CN103675028B - Semiconductor gas sensor and preparation method thereof - Google Patents
Semiconductor gas sensor and preparation method thereof Download PDFInfo
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Abstract
Present invention is disclosed a kind of semiconductor gas sensor and preparation method thereof, wherein this semiconductor gas sensor comprises: substrate, and described substrate has surface; Be arranged on the heating electrode on described surface; Be positioned at the signal sensing electrode of the thermal field that described heating electrode is formed, described signal sensing electrode comprises conductive electrode and is electrically connected the gas sensitive of described conductive electrode; Wherein, insulating medium layer is provided with between described heating electrode and described signal sensing electrode.Semiconductor gas sensor provided by the invention prepares insulating medium layer by adopting the mode of ink jet printing, can greatly reduce the production cost of sensor, and the resolution of ink jet printing is high, can the accurate pattern that designs of positioning printing, technological process is simple.
Description
Technical field
The invention belongs to electronic device manufacturing technology field, be specifically related to the preparation method of a kind of semiconductor gas sensor and this semiconductor gas sensor.
Background technology
Along with the development of society and the progress of science and technology, commercial production scale expands gradually, but the accident caused thus also constantly occurs, inflammable and explosive, the poisonous and hazardous gas that such as petrochemical complex and colliery industry produce, these gases are once exceed standard, leak, by having a strong impact on producers and the healthy of resident of living around, will cause casualties and property loss if set off an explosion.In addition, along with the raising of people's living standard and people are to the transformation of domestic environment finishing requirements, indoor air quality issues is become increasingly conspicuous, due to fit up rear poisonous exceed standard the pernicious case that causes especially time have report.In order to ensure safety and preventing trouble before it happens, be developed various detection method and detecting instrument, wherein gas sensor has been widely used in production and the sphere of life of every profession and trade.
Gas sensor is mainly divided into electric chemical formula, semiconductor-type, thermal conductivity and optical profile type etc.Wherein semiconductor transducer because detection sensitivity is high, response recovery time is short, component size is small, the life-span is long, cheap and be more and more subject to people's attention.Especially in recent years along with the development of micromachining technology, by means of microelectronic technique semiconductor gas sensor especially towards integrated, intelligent direction development.Owing to just showing good sensitivity characteristic when needing to be heated to higher temperature as the metal-oxide semiconductor (MOS) of gas sensitive material, therefore first must prepare the heating electrode of gas sensitive when preparing semiconductor gas sensor, and then prepare signal sensing electrode.
At present, the semiconductor gas sensor prepared with microelectronic technique generally has two kinds of structures, and heating electrode and signal sensing electrode are arranged at the both sides of substrate by the first, and heating electrode is signal sensing heated by electrodes across substrate, and required power consumption is larger; Heating electrode and signal sensing electrode are arranged at the homonymy of substrate by the second, in this kind of structure, homonymy needs heating electrode and signal sensing electrode to be separated with one deck insulating medium layer, this layer of insulating medium layer adopts the mode of physical vapour deposition (PVD) to prepare, need expensive Pvd equipment and grasp complicated etching technics, improve the production cost of sensor.
Summary of the invention
An object of the present invention is to provide a kind of semiconductor gas sensor, and its production cost is lower.
The present invention also aims to the preparation method that a kind of semiconductor gas sensor is provided.
One of for achieving the above object, the invention provides a kind of semiconductor gas sensor, comprising:
Substrate, described substrate has surface;
Be arranged on the heating electrode on described surface;
Be positioned at the signal sensing electrode of the thermal field that described heating electrode is formed, described signal sensing electrode comprises conductive electrode and is electrically connected the gas sensitive of described conductive electrode, and described gas sensitive is positioned on conductive electrode; Wherein,
Insulating medium layer is provided with between described heating electrode and described signal sensing electrode.
As a further improvement on the present invention, the material of described insulating medium layer is selected from one or more in aluminium oxide, silicon dioxide, hafnium oxide.
