A biosensor has been developed based on induced wavelength shifts in the Fabry-Perot fringes in the visible-light reflection spectrum of appropriately derivatized thin films of porous silicon semiconductors. Binding of molecules induced changes in the refractive index of the porous silicon. The validity and sensitivity of the system are demonstrated for small organic molecules (biotin and digoxigenin), 16-nucleotide DNA oligomers, and proteins (streptavidin and antibodies) at pico- and femtomolar analyte concentrations. The sensor is also highly effective for detecting single and multilayered molecular assemblies.

https://science.sciencemag.org/content/sci/278/5339/840.full.pdf

A Porous Silicon-Based Optical Interferometric Biosensor

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

Porous silicon: a quantum sponge structure for silicon based optoelectronics

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.

/pdf/luminescence-photophysics-in-semiconductor-nanocrystals-of1k9whjnp.pdf

Luminescence Photophysics in Semiconductor Nanocrystals

The size and shape dependent electronic and chemical properties of metal nanoparticles has drawn the attention of chemists, physicists, biologists, and engineers who wish to use them for the development of new generation nanodevices. In this article, we report the synthesis of gold nanotriangles using tamarind leaf extract as the reducing agent. On treating aqueous chloroauric acid solution with tamarind leaf extract, rapid reduction of the chloroaurate ions is observed leading to the formation of flat and thin single crystalline gold nanotriangles. Atomic force microscopy analysis of the gold nanotriangles indicated that they ranged in thickness from 20 to 40 nm. These gold nanotriangles with unique and highly anisotropic planer shapes might find application in photonics, optoelectronics, and optical sensing. We investigated the effect of different organic solvent vapors like methanol, benzene and acetone on the conductivity of tamarind leaf extract reduced gold nanotriangles. I‐V characteristics measure...

Gold Nanotriangles Biologically Synthesized using Tamarind Leaf Extract and Potential Application in Vapor Sensing

Large wavelength shifts have been measured in the reflectivity spectra of Bragg mirrors etched in porous silicon after exposure of the mirrors to vapor from organic solvents. The shift in the Bragg wavelength of the mirror arises from refractive index changes, induced by capillary condensation of the vapor in the mesoporous silicon, in the layers of the mirrors. Modeling of the reflectivity changes shows that the layer liquid volume fraction occurring in the measurements was 0.29 for acetone and 0.33 for chlorobenzene. Time-resolved measurements show that condensation occurs on the time scale of tens of seconds.

Vapor sensing using the optical properties of porous silicon Bragg mirrors

Porous silicon (p type) has been exposed to several chemical vapors at various partial pressures. The quenching of the photoluminescence by the adsorbates has been quantified and correlation to the electrical conductivity of the porous silicon sample has been studied. Some gases, e.g., water and benzene, have a small effect on the photoluminescence and on the conductivity, while others, e.g., methanol, reduce the photoluminescence by a factor of 2 and increase the conductivity by four orders of magnitude. This is accompanied with a qualitative change in the current‐voltage characteristics. These changes have been found to be reversible and the temporal behavior of the system has been investigated.

Adsorbate effects on photoluminescence and electrical conductivity of porous silicon

Conductivity of porous silicon layers (p-type) has been investigated for organic vapor sensing. A many orders of magnitude increase in conductivity in response to a vapor pressure change from 0 to 100% has been measured for some compounds. The conductivity (at a constant pressure) varies exponentially with the compound's dipole moment The temporal response of the porous silicon layers is in the seconds range, and the recovery is much slower (minutes). However, due to the tremendous conductivity changes and the low background noise, a complete recovery is not needed for sensing purposes. The mechanism of conductivity enhancement has been studied using several methods. It is attributed to an increase in the density of charge carriers. An additional mechanism based on increased diffusivity may take place in microporous silicon. The observed characteristics suggest the application of porous silicon to future chemical sensors. The sensors have the potential to be integrated monolithically with other silicon devices using current technologies.

Gas sensing properties of porous silicon

We describe a method for interferometric distance measurements in the presence of phase noise. The method is based on the beating between white light and a reference beam that travel along the same path through the interferometer. Since both the reference and the white light suffer the same phase noise, the envelope of the high frequency fringes is not affected by the noise. By measuring the signal variance, we recover the envelope while averaging out the high frequency fringes. We demonstrate the usefulness of the method for surface profilometers.

Moshe. Ben-Chorin

Papers

Adsorbate effects on photoluminescence and electrical conductivity of porous silicon

Gas sensing properties of porous silicon

Distance measurements using a noisy white light interferometer