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.     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

Light absorption in Ge nanoclusters embedded in SiO2: comparison between magnetron sputtering and sol–gel synthesis

SiGeO films have been produced by a sol–gel derived approach and by magnetron sputtering deposition. Post-thermal annealing of SiGeO films in forming gas or nitrogen atmosphere between 600 and 900 °C ensured the phase separation of the SiGeO films and synthesis and growth of Ge nanoclusters (NCs) embedded in SiO₂. Rutherford backscattering spectrometry analysis evidenced a similar Ge concentration (~12 %), but a different Ge out-diffusion after annealing between the two types of techniques with the formation of a pure SiO₂ surface layer (~30 nm thick) in sol–gel samples. The thermal evolution of Ge NCs has been followed by transmission electron microscopy and Raman analysis. In both samples, Ge NCs form with similar size increase (from ~3 up to ~7 nm) and with a concomitant amorphous to crystalline transition in the 600–800 °C temperature range. Despite a similar Ge concentration, a significant lower NCs density is observed in sol–gel samples attributed to an incomplete precipitation of Ge, which probably remains still dispersed in the matrix. The optical absorption of Ge NCs has been measured by spectrophotometry analyses. Ge NCs produced by the sol–gel method evidence an optical band gap of around 2 eV, larger than that of NCs produced by sputtering (~1.5 eV). These data are presented and discussed also considering the promising implications of a low-cost sol–gel based technique towards the fabrication of light harvesting devices based on Ge nanostructures.     

Band structure and valence-band offset of HfO2 thin film on?Si?substrate from photoemission spectroscopy

Synchrotron radiation photoemission spectroscopy and optical transmission spectrum measurements have been performed on an HfO₂ thin film grown on a Si(100) substrate to determine the band structure of the HfO₂/Si stack. The result shows a valence-band offset of 2.5 eV and a conduction-band offset of 2.2 eV for the HfO₂/Si interface. The Schottky barrier height between Au and HfO₂ is obtained from current density–voltage measurement. The characterization reveals that the dominant conduction mechanism in the region of low field under gate injection is Schottky emission. The energy-band diagram of an Au–HfO₂–Si MOS stack was obtained from these results.     

Characteristics improvement of HfO2/Ge gate stack structure by fluorine treatment of germanium surface

Chemical reactivity of fluorine molecule (F₂)-germanium (Ge) surface and dissociation of fluorine (F)-Ge bonding have been simulated by semi-empirical molecular orbital method theoretically, which shows that F on Ge surface is more stable compared to hydrogen. Ge MIS (metal insulator semiconductor) capacitor has been fabricated by using F₂-treated Ge(1 0 0) substrate and HfO₂ film deposited by photo-assisted MOCVD. Interface state density observed as a hump in the C-V curve of HfO₂/Ge gate stack and its C-V hysteresis were decreased by F₂-treatment of Ge surface. XPS (X-ray photoelectron spectroscopy) depth profiling reveals that interfacial layer between HfO₂ and Ge is sub-oxide layer (GeO_x or HfGeO_x), which is believed to be origin of interface state density.F was incorporated into interfacial layer easily by using F₂-treated Ge substrate. These results suggest that interface defect of HfO₂/Ge gate stack structure could be passivated by F effectively.     

Investigation of Auger recombination in Ge and Si nanocrystals embedded in SiO2 matrix

We study theoretically the optical properties of embedded Ge and Si nanocrystals (NCs) in wide band-gap matrix and compared the obtained results for both NCs embedded in SiO₂ matrix. We calculate the ground and excited electron and hole levels in both Ge and Si nanocrystals (quantum dots) in a multiband effective mass approximation. We use the envelope function approximation taking into account the elliptic symmetry of the bottom of the conduction band and the complex structure of the top of the valence band in both Si and Ge (NCs). The Auger recombination (AR) in both nanocrystals is thoroughly investigated. The excited electron (EE), excited hole (EH) and biexciton AR types are considered. The Auger recombination (AR) lifetime in both NCs has been estimated and compared.     

Surface acoustic phonon modes of Ge nanocrystals embedded in SiO2

Ge nanocrystals (NCs) embedded in SiO₂ are synthesized by ion implantation, and the surface vibrational modes of the Ge NCs are investigated using the low-frequency Raman scattering (LFRS) technique. LFRS studies show distinct low-frequency Raman modes in the range 6.5-21.2 cm⁻¹ for the Ge NCs depending on the implant dose and annealing temperature. These low-frequency Raman modes are attributed to the confined surface acoustic phonon modes of Ge NCs with (0,0) spheroidal mode and (0,3) torsional modes. Our results are in excellent agreement with the recent theoretical predictions of surface vibrational modes in Ge NCs.     

