CN101290302A - Micro-cavity gas-sensitive sensor based on simple root metallic oxide nanometer lines field effect tube - Google Patents
Micro-cavity gas-sensitive sensor based on simple root metallic oxide nanometer lines field effect tube Download PDFInfo
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- CN101290302A CN101290302A CNA2007100459421A CN200710045942A CN101290302A CN 101290302 A CN101290302 A CN 101290302A CN A2007100459421 A CNA2007100459421 A CN A2007100459421A CN 200710045942 A CN200710045942 A CN 200710045942A CN 101290302 A CN101290302 A CN 101290302A
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Abstract
The invention belongs to the nano and gas sensor technical field, in particular relating to a microcavity gas sensor for a field effect tube. The sensor adopts the design of a gas-sensitive chip based on a single metallic oxide nano wire in a microcavity, wherein, nano-wire materials can be ZnO, SnO2, TiO2 or In2O and so on. The gas sensor has high sensitivity, quick response speed, and low power consumption, does not need external heating, can utilize grid voltage to modulate the sensitivity and the selectivity, is convenient for being combined with other disconnecting gears for selective detection, and can be used for detection of gas such as O2, NO2, CO, H2, formaldehyde, alcohol and so on.
Description
Technical field
The invention belongs to nanometer and gas sensor technical field, be specifically related to a kind of micro-cavity gas-sensitive sensor of field effect transistor.
Background technology
As everyone knows, survey O
2And poisonous and inflammable gas such as NO
2, CO, H
2, formaldehyde and alcohol gas etc. gas sensor take precautions against natural calamities in daily life, commercial production, biology and medical treatment, environmental protection, anti-terrorism, all many-sides such as military and national defense have a wide range of applications.The material that uses is common ZnO[1], SnO
2[2], In
2O
3[3] ... and their alloy etc.But no matter be commercial or the research document, the overwhelming majority who relates to is block of material, film or thick film (comprising the thick film of being made up of a nanostructured) material.The air chamber in their whens work big (mostly be greatly tens even hundreds of cubic centimetre), this has just influenced their response speed greatly.Their working temperature too high (mostly being 200-500 ℃ greatly) in addition, power consumption is excessive when working like this, uses inconvenience, some occasions even at all can not use.
On the other hand, be that the research of the monodimension nanometer material of representative has caused and internationally extensively attractes attention recently with the ZnO nano wire.Scientists prepared the perfect ZnO nano wire of a series of crystalline networks, nano belt, nano-rings etc., and studied their application [4-6] at aspects such as photodetection, Ultra-Violet Laser, conversion of solar energy, nano-machine generatings.The research report [7-8] of the nanostructured of many ZnO of utilization (or the back of mixing) as the air-sensitive sensing also arranged simultaneously, but all be the form of utilizing thick film basically, exist above-mentioned working temperature height, response speed to wait problem slowly equally.
Summary of the invention
The objective of the invention is to propose the field effect micro-cavity gas-sensitive sensor that a kind of response speed is fast, highly sensitive, power consumption is little.
Field effect transistor (FET) micro-cavity gas-sensitive sensor of the present invention's design is made up of air-sensitive chip 1, spun gold lead-in wire 2, base 3 and glass cover 4, and its structure as shown in Figure 1.Wherein, air-sensitive chip 1 is bonded on the base 3, by spun gold 2 extraction electrodes that go between, and glass cover 4 and base 3 sealed knots, the middle microcavity (being about 0.6-10cm3) that forms, two ends are drawn by tubule 5, in order to import gas to be detected.
Among the present invention, the structural principle of described air-sensitive chip 1 is seen shown in Figure 2.It is made up of metal oxide nano-wire, square matrix electrodes and substrate, wherein, simple root metallic oxide nanometer lines 8 is pressed under the square matrix electrodes that is prepared by photoetching, the source electrode 6 and the drain electrode 9 of field effect transistor done at two ends, the P+ silicon chip is adopted in substrate 10, as the grid of field effect transistor, the preparation of substrate 10 upper surface has oxide layer 7.
Among the present invention, the material of described metal oxide nano-wire 8 can be ZnO, SnO
2, TiO
2, In
2O
3Deng.The material of described oxide layer 7 can be SiO
2, Si
3N
4, Al
2O
3Deng.
