CN108375498B - Gas concentration and sensing integrated device and preparation method thereof - Google Patents
Gas concentration and sensing integrated device and preparation method thereof Download PDFInfo
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- CN108375498B CN108375498B CN201810120026.8A CN201810120026A CN108375498B CN 108375498 B CN108375498 B CN 108375498B CN 201810120026 A CN201810120026 A CN 201810120026A CN 108375498 B CN108375498 B CN 108375498B
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Abstract
The invention discloses a gas concentration and sensing integrated device and a preparation method thereof. The integrated device is a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater, an annular insulating layer and an annular gas concentrator which are sequentially arranged on a silicon chip with a mesoporous heat-insulating layer coated on the surface, wherein the width of the annular platinum micro-heater is less than or equal to 1 mu m, the thickness of the annular platinum micro-heater is 200-500nm, and the electrodes are respectively electrically connected with the platinum micro-heater and a power supply; the method comprises the steps of coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface for multiple times, etching a pattern of a corresponding device on the electron beam resist by an electron beam exposure method, sputtering or evaporating the corresponding device on the pattern, and growing a gas concentrator on the annular insulating layer to obtain the target product. The gas detection device has the advantages of compact structure, low power consumption, high detection limit, real-time performance and convenience, and is extremely easy to be widely applied to high-sensitivity detection of gas, so that the gas detection device has wide application prospect in the fields of wearable or embeddable intelligent terminals and the like.
Description
Technical Field
The invention relates to an integrated device and a preparation method thereof, in particular to a gas concentration and sensing integrated device and a preparation method thereof.
Background
Trace gas in indoor and outdoor environments carries important information related to environment and health, and the micro semiconductor gas sensor which is wearable or can be embedded into the intelligent terminal is researched and developed, is in the development front of the era of the Internet of things, and has wide market application prospect. Recently, some beneficial attempts and efforts have been made to further raise the detection limit of oxide semiconductor gas sensors to strongly promote their application in the fields of trace amount of polluted gas, detection of respiratory gas, etc., such as "apparatus Measurement of Acetone from Skin Using Zeol ite" heated Development of a Wearable Monitor of a Fat monitoring of Fat metabolism, Analytical Chemistry87(2015)7588-7594 (detection of acetone released by the skin using zeolite: development of a wearable fat metabolism monitoring sensor ", analytical chemistry 2015, volume 87, page 7588-7594). The monitoring sensor mentioned in the article is a gas concentrator which is arranged in a glass bottle and is internally provided with an acetone sensor and a platinum heating wire wound outside the acetone sensor, wherein both ends of the acetone sensor and the platinum heating wire are connected with electrodes, the gas concentrator is zeolite, and the electrodes are connected with a power supply outside the bottle; during measurement, the glass bottle mouth is covered on the skin region to be measured for a period of time to enable the zeolite to fully adsorb acetone molecules in the region to be measured, and then the zeolite is heated through the platinum electric heating wire, so that the acetone molecules enriched on the zeolite are quickly desorbed and diffused on the surface of the acetone sensor, and the purpose of improving the detection limit of the acetone sensor is achieved. The monitoring sensor can be used for detecting trace acetone gas, but has the defects that the monitoring sensor is large in size, the volume of a glass bottle for placing a whole set of concentration measuring device is up to 16.9ml, and the monitoring sensor cannot be integrated into intelligent terminals such as mobile phones; secondly, the acetone sensor is far away from the gas concentrator, and is centimeter-level, so that the concentration effect of the gas concentrator is seriously weakened; thirdly, the volume of the platinum heating wire for heating the zeolite gas concentrator is over-large-300 multiplied by 500 mu m3Not only causes the power consumption of the platinum heating wire to be larger, but also causes the thermal relaxation time of the acetone sensor and the gas concentrator to be longer, which is not beneficial to carrying out rapid sampling test.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a gas concentration and sensing integrated device which is compact in structure, low in power consumption and convenient and fast to detect.
The invention also provides a preparation method of the gas concentration and sensing integrated device.
In order to solve the technical problem of the invention, the technical scheme is that the gas concentration and sensing integrated device consists of a gas sensor, a gas concentrator, an electric heater and electrodes in a positioning shell, and a power supply connected with the electrodes, in particular to the gas concentration and sensing integrated device which comprises:
the positioning shell is a silicon wafer with a mesoporous heat insulation layer covered on the surface;
the gas sensor is a metal oxide gas sensor, and the metal oxide gas sensor is attached to the silicon chip with the surface covered with the mesoporous heat insulation layer;
the gas concentrator is annular and is attached to the periphery of the metal oxide gas sensor;
the electric heater is a platinum (Pt) micro-heater with the width less than or equal to 1 mu m and the thickness of 200-500nm, and the platinum micro-heater is positioned below the annular gas concentrator;
annular insulating layers are arranged between the platinum micro-heater and the periphery of the metal oxide gas sensor and between the platinum micro-heater and the annular gas concentrator;
the electrode is respectively and electrically connected with the metal oxide gas sensor and the platinum micro-heater.
