CN107565020B - A kind of formaldehyde sensor and preparation method thereof based on organic field-effect tube - Google Patents
A kind of formaldehyde sensor and preparation method thereof based on organic field-effect tube Download PDFInfo
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Abstract
The invention belongs to sensor technical fields, a kind of formaldehyde sensor and preparation method thereof based on organic field-effect tube are disclosed, for solving the problems, such as that Monitoring lower-cut existing for existing formaldehyde sensor is not high.Formaldehyde sensor based on organic field effect tube of the invention, including substrate, gate electrode, gate insulating layer and the organic semiconductor layer set gradually from top to bottom, the upper end of the organic semiconductor layer is connected with source electrode and drain electrode, 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 flexibility is poor, the problems such as easily polluting the environment.
Description
Technical field
The invention belongs to sensor technical fields, and in particular to a kind of formaldehyde sensor based on organic field-effect tube and its
Preparation method.
Background technique
Formaldehyde is a kind of colourless, gas of irritating smell, to the irritating effect such as human eye, nose, 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, medicine and work
There is increasingly consequence in agricultural production.
Formaldehyde sensor it is many kinds of, currently, research hotspot both domestic and external be concentrated mainly on oxidation of formaldehyde object 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 vulnerable to ambient enviroment, error is relatively large, precision is insufficient, detection parameters list
One, it is not easy to realize that flexible, miniaturization, inorganic semiconductor material that is integrated, using are easy to cause secondary pollution etc. to lack environment
Point.
Summary of the invention
The present invention is not high in order to solve the problems, such as Monitoring lower-cut existing for existing formaldehyde sensor, and provides one kind and be based on having
The formaldehyde sensor and preparation method thereof of machine field-effect tube, solve the problems, such as Monitoring lower-cut existing for existing formaldehyde sensor it is high with
And flexibility existing for existing formaldehyde sensor is poor, easy the problems such as polluting the environment.
In order to solve the technical problem, the technical scheme adopted by the invention is that:
A kind of formaldehyde sensor based on organic field effect tube, including substrate, the grid electricity set gradually from top to bottom
Pole, gate insulating layer and organic semiconductor layer, the upper end of the organic semiconductor layer are connected with source electrode and drain electrode, feature
Be: 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, polyetherimide, polyethylene naphthalate, shellac, mica or silicon
One of algal gel.
The material of the gate insulating layer is polyvinyl alcohol, polyimides, polystyrene, polymethyl methacrylate, gathers
Ethylene it is one or more, the gate insulating layer with a thickness of 20~520nm.
The organic semiconductor layer with a thickness of 50~120nm.
The gate electrode, source electrode and drain electrode material be graphene, carbon nanotube, metal simple-substance nano wire, oxygen
Change one of zinc, titanium oxide, tin indium oxide or polymer electrode material or a variety of, the gate electrode, source electrode and drain electrode
Thickness is 50~80nm.
The metal simple-substance nano wire is Fe nanowire, copper nano-wire, silver nanowires, nanowires of gold, aluminium nano wire, nickel are received
One of rice noodles, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires
Or it is a variety of.
The polymer electrode material is poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) or 3,4- polyethylene
One of dioxy thiophene.
A kind of preparation method of the formaldehyde sensor based on organic field effect tube, which is characterized in that including following step
It is rapid:
1. being carried out first with one of detergent, acetone soln, deionized water and aqueous isopropanol or a variety of pairs of substrates
Cleaning, it is dry after cleaning；
2. the surface in substrate prepares gate electrode, the figure of gate electrode is formed；
3. preparing gate insulating layer 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
It covers and prepares organic semiconductor layer just adult on the substrate of gate insulating layer, then 70 DEG C thermal annealing 20 minutes, be made organic half
Conductor layer；
5. preparing source electrode and electric leakage grade 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,
The preparation of one of chemical vapor deposition, silk-screen printing, printing or the spin coating of plasma enhancing method.
The step 4. in, the organic semiconductor layer be by the chemical vapor deposition of plasma enhancing, thermal oxide,
One of spin coating, vacuum evaporation, roller coating, drop film, pressure institute, printing or gas blowout method preparation.
