CN111024775B - Gas-sensitive sensing device for ozone gas sensor and preparation method - Google Patents
Gas-sensitive sensing device for ozone gas sensor and preparation method Download PDFInfo
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Abstract
The invention provides a gas-sensitive sensing device for an ozone gas sensor, which comprises an oxide semiconductor film and nanoparticles dispersed on the surface of the oxide semiconductor film, wherein the nanoparticles have the capability of responding to ozone gas and the conductivity of the nanoparticles is higher than that of the oxide semiconductor film. The present invention also provides a method of preparing a gas sensor device for an ozone gas sensor, the method comprising the steps of: 1) preparing an oxide semiconductor film; 2) and growing dispersed nano-particles on the surface of the oxide semiconductor film under room temperature conditions. The ozone gas sensor provided by the invention improves various response performances of the ozone concentration sensor by regulating and controlling the size, density and distribution of the nano particles, is simple to operate and is easy to realize industrialization.
Description
Technical Field
The invention belongs to the field of semiconductor sensors, and particularly relates to a gas-sensitive sensing device for an ozone gas sensor, and a preparation method and application thereof.
Background
Ozone (Ozone) is a gas that is stably present in the natural world and has a very important influence on the life of people. Because of the strong oxidizing property of ozone and the non-toxicity of decomposition products, ozone is often used as a disinfectant and a purifying agent for sewage discharged by people in daily production and life; in addition to water purification and disinfection, ozone gas is widely used in food and pharmaceutical industries. However, excessive amounts of ozone can have many adverse effects on human health, agricultural production, and the ecosystem. Therefore, monitoring of ozone content is important in the production and living fields. Through decades of development, the current commercial ozone detection methods mainly include an ultraviolet light absorption method, a chemiluminescence method, an iodine element method and the like. These measurement methods are mainly carried out by large-scale equipment, and ozone gas sensors are often used for outdoor real-time surveys due to difficulty in movement.
Currently, Ozone gas sensors (Ozone sensors) are mainly classified into resistive type and non-resistive type, wherein tin oxide, indium oxide, zinc oxide, iron oxide, and the like are used as materials. Resistance type ozone gas sensors, such as tin oxide high temperature sintered ceramic type ozone gas sensors, are simple in structure, convenient to manufacture and use, but low in sensitivity; while a non-resistance type ozone gas sensor, such as a copper oxide-barium titanate capacitance type ozone gas sensor, has high sensitivity, but the manufacturing process is relatively complex and has poor stability (sensor principle and application, royal cinnamon, chinese electric power publishing, 2010). In addition, the existing ozone gas sensor has a series of problems that the working temperature window is narrow, the price is expensive, the service life is relatively short, and the existing ozone gas sensor cannot be integrated with flexible wearable equipment to realize portable integrated application.
The oxide semiconductor film has high sensitivity to gas containing oxygen, and is expected to replace the traditional material and become a sensing layer material of a new generation of ozone gas sensor because of the characteristics of wide growth temperature control window, rich material sources, low price, easy preparation, stable chemical properties, capability of manufacturing flexible transparent devices and the like. It is known that increasing the specific surface area of the sensing layer material, decreasing the initial resistance of the sensing layer material is an effective method to improve the performance of ozone gas sensors. The existing growth method of the sensing layer material mainly comprises a hydrothermal method, a molecular beam epitaxy growth method, a chemical vapor deposition growth method and the like, but the sensing layer material prepared by the method has the defects of high price, long preparation period, difficulty in large-scale production and the like; most importantly, they still do not depart from the high temperature preparation process and the high temperature working conditions, and the responsivity and response speed at low temperature including room temperature still hardly reach the practical level, thereby greatly limiting the further research and development of such devices. In contrast, the oxide semiconductor thin film sensing layer manufactured by the magnetron sputtering method and the like can well solve the problems; however, they also have problems of small specific surface area, high initial resistance, and the like, and have a large distance from practical use.
Based on this, it is a problem to be urgently needed to solve at present to develop an ozone gas sensor which is low in cost, simple in preparation process, capable of working at room temperature, high in sensitivity, good in stability, and convenient to carry and integrate.
Disclosure of Invention
Accordingly, it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and to provide a gas sensor device for an ozone gas sensor and a method of manufacturing the gas sensor device. The invention also provides an ozone gas sensor comprising the gas-sensitive sensing device. The ozone gas sensor provided by the invention has the advantages that various response performances are obviously improved, the operation is simple, and the industrialization is easy to realize.
