新型4,4′-双取代-2,2′-二吡啶衍生物的合成及其光学性能

以4,4′-二甲基-2,2′-二联吡啶为原料,经酸化、酰氯化,酯化和缩合反应合成了两个新型的4,4′-双取代-2,2′-二吡啶衍生物—4,4′双(4,5-二苯基嗯唑-2-基)-2,2′-二吡啶(6a)和4,4′-双(4,5-二对甲氧基苯嗯唑-2-基)-2,2′-二毗啶(6b),其结构经1H NMR,IR和MS表征.用UV-Vis和荧光激发光谱测定了6a和6b的光学性能,结果表明,6a和6b的λmax分别为229 nm和238 nm;最大发射波长均为432 nm.     

聚芳砜热降解残余物性能的研究

<正> 由双酚A和4,4′-二氯二苯基砜合成制得的聚芳砜具有良好的力学性能,聚芳砜在高温下的热裂解行为以及降解机理等也有过报道,但是对裂解残余物的性质及其与降解机理的关系却未得到注意,Hale等曾指出热降解后的碳化残余物是完全不溶的,元     

新型砜基聚苯并咪唑的合成

采用新的合成路线,以多聚磷酸催化4,4′-二羧基二苯砜与邻苯二胺反应制得双苯并咪唑二苯砜(3);以3和4,4′-二氟二苯砜为单体,环丁砜为溶剂,在无水碳酸钾存在下合成了新型砜基聚苯并咪唑,其结构经1H NMR,IR,MS和元素分析表征.     

高性能环氧树脂/碳纳米管复合物的热分析研究

用差示扫描量热仪(DSC)、热失重分析仪(TGA)和动态力学热分析仪(DMTA)研究了多壁碳纳米管(MWNTs)/高性能4,4′-二氨基二苯甲烷四缩水甘油环氧树脂(TGDDM)/4,4′-二氨基二苯基砜(DDS)复合物的热性能.Kissinger和Flynn-Wall-Ozawa的非等温固化动力学研究发现,随着MWNTs含量的增加,复合物固化反应的活化能先减小后增大.TGA研究表明,MWNTs的添加对环氧树脂热稳定性影响很小.碳纳米管填充到TGDDM/DDS体系后,复合物的储存模量随着MWNTs含量的增加而增大,而玻璃化温度却随之减小.     

查尔酮环氧树脂的合成及其固化性能

以4,4′-二羟基查尔酮为原料,和环氧氯丙烷反应合成了主链含有双键结构的查尔酮环氧树脂（CER），其结构经¹H NMR和FT-IR确证。采用非等温DSC法研究了甲基四氢邻苯二甲酸酐和4,4′-二氨基二苯基砜两种固化剂对CER的固化反应热行为，通过动态热机械分析和热失重分析对CER的热性能进行了研究。结果表明：甲基四氢邻苯二甲酸酐体系固化的CER的T_g为152.73 ℃,初始热分解温度为350.6 ℃， 800 ℃时的残碳率为19.29%； 4,4′-二氨基二苯基砜体系固化的CER的T_g为251.94 ℃,初始分解温度为365.7 ℃， 800 ℃时的残碳率为46.44%。     

用新显色剂1,1′-[2,2′-(4,4′-双噻唑基)-双偶氮]-2,2′-双萘酚与TritonX-100体系析相光度法测定微量铀

将新显色剂1,1′-[2,2′-(4,4′-双噻唑基)-双偶氮]-2,2′-双萘酚(简称4,4′-bi-TAN),用作为测定铀的高选择性的试剂。析相体系为UO_2~(2+)-4,4′-bi-TAN-TritonX-100,在580nm波长下测定UO_2~(2+),许多共存离子不干扰测定,用此法测定了铀矿废水中UO_2~(2+)的含量,结果令人满意。     

N,N,N′,N′-四炔丙基-4,4′-二氨基-二苯甲烷与4,4′-联苯二苄叠氮固化动力学研究

分别利用FTIR和DSC技术对由N,N,N,′N′-四炔丙基-4,4′-二氨基-二苯甲烷(TPDDM)与4,4′-联苯二苄叠氮(BAMBP)形成的一种新型三唑树脂的固化反应及其动力学进行了研究.TPDDM与BAMBP通过1,3-偶极环加成反应形成三唑五元环结构的聚合物,固化起始温度约为70℃,体系在较低温度下即可固化.反应体系的固化反应是一级反应,采用DSC法与FTIR法分别获得了表观聚合反应动力学参数,其结果具有一定的可比性.     

