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A new class of porous membrane has been fabricated that is unique in its combination of nanoscale thickness (1, and is being scaled-up to commercial volumes by a startup company, SiMPore, Inc. Standard commercial separation membranes with pores in this size regime are polymeric materials (poly ether sulphone, cellulose, etc.), microns in thickness, leading to pore morphologies that resemble long narrow tubes or tortuous-path 3-D matrices. As pnc-Si membrane thickness approaches the pore diameters, a simplified structure of holes in a thin sheet results, greatly enhancing both diffusive and forced flow transport through the membrane, as predicted by classical transport theories2. Pnc-Si has confirmed these theoretical predictions, demonstrating record-breaking transport rates, in addition to precise size-separation of nanoparticles, viruses, proteins, and nucleic acids. Applications for this highly precise silicon-based membrane range from highly efficient separations and purification of biomolecules, complexes, and nanoparticles, to substrates for microscopy to cell culture and co-culture. SiMPore is focused on navigating this application space with the goal of quickly introducing products that will allow the company to become self-sustaining and profitable though direct sales or partnerships with market leaders. Key product development drivers include potential competitive performance advantages and perceived value to a particular market, the IP landscape, development costs of the membrane and the device package/interface, and alignment with existing in-house capabilities.

Miniaturized and highly sensitive bio-sensors are attractive in various applications, such as medicine or food safety. Photonic crystal (PhC) microcavities present multiple advantages for rapid and accurate label-free optical detection. But their principle of operation (i.e. observation of a peak in transmission) makes their integration in serial arrays difficult. We present in this paper a multi-channel sensor consisting of several resonant PhC microcavities coupled to the same waveguide. The transmission spectrum shows as many dips as there are cavities, and each of the microcavities can act as an independent sensor. Preliminary results show the fabrication and characterization of a double-channel structure with small defects used as a solvent sensor.

The feasibility of a templated seedless approach for growing segmented p-i-n nanowires –based diodes based on selective epitaxial growth is demonstrated. Such diodes are the basic structure for a TunnelFET device. This approach has the potential for being easily scalable at a full-wafer processing, and there is no theoretical limitation for control on nanowires growth and properties when scaling down their diameters, as opposed to an unconstrained vapor-liquid-solid growth. Moreover, Si/SixGe1-x hetero-structures are implemented, showing that this can improve the TFET ON current not only thanks to the lowered barrier for the band-to-band source-channel tunneling, but additionally thanks to its lower thermal budget for growth, allowing for better control of the abruptness of the doping profile at the source-channel tunneling interface.

Here we discuss a novel capacitive-type chemical sensor structure that uses recently discovered porous nanocrystalline silicon (pnc-Si) membranes [1] covered with metal as the capacitor plates while a polymer layer sandwiched between them serves as the sensing layer for solvent vapor detection. Pnc-Si is new ultrathin (15 nm) membrane material with pore sizes ranging from 5 to 50 nm and porosities from < 0.1 to 15 % that is fabricated using standard silicon semiconductor processing techniques. We present a study of pnc-Si membranes as a platform for such a sensor. The degree of swelling and the reversibility of the polymer/pnc-Si membrane system immersed in analyte-containing vapors are observed using optical and electrical techniques.

The integration of high-density CNT bundles as via interconnects in a CNT/Cu-hybrid BEOL stack is evaluated. CNT via-conduits may greatly improve heat dissipation and as such lower interconnect resistance and improve electromigration resistance. Each carbon shell of the nanotube contributes to electrical and thermal conduction and densities as high as 5×1013 shells per cm2 are estimated necessary. CNT growth processes on BEOL compatible metals are presented with tube densities up to 1012cm−2 and shell densities approaching 1013 cm−2 on blanket substrates. Selective growth of CNT bundles with carbon shell densities around 1012cm−2 is demonstrated with high yield. Ohmic behavior of TiN/CNT/Ti contacts is shown with a CNT via resistivity of 1.2 mΩ cm.

Establishing a cost-effective technology for the metallization of through-Si vias (TSV) is an important factor in the realization and volume manufacturing of 3D-stacked integrated circuits (3D-SIC). Cu electroplating, which is the preferred technique, should provide not only a void-free TSV fill, but also short filling time and small overburden. The duration of the plating process is a significant contributor to the overall 3D process cost, and thus needs to be minimized. The overburden, the thickness of the material deposited on the top surface of the wafer, has to be limited for compatibility with the following processing steps (e.g. chemical mechanical polishing, CMP). In this paper we report on Cu plating of TSV-s with a thin Ta film on the field. The thin Ta film is sputtered on top of the Ta barrier/Cu seed, and inhibits Cu plating outside the TSV-s. We show that the use of this Ta-cap and in situ electrochemical monitoring techniques leads to significant savings in plating and polishing time, and thus savings in manufacturing costs of 3D-stacked integrated circuits.

