Synthesis and optical properties of single crystalline GaN nanorods with a rectangular cross-section

GaN nanorods were synthesized from the reaction of a Ga/Ga₂O₃ mixture with NH₃ on Si substrates by chemical vapor deposition. The synthesized products were characterized by scanning and transmission electron microscopy, X-ray diffraction, photoluminescence and Raman spectroscopy. The nanorods are highly single crystalline and possess uniform smooth surfaces. PL revealed only a strong emission at 3.268 eV, ascribed to free exciton (FX) transitions, at room temperature; while the well-known yellow luminescence band centered at 2.2-2.3 eV was not detected. Four first-order phonon modes, corresponding to the A₁(TO), E₁(TO), E₂(high), and A₁(LO) at ∼531, 554, 564, and 721 cm⁻¹, respectively, were observed by Raman backscattering. The red-shift of the FX emission peak and the down-shifts of the Raman modes by a few wave numbers are attributed to the presence of tensile strain inside GaN nanorods.     

Preparation and characterization of CdS/Si coaxial nanowires

CdS/Si coaxial nanowires were fabricated via a simple one-step thermal evaporation of CdS powder in mass scale. Their crystallinities, general morphologies and detailed microstructures were characterized by using X-ray diffraction, scanning electron microscope, transmission electron microscope and Raman spectra. The CdS core crystallizes in a hexagonal wurtzite structure with lattice constants of a=0.4140 nm and c=0.6719 nm, and the Si shell is amorphous. Five Raman peaks from the CdS core were observed. They are 1LO at 305 cm⁻¹, 2LO at 601 cm⁻¹, A₁-TO at 212 cm⁻¹, E₁-TO at 234 cm⁻¹, and E₂ at 252 cm⁻¹. Photoluminescence measurements show that the nanowires have two emission bands around 510 and 590 nm, which originate from the intrinsic transitions of CdS cores and the amorphous Si shells, respectively.     

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.     

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.     

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.     

Synthesis and characterization of GaN nanowires by ammoniating Ga2O3/Cr thin films deposited on Si(1 1 1) substrates

GaN nanowires have been successfully synthesized on Si(1 1 1) substrates by magnetron sputtering through ammoniating Ga₂O₃/Cr thin films at 950 °C. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), FT-IR spectrophotometer, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), and photoluminescence (PL) spectrum were carried out to characterize the microstructure, morphology, and optical properties of GaN samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure and high-quality crystalline, have the size of 30-80 nm in diameter and several tens of microns in length with good emission properties. The growth direction of GaN nanowires is perpendicular to the fringe of (1 0 1) plane. The growth mechanism of GaN nanowires is also discussed in detail.     

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.     

Surface optical Raman modes in GaN nanoribbons

Raman scattering studies were performed in GaN nanoribbons grown along [1 0 0]. These samples were prepared inside Na‐4 mica nanochannels by the ion‐exchange technique and subsequent annealing in NH₃ ambient. Detailed morphological and structural studies including the crystalline orientation were performed by analyzing the vibrational properties in these GaN nanoribbons. Pressure in the embedded structure was calculated from the blue shift of the E₂(high) phonon mode of GaN. Possible red shift of optical phonon modes due to the quantum confinement is also discussed. In addition to the optical phonons allowed by symmetry, two additional Raman peaks were also observed at ∼633 and 678 cm⁻¹ for these nanoribbons. Calculations for the wavenumbers of the surface optical (SO) phonon modes in GaN in Na‐4 mica yielded values close to those of the new Raman modes. The SO phonon modes were calculated in the slab (applicable to belt‐like nanoribbon) mode, as the wavenumber and intensity of these modes depend on the size and the shape of the nanostructures. The effect of surface‐modulation‐assisted electron–SO phonon scattering is suggested to be responsible for the pronounced appearance of SO phonon modes. A scaling factor is also estimated for the interacting surface potential influencing the observed SO Raman scattering intensities. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of GaN nanowires

In this work, GaN nanowires were fabricated on Si substrates coated with NiCl₂ thin films using chemical vapor deposition (CVD) method by evaporating Ga₂O₃ powder at 1100 °C in ammonia gas flow. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and photoluminescence (PL) spectrum are used to characterize the samples. The results demonstrate that the nanowires are single-crystal GaN with hexagonal wurtzite structure. The growth mechanism of GaN nanowires is also discussed.     

