Light emission from nanocrystalline silicon clusters embedded in silicon dioxide: Role of the suboxide states

Silicon clusters embedded in a silicon dioxide matrix were prepared by ultrasound-assisted implantation resulting in a modified concentration of suboxide states as revealed by high-resolution photoelectron spectroscopy. It is suggested that ultrasound treatment results in formation of different interface structure between silicon cluster and silicon dioxide matrix which is characterized by a distinctly reduced concentration of the suboxide states. It is observed that photoluminescence properties are strongly correlated with the concentration of the suboxide states thereby providing an evidence that besides a quantum confinement effect a closer look at the chemical composition of the nc-Si/SiO₂ system is important.     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Temperature dependence of photoluminescence of semiconductor quantum dots upon indirect excitation in a SiO2 dielectric matrix

The processes of excitation and relaxation of confined excitons in semiconductor quantum dots upon indirect high-energy excitation have been considered. The temperature behavior of photoluminescence of quantum dots in a SiO₂ dielectric matrix has been described using a model accounting for the process of population of quantum-dot triplet states upon excitation transfer through mobile excitons of the matrix. Analytical expressions that take into account the two-stage and three-stage schemes of relaxation transitions have been obtained. The applicability of these expressions for analyzing fluorescence properties of semiconductor quantum dots has been demonstrated using the example of silicon and carbon nanoparticles in the thin-film SiO₂ matrix. It has been shown that the complex character of the temperature dependences of the photoluminescence upon indirect excitation can be an indication of a multistage relaxation of excited states of the matrix and quantum dots. The model concepts developed in this study allow one to predict the form of temperature dependences of the photoluminescence for different schemes of indirect excitation of quantum dots.

     

Erbium ion luminescence of silicon nanocrystal layers in a silicon dioxide matrix measured under strong optical excitation

The photoluminescence (PL) spectra and kinetics of erbium-doped layers of silicon nanocrystals dispersed in a silicon dioxide matrix (nc-Si/SiO₂) are studied. It was found that optical excitation of nc-Si can be transferred with a high efficiency to Er³⁺ ions present in the surrounding oxide. The efficiency of energy transfer increases with increasing pumping photon energy and intensity. The process of Er³⁺ excitation is shown to compete successfully with nonradiative recombination in the nc-Si/SiO₂ structures. The Er³⁺ PL lifetime was found to decrease under intense optical pumping, which implies the establishment of inverse population in the Er³⁺ system. The results obtained demonstrate the very high potential of erbium-doped nc-Si/SiO₂ structures when used as active media for optical amplifiers and light-emitting devices operating at a wavelength of 1.5 μm.     

Controlling surface states and photoluminescence of porous silicon by low-energy-ion irradiation

Porous silicon (PS) was irradiated by three kinds of low-energy ions with different chemical activity, namely argon ions, nitrogen ions and oxygen ions. The chemical activity of ions has significant effect on the surface states and photoluminescence (PL) properties of PS, The photoluminescence quenching after argon ions and nitrogen ions irradiation is ascribed to the broken Si-Si bonds, while the PL recovery is attributed to the oxidation of Si-H back bonds. Oxygen ions irradiation leads to the formation of a SiO_x layer with oxygen defects and PS shows different PL evolution than PS irradiated by argon ions and nitrogen ions.     

Model of photoluminescence from ion-synthesized silicon nanocrystal arrays embedded in a silicon dioxide matrix

A four-level model of photoluminescence from Si nanocrystal arrays embedded in a SiO₂ matrix is suggested. The model allows for thermally activated transitions between singlet and triplet levels in the exchange-split energy state of an exciton in an excited silicon nanocrystal. An expression is derived for the temperature dependence of the intensity of photoluminescence monochromatic components. A correlation is found between the amount of splitting and the emitted photon energy by comparing model data with our experimental data for ion-synthesized Si nanocrystals in a SiO₂ matrix. The model explains the finiteness of the photoluminescence intensity at temperatures close to 0 K and the nonmonotonicity of the temperature run of the intensity.     

Radiative and nonradiative recombination of self-trapped exciton on silicon nanocrystal interface

The theory of the multiphonon and radiative recombination of a self-trapped exciton on the interface of a silicon nanocrystal in a SiO₂ matrix is developed. Self-trapped excitons play a key role in the hot carrier dynamics in nanocrystals under photoexcitation. The ratio of the probabilities of the multiphonon and radiative recombination of the self-trapped exciton is estimated. The probabilities of exciton tunnel transition from the self-trapped state to a nanocrystal are calculated for nanocrystals of various sizes. The infrared range spectrum of the luminescence of the self-trapped exciton is obtained.     

