Photoluminescence of GeO<Subscript>2</Subscript> films containing germanium nanocrystals

Germanium nanocrystals were formed in a GeO₂ film during the process of germanium monoxide gas-phase deposition onto a sapphire substrate and studied by photoluminescence (PL) and Raman scattering spectroscopy. A PL peak in this heterosystem was observed in the visible region at room temperature. The sizes of Ge nanocrystals were estimated from the position of a Raman peak corresponding to scattering by localized optical phonons in germanium. The PL peak position calculated with allowance for the electron and hole size quantization in Ge nanocrystals coincides well with the experimentally observed position of this peak.     

Surface chemistry study of Mn-doped germanium nanowires

Single crystal germanium nanowires have been grown by vapour-liquid-solid deposition onto silicon oxide substrates with Au catalyst nanoparticles. They have been doped by two different techniques: Ge and Mn co-evaporation during growth and post-growth Mn implantation. Scanning electron microscopy images show that Mn-implanted nanowires have a lower surface density and a smaller average diameter (18.8 nm) than the un-doped ones and those Mn doped by co-deposition. The effectiveness of Mn doping has been verified by X-ray photoemission spectroscopy and by energy-dispersive X-ray measurements, indicating in the two cases significant Mn atomic concentration in the nanowire. X-ray diffraction indicates that the nanowires are single crystals and that they do not contain precipitates of Mn extrinsic phases. Both SEM and XPS experimental evidences are in line to indicate that the Mn doping by ion implantation is preferable with respect to that one performed by co-evaporation as it reduces the thickness of the outer oxide sheath of the nanowires and their diameter.     

In situ monitoring of nucleation and evolution of Ge nanodots on faintly oxidized Si(1 1 1) surfaces

We have investigated the nucleation and evolution of germanium (Ge) nanodot (ND)s taking place while depositing Ge onto the silicon (Si) (1 1 1) surfaces with ultra-thin Si oxide films by using ultra-high vacuum in situ high-resolution transmission electron microscopy in the profile-imaging geometry. Various types of growth phenomena such as nucleation, growth and coalescence of Ge NDs have successfully been observed. The results show that the growth phenomena of the Ge NDs are dramatically rapid after their size reaches the size of the critical nucleus. The critical nucleus size estimated from a model using the cohesive energy of the Ge NDs has been consistent with observed one.     

SEM-mapped micro-photoluminescence studies of highly luminescent micro-clusters in erbium-doped silicon-rich silicon oxide

This paper reports on the formation of unique micrometer-scale clusters in erbium-doped silicon-rich silicon oxide (ErSRSO) thin films produced by thermal evaporation. Through scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), we identify these micro-clusters as structures where the film curves away from the substrate to encase erbium-rich aggregates. Even though erbium aggregation has been reported to cause quenching, we demonstrate that the micro-clusters as a whole can exhibit significantly enhanced erbium photoluminescence (PL), with emissions over 24 times brighter than the surrounding non-cluster region. Mapping micro-photoluminescence measurements onto SEM images reveals that the erbium aggregates alone do not generate the enhanced PL, but rather the thin film encasing the aggregates is the origin of the emissions. Analysis of the PL Stark splitting shows a correlation between the micro-clusters’ fine structure and the strength of their PL. Taken together, the above evidence indicates that the micro-clusters’ strong PL is produced by changes in the local environment of the Er³⁺ inside the thin film surrounding the erbium-rich aggregates.     

Effect of ion irradiation on the structure and luminescence characteristics of porous silicon impregnated with tungsten-telluride glass doped by Er and Yb impurities

Using transmission electron microscopy and elemental analysis, it has been shown that tungsten telluride glass (TTG) containing erbium and ytterbium as impurities penetrates into pores of porous silicon (PS) when melted in vacuum at 500°C. It has been found that the intensity of photoluminescence (PL) of erbium at the wavelength of 1.54 μm in PS: TTG layers increases by a factor of up to 5 in the layers irradiated by P⁺ and Ar⁺ ions. This is assigned to ion mixing which favors interaction among the Er ions and PS-embedded Si nanocrystals initiating sensitization of the PL, as well as to broadening of the glass-impregnated PS region. Implantation of the lighter Ne⁺ ions affects only weakly the PL of erbium ions.     

