CN102175755B - Carbon nanotube film micro-nano ionizing sensor and manufacture method thereof - Google Patents
Carbon nanotube film micro-nano ionizing sensor and manufacture method thereof Download PDFInfo
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- CN102175755B CN102175755B CN 201110037965 CN201110037965A CN102175755B CN 102175755 B CN102175755 B CN 102175755B CN 201110037965 CN201110037965 CN 201110037965 CN 201110037965 A CN201110037965 A CN 201110037965A CN 102175755 B CN102175755 B CN 102175755B
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Abstract
The invention discloses a carbon nanotube film micro-nano ionizing sensor and a manufacture method thereof, wherein the sensor comprises a first electrode, a second electrode and a third electrode which are distributed from upper to lower in sequence; the first electrode is provided with an air hole; a metal film substrate distributed with a carbon nanotube film is attached on the inner surface of the first electrode; the second electrode is composed of a lead-out pole plate provided with a lead-out hole at the centre of the lead-out pole plate; and the third electrode is composed of a collector provided with a blind hole at the plate face of the collector; the three electrodes are isolated by insulating struts. The method comprises the following steps: respectively manufacturing the mask plates of the three electrodes, washing a silicon wafer, and sputtering a metal mask; etching the metal mask and patterns, removing the mask, and washing the silicon wafer; sputtering a multilayered metal film, and manufacturing a gold pad; screen printing an insulation slurry or splicing polymer insulation strips; growing or screen printing the carbon nanotube film on the metal film substrate at the inner side of the first electrode; gluing the three electrodes, bonding electrode lead wires, and encapsulating the sensor. The sensor has the characteristics of simple structure, good linearity of gas detection and high accuracy.
Description
Technical field
The present invention relates to micro-nano technical field of sensor manufacture, particularly a kind of adopt carbon nano-tube film, have the monodrome input-output characteristic, gas concentration, temperature and humidity had micro-nano ionizing transducer of sensitivity characteristic and preparation method thereof.
Background technology
Along with commercial production and environment measuring in the urgent need to and the development of nanometer technology, nano-sensor has obtained considerable progress.Especially along with the discovery of carbon nano-tube in latter stage in 20th century, carbon nano-tube shows tempting application prospect in gas, temperature and humidity measure field.Carbon nano-tube film two electrode ionizing transducers in carbon nano-tube gas-sensitive, temperature sensitive, the moisture sensor, high with its detection sensitivity, detect the advantages such as gas wide ranges, response be fast, become the study hotspot in gas, temperature and humidity measure field.Carbon nano-tube film two electrode Gas-Sensitive Sensor of Ionized Type have overcome the shortcoming of carbon nano-tube gas-sensitive sensors saturated poisoning in tested gas of other type based on gas discharge principle, and gas concentration measurement scope and tested gaseous species scope are wider.As air-sensitive, temperature sensitive, moisture sensor that sensitive material consists of, have the irreplaceable advantage of conventional sensors with carbon nano-tube: the one, the specific surface area of carbon nano-tube is large, in the situation that the sensor overall dimensions is less, can greatly improve the area of electrode; Two are based on the tip curvature radius of carbon nanotube level, and working sensor voltage is greatly reduced, and obtain extremely strong electric field intensity near the carbon nano-tube tip, make tested gas ionization under low-voltage; The 3rd, the size of greatly having dwindled sensor, dynamic response is fast.Therefore, it has widely development prospect at aspects such as biology, chemistry, machinery, aviation, military affairs, anti-terrorisms.
