CN102911145A - Dibenzo-heterocyclic spirobifluorene compound, preparation method thereof and organic electrophosphorescent device - Google Patents
Dibenzo-heterocyclic spirobifluorene compound, preparation method thereof and organic electrophosphorescent device Download PDFInfo
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Abstract
The invention provides a dibenzo-heterocyclic spirobifluorene compound having a structure shown in formula I, wherein X refers to O or S, and Ar refers to substituent shown in formula II or formula III. The compound serving as a main material of an organic electrophosphorescent device is good in stability and high in luminescent intensity and current efficiency. The invention further provides a preparation method of the compound shown in the formula I and the organic electrophosphorescent device comprising the compound shown in the formula I.
Description
Technical field
The present invention relates to organophosphorus photoinitiator dye field, relate in particular to a kind of dibenzo heterocycle and connect spiro-bisfluorene compound and preparation method thereof and a kind of organic electro phosphorescent device.
Background technology
Prepare with Alq by vacuum deposition method from people's reported first such as the C.W.Tang of Kodak in 1987
3Since the bi-layer devices structure for luminescent material, organic electroluminescent has just obtained people's very big concern.
Organic electroluminescent can be divided into the fluorescence and phosphorescence electroluminescent.According to spin quantum statistical theory, the formation probability ratio of singlet state exciton and triplet exciton is 1:3, namely the singlet state exciton only account for " electron-hole pair " 25%.Therefore, the fluorescence that comes from the radiative transition of singlet state exciton just only accounts for 25% of total input energy, and the electroluminescent of phosphor material just can utilize the energy of whole excitons, thereby has larger superiority.
Mostly adopt the Subjective and Objective structure in the present electrophosphorescence device, soon the phosphorescent emissions material in material of main part, to avoid burying in oblivion of concentration quenching and triplet state-triplet state, improves phosphorescent emissions efficient with certain doped in concentrations profiled.
[M.A.Baldo, S.Lamansky, P.E.Burroes, M.E.Thompson, S.R.Forrest.Appl.Phys.Lett., 1999,75,4] such as Forrest in 1999 and Thompson are with green phosphorescent material Ir (ppy)
3With the doped in concentrations profiled of 6wt% 4,4 '-N, in the material of main part of N '-two carbazoles-biphenyl (CBP), and introduced hole barrier layer material 2,9-dimethyl 4,7-phenylbenzene-1,10-phenanthroline (BCP), the maximum external quantum efficiency of the green glow OLED of acquisition reaches 8%, and power efficiency reaches 31lm/W, all substantially exceed the electroluminescent fluorescent luminescent device, caused immediately the extensive concern of people to the heavy metal complex luminescent material.
[Adachi, Chihaya.Baldo, Marc A.Forrest, Stephen R.Thompson, Mark E., Appl.Phys.Lett., 2000,77,904] such as Forrest were with Ir (ppy) in 2000
3Be entrained in the main body 3-phenyl-4-(1 '-naphthyl) of electron-transporting type-5-phenyl-1,2, in the 4-triazole (TAZ), obtain the device maximum power efficiency and reach 40 ± 2lm/W.
Forrest (Holmes, R.J.Forrest, S.R.Tung in 2003, Y.-J.Kwong, R.C.and Brown, J.J.Garon, S.Thompson, M.E., Appl Phys Let, 2003,82,2422) realized again blue light complex of iridium FIrpic, it has been entrained in main body N, device maximum current efficient and the power efficiency of preparation are respectively 7.5 ± 0.8cd/A and 8.9 ± 0.9lm/W in N '-two carbazyl-3,5-substituted benzene (mCP).
But the material of main part that the organic electro phosphorescent device that provides in the prior art uses does not all have cavity transmission ability, and luminous less stable, and brightness and luminous power all can not reach service requirements behind the Doping Phosphorus photoinitiator dye,
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of good stability, material of main part that luminous intensity is high, current efficiency is high and preparation method thereof, and the organic electro phosphorescent device that comprises described material of main part.
