CN108878651B - 2,6- bis- (2- naphthalene) anthracenes are preparing the application in field effect transistor - Google Patents
2,6- bis- (2- naphthalene) anthracenes are preparing the application in field effect transistor Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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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]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
Abstract
The invention discloses the new applications of 2,6- bis- (2- naphthalene) anthracene.The new application of 2,6- bis- (2- naphthalene) anthracene provided by the present invention is it as organic semiconducting materials and is preparing the application in organic field effect tube and/or organic light-emitting field effect transistor.Using anthracene derivative shown in Formulas I as semiconductor layer material, it is prepared for the field effect transistor based on its film and monocrystalline respectively.Above-mentioned device shows typical p-type charge transport properties.Its mobility with higher, single crystal device mobility reach as high as 12.3cm2·V‑1·s‑1；With lower threshold voltage, about -10V；On-off ratio with higher, up to 107~108。
Description
Technical field
The invention belongs to organic semiconductor material fields, and in particular to 2,6- bis- (2- naphthalene) anthracenes are preparing field effect transistor
Application in pipe.
Background technique
Field effect transistor is the active device controllably injected based on free carrier to semiconductor, evaluates field effect transistor
The basic parameter of tube device performance specifically includes that mobility, threshold voltage and on-off ratio.Organic field effect tube is because it is saturating
The application prospect of bright circuit, flexible display device, sensing etc. and receive the extensive concern of people.In recent years, organic field
The research of effect transistor is fast-developing, wherein solution processable, high mobility, low operating voltage etc. all achieve
Good progress.In the practicalization of organic field effect tube, novel, high performance semiconductor material design with
Synthesis is performed meritorious deeds never to be obliterated, and the material for having both high mobility and low threshold voltage is always the target that people seek.
And benzene material is a kind of semiconductor material for studying at present more.Pentacene is as star's semiconductor point
Son, molecular conjugation degree is high, and monocrystalline mobility has reached 15-40cm2V-1s-1, but pentacene itself has relatively narrow energy gap
Cause its stability poor, it is difficult to practical.Compared to pentacene, anthracene class material and its derivative have that energy gap is big, stability
Well, it is easy to the features such as being chemically modified.
Summary of the invention
The object of the present invention is to provide the new applications of 2,6- bis- (2- naphthalene) anthracene.
The new application of 2,6- bis- (2- naphthalene) anthracene provided by the present invention is that it is being prepared with as organic semiconducting materials
Application in field effect transistors and/or organic light-emitting field effect transistor is especially preparing organic field effect tube
And/or the application in the semiconductor layer of organic light-emitting field effect transistor.
The present invention also protects a kind of organic field effect tube and/or organic light-emitting field effect transistor.
The organic field effect tube or organic light-emitting field effect transistor, the material of semiconductor layer include I institute of formula
The compound shown.
Wherein, the semiconductor layer is organic thin film layer or organic single-crystal layer.
The organic field effect tube includes organic film FET and organic single-crystal field effect transistor.
The organic light-emitting field effect transistor includes organic thin-film light emitting field effect transistor and organic single-crystal illuminated field
Effect transistor.
The structural formula of 2,6- bis- (2- naphthalene) anthracene is as shown in formula I:
The preparation method of 2,6- bis- (2- naphthalene) anthracene, includes the following steps:
1) by compound 1, Na2CO3、NaBH4It is reacted in solvent, when no longer generating gas, reactant is heated
To 80 DEG C, and 3h is reacted at such a temperature, be acidified to its pH value less than 7 to obtained mixed system, then filter, collect
Solid, as compound 2；
2) compound 2 for being cooled to -30 DEG C -78 DEG C and trifluoromethanesulfanhydride anhydride are urged in triethylamine
It is reacted under change, after temperature of reaction system is warmed to room temperature, the reaction was continued 1-10h obtains compound 3；
3) compound 3, compound 4, catalyst and alkali in an inert atmosphere, is made to carry out Suzuki coupling in solvent
Reaction, obtains 2,6- bis- shown in formula I (2- naphthalene) anthracene.
