Pulsed laser deposition of single-crystalline Cu7In3/CuIn0.8Ga0.2Se2 core/shell nanowires

Single-crystalline Cu₇In₃/CuIn_0.8Ga_0.2Se₂ (CI/CIGS) core/shell nanowires are fabricated by pulsed laser deposition with Ni nanoparticles as catalyst. The CI/CIGS core/shell nanowires are made up of single-crystalline CI cores surrounded by single-crystalline CIGS shells. The CI/CIGS nanowires are grown at a considerably low temperature (350°C ~ 450°C) by vapor-liquid-solid mode combined with vapor-solid mode. The distribution density of the nanowires increases with the increasing of the deposition duration, and the substrate temperature determines the lengths of the nanowires. The U-V absorption spectra of the CIGS thin films with and without the CI/CIGS core/shell nanowires demonstrate that the CI/CIGS nanowires can remarkably enhance the absorption of CIGS thin films in the spectrum range of 300 to 900 nm.

PACS

61.46. + w; 61.41.e; 81.15.Fg; 81.07.b     

Reduced temperature-dependent thermal conductivity of magnetite thin films by controlling film thickness

We report on the out-of-plane thermal conductivities of epitaxial Fe₃O₄ thin films with thicknesses of 100, 300, and 400 nm, prepared using pulsed laser deposition (PLD) on SiO₂/Si substrates. The four-point probe three-omega (3-ω) method was used for thermal conductivity measurements of the Fe₃O₄ thin films in the temperature range of 20 to 300 K. By measuring the temperature-dependent thermal characteristics of the Fe₃O₄ thin films, we realized that their thermal conductivities significantly decreased with decreasing grain size and thickness of the films. The out-of-plane thermal conductivities of the Fe₃O₄ films were found to be in the range of 0.52 to 3.51 W/m · K at 300 K. For 100-nm film, we found that the thermal conductivity was as low as approximately 0.52 W/m · K, which was 1.7 to 11.5 order of magnitude lower than the thermal conductivity of bulk material at 300 K. Furthermore, we calculated the temperature dependence of the thermal conductivity of these Fe₃O₄ films using a simple theoretical Callaway model for comparison with the experimental data. We found that the Callaway model predictions agree reasonably with the experimental data. We then noticed that the thin film-based oxide materials could be efficient thermoelectric materials to achieve high performance in thermoelectric devices.     

Synthesis and characterization of single-crystalline zinc tin oxide nanowires

Crystalline zinc tin oxide (ZTO; zinc oxide with heavy tin doping of 33 at.%) nanowires were first synthesized using the electrodeposition and heat treatment method based on an anodic aluminum oxide (AAO) membrane, which has an average diameter of about 60 nm. According to the field emission scanning electron microscopy (FE-SEM) results, the synthesized ZTO nanowires are highly ordered and have high wire packing densities. The length of ZTO nanowires is about 4 μm, and the aspect ratio is around 67. ZTO nanowires with a Zn/(Zn + Sn) atomic ratio of 0.67 (approximately 2/3) were observed from an energy dispersive spectrometer (EDS). X-ray diffraction (XRD) and corresponding selected area electron diffraction (SAED) patterns demonstrated that the ZTO nanowire is hexagonal single-crystalline. The study of ultraviolet/visible/near-infrared (UV/Vis/NIR) absorption showed that the ZTO nanowire is a wide-band semiconductor with a band gap energy of 3.7 eV.     

Structural and nanomechanical properties of BiFeO3 thin films deposited by radio frequency magnetron sputtering

The nanomechanical properties of BiFeO₃ (BFO) thin films are subjected to nanoindentation evaluation. BFO thin films are grown on the Pt/Ti/SiO₂/Si substrates by using radio frequency magnetron sputtering with various deposition temperatures. The structure was analyzed by X-ray diffraction, and the results confirmed the presence of BFO phases. Atomic force microscopy revealed that the average film surface roughness increased with increasing of the deposition temperature. A Berkovich nanoindenter operated with the continuous contact stiffness measurement option indicated that the hardness decreases from 10.6 to 6.8 GPa for films deposited at 350°C and 450°C, respectively. In contrast, Young''s modulus for the former is 170.8 GPa as compared to a value of 131.4 GPa for the latter. The relationship between the hardness and film grain size appears to follow closely with the Hall–Petch equation.     

