Study on the relationships between Raman shifts and temperature range for α-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.     

Temperature dependences of Raman scattering in different types of GaN epilayers

First-order Raman scatterings of hexagonal GaN layers deposited by the hydride vapour phase epitaxy and by metal-organic chemical vapour deposition on SiC and sapphire substrates are studied in a temperature range between 303 K and 503 K. The temperature dependences of two GaN Raman modes (A₁ (LO) and E₂ (high)) are obtained. We focus our attention on the temperature dependence of E₂ (high) mode and find that for different types of GaN epilayers their temperature dependences are somewhat different. We compare their differences and give them an explanation. The simplified formulas we obtained are in good accordance with experiment data. The results can be used to determine the temperature of a GaN sample.     

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.     

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)     

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.     

Prediction of superconductivity of Ta2AlC: in situ Raman spectrometry and density functional investigations

In this paper, in situ Raman spectra of Ta₂AlC are measured in the temperature range of 80–500 K at ambient pressure. The frequencies of the Raman modes decrease with increasing temperature, which have been explained by the anharmonic and thermal expansion effects. The line‐width of E_2g (ω₃) mode increases at elevated temperatures, which is found to be due to the anharmonic phonon–phonon scatterings. On the other hand, the line‐widths of E_2g (ω₁) and A_1g (ω₄) modes decrease continuously with increasing temperature, which is explained by the electron–phonon couplings of these two phonon modes with the Ta 5d electrons. The electron–phonon coupling strengths are obtained both in experiments and density functional calculations. Finally, Ta₂AlC is predicted to be a new superconductive MAX phase. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Stress and morphology of a nonpolar a-plane GaN layer on r-plane sapphire substrate

The anisotropic strain of a nonpolar (1120) a-plane GaN epilayer on an r-plane (1102) sapphire substrate, grown by low-pressure metal-organic vapour deposition is investigated by Raman spectroscopy. The room-temperature Raman scattering spectra of nonpolar a-plane GaN are measured in surface and edge backscattering geometries. The lattice is contracted in both the c- and the m-axis directions, and the stress in the m-axis direction is larger than that in the c-axis direction. On the surface of this sample, a number of cracks appear only along the m-axis, which is confirmed by the scanning electron micrograph. Atomic force microscopy images reveal a significant decrease in the root-mean-square roughness and the density of submicron pits after the stress relief.     

Raman scattering in InN films and nanostructures

Studies of lattice dynamics devoted to wurtzite InN are presented. Raman scattering experiments on both InN thin films and nanometric islands grown by Metal–Organic Vapor Phase Epitaxy (MOVPE) were performed at room temperature. From the Raman spectra recorded from InN films under hydrostatic pressure up to 13 GPa, linear pressure coefficients and the corresponding Grüneisen parameters for both E₂ and A₁(LO) phonons were extracted for the wurtzite structure up to 11 GPa, close to the starting pressure of the hexagonal to rock-salt phase transition of InN. Spectra at higher pressure suggest that InN undergoes a gradual phase transition, and the reverse transition exhibits a strong hysteresis effect during the downstroke. Then, we discuss recent results on large single InN islands grown on GaN buffer layers, obtained by spatially resolved micro-Raman measurements. The magnitude of the residual strain is estimated, using a recent determination of phonon deformation potentials. It is found to vary linearly as a function of island height.     

Optical spectroscopy of a-plane-oriented ZnO epilayers grown by plasma-assisted molecular beam epitaxy

a-plane ZnO layers were successfully grown, by plasma-assisted molecular beam epitaxy, on r-plane (011–2) sapphire substrates. Several features attributed to the A, B and C free excitonic transitions are identified through temperature-dependent photoluminescence (PL) and reflectivity measurements. The temperature dependence of the peak energy positions of these transitions was studied from 8 K to 300 K. So, the PL peak energy of the A free exciton was plotted and fitted with a Varshni empirical equation. In the σ polarization (E⊥c), for which A and B are allowed, the reflectivity spectrum measured at 8 K was fitted by using a program based on the theory of the spatial resonance dispersion Hopfield model. Our results indicate that the A and B free excitonic features are at a higher energy than those in ZnO on c-oriented sapphire and show a good PL even at 250 K. These results also show that the new and intense emission peak observed in the region of the first phonon replica (3.33–3.28 eV) and identified as a stacking fault in the epilayer disappears at high temperature above 150 K.     

Physical insight of superconductivity of Nb2AlC: in situ Raman spectrometry investigation

Superconductivity of Nb₂AlC has been previously reported, but the origin is not clear. In this paper, in situ Raman spectra of Nb₂AlC are measured in the temperature range from 80 to 380 K at ambient pressure. The line‐width of E_2g (ω₁) mode increases with temperature which originates from the anharmonic phonon–phonon scattering. On the contrary the line‐widths of E_2g (ω₂) and A_1g (ω₄) modes decrease continuously at elevated temperature. The phenomenon is explained by the electron–phonon coupling. The origin of superconductivity is therefore interpreted by the coupling of Nb 4d electrons with E_2g (ω₂) and A_1g (ω₄) phonon modes. Copyright © 2013 John Wiley & Sons, Ltd.     

