The widely used hole-transporting host 4,4′,4″-tris(N-carbazolyl)-triphenylamine (TCTA) blended with either a hole-transporting or an electron-transporting small-molecule material as a mixed-host was investigated in the phosphorescent organic light-emitting diodes (OLEDs) fabricated by the low-cost solution-process. The performance of the solution-processed OLEDs was found to be very sensitive to the composition of the mixed-host systems. The incorporation of the hole-transporting 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) into TCTA as the mixed-host was demonstrated to greatly reduce the driving voltage and thus enhance the efficiency due to the improvement of hole injection and transport. On the basis of the mixed-host of TCTA:TAPC, we successfully fabricated low driving voltage and high efficiency blue and white phosphorescent OLEDs. A maximum forward viewing current efficiency of 32.0 cd/A and power efficiency of 25.9 lm/W were obtained in the optimized mixed-host blue OLED, which remained at 29.6 cd/A and 19.1 lm/W at the luminance of 1000 cd/m2 with a driving voltage as low as 4.9 V. The maximum efficiencies of 37.1 cd/A and 32.1 lm/W were achieved in a single emissive layer white OLED based on the TCTA:TAPC mixed-host. Even at 1000 cd/m2, the efficiencies still reach 34.2 cd/A and 23.3 lm/W and the driving voltage is only 4.6 V, which is comparable to those reported from the state-of-the-art vacuum-evaporation deposited white OLEDs.Keywords: blue and white OLEDs; mixed-host; phosphorescence; small molecules; solution-processed;

We present a simple hybrid white organic light-emitting diodes (WOLED) consisting of only two layers, i.e., a hole-transporting layer and an emitting layer. The emitting layer is formed by simply co-doping a green phosphor and a red phosphor in bis[2-(2-hydroxyphenyl)-pyridine]beryllium (Bepp2), which acts as the blue emitter, electron-transport material, and high triplet energy host for the phosphors, i.e., a multifunctional chromophore. This simple device exhibits a maximum power and quantum efficiency of 46.8 lm W−1 and 16.5%, respectively, with a good CRI up to 90. The versatile experimental techniques are performed to gain a deep understanding of the emission mechanism. We believe that this simple design concept can provide a new avenue for achieving ultrahigh performance WOLEDs for lighting application.Graphical abstractAn ultra-simple hybrid WOLED with high efficiency (46.8 lm W-1 and 16.5%) and CRI (90) is reported. This is one of the best hybrid WOLEDs’ stories so far considering the comprehensive properties. Versatile experimental techniques are performed to gain a deep understanding of the emission mechanism. We believe that this simple design concept can provide a new avenue for achieving ultrahigh-performance hybrid WOLEDs for lighting application.Highlights► Highly efficient hybrid white organic light-emitting diode was proposed. ► The simple device consists of a hole-transporting layer and an emitting layer. ► The maximum power efficiency of 46.8 lm W−1 with CRI up to 90 was achieved. ► This concept offers a low-cost fabrication process for hybrid white device.

•Introducing F, Cl or Br atom to the 4-position of pyridine ring in sky-blue emitter FIrpic.•The 4-Cl-FIrpic based PhOLEDs showed maximum 39 cd A−1, 41 lm W−1 and EQE of 16%.•The 4-F-FIrpic based PhOLEDs showed maximum 29 cd A−1, 29 lm W−1 and EQE of 14.6%.Three new iridium compounds, 4-F-FIrpic, 4-Cl-FIrpic and 4-Br-FIrpic, were designed and synthesized by introducing the F, Cl and Br atoms to the 4-position of pyridine ring in the frame of sky-blue emitter, FIrpic. Adding F atom stabilizes the HOMO level of FIrpic but keeps the LUMO level of FIrpic almost unchanged, which consequently broadens the HOMO–LUMO gap of FIrpic and finely tunes the emission to 465 nm of 4-F-FIrpic from 470 nm of FIrpic. In contrast, introducing of Cl and Br atoms simultaneously lowers the HOMO and LUMO levels of FIrpic, which brings about the squeeze of HOMO–LUMO gap in FIrpic and makes the emissions of 4-Cl-FIrpic and 4-Br-FIrpic red-shift to 475 and 479 nm, respectively. The phosphorescent organic light-emitting devices using the three iridium compounds as dopants were fabricated with the following configuration: ITO/MoO3/TAPC/TCTA:dopants/Tm/LiF/Al. The device based on 4-F-FIrpic showed a blue emission with the Commission Internationale de L’Eclairage coordinate of (0.15, 0.28), and revealed rather high efficiencies, with maximum current efficiency of 29 cd A−1, power efficiency of 29 lm W−1 and external quantum efficiency of 14.6%.Graphical abstract

