Growth kinetics of vanadium pentoxide nanostructures under hydrothermal conditions

The work reported here involved a study of the growth kinetics of V₂O₅nH₂O nanostructures under hydrothermal conditions. The coarsening process of V₂O₅nH₂O nanoribbons was followed by subjecting the as-prepared suspensions to hydrothermal treatments at 80 °C for periods ranging from 0 to 7200 min. X-ray diffraction (XRD) confirms that the hydrothermal treatments at 80 °C caused no significant modification of the long-range order structure of samples subjected to different periods of hydrothermal treatment. Field emission scanning transmission electron microscope (FE-STEM) was used to analyze the morphology and width distribution of the nanostructures. The results indicated that the crystal growth mechanism in the [1 0 0] direction of vanadium pentoxide 1D nanostructure under hydrothermal conditions is well described by the oriented attachment (OA) mechanism. This evidence was supported by HRTEM images showing the existence of defects at the interface between nanostructures, which is characteristic of the oriented attachment (OA) mechanism.     

Growth and microstructural features of laser ablated LiCoO2 thin films

Thin films of LiCoO₂ were prepared by pulsed laser deposition technique and the properties were studied in relation to the deposition parameters. The films deposited from a sintered composite target (LiCoO₂+Li₂O) in an oxygen partial pressure of 100 mTorr and at a substrate temperature of 300 °C exhibited preferred c-axis (0 0 3) orientation perpendicular to the substrate surface. The AFM data demonstrated that the films are composed of uniform distribution of fine grains with an average grain size of 80 nm. The grain size increased with an increase in substrate temperature. The (0 0 3) orientation decreased with increase in (1 0 4) orientation for the films deposited at higher substrate temperatures (>500 °C) indicating that the films’ growth is parallel to the substrate surface. The composition of the experimental films was analyzed using X-ray photoelectron spectroscopy (XPS). The binding energy peaks of Co(2p_3/2) and Co(2p_1/2) are, respectively, observed at 779.3 and 794.4 eV, which can be attributed to the Co³⁺ bonding state of LiCoO₂. The electrochemical measurements were carried out on Li//LiCoO₂ cells with a lithium metal foil as anode and LiCoO₂ film as cathode of 1.5 cm² active area using a Teflon home-made cell hardware. The Li//LiCoO₂ cells were tested in the potential range 2.6-4.2 V. Specific capacity as high as 205 mC/cm² μm was measured for the film grown at 700 °C. The growth of LiCoO₂ films were studied in relation to the deposition parameters for their effective utilization as cathode materials in solid-state microbattery application.     

In-situ cyclic pulse annealing of InN on AlN/Si during IR-lamp-heated MBE growth

To improve crystal quality of InN, an in-situ cyclic rapid pulse annealing during growth was carried out using infrared-lamp-heated molecular beam epitaxy. A cycle of 4 min growth of InN at 400 °C and 3 s pulse annealing at a higher temperature was repeated 15 times on AlN on Si substrate. Annealing temperatures were 550, 590, 620, and 660 °C. The back of Si was directly heated by lamp irradiation through a quartz rod. A total InN film thickness was about 200 nm. With increasing annealing temperature up to 620 °C, crystal grain size by scanning electron microscope showed a tendency to increase, while widths of X-ray diffraction rocking curve of (0 0 0 2) reflection and E₂ (high) mode peak of Raman scattering spectra decreased. A peak of In (1 0 1) appeared in X-ray diffraction by annealing higher than 590 °C, and In droplets were found on the surface by annealing at 660 °C.     

