CN109456327A - High mobility emitting semiconductor and preparation method thereof, purposes and methods for using them - Google Patents
High mobility emitting semiconductor and preparation method thereof, purposes and methods for using them Download PDFInfo
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Abstract
The invention discloses high mobility emitting semiconductors and preparation method thereof, purposes and methods for using them, the preparation method of high mobility emitting semiconductor includes the Suzuki coupled chemical reactions between aryl bromo-derivative or iodo object and aryl boric acid or borate, the method for being applied to device of high mobility emitting semiconductor, device uses bottom gate top contact device architecture, grid uses the doped silicon of N-shaped, the SiO of thermally grown one layer of 300nm2As insulating layer, before Deposit organic semiconductor layer, gate insulating layer is modified with OTS at 120 DEG C of vacuum drying oven, forms single layer OTS decorative layer；Decorative layer uses chloroform, n-hexane in succession, and isopropanol and acetone are cleaned, and plated film is carried out in the way of spin coating by high mobility emitting semiconductor.The material that the present invention synthesizes shows the property of aggregation-induced emission, and traditional fluorescent dye then has the phenomenon that aggregation inducing fluorescent quenching under a high concentration condition, therefore effectively overcomes the defect of traditional fluorescent dye.
Description
Technical field
The invention belongs to the technical field of organic photoelectrical material more particularly to high mobility emitting semiconductor and its preparation sides
Method, purposes and methods for using them.
Background technique
Many flexible photoelectric devices such as Organic Light Emitting Diode, organic field effect tube are organic again for organic semiconductor
There is important application in the fields such as photovoltaic.Although the organic semiconductor of high mobility and the Organic Light Emitting Diode of high-luminous-efficiency are equal
Good development is obtained, while having the organic semiconducting materials of high mobility and high brightness is still to be one to challenge.
High mobility organic luminous semiconductor can be used for preparing mailing lighting transistor, pumping laser etc., in addition, organic hair of near-infrared
Photosemiconductor has application in night vision, encryption display and fluorescence probe etc..
Summary of the invention
The object of the present invention is to provide high mobility emitting semiconductor and preparation method thereof, using and methods for using them, solution
The technical issues of be that the existing most mobility of AIE luminescent material is lower, and the semiconductor material of high mobility is mostly in solid-like
Fluorescence is quenched under state.The present invention is directed to which the thought of aggregation-induced emission to be used for the design of high migration semiconductor, it is expected to combine
The semiconductor material simultaneously a little with high mobility and high-luminous-efficiency of the two.
The technical solution adopted by the present invention to solve the technical problems is:
High mobility gathering induced luminescence material, it is characterised in that: including following chemical formula:
The R1, R2 and R3 are H or various acid imide receptors, and wherein receptor specifically includes following structural formula:
R5 is alkyl chain or glycol chain CnOmH2n+1O, n=1~24, m=0~10.
It is further preferred that the R1, R2, R3 and R4 specific structure are as follows,
Wherein, acceptor is the receptor.
Further, the number of C is 1-24 in the R5, and the number of O is 0-10.
The preparation method of high mobility emitting semiconductor, it is characterised in that: the preparation of the high mobility emitting semiconductor
Method includes the Suzuki coupled chemical reactions between aryl bromo-derivative or iodo object and aryl boric acid or borate, specifically include with
Lower chemical formula:
Wherein, acceptor is the receptor.
It is further preferred that high mobility emitting semiconductor includes TriPE-nPDI series compound, wherein n=1,2 or 3.
The purposes of high mobility emitting semiconductor, it is characterised in that: the high mobility emitting semiconductor for OLED,
OFET and OLET.
The method for being applied to device of high mobility emitting semiconductor, it is characterised in that: the device uses bottom gate apical grafting
Device architecture is touched, grid uses the doped silicon of N-shaped, the SiO of thermally grown one layer of 300nm2As insulating layer, organic partly led depositing
Before body layer, gate insulating layer is modified with OTS at 120 DEG C of vacuum drying oven, forms single layer OTS decorative layer；The decorative layer phase
Cleaned after with chloroform, n-hexane, isopropanol and acetone, and by high mobility emitting semiconductor in the way of spin coating into
Row plated film.
