CN110511212A - A kind of bipolarity D-A type material of main part and organic electroluminescence device - Google Patents
A kind of bipolarity D-A type material of main part and organic electroluminescence device Download PDFInfo
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract
It is that there is the bipolarity compound comprising carbazole unit and pyridines unit, bipolarity carrier transmission performance of the series compound with good thermal stability and dissolubility, film forming and balance the invention discloses a kind of bipolarity D-A type material of main part.Meanwhile the preparation method is simple, synthetic thread is short out, yield is high, raw material are easy to get, environmental-friendly, has huge application prospect in terms of high-performance solwution method prepares device.Bipolarity D-A type material of main part of the invention is applied in OLED device, the performance of device is significantly improved.
Description
Technical field
The present invention relates to a kind of organic compound and organic electroluminescence devices, more particularly to a kind of bipolarity D-A type
Material of main part and organic electroluminescence device.
Background technique
Organic electroluminescence device (OLEDs) has that low cost, low-power consumption, that flexible, rich in color, visual angle is wide etc. is excellent
Point, in fields such as solid-state lighting, FPD using increasingly extensive.It is further deep for the research of OLEDs at present, but it is logical
It is still a problem that the solwution method for crossing low cost, which prepares efficient, stable device,.
For traditional phosphor material, be entrained in material of main part as object can effectively avoid concentration quenching or
Person's triplet state buries in oblivion (Baldo, M.A.；O ' Brien, D.F.；You, Y.；Shoustikov, A.；Sibley, S.；Thompson,
M.E.；Forrest, S.R.Nature 1998,395,151-154), but by way of host-guest system, be conducive to shine
The level-density parameter of material reduces the potential barrier of charge transmission, improves the luminous efficiency of device.Choi et al. (Choi S, Godumala
M, Lee J H, et a1.Journal of Materials Chemistry C, 2017,5 (26): 6570-6577) synthesis
A series of by core, pyridine, carbazole of silicon tetraphenyl is the material of main part SiCz3Py1, SiCz2Py2, SiCz1Py3 of arm, device
EQEs respectively reached 15.1%, 18.7%, 18.8%.Kwon et al. (Ahn D H, Moon J S, Kim S W, et
A1.Organic Electronics, 2018,59 (59): 39-44) synthesize two kinds of carbazole derivates main bodys comprising phosphorus oxygen base
Material PPO2,3DCPO, triplet with higher, the device EQE after adulterating blue light TADF material DMAC-DPS reach
27.8% and 23.1%.Yasuda et al. (Park IS, Seo H, Tachibana H, et a1.ACS applied
Materials&interfaces, 2017,9 (3): 2693-2700) carbazole derivates bipolarity main body of the synthesis comprising phosphorus oxygen base
Material C z-PO, the material have preferable stability and higher triplet, and the film for mixing 4CzIPN is with higher
Fluorescence quantum efficiency, EQE reach 21.7%.Kippelen et al. (Gaj MP, Fuentes-Hernandez C, Zhang Y, et
A1.Organic Electronics, 2015,16 (16): 109-112) synthesize a kind of carbazole analog derivative pair comprising sulfuryl
Polarity main body mCPSOB, EQE have reached 26.5%.Pei et al. (Pei J, Du X, Li C, et al..Organic
Electronics, 2017,50 (50): 153-160) synthesize the carbazole derivates master that two include the high distortion of pyridyl group
Body material: CzDPPy and tCzDPPy, triplet reach 2.6eV, and current efficiency reaches 34.8cd/A and 28.9cd/A,
Luminous efficiency reaches 33.1lm/W and 23.3lm/W.Li et al. (LiW, Li J, Wang F, et al.ACS applied
Materials&interfaces, 2015,7 (47): 26206-26216) synthesized it is a series of using pyrroles as receptor, carbazole be to
The D-A type material of main part qo-CzDPz of body, the device efficiency of the material doped 2CzPN reach 26.2cd/A and 15.6lm/W.
Above-mentioned material is prepared by the mode based on small molecule vacuum evaporation mostly, is difficult to be suitable for cheap solwution method preparation
Device.Solwution method prepares device, it is desirable that material system has good film forming and morphology stability, good carrier transport
Ability, higher triplet.It is compared than traditional vacuum evaporation apparent advantage, such as at low cost；Utilize big face
Long-pending spin coating, inkjet printing and printing technology keep its processing performance good；The waste of material is relatively fewer, while can be accurately
Control doping concentration.
Summary of the invention
Goal of the invention: an object of the present invention is to provide a kind of bipolarity D-A type material of main part, is suitble to solwution method preparation
Electroluminescent device, and with the bipolarity carrier transport of good thermal stability and dissolubility, film forming and balance
Performance, preparation method is simple, yield is high；The second object of the present invention is to provide a kind of organic electroluminescence device, by bipolarity
D-A type material of main part is applied in preparing electroluminescent device, and the performance of device is improved.
Technical solution: bipolarity D-A type material of main part of the invention, structural formula are any in following six kinds of structures
Kind:
Wherein, the English code name below above-mentioned every kind of structural formula (3PymCz, 4PymCz, 3PypCz, 4PypCz, 3PyoCz,
It 4PyoCz) is respectively the abbreviation for corresponding to every kind of structural formula.
The general structure of the bipolarity D-A type material of main part are as follows:
Wherein, A indicates receptor unit, and the structural formula of A isOrReceptor unit is by changing the position linked
It sets, there is two kinds of on-link mode (OLM)s of 3- pyridine and 4- pyridine respectively；
Have three groups of link positions on the middle meta-terphenyl of above structure general formula, be respectively meta position (m, m '), contraposition (p, p '),
Ortho position (o, o '), one donor monomer D of any group of link in this three groups of link positions, wherein the structural formula of D be
The preparation method of above-mentioned bipolarity D-A type material of main part includes synthetic intermediate 1,2,3；Intermediate 4,5,6；It is intermediate
Body 7,8；Specifically comprise the following steps:
(1) synthesis of intermediate 1,2,3:
The synthesis of intermediate 1: 3,6- di-t-butyl carbazole and a bromo-iodobenzene being added in flask, and potassium carbonate is added,
DMPU and o-dichlorohenzene are injected after pump drainage in crown ether -6 18- under nitrogen atmosphere；After stirring at normal temperature, cuprous iodide is added and carries out
Reaction synthesis；
The synthesis of intermediate 2: bromo-iodobenzene between in above-mentioned 1 synthetic method of intermediate is changed to bromo-iodobenzene；
The synthesis of intermediate 3: bromo-iodobenzene between in above-mentioned 1 synthetic method of intermediate is changed to adjacent bromo-iodobenzene.
(2) synthesis of intermediate 4,5,6:
The synthesis of intermediate 4: by intermediate 1 and connection boric acid pinacol rouge, potassium acetate, the dioxane strictly removed water is added
It mixes, after stirring at normal temperature, palladium acetate is added and is protected from light under nitrogen atmosphere；
Similarly, during the synthetic method of intermediate 5,6 only need to change respectively the intermediate 1 in 4 synthesis process of intermediate into
Mesosome 2, intermediate 3.
