CN106505148A - A kind of organic film FET based on laminate patch electrode and preparation method thereof - Google Patents
A kind of organic film FET based on laminate patch electrode and preparation method thereof Download PDFInfo
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- CN106505148A CN106505148A CN201510564121.3A CN201510564121A CN106505148A CN 106505148 A CN106505148 A CN 106505148A CN 201510564121 A CN201510564121 A CN 201510564121A CN 106505148 A CN106505148 A CN 106505148A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/80—Constructional details
- H10K10/82—Electrodes
Abstract
The invention discloses a kind of organic film FET based on laminate patch electrode and preparation method thereof, methods described comprises the steps：1) laminate patch electrode is prepared；2) by organic film and step 1) described in laminate patch electrode combine, you can obtain.The organic film FET with flexible structure, non-flexible face-to-face structure or volume to volume structure face-to-face is obtained by pressing, without the need for electrode evaporation, it is to avoid damage of the heat radiation to electrode and organic semiconductor thin-film；Furthermore, laminate patch electrode is flexible, and organic semiconductor thin-film also can be flexible；Additionally, organic film FET and circuit can achieve the volume to volume structure of Grazing condition, beneficial to large area preparation is realized, with certain commercial promise.
Description
Technical field
The invention belongs to organic electronic field, and in particular to a kind of organic film FET based on laminate patch electrode
And preparation method thereof.
Background technology
Since nineteen forty-seven, first transistor came out, the inorganic electronic research based on silicon-based electronic at present has become
In maturation, (Applied Physics Letters 2003,83,4773), until 3 scientist (Alan G. in 2000
MacDiarmid, Alan Heeger, Hideki Shirakawa) lead because invention one kind is referred to as the new of " organic electronic "
Electric polymer wins Nobel chemistry Prize, organic electronics is paid attention to by countries in the world research people.With without electromechanics
Son is compared, and organic electronic has large area, inherent advantages (the Applied Physics Letters such as inexpensive and flexible
2003,82,1739), so the short more than ten years, are emerged in multitude based on the new product of organic electronic, new opplication.According to state
The well-known organic electronic advisory organization IDTechEx predictions in border, can be beautiful more than 25,000,000,000 in the market of organic electronic in 2025
Unit.Can compare favourably with silicon-based electronic, become a huge commercial field.And wherein 75% market fund will put into
Arrive following organic electronic application：Logic circuit, memory, OLED show, sensor etc., these applications
Basis and one of core are organic field effect tube (organic field-effect transistors, OFET) and circuit,
So the research to OFET becomes the focus of current scientific research.
Although in recent years, achieved with the development that advances by leaps and bounds, large area prepares organic electronic and remains mesh organic electronic
The difficult problem that front researchers face.As organic semiconductor is interacted by weak van der waals force, mature
Inorganic electronic technology can not be directly applied on organic electronic.Inorganic electronic technology causes can organic semiconductor can not be extensive
The method for commonly using electron beam exposure in multiple damage, such as inorganic electronic technology prepares electrode, and high-power electron beam can make organic
Semiconductor loses field effect behavior.Therefore to realize that large area prepares organic field effect tube and circuit, needs to develop
New technology, this are also the important topic of current research.
Researchers report several methods for preparing large area organic field effect tube and circuit：1st, conventional method
Using vacuum evaporation, vacuum evaporation technology, realizes that large area prepares organic assembly and circuit.This method is conventional at present
The method for preparing broad area device, such as Li Dexin et al. profits are prepared for 300 in this way in the flexible substrate of PET
The pentacene device (Applied Physics Letters 2011,99,183304) of mm × 300mm sizes.But
When being that profit prepares broad area device in this way, certain problem is there is also, such as in semiconductor surface electrode evaporation,
Therefore heat radiation can be caused to semiconductor to damage, serious even can lose field effect behavior；2nd, nanometer embossing,
This method by Stephen Y Chou teach 1995 propose (Applied Physics Letters 1995,67 (21),
3114) heat radiation, can be effectively avoided to damage organic semi-conductor.Nanometer embossing is needed previously prepared
Seal on be deposited with organic semiconductor or metallic film, by realizing prepared by broad area device on Multi-layer imprinting to substrate.
