Film Growth Direction Research Articles

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO2 thin films at deposition temperature in the range of 300–750°C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OiPr)4} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me2N)2Ti(OiPr)2} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO2 polycrystalline thin films with anatase phase were deposited on Si(100) with TIP at temperature as low as 450°C. XRD and TED data showed that below 500°C, the TiO2 thin films were dominantly grown in the [211] direction on Si(100), whereas with increasing the deposition temperature to 700°C, the main film growth direction was changed to [200]. Above 700°C, however, rutile phase TiO2 thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(100) below 450°C while a highly oriented anatase TiO2 film in the [200] direction was obtained at 500°C. With further increasing deposition temperatures over 600°C, the main film growth direction shows a sequential change from rutile [101] to rutile [400], indicating a possibility of getting single crystalline TiO2 film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO2 film synthesized with BTDIP precursor to apply dye-sensitized solar cell.

Structural, electrical and photoluminescence properties of ZnO:Al network films grown on nanochannel Al2O3 substrates by direct current magnetron sputtering with an oblique target

ZnO:Al network films were grown on nanochannel Al2O3 substrates at 300K by direct current magnetron sputtering with an oblique target. The film thicknesses are 60nm, 160nm and 190nm. The holes of the network films diminish with increasing film thickness. For the 60-nm thick film, the network is formed by connecting grains. For the 160-nm and 190-nm thick films, however, the network is formed by connecting granules. The granules consist of many small grains. All the network films have a wurtzite structure. The 60-nm and 160-nm thick network films mainly have a [101] orientation in the film growth direction while the 190-nm thick network film grows with a random crystallographic orientation. A temperature dependence of the resistance within 160–300K reveals that the network films exhibit a semiconducting behavior and their carrier transport mechanism is thermally activated band conduction. Room temperature photoluminescence spectra for wavelengths between 300nm and 700nm reveal a violet emission centered at 405nm for the 60-nm thick network film and a blue emission centered at 470nm for both the 160-nm and the 190-nm thick network films. Annealing decreases the resistivity of the network film.

Nanoassembly control and optical absorption in CdTe-ZnO nanocomposite thin films

The spatial distribution of CdTe nanoparticles within a ZnO thin-film matrix was manipulated using a dual-source, sequential radio-frequency (RF)-sputter deposition technique to produce nanocomposite materials with tuned spectral absorption characteristics. The relative substrate exposure time to each sputtering source was used to control the semiconductor phase connectivity, both within the film plane and along the film growth direction, to influence the degree of photocarrier confinement and the resulting optical transition energies exhibited by the CdTe phase. Significant changes (up to ΔE ≈ 0.3 eV) in the absorption onset energy for the CdTe nanoparticle ensemble were produced through modification in the extended structure of the semiconductor phase. Raman spectroscopy, cross-sectional transmission electron microscopy, and x-ray diffraction were used to confirm the phase identity of the CdTe and ZnO and to characterize the nanostructures produced in these composite films. Isochronal annealing for 5 min at temperatures up to 800 °C further indicated the potential to improve film crystallinity as well as to establish the post-deposition thermal processing limits of stability for the semiconductor phase. The study highlights the significance of ensemble behavior as a means to influence quantum-scale semiconductor optical characteristics of import to the use of such materials as the basis for a variety of optoelectronic devices, including photosensitized heterojunction components in thin film photovoltaics.

Orientation degree characterization of diamond etched with Ce-7%Fe alloy

An increasing {110} orientation degree behavior was observed during etching of chemical vapor deposition (CVD) diamond films by partially melting Ce-7%Fe alloys. In order to accurately investigate this phenomenon, the X-ray diffraction method was used to identify the changes in the surface crystal orientation of the diamond films etched by Ce-7%Fe alloys, and evolution of orientation along the growth direction of the un-etched diamond film was analyzed by electron backscattering diffraction (EBSD), and then the morphology of etched diamond surface was observed by scanning electron microscopy (SEM). The results showed that the {110} orientation degree of diamond surface increased due to the anisotropy in diamond etching with Ce-7%Fe, which was verified by the etching “pit” in SEM micrographs.

