CN101701928A - Gas-sensitive transducer with nano wall structure and preparation method thereof - Google Patents
Gas-sensitive transducer with nano wall structure and preparation method thereof Download PDFInfo
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- CN101701928A CN101701928A CN200910272543A CN200910272543A CN101701928A CN 101701928 A CN101701928 A CN 101701928A CN 200910272543 A CN200910272543 A CN 200910272543A CN 200910272543 A CN200910272543 A CN 200910272543A CN 101701928 A CN101701928 A CN 101701928A
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Abstract
The invention provides a gas-sensitive transducer with a nano wall structure and a preparation method thereof. The transducer sequentially comprises a measurement circuit, a measurement electrode, a nano wall structure sensitive material, porous alumina, compact alumina, pure aluminum, a sensitive material, a heating material, a heating electrode and a heating circuit which are in close contact from top to bottom. The preparation method of the transducer comprises the steps of: preprocessing the pure aluminum, and then forming a porous anode oxidation template by using a secondary anode oxidation method, wherein the surface of the porous anode oxidation template is provided with the porous alumina and the bottom layer is provided with the compact alumina; preparing the sensitive material with the nano wall structure on the template by adopting a sol-gel coating method; and preparing the measurement circuit, the measurement electrode, the heating material, the heating electrode and the heating circuit by adopting a screen printing method, i.e. assembling the gas-sensitive transducer with the nano wall structure. The transducer has better sensitivity, optimized performance and controllable structure.
Description
Technical field
The present invention relates to a kind of gas sensor, particularly relating to a kind of is that substrate preparation (assembling) has the controlled and consistance of performance and good stability, gas sensor highly sensitive, that working temperature is low is popped one's head in and preparation method thereof with the porous anodic alumina template.
Background technology
Along with the raising of people's living standard with to the pay attention to day by day of environmental protection, detection to various poisonous, harmful gases, all have higher requirement to the monitoring of atmospheric pollution, industrial gaseous waste and to the detection of food and human settlement's quality, therefore the gas sensor as one of sense organ or stimulus part is absolutely necessary.Gas sensor can detect and analyze all gases in real time, has advantages such as highly sensitive, response time weak point; Add developing rapidly of microelectronics, micro-processing technology and robotization, intellectualized technology, make gas sensor smaller volume, cheap, easy to use, so it has obtained using widely in fields such as military affairs, medical science, traffic, environmental protection, quality inspection, false proof, households.But still there are some problems in commercially available gas sensor at present, as selectivity and less stable etc.The further raising of the every performance index of gas sensor, new gas sensitive and the exploitation of new gas sensor are come into one's own just day by day, and countries in the world are thrown the research that huge fund is carried out this field one after another.The sensor industry of China is started late, and through years development, whole industry begins to take shape, has entered into Rapid development stage.But, the sensor industry of China mainly concentrates on the mid and low-end products, the exploitation high-end product enters high-end product market, overcomes the situation of high-end product dependence on import, need sell simultaneously at aspects such as estate planning, financial support, policy favour, personnel trainings.
Summary of the invention
Technical matters to be solved by this invention is: a kind of gas-sensitive transducer with nano wall structure and preparation method thereof is provided, and this sensor sensing is better, and performance is optimized.
The technical solution adopted in the present invention is: gas-sensitive transducer with nano wall structure comprises metering circuit, potential electrode, nano wall structure sensitive material, Woelm Alumina, compact aluminum oxide, fine aluminium, sensitive material, heating material, heating electrode and the heater circuit of tight contact from top to bottom successively.
The preparation method of described gas-sensitive transducer with nano wall structure: after the fine aluminium pre-service, use the two-step anodization method to prepare porous anodic alumina template; On this template, adopt the sol-gelatin plating method preparation to have the sensitive material of nano wall structure; Prepare metering circuit, potential electrode, heating material, heating electrode and heater circuit by method for printing screen at last, promptly be assembled into gas-sensitive transducer with nano wall structure.
Advantage of the present invention: this method is template with the Woelm Alumina, obtains to have the sensitive material coating of nano wall structure, utilizes surface effect, the size effect of material, can improve the sensitive property of sensitive material.This method is also optimized thickness, the structure of sensitive thin film layer in the sensor probe package assembly, the hole degree of depth of porous alumina formwork, hole density, aperture size, barrier layer thickness etc., the high sensor probe of obtained performance optimization, controllable structure.
Sensor performance is sensitivity and reaction time and release time to characterize sensitivity definition: the ratio of the resistance in the aerial resistance of gas sensor and the resistance in tested atmosphere.Sensitivity is represented with S: S=R
0/ R, R are illustrated in the resistance value of sensor in the test atmosphere, R
0The aerial resistance value of expression sensor.Contact with tested gas from sensor, to the gas sensor sensor with tested gas effect after, its resistance reduces (perhaps increasing) and to the 90% o'clock needed time of original resistance value, is called the response time; Sensor is in desorption process, and its resistance increases (perhaps reducing) and to the 90% o'clock needed time of original resistance value, is called release time.