The precision comparison that although this method prepares device is high, but in preparation process, needs for pattern machinery to be transferred to substrate
On, semiconductor can be caused mechanical damage (American Vacuum Society 1996,14 (6), 4129), and
Be not suitable for high-volume industrial production, therefore nanometer embossing development stagnation in recent years；3rd, inkjet technology,
It is the method for the preparation broad area device and circuit of rising in recent years.This method is that electric ink is sprayed on substrate,
Then using heating anneal, broad area device is finally deposited into.Jooho Moon seminars are beaten using ink-jet within 2009
Print technology is prepared for flexible device (the Electrochemical and Solid State of TIPS- pentacenes in plastic supporting base
Letters 2009,12 (6), H195).This technology needs semiconductor and electrode to dissolve in solution, but solvable at present
Few in number in the organic semiconductor of solution, and this method there is also prepare device limited precision, print speed compared with
Slow and be not suitable for a series of problems, such as producing in batches.Accordingly, it is desirable to provide a kind of new preparation large area organic field effect
The method for answering transistor and circuit, not only can realize prepared by device and the large area of circuit, and can avoid hot spoke
Penetrate and organic semi-conductor is damaged with mechanical stress.
Content of the invention
It is an object of the invention to provide a kind of organic film FET and its preparation side based on laminate patch electrode
Method.
The preparation method of the organic film FET based on laminate patch electrode provided by the present invention, including following step
Suddenly：
1) laminate patch electrode is prepared；
2) by organic film and step 1) described in laminate patch electrode combine, you can obtain the having based on laminate patch electrode
Machine TFT.
In above-mentioned preparation method, step 1) in, the laminate patch electrode is according to patent (application number 201410341757.7；
104112819 A of Publication No. CN) in method prepare, concrete preparation process is as follows：
(1) circuit mask plate is prepared, is comprised the steps：A) using L-editor softwares separately design source electrode,
The circuit reticle pattern of drain electrode and grid；B) in quartz/spin-on-glass polymethyl methacrylate, using sharp
The circuit reticle pattern that light direct-write methods etch step a) is obtained；Then chromium is deposited with, and removes the poly- methyl-prop
E pioic acid methyl ester, obtains the circuit mask plate of the source electrode, the drain electrode and the grid；
(2) prepare with the embedded laminate patch electrode of figuratum flexible flat, comprise the steps：A) on the surface of substrate
Connection octadecyl trichlorosilane alkane；B) on the substrate after through step a) modifications, using the method and steps (1) of photoetching
The circuit mask plate for obtaining prepares source electrode, drain electrode and gate electrode respectively；And in the source electrode, the drain electrode
Surface of metal electrode connection mercaptopropyl trimethoxysilane with the gate electrode；C) step b) obtain described
The surface of metal electrode difference spin coating dimethyl silicone polymer of source electrode, the drain electrode and the gate electrode, and carry out
Solidification；D) gate electrode that spin coating has dimethyl silicone polymer is shifted from the substrate；By grid electricity
The polydimethylsiloxanes of the surface of metal electrode of pole, the dimethyl silicone polymer surface of the source electrode and the drain electrode
Alkane surface carries out oxygen plasma process respectively, i.e., form hydroxyl on surface；E) source electrode and the electric leakage are cut out
Pole；By the surface of metal electrode of the gate electrode, the dimethyl silicone polymer surface of the source electrode and the drain electrode
Dimethyl silicone polymer surface aligned and heated, then by the gate electrode, the source electrode and the drain electrode
Connection shape is integral, that is, obtain the embedded laminate patch electrode of the flexible flat.
Wherein, step (2) a) in, described connection octadecyl trichlorosilane alkane the step of as follows：Institute after by cleaning
It is 7 to state substrate and be statically placed in the concentrated sulfuric acid with hydrogen peroxide volume ratio：In 3 mixed solution；Then the substrate is cleaned,
It is 1000 that the substrate is placed in normal heptane with octadecyl trichlorosilane alkane volume ratio again：In 1 mixed solution, i.e.,
The octadecyl trichlorosilane alkane in substrate surface connection.
Step (2) b) in, the method for the photoetching is as follows：Spin coating photoresist, heated rearmounted over the substrate
Be exposed under the uviol lamp under 365nm, then developed and fixing successively after, carry out evaporation metal.
