CN107565020A - A kind of formaldehyde sensor based on organic field-effect tube and preparation method thereof - Google Patents
A kind of formaldehyde sensor based on organic field-effect tube and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to sensor technical field, discloses a kind of formaldehyde sensor based on organic field-effect tube and preparation method thereof, for solving the problems, such as that Monitoring lower-cut is not high existing for existing formaldehyde sensor.The formaldehyde sensor based on organic field effect tube of the present invention, including substrate, gate electrode, gate insulator and the organic semiconductor layer set gradually from top to bottom, the upper end connection active electrode and drain electrode of the organic semiconductor layer, the organic semiconductor layer is to be mixed by indigo or indigo derivative with diatom ooze, and the mass percent of diatom ooze is 3%~20% in the organic semiconductor layer.The present invention solve the problems, such as that Monitoring lower-cut existing for existing formaldehyde sensor is high and existing formaldehyde sensor existing for pliability is poor, the problems such as easily being polluted to environment.
Description
Technical field
The invention belongs to sensor technical field, and in particular to a kind of formaldehyde sensor based on organic field-effect tube and its
Preparation method.
Background technology
Formaldehyde is a kind of colourless, has the gas of penetrating odor, there is stimulation to human eye, nose etc., while again with the mankind's
Social activities is closely related, and with the development of modernization, the accurate measurement of formaldehyde is in daily life, meteorology, medical science and work
There is increasingly consequence in agricultural production.
The species of formaldehyde sensor is various, and at present, study hotspot both domestic and external is concentrated mainly on oxidation of formaldehyde thing gas biography
Sensor, formaldehyde gas molecular sieve sensor, formaldehyde sonic surface wave gas sensors, visualization fluorescence formaldehyde sensor and formaldehyde gas
Body electronic nose etc..However, traditional formaldehyde sensor still have this such as detection limit not enough, usually require temperature-compensating,
Selectivity is not high, volume is relatively large, the interference that is vulnerable to surrounding environment, error is relatively large, precision is insufficient, detection parameters list
First, it is not easy to realize that flexible, miniaturization, inorganic semiconductor material that is integrated, using easily cause environment secondary pollution etc. to lack
Point.
The content of the invention
The present invention provides one kind and is based on having to solve the problems, such as that Monitoring lower-cut is not high existing for existing formaldehyde sensor
Formaldehyde sensor of machine FET and preparation method thereof, solve the problems, such as Monitoring lower-cut existing for existing formaldehyde sensor it is high with
And pliability existing for existing formaldehyde sensor is poor, the problems such as easily being polluted to environment.
To solve technical problem, the technical solution adopted in the present invention is：
A kind of formaldehyde sensor based on organic field effect tube, including substrate, the grid electricity set gradually from top to bottom
Pole, gate insulator and organic semiconductor layer, the upper end connection active electrode and drain electrode of the organic semiconductor layer, its feature
It is：The organic semiconductor layer is to be mixed by indigo or indigo derivative with diatom ooze, in the organic semiconductor layer
The mass percent of diatom ooze is 3%~20%.
The material of the substrate is polyimides, PEI, polyethylene naphthalate, shellac, mica or silicon
One kind in algal gel.
The material of the gate insulator is polyvinyl alcohol, polyimides, polystyrene, polymethyl methacrylate, poly-
The one or more of ethene, the thickness of the gate insulator is 20~520nm.
The thickness of the organic semiconductor layer is 50~120nm.
The material of the gate electrode, source electrode and drain electrode is graphene, CNT, metal simple-substance nano wire, oxygen
Change the one or more in zinc, titanium oxide, tin indium oxide or polymer electrode material, the gate electrode, source electrode and drain electrode
Thickness is 50~80nm.
The metal simple-substance nano wire is Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel are received
One kind in rice noodles, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires
It is or a variety of.
The polymer electrode material is poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) or 3,4- polyethylene
One kind in dioxy thiophene.