(3) synthesis of intermediate 7,8:
The synthesis of intermediate 7: by 1,3,5- tribromo-benzene and 3- pyridine boronic acid pinacol ester and toluene, ethyl alcohol, potassium carbonate
Solution mixes, and after stirring at normal temperature, tetrakis triphenylphosphine palladium is added, then heating is reacted to obtain the final product；
The synthesis of intermediate 8: the 3- pyridine boronic acid pinacol ester in the synthetic method of intermediate 7 is changed into 4- pyridine boronic acid
Pinacol ester.
(4) synthesis of material of main part:
The synthesis of 3PymCz: intermediate 4, intermediate 7 are mixed, and the solution of potassium carbonate of toluene, ethyl alcohol sum, room temperature are added afterwards
After stirring, tetrakis triphenylphosphine palladium is added, heating is reacted to obtain the final product；
The synthesis of 4PymCz: intermediate 4, intermediate 8 are synthesized according to the synthetic route of 3PymCz to obtain the final product；
The synthesis of 3PypCz: intermediate 5, intermediate 7 are synthesized according to the synthetic route of 3PymCz to obtain the final product；
The synthesis of 4PypCz: intermediate 5, intermediate 8 are synthesized according to the synthetic route of 3PymCz to obtain the final product；
The synthesis of 3PyoCz: intermediate 6, intermediate 7 are synthesized according to the synthetic route of 3PymCz to obtain the final product；
The synthesis of 4PyoCz: intermediate 6, intermediate 8 are synthesized according to the synthetic route of 3PymCz to obtain the final product.
The synthetic route of D-A bipolar host material of the invention is as follows, and reflux therein indicates to be condensed back.
Preferably, the bipolarity D-A type material of main part is 3PyoCz or 4PypCz；It has good as material of main part
Good film forming and morphology stability, good carrier transport ability, higher triplet.
The present invention also provides a kind of organic electroluminescence device, including luminescent layer, the material of the luminescent layer is above-mentioned
D-A bipolar host material.The preparation method of device uses routine preparation method in the prior art.
In order to further increase the performance of OLED, the material of the luminescent layer further includes being entrained in the D-A bipolarity master
Phosphor material in body material.
Preferably, the phosphor material is blue emitting phosphor material, orange phosphor material or green phosphorescent material；The doping
Phosphor material in luminescent layer proportion be 5wt%~30wt%.Wherein blue phosphor materials can for FIrpic or its
His common blue phosphor materials；Orange phosphor material can be Ir (bt)2Acac or other common orange phosphor materials；It is green
Color phosphor material can be Ir (ppy)2Acac or other common green phosphorescent materials.
Preferably, the material of main part is 3PyoCz, and the phosphor material of doping proportion in luminescent layer is
5wt%~10wt%.The selection of material of main part and phosphor material mix in proper proportions, so that the comprehensive performance of device reaches
To optimal value.
Preferably, the material of main part is 3PyoCz or 4PypCz；The phosphor material of the doping is orange phosphor material
Or green phosphorescent material.
Further, in order to improve the performance of device, the luminescent layer further includes being entrained in material of main part 3PyoCz
TAPC and/or TCTA forms hybrid agent with material of main part 3PyoCz.When the material of main part forms hybrid agent, than
It is more excellent using the reference device performance of single main body.
Preferably, the incorporation of TAPC, TCTA also have larger impact to the performance of device；TAPC and TCTA are mixed when simultaneously
Hybrid agent is formed, the mass ratio of described 3PyoCz, TAPC, TCTA are 6~8: 1~3: 1.
When individually incorporation TAPC forms hybrid agent, the mass ratio of described 3PyoCz, TAPC are 3~5: 1.
Inventive principle: to-receptor type (D-A) bipolarity small organic molecule material of main part, transmission electronics and sky are provided simultaneously with
The ability in cave can simplify device architecture, improve device efficiency, is one of the preferred material of solwution method processing device；But mesh
The bipolar host material that preceding suitable solwution method prepares electroluminescent device is also fewer；Therefore the present invention provides a kind of bipolar
Property material of main part preparation method, provide series include carbazole unit and pyridines unit bipolarity compound, the series
Compound is suitble to the bipolarity carrier transmission performance of good thermal stability and dissolubility, film forming and balance
Solwution method prepares electroluminescent device；Meanwhile the preparation method is simple, synthetic thread is short out, yield is high, raw material are easy to get, environment
Close friend has huge application prospect in terms of high-performance solwution method prepares device；By bipolarity D-A type main body material of the invention
Material is applied in OLED device, and the performance of device is significantly improved.
The utility model has the advantages that compared with prior art
(1) bipolarity D-A type material of main part of the invention has good film forming and morphology stability, is suitble to solwution method
Prepare electroluminescent device；
(2) bipolarity D-A type material of main part of the invention has good carrier transport ability, wherein being made with 3PyoCz
Based on material device electronic mobility be 2.60 × 10-3cm2/ (VS), and the mobility in hole is 5.97 × 10-4cm2/
(VS), be conducive to the injection and transmission of carrier；
(3) bipolarity D-A type material of main part of the invention has suitable HOMO, lumo energy, energy level between Subjective and Objective
Carrier transport is convenient in matching；
(4) synthetic method for being used to prepare bipolarity D-A type material of main part in the present invention is simple, strong operability, synthesis
It is at low cost；
(5) bipolarity D-A type material of main part of the invention has good application prospect, the OLED device of preparation in OLED
The maximum current efficiency of part has reached 45.2cd/A, and maximum brightness has reached 36917cd/m2；
(6) present invention forms hybrid agent, hybrid agent and phosphorescence material by mixing TAPC, TCTA in material of main part
Material is used as luminescent layer, and device performance is more excellent than the device performance of single main body；
Detailed description of the invention
Fig. 1 is six kinds of D-A type bipolar host materials abosrption spectrogram under filminess；
Fig. 2 is six kinds of D-A type bipolar host materials abosrption spectrogram in different solutions respectively；
Fig. 3 is six kinds of D-A type bipolar host materials fluorescent emission spectrogram in different solutions respectively；
Fig. 4 is the antenna effect spectrogram of six kinds of D-A type bipolar host materials；
Fig. 5 is the differential scanning calorimetric thermogram and thermogravimetric analysis figure of six kinds of D-A type bipolar host materials；
Fig. 6 is that 3PyoCz adulterates various concentration Ir (ppy)2The film morphology phenogram of acac.