A new class of silicon-based chemical and biological sensors that offer an electrical response to a variety of substances is described. The devices utilize silicon flow-through sensing membranes with deep trench structures formed to depths up to 100μm, fabricated by electrochemical etching which transforms the silicon into macro-porous silicon (MPS). The sensors have demonstrated the ability to detect the presence of certain chemical and biological materials. Although the principle of operation of the devices is fairly complex, the transduction mechanisms can be compared to chemiresistors and chemically sensitive field-effect transistors (chemFETs). The electrical responses that have shown the most sensitivity are AC conductance and capacitance. Previous work has demonstrated that upon exposure to organic solvents (i.e. ethanol, acetone, benzene) the devices exhibit a characteristic impedance signature. The devices have also shown the ability to detect the hybridization of complementary DNA. The incorporation of other materials that have demonstrated sensitivity to low ambient levels of contaminants is also under investigation. The sensors have been designed and fabricated in linear array configurations; a microfluidic transport chip/package co-design is currently in progress.

Single layers of isolated, size-controlled silicon nanocrystals were prepared by thermal crystallization of a thin amorphous silicon layer sandwiched between silicon dioxide layers. A subsequent oxidation treatment ensured controlled increase in their lateral separation. The size of the nanocrystals, separation of the nanocrystals (from < 1 nm to ∼ 4 nm), stoichiometry of the resulting oxide and surface morphology were monitored with transmission electron microscopy, scanning transmission electron microscopy, atomic force microscopy, and x-ray photoelectron spectroscopy. Mesoscopic charge transport studies performed with an electrostatic force microscope (EFM) revealed rapid lateral transport of charges when the nanocrystals were tightly packed (< 1 nm average separation) and interconnected. As the inter-nanocrystal separation was increased, lateral charge transport was rapidly suppressed. Nanocrystals separated by up to 3.6 nm retained the injected charges in a well-defined localized region (∼ 62 nm diameter region) for a time of the order of several days. The ability to switch from a very short to a very long retention time using the same structure by simply changing the post-growth processing conditions is attractive for various applications involving charge transport and localization.

The sensitivity of Porous Silicon (PSi) to the presence of charged molecules and its large internal surface area represent two important properties that make this material and ideal candidate for electrical biosensor development. We have demonstrated the use of a macroporous silicon electrical sensor for label-free detection of DNA hybridization in real time as well as identification of organic solvents in liquid phase. Binding of DNA inside the PSi matrix induces a change in capacitance and conductance. Having demonstrated the suitability of macroporous silicon layers for real time detection of DNA hybridization on single devices, we have extended our findings to the fabrication of a microarray with individual device electrical addressing capabilities. On a crystalline p-type silicon wafer, process steps such as KOH etching and electrochemical dissolution are employed in selected regions to create a free-standing porous membrane for sensing applications. Individual electrical contacts are made on the front side of the wafer while the infiltration of the probe and target molecules is done from the back avoiding any direct interaction of the molecules with the contact sites. We will report on the design considerations of the electrical porous silicon array and the preliminary results obtained using synthetic DNA as a model molecule.

An electrochemical etching technique has been developed that provides continuous control over the porosity of a porous silicon (PSi) layer as a function of etching depth. Thin films with engineered porosity gradients, and thus a controllable refractive index gradient, have been used to demonstrate broadband antireflection (AR) properties on silicon wafers and solar cell substrates. This low broadband reflectivity is a direct result of the formation of a refractive index gradient at the substrate surface, where the transition between air and silicon occurs continuously throughout the thickness of a PSi film. These graded index films are formed by applying a continuously changing current function to the electrochemical cell during the PSi etch. The application of these films as solar cell AR coatings is of particular interest, where their broadband nature is a critical advantage. For this application, graded index PSi films must not only offer superior AR properties, but must also prove minimally disruptive to the electrical properties of the underlying solar cell. This requirement limits the total thickness of these films to approximately 120 nm, creating several challenges for this process. However, the simplicity and highly reproducible nature of this technique, in combination with its short duration (less than 10 seconds), make it a strong alternative to current vacuum deposited AR coating technology.

We report a successful unification of standard lithographic approaches (top down), anisotropic etching of atomically smooth surfaces, and controlled crystallization of silicon quantum dots (bottom up) to produce silicon nanoclusters at desired locations. These results complement our previous demonstration of silicon nanocrystal uniformity in size, shape, and crystalline orientation in nanocrystalline silicon (nc-Si)/SiO2 superlattices, and could lead to practical applications of silicon nanocrystals in electronic devices. The goal of this study was to induce silicon nanocrystal nucleation at specific lateral sites in a continuous amorphous silicon (a-Si) film. Nearly all previous studies of silicon nanocrystals are based on films containing isolated nanocrystals with random lateral position and spacing. The ability to define precise two-dimensional arrays of quantum dots would allow each quantum dot to be contacted using standard photolithographic techniques, leading to practical device applications like high-density memories. In this work, a template substrate consisting of an array of pyramid-shaped holes in a (100) silicon wafer was formed using standard microfabrication techniques. The geometry of this substrate then influenced the crystallization of an a-Si/SiO2 superlattice that was deposited on it, resulting in preferential nucleation of silicon nanoclusters near the bottom of the pyramid holes. These clusters are clearly visible in transmission electron microscopy (TEM) images, while no clusters have been observed on the planar surface areas of the template. Possible explanations for this selective nucleation and future device structures will be discussed.

