气相沉积法制备聚酰亚胺薄膜的热环化研究

采用两种单体同时蒸发沉积聚合方法制备得到聚酰亚胺（PI）薄膜。对不同温度下和不同恒温时间的聚酰胺酸（PAA）薄膜进行了红外分析,将300 ℃恒温3 h以上的薄膜脱膜,用白光干涉仪测量了PI薄膜热环化前后表面质量。采用热重分析仪在不同升温速率条件下对薄膜进行了分析。结果表明,在热环化过程中,随着温度增加亚胺化程度逐渐增加。在300 ℃时随着恒温时间增加亚胺化程度逐渐增加,恒温3 h以上薄膜亚胺化较为完全,可以获得完整且不易破损的自支撑薄膜。在热环化过程中,升温速率较低时薄膜的亚胺化程度在低温区转化率提高,过量单体蒸发更完全,故一般选择较小的升温速率,约10 ℃/min甚至更低。采用上述热环化工艺得到了亚胺化程度较高且不易破损的PI薄膜,其表面均方根粗糙度为9.8 nm。     

自支撑聚酰亚胺/锆膜的制备及性能改善

 采用直流磁控溅射法制备自支撑锆(Zr)膜,采用二步法制备聚酰亚胺(PI)膜,在Zr膜表面沉积PI膜得到自支撑PI/Zr复合膜。均苯四甲酸酐(PMDA)和二甲基二苯醚(ODA)在二甲基乙酰胺(DMAC)中反应得到聚酰胺酸(PAA),然后PAA高温亚胺化得到PI;PI成膜时采用提拉法成膜。经国家同步辐射实验室计量线站测定,实际测量结果与理论分析一致,PI膜的引入虽然会导致自支撑薄膜透过率有所下降,但在类镍-银软X射线13.9 nm波段PI(200 nm)/Zr(300 nm)和PI(200 nm)/Zr(400 nm)自支撑薄膜的透过率仍然分别达到14.9%和7.5%。     

自支撑Zr膜制备及软X射线透过性能研究

软X射线波段滤光膜材料大都为自支撑金属薄膜,实验室环境下自支撑薄膜长期与空气接触表面易氧化,空气中的杂质原子进入自支撑薄膜内部,致使自支撑膜光学性能大幅下降.5 nm至20 nm软X射线波段Zr具有较低的质量吸收系数和较小的密度,在该波段Zr滤光膜透过率较高.采用脱模剂法制备自支撑Zr膜,在洁净的浮法玻璃上蒸镀一层Na...     

有机电致发光器件材料的椭偏研究

本文报道了用可变入射角椭圆偏振仪（Variable angle incidence Spectroscopic Ellipsometer）测量Alq3,NPB,CuPc,Rubrene薄膜的光学常数，我们采用真空蒸镀法在硅衬底上分别制备了以上四种薄膜，然后我们用可变入射角椭圆偏振仪对四种薄膜进行了测量，测量在大气中进行，光谱范围从200到1000nm（或1.24到5cV），测量角度为65℃、70℃、75℃、80℃，接着，用Wvase32软件对四种薄膜的光学常数随波长（光子能量）的变化函数进行拟合，通过拟合我们得到了真空蒸镀的Alq3,NPB,CuPc,薄膜的光学常数随波长的变化函数及曲线，并且从材料吸收谱的吸收边，我们还得到了这些材料的光学禁带宽度。     

自支撑Zr膜制备及软X射线透过性能研究

软X射线波段滤光膜材料大都为自支撑金属薄膜,实验室环境下自支撑薄膜长期与空气接触表面易氧化,空气中的杂质原子进入自支撑薄膜内部,致使自支撑膜光学性能大幅下降.5 nm至20 nm软X射线波段Zr具有较低的质量吸收系数和较小的密度,在该波段Zr滤光膜透过率较高.采用脱模剂法制备自支撑Zr膜,在洁净的浮法玻璃上蒸镀一层NaCl做为脱膜剂,直流磁控溅射沉积Zr膜,脱膜后的到自支撑Zr膜.为防止薄膜表面氧化及空气中杂质原子进入薄膜内部,在Zr膜两面各直流磁控溅射沉积一层10 nm厚的C或Si膜作为保护膜,得到C/Zr/C、Si/Zr/Si复合膜,测试结果显示C或Si膜的引入对于自支撑Zr膜光学性能基本无影响.     

