Orthogonally substituted aryl derivatives as bipolar hosts for blue phosphorescent organic light-emitting diodes

Four novel bipolar hosts, namely 9,9′-(2-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole) (2CzPm), 9,9′-(2-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di-tert-butyl-9H-carbazole) (2TCzPm), 5,5′-(2-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(5H-benzofuro[3,2-c]carbazole) (2BFCzPm) and 5,5′-(2-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(5H-benzofuro[3,2-c]carbazole) (2BFCzTrz) were designed and synthesized with diphenylpyrimidine and diphenyltriazine as electron-transporting units and carbazole derivatives as hole-transporting motifs for the application in blue phosphorescent organic light-emitting diodes (PHOLEDs). These electron-accepting and -donating functional groups were attached to the central phenylene bridge in an ortho-substituted fashion, which led to high triplet energies (2.97–3.00 eV) and wide bandgap (3.43–3.55 eV). The effect of modulation of electron-accepting and donating groups on the photophysical properties, frontier orbital energy levels, charge carrier transport properties and device performance of these four hosts has been investigated. 2BFCzPm and 2BFCzTrz featured with large conjugation system exhibited high thermal stability as compared to 2CzPm and 2TCzPm. The bis[2-(4,6-difluorophenyl)-pyridinato-C2,N](picolinato)iridium(III) (FIrpic) based blue PHOLEDs hosted by 2BFCzPm exhibited excellent electroluminescence performance with a peak current efficiency of 38.2 cd/A and a maximum external quantum efficiency of 19.0%, which could be ascribed to the enhanced thermal stability, high triplet energy and good bipolar charge transport properties of the host material.     

Highly efficient near-infrared thermally activated delayed fluorescence material based on a spirobifluorene decorated donor

The development of red/near-infrared (NIR) thermally activated delayed fluorescence (TADF) emitters are relatively lagging due to the spin statistics and energy gap law. Herein, we designed and synthesized a new NIR TADF emitter, 3-(4-(9,9′-spirobi[fluorene]-3-yl(phenyl)amino)phenyl)acenaphtho[1,2-b]pyrazine-8,9-dicarboni-trile (SDPA-APDC), by incorporating a spiro-type electron-donating moiety N,N-diphenyl-9,9′-spirobi[fluorene]-2-amine (SDPA) to an electron-withdrawing unit acenaphtho[1,2-b]pyrazine-8,9-dicarbonitrile (APDC). The photophysical, electrochemical and thermal properties of SDPA-APDC have been systematically explored. Consequently, the emitter was found high photoluminescence quantum yield (PLQY), narrow bandgap, small singlet-triplet energy gap (ΔE_ST) and excellent thermal stability. Furthermore, SDPA-APDC was developed for electroluminescence devices. The doped devices of SDPA-APDC achieved a red emission peak at 696 nm with a maximum external quantum efficiency (EQE) of 10.75%. And the non-doped device exhibited a NIR emission peak at 782 nm with a maximum EQE of 2.55%     

meta-Linked spirobifluorene/phosphine oxide hybrids as host materials for deep blue phosphorescent organic light-emitting diodes

This study investigated the use of a novel modification in molecular design to get two new electron-transport host materials, SF3PO and BSF3PO. By linking the phosphine oxide moieties at meta-position of spirobifluorene rings, higher triplet energies could be easily achieved for these two new materials. The steric spirobifluorene structures could guarantee their good thermal stabilities. According to these properties, their applications as host materials for deep blue phosphorescent organic light-emitting diodes (PHOLEDs) were explored. As expected, the deep blue emitting devices with Ir-complex FIr6 as phosphorescent dopants and SF3PO and BSF3PO as hosts had been fabricated and showed high efficiency of 28.5 and 22.0 cd/A, respectively, which were significantly higher than that of the para-linked analogue SPPO1.     