Step (2) c) in, on the gate electrode, the thickness of the dimethyl silicone polymer of spin coating is 50～500 μm；
In the source electrode and the drain electrode, the thickness of the dimethyl silicone polymer of spin coating is 0.8～5 μm；Described solid
The temperature of change is 70～100 DEG C, and the time of the solidification is 2～12h.
Step (2) d) in, the time that the oxygen plasma is processed is 10～60s.
Step (2) e) in, the temperature of the heating is 70～100 DEG C, and the time of the heating is 10～30min.
In above-mentioned preparation method, step 2) in, the organic film is pentacene thin film, phthalocyanine copper film or phthalocyanine
Any one in zinc film, specially pentacene thin film.
The mode of the combination is concretely pressed.
The pressing is concretely：Will evaporation on substrate the organic film and the laminate patch electrode using aspectant
Mode is pressed, you can obtain the organic film FET based on laminate patch electrode, and the pressing is concrete
Can operate on probe station is carried out." face-to-face " is just referred to and for the organic film to be attached at the laminate patch electrode herein
Surface.
Wherein, the condition of the evaporation is as follows：The substrate is placed in high vacuum deposition chamber, is adjusted true in cavity
Reciprocal of duty cycle is 1 × 10-4～9 × 10-4Pa, specially 6 × 10-4Pa；Heating prepares organic semiconducting materials needed for organic film
Its rate of sublimation is caused to beSpeciallyIt is 20～100nm's in the substrate surface deposit thickness
The organic film, specially 50nm, obtain depositing the organic film over the substrate.
The substrate is flexible substrate or non-flexible substrate.
The flexible substrate that the flexible substrate is commonly used for those skilled in the art, concretely poly-methyl methacrylate
Ester flexible substrate or polystyrene flexible substrate, can prepare the institute with flexible structure face-to-face on flexible substrates
State the organic film FET based on laminate patch electrode.
The polystyrene flexible substrate can be prepared as follows：Silicon chip after first clean acetone is statically placed in
The concentrated sulfuric acid is 7 with hydrogen peroxide volume ratio：30min in 3 mixed solution；Then by the silicon chip be placed in normal heptane with
Octadecyl trichlorosilane alkane volume ratio is 1000：3～12h in 1 mixed solution, takes out the silicon chip and adds in 100 DEG C
Hot 5min；Polystyrene (PS) is dissolved in toluene solution and according to 4000r/min, the condition of 40s is spin-coated on the OTS
On the silicon chip of modified, baking and curing under 60～80 DEG C (concretely 70 DEG C) is then shifted from silicon chip,
Polystyrene flexible substrate is obtained.
The non-flexible substrate concretely in silicon chip, sheet glass and sapphire sheet any one, the non-flexible substrate exists
Also included successively with acetone, chromic acid and Piranha washing lotion (concentrated sulfuric acid and hydrogen peroxide volume ratio 7 using front:3 solution)
The step of cleaning.Can prepare on non-flexible substrate with described in non-flexible face-to-face structure be based on laminate patch electrode
Organic film FET.
In order to prepare with the organic film FET described in flexible volume to volume structure based on laminate patch electrode, also
Comprise the steps：Two roller bearings rotated using identical speed rightabout, by the laminate patch electrode and the vacuum
Deposition organic film on flexible substrates is parallel to be placed between two roller bearings, is rolled, you can obtain with flexibility
The organic film FET based on laminate patch electrode of volume to volume structure.
The preparation-obtained organic film FET based on laminate patch electrode of the present invention falls within the protection of the present invention
Scope.
For the difficult problem for preparing large area organic assembly at present, invented a kind of new large area flexible for preparing has the present invention
The method of field effect transistors, avoids solution and heat radiation completely to preparing organic semiconducting materials needed for organic film
Damage, in hard substrates (such as：Silicon substrate) and flexible substrate on can prepare large area organic field effect tube.
Source electrode, drain and gate in the present invention is made by the way of laminate patch electrode, then by laminate patch electrode and organic half
Conductor thin film is laminated again, you can prepare large area organic film FET.
Compared with prior art, the present invention has the advantage that：
Organic film FET prepared by the present invention, not only need not be in semiconductor surface electrode evaporation, it is to avoid
Damage of the heat radiation to electrode and organic semiconductor thin-film；And because laminate patch electrode is embedded electrode, film
More preferable with electrode laminating, be conducive to carrier transport；Furthermore, laminate patch electrode is flexible, organic semiconductor thin-film
But also flexibility, it is possible to achieve bending；Additionally, organic film FET can achieve the volume to volume of Grazing condition
Structure, beneficial to large area preparation is realized, with certain commercial promise.
