CN102778479B - Integratable amorphous metal oxide semiconductor gas sensor - Google Patents
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- CN102778479B CN102778479B CN201110117658.7A CN201110117658A CN102778479B CN 102778479 B CN102778479 B CN 102778479B CN 201110117658 A CN201110117658 A CN 201110117658A CN 102778479 B CN102778479 B CN 102778479B
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Abstract
The invention provides an integratable amorphous metal oxide semiconductor gas sensor. The gas sensor provided by the invention comprises a substrate, a heating electrode formed on the substrate, a signal detection electrode formed on the substrate and located at a same side as the heating electrode does and a gas-sensitive detection film formed on the substrate, the heating electrode and the signal detection electrode, and the gas sensor is characterized in that the gas-sensitive detection film includes an amorphous metal oxide semiconductor. According to the gas sensor provided by the invention, since the amorphous semiconductor is used as the gas-sensitive detection film, a standard manufacturing process for semiconductors can be used for preparation of the gas sensor, and therefore, cost is reduced, uniformity and the response speed of a device are improved, and working temperature and power consumption are reduced; thus, high-efficiency low-cost large-area integration of the gas sensor is realized.
Description
Technical field
The present invention relates to a kind of semiconductor sensor part, particularly relate to the semi-conductive gas sensor of amorphous metal oxide that a kind of efficient low-cost large scale can be integrated.
Background technology
Along with the development of social life and industrial technology, gas sensor has more and more important effect in 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; The monitoring of CO during life is produced; Detection to ethanol, methyl alcohol; To detection of vehicle exhaust etc.
Since the sixties in last century, metal-oxide semiconductor (MOS) gas sensor just with higher sensitivity, respond the principal market that the advantage such as rapid occupies gas sensor.Initial gas sensor mainly adopts SnO
2, ZnO is gas sensitive, researched and developed again in recent years some new materials, except a small amount of single metal oxide materials, as WO
3, In
2o
3, TiO
2, Al
2o
3deng outside, the focus of exploitation mainly concentrates on composite metal oxide and potpourri metal oxide is as shown in table 1.
The metal oxide sensitive material that all kinds of detection gas of table 1 is corresponding
Metal oxide semiconductor sensor can be divided into two kinds of resistance-type and non-resistance-types ultimate principle.
SnO
2, ZnO constant resistance formula metal oxide semiconductor sensor ultimate principle be to utilize the oxide semiconductor adsorption of gas and the resistance characteristic that catalysis double effect changes material to external world, thereby reach monitoring object, belong to surperficial control type, but the serviceability temperature of such semiconductor transducer is higher, at 200～500 ℃, just possesses greatly higher sensitivity.Some are improved one's methods is in basic material, to add some noble metals (as Ag, Au, Pb etc.), activator and adhesive A l
2o
3, SiO
2, ZrO
2deng improving sensitivity, improve the response time, reduce working temperature, improve selectivity etc.The method of 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 being developed into the earliest, and when hydrogen and Pd have an effect, the threshold voltage of FET will change with density of hydrogen, with this, detect hydrogen.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.Directly-heated type slug type is mainly comprised of gas sensitive material, heater strip and signal silk.Heater strip and measure silk and be all directly embedded in gas sensitive, the heater strip heating that is used for switching on, 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 element function consistance is poor.Because element is little, thermal capacity is also little, affected by ambient windstream, and between measuring circuit and heating circuit, not isolation, interacts.Heater strip is in heating and under heated condition, can not produce breathing, easily causes the loose contact of material.
Heater-type structure is in tube core inside, to have increased a capillary ceramic pipe, and heater strip penetrates in ceramic pipe, outside pipe, coats gold electrode as the signal electrode of measuring sensor resistance, is coated with sensitive material outward, fired forming at gold electrode.This structure has overcome some shortcoming of directly-heated type element, because heater strip does not contact with gas sensitive, avoided the phase mutual interference between measuring circuit and heating circuit, the consistance of element function improves a lot, physical strength is also greatly improved, and becomes a kind of major structural types of current commercialization gas sensor.
It is substrate that thick-film type sensor generally be take very thin oxidation pot potsherd, the back side at substrate coats from heater core, the methods such as evaporation for another side, sputter are made bar shaped gold (or platinum) electrode, on electrode, adopt the acute technology of screen printing, the air-sensitive slurry preparing is coated with and is stamped, then drying sintering forms.