Molecular design of large-bandgap host materials and their application to blue phosphorescent organic light-emitting diodes

New large-bandgap host materials with carbazole and carboline moieties were designed and synthesized for high-performance blue phosphorescent organic light-emitting diodes (PhOLEDs). The two kinds of host materials, 9-(4-(9H-carbazol-9-yl)phenyl)-6-(9H-carbazol-9-yl)-9H-pyrido[2,3-b]indole (pP2CZCB) and 9-(3-(9H-carbazol-9-yl)phenyl)-6-(9H-carbazol-9-yl)-9H-pyrido[2,3-b]indole (mP2CZCB), displayed promisingly high triplet energies of ∼2.92–2.93 eV for enhancing the exothermic energy transfer to bis[2-(4,6-difluorophenyl)pyridinato-C²,N](picolinato)iridium(III) (FIrpic) in PhOLED devices. It was found that the blue PhOLEDs bearing the new host materials and the FIrpic dopant exhibited markedly higher external quantum efficiencies (EQEs) than a device made with 1,3-bis(N-carbazolyl)benzene (mCP) as the host. In particular, the PhOLED device made with 3 wt% FIrpic as the dopant and mP2CZCB as the host material displayed a low driving voltage of 4.13 V and the high EQE of 25.3% at 1000 cd m⁻².     

4, 6-Bis[3-(dibenzothiophen-2-yl)phenyl] pyrimidine bipolar host for bright,efficient and low efficiency roll-off phosphorescent organic light-emitting devices

A bipolar host 4, 6-Bis[3-(dibenzothiophen-2-yl)phenyl] pyrimidine (DBTPhPm) with small singlet-triplet splitting has been synthesized and confirmed through a series of photophysical and electrochemical properties. Monochromatic phosphorescent organic light-emitting devices (PHOLEDs) based on different hosts [(4,4′-N,N'-dicarbazole) biphenyl, 2,7-bis (diphenylphosphoryl)-9-[4-(N,Ndiphenylamino) phenyl]-9-phenylfluorene, (3,3'-bicarbazole) phenyl and DBTPhPm] and dopants are fabricated. Compared to other hosts, the DBTPhPm-based PHOLEDs exhibited high brightness, high efficiency and low efficiency roll-off. The maximum power efficiency of the DBTPhPm-based red (R), green (G), blue (B), yellow (Y), and orange (O) PHOLEDs are 12.2, 47.2, 17.6, 42.6 and 15.1 lm/W, respectively. The current efficiency roll-off of the R, G, B, Y, and O PHOLEDs are 29.8%, 8.6%, 18.2%, 5.9%, and 22.4% from the maximum current efficiency to the high brightness of 5000 cd/m². The detailed working mechanism of the DBTPhPm-based device is discussed.     

Thermally stable carboline derivative as a host material for blue phosphorescent organic light-emitting diodes

A α-carboline based high triplet energy material, 9,9′-(5′-(carbazol-9-yl)-[1,1′:3′,1″-terphenyl]-3,3″-diyl)di-α-carboline (2CbCzT), was designed and synthesized as the thermally stable host material for blue phosphorescent organic light-emitting diodes (PHOLEDs). The 2CbCzT host showed high glass transition temperature of 149 °C and high decomposition temperature of 518 °C at 5% weight loss. In addition, the 2CbCzT exhibited bipolar charge transport properties due to hole transport type carbazole and electron transport type α-carboline units. Blue PHOLEDs were developed using the high triplet energy 2CbCzT host material and a high quantum efficiency of 22.1% was obtained.     

Efficient blue organic light-emitting diodes based on triphenylimidazole substituted anthracene derivatives

A series of new blue emissive materials based on the conjugates of highly fluorescent diaryl anthracene and electron-transporting triphenylimidazole moieties: 2-(4-(anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (ACBI), 2-(4-(10-(naphthalen-1-yl)anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (1-NaCBI), 2-(4-(10-(naphthalen-2-yl)anthracen-9-yl)phenyl)-1,4,5-triphenyl-1H-imidazole (2-NaCBI) were designed and synthesized successfully. These materials exhibit good film-forming properties and excellent thermal stabilities. Meanwhile, the decreased π-conjugation in these compounds compared with phenanthroimidazole derivatives leads to obvious hypsochromic shift. To explore the electroluminescence properties of these materials, typical three-layer organic light-emitting devices were fabricated. With respect to the three layer device 2 using 1-NaCBI as the emitting layer, its maximum current efficiency reaches 3.06 cd A⁻¹ with Commission Internationale del’Eclairage (CIE) coordinates of (0.149, 0.092). More interestingly, sky blue doped device 5 based on 1-NaCBI achieved a maximum current efficiency of 15.53 cd A⁻¹ and a maximum external quantum efficiency of 8.15%, high EQE has been proved to be induced by the up-conversion of a triplet excited state.     

