Effects of gas pressure on the synthesis and photoluminescence properties of Si nanowires in VHF-PECVD method

Silicon nanowires (SiNWs) were grown on an Au-coated Si(111) substrate at various gas pressures by very high frequency plasma enhanced chemical vapor deposition via the vapor–liquid–solid mechanism. The synthesized SiNWs were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, Raman spectroscopy and photoluminescence (PL). The SiNWs were sharp needle-shaped and possessed highly crystalline core and oxide amorphous shell. As the gas pressure increases from 70 mtorr to 85 mtorr, the average diameter of the SiNWs decreases from 250 nm to 70 nm. Furthermore, the density of the nanowires increases with the gas pressure. The PL spectra revealed a peak at about 400 nm and a broadband emission at about 700 nm.     

Strong photoluminescence anisotropy in porous silicon layers prepared by polarized-light assisted anodization

Linearly-polarized infrared (1.06 μm) laser light with intensities ranging from 5.3 to 97 mW/cm² has been used to obtain anisotropically luminescent porous silicon (PSi) layers by photoanodic etching in a hydrofluoric acid solution. Remarkably large photoluminescence (PL) anisotropy has been observed in samples prepared with the highest illumination intensity. These samples show very low degrees of linear polarization when the PL excitation light is polarized parallel to the polarization direction of the etching light. When the excitation light is polarized perpendicular to that, we obtain usual degrees of linear polarization of several percent. This result indicates that anisotropic Si nanostructures in PSi layers can be made isotropic with high orientation selectivity by the polarized-light assisted technique. A simple two-dimensional model is presented to explain the observed prominent anisotropy.     

Y2O3:Bi,Yb减反转光薄膜的制备及其性能研究

采用脉冲激光沉积(PLD)方法在湿法腐蚀后的Si(100)衬底上制备了Y₂O₃:Bi,Yb减反转光薄膜。所制备的薄膜在300~800 nm波长范围内的平均反射率最低至5.28%,同时在晶体硅太阳能电池最佳响应范围内的980 nm附近表现出了良好的下转光特性。与非减反下转光薄膜相比较,具有减反结构的Y₂O₃:Bi,Yb下转换薄膜的转光强度有了明显的提升。随着衬底腐蚀时间在一定范围内的延长,Bi³⁺和Yb³⁺的发射峰强度线性增大。该减反转光薄膜为太阳能电池效率提高提供了一种简单可行的方法。     

Fabrication and field emission properties of multi-walled carbon nanotube/silicon nanowire array

Silicon nanowire (SiNW) arrays were fabricated on silicon wafers by the metal-assisted chemical etching method. Varied average diameters of SiNW arrays were realized through further treatment in a mixed agent of HF and HNO₃ of certain concentrations. After the treatment, there were more than 93% SiNWs with diameters smaller than 100 nm. The tip of each SiNW was subsequently wrapped with multi-walled carbon nanotubes (MWCNTs) with chemical vapor deposition method. The as-fabricated MWCNT/SiNW arrays were fabricated into electric field emitters, with turn-on field of 2.0 V/μm (current density: 10 μA/cm²), much lower than that of SiNW array (5.0 V/μm). The turn-on electric field of MWCNT/SiNW array decreased with the decreasing of the average diameter of SiNWs, indicating the performance of the field emission is relative to the morphology of SiNWs. As the SiNW array is uniform in height and easy to fabricate, the MWCNT/SiNW array shows potential applications in flat electric display.     

Identification of about 100-meV acceptor level in?ZnO?nanostructures by photoluminescence

ZnO nanorod arrays and nanowires were grown by hydrothermal and vapor phase deposition methods, respectively. At low temperature, the photoluminescence (PL) spectra of both samples are dominated by a broad peak around 3.34 eV. Combined with excitation density-dependent PL spectra and surface passivation process, it is indicated from temperature-dependent PL results that the 3.34 eV emission could be attributed to free electron-to-neutral acceptor transitions. The acceptor level is estimated to be ∼100 meV.     