The structure of film-type sensor and thick film device are similar, and difference is not only to adopt screen printing technique to adopt in the preparation of gas sensing layer, but adopts the 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 is prepared on silicon substrate, can utilize the advanced technologies such as semiconductor planar processing technology, be conducive to the integrated of difference in functionality element, and on silicon substrate, make micro-hotplate structure, power consumption is very little, about milliwatt magnitude is the main development 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 be subject to certain restrictions.Utilize the advanced technologies such as semiconductor planar technique, the film-type element of difference in functionality can be integrated on 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 structures are respectively had its own relative merits, the element technique of thick-film type and heater-type structure comparatively speaking fairly simple, cost is low, but power consumption is large, consistance is poor, it is not high enough to respond, volume is large, 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 technique that flakiness structure is corroded in back, the structures such as successively deposit thereon and formation dielectric isolation layer, METAL HEATING PROCESS electrode, heat rejection absciss layer, gas sensitive and extraction electrode, because heating and the large portion silicon materials at back, sensitizing range are removed, 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 conventional cmos circuit of silicon substrate, realize monolithic integrated simultaneously, reduce sensor bulk and overall cost.This structure is called as micro-hotplate integrated sensor.
Yet conventional micro-hotplate integrated sensor is based upon on silicon substrate and is applied to special MEMS technique, so cost is higher.The potpourri that 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 are just to overcome series of problems such as technique, cost, homogeneity, response efficiency, reaction velocity, working temperature and power consumption in existing film integrated-type gas sensor the amorphous oxide semiconductor material that is applied to detection of gas and the device architecture that a kind of novel high efficiency, low cost Large-Area-Uniform can be integrated are provided.
The invention provides a kind of gas sensor, comprising: substrate; Heating electrode, is formed on described substrate; Signal detection electrode, is formed on described substrate, coplanar with described heating electrode; Gas sensitization is surveyed film, is formed in described substrate, described heating electrode and described signal detection electrode; It is characterized in that, described gas sensitization is surveyed film and is comprised non-crystal oxide semiconductor.
The present invention also provides a kind of gas sensor, comprising: substrate; Heating electrode, is formed on described substrate; Isolation insulating film, is formed on described substrate and described heating electrode; Gas sensitization is surveyed film, is formed on described isolation insulating film; Signal detection electrode, is formed on described gas sensitization and surveys on film; It is characterized in that, described gas sensitization is surveyed film and is comprised non-crystal oxide semiconductor.
Wherein, described non-crystal oxide semiconductor comprises the zno-based semiconductor of mixing In, described in mix In zno-based semiconductor comprise InGaZnO, InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO.Wherein, described in mix [In]/([In]+[the 3rd metal]) in the zno-based semiconductor of In atom counting than being 35%～80%, 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, described non-crystal oxide semiconductor comprises In
2o
3, ZTO, ITO, ZnO, SnO
x.
Wherein, described non-crystal oxide semiconductor thickness is 1 to 10000nm.
Wherein, at the bottom of described substrate comprises the silicon wafer-based of surface for the silicon chip of insulation course, glass, quartz, plastics or back hollow out.Wherein, the material of described heating electrode and/or described signal detection electrode comprises Mo, Pt, Al, Ti, Co, Au, Cu, polysilicon, TiN, TaN and combination thereof.Wherein, the material of described isolation insulating film comprises silicon dioxide, silicon nitride, silicon oxynitride or high k material.
According to gas sensor of the present invention, owing to having adopted amorphous semiconductor, as gas sensitization, survey film, make gas sensor can adopt semiconductor standard manufacture technique, reduced cost, homogeneity, the response speed of device have been improved, reduced working temperature and power consumption, therefore can high efficiency, low cost integrated in large area.
Object of the present invention, and in these other unlisted objects, in the scope of the application's independent claims, met.Embodiments of the invention are limited in independent claims, and specific features is limited in its dependent claims.
Accompanying drawing explanation
Referring to accompanying drawing, describe technical scheme of the present invention in detail, 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 Electro 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 Electro 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
3C heating electrode
4, isolation insulating film
Embodiment
Referring to accompanying drawing, also in conjunction with schematic embodiment, describe feature and the technique effect thereof of technical solution of the present invention in detail, disclose amorphous metal oxide semiconductor gas sensor that can be integrated.It is pointed out that structure like similar Reference numeral representation class, term " first " used in the application, " second ", " on ", D score etc. can be used for modifying various device architectures.These modify space, order or the hierarchical relationship that not implies unless stated otherwise institute's modification device architecture.
