CN110396051A - A kind of small organic molecule hole injection/transmission material and the preparation method and application thereof - Google Patents
A kind of small organic molecule hole injection/transmission material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to small organic molecule hole injection/transmission material technical field, a kind of small organic molecule hole injection/transmission material and the preparation method and application thereof is disclosed.Small organic molecule hole injection/transmission material structural formula is as follows, whereinWherein, Ar1、Ar2With Ar3It independently is unsubstituted phenyl ring, condensed ring or loop coil aromatic hydrocarbons, or independently is phenyl ring, condensed ring or the loop coil aromatic hydrocarbons replaced through alkyl, alkoxy or alkylthio group that carbon atom number is respectively 1~6；Wherein the carbon atom number of phenyl ring, condensed ring or loop coil aromatic hydrocarbons is 6-40.Present invention employs the arylamine units of multiple nonplanar structures, also introduce methoxy end group, so that the material has high thermal stability, high glass-transition temperature, high HOMO energy level, high hole mobility and good dissolubility, there is important application prospect in the opto-electronic device.
Description
Technical field
The invention belongs to the technical fields of organic micromolecular photoelectric material, are related to a kind of small organic molecule hole injection/biography
Defeated material and the preparation method and application thereof.
Background technique
Organic electroluminescent LED (OLEDs) is with important application prospects in display and lighting area.High HOMO
Energy level hole-injecting material is the necessary component of OLED device.Patent Publication CN107954884A, which discloses one kind, to be had
Machine hole-injecting material XL1, the glass transition temperature of the material is 99 DEG C, HOMO energy level -5.05eV, it is undoped under the conditions of
Hole mobility about 1.45 × 10-4cm2V-1s-1, but in order to be satisfied with the practical application of OLED device, the glass transition of XL1
There is still a need for promotions for temperature.However, to have both high glass-transition temperature (>=120 DEG C) organic with high hole mobility for design synthesis
Small molecule hole injection/transmission material, it is challenging.
Summary of the invention
For overcome the deficiencies in the prior art, the primary purpose of the present invention is that providing a kind of small organic molecule hole note
Enter/transmission material.
Another object of the present invention is to provide the preparation methods of above-mentioned small organic molecule hole injection/transmission material.
A further object of the present invention is to provide above-mentioned small organic molecule hole injection/transmission materials in organic electroluminescent
Application in the photoelectric devices such as device and efficient calcium titanium photovoltaic device.
The purpose of the present invention is achieved through the following technical solutions:
A kind of small organic molecule hole injection/transmission material, structural formula is as shown in formula I:
It is describedWherein, Ar1、Ar2With Ar3It independently is unsubstituted phenyl ring, condensed ring or loop coil virtue
Hydrocarbon, or it independently is the phenyl ring, condensed ring or loop coil virtue replaced through alkyl, alkoxy or alkylthio group that carbon atom number is respectively 1~6
Hydrocarbon；Wherein the carbon atom number of phenyl ring, condensed ring or loop coil aromatic hydrocarbons is 6-40.
The chemical structure that the R group is preferably as follows:
Wherein * indicates the tie point of the R group.
One of described preferably following chemical structure of small organic molecule hole injection/transmission material:
A kind of preparation method of above-mentioned small organic molecule hole injection/transmission material, comprising the following steps:
(1) it in organic solvent and catalyst system, is carried out after bromine iodine substituted aromatic compound is mixed with aminated compounds
Reaction, reaction solution is purified, obtain brominated intermediate after reaction；
(2) in organic solvent and catalyst system, by brominated intermediate and (the 4- methoxybenzene of N, N- bis- obtained by step (1)
Base) coupling reaction is carried out after the mixing of -6- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan base) -2- naphthylamines, reaction knot
Crude product is obtained after beam, by after purification, obtaining small organic molecule hole injection/transmission material.
Catalyst system described in step (1) generally includes alkali compounds and catalyst；Wherein, the alkali compounds
For at least one of sodium tert-butoxide or potassium tert-butoxide；The catalyst is 1,10- ferrosin and cuprous iodide；
Step (1) the bromine iodine substituted aromatic compound is the bromo- 4- iodobenzene of 1-.
Step (1) aminated compounds is at least one of aniline and 4- aminoanisole；
Step (1) organic solvent is at least one of toluene, N,N-dimethylformamide and anhydrous tetrahydro furan.
Aminated compounds described in step (1), bromine iodine substituted aromatic compound, alkali compounds, 1,10- ferrosin and
The molar ratio of cuprous iodide is 1:(2.1~3): (3~6): (0.1~0.2): (0.2~0.4).
The dosage of step (1) described organic solvent meet every 1mol bromine iodine substituted aromatic compound it is corresponding be added 300~
The organic solvent of 1000mL.
Reaction described in step (1) is in 110 DEG C~120 DEG C 15~30h of reaction；
Step (1) reaction preferably carries out under atmosphere of inert gases；The inert gas is nitrogen.
