The semiconductor layer of organic semiconducting materials composition and organic field effect tube and its
Preparation method
Technical field
This disclosure relates to organic electronic device, in particular it relates to a kind of organic semiconducting materials composition and organic field effect
Answer semiconductor layer of transistor and preparation method thereof.
Background technology
Organic field effect tube (Organic Thin Film Transistor, OFET) is extensive because of its application prospect,
Cost is low, and it is convenient to prepare, and causes the common interest of people.OFET is by electrode (source electrode, drain electrode, grid), insulating barrier and organic half
Conductor layer is constituted, and current OFET electrode part is prepared by vacuum deposition method more, and insulating barrier is prepared by spin coating method more, is partly led
Body layer is then prepared by drop film or spin coating proceeding more.
Organic semiconductor is OFET important component, and according to the type of transmission carrier, organic semiconductor is divided into biography
The n-type material of son of transmitting electricity and the p-type material of transporting holes.One of important application for OFET, organic complementary circuit
(Organic Complementary Circuits), both materials are all indispensable, but it is steady still to lack air at present
The n-type material of fixed solution processable, therefore the development of p-type material is much better than n-type material.
Realize one of important channel prepared by the large area of organic field effect tube be full printing OFET (i.e. electrode, absolutely
The technique that the preparation of three parts of edge layer and semiconductor layer depends on printing is completed).The OFET devices printed entirely at present, especially
OFET based on type n semiconductor material is rarely reported.
Existing type n semiconductor material, which can not be met, can print and post-process the work for preparing full printing OFET in atmosphere
Skill requirement, therefore, it is difficult to realize prepared by large area, in addition, existing type n semiconductor material can not have been prepared on a flexible substrate
Field effect transistors device, limits the extensive use of related device.
The content of the invention
The purpose of the disclosure is:First aspect can be used for there is provided a kind of organic semiconducting materials composition, said composition
The semiconductor layer of organic field effect tube is prepared by impact system;Second aspect uses disclosure first aspect there is provided one kind
The method that the composition provided prepares the semiconductor layer of organic field effect tube;There is provided a kind of disclosure for the third aspect
The semiconductor layer for the organic field effect tube made by method that two aspects are provided;Fourth aspect contains this there is provided one kind
The organic field effect tube for the semiconductor layer that the open third aspect is provided.
To achieve these goals, there is provided a kind of organic semiconducting materials composition, the combination for disclosure first aspect
Thing contains benzene-naphthalene diimide derivative, polymeric additive and organic solvent;The organic solvent relative to 1mL, the naphthalene
The content of diimide derivative is 1-40mg, and the content of the polymeric additive is 1-40mg;The polymeric additive
For insulating polymer and/or semi-conducting polymer;The benzene-naphthalene diimide derivative has the structure as shown in formula (1):
Wherein, R1And R2It is each independently selected from C1-C30Alkyl.
Alternatively, the weight average molecular weight of the polymeric additive is 10,000-8,000,000.
Alternatively, the weight ratio of the benzene-naphthalene diimide derivative and the polymeric additive is 1:(0.5-1.5).
Alternatively, the insulating polymer is in polystyrene, polymethylstyrene, polymethyl methacrylate
It is at least one;The semi-conducting polymer is p-type semiconductor polymer, and the p-type semiconductor polymer is selected from poly- 3- hexyls
Thiophene, the polymer containing alkyl-substituted pyrrolo-pyrrole-dione unit, the polymer containing diazosulfide unit, contain
At least one of the polymer of benzene thiophene unit or polymer containing bioxindol unit.
Alternatively, the polymeric additive is insulating polymer, and the insulating polymer is polystyrene and poly- methyl
Methyl acrylate, the weight ratio of the polystyrene and polymethyl methacrylate is 1:(0.1-5).
Alternatively, the organic solvent is selected from toluene, meta-xylene, paraxylene, ortho-xylene, 1,2,3- front threes
At least one of benzene, 1,2,4- trimethylbenzenes, 1,3,5- trimethylbenzenes or naphthane.
Alternatively, the organic solvent is selected from 1,2,3- trimethylbenzene, 1,2,4- trimethylbenzenes, 1,3,5- trimethylbenzenes or tetrahydrochysene
At least one of naphthalene.
Alternatively, the viscosity at 20 DEG C of said composition is 0.6-6mPas.
