Effect of atomic layer deposition coatings on the surface structure of anodic aluminum oxide membranes

Anodic aluminum oxide (AAO) membranes were characterized by UV Raman and FT-IR spectroscopies before and after coating the entire surface (including the interior pore walls) of the AAO membranes by atomic layer deposition (ALD). UV Raman reveals the presence of aluminum oxalate in bulk AAO, both before and after ALD coating with Al2O3, because of acid anion incorporation during the anodization process used to produce AAO membranes. The aluminum oxalate in AAO exhibits remarkable thermal stability, not totally decomposing in air until exposed to a temperature >900 degrees C. ALD was used to cover the surface of AAO with either Al2O3 or TiO2. Uncoated AAO have FT-IR spectra with two separate types of OH stretches that can be assigned to isolated OH groups and hydrogen-bonded surface OH groups, respectively. In contrast, AAO surfaces coated by ALD with Al2O3 display a single, broad band of hydrogen-bonded OH groups. AAO substrates coated with TiO2 show a more complicated behavior. UV Raman results show that very thin TiO2 coatings (1 nm) are not stable upon annealing to 500 degrees C. In contrast, thicker coatings can totally cover the contaminated alumina surface and are stable at temperatures in excess of 500 degrees C.     

Preparation of nearly monodisperse multiply coated submicrospheres with a high refractive index

Nearly monodisperse SiO2/TiO2/SiO2 multiply coated submicrospheres with nearly monodisperse silica submicrospheres as cores, thick titania layers, and thin silica skin were prepared to increase the refractive index of complex submicrospheres while keeping their near monodispersity and perfect surface properties. Nearly monodisperse colloidal silica submicrospheres as cores with a diameter of 200 nm were synthesized by a seeding technique on the basis of the hydrolysis of tetraethyl orthosilicate (TEOS) in an aqueous ethanol solution with ammonia as catalyst. On the basis of the hydrolysis of tetrabutyl orthotitanate, a procedure combining continuous feeding with multistep coating was determined to prepare titania coatings about 40 nm thick and increase the refractive index of the complex submicrospheres. The hydrolysis of TEOS was still used to get the outmost silica coating about 10 nm thick on titania coated silica submicrospheres to eliminate random aggregation caused by the TiO2 surface properties of the TiO2/SiO2 complex submicrospheres during the final fabrication of photonic crystals.     

Atomic force microscopy of coated glasses

Atomic force microscopy has been used to investigate the topology of alkoxide gel dip coatings on different substrates. Results of SiO(2) - TiO(2) - ZrO(2) (STZ) coatings are presented on float glass, on polished fused silica, on commercially coated insulating flat glass, and on PtRh. Consolidated STZ coatings display the so-called glass pattern with ripples equal or less than 2 nm high. The same pattern is seen on partially dense STZ coatings, as soon as the surface is stiff enough for scanning, and also on the bottom of a 50 nm deep sputtering crater in the consolidated coating. The vitreous STZ coating on the fire side of the float glass is as flat as the float glass itself. It has the same tendency to contamination. 100 nm wide and 50 nm deep polishing grooves on fused silica have been filled up with the 80 nm thick coating, only dips of a few nm remain. The trenches between the SnO(2) crystallites on the insulating flat glass were filled up and the roughness of the substrate was partially reduced. PtRh sheet remained rough even after the coating. On the partially densified STZ coating, sputtering generates a grained surface.     

Ultrathin SiO(x) Film Coating Effect on the Wettability Change of TiO(2) Surfaces in the Presence and Absence of UV Light Illumination

Wettability of sol-gel TiO(2) film surfaces has been studied by following the H(2)O contact angle (straight theta) as functions of illumination time and subsequent dark storage time. Upon illumination of the TiO(2) surface (lambda(ex)>300 nm), the value of straight theta rapidly decreased to reach approximately zero (photoprocess). When the resultant superhydrophilic sample was stored in the dark, the straight theta value increased slowly with increasing storage time (dark process). Ultrathin SiO(x) films were formed on the surface of TiO(2) by repeating chemisorption of 1,3,5,7-tetramethylcyclotetrasiloxane and its photooxidation. With increasing thickness of the SiO(x) monolayer coating, the rate for the dark process significantly decreased, while that for the photoprocess also decreased. Both X-ray photoelectron spectroscopic studies and product analyses during the photoprocess clarified that photocatalytic oxidation of organic adsorbates in air causes the superhydrophilicity of the TiO(2) surfaces. Copyright 2000 Academic Press.     