Fig. 7 is the chemical property analysis chart of six kinds of D-A type bipolar host materials；
Fig. 8 is the not lower six kinds of D-A types bipolar host material list carrier transmission performance figure of same electric field；It is wherein a) electric for list
Son；B) single hole；
Fig. 9 is that object FIrpic is doped to the device performance figure after six kinds of D-A type bipolar host materials；It wherein a) is electricity
Current density-voltage curve, b) be brightness-voltage curve, c) be current efficiency-brightness curve, d) it is electroluminescent light spectrogram；
Figure 10 is that 3PyoCz adulterates a small amount of TAPC, TCTA as the blue-light device performance map after hybrid agent；It a) is electricity
Current density-voltage curve, b) be brightness-voltage curve, c) be current efficiency-brightness curve, d) it is electroluminescent light spectrogram；
Figure 11 is object Ir (bt)2Acac is doped to the device performance figure after six kinds of D-A type bipolar host materials；A) it is
Current density voltage curve, b) be brightness-voltage curve, c) be current efficiency-brightness curve, d) it is electroluminescent light spectrogram；
Figure 12 is object Ir (ppy)2Acac is doped to the device performance figure after six kinds of D-A type bipolar host materials；a)
It is brightness-voltage curve, c for current efficiency-brightness curve, b)) be current density voltage curve, d) it is electroluminescent spectrum
Figure；
Figure 13 is that 3PyoCz adulterates a small amount of TAPC, TCTA as the green device performance map after hybrid agent；It a) is electricity
Current density-voltage curve, b) be brightness-voltage curve, c) be current efficiency-brightness curve, d) it is electroluminescent light spectrogram.
Specific embodiment
The reagent and material used in following embodiment can be commercially available on the market unless otherwise specified.Following reality
Applying 1HNMR and 13C NMR spectra involved in characterization of compound in example is the Varian produced by BruKer company
Mercury 400MHz nuclear magnetic resonance chemical analyser measures, and all samples are tested in deuterated chloroform；Mass spectrum is in cloth Shandong
It is measured on the Autoflex Speed MALDI-TOF of gram dalton company production.TMS,BF3Diethyl ether solution as reference into
Row measurement.
In following embodiment: FIrpic be bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics conjunction iridium, TAPC 4,
4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline], TCTA 4,4 ', 4 '-three (carbazole -9- base) triphenylamine, Ir (bt)
2acac is bis- (2- phenyl benzo thiophene) (acetylacetone,2,4-pentanedione) iridium, Ir (ppy)2Acac is acetopyruvic acid two (2- phenylpyridine) iridium；
The material that other English indicate unless otherwise specified, is well known to those skilled in the art common used material.
Synthetic example 1:
The present embodiment synthesizes the compound of structure shown in 3PymCz, the specific steps are as follows:
(1) synthetic intermediate 1: by bromine iodine between 5g (17.9mmol) 3,6- di-t-butyl carbazole and 5.07g (17.9mmol)
Benzene is added in three-necked flask, and 4.05g (29.1mmol) potassium carbonate, 0.05g (0.2mmol) 18- crown ether -6 is added.Pump drainage three
It is secondary, 2mL DMPU and 12mL o-dichlorohenzene is injected under nitrogen atmosphere.After stirring at normal temperature 15min, 0.343g is added
(0.179mmol) cuprous iodide, 150 DEG C of reaction about 3h, thin layer chromatography method point board monitoring extent of reaction.To the end of reacting
Afterwards, it is cooled to room temperature, vacuum distillation is washed with water after removing solvent, methylene chloride liquid separation extraction is added later, by what is obtained
Solution is spin-dried for, and with silica gel column chromatography column separating purification (eluant, eluent is pure petroleum ether), obtaining white solid intermediate 1 is 6.78g, is produced
Rate 87.3%.
Nucleus magnetic hydrogen spectrum: δ=8.13 (s, 2H) 1H NMR (400MHz, Chloroform-d), 7.74 (s, 1H), 7.56 (d, J
=7.8Hz, 1H), 7.52 (d, J=8.5Hz, 1H), 7.48 (d, J=8.5Hz, 2H), 7.45 (s, 1H), 7.36 (d, J=
8.6Hz, 2H), 1.47 (s, 18H).
(2) synthetic intermediate 4: take 4.344g (10.0mmol) intermediate 1 and 3.048g (12.0mmol) join boric acid frequency that
Alcohol ester is added in the strict drying three-necked flask of a 250mL, then the potassium acetate of 1.960g (20mmol), pump drainage are added immediately
After three times, the dioxane 60mL strictly removed water is added, after stirring at normal temperature half an hour, the vinegar of 0.029g (0.4mmol) is added
Sour palladium is protected from light under nitrogen atmosphere, 100 DEG C of reaction 48h.After reaction stops, washing, liquid separation extraction, with silica gel column chromatography point
From purifying (eluant, eluent is petroleum ether: ethyl acetate 20: 1, V/V), faint yellow solid 2.567g, yield 53.3% are obtained.
Nucleus magnetic hydrogen spectrum:1δ=8.14 (s, 2H) H NMR (400MHz, Chloroform-d), 7.99 (s, 1H), 7.87 (d, J
=6.9Hz, 1H), 7.63 (d, J=6.1Hz, 1H), 7.58 (t, J=7.4Hz, 1H), 7.46 (d, J=8.6Hz, 2H), 7.32
(d, J=8.6Hz, 2H), 1.47 (s, 18H), 1.35 (s, 12H).
(3) synthetic intermediate 7: by 1,3,5- tribromo-benzene of 0.944g (3.0mmol) and 0.615g (3.0mmol) 3- pyridine boron
Sour pinacol ester is added in three-necked flask, pump drainage three times after, be implanted sequentially 15mL toluene, 2mL ethyl alcohol, 3mL potassium carbonate is molten
After stirring at normal temperature half an hour, 0.139g (12%mmol) tetrakis triphenylphosphine palladium is added in liquid (2M).110 DEG C are subsequently heated to,
About for 24 hours, thin layer chromatography method contact plate monitors extent of reaction for reaction.After reaction, it is cooled to room temperature, with water and methylene chloride
Liquid separation extraction is carried out, subsequent column chromatography (eluant, eluent is petrol ether/ethyl acetate 5: 1, V/V) isolates and purifies, and obtains pale yellow colored solid
Body 3- (3,5- dibromobenzene) pyridine (7) 0.68g, yield 72.4%.
Nucleus magnetic hydrogen spectrum: δ=8.81 (s, 1H) 1H NMR (400MHz, Chloroform-d), 8.67 (d, J=7.9Hz,
1H), 7.84 (d, J=7.9Hz, 1H), 7.72 (s, 1H), 7.67 (s, 2H), 7.41 (t, J=4.0Hz, 1H).
(4) it synthesizes 3PymCz: 0.963g midbody compound 4 and 0.313g midbody compound 7 is added to three mouthfuls of burnings
Bottle in, pump drainage three times after, be implanted sequentially toluene 7mL, the solution of potassium carbonate 1mL of ethyl alcohol 2mL and 2mol/L.Stirring at normal temperature half is small
0.092g (8%mmol) tetrakis triphenylphosphine palladium is added in Shi Hou.110 DEG C are then raised temperature to, 48h is reacted.After stopping reaction, use
It after water and methylene chloride liquid separation extraction, is spin-dried for, crosses column (eluant, eluent is petroleum ether: ethyl acetate 10: 1, V/V) purification, obtain yellowish
Color solid 3PymCz 0.68g, yield 79.1%.