Embedded silicon nanocrystal interface structure and strain

The structure of nanocrystal-matrix interface and strain in embedded nanocrystals are studied using large-scale atomistic simulations, with the examples of Si nanocrystal embedded in amorphous matrix of SiO₂. Photoluminescence from silicon nanocrystals embedded in a dielectric matrix like SiO₂ and Si₃N₄ are promising for Si-based optical devices. The nanocrystal-matrix interface plays a crucial role in understanding its optical and electrical properties. Nanocrystals with diameters varying from 2.17 to 4.56 nm are studied. A detailed quantitative analysis of the variation of Si/SiO₂ interface structure and strain distribution with nanocrystal diameter is reported. A linear variation of the interface width with nanocrystal diameter is observed with thinner interfaces for larger nanocrystals. Local deformation analysis reveals that the smaller nanocrystals are highly strained, whereas the strain in the larger ones shifts to the interface. This is in accordance with observed increase in total percentage of defect states in the interface from 39 to 70% for diameter increasing from 2.17 to 4.56 nm. Moreover, based on the atomic arrangements at the interface, optically active defects like Pb centres, E centres and non-bridging oxygen centres are identified and a dominance of Pb centres is observed for all the nanocrystals. The detailed structural characterization-related investigations using the proposed simulation approach will find useful application in designing system-level response of embedded nanocrystals and also to correlate various experimental observations.     

Spectral diffusion of quasi localized excitons in single silicon nanocrystals

Evolution in time of photoluminescence spectra of SiO_x capped single silicon nanocrystals has been investigated by means of confocal optical spectroscopy at room temperature. Large spectral jumps between subsequent spectra of up to 40 meV have been detected leading to noticeable line broadening and variation in the electron–phonon coupling. Further, a correlation between emission energy and emission intensity has been found and discussed in terms of an intrinsic Stark effect. Anti-correlated variations of the electron–phonon coupling to Si and SiO₂ phonons as a function of photoluminescence energy indicate that the nearly localized excition is to some extent coupled to phonons in the shell covering the silicon nanocrystal. However, coupling is reduced upon increasing Stark effect, while at the same time coupling to phonons of the Si core increases.     

Luminescence and structure of nanosized inclusions formed in SiO2 layers under double implantation of silicon and carbon ions

Luminescent and structural characteristics of SiO₂ layers exposed to double implantation by Si⁺ and C⁺ ions in order to synthesize nanosized silicon carbide inclusions have been investigated by the photoluminescence, electron spin resonance, transmission electron microscopy, and electron spectroscopy methods. It is shown that the irradiation of SiO₂ layers containing preliminary synthesized silicon nanocrystals by carbon ions is accompanied by quenching the nanocrystal-related photoluminescence at 700–750 nm and by the enhancement of light emission from oxygen-deficient centers in oxide in the range of 350–700 nm. Subsequent annealing at 1000 or 1100°C results in the healing of defects and, correspondingly, in the weakening of the related photoluminescence peaks and also recovers in part the photoluminescence of silicon nanocrystals if the carbon dose is less than the silicon dose and results in the intensive white luminescence if the carbon and silicon doses are equal. This luminescence is characterized by three bands at ～400, ～500, and ～625 nm, which are related to the SiC, C, and Si phase inclusions, respectively. The presence of these phases has been confirmed by electron spectroscopy, the carbon precipitates have the sp ³ bond hybridization. The nanosized amorphous inclusions in the Si⁺ + C⁺ implanted and annealed SiO₂ layer have been revealed by high-resolution transmission electron microscopy.     

Photoluminescence of Er<Superscript>3+</Superscript> ions in layers of quasi-ordered silicon nanocrystals in a silicon dioxide matrix

The spectra and kinetics of photoluminescence from multilayered structures of quasi-ordered silicon nanocrystals in a silica matrix were studied for undoped samples and samples doped with erbium. It was shown that the optical excitation energy of silicon nanocrystals could be effectively transferred to Er³⁺ ions, which was followed by luminescence at a wavelength of 1.5 µm. The effectiveness of energy transfer increased as the size of silicon nanocrystals decreased and the energy of exciting light quanta increased. The excitation of erbium luminescence in the structures was explained based on dipole-dipole interaction (the Förster mechanism) between excitons in silicon nanocrystals and Er³⁺ ions in silica surrounding them.     

Erbium excitation in a SiO<Subscript>2</Subscript>: Si-nc matrix under pulsed pumping

The photoluminescence of Er³⁺ ions in a SiO₂ matrix containing silicon nanocrystals 3.5 nm in diameter is studied under resonant and nonresonant pulsed pumping with pulses 5 ns in duration. The effective erbium excitation cross section under pulsed pumping, σ_eff = 8.7 × 10^?17 cm₂, is close to that for nanocrystals. Comparison of the erbium photoluminescence intensity obtained for a SiO₂ matrix with and without nanocrystals made it possible to determine the absolute concentration of optically active nanocrystals capable of exciting erbium ions, the concentration of optically active erbium, and the average number of erbium ions excited by one nanocrystal. The study revealed that excitation transfer from one erbium ion to another is a relatively slow process, which accounts for the low efficiency of erbium ion excitation under pulsed pumping in a SiO₂ matrix containing silicon nanocrystals.     