In one aspect, the present invention provides a gas sensor device for an ozone gas sensor, the gas sensor device comprising an oxide semiconductor thin film and nanoparticles dispersed on a surface of the oxide semiconductor thin film, the nanoparticles having a capability of responding to ozone gas and having a higher electrical conductivity than the oxide semiconductor thin film.
The gas sensor according to the present invention, wherein the oxide semiconductor thin film is prepared on a substrate selected from Mica (Mica), polyethylene terephthalate, polyethylene naphthalate (PEN), Polyimide (PI), polyvinyl chloride (PVC), Polycarbonate (PC) or Polystyrene (PS), Polyethylene (PE), polypropylene (PP), sapphire (Al), and the like2O3) Silicon wafer (Si), silicon carbide (SiC), and quartz glass (SiO)2) Or gallium arsenide wafers (GaAs).
Preferably, the substrate is selected from Mica (Mica), polyethylene terephthalate, polyethylene naphthalate (PEN), Polyimide (PI), polyvinyl chloride (PVC), Polycarbonate (PC) or Polystyrene (PS), Polyethylene (PE) or polypropylene (PP).
The gas sensor according to the present invention, wherein the oxide semiconductor thin film is made of gallium oxide, indium gallium zinc oxide, indium oxide, tin oxide, zinc oxide, titanium oxide, cerium oxide, niobium oxide, tungsten oxide, cadmium oxide, iron oxide, zirconium oxide, or strontium titanium oxide.
The gas sensor according to the present invention, wherein the thickness of the oxide semiconductor thin film is 50nm to 1000nm, preferably 60 nm to 800nm, more preferably 100nm to 500nm, and still more preferably 150nm to 200 nm.
The gas-sensitive sensing device according to the present invention, wherein the nanoparticles are selected from Indium Gallium Zinc Oxide (IGZO) particles, indium oxide (In)2O3) Particles, tin oxide (SnO)2) Particles, zinc oxide (ZnO) particles, cadmium oxide (CdO) particles, nickel oxide (NiO)2) Granules, calcium oxide (CaO) granules, cobalt oxide (Co)3O4) Particles, molybdenum oxide (MoO)3) Particles, tungsten oxide (WO)3) Particles, nickel (Ni) particles, lead (Pb) particles, platinum (Pt) particles, palladium (Pd) particles, copper (Cu) particles, gold (Au) particles, silver (Ag) particles, iron (Fe) particles, or aluminum (Al) particles.
The diameter of the dispersible nanoparticles is 1nm to 100nm, preferably 5nm to 20nm, more preferably 6nm to 15nm, and still more preferably 8nm to 10 nm.
The gas-sensitive sensing device further comprises an electrode, wherein the electrode is made of Indium Tin Oxide (ITO), Aluminum Zinc Oxide (AZO), Gallium Zinc Oxide (GZO), chromium (Cr), copper (Cu), silver (Ag), gold (Au), titanium gold (Ti/Au), aluminum (Al) or platinum (Pt).
In another aspect, the present invention further provides a method for preparing a gas sensor device for an ozone gas sensor, the method comprising the steps of:
1) preparing an oxide semiconductor film;
2) and growing dispersed nano-particles on the surface of the oxide semiconductor film under room temperature conditions.
The production method according to the present invention, wherein, in the step 1), the oxide semiconductor thin film is produced using a method selected from the group consisting of: magnetron sputtering, pulsed laser deposition, atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition or metal organic chemical vapor deposition.
More preferably, in the step 1), the oxide semiconductor thin film is prepared using a magnetron sputtering method;
preferably, the sputtering power of the magnetron sputtering method is 50W-120W, and the sputtering time is 5-30 minutes;
the production method according to the present invention, wherein, in the step 2), the dispersed nanoparticles are grown on the surface of the oxide semiconductor thin film by a method selected from the group consisting of: magnetron sputtering, sol-gel method, hydrothermal method, vacuum evaporation coating method, chemical vapor deposition method;
more preferably, in the step 2), the sputtering power of the magnetron sputtering method is 50W-120W, and the sputtering time is 20-120 seconds;
further preferably, the method further comprises:
3) carrying out micro-nano processing on the film obtained in the step 2); to form a desired planar structure such as a metal-semiconductor-metal (MSM) structure or a vertical structure such as a P-type semiconductor-intrinsic semiconductor-N-type semiconductor (PIN) structure;
4) and preparing an electrode on the surface of the structure subjected to micro-nano processing at room temperature.
