双光子技术在光生酸剂中的应用研究

自2000年以来,双光子技术开始应用于光生酸剂体系中,并取得了一定的研究进展。双光子技术在光生酸剂中的应用主要有两种情况:一是单分子体系,即光生酸剂分子本身具有较高的双光子吸收截面,可以在双光子激发下产生光酸;二是双分子体系,由具有较高吸收截面的敏化剂分子和光生酸剂分子组成,通过分子间电子转移的方式产生光酸。本文就这一类具有特殊光学性质的有机分子体系的构成及其应用进行了综述,介绍了不同类型的可以利用双光子技术的光生酸剂体系,总结了双光子技术在光生酸剂发展中面临的一些关键问题,展望了双光子技术在光生酸剂中的发展方向。     

The 1.4 and 248 nm radiation response of chemically amplified resists containing arylmethyl sulfone photoacid generators

The X-ray (1.4 nm) and deep UV (248 nm) radiation responses of chemically amplified photoresists incorporating arylmethyl sulfone photoacid generators were evaluated. The arylmethyl sulfones were primarily derivatives of benzyl phenyl sulfone, selected to reveal the importance of desulfonylation and internal abstraction with regard to the photochemical efficiency of acid generation. At 1.4 nm, benzyl phenyl sulfone gave a much more sensitive resist than dibenzyl sulfone, while the methyl derivatives of benzyl phenyl sulfone did not give much improvement over the parent compound. This suggests that desulfonylation is more important than internal abstraction for increased photochemical efficiency. At 248 nm, similar trends were observed, but with some modifications arising from the variation in extinction coefficient among the sulfones. Sensitivities at or below 20 mJ/cm² were obtained for both wavelength ranges.     

Novel Anionic Photoacid Generators (PAGs) and Corresponding PAG Bound Polymers

Summary: A new series of functionalized anionic photoacid generators (PAGs), and corresponding polymers were prepared in moderate to good yield and characterized. The thermostability of PAG bound polymers was superior to PAG blend polymers. The fluorine‐free PAG bound or blend polymers exhibited higher stability than fluorine‐substituted PAG bound or blend polymers. Although the acid generating efficiency of PAG blend polymers was higher than that of PAG bound polymers, yet it is anticipated that PAG incorporated into the polymer main chain may improve acid diffusion compared with the PAG blend polymers. This was demonstrated by preliminary electron beam lithography (EBL) results: the fluorine PAG bound polymer resist HE‐F4‐MBS‐TPS gave 35 nm 1:1 L/S and showed better resolution than the blend sample HE Blend F4‐IBBS‐TPS. The PAG bound resist showed the capability for higher resolution, since 30 nm 2:1 L/S patterned. Based on these preliminary EBL results, the PAG bound polymer samples are anticipated to have a resolution capability for the 32 nm node for EUVL.

Design of microstructures for EUV lithography.     

Photosensitive polybenzoxazole based on a poly(o‐hydroxy amide), a dissolution inhibitor,and a photoacid generator

A positive‐type photosensitive polybenzoxazole (PSPBO), based on a poly(o‐hydroxy amide) (PHA), the dissolution inhibitor (DI) 9,9‐bis(4‐tert‐butoxycarbonyloxyphenyl)fluorene (t‐Boc BHF), and the photoacid generator (5‐propylsulfonyloxyimino‐5H‐thiophene‐2‐ylidene)‐(2‐methylphenyl)acetonitrile (PTMA), was developed. Several new tert‐butoxycarbonylated compounds as DIs for PSPBOs were prepared from phenolic compounds having a cardolike structure with di‐tert‐butyl dicarbonate in the presence of 4‐dimethylaminopyridine. Among them, t‐Boc BHF and 5,5′,6,6′‐tetra(tert‐butoxycarbonyl)‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobiindane acted as excellent DIs, giving a large dissolution contrast between the exposed and unexposed areas in a 2.38 wt % tetramethylammonium hydroxide solution (TMAHaq)/5 wt % iso‐propanol (i‐PrOH). The dissolution behavior of this PSPBO system was studied in relation to the PTMA and t‐Boc BHF loadings and postexposure baking temperature. A PSPBO consisting of PHA (77 wt %), t‐Boc BHF (20 wt %), and PTMA (3 wt %) exhibited a sensitivity of 34 mJ/cm² and a contrast of 5.8 when exposed to 365‐nm light (i‐line) and developed with an aqueous alkaline developer, 2.38 wt % TMAHaq/5 wt % i‐PrOH. A clear, positive image with 6‐μm features and a 10‐μm‐thick pattern with high sensitivity and contrast was produced by contact printing and converted into polybenzoxazole patterns upon heating at 350 °C for 1 h. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 661–668, 2007     

