CN102866181B - 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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- CN102866181B CN102866181B CN201210376831.XA CN201210376831A CN102866181B CN 102866181 B CN102866181 B CN 102866181B CN 201210376831 A CN201210376831 A CN 201210376831A CN 102866181 B CN102866181 B CN 102866181B
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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 in storage, commercial production, process control, environmental monitoring etc., and play a part to become more and more important in modern development in science and technology and people's life, constantly pursue high-performance, low cost, small size etc. become a sensor industry difficult problem urgently 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 the large class of organic conductive polymer two.Inorganic semiconductor gas sensitive needs just to be used under the high temperature conditions to detect gas (just can have good vapor sensitivity under often needing that sensor element is heated to the operating temperature of hundreds of degree Celsius) usually, but high temperature detects and brings much inconvenience to the operation of reality, the gas sensor that research and development high sensitivity has again room temperature response characteristic seems particularly important.Organic conductive polymer gas sensitive is because its long-time stability are poor, and its practical application of the drawbacks limit such as response sensitivity is low, in addition, organic conductive polymer, owing to insolublely not melt, to be difficult to processing, also limit its application.
Along with developing rapidly of nanosecond science and technology, organic conductive polymer in recent years/inorganic nano combined gas sensitive becomes the quite concerned class material of gas sensor research field, the large specific surface area that the nanostructured of its uniqueness is brought is conducive to gas absorption and diffusion, gas sensor can be made to add fast-response, improve response recovery, be conducive to the raising of its response sensitivity simultaneously; And toward contact, there is cooperative effect between organic conductive polymer and inorganic semiconductor two kinds of gas sensitives, the response sensitivity of gas sensor can be significantly improved, and be conducive to the increase of its stability, and the room temperature that can realize gas detects.
The organic conductive polymer gas sensitive often had has polyaniline, polypyrrole and polythiophene etc., inorganic semiconductor gas sensitive has carbon nano-tube, titania, zinc paste, tin ash etc., but at present organic conductive polymer/many employings of inorganic nano combined gas sensitive under inorganic nano-particle existent condition with polymer monomer (as aniline, pyrroles, thiophene) for monomer carries out polyreaction, obtained polyaniline/inorganic nano air-sensitive compound substance, polypyrrole/inorganic nano air-sensitive compound substance, polythiophene // inorganic nano air-sensitive compound substance respectively.Have 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 too favour tinkling of pieces of jade, 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 in nano titania colloid and aniline monomer solution, cause aniline monomer and carry out the obtained Polyaniline/Titanium Oxide Composite Thin Films gas sensitive of in-situ solution polymerization, using this gas sensitive as the gas sensor of sensitive function layer, there is higher gas detect sensitivity and respond faster, show the excellent properties of polyaniline/titanium dioxide nano compound film as gas sensitive.But said method also exists preparation process to be difficult to control, prepare the defects such as element consistance difference, the gas sensor sensitive membrane prepared by the method is thicker (several microns to hundreds of micron) usually, and in product, there is the conducting polymer residue that cannot reuse in a large number, difficult treatment, works the mischief to environment.Further, adopt nanofiber or nano wire composition that gas sensor laminated film obtained in this way has random arrangement, the contact of sensitive membrane and sensor base should not be controlled, less stable.
The conducting polymers such as traditional polyaniline are insoluble not molten, this causes great difficulty to operations such as device film forming, compared to other organic molecule acid such as the acid of traditional inorganic molecules or camphorsulfonic acid such as hydrochloric acid, sulfuric acid, nitric acid, with the polyaniline of polystyrolsulfon acid doping, there is good water dispersible, be easy to process operation, and flux is water, more environmental protection.It is simple that the titanium dioxide nano-particle prepared with sol-gal process has method equally, size tunable, is easy to operation, avoids the processes such as high-temperature calcination, achieve energy-conserving and environment-protective equally.Layer upon layer electrostatic self assembly a kind ofly utilizes the electrostatic attraction between material to prepare the self-assembled composite film of nano-level, its process is very simple, easy control, because the polyaniline of aqueous dispersion is electronegative, and titanium dioxide nano-particle positively charged under sour environment, so polyaniline/titanium dioxide nano composite air-sensitive film can be prepared by the method for layer upon layer electrostatic self assembly easily, the conducting polymer prepared by the method/inorganic nano combined gas sensor, is expected to realize the excellent air-sensitive response characteristic for gas under room temperature.
