首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 78 毫秒
1.
The synthesis of organic‐functionalized pure‐silica‐zeolites (PSZs) with MFI‐ and MEL‐type structures for low‐k applications prepared through a direct‐synthesis method by adding a fluorinated silane to the synthesis solution is reported. The added fluorine functionality increases the hydrophobicity of the zeolites, which are characterized by scanning electron microscopy, X‐ray diffraction, 29Si and 19F solid‐state NMR spectroscopy, nitrogen adsorption, and thermogravimetric analysis. The functionalized zeolite powders have low water content and calcined spin‐on films prepared from the functionalized nanoparticle suspensions exhibit higher water contact angles and lower k values (2.1 and 1.8 for the functionalized MFI‐ and MEL‐type zeolites, respectively) than PSZ films. The use of a direct‐synthesis method to decrease the moisture adsorption in the films eliminates the extra post‐spin‐on silylation steps that are traditionally used to render the zeolite films hydrophobic.  相似文献   

2.
A method of simultaneous field‐ and flow‐directed assembly of anisotropic titania (TiO2) nanoparticle films from a colloidal suspension is presented. Titania particles are oriented by an alternating (ac) electric field as they simultaneously advect towards a drying front due to evaporation of the solvent. At high field frequencies (ν > ~25 kHz) and field strengths (E > 300 V cm?1), the particles orient with their major axis along the field direction. As the front recedes, a uniform film with thicknesses of 1–10 µm is deposited on the substrate. The films exhibit a large birefringence (Δn ≈ 0.15) and high packing fraction (? = 0.75 ± 0.08), due to the orientation of the particles. When the frequency is lowered, the particle orientation undergoes a parallel–random–perpendicular transition with respect to the field direction. The orientation dependence on field frequency and strength is explained by the polarizability of ellipsoidal particles using an interfacial polarization model. Particle orientation in the films also leads to anisotropic mechanical properties, which are manifested in their cracking patterns. In all, it is demonstrated that the field‐directed assembly of anisotropic particles provides a powerful means for tailoring nanoparticle film properties in situ during the deposition process.  相似文献   

3.
An amphiphilic block copolymer, poly(methylacrylate)82block‐poly(N‐(acryloyloxy)succinimide0.29co‐(N‐acryloylmorpholine)0.71)155 (PMA82b‐P(NAS0.29co‐NAM0.71)155), was synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization and then was supramolecularly assembled into micelles in aqueous solution, followed by chemical crosslinking throughout the shell region upon the introduction of 2,2′‐(ethylenedioxy)‐bis(ethylamine) as a crosslinker to afford well‐defined shell crosslinked nanoparticles (SCKs). The number‐averaged hydrodynamic diameters of the micelles and SCKs were (17 ± 4) nm and (16 ± 3) nm, respectively, by dynamic light scattering (DLS), and (15 ± 2) nm and (13 ± 2) nm, respectively, by transmission electron microscopy (TEM). In an attempt to narrow the particle size distributions, the dodecyl trithiocarbonate chain end of the block copolymer was replaced by a 2‐cyanoisopropyl moiety. Each nanoparticle system was characterized by DLS, electrophoretic light scattering (ELS), TEM, and small‐angle X‐ray scattering (SAXS). SAXS was of particular importance, as it provided definitive observation and quantification of shell contraction and densification upon shell crosslinking. The direct incorporation of NAS into the block copolymers during their preparation allowed for unique crosslinking chemistry to proceed with added diamino crosslinkers. The primary advantages of this system include the ability to conduct in situ synthesis of SCKs that are crosslinked directly and derivatized easily by adding nucleophilic ligands before, during, or after the crosslinking.  相似文献   

4.
A simple method to prepare large‐scale graphene sponges and free‐standing graphene films using a speed vacuum concentrator is presented. During the centrifugal evaporation process, the graphene oxide (GO) sheets in the aqueous suspension are assembled to generate network‐linked GO sponges or a series of multilayer GO films, depending on the temperature of a centrifugal vacuum chamber. While sponge‐like bulk GO materials (GO sponges) are produced at 40 °C, uniform free‐standing GO films of size up to 9 cm2 are generated at 80 °C. The thickness of GO films can be controlled from 200 nm to 1 µm based on the concentration of the GO colloidal suspension and evaporation temperature. The synthesized GO films exhibit excellent transparency, typical fluorescent emission signal, and high flexibility with a smooth surface and condensed density. Reduced GO sponges and films with less than 5 wt% oxygen are produced through a thermal annealing process at 800 °C with H2/Ar flow. The structural flexibility of the reduced GO sponges, which have a highly porous, interconnected, 3D network, as well as excellent electrochemical properties of the reduced GO film with respect to electrode kinetics for the [Fe(CN)6]3?/4? redox system, are demonstrated.  相似文献   