The semiconductor industry association roadmap has identified interconnects as a major barrier to progress starting in 2010. Optical interconnects (OI) offer an attractive solution for chip-to-chip communications, however there is no general agreement on how to design them. Eventually, OI may also perform a large amount of intra-chip clocking and signaling, which implies that any chip-to-chip OI system must be designed to be compatible with intra-chip OI, from the points of view of manufacturability, architecture, and device design. We are exploring the use of nanoscale silicon for OI. This paper reports progress toward the demonstration of two basic building blocks of an OI system, namely a Si laser and a Si-based modulator.

Silicon (Si) nanocrystals formed by controlled thermal crystallization of amorphous silicon dioxide (a-SiO2)/amorphous silicon (a-Si)/amorphous silicon dioxide (a-SiO2) layers hold considerable promise for application in non-volatile memory products and optoelectronic devices. The size of the nanocrystals is fixed by the thickness of the Si layer and strong quantum confinement is provided in the vertical (growth) direction by the insulating a-SiO2 layers. However, the extent of quantum confinement in the lateral dimensions remains to be established. Electron energy loss spectroscopy (EELS) measurements performed within a scanning transmission electron microscope (STEM) indicate that the nanocrystals are laterally isolated by approximately 2nm of a-SiO2. The confinement potential provided by this barrier is insufficient to localize carriers within a nanocrystal for prolonged durations and can permit quantum mechanical tunneling via wave function overlap between adjacent nanocrystals. Charge leakage kinetics within a sheet of Si nanocrystals was studied using electric force microscopy. Approximately 750 electrons were injected within a 100nm radius circular patch with an atomic force microscope cantilever. The entire charge dissipated from this area in 70min via lateral conduction routes. With a goal of localizing the injected charge and enhancing its retention time, the samples were subjected to relatively low temperature dry oxidation at 750°C. After 20 min of oxidation, retention times above 400 minutes were observed.

Today, the overall performance of a multi-chip computing system is limited by the interconnection delay between chips. Conventional interconnects based on metal lines are expected to cause unmanageable problems with speed and power dissipation. Optical interconnects provide a solution to these problems. However, the low quantum efficiency associated with radiative recombination in silicon has so far prevented the demonstration of a practical laser. Recently stimulated emission has been demonstrated in Si nanocrystals prepared by ion-implantation. The reported material gain is high enough to realize a practical Si based laser. However, the optical filling factor in these samples was less than 10% due to the poor wave guiding nature of these structures.In this work, we explore a possible way to achieve optical gain in nanocrystalline silicon superlattices. The samples are produced by growing alternating layers of amorphous silicon and SiO2 and then using a two step crystallization method to transform each amorphous silicon layer into a high density array of silicon nanocrystals having identical size. The waveguide structure is formed by sandwiching the superlattice between cladding layers. To measure optical gain we use the variable stripe length method where the amplified spontaneous emission emitted from the edge is measured as a function of the excitation length. Tuning from loss to gain was observed by just varying the pump power.

The highly sensitive surface of porous silicon (PSi) and the possibility to measure changes in its electrical properties can be used for electrical biosensor applications. The sensing scenario can be extended from the well-characterized organic solvents and pH sensors to detection of biological processes involving the presence of charged molecules. We have investigated the change in electrical properties (capacitance and conductance) of macroporous silicon layers upon exposure to organic solvents and water. Evaluation of our sensor to detect a biological event was done by addressing DNA hybridization. As opposed to the previous work published in this field, in our devices the electrical contact is made on the crystalline silicon (c-Si) substrate. This allows a complete exposure of the surface to the sensing species and reduces the generation of ionic currents through the porous silicon matrix. We will report results of a complete characterization of our device including response speed, selectivity and sensitivity.

Electrochemical deposition of FeCo alloys with 1:1 atomic ratio has proved difficult due to cracking from high stress. By using a sulfamate electrolyte and optimizing other deposition parameters, we successfully electrodeposited high quality FeCo films of 20-25 mm in thickness and 7 mm in diameter. Using a suspension of hard oxide nanoparticles (25 nm TiO2) in the electrolyte, we produced oxide-dispersion-strengthened FeCo/TiO2 nanocomposite films with large grains. Enhanced strength was observed from these nanocomposites relative to pure FeCo alloys as determined from Knoop hardness measurements. In order to further improve the ductility of the alloys, vanadium has been codeposited with FeCo. Some preliminary results of FeCoV alloy deposition are reported.

An atomic force microscope (AFM) has been used to optimize the radio frequency (rf)/ radio frequency magnetron sputtering deposition conditions for obtaining atomically smooth, hydrogen free amorphous silicon (a-Si) and silicon dioxide (a-SiO2) thin films. Superlattices composed of periodically repeating units of nanoscale (a-Si/a-SiO2) units were fabricated at these optimized conditions and subsequently crystallized. The amorphous and crystallized superlattices were characterized by AFM and Raman spectroscopy. Raman spectroscopy of the superlattices was performed by enhancing the weak scattered signal and eliminating the silicon substrate signal by using either waveguiding, cross polarization or interferometric enhancement techniques. The enhanced Raman spectrum clearly indicates formation of nanocrystals after crystallization.

We have studied carrier transport and lateral electrical properties of nanocrystalline Si layers containing size controlled Si nanocrystals. Using results from direct current (dc) and alternating current (ac) conductivity measurements, the charging of Si nanocrystals and Coulomb blockade effect are discussed.