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 set gradually, interdigital gold electrode and air-sensitive film, described interdigital gold electrode is connected with lead-in wire, interdigital gold electrode is had at described ceramic matrix surface deposition, deposit air-sensitive film at described ceramic matrix and interdigital gold electrode surfaces, described air-sensitive film is made up of the polyaniline of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and upper covering thereof.
As preferably, the interdigital gold electrode of described ceramic matrix surface deposition is 5 ~ 16 right, and the interdigital width of interdigital gold electrode 2 is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm;
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 polyaniline by layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid doping and obtained;
As preferably, described polyaniline is the polyaniline of polystyrolsulfon acid doping;
As preferably, the mean grain size of described titanium dioxide nano-particle is 5 ~ 50 nm, and the mean grain size of the polyaniline of polystyrolsulfon acid doping is 2 ~ 10 nm;
The air-sensitive film of gas sensor of the present invention is made up of the polyaniline of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and upper covering thereof, polyaniline and titania two kinds of semiconductors serve good cooperative effect, substantially increase the performance of sensor; In laminated film, the introducing of titanium dioxide nano-particle can improve roughness of film, increase specific surface area, be conducive to the raising of response sensitivity and response speed, and the p/n existed between p-type semiconductor polyaniline and n-type semiconductor titania ties, by promoting the charge migration of air-sensitive film, be conducive to the increase of response sensitivity.And, titanium dioxide nano-particle achieves arrangement orderly between layers in laminated film, make between dissimilar semiconductor to meet effect more direct, and the number of plies of self-assembled film can be regulated, directly can realize the regulation and control to film thickness, the i.e. regulation and control of complex effect power, the regulation and control of more convenient device performance.The film being carried out self assembly by electrostatic has adhesion more closely, makes the sensor sensing film obtained have better stability.
Polyaniline has good electric conductivity, reduce the impedance of gas sensor, avoid because introduce titania, the electric conductivity of element being reduced, thus be difficult to test it for the room temperature response characteristic detecting gas, polyaniline can play the effect well reducing sensor sensing membrane impedance, and can improve the performance of adsorbed gas.
Second object of the present invention is to provide the method for the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide, comprises the steps:
1) interdigital gold electrode is deposited on ceramic matrix surface by the method for evaporation or photoetching, the obtained ceramic matrix with interdigital gold electrode;
2) process has the ceramic matrix of interdigital gold electrode, the ceramic matrix with interdigital gold electrode of obtained modified;
3) on the ceramic matrix with interdigital gold electrode of modified, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film is deposited;
4) on polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film, polyaniline is deposited, the obtained 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) comprise the steps:
1. the ceramic matrix 20 ~ 40 minutes with interdigital gold electrode is soaked with Piranha solution, dry up with nitrogen or argon gas with deionized water drip washing 1 ~ 2 minute, negative charge group on the ceramic matrix band making to have interdigital gold electrode like this, and washed away other unnecessary impurity;
2. then the ceramic matrix dried up being immersed concentration is in the PDDA aqueous solution of 1 ~ 3%wt 5 ~ 10 minutes, and taking-up deionized water drip washing 1 ~ 2 minute also dries up with nitrogen or argon gas;
3. it is in the kayexalate of 1 ~ 3%wt 5 ~ 10 minutes that the ceramic matrix that step 2. dried up immerses concentration, and taking-up deionized water drip washing 1 ~ 2 minute also dries up with nitrogen or argon gas;
4. repeat successively step 2. with step 3. 2 ~ 5 times, obtain the ceramic matrix with interdigital gold electrode of modified, more negative charge group on the ceramic matrix band making to have interdigital gold electrode like this, can have better adhesiveness with the layer upon layer electrostatic self assembly laminated film deposited afterwards.
Described Piranha solution is a kind of potent cleaning solution, by the 7 parts of concentrated sulphuric acid (H by volume
2hydrogen peroxide (the H of SO4) and 3 part 30%
2o
2) composition.