Nucleus magnetic hydrogen spectrum: δ=9.02 (s, 1H) 1H NMR (400MHz, Chloroform-d), 8.69 (s, 1H), 8.21 (s,
4H), 8.02 (d, J=7.9Hz, 1H), 7.97 (d, J=4.0Hz, 1H), 7.95 (s, 2H), 7.88 (s, 2H), 7.81 (d, J=
7.7Hz, 2H), 7.75 (t, J=7.8Hz, 2H), 7.65 (d, J=7.8Hz, 2H), 7.52 (d, J=8.7Hz, 4H), 7.46 (d,
J=8.6Hz, 4H), 7.44 (t, J=1.6Hz, 1H), 1.52 (s, 36H).Nuclear-magnetism carbon spectrum: 13C NMR (101MHz,
Chloroform-d) δ=148.96,148.46,143.03,142.48,142.12,139.48,139.30,138.99,
134.70,130.44,126.22,126.09,126.01,125.68,125.58,123.74,123.50,116.37,109.20,
77.40,77.08,76.77,34.80,32.08.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+calcd.For C63H63N3,
862.22；Found, 861.581.
Synthetic example 2:
The present embodiment synthesizes the compound of structure shown in 4PymCz, the specific steps are as follows:
(1) synthetic intermediate 1: with the step (1) in synthetic example 1；
(2) synthetic intermediate 4: with the step (2) in synthetic example 1；
(3) synthetic intermediate 8: synthetic method and the synthesis process of 1 step of synthetic example (3) intermediate 7 are essentially identical,
The difference is that changing 3- pyridine boronic acid pinacol ester in reactant into corresponding 4- pyridine boronic acid pinacol ester, yield
It is 78.0%.
Nucleus magnetic hydrogen spectrum:1δ=8.72 (d, J=5.5Hz, 2H) H NMR (400MHz, Chloroform-d), 7.76 (s,
1H), 7.71 (d, J=1.7Hz, 2H), 7.47 (s, 1H), 7.45 (s, 1H).
(4) 4PymCz: the basic phase of synthesis process of synthetic method and the 3PymCz of step (4) in synthetic example 1 is synthesized
Together, the difference is that changing intermediate 7 into intermediate 8, yield 78.2%.
Nucleus magnetic hydrogen spectrum:1δ=8.72 (s, 2H) H NMR (400MHz, Chloroform-d), 8.18 (s, 4H), 7.98 (s,
1H), 7.90 (d, J=1.5Hz, 2H), 7.89 (s, 2H), 7.78 (d, J=6.9Hz, 2H), 7.73 (t, J=7.8Hz, 2H),
7.66 (d, J=5.9Hz, 2H), 7.63 (d, J=7.7Hz, 2H), 7.49 (d, J=8.7Hz, 4H), 7.43 (d, J=8.7Hz,
4H), 1.49 (s, 36H).Nuclear-magnetism carbon spectrum:13C NMR (101MHz, Chloroform-d) δ=143.03,142.23,139.25,
130.45,126.30,125.98,125.66,125.36,123.71,123.46,116.37,109.14,77.37,77.05,
76.73,34.77,32.04.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+calcd.For C63H63N3, 862.22；Found,
861.479。
Synthetic example 3:
The present embodiment synthesizes the compound of structure shown in 3PypCz, the specific steps are as follows:
(1) synthetic intermediate 2: synthetic method and the synthesis process of 1 step of synthetic example (1) intermediate 1 are essentially identical,
The difference is that bromo-iodobenzene changes into bromo-iodobenzene, yield 89.4% by between.
The nucleus magnetic hydrogen spectrum of intermediate 2:1δ=8.13 (s, 2H) H NMR (400MHz, Chloroform-d), 7.70 (d, J=
8.7Hz, 2H), 7.46 (d, J=7.8Hz, 2H), 7.44 (d, J=8.6Hz, 2H), 7.32 (d, J=8.7Hz, 2H), 1.47 (s,
18H)。
(2) synthetic intermediate 5: synthetic method and the synthesis process of 1 step of synthetic example (2) intermediate 4 are essentially identical,
The difference is that changing intermediate 1 into intermediate 2, yield 66.2%.
The nucleus magnetic hydrogen spectrum of intermediate 5:1δ=8.14 (s, 2H) H NMR (400 MHz, Chloroform-d), 8.03 (d, J
=8.2Hz, 2H), 7.59 (d, J=8.2Hz, 2H), 7.46 (d, J=6.8Hz, 2H), 7.40 (d, J=8.6Hz, 2H), 1.47
(s, 18H), 1.40 (s, 12H).
(3) synthetic intermediate 7: synthetic method is the same as the step (3) in synthetic example 1；
(4) 3PypCz: the basic phase of synthesis process of synthetic method and the 3PymCz of step (4) in synthetic example 1 is synthesized
Together, the difference is that changing intermediate 4 into intermediate 5, yield 78.9%.
Nucleus magnetic hydrogen spectrum:1δ=9.15 (s, 1H) H NMR (400MHz, Chloroform-d), 8.77 (s, 1H), 8.27 (s,
4H), 8.15 (d, J=8.0Hz, 1H), 8.12 (s, 1H), 8.02 (d, J=8.4Hz, 4H), 7.99 (s, 2H), 7.94 (t, J=
12.0Hz, 1H), 7.79 (d, J=8.4Hz, 4H), 7.58 (d, J=10.2Hz, 4H), 7.53 (d, J=8.6Hz, 4H), 1.57
(s, 36H).Nuclear-magnetism carbon spectrum:13C NMR (101 MHz, Chloroform-d) δ=148.61,148.21,143.12,142.11,
139.19,138.09,135.06,128.73,127.14,126.01,125.29,123.76,123.59,116.39,109.31,
77.42,77.10,76.78,34.74,32.10.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+calcd.For C63H63N3,
862.22；Found, 861.581.
Synthetic example 4:
The present embodiment synthesizes the compound of structure shown in 4PypCz, the specific steps are as follows:
(1) synthetic intermediate 2: with the step (1) in synthetic example 3；
(2) synthetic intermediate 5: with the step (2) in synthetic example 3；
(3) synthetic intermediate 8: synthetic method is identical as synthetic example 2 step (3).
(4) 4PypCz: the basic phase of synthesis process of synthetic method and the 3PypCz of step (4) in synthetic example 3 is synthesized
Together, the difference is that changing intermediate 7 into intermediate 8, yield 83.2%.
Nucleus magnetic hydrogen spectrum:1δ=8.80 (s, 2H) H NMR (400MHz, Chloroform-d), 8.20 (s, 4H), 8.10 (s,
1H), 7.99 (d, J=1.7Hz, 4H), 7.97 (s, 2H), 7.75 (d, J=8.5Hz, 6H), 7.54 (d, J=8.7Hz, 4H),
7.48 (d, J=8.6Hz, 4H), 1.52 (s, 35H).Nuclear-magnetism carbon spectrum:13C NMR (101 MHz, Chloroform-d) δ=
150.39,143.11,142.21,139.15,139.01,138.09,128.69,127.12,125.09,123.71,123.55,
116.36,109.23,77.35,77.04,76.72,34.79,32.05.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+
Calcd.For C63H63N3,862.22；Found, 861.663.