Purifying described in step (1) is to be extracted after reaction solution is concentrated with organic solvent and water, will be had after liquid separation
Machine layer is concentrated and carries out column chromatography for separation purification.Preferably, reaction solution is is evaporated under reduced pressure by the first time concentration, and second
Secondary concentration is with anhydrous magnesium sulfate then organic layer drying to be filtered, is evaporated under reduced pressure；The organic solvent is methylene chloride and second
At least one of acetoacetic ester；The solvent of the column chromatography for separation purification is at least one of petroleum ether and n-hexane.
The chemical structure of brominated intermediate described in step (1) is as follows:
Step (2) organic solvent is at least one of toluene and tetrahydrofuran；
Catalyst system described in step (2) includes catalyst and alkali compounds aqueous solution；
Wherein, the catalyst includes tetra-triphenylphosphine palladium and phase transfer catalyst；Preferably, the phase transfer catalysis (PTC)
Agent is ethyl alcohol.The alkali compounds aqueous solution is at least one of wet chemical and aqueous sodium carbonate；Described
The concentration of alkali compounds aqueous solution is 0.5~5mol/L；Preferably 1~3mol/L, more preferably 2mol/L；
Step (2) the brominated intermediate and N, N- bis- (4- methoxyphenyl) -6- (4,4,5,5- tetramethyl -1,3,2-
Dioxaborolan base) -2- naphthylamines, tetra-triphenylphosphine palladium, phase transfer catalyst and alkali compounds molar ratio be 1:
(2.05~2.2): (0.01~0.03): (20~50): (3~5).
Coupling reaction condition described in step (2) is that 9~14h is reacted at 100~120 DEG C.
Coupling reaction described in step (2) preferably carries out in atmosphere of inert gases；The inert gas is nitrogen；
Purifying described in step (2) refer to by crude product by vacuum distillation remove after solvent with organic solvent and water into
Row extraction, organic layer is concentrated under reduced pressure after liquid separation, then use column chromatography purification；Preferably, the column chromatographs solvent first
Using the mixed solvent of petroleum ether and methylene chloride, volume ratio 3:1；Then gradually with the concentration gradient of volume ratio 2:1,1:1
Increase polarity, finally using methylene chloride as solvent.
Above-mentioned small organic molecule hole injection/transmission material is in organic electroluminescence device and efficient calcium titanium photovoltaic device
Application in equal photoelectric devices.
Preferably, the organic electroluminescence device is phosphorescence red device, and the efficient perovskite photovoltaic device is positive
To type perovskite photovoltaic device.
The principle of the present invention is as follows:
Present invention employs the arylamine units of multiple nonplanar structures, so that molecular rigidity enhancing, molecular weight increase, thus
Improve the glass transition temperature of material；Simultaneously because the strong of arylamine unit is given electrically, so that there is material high hole to move
Shifting rate and conductivity；And the presence of multiple methoxy end groups, not only HOMO (highest occupied molecular orbital) energy level of adjustable material,
The dissolubility that material can also be improved simultaneously, makes it be readily synthesized and purify, and can pass through vapor deposition or solution in device application
Processing.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) small organic molecule hole injection/transmission material of the invention have good thermal stability, wherein TPA1 and
The decomposition temperature when weightlessness 1% of TPA2 is respectively 434 DEG C and 431 DEG C；
(2) small organic molecule hole injection/transmission material of the invention has high glass-transition temperature, TPA1 and TPA2
Glass transition temperature respectively be up to 136 DEG C and 131 DEG C；
(3) small organic molecule hole injection of the invention/transmission material tool suitable HOMO energy level and high hole mobility,
It is 5.62 × 10 that wherein TPA1, which adulterates the mobility of 4%F4-TCNQ,-4cm2V-1s-1, the mobility of TPA2 doping 4%F4-TCNQ
It is 3.72 × 10-4cm2V-1s-1；
(4) small organic molecule hole injection/transmission material of the invention has suitable HOMO energy level, is conducive to hole
Injection and taking-up, are suitable for OLEDs and perovskite photovoltaic device；
(5) small organic molecule hole injection/transmission material of the invention has good dissolubility, is conducive to separation and mentions
It is pure, vapor deposition or solution processing can be used；
(6) small organic molecule hole injection/transmission material of the invention has easy synthetic method, and yield is high.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare small organic molecule hole injection/transmission material TPA1 nuclear magnetic resonance spectroscopy (a) and
Carbon-13 nmr spectra (b) figure.
Fig. 2 be embodiment 1 prepare small organic molecule hole injection/transmission material TPA1 ultraviolet-visible absorption spectroscopy and
Fluorescence emission spectrum (a) and antenna effect emission spectrum (b) figure.
Fig. 3 is small organic molecule hole injection/transmission material TPA1 TGA (a) and DSC (b) curve prepared by embodiment 1
Figure.
Fig. 4 is the low of small organic molecule hole injection/transmission material TPA1 ultraviolet photoelectron spectroscopy prepared by embodiment 1
The valence band spectrogram in kinetic energy area (a) and close fermi level area (b).