A kind of preparation method of the formaldehyde sensor based on organic field effect tube, it is characterised in that including following step
Suddenly：
1. first with one or more to substrate progress in detergent, acetone soln, deionized water and aqueous isopropanol
Cleaning, dried after cleaning；
2. preparing gate electrode on the surface of substrate, the figure of gate electrode is formed；
3. gate insulator is prepared on surface gate electrode；
4. diatom ooze solution is miscible according to percent mass proportioning progress with indigo or indigo derivative solution, then at oneself
Cover and organic semiconductor layer just adult is prepared on the substrate of gate insulator, then 70 DEG C of thermal annealings 20 minutes, be made organic half
Conductor layer；
5. source electrode and electric leakage level are prepared on organic semiconductor layer；
6. the organic field effect tube 5. step is made after is packaged.
The step 2. with step 5. in, gate electrode, source electrode, drain electrode be by vacuum thermal evaporation, magnetron sputtering,
It is prepared by a kind of method in the chemical vapor deposition of plasma enhancing, silk-screen printing, printing or spin coating.
The step 4. in, the organic semiconductor layer be by the chemical vapor deposition of plasma enhancing, thermal oxide,
It is prepared by a kind of method in spin coating, vacuum evaporation, roller coat, drop film, pressure institute, printing or gas blowout.
The invention provides a kind of formaldehyde sensor based on organic field effect tube and preparation method thereof, by water solubility
Diatom ooze and indigo or indigo derivative are mixed according to a certain percentage, using the unique material property of water-soluble silicon algal gel,
Accuracy controlling is carried out to the pattern of organic semiconductor layer film, using the ability of the stronger formaldehyde adsorption of diatom ooze, and itself is
The characteristics of molecular porous structure, meanwhile, control the chi of semi-conducting material crystal grain in organic semiconductor by adjusting mixed proportion
Very little size so that organic semiconductor layer will be intended to form the pattern with more little crystal grain.When crystal grain is smaller, it is meant that have
There is more crystal grain gaps in machine semiconductive thin film, this is beneficial to formaldehyde molecule and is more rapidly diffused into current-carrying cunette
Among road, so as to strengthen the effective detection of formaldehyde sensor PARA FORMALDEHYDE PRILLS(91,95) molecule.
Simultaneously as diatom ooze has excellent water absorption character and stronger pliability, therefore, in organic semiconductor layer
After middle introducing diatom ooze, suction-operated of the half organic conductor layer to hydrone can be obviously improved, can be significantly reduced under detection
Limit, increase the responsiveness of formaldehyde sensor, while the effectively mechanical strength and pliability of lifting electronic component.
In summary, compared with prior art, the invention has the advantages that：
1st, introduced in indigo or indigo derivative semiconductor layer after a certain amount of water-soluble silicon algal gel, in the present invention
The responsiveness of formaldehyde sensor is obviously improved, and detection limit is lower.
2nd, introduced in indigo or indigo derivative semiconductor layer after a certain amount of water-soluble silicon algal gel, in the present invention
Formaldehyde sensor will have faster response speed, can realize the quick detection of gas.
3rd, compared with existing formaldehyde sensor, the organic semiconductor layer material that the sensor in the present invention uses is to environment friend
Good, the sensor based on organic field effect tube can be degradable, effectively solves the problems, such as secondary pollution caused by electronic waste.
4th, indigo, indigo derivative and water-soluble silicon algal gel belong to the common materials in nature, wide material sources, cost
Cheap, preparation technology is simple, it is easy to accomplish industrialization large-scale production.
Brief description of the drawings
Fig. 1 is the structural representation of the formaldehyde sensor based on organic field-effect tube of the present invention；
Fig. 2 is the change curve of the formaldehyde sensor performance under the conditions of different formaldehyde prepared for embodiment 5；It can be seen that
Device is under the conditions of different formaldehyde, and there occurs larger for the performance parameter (saturation current, carrier mobility, threshold voltage) of device
Change, serve the effect accurately detected；
Marked in figure：1st, substrate, 2, gate electrode, 3, gate insulator, 4, organic semiconductor layer, 5, source electrode, 6, electric leakage
Pole.
