Synthesis and characterization of novel perfluorinated polyimides with 3D‐controlled structures for photonic applications

We have designed and synthesized novel perfluorinated polyimides with 3D controlled structure. At first, we successfully developed the new synthetic routes to diamines with pendant bulky perfluorinated aromatic units in a multi‐step synthetic procedure. Novel perfluorinated polyimides were prepared in a two‐step reaction in N‐methyl‐2‐pyrrolidinone (NMP) solution: The first step was for the synthesis of polyamic acids (PAAs) and the second reaction was for the imidization of PAA. The polymer yield was over 89% and the inherent viscosity of PAAs was in the range of 0.24–0.36 dL/g. The thin films were prepared by spin‐coating the PAA solution in NMP onto various substrates such as a Si wafer or a KBr pellet, dried at 80 °C and further cured at 230 °C. The resultant polyimides are thermally stable over 400 °C. The refractive index and birefringence of the resultant polyimides are 1.5858–1.6452 and 0.01–0.005, respectively. The refractive index of polyimide decreases with increasing the fluorine content. The copolymerization and the ether linkages into the backbone reduce the birefringence of polyimides. Surprisingly, the pendant ether linkage is not a crucial factor in reducing the polyimide birefringence. Their birefringence is comparatively very low, compared with that of previous polyimides. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1326–1342, 2006     

Direct single-layered fabrication of 3D concavo–convex patterns in nano-stereolithography

A nano-surfacing process (NSP) is proposed to directly fabricate three-dimensional (3D) concavo–convex-shaped microstructures such as micro-lens arrays using two-photon polymerization (TPP), a promising technique for fabricating arbitrary 3D highly functional micro-devices. In TPP, commonly utilized methods for fabricating complex 3D microstructures to date are based on a layer-by-layer accumulating technique employing two-dimensional sliced data derived from 3D computer-aided design data. As such, this approach requires much time and effort for precise fabrication. In this work, a novel single-layer exposure method is proposed in order to improve the fabricating efficiency for 3D concavo–convex-shaped microstructures. In the NSP, 3D microstructures are divided into 13 sub-regions horizontally with consideration of the heights. Those sub-regions are then expressed as 13 characteristic colors, after which a multi-voxel matrix (MVM) is composed with the characteristic colors. Voxels with various heights and diameters are generated to construct 3D structures using a MVM scanning method. Some 3D concavo–convex-shaped microstructures were fabricated to estimate the usefulness of the NSP, and the results show that it readily enables the fabrication of single-layered 3D microstructures. PACS 85.40.Hp; 81.16.Nd; 42.82.Cr     

Local chemical distribution and electronic structure of Ge1−xTx DMS single crystals (T=Cr,Mn, Fe)

The spatial concentration distribution and local electronic structure of ferromagnetic Ge_1−xT_x (T=Cr, Mn, Fe) DMS single crystals have been investigated by using scanning photoelectron microscopy (SPEM), X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES). It is found that doped T ions in Ge_1−xT_x crystals are chemically phase-separated, suggesting that the observed ferromagnetism arises from the phase-separated T-rich phases in Ge_1−xT_x.     

高分子阳离子絮凝剂用于炼油废水处理研究

用聚二甲基二烯丙基氯化铵型高分子阳离子絮凝剂处理炼油废水考察了险油和化学耗氧量的动态变化规律。对产生的浮渣性质及滤饼的成份进行了研究。并且与聚合铝的处理效果进行对照。研究结果表明，ＨＣＡ除油和化学耗管氧量的性能优于ＰＡＣ，ＨＣＡ产生的浮渣是ＰＡＣ的三分之一，而浮渣中的含油量则是ＰＡＣ的三倍。     

A high-gain porous silicon metal–semiconductor–metal photodetector through rapid thermal oxidation and rapid thermal annealing

2 tungsten lamp at 1.83 mA excited by a 0.85-mW 675-nm laser diode. We also demonstrate that the dark current could be greatly reduced through rapid thermal oxidation and rapid thermal annealing. Received: 4 August 1997/Accepted: 28 May 1998     

Investigation by EPR and ENDOR spectroscopy of the novel 4Fe ferredoxin fromPyrococcus furiosus

The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe₄S₄] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe₄S₄]⁺, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g₁ = 2.09, g₂ = 1.95, g₃ = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using¹³CN^? and C¹⁵N^? ligands.¹³C and¹⁵N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (a_iso(¹³C)～ ?3 MHz, a_iso(¹⁵N) ～ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the¹³C hyperfine coupling has a large isotropic component (a_iso(¹³C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as⁵⁷Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [⁵⁷FeFe₃S₄]⁺ and [Fe⁵⁷Fe₃S₄]⁺, show hyperfine coupling characteristic for [Fe₄S₄]⁺ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on¹³C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand.