CN102866181A - Polyaniline/ titanium dioxide nanometer composite impedance type thin film gas sensor and preparation method thereof - Google Patents
Polyaniline/ titanium dioxide nanometer composite impedance type thin film gas sensor and preparation method thereof Download PDFInfo
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- CN102866181A CN102866181A CN201210376831XA CN201210376831A CN102866181A CN 102866181 A CN102866181 A CN 102866181A CN 201210376831X A CN201210376831X A CN 201210376831XA CN 201210376831 A CN201210376831 A CN 201210376831A CN 102866181 A CN102866181 A CN 102866181A
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Abstract
The invention discloses a polyaniline/ titanium dioxide nanometer composite impedance type thin film gas sensor and a preparation method thereof. The gas sensor comprises a ceramic base body, an interdigital gold electrode and a gas-sensitive thin film. The gas-sensitive thin film is composed of a polyaniline/ titanium self-assembly layer and a polyaniline layer, wherein the polyaniline/ titanium self-assembly layer can greatly improve response sensitivity of the sensor to gas under room temperature, accelerates response and improves stability, and the polyaniline layer can reduce impedance of elements well. The gas sensor has high response sensitivity to ammonia gas under the room temperature, has extremely good responding performance, responds quickly, is good in stability, and can be widely applied to accurate measurement and control of ammonia gas concentration in the industrial and agricultural production process and the atmospheric environment. The invention further provides the method for preparing the gas sensor. The method is simple in process, low in cost and extremely suitable for mass production.
Description
Technical field
The present invention relates to sensor field, be specifically related to a kind of polyaniline/titanium dioxide impedance type thin film gas sensor and preparation method thereof.
Background technology
Gas sensor is the important chemical sensor of a class, have a wide range of applications at aspects such as storage, commercial production, process control, environmental monitorings, and in modern development in science and technology and people's life, play a part to become more and more important, constantly pursue high-performance, low cost, small size etc. become the difficult problem that the sensor industry needs to be resolved hurrily.In addition, the introducing of new material new technology and innovation make these difficult problems of solution become possibility.
Traditional gas sensor sensitive material comprises inorganic semiconductor material and organic conductive polymkeric substance two large classes.The inorganic semiconductor gas sensitive need to just can be used for detecting gas (often need be heated under the operating temperature of hundreds of degree centigrade just preferably vapor sensitivity can be arranged) usually to sensor element under hot conditions, but the operation that high temperature detects to reality has brought many inconvenience, and the gas sensor that the research and development high sensitivity has again the room temperature response characteristic seems particularly important.Organic conductive polymkeric substance air-sensitive material is because its long-time stability are relatively poor, the drawbacks limit such as response sensitivity is low its practical application, in addition, the organic conductive polymkeric substance has also limited its application owing to insolublely do not melt, be difficult to processing.
Along with developing rapidly of nanosecond science and technology, organic conductive polymer/inorganic nanometer composite air-sensitive material becomes the quite concerned class material of gas sensor research field in recent years, the large specific surface area that its unique nanostructured is brought is conducive to gas absorption and diffusion, can make gas sensor add fast-response, improve the response recovery, be conducive to simultaneously the raising of its response sensitivity; And have cooperative effect toward contact between two kinds of gas sensitives of organic conductive polymkeric substance and inorganic semiconductor, can significantly improve the response sensitivity of gas sensor, and be conducive to the increase of its stability, and can realize that the room temperature of gas detects.
The organic conductive polymkeric substance air-sensitive material that often has has polyaniline, polypyrrole and polythiophene etc., the inorganic semiconductor gas sensitive has carbon nano-tube, titania, zinc paste, tin ash etc., but the at present many employings of organic conductive polymer/inorganic nanometer composite air-sensitive material take polymer monomer (such as aniline, pyrroles, thiophene) as monomer carries out polyreaction, make respectively polyaniline/inorganic nano air-sensitive compound substance, polypyrrole/inorganic nano air-sensitive compound substance, polythiophene // inorganic nano air-sensitive compound substance under the condition that inorganic nano-particle exists.Existing bibliographical information Polyaniline/Titanium Oxide Composite Thin Films gas sensor functional material and preparation method thereof (H.L. Tai, Y.D. Jiang, G.Z. Xie, J.S. Yu, X. Chen, Sensor Actuat. B-Chem. 125 (2007) 644-650; The favour tinkling of pieces of jade too, Jiang Yadong, Xie Guangzhong, Du Xiaosong, Chen Xuan, the preparation of Polyaniline/Titanium Oxide Composite Thin Films and air-sensitive performance thereof, Acta PhySico-Chimica Sinica, 2007,23 (6): 883-888), blank electrode is placed nano titania colloid and aniline monomer solution, the initiation aniline monomer carries out the in-situ solution polymerization and makes the Polyaniline/Titanium Oxide Composite Thin Films gas sensitive, have higher gas detection sensitivity and faster response with this gas sensitive as the gas sensor of sensitive function layer, shown the excellent properties of polyaniline/titanium dioxide nano compound film as gas sensitive.But the defectives such as preparation process is difficult to control, preparation element consistance is poor that said method exists, with the gas sensor sensitive membrane of the method preparation usually thicker (several microns to the hundreds of micron), and the conducting polymer residue that existence can't reuse in a large number in the product, difficult treatment works the mischief to environment.And the gas sensor laminated film that adopts this method to make has the nanofiber of random arrangement or nano wire forms, and that should not control sensitive membrane and sensor base contacts less stable.