Nanometer wall gas sensor of the present invention can reach 95 350 ℃ of sensitivity during to concentration of alcohol 100ppm, and the response time is less than 5 seconds, about 15 seconds of turnaround time; Sensitivity during to concentration of alcohol 1000ppm can reach 150, and the reaction time is less than 5 seconds, about 20 seconds of turnaround time.
Description of drawings
Fig. 1 is preparation technology's process flow diagram of sensor probe of the present invention;
Fig. 2 is the package assembly synoptic diagram of sensor probe of the present invention;
Fig. 3 is the sem photograph of the porous anodic alumina films plate hole gap structure of sensor probe of the present invention;
Fig. 4 is the sem photograph of the responsive rete micromechanism of ZnO of sensor probe of the present invention.
Among Fig. 2,1. metering circuit; 2. potential electrode; 3. nano wall structure sensitive material; 4. Woelm Alumina; 5. compact aluminum oxide; 6. fine aluminium; 7. insulation course; 8. heating material; 9. heating electrode; 10. heater circuit.
Embodiment
Principle of the present invention is the nano wall structure sensitive material coating of preparation bigger serface, utilizes surface effect, the size effect of material, improves its sensitive property.Nano wall structure is to be template with the porous anodic aluminium oxide, covers its hole wall and forms.Sensitive material can be zinc paste, and coating adopts the sol-gel method preparation; Gained nanometer wall microstructure sensitive material can be applicable on the gas sensor probe.ZnO nano particle adsorb oxygen molecule in the air of cleaning, oxygen molecule becomes O from ZnO nano grain surface electron gain
2 -, O
-Even O
2-In negative ion, material surface resistance is increased.When reducibility gas such as ethanol arrive the ZnO nano grain surface, they can give negative oxygen ion with the electron transfer of self, the electronics that negative oxygen ion will originally be captured is restored in the ZnO nano particle, makes its conduction band electron concentration increase, surface resistance descend, thereby show air-sensitive character.ZnO gas-sensitive transducer with nano wall structure of the present invention, because ZnO is deposited in the hole of nano-scale Woelm Alumina, the ZnO of same quality has just had bigger specific surface area, generates negative oxygen ion thereby can adsorb more oxygen molecule from air.When sensor surface touches tested gas molecule, these molecules will be diffused in the whole rete rapidly, and with originally be adsorbed on the lip-deep negative oxygen ion of cell walls and reacted, the electronics that causes negative oxygen ion to be caught comes back in the ZnO alloy granular solids, the surface resistance of ZnO is descended, thereby show better sensitivity and shorter response time and release time.
As shown in Figure 2, gas-sensitive transducer with nano wall structure of the present invention comprises metering circuit 1, potential electrode 2, nano wall structure sensitive material 3, Woelm Alumina 4, compact aluminum oxide 5, fine aluminium 6, insulation course 7, heating material 8, heating electrode 9 and the heater circuit 10 of tight contact from top to bottom successively.
The insulation course 7 of lower floor among Fig. 2 is when preparation one deck sensitive material at the backside deposition of sensor probe, and this sensitive material is identical with the composition of nano wall structure sensitive material 3.It is exactly to insulate that but the sensitive material of insulation course 7 also has an effect, because the aluminium resistance ratio is lower, aluminium and heating electrode and material kept apart to strengthen adds thermal effect.
As shown in Figure 1, the preparation method of described gas sensor is: after fine aluminium 6 pre-service, use the two-step anodization method, forming the surface is the porous anode template of compact aluminum oxide 5 for Woelm Alumina 4, bottom; On this template, adopt sol-gelatin plating method to prepare sensitive material 3, and form insulation course 7 at the another side of fine aluminium 6 with nano wall structure; Prepare metering circuit 1, potential electrode 2, heating material 8, heating electrode 9 and heater circuit 10 by method for printing screen at last, promptly be assembled into gas-sensitive transducer with nano wall structure.Sensitive material can be zinc paste.
