New n-type organic semiconductors: synthesis, single crystal structures, cyclic voltammetry, photophysics, electron transport, and electroluminescence of a series of diphenylanthrazolines

The synthesis, properties, and electroluminescent device applications of a series of five new diphenylanthrazoline molecules 1a-1e are reported. Compounds 1b, 1c, and 1d crystallized in the monoclinic system with the space groups P2(1)/c, C2/c, and P2(1)/c, respectively, revealing highly planar molecules. Diphenylanthrazolines 1a-1e have a formal reduction potential in the range -1.39 to -1.58 V (versus SCE) and estimated electron affinities (LUMO levels) of 2.90-3.10 eV. Compounds 1a-1e emit blue light with fluorescence quantum yields of 58-76% in dilute solution, whereas they emit yellow-green light as thin films. The diphenylanthrazoline molecules as the emissive layers in light-emitting diodes gave yellow light with a maximum brightness of 133 cd/m(2) and an external quantum efficiency of up to 0.07% in ambient air. Bilayer light-emitting diodes using compounds 1a-1e as the electron-transport layer and poly(2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene) as the emissive layer had a maximum external efficiency of 3.1% and 2.0 lm/W and a brightness of up to 965 cd/m(2) in ambient air. These results represent enhancements of up to 50 times in external quantum efficiency and 17 times in brightness when using 1a-1e as the electron-transport materials in polymer light-emitting diodes. These results demonstrate that the new diphenylanthrazolines are promising n-type semiconductors for organic electronics.     

Solid-state highly fluorescent diphenylaminospirobifluorenylfumaronitrile red emitters for non-doped organic light-emitting diodes

Bright (maximum 11,000 cd m(-2) and 500 cd m(-2) at 20 mA cm(-2)) and efficient (maximum external quantum efficiency of 3.1% at 1 mA cm(-2)) red (CIE, x = 0.66, y = 0.34) organic light-emitting diodes (OLEDs) employ arylaminospirobifluorene-substituted fumaronitriles as the novel non-dopant red emitter.     

Solution-Processed Yellow Organic Light-Emitting Diodes Based on Two New Ionic Ir (III) Complexes

Two new and efficient cationic yellow-emissive Ir (III) complexes (Ir1 and Ir2) are rationally designed by using 2-(4-chloro-3-(trifluoromethyl)phenyl)-4-methylquinoline as the main ligand, and, respectively, 4,4′-dimethyl-2,2′-bipyridyl and 4,4′-dimethoxy-2,2′-bipyridyl as the ancillary ligands. Both complexes show enhanced phosphorescence (546 nm with 572 nm as shoulder and high phosphorescent quantum efficiency in solution, which is in favor of efficient solution-processed phosphorescent organic light-emitting diodes. Compared with Ir2, the Ir1-based device displays excellent device performance, with maximum external quantum efficiency, current efficiency, and power efficiency of up to 7.92%, 26.32 cd/A and 15.31 lm/W, respectively, thus proving that the two new ionic Ir (III) complexes exhibit great potential for future solution-processed electroluminescence.     

Molecularly "engineered" anode adsorbates for probing OLED interfacial structure-charge injection/luminance relationships: large, structure-dependent effects

Molecule-scale structure effects at organic light-emitting diodes (OLED) anode-organic transport layer interfaces are probed via a self-assembly approach. A series of ITO anode-linked silyltriarylamine molecules differing in aryl group and linker density are synthesized for this purpose and used to probe the relationship between nanoscale interfacial chemical structure, charge injection and electroluminescence properties. Dramatic variations in hole injection magnitude and OLED performance can be correlated with the molecular structures and electrochemically derived heterogeneous electron-transfer rates of such triarylamine fragments, placed precisely at the anode-hole transport layer interface. Very bright and efficient ( approximately 70 000 cd/m2 and approximately 2.5% forward external quantum efficiency) OLEDs have thereby been fabricated.     