Alkaline-developable positive-type photosensitive polyimide with high mechanical strength and high resolution based on chain extendable poly(amic acid), thermally degradable cross-linker and photoacid generator

A positive-type photosensitive polyimide ( PSPI ) based on a chain extendable poly(amic acid) ( PAA ), a thermally degradable cross-linker 1,3,5-tris[(2-vinyloxy)ethoxy]benzene ( TVEB ), and a photoacid generator (PAG) (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile ( PTMA ) has been developed. The chain extendable PAA was prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride ( BPDA ) and 4,4′-oxydianiline ( ODA ) and end-capped with di-tert-butyl dicarbonate ( DIBOC ) in N-methyl-2-pyrrolidone (NMP), which has a controlled molecular weight for developing in a 2.38 wt% tetramethyl ammonium hydroxide aqueous solution ( TMAH _aq ) and undergoes a chain extending reaction during curing stage. The photosensitive resist solution was formulated with the polymerization solution (30 wt% in NMP), TVEB (15 wt% for the polymer), and PAG (4.5 wt% for the polymer). The PSPI showed a sensitivity of 47 mJ cm⁻² and a contrast of 5.8 when exposed to 365-nm light, followed by postexposure baking at 90 °C for 10 min and development with the 2.38 wt% TMAH _aq at room temperature. A fine-positive image with 3-μm line-and-space patterns was obtained on a 3-μm thick film exposed to UV light at 365 nm in the contact-printed mode. After thermal curing at 350 °C for 1 hr, the resulting PSPI features excellent mechanical strength and elongation.     

Synthesis and properties of polymer brushes composed of poly(diphenylacetylene) main chain and poly(ethylene glycol) side chains

Novel cylindrical polymer brushes consisting of poly(diphenylacetylene) main chain and poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) side chains were synthesized by the diphenylacetylene macromonomer or side chain initiated atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether monomethacrylate (PEGMA) from an bromo isobutyryl-bearing poly(diphenylacetylene) (poly(BrDPA)) method. The diphenylacetylene macromonomer, namely, DPA-PPEGMA, were prepared by the ATRP of PEGMA from bromo isobutyryl-bearing diphenylacetylene. DPA-PPEGMA was polymerized successfully with WCl₆-Ph₄Sn catalyst to give high molecular weight polymer brushes poly(DPA-PPEGMA). Meanwhile, polymer brushes (PDPA-g-PPEGMA) were obtained by ATRP of PEGMA from poly(BrDPA). The molecular weight of the side chains of PPEGMA could be controlled simply by modulating the ATRP time. The macromonomer and polymer brushes are soluble in nonpolar solvents such as toluene and chloroform. The polymers of poly(BrDPA) and poly(DPA-PPEGMA) absorb in the longer wavelength region, with two peaks at around 370 and 414 nm. The polymers are thermally stable and exhibit double crystallization and melting peaks during the cooling and heating scans.     

Development of 1‐Hydroxy‐2(1H)‐quinolone‐Based Photoacid Generators and Photoresponsive Polymer Surfaces

A new class of carboxylate and sulfonate esters of 1‐hydroxy‐2(1H)‐quinolone has been demonstrated as nonionic photoacid generators (PAGs). Irradiation of carboxylates and sulfonates of 1‐hydroxy‐2(1H)‐quinolone by UV light (λ≥310 nm) resulted in homolysis of weak N? O bond leading to efficient generation of carboxylic and sulfonic acids, respectively. The mechanism for the homolytic N? O bond cleavage was supported by time‐dependent DFT calculations. Photoresponsive 1‐(p‐styrenesulfonyloxy)‐2‐quinolone–methyl methacrylate (SSQL‐MMA) and 1‐(p‐styrenesulfonyloxy)‐2‐quinolone–lauryl acrylate (SSQL‐LA) copolymers were synthesized from PAG monomer 1‐(p‐styrenesulfonyloxy)‐2‐quinolone, and subsequently controlled surface wettability was demonstrated for the above‐mentioned photoresponsive polymers.     