Fabrication of nanopatterned germanium surface by laser-induced etching: AFM, Raman and PL studies

Fabrication of the nanopatterned germanium (Ge) surface is done by laser-induced etching. Atomic force microscopy is utilized here to study the surface and sizes of Ge nanoparticles. Raman and photoluminescence (PL) spectroscopy have been used to characterize their vibrational and light emission properties. Wavelength-dependent Raman investigations of these nanopatterned Ge surface reveal spatial distribution of sizes of nanoparticles. Nanopatterned Ge structures (etched for 60 min) emit a broad PL band having two maxima at 2.1 and 2.35 eV.     

第一性原理研究[112]硅锗异质结纳米线的电子结构与光学性质

基于密度泛函理论体系下的广义梯度近似,本文利用第一性原理方法着重研究了[112]晶向硅锗异质结纳米线的电子结构与光学性质.能带结构计算表明:随着锗原子数的增加,[112]晶向硅锗纳米线的带隙逐渐减小;对Si_(36)Ge_(24)H_(32)纳米线施加单轴应变,其能量带隙随拉应变的增加而单调减小.光学性质计算则表明:随着锗原子数的增加,[112]硅锗纳米线介电函数的峰位和吸收谱的吸收边均向低能量区移动;而随着拉应变的增大,吸收系数峰值呈现出逐渐减小的趋势,且峰位不断向低能量区移动,上述结果说明锗原子数的增加与施加拉应变均导致[112]硅锗纳米线的吸收谱产生红移.本文的研究为硅锗异质结纳米线光电器件研究与设计提供一定的理论参考.     

Quasi-direct optical transitions in Ge nanocrystals embedded in GeO<Subscript>2</Subscript> matrix

GeO₂ films with germanium nanocrystals (NCs) were deposited from supersaturated GeO vapor with subsequent dissociation on Ge:GeO₂. The films were studied using photoluminescence (PL), Raman scattering, IRspectroscopy techniques. Ge NCs in initial film have sizes about 6–8 nm and have no visible PL signal. The broad green-red PL peak was detected in Ge:GeO₂ films after thermal annealings. According to effective mass approach, maximum of PL signal from such relatively big Ge NCs should be in IR region. The experimentally observed PL signal is presumably originated due to quasi-direct L ₁-L ₃’ optical transitions “folded” in germanium NCs. The article is published in the original.     

Strain control in germanium nanowires: the use of a silicon nitride shell

The core–shell geometry is a strong tool for inducing and controlling strains in nano‐objects in order to tune their optoelectronic properties. We synthesized and characterized core–shell nanostructures by depositing a non‐epitaxial silicon nitride shell around germanium nanowires. Scanning electron microscopy as well as energy dispersive X‐ray spectroscopy confirms the structural integrity of the heterostructures, and grazing incidence X‐ray diffraction measurements reveal the presence of a radial tensile strain in the Ge nanowires. A control of this strain is then demonstrated up to 0.3% by adjusting the SiN_x shell thickness versus Ge nanowire diameter. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self-assembled germanium nano-structures by laser-assisted oxidation

The investigation on the oxidation behaviour of Si自聚集锗 纳米结构 激光辅助氧化 PL光谱low-temperature oxidation, laser-assisted, nano-structure, PL spectraProject supported by the Natural Science Foundation of Guizhou Province, China (Grant No 3067(2004)).2005-04-202005-04-202005-10-08The investigation on the oxidation behaviour of Si1-xGex alloys （x=0.05, 0.15, and 0.25） is carried out. It is found for the first time that on the oxide film a germanium nano-cap with a thickness of 1.8-2.8nm and a few Ge nanoparticles with diameters ranging from 5.5 nm to 10 nm are formed by the low-temperatu.re laser-assisted dry oxidation of Si1-xGex substrate. A new scanning method on the decline cross-section of the multiple-layer sample is adopted to measure the layer thickness and the composition. Some new peaks in photoluminescence （PL） spectra are discovered, which could be related to the nano-cap and the nano-particles of germanium. A suitable model and several new calculating formulae with the unrestricted Hartree-Fock-Roothaan （UHFR） method and quantum confinement analysis are proposed to interpret the PL spectra and the nano-structure mechanism in the oxide.     