As a further improvement on the present invention, tack coat is respectively arranged with between described substrate, heating electrode and signal sensing electrode.
As a further improvement on the present invention, described tack coat is Ti metallic film or Cr metallic film or Ti/Cr alloy firm.
As a further improvement on the present invention, described substrate is selected from the one in the silicon chip of surface oxidation, glass sheet, piezoid, alumina ceramic plate, alumimium nitride ceramic sheet, zirconia ceramics sheet, Kapton, and the thickness of described substrate is 100um ~ 1000um.
As a further improvement on the present invention, the material of described heating electrode is selected from the one in gold, silver, platinum, copper, tungsten, platinum alloy, silver palladium alloy, nickel-chrome, molybdenum manganese alloy, titanium nitride, ruthenium-oxide, and the material of described conductive electrode is selected from the one in gold, silver, platinum, copper, tungsten.
As a further improvement on the present invention, described heating electrode is square wave or sawtooth wave or triangular wave or sinusoidal wave or snakelike.
As a further improvement on the present invention, described insulating medium layer is obtained by the mode of ink jet printing.
For realizing another goal of the invention above-mentioned, the invention provides a kind of preparation method of semiconductor gas sensor, the method comprises the following steps:
S1, in substrate, make heating electrode;
S2, in substrate the precursor ink of ink jet printing one deck insulating medium layer;
S3, the substrate through step S2 process to be annealed, obtain being formed in suprabasil insulating medium layer;
S4, on described insulating medium layer, make conductive electrode, and deposit gas sensitive on described conductive electrode, obtain semiconductor gas sensor.
As a further improvement on the present invention, the annealing temperature in step S3 is 500 DEG C ~ 1000 DEG C, and the time of annealing in process is 10min ~ 24h.
As a further improvement on the present invention, the thickness of the insulating medium layer formed in step S3 is 200nm ~ 2um.
Compared with prior art, semiconductor gas sensor provided by the invention prepares insulating medium layer by adopting the mode of ink jet printing, can greatly reduce the production cost of sensor, and, the resolution of ink jet printing is high, can the accurate pattern that designs of positioning printing, and technological process is simple.
Accompanying drawing explanation
Fig. 1 is the structural representation of semiconductor gas sensor one embodiment of the present invention;
Semiconductor gas sensor shown in Fig. 2 Fig. 1 does not make structural representation during signal sensing electrode;
Fig. 3 is in the semiconductor gas sensor shown in Fig. 1, substrate is manufactured with the structural representation of heating electrode;
Fig. 4 is the structural representation of the another embodiment of semiconductor gas sensor of the present invention;
Fig. 5 is the structural representation of the another embodiment of semiconductor gas sensor of the present invention;
Fig. 6 is the structural representation of the another embodiment of semiconductor gas sensor of the present invention;
Fig. 7 is the structural representation of the another embodiment of semiconductor gas sensor of the present invention;
Fig. 8 is the schematic shapes of the wavy heating electrode of sawtooth;
Fig. 9 is the schematic shapes of the wavy heating electrode of triangle;
Figure 10 and Figure 11 is the schematic shapes of sinusoidal wave shape heating electrode;
Figure 12 is the process flow diagram of the preparation method of semiconductor gas sensor of the present invention.
Embodiment
Describe the present invention below with reference to embodiment shown in the drawings.But these embodiments do not limit the present invention, the structure that those of ordinary skill in the art makes according to these embodiments, method or conversion functionally are all included in protection scope of the present invention.
Ginseng Fig. 1 to Fig. 3, introduce the embodiment of semiconductor gas sensor of the present invention, this semiconductor gas sensor 100 comprises substrate 10, signal sensing electrode 30, heating electrode 20 and insulating medium layer 40.
Substrate 10 has surface 11, this surface 11 is determined to carry out follow-up circuit layout relatively, heating electrode 20 is made on this surface 11, signal sensing electrode 30 be arranged in heating electrode 20 formed thermal field, insulating medium layer 40 be arranged between heating electrode 20 and signal sensing electrode 30 with by heating electrode 20 and signal sensing electrode 30 insulated from each other.