As a further improvement of the gas concentration and sensing integrated device:
preferably, the metal oxide gas sensor has a length of 3-5 μm, a width of 0.3-1.5 μm, and a thickness of 100-200nm, wherein the metal oxide is tin dioxide (SnO)2) Or indium oxide (In 2O)3) Or gallium oxide (Ga 2O)3) Or tungsten trioxide (WO)3) Or molybdenum trioxide (MoO)3) Or copper oxide (CuO), or nickel oxide (NiO), or chromium oxide (Cr 2O)3)。
Preferably, the annular gas concentrator is annular and is concentric with the metal oxide gas sensor, the radius of the inner ring is 4-6 μm, the radius of the outer ring is 8-12 μm, and the thickness is 500-1000nm, and the material of the annular gas concentrator is organic mesoporous material, or inorganic mesoporous material, or oxide nanowire array.
Preferably, the layer thickness of the annular insulating layer is more than or equal to 80nm, and the annular insulating layer is an annular silicon dioxide insulating layer, an annular aluminum oxide insulating layer or an annular zirconium dioxide insulating layer.
In order to solve another technical problem of the present invention, another technical solution is that the method for manufacturing the gas concentration and sensing integrated device includes an electron beam exposure method, and particularly includes the following main steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, then etching a sensor pattern on the silicon wafer by an electron beam exposure method, sputtering a metal oxide gas sensor on the sensor pattern by a magnetron sputtering method, then placing the sensor pattern in a dimethylformamide solution to strip the electron beam resist, and obtaining the silicon wafer with the metal oxide gas sensor on the surface and the mesoporous heat insulation layer;
step 3, coating an electron beam resist on a silicon wafer, which is coated with a mesoporous thermal insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method, sputtering an insulation layer on the ring shape by using a magnetron sputtering method, placing the ring shape in a dimethylformamide solution, and stripping the electron beam resist to obtain the metal oxide gas sensor coated with the connecting electrode and the silicon wafer coated with the mesoporous thermal insulation layer on the surface of the ring insulation layer in sequence;
step 4, coating an electron beam resist on a silicon wafer on which a metal oxide gas sensor for connecting electrodes and a mesoporous heat insulation layer are sequentially coated, etching a platinum micro-heater graph on the annular insulation layer by an electron beam exposure method, evaporating a platinum micro-heater on the platinum micro-heater graph, and then placing the platinum micro-heater graph in a dimethylformamide solution to strip the electron beam resist to obtain the silicon wafer on which the metal oxide gas sensor for connecting electrodes, the annular insulation layer and the mesoporous heat insulation layer are sequentially coated;
and 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is sequentially coated with a metal oxide gas sensor for connecting electrodes, an annular insulating layer and a mesoporous heat insulating layer on the surface of the annular platinum micro-heater, then engraving an annular platinum micro-heater by using an electron beam exposure method, sputtering the insulating layer on the annular platinum micro-heater by using a magnetron sputtering method, growing a gas concentrator on the annular platinum micro-heater, and then placing the annular platinum micro-heater in a dimethylformamide solution to strip the electron beam resist to obtain the gas concentration and sensing integrated device.
The preparation method of the integrated gas concentration and sensing device is further improved as follows:
preferably, the electron beam resist is a ZEP 520A electron beam resist, or a Polymethylmethacrylate (PMMA) electron beam resist.
Preferably, the sputtering power is 80-120W, the sputtering time is 10-60min, the length of the metal oxide gas sensor is 3-5 μm, the width is 0.3-1.5 μm, and the thickness is 100-200nm when the magnetron sputtering method is used for sputtering the metal oxide gas sensor in the step 1, wherein the metal oxide is tin dioxide (SnO)2) Or indium oxide (In 2O)3) Or gallium oxide (Ga 2O)3) Or tungsten trioxide (WO)3) Or molybdenum trioxide (MoO)3) Or copper oxide (CuO), or nickel oxide (NiO), or chromium oxide (Cr 2O)3)。
Preferably, the evaporation of the electrode and the platinum sheet is magnetron sputtering, or direct current sputtering, or electron beam evaporation.
Preferably, the layer thickness of the annular insulating layer is more than or equal to 80nm, and the annular insulating layer is an annular silicon dioxide insulating layer, an annular aluminum oxide insulating layer or an annular zirconium dioxide insulating layer.
Preferably, the growth process of the gas concentrator comprises the steps of firstly carrying out oxygen plasma cleaning on a silicon wafer, the surface of which is covered with a mesoporous heat-insulating layer, a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater and an annular insulating layer, which are sequentially covered with a connecting electrode, and an electron beam resist, and then soaking the silicon wafer into a mixed solution of 15-25mmol/L zinc nitrate methanol solution and 35-45 mmol/L2-methylimidazole methanol solution for standing for 20-40min to obtain a molecular sieve concentrator positioned on the annular insulating layer; wherein, the radio frequency power when the oxygen plasma is cleaned is 80-120W, the oxygen pressure is 0.5-1.5Torr, the cleaning time is more than or equal to 20s, the volume ratio of the zinc nitrate methanol solution to the 2-methylimidazole methanol solution in the mixed solution is 0.8-1.2: 0.8-1.2.
