Solution-processible multi-component cyclometalated iridium phosphors for high-efficiency orange-emitting OLEDs and their potential use as white light sources

The synthesis and photophysical studies of several multifunctional phosphorescent iridium(III) cyclometalated complexes consisting of the hole-transporting carbazole and fluorene-based 2-phenylpyridine moieties are reported. All of them are isolated as thermally and morphological stable amorphous solids. Extension of the pi-conjugation through incorporation of electron- pushing carbazole units to the fluorene fragment leads to bathochromic shifts in the emission profile, increases the highest oc- cupied molecular orbital levels and improves the charge balance in the resulting complexes because of the propensity of the carbazole unit to facilitate hole transport. These iridium-based triplet emitters give a strong orange phosphorescence light at room temperature with relatively short lifetimes in the solution phase. The photo- and electroluminescence properties of these phosphorescent carbazolylfluorene-functionalized metalated complexes have been studied in terms of the coordinating position of carbazole to the fluorene unit. Organic light-emitting diodes (OLEDs) using these complexes as the solution-processed emissive layers have been fabricated which show very high efficiencies even without the need for the typical hole-transporting layer.I These orange-emitting devices can produce a maximum current efficiency of similar to 30 cd A(-1) corresponding to an external quantum efficiency of similar to 10 % ph/el (photons per electron) and a power efficiency of similar to 14 Im W-1.

Wavefront measurement of double-clad pulsed ytterbium fiber laser

Because of high efficiencies, compact structure, and excellent heat dissipation, high-power fiber lasers are extremely useful for applications such as cutting, welding, precision drilling, trimming, sensing, optical transmitter, material processing, micromachining, and so on. However, the wavefront of the double clad fiber laser doped with ytterbium is still unknown. In this paper, wavefront of a fiber laser is measured and the traditional Hartmann-shack wavefront sensing method is adopted. We measured a double clad fiber laser doped with ytterbium which produces pulse wave output at infrared wavelength. The wavefront shape and contour are reconstructed and the result shows that wavefront is slightly focused and not an ideal plane wavefront. Wavefront measurement of fiber laser will be useful to improving the lasers' performance and developing the coherent technique for its applications.

Wideband two-port beam splitter of a binary fused-silica phase grating

The usual beam splitter of multilayer-coated film with a wideband spectrum is not easy to achieve. We describe the realization of a wideband transmission two-port beam splitter based on a binary fused-silica phase grating. To achieve high efficiency and equality in the diffracted 0th and -1st orders, the grating profile parameters are optimized using rigorous coupled-wave analysis at a wavelength of 1550 nm. Holographic recording and the inductively coupled plasma dry etching technique are used to fabricate the fused-silica beam splitter grating. The measured efficiency of (45% x 2) = 90% diffracted into the both orders can be obtained with the fabricated grating under Littrow mounting. The physical mechanism of such a wideband two-port beam splitter grating can be well explained by the modal method based on two-beam interference of the modes excited by the incident wave. With the high damage threshold, low coefficient of thermal expansion, and wideband high efficiency, the presented beam splitter etched in fused silica should be a useful optical element for a variety of practical applications. (C) 2008 Optical Society of America.

