Layer-by-layer assembled charge-trap memory devices with adjustable electronic properties

We describe a versatile approach for preparing flash memory devices composed of polyelectrolyte/gold nanoparticle multilayer films. Anionic gold nanoparticles were used as the charge storage elements, and poly(allylamine)/poly(styrenesulfonate) multilayers deposited onto hafnium oxide (HfO2)-coated silicon substrates formed the insulating layers. The top contact was formed by depositing HfO2 and platinum. In this study, we investigated the effect of increasing the number of polyelectrolyte and gold nanoparticle layers on memory performance, including the size of the memory window (the critical voltage difference between the 'programmed' and 'erased' states of the devices) and programming speed. We observed a maximum memory window of about 1.8 V, with a stored electron density of 4.2 x 1012 cm-2 in the gold nanoparticle layers, when the devices consist of three polyelectrolyte/gold nanoparticle layers. The reported approach offers new opportunities to prepare nanostructured polyelectrolyte/gold nanoparticle-based memory devices with tailored performance.     

静电自组装膜研究进展

由静电自组装技术来制备功能型薄膜是发展迅速的新研究领域。本文着重阐述了静电自组装聚电解质-聚电解质复合膜、静电自组装聚电解质-无机纳米粒子复合膜、静电自组装聚合物-半导体纳米粒子复合膜、静电自组装其他多层膜体系制备方法和特点,展望了静电自组装在渗透分离膜、基因传输、传感器系统、光伏设备等领域的应用前景。     

强化自组装技术在多层复合分离膜领域的应用

强化自组装技术是近年来被发展的一种制备聚电解质复合物多层膜的新方法,该法巧妙地利用外加力与聚合物间作用力的协同效应,强化组装过程,简化成膜程序,提高膜分离性能.总结了近年来课题组在这一领域的研究进展.     

氧化锌/二氧化硅复合膜的结构色研究

采用静电自组装技术,以氧化锌（ZnO）和二氧化硅（SiO2）溶胶颗粒为前驱体,通过控制双组分膜层的不同厚度,制备出结构色鲜艳的ZnO/SiO2复合膜,并利用分光测色仪、多角度分光光度仪及扫描电子显微镜等研究复合膜的颜色、微观结构和形态特征。研究结果发现,ZnO/SiO2复合膜的亮度和色度均较单一组分薄膜的高,复合薄膜的颜色仍随厚度和观察角度的变化而变化。通过对薄膜的微观结构分析,结合其厚度随周期数的变化规律,发现复合薄膜的厚度随着自组装循环次数的增加而增加,薄膜中的纳米粒子并没有形成明显的高低折射率交替分布的双层结构,可能形成的是高折射率层（H层）、有效折射率层（eff层）和低折射率层（L层）的多层微观结构。这种特殊的多层结构与光作用发生干涉,形成了鲜亮度和饱和度更高的结构色。     

PSS／PAH聚电解质复合纳滤膜制备及其性能研究

采用LbL法在多孔PES基膜上制备了PSS／PAH聚电解质复合纳滤膜，利用SEM研究了复合膜的表面形貌，使用ATR-IR研究了复合膜在PES基膜上的生长规律，并研究了双层膜层数和组装时间对其离子截留性能的影响．研究表明，所制复合纳滤膜对不同的盐溶液的离子截留性能差异显著．如[PSS／PAH]5膜对1000mg／L的MgSO4溶液的截留率可达90％，但对1000mg／L的NaCl溶液的截留率仅为33％，故可应用于水溶液中一、二价离子的分离。     

In situ FT-IR measurements of competitive vapor adsorption into porous thin films containing silica nanoparticles

Vapor adsorption into porous ultrathin films on a gold surface is investigated with in situ surface plasmon resonance (SPR) and polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The thin films are prepared by the electrostatic self-assembly of oppositely charged poly(L-lysine) (PL) and silica nanoparticles on a chemically modified gold surface. Characterization with ex situ SPR and PM-IRRAS demonstrates the buildup of multiple PL/SiO2 bilayers as well as an excellent correlation between the quantitative results from these two techniques. In situ vapor adsorption experiments with these thin films show evidence of porosity, reproducibility, and rapid reversibility. Exposure to acetone vapor (P/P0 = 0.032) causes the film to adsorb 9% acetone by volume, which corresponds to coverage of approximately one-half of the silica nanoparticle surface area. In situ PM-IRRAS provides much information about the molecular interactions occurring in the film upon adsorption or desorption of vapors. Dosing with a mixture of vapors leads to a competition for adsorption into the film, and PM-IRRAS results show that acetone slightly outcompetes nitromethane. These experiments with nanoparticle thin films demonstrate the advantages of using in situ PM-IRRAS for studying reversible adsorption in the presence of vapor mixtures.     