Synthetic example 5:
The present embodiment synthesizes the compound of structure shown in 3PyoCz, the specific steps are as follows:
(1) synthetic intermediate 3: synthetic method and the synthesis process of 1 step of synthetic example (1) intermediate 1 are essentially identical,
The difference is that bromo-iodobenzene changes adjacent bromo-iodobenzene, yield 74.3% by between.
The nucleus magnetic hydrogen spectrum of intermediate (3): δ=8.34 (s, 2H) 1HNMR (400MHz, Chloroform-d), 7.96 (d, J
=7.8Hz, 1H), 7.59 (d, J=8.6Hz, 2H), 7.47 (t, J=8.0Hz, 1H), 7.30 (t, J=6.4Hz, 1H), 7.14
(d, J=8.6Hz, 2H), 7.10 (d, J=8.6Hz, 1H), 1.63 (s, 18H).
(2) synthetic intermediate 6: synthetic method and the synthesis process of 1 step of synthetic example (2) intermediate 4 are essentially identical,
The difference is that changing intermediate 1 into intermediate 3, yield 24.6%.
The nucleus magnetic hydrogen spectrum of intermediate (6):1δ=8.13 (s, 2H) H NMR (400 MHz, Chloroform-d), 7.92 (d,
J=7.4Hz, 1H), 7.66 (t, J=8.0Hz, 1H), 7.52 (d, J=7.6Hz, 1H), 7.48 (t, J=6.8Hz, 1H), 7.42
(d, J=8.6Hz, 2H), 7.15 (d, J=8.6Hz, 2H), 1.48 (s, 18H), 0.81 (s, 12H).
(3) synthetic intermediate 7: synthetic method is the same as the step (3) in synthetic example 1；
(4) 3PyoCz: the basic phase of synthesis process of synthetic method and the 3PymCz of step (4) in synthetic example 1 is synthesized
Together, the difference is that changing intermediate 4 into intermediate 6, yield 62.4%%.
Nucleus magnetic hydrogen spectrum:1δ=8.35 (d, J=4.1Hz, 1H) H NMR (400MHz, Chloroform-d), 8.07 (s,
4H), 7.85 (s, 1H), 7.54 (d, J=7.5Hz, 2H), 7.50 (t, J=3.9Hz, 2H), 7.45 (t, J=3.9Hz, 2H),
7.37 (dd, J=8.6,1.5Hz, 4H), 6.96 (s, 2H), 6.92 (d, J=10.6Hz, 4H), 6.89 (t, J=4.0Hz, 1H),
6.64 (s, 2H), 6.26 (d, J=7.9Hz, 1H), 1.46 (s, 36H).Nuclear-magnetism carbon spectrum:13C NMR (101MHz, Chloroform-
D) δ=147.82,142.38,141.11,139.98,138.64,136.58,135.98,135.23,134.07,130.96,
129.87,128.85,128.62,127.50,125.39,123.40,122.92,122.84,115.90,109.38,77.38,
77.27,77.07,76.75,34.61,32.09.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+calcd.For C63H63N3,
862.22；Found, 861.581.
Synthetic example 6:
The present embodiment synthesizes the compound of structure shown in 4PyoCz, the specific steps are as follows:
(1) synthetic intermediate 3: with the step (1) in synthetic example 5；
(2) synthetic intermediate 6: with the step (2) in synthetic example 5；
(3) synthetic intermediate 8: synthetic method is identical as (3) the step of synthetic example 4.
(4) 4PypCz: the basic phase of synthesis process of synthetic method and the 3PypCz of step (4) in synthetic example 5 is synthesized
Together, the difference is that changing intermediate 7 into intermediate 8, yield 68.4%.
Nucleus magnetic hydrogen spectrum:1δ=8.17 (d, J=5.9Hz, 2H) H NMR (400 MHz, Chloroform-d), 8.03 (s,
4H), 7.54 (t, J=10.9,4.0Hz, 2H), 7.51 (d, J=8.0Hz, 2H), 7.47 (t, J=8.0Hz, 2H), 7.36 (d, J
=8.6Hz, 4H), 7.04 (s, 1H), 7.01 (d, J=7.4Hz, 2H), 6.94 (d, J=8.6Hz, 4H), 6.63 (s, 2H),
5.99 (d, J=6.0Hz, 2H), 1.43 (s, 36H).Nuclear-magnetism carbon spectrum:13C NMR (101 MHz, Chloroform-d) δ=
149.52,147.50,142.42,141.14,140.01,138.73,136.73,135.24,130.91,129.98,128.98,
128.70,128.37,125.25,123.41,122.83,121.19,115.94,109.47,77.38,77.06,76.74,
34.60 32.04.Mass spectrum: MS (MADLI-TOF): m/z (M+H)+calcd.For C63H63N3, 862.22；Found,
861.253。
Above-mentioned six kinds of D-A bipolar host materials be respectively 3PymCz, 4PymCz, 3PypCz, 4PypCz, 3PyoCz,
4PyoCz carries out Photophysics test against six kinds of material of main parts, and test result difference is as shown in figs. 1 to 6.
In methylene chloride by material of main part dissolution, film is made in spin coating, and Fig. 1 is the suction that this six kinds of materials are made into film
Receiving curve has a comparison in 297nm, 330nm respectively it may be seen that the position of the absorption peak of six kinds of materials is almost consistent
Apparent absorption peak.Compared to other five kinds of materials, 3PymCz shows strongest absorption in the film, and in addition it is in 345nm
There are one weaker absorption peaks at left and right.
Fig. 2 is six kinds of D-A type bipolar host materials abosrption spectrogram in different solutions respectively；For six kinds of materials
Material, has surveyed the UV absorption feelings in n-hexane, methylene chloride, tetrahydrofuran, four kinds of solution of n,N-Dimethylformamide respectively
Condition.The absorption in solution in methylene chloride of six kinds of materials, it can be seen that the position of the absorption peak of six kinds of materials is almost consistent, point
The absorption peak for not having a comparison sharp in 273nm, 336nm, the absorption peak of 273nm or so belong to molecule this belong to π-π *
Transition, the absorption peak of 336nm or so then belongs to the n- π * transition on carbazole group, and has in 370-400nm a than wider
Absorption band then belongs to the electric charge transfer of intramolecular.Compared to the absorption in dichloromethane solution, in n-hexane, tetrahydro furan
It mutters, is absorbed in n,N-Dimethylformamide solution and all show different degrees of blue shift or red shift.
Fig. 3 is six kinds of D-A type bipolar host materials fluorescence emission spectrogram of compound in different solutions respectively；Material
For 4PymCz compared to other materials, emission peak positions are almost unchanged, show most blue transmitting, emission peak 360nm, and
Possess most narrow half-peak breadth, hardly influenced by solvent polarity, implies that it has highest singlet energy level.And it is other
5 compounds then show almost consistent solvation effect, and with the increase of solvent polarity, the position of emission peak is continuous
Red shift.With the red shift of emission peak, half-peak breadth is also constantly increasing, and emits peak position by 360nm red shift to 440nm or so, still
So belong to blue region.