Existing carbon nano-tube film two electrode ionizing transducers comprise by people such as Liu Junhua, the Zhang Yong of Xi'an Communications University, Li Xin, professors Zhu Changchun at the disclosed carbon nano-tube film two electrode ionization type gas sensors (shown in Figure 1) of the 14th the IVMC international vacuum microelectronics international conference of calendar year 2001.This working sensor is afterwards because interpolar discharge rear space electric charge is difficult to diffusion, sensor is difficult to return to original state, and present multivalued relation (Fig. 2, Fig. 3) between sensor voltage breakdown, breakdown current and the gas concentration, can't measure gas concentration.The people such as the Nikhil Koratkar of U.S. Rensselaer Polytech Inst (Rensselaer Polytechnic Institute) and Pulickel M professor Ajayan have developed carbon nano-tube film positive C NTFA (carbon nanotube film anode) two-electrode gas sensor.Present nonlinear relationship between this sensor voltage breakdown and the gas concentration, linear error is larger between disruptive discharge electric current and the gas concentration; Simultaneously this sensor must with the chromatograph coupling, substitute gas detector in traditional chromatograph with CNTFA, adopt the chromatographic column isolation technics, solve CNTFA to identification and the measurement of concetration problem of mixed gas; This sensor sparking voltage and discharge current are all larger; And can't realize that CNTFA is to the measurement of pure gas and mixed gas.The Hui Guohua of Zhejiang University's biomedical engineering and instrumental science institute, Chen Yuquan professor develops CNT lamel cathode two-electrode gas sensor under the condition of 120 microns die openings, studied the flash-over characteristic of sensor in three kinds of pure gases, because sensitivity is lower, do not consist of the gas sensor of measuring concentration.And temperature-sensing property (Fig. 4) and the wet sensitive characteristic (Fig. 5) of CNT lamel cathode two electrode sensors, the i.e. relation of voltage breakdown and temperature, humidity in the air have been studied.Voltage breakdown is up to 360 volts when temperature is 10 degrees centigrade for this two electrode sensor, and voltage breakdown was also more than 150 volts when temperature was 60 degrees centigrade; And sensor voltage breakdown and humidity have many-valued nonlinear characteristic, do not consist of carbon nano-tube film two electrode ionization type temperature and moisture sensors.
Therefore, at present to the carbon-nano-tube membrane micron-nano ionization type gas of all kinds of gas sensitizations, the development of temperature and moisture sensors, become the technical matters that needs to be resolved hurrily.
Summary of the invention
The purpose of this invention is to provide a kind of micronano ionizing sensor of carbon nanotube film, the output current of carbon nano-tube film two electrode sensors is divided into electron stream and ion current, set up the single-valued relationship of ion current that micronano ionizing sensor of carbon nanotube film collector of the present invention collects and gas concentration, humidity, overcome the many-valued nonlinear problem of carbon nano-tube film two electrode sensor gas-sensitive properties and wet sensitive characteristic.This sensor construction is simple, and cost is low, detects gas sensitivity high, and accuracy is high, is suitable for promoting the use of.
The objective of the invention is to realize by following technical proposals.
A kind of micronano ionizing sensor of carbon nanotube film, it is characterized in that: comprise three the first electrode, the second electrode and third electrodes that distribute successively from top to bottom, described the first electrode adheres to the electrode that metallic film base is arranged and be provided with bleeder vent by inside surface and consists of, and carbon nano-tube film is distributing on the described metallic film base; The second electrode is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made of the collector that the plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column respectively;
Adjacent two interelectrode die openings are 30 ~ 250 μ m in described three electrodes.
Described the first electrode and the second electrode pad are 0.01 ~ 170mm over against area
2, the second electrode and third electrode pole plate are 0.01 ~ 190mm over against area
2
The further architectural feature of the present invention is:
The bleeder vent of the electrode surface of described the first electrode is 1 ~ 4, and the metallic film base growth or the screen printing that adhere at the electrode inner surface are brushed with carbon nano-tube film.
Described the second electrode extraction pole center is provided with 1 ~ 4 fairlead.
Described third electrode collector blind hole is corresponding with the fairlead of the second electrode, and the quantity of blind hole is 1 ~ 4.
Described insulation column is distributed in three electrode inner face both sides.
Described the first electrode, the second electrode and third electrode all adopt silicon sheet material to make, and the two sides of the first electrode and third electrode medial surface, the second electrode are equipped with metal film.
Described bleeder vent and fairlead are circle, triangle, quadrilateral, pentagon or hexagon.
Described blind hole is right cylinder, cone, 3 ~ 6 prisms or pyramid.