Fig. 5 is that small organic molecule hole injection/transmission material TPA1 prepared by embodiment 1 adulterates the single empty of 4%F4-TCNQ
The current density voltage curve (a) and current density of cave mobility test1/2Voltage curve (b) figure.
Fig. 6 is that small organic molecule hole injection/transmission material TPA1 prepared by embodiment 1 adulterates 4%F4-TCNQ Organic Electricity
Cause Current density-voltage-brightness curve (a) of feux rouges phosphorescent devices；Current efficiency-brightness curve (b)；Power efficiency-brightness
Curve (c)；Electroluminescent intensity-wavelength curve (d) and brightness-time graph (e) figure.
With bustamentite caesium after the small organic molecule hole injection that Fig. 7 is prepared for embodiment 1/transmission material TPA1 doping 4%LAD
For the current density voltage curve figure of the positive type perovskite photovoltaic device of active layer.
Fig. 8 be embodiment 2 prepare small organic molecule hole injection/transmission material TPA2 nuclear magnetic resonance spectroscopy (a) and
Carbon-13 nmr spectra (b) figure.
Fig. 9 is small organic molecule hole injection/transmission material TPA2 ultravioletvisible absorption and fluorescence prepared by embodiment 2
Emission spectrum (a) and antenna effect emission spectrum (b) figure.
Figure 10 is that small organic molecule hole injection/transmission material TPA2 TGA (a) and DSC (b) prepared by embodiment 2 are bent
Line chart.
Figure 11 is small organic molecule hole injection/transmission material TPA2 ultraviolet photoelectron spectroscopy prepared by embodiment 2
The valence band spectrogram of low kinetic energy area (a) and close fermi level area (b).
Figure 12 is the list that small organic molecule hole injection/transmission material TPA2 prepared by embodiment 2 adulterates 4%F4-TCNQ
The current density voltage curve (a) and current density of hole mobility test1/2Voltage curve (b) figure.
Figure 13 is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 is organic
Current density-voltage-brightness curve (a) of red electroluminescent phosphorescent devices；Current efficiency-brightness curve (b)；Power efficiency-is bright
It writes music line (c)；Electroluminescent intensity-wavelength curve (d) and brightness-time graph (e) figure.
With bustamentite after the small organic molecule hole injection that Figure 14 is prepared for embodiment 2/transmission material TPA2 doping 4%LAD
Caesium is the current density voltage curve figure of the positive type perovskite photovoltaic device of active layer.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
N in embodiment, N- bis- (4- methoxyphenyl) -6- (4,4,5,5- tetramethyl -1,3,2- dioxaborolan
Base) -2- naphthylamines preparation method refer to Chinese patent disclosure CN 107954884A.
Embodiment 1
Small organic molecule hole injection/transmission material structural formula of the present embodiment is specific as follows:
Small organic molecule hole injection/transmission material TPA1 preparation method of the present embodiment is as follows:
Step 1:4, the preparation of 4 '-dibromo triphenylamines (1), reaction equation are as follows:
The bromo- 4- iodobenzene (41.7g, 0.148mol) of 1- and aniline (5.5g, 0.059mol) are dissolved in 100mL dry toluene
In, sodium tert-butoxide (22.7g, 0.236mol) then is added, CuI (2.3g, 0.012mol) and 1,10- ferrosin (4.3g,
0.023mol), it is heated to 115 DEG C of reaction 18h under nitrogen atmosphere, is concentrated after cooling and removes toluene, deionized water and dichloro is added
Methane is extracted, and the organic layer obtained through liquid separation is dry with anhydrous magnesium sulfate, filters, after vacuum distillation, using petroleum ether as
Solvent carries out column chromatography for separation purification, obtains thick product, yield about 85% (20.2g)；
Step 2:6- (4- ((4- (6- (two (4- methoxyphenyl) amino) naphthylamines -2- base) phenyl) (phenyl) amino) benzene
Base)-N, the preparation of (4- methoxyphenyl) naphthalene -2- amine of N- bis- (TPA1), reaction equation is as follows:
In N2Under atmosphere, by 4,4 '-dibromo triphenylamines (2.0g, 4.96mmol), N, N- bis- (4- methoxyphenyl) -6-
(4,4,5,5- tetramethyl -1,3,2- dioxaborolan base) -2- naphthylamines (5.0g, 10.42mmol), tetra-triphenylphosphine palladium
(62mg, 0.053mmol), wet chemical (2mol/L, 10ml) and ethyl alcohol (10mL) are added in toluene (70mL), reaction
110 DEG C of stirring 10h are heated to, crude product is concentrated after having reacted and removes toluene, are then extracted with deionized water and methylene chloride
It takes, carries out separating-purifying using silica gel column chromatography after organic layer is concentrated, the solvent of column chromatography for separation uses dense first
Degree gradient is the mixed solution of petroleum ether and methylene chloride that volume ratio is 3:1,2:1,1:1, is finally directly made with methylene chloride
It for solvent, obtains product as light yellow solid (TPA1), yield about 87% (4.1g)；
1 small organic molecule hole injection of the embodiment of the present invention/transmission material TPA1 is tested below:
Fig. 1 be embodiment 1 prepare small organic molecule hole injection/transmission material TPA1 nuclear magnetic resonance spectroscopy (a) and
Carbon-13 nmr spectra (b) figure.
