CN110907503A - Manufacturing method of hierarchical porous structure metal oxide and metal oxide semiconductor gas sensor - Google Patents
Manufacturing method of hierarchical porous structure metal oxide and metal oxide semiconductor gas sensor Download PDFInfo
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Abstract
A manufacturing method of a hierarchical porous structure metal oxide and a metal oxide semiconductor gas sensor are provided, wherein the method comprises the following steps: washing the obtained butterfly wing with deionized water; soaking the washed butterfly wing for the first time by using dilute hydrochloric acid, and then soaking for the second time by using a dilute sodium hydroxide solution; washing the soaked butterfly wing with deionized water again, and airing in the air to be half-dry; spreading the butterfly wings aired to be half-dry, immersing the butterfly wings into sol-gel containing metal ion complexes, carrying out third immersion, taking out the butterfly wings with the metal ions adsorbed on the surfaces, and drying to obtain the butterfly wings coated by the metal ions, namely the hierarchical porous metal oxide. The invention not only saves the tedious steps of artificially synthesizing the template, saves raw materials, saves the preparation period, and reduces the requirement and loss of experimental equipment; and the requirements of experimental equipment are reduced, materials are effectively saved, loss is reduced, and the manufacturing cost of devices is reduced.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a manufacturing method of a hierarchical porous structure metal oxide and a metal oxide semiconductor gas sensor.
Background
A gas sensor is a device or device that senses some or all of the gas and its content in the environment. The gas detector can convert the type and content information of gas into electric or optical signals for output, and can obtain the existence information of the gas to be detected in the environment according to the strength of the signals.
Gas sensors can be classified into semiconductor gas sensors, solid electrolyte gas sensors, contact combustion gas sensors, optical gas sensors, surface acoustic wave gas sensors, quartz resonator gas sensors, and the like, and metal oxide semiconductor gas sensors have been studied most widely in recent years. The semiconductor gas sensor mainly includes a metal oxide semiconductor sensor and an organic semiconductor gas sensor. The metal oxide semiconductor gas sensor has the characteristics of wide measurement range, high sensitivity, quick response, good thermal stability, long service life, low cost, simplicity in manufacture, mature process, convenience in use and maintenance, easiness in doping modification and batch production, convenience in online dynamic detection and the like, and becomes the most widely researched gas sensor with the most application prospect and research value at the present stage. The metal oxide gas sensor is a 'gas-electricity' converter, which mainly utilizes the change of the conductivity of the metal oxide material when the metal oxide material contacts with the gasThe principle design and manufacture. The contact gas may be an oxidizing gas such as NO2、Cl2Etc., or a reducing gas such as H2、CO、CH4And the like. The core component of the metal oxide gas sensor is a metal oxide-based gas-sensitive material which is very sensitive to a certain gas or a plurality of gases in the external environment and can detect, distinguish and judge the gases, and the working principle is that the metal oxide is made into a semiconductor in a mode of doping or changing non-stoichiometric ratio, so that the resistance value of the metal oxide is changed along with the change of the gases, and the purpose of selectively responding to the gas or the plurality of gases is realized. For a metal oxide gas sensor, the performance of the metal oxide gas sensor is mainly determined by the performance of a gas sensitive material, and because a gas sensitive reaction is generated on a gas-solid interface on the surface of a semiconductor, the component elements, the micro morphology and whether the gas sensitive material has the modification doping of a surface substance with catalytic activity are one of the key factors for determining the performance of the gas sensor.