A quantum structure based on Si/SiO2 and fabricated using standard Si technology has strong potential for applications in non-volatile and scaled dynamic memories. Among standard requirements, such as long retention time and endurance, a structure utilizing resonant tunneling offers lower bias operation and faster write/read cycle. In addition, degradation effects associated with Fowlher-Nordheim (FN) hot electron tunneling can be avoided. Superlattices of nanometer size layers of silicon and silicon dioxide were obtained by sputtering. The size of the silicon nanocrystallites (nc-Si) is fixed by the thickness of the silicon layer which limits the size dispersion. A detailed analysis of the storage of charges in the dots, as a function of the nanocrystals size, is investigated using capacitance methods. Constant voltage and constant capacitance techniques are used to monitor the discharge of the structure. Room temperature non-volatile memory with retention times as long as months is evidenced.

Two-dimensional periodic arrays of inverted pyramid holes with nanometer scale have been patterned on the surface of a (100) silicon wafer and studied for possible application in nanoscale silicon based devices. The surface patterning employed a simple microelectronic processing scheme in which the standing wave intensity pattern from two interfering 458nm laser beams was used to expose holes in a photoresist layer. Subsequent dry etching through an underlying oxide mask layer, followed by a KOH etching step yielded a highly periodic, large area array of inverted pyramids. The pyramid geometry is formed during the anisotropic KOH etch, which stops at the (111) pyramid walls. Therefore, the tips of all inverted pyramids are formed by the intersection of (111) silicon crystal planes and have identical geometry. This study focuses on the use of these features as templates for the controlled crystallization of amorphous silicon layers and also as electric field concentrating “funnels” in MOS-type structures. We will discuss a proposed device in which silicon nanocrystals will be incorporated into the concentrated electric field region at the tip of each inverted pyramid. With this structure, the charging of identical addressable nanocrystals may be possible, leading to the development of practical nanoscale silicon devices.

We use Raman spectroscopy to study the size, shape and crystallographic orientation of silicon nanocrystals formed by solid phase crystallization of amorphous Si/SiO₂ superlattices (SLs) grown by radio-frequency sputtering. The first and second Raman peaks broadening, their relative positions and intensities indicate the presence of nanoscale Si objects with a degree of disorder (grain boundaries) and strain (Si/SiO₂ interfaces). Shapes of Si nanocrystals sandwiched between SiO₂ layers strongly influence the Si/SiO₂ interface roughness, which is inferred from the intensities of folded acoustic phonon scattering. The averaged crystallographic orientation of Si nanocrystals is determined by polarized Raman analysis. The laterally elongated nanocrystals exhibit preferred crystallographic orientation along the SL axis due to orientation-dependent crystallization rates. These results demonstrate that control over Si nanocrystals structural parameters has been achieved and that solid phase crystallization of nanometer-thick amorphous Si films remains one of the most promising techniques for Si-based nanoelectronic device fabrication., Symposium F – Microcrystaline & Nanocrystalline Semiconductors-2000, Series: MRS Symposium Proceedings

Control over the 1.5 µm emission from erbium is desirable for communication and computational technologies because the erbium emission falls in the window of maximum transmission for silica based fiber optics. Tunable, narrow, directional, and enhanced erbium emission from silicon based 1-D photonic bandgap structures will be demonstrated. The structures are prepared by anodic etching of crystalline silicon and consist of two highly reflecting Bragg reflectors sandwiching an active layer. The cavities are doped by electro-migrating the erbium ions into the porous silicon matrix, followed by high temperature oxidation. By controlling the oxidation temperature, porosity, and thickness of the structure, the position of the erbium emission is tuned to emit in regions where the normal erbium emission is very weak. The erbium emission from the cavity is narrowed to a full width at half maximum (FWHM) of 12 nm with a cavity quality factor Q of 130, highly directional with a 20 degree emission cone around the normal axis, and enhanced by more than one order of magnitude when compared to its lateral emission. Erbium photoluminescence (PL) from porous silicon 2-D photonic bandgap structures is also demonstrated.

The large surface area of porous silicon provides numerous sites for many potential species to attach, which makes it an ideal host for sensing applications. The average pore size can be easily adjusted to accommodate either small or large molecular species. When porous silicon is fabricated into a structure consisting of two high reflectivity multilayer mirrors separated by an active layer, a microcavity is formed. Multiple narrow and visible luminescence peaks are observed with a full width at half maximum value of 3 nm. The position of these peaks is extremely sensitive to small changes in refractive index, such as that obtained when a biological object is attached to the large internal surface of porous silicon. We demonstrate the usefulness of this microcavity resonator structure as a DNA optical biosensor which displays appropriate sensitivity, selectivity, and response speed. A probing strand of DNA is initially immobilized in the porous silicon matrix, and then subsequently exposed to its sensing complementary DNA strand. Red-shifts in the luminescence spectra are observed and detected for various DNA concentrations. The spectral shifts confirm successful recognition and binding of DNA molecules within the porous structure. Detailed device fabrication procedures and the results of extensive testing will be presented. The detection scheme has also been extended to include the detection of viral DNA, proteins, and potentially bacteria. This work will lead to the development of a “smart bandage”, where the detection of bacteria or viruses can be diagnosed and an antibiotic treatment can be recommended.

