CN102778479A - Integratable amorphous metal oxide semiconductor gas sensor - Google Patents
Integratable amorphous metal oxide semiconductor gas sensor Download PDFInfo
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- CN102778479A CN102778479A CN2011101176587A CN201110117658A CN102778479A CN 102778479 A CN102778479 A CN 102778479A CN 2011101176587 A CN2011101176587 A CN 2011101176587A CN 201110117658 A CN201110117658 A CN 201110117658A CN 102778479 A CN102778479 A CN 102778479A
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Abstract
The invention provides an integratable amorphous metal oxide semiconductor gas sensor, which comprises: a substrate; a heating electrode formed on the substrate; a signal detection electrode formed on the substrate to be coplanar with the heating electrode; a gas sensitive detection film formed on the substrate, the heating electrode and the signal detection electrode; wherein the gas-sensitive detection film comprises an amorphous oxide semiconductor. According to the gas sensor, the amorphous semiconductor is adopted as the gas sensitive detection film, so that the gas sensor can adopt a semiconductor standard manufacturing process, the cost is reduced, the uniformity and the response speed of a device are improved, the working temperature and the power consumption are reduced, and the gas sensor can be integrated efficiently at low cost in a large area.
Description
Technical field
The present invention relates to a kind of semiconductor sensor spare, particularly relate to the semi-conductive gas sensor of amorphous metal oxide that a kind of low-cost efficiently large scale can be integrated.
Background technology
Along with the continuous development of social life and industrial technology, gas sensor has more and more important effect on monitoring toxic and harmful, industrial gaseous waste, atmospheric pollution and raising food and human settlement's Environmental Protection Level.Main example application has NO in pair atmosphere
x, SO
x, CO
2Monitoring Deng harmful gas; Monitoring to CO in the life production; Detection to ethanol, methyl alcohol; To detection of vehicle exhaust etc.
Since the sixties in last century, the metal-oxide semiconductor (MOS) gas sensor just occupies the principal market of gas sensor with higher sensitivity, response advantage such as rapid.Initial gas sensor mainly adopts SnO
2, ZnO is gas sensitive, researched and developed some new materials in recent years again, except a small amount of single metal oxide materials, like WO
3, In
2O
3, TiO
2, Al
2O
3Deng outside, hot of research and development mainly concentrates on composite metal oxide and the potpourri metal oxide is as shown in table 1.
The corresponding metal oxide sensitive material of all kinds of detected gas of table 1
Metal oxide semiconductor sensor can be divided into two kinds of resistance-type and non-resistance-types on ultimate principle.
SnO
2, ZnO constant resistance formula metal oxide semiconductor sensor ultimate principle be to utilize the oxide semiconductor surface adsorption of gas and the resistance characteristic that the catalysis double effect changes material to external world; Thereby reach monitoring purposes; Belong to surperficial control type; But the serviceability temperature of such semiconductor transducer is higher, under 200～500 ℃, just possesses higher sensitivity greatly.Some are improved one's methods is in basic material, to add some noble metals (like Ag, Au, Pb etc.), activator and adhesive A l
2O
3, SiO
2, ZrO
2Wait and improve sensitivity, raising response time, reduction working temperature, the selectivity etc. that improves.The method for preparing these sensitive materials has sintering process, sol-gal process, chemical vapour deposition technique and physical deposition method etc.
Non-resistance-type metal-oxide semiconductor (MOS) gas sensor mainly comprises metal oxide semiconductor field effect tube (MOSFET) type gas sensor and diode-type gas sensor etc.The quick Pd grid of hydrogen MOSEFT is the catalytic metal gate field-effect gas sensor that is developed into the earliest, and when hydrogen and Pd have an effect, the threshold voltage of FET will change with density of hydrogen, detect hydrogen with this.Adopt yttria-stabilized zirconia (YSZ) to make the grid of MOSFET, Pt can be made into the quick FET type of oxygen gas sensor as metal gate.The metal gate of MOSFET is removed, adopt La
0.7Sr
0.3FeO
3Oxide semiconductor field effect pipe (OSFET) the formula gas sensor that nano thin-film has been made micron-scale, working and room temperature as grid has successfully been realized the detection to alcohol gas.