(1) nuclear magnetic resonance spectroscopy:
1H NMR (400MHz, DMSO) δ 8.01 (s, 2H), 7.80-7.59 (m, 10H), 7.38-7.30 (t, J=8.2Hz,
2H),7.17–7.01(m,19H),6.920(dt,J1=9.0, J2=3.4Hz, 8H), 3.74 (s, 12H)
Carbon-13 nmr spectra:
13C NMR(126MHz,DMSO)δ156.21,147.40,146.71,146.69,140.69,134.89,134.80,
133.65,130.10,129.48,129.22,127.99,127.49,127.00,125.53,124.75,124.61,124.40,
123.82,122.42,115.44,114.88,55.69.
(2) Photophysics
To embodiment 1 prepare small organic molecule hole injection/transmission material TPA1 in toluene solution (1.0 × 10-5mol
L-1) and quartz glass on film carry out respectively ultravioletvisible absorption and photoluminescence spectra characterization.Fig. 2 is the preparation of embodiment 1
Small organic molecule hole injection/transmission material TPA1 ultraviolet-visible absorption spectroscopy and fluorescence emission spectrum (a) and low temperature phosphorus
Optical emission spectroscopy (b) figure.The optical band gap that TPA1 can be calculated from the ABSORPTION EDGE of the film of Fig. 2 (a) is 2.84eV；From figure
The triplet that TPA1 can be calculated in 2 (b) antenna effect emission peak is 2.63eV.
(3) macroscopic property:
Thermogravimetic analysis (TGA) (TGA) is to lead to nitrogen protection on TGA2050 (TA instruments) thermogravimetric analyzer with 20
DEG C/determination of heating rate of min；Differential scanning calorimetric analysis (DSC) uses 204 F1 thermal analyzer of NETZSCH DSC, In
Under nitrogen protection, with the heating rate of 10 DEG C/min to 400 DEG C since -30 DEG C, -30 DEG C then are cooled to 20 DEG C/min,
Constant temperature 5min is tested with the heating rate of 10 DEG C/min to 400 DEG C again.
Fig. 3 is small organic molecule hole injection/transmission material TPA1 thermal weight loss (TGA) curve (a) prepared by embodiment 1
Calorimetric (DSC) curve (b) is scanned with differential.
Available by TGA curve, the decomposition temperature (temperature when weightlessness 1%) of TPA1 is 434 DEG C, can by DSC curve
To obtain, the glass transition temperature of TPA1 is up to 136 DEG C, it can be seen that, TPA1 has high thermal stability and good
Film morphological stability.
(4) energy level is tested:
HOMO energy level is calculated by ultraviolet photoelectron spectroscopy, the TPA1 film that 10nm is deposited on ITO is tested.Figure
The low kinetic energy area (a) of the 4 small organic molecule hole injection/transmission material TPA1 ultraviolet photoelectron spectroscopys prepared for embodiment 1
With the valence band spectrum close to fermi level area (b).It is -5.07eV that HOMO energy level, which is calculated, shows that material has suitable HOMO
Value, is conducive to the injection and taking-up in hole；It is about -2.23eV that its lumo energy, which is calculated, according to the optical band gap of TPA1.
(5) hole mobility is tested:
Preparation list hole device ITO/TPA1:F4-TCNQ (150nm, 4%)/Al, F4-TCNQ (2,3,5,6- tetra- fluoro- 7,
Tetra- cyanogen dimethyl-parabenzoquinone of 7', 8,8'-) it is P-type dopant.
Specially by resistance be 10-20 Ω/sq. tin indium oxide (ITO) electro-conductive glass substrate successively through deionized water,
Acetone, detergent, deionized water and isopropanol are cleaned by ultrasonic 15min respectively.After oven drying, by above-mentioned processed ITO
Glass substrate is 3 × 10-4Under the vacuum of Pa, each organic function layer and metal Al cathode is successively deposited.Film thickness Veeco
The measurement of Dektak150 step instrument, the deposition rate of metal electrode vapor deposition and its thickness/speed of thickness Sycon Instrument
Spend instrument STM -100 measurement.According to current density voltage curve, hole is calculated by space charge limited current (SCLC) method and is moved
Shifting rate.
Fig. 5 is that small organic molecule hole injection/transmission material TPA1 prepared by embodiment 1 adulterates the single empty of 4%F4-TCNQ
The current density voltage curve (a) and current density of cave mobility test1/2Voltage curve (b) figure.
