Investigating Electronic, Optical, and Phononic Properties of Bulk γ-M<inf>2</inf>ON<inf>2</inf>and β-M<inf>7</inf>O<inf>8</inf>N<inf>4</inf>(M = Hf and Zr) Insulators Using Density Functional Theory

Hafnium and zirconium oxynitrides have similar properties, yet a consolidated investigation of their intrinsic properties has not been carried out. In this paper, we perform first-principles density functional theory calculations of γ- and β-phase hafnium and zirconium oxynitrides, which show that the γ-M2ON2(M = Hf and Zr) is an indirect band-gap (Eg) insulator, while the β-M7O8N4has a "pseudo-direct" type of Eg. β-phase has higher Egthan γ-phase, with concomitant disappearance of the conduction band tail. Optical properties in γ-M2ON2show that the anisotropy is negligible, and the optical constant values are in the range of other superhard materials. Phonon calculations present peculiar characteristics such as a small phonon band gap in γ-Hf2ON2and imaginary phonon frequencies in β-phases relating to lattice instability. The phononic properties are unfavorable for their potential use as an absorber material of the hot carrier solar cell-an emerging photovoltaic concept

Free charges versus excitons: photoluminescence investigation of InGaN/GaN multiple quantum well nanorods and their planar counterparts

InGaN/GaN multiple quantum well (MQW) nanorods have demonstrated significantly improved optical and electronic properties compared to their planar counterparts. However, the exact nature of the processes whereby nanorod structures impact the optical properties of quantum wells is not well understood, even though a variety of mechanisms have been proposed. We performed nanoscale spatially resolved, steady-state, and time-resolved photoluminescence (PL) experiments confirming that photoexcited electrons and holes are strongly bound by Coulomb interactions (i.e., excitons) in planar MQWs due to the large exciton binding energy in InGaN quantum wells. In contrast, free electron–hole recombination becomes the dominant mechanism in nanorods, which is ascribed to efficient exciton dissociation. The nanorod sidewall provides an effective pathway for exciton dissociation that significantly improves the optical performance of InGaN/GaN MQWs. We also confirm that surface treatment of nanorod sidewalls has an impact on exciton dissociation. Our results provide new insights into excitonic and charge carrier dynamics of quantum confined materials as well as the influence of surface states

Assessment of the composition of Silicon-Rich Oxide films for photovoltaic applications by optical techniques

Abstract The deposition of sub-stoichiometric silicon rich oxide (SRO) is the first step to obtain well ordered silicon Quantum Dots (QDs) in a dielectric matrix. This structure is used also for third generation photovoltaic devices operating in a tandem architecture. A precise control and assessment of the stoichiometry of these films is crucial to tune the electrical and optical properties of the device. In this paper we discuss two optical techniques to assess the composition of such films and we compare their results

Si solid-state quantum dot-based materials for tandem solar cells

The concept of third-generation photovoltaics is to significantly increase device efficiencies whilst still using thin-film processes and abundant non-toxic materials. A strong potential approach is to fabricate tandem cells using thin-film deposition that can optimise collection of energy in a series of cells with decreasing band gap stacked on top of each other. Quantum dot materials, in which Si quantum dots (QDs) are embedded in a dielectric matrix, offer the potential to tune the effective band gap, through quantum confinement, and allow fabrication of optimised tandem solar cell devices in one growth run in a thin-film process. Such cells can be fabricated by sputtering of thin layers of silicon rich oxide sandwiched between a stoichiometric oxide that on annealing crystallise to form Si QDs of uniform and controllable size. For approximately 2-nm diameter QDs, these result in an effective band gap of 1.8 eV. Introduction of phosphorous or boron during the growth of the multilayers results in doping and a rectifying junction, which demonstrates photovoltaic behaviour with an open circuit voltage (VOC) of almost 500 mV. However, the doping behaviour of P and B in these QD materials is not well understood. A modified modulation doping model for the doping mechanisms in these materials is discussed which relies on doping of a sub-oxide region around the Si QDs

Optical characterisation of silicon nanocrystals embedded in SiO2/Si3N4 hybrid matrix for third generation photovoltaics