The performance of the current metal oxide semiconductor gas sensor (higher sensitivity and lower detection limit) has been improved, and research and development of a high-performance gas sensor is one of the currently important research subjects. Summarizing recent research, we believe that improving the sensitivity of metal oxide semiconductor gas sensors starts from the aspects of the design and preparation of sensing materials. Mainly, work is carried out around improving the identification function, the conversion function and the utilization efficiency of the sensitive body of the metal oxide semiconductor. The low-dimensional, porous and hierarchical structure of the metal oxide semiconductor obviously improves the specific surface area, the active site density, the porosity and the permeability of the sensing material, and obviously improves three key factors determining the sensitivity of the metal oxide semiconductor sensor. Particularly, under the nanoscale, the composition and assembly of different metal oxide semiconductor sensing materials can realize the synergistic sensitization effect among different components, and the improvement of sensitivity is facilitated. In addition, aiming at the nano structure of the metal oxide semiconductor, the surface activity of the sensing material can be enhanced by doping the noble metal or the metal oxide in situ, the reaction of the gas on the surface is promoted, and the recognition function of the metal oxide semiconductor to the target gas is further improved. In a plurality of metal oxide semiconductor nano structures, the hierarchical structure has the advantage of designable preparation according to functional requirements, and the identification function, the conversion function and the utilization efficiency of the sensitive body can be simultaneously enhanced on the hierarchical structure by regulating and controlling the structural units and the assembly form, so that a new strategy is provided for designing a high-performance gas sensor.
The hierarchical structure refers to a high-dimensional (3-dimensional) nanostructure assembled by low-dimensional nanostructures (0/1/2 dimensions) such as nanoparticles, nanorods, nanowires, nanotubes, nanosheets, etc., and the microscopic morphology of the nanostructure shows the characteristics of a sleeve, a multilayer sheet, a porous structure, etc. Wherein the hierarchical porous structure has the comprehensive structural characteristics of nano materials and mesoporous/macroporous materials. In the field of gas-sensitive application, the hierarchical porous structure, particularly the open hierarchical porous structure, can inhibit the agglomeration and growth of nano particles, retain the high specific surface area of the nano material, and can also construct developed hierarchical pore channels (including mesopores and macropores) to enhance the transmission of gas in the material, so that the hierarchical porous structure is an ideal structure for constructing a gas-sensitive material with high sensitivity and quick response, and is widely concerned. However, the research on the graded porous gas-sensitive material at the present stage still has the following problems and challenges, in particular:
firstly, the synthesis means of the porous structure (artificial template method, hydrothermal method, solvothermal method, spray decomposition method, ostwald ripening method, Kirkendall effect method, liquid phase growth method, etc.) generally requires high cost, expensive equipment, complicated operation procedures, special reaction conditions, etc.;
and secondly, the artificially synthesized porous structure has single type and simple structure, and is difficult to realize the comprehensive control of a hierarchical structure with multiple layers, multiple structures and multiple pore diameters, thereby hindering the further development of the hierarchical porous structure, in particular the gas-sensitive material with the open hierarchical porous structure.
Therefore, how to prepare the metal oxide gas-sensitive material with multiple layers, multiple structures and multiple pore diameters by an experimental method with simple procedures and convenient operation is a key problem to be solved urgently at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a manufacturing method of a hierarchical porous structure metal oxide and a metal oxide semiconductor gas sensor.
In order to achieve the above object, the present invention provides a method for preparing a hierarchical porous metal oxide, comprising the steps of:
s1, washing the obtained butterfly wings with deionized water;
s2, soaking the washed butterfly wing for the first time through dilute hydrochloric acid, and then soaking for the second time through a dilute sodium hydroxide solution;
s3, washing the soaked butterfly wing with deionized water again, and airing in the air to be half-dry;
s4, spreading and immersing the butterfly wings aired to be half-dry into sol-gel containing metal ion complexes, carrying out third immersion, taking out the butterfly wings with the metal ions adsorbed on the surfaces, and drying to obtain the butterfly wings coated by the metal ions, namely the hierarchical porous metal oxide.
In a more preferred embodiment of the present invention, the butterfly wing is a wing of a green phoenix butterfly, or a wing of a green phoenix butterfly.
As a further preferable technical scheme of the invention, the washing times of deionized water are not less than three times.