Novel dibenzothiophene based host materials incorporating spirobifluorene for high-efficiency white phosphorescent organic light-emitting diodes

Two host materials, DBTSF2 and DBTSF4, were designed and synthesized, incorporating dibenzothiophene (DBT) and spirobifluorene (SF) blocks. Their thermal, electrochemical and photo-physical properties were fully characterized. DBTSF4, which adopted an ortho-linkage between DBT and SF moieties, showed a significantly higher T₁ energy of 2.82 eV as compared to its para-linkage analogue DBTSF2 (2.49 eV). Their applications as host for green, blue and white phosphorescent organic light-emitting diodes (PHOLEDs) were explored. The DBTSF4 based blue PHOLED has a highest current efficiency of 23.5 cd A^?1. And using DBTSF4 as a single host, two-color based white PHOLEDs were achieved from cold white emission with CIE coordinate of (0.31, 0.43) to yellowish warm white emission (0.44, 0.49) with maximum current efficiencies varying from 35.8 to 52.3 cd A^?1 and maximum external quantum efficiencies from 13.1% to 16.9% respectively. The white PHOLED devices also showed a low efficiency roll-off even at 10,000 cd m^?2.     

Stable and efficient blue fluorescent organic light-emitting diode by blade coating with or without electron-transport layer

Multi-layer small-molecule blue fluorescent organic light-emitting diode (OLED) is fabricated by blade coating. The emission layer is based on a mixed host of 1-(7-(9,9′-bianthracen-10-yl)-9,9-dioctyl-9H-fluoren-2-yl)pyrene (PT-404) and electron-transport material 2,7-Bis(diphenylphosphoryl)-9,9′ -spirobifluorene (SPPO13), and the blue guest emitter is 4-4′-(1E,1′E)-2,2′-(naphthalene-2,6-diyl)bis(ethane-2,1-diyl)bis(N,N-bis(4-hexyl- Phenyl) aniline) (Blue D). A hole-transport layer of Poly-(9, 9-dioctylfluorenyl-2, 7-diyl)-co-(4, 4-(N-(4-sec-butylphenyl)) diphenylamine) (TFB) is added on top of PEDOT: PSS anode. The electrons are blocked away from TFB by a layer of pure host emission layer of PT-404 between TFB and the mixed –host emission layer. For the device with the electron transport layer of Tris(8-hydroxyquinolinato)aluminum (Alq₃) blade-coated over the emission layer the efficiency and lifetime at initial brightness of 500 cd m⁻² are 7.5 cd A⁻¹ and 150 h for Alq₃/CsF/Al cathode. When the Alq₃/CsF/Al is replaced by simply CsF/Al over the mixed-host emission layer the efficiency and lifetime are 6.4 cd A⁻¹ and 300 h (2 times longer than that of the Alq₃/CsF/Al cathode). The lifetime depends on the electron-hole balance tuned by the mixed-host blending ratio as well as the electron injection from the cathode. This work shows good stability is possible for all-solution-processed blue OLED.     

Design of bicarbazole type host materials for long-term stability in blue phosphorescent organic light-emitting diodes

Two bicarbazole type host materials, 9-(dibenzo [b,d]thiophen-4-yl)-9ʹ-phenyl-9H,9′H-3,3ʹ-bicarbazole (DBTBCz) and 9,9ʹ-bis(dibenzo [b,d]thiophen-4-yl)-9H,9′H-3,3ʹ-bicarbazole (DDBTBCz), were developed as lifetime enhancing host materials for blue phosphorescent organic light-emitting diodes (PhOLEDs). The DBTBCz and DDBTBCz host materials were prepared by substituting one or two dibenzothiophene units to a 3,3ʹ-bicarbazole backbone structure for the purpose of improving thermal stability and rigidity of the host materials for stable operational lifetime. Device characterization of the host materials revealed that the dibenzothiophene modification via 4- position is better than that via 2- position for improved lifetime of blue PhOLEDs.     

