A simple pathway to ordered silica nanopattern from self-assembling of block copolymer containing organic silicon block

Self-assembly of block copolymer is an effective strategy to prepare periodic structures at nanoscale. In this paper an unique and very simple method to prepare inorganic silica nanopattern is demonstrated from self-assembling of poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) on the surface of silicon wafer. To simplify the patterning process, at first we obtain highly ordered PDMS microdomains, which are covered with PS layer by controlling solvent vapor annealing conditions. Following exposure to UV/O₃ irradiation, nanopatterned surface consisting of silicon oxide is fabricated directly via selectively etching PS phase and converting PDMS phase into silicon oxide. As tuning the composition of the block copolymer, hexagonally packing dot and straight stripe pattern can be obtained. Finally, the time evolution from spheres morphology to aligned long cylinders is discussed. These results hold promise for nanolithography and the fabrication of nanodevices.     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.     

Crystallization Behavior of PEO in Nano‐Structured PEO‐b‐PS/PPO Blends

Blends of poly (ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) homopolymer were obtained by solution blending, and the morphologies of PEO dispersed nanoparticles in PPO/PS matrix were observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The isothermal crystallization kinetics was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nonisothermal crystallization kinetics was studied using DSC. The results showed that PEO segments were easier to crystallize in the blend than in the copolymer probably due to the interfaces of PPO acting as nucleation sites to promote the crystallization of PEO. The crystallization of PEO blocks destroyed the pre‐existing microdomain structure even though the glass transition temperature of the matrix was much higher than the crystallization temperature.     

Polymer concentration, shear and stretch field effects on the surface morphology evolution during the spin-coating

Polymer concentration and shear and stretch field effects on the surface morphology evolution of three different kinds of polymers (polystyrene (PS), polybutadiene (PB) and polystyrene-b-polybutadiene-b-polystyrene (SBS)) during the spin-coating were investigated by means of atomic force microscopy (AFM). For PS and SBS, continuous film, net-like structure and particle structure were observed at different concentrations. For PB, net-like structures were not observed and continuous films and radial array of droplets emerged. Moreover, we compared surface morphology transitions on different substrate locations from the center to the edge. For PS, net-like structure, broken net-like structure and irregular array of particles were observed. For SBS, net-like structure, periodically orientated string-like structure and broken-line structure appeared. But for PB, flower-like holes in the continuous film, distorted stream-like structure and irregular distributions of droplets emerged. These different transitions of surface morphologies were discussed in terms of individual material property.     

Self-assembled block polymer templates as high resolution lithographic masks

Diblock copolymer thin films have recently received more attention due to their ability to organize into nanometric structures under thermal annealing. This phenomenon was studied for an asymmetric poly(styrene-block-methyl methacrylate) (PS-b-PMMA) diblock copolymer with PMMA weight fraction of 0.3 and MW = 67,100 g mol⁻¹. First, the surface chemistry of the substrate was modified to favor the formation of vertical PMMA cylinders surrounded by a PS matrix. We have also found that the mean pore area of cylinders increases with their coordination number. Finally, these films were used as a deposition or etching mask to produce well-organized arrays of holes, dots and nanopillars.     

Solvent vapor induced morphology transition in thin film of cylinder forming diblock copolymer

The morphology formation and transition of thin film of a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer annealed under 1,1,2-trichloroethane (Tri-CE), toluene (Tol), and their binary mixed solvent vapors is investigated by using optical microscopy (OM) and transmission electronic microscopy (TEM). By modulating the annealing solvent vapor pressure and the preferential affinities, a detailed morphology evolution with increasing the vapor pressure and a series of morphologies depending on the preferential affinities have been observed. A phase diagram by plotting the morphologies as a function of the annealing solvent vapor pressure and its preferential affinity is subsequently constructed.     

