CN102175755A - 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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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 pressing for and the development of nanometer technology of commercial production and environment measuring, 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, Humidity Detection field.Carbon nano-tube film two electrode ionizing transducers in carbon nano-tube gas-sensitive, temperature sensitive, the moisture sensor with advantages such as its detection sensitivity height, detected gas wide ranges, response are fast, become the research focus in gas, temperature, Humidity Detection 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 wideer.As air-sensitive, temperature sensitive, moisture sensor that sensitive material constitutes, have the irreplaceable advantage of conventional sensors with carbon nano-tube: the one, the specific surface area of carbon nano-tube is big, under the less situation of sensor overall dimensions, can improve the area of electrode greatly; 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 having dwindled sensor greatly, dynamic response is fast.Therefore, it has result of extraction 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 international vaccum microelectronics international conference of the 14th IVMC 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 (Fig. 2 Fig. 3), can't measure gas concentration to present multivalued relation between sensor voltage breakdown, breakdown current and the gas concentration.People such as 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 bigger 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 identification and the measurement of concetration problem of CNTFA to mixed gas; This sensor sparking voltage and discharge current are all bigger; And can't realize the measurement of CNTFA to 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 constitute the gas sensor of measuring concentration.And temperature-sensing property (Fig. 4) and wet quick characteristic (Fig. 5), the i.e. relation of voltage breakdown and temperature, humidity in the air of CNT lamel cathode two electrode sensors 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 constitute carbon nano-tube film two electrode ionization type temperature and humidity sensors.
Therefore, to the development of the micro-nano ionization type gas of the carbon nano-tube film of all kinds of gas sensitizations, temperature and humidity sensor, become the technical matters that needs to be resolved hurrily at present.
Summary of the invention
The purpose of this invention is to provide the micro-nano ionizing transducer of a kind of carbon nano-tube film, the output current of carbon nano-tube film two electrode sensors is divided into electron stream and ion flow, set up the single-valued relationship of ion flow that the micro-nano ionizing transducer collector of carbon nano-tube film of the present invention collects and gas concentration, humidity, overcome carbon nano-tube film two electrode sensor gas-sensitive properties and the many-valued nonlinear problem of the quick characteristic that wets.This sensor construction is simple, and cost is low, and detected gas is highly sensitive, and the accuracy height is suitable for promoting the use of.
The objective of the invention is to realize by following technical proposals.
The micro-nano ionizing transducer of a kind of carbon nano-tube film, it is characterized in that: comprise three first electrode, second electrode and third electrodes that distribute successively from top to bottom, the electrode that described first electrode adheres to the metallic film base that the carbon nano-tube film that distributing is arranged by inside surface and is provided with bleeder vent constitutes; 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.
The further architectural feature of the present invention is:
Adjacent two interelectrode die openings are 30～250 μ m in described three electrodes.
Described first electrode and second electrode pad are 0.01～170mm over against area
2, second electrode and third electrode pole plate are 0.01～190mm over against area
2
The bleeder vent of the electrode surface of described first electrode is 1～4, and growth or serigraphy have carbon nano-tube film on the metallic film base that the electrode inner surface adheres to.
The described second electrode extraction pole center is provided with 1～4 fairlead.
Described third electrode collector blind hole is corresponding with the fairlead of second electrode, and the quantity of blind hole is 1～4.
Described insulation column is distributed in three electrode inner face both sides.