Traditional conducting polymers such as polyaniline are insoluble not molten, this has caused great difficulty to operations such as device film forming, than the acid of the organic molecules such as other traditional inorganic molecules acid such as hydrochloric acid, sulfuric acid, nitric acid or camphorsulfonic acid, the polyaniline that mixes with polystyrolsulfon acid has good water dispersible, be easy to process operation, and flux is water, more environmental protection.It is simple to have equally method with the titanium dioxide nano-particle of sol-gal process preparation, and particle diameter is controlled, and easy operating has been avoided the processes such as high-temperature calcination, has realized equally energy-conserving and environment-protective.The layer upon layer electrostatic self assembly is a kind of self-assembled composite film that utilizes electrostatic attraction between material to prepare nano-level, its process is very simple, easily control, because the polyaniline of aqueous dispersion is electronegative, and titanium dioxide nano-particle positively charged under sour environment, so can be easily prepare polyaniline/titanium dioxide nano composite air-sensitive film with the method for layer upon layer electrostatic self assembly, with the conducting polymer of the method preparation/inorganic nano combined gas sensor, be expected to realize under the room temperature the good air-sensitive response characteristic for gas.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide, this gas sensor at room temperature has higher response sensitivity for gas to be measured, and response is fast, recovery is good, and has better stability.
For this reason, the present invention adopts following technical scheme:
The nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide, comprise the ceramic matrix that sets gradually, interdigital gold electrode and air-sensitive film, be connected with lead-in wire at described interdigital gold electrode, at described ceramic matrix surface deposition interdigital gold electrode is arranged, deposit air-sensitive film at described ceramic matrix and interdigital gold electrode surfaces, described air-sensitive film is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and the upper polyaniline layer that covers thereof.
As preferably, the interdigital gold electrode of described ceramic matrix surface deposition is 5～16 pairs, and the interdigital width of interdigital gold electrode 2 is 20～200 μ m, and interdigital gap is 20～200 μ m;
As preferably, the thickness of described air-sensitive film is 100～600 nm;
As preferably, described polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film is to make by the polyaniline that layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid mix;
As preferably, described polyaniline layer is the polyaniline that polystyrolsulfon acid mixes;
As preferably, the mean grain size of described titanium dioxide nano-particle is 5 ~ 50 nm, and the mean grain size of the polyaniline that polystyrolsulfon acid mixes is 2 ~ 10 nm;
The air-sensitive film of gas sensor of the present invention is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and the upper polyaniline layer that covers thereof, two kinds of semiconductors of polyaniline and titania have played good cooperative effect, have greatly improved the performance of sensor; The introducing of titanium dioxide nano-particle can improve roughness of film in the laminated film, increase specific surface area, be conducive to the raising of response sensitivity and response speed, and the p/n that exists between p-type semiconductor polyaniline and N-shaped semiconductor titania knot, with promoting the charge migration of air-sensitive film, be conducive to the increase of response sensitivity.And, titanium dioxide nano-particle has been realized in the laminated film orderly between layers arrangement, make between the dissimilar semiconductors to meet effect more direct, and the number of plies that can regulate self-assembled film, directly can realize the regulation and control to film thickness, be the regulation and control of complex effect power, the regulation and control of more convenient device performance.The film that carries out self assembly by static has more closely adhesion, makes the sensor sensing film that makes have better stability.
The polyaniline layer has good electric conductivity, reduce the impedance of gas sensor, avoid because introduce titania the electric conductivity of element being reduced, thereby be difficult to test it for the room temperature response characteristic that detects gas, the polyaniline layer can play the effect of good reduction sensor sensing membrane impedance, and can improve the performance of adsorbed gas.