5.
The fabrication of ultrasmall nanogaps (sub‐1 nm) with high density is of significant interest and importance in physics, chemistry, life science, materials science, surface science, nanotechnology, and environmental engineering. However, it remains a challenge to generate uncovered and clean sub‐1‐nm gaps with high density and uniform reproducibility. Here, a facile and low‐cost approach is demonstrated for the fabrication of high‐density sub‐1‐nm gaps from Au nanoparticle monolayers as reproducible surface‐enhanced Raman scattering (SERS) substrates. Au nanoparticles with larger diameters possess lower surface charge, thus the obtained large‐area nanoparticle monolayer generates a high‐density of sub‐1‐nm gaps. In addition, a remarkable SERS performance with a 1011 magnitude for the Raman enhancement is achieved for 120 nm Au nanoparticle monolayers due to the dramatic increase in the electromagnetic field enhancement when the obtained gap is smaller than 0.5 nm. The Au nanoparticle monolayer is also transferred onto a stretchable PDMS substrate and the structural stability and reproducibility of the high‐density sub‐1‐nm gaps in Au monolayer films are illustrated. The resultant Au nanoparticle monolayer substrates with an increasing particle diameter exhibit tunable plasmonic properties, which control the plasmon‐enhanced photocatalytic efficiency for the dimerization of p‐aminothiophenol. The findings reported here offer a new opportunity for expanding the SERS application.  相似文献   

6.
Understanding and controlling 3D nanocrystal self‐assembly is a fundamental challenge in materials science. Assembly enables the unique optical and electronic properties of nanocrystals to be exploited in macroscopic materials, and also opens up the possibility to couple the optical response of nanocrystals to the optical modes of the superlattice. To date, assembly of such nanocrystal superlattices (NCSL) has focussed on fixed, close packed structures with particle separations of just 1–3 nm. To achieve highly crystalline structures with tunable optical response, the nanocrystal interparticle separation needs to be precise and easily variable but >50 nm. Here, we show the preparation of nanocrystal superlattices with spacings of 50–500 nm assembled from gold‐poly‐N‐isopropylacrylamide core‐shell particles and the characterization of their fascinating diffraction behavior by means of UV‐vis spectroscopy. These nanocrystal superlattices exhibit pronounced diffraction in the visible (440‐560 nm) with peak half‐widths of the order of 10 nm. The position of the Bragg peak is simply tuned by adjusting the particle volume fraction. Due to the thermoresponsive nature of the polymer shell, temperature is used to initiate crystallization or melting of the superlattice. Heating and cooling cycles cause highly reversible melting/recrystallization in less than a minute.  相似文献   

7.
Nanodielectrics is an emerging field with applications in capacitors, gate dielectrics, energy storage, alternatives to Li‐ion batteries, and frequency modulation in communications devices. Self‐assembly of high k dielectric nanoparticles is a highly attractive means to produce nanostructured films with improved performance—namely dielectric tunability, low leakage, and low loss—as a function of size, composition, and structure. One of the major challenges is conversion of the nanoparticle building block into a reliable thin film device at conditions consistent with integrated device manufacturing or plastic electronics. Here, the development of BaTiO3 and (Ba,Sr)TiO3 superparaelectric uniform nanocrystal (8–12 nm) films prepared at room temperature by evaporative driven assembly with no annealing step is reported. Thin film inorganic and polymer composite capacitors show dielectric constants in the tunable range of 10–30, dependent on composition, and are confirmed to be superparaelectric. Organic thin film transistor (TFT) devices on flexible substrates demonstrate the readiness of nanoparticle‐assembled films as gate dielectrics in device fabrication.  相似文献   

8.
Low‐dielectric‐constant (low‐κ) materials are a critical requirement for future generations of computer microprocessors. As a unique class of porous silicas, pure silica zeolites (PSZs) have been shown to be a promising low‐κ material with excellent mechanical strength (e.g., elastic modulus of 16–18 GPa) due to their crystalline nature. In the present study, we show for the first time that higher crystallinity of spin‐on PSZ MFI films leads to lower κ values and less moisture sensitivity—two critical properties of a porous low‐κ material. We have also advanced the two‐stage synthesis method to produce zeolite nanoparticles with high yield (77 %) and a small diameter (< 80 nm). A κ value of 1.6 is obtained from the silylated highly crystalline PSZ MFI film and the κ value only increases by 12.5 % after exposure to ambient conditions for a period of 24 h.  相似文献   