Effect of polyaniline (PANI) on Poly(vinylidene fluoride-co-hexaflouro propylene) (PVDF-co-HFP) polymer electrolyte membrane prepared by breath figure method

Poly(vinylidene fluoride-co-hexaflouro propylene) is a well-known material for polymer electrolyte membranes (PEMs) due to its low cost, high mechanical integrity and excellent chemical resistance; however, its pure form has limited characteristics that require further modification to achieve optimum results. Therefore, the different dosages of polyaniline (PANI) (10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%) were incorporated into PVDF-HFP blend to fabricate PVDF-HFP/PANI polymer electrolyte membrane by using breath-figure method. The FTIR peaks of PVDF-HFP and PVDF-HFP/PANI membrane confirms the successful incorporation of PANI into PVDF-HFP blend, while TGA, DSC and XRD analysis shows the PANI effect on stability and ionic conductivity of PVDF-HFP membrane. The PVDF-HFP/PANI membrane with 30 wt% PANI found superior with the highest porosity of 83%, electrolyte uptake of 270% and ionic conductivity of 1.96 mS cm⁻¹; however, the other concentrations of PANI were also effective and enhanced the performance of PVDF-HFP membrane. This shows the improved performances of PVDF-HFP membrane were attributed to successful incorporation of PANI and the proposed membrane can be a suitable alternative PEM or a separator for energy devices.     

Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend composition and of the feed mixture composition. The results showed that a polymer blending method could be very useful to develop new membranes with improved permselectivity. The pervaporation properties could be optimized by adjusting the blend composition. All the blend membranes tested showed a decrease in flux with increasing poly(vinyl alcohol) content for both methanol—toluene and ethanol—toluene liquid mixtures. The alcohols permeated preferentially through all tested blend membranes, and the selectivity values increased with increasing poly(vinyl alcohol) content. The pervaporation characteristics of the blend membranes were also strongly influenced by the feed mixture composition. The fluxes increased exponentially with increasing alcohol concentration in the feed mixtures, whereas the selectivities decreased for both liquid mixtures.     

Photoacid generators (PAGs) based on N-acyl-N-phenylhydroxylamines for carboxylic and sulfonic acids

Simple and efficient photoacid generators (PAGs) for carboxylic and sulfonic acids based on N-acyl-N-phenylhydroxylamines have been demonstrated. Irradiation of o-carboxylates and thermally rearranged o-arenesulfonates of N-acyl-N-phenylhydroxylamines using UV light (≥254 nm) in aqueous methanolic solution resulted in efficient generation of carboxylic and sulfonic acids, respectively. The carboxylic acid generation ability of N-acyl-N-phenylhydroxylamines was found to be dependent on their N-acyl substituents. Further, polymer bearing o-arenesulfonates of N-acyl-N-phenylhydroxylamine was synthesized and demonstrated as PAG for sulfonic acids.     

Direct patterning of poly(amic acid) and low‐temperature imidization using a crosslinker,a photoacid generator,and a thermobase generator

A positive‐type photosensitive polyimide (PSPI) based on poly(amic acid) (PAA), a crosslinker 1,1,1‐tris{4‐[2‐(vinyloxy)ethoxy]phenyl}ethane (TVPE), a photoacid generator (PAG) (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐2‐(methylphenyl)acetonitrile (PTMA), and a thermobase generator (TBG) t‐butyl 2,6‐dimethylpiperidine‐1‐carboxylate (BDPC) has been developed as a promising material in microelectronics. The PAA was prepared from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐oxydianiline (ODA) in dimethyl sulfoxide (DMSO). The PSPI, consisting of PAA (69 wt %), TPVE (21 wt %), PTMA (3 wt %), and BDPC (7 wt %), showed high sensitivity of 21 mJ/cm² and a high contrast of 6.8 when it was exposed to a 436‐nm line (g‐line), postbaked at 90 °C for 5 min, and developed with 1.69 wt % TMAHaq. A clear positive image of 8 μm line and space pattern was printed on film, which was exposed to 50 mJ/cm² of g‐line by a contact printing mode and fully converted to the corresponding polyimide (PI) pattern on heating at 200 °C, confirmed by FTIR spectroscopy. Thus, this system will be a good candidate for next generation PSPIs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3362–3369, 2009     

Polymerizable cationic iridium(III) complexes exhibiting color tunable light emission and their corresponding conducting metallopolymers

