CN104934513A - Biosafety flexible photosensitive sensor of organic filed effect transistor and fabrication method thereof - Google Patents
Biosafety flexible photosensitive sensor of organic filed effect transistor and fabrication method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Light Receiving Elements (AREA)
Abstract
The invention relates to a biosafety flexible photosensitive sensor of organic filed effect transistor (OFET) and a fabrication method thereof. The biosafety flexible photosensitive sensor comprises a polylactic acid (PLA) thin film serving as a dielectric layer, a gold thin film is evaporated at the bottom of the PLA thin film and serves as a gate electrode, an organic semiconductor layer is evaporated at the top of the PLA thin film and serves as a conductive layer, and gold thin films which are separated mutually are evaporated at the top of the conductive layer and serve as a source and a drain. Compared with the prior art, the OFET disclosed by the invention has the advantages of low cost, excellent photosensitive performance, and compatibility with flexibility and biosafety and the like.
Description
Technical field
The present invention relates to a kind of light sensor, especially relate to a kind of bio-safety flexible photosensitive transducer based on organic field effect tube and preparation method thereof.
Background technology
Based on the light sensor excellent performance of organic field effect tube (OFET), be widely used, comprise optical detection, optical switch, light trigger amplifier and pattern imaging etc.But traditional OFET light sensor requires that organic semiconducting materials itself has higher mobility and good photosensitive property concurrently, so high requirement limits the large-scale promotion application of OFET light sensor.On the other hand, utilize the structural design of OFET device also can obtain possessing the transducer of excellent properties, as Bao Zhenan team of Stanford Univ USA reports a kind of dimethyl silicone polymer based on having complex micro structure, (OFET of PDMS dielectric layer, this OFET has very high pressure-sensitivity characteristic.Our team also reports temp-sensitive sensor prepared by a kind of OFET of utilization dielectric layer and organic semiconductor layer interface interaction, can be applied to the temperature sensing of artificial skin.The transducer obtained by these modes no longer requires that organic semiconductor itself is to stimulating or the sensitive property of signal, therefore has material compatibility widely.And the light sensor based on this mode was not also in the news.
Have light sensor that is flexible and biological safety concurrently to be with a wide range of applications, as John A.Rogers reports the compound eye structural using flexible photosensitive transducer to copy insect, prepare the flexible ball surface imaging equipment possessing the excellent properties such as wide viewing angle, low aberration; He there was reported and the electronic device such as miniature LED light source, light sensor of bio-safety is integrated the brain getting involved in mouse, thus have studied the neural smooth genetic behavior of organism in a creative way.But the material used in above-mentioned device comprises PDMS and inorganic silicon-based semi-conducting material, and its biological safety and flexibility all have much room for improvement.
Summary of the invention
Object of the present invention is exactly provide a kind of have excellent photosensitive property to overcome defect that above-mentioned prior art exists and have bio-safety flexible photosensitive transducer and the preparation method of the organic field effect tube of biological safety concurrently.
Object of the present invention can be achieved through the following technical solutions:
A bio-safety flexible photosensitive transducer for organic field effect tube, comprising:
As the PLA film of dielectric layer,
Bottom PLA film, the gold thin film of evaporation is as gate electrode,
At PLA film top evaporation organic semiconductor layer as conductive layer,
The gold thin film mutually completely cut off at conductive layer top evaporation is as source electrode and drain electrode.
Described PLA film thickness is 1-5 μm.
Gold thin film thickness as gate electrode is 50-100nm.
The thickness of described organic semiconductor layer is 50-100nm, and material is dinaphtho thienone.
Distance between described source electrode and drain electrode is 10-500 μm.
The preparation method of the bio-safety flexible photosensitive transducer of organic field effect tube, adopts following steps:
A) clean of substrate: use acetone, at the bottom of isopropyl alcohol ultrasonic cleaning silicon wafer-based successively, then use absolute ethyl alcohol and deionized water rinsing, finally dry up substrate surface with nitrogen;
B) the surface anti sticking process of substrate: be that (13 fluoro-1,1,2,2-tetrahydrochysene octane)-trichlorosilane (FOTS) solution in chloroform of 1-5% is spun to above-mentioned clean silicon chip surface as adherent layer by volumetric concentration;
C) 7 × 10
-4gate electrode is formed by hot for gold evaporation to silicon chip under the vacuum of Pa;
D) product c) is vertically placed in the PLA chloroformic solution of 50g/L, slowly lifts with the speed of 15 μm/s and leave solution surface, obtain the PLA film as OFET dielectric layer;
E) 7 × 10
-4under the vacuum of Pa, by the thermal evaporation of dinaphtho thienone on above-mentioned PLA film;
F) use c) identical method, the mode utilizing mask plate to block by hot for gold evaporation on product e), as source electrode and the drain electrode of OFET;
G) PLA film being taken off from there being the silicon chip of FOTS process, obtaining flexible photosensitive transducer.