Effect of Al mole fraction on structural and electrical properties of AlxGa1−xN/GaN heterostructures grown by plasma-assisted molecular beam epitaxy

The effect of Al mole fractions on the structural and electrical properties of Al_xGa_1−xN/GaN thin films grown by plasma-assisted molecular beam epitaxy (PA-MBE) on Si (1 1 1) substrates has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and current-voltage (I-V) measurements. X-ray results revealed that the AlGaN/GaN/AlN was epitaxially grown on Si substrate. By applying Vegard's law, the Al mole fractions of Al_xGa_1−xN samples were found to be 0.11, 0.24, 0.30 and 0.43, respectively. The structural and morphology results indicated that there is a relatively larger tensile strain for the sample with the smallest Al mole fraction; while a smaller compressive strain and larger grain size appear with Al mole fraction equal to 0.30. The strain gets relaxed with the highest Al mole fraction sample. Finally, the linear relationship between the barrier height and Al mole fraction was obtained.     

Effect of Nanoparticles on the Phase Behavior of Polystyrene/Poly(vinyl methyl ether) Blends with Different Polydispersities

Effects of two kinds of silica nanoparticles on the phase behavior of blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS), with the same number average molecular weight but different polydispersities, were studied by using optical microscopy. The addition of both the hydrophilic A200-SiO₂ and hydrophobic R974-SiO₂ nanoparticles made the miscibility become worse. The decrease in the phase separation temperatures of PS/PVME with polydisperse PS (pPS) was larger than that of PS/PVME with monodisperse PS (mPS) in the presence of A200-SiO₂; the shifts of the phase separation temperatures of mPS/PVME and pPS/PVME were comparable for the incorporation of R974-SiO₂. The addition of both kinds of silica accelerated the phase separation during the nonisothermal phase separation. The domain size changes of the phase morphology of mPS/PVME (50/50) and pPS/PVME (50/50) were almost the same during the nonisothermal phase separation in the presence of nanoparticles. During the isothermal phase separation, the introduction of silica slowed down the phase separation dynamics by hindering the phase structure transition. The morphology changes of pPS/PVME (50/50) were more evident than those of mPS/PVME (50/50) with the incorporation of SiO₂.     

Preferential surface segregation of homopolymer and copolymer blend films

Surface film properties of the homopolymers polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(butyl methacrylate) (PBMA) and the copolymer poly(methyl methacrylate)-co-poly(butyl methacrylate) (PMMA-co-PBMA) and their blends with PS have been examined by atomic force microscopy (AFM) and contact angle measurements. The total and the Lifshitz-van der Waals, acid and base components of the surface free energy together with the work of adhesion and its components, the cohesive energy density and the solubility parameters of the homopolymer, copolymer and blend films were determined. Films of about 3 μm were considered. The results are discussed in terms of surface migration mechanisms based on surface free energy and solubilities of the polymers in the solvent, toluene in this paper. AFM imaging and contact angles revealed surface enrichment at the air polymer interface of PBMA for both the PS/PBMA blend and the copolymer PMMA-co-PBMA, whereas the PS/PMMA and PS/PMMA-co-PBMA blend film surfaces show island-like phase-separated structure of typical size 27.4-86.5 nm in diameter and 6.9-15.6 nm in height for PS/PMMA, while for PS/ PMMA-co-PBMA film surface the typical size is 49.6-153.3 nm in diameter and 1.6-14.2 nm in height.     

Polyblends of poly(styrene-b-butadiene-b-styrene) and polystyrene. II. Electron microscopy

Electron micrographs of a series of polyblends of poly(styrene-b-butadiene-b-styrene (SBS) and polystyrene (PS) are presented. These poly blends were cast from three different solvents, i.e., tetrahydrofuran—methyl ethyl ketone (THF/ MEK), benzene—heptane, and carbon tetrachloride. PS of four different molecular weights were used. It is shown that when the molecular weight of PS exceeds that in the block copolymer, a third phase in the form of “islands” is formed. Lamellarlike structures are formed in the block domains upon the addition of homopolymer. Stretching perturbs the morphology of the block domains somewhat, and produces craze marks in the PS islands. The craze marks are removed upon annealing. These results are discussed in conjunction with the observed mechanical behavior of the same polyblends reported in Part I of this series.     

Effect of humidity on domain switching behaviors of BaTiO3 single crystal under sustained load

Domain switching behaviors of BaTiO₃ single crystal in humidity conditions were studied by polarized light microscopy (PLM) and atomic force microscopy (AFM). The results showed that the low humidity has no effect on both a-b domain configuration and a-c domain configuration under sustained load. However, the high humidity can promote a domain switching to c domain under sustained load. The difference of energy reduction induced by H₂O molecules between c domains and a(b) domains leads to this phenomenon.     