There is provided a kind of method for the semiconductor layer for preparing organic field effect tube for disclosure second aspect;This method
Organic semiconducting materials composition including being provided disclosure first aspect using solwution method is processed film forming and located after carrying out
Reason, obtains the semiconductor layer of the organic field effect tube;The solwution method be selected from drop film, inkjet printing, silk-screen printing,
At least one of spin coating or blade coating.
Alternatively, the solwution method is inkjet printing or drop film.
Alternatively, the temperature of the post processing is 100-170 DEG C.
Alternatively, this method also includes:Before the inkjet printing steps, make what disclosure first aspect provided to have
Machine semiconductor material combinations thing is stirred successively after mixing, ultrasonic and filtering.
Organic effect made by a kind of method that the disclosure third aspect is provided there is provided disclosure second aspect is brilliant
The semiconductor layer of body pipe.
Disclosure fourth aspect is described to have there is provided a kind of organic field effect tube, including substrate, insulating barrier and electrode
Field effect transistors also include the semiconductor layer that the disclosure third aspect is provided.
Alternatively, the substrate is flexible substrates, and the flexible substrates are selected from PEN, gathered to benzene
At least one of naphthalate, polyimides or dimethyl silicone polymer.
Alternatively the insulating barrier and electrode are prepared by solwution method;The solwution method is selected from drop coating, inkjet printing, silk screen
At least one of printing, spin coating or blade coating.
Alternatively, the insulating barrier and electrode are prepared by ink-jet printing process.
There is provided for preparing organic effect crystal by allocating the composition of organic semiconducting materials composition for the disclosure
The organic semiconducting materials composition of pipe semiconductor layer, said composition has suitable viscosity and surface tension, can be using spray
The method of ink printing prepares semiconductor layer, can realize that whole soln method, even full impact system prepare n-type organic effect crystalline substance
Body pipe, improves the production efficiency and production scale of organic field effect tube;And said composition property stable in the air is high, prepares
Semiconductor layer crystal property it is good, improve the performance of transistor, and it is (small in low-voltage to realize organic field effect tube
In equal to 5V) under work.The semiconductor composition being related in the disclosure employs the non-chlorine to environment and the mankind's all less pollutions
Solvent, instead of conventional in current organic semiconductor field be difficult by the chlorinated solvents of microbial metabolism in environment.
Other feature and advantage of the disclosure will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing further understanding of the disclosure, and to constitute a part for specification, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute limitation of this disclosure.In the accompanying drawings:
Fig. 1 is a kind of transistor of embodiment preparation for the organic semiconducting materials composition that the disclosure is provided
Transfer characteristic curve;
Fig. 2 is a kind of transistor of embodiment preparation for the organic semiconducting materials composition that the disclosure is provided
Transfer characteristic curve.
Embodiment
Embodiment of this disclosure is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explained the disclosure, is not limited to the disclosure.
Disclosure first aspect contains benzene-naphthalene diimide and spread out there is provided a kind of organic semiconducting materials composition, said composition
Biological, polymeric additive and organic solvent;The organic solvent relative to 1mL, the benzene-naphthalene diimide derivative contains
Measure as 1-40mg, the content of the polymeric additive is 1-40mg;The polymeric additive is insulating polymer and/or half
Conductive polymers;The benzene-naphthalene diimide derivative has the structure as shown in formula (1):
Wherein, R1And R2It is each independently selected from C1-C30Alkyl.
There is provided for preparing organic effect crystal by allocating the composition of organic semiconducting materials composition for the disclosure
The organic semiconducting materials composition of pipe semiconductor layer, said composition has suitable viscosity and surface tension, can be using spray
The method of ink printing prepares semiconductor layer, can realize that whole soln method, even full impact system prepare organic field effect tube,
Improve the production efficiency and production scale of organic field effect tube;And said composition property stable in the air is high, the half of preparation
The crystal property of conductor layer is good, it is possible to increase the performance of transistor, realizes that organic field effect tube (is less than or equal in low-voltage
Worked under 5V).The semiconductor composition being related in the disclosure employs the non-chlorine solvent to environment and the mankind's all less pollutions, takes
It is difficult for what is commonly used in current organic semiconductor field by the chlorinated solvents of microbial metabolism in environment.