Embodiment
With reference to embodiment, the invention will be further described, and described embodiment is only a present invention part
Embodiment, it is not whole embodiments.Based on the embodiment in the present invention, one of ordinary skill in the art is not making
Other embodiments used obtained under the premise of creative work, belong to protection scope of the present invention.
With reference to accompanying drawing, the formaldehyde sensor provided by the invention based on organic field effect tube, including from top to bottom according to
Substrate 1, gate electrode 2, gate insulator 3 and the organic semiconductor layer 4 of secondary setting, the upper end connection of the organic semiconductor layer 4
Active electrode 5 and drain electrode 6, the organic semiconductor layer 4 is to be mixed by indigo or indigo derivative with diatom ooze, described
The mass percent of diatom ooze is 3%~20% in organic semiconductor layer.
The substrate 1 uses flexible substrate, and the material of substrate is polyimides (PI), PEI (PEI), gathered to naphthalene
One kind in dioctyl phthalate second diester (PEN), shellac, mica or diatom ooze；Substrate needs that there is certain anti-steam and oxygen to ooze
Saturating ability, while also need to that there is preferable surface smoothness.
For the gate insulator 3 using the material with good dielectric properties, the material of gate insulator 3 is polyethylene
Alcohol (PVA), polyimides (PI), polystyrene (PS), polymethyl methacrylate (PMMA), one kind or more of polyethylene (PE)
Kind, preparation method can be one kind side in chemical vapor deposition, thermal oxide, spin coating or the vacuum evaporation of plasma enhancing
Method；The thickness of the gate insulator 3 is 20~520nm.
The preparation method of machine semiconductor layer can be chemical vapor deposition, thermal oxide, spin coating, the vacuum of plasma enhancing
A kind of method in evaporation, drop film, impressing, printing or gas blowout；The thickness of organic semiconductor layer 4 is 50~120nm.
The material of the gate electrode, source electrode and drain electrode is graphene, CNT, metal simple-substance nano wire, oxygen
Change the one or more in zinc, titanium oxide, tin indium oxide or polymer electrode material, preparation method can be vacuum thermal evaporation,
One kind in the various deposition process such as magnetron sputtering, the chemical vapor deposition of plasma enhancing, silk-screen printing, printing, spin coating.
The gate electrode, source electrode and drain electrode thickness are 50~80nm.
The metal simple-substance nano wire is Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel are received
One kind in rice noodles, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires
It is or a variety of.
The polymer electrode material is poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) or 3,4- polyethylene
One kind in dioxy thiophene.
A kind of preparation method of the formaldehyde sensor based on organic field effect tube, comprises the following steps：
1. first with one or more to substrate progress in detergent, acetone soln, deionized water and aqueous isopropanol
Cleaning, dried after cleaning；
2. preparing gate electrode on the surface of substrate, the figure of gate electrode is formed；
3. gate insulator is prepared on surface gate electrode；
4. diatom ooze solution is miscible according to percent mass proportioning progress with indigo or indigo derivative solution, then at oneself
Cover and organic semiconductor layer just adult is prepared on the substrate of gate insulator, then 70 DEG C of thermal annealings 20 minutes, be made organic half
Conductor layer；
5. source electrode and electric leakage level are prepared on organic semiconductor layer；
6. the organic field effect tube 5. step is made after is packaged.
The step 2. with step 5. in, gate electrode, source electrode, drain electrode be by vacuum thermal evaporation, magnetron sputtering,
It is prepared by a kind of method in the chemical vapor deposition of plasma enhancing, silk-screen printing, printing or spin coating.
