Investigation of structural features of hexadecafluorinated copper and zinc phthalocyanine films

The structural features of hexadecafluorinated copper and zinc phthalocyanine (MPcF₁₆) films (M = Cu, Zn) obtained by vacuum thermal deposition are investigated. The dependence of structural features of these films on the film thickness is studied by means of optical and Raman spectroscopy. It is shown that an increase in the thickness of MPcF₁₆ films, as well as film annealing under vacuum conditions at a temperature of 220°C, leads to the formation of the phase whose crystalline structure differs from that of the 20-to 50-nm-thick initial films.     

Interaction of ranked copper phthalocyanine films with dry nitrogen dioxide on the basis of ESR data

The calculation procedure of the orientation distribution of molecules by the angular dependence of electron spin resonance (ESR) spectra was used to study copper(II) phthalocyanine (CuPc) films of different thickness, obtained by the molecular complex deposition on flat quartz plates. In the first stage of the deposition, the formation of the layer of the α-phase of CuPc with the predominant orientation of molecular stacks (theb-axis of the crystalline lattice) along the plate surface was formed. In the second stage, the layer with the normal disposition of molecular stacks is condensed over the first layer. The copper binuclear associates were formed during the reaction of CuPc with NO₂. The ESR spectra analysis allows us to make an assumption about the construction of associates and to calculate the distance between paramagnetic copper(II) ions. It was shown that the orientation distribution of axially symmetric CuPc associates in the film depends both on the initial film order and the conditions under which it was treated.     

Quantitative analysis of the supramolecular structure of metastable polycrystalline films by infrared spectropolarimetry

A method of quantitative estimation of the structural anisotropy of metastable organic polycrystalline films based on infrared spectropolarimetry is used to investigate the structural features films of the α form of copper phthalocyanine. Due to the separation of the inverse problem of reconstruction of the optical parameters of the medium into a number of stages with optimization over no more than two unknown parameters, the graphical tracking of the optimization process and, as a consequence, the minimization of errors and on-line correction of ambiguity are performed at each stage of the solution. It is demonstrated that the structure of copper phthalocyanine films vacuum-deposited onto a substrate can be changed by varying the substrate temperature, the angle of incidence of a molecular beam during the deposition, and the electrostatic field applied to the substrate.     

Hydrothermal synthesis and gas sensing properties of?single-crystalline ultralong ZnO nanowires

Ultralong ZnO nanowires were successfully synthesized by a simple hydrothermal reaction of Zn foil and aqueous Na₂C₂O₄ solution at 140°C. The as-synthesized ZnO nanowires are single crystalline with the wurtzite structure and grow in the [0001] direction. The role of Na₂C₂O₄ in the formation of ultralong ZnO nanowires was investigated, and a possible mechanism was also proposed to account for the formation of the ultralong ZnO nanowires. The gas sensor fabricated on the basis of the ultralong ZnO nanowires showed excellent response characteristics towards NH₃ and N(C₂H₅)₃ vapors with low concentration, and its detection limits for NH₃ and N(C₂H₅)₃ are about 0.2 and 0.15 ppm at the working temperature of 180°C, respectively. This result suggests potential applications of the ultralong ZnO nanowires in monitoring flammable, toxic and corrosive gases.     

TBT/CuPc复合薄膜的制备及能量/电荷转移研究

在4,7-二(4-三-苯胺基)-2,1,3-苯并噻二唑[4,7-bis(4-triphenylamino)-2,1,3-benzothiadiazole,TBT]和酞菁铜(copper phthalocyanine,CuPc)的混合硝基甲烷溶液中,采用质子化-共电沉积( PCD)的方法制备得到了TBT∶CuPc共混复合...     

A scanning tunneling microscopy study on the effect of post-deposition annealing of copper phthalocyanine thin films

Using scanning tunneling microscopy, overlayer lattice structures and thin film morphology of copper phthalocyanine (CuPc) have been investigated while varying posterior, annealing temperatures. The room temperature deposition of CuPc on Ag(1 1 1) resulted in ordered domains, which were three molecular layers high and separated with disordered regions. The ordered surface also exhibited an oblique lattice with the lattice constants of 13.3 Å and 16.4 Å and the angle of 74° between the two. By annealing the thin films systematically to 580 K, the symmetry of overlayer lattice increased from the oblique to the square lattice, commonly observed on various substrates. Further annealing to 780 K desorbed much of the CuPc molecules. However, the remaining molecules reacted and formed dendrite-like chains, in which each CuPc molecule was linked through its isoindole rings. A possible model for the formation of dendritic chains through polymerization is discussed.     