多重射流燃烧反应制备的TiO2/ SiO2纳米复合颗粒的形态和结构

TiO₂-SiO₂ nanocomposite particles were prepared in premixed H₂ / Air flame, and the morphology and structure of these nanocomposites were characterized by FTIR, XRD, TEM and HRTEM. The morphology of SiO₂ / TiO₂ nanocomposites was different from that of pure TiO₂ or SiO₂ nanoparticles, and the chemical bond of Ti-O-Si was found in the nanocomposites indicating that the TiO₂ / SiO₂ nanocomposites were not merely a physical mixture of TiO₂ and SiO₂. TiO₂ nanocrystalline grains with sizes of 1～2 nm were homogeneously dispersed in the amorphous SiO₂ matrix when TiCl₄ and SiCl₄ were mixed at molecular level in the flame. The particle size and rutile content decreased with increasing of SiO₂ molar ratio.     

Synthesis and Characterization of Magnetic TiO2/SiO2/NiFe2O4 Composite Photocatalysts

Magnetic TiO2/SiO2/NiFe2O4 composite photocatalytic particles with high crystalline TiO2 shell were synthesized via a mild solution route.The prepared composite particles were characterized with X-ray diffraction(XRD),transmission electron microscopy(TEM),high resolution transmission electron microscopy(HRTEM),scanning electron microscopy(SEM),ultraviolet-visible(UV-Vis) spectroscopy and vibrating sample magnetometer(VSM).The results show that the obtained TiO2/SiO2/NiFe2O4 composite particles were composed...     

Silica-coated, Au/Ag striped nanowires for bioanalysis

Striped metallic nanowires (NW) have been coated with a silica shell of controllable thickness (6-150 nm), and the assay performance of coated vs uncoated NW has been compared. The silica coating does not interfere with identification of the metal striping pattern and protects Ag segments from oxidation, extending the range of assay conditions under which barcoded NW can be used. Much higher and more uniform fluorescence intensities were observed for dye-labeled ssDNA bound to SiO2-coated as compared to intensities for uncoated NW. Simultaneous, multiplexed DNA hybridization assays for three pathogen-specific target sequences on SiO2-coated NW showed good discrimination of complementary from noncomplementary targets. Application of SiO2-coated NW in discrimination of single base mismatches corresponding to a mutation of the p53 gene was also demonstrated. Finally, we have shown that thiolated probe DNA resists desorption under thermocycling conditions if attached via siloxane chemistry to SiO2-coated NW, but not if it is attached via direct adsorption to bare Au/Ag NW.     

Tailoring nanoporous materials by atomic layer deposition

Atomic layer deposition (ALD) is a cyclic process which relies on sequential self-terminating reactions between gas phase precursor molecules and a solid surface. The self-limiting nature of the chemical reactions ensures precise film thickness control and excellent step coverage, even on 3D structures with large aspect ratios. At present, ALD is mainly used in the microelectronics industry, e.g. for growing gate oxides. The excellent conformality that can be achieved with ALD also renders it a promising candidate for coating porous structures, e.g. for functionalization of large surface area substrates for catalysis, fuel cells, batteries, supercapacitors, filtration devices, sensors, membranes etc. This tutorial review focuses on the application of ALD for catalyst design. Examples are discussed where ALD of TiO(2) is used for tailoring the interior surface of nanoporous films with pore sizes of 4-6 nm, resulting in photocatalytic activity. In still narrower pores, the ability to deposit chemical elements can be exploited to generate catalytic sites. In zeolites, ALD of aluminium species enables the generation of acid catalytic activity.     