Preferably, the growth process of the gas concentrator comprises the steps of sputtering a zinc oxide seed layer with the thickness of 1-20nm on a silicon wafer, the silicon wafer is sequentially coated with a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater and an annular insulating layer which are connected with electrodes, and an electron beam resist, the surface of the silicon wafer is coated with a mesoporous heat-insulating layer, and then growing a zinc oxide nanowire array on the zinc oxide seed layer by using a solution method; wherein, the precursor solution in the solution method is a solution prepared by the following steps of (1) volume ratio of 0.8-1.2: 0.4-0.6mmol/L zinc nitrate (Zn (NO) of 0.8-1.23)2) The mixed solution of the solution and 0.4-0.6mmol/L hexamethylenetetramine solution is grown at 90-100 ℃ for 1-3 h.
Compared with the prior art, the beneficial effects are that:
firstly, after adopting such a compact structure, the invention has a plane size less than or equal to (100 x 100) mu m2The thickness is less than or equal to 5 mu m, so that the sensor is easy to meet the requirements of chip integration and wearable sensing devices; because the periphery of the metal oxide gas sensor surrounds the annular gas concentrator, and the space distance between the metal oxide gas sensor and the annular gas concentrator is very small and is only less than or equal to 10 mu m, the molecular flux diffused into the metal oxide gas sensor area is in a maximum value when gas molecules enriched on the annular gas concentrator are heated and desorbed, and the function of the gas concentrator in the aspect of trace gas molecule enrichment is fully exerted; the mesoporous heat insulation layer is covered on the surface of the silicon chip, and the sizes and the intervals of all devices arranged on the silicon chip are smaller, so that the size and the power consumption of the platinum micro-heater are greatly reduced, the thermal relaxation time of the metal oxide gas sensor and the gas concentrator is also greatly shortened, namely, the thermal relaxation time is only millisecond level, and the rapid sampling test is greatly facilitated; furthermore, the pertinence of the gas type detection of the invention is greatly improved by combining the selection of the applicable metal oxide gas sensor because the organic mesoporous material, the inorganic mesoporous material or the oxide nanowire array can be used as the material of the gas concentratorAnd (5) lifting.
Secondly, the preparation method is scientific and efficient. The gas concentration and sensing integrated device which is a target product with compact structure, low power consumption and convenient and fast detection is manufactured; the gas detection device also has the advantages of high detection limit, real time and convenience for gas detection; and then the target product is extremely easy to be widely applied to high-sensitivity detection of gas, so that the target product has wide application prospect in the fields of wearable or embeddable intelligent terminals and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of one basic structure of the present invention.
Fig. 2 is one of results of characterization of the platinum micro-heater in the present invention using a gishley (Keithley)4200 semiconductor characteristic analysis system and a scanning electron microscope. Wherein, the graph a in FIG. 2 is the result graph of the test using the Giaxle 4200 semiconductor characteristic analysis system, since the resistance of the platinum micro-heater increases with the temperature increase, the temperature coefficient of resistance of platinum is 0.003K-1Estimating the temperature of the micro heater under different input powers, wherein the temperature of the micro heater given by a secondary coordinate shows that the platinum micro heater can be heated to 500 ℃ at most, and when the input power is 23mW, the platinum micro heater can be heated to 300 ℃; the b and c images are SEM images before and after the platinum micro-heater is heated to 500 ℃, and it can be seen that the platinum micro-heater after high-temperature operation has no obvious degradation.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
First commercially available or manufactured on its own:
ZEP 520A electron beam resist and polymethyl methacrylate electron beam resist as electron beam resists;
tin dioxide, indium oxide, gallium oxide, tungsten trioxide, molybdenum trioxide, copper oxide, nickel oxide, and chromium oxide as metal oxides;
silicon dioxide, aluminum oxide and zirconium dioxide as materials for the annular insulating layer;
organic mesoporous materials, inorganic mesoporous materials and oxide nanowire arrays as materials of the gas concentrator.
Wherein:
the growth process of the molecular sieve gas concentrator comprises the steps of firstly carrying out oxygen plasma cleaning on a silicon wafer, the surface of which is covered with a mesoporous heat-insulating layer, a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater and an electron beam corrosion inhibitor, which are sequentially covered with a connecting electrode, and then soaking the silicon wafer into a mixed solution of 15-25mmol/L zinc nitrate methanol solution and 35-45 mmol/L2-methylimidazole methanol solution for standing for 20-40min to obtain the molecular sieve concentrator positioned on the annular insulating layer; wherein, the radio frequency power when the oxygen plasma is cleaned is 80-120W, the oxygen pressure is 0.5-1.5Torr, the cleaning time is more than or equal to 20s, the volume ratio of the zinc nitrate methanol solution to the 2-methylimidazole methanol solution in the mixed solution is 0.8-1.2: 0.8-1.2.
The growth process of the zinc oxide nanowire array gas concentrator comprises the steps of sputtering a zinc oxide seed layer with the thickness of 1-20nm on a silicon wafer, wherein the silicon wafer is sequentially coated with a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater, an annular insulating layer and an electron beam resist, the surface of the silicon wafer is coated with a mesoporous heat insulating layer, and then growing the zinc oxide nanowire array on the zinc oxide seed layer by using a solution method; wherein, the precursor solution in the solution method is a solution prepared by the following steps of (1) volume ratio of 0.8-1.2: 0.8-1.2, 0.4-0.6mmol/L zinc nitrate solution and 0.4-0.6mmol/L hexamethylenetetramine solution, the temperature is 90-100 ℃ and the time is 1-3h during growth.