The present invention provides a kind of formaldehyde sensor and preparation method thereof based on organic field effect tube, will be water-soluble
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 stronger formaldehyde adsorption of diatom ooze ability and itself be
The characteristics of molecular porous structure, meanwhile, the ruler of semiconductor material crystal grain in organic semiconductor is controlled 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
In road, to enhance effective detection of formaldehyde sensor PARA FORMALDEHYDE PRILLS(91,95) molecule.
Simultaneously as diatom ooze has excellent water absorption character and stronger flexibility, therefore, in organic semiconductor layer
After middle introducing diatom ooze, it can be obviously improved suction-operated of the half organic conductor layer to hydrone, can be significantly reduced under detection
Limit increases the response rate of formaldehyde sensor, while effectively promoting the mechanical strength and flexibility of electronic component.
In conclusion compared with prior art, the invention has the following advantages:
1, it is introduced in indigo or indigo derivative semiconductor layer after a certain amount of water-soluble silicon algal gel, in the present invention
The response rate of formaldehyde sensor is obviously improved, and detection limit is lower.
2, it is 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, be able to achieve the quick detection of gas.
3, 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.
4, indigo, indigo derivative and water-soluble silicon algal gel belong to the common materials in nature, from a wealth of sources, cost
Cheap, preparation process is simple, it is easy to accomplish industrialization large-scale production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the formaldehyde sensor of the invention based on organic field-effect tube；
Fig. 2 is the change curve of formaldehyde sensor performance under the conditions of different formaldehyde prepared for embodiment 5；It can be seen that
Under the conditions of different formaldehyde, the performance parameter (saturation current, carrier mobility, threshold voltage) of device has occurred larger device
Variation, play the effect accurately detected；
Marked in the figure: 1, substrate, 2, gate electrode, 3, gate insulating layer, 4, organic semiconductor layer, 5, source electrode, 6, electric leakage
Pole.
Specific embodiment
The present invention will be further described with reference to the examples below, and described embodiment is only present invention a part
Embodiment is not whole embodiment.Based on the embodiments of the present invention, those skilled in the art are not making
Other embodiments used obtained, belong to protection scope of the present invention under the premise of creative work.
In conjunction with attached 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 insulating layer 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), polyetherimide (PEI), gathers to naphthalene
One of dioctyl phthalate second diester (PEN), shellac, mica or diatom ooze；Substrate needs that there is certain anti-steam and oxygen to seep
Saturating ability, while also needing that there is preferable surface smoothness.
The gate insulating layer 3 is polyethylene using the material with good dielectric properties, the material of gate insulating layer 3
One kind or more of alcohol (PVA), polyimides (PI), polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene (PE)
Kind, preparation method can be one of chemical vapor deposition, thermal oxide, spin coating or vacuum evaporation of plasma enhancing side
Method；The gate insulating layer 3 with a thickness of 20~520nm.
The preparation method of machine semiconductor layer can be chemical vapor deposition, thermal oxide, spin coating, the vacuum of plasma enhancing
One of vapor deposition, drop film, coining, printing or gas blowout method；Organic semiconductor layer 4 with a thickness of 50~120nm.
The gate electrode, source electrode and drain electrode material be graphene, carbon nanotube, metal simple-substance nano wire, oxygen
Change one of zinc, titanium oxide, tin indium oxide or polymer electrode material or a variety of, preparation method can be vacuum thermal evaporation,
One of various deposition methods 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, silver nanowires, nanowires of gold, aluminium nano wire, nickel are received
One of rice noodles, cobalt nanowire, manganese nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires
Or it is a variety of.
The polymer electrode material is poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) or 3,4- polyethylene
One of dioxy thiophene.
A kind of preparation method of the formaldehyde sensor based on organic field effect tube, comprising the following steps:
1. being carried out first with one of detergent, acetone soln, deionized water and aqueous isopropanol or a variety of pairs of substrates
Cleaning, it is dry after cleaning；
2. the surface in substrate prepares gate electrode, the figure of gate electrode is formed；
3. preparing gate insulating layer 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
It covers and prepares organic semiconductor layer just adult on the substrate of gate insulating layer, then 70 DEG C thermal annealing 20 minutes, be made organic half
Conductor layer；
5. preparing source electrode and electric leakage grade 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,
The preparation of one of chemical vapor deposition, silk-screen printing, printing or the spin coating of plasma enhancing method.