Simple bipolar molecules constructed from biphenyl moieties as host materials for deep-blue phosphorescent organic light-emitting diodes

Simple is good! Based on biphenyl molecules, two bipolar host materials with high triplet energies have been rationally designed, synthesized, and fully characterized. Deep blue phosphorescent organic light-emitting diodes, which employ the new hosts and an iridium(III) complex as triplet emitter, show a maximum current efficiency of 40 cd A(-1), a maximum power efficiency of 36 lm W(-1), and a maximum external quantum efficiency of 19.5 %.     

Solution-processable high-efficiency bis(trifluoromethyl)phenyl functionalized phosphorescent neutral iridium(III) complex for greenish yellow electroluminescence

A novel and highly efficient bis(trifluoromethyl)phenyl functionalized iridium(III) complex is designed and synthesized. The complex shows intensive greenish yellow phosphorescence (525?nm with 563?nm as shoulder), high photoluminescence efficiency (0.90) and moderate full width at half maximum (72?nm). The bulky bis(trifluoromethyl)phenyl moiety introduced into the complex provides the excellent solubility and effective steric hindrance for solution-processed organic light-emitting diodes. The maximum power efficiency and current efficiency of electroluminescence are 4.13?lm/W and 9.54?cd/A, respectively.     

High-efficiency red electrophosphorescence based on neutral bis(pyrrole)-diimine platinum(II) complex

Efficient red electroluminescence from the excimer or oligomer of neutral phosphorescent bis(pyrrole)-diimine Pt(II) complex has been achieved with maximum external quantum efficiency, luminous efficiency, power efficiency and brightness of 6.5%, 9.0 cd A(-1), 4.0 lm W(-1) and 11 100 cd m(-2), respectively.     

A codeposition route to CuI-pyridine coordination complexes for organic light-emitting diodes

We demonstrate a new approach for utilizing CuI coordination complexes as emissive layers in organic light-emitting diodes that involves in situ codeposition of CuI and 3,5-bis(carbazol-9-yl)pyridine (mCPy). With a simple three-layer device structure, pure green electroluminescence at 530 nm from a Cu(I) complex was observed. A maximum luminance and external quantum efficiency (EQE) of 9700 cd/m(2) and 4.4%, respectively, were achieved. The luminescent species was identified as [CuI(mCPy)(2)](2) on the basis of photophysical studies of model complexes and X-ray absorption spectroscopy.     

New carbazole-substituted siloles for the fabrication of efficient non-doped OLEDs

New aggregation-induced emission molecules of carbazole-substituted siloles are prepared, based on which efficient non-doped OLEDs are fabricated, offering high external quantum efficiencies of up to 5.63%.     

A single-molecule excimer-emitting compound for highly efficient fluorescent organic light-emitting devices

A pyrene-containing single-molecule excimer-emitting compound, 1,8-bis(pyren-2-yl)naphthalene (BPyN), was synthesized. With BPyN as a host emitter, C545T-based green OLEDs were fabricated, exhibiting high efficiencies of 22 lm W(-1), 22 cd A(-1) and 6.2% external quantum efficiency (EQE) at 100 cd m(-2), and 19 lm W(-1), 22 cd A(-1) and 6.2% EQE at 1000 cd m(-2).     

Optimization of high-performance blue organic light-emitting diodes containing tetraphenylsilane molecular glass materials