The preparation method specifically comprises following steps:
1) substrate made from fine aluminium is carried out pre-service:
To eliminate the unrelieved stress of aluminium flake, reach electrochemical polish to eliminate the aluminium flake surface scratch by high annealing, purpose is to avoid cut that the systematicness of aluminium flake oxidation growth is damaged;
2) step 1) gained fine aluminium substrate 6 is carried out anodic oxidation:
Be divided into for three steps, i.e. an anodic oxidation, the oxide film and the two-step anodization of removal once oxidation; Forming the surface at last is the porous anode template of compact aluminum oxide 5 for Woelm Alumina 4, bottom;
3) to step 2) gained porous anode template carries out reaming and handles:
The hole that forms is corroded to increase its diameter;
4) carry out the sensitive material deposition on the porous anode template after step 3) is handled:
Be divided into for three steps, i.e. sensitive material colloidal sol configuration lifts plated film, sensitive material drying and sintering; Make sensitive material 3 at last, and form insulation course 7 at the another side of fine aluminium 6 with nano wall structure;
5) printing of heating material and electrode:
Be divided into for four steps, i.e. electrode coating slurry modulation, the preparation of serigraphy web plate, serigraphy and printing material sintering curing; This step makes metering circuit 1, potential electrode 2, heating material 8, heating electrode 9 and heater circuit 10, finally is assembled into gas-sensitive transducer with nano wall structure.
The pre-service of step 1) fine aluminium substrate specifically comprises:
(a) stress relief annealing:
Selecting purity for use is 99.999% aluminium flake, cleans roughly with deionized water, absolute ethyl alcohol; Be placed on then in the resistance furnace and be warming up to 480 ℃ with stove, be incubated 1 hour, cool to room temperature with the furnace, the aluminium flake that obtains low unrelieved stress, uniform crystal particles is standby;
(b) surface finish:
With the ultrasonic cleaning 30 minutes in acetone of the aluminium flake after the annealing, to remove the grease contamination on surface, then be positioned in the NaOH solution of 0.2mol/l and soaked 2 minutes, thoroughly clean with deionized water; Then aluminium flake in being the mixed electrolytic solution of 1: 4 perchloric acid and absolute ethyl alcohol, volume ratio is carried out electropolishing, to eliminate the surface scratch that aluminium flake stays in process of production, anode is the aluminium flake of above-mentioned processing, negative electrode is the common aluminium flake that cleans up, electrolysis is 2 minutes under the 20V DC voltage, till range estimation anode aluminium flake under high light becomes light, clean up standby again with deionized water.
Step 2) anodic oxidation of fine aluminium 6 specifically comprises:
(a) anodic oxidation:
With analytically pure sulfuric acid or oxalic acid and deionized water, be mixed with the oxalic acid solution of 0.5mol/l or the sulfuric acid solution of 1.5mol/l, as anodised electrolytic solution once, anode is the aluminium flake that step 1) was handled, negative electrode is the common aluminium flake that cleans up, be fixed on the homemade oxidation support, distance between electrodes is 7cm, adopts constant voltage mode, oxidization time 2～4 hours, the sulfuric acid electrolyte oxidation voltage is 15～30V, oxalic acid electrolytic solution oxidation voltage is 30～50V, adopts water-bath during the oxidation reaction, and the temperature in the reactive tank is controlled at 10 ℃, oxidization time reaches the back and takes out sample, cleans up with deionized water;
(b) remove the once oxidation film:
With analytically pure phosphoric acid and chromic acid and deionized water, be mixed with the phosphoric acid solution of 6wt% and the chromic acid solution of 1.8wt% respectively, two kinds of solution are mixed, mixed solution is heated to 60 ℃ then, the sample after the once oxidation is placed in one soaked 3 hours at last;
(c) two-step anodization:
The parameter of two-step anodization identical with anodised each parameter of the first step (parameter comprises electrolytic solution and concentration thereof, voltage, temperature), oxidization time is adjusted (as 5 hours) according to actual needs, oxidization time reaches the back and takes out sample, cleans up with deionized water.
The reaming of step 3) porous anode template is handled and is specifically comprised:
The phosphoric acid solution that pure phosphoric acid and deionized water are configured to 0.5mol/l will be analyzed, making reaming and handle the solution of usefulness, with step 2) sample of gained secondary oxidation is immersed in the reaming solution, carries out reaming and handled 1 hour, time reaches the back and takes out sample, cleans up with deionized water.