聚酰亚胺薄膜表面粗糙度的影响因素

 采用热蒸发气相沉积聚合方法（VDP）制备了聚酰亚胺(PI)薄膜,研究了设备、衬底温度、升温过程和单体配比因素对PI薄膜表面形貌的影响。利用干涉显微镜和扫描电镜对薄膜表面形貌进行了分析;利用原子力显微镜测定了薄膜表面粗糙度。结果表明：设定蒸发源-衬底距离为74 cm时可成连续膜;蒸发源采用一段升温和多段升温时,膜表面均方根粗糙度分别为291.23 nm和61.99 nm;采用细筛网可防止原料的喷溅;均苯四甲酸二酐和4,4′-二氨基二苯醚（PMDA和ODA）单体沉积速率比值为0.9∶1时,膜表面均方根粗糙度值可减小至3.30 nm;沉积衬底温度保持30 ℃左右时,膜表面均方根粗糙度为4.01 nm, 随温度的上升,膜表面质量会逐渐变差。     

溶胶-凝胶法制备疏水性自组装SiO2薄膜

 以正硅酸乙酯（TEOS）和六甲基二硅氮烷（HMDS）为前驱体,研究了引入聚乙烯吡咯烷酮（PVP）对膜层的影响,在碱催化条件下制备了改性的二氧化硅溶胶,并采用提拉涂膜的方法在石英基底上涂膜。对不同组分的薄膜,先经热处理或紫外辐照处理,然后用十八烷基三氯硅烷（OTS）/甲苯溶液对膜层表面进行化学修饰,制备出疏水性能良好的纳米二氧化硅自组装薄膜,分析了不同后处理方法对膜层透过率、接触角、膜层表面微观形貌和激光损伤阈值影响。实验结果表明：溶胶中加入PVP提高了膜层的平整度,经OTS改性后膜层疏水性和激光损伤阈值均得到提高。     

自旋阀型[NiFe/Cu/Co/Cu]多层膜的磁电阻、矫顽力和稳定性研究

用电子束蒸镀工艺制备了自旋阀型［NiFe/Cu/Co/Cu］_N多层膜．研究了工艺过程及磁层、非磁层厚度和矫顽力对磁电阻的影响．还研究了磁电阻的稳定性和降低中心磁场等问题．用较优化的方法，制备了中心磁场为（10—20）（10³/4π）A/m，优值大于0.2%（（10³/4π）A/m）^-1的多层膜．实验表明，磁电阻随磁场的变化在中心区内是可逆的．经200℃退火15min，中心磁场略有减小，磁电阻稍有增加．一些样品经一年多老 关键词：     

电感耦合等离子体CVD低温生长硅薄膜过程中的铝诱导晶化

利用电感耦合等离子体CVD方法在350℃的低温下在镀Al玻璃衬底上制备出具有良好结晶性的Si薄膜.利用x射线衍射、紫外-可见分光椭圆偏振谱、原子力显微镜及x射线光电子谱等研究了薄膜的结构、表面形貌和成分分布等.结果表明，用这种方法制备的Si薄膜不但晶化程度高，而且具有良好的（111）结晶取向性，晶粒尺寸大于300nm，样品中无Al的残留.结合电感耦合等离子体的高电子密度特征讨论了低温生长过程中Al诱导Si薄膜晶化的机理. 关键词： 电感耦合等离子体CVD Al诱导晶化 Si薄膜 低温生长     

热蒸镀法制备Z箍缩用铝镁合金箔材及其性能

厚度低于5 m的AlMg合金箔材可作为带材切割的原材料应用于Z箍缩物理实验。利用热蒸镀方法,通过控制沉积速率在超光滑的NaCl基片上获得了AlMg薄膜,最终在脱膜后获得了厚度低于5 m的无支撑AlMg箔材。实验对该箔材的厚度均匀性、表面粗糙度、衍射峰位、晶粒尺寸及距表面不同距离下的成份进行了分析表征。实验发现,此热蒸镀法制备的AlMg合金箔材的厚度均匀性优于8%,两面的表面粗糙度均小于180 nm,晶粒尺寸约20 nm;不同厚度样品的衍射峰位未明显偏移,箔材内应力很小;不同深度下Mg含量稳定分布,而在箔材表面杂质含量较高,在距表面6 nm以下合金含量达到预期值并趋于稳定。热蒸镀法制得的无支撑AlMg合金箔材具有厚度可控且均匀、成分稳定、内应力小的特点,适用于制备Z箍缩带阵负载。     

Microstructure,interfacial interaction,and properties of polyimide/poly(vinylsilsesquioxane)/titania ternary hybrid nanocomposites

Ternary hybrid nanocomposites of polyimide (PI), poly(vinylsilsesquioxane) (PVSSQ), and titania (PI/PVSSQ/Ti) were prepared by thermal imidization from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA)-4,4'-oxydianiline (ODA) polyamic acid (BPDA–ODA PAA) and a sol-gel process from vinyltriethoxysilane(VSSQ) and titanium isopropoxide(Ti(OPr)₄). The microstructure, interfacial interaction, and optical and thermo-mechanical properties of the hybrid films have been investigated. The phase morphology and the properties are influenced by the composition of PVSSQ and titania. For the PI/VSSQ/titania ternary hybrid systems, the particle size is significantly decreased and the inorganic particles are extremely finely distributed in the nanometer scale, suggesting that the interaction between the particles and the matrix increases. It is concluded that the addition of titania plays a compatibilizing role for the PI/PVSSQ binary hybrids, resulting in the enhancement of optical transparencies and thermo-mechanical properties of the binary hybrids.     

