Optical emission from Si O2 -embedded silicon nanocrystals: A high-pressure Raman and photoluminescence study

© 2015 American Physical Society. We investigate the optical properties of high-quality Si nanocrystals (NCs)/SiO2 multilayers under high hydrostatic pressure with Raman scattering and photoluminescence (PL) measurements. The aim of our study is to shed light on the origin of the optical emission of the Si NCs/SiO2. The Si NCs were produced by chemical-vapor deposition of Si-rich oxynitride (SRON)/SiO2 multilayers with 5- and 4-nm SRON layer thicknesses on fused silica substrates and subsequent annealing at 1150°C, which resulted in the precipitation of Si NCs with an average size of 4.1 and 3.3 nm, respectively. From the pressure dependence of the Raman spectra we extract a phonon pressure coefficient of 8.5±0.3cm-1/GPa in both samples, notably higher than that of bulk Si(5.1cm-1/GPa). This result is ascribed to a strong pressure amplification effect due to the larger compressibility of the SiO2 matrix. In turn, the PL spectra exhibit two markedly different contributions: a higher-energy band that redshifts with pressure, and a lower-energy band which barely depends on pressure and which can be attributed to defect-related emission. The pressure coefficients of the higher-energy contribution are (-27±6) and (-35±8)meV/GPa for the Si NCs with a size of 4.1 and 3.3 nm, respectively. These values are sizably higher than those of bulk Si(-14meV/GPa). When the pressure amplification effect observed by Raman scattering is incorporated into the analysis of the PL spectra, it can be concluded that the pressure behavior of the high-energy PL band is consistent with that of the indirect transition of Si and, therefore, with the quantum-confined model for the emission of the Si NCs.Work supported by the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement No. 245977 (project NASCEnT). Financial support by the Spanish Government through projects LEOMIS (TEC2012-38540-C02-01) and MAT2012-38664-C02-02 is also acknowledgedPeer Reviewe

Resistive switching and charge transport mechanisms in ITO/ZnO/p-Si devices

[EN] The resistive switching properties of ITO/ZnO/p-Si devices have been studied, which present well-defined resistance states with more than five orders of magnitude difference in current. Both the high resistance state (HRS) and the low resistance state (LRS) were induced by either sweeping or pulsing the voltage, observing some differences in the HRS. Finally, the charge transport mechanisms dominating the pristine, HRS, and LRS states have been analyzed in depth, and the obtained structural parameters suggest a partial re-oxidation of the conductive nanofilaments and a reduction of the effective conductive area.This work was financially supported by the Spanish Ministry of Economy and Competitiveness (Project Nos. TEC2012-38540-C02-01 and TEC2016-76849-C2-1-R). O.B. also acknowledges the subprogram "Ayudas para Contratos Predoctorales para la Formacion de Doctores" of the Spanish Ministry of Economy and Competitiveness for economical support. 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M., Panda, D., Tsai, T.-L., Lin, C.-A., Wei, K.-H., & Tseng, T.-Y. (2015). Enhancing the memory window of AZO/ZnO/ITO transparent resistive switching devices by modulating the oxygen vacancy concentration of the top electrode. Journal of Materials Science, 50(21), 6961-6969. doi:10.1007/s10853-015-9247-ySimanjuntak, F. M., Prasad, O. K., Panda, D., Lin, C.-A., Tsai, T.-L., Wei, K.-H., & Tseng, T.-Y. (2016). Impacts of Co doping on ZnO transparent switching memory device characteristics. Applied Physics Letters, 108(18), 183506. doi:10.1063/1.4948598Simanjuntak, F. M., Panda, D., Tsai, T.-L., Lin, C.-A., Wei, K.-H., & Tseng, T.-Y. (2015). Enhanced switching uniformity in AZO/ZnO1−x/ITO transparent resistive memory devices by bipolar double forming. Applied Physics Letters, 107(3), 033505. doi:10.1063/1.4927284Liu, Q., Guan, W., Long, S., Jia, R., Liu, M., & Chen, J. (2008). Resistive switching memory effect of ZrO[sub 2] films with Zr[sup +] implanted. 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New strategies in laser processing of TCOs for light management improvement in thin-film silicon solar cells

Light confinement strategies play a crucial role in the performance of thin-film (TF) silicon solar cells. One way to reduce the optical losses is the texturing of the transparent conductive oxide (TCO) that acts as the front contact. Other losses arise from the mismatch between the incident light spectrum and the spectral properties of the absorbent material that imply that low energy photons (below the bandgap value) are not absorbed, and therefore can not generate photocurrent. Up-conversion techniques, in which two sub-bandgap photons are combined to give one photon with a better matching with the bandgap, were proposed to overcome this problem. In particular, this work studies two strategies to improve light management in thin film silicon solar cells using laser technology. The first one addresses the problem of TCO surface texturing using fully commercial fast and ultrafast solid state laser sources. Aluminum doped Zinc Oxide (AZO) samples were laser processed and the results were optically evaluated by measuring the haze factor of the treated samples. As a second strategy, laser annealing experiments of TCOs doped with rare earth ions are presented as a potential process to produce layers with up-conversion properties, opening the possibility of its potential use in high efficiency solar cells

Modulation of the electroluminescence emission from ZnO/Si NCs/p-Si light-emitting devices via pulsed excitation