Ferromagnetism and optical properties of La1???x Al x FeO3 nanopowders

La_{1 − x} Al _x FeO₃ (x = 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) nanopowders were prepared by polymerization complex method. All prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectrophotometry (UV-vis). The magnetic properties were investigated using a vibrating sample magnetometer (VSM). The X-ray results of all samples show the formation of an orthorhombic phase with the second phase of α-Fe₂O₃ in doped samples. The crystallite sizes of nanoparticles decreased with increasing Al content, and they are found to be in the range of 58.45 ± 5.90 to 15.58 ± 4.64 nm. SEM and TEM images show the agglomeration of nanoparticles with average particle size in the range of 60 to 75 nm. The FT-IR spectra confirm the presence of metal oxygen bonds of O-Fe-O and Fe-O in the FeO₆ octahedra. The UV-vis spectra show strong absorption peaks at approximately 285 nm, and the calculated optical band gaps are found to be in the range of 2.05 to 2.09 eV with increasing Al content. The M-H loop of the pure sample is antiferromagnetic, whereas those of the doped samples tend to be ferromagnetic with increasing Al content. The magnetization, remanent magnetization, and coercive field of the Al-doped sample with x = 0.5 are enhanced to 1.665 emu/g, 0.623 emu/g, and 4,087.0 Oe, respectively.     

A nontoxic and low-cost hydrothermal route for synthesis of hierarchical Cu2ZnSnS4 particles

We explore a facile and nontoxic hydrothermal route for synthesis of a Cu₂ZnSnS₄ nanocrystalline material by using l-cysteine as the sulfur source and ethylenediaminetetraacetic acid (EDTA) as the complexing agent. The effects of the amount of EDTA, the mole ratio of the three metal ions, and the hydrothermal temperature and time on the phase composition of the obtained product have been systematically investigated. The addition of EDTA and an excessive dose of ZnCl₂ in the hydrothermal reaction system favor the generation of kesterite Cu₂ZnSnS₄. Pure kesterite Cu₂ZnSnS₄ has been synthesized at 180°C for 12 h from the reaction system containing 2 mmol of EDTA at 2:2:1 of Cu/Zn/Sn. It is confirmed by Raman spectroscopy that those binary and ternary phases are absent in the kesterite Cu₂ZnSnS₄ product. The kesterite Cu₂ZnSnS₄ material synthesized by the hydrothermal process consists of flower-like particles with 250 to 400 nm in size. It is revealed that the flower-like particles are assembled from single-crystal Cu₂ZnSnS₄ nanoflakes with ca. 20 nm in size. The band gap of the Cu₂ZnSnS₄ nanocrystalline material is estimated to be 1.55 eV. The films fabricated from the hierarchical Cu₂ZnSnS₄ particles exhibit fast photocurrent responses under intermittent visible-light irradiation, implying that they show potentials for use in solar cells and photocatalysis.     

Cu2ZnSnSe4 nanocrystals capped with S2? by ligand exchange: utilizing energy level alignment for efficiently reducing carrier rec ombination

In this work, we employed a convenient one-step synthesis method for synthesizing Cu₂ZnSnSe₄ (CZTSe) nanocrystals (NCs) in an excess selenium environment. This excess selenium situation enhanced the reaction of metal acetylacetonates with selenium, resulting in the burst nucleation of NCs at relatively low temperatures. The phase morphology and surface and optoelectronic properties of NCs before and after ligand exchange were discussed in depth. It was found that pure tetragonal-phase structure CZTSe NCs with approximately 1.7-eV bandgap could be synthesized. The removal of large organic molecules on CZTSe NCs after ligand exchange by S²⁻ decreased the resistivity. The bandgap of the films after ligand exchange by 550°C selenization was also decreased due to better crystallinity. For potential application in CZTSe solar cells, we constructed an energy level diagram to explain the mutual effect between the absorption layer and CdS layer. Using cyclic voltammetry (CV) measurement, we found that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of CZTSe films shifted down after ligand exchange. After energy level alignment at the CdS/CZTSe interface, a type I band alignment structure was more conveniently formed after ligand exchange. This structure acted as the barrier against injection electrons from ZnO to the CZTSe layer, and recombination would subsequently be depressed.     