Then:
example 1
The preparation method comprises the following specific steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, and then etching a sensor pattern with the length of 3 microns and the width of 1.5 microns on the silicon wafer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Sputtering a metal oxide gas sensor on the sensor pattern by using a magnetron sputtering method, placing the sensor pattern in a dimethylformamide solution, and stripping an electron beam resist to obtain a silicon wafer with a metal oxide gas sensor covered on the silicon wafer and a mesoporous heat insulation layer covered on the surface of the silicon wafer; wherein, the sputtering power is 80W, the sputtering time is 60min when the metal oxide gas sensor is sputtered by a magnetron sputtering method, the thickness of the metal oxide gas sensor is 200nm, and the metal oxide is tin dioxide.
And 3, coating an electron beam resist on a silicon wafer which is coated with a mesoporous heat insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, and then engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method. Then, sputtering an insulating layer with the thickness of 80nm on the ring by using a magnetron sputtering method, placing the insulating layer in a dimethylformamide solution, and stripping an electron beam resist to obtain a metal oxide gas sensor on which a connecting electrode is sequentially covered and a silicon wafer of which the surface of the ring insulating layer is covered with a mesoporous heat insulating layer; wherein, the material of the annular insulating layer is silicon dioxide.
Step 4, coating an electron beam resist on a silicon wafer which is sequentially covered with a metal oxide gas sensor of a connecting electrode and a mesoporous heat insulation layer on the surface of the annular insulation layer, and then engraving a platinum micro-heater graph with the width of 0.2 mu m on the annular insulation layer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then, after a platinum micro-heater with the thickness of 500nm is evaporated on the pattern of the platinum micro-heater, the platinum micro-heater is placed in a dimethylformamide solution to strip the electron beam resist, and a silicon wafer with a metal oxide gas sensor, an annular insulating layer and an annular platinum micro-heater, which are sequentially covered with a connecting electrode, and a mesoporous heat insulating layer is covered on the surface of the annular platinum micro-heater is obtained; wherein, the evaporation is electron beam evaporation.
Step 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is coated with a metal oxide gas sensor, an annular insulating layer and a mesoporous heat insulating layer, and the surface of the annular platinum micro-heater is sequentially coated with a connecting electrode, and then engraving an annular platinum micro-heater by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then sputtering an insulating layer with the thickness of 80nm on the ring by using a magnetron sputtering method, and growing a gas concentrator with the radius of an inner ring of 4 mu m, the radius of an outer ring of 12 mu m and the thickness of 500nm on the insulating layer; wherein, the material of annular insulating layer is silicon dioxide, and the gas concentrator is zinc oxide nanowire array gas concentrator. Then, the substrate was placed in a dimethylformamide solution to peel off the electron beam resist, and a gas concentration sensor integrated device similar to that shown in fig. 1 was obtained.
Example 2
The preparation method comprises the following specific steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, and then, etching a sensor pattern with the length of 3.5 microns and the width of 1.2 microns on the silicon wafer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Sputtering a metal oxide gas sensor on the sensor pattern by using a magnetron sputtering method, placing the sensor pattern in a dimethylformamide solution, and stripping an electron beam resist to obtain a silicon wafer with a metal oxide gas sensor covered on the silicon wafer and a mesoporous heat insulation layer covered on the surface of the silicon wafer; wherein, the sputtering power is 90W, the sputtering time is 48min when the metal oxide gas sensor is sputtered by a magnetron sputtering method, the thickness of the metal oxide gas sensor is 175nm, and the metal oxide is tin dioxide.
And 3, coating an electron beam resist on a silicon wafer which is coated with a mesoporous heat insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, and then engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method. Sputtering an insulating layer with the thickness of 90nm on the ring by using a magnetron sputtering method, placing the insulating layer in a dimethylformamide solution, and stripping an electron beam resist to obtain a metal oxide gas sensor on which a connecting electrode is sequentially covered and a silicon wafer of which the surface of the ring insulating layer is covered with a mesoporous heat insulating layer; wherein, the material of the annular insulating layer is silicon dioxide.
Step 4, coating an electron beam resist on a silicon wafer which is sequentially covered with a metal oxide gas sensor of a connecting electrode and a mesoporous heat insulation layer on the surface of an annular insulation layer, and then engraving a platinum micro-heater graph with the width of 0.4 mu m on the annular insulation layer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then, after a platinum micro-heater with the thickness of 425nm is evaporated on the pattern of the platinum micro-heater, the platinum micro-heater is placed in a dimethylformamide solution to strip the electron beam resist, and a silicon wafer with a metal oxide gas sensor, an annular insulating layer and an annular platinum micro-heater, which are sequentially covered with a connecting electrode, and a mesoporous heat insulating layer is covered on the surface of the annular platinum micro-heater is obtained; wherein, the evaporation is electron beam evaporation.
