Preparation and photochromic behavior of crosslinked polymer thin films containing polyoxometalates

A series of reversible photochromic nanocomposite films were prepared by entrapping phosphotungstic acid (PWA) and molybdenumphsophoric acid (PMoA) into P(VP-BVA), which was a crosslinked polymer based on N-vinylpyrrolidone (VP) and bisvinyl-A (BVA). The microstructure, photochromic behavior and mechanism of the films were studied with transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectra (UV-vis) and electron resonance spectra (ESR). The TEM image showed that the polyoxometalates particles had regular microstructure with narrow size distribution (average diameter of 30 nm) in hybrid films. FT-IR results showed that the Keggin geometry of polyoxometalates (POM) was still preserved inside the composites and strong coulombic interaction between POM and crosslinked polymer matrix was built. Irradiated with ultraviolet light, the transparent films changed from colorless to blue and showed reversible photochromism. Oxygen plays an important role during the bleaching process. PMoA/P(VP-BVA) film had higher photochromic efficiency and slower bleaching reaction than PWA/P(VP-BVA) film. The characteristic signals of W (V) or Mo (V) in ESR spectra indicated that electron transfer occurred between the organic substrates and heteropolyanions under UV irradiation, which induced heteropolyanions to heteropolybules with simultaneous oxidation of the organic substrates.     

Structure and photochromism of polyoxometalates nanoparticles in cross-linked polymer networks

Cross-linked polymer (P(VP-MB)) based on N-vinylpyrrolidone (VP) and N, N′-methylene-bis-acrylamide (MB) was used as polymer matrix to construct photochromic nanocomposite thin films with entrapping the Keggin-type polyoxometalates (POM). The microstructure, photochromic behavior, and mechanism of the films were studied with transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectra (UV-vis), and electron resonance spectra (ESR). The transparent films changed from colorless to blue under UV irradiation. The films showed good reversible photochromism and could recover the colorless state gradually in the air, where oxygen plays an important role during the bleaching process. The heteropolyanions dispersed in composite films uniformly and exhibited strong coulombic interaction with cross-linked polymer. Composite films contained molybdenum had higher photochromic efficiency and slower bleaching reaction than films contained tungsten. According to ESR, the photochromic mechanism was followed by charge-transfer happened between POM and cross-linked polymer.     

Preparation and photochromism of nanocomposite thin film based on polyoxometalate and polyethyleneglycol

A photochromic nanocomposite based on Keggin structure phosphomolybdic acid (PMoA) well dispersed in polyethyleneglycol (PEG) was fabricated. TEM image showed that PMoA nanoparticles with narrow size distribution were finely dispersed in polymer matrix. FT-IR results showed that the Keggin geometry of polyoxometalates was still preserved inside the composites and strong coulombic interaction was built between PMoA and polymer matrix. Under UV irradiation, the film was reduced photochemically to yield a blue species, which was in accordance with a charge-transfer mechanism.     

Preparation of Pb0.98La0.02(Zr0.65Ti0.35)O3 films and their fine patterning

The photosensitive lanthanum-doped lead zirconate titanate (PLZT) gel films were prepared by chemical modification with acetylacetone (AcAcH), and their fourier transform infrared (FT-IR) spectra and ultraviolet visible (UV-Vis) spectra were measured. The results show that the chelate rings of AcAcH with Ti or Zr are formed in the PLZT gel films. With irradiation of UV light, the chelate rings are photolyzed, and lead to a change of the solubility of the PLZT gel films in methanol. Transmission electron microscope (TEM) observations show that the perovskite phase is crystallized in PLZT thin film after heat treatment at 700 °C, whose grain sizes are less than or equal to 60 nm. The PLZT thin films exhibited hysteresis loops and good fatigue properties.     