In situ monitoring of atomic layer deposition in nanoporous thin films using ellipsometric porosimetry

Ellipsometric porosimetry (EP) is a handy technique to characterize the porosity and pore size distribution of porous thin films with pore diameters in the range from below 1 nm up to 50 nm and for the characterization of porous low-k films especially. Atomic layer deposition (ALD) can be used to functionalize porous films and membranes, e.g., for the development of filtration and sensor devices and catalytic surfaces. In this work we report on the implementation of the EP technique onto an ALD reactor. This combination allowed us to employ EP for monitoring the modification of a porous thin film through ALD without removing the sample from the deposition setup. The potential of in situ EP for providing information about the effect of ALD coating on the accessible porosity, the pore radius distribution, the thickness, and mechanical properties of a porous film is demonstrated in the ALD of TiO(2) in a mesoporous silica film.     

钛基多孔HA/SiO2复合涂层的制备及性能研究

为了制得表面多孔且与基材结合强度高的羟基磷灰石(HA)涂层,实验中以正丁醇为分散介质,以SiO2粉末为添加剂,纯钛片为基材,电泳沉积制备羟基磷灰石/二氧化硅/壳聚糖/(HA/SiO2/CS)复合涂层,经后续热处理得到多孔HA/SiO2复合涂层,采用扫描电镜(SEM)、傅立叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)、万能材料试验机对涂层的表面形貌、组成、结构和结合强度进行测试和表征,并通过模拟体液(SBF)浸泡法对复合涂层的生物活性进行评价.结果表明:当悬浮液中的HA/SiO2/CS质量比为1∶1∶1时,制得的HA/SiO2/CS涂层经700℃热处理后获得的HA/SiO2复合涂层孔洞分布均匀,大孔孔径在10～15μm,小孔孔径在1～5μm;涂层与基材的结合强度达到25.5 MPa;多孔HA/SiO2复合涂层在SBF中浸泡7 d后,涂层表面碳磷灰石化;说明实验中添加SiO2所制得的多孔HA/SiO2复合涂层与钛基材结合强度高,且具有良好的生物活性.     

甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜的发光性能

采用溶胶-凝胶(Sol-Gel)法, 以正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES)为先驱物, 盐酸为催化剂, 用二步水解法制备了Ti3+/SiO2薄膜和甲基三乙氧基硅烷修饰的Ti3+/SiO2复合薄膜. 采用红外光谱仪、X射线衍射仪、椭偏仪、荧光光谱仪等对膜层性质进行了分析. 结果表明, 掺杂Ti3+的SiO2薄膜分别在250 nm附近有一弱的激发峰, 294 nm附近有一强的激发峰, 在393 nm附近出现一强的发射峰. IR光谱发现, MTES修饰的Ti3+/SiO2复合薄膜的Si—OH的吸收峰强度比Ti3+/SiO2薄膜的略减小, Si—O—Si的吸收峰明显增强, 表明复合薄膜硅氧网络结构更规则, 有利于Ti3+的均匀分散. Ti3+/SiO2薄膜与复合薄膜的孔隙率分别为13.64%和6.66%, 表明MTES的加入使薄膜更致密. 在空气中陈放30 d后, Ti3+/SiO2薄膜已经检测不到荧光发射峰, 而MTES修饰的Ti3+/SiO2复合薄膜荧光强度只下降了18%. 在氮气中陈放30 d后, 普通薄膜与复合薄膜的荧光强度均仅下降了10%. 表明Ti3+的荧光猝灭的主要原因是由于Ti3+被氧化造成的. 溶胶中加入MTES后, 薄膜表面结构得到改善, 有效地防止了Ti3+的氧化, 荧光强度更稳定.     