Step 4) is carried out the sensitive material deposition and is specifically comprised on porous anodic alumina template:
(a) colloidal sol configuration:
Accurately take by weighing a certain amount of Zn (CH with electronic balance
3COO)
22H
2O is dissolved in the absolute ethyl alcohol of 50ml, is placed on then on the magnetic stirring apparatus in 50 ℃ of heated and stirred, is emulsus until solution; Accurately measure a certain amount of diethanolamine (NH (C with graduated cylinder then
2H
5O)
2), dropwise join in the solution, in 30s, finish, make x[Zn (CH
3COO)
22H
2O]: y[NH (C
2H
5O)
2] mol ratio be 1: 2; Accurately measure a certain amount of deionized water with graduated cylinder again, join in the solution, make x[Zn (CH
3COO)
22H
2O]: y[H
2O] mol ratio be 1: 1, continue to stir 3 hours, at last certain density transparent, stable colourless colloidal sol is standby;
(b) lift plated film:
With the colloidal sol sealing that (a) prepares, ageing at room temperature placed under 70 ℃ of water-baths again and placed 2 hours after 24 hours; With the glass substrate that cleans up vertically, at the uniform velocity immerse in the colloidal sol for preparing, leave standstill 60s after, vertically, at the uniform velocity upwards lift substrate with the speed of 6cm/min, the baking oven inner drying of 100 ℃ of constant temperature 10 minutes, repeat aforesaid operations then with the preparation multilayer film.The process that for example repeats 3 times " glass substrate that cleans up vertically, at the uniform velocity being immersed in the colloidal sol for preparing; after leaving standstill 60s; the speed with 6cm/min vertically, at the uniform velocity upwards lifts substrate, then the baking oven inner drying of 100 ℃ of constant temperature 10 minutes " can obtain 3 layer films.
(c) drying and sintering:
After having plated last tunic, again the baking oven inner drying of 100 ℃ of constant temperature 1 hour; Then dried ZnO gel mould is put into chamber type electric resistance furnace, with certain heat treating regime sample is carried out aftertreatment, wherein 3 ℃/min of programming rate is incubated 30 minutes under 300 ℃ holding temperature, again required post-processing temperature place (as 500 ℃) insulation 1 hour; Naturally cool to room temperature with stove at last, can obtain wall construction ZnO film (being 3 among Fig. 2), and form insulation course 7 at the another side of fine aluminium 6.
The printing of step 5) heating material and electrode specifically comprises:
(a) slurry modulation (all batching number percents of the present invention are mass percent):
The configuration of resistance slurry: medicine and reagent are to be analyzed purely, chooses mass percent and is respectively 5% RuO
2With 95% frit, the batching proportioning of this frit is PbO:70%, B
2O
3: 3%, SiO
2: 25%, Al
2O
3: 2%; With RuO
2Melt in the Pt crucible with frit, glaze is pulverized after 325 order terylene screen clothes sieve; Add 50～70% organic carrier at last and stir, the batching proportioning of this organic carrier solute is an ethyl cellulose: 10%, and butyl carbitol: 90%;
The configuration of electrode slurry: choose analytically pure Ag powder and organic carrier, the diameter of this Ag powder is less than 0.5 μ m, and this organic carrier batching proportioning is an ethyl cellulose: 10%, and butyl carbitol: 90%; With Ag powder, organic carrier, activator (as cyclohexanone) (as quality proportioning 45: 4: 1) proportioning in accordance with the appropriate ratio, put into ultrasonic-wave crushing and mix and made slurry in 2～3 hours;
(b) screen template preparation:
Choose 200 order terylene screen clothes, adopt Scroll from stretching tight frame; After the terylene screen cloth cleaned with 20% NaOH solution, with deionized water rinsing and dry; 3 layers of coating film films are according to the printing down 20 seconds under uviol lamp of the circuit diagram of design; Masterplate after the exposure is put into absolute ethyl alcohol developed 2 minutes, take out back hot blast drying under less than 45 ℃ temperature; Check the masterplate quality at last, through suitably repairing the preparation of finishing screen template;
(c) serigraphy:
Adopt hand-screen, on print station, operate; Use standard round end doctor prints heating material 8, heating electrode 9 and heater circuit 10 successively in the heated side of insulation course 7, prints metering circuit 1 and potential electrode 2 successively in the measurement side of nano wall structure sensitive material 3;
(d) sintering curing:
Material after the serigraphy was placed 100 ℃ of dry solidifications 30 minutes; Then place 150 ℃ of dryings 30 minutes to remove butyl carbitol; Place 350 ℃ of sintering 30 minutes to remove ethyl cellulose then; Placed 500 ℃ of densification sinterings at last 1 hour, and made the glassy phase fusing combine with substrate.
Prepare gas sensor of the present invention as stated above.
The invention will be further described below in conjunction with the embodiment with form, but do not limit the present invention.Structural controllability of the present invention is embodied in controlled to the sensitive material specific surface area, by changing the preparation parameter (voltage, time) of porous alumina formwork, size, distribution density and the degree of depth that can the control template hole be controlled the sensitive material specific surface area thereby reach.