Structure and growth morphology of Gd2O3-doped CeO2 thin films

Gd₂O₃-doped CeO₂ (Gd_0.1Ce_0.9O_1.95, GDC) thin films were synthesized on (1 0 0) Si single crystal substrates by a reactive radio frequency magnetron sputtering technique. Structures and surface morphologies were characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and one-dimensional power spectral density (1DPSD) analysis. The XRD patterns indicated that, in the temperature range of 200–700 °C, f.c.c. structured GDC thin films were formed with growth orientations varying with temperature—random growth at 200 °C, (2 2 0) textures at 300–600 °C and (1 1 1) texture at 700 °C. GDC film synthesized at 200 °C had the smoothest surface with roughness of R_rms=0.973 nm. Its 1DPSD plot was characterized with a constant part at the low frequencies and a part at the high frequencies that could be fitted by the f^−2.4 power law decay. Such surface feature and scaling behavior were probably caused by the high deposition rate and random growth in the GDC film at this temperature. At higher temperatures (300–700 °C), however, an intermediate frequency slope (−γ₂≈−2) appeared in the 1DPSD plots between the low frequency constant part and the high frequency part fitted by f⁻⁴ power law decay, which indicated a roughing mechanism dominated by crystallographic orientation growth that caused much rougher surfaces in GDC films (R_rms>4 nm).     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Influence of annealing on the physical properties of filtered vacuum arc deposited tin oxide thin films

Tin oxide (SnO₂) thin films were deposited on UV fused silica (UVFS) substrates using filtered vacuum arc deposition (FVAD). During deposition, the substrates were at room temperature (RT). As-deposited films were annealed at 400 and 600 °C in Ar for 30 min. The film structure, composition, and surface morphology were determined as function of the annealing temperature using X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The XRD patterns of the SnO₂ thin films deposited on substrates at RT indicated that the films were amorphous, however, after the annealing the film structure became polycrystalline. The grain size of the annealed films, obtained from the XRD analysis, increased with the annealing temperature, and it was in the range 8-34 nm. The AFM analysis of the surface revealed an increase in the film surface average grain size from 15 nm to 46 nm, and the surface roughness from 0.2 to 1.8 nm, as function of the annealing temperature. The average optical transmission of the films in the visible spectrum was >80%, and increased by the annealing ∼10%. The films’ optical constants in the 250-989 nm wavelength range were determined by variable angle spectroscopic ellipsometry (VASE). The refractive indexes of as-deposited and annealed films were in the range 1.83-2.23 and 1.85-2.3, respectively. The extinction coefficients, k(λ), of as-deposited and annealed films were in the range same range ∼0-0.5. The optical energy band gap (E_g), as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths, increased with the annealing temperature from 3.90 to 4.35 eV. The lowest electrical resistivity of the as-deposited tin oxide films was 7.8 × 10⁻³ Ω cm, however, film annealing resulted in highly resistive films.     

Sublimation crystal growth of yttrium nitride

The sublimation–recombination crystal growth of bulk yttrium nitride crystals is reported. The YN source material was prepared by reacting yttrium metal with nitrogen at 1200 °C and 800 Torr total pressure. Crystals were produced by subliming this YN from the source zone, and recondensing it from the vapor as crystals at a lower temperature (by 50 °C). Crystals were grown from 2000 to 2100 °C and with a nitrogen pressure from 125 to 960 Torr. The highest rate was 9.64×10⁻⁵ mol/h (9.92 mg/h). The YN sublimation rate activation energy was 467.1±21.7 kJ/mol. Individual crystals up to 200 μm in dimension were prepared. X-ray diffraction confirmed that the crystals were rock salt YN, with a lattice constant of 4.88 Å. The YN crystals were unstable in air; they spontaneously converted to yttria (Y₂O₃) in 2–4 h. A small fraction of cubic yttria was detected in the XRD of a sample exposed to air for a limited time, while non-cubic yttria was detected in the Raman spectra for a sample exposed to air for more than 1 h.     