Aminoborane-based bipolar host material for blue and white-emitting electrophosphorescence devices

A novel aminoborane-based host material, 9-(dimesitylboryl)-9′-phenyl-9H, 9′H-3,3′-bicarbazole (BCzBMes) was developed for blue and white phosphorescent OLEDs (PHOLEDs). The thermal, photophysical and electrochemical properties were systematically investigated. BCzBMes not only has a high triplet energy but also shows a bipolar behavior. To validate the superior properties of BCzBMes, blue and white PHOLEDs were fabricated using BCzBMes as a bipolar host material. A blue PHOLED containing Bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium (FIrPic) as a dopant exhibited excellent performance with a maximum external quantum efficiency (EQE) of 16.7%. In particular, the blue PHOLED exhibited an extraordinary low efficiency roll-off of 10.1% at a brightness of 5000 cd/m². Meanwhile, an all-phosphor near-white device hosted by BCzBMes was also fabricated, and a high EQE of 18.8% was achieved. This excellent performance suggests that BCzBMes is a potential bipolar host material for the PHOLEDs.     

Acridine derived stable host material for long lifetime blue phosphorescent organic light-emitting diodes

A host material having acridine as a hole transport moiety, 10-(3′-(9H-carbazol-9-yl)-[1,1′-biphenyl]-3-yl)-9,9-dimethyl-9,10-dihydroacridine (CZBPAC), was explored as the host material of phenylimidazole type Ir triplet emitter to realize both high quantum efficiency and stable operational lifetime. The acridine containing CZBPAC was superior to carbazole based host material with the same backbone structure in that it can improve driving voltage, quantum efficiency and lifetime of the blue phosphorescent organic light-emitting diodes simultaneously.     

Synthesis and device properties of mCP analogues based on fused-ring carbazole moiety

Novel mCP analogues consisting of blue phosphorescent host materials with fused-ring, 1,3-bis(5H-benzofuro[3,2-c]carbazol-5-yl)benzene (BFCz) and 1,3-bis(5H-benzo[4,5]thieno[3,2-c]carbazol-5-yl)benzene (BTCz) were designed and synthesized using benzofurocarbazole and benzothienocarbazole donor moieties. BFCz and BTCz exhibit high glass transition temperatures of 147 and 157 °C, respectively, and high triplet bandgaps of 2.94 and 2.93 eV, respectively. To explore the electroluminescence properties of these materials, multilayer blue phosphorescent organic light-emitting diodes (PHOLEDs) were fabricated in the following device structure: indium–tin-oxide (ITO)/PEDOT:PSS/4,4’-cyclohexylidene bis[N,N-bis(4-methylphenyl)aniline] (TAPC)/1,3-bis(N-carbazolyl) benzene (mCP)/host:FIrpic/diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1)/LiF)/Al. The PHOLEDs with BTCz exhibited efficient blue emission with luminous and quantum efficiencies of 30.9 cd/A and 15.5% at 1000 cd/m², respectively.     

Synthesis,photoluminescence and electroluminescence properties of iridium complexes with bulky carbazole dendrons