In order to further improve organic semiconducting materials composition filming performance and can inkjet performance, it is preferable that it is relative
In organic solvent described in 1mL, the content of benzene-naphthalene diimide derivative can be 5-30mg, and the content of polymeric additive can be
5-30mg。
According to the disclosure, the relative amount of benzene-naphthalene diimide derivative and polymeric additive can become interior in a big way
Change, under preferable case, the weight ratio of benzene-naphthalene diimide derivative and polymeric additive can be 1:(0.5-1.5), be preferably
1:When the weight ratio of (0.6-1.2), benzene-naphthalene diimide derivative and polymeric additive is in above-mentioned preferred scope, by organic half
Transistor prepared by conductor material compositions has more preferable carrier mobility and on-off ratio.
According to the disclosure in a first aspect, described benzene-naphthalene diimide derivative is 2- (the ylide alkene of 1,3- bis- sulphur-two)
The benzene-naphthalene diimide derivative (NDI-DTYM2) of third dicyan fusion, is the high performance n-type organic semiconducting materials of a class, structure
In formula (1), C1-C30Alkyl refer to carbon number be 1-30 alkyl, R1And R2Can be with identical or different, R1And R2Each solely
It is preferably on the spot the alkyl that carbon number is 5-30, more preferably carbon number is 10-20 alkyl.
According to the disclosure in a first aspect, polymeric additive can play the viscous of regulation and control organic semiconducting materials composition
The effect of degree and surface tension, makes composition disclosure satisfy that the technological requirement of ink-jet printing process, with the good difference of forming properties
The film of thickness, it is often more important that, polymeric additive adds the continuity and crystallinity for the semiconductive thin film being made, to property
The lifting of energy has very great help.Wherein the weight average molecular weight of polymeric additive can be in interior change in a big way, in order to enter one
Walk the surface tension and viscosity of effective regulation composition, it is preferable that the weight average molecular weight of polymeric additive can be 10,000-
8,000,000, more preferably 10,000-92,000;Insulating polymer is preferably selected from polystyrene, polymethylstyrene or poly-
At least one of methyl methacrylate, semi-conducting polymer is preferably p-type semiconductor polymer, and the p-type semiconductor is gathered
Compound can be selected from poly- 3- hexyl thiophenes, the polymer containing alkyl-substituted pyrrolo-pyrrole-dione unit, contain benzo
In the polymer of thiadiazole unit, the polymer containing benzene thiophene unit or the polymer containing bioxindol unit at least
It is a kind of.Wherein, the described polymer containing alkyl-substituted pyrrolo-pyrrole-dione unit refers to by alkyl-substituted pyrroles
And pyrroledione monomer or the monomer mixture containing alkyl-substituted pyrrolo-pyrrole-dione polymerize obtained polymer,
Substituent in alkyl-substituted pyrrolo-pyrrole-dione can be the alkyl that carbon number is 1-10, for example, methyl, ethyl,
N-propyl, isopropyl, normal-butyl, octyl group etc.;The described polymer containing diazosulfide unit refers to by diazosulfide
Monomer or monomer mixture containing diazosulfide polymerize obtained polymer;Described contains benzene thiophene unit
Polymer refer to by benzene thiophene monomer or the monomer mixture containing benzene thiophene polymerize obtained polymer;
The described polymer containing bioxindol unit refers to that the monomer mixture by bioxindol monomer or containing bioxindol is polymerize
Obtained polymer.
In a kind of preferred embodiment of the disclosure, polymeric additive can be insulating polymer, and insulation is poly-
Compound is preferably polystyrene and polymethyl methacrylate, it is highly preferred that the weight of polystyrene and polymethyl methacrylate
It can be 1 to measure ratio:(0.1-5).It is above-mentioned preferred embodiment in, the organic semiconducting materials composition of the disclosure has more
There is good film-formability energy and inkjet performance, the semiconductor layer prepared using said composition higher on-off ratio and carrier to move
Shifting rate, can realize and be worked under low-voltage.
According to the disclosure in a first aspect, organic solvent is well-known to those skilled in the art, have for the ease of preparing
The semiconductor layer of field effect transistors, can choose boiling point and be less than 200 DEG C of organic solvent, be preferably selected from toluene, two
In toluene, paraxylene, ortho-xylene, 1,2,3- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1,3,5- trimethylbenzenes or naphthane at least
One kind, more preferably selected from 1,2,3- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1, at least one of 3,5- trimethylbenzenes or naphthane.