Cyclometalated iridium(III) complexes have been synthesized for use in a variety of photophysical applications, including polymer light emitting diodes (PLEDs). A series of new complexes with one electrochemically polymerizable ligand and two phenylpyridine(ppy)-based ligands have been prepared: [Ir(ppy)₂L][PF₆](1), [Ir(F-mppy)₂L][PF₆](2), and [Ir(Br-mppy)₂L][PF₆](3), where L = 3,8-bis(2,2′-bithien-5-yl)-1,10-phenanthroline. The ancillary ppy ligands can be easily varied synthetically to tune emission color of the monomer from blue–green to red. The solid state structure of complex 1 has been obtained by single crystal X-ray crystallography. Conducting polymer materials have been prepared by electropolymerization of monomers and were characterized through XPS analysis and spectroscopic studies.     

Effect of anti-parallel and twisted alignment techniques on various propertiesof polymer stabilised liquid crystal (PSLC) films

Thin composite films consisting of liquid crystal (LC) domains surrounded by polymer networks, termed as polymer stabilised liquid crystals (PSLCs), were prepared by photo-polymerisation of a pre-polymer dissolved in LC. Four composite films were prepared with different rubbing directions and with and without electric field during photo-polymerisation. Morphological characterisation carried our using a polarising optical microscope (POM) and a scanning electron microscope (SEM) reveal significant changes in LC domain morphology and associated polymer networks with the application of electric field during the fabrication of the films. The electro-optic (EO) properties of PSLC films placed between two crossed polarisers were studied using a He–Ne laser under an action of externally applied electric field. It was found that the PSLC film with twisted alignment and polymerised in the presence of electric field showed better EO properties than other films. Transmittance obtained by EO studies was verified with absorbance studies using a Ultraviolet-Visible spectrophotometer. The dielectric behaviour of PSLC films in the frequency range 20–20 MHz was investigated using a precision impedance analyser. The obtained data were modelled using Debye and Cole–Cole methods to calculate relaxation time and distribution parameter. The relaxation time calculated through the Cole–Cole model is in agreement with response time.     

Cu(I) and Zn(II) chelations on polymer beads modified by attachment of a bipyridyl-calixarene-based chelate

A new chelating calix[4]arene derivative incorporating two bipyridyl groups and one primary amino attachment function at the lower rim has been synthesised and coupled to Wang benzaldehyde resin. The new material effectively displayed complexation abilities towards Cu(I) and Zn(II) transition metal cations. The grafting efficiency was evaluated and quantified by complexation experiments, using UV/visible spectrophotometry, and ionic chromatography.     

Effects of ceramic filler in poly(vinyl chloride)/poly(ethyl methacrylate) based polymer blend electrolytes

Effects of nano-ceramic filler titanium oxide (TiO₂) have been investigated on the ionic conductance of polymeric complexes consisting of poly(vinyl chloride) (PVC)/poly(ethyl methacrylate) (PEMA), and lithium perchlorate (LiClO₄). The composite polymer blend electrolytes were prepared by solvent casting technique. The TiO₂ nanofillers were homogeneously dispersed in the polymer electrolyte matrix and exhibited excellent interconnection with PVC/PEMA/PC/LiClO₄ polymer electrolyte. The addition of TiO₂ nanofillers improved the ionic conductivity of the polymer electrolyte to some extent when the content of TiO₂ is 15 wt%. The addition of TiO₂ also enhanced the thermal stability of the electrolyte. The changes in the structural and complex formation properties of the materials are studied by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The scanning electronmicroscope image of nano-composite polymer electrolyte membrane confirms that the TiO₂ nanoparticles were distributed uniformly in the polymer matrix.     

Dynamic behaviour of chlorofluoroethanes at fluorinated chromia aerogels and fluorinated zinc(II) or magnesium(II) doped chromia aerogels

The preparation and characterisation of two series of fluorinated chromia aerogel materials, lightly doped with zinc(II) or magnesium(II), are described. They behave as heterogeneous catalysts for transformations of 1,1,2-trichlorotrifluoroethane under HF-free conditions and at moderate temperatures. Product distributions depend critically on the contact time. When the latter is very long (static conditions) the surface becomes chlorinated, notwithstanding its fluorinated nature. Rather surprisingly, in view of previous work, the catalytic behaviour of the materials is almost identical to that of the undoped fluorinated chromia aerogel. The nature of reactions occurring under HF-free conditions and low levels of doping achievable are discussed as possible factors in determining catalytic behaviour.     