Molecular glass material (4-(5-(4-(diphenylamino)phenyl)-2-oxadiazolyl)phenyl)triphenylsilane (Ph(3)Si(PhTPAOXD)) was used as the blue light-emitting material in the fabrication of high-performance organic light-emitting diodes (OLEDs). In the optimization of performance, five types of OLEDs were constructed from Ph(3)Si(PhTPAOXD): device I, ITO/NPB/Ph(3)Si(PhTPAOXD)/Alq(3)/Mg:Ag, where NPB and Alq(3) are 1,4-bis(1-naphylphenylamino)biphenyl and tris(8-hydroxyquinoline)aluminum, respectively; device II, ITO/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where TPBI is 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene; device III, ITO/Ph(2)Si(Ph(NPA)(2))(2)/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag, where Ph(2)Si(Ph(NPA)(2))(2) is bis(3,5-bis(1-naphylphenylamino)phenyl)-diphenylsilane, a newly synthesized tetraphenylsilane-containing triarylamine as hole-transporting material; device IV, ITO/Ph(2)Si(Ph(NPA)(2))(2)/NPB/Ph(3)Si(PhTPAOXD)/TPBI/Mg:Ag; device V, ITO/CuPc/NPB /Ph(3)Si(PhTPAOXD)/Alq(3)/LiF/Al, where CuPc is Cu(II) phthalocyanine. Device performances, including blue color purity, electroluminescence (EL) intensity, current density, and efficiency, vary drastically by changing the device thickness (100-600 A of the light-emitting layer) and materials for hole-transporting layer (NPB and/or Ph(2)Si(Ph(NPA)(2))(2)) or electron-transporting material (Alq(3) or TPBI). One of the superior OLEDs is device IV, showing maximum EL near 19 000 cd/m(2) with relatively low current density of 674 mA/cm(2) (or near 3000 cd/m(2) at 100 mA/cm(2)) and high external quantum efficiency of 2.4% (1.1 lm/W or 3.1 cd/A). The device possesses good blue color purity with EL emission maximum (lambda(max)(EL)) at 460 nm, corresponding to (0.16, 0.18) of blue color chromaticity on CIE coordinates. In addition, the device is reasonably stable and sustains heating over 100 degrees C with no loss of luminance on the basis of the annealing data for device V. Formation of the exciplex at the interface of NPB and Ph(3)Si(PhTPAOXD) layers is verified by EL and photoluminescence (PL) spectra studies on the devices with a combination of different charge transporting materials. The EL due to the exciplex (lambda(max)(EL) at 490-510 nm) can be properly avoided by using a 200 A layer of Ph(3)Si(PhTPAOXD) in device I, which limits the charge-recombination zone away from the interface area.     

Hybridized local and charge-transfer excited state fluorophores enabling organic light-emitting diodes with record high efficiencies close to 20%

Pure organic emitters with full utilization of triplet excitons are in high demand for organic light-emitting diodes (OLEDs). Herein, through modulation of electron donors and introduction of phenyl rings as π spacers, we present three pure organic fluorophores (BCz, BTCz and BPTCz) with the hybridized local and charge-transfer (HLCT) excited state feature for OLED fabrication. Importantly, the introduction of π spacers in BPTCz not only enhances locally excited character with a fast radiative decay but also promotes intermolecular interactions to suppress non-radiative decays, contributing to a high solid-state fluorescence efficiency over 90%. Significantly, BPTCz not only endows its doped OLEDs with an external quantum efficiency (EQE) up to 19.5%, but also its non-doped OLED with a high EQE of 17.8%, and these outstanding efficiencies are the state-of-the-art performances of HLCT-based OLEDs.

Three purely organic fluorophores with a hybridized local and charge-transfer excited state feature are presented and enabled organic light-emitting diodes with record high external quantum efficiencies close to 20%.     

高效溶液法小分子磷光电致发光器件研究

以小分子化合物CDBP[4,4′-bis(carbazol-9-yl)-9,9-dimethyl-fluorene]为主体材料,Ir(pppy)3[tris(5-phenyl-10,10-dimethyl-4-aza-tricycloundeca-2,4,6-triene)Iridium(III)]为磷光客体材料,采用溶液法和真空蒸镀法相结合的制备工艺,制作了小分子磷光电致发光器件.研究表明,通过器件结构的优化,Ir(pppy)3(重量百分比为2)掺杂的多层绿光电致发光器件效率达22.0 cd/A,最大亮度达到26600 cd/m²,这一结果可与当今基于真空蒸镀的小分子或基于溶液法的高分子磷光电致发光器件性能相媲美.本工作为降低有机电致发光器件的成本,扩展溶液法有机电致发光器件制备工艺中材料的选择范围提供了实验依据.     