Semiconductor gas sensor can be divided into slug type, thick-film type and film-type etc. from manufacture craft.
Slug type can be divided into directly-heated type and heater-type again by type of heating.The directly-heated type slug type mainly is made up of gas sensitive material, heater strip and signal silk.Heater strip with measure silk and all directly be embedded in the gas sensitive, heater strip is used for the energising heating, measures silk and is used for measuring sensor resistance.The advantage of this element is: preparation technology is simple, power consumption is little, cost is low.Shortcoming is that the element function consistance is poor.Because element is little, thermal capacity is also little, influenced by ambient windstream, measures between loop and heating circuit and does not isolate, and interacts.Heater strip is in heating and can not produce breathing under the heated condition, causes the loose contact of material easily.
The heater-type structure is to have increased a capillary ceramic pipe in tube core inside, and heater strip penetrates in the ceramic pipe, outside pipe, coats the signal electrode of gold electrode as measuring sensor resistance, outside gold electrode, is coated with sensitive material, fired forming.This structure has overcome some shortcoming of directly-heated type element; Because heater strip does not contact with gas sensitive; Avoided measuring the mutual interference mutually between loop and the heating circuit; The consistance of element function improves a lot, and physical strength also is greatly improved, and becomes a kind of major structural types of present commercialization gas sensor.
The thick-film type sensor is a substrate with very thin oxidation pot potsherd generally; The back side at substrate coats from heater core; Another side is made bar shaped gold (or platinum) electrode with methods such as evaporation, sputters; It is acute technological on electrode, to adopt silk screen to print, and the air-sensitive slurry for preparing is coated with stamp, and forms through drying and sintering again.
The structure of film-type sensor and thick film device are similar, and difference is not to adopt screen printing technique to adopt in the preparation of gas sensing layer only, but adopts methods such as evaporation, sputter, and gas sensing layer thickness is thin more than thick-film type.Thin film type gas-sensitive device major part prepares on silicon substrate; Can utilize advanced technologies such as semiconductor planar processing technology; Help the integrated of difference in functionality element, and on silicon substrate, make the micro-hotplate structure, power consumption is very little; About milliwatt magnitude is the main developing direction of semiconductor gas sensor from now on.This element manufacturing is simple, is suitable for producing in enormous quantities, but because gas sensing layer adopts general method for manufacturing thin film, makes doping vario-property become difficult, thereby receive certain restriction.Utilize advanced technologies such as semiconductor planar technology; Can the film-type element of difference in functionality be integrated on the same substrate; Thereby preparing multifunctional integrated novel sensor array, realize the improvement of sensor performance, is the important directions of sensor development from now on.
Several kinds of structures each have its relative merits, and the element technology of thick-film type and heater-type structure is fairly simple comparatively speaking, cost is low, but power consumption is big, consistance is poor, response is not high enough, volume is big, it is integrated to be unfavorable for; The component size of film-type structure is little, it is integrated to be beneficial to, and power consumption is little, is the direction of gas sensor development.
A kind of common film integrated-type gas sensor is on silicon substrate, to utilize MEMS technology that the flakiness structure is corroded at the back; Deposit successively above that and structures such as formation dielectric isolation layer, METAL HEATING PROCESS electrode, heat rejection absciss layer, gas sensitive and extraction electrode; Because heating is removed with the big portion silicon materials at back, sensitizing range; Cause air insulated, thermal conduction path greatly weakens, and the power consumption that therefore makes heating resistor reach required working temperature greatly reduces.With the integrated signal processing function that can make full use of the conventional cmos circuit of silicon substrate, realize that monolithic is integrated simultaneously, reduce sensor bulk and overall cost.This structure is called as the micro-hotplate integrated sensor.