As shown in Fig. 5 (a), the conductivity for being derived by 1 gained TPA1 of the embodiment of the present invention is 3.2 × 10-4S m-1, again
By being calculated according to SCLC shown in Fig. 5 (b), hole injection/transmission material TPA1 doping 4%F4-TCNQ of embodiment 1
Hole mobility is 5.62 × 10-4cm2V-1s-1。
(6) TPA1 is as doping hole-injecting material, using the table of the organic electroluminescence feux rouges phosphorescent devices of vacuum vapour deposition
Levy result:
Specific device architecture are as follows: ITO/TPA1:F4-TCNQ (100nm, 4%)/NPB (20nm)/Bebq2:Ir(MDQ)2
(acac) (40nm, 5%)/TRZ-m-Phen:Liq (30nm, mass ratio 1:1)/Liq (1nm)/Al.Wherein, TPA1:F4-
TCNQ is used as hole as hole injection layer, NPB (N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines)
Transport layer, Bebq2(bis- (10- hydroxy benzo [h] quinoline) berylliums): Ir (MDQ)2(acac) ((acetylacetone,2,4-pentanedione) bis- (2- methyldiphenyls
And [f, h] quinoxaline) close iridium) it is used as phosphorescence red light luminescent layer, TRZ-m-Phen:Liq is as electron transfer layer (preparation method ginseng
Pass the examination 108409730 A of state Patent Publication CN), Liq (8-hydroxyquinoline-lithium) is used as electron injecting layer.
Device detailed preparation process is as follows:
By resistance be 10-20 Ω/sq. tin indium oxide (ITO) electro-conductive glass substrate successively through deionized water, acetone, wash
It washs agent, deionized water and isopropanol and is cleaned by ultrasonic 20min respectively.After oven drying, by above-mentioned processed ito glass substrate
3 × 10-4Under the vacuum of Pa, each organic function layer and metal Al cathode is successively deposited.Film thickness Veeco
The measurement of Dektak150 step instrument.The deposition rate of metal electrode vapor deposition and its thickness/speed of thickness Sycon Instrument
Spend instrument STM -100 measurement.
Fig. 6 (a) is that small organic molecule hole injection/transmission material TPA1 doping 4%F4-TCNQ prepared by embodiment 1 has
Current density-voltage-brightness curve of machine red electroluminescent phosphorescent devices；
Fig. 6 (b) is that small organic molecule hole injection/transmission material TPA1 doping 4%F4-TCNQ prepared by embodiment 1 has
Current efficiency-brightness curve of machine red electroluminescent phosphorescent devices；
Fig. 6 (c) is that small organic molecule hole injection/transmission material TPA1 doping 4%F4-TCNQ prepared by embodiment 1 has
Power efficiency-brightness curve of machine red electroluminescent phosphorescent devices；
Fig. 6 (d) is that small organic molecule hole injection/transmission material TPA1 doping 4%F4-TCNQ prepared by embodiment 1 has
Electroluminescent intensity-wavelength curve of machine red electroluminescent phosphorescent devices；
Fig. 6 (e) is that small organic molecule hole injection/transmission material TPA1 doping 4%F4-TCNQ prepared by embodiment 1 has
Brightness-time graph of machine red electroluminescent phosphorescent devices；
It is available by Fig. 6 (a)~(c), F4-TCNQ is being adulterated as the organic electroluminescence feux rouges of hole injection layer using TPA1
In phosphorescent devices, in 1000cd/m2Brightness under, the current efficiency of device is 12.8cd A-1, power efficiency is 10.0lm W-1；
Fig. 6 (d) shows the electroluminescent peak value about 618nm of the device, is typical red emission.
It it can be seen that, is 1000cd m in starting brightness by Fig. 6 (e)-2When, the service life t of device95(t95For the brightness of device
From 1000cd m-2Decay to 950cd m-2Time used) it is up to 480h, show TPA1 in the hot evaporation feux rouges phosphorescent devices
In have good device stability.
(7) TPA1 is as doping hole mobile material, by the way of solution spin coating processing, in perovskite photovoltaic device
Characterization result:
Specific device architecture are as follows: ITO/SnO2/CsPbI3/TPA1:LAD/MoO3/Al
Device fabrication process: by resistance be 10-20 Ω/mouth tin indium oxide (ITO) electro-conductive glass substrate successively gone from
Sub- water, acetone, detergent, deionized water and isopropanol are cleaned by ultrasonic 20min respectively, then in oven drying, through oxygen plasma
Body handles 1min, then spin coating SnO2Nanoparticle glue liquid solution (is purchased from Alfa Aesar), 20~30nm of thickness, revolving speed
3500rpm, 150 DEG C of annealing 30min.Then, in SnO2Surface spin coating CsPbI3(by PbI2Body is added with molar ratio 1:1 with CsI
Product ratio is to be uniformly mixed and be prepared in the DMF/DMSO mixed solution of 4:1.The wherein PbI of every 0.80mmol2It is corresponding to be added
The DMF/DMSO of 1mL), revolving speed and time are 1500rpm/9s and 4000rpm/30s, then in 330 DEG C of annealing 2min.Exist again
CsPbI3The chlorobenzene of surface spin quality ratio TPA1:LAD (LAD=tri- (pentafluorophenyl group) boron, CAS:1109-15-5)=1:0.04
(total concentration is 40mg mL to solution–1), revolving speed 3000rpm.Then < 5 × 10-4Under the vacuum of Pa, MoO is deposited3(vapor deposition speed
Rate isWith a thickness of 10nm.Finally, < 5 × 10-4Under the vacuum of Pa, evaporated metal layer arrives 120nm's with a thickness of 80
Al.The effective area of the device is 0.058cm2.Cleaning and SnO except ITO2The preparation process of film is complete in atmospheric environment
At, remaining all link is completed in the glove box of nitrogen atmosphere.