Synthesis of silver nanoparticles in poly(vinyl alcohol) matrix in solution and thin films through laser irradiation

Here we communicate our experimental results on the synthesis of silver nanoparticles in solution and thin films using silver nitrate and poly vinyl alcohol (PVA) mixture at different concentrations and different laser irradiations. Detailed studies were carried out by varying pulse width, wavelength, exposure time, and energy of the laser. Formation of nanoparticles was confirmed through color change from transparent to yellow. Irradiated solutions and thin films at different concentrations showed plasmon peak in the absorption spectra. Formation of different sized nanoparticles at different energies with peak shift is observed. Transmission electron microscope (TEM) results confirmed the formation of nanoparticles with size of the particles varying from 2 to 200 nm. Formation of silver nanoparticles with hexagonal and different shapes were observed in particular with 355 nm laser irradiation. Influence of wavelength, pulse width, exposure time, and energy in the synthesis of silver nanoparticles is highlighted. Electron diffraction patten of a single nanoparticle in TEM showed polycrystallinity with cubic nature for the silver nanoparticles prepared. We also compared the linear and nonlinear absorption properties of the freshly prepared nanoparticles with nanoparticles solution left in a shelf for a long period of time.     

Characteristics of organic-inorganic hybrid plasma polymer thin films for low-κ ILD applications

This study investigated the effects of plasma power and tetraethylorthosilane (TEOS) to cyclohexene ratios on low-κ organic-inorganic hybrid plasma polymer thin films deposited on silicon (100) substrates. These films were deposited using a plasma enhanced chemical vapor deposition (PECVD) method, in addition to the electrical and mechanical properties of the resulting composites. Cyclohexene and TEOS were used as organic and inorganic precursors, respectively, with hydrogen and argon as precursor bubbler gases. Furthermore, additional argon was used as a carrier gas. The as-grown polymerized thin films were analyzed using ellipsometry, Fourier-transform infrared (FT-IR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The ellipsometry results showed the thickness of the hybrid thin film, and the FT-IR spectra showed that the hybrid polymer thin films were completely fragmented and polymerized between cyclohexene and TEOS. AFM results showed that polymer films with a smooth surface could be grown under various deposition conditions, while TEM and XRD showed that the hybrid thin film was an amorphous plasma polymer thin film without porosity. In addition, current-voltage (C-V) curves were prepared to calculate the dielectric constants. Post-annealing was applied to investigate the thermal stability of hybrid plasma polymer thin films in the hardness, Young's modulus, thermal shrinkage, and the dielectric constant at 400 °C.     

Synthesis and characterization of polyimide-based hybrid thin films from a novel colloidal core-shell nanocomposite particles

In this study, poly(4,4-(hexafluoroisopropylidenediphthalic anhydride)-co-oxydianiline) (6FDA-ODA) and a novel core-shell nanoparticle consisting of a core (SnO2/TiO2) and a shell (ZrO2/Sb2O3) with the composition (SnO2:TiO2:ZrO2:Sb2O3 = 18:5:3:4) were used to prepare polyimide/nanoparticles hybrid thin films. The resultant hybrid thin films were investigated by FTIR, TGA, DSC, TEM, SEM, AFM, alpha-step, UV-Vis, and n&k analyses. The results show that the prepared hybrid thin films had a good thermal stability. The size of nanoparticles was effectively controlled in the range of 8-10 nm in the hybrid thin films. These nanoparticles were evenly distributed across the hybrid thin films and no phase separation occurred. In terms of the optical properties, the prepared hybrid thin films had good transparency in the range of visible light. The cutoff wavelength had a blue shift as the content of the nanoparticles increased. The refractive index of prepared hybrid thin films increased with corresponding increases in nanoparticle content. Moreover, the prepared polyimide/core-shell nanoparticle hybrid thin films displayed excellent film formability and planarity.     