In order to solve above technical problem, the invention provides the compound shown in a kind of formula I:
Wherein, X is S or O; Ar is the substituting group shown in formula II or the formula III:
The preparation method of compound shown in a kind of formula 1 comprises:
Compound shown in formula IV or the formula V is mixed in organic solvent with the compound shown in the formula VI and alkali-metal carbonate, the Suzuki linked reaction occurs under the effect of catalyzer, obtain crude product;
With described crude product reflux, extracting operation, with carrying out silica gel column chromatography after the extraction liquid drying, obtain the compound shown in the formula I;
Wherein X is O or S, X
1Be F, Cl, Br or I.
Preferably, described catalyzer is tetrakis triphenylphosphine palladium.
Preferably, described organic solvent is tetrahydrofuran (THF).
Preferably, the compound shown in the compound shown in described formula IV or the formula V and the formula VI is in mass ratio: (3.5 ~ 6): (3 ~ 4).
Preferably, the compound shown in described catalyzer and the formula VI is (0.6 ~ 0.7) in mass ratio: (3 ~ 4).
A kind of organic electro phosphorescent device comprises:
Glass;
Be attached to described substrate on glass;
Be arranged on the hole injection layer on the described substrate;
Be arranged on the hole transmission layer on the described hole injection layer;
Be arranged on the luminescent layer on the described hole transmission layer;
Be arranged on the hole blocking layer on the described luminescent layer;
Be arranged on the electron transfer layer on the described hole blocking layer;
Be arranged on the cathode layer on the electron transfer layer;
Wherein, described luminescent layer is comprised of material of main part and dopant material, and described material of main part is the compound shown in the formula 1;
Wherein, X is S or O; Ar is the substituting group shown in formula II or the formula III:
Preferably, described dopant material is the complex of iridium of cyclic metal complexes.
Preferably, the complex of iridium of described cyclic metal complexes is one or more in the compound shown in formula 1 ~ formula 4:
Preferably, the doping ratio of described dopant material in described material of main part is 3wt% ~ 15wt%.
Compound shown in the formula I provided by the invention has the dibenzo heterocycle structure, wherein said heterocycle is furan structure or thiophene-structure, has again the spiro-bisfluorene substituting group shown in formula II or the formula III, with the compound shown in the formula I during as material of main part, the dibenzo heterocycle structure has cavity transmission ability, and the spiro-bisfluorene substituting group has satisfactory stability, so that the compound shown in the formula I has the electroluminescent properties better than prior art.
The present invention also provides the preparation method of the compound shown in the described I, dibenzo heterocyclic boronic acids shown in compound halo spiro-bisfluorene compound shown in formula IV or the formula V and the formula VI is reacted, owing to containing halogen on formula IV or the formula V, and have boric acid base group on the compound shown in the formula VI, so reacting, this is the Suzuki linked reaction.Owing to being the Suzuki linked reaction, so reaction conditions is gentle, productive rate is higher, is fit to large-scale industrial production.
The present invention also provides a kind of organic electro phosphorescent device that comprises compound shown in the formula I, comprising: glass; Be attached to described substrate on glass; Be arranged on the hole injection layer on the described substrate; Be arranged on the hole transmission layer on the described hole injection layer; Be arranged on the luminescent layer on the described hole transmission layer; Be arranged on the hole blocking layer on the described luminescent layer; Be arranged on the electron transfer layer on the described hole blocking layer; Be arranged on the cathode layer on the electron transfer layer; Described luminescent layer is entrained in by phosphorescent coloring in the material of main part of the compound formation shown in the formula I and forms, because the compound shown in the described formula I has dibenzo heterocyclic group and spiro-bisfluorene group, so on the basis that has had the hole transport performance concurrently, increase the stability of described organic electro phosphorescent device, improved maximum brightness, current efficiency and power efficiency.Keithley source measuring system by silicon photoelectric diode detects, organic electro phosphorescent device provided by the invention, when described phosphorescence device blue light-emitting, maximum current efficient is up to 23.5cd/A, during green light, maximum current efficient is 64cd/A, when emitting white light, maximum current efficient is 50cd/A, and performance is better than prior art.
Description of drawings
The uv-visible absorption spectra figure of the material of main part that Fig. 1 embodiment of the invention 3 provides;
The photoluminescence figure of the material of main part that Fig. 2 embodiment of the invention 3 provides;
Fig. 3 EL device structure schematic diagram of the present invention;
The emmission spectrum of Fig. 4 electroluminescent device of the present invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of dibenzo heterocycle and connect the spiro-bisfluorene compound, have structure shown in the formula I:
Wherein, X is O or S; Ar is the substituting group shown in formula II or the formula III.