9.
The present work describes the synthesis of difluoro‐boradiazaindacenes (Bodipy) functionalized at the central 8‐position by phenylamino moieties easily transformable into phenyl amide scaffoldings. Molecules carrying three linear or branched chains were prepared and characterized. An X‐ray crystal structure for the pivotal trimethoxyphenyl‐Bodipy derivative was determined, and the packing is discussed in terms of molecular interactions; a key feature for the formation of thin films. All of the dyes are thermally stable up to 170 °C but no liquid‐crystalline phases are observed. Reversible reduction and oxidation processes occur around +0.97 and −1.34 V, respectively, versus saturated calomel electrode in solution and the electroactivity and photoluminescence are maintained in thin films produced by vacuum evaporation. Interestingly, two distinct emissions are observed at 550 and 635 nm by electroluminescence of the trimethoxyphenyl‐Bodipy derivative, corresponding to the luminescence of isolated molecules and dimers, respectively. Doping Alq3 films with this Bodipy molecule by vacuum evaporation produces organic light‐emitting diodes (OLEDs) in which very efficient energy transfer from the Alq3 matrix to the Bodipy occurs by a resonance mechanism involving the first Bodipy excited state. Yellow light (550 nm, 344 cd m−2 at 15 V) is emitted at low doping concentration (7 mol %), whereas red light (635 nm, 125 cd m−2 at 15 V) is emitted at higher concentration (19 mol %). Dispersion of the Bodipy into a fluorescent poly(N‐vinylcarbazole) polymer (PVK) (≈3 mol % per repeating unit of PVK) by solution processing exclusively produces yellow emission owing to the isolated Bodipyfluorophore (550 nm, 213 cd m−2 at 15 V). The second excited state of the Bodipy dye is likely involved during energy transfer from the PVK matrix.  相似文献   

10.
A low‐temperature synthesis coupled with mild activation produces zeolite films exhibiting low dielectric constant (low‐k) matching the theoretically predicted and experimentally measured values for single crystals. This synthesis and activation method allows for the fabrication of a device consisting of a b‐oriented film of the pure‐silica zeolite MFI (silicalite‐1) supported on a gold‐coated silicon wafer. The zeolite seeds are assembled by a manual assembly process and subjected to optimized secondary growth conditions that do not cause corrosion of the gold underlayer, while strongly promoting in‐plane growth. The traditional calcination process is replaced with a nonthermal photochemical activation to ensure preservation of an intact gold layer. The dielectric constant (k), obtained through measurement of electrical capacitance in a metal–insulator–metal configuration, highlights the ultralow k ≈ 1.7 of the synthetized films, which is among the lowest values reported for an MFI film. There is large improvement in elastic modulus of the film (E ≈ 54 GPa) over previous reports, potentially allowing for integration into silicon wafer processing technology.  相似文献   

11.
Continuous, thin, oriented zeolite A membranes are produced by a two‐step synthesis on macroporous α‐Al2O3 supports. In the first step, zeolite A nano‐cubes with ~350‐nm edges are prepared as a native impurity phase in zeolite Y synthesis dispersions, the support surface is pre‐modified with a cationic polymer having a selective affinity for zeolite A. The thus‐treated support is contacted with a colloidally stable dispersion of zeolite A and Y mixture in water, which results in selective, dense‐packed deposition of the zeolite A cubes with one face aligned to the average support surface. In a second step of hydrothermal epitaxial growth, the seed layer grows epitaxially into a continuous, meso‐defect free, ~1 µm thick zeolite A layer, already after 1 h of treatment. This microstructure of the membrane compares very favorably to what is commonly obtained. The pH value of the zeolite mixture suspension is found to have a major influence on seed layer morphology, and thereby, on the quality and orientation of zeolite A membrane after short synthesis times. The final zeolite A membrane thickness and morphology is controlled by varying secondary growth synthesis time. The approach presented is thought to be of generic use for the preparation of oriented zeolite membranes.  相似文献   