Morphology controlled open circuit voltage in polymer solar cells

We report a strong dependence of open circuit voltage on the altered morphology of block copolymer (P3HT‐b ‐PPerAcr) based solar cells. The open circuit voltage increases dramatically by about 300 mV by increasing the amount of acceptor homopolymer within the block copolymer/homopolymer blends. The change in open circuit voltage is found to be in correlation with the enrichment of acceptor moiety at the film surface as identified by Atomic force microscopy (AFM) and X‐ray photoelectron spectroscopy (XPS). Based on this fact, an additional increase in open circuit voltage to its maximum values is achieved by introducing an acceptor buffer layer at the cathode interface. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A comparative morphological study of electron beam co-deposited binary optical thin films of HfO2:SiO2 and ZrO2:SiO2

A comparative morphology, grain structure and optical properties studies of reactive electron beam co-evaporated mixed thin films of hafnia–silica (HfO₂:SiO₂) and zirconia–silica (ZrO₂:SiO₂) systems have been carried out using atomic force microscopy and phase modulated ellipsometry. The addition of silica, especially with small fractions, has demonstrated altogether different types of evolutions in the microstructure and morphology in these binary thin film systems possibly forming new solid solution phases. Such morphological evolutions are probed through RMS roughness, power spectral density, height–height correlation and autocorrelation analyses of the topographic data acquired through atomic force microscopy. The present investigations indicated that with composition-control morphological quality improvement is more favourable in composite hafnia–silica over the zirconia–silica films. So for ultraviolet optical coating applications which demand low light scattering thin film microstructure, hafnia–silica binary composite system has a definite edge over the zirconia–silica counterpart.     

Shallow hydroxyapatite coatings pulsed laser deposited onto Al2O3 substrates with controlled porosity: correlation of morphological characteristics with in vitro testing results

We studied the influence of porous Al₂O₃ substrates on Ce-stabilized ZrO₂-doped hydroxyapatite thin films morphology pulsed laser deposited on their top. The porosities of substrates were monitored by changing sintering temperatures and measured with a high pressure Hg porosimeter.The depositions were conducted in 50 Pa water vapors by multipulse ablation of the targets with an UV KrF* (λ = 248 nm, τ ∼ 25 ns) excimer laser. The surface morphology of synthesized nanostructures was investigated by scanning electron microscopy and atomic force microcopy. Ca/P ratio within the range 1.67-1.70 was found for hydroxyapatite coatings by energy dispersive spectroscopy.The films were further seeded with mesenchymal stem cells for in vitro tests. The cells showed good attachment and spreading uniformly covering the entire surface of samples. The complexity of film morphology which is increasing with substrate porosity was shown to have a positive influence on cultivated cells density.     

Annealing effects on the surface morphologies of thin PS/PMMA blend films with different film thickness

The surface morphology evolution of three thin polystyrene (PS)/polymethyl methacrylate (PMMA) blend films (<70 nm) on SiO_x substrates upon annealing were investigated by atomic force microscopy (AFM) and some interesting phenomena were observed. All the spin-coated PS/PMMA blend films were not in thermodynamic equilibrium. For the 67.1 and the 27.2 nm PS/PMMA blend films, owing to the low mobility of the PMMA-rich phase layer at substrate surfaces and interfacial stabilization caused by long-range van der Waals forces of the substrates, the long-lived metastable surface morphologies (the foam-like and the bicontinuous morphologies) were first observed. For the two-dimensional ultrathin PS/PMMA blend film (16.3 nm), the discrete domains of the PS-rich phases upon the PMMA-rich phase layer formed and the secondary phase separation occurred after a longer annealing time.     