Described step 3) comprise the steps:
1. polystyrolsulfon acid is put into water wiring solution-forming, then aniline monomer is added, after stirring, add ammonium persulfate again, stop after stirring stirring, reactant reacts 3 ~ 8 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, described polystyrolsulfon acid and the mol ratio of aniline monomer are 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 the titanium dioxide nano-particle aqueous solution 5 ~ 10 minutes that concentration is 1 ~ 3 mg/mL, taking-up pH value is the sour drip washing 1 ~ 2 minute of 1.5 and dries up with nitrogen or argon gas, and described acid is hydrochloric acid, sulfuric acid or nitric acid;
By each pickling, the titanium dioxide nano-particle thickness in each self assembly can well be controlled, can wash away and unnecessary do not adsorbed firmly titanium dioxide nano-particle;
3. then the ceramic matrix dried up is immersed the polyaniline aqueous solution 5 ~ 10 minutes that concentration is 1 ~ 3 mg/mL polystyrolsulfon acid doping, taking-up pH value is the sour drip washing 1 ~ 2 minute of 1.5 and dries up with nitrogen or argon gas, and described acid is hydrochloric acid, sulfuric acid or nitric acid;
By each pickling, the polyaniline thickness of the polystyrolsulfon acid doping in each self assembly can well be controlled, can wash away and unnecessary do not adsorbed the polyaniline of firmly polystyrolsulfon acid doping;
4. repeat successively step 2. with step 3. 5 ~ 40 times, obtain the ceramic matrix depositing polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film.
Described step 4) comprise the steps:
1. the polyaniline aqueous solution that the polystyrolsulfon acid being 1 ~ 3 mg/mL by the ceramic matrix immersion concentration depositing polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film adulterates 5 ~ 10 minutes;
2. taking-up nitrogen or argon gas dry up, and polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film deposits polyaniline, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
In preparation method of the present invention, described interdigital gold electrode is 5 ~ 16 right, and the interdigital width of interdigital gold electrode is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm.
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 shown in Fig. 3, first on ceramic matrix, interdigital gold electrode is deposited, 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 bring 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 kayexalate and PDDA is adopted to modify in advance the ceramic matrix with interdigital gold electrode, the adhesiveness between the polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film of subsequent deposition and ceramic matrix can be significantly improved, thus significantly improve the long-time stability of gas sensor; Electrostatic self-assembled titanium dioxide nano-particle and polyaniline layer by layer on the ceramic matrix with interdigital gold electrode of modified, obtained polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film; Deposit one deck polyaniline again, make the sensitive membrane of whole sensor have lower impedance, and there is better gas absorption performance, the obtained 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 made up of the polyaniline of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film and upper covering thereof, polyaniline and titania two kinds of semiconductors serve good cooperative effect, substantially increase the performance of sensor;
2) on layer upon layer electrostatic self assembly polyaniline/titanium dioxide nano compound film, polyaniline is covered again, the electric conductivity that polyaniline is good can be utilized, reduce the impedance of gas sensor, avoid because introduce titania, the electric conductivity of element being reduced, thus be difficult to test it for the room temperature response characteristic detecting 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 response fast (respond and be all less than 1 minute turnaround time);
4) the present invention adopts layer upon layer electrostatic self-assembly method to prepare polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film, between each film functional layer, there is good adhesion, laminated film is made to have fabulous stability, and by controlling the number of plies of self assembly, accurately can control the thickness of gas sensitization film, thus regulate sensor sensing performance;
5) polyaniline that the polystyrolsulfon acid that the present invention obtains adulterates has water-soluble, can be dispersed in water well, solve 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.
Accompanying drawing explanation
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 the response characteristic figure of the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide of the embodiment of the present invention 1 for ammonia;
Fig. 5 is that the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide that the embodiment of the present invention 1 obtains is schemed for the response repeatability of ammonia;
Fig. 6 is that the self assembly number of plies of the polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films layer by layer of sensor of the present invention is for the response diagram of gas sensor to ammonia;
Fig. 7 is the polyaniline particle of polystyrolsulfon acid of the present invention doping and the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle, the scanning electron microscope (SEM) photograph of the polyaniline particle that (a) adulterates for polystyrolsulfon acid in figure, the scanning electron microscope (SEM) photograph that (b) is titanium dioxide nano-particle;
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 sensor air-sensitive film of the present invention.
Shown in 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.
Embodiment
The present invention is further illustrated 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, described interdigital gold electrode is connected with lead-in wire 4, interdigital gold electrode 2 is had at described ceramic matrix surface deposition, have air-sensitive film 3 at described ceramic matrix 1 and interdigital gold electrode 2 surface deposition, described air-sensitive film 3 is made up of the polyaniline 6 of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 and upper covering thereof.