Substrate 10 can be selected from the one in the silicon chip of surface oxidation, glass sheet, piezoid, alumina ceramic plate, alumimium nitride ceramic sheet, zirconia ceramics sheet, Kapton, and the thickness of substrate 10 is 100um ~ 1000um.The material of heating electrode 20 is selected from the one in gold, silver, platinum, copper, tungsten, platinum alloy, silver palladium alloy, nickel-chrome, molybdenum manganese alloy, titanium nitride, ruthenium-oxide.
Signal sensing electrode 30 comprises two conductive electrodes 31 and is electrically connected the gas sensitive (not shown) of two conductive electrodes.Conductive electrode 31 can adopt metal, such as, one in Pt, Au, Ag, Cu, Al, Ni, W obtains, at least comprise two signal sensing electrodes 30 in a semiconductor gas sensor 100, according to the difference of kind of sensor, more signal sensing electrodes can be provided with.
Gas sensitive is the crucial component part of semiconductor gas sensor one, to provide semiconductor gas sensor, the gas sensitive wherein selected is nano-metal-oxide functionalized carbon nano-tube material, this nano-metal-oxide functionalized carbon nano-tube material comprises carbon nano-tube and nickel oxide, and the mass ratio of carbon nano-tube and nickel oxide is 1:0.1 ~ 1:30.Further, the mass ratio being further preferably carbon nano-tube and nickel oxide is 1:1 ~ 1:20, and even further, the mass ratio of carbon nano-tube and nickel oxide is 1:1.7 ~ 1:18.Carbon nano tube surface, with hydroxyl bond, with adsorption and oxidation nickel, and more preferably can produce maintenance effect to nickel oxide.
It is random overlap joint between microcosmic carbon nano-tube in the nano-metal-oxide functionalized carbon nano-tube material provided, there is more space each other, nickel oxide is not only adsorbed in the surface of functional layer, in the above-mentioned space in whole carbon nano-tube material region, capital is adsorbed with nickel oxide, like this, flow between the space that gas to be detected can be formed at carbon nano-tube overlap joint, make the Detection results of sensor better.
The material of insulating medium layer is selected from one or more in aluminium oxide, silicon dioxide, hafnium oxide.The thickness of insulating medium layer, relative to the thinner thickness of substrate, can not propose too high demand, and insulation effect is better to the efficiency of heating surface of heating electrode.This insulating medium layer is obtained by the mode of ink jet printing, and ink jet printing resolution is high, can be accurate to several microns, can the accurate pattern that designs of positioning printing, and technological process simply, and easy to operate, cost is lower.
In order to improve the bond strength between substrate 10, heating electrode 20, signal sensing electrode 30, between three, be provided with tack coat (not shown).Tack coat can be Ti metallic film or Cr metallic film or Ti/Cr alloy firm.
Heating electrode 20 is arranged around signal sensing electrode 30, to provide uniform thermal field.Mentioned here " around " can be closed or non-enclosed, uniform thermal field can be provided, to produce better heating effect to signal sensing electrode around the heating electrode 20 arranged.Further, due to the existence of insulating medium layer 40, can there is staggered part in heating 20 and signal sensing electrode 30 each other.
Ginseng Fig. 4, illustrating in an embodiment of semiconductor gas sensor 100, it should be noted that, here in order to be clearly shown that one preferred embodiment, being saved by the insulating medium layer 40 between heating electrode 20 and signal sensing electrode 30 in figure.The secondary heating part 22 that heating electrode 20 comprises main heating part 21 and is connected with main heating part 21, main heating part 21 comprises symmetrically arranged first main bringing-up section 211 and the second main bringing-up section 212, and signal sensing electrode 30 is between the first main bringing-up section 211 and the second main bringing-up section 212.Main heating part 21 is in position relative to secondary heating part 22 adjacent signal sensing electrode 30 more, should be understood that, said " main heating part 21 ", " secondary heating part 22 " are only used to the convenience applying for describing and define, and not represent it and are making differentiation relation processing technology or structure existed fundamentally.Further, although the signal sensing electrode 30 shown in figure is between the first main bringing-up section 211 and the second main bringing-up section 212, due to the existence of insulating medium layer, can have in fact staggered between signal sensing electrode 30 and heating electrode.