In yet another aspect, the present invention also provides an ozone gas sensor comprising the gas sensor device of the present invention or a gas sensor device prepared according to the method of the present invention.
According to the ozone gas sensor of the present invention, preferably, the ozone gas sensor is a metal-semiconductor-metal (MSM) structure ozone gas sensor, a schottky diode structure ozone gas sensor, or a field effect transistor structure ozone gas sensor.
The invention also provides the use of the gas sensor or the gas sensor prepared according to the method in the preparation of an ozone gas sensor for detecting ozone;
preferably, the ozone gas sensor is a metal-semiconductor-metal (MSM) structure ozone gas sensor, a schottky diode structure ozone gas sensor, or a field effect transistor structure ozone gas sensor.
It is known to those skilled in the art that oxide films prepared under low temperature conditions have many oxygen vacancy defects, and their concentration changes will have a significant effect on the resistance of the sample. The oxygen vacancy has very sensitive reaction on ozone gas, mainly embodied that when ozone is introduced, the ozone occupies the oxygen vacancy, takes electrons on the surface of a sample and becomes oxygen anions, so that the resistance of the sample is increased; when the ozone is turned off, the oxygen anions can reinject electrons into the sample, change the electrons back into ozone molecules and leave the surface of the sample, so that oxygen vacancy point defects are reserved on the surface of the sample, and the resistance of the sample is reduced. Due to some oxide films (e.g. amorphous Ga)2O3Thin films) have a large band gap and low conductivity, so that their resistance changes in an ozone environment are less pronounced, and the responsivity and recovery time are less than ideal. The inventor finds that growing a layer of nanoparticles with higher conductivity on the surface of the oxide film can effectively solve the problem. The inventors found that the oxide thin film produced by this method has the following characteristics:
1) after the nano particles with higher conductivity grow on the surface of the oxide semiconductor film, the initial resistance of a sample can be effectively reduced, so that the resistance of the sensing layer changes more obviously in an ozone environment;
2) because the oxide nano particles contain a plurality of oxygen vacancy defects, the oxide nano particles have certain response to ozone, and the overall responsiveness can be effectively improved after the oxide nano particles are combined with the oxide semiconductor film; in addition, the noble metal particles such as gold, silver, platinum and the like have a catalytic effect, so that active sites on the surface of the oxide film are increased, the separation and transfer of surface electrons are accelerated, and the effects of improving the responsiveness and the response speed can be achieved.
3) The nano particles can form a heterojunction structure with the oxide film, so that the barrier height is provided, the separation of electrons and holes is facilitated, and the responsivity and the response speed are improved;
4) the introduction of the nano-particles increases the specific surface area of the oxide film surface, and the specific surface area has a crucial influence on improving the sensitivity of gas detection.
In addition, compared with the prior art, the invention also has the following advantages:
the oxide film and the nano-particle material used in the sensing layer are both non-toxic materials with low cost, the selection range is wide, the preparation process is simple, the preparation temperature is low, the regulation window is large, and the flexibility can be realized.
The ozone gas sensor prepared by the oxide film with the nano-particle microstructure modification on the surface can reduce the cost to a great extent, is suitable for large-scale production, and can be compatible with other micro-nano process devices; can work normally under the condition of low temperature even room temperature, and is particularly suitable for preparing a flexible ozone gas sensor.
The invention improves each response performance of the ozone concentration sensor by regulating and controlling the size, density and distribution of the nano particles, has simple operation and is easy to realize industrialization.