Fig. 7 be the embodiment of the present invention 1 prepare the injection of small organic molecule hole/transmission material TPA1 adulterate 4%LAD after with
Bustamentite caesium is the current density voltage curve of the positive type perovskite photovoltaic device of active layer.It can be obtained, be passed through by device detection result
Light intensity is 100mW cm-2Solar simulation light irradiation, acquired device performance is as follows, open-circuit voltage (Voc): 0.96V, short circuit
Electric current (Jsc): 18.87mA cm-2, fill factor (FF): 63.08%, energy conversion efficiency (PCE): 11.47%.
Embodiment 2
Small organic molecule hole injection/transmission material structural formula of the present embodiment is specific as follows:
Small organic molecule hole injection/transmission material TPA2 preparation method of the present embodiment is as follows:
The preparation of the bromo- N- of step 1:4- (4- bromophenyl)-N- (4- methoxyphenyl) aniline, reaction equation are as follows:
Step (1) in step (1) and embodiment 1 the difference is that, the aniline 4- first of step (1) in embodiment 1
Oxygroup aniline replaces, yield about 80% (14.0g)；
Step 2:6- (4- ((4- (6- (two (4- methoxyphenyl) amino) naphthylamines -2- base) phenyl) (4- methoxyphenyl)
Amino) phenyl)-N, the preparation of (4- methoxyphenyl) naphthalene -2- amine of N- bis- (TPA2), reaction equation is as follows:
Step (2) operating process and 1 step of embodiment (2) the difference is that, the reaction of step (2) in embodiment 1
4,4 '-dibromo triphenylamine of object is replaced with the bromo- N- of 4- (4- bromophenyl)-N- (4- methoxyphenyl) aniline, column chromatography for separation expansion
Agent uses volume ratio petroleum ether at the beginning: then methylene chloride=2:1 arrives 1:1, finally directly uses methylene chloride.Yield is about
81% (4.6g)；
2 small organic molecule hole injection of the embodiment of the present invention/transmission material TPA2 is tested below:
Fig. 8 (a) and Fig. 8 (b) is respectively small organic molecule hole injection/transmission material prepared by the embodiment of the present invention 2
The nuclear magnetic resonance spectroscopy and carbon-13 nmr spectra of TPA2.
(1) nuclear magnetic resonance spectroscopy:
1H NMR (400MHz, DMSO) δ 8.00 (s, 2H), 7.76 (d, J=8.8Hz, 2H), 7.71-7.60 (m, 8H),
7.13–7.02(m,18H),6.99–6.90(m,10H),3.76(s,3H),3.74(s,12H).
Carbon-13 nmr spectra:
13C NMR(126MHz,DMSO)δ156.69,156.20,147.06,146.62,140.71,140.04,135.00,
133.92,133.58,129.44,129.26,127.94,127.83,127.47,126.97,125.52,124.43,123.13,
122.43,115.60,115.44,114.94,55.72,55.69
(2) Photophysics
To embodiment 2 prepare small organic molecule hole injection/transmission material TPA2 in toluene solution (1.0 × 10-5mol
L-1) and quartz glass on film carry out ultraviolet-ray visible absorbing, photoluminescence spectra and antenna effect emission spectrum characterization.Fig. 9
The small organic molecule hole injection/transmission material TPA2 ultravioletvisible absorption and fluorescence emission spectrum (a) prepared for embodiment 2
With antenna effect emission spectrum (b) figure.The optical band gap that TPA2 can be calculated from the ABSORPTION EDGE of the film of Fig. 9 (a) is
2.77eV；The triplet that TPA2 can be calculated from the antenna effect emission peak of Fig. 9 (b) is 2.65eV.
(3) macroscopic property:
Thermogravimetic analysis (TGA) (TGA) is to lead to nitrogen protection on TGA2050 (TA instruments) thermogravimetric analyzer with 20
DEG C/determination of heating rate of min；Differential scanning calorimetric analysis (DSC) uses 204 F1 thermal analyzer of NETZSCH DSC, In
Under nitrogen protection, with the heating rate of 10 DEG C/min to 390 DEG C since -30 DEG C, -30 DEG C then are cooled to 20 DEG C/min,
Constant temperature 5min is tested with the heating rate of 10 DEG C/min to 390 DEG C again.