In main heating part 21, the thermal field temperature difference that the first main bringing-up section 211 and the second main bringing-up section 212 produce is less than 100 DEG C, and further, this thermal field temperature difference controls as being less than 50 DEG C, with ensure semiconductor gas sensor to object gas detect reliably sensitive.Certainly, in optimal replacement embodiment, the resistance value of the first main bringing-up section 211 and the second main bringing-up section 212 is equal, to ensure that the first main bringing-up section 211 is identical with the temperature of thermal field that the second main bringing-up section 212 produces.
Distance between the conductive electrode 31 that first main bringing-up section 211 is adjacent equals distance between conductive electrode 31 that the second main bringing-up section 212 is adjacent to ensure being heated evenly of conductive electrode, secondary heating part 22 comprises that bringing-up section 211 main with first and the second main bringing-up section 212 be respectively connected first time bringing-up section 221 and second time bringing-up section 222, and this first time bringing-up section 221 and the resistance value of bringing-up section 222 for the second time be also preferably equal.
On the direction overlooked, first time the bringing-up section 221 and pattern congruence that forms of second time bringing-up section 222, meanwhile, more preferably, this first time bringing-up section 221 and for the second time bringing-up section 222 to be mutually symmetrical setting.
Meet above-mentioned to heating electrode 20 in all or part of feature restriction under, the shape of multiple concrete heating electrode can be designed with, below preferentially choose some specific embodiments and do exemplary explanation, same, insulating medium layer in these embodiments is also removed, and, owing to being provided with insulating medium layer 40, also part interlaced with each other can be there is in the heating electrode in these embodiments and signal sensing electrode, and also without limitation as shown in FIG..
The embodiment of ginseng Fig. 4, main heating part 21 is in a flat U-shaped, and around signal sensing electrode 30, heating electrode 20 entirety is in square waveform, and its entirety is arranged along signal sensing electrode 31 in specular.The live width of heating electrode 20 is 10um ~ 200um, and in heating electrode 20, the spacing of each several part changes between 10um ~ 100um.
The embodiment of ginseng Fig. 5, with Fig. 4 unlike, in the present embodiment, the first time bringing-up section 221a of 21a both sides, main heating part and second time bringing-up section 222a is set to the extension of more square-wave-shaped, with provide more powerful heating effect and evenly thermal field.The live width of heating electrode 20a is 10um ~ 200um, and in heating electrode, the spacing of each several part changes between 10um ~ 100um.
The embodiment of ginseng Fig. 6, main heating part 21b is in the folded U-shaped connected, and secondary heating part 22b connects main heating part 21b, and the length of the heating electrode 20b of signal sensing electrode 30b both sides is roughly equal, to provide uniform thermal field.The live width of heating electrode 20b is 10um ~ 200um, and in heating electrode 20b, the spacing of each several part changes between 10um ~ 100um.
The embodiment of ginseng Fig. 7, heating electrode 20c entirety is in snakelike, and the length of the heating electrode of signal sensing electrode 30c both sides is roughly equal, to provide uniform thermal field.The live width of heating electrode 20c is 10um ~ 200um, and in heating electrode 20c, the spacing of each several part changes between 10um ~ 100um.
Heating electrode can also in zig-zag as shown in Figure 8, the triangular waveform shown in Fig. 9, the sinusoidal waveform shown in Figure 10, Figure 11.
Continue ginseng Fig. 1, in the present embodiment, heating electrode 20 has fixed width, and because the thickness of the heating electrode 20 made is equal, therefore heating electrode 20 is in its efficient heat generation region, provides the thermal value of each several part equalization.
