Synthesis and characterization of GaN nanowires by a catalyst assisted chemical vapor deposition

GaN nanowires have been fabricated on Si(1 1 1) substrates by chemical vapor deposition (CVD) method with NiCl₂ as catalyst and their compositions, microstructures, morphologies and light emitting properties were characterized by X-ray diffraction (XRD), FT-IR spectrophotometer (FTIR), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), Raman spectroscopy and photoluminescence (PL). The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 20-50 nm in diameter and several tens of microns in length with some nano-droplets on their tips, which reveals that the growth mechanism of GaN nanowires agrees with vapor-liquid-solid (VLS) process. Five first-order Raman active phonon bands move to low shift and A₁(TO), E₁(TO), and E₂ (high) bands are overlapped and broaden, which is caused by uncertainty in the phonon wave vector. Five non-first-order active Raman phonons also appear, which is caused by the small dimension and high surface disorder degree. A blue-shift of the band-gap emission occurs due to quantum confinement effect.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

E(transverse optical)-mode properties in the LiTaO3: Nd crystal at room temperature

E(TO)-mode properties in LiTaO₃:Nd crystal were examined by analyzing the Raman spectra measured.E(TO) modes appear in the transverseA ₁ spectrum. Their intensities obviously increase in theE andE+A ₁ mixed-symmetry spectra but decrease in theE spectrum which shows new vibrational modes. In particular, in the transverse-E spectrum of y(xz) geometry, the properties ofE(TO) modes are similar to those of pure LiTaO₃ of the same geometry, whereas in the transverse-E spectrum in x(yz) geometry these modes are turned intoA ₁ (TO) modes. We attribute these properties to both the surface strain produced by mechanical polishing of the sample and the microstructural change of the LiTaO₃ crystal resulting from Nd doping.     

Hydrothermal synthesis of chalcopyrite CuInS2, CuInSe2 and CuInTe2 nanocubes and their characterization

CuInS₂, CuInSe₂ and CuInTe₂ nanocubes of chalcopyrite structure have been successfully synthesized by hydrothermal process using deionized water as solvent at 180 °C for 20 h. The crystallinity, compositional, morphological and optical properties of the synthesized samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), Raman and photoluminescence (PL) spectra analyses. The Raman spectra of the synthesized CuInS₂, CuInSe₂ and CuInTe₂ samples show the dominant A₁ modes at 293, 172 and 121 cm⁻¹ respectively. The possible chemical reaction and mechanism of nanocubes formation were discussed. The emission wavelength of as synthesized CuInS₂, CuInSe₂ and CuInTe₂ samples were blue shifted at 746 nm (1.66 eV), 863 nm (1.43 eV) and 859 nm (1.44 eV) respectively.     

Photoluminescence studies of ZnO thin films on R-plane sapphire substrates grown by sol–gel method

Zinc oxide (ZnO) thin films on R-plane sapphire substrates were grown by the sol–gel spin-coating method. The optical properties of the ZnO thin films were investigated using photoluminescence. In the UV range, the asymmetric near-band-edge emission was observed at 300 K, which consisted of two emissions at 3.338 and 3.279 eV. Eight peaks at 3.418, 3.402, 3.360, 3.288, 3.216, 3.145, 3.074, and 3.004 eV, which respectively correspond to the free exciton (FX), bound exciton, transverse optical (TO) phonon replica of FX recombination, and first-order longitudinal optical phonon replica of FX and the TO (1LO+TO), 2LO+TO, 3LO+TO, 4LO+TO, and 5LO+TO, were obtained at 12 K. From the temperature-dependent PL, it was found that the emission peaks at 3.338 and 3.279 eV corresponded to the FX and TO, respectively. The activation energy of the FX and TO emission peaks was found to be about 39.3 and 28.9 meV, respectively. The values of the fitting parameters of Varshni's empirical equation were α=4×10^?3 eV/K and β=4.9×10³ K, and the S factor of the ZnO thin films was 0.658. With increasing temperature, the exciton radiative lifetime of the FX and TO emissions increased. The temperature-dependent variation of the exciton radiative lifetime for the TO emission was slightly higher than that for the FX emission.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