Described first electrode, second electrode and third electrode all adopt silicon sheet material to make, and the two sides of first electrode and third electrode medial surface, 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 the preparation method of the micro-nano ionizing transducer of a kind of carbon nano-tube film, and this method comprises the steps:
1) makes the mask plate of three electrodes respectively;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean 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) carrying out graphical photoetching on 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 litho pattern Al mask down, corrode 15s in 50 ℃～60 ℃; And remove remaining photoresist on the silicon chip with acetone;
6) employing ICP dry etching obtains the figure on three electrodes; Control the charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane respectively, 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 promptly obtains three electrodes;
8) cleaning, patterned three the electrode silicon chips of drying; On three electrodes, distinguish sputtered titanium, nickel, golden three-layered metal film successively, and make the gold solder dish;
9) with three electrode short annealing 30～80s of splash-proofing sputtering metal film, annealing temperature is 400～500 ℃;
10) sputter one deck 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, in temperature is that 100～120 ℃, pressure are 9～10MPa hot setting, 5～7min, 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 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 promptly 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 a 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, sputter titanium film, nickel film and golden film successively on three substrates respectively 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 constitutes by three electrode mutual superposition can detected gas, the sensor of temperature and humidity, on three electrodes, apply different voltage, the control electron stream effectively separates with ion flow, acquisition and gas concentration, gas temperature, humidity have the output (Fig. 8, Fig. 9, shown in Figure 10) of the ion flow of single valued relation, are successfully constructed three kinds of micro-nano ionization type gases of novel carbon nano-tube film, 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 adopt 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 micromachined technology to realize that size is little, and is simple in structure, do not need to combine with chromatograph, can constitute three kinds of new gas concentration, gas temperature and humidity sensors separately.
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 the micro-nano ionizing transducer structural representation of carbon nano-tube film of the present invention.
Fig. 7 is the micro-nano ionizing transducer spatial structure of a carbon nano-tube film of the present invention side view.
Fig. 8 is the gas discharge ion flow of the micro-nano ionizing transducer output of carbon nano-tube film of the present invention and the single valued relation of gas concentration.
Fig. 9 is the gas discharge ion flow of the micro-nano ionizing transducer output of carbon nano-tube film of the present invention and the single valued relation of air themperature.
Figure 10 is the gas discharge ion flow of the micro-nano ionizing transducer output of carbon nano-tube film of the present invention and the single valued relation of humidity.
Among the figure: 1, first electrode; 2, 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.
As Fig. 6, shown in Figure 7, the micro-nano ionizing transducer of this carbon nano-tube film, comprise by three successively from top to bottom the electrode of mutual superposition constitute, these three mutual superposition electrodes are respectively equipped with first electrode 1, second electrode 2 and third electrode 3, and the electrode 4 that described 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 constitutes; 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; First electrode 1 and second electrode, 2 pole plates are 100mm over against area
2, second electrode 2 is 120mm with third electrode 3 pole plates over against area
2
Among the micro-nano ionizing transducer embodiment of carbon nano-tube film shown in Figure 6, the bleeder vent of the electrode surface of 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.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 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 first electrode and second electrode 2, between second electrode 2 and the third electrode 3, promptly insulation column 7 is distributed in second electrode 2 over against the surperficial both sides of first electrode 1 and the both sides on the inboard golden film surface of third electrode 3.
The present invention's first electrode 1 adopts silicon sheet material to make, and a side surface of 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, and carbon nano-tube film 6 is made in growth on metallic film base 5, and perhaps the serigraphy carbon nano-tube film 6.Second electrode 2 and third electrode 3 all adopt silicon wafer to manufacture.The two sides of first electrode 1 and third electrode 3 medial surfaces, second electrode 2 are equipped with metal film.
On the electrode in the present invention's 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 first electrode, 1 one side surfaces; On second electrode 2 fairlead is arranged; Third electrode 3 collectors can be collected the positive ion stream that gas ionization produces.Between first electrode 1 and second electrode 3, isolate mutually by insulation column 7 between 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.
The micro-nano ionizing transducer of carbon nano-tube film of the present invention is added in voltage on first electrode 1 and second electrode 2 by control, can make the gas between first electrode 1 and second electrode 2 produce discharge; Be added in voltage on second electrode 2 and the third electrode 3 by control, the electronics and the ion isolation of first electrode 1 and 2 generations of second electrode can be opened.The electron stream that electronics forms flows back to first electrode 1 by second electrode 2, and the ion flow that ion forms is drawn by third electrode 3, flows back to first electrode 1.Three electrode structure ionizing transducers of the present invention, draw ion flow by third electrode 3, can reduce the labile factor of first electrode 1 and 2 gas discharges of second electrode greatly, obtain the ion flow (Fig. 9, shown in Figure 10) that has the ion flow (shown in Figure 8) of single valued relation and have single valued relation respectively with gas temperature, humidity with gas concentration.