Variation of Nanopore Diameter Along Porous Anodic Alumina Channels by Multi-Step Anodization

In order to form tapered nanocapillaries, we investigated a method to vary the nanopore diameter along the porous anodic alumina (PAA) channels using multi-step anodization. By anodizing the aluminum in either single acid (H3PO4) or multi-acid (H2SO4, oxalic acid and H3PO4) with increasing or decreasing voltage, the diameter of the nanopore along the PAA channel can be varied systematically corresponding to the applied voltages. The pore size along the channel can be enlarged or shrunken in the range of 20 nm to 200 nm. Structural engineering of the template along the film growth direction can be achieved by deliberately designing a suitable voltage and electrolyte together with anodization time.

Structural, electrical and photoluminescence properties of ZnO:Al films grown on MgO(0 0 1) by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on MgO(0 0 1) substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and a c-axis orientation in the film growth direction. The films deposited at 300 K initially grow with thin columnar grains and subsequently grow with large granular grains on the thin columnar grains. However, the films grown at 673 K consist mainly of dense columnar grains perpendicular to the substrate surface. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity, the highest free electron concentration and Hall's mobility. A temperature dependence of the resistivity within 5–300 K reveals that the films grown at 300 K exhibit a semiconducting behavior and those grown at 673 K show a metal–semiconductor transition. The carrier transport mechanism is Mott's variable range hopping in the temperature range below 90 K for all the films and thermally activated band conduction above 215 K for the films grown at 300 K. Room temperature photoluminescence spectra for wavelengths between 300 nm and 800 nm reveal mainly blue-green emissions centered at 452 nm, 475 nm and 515 nm.

Residual Strain Evaluation by Cross-Sectional Micro-Reflectance Spectroscopy of Freestanding GaN Grown by Hydride Vapor Phase Epitaxy

Distributions of residual stresses in the cross-section of as-grown c-plane freestanding GaN substrates grown by hydride vapor phase epitaxy (HVPE) were precisely measured by low temperature cross-sectional micro-reflectance spectroscopy. Based on the measured residual stresses in the cross-section area, the depth profile of in-plane isotropic biaxial intrinsic strain in the as-grown GaN wafer was also established according to the elastic theory for thin films. It is found that the intrinsic strain increases nearly linearly with the increasing distance to the Ga-face of the freestanding GaN substrate, and is greatly reduced by the introduction of three-dimensional (3D) GaN islands growth in the starting stage of the HVPE growth. According to the relationship between the intrinsic strain and threading dislocation density, the current research suggests that the bending of freestanding GaN is caused by the reduction of threading dislocation density along the film growth direction.

Effect of analysis direction on the measurement of interfacial mixing in thin metal layers with atom probe tomography

The accuracy and precision of thin-film interfacial mixing as measured with atom probe tomography (APT) are assessed by considering experimental and simulated field-evaporation of a Co/Cu/Co multilayer structure. Reconstructions were performed using constant shank angle and Z-scale reordering algorithms. Reconstruction of simulated data (zero intermixing) results in a 10-90% intermixing width of ~0.2 nm while experiential intermixing (measured from multiple runs) was 0.47 ± 0.19 and 0.49 ± 0.10nm for Co-on-Cu and Cu-on-Co interfaces, respectively. The experimental data were collected in analysis orientations both parallel and anti-parallel to film growth direction and the impact of this on the interfacial mixing measurements is discussed. It is proposed that the resolution of such APT measurements is limited by the combination of specimen shape and reconstruction algorithms rather than by an inherent instrumentation limit.