静电自组装制备含苝衍生物的纳米层状复合膜

采用静电自组装方法制备了稳定的含苝衍生物纳米层状复合膜．用石英晶体微天平(QCM)对静电自组装过程进行了原位监控，发现组装次数与QCM频率变化呈线性关系，通过静电吸附得到的多层累积薄膜具有层状结构，X射线光电子能谱图上出现苝衍生物的特征峰表明组装的薄膜中含有苝衍生物．原子力显微镜表征结果表明，复合膜在一定程度上规整并且均匀的覆盖在电极表面，但存在分子团聚现象，将苝衍生物小分子溶解在聚电解质溶液中作混合浸渍液，提高了组装薄膜的稳定性．     

碳纳米管和壳聚糖的层层静电自组装多层膜(英文)

将多壁碳纳米管(MWCNT)置于混酸(硝酸∶硫酸=1∶3)中,利用超声波振荡截短碳纳米管、并使其与羧基链接,而后基于阳离子聚合电解质壳聚糖(CS)和阴离子短切碳纳米管之间的静电作用,在玻璃衬底上通过层层的模式均匀稳定地自组装形成复合壳聚糖多层膜。UV-vis光谱显示:组装过程呈现均匀而连续的生长。AFM和SEM观察表明:CS/MWCNT多层膜具有良好的光学特性,在生物传感器方面具有潜在的应用前景。     

Responding Depth of Photocatalytic Activity of TiO2 Self-assembled Films

The electrostatically self-assembly method is getting strategically important to prepare multilayer thin films. With careful choice of component materials, this method should allow for the preparation of multilayer thin films with a variety of excellent technological properties. Ti02/PSS multilayer thin films with ordered structure were prepared by electrostatic self-assembly method. UV-Vis-NIR spectrophotometer, X-ray photoelectron spectroscopy (XPS), and atom force microscopy (AFM) were used to characterize the structure and performance of the multilayer films. Because electrostatically self-assembly method allows molecular-level control over the film composition and thickness, this paper studied the responding depth of photocatalytic activity of Ti02 self-assembled films in detail.     

Electrostatically stabilised nanoparticles: self-organization and electron-beam patterning

The self-organisation of citrate- and magnesium oleate-stabilised gold nanoparticles on SiO2/Si substrates was investigated. In drop deposition, nucleation of citrate-stabilised gold nanoparticles was observed at the rim of the droplet, symmetric or multibranched dendroid gold structures were found in the area between the rim and the central part of the droplet, depending on the drying temperature. Homogeneous submonolayer nanoparticle coverage was obtained by immersion of amineterminated SiO2/Si surfaces into a citrate-stabilised colloidal gold acidic solution. Drop deposition of magnesium oleate-stabilised gold nanoparticles onto the SiO2/Si surfaces resulted in the formation of uniformly close-packed nanoparticle arrays. Under electron beam irradiation, no apparent changes were found for monolayer films of citrate-stabilized particles, but sintering of the nanoparticles was observed in multilayer films. In contrast, coalescence of magnesium oleate-stabilised gold nanoparticle occurred in monolayer films after electron irradiation.     

Consecutively spin-assembled layered nanoarchitectures of poly(sodium 4-styrene sulfonate) and poly(allylamine hydrochloride)

The recently established spin-coating electrostatic self-assembly (SCESA) technique has been shown to facilitate not only the rapid fabrication of polyelectrolyte multilayer assemblies, but also allow each layer to be easily controlled on a monomolecular scale by minimizing the film thickness across a substrate surface. In this paper, the influence of polyelectrolyte concentration on the amount and thickness of spin-deposited polymer films has been examined for a multilayer system of poly(allyamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS), when the washing steps employed for removing weakly bound polyelectrolytes on a resultant film on a substrate are excluded from the standard fabrication procedure of the SCESA method. The thickness of the spin-deposited PAH/PSS bilayer increased linearly for the PSS concentrations in the range from 1 to 10 mM with PAH constant at 1 mM, which demonstrates the uniform deposition of each layer material onto the thin film. The thickness of PAH/PSS bilayers increased from 1.43 ± 0.06 to 3.37 ± 0.08 nm as the PSS concentration increased from 1 to 10 mM, while the PAH concentration was kept constant at 1 mM. The multilayer films were found to be stable in a good solvent (H₂O) for at least 30 h, without any noticeable loss of the adsorbed layer component of the polyelectrolyte. This improvement to the SCESA method (exclusion of washing steps) provides a convenient way to create multilayer heterostructures with the thickness of each layer being easily adjusted.     