The present invention gives a kind of preparation method of micronano ionizing sensor of carbon nanotube film, and the method comprises the steps:
1) makes respectively the mask plate of three electrodes;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean the silicon chip as three electrodes, the silicon chip after the cleaning is in 150 ~ 250 ℃ of drying 5 ~ 10min;
3) respectively on cleaned silicon chip, by the Al mask of magnetron sputtering 200nm;
4) carry out graphical photoetching at the silicon chip of sputter Al mask respectively: at first adopting static gluing method that positive photoresist is spread upon sputter has on the silicon chip of Al mask, then in 85 ~ 120 ℃ of dry 60s; The mask plate of three electrodes is contacted with the photoresist layer aligning, carry out uv-exposure; Be that 0.26 Tetramethylammonium hydroxide TMAH solution is at 15 ~ 25 ℃ of development 30s with standardization equivalent concentration; At 100 ~ 130 ℃ of baking 1 ~ 2min, can obtain the litho pattern of three electrodes at last;
5) adopt wet etching method, etch step 4) in Al mask under the litho pattern, in 50 ℃ ~ 60 ℃ corrosion 15s; And remove remaining photoresist on the silicon chip with acetone;
6) employing ICP dry etching obtains the figure on three electrodes; Control respectively charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane, control coil power, dull and stereotyped power are respectively 600W and 22W; Carry out bleeder vent and fairlead and blind hole in three electrodes of etching;
7) wet etching is removed residue Al mask, and the same step 5) of method namely obtains three electrodes;
8) clean, drying patterned three electrode silicon chips; In three electrodes difference successively sputtered titanium, nickel, golden three-layered metal film, and make the gold solder dish;
9) with three electrode short annealing 30 ~ 80s of sputtering metal membrane, annealing temperature is 400 ~ 500 ℃;
10) sputter layer of gold film again on the metal film of the electrode silicon chip after the annealing;
11) in the second electrode inner face both sides over against the carbon nano-tube film end face, and the inner face both sides of third electrode, interelectrode insulation strip made with the serigraphy insulation paste, at 280 ~ 300 ℃ of insulation 0.5 ~ 1h; Perhaps adopt the interelectrode insulation strip of polymer blending fabrication techniques, tygon is mixed with the mass ratio of carbon black according to 100:40, be that 100 ~ 120 ℃, pressure are 9 ~ 10MPa hot setting, 5 ~ 7min in temperature, the insulation strip made is bonded in the second electrode inner face both sides over against the carbon nano-tube film end face and the inner face both sides of third electrode with insulating gel;
12) carbon nano-tube film in the substrate of the first electrode perhaps adopts silk-screen printing technique printed carbon nanotube film in substrate;
13) three electrodes are bonded together with insulating gel; Bonding gold wire is as electrode outlet line;
14) three bonding electrodes are bonded on the outer casing base, in 140 ~ 150 ℃ of curing 2h, encapsulation namely gets sensor.
Described step 2) in, cleaning fluid is H according to weight ratio
2SO
4: H
2O
2The preparation of=4: 1 ratio.
In the described step 5), etchant solution is nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2: 10: 50: the preparation of 9 ratios.
In the described step 8), be 2.5 * 10 in vacuum tightness
-3Pa, respectively successively sputter titanium film, nickel film and golden film on three substrates under 30 ~ 40 ℃, sputtering time is respectively 7min, 50min and 13min, and three-layer thin-film thickness is respectively 50nm, 400nm and 125nm.
The present invention mutually superposes by three electrodes and consists of the sensor that can detect gas, temperature and humidity, apply different voltage at three electrodes, control electron stream and ion current effective separation, acquisition and gas concentration, gas temperature, humidity have the output (Fig. 8, Fig. 9, shown in Figure 10) of the ion current of single valued relation, are successfully constructed three kinds of novel carbon-nano-tube membrane micron-nano ionization type gases, gas temperature and humidity sensors.Three electrode probes that use in this novel sensor and the existing ionization detector chromatograph are compared, do electrode owing to adopting carbon nano-tube film, the tip curvature radius of carbon nanotube level is with the detector operating voltage, from the safe and practical scope below 600 volts of high pressure drop to 200 volts of ionization detector.Novel sensor of the present invention adopts miromaching to realize, size is little, and is simple in structure, do not need to combine with chromatograph, can consist of separately three kinds of new gas concentration, gas temperature and humidity sensors.
Description of drawings
Fig. 1 is prior art carbon nano-tube thin film cathode two electrode sensor structural representations.
Fig. 2 is the voltage breakdown of prior art carbon nano-tube film two-electrode gas sensor and the many-valued non-linear gas-sensitive property of gas concentration.
