CN105301055A - Organic thin-film transistor nitrogen dioxide sensor - Google Patents
Organic thin-film transistor nitrogen dioxide sensor Download PDFInfo
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- CN105301055A CN105301055A CN201510830580.1A CN201510830580A CN105301055A CN 105301055 A CN105301055 A CN 105301055A CN 201510830580 A CN201510830580 A CN 201510830580A CN 105301055 A CN105301055 A CN 105301055A
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Abstract
The present invention discloses an organic thin-film transistor nitrogen dioxide sensor, which sequentially comprises a substrate, a gate electrode and an insulating layer from bottom to top, wherein a zinc oxide nanometer particle layer is dispersed on the insulating layer surface, an organic semiconductor layer being a non-continuous film is arranged on the zinc oxide nanometer particle layer, impurity organic semiconductor molecules contacting the zinc oxide nanometer particles are precipitated on the organic semiconductor layer or in the gap, and the impurity organic semiconductor molecules are provided with a source electrode and a drain electrode. According to the present invention, the impurity organic semiconductor molecules are introduced into the non-continuous organic semiconductor layer to reduce the organic thin-film transistor performance so as to improve the responsiveness to the nitrogen dioxide, and the zinc oxide nanometer particles can improve the selectivity to the nitrogen dioxide so as to achieve the high-sensitivity and high-response detection of the device on the nitrogen dioxide; and the preparation of the organic thin-film transistor nitrogen dioxide sensor is simple, the work voltage is low, and flexibility, transparency and other characteristics can be achieved only by replacing the substrate.
Description
Technical field
The invention belongs to sensor preparing technical field, particularly a kind of organic field-effect tube nitrogen dioxide sensor.
Background technology
In the daily productive life of the mankind, direct or indirect releases a lot of harmful gas in air, as ammonia, nitrogen dioxide, sulphuric dioxide, formaldehyde, sulfuretted hydrogen etc.These harmful gases drastically influence the healthy of the mankind, high concentration go back entail dangers to life security.
In more than ten years in the past, researcher have developed a large amount of gas sensors based on metal-oxide film, optical fiber and biomaterial.From principle of work, the gas sensor of main flow, mostly is resistance sensor in the market, and being reacted at film surface by gas molecule causes the change of conductivity, macroscopically by the change of detection resistance value to realize the detection to gas concentration.And the detection of non-resistor mainly by utilizing some physical influences and device property to realize gas, the such as change of electric capacity (C-V), the volt-ampere characteristic of schottky diode and gold belong to the characteristics such as – oxygen thing – semiconductor field (MOSFET) threshold voltage variation.Based in the sensor of transistor, grid voltage can produce slight change due to the impact of measured matter, due to the amplification of transistor itself, the obvious channel current of change will be obtained, can realize the detection to test substance by detection channel current, the resistance compared to more difficult monitoring is easier to detection.
Develop rapidly along with organic electronics and the application in sensor field thereof, with organic field-effect tube (organicthin-filmtransistor, OTFT) chemical sensor formed based on becomes a study hotspot of sensor field, is applied to inorganic and detection that is volatile organic compounds and has wide coverage.Compared with traditional gas sensor, based on OTFT structure gas sensor except have highly sensitive, the advantage such as can to use at normal temperatures except, also there is several remarkable advantage:
1) transistor fundamental characteristics is utilized to be the curent change easily detected by the high resistance change transitions being difficult to detect;
2) sensitivity of sensor is regulated by the gate operational voltages of suitable selector;
3) multiparameter model more has the identification and analysis that utilize gas;
4) by can regulate the electrical property of sensor easily to the chemical modification of organic molecule, sensitivity is improved;
5) organism pliability is good, can bend, and is easy to make various shape;
6) be easy to integrated, large area sensor array can be prepared, be convenient to integrated, microminiaturized future development.
Summary of the invention
The object of the invention is the shortcoming overcoming traditional gas sensor, there is provided a kind of preparation technology simple, low production cost, can be used for gas detect and can a kind of organic field-effect tube gas sensor based on mix insulation layer and preparation method thereof of multiparameter response.