The step 4. in, the organic semiconductor layer be by the chemical vapor deposition of plasma enhancing, thermal oxide,
It is prepared by a kind of method in spin coating, vacuum evaporation, roller coat, drop film, pressure institute, printing or gas blowout.
The invention provides a kind of formaldehyde sensor based on organic field effect tube and preparation method thereof, by water solubility
Diatom ooze and indigo or indigo derivative are mixed according to a certain percentage, using the unique material property of water-soluble silicon algal gel,
Accuracy controlling is carried out to the pattern of organic semiconductor layer film, using the ability of the stronger formaldehyde adsorption of diatom ooze, and itself is
The characteristics of molecular porous structure, meanwhile, control the chi of semi-conducting material crystal grain in organic semiconductor by adjusting mixed proportion
Very little size so that organic semiconductor layer will be intended to form the pattern with more little crystal grain.When crystal grain is smaller, it is meant that have
There is more crystal grain gaps in machine semiconductive thin film, this is beneficial to formaldehyde molecule and is more rapidly diffused into current-carrying cunette
Among road, so as to strengthen the effective detection of formaldehyde sensor PARA FORMALDEHYDE PRILLS(91,95) molecule.
Simultaneously as diatom ooze has excellent water absorption character and stronger pliability, therefore, in organic semiconductor layer
After middle introducing diatom ooze, suction-operated of the half organic conductor layer to hydrone can be obviously improved, can be significantly reduced under detection
Limit, increase the responsiveness of formaldehyde sensor, while the effectively mechanical strength and pliability of lifting electronic component.
Embodiment 1
Preparation method is as follows：
1. thoroughly being cleaned as the PI substrates of gate electrode to having sputtered 50nmITO, dry nitrogen air-blowing is used after cleaning
It is dry；
2. PS films are prepared on ITO using spin-coating method forms gate insulator 100nm；
3. the PS film good to spin coating is through row heated baking；
4. spin coating is indigo on gate insulator:Diatom ooze mass ratio is 97:3 organic semiconductor layer 100nm；
5. copper source electrode and drain electrode 80nm are prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=6 μ A, carrier mobility μ
=2 × 10-3cm2/ Vs, threshold voltage VTH=-14V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Embodiment 2
Preparation method is as follows：
1. thoroughly being cleaned as the PEI substrates of gate electrode to having sprayed 80nm nano silver wires, drying is used after cleaning
Nitrogen dries up；
2. PMMA films are prepared on nano silver wire using spin-coating method forms gate insulator 520nm；
3. the PMMA film good to spin coating is through row heated baking；
4. spin coating is indigo on gate insulator:Diatom ooze mass ratio is 94:6 organic semiconductor layer 120nm；
6. silver-colored source electrode and drain electrode 70nm are prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=12 μ A, carrier mobility μ
=0.004cm2/ Vs, threshold voltage VTH=-16V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Embodiment 3
Preparation method is as follows：
1. thoroughly being cleaned as the shellac substrate of gate electrode to having sputtered 70nmITO, drying nitrogen is used after cleaning
Drying；
2. PVA film is prepared on ITO using spin-coating method forms gate insulator 20nm；
3. to the good PVA film of spin coating through row heated baking；
4. spin coating is indigo on gate insulator:Diatom ooze mass ratio is 90:10 organic semiconductor layer 100nm；
5. gold source and drain electrode 50nm is prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=0.5 μ A, carrier mobility
μ=0.001cm2/ Vs, threshold voltage VTH=-13V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Embodiment 4
Preparation method is as follows：
1. thoroughly being cleaned as the PI substrates of gate electrode to having sprayed 60nm graphenes, drying nitrogen is used after cleaning
Drying；
2. one layer of 20nm PS is generated as gate insulator using the method for spin coating；
3. spin coating prepares indigo on gate insulator:Diatom ooze mass ratio is 88:12 organic semiconductor layer 125nm；
4. gold source and drain electrode 60nm is prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=1.5 μ A, carrier mobility
μ=0.04cm2/ Vs, threshold voltage VTH=-18V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Embodiment 5
Its preparation method is as follows：
1. thoroughly being cleaned as the substrate of gate electrode to 60nm gold has been deposited, dried up after cleaning with drying nitrogen；
2. 300nmPS films are prepared on gold using spin-coating method forms gate insulator；
3. the PS film good to spin coating is through row heated baking；
4. spin coating prepares indigo on gate insulator:Diatom ooze mass ratio is 85:15 organic semiconductor layer 50nm；
5. silver-colored source electrode and drain electrode 70nm are prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=19 μ A, carrier mobility μ
=0.01cm2/ Vs threshold voltages VTH=-18V, PARA FORMALDEHYDE PRILLS(91,95) response is fine at room temperature.