12.
A new electrontransport polymer, poly{[N,N′‐dioctylperylene‐3,4,9,10‐bis(dicarboximide)‐1,7(6)‐diyl]‐alt‐[(2,5‐bis(2‐ethyl‐hexyl)‐1,4‐phenylene)bis(ethyn‐2,1‐diyl]} (PDIC8‐EB), is synthesized. In chloroform, the polymer undergoes self‐assembly, forming a nanowire suspension. The nanowire's optical and electrochemical properties, morphological structure, and field‐effect transistor (FET) characteristics are investigated. Thin films fabricated from a PDIC8‐EB nanowire suspension are composed of ordered nanowires and ordered and amorphous non‐nanowire phases, whereas films prepared from a homogeneous PDIC8‐EB solution consist of only the ordered and amorphous non‐nanowire phases. X‐ray scattering experiments suggest that in both nanowires and ordered phases, the PDIC8 units are laterally stacked in an edge‐on manner with respect to the film plane, with full interdigitation of the octyl chains, and with the polymer backbones preferentially oriented within the film plane. The ordering and orientations are significantly enhanced through thermal annealing at 200 °C under inert conditions. The polymer film with high degree of structural ordering and strong orientation yields a high electron mobility (0.10 ± 0.05 cm2 V?1 s?1), with a high on/off ratio (3.7 × 106), a low threshold voltage (8 V), and negligible hysteresis (0.5 V). This study demonstrates that the polymer in the nanowire suspension provides a suitable material for fabricating the active layers of high‐performance n‐channel FET devices via a solution coating process.  相似文献   

13.
Films of gold nanoscaled islands with thicknesses ranging between 0.5 and 15 nm were prepared by thermal evaporation onto untreated and aminosilane‐pretreated glass substrates. Post‐deposition annealing was found to modify the morphological characteristics of the islands (e.g., average island area and height, inter‐island distance, etc.), resulting in changes of the localized surface plasmon resonance (SPR) characteristics and, therefore, modifying the nonlinear optical (NLO) response of the films. The NLO response of both unannealed and annealed (20 h at 200 °C) films was studied by means of the optical Kerr effect (OKE), using 35 ps, 532 nm laser excitation, while measurements performed by means of the Z‐scan technique allowed for the determination of both the nonlinear refraction and absorption characteristics of the films. The results are discussed and compared with other reports.  相似文献   

14.
Facile synthesis of white‐emitting, protein‐based, metal‐free, stable, nontoxic, and pH sensitive, advanced functional nanoparticles (GlowDots), as alternatives to quantum dots, is reported here. Controlled cross‐linking of bovine serum albumin resulted in facile formation of spherical nanoparticles of 35 nm in diameter with a sharp size distribution (±10 nm), which were then conjugated with specific dyes to produce white‐emitting particles with tunable excitation wavelengths. Chemical novelty is that the particle size, size distribution, stability, surface chemistry, and emission properties are under full chemical control where the size and absorption/emission properties are independently tuned. Up to 100 dye molecules were attached to each particle, on an average, and hence, particles acquired strong absorption cross‐sections as well as high brightness. White fluorescence of GlowDots is strongly sensitive to pH over a range of pH 2–11, and pH‐induced emission changes are fully reversible. The particles readily entered HeLa cells and emission color depended on particle location in the live cells, which is most likely due to the local environment surrounding the particles. These are the very first reports of white‐emitting advanced functional nanoparticles that are biodegradable, sensitive to pH, and amenable for live cell imaging to probe the subcellular compartments.  相似文献   

15.
The use of bio‐based nanoscaled cellulose for the construction of novel functional materials has progressed rapidly over the past years. In comparison to most of studies starting with the hydrophilic nanoscaled cellulose, surface‐stearoylated cellulose nanoparticles (SS‐CNPs) are used in this report for the construction of multifunctional, responsive films. SS‐CNPs with an average size of 115 ± 0.5 nm are obtained after the surface‐modification of cellulose under heterogeneous conditions. Crystalline cellulose core is present within SS‐CNPs according to solid‐state 13C nuclear magnetic resonance (NMR) spectroscopy. SS‐CNPs show excellent dispersibility in nonpolar solvents and form temperature‐responsive organogels in tetrahydrofuran (THF) at low temperature or after long time storage at room temperature. Moreover, transparent and self‐standing films of SS‐CNPs from their THF‐suspension show solvent‐responsive surface wettability and responsive shape‐memory property. SS‐CNPs can also be used for the fabrication of nanocomposite films together with nonpolar compounds, such as (2‐stearoylaminoethyl) rhodamine B. Thus, these novel SS‐CNPs derived from sustainable cellulose fibers are promising candidates for the construction of novel functional materials.  相似文献   