Description of the drawings
Fig. 1 is the structural representation that vacuum evaporation technology prepares organic film FET.
Fig. 2 is the structural representation that inkjet technology prepares organic film FET.
Fig. 3 is the structural representation that nanometer embossing prepares organic film FET.
Fig. 4 is the structural representation that the present invention prepares organic film FET.
Fig. 5 is the structural representation that the present invention prepares non-flexible face-to-face structure organic film FET.
Fig. 6 is the structural representation that the present invention prepares flexible structure organic film FET face-to-face.
Fig. 7 is the structural representation that the present invention prepares volume to volume structure organic film FET.
Fig. 8 be the face-to-face structure of non-flexible pentacene thin film field-effect transistor prepared by embodiment 1 schematic diagram,
Pictorial diagram and performance curve.Schematic diagrames of the Fig. 8 (a) for the face-to-face structure of pentacene thin film field-effect transistor；Fig. 8
B () is pentacene thin film and the optical microscope after the laminating of laminate patch electrode；Fig. 8 (c) is imitated for pentacene thin film field
Answer the performance curve of the face-to-face structure of transistor.
Fig. 9 is the structural representation of the flexible pentacene thin film field-effect transistor of structure face-to-face prepared by embodiment 2
Figure, pictorial diagram and performance comparison figure.Fig. 9 (a) is the structural representation on flexible organic film transistor planar；Figure
9 (b) is the transfer curve that flexible organic film transistor is placed on the plane；Fig. 9 (c) is flexible organic film crystal
Pipe is placed on the pictorial diagram on sphere；Fig. 9 (d) is placed on performance and plane performance on sphere for flexible organic film transistor
Comparison diagram, wherein black curve 1 are performance curve in the plane, and red curve 2 is the performance curve on sphere；
Fig. 9 (e) is pictorial diagram when flexible organic film transistor bends；Fig. 9 (f) is that flexible organic film transistor is curved
Folding 100 times afterwards with plane performance comparison diagram, wherein black curve 1 is performance curve in the plane, red curve
2 is to bend 100 performance curves afterwards.
Specific embodiment
The method of the present invention is illustrated below by specific embodiment, but the invention is not limited in this.
Experimental technique described in following embodiments, if no special instructions, is conventional method；The reagent and material,
If no special instructions, commercially obtain.
The structural representation of the organic film FET prepared by the present invention is as shown in Figure 4.
Structural representation such as Fig. 5 institutes of the non-flexible face-to-face structure organic film FET prepared by the present invention
Show.
Structural representation such as Fig. 6 institutes of the flexible structure organic film FET face-to-face prepared by the present invention
Show.
The structural representation of the volume to volume structure organic film FET prepared by the present invention is as shown in Figure 7.
Embodiment 1, the pentacene thin film field-effect transistor for preparing non-flexible face-to-face structure：
1st, laminate patch electrode is prepared：According to patent (application number 201410341757.7；104112819 A of Publication No. CN)
Prepare：Comprise the following steps that：
1) circuit mask plate is prepared：Source electrode, drain electrode, grid and external electricity are separately designed using L-editor softwares
The circuit reticle pattern of pole；Then spin coating polymethyl methacrylate on quartz, is etched using laser direct writing method
Circuit reticle pattern；Then evaporation chromium (100nm), and removes polymethyl methacrylate, obtain source electrode,
The circuit mask plate of drain electrode, grid and external electrode；
2) the embedded laminate patch electrode of flexible flat is prepared：
A) one layer of octadecyl trichlorosilane alkane is modified using liquid phase method in substrate silicon surface：First dry for substrate surface cleaning
Only；Then substrate is put into Piranha washing lotion (concentrated sulfuric acid and hydrogen peroxide volume ratio 7:3 solution) in；Clear again
Wash substrate；Substrate is put into volume ratio for 1000:In the OTS solution of 1 normal heptane dilution, substrate surface is made to form one
Layer OTS.