Realizing green phosphorescent light-emitting materials from rhenium(i) pyrazolato diimine complexes

Two neutral pyrazolato diimine rhenium(I) carbonyl complexes with formula [Re(CO)(3)(N-N)(btpz)] where N-N = 2,2'-bipyridine (1) and 1,10-phenanathroline (2), and btpz = 3,5-bis(trifluoromethyl) pyrazolate, were synthesized and characterized by elemental analysis, routine spectroscopic methods, and single-crystal X-ray diffraction study. Ground and excited state properties of these complexes were investigated by steady-state and time-resolved spectroscopies. Complexes 1 and 2 show photoluminescent emission in both solution and solid-state at room temperature, arising from metal to ligand charge-transfer (MLCT) transition with strong overlapping of intraligand pi --> pi transitions. The long-lived excited state lifetimes of complexes 1 and 2, which are on the order of microseconds, indicate the presence of phosphorescent emission. As these complexes hold the potential to serve as phosphors for organic light-emitting diodes (OLEDs), their electroluminescent performances were evaluated by employing them as dopants of various electron transport layer (ETL) or hole transport layer (HTL) hosts. For complex 1, a green electrophosphorescence emission centered at lambda(max) = 530 nm was observed at low turn-on voltage ( approximately 6 V) with luminous power efficiency of 0.72 lm/W, external quantum efficiency of 0.82%, and luminance of 2300 cd/m(2) at a current density of 100 mA/cm(2).     

Sky-blue phosphorescent organic light-emitting diode with superior performance based on novel chlorine functionalized iridium(III) complex

A novel and highly efficient chlorine functionalized iridium(III) complex is designed and synthesized. The complex shows intensive sky-blue phosphorescence (with a peak of 492?nm and a shoulder at 524?nm), high photoluminescence efficiency (0.78) and moderate full width at half maximum (62?nm). The aromatic chlorine introduced into the complex provides the robust chemical stability and effective sky-blue phosphorescence for organic light-emitting diodes (OLEDs). The maximum power efficiency, current efficiency and external quantum efficiency for the complex based OLED are up to 48.46?lm/W, 55.04?cd/A and 18.47%, respectively.     

Substituent effect on the photophysical properties, electrochemical properties and electroluminescence performance of orange-emitting iridium complexes

A series of bis(2-phenylbenzothiozolato-N,C(2'))iridium(acetylacetonate) [(bt)(2)Ir(acac)] derivatives, 1-4, were synthesized. Different substituents (CF(3), F, CH(3), OCH(3)) were introduced in the benzothiazole ring to study the substituent effect on the photophysical, electrochemical properties and electroluminescent performance of the complexes, and finally to select high-performance phosphors for use in organic light-emitting diodes (OLEDs). All complexes 1-4 and (bt)(2)Ir(acac) are orange-emitting with tiny spectral difference, despite the variation of the substituent. However, the phosphorescent quantum yield increases with the electron-withdrawing ability of the substituent. This is in contrast to the previous observation that the substituent in the phenyl ring bonded to the metal center of (bt)(2)Ir(acac) not only affected the luminescent quantum efficiency but also greatly tuned the emission color of the complexes. Quantum chemical calculations revealed that the substituents in this position do not make a significant contribution to both the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), which probably accounts for the fact that they do no strongly influence the bandgap and emission color of the complexes. Orange OLEDs were fabricated using 1-4 as doped emitters. The electron-withdrawing CF(3) and F groups favor improving the electroluminescence efficiency in comparison with that of the parent (bt)(2)Ir(acac), while electron-donating CH(3) and OCH(3) are not favorable for light emission. The complex 1 based OLED exhibited a maximum luminance efficiency of 54.1 cd A(-1) (a power efficiency of 24 lm W(-1) and an external quantum efficiency of 20%), which are among the best results ever reported for vacuum deposited orange OLEDs so far.     

