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.     

A highly efficient OLED based on terbium complexes

A neutral ligand 9-(4-tert-butylphenyl)-3,6-bis(diphenylphosphineoxide)-carbazole (DPPOC) and its complex Tb(PMIP)₃DPPOC (A, where PMIP stands for 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) were synthesized. DPPOC has a suitable lowest triplet energy level (24,691 cm^?1) for the sensitization of Tb(III) (⁵D₄: 20,400 cm^?1) and a significantly higher thermal stability (glass transition temperature 137 °C) compared with the familiar ligand triphenylphosphine oxide (TPPO). Experiments revealed that the emission layer of the Tb(PMIP)₃DPPOC film could be prepared by vacuum co-deposition of the complex Tb(PMIP)₃(H₂O)₂ (B) and DPPOC (molar ratio = 1:1). The electroluminescent (EL) device ITO/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-diphenyl-4,4′-diamine (NPB; 10 nm)/Tb(PMIP)₃ (20 nm)/co-deposited Tb(PMIP)₃DPPOC (30 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP; 10 nm)/tris(8-hydroxyquinoline) (AlQ; 20 nm)/Mg_0.9Ag_0.1 (200 nm)/Ag (80 nm) exhibited pure emission from terbium ions, even at the highest current density. The highest efficiency obtained was 16.1 lm W^?1, 36.0 cd A^?1 at 6 V. At a practical brightness of 119 cd m^?2 (11 V) the efficiency remained above 4.5 lm W^?1, 15.7 cd A^?1. These values are a significant improvement over the previously reported Tb(PMIP)₃(TPPO)₂ (C).     

Multifunctional homoleptic iridium(III) dendrimers towards solution-processed nondoped electrophosphorescence with low efficiency roll-off

A series of new iridium dendrimers comprised of bifunctional charge transport peripheral groups have been designed and facilely synthesized. The relationship between the structures and their photophysical, electrochemical and electrophosphorescent performances is investigated. Through the incorporation of rigid electron-transporting phosphine oxide groups and/or hole-transporting arylamine units, the new complexes all have good thermal stabilities with high glass-transition temperature up to 284 °C. Besides, the peripheries sufficiently shield the emissive core from the intermolecular interactions and prevent luminance quenching in neat films. Solution-processed phosphorescent organic light-emitting device (PhOLED) based on bipolar phosphor 2 as neat emitter achieves a maximum current efficiency of 12.4 cd A⁻¹ with Commission Internationale de l’Eclairage coordinates of (0.57, 0.42), and the value remains at 11.5 cd A⁻¹ at a practical luminance of 1000 cd m⁻². This low roll-off can be attributed to the bipolar nature of the emitter. This indicates that rational incorporation of charge-transporting moieties into the sphere of iridium(III) core is a simple and effective approach to develop efficient host-free phosphors for solution-processable nondoped PhOLEDs.     

Efficient solution-processed electrophosphorescent devices using ionic iridium complexes as the dopants

Efficient solution-processed electrophosphorescent devices using two blue-emitting ionic iridium complexes (complex 1 and complex 2) were fabricated, with poly(N-vinylcarbazole) (PVK):1,3-bis(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)benzene (OXD-7) as the host and Cs₂CO₃/Al as the cathode. Using complex 1 as the dopant, we obtained efficient blue-green electrophosphorescence from single-layer devices with a maximum efficiency of 12.2 cd A^?1, a maximum brightness of 12,600 cd m^?2 and CIE (Commission Internationale de l’Éclairage) coordinates of (0.19, 0.45). And the maximum efficiency of the device based on complex 1 can be further improved to 20.2 cd A^?1, when a thin 1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (TPBI) layer was inserted between the light-emitting layer and the cathode. Using complex 2 as the dopant, we obtained deep-blue electrophosphorescence with the emission peak at 458 nm and CIE coordinates of (0.16, 0.22). Our work suggests that ionic iridium complexes are promising phosphors for obtaining efficient electrophosphorescence in the blue region.     