The dibenzo heterocycle structure has and the akin structure of carbazole in the structure shown in the formula I, so have good cavity transmission ability, has increased the transmission speed of hole in material of main part, thereby has improved current efficiency and luminous intensity.And that the spiro-bisfluorene substituting group shown in formula II and the formula III has the main body of 2 symmetries is fluorene structured, electronics and cavity transmission ability have obtained greatly improving, the luminescent properties of main body fluorenes has obtained reservation, delocalized pi-bond in its conjugated structure is so that the fluorescence enhancing, be the relative absorption spectrum Einstein shift of emmission spectrum, energy reduces, and oscillator strength strengthens, and owing to being the two fluorene structured of symmetry, its stability also further strengthens.In sum, has the speciality that the compound shown in the formula I of thionaphthene or cumarone structure and spiro-bisfluorene structure meets the bipolar carrier transmission performance material.Good stability, luminous intensity is high, current efficiency is high.
The present invention also provides the preparation method of the compound shown in a kind of formula I, comprising:
The preparation method of compound shown in a kind of formula 1 comprises:
Compound shown in formula IV or the formula V is mixed in organic solvent with the compound shown in the formula VI and alkali-metal carbonate, the Suzuki linked reaction occurs under the effect of catalyzer, obtain crude product;
With described crude product reflux, extracting operation, with carrying out silica gel column chromatography after the extraction liquid drying, obtain the compound shown in the formula I;
Wherein X is O or S, X
1Be F, Cl, Br or I.
Owing to being in organic solvent, to be mixed with the compound shown in the formula VI and alkali-metal carbonate by the compound shown in IV or the formula V, can find out the linked reaction that is actually between phenyl ring and the phenyl ring by the structural formula of observing starting compound, because the compound shown in the formula I is for organic electro phosphorescent device, so in the process of preparation, can not use too harsh reaction conditions, so the present invention prepares with the Suzuki linked reaction in the preparation, mild condition, productive rate is high.In the Suzuki linked reaction, catalyzer is preferably palladium series catalyst, more preferably tetrakis triphenylphosphine palladium (Pd (PPh
3)
4).Compound shown in described catalyzer and the formula VI is preferably (0.6 ~ 0.7) in mass ratio: (3 ~ 4).Compound shown in compound shown in described formula IV or the formula V and the formula VI is preferably in mass ratio: (3.5 ~ 6): (3 ~ 4).Described organic solvent is preferably tetrahydrofuran (THF).
The present invention also provides a kind of organic electro phosphorescent device, comprising:
Glass;
Be attached to described substrate on glass;
Be arranged on the hole injection layer on the described substrate;
Be arranged on the hole transmission layer on the described hole injection layer;
Be arranged on the luminescent layer on the described hole transmission layer;
Be arranged on the hole blocking layer on the described luminescent layer;
Be arranged on the electron transfer layer on the described hole blocking layer;
Be arranged on the cathode layer on the electron transfer layer;
Wherein, described luminescent layer is comprised of material of main part and dopant material, and described material of main part is the compound shown in the formula 1.
The luminescent layer material that uses in the organic electro phosphorescent device provided by the invention is entrained in the material of main part as dopant material and forms, and described dopant material is the organophosphorus photoinitiator dye, and material of main part is the material of main part of the compound formation shown in the formula I.As shown in Figure 3, the organic electro phosphorescent device for the embodiment of the invention provides comprises: glass and substrate 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6, cathode layer 7.
According to the present invention, the organophosphorus photoinitiator dye of described doping is preferably the complex of iridium of cyclic metal complexes; The more preferably compound shown in formula 1 ~ formula 3, the i.e. Ir of green light (ppy)
3, Ir (ppy)
2(acac) or the FIrpic of blue light-emitting:
The doping ratio of described dopant material in described material of main part is 8wt% ~ 15wt%.Wherein the doping weight ratio of green phosphorescent dye is preferably 8wt% ~ 10wt%, and the doping ratio of blue phosphorescent dyestuff is preferably 8wt% ~ 15wt%.