Drawings
Embodiments of the invention are further described below with reference to the accompanying drawings, in which:
FIG. 1 is amorphous Ga of non-sputtered IGZO nanoparticles observed by atomic force microscope2O3A film surface topography map;
FIG. 2 shows amorphous Ga in example 1 according to the present invention2O3The surface topography of the nano particles grown on the surface of the film;
FIG. 3 shows amorphous Ga in example 2 according to the present invention2O3The surface topography of the nano particles grown on the surface of the film;
FIG. 4 shows amorphous Ga in example 3 according to the present invention2O3The surface topography of the nano particles grown on the surface of the film;
fig. 5 is a schematic structural cross-sectional view of an MSM-structured ozone gas sensor comprising an oxide thin film having a surface nanoparticle microstructure prepared according to examples 1-4 of the present invention;
FIG. 6 is a schematic top view of the structure of an MSM interdigitated structure ozone gas sensor containing an oxide thin film with surface nanoparticle microstructure prepared according to examples 5-8 of the present invention;
FIG. 7 is a schematic view showing that amorphous Ga prepared according to the present invention is not contained2O3Film and amorphous Ga with surface nanoparticle microstructure prepared according to example 3 of the present invention2O3And a current-time curve comparison graph of the performance test result of the thin-film MSM ozone gas sensor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail by embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Amorphous Ga with IGZO (indium gallium Zinc oxide) nanoparticle microstructure on surface2O3The thin film ozone concentration sensing device and the preparation method thereof comprise the following steps:
1) amorphous Ga is grown on a quartz substrate with the thickness of 200 mu m by utilizing a magnetron sputtering method at room temperature2O3Film, sputtering power is 60W, sputtering time is 30 minutes, amorphous Ga2O3The thickness of the film is about 200 nm;
2) amorphous Ga at 200nm by magnetron sputtering at room temperature2O3IGZO nano-particles grow on the film, the sputtering power is 70W, the sputtering time is 60 seconds, the size of the IGZO nano-particles is about 10nm, and uniform dispersion distribution is realized;
3) carrying out micro-nano processing on the sample obtained in the step 2), and obtaining an interdigital structure with a distance of 5 mu m by utilizing an ultraviolet lithography technology;
4) growing an ITO (indium tin oxide) film on the surface of the interdigital structure by utilizing a magnetron sputtering method at room temperature, wherein the sputtering power is 50W, the sputtering time is 8 minutes, and the thickness of the ITO film is about 80 nm;
5) and D, carrying out elution treatment on the sample obtained in the step four to obtain the sensing device.
Example 2
A sensor device was prepared in the same manner as in the method step of example 1, except that the sputtering time in step 2) was 90 seconds.
Example 3
A sensor device was prepared in the same manner as in example 1, except that the sputtering time in step 2) was 120 seconds.
Comparison of results of examples 1 to 3
The diameters, densities and distributions of the IGZO nanoparticles produced in examples 1 to 3 were different depending on the sputtering time.
In example 1, the magnetron sputtering time was 60 seconds, the IGZO particle diameter was about 10nm, and a uniform dispersion distribution was exhibited. In example 2, the magnetron sputtering time was 90 seconds, the IGZO particle diameter was about 10nm, and a uniform dispersion distribution was exhibited, but the particle density was significantly higher than that of the sample of example 1 having 60 seconds. In example 3, the magnetron sputtering time was 120 seconds, the IGZO particles had already started to form a film, and a part of the area began to appear as macromolecular clusters and no longer in the nanoparticle structure.
Referring to FIGS. 1 to 4, FIG. 1 is amorphous Ga of non-sputtered IGZO nanoparticles observed by atomic force microscope2O3Surface topography of the film, FIGS. 2-4 are graphs of amorphous Ga in examples 1-3, respectively2O3And the surface topography of the film after sputtering the IGZO nano-particles.
It can be seen that amorphous Ga of IGZO nanoparticles is not sputtered2O3The surface of the film is flat and uniform, after the IGZO is sputtered, the surface of the sample has uniformly distributed nano-particles, and the diameters of the IGZO nano-particles are equal to each other with the continuous increase of the sputtering timeThe density is increased; in addition, the inventors found through experiments that after the sputtering time reached 120 seconds, the IGZO was continuously sputtered to form amorphous Ga2O3The IGZO nano particles on the surface of the film begin to generate regional macromolecular clusters, and the phenomenon of uniform dispersion is not generated.
The amorphous Ga prepared in examples 1 to 3 and having the IGZO nanoparticle microstructure on the surface2O3The film ozone gas sensing device is used for carrying out related performance tests and is not in contact with amorphous Ga with an IGZO nano-particle microstructure on the surface2O3The performances of the thin-film ozone gas sensor are compared, and the surface microstructure is verified to effectively improve the responsivity and the responsivity speed of the sensor to ozone gas.
Referring to FIG. 5, FIG. 5 shows an amorphous Ga alloy having surface IGZO nanoparticle microstructure prepared in examples 1 to 32O3The sectional view of the thin-film metal-semiconductor-metal (MSM) ozone gas sensor comprises an ITO electrode 0501 and a sensing layer (i.e. amorphous Ga with an IGZO nanoparticle microstructure on the surface) from top to bottom2O3Film) 0502, and a quartz substrate 0503.
