CN104849336A - Organic field effect transistor gas sensor and preparation method thereof - Google Patents
Organic field effect transistor gas sensor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic field effect transistor gas sensor and a preparation method thereof, belongs to the technical field of electronic components, and solves the problems that the size of crystal grains in an organic material cannot be accurately controlled and room temperature detection of the organic field effect transistor gas sensor cannot be realized in the prior art. The organic semiconductor layer is soluble, and 5% -15% of shellac is added into the organic semiconductor layer for mixing. The invention is used for accurately controlling the size of crystal grains in the organic material and realizing the room temperature detection of the organic field effect transistor gas sensor.
Description
Technical field
A kind of organic field effect tube gas sensor and preparation method thereof, for accurately controlling the size of crystal grain in organic material, realizing the room temperature detection of organic field effect tube gas sensor, belonging to technical field of electronic components.
Background technology
Field effect transistor is one of forward position research direction of photoelectron and electronic technology field, because it can work under the condition of small area analysis, low-voltage, is therefore widely used in large scale integrated circuit.At present, organic field effect tube (Organic field-effect transistor is called for short OFET) significantly improves the electronic information field present situation based on inorganic field effect transistor in all many-sides.In recent years, based on the gas sensor of the organic field effect tube of organic semiconducting materials, obtain the extensive concern of people because it has the characteristic of multiparameter response and parameter amplification.Gas sensor based on organic field effect tube has following advantage:
1. the more renewals of the film technique of organic material, make the size of device littlely can be convenient to integrated production, and organic material ratio is easier to obtain, and price is relatively cheap, preparation technology is also more simple, and preparation condition is gentleer, effectively can reduce device cost;
2. organic field effect tube has good pliability, and quality is light, is easy to carry.In proper range, bending or twisting is repeatedly carried out to flexible OFET, can not its electric property of appreciable impact;
3. multiple parameters of organic field effect tube may be used for the indication parameter of OFET sensor, realize the regulation and control model of multiparameter, make the sensor based on OFET have better response characteristic;
4. organic field effect tube has the advantages that parameter is amplified, and makes the gas sensor based on OFET more responsive.
In order to improve responsiveness based on OFET gas sensor and recovery, usually requiring to detect under heating environment, and still there is larger limitation in room temperature detection.The size of adjustment organic semiconductor layer crystal grain significantly can improve the detection of gas performance of device, the object detected under reasonably selecting the size of crystal grain can realize room temperature, reason is the high-performance that suitable large grain size ratio can ensure OFET, and the introducing of little crystal grain can significantly improve the responsiveness of OFET sensor.At present, the main method controlling organic semiconducting materials grain size is the technique controlling film forming speed and adopt after annealing.The subject matter existed is that the grain size formed is difficult to accurate control, does not reach the application requirement of OFET gas sensor; And post growth annealing takes time and effort, require harsh to the temperature capacity of other functional layers in device.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part and provide a kind of organic field effect tube gas sensor and preparation method thereof, solve the problem of the size that accurately can not control crystal grain in organic material in prior art, the room temperature that can not realize OFET gas sensor detection.
To achieve these goals, the technical solution used in the present invention is:
A kind of organic field effect tube gas sensor, its structure comprises the substrate, gate electrode, gate insulator, the organic semiconductor layer that set gradually from top to bottom, the source electrode that organic semiconductor layer is arranged and drain electrode, it is characterized in that: described organic semiconductor layer is solubility, and the shellac adding 5% ~ 15% at organic semiconductor layer mixes.
Further, described gate insulator is solubility, is one or more organic polymer insulating material or the silicon dioxide (SiO of polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl alcohol (PVA) (PVA), polyvinylidene fluoride (PVDF), polyimide (PI)
2), alundum (Al2O3) (Al
2o
3), titanium dioxide (TiO
2) one or more inorganic insulating materials, thickness is 150 ~ 650nm.
Further, described organic semiconductor layer is one or more soluble organic semiconductor materials of poly-3-hexyl thiophene (P3HT), Tips-pentacene (Tips-pentacene), and thickness is 35 ~ 350nm.