The micro-cavity gas-sensitive sensor of the present invention's design has following characteristics:
A. single nano-wire fet can be arranged in the very small cavity, because cavity little (being that the background gas volume is little), can be fast and funtion part effect (can do the trace detection) as long as the tested gas of minute quantity just enters, thereby response speed improves greatly, also can shorten greatly release time;
B. single nano-wire forms good the contact with electrode easily;
C. utilize the characteristics of nano wire high-ratio surface and high surface, can improve measurement sensitivity;
D. utilize working current as heating certainly, and because the required working current of nano wire very little (being generally several amperage magnitudes of receiving), so power consumption is very little;
E. can utilize grid voltage to come modulation sensitivity, selectivity etc.
F. be convenient to combine the detection of electing property with other tripping device.
In addition, can walk abreast in the same microcavity prepares a plurality of air-sensitive chip devices, and one side can be used as standby, can apply the different operating electric current simultaneously to a plurality of devices on the other hand, utilize the different characteristics of the required working temperature of detection of gas with various, be expected to detect simultaneously several gases.
Description of drawings
Fig. 1 is the photo of the ZnO nano wire of steaming process preparation.
Fig. 2 is a micro-cavity gas-sensitive sensor structural diagrams of the present invention.
Fig. 3 is the air-sensitive chip structure schematic diagram based on simple root metallic oxide nanometer lines.
Fig. 4 is the gas-sensitive property of single ZnO nano wire.Wherein, (A) electric current under the different oxygen concentrations changes (B) oxygen air-sensitive response characteristic (C) alcohol air-sensitive response characteristic.
Fig. 5 is the wet quick characteristic of gas sensor, wherein, (a) be in the microcavity under the different humidity sample resistance change situation, the influencing characteristic when (b) being variation of ambient temperature.
Number in the figure: 1. air-sensitive chip, 2. gold wire, 3. base, 4. gland bonnet, 5. wireway, 6. gold electrode (source), 7. oxide layer, 8. nano wire, 9. gold electrode (leakage), 10.P+ silicon chip.
Embodiment
The invention is further illustrated by the following examples.
1, device preparation
As gas sensitive, the oxide layer 7 of substrate adopts SiO to the present embodiment material with single ZnO nano wire
2, preparation of devices is divided into the preparation of air-sensitive chip and two steps of encapsulation of gas sensor.
The preparation of air-sensitive chip:
(1) adopts steam to capture chemical vapour deposition technique [4] and prepare ZnO nano wire 8 (as shown in Figure 1).
(2) adopt the P+ silicon chip as substrate 10, the oxide layer 7 of its surface preparation one deck 100-500 nanometer thickness.
(3) drip after the nano wire that will make disperses with alcohol and be sprinkled upon on the substrate surface.
(4) photoresist of 1.5 microns-3 microns of spin coatings in substrate, develop in the exposure back under square matrix electrodes masterplate.
(5) at the Au/Ti or the Au/Ni electrode that get deposition one deck 100-200 nano thickness on the sample, concrete thickness of electrode is decided on the diameter of nano wire
(6) peel off, obtain required litho pattern, wherein the interval between the square matrix electrodes is at the 2-10 micron.
Make basic gas sensor element through certain encapsulation after the air-sensitive chip makes, concrete preparation process is as follows:
(1) by being pressed with the basal region of nano wire under the operable electrode in SEM scanning location;
(2) the air-sensitive chip is bonded on the base 3 with the silver slurry, and draws respective electrode 3 by gold ball bonding;
(3) become confined space with glass 4 via the silicon rubber sealed knot on the base 3, and reserve two ends conduit 5 supplied gas and introduce.
The device for preparing feeds gas to be measured by wireway, and base inserts the related circuit loop.By detecting the variation of loop current, promptly obtain the air-sensitive and the wet quick characteristic of device.
2, the test of sample device
The preliminary single ZnO nano wire of test shows has following sensing characteristics:
(1) oxidation/reducibility gas such as oxygen, alcohol gas had the gas-sensitive property (see figure 4)
(2) humidity sensitivity characteristics (Fig. 5)
Fig. 4 is the gas-sensitive property test result of embodiment senser element.