Fig. 3 is the breakdown current of prior art carbon nano-tube film two-electrode gas sensor and the many-valued non-linear gas-sensitive property of gas concentration.
Fig. 4 is the voltage breakdown of prior art carbon nano-tube film two electrode temperature sensors and the relation of temperature.
Fig. 5 is the many-valued non-linear humidity sensitive characteristic of prior art carbon nano-tube film two electrode humidity sensors.
Fig. 6 is micronano ionizing sensor of carbon nanotube film structural representation of the present invention.
Fig. 7 is micronano ionizing sensor of carbon nanotube film spatial structure side view of the present invention.
Fig. 8 is the gas discharge ion current of micronano ionizing sensor of carbon nanotube film output of the present invention and the single valued relation of gas concentration.
Fig. 9 is the gas discharge ion current of micronano ionizing sensor of carbon nanotube film output of the present invention and the single valued relation of air themperature.
Figure 10 is the gas discharge ion current of micronano ionizing sensor of carbon nanotube film output of the present invention and the single valued relation of humidity.
Among the figure: 1, the first electrode; 2, the second electrode; 3, third electrode; 4, be provided with the electrode of bleeder vent; 5, metallic film base; 6, carbon nano-tube film; 7, insulation column.
Embodiment
The present invention will be further described below in conjunction with drawings and the specific embodiments.
Such as Fig. 6, shown in Figure 7, this micronano ionizing sensor of carbon nanotube film, comprise by three electrodes that mutually superpose from top to bottom successively and consisting of, these three mutual overlay electrodes are respectively equipped with the first electrode 1, the second electrode 2 and third electrode 3, and the electrode 4 that described the first electrode 1 adheres to the metallic film base 5 that the carbon nano-tube film 6 that distributing is arranged by inside surface and is provided with bleeder vent consists of; The second electrode 2 is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode 3 is made of the collector that the battery lead plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column 7 respectively.Adjacent two interelectrode die openings are 100 μ m in three electrodes; The first electrode 1 and the second electrode 2 pole plates are 100mm over against area
2, the second electrode 2 is 120mm with third electrode 3 pole plates over against area
2
Among the micronano ionizing sensor of carbon nanotube film embodiment shown in Figure 6, the bleeder vent of the electrode surface of the first electrode 1 has 2, and bleeder vent is circular; Side surface at this bleeder vent is attached with metallic film base 5, is distributed with carbon nano-tube film 6 on it, and this carbon nano-tube mouth of pipe is downward.The second electrode 2 centers are provided with 1 ~ 4 fairlead, have provided among Fig. 6, Fig. 7 a fairlead and fairlead are set are circular embodiment.Third electrode 3 collector blind holes are corresponding with the fairlead of the second electrode, and the quantity of blind hole is 1 ~ 4, provided among Fig. 6, Fig. 7 a blind hole to be set and blind hole is the embodiment of cylindrical structure.Insulation column 7 is separately positioned between the first electrode and the second electrode 2, between the second electrode 2 and the third electrode 3, namely insulation column 7 is distributed in the second electrode 2 over against the surperficial both sides of the first electrode 1 and the both sides on the inboard golden film surface of third electrode 3.
The present invention's the first electrode 1 adopts silicon sheet material to make, and a side surface of the first electrode 1 is attached with metallic film base 5; Described carbon nano-tube film 6 can adopt FePC as catalyzer, and adopts carbon source, makes carbon nano-tube film 6 in metallic film base 5 growths, and perhaps the serigraphy carbon nano-tube film 6.The second electrode 2 and third electrode 3 all adopt silicon wafer to manufacture.The two sides of the first electrode 1 and third electrode 3 medial surfaces, the second electrode 2 are equipped with metal film.
On the electrode in the present invention's the first electrode 1 some bleeder vents are arranged, be convenient to gas to be detected and enter electrode gap; Metallic film base 5 is attached to the first electrode 1 one side surfaces; On the second electrode 2 fairlead is arranged; Third electrode 3 collectors can be collected the positive ion stream that gas ionization produces.Between the first electrode 1 and the second electrode 3, mutually isolate by insulation column 7 between the second electrode 2 and the third electrode 3; Tested gas enters in the gap of adjacent two electrodes of sensor by the gap between the sensor peripheral electrode.
