CN109298030A - A kind of niobium doped anatase phase titanic oxide film gas sensor and preparation method thereof - Google Patents
A kind of niobium doped anatase phase titanic oxide film gas sensor and preparation method thereof Download PDFInfo
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- CN109298030A CN109298030A CN201811399302.5A CN201811399302A CN109298030A CN 109298030 A CN109298030 A CN 109298030A CN 201811399302 A CN201811399302 A CN 201811399302A CN 109298030 A CN109298030 A CN 109298030A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
The present invention provides a kind of niobium doped anatase phase titanic oxide film gas sensors and preparation method thereof, belong to sensor field.The present invention sputters the titania-doped seed layer of niobium in substrate surface first, then forms niobium doped anatase phase titanic oxide seed layer by annealing；Then niobium doped anatase phase titanic oxide air-sensitive film is grown on seed layer by hydro-thermal method, prepares Pt interdigital electrode after being annealed again on film, obtains niobium doped anatase phase titanic oxide film gas sensor.The present invention prepares niobium doped anatase phase titanic oxide air-sensitive film by one step of hydro-thermal method, and step is simple, and by effective niobium doping vario-property, sensor is enable to work at normal temperature, and has both low detectable limit and wide detection range；Further, the substrate at low cost such as glass can be used in sensor of the invention, further reduces the preparation cost of sensor.
Description
Technical field
The present invention relates to sensor technical field, in particular to a kind of niobium doped anatase phase titanic oxide film gas-sensitive passes
Sensor and preparation method thereof.
Background technique
Gas sensor is ceased in current industry, electronic information, metallurgical industry, national defence, space flight and aviation and numerous and life
Relevant field is ceased to be widely used.The core of gas sensor design is gas sensitive, based on metal oxide half
The gas sensor of conductor (MOS) material has the characteristics that easily manufactured, low in cost, high sensitivity is widely paid close attention to,
Wherein titanium dioxide is more because of its inexpensive, nontoxic, high stability, and becomes mos sensor field material most with prospects
One of.Design have low cost, highly sensitive, wide detection range, response quickly, working and room temperature titanium dioxide gas sensor
Have great importance to meet actual demand.
In recent years, people are the performance for improving titanium dioxide gas sensor, are carried out in terms of being synthetically prepared with modification
A large amount of research work.The surface area for expanding film by preparing meso-porous nano pipe titanium dioxide, promotes the diffusion of detection gas
With adsorption；The catalysis reaction of detection gas is promoted to improve sensor performance by the modification of surface noble metal；Pass through doping
It is modified, promote the absorption of gas, transmission of charge etc. improves the performance of Metal Oxide Semiconductor Gas Sensing sensor various aspects.
Currently, the preparation of titanium dioxide gas sensor is usually in FTO (F adulterates SnO transparent conductive film) substrate
It is upper that the nano-pillar titanium dioxide air-sensitive film of [002] oriented growth is prepared for seed layer, then hydro-thermal by magnetic control.But mesh
The method that preceding hydro-thermal method prepares the titania-doped air-sensitive film of niobium is completed using 2 footworks, and first step hydro-thermal prepares niobium and mixes
Powder is prepared into after mud and forms film using the methods of spin coating, inkjet printing preparation by miscellaneous titania powder, second step, most
High temperature sintering is prepared into air-sensitive film afterwards, and complex process is with high costs；And the H of current titanium dioxide gas sensor2Air-sensitive
Characteristic is difficult to have both low detectable limit and wide detection range at normal temperature.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of niobium doped anatase phase titanic oxide film gas sensor and
Preparation method.Preparation method step provided by the invention is simple, at low cost, and prepared sensor is to H2, CO etc.