Technical scheme of the present invention is:
A kind of organic field-effect tube nitrogen dioxide sensor, from top to bottom as substrate, gate electrode, insulation course, Zinc oxide nanoparticle, organic semiconductor layer, impurity molecule organic semiconductor, source electrode and drain electrode, it is characterized in that, described organic semiconductor layer is discontinuous film; Described surface of insulating layer is dispersed with Zinc oxide nanoparticle; Described impurity molecule organic semiconductor to be deposited in organic semiconductor lamellar spacing and to contact with Zinc oxide nanoparticle.
Further, described organic semiconductor layer is made up of P type small molecule organic semiconductor material, comprise aphthacene, pentacene, 6, the one in the silica-based acetylene pentacene of 13 – bis-or three isopropyl ester, rubrene or six thiophene, described organic semiconductor layer thickness is 20nm-30nm.
Further, described impurity molecule organic semiconductor is the p-type Small molecular of N-shaped Small molecular or high electron density, and described N-shaped Small molecular comprises, C60, N, N '-diamyl-3,4,9,10-perylene dicarboximide, N, N '-diphenyl-3,4,9,10-perylene dicarboximide, N, N '-dioctyl-3,4,9,10-perylene dicarboximide, N, N'-two (2,5-di-tert-butyl-phenyl)-3,4,9,10-perylene dicarboximide, perfluor CuPc, 1,4,5,8-naphthalenetetracarbacidic acidic acid anhydride, described p-type Small molecular comprises CuPc, Phthalocyanine Zinc, Cobalt Phthalocyanine;
Further, described thickness of insulating layer is 500nm – 2000nm, and described Zinc oxide nanoparticle diameter is 5nm – 10nm.
Further, the material of described polymer insulation layer is the one in polystyrene, poly-а-methyl styrene, polymethylmethacrylate, polycarbonate, dimethyl silicone polymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone or pla-pcl and the multipolymer between them.
Further, gate electrode, source electrode and drain electrode are made up of the one in gold, silver or copper and alloy material thereof, and the thickness of source electrode and drain electrode is 50 ~ 100nm.
Further, described substrate is one or more in silicon chip, glass, thin polymer film, metal forming, vegetable fibre, fibrin gel, gelatin, PLA, viral fiber element, Poly(D,L-lactide-co-glycolide.
The invention also discloses a kind of preparation method of organic field-effect tube nitrogen dioxide sensor, comprise the following steps:
1. first substrate is cleaned thoroughly, dry after cleaning;
2. gate electrode is prepared at substrate surface;
3. on described gate electrode, preparation surface is dispersed with the insulation course of Zinc oxide nanoparticle;
4. on described insulation course, discontinuous organic semiconductor layer is prepared;
5. on described organic semiconductor layer, source electrode and drain electrode is prepared.
Further, step 3. in, insulation course is by spin coating, roller coat, a kind of method preparation of dripping in film, impression, printing or spraying, and Zinc oxide nanoparticle adopts a kind of method preparation in quick spin coating, printing or spraying.
Further, step 2. 5. in, gate electrode, source electrode, drain electrode are by a kind of method preparation in the chemical vapor deposition of vacuum thermal evaporation, magnetron sputtering, plasma enhancing, serigraphy, printing or spin coating, described step 4. in, described organic semiconductor layer is by the chemical vapor deposition of plasma enhancing, thermal oxide, spin coating, vacuum evaporation, roller coat, a kind of method preparation of dripping in film, impression, printing or spraying.