Compared with prior art, the present invention has the following advantages:
1, adopt PLA and DNTT respectively as the substrate of OFET and dielectric layer and organic semiconducting materials, because the chemical polarity group in PLA has attraction capture effect to the charge carrier in DNTT, and this effect can by the impact of illumination, thus making the OFET prepared possess photosensitive property, optical switch ratio reaches 10
4doubly, can be used as photistor, and pattern imaging can be applied to;
2, the OFET of preparation has flexibility and biocompatibility concurrently, is twisted in by device on object that radius is less than 800 μm and can also keep normal performance; PLA itself is the macromolecular material of biocompatibility excellence, and DNTT accounts for the mass fraction of OFET less than 1%, and therefore the biological safety of OFET entirety is good, and in the extract of device and the co-culture experiments of L929 cell, the rate of growth of cell is all higher than 80%;
3, this technology preparation technology is simple, without the need to the apparatus for preparation of precision, with low cost, is convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is OFET service behaviour prepared by the present invention, i.e. its output characteristic curve.
Fig. 2 is that the flexibility of OFET prepared by the present invention is shown, its mobility is with the situation of change of crimp radius.
Fig. 3 is that the biocompatibility of OFET prepared by the present invention is shown, with the rate of growth of its co-cultured cell.
Fig. 4 is the photosensitive property adopting this technology to prepare flexible OFET, and namely its transfer characteristic curve is with the change of light intensity.
Fig. 5 adopts the flexible OFET for preparing of this technology when not adding field voltage as the output characteristic curve of photistor.
Fig. 6 adopts the flexible OFET light sensor prepared of this technology to the imaging applications of five-pointed star pattern.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
A kind of bio-safety flexible photosensitive transducer of organic field effect tube, comprise as dielectric layer, thickness is the PLA film of 1-5 μm, bottom PLA film, evaporation thickness is that the gold thin film of 50-100nm is as gate electrode, at PLA film top, evaporation thickness is 50-100nm, material be dinaphtho thienone organic semiconductor layer as conductive layer, the gold thin film mutually completely cut off at conductive layer top evaporation is as source electrode and drain electrode, and the distance between source electrode and drain electrode is 10-500 μm.
Au gate electrode blocks after heat evaporation by mask plate, its width is slightly larger than the channel width between top Au source electrode and drain electrode, both ensured that the organic semiconductor in raceway groove was all in field voltage, reduce again overlapping with between the source/drain of top of bottom gate thin film as far as possible, reduce the risk of OFET device breakdown electric leakage.The dielectric material PLA used in OFET and the molecular formula of organic semiconducting materials DNTT are as shown in Figure 2.PLA molecular weight is 10-20 ten thousand, uses after purchasing the Methods For Purification of rear use dissolution precipitation, and solvent is chloroform, and precipitation reagent is methyl alcohol.DNTT synthesizes in the steps below:
Step 1, it is pure that all chemical reagent purity is analysis.Oxolane all passes through except water treatment before use, and institute responds and all carries out under anhydrous and oxygen-free environment, uses argon shield.The trimethyl ethylenediamine of 2.87mL (21mmol) is joined in the oxolane of 35mL, mixes with the hexane solution (concentration 1.59M, 13.2mL) of n-BuLi at subzero 30 DEG C.Be uniformly mixed solution at the same temperature after 15 minutes, the tetrahydrofuran solution (2.0g 2-naphthaldehyde joins in 10mL oxolane) of slow dropping (adding for 5 minutes) 2-naphthaldehyde, add the n-BuLi hexane solution that 24.15mL concentration is 38.4mmol afterwards again, at subzero 30 DEG C, be uniformly mixed liquid 3.5 hours.Add excessive DMDS (5.67mL, 64mmol) and at room temperature stir after 2 hours, adding 20mL hydrochloric acid (concentration is 1M).Final mixture uses 60mL carrene to extract after stirring 10 hours.Vacuumize again after extract use MgSO4 drying.Use chromatographic column to purify solid residue, obtain yellow solid solid 1a (1.49g), chromatographic solution is the mixed liquor (volume ratio is 9:1) of n-hexane and ethyl acetate.