Yet conventional micro-hotplate integrated sensor is based upon on the silicon substrate and is applied to special MEMS technology, so cost is higher.The potpourri that the while sensitive thin film is generally particulate form is unfavorable for the integrated of thin film electronic.
Summary of the invention
Therefore, the technical issues that need to address of the present invention provide the non-crystal oxide semiconductor material and the device architecture that are applied to detection of gas that a kind of novel high efficiency, low cost large tracts of land evenly can be integrated with regard to being to overcome a series of problems such as technology, cost, homogeneity, response efficiency, reaction velocity, working temperature and power consumption in the existing film integrated-type gas sensor.
The invention provides a kind of gas sensor, comprising: substrate; Heating electrode is formed on the said substrate; Signal detection electrode is formed on the said substrate, with said heating electrode coplane; Gas sensitization is surveyed film, is formed on said substrate, said heating electrode and the said signal detection electrode; It is characterized in that said gas sensitization is surveyed film and comprised the non-crystal oxide semiconductor.
The present invention also provides a kind of gas sensor, comprising: substrate; Heating electrode is formed on the said substrate; Isolation insulating film is formed on said substrate and the said heating electrode; Gas sensitization is surveyed film, is formed on the said isolation insulating film; Signal detection electrode is formed on said gas sensitization and surveys on the film; It is characterized in that said gas sensitization is surveyed film and comprised the non-crystal oxide semiconductor.
Wherein, said non-crystal oxide semiconductor comprises the zno-based semiconductor of mixing In, and the zno-based semiconductor of the said In of mixing comprises InGaZnO, InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO.Wherein, the atom of [In]/([In]+[the 3rd metal]) counting is than being 35%～80% in the zno-based semiconductor of the said In of mixing, and the atom of [Zn]/([In]+[Zn]) is counted than being 40%～85%.Wherein, each element atom counting is than being [In]: [the 3rd metal]: [Zn]: [O]=1: 1: 1: 1 or 1: 1: 1: 2 or 2: 2: 2: 1 or 1: 1: 1: 4.
Wherein, said non-crystal oxide semiconductor comprises In
2O
3, ZTO, ITO, ZnO, SnO
x
Wherein, said non-crystal oxide semiconductor thickness is 1 to 10000nm.
Wherein, said substrate comprises at the bottom of the silicon wafer-based of surface for the silicon chip of insulation course, glass, quartz, plastics or back hollow out.Wherein, the material of said heating electrode and/or said signal detection electrode comprises Mo, Pt, Al, Ti, Co, Au, Cu, polysilicon, TiN, TaN and combination thereof.Wherein, the material of said isolation insulating film comprises silicon dioxide, silicon nitride, silicon oxynitride or high k material.
According to gas sensor of the present invention; Owing to adopted amorphous semiconductor to survey film as gas sensitization; Make gas sensor can adopt semiconductor standard manufacture technology, reduced cost, improved homogeneity, the response speed of device; Reduced working temperature and power consumption, therefore can high efficiency, low cost integrated in large area.
Purpose according to the invention, and in these other unlisted purposes, in the scope of the application's independent claims, be able to satisfy.Embodiments of the invention are limited in the independent claims, and concrete characteristic is limited in its dependent claims.
Description of drawings
Followingly specify technical scheme of the present invention with reference to accompanying drawing, wherein:
Figure 1A is the diagrammatic cross-section according to the direct resistor-type structure of non-crystal oxide semiconductor of the present invention gas sensor;
Figure 1B is the top view according to the direct resistor-type structure of non-crystal oxide semiconductor of the present invention gas sensor;
Fig. 2 A is the diagrammatic cross-section according to non-crystal oxide semiconductor indirect resistance type TFT structure gas sensor of the present invention; And
Fig. 2 B is the top view according to non-crystal oxide semiconductor indirect resistance type TFT structure gas sensor of the present invention.