•We synthesized two spiro-annulated triphenylamine/fluorene hybrids as host materials.•The materials show ET of 2.83 eV, HOMO level of −5.31 eV and Tg of 189 °C.•The device showed maximum power efficiency of 42 lm W−1 and EQE of 19.1%.Two spiro-annulated triphenylamine/fluorene oligomers, namely 4′-(9,9′-spirobifluoren-4-yl)-10-phenyl-10H-spiro[acridine-9,9′-fluorene] (NSF-SF), and 4,4′-di(spiro(triphenylamine-9,9′-fluorene)-2-yl)-spiro(triphenylamine-9,9′-fluorene) (NSF-NSF), are designed and synthesized. Their thermal, electrochemical and photophysical properties were investigated. The introduction of spiro-annulated triphenylamine moieties assurances the high HOMO energy levels of NSF-NSF and NSF-SF at −5.31 eV and −5.33 eV, respectively, which accordingly facilitates the hole injection from nearby hole-transporting layer. Meanwhile, the perpendicular arrangement of the spiro-conformation and the full ortho-linkage effectively prevents the extension of the π-conjugation and consequently guarantees their high triplet energies of 2.83 eV. Phosphorescent organic light-emitting devices (PhOLEDs) with the configurations of ITO/MoO3/TAPC/EML/TmPyPB/LiF/Al were fabricated by using the two compounds as host materials and bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) picolate (FIrpic) as the dopant. The turn-on voltage of the device B based on NSF-NSF was 2.8 V. Simultaneously, the device exhibited excellent performance with the maximum current efficiency of 41 cd A−1, the maximum power efficiency of 42 lm W−1 and the maximum external quantum efficiency (EQE) of 19.1%. At a high brightness of 1000 cd m−2, the device remained EQE of 16.2% and the roll-off value of external quantum efficiency is 15%.

The widely used hole-transporting host 4,4′,4″-tris(N-carbazolyl)-triphenylamine (TCTA) blended with either a hole-transporting or an electron-transporting small-molecule material as a mixed-host was investigated in the phosphorescent organic light-emitting diodes (OLEDs) fabricated by the low-cost solution-process. The performance of the solution-processed OLEDs was found to be very sensitive to the composition of the mixed-host systems. The incorporation of the hole-transporting 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) into TCTA as the mixed-host was demonstrated to greatly reduce the driving voltage and thus enhance the efficiency due to the improvement of hole injection and transport. On the basis of the mixed-host of TCTA:TAPC, we successfully fabricated low driving voltage and high efficiency blue and white phosphorescent OLEDs. A maximum forward viewing current efficiency of 32.0 cd/A and power efficiency of 25.9 lm/W were obtained in the optimized mixed-host blue OLED, which remained at 29.6 cd/A and 19.1 lm/W at the luminance of 1000 cd/m2 with a driving voltage as low as 4.9 V. The maximum efficiencies of 37.1 cd/A and 32.1 lm/W were achieved in a single emissive layer white OLED based on the TCTA:TAPC mixed-host. Even at 1000 cd/m2, the efficiencies still reach 34.2 cd/A and 23.3 lm/W and the driving voltage is only 4.6 V, which is comparable to those reported from the state-of-the-art vacuum-evaporation deposited white OLEDs.Keywords: blue and white OLEDs; mixed-host; phosphorescence; small molecules; solution-processed;