The two-part ITO electrode is connected to a Keithley 6487 source meter through a conducting wire by conductive silver adhesive, and the change of current under the condition of introducing and closing ozone gas is tested under the assistance of ultraviolet illumination, so that the change of the resistance (namely the responsivity) of the sensor sensing layer caused by the introduction of the ozone gas is reflected.
Referring to FIG. 7, FIG. 7 is a schematic view of a semiconductor device not containing amorphous Ga prepared according to the present invention2O3Thin film 0701 and amorphous Ga with nano-particle microstructure on surface prepared according to embodiment 3 of the invention2O3I-V curve comparison chart of MSM structure ozone gas sensor performance test result of film 0702. The responsivity of the ozone gas sensor comprising the amorphous oxide film 0702 with a nanoparticle microstructure shown in fig. 3 is increased by about 16 times and the response time (recovery time) is shortened by about 200% compared to the ozone gas sensor comprising the amorphous oxide film 0701 with a nanoparticle-free microstructure. And the surface shown in figure 2 and figure 4 is provided with nano-particlesThe responsivity of the ozone gas sensor of the amorphous oxide film with the microstructure is respectively increased by 9 times and 14 times, and the responsivity is respectively shortened by about 30 percent and 180 percent.
From this, it can be seen that the performance of the ozone sensor of example 2 in which the nanoparticles are grown by sputtering for 90 seconds is the best. The possible reasons are as follows: 1. in the initial stage of the magnetron sputtering growth of the nano particles, the number of the nano particles is small, the diameter of the nano particles is small and the influence on the surface of the amorphous oxide film is weak due to low nucleation density; with the continuous increase of the sputtering time, the diameter and the density of the nano particles are gradually increased to reach the optimal state of uniform distribution; 2. the density and the size of the nano particles are continuously increased by continuing the sputtering process, the situation that local macromolecules are connected into islands begins to appear, the islands do not appear in a uniform distribution state any more, the responsivity of the amorphous oxide thin film sensor layer can be enhanced, but the performance of the device tends to be unstable due to the weakening of the modification effect of the amorphous oxide thin film sensor layer, namely the responsivity of the device is reduced to a certain extent along with the increase of the test times, and the recovery speed is accelerated to a certain extent.
Therefore, the amorphous Ga prepared by the method and provided with the IGZO nano-particle microstructure on the surface2O3The film can greatly improve the detection performance of the ozone gas sensor and achieve the optimum when the size of the nano particles is between 8 and 10 nm.
Example 4
This example provides another amorphous Ga with Pt (platinum) nanoparticle microstructure on its surface2O3The steps of the thin film ozone gas sensing device and the preparation method thereof are the same as those of the embodiment 1, and the difference is the step 2):
2) at room temperature, amorphous Ga is formed by magnetron sputtering method2O3The Pt nano particles are sputtered on the surface of the film, the sputtering power is 50W, the sputtering time is 85 seconds, the size of the Pt nano particles is about 10nm, and the uniform dispersion distribution is realized.
The amorphous Ga prepared in the example and having Pt nano particle microstructure on the surface2O3Application of thin films to Metal-semiconductor-Metal (MS)M) interdigital structure ozone gas sensor, referring to FIG. 5, FIG. 5 shows an example of Pt nanoparticle enhanced amorphous Ga-containing material prepared by the method of the embodiment2O3The sectional view of the thin-film ozone gas sensor is that an ITO electrode 0501 and a sensing layer (namely amorphous Ga with a Pt nano-particle microstructure on the surface) are arranged from top to bottom in sequence2O3Film) 0502, and a quartz substrate 0503.
And connecting two parts of ITO electrodes to a Kethely 6487 source meter through conducting wires by using conductive silver adhesive, keeping the voltage constant under the assistance of ultraviolet illumination, and testing the change condition of current under the condition of introducing and closing ozone gas, wherein the change condition (namely the responsivity) of the resistance of a sensor sensing layer caused by the introduction of the ozone gas is reflected. And amorphous Ga containing microstructure without Pt nano particles on surface2O3Compared with the thin-film ozone gas sensor, the amorphous Ga prepared by the embodiment and having the Pt nano-particle microstructure on the surface2O3The responsivity of the thin-film ozone gas sensor is increased by about 8 times, and the response time (recovery time) is shortened by about 30%, which shows that the detection performance of the ozone gas sensor prepared by the embodiment is greatly improved.