Embodiment 1: technical scheme
| Aluminium base pre-service | The anodic oxidation of fine aluminium substrate | Sensitive material is coated with | Print electrode and circuit |
| Stress relief annealing: 480 ℃ of insulations annealing in 1 hour.Soaked in the NaOH solution of surface finish: 0.2mol/ |
An anodic oxidation: be mixed with the oxalic acid solution of 0.5mol/l, 30V, 10 ℃ of oxidations |
Colloidal sol configuration: x[Zn (CH
3COO)
22H
2O]: y [NH (C
2H
5O)
2]: z[H
2O]=1: 2: 1 preparation Zn colloidal sol, the titration time 30s of diethanolamine.Lift plated film: room temperature ageing 24 hours, 70 ℃ of water- |
Slurry configuration: configuration in proportion.During the resistance slurry configuration, finally churned organic carrier is 50%.During the electrode slurry configuration, the last 3 hours ultrasonic-wave crushing time.The screen stencil preparation: the terylene screen cloth cleans through 20% NaOH, 3 layers of coating film films, and printing down is 20 seconds under the uviol lamp, develops 2 minutes in the absolute ethyl alcohol, less than drying up under 45 ℃ the temperature.Serigraphy: print heating material 8, |
The sensor performance of embodiment 1 preparation:
Embodiment 2: technical scheme
| Aluminium base pre-service | The anodic oxidation of fine aluminium substrate | Sensitive material is coated with | Print electrode and circuit |
| With |
During an anodic oxidation, 30V was 10 ℃ of oxidations |
With |
During the resistance slurry configuration, finally churned organic carrier is 70%.During the electrode slurry configuration, the last 2 hours ultrasonic-wave crushing time.All the other are with |
The sensor performance of embodiment 2 preparations:
Embodiment 3: technical scheme
| Aluminium base pre-service | Anodic oxidation | Sensitive material is coated with | Print electrode and circuit |
| With |
During an anodic oxidation, 40V was 10 ℃ of oxidations |
With |
During the resistance slurry configuration, finally churned organic carrier is 60%.During the electrode slurry configuration, the last 2.5 hours ultrasonic-wave crushing time.All the other are with |
The sensor performance of embodiment 3 preparations:
Embodiment 4: technical scheme
| Aluminium base pre-service | Anodic oxidation | Sensitive material is coated with | Print electrode and circuit |
| With |
During an anodic oxidation, 20V was 10 ℃ of oxidations |
With |
With |
The sensor performance of embodiment 4 preparations:
Embodiment 5: technical scheme
| Aluminium base pre-service | Anodic oxidation | Sensitive material is coated with | Print electrode and circuit |
| With |
During an anodic oxidation, 50V was 10 ℃ of oxidations |
With |
With |
The sensor performance of embodiment 5 preparations:
Embodiment 6: technical scheme
| Aluminium base pre-service | Anodic oxidation | Sensitive material is coated with | Print electrode and circuit |
| With |
During an anodic oxidation, 15V was 10 ℃ of oxidations |
With |
With |
The sensor performance of embodiment 6 preparations
Claims (8)
1. gas-sensitive transducer with nano wall structure, it is characterized in that: it comprises metering circuit, potential electrode, nano wall structure sensitive material, Woelm Alumina, compact aluminum oxide, fine aluminium, insulation course, heating material, heating electrode and the heater circuit of tight contact from top to bottom successively.
2. the preparation method of gas-sensitive transducer with nano wall structure according to claim 1 is characterized in that: after the fine aluminium pre-service, use two-step anodization method preparation surface to be Woelm Alumina, the bottom porous anodic alumina template as compact aluminum oxide; On this template, adopt sol-gelatin plating method to prepare sensitive material, and form insulation course at the another side of fine aluminium with nano wall structure; Prepare metering circuit, potential electrode, heating material, heating electrode and heater circuit by method for printing screen at last, promptly be assembled into gas-sensitive transducer with nano wall structure.
3. preparation method according to claim 2 is characterized in that specifically comprising following steps:
1) the substrate pre-service to making with fine aluminium:
To eliminate the unrelieved stress of aluminium flake, reach electrochemical polish by high annealing to eliminate the aluminium flake surface scratch;
2) step 1) gained fine aluminium substrate is carried out anodic oxidation:
Be divided into for three steps, i.e. an anodic oxidation, the oxide film and the two-step anodization of removal once oxidation; Forming the surface at last is the porous anode template of compact aluminum oxide for Woelm Alumina, bottom;
3) to step 2) gained porous anode template carries out reaming and handles:
The hole that forms is corroded to increase its diameter;
4) deposit sensitive material on the template after step 3) is handled:
Be divided into for three steps, i.e. sensitive material colloidal sol configuration lifts plated film, sensitive material drying and sintering; Make sensitive material at last, and form insulation course at the another side of fine aluminium with nano wall structure;
5) printing of heating material and electrode: be divided into for four steps, i.e. electrode coating slurry modulation, the preparation of serigraphy web plate, serigraphy and printing material sintering curing; This step makes metering circuit, potential electrode, heating material, heating electrode and heater circuit, finally is assembled into gas-sensitive transducer with nano wall structure.