手性有机小分子路易斯碱催化剂的设计、合成及其在亚胺不对称还原中的应用

手性胺是合成天然产物和手性药物的重要中间体，亚胺的不对称催化还原是制备光学活性手性胺的最直接有效的方法之一。但是，由于C＝N双键的反应活性较弱以及容易发生E/Z异构等问题，亚胺的不对称催化还原具有很大的挑战性，既具有高对映选择性又具有宽广底物普适性的催化剂很少。 本文分别由手性脯氨酸、哌啶酸、哌嗪酸以及氨基醇出发，设计和合成了一系列结构新颖、合成简便、性能优良的酰胺类有机小分子路易斯碱催化剂，以廉价的三氯氢硅为氢源，用这些催化剂催化亚胺不对称还原，得到了非常优良的收率、对映选择性和前所未有的底物普适性。 文献研究认为，除N-甲酰基外，分子内含有芳香酰胺是能催化亚胺还原的有机小分子路易斯碱催化剂具有较高对映选择性的必要条件，我们研究发现N-甲酰脯氨酸非芳香酰胺类催化剂（包括结构简单的C2-对称型脯氨酰胺类催化剂），对N-芳基酮亚胺的还原可获得达86%的对映选择性，远高于同类芳香酰胺催化剂，证明N-甲酰非芳香酰胺类路易斯碱催化剂在亚胺还原中也能得到高的对映选择性。 在进一步研究中，我们以手性六元哌啶酸为模板，分别设计合成了N-甲酰哌啶酸芳香酰胺和N-甲酰哌啶酸非芳香酰胺两类催化剂，其中芳香酰胺催化剂（S）-N-（甲酰基）哌啶-2-酸-1-萘基酰胺（28）和非芳香酰胺催化剂（2S,1'S,2'S）-N-（甲酰基）-哌啶-2-酸（1',2'-二苯基-2'-乙酰氧基-乙基）酰胺（30）显示出非常优良的催化活性和对映选择性，对于N-芳基芳香酮亚胺的还原，无论是缺电子体系还是富电子体系，绝大部分都能得到很高的收率（达98%）和对映选择性（达96% ee)。特别值得一提的是30对一些脂肪族亚胺和α,β-不饱和亚胺的还原，虽然底物为E/Z混合物，也能得到很高的收率（达93%）和对映选择性（达95% ee)，这样的底物普适性在过渡金属催化体系中也是前所未有的。 现有的催化亚胺还原的高对映选择性催化体系大多仅适用于甲基酮亚胺底物，对位阻较大的非甲基酮亚胺很难获得好的结果。我们以L-哌嗪酸为模板设计和合成出的（S）-N-（甲酰基）-哌嗪-2-酸-4-对叔丁基苯磺酰基-苯基酰胺不但对N-芳基甲基酮亚胺有很好的对映选择性（达90% ee)，而且对于大位阻的N-芳基非甲基酮亚胺有更好的对映选择性（达97% ee)。该催化剂与30在底物普适性方面具有很好的互补性。 我们还设计了基于1,2-二苯基氨基醇为模板的新型N-甲酰路易斯碱有机小分子催化剂，首次发现结构简单的N-甲酰（1S,2R）二苯基氨基醇能较好的催化N-芳基酮亚胺，最高可以得到82%的对映选择性。 针对我们设计合成的结构新颖、性能优良的催化剂，我们对催化机理进行了探讨和解释，提出了几个假想的机理模型。 Catalytic enantioselective reduction of imines represents one of the most straightforward and efficient methods for the preparation of chiral amines, an important intermediate for the synthesis of natural products and chiral drugs. However, asymmetric reduction of imines remains a big challenge and highly enantioselective catalysts with a satisfactorily broad substrate scope remain elusive. Factors contributing to the difficulty of this transformation include the weak reactivity of the C=N bond and the existence of inseparable mixtures of E/Z isomers. Starting from chiral proline, pipecolinic acid, piperazine-2-carboxylic acid and 1,2-diphenyl amino alcohol, a series of structurally simple and easily prepared amides were developed as highly effective Lewis basic organocatalysts for the asymmetric reduction of imines with trichlorosilane as the reducing agent, which promoted the reduction of N-aryl imines with high yields and excellent enantioselectivities with an unprecedented substrate spectrum. In the literature, it has been believed that besides the N-formyl group, the existence of an arylamido group in the structure of Lewis basic organocatalysts is a prerequisite for obtaining high enantioselectivity in the catalytic reduction of imines. However, we found that the N-formyl-L-prolinamides bearing non-arylamido groups, including structurally simple C2-symmetric tetraamides, could also work as effective Lewis basic catalysts to promote the asymmetric reduction of ketimines with high enantioselectivities (up to 86% ee), which are even more enantioselective than the analogues with arylamido groups. In further studies, we developed novel N-formamides with arylamido groups and non-arylmido groups as Lewis basic catalysts using the commercially available L-pipecolinic acid as the template. The catalysts (S)-1-formyl-piperidine-2-carboxylic acid naphthylamide 28 and (2S,1'S,2'S)-acetic acid 2-[(1-formyl-piperidine-2-carbonyl) -amino]-1,2-diphenyl-ethyl ester 30 were found to promote the reduction of a broad range of N-aryl imines in high yields (up to 98%) and excellent ee values (up to 96%) under mild conditions. Furthermore, catalyst 30 also exhibited high enantioselectivities (up to 95% ee) for the challenging aliphatic ketimines and α,β-unsaturated imines despite that these imines exist as E/Z isomeric mixtures. The broad substrate spectrum of this catalyst is unprecedented in catalytic asymmetric imine reduction, including transition-metal-catalyzed hydrogenation processes. Many of the currently available highly enantioselective catalytic systems only tolerate methyl ketimines, which gave poor results for bulkier non-methyl ketimines. Starting from L-piperazine-2-carboxylic acid, we developed (S)-4-(4-tert- butylbenzenesulfonyl)-1-formyl-N-phenyl-piperazine-2-carboxamide as highly enantioselective Lewis basic catalysts for the hydrosilylation of both methyl ketimines and steric bulky non-methyl ketimines. Moreover, higher enantioselectivities were obtained for non-methyl ketimines than methyl ketimines under the catalysis of this catalyst. Thus, this catalyst system complements with 30 in terms of the substrate scope. We also found that easily accessible (1R,2S)-N-formyl-1,2-diphenyl- 2-aminoethanol worked as an effective Lewis basic catalyst in the enantioselective hydrosilylation of ketimines, affording high enantioselectivities (up to 82% ee) for a broad range of ketimines. To rationalize the high efficiencies of the structurally novel catalysts we developed, several catalytic models have been proposed.