16.
Nanometer‐sized surfactant‐templated materials are prepared in the form of stable suspensions of colloidal mesoporous silica (CMS) consisting of discrete, nonaggregated particles with dimensions smaller than 200 nm. A high‐yield synthesis procedure is reported based on a cationic surfactant and low water content that additionally enables the adjustment of the size range of the individual particles between 50 and 100 nm. Particularly, the use of the base triethanolamine (TEA) and the specific reaction conditions result in long‐lived suspensions. Dynamic light scattering reveals narrow particle size distributions in these suspensions. Smooth spherical particles with pores growing from the center to the periphery are observed by using transmission electron microscopy, suggesting a seed‐growth mechanism. The template molecules could be extracted from the nanoscale mesoporous particles via sonication in acidic media. The resulting nanoparticles give rise to type IV adsorption isotherms revealing typical mesopores and additional textural porosity. High surface areas of over 1000 m2 g–1 and large pore volumes of up to 1 mL g–1 are obtained for these extracted samples.  相似文献   

17.
Self‐assembly of different sized colloidal particles into multicomponent crystals results in novel material properties compared to the properties of the individual components alone. The formation of binary and, for the first time, ternary colloidal crystals through a simple and inexpensive confined‐area evaporation‐induced layer‐by‐layer (LBL) assembly method is reported. The proposed method produces high quality multicomponent colloidal crystal films over a broad range of particle size‐ratios and large surface areas (cm2) from silica/polystyrene colloidal suspensions of low concentration. By adjusting the size‐ratio and concentration of the colloidal particles, complex crystals of tunable stoichiometries are fabricated and their structural characteristics are further confirmed with reported crystal analogues. In addition, complex structures form as a result of the interplay of the template layer effect, the surface forces exerted by the meniscus of the drying liquid, the space filling principle, and entropic forces. Thus, this LBL approach is a versatile way to grow colloidal crystals with binary, ternary, or more complex structures.  相似文献   

18.
A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 103 per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd2+ after the dissolution of the CdTe tags with HNO3. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.  相似文献   

19.
Here, reactive imprint lithography (RIL) is introduced as a new, one‐step lithographic tool for the fabrication of large‐area topographically patterned, chemically activated polymer platforms. Films of polystyrene‐block‐poly(tert‐butyl acrylate) (PS‐b‐PtBA) are imprinted with PDMS master stamps at temperatures above the corresponding glass transition and chemical deprotection temperatures to yield structured films with exposed carboxylic acid and anhydride groups. Faithful pattern transfer is confirmed by AFM analyses. Transmission‐mode FTIR spectra shows a conversion of over 95% of the tert‐butyl ester groups after RIL at 230 °C for 5 minutes and a significantly reduced conversion to anhydride compared to thermolysis of neat films with free surfaces in air or nitrogen. An enrichment of the surface layer in PS is detected by angle‐resolved X‐ray photoelectron spectroscopy (XPS). In order to demonstrate application potentials of the activated platforms, a 7 nm ± 1 nm thick NH2‐terminated PEG layer (grafting density of 0.9 chains nm?2) is covalently grafted to RIL‐activated substrates. This layer reduces the non‐specific adsorption (NSA) of bovine serum albumin by 95% to a residual mass coverage of 9.1 ± 2.9 ng cm?2. As shown by these examples, RIL comprises an attractive complementary approach to produce bio‐reactive polymer surfaces with topographic patterns in a one‐step process.  相似文献   

20.
The antimicrobial equipment of materials is of great importance in medicine but also in daily life. A challenge is the antimicrobial modification of hydrophobic surfaces without increasing their low surface energy. This is particularly important for silicone‐based materials. Because most antimicrobial surface modifications render the materials more hydrophilic, methods are needed to achieve antimicrobial activity without changing the high water‐contact‐angle. This is achieved in the present work, where SiO2 nanoparticles are prepared and functionalized with 3‐(trimethoxysilyl)‐propyldimethyloctadecyl ammonium chloride (QAS) in a one‐pot synthesis. The modified nanoparticles are applied onto a silicone surface from suspension with no need of elaborate pretreatment. The resulting surface exhibits a Lotus‐Effect combined with contact‐active antimicrobial properties. The particle surfaces show self‐organizing micro‐ and nanostructures that afford a water‐contact angle of 144° and a hysteresis below 10°. The particles are self‐adhering on the silicone after solvent evaporation and resistant against immersion into and washing with water for at least 5 d. Thereby, the adhesion of the bacterial strain Staphylococcus aureus to these surfaces is reduced and the remaining bacterial cells are killed within 16 h. This is the first example of a Lotus‐Effect surface with intrinsic contact‐active antimicrobial properties.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号