Fig. 4 is the antenna effect spectrogram of six kinds of D-A type bipolar host materials；From figure it will be seen that
3PymCz has a stronger emission peak in 469nm, and there are one weaker emission peaks in 442nm, is sent out according to highest energy
Penetrating peak and can calculating triplet is 2.80eV；Similar, 3PyoCz has a weaker emission peak in 445nm, another
For stronger emission peak in 468nm, can calculate its triplet is 2.79eV；3PypCz has a stronger emission peak to exist
455nm, another emission peak is in 483nm, triplet 2.73eV；Also there are two more apparent transmittings by 4PymCz
Peak, respectively in 416nm and 444nm, triplet 2.98eV；4PyoCz has a stronger emission peak 461nm and one
A weaker emission peak is in 434nm, triplet 2.86eV；4PypCz has a stronger position in the hair of 456nm
Emission peak of She Feng and weaker position in 484nm, triplet 2.72eV.It can be seen that our six kinds
For the triplet of material all in 2.7eV or more, sufficiently high triplet can guarantee the energy transfer between host-guest
It can be normally carried out, the anti-transition without exciton occurs.FIrpic is as classical blue emitting material, triplet
For 2.62eV, it is contemplated that our material can be as the material of main part of most of phosphor material.
The differential scanning calorimetric thermogram and thermogravimetric analysis figure of six kinds of materials are shown in Fig. 5,3PymCz, 3PyoCz, 3PypCz,
Corresponding temperature (Td) is at 300 DEG C or more when the weightlessness 5% of 4PymCz, 4PyoCz and 4PypCz, and wherein 4PymCz is showed most
It is good, and the thermal decomposition temperature of 3PyoCz and 4PypCz is slightly lower, this is related with their space structure.The vitrifying of six kinds of compounds
Transition temperature TgMost of the performance of 3PypCz is preferable within the scope of 90-120 DEG C, is 167 DEG C.In addition, all materials are all bright
The melting transition temperature more than 300 DEG C is shown aobviously.Glass transition temperature and the device preparation of six kinds of materials are commonly used
Material of main part CBP (Tg=62 DEG C) compare, perform better than, better thermal stability be conducive to device architecture stability and
Extend device lifetime.
Fig. 6 is 3PyoCz doping 5%, 10%, 15% and 20% 4 kind of various concentration Ir (ppy)2The film morphology of acac
Phenogram.The amorphous form of non crystalline structure is presented in material surface, without the appearance of apparent crystalline state or state of aggregation, surface
Also occur without biggish protrusion and pit-hole etc., there is good film forming, adulterate Ir (ppy)2The concentration of acac from 5% to
20%, have no that its pattern has significant change, r.m.s. roughness is 0.35nm or so, shows the good film forming of material.
Fig. 7 is the chemical property analysis chart of six kinds of D-A type bipolar host materials.It is all when CV is aoxidized and tested
Six kinds of materials show extraordinary invertibity, restore in test, and 4PymCz and 4PyoCz show preferable invertibity,
Then invertibity is unobvious for other materials.3PymCz, 3PyoCz, 3PypCz are calculated by oxidation peak position, 4PymCz, 4PyoCz and
The HOMO energy level of six kinds of materials of 4PypCz be respectively -5.31eV, -5.28eV, -5.40eV, -5.45eV, -5.23eV and -
5.27eV.Likewise, LUMO respectively -1.72eV, -1.95eV, -1.52eV can be calculated by reduction peak position, -
2.05eV, -1.92eV and -2.03eV.
Fig. 8 is single carrier transmission performance figure of six kinds of D-A type bipolar host materials, has done electrons and holes respectively
Single charge carrier device, single-electron device structure are ITO/Al (40nm)/active layer/TPBI (35nm)/Ca:Ag, single hole device
Structure is ITO/PEDOT:PSS/ active layer/NPB (40nm)/Au.Wherein, TPBI is as electron transfer layer and hole barrier
Layer, for NPB as hole transmission layer and electronic barrier layer, active layer is respectively six kinds of materials that we synthesize, spin coating about 100nm
The preparation method of thickness, device is the prior art, and this is not described in detail here.As a result as shown in fig. 7, when electric field is 500V/cm, with
3PyoCz is 2.60 × 10 as the electron mobility of the device of material of main part-3cm2/ (VS), and the mobility in hole is 5.97
×10-4cm2The advantages of/(VS), the two more balances, this is this serial material of main part and device can obtain high efficiency
One of the reason of.
Device embodiments 1:
Blue phosphor materials FIrpic is doped in above-mentioned six kinds of material of main parts by the present embodiment respectively with different concentration
A series of blue-light device is made.Device architecture is ITO/PEDOT:PSS/ (Host:Xwt%FIrpic) (50nm)/TPBI
(35nm)/Ca:Ag, wherein ITO is as anode；PEDOT:PSS is as interface-modifying layer and hole injection layer；Luminescent layer is then
It is the FIrpic of the material of main part doping various concentration of above-mentioned synthesis, ratio FIrpic shared in luminescent layer is Xwt%,
Middle X=5,10,15,20,30；TPBI is as electron injecting layer；Ca:Ag is as cathode.Therefore, 30 groups of different subjects have been carried out
Material mixes the device of various concentration FIrpic, and device performance data are as shown in the table.
Device performance of the 1 different subjects material of table in incorporation different proportion FIrpic summarizes
It can be seen that material of main part 3PymCz, 3PyoCz, 3PypCz, 4PymCz, 4PyoCz and six kinds of materials of 4PypCz
Device performance is optimal when doping concentration is respectively 15wt%, 5wt%, 15wt%, 20wt%, 20wt% and 15wt%.This six kinds
Test results are shown in figure 9 for the device performance of best performance, and Fig. 9 is by blue phosphor materials FIrpic with different doped in concentrations profiled
The a series of blue-light device photoelectric characteristic figure being doped in this 6 kinds of material of main parts respectively.As can be seen that from figure a) in we can
To see that, on year-on-year basis in other materials, the current density of 3PypCz relative maximum under same voltage illustrates that device has stronger electricity
Lotus transmittability, and 3PyoCz it is year-on-year under show relatively worst charge transport ability；Figure b) in minimum open bright voltage
It shows that 3PypCz has lesser injection barrier, and 3PyoCz is used to reach as the device maximum brightness of material of main part
15149cd/m2, be it is all mix it is highest in specific concentration；C) be all devices current efficiency-brightness curve, wherein 3PyoCz
The maximum current efficiency of device as material of main part has reached 16.7cd/A；Figure is d) their electroluminescent curve, from figure
In it can be seen that 4PymCz and 4PyoCz there are also the emission peak of portion body material (400nm or so), other materials then only have
Two characteristic peaks of guest materials FIrpic, the energy transfer shown between Subjective and Objective are more complete.