Reference numeral
1, substrate
2, gas sensitization is surveyed film
3, electrode layer
3A, 3B signal detection electrode
The 3C heating electrode
4, isolation insulating film
Embodiment
Following with reference to accompanying drawing and combine schematic embodiment to specify the characteristic and the technique effect thereof of technical scheme of the present invention, amorphous metal oxide semiconductor gas sensor that can be integrated is disclosed.It is pointed out that structure like the similar Reference numeral representation class, used term " first " among the application, " second ", " on ", D score or the like can be used for modifying various device architectures.These are modified is not space, order or the hierarchical relationship of hint institute modification device architecture unless stated otherwise.
Shown in Figure 1A, be synoptic diagram according to the direct resistor-type structure of a kind of non-crystal oxide semiconductor of the present invention gas sensor, comprise substrate 1, gas sensitization detection film 2 and electrode 3 (comprising heating and signal detection electrode).Wherein, Substrate 1 is dielectric substrate and provides support; Its material for example (is preferably silicon-on-insulator SOI for the surface for the silicon chip of insulation course; Also can on the body silicon substrate, deposit or the laying of silicon dioxide is processed in thermal oxide; Can also on body silicon, form the insulation course of silicon nitride or silicon oxynitride), at the bottom of the silicon wafer-based of glass (can be doped to boron-phosphorosilicate glass BPSG commonly used, also can be spin-coating glass SOG, and glass substrate 1 preferably has rectangular shape to be suitable for cutting and large tracts of land manufacturing), quartz, plastics (being preferably composition) and back hollow out etc. with higher melt and hardness and good insulation properties.Substrate 1 is a tabular basically, comprises a pair of first type surface, also is lower surface and upper surface, also comprises the side surface between upper and lower major surfaces.The upper surface of substrate 1 can have coarse structure, periodicity concaveconvex structure; So that enhancing bond strength; For example realize, can also form cushion to slow down stress or bonding coat to strengthen bond strength (cushion or bonding coat are not shown) through common technologies such as rare HF acid wet etching or plasma etchings.
On the upper surface of substrate 1, form electrode layer 3; The preferred mode that adopts sputtering deposit, its material is Mo, Pt, Al, Ti, Co, Au, Cu etc. for example, can be the other materials with conducting function in addition; For example DOPOS doped polycrystalline silicon, for example metal nitride such as TiN, TaN or the like.Can be earlier during preparation even sputtering deposit one deck electrode layer material, carry out etching according to the electrode domain then and remove unwanted part.Stay the electrode 3A and the 3B of pair of opposing after the etching; Constitute signal detection electrode; In the signal detection electrode 3A plane identical, also be provided with heating of metal electrode 3C with 3B; Heating electrode 3C can adopt same material form with signal detection electrode 3A/3B, also can adopt two step depositing operations to use different materials and forms.Shown in Figure 1B, signal detection electrode 3A and 3B are oppositely arranged, and are preferably formed to staggered pair of electrodes to be used for bias voltage and to draw.The shape of signal detection electrode 3A and 3B is not limited to shown in the figure, can also be parallel or uneven straight line, broken line or curve, and the required electrology characteristic of concrete wiring basis signal detection means structure needs and sets.Heating electrode 3C can intert and is arranged between relative the signal detection electrode 3A and 3B, and preferably parallel with both or spacing equates, so that evenly heating.The end of three electrodes is formed with contact pad separately, is used for being connected with external circuit.Heating electrode 3C also can be around signal detection electrode 3A/3B, or parallel with it or the like, need not shown in Figure 1B, to be defined as and can only be plugged in therebetween.The width of electrode 3A/3B/3C and thickness need and be set according to the electric property and the heating of measuring element structure; The width and the thickness that are not limited among Figure 1B all equate; But, be preferably the identical and width-adjustable of three's thickness from the consideration of being convenient to sputtering technology control.