Nonconjugated Carbazoles: A Series of Novel Host Materials for Highly Efficient Blue Electrophosphorescent OLEDs

A series of carbazole derivatives was synthesized and their electrical and photophysical properties were investigated. It is shown that the triplet energy levels of these hosts are higher than that of the most popular blue phosphorescent material iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C-2'] picolinate (FIrpic) and the most extensively used phosphorescent host material 4,4'-N,N'-dicarbazole-biphenyl (CBP). These new host materials also showed good thermal stability and high glass transition temperatures (T-g) ranging from 78 to 115 degrees C as the linkage group between the carbazoles was altered. Photophysical measurements indicate that the energy transfer between these new hosts and FIrpic is more efficient than that between CBP and FIrpic. Devices incorporating these novel carbazole derivatives as the host material doped with FIrpic were fabricated with the configurations of ITO/NPB (40 nm)/host:FIrpic (30 nm)/BCP (15 nm)/AlQ (30 nm)/LiF (1 nm)/Al (150 nm). High efficiencies (up to 13.4 cd/A) have been obtained when 1,4-bis (4-(9H-carbazol-9-yl)phenyl)cyclohexane (CBPCH) and bis(4-(9H-carbazol-9-yl)phenyl) ether (CBPE) were used as the host, respectively.

Tuning the energy level and photophysical and electroluminescent properties of heavy metal complexes by controlling the ligation of the metal with the carbon of the carbazole unit

Four novel Ir-III and Pt-II complexes with cyclometalated ligands bearing a carbazole framework are prepared and characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. Single-crystal X-ray diffraction studies of complexes 1, 3, and 4 reveal that the 3- or 2-position C atom of the carbazole unit coordinates to the metal center. The difference in the ligation position results in significant shifts in the emission spectra with the changes in wavelength being 84 nm for the Ir complexes and 63 nm for the Pt complexes. The electrochemical behavior and photophysical properties of the complexes are investigated, and correlate well with the results of density functional theory (DFT) calculations. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ(3)/LiF/Al can attain very high efficiencies.

Generation of a high-quality partially coherent dark hollow beam with a multimode fiber

We report the experimental generation of a high-quality partially coherent dark hollow beam (DHB) by coupling a partially coherent beam into a multimode fiber (MMF) with a suitable incidence angle. The interference experiment of the generated partially coherent DHB passing through double slits is demonstrated. It is found that the coupling efficiency of the MMF, the quality, and the coherence of the generated partially coherent DHB are closely controlled by the coherence of the input beam. (c) 2008 Optical Society of America.

High-efficiency reflective diffraction gratings in fused silica as (de)multiplexers at 1.55 mu m for dense wavelength division multiplexing application

We describe high-efficiency, high-dispersion reflection gratings fabricated in bulk fused Silica illuminated by incident lights in the C + L bands as (de)multiplexers for dense wavelength division multiplexing (DWDM) application. Based on the phenomenon of total internal reflection, gratings with optimized profile parameters exhibit diffraction efficiencies of more than 90% under TM- and TE-polarized incident lights for 101-nm spectral bandwidths (1520-1620 nm) and can reach an efficiency of greater than 97% for both polarizations at a wavelength of 1550 nm. Without loss of metal absorption, without coating of dielectric film layers, and independent of tooth shape, this new kind of grating should be of great interest for DWDM application. (C) 2005 Optical Society of America.

High-efficiency diffraction gratings in fused silica at the wavelength of 632.8 nm

We describe high-efficiency diffraction gratings fabricated in fused silica at the wavelength of 632.8 nm by rigorous coupled-wave analysis (RCWA). High-density holographic gratings, if the groove density falls within the range of 1575-1630 lines/mm and the groove depth within the range of 1.1-1.3 microns, can realize high diffraction efficiencies at the wavelength of 632.8 nm, e.g., the first Bragg diffraction efficiency can theoretically achieve more than 93% both in TE- and TM-polarized incidences, which greatly reduces the polarization-dependent losses. Note that with different groove profiles further optimized, the maximum efficiency of more than 99.69% can be achieved for TM-polarized incidence, or 97.81% for TE-polarized incidence.