Conductive and transparent multilayer films for low-temperature TiO2/Ag/SiO2 electrodes by E-beam evaporation with IAD

Conductive and transparent multilayer thin films consisting of three alternating layers (TiO₂/Ag/SiO₂, TAS) have been fabricated for applications as transparent conducting oxides. Metal oxide and metal layers were prepared by electron-beam evaporation with ion-assisted deposition, and the optical and electrical properties of the resulting films as well as their energy bounding characteristics and microstructures were carefully investigated. The optical properties of the obtained TAS material were compared with those of well-known transparent metal oxide glasses such as ZnO/Ag/ZnO, TiO₂/Ag/TiO₂, ZnO/Cu/ZnO, and ZnO/Al/ZnO. The weathering resistance of the TAS film was improved by using a protective SiO₂ film as the uppermost layer. The transmittance spectra and sheet resistance of the material were carefully measured and analyzed as a function of the layer thickness. By properly adjusting the thickness of the metal and dielectric films, a low sheet resistance of 6.5 ohm/sq and a high average transmittance of over 89% in the 400 to 700 nm wavelength regions were achieved. We found that the Ag layer played a significant role in determining the optical and electrical properties of this film.     

Valence band offset of β-Ga2O3/wurtzite GaN heterostructure measured by X-ray photoelectron spectroscopy

A sample of the β-Ga₂O₃/wurtzite GaN heterostructure has been grown by dry thermal oxidation of GaN on a sapphire substrate. X-ray diffraction measurements show that the β-Ga₂O₃ layer was formed epitaxially on GaN. The valence band offset of the β-Ga₂O₃/wurtzite GaN heterostructure is measured by X-ray photoelectron spectroscopy. It is demonstrated that the valence band of the β-Ga₂O₃/GaN structure is 1.40 ± 0.08 eV.     

Microstructure and optical properties of nanocrystalline Cu2O thin films prepared by electrodeposition

Cuprous oxide (Cu₂O) thin films were prepared by using electrodeposition technique at different applied potentials (−0.1, −0.3, −0.5, −0.7, and −0.9 V) and were annealed in vacuum at a temperature of 100°C for 1 h. Microstructure and optical properties of these films have been investigated by X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), UV-visible (vis) spectrophotometer, and fluorescence spectrophotometer. The morphology of these films varies obviously at different applied potentials. Analyses from these characterizations have confirmed that these films are composed of regular, well-faceted, polyhedral crystallites. UV–vis absorption spectra measurements have shown apparent shift in optical band gap from 1.69 to 2.03 eV as the applied potential becomes more cathodic. The emission of FL spectra at 603 nm may be assigned as the near band-edge emission.     

Growth and characterization of TiO2 nanotubes from sputtered Ti film on Si substrate

In this paper, we present the synthesis of self-organized TiO₂ nanotube arrays formed by anodization of thin Ti film deposited on Si wafers by direct current (D.C.) sputtering. Organic electrolyte was used to demonstrate the growth of stable nanotubes at room temperature with voltages varying from 10 to 60 V (D.C.). The tubes were about 1.4 times longer than the thickness of the sputtered Ti film, showing little undesired dissolution of the metal in the electrolyte during anodization. By varying the thickness of the deposited Ti film, the length of the nanotubes could be controlled precisely irrespective of longer anodization time and/or anodization voltage. Scanning electron microscopy, atomic force microscopy, diffuse-reflectance UV–vis spectroscopy, and X-ray diffraction were used to characterize the thin film nanotubes. The tubes exhibited good adhesion to the wafer and did not peel off after annealing in air at 350 °C to form anatase TiO₂. With TiO₂ nanotubes on planar/stable Si substrates, one can envision their integration with the current micro-fabrication technique large-scale fabrication of TiO₂ nanotube-based devices.     

Direct bandgap materials based on the thin films of SexTe100 ? x nanoparticles

In this study, we fabricated thin films of Se_xTe_{100 − x} (x = 0, 3, 6, 9, 12, and 24) nanoparticles using thermal evaporation technique. The results obtained by X-ray diffraction show that the as-synthesized nanoparticles have polycrystalline structure, but their crystallinity decreases by increasing the concentration of Se. They were found to have direct bandgap (E_g), whose value increases by increasing the Se content. These results are completely different than those obtained in the films of Se_xTe_{100 − x} microstructure counterparts. Photoluminescence and Raman spectra for these films were also demonstrated. The remarkable results obtained in these nanoparticles specially their controlled direct bandgap might be useful for the development of optical disks and other semiconductor devices.     