Preferred, the present invention also provides the organic electro phosphorescent device with two-layer luminescent layer, different phosphorescent colorings mixes respectively in two-layer luminescent layer, can excited white light, wherein the preferred doped, blue phosphorescent coloring of one deck is the compound shown in the formula 3, the preferred doping yellow phosphorescence dyestuff PO-01 of another layer, its structure is suc as formula shown in the IV.The dye adulterated amount of blue phosphorescent shown in the described formula 3 is 8wt% ~ 15wt%, and the doping of described PO-01 is 3% ~ 5%.
Be specific embodiments of the invention below, elaborated the present invention program: used raw material is commercially available among the embodiment.
The preparation of 4-2-spiro-bisfluorene base-diphenylene-oxide (being abbreviated as Host1)
4.00 gram 2-bromine spiro-bisfluorenes and 3.20 gram 4-diphenylene-oxide boric acid are added in 50 ml flasks, add catalyst P d (PPh
3)
4650 milligrams, 42 milliliters of tetrahydrofuran (THF)s, 2M K
2CO
314 milliliters of solution, lower 70 ℃ of argon shield refluxed 24 hours, use dichloromethane extraction after the cooling, and organic layer is spin-dried for after with anhydrous sodium sulfate drying, crosses post with methylene dichloride/sherwood oil=1:5, were spin-dried for to get target compound 4.25 and restrain productive rate 87.3%.
1H?NMR(400MHz,CDCl
3)δ(ppm):8.00-8.07(m,2H),7.91(d,J=7.6Hz,2H),7.82-7.87(m,3H),7.36–7.46(m,6H),7.27–7.34(m,2H),7.12–7.17(m,4H),6.84(d,J=7.6Hz,2H),6.79(d,J=7.6Hz,1H).
13C?NMR(100?MHz,CDCl
3)δ(ppm):155.9,153.1,149.4,149.1,148.7,141.8,141.5,141.3,135.9,128.7,127.9,127.8,127.7,127.1,126.6,125.6,124.7,124.2,124.1,123.0,122.6,120.6,120.1,120.0,119.5,111.7,66.1.MS(EI):m/z?482.22(M
+).
The preparation of 4-2-spiro-bisfluorene base-dibenzothiophene (being abbreviated as Host2)
Adopt way similar to Example 1, use raw material to adopt 2-bromine spiro-bisfluorene and 4-dibenzothiophene boric acid can make 4-2-spiro-bisfluorene base-dibenzothiophene, productive rate 92.2%.
1H?NMR(400MHz,CDCl
3)δ(ppm):8.11(t,J=4.8Hz,1H),8.03(d,J=7.6Hz,1H),7.98(d,J=8.0Hz,1H),7.90(d,J=7.6Hz,1H),7.80-7.85(m,3H),7.75(t,J=5.2Hz,1H),7.33-7.45(m,6H),7.32(d,J=7.6Hz,1H),7.14(t,J=7.6Hz,3H),7.05(s,1H),6.85(d,J=7.6Hz,2H),6.78(d,J=7.6Hz,1H).
13C?NMR(100MHz,CDCl
3)δ(ppm):149.6,149.1,148.5,141.8,?141.6,141.3,140.1,139.4,138.5,136.8,136.1,135.6,128.0,127.8,127.7,126.7,126.6,124.9,124.2,124.1,122.5,121.6,120.3,120.1,120.0,66.0.MS(EI):m/z?498.08(M
+).
The preparation of 4-4-spiro-bisfluorene base-diphenylene-oxide (being abbreviated as Host3)
Adopt way similar to Example 1, raw material choose 4-bromine bromine spiro-bisfluorene and 4-diphenylene-oxide boric acid.Can make 4-4-spiro-bisfluorene base-diphenylene-oxide.Productive rate 75.4%.
1H?NMR(400MHz,CDCl
3)δ(ppm):8.11(d,J=7.6Hz,1H),8.06(d,J=7.6Hz,1H),7.87(d,J=7.6Hz,2H),7.67(d,J=7.6Hz,1H),7.51–7.57(m,2H),7.36–7.47(m,5H),7.13-7.24(m,3H),6.80-6.97(m,5H),6.68-6.74(m,2H).