This report presents an investigation on carrier transport in LED structures based on oxide passivated nanocrystalline silicon (OPNSi), formed by oxidation of porous silicon. This material, like its precursor, can luminesce quite efficiently while demonstrating several advantages in stability (i.e. chemical, thermal, electrical and electroluminescence). OPNSi can be best described as a porous glass structure with defects that facilitate transport, and remaining embedded nanocrystals of silicon that support light emission. Although this study does not provide a direct measurement of the density of states in OPNSi, the following transport study suggests a high density of states having a broad energy distribution that readily exchange charge with the silicon electrodes. Experimental data also suggests the existence of deeper trap centers that do not facilitate transport, yet influence transport behavior significantly. The device operation is explained by bipolar injection from an electron-injection cathode and a hole-injection anode into the semi-insulating OPNSi layer. The device is modeled as a “field effect diode”, where untraditional concepts are applied in the interpretation of experimental observations. Extensive electrical characterization of OPNSi LEDs has lead to the development of a comprehensive transport model that is self-consistent with all experimental observations.

The tuning of one-dimensional photonic band gap structures based on porous silicon will be presented. The photonic structures are prepared by applying a periodic pulse of current density to form alternating high and low porosity layers. The width and position of the photonic bandgap are determined by the dielectric function of each layer, which depends on porosity, and their thickness. In this work we show that by controlling the oxidation of the porous silicon structures, it is possible to tune the photonic bandgap towards shorter wavelengths. The formation of silicon dioxide during oxidation causes a reduction of the refractive index, which induces the blue shift. The photonic band gap is determined experimentally by taking the total reflection of the structures. In order to understand the tuning of the photonic band gap, we developed a geometrical model using the effective medium approximation to calculate the dielectric function of each of the oxidized porous silicon layers. The two key parameters are the porosity and the parameter β, defined as the ratio between the silicon dioxide thickness and the pore radius before oxidation. Choosing the parameter β, to fit the experimental photonic band gap of the oxidized structures, we extract the fraction of oxide that is present. For example, the measured 240 nm blue shift of a photonic bandgap that was centered at 1.7 microns corresponds to the transformation of 30% of the structure into silicon dioxide. A similar approach can be used for oxidized two-dimensional porous silicon photonic structures.

Photoconductance spectroscopy was used to probe the effects of quantum confinement in nanocrystalline (nc)-Si/amorphous (a)-SiO2 superlattices (SLs). A Metal-Oxide-Semiconductor (MOS)-like structure with the nc-Si SL incorporated in the oxide was fabricated to study charging/discharging processes in Si nanocrystals. The fine structure observed in photoconductance spectra at low temperatures was interpreted in terms of singularities in the carrier density of states, possibly due to energy quantization. In addition, a low-resistance sample exhibited photocurrent oscillations with a frequency of several kHz, which could be a manifestation of sequential resonant carrier tunneling in the nc-Si/a-SiO2 SL.

Low-temperature crystallization of a-Si is important for display and Silicon-On- Insulator (SOT) technologies. We present optical characterization (Raman scattering and photoluminescence) of H2 and O2 plasma enhanced crystallization of a-Si:H films. H2 plasma treatment is shown to be the most efficient, leading to larger grain sizes, and both H2 and O2 plasma lead to visible photoluminescence (PL). Recently, the PL of re-crystallized a-Si films has been explained in terms of quantum confinement [1]. The mean size of the crystallites in our re-crystallized films is determined by Raman scattering for different treatments parameters. No correlation between size and the photon energy of the visible emission is found. However, we can clearly distinguish between the PL from purely amorphous and re-crystallized a-Si:H films: Their PL temperature dependence and spectra are very different. The origin of the visible PL in re-crystallized thin Si films is discussed.

Porous silicon multilayer structures are easily manufactured using a periodic current density square pulse during the electrochemical dissolution process. The difference in porosity profile, corresponding to a variation in current density, is attributed to a difference in refractive index. Manipulating the difference in refractive index, high quality optical filters can be made with a maximum reflectivity peak ˜ 100%. The next logical step to further exploit these optical mirrors is to incorporate them into an LED device. The benefit of adding a multilayer mirror below a luminescent film of porous silicon is to significantly reduce the amount of light loss to the silicon substrate and increase the light output. However, oxidation is required to stabilize the as-anodized porous silicon film. This disrupts the overall index profile of the multilayer stack, causing the peak reflectance to blue shift. This phenomenon must be quantified and accounted before device implementation. We present a detailed study on the effects of oxidation temperature, gas environment, and annealing time of porous silicon multilayer structures in a device configuration.

The present work is concerned with Er-doped oxidized porous silicon (PS). The characteristic feature of the work is that PS doping has been realized by an electrochemical procedure followed by a high temperature treatment. 5-μm thick PS layers were formed on p-type Si of 0.3-Ohm-cm resistivity. Er incorporation was performed by a cathodic polarization of PS in a 0.1 M Er(NO3)3 aqueous solution. A high temperature treatment in an oxidizing ambient at 500-1000°C was utilized to provide either partial or total oxidation of PS:Er layers. X-ray microanalysis was used to study chemical composition of the samples. Photoluminescence (PL) and photoluminescence excitation (PLE) spectra were investigated. After the partial oxidation (in the temperature range of 600-800°C), weak Er3+-related PL at 1.53 ptm was observed. A high temperature anneal in Ar atmosphere at the temperature of 1100°C caused a significant increase in the Er3+-related PL intensity. Resonant features were observed in PLE spectra of fully oxidized PS. Five peaks at 381, 492, 523, 654 and 980 nm were revealed. The strongest excitation occurred at 381 and 523 nm. The excitation of different Er3+ energy levels, cross-relaxation interactions and emission due to the 4I13/2→4I15/2 transitions were considered. Application of the Er-doped oxidized PS for integrated optical waveguides is presented.