二氧化硅纳米颗粒/硅树脂复合超疏水功能涂层的制备和性能研究

将二氧化硅纳米颗粒和硅树脂制成混合液,采用喷涂法(spray-coating)制备出了具备超疏水性的复合涂层.研究了二氧化硅、硅树脂不同含量配比对涂层疏水性能的影响,结果表明复合涂层的接触角随二氧化硅含量的增加而增加.在二氧化硅含量大于3%(质量分数)时,涂层显现超疏水性;当二氧化硅含量为3%(质量分数)、硅树脂含量为7%(质量分数)时,涂层与水的接触角达到151.6°,滚动角接近0°.通过扫描电子显微镜(SEM)观察涂层表面的微观结构,发现超疏水性的涂层具备微-纳复合阶层结构,类球状突起粒径在5μm左右,类球状突起上分布纳米团聚颗粒,直径约为50 nm.这种类似荷叶表面的微(纳复合阶层结构,结合硅树脂的低表面能,使得复合涂层具备了超疏水性能.     

Atomic layer deposition chemistry: recent developments and future challenges

New materials, namely high-k (high-permittivity) dielectrics to replace SiO(2), Cu to replace Al, and barrier materials for Cu, are revolutionizing modern integrated circuits. These materials must be deposited as very thin films on structured surfaces. The self-limiting growth mechanism characteristic to atomic layer deposition (ALD) facilitates the control of film thickness at the atomic level and allows deposition on large and complex surfaces. These features make ALD a very promising technique for future integrated circuits. Recent ALD research has mainly focused on materials required in microelectronics. Chemistry, in particular the selection of suitable precursor combinations, is the key issue in ALD; many interesting results have been obtained by smart chemistry. ALD is also likely to find applications in other areas, such as magnetic recording heads, optics, demanding protective coatings, and micro-electromechanical systems, provided that cost-effective processes can be found for the materials required.     

单分散α-Fe_2O_3纳米结构空心亚微球的制备及表征

采用一种新的溶液生长法结合多步包覆法在自制的不同粒径SiO2单分散亚微球表面包覆不同厚度的β-FeOOH涂层,得到单分散β-FeOOH/SiO2核壳结构亚微球.实验结果表明,SiO2核心颗粒尺寸对表面涂层的形态和包覆均匀性有很大影响.当SiO2核心颗粒的平均粒径为250 nm左右时,β-FeOOH表面涂层均匀,颗粒间团聚较少,一次包覆后涂层厚度约为35 nm.涂层中β-FeOOH纳米棒的尺寸随着所选SiO2核心颗粒粒径的增大而相应增大.经多次包覆能够显著提高涂层的厚度,3次包覆后β-FeOOH表面涂层厚约100 nm.β-FeOOH/SiO2核壳结构亚微球与质量分数5%的NaOH溶液反应后,于600℃焙烧2 h得到了单分散α-Fe2O3空心微球.单分散α-Fe2O3空心亚微球表层是由α-Fe2O3纳米棒搭建而成的三维网络结构,α-Fe2O3纳米棒的尺寸与核壳结构中β-FeOOH纳米棒的尺寸基本一致.     

TiO2/SiO2气凝胶微球的制备及其表征

以TiOSO4和硅溶胶为原料, 加入甲酰胺作为干燥控制化学添加剂, 采用W/O乳状液中的溶胶-凝胶法制备TiO2/SiO2凝胶微球, 通过正硅酸乙酯母液浸泡、溶剂交换、陈化和常压干燥技术制备TiO2/SiO2气凝胶微球, 采用光学显微镜、SEM、TEM和BET比表面及孔分布测定等手段对所得样品进行表征. 典型的气凝胶微球样品是由粒径15 nm左右, 粒度分布相当均匀的球状纳米粒子构成的轻质纳米多孔材料, 表观密度为177 kg•m-3, 比表面积372 m2•g-1, 平均孔径22.78 nm, 孔隙率高达92.0％, 微球的宏观粒径为50 m. 依据制备条件的变化, TiO2/SiO2气凝胶微球的宏观粒径可控在10～200 m之间, 表观密度为150～300 kg•m-3, 比表面积为300～400 m2•g-1, 平均孔径在18.71～22.78 nm之间变化.     