Figure 10 is that small organic molecule hole injection/transmission material TPA2 TGA (a) and DSC (b) prepared by embodiment 2 are bent
Line chart.Available by TGA curve, the thermal decomposition temperature of TPA2 (temperature when weightlessness 1%) is 431 DEG C, can be with by DSC curve
It obtains, the glass transition temperature of TPA2 is up to 131 DEG C, shows that TPA thermal stability is good, is conducive to device stability.
(4) energy level is tested:
By ultraviolet photoelectron spectroscopy test result calculations HOMO energy level, the TPA2 film that 10nm is deposited on ITO is carried out
Test.Figure 11 is the low dynamic of small organic molecule hole injection/transmission material TPA2 ultraviolet photoelectron spectroscopy prepared by embodiment 2
It can area (a) and the valence band spectrogram close to fermi level area (b).Calculating HOMO energy level is -5.02eV, shows that material has and is suitable for
HOMO value, be conducive to the injection and taking-up in hole.According to the optical band gap of TPA2 be calculated its lumo energy about-
2.25eV。
(5) hole mobility is tested:
List hole device ITO/TPA2:F4-TCNQ (150nm, 4%)/Al is prepared, F4-TCNQ is P-type dopant.
According to current density voltage curve, hole mobility is calculated by space charge limited current SCLC method.
Device fabrication process, the hole mobility test of reference implementation example 1.
Figure 12 is the list that small organic molecule hole injection/transmission material TPA2 prepared by embodiment 2 adulterates 4%F4-TCNQ
The current density voltage curve (a) and current density of hole mobility test1/2Voltage curve (b) figure.
As shown in Figure 12 (a), the conductivity that 2 gained TPA2 of embodiment is calculated is 3.2 × 10-4S m-1, and by Figure 12
(b) it shown in, is calculated according to SCLC, the hole hole injection/transmission material TPA2 doping 4%F4-TCNQ of embodiment 2 is moved
Shifting rate is 3.72 × 10-4cm2V-1s-1。
(6) TPA2 is as doping hole-injecting material, using the table of the organic electroluminescence feux rouges phosphorescent devices of vacuum vapour deposition
Levy result:
Specific device architecture are as follows: ITO/TPA2:F4-TCNQ (100nm, 4%)/NPB (20nm)/Bebq2:Ir(MDQ)2
(acac) (40nm, 5%)/TRZ-m-Phen:Liq (30nm, 1:1)/Liq (1nm)/Al.Wherein, TPA2:F4-TCNQ is as empty
Cave implanted layer, NPB is as hole transmission layer, Bebq2:Ir(MDQ)2(acac) it is used as phosphorescence red light luminescent layer, TRZ-m-Phen:
Liq is as electron transfer layer, and Liq is as electron injecting layer.
Device detailed preparation process, referring to embodiment 1.
Figure 13 (a) is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 has
Current density-voltage-brightness curve of machine red electroluminescent phosphorescent devices；
Figure 13 (b) is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 has
Current efficiency-brightness curve of machine red electroluminescent phosphorescent devices；
Figure 13 (c) is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 has
Power efficiency-brightness curve of machine red electroluminescent phosphorescent devices；
Figure 13 (d) is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 has
Electroluminescent intensity-wavelength curve of machine red electroluminescent phosphorescent devices；
Figure 13 (e) is that small organic molecule hole injection/transmission material TPA2 doping 4%F4-TCNQ prepared by embodiment 2 has
Brightness-time graph of machine red electroluminescent phosphorescent devices；
It is available by Figure 13 (a)~(c), red using the organic electroluminescence of TPA2 doping F4-TCNQ as hole injection layer
In light phosphorescent devices, in 1000cd/m2Brightness under, the current efficiency of device is 12.6cdA-1, power efficiency is 9.4lm W-1；
By the electroluminescent peak value about 618nm of the available device of Figure 13 (d).
It it can be seen that, is 1000cd m in starting brightness by Figure 13 (e)-2When, the service life t of device95Up to 569h.
(7) TPA2 is as doping hole mobile material, by the way of solution spin coating processing, in perovskite photovoltaic device
Characterization result:
Specific device architecture are as follows: ITO/SnO2/CsPbI3/TPA2:LAD/MoO3/Al
Device fabrication process difference from example 1 is that, TPA1 is replaced with TPA2.
Figure 14 is after small organic molecule hole injection/transmission material TPA2 prepared by the embodiment of the present invention 2 adulterates 4%LAD
Using bustamentite caesium as the current density voltage curve of the positive type perovskite photovoltaic device of active layer.As seen from the figure, it is through light intensity
100mW cm-2Solar simulation light irradiation, acquired device performance is as follows: open-circuit voltage (Voc): 0.97V, short circuit current
(Jsc):18.93mA cm-2, fill factor (FF): 62.57%, energy conversion efficiency (PCE): 11.53%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. small organic molecule hole injection/transmission material, which is characterized in that its structural formula is as shown in formula I:
WhereinWherein, Ar1、Ar2With Ar3It independently is unsubstituted phenyl ring, condensed ring or loop coil aromatic hydrocarbons,
Or it independently is phenyl ring, condensed ring or the loop coil aromatic hydrocarbons replaced through alkyl, alkoxy or alkylthio group that carbon atom number is respectively 1~6；
Wherein the carbon atom number of phenyl ring, condensed ring or loop coil aromatic hydrocarbons is 6-40.