13C?NMR(100MHz,CDCl
3)δ(ppm):156.3,153.9,149.5,149.0,148.9,141.9,141.7,141.5,139.6,131.4,130.2,128.4,127.8,127.7,127.5,127.4,127.3,125.1,124.7,124.1,123.7,123.6,123.0,122.8,122.4,120.7,120.3,120.0,112.1,65.7.MS(EI):m/z?482.23(M
+).
The preparation of 4-4-spiro-bisfluorene base-dibenzothiophene (being abbreviated as Host4)
Adopt way similar to Example 1, raw material choose 4-bromine bromine spiro-bisfluorene and 4-dibenzothiophene can make 4-4-spiro-bisfluorene base-dibenzothiophene.Productive rate 79.9%.
1H?NMR(400MHz,CDCl
3)δ(ppm):8.32(d,J=7.6Hz,1H),8.27(d,J=7.6Hz,1H),7.87(d,J=7.2Hz,2H),7.79(d,J=7.6Hz,1H),7.70(t,J=7.6Hz,1H),7.66(d,J=6.8Hz,1H),7.44-7.54(m,2H),7.40(t,J=7.2Hz,2H),7.34?(d,J=7.2Hz,1H),7.36–7.47(m,5H),7.13-7.24(m,3H),6.80-6.97(m,5H),6.69(d,J=7.2Hz,1H),6.57(d,J=7.6Hz,1H).
13C?NMR(100MHz,CDCl
3)δ(ppm):149.7,149.0,148.9,148.7,142.0,141.6,141.1,140.2,140.0,139.0,135.8,135.1,129.2,128.0,127.8,127.7,127.6,127.4,127.1,126.8,125.0,124.4,124.2,124.1,123.8,123.6,122.9,122.6,121.8,120.9,120.0,65.8.MS(EI):m/z?498.09(M
+).
The preparation of electro phosphorescent device
As shown in Figure 3, take the electro phosphorescent device of the present invention as the luminescent layer material of main part, can comprise glass and conductive glass (ITO) substrate layer 1, hole injection layer 2(molybdic oxide MoO
3), hole transmission layer 3(4,4 '-two (how basic N-phenyl-N-is)-biphenyl NPB), exciton barrier-layer 4(4,4', 4 " three (carbazole-9-yl) triphenylamine TCTA) the described material of main part of luminescent layer 5(claim 1 phosphorescent iridium complex claimed in claim 2 that mixes); hole blocking layer 6(1,3,5-three (1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene TPBi); electron injecting layer 6(three-oxine lithium Liq), cathode layer 7(aluminium).
Electroluminescent device can be made by means known in the art, as presses the disclosed method of reference (Adv.Mater.2003,15,277.) and make.Concrete grammar is: under high vacuum condition, and the MoO of evaporation 10nm successively on through conductive glass (ITO) substrate that cleans
3, the NPB of 80nm, the luminescent layer of 20nm, the TPBi of 40nm, the Liq of 2nm and the Al of 100nm.Make as shown in Figure 3 device with the method, the structure of various devices is as follows:
Device 1 (D1):
ITO/MoO
3(10nm)/NPB(80nm)/TCTA(5nm)/HOST3:FIrpic?8wt%(20nm)/TPBi(40nm)/Liq(2nm)/Al(100nm)
Device 2 (D2):
ITO/MoO
3(10nm)/NPB(80nm)/TCTA(5nm)/HOST4:FIrpic?8wt%(20nm)/TPBi(40nm)/Liq(2nm)/Al(100nm)
Device 3 (D3):
ITO/MoO
3(10nm)/NPB(35nm)/TCTA(10nm)/HOST1:Ir(ppy)
2acac?8wt%(15nm)/TPBi(65nm)/Liq(20nm)/Al?(100nm)
Device 4 (D4):
ITO/MoO
3(10nm)/NPB(35nm)/TCTA(10nm)/HOST2:Ir(ppy)
2acac?8wt%(15nm)/TPBi(65nm)/Liq(20nm)/Al(100nm)
Device 5 (D5):
ITO/MoO
3(10nm)/NPB(35nm)/TCTA(10nm)/HOST3:Ir(ppy)
2acac?8wt%(15nm)/TPBi(65?nm)/Liq(20nm)/Al(100nm)
Device 6 (D6):
ITO/MoO
3(10nm)/NPB(35nm)/TCTA(10nm)/HOST4:Ir(ppy)
2acac?8wt%(15nm)/TPBi(65?nm)/Liq(20nm)/Al(100nm)
Device 7 (D7):
ITO/MoO
3(10nm)/NPB(80nm)/TCTA(10nm)/HOST3:PO-013wt%(1nm)/HOST4:FIrpic?8wt%(19nm)/TPBi(40nm)/Liq(2nm)/Al(100nm)
Device 8 (D8):
ITO/MoO
3(10nm)/NPB(80nm)/TCTA(10nm)/HOST4:PO-013wt%(1nm)/HOST4:FIrpic?8wt%(19nm)/TPBi(40nm)/Liq(2nm)/Al(100nm)
Electric current-the brightness-voltage characteristic of device is to be finished by the Keithley source measuring system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) with corrected silicon photoelectric diode, electroluminescent spectrum is by the Photo research PR655 of company spectrometer measurement, and all measurements are all finished in atmosphere at room temperature.