Infrared photoluminescence (PL) and electroluminescence (EL) from erbium-doped porous silicon (PSi) structures are studied. The PL and EL from the Er-doped PSi structures and the absence of silicon band edge recombination, point defect, and dislocation luminescence bands suggest that the Er-complex centers are the most efficient recombination sites. PSi multilayers with very high reflectivity (R ≥ 90%) in the 1.5 gim range have been incorporated in the structures resulting in a PL enhancement of over 100%. Stable and intense EL is obtained from the Er-doped structures. The EL spectrum is similar to that of the PL, but shifted towards higher energy. The unexpected shift in emission opens up the possibility for erbium related luminescence to encompass a larger part of the optimal wavelength window for fiber optic communications.

The effect of surface passivation and crystallite size on the photoluminescence of porous silicon is reported. Oxygen-free porous silicon samples with medium to ultra high porosities have been prepared by using electrochemical etching followed by photoassisted stain etching. As long as the samples were hydrogen-passivated the PL could be tuned from the red (750nm) to the blue (400nm) by increasing the porosity. We show that when surface oxidation occurred, the photoluminescence was red-shifted. For sizes smaller than 2.8nm, the red shift can be as large as 1eV but for larger sizes no shift has been observed. Comparing the experimental results with theoretical calculations, we suggest that the decrease in PL energy upon exposure to oxygen is related to recombination involving an electron or an exciton trapped in Si=O double bonds. This result clarifies the recombination mechanisms in porous silicon.

The optical properties of oxidized free-standing porous silicon films excited by a cw laser have been investigated. It is found that samples oxidized at 800–950 °C show a strongly superlinear light emission at an excitation intensity of ∼10 W/cm2. This emission has a peak at 900–1100 nm and shows a blueshift as the oxidation temperature is increased. These samples also show a very large induced absorption, where the transmittance is found to decrease reversibly by ≤99.7 %.The induced absorption increases linearly with increasing pump laser intensity. Both the superlinear emission and the large induced absorption are quenched when the samples are attached to materials with a higher thermal conductivity, suggesting that laser-induced thermal effects are responsible for these phenomena.

Light emitting devices (LEDs) based on porous polysilicon (PPS) have been fabricated on a transparent quartz substrate. Several structures have been developed, each consisting of a backside contact (ITO or p+ polysilicon), a light emitting PPS layer, a capping layer, and a metal top contact. Photoluminescence (PL) from PPS is similar to that of etched crystalline Si, peaking near 750 nn and showing degradation during 515 nm laser excitation with intensity 2. This degradation disappears if PPS is oxidized after formation. Visible electroluminescence (EL) has been achieved in both oxidized and non-oxidized PPS devices with voltages under 10 V and current densities 2.

Porous silicon (PSi) was doped by Er using electromigration from a solution and converted to Er-doped silicon-rich silicon oxide (SRSO:Er) by partial thermal oxidation at 600–950°C following densification at 1100°C in an inert atmosphere. Room-temperature photoluminescence (PL) at ∼1.5 μm is intense and decreases by less than 20% from 12 K to 300 K. The PL spectrum of SRSO:Er reveals no luminescence bands related to Si-bandedgerecombination, point defects or dislocations, and shows that the Er3+ centers are the most efficient radiative recombination centers. A light-emitting diode (LED) with an active layer made of SRSO:Er was manufactured using a pre-oxidation cleaning step to increase the quality of the interface between SRSO:Er and the top electrode. Room temperature electroluminescence at ∼1.5 μm was demonstrated.

Amorphous SiOx alloys containing Ge or GeO2 nanocrystals are produced by dc-magnetron sputtering and controlled crystallization. The samples are investigated by Raman scattering, transmission electron microscopy, photo luminescence and excitation spectroscopy. Under UV excitation, both types of films luminesce around 3.1 eV, with identical PL line shapes and subnanosecond PL dynamics. The strongest PL intensity is found for the films containing GeO2 crystals and for the largest nanocrystals. These results are a clear indication that although the blue luminescence is without a doubt correlated with the formation of Ge (or GeO2) nanocrystals, it is not produced by the radiative recombination of excitons confined in the nanocrystals. Possible mechanisms for the luminescence are discussed, including defects at the nanocrystal/matrix interface or in the matrix itself.

Impressive advances have been made over the last few years in teaching silicon how to emit light. Recently, light-emitting devices made of porous silicon and other forms of nanoscale silicon have been demonstrated with specifications that start to make them attractive for commercial applications. This paper reviews the state-of-the-art in the materials science and device properties of nanoscale silicon-based LEDs, including their integration with microelectronic circuits.