DNA functionalization of carbon nanotubes for ultrathin atomic layer deposition of high kappa dielectrics for nanotube transistors with 60 mV/decade switching

For single-walled carbon nanotube (SWNT) field effect transistors, vertical scaling of high kappa dielectrics by atomic layer deposition (ALD) currently stands at approximately 8 nm with a subthreshold swing S approximately 70-90 mV/decade at room temperature. ALD on as-grown pristine SWNTs is incapable of producing a uniform and conformal dielectric layer due to the lack of functional groups on nanotubes and because nucleation of an oxide dielectric layer in the ALD process hinges upon covalent chemisorption on reactive groups on surfaces. Here, we show that by noncovalent functionalization of SWNTs with poly-T DNA molecules (dT40-DNA), one can impart functional groups of sufficient density and stability for uniform and conformal ALD of high kappa dielectrics on SWNTs with thickness down to 2-3 nm. This enables approaching the ultimate vertical scaling limit of nanotube FETs and reliably achieving S approximately 60 mV/decade at room temperature, and S approximately 50 mV/decade in the band-to-band tunneling regime of ambipolar transport. We have also carried out microscopy investigations to understand ALD processes on SWNTs with and without DNA functionalization.     

Atomic Force Microscopy Study of NaOH Corroded Al2O3-TiO2-SiO2 Coatings on Glass

Atomic force microscopy (AFM) was used to study the performance of 80 nm thick Al2O3-TiO2-SiO2 sol-gel coatings on glass substrates following corrosion in 1 M NaOH solutions at 60°C. The as-prepared coatings were homogeneous on a nanoscale and displayed the glass pattern before corrosion. Layers with different compositions behaved differently during the corrosion process. Thus, TiO2 or TiO2-dominated layers had tetragonal-like crystals on their surfaces after corrosion, possibly of anatase composition. On the other hand, layers with a molar ratio Al2O3 : SiO2 near 1 : 2 displayed a pseudo-hexagonal morphology, possibly with a nepheline (Na2O · Al2O3 · 2SiO2) composition. Layers of 5Al2O3-40TiO2-55SiO 2 were corroded is a stepwise fashion and had no special surface morphology.     

Interfacial chemical bonding effect on the photocatalytic activity of TiO2-SiO2 nanocoupling systems

TiO(2) nanoparticles (NPs) were deposited on the surfaces of SiO(2) microspheres with a mesoporous structure prepared by a hydrolysis-controlled sol-gel technique. The TiO(2) NPs were firmly combined on the surfaces of SiO(2) microspheres through the interfacial Si-O-Ti bonds. The coupling causes the bandgap widening up to 3.37 eV, enhancing the photocatalytic activity for the decomposition of acetaldehyde under illumination of UV-light (330 < λ < 400 nm). Density functional theory calculations for model clusters suggested that the observed results are derived from the lowering in the valence band edge energy with the interfacial bond formation.     

有机硅聚醚共聚物功能化处理制备多壁碳纳米管悬浊液

以有机硅聚醚共聚物(PSPEO)为分散剂, 水为溶剂, 超声波作用下对硝酸纯化的多壁碳纳米管、浓硫酸与浓硝酸组成的混酸剪切的多壁碳纳米管功能化处理, 分别得到1～2.5 mg/mL和3～5 mg/mL的多壁碳纳米管悬浊液. 所得悬浊液有较好的稳定性, 这得益于有机硅聚醚共聚物独特的结构与性能. 用TEM, HRTEM, UV-vis, Raman光谱等技术对多壁碳纳米管悬浊液进行表征, 结果表明5～10 nm的PSPEO覆盖在碳纳米管表面并与碳纳米管强相互作用, 实现了碳纳米管的分散.     

Three-Dimensional Arrays Formed by Monodisperse TiO(2) Coated on SiO(2) Spheres

Uniform coatings of TiO(2) on monodisperse spheres of silica have been obtained. The resulting particle sizes are within the range 0.4 to 1 μm. The thickness of the coating can be controlled by adjusting nuclei sizes (silica sphere), reaction times, and water and surfactant concentrations. The TiO(2)/SiO(2) spheres were sedimented to achieve structures with three-dimensional order. Three-dimensional ordered materials with higher refractive index were obtained by transforming the amorphous titania layer to rutile by thermal treatment with improved mechanical rigidity. The sphere composition, quality, and morphology have been assessed by different techniques. Copyright 2000 Academic Press.