It is further preferred that the specific side for carrying out plated film in the way of spin coating by high mobility emitting semiconductor
Method are as follows:
By TriPE-1PDI be dissolved in concentration be 7mg/mL chloroform, after be applied on device, spin speed be the 3000rpm time
For 30s, TriPE-2PDI is dissolved in the chloroform that concentration is 5mg/mL, after be applied on device, spin speed is the 3000rpm time to be
It is to be carried out later at 100 DEG C with 0.22 μm of filter in 2mg/ml meta-xylene that 30s, last TriPE-3PDI, which are dissolved in concentration,
Drop coating is stood overnight at room temperature on device after filter；It is 8mg/ml chloroformic solution that compound TriPE-3PDIL, which is dissolved in concentration,
After be applied on device, 30s is applied under 3000rpm revolving speed, in organic surface by the gold of mask vacuum evaporation 50nm as source
Electric leakage machine, the channel length of device are that 31 μm of width are 273 μm, device are annealed 40min in 140 DEG C of nitrogen atmospheres, so far
Plated film is carried out in the way of spin coating by high mobility emitting semiconductor to finish.
It is further preferred that being applied to device also and needing for high mobility emitting semiconductor carries out source-drain current test, specifically
Step is, using being tested in Keithley4200 at room temperature nitrogen, mobility and threshold voltage VTHCalculating be by source
Linear fit, formula I are carried out after the curve saturation region evolution of leakage current opposing gate voltageDS=(W/2L) μeCi(VG-VTH)2；
IDSIt is source-drain current, μ is mobility, and W is channel width, and L is channel length, CiGate insulating layer unit area
Capacitor, VTHIt is threshold voltage.
It is further preferred that the capacitor of the insulating layer is 10nFcm-2。
Implement the present invention can achieve it is following the utility model has the advantages that
The invention proposes high mobility emitting semiconductor MOLECULE DESIGNs to synthesize new strategy, realizes such molecule in charge
Transmission and shine between it is perfectly balanced, can be widely applied and OLED, OFET, OLET in；
The material state of aggregation luminous efficiency that the present invention synthesizes is high, and fluorescence quantum yield is up to 30%；
The material that the present invention synthesizes shows the property of aggregation-induced emission, and traditional fluorescent dye is highly concentrated
Then there is the phenomenon that aggregation inducing fluorescent quenching under the conditions of degree, therefore effectively overcome the defect of traditional fluorescent dye；
The material that synthesis of the invention obtains shows feux rouges and near-infrared luminous characteristic；
The material that synthesis of the invention obtains shows higher electron mobility, up to 0.04cm2V-1s-1。
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound 2；
Fig. 2 is the carbon-13 nmr spectra of compound 2；
Fig. 3 is the high resolution mass spectrum of compound 2；
Fig. 4 is the nuclear magnetic resonance spectroscopy of compound 3；
Fig. 5 is the carbon-13 nmr spectra of compound 3；
Fig. 6 is the high resolution mass spectrum of compound 3；
Fig. 7 is compound TriPE-1PDI nuclear magnetic resonance spectroscopy；
Fig. 8 is compound TriPE-1PDI carbon-13 nmr spectra；
Fig. 9 is compound TriPE-1PDI high resolution mass spectrum；
Figure 10 is the nuclear magnetic resonance spectroscopy of compound TriPE-2PDI；
Figure 11 is the high resolution mass spectrum of compound TriPE-2PDI；
Figure 12 is the nuclear magnetic resonance spectroscopy of compound TriPE-3PDI；
Figure 13 is the high resolution mass spectrum of compound TriPE-3PDI；
Figure 14 is the nuclear magnetic resonance spectroscopy of compound TriPE-3PDIL；
Figure 15 is the high resolution mass spectrum of compound TriPE-3PDIL；
Figure 16 is the carbon-13 nmr spectra of compound TriPE-3NDI；
Figure 17 is the high resolution mass spectrum of compound TriPE-3NDI；
Figure 18 is in molar extinction coefficient (B) chloroformic solution of compound TriPE-nPDIs (A) in chloroformic solution
Normalization fluorescence spectrum (C) normalized ultra-violet absorption spectrum and the normalized absorption spectrum concentration of (D) film: 10 μM；
Figure 19 is TriPE-1PDI (A), and TriPE-2PDI (B), TriPE-3PDI (C) is with different n-hexane ratios
Emission spectrum compound concentration in chloroform/n-hexane: (10 μM)；λ ex:572nm. (D-F) compound TriPE-1PDI (D),