Step 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is coated with a metal oxide gas sensor, an annular insulating layer and a mesoporous heat insulating layer, and the surface of the annular platinum micro-heater is sequentially coated with a connecting electrode, and then engraving an annular platinum micro-heater by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then sputtering an insulating layer with the thickness of 90nm on the ring by using a magnetron sputtering method, and growing a gas concentrator with the radius of an inner ring of 4.5 mu m, the radius of an outer ring of 11 mu m and the thickness of 625nm on the insulating layer; wherein, the material of annular insulating layer is silicon dioxide, and the gas concentrator is zinc oxide nanowire array gas concentrator. Then, the substrate was placed in a dimethylformamide solution to peel off the electron beam resist, and a gas concentration sensor integrated device similar to that shown in fig. 1 was obtained.
Example 3
The preparation method comprises the following specific steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, and then, etching a sensor pattern with the length of 4 microns and the width of 0.9 microns on the silicon wafer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Sputtering a metal oxide gas sensor on the sensor pattern by using a magnetron sputtering method, placing the sensor pattern in a dimethylformamide solution, and stripping an electron beam resist to obtain a silicon wafer with a metal oxide gas sensor covered on the silicon wafer and a mesoporous heat insulation layer covered on the surface of the silicon wafer; wherein, the sputtering power is 100W, the sputtering time is 35min when the metal oxide gas sensor is sputtered by a magnetron sputtering method, the thickness of the metal oxide gas sensor is 150nm, and the metal oxide is tin dioxide.
And 3, coating an electron beam resist on a silicon wafer which is coated with a mesoporous heat insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, and then engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method. Then, sputtering an insulating layer with the thickness of 100nm on the ring by using a magnetron sputtering method, placing the insulating layer in a dimethylformamide solution, and stripping an electron beam resist to obtain a metal oxide gas sensor on which a connecting electrode is sequentially covered and a silicon wafer of which the surface of the ring insulating layer is covered with a mesoporous heat insulating layer; wherein, the material of the annular insulating layer is silicon dioxide.
Step 4, coating an electron beam resist on a silicon wafer which is sequentially covered with a metal oxide gas sensor of a connecting electrode and a mesoporous heat insulation layer on the surface of the annular insulation layer, and then engraving a platinum micro-heater graph with the width of 0.6 mu m on the annular insulation layer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then, after a platinum micro-heater with the thickness of 350nm is evaporated on the platinum micro-heater pattern, the platinum micro-heater pattern is placed in a dimethylformamide solution to strip an electron beam resist, and a silicon wafer with a metal oxide gas sensor, an annular insulating layer and an annular platinum micro-heater, which are sequentially covered with connecting electrodes, and a mesoporous heat insulating layer is covered on the surface of the annular platinum micro-heater is obtained; wherein, the evaporation is electron beam evaporation.
Step 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is coated with a metal oxide gas sensor, an annular insulating layer and a mesoporous heat insulating layer, and the surface of the annular platinum micro-heater is sequentially coated with a connecting electrode, and then engraving an annular platinum micro-heater by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then sputtering an insulating layer with the thickness of 100nm on the ring by using a magnetron sputtering method, and growing a gas concentrator with the radius of an inner ring of 5 mu m, the radius of an outer ring of 10 mu m and the thickness of 750nm on the insulating layer; wherein, the material of annular insulating layer is silicon dioxide, and the gas concentrator is zinc oxide nanowire array gas concentrator. Then, the substrate was placed in a dimethylformamide solution to peel off the electron beam resist, and the gas concentration and sensing integrated device shown in fig. 1 was obtained.
Example 4
The preparation method comprises the following specific steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, and then, etching a sensor pattern with the length of 4.5 microns and the width of 0.6 microns on the silicon wafer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Sputtering a metal oxide gas sensor on the sensor pattern by using a magnetron sputtering method, placing the sensor pattern in a dimethylformamide solution, and stripping an electron beam resist to obtain a silicon wafer with a metal oxide gas sensor covered on the silicon wafer and a mesoporous heat insulation layer covered on the surface of the silicon wafer; wherein, the sputtering power is 110W, the sputtering time is 23min when the metal oxide gas sensor is sputtered by a magnetron sputtering method, the thickness of the metal oxide gas sensor is 125nm, and the metal oxide is tin dioxide.
And 3, coating an electron beam resist on a silicon wafer which is coated with a mesoporous heat insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, and then engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method. Then, sputtering an insulating layer with the thickness of 110nm on the ring by using a magnetron sputtering method, placing the insulating layer in a dimethylformamide solution, and stripping an electron beam resist to obtain a metal oxide gas sensor on which a connecting electrode is sequentially covered and a silicon wafer of which the surface of the ring insulating layer is covered with a mesoporous heat insulating layer; wherein, the material of the annular insulating layer is silicon dioxide.
Step 4, coating an electron beam resist on a silicon wafer which is sequentially covered with a metal oxide gas sensor of a connecting electrode and a mesoporous heat insulation layer on the surface of the annular insulation layer, and then engraving a platinum micro-heater graph with the width of 0.8 mu m on the annular insulation layer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then, after a platinum micro heater with the thickness of 275nm is evaporated on the platinum micro heater pattern, the platinum micro heater pattern is placed in a dimethylformamide solution to strip the electron beam resist, and a silicon wafer with a metal oxide gas sensor, an annular insulating layer and an annular platinum micro heater, which are sequentially covered with a connecting electrode, and a mesoporous heat insulating layer is covered on the surface of the silicon wafer is obtained; wherein, the evaporation is electron beam evaporation.