As a further preferable technical scheme of the invention, the concentration of the dilute hydrochloric acid adopted for the first soaking is 10%, and the soaking time is 3 h; the concentration of the dilute sodium hydroxide adopted by the second soaking is 8%, and the soaking time is 4 h; the third soaking is soaking for 18 hours at room temperature; .
As a further preferable technical solution of the present invention, the drying process comprises: the butterfly wings are clamped by two quartz plates to keep flat, and the butterfly wings are dried for 30min at the temperature of 60 ℃.
In a further preferred embodiment of the present invention, the metal ion refers to a metal phase in a semiconductor metal oxide, and the metal ion includes Sn4+、Zn2+、Ti4+Or Cu2+。
According to another aspect of the present invention, the present invention further provides a metal oxide semiconductor gas sensor, which includes a substrate, a metal electrode, and a metal oxide prepared by the method for manufacturing a metal oxide having a hierarchical porous structure according to any one of the above aspects, wherein the metal electrode is disposed on the substrate, at least one piece of the metal oxide having a hierarchical porous structure is placed on the substrate after sintering and subsequent grinding, and is connected to the metal electrode through annealing.
As a further preferable technical solution of the present invention, a specific manufacturing method of the metal oxide semiconductor gas sensor is as follows:
evaporating an electrode mask plate on a substrate in a vacuum evaporation instrument to form a metal electrode;
clamping the hierarchical porous structure metal oxide by using a quartz plate and placing the hierarchical porous structure metal oxide in a corundum porcelain boat;
placing the corundum porcelain boat which is placed into the metal oxide with the hierarchical porous structure in a muffle furnace, and sintering in an oxygen atmosphere;
closing the furnace after the sintering process is finished, cooling the furnace to room temperature, taking out a sintering product, putting the sintering product into a mortar, adding a proper amount of deionized water, grinding the mixture into a slurry shape, and coating the slurry on a metal electrode of a substrate;
and placing the substrate coated with the slurry on a heating table for annealing treatment, and finally obtaining the metal oxide semiconductor gas sensor based on the hierarchical porous butterfly wing structure.
As a further preferable technical scheme of the invention, the corundum porcelain boat which is put into the metal oxide with the hierarchical porous structure is placed in a muffle furnace, and the sintering process in the atmosphere with oxygen comprises the following specific steps:
firstly, heating to 120 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 min;
then heating to 350 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 10 min;
finally, the temperature is raised to 550 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 90 min.
In a further preferred embodiment of the present invention, the temperature of the heating stage during the annealing treatment is controlled to be 250 ℃, and the time for annealing is 24 hours.
The invention relates to a manufacturing method of a metal oxide with a hierarchical porous structure and a metal oxide semiconductor gas sensor, wherein the metal oxide semiconductor gas sensor manufactured based on the metal oxide with the hierarchical porous structure has the following beneficial effects:
1) the butterfly wing biological template is introduced to obtain a multi-scale and multi-morphology intercommunicating pore structure which is not possessed by the conventional grading material, the complicated step of artificially synthesizing the template is omitted, the raw material is saved, the preparation period is saved, and the requirement and the loss of experimental equipment are reduced;
2) the sol-gel method is adopted to prepare the metal oxide with the hierarchical porous structure, so that the requirements of experimental equipment can be reduced, the materials are effectively saved, the loss is reduced, and the manufacturing cost of devices is reduced;
3) the structure designed by the invention can obviously improve the sensitivity and the selectivity of the metal oxide semiconductor gas sensor.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a flow chart of a method of an example provided by a method of fabricating a hierarchical porous structure metal oxide according to the present invention;
FIG. 2 is a schematic structural diagram of a MOS gas sensor fabricated according to an embodiment;
FIG. 3(a) is a scanning electron microscope photograph of a white sintered product obtained by the example with an accuracy of 2 μm;
FIG. 3(b) is a scanning electron microscope photograph of a white sintered product obtained by the example with an accuracy of 1 μm;
FIG. 3(c) is a transmission electron microscope photograph of a white sintered product obtained by the example with an accuracy of 1 μm;
FIG. 4 shows a porous-structure-based metal oxide semiconductor SnO prepared by the following example2And the gas response performance of the gas sensor to ethanol and acetone at different working temperatures is shown.
