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.     

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.     

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)     

Raman scattering studies on manganese ion-implanted GaN

This paper reports that the Raman spectra have been recorded on the metal-organic chemical vapour deposition epitaxially grown GaN before and after the Mn ions implanted. Several Raman defect modes have emerged from the implanted samples. The structures around 182 cm^-1 modes are attributed to the disorder-activated Raman scattering, whereas the 361 cm^-1 and 660 cm^-1 peaks are assigned to nitrogen vacancy-related defect scattering. One additional peak at 280 cm^-1 is attributed to the vibrational mode of gallium vacancy-related defects and/or to disorder activated Raman scattering. A Raman-scattering study of lattice recovery is also presented by rapid thermal annealing at different temperatures between 700 °C and 1050 °C on Mn implanted GaN epilayers. The behaviour of peak-shape change and full width at half maximum (FWHM) of the A₁(LO) (733 cm^-1) and E^H₂ (566 cm^-1) Raman modes are explained on the basis of implantation-induced lattice damage in GaN epilayers.     

On the origin of the 2.2-2.3 eV photoluminescence from chemically etched germanium

The photoluminescence (PL) at ∼2.2-2.3 eV from Ge-based nanocrystalline materials is described in the literature as nanocrystal size-independent. We have observed visible luminescence from two different types of stain-etched Ge samples, one prepared after Sendova-Vassileva et al. (Thin Solid Films 255 (1995) 282) in a solution of H₂O₂:HF at 50:1 volume ratio, and the other in a solution of HF:H₃PO₄:H₂O₂ at 34:17:1 volume ratio. Energy dispersive X-ray analysis (EDX), Raman and FTIR spectroscopy, and the near edge X-ray absorption structure (XANES), indicate that the chemically etched Ge layers of the former type of samples are composed of non-stoichometric Ge oxides, i.e. GeO_x (0<x<2), and free from any Ge nanoconstructions. It is also suggested from XANES that the latter type of chemically etched Ge samples comprise 8-9 nm nanocrystals of Ge, surface-covered with mainly oxygen. Photoluminescence occurred at ∼2.3 eV for all samples. The PL behavior of the latter type of chemically etched Ge on annealing in different chemical environments (air or H) allowed us to conclude that the PL from these materials, as well as that from those Ge-based nanocrystalline materials reported in the literature, is from GeO_xs.     

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.     

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.     

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.     

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.     

Structural and optical features of nanoporous silicon prepared by electrochemical anodic etching

Nanoporous silicon (NPS) samples were prepared by electrochemical anodic etching of p-type (0 0 1) silicon wafers in HF solution, and some of them were aged in air. The nanostructural, optical and chemical features of the NPS were investigated in terms of etching and aging conditions. The surface of the porous Si exhibits an etched layer with a thickness of 30–40 nm; this layer appears to consist of aggregates of 5–10 nm size nano-crystallites. The NPS exhibited broad photoluminescence (PL) spectra with its peak in the red light region (740 nm). After aging the porous samples for 4 weeks in air, we observed the PL intensity became approximately a fifth of that of the as-prepared one, along with a blue shift. It is very likely that the blue shift of the PL peak was caused by the shrinkage of the Si nano-crystallites due to the oxidation in the surface of the nano-crystallites.     

γ-LiAlO2上a面ZnO薄膜的光谱特性研究

利用激光脉冲沉积(PLD)技术在(302)γ-LiAlO₂衬底上成功生长了非极性的a面(1120)ZnO薄膜,光致发光谱(PL)带边发射峰半峰宽仅为115meV.研究了非极性ZnO薄膜光谱特性的面内各向异性,发现随着入射光偏振方向改变,在偏振透射光谱上,吸收边移动了20meV,这与A、B激子和C激子的能量差一致;而在拉曼光谱上,激发光偏振方向的改变导致E₂模式的强度发生明显改变. 关键词： 非极性ZnO 2')" href="#">γ-LiAlO₂ PLD     