Gas has good detection performance, can work at room temperature, and detection range is wide, detectable limit concentration is low.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of niobium doped anatase phase titanic oxide film gas sensor, comprising the following steps:
(1) the titania-doped seed layer of niobium is sputtered in substrate surface；The sputtering target material is NbxTi2-xO3, wherein x
=0.05~0.2；
(2) substrate in the step (1) with the titania-doped seed layer of niobium is subjected to the first annealing, in substrate table
Face forms niobium doped anatase phase titanic oxide seed layer；
(3) seed layer for the substrate with niobium doped anatase phase titanic oxide seed layer for obtaining the step (2)
It is immersed in hydro-thermal reaction precursor solution downwards, carries out hydro-thermal reaction, form niobium doped anatase phase two in seed crystal surface
Thin film of titanium oxide；It include water, hydrochloric acid, TiO 2 precursor and ethyl alcohol niobium in the hydro-thermal reaction precursor solution；
(4) the substrate progress second with niobium doped anatase phase titanic oxide film for obtaining the step (3) is moved back
Then fire prepares Pt interdigital electrode on niobium doped anatase phase titanic oxide film, obtains niobium doped anatase phase titanium dioxide
Titanium film gas sensor.
Preferably, the material of substrate is glass, silicon wafer, quartz, plastics or FTO electro-conductive glass in the step (1).
Preferably, target is 50~70mm at a distance from substrate in the step (1)；The power of the sputtering be 30~
100W, time are 10~100min.
Preferably, the temperature of the first annealing is 300~500 DEG C in the step (2), and the time is 0.5~1h.
Preferably, TiO 2 precursor is in butyl titanate, isopropyl titanate and titanium ethanolate in the step (3)
It is one or more of；
The atomic ratio of Nb and Ti is 0.5%~3.5% in the hydro-thermal reaction precursor solution.
Preferably, the volume ratio of water in the hydro-thermal reaction precursor solution, hydrochloric acid, TiO 2 precursor and ethyl alcohol niobium is
The μ of 22~35mL:20~40mL:0.5~3mL:1.8~75.6 L；The mass fraction of the hydrochloric acid is 36~38%.
It preferably, further include alcohol in the hydro-thermal reaction precursor solution；The alcohol includes methanol, ethyl alcohol, propyl alcohol and butanol
One or more of；
When including alcohol in the hydro-thermal reaction precursor solution, in hydro-thermal reaction precursor solution the volume ratio of water and alcohol be 22~
35:0.5~5.
Preferably, the temperature of hydro-thermal reaction is 120~180 DEG C in the step (3), and the time is 4~10h.
Preferably, the temperature of the second annealing is 300~500 DEG C in the step (4), and the time is 10~60min.
The present invention provides the niobium doped anatase phase titanic oxide film gas-sensitives of the preparation of preparation method described in above scheme
Sensor successively includes substrate, seed layer, niobium doped anatase phase titanic oxide film and Pt interdigital electrode from bottom to top.
The present invention provides a kind of preparation method of niobium doped anatase phase titanic oxide film gas sensor, the present invention
The titania-doped seed layer of niobium is sputtered in substrate surface first, then niobium doped anatase phase titanic oxide seed is formed by annealing
Crystal layer；Then niobium doped anatase phase titanic oxide film is grown on seed layer by hydro-thermal reaction, after being annealed again
Pt interdigital electrode is prepared on niobium doped anatase phase titanic oxide film, obtains niobium doped anatase phase titanic oxide film gas
Dependent sensor.The present invention prepares niobium doped anatase phase titanic oxide air-sensitive film by one step of hydro-thermal method, and step is simple；This hair
The bright sensitivity that sensor is improved by effective niobium doping vario-property, the titanium dioxide air-sensitive film after enabling niobium to adulterate is in room temperature
Lower work, and have both low detectable limit and wide detection range；Further, sensor of the invention can be used glass etc. at
This low substrate further reduces the preparation cost of sensor.Embodiment the result shows that, sensor prepared by the present invention exists
Performance review H under room temperature2Sensitivity is 9.3% when concentration 1ppm, has the low detectable concentration limit, and in H2Have under concentration 1ppm
There is higher sensitivity value；Check H2Sensitivity reaches 96.8% when concentration is 12000ppm, has high H2Concentration detecting capability, and
In wide H2All there is excellent detection performance in concentration range (1ppm~12000ppm).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of niobium doped anatase phase titanic oxide film gas sensor of the invention；
In Fig. 1: 1- substrate, 2-Nb adulterate TiO2Seed layer, 3-Nb doped anatase phase TiO2Film, 4-Pt interdigital electrode；
Fig. 2 is Nb doped anatase phase TiO prepared by embodiment 12The scanning electron microscope (SEM) photograph of film；
Fig. 3 is the scanning electron microscope (SEM) photograph of the longitudinal section of niobium doped anatase phase titanic oxide film gas-sensitive prepared by embodiment 1；
Fig. 4 is Nb doped anatase phase TiO prepared by embodiment 12The X-ray energy spectrum analytical element distribution map of film；
Fig. 5 is Nb doped anatase phase TiO prepared by embodiment 12The selective electron diffraction figure of film；
Fig. 6 is the hydrogen gas characteristic of niobium doped anatase phase titanic oxide film gas sensor prepared by embodiment 1
Figure；
The CO gas-sensitive property figure of niobium doped anatase phase titanic oxide film gas sensor prepared by Fig. 7 embodiment 1.
