Nonlinear Optics and Carrier Dynamics in Nanostructured and Two-Dimensional Materials

Understanding and measuring the interaction of light with sub-wavelength structures and atomically thin materials is of critical importance for the development of next generation photonic devices.  One approach to achieve the desired optical properties in a material is to manipulate its mesoscopic structure or its composition in order to affect the properties of the light-matter interaction.  There has been tremendous recent interest in so called two-dimensional materials, consisting of only a single to a few layers of atoms arranged in a planar sheet.  These materials have demonstrated great promise as a platform for studying unique phenomena arising from the low-dimensionality of the material and for developing new types of devices based on these effects.  A thorough investigation of the optical and electronic properties of these new materials is essential to realizing their potential.  In this work we present studies that explore the nonlinear optical properties and carrier dynamics in nanoporous silicon waveguides, two-dimensional graphite (graphene), and atomically thin black phosphorus. We first present an investigation of the nonlinear response of nanoporous silicon optical waveguides using a novel pump-probe method. A two-frequency heterodyne technique is developed in order to measure the pump-induced transient change in phase and intensity in a single measurement. The experimental data reveal a characteristic material response time and temporally resolved intensity and phase behavior matching a physical model dominated by free-carrier effects that are significantly stronger and faster than those observed in traditional silicon-based waveguides.  These results shed light on the large optical nonlinearity observed in nanoporous silicon and demonstrate a new measurement technique for heterodyne pump-probe spectroscopy. Next we explore the optical properties of low-doped graphene in the terahertz spectral regime, where both intraband and interband effects play a significant role. Probing the graphene at intermediate photon energies enables the investigation of the nonlinear optical properties in the graphene as its electron system is heated by the intense pump pulse. By simultaneously measuring the reflected and transmitted terahertz light, a precise determination of the pump-induced change in absorption can be made. We observe that as the intensity of the terahertz radiation is increased, the optical properties of the graphene change from interband, semiconductor-like absorption, to a more metallic behavior with increased intraband processes. This transition reveals itself in our measurements as an increase in the terahertz transmission through the graphene at low fluence, followed by a decrease in transmission and the onset of a large, photo-induced reflection as fluence is increased.  A hybrid optical-thermodynamic model successfully describes our observations and predicts this transition will persist across mid- and far-infrared frequencies.  This study further demonstrates the important role that reflection plays since the absorption saturation intensity (an important figure of merit for graphene-based saturable absorbers) can be underestimated if only the transmitted light is considered. These findings are expected to contribute to the development of new optoelectronic devices designed to operate in the mid- and far-infrared frequency range.  Lastly we discuss recent work with black phosphorus, a two-dimensional material that has recently attracted interest due to its high mobility and direct, configurable band gap (300 meV to 2eV), depending on the number of atomic layers comprising the sample. In this work we examine the pump-induced change in optical transmission of mechanically exfoliated black phosphorus flakes using a two-color optical pump-probe measurement. The time-resolved data reveal a fast pump-induced transparency accompanied by a slower absorption that we attribute to Pauli blocking and free-carrier absorption, respectively. Polarization studies show that these effects are also highly anisotropic - underscoring the importance of crystal orientation in the design of optical devices based on this material. We conclude our discussion of black phosphorus with a study that employs this material as the active element in a photoconductive detector capable of gigahertz class detection at room temperature for mid-infrared frequencies.

Silicon nanopore array structure using porous anodic alumina

A free-standing, bidirectionally permeable and ultra-thin (500-1000 nm) porous anodic alumina membrane was fabricated using a two-step aluminium anodization process, which was then placed on top of a silicon film as an etching mask. The pattern was transferred to silicon using dry-etching technology, and the silicon nanopore array structure was formed. The factors which afflct the pattern transfer process are discussed. Observation of the nanopatterned sample under a scanning electron microscope shows that the structure obtained by this method is made up of uniform and highly ordered holes, which attains to 125 nm depth. The photoluminescence spectrum from the nanopatterned sample,the surface of which has been thermal-oxidized, shows that the the luminesce is evidently enhanced, the mechanism of which is based on the normally weak TO phonon assisted bandgap light-emission process, and the physical reasons that underlic the enhancement have been analyzed. The PL results do show an attractive optical characteristic, which provides a promising pathway to achieve efficient light emission from silicon.

Blue-shift photoluminescence from porous InAlAs

A porous InAlAs structure was first obtained by electrochemical etching. Nano-pore arrays were formed when the In0.52Al0.48As membrane was anodized at constant voltages in an HF aqueous solution. These self-assembled structures showed evident blue-shift photoluminescence emissions. While a quantum size effect alone underestimates the blue-shift energy for a sample with a relatively large average pore wall thickness, a novel effect caused by the asymmetric etching is proposed to account for this phenomenon. The results inferred from the x-ray double crystal diffraction are in good agreement with the experimental data.