B) method for being utilized respectively photoetching on the substrate of OTS modifications prepares the source/drain electrode layer of circuit pattern, grid electricity
Pole layer, external electrode layer, and mercaptopropyl trimethoxysilane MPT is modified in surface of metal electrode：
Photoetching (baking temperature is distinguished on substrate first with AZ5214E photoresists：100℃；Baking time：3min；
Time for exposure：20s；Developing time：60s；Fixing time：30s) source/drain electrode and gate electrode；Then vacuum is steamed
Plating 25nm gold (vacuums：10-6torr；Evaporation rate：0.01nm/s)；Before going removing glue, in metal surface profit
With vaccum gas phase law, (concrete grammar is while being put into source, leakage, gate electrode and 30 μm of mercaptopropyl trimethoxysilanes
In vacuum system, 7000Pa pressure 20min are kept) one layer of MPT molecule (1～5nm) of modification；MPT is modified
Afterwards, 1-METHYLPYRROLIDONE solution is recycled to remove photoresist, it is therefore an objective to only to modify MPT in metal surface, substrate surface does not have
There are MPT molecules.
C) spin coating different-thickness is distinguished on the source/drain electrode after photoetching and modification MPT, gate electrode and external electrode layer
Dimethyl silicone polymer (PDMS) and solidify：
With 10:1(PDMS：Curing agent, volume ratio) proportional arrangement PDMS solution, after stirring stand 2 hours；
Directly one layer of 200 μm of PDMS solution of spin coating on the gate electrode after photoetching and modification MPT, are then placed in baking oven
70 degree are heating and curing 12 hours；PDMS after standing is put in the solution of n-hexane and is diluted, and volume ratio is
1:10, stir and stand；Photoetching and modification MPT after source/drain electrode on one layer of 1 μm of PDMS of spin coating just oneself
Alkane solution, is then placed in baking oven 70 degree and is heating and curing 12 hours.
D) oxygen plasma processes source/drain and surface gate electrode：First the PDMS with grid is turned from silicon substrate
Shifting is got off；Then the grid for transfer being got off is processed while putting in oxygen plasma with the source/drain electrode with PDMS
60s.
E) gate electrode and source/drain electrode heating are aligned：Using aligning tool (leveling up and down can be realized) aobvious
Align gate electrode and source/drain electrode under micro mirror；Electrode after aligning is put in 70 degree of baking ovens and is heated 10 minutes,
Purpose is to make gate electrode and source/drain electrode form irreversible key so as to closely connect, so far, source/drain electrode
PDMS layer is linked together with the surface of metal electrode of grid.
F) the source/drain electrode global transfer with thin PDMS is got off using the gate electrode with thicker PDMS,
Form laminate patch electrode.
2nd, pentacene thin film is prepared：
1) cut and clean silicon substrate：
A) silicon chip of 1cm × 1cm sizes is cut with diamant first；
B) silicon chip of step a) well cuttings is placed in beaker, pours the acetone of 20ml into, be put into supersonic wave cleaning machine
Interior ultrasonic 15min；Then deionized water flushing silicon chip three to five times, then place the substrate into Piranha washing lotion (dense sulphur
Acid is 7 with hydrogen peroxide volume ratio:3 solution) middle immersion 10min；Finally, reuse deionized water to enter silicon chip
Row is repeatedly rinsed, and purpose is essentially consisted in makes substrate clean, to obtain the preferable pentacene thin film of crystallinity；
2) pentacene thin film is prepared on a silicon substrate with vacuum deposition method：
A) by step 1) in the silicon substrate of wash clean be fixed on the sample stage in equipment vacuum cavity, and by 0.2g
Pentacene be put at evaporation source；
B) after the rate of sublimation of pentacene stabilizes to 2nm/min, the heating-up temperature for controlling sample stage is 50 DEG C；
C) baffle plate of the gear on substrate is opened, while open film thickness detector the thickness of pentacene thin film is detected,
It is 50nm to make its deposit thickness.
3rd, the pentacene thin film field-effect transistor of non-flexible face-to-face structure is prepared：
The organic film with silicon as substrate prepared in step 2 is fixed on support using the base on probe station
Side, film surface down, then, the laminate patch electrode for preparing are placed on probe station, make under probe station in steps 1
Fall, so that the two is fitted in aspectant mode, finally, it is seen that infiltration phenomenon, that is, prepare.