Step 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is coated with a metal oxide gas sensor, an annular insulating layer and a mesoporous heat insulating layer, and the surface of the annular platinum micro-heater is sequentially coated with a connecting electrode, and then engraving an annular platinum micro-heater by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then sputtering an insulating layer with the thickness of 110nm on the ring by using a magnetron sputtering method, and growing a gas concentrator with the inner ring radius of 5.5 mu m, the outer ring radius of 9 mu m and the thickness of 875nm on the insulating layer; wherein, the material of annular insulating layer is silicon dioxide, and the gas concentrator is zinc oxide nanowire array gas concentrator. Then, the substrate was placed in a dimethylformamide solution to peel off the electron beam resist, and a gas concentration sensor integrated device similar to that shown in fig. 1 was obtained.
Example 5
The preparation method comprises the following specific steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, and then, etching a sensor pattern with the length of 5 microns and the width of 0.3 microns on the silicon wafer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Sputtering a metal oxide gas sensor on the sensor pattern by using a magnetron sputtering method, placing the sensor pattern in a dimethylformamide solution, and stripping an electron beam resist to obtain a silicon wafer with a metal oxide gas sensor covered on the silicon wafer and a mesoporous heat insulation layer covered on the surface of the silicon wafer; wherein, the sputtering power is 120W, the sputtering time is 10min when the metal oxide gas sensor is sputtered by a magnetron sputtering method, the thickness of the metal oxide gas sensor is 100nm, and the metal oxide is tin dioxide.
And 3, coating an electron beam resist on a silicon wafer which is coated with a mesoporous heat insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, and then engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method. Sputtering an insulating layer with the thickness of 120nm on the ring by using a magnetron sputtering method, placing the insulating layer in a dimethylformamide solution, and stripping an electron beam resist to obtain a metal oxide gas sensor with a connecting electrode sequentially covered on the insulating layer and a silicon wafer with a mesoporous heat insulating layer covered on the surface of the ring insulating layer; wherein, the material of the annular insulating layer is silicon dioxide.
Step 4, coating an electron beam resist on a silicon wafer which is sequentially covered with a metal oxide gas sensor of a connecting electrode and a mesoporous heat insulation layer on the surface of an annular insulation layer, and then engraving a platinum micro-heater graph with the width of 1 micrometer on the annular insulation layer by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then, after a platinum micro-heater with the thickness of 200nm is evaporated on the pattern of the platinum micro-heater, the platinum micro-heater is placed in a dimethylformamide solution to strip the electron beam resist, and a silicon wafer with a metal oxide gas sensor, an annular insulating layer and an annular platinum micro-heater, which are sequentially covered with a connecting electrode, and a mesoporous heat insulating layer is covered on the surface of the annular platinum micro-heater is obtained; wherein, the evaporation is electron beam evaporation.
Step 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is coated with a metal oxide gas sensor, an annular insulating layer and a mesoporous heat insulating layer, and the surface of the annular platinum micro-heater is sequentially coated with a connecting electrode, and then engraving an annular platinum micro-heater by an electron beam exposure method; wherein the electron beam resist is ZEP 520A electron beam resist. Then sputtering an insulating layer with the thickness of 120nm on the ring by using a magnetron sputtering method, and growing a gas concentrator with the radius of an inner ring of 6 mu m, the radius of an outer ring of 8 mu m and the thickness of 1000nm on the insulating layer; wherein, the material of annular insulating layer is silicon dioxide, and the gas concentrator is zinc oxide nanowire array gas concentrator. Then, the substrate was placed in a dimethylformamide solution to peel off the electron beam resist, and a gas concentration sensor integrated device similar to that shown in fig. 1 was obtained.
Then, the ZEP 520A electron beam resist or the polymethyl methacrylate electron beam resist as the electron beam resist, the tin dioxide or the indium oxide or the gallium oxide or the tungsten trioxide or the molybdenum trioxide or the copper oxide or the nickel oxide or the chromium oxide as the metal oxide are respectively selected, the magnetron sputtering or the direct current sputtering or the electron beam evaporation is selected for the vapor deposition, the silicon dioxide or the aluminum oxide or the zirconium dioxide as the material of the annular insulating layer, the organic mesoporous material or the inorganic mesoporous material or the oxide nanowire array as the material of the gas concentrator are used, the above examples 1 to 5 are repeated, and the gas concentration and sensing integrated device as or similar to that shown in fig. 1 is also prepared.
It is apparent that those skilled in the art can make various changes and modifications to the gas concentration sensing integrated device and the method for manufacturing the same of the present invention without departing from the spirit and scope of the present invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (10)
1. The utility model provides an integrative device of concentrated sensing of gas, comprises gas sensor, gas concentrator, electric heater and the electrode in the location shell to and the power of being connected with the electrode, its characterized in that:
the positioning shell is a silicon wafer with a mesoporous heat insulation layer covered on the surface;
the gas sensor is a metal oxide gas sensor, and the metal oxide gas sensor is attached to the silicon chip with the surface covered with the mesoporous heat insulation layer;
the gas concentrator is annular and is attached to the periphery of the metal oxide gas sensor;
the electric heater is a platinum micro-heater with the width less than or equal to 1 mu m and the thickness of 200 and 500nm, and the platinum micro-heater is positioned below the annular gas concentrator;
annular insulating layers are arranged between the platinum micro-heater and the periphery of the metal oxide gas sensor and between the platinum micro-heater and the annular gas concentrator;
the electrode is respectively and electrically connected with the metal oxide gas sensor and the platinum micro-heater.
