Au deposits on graphite: On the nature of high temperature desorption peaks in CO thermal desorption spectra

Due to the discovery of Au as a catalyst for low temperature CO oxidation, the adsorption of CO on Au surfaces has attracted a lot of attention recently. On stepped and rough single crystal surfaces as well as on deposited particles two characteristic desorption states above 100 K have been observed via TPD. We have studied Au deposits on graphite in order to elucidate the nature of these desorption peaks in more detail. For this purpose, Au was deposited at 100 K and 300 K on HOPG as a weakly interacting support. In analogy to other supports, we obtain two desorption states (∼140 K and ∼170 K) whose relative intensities depend strongly on the deposition temperature with the high temperature peak being much more pronounced for the 100 K deposits. After annealing to 600 K, both states drastically lose intensity. XP spectra, on the other hand, show virtually no decrease of the Au 4f intensity as would be expected for desorption or significant changes of the particle morphologies. We conclude that both desorption peaks are defect-related and connected with under-coordinated Au atoms that are lost for the most part upon annealing. These sites could be located at the perimeter of dendritic islands or on small, defect-rich particles in addition to larger particles not adsorbing CO at 100 K. Preliminary STM results are in favour of the second interpretation.     

Charge storage and electron/light emission properties of silicon nanocrystals

Monodispersed silicon nanocrystals show novel electrical and optical characteristics of silicon quantum dots, such as single-electron tunneling, ballistic electron transport, visible photoluminescence and high-efficiency electron emission.Single-electron memory effects have been studied using a short-channel MOSFET incorporating Si quantum dots as a floating gate. Surface nitridation of Si nanocrystal memory nodes extends the charge-retention time significantly. Single-electron storage in individual Si dots has been evaluated by Kelvin probe force microscopy.Photoluminescence and electron emission are observed for surface-oxidized silicon nanocrystals. Efficiency of the no-phonon-assisted transition increases with decreasing core Si size. Electron emission efficiency as high as 5% has been achieved for the Si-nanocrystal-based cold electron emitter devices. The non-Maxwellian energy distribution of emitted electrons suggests that the mechanism of electron emission is due to ballistic transport through arrays of surface-oxidized Si nanocrystals. Combined with the ballistic electron emission, the quasi-direct light emission properties can be used for developing Si-based lasers.     

Quantitative analysis of thermally induced desorption during halogen-etching of a silicon (1 1 1) surface

Thermal desorption at a chlorine-adsorbed Si(1 1 1) surface was measured with high precision. High-sensitivity measurements of the temperature dependence of the isothermal process, and thermal desorption spectra (TDS) with various parameters, heating rates and levels of surface coverage, indicated that the desorption is a second-order reaction with an activation energy of 2.2 eV. The wide dynamic-range data throw light on the ability of various methods of thermal desorption measurement to describe quantitatively the surface reaction. It is important to obtain a precise energy value, which can be done by considering the whole TDS shape, as well as isothermal data, in order to distinguish various reaction processes. Our results are consistent with model calculations.     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embeded in an SiO₂ matrix is compared with that of unpassivated ones. We investigate the relative enhancement of PL intensity (I_R) as a function of annealing temperature and implanted Si ion dose. The I_R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization via varying the annealing temperature. The increase in I_R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Hydrogen desorption kinetics and band bending for 6H-SiC(0 0 0 1) surfaces