In fig. 2: 1. a substrate, 2, a metal electrode, 3, and a hierarchical porous structure metal oxide.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
The method for manufacturing the metal oxide with the hierarchical porous structure shown in fig. 1 comprises the following steps:
s1, washing the obtained butterfly wings with deionized water;
s2, soaking the washed butterfly wing for the first time through dilute hydrochloric acid, and then soaking for the second time through a dilute sodium hydroxide solution;
s3, washing the soaked butterfly wing with deionized water again, and airing in the air to be half-dry;
s4, spreading and immersing the butterfly wings aired to be half-dry into sol-gel containing metal ion complexes, carrying out third immersion, taking out the butterfly wings with the metal ions adsorbed on the surfaces, and drying to obtain the butterfly wings coated with the metal ions, wherein the butterfly wings coated with the metal ions are the metal oxides with the hierarchical porous structure.
In a specific implementation, the butterfly wing is a wing of a green phoenix in paris, a wing of a green phoenix or a wing of a green phoenix, but may be other types of butterfly wings.
In specific implementation, the washing times of deionized water are not less than three times.
In specific implementation, the concentration of the dilute hydrochloric acid adopted for the first soaking is 10%, and the soaking time is 3 hours; the concentration of the dilute sodium hydroxide adopted by the second soaking is 8%, and the soaking time is 4 h; the third soaking is soaking for 18 hours at room temperature; .
In the specific implementation, the drying process is to clamp the butterfly wings to keep flat through two quartz plates, and the butterfly wings are dried for 30min at the temperature of 60 ℃.
In specific implementation, the metal ions refer to a metal phase in a semiconductor metal oxide, and the metal ions comprise Sn4 +、Zn2+、Ti4+Or Cu2+The sol gel is Sn4+、Zn2+、Ti4+Or Cu2+And the like, and when used for preparing a template, may contain a metal ion complex, and of course, may contain other metal ions.
As shown in fig. 2, the metal oxide semiconductor gas sensor includes a substrate 1, a metal electrode 2, and a hierarchical porous metal oxide 3 prepared by the method for manufacturing a hierarchical porous metal oxide according to any of the embodiments, wherein the metal electrode 2 is disposed on the substrate 1, at least one hierarchical porous metal oxide 3 is sintered and ground into slurry, and then the slurry is coated on the substrate 1, annealed, and then tightly connected to the metal electrode 2. The metal oxide semiconductor gas sensor adopts the metal oxide with the hierarchical porous structure as the semiconductor material, so that the metal oxide semiconductor gas sensor has the hierarchical porous structure of the butterfly-wing template, a multi-scale and multi-morphology intercommunicating pore structure which is not possessed by the conventional hierarchical material can be obtained, the complicated step of artificially synthesizing the template is omitted, the raw material is saved, the preparation period is saved, and the requirement and the loss of experimental equipment are reduced.
In order to further understand the technical solution of the present invention, the following examples illustrate the preparation process of the metal oxide semiconductor gas sensor based on the hierarchical porous structure metal oxide.