The effects of annealing on non-polar (1 1 2¯ 0) a-plane GaN films

Non-polar a-plane (1 1 2¯ 0) GaN films were grown on r-plane sapphire by metal–organic vapor phase epitaxy and were subsequently annealed for 90 min at 1070 °C. Most dislocations were partial dislocations, which terminated basal plane stacking faults. Prior to annealing, these dislocations were randomly distributed. After annealing, these dislocations moved into arrays oriented along the [0 0 0 1] direction and aligned perpendicular to the film–substrate interface throughout their length, although the total dislocation density remained unchanged. These changes were accompanied by broadening of the symmetric X-ray diffraction 1 1 2¯ 0 ω-scan widths. The mechanism of movement was identified as dislocation glide, occurring due to highly anisotropic stresses (confirmed by X-ray diffraction lattice parameter measurements) and evidenced by macroscopic slip bands observed on the sample surface. There was also an increase in the density of unintentionally n-type doped electrically conductive inclined features present at the film–substrate interface (as observed in cross-section using scanning capacitance microscopy), suggesting out-diffusion of impurities from the substrate along with prismatic stacking faults. These data suggest that annealing processes performed close to film growth temperatures can affect both the microstructure and the electrical properties of non-polar GaN films.     

Large-scale synthesis of ZnSe nanoribbons on zinc substrate

ZnSe nanoribbons have been successfully synthesized on a large scale by solvothermal treatment of Zn and Se powder in the mixture of hydrazine hydrate and diethanolamine at 140 °C for 24 h and subsequent annealing in Ar. The morphology of the final products strongly depended on the volume ratio of hydrazine hydrate and diethanolamine. Scanning electron microscopy (SEM) explorations indicated that the as-prepared ZnSe nanoribbons were mostly about 40 nm in thickness, 100 nm in width, and 50 μm in length. X-ray diffraction pattern (XRD) and transmission electron microscopy (TEM) investigations confirmed that resulting ZnSe nanoribbons are wurtzite structures and have a [0 0 1] growth direction. PL (photoluminescence) spectrum of the products exhibited a visible light emission. Based on these investigations, the products were expected to find wide applications in optoelectronic, field emission and catalytic fields.     

The effect of thermal annealing on the structural and mechanical properties of a-C:H thin films prepared by the CFUBM magnetron sputtering method

a-C:H films were prepared by closed-field unbalanced magnetron (CFUBM) sputtering on silicon substrates using argon (Ar) and acetylene (C₂H₂) gases, and the effects of post-annealing temperature on structural and mechanical properties were investigated. Films were annealed at temperatures ranging from 300 °C to 700 °C in increments of 200 °C using rapid thermal annealing equipment in vacuum ambient. Variations in microstructure were examined using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Surface and mechanical properties were investigated by atomic force microscopy (AFM), nano-indentation, residual stress tester, and nano-scratch tester. We found that the mechanical properties of a-C:H films deteriorated with increased annealing temperature.     

Growth of GaN films on PLD-deposited TaC substrates

GaN films were grown by metal organic chemical vapor deposition on TaC substrates that were created by pulsed laser deposition of TaC onto (0 0 0 1) SiC substrates at ∼1000 °C. This was done to determine if good quality TaC films could be grown, and if good quality GaN films could be grown on this closely lattice matched to GaN, conductive material. This was done by depositing the TaC on on-axis and 3° or 8° off-axis (0 0 0 1) SiC at temperatures ranging from 950 to 1200 °C, and examining them using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The GaN films were grown on as-deposited TaC films, and films annealed at 1200, 1400, or 1600 °C, and examined using the same techniques. The TaC films were polycrystalline with a slight (1 1 1) texture, and the grains were ∼200 nm in diameter. Films grown on-axis were found to be of higher quality than those grown on off-axis substrates, but the latter could be improved to a comparable quality by annealing them at 1200–1600 °C for 30 min. TaC films deposited at temperatures above 1000 °C were found to react with the SiC. GaN films could be deposited onto the TaC when the surface was nitrided with NH₃ for 3 min at 1100 °C and the low temperature buffer layer was AlN. However, the GaN did not nucleate easily on the TaC film, and the crystallites did not have the desired (0 0 0 1) preferred orientation. They were ∼10 times larger than those typically seen in films grown on SiC or sapphire. Also the etch pit concentration in the GaN films grown on the TaC was more than 2 orders of magnitude less than it was for growth on the SiC.     