The photo of TriPE-2PDI (E), TriPE-2PDI (F) in chloroform/n-hexane with different n-hexane ratios, excitation wavelength
365nm；
Figure 20 is the thermal gravimetric analysis curve of series compound TriPE-nPDI, test condition: nitrogen atmosphere, heating speed 10
℃/min；
Figure 21 is the differential scanning calorimetric curve of series compound TriPE-nPDI, test condition: nitrogen atmosphere, heating speed
Spend 10 DEG C/min；
Figure 22 is compound (A) TriPE-1PDI, the cyclic voltammetry curve of (B) TriPE-2PDIandTriPE-3PDI；It surveys
Strip part: 0.1MBu4+NPF6- chloroformic solution, scanning speed: 100mV/s；
Figure 23 is compound TriPE-3PDI (AandB) andTriPE-3PDIL (CandD) organic under 140 DEG C of annealing
Field effect transistor output and transfer curve；
Figure 24 is transfer curve (B, C) the compound TriPE-2PDI of compound (A) TriPE-1PDI at room temperature 140
Output and transfer curve under DEG C annealing temperature；
Figure 25 is compound TriPE-1PDI, and TriPE-2PDI, TriPE-3PDI and TriPE-3PDIL are in room temperature and 140
The AFM picture and XRD diagram piece of film under DEG C annealing temperature；
Figure 26 is Absorption and emission spectra of the TriPE-3PDIL under chloroformic solution and filminess.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, now control attached drawing is described in detail
A specific embodiment of the invention.Obviously, described embodiments are only a part of the embodiments of the present invention, rather than whole
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
High mobility gathering induced luminescence material, it is characterised in that: including following chemical formula:
R1, R2 and R3 are H or various acid imide receptors, and wherein receptor specifically includes following structural formula:
R5 is alkyl chain or glycol chain CnOmH2n+1O, the number of C is 1-24, of O in n=1~24 and m=0~10, R5
Number is 0-10, R1, and R2, R3 and R4 specific structure are as follows,
Wherein, acceptor is the receptor.
The preparation method of high mobility emitting semiconductor includes aryl bromo-derivative or iodo object and aryl boric acid or borate
Between Suzuki coupled chemical reactions, specifically include following below formula:
Wherein, acceptor is above-mentioned receptor, and high mobility emitting semiconductor includes that (acid imide replaces TriPE-nPDI
Triphenylethylene) series compound, wherein n=1,2 or 3.
By taking the synthesis of TriPE-nPDI (n=1,2,3) series compound as an example:
The synthesis of aryl boric acid or borate are as follows:
Compound 2 (above-mentioned chemical equation mark 2 is compound 2) specific synthesis step:
Benzyl chloride (3g, 23.7mmol) is dissolved in after triethyl phosphite (4.92g, 29.6mmol) that 2h is stirred at room temperature is right
5h is reacted at 170 DEG C afterwards, until be cooled to after room temperature, 4,4'- dibromobenzo-phenones (7.3g, 21.3mmol), tetrahydrofuran
(40mL), potassium tert-butoxide (5.8g, 52.1mmol) stir 20h after being sequentially added reaction system at room temperature.After being cooled to room temperature, reaction
System is washed with water twice, and methylene chloride extracts organic phase, and n-hexane is chromatographed as eluent column, obtains (the above-mentioned chemistry of compound 4
Reaction equation mark 4 is compound 4), yield 90%, by compound 4 (500mg, 1.21mmol), PdCl under nitrogen protection2
[P(cy)3]2(99mg, 10%mmol), which alcohol borate (767mg, 3.02mmol) of piece, potassium acetate (949mg, 9.66mmol) are molten
For 24 hours in dioxane reflux.After water quenching reaction, organic phase is washed twice with saturated ammonium chloride, and anhydrous sodium sulfate is dry, and decompression is steamed
Solvent is removed in distillation, and crude product flash column chromatography, eluent is n-hexane: methylene chloride=1:1 is obtained with 70% yield
To compound 2,
The chemical structure of compound 2 is characterized, and hydrogen nuclear magnetic resonance modal data is obtained:1HNMR (400MHz, CDCl3, δ):
7.78-7.74 (t, J=8Hz, 4H, ArH), 7.32-7.30 (d, J=8Hz, 2H；ArH), 7.23-7.21 (d, J=8Hz, 2H；
ArH), 7.14-7.11 (m, 3H；ArH), 7.06-7.02 (m, 3H；ArH), 1.38-1.27 (br, 24H, CH3), such as Fig. 1；Chemical combination
Carbon-13 nmr spectra (Fig. 2) data of object 2:13CNMR (100MHz, CDCl3, δ): 146.1,143.3,142.4,137.1,
135.0,134.7,129.8,129.6,129.1,128.0,127.0,126.9,83.9,83.8,83.5,25.0,24.9；Chemical combination
High resolution mass spectrum (Fig. 3) data of object 2: HRMS (MALDI-TOF) m/z:[M]+Theoretical value C32H38B2O4, 508.2956；It is practical
Value, 508.3000.