Second purpose of the present invention provides the method for the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide, comprises the steps:
1) deposits interdigital gold electrode on the ceramic matrix surface by the method for evaporation or photoetching, make the ceramic matrix with interdigital gold electrode;
2) process the ceramic matrix with interdigital gold electrode, make the ceramic matrix with interdigital gold electrode of modified;
3) ceramic matrix with interdigital gold electrode at modified deposits polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film;
4) at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film deposition polyaniline layer, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Above-mentioned steps all can at room temperature be carried out.
Particularly,
Described step 2) comprises the steps:
1. soak the ceramic matrix 20 ~ 40 minutes with interdigital gold electrode with Piranha solution, dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas, like this so that have negative charge group on the ceramic matrix band of interdigital gold electrode, and flush away other unnecessary impurity;
2. then the ceramic matrix that dries up was immersed in the PDDA aqueous solution that concentration is 1～3%wt 5～10 minutes, and took out and dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas;
3. the ceramic matrix that 2. step dried up immersed in the kayexalate that concentration is 1～3%wt 5～10 minutes, took out to dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas;
4. successively repeating step 2. with step 3. 2～5 times, obtain the ceramic matrix with interdigital gold electrode of modified, make so more negative charge group on the ceramic matrix band with interdigital gold electrode, can have better adhesiveness with the layer upon layer electrostatic self assembly laminated film that deposits afterwards.
Described Piranha solution is a kind of potent cleaning solution, by the 7 parts of concentrated sulphuric acid (H by volume
2SO4) and 3 part 30% hydrogen peroxide (H
2O
2) form.
Described step 3) comprises the steps:
1. polystyrolsulfon acid is put into the water wiring solution-forming, then add aniline monomer, after stirring, add again ammonium persulfate, stop after stirring stirring, reactant reacted in ice-water bath 3 ~ 8 hours, made the polyaniline that polystyrolsulfon acid mixes, the mol ratio of described polystyrolsulfon acid and aniline monomer is 1:1, and the mol ratio of ammonium persulfate and aniline monomer is 1:1;
2. the ceramic matrix with interdigital gold electrode of modified is immersed concentration and is the titanium dioxide nano-particle aqueous solution 5～10 minutes of 1～3 mg/mL, taking-up is 1.5 sour drip washing 1～2 minute with the pH value and dries up with nitrogen or argon gas that described acid is hydrochloric acid, sulfuric acid or nitric acid;
By each pickling, can well control the titanium dioxide nano-particle thickness in each self assembly, can the flush away unnecessary firmly titanium dioxide nano-particle that is not adsorbed;
3. then the ceramic matrix that dries up is immersed concentration and is the polyaniline aqueous solution 5～10 minutes that 1～3 mg/mL polystyrolsulfon acid mixes, taking-up is 1.5 sour drip washing 1～2 minute with the pH value and dries up with nitrogen or argon gas that described acid is hydrochloric acid, sulfuric acid or nitric acid;
By each pickling, can well control the polyaniline thickness that the polystyrolsulfon acid in each self assembly mixes, can flush away unnecessary be adsorbed the polyaniline that polystyrolsulfon acid firmly mixes;
4. successively repeating step 2. with step 3. 5～40 times, obtain depositing the ceramic matrix of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film.