Structure and Optical Behavior of Nanocomposite Hybrid Films of Well Monodispersed ZnO Nanoparticles into Poly （vinylpyrrolidone）

We fabricated an inorganic-polymeric photoluminescent thin film based on ZnO nanoparticles, which were grown directly in the poly（vinylpyrrolidone） （PVP） matrix. The microstructure, composition, thermal stability, and the temperature-dependent photoluminescence of the thin film were investigated. X-ray diffraction （XRD） and transmission electron microscopy （TEM） results indicated that all the ZnO nanoparticles with a polycrys talline hexagonal wurzite structure were well separated from each other and were dispersed in the polymeric matrix homogeneously and randomly. Raman spectrum （Raman） showed a typical resonant multi-phonon process within the hybrid thin film. The shifts of infrared bands for PVP in the hybrid film should be attributed to strong coulombic interaction between ZnO and polymeric matrix. The stability of the hybrid film and the effect of the perturbation of ZnO on the stability were determined by means of the thermogravimetric analysis （TG） and differential thermal analysis （DTA）. The ultraviolet-visible adsorption （UV-vis） showed distinct excitonic features. The photoluminescent spectrum （PL） of the ZnO nanoparticles modified by PVP molecules showed markedly enhanced ultraviolet emission and significantly reduced green emission, which was due to the Perfect surface passivation of ZnO nanoparticles. Temperature dependent photoluminescent spectrum studies suggested that the ultraviolet emission was associated with bound exciton recombination.     

非晶ZrO2-SiO2系薄膜及微细图形的制备

采用溶胶－凝胶与化学修饰相结合的方法制备了ZrO2-SiO2系薄膜，研究了这种凝胶薄膜的FT－IR光谱特性及随紫外线照射时的变化，发现在1600－1400cm^-1之间有一些与含锆螯合物相关的峰，这些峰值随紫外线照射而减弱，表明这些螯合物发生分解，伴随着螯合物的分解，薄膜的乙醇中的溶解能力也发生变化，利用这特性，紫外光通过掩膜照射凝胶薄膜，用有机溶剂溶洗后，获得凝胶薄膜的微细图形，再进行热处理，消除薄膜中的有机物就可得到非晶质ZrO2-SiO2系薄膜的微细图形。     

Microstructural analysis and mechanical properties of TaN-Ag nanocomposite thin films

TaN-Ag nanocomposite thin films with Ag nanoparticles dispersed in TaN matrix and surface were prepared by reactive co-sputtering of Ta and Ag in a plasma of N₂ and Ar. The films were then annealed using RTA (Rapid Thermal Annealing) at various annealing times and annealing temperatures to induce the nucleation and growth of Ag particles in the TaN matrix and on the film surface. Transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM) were applied to examine the microstructure and surface morphology of TaN-Ag thin films. It is found that Ag tends to precipitate on the columnar boundaries when Ag concentration is low. In this case, the hardness as well as the resistance-to-crack can be enhanced. When Ag concentration is high, the TaN columnar structure is disrupted which can reduce the hardness and resistance-to-crack. Overall, the results reveal that the hardness and crack resistance of these films can be controlled by varying Ag contents and annealing conditions.     

Quantum confinement effect of CdS nanoparticles dispersed within PVP/PVA nanocomposites

Nanocomposite films of CdS nanoparticles within PVP/PVA blend were prepared. The prepared films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, Ultraviolet–visible spectroscopy (UV–vis), transmission electron microscopy (TEM) and photoluminescence (PL) spectra. The amount of Cd⁺ used strongly influenced the size of the CdS nanoparticles, which was confirmed by XRD, UV–vis absorption spectra, PL emission spectra and TEM images. Smaller sized CdS nanoparticles were formed in higher content of cadmium. The results of XRD indicate that CdS nanoparticles were formed with hexagonal phase in the polymeric matrix. PL and UV–vis spectra reveal that nanocomposite films shows quantum confinement effect. Optical band gap and particle size were calculated and is in agreement with the results obtained from TEM data. The direct energy band gap was increased up to 2.86 eV.     