一种侧链含偶氮基团共聚物的合成及其多层膜的制备与表征

环氧氯丙烷与4,4′-二羟基偶氮苯(AZO)经缩聚反应合成了预聚物DGAZO(聚4,4′-二缩水甘油醚偶氮苯); DGAZO通过开环加成反应与PEI(枝化聚乙烯亚胺)连接制得侧链含偶氮基团的共聚物DGAZO-co-PEI(聚4,4′-二缩水甘油醚偶氮苯-co-聚乙烯亚胺),其结构经UV,IR和荧光光谱表征.DGAZO-...     

气相生长碳纤维对环氧树脂固化反应的影响及其复合物固化动力学研究

用示差扫描量热方法研究了气相生长碳纤维作为填料对4,4′-二氨基二苯甲烷四缩水甘油环氧树脂(TGDDM)/4,4′-二氨基二苯基砜(DDS)等温固化反应的影响.与纯环氧树脂一样,气相生长碳纤维复合物的固化反应也属于自催化反应类型.气相生长碳纤维对环氧树脂的固化反应动力学影响很小.固化反应的过程可以用一种修正过的自催化动力学模型来描述,在整个固化反应过程中纯TGDDM/DDS环氧树脂及其气相生长碳纤维复合物模型拟合得到的结果和实验数据相当一致.     

非等温法研究TGDDM/DDS体系固化反应动力学

采用DSC对4,4′-四缩水甘油基二氨基二苯基甲烷(TGDDM)和3,3′-二氨基二苯基砜(DDS)体系的固化反应动力学进行了研究.分别通过n级反应法和Malek的最大概然机理函数法确定了固化反应机理函数,求解了固化反应动力学参数,得到了固化反应动力学模型.结果表明,通过Kissinger,Crane方法求解动力学参数所得到的n级反应模型与实验值差别较大;而采用Malek方法判别机理,表明该固化反应按照自催化反应机理进行,实验得到的DSC曲线与模型计算所得到的曲线吻合的较好,所确立的模型在5~20K/min的升温速率下能较好地描述TGDDM/DDS体系的固化反应过程,并为工艺参数的选择和工艺窗口的优化提供了理论依据.     

碘代聚苯乙烯——负型电子束、远紫外抗蚀剂

本文合成了碘代聚苯乙烯,它是一种高灵敏度的负型电子束和远紫外抗蚀剂。作为电子束抗蚀剂,其灵敏度为1.5×10^-6C/cm²,分辨率为0.75μm,反差为2,曝光之后在真空中几乎没有后交联现象。作为负型远紫外抗蚀剂,使用500W JB-05型远紫外曝光机所需的曝光时间为20秒,能分辨1.0μm的线条。     

干法显影的电子束抗蚀剂——聚环己烯砜叠氮系

本文研究了用四氟化碳-氧等离子体进行干法显影的电子束刻蚀技术。负型电子束抗蚀剂是由聚环己烯砜和2,6-双-(4'-叠氮苯亚甲基)-4-甲基环己酮组成,其灵敏度为1.5×10^-5C/cm²,分辨率小于1μm,反差约1.43。并讨论了干法显影的影响因素和机理。     

Chemical amplification resists: Inception,implementation in device manufacture,and new developments

The chemical amplification concept aimed at dramatically boosting the resist sensitivity was invented at IBM Research in San Jose, CA, in 1980. The sensitivity enhancement is achieved by generating acid by irradiation, which induces a cascade of chemical transformations in a resist film. A chemically amplified resist based on acid‐catalyzed deprotection was quickly employed in the mid‐80s in manufacture of 1 megabit (Mbit) dynamic random access memory (DRAM) devices by deep ultraviolet (UV) (～250 nm) lithography in IBM. The unexpectedly high‐resolution capability of chemical amplification resists promoted their acceptance in the resist community and the microelectronics industry. All the advanced lithographic technologies (current workhorse 248 nm, maturing 193 nm, and emerging 157 nm, extreme UV, and projection electron beam) depend on chemical amplification resists. This article describes the invention, implementation in device manufacturing, current status, and future perspective of chemical amplification resists. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3863–3870, 2003     

正性远紫外抗蚀剂 Ⅰ.聚苯乙烯砜的研究

合成了一种高分辨率的正性远紫外抗蚀剂—聚苯乙烯砜。其灵敏度比PMMA高6.5倍。分辨率达0.75微米,并发现灵敏度与分子量和膜厚有较大的依赖关系,分子量越大,灵敏度越高;膜越薄,灵敏度越高,紫外和红外光谱表明,在光照过程中生成了氢过氧化物和羰基化合物。     

A study of the photochemical response of o-nitrobenzyl cholate derivatives in P(MMA-MAA) matrices

Ortho-nitrobenzyl cholate esters have been successfully used as photosensitive components in solution inhibition deep UV photoresists. The photochemical behavior of a variety of substituted o-nitrobenzyl cholate derivaties has been examined and resist sensitivity is related to the quantum yield of the reaction. The most efficient system examined is o, o′-dinitrobenzyl cholate/P(MMA-MMA), where the quantum yield of photoreaction is 0.2 and resist sensitivity is ca. 150 mJ/cm² for a 1.5 μm film. The mode of resist behaviour on irradiation and development is also reported.     

