Silicon has long been established as the material of choice for the microelectronics industry. This is not yet true in photonics, where the limited degrees of freedom in material design combined with the indirect bandgap are a major constraint. Recent developments, especially those enabled by nanoscale engineering of the electronic and photonic properties, are starting to change the picture, and some silicon nanostructures now approach or even exceed the performance of equivalent direct-bandgap materials. Focusing on two application areas, namely communications and photovoltaics, we review recent progress in silicon nanocrystals, nanowires and photonic crystals as key examples of functional nanostructures. We assess the state of the art in each field and highlight the challenges that need to be overcome to make silicon a truly high-performing photonic material.

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Silicon nanostructures for photonics and photovoltaics

Silicon quantum dots (SiQDs) hold great promise for many future technologies. Silicon is already at the core of photovoltaics and microelectronics, and SiQDs are capable of efficient light emission and amplification. This is crucial for the development of the next technological frontiers—silicon photonics and optoelectronics. Unlike any other quantum dots (QDs), SiQDs are made of non-toxic and abundant material, offering one of the spectrally broadest emission tunabilities accessible with semiconductor QDs and allowing for tailored radiative rates over many orders of magnitude. This extraordinary flexibility of optical properties is achieved via a combination of the spatial confinement of carriers and the strong influence of surface chemistry. The complex physics of this material, which is still being unraveled, leads to new effects, opening up new opportunities for applications. In this review we summarize the latest progress in this fascinating research field, with special attention given to surface-induced effects, such as the emergence of direct bandgap transitions, and collective effects in densely packed QDs, such as space separated quantum cutting.

https://iopscience.iop.org/article/10.1088/0953-8984/26/17/173201/pdf

Silicon quantum dots: surface matters

We show that the optical and electronic properties of nanocrystalline silicon can be efficiently tuned using impurity doping. In particular, we give evidence, by means of ab initio calculations, that by properly controlling the doping with either one or two atomic species, a significant modification of both the absorption and the emission of light can be achieved. We have considered impurities, either boron or phosphorous (doping) or both (codoping), located at different substitutional sites of silicon nanocrystals with size ranging from $1.1\phantom{\rule{0.3em}{0ex}}\text{to}\phantom{\rule{0.3em}{0ex}}1.8\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$ in diameter. We have found that the codoped nanocrystals have the lowest impurity formation energies when the two impurities occupy nearest neighbor sites near the surface. In addition, such systems present band-edge states localized on the impurities, giving rise to a redshift of the absorption thresholds with respect to that of undoped nanocrystals. Our detailed theoretical analysis shows that the creation of an electron-hole pair due to light absorption determines a geometry distortion that, in turn, results in a Stokes shift between adsorption and emission spectra. In order to give a deeper insight into this effect, in one case we have calculated the absorption and emission spectra beyond the single-particle approach, showing the important role played by many-body effects. The entire set of results we have collected in this work give a strong indication that with the doping it is possible to tune the optical properties of silicon nanocrystals.

Engineering silicon nanocrystals : Theoretical study of the effect of codoping with boron and phosphorus

Optical gain in different silicon nanocrystal systems

Field effect induced luminescence has been achieved by alternate tunnel injection of electrons and holes into Si nanocrystals. The emitting device is a metal-oxide-semiconductor structure with a semitransparent polycrystalline Si contact ∼250nm thick and a silicon-rich silicon oxide layer of about 40nm deposited on a p-type Si substrate by plasma-enhanced chemical vapor deposition. The electroluminescence is optimized for a Si excess of 17% and annealing at 1250°C for 1h in nitrogen-rich atmosphere. The pulsed emission presents typical decay times of ∼5μs and external quantum efficiencies of ∼0.03%.

