Self-Enhancement of Scalar and Vector Holographic Gratings in Azobenzene Molecular Glassy Films

Self-enhancement (SE) effect of scalar and vector holographic gratings (HG) recorded in three different azobenzene molecular glassy films is experimentally studied in both transmission and reflection modes at 532 and 633 nm. The maximal SE factor (the ratio of diffraction efficiency to its initial value) SEF = 42 has been achieved. It is shown that the model of complementary HG can be applied also in scalar transmission thin HG case to explain coherent SE. The possibility of vector HG coherent SE in transmission mode is experimentally demonstrated for the first time (SEF = 4.3). The possibility of coherent HG SE in reflection mode is also established for the first time (SEF = 21). HG recording processes as well as coherent SE processes are found to be independent in transmission and reflection modes being determined by volume and surface relief HG, respectively. The permittivity gradient mechanism is proposed to explain the coherent SE of surface relief HG. Both HG recording and coherent SE efficiencies strongly decrease when HG period is decreased from 2 mm to 0.5 mm. No relaxational SE effect is found. Coherent SE effect in molecular glasses is found to be weaker than in inorganic materials.

Chemically Amplified Resist Based on Dendritic Molecular Glass for Electron Beam Lithography

A novel dendritic molecular glass(MG)containing adamantane core(AD-15)was synthesized and characterized.It exhibits good solubility in common organic solvents and a stable amorphous state at room temperature,which contributes to forming films with different thicknesses by spin-coating.The thermal analysis of AD-15 indicates that no apparent glass transition temperature(Tg)is observed before the thermal decomposition temperature(Td=160℃).The good thermal resistance suggests that it can satisfy the lithographic process and is a candidate for photoresist materials.The patterning properties of AD-15 resist were evaluated by electron beam lithography(EBL).By optimizing the lithographic process parameters,AD-15 resist can achieve 40 nm half-pitch patterns with a line-edge roughness of 4.0 nm.The contrast and sensitivity of AD-15 resist were 1.9 and 67µC/cm^(2),respectively.Compared with the commercial PMMA(950k)electron beam resist,the sensitivity of AD-15 resist increases by 6 times.This study provides a new example of molecular glass resist with high resolution and sensitivity for EBL.

Outgassing analysis of molecular glass photoresists under EUV irradiation

A device was designed and assembled to analyze the outgassing of molecular glass(MG)photoresists under extreme ultraviolet(EUV)exposure.The outgassing of the photoresists with different components and different concentrations of tert-butoxycarbonyl(t-Boc),photo-generated acid(PAG),and acid quencher was systematically investigated.Based on experiments,some solutions for reducing the outgassing of MG photoresists were proposed.

Single-component chemically amplified i-line molecular glass photoresist based on calix[4]resorcinarenes

Calix[4]resorcinarene, prepared by the acidcatalyzed condensation of resorcinol and paraldehyde, was used as the core of the molecular glass compound. The hydroxyl groups of calix[4]resorcinarene were partly protected by tert-butoxycarbonyl(t-BOC) and then esterified with 2-diazo-1-naphthoquinone-4-sulfonyl chloride(2,1,4-DNQ-Cl). Upon irradiation to 365 nm light, the 2,1,4-DNQ groups undergo photolysis to generate a small quantity of sulfonic acid other than indene carboxylic acid. The generated sulfonic acid can further catalyze the deprotection of the t-BOC group. So, a new type of single-component chemically amplified i-line positive photoresist can be formed by the molecular glass compounds. The lithographic performance of the resist was evaluated with high resolution and photosensitivity with an i-line stepper.

Immobilization of radioactive fluoride waste in aluminophosphate glass:a molecular dynamics simulation

Molecular dynamics(MD) simulations were conducted to investigate the structural and chemical environment of aluminum in aluminophosphate glasses.Such glasses have the potential for application in the disposal of radioactive fluoride waste from molten salt reactors(MSR).Due to the risks of studying these materials and the limitations of realistic research conditions,MD simulations were used as an alternative method to study the vitrification of radioactive fluoride waste.In the past decades,aluminophosphate glasses have been studied and they exhibit certain favorable properties for high-level radioactive waste management.This work focuses on the effects of fluorine addition on structural changes in the glass.We observed that glass with composition P_2O_5–Al_2O_3–Na_2O–CaO exhibited a good performance in immobilizing fluoride at low F concentrations(approximately under25 mol%).Significant changes were observed where PO_3F_2 units replaced PO_3F units in the glass.The fourcoordinated AlO_4 units were increasingly converted into five-coordinated [AlO_xF_y] with the increasing F content.The radionuclide Sr in the simulation had the tendency to form six-coordinated octahedrons in the glass.We conclude that the structural changes resulting from the fluoridewaste added to aluminophosphate glasses does not adversely affect their chemical stability at relatively low F concentrations,i.e.,under 25 mol%.Hence,the use of phosphate glasses is a potential alternative method of fluoride waste disposal.