4. preparation method according to claim 3 is characterized in that the pre-service of step 1) fine aluminium substrate specifically comprises:
(a) stress relief annealing:
Employing purity is 99.999% aluminium flake, cleans roughly with deionized water, absolute ethyl alcohol; Be placed on then in the resistance furnace and be warming up to 480 ℃ with stove, be incubated 1 hour, cool to room temperature with the furnace, the aluminium flake that obtains low unrelieved stress, uniform crystal particles is standby;
(b) surface finish:
With the ultrasonic cleaning 30 minutes in acetone of the aluminium flake after the annealing, to remove the grease contamination on surface, then be positioned in the NaOH solution of 0.2mol/l and soaked 2 minutes, thoroughly clean with deionized water; Then aluminium flake in being the mixed electrolytic solution of 1: 4 perchloric acid and absolute ethyl alcohol, volume ratio is carried out electropolishing, to eliminate the surface scratch that aluminium flake stays in process of production, anode is the aluminium flake of above-mentioned processing, negative electrode is the common aluminium flake that cleans up, electrolysis is 2 minutes under the DC voltage of 20V, till range estimation anode aluminium flake under high light becomes light, clean up standby again with deionized water.
5. preparation method according to claim 3 is characterized in that step 2) anodic oxidation of having handled the fine aluminium substrate specifically comprises:
(a) anodic oxidation:
With analytically pure sulfuric acid or oxalic acid and deionized water, be mixed with the oxalic acid solution of 0.5mol/l or the sulfuric acid solution of 1.5mol/l, as anodised electrolytic solution once, anode is the aluminium flake that step 1) was handled, negative electrode is the common aluminium flake that cleans up, be fixed on the oxidation support, distance between electrodes is 7cm, adopts constant voltage mode, oxidization time 2～4 hours, the sulfuric acid electrolyte oxidation voltage is 15～30V, oxalic acid electrolytic solution oxidation voltage is 30～50V, adopts water-bath during the oxidation reaction, and the temperature in the reactive tank is controlled at 10 ℃, oxidization time reaches the back and takes out sample, cleans up with deionized water;
(b) remove the once oxidation film:
With analytically pure phosphoric acid and chromic acid and deionized water, be mixed with the phosphoric acid solution of 6wt% and the chromic acid solution of 1.8wt% respectively, two kinds of solution are mixed, mixed solution is heated to 60 ℃ then, the sample after the once oxidation is placed in one soaked 3 hours at last;
(c) two-step anodization:
The parameter of two-step anodization is identical with anodised each parameter of the first step, and oxidization time is adjusted according to actual needs, and oxidization time reaches the back and takes out sample, cleans up with deionized water.
6. preparation method according to claim 3, the reaming processing that it is characterized in that the step 3) porous alumina formwork specifically comprises: will analyze the phosphoric acid solution that pure phosphoric acid and deionized water are configured to 0.5mol/l, make reaming and handle the solution of usefulness, with step 2) sample of gained secondary oxidation is immersed in the reaming solution, carrying out reaming handled 1 hour, time reaches the back and takes out sample, cleans up with deionized water.
7. preparation method according to claim 3 is characterized in that step 4) deposits sensitive material and specifically comprises on porous alumina formwork:
(a) colloidal sol configuration:
Accurately take by weighing a certain amount of Zn (CH with electronic balance
3COO)
22H
2O is dissolved in the absolute ethyl alcohol of 50ml, is placed on then on the magnetic stirring apparatus in 50 ℃ of heated and stirred, is emulsus until solution; Accurately measure a certain amount of diethanolamine with graduated cylinder then, dropwise join in the solution, finish, make x[Zn (CH at 30s
3COO)
22H
2O]: y[NH (C
2H
5O)
2] mol ratio be 1: 2; Accurately measure a certain amount of deionized water with graduated cylinder again, join in the solution, make x[Zn (CH
3COO)
22H
2O]: y[H
2O] mol ratio be 1: 1, continue to stir 3 hours, at last certain density transparent, stable colourless colloidal sol is standby;
(b) lift plated film:
With the colloidal sol sealing that (a) prepares, ageing at room temperature places 70 ℃ water-bath to place 2 hours down after 24 hours again; With the glass substrate that cleans up vertically, at the uniform velocity immerse in the colloidal sol for preparing, leave standstill 60s after, vertically, at the uniform velocity upwards lift substrate with the speed of 6cm/min, the baking oven inner drying of 100 ℃ of constant temperature 10 minutes, repeat aforesaid operations then with the preparation multilayer film.
(c) drying and sintering:
After having plated last tunic, again the baking oven inner drying of 100 ℃ of constant temperature 1 hour; Then dried ZnO gel mould is put into chamber type electric resistance furnace, with certain heat treating regime sample is carried out aftertreatment, wherein 3 ℃/min of programming rate is incubated 30 minutes under 300 ℃ holding temperature, is incubated 1 hour again under 500 ℃ post-processing temperature; Naturally cool to room temperature with stove at last, can obtain the wall construction ZnO film, and form insulation course at the another side of fine aluminium.