Fig. 8 is schematic diagram, pictorial diagram and the performance curve of the face-to-face structure of pentacene thin film field-effect transistor, wherein,
Schematic diagrames of the Fig. 8 (a) for the face-to-face structure of pentacene thin film field-effect transistor；Fig. 8 (b) be pentacene thin film and
Pictorial diagram after the laminating of laminate patch electrode；Fig. 8 (c) is bent for the performance of the face-to-face structure of pentacene thin film field-effect transistor
Line, wherein, VGRepresent grid voltage, ISDRepresent source-drain current.
This patent is with using vacuum evaporation technology, (structure of the organic film FET for preparing as shown in Figure 1 is shown
It is intended to) realize that pentacene thin film prepared by large area is compared, in experimentation, electrode and pentacene are to be deposited with respectively
, it is to avoid damage semiconductor caused in electrode evaporation (Applied Physics Letters 2011,
99,183304)；With the nanometer embossing (structural representation of the organic film FET for preparing as shown in Figure 3
Figure) compare, pentacene thin film field-effect transistor prepared by our this example damages little to organic semi-conductor；
Prepare with inkjet technology (structural representation of the organic film FET as prepared by Fig. 2) is utilized
The broad area device of large area TIPS- pentacene is compared, and electrode and semiconductor need not be not only dissolved in by our experiment
In solvent, and the photoetching technique for adopting prepares electrode, higher (the Electrochemical and Solid State of precision
Letters 2009,12 (6), H195).
Embodiment 2, the pentacene thin film field-effect transistor for preparing flexible structure face-to-face：
1st, laminate patch electrode is prepared：Preparation process is with the method in embodiment 1.
2nd, the organic film with flexible polystyrene as substrate is prepared, is comprised the steps：
1) silicon chip of 1cm × 1cm sizes is cut with diamant；It is then placed in beaker, pours the third of 20ml into
Ketone, is put into ultrasound 15min in supersonic wave cleaning machine；Deionized water flushing silicon chip three to five times, with the chromic acid for preparing
Solution soaks 10min；Finally reuse deionized water repeatedly to rinse silicon chip.The purpose of cleaning mainly makes
Film is deposited on a clean substrate, obtains more preferable film quality；
2) OTS (octadecyl trichlorosilane alkane) modifications are carried out to silicon chip：The positive heptan that washed silicon chip is put into 80ml
1h in the solution that the OTS solution of alkane and 80 μ l is prepared.Purpose is to make silicon chip hydrophobic, beneficial to flexible substrate afterwards and silicon
Piece departs from；
3) spin coating polystyrene solidify on silicon chip：Directly in step 2) in silicon chip on spin coating polystyrene first
Benzole soln, is then placed in baking oven 70 DEG C of 10min that are heating and curing as substrate；
4) pentacene thin film is prepared on Polystyrene substrates with vacuum deposition method：First by step 3) in be rotary with polyphenyl
The silicon chip of ethene is fixed on the sample stage in equipment vacuum cavity, and the pentacene of 0.2g is put at evaporation source；So
Afterwards cavity is vacuumized, treats that internal vacuum reaches 10-4During Pa, evaporation source is heated；Until the distillation speed of pentacene
Rate is that control sample stage is heated to 50 DEG C after 2nm/min stablizes；Gear baffle plate on sample is finally opened, while beating
Open film thickness detector to detect the thickness of pentacene thin film, deposit 50nm.
3rd, the pentacene thin film field-effect transistor of flexible face-to-face structure is prepared：To be walked using the base on probe station
Rapid 4) in the organic film with polystyrene as substrate for preparing shift from silicon substrate, and be fixed on
Above frame, film surface down, then, the laminate patch electrode for preparing is placed on probe station, probe is made in step 1
Platform falls, and so that the two is fitted in aspectant mode, finally, it is seen that infiltration phenomenon, that is, prepares.
Fig. 9 is the structural representation of the flexible pentacene thin film field-effect transistor of structure face-to-face prepared by embodiment 2
Figure, pictorial diagram and performance comparison figure.Fig. 9 (a) is the structural representation on flexible organic film transistor planar；Figure
9 (b) is the transfer curve that flexible organic film transistor is placed on the plane.Fig. 9 (c) is flexible organic film crystal
Pipe is placed on the pictorial diagram on sphere, and Fig. 9 (d) is placed on performance and plane performance on sphere for flexible organic film transistor
Comparison diagram, wherein black curve 1 are performance curve in the plane, and red curve 2 is the performance curve on sphere.