Structural and optical properties of Ge nanocrystals obtained by hot ion implantation into SiO2 and further ion irradiation

In this work, SiO₂ layers containing Ge nanocrystals (NCs) obtained by the hot implantation approach were submitted to an ion irradiation process with different 2 MeV Si⁺ ion fluences. We have investigated the photoluminescence (PL) behavior and structural properties of the irradiated samples as well as the features of the PL and structural recovery after an additional thermal treatment. We have shown that even with the highest ion bombardment fluence employed (2×10¹⁵ Si/cm²) there is a residual PL emission (12% from the original) and survival of some Ge NCs is still observed by transmission electron microscopy analysis. Even though the final PL and mean diameter of the nanoparticles under ion irradiation are independent of the implantation temperature or annealing time, the PL and structural recovery of the ion-bombarded samples have a memory effect. We have also observed that the lower the ion bombardment fluence, the less efficient is the PL recovery. We have explained such behavior based on current literature data.     

Synchrotron investigations of the specific features in the electron energy spectrum of silicon nanostructures

The Si L _{2, 3} x-ray absorption near-edge structure (XANES) spectra of porous silicon nanomaterials and nanostructures with epitaxial silicon layers doped by erbium or containing germanium quantum dots are measured using synchrotron radiation for the first time. A model of photoluminescence in porous silicon is proposed on the basis of the results obtained. According to this model, the photoluminescence is caused by interband transitions between the energy levels of the crystalline phase and oxide phases covering silicon nanocrystals. The stresses generated in surface silicon nanolayers by Ge quantum dots or clusters with incorporated Er atoms are responsible for the fine structure of the spectra in the energy range of the conduction band edge and can stimulate luminescence in these nanostructures.     

X-ray photoelectron and auger spectroscopy analysis of Ge:Mn-based magnetic semiconductor layers

Thin (～60 nm) germanium layers supersaturated with a manganese impurity of 10–16 at % have been studied by x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The layers have been fabricated by pulsed laser deposition onto a semi-insulating single-crystal GaAs substrate. The results of XPS analysis of the Ge:Mn layers reveal a change in the line shape of germanium and manganese (2p) in the surface region compared to deeper layers, which indicates a transition from the oxidized form of the base material (Ge²⁺ and Ge¹⁺) and impurity (Mn²⁺) near the surface to the unoxidized state of germanium (Ge ⁰) and manganese (Mn⁰) in the interior of the layer. The XPS spectra of the valence electrons of the Ge:Mn structure indicate that the density of states in the valence band of the ferromagnetic Ge:Mn structures is caused not only by mechanical mixing of germanium and manganese. The composition of heterogeneous inclusions in Ge:Mn films has been studied using scanning Auger microscopy.     

Time-resolved photoluminescence study of the red emission in nanoporous SiGe alloys

Porous Si_1−xGe_x (PSiGe) layers with efficient room temperature visible photoluminescence (PL) were elaborated by anodical etching from p-type doped epitaxial layers with Ge contents from 5 to 30%. The luminescence is characterised by a broad PL band centred at 1.8 eV. Time resolved photoluminescence decay is studied in porous silicon germanium as a function of germanium content, temperature, emission energies and surface passivation. The PL decay line shape is well described by a stretched exponential in all cases. The effective lifetime at low temperature in as prepared porous Si_1−xGe_x is 400 μs, i.e. an order of magnitude less than in porous silicon. After the formation of a 20 Å thick oxide surface layer we observe a decrease of the effective lifetime to 20 μs at T=4 K.     

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.     