Device embodiments 2:
When the present embodiment uses 3PyoCz with material of main part in device embodiments 1, the FIrpic blue phosphorescent of 5wt% is mixed
Material is optimization basis, mixes TAPC, TCTA on its basis as hybrid agent, wherein three kinds of materials in hybrid agent
3PyoCz: TAPC: TCTA mass ratio is 7: 2: 1.
Device architecture is ITO/PEDOT:PSS/Host:FIrpic (50nm)/TPBI (35nm)/Ca:Ag, and wherein ITO makees
For anode, PEDOT:PSS is as interface-modifying layer and hole injection layer, and TPBI is as hole transport and exciton barrier-layer, Ca:Ag
As cathode.
As shown in Figure 10 for 3PyoCz optimization after device performance figure, from figure a) in it will be seen that with TAPC,
The addition of TCTA, the current density with device under voltage are improved, and illustrate that the addition of TAPC improves the carrier of device
Transmittability；Can see the device for using hybrid agent from b) figure simultaneously opens bright voltage as 4V or so, illustrates mixed when using
When closing main body as material of main part, reduce the injection barrier of carrier；And in terms of efficiency, use 3PyoCz:
The maximum current efficiency of the device of TAPC hybrid agent has reached 24.1cd/A, using 3PyoCz: TAPC: TCTA hybrid agent
The maximum current efficiency of device has reached 22.7cd/A, the maximum current efficiency of the reference device than using single main body 3PyoCz
44.4% and 35.9% has been respectively increased in 16.7cd/A, in the OLED blue phosphorescent device of solwution method preparation very efficiently；From
D) figure can see using the device of hybrid agent for compared to reference device, and wherein reference device is in device embodiments 1
The FIrpic blue phosphor materials of 3PyoCz incorporation incorporation 5wt% are as single main body, it can be seen that the device of hybrid agent
The emission peak of 400nm or so disappears, meanwhile, two emission peaks of Flrpic, emission peak at 470nm relative to 495nm at
Emission peak is higher, all shows that the energy of hybrid agent can more effectively be transferred to guest materials.
Device embodiments 3:
Device preparation method and device embodiments 2 in the present embodiment is essentially identical, the difference is that changing mixing master
The mass ratio of three kinds of materials 3PyoCz, TAPC and TCTA in body, 3PyoCz: TAPC: TCTA mass ratio be set to 6: 3: 1 with
And 8: 1: 1.The device detection result being prepared is consistent with the result of device embodiments 2, using the device performance of hybrid agent
Better than the device using single main body.
Device embodiments 4:
Device preparation method and device embodiments 2 in the present embodiment is essentially identical, the difference is that changing mixing master
Material in body, mixes TAPC in material of main part 3PyoCz, and 3PyoCz: TAPC mass ratio is 4: 1.It obtains after tested, this
The device performance that embodiment is prepared is better than using device of the 3PyoCz as single main body in device embodiments 1, but compares
It is poor collectively as the device performance of hybrid agent using 3PyoCz, TAPC and TCTA in device embodiments 2.
Device embodiments 5:
Device preparation method and device embodiments 4 in the present embodiment is essentially identical, the difference is that changing mixing master
The mass ratio of three kinds of materials 3PyoCz, TAPC in body, 3PyoCz: TAPC mass ratio are set to 3: 1 and 5: 1.It is prepared into
To device detection result be consistent with the result of device embodiments 4, the device performance using 3PyoCz, TAPC as hybrid agent
It is but poorer collectively as the device performance of hybrid agent than 3PyoCz, TAPC and TCTA better than the device using single main body.
Device embodiments 6:
The present embodiment is by orange phosphor material Ir (bt)2Acac is doped to a series of in above-mentioned six kinds of material of main parts respectively
Orange light device, device architecture are as follows: ITO/PEDOT:PSS/ [Host:X wt%Ir (bt) 2acac]/TPBI (35nm)/Ca:Ag,
Wherein luminescent layer be respectively adopted aforementioned body material 3PymCz, 3PyoCz, 3PypCz, 4PymCz, 4PyoCz and 4PypCz as
Single main body material adulterates the light-emitting guest Ir (bt) of various concentration respectively2Acac, X=5,10,15,20,30.
Therefore 30 groups of different subjects material incorporations various concentration Ir (bt) have been carried out2The device of acac, after to device into
Row performance test, test find material of main part 3PymCz, 3PyoCz, 3PypCz, 4PymCz, 4PyoCz and six kinds of materials of 4PypCz
Doping concentration when being respectively 30wt%, 5wt%, 30wt%, 20wt%, 15wt% and 5wt% device performance it is optimal.This six kinds
The device performance test result of best performance is as shown in figure 11, and Figure 11 is orange light material Ir (bt)2Acac is doped in 6 main respectively
Device performance analysis chart in body material: wherein a) figure is current density voltage curve, shows that different materials have similar load
Flow sub- transmittability；Figure is b) change curve of the brightness with voltage, and 3PyoCz and 4PypCz are as main body as we can see from the figure
The brightness of the device of material is higher compared to other devices, and the maximum brightness of two devices is respectively 36960cd/m2With
33840cd/m2；Figure c) is current efficiency with brightness variation curve, Cong Tuzhong maximum current efficiency be respectively 24.8cd/A and
22.6cd/A；Figure d) be device electroluminescent spectrum, from the figure, it can be seen that in addition to the transmitting at the 560nm of guest materials
Outside peak, emission peak not from material of main part or other exciplexs indicates that Subjective and Objective system has efficient exciton
Compound and energy transfer.
Device embodiments 7:
When the present embodiment uses 3PyoCz with material of main part in device embodiments 6, the Ir (bt) of 5wt% is mixed2Acac orange
Color phosphor material is optimization basis, mixes TAPC, TCTA on its basis as hybrid agent, three groups of parallel tests are arranged,
The mass ratio of three kinds of materials 3PyoCz: TAPC: TCTA is 7: 2: 1,6: 3: 1 and 8: 1: 1 in middle hybrid agent.
Device is tested afterwards, test result shows the device performance of hybrid agent better than the list in device embodiments 6
The device performance of one main body.
Device embodiments 8:
When the present embodiment uses 3PyoCz with material of main part in device embodiments 6, the Ir (bt) of 5wt% is mixed2Acac orange
Color phosphor material is optimization basis, mixes TAPC on its basis as hybrid agent, three groups of parallel tests is arranged, wherein mixing
The mass ratio of three kinds of materials 3PyoCz: TAPC is 3: 1,4: 1 and 5: 1 in main body.
Device is tested afterwards, test result shows the device performance of hybrid agent better than the list in device embodiments 6
The device performance of one main body, but it is poorer than the device performance of 3PyoCz, TAPC, TCTA hybrid agent in device embodiments 7.
Device embodiments 9:
The present embodiment is by green phosphorescent material Ir (ppy)2Acac is done with different doped in concentrations profiled into six kinds of material of main parts
A series of green devices, device architecture are prepared for for luminescent layer are as follows: ITO/PEDOT:PSS/Host:Xwt%Ir (ppy)2acac
(50nm)/TPBI (35 nm)/Ca:Ag, wherein 6 kinds of different materials adulterate the green phosphorescent luminescent material of various concentration respectively
Ir(ppy)2Acac is as luminescent layer, X=5, and 10,15,20,30.Wherein, anode of the ITO as device, PEDOT:PSS conduct
Interface-modifying layer and hole injection layer, TPBI is as electron transfer layer and exciton barrier-layer, and metal Ca:Ag is as cathode.