Nature of chemical states of sulfur embedded in atomic‐layer‐deposited HfO2 film on Ge substrate for interface passivation

Sulfur was embedded in atomic‐layer‐deposited (ALD) HfO₂ films grown on Ge substrate by annealing under H₂S gas before and after HfO₂ ALD. The chemical states of sulfur in the film were examined by S K‐edge X‐ray absorption spectroscopy. It was revealed that the valences of S‐ions were mostly –2 at Ge/HfO₂ interface (GeS_x or HfO_2–yS_y to passivate the interface), while they were mostly +6 in HfO₂ layers (sulfates; HfO_2–z(SO₄)_z). The leakage current density in post‐deposi‐tion‐treated film was lower than that in pre‐deposition‐treated one. This suggests that the passivation of defects in oxide layer by sulfate ions is more effective to lower the leakage current rather than the interface defect passivation by S^2– ions. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Interfaces under ion irradiation: growth and taming of nanostructures

We have investigated the synthesis of nanostructures, as well as the control of their size and location by means of ion beams. The phase separation and interface kinetics under ion irradiation give new possibilities for controlling the growth of nanostructures. Additionally, the chemical decomposition of the host matrix by collisional mixing can contribute to the self-organization of nanostructures, especially at interfaces. It is shown how collisional mixing during ion implantation affects nanocrystal (NC) synthesis and how ion irradiation through NCs modifies their size and size distribution. An analytical expression for solute concentration around an ion-irradiated NC was found, which may be written like the well-known Gibbs–Thomson relation. However, parameters have modified meanings, which has a significant impact on the evolution of NC ensembles. “Inverse Ostwald ripening” of NCs, resulting in an unimodal NC size distribution, is predicted, which has been confirmed experimentally for Au NCs in SiO₂ and by kinetic lattice Monte Carlo simulations. At interfaces, the same ion-irradiation-induced mechanism may result in self-organization of NCs into a thin δ-layer. Collisional decomposition of SiO₂ may enhance the NC δ-layer formation in SiO₂ at the Si/SiO₂ interface. The distance of the self-organized NC δ-layer from the SiO₂/Si interface renders the structure interesting for non-volatile memory applications. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-351-260-3285, E-mail: K.-H.Heinig@fz-rossendorf.de     

Nanocomposites of titania and hybrid matrix with high refractive index

A sol–gel route for TiO₂ nanocrystals (NCs) synthesis has been developed at low temperature without surfactants. Synthetic and processing parameters have been optimized to maximize particles’ colloidal stability and crystallinity. The obtained TiO₂ NCs can be homogeneously dispersed in a sol–gel derived organic–inorganic hybrid material, resulting in homogeneous composite films when prepared by spin coating. High refractive index films were obtained with high TiO₂ NCs loading and good transparency. Furthermore, TiO₂ colloidal solutions can be used for depositing porous crystalline films, whose structural evolution has been followed under different annealing treatments. Nanocrystals were characterized by UV–Vis absorption, TEM, FT-Raman, and XRD techniques, while nanocomposite and TiO₂ films were analyzed by SEM, TEM, and spectroscopic ellipsometry.     

Memory properties of a Ge nanocrystal MOS device fabricated by pulsed laser deposition

The charge–storage properties of Ge nanocrystal (Nc) memory devices with MOS structure have been studied. The Ge nanocrystals (Ncs) were prepared on a p-Si (100) matrix by means of pulsed laser deposition (PLD) combined with rapid annealing in the presence of Ar gas. The device is characteristic of better switching characteristics (the I _on/I _off>10⁵), low leakage current, which was attributed to the effect of Coulomb blockade preventing injection. A significant threshold-voltage shift of 0.85 V was observed when an operating voltage of 5 V was implemented on the device. The kind of hysteresis behavior in the double sweep suggests that the device has a good electrostatic control over the Ge Nc channel.     