Temperature characterization of Raman scattering in an AlGaN/GaN heterostructure

Raman scattering from an AlGaN/GaN heterostructure was performed in the temperature range from 77 to 773 K. The first- and second-order Raman scattering of the A₁ longitudinal-optical phonon–plasmon coupled mode from an AlGaN/GaN interface as well as the Raman scattering from the GaN layer were observed. All the modes downshift, and their intensities weaken with increasing temperature. The free-carrier concentration estimated by the frequency of the coupled mode from an AlGaN/GaN interface is 7.5 times as high as that of n-AlGaN, indicating mass free-carrier transfer from the AlGaN barrier to the GaN well. Moreover, the temperature dependence of the phonon frequency is well described by an empirical formula. PACS 78.30.Fs; 63.20.Ls; 61.82.Fk; 68.60.Dv; 81.15.Gh     

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.     

Characterization of a-plane orientation ZnO film grown on GaN/Sapphire template by pulsed laser deposition

In this study, the authors have investigated the structural and optical properties of ZnO layer grown by pulsed laser deposition on GaN/r-plane sapphire. X-ray diffraction results demonstrate the ZnO film to be highly preferentially deposited at a-axis orientation; the different rocking curve values along the two orthogonal directions indicate the low C_2v symmetry in the growth a-plane ZnO. From free stress to large tensile stress (about 1.34 × 10⁹ Pa) distribution along the growth direction of ZnO is revealed by visible Raman mapping spectra. The enhanced significantly high-order longitudinal-optical (LO) phonon modes up to 4th and no TO phonons have been observed in Raman spectrum under UV 325 nm by resonance conditions; an intense and broad disorder activated surface phonon mode is also observed, resulting from the increased disorder on the film surface with stripe-like growth features. Low-temperature photoluminescence measurements reveal that the band-edge emission of ZnO is dominated by neutral donor-bound exciton and free electrons to neutral acceptor emissions. Interfacial microstructure of ZnO/GaN has been examined by transmission electron microscopy, with the epitaxial relationship () ZnO//() GaN. All these results indicated that GaN template played an important role in the growth of ZnO film, with full advantage of small lattice mismatch.     

Structural and optical properties of nearly stress-free m-plane ZnO film on (1 0 0) γ-LiAlO2 with a GaN buffer layer by metal-organic chemical vapor deposition

m-plane ZnO film was epitaxially deposited on (1 0 0) γ-LiAlO₂ by metal-organic chemical vapor deposition at 600 °C with a GaN buffer layer. The epitaxial relationships between ZnO and GaN, GaN and (1 0 0) γ-LiAlO₂ were determined by X-ray diffraction Φ-scans. There exhibits very small decrease for the E₂ mode shift (0.3 cm⁻¹) of ZnO in the Raman spectrum, which indicates the epitaxial ZnO film was under a slight tensile stress (5.77 × 10⁷ Pa). Unlike the highly strained a-plane ZnO, temperature dependent photoluminescence spectra show that the free A exiton emission was observed with the temperature ≤138 K.     

GaN外延层的拉曼散射研究

ＧａＮ外延层的拉曼散射研究１李国华１韩和相１汪兆平２段树琨３王晓亮（１半导体超晶格国家重点实验室２集成光电子学国家重点联合实验室３半导体材料科学实验室中国科学院半导体研究所北京１０００８３）ＲａｍａｎＳｃａｔｅｒｉｎｇｏｆＧａＮＥｐｉｌａｙｅｒ１Ｌ...     

纤锌矿GaN外延层薄膜热膨胀行为的变温Raman散射研究

本文对纤锌矿结构GaN外延层薄膜的热膨胀行为进行了研究,结合热膨胀系数的物理意义与变温Raman散射时声子频移的变化规律,研究了热膨胀系数与变温Raman散射之间的关系.结果表明:通过测量Raman声子E_2(high),A_1(TO)和E_1(TO)频移与温度之间的线性关系,结合相应声子Gruneisen参数的涵义,可对纤锌矿结构GaN外延层薄膜在一定温度范围内的热膨胀系数进行测量.本文提供了一种表征纤锌矿结构GaN外延层薄膜热膨胀行为的有效方法,为进一步研究III族氮化物外延层薄膜在生长过程中热膨胀系数的匹配、降低外延层薄膜中的位错密度并提高发光二极管的发光效率提供了理论依据.     

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.     

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.     

Optical properties of nonpolar -plane GaN layers

We have studied optical properties of nonpolar a-plane GaN layers grown on r-plane sapphire by metalorganic chemical vapor deposition and hydride vapor phase epitaxy using different nucleation schemes. Several emission bands, which are not typical for c-plane GaN, are observed in the photoluminescence spectra and their excitation-intensity, temperature, and polarization dependencies are examined. In addition, the spatial distribution of the emissions was examined by cathodoluminescence imaging and relations of the different emissions with particular structural features in the layers are revealed. The results are discussed with emphasis on the origin of the emission line and particular recombination mechanisms.