Solvent described in the step 1) is water；The compound 1, Na2CO3、NaBH4Molar ratio be followed successively by 1:(10~
20): (10~20), concretely 1:15:12；The reaction temperature of the reaction is 5-40 DEG C, specially 25 DEG C；
Inert atmosphere described in the step 2) and step 3) is nitrogen atmosphere or argon atmosphere；
The molar ratio of compound 2 described in the step 2) and trifluoromethanesulfanhydride anhydride is 1:2-5, specially 1:2.5；It is described
The molar ratio of triethylamine and compound 2 is 4-7:1, specially 5:1；
In the step 3), the catalyst is two (triphenyl phosphorus) palladium chlorides and/or four (triphenyl phosphorus) palladiums
In the step 3), the alkali in sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and cesium carbonate extremely
Few one kind；Alkali herein plays the role of assistant metal exchange and activation boric acid in the reaction.
In the step 3), the solvent is made of water, ethyl alcohol and solvent A, wherein solvent A is selected from toluene, tetrahydrofuran
At least one of with 1,4- dioxane；Concretely it is made of 1,4- dioxane, second alcohol and water according to volume ratio 4: 1: 1
Mixed liquor.
In the step 3), the temperature of the Suzuki coupling reaction is 50-200 DEG C, specially 100 DEG C, time 5-
30 hours, specially 24 hours.
The present invention, as organic semiconducting materials, is prepared for based on its film with 2,6- bis- shown in Formulas I (2- naphthalene) anthracene
With the field effect transistor of monocrystalline, have the effect that
(1) higher mobility, single crystal device mobility reach as high as 12.3cm2·V-1·s-1。
(2) lower threshold voltage, about -10V.
(3) higher on-off ratio, up to 107~108。
Detailed description of the invention
Fig. 1 is the thin film transistor device architecture schematic diagram based on 2,6- bis- (2- naphthalene) anthracene.
Fig. 2 is the atomic force microscopy diagram (AFM) of 2,6- bis- (2- naphthalene) anthracene film.
Fig. 3 is the X-ray diffraction result of 2,6- bis- (2- naphthalene) anthracene film.
Fig. 4 is transfer and the curve of output of the thin film transistor based on 2,6- bis- (2- naphthalene) anthracene.
Fig. 5 is the optical microscope of 2,6- bis- (2- naphthalene) anthracene crystal.
Fig. 6 is the atomic force microscopy diagram (AFM) of 2,6- bis- (2- naphthalene) anthracene crystal.
Fig. 7 is the single-crystal field effect transistor device optical microscope figure based on 2,6- bis- (2- naphthalene) anthracene.
Fig. 8 is transfer and the curve of output of the prepared single-crystal field effect transistor based on 2,6- bis- (2- naphthalene) anthracene.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, preparation 2,6- bis- (2- naphthalene) anthracene
(1) 300mL Na is added in 1000mL three neck round bottom flask2CO3Solution (1M), is then added NaBH4Solid
14.25g (0.375mol) is slowly added to 6.00g (0.025mol) 2,6- dihydroxy anthraquinone after solid is completely dissolved, observation
Become brownish black to solution from colourless, there are a large amount of bubbles to generate.After reacting a period of time, solution colour shoals, and bubble is reduced.
When no longer generating gas, reactant is heated to 80 DEG C, and react 3h at such a temperature.Later, mixture is transferred to
It in 1000mL beaker, is slowly acidified with 3M hydrochloric acid solution, after checking solution in acidity with pH test paper, is filtered, it is dry, it is solid to obtain grey
Body.With acetone washing solid, revolving obtains brown solid crude product 2,6- dihydroxy-anthracene 2.40g.
(2) raw material 2 is added in 100mL three neck round bottom flask, 6- hydroxyl anthracene (2.248g, 4.74mmol) is vacuumized, filled
Argon gas is repeatedly for three times.Later, be added 25mL methylene chloride be completely dissolved raw material, add triethylamine (7.38mL,
53.04mmol), -30 DEG C are cooled to, trifluoromethanesulfanhydride anhydride (26.6mmol, 4.48mL) is slowly added to.After -30 DEG C of reaction 7h,
2h is reacted at room temperature.After 2h, 50mL water is added into reaction system, liquid separation retains organic phase, water phase CH2Cl2
(20mL) is washed 3 times, merges organic phase.Organic phase is rotated, brown powder solid is obtained.Crude product is purified with silica gel column chromatography
(eluent is petroleum ether) obtains the pure solid product 2.21g of white powder.