Epoxy-based azo molecular glasses with four-arm architecture:Preparation, characterization and holographic recording

In this study,a series of epoxy-based azo molecular glasses with four-arm architecture was synthesized based on an intermediate(MDGA-AN),which was obtained from ring-opening reaction between 4,4'-methylene-bis(N,N’-diglycidylaniline)and N-methylaniline.The azo compounds were then synthesized through azo-coupling reaction between MDGA-AN and diazonium salts of 4-nitroaniline,4-aminobenzonitrile,4-aminobenzoic acid,4-fluoroaniline and 4-methoxyaniline,respectively.The azo compounds were thoroughly characterized and the photoresponsive properties of their solid films were investigated at three different wavelengths(λex=488,532 and 589 nm).The results show that the electron-withdrawing groups on the azo chromophores can significantly affect the absorption band positions in visible light range,which shift to the longer wavelength with the enhanced push-pull effect.Both photoinduced birefringence and surface-relief-grating formation are closely related to the electronwithdrawing groups and excitation wavelengths of the actinic light,which show significant influences on the growth rates and saturated values of the photoinduced variations.In this series,the azo molecular glasses containing cyano and carboxyl groups as the electron-withdrawing groups show the significantly higher efficiency for both the photoinduced birefringence growth and the SRG formation compared with others under the same light irradiation conditions.The capability of the materials as a photo-storage medium is demonstrated by holographic recording.

Molecular Dynamic Simulation Study on Glass Transition Temperature of DGEBA-THPA/SWCNTs Composites

Molecular dynamic (MD) simulations were carried out to predict the thermo-mechanical properties of the cured epoxy network composed of diglycidyl ether bisphenol A (DGEBA) epoxy resin and tetrahydrophthalic anhydride (THPA) curing agent and their single-walled carbon nanotubes (SWCNT) reinforced the epoxy matrix composites. Different characters such as the density of the materials and mean square displacements (MSDs) were calculated to estimate the glass transition temperatures (Tgs) of of the materials. 365 K and 423 K of the Tgs were obtained respectively, whereas the latter is much higher than the former. The simulation results indicated that the incorporation of SWCNTs in the epoxy matrix can significantly improve the Tg of the cured epoxy. The approach presented in this study is ready to be applied more widely to a large group of candidate polymers and nanofillers.

Icosahedral medium-range order formed in Mg_(70)Zn_(30) metallic glass: a larger-scale molecular dynamics simulation

A larger-scale Mg70Zn30 alloy system including 100000 atoms has been simulated by using the molecular dynamics method to investigate the icosahedral medium-range order （IMRO） formed in the MgToZn30 metallic glass. It is found that the simulated pair distribution function of Mg70Zn30 metallic glass is in good agreement with the experimental results. The glass transition temperature Tg is near 450 K under the cooling rate of 1×10^12 K/s. The icosahedral local structures play a critical role in the formation of metallic glass, and they are the dominant local configurations in the Mg70Zn30 metallic glass. The IMRO in the Mg70Zn30 metallic glass is characterized by certain types of extended icosahedral clusters combined by intercross-sharing atoms in the form of chains or dendrites. The size distributions of these IMRO clusters present a magic number sequence of 19, 23, 25, 27, 29, 31, 33, 35, 37, 39,..., and the magic clusters can be classified into three types according to their compactness. The IMRO clusters grow rapidly in a low-dimensional way with cooling, but this growth is limited near Tg.

Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.

Ab initio molecular dynamics study on the local structures in Ce_(70)Al_(30) and La_(70)Al_(30) metallic glasses

Ab initio molecular dynamics simulations were performed to investigate the effect of similar elements on the shortto medium-range atomic packing features in Ce70Al30 and La70Al30 glass-forming alloys. 4 f electrons of Ce element in Ce70Al30 alloy were properly treated in electronic calculations. The local atomic structures in both alloys are qualitatively similar. However, the local environments of Al atoms in Ce70Al30 alloy show fluctuation with temperature in the cooling process, which could result from 4 f electrons of Ce elements. Surprisingly, the medium-range atomic packing features of Al atoms in both MGs are quite different, although Ce and La elements are similar. These findings are useful for understanding the enhanced glass-forming ability by similar element substitution in RE-based MGs from a medium-range structure perspective.