The performance of devices data see the following form:
Device 1-2 launches blue light, electroluminescent properties apparently higher than documents (C.Han, G.Xie, J.Li, Z.Zhang, H.Xu, Z.Deng, Y.Zhao, P.Yan and S.Liu, Chem.Eur.J.2011,17,8947-8956.).Maximum current efficient is maximum value so far up to every ampere of 23.5 Kan Tela.Its corresponding green glow performance of device 3-6 is especially well beyond comparative device.Device 7-8 transmitting white, every ampere of maximum current efficient 50 Kan Tela are one of present this type of material of main part maximums.Therefore, compare with other material of main parts, material of main part of the present invention contains again the spiro-bisfluorene unit that tool improves the material settling out performance owing to both having contained the diphenylene-oxide/thiophene unit of tool hole transport performance, obtain good electroluminescent properties, be conducive to develop efficient full-color display.
Above a kind of dibenzo heterocycle provided by the invention is connected spiro-bisfluorene compound and preparation method thereof and a kind of organic electro phosphorescent device is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the compound shown in the formula I:
Wherein, X is S or O; Ar is the substituting group shown in formula II or the formula III:
2. the preparation method of compound shown in the formula 1 is characterized in that, comprising:
Compound shown in formula IV or the formula V is mixed in organic solvent with the compound shown in the formula VI and alkali-metal carbonate, the Suzuki linked reaction occurs under the effect of catalyzer, obtain crude product;
With described crude product reflux, extracting operation, with carrying out silica gel column chromatography after the extraction liquid drying, obtain the compound shown in the formula I;
Wherein X is O or S, X
1Be F, Cl, Br or I.
3. preparation method according to claim 2 is characterized in that, described catalyzer is tetrakis triphenylphosphine palladium.
4. preparation method according to claim 2 is characterized in that, described organic solvent is tetrahydrofuran (THF).
5. preparation method according to claim 2 is characterized in that, the compound shown in the compound shown in described formula IV or the formula V and the formula VI is in mass ratio: (3.5 ~ 6): (3 ~ 4).
6. preparation method according to claim 2 is characterized in that, the compound shown in described catalyzer and the formula VI is (0.6 ~ 0.7) in mass ratio: (3 ~ 4).
7. an organic electro phosphorescent device is characterized in that, comprising:
Glass;
Be attached to described substrate on glass;
Be arranged on the hole injection layer on the described substrate;
Be arranged on the hole transmission layer on the described hole injection layer;
Be arranged on the luminescent layer on the described hole transmission layer;
Be arranged on the hole blocking layer on the described luminescent layer;
Be arranged on the electron transfer layer on the described hole blocking layer;
Be arranged on the cathode layer on the electron transfer layer;
Wherein, described luminescent layer is comprised of material of main part and dopant material, and described material of main part is the compound shown in the formula 1;
Wherein, X is S or O; Ar is the substituting group shown in formula II or the formula III:
8. organic electro phosphorescent device according to claim 7 is characterized in that, described dopant material is the complex of iridium of cyclic metal complexes.