Raman-scattering spectrum of GaN straight nanowires

The Raman spectrum of GaN straight nanowires deposited on a LaAlO₃ crystal substrate was studied. The E₂ (high) phonon frequency at 560 cm^-1 shows a 9 cm^-1 shift compared with the calculated value. The low-energy shift and band broadening of the Raman modes result from the nanosize effect. The unique property of the low intensity ratio of I_E2/I_A1(LO) on the Raman spectrum from the GaN straight nanowires was observed. Received: 5 June 2000 / Accepted: 7 June 2000 / Published online: 2 August 2000     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Effect of different electrolytes on porous GaN using photo-electrochemical etching

This article reports the properties and the behavior of GaN during the photoelectrochemical etching process using four different electrolytes. The measurements show that the porosity strongly depends on the electrolyte and highly affects the surface morphology of etched samples, which has been revealed by scanning electron microscopy (SEM) images. Peak intensity of the photoluminescence (PL) spectra of the porous GaN samples was observed to be enhanced and strongly depend on the electrolytes. Among the samples, there is a little difference in the peak position indicating that the change of porosity has little influence on the PL peak shift, while it highly affecting the peak intensity. Raman spectra of porous GaN under four different solution exhibit phonon mode E₂ (high), A₁ (LO), A₁ (TO) and E₂ (low). There was a red shift in E₂ (high) in all samples, indicating a relaxation of stress in the porous GaN surface with respect to the underlying single crystalline epitaxial GaN. Raman and PL intensities were high for samples etched in H₂SO₄:H₂O₂ and KOH followed by the samples etched in HF:HNO₃ and in HF:C₂H₅OH.     

Synthesis of GaN nanowires by Tb catalysis

Rare earth metal seed Tb was employed as catalyst for the growth of GaN wires. GaN nanowires were synthesized successfully through ammoniating Ga₂O₃/Tb films sputtered on Si(1 1 1) substrates. The samples characterization by X-ray diffraction and Fourier transform infrared indicated that the nanowires are constituted of hexagonal wurtzite GaN. Scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy showed that the samples are single-crystal GaN nanowire structures. The growth mechanism of the GaN nanowires is discussed.     

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.     

Investigation of structural and optical properties of nanoporous GaN film

The structural and optical characteristics of porous GaN prepared by Pt-assisted electroless etching under different etching durations are reported. The porous GaN samples were investigated by scanning electron microscopy (SEM), high-resolution X-ray diffraction (HR-XRD), photoluminescence (PL) and Raman scattering. SEM images indicated that the density of the pores increased with the etching duration; however, the etching duration has no significant effect on the size and shape of the pores. XRD measurements showed that the (0 0 0 2) diffraction plane peak width of porous samples was slightly broader than the as-grown sample, and it increased with the etching duration. PL measurements revealed that the near band edge peak of all the porous samples were red-shifted; however, the porosity-induced PL intensity enhancement was only observed in the porous samples; apart from that, two additional strain-induced structural defect-related PL peaks observed in as-grown sample were absent in porous samples. Raman spectra showed that the shift of E₂ (high) to lower frequency was only found in samples with high density of pores. On the contrary, the absence of two forbidden TO modes in the as-grown sample was observed in some of porous samples.     

The testing of stress-sensitivity in heteroepitaxy GaN/Si by Raman spectroscopy

In this paper the stress-sensitive features of hexagonal-GaN (H-GaN) and cubic-Si (C-Si) were investigeted. The H-GaN films have been grown on Si (1 1 1) substrates by metal-organic chemical vapor deposition (MOCVD). The Raman peaks of GaN E₂ (high) and Si (TO) have a blueshift when applying displacement-loadings which parallel the (0 0 0 2) plane of H-GaN. According to the relationship between stress changing and Raman peak shifts, the values of compressive stress in both materials were larger with increasing the displacement-loadings. The stress-sensitivity of H-GaN up to 93.5 MPa/μm which higher than C-Si which testing is 467.9 MPa/μm and the nonlinear error σ of GaN films is 0.1639 and Si is 0.0698. The measurement has a great significance to deeply research the piezoelectric polarization of H-GaN in future. This finding is important for the understanding and application of nitride semiconductors.     