The desorption kinetics of hydrogen from polished 6H-SiC(0 0 0 1) surfaces exposed to various sources of hydrogen have been determined using temperature programmed desorption (TPD). For (3 × 3) 6H-SiC(0 0 0 1) surfaces prepared via annealing and cooling in SiH₄, desorption of 0.2 ± 0.05 monolayer of molecular hydrogen was observed to occur at ≈590 °C. This β₁ H₂ desorption peak exhibited second order kinetics with an activation energy of 2.4 ± 0.2 eV. For (3 × 3) 6H-SiC surfaces exposed to atomic hydrogen generated via either a hot rhenium filament or remote hydrogen plasma, low energy electron diffraction patterns showed an eventual conversion back to (1 × 1) symmetry. Spectra acquired using Auger electron and X-ray photoelectron spectroscopies revealed that the atomic hydrogen exposure removed the excess Si. Photoelectron spectroscopy results also showed a 0.5 eV increase in binding energy for the Si2p and C1s core levels after removal of the Si-Si bilayer that is indicative of a decrease in band bending at the SiC surface. TPD from the (3 × 3) 6H-SiC(0 0 0 1) surfaces exposed to atomic hydrogen showed substantially more molecular hydrogen desorption (1-2 ML) through the appearance of a new desorption peak (β_2,3) that started at ≈200 °C. The β_2,3 peak exhibited second order desorption kinetics and a much lower activation energy of 0.6 ± 0.2 eV. A third smaller hydrogen desorption state was also detected in the 650-850 °C range. This last feature could be resolved into two separate desorption peaks (α₁ and α₂) both of which exhibited second order kinetics with activation energies of 4.15 ± 0.15 and 4.3 ± 0.15 eV, respectively. Based on comparisons to hydrogen desorption from Si and diamond surfaces, the β and α desorption peaks were assigned to hydrogen desorption from Si and C sites, respectively.     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in a silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embedded in a SiO 2 matrix is compared with that of unpassivated Si NCs. We investigate the relative enhancement of PL intensity (I R ) as a function of annealing temperature and implanted Si ion dose. The I R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization varying via the annealing temperature. The increase in I R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Laser pyrolysis synthesis and characterization of luminescent silicon nanocrystals

Quantum dots of silicon are very attractive materials due to their photoluminescence (PL) emission that can be very strong at room temperature in the visible range under UV illumination. Weighable batches are demanded for several applications in opto-electronic, photovoltaic, medicine, and so on. Laser pyrolysis of silane in a flow reactor is an efficient method to synthesize silicon nanocrystals, but up to now the production rate for the smallest particles was very low. We present here results of a work aimed to overcome this limitation. Optimization of the laser pyrolysis process has been performed through an elaborate study of the synthesis parameters. Weighable batches of very small silicon particles were obtained in a controlled and reproducible way, with production rate in the 0.1–1 g/h. High-resolution electron microscopy and specific surface measurements show that the particles were true silicon nanocrystals in the 4–9 nm range. We have then studied their PL properties. For this purpose, we have paid a particular attention to the surface passivation, an essential step to obtain efficient PL. Various ways were explored: natural oxidation under air and dispersion in liquids. We show that after natural oxidation, the PL properties are, as expected, in agreement with the quantum confinement model. Strong PL is also obtained by dispersion in solvents, but the interpretation is less straightforward in this case, and as discussed in the paper, needs further investigation.     

Optical losses and absorption cross-section of silicon nanocrystals

 Si-rich silicon oxide and SiO₂ (SRSO)/SiO₂ multilayer (ML) samples were grown by reactive magnetron sputtering and then annealed at high temperature to induce the formation of Si-nc with mean size of 3-4 nm and density of about 3.5×10¹⁸ cm⁻³ as deduced from high resolution TEM micrographs. Refractive index and thickness have been determined by m-line measurements, which have shown a birefringence of about 1.5% due to the ML structure. Rib-loaded waveguides have been fabricated to measure propagation losses in the visible-infrared range. The analysis of the different contributions to optical losses such as Mie scattering and scattering due to waveguide roughness has allowed us to isolate the contribution due to the absorption losses and thus to extract the absorption cross-section at different wavelengths. Values of about 3.5×10⁻¹⁸ cm² have been found at 830 nm, increasing with decreasing of the wavelength.     

Studies of silicon nanocrystals in phosphorus rich SiO2 matrices

In this contribution we present a new type of optoelectronic silicon nanocrystal (Si-nc) based material, namely, Si-nc embedded into solidified pure or doped spin-on-glasses. The resulting self-supporting samples contain thin layers with high Si-nc concentrations. The visible photoluminescence (PL) maximum at room temperature is blue-shifted when the concentration of phosphorus in the spin-on-glass is increased.     