(3) 2,6- bis- (trifluoro methylsulfonyl) anthracene (1.422g, 3mmol), 2- naphthalene boron are added in 250mL three neck round bottom flask
Sour (9mmol, 1.548g), Pd (PPh3)4(0.208g, 0.18mmol), K2CO3(1.656g, 12mmol), vacuumizes applying argon gas
Continuously three times.30mL mixed solvent (Isosorbide-5-Nitrae-dioxane: ethyl alcohol: water=4:1:1, v/v/v) is added with syringe, at 100 DEG C
It is reacted.It observes that solution is gradually become cloudy by light yellow, dark yellow turbid solution is finally presented.After reaction for 24 hours, filtering,
Discard filtrate.Filter cake is successively washed with water, ethyl alcohol, triethylamine, chloroform respectively, obtains crude product.Crude product with 1,1,2,
2- tetrachloroethanes is recrystallized to give yellow crystals.Later, it is purified by the method for distillation, obtains 2,6- bis- shown in formula I
(2- naphthalene) anthracene (1.197g, yield 93%).
The structural characterization data of I compound represented of formula:
Mp>340℃；1HNMR:8.60 (s, 2H), 8.40 (s, 2H), 8.28 (s, 2H), 8.21 (d, 4H), 8.03 (m,
10H), 7.58 (m, 4H)；MS (EI) m/z:430 [M+]；Elemental analysis: C (94.50%), H (5.65%).
The preparation and property of embodiment 2, organic film FET based on 2,6- bis- (2- naphthalene) anthracene shown in formula I
It can test
(1) using the silicon wafer with a thickness of 1mm as grid, on the grid layer with the preparation of the method for thermal oxide growth with a thickness of
The SiO of 300nm2Octadecyl trichlorosilane alkane (OTS) unimolecule is prepared by vapor phase method as insulating layer, then on which insulating layer
Layer (about 2nm) is insulation decorative layer.Bottom gate top contact FET device is constructed, device schematic diagram is as shown in Figure 1.
(2) 2,6- bis- shown in formula I is deposited by the method for vacuum evaporation on the insulation decorative layer described in step (1)
The film of (2- naphthalene) anthracene, vacuum degree 10-4Pa, rateSubstrate temperature TSIt is 80 DEG C, thickness 40nm.Prepared half
The atomic force microscopy diagram (AFM) of conductor thin film is as shown in Fig. 2, as can be known from Fig. 2, stratiform is presented in prepared semiconductive thin film
Growth, crystallite dimension reach 2 μm or more, and crystal boundary is few, are very beneficial for charge transmission.The X-ray of prepared semiconductive thin film
Diffraction patterns are as shown in figure 3, a series of high-intensitive equidistant diffraction maximum illustrates that the film is the good crystalline state of crystallinity
Film, average d spacing areWith the thickness degree obtained in AFM figureQuite, illustrate molecular stages in film
It stands in insulating layer substrate, is a kind of arrangement mode effectively transmitted conducive to charge.
(3) gold of 40nm thickness is deposited on the film described in step (2) as source-drain electrode, prepared device is in the sky
It is tested using Keithly4200 equipment.
(4) organic film FET property
Determine the property of organic field effect tube (Organic field-effect transistors, abbreviation OFETs)
Two key parameters of energy are: the mobility (μ) of carrier and the on-off ratio (I of deviceon/Ioff).Mobility refers in unit electricity
Under field action, (unit is cm to the average drift velocity of carrier2V-1s-1), it reflects hole under the electric field or electronics and is partly leading
Transfer ability in body.On-off ratio is defined as: electric current the ratio between of the transistor under "On" state and "Off" state, it reflects device
The superiority and inferiority of part switch performance.Field effect transistor high performance for one, mobility and on-off ratio should be high as far as possible.