Structural and photoluminescence investigation on the hot-wire assisted plasma enhanced chemical vapor deposition growth silicon nanowires

High density of silicon nanowires (SiNWs) were synthesized by a hot-wire assisted plasma enhanced chemical vapor deposition technique. The structural and optical properties of the as-grown SiNWs prepared at different rf power of 40 and 80 W were analyzed in this study. The SiNWs prepared at rf power of 40 W exhibited highly crystalline structure with a high crystal volume fraction, X_C of ～82% and are surrounded by a thin layer of SiO_x. The NWs show high absorption in the high energy region (E>1.8 eV) and strong photoluminescence at 1.73 to 2.05 eV (red–orange region) with a weak shoulder at 1.65 to 1.73 eV (near IR region). An increase in rf power to 80 W reduced the X_C to ～65% and led to the formation of nanocrystalline Si structures with a crystallite size of <4 nm within the SiNWs. These NWs are covered by a mixture of uncatalyzed amorphous Si layer. The SiNWs prepared at 80 W exhibited a high optical absorption ability above 99% in the broadband range between 220 and ～1500 nm and red emission between 1.65 and 1.95 eV. The interesting light absorption and photoluminescence properties from both SiNWs are discussed in the text.     

Near-IR photoluminescence from Si/Ge nanowire-grown silicon wafers: effect of HF treatment

We present the room-temperature near-infrared (NIR) photoluminescence (PL) properties of Si/Ge nanowire (NW)-grown silicon wafers which were treated by vapor of HF:HNO₃ chemical mixture. This treatment activates or enhances the PL intensity in the NIR region ranging from 1000 nm to 1800 nm. The PL consists of a silicon band-edge emission and a broad composite band which is centered at around 1400–1600 nm. The treatment modifies the wafer surface particularly at defect sites especially pits around NWs and NW surfaces by etching and oxidation of Si and Ge. This process can induce spatial confinement of carriers where band-to-band (BB) emission is the dominant property in Si-capped strained Si/Ge NW-grown wafers. Strong signals were observed at sub-band-gap energies in Ge-capped Si/Ge NW-grown wafers. It was found that NIR PL is a competitive property between the Si BB transition and deep-level emission, which is mainly attributable to Si-related defects, Ge dots and strained Ge layers. The enhancement in BB and deep-level PL is discussed in terms of strain, oxygen-related defects, dot formation and carrier-confinement effects. The results demonstrate the effectiveness of this method in enhancing and tuning NIR PL properties for possible applications.     

The effect of differently sized Ag catalysts on the fabrication of a silicon nanowire array using Ag-assisted electroless etching

A simple and low cost method to generate single-crystalline, well-aligned silicon nanowires (SiNWs) of large area, using Ag-assisted electroless etching, is presented and the effect of differently sized Ag catalysts on the fabrication of SiNWs arrays is investigated. The experimental results show that the size of the Ag catalysts can be controlled by adjusting the pre-deposition time in the AgNO₃/HF solution. The optimum pre-deposition time for the fabrication of a SiNWs array is 3 min (about 162.04 ± 38.53 nm Ag catalyst size). Ag catalysts with smaller sizes were formed in a shorter pre-deposition time (0.5 min), which induced the formation of silicon holes. In contrast, a large amount of Ag dendrites were formed on the silicon substrate, after a longer pre-deposition time (4 min). The existence of these Ag dendrites is disadvantageous to the fabrication of SiNWs. Therefore, a proper pre-deposition time for the Ag catalyst is beneficial to the formation of SiNWs.SiNWs were synthesized in the H₂O₂/HF solution system for different periods of time, using Ag-assisted electroless etching (pre-deposition of the Ag catalyst for 3 min). The length of the SiNWs increases linearly with immersion time. From TEM, SAED and HRTEM analysis, the axial orientation of the SiNWs is identified to be along the [001] direction, which is the same as that of the initial Si wafer. The use of HF may induce Si–H_x bonds onto the SiNW array surface. Overall, the Ag-assisted electroless etching technique has advantages, such as low temperature, operation without the need for high energy and the lack of a need for catalysts or dopants.     

Power density and temperature dependent multi-excited states in InAs/GaAs quantum dots

Self-assembled InAs/GaAs (001) quantum dots (QDs) were grown by molecular beam epitaxy using ultra low-growth rate. A typical dot diameter of around 28 ± 2 nm and a typical height of 5 ± 1 nm are observed based on atomic force microscopy image. The photoluminescence (PL) spectra, their power and temperature dependences have been studied for ground (GS) and three excited states (1–3ES) in InAs QDs. By changing the excitation power density, we can significantly influence the distribution of excitons within the QD ensemble. The PL peak energy positions of GS and ES emissions bands depend on an excitation light power. With increasing excitation power, the GS emission energy was red-shifted, while the 1–3ES emission energies were blue-shifted. It is found that the full width at half maximum of the PL spectra has unusual relationship with increasing temperature from 9 to 300 K. The temperature dependence of QD PL spectra shown the existence of two stages of PL thermal quenching and two distinct activation energies corresponding to the temperature ranges I (9–100 K) and II (100–300 K).     