Comparative Analysis of Temperature-dependent Raman Spectra of GaN and GaN/Mg Films

The Raman spectra of unintentionally doped gallium nitride (GaN) and Mg-doped GaN films were investigated and compared at room temperature and low temperature. The differences of E₂ and A₁(LO) mode in two samples are discussed. Stress relaxation is observed in Mg-doped GaN, and it is suggested that Mg-induced misfit dislocation and electron–phonon interaction are the possible origins. A peak at 247 cm^?1 is observed in both the Raman spectra of GaN and Mg-doped GaN. Temperature-dependent Raman scattering experiment of Mg-doped GaN shows the frequency and intensity changes of this peak with temperature. This peak is attributed to the defect-induced vibrational mode.     

Characterization of crystal lattice constant and dislocation density of crack-free GaN films grown on Si(1 1 1)

GaN have sphalerite structure (Cubic-GaN) and wurtzite structure (hexagonal GaN). We report the H-GaN epilayer with a LT-AlN buffer layer has been grown on Si(1 1 1) substrate by metal-organic chemical vapor deposition (MOCVD). According to the FWHM values of 0.166° and 14.01 cm⁻¹ of HDXRD curve and E₂ (high) phonon of Raman spectrum respectively, we found that the crystal quality is perfect. And based on the XRD spectrum, the crystal lattice constants of Si (a = 5.3354 ?) and H-GaN (a_epi = 3.214 ?, c_epi = 5.119 ?) have been calculated for researching the tetragonal distortion of the sample. These results indicate that the GaN epilayer is in tensile strain and Si substrate is in compressive strain which were good agreement with the analysis of Raman peaks shift. Comparing with typical values of screw-type (D_screw = 7 × 10⁸ cm⁻²) and edge-type (D_edge = 2.9 × 10⁹ cm⁻²) dislocation density, which is larger than that in GaN epilayers growth on SiC or sapphire substrates. But our finding is important for the understanding and application of nitride semiconductors.     

Raman spectroscopy of ZnS nanostructures

We report Raman scattering results of wurtzite ZnS nanowires, nanocombs, and nanobelts. The Raman spectrum obtained from ZnS nanowires exhibits first‐order phonon modes at 272, 284, and 350 cm⁻¹, corresponding to A₁/E₁ transverse optical, E₂ transverse optical, and A₁/E₁ longitudinal optical phonons, respectively. Several multiphonon modes are also observed. The longitudinal optical phonon mode varies in wavenumber for nanocombs and nanobelts, indicating that the residual strain varies during the morphological change from ZnS nanowires to nanocombs and ultimately to nanobelts. Interestingly, a surface optical (SO) phonon mode varies in wavenumber depending on the shape and surface roughness of the ZnS nanostructures. The surface modulation wavelengths of the ZnS nanowires, nanocombs, and nanobelts are estimated using the SO phonon dispersion relations and the observed SO phonon wavenumbers. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparative Analysis of Temperature-dependent .Raman Spectra of GaN and GaN/Mg Films

The Raman spectra of unintentionally doped gallium nitride (GaN) and Mg-doped GaN films were investigated and compared at room temperature and low temperature. The differences of E₂ and A₁(LO) mode in two samples are discussed. Stress relaxation is observed in Mg-doped GaN, and it is suggested that Mg-induced misfit dislocation and electron–phonon interaction are the possible origins. A peak at 247 cm⁻¹ is observed in both the Raman spectra of GaN and Mg-doped GaN. Temperature-dependent Raman scattering experiment of Mg-doped GaN shows the frequency and intensity changes of this peak with temperature. This peak is attributed to the defect-induced vibrational mode. Translated from Chinese Journal of Semiconductors, 2005, 26(4) (in Chinese)