The synthetic route of compound 3 (above-mentioned chemical equation mark 3 is compound 3) is with 2. yield of compound: 89%.
The chemical structure of compound 3 is characterized, hydrogen nuclear magnetic resonance modal data is obtained:1HNMR (400MHz, CDCl3,
δ): 7.76-7.74 (d, 4H, J=8Hz), 7.57-7.55 (d, 2H；J=8Hz), 7.33-7.31 (d, 2H, J=8Hz), 7.20-
7.18 (d, J=8Hz, 2H), 7.03-7.01 (d, J=8Hz, 2H), 1.38-1.32 (br, 36H, CH3), such as Fig. 4；Compound 3
Carbon-13 nmr spectra (figure five) data:13CNMR (100MHz, CDCl3, δ): 145.9,143.4,143.1,140.0,135.0,
134.7,134.4,129.8,129.1,128.9,127.1,83.9,83.80,83.7,25.0,24.9；The high-resolution of compound 3
Mass spectrum (Fig. 6) data: HRMS (MALDI-TOF) m/z:[M]+Theoretical value C38H49B3O6, 634.3808；Actual value 634.3775.
It synthesizes compound TriPE-1PDI (the mono-substituted triphenylethylene of acid imide):
Compound 1 (40mg, 0.13mmol) under nitrogen protection, 1Br-PDI-2EH (102mg, 0.15mmol), above-mentioned chemistry
Reaction equation mark 1 is compound 1, Pd (PPh3)4(49mg, 28%) and potassium carbonate (21mg, 1.5mmol), which are dissolved in, newly to be distilled
48h is reacted at 80 DEG C of tetrahydrofuran (10mL) and deoxygenated water (4mL).After being cooled to room temperature, mixture is washed with water uses dichloro afterwards twice
Methane extracts, and recrystallizes after column chromatographic purifying, obtains 65mgTriPE-1PDI, yield: 58%.
The chemical structure of compound TriPE-1PDI is characterized, hydrogen nuclear magnetic resonance modal data as shown in Figure 7 is obtained:1HNMR (400MHz, CDCl3, δ): 8.64-8.59 (m, 2H), 8.52-8.50 (m, 2H), 8.13-8.11 (d, J=8Hz, 2H),
7.81-7.79 (d, J=8Hz, 2H), 7.40-7.34 (m, 8H), 7.29-7.28 (m, 2H), 7.26-7.16 (m, 4H), 7.06
(s, 1H), 4.16-4.11 (m, 4H), 1.58 (m, 2H), 1.40-1.32 (m, 16H), 0.97-0.89 (m, 12H), compound
Carbon-13 nmr spectra (Fig. 8) data of TriPE-1PDI:13CNMR (100MHz, CDCl3, δ): 163.7,163.6,144.3,
143.1,141.4,140.3,140.1,138.2,135.7,134.4,134.1,131.5,130.8,130.6,130.4,
129.9,129.8,128.8,128.7,128.3,128.0,127.9,127.78,127.2,127.1,123.3,123.1,
123.0,122.4,122.1,122.0,44.3,44.2,38.0,30.8,28.8,28.7,24.1,24.0,23.1,14.1,
10.7；High resolution mass spectrum (Fig. 9) data of compound TriPE-1PDI: HRMS (MALDI-TOF) m/z:[M]+Theoretical value
C60H56N2O4, 868.4240；Actual value, 868.4231.
It synthesizes compound TriPE-2PDI (the disubstituted triphenylethylene of acid imide):
Compound 2 (30mg, 0.059mmol) under nitrogen protection, 1Br-PDI-2EH (90mg, 0.13mmol), Pd (PPh3)4
(19mg, 28%) and potassium carbonate (81mg, 0.59mmol) are dissolved in 80 DEG C of reaction 48h of tetrahydrofuran (10mL) and deoxidized water (4mL),
After being cooled to room temperature, mixture is washed with water to be extracted with dichloromethane afterwards twice, is recrystallized after column chromatographic purifying, is obtained 55mgTriPE-
2PDI, yield: 63%.