静电自组装铁电复合超薄膜及特性研究

将极化处理后充负电荷的聚偏氟乙烯（PVDF）有机铁电聚合物薄膜经溶解,与BaTiO₃无机纳米粉体形成良好分散的PVDF-BT荷电阴离子溶液和聚二丙烯基二甲基氯化铵（PDDA）聚阳离子溶液,通过静电作用在石英基片上交替自组装PDDA/PVDF-BT铁电复合超薄膜. 采用石英晶体微天平（QCM）、扫描电子显微镜（SEM）、X射线衍射分析（XRD）对该铁电复合超薄膜进行了表征. 研究结果表明：自组装12层PDDA/PVDF BT铁电复合超薄膜厚度为82nm,且静电自组装过程均匀,复合超薄膜表面平整、致密,无机纳米颗粒规整并均匀地覆盖在石英基底表面. 通过在PDDA/PVDF复合超薄膜间引入BaTiO₃无机纳米铁电粉体,可实现对超薄膜内部结构以及膜厚度的控制,极化强度可提高到约3μC/cm².     

Mapping bacterial surface layers affinity to polyelectrolytes through the building of hybrid macromolecular structures

A novel hybrid sandwich-like supramolecular structure (polyelectrolyte multilayer/S-layer/ polyelectrolyte multilayer/S-layer) has been built by combining polyelectrolyte multilayer deposition and self-assembly of isolated SbpA proteins from Bacillus sphaericus CCM2177. Neutron reflectometry measurements were used to confirm the formation of an S-layer on negative poly(styrene sulphonate) (PSS) terminated multilayers, further adsorption of cationic poly(allylamine hydrochloride) polyelectrolyte on the exposed S-layer surface, and final polyelectrolyte multilayer deposition. Surface topography investigations with atomic force microscopy showed that: (i) the two dimensional structure of the S-layer is similar to those found in bacteria, (ii) cationic poly(allylamine hydrochloride) adsorbs on the bacterial protein side that faces the aqueous media, and (iii) anionic poly(styrene sulphonate) does not adsorb on the S-layer surface. Mechanical stability studies on recrystallized S-layers on anionic negative poly(styrene sulphonate) reveal that loads of 20 nN are able to unfold the S-layer protein. A second adsorption of SbpA monomers on top of a structure composed of polyelectrolyte multilayer/S-layer/polyelectrolyte multilayer led to the formation of S-layers patches mechanically stable for loads up to 9 nN. This hybrid polymer-protein supramolecular complex has permitted to elucidate the nature of the affinity of the bacterial cell surface protein to polyelectrolytes.     

Layer-by-layer self-assembly of polyimide precursor/layered double hydroxide ultrathin films

The layer-by-layer (LBL) self-assembly has been extensively used as a simple and effective method for the preparation of polyelectrolyte multilayer films. In this work, we utilized this unique method to prepare polyimide precursor/layered double hydroxide (LDH) ultrathin films. Well-crystallized Co-Al-CO₃ LDH and subsequent anion exchanged Co-Al-NO₃ LDH were prepared and characterized by scanning electron microscopy and X-ray diffraction (XRD). By vigorous shaking of the as-prepared Co-Al-NO₃ LDH, positively charged and exfoliated LDH nanosheets were obtained. Atomic force microscopy and XRD investigations indicated the delamination of LDH nanosheets. The precursor of polyimide, poly(amic acid) tertiary amine salt (PAS) was prepared by the polycondensation of dianhydride and diamine, and subsequent amine salt formation. By using the LBL method, heterogeneous ultrathin films of PAS and LDH were prepared. The formation of the ordered nanostructured assemblies was confirmed by the progressive enhancement of UV absorbance and the XRD results.     

Production of free standing composite membranes or of patterned films after sol–gel reactions in an exponential layer-by-layer architecture

This paper aims at describing that polyelectrolyte multilayer (PEM) films, made of biocompatible molecules, Hyaluronic acid (HA) and Poly(6-lysine) (PLL), can entrap negatively charged precursors of titania or silica. These precursors undergo hydrolysis and polycondensation in contact with the amino groups of PLL leading to the formation of oxides (TiO₂ or SiO₂) within the films. Moreover, this work shows that these composite thin films, a few μm thick, can be easily detached as free standing membranes containing photoactive TiO₂. To this aim the PEM film containing TiO₂ was thermally cross-linked to form amide bonds. Immersion of the film in diluted hydrofluoric acid (2% (v/v)) allowed then the formation of a free standing membrane. We extend the concept of sol–gel reaction in PEM films to films made from poly(L-glutamic acid) (PGA) and Poly(allylamine) (PAH) and show that the composition of the multilayer film influences the distribution of the inorganic material in the films: the TiO₂ distribution seems homogeneous in (PLL–HA)_n films whereas the (PAH–PGA)_n films are self patterned with inorganic aggregates tens of micrometers in diameter. The free standing membranes or self patterned composite films obtained in this investigation may present interesting bio-applications.     