Micronano ionizing sensor of carbon nanotube film of the present invention is added in voltage on the first electrode 1 and the second electrode 2 by control, can make the γ-ray emission discharge between the first electrode 1 and the second electrode 2; Be added in voltage on the second electrode 2 and the third electrode 3 by control, electronics and the ion isolation of the first electrode 1 and 2 generations of the second electrode can be opened.The electron stream that electronics forms flows back to the first electrode 1 by the second electrode 2, and the ion current that ion forms is drawn by third electrode 3, flows back to the first electrode 1.Three electrode structure ionizing transducers of the present invention, draw ion current by third electrode 3, can greatly reduce the labile factor of the first electrode 1 and 2 gas discharges of the second electrode, obtain the ion current (Fig. 9, shown in Figure 10) that has the ion current (shown in Figure 8) of single valued relation and have respectively single valued relation with gas temperature, humidity with gas concentration.
The present invention controls the second electrode 2 current potentials and is higher than the first electrode 1, and third electrode 3 current potentials are lower than the second electrode 2 and are higher than the first electrode 1.Control the second electrode 2 and the first electrode 1 formation electron stream loop, control third electrode 3 and the first electrode 1 form the ion current loop, realize electron stream is separated with ion current.The first electrode 1 produces very strong electric field near the carbon nano-tube tip of carbon nano-tube film under the impressed voltage effect, the tested gas in the gap between the first electrode 1 and the second electrode 2 is ionized under low voltage.The charged positive ion that the first electrode 1 and the second electrode are 2 under the effect of the second electrode 2 and third electrode 3 interpolar electric fields, forms positive-ion currents to third electrode 3 motions.Between the ion current of micronano ionizing sensor of carbon nanotube film output and gas concentration, gas temperature, the humidity, apply on the basis of certain voltage at the second electrode 2, present single valued relation (Fig. 8, Fig. 9, shown in Figure 10), can consist of can practical gas concentration, gas temperature and humidity sensor.Non-self-maintained discharge voltage, non-self-maintained discharge dark current and sensor electrode die opening are the characteristic parameters of micronano ionizing sensor of carbon nanotube film.
The method that the present embodiment is made micronano ionizing sensor of carbon nanotube film comprises the steps:
1) makes respectively the mask plate of three electrodes;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean the silicon chip as three electrodes, the silicon chip after the cleaning is in 150 ℃ of dry 10min; Wherein, cleaning fluid is H according to weight ratio
2SO
4: H
2O
2The preparation of=4: 1 ratio;
3) respectively on cleaned silicon chip, by the Al mask of magnetron sputtering 200nm;
4) carry out graphical photoetching at the silicon chip of sputter Al mask respectively: at first adopting static gluing method that positive photoresist is spread upon sputter has on the silicon chip of Al mask, then in 85 ℃ of dry 60s; The mask plate of three electrodes is contacted with the photoresist layer aligning, carry out uv-exposure; Be that 0.26 Tetramethylammonium hydroxide TMAH solution is at 15 ℃ of development 30s with standardization equivalent concentration; At 100 ℃ of baking 2min, can obtain the litho pattern of three electrodes at last;
5) adopt wet etching method, etch step 4) in Al mask under the litho pattern, in 50 ℃ of corrosion 15s; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2: 10: 50: the preparation of 9 ratios;
6) employing ICP dry etching obtains the figure on three electrodes; Control respectively charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane, control coil power, dull and stereotyped power are respectively 600W and 22W; Carry out bleeder vent and fairlead and blind hole in three electrodes of etching;
7) wet etching is removed residue Al mask, and the same step 5) of method namely obtains three electrodes;
8) clean, drying patterned three electrode silicon chips; In three electrodes difference successively sputtered titanium, nickel, golden three-layered metal film, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, respectively successively sputter titanium film, nickel film and golden film on three substrates under 30 ℃, sputtering time is respectively 7min, 50min and 13min, and three-layer thin-film thickness is respectively 50nm, 400nm and 125nm.