Specific embodiment
A kind of preparation method of niobium doped anatase phase titanic oxide film gas sensor, comprising the following steps:
(1) the titania-doped seed layer of niobium is sputtered in substrate surface；The sputtering target material is NbxTi2-xO3, wherein x
=0.05~0.2；
(2) substrate that sputtering in the step (1) has the titania-doped seed layer of niobium is subjected to the first annealing, in substrate
Surface forms niobium doped anatase phase titanic oxide seed layer；
(3) surface that the step (2) obtains is had to the seed crystal of the substrate of niobium doped anatase phase titanic oxide seed layer
Level is immersed in downwards in hydro-thermal reaction precursor solution, carries out hydro-thermal reaction, forms niobium doped anatase phase two in substrate surface
Thin film of titanium oxide；It include water, hydrochloric acid, TiO 2 precursor and ethyl alcohol niobium in the hydro-thermal reaction precursor solution；
(4) the substrate progress second with niobium doped anatase phase titanic oxide film for obtaining the step (3) is moved back
Then fire prepares Pt interdigital electrode on the niobium doped anatase phase titanic oxide film, obtains niobium doped anatase phase two
Thin film of titanium oxide gas sensor.
The present invention sputters the titania-doped seed layer of niobium in substrate surface.In the present invention, the material of the substrate is
Preferably glass, silicon wafer, quartz, plastics or FTO；Requirement of the preparation method of the present invention to substrate is lower, has support
The substrate of effect, the present invention more preferably use glass substrate cheap and easy to get, can further reduce the cost.
Present invention preferably uses magnetron sputtering methods to prepare the titania-doped seed layer of niobium.The present invention preferably cleans substrate
And after drying, then carry out magnetron sputtering.The present invention preferably successively carries out ultrasound clearly to substrate using acetone, ethyl alcohol, deionized water
It washes, the present invention does not have particular/special requirement to the actual conditions of the ultrasonic cleaning, as long as can clean up impurity on substrate surface i.e.
It can.
In the present invention, the sputtering target material is NbxTi2-xO3, wherein x=0.05~0.2, preferably 0.1~0.15,
More preferably 0.12；The target is preferably 50~70mm at a distance from substrate, more preferably 60mm；The power of the sputtering is excellent
It is selected as 30~100W, more preferably 60W, the time is preferably 10~100min, more preferably 40min.
After substrate surface forms the titania-doped seed layer of niobium, sputtering is had the titania-doped seed crystal of niobium by the present invention
The substrate of layer carries out the first annealing, forms niobium doped anatase phase titanic oxide seed layer in substrate surface.In the present invention, institute
The temperature for stating the first annealing is preferably 300~500 DEG C, and more preferably 400 DEG C, the time is preferably 0.5~1h, more preferably 1h；
First annealing preferably carries out under vacuum conditions, and the vacuum degree of first annealing is preferably smaller than 10-3Pa.The present invention passes through
First annealing obtains anatase phase titanium dioxide.