Described step 4) comprises the steps:
It is the polystyrolsulfon acid of 1～3 mg/mL polyaniline aqueous solution of mixing 5～10 minutes that the ceramic matrix that 1. will deposit polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film immerses concentration;
2. take out with nitrogen or argon gas and dry up, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film deposition polyaniline layer, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Among the preparation method of the present invention, described interdigital gold electrode is 5～16 pairs, and the interdigital width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
Preparation method's process flow diagram of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention is seen Fig. 3, at first at the interdigital gold electrode of ceramic matrix deposition, then with the ceramic matrix with interdigital gold electrode of Piranha solution-treated, the ceramic matrix with interdigital gold electrode of Piranha solution-treated, make it be with more negative charge group, and make the polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film of subsequent deposition have better adhesiveness; Then adopt kayexalate and PDDA that the ceramic matrix with interdigital gold electrode is modified in advance, can significantly improve the polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film of subsequent deposition and the adhesiveness between the ceramic matrix, thereby significantly improve the long-time stability of gas sensor; Layer by layer electrostatic self-assembled titanium dioxide nano-particle and polyaniline on the ceramic matrix with interdigital gold electrode of modified make polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film; Deposit again one deck polyaniline layer, make the sensitive membrane of whole sensor have lower impedance, and have better gas absorption performance, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Advantage of the present invention is as follows:
1) air-sensitive film of gas sensor of the present invention is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and the upper polyaniline layer that covers thereof, two kinds of semiconductors of polyaniline and titania have played good cooperative effect, have greatly improved the performance of sensor;
2) on layer upon layer electrostatic self assembly polyaniline/titanium dioxide nano compound film, cover again the polyaniline layer, can utilize the good electric conductivity of polyaniline, reduce the impedance of gas sensor, avoid because introduce titania the electric conductivity of element being reduced, thereby be difficult to test it for the room temperature response characteristic that detects gas;
3) the air-sensitive film thickness of gas sensor of the present invention is thinner, be conducive to adsorption and desorption and the diffusion of gas to be measured, make sensor have very high response sensitivity, good recovery and fast response (response and turnaround time are all less than 1 minute);
4) the present invention adopts the layer upon layer electrostatic self-assembly method to prepare polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film, has good adhesion between each film functional layer, so that laminated film has fabulous stability, and the number of plies by the control self assembly, can accurately control the thickness of gas sensitization film, thereby regulate the sensor sensing performance;
5) polyaniline that mixes of the polystyrolsulfon acid that makes of the present invention has water-solublely, can be dispersed in water well, has solved the unmanageable difficulty of polyaniline;
6) the present invention prepare the method for gas sensor simple to operate, with low cost, be applicable to large-scale industrial production.
Description of drawings
Fig. 1 is the structural representation of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention;
Fig. 2 is the structural representation of the air-sensitive film 3 of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention;
Fig. 3 is the preparation flow figure of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention;
Fig. 4 is that the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide that makes of the embodiment of the invention 1 is for the response characteristic figure of ammonia;
Fig. 5 is that the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide that the embodiment of the invention 1 makes is schemed for the response repeatability of ammonia;
Fig. 6 be sensor of the present invention the polyaniline/titanium dioxide nanometer layer by layer the self assembly number of plies of Electrostatic Self-Assembled Films for the response diagram of gas sensor to ammonia;
Fig. 7 is the polyaniline particle of polystyrolsulfon acid doping of the present invention and the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle, (a) (b) is the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle for the scanning electron microscope (SEM) photograph of the polyaniline particle of polystyrolsulfon acid doping among the figure;
Fig. 8 is the scanning electron microscope (SEM) photograph of the air-sensitive film of sensor of the present invention;
Fig. 9 is the uv absorption spectra of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film in the sensor air-sensitive film of the present invention.
Shown in the figure: 1. ceramic matrix, 2. interdigital gold electrode, 3. gas sensitization film, 4. contact conductor,
5. layer upon layer electrostatic self assembly sensitive layer, 6. polyaniline layer.
Embodiment
Further specify the present invention below in conjunction with drawings and Examples.
As depicted in figs. 1 and 2, the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention, comprise the ceramic matrix 1, interdigital gold electrode 2 and the air-sensitive film 3 that set gradually, be connected with lead-in wire 4 at described interdigital gold electrode, at described ceramic matrix surface deposition interdigital gold electrode 2 is arranged, at described ceramic matrix 1 and interdigital gold electrode 2 surface depositions air-sensitive film 3 is arranged, described air-sensitive film 3 is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 and the upper polyaniline layer 6 that covers thereof.
Air-sensitive film 3 of the present invention is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 and the upper polyaniline layer 6 that covers thereof, and wherein the thickness of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 is to regulate and control by the change of the control self assembly number of plies.
As preferably, the interdigital gold electrode 2 of described ceramic matrix surface deposition is 5～16 pairs, and the interdigital width of interdigital gold electrode 2 is 20～200 μ m, and interdigital gap is 20～200 μ m;
As preferably, the thickness of described air-sensitive film 3 is 100～600 nm;
As preferably, described polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 is to make by the polyaniline that layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid mix;
As preferably, described polyaniline layer 6 is the water dispersible polyanilines that mix through polystyrolsulfon acid;
As preferably, the mean grain size of described titanium dioxide nano-particle is 5 ~ 50nm, and the mean grain size of water dispersible polyanilines is 2 ~ 10 nm.