Air-sensitive film 3 of the present invention is made up of the polyaniline 6 of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 and upper covering thereof, and wherein the thickness of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 can regulate and control by controlling the change of the self assembly number of plies.
As preferably, the interdigital gold electrode 2 of described ceramic matrix surface deposition is 5 ~ 16 right, and the interdigital width of interdigital gold electrode 2 is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm;
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 polyanilines by layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid doping and obtained;
As preferably, described polyaniline 6 is the water dispersible polyanilines through polystyrolsulfon acid doping;
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) interdigital gold electrode 2 is deposited on ceramic matrix 1 surface by the method for evaporation or photoetching, the obtained ceramic matrix 1 with interdigital gold electrode;
2) process has the ceramic matrix 1 of interdigital gold electrode, the ceramic matrix 1 with interdigital gold electrode of obtained modified;
3) on the ceramic matrix 1 with interdigital gold electrode of modified, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 is deposited;
4) on polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5, polyaniline 6 is deposited, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Described interdigital gold electrode is 5 ~ 16 right, and the interdigital width of interdigital gold electrode is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm
The preparation method of the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide is described below in detail.
Embodiment 1:
(1) depositing 5 to interdigital width on ceramic matrix 1 surface by evaporation method is 200 μm, and interdigital gap is the interdigital gold electrode 2 of 200 μm, the obtained ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2hydrogen peroxide (the H of SO4) and 3 part 30%
2o
2) composition) soak the ceramic matrix 30 minutes with interdigital gold electrode under room temperature, with deionized water drip washing 2 minutes, and dry up with nitrogen;
(3) ceramic matrix 1 dried up being immersed concentration is in the PDDA aqueous solution of 2%wt 5 minutes, and taking-up deionized water drip washing 1 minute also dries up with nitrogen;
(4) ceramic matrix 1 dried up obtained for step (3) being immersed concentration is in the kayexalate of 2%wt 10 minutes, and taking-up deionized water drip washing 2 minutes also dries up with nitrogen;
(5) repeat step (3) and step (4) 2 times successively, obtain the ceramic matrix 1 with interdigital gold electrode of modified;
(6) taking 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in 20mL water, 0.2mL aniline (be 1:1 with the mol ratio of aniline monomer) is added in ice-water bath, continue stirring 1 hour, then 0.5g ammonium persulfate (be 1:1 with the mol ratio of aniline monomer) is slowly dripped, stop after stirring stirring, react 6 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 2mg/mL;
(7) ceramic matrix 1 with interdigital gold electrode of modified obtained for step (5) is immersed the titanium dioxide nano-particle aqueous solution 10 minutes that concentration is 2 mg/mL, taking-up pH value is the hydrochloric acid drip washing 2 minutes of 1.5 and dries up with nitrogen;
(8) ceramic matrix 1 with interdigital gold electrode obtained for step (7) is immersed the polyaniline aqueous solution 10 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 2 mg/mL, taking-up pH value is the hydrochloric acid drip washing 2 minutes of 1.5 and dries up with nitrogen;
(9) repeat step (7) and step (8) 15 times successively, obtain depositing the ceramic matrix 1 of polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 layer by layer;
(10) obtained for step (9) ceramic matrix 1 depositing polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 is layer by layer immersed the polyaniline aqueous solution 10 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 2 mg/mL, taking-up nitrogen dries up, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposits polyaniline 6, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Obtained polyaniline/titanium dioxide nano combined impedance type thin film gas sensor has very high sensitivity and response repeatability for gas to be measured, as shown in Figure 4, polyaniline/titanium dioxide prepared by the present invention nano combined impedance type thin film gas sensor at room temperature has highly sensitive response for the ammonia of 5-200 ppm, and response has good recovery; As shown in Figure 5, polyaniline/titanium dioxide prepared by the present invention nano combined impedance type thin film gas sensor at room temperature carries out multiple loop test for the ammonia of 50 ppm, and its response has good repeatability.
In order to investigate the self assembly number of plies of polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films layer by layer for the impact of gas sensor performance, embodiment 2 ~ 5 only changes the number of times repeating step (7) and step (8) in embodiment 1 step (9) successively, and all the other conditions are identical with embodiment 1.
Embodiment 2:
Step (9): repeat step (7) and step (8) 5 times successively, all the other conditions are identical with embodiment 1.
Embodiment 3:
Step (9): repeat step (7) and step (8) 10 times successively, all the other conditions are identical with embodiment 1.