2. The integrated gas concentration and sensing device as claimed in claim 1, wherein the metal oxide gas sensor has a length of 3-5 μm, a width of 0.3-1.5 μm, and a thickness of 100-200nm, and wherein the metal oxide is tin dioxide, or indium oxide, or gallium oxide, or tungsten trioxide, or molybdenum trioxide, or copper oxide, or nickel oxide, or chromium oxide.
3. The integrated gas concentration and sensing device as claimed in claim 1, wherein the annular gas concentrator is annular and concentric with the metal oxide gas sensor, and has an inner ring radius of 4-6 μm, an outer ring radius of 8-12 μm and a thickness of 500-1000nm, and is made of an organic mesoporous material, an inorganic mesoporous material or an oxide nanowire array.
4. The integrated gas concentration and sensing device as claimed in claim 1, wherein the annular insulating layer has a thickness of 80nm or more and is an annular silicon dioxide insulating layer, an annular aluminum oxide insulating layer or an annular zirconium dioxide insulating layer.
5. A method for preparing the gas concentration and sensing integrated device of claim 1, which comprises an electron beam exposure method, and is characterized by mainly comprising the following steps:
step 1, coating an electron beam resist on a silicon wafer with a mesoporous heat insulation layer on the surface, then etching a sensor pattern on the silicon wafer by an electron beam exposure method, sputtering a metal oxide gas sensor on the sensor pattern by a magnetron sputtering method, then placing the sensor pattern in a dimethylformamide solution to strip the electron beam resist, and obtaining the silicon wafer with the metal oxide gas sensor on the surface and the mesoporous heat insulation layer;
step 2, coating an electron beam resist on a silicon wafer which is coated with a metal oxide gas sensor and is coated with a mesoporous heat insulation layer on the surface, etching electrode patterns at two ends of the metal oxide gas sensor by an electron beam exposure method, evaporating electrodes on the electrode patterns, placing the electrode patterns in a dimethylformamide solution, and stripping the electron beam resist to obtain the silicon wafer which is coated with the metal oxide gas sensor and is connected with the electrodes and is coated with the mesoporous heat insulation layer on the surface;
step 3, coating an electron beam resist on a silicon wafer, which is coated with a mesoporous thermal insulation layer on the surface of the metal oxide gas sensor coated with the connecting electrode, engraving a ring shape on the periphery of the metal oxide gas sensor by an electron beam exposure method, sputtering an insulation layer on the ring shape by using a magnetron sputtering method, placing the ring shape in a dimethylformamide solution, and stripping the electron beam resist to obtain the metal oxide gas sensor coated with the connecting electrode and the silicon wafer coated with the mesoporous thermal insulation layer on the surface of the ring insulation layer in sequence;
step 4, coating an electron beam resist on a silicon wafer on which a metal oxide gas sensor for connecting electrodes and a mesoporous heat insulation layer are sequentially coated, etching a platinum micro-heater graph on the annular insulation layer by an electron beam exposure method, evaporating a platinum micro-heater on the platinum micro-heater graph, and then placing the platinum micro-heater graph in a dimethylformamide solution to strip the electron beam resist to obtain the silicon wafer on which the metal oxide gas sensor for connecting electrodes, the annular insulation layer and the mesoporous heat insulation layer are sequentially coated;
and 5, coating an electron beam resist on a silicon wafer, wherein the silicon wafer is sequentially coated with a metal oxide gas sensor for connecting electrodes, an annular insulating layer and a mesoporous heat insulating layer on the surface of the annular platinum micro-heater, then engraving an annular platinum micro-heater by using an electron beam exposure method, sputtering the insulating layer on the annular platinum micro-heater by using a magnetron sputtering method, growing a gas concentrator on the annular platinum micro-heater, and then placing the annular platinum micro-heater in a dimethylformamide solution to strip the electron beam resist to obtain the gas concentration and sensing integrated device.
6. The method for manufacturing the gas concentration and sensing integrated device according to claim 5, wherein the electron beam resist is ZEP 520A electron beam resist or polymethyl methacrylate (PMMA) electron beam resist.
7. The method for manufacturing a gas concentration and sensing integrated device as defined in claim 5, wherein the sputtering power of the magnetron sputtering method used for sputtering the metal oxide gas sensor in step 1 is 80-120W, the sputtering time is 10-60min, the length of the metal oxide gas sensor is 3-5 μm, the width is 0.3-1.5 μm, and the thickness is 100-200nm, wherein the metal oxide is tin dioxide, indium oxide, gallium oxide, tungsten trioxide, molybdenum trioxide, copper oxide, nickel oxide, or chromium oxide.
8. The method for preparing a gas concentration and sensing integrated device according to claim 5, wherein the annular insulating layer has a layer thickness of 80nm or more and is an annular silicon dioxide insulating layer, an annular aluminum oxide insulating layer or an annular zirconium dioxide insulating layer.