Synthesis and Optical Characterization of CdS Nanowires by Chemical Process

Cadmium sulfide (CdS) nanostructured materials were synthesized by a wet chemical route without using any capping agent. X-ray diffraction pattern showed the typical interplanar spacings corresponding to the cubic phase of CdS. Transmission electron microscopy studies showed the nanowires formation with length in the range 0.1–1.5 μm and the diameter 25–30 nm. UV–visible optical spectroscopy study was carried out to determine the bandgap of the nanostructured CdS thin films and it showed blue shift with respect to the bulk value. Variation of band gap energies with annealing temperature was also studied in detail. Room temperature photoluminescence of the nano-CdS films was measured and the spectrum showed a broad band centered at ~567 nm, which originated from trap states existing in the forbidden energy gap.     

Paschen curve approach to investigate electron density and deposition rate of Cu in magnetron sputtering system

In this work, Paschen curve for argon gas was obtained during copper deposition using a DC magnetron sputtering system. Five process parameters of Paschen curve were used to obtain the electron density and deposition rate of the deposited nanostructured thin films. Plasma parameter such as electron density was correlated with the deposition rate. It is observed that a minimum deposition rate was obtained for the plasma process parameter corresponding to the Paschen minimum. This investigation helps to understand and optimize the quality of nanostructured thin films depending on the process parameters.     

Controlled growth behavior of chemical vapor deposited Ni nanostructures

Isolation of four distinct nanostructured Ni products is demonstrated in a well-controlled chemical vapor deposition process. These nanostructures include core–shell Ni–NiO nanowires, horizontally oriented nanowires, vertically oriented nanowires, and fully isometric cubic crystals all obtained upon an amorphous SiO₂|Si growth substrate from an identical metal halide precursor. Transmission electron microscopy indicates the horizontally- and vertically-oriented nanowire products to be high-quality single crystals with a preferred growth axis along the ?001? direction while the Ni–NiO core–shell nanowires are polycrystalline metal at the center and surrounded by an outer oxide. The differing crystal structures are reflected in the magnetic response of each nanowire type, as evidenced by magnetoresistance measurements. Detailed discussion of the formation mechanisms leading to each of the four nanostructured Ni products is presented along with a discussion of the general applicability of this non-epitaxial growth process to other material systems.     

Atomistic study of deposition process of Al thin film on Cu substrate

In this paper we report molecular dynamics based atomistic simulations of deposition process of Al atoms onto Cu substrate and following nanoindentation process on that nanostructured material. Effects of incident energy on the morphology of deposited thin film and mechanical property of this nanostructured material are emphasized. The results reveal that the morphology of growing film is layer-by-layer-like at incident energy of 0.1-10 eV. The epitaxy mode of film growth is observed at incident energy below 1 eV, but film-mixing mode commences when incident energy increase to 10 eV accompanying with increased disorder of film structure, which improves quality of deposited thin film. Following indentation studies indicate deposited thin films pose lower stiffness than single crystal Al due to considerable amount of defects existed in them, but Cu substrate is strengthened by the interface generated from lattice mismatch between deposited Al thin film and Cu substrate.     

Influence of the substrate temperature during deposition on film characteristics of copper phthalocyanine and field-effect transistor properties

In this paper, we employ different substrate temperatures during the deposition process and observe a highly ordered structure and strong orientation of copper phthalocyanine (CuPc) molecules on Si/SiO₂ by using X-ray-diffraction and transmission electron microscopy analysis. The results show the effect of CuPc morphology at different substrate temperatures on the organic field-effect-transistor performance. When the substrate temperature for deposition of CuPc is 120 °C, a mobility of 3.75×10^-3 cm²/V s can be obtained. PACS 73.61.Ph; 85.30.Tv; 78.66.Tr     

Formation of CuO nanowires by thermal annealing copper film deposited on Ti/Si substrate