Further, described gate electrode, source electrode and leak electricity very metal or conductive film, source electrode and drain electrode thickness are 15 ~ 350nm, described metal be gold, silver, copper one or more, described conductive film is one or more of tin indium oxide and ZnO transparent.
A preparation method for organic field effect tube gas sensor, is characterized in that, comprises the following steps:
1. utilize washing agent, acetone soln, deionized water and the aqueous isopropanol substrate to the transparent gate electrode ITO of band to clean, dry up with nitrogen after cleaning;
2. on gate electrode, gate insulator is prepared;
3. same ethanol is carried out 1:10 dilution shellac stir after, with soluble organic semiconductor material solution carry out 5% ~ 15% miscible, on gate insulator, prepare shellac-organic semiconductor layer solution, 90 DEG C are carried out thermal annealing;
4. on organic semiconductor layer, source electrode and drain electrode is prepared;
5. the organic field effect tube device after step 4. being obtained encapsulates at glove box, and glove box is atmosphere of inert gases.
Further, described step 2. in shellac-gate insulator, step 3. in organic semiconductor layer, step 4. in source electrode and drain electrode be formed by one or several modes in vacuum evaporation, ionized cluster beam deposition, ion plating, DC sputtering deposition, radio-frequency sputtering plated film, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductive coupling plasma source chemical vapor deposition, catalyst chemical vapor deposition, magnetron sputtering, plating, spin coating, dip-coating, inkjet printing, roller coat, LB film.
Compared with prior art, the invention has the advantages that:
One, add shellac having in soluble organic semiconductor layer, accurately easy control can be carried out by regulation and control shellac proportion size to the island structure that the crystal grain of organic material or multiple crystal grain are assembled in soluble gate insulator layer;
Two, add shellac having in soluble organic semiconductor layer, reach the object of OFET room temperature detection, simultaneously by the ratio of adjustment grain size, play the effect improving organic field effect tube performance.
Accompanying drawing explanation
Fig. 1 is the structural representation of structure of the present invention, is followed successively by from top to bottom: 1-source electrode, 2-drain electrode, 3-organic semiconductor layer, 4-gate insulator, 5-gate electrode, 6-substrate;
Fig. 2 is that the present invention adopts P3HT: shellac is that the OFET normal temperature of 85:15 is to the detection of nitrogen dioxide.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated.
As shown in Figure 1, the substrate 6 that device architecture sets gradually from top to bottom, gate electrode 5, gate insulator 4, organic semiconductor layer 3, the source electrode 1 that organic semiconductor layer 3 is arranged and drain electrode 2.
Described soluble gate insulator layer is polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl alcohol (PVA) (PVA), polyvinylidene fluoride (PVDF), one or more organic polymer insulating material of polyimide (PI) or silicon dioxide (SiO
2), alundum (Al2O3) (Al
2o
3), titanium dioxide (TiO
2) one or more inorganic insulating materials, thickness is 150 ~ 650nm; Described organic semiconductor layer is one or more soluble organic semiconductor materials of poly-3-hexyl thiophene (P3HT), Tips-pentacene (Tips-pentacene), and thickness is 35 ~ 350nm; Described gate electrode, source electrode and leak electricity very metal or conductive film, wherein source electrode and drain electrode thickness are 15 ~ 350nm, described metal comprise gold, silver, copper one or more, described conductive film be tin indium oxide, ZnO transparent one or more.