Example 5
This example provides an amorphous Ga having a ZnO (zinc oxide) nanoparticle microstructure on its surface2O3The steps of the thin film ozone gas sensing device and the preparation method thereof are the same as the steps of the embodiment 1, except that:
step 2): at room temperature, amorphous Ga is prepared by magnetron sputtering method2O3Sputtering ZnO nanoparticles on the surface of the film. The sputtering power is 70W, the sputtering time is 100 seconds, the ZnO nano-particle size is about 8nm, and the uniform dispersion distribution is presented.
The amorphous Ga prepared in the example and having the ZnO nanoparticle microstructure on the surface2O3The thin film sensing layer is applied to a metal-semiconductor-metal (MSM) interdigital structure ozone gas sensor, referring to FIG. 6, FIG. 6 shows an amorphous Ga sensor with a surface ZnO nanoparticle microstructure prepared according to the embodiment2O3Thin film ozone gasThe structure of the sensor is a schematic plan view, which comprises an ITO electrode 0601 and a sensing layer (i.e. amorphous Ga with surface ZnO nanoparticle microstructure) from top to bottom2O3Thin film) 0602, and a quartz substrate 0603.
And connecting two parts of ITO electrodes to a Kethely 6487 source meter through conducting wires by using conductive silver adhesive, keeping the voltage constant under the assistance of ultraviolet illumination, and testing the change condition of current under the condition of introducing and closing ozone gas, wherein the change condition (namely the responsivity) of the resistance of a sensor sensing layer caused by the introduction of the ozone gas is reflected. And amorphous Ga containing microstructure without ZnO nano particles on surface2O3Compared with the ozone gas sensor of a thin film, the amorphous Ga with the ZnO nanoparticle microstructure on the surface prepared by the embodiment2O3The responsivity of the thin-film ozone gas sensor is increased by about 10 times, and the response time (recovery time) is shortened by about 20 percent, namely the detection performance of the ozone gas sensor is greatly improved.
Example 6
The embodiment provides a polycrystalline ZnO (zinc oxide) thin film ozone gas sensing device with a CaO (calcium oxide) nanoparticle microstructure on the surface and a preparation method thereof, wherein the steps are the same as those of embodiment 1, except that:
1) growing a polycrystalline ZnO film on a 150-micron-thick n-type Si substrate by using a chemical vapor deposition method at room temperature, putting high-purity Zn powder (99.999%) on a quartz boat in the center of a tube furnace, taking 60sccm oxygen as a raw material and 200sccm high-purity argon as a carrier gas, wherein the growth temperature is 70 ℃, the growth time is 20 minutes, and the thickness of the polycrystalline ZnO film is about 50 nm;
2) and sputtering CaO nano particles on the surface of the polycrystalline ZnO film by a magnetron sputtering method at room temperature. The sputtering power is 70W, the sputtering time is 90 seconds, the CaO nano-particle size is about 9nm, and uniform dispersion distribution is presented.
The polycrystalline ZnO thin film sensing layer having a CaO nanoparticle microstructure on the surface prepared in this example is applied to a metal-semiconductor-metal (MSM) interdigital structure ozone gas sensor, and referring to fig. 6, fig. 6 is a schematic top view of the structure of the polycrystalline ZnO thin film ozone gas sensor having a CaO nanoparticle microstructure on the surface prepared in this example, and an ITO electrode 0601, a sensing layer (i.e., a polycrystalline ZnO thin film having a CaO nanoparticle microstructure on the surface) 0602, and an n-type Si substrate 0603 are sequentially arranged from top to bottom.
And connecting two parts of ITO electrodes to a Kethely 6487 source meter through conducting wires by using conductive silver adhesive, keeping the voltage constant under the assistance of ultraviolet illumination, and testing the change condition of current under the condition of introducing and closing ozone gas, wherein the change condition (namely the responsivity) of the resistance of a sensor sensing layer caused by the introduction of the ozone gas is reflected. Compared with the ozone gas sensor comprising the polycrystalline ZnO film with the surface having no CaO nanoparticle microstructure, the polycrystalline ZnO film ozone gas sensor comprising the CaO nanoparticle microstructure prepared in the embodiment has the responsivity increased by about 7 times, and the response time (recovery time) shortened by about 110%, i.e., the detection performance of the ozone gas sensor is greatly improved.