Embodiment 4:
Step (9): repeat step (7) and step (8) 20 times successively, all the other conditions are identical with embodiment 1.
Embodiment 5:
Step (9): repeat step (7) and step (8) 40 times successively, all the other conditions are identical with embodiment 1.
Fig. 6 is that the self assembly number of plies of the polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films layer by layer of sensor of the present invention is 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 to interdigital width on ceramic matrix 1 surface by evaporation method is 20 μm, and interdigital gap is the interdigital gold electrode 2 of 20 μm, the obtained ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2hydrogen peroxide (the H of SO4) and 3 part 30%
2o
2) composition) soak the ceramic matrix 20 minutes with interdigital gold electrode under room temperature, with deionized water drip washing 1 minute, and dry up with nitrogen;
(3) ceramic matrix 1 dried up being immersed concentration is in the PDDA aqueous solution of 1%wt 5 minutes, and taking-up deionized water drip washing 1 minute also dries up with nitrogen;
(4) ceramic matrix 1 dried up obtained for step (3) being immersed concentration is in the kayexalate of 1%wt 5 minutes, and taking-up deionized water drip washing 1 minute also dries up with nitrogen;
(5) repeat step (3) and step (4) 2 times successively, obtain the ceramic matrix 1 with interdigital gold electrode of modified;
(6) taking 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in 20mL water, 0.2mL aniline (be 1:1 with the mol ratio of aniline monomer) is added in ice-water bath, continue stirring 1 hour, then 0.5g ammonium persulfate (be 1:1 with the mol ratio of aniline monomer) is slowly dripped, stop after stirring stirring, react 3 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 1 mg/mL;
(7) ceramic matrix 1 with interdigital gold electrode of modified obtained for step (5) is immersed the titanium dioxide nano-particle aqueous solution 5 minutes that concentration is 1 mg/mL, taking-up pH value is the hydrochloric acid drip washing 1 minute of 1.5 and dries up with nitrogen;
(8) ceramic matrix 1 with interdigital gold electrode obtained for step (7) is immersed the polyaniline aqueous solution 5 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 1 mg/mL, taking-up pH value is the hydrochloric acid drip washing 1 minute of 1.5 and dries up with nitrogen;
(9) repeat step (7) and step (8) 10 times successively, obtain depositing the ceramic matrix 1 of polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 layer by layer;
(10) obtained for step (9) ceramic matrix 1 depositing polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 is layer by layer immersed the polyaniline aqueous solution 5 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 1 mg/mL, taking-up nitrogen dries up, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposits polyaniline 6, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Embodiment 7:
(1) lithographically depositing 10 to interdigital width on ceramic matrix 1 surface is 100 μm, and interdigital gap is the interdigital gold electrode 2 of 100 μm, the obtained ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2hydrogen peroxide (the H of SO4) and 3 part 30%
2o
2) composition) soak the ceramic matrix 30 minutes with interdigital gold electrode under room temperature, with deionized water drip washing 2 minutes, and dry up with argon gas;
(3) ceramic matrix 1 dried up being immersed concentration is in the PDDA aqueous solution of 3%wt 10 minutes, and taking-up deionized water drip washing 2 minutes also dries up with argon gas;
(4) ceramic matrix 1 dried up obtained for step (3) being immersed concentration is in the kayexalate of 3%wt 10 minutes, and taking-up deionized water drip washing 2 minutes also dries up with argon gas;
(5) repeat step (3) and step (4) 5 times successively, obtain the ceramic matrix 1 with interdigital gold electrode of modified;
(6) taking 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in 20mL water, 0.2mL aniline (be 1:1 with the mol ratio of aniline monomer) is added in ice-water bath, continue stirring 1 hour, then 0.5g ammonium persulfate (be 1:1 with the mol ratio of aniline monomer) is slowly dripped, stop after stirring stirring, react 5 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 3mg/mL;
(7) ceramic matrix 1 with interdigital gold electrode of modified obtained for step (5) is immersed the titanium dioxide nano-particle aqueous solution 10 minutes that concentration is 3 mg/mL, taking-up pH value is the sulfuric acid drip washing 2 minutes of 1.5 and dries up with argon gas;
(8) ceramic matrix 1 with interdigital gold electrode obtained for step (7) is immersed the polyaniline aqueous solution 10 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 3 mg/mL, taking-up pH value is the sulfuric acid drip washing 2 minutes of 1.5 and dries up with argon gas;
(9) repeat step (7) and step (8) 5 times successively, obtain depositing the ceramic matrix 1 of polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 layer by layer;