According to the disclosure in a first aspect, the viscosity of organic semiconducting materials composition can in interior change in a big way,
In order to further improve said composition can inkjet performance and filming performance, under preferable case, the viscosity at 20 DEG C of said composition
For 0.6-6mPas, more preferably 0.7-5.0mPas;The surface tension of composition can be 20-32mN/m, more excellent
Elect 25-30mN/m as.Wherein, U.S. RheoSense microVISC are passed throughTMPortable viscometer measures the viscosity at 20 DEG C,
Surface tension is measured by platinum plate method using BZY-101 full-automatic surface tension instruments.
There is provided a kind of method for the semiconductor layer for preparing organic field effect tube for disclosure second aspect;This method bag
The organic semiconducting materials composition that disclosure first aspect is provided using solwution method is included to process film forming and post-processed,
Obtain the semiconductor layer of the organic field effect tube;The solwution method can be selected from drop film, inkjet printing, screen printing
At least one of brush, spin coating or blade coating, preferably inkjet printing or drop film.
According to the second aspect of the disclosure, this method can also include:Organic half that disclosure first aspect is provided
Conductor material compositions are stirred successively after mixing, ultrasonic and filtering.Stirring, ultrasound and filtering are those skilled in the art institutes
Well known, stirring and ultrasound are used for each component in dispersive composition, reduce precipitation, and mixing time can be 0.1-2h, supersonic frequency
Rate can be 20-40kHz, and the time can be 1-10min;The sediment fraction that filtration treatment is used in filter combination, prevents from beating
Print machine shower nozzle is blocked and improves printing effect, and its filtering accuracy can be 0.1-0.5 μm.
According to the second aspect of the disclosure, organic semiconducting materials composition carries out post processing after inkjet printing to be located
Reason removes organic solvent, and the temperature of post processing can be 100-170 DEG C, and preferably 120-160 DEG C, finishing time can be 5-
45min, preferably 30-40min.This method is more without being removed in the particular/special requirement environment such as vacuum drying chamber, nitrogen glove box
Remaining solvent, without completely cutting off oxygen in air, it is not necessary to post-processed under the light conditions such as infrared lamp and laser, it is not required that
Operated in dust free room, simplify the preparation process of semiconductor layer.In addition, above-mentioned preferred post-processing temperature is suitable, will not be right
Substrate is damaged, and can making the organic semiconducting materials composition of the disclosure, printing prepares semiconductor layer on a flexible substrate.
There is provided the organic field made by a kind of method provided by disclosure second aspect for the disclosure third aspect
The semiconductor layer of effect transistor.
Disclosure fourth aspect is described there is provided a kind of organic field effect tube, including substrate, insulating barrier and electrode
Organic field effect tube also includes the semiconductor layer that the disclosure third aspect is provided.
Wherein, substrate material can be conventional kind, preferably flexible substrates, and the flexible substrates can be selected from poly- naphthalene
At least one of naphthalate, polyethylene terephthalate, polyimides or dimethyl silicone polymer.Using
Organic field effect tube prepared by above-mentioned flexible substrates has flexibility, can widen the application of transistor with bending.
According to disclosure fourth aspect, the insulating barrier and electrode of organic field effect tube can be using this area routines
Prepared by method, in order to improve production efficiency, realize and produce in enormous quantities, under preferable case, insulating barrier and electrode can be by solwution methods
Prepare;The solwution method can be selected from least one of inkjet printing, silk-screen printing, spin coating or blade coating, it is highly preferred that absolutely
Edge layer and electrode can be prepared by ink-jet printing process, to realize that full impact system prepares organic field effect tube, improve organic field
The production efficiency and production scale of effect transistor.
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
In following embodiments of the disclosure, N, N-3- hexyls-undecyl -2- (1,3- dithiole -2- subunits -1- the third two
Cyanogen benzene-naphthalene diimide (NDI3HU-DTYM2) is prepared using the method disclosed in the A of CN 103408570, and polystyrene is purchased from
SIGMA-ALDRICH companies;Polymethyl methacrylate is purchased from Acros companies, and the trade mark is A0343872, and weight average molecular weight is
15,000;Remaining reagent is commercial products.
Embodiment 1
The present embodiment is used for the organic semiconducting materials composition for illustrating the disclosure.
Take 5mg NDI3HU-DTYM2,1mg polymers polystyrene (trade mark is BCBS8212V, and weight average molecular weight is 560,
000) mixed with the trimethylbenzene of 1mL solvents 1,3,5-, be sufficiently stirred for, obtain the organic semiconducting materials composition of the present embodiment.