Synthesis, photophysical and electrophosphorescent properties of fluorene-based platinum(II) complexes

A series of platinum(II) complexes bearing tridentate cyclometalated C^N^N (C^N^N=6-phenyl-2,2'-bipyridine and π-extended R-C^N^N=3-[6'-(naphthalen-2'-yl)pyridin-2'-yl]isoquinoline) ligands with fluorene units have been synthesised and their photophysical properties have been studied. The fluorene units are incorporated into the cyclometalated ligands by a Suzuki coupling reaction. An increase in the π-conjugation of the cyclometalated ligands confers favourable photophysical properties compared to the 6-phenyl-2,2'-bipyridine analogues. The fluorene-based platinum(II) complexes display vibronic-structured emission bands with λ(max)=558-601 nm, and high emission quantum yields up to 0.76 in degassed dichloromethane. Their emissions are tentatively assigned to excited states with mixed (3)IL/(3)MLCT parentage (IL=intraligand, MLCT=metal-to-ligand charge transfer). The crystal structures of these platinum(II) complexes reveal extensive Pt(II)···π and/or π-π interactions. The fluorene-based platinum(II) complexes are soluble in organic solvents, have high thermal stability with decomposition temperature >350 °C, and can be thermally vacuum-sublimed or solution-processed as phosphorescent dopants for the fabrication of organic light-emitting diodes (OLEDs). A monochromic OLED with 3d as dopant (2 wt%) fabricated by vacuum deposition gave a current efficiency of 14.7 cd A(-1) and maximum brightness of 27000 cd m(-2). A high current efficiency (9.2 cd A(-1)) has been achieved in a solution-processed OLED using complex 3f (5 wt%) doped in a PVK (poly(9-vinylcarbazole)) host.     

含稀土铕络合物的三元共聚物的光电性质

合成了可平衡电荷(空穴与电子)传输的三功能合一的稀土铕发光材料,将几种稀土铕络合物单体与乙烯基咔唑、甲基丙烯酸甲酯共聚制得含咔唑和稀土铕络合物的空穴传输层发光层电子传输层(HTLEMLETL)三功能合一的聚合物,并研究它们的电化学及电致发光性能.电化学分析表明这类三元共聚物兼有氧化性和还原性,氧化电位及还原电位分别为0.75V和-1.8V左右,可见这类材料同时具有空穴传输和电子传输功能.从测定的电致发光谱看,AlQ3、TPD及咔唑基等发光单元在器件中没有共发光,而是起电荷传输作用,以这些材料制作的电致发光器件所发的红光纯度都比较高.     

Poly(distyrylbenzene-block-sexi(ethylene oxide)), a highly luminescent processable derivative of PPV

A block copolymer of distyrylbenzene with sexi(ethylene oxide) spacers displays high solid state photoluminescence efficiency (34%). Single layer light-emitting diodes with calcium or aluminium cathodes exhibit luminances over 2000 cd m-2 and efficiencies of 0.5 cd A-1.     

两种基于氮杂环结构铱(Ⅲ)配合物的合成及有机电致发光性能

以苯基嘧啶/吡啶基嘧啶为母核, 同时引入2个三氟甲基(CF₃)合成了2-[3,5-二（三氟甲基）苯基]-5-氟基嘧啶(tfmphfppm)和2-[2,6-二（三氟甲基）-4-吡啶基]-5-氟基嘧啶(tfmpyfppm)主配体, 并以2-(5-苯基-1,3,4-噁二唑-2-)苯酚(pop)为辅助配体合成了2种铱(III)配合物Ir(tfmphfppm)₂(pop)和Ir(tfmpyfppm)₂(pop), 其发射光谱峰分别位于484和504 nm, 分别属于蓝绿光和绿光发射, 发光量子效率分别达到76%和89%. 由于氮杂环和2,5-二苯基-1,3,4-噁二唑基团的存在, 配合物具有较低的最低未占据分子轨道(LUMO)能级和较高的电子迁移率. 以2种 铱(III)配合物为发光中心制备的有机电致发光器件(OLED)显示了较好的器件性能, 其最大亮度(L_max)、 最大电流效率(η_{c, max})、 最大功率效率(η_{p, max})和最大外量子效率(EQE_max)分别为33379 cd/m², 76.55 cd/A, 31.59 lm/W和26.7%; 并且该器件显示了比较小的效率滚降, 在亮度为1000 cd/m²时, 器件的η_c仍然可以达到72.71 cd/A. 本文结果表明, 氮杂环、 2,5-二苯基-1,3,4-噁二唑和三氟甲基基团可以有效提高铱(Ⅲ)配合物的发光性能和电子迁移率, 从而提高器件的性能.