The present invention controls second electrode, 2 current potentials and is higher than first electrode 1, and third electrode 3 current potentials are lower than second electrode 2 and are higher than first electrode 1.Control second electrode 2 and first electrode, 1 formation electron stream loop, the control third electrode 3 and first electrode 1 form the ion flow loop, realize electron stream is separated with ion flow.First electrode 1 produces very strong electric field near the carbon nano-tube tip of carbon nano-tube film under the impressed voltage effect, make the tested gas ionization under low voltage in the gap between first electrode 1 and second electrode 2.The charged positive ion that first electrode 1 and second electrode are 2 under second electrode 2 and third electrode 3 interpolar effect of electric field, forms positive-ion currents to third electrode 3 motions.Between the ion flow of the micro-nano ionizing transducer output of carbon nano-tube film and gas concentration, gas temperature, the humidity, apply on the basis of certain voltage at second electrode 2, present single valued relation (Fig. 8, Fig. 9, shown in Figure 10), can constitute 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 the micro-nano ionizing transducer of carbon nano-tube film.
The method that present embodiment is made the micro-nano ionizing transducer of carbon nano-tube film comprises the steps:
1) makes the mask plate of three electrodes respectively;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean 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) carrying out graphical photoetching on 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 litho pattern Al mask down, corrode 15s in 50 ℃; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is a 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 the charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane respectively, 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 promptly obtains three electrodes;
8) cleaning, patterned three the electrode silicon chips of drying; On three electrodes, distinguish sputtered titanium, nickel, golden three-layered metal film successively, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, sputter titanium film, nickel film and golden film successively on three substrates respectively 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 splash-proofing sputtering metal film, annealing temperature is 500 ℃;
10) golden again film 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 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 promptly gets sensor.
Present embodiment basic structure is with embodiment 1, and different is: adjacent two interelectrode die openings are 30 μ m in three electrodes of the micro-nano ionizing transducer of carbon nano-tube film; First electrode 1 and second electrode, 2 pole plates are 0.01mm over against area
2, second electrode 2 is 0.01mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of first electrode 1 has 1, and bleeder vent is a triangle; Second electrode, 2 center fairleads are 4, and fairlead is a triangle; The quantity of third electrode 3 blind holes is 4, and blind hole is a cone.
The method that present embodiment is made the micro-nano ionizing transducer of carbon nano-tube film comprises the steps:
1) makes the mask plate of three electrodes respectively;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean 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) carrying out graphical photoetching on 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 litho pattern Al mask down, corrode 15s in 55 ℃; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is a 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 the charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane respectively, 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 promptly obtains three electrodes;
8) cleaning, patterned three the electrode silicon chips of drying; On three electrodes, distinguish sputtered titanium, nickel, golden three-layered metal film successively, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, sputter titanium film, nickel film and golden film successively on three substrates respectively 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 splash-proofing sputtering metal film, annealing temperature is 450 ℃;
10) sputter one deck 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 that 9.6MPa curing 6min (or is 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 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 promptly gets sensor.
Present embodiment basic structure is with embodiment 1, and different is: adjacent two interelectrode die openings are 250 μ m in three electrodes of the micro-nano ionizing transducer of carbon nano-tube film, and first electrode 1 and second electrode, 2 pole plates are 170mm over against area
2, second electrode 2 is 190mm with third electrode 3 pole plates over against area
2
The bleeder vent of the electrode surface of first electrode 1 has 4, and bleeder vent is quadrilateral, pentagon or hexagon; 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 present embodiment is made the micro-nano ionizing transducer of carbon nano-tube film comprises the steps:
1) makes the mask plate of three electrodes respectively;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean 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) carrying out graphical photoetching on 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 litho pattern Al mask down, corrode 15s in 60 ℃; And remove remaining photoresist on the silicon chip with acetone; Wherein, etchant solution is a 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 the charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane respectively, 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 promptly obtains three electrodes;
8) cleaning, patterned three the electrode silicon chips of drying; On three electrodes, distinguish sputtered titanium, nickel, golden three-layered metal film successively, and make the gold solder dish;
Wherein, be 2.5 * 10 in vacuum tightness
-3Pa, sputter titanium film, nickel film and golden film successively on three substrates respectively 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 splash-proofing sputtering metal film, annealing temperature is 400 ℃;
10) sputter one deck 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 first electrode, adopt silk-screen printing technique printed carbon nanotube film on the metallic film base of 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 promptly gets sensor.
