Electronic and optical properties of Si and Ge nanocrystals: An ab initio study

First-principles calculations within density functional theory and many-body perturbation theory have been carried out in order to investigate the structural, electronic and optical properties of undoped and doped silicon nanostructures. We consider Si nanoclusters co-doped with B and P. We find that the electronic band gap is reduced with respect to that of the undoped crystals, suggesting the possibility of impurity based engineering of electronic and optical properties of Si nanocrystals. Finally, motivated by recent suggestions concerning the chance of exploiting Ge dots for photovoltaic nanodevices, we present calculations of the electronic and optical properties of a Ge₃₅H₃₆ nanocrystal, and compare the results with those for the corresponding Si₃₅H₃₆ nanocrystals and the co-doped Si₃₃BPH₃₆.     

Silicon nanocrystal synthesis by implantation of natural Si isotopes

Implantations of pure , , and into SiO₂ can provide significant insight into the formation of silicon nanocrystals (Si-nc) and their light emission properties. Si-nc produced with different fractions of the heavier Si isotopes have been characterized by Raman and photoluminescence spectroscopy. Weak Stokes shifts of the Si-nc phonon peaks indicate that both the implanted Si and the native Si from the SiO₂ substrate contribute to Si-nc nucleation. The Raman measurements also indicate that the Si isotopic composition of the Si-nc is similar to the Si isotopic fraction of the implanted SiO₂. The Si-nc photoluminescence (PL) spectra are shifted towards the blue with increasing Si isotope mass, an indication that the increase of the Si-nc effective mass enhances the excitonic bandgap. Measurements from samples implanted with heavy isotopes at high Si excess concentrations indicate that the Si-nc isotope fraction evolves with annealing time such that the heaviest Si isotope are more concentrated in the vicinity of the Si-nc/SiO₂ interface, which can modify the energy states involved in the radiative transitions associated with Si-nc.     

Doping in silicon nanocrystals: An ab initio study of the structural, electronic and optical properties

There are experimental evidences that doping control at the nanoscale can significantly modify the optical properties with respect to the pure systems. This is the case of silicon nanocrystals (Si-nc), for which it has been shown that the photoluminescence (PL) peak can be tuned also below the bulk Si band gap by properly controlling the impurities, for example by boron (B) and phosphorus (P) codoping. In this work, we report on an ab initio study of impurity states in Si-nc. We consider B and P substitutional impurities for Si-nc with a diameter up to 2.2 nm. Formation energies (FEs), electronic, optical and structural properties have been determined as a function of the cluster dimension. For both B-doped and P-doped Si-nc the FE increases on decreasing the dimension, showing that the substitutional doping gets progressively more difficult for the smaller nanocrystals. Moreover, subsurface impurity positions result to be the most stable ones. The codoping reduces the FE strongly favoring this process with respect to the simple n-doping or p-doping. Such an effect can be attributed to charge compensation between the donor and the acceptor atoms. Moreover, smaller structural deformations, with respect to n-doped and p-doped cases, localized only around the impurity sites are observed. The band gap and the optical threshold are largely reduced with respect to the undoped Si-nc showing the possibility of an impurity-based engineering of the Si-nc PL properties.     

Design of a nanoscale silicon laser

The recent observation of optical gain from silicon nanocrystals embedded in SiO₂ opens an opportunity to develop a nanoscale silicon-based laser. However, the challenge remains to design and develop a laser architecture using CMOS-compatible materials. In this paper we present two designs for a waveguide laser in which silicon nanocrystals embedded in SiO₂ are used as the optical gain media. One design employs a SiO₂ membrane containing encapsulated Si nanocrystals. Preliminary calculations given here show that a highly resonant laser cavity can be produced in a SiO₂ membrane using sub-wavelength structures. This photonic crystal architecture, used to guide and contain the light, can be combined with a gain medium of optically active Si nanocrystals synthesized in the SiO₂ membrane using ion implantation/thermal annealing to produce a Si-based laser. The laser cavity dimensions can be matched to the near-infrared wavelengths where optical gain has been observed from Si nanocrystals. The second design utilizes silicon nanocrystals embedded in a distributed-feedback laser cavity fabricated in SiO₂. Lasing action over a broad wavelength range centered at ∼770 nm should be possible in both of these configurations. Received: 20 December 2002 / Accepted: 7 January 2003 / Published online: 11 April 2003 RID="*" ID="*"Corresponding author. Fax: +1-434/982-2037, E-mail: supriya@virginia.edu     

Sensitisation of erbium emission by silicon nanocrystals-doped SnO2

SnO₂ thin films undoped and doped with antimony (Sb), erbium (Er) and Si nanocrystals (Si-nc) have been grown on silicon (Si) substrate using sol-gel method. Room-temperature photoluminescence (PL) measurement of undoped SnO₂, under excitation at 280 nm, shows only one broad emission at 395 nm, which is related to oxygen vacancies. The PL of Er³⁺ ions was found to be enhanced after doping SnO₂ with Sb and Si-nc. The excitation process of Er is studied and discussed. The calculation of cross-section suggests a sensitisation of Er PL by Si-nc.     