分子量对PA1012及其复合材料性能的影响

以三种不同分子量及分子量分布的长碳链AABB型偶-偶尼龙1012(PA1012)为原料,探究了分子量及分布对纯PA1012以及PA1012/玻璃纤维(GF)复合材料结构与性能的影响。对不同分子量及分子量分布的PA1012的基础物理性能、热力学性能以及结晶行为进行表征和分析,结果表明,高分子量和宽分子量分布的PA1012具有更高的韧性、更小的热变形温度和更大的模塑收缩率。与GF复合后,PA1012/GF复合材料的力学性能和耐热性能相较于纯PA1012得到大幅提高,同时吸水率和收缩率明显下降。高分子量和宽分子量分布会降低PA1012/GF复合材料的结晶能力,有利于复合材料的韧性提高,使其刚性和耐热性能下降,纵向/横向收缩率差值增加。实际应用中如对材料刚性有较高要求,可选择分子量低/分子量分布窄的PA1012产品;若要求材料具有较高韧性,可选择分子量高/分子量分布宽的PA1012产品。

具有双重显影特性的多用途单分子树脂化学放大光刻胶

化学放大光刻胶(CARs)由于其在分辨率和灵敏度方面的出色性能而广泛应用于光刻领域。本文报道了一种基于单分子树脂的多用途化学放大光刻胶SP8-PAG_(AN),可同时用于365 nm光刻和电子束光刻。该体系主要由螺二芴结构的单分子树脂主体材料(SP-8Boc)和N-(三氟甲基磺酸酯基)蒽-1,9-二羧酰亚胺非离子型光致产酸剂(PAGAn)组成。测试了产酸剂PAGAN在365 nm紫外光激发下的光致产酸效率ΦH+为23%。研究了SP8-PAG_(AN)光刻胶的365 nm光刻和电子束光刻性能。365 nm光刻中,分别利用四甲基氢氧化胺(TMAH,质量分数2.38%)水溶液和正己烷作为显影液,可实现1μm正性和负性光刻图案。电子束光刻中,可实现50 nm Line/Space(L/S)的正性密集线条图案(曝光剂量110μC/cm^(2)),32 nm L/S的负性密集线条图案(曝光剂量40μC/cm^(2))以及19 nm L/3S负性半密集线条图案(曝光剂量96μC/cm^(2))。本研究工作提供了一种具有双重显影特性的多用途单分子树脂化学放大光刻胶的新范例。

NiNb金属玻璃原子结构和力学性能的分子动力学研究

采用分子动力学模拟的方法,对不同成分的NiNb合金进行原子结构和力学性能方面的研究。通过对降温过程中玻璃转变温度的变化和高温熔体混合焓、混合熵的变化对比发现,在成分点c_(Ni)=0.65前后,合金表现出截然不同的变化趋势。同时利用双体分布函数,配位数,Warren-Cowley参数,键对分析,准近邻原子等方法对NiNb合金进行原子结构相关分析,发现在c_(Ni)=0.65前后,部分结构参数也表现出不同趋势,说明在此成分点前后,NiNb金属玻璃在原子结构上差异较大。综合热力学和结构参数的变化,c_(Ni)=0.65可能是两个合金体系的分界点,c_(Ni)=0.65之前为Nb基,c_(Ni)=0.65之后为Ni基。最后对力学性能进行了模拟,发现力学性能的表现主要和不同成分下NiNb之间的结合方式相关。此项研究有利于加深对金属玻璃原子结构和力学性能的理解。

退火处理对Pt基块体金属玻璃塑性动力学行为的影响

采用退火的热诱导方法向Pt基块体金属玻璃(Pt-BMG)基体内原位引入纳米晶,通过纳米压痕实验,考察了Pt-BMG在铸态和在玻璃转变温度Tg之上(250℃)退火15 min,2 h和6 h的力学性能和塑性动力学行为.研究结果表明,退火时间从15 min增加到6 h时,Pt-BMG的结晶度从34%增加到57%,平均晶粒尺寸从25.6 nm增加到38.3 nm,硬度和折合模量分别从5.66 GPa和133.83 GPa增加到8.65 GPa和182.89 GPa,同时载荷-位移曲线上的锯齿流变行为呈现从可明显观察到不连续的位移突变到比较平滑的变化规律.通过分子动力学模拟进一步证明,随着纳米晶尺寸的增加,剪切转变区的激活与剪切带的成核呈现先促进后抑制、先增加后减小的趋势.这是由于金属玻璃在塑性变形过程中,小尺寸纳米晶会被剪切带所包裹或溶解,促进了金属玻璃塑性变形的形成;而大尺寸纳米晶在承受载荷时,在晶体内部产生了位错和滑移,进一步抑制了剪切带的成核与传播.本文结合纳米压痕实验和分子动力学模拟,从原子尺度上揭示了纳米晶的尺寸影响非晶合金塑性变形的内在机理,为设计理想性能的金属玻璃提供了有效的实验基础与理论支撑.