A Study on Compatibility and Properties of POE/PS/SEBS Ternary Blends

Ethylene‐α‐olefin copolymer (POE)/polystyrene (PS)/poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) blends were prepared via melt blending in a co‐rotating twin‐screw extruder. The effects of SEBS copolymer on the morphology and rheological and mechanical properties of the blends were studied. Scanning electron microscopy (SEM) photos showed that the addition of SEBS copolymer resulted in finer dispersion of PS particles in the POE matrix and better interfacial adhesion between POE and PS compared with POE/PS blends, which exhibited a very coarse morphology due to the immiscibility between them. Interestingly, the tensile strength increased from 12.5 MPa for neat POE to 23.5 MPa for the POE/PS/SEBS (60/10/30) blend, whereas the tensile strengths of POE/PS (85.7/14.3) blend and POE/SEBS (66.7/33.3) blend were only 10.5 and 16.5 MPa, respectively. This indicates that both SEBS copolymer and PS have a synergistic reinforcing effect on POE. Dynamic mechanical thermal analysis (DMTA) and dynamic rheological property measurement also revealed that there existed some interactions between POE and SEBS as well as between SEBS and PS. DMTA results also showed that the storage modulus of POE increased when PS and SEBS were incorporated, especially at high temperature, which means that the service temperature of POE was improved.     

Surface treatment of nanoporous silicon with noble metal ions and characterizations

A very large surface to volume ratio of nanoporous silicon (PS) produces a high density of surface states, which are responsible for uncontrolled oxidation of the PS surface. Hence it disturbs the stability of the material and also creates difficulties in the formation of a reliable electrical contact. To passivate the surface states of the nanoporous silicon, noble metals (Pd, Ru, and Pt) were dispersed on the PS surface by an electroless chemical method. GIXRD (glancing incidence X-ray diffraction) proved the crystallinity of PS and the presence of noble metals on its surface. While FESEM (field emission scanning electron microscopy) showed the morphology, the EDX (energy dispersive X-ray) line scans and digital X-ray image mapping indicated the formation of the noble metal islands on the PS surface. Dynamic SIMS (secondary ion mass spectroscopy) further confirmed the presence of noble metals and other impurities near the surface of the modified PS. The variation of the surface roughness after the noble metal modification was exhibited by AFM (atomic force microscopy). The formation of a thin oxide layer on the modified PS surface was verified by XPS (X-ray photoelectron spectroscopy).     

Elaboration and characterization of TiO2 nanoparticles incorporated in SiO2 host matrix

Nanometer-scale TiO₂ particles have been synthesized by sol-gel method. It was incorporated in a glass-based silica aerogel. The composite was characterized by various techniques such as particle size analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and photoluminescence (PL). The bulk glass presents a strong luminescence at wavelengths ranging from 750 to 950 nm. This PL was attributed to various non-bridging oxygen hole centers (NBOHCs) defects resulting from thermal treatment and crystallization of TiO₂ at the interface between titania nanoparticles and silica host matrix.     

Morphological characterization of ITO thin films surfaces

In this study, indium tin oxide (ITO) thin films were deposited by electron beam evaporation method on glass substrates at room temperature, followed by postannealing at 200 and 300 °C for annealing time up to 1 h. Fractal image processing has been applied to describe the surface morphology of ITO thin films from their atomic force microscopy (AFM) images. These topographical images of the ITO thin films indicate changes in morphological behavior of the film. Also, the results suggest that the fractal dimension D can be used to explain the change of the entire grain morphology along the growth direction.     

Nanoscale semiconductor Pb1−xSnxSe (x = 0.2) thin films synthesized by electrochemical atomic layer deposition

In this paper the fabrication and characterization of IV-VI semiconductor Pb_1−xSn_xSe (x = 0.2) thin films on gold substrate by electrochemical atomic layer deposition (EC-ALD) method at room temperature are reported. Cyclic voltammetry (CV) is used to determine approximate deposition potentials for each element. The amperometric I-t technique is used to fabricate the semiconductor alloy. The elements are deposited in the following sequence: (Se/Pb/Se/Pb/Se/Pb/Se/Pb/Se/Sn …), each period is formed using four ALD cycles of PbSe followed by one cycle of SnSe. Then the deposition manner above is cyclic repeated till a satisfactory film with expected thickness of Pb_1−xSn_xSe is obtained. The morphology of the deposit is observed by field emission scanning electron microscopy (FE-SEM). X-ray diffraction (XRD) pattern is used to study its crystalline structure; X-ray photoelectron spectroscopy (XPS) of the deposit indicates an approximate ratio 1.0:0.8:0.2 of Se, Pb and Sn, as the expected stoichiometry for the deposit. Open-circuit potential (OCP) studies indicate a good p-type property, and the good optical activity makes it suitable for fabricating a photoelectric switch.