Possibility of graphene growth by close space sublimation

Carbon films on the Si/SiO₂ substrate are fabricated using modified method of close space sublimation at atmospheric pressure. The film properties have been characterized by micro-Raman and X-ray photoelectron spectroscopy and monochromatic ellipsometry methods. Ellipsometrical measurements demonstrated an increase of the silicon oxide film thickness in the course of manufacturing process. The XPS survey spectra of the as-prepared samples indicate that the main elements in the near-surface region are carbon, silicon, and oxygen. The narrow-scan spectra of C1s, Si2p, O1s regions indicate that silicon and oxygen are mainly in the SiO _x (x ≈ 2) oxide form, whereas the main component of C1s spectrum at 284.4 eV comes from the sp²-hybridized carbon phase. Micro-Raman spectra confirmed the formation of graphene films with the number of layers that depended on the distance between the graphite source and substrate.     

Cyclic durable high-capacity Sn/Cu6Sn5 composite thin film anodes for lithium ion batteries prepared by electron-beam evaporation deposition

Sn/Cu₆Sn₅ alloy composite thin films were directly prepared by electron-beam deposition for anodes of lithium ion batteries. The thin film was comprised of micro/sub-microcrystalline Sn and Cu₆Sn₅, where the polyhedral micro-sized Sn grains were uniformly dispersed in the loose Cu₆Sn₅ matrix. Lithiation reaction kinetics were confirmed to be controlled by a diffusion step and the diffusion coefficient of Li⁺ in the thin film anode was determined to be 1.91 × 10⁻⁷ cm²/s. The galvanostatic cycling behavior of Sn/Cu₆Sn₅ composite thin film anodes was studied under different conditions. Stable capacities of more than 370 mAh/g were obtained by discharging from 1.25 to 0.1 V. Structure changes and fading mechanism of the thin film electrodes was discussed based on SEM, XRD and EDX investigations. The present results demonstrated that the multi-phase composite structure can improve electrochemical performance of the Cu-Sn alloy thin film electrodes.     

In situ growth of CuInS2 nanocrystals on nanoporous TiO2 film for constructing inorganic/organic heterojunction solar cells

Inorganic/organic heterojunction solar cells (HSCs) have attracted increasing attention as a cost-effective alternative to conventional solar cells. This work presents an HSC by in situ growth of CuInS₂(CIS) layer as the photoabsorption material on nanoporous TiO₂ film with the use of poly(3-hexylthiophene) (P3HT) as hole-transport material. The in situ growth of CIS nanocrystals has been realized by solvothermally treating nanoporous TiO₂ film in ethanol solution containing InCl₃ · 4H₂O, CuSO₄ · 5H₂O, and thioacetamide with a constant concentration ratio of 1:1:2. InCl₃ concentration plays a significant role in controlling the surface morphology of CIS layer. When InCl₃ concentration is 0.1 M, there is a layer of CIS flower-shaped superstructures on TiO₂ film, and CIS superstructures are in fact composed of ultrathin nanoplates as ‘petals’ with plenty of nanopores. In addition, the nanopores of TiO₂ film are filled by CIS nanocrystals, as confirmed using scanning electron microscopy image and by energy dispersive spectroscopy line scan analysis. Subsequently, HSC with a structure of FTO/TiO₂/CIS/P3HT/PEDOT:PSS/Au has been fabricated, and it yields a power conversion efficiency of 1.4%. Further improvement of the efficiency can be expected by the optimization of the morphology and thickness of CIS layer and the device structure.     

Si-rich Al2O3 films grown by RF magnetron sputtering: structural and photoluminescence properties versus annealing treatment

Silicon-rich Al₂O₃ films (Si_x(Al₂O₃)_1−x) were co-sputtered from two separate silicon and alumina targets onto a long silicon oxide substrate. The effects of different annealing treatments on the structure and light emission of the films versus x were investigated by means of spectroscopic ellipsometry, X-ray diffraction, micro-Raman scattering, and micro-photoluminescence (PL) methods. The formation of amorphous Si clusters upon the deposition process was found for the films with x ≥ 0.38. The annealing treatment of the films at 1,050°C to 1,150°C results in formation of Si nanocrystallites (Si-ncs). It was observed that their size depends on the type of this treatment. The conventional annealing at 1,150°C for 30 min of the samples with x = 0.5 to 0.68 leads to the formation of Si-ncs with the mean size of about 14 nm, whereas rapid thermal annealing of similar samples at 1,050°C for 1 min showed the presence of Si-ncs with sizes of about 5 nm. Two main broad PL bands were observed in the 500- to 900-nm spectral range with peak positions at 575 to 600 nm and 700 to 750 nm accompanied by near-infrared tail. The low-temperature measurement revealed that the intensity of the main PL band did not change with cooling contrary to the behavior expected for quantum confined Si-ncs. Based on the analysis of PL spectrum, it is supposed that the near-infrared PL component originates from the exciton recombination in the Si-ncs. However, the most intense emission in the visible spectral range is due to either defects in matrix or electron states at the Si-nc/matrix interface.     