Functionalized terfluorene for solution-processed high efficiency blue fluorescence OLED and electrophosphorescent devices

A new multifunctional blue-emitting terfluorene derivative (TFDPA) featured with triphenylamine groups for hole-transportation and long alkyl chains for solution processability on the conjugation inert bridge centers was reported. TFDPA can give homogeneous thin film by solution process and exhibits high hole mobility (μ_h ≈ 10^?3 cm² V^?1 s^?1) and suitable HOMO for hole injection. Particularly, TFDPA performs efficient deep-blue emission with high quantum yield (～100% in solution, 43% in thin film) and suitable triplet energy (E_T = 2.28 eV), making solution-processed OLED devices of using TFDPA as blue emitter and as host for iridium-containing phosphorescent dopants feasible. The solution-processed nondoped blue OLED device gives saturated deep-blue electroluminescence [CIE = (0.17, 0.07)] with EQE of 2.7%. TFDPA-hosted electrophosphorescent devices performed with EQE of 6.5% for yellow [(Bt)₂Ir(acac)], 9.3% of orange [Ir(2–phq)₃], and 6.9% of red [(Mpq)₂Ir(acac)], respectively. In addition, with careful control on the doping concentration of [(Bt)₂Ir(acac)], a solution-processed fluorescence–phosphorescence hybrided two-color-based WOLED with EQE of 3.6% and CIE coordinate of (0.38, 0.33) was successfully achieved.     

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.     

High-efficiency hybrid organic–inorganic light-emitting devices

We report efficient red, orange, green and blue organic–inorganic light emitting devices using light emitting polymers and polyethylenimine ethoxylated (PEIE) interlayer with the respective luminance efficiency of 1.3, 2.7, 10 and 4.1 cd A⁻¹, which is comparable to that of the analogous conventional devices using a low work-function metal cathode. This is enabled by the enhanced electron injection due to the effective reduction of the ZnO work-function by PEIE, as well as hole/exciton-blocking function of PEIE layer. Due to the benign compatibility between PEIE and the neighboring organic layer, the novel phosphorescent organic–inorganic devices using solution-processed small molecule emissive layer show the maximum luminance efficiency of 87.6 cd A⁻¹ and external quantum efficiency of 20.9% at 1000 cd m⁻².     

Synthesis and photovoltaic properties of new small molecules with rhodanine derivative as the end-capped blocks

Two new acceptor–donor–acceptor (A–D–A) type small molecules DCAO3TIDT and DCNR3TIDT, with 4,4,9,9-tetrakis(4-(dodecyloxy)phenyl)-4,9-dihydro-s-indaceno-[1,2-b:5,6-b′]dithiophene (IDT) as the core group and 2-ethylhexyl cyanoacetate (CAO) and 2-(1,1-dicyanomethylene)-3-octyl rhodanine (CNR) as different end-capped blocks, have been designed and synthesized. Both of them have been employed as donor for solution-processed bulk hetero-junction (BHJ) organic solar cells (OSCs). The two compounds showed deep highest occupied molecular orbital (HOMO) energy levels (∼−5.30 eV) and strong absorption. The DCAO3TIDT and DCNR3TIDT with PC₇₁BM as acceptor based BHJ solar cell devices showed short circuit current density (J_sc) of 6.93 mA/cm² and 8.59 mA/cm², power conversion efficiency (PCE) of 3.34% and 4.27%, respectively, and with almost same open-circuit voltage (∼0.93 V), under the illumination of AM 1.5 G, 100 mW/cm². The high J_sc for DCNR3TIDT could result from its wider and red-shifted absorption than that of DCAO3TIDT, which was probably induced by the end-capped block rhodanine derivative. The results demonstrate that the end group would be taken into full account when designing new solution-processed small molecules, which is an important factor to determine their photovoltaic properties.     

High-efficiency and multi-function blue fluorescent material for organic electroluminescent devices

We demonstrate one high-efficiency blue fluorescent material, N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine, with an emissive peak of 472 nm and the hole-transporting property speculated from different devices. It can function either as the single emissive layer or as the dye doped in N,N′-dicarbazolyl-4-4′-biphenyl (CBP). The former shows a maximum current efficiency and luminance of 7.06 cd/A (0.04 mA/cm²) and 16 930 cd/m², in contrast to 11.5 cd/A (4.35 mA/cm²) and 25 690 cd/m² for the latter. The better performance of the latter can be attributed to the bipolar carrier transport property of CBP and the hole-blocking and electron-transporting characteristic of 4,7-diphenyl-1,10-phenanthroline (BPhen), which resulting in a good balance of holes and electrons. Moreover, the Commission Internationale De L’Eclairage coordinates of the latter change slightly from (0.162, 0.3) to (0.148, 0.268) upon increasing the voltage from 3 V to 14 V.     