X-ray absorption study of light emitting silicon nanocrystals

X-ray absorption spectra obtained by total electron yield (TEY) at the Si absorption K-edge have been measured to have chemical and structural information about Si nanocrystals (Si-nc) produced by plasma-enhanced chemical vapour deposition (PECVD). The TEY technique has been employed to investigate the formation of Si-nc and the modification of the silica matrix as a function of annealing temperature (500–1250°C) and of silicon content in the film (35–46 at%). The amount of silicon present in the Si-nc has been evaluated by TEY. Thanks to Rutherford backscattering spectrometry measurements, the amount of Si atoms bonded to oxygen and to nitrogen, incorporated by PECVD, has been assessed. A compositional model that interprets the experimental findings is presented.     

1.54 μm room temperature emission from Er-doped Si nanocrystals deposited by ECR-PECVD

In this work, silicon nanocrystals (Si-nc) embedded in a silicon-rich silicon oxide (SRSO) matrix doped with Er³⁺ ions for different erbium and silicon concentrations have been deposited by electron-cyclotron resonance plasma-enhanced chemical-vapor-deposition (ECR-PECVD) technique. Their optical properties have been investigated by photoluminescence (PL) and reflectance spectroscopy.Room temperature emission bands centered at ∼1.54 and at 0.75 μm have been obtained for all samples. The most intense emission band at ∼1.54 μm was obtained for samples with concentrations of 0.45% and 39% for erbium and silicon, respectively. Moreover, it has been found that the broad emission band centered at ∼0.75 μm for all samples shows a very strong interference pattern related to the a specific sample structure and a high sample quality.     

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.     

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.     

Study on phase separation in a-SiOx for Si nanocrystal formation through the correlation of photoluminescence with structural and optical properties

The phase separation in amorphous silicon suboxide (a-SiO_x) films upon thermal annealing for the formation of light emitting silicon nanocrystals (Si-NCs) was studied through the correlation of photoluminescence (PL) and photoluminescence excitation (PLE) with structural and optical properties. The PL and PLE features and the structural and optical properties show a strong dependence on the annealing process and reveal that the precipitation of the excess Si in a-SiO_x and the formation of Si-NCs from the precipitated Si are two separate processes which should be distinguished in the phase separation in a-SiO_x. They proceed at different temperatures and the formation of Si-NCs is a slow process compared with the precipitation of the excess Si. The nanocrystal size and size distribution evolve with annealing time at the initial stages and are mainly dependent on annealing temperature for a certain O content in the initial a-SiO_x with the density of the formed Si-NCs increasing with longer annealing duration.     

Ab initio calculation of optical absorption and reflectivity of Si(0 0 1)/SiO2 superlattices with varying interfaces

Using first-principles calculations we investigate the influence of interface modification and layer thicknesses on the optical properties of Si/SiO₂ superlattices. Four interface models with different dangling-bond passivation are considered. The results demonstrate confinement effects not only for the fundamental band gaps but also for the optical properties. While for a large Si layer thickness of the Si/SiO₂ superlattices the interface dependence is small, the calculations show a significant structure dependence for thin Si layers. © 2007 Elsevier Science. All rights reserved.     

One step towards the fabrication of a nanoscale Si-nc based laser cavity

In this paper, we report on the design of two major components of a laser architecture using Si-nc embedded in SiO₂ as the optical gain medium and sub-wavelength periodic structures to form the resonant cavity. Dimensions of the structures have been matched to near-infrared wavelengths (∼850 nm) of the maximum photoluminescent emission where optical gain has been observed from Si-nc. Both the front (FM) and rear (RM) mirrors have been fabricated by the implantation of Si ions (50 keV, 2×10¹⁷ Si⁺/cm²) through a mask, in order to produce a Bragg reflector by optical index contrast between the implanted and the non-implanted zones. Two closely spaced Bragg reflectors are used in the FM structure to allow a narrow bandpass (partial transmission) centered at 850 nm. The implanted structures have been annealed to produce Si-nc and passivation. Scanning electron microscopy (SEM) images show that the design dimensions of the structure have been obtained. Characterization of the structures by laser excitation reveals an optical gap in both mirrors between 825 and 870 nm, as per the design parameters. A quality factor Q∼95 and a reflectivity R∼0.2 have been measured for the FM. These results support the concept that a complete Si-nc based laser cavity can be built to emit coherent light.     