•Introducing F, Cl or Br atom to the 4-position of pyridine ring in sky-blue emitter FIrpic.•The 4-Cl-FIrpic based PhOLEDs showed maximum 39 cd A−1, 41 lm W−1 and EQE of 16%.•The 4-F-FIrpic based PhOLEDs showed maximum 29 cd A−1, 29 lm W−1 and EQE of 14.6%.Three new iridium compounds, 4-F-FIrpic, 4-Cl-FIrpic and 4-Br-FIrpic, were designed and synthesized by introducing the F, Cl and Br atoms to the 4-position of pyridine ring in the frame of sky-blue emitter, FIrpic. Adding F atom stabilizes the HOMO level of FIrpic but keeps the LUMO level of FIrpic almost unchanged, which consequently broadens the HOMO–LUMO gap of FIrpic and finely tunes the emission to 465 nm of 4-F-FIrpic from 470 nm of FIrpic. In contrast, introducing of Cl and Br atoms simultaneously lowers the HOMO and LUMO levels of FIrpic, which brings about the squeeze of HOMO–LUMO gap in FIrpic and makes the emissions of 4-Cl-FIrpic and 4-Br-FIrpic red-shift to 475 and 479 nm, respectively. The phosphorescent organic light-emitting devices using the three iridium compounds as dopants were fabricated with the following configuration: ITO/MoO3/TAPC/TCTA:dopants/Tm/LiF/Al. The device based on 4-F-FIrpic showed a blue emission with the Commission Internationale de L’Eclairage coordinate of (0.15, 0.28), and revealed rather high efficiencies, with maximum current efficiency of 29 cd A−1, power efficiency of 29 lm W−1 and external quantum efficiency of 14.6%.Graphical abstract

•We synthesized two spiro-annulated triphenylamine/fluorene hybrids as host materials.•The materials show ET of 2.83 eV, HOMO level of −5.31 eV and Tg of 189 °C.•The device showed maximum power efficiency of 42 lm W−1 and EQE of 19.1%.Two spiro-annulated triphenylamine/fluorene oligomers, namely 4′-(9,9′-spirobifluoren-4-yl)-10-phenyl-10H-spiro[acridine-9,9′-fluorene] (NSF-SF), and 4,4′-di(spiro(triphenylamine-9,9′-fluorene)-2-yl)-spiro(triphenylamine-9,9′-fluorene) (NSF-NSF), are designed and synthesized. Their thermal, electrochemical and photophysical properties were investigated. The introduction of spiro-annulated triphenylamine moieties assurances the high HOMO energy levels of NSF-NSF and NSF-SF at −5.31 eV and −5.33 eV, respectively, which accordingly facilitates the hole injection from nearby hole-transporting layer. Meanwhile, the perpendicular arrangement of the spiro-conformation and the full ortho-linkage effectively prevents the extension of the π-conjugation and consequently guarantees their high triplet energies of 2.83 eV. Phosphorescent organic light-emitting devices (PhOLEDs) with the configurations of ITO/MoO3/TAPC/EML/TmPyPB/LiF/Al were fabricated by using the two compounds as host materials and bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III) picolate (FIrpic) as the dopant. The turn-on voltage of the device B based on NSF-NSF was 2.8 V. Simultaneously, the device exhibited excellent performance with the maximum current efficiency of 41 cd A−1, the maximum power efficiency of 42 lm W−1 and the maximum external quantum efficiency (EQE) of 19.1%. At a high brightness of 1000 cd m−2, the device remained EQE of 16.2% and the roll-off value of external quantum efficiency is 15%.