Superlinear photoluminescence in silicon nanocrystals: The role of excitation wavelength

We study the influence of the wavelength of picosecond excitation pulses on the properties of photoluminescence (PL) in a series of samples of silicon nanocrystals prepared by ion implantation into silica matrix. We observed a gradual change in the behaviour of the PL fast component (spectral shape, decay times, pump-intensity dependence) when tuning the excitation wavelength from 355 to 532 nm. We interpret the results in terms of an interplay between the PL originating from volume states of nanocrystals containing two photoexcited carrier pairs, and the PL due to the silicon oxide states. We discuss also the role of the implant fluence on the PL properties of samples.     

Surface control of optical properties in silicon nanocrystals produced by laser pyrolysis

Macroscopic quantities (g/h) of Si nanoparticles were prepared by laser pyrolysis of silane and showed photoluminescence (PL) emission in the range 700-1050 nm after oxidation in air at a temperature T ≥ 700 °C. Two different strategies were followed to reduce as-produced particle agglomeration which hinders most of the applications, namely etching with either acid or alkaline solutions. Well isolated single particles were detected after acid etching in HF. Disaggregation was also achieved by the combined effect of the high power sonication and alkaline etching by tetra-methyl ammonium hydroxide (TMAH), which leaves OH terminated surfaces. However, in both cases re-aggregation was observed within a few hours after oxide removal. Stable dispersions of Si nanoparticles in different solvents were obtained by treatments of H-terminated surfaces with the surfactant TOPO (C₂₄H₅₁PO, trioctylphospine oxide) and by treatment of OH-terminated surfaces with Na₃PO₄.     

Electronic structure and optical properties of silicon nanocrystals along their aggregation stages

The structural control of silicon nanocrystals is an important technological problem. Typically, a distribution of nanocrystal sizes and shapes emerges under the uncontrolled aggregation of smaller clusters. The aim of this computational study is to investigate the evolution of the nanocrystal electronic states and their optical properties throughout their aggregation stages. To realistically tackle such systems, an atomistic electronic structure tool is required that can accommodate about tens of thousand nanocrystal and embedding lattice atoms with very irregular shapes. For this purpose, a computationally efficient pseudopotential-based electronic structure tool is developed that can handle realistic nanostructures based on the expansion of the wavefunction of the aggregate in terms of bulk Bloch bands of the constituent semiconductors. With this tool, the evolution of the electronic states as well as the polarization-dependent absorption spectra correlated with the oscillator strengths over their aggregation stages is traced. The low-lying aggregate nanocrystal states develop binding and anti-binding counterparts of the isolated states. Such information may become instrumental with the maturity of the controlled aggregation of these nanocrystals.     

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.     

Electron-induced H atom desorption patterns created with a scanning tunneling microscope: Implications for controlled atomic-scale patterning on H-Si(1 0 0)

We have used scanning tunneling microscopy (STM) to explore the details of single and multiple H atom desorption from the H-Si(1 0 0)-2 × 1 surface induced by the inelastic scattering of electrons from an STM tip. The desorption of pairs of H atoms from individual Si dimers is rarely observed. Two-H atom desorption most often involves pairs of dimers, in the same or adjacent rows. This suggests that recombinative H₂ desorption via an interdimer reaction pathway, like that observed recently under nanosecond laser heating, may also be operative for electron-induced excitation using STM. Repeatable fabrication of desired size-selected dangling bond (DB) clusters is also achieved. The single atomic precision of the fabrication is a result of the intrinsically unfavorable paired H atom desorption from a single dimer, but does not result from the spatial localization of excitation energy of the Si-H bond under the STM tip as suggested in previous studies.     

A scanning tunneling microscopy study of water on Si(111)-(7 × 7): adsorption and oxide desorption

Scanning tunneling microscopy and temperature-programmed desorption have been used to investigate the chemistry of water on Si(111)-(7 × 7) substrates which were misoriented 2° toward the [ 10] direction. Upon room temperature exposure to water, the adatoms of the (7 × 7) unit cell are still evident even after high exposures, implying that major modifications of the substrate do not occur. At high coverages, the distribution of reacted adatoms shifts from one controlled by dissociative adsorption across the adatom-rest atom pair to a statistical distribution based on the availability of dangling bonds. Desorption of the oxide layer which remains after water adsorption and the desorption of hydrogen have also been characterized. The oxide desorption occurs along well-defined wavefronts which originate at step edges and advance in directions consistent with the underlying substrate symmetry, primarily the [ 2] direction (i.e. the wave vector points in the [ 2] direction). In regions of the surface where the oxide has desorbed, the (7 × 7) unit cell can be seen clearly. Vacancies resulting from the loss of surface silicon atoms (via the etching) coalesce into islands in the clean regions of the terraces, but unlike desorption of oxide layers from Si(100), the desorption does not occur from the boundaries of these vacancy islands.     