静电自组装制备CdTe量子点纳米薄膜

以巯基丙酸为稳定剂, 在水相中合成了表面带负电荷、具有良好的分散性、平均粒径为5nm的CdTe量子点. 通过CdTe量子点与阳离子聚电解质聚二烯丙基二甲基氯化铵(PDDA)和阴离子聚电解质聚苯乙烯磺酸钠(PSS)之间的静电相互作用, 在石英基片表面通过层层静电自组装方法制备了多层CdTe量子点纳米薄膜. 以荧光分光光度计、UV-Vis、XPS、AFM等测试手段对所得的CdTe量子点纳米薄膜进行了表征. 研究结果表明, CdTe量子点自组装多层薄膜的UV-Vis吸光度与组装层数基本呈线性关系, 薄膜成膜质量良好. 自组装薄膜基本上规整并均匀地覆盖在石英基底表面, 但薄膜中存在部分CdTe量子点聚集现象. 通过在相邻的两层CdTe量子点之间引入基本结构单元为PDDA/PSS/PDDA的聚电解质复合层, 可有效提高CdTe量子点纳米薄膜的成膜质量. 所得的CdTe量子点纳米薄膜具有良好的荧光光致发光性.     

Preparation and characterization of conducting poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Langmuir-Blodgett film

The self-assembly of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) nanoparticles at an air/water interface was achieved by means of the electrostatic force between an octadecylamine (ODA) monolayer and PEDOT-PSS nanoparticles. A surface pressure (π)-area (A) isotherm and X-ray photoelectron spectroscopy of the composite film were used to confirm the electrostatic force between the SO₃⁻ group of PSS and the NH₄⁺ group of aliphatic amines. Monolayer and multilayer composite films of ODA/PEDOT-PSS and ODA-stearic acid (SA)/PEDOT-PSS were fabricated. These solid Langmuir-Blodgett films were investigated by the UV-Vis spectrum, atomic force microscopy, and X-ray diffraction method. It is observed that ODA-SA/PEDOT-PSS films had a higher film-forming capability than ODA/PEDOT-PSS films and an ordered multilayer structure was developed. The conductive properties of ODA-SA/PEDOT-PSS LB films were investigated in detail. Factors influencing the film conductivity such as the layer number and surface pressure were discussed and the conductive mechanism was also studied.     

硼钨铜杂多酸/聚酰胺-胺多层膜的制备及其电催化性能

通过层层自组装技术在氧化锢锡(ITO)电极上制备Keggin型硼钨铜杂多酸/聚酰胺-胺有机-无机复合多层膜.利用X射线光电子能谱(XPS),UV-Vis光谱和原子力显微镜(AFM)等手段对多层膜的组成和表面形貌进行了表征.结果表明,杂多酸阴离子和聚酰胺-胺树形分子通过静电相互作用形成了多层膜且膜的增长均匀.杂多酸阴离子...     

Layer-by-layer self-assembly of dye-polyoxometalate multilayer composite films and their fluorescent properties

The layer-by-layer (LbL) self-assembly technique was successfully applied to the fabrication of dye-polyoxometalate multilayer composite films consisting of two dye molecules Rhodamine B (RB) and Rhodamine 6G (R6G) and a Keggin-type polyoxometalate [α-SiW₁₂O₄₀]⁴⁻ (α-SiW₁₂). The composite films were characterized by UV-vis spectroscopy, scanning electron microscopy (SEM), and fluorescence spectroscopy. UV-vis spectra show that the characteristic absorbance values of the multilayer films increase almost linearly with the number of dye/α-SiW₁₂ bilayers, suggesting that the deposition process is regular and highly reproducible from layer to layer. SEM micrographs indicate that the film surface is a little rough with some individual granular domains. In addition, the fluorescent properties of these composite films were also investigated by fluorescence spectroscopy.     

Effect of filler types and calcination temperature on the microstructure and the nitric oxide photocatalytic activity of composite titanium dioxide films

The composite titanium dioxide (TiO(2)) films coating on the woven glass fabric were prepared by a modified sol-gel process, using pre-calcinated TiO(2) nanoparticle or silica gel as filler. The characterized physicochemical properties of the prepared catalyst films showed that the specific surface area, the microstructure and the crystal structure of the catalysts were greatly affected by the fillers and the calcination temperature. The physicochemical properties of composite films and the photocatalytic activity of nitric oxide (NO) show that the pre-calcinated TiO(2) nanoparticle is more favorable than silica gel as filler. The pre-calcinated TiO(2) nanoparticle filler can increase the photocatalytic activities of the catalysts by increasing the specific surface area, introducing a bimodal mesoporous structure, and creating a polymorphous crystal structure. And the TiO(2)-TiO(2) film calcinated at 400 degrees C exhibits the highest photocatalytic activity for NO oxidation and is more active than Degussa P25.