As shown in Figure 1A, be the schematic 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 is for example for surface (is preferably silicon-on-insulator SOI for the silicon chip of insulation course, also can on body silicon substrate, deposit or the laying of silicon dioxide is made in thermal oxide, can also on body silicon, form the insulation course of silicon nitride or silicon oxynitride), glass (can be doped to conventional boron-phosphorosilicate glass BPSG, also can be spin-coating glass SOG, glass substrate 1 preferably has rectangular shape to be suitable for cutting and large area manufacture), quartzy, at the bottom of the silicon wafer-based of plastics (being preferably the composition with higher melt and hardness and good insulation properties) and back hollow out etc.Substrate 1 is tabular substantially, comprises a pair of first type surface, is also 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, such as realizing by common technologies such as rare HF acid wet etching or plasma etchings, can also form cushion to slow down stress or bonding coat to strengthen bond strength (cushion or bonding coat are not shown).
On the upper surface of substrate 1, form electrode layer 3, preferably adopt the mode of sputtering deposit, its material, such as being Mo, Pt, Al, Ti, Co, Au, Cu etc., can be the other materials with conducting function in addition, doped polycrystalline silicon for example, metal nitrides such as TiN, TaN etc.Can be first during preparation even sputtering deposit one deck electrode layer material, then according to electrode domain, carry out etching and remove unwanted part.After etching, leave electrode 3A and the 3B of pair of opposing, form signal detection electrode, in the signal detection electrode 3A plane identical with 3B, be also provided with heating of metal electrode 3C, heating electrode 3C forms together with can adopting same material with signal detection electrode 3A/3B, also can adopt two step depositing operations to use different materials and form.As shown in Figure 1B, signal detection electrode 3A and 3B are oppositely arranged, and are preferably formed as staggered pair of electrodes is for bias voltage and drawing.The shape of signal detection electrode 3A and 3B is not limited to shown in 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 signal detection electrode 3A and 3B, and preferably or spacing parallel with both equates, so that homogeneous heating.The end of three electrodes is formed with contact pad separately, for being connected with external circuit.Heating electrode 3C also can be around signal detection electrode 3A/3B, or parallel etc. with it, without being defined as shown in Figure 1B, can only be plugged in therebetween.The width of electrode 3A/3B/3C and thickness need and set according to electric property and the heating of measuring element structure, the width and the thickness that are not limited in Figure 1B all equate, but for the consideration of being convenient to sputtering technology and controlling, be preferably that three's thickness is identical and width is adjustable.
Subsequently at upper surface and signal detection electrode 3A and the 3B of substrate 1, and on heating electrode 3C, be formed with gas sensitization and survey film 2, (this window can be by nitride for the exposure window of the region foundation gas to be measured of formation gas sensitization detection film 2, the passivating film of the formation such as oxide and defining, can form passivation film after etching and go out window deposition gases sensitive detection film 2 again, also can after deposition gases sensitive detection film 2, form again passivation film and etch window) and determine, for example, shown in Figure 1B rectangular area, but can be also other geometric configuratioies, triangle for example, parallelogram, trapezoidal, regular polygon, circular etc.Gas sensitization is surveyed film 2 and is consisted of non-crystal oxide semiconductor, can from table 1, select corresponding oxide semiconductor, particularly broad-band gap (>=2.0eV) non-crystal oxide semiconductor according to probe gas type difference.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, the zno-based semiconductor of mixing In is for example GaInZnO (IGZO), InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO, and other binary or multicomponent amorphous oxide semiconductor are for example 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 material, In atom outer-shell electron is main conduction electrons source, by adjacent oxygen room, conduct electricity, Zn atom plays the effect of stablizing micro-cell configuration, thereby and grade in an imperial examination three adulterants such as other Ga, Hf, Ta, Zr, Y, Al, Sn start to control the generation rate in oxygen room changes 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 in the present invention magnetron sputtering method.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, select suitable Ar/O
2ratio, sputtering pressure, sputtering power, underlayer temperature, annealing time and temperature etc.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 to be selected to form is surveyed film 2 according to 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 by 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 by adding the 3rd metal or being adjusted to film thickness, obtain required non-crystal oxide semiconductor, these technology are known conventional to those skilled in the art.
During device work, from the two ends of heating electrode 3C, apply power supply with heated air sensitive detection film 2, gas sensitization is surveyed film 2 and is received by being exposed to outer window area the gas coming from the outside, as shown in arrow in Figure 1A, therefore the resistance that gas sensitization is surveyed film 2 change, also make signal detection electrode change to the resistance between 3A and 3B, thereby can determine by the outer detecting circuit being attached thereto the existence of certain special gas.