Equivalent oxide thickness scaling of Al2O3/Ge metal-oxide-semiconductor capacitors with ozone post oxidation

Aluminum-oxide films deposited as gate dielectrics on germanium （Ge） by atomic layer deposition were post oxidized in an ozone atmosphere. No additional interfacial layer was electron microscopy and X-ray photoelectron spectroscopy detected by the high-resolution cross-sectional transmission measurements made after the ozone post oxidation （OPO） treatment. Decreases in the equivalent oxide thickness of the OPO-treated Al2O3/Ge MOS capacitors were confirmed. Furthermore, a continuous decrease in the gate leakage current was achieved with increasing OPO treatment time. The results can be attributed to the film quality having been improved by the OPO treatment.     

Fabrication, morphology and structural characterization of ordered single-crystal Ag nanowires

Highly aligned Ag nanowires have been synthesized by dc electrodeposition within a hexagonal close-packed nanochannel anodic aluminum oxide template. The pore diameter varies from 20 nm to 50 nm depending on the anodization voltage and temperature for the two types of aqueous solutions, sulphuric and oxalic acids, respectively. The size and morphology of the Ag nanowire arrays were measured by scanning electron microscopy and transmission electron microscopy. The images indicate that the highly aligned Ag nanowires grow in the uniform nanochannels of the anodic alumina template and that the size of the nanowires depends on the size of the nanochannels. X-ray diffraction, selected area electron diffraction pattern and high-resolution transmission electron microscopy images show that the Ag nanowires are single-crystal. The temperature coefficient of resistivity (temperature range from 4.2 K to 300 K) of the Ag nanowire arrays decreases with decreasing diameter of the nanowires. Received: 5 November 2001 / Revised version: 12 March 2002 / Published online: 6 June 2002     

Hexagonal germanium formed via a pressure‐induced phase transformation of amorphous germanium under controlled nanoindentation

We have studied the stable end phase formed in amorphous germanium (a‐Ge) films that have been subjected to a pressure‐induced phase transformation under indentation loading using a large (20 µm) spherical indenter. After indentation the samples have been annealed at room temperature to remove any residual unstable R8 and BC8 phases. Raman spectroscopy indicates a single broad peak centred around 292 cm^–1 and we have used first principles density functional perturbation theory calculations and simulated Raman spectra for nano‐crystalline diamond cubic germanium (DC‐Ge) to help identification of the final phase as hexagonal diamond germanium (HEX‐Ge). Transmission electron microscopy and selected area diffraction analysis confirmed the presence of a dominant HEX‐Ge end phase. These results help explain significant inconsistencies in the literature relating to indentation‐induced phase transitions in DC‐ and a‐Ge. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Titanium-induced germanium nanocones synthesized by vacuum electron-beam evaporation: growth mechanism and morphology evolution

High-vacuum electron-beam evaporation method is used for large area, metal-nucleated germanium (Ge) nanodots and nanocones on Si₃N₄/Si preparation. Nanodot and nanocone arrays with uniform size in bulk-quantity are synthesized using titanium (Ti) nanocrystals as nucleating center at 750 °C with different Ge deposition amount, respectively. The morphology evolution from nanodot to nanocone is studied by atomic force microscopy (AFM). The structure of the prepared sample is characterized by X-ray diffraction (XRD) and Raman scattering. Ge nanocones formed by this convenient fabrication process could have potential applications on nanoelectronics and vacuum electron field emission.     

Self-trapping of single and paired electrons in Ge2Se3

We report the theoretical prediction of single and paired electron self-trapping in Ge(2)Se(3). In finite atomic cluster, density functional calculations, we show that excess single electrons in Ge(2)Se(3) are strongly localized around single germanium dimers. We also find that two electrons prefer to trap around the same germanium dimer, rupturing a neighboring Ge-Se bond. Localization is less robust in periodic, density functional calculations. While paired electron self-trapping is present, as shown by wavefunction localization around a distorted Ge-Ge dimer, single-electron trapping is not. This discrepancy appears to depend only on the boundary conditions and not on the exchange-correlation potential or basis set. For single- and paired-electron trapping, we report the adiabatic barriers to motion and we estimate hopping rates and freeze-in temperatures. For the single trapped electron, we also predict the (73)Ge and (77)Se hyperfine coupling constants.