Charge transfer polycondensation of diethyl chelidonate with diamines in the presence of polyvinylcarbazole

Polycondensation of diethyl chelidonate (DEC), which contains an electron-accepting γ-pyrone nucleus, with hexamethylenediamine (HMD) takes place easily even at room temperature to form a corresponding polyamide. Since DEC was expected to form a charge transfer complex with an electron-donating compound such as polyvinylcarbazole (PVK), the polycondensation of DEC with diamines was carried out in the presence of PVK as a matrix. It was found that the rate of the polycondensation of DEC with diamines in dioxane was enhanced either by the presence of PVK or by the irradiation with ultraviolet (UV) light. Moreover, the polycondensation of DEC with HMD in the presence of PVK was accelerated by the UV irradiation, probably owing to the transfer of light energy.     

Photophysical processes and photochemical reactions involved in poly(N-vinylcarbazole) and in copolymers with carbazole units

This paper is devoted to the analysis of the photochemical behaviour of copolymers with carbazole units exposed to long-wavelength radiation. These copolymers are constituted of two types of carbazolylethyl methacrylate units (CEM) with octyl methacrylate moieties (OMA). The exposure of copolymers and PVK to UV light results in dramatic modifications of the physical and photophysical properties of the polymer. These modifications can be correlated with modifications of the chemical structure of the matrix. The photoageing of copolymers and PVK has been analysed by fluorescence, ESR, UV-vis and infrared spectroscopies. The effects of crosslinking and chain scissions were determined by gel fraction measurements and size exclusion chromatography.     

INDUCTION OF SKIN TUMORS IN THE RAT BY SINGLE EXPOSURE TO ULTRAVIOLET RADIATION

Abstract— The dose response for tumor induction in albino rat skin by single exposures of UV radiation has been characterized. The shaved dorsal skin of 202 animals was exposed to either of two sources: one emitting a broad spectrum of wavelengths from 275 to 375 nm, and the other emitting at 254 nm. Skin tumors began to appear within 10 weeks of exposure and continued to appear for 70 weeks. The highest tumor yield was 5.5 tumors per rat and occurred when the rats were exposed to 13.0 times 10⁴ J/m² of the 275–375 nm UV. The 275–375 nm UV was about eight times as effective as the 254 nm UV for the induction of tumors throughout the exposure range from 0.8 times 10⁴ to 26.0 times 10⁴J/m². Tissue destruction and hair follicle damage was found at the highest exposure to 275–375 nm UV but at none of the exposures to 254 nm UV. Repeated weekly exposures to 275–375 nm UV proved less effective than an equivalent single exposure for inducing tumors, even though the multiple exposures caused more severe skin damage. The transmission of the UV through excised samples of rat epidermis indicated that the exposure to the basal cell layer was about 3% of the surface exposure at 254 nm and about 15% of the surface exposure between 275 and 320 nm. The dependence of tumor yield on UV exposure was linear for 254 nm UV but was more complex for the 275–375 nm UV. For the latter more tumors were produced per unit exposure at lower exposures than at higher exposures.     

CARRIER PHOTOGENERATION IN POLY（N-VINYL-CARBAZOLE）-BASED PHOTOCONDUCTIVE THIN-FILM DEVICES

In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.     

Towards environmentally friendly, dry deposited, water developable molecular glass photoresists

Photoresists based on molecular glasses are gaining more and more importance as resist material to replace polymer based photoresist. In addition environmental issues have to be considered in the long-term. Therefore the paper describes novel negative photoresists containing a ternary mixture of a glassy low molecular functional polyphenol where the film preparation is possible by solvent-free physical vapor deposition. After UV light exposure and a thermal annealing process to enable acid catalyzed crosslinking between the molecular glass and the crosslinker, the photoresist was developed using only water to give well-defined patterns. In order to experimentally study efficiently the multiple parameters such as composition, exposure dose, and development times combinatorial PVD techniques were utilized.