Compare polycrystalline, crystalline state and crystallite semiconductor, amorphous semiconductor shows shortrange order, isotropy, manufacture craft is simple, easily make large area film, and in being with defect more, introduce more local energy level, be more conducive to the absorption of oxonium ion in gas.Take typical material IGZO as example, and ternary mixed type non-crystal oxide metal semiconductor IGZO is by In
2o
3, Ga
2o
3form with ZnO, energy gap, in 3.4eV left and right, is a kind of ionic amorphous state N-type semiconductor material.In
2o
3in In
3+can form 5S electron trajectory, be conducive to the high-speed transfer of charge carrier; Ga
2o
3there is very strong ionic link, can suppress the generation in O room; Zn in ZnO
2+can form stable tetrahedral structure, can make in theory metal oxide IGZO form the non crystalline structure of stable higher conduction.Non-crystal oxide semiconductor belongs to ionic amorphous semiconductor, and conduction is by the mutual overlapping carrier transport of realizing of atom outer-shell electron cloud of large radius, thereby the large (10～100cm of mobility
2/ Vs).
The conductive characteristic of IGZO film is subject to external environment parameters, comprises the impact of the many factors of air humidity, air pressure and temperature.Such as, the external environment parameters particularly dividing potential drop of oxygen has significant impact to the electric conductivity of oxide.The electronic conduction of IGZO need to 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 gate voltage effect, there is field and help 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 be associated with the intrinsic change in resistance of material.The dividing potential drop of hydrogen has material impact to the isoionic combination of H-O, OH and generation simultaneously, also has influence on the absorption to this type of ion of semiconductive thin film, thereby changes to 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) to produce in sull adsorption process are carried out perception gas, and this reaction is based upon on certain surface state.The absorption of gas on 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 from semiconductor to adatom or moves to semiconductor from foreign atom, all will cause that 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 enters physics and chemistry absorption on gas sensitive surface, comprise two kinds of physisorption and chemisorption, and under room temperature, this process is carried out slowlyer, if temperature is higher, and O
2-can be further converted to O
-form.O
-activity very high, can be adsorbed on lip-deep other reducibility gas ionic group of gas sensitive and react rapidly, as C
2h
5oH etc., will the redox chemical reaction of generating polynomial, and the extra electron that course of reaction produces enters conduction band, causes gas sensitive resistance variations; In addition, for intermediate oxide gas sensitive, except above-mentioned oxygen absorption, also have OH-absorption, be conducive to adsorbent and carry out redox reaction at metal oxide surface, the electronics wherein discharging enters conduction band, causes gas sensitive resistance variations.This type of material and ambient humidity have compared with Important Relations.
By above-mentioned Analysis on Mechanism, can find out that 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 state, particulate form, crystallite states, amorphous attribute can provide more reaction table area, from atom level, provides the chemical reaction of gas sensitization, thereby has improved the overall susceptibility of film simultaneously.
In addition, the zno-based semiconductor film material of mixing In used in the present invention can also be for other field, ultraviolet detector etc. for example, according to gas detector of the present invention can also with the integrated manufacture of these other semiconductor devices, further reduce cost and improved efficiency.
As shown in Figure 2 A, be the 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., first sputtering deposit is formed with ground floor electrode material layer, electrode layer material is similar to Example 1, at this, no longer strolls and states.This electrode layer of etching forms heating electrode 3C, and heating electrode 3C surveys film heating gas sensitization except applying power supply by 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 same plane with heating electrode 3C, but mutually insulated isolation, the power supply that the grid bias applying applies while being also different from heating.
After forming heating electrode 3C, on whole device architecture, pass through such as being the conventional method formation isolation insulating films 4 such as CVD, PVD.For accelerating heat conducting consideration, preferably those have the isolated insulation material of higher heat-conductivity; For the consideration of electrical insulation isolation, can adopt the material of those relative dielectric constants higher (being for example greater than 3.9).Particularly, isolation insulating film 4 can be silicon dioxide, silicon nitride, silicon oxynitride, or hafnia, tantalum oxide, the contour k material of 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 etc. and form, be preferably magnetron sputtering method.Its material is similar to Example 1, can from table 1, select corresponding oxide semiconductor, particularly broad-band gap (>=2.0eV) non-crystal oxide semiconductor according to probe gas type difference.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, the zno-based semiconductor of mixing In is for example GaInZnO (IGZO), InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO, and other binary or multicomponent amorphous oxide semiconductor are for example 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.