Carrier mobility can be obtained by equation calculation:
IDS=(W/2L) Ciμ(VG–VT)2(saturation region)
Wherein, IDSFor drain current, μ is carrier mobility, and VG is grid voltage, and VT is threshold voltage, and W is ditch road width
Degree, L is channel length, CiFor the body capacitance that insulate.Utilize (IDS, sat)1/2It maps to VG, and makees linear regression, can thus return
The slope of line extrapolates carrier mobility (μ), acquires V by the section of the tropic and X-axisT.Mobility can according to formula from
The slope of transfer curve is calculated.On-off ratio can be obtained by the ratio between the maxima and minima of the side Fig. 4 source-drain current.
Fig. 4 is transfer and the curve of output of organic film FET prepared by step (3).
As shown in Figure 4, which shows typical p-type charge transport properties.Cut-in voltage is~-10V, and mobility is
2.1cm2·V-1·s-1, on-off ratio 107~108.In transfer curve, (- IDS)1/2~VGCurve has very good linear, says
Bright mobility does not have grid voltage dependence, is conducive to the functionization of device.
The preparation and property of embodiment 3, organic single-crystal field effect transistor based on 2,6- bis- (2- naphthalene) anthracene shown in formula I
It can test
(1) using the silicon wafer with a thickness of 1mm as grid, on the grid layer with the preparation of the method for thermal oxide growth with a thickness of
The SiO of 300nm2It is single by method preparation octadecyl trichlorosilane alkane (OTS) of distillation as insulating layer, then on which insulating layer
Molecular layer (about 3nm) is insulation decorative layer.
(2) 2,6- bis- shown in the method preparation formula I on the insulation decorative layer obtained by step (1) with physical vapour deposition (PVD)
The monocrystalline of (2- naphthalene) anthracene, gained monocrystalline is the organic single-crystal with parallelogram sturcutre, with a thickness of 20nm, optical microphotograph
Mirror figure is as shown in figure 5, atomic force microscopy diagram is as shown in Figure 6.
(3) with vacuum evaporation (vacuum degree 10 on the organic single-crystal obtained by step (2)-4Pa, evaporation rate are)
Or the method preparation for film of gilding obtains organic single-crystal field effect respectively as source electrode and drain electrode with a thickness of the gold electrode of 40nm
Transistor is answered, prepared device optical microscope figure is as shown in Figure 7.Prepared device utilizes in air
Keithly4200 equipment is tested.
(4) organic single-crystal field effect transistor property
Fig. 8 is transfer and the curve of output of prepared organic single-crystal field effect transistor.As seen from the figure, which shows
Typical p-type charge transport properties, cut-in voltage are~-10V, mobility 12.3cm2·V-1·s-1, on-off ratio 107~
108.In transfer curve, (- IDS)1/2~VGCurve have it is good linear, shown in the high mobility formula I of single crystal device
2,6- bis- (2- naphthalene) anthracenes have excellent charge transport properties, and field effect transistor, lighting transistor etc. have very
Good application prospect.
Claims (8)
1. compound shown in formula I is preparing organic field effect tube or organic light-emitting field effect crystalline substance as organic semiconducting materials
Application in body pipe；
2. compound shown in formula I is in the semiconductor layer for preparing organic field effect tube or organic light-emitting field effect transistor
Using；
3. application according to claim 1 or 2, it is characterised in that: the organic field effect tube includes organic film
Field effect transistor and organic single-crystal field effect transistor；The organic light-emitting field effect transistor includes organic light emitting film field
Effect transistor and organic light emission single-crystal field effect transistor.
4. a kind of organic field effect tube, the material of semiconductor layer includes I compound represented of claim 1 Chinese style.
5. organic field effect tube according to claim 4, it is characterised in that: the semiconductor layer is organic thin film layer
Or organic single-crystal layer.
6. organic field effect tube according to claim 4 or 5, it is characterised in that: the organic field effect tube
It from the bottom to top successively include grid, insulating layer, insulation decorative layer, semiconductor layer and source-drain electrode.
7. a kind of organic light-emitting field effect transistor, the material of semiconductor layer includes chemical combination shown in claim 1 Chinese style I
Object.
8. organic light-emitting field effect transistor according to claim 7, it is characterised in that: the semiconductor layer is organic thin
Film layer or organic single-crystal layer.
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