Compared with prior art, the invention has the advantages that:
One, by Zinc oxide nanoparticle is introduced surface of insulating layer, change the wellability of surface of insulating layer, thus make the organic semiconductor layer of subsequent growth form discontinuous film;
Two, impurity molecule organic semiconductor is deposited in the gap of discontinuous organic semiconductor layer, because itself characteristic serves the effect of hole trap, reduce the initial performance of device, when device is exposed in nitrogen dioxide gas, the trap effect of impurity molecule organic semiconductor greatly can weaken and even disappears, thus device performance is significantly promoted, and then obtain higher response;
Three, the Zinc oxide nanoparticle of surface of insulating layer is in after absorption nitrogen dioxide gas, considerable influence can be produced to device threshold voltage, thus make device threshold voltage follow nitrogen dioxide gas concentration linear, and then the multiparameter realizing whole device detects;
Four, the present invention can at room temperature work, and without the need to heating source, reduces device cost and energy resource consumption, and Zinc oxide nanoparticle and required insulating material wide material sources, realize suitability for industrialized production all, and this advantage is particularly important for a large amount of sensor used.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
In figure: 1-1 source electrode, 1-2 drain electrode, 2-impurity molecule organic semiconductor, 3-organic semiconductor layer, 4-Zinc oxide nanoparticle 5-insulation course, 6-gate electrode, 7-substrate.
Fig. 2 is principle schematic of the present invention;
Fig. 3 is embodiment 1, for the response curve of the nitrogen dioxide of variable concentrations.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
With reference to Fig. 1, a kind of organic field-effect tube gas sensor based on mix insulation layer of the present invention, comprise substrate 7, gate electrode 6, insulation course 5, Zinc oxide nanoparticle 4, organic semiconductor layer 3, impurity molecule organic semiconductor 2, source electrode and drain electrode 1, described gate electrode is arranged and substrate, insulation course is arranged on gate electrode, and source electrode and drain electrode are arranged on organic semiconductor layer respectively; Described organic semiconductor layer is discontinuous film; Described surface of insulating layer is dispersed with Zinc oxide nanoparticle; Described impurity molecule organic semiconductor to be deposited in organic semiconductor lamellar spacing and to contact with Zinc oxide nanoparticle.
Below specific embodiments of the invention:
Embodiment 1:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, thickness is 50nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 500nm, a zinc-oxide nano diameter is 5nm, organic semiconductor layer material is pentacene, and thickness is 20nm, and impurity molecule organic semiconductor is CuPc, source electrode drain electrode is Au, and thickness is 50nm.
Preparation method is as follows:
1. the glass substrate 7 having sputtered gate electrode ITO is cleaned thoroughly, dry up with drying nitrogen after cleaning;
2. adopt spin-coating method on ITO, prepare mix insulation layer 5;
3. spin-coating method is adopted to prepare Zinc oxide nanoparticle at surface of insulating layer;
4. vacuum vapour deposition is adopted to prepare pentacene organic semiconductor layer and CuPc impurity molecule organic semiconductor;
4. vacuum vapour deposition is adopted to prepare source electrode drain electrode.
Embodiment 2:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, thickness is 100nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 2000nm, a zinc-oxide nano diameter is 10nm, organic semiconductor layer material is pentacene, and thickness is 30nm, and impurity molecule organic semiconductor is CuPc, source electrode drain electrode is Au, and thickness is 100nm.
Preparation method is as embodiment 1.
Embodiment 3:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, and thickness is 80nm, mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 1000nm, and a zinc-oxide nano diameter is 8nm, organic semiconductor layer material is pentacene, and thickness is 25nm, and impurity molecule organic semiconductor is N, N '-diamyl-3,4,9,10-perylene dicarboximide, source electrode drain electrode is Au, and thickness is 80nm.
Preparation method is as embodiment 1.
Embodiment 4:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, and thickness is 80nm, mix insulation layer 5 is for be mixed by polystyrene, and thickness is 2000nm, and a zinc-oxide nano diameter is 8nm, organic semiconductor layer material is pentacene, and thickness is 25nm, and impurity molecule organic semiconductor is N, N '-diamyl-3,4,9,10-perylene dicarboximide, source electrode drain electrode is Au, and thickness is 80nm.
Preparation method is as embodiment 1.
Embodiment 5:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, and thickness is 80nm, mix insulation layer 5 is for be mixed by polystyrene, and thickness is 2000nm, and a zinc-oxide nano diameter is 8nm, organic semiconductor layer material is six thiophene, and thickness is 25nm, and impurity molecule organic semiconductor is N, N '-diamyl-3,4,9,10-perylene dicarboximide, source electrode drain electrode is Au, and thickness is 80nm.
