A large amount of work world-wide has been directed towards obtaining an understanding of the fundamental characteristics of porous Si. Much progress has been made following the demonstration in 1990 that highly porous material could emit very efficient visible photoluminescence at room temperature. Since that time, all features of the structural, optical and electronic properties of the material have been subjected to in-depth scrutiny. It is the purpose of the present review to survey the work which has been carried out and to detail the level of understanding which has been attained. The key importance of crystalline Si nanostructures in determining the behaviour of porous Si is highlighted. The fabrication of solid-state electroluminescent devices is a prominent goal of many studies and the impressive progress in this area is described.

The structural and luminescence properties of porous silicon

Organometallic chemistry on silicon and germanium surfaces.

http://nathan.instras.com/documentDB/paper-69.pdf

Porous silicon: a quantum sponge structure for silicon based optoelectronics

This review is concerned with quantum confinement effects in low-dimensional semiconductor systems. The emphasis is on the optical properties, including luminescence, of nanometre-sized microcrysta...

Low-dimensional systems: quantum size effects and electronic properties of semiconductor microcrystallites (zero-dimensional systems) and some quasi-two-dimensional systems

Introduction Sp3-hybridized semiconductors (including InP, GaAs, CdSe, and Si) are remarkable from the perspective of physical chemistry. A single electron created by HOMOLUMO promotion moves rapidly in response to an applied electric field, because there is little lattice distortion (i.e., small Franck-Condon factors) accompanying its creation. According to Marcus-Hush electron transfer theory, electron motion is resonant in the limit of vanishing reorganization energy. Franck-Condon factors are also small around an electron-hole pair, which is an electronically excited state. As a consequence, radiationless internal conversion (unimolecular decay converting electronic energy into heat) is extremely slow. Excited states decay radiatively in a defect-free, direct gap semiconductor such as CdSe. These simple spectroscopic facts have important practical consequences. Semiconductor lightemitting diodes have narrow emission bands and can show near 30% efficiency in converting electrical power into light. Semiconductor lasers and diodes also show excellent long-term stability against photochemical and current-induced degradation, when compared with many organic materials. All these properties reflect the strong chemical bonding, and the extremely delocalized nature of the electronic wave functions. Semiconductor nanocrystals lie between the traditional regimes of chemistry and solid-state physics.1 Nanocrystal research was initially motivated by an effort to understand the evolution of bulk structural and electronic properties from the molecular scale.2 Presently, technological interest in nanocrystals stems from the prospect of creating novel materials with distinct physical properties. Nanocrystals act like molecules as they interact with light via their electronic transition dipoles. Yet, their delocalized solid-state parentage causes them to display unusual photophysics relative to molecules. In many molecules vibronic interaction in the excited state is strong as the wave function is localized on just one or a few bonds. The molecular excited state has a different structure which promotes fast nonradiative deactivation into the ground state. Emission quantum yields can be low, and often sensitive to quenching by the local environment. The situation is different in nanocrystals. In a 23 A diameter nanocrystal, for example, the wave function is delocalized over ∼100 unit cells with little probability density at the surface. This suggests that, in the absence of defects, internal or surface, a nanocrystal should exhibit near unity fluorescence quantum yield, and partial protection from quenching. The emission spectrum should be sharp as the Franck-Condon factors are small. At room temperature nanocrystals can be better photoemitters than bulk semiconductors because in nanocrystals the electron and hole remain superimposed due to quantum confinement. Nanocrystals have the potential to serve as ideal chromophores if their surface chemistry can be understood and controlled. In this Account we describe nanocrystal photophysics and make comparisons between inorganic solid-state materials and organic dye molecules.

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Luminescence Photophysics in Semiconductor Nanocrystals

Porous silicon/silicon structures under anodic oxidation conditions give rise to an electroluminescence phenomenon in the visible range. Using an optical multichannel analyzer the spectral distribution of the emitted light was measured−in situ−during the anodic oxidation step. Recorded spectra show a maximum which shifts continuously from red‐orange at the beginning of the process towards the yellow range. The visible emission well above the band gap of bulk silicon is attributed to a quantum size effect in the very small size (5–20 A) silicon island which constitutes the porous silicon skeleton. The light emission is interrupted when the current flow stops due to the formation of a continuous oxide layer at the porous silicon/silicon interface.

Electroluminescence in the visible range during anodic oxidation of porous silicon films

In situ boron‐doped hydrogenated silicon films plasma‐deposited on various conductive substrates (including transparent oxides on glass) have been anodized in hydrofluoric acid solutions and subsequently electrochemically oxidized in an aqueous electrolyte. At room temperature, the resulting layers yield visible photoluminescence and electroluminescence intensities and spectral shapes similar to those of p‐type crystalline porous silicon obtained in the same way. The results demonstrate the technological feasibility of light‐emitting devices by applying electrochemical processes to deposited silicon‐based films.

Visible light emission at room temperature from anodized plasma‐deposited silicon thin films

The voltage‐tunable electroluminescence (VTEL) observed on porous silicon‐electrolyte system is investigated in relation with the material photoluminescence (PL). It is shown that the PL line is the envelope of all the emitted EL spectra obtained upon the bias variation. Consequently, a blueshift of the (PL) line leads to a similar shift of all the corresponding EL lines. This strongly suggests a common origin of these two phenomenon. Moreover, this study seems to indicate that the VTEL of porous silicon is related to the size and efficiency distributions of the silicon nanocrystallites associated with an electrically induced selective carrier injection.

Relation between porous silicon photoluminescence and its voltage-tunable electroluminescence

Heavily Boron-doped micrometer-thick amorphous (a-Si:B:H) or nanocrystalline (nc-Si) silicon layers have been deposited on a variety of conductive substrates by the 50 KHz PECVD of SiH4 / B2H6 / H2 mixtures at 320°C. These films have been partially electro-oxidized in a HF solution and then anodically oxidized in water in a manner similar to that yielding luminescent porous monocrystalline silicon layers (PcSL). Although the anodized films are x-ray amorphous, they yield intense luminescence properties at room temperature very similar to those of anodically oxidized PcSL with a similar vibrational spectrum. In both anodically oxidized materials, aging is shown to improve the external quantum efficiency. In amorphous anodized layers, optical microscopy under UV excitation showed strongly luminescent strain-related heterogeneities (20 μm in diameter) connected by non luminescent channels. The incidence of our results on the current debate about the origin of visible room-temperature luminescence in porous silicon and Si:O:H systems is discussed.

F. Muller

Papers

Electroluminescence in the visible range during anodic oxidation of porous silicon films

Visible light emission at room temperature from anodized plasma‐deposited silicon thin films

Relation between porous silicon photoluminescence and its voltage-tunable electroluminescence

Intense Rt Visible Photoluminescence from Anodized Amorphous and Nanocrystalline Silicon Films