We report the fabrication of nanocomposites by the infiltration of polymers into porous silicon. Polymers such as polyamide, polystyrene, PMMA, and PVC were chosen because they are commonly available and have been extensively studied. The pore-filling was accomplished by either diffusion of the polymer molecules into porous silicon or in-situ polymerization of the monomer. The Vickers hardness arid the thermal conductivity of the samples were measured. There was a difference in the nanocomposite characteristics depending on whether the samples were as-anodized or had been annealed in oxygen. By infiltrating polyamide into an as-anodized sample, a 42% increase in hardness and a 24% increase in thermal conductivity were observed at room temperature, without any degradation of luminescence.

We report the fabrication of photovoltaic devices by the anodization of microcrystalline silicon films on single crystal silicon substrates. The porosity of the films was varied from 20% to 60% by changing the anodization conditions. An unetched μc-Si based device was used for reference. The influence of the porosity on the series resistance (Rs), the reflectance, and the spectral response of the devices was studied in detail. In order to determine Rs, the current-voltage characteristics were analyzed, both in the dark and under illumination. We observed that the value of Rs increased from 3.1 Ω to 97 Ω and the value of the reflectance decreased from 24% to 7% when the porosity increased from 20% to 60%. Initially, an optimum device performance (fill factor of 0.53 and efficiency of 7.2%) was achieved for a porosity of 40%, which was about a 40% improvement as compared to the reference (unetched) μc-si based device. Due to a further reduction in Rs by using an intermediate ITO layer and a superior grid-contact architecture, a device efficiency of 10% has been recently achieved.

LEDs based on silicon-rich silicon oxide (SRSO) have been fabricated utilizing thermal oxidation of electrochemically etched c-Si and standard microelectronic processes including LPCVD, photolithography, ion implantation and metallization. The bipolar devices consist of heavily-doped polycrystalline Si, a transition layer made of oxidized mesoporous Si, an active SRSO layer (doped or intrinsic) and a crystalline Si substrate. The LED's electrical properties exhibit a low interface state density which is explained by the partial filling of the micropores within the transition layer by polycrystalline Si. The dominant carrier transport in SRSO is due to thermally-assisted tunneling at low fields and electric field-assisted (Fowler-Nordheim) tunneling at high fields. The electroluminescence (EL) is stable and the EL modulation is limited by the carrier transition time (not by the carrier lifetime) which explains the high modulation speed (≥ 10 MHz). We have fabricated a prototype alphanumeric 7-segment display with an isolated version of the LEDs and standard microelectronic processing techniques.

Highly luminescent free-standing porous silicon thin films of excellent optical quality have been manufactured by using electrochemical etching and lift-off steps combined with supercritical drying. One to 50 μm thick free-standing layers made from highly (p+) and moderately (p) Boron doped single crystal silicon (c-Si) substrates have been produced with porosities (P) up to 95 %. The Fabry-Pérot fringes observed in the transmission and photoluminescence (PL) spectra are used to determine the refractive index. At the highest P the index of refraction is below 1.2 from the IR to 2 eV. The absorption coefficients follow a nearly exponential behavior in the energy range from 1.2 eV and 4 eV. The porosity corrected absorption spectra of free-standing films made from p type c-Si substrates are blue shifted with respect to those prepared from p+ substrates. For P > 70 % a blue shift is also observed in PL. At equal porosities the luminescence intensities of porous silicon films made from p+ and p type c-Si are different by one order of magnitude.

Silicon-rich silicon oxide (SRSO) films were prepared by thermal oxidation (700°C-950°C) of electrochemically etched crystalline silicon (c-Si). The annealing-oxidation conditions are responsible for the chemical and structural modification of SRSO as well as for the intrinsic light-emission in the visible and near infra-red spectral regions (2.0–1.8 eV, 1.6 eV and 1.1 eV). The extrinsic photoluminescence (PL) is produced by doping (via electroplating or ion implantation) with rare-earth (R-E) ions (Nd at 1.06 μm, Er at 1.5 μm) and chalcogens (S at ∼1.6 μm). The impurities can be localized within the Si grains (S), in the SiO matrix (Nd, Er) or at the Si-SiO interface (Er). The Er-related PL in SRSO was studied in detail: the maximum PL external quantum efficiency (EQE) of 0.01–0.1% was found in samples annealed at 900°C in diluted oxygen (∼ 10% in N2). The integrated PL temperature dependence is weak from 12K to 300K. Light emitting diodes (LEDs) with an active layer made of an intrinsic and doped SRSO are manufactured and studied: room temperature electroluminescence (EL) from the visible to 1.6 μmhas been demonstrated.

Silicon-based optoelectronic devices enable the realization of optoelectronic systems that are compatible with integrated circuit manufacturing technology. This work reports on silicon-based visible light-emitting devices (LEDs) that have been successfully integrated into a standard bipolar fabrication sequence. The basic LED structure consists of a 0.5–1.0μm thick silicon-rich silicon oxide (SRSO) active light-emitting layer formed on a p-type silicon wafer by partial oxidation of porous silicon (PSi), with an n+ doped polysilicon cathode. The LEDs exhibit bright electroluminescence (EL) with a spectral peak between 1.75 and 1.90e. The LEDs are connected in a common-emitter configuration to integrated vertical pnp bipolar driver transistors. This is the first demonstration of an all-silicon visible light emitter / bipolar transistor optoelectronic integrated circuit. The LED device fabrication, process integration, and optoelectronic device characteristics are discussed.