The present invention also provides the preparation method of the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide, comprises the steps:
1) deposits interdigital gold electrode 2 on ceramic matrix 1 surface by the method for evaporation or photoetching, make the ceramic matrix 1 with interdigital gold electrode;
2) process the ceramic matrix 1 with interdigital gold electrode, make the ceramic matrix with interdigital gold electrode 1 of modified;
3) ceramic matrix with interdigital gold electrode 1 at modified deposits polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5;
4) at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposition polyaniline layers 6, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Described interdigital gold electrode is 5～16 pairs, and the interdigital width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m
The below describes the preparation method of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide in detail.
Embodiment 1:
(1) depositing 5 pairs of interdigital width on ceramic matrix 1 surface by evaporation method is 200 μ m, and interdigital gap is the interdigital gold electrode 2 of 200 μ m, makes the ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2SO4) and 3 part 30% hydrogen peroxide (H
2O
2) form) soak the ceramic matrix 30 minutes with interdigital gold electrode under the room temperature, with deionized water drip washing 2 minutes, and dry up with nitrogen;
(3) ceramic matrix 1 that dries up is immersed in the PDDA aqueous solution that concentration is 2%wt 5 minutes, take out and dry up with deionized water drip washing 1 minute and with nitrogen;
(4) ceramic matrix that dries up 1 that step (3) is made immersed in the kayexalate that concentration is 2%wt 10 minutes, took out to dry up with deionized water drip washing 2 minutes and with nitrogen;
(5) successively repeating step (3) and step (4) 2 times obtain the ceramic matrix with interdigital gold electrode 1 of modified;
(6) taking by weighing 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in the 20mL water, in ice-water bath, add 0.2mL aniline (with the mol ratio of aniline monomer be 1:1), continue to stir 1 hour, then slowly drip the 0.5g ammonium persulfate (with the mol ratio of aniline monomer be 1:1), stop after stirring stirring, reaction is 6 hours in ice-water bath, make the polyaniline that polystyrolsulfon acid mixes, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 2mg/mL;
The ceramic matrix with interdigital gold electrode 1 of the modified that (7) step (5) is made immerses the titanium dioxide nano-particle aqueous solution 10 minutes that concentration is 2 mg/mL, takes out with the pH value to be 1.5 hydrochloric acid drip washing 2 minutes and to dry up with nitrogen;
(8) it is the polystyrolsulfon acid of the 2 mg/mL polyaniline aqueous solution of mixing 10 minutes that the ceramic matrix with interdigital gold electrode 1 that step (7) is made immerses concentration that step (6) makes, takes out with the pH value to be 1.5 hydrochloric acid drip washing 2 minutes and to dry up with nitrogen;
(9) successively repeating step (7) and step (8) 15 times obtain depositing the layer by layer ceramic matrix 1 of Electrostatic Self-Assembled Films 5 of polyaniline/titanium dioxide nanometer;
(10) step (9) is made deposit the polyaniline/titanium dioxide nanometer layer by layer the ceramic matrix 1 of Electrostatic Self-Assembled Films 5 to immerse concentration that step (6) makes be the polystyrolsulfon acid of the 2 mg/mL polyaniline aqueous solution of mixing 10 minutes, taking-up dries up with nitrogen, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposition polyaniline layers 6, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide and for gas to be measured very high sensitivity and response repeatability are arranged, as shown in Figure 4, the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention's preparation at room temperature has highly sensitive response for the ammonia of 5-200 ppm, and response has good recovery; As shown in Figure 5, the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the present invention's preparation at room temperature carries out a plurality of loop tests for the ammonia of 50 ppm, and its response has good repeatability.
For investigate the polyaniline/titanium dioxide nanometer layer by layer the self assembly number of plies of Electrostatic Self-Assembled Films for the impact of gas sensor performance, embodiment 2～5 only changes in embodiment 1 step (9) the successively number of times of repeating step (7) and step (8), and all the other conditions are identical with embodiment 1.
Embodiment 2:
Step (9): repeating step (7) and step are (8) 5 times successively, and all the other conditions are identical with embodiment 1.
Embodiment 3:
Step (9): repeating step (7) and step are (8) 10 times successively, and all the other conditions are identical with embodiment 1.
Embodiment 4:
Step (9): repeating step (7) and step are (8) 20 times successively, and all the other conditions are identical with embodiment 1.
Embodiment 5:
Step (9): repeating step (7) and step are (8) 40 times successively, and all the other conditions are identical with embodiment 1.