Step 2, adds 0.39g zinc powder in 10mL oxolane, slowly adds 0.66mL titanium tetrachloride and adds hot reflux 1.5 hours.After solution drops to room temperature, slowly add the tetrahydrofuran solution (0.405g 1a joins in 10ml oxolane) of 1a, mixed liquor condensing reflux 10 hours.After temperature drops to room temperature, with 30mL saturated sodium bicarbonate aqueous solution and 30mL carrene, it is diluted, stir 3.5 hours.Use diatomite to filter, filtrate is divided into organic layer and water layer.Use 60mL carrene to extract water layer, which floor will have use vacuumize again after MgSO4 drying.Run plate (silica gel plate) through carrene cleaning to purify, obtain yellow crystals 2a (0.299g).
Step 3,0.2235g 2a and 4.87g iodine join successively in 15mL chloroform and reflux 21 hours.After temperature drops to room temperature, add the saturated aqueous solution of sodium bisulfite of 20mL, filter out precipitation and use water and chloroform to clean.The crude product obtained is purified by vacuum sublimation and is obtained yellow solid, is DNTT.
The OFET work prepared is good, and its transistor characteristic curve as shown in Figure 1.
Embodiment 2
OFET prepared by this technology has excellent flexibility, rollable folding, and still can the electric property of retainer member under curling state.For characterizing the working condition of OFET under rolled state in the present invention, first being wrapped in tightly by OFET device has on the cylindrical object of different radii, test the transistor performance of OFET in this case, the radius parameter chosen in this example is from infinitely great (namely OFET is in flat condition) to 800 ч m.Illustrate the change of mobility with its crimp radius of OFET in Fig. 2, visible when on the radius that device is crimped onto 800 ч m, its mobility only reduces 4%, illustrates that the OFET device in the present invention has the flexibility of excellence.
Embodiment 3
OFET sample the present invention prepared is immersed in the RPMI1640 solution of 2mL, keeps 24 or 48h in 37 DEG C, is then filtered by solution, is diluted to 1 to 1/8 times, finally mixes with the calf serum solution of volume fraction 10%.Be 1 × 10 by concentration
4the L929 cell of individual/mL and above-mentioned solution Mixed culture 7 days, every 24 hours supplementary fresh solution.L929 cell as blank group is placed in not to be cultivated 7 days containing the cell culture fluid of OFET extract.The MTT solution of 5mg/mL is added in above-mentioned cell culture liquid, after 3.5 hours, the precipitation of generation is leached, be dissolved in dimethyl sulfoxide (DMSO) (DMSO), under the illumination of 570nm, test its OD value (optical density, O.D.).And the cell compatibility of OFET sample can use rate of growth (the relative growth rations of co-cultured cell, RGR) represent, it equals the O.D. value of O.D. value divided by blank group of OFET sample, and its value is higher, and the cell compatibility of sample is better.Illustrate the growth situation of L929 cell co-culture experiments in the OFET extraction liquids of different extraction time, different extension rate in Fig. 3, RGR value is all greater than 80% in all cases, illustrates that OFET prepared by this technology has good biological safety.
Embodiment 4
Use the above-mentioned OFET of wide spectrum LED collimation light source irradiation, regulate and irradiate light intensity from 0.5-100mW/cm2, with output characteristic curve and the transfer characteristic curve of semiconductor parameter instrument test OFET, draw the change with light intensity such as the electric current of OFET, mobility and threshold voltage.Illustrate the transfer characteristic curve that different light intensity irradiates lower OFET in Fig. 6, the optical switch ratio of OFET light sensor prepared by known the present invention is 10
2-10
4.Source/drain current-voltage curve is with the change of light intensity when not adding field voltage to illustrate device in Fig. 4, and the device prepared by surperficial the present invention can be used as photistor simultaneously.
The object (using pentalpha cardboard in this example) with given shape pattern is covered on the OFET matrix of device of 10 × 10, the electrical parameter testing each components under again matrix of device being placed in illumination, as electric current, mobility and threshold voltage etc. and the ratio of element electrical parameter each when not having object to cover, provides the photosensitive imaging of OFET matrix of device for this object.The OFET matrix of device signal that Fig. 5 provides exports the pattern clearly demonstrating five-pointed star, illustrates that OFET light-sensitive device prepared by the present invention has good pattern imaging capability.
Claims (6)
1. a bio-safety flexible photosensitive transducer for organic field effect tube, is characterized in that, comprising:
As PLA (PLA) film of dielectric layer,
Bottom PLA film, the gold thin film of evaporation is as gate electrode,
At PLA film top evaporation organic semiconductor layer as conductive layer,
The gold thin film mutually completely cut off at conductive layer top evaporation is as source electrode and drain electrode.