Nanowires of various inorganic materials have been fabricated due to the realization of their applications in different fields. Large-area and uniform cupric oxide (CuO) nanowires were successfully synthesized by a very simple thermal oxidation of copper thin films. The copper films were deposited by electron beam evaporation onto Ti/Si substrates, in which Ti film was first deposited on silicon substrate to serve as adhesion layer. The structure characterization revealed that these nanowires are monoclinic structured single crystallites. The effects of different growth parameters, namely, annealing time, annealing temperature, and film thickness on the fabrication of the CuO nanowires were investigated by scanning electron microscopy. A typical procedure simply involved the thermal oxidation of these substrates in air and within the temperature range from 300 to 700 °C. It is found that nanowires can only be formed at thermal temperature of 400 °C. It is observed that the growth time has an important effect on the length and density of the CuO nanowires, whereas the average diameter is almost the same, i.e.50 nm. Different from the vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism, the growth of nanowires is found to be based on the accumulation and relaxation of the stress.     

LB薄膜中四新戊氧基酞菁锌和四壬基酞菁铜分子聚集体的吸收光谱的温度特性

本文制备了四新戊氧基酞菁锌(Tetra-neopentoxy phthalocyanine zine)(TNPPeZn)和四壬基酞菁铜(Tetra-nonyl phthalocyanine copper)(TNPeCu)两种酞菁衍生物的Langmuir-Blodgett(LB)薄膜.通过测量10～473K温度下的吸收光谱,研究了两种薄膜的分子聚集状态.TNPPeZn的LB薄膜中,存在着分子单体和分子二聚体,在吸收光谱中分别表现为680nm和620nm的吸收峰.随着温度的升高,分子单体逐渐转变为分子二聚体,这个过程是不可逆的.TNPeCu的LB薄膜中,除了分子单体和分子二聚体以外,还有吸收为740nm的分子J聚集体存在.随着温度的变化,J聚集体发生可逆变化.     

Structure and morphology of CuPc and F16CuPc pn heterojunction

This article reports structure and morphology of copper phthalocyanine (CuPc) and fluorinated copper phthalocyanine (F₁₆CuPc) pn heterojunction. Highly ordered CuPc and F₁₆CuPc polycrystalline thin films with the 2 0 0 plane spacing s of 1.30 and 1.56 nm, respectively, could be continuously grown via an intermediate-phase layer. Compared with CuPc, the intermediate-phase layer is much thinner when F₁₆CuPc is used as the first layer. The rougher the first layer is, the thicker the intermediate-phase layer is. Similarly, the 2 0 0 plane spacings of the intermediate-phase layer are dependent on morphology of the first layer. Furthermore, morphology of the heterostructure is mainly dominated by that of CuPc films. Due to the thicker intermediate-phase layer in the CuPc/F₁₆CuPc heterostructure, the thin film transistors (TFT) performance is obviously inferior to that of the F₁₆CuPc/CuPc device.     

Optical properties of selenium-tellurium nanostructured thin film grown by thermal evaporation

Se-Te nanostructured thin films were deposited on glass substrates in the presence of oxygen and argon by thermal evaporation. The properties of Se-Te thin films strongly depend on the deposition method. During the process used, the substrate is cooled to a temperature of 77 K employing liquid nitrogen. The nanostructured thin films of Se_100−xTe_x (where x=4, 8 and 16) are deposited on glass substrate. The surface morphology of the deposited films was investigated through Scanning Electron Microscopy (SEM). The typical size of these nanostructures is in the range 40-100 nm and the length is of the order of several micrometers. The optical parameters i.e. optical gap (E_g), absorption coefficient (α), and extinction coefficient (k) are calculated in the wavelength range 190-1100 nm. It was found that the optical band gap decreased from 3.4 to 2.9 eV when Te concentration was increased in the Se_100−xTe_x nanostructured thin films. The large bandgap may be attributed to the decrease in particle size which clearly exhibits a quantum size effect. XRD analysis was performed to confirm glassy nature of the nanostructured thin films.     