Fig. 6 be sensor of the present invention the polyaniline/titanium dioxide nanometer layer by layer the self assembly number of plies of Electrostatic Self-Assembled Films for the response diagram of gas sensor to ammonia, as shown in Figure 6, the self assembly number of plies of electrostatic self-assembled laminated film has a significant effect for the response characteristic of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Embodiment 6:
(1) depositing 16 pairs of interdigital width on ceramic matrix 1 surface by evaporation method is 20 μ m, and interdigital gap is the interdigital gold electrode 2 of 20 μ m, makes the ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2SO4) and 3 part 30% hydrogen peroxide (H
2O
2) form) soak the ceramic matrix 20 minutes with interdigital gold electrode under the room temperature, with deionized water drip washing 1 minute, and dry up with nitrogen;
(3) ceramic matrix 1 that dries up is immersed in the PDDA aqueous solution that concentration is 1%wt 5 minutes, take out and dry up with deionized water drip washing 1 minute and with nitrogen;
(4) ceramic matrix that dries up 1 that step (3) is made immersed in the kayexalate that concentration is 1%wt 5 minutes, took out to dry up with deionized water drip washing 1 minute and with nitrogen;
(5) successively repeating step (3) and step (4) 2 times obtain the ceramic matrix with interdigital gold electrode 1 of modified;
(6) taking by weighing 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in the 20mL water, in ice-water bath, add 0.2mL aniline (with the mol ratio of aniline monomer be 1:1), continue to stir 1 hour, then slowly drip the 0.5g ammonium persulfate (with the mol ratio of aniline monomer be 1:1), stop after stirring stirring, reaction is 3 hours in ice-water bath, make the polyaniline that polystyrolsulfon acid mixes, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 1 mg/mL;
The ceramic matrix with interdigital gold electrode 1 of the modified that (7) step (5) is made immerses the titanium dioxide nano-particle aqueous solution 5 minutes that concentration is 1 mg/mL, takes out with the pH value to be 1.5 hydrochloric acid drip washing 1 minute and to dry up with nitrogen;
(8) it is the polystyrolsulfon acid of the 1 mg/mL polyaniline aqueous solution of mixing 5 minutes that the ceramic matrix with interdigital gold electrode 1 that step (7) is made immerses concentration that step (6) makes, takes out with the pH value to be 1.5 hydrochloric acid drip washing 1 minute and to dry up with nitrogen;
(9) successively repeating step (7) and step (8) 10 times obtain depositing the layer by layer ceramic matrix 1 of Electrostatic Self-Assembled Films 5 of polyaniline/titanium dioxide nanometer;
(10) step (9) is made deposit the polyaniline/titanium dioxide nanometer layer by layer the ceramic matrix 1 of Electrostatic Self-Assembled Films 5 to immerse concentration that step (6) makes be the polystyrolsulfon acid of the 1 mg/mL polyaniline aqueous solution of mixing 5 minutes, taking-up dries up with nitrogen, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposition polyaniline layers 6, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Embodiment 7:
(1) depositing 10 pairs of interdigital width on ceramic matrix 1 surface by photoetching process is 100 μ m, and interdigital gap is the interdigital gold electrode 2 of 100 μ m, makes the ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2SO4) and 3 part 30% hydrogen peroxide (H
2O
2) form) soak the ceramic matrix 30 minutes with interdigital gold electrode under the room temperature, with deionized water drip washing 2 minutes, and dry up with argon gas;
(3) ceramic matrix 1 that dries up is immersed in the PDDA aqueous solution that concentration is 3%wt 10 minutes, take out and dry up with deionized water drip washing 2 minutes and with argon gas;
(4) ceramic matrix that dries up 1 that step (3) is made immersed in the kayexalate that concentration is 3%wt 10 minutes, took out to dry up with deionized water drip washing 2 minutes and with argon gas;
(5) successively repeating step (3) and step (4) 5 times obtain the ceramic matrix with interdigital gold electrode 1 of modified;
(6) taking by weighing 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in the 20mL water, in ice-water bath, add 0.2mL aniline (with the mol ratio of aniline monomer be 1:1), continue to stir 1 hour, then slowly drip the 0.5g ammonium persulfate (with the mol ratio of aniline monomer be 1:1), stop after stirring stirring, reaction is 5 hours in ice-water bath, make the polyaniline that polystyrolsulfon acid mixes, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 3mg/mL;
The ceramic matrix with interdigital gold electrode 1 of the modified that (7) step (5) is made immerses the titanium dioxide nano-particle aqueous solution 10 minutes that concentration is 3 mg/mL, takes out with the pH value to be 1.5 sulfuric acid drip washing 2 minutes and to dry up with argon gas;