退火时间对BNT-BT6薄膜微结构及压电性能的影响

采用溶胶-凝胶法(Sol-Gel)在Pt/Ti/SiO2/Si(100)衬底上制备了0.94(Na0.5Bi0.5)TiO3-0.06BaTiO3(BNT-BT6)薄膜,研究了不同退火时间对其微结构和压电性能的影响。X射线衍射(XRD)结果表明,制备的BNTBT6薄膜为钙钛矿型铁电薄膜,随着退火时间的延长,晶粒尺寸略有增加。原子力显微镜(AFM)结果表明,制备的薄膜表面比较平整、无裂缝。随着退火时间的延长,薄膜的粗糙度有所增加。在退火时长为60min时薄膜表面具有最佳的均一性,在退火时间为90min时薄膜均一性最差;优化退火时间,可提高薄膜结晶程度,避免焦绿石相的生成,进而提高BNT-BT6薄膜压电性能。压电力显微镜(PFM)结果表明,BNT-BT6薄膜的电畴为多畴结构。在不同退火时间下均有明显的压电响应,特别是在退火时间为60min时,BNT-BT6原始电畴有着最高的振幅强度。在30min、40min、60min和90min退火时间时,其平均压电系数d33分别为48pm/V、157pm/V、186pm/V和142pm/V。     

Characterization of infrared matrix-assisted laser desorption ionization samples by Fourier transform infrared attenuated total reflection spectroscopy

Fourier transform infrared attenuated total reflection (FT-IR ATR) spectroscopy was used to characterize thin films of succinic acid, a matrix compound commonly used with infrared matrix-assisted laser desorption ionization (IR-MALDI) mass spectrometry. IR spectra of succinic acid thin films deposited alone and in combination with the analyte biomolecules insulin and cytochrome c were obtained by FT-IR ATR spectroscopy. Spectra of analyte and matrix alone were similar to those obtained previously from KBr pellets, Nujol mull, or thin-film absorption, although the ATR spectra have significantly lower background interferences. Thin films deposited from mixtures of water and methanol have additional peaks compared to films deposited from a methanol solution. These additional peaks are attributed to carboxylate groups stabilized by residual water molecules. No evidence was found to suggest that residual water absorption contributes to absorption at wavelengths typically used for IR-MALDI. Absorption of energy by analyte vibrational modes with rapid energy transfer to the matrix is suggested as a contributor to desorption and ionization consistent with the FT-IR ATR results.     

超支化聚(胺-酯)为模板Ag纳米粒子的制备

以超支化聚(胺-酯)为模板,采用NaBH4直接还原和紫外灯光照射合成了Ag纳米粒子。超支化聚(胺-酯)对Ag纳米粒子形成起着重要的作用。TEM分析表明,Ag纳米粒子形貌为球形结构,分布均匀,粒径约为45 nm(NaBH4还原)和20 nm(紫外灯光照射)。发现在UV-Vis谱图中420 nm左右有Ag纳米粒子特征表面等离子共振吸收峰。FT-IR分析发现Ag纳米粒子和超支化聚(胺-酯)之间有较强的相互作用,超支化聚(胺-酯)对Ag纳米粒子的稳定性起保护作用。     

Effect of inorganic-organic composite coating on the dispersion of silicon carbide nanoparticles in non-aqueous medium

In order to disperse silicon carbide (SiC) nanoparticles homogeneously in a non-aqueous medium, the surface of SiC nanoparticles needs to be modified via surface organic functionalization. A method of SiC nanoparticle surface modification by grafting of polyacetals via inorganic-organic composite coating was developed. The resulting graft percentage of up to 10.5% was much higher than that of direct grafting. The inorganic-organic composite coating on a SiC nanoparticle surface led to an almost complete decomposition of the secondary structure of the agglomerates and the formation of the primary structure. Dispersibility of the modified version was studied by using a transmission electron microscope (TEM) and size distribution analyser. The sedimentation experiments showed that the coated SiC nanoparticles exhibited good suspension stability in butanone. The composition of the inorganic-organic composite coating on the SiC nanoparticles was investigated by energy dispersive x-ray analyses (EDX), hydrogen nuclear magnetic resonance ((1)H NMR) and Fourier-transformed infrared spectroscopy (FT-IR). This work provides a novel concept of surface grafting modification for non-oxide nanoparticles to improve their dispersibility in non-aqueous medium.     