On the upper surface of substrate 1 and signal detection electrode 3A and 3B and heating electrode 3C, be formed with gas sensitization subsequently and survey film 2; Form gas sensitization and survey the zone of film 2 according to the exposure window of the gas to be measured (passivating film that this window can be formed by nitride, oxide etc. and defining; Can form the passivation film after etching and go out window deposition gases sensitive detection film 2 again; Also can form passivation film again and etch window after the deposition gases sensitive detection film 2) and decide; For example shown in Figure 1B rectangular area, but also can be other geometric configuratioies, for example triangle, parallelogram, trapezoidal, regular polygon, circular or the like.Gas sensitization is surveyed film 2 and is made up of the non-crystal oxide semiconductor, can be different and from table 1, select corresponding oxide semiconductor, particularly broad-band gap (＞=2.0eV) non-crystal oxide semiconductor according to the probe gas type.According to amorphous state MOS gas sensor that can be integrated of the present invention; It is to mix zno-based semiconductor or other binary non-crystal oxide semiconductor of In that its non-crystal oxide semiconductor is selected material for use; The zno-based semiconductor of mixing In for example is GaInZnO (IGZO), InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO, and other binary or multicomponent amorphous oxide semiconductor for example are In
2O
3, ZTO, ITO, ZnO, SnO
x(x=1～2) etc.Wherein, the atom counting of mixing [In]/([In]+[the 3rd metal]) in the ZnO based semiconductor of In is than being 35%～80%, and the atom of [Zn]/([In]+[Zn]) is counted than being 40%～85%.Preferred each element atom counting is than being [In]: [the 3rd metal]: [Zn]: [O]=1: 1: 1: 1 or 1: 1: 1: 2 or 2: 2: 2: 1 or 1: 1: 1: 4 etc.In atom outer-shell electron is main conduction electrons source in the material; Conduct electricity through adjacent oxygen room; The Zn atom plays the effect of stablizing crystallite born of the same parents structure, thereby and grade in an imperial examination three adulterants such as other Ga, Hf, Ta, Zr, Y, Al, Sn play the generation rate in control oxygen room and change semi-conductive conductance.Common method for making is magnetron sputtering method (Sputter), chemical vapour deposition technique (CVD), metal-organic chemical vapor deposition equipment method (MOCVD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (SOL-GEL), hydro-thermal method etc., preferably uses magnetron sputtering method in the present invention.The parameter of controlling its manufacturing process is controlled the semi-conductive material characteristic of zno-based of the formed In of mixing, for example selects proper A r/O
2Ratio, sputtering pressure, sputtering power, underlayer temperature, annealing time and temperature or the like.Optimum condition: Ar/O
2=100: x, x: 0～50; Air pressure 10～1000mtorr; Power 50～500W; Sputter underlayer temperature room temperature to 400 ℃; Anneal 100～450 ℃ 10min～10hr.Can need and be 1 to 10000nm for the thickness that the gas sensitization that the susceptibility of gas to be measured need be selected to form is surveyed film 2 according to the device electric property, be preferably 20 to 2000nm, especially 40 to 200nm, particularly 60nm.For other binary or multicomponent amorphous oxide semiconductor; Can be controlled to membrane stage through reasonable adjustment atom counting ratio and splash-proofing sputtering process parameter; Similar with the zno-based non-crystal oxide of mixing In; Can for example obtain required non-crystal oxide semiconductor through adding the 3rd metal or being adjusted to film thickness, these technology are known commonly used to those skilled in the art.
During device work; Apply power supply with heated air sensitive detection film 2 from the two ends of heating electrode 3C; Gas sensitization is surveyed film 2 and is received the gas that comes from the outside through being exposed to outer window area, and shown in arrow among Figure 1A, therefore the resistance that gas sensitization is surveyed film 2 change; Make promptly that also signal detection electrode changes to the resistance between 3A and the 3B, thereby can determine the existence of certain special gas through the outer detecting circuit that is attached thereto.