Finally, at gas sensitization, survey on film 2 and form signal detection electrode 3A and 3B, its forming process, material, shape etc. are similar to Example 1, at this, no longer stroll and state.When the present invention adopts extra TFT grid, signal detection electrode 3A and 3B are preferably symmetrical around TFT grid.
During device work, to TFT gate electrode, 3D applies bias voltage, then from the two ends of heating electrode 3C, apply power supply to see through isolation insulating film 4 indirect heating gas sensitizations detection films 2, gas sensitization is surveyed film 2 and is received by being exposed to outer window area the gas coming from the outside, as shown in arrow in Fig. 2 A, therefore the electric isolation characteristic that gas sensitization is surveyed film 2 changes, therefore as the signal detection electrode 3A of TFT source-drain electrode and the voltage-current characteristic between 3B, change, thereby judge through outer detecting circuit the existence of determining special gas.In non-crystal oxide semiconductor indirect resistance TFT type gas sensor, the gas sensitization of reactive film conduction that can be sensitiveer under active condition (grid-control bias voltage) by the susceptibility of surface resistance and the high mobility of material changes, thereby further improves the susceptibility of device.In addition, the good electrical characteristic of this device is conducive to the integration of online pre-service monolithic integrated signal circuit, realizes single chip integrated gas sensor.
According to gas sensor of the present invention, owing to having adopted amorphous semiconductor, as gas sensitization, survey film, make gas sensor can adopt semiconductor standard manufacture technique, reduced cost, homogeneity, the response speed of device have been improved, 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 without departing from the scope of the invention device architecture is made to various suitable changes and equivalents.In addition, by disclosed instruction, can make and manyly may be suitable for the modification of particular condition or material and not depart from the scope of the invention.Therefore, object of the present invention does not lie in and is limited to as the disclosed specific embodiment for realizing preferred forms of the present invention, and disclosed device architecture and manufacture method thereof will comprise all embodiment that fall in the scope of the invention.
Claims (9)
1. a gas sensor, comprising:
Substrate;
Heating electrode, is formed on described substrate;
Signal detection electrode, is formed on described substrate, coplanar with described heating electrode;
Gas sensitization is surveyed film, is formed in described substrate, described heating electrode and described signal detection electrode;
It is characterized in that,
Described gas sensitization is surveyed film and is comprised non-crystal oxide semiconductor, and described non-crystal oxide semiconductor comprises zno-based semiconductor, the In that mixes In
2o
3, ITO, the semi-conductive band gap of described non-crystal oxide is more than or equal to 2.0eV.
2. a gas sensor, comprising:
Substrate;
Heating electrode, is formed on described substrate;
Isolation insulating film, is formed on described substrate and described heating electrode;
Gas sensitization is surveyed film, is formed on described isolation insulating film;
Signal detection electrode, is formed on described gas sensitization and surveys on film;
It is characterized in that,
Described gas sensitization is surveyed film and is comprised non-crystal oxide semiconductor, and described non-crystal oxide semiconductor comprises zno-based semiconductor, the In that mixes In
2o
3, ITO, the semi-conductive band gap of described non-crystal oxide is more than or equal to 2.0eV.
3. gas sensor as claimed in claim 1 or 2, wherein, described in mix In zno-based semiconductor comprise InGaZnO, InZnO, HfInZnO, TaInZnO, ZrInZnO, YInZnO, AlInZnO, SnInZnO.
4. gas sensor as claimed in claim 3, wherein, described in mix [In]/([In]+[the 3rd metal]) in the zno-based semiconductor of In atom counting than being 35%～80%, 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. gas sensor as claimed in claim 1 or 2, wherein, described non-crystal oxide semiconductor thickness is 1 to 10000nm.
7. gas sensor as claimed in claim 1 or 2, wherein, at the bottom of described substrate comprises the silicon wafer-based of surface for the silicon chip of insulation course, glass, quartz, plastics or back hollow out.
8. gas sensor as claimed in claim 1 or 2, wherein, the material of described heating electrode and/or described signal detection electrode comprises Mo, Pt, Al, Ti, Co, Au, Cu, polysilicon, TiN, TaN and combination thereof.
9. gas sensor as claimed in claim 2, wherein, the material of described isolation insulating film comprises silicon dioxide, silicon nitride, silicon oxynitride or high k material.
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