The chemical structure of compound TriPE-2PDI is characterized, hydrogen nuclear magnetic resonance modal data is obtained:1HNMR
(400MHz, CDCl3, δ): 8.68-8.56 (m, 10H), 8.19-8.17 (d, J=8Hz, 2H), 8.04-8.02 (d, J=8Hz,
1H), 7.97-7.95 (d, J=8Hz, 1H), 7.55-7.54 (m, 8H), 7.49-7.34 (m, 5H), 7.16 (s, 1H), 4.12-
4.02 (m, 8H), 1.95-1.88 (m, 4H), 1.34-1.31 (m, 32H), 0.89-0.87 (m, 24H), such as Figure 10；Compound
High resolution mass spectrum (Figure 11) data of TriPE-2PDI: HRMS (MALDI-TOF) m/z:[M+H]+Theoretical value C100H96N4O8,
1481.7301；Actual value, 1481.7263.
It synthesizes compound TriPE-3PDI (the trisubstituted triphenylethylene of acid imide):
Compound 3 (30mg, 0.047mmol) under nitrogen protection, 1Br-PDI-2EH (105mg, 0.15mmol), Pd
(PPh3)4(15mg, 28%) and potassium carbonate (52mg, 0.38mmol) are dissolved in tetrahydrofuran (8mL) and deoxidized water (2mL) in 80 DEG C
React 48h.After being cooled to room temperature, mixture is washed with water to be extracted with dichloromethane afterwards twice, is recrystallized, is obtained after column chromatographic purifying
76mgTriPE-3PDI, yield:77%.
The chemical structure of compound TriPE-3PDI is characterized, hydrogen nuclear magnetic resonance modal data is obtained:1HNMR
(400MHz, CDCl3, δ): 8.79-8.62 (m, 12H), 8.56-8.53 (dd, J=4Hz, 2H), 8.41-8.33 (m, 2H),
8.15-8.13 (br, 1H), 7.92-7.88 (m, 2H), 7.81-7.69 (m, 14H), 4.24 (br, 8H), 3.37 (br, 2H),
3.24 (br, 2H), 2.09-2.06 (m, 4H), 1.49-1.41 (m, 36H), 1.04-0.97 (m, 38H), 0.81-0.70 (m,
12H), such as Figure 12；High resolution mass spectrum (Figure 13) data of compound TriPE-3PDI: HRMS (MALDI-TOF) m/z:[M+H]+
Theoretical value C100H96N4O8, 1481.7301；Actual value, 1481.7263.
It synthesizes compound TriPE-3PDIL (the trisubstituted triphenylethylene of long chain imide):
Compound 3 (30mg, 0.047mmol) under nitrogen protection, 1Br-PDI (105mg, 0.15mmol), Pd (PPh3)4
(15mg, 28%) and potassium carbonate (52mg, 0.38mmol) are dissolved in tetrahydrofuran (8mL) and deoxidized water (2mL) is reacted at 80 DEG C
48h.After being cooled to room temperature, mixture is washed with water to be extracted with dichloromethane afterwards twice, is recrystallized, is obtained after column chromatographic purifying
76mgTriPE-3PDIL, yield:77%.
The chemical structure of compound TriPE-3PDIL is characterized, hydrogen nuclear magnetic resonance modal data is obtained:1HNMR
(400MHz, CDCl3, δ): 8.71-8.49 (m, 14H), 8.31-8.28 (m, 2H), 8.01 (br, 1H), 7.75-7.61 (m,
16H), 7.37 (s, 1H), 4.15-4.09 (br, 8H), 3.23 (s, 2H), 3.05 (s, 2H), 2.01 (br, 4H), 1.75 (m,
2H), 1.24-1.06 (m, 138H), 0.84-0.79 (br, 42H), such as Figure 14；The high resolution mass spectrum of compound TriPE-3PDIL
(Figure 15) data: HRMS (MALDI-TOF) m/z:[M+H]+Theoretical value C188H232N6O12, 2766.7801；Actual value,
2766.7813.
Synthesize compound TriPE-3NDI:
The same TriPE-3PDI of the synthetic route of compound TriPE-3NDI.Yield: 90%.