We synthesized solution-processable iridium complexes having bulky carbazole dendrons, fac-tris[2-{3-(3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl)Phenyl)pyridine]iridium (III) (mCP)₃Ir and fac-bis[2-{3-(3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl)phenyl}pyridine][2-{3-(3,5-di(4-pyridyl)phenyl)phenyl}pyridine]iridium (III) (mCP)₂(bpp)Ir. Photoluminescence quantum efficiencies (PLQEs) of (mCP)₃Ir and (mCP)₂(bpp)Ir in their diluted solutions were 91% and 84%, respectively. They showed high PLQEs of 49% for (mCP)₃Ir and 29% for (mCP)₂(bpp)Ir even in a neat film. The triplet exciton energy level of the dendronized ligand (2.8 eV), 2-[3-{3,5-bis(3,6-di-n-butylcarbazol-9-yl)phenyl}]pyridine 10, and the dendron (2.9 eV), 3,5-bis(3,6-di-n-butylcarbazol-9-yl)benzene 7, are enough higher than that of the core complex Ir(ppy)₃ (2.6 eV). External quantum efficiency (EQE) of single layer light-emitting device with (mCP)₂(bpp)Ir was much higher than that of (mCP)₃Ir because of better affinity of (mCP)₂(bpp)Ir to cathode metal. When an electron transporting and hole-blocking material was used, the EQEs of double layer devices were dramatically improved to 8.3% for (mCP)₃Ir and 5.4% for (mCP)₂(bpp)Ir at 100 cd/m².     

Two trans-1-(9-anthryl)-2-phenylethene derivatives as blue-green emitting materials for highly bright organic light-emitting diodes application

1-(9-Anthryl)-2-phenylethene (t-APE) is a blue-green material with high fluorescence quantum yield (Ф_f 0.44). However, it is easily crystallized. Herein, Two asymmetric blue-green emitting materials based on t-APE, (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-1-yl)anthracene (6) and (E)-9-(4-(2-(anthracen-9-yl)vinyl)phenyl)-10-(naphthalen-2-yl)anthracene (7) were firstly designed and synthesized. The two compounds possess high thermal stability, morphological durability, and bipolar characteristics. The non-doped blue-green organic light-emitting diodes (OLEDs) using 6 and 7 as emitting layers showed emission at 495 nm, full width at half maximum of 80 nm, maximum brightness of 13,814, 10,579 cd m⁻², maximum current efficiency of 3.62, 7.16 cd A⁻¹, and Commission Internationale de L'Eclairage (CIE) coordinate of (0.20, 0.43), respectively. Furthermore, when employing 6 and 7 as blue-green emitting layers and rubrene doped in tris-(8-hydroxyquinolinato)aluminum (Alq3) as the orange emitting layers to fabricate white OLEDs (WOLEDs), the WOLEDs exhibit a maximum brightness of 10,984, 14,652 cd m⁻², maximum current efficiency of 2.04, 2.70 cd A⁻¹, and CIE coordinate of (0.30, 0.40), (0.37, 0.47), Color Rendering Index (CRI) of 65, 60, stable EL spectra, respectively. This study demonstrates that the t-APE-type derivatives have the excellent properties for the emitting materials of OLEDs.     

Deep blue phosphorescent organic light-emitting diodes with excellent external quantum efficiency

Highly efficient deep blue phosphorescent organic light-emitting diodes (PHOLEDs) using two heteroleptic iridium compounds, (dfpypy)₂Ir(acac) and (dfpypy)₂Ir(dpm), as a dopant and 9-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-3-yl)diphenylphosphine oxide as a host material have been developed. The electroluminescent device of (dfpypy)₂Ir(dpm) at the doping level of 3 wt% shows the best performance with external quantum efficiency of 18.5–20.4% at the brightness of 100–1000 cd/m² and the color coordinate of (0.14, 0.18) at 1000 cd/m².     

Charge carrier mobility through vacuum–sublimed glassy films of s-triazine- and carbazole-based bipolar hybrid and unipolar compounds

Instead of physical mixtures as bipolar charge transport media for organic electronics, chemical hybrids comprising non-conjugated spacers are explored to strive for miscibility and morphological stability. Bipolar TRZ-3Cz(MP)2 and TRZ-1Cz(MP)2 as well as unipolar C3-2TRZ(2tBu), C2-2TRZ(2tBu) and C3-2Cz(MP)2 were synthesized with propylene or ethylene spacers serving to decouple the Cz(MP)2 and TRZ moieties. Glassy films were prepared by vacuum sublimation for the characterization of transport properties using the photocurrent time-of-flight technique. The results indicate that both the TRZ:Cz(MP)2 ratio and the spacer length enable charge-carrier mobility to be modulated across orders of magnitude. The C2-2TRZ(2tBu) film exhibits the highest electron mobility of all the unipolar TRZ-based glassy films reported to date.     