2. small organic molecule hole injection/transmission material according to claim 1, which is characterized in that the R group represents
Chemical structure it is as follows:
Wherein * indicates the tie point of the R group.
3. small organic molecule hole injection/transmission material according to claim 1, which is characterized in that its structural formula is
One of TPA1 or TPA2:
4. the preparation method of a kind of claims 1 or 2 or the 3 small organic molecule hole injection/transmission materials, feature exist
In, comprising the following steps:
(1) it in organic solvent and catalyst system, is reacted after bromine iodine substituted aromatic compound is mixed with aminated compounds,
Reaction solution is purified after reaction, obtains brominated intermediate；
(2) in organic solvent and catalyst system, by brominated intermediate and N, N- bis- (4- methoxyphenyl)-obtained by step (1)
Coupling reaction is carried out after the mixing of 6- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan base) -2- naphthylamines, after reaction
Crude product is obtained, by after purification, obtaining small organic molecule hole injection/transmission material.
5. the preparation method of small organic molecule hole injection/transmission material according to claim 4, it is characterised in that:
Catalyst system described in step (1) includes alkali compounds and catalyst；Wherein, the alkali compounds is the tert-butyl alcohol
At least one of sodium or potassium tert-butoxide；The catalyst is 1,10- ferrosin and cuprous iodide；
Step (1) the bromine iodine substituted aromatic compound is the bromo- 4- iodobenzene of 1-；
Step (1) aminated compounds is at least one of aniline and 4- aminoanisole；
Step (1) organic solvent is at least one of toluene, N,N-dimethylformamide and anhydrous tetrahydro furan.
6. the preparation method of small organic molecule hole injection/transmission material according to claim 5, it is characterised in that:
Aminated compounds described in step (1), bromine iodine substituted aromatic compound, alkali compounds, 1,10- ferrosin and iodate
Cuprous molar ratio is 1:(2.1~3): (3~6): (0.1~0.2): (0.2~0.4)；
The dosage of step (1) described organic solvent meet every 1mol bromine iodine substituted aromatic compound it is corresponding be added 300~
The organic solvent of 1000mL.
7. the preparation method of small organic molecule hole injection/transmission material according to claim 4, it is characterised in that:
Step (2) organic solvent is at least one of toluene and tetrahydrofuran；
Catalyst system described in step (2) includes catalyst and alkali compounds aqueous solution；Wherein, the catalyst includes four
Triphenylphosphine palladium and phase transfer catalyst；The alkali compounds aqueous solution is in wet chemical and aqueous sodium carbonate
It is at least one.
8. the preparation method of small organic molecule hole injection/transmission material according to claim 4, it is characterised in that:
Step (2) the brominated intermediate and N, N- bis- (4- methoxyphenyl) -6- (4,4,5,5- tetramethyl -1,3,2- dioxy
Miscellaneous boron heterocycle amyl) -2- naphthylamines, tetra-triphenylphosphine palladium, phase transfer catalyst and alkali compounds molar ratio be 1:(2.05
~2.2): (0.01~0.03): (20~50): (3~5).
9. the preparation method of small organic molecule hole injection/transmission material according to claim 4, it is characterised in that:
Reaction described in step (1) is in 110 DEG C~120 DEG C 15~30h of reaction；
Coupling reaction condition described in step (2) is that 9~14h is reacted at 100~120 DEG C.
10. any one small organic molecule hole injection/transmission material is in organic electroluminescence according to claim 1~3
Application in part and efficient calcium titanium photovoltaic device.
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| WO2021036158A1 (en) * | 2019-08-28 | 2021-03-04 | 华南理工大学 | Organic small molecule hole injection/transport material and preparation method therefor and application thereof |
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| US20080076942A1 (en) * | 2006-09-22 | 2008-03-27 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescence device using the same |
| CN107954884A (en) * | 2017-11-16 | 2018-04-24 | 华南理工大学 | High glass-transition temperature hole-injecting material and its preparation and application |
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| US20080076942A1 (en) * | 2006-09-22 | 2008-03-27 | Idemitsu Kosan Co., Ltd. | Aromatic amine derivative and organic electroluminescence device using the same |
| CN107954884A (en) * | 2017-11-16 | 2018-04-24 | 华南理工大学 | High glass-transition temperature hole-injecting material and its preparation and application |
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| CN111233676A (en) * | 2020-01-17 | 2020-06-05 | 华南理工大学 | High-performance hole transport material and preparation and application thereof |
| CN111233676B (en) * | 2020-01-17 | 2022-03-29 | 华南理工大学 | High-performance hole transport material and preparation and application thereof |
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