After forming niobium doped anatase phase titanic oxide seed layer, there is niobium doped anatase phase titanium dioxide on surface by the present invention
The seed layer of the substrate of titanium seed layer is immersed in downwards in hydro-thermal reaction precursor solution, hydro-thermal reaction is carried out, in substrate surface
Form niobium doped anatase phase titanic oxide film.In the present invention, in the hydro-thermal reaction precursor solution include water, hydrochloric acid,
TiO 2 precursor and ethyl alcohol niobium；The TiO 2 precursor is preferably butyl titanate, isopropyl titanate and titanium ethanolate
One or more of；More preferably butyl titanate；The atomic ratio of Nb and Ti is preferably in the hydro-thermal reaction precursor solution
0.5%~3.5%, more preferably 2%；Water, hydrochloric acid, TiO 2 precursor and ethyl alcohol niobium in the hydro-thermal reaction precursor solution
Volume ratio be preferably the μ of 22~35mL:20~40mL:0.5~3mL:1.8~75.6 L；More preferably 28mL:30mL:1mL:
14.5μL；The mass fraction of the hydrochloric acid is preferably 36~38%.
In the present invention, it is also preferable to include alcohol in the hydro-thermal reaction precursor solution；The alcohol preferably includes methanol, second
One or more of alcohol, propyl alcohol and butanol, more preferably ethyl alcohol；When in the hydro-thermal reaction precursor solution including alcohol, water
The volume ratio of water and alcohol is preferably 22~35:0.5~5, more preferably 28:2 in thermal response precursor solution.In the present invention, institute
The growth of film can be promoted in hydrothermal reaction process by stating alcohol.
In the present invention, the temperature of the hydro-thermal reaction is preferably 120~180 DEG C, and more preferably 130~160 DEG C, into one
Preferably 150 DEG C of step, the time is preferably 4~10h, more preferably 5~9h, further preferably 8h.The present invention is preferably poly- four
Hydro-thermal reaction is carried out in the hydrothermal reaction kettle of vinyl fluoride liner.In a specific embodiment of the present invention, preferably by the seed crystal of substrate
What level tilted down leans against on reaction kettle inner wall, and hydro-thermal reaction precursor solution, which is placed in reaction kettle, submerges substrate.
In hydrothermal reaction process of the invention, seed layer provide hydro-thermal reaction nucleating point, TiO 2 precursor and
Hydrolysis and polymerization reaction (including dehydration polymerization and dealcoholysis polymerization) occur for ethyl alcohol niobium, finally form niobium in seed crystal surface and mix
Miscellaneous anatase phase titanium dioxide film；Nb doping can effectively facilitate the transmission of charge in the film, facilitate sensor for gas
Bulk concentration signal is converted into reliable electrical signal；And Nb doping can be improved surface anatase phase titanium dioxide and Pt electrode
The schottky barrier height of formation promotes the absorption of device Surface Oxygen ion, the effective sensitivity for improving device.
After the completion of hydro-thermal reaction, the present invention is preferably by substrate and hydro-thermal reaction liquid cooled to room temperature, then by substrate
Ultrapure water cleaning and natural air drying are used after taking-up.
After air-drying, the substrate with niobium doped anatase phase titanic oxide film that the present invention obtains carries out the second annealing.
In the present invention, the temperature of second annealing is preferably 300~500 DEG C, and more preferably 350~450 DEG C, further preferably
400 DEG C, the time is preferably 10~60min, more preferably 15~50min, further preferably 20min；Second annealing is excellent
It is selected under the conditions of inert gas shielding and carries out.In the present invention, after hydro-thermal reaction, the niobium that the seed crystal surface of substrate is formed is adulterated
There are the alcohol in hydro-thermal reaction precursor solution in anatase phase titanium dioxide film, the residues such as HCl, the present invention is moved back by second
Residue in fire removal film, and the defects of film can be reduced by the second annealing, be conducive to charge transmission, improve
The performance of sensor.
After the completion of second annealing, the present invention prepares Pt interdigital electrode on niobium doped anatase phase titanic oxide film, obtains
To niobium doped anatase phase titanic oxide film gas sensor.Present invention preferably uses magnetron sputtering methods to prepare interdigital electrode,
The power of the magnetron sputtering is preferably 40W, and the time is preferably 5min；In a specific embodiment of the present invention, preferably in film
The mask plate for having a predetermined pattern is placed on surface, is sputtered using pure Pt as target, and the Pt plasma sputtered out can be
Deposition forms Pt interdigital electrode on film surface.