Structural modifications of GaN after cerium implantation

Among the family of rare earth (RE) dopants, the doping of first member Ce into GaN is the least studied system. This article reports structure properties of Ce‐doped GaN realized by technique of ion implantation. Ce ions were implanted into metal organic chemical vapor deposition grown n‐ and p‐GaN/sapphire thin films at doses 3 × 10¹⁴ and 2 × 10¹⁵ cm⁻². X‐ray diffraction scans and Raman scattering measurements exhibited expansion of lattice in the implanted portion of the samples. First order Raman scattering spectra show appearance of several disorder‐activated Raman scattering modes in addition to typical GaN features. A dose‐dependent decrease in intensity of E₂ mode was observed in Raman the spectra of the implanted samples. Ultraviolet Raman spectra of implanted samples show complete quenching of photoluminescence emission and appearance of multiple A₁(LO) phonon scattering modes up to fifth order. Moreover, a decrease in intensity and an increase in line width of LO modes as a function of wavenumber were observed for implanted samples. Copyright © 2012 John Wiley & Sons, Ltd.     

Study on the relationships between Raman shifts and temperature range for a-plane GaN using temperature-dependent Raman scattering

In this paper, Raman shifts of a-plane GaN layers grown on r-plane sapphire substrates by low-pressure metal-organic chemical vapor deposition (LPMOCVD) are investigated. We compare the crystal qualities and study the relationships between Raman shift and temperature for conventional a-plane GaN epilayer and insertion AlN/AlGaN superlattice layers for a-plane GaN epilayer using temperature-dependent Raman scattering in a temperature range from 83 K to 503 K. The temperature-dependences of GaN phonon modes (A₁ (TO), E₂ (high), and E₁ (TO)) and the linewidths of E₂ (high) phonon peak are studied. The results indicate that there exist two mechanisms between phonon peaks in the whole temperature range, and the relationship can be fitted to the pseudo-Voigt function. From analytic results we find a critical temperature existing in the relationship, which can characterize the anharmonic effects of a-plane GaN in different temperature ranges. In the range of higher temperature, the relationship exhibits an approximately linear behavior, which is consistent with the analyzed results theoretically.     

Hydrothermal growth of ZnO on annealed electrodeposited titanate film: Influence of zinc nitrate and methenamine

Hydrothermal growth of hexagonal ZnO nanorods on the annealed titanate nanotube films is reported as a function of molar ratio of Zn(NO₃)₂ and methenamine (1:1-1:4). The molar ratio of 1:4 results in a dense and thinner rod in comparison with other molar ratios. Corn-like structures of the rods are believed to be due to the higher amine concentration. Raman peaks at 437 and 331 cm⁻¹ are assigned to E₂ and E_2H-E_2L modes. Near band gap edge and green photoluminescence emission indicates the structural and oxygen vacancy. O 1s peak is found built-up of sub-peaks at 530.62, 531.8 and 532.84 eV corresponding to O²⁻ on normal wurtzite structure and OH and oxygen vacancies of ZnO, respectively.     

六方相InGaN外延膜的显微Raman散射

用X射线衍射(XRD)技术和显微Raman散射方法对金属有机化学气相沉积(MOCVD)法生长的六方相In_xGa_1-xN薄膜样品进行了研究，观察到了相分离现象和LO声子-等离子耦合模(LPP⁺)，讨论了In_xGa_1-xN的A₁(LO)模被屏蔽的主要物理机制.同时，对Raman谱中E₂和A₁(TO)声子模进行了分析和讨论.在In_xGa_1-xN样品的低温Raman谱中还观察到单电子跃迁产生的Raman散射信号. 关键词： Raman散射 X射线衍射 相分离 应力 LO声子-等离子耦合     

Anionic polymerization in Co and Fe doped ZnO: Nanorods,magnetism and photoactivity

The growth mechanism of Zn_1−xCo_xO (ZC) and Zn_1−xFe_xO (ZF) nanorods, and resulting magnetic and optical properties have been studied. The ZC and ZF nanorods were prepared by sol–gel synthesis route. X-ray diffraction results in polycrystalline phase with wurtzite structure of ZC and ZF nanorods. The transmission electron microscopy images show the formation of nanorods. The growth mechanism of nanorods is explained on the basis of agglomeration of Zn²⁺ with OH⁻ ions which is react with poly vinyl alcohol involve anionic polymerization of oriented growth. Magnetic measurement of ZC and ZF nanorods exhibit superferromagnetic behavior and the large value of saturation magnetization observed at room temperature. The magnetization below room temperature measurement confirms the origin of observed magnetism. Raman and photoluminescence spectra show good photoactivity. The observed Raman active modes show wurtzite structure belongs to C_6v symmetry group. Photoluminescence measurements of ZC and ZF nanorods exhibit ultraviolet peaks at 413.90 nm (∼3 eV) due to free exciton emission and at 546.31 nm (∼2.27 eV) due to transition from deep donor states which arises from oxygen vacancy.     