Transient photocurrent measurements are reported in an electroluminescent porous silicon diode. Electron drift mobilities are obtained from the data as a function of temperature. Electron transport is dispersive, with a typical dispersion parameter α≈ 0.5. The range of mobilities is 10−5 − 10−4 cm2Vs between 225 K amd 400 K. This temperature-dependence is much less than expected for multiple-trapping models for dispersion, and suggests that a fractal structure causes the dispersion and the small mobilities.

We have studied the photoluminescence (PL) in oxidized porous silicon (PSi), prepared from anodized crystalline Si followed by annealing at temperatures ranging from 700 to 1000°C. It has been found that two PL bands with spectral peaks at 1.6 e V (near-IR band) and near 2 eV (red band) exist with a strong dependence on preparation (annealing) conditions. Recent experimental results show a correlation between the intensity of the near-IR band and the level of leakage current in the diode-like structure. The suppression of the near-IR emission results in improved carrier transport, and the enhancement of the red band emission maximizes the electroluminescence (EL) efficiency. The PL study of thermally oxidized PSi indicates different recombination mechanisms. The red PL band is associated with a mechanism similar to band-tail-recombination within the quasi-bandgap of Si nanograins, whereas the near infra-red PL is associated with recombination via defect centers. These mechanisms will be discussed.

Optical properties of size restricted Cu2O obtained through aqueous and non aqueous preparations are compared with those of commercially available bulk crystals. One method of synthesis involved using polyvinyl alcohol as a restraining agent in an aqueous preparation to produce nanocrystals having diameters with a mean of 11 nm and a standard deviation of 6 nm. Low-temperature spectroscopie studies indicate size restriction effects are manifest by a decrease in exciton luminescence and a 3.0 to 9.0 meV blue shift in 0,0 transition. No noticeable changes in the dynamics were observed for the nanocrystals, indicating no alteration or relaxation of the selection rules for the direct forbidden transition.

Scanning stage microscopes have traditionally been used to provide high resolution, large area photocurrent mapping of solar cells and detectors. This imaging method, while very useful in the characterization and quality control of solar cells, is unfortunately slow (image acquisition takes several minutes). This paper describes a confocal scanning beam MACROscope-Microscope which can image specimens from 25×25 μm up to 7.5×7.5 cm in size, a zoom factor of 3000, using reflected light, photoluminescence, and optical beam induced current in less than 10s. Resolutions range from 0.25 to 10 μ;m laterally and 0.5 to 300 pm axially depending upon whether microscope or MACROscope mode is used. This instrument can therefore be used to characterize and provide quick and efficient quality control for solar cells and detectors at a microscopic and macroscopic level.A brief description of the MACROscope-Microscope is given. The MACROscope- Microscope's many abilities are highlighted by showing various reflected-light, photolhminescence and optical beam induced current images from CdZnS/CulnSe2 thin film solar cells and porous silicon devices.

We have investigated several methods to form submicron-size porous silicon regions. Porous silicon can emit light from the violet to past 1.5 μm with high photoluminescence efficiency at room temperature. It is composed of a high density of nanometer-scale crystalline silicon wires or dots. To integrate light-emitting porous silicon (LEPSi) LEDs with conventional Si microelectronics, it is necessary to produce miniature LEPSi regions adjacent to fully protected crystalline silicon regions. These techniques can be divided into two groups. In the first group formation of LEPSi is prevented during electrochemistry. Using optical and electron beam lithography, and a trilayer process with silicon nitride or amorphization by ion-implantation, we have made LEPSi patterns as small as 100 nm. In the second group, the formation of LEPSi during electrochemistry is enhanced by ion-milling or reactive ion-etching which we have found to help the pore nucleation. We have used a variety of mapping techniques, such as photoluminescence, atomic force and electron beam microscopies, to characterize the sharpness of the interface between the porous silicon and crystalline silicon regions.

The presence of point defects is expected to influence the properties of free carrier in semiconductors. We have used the techniques of ultrafast laser spectroscopy to characterize the dynamics of photoinjected carriers in several III–V semiconductors grown at low temperature. The initial scattering time and the lifetime of the carriers become very short at low growth temperatures. Results obtained with low-temperature grown III–Vs are compared to those obtained with III–Vs grown at normal temperatures and amorphous silicon.

This work presents a systematic investigation of carrier injection and transport mechanisms in light emitting porous silicon (LEPSI). In addition to optical characterization of the LEPSI film, the electrical characteristics of LEPSI light emitting diodes (LEDs) and the device parameter effects on electroluminescence (EL) efficiency are explored including junction structure, LEPSI layer thickness, and chemical treatment. Au/LEPSI device structures exhibit a power-law current-voltage relationship (I∼Vm) and LEPSI pn junction device structures exhibit an exponential current-voltage relationship (I∼eeV/nkT). The carrier transport mechanisms are discussed, and theoretical simulations match well with the experimental data. An increase in EL efficiency has been achieved by adjusting the LEPSI layer thickness, implementing chemical treatment, and improving the quality of the contacts. The EL response to the frequency modulation of LEPSI LEDs was studied, resulting in a cutoff frequency in excess of 100 kHz. LEPSI LEDs have demonstrated stable EL at applied voltages as low as 5 volts with EL efficiencies of 0.01%.