Solution-processable and thermal-stable triphenylamine-based dendrimers with truxene cores as hole-transporting materials for organic light-emitting devices

Two solution processable π-conjugated triphenylamine-based dendrimers, Tr-TPA3 and Tr-TPA9 were served as hole-transporting materials (HTMs) for organic light-emitting devices (OLEDs). The two dendrimers exhibit similar absorption and emission behaviors in solutions and thin films, which demonstrate that these dendrimers can form amorphous states in their films. The dendrimers showed excellent solubility, which are soluble in common organic solvents such as chloroform, tetrahydrofuran, and 1,1,2,2-tetrachloroethane, high thermal stability with high glass-transition temperature (T_g) of 115 °C for Tr-TPA3 and 140 °C for Tr-TPA9, high the highest unoccupied molecular orbital (HOMO) energy level (?5.12 eV for Tr-TPA3 and ?4.95 eV for Tr-TPA9, respectively) and good film forming property. When we employed these dendrimers as hole transport layer (HTL) in tris-(8-hydroxyquinoline) aluminum (Alq₃)-emitting electroluminescence (EL) devices, the Tr-TPA9-based double-layer device exhibited the turn-on voltage of 2.5 V, the maximum luminance of about 11,058 cd m^?2 and the maximum current efficiency of 4.01 cd A^?1. The comparison of the properties between the EL devices with dendrimers as HTL and the EL device with 1,4-bis(1-naphthylphenylamino)biphenyl (NPB) as HTL indicated that this series of dendrimers can be good candidates for HTM in OLEDs.     

Synthesis,characterization and semiconducting properties of oligo(2,6-naphthalene)s

Oligo(2,6-naphthalene)s (nNs) with the number of repeating unit (n) of 3–5 and dioctyl substituted trimer (DO-3N) and tetramer (DO-4N) were synthesized and characterized. Except of DO-4N that decomposed at 331 °C, all other oligomers display good thermal stability with 5% weight loss temperatures beyond 350 °C. For 4N and DO-4N, only one phase transition corresponding to melting can be found. However, DO-3N and 5N exhibit multiple phase transitions. The film absorption maximum of the oligomers at the long wavelength exhibits a red-shift with increasing the number of repeating unit. Meanwhile, the highest occupied molecular orbital (HOMO) levels increase from −5.96 eV of 3N to −5.91 eV of 4N and then −5.85 eV of 5N. The introduction of octyl group has negligible effect on the photophysical properties. Highly ordered films of 4N, 5N, DO-3N and DO-4N in which the molecules orient with their long axis standing on the substrates can be prepared by vacuum deposition. Organic thin-film transistors (OTFTs) with top-contact and bottom-gate geometry have been fabricated based on these films. The introduction of octyl groups results in the films with higher order and therefore higher field-effect mobilities (μ) of OTFT devices. Among these oligomers, DO-3N exhibits the highest mobility of 0.50 cm²/V s when the film deposited on the octyltrichlorosilane (OTS) modified substrate.     

Hole mobilities of thermally polymerized triaryldiamine derivatives and their application as hole-transport materials in organic light-emitting diodes (OLEDs)

This paper describes the synthesis of three triaryldiamine derivatives presenting two thermally polymerizable trifluorovinyl ether groups that can be polymerized through thermal curing to form perfluorocyclobutyl (PFCB) polymers. These PFCB polymers, studied using time-of-flight techniques for the first time, exhibited remarkable non-dispersive hole-transport properties, with values of μ_h of ca. 10^?4 cm² V^?1 s^?1. When we employed these thermally polymerized polymers as hole-transport layers (HTLs) in electroluminescence devices containing tris(8-hydroxyquinolate) aluminum (Alq₃) as the emission layer, we obtained high current densities (ca. 3400 mA cm^?2), impressive brightnesses (5 × 10⁴ cd m^?2), and high external quantum efficiencies (EQEs = 1.43%). These devices exhibited the same turn-on voltage, but higher EQEs, relative to those incorporating the vacuum-processed model compound N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (α-NPD) (EQE = 1.37%) as the HTL under the same device structure.     