Enhancement of the photoluminescence of silicon nanocrystals under the influence of electric field

The effect of electric field generated by the application of surface acoustic waves on photoluminescence (PL) of silicon nanocrystals embedded in SiO₂ films is studied. It is shown that the application of electric field results in an increase in the intensity of nanocrystal PL, the increase amounting to 10% at a field amplitude of 6 kV cm⁻¹. The results are discussed within the frame of the self-trapped exciton model.     

Resonant electronic energy transfer from excitons confined in silicon nanocrystals to oxygen molecules

We demonstrate efficient resonant energy transfer from excitons confined in silicon nanocrystals to molecular oxygen (MO). Quenching of photoluminescence (PL) of silicon nanocrystals by MO physisorbed on their surface is found to be most efficient when the energy of excitons coincides with triplet-singlet splitting energy of oxygen molecules. The dependence of PL quenching efficiency on nanocrystal surface termination is consistent with short-range resonant electron exchange mechanism of energy transfer. A highly developed surface of silicon nanocrystal assemblies and a long radiative lifetime of excitons are favorable for achieving a high efficiency of this process.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

Photoexcited charge carrier dynamics in silicon nanocrystal/SiO2 superlattices

We report in detail on the dynamics of photoexcited charge carriers in size-controlled silicon nanocrystals in silicon nanocrystal/SiO₂ superlattices. The samples were prepared using plasma enhanced chemical vapor deposition and subsequent thermally induced phase separation. This unique approach allows preparation of well-defined Si nanocrystals. Experimental techniques of time-resolved absorption and photoluminescence were used to monitor the carrier dynamics on a wide time scale from picoseconds to milliseconds for a set of samples with different parameters (nanocrystal size, hydrogen annealing). The initial fast decay (tens of picoseconds) dependent on pump intensity for excitation levels exceeding one electron–hole pair per nanocrystal can be interpreted in terms of the bimolecular recombination with constant B=(2–3)×10⁻¹⁰ cm³ s⁻¹. The slow pump intensity independent decay (microseconds) can be reproduced well by a stretched-exponential function. The dependence of stretched-exponential parameters on photoluminescence photon energy and sample properties agrees well with the picture of trapped carriers.     

Blue–violet photoluminescence from colloidal suspension of nanocrystalline silicon in silicon oxide matrix

We report room temperature visible photoluminescence (PL), detectable by the unaided eye, from colloidal suspension of silicon nanocrystals (nc-Si) prepared by mechanical milling followed by chemical oxidation. The PL bands for samples prepared from Si wafer and Si powder peak at 3.11 and 2.93 eV respectively, under UV excitation, and exhibit a very fast (～ns) PL decay. Invasive oxidation during chemical treatment reduces the size of the nc-Si domains distributed within the amorphous SiO₂ matrix. It is proposed that defects at the interface between nc-Si and amorphous SiO₂ act as the potential emission centers. The origin of blue–violet PL is discussed in relation to the oxide related surface states, non-stoichiometric suboxides, surface species and other defect related states.     

Influence of the dielectric matrix on photoluminescence and energy exchange in ensembles of silicon nanocrystals

The results of a numerical simulation of photoluminescence in ensembles of Si nanocrystals incorporated into SiO₂ and ZrO₂ matrices are presented. It is shown that, in the ZrO₂ matrix, which produces a lower potential barrier for electrons and holes in nanocrystals, the photoluminescence intensity decreases significantly and the spectral peak shifts towards lower energies.     

Ab-initio calculations of luminescence and optical gain properties in silicon nanostructures

Density-functional and many body perturbation theory calculations have been carried out in order to study the optical properties both in the ground and excited state configurations, of silicon nanocrystals in different conditions of surface passivation. Starting from hydrogenated clusters, we have considered different Si/O bonding geometries at the interface. We provide strong evidence that not only the quantum confinement effect but also the chemistry at the interface has to be taken into account in order to understand the physical properties of these systems. In particular, we show that only the presence of a surface Si–O–Si bridge bond induces an excitonic peak in the emission-related spectra, redshifted with respect to the absorption onset, able to provide an explanation for both the observed Stokes shift and the near-visible PL experimentally observed in Si-nc. For the silicon nanocrystals embedded in a SiO₂ matrix, the optical properties are discussed in detail. The strong interplay between the nanocrystal and the surrounding host environment and the active role of the interface region between them is pointed out, in very good agreement with the experimental results. For each system considered, optical gain calculations have been carried out giving some insights on the system characteristics necessary to optimize the gain performance of Si-nc. To cite this article: E. Degoli et al., C. R. Physique 10 (2009).     

Analytical temperature dependence of the photoluminescence of semiconductor quantum dots

The excitation and relaxation of spatially confined excitons in semiconductor quantum dots have been considered. The temperature dependence of the luminescence of quantum dots in dielectric matrices is described by the model taking into account the singlet-triplet intercombination conversion of spatially confined excitons. The analytical expression describing the temperature dependence of photoluminescence is derived and the physical meaning of the constants involved in this expression is determined. The applicability of the expression to the analysis of the luminescent properties of the quantum dots is demonstrated by the example of silicon nanoclusters in a thin-film SiO₂ matrix.