The present invention also provides the niobium doped anatase phase titanic oxide film gas of the preparation of preparation method described in above scheme
Dependent sensor, from bottom to top successively include substrate, seed layer, niobium doped anatase phase titanic oxide film and Pt interdigital electrode,
Structural schematic diagram is as shown in Figure 1.In the present invention, the thickness of the niobium doped anatase phase titanic oxide film be preferably 50~
500nm, more preferably 166nm；The present invention does not have particular/special requirement to the thickness of the seed layer, as long as being capable of providing hydro-thermal reaction
Nucleating point.The present invention does not have particular/special requirement to the thickness of the Pt interdigital electrode, and use is well known to those skilled in the art
Thickness.
In the present invention, it is dense to can be used for detection gas for the niobium doped anatase phase titanic oxide film gas sensor
Degree, it is specific such as H2And CO, work at normal temperature, in use, by Pt interdigital electrode both ends respectively with work station just
Cathode connection, carries out the measurement of resistance, and the concentration of object gas can be obtained according to the resistance variations being passed through before and after object gas
Value.
Below with reference to embodiment to a kind of niobium doped anatase phase titanic oxide film gas sensor provided by the invention
And preparation method thereof be described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) acetone, ethyl alcohol, deionized water are successively used, glass substrate is cleaned by ultrasonic, is dried in drying box；
(2) the titania-doped seed layer of magnetron sputtering niobium: by Nb0.12Ti1.88O3Target is installed on magnetic control sputtering system yin
Pole target position, adjusting target is 60mm at a distance from substrate, adjusts Nb0.12Ti1.88O3The rf sputtering power of target is 60w, is continued clear
Sputtering sedimentation 40min in glass substrate after washing drying forms the titania-doped seed layer of niobium in substrate surface；
(3) sample obtained to step 2 400 DEG C of annealing 1h under a high vacuum, obtain niobium doped anatase phase titanic oxide
Seed layer, vacuum degree of annealing is less than 10-3Pa；
(4) hydro-thermal reaction is carried out:
Configure hydro-thermal reaction precursor solution: by water, ethyl alcohol (analysis pure >=99.7%), hydrochloric acid (analysis pure 36%~
38%), butyl titanate (analysis pure >=99.0%), ethyl alcohol niobium (>=99.9%) are configured according to following volumes percentage, are obtained
Hydro-thermal reaction precursor solution.
Deionized water: 28ml (46%)
Ethyl alcohol: 2ml (3.3%)
Hydrochloric acid: 30ml (49%)
Butyl titanate 1ml (1.6%)
14.5 μ L of ethyl alcohol niobium
Atomic ratio Nb/Ti=2% in gained hydro-thermal reaction precursor solution.
Hydro-thermal reaction precursor solution is poured into polytetrafluoroethyllining lining hydrothermal reaction kettle, step (3) preparation is had into niobium
The glass substrate of doped anatase phase titanic oxide seed layer, seed layer obliquely lean against on inner liner of reaction kettle wall down, leaching
Enter in hydro-thermal reaction precursor solution；Reaction kettle is covered tightly to be placed in constant temperature oven, 150 DEG C hydro-thermal process 8h hours；Reaction is completed
The reaction kettle that will be cooled to room temperature afterwards takes out, and takes out glass substrate, cleans simultaneously natural air drying with ultrapure water, obtains niobium doping rutile titania
Mine phase titanic oxide film.
(5) by the film sample of natural air drying in step (4) under Ar atmosphere protection 400 DEG C of annealing 20min；
(6) it prepares Pt interdigital electrode: high-purity Pt target being installed on magnetic control sputtering system cathode target position, adjusts direct current Pt target
Power is 40W, carries out 5min sputter coating to target, forms the interdigital electricity of Pt on niobium doped anatase phase titanic oxide film
Pole obtains niobium doped anatase phase titanic oxide film gas sensor.