Embodiment 6
Preparation method is as follows：
1. thoroughly being cleaned to the PEI substrates for having sputtered 50nmITO gate electrodes, dried up after cleaning with drying nitrogen；
2. 50nm PMMA films are prepared on ITO using spraying process forms gate insulator；
3. spin coating prepares indigo on gate insulator:Diatom ooze mass ratio is 83:17 organic semiconductor layer 120nm；
4. copper source electrode and drain electrode 60nm are prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=11 μ A, carrier mobility μ
=0.07cm2/ Vs, threshold voltage VTH=-17V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Embodiment 7
Preparation method is as follows：
1. thoroughly being cleaned to the PI substrates for having sputtered 60nmITO gate electrodes, dried up after cleaning with drying nitrogen；
2. 50nm PMMA films are prepared on ITO using spraying process forms gate insulator；
3. spin coating prepares indigo on gate insulator:Diatom ooze mass ratio is 80:20 organic semiconductor layer 120nm；
4. gold source and drain electrode 80nm is prepared using vacuum evaporation.
The formaldehyde response characteristic of device is tested, measures the saturation current I of deviceSD=10 μ A, carrier mobility μ
=0.03cm2/ Vs, threshold voltage VTH=-19V, at room temperature PARA FORMALDEHYDE PRILLS(91,95) respond.
Claims (10)
1. a kind of formaldehyde sensor based on organic field effect tube, including set gradually from top to bottom substrate, gate electrode,
Gate insulator and organic semiconductor layer, the upper end connection active electrode and drain electrode, its feature of the organic semiconductor layer exist
In：The organic semiconductor layer is to be mixed by indigo or indigo derivative with diatom ooze, silicon in the organic semiconductor layer
The mass percent of algal gel is 3%~20%.
2. the formaldehyde sensor according to claim 1 based on organic field effect tube, it is characterised in that the substrate
Material be polyimides, PEI, polyethylene naphthalate, shellac, mica or diatom ooze in one kind.
3. the formaldehyde sensor according to claim 1 based on organic field effect tube, it is characterised in that the grid
The material of insulating barrier is polyvinyl alcohol, polyimides, polystyrene, polymethyl methacrylate, the one or more of polyethylene,
The thickness of the gate insulator is 20~520nm.
4. the formaldehyde sensor according to claim 1 based on organic field effect tube, it is characterised in that described organic
The thickness of semiconductor layer is 50~120nm.
5. the formaldehyde sensor according to claim 1 based on organic field effect tube, it is characterised in that the grid electricity
The material of pole, source electrode and drain electrode is graphene, CNT, metal simple-substance nano wire, zinc oxide, titanium oxide, oxidation
One or more in indium tin or polymer electrode material；The gate electrode, source electrode and drain electrode thickness are 50~80nm.
6. the formaldehyde sensor according to claim 5 based on organic field effect tube, it is characterised in that the metal
Simple substance nano wire is Fe nanowire, copper nano-wire, nano silver wire, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese
One or more in nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires.