非晶合金结构演变影响玻璃形成能力的分子动力学研究

通过分子动力学方法模拟了Ti_(75)Al_(25)、Ni_(50)Zr_(50)和Cu_(50)Zr_(50)非晶合金的玻璃转变过程,得到并分析了平均原子体积和双体分布函数等结构参数,并应用Voronoi多面体指数分析法统计了玻璃转变过程中二十面体及类二十面体团簇的数量,通过分析团簇在玻璃转变过程中种类和数量的涨落趋势,研究了非晶原子由短程序连接至中程序再至长程无序的动力学演化过程.结果表明,非晶合金的玻璃形成能力以及塑性变形能力与动力学演化过程中Voronoi团簇的种类和数量密切相关.在玻璃转变过程中局部五次对称性高的团簇倾向于连接在一起形成链,从而密排整个空间,降低系统的动力学行为从而提高玻璃形成能力.塑性形变倾向于发生在局部五次对称性较低的区域.在玻璃转变温度附近团簇种类和数量的突变反映出非晶合金的自组织临界行为,蕴含着丰富的非线性动力学现象.

热氧老化对马来酸酐接枝聚丙烯的结构与性能的影响

以自制的马来酸酐接枝聚丙烯(PP-g-MAH)为研究对象,研究了PP-g-MAH对玻璃纤维增强聚丙烯材料性能的影响以及热氧老化对PP-g-MAH分子结构和性能的影响。结果表明,自制的PP-g-MAH大幅度提高了30%玻纤增强聚丙烯材料的力学性能;随着热氧老化时间的延长,PP-g-MAH的MFR不断增加,对玻璃纤维增强聚丙烯材料的力学性能的提升作用不断降低;通过凝胶色谱仪(GPC)、红外光谱(IR)和马来酸酐(MAH)接枝率测定结果的分析,热氧老化过程没有对PP分子链接枝的马来酸酐产生明显的影响,而是引起了聚丙烯分子链的断裂,造成PP-g-MAH分子量下降,导致自身力学性能下降,使得PP与玻璃纤维之间的界面强度下降,使得PP-g-MAH对玻璃纤维增强聚丙烯材料的力学性能提升作用下降。

基于分子动力学模拟下CuZr金属玻璃的局域连接度对拉伸性能的影响

二十面体连接网络是由二十面体相互连接而形成的中程有序结构。利用分子动力学模拟方法研究了CuZr金属玻璃在拉伸过程中的二十面体连接网络的演变。结果表明,二十面体连接网络会因为变形而断裂,从而出现孤立的二十面体,或是转变成其他团簇。高的米瑟斯应力和屈服时更少的连接度数量百分比可以解释Cu含量低的样品中的较低强度和良好塑性。此外,在Cu含量高的样品中,低连接度在变形后更倾向于向高连接度转变,让样品在变形后仍保持着较高的连接度,呈现为强度高、塑性低的力学性能。

基于分子动力学模拟研究交联密度对氢化丁腈橡胶性能的影响

采用分子动力学构建交联密度为0,10%,20%,30%和40%的氢化丁腈橡胶(HNBR)分子模型,研究交联密度对HNBR性能的影响。结果表明:HNBR分子模型的玻璃化转变温度(T_(g))随着交联密度的增大而升高,交联密度为0~10%时,T_(g)升高较快,交联密度大于10%时,T_(g)升高速率趋于平缓;HNBR分子模型的均方位移(MSD)随着交联密度的增大而减小,分子链的柔顺性变差,交联密度达到30%后,MSD变化较小;交联密度为0~30%时,HNBR分子模型的拉伸性能随着交联密度的增大而提高,交联密度为30%时,HNBR分子模型的拉伸性能最好,交联密度大于30%时,晶格内应力集中,HNBR分子模型的拉伸性能随交联密度的增大而降低。

基于分子动力学模拟预测环氧树脂形状记忆性能研究

形状记忆环氧树脂是制备可展开空间结构的重要材料之一,通过分子动力学模拟预测环氧树脂的形状记忆性能是设计与制备形状记忆环氧树脂的有效指导手段。在pcff力场下,通过分子动力学模拟方法,构建了交联度分别为36%、48%、59%、72%和84%的三乙烯四胺固化的双酚A环氧树脂聚合物模型,并模拟计算了其玻璃化转变温度、力学性能及形状记忆性能。结果表明,不同交联度的环氧树脂聚合物模型均表现出较好的形状固定率,为80%~86%;分析聚合物模型的x、y、z三轴回复性可知,36%交联度的环氧树脂不具有形状记忆性能,48%交联度的环氧树脂形状记忆性能较差,而59%、72%、84%交联度的环氧树脂的形状回复率均能达到80%以上,具有良好的形状记忆性能,且交联度越高形状回复速度越慢。