(10) obtained for step (9) ceramic matrix 1 depositing polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 is layer by layer immersed the polyaniline aqueous solution 10 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 3 mg/mL, taking-up argon gas dries up, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposits polyaniline 6, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
Embodiment 8:
(1) lithographically depositing 8 to interdigital width on ceramic matrix 1 surface is 150 μm, and interdigital gap is the interdigital gold electrode 2 of 150 μm, the obtained ceramic matrix 1 with interdigital gold electrode;
(2) with Piranha solution (by the 7 parts of concentrated sulphuric acid (H by volume
2hydrogen peroxide (the H of SO4) and 3 part 30%
2o
2) composition) soak the ceramic matrix 40 minutes with interdigital gold electrode under room temperature, with deionized water drip washing 1 minute, and dry up with nitrogen;
(3) ceramic matrix 1 dried up being immersed concentration is in the PDDA aqueous solution of 2%wt 6 minutes, and taking-up deionized water drip washing 1 minute also dries up with nitrogen;
(4) ceramic matrix 1 dried up obtained for step (3) being immersed concentration is in the kayexalate of 2%wt 7 minutes, and taking-up deionized water drip washing 1 minute also dries up with nitrogen;
(5) repeat step (3) and step (4) 3 times successively, obtain the ceramic matrix 1 with interdigital gold electrode of modified;
(6) taking 1.25g polystyrolsulfon acid aqueous solution (30%wt) is dissolved in 20mL water, 0.2mL aniline (be 1:1 with the mol ratio of aniline monomer) is added in ice-water bath, continue stirring 1 hour, then 0.5g ammonium persulfate (be 1:1 with the mol ratio of aniline monomer) is slowly dripped, stop after stirring stirring, react 8 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, and configuration concentration is the polyaniline aqueous solution of the polystyrolsulfon acid doping of 2mg/mL;
(7) ceramic matrix 1 with interdigital gold electrode of modified obtained for step (5) is immersed the titanium dioxide nano-particle aqueous solution 7 minutes that concentration is 2 mg/mL, taking-up pH value is the nitric acid drip washing 1 minute of 1.5 and dries up with nitrogen;
(8) ceramic matrix 1 with interdigital gold electrode obtained for step (7) is immersed the polyaniline aqueous solution 7 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 2 mg/mL, taking-up pH value is the nitric acid drip washing 1 minute of 1.5 and dries up with nitrogen;
(9) repeat step (7) and step (8) 20 times successively, obtain depositing the ceramic matrix 1 of polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 layer by layer;
(10) obtained for step (9) ceramic matrix 1 depositing polyaniline/titanium dioxide nanometer Electrostatic Self-Assembled Films 5 is layer by layer immersed the polyaniline aqueous solution 7 minutes that the obtained concentration of step (6) is the polystyrolsulfon acid doping of 2 mg/mL, taking-up nitrogen dries up, polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film 5 deposits polyaniline 6, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
The polyaniline particle of polystyrolsulfon acid doping of the present invention and the scanning electron microscope (SEM) photograph of titanium dioxide nano-particle are shown in Fig. 7, the scanning electron microscope (SEM) photograph of the polyaniline particle that (a) adulterates for polystyrolsulfon acid in figure, b scanning electron microscope (SEM) photograph that () is titanium dioxide nano-particle, as can be seen from Figure 7, the particle diameter of the polyaniline particle of polystyrolsulfon acid doping only has a few nanometer, 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, is only hundreds of nanometer.
In order to the amount characterizing polyaniline and titania in each layer upon layer electrostatic self assembly is certain, can be illustrated by the uv absorption intensity of testing electrostatic self-assembled laminated film film 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 increase of laminated film, proves the realization of the polyaniline that polystyrolsulfon acid adulterates and titanium dioxide nano-particle electrostatic self-assembled process.
Above-described embodiment is only not used in for illustration of the present invention and limits the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (8)
1. the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide, comprise the ceramic matrix (1) set gradually, interdigital gold electrode (2) and air-sensitive film (3), described interdigital gold electrode is connected with lead-in wire (4), it is characterized in that: have interdigital gold electrode (2) at described ceramic matrix surface deposition, air-sensitive film (3) is had at described ceramic matrix (1) and interdigital gold electrode (2) surface deposition, described air-sensitive film (3) is made up of the polyaniline (6) of polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) and upper covering thereof, described polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) be by layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid doping polyaniline and obtained, described polyaniline (6) is the polyaniline of polystyrolsulfon acid doping.