8. preparation method according to claim 3 is characterized in that the printing of step 5) heating material and electrode specifically comprises:
(a) slurry modulation:
The configuration of resistance slurry: medicine and reagent are to be analyzed purely, chooses mass percent and is respectively 5% RuO
2With 95% frit, the charge ratio of this frit is respectively PbO: 70%, and B
2O
3: 3%, SiO
2: 25%, Al
2O
3: 2%; With RuO
2Melt in the Pt crucible with frit, glaze is pulverized after 325 order terylene screen clothes sieve; Add 50～70% organic carrier at last and stir, this organic carrier charge ratio is: ethyl cellulose 10%, butyl carbitol 90%;
The configuration of electrode slurry: choose and analyze pure Ag powder and organic carrier, the diameter of this Ag powder is less than 0.5 μ m, and this organic carrier charge ratio is: ethyl cellulose 10%, butyl carbitol 90%; With Ag powder, organic carrier and a certain amount of activator proportioning in accordance with the appropriate ratio, put into ultrasonic-wave crushing and mix and made slurry in 2～3 hours;
(b) screen template preparation:
Choose 200 order terylene screen clothes, adopt Scroll from stretching tight frame; After the terylene screen cloth cleaned with 20% NaOH solution, with deionized water rinsing and dry; 3 layers of coating film films are according to the printing down 20 seconds under uviol lamp of the circuit diagram of design; Masterplate after the exposure is put into absolute ethyl alcohol developed 2 minutes, take out back hot blast drying under less than 45 ℃ temperature; Check the masterplate quality at last, through suitably repairing the preparation of finishing screen template;
(c) serigraphy:
Adopt hand-screen, on print station, operate; Use standard round end doctor prints heating material, heating electrode and heater circuit successively in the heated side of insulation course, prints potential electrode and metering circuit successively in the measurement side of nano wall structure sensitive material;
(d) sintering curing:
Step (d) gained is prepared sample placed 100 ℃ of dry solidifications 30 minutes; Then place 150 ℃ of dryings 30 minutes to remove butyl carbitol; Place 350 ℃ of sintering 30 minutes to remove ethyl cellulose then; Placed 500 ℃ of sintering at last 1 hour, and made the glassy phase fusing combine with substrate.
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| CN (1) | CN101701928A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101975796A (en) * | 2010-09-03 | 2011-02-16 | 郑州炜盛电子科技有限公司 | Leadless ceramic chip type gas sensor |
| CN102162115A (en) * | 2011-01-20 | 2011-08-24 | 浙江大学 | Color regulation and control method based on porous alumina and single atom deposition technology |
| CN102191528A (en) * | 2011-04-02 | 2011-09-21 | 河北师范大学 | Preparation method of Co nanotube and alumina composite film with bright colors and different patterns |
| CN102807190A (en) * | 2012-09-07 | 2012-12-05 | 天津大学 | Method for eliminating internal stress of nanodevice |
| CN102832120A (en) * | 2012-09-07 | 2012-12-19 | 天津大学 | Method for applying prestress on nanometer device surface |
| CN103009840A (en) * | 2012-12-25 | 2013-04-03 | 衡水英利新能源有限公司 | Rapid repair method of screen plate |
| CN103424439A (en) * | 2013-09-04 | 2013-12-04 | 浙江工商大学 | Gas sensor for detecting trace benzene |
| CN103522783A (en) * | 2013-10-24 | 2014-01-22 | 天津理工大学 | Method for preparing low-cost interdigital transducer and reflecting grating by utilizing silk-screen printing process |
| CN105021303A (en) * | 2015-07-15 | 2015-11-04 | 哈尔滨工程大学 | Method for manufacturing temperature sensor of aluminum-based sensitive material |
| CN105021655A (en) * | 2015-07-03 | 2015-11-04 | 西安工业大学 | ZnO nano wall/RGO heterojunction gas-sensitive sensor and preparation method thereof |
| CN105611717A (en) * | 2016-01-22 | 2016-05-25 | 江西宝盛半导体能源科技有限公司 | Ultrahigh heat-conduction metal-based circuit board and fabrication method thereof |
| CN105603490A (en) * | 2016-01-22 | 2016-05-25 | 江西宝盛半导体能源科技有限公司 | Insulating coating material with ultrahigh thermal conductivity and method for preparing insulating coating material |