On the mixed nature of the 740 cm band in wurtzite GaN films: A polarized Raman scattering investigation

A detailed study of the polarized Raman scattering of wurtzite GaN films is presented, focusing on the nature of the band centered at 740 cm⁻¹ observed in the X(Z, Z)X configuration. The origin of this band is ascribed to the mixed contribution of the A₁ and E₁ longitudinal phonon modes coupled with the free carrier excitation. The spectral profile of the 740 cm⁻¹ Raman band has been successfully reconstructed through a linear combination of the A₁-E₁ longitudinal phonon plasmon-coupled modes, leading to a free carrier concentration in good agreement with Hall effect measurements.     

First order Raman scattering analysis of transition metal ions implanted GaN

Transition Metal (TM) ions V, Cr, Mn and Co were implanted into GaN/sapphire films at fluences 5×10¹⁴, 5×10¹⁵ and 5×10¹⁶ cm⁻². First order Raman Scattering (RS) measurements were carried out to study the effects of ion implantation on the microstructure of the materials, which revealed the appearance of disorder and new phonon modes in the lattice. The variations in characteristic modes 1GaN i.e. E₂(high) and A₁(LO), observed for different implanted samples is discussed in detail. The intensity of nitrogen vacancy related vibrational modes appearing at 363 and 665 cm⁻¹ was observed for samples having different fluences. A gallium vacancy related mode observed at 277/281 cm⁻¹ for TM ions implanted at 5×10¹⁴ cm⁻² disappeared for all samples implanted with rest of fluences. The fluence dependent production of implantation induced disorder and substitution of TM ions on cationic sites is discussed, which is expected to provide necessary information for the potential use of these materials as diluted magnetic semiconductors in future spintronic devices.     

Temperature dependence of Raman scattering in Co-doped AlN whiskers

Raman studies are reported for the A ₁ (TO), E ₂ (high) and E ₁ (LO) phonons of Co-doped AlN whiskers from 78 K to 778 K. The temperature dependence of the Raman shifts and line widths of these phonons can be well described by an empirical model which takes into account the contribution of the thermal expansion of the lattice and the symmetric decay of phonons into two and three identical phonons with lower energy. Our results show that the three-phonon process is the dominant decay channel in A ₁ (TO), E ₂ (high) and E ₁ (LO). The symmetric decay of A ₁ (TO) may be attributed to the production of two LA phonons near the M symmetry point of the Brillouin zone. For E ₂ (high), the symmetric decay may be near the M and L symmetry points. The E ₁ (LO) phonon, whose decay behavior has not been identified in AlN, may decay near the H and K symmetry points of the Brillouin zone. Compared with undoped AlN, the stronger temperature dependence of the A ₁ (TO) and E ₂ (high) phonons in Co-doped AlN whiskers was observed, which is probably due to the distortion of the lattice and the much larger tensile stress after doping Co into AlN.     

Synthesis and photoluminescence of single-crystal GaN nanorods prepared by sol-gel method

A new method was applied to prepare GaN nanorods. In this method, gallium oxide (Ga₂O₃) gel was firstly formed by a sol-gel processing using gallium ethanol, Ga(OC₂H₅)₃, as a new precursor. GaN nanorods were successfully synthesized after annealing of the Ga₂O₃ gel at 1000 °C for 20 min in flowing ammonia. The as-prepared nanorods were confirmed as single crystalline GaN with wurtzite structure by X-ray diffraction (XRD), selected-area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). Transmission electron microscopy (TEM) displayed that the GaN nanorods were straight and smooth, with diameters ranging from 200 nm to 1.8 μm and lengths typically up to several tens of microns. When excited by 280 nm light at room temperature, the GaN nanorods had a strong ultraviolet luminescence peak located at 369 nm and a blue luminescence peak located at 462 nm, attributed to GaN band-edge emission and the existence of the defects or surface states, respectively.     