The chemical structure of compound TriPE-3NDI is characterized, carbon-13 nmr spectra data, such as Figure 16 are obtained:13CNMR (100MHz, CDCl3, δ): 164.2,164.0,146.2,142.3,138.5,137.7,137.3,131.2,130.8,
130.6,130.1,130.0,129.8,128.7,128.0,127.9127.8,126.9,126.8,123.0,40.5,31.6,
High resolution mass spectrum (Figure 17) data of 28.0,26.8,22.6,14.0. compound TriPE-3NDI: HRMS (MALDI-TOF) m/
Z:[M+H]+Theoretical value C74H67N3O6, 1094.5103；Actual value, 1094.5134.
The purposes of high mobility emitting semiconductor, high mobility emitting semiconductor are used for OLED, OFET and OLET.
The method for being applied to device of high mobility emitting semiconductor, device use bottom gate top contact device architecture, grid
Using the doped silicon of N-shaped, the SiO of thermally grown one layer of 300nm2As insulating layer, the capacitor of insulating layer is 10nFcm-2, depositing
Before organic semiconductor layer, gate insulating layer is modified with OTS at 120 DEG C of vacuum drying oven, forms single layer OTS decorative layer；It is described
Decorative layer uses chloroform, n-hexane in succession, and isopropanol and acetone are cleaned, and uses spin coating using high mobility emitting semiconductor
Mode carry out plated film
The chemical structure of TriPE-1PDI and certain key intermediates characterization:
Nuclear-magnetism characterization (Fig. 1~figure has been carried out to the chemical structure of TriPE-nPDI and TriPE-NDI that synthesis obtains
17)。
Photophysical property characterization:
The photophysical property of series compound TriPE-nPDIs is studied with ultravioletvisible absorption and fluorescence spectrum
(Figure 18 and Figure 19).In dilute chloroformic solution, the absorption of compound TriPE-1PDI, TriPE-2PDI and TriPE-3PDI
Spectrum is about the same, mainly shows 500 and 536nm, two absorption peaks.The molar absorbance value of compound is with imido
Number linearly increases.Compound TriPE-1PDI, TriPE-2PDI and the TriPE-3PDI equal table under solution and solid state
Reveal feux rouges and near infrared emission (650-900nm).From solution to solid, the transmitting of compound shows red shift, wherein chemical combination
The launch wavelength red shift of object TriPE-3PDI is to 680nm.Have studied the aggregation-induced emission of series compound TriPE-nPDIs
Matter.Three compounds show luminescent behavior in the solution, and the fluorescence quantum yield of TriPE-1PDI is 2.5%, TriPE-
2PDI is 17%, TriPE-3PDI 8%.N-hexane is added in the chloroformic solution of three compounds, fluorescence intensity is gradually
Enhancing.The fluorescence quantum yield of lower three compounds of solid state be (TriPE-1PDI:11%, TriPE-2PDI:4% and
TriPE-3PDI:30%).
Macroscopic property and electrochemical properties are key parameters required for prepared by device.Thermogravimetric analysis shows three chemical combination
Object TriPE-1PDI, TriPE-2PDI and TriPE-3PDI show good thermal stability, and 5% thermal weight loss temperature is
435,447 and 453 DEG C (Figure 20).Differential scanning calorimetry shows compound TriPE-1PDI, TriPE-2PDI and TriPE-3PDI
Glass transition temperature be followed successively by 107,203 and 239 DEG C.The fusing point of three compounds is followed successively by 210 DEG C, 315 DEG C and 382
℃.Heat analysis shows that three compounds have good thermodynamic stability and morphology stability (Figure 21).Electro-chemical test table
The HOMO/LUMO energy level of tri- compounds of bright TriPE-nPDIs be respectively -5.43/-3.79eV, -5.52/-3.82eV and -
5.50/-3.84eV.Lower lumo energy is suitable for electron-transport (Figure 22).