When wherein (A) is gate voltage Vg=0V, O in the microcavity
2Concentration is respectively between the source-drain voltage of device under 0ppm, 250ppm, 500ppm, 750ppm, the 1000ppm condition and the electric current and concerns.Electric current minimizing along with sample under the identical voltage conditions of the increase of oxygen concentration.
(B) the attach most importance to response characteristic of device when to be added with into concentration be the oxygen of 500ppm.Its medium sensitivity is defined as | R
1-R
0|/R
0(R1 is the resistance of sample behind the adding gas, and R0 is for adding the resistance of the preceding sample of gas), oxygen is drawn out of at the OFF place in time arrival ON place's adding.
(C) the attach most importance to response characteristic of device when to be added with into concentration be the alcohol gas of 500ppm.Vg is 0V in the test of B and C.
Fig. 5 is the wet quick characteristic of embodiment senser element.
(a) be the change of sample resistance under the different humidity condition in the microcavity, standard saturated salt solution method is used in the generation of humidity environment: microcavity is connected respectively to 20 ℃ saturated MgCl is housed
2, Mg (NO
3)
2, NaBr solution and water closed container, wait for gas-liquid equilibrium after, the humidity of microcavity is respectively 33%, 54%, 59%, 100%.
The response characteristic of device when (b) changing for ambient humidity.Sensitivity definition is with the test of gas-sensitive property, add at the ON place give join earlier the air of 100% humidity, in the gas bleeding of OFF place.
List of references
[1]Baratto?C，Sberveglieri?G，Onischuk?A，Caruso?B?and?Stasio?S?D，Sensors?Actuators?B，2004100?261
[2]Liu?Y，Koep?E?and?Liu?ML，CHEMISTRY?OF?MATERIALS，2005，17?3997
[3]Chu?XF，Wang?CH，Jiang?DL?and?Zheng?CM，CHEMICAL?PHYSICS?LETTERS，2004，399?461
[4]Huang，Michael?H.，Mao，et?al.Science，2001，292?5523
[5]Lori?E.Greene，Benjamin?D.and?Peidong?Yang，Inorg.Chem.，2006，45?7535
[6]Zhong?Lin?Wang，et?al.，Science，2006，312?242
[7]J?X?Wang，X?W?Sun，Y?Yang，H?Huang，Y?C?Lee，O?K?Tan?and?L?Vayssieres，NANOTECHNOLOGY，2007，17?4995
[8]Yongsheng?Zhang，Ke?Yu，Desheng?Jiang，Ziqiang?Zhua，Haoran?Genge，Laiqiang?Luo，Applied?Surface?Science，2005，242?212。
Claims (4)
1, a kind of micro-cavity gas-sensitive sensor based on the simple root metallic oxide nanometer lines field effect transistor, it is characterized in that forming by air-sensitive chip (1), spun gold lead-in wire (2), base (3) and glass cover (4), wherein, air-sensitive chip (1) is bonded on the base (3), by spun gold lead-in wire (2) extraction electrode, glass cover (4) and base (3) sealed knot, the middle microcavity that forms, two ends are drawn by tubule (5), in order to import gas to be detected;
Described air-sensitive chip (1) is made up of metal oxide nano-wire, square matrix electrodes and substrate, wherein, simple root metallic oxide nanometer lines (8) is pressed under the square matrix electrodes that is prepared by photoetching, the source electrode (6) and the drain electrode (9) of field effect transistor done at two ends, the P+ silicon chip is adopted in substrate (10), as the grid of field effect transistor, the preparation of substrate (10) upper surface has oxide layer (7).
2, the micro-cavity gas-sensitive sensor based on the simple root metallic oxide nanometer lines field effect transistor according to claim 1, the material that it is characterized in that described metal oxide nano-wire (8) is ZnO, SnO
2, TiO
2Or In
2O
3, or their alloy.
3, the micro-cavity gas-sensitive sensor based on the simple root metallic oxide nanometer lines field effect transistor according to claim 1, the material that it is characterized in that described oxide layer (7) is SiO
24, Si
3N
4Or A1
2O
3
4, the micro-cavity gas-sensitive sensor based on the simple root metallic oxide nanometer lines field effect transistor according to claim 1 is characterized in that parallel a plurality of air-sensitive chip devices are arranged in the described microcavity.
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Application publication date: 20081022 |