The step 4. in, the organic semiconductor layer be by the chemical vapor deposition of plasma enhancing, thermal oxide,
One of spin coating, vacuum evaporation, roller coating, drop film, pressure institute, printing or gas blowout method preparation.
The present invention provides a kind of formaldehyde sensor and preparation method thereof based on organic field effect tube, will be water-soluble
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 stronger formaldehyde adsorption of diatom ooze ability and itself be
The characteristics of molecular porous structure, meanwhile, the ruler of semiconductor material crystal grain in organic semiconductor is controlled 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
In road, to enhance effective detection of formaldehyde sensor PARA FORMALDEHYDE PRILLS(91,95) molecule.
Simultaneously as diatom ooze has excellent water absorption character and stronger flexibility, therefore, in organic semiconductor layer
After middle introducing diatom ooze, it can be obviously improved suction-operated of the half organic conductor layer to hydrone, can be significantly reduced under detection
Limit increases the response rate of formaldehyde sensor, while effectively promoting the mechanical strength and flexibility of electronic component.
Embodiment 1
The preparation method is as follows:
1. thoroughly being cleaned to PI substrate of the 50nmITO as gate electrode has been sputtered, dry nitrogen air-blowing is used after cleaning
It is dry；
2. preparing PS film on ITO using spin-coating method forms gate insulating layer 100nm；
3. the PS film good to spin coating is through row heated baking；
4. spin coating is indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 100nm of 97:3；
5. preparing copper source electrode and drain electrode 80nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=6 μ A, carrier mobility μ
=2 × 10-3cm2/ Vs, threshold voltage VTH=-14V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
Embodiment 2
The preparation method is as follows:
1. thoroughly being cleaned to PEI substrate of the 80nm silver nanowires as gate electrode has been sprayed, drying is used after cleaning
It is dried with nitrogen；
2. preparing PMMA film in silver nanowires using spin-coating method forms gate insulating layer 520nm；
3. the PMMA film good to spin coating is through row heated baking；
4. spin coating is indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 120nm of 94:6；
6. preparing silver-colored source electrode and drain electrode 70nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=12 μ A, carrier mobility μ
=0.004cm2/ Vs, threshold voltage VTH=-16V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
Embodiment 3
The preparation method is as follows:
1. thoroughly being cleaned to shellac substrate of the 70nmITO as gate electrode has been sputtered, drying nitrogen is used after cleaning
Drying；
2. preparing PVA film on ITO using spin-coating method forms gate insulating layer 20nm；
3. to the good PVA film of spin coating through row heated baking；
4. spin coating is indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 100nm of 90:10；
5. preparing gold source and drain electrode 50nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=0.5 μ A, carrier mobility
μ=0.001cm2/ Vs, threshold voltage VTH=-13V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
Embodiment 4
The preparation method is as follows:
1. thoroughly being cleaned to PI substrate of the 60nm graphene as gate electrode has been sprayed, drying nitrogen is used after cleaning
Drying；
2. generating one layer of 20nm PS as gate insulating layer using the method for spin coating；
3. spin coating prepares indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 125nm of 88:12；
4. preparing gold source and drain electrode 60nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=1.5 μ A, carrier mobility
μ=0.04cm2/ Vs, threshold voltage VTH=-18V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
Embodiment 5
Preparation method is as follows:
1. thoroughly being cleaned to substrate of the 60nm gold as gate electrode has been deposited, dried up after cleaning with drying nitrogen；
2. preparing 300nmPS film on gold using spin-coating method forms gate insulating layer；
3. the PS film good to spin coating is through row heated baking；
4. spin coating prepares indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 50nm of 85:15；
5. preparing silver-colored source electrode and drain electrode 70nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=19 μ A, carrier mobility μ
=0.01cm2/ Vs threshold voltage VTH=-18V, PARA FORMALDEHYDE PRILLS(91,95) response is fine at room temperature.