Loading of itraconazole into porous silica and silicon microparticles: characterization and dissolution tests

Most new drug molecules discovered today suffer from poor bioavailability. Poor oral bioavailability results mainly from poor dissolution properties of hydrophobic drug molecules, because the drug dissolution is often the rate-limiting event of the drug’s absorption through the intestinal wall into the systemic circulation. During the last few years, the use of mesoporous silica and silicon particles as oral drug delivery vehicles has been widely studied, and there have been promising results of their suitability to enhance the physicochemical properties of poorly soluble drug molecules. Mesoporous silica and silicon particles can be used to enhance the solubility and dissolution rate of a drug by incorporating the drug inside the pores, which are only a few times larger than the drug molecules, and thus, breaking the crystalline structure into a disordered, amorphous form with better dissolution properties. Also, the high surface area of the mesoporous particles improves the dissolution rate of the incorporated drug. In addition, the mesoporous materials can also enhance the permeability of large, hydrophilic drug substances across biological barriers. T he loading process of drugs into silica and silicon mesopores is mainly based on the adsorption of drug molecules from a loading solution into the silica or silicon pore walls. There are several factors that affect the loading process: the surface area, the pore size, the total pore volume, the pore geometry and surface chemistry of the mesoporous material, as well as the chemical nature of the drugs and the solvents. Furthermore, both the pore and the surface structure of the particles also affect the drug release kinetics. In this study, the loading of itraconazole into mesoporous silica (Syloid AL-1 and Syloid 244) and silicon (TOPSi and TCPSi) microparticles was studied, as well as the release of itraconazole from the microparticles and its stability after loading. Itraconazole was selected for this study because of its highly hydrophobic and poorly soluble nature. Different mesoporous materials with different surface structures, pore volumes and surface areas were selected in order to evaluate the structural effect of the particles on the loading degree and dissolution behaviour of the drug using different loading parameters. The loaded particles were characterized with various analytical methods, and the drug release from the particles was assessed by in vitro dissolution tests. The results showed that the loaded drug was apparently in amorphous form after loading, and that the loading process did not alter the chemical structure of the silica or silicon surface. Both the mesoporous silica and silicon microparticles enhanced the solubility and dissolution rate of itraconazole. Moreover, the physicochemical properties of the particles and the loading procedure were shown to have an effect on the drug loading efficiency and drug release kinetics. Finally, the mesoporous silicon particles loaded with itraconazole were found to be unstable under stressed conditions (at 38 qC and 70 % relative humidity).

Ethylenediamine assisted synthesis of wurtzite zinc sulphide nanosheets and porous zinc oxide nanostructures: near white light photoluminescence emission and photocatalytic activity under visible light irradiation

Porous fungus-like ZnO nanostructures have been synthesized by simple thermal annealing of the hydrothermally synthesized sheet-like ZnS(en)(0.5) complex precursor in air at 600 degrees C. Structural and morphological changes occurring during ZnS(en)(0.5) -> ZnS -> ZnO transformations have been observed closely by annealing the as-synthesized precursor at 100-600 degrees C. Wurtzite ZnS nanosheets and ZnS-ZnO composites are obtained at temperatures of 400 degrees C and 500 degrees C, respectively. Thermal decomposition and oxidation of the ZnS(en) 0.5 nanosheets have been confirmed by differential scanning calorimetry and thermo-gravimetric analysis. The visible light driven photocatalytic degradation of methylene blue dye has been demonstrated in the synthesized samples. ZnS-ZnO composite shows the highest dye degradation efficiency of 74% due to the formation of surface complex as well as higher visible light absorption as a result of band-gap narrowing effect. The porous ZnO nanostructures show efficient visible photoluminescence (PL) emission with a colour coordinate of (0.29, 0.35), which is close to that of white light (0.33, 0.33). The efficient visible PL emission as well as visible light driven photocatalytic activity of the materials synthesized in the present work might be very attractive for their applications in future optoelectronic devices, including in white light emitting devices.

Strong visible and infrared photoluminescence from Er-implanted silicon nitride films

Silicon nitride films were deposited by plasma-enhanced chemical-vapour deposition. The films were then implanted with erbium ions to a concentration of 8 x 10(20) cm(-3). After high temperature annealing, strong visible and infrared photoluminescence (PL) was observed. The visible PL consists mainly of two peaks located at 660 and 750 nm, which are considered to originate from silicon nanocluster (Si-NCs) and Si-NC/SiNx interface states. Raman spectra and HRTEM measurements have been performed to confirm the existence of Si-NCs. The implanted erbium ions are possibly activated by an energy transfer process, leading to a strong 1.54 mu m PL.