Temperature-dependent photoluminescence of arsenic-doped Si nanocrystals

The characteristics of temperature-dependent photoluminescence (PL) from Si nanocrystals and effects of arsenic-doping (As-doping) were investigated. The Si nanocrystals on a p-type Si substrate were prepared by low pressure chemical vapor deposition and post-deposition thermal oxidation. The As-doping process was carried out using the gas-phase-doping technique. Temperature-dependent PL from Si nanocrystals exhibited considerable differences between samples with/without As-doping. Phase transition between electron-hole liquid and free exciton was observed in the undoped Si nanocrystals, leading to the increase in PL intensity with temperature less than 50 K. Electron emission from As-doped Si nanocrystals to the p-Si substrate was responsible for the significant increase in PL intensity with temperature greater than 50 K. Characteristics of light emission from Si nanocrystals will facilitate the development of silicon-based nanoscaled light-emitting devices.     

A simple method for well-defined and clean all-SiC nano-ripples in ambient air

Well-defined and clean all-SiC nano-ripples with a period of about 150 nm are produced via the combination of 800-nm femtosecond laser irradiation and chemical selective etching with mixture solution of 65 wt% HNO₃ acid (20 mL) and 40 wt% HF acid (20 mL). The incorporation mechanism of oxygen (O) species into the laser induced obscured nano-ripples is attributed to femtosecond laser induced trapping effect of dangling bonds, while that of chemical etching induced well-defined and clean nano-ripples is assigned to chemical reactions between mixture acid solution and amorphous silicon carbide (SiC) or silicon oxide (SiO₂). Results from EDX analysis show that the incorporated foreign O species (atomic percentages of 9.39%) was eliminated effectively via chemical etching, while the atomic percentages of silicon (Si) and carbon (C) were about 47.82% and 52.18% respectively, which were similar to those of original SiC material. And the influences of laser irradiation parameters on the nano-ripples are also discussed.     

Enhanced photoluminescence in grooved silicon microstructures

Grooved silicon structures formed by anisotropic chemical etching of crystalline silicon (c-Si) wafers in alkaline solution and composed by c-Si walls and voids (grooves) with thicknesses of several micrometers were found to exhibit efficient photoluminescence after excitation with laser radiation at 1.06 μm. The photoluminescence emission which originates from the interband radiative recombination of charge carriers in c-Si walls was represented by a broad spectral band centered at 1.1 eV. Independently on the polarization direction of the excitation light the photoluminescence of grooved silicon structures was partially linear-polarized with the polarization degree of 0.15–0.24 along c-Si walls and the photoluminescence intensity was strongly enhanced in comparison with that of c-Si substrate. These experimental observations are explained by considering an enhancement of the photoluminescence excitation due to both partial light localization in c-Si walls and a low rate of the non-radiative recombination at surface defects on c-Si walls. The defect density could be modified by additional chemical treatment or thermal annealing, which resulted in significant changes of the photoluminescence intensity of the grooved Si structures. The obtained results are discussed in view of possible applications of grooved Si in optoelectronics and molecular sensorics.     

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.     

Quantitative analysis of the phonon confinement effect in arbitrarily shaped Si nanocrystals decorated on Si nanowires and its correlation with the photoluminescence spectrum

Arrays of single‐crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) are grown by a metal‐assisted chemical etching process using silver (Ag) as the noble metal catalyst. The metal‐assisted chemical etching‐grown Si NWs exhibit strong photoluminescence (PL) emission in the visible and near infrared region at room temperature. Quantum confinement of carriers in the Si NCs is believed to be primarily responsible for the observed PL emission. Raman spectra of the Si NCs decorated on Si NWs exhibit a red shift and an asymmetric broadening of first‐order Raman peak as well as the other multi‐phonon modes when compared with that of the bulk Si. Quantitative analysis of confinement of phonons in the Si NCs is shown to account for the measured Raman peak shift and asymmetric broadening. To eliminate the laser heating effect on the phonon modes of the Si NWs/NCs, the Raman measurement was performed at extremely low laser power. Both the PL and Raman spectral analysis show a log‐normal distribution for the Si NCs, and our transmission electron microscopy results are fully consistent with the results of PL and Raman analyses. We calculate the size distribution of these Si NCs in terms of mean diameter (D₀) and skewness (σ) by correlating the PL spectra and Raman spectra of the as‐grown Si NCs decorated on Si NWs. Copyright © 2015 John Wiley & Sons, Ltd.     