Substrate Dependent Structural and Magnetic Properties of Pulsed Laser Deposited Fe<SUB>3</SUB>O<SUB>4</SUB> Thin Films

Nanocrystalline iron oxide thin films have been deposited on various substrates such as quartz, MgO(100), and Si(100) by pulsed laser deposition technique using excimer KrF laser (248 nm). The orientations, crystallite size and lattice parameters were studied using X-ray diffraction. The XRD results show that the films deposited on MgO and Si substrates are highly oriented and show only (400) and (311) reflections respectively. On the other hand, the orientation of the films deposited on quarts substrate changed from (311) to (400) with an increase in the substrate temperature from 400 degrees C to 600 degrees C, indicating thereby that the film growth direction is highly affected with nature of substrate and substrate temperature. The surface morphology of the deposited films was studied using Atomic Force Microscopy (AFM) and spherical ball like regular features of nanometer size grains were obtained. The magnetic properties were studied by Superconducting Quantum Interference Device (SQUID) magnetometer in the magnetic field +/- 6 Tesla. The magnetic field dependent magnetization (M-H) curves of all the Fe3O4 thin films measured at 5 K and 300 K show the ferrimagnetic nature. The electrochemical sensing of dopamine studied for these films shows that the film deposited on MgO substrate can be used as a sensing electrode.

Low-temperature fabrication of superconducting FeSe thin films by pulsed laser deposition

Superconducting FeSe thin films were prepared at a substrate temperature of 320 °C by pulsed laser deposition. X-ray diffraction and transmission electron microscopic analyses showed that highly c-axis-orientated and high-quality films were obtained on various substrate materials, including single-crystal MgO, LaAlO 3, SrTiO 3 and (100)-Si, and amorphous-SiO x, at such low temperature. From transport measurements all the films showed low-temperature structural phase transition at ∼ 60–90 K and superconducting transition at onset temperature varies from ∼ 7 K to < 2 K, depending on the substrate used. The transport property of FeSe film on Si was found most different from all the others, in spite of their similarity in structural analysis. Chemical analysis demonstrated that Fe and Se homogeneously distributed in the film and the stoichiometry of FeSe and the bonding states of Fe and Se are as well uniform along the film growth direction.

Interplay among helical order, surface effects, and range of interacting layers in ultrathin films

The properties of helical thin films have been thoroughly investigated by classical Monte Carlo simulations. The employed model assumes classical planar spins in a body-centered tetragonal lattice, where the helical arrangement along the film growth direction has been modeled by nearest-neighbor and next-nearest-neighbor competing interactions, the minimal requirement to get helical order. We obtain that, while the in-plane transition temperatures remain essentially unchanged with respect to the bulk ones, the helical or fan arrangement is stabilized at lower and lower temperatures when the film thickness, $n$, decreases; in the ordered phase, increasing the temperature, a softening of the helix pitch wave vector is also observed. Moreover, we show also that the simulation data around both transition temperatures lead us to exclude the presence of a first-order transition for all analyzed sizes. Finally, by comparing the results of the present work to those obtained for other models previously adopted in literature, we can get a deeper insight about the entwined role played by the number (range) of interlayer interactions and surface effects in noncollinear thin films.

Cathodoluminescence study on in composition inhomogeneity of thick InGaN layer

We have investigated the optical properties of thick InGaN film grown on GaN by cathodeluminescence (CL) spectroscopy. It is found that there is obvious In composition variation in both growth and lateral direction of InGaN film. The depth distribution of In composition is closely related to the strain relaxation process of InGaN film. Accompanied with the relaxation of compressive strain, the In composition of InGaN layer increases and the CL peak energy shifts towards red. Moreover, a rather apparent In composition fluctuation is found in the relaxed upper part of InGaN layer as confirmed by CL imaging.

Effective continuous model for surface states and thin films of three-dimensional topological insulators

Two-dimensional (2D) effective continuous models are derived for the surface states and thin films of a three-dimensional topological insulator (3DTI). Starting from an effective model for 3DTI based on first-principles calculations (Zhang et al 2009 Nat. Phys.5 438), we present solutions for both the surface states in a semi-infinite boundary condition and those in a thin film with finite thickness. The coupling between opposite topological surfaces and structure inversion asymmetry (SIA) gives rise to gapped Dirac hyperbolas with Rashba-like splittings in the energy spectrum. In addition, SIA leads to asymmetric distributions of wavefunctions for the surface states along the film growth direction, making some branches in the energy spectra much harder than others to probe by light. These features agree well with the recent angle-resolved photoemission spectra of Bi2Se3 films grown on SiC substrate (Zhang et al 2009 arXiv:0911.3706). More importantly, using the parameters fitted by experimental data, the result indicates that the thin film Bi2Se3 lies in the quantum spin Hall (QSH) region based on the calculation of the Chern number and Z2 invariant. In addition, strong SIA always tends to destroy the QSH state.