9) with three electrode short annealing 30s of sputtering metal membrane, annealing temperature is 500 ℃;
10) golden film again on the metal film of the electrode silicon chip after the annealing;
11) in the second electrode inner face both sides over against the carbon nano-tube film end face, and the inner face both sides of third electrode, interelectrode insulation strip made with the serigraphy insulation paste, at 280 ℃ of insulation 1h;
12) carbon nano-tube film in the substrate of four layers of metal film of sputter of the first electrode;
13) three electrodes are bonded together with insulating gel; Bonding gold wire is as electrode outlet line;
14) three bonding electrodes are bonded on the outer casing base, in 140 ℃ of curing 2h, encapsulation namely gets sensor.
The present embodiment basic structure is with embodiment 1, and difference is: adjacent two interelectrode die openings are 30 μ m in three electrodes of micronano ionizing sensor of carbon nanotube film; The first electrode 1 and the second electrode 2 pole plates are 0.01mm over against area
2, the second electrode 2 is 0.01mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of the first electrode 1 has 1, and bleeder vent is triangle; The second electrode 2 center fairleads are 4, and fairlead is triangle; The quantity of third electrode 3 blind holes is 4, and blind hole is cone.
The method that the present embodiment is made micronano ionizing sensor of carbon nanotube film comprises the steps:
1) makes respectively the mask plate of three electrodes;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean the silicon chip as three electrodes, the silicon chip after the cleaning is in 200 ℃ of dry 7min; Wherein, cleaning fluid is H according to weight ratio
2SO
4: H
2O
2The preparation of=4: 1 ratio;
3) respectively on cleaned silicon chip, by the Al mask of magnetron sputtering 200nm;
4) carry out graphical photoetching at the silicon chip of sputter Al mask respectively: at first adopting static gluing method that positive photoresist is spread upon sputter has on the silicon chip of Al mask, then in 100 ℃ of dry 60s; The mask plate of three electrodes is contacted with the photoresist layer aligning, carry out uv-exposure; Be that 0.26 Tetramethylammonium hydroxide TMAH solution is at 20 ℃ of development 30s with standardization equivalent concentration; At 120 ℃ of baking 1.5min, can obtain the litho pattern of three electrodes at last;
5) adopt wet etching method, etch step 4) in Al mask under the litho pattern, in 55 ℃ of corrosion 15s; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2: 10: 50: the preparation of 9 ratios;
6) employing ICP dry etching obtains the figure on three electrodes; Control respectively charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane, control coil power, dull and stereotyped power are respectively 600W and 22W; Carry out bleeder vent and fairlead and blind hole in three electrodes of etching;
7) wet etching is removed residue Al mask, and the same step 5) of method namely obtains three electrodes;
8) clean, drying patterned three electrode silicon chips; In three electrodes difference successively sputtered titanium, nickel, golden three-layered metal film, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, respectively successively sputter titanium film, nickel film and golden film on three substrates under 30 ℃, sputtering time is respectively 7min, 50min and 13min, and three-layer thin-film thickness is respectively 50nm, 400nm and 125nm.
9) with three electrode short annealing 50s of sputtering metal membrane, annealing temperature is 450 ℃;
10) sputter layer of gold film again on the metal film of the electrode silicon chip after the annealing;
11) adopting the interelectrode insulation strip of polymer blending fabrication techniques, tygon is mixed with the mass ratio of carbon black according to 100:40, is that 110 ℃, pressure are 9.6MPa curing 6min(or are that 100 ℃, pressure are 9MPa curing 7min in temperature in temperature; Or be that 120 ℃, pressure are that 10MPa solidifies 5min in temperature), and the insulation strip made is bonded in the second electrode inner face both sides over against the carbon nano-tube film end face and the inner face both sides of third electrode with insulating gel;
12) carbon nano-tube film in the substrate of four layers of metal film of sputter of the first electrode;
13) three electrodes are bonded together with insulating gel; Bonding gold wire is as electrode outlet line;
14) three bonding electrodes are bonded on the outer casing base, in 145 ℃ of curing 2h, encapsulation namely gets sensor.
The present embodiment basic structure is with embodiment 1, and difference is: adjacent two interelectrode die openings are 250 μ m in three electrodes of micronano ionizing sensor of carbon nanotube film, and the first electrode 1 and the second electrode 2 pole plates are 170mm over against area
2, the second electrode 2 is 190mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of the first electrode 1 has 4, and bleeder vent is quadrilateral, pentagon or hexagon; The second electrode 2 center fairleads are 2, and fairlead is quadrilateral, pentagon or hexagon; The quantity of third electrode 3 blind holes is 2, and blind hole is 3 ~ 6 prisms or pyramid.