Therefore 30 groups of different subjects material incorporations various concentration Ir (ppy) have been carried out2The device of acac, after to device into
Row performance test, test find material of main part 3PymCz, 3PyoCz, 3PypCz, 4PymCz, 4PyoCz and six kinds of materials of 4PypCz
Doping concentration when being respectively 30wt%, 5wt%, 30wt%, 20wt%, 15wt% and 5wt% device performance it is optimal.This six kinds
The device performance test result of best performance is as shown in figure 12, and Figure 12 is green phosphorescent material Ir (ppy)2Acac is with different dense
Degree is doped to a series of the performance test results for being prepared for devices in material as luminescent layer, wherein scheming a) is that current efficiency-is bright
It writes music line, under same brightness, material 3PyoCz is obviously more outstanding as the device of material of main part, maximum value 29.0cd/
A；Figure b) is brightness-voltage curve, material 3PyoCz and 4PypCz as the device of material of main part brightness compared to other devices
Part is bigger, respectively 23818cd/m2And 30603cd/m2, when driving voltage reaches 14V, the brightness of device is not shown also
The trend for showing decaying shows its brilliant stability；Figure c) be current density and voltage relational graph, all devices all have
There is higher current density, shows that the ability of their transmission charge is all stronger；D) figure is electroluminescent light spectrogram, Cong Tuzhong
It may be seen that the luminescent spectrum of all devices is all more stable, and the not emission peak in addition to object characteristic peak, host and guest
Energy transfer between body is more complete.
Device embodiments 10:
When the present embodiment uses 3PyoCz with material of main part in device embodiments 9, the Ir (ppy) of 5wt% is mixed2Acac is green
Color phosphor material is optimization basis, mixes TAPC, TCTA on its basis as hybrid agent, wherein three kinds of materials in hybrid agent
The mass ratio of material 3PyoCz: TAPC: TCTA is 7: 2: 1.
Device embodiments 11:
When the present embodiment uses 3PyoCz with material of main part in device embodiments 9, the Ir (ppy) of 5wt% is mixed2Acac is green
Color phosphor material is optimization basis, mixes TAPC on its basis as hybrid agent, wherein three kinds of materials in hybrid agent
3PyoCz: TAPC mass ratio is 4: 1.
It by the device for the hybrid agent being prepared in device embodiments 10, device embodiments 11, is tested for the property, surveys
Test result is as shown in figure 13.Wherein a) figure is current density voltage curve, under identical voltage, current density ratio single main body
It is bigger, show that the carrier transmission performance of hybrid agent is more preferable；B) figure is brightness-voltage curve, using the device of hybrid agent
The bright voltage that opens of part is reduced, and shows its lower injection barrier, meanwhile, maximum brightness has also reached 31815cd/m2
(3PyoCz: TAPC) and 35451cd/m2(3PyoCz:TAPC:TCTA)；C) figure is current efficiency with brightness variation curve, efficiency
Also get a promotion, maximum current efficiency reached 45.2cd/A (3PyoCz: TAPC) and 42.9cd/A (3PyoCz: TAPC:
TCTA)；D) figure is the electroluminescent spectrum of device, and using the emission peak of the device of hybrid agent, acromion almost disappears, half-peak
It is wide smaller, show that energy more effectively transmits.
Claims (10)
1. a kind of bipolarity D-A type material of main part, it is characterised in that: its structural formula is any one of following six kinds of structures:
2. bipolarity D-A type material of main part according to claim 1, it is characterised in that: its structural formula is
3. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that: the material of the luminescent layer includes claim
D-A bipolar host material described in 1.
4. organic electroluminescence device according to claim 3, it is characterised in that: the material of the luminescent layer further includes mixing
The miscellaneous phosphor material in the D-A bipolar host material.
5. organic electroluminescence device according to claim 4, it is characterised in that: the phosphor material is blue emitting phosphor material
Material, orange phosphor material or green phosphorescent material；The phosphor material of the doping in luminescent layer proportion be 5wt%~
30wt%.
6. organic electroluminescence device according to claim 4, it is characterised in that: the material of main part is 3PyoCz, institute
Stating the phosphor material of the doping proportion in luminescent layer is 5wt%~10wt%.
7. organic electroluminescence device according to claim 4, it is characterised in that: the material of main part be 3PyoCz or
4PypCz；The phosphor material of the doping is orange phosphor material or green phosphorescent material.
8. organic electroluminescence device according to claim 4, it is characterised in that: further include being entrained in material of main part
TAPC and/or TCTA in 3PyoCz form hybrid agent with material of main part 3PyoCz.
9. organic electroluminescence device according to claim 8, it is characterised in that: at the same mix TAPC and TCTA formed it is mixed
Main body is closed, the mass ratio of described 3PyoCz, TAPC, TCTA are 6~8: 1~3: 1.
10. organic electroluminescence device according to claim 8, it is characterised in that: individually incorporation TAPC forms mixing master
Body, the mass ratio of described 3PyoCz, TAPC are 3~5: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675359A (en) * | 2021-07-28 | 2021-11-19 | 合肥工业大学 | Method for improving efficiency of bipolar TADF material assisted doping mixed host green phosphorescent OLED device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934213A (en) * | 2004-03-08 | 2007-03-21 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| JP2010090084A (en) * | 2008-10-10 | 2010-04-22 | Chemiprokasei Kaisha Ltd | Novel bis(carbazolylphenyl) derivative, host material, and organic electroluminescent element each employing the same |
| CN104017563A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Bipolar blue-phosphorescence material, preparation method thereof and organic electroluminescent device |
| CN104419402A (en) * | 2013-08-29 | 2015-03-18 | 海洋王照明科技股份有限公司 | Carbazolyl blue phosphorescent host material as well as preparation method and application thereof |
-
2019
- 2019-09-12 CN CN201910869344.9A patent/CN110511212B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934213A (en) * | 2004-03-08 | 2007-03-21 | 出光兴产株式会社 | Material for organic electroluminescent device and organic electroluminescent device using the same |
| JP2010090084A (en) * | 2008-10-10 | 2010-04-22 | Chemiprokasei Kaisha Ltd | Novel bis(carbazolylphenyl) derivative, host material, and organic electroluminescent element each employing the same |
| CN104017563A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Bipolar blue-phosphorescence material, preparation method thereof and organic electroluminescent device |
| CN104419402A (en) * | 2013-08-29 | 2015-03-18 | 海洋王照明科技股份有限公司 | Carbazolyl blue phosphorescent host material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汪红姣: "双极性主体材料合成及OLEDs器件研究", 《南京邮电大学硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675359A (en) * | 2021-07-28 | 2021-11-19 | 合肥工业大学 | Method for improving efficiency of bipolar TADF material assisted doping mixed host green phosphorescent OLED device |
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