It is prepared for the organic field effect tube device of three compounds.Device architecture is bottom gate top contact device.Device
Performance test carries out under nitrogen atmosphere.In general, the equal table of compound TriPE-1PDI, TriPE-2PDI and TriPE-3PDI
Reveal electronic transport property, with the increase of PDI unit, the mobility of compound is in gradually rise trend (Figure 23 and 24).Change
The electron mobility for closing object TriPE-1PDI film is~10-4cm2V-1s-1, threshold voltage 22V, on-off ratio 102.140 DEG C of annealing
Performance is declined after processing.The electron mobility of compound TriPE-2PDI, threshold voltage and on-off ratio make moderate progress.Change
It closes object TriPE-3PDI and shows the electron mobility for being much higher than TriPE-1PDI and TriPE-2PDI, about 0.01cm2V-1s-1。
After the side chain of compound TriPE-3PDI is lengthened, film forming is greatly improved, and mobility is further promoted to
0.04cm2V-1s-1We have studied the film morphology of compound with film X-ray diffraction (XRD) and atomic force microscope (AFM)
And crystallinity (Figure 25).The result shows that the unbodied film of compound TriPE-1PDI shows lower mobility, crystallinity
Film does not have performance.Compound TriPE-2PDI equally shows amorphous thin film, and film morphology is not influenced by annealing temperature.
Compound TriPE-3PDI film shows poor crystallinity, and film continuity is poor.After introducing long-chain, film morphology is obtained
To being obviously improved, therefore high mobility is shown, in addition, compound TriPE-3PDI still keeps preferable after long-chain introduces
Luminosity (Figure 26).The photophysical property and device property of compound are summarized in the table (Tables 1 and 2), HOMO in table
Indicate that highest has occupied empty track；LUMO indicates minimum and does not occupy unoccupied orbital；Td/Tg indicates that thermal decomposition temperature/vitrifying turns
Temperature, Ion/IoffIndicate that on-off ratio, VT indicate that threshold voltage, μ e indicate electron mobility.
The photophysical property of table 1, compound TriPE-nPDI, TriPE-2PDI, TriPE-3PDI summarizes
The field effect behavior of table 2, compound TriPE-nPDI and TriPE-3PDIL summarizes
The purposes of high mobility emitting semiconductor, high mobility emitting semiconductor for OLED (Organic Light Emitting Diode),
OFET (Organic Thin Film Transistors) and OLET (organic light-emitting transistor).
The method for being applied to device of high mobility emitting semiconductor, device use bottom gate top contact device architecture, grid
Using the doped silicon of N-shaped, the SiO of thermally grown one layer of 300nm2As insulating layer, before Deposit organic semiconductor layer, grid is exhausted
Edge layer is modified with OTS at 120 DEG C of vacuum drying oven, and single layer OTS decorative layer is formed；The decorative layer uses chloroform in succession, n-hexane,
Isopropanol and acetone are cleaned, and plated film is carried out in the way of spin coating by high mobility emitting semiconductor.
Plated film is carried out in the way of spin coating by high mobility emitting semiconductor method particularly includes:
By TriPE-1PDI be dissolved in concentration be 7mg/mL chloroform, after be applied on device, spin speed be the 3000rpm time
For 30s, TriPE-2PDI is dissolved in the chloroform that concentration is 5mg/mL, after be applied on device, spin speed is the 3000rpm time to be
It is to be carried out later at 100 DEG C with 0.22 μm of filter in 2mg/ml meta-xylene that 30s, last TriPE-3PDI, which are dissolved in concentration,
Drop coating is stood overnight at room temperature on device after filter；It is 8mg/ml chloroformic solution that compound TriPE-3PDIL, which is dissolved in concentration,
After be applied on device, 30s is applied under 3000rpm revolving speed, in organic surface by the gold of mask vacuum evaporation 50nm as source
Electric leakage machine, the channel length of device are that 31 μm of width are 273 μm, device are annealed 40min in 140 DEG C of nitrogen atmospheres, so far
Plated film is carried out in the way of spin coating by high mobility emitting semiconductor to finish.High mobility emitting semiconductor is applied to device
Part also needs to carry out source-drain current test, the specific steps are, using being tested in Keithley4200 at room temperature nitrogen, mobility and
Threshold voltage VTHCalculating be by carrying out linear fit after the curve saturation region evolution to source-drain current opposing gate voltage, it is public
Formula is
IDS=(W/2L) μeCi(VG-VTH)2
IDSIt is source-drain current, μ is mobility, and W is channel width, and L is channel length, CiGate insulating layer unit area
Capacitor, VTHIt is threshold voltage.
The embodiment of the present invention is described with above attached drawing, but the invention is not limited to above-mentioned specific
Embodiment, the above mentioned embodiment is only schematical, rather than restrictive, those skilled in the art
Under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, it can also make very much
Form, all of these belong to the protection of the present invention.