Preparation method is as embodiment 1.
Embodiment 6:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, thickness is 50nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 500nm, a zinc-oxide nano diameter is 5nm, organic semiconductor layer material is six thiophene, and thickness is 20nm, and impurity molecule organic semiconductor is CuPc, source electrode drain electrode is Au, and thickness is 50nm.
Preparation method is as embodiment 1.
Embodiment 7:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, thickness is 50nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 500nm, a zinc-oxide nano diameter is 5nm, organic semiconductor layer material is six thiophene, and thickness is 20nm, and impurity molecule organic semiconductor is perfluor CuPc, source electrode drain electrode is Au, and thickness is 50nm.
Preparation method is as embodiment 1.
Embodiment 8:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, thickness is 50nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 500nm, a zinc-oxide nano diameter is 5nm, organic semiconductor layer material is rubrene, and thickness is 20nm, and impurity molecule organic semiconductor is perfluor CuPc, source electrode drain electrode is Au, and thickness is 50nm.
Preparation method is as embodiment 1.
Embodiment 9:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, and thickness is 50nm, and mix insulation layer 5 is for be mixed by polymethylmethacrylate, thickness is 500nm, a zinc-oxide nano diameter is 5nm, and organic semiconductor layer material is the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester, thickness is 20nm, impurity molecule organic semiconductor is CuPc, and source electrode drain electrode is Au, and thickness is 50nm.
Preparation method is as follows:
1. the glass substrate 7 having sputtered gate electrode ITO is cleaned thoroughly, dry up with drying nitrogen after cleaning;
2. adopt spin-coating method on ITO, prepare mix insulation layer 5;
3. spin-coating method is adopted to prepare Zinc oxide nanoparticle at surface of insulating layer;
4. spraying process is adopted to prepare 6,13 – bis-or three isopropyl ester silica-based acetylene pentacene organic semiconductor layer;
5. vacuum vapour deposition is adopted to prepare impurity molecule organic semiconductor CuPc;
4. vacuum vapour deposition is adopted to prepare source electrode and drain electrode.
Embodiment 10:
As shown in Figure 1: substrate 7 is glass, gate electrode 6 is ITO, and thickness is 100nm, mix insulation layer 5 is for be mixed by polymethylmethacrylate, and thickness is 200nm, and a zinc-oxide nano diameter is 5nm, organic semiconductor layer material is the silica-based acetylene pentacene of 6,13 – bis-or three isopropyl ester, and thickness is 30nm, impurity molecule organic semiconductor is N, N '-diamyl-3,4,9,10-perylene dicarboximide, source electrode drain electrode is Au, and thickness is 50nm.。
Preparation method is as follows:
1. the glass substrate 7 having sputtered gate electrode ITO is cleaned thoroughly, dries up after cleaning with drying nitrogen;
2. adopt spin-coating method on ITO, prepare mix insulation layer 5;
3. spin-coating method is adopted to prepare Zinc oxide nanoparticle at surface of insulating layer;
4. spraying process is adopted to prepare 6,13 – bis-or three isopropyl ester silica-based acetylene pentacene organic semiconductor layer;
5. adopt spraying process legal system for impurity molecule organic semiconductor N, N '-diamyl-3,4,9,10-perylene dicarboximide;
5. vacuum vapour deposition is adopted to prepare source electrode and drain electrode.
The embodiment of the present invention is better embodiment, but it specifically implements to be not limited to this, and those of ordinary skill in the art is very easily according to above-described embodiment; understand spirit of the present invention; and make different amplifications and change, only otherwise depart from the present invention, all belong within protection scope of the present invention.
Claims (10)
1. an organic field-effect tube nitrogen dioxide sensor, be followed successively by substrate (7), gate electrode (6), insulation course (5) from top to bottom, it is characterized in that, described insulation course (5) Dispersion on surface has Zinc oxide nanoparticle layer (4); Zinc oxide nanoparticle layer (4) is arranged the organic semiconductor layer (4) of promising discontinuous film, precipitate on organic semiconductor layer (4) and in gap and have the impurity molecule organic semiconductor (2) contacted with Zinc oxide nanoparticle (4), impurity molecule organic semiconductor (2) is provided with source electrode (1-1) and drain electrode (1-2).
2. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, it is characterized in that, described organic semiconductor layer (4) is made up of P type small molecule organic semiconductor material, comprise aphthacene, pentacene, 6, one in the silica-based acetylene pentacene of 13 – bis-or three isopropyl ester, rubrene or six thiophene, described organic semiconductor layer thickness is 20nm-30nm.
3. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, it is characterized in that, the p-type Small molecular that described impurity molecule organic semiconductor (2) is N-shaped Small molecular or high electron density, described N-shaped Small molecular comprises, C60, N, N '-diamyl-3, 4, 9, 10-perylene dicarboximide, N, N '-diphenyl-3, 4, 9, 10-perylene dicarboximide, N, N '-dioctyl-3, 4, 9, 10-perylene dicarboximide, N, N'-two (2, 5-di-tert-butyl-phenyl)-3, 4, 9, 10-perylene dicarboximide, perfluor CuPc, 1, 4, 5, 8-naphthalenetetracarbacidic acidic acid anhydride, described p-type Small molecular comprises CuPc, Phthalocyanine Zinc, Cobalt Phthalocyanine.
4. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, is characterized in that, described insulation course (5) thickness is 500nm – 2000nm, and the particle diameter of described Zinc oxide nanoparticle layer (4) is 5nm – 10nm.
5. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, it is characterized in that, described insulating material is the one in polystyrene, poly-а-methyl styrene, polymethylmethacrylate, polycarbonate, dimethyl silicone polymer, polyvinyl alcohol (PVA), polyvinylpyrrolidone or pla-pcl and the multipolymer between them.
6. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, it is characterized in that, gate electrode (6), source electrode (1-1) and drain electrode (1-2) are made up of the one in gold, silver or copper and alloy material thereof, and the thickness of source electrode (1-1) and drain electrode (1-2) is 50 ~ 100nm.
7. a kind of organic field-effect tube nitrogen dioxide sensor according to claim 1, it is characterized in that, described substrate (7) is silicon chip, glass, thin polymer film, metal forming, vegetable fibre, fibrin gel, gelatin, PLA, viral fiber element, one or more in Poly(D,L-lactide-co-glycolide.
8. the preparation method of a kind of organic field-effect tube nitrogen dioxide sensor according to any one of claim 1-7, is characterized in that, comprise the following steps:
1. first substrate is cleaned thoroughly, dry after cleaning;
2. gate electrode is prepared at substrate surface;
3. on described gate electrode, preparation surface is dispersed with the insulation course of Zinc oxide nanoparticle;
4. on described insulation course, discontinuous organic semiconductor layer is prepared;
5. on described organic semiconductor layer, source electrode and drain electrode is prepared.
9. the preparation method of a kind of organic field-effect tube nitrogen dioxide sensor according to claim 7, it is characterized in that, step 3. in, insulation course is by spin coating, roller coat, a kind of method preparation of dripping in film, impression, printing or spraying, and Zinc oxide nanoparticle adopts a kind of method preparation in quick spin coating, printing or spraying.
10. the preparation method of a kind of organic field-effect tube nitrogen dioxide sensor according to claim 7, it is characterized in that, step 2. 5. in, gate electrode, source electrode, drain electrode are by a kind of method preparation in the chemical vapor deposition of vacuum thermal evaporation, magnetron sputtering, plasma enhancing, serigraphy, printing or spin coating, described step 4. in, described organic semiconductor layer is by the chemical vapor deposition of plasma enhancing, thermal oxide, spin coating, vacuum evaporation, roller coat, a kind of method preparation of dripping in film, impression, printing or spraying.
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| CN110501385A (en) * | 2019-08-29 | 2019-11-26 | 电子科技大学 | A kind of Organic Thin Film Transistors nitrogen dioxide sensor and preparation method thereof based on air dielectric layer |
| CN112649472A (en) * | 2021-01-09 | 2021-04-13 | 长春工业大学 | NO based on electrostatic spraying polymer insulation layer2Preparation method of gas sensor |
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