Field effect luminescence from Si nanocrystals obtained by plasma-enhanced chemical vapor deposition

Porous silicon grains embedded in the phosphorus doped SiO2 matrix exhibit improved photoluminesce properties and better stability in comparison with native porous silicon samples. We have tested this material for the presence of room temperature optical amplification under femtosecond (100 fs, 395 nm) excitation. Combined variable stripe length and shifted excitation spot experiments reveal positive optical gain, the net modal gain coefficient reaching 25 cm−1 at a pump intensity of 1.1 W/cm2 (mean power). The gain spectrum is broad (full width at half maximum ∼130 nm), peaked at ∼650 nm, and is slightly blueshifted with regard to the standard photoluminescence emission.

Optical gain in porous silicon grains embedded in sol-gel derived SiO2 matrix under femtosecond excitation

We report on a continuously emitting electroluminescent device fabricated by Si+-ion implantation and subsequent annealing of a SiO2 layer on a silicon substrate. The SiO2 layer with a thickness of 250 nm was prepared by the sol–gel technique. Four different Si+-ion energies and implantation doses were applied in order to obtain a flat Si+-ion profile across the SiO2 film thickness with an atomic Si excess of 5%. Electroluminescence (EL) occurs above a low-voltage threshold (∼5 V, 1 A/cm2) at one bias polarity only even if the device in fact does not exhibit rectifying properties. EL microscopy reveals that EL at 295 K is emitted from a small number of bright spots with diffraction-limited size. EL spectra of individual bright spots were measured using an imaging spectrometer. The wide EL emission band (situated in the red region ∼750 nm) obtained with spatial averaging over the semitransparent indium–tin–oxide contact represents the envelope of these individual contributions. We suggest that the EL is du...

Red electroluminescence in Si+-implanted sol–gel-derived SiO2 films

Optical properties of commonly investigated Si + -implanted SiO 2 layers (thin SiO 2 films prepared by thermal growth on c-Si substrate) are compared with those of non-conventional SiO 2 layers fabricated by sol–gel process. The sol–gel films, deposited on different substrates, were implanted and annealed in a similar way as the thermal SiO 2 films on c-Si. Striking differences between these two types of samples were found. The conventional Si + -implanted SiO 2 /c-Si layers contain Si nanocrystals and their photoluminescence (PL) properties were found very similar to porous silicon (PL in the red/NIR spectral regions, PL decay time of the order of 10 μs, PL temperature dependence well described by the exciton singlet–triplet splitting model). On the other hand, the Si + -implanted sol–gel SiO 2 films exhibit room temperature PL spectra peaked in the blue–green region, PL decay is considerably faster (of the order of 1 ns) and also PL temperature dependence differs substantially from the samples of the first type. Possible influence of different substrates (silica, c-Si) is also investigated and it is shown that the observed PL is an inherent property of the implanted sol–gel SiO 2 layers. The slow red PL, in agreement with other authors, is ascribed to radiative recombination of excitons in Si nanocrystals, while the fast blue PL characteristic of ion-implanted sol–gel derived SiO 2 films is obviously of defect origin.

Optical properties of Si+-ion implanted sol–gel derived SiO2 films

Recent reports on experimental observation of optical gain in silicon nanostructures in the visible region, performed at several laboratories all over the world, have triggered an extraordinary surge of interest in silicon lasing. However, attempts aimed at reproducing the red stimulated emission from „standard“silicon nanocrystals (sized 3-5 nm) at some other laboratories either failed, or. did not come to definite conclusions. Therefore, more detailed measurements of optical gain in a wider variety of samples containing Si nanocrystals are required in order to unravel whether or not the observation of optical gain is an intrinsic property of Si nanocrystals. We have performed a detailed study of optical gain in layers of densely packed Si nanocrystals in SiO2, prepared on the basis of porous Si, using the variable-stripe-length (VSL) method in combination with the shifted-excitation-spot (SES) method. In selected samples we have observed a distinct difference in behaviour between VSL and SES curves, indicating the occurrence of positive optical gain of ~ 24 cm-1. Preliminary reports on transport and electroluminescence measurements in thin films of SiO2 doped with porous silicon grains, prepared by spin-coating technique, are also discussed.

Grains of Porous Silicon Embedded in SiO 2 :Studies of Optical Gain and Electroluminescence

Stimulated emission in blue-emitting Si[sup +]-implanted SiO[sub 2] films?

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