Ultrafast Deposition of Crystalline Si Films Using a High Density Microwave Plasma

AbstractA multi-pressure microwave plasma source is developed and is applied for the fast deposition of crystalline silicon films. In this paper, the plasma source is diagnosed firstly. Electron density, electron temperature and discharge gas temperature of the plasmas generated in ambient air are studied using optical emission spectroscopy (OES) method. By using the high density microwave plasma source, depositions of crystalline silicon films from SiH4+He mixture at reduced pressure conditions are investigated systematically. After optimizing the film deposition conditions, highly crystallized Si films are deposited at a rate higher than 700 nm/s. We also find that the deposited films are fully crystallized and crystalline structure of the deposited film evolves along the film growth direction, i.e. large grains in surface region while small grains in the bottom region of the film. Based on the observed results, a possible mechanism, the annealing-assisted plasma-enhanced chemical vapor deposition, is proposed to describe the film growth process.

In Situ Analysis of Dopant Incorporation, Activation, and Film Growth during Thin Film ZnO and ZnO:Al Atomic Layer Deposition

In situ characterization of low temperature atomic layer deposition (ALD) of ZnO and aluminum-doped ZnO (ZnO:Al) establishes a relationship between species adsorption, mass uptake, and surface electrical conductance during deposition and dopant atom incorporation. Conductance measured in situ during ZnO ALD oscillates with species surface adsorption, consistent with surface potential modulation and charge transfer during surface reaction. Dopant introduction using trimethylaluminum impedes both surface potential modulation and film growth, and a reaction scheme involving surface proton exchange complexes is presented to understand the observed results. Electronically active doping is achieved only after Al species transition four to five monolayers into the film bulk, consistent with a nonuniform dopant atom distribution in the direction of film growth. Results have important implications in understanding relations between dopant incorporation, activation, and film growth mechanisms in atomic layer deposi...

Ferroelectric Properties of Bi3.25La0.75 Ti3O12 Thin Films Crystallized in Different N2/O2 Ambients

Bi3.25La0.75 Ti3O12 (BLT) ferroelectric thin films are deposited by sol-gel method and annealed for crystallizaion in total 1sccm N2/O2 mixed gas with various ratio at 750°C for 30 min. The effect of crystallization ambient on the structural and ferroelectric properties of the BLT films is studied. The growth direction and grain size of BLT film are revealed to affect ferroelectric properties. After the BLT film is annealed in 20% O2, the largest Pr value is obtained, which is ascribed to an increase of random orientation and large grain size. The fatigue property is improved with the concentration of oxygen in the ambient increasing, which is ascribed to annealing in the ambient with high concentrated oxygen adequately decreasing the defects related to lack of oxygen.

Effect of Pyrolysis Atmosphere on Ferroelectric Properties of Bi3.25La0.75Ti3O12 Films Prepared by Sol-Gel Method

The effect of pyrolysis atmosphere is investigated for Bi3.25La0.75 Ti3 O12 (BLT) films prepared on Pt/TiO2/SiO2/p-Si(100) substrates by sol-gel processes. The pyrolysis is carried out at 400° C for 20 min under air or O2 atmosphere and the successive anneal is performed at 700° C for 30 min under O2 atmosphere. The pyrolysis under O2 is enough for complete removal of organic species, however after pyrolysis under air, carbon and hydrogen atomic species as organic fragment are partly remained in the film. This incomplete removal of organic fragments affects the grain growth and cause more defects in the film or between interfaces during the annealing for the crystallization of BLT film. The growth direction and grain size of the BLT film is revealed to affect ferroelectric properties. The remanent polarization Pr for the BLT films of pyrolysis in O2 and air are measured to be 18.85 μC/cm2 and 12.56 μC/cm2, respectively. The defects degrade the fatigue property dramatically for the film of pyrolysis in air. It can be concluded that the pyrolysis is an important procedure to control ferroelectric properties.