Silicon nanocrystals with an average size of approximately 4 nm dispersed in SiO2/Si3N4 hybrid matrix have been synthesised by magnetron sputtering followed by a high-temperature anneal. To gain understanding of the photon absorption and emission mechanisms of this material, several samples are characterised optically via spectroscopy and photoluminescence measurements. The values of optical band gap are extracted from interference-minimised absorption and luminescence spectra. Measurement results suggest that these nanocrystals exhibit transitions of both direct and indirect types. Possible mechanisms of absorption and emission as well as an estimation of exciton binding energy are also discussed

Enhancement of two photon processes in quantum dots embedded in subwavelength metallic gratings

We show a large enhancement of two-photon absorption processes in nanocrystal quantum dots and of light upconversion efficiency from the IR to the near-IR spectral regime, using a hybrid optical device in which near-IR emitting InAs quantum dots were embedded on top a metallic nanoslit array. The resonant enhancement of these nonlinear optical processes is due to the strong local electromagnetic field enhancements inside the nanoslit array structure at the extraordinary transmission resonances. A maximal two-photon absorption enhancement of more than 20 was inferred. Different high field regions were identified for different polarizations, which can be used for designing and optimizing efficient nonlinear processes in such hybrid structures. Combining nanocrystal quantum dots with subwavelength metallic nanostructures is therfore a promising way for a range of possible nonlinear optical devices.Comment: 14 pages, 7 figure

SiOx/SiNy multilayers for photovoltaic and photonic applications

Microstructural, electrical, and optical properties of undoped and Nd3+-doped SiOx/SiNy multilayers fabricated by reactive radio frequency magnetron co-sputtering have been investigated with regard to thermal treatment. This letter demonstrates the advantages of using SiNy as the alternating sublayer instead of SiO2. A high density of silicon nanoclusters of the order 1019 nc/cm3 is achieved in the SiOx sublayers. Enhanced conductivity, emission, and absorption are attained at low thermal budget, which are promising for photovoltaic applications. Furthermore, the enhancement of Nd3+ emission in these multilayers in comparison with the SiOx/SiO2 counterparts offers promising future photonic applications

Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites

The hot-phonon bottleneck effect in lead-halide perovskites (APbX3) prolongs the cooling period of hot charge carriers, an effect that could be used in the next-generation photovoltaics devices. Using ultrafast optical characterization and first-principle calculations, four kinds of lead-halide perovskites (A=FA(+)/MA(+)/Cs(+), X=I(-)/Br(-)) are compared in this study to reveal the carrier-phonon dynamics within. Here we show a stronger phonon bottleneck effect in hybrid perovskites than in their inorganic counterparts. Compared with the caesium-based system, a 10 times slower carrier-phonon relaxation rate is observed in FAPbI3. The up-conversion of low-energy phonons is proposed to be responsible for the bottleneck effect. The presence of organic cations introduces overlapping phonon branches and facilitates the up-transition of low-energy modes. The blocking of phonon propagation associated with an ultralow thermal conductivity of the material also increases the overall up-conversion efficiency. This result also suggests a new and general method for achieving long-lived hot carriers in materials.Jianfeng Yang, Xiaoming Wen, Hongze Xia, Rui Sheng, Qingshan Ma, Jincheol Kim, Patrick Tapping, Takaaki Harada, Tak W. Kee, Fuzhi Huang, Yi-Bing Cheng, Martin Green, Anita Ho-Baillie, Shujuan Huang, Santosh Shrestha, Robert Patterson, Gavin Conibee

Recent progress with hot carrier solar cells

Hot carrier solar cells offer one of the most promising options for high performance “third generation” photovoltaic devices. For successful operation, these need to be thin, strongly absorbing, radioactively efficient devices in a simple 2-terminal configuration. Nonetheless, they offer potential performance close to the maximum possible for solar conversion, equivalent to a multi-cell stack of six or more tandem cells possibly without some of the limitations, such as spectral sensitivity. However, hot carrier cells offer some quite fundamental challenges in implementation that our team is addressing in an internationally collaborative effort

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix.

In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed.D.D. acknowledges the Department of Physics, University of Cambridge and the KACST-Cambridge University Joint Centre of Excellence for financial support. G.L. thanks the Gates Cambridge Trust for support. Q.S. acknowledges the Imperial College Junior Research Fellowship. J.L.M.D. acknowledges ERC Advanced Investigator Grant, Novox, ERC-2009-adG247276. This work was supported by the Engineering and Physical Sciences Research Council, UK.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jz502615e