(8) it is the polystyrolsulfon acid of the 3 mg/mL polyaniline aqueous solution of mixing 10 minutes that the ceramic matrix with interdigital gold electrode 1 that step (7) is made immerses concentration that step (6) makes, takes out with the pH value to be 1.5 sulfuric acid drip washing 2 minutes and to dry up with argon gas;
(9) successively repeating step (7) and step (8) 5 times obtain depositing the layer by layer ceramic matrix 1 of Electrostatic Self-Assembled Films 5 of polyaniline/titanium dioxide nanometer;
(10) step (9) is made deposit the polyaniline/titanium dioxide nanometer layer by layer the ceramic matrix 1 of Electrostatic Self-Assembled Films 5 to immerse concentration that step (6) makes be the polystyrolsulfon acid of the 3 mg/mL polyaniline aqueous solution of mixing 10 minutes, taking-up dries up with argon gas, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposition polyaniline layers 6, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Embodiment 8:
(1) depositing 8 pairs of interdigital width on ceramic matrix 1 surface by photoetching process is 150 μ m, and interdigital gap is the interdigital gold electrode 2 of 150 μ m, makes the ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2SO4) and 3 part 30% hydrogen peroxide (H
2O
2) form) soak the ceramic matrix 40 minutes with interdigital gold electrode under the room temperature, with deionized water drip washing 1 minute, and dry up with nitrogen;
(3) ceramic matrix 1 that dries up is immersed in the PDDA aqueous solution that concentration is 2%wt 6 minutes, take out and dry up with deionized water drip washing 1 minute and with nitrogen;
(4) ceramic matrix that dries up 1 that step (3) is made immersed in the kayexalate that concentration is 2%wt 7 minutes, took out to dry up with deionized water drip washing 1 minute and with nitrogen;
(5) successively repeating step (3) and step (4) 3 times obtain the ceramic matrix with interdigital gold electrode 1 of modified;
(6) taking by weighing 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in the 20mL water, in ice-water bath, add 0.2mL aniline (with the mol ratio of aniline monomer be 1:1), continue to stir 1 hour, then slowly drip the 0.5g ammonium persulfate (with the mol ratio of aniline monomer be 1:1), stop after stirring stirring, reaction is 8 hours in ice-water bath, make the polyaniline that polystyrolsulfon acid mixes, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 2mg/mL;
The ceramic matrix with interdigital gold electrode 1 of the modified that (7) step (5) is made immerses the titanium dioxide nano-particle aqueous solution 7 minutes that concentration is 2 mg/mL, takes out with the pH value to be 1.5 nitric acid drip washing 1 minute and to dry up with nitrogen;
(8) it is the polystyrolsulfon acid of the 2 mg/mL polyaniline aqueous solution of mixing 7 minutes that the ceramic matrix with interdigital gold electrode 1 that step (7) is made immerses concentration that step (6) makes, takes out with the pH value to be 1.5 nitric acid drip washing 1 minute and to dry up with nitrogen;
(9) successively repeating step (7) and step (8) 20 times obtain depositing the layer by layer ceramic matrix 1 of Electrostatic Self-Assembled Films 5 of polyaniline/titanium dioxide nanometer;
(10) step (9) is made deposit the polyaniline/titanium dioxide nanometer layer by layer the ceramic matrix 1 of Electrostatic Self-Assembled Films 5 to immerse concentration that step (6) makes be the polystyrolsulfon acid of the 2 mg/mL polyaniline aqueous solution of mixing 7 minutes, taking-up dries up with nitrogen, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposition polyaniline layers 6, make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
The polyaniline particle that polystyrolsulfon acid of the present invention mixes and the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle are seen Fig. 7, (a) is the scanning electron microscope (SEM) photograph of the polyaniline particle of polystyrolsulfon acid doping among the figure, (b) be the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle, as can be seen from Figure 7, the particle diameter of the polyaniline particle that polystyrolsulfon acid mixes only has several nanometers, and the particle diameter of titanium dioxide nano-particle is tens nanometers.
Fig. 8 is the scanning electron microscope (SEM) photograph of the air-sensitive film of sensor of the present invention, and the thickness of air-sensitive film is very little as shown in Figure 8, only is the hundreds of nanometer.
The amount of polyaniline and titania is certain in each layer upon layer electrostatic self assembly in order to characterize, can the uv absorption intensity of electrostatic self-assembled laminated film film illustrates by testing layer by layer, Fig. 9 is the uv absorption spectra of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film of the present invention, as seen from Figure 9, the uv absorption intensity self assembly number of plies linear growth of laminated film proves the polyaniline of polystyrolsulfon acid doping and the realization of titanium dioxide nano-particle electrostatic self-assembled process.