Fig. 9 (e) is pictorial diagram when flexible organic film transistor bends；Fig. 9 (f) is that flexible organic film transistor is curved
Folding 100 times afterwards with plane performance comparison diagram, wherein black curve 1 is performance curve in the plane, red curve
2 is to bend 100 performance curves afterwards.
As can be seen from Figure 9：This TFT can test out performance with bending 100 times on curved surface afterwards,
Can be seen that performance in curved surface and plane without significant change from 9 (d) figure, it is seen that the pentacene of flexible structure face-to-face is thin
The flexibility of film field-effect transistor is excellent；From 9 (f) figure can be seen that bending 100 times after performance change unobvious, can
See that the pentacene thin film field-effect transistor of flexible structure face-to-face has certain bend resistance ability.
Embodiment 3, the pentacene thin film field-effect transistor for preparing flexible volume to volume structure：
1st, laminate patch electrode is prepared：Preparation process is with the method in embodiment 1.
2nd, the organic film with polystyrene as substrate is prepared, is comprised the steps：
1) silicon chip of 1cm × 1cm sizes is cut with diamant；It is then placed in beaker, pours the third of 20ml into
Ketone, is put into ultrasound 15min in supersonic wave cleaning machine；Deionized water flushing silicon chip three to five times, with the chromic acid for preparing
Solution soaks 10min；Finally reuse deionized water repeatedly to rinse silicon chip.The purpose of cleaning mainly makes
Film is deposited on a clean substrate, obtains more preferable film quality.
2) OTS (octadecyl trichlorosilane alkane) modifications are carried out to silicon chip：The positive heptan that washed silicon chip is put into 80ml
1h in the solution that the OTS solution of alkane and 80 μ l is prepared.Purpose is to make silicon chip hydrophobic, beneficial to flexible substrate afterwards and silicon
Piece departs from.
3) spin coating polystyrene solidify on silicon chip：Directly in step 2) in silicon chip on spin coating polystyrene first
Benzole soln, is then placed in baking oven 70 DEG C of 10min that are heating and curing as substrate；
4) pentacene thin film is prepared on Polystyrene substrates with vacuum deposition method：First by step 3) in be rotary with polyphenyl
The silicon chip of ethene is fixed on the sample stage in equipment vacuum cavity, and the pentacene of 0.2g is put at evaporation source；So
Afterwards cavity is vacuumized, treats that internal vacuum reaches 10-4During Pa, evaporation source is heated；Until the distillation speed of pentacene
Rate is that control sample stage is heated to 50 DEG C after 2nm/min stablizes；Gear baffle plate on sample is finally opened, while beating
Open film thickness detector to detect the thickness of pentacene thin film, deposit 50nm.
3rd, the pentacene thin film field-effect transistor of flexible volume to volume structure is prepared：Schematic diagram, adopts as shown in Figure 7
Two roller bearings of identical speed rightabout rotation, laminate patch electrode prepared by step 1 and step 2 are on flexible substrates
The organic semiconductor thin-film of preparation is parallel to be placed between two roller bearings, and both are fitted well, flexible volume is prepared
Pentacene thin film field-effect transistor to volume structure.
Claims (9)
1. a kind of preparation method of the organic film FET based on laminate patch electrode, comprises the steps：
1) laminate patch electrode is prepared；
2) by organic film and step 1) described in laminate patch electrode combine, obtain described based on the organic thin of laminate patch electrode
Film field-effect transistor.
2. preparation method according to claim 1, it is characterised in that：Step 2) in, the mode of the combination
For pressing.
3. preparation method according to claim 2, it is characterised in that：The pressing is：By vacuum evaporation in lining
On bottom, the organic film and the laminate patch electrode are pressed using aspectant mode, are obtained described based on laminate patch electricity
The organic film FET of pole；
Or, two roller bearings rotated using identical speed rightabout, by the laminate patch electrode and the evaporation soft
On property substrate, the organic film is parallel is placed between two roller bearings, is rolled, is obtained with flexible volume to volume structure
The organic film FET based on laminate patch electrode.