9. organic electro phosphorescent device according to claim 8 is characterized in that, the complex of iridium of described cyclic metal complexes is one or more in the compound shown in formula 1 ~ formula 4:
10. organic electro phosphorescent device according to claim 9 is characterized in that, the doping ratio of described dopant material in described material of main part is 3wt% ~ 15wt%.
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| CN104418828A (en) * | 2013-08-30 | 2015-03-18 | 关东化学株式会社 | hole transporting material |
| CN105131940A (en) * | 2015-09-08 | 2015-12-09 | 苏州大学 | Organic luminescent material containing spirobifluorene and dibenzothiophene and luminescent device |
| WO2017117960A1 (en) * | 2016-01-04 | 2017-07-13 | 京东方科技集团股份有限公司 | Compound and preparation method therefor, and organic electroluminescent device |
| WO2018198976A1 (en) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | Light-emitting element |
| WO2018198974A1 (en) * | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | Light-emitting element |
| WO2018198971A1 (en) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | Composition and light-emitting element in which same is used |
| WO2018198973A1 (en) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | Composition and light-emitting element using same |
| US20190363260A1 (en) * | 2017-06-07 | 2019-11-28 | Lg Chem, Ltd. | Novel heterocyclic compound and organic light emitting device comprising the same |
| CN111205278A (en) * | 2020-03-03 | 2020-05-29 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787988A (en) * | 2003-05-15 | 2006-06-14 | 出光兴产株式会社 | Arylamine compounds and organic electroluminescent devices containing the same |
| CN102127420A (en) * | 2010-12-13 | 2011-07-20 | 南京邮电大学 | Spiro-iridium organic electrophosphorescent material and preparation method thereof |
| WO2012048820A1 (en) * | 2010-10-11 | 2012-04-19 | Solvay (Societe Anonyme) | A spirobifluorene compound for light emitting devices |
-
2012
- 2012-09-20 CN CN2012103531003A patent/CN102911145A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787988A (en) * | 2003-05-15 | 2006-06-14 | 出光兴产株式会社 | Arylamine compounds and organic electroluminescent devices containing the same |
| WO2012048820A1 (en) * | 2010-10-11 | 2012-04-19 | Solvay (Societe Anonyme) | A spirobifluorene compound for light emitting devices |
| CN102127420A (en) * | 2010-12-13 | 2011-07-20 | 南京邮电大学 | Spiro-iridium organic electrophosphorescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHOU-CHENG DONG，等: "New dibenzofuran/spirobifluorene hybrids as thermally stable host materials for efficient phosphorescent organic light-emitting diodes with low efficiency roll-off", 《PHYS.CHEM.CHEM.PHYS.》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104250242A (en) * | 2013-06-26 | 2014-12-31 | 海洋王照明科技股份有限公司 | Dibenzothiophene unit-containing blue light phosphorescent body material, preparation method thereof and organic electroluminescent device |
| CN104418828A (en) * | 2013-08-30 | 2015-03-18 | 关东化学株式会社 | hole transporting material |
| CN105131940A (en) * | 2015-09-08 | 2015-12-09 | 苏州大学 | Organic luminescent material containing spirobifluorene and dibenzothiophene and luminescent device |
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| KR20190141714A (en) | 2017-04-27 | 2019-12-24 | 스미또모 가가꾸 가부시키가이샤 | Composition and Light-Emitting Device Using the Same |
| KR20190141713A (en) | 2017-04-27 | 2019-12-24 | 스미또모 가가꾸 가부시키가이샤 | Composition and Light-Emitting Device Using the Same |
| CN110574497B (en) * | 2017-04-27 | 2022-10-18 | 住友化学株式会社 | Composition and light-emitting element using same |
| US20190363260A1 (en) * | 2017-06-07 | 2019-11-28 | Lg Chem, Ltd. | Novel heterocyclic compound and organic light emitting device comprising the same |
| CN111205278B (en) * | 2020-03-03 | 2021-11-16 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
| CN111205278A (en) * | 2020-03-03 | 2020-05-29 | 苏州大学 | Spirofluorene triphenylamine derivative and application thereof in organic electroluminescent device |
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