Optical description of HfO2/Al/HfO2 multilayer thin film devices

A three-layer system of dielectric/metal/dielectric (D/M/D) has been prepared on Marienfeld commercial glass substrates with Metal = Al, and Dielectric = HfO₂ for energy efficient windows applications. Subsequently, HfO₂/Al/HfO₂ multilayers have been deposited with 10 nm each HfO₂ layer and 5 nm thick Al layer using electron beam evaporation. The microstructural characteristics of D/M/D thin films have been investigated using X-ray diffraction (XRD) and atomic force microscopy (AFM). Present results indicate the formation of HfO₂ weak polycrystals embedded in the disordered lattice. AFM data reveals quite a smooth surface involving a structure of slightly elongated grains with almost Gaussian size distribution with mean grain size in the range from 7 to 23 nm. Regarding optical properties, maximum transmittance of the D/M/D structure is noticed to occur in the UV-region, whereas reflectance rises to ∼60% in the visible to near infrared (NIR)-regions. To optimize the performance of these D/M/D devices, computer calculations have been performed by varying either the thickness of both HfO₂ layers and/or thickness of metallic Al layer. A satisfactory agreement between theoretical and experimental spectra is noticed. Such D/M/D structures can be useful in heat mirror applications involving energy efficient windows etc.     

Evidence of GeO volatilization and its effect on the characteristics of HfO2 grown on Ge substrate

HfO₂ films are deposited by atomic layer deposition (ALD) using tetrakis ethylmethylamino hafnium (TEMAH) as the hafnium precursor, while O₃ or H₂O is used as the oxygen precursor. After annealing at 500℃ in nitrogen, the thickness of Ge oxide's interfacial layer decreases, and the presence of GeO is observed at the H₂O-based HfO₂ interface due to GeO volatilization, while it is not observed for the O₃-based HfO₂. The difference is attributed to the residue hydroxyl groups or H₂O molecules in H₂O-based HfO₂ hydrolyzing GeO₂ and forming GeO, whereas GeO is only formed by the typical reaction mechanism between GeO₂ and the Ge substrate for O₃-based HfO₂ after annealing. The volatilization of GeO deteriorates the characteristics of the high-κ films after annealing, which has effects on the variation of valence band offset and the C–V characteristics of HfO₂/Ge after annealing. The results are confirmed by X-ray photoelectron spectroscopy (XPS) and electrical measurements.     

Intensely emitting CdTe nanocrystals retained initial photoluminescence efficiency in sol–gel derived Si<Subscript>1-x</Subscript>Zr<Subscript>x</Subscript>O<Subscript>2</Subscript> glass

Emitting CdTe nanocrystals (NCs) were embedded in pure glass matrices (Si_1-xZr_xO₂, x≤0.15) using a controlled sol–gel method, where the pre-hydrolyzed condition, the molar ratio of Zr/Si, the gelation time, the pH, and the amount of alcohol were judiciously optimized considering the surface condition of the NCs and the mechanism of the glass formation. As a result, the prepared glass phosphor exhibited high photoluminescence efficiencies (40% for green and 60% for red when Zr/Si was 5–10%) by retaining their initial values as in CdTe colloidal solution. To our knowledge, these values are the highest among those ever obtained for any solid matrices containing NCs. Because of the existence of Zr, the prepared glasses exhibit much better resistance against the ambient atmosphere, heat-treatment, and boiling water compared with pure silica glass (x=0) or the glass prepared from our other methods using a silane coupling agent. Thus, the obtained glass is promising for applications such as optical devices. PACS 78.67.Bf; 78.55.Qr; 78.55.Et     

Synthesis of Ge nanocrystals by atom beam sputtering and subsequent rapid thermal annealing

Ge nanocrystals embedded in an SiO₂ matrix were prepared by the atom beam co-sputtering (ABS) method from a composite target of Ge and SiO₂. The as-deposited films were rapid thermally annealed at the temperatures 700 and 800 °C in nitrogen ambience. The structure of the films was evaluated by using X-ray diffraction (XRD) and Raman spectroscopy. XRD results reveal that as-deposited films are amorphous in nature whereas annealed samples show crystalline nature. Raman scattering spectra showed a peak of Ge–Ge vibrational mode shifted downwards to 297 cm^?1, presumably caused by quantum confinement of phonons in the Ge nanocrystals. Rutherford backscattering spectrometry has been used to measure the thickness and Ge composition of the composite films. Size variation of Ge nanocrystals with annealing temperature has been discussed. The advantages of ABS over other methods are highlighted.     