Effects of impurities containing phosphorus on the surface properties and catalytic activity of TiO2 nanotube arrays

TiO₂ nanotube arrays were prepared by titanium anodic oxidation with either HF or H₃PO₄/NH₄F aqueous electrolyte solutions. The samples were characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscope, photoluminescence spectra (PL) and photocurrent response. Aqueous solutions of methylene blue or Cr(VI) ions were used as the target pollutants to compare catalytic activities of the two nanotube array types. The amorphous impurities containing phosphorus were confirmed by XRD and IR, for the sample synthesized with H₃PO₄/NH₄F electrolytes. They closed a portion of the active sites, acted as recombination centers of photo-generated charges, and were also involved in the negative reactions of competing photo-generated holes or OH radicals. The TiO₂ nanotube arrays formed in the H₃PO₄/NH₄F electrolytes exhibited a stronger fluorescence spectrum, a weaker photocurrent and a lower catalytic activity than the sample fabricated with HF electrolyte without phosphorus impurities.     

How does the substrate affect the Raman and excited state spectra of a carbon nanotube?

We study the optical properties of a single, semiconducting single-walled carbon nanotube (CNT) that is partially suspended across a trench and partially supported by a SiO₂-substrate. By tuning the laser excitation energy across the E ₃₃ excitonic resonance of the suspended CNT segment, the scattering intensities of the principal Raman transitions, the radial breathing mode (RBM), the D mode and the G mode show strong resonance enhancement of up to three orders of magnitude. In the supported part of the CNT, despite a loss of Raman scattering intensity of up to two orders of magnitude, we recover the E ₃₃ excitonic resonance suffering a substrate-induced red shift of 50 meV. The peak intensity ratio between G band and D band is highly sensitive to the presence of the substrate and varies by one order of magnitude, demonstrating the much higher defect density in the supported CNT segments. By comparing the E ₃₃ resonance spectra measured by Raman excitation spectroscopy and photoluminescence (PL) excitation spectroscopy in the suspended CNT segment, we observe that the peak energy in the PL excitation spectrum is red-shifted by 40 meV. This shift is associated with the energy difference between the localized exciton dominating the PL excitation spectrum and the free exciton giving rise to the Raman excitation spectrum. High-resolution Raman spectra reveal substrate-induced symmetry breaking, as evidenced by the appearance of additional peaks in the strongly broadened Raman G band. Laser-induced line shifts of RBM and G band measured on the suspended CNT segment are both linear as a function of the laser excitation power. Stokes/anti-Stokes measurements, however, reveal an increase of the G phonon population while the RBM phonon population is rather independent of the laser excitation power.     

Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.     

Morphology and optical properties of p-type porous GaAs(1 0 0) layers made by electrochemical etching

Porous GaAs layers were formed by electrochemical etching of p-type GaAs(1 0 0) substrates in HF solution. A surface characterization has been performed on p-type GaAs samples using X-ray photoelectron spectroscopy (XPS) technique in order to get information about the chemical composition, particularly on the surface contamination. According to the XPS spectra, the oxide layer on as-received porous GaAs substrates contains As₂O₃, As₂O₅ and Ga₂O₃. Large amount of oxygen is present at the surface before the surface cleaning.Compared to untreated GaAs surface, room temperature photoluminescence (PL) investigations of the porous layers reveal the presence of two PL bands: a PL peak at ∼871 nm and a “visible” PL peak at ∼650-680 nm. Both peak wavelengths and intensities varied from sample to sample depending on the treatment that the samples have undergone. The short PL wavelength at 650-680 nm of the porous layers is attributed to quantum confinement effects in GaAs nano-crystallites. The surface morphology of porous GaAs has been studied using atomic force microscopy (AFM). Nano-sized crystallites were observed on the porous GaAs surface. An estimation of the mean size of the GaAs nano-crystals obtained from effective mass theory and based on PL data was close to the lowest value obtained from the AFM results.     