Claims (10)
1. high mobility gathering induced luminescence material, it is characterised in that: including following chemical formula:
The R1, R2 and R3 are H or various acid imide receptors, and wherein receptor specifically includes following structural formula:
R5 is alkyl chain or glycol chain CnOmH2n+1O, n=1~24, m=0~10.
2. high mobility emitting semiconductor as described in claim 1, it is characterised in that: the R1, R2, R3 and R4 specific structure
It is as follows,
R3=R4=acceptor or
R1=H,R3=R4=acceptor or
R1=R4=H,R3=acceptor or
R1=H,R3=H, R4=acceptor or
R1=R2=CN, R3=R4=acceptor or
R1=H, R2=CN, R3=R4=acceptor or
R1=R2=H, R3=R4=acceptor；
Wherein, acceptor is the receptor.
3. high mobility emitting semiconductor as described in claim 1, it is characterised in that: the number of C is 1-24, O in the R5
Number be 0-10.
4. the preparation method of high mobility emitting semiconductor as described in claim 1, it is characterised in that: the high mobility hair
The preparation method of photosemiconductor includes the Suzuki conjugation chemistry between aryl bromo-derivative or iodo object and aryl boric acid or borate
Reaction, specifically includes following below formula:
Wherein, acceptor is the receptor.
5. the preparation method of high mobility emitting semiconductor as claimed in claim 4, it is characterised in that: the high mobility hair
Photosemiconductor includes TriPE-nPDI series compound, wherein n=1,2 or 3.
6. the purposes of high mobility emitting semiconductor as claimed in any one of claims 1 to 5, wherein, it is characterised in that: the height
Mobility emitting semiconductor is used for OLED, OFET and OLET.
7. the method for being applied to device of high mobility emitting semiconductor as claimed in any one of claims 1 to 5, wherein, feature
Be: the device uses bottom gate top contact device architecture, and grid uses the doped silicon of N-shaped, the SiO of thermally grown one layer of 300nm2
As insulating layer, before Deposit organic semiconductor layer, gate insulating layer is modified with OTS at 120 DEG C of vacuum drying oven, is formed single
Layer OTS decorative layer；The decorative layer uses chloroform, n-hexane in succession, and isopropanol and acetone are cleaned, and is sent out using high mobility
Photosemiconductor carries out plated film by the way of spin coating.
8. the method for being applied to device of high mobility emitting semiconductor as claimed in claim 7, which is characterized in that the benefit
Plated film is carried out by the way of spin coating with high mobility emitting semiconductor method particularly includes:
By TriPE-1PDI be dissolved in concentration be 7mg/mL chloroform, after be applied on device, spin speed is the 3000rpm time to be
30s, by TriPE-2PDI be dissolved in concentration be 5mg/mL chloroform, after be applied on device, spin speed is the 3000rpm time to be
It is to be carried out later at 100 DEG C with 0.22 μm of filter in 2mg/ml meta-xylene that 30s, last TriPE-3PDI, which are dissolved in concentration,
Drop coating is stood overnight at room temperature on device after filter；It is 8mg/ml chloroformic solution that compound TriPE-3PDIL, which is dissolved in concentration,
After be applied on device, 30s is applied under 3000rpm revolving speed, in organic surface by the gold of mask vacuum evaporation 50nm as source
Electric leakage machine, the channel length of device are that 31 μm of width are 273 μm, and device is annealed 40min in 140 DEG C of nitrogen atmospheres, so far,
Plated film is carried out in the way of spin coating by high mobility emitting semiconductor to finish.
9. the method for being applied to device of high mobility emitting semiconductor as claimed in claim 8, which is characterized in that height migration
Being applied to device also and needing for rate emitting semiconductor carries out source-drain current test, and the specific steps are using Keithley4200 in room
It is tested in the lower nitrogen of temperature, mobility and threshold voltage VTHCalculating be to be saturated by curve to source-drain current opposing gate voltage
Linear fit, formula I are carried out after area's evolutionDS=(W/2L) μeCi(VG-VTH)2；
IDSIt is source-drain current, μ is mobility, and W is channel width, and L is channel length, CiThe electricity of gate insulating layer unit area
Hold, VTHIt is threshold voltage.
10. the method for being applied to device of high mobility emitting semiconductor as claimed in claim 8, which is characterized in that described
The capacitor of insulating layer is 10nFcm-2。
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