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 right, the interdigital width of interdigital gold electrode (2) is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm.
3. the nano combined impedance type thin film gas sensor of a kind of polyaniline/titanium dioxide according to claim 1, is characterized in that: the thickness of described air-sensitive film (3) is 100 ~ 600nm.
4. a preparation method for the nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide, is characterized in that comprising the steps:
1) interdigital gold electrode (2) is deposited on ceramic matrix (1) surface by the method for evaporation or photoetching, the obtained ceramic matrix (1) with interdigital gold electrode;
2) process has the ceramic matrix (1) of interdigital gold electrode, the ceramic matrix (1) with interdigital gold electrode of obtained modified;
3) at upper deposition polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film of the ceramic matrix (1) with interdigital gold electrode (5) of modified; Described polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) be by layer upon layer electrostatic self assembly titanium dioxide nano-particle and polystyrolsulfon acid doping polyaniline and obtained;
4) in polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5), polyaniline (6) is deposited, described polyaniline (6) is the polyaniline of polystyrolsulfon acid doping, the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
5. preparation method according to claim 4, 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 nitrogen or argon gas with deionized water drip washing 1 ~ 2 minute;
2. then the ceramic matrix (1) dried up being immersed concentration is in the PDDA aqueous solution of 1 ~ 3%wt 5 ~ 10 minutes, and taking-up deionized water drip washing 1 ~ 2 minute also dries up with nitrogen or argon gas;
3. it is in the kayexalate of 1 ~ 3%wt 5 ~ 10 minutes that the ceramic matrix (1) that step 2. dried up immerses concentration, and taking-up deionized water drip washing 1 ~ 2 minute also dries up with nitrogen or argon gas;
4. repeat successively step 2. with step 3. 2 ~ 5 times, obtain the ceramic matrix (1) with interdigital gold electrode of modified.
6. preparation method according to claim 4, is characterized in that described step 3) comprise the steps:
1. polystyrolsulfon acid is put into water wiring solution-forming, then aniline monomer is added, after stirring, add ammonium persulfate again, stop after stirring stirring, reactant reacts 3 ~ 8 hours in ice-water bath, the polyaniline of obtained polystyrolsulfon acid doping, described polystyrolsulfon acid and the mol ratio of aniline monomer are 1:1, and the mol ratio of ammonium persulfate and aniline monomer is 1:1;
2. the ceramic matrix (1) with interdigital gold electrode of modified is immersed the titanium dioxide nano-particle aqueous solution 5 ~ 10 minutes that concentration is 1 ~ 3mg/mL, taking-up pH value is the sour drip washing 1 ~ 2 minute of 1.5 and dries up with nitrogen or argon gas, and described acid is hydrochloric acid, sulfuric acid or nitric acid;
3. then the ceramic matrix (1) dried up is immersed the polyaniline aqueous solution 5 ~ 10 minutes that concentration is the doping of 1 ~ 3mg/mL polystyrolsulfon acid, taking-up pH value is the sour drip washing 1 ~ 2 minute of 1.5 and dries up with nitrogen or argon gas, and described acid is hydrochloric acid, sulfuric acid or nitric acid;
4. repeat successively step 2. with step 3. 5 ~ 40 times, obtain the ceramic matrix (1) depositing polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5).
7. preparation method according to claim 4, is characterized in that described step 4) comprise the steps:
1. the polyaniline aqueous solution that the polystyrolsulfon acid being 1 ~ 3mg/mL by ceramic matrix (1) the immersion concentration depositing polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) adulterates 5 ~ 10 minutes;
2. taking-up nitrogen or argon gas dry up, and polyaniline/titanium dioxide layer upon layer electrostatic self assembly laminated film (5) deposits polyaniline (6), the obtained nano combined impedance type thin film gas sensor of polyaniline/titanium dioxide.
8. the preparation method according to any one of claim 4 to 7, described interdigital gold electrode is 5 ~ 16 right, and the interdigital width of interdigital gold electrode is 20 ~ 200 μm, and interdigital gap is 20 ~ 200 μm.
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