Though the present invention has made detailed description with above-mentioned preferred embodiment to the present invention, the foregoing description also is not used in qualification the present invention.Under the situation that does not break away from 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 (10)
1. micro-nano ionizing transducer of carbon nano-tube film, it is characterized in that: comprise three first electrode, second electrode and third electrodes that distribute successively from top to bottom, the electrode that described first electrode adheres to the metallic film base that the carbon nano-tube film that distributing is arranged by inside surface and is provided with bleeder vent constitutes; 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.
2. the micro-nano ionizing transducer of carbon nano-tube film according to claim 1 is characterized in that: adjacent two interelectrode die openings are 30～250 μ m in described three electrodes; Described first electrode and second electrode pad are 0.01～170mm over against area
2, second electrode and third electrode pole plate are 0.01～190mm over against area
2
3. the micro-nano ionizing transducer of carbon nano-tube film according to claim 1, it is characterized in that: the bleeder vent of the electrode surface of described first electrode is 1～4, and growth or serigraphy have carbon nano-tube film on the metallic film base that the electrode inner surface adheres to;
The described second electrode extraction pole center is provided with 1～4 fairlead;
Described third electrode collector blind hole is corresponding with the fairlead of second electrode, and the quantity of blind hole is 1～4.
4. the micro-nano ionizing transducer of carbon nano-tube film according to claim 1 is characterized in that: described insulation column is distributed in three electrode inner face both sides.
5. the micro-nano ionizing transducer of carbon nano-tube film according to claim 1, it is characterized in that: described first electrode, second electrode and third electrode all adopt silicon sheet material to make, and the two sides of first electrode and third electrode medial surface, second electrode are equipped with metal film.
6. the micro-nano ionizing transducer of carbon nano-tube 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.
7. the preparation method of the micro-nano ionizing transducer of carbon nano-tube film, it is characterized in that: this method comprises the steps:
1) makes the mask plate of three electrodes respectively;
2) use H
2SO
4And H
2O
2As cleaning fluid, clean 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) carrying out graphical photoetching on 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 litho pattern Al mask down, corrode 15s in 50 ℃～60 ℃; And remove remaining photoresist on the silicon chip with acetone;
6) employing ICP dry etching obtains the figure on three electrodes; Control the charge flow rate 180sccm and the 85sccm of sulfur hexafluoride, octafluorocyclobutane respectively, 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 promptly obtains three electrodes;
8) cleaning, patterned three the electrode silicon chips of drying; On three electrodes, distinguish sputtered titanium, nickel, golden three-layered metal film successively, and make the gold solder dish;
9) with three electrode short annealing 30～80s of splash-proofing sputtering metal film, annealing temperature is 400～500 ℃;
10) sputter one deck 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, in temperature is that 100～120 ℃, pressure are 9～10MPa hot setting, 5～7min, 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 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 promptly gets sensor.
8. the preparation method of the micro-nano ionizing transducer of a kind of carbon nano-tube film according to claim 7 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.
9. the preparation method of the micro-nano ionizing transducer of a kind of carbon nano-tube film according to claim 7 is characterized in that: in the described step 5), etchant solution is a nitric acid according to weight ratio: acetic acid: phosphoric acid: water=2: 10: 50: the preparation of 9 ratios.
10. the preparation method of the micro-nano ionizing transducer of a kind of carbon nano-tube film according to claim 7 is characterized in that: in the described step 8), be 2.5 * 10 in vacuum tightness
-3Pa, sputter titanium film, nickel film and golden film successively on three substrates respectively 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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