Effect of substituents on the properties of indolo[3,2-b]carbazole-based hole-transporting materials

Three new compounds based on indolo[3,2-b]carbazole,2,8-bis(4-diphenylaminophenyl)-5,11-di-n-octylindolo[3,2-b]carbazole (BTOICZ), 2,8-bis(9,9′-di-n-butylfluorenyl)-5,11-di-n-octylindolo[3,2-b]carbazole (BFOICZ) and 2,8-bis[N-(n-butyl)carbazolyl]-5,11-di-n-octylindolo[3,2-b]carbazole (BCOICZ), as hole-transporting materials have been synthesized by Suzuki coupling reaction. The effects of substituents on the optical, thermal and electrochemical properties of indolo[3,2-b]carbazole derivatives have been studied carefully. Electroluminescent (EL) devices using these compounds as hole-transporting layer in combination with Alq₃ as electron-transporting and emitting layer have been fabricated and characterized. The devices based on BTOICZ or BFOICZ showed green emission at 526 nm, while the device based on BCOICZ emitted very weak light. The turn-on voltages are 4.1 and 5.4 V for BTOICZ and BFOICZ, respectively. The maximal luminance efficiencies are 0.738 and 0.767 lm/W for BTOICZ and BFOICZ, respectively. The difference of the EL performances of these compounds reveals that the substituent effects have great effect on the hole-transporting performance of the indolo[3,2-b]carbazole-based compounds.     

Fluorene trimers with various 9,9′-substituents: The synthesis,characteristics, condensed state structures,and electroluminescence properties

The four fluorene-based trimers with various aromatic and alkyl substituents (T1–T4) are synthesized and characterized. These oligomers show the similar electronic absorption and emission characteristics (e.g., absorption peak at 351 nm, and highly efficient deep blue emission at 394 nm in solution), indicating that the major electronic properties of the core chromophore are essentially independent of the substituents. However, the condensed state structures and thermal properties of four trimers are found to be different from each other, from crystalline (full alkyl (T1) or full aromatic (T2) substituted trimers) to amorphous (mixed aromatic and alkyl (T4) substituted trimers). The effect of different condensed state structures on electroluminescence device properties is presented: The blue light-emitting devices with accordant structure of ITO/PEDOT:PSS/TCTA (40 nm)/trimers (40 nm)/BCP (10 nm)/Alq₃ (20 nm)/LiF/Al exhibit different EL efficiency (2.9% of T2, 1.8% of T3 and 2.7% of T4). Using amorphous T4, the white light-emitting device of ITO/TCTA (40 nm)/rubrene (0.1 nm)/T4 (8 nm)/Alq₃(52 nm)/LiF/Al is fabricated with high efficiency (6.15 cd A⁻¹), high brightness (9500 cd m⁻²) and good white light CIE coordinates (0.32, 0.37).     

A new ambipolar blue emitter for NTSC standard blue organic light-emitting device

A novel blue emitter, In2Bt, featured with a rigid and coplanar distyryl-p-phenylene backbone flattened by two different bridging atoms (i.e. carbon and sulfur) exhibits high thermal and morphological stability (T_g ～ 192 °C) and ambipolar charge carrier mobilities in the range of 10^?4 ～ 10^?5 cm² V^?1 s^?1. OLED device: ITO/PEDOT:PSS (300 Å)/α-NPD (200 Å)/TCTA (100 Å)/In2Bt (200 Å)/TPBI (500 Å)/LiF (5 Å)/Al (1500 Å) utilized In2Bt as an emitter gave a maximum brightness as high as 8000 cd m^?2 (12 V) and saturated-blue emission with CIE chromaticity coordinates of (0.16, 0.08), which is very close to the National Television Standards Committee (NTSC) standard blue gives an enlarged palette of colors for color displays.     