Example 7
The present embodiment provides a polycrystalline ZnO (zinc oxide) thin film ozone gas sensor with an Al (aluminum) nanoparticle microstructure on the surface and a method for manufacturing the same, the steps of which are the same as those in embodiment 1, except that:
1) growing a polycrystalline ZnO film on a quartz substrate with the thickness of 200 mu m by utilizing a magnetron sputtering method at room temperature, wherein the sputtering power is 70W, the sputtering time is 20 minutes, and the thickness of the polycrystalline ZnO film is about 200 nm;
2) and evaporating Al nano particles on the surface of the polycrystalline ZnO film by using a thermal evaporation coating method at room temperature. The evaporation power is 20W, the evaporation time is 60 seconds, the size of Al nano particles is about 10nm, and the uniform dispersion distribution is presented.
The polycrystalline ZnO thin film sensing layer having an Al nanoparticle microstructure on the surface prepared in this example is applied to a metal-semiconductor-metal (MSM) interdigital structure ozone gas sensor, and referring to fig. 6, fig. 6 is a schematic top view of the structure of the polycrystalline ZnO thin film ozone gas sensor having an Al nanoparticle microstructure on the surface prepared in this example, and an ITO electrode 0601, a sensing layer (i.e., a polycrystalline ZnO thin film having an Al nanoparticle microstructure on the surface) 0602, and a quartz substrate are sequentially arranged from top to bottom.
And connecting two parts of ITO electrodes to a Kethely 6487 source meter through conducting wires by using conductive silver adhesive, keeping the voltage constant under the assistance of ultraviolet illumination, and testing the change condition of current under the condition of introducing and closing ozone gas, wherein the change condition (namely the responsivity) of the resistance of a sensor sensing layer caused by the introduction of the ozone gas is reflected. Compared with the ozone gas sensor comprising the polycrystalline ZnO film with the surface without the Al nanoparticle microstructure, the polycrystalline ZnO film with the surface having the Al nanoparticle microstructure prepared by the embodiment has the advantages that the responsivity is increased by about 12 times, and the response time (recovery time) is shortened by about 80%, namely the detection performance of the ozone gas sensor is greatly improved.
Example 8
This example provides a polycrystalline In with CdO (cadmium oxide) nanoparticle microstructure on the surface2O3The method for preparing the ozone gas sensor by using the (indium oxide) film is the same as the method in the embodiment 1 in the steps 3) to 5), except that:
1) polycrystalline In was grown on a 200 μm thick quartz substrate by magnetron sputtering at room temperature2O3Film, sputtering power is 70W, sputtering time is 22 minutes, polycrystal In2O3The thickness of the film is about 200 nm;
2) polycrystalline In by magnetron sputtering at room temperature2O3Sputtering CdO nano particles on the surface of the film. The sputtering power is 85W, the sputtering time is 80 seconds, the size of CdO nano particles is about 9nm, and uniform dispersion distribution is realized.
Polycrystalline In prepared according to this example and having CdO nanoparticle microstructure on the surface2O3The thin film sensing layer is applied to a metal-semiconductor-metal (MSM) interdigital structure ozone gas sensor, referring to FIG. 6, FIG. 6 is a polycrystalline In containing microstructure with CdO nano-particle on the surface prepared by the embodiment2O3The structure of the thin-film ozone gas sensor is schematically shown in a plan view, and comprises an ITO electrode 0601 and a sensing layer (namely a watch) in sequence from top to bottomPolycrystalline In faced with CdO nanoparticle microstructure2O3Thin film) 0602, and a quartz substrate 0603.
And connecting two parts of ITO electrodes to a Kethely 6487 source meter through conducting wires by using conductive silver adhesive, keeping the voltage constant under the assistance of ultraviolet illumination, and testing the change condition of current under the condition of introducing and closing ozone gas, wherein the change condition (namely the responsivity) of the resistance of a sensor sensing layer caused by the introduction of the ozone gas is reflected. And polycrystalline In comprising a surface CdO-free nanoparticle microstructure2O3Compared with the ozone gas sensor of a thin film, the polycrystalline In containing the CdO nanoparticle microstructure prepared In the embodiment2O3The responsivity of the thin-film ozone gas sensor is increased by about 7 times, and the response time (recovery time) is shortened by about 45 percent, namely the detection performance of the ozone gas sensor is greatly improved.