Ginseng Figure 12, below provides an embodiment of the preparation method of semiconductor gas sensor of the present invention.In the present embodiment, the method comprises the following steps:
S1, in substrate, make heating electrode.
Heating electrode can adopt the method for physical vapour deposition (PVD) or printing to prepare, and the shape of heating electrode preferably can adopt square piece shape or snakelike.
S2, in substrate the precursor ink of ink jet printing one deck insulating medium layer.
Precursor ink is the combination of one or more in aluminium oxide ink, silicon dioxide ink, hafnium oxide ink.
S3, the substrate through step S2 process to be annealed, obtain being formed in suprabasil insulating medium layer.
Annealing temperature is 500 DEG C ~ 1000 DEG C, and annealing time is 10min ~ 24h, and the final insulating medium layer formed controls at 200nm ~ 2um.
S4, on described insulating medium layer, make conductive electrode, and deposit gas sensitive on described conductive electrode, obtain semiconductor gas sensor.
Below introduce the specific embodiment that some make semiconductor gas sensor of the present invention.
Embodiment 1
Spin coating one deck photoresist in soda-lime glass substrate, through exposure and development after by snakelike heating electrode design transfer on glass, and sputter the thick nickel-chrome formation heating electrode of one deck 500nm with magnetically controlled sputter method, be formed with the thick alumina insulation dielectric layer of soda-lime glass print on substrates one deck 200nm of heating electrode in sputtering with ink-jet printer, and the 10h that anneals at 500 DEG C, finally on insulating medium layer, sputter one deck gold as conductive electrode using magnetically controlled sputter method, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
Embodiment 2
Spin coating one deck photoresist in aluminium oxide ceramics substrate, through exposure and development after by snakelike heating electrode design transfer on glass, and sputter the thick silver palladium alloy formation heating electrode of one deck 800nm with magnetically controlled sputter method, the aluminium oxide ceramics substrate being formed with heating electrode in sputtering with ink-jet printer prints one deck 800nm thick silicon oxide insulating medium layer, and the 10min that anneals at 1000 DEG C, finally on insulating medium layer, sputter one deck gold as conductive electrode using magnetically controlled sputter method, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
Embodiment 3
Aluminium oxide ceramics substrate prints the snakelike heating electrode of the thick silver palladium alloy of one deck 5um with method for printing screen, with ink-jet printer at the thick alumina insulation dielectric layer of the print on substrates one deck 1um being formed with heating electrode, and the 5h that anneals at 1000 DEG C, finally on insulating medium layer, sputter one deck platinum as conductive electrode using magnetically controlled sputter method, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
Embodiment 4
Quartz glass substrate prints the thick ruthenic oxide box-shaped heating electrode of one deck 2um with method for printing screen, with ink-jet printer at the thick hafnia insulating medium layer of the print on substrates one deck 2um being formed with heating electrode, and the 10h that anneals at 700 DEG C, finally on insulating medium layer, sputter one deck silver for conductive electrode with magnetically controlled sputter method, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
Embodiment 5
Aluminium nitride ceramics substrate prints the thick silver-colored palladium box-shaped heating electrode of one deck 10um with method for printing screen, with ink-jet printer at the thick alumina insulation dielectric layer of the print on substrates one deck 800nm being formed with heating electrode, and the 24h that anneals at 700 DEG C, finally on insulating medium layer, print one deck silver as conductive electrode electrode with method for printing screen, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
Embodiment 6
Spin coating one deck photoresist in hafnia ceramic bases, through exposure and development after by snakelike heating electrode design transfer in hafnia ceramic bases, the thick gold of one deck 800nm is sputtered as heating electrode with magnetically controlled sputter method, the thick hafnia insulating medium layer of print on substrates one deck 500nm of heating electrode is formed with in sputtering with ink-jet printer, and the 1h that anneals at 800 DEG C, finally print one deck gold as conductive electrode with method for printing screen, conductive electrode deposits gas sensitive and obtains semiconductor gas sensor chip.