A facile approach to synthesize SiO2?·?Re2O3 (Re?=?Y,Eu, La,Sm, Tb,Pr) hollow sphere and its application in drug release

Multifunctional SiO₂ · Re₂O₃ (Re = Y, Eu, La, Sm, Tb, Pr) hollow spheres (HSs) have been fabricated using an acidic Re³⁺ ion solution. Under ultraviolet radiation, functional HSs emit different colors of light according to the different rare-earth ions embedded into the shell of SiO₂ hollow spheres. The as-prepared hollow capsules were characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, Brunauer-Emmett-Teller method, scanning electron microscopy, and energy-dispersive spectrometry. Drug loading and release experiments have been carried out using SiO₂ · Eu₂O₃ HSs that acted as drug carriers. The results demonstrate that the multifunctional HSs exhibit a high storage capacity and the ability of retaining drug stability and activity, which indicates that the as-synthesized fluorescent hollow capsules are a potential candidate as drug delivery materials.     

Optical and microstructural properties of ZnO/TiO2 nanolaminates prepared by atomic layer deposition

ZnO/TiO₂ nanolaminates were grown on Si (100) and quartz substrates by atomic layer deposition at 200°C using diethylzinc, titanium isopropoxide, and deionized water as precursors. All prepared multilayers are nominally 50 nm thick with a varying number of alternating TiO₂ and ZnO layers. Sample thickness and ellipsometric spectra were measured using a spectroscopic ellipsometer, and the parameters determined by computer simulation matched with the experimental results well. The effect of nanolaminate structure on the optical transmittance is investigated using an ultraviolet–visible-near-infrared spectrometer. The data from X-ray diffraction spectra suggest that layer growth appears to be substrate sensitive and film thickness also has an influence on the crystallization of films. High-resolution transmission electron microscopy images show clear lattice spacing of ZnO in nanolaminates, indicating that ZnO layers are polycrystalline with preferred (002) orientation while TiO₂ layers are amorphous.     

Enhanced resistive switching memory characteristics and mechanism using a Ti nanolayer at the W/TaOx interface

Enhanced resistive memory characteristics with 10,000 consecutive direct current switching cycles, long read pulse endurance of >10⁵ cycles, and good data retention of >10⁴ s with a good resistance ratio of >10² at 85°C are obtained using a Ti nanolayer to form a W/TiO_x/TaO_x/W structure under a low current operation of 80 μA, while few switching cycles are observed for W/TaO_x/W structure under a higher current compliance >300 μA. The low resistance state decreases with increasing current compliances from 10 to 100 μA, and the device could be operated at a low RESET current of 23 μA. A small device size of 150 × 150 nm² is observed by transmission electron microscopy. The presence of oxygen-deficient TaO_x nanofilament in a W/TiO_x/TaO_x/W structure after switching is investigated by Auger electron spectroscopy. Oxygen ion (negative charge) migration is found to lead to filament formation/rupture, and it is controlled by Ti nanolayer at the W/TaO_x interface. Conducting nanofilament diameter is estimated to be 3 nm by a new method, indicating a high memory density of approximately equal to 100 Tbit/in.².     

Effect of annealing temperature on wettability of TiO2 nanotube array films

Highly ordered TiO₂ nanotube array (TN) films were prepared by anodization of titanium foil in a mixed electrolyte solution of glycerin and NH₄F and then annealed at 200°C, 400°C, 600°C, and 800°C, respectively. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), water contact angle (WCA), and photoluminescence (PL). It was found that low temperature (below 600°C) has no significant influence on surface morphology, but the diameter of the nanotube increases from 40 to 50 nm with increasing temperature. At 800°C, the nanotube arrays are completely destroyed and only dense rutile film is observed. Samples unannealed and annealed at 200°C are amorphous. At 400°C, anatase phase appears. At 600°C, rutile phase appears. At 800°C, anatase phase changes into rutile phase completely. The wettability of the TN films shows that the WCAs for all samples freshly annealed at different temperatures are about 0°. After the annealed samples have been stored in air for 1 month, the WCAs increase to 130°, 133°, 135°, 141°, and 77°, respectively. Upon ultraviolet (UV) irradiation, they exhibit a significant transition from hydrophobicity to hydrophilicity. Especially, samples unannealed and annealed at 400°C show high photoinduced hydrophilicity.