Although the present invention has been described by way of preferred embodiments, the present invention is not limited to the embodiments described herein, and various changes and modifications may be made without departing from the scope of the present invention.
Claims (14)
1. A gas-sensitive sensor device for an ozone gas sensor, characterized in that the gas-sensitive sensor device comprises an oxide semiconductor thin film and nanoparticles dispersed on the surface of the oxide semiconductor thin film, the nanoparticles having a response ability to ozone gas and having a higher electrical conductivity than the oxide semiconductor thin film, and the oxide semiconductor thin film has a thickness of 150nm to 200nm and the dispersed nanoparticles have a diameter of 8nm to 10 nm;
wherein the dispersible nanoparticles are selected from indium gallium zinc oxide particles, indium oxide particles, tin oxide particles, zinc oxide particles, cadmium oxide particles, nickel oxide particles, calcium oxide particles, cobalt oxide particles, molybdenum oxide particles, tungsten oxide particles, nickel particles, lead particles, platinum particles, palladium particles, copper particles, gold particles, silver particles, iron particles, or aluminum particles;
and, the method for preparing the gas sensor device of the ozone gas sensor comprises the following steps:
1) preparing an oxide semiconductor film;
2) growing dispersed nano particles on the surface of the oxide semiconductor film by a magnetron sputtering method at room temperature; the sputtering power of the magnetron sputtering method is 50W-120W, and the sputtering time is 20-120 seconds.
2. The gas sensor device according to claim 1, wherein the oxide semiconductor thin film is prepared on a substrate selected from mica, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyvinyl chloride, polycarbonate, polystyrene, polyethylene, polypropylene, sapphire, silicon wafer, silicon carbide, quartz glass, or gallium arsenide wafer.
3. The gas sensing device of claim 2, wherein the substrate is selected from mica, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyvinyl chloride, polycarbonate, polystyrene, polyethylene, or polypropylene.
4. The gas sensor of claim 1, wherein the oxide semiconductor thin film is composed of gallium oxide, indium gallium zinc oxide, indium oxide, tin oxide, zinc oxide, titanium oxide, cerium oxide, niobium oxide, tungsten oxide, cadmium oxide, iron oxide, zirconium oxide, or strontium titanium oxide.
5. A method of manufacturing the gas sensor device for an ozone gas sensor as claimed in any one of claims 1 to 4, the method comprising the steps of:
1) preparing an oxide semiconductor film;
2) growing dispersed nano particles on the surface of the oxide semiconductor film by a magnetron sputtering method at room temperature; the sputtering power of the magnetron sputtering method is 50W-120W, and the sputtering time is 20-120 seconds.
6. The method according to claim 5, wherein, in the step 1), the oxide semiconductor thin film is prepared using a method selected from the group consisting of: magnetron sputtering, pulsed laser deposition, atomic layer deposition, chemical vapor deposition, plasma enhanced chemical vapor deposition or metal organic chemical vapor deposition.
7. The method according to claim 6, wherein in the step 1), the oxide semiconductor thin film is prepared using a magnetron sputtering method.
8. The method of claim 7, wherein the magnetron sputtering method has a sputtering power of 50W to 120W and a sputtering time of 5 to 30 minutes.
9. The method of claim 5, wherein the method further comprises:
3) carrying out micro-nano processing on the film obtained in the step 2); to form a desired planar or vertical structure;
4) and preparing an electrode on the surface of the structure subjected to micro-nano processing at room temperature.
10. The method of claim 9, wherein the planar structure is a metal-semiconductor-metal structure; the vertical structure is a P-type semiconductor-intrinsic semiconductor-N-type semiconductor structure.
11. An ozone gas sensor comprising the gas sensing device of any one of claims 1-4 or the gas sensing device prepared according to the method of any one of claims 5-10.
12. The ozone gas sensor of claim 11, wherein the ozone gas sensor is a metal-semiconductor-metal structure ozone gas sensor, a schottky diode structure ozone gas sensor, or a field effect transistor structure ozone gas sensor.
13. Use of the gas sensing device of any one of claims 1-4 or prepared according to the method of any one of claims 5-10 in the preparation of an ozone gas sensor for detecting ozone.
14. The use according to claim 13, wherein the ozone gas sensor is a metal-semiconductor-metal structure ozone gas sensor, a schottky diode structure ozone gas sensor or a field effect transistor structure ozone gas sensor.
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