Shellac is a kind of natural resin, comprise the resin of 80 ~ 90%, the lac pigment of 4 ~ 7%, the shellac wax of 4 ~ 7% and the water of 2 ~ 6%, there is unique good characteristic, be widely used in food, medicine, plastics, military affairs, electrically, the industry such as rubber, ink, leather, coating, dyestuff and bonding agent.Shellac is nontoxic, is mainly used in the capsule etc. of nutrients that the moistureproof sugar-coat of pill tablet, medication containment, glazing, enteric cartridge bag clothing and developed recently get up and cosmetics at present in medical industry.Shellac coating can be used for a lot of aspects of food industry equally, can be absorbed by the body, can natural degradation, such as, after candy and cake have been coated with shellac coating, can become very attractive in appearance, bright, can protection against the tide, anti-caking, anti-metamorphic and prolongation period of storage etc.Fruit, with after shellac coating film, can suppress moisture to evaporate over a period to come, keep fresh, reduces and rots, improve outward appearance, produces the effect of increasing economic efficiency.Shellac product has good tensile strength, wearing quality, rebound resilience and hardness, has desirable mechanical property.Electric property aspect, the dielectric strength of shellac is high, and after arranging by electric arc, without electric conductivity, adds that it has good stickability and thermoplasticity, electrical apparatus insulation has special purposes.In addition, the film that the film that the shellac be hydrolyzed is formed is formed than natural shellac is more soft, and this is relevant with the increase of barras in shellac.But the steam impregnability of hydrolysis shellac film is than lower with natural shellac film, so need to carry out the water oxygen obstructing capacity that some process ensure shellac.
Embodiment 1
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the PMMA gate insulator of transparent conductive cathode ITO surface rotary coating 150nm, and formed film is dried; Spin coating P3HT on gate insulator: shellac volume ratio is the organic semiconductor layer 35nm of 95:5, and is dried by formed film; Thermal evaporation gold source-drain electrode 15nm on organic semiconductor layer.Record the saturation current (I of device
sD)=7 μ A, threshold voltage (V
tH)=-5V, P3HT large grain size accounts for leading, and little crystal grain is less, under room temperature to oxidizing gas without response.
Embodiment 2
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the PS gate insulator of transparent conductive cathode ITO surface rotary coating 250nm, and formed film is dried; Spin coating P3HT on gate insulator: shellac volume ratio is the organic semiconductor layer 100nm of 93:7; Thermal evaporation silver source-drain electrode 100nm on organic semiconductor layer.Record the saturation current (I of device
sD)=8 μ A, threshold voltage (V
tH)=-5V, P3HT large grain size accounts for leading, and little crystal grain is less, under room temperature to oxidizing gas without response.
Embodiment 3
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the PVA gate insulator of transparent conductive cathode ITO surface rotary coating 350nm, and formed film is dried; Spin coating P3HT on gate insulator: shellac volume ratio is the organic semiconductor layer 150nm of 91:9, and is dried by formed film; Thermal evaporation copper source-drain electrode 150nm on organic semiconductor layer.Record the saturation current (I of device
sD)=9 μ A, threshold voltage (V
tH)=-5V, P3HT large grain size is more, and little crystal grain is less, under room temperature to oxidizing gas without response.
Embodiment 4
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the PVDF gate insulator of transparent conductive cathode ITO surface rotary coating 450nm, and formed film is dried; Spin coating Tips-pentacene on gate insulator: shellac volume ratio is the organic semiconductor layer 200nm of 89:11, and is dried by formed film; Thermal evaporation gold source-drain electrode 200nm on organic semiconductor layer.Record the saturation current (I of device
sD)=10 μ A, threshold voltage (V
tH)=-5V, Tips-pentacene large grain size is more, and little crystal grain is less, poor to oxidizing gas response under room temperature.Embodiment 5
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the PI gate insulator of transparent conductive cathode ITO surface rotary coating 550nm, and formed film is dried; Spin coating Tips-pentacene on gate insulator: shellac volume ratio is the organic semiconductor layer 250nm of 88:12, and is dried by formed film; Thermal evaporation gold source-drain electrode 250nm on organic semiconductor layer.Record the saturation current (I of device
sD)=11 μ A, threshold voltage (V
tH)=-5V, Tips-pentacene large grain size is more, and little crystal grain is less, poor to oxidizing gas response under room temperature.
Embodiment 6
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; The SiO of 600nm is prepared at transparent conductive cathode ITO surface chemistry vapour deposition process
2gate insulator, and formed film is dried; Spin coating Tips-pentacene on gate insulator: shellac volume ratio is the organic semiconductor layer 300nm of 87:13, and is dried by formed film; Thermal evaporation gold source-drain electrode 300nm on organic semiconductor layer.Record the saturation current (I of device
sD)=12 μ A, threshold voltage (V
tH)=-5V, Tips-pentacene large grain size is dominated, and little crystal grain is more, medium to oxidizing gas response under room temperature.