2. the bio-safety flexible photosensitive transducer of a kind of organic field effect tube according to claim 1, is characterized in that, described PLA film thickness is 1-5 μm.
3. the bio-safety flexible photosensitive transducer of a kind of organic field effect tube according to claim 1, is characterized in that, the gold thin film thickness as gate electrode is 50-100nm.
4. the bio-safety flexible photosensitive transducer of a kind of organic field effect tube according to claim 1, is characterized in that, the thickness of described organic semiconductor layer is 50-100nm, and material is dinaphtho thienone.
5. the bio-safety flexible photosensitive transducer of a kind of organic field effect tube according to claim 1, is characterized in that, the distance between described source electrode and drain electrode is 10-500 μm.
6. the preparation method of the bio-safety flexible photosensitive transducer of the organic field effect tube according to any one of claim 1-5, is characterized in that, the method adopts following steps:
A) clean of substrate: use acetone, at the bottom of isopropyl alcohol ultrasonic cleaning silicon wafer-based successively, then use absolute ethyl alcohol and deionized water rinsing, finally dry up substrate surface with nitrogen;
B) the surface anti sticking process of substrate: be that (13 fluoro-1,1,2,2-tetrahydrochysene octane)-trichlorosilane (FOTS) solution in chloroform of 1-5% is spun to above-mentioned clean silicon chip surface as adherent layer by volumetric concentration;
C) 7 × 10
-4gate electrode is formed by hot for gold evaporation to silicon chip under the vacuum of Pa;
D) product c) is vertically placed in the PLA chloroformic solution of 50g/L, slowly lifts with the speed of 15 μm/s and leave solution surface, obtain the PLA film as OFET dielectric layer;
E) 7 × 10
-4under the vacuum of Pa, by the thermal evaporation of dinaphtho thienone on above-mentioned PLA film;
F) use c) identical method, the mode utilizing mask plate to block by hot for gold evaporation on product e), as source electrode and the drain electrode of OFET;
G) PLA film being taken off from there being the silicon chip of FOTS process, obtaining flexible photosensitive transducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510341003.6A CN104934513B (en) | 2015-06-18 | 2015-06-18 | The bio-safety flexible photosensitive sensor and preparation method of organic field effect tube |
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Cited By (3)
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| CN108543113A (en) * | 2018-03-21 | 2018-09-18 | 浙江理工大学 | A kind of preparation method of transparent photosensitive artificial skin sensor |
| CN109326724A (en) * | 2018-09-19 | 2019-02-12 | 电子科技大学 | A kind of photosensitive sensor and preparation method thereof based on organic field-effect tube |
| CN111129312A (en) * | 2019-12-23 | 2020-05-08 | 同济大学 | Double-function photosensitive-optical memory organic transistor and preparation method thereof |
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| CN103579502A (en) * | 2013-11-07 | 2014-02-12 | 电子科技大学 | Organic field effect transistor and manufacturing method thereof |
| CN103855305A (en) * | 2014-03-19 | 2014-06-11 | 北京科技大学 | Manufacturing method of fluorine-containing graphene decorative layer organic field effect transistor |
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| CN103579502A (en) * | 2013-11-07 | 2014-02-12 | 电子科技大学 | Organic field effect transistor and manufacturing method thereof |
| CN103855305A (en) * | 2014-03-19 | 2014-06-11 | 北京科技大学 | Manufacturing method of fluorine-containing graphene decorative layer organic field effect transistor |
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| JOHANNES MILVICHA;TAREK ZAKIA;MAHDIEH AGHAMOHAMMADIB ET AL.: ""Flexible low-voltage organic phototransistors based on air-stable dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT)"", 《ORGANIC ELECTRONICS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108543113A (en) * | 2018-03-21 | 2018-09-18 | 浙江理工大学 | A kind of preparation method of transparent photosensitive artificial skin sensor |
| CN109326724A (en) * | 2018-09-19 | 2019-02-12 | 电子科技大学 | A kind of photosensitive sensor and preparation method thereof based on organic field-effect tube |
| CN111129312A (en) * | 2019-12-23 | 2020-05-08 | 同济大学 | Double-function photosensitive-optical memory organic transistor and preparation method thereof |
| CN111129312B (en) * | 2019-12-23 | 2023-11-03 | 同济大学 | Dual-function photosensitive-optical memory organic transistor and preparation method thereof |
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