Photoluminescence studies from silicon nanocrystals embedded in spin on glass thin films

Photoluminescence (PL) from silicon nanocrystals (Si-nc) prepared from pulverised porous silicon and embedded in undoped (SOG) or phosphorus-doped spin-on-glass (SOD) solutions was studied. Effects of rapid thermal annealing on the PL was also investigated. A strong room temperature PL signal was observed at 710 nm due to the recombination of electron-hole pairs in Si-nc and the PL maximum shifts to the blue region as the phosphorus concentration in the spin on glass increases. However, the rapid thermal annealing process (30 s, 900°C) quenches the PL response. These results suggest that for Si-nc/SOG (SOD) the surface termination is efficient but high phosphorus doping of Si-nc is detrimental to the PL.     

Strong explosive interaction of hydrogenated porous silicon with oxygen at cryogenic temperatures

We report new types of heterogeneous hydrogen-oxygen and silicon-oxygen branched chain reactions which have been found to proceed explosively after the filling of pores of hydrogen-terminated porous silicon (Si) by condensed or liquid oxygen in the temperature range of 4.2-90 K. Infrared vibrational absorption spectroscopy shows that, while initially Si nanocrystals assembling the layers have hydrogen-terminated surfaces, the final products of the reaction are SiO2 and H2O. Time-resolved optical experiments show that the explosive reaction develops in a time scale of 10(-6) s. We emphasize the remarkable structural properties of porous Si layers which are crucial for the strong explosive interaction.     

Erbium-doped Si nanocrystals: optical properties and electroluminescent devices

In the last decade, a strong effort has been devoted towards the achievement of efficient light emission from silicon. Among the different approaches, rare-earth doping and quantum confinement in Si nanostructures have shown great potentialities. In the present work, the synthesis and properties of low-dimensional silicon structures in SiO₂ will be analyzed. All of these structures present a strong room temperature optical emission, tunable in the visible by changing the crystal size. Moreover, Si nanocrystals (nc) embedded in SiO₂ together with Er ions show a strong coupling with the rare earth. Indeed each Si nc absorbs energy which is then preferentially transferred to the nearby Er ions. The signature of this interaction is the strong increase of the excitation cross section for an Er ion in the presence of Si nc with respect to a pure oxide host. We will show the properties of Er-doped Si nc embedded within Si/SiO₂ Fabry–Pérot microcavities. Very narrow, intense and highly directional luminescence peaks can be obtained. Moreover, the electroluminescence (EL) properties of Si nc and Er-doped Si nc in MOS devices are investigated. It is shown that an efficient carrier injection at low voltages and quite intense room temperature EL signals can be achieved, due to the sensitizing action of Si nc for the rare earth. These data will be presented and the impact on future applications discussed.     

Connection of silicon nanocrystals (Si-nc) with multi-walled carbon nanotubes

During the last decade silicon nanocrystals (Si-nc) have received widespread interest because of their high quantum efficiency for light emission at room temperature. However, the challenge still ahead is to study and apply these to single Si-ncoptoelectronics, i.e., solving problems linked with connection and manipulation. In this letter we report on connecting (wiring) single Si-nc with conducting multi-walled carbon nanotubes (MWNTs). We have been able to establish a strong mechanical connection by direct growth of MWNTs on Si-nc used as support of iron nanoparticles, by catalytic chemical vapor deposition (CCVD). To monitor the initial stage of the MWNTs growth process, we used a tapered element oscillating microbalance (TEOM). We compared the growth process on Si-nc coated by iron (Fe/Si-nc) to the standard process of growing MWNTs on alumina as support for iron (Fe/Al). The results showed that in the case of Fe/Si-nc catalyst, we obtained three times larger diameter of multi-walled CNTs compared to Fe/Al. This was mainly due to the Si-nc size. The diameter of the CNTs only depended on the size of the Si-nc particles that rested stuck on the tip of the MWNTs. The connected Si-nc kept their photoluminescence properties at room temperature. The present findings open new opportunities in the development of nanodevices for the optoelectronic application field. PACS 81.07.Bc; 81.07.Lk; 81.07.De     