In this example, SnO2For example, the metal oxide semiconductor gas sensor is prepared by removing the biological template from the hierarchical porous metal oxide 3 by sintering treatment, and then replacing the biological template with metal oxideThe compound, i.e. the sintered product is ground into slurry and is tightly connected with the substrate 1 plated with the metal electrode 2 through annealing treatment, and the specific method is as follows:
step one, preparing Sn-containing4+Taking 50ml of 65 wt% concentrated nitric acid and 300ml of deionized water from sol-gel of a metal ion complex, slowly injecting the concentrated nitric acid into the deionized water on a stirring table to obtain a dilute nitric acid solution, and putting 250ml of the dilute nitric acid solution into a beaker and putting the beaker on the stirring table; weighing 5.0g of metallic tin powder with the purity not lower than 99.5 percent, and slowly adding the metallic tin powder into 250ml of dilute nitric acid solution; stirring for 8h under electromagnetic force until the solution is bright yellow; stopping electromagnetic stirring, standing to layer the solution, and taking the upper layer of light yellow transparent solution for later use after 24 hours, wherein the upper layer of light yellow transparent solution is sol-gel;
step two, adopting the sol-gel and manufacturing according to a manufacturing method of the hierarchical porous structure metal oxide to obtain the required hierarchical porous structure metal oxide 3, wherein the wing of the butterfly is the front wing of the green belt butterflyer;
thirdly, evaporating an electrode mask plate on a substrate 1 in a vacuum evaporation instrument to form a metal electrode 2, wherein the substrate 1 is a planar interdigitated ceramic substrate, and the metal electrode 2 is an aluminum electrode;
step four, clamping the hierarchical porous structure metal oxide 3 by a quartz plate and placing the same in a corundum porcelain boat, then placing the corundum porcelain boat in which the hierarchical porous structure metal oxide 3 is placed in a muffle furnace, preferably compacting the same by the corundum plate, and then sintering the same in an oxygen atmosphere, wherein the sintering process is as follows: firstly, heating to 120 ℃ at a heating rate of 5 ℃/min, and preserving heat for 5 min; then heating to 350 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 10 min; finally, heating to 550 ℃ at the heating rate of 1 ℃/min, and preserving the heat for 90 min;
step five, closing the furnace after the sintering process is finished, cooling the furnace to room temperature, taking out a sintered product, selecting a flagellum area of the original butterfly wing template, putting the flagellum area into a mortar, adding a proper amount of deionized water, grinding the mixture into a slurry shape, and coating the slurry shape on the metal electrode 2 of the substrate 1;
and sixthly, placing the substrate 1 coated with the slurry on a heating table, and annealing at 250 ℃ for 24 hours to finally obtain the metal oxide semiconductor gas sensor based on the hierarchical porous butterfly fin micro-tube structure. The butterfly wing structure coated with metal ions before sintering is the hierarchical porous structure metal oxide 2, the biological template is removed in the sintering process, and only the metal oxide replacing the butterfly wing structure is left.
The method has the advantages that the graded porous metal oxide 3 material is firmly combined with the metal electrode 2 with a plane structure, a sensing device with a larger size can be manufactured, and the device structure of the metal oxide semiconductor gas sensor is shown in figure 2.
In this example, the hierarchical porous structure metal oxide 3 is SnO2Scanning electron micrographs of the white sintered product obtained in step four are shown in FIGS. 3(a) and 3(b), and transmission electron micrographs are shown in FIG. 3 (c). From FIGS. 3(a) to 3(c), it can be seen that SnO is graded to be porous2The microtubule structure of the flagella of the butterfly wings is completely copied, the 3D network structure and the pore shape are kept excellent, and the specific surface area and the porosity are large.