Simple-structured efficient white organic light emitting diode via solution process

High-efficiency white emission is crucial to the design of energy-saving display and lighting panels, whereas solution-process feasibility is highly desirable for large area-size and cost-effective roll-to-roll manufacturing. In this study, we demonstrate highly-efficient, bright and chromaticity stable white organic light emitting diodes (OLEDs) with solution-processed single emissive layer. The resultant best white OLED shows excellent electroluminescence performance with forward-viewing external quantum efficiency, current efficiency and power efficiency of 22.7%, 48.8 cd A^− 1 and 27.8 lm W^− 1 at 100 cd m^− 2, respectively, with a maximum luminance of 19,590 cd m^− 2. Furthermore, we also observed an increment of 112% in the power efficiency, 86.9% in the current efficiency and a decrement of 39.2% in the external quantum efficiency at 100 cd m^− 2 as the doping concentration of blue dye was increased from 10 wt% to 25 wt% in the devices. The better efficiency performance may be attributed to the effective exciton-confining device architecture and low-energy barrier for electrons to inject from the hole-blocking electron-transport layer to the host layer.     

Tuning the energy gap and charge balance property of bipolar host by molecular modification: Efficient blue electrophosphorescence devices based on solution-process

Three bipolar hosts composed of electron-accepting diphenylphosphine oxide and electron-donating carbazole/triphenylamine have been synthesized and characterized. With structural topology modification, the particular physical properties of the materials can be subtly optimized, such as the thermal stability, singlet–triplet energy gap and charge balance ability. Both DFT calculation and experiment results demonstrate that the introduced triphenylamine can effective minimize the HOMO–LUMO energy gap, while the carbazole units can prevent the excited energy loss and keep high triplet energy (E_T = 3.0 eV) due to the enhanced molecular rigidity. As a result, solution-processed blue PHOLEDs exhibited a high current efficiency of 25.2 cd A⁻¹ and a power efficiency of 11.5 lm W⁻¹, which implies that the unique molecular modulation is very cost-effective and competitive for the device performance improving.     

White emission polymer light-emitting devices with efficient electron injection from alcohol/water-soluble polymer/Al bilayer cathode

We demonstrate highly efficient white emission polymer light-emitting diodes (WPLEDs) from multilayer structure formed by solution processed technique, in which alcohol/water-soluble polymer, poly [(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) was incorporated as electron-injection layer and Al as cathode. It was found that the device performance was very sensitive to the solvents from solution of which the PFN electron-injection layer was cast. Devices with electron-injection layer cast from methanol solution show degraded performance while the best device performance was obtained when mixed solvent of water and methanol with ratio of 1:3 was used. We attribute the variation in device performance to washing out the electron transport material in the emissive layer due to rinse effect. As a result of alleviative loss of electron transport material in the emissive layer, the optimized device with a peak luminous efficiency of 18.5 cd A^?1 for forward-viewing was achieved, which is comparable to that of the device with same emissive layer but with low work-function metal Ba cathode (16.6 cd A^?1). White emission color with Commission International de I’Eclairage coordinates of (0.321, 0.345) at current 10 mA cm^?2 was observed.     

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.     

Concentration-insensitive and low-driving-voltage OLEDs with high efficiency and little efficiency roll-off using a bipolar phosphorescent emitter

A series of simplified trilayer phosphorescent organic light-emitting diodes (PHOLEDs) with high efficiency and little efficiency roll-off based on a bipolar iridium emitter Iridium(III) bis(2-phenylpyridinato)-N,N′-diisopropyl-diisopropyl-guanidinate (ppy)₂Ir(dipig) has been demonstrated. They are dominated by the efficient direct-exciton-formation mechanism and show gratifying concentration-insensitive and low-driving-voltage features. In particular, very high and stable electroluminescence (EL) efficiencies (maximum power efficiency and external quantum efficiency >98 lm W^?1 and 25% respectively, and external quantum efficiency >20% over a wide luminance range of 1–15,000 cd m^?2) are achieved in the PHOLEDs based on emitting layers (EMLs) consisting of (ppy)₂Ir(dipig) codeposited with common host CBP in an easily controlled doping concentration range (15–30 wt%). The EL performance of the PHOLEDs is comparable to the highest PHOLEDs reported in scientific literature.