A comparison of silicon oxide and nitride as host matrices on the photoluminescence from Er3+ ions

This paper compares the properties of silicon oxide and nitride as host matrices for Er ions. Erbium-doped silicon nitride films were deposited by a plasma-enhanced chemical-vapour deposition system. After deposition, the films were implanted with Er3+ at different doses. Er-doped thermal grown silicon oxide films were prepared at the same time as references. Photoluminescence features of Er3+ were inspected systematically. It is found that silicon nitride films are suitable for high concentration doping and the thermal quenching effect is not severe. However, a very high annealing temperature up to 1200 degrees C is needed to optically activate Er3+ which may be the main obstacle to impede the application of Er-doped silicon nitride.

Room temperature photoluminescence of tensile-strained Ge/Si0.13Ge0.87 quantum wells grown on silicon-based germanium virtual substrate

We report a room temperature study of the direct band gap photoluminescence of tensile-strained Ge/Si0.13Ge0.87 multiple quantum wells grown on Si-based germanium virtual substrates by ultrahigh vacuum chemical vapor deposition. Blueshifts of the luminescence peak energy from the Ge quantum wells in comparison with the Ge virtual substrate are in good agreement with the theoretical prediction when we attribute the luminescence from the quantum well to the c Gamma 1-HH1 direct band transition. The reduction in direct band gap in the tensile strained Ge epilayer and the quantum confinement effect in the Ge/Si0.13Ge0.87 quantum wells are directly demonstrated by room temperature photoluminescence.

Novel room temperature photoluminescence of Ge/Si islands in multilayer structure grown on silicon-on-insulator substrate

Novel room temperature photoluminescence (PL) of the Ge/Si islands in multilayer structure grown on silicon-on-insulator substrates is investigated. The cavity formed by the mirrors at the surface and the buried SiO2 interface has a strong effect on the PL emission. The peak position is consistent with the theoretical calculation and independent of the exciting power, which is the evidence of cavity effect on the room temperature photoluminescence. (C) 2004 Elsevier B.V. All rights reserved.

Cavity-enhanced photoluminescence of SiGe/Si multiquantum wells grown on silicon-on-insulator substrate

Sharp and strong room-temperature photoluminescence (PL) of the Si0.59Ge0.41/Si multiquantum wells grown on the silicon-on-insulator substrate is investigated. The cavity formed by the mirrors at the surface and the buried SiO2 interface enhances the PL emission and has a wavelength-selective effect on the luminescence. The peak position is consistent with the simulation result and independent of the exciting power, which indicates a strong cavity effect on the room-temperature PL. (C) 2004 American Institute of Physics.

Photoluminescence of Er-doped hydrogenated amorphous silicon nitride

Er photoluminescence (Er PL) and dangling bonds (DBs) of annealed Er-doped hydrogenated amorphous silicon nitride (a-SiN:H(Er)) with various concentrations of nitrogen are studied in the temperature range 62-300 K. Post-annealing process is employed to change the DBs density of a-SiN:H(Er). PL spectra, DBs density and H, N concentrations are measured. The intensity of Er PL displays complicated relation with Si DBs density within the annealing temperature range 200-500 degreesC. The intensity of Er PL first increases with decreasing density of Si dangling bonds owing to the structural relaxation up to 250 degreesC, and continues to increase up to 350 degreesC even though the density of Si DBs increases due to the improvement of symmetry environment of Er3+. (C) 2003 Elsevier B.V. All rights reserved.

Enhanced near-infrared photoluminescence from isoelectronic luminescent centers in sulfur-implanted silicon with copper or silver coimplantation

Enhanced near-infrared photoluminescence (PL) from sulfur-related isoelectronic luminescent centers in silicon was observed from thermally quenched sulfur-implanted silicon in which additional copper or silver ions had been coimplanted. The PL from the sulfur and copper coimplanted silicon peaked between 70 and 100 K and persisted to 260 K. This result strongly supports the original conjecture from the optical detection of magnetic resonance studies that the strong PL from sulfur-doped silicon comes from S-Cu isoelectronic complexes [Frens , Phys. Rev. B 46, 12316 (1992); Mason , ibid. 58, 7007 (1998).]. (c) 2007 American Institute of Physics.

Synthesis and photoluminescence properties of vertically aligned ZnO nanorod-nanowall junction arrays on a ZnO-coated silicon substrate

Arrays of vertically well-aligned ZnO nanorod-nanowall junctions have been synthesized on an undoped ZnO-coated silicon substrate by a carbothermal reduction and vapour phase transport method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the nanostructures are well-oriented with the c-axis perpendicular to the substrate. The room temperature photoluminescence (PL) spectrum of the as-prepared ZnO nanostructure reveals a dominant near-band-edge (NBE) emission peak and a weak deep level (DL) emission, which demonstrates its good optical properties. Temperature-dependent PL spectra show that both the intensity of NBE and DL emissions increased with decreasing temperature. The NBE emission at 3.27 eV is identified to originate from the radiative free exciton recombination. The possible growth mechanism of ZnO nanorod-nanowall junctions is also proposed.