High power single transverse mode operation of a tapered large-mode-area fiber laser

To get high output power with good beam quality, a tapered section is introduced to large-mode-area (LMA) Yb-doped fiber laser. Output characteristics of the fiber laser without tapered section and with tapered section are compared experimentally. When the launched pump power is 119.1 W, 77.9 W with M-2 3.08 and 56.4 W with M-2 1.14 can be obtained, respectively. The corresponding slope efficiencies are 71.8% and 54.1%, respectively. Although output power of the tapered fiber laser has 30.6% penalty, brightness of it is as much as 5.28 times of the fiber laser without tapered section. Moreover, spectra of them are measured. It is found that tapered section makes lasing wavelength of the fiber laser shorter. (c) 2007 Elsevier B.V. All rights reserved.

Spectroscopic properties of neodymium doped high silica glass and aluminum codoping effects on the enhancement of fluorescence emission

Nd3+ -codoped and Al3+-Nd3+-codoped high silica glasses have been prepared by sintering nanoporous glasses impregnated with Nd3+ stop and Al3+ ions. The Judd-Ofelt intensity parameters Omega(2,4,6) of Nd3+-doped high silica glasses were obtained and used to analyze aluminum codoping effects. Fluorescence properties of Nd3+-doped high silica glasses strongly depend on the Al3+ concentration. While Nd3+ ion absorption and emission intensities of obviously increase when aluminum is added to Nd3+-doped high silica glasses, fluorescence lifetimes decrease and aluminum codoping has almost no influence on the radiative quantum efficiencies. This indicates that aluminum codoping is responsible for an anti-quenching effect through a local modification of rare-earth environments rather than through physical cluster dispersion.

Design of high-efficiency diffraction gratings based on total internal reflection for pulse compressor

We present designs of high-efficiency compression grating based on total internal reflection (TIR) for picosecond pulse laser at 1053 nm. The setup is devised by directly etching gratings into the bottom side of a prism so that light can successfully enter (or exit) the compression grating. Dependence of the -1 order diffraction efficiencies on the constructive parameters is analyzed for TE- and TM-polarized incident light at Littrow angle by using Fourier modal method in order to obtain optimal grating structure. The electric field enhancement within the high-efficiency TIR gratings is regarded as another criterion to optimize the structure of the TIR gratings. With the criterion of high diffraction efficiency, low electric field enhancement and sufficient manufacturing latitude, TIR compression gratings with optimized constructive parameters are obtained for TE- and TM-polarized incident light, respectively. The grating for TE-polarized light exhibits diffraction efficiencies higher than 0.95 within 23 nm bandwidth and relatively low square of electric field enhancement ratio of 5.7. Regardless of the internal electric field enhancement, the grating for TM-polarized light provides diffraction efficiencies higher than 0.95 within 42 nm bandwidth. With compact structure, such TIR compression gratings made solely of fused silica should be of great interest for application to chirped pulse amplification (CPA) systems. (c) 2007 Elsevier B.V. All rights reserved.

High efficiency and broad bandwidth grating coupler between nanophotonic waveguide and fibre

A high efficiency and broad bandwidth grating coupler between a silicon-on-insulator (SOI) nanophotonic waveguide and fibre is designed and fabricated. Coupling efficiencies of 46% and 25% at a wavelength of 1.55 mu m are achieved by simulation and experiment, respectively. An optical 3 dB bandwidth of 45 nm from 1530 nm to 1575 nm is also obtained in experiment. Numerical calculation shows that a tolerance to fabrication error of 10 nm in etch depth is achievable. The measurement results indicate that the alignment error of +/-2 mu m results in less than 1 dB additional coupling loss.

The study on high efficient AlxGa1-xAs/GaAs solar cells

The investigation of AlxGa1-xAs/GaAs solar cells is carried out by means of both metalorganic chemical vapor deposition (MOCVD) and liquid-phase epitaxial (LPE) technique. The measurements of illuminated I-V characteristics, dark I-V characteristics and quantum efficiencies were performed for the GaAs solar cells made in author's laboratory. The measuring results revealed that the quality of materials in GaAs solar cell's structures is the key factor for getting high-efficient GaAs solar cells, but the effect of post-growth technology on the performances of GaAs solar cells is also very strong. The 21.95% (AM0, 2 x 2cm(2), 25 degreesC) high conversion efficiency in a typical GaAs solar cell has been achieved owing to improving the quality of materials as well as optimizing the post-growth technology of devices. (C) 2001 Elsevier Science B.V. All rights reserved.

Analysis of output coupling efficiencies for directional emission triangle and square microlasers

Output coupling efficiencies are analyzed for triangular and square microlasers connected with an output waveguide by FDTD simulation. The results show that square resonator with an output waveguide connected to the midpoint of one side can have high output coupling efficiency and a good mode selection.