Compare polycrystalline, crystalline state and crystallite semiconductor, amorphous semiconductor shows shortrange order, isotropy; Manufacture craft is simple; Be prone to make large area film, and the local energy level that defective is more in being with, introducing is more, more help the absorption of oxonium ion in the gas.With typical material IGZO is example, and ternary mixed type non-crystal oxide metal semiconductor IGZO is by In
2O
3, Ga
2O
3Constitute with ZnO, energy gap is a kind of ionic amorphous state N-type semiconductor material about 3.4eV.In
2O
3In In
3+Can form the 5S electron trajectory, help the high-speed transfer of charge carrier; Ga
2O
3Very strong ionic link is arranged, can suppress the generation in O room; Zn among the ZnO
2+Can form stable tetrahedral structure, can make metal oxide IGZO form the non crystalline structure of stablizing higher conduction in theory.The non-crystal oxide semiconductor belongs to ionic amorphous semiconductor, and the atom outer-shell electron cloud of conduction through long radius overlaps each other and realize carrier transport, thereby the big (10～100cm of mobility
2/ Vs).
The conductive characteristic of IGZO film receives external environment parameters, comprises the influence of various factors of air humidity, air pressure and temperature.Such as, external environment parameters particularly the dividing potential drop of oxygen the electric conductivity of oxide is had significant impact.The electronic conduction of IGZO need be undertaken by the oxygen room of material internal, and oxygen vacancy concentration directly has influence on the semi-conductive intrinsic conductivity of IGZO.Under the gate voltage effect, the field takes place and helps reversible absorption and dissociation reaction in the oxygen atom of back raceway groove and extraneous oxygen molecule, thereby changes the oxygen vacancy concentration of raceway groove, and then is associated with the intrinsic change in resistance of material.The dividing potential drop of hydrogen has material impact to H-O, the isoionic combination of OH and generation simultaneously, also has influence on the absorption to this type of ion of semiconductive thin film, thereby changes to the film conductive characteristic, forms the good sensitivity response to H class gas.
The gas sensitization principle of oxide semiconductor is that the physics, the chemical process that rely on gas molecule (atom) in sull surface adsorption process, to produce are come perception gas, and this reaction is based upon on certain surface state.The absorption of gas on the oxide semiconductor film surface can be divided into negative ion absorption and positive ion absorption: when adatom produces negative ion absorption when semiconductor surface is obtained electronics, when adatom produces positive ion absorption when semiconductor surface is supplied with electronics.No matter be that electronics moves to semiconductor to the adatom migration or from foreign atom from semiconductor, will cause that all band curvature changes work function and conductivity.The general I of gas sensor does in air, wherein to contain a large amount of oxygen, belongs to strong oxidizing property gas.Oxygen very easily advances physics and chemisorption on the gas sensitive surface, comprises two kinds of physisorption and chemisorption, and this process is carried out slowlyer under the room temperature, if temperature is higher, and O
2-Can further be converted into O
-Form.O
-Activity very high, can be adsorbed on lip-deep other reducibility gas ionic group of gas sensitive and react rapidly, like C
2H
5OH etc. will the redox chemical reaction of generating polynomial, and the extra electron that course of reaction produces gets into conduction band, causes the gas sensitive resistance variations; In addition, for the intermediate oxide gas sensitive, except above-mentioned oxygen absorption, also have OH-absorption, help adsorbent and carry out redox reaction at metal oxide surface, the electronics that wherein discharges gets into conduction band, causes the gas sensitive resistance variations.This type of material and ambient humidity have bigger relation.
Through above-mentioned Analysis on Mechanism, can find out that the amorphous metal oxide semiconductor meets general gas sensitization basic norm, shows the high susceptibility to oxygen, OH class gas and other multiple gases.Than materials such as other crystalline state, polycrystalline attitude, particulate form, crystallite attitudes, amorphous attribute can provide more reaction table area, from atom level the chemical reaction of gas sensitization is provided, thereby has improved the overall susceptibility of film simultaneously.