Laser-induced thermal effects on Si/SiO<Subscript>2</Subscript> free-standing superlattices

The thermal effects produced by continuous-wave laser radiation on free-standing Si/SiO₂ superlattices are studied. We compare two samples with different SiO₂ layer thicknesses (2 and 6 nm) and the same Si layer thickness (2 nm). The as-prepared free-standing superlattices contain some amount of Si nanocrystals (Si-nc). Intense laser irradiation at 488 nm of the as-prepared samples enhances the Raman scattering of Si-nc by two orders of magnitude. This laser-induced crystallization originates from melting of Si nanostructures in silica, which makes Si-nc better ordered and better isolated from the oxide surrounding. Continuous-wave laser control of Si-nc stress was achieved in these samples. In the proposed model, intense laser radiation melts Si-nc, and Si crystallization upon cooling down from the liquid phase in a silica matrix leads to compressive stress. The Si-nc stress can be tuned in the ∼3 GPa range using laser annealing below the Si melting temperature. The high laser-induced temperatures were verified with Raman spectroscopy. The laser-induced heat leads to a strongly nonlinear rise of light emission. The light emission is also observed in the anti-Stokes region, and its temperature dependence is practically the same for the two studied samples. The laser-induced temperature is essentially controlled by the absorbed laser power. PACS 78.55.-m; 78.20.-e; 68.55.-a; 78.30.-j     

X-ray photoelectron spectroscopy investigations of Si in non-stoichiometric SiNx LPCVD multilayered coatings

Si nanocrystals were formed in the non-stoichiometric Si-enriched SiN_x low-pressure chemical vapor deposited (LPCVD) coatings on Si wafers treated by various modes. The coating structure as a function of technological conditions was investigated by ellipsometry and X-ray photoelectron spectroscopy (XPS) depth profiling. It was found that nanocomposites on base of SiN_x films enriched by Si have a complex multilayered structure varying in dependence of deposition and annealing parameters. Analysis of the XPS spectra and Si 2s peaks shows the existence and quantity of four chemical structures corresponding to the Si–O, Si–N states, nanocrystalline and amorphous Si. The XPS results show evolution of the chemical structure of silicon nitride and formation of Si nanocrystals. It was found:

• The LPCVD technology of nanocrystals formation allows to get enough high concentration of Si nanocrystals on different depths from the sample surface.

• The volume fraction of nanocrystalline and amorphous Si is changed with depth; this relation depends from SiN_x composition and annealing parameters.

• XPS detects these two phase compositions of Si nanoparticles in SiN_x and SiO₂ layers. The ellipsometry, HR-TEM, and XPS results are in good agreement.

Nanosilicon photonics

Silicon photonics is no longer an emerging field of research and technology but a present reality with commercial products available on the market, where low‐dimensional silicon (nanosilicon or nano‐Si) can play a fundamental role. After a brief history of the field, the optical properties of silicon reduced to nanometric dimensions are introduced. The use of nano‐Si, in the form of Si nanocrystals, in the main building blocks of silicon photonics (waveguides, modulators, sources and detectors) is reviewed and discussed. Recent advances of nano‐Si devices such as waveguides, optical resonators (linear, rings, and disks) are treated. Emphasis is placed on the visible optical gain properties of nano‐Si and to the sensitization effect on Er ions to achieve infrared light amplification. The possibility of electrical injection in light‐emitting diodes is presented as well as the recent attempts to exploit nano‐Si for solar cells. In addition, nonlinear optical effects that will enable fast all‐optical switches are described.     

Photoluminescence of Si from Si nanocrystal-doped SiO2/Si multilayered sample

A multilayered Si nanocrystal-doped SiO₂/Si (or Si-nc:SiO₂/Si) sample structure is studied to acquire strong photoluminescence (PL) emission of Si via modulating excess Si concentration. The Si-nc:SiO₂ results from SiO thin film after thermal annealing. The total thickness of SiO layer remains 150 nm, and is partitioned equally into a number of sublayers (N = 3, 5, 10, or 30) by Si interlayers. For each N-layered sample, a maximal PL intensity of Si can be obtained via optimizing the thickness of Si interlayer (or d_Si). This maximal PL intensity varies with N, but the ratio of Si to O is nearly a constant. The brightest sample is found to be that of N = 10 and d_Si = 1 nm, whose PL intensity is ∼5 times that of N = 1 without additional Si doping, and ∼2.5 times that of Si-nc:SiO₂ prepared by co-evaporating of SiO and Si at the same optimized ratio of Si to O. Discussions are made based on PL, TEM, EDX and reflectance measurements.