Conversion--electron gamma--ray coincidence spectroscopy of superdeformed 135Nd

Three mini-orange conversion–electron spectrometers and four Euroball Ge Cluster detectors have been used for γ–e^- coincidence spectroscopy of superdeformed ¹³⁵Nd. Transitions within the superdeformed band are shown to have the expected E2 multipolarity. The 766.5–keV transition which links the band to a positive-parity state has a conversion coefficient consistent with M1 multipolarity. Consequently, positive parity is deduced for the superdeformed band. No evidence for E0 transitions was found. Received: 22 December 1997 / Revised version: 19 January 1998     

Hafnium oxide thin films deposited from a filtered cathodic vacuum arc

The electrical and structural characteristics of hafnium oxide thin films reactively deposited from a filtered cathodic vacuum arc have been investigated. X-ray photoelectron spectroscopy was used to determine the deposition conditions (Ar/O₂ ratio) which produced stoichiometric HfO₂ films. Cross-sectional transmission electron microscopy showed that the micro-structure of the films was highly disordered with electron-diffraction analysis providing evidence for the presence of sub-nano-metre crystallites of the monoclinic HfO₂ (P2₁/c) phase. Further evidence for the presence of this phase was provided by measuring the O k-edge using electron energy loss spectroscopy and comparing it with calculations performed using FEFF8.2, a multiple scattering code. Surface imaging revealed that local film damage occurred in films deposited with substrate bias voltages exceeding −200 V. The current-leakage characteristics of the HfO₂ films deposited with a bias of approximately −100 V suggest that device grade HfO₂ films can be produced from a filtered cathodic vacuum arc.     

Synthesis of hybrid organic–inorganic nanocomposite materials based on CdS nanocrystals for energy conversion applications

Efficient solar energy conversion is strongly related to the development of new materials with enhanced functional properties. In this context, a wide variety of inorganic, organic, or hybrid nanostructured materials have been investigated. In particular, in hybrid organic–inorganic nanocomposites are combined the convenient properties of organic polymers, such as easy manipulation and mechanical flexibility, and the unique size-dependent properties of nanocrystals (NCs). However, applications of hybrid nanocomposites in photovoltaic devices require a homogeneous and highly dense dispersion of NCs in polymer in order to guarantee not only an efficient charge separation, but also an efficient transport of the carriers to the electrodes without recombination. In previous works, we demonstrated that cadmium thiolate complexes are suitable precursors for the in situ synthesis of nanocrystalline CdS. Here, we show that the soluble [Cd(SBz)₂]₂·(1-methyl imidazole) complex can be efficiently annealed in a conjugated polymer obtaining a nanocomposite with a regular and compact network of NCs. The proposed synthetic strategies require annealing temperatures well below 200 °C and short time for the thermal treatment, i.e., less than 30 min. We also show that the same complex can be used to synthesize CdS NCs in mesoporous TiO₂. The adsorption of cadmium thiolate molecule in TiO₂ matrix can be obtained by using chemical bath deposition technique and subsequent thermal annealing. The use of NCs, quantum dots, as sensitizers of TiO₂ matrices represents a very promising alternative to common dye-sensitized solar cells and an interesting solution for heterogeneous photocatalysis.     

Laser induced breakdown spectroscopy of germane plasma induced by IR CO2 pulsed laser

Laser-induced breakdown spectroscopy (LIBS) in germane (GeH₄), initially at room temperature and pressures ranging from 2 to 10 kPa, was studied using a high-power transverse excitation atmospheric (TEA) CO₂ laser (λ=10.653 μm, τ _FWHM=64 ns and power densities ranging from 0.28 to 5.52 GW cm⁻²). The strong emission spectrum of the generated plasma is mainly due to electronic relaxation of excited Ge, H and ionic fragments Ge⁺, Ge²⁺ and Ge³⁺. The weak emission is due to molecular bands of H₂. Excitation temperatures of 8100±300 K and 23,500±2500 K were estimated by Ge atomic and Ge⁺ singly ionized lines, respectively. Electron number densities of the order of (0.7–6.2)×10¹⁷ cm⁻³ were deduced from the Stark broadening of several atomic Ge lines. The characteristics of the spectral emission intensities from different species have been investigated as functions of the germane pressure and laser irradiance. Optical breakdown threshold intensities in germane at 10.653 μm have been determined. The mechanism of initiation of the laser-induced plasma in germane has been analyzed.