Above-described embodiment only is not used in for explanation the present invention and limits the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide, comprise the ceramic matrix (1) that sets gradually, interdigital gold electrode (2) and air-sensitive film (3), be connected with lead-in wire (4) at described interdigital gold electrode, it is characterized in that: at described ceramic matrix surface deposition interdigital gold electrode (2) is arranged, at described ceramic matrix (1) and interdigital gold electrode (2) surface deposition air-sensitive film (3) is arranged, described air-sensitive film (3) is comprised of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) and the upper polyaniline layer (6) that covers thereof.
2. the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide according to claim 1, it is characterized in that: the interdigital gold electrode (2) of described ceramic matrix surface deposition is 5～16 pairs, the interdigital width of interdigital gold electrode (2) is 20～200 μ m, and interdigital gap is 20～200 μ m.
3. the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide according to claim 1, it is characterized in that: the thickness of described air-sensitive film (3) is 100～600 nm.
4. the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide according to claim 1 is characterized in that: described polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) is to make by the polyaniline that layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid mix.
5. the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide according to claim 1 is characterized in that: described polyaniline layer (6) is the polyaniline that polystyrolsulfon acid mixes.
6. the preparation method of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide is characterized in that comprising the steps:
1) method by evaporation or photoetching deposits interdigital gold electrode (2) on ceramic matrix (1) surface, makes the ceramic matrix (1) with interdigital gold electrode;
2) process the ceramic matrix (1) with interdigital gold electrode, make the ceramic matrix with interdigital gold electrode (1) of modified;
3) ceramic matrix with interdigital gold electrode (1) at modified deposits polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5);
4) at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) deposition polyaniline layer (6), make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
7. preparation method according to claim 6 is characterized in that described step 2) comprise the steps:
1. soak the ceramic matrix (1) 20 ~ 40 minute with interdigital gold electrode with Piranha solution, dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas;
2. then the ceramic matrix (1) that dries up was immersed in the PDDA aqueous solution that concentration is 1～3%wt 5～10 minutes, and took out and dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas;
3. the ceramic matrix that 2. step is dried up (1) immersed in the kayexalate that concentration is 1～3%wt 5～10 minutes, took out to dry up with deionized water drip washing 1～2 minute and with nitrogen or argon gas;
4. successively repeating step 2. with step 3. 2～5 times, obtain the ceramic matrix with interdigital gold electrode (1) of modified.
8. preparation method according to claim 6 is characterized in that described step 3) comprise the steps:
1. polystyrolsulfon acid is put into the water wiring solution-forming, then add aniline monomer, after stirring, add again ammonium persulfate, stop after stirring stirring, reactant reacted in ice-water bath 3 ~ 8 hours, made the polyaniline that polystyrolsulfon acid mixes, the mol ratio of described polystyrolsulfon acid and aniline monomer is 1:1, and the mol ratio of ammonium persulfate and aniline monomer is 1:1;
2. the ceramic matrix with interdigital gold electrode (1) of modified is immersed concentration and is the titanium dioxide nano-particle aqueous solution 5～10 minutes of 1～3 mg/mL, taking-up is 1.5 sour drip washing 1～2 minute with the pH value and dries up with nitrogen or argon gas that described acid is hydrochloric acid, sulfuric acid or nitric acid;
3. then the ceramic matrix (1) that dries up is immersed concentration and is the polyaniline aqueous solution 5～10 minutes that 1～3 mg/mL polystyrolsulfon acid mixes, taking-up is 1.5 sour drip washing 1～2 minute with the pH value and dries up with nitrogen or argon gas that described acid is hydrochloric acid, sulfuric acid or nitric acid;
4. successively repeating step 2. with step 3. 5～40 times, obtain depositing the ceramic matrix (1) of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5).
9. preparation method according to claim 6 is characterized in that described step 4) comprise the steps:
It is the polystyrolsulfon acid of 1～3 mg/mL polyaniline aqueous solution of mixing 5～10 minutes that the ceramic matrix (1) that 1. will deposit polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) immerses concentration;
2. take out with nitrogen or argon gas and dry up, at polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) deposition polyaniline layer (6), make the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
10. according to claim 6 to 9 each described preparation methods, described interdigital gold electrode is 5～16 pairs, and the interdigital width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
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