Embodiment 6
The preparation method is as follows:
1. thoroughly being cleaned to the PEI substrate for having sputtered 50nmITO gate electrode, dried up after cleaning with drying nitrogen；
2. preparing 50nm PMMA film on ITO using spray coating method forms gate insulating layer；
3. spin coating prepares indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 120nm of 83:17；
4. preparing copper source electrode and drain electrode 60nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=11 μ A, carrier mobility μ
=0.07cm2/ Vs, threshold voltage VTH=-17V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
Embodiment 7
The preparation method is as follows:
1. thoroughly being cleaned to the PI substrate for having sputtered 60nmITO gate electrode, dried up after cleaning with drying nitrogen；
2. preparing 50nm PMMA film on ITO using spray coating method forms gate insulating layer；
3. spin coating prepares indigo on gate insulating layer: diatom ooze mass ratio is the organic semiconductor layer 120nm of 80:20；
4. preparing gold source and drain electrode 80nm using vacuum evaporation.
The formaldehyde response characteristic of device is tested, the saturation current I of device is measuredSD=10 μ A, carrier mobility μ
=0.03cm2/ Vs, threshold voltage VTH=-19V, PARA FORMALDEHYDE PRILLS(91,95) responds at room temperature.
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 insulating layer and organic semiconductor layer, the upper end of the organic semiconductor layer are connected with source electrode and drain electrode, and feature exists
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, which is characterized in that the substrate
Material be one of polyimides, polyetherimide, polyethylene naphthalate, shellac, mica or diatom ooze.
3. the formaldehyde sensor according to claim 1 based on organic field effect tube, which is characterized in that the grid
The material of insulating layer be polyvinyl alcohol, polyimides, polystyrene, polymethyl methacrylate, polyethylene it is one or more,
The gate insulating layer with a thickness of 20~520nm.
4. the formaldehyde sensor according to claim 1 based on organic field effect tube, which is characterized in that described organic
Semiconductor layer with a thickness of 50~120nm.
5. the formaldehyde sensor according to claim 1 based on organic field effect tube, which is characterized in that the grid electricity
Pole, source electrode and drain electrode material be graphene, carbon nanotube, metal simple-substance nano wire, zinc oxide, titanium oxide, oxidation
One of indium tin or polymer electrode material are a variety of；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, which is characterized in that the metal
Simple substance nano wire is Fe nanowire, copper nano-wire, silver nanowires, nanowires of gold, aluminium nano wire, nickel nano wire, cobalt nanowire, manganese
One of nano wire, cadmium nano wire, indium nano wire, stannum nanowire, tungsten nanowires or Pt nanowires are a variety of.
7. the formaldehyde sensor according to claim 5 based on organic field effect tube, which is characterized in that the polymerization
Object electrode material is one in poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid) or 3,4- polyethylene dioxythiophene
Kind.
8. a kind of preparation method of the formaldehyde sensor based on organic field effect tube, which comprises the following steps:
1. it is cleaned first with one of detergent, acetone soln, deionized water and aqueous isopropanol or a variety of pairs of substrates,
It is dry after cleaning；
2. the surface in substrate prepares gate electrode, the figure of gate electrode is formed；
3. preparing gate insulating layer 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 insulating layer, then 70 DEG C thermal annealing 20 minutes, are made organic semiconductor
Layer；
5. preparing source electrode and electric leakage grade 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, feature exist
In, step 2. with step 5. in, gate electrode, source electrode, drain electrode are by vacuum thermal evaporation, magnetron sputtering, plasma
The preparation of one of chemical vapor deposition, silk-screen printing, printing or the spin coating of enhancing method.
10. the preparation method of the formaldehyde sensor according to claim 8 based on organic field effect tube, feature exist
In, step 4. in, the organic semiconductor layer is by the chemical vapor deposition of plasma enhancing, thermal oxide, spin coating, vacuum
One of vapor deposition, roller coating, drop film, pressure institute, printing or gas blowout method preparation.
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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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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