Polyimide/hollow silica sphere hybrid films with low dielectric constant

Abstract

Polyimide (PI)/hollow silica (HS) sphere hybrid films with low dielectric constant values (low-k) were synthesized via thermal imidization process using pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA) as the polymer matrix and HS spheres as inorganic particles with the closed air voids. The monodispersed HS spheres were synthesized via a one-step process, which means that the formation of silica shells and dissolution of the core particles (polystyrene particles) occurs in the same medium. The HS particles have uniform size of ca. 1.5 μm in diameter and ca. 100 nm in shell thickness. PI/HS sphere hybrid films synthesized using mixture of polyamic acid (PAA) and HS spheres prepared via one-pot process, which means that the production of PAA and HS spheres mixture occurs with the polymerization of PMDA and ODA in the same bottle. HS spheres of two different kinds (pristine HS spheres (PHS spheres) and amine-modified HS spheres (AHS spheres)) were used for the preparation of the hybrid films. With the varying contents of AHS spheres in the range of 1–10 wt%, the dielectric constants of the PI/AHS sphere hybrid films were reduced from 3.1 of pure PI to 1.81 by incorporating 5 wt% AHS. The dielectric constants of the PI/PHS sphere hybrid films were reduced to 1.86 by incorporating 5 wt% PHS. Organic–inorganic hybrid porous polyimides may be expected as prime candidates for polymeric insulators due to their high thermal stability, good mechanical properties, solvent resistance, and low-k.     

气相沉积法制备聚酰亚胺薄膜不同单体配比的表征及其性能影响

聚酰亚胺微球作为惯性约束聚变的重要候选靶丸之一,其力学性能和热学性能的提高对于实现聚变点火有重要意义.本文以均苯四甲酸二酐和二氨基二苯醚为原料,采用气相沉积法制备了不同单体配比的聚酰胺酸薄膜,研究了制备聚酰胺酸薄膜过程中不同单体蒸发温度对薄膜组成的影响,并对聚酰胺酸薄膜进行热环化处理.采用红外光谱仪分析了聚酰胺酸薄膜和聚酰亚胺薄膜的组成,结果表明:随着二酐蒸发温度的增加,聚酰胺酸薄膜中过量二酐单体的红外吸收振动特征峰(1780 cm~(-1),1850 cm~(-1)强度增加,单体配比由二胺过量到二酐二胺配比均衡再到二酐过量.热环化处理的过程中,薄膜中过量单体会再次蒸发,其红外图谱显示最终产物只有聚酰亚胺,但单体配比接近样品聚酰亚胺红外特征振动峰(1380 cm~(-1))强度更大.X射线衍射图谱显示配比接近的样品具有更高的晶化程度,说明过量单体的存在抑制了聚酰胺酸分子链的生长,造成分子量降低.采用纳米压痕仪和热重分析仪分别测量了聚酰亚胺薄膜的弹性模量和硬度以及失重曲线,结果表明分子量的降低会造成聚酰亚胺薄膜的弹性模量和硬度的降低,同时热稳定性也变差.扫描电子显微镜图像显示聚酰亚胺薄膜呈层状结构,单体配比接近的样品表面状况更好,这一点与聚酰亚胺分子的生长规律相符合.     

Atomic oxygen erosion resistance of polyimide/ZrO2 hybrid films

A series of polyimide/zirconia (PI/ZrO₂) hybrid films were synthesized based on zirconium n-butoxide, pyromellitic acid dianhydride (PMDA) and 4,4′-oxydianiline (ODA) by a sol-gel process. The atomic oxygen (AO) exposure tests were carried out using a ground-based atomic oxygen effects simulation facility. The effects of ZrO₂ content on the morphology and structure evolvement of PI/ZrO₂ hybrid films were investigated using field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectrometer (XPS), respectively. The results indicated that a zirconia-rich layer was formed on the polyimide film sourcing from the zirconium n-butoxide after AO exposure, which decreased the erosion rate and obviously improved the AO resistance of polyimide films.     