9. The method for preparing the gas concentration and sensing integrated device according to claim 5, wherein the gas concentrator is grown by cleaning a silicon wafer, which is coated with a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater, an annular insulating layer and an electron beam resist, which are sequentially coated with a connecting electrode, and a mesoporous thermal insulation layer on the surface, with oxygen plasma, immersing the silicon wafer into a mixed solution of 15-25mmol/L zinc nitrate methanol solution and 35-45 mmol/L2-methylimidazole methanol solution, and standing for 20-40min to obtain a molecular sieve concentrator on the annular insulating layer; wherein, the radio frequency power when the oxygen plasma is cleaned is 80-120W, the oxygen pressure is 0.5-1.5Torr, the cleaning time is more than or equal to 20s, the volume ratio of the zinc nitrate methanol solution to the 2-methylimidazole methanol solution in the mixed solution is 0.8-1.2: 0.8-1.2.
10. The method for preparing the gas concentration and sensing integrated device according to claim 5, wherein the gas concentrator is grown by sputtering a zinc oxide seed layer with a thickness of 1-20nm on a silicon wafer, which is coated with a metal oxide gas sensor, an annular insulating layer, an annular platinum micro-heater, an annular insulating layer and an electron beam resist, the metal oxide gas sensor, the annular insulating layer, the annular platinum micro-heater and the electron beam resist are sequentially coated with a connecting electrode, and a mesoporous thermal insulation layer is coated on the surface of the silicon wafer, and then growing a zinc oxide nanowire array on the zinc oxide seed layer by using a; wherein, the precursor solution in the solution method is a solution prepared by the following steps of (1) volume ratio of 0.8-1.2: 0.8-1.2, 0.4-0.6mmol/L zinc nitrate solution and 0.4-0.6mmol/L hexamethylenetetramine solution, the temperature is 90-100 ℃ and the time is 1-3h during growth.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847838A (en) * | 2006-04-07 | 2006-10-18 | 福建师范大学 | Gas sensor based on nanometer line array and its prepn process |
| CN102279210A (en) * | 2011-07-29 | 2011-12-14 | 吉林大学 | Double-sensitive-layer gas sensor based on nano fiber and particle adhesion layer and preparation method of double-sensitive-layer gas sensor |
| CN102426176A (en) * | 2011-11-18 | 2012-04-25 | 南京工业大学 | Gas sensor and manufacturing technique thereof |
| CN104142359A (en) * | 2014-07-18 | 2014-11-12 | 苏州能斯达电子科技有限公司 | MEMS gas sensor and machining method thereof |
| CN104576713A (en) * | 2014-12-31 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Pn junction and preparation method |
| CN105606661A (en) * | 2016-03-09 | 2016-05-25 | 中国科学院微电子研究所 | Thin film type MOS gas sensor with integral nano-structure and manufacturing method of sensor |
| CN106324038A (en) * | 2015-06-30 | 2017-01-11 | 台湾积体电路制造股份有限公司 | Gas sensor, integrated circuit device using the same, and manufacturing method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050063865A1 (en) * | 2002-09-27 | 2005-03-24 | Ulrich Bonne | Phased VII micro fluid analyzer having a modular structure |
| US7228725B2 (en) * | 2004-01-27 | 2007-06-12 | H2Scan Llc | Thin film gas sensor configuration |
| EP2475612A4 (en) * | 2009-09-11 | 2017-09-13 | Jp Laboratories, Inc. | Monitoring devices and processes based on transformation, destruction and conversion of nanostructures |
| US9953972B2 (en) * | 2009-10-12 | 2018-04-24 | Monolithic 3D Inc. | Semiconductor system, device and structure |
| JP5984505B2 (en) * | 2012-05-22 | 2016-09-06 | 株式会社日立製作所 | Semiconductor gas sensor and manufacturing method thereof |
| CN104181203B (en) * | 2014-08-13 | 2017-12-22 | 苏州能斯达电子科技有限公司 | A kind of MEMS gas sensors and preparation method thereof |
-
2018
- 2018-02-05 CN CN201810120026.8A patent/CN108375498B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847838A (en) * | 2006-04-07 | 2006-10-18 | 福建师范大学 | Gas sensor based on nanometer line array and its prepn process |
| CN102279210A (en) * | 2011-07-29 | 2011-12-14 | 吉林大学 | Double-sensitive-layer gas sensor based on nano fiber and particle adhesion layer and preparation method of double-sensitive-layer gas sensor |
| CN102426176A (en) * | 2011-11-18 | 2012-04-25 | 南京工业大学 | Gas sensor and manufacturing technique thereof |
| CN104142359A (en) * | 2014-07-18 | 2014-11-12 | 苏州能斯达电子科技有限公司 | MEMS gas sensor and machining method thereof |
| CN104576713A (en) * | 2014-12-31 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Pn junction and preparation method |
| CN106324038A (en) * | 2015-06-30 | 2017-01-11 | 台湾积体电路制造股份有限公司 | Gas sensor, integrated circuit device using the same, and manufacturing method thereof |
| CN105606661A (en) * | 2016-03-09 | 2016-05-25 | 中国科学院微电子研究所 | Thin film type MOS gas sensor with integral nano-structure and manufacturing method of sensor |
Non-Patent Citations (1)
| Title |
|---|
| "三维中空氧化物/高分子膜核壳纳米结构电极的构建及稳定性研究";杨红艳;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170930;第17页 * |
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