Embodiment 2-8
The composition and content of organic semiconducting materials composition are shown in Table 1, and the step of embodiment 1 is respectively adopted prepares reality
Apply the organic semiconducting materials composition of a 2-8.
Wherein, in embodiment 8, the polystyrene trade mark is MKBQ8943V, and weight average molecular weight is 5,000.
Comparative example 1
This comparative example is used to illustrate the inks different from the disclosure.
Using the raw material and preparation method of embodiment 6, except that, the trimethylbenzene of solvent 1,3,5- is replaced with equal volume
Chloroform.
Comparative example 2
Using the raw material and preparation method of embodiment 6, except that, the ink of this comparative example does not contain polymer addition
Agent.
Comparative example 3
Using the raw material and preparation method of embodiment 6, except that, NDI3HU-DTYM2 is replaced with to the naphthalene of equivalent
Imidodicarbonic diamide and di- thiophene copolymers (N2200), shown in N2200 molecular structure such as formula (2), purchased from Polyera companies, board
Number CZH-XIV-115B-22, obtains the organic semiconducting materials composition of this comparative example.N2200 is that those skilled in the art are ripe
Printable type n semiconductor material know, currently the only, but its air stability is poor, it is necessary under nitrogen atmosphere protection
Post-process, the organic transistor device of preparation can be only achieved performance.
Testing example 1
Ultrasound 5min after embodiment 1-8 and comparative example 1-3 organic semiconducting materials composition is stirred into 1h through magnetic, then
Filtered using 0.22 μm of organic filter head, its viscosity is tested respectively, test result is listed in table 2, and wherein viscosity is used based on micro-
The RheoSense companies of electromechanical (MEMS, Micro-Electro-Mechanical System) and micro-fluidic technologies
microVISCTMPortable viscometer is measured.
Above-mentioned organic semiconducting materials composition is respectively charged into the print cartridge of ink jet printing device (Dimatix companies)
Row inkjet printing:Shower nozzle voltage is 26-27V, and nozzle temperature is 45 DEG C, puts 5 μm of spacing;By embodiment 1-8's and comparative example 1-2
The semi-conducting material film of printing is put on warm table in heating 30min at 120 DEG C, obtains semiconductor layer, and be respectively prepared organic
FET device;The semi-conducting material film printed in comparative example 3 is moved back in glove box (in nitrogen atmosphere) at 150 DEG C
Fiery 30min, is then spin coated onto insulating barrier, and organic field effect tube device is made in printing electrode.
The output and transfer for testing above-mentioned organic field effect tube using the semiconductor test systems of Keithley 4200 are special
Linearity curve, draws the carrier mobility of device by transfer curve saturation region carrier mobility calculation formula formula (3) and opens
Ratio is closed, test result is listed in Table 2 below.Wherein μ is carrier mobility, and L and W are respectively the length and width of raceway groove, CiTo be exhausted
The electric capacity of edge layer unit area, ISDFor the electric current between source-drain electrode, VGFor grid voltage.
Wherein, the organic field effect tube device prepared by the organic semiconducting materials composition of embodiment 1 and embodiment 5
The transfer characteristic curve difference of part is as depicted in figs. 1 and 2.
Table 1
Table 2
According to the data of table 1, contrasted from embodiment 1-8 and comparative example 1-3, the organic semiconducting materials combination of the disclosure
Organic field effect tube device prepared by thing has higher carrier mobility and on-off ratio, and the performance of transistor device is more
It is good, and printing post-treatment condition is gentle, be easy to the rapid and large-scale production of organic field effect tube.
From the data comparison of embodiment 3 and embodiment 4, in the preferred benzene-naphthalene diimide derivative of the disclosure and polymerization
The weight ratio of thing additive is 1:In the case of (0.5-1.5), the organic effect prepared by organic semiconducting materials composition
Transistor device has higher carrier mobility and on-off ratio;The data comparison of embodiment 6 and embodiment 8 can be seen that
In the case where the weight average molecular weight of the preferred polymeric additive of the disclosure is 10,000-8,000,000, by organic semiconductor
The performance of organic field effect tube device prepared by material compositions is more preferable.
The preferred embodiment of the disclosure described in detail above, still, the disclosure are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the disclosure, a variety of simple variants can be carried out with technical scheme of this disclosure, this
A little simple variants belong to the protection domain of the disclosure.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the disclosure to it is various can
The combination of energy no longer separately illustrates.
In addition, can also be combined between a variety of embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought, it should equally be considered as disclosure disclosure of that.