Embodiment 7
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the Al of transparent conductive cathode ITO surface sputtering 650nm
2o
3gate insulator, and formed film is dried; Spin coating Tips-pentacene on gate insulator: shellac volume ratio is the organic semiconductor layer 650nm of 86:14, and is dried by formed film; Thermal evaporation gold source-drain electrode 350nm on organic semiconductor layer.Record the saturation current (I of device
sD)=13 μ A, threshold voltage (V
tH)=-5V, Tips-pentacene large grain size is dominated, and little crystal grain is more, responds under room temperature to oxidizing gas.
Embodiment 8
The substrate be made up of transparent substrates and electrically conducting transparent ITO is cleaned, dries up with nitrogen after cleaning; At the TiO of transparent conductive cathode ITO surface spin coating 650nm
2gate insulator, and formed film is dried; Spin coating Tips-pentacene on gate insulator: shellac volume ratio is the organic semiconductor layer 650nm of 85:15, and is dried by formed film; Thermal evaporation gold source-drain electrode 350nm on organic semiconductor layer.Record the saturation current (I of device
sD)=14 μ A, threshold voltage (V
tH)=-5V, Tips-pentacene large grain size is dominated, and little crystal grain is more, under room temperature to oxidizing gas response very well.
Table 1: the device parameter performance table adding the shellac of different proportion
| P3HT: shellac | I SD(μA) | To the response of oxidizing gas under room temperature |
| 0 | 5 | Nothing |
| 95:5 | 7 | Nothing |
| 93:7 | 8 | Nothing |
| 91:9 | 9 | Nothing |
| 89:11 | 10 | Poor |
| 88:12 | 11 | Poor |
| 87:13 | 12 | Medium |
| 86:14 | 13 | Good |
| 85:15 | 14 | Very well |
Claims (6)
1. an organic field effect tube gas sensor, its structure comprises the substrate (6), gate electrode (5), gate insulator (4), the organic semiconductor layer (3) that set gradually from top to bottom, at source electrode (1) and the drain electrode (2) of the upper setting of organic semiconductor layer (3), it is characterized in that: described organic semiconductor layer (3) is solubility, and the shellac adding 5% ~ 15% at organic semiconductor layer mixes.
2. a kind of organic field effect tube gas sensor according to claim 1, it is characterized in that: described gate insulator (4) is solubility, is one or more organic polymer insulating material or the silicon dioxide (SiO of polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl alcohol (PVA) (PVA), polyvinylidene fluoride (PVDF), polyimide (PI)
2), alundum (Al2O3) (Al
2o
3), titanium dioxide (TiO
2) one or more inorganic insulating materials, thickness is 150 ~ 650nm.
3. a kind of organic field effect tube gas sensor according to claim 1, it is characterized in that: described organic semiconductor layer (3) is one or more soluble organic semiconductor materials of poly-3-hexyl thiophene (P3HT), Tips-pentacene (Tips-pentacene), and thickness is 35 ~ 350nm.
4. a kind of organic field effect tube gas sensor according to claim 1, it is characterized in that: described gate electrode (5), source electrode (1) and drain electrode (2) are metal or conductive film, source electrode (1) and drain electrode (2) thickness are 15 ~ 350nm, described metal be gold, silver, copper one or more, described conductive film be tin indium oxide, ZnO transparent one or more.
5. a preparation method for organic field effect tube gas sensor, is characterized in that, comprises the following steps:
1. utilize washing agent, acetone soln, deionized water and the aqueous isopropanol substrate (6) to the transparent gate electrode ITO of band to clean, dry up with nitrogen after cleaning;
2. on gate electrode (5), gate insulator (4) is prepared;
3. same ethanol is carried out 1:10 dilution shellac stir after, with soluble organic semiconductor layer (3) solution carry out 5% ~ 15% miscible, on gate insulator (4), prepare shellac-organic semiconductor layer, 90 DEG C are carried out thermal annealing;
4. on organic semiconductor layer (3), source electrode (1) and drain electrode (2) is prepared;
5. the organic field effect tube device after step 4. being obtained encapsulates at glove box, and glove box is atmosphere of inert gases.