In addition; The zno-based semiconductor film material of the In of mixing used in the present invention can also be used for other field; Ultraviolet detector or the like for example, according to gas detector of the present invention can also with the integrated manufacturing of these other semiconductor devices, further reduce cost and improved efficient.
Shown in Fig. 2 A, be diagrammatic cross-section according to a kind of non-crystal oxide semiconductor indirect resistance thin film transistor (TFT) of the present invention (TFT) type gas sensor.Wherein, as the silicon wafer-based of surface for the silicon chip of insulation course, back hollow out at the bottom of, on the substrate 1 of glass, quartz, plastics etc. at first sputtering deposit be formed with the ground floor electrode material layer, electrode layer material and embodiment 1 are similar, no longer stroll at this and state.This electrode layer of etching forms heating electrode 3C, and heating electrode 3C surveys the film heating gas sensitization except applying power supply through two ends, can also doublely do the grid of the TFT structure that will form after a while, therefore in Fig. 2 A, has only shown heating electrode 3C.It should be noted that the present invention can also adopt extra TFT grid, be formed in the same plane, but mutually insulated is isolated the power supply that the grid bias that is applied applies when also being different from heating with heating electrode 3C.
Form after the heating electrode 3C, on the entire device structure, passing through for example is that conventional methods such as CVD, PVD form isolation insulating films 4.From quickening heat conducting consideration, preferably those have the isolated insulation material of higher heat-conductivity; From the consideration that electrical insulation is isolated, can adopt the material of those relative dielectric constants higher (for example greater than 3.9).Particularly, isolation insulating film 4 can be silicon dioxide, silicon nitride, silicon oxynitride, or high k material such as hafnia, tantalum oxide, BTO.
Subsequently; On isolation insulating film 4, form gas sensitization and survey film 2; Can pass through magnetron sputtering method (Sputter), chemical vapour deposition technique (CVD), metal-organic chemical vapor deposition equipment method (MOCVD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel process (SOL-GEL), hydro-thermal method or the like and form, be preferably magnetron sputtering method.Its material and embodiment 1 are similar, can be different and from table 1, select corresponding oxide semiconductor, particularly broad-band gap (＞=2.0eV) non-crystal oxide semiconductor according to the probe gas type.According to amorphous state MOS gas sensor that can be integrated of the present invention; It is to mix zno-based semiconductor or other binary non-crystal oxide semiconductor of In that its non-crystal oxide semiconductor is selected material for use; The zno-based semiconductor of mixing In for example is GaInZnO (IGZO), InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO, and other binary or multicomponent amorphous oxide semiconductor for example are In
2O
3, ZTO, ITO, ZnO, SnO
x(x=1～2) etc.Wherein, the atom counting of mixing [In]/([In]+[the 3rd metal]) in the ZnO based semiconductor of In is than being 35%～80%, and the atom of [Zn]/([In]+[Zn]) is counted than being 40%～85%.Preferred each element atom counting is than being [In]: [the 3rd metal]: [Zn]: [O]=1: 1: 1: 1 or 1: 1: 1: 2 or 2: 2: 2: 1 or 1: 1: 1: 4 etc.
At last, survey formation signal detection electrode 3A and 3B on the film 2 at gas sensitization, its forming process, material, shape etc. are similar with embodiment 1, no longer stroll at this and state.When the present invention adopted extra TFT grid, signal detection electrode 3A and 3B were preferably around TFT grid symmetry.