新型含磷和氟聚芳醚的制备、表征及性能

通过分子设计, 成功合成了一种含有三苯基膦结构的二氟单体--4,4’-二氟二苯苯磷氧(BFPPO). 在碱催化条件下, BFPPO与2-双-(4-羟苯基)六氟丙烷(六氟双酚A)缩聚得到一种新型含三苯基膦结构的聚芳醚材料(6F-PAEPO). 使用FTIR,1H NMR, 31P NMR, 和16F NMR等表征手段确定了聚合物的结构, 聚合物表现出良好的热稳定性、有机可溶性、机械性能和光透过性能, 其中聚合物的玻璃化转变温度高达211℃, 空气气氛和氮气气氛下5%热失重温度分别为512℃和523℃, 聚合物薄膜的最大光透过率超过80%. 尤其, 聚合物由于主链中三苯基磷氧结构的存在, 表现出了优异的阻燃性能, 有限氧指数(LOI)达到39.9%.     

新型含萘含氟聚芳醚酮的合成与表征

聚芳醚酮是一类具有独特的耐热性、耐疲劳性、耐辐射性、化学稳定性和介电性等诸多优异性能的工程塑料,广泛应用于航天、军事、电子、信息、核能和精密仪器等领域中．氟元素的引入可以降低材料的介电常数、折光率和吸水率,增加材料透明度,因此这类聚合物在光电子、光学和微电子等应用领域的研究备受关注．     

苯乙炔封端的可交联含氟聚芳醚的合成及性能

从光电集成器件对于材料性能的需要出发 ,我们相继合成了一系列可溶性的含氟聚芳醚和聚芳醚酮[1～ 5] .为了满足器件的多层化制备过程以及使器件成型后具有优异的性能 ,本文在间三氟甲基苯取代的聚芳醚 (1 1 F- PAE)中引进可交联的苯乙炔端基 ,合成了可热交联的高含氟量聚芳醚 ,并对其性能进行了初步研究 .1　实验部分1 .1　试剂与仪器　 4-苯乙炔苯酚 (PEP)按文献 [6 ]方法制备 ;3 -氟甲基苯代对苯二酚 (3 F- PH)按文献[2 ]方法制备 ;十氟联苯 ,Aldrich公司 ,99%;无水碳酸钾 ,A.R.级 ,天津化学试剂厂 ;甲苯 ,A.R.级 ,北京化工厂 ;N-…     

ESR imaging and FTIR study of thermally treated poly(acrylonitrile-butadiene-styrene) (ABS) containing a hindered amine stabilizer: Effect of polymer morphology, and butadiene and stabilizer content

Electron spin resonance imaging (ESRI) was applied to the study of thermal degradation at 393 K of poly(acrylonitrile-butadiene-styrene) (ABS) prepared by emulsion polymerization and containing 25% wt butadiene (ABS-25B). The polymer was doped with 1 or 2% wt Tinuvin 770 as the hindered amine stabilizer (HAS). The spatial distribution of the HAS-derived nitroxide radicals, obtained by 1D ESRI, was initially homogeneous, but became heterogeneous through sample depth with increasing treatment time, t. The spatial variation of ESR line shaping with sample depth was visualized by 2D spectral-spatial ESRI. ESR spectra along the sample depth, obtained by nondestructive (“virtual”) slicing of the 2D images, were used to deduce the relative intensity of nitroxide radicals present in two dynamically distinct sites; the sites were assigned to butadiene-rich (fast component) and SAN-rich domains (slow component), respectively. 1D and 2D ESRI allowed the determination of the extent of degradation within morphologically-distinct domains as a function of sample depth and treatment time. The results from the ESRI experiments were substantiated by attenuated total reflectance (ATR)-FTIR spectroscopy of the outer layer (500 μm thick) of the polymer. Both techniques indicated faster degradation of polymer samples that contained the higher HAS content, 2% wt. Comparison with the results obtained for a parallel study of ABS prepared by mass polymerization and containing 10% wt butadiene (ABS-10B) indicated clearly that the rate of degradation of the polymer prepared by emulsion polymerization (ABS-25B) is significantly reduced. This result can be explained by the formation of cross-linked “composite” networks during emulsion polymerization, which leads to greater thermal stability.