The method that the present embodiment is made micronano ionizing sensor of carbon nanotube film comprises the steps:
1) makes respectively the mask plate of three electrodes;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean the silicon chip as three electrodes, the silicon chip after the cleaning is in 250 ℃ of dry 5min; Wherein, cleaning fluid is H according to weight ratio
2SO
4: H
2O
2The preparation of=4: 1 ratio;
3) respectively on cleaned silicon chip, by the Al mask of magnetron sputtering 200nm;
4) carry out graphical photoetching at the silicon chip of sputter Al mask respectively: at first adopting static gluing method that positive photoresist is spread upon sputter has on the silicon chip of Al mask, then in 120 ℃ of dry 60s; The mask plate of three electrodes is contacted with the photoresist layer aligning, carry out uv-exposure; Be that 0.26 Tetramethylammonium hydroxide TMAH solution is at 25 ℃ of development 30s with standardization equivalent concentration; At 130 ℃ of baking 1min, can obtain the litho pattern of three electrodes at last;
5) adopt wet etching method, etch step 4) in Al mask under the litho pattern, in 60 ℃ of corrosion 15s; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2: 10: 50: the preparation of 9 ratios;
6) employing ICP dry etching obtains the figure on three electrodes; Control respectively charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane, control coil power, dull and stereotyped power are respectively 600W and 22W; Carry out bleeder vent and fairlead and blind hole in three electrodes of etching;
7) wet etching is removed residue Al mask, and the same step 5) of method namely obtains three electrodes;
8) clean, drying patterned three electrode silicon chips; In three electrodes difference successively sputtered titanium, nickel, golden three-layered metal film, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, respectively successively sputter titanium film, nickel film and golden film on three substrates under 30 ℃, sputtering time is respectively 7min, 50min and 13min, and three-layer thin-film thickness is respectively 50nm, 400nm and 125nm.
9) with three electrode short annealing 80s of sputtering metal membrane, annealing temperature is 400 ℃;
10) sputter layer of gold film again on the metal film of the electrode silicon chip after the annealing;
11) in the second electrode inner face both sides over against the carbon nano-tube film end face, and the inner face both sides of third electrode, adopt the serigraphy insulation paste to make interelectrode insulation strip, at 300 ℃ of insulation 0.5h;
12) in the substrate of four layers of metal film of sputter of the first electrode, adopt silk-screen printing technique printed carbon nanotube film on the metallic film base of the first electrode;
13) three electrodes are bonded together with insulating gel; Bonding gold wire is as electrode outlet line;
14) three bonding electrodes are bonded on the outer casing base, in 150 ℃ of curing 2h, encapsulation namely gets sensor.
Although the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, above-described embodiment is not intended to limit the present invention.In the situation that does not break away from the given technical characterictic of technical solution of the present invention and range of structures, the increase that technical characterictic is done, distortion or with the replacement of the same content in this area all should belong to protection scope of the present invention.
Claims (8)
1. micronano ionizing sensor of carbon nanotube film, it is characterized in that: comprise three the first electrode, the second electrode and third electrodes that distribute successively from top to bottom, described the first electrode adheres to the electrode that metallic film base is arranged and be provided with bleeder vent by inside surface and consists of, and carbon nano-tube film is distributing on the described metallic film base; The second electrode is made of the extraction pole pole plate that the center is provided with fairlead; Third electrode is made of the collector that the plate face is provided with blind hole; These three electrodes are isolated mutually by insulation column respectively;
Adjacent two interelectrode die openings are 30～250 μ m in described three electrodes; Described the first electrode and the second electrode pad are 0.01～170mm over against area
2, the second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described the first electrode is 1～4, and the metallic film base growth or the screen printing that adhere at the electrode inner surface are brushed with carbon nano-tube film;
Described the second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of the second electrode, and the quantity of blind hole is 1～4.
2. micronano ionizing sensor of carbon nanotube film according to claim 1, it is characterized in that: described insulation column is distributed in three electrode inner face both sides.