Triphenyl phosphine oxide-bridged bipolar host materials for green and red phosphorescent organic light-emitting diodes

Two wide band gap functional compounds of phenylbis(4-(spiro [fluorene-9,9'-xanthen]-2-yl)phenyl)phosphine oxide (2SFOPO) and (4-(9-ethyl-9H- carbazol-3-yl)phenyl)(phenyl)(4-(spiro[fluorene-9,9′-xanthen]-2-yl)phenyl)phosphine oxide (SFOPO-CZ) were designed, synthesized and characterized. Their thermal, photophysical, electrochemical properties and device applications were further investigated to correlate the chemical structure of bipolar host materials with the electroluminescent performance for phosphorescent organic light-emitting diodes (PhOLEDs). Both of them show high thermal stability with glass transition temperatures in a range of 105–122 °C and thermal decomposition temperatures at 5% weight loss in a range of 406–494 °C. The optical band gaps of compound 2SFOPO and SFOPO-CZ in CH₂Cl₂ solution are 3.46 and 3.35 eV, and their triplet energy levels are 2.51 eV and 2.52 eV, respectively. The high photoluminescent quantum efficiency of emissive layer of doped green device up to 50% is obtained. Employing the developed materials, efficient green and red PhOLED in simple device configurations have been demonstrated. As a result, the green PhOLEDs of compound SFOPO-CZ doped with tris(2-phenylpyridine) iridium shows electroluminescent performance with a maximum current efficiency (CE_max) of 52.83 cd A⁻¹, maximum luminance of 34,604 cd/m², maximum power efficiency (PE_max) of 39.50 lm W⁻¹ and maximum external quantum efficiency (EQE_max) of 14.1%. The red PhOLED hosted by compound 2SFOPO with bis(2-phenylpyridine)(acetylacetonato) iridium(III) as the guest exhibits a CE_max of 20.99 cd A⁻¹, maximum luminance of 33,032 cd/m², PE_max of 20.72 lm W⁻¹ and EQE_max of 14.0%. Compound SFOPO-CZ exhibits better green device performance, while compound 2SFOPO shows better red device performance in PhOLEDs.     

Soluble processed low-voltage and high efficiency blue phosphorescent organic light-emitting devices using small molecule host systems

We report low voltage driving and highly efficient blue phosphorescence organic light emitting diodes (PHOLEDs) fabricated by soluble process. A soluble small molecule mixed host system consisting of hole transporting 4,4’,4’’ tris(N-carbazolyl)triphenylamine (TCTA) and bipolar carrier transporting 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine (26DCzPPy) exhibits high solubility with smooth surface properties. Moreover, this small molecule host shows the smoothest morphological property similar to a vacuum deposited amorphous film. A low driving voltage of 5.4 V at 1000 cd/m² and maximum external quantum efficiency 14.6% obtained in the solution processed blue PHOLEDs are useful for large area low cost manufacturing.     

Fully solution-processed and multilayer blue organic light-emitting diodes based on efficient small molecule emissive layer and intergrated interlayer optimization

Efficient and fully solution-processed blue organic light-emitting diodes (OLEDs) based on fluorescent small-molecule and methanol/water soluble conjugated polymer as electron-injection material are reported. The emitting layer is 3,6-bis(9,9,9′,9′-tetrakis (6-(9H-carbazol-9-yl)hexyl)-9H,9′H-[2,2′-bifluoren]-7-yl)dib-nzo[b, d]thiophene 5, 5-dioxide (OCSoC) with a blue-fluorescent small-molecule, and a methanol/water soluble polymer poly[(9,9-bis(30-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene)] (PFN) acted as electron-injection layer (EIL). All the organic layers are spin-coated from solution. The multilayer device structure with emitting layer/electron-injection layer is achieved by solution-processed method without the dissolution problem between layers. The performances of the devices show that the maximum luminous efficiency of the multilayer device is increased about 43%, compared to the single-layer device. PFN acting as the EIL material plays a key role in the improvement of the device performance when used in solution-processed small-molecule OLEDs.