7. the formaldehyde sensor according to claim 5 based on organic field effect tube, it is characterised in that the polymerization
Thing electrode material is one in poly- (3,4- Ethylenedioxy Thiophenes)-poly- (styrene sulfonic acid) or 3,4- polyethylene dioxythiophenes
Kind.
8. a kind of preparation method of the formaldehyde sensor based on organic field effect tube, it is characterised in that comprise the following steps：
1. substrate is cleaned first with the one or more in detergent, acetone soln, deionized water and aqueous isopropanol,
Dried after cleaning；
2. preparing gate electrode on the surface of substrate, the figure of gate electrode is formed；
3. gate insulator is prepared on surface gate electrode；
4. diatom ooze solution is miscible according to percent mass proportioning progress with indigo or indigo derivative solution, then in oneself covering
Organic semiconductor layer just adult is prepared on the substrate of gate insulator, then 70 DEG C of thermal annealings 20 minutes, are made organic semiconductor
Layer；
5. source electrode and electric leakage level are prepared on organic semiconductor layer；
6. the organic field effect tube 5. step is made after is packaged.
9. the preparation method of the formaldehyde sensor according to claim 8 based on organic field effect tube, its feature exist
In, step 2. with step 5. in, gate electrode, source electrode, drain electrode are by vacuum thermal evaporation, magnetron sputtering, plasma
It is prepared by a kind of method in the chemical vapor deposition of enhancing, silk-screen printing, printing or spin coating.
10. the preparation method of the formaldehyde sensor according to claim 8 based on organic field effect tube, its feature exist
In, step 4. in, the organic semiconductor layer is by the chemical vapor deposition of plasma enhancing, thermal oxide, spin coating, vacuum
It is prepared by a kind of method in evaporation, roller coat, drop film, pressure institute, printing or gas blowout.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111505088A (en) * | 2020-04-14 | 2020-08-07 | 电子科技大学 | High-stability skin touch sensor and preparation method thereof |
| CN111610234A (en) * | 2020-07-07 | 2020-09-01 | 上海大学 | Acetone gas sensor of field effect transistor and preparation method thereof |
| CN112051316A (en) * | 2020-08-28 | 2020-12-08 | 电子科技大学 | Ammonia gas sensor based on organic thin film transistor and preparation method thereof |
| CN113640361A (en) * | 2021-07-19 | 2021-11-12 | 湘潭大学 | Grid sensitive FET gas sensor array for trace formaldehyde gas detection and preparation method thereof |
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| CN201654013U (en) * | 2010-01-29 | 2010-11-24 | 深圳市汇益德环保材料有限公司 | Detection device for diatom mud |
| CN106198635A (en) * | 2016-07-13 | 2016-12-07 | 电子科技大学 | A kind of humidity sensor based on organic field effect tube and preparation method thereof |
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| CN201654013U (en) * | 2010-01-29 | 2010-11-24 | 深圳市汇益德环保材料有限公司 | Detection device for diatom mud |
| CN106198635A (en) * | 2016-07-13 | 2016-12-07 | 电子科技大学 | A kind of humidity sensor based on organic field effect tube and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111505088A (en) * | 2020-04-14 | 2020-08-07 | 电子科技大学 | High-stability skin touch sensor and preparation method thereof |
| CN111610234A (en) * | 2020-07-07 | 2020-09-01 | 上海大学 | Acetone gas sensor of field effect transistor and preparation method thereof |
| CN111610234B (en) * | 2020-07-07 | 2021-09-07 | 上海大学 | Acetone gas sensor of field effect transistor and preparation method thereof |
| CN112051316A (en) * | 2020-08-28 | 2020-12-08 | 电子科技大学 | Ammonia gas sensor based on organic thin film transistor and preparation method thereof |
| CN113640361A (en) * | 2021-07-19 | 2021-11-12 | 湘潭大学 | Grid sensitive FET gas sensor array for trace formaldehyde gas detection and preparation method thereof |
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