4. preparation method according to claim 3, it is characterised in that：The condition of the vacuum evaporation is as follows：Will
The substrate is placed in vacuum moulding machine cavity, and it is 1 × 10 to adjust vacuum in cavity-4～9 × 10-4Pa；Heating preparation has
Organic semiconducting materials needed for machine film cause its rate of sublimation to beIn the substrate surface deposit thickness it is
The organic film of 20～100nm, obtains depositing the organic film over the substrate.
5. the preparation method according to any one of claim 1-4, it is characterised in that：The organic film is for simultaneously
Any one in pentaphene film, phthalocyanine copper film and Phthalocyanine Zinc film；
The substrate is flexible substrate or non-flexible substrate.
6. preparation method according to claim 5, it is characterised in that：The flexible substrate is polymethylacrylic acid
Methyl esters flexible substrate or polystyrene flexible substrate；
The non-flexible substrate is any one in silicon chip, sheet glass and sapphire sheet；
The non-flexible substrate is also including the step of being cleaned successively, wherein, institute with acetone and Piranha washing lotion using front
Piranha washing lotion is stated for the concentrated sulfuric acid and hydrogen peroxide volume ratio 7:3 solution.
7. the preparation method according to any one of claim 1-6, it is characterised in that：Step 1) in, described
Laminate patch electrode is to be prepared as follows to obtain：
(1) circuit mask plate is prepared, is comprised the steps：A) using L-editor softwares separately design source electrode,
The circuit reticle pattern of drain electrode and grid；B) in quartz/spin-on-glass polymethyl methacrylate, using sharp
The circuit reticle pattern that light direct-write methods etch step a) is obtained；Then chromium is deposited with, and removes the poly- methyl-prop
E pioic acid methyl ester, obtains the circuit mask plate of the source electrode, the drain electrode and the grid；
(2) prepare the flexible flat with circuit pattern and embed laminate patch electrode, comprise the steps：A) in substrate
Surface connects octadecyl trichlorosilane alkane；B) on the substrate after through step a) modifications, using the method and step of photoetching
Suddenly the circuit mask plate that (1) obtains prepares source electrode, drain electrode and gate electrode respectively；And in the source electrode, described
The surface of metal electrode connection mercaptopropyl trimethoxysilane of drain electrode and the gate electrode；C) obtaining in step b)
The source electrode, the drain electrode and the gate electrode surface of metal electrode difference spin coating dimethyl silicone polymer,
And solidified；D) gate electrode that spin coating has dimethyl silicone polymer is shifted from the substrate；By institute
State the poly- diformazan of surface of metal electrode, the dimethyl silicone polymer surface of the source electrode and the drain electrode of gate electrode
Radical siloxane surface carries out oxygen plasma process respectively, i.e., form hydroxyl on surface；E) source electrode and institute are cut out
State drain electrode；By the surface of metal electrode of the gate electrode, the dimethyl silicone polymer surface of the source electrode and described
The dimethyl silicone polymer surface of drain electrode is aligned and is heated, then by the gate electrode, the source electrode and described
Drain electrode connection shape is integral, obtains the embedded laminate patch electrode of the flexible flat.
8. preparation method according to claim 7, it is characterised in that：Step (2) a) in, the connection ten
The step of eight alkyltrichlorosilanes, is as follows：The substrate after by cleaning is statically placed in the concentrated sulfuric acid
7：In 3 mixed solution；Then the substrate is cleaned, then the substrate is placed in normal heptane and octadecyl trichlorine
Silane volume ratio is 1000：In 1 mixed solution, the octadecyl trichlorosilane in substrate surface connection
Alkane；
Step (2) b) in, the method for the photoetching is as follows：Spin coating photoresist, heated rearmounted over the substrate
Be exposed under the uviol lamp under 365nm, then developed and fixing successively after, carry out evaporation metal；
Step (2) c) in, on the gate electrode, the thickness of the dimethyl silicone polymer of spin coating is 50～500 μm；
In the source electrode and the drain electrode, the thickness of the dimethyl silicone polymer of spin coating is 0.8～5 μm；Described solid
The temperature of change is 70～100 DEG C, and the time of the solidification is 2～12h；
Step (2) d) in, the time that the oxygen plasma is processed is 10～60s；
Step (2) e) in, the temperature of the heating is 70～100 DEG C, and the time of the heating is 10～30min.
9. the organic film field obtained from the preparation method any one of claim 1-8 based on laminate patch electrode is imitated
Answer transistor.
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