Electron stimulated desorption induced by the scanning tunneling microscope

The use of the scanning tunneling microscope (STM) as an excitation source and a probe of electron stimulated desorption on the atomic scale is reviewed. The case of H desorption from H-terminated Si(001) is examined in detail. Experimental results on excitation thresholds, desorption cross-sections, isotope effects and site-selectivities are presented. Evidence for mechanisms involving direct electronic and hot ground-state desorption, as well as a novel multiple-vibrational excitation mechanism is discussed. Using the latter mechanism, the ultimate resolution limit of selective single atom desorption is achieved. New results on desorption from Si dihydride, including a proposed mechanism for the STM-induced H/Si(001)-3 × 1 to 2 × 1 conversion, are presented. Possible applications of STM-induced desorption in nanofabrication are considered.     

Optical inter- and intra-band transitions in silicon nanocrystals: The role of surface vibrations

Silicon nanocrystals (ncs) belong to an interesting class of semiconductor nanostructures that manifest size dependent electronic properties. This well known effect of quantum confinement can explain many properties of silicon ncs. However, with decreasing size and dimension of the ncs, the role of surface phenomena becomes substantial. For example, we have shown recently that the strong luminescence from these ncs should be assigned to the exclusion of nonradiative channels rather than to the enhancement of radiative inter-band transitions. In addition, using infrared intra-band transitions spectroscopy, we were able to resolve the quantized electronic sublevels of small silicon ncs. We have found that under appropriate conditions, these electronic sublevels are resonantly coupled to surface vibrations. We suggest that this coupling mechanism is responsible for the exclusion of nonradiative channels in silicon ncs.     

Electrical and memory properties of silicon nitride structures with embedded Si nanocrystals

In this work, the electrical and memory behaviour of metal-silicon nitride-silicon structures with an embedded nanocrystalline silicon layer, which either consists of separated silicon nanocrystals, or is a continuous nanocrystalline layer, are presented. The structures were prepared by low-pressure chemical vapour deposition (LPCVD). The effect of the duration of deposition and the structure of the nanocrystalline layer were studied. The writing/erasing behaviour was similar for all the structures, but the retention properties were much worse in the structure with a continuous nanocrystalline layer, than in the structures with separated Si nanocrystals. This indicates that Si nanocrystals play role in charge storage in the studied structures.     

An AFM study of the processing of hydrogen passivated silicon(1 1 1) of a low miscut angle

We present atomic force microscopy (AFM) measurements from a passivated silicon crystal miscut by 0.1° and show the etching regime to be significantly different from surfaces with a larger miscut angle. A simple kinetic model is developed to explain the results and is used to derive the optimal etching conditions for nominally flat Si(1 1 1)–(1×1)H. We show that small changes in miscut angle can alter the kinetic steady state and promote the formation of deep etch pits, even on the least stable, miscut surface. Collisions of steps with these pits result in arrays of stable, self-aligned ‘etch hillocks' over micron dimensions. Following preparation, we use AFM to observe the initial growth of native oxide on the Si(1 1 1)–(1×1)H surface, and demonstrate that AFM is a sensitive probe to surface oxidation in the sub-monolayer regime.     

Internal quantum efficiency enhancement of silicon nanocrystals using double layer Au-rich cermet films

To improve the internal quantum efficiency of silicon nanocrystals, a double layer structure with Au-rich cermet is proposed. In the region far below surface plasmon resonance energy, effective enhancement can be still obtained, which indicates means to make surface plasmon mediated enhancement efficient in a wide wavelength region especially for long wavelength.