3. micronano ionizing sensor of carbon nanotube film according to claim 1, it is characterized in that: described the first electrode, the second electrode and third electrode all adopt silicon sheet material to make, and the two sides of the first electrode and third electrode medial surface, the second electrode are equipped with metal film.
4. micronano ionizing sensor of carbon nanotube film according to claim 1 is characterized in that: described bleeder vent and fairlead are circle, triangle, quadrilateral, pentagon or hexagon; Described blind hole is right cylinder, cone, 3～6 prisms or pyramid.
5. the preparation method of a micronano ionizing sensor of carbon nanotube film as claimed in claim 1, it is characterized in that: the method comprises the steps:
1) makes respectively the mask plate of three electrodes;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean the silicon chip as three electrodes, the silicon chip after the cleaning is in 150～250 ℃ of drying 5～10min;
3) respectively on cleaned silicon chip, by the Al mask of magnetron sputtering 200nm;
4) carry out graphical photoetching at the silicon chip of sputter Al mask respectively: at first adopting static gluing method that positive photoresist is spread upon sputter has on the silicon chip of Al mask, then in 85～120 ℃ of dry 60s; The mask plate of three electrodes is contacted with the photoresist layer aligning, carry out uv-exposure; Be that 0.26 Tetramethylammonium hydroxide TMAH solution is at 15～25 ℃ of development 30s with standardization equivalent concentration; At 100～130 ℃ of baking 1～2min, can obtain the litho pattern of three electrodes at last;
5) adopt wet etching method, etch step 4) in Al mask under the litho pattern, in 50 ℃～60 ℃ corrosion 15s; And remove remaining photoresist on the silicon chip with acetone;
6) employing ICP dry etching obtains the figure on three electrodes; Control respectively charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane, control coil power, dull and stereotyped power are respectively 600W and 22W; Carry out bleeder vent and fairlead and blind hole in three electrodes of etching;
7) wet etching is removed residue Al mask, and the same step 5) of method namely obtains three electrodes;
8) clean, drying patterned three electrode silicon chips; In three electrodes difference successively sputtered titanium, nickel, golden three-layered metal film, and make the gold solder dish;
9) with three electrode short annealing 30～80s of sputtering metal membrane, annealing temperature is 400～500 ℃;
10) sputter layer of gold film again on the metal film of the electrode silicon chip after the annealing;
11) in the second electrode inner face both sides over against the carbon nano-tube film end face, and the inner face both sides of third electrode, interelectrode insulation strip made with the serigraphy insulation paste, at 280～300 ℃ of insulation 0.5～1h; Perhaps adopt the interelectrode insulation strip of polymer blending fabrication techniques, tygon is mixed with the mass ratio of carbon black according to 100:40, be that 100～120 ℃, pressure are 9～10MPa hot setting, 5～7min in temperature, the insulation strip made is bonded in the second electrode inner face both sides over against the carbon nano-tube film end face and the inner face both sides of third electrode with insulating gel;
12) carbon nano-tube film in the substrate of the first electrode perhaps adopts silk-screen printing technique printed carbon nanotube film in substrate;
13) three electrodes are bonded together with insulating gel; Bonding gold wire is as electrode outlet line;
14) three bonding electrodes are bonded on the outer casing base, in 140～150 ℃ of curing 2h, encapsulation namely gets sensor.
6. the preparation method of a kind of micronano ionizing sensor of carbon nanotube film according to claim 5, it is characterized in that: described step 2), cleaning fluid is H according to weight ratio
2SO
4: H
2O
2The preparation of=4:1 ratio.
7. the preparation method of a kind of micronano ionizing sensor of carbon nanotube film according to claim 5, it is characterized in that: in the described step 5), etchant solution is nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2:10:50:9 ratio preparation.
8. the preparation method of a kind of micronano ionizing sensor of carbon nanotube film according to claim 5 is characterized in that: in the described step 8), be 2.5 * 10 in vacuum tightness
-3Pa, respectively successively sputter titanium film, nickel film and golden film on three substrates under 30～40 ℃, sputtering time is respectively 7min, 50min and 13min, and three-layer thin-film thickness is respectively 50nm, 400nm and 125nm.
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| CN112903183B (en) * | 2019-11-19 | 2022-11-22 | 北京大学 | On-chip miniature ionization vacuum sensor and manufacturing method thereof |
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