressing as 10Pa according to research oxygen before, ZnO film crystalline quality is best.
(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 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.
the 3rd pace pulse 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.
The 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, the noble metal loading time is set as 0S, 2S, 5S, 10S, 15S, 20S(and distinguishes pulse 0 time, 2 times, 5 times, 10 times, 15 times, 20 times), the different number of times of pulse has determined the concentration of Pd particle, finds out the highest Pd particle doping content of sensitivity; Respectively different precious metal concentration doping are tested, 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 200ppm, and sensor heating-up temperature is 100 ℃.Result shows intrinsic ZnO, 2s-Pd-ZnO, 5s-Pd-ZnO, 10s-Pd-ZnO, 15s-Pd-ZnO and 20s-Pd-ZnO to detect 200ppm ethanol and 200ppm H
2, to ethanol, sensitivity is respectively 1.51,5.80,6.53,7.15,6.86,5.23; To H
2sensitivity is respectively 1.35,3.05,3.61,3.83,2.99,2.85.Experimental result is shown in Fig. 5, as can be seen from the figure: when doping is 10s-Pd-ZnO, the highest to the sensitivity of ethanol and hydrogen, be respectively 7.15 and 3.83, and higher to the selectivity of ethanol.
Parameter arranges (laser energy: 400mJ; Frequency 1Hz; Depositing temperature: 30 ℃; Sedimentation time: 10S), operation laser (RUN+EXE), then open baffle plate metal-oxide film is carried out to noble metal deposition, obtain mixing the integrated gas sensors of Pd particle and ZnO film, Pd particle is monatomic covering on ZnO film, coverage is 0.05% of membrane surface area, and particle size is 0.27nm, evenly distributed at random.Test 200ppm alcohol gas, sensitivity (S=Ra/Rg) is brought up to 9.46 of noble metal-metal oxide by 1.51 of pure metal oxides; The gas-sensitive reaction temperature of metal-oxide film only needs 150 ℃, has greatly reduced power consumption.
Claims (6)
1. a specific admixture noble metal is mixed the integrated gas sensors of particle and metal-oxide film, comprise substrate, heating electrode, heat conductive insulating layer, detecting electrode and metal-oxide film, heating electrode preparation on substrate, heat conductive insulating layer is between heating electrode and detecting electrode, metal-oxide film covers on detecting electrode, it is characterized in that: on metal-oxide film, deposit noble metal, noble metal is monatomic covering on sull, coverage is 0.05%-10%, and particle size is 0.2nm-0.4nm.
2. described in claim 1, mix the integrated gas sensors that noble metal is mixed particle and metal-oxide film, it is characterized in that: described noble metal is one or more in Au, Ag, Pt, Pd, Rh, Ru, Os, Ir.
3. described in claim 1, mix the integrated gas sensors that noble metal is mixed particle and metal-oxide film, it is characterized in that: metal-oxide film thickness is 20-2000nm.
4. described in claim 1, mix the integrated gas sensors that noble metal is mixed particle and metal-oxide film, it is characterized in that: described noble metal coverage is 0.5%.
5. described in claim 1, mix the integrated gas sensors that noble metal is mixed particle and metal-oxide film, it is characterized in that: the particle size of described noble metal is 0.27nm.
6. in claim 1 ~ 5, described in any one, mix the preparation method that noble metal is mixed the integrated gas sensors of particle and metal-oxide film, it is characterized in that comprising the steps:
1) cleaning of substrate;
2) photoetching heating electrode pattern;
3) physical deposition plating heating electrode, adopts magnetron sputtering plated electrode or electron beam deposition electrode;
4) physical deposition heat conductive insulating layer, adopts magnetron sputtering deposition or electron beam deposition on heating electrode, to prepare heat conductive insulating layer; 5) secondary photoetching and etching;
6) photoetching detecting electrode pattern, adopts photoetching technique to prepare detecting electrode pattern;
7) physical deposition detecting electrode, adopts magnetron sputtering deposition or electron beam deposition on insulation course, to prepare detecting electrode;
8) pulsed laser deposition is prepared metal oxide nano film, and depositing temperature is 200 ~ 600 ℃, and it is 0 ~ 50Pa that oxygen is pressed, and pulse energy is 100 ~ 700mJ, and pulsed frequency is 1 ~ 100Hz, and sedimentation time is 1 ~ 180min;
9) pulsed laser deposition noble metal modifying metallic oxide film, depositing temperature is 25 ~ 600 ℃, and it is 0 ~ 10Pa that oxygen is pressed, and pulse energy is 200 ~ 500mJ, and pulsed frequency is 1 ~ 10Hz, sedimentation time is 1 ~ 60s.
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Application publication date: 20140910 |