•Two bipolar host materials mCPpPO and mCPmPO have been disigned and synthesized.•High efficiency and low roll off blue device were fabricated.•The high efficiency single emission layer white PhOLED basd on mCPmPO was obtained.Two bipolar host materials, mCPpPO and mCPmPO have been synthesized by Ni(II)/Zn-catalyzed cross-coupling of diphenylphosphine oxide and corresponding aryl bromide. The photophysical properties, HOMO/LUMO orbital distribution and triplet levels of these host materials are investigated and optimized by tuning the linking modes between electron acceptor triphenylphosphine oxide and electron donor N,N′-dicarbazolyl-3,5-benzene (mCP). When mCP is linked to the meta-position of benzene of triphenylphosphine oxide, the hybrid (mCPmPO) shows much higher steric hinderance than the para-position linked analogue (mCPpPO) so that it possesses a higher triplet energy. Equipped with the bipolar transport properties, mCPmPO-based blue PhOLED doped FIrpic shows a maximum current efficiency (ηc,max) of 40.0 cd/A, a maximum power efficiency (ηp,max) of 39.7 lm/W, corresponding the maximum external quantum efficiency (ηEQE,max) of 20.3%, and the current efficiency still maintain to 34.8 cd/A even at 1000 cd/m2. Based on the optimized triplet energy level, the single emission layer white PhOLED hosted by mCPmPO shows ηc,max, ηp,max and ηEQE,max of 46.9 cd/A, 39.7 lm/W and 17.6%, respectively.Graphical abstract

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;

•Multimode TWOLED is realized by changing the thickness of hole transport layer.•The multimode TWOLED exhibits improved color purity and a wider color gamut.•Good performances are attributed to intrinsic emission and microcavity structure.By changing the thickness of hole transport layer to control the cavity length, a top-emitting white organic light-emitting diode (TWOLED) with three individual narrow peaks matching well with the three primary color filters has been successfully realized. It is very important to carefully design the multimode microcavity for the achievement of the three-peak spectrum. Compared with the bottom-emitting white organic light-emitting diodes (BWOLEDs), the TWOLEDs exhibit improved color purity and a wider color gamut due to the narrow emissive spectrum. The maximum current efficiency and power efficiency of TWOLED reach 28.9 cd/A and 27.5 lm/W, respectively. It is predicted that this kind of three-peak TWOLEDs is suitable for the high-quality display application.Graphical abstract

•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

•Green TWOLED with enhanced coupling efficiency is realized by coupling layer design.•The refractive indices of the coupling layers reduce smoothly.•The doping layer acts as a diffuser film to gives stable colors over angles.By means of refractive index gradually changed coupling layers, a highly efficient green top-emitting OLED (TOLED) with enhanced light coupling efficiency and stable colors over angles has been realized. The refractive index transition of the coupling layers including the doping layer smoothes light extraction from the semitransparent cathode metal to the air, which is the reason for the enhancement of light coupling efficiency. The doping layer in the coupling layers also acts as a microparticle diffuser to eliminate the shift in EL spectra with viewing angles. A universal simulation has also been carried out, and the result suggests that the light coupling efficiency will be enhanced further if the refractive index transition of the coupling layers is continuous.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;

In this paper, highly efficient and simple monochrome blue, green, orange, and red organic light emitting diodes (OLEDs) based on ultrathin nondoped emissive layers (EMLs) have been reported. The ultrathin nondoped EML was constructed by introducing a 0.1 nm thin layer of pure phosphorescent dyes between a hole transporting layer and an electron transporting layer. The maximum external quantum efficiencies (EQEs) reached 17.1%, 20.9%, 17.3%, and 19.2% for blue, green, orange, and red monochrome OLEDs, respectively, indicating the universality of the ultrathin nondoped EML for most phosphorescent dyes. On the basis of this, simple white OLED structures are also demonstrated. The demonstrated complementary blue/orange, three primary blue/green/red, and four color blue/green/orange/red white OLEDs show high efficiency and good white emission, indicating the advantage of ultrathin nondoped EMLs on constructing simple and efficient white OLEDs.Keywords: interface doping; nondoped emissive layer; organic light-emitting diode; simple; ultrathin emissive layer; white;

•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%.

•Two bipolar host materials mCPpPO and mCPmPO have been disigned and synthesized.•High efficiency and low roll off blue device were fabricated.•The high efficiency single emission layer white PhOLED basd on mCPmPO was obtained.Two bipolar host materials, mCPpPO and mCPmPO have been synthesized by Ni(II)/Zn-catalyzed cross-coupling of diphenylphosphine oxide and corresponding aryl bromide. The photophysical properties, HOMO/LUMO orbital distribution and triplet levels of these host materials are investigated and optimized by tuning the linking modes between electron acceptor triphenylphosphine oxide and electron donor N,N′-dicarbazolyl-3,5-benzene (mCP). When mCP is linked to the meta-position of benzene of triphenylphosphine oxide, the hybrid (mCPmPO) shows much higher steric hinderance than the para-position linked analogue (mCPpPO) so that it possesses a higher triplet energy. Equipped with the bipolar transport properties, mCPmPO-based blue PhOLED doped FIrpic shows a maximum current efficiency (ηc,max) of 40.0 cd/A, a maximum power efficiency (ηp,max) of 39.7 lm/W, corresponding the maximum external quantum efficiency (ηEQE,max) of 20.3%, and the current efficiency still maintain to 34.8 cd/A even at 1000 cd/m2. Based on the optimized triplet energy level, the single emission layer white PhOLED hosted by mCPmPO shows ηc,max, ηp,max and ηEQE,max of 46.9 cd/A, 39.7 lm/W and 17.6%, respectively.Graphical abstract

•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