Porous Silicon as an Intermediate Buffer Layer for Zinc Oxide Nanorods

Zinc thin films were deposited onto porous silicon (PSi) substrates by dc sputtering using a Zn target. These films were then annealed under flowing (6 l/min) oxygen gas environment in the furnace at 600°C for 2 h. Porous silicon is used as an intermediate layer between silicon and ZnO films and it provides a large area composed of an array of voids. The PSi samples were prepared using photoelectrochemical method on n-type silicon wafer with (111) and (100) orientation. To prepare porous structures, the samples were dipped into a mixture of HF:ethanol (1:1) for 5 min with current densities of 50 mA/cm², and subjected to external illumination with a 500 W UV lamp. The surface morphology and the nanorod structure of the ZnO films were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD). We synthesized the ZnO nanorods with diameter of 80–100 nm without any catalysts or templates. The XRD pattern confirmed that the ZnO nanorods were of polycrystalline structure. The surface-related optical properties have been investigated by photoluminescence (PL) and Raman measurements at room temperature. Micro-Raman results showed that A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at 522 cm^–1 and 530 cm^–1, respectively. PL spectra peaks are clearly visible at 366 cm^–1 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The PL spectral peak position in ZnO nanorods on porous silicon is blue-shifted with respect to that in unstrained ZnO (381 nm).     

Effect of surface modification by thermally oxidization and HF etching on UV photoluminescence emission of porous silicon

Photoluminescence of porous silicon (PS) is instable due perhaps to the nanostructure modification in air. The controllable structure modification processes on the as-prepared PS were conducted by thermal oxidization and/or HF etching. The PL spectra taken from thermally oxidized PS showed a stable photoluminescence emission of 355 nm. The photoluminescence emission taken from both of PS and oxidized porous silicon (OPS) samples etched with HF were instable, which can be reversibly recovered by the HF etching procedure. The mechanism of UV photoluminescence is discussed and attributed to the transformation of luminescence centers from oxygen deficient defects to the oxygen excess defects in the thermal oxidized PS sample and surface absorbed silanol groups on PS samples during the chemical etched procedure.     

Bi-assisted chemical etching of silicon in HF/Co(NO3)2 solution

The morphology and the photoluminescence (PL) of Bi-assisted electroless etched p-type silicon in HF–Co(NO₃)₂–H₂O solution as a function of etching time were studied. The scanning electron microscopy (SEM) observations have shown that the morphology of etched layers strongly depends on the etching time and it was observed that macropores filled with silicon crystallites are formed for etching time higher than 50 min. Moreover, it was found that the PL spectra show a red emission with a peak centred at 640 nm. The PL peak intensity reaches a maximum for etching time of 50 min, and then it decreases with increasing etching time. The Fourier transform infrared (FTIR) measurements have shown a strong increase in intensities of the relevant Si–H and in the amount of oxide (absorption band at 1070 cm^?1) for long etching time which was ascribed to an increase in the number of Si crystallites formed in the macropores.     

Multilayer based interferential-plasmonic structure: metal cluster 3D grating combined with dielectric mirror

This paper reports strong deep-ultraviolet and visible photoluminescence (PL) of the GaN nanoparticles depending on the conversion time from Ga₂O₃ to GaN. Monoclinic β-Ga₂O₃ nanoparticles with a diameter of approximately 2.5–5.0 nm were fabricated prior to conversion to GaN. The Ga₂O₃ nanoparticles were converted to GaN in the tube furnace with NH₃ flow at 900°C for 10, 30, 60, and 120 min. Depending on the conversion time, the converted GaN nanoparticle size became bigger with the increase of the conversion time. The characteristic GaN x-ray diffraction (XRD) peaks became bigger when the conversion time increased. The PL intensity drastically increased with the increase of the conversion time. The spectra profile completely overlapped for GaN samples converted for 10, 30, and 60 min, with the maximum peak at 390 nm. However, the PL spectrum slightly narrowed and red-shifted with the maximum peak at 400 nm for the GaN nanoparticles converted for 120 min.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.