A catalyst-free method to silicon nanowires at relative low temperature

Well-crystallized straight Si nanowires (SiNWs) were successfully prepared in large scale via a facile reaction between NaN₃ and Na₂SiF₆ at 600 °C without using any catalyst. Characterization by X-ray powder diffraction and transmission electron microscopy demonstrates that the as-obtained product is pure-phase cubic SiNWs with diameters of 40 nm or so, and lengths of several micrometers. And the SiNWs with spherical tips can be obtained at a temperature as low as 300 °C. Heating temperature and holding time have crucial influence on the synthesis and morphology of the SiNWs. An oxide-assisted growth mechanism is responsible for the formation of the SiNWs.     

Fabrication and characterization of GaAs quantum well buried in AlGaAs/GaAs heterostructure nanowires

We developed a growth method for forming a GaAs quantum well contained in an AlGaAs/GaAs heterostructure nanowire using selective-area metal organic vapor phase epitaxy. To find the optimum growth condition of AlGaAs nanowires, we changed the growth temperature between 800 and 850 °C and found that best uniformity of the shape and the size was obtained near 800 °C but lateral growth of AlGaAs became larger, which resulted in a wide GaAs quantum well grown on the top (1 1 1)B facet of the AlGaAs nanowire. To form the GaAs quantum well with a reduced lateral size atop the AlGaAs nanowire, a GaAs core nanowire about 100 nm in diameter was grown before the AlGaAs growth, which reduced the lateral size of AlGaAs to roughly half compared with that without the GaAs core. Photoluminescence measurement at 4.2 K indicated spectral peaks of the GaAs quantum wells about 60 meV higher than the acceptor-related recombination emission peak of GaAs near 1.5 eV. The photoluminescence peak energy showed a blue shift of about 15 meV, from 1.546 to 1.560 eV, as the growth time of the GaAs quantum well was decreased from 8 to 3 s. Transmission electron microscopy and energy dispersive X-ray analysis of an AlGaAs/GaAs heterostructure nanowire indicated a GaAs quantum well with a thickness of 5−20 nm buried along the 〈1 1 1〉 direction between the AlGaAs shells, showing a successful fabrication of the GaAs quantum well.     

Growth of hexagonal and cubic InN nanowires using MOCVD with different growth temperatures

We have performed a detailed investigation of the metal-organic chemical vapor deposition (MOCVD) growth and characterization of InN nanowires formed on Si(1 1 1) substrates under nitrogen rich conditions. The growth of InN nanowires has been demonstrated by using an ion beam sputtered (∼10 nm) Au seeding layer prior to the initiation of growth. We tried to vary the growth temperature and pressure in order to obtain an optimum growth condition for InN nanowires. The InN nanowires were grown on the Au+In solid solution droplets caused by annealing in a nitrogen ambient at 700 °C. By applying this technique, we have achieved the formation of InN nanowires that are relatively free of dislocations and stacking faults. Scanning electron microscopy (SEM) showed wires with diameters of 90–200 nm and lengths varying between 3 and 5 μm. Hexagonal and cubic structure is verified by high resolution X-ray diffraction (HR-XRD) spectrum. Raman measurements show that these wurtzite InN nanowires have sharp peaks E₂ (high) at 491 cm⁻¹ and A₁ (LO) at 591 cm⁻¹.     