Effect of Si doping on epitaxial lateral overgrowth of GaN: A spatially resolved micro-Raman scattering study

We report spatially resolved Raman scattering from Si-doped epitaxial laterally overgrown GaN structures to investigate spatial variations in stress and free electron concentration. The doping-induced increase in the free electron concentration is relatively higher in the laterally overgrown regions than in the coherently grown regions due to the increased contribution of the high-energy A₁ longitudinal optical phonon–plasmon coupled mode. In addition, the E₂(high) [E₂(low)] phonon energy shifts downward (upward) more significantly in the laterally overgrown regions than in the coherently grown regions. The doping-induced Raman shifts of the E₂(high) and E₂(low) phonons in the laterally overgrown regions are approximately ?0.6 and 0.11 cm^?1, respectively, corresponding to the in-plane stress of ～0.22 GPa.     

Fabrication, morphology, and photoluminescence properties of GaN nanowires and nanorods by ammoniating Ga2O3/V films on Si(1 1 1)

GaN nanowires and nanorods have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniating Ga₂O₃/V films at 900 °C in a quartz tube. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectrum were carried out to characterize the structure, morphology, and photoluminescence properties of GaN sample. The results show that the GaN nanowires and nanorods with pure hexagonal wurtzite structure have good emission properties. The growth direction of nanostructures is perpendicular to the fringes of (1 0 1) plane. The growth mechanism is also briefly discussed.     

Growth and characterization of pine-needle-shaped GaN nanorods by sputtering and ammoniating process

Pine-needle-shaped GaN nanorods have been successfully synthesized on Si(111) substrates by ammoniating Ga₂O₃/Nb films at 950 ^°C in a quartz tube. The products are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and field-emission transmission electron microscope (FETEM). The results show that the pine-needle-shaped nanorods have a pure hexagonal GaN wurtzite with a diameter ranging from 100 to 200 nm and a length up to several microns. The photoluminescence spectra (PL) measured at room temperature only exhibit a strong emission peak at 368 nm. Finally, the growth mechanism of GaN nanorods is also briefly explored.     

Morphology of InN nanorods using spectroscopic Raman imaging

We report the vibrational properties of vertical and oblique InN nanorods (NRs) grown by molecular beam epitaxy (MBE). Surface optical (SO) Raman mode at 561 cm⁻¹, belonging to E₁ symmetry [SO(E₁)], is identified along with symmetry allowed Raman modes of E₂(low), E₂(high), and E₁(LO) at 87, 489, and 589 cm⁻¹, respectively, corresponding to wurtzite InN phase. Usually, SO phonon modes arise due to breakdown of translational symmetry of surface potential at surface defects, which are attributed by the surface roughness. Intensity distribution of E₁(LO) and SO(E₁) phonon modes over a specified area have been analysed using Raman area mapping with an optical resolution of 400 nm. Imaging with E₁(LO) phonon mode, originating from the bulk of the sample, distinguishes the vertical NRs alone. We are able to resolve NR morphologies in both vertical and oblique cases with additional Raman mapping analysis of SO(E₁) phonon mode, emerging from the surface irregularities, which are confined to the tip of MBE grown NRs. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural,optical and electrical properties of undoped and Si-doped AlxGa1−xN thin films on Si (1 1 1) substrate grown by PA-MBE

We have studied the structural properties of undoped and Si-doped Al_xGa_1?xN/GaN/AlN on Si (1 1 1) substrate prepared by plasma-assisted molecular beam epitaxy (PA-MBE) using high-resolution X-ray diffraction (HR-XRD) and atomic force microscopy (AFM). In comparison with undoped AlGaN, the roughness and dislocation density on the surface of the AlGaN layer decrease with Si doping. Full width half maximum (FWHM) of the undoped and Si-doped samples were equal to 0.69° and 0.52°, respectively. This indicates that the Si doping improves the crystalline quality of the Al_xGa_1?xN layer compared with the undoped one. Raman scattering measurement reveals that the optical phonon modes of A₁(LO) and E₂(H) of the AlGaN show a one-mode and two-modes behavior, respectively. The Fourier-transform infrared reflectance (FTIR) investigation confirms the one-mode (two-mode) behavior of the LO (TO) phonon in our samples. This is in good agreement with Raman measurement. Finally, the barrier height (Φ_B) of undoped and Si-doped Al_xGa_1?xN samples was found to be 0.86 and 0.74 eV, respectively.