The present invention is by above-mentioned embodiment, there is following beneficial effect: semiconductor gas sensor provided by the invention prepares insulating medium layer by adopting the mode of ink jet printing, the production cost of sensor can be greatly reduced, and, the resolution of ink jet printing is high, can the accurate pattern that designs of positioning printing, technological process is simple.
Be to be understood that, although this instructions is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of instructions is only for clarity sake, those skilled in the art should by instructions integrally, technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
A series of detailed description listed is above only illustrating for feasibility embodiment of the present invention; they are also not used to limit the scope of the invention, all do not depart from the skill of the present invention equivalent implementations done of spirit or change all should be included within protection scope of the present invention.
Claims (10)
1. a semiconductor gas sensor, is characterized in that, comprising:
Substrate, described substrate has surface;
Be arranged on the heating electrode on described surface;
Be positioned at the signal sensing electrode of the thermal field that described heating electrode is formed, described signal sensing electrode comprises conductive electrode and is electrically connected the gas sensitive of described conductive electrode, and described gas sensitive is positioned on conductive electrode; Wherein,
Insulating medium layer is provided with between described heating electrode and described signal sensing electrode.
2. semiconductor gas sensor according to claim 1, is characterized in that, the material of described insulating medium layer is selected from one or more in aluminium oxide, silicon dioxide, hafnium oxide.
3. semiconductor gas sensor according to claim 1, is characterized in that, is respectively arranged with tack coat between described substrate, heating electrode and signal sensing electrode.
4. semiconductor gas sensor according to claim 3, is characterized in that, described tack coat is Ti metallic film or Cr metallic film or Ti/Cr alloy firm.
5. semiconductor gas sensor according to claim 1, it is characterized in that, described substrate is selected from the one in the silicon chip of surface oxidation, glass sheet, piezoid, alumina ceramic plate, alumimium nitride ceramic sheet, zirconia ceramics sheet, Kapton, and the thickness of described substrate is 100um ~ 1000um.
6. semiconductor gas sensor according to claim 1, it is characterized in that, the material of described heating electrode is selected from the one in gold, silver, platinum, copper, tungsten, platinum alloy, silver palladium alloy, nickel-chrome, molybdenum manganese alloy, titanium nitride, ruthenium-oxide, and the material of described conductive electrode is selected from the one in gold, silver, platinum, copper, tungsten.
7. semiconductor gas sensor according to claim 1, is characterized in that, described heating electrode is square wave or sawtooth wave or triangular wave or sinusoidal wave or snakelike.
8. semiconductor gas sensor according to claim 1, is characterized in that, described insulating medium layer is obtained by the mode of ink jet printing.
9. a preparation method for semiconductor gas sensor, is characterized in that, the method comprises the following steps:
S1, in substrate, make heating electrode;
S2, in substrate the precursor ink of ink jet printing one deck insulating medium layer;
S3, the substrate through step S2 process to be annealed, obtain being formed in suprabasil insulating medium layer;
S4, on described insulating medium layer, make conductive electrode, and deposit gas sensitive on described conductive electrode, obtain semiconductor gas sensor.
10. method according to claim 9, is characterized in that, the annealing temperature in step S3 is 500 DEG C ~ 1000 DEG C, and the time of annealing in process is 10min ~ 24h, and the thickness of the insulating medium layer of formation is 200nm ~ 2um.
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| CN104931539B (en) * | 2015-06-11 | 2017-12-19 | 福建工程学院 | A kind of semiconductor gas sensing device and preparation method thereof |
| CN105699453A (en) * | 2016-01-24 | 2016-06-22 | 西南大学 | Preparation method and application of ink jet printing plane three-electrode system |
| CN106018484A (en) * | 2016-07-13 | 2016-10-12 | 苏州纳格光电科技有限公司 | Semiconductor gas sensor chip, sensor and preparation method of sensor |
| IT202100029513A1 (en) | 2021-11-22 | 2023-05-22 | Milano Politecnico | Gas sensor |
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