Influence of hydrogen on structural and optical properties of low temperature polycrystalline Ge films deposited by RF magnetron sputtering

To improve the properties of polycrystalline Ge thin films, which are a candidate material for the bottom cells of low cost monolithic tandem solar cells, ∼300 nm in situ hydrogenated Ge (Ge:H) thin films were deposited on silicon nitride coated glass by radio-frequency magnetron sputtering. The films were sputtered in a mixture of 15 sccm argon and 10 sccm hydrogen at a variety of low substrate temperatures (T_s)≤450 °C. Structural and optical properties of the Ge:H thin films were measured and compared to those of non-hydrogenated Ge thin films deduced in our previous work. Raman and X-ray diffraction spectra revealed a structural evolution from amorphous to crystalline phase with increase in T_s. It is found that the introduction of hydrogen gas benefits the structural properties of the polycrystalline Ge film, sputtered at 450 °C, although the onset crystallization temperature is ∼90 °C higher than in those sputtered without hydrogen. Compared with non-hydrogenated Ge thin films, hydrogen incorporated in the films leads to broadened band gaps of the films sputtered at different T_s.     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

Improvement in crystallinity and optical properties of ZnO epitaxial layers by thermal annealed ZnO buffer layers with oxygen plasma

ZnO epitaxial layers with treated low-temperature (LT) ZnO buffer layers were grown by plasma-assisted molecular beam epitaxy (PA-MBE) on p-type Si (1 0 0) substrates. The LT-ZnO buffer layers were treated by thermal annealing in O₂ plasma with various radio frequency (RF) power ranging from 100 to 300 W before the ZnO epilayers growth. Atomic force microscopy (AFM), high-resolution X-ray diffraction (HR-XRD), and room-temperature (RT) photoluminescence (PL) were carried out to investigate their structural and optical properties. The surface roughness measured by AFM was improved from 2.71 to 0.59 nm. The full-width at half-maximum (FWHM) of the rocking curve observed for ZnO (0 0 2) XRD and photoluminescence of the ZnO epilayers was decreased from 0.24° to 0.18° and from 232 to 133 meV, respectively. The intensity of the XRD rocking curve and the PL emission peak were increased. The XRD intensity ratio of the ZnO (0 0 2) to Si substrates and PL intensity ratio of the near-band edge emissions (NBEE) to the deep-level emissions (DLE) as a function of the RF power was increased from 0.166 to 0.467 and from 2.54 to 4.01, respectively. These results imply that the structural and optical properties of ZnO epilayers were improved by the treatment process.     

Ammonothermal epitaxy of wurtzite GaN using an NH4I mineralizer

Purely wurtzite phase needle crystals and epitaxial layers of GaN were grown by the ammonothermal method using an NH₄I mineralizer. The inclusion of zincblende phase GaN was effectively eliminated by increasing the growth temperature higher than 500 °C. Accordingly, an approximately 20-μm-thick GaN epitaxial layer was achieved on the Ga-polar face of a c-plane GaN seed wafer at 520 °C. Although the characteristic deep state emission band dominated the room temperature photoluminescence spectrum, the near-band-edge emission of GaN was observed for both the needle crystals and the epitaxial layers. These results encourage one to grow better quality GaN crystals at a high growth rate under high-temperature growth conditions.     

Thermal stability of thin InGaN films on GaN

The thermal stability of ∼200-nm-thick InGaN thin films on GaN was investigated using isothermal and isochronal post-growth anneals. The In_xGa_1−xN films (x=0.08–0.18) were annealed in N₂ at 600–1000 °C for 15–60 min, and the resulting film degradation was monitored using X-ray diffraction (XRD) and photoluminescence (PL) measurements. As expected, films with higher indium concentration showed more evidence for decomposition than the samples with lower indium concentration. Also for each alloy composition, decreases in the PL intensity were observed starting at much lower temperatures compared to decreases in the XRD intensity. This difference in sensitivity of the PL and XRD techniques to the InGaN decomposition suggest that defects that quench luminescence are generated prior to the onset of structural decomposition. For the higher indium concentration films, the bulk decomposition proceeds by forming metallic indium and gallium regions as observed by XRD. For the 18% indium concentration film, measurement of the temperature-dependent InGaN decomposition yields an activation energy, E_A, of 0.87±0.07 eV, which is similar to the E_A for bulk InN decomposition. The InGaN integrated XRD signal of the 18% film displays an exponential decrease vs. time, implying InGaN decomposition proceeds via a first-order reaction mechanism.