Niobium doped anatase phase titanic oxide film is characterized:
The niobium doped anatase phase titanic oxide film that hydro-thermal reaction is prepared is observed using scanning electron microscope, institute
It is as shown in Figure 2 to obtain scanning electron microscope (SEM) photograph；According to fig. 2 as can be seen that film is formed by pruning octahedra accumulate on pinnacle, and institute
It is very fine and close to obtain film.
It is observed using longitudinal section of the scanning electron microscope to the niobium doped anatase phase titanic oxide film of preparation, gained knot
Fruit is as shown in Figure 3；Seed layer and niobium doped anatase phase titanic oxide film can be significantly seen according to Fig. 3, wherein seed crystal
The thickness of layer is about 60nm, and the thickness of niobium doped anatase phase titanic oxide film is about 166nm.
Fig. 4 is the X-ray energy spectrum analytical element distribution map of niobium doped anatase phase titanic oxide film；It can be with according to Fig. 4
Find out, elemental niobium is uniformly distributed in titanium dioxide, illustrates that niobium uniformly mixes in titanium dioxide.
Fig. 5 is the selective electron diffraction figure of niobium doped anatase phase titanic oxide film；According to Fig. 5 as can be seen that film
Crystal structure be it is anatase structured, be freely present anatase crystal and octahedra accumulated and formed, octahedral by prune pinnacle
The pinnacle face of body is 2 { 001 } faces, and side is 8 { 101 } faces.The titania-doped film of the bright niobium of selective electron diffraction chart
For Anatase structure.
The air-sensitive performance of niobium doped anatase phase titanic oxide film gas sensor is tested:
(a) using niobium doped anatase phase titanic oxide film gas sensor manufactured in the present embodiment to density of hydrogen into
Row test, test temperature are 25 ± 5 DEG C, and density of hydrogen range is 1ppm~12000ppm；
Gained hydrogen gas performance plot as shown in fig. 6, according to Fig. 6 can be seen that sensor density of hydrogen be 1ppm~
All there is good sensitivity behaviour in 12000ppm wide scope.It can be realized the density of hydrogen detection of wide scope.
The sensitivity of sensor is calculated according to the resistance value being passed through before and after hydrogen, the calculation method of sensitivity is as follows: sensitive
Degree (S) is defined as S=(Rair-Rgas)/Rair, and wherein Rair is film gas-sensitive device in room temperature, and humidity is about that (30%) is empty
Resistance in gas, Rgas are the resistance after being passed through object gas.
It can be calculated: H2The sensitivity of sensor is 9.3% when concentration 1ppm, has the low detectable concentration limit, and 1ppm
With higher sensitivity value；H2When concentration is 12000ppm, the sensitivity of sensor reaches 96.8%.
(b) CO concentration is carried out using niobium doped anatase phase titanic oxide film gas sensor manufactured in the present embodiment
Test, test temperature are 25 ± 5 DEG C, and CO concentration range is 50ppm-8000ppm；Gained hydrogen CO gas-sensitive property figure as shown in fig. 7,
According to Fig. 7 as can be seen that sensor provided by the invention equally has preferable sensitivity to CO at normal temperature.
Embodiment 2
Other conditions and embodiment 1 are identical, and the hydrothermal temperature in step (4) is only changed to 120 DEG C, when hydro-thermal reaction
Between be changed to 5h.
Embodiment 3
Other conditions and embodiment 1 are identical, and the hydrothermal temperature in step (4) is only changed to 180 DEG C, when hydro-thermal reaction
Between be changed to 10h.
Embodiment 4
Other conditions and embodiment 1 are identical, only remove the ethyl alcohol in step (4) in hydro-thermal reaction precursor solution.
Embodiment 5
Other conditions and embodiment 1 are identical, only carry out the hydro-thermal reaction precursor liquid in step (4) according to following volumes ratio
Configuration:
Deionized water: 22ml
Ethyl alcohol: 0.5ml
Hydrochloric acid: 25ml
Butyl titanate 1.5ml
14.5 μ L of ethyl alcohol niobium
Atomic ratio Nb/Ti=1.3% in gained hydro-thermal reaction precursor solution.