| CN105887154A (en) * | 2016-04-29 | 2016-08-24 | 南阳师范学院 | Preparing method for aluminum oxide two-dimensional photonic crystal |
| CN108751706A (en) * | 2018-05-22 | 2018-11-06 | 山东华菱电子股份有限公司 | A kind of wear resistant corrosion resistant glass glaze |
| CN109334141A (en) * | 2018-09-12 | 2019-02-15 | 中山波利马塑胶科技有限公司 | A kind of plate construction of incubator and preparation method thereof |
| CN110220946A (en) * | 2019-07-02 | 2019-09-10 | 云南中烟工业有限责任公司 | A kind of honey quality analysis gas sensor and its preparation method and application |
| CN110497682A (en) * | 2019-09-11 | 2019-11-26 | 吴坤苗 | Printing machine environmental protection offset plate guiding conveying quenching unit |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101975796B (en) * | 2010-09-03 | 2013-01-09 | 郑州炜盛电子科技有限公司 | Leadless ceramic chip type gas sensor |
| CN101975796A (en) * | 2010-09-03 | 2011-02-16 | 郑州炜盛电子科技有限公司 | Leadless ceramic chip type gas sensor |
| CN102162115B (en) * | 2011-01-20 | 2012-05-02 | 浙江大学 | Color regulation and control method based on porous alumina and single atom deposition technology |
| CN102162115A (en) * | 2011-01-20 | 2011-08-24 | 浙江大学 | Color regulation and control method based on porous alumina and single atom deposition technology |
| CN102191528A (en) * | 2011-04-02 | 2011-09-21 | 河北师范大学 | Preparation method of Co nanotube and alumina composite film with bright colors and different patterns |
| CN102807190A (en) * | 2012-09-07 | 2012-12-05 | 天津大学 | Method for eliminating internal stress of nanodevice |
| CN102832120A (en) * | 2012-09-07 | 2012-12-19 | 天津大学 | Method for applying prestress on nanometer device surface |
| CN103009840A (en) * | 2012-12-25 | 2013-04-03 | 衡水英利新能源有限公司 | Rapid repair method of screen plate |
| CN103424439A (en) * | 2013-09-04 | 2013-12-04 | 浙江工商大学 | Gas sensor for detecting trace benzene |
| CN103522783A (en) * | 2013-10-24 | 2014-01-22 | 天津理工大学 | Method for preparing low-cost interdigital transducer and reflecting grating by utilizing silk-screen printing process |
| CN105021655B (en) * | 2015-07-03 | 2017-08-22 | 西安工业大学 | ZnO nano wall/RGO hetero-junctions gas sensors and preparation method thereof |
| CN105021655A (en) * | 2015-07-03 | 2015-11-04 | 西安工业大学 | ZnO nano wall/RGO heterojunction gas-sensitive sensor and preparation method thereof |
| CN105021303A (en) * | 2015-07-15 | 2015-11-04 | 哈尔滨工程大学 | Method for manufacturing temperature sensor of aluminum-based sensitive material |
| CN105021303B (en) * | 2015-07-15 | 2018-04-17 | 哈尔滨工程大学 | A kind of manufacturing method of temperature sensor of aluminium base sensitive material |
| CN105611717A (en) * | 2016-01-22 | 2016-05-25 | 江西宝盛半导体能源科技有限公司 | Ultrahigh heat-conduction metal-based circuit board and fabrication method thereof |
| CN105603490A (en) * | 2016-01-22 | 2016-05-25 | 江西宝盛半导体能源科技有限公司 | Insulating coating material with ultrahigh thermal conductivity and method for preparing insulating coating material |
| CN105611717B (en) * | 2016-01-22 | 2019-01-22 | 江西宝盛半导体能源科技有限公司 | A kind of metal base circuit board of super-high heat-conductive and preparation method thereof |
| CN105887154A (en) * | 2016-04-29 | 2016-08-24 | 南阳师范学院 | Preparing method for aluminum oxide two-dimensional photonic crystal |
| CN105887154B (en) * | 2016-04-29 | 2018-11-16 | 南阳师范学院 | A kind of aluminium oxide 2 D photon crystal preparation method |
| CN108751706A (en) * | 2018-05-22 | 2018-11-06 | 山东华菱电子股份有限公司 | A kind of wear resistant corrosion resistant glass glaze |
| CN109334141A (en) * | 2018-09-12 | 2019-02-15 | 中山波利马塑胶科技有限公司 | A kind of plate construction of incubator and preparation method thereof |
| CN109334141B (en) * | 2018-09-12 | 2023-11-10 | 中山波利马塑胶科技有限公司 | Plate structure of insulation box and preparation method thereof |
| CN110220946A (en) * | 2019-07-02 | 2019-09-10 | 云南中烟工业有限责任公司 | A kind of honey quality analysis gas sensor and its preparation method and application |
| CN110497682A (en) * | 2019-09-11 | 2019-11-26 | 吴坤苗 | Printing machine environmental protection offset plate guiding conveying quenching unit |
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