Preparation and electro-optic properties of hybrid sol-gel films containing imidazole chromophore

An alkoxysilane precursor based on imidazole chromophore, namely 2-((4-(ethyl(2-hydroxyethyl)amino)phenyl)diazenyl)-4,5-dicyano-1H-imidazole (IZ), has been successfully synthesized through a urethane forming reaction. Following a sol-gel process of the resultant precursor, inorganic-organic hybrid films were obtained by spin-coating. Their structures were verified by ¹H NMR, FT-IR, UV-vis spectra and elemental analysis. After corona poling, the electro-optic (EO) properties of the hybrid films were characterized by a simple reflection technique, and the EO coefficient (r₃₃) of a sample was determined to be 1.6 pm/V at a wavelength of 1310 nm.     

Effect of sulfurization in hydrogen sulfide on the properties of Cu(In,Ga)Se2 thin-film absorbers

In this research Cu(In,Ga)Se₂ thin films were sulfurized in H₂S–Ar gas mixture with processing temperatures ranging from 400 to 550 °C and time ranging from 10 to 60 min. The change in crystal phases, microstructure and chemical compositions of the absorber layers after sulfurization were investigated by X-ray diffraction, high resolution TEM, scanning electron microscopy, Raman scattering spectrum, energy dispersive X-ray spectrometer. In the process of sulfurization, the crystallinity and sulfurization degree of the Cu(In,Ga)(S,Se)₂ films depend strongly on the sulfurization temperature. The ‘Cu–Au’ phase was found for samples grown at low sulfurization temperature and transformed to chalcopyrite-type phase at high sulfurization temperature. The Se–S vibration mode of Cu(S,Se) alloy was also observed in the Raman spectra.     

壳聚糖/纳米TiO2杂化材料的制备及抗菌性能表征

制备了壳聚糖/纳米TiO2杂化膜,表征了其抗菌性能,分析了影响TiO2纳米粒子在壳聚糖溶液中分散性的影响因素。FT-IR、AFM分析了杂化膜的结构与形态。表明促进TiO2颗粒良好分散有四个主要因素:(1)表面电荷的重新分布;(2)空间保护作用;(3)化学键的相互作用;(4)超声分散。抗菌实验表明壳聚糖/纳米TiO2杂化膜具有很强的抗菌性能,细菌的形态学变化具有两个显著的特点:(1)细胞内物质渗漏,在细胞周围形成了环状结构;(2)细胞表面囊泡的形成。     

Preparation and optical properties of Au/Teflon nanocomposites

Using thermal deposition technique, we have prepared Au/Teflon thin films on glass substrates. To control the film microstructure, both TEM and AFM characterization have been carried out. The visible optical transmission spectra have been measured in-situ. The peak positions and linewidths in the spectra have been identified in terms of the gold nanoparticle shape, size, and arrangement. The results obtained provide evidence for formation of both sphere-like and cylinder-like gold nanoparticles in the films. The fraction of each kind of the particles depends on whether the plasma treatment has been used. The treatment is shown to enhance the fraction of the cylinder-like particles.     

表面改性及原位还原法制备聚酰亚胺/镍纳米复合薄膜

通过对均苯四甲酸二酐-4,4’-二胺基二苯醚(PMDA-4,4’-ODA)型聚酰亚胺(PI)成品薄膜的表层水解处理、并在硫酸镍水溶液中实施离子交换以及随后的乙二醇热还原的方法,制备了聚酰亚胺/镍纳米复合薄膜。通过X射线衍射仪(XRD)、傅立叶变换红外光谱仪(FT-IR),透射电子显微镜(TEM)等方法研究了复合薄膜结构的变化,结果表明,经乙二醇热还原后,水解后的聚酰亚胺表层又重新形成亚胺环结构,并在其内部形成了均匀分散的具有面心立方晶型(FCC)的金属镍粒子,直径约为100 nm~200 nm。