AFM investigation of polymer LB films on the alignment of ferroelectric liquid crystal

A kind of newly synthesized polyimide (PI) LB films were fabricated to align ferroelectric liquid crystal (FLC). The topologies of PI LB films treated by different imidization processes were investigated by atomic force microscopy (AFM). It is found that the imidization temperature influences the crystalline structure of the LB films and high-temperature imidized LB films can provide the energy barrier for the realization of excellent bistability, while the ultra-thinness of LB films is helpful for the quick response of the FLC cell.     

小牛胸腺DNA分子Langmuir-Blodgett复合膜的表面增强拉曼光谱研究

本文利用Langmuir-Blodgett(LB)技术将小牛胸腺DNA分子沉积在银基底上,测试并讨论了它的π-A等温曲线,原子力图及表面增强拉曼光谱(SERS)。通过利用LB技术,获得了DNA分子的LB复合膜的高质量的SERS。在DNA分子LB膜的表面增强拉曼光谱中,DNA的核糖和碱基腺嘌呤是吸附活性部位,它们的振动光谱得到增强。DNA的其它碱基和磷酸基团的拉曼光谱强度也明显的得到增强。分析认为DNA分子增强的拉曼光谱主要是由于LB膜的有序结构的贡献,使得SERS效应得到进一步的增强。因此利用LB技术是得到DNA的高质量SERS很好的方法。     

Preparation and Characterization of 2,2-bis[4-(3-Aminophenoxy)phenyl]propane/4,4′-Oxydianiline/4,4′-Oxydiphthalic Anhydride (3-BAPOPP/44ODA/ODPA) Polyimide Films with Various Co-monomer Ratios

A new diamine monomer 2,2-bis[4-(3-aminophenoxy)phenyl]propane (3-BAPOPP) was synthesized through two steps and its melting point was determined by differential scanning calorimetry (DSC). It was then copolymerized with 4,4′-oxydianiline (44ODA) and 4,4′-oxydiphthalic anhydride (ODPA) to obtain a series of aromatic polyimide(3-BAPOPP/44ODA/ODPA-PI) films. Fourier transform infrared (FT-IR) was used to characterize the structures of the monomer and the polyimide films. Water absorption, ultraviolet-visible (UV-Vis) spectroscopy, contact angle, DSC, and thermo-gravimetric analysis (TGA) were used to characterize the properties of 3-BAPOPP/44ODA/ODPA-P films. The results showed that the PI films had low water absorption in the range of 1.5%～1.9%, low surface energy in the range of 43.3 ～43.5 mJ/m², glass transition temperature (T_g) in the range of 192.5°C～226.1°C, and dielectric constant in the range of 2.79～3.02 at 1 MHz. The films also exhibited good thermal properties and good optical properties, with the ultra violet cut-off wavelength being in the range of 346～364 nm.     

Microstructure and interfacial interaction of polyimide/silica hybrid nanocomposites prepared with 3-aminopropyltriethoxysilane

A series of polyimide (PI)-silica hybrid nanocomposites are prepared from 3,3′,4,4′biphenyltetracarboxylic dianhydride (BPDA)-4,4′-oxydianiline (ODA) polyamic acid (PAA) and tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) by the sol-gel process. 3-Aminopropyltriethoxysilane (3-APS) is used to enhance the interfacial interaction between polyimide and silica. The morphology, interfacial interaction, and properties of the hybrids are investigated using scanning electron microscope (SEM), UV-vis spectroscopy, atomic force microscope (AFM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). SEM and AFM images indicate that silica particles of ca. 45-55 nm size are uniformly distributed in polyimide matrices and that the interfacial interaction between PI and TEOS is better than that between PI and TMOS. The optical transparencies of the PI/TEOS hybrids are better than that of the PI/TMOS hybrids. FTIR spectra confirm the Si O Si bond as well as the conversion of PAA to polyimide and PI/silica hybrid films. The thermal stability is increased after incorporation of the silicas in the polyimide matrix.     

Synthesis and photocatalytic properties of porous TiO2 films prepared by ODA/sol-gel method

Porous TiO₂ films were deposited on SiO₂ pre-coated glass-slides by sol-gel method using octadecylamine (ODA) as template. The amount of ODA in the sol played an important role on the physicochemical properties and photocatalytic performance of the TiO₂ films. The films prepared at different conditions were all composed of anatase titanium dioxide crystals, and TiO₂ crystalline size got larger with increasing ODA amount. The maximum specific surface area of 41.5 m²/g was obtained for TiO₂ powders prepared from titanium sol containing 2.0 g ODA. Methyl orange degradation rate was enhanced along with increasing ODA amount and reached the maximal value at 2.0 g addition of ODA. After 40 min of UV-light irradiation, methyl orange degradation rate reached 30.5% on the porous film, which was about 10% higher than that on the smooth film. Porous TiO₂ film showed almost constant activity with slight decrease from 30.5% to 28.5% after 4 times of recycles.