Referring to FIG. 4, a hierarchical porous SnO based on flagella structure of butterfly wings made from this example is shown2The gas-sensitive performance of the metal oxide semiconductor gas sensor on ethanol and acetone with the concentration of 200ppm at different temperatures. Corresponding to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, SnO2The responsivity of the metal oxide semiconductor gas sensor to ethanol with the concentration of 200ppm is respectively 1.00, 1.09, 1.95, 2.47, 2.92, 6.09, 8.17, 14.31, 18.44, 25.72, 42.23, 58.30, 87.80, 194.82, 219.67, 176.21 and 79.02, and experiments show that SnO is not oxidized2The metal oxide semiconductor gas sensor has the best ethanol response performance at 380 ℃. Corresponding to 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, SnO2The responsivity of the metal oxide semiconductor gas sensor to acetone with the concentration of 200ppm is respectively 2.28, 3.44, 3.50, 13.16, 21.85, 51.30, 54.04, 54.01, 45.60 and 19.10, and experiments show that SnO is2Metal oxide semiconductor gas sensor inThe acetone response performance is optimal at 360-380 ℃. Experimental results show that the SnO with a porous intercommunicating structure is completely reserved2The metal oxide semiconductor gas sensor has excellent gas sensing performance.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (10)
1. A method for manufacturing a hierarchical porous structure metal oxide is characterized by comprising the following steps:
s1, washing the obtained butterfly wings with deionized water;
s2, soaking the washed butterfly wing for the first time through dilute hydrochloric acid, and then soaking for the second time through a dilute sodium hydroxide solution;
s3, washing the soaked butterfly wing with deionized water again, and airing in the air to be half-dry;
s4, spreading and immersing the butterfly wings aired to be half-dry into sol-gel containing metal ion complexes, carrying out third immersion, taking out the butterfly wings with the metal ions adsorbed on the surfaces, and drying to obtain the butterfly wings coated by the metal ions, namely the hierarchical porous metal oxide.
2. The method of claim 1, wherein the butterfly wing is a wing of a Pacific Papilio pteri, a wing of a green belt Papilio pteri, or a wing of a celosia pteris.
3. The method of claim 2, wherein the number of rinsing with deionized water is not less than three times.
4. The method for preparing a metal oxide with a hierarchical porous structure according to claim 3, wherein the concentration of dilute hydrochloric acid used for the first soaking is 10%, and the soaking time is 3 hours; the concentration of the dilute sodium hydroxide adopted by the second soaking is 8%, and the soaking time is 4 h; the third soaking is soaking for 18 hours at room temperature; .
5. The method for producing a hierarchical porous structure metal oxide according to claim 4, wherein the drying process is performed by: the butterfly wings are clamped by two quartz plates to keep flat, and the butterfly wings are dried for 30min at the temperature of 60 ℃.
6. The method according to any one of claims 1 to 5, wherein the metal ions refer to a metal phase in a semiconductor metal oxide, and the metal ions include Ti4+、Sn4+、Zn2+Or Cu2+。
7. A metal oxide semiconductor gas sensor comprising a substrate, a metal electrode, and a hierarchical porous metal oxide produced by the method of any one of claims 1 to 6, wherein the metal electrode is disposed on the substrate, and at least one piece of the hierarchical porous metal oxide is sintered and then ground into a slurry to be applied on the substrate and connected to the metal electrode.
8. The metal oxide semiconductor gas sensor according to claim 7, wherein the metal oxide semiconductor gas sensor is produced by the following method:
evaporating an electrode mask plate on a substrate in a vacuum evaporation instrument to form a metal electrode;
clamping the hierarchical porous structure metal oxide by using a quartz plate and placing the hierarchical porous structure metal oxide in a corundum porcelain boat;
placing the corundum porcelain boat which is placed into the metal oxide with the hierarchical porous structure in a muffle furnace, and sintering in an oxygen atmosphere;
closing the furnace after the sintering process is finished, cooling the furnace to room temperature, taking out a sintering product, putting the sintering product into a mortar, adding a proper amount of deionized water, grinding the mixture into a slurry shape, and coating the slurry on a metal electrode of a substrate;
and placing the substrate coated with the slurry on a heating table for annealing treatment, and finally obtaining the metal oxide semiconductor gas sensor based on the hierarchical porous butterfly wing structure.
9. The metal oxide semiconductor gas sensor according to claim 8, wherein the corundum porcelain boat containing the metal oxide of hierarchical porous structure is placed in a muffle furnace, and the sintering in an atmosphere of oxygen is carried out by the following steps:
firstly, heating to 120 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 min;
then heating to 350 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 10 min;
finally, the temperature is raised to 550 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 90 min.
10. The metal oxide semiconductor gas sensor according to claim 8, wherein the controlled temperature of the heating stage during the annealing is 250 ℃ and the annealing time is 24 hours.
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