During device work; 3D applies bias voltage to the TFT gate electrode; Two ends from heating electrode 3C apply power supply to see through isolation insulating film 4 indirect heating gas sensitizations detection film 2 then; Gas sensitization is surveyed film 2 and is received the gas that comes from the outside through being exposed to outer window area, and shown in arrow among Fig. 2 A, therefore the electric isolation characteristic that gas sensitization is surveyed film 2 changes; Therefore change as the signal detection electrode 3A of TFT source-drain electrode and the voltage-current characteristic between the 3B, thereby judge the existence of confirming special gas through outer detecting circuit.In non-crystal oxide semiconductor indirect resistance TFT type gas sensor; The susceptibility through surface resistance and the high mobility of material can change by the gas sensitization of sensitiveer reactive film conduction under active condition (grid-control bias voltage), thereby further improve the susceptibility of device.In addition, the good electrical characteristic of this device helps the integration of the integrated signal circuit of online pre-service monolithic, realizes single chip integrated gas sensor.
According to gas sensor of the present invention; Owing to adopted amorphous semiconductor to survey film as gas sensitization; Make gas sensor can adopt semiconductor standard manufacture technology, reduced cost, improved homogeneity, the response speed of device; Reduced working temperature and power consumption, therefore can high efficiency, low cost integrated in large area.
Although with reference to one or more exemplary embodiments explanation the present invention, those skilled in the art can know and need not to break away from the scope of the invention and device architecture is made various suitable changes and equivalents.In addition, can make by disclosed instruction and manyly possibly be suitable for the modification of particular condition or material and do not break away from the scope of the invention.Therefore, the object of the invention does not lie in and is limited to as being used to realize preferred forms of the present invention and disclosed specific embodiment, and disclosed device architecture and manufacturing approach thereof will comprise all embodiment that fall in the scope of the invention.
Claims (10)
1. gas sensor comprises:
Substrate;
Heating electrode is formed on the said substrate;
Signal detection electrode is formed on the said substrate, with said heating electrode coplane;
Gas sensitization is surveyed film, is formed on said substrate, said heating electrode and the said signal detection electrode;
It is characterized in that,
Said gas sensitization is surveyed film and is comprised the non-crystal oxide semiconductor.
2. gas sensor comprises:
Substrate;
Heating electrode is formed on the said substrate;
Isolation insulating film is formed on said substrate and the said heating electrode;
Gas sensitization is surveyed film, is formed on the said isolation insulating film;
Signal detection electrode is formed on said gas sensitization and surveys on the film;
It is characterized in that,
Said gas sensitization is surveyed film and is comprised the non-crystal oxide semiconductor.
3. according to claim 1 or claim 2 gas sensor; Wherein, Said non-crystal oxide semiconductor comprises the zno-based semiconductor of mixing In, and the zno-based semiconductor of the said In of mixing comprises InGaZnO, InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO.
4. gas sensor as claimed in claim 3, wherein, the atom of [In]/([In]+[the 3rd metal]) counting is than being 35%～80% in the zno-based semiconductor of the said In of mixing, the atom of [Zn]/([In]+[Zn]) is counted than being 40%～85%.
5. gas sensor as claimed in claim 4, wherein, each element atom counting is than being [In]: [the 3rd metal]: [Zn]: [O]=1: 1: 1: 1 or 1: 1: 1: 2 or 2: 2: 2: 1 or 1: 1: 1: 4.
6. according to claim 1 or claim 2 gas sensor, wherein, said non-crystal oxide semiconductor comprises In
2O
3, ZTO, ITO, ZnO, SnO
x
7. according to claim 1 or claim 2 gas sensor, wherein, said non-crystal oxide semiconductor thickness is 1 to 10000nm.
8. according to claim 1 or claim 2 gas sensor, wherein, said substrate comprises at the bottom of the silicon wafer-based of surface for the silicon chip of insulation course, glass, quartz, plastics or back hollow out.
9. according to claim 1 or claim 2 gas sensor, wherein, the material of said heating electrode and/or said signal detection electrode comprises Mo, Pt, Al, Ti, Co, Au, Cu, polysilicon, TiN, TaN and combination thereof.
10. gas sensor as claimed in claim 2, wherein, the material of said isolation insulating film comprises silicon dioxide, silicon nitride, silicon oxynitride or high k material.
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