Black-body emission from nanostructured materials

Photoluminescence (PL) experiments on materials of low thermal conductance can cause black-body emission from the sample even at low intensities of laser excitation. This thermal emission may be misinterpreted in terms of quantum emission. Although the quantum origin of most radiative emissions in nanostructured materials such as porous silicon is well established, we show in this paper that SiC nanoparticles and mechanically milled Si do exhibit thermal emission at typical excitation intensities for PL measurements provided the samples are under vacuum. An Si membrane was also investigated and the fact that it did not emit black-body radiation is explained with a simple analysis of the heating in materials of reduced dimensionality.     

Luminescence study of Si/Ge quantum dots

We present a photoluminescence (PL) study of Ge quantum dots embedded in Si. Two different types of recombination processes related to the Ge quantum dots are observed in temperature-dependent PL measurements. The Ge dot-related luminescence peak near 0.80 eV is ascribed to the spatially indirect recombination in the type-II band lineup, while a high-energy peak near 0.85 eV has its origin in the spatially direct recombination. A transition from the spatially indirect to the spatially direct recombination is observed as the temperature is increased. The PL dependence of the excitation power shows an upshift of the Ge quantum dot emission energy with increasing excitation power density. The blueshift is ascribed to band bending at the type-II Si/Ge interface at high carrier densities. Comparison is made with results derived from measurements on uncapped samples. For these uncapped samples, no energy shifts due to excitation power or temperatures are observed in contrast to the capped samples.     

MOVPE 生长GaN薄膜的 光致黄带发光与激发光源的相关性

用四种不同光源作为激发光源,研究了蓝宝石衬底金属有机物汽相外延方法生长的氮化镓薄膜的光致发光特性。结果发现用连续光作为激发光源时,光致发光谱中除出现365 nm的带边发射峰外,同时观察到中心波长位于约550 nm 的较宽黄带发光;而用脉冲光作为激发光源时其发光光谱主要是365 nm附近的带边发光峰,未观察到黄带发光。氮化镓薄膜的光致发光特性依赖于所用的激发光源性质。     

Emission properties of a distributed feedback laser cavity containing silicon nanocrystals

We report on light emission from silicon nanocrystals (Si-nc) in a laser cavity. Using modified electrochemical etching of Si wafers we prepare Si-nc with blue-shifted photoluminescence spectrum down to 580-620 nm, embedded at high-volume fractions in a SiO₂-based solid matrix. We insert this active medium into an optically pumped resonator. Since our samples are only partially homogeneous, we cannot use external mirrors in order to achieve optical feedback: we induced optically an internal distributed cavity by intense, spatially periodical excitation. Mode selection was simulated by a simplified theoretical model, based on an approach of multiple reflections. In the framework of the model we discuss the experimentally observed spectral emission changes induced by the distributed cavity.     

Effects of silver and gold catalytic activities on the structural and optical properties of silicon nanowires

The metal-assisted chemical etching of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large area, uniform silicon nanowire (SiNW) arrays. In this study, silver (Ag) and gold (Au) are considered as catalysts and the effect of different catalysts with various thicknesses on the structural and optical properties of the fabricated SiNWs is investigated. The morphology of deposited catalysts on the silicon wafer is characterized by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is shown that the morphology of the fabricated silicon nanostructures remarkably depends upon the catalyst layer thickness, and the catalyst etching time directly affects the structural and optical properties of the synthesized SiNWs. FESEM images show a linear increment of the nanowire length versus time, whereas the etching rate for the Au-etched SiNWs was lower than the Ag-etched ones. Strong light scattering in SiNWs caused the total reflection to decrease in the range of visible light, and this decrement was higher for the Ag-etched SiNW sample, with a longer length than the Au-etched one. A broadband visible photoluminescence (PL) with different peak positions is observed for the Au- and Ag-etched samples. The synthesized optically active SiNWs can be considered as a promising candidate for a new generation of nano-scale opto-electronic devices.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.