Embodiment 6
Other conditions and embodiment 1 are identical, and the annealing temperature in step (3) is only changed to 350 DEG C, and the time is changed to 0.5h,
Annealing temperature in step (5) is changed to 300 DEG C, the time is changed to 15min.
2~6 gained niobium doped anatase phase titanic oxide film gas-sensitive of embodiment is sensed according to the method in embodiment 1
Device carries out air-sensitive performance test, and acquired results and embodiment 1 are similar, and gained sensor has both low detectable limit and wide detection model
It encloses.
As can be seen from the above embodiments, the present invention prepares niobium doped anatase phase titanic oxide gas by one step of hydro-thermal method
Sensitive film, step are simple；The present invention is by effective niobium doping vario-property, and the titanium dioxide air-sensitive film after enabling niobium to adulterate is normal
The lower work of temperature, and have both low detectable limit and wide detection range；And the costs such as glass can be used in sensor of the invention
Low substrate further reduces the preparation cost of sensor.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of niobium doped anatase phase titanic oxide film gas sensor, which is characterized in that including following
Step:
(1) the titania-doped seed layer of niobium is sputtered in substrate surface；The sputtering target material is NbxTi2-xO3, wherein x=
0.05~0.2；
(2) substrate in the step (1) with the titania-doped seed layer of niobium is subjected to the first annealing, in substrate surface shape
At niobium doped anatase phase titanic oxide seed layer；
(3) seed layer for the substrate with niobium doped anatase phase titanic oxide seed layer for obtaining the step (2) towards
Under be immersed in hydro-thermal reaction precursor solution, carry out hydro-thermal reaction, seed crystal surface formed niobium doped anatase phase titanium dioxide
Titanium film；It include water, hydrochloric acid, TiO 2 precursor and ethyl alcohol niobium in the hydro-thermal reaction precursor solution；
(4) substrate with niobium doped anatase phase titanic oxide film for obtaining the step (3) carries out the second annealing, so
Pt interdigital electrode is prepared on niobium doped anatase phase titanic oxide film afterwards, obtains niobium doped anatase phase titanic oxide film
Gas sensor.
2. preparation method according to claim 1, which is characterized in that the material of substrate is glass, silicon in the step (1)
Piece, quartz, plastics or FTO electro-conductive glass.
3. preparation method according to claim 1, which is characterized in that target is at a distance from substrate in the step (1)
50~70mm；The power of the sputtering is 30~100W, and the time is 10~100min.
4. preparation method according to claim 1, which is characterized in that the temperature of the first annealing is 300 in the step (2)
~500 DEG C, the time is 0.5~1h.
5. preparation method according to claim 1, which is characterized in that TiO 2 precursor is titanium in the step (3)
One or more of sour four butyl esters, isopropyl titanate and titanium ethanolate；
The atomic ratio of Nb and Ti is 0.5%~3.5% in the hydro-thermal reaction precursor solution.
6. preparation method according to claim 5, which is characterized in that water, hydrochloric acid, two in the hydro-thermal reaction precursor solution
The volume ratio of titania precursor body and ethyl alcohol niobium is the 22~35mL:20~μ of 40mL:0.5~3mL:1.8~75.6 L；The hydrochloric acid
Mass fraction be 36~38%.
7. preparation method according to claim 1 or 6, which is characterized in that further include in the hydro-thermal reaction precursor solution
Alcohol；The alcohol includes one or more of methanol, ethyl alcohol, propyl alcohol and butanol；
When including alcohol in the hydro-thermal reaction precursor solution, the volume ratio of water and alcohol is 22~35 in hydro-thermal reaction precursor solution:
0.5~5.
8. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction is 120 in the step (3)
~180 DEG C, the time is 4~10h.
9. preparation method according to claim 1, which is characterized in that the temperature of the second annealing is 300 in the step (4)
~500 DEG C, the time is 10~60min.
10. the niobium doped anatase phase titanic oxide film gas-sensitive of the preparation of preparation method described in claim 1~9 any one passes
Sensor successively includes substrate, seed layer, niobium doped anatase phase titanic oxide film and Pt interdigital electrode from bottom to top.
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