Nanostructured morphology of polymer films prepared by matrix assisted pulsed laser evaporation

As recently illustrated, nanostructured glassy polymer films with exceptional thermal and kinetic stability can be formed via Matrix Assisted Pulsed Laser Evaporation (MAPLE) (Guo et al. in Nat. Mater. 11:337, 2012). Relative to the standard poly(methyl methacrylate) glass formed on cooling at standard rates, glasses prepared by MAPLE can be 40 % less dense and have a 40 K higher glass transition temperature (T _g ). Furthermore, the kinetic stability in the glassy state can be enhanced by 2 orders-of-magnitude. Here, we examine the stability of the structured morphology. We show that nanostructured glasses may be formed even when the substrate is held at temperatures greater than the polymer T _g during deposition. In addition, we discuss the origin of the enhanced stability and the mechanism of nanostructured film formation within the framework of the Zhigilei model. Finally, we compare the nanostructured morphology to the surface morphology of other MAPLE-deposited films in the literature.     

Birefringence measurements of MnPc thin film by polarization microscopy

We have studied optical properties of near-infrared (NIR) spectra and birefringence of the manganese phthalocyanine (MnPc) thin films. The morphology of the MnPc thin film grown on KCl (0 0 1) substrates was observed by using an atomic force microscope. The NIR spectral range of 1.0-1.7 μm was studied in this study, because that of 1.3-1.5 μm is known as an optical communication wavelength. The birefringence was measured with changing the growth condition of a deposition rate and a substrate temperature. The birefringence of the film was most affected by the deposition rate.     

Thin films prepared by simultaneous deposition of copper and free-base phthalocyanine

Composite films of metals and dielectrics attracted considerable attention in the past for their novel optical and mechanical properties which can be tailored precisely by changing their structure and composition. In this work we present a probe into a related but hitherto unexplored field of composites where metal is combined with molecular semiconductor. As model materials we chose free-base phthalocyanine and copper. Films were prepared by simultaneous deposition of copper and free-base phthalocyanine in the dual ICB system. An answer to two basic questions was sought after: 1) does the copper combine with freebase phthalocyanine to form a copper phthalocyanine complex, 2) what is the structure of the films if there is non-stoichiometric surplus of copper in the films? We report results of structural study by a transmission electron microscope. Optical behaviour of the composite was characterized by optical reflectance and transmittance measurement in UV/VIS/NIR range and complemented by FT IR spectra.     

Growth,structure, and cathodoluminescence of Dy-doped ZnO nanowires

Dy-doped ZnO nanowires have been prepared using high-temperature and high-pressure pulsed-laser deposition. The morphology, structure, and composition of the as-prepared nanostructures are characterized by field emission scanning electron microscopy, X-ray diffraction, Raman scattering spectrometry, X-ray photoelectron spectrometry, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The alloying droplets are located at the top of the as-prepared Dy-doped ZnO nanowires, which means that the growth of the Dy-doped ZnO nanowires is a typical vapor-liquid-solid process. The luminescence properties of Dy-doped ZnO nanowires are characterized by cathodoluminescence spectra and photoluminescence spectra at low temperature (8 K). Two peaks at 481 and 583 nm, respectively, are identified to be from the doped Dy³⁺ ions in the CL spectra of Dy-doped ZnO nanowires.     

Growth of hierarchical based ZnO micro/nanostructured films and their tunable wettability behavior

Hierarchical zinc oxide (ZnO) micro/nanostructured thin films were grown onto as-prepared and different annealed ZnO seed layer films by a simple two step chemical process. A cost effective successive ionic layer adsorption and reaction (SILAR) method was employed to grow the seed layer films at optimal temperature (80 °C) and secondly, different hierarchical based ZnO structured thin films were deposited over the seed layered films by chemical bath deposition (CBD). The influence of seed layer on the structural, surface morphological, optical and wettability behavior of the ZnO thin films were systematically investigated. The XRD analysis confirms the high crystalline nature of both the seed layer and corresponding ZnO micro/nanostructured films with a perfect hexagonal structure oriented along (0 0 2) direction. The surface morphology revels a complex and orientated hierarchical based ZnO structured films with diverse shapes from plates to hexagonal rod-like crystal to tube-like structure and even much more complex needle-like shapes during secondary nucleation, by changing the seed layer conditions. The water contact angle (WCA) measurements on hierarchical ZnO structured films are completely examined to study its surface wettability behavior for its suitability in future self-cleaning application. Photoluminescence (PL) spectra of the ZnO structured film exhibit UV and visible emissions in the range of 420-500 nm. The present approach demonstrates its potential for low-temperature, large-scale, controlled synthesis of crystalline hierarchical ZnO nanostructures films.