Constructing Thin Polythiophene Film Composed of Aligned Lamellae via Controlled Solvent Vapor Treatment

Thin poly(3-butylthiophene) (P3BT) film composed of aligned lamellae attached to the edge of the original film has been achieved via a controlled solvent vapor treatment (C-SVT) method. The polarized optical microscopy operated at both single-polarization and cross-polarization modes has been used to investigate the alignment of the fiber-like lamellae. A numerical simulation method is used to quantitatively calculate angle distributions of the lamellae deviated from the film growth direction. Prepatterned P3BT film edge acts as nuclei which densely initialize subsequent crystal growth by exhausting the materials transported from the partially dissolved film. The growth of new film upon crystallization is actually a self-healing process where the two-dimensional geometric confinement is mainly responsible for this parallel alignment of P3BT crystals. The solvent vapor pressure should be carefully chosen so as to induce crystal growth but avoid liquid instability which will destroy the continuity of the film. The combination of microfabrication technique and C-SVT method provides a novel method to fabricate hierarchical structure within thin polymer film with multiscale morphology via utilizing both up-bottom and bottom-up approaches.

Characteristics of Ni films deposited on SiO 2/Si(1 0 0) and MgO(0 0 1) by direct current magnetron sputtering system with the oblique target

280 nm-thick Ni films were deposited on SiO 2/Si(1 0 0) and MgO(0 0 1) substrates at 300 K, 513 K and 663 K by a direct current magnetron sputtering system with the oblique target. The films deposited at 300 K mainly have a [1 1 0] crystalline orientation in the film growth direction. The [1 1 0]-orientation weakens and the [1 1 1]- and [1 0 0]-orientations enhance with increasing deposition temperature. The lattice constant of the Ni films is smaller than that of the Ni bulk, except for the film grown on MgO(0 0 1) at 663 K. Furthermore, as the deposition temperature increases, the lattice constant of the films grown on the SiO 2/Si(1 0 0) decreases whereas that of the films grown on the MgO(0 0 1) increases. The films deposited at 300 K and 513 K grow with columnar grains perpendicular to the substrate. For the films deposited at 663 K, however, the columnar grain structure is destroyed, i.e., an about 50 nm-thick layer consisting of granular grains is formed at the interface between the film and the substrate and then large grains grow on the layer. The Ni films deposited at 300 K consist of thin columnar grains and have many voids at the grain boundaries. The grains become thick and the voids decrease with increasing deposition temperature. The resistivity of the film decreases and the saturation magnetization increases with increasing deposition temperature.

Structural and physical properties of ZnO:Al films grown on glass by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on glass substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and grow with a c-axis orientation in the film growth direction. The films grow mainly with columnar grains perpendicular to the substrate and some granular grains also exist in the films. The film deposited at 673 K and 0.4 Pa has the largest grains whereas that prepared at 300 K and 0.4 Pa consists of the smallest grains and is porous. The films exhibit an n-type semiconducting behavior at room temperature. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity (3.40 × 10 −3 Ω cm), the highest free electron concentration (4.63 × 10 20 cm −3) and a moderate Hall mobility (4.0 cm 2 V −1 s −1). The film deposited at 300 K and 0.4 Pa has the highest resistivity and the lowest free electron concentration and Hall mobility. A temperature dependence of the resistivity reveals that the carrier transport mechanism is Mott’s variable range hopping in the temperature region below 100 K and thermally activated band conduction above 215 K. The activation energy for the film deposited at 300 K and 0.4 Pa is 41 meV and that for the other films is about 35 meV. All the films have an average optical transmittance of over 85% in the visible wavelength range. The absorption edge of the film deposited at 300 K and 0.4 Pa shifts to the longer wavelength (redshift) relative to the films prepared under the other conditions.