6. the preparation method of a kind of organic field effect tube gas sensor according to claim 5, it is characterized in that: described step 2. in shellac-gate insulator (4), step 3. in organic semiconductor layer (3), step 4. in source electrode (1) and drain electrode (2) be pass through vacuum evaporation, ionized cluster beam deposition, ion plating, DC sputtering deposition, radio-frequency sputtering plated film, ion beam sputtering deposition, ion beam assisted depositing, plasma reinforced chemical vapour deposition, high density inductive coupling plasma source chemical vapor deposition, catalyst chemical vapor deposition, magnetron sputtering, plating, spin coating, dip-coating, inkjet printing, roller coat, one or several modes in LB film are formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194945.6A CN104849336B (en) | 2015-04-22 | 2015-04-22 | Organic field effect tube gas sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194945.6A CN104849336B (en) | 2015-04-22 | 2015-04-22 | Organic field effect tube gas sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104849336A true CN104849336A (en) | 2015-08-19 |
| CN104849336B CN104849336B (en) | 2018-01-19 |
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| CN105510389A (en) * | 2015-11-26 | 2016-04-20 | 电子科技大学 | Humidity sensor based on organic field-effect transistor and preparation method thereof |
| CN106098941A (en) * | 2016-06-17 | 2016-11-09 | 同济大学 | There is micro-nano pore structure organic field effect tube sensor and making thereof and application |
| CN106433310A (en) * | 2016-09-12 | 2017-02-22 | 清华大学深圳研究生院 | Ink, sensitive layer, biosensor and preparation method of ink |
| CN107565019A (en) * | 2017-08-30 | 2018-01-09 | 电子科技大学 | One kind is based on organic field-effect tube ammonia gas sensor and preparation method thereof |
| CN110530933A (en) * | 2019-07-18 | 2019-12-03 | 广东工业大学 | A kind of sensor film for detecting low molecular weight alcohols gas and preparation method thereof and sensor |
| CN111430539A (en) * | 2020-03-16 | 2020-07-17 | 电子科技大学 | Long-life electronic skin and preparation method thereof |
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| CN105334257A (en) * | 2015-11-25 | 2016-02-17 | 电子科技大学 | OFET (Organic Field Effect Transistor) ammonia gas sensor containing functional insulation layer |
| CN105510389A (en) * | 2015-11-26 | 2016-04-20 | 电子科技大学 | Humidity sensor based on organic field-effect transistor and preparation method thereof |
| CN106098941A (en) * | 2016-06-17 | 2016-11-09 | 同济大学 | There is micro-nano pore structure organic field effect tube sensor and making thereof and application |
| CN106433310A (en) * | 2016-09-12 | 2017-02-22 | 清华大学深圳研究生院 | Ink, sensitive layer, biosensor and preparation method of ink |
| CN106433310B (en) * | 2016-09-12 | 2021-03-12 | 清华大学深圳研究生院 | Ink, sensitive layer, biosensor and preparation method thereof |
| CN107565019A (en) * | 2017-08-30 | 2018-01-09 | 电子科技大学 | One kind is based on organic field-effect tube ammonia gas sensor and preparation method thereof |
| CN110530933A (en) * | 2019-07-18 | 2019-12-03 | 广东工业大学 | A kind of sensor film for detecting low molecular weight alcohols gas and preparation method thereof and sensor |
| CN111430539A (en) * | 2020-03-16 | 2020-07-17 | 电子科技大学 | Long-life electronic skin and preparation method thereof |
| CN111505088A (en) * | 2020-04-14 | 2020-08-07 | 电子科技大学 | High-stability skin touch sensor and preparation method thereof |
| CN112666239A (en) * | 2021-01-13 | 2021-04-16 | 长春工业大学 | Preparation method of OFET gas sensor based on polymer blend dielectric layer |
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