In this work, the electroluminescence (EL) emission of zinc oxide (ZnO)/Si nanocrystals (NCs)-based light-emitting devices was studied under pulsed electrical excitation. Both Si NCs and deep-level ZnO defects were found to contribute to the observed EL. Symmetric square voltage pulses (50-μs period) were found to notably enhance EL emission by about one order of magnitude. In addition, the control of the pulse parameters (accumulation and inversion times) was found to modify the emission lineshape, long inversion times (i.e., short accumulation times) suppressing ZnO defects contribution. The EL results were discussed in terms of the recombination dynamics taking place within the ZnO/Si NCs heterostructure, suggesting the excitation mechanism of the luminescent centers via a combination of electron impact, bipolar injection, and sequential carrier injection within their respective conduction regimes

Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure

Antimony trisulfide (Sb2S3), found in nature as the mineral stibnite, has been studied under compression at room temperature from a joint experimental and theoretical perspective. X-ray diffraction and Raman scattering measurements are complemented with ab initio total-energy, lattice-dynamics, and electronic structure calculations. The continuous changes observed in the volume, lattice parameters, axial ratios, bond lengths, and Raman mode frequencies as a function of pressure can be attributed to the different compressibility along the three orthorhombic axes in different pressure ranges, which in turn are related to the different compressibility of several interatomic bond distances in different pressure ranges. The structural and vibrational properties of Sb2S3 under compression are compared and discussed in relation to isostructural Bi2S3 and Sb2Se3. No first-order phase transition has been observed in Sb2S3 up to 25 GPa, in agreement with the stability of the Pnma structure in Bi2S3 and Sb2Se3 previously reported up to 50 GPa. Our measurements and calculations do not show evidence either for a pressure-induced second-order isostructural phase transition or for an electronic topological transition in Sb2S3.This work has been performed under financial support from Spanish MINECO under Projects MAT2013-46649-C4-2/3-P and MAT2015-71070-REDC. This publication is fruit of "Programa de Valoracion y Recursos Conjuntos de I+D+i VLC/CAMPUS" and has been financed by the Spanish Ministerio de Educacion, Cultura y Deporte, as part of "Programa Campus de Excelencia Internacional" through Projects SP20140701 and SP20140871. These experiments were performed at BL04-MSPD beamline at ALBA Synchrotron with the collaboration of ALBA staff. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. J.A.S. acknowledges financial support through Juan de la Cierva fellowship.Ibáñez, J.; Sans-Tresserras, JÁ.; Popescu, C.; López-Vidrier, J.; Elvira-Betanzos, J.; Cuenca Gotor, VP.; Gomis, O.... (2016). Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure. Journal of Physical Chemistry C. 19(120):10547-10558. https://doi.org/10.1021/acs.jpcc.6b01276S10547105581912

Determining the crystalline degree of silicon nanoclusters/SiO2 multilayers by Raman scattering

We use Raman scattering to investigate the size distribution, built-in strains and the crystalline degree of Si-nanoclusters (Si-nc) in high-quality Si-rich oxynitride/SiO2 multilayered samples obtained by plasma enhanced chemical vapor deposition and subsequent annealing at 1150 °C. An initial structural characterization of the samples was performed by means of energy-filtered transmission electron microscopy (EFTEM) and X-ray diffraction (XRD) to obtain information about the cluster size and the presence of significant amounts of crystalline phase. The contributions to the Raman spectra from crystalline and amorphous Si were analyzed by using a phonon confinement model that includes the Si-nc size distribution, the influence of the matrix compressive stress on the clusters, and the presence of amorphous Si domains. Our lineshape analysis confirms the existence of silicon precipitates in crystalline state, in good agreement with XRD results, and provides also information about the presence of a large compressive stress over the Si-nc induced by the SiO2 matrix. By using the Raman spectra from low temperature annealed samples (i.e., before the crystallization of the Si-nc), the relative scattering cross-section between crystalline and amorphous Si was evaluated as a function of the crystalline Si size. Taking into account this parameter and the integrated intensities for each phase as extracted from the Raman spectra, we were able to evaluate the degree of crystallization of the precipitated Si-nc. Our data suggest that all samples exhibit high crystalline fractions, with values up to 89% for the biggest Si-nc. The Raman study, supported by the EFTEM characterization, indicates that this system undergoes a practically abrupt phase separation, in which the precipitated Si-nanoclusters are formed by a crystalline inner part surrounded by a thin amorphous shell of approximately 1-2 atomic layers. © 2014 AIP Publishing LLC.The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007–2013) under Grant Agreement No: 245977, under the project title NASCEnT. The present work was supported by the Spanish national project LEOMIS (TEC2012-38540-C02-01) and MAT2010-16116.Peer reviewe

Defect-Induced Luminescence Quenching vs. Charge Carrier Generation of Phosphorus Incorporated in Silicon Nanocrystals as Function of Size

© The Author(s) 2017. Phosphorus doping of silicon nanostructures is a non-trivial task due to problems with confinement, self-purification and statistics of small numbers. Although P-atoms incorporated in Si nanostructures influence their optical and electrical properties, the existence of free majority carriers, as required to control electronic properties, is controversial. Here, we correlate structural, optical and electrical results of size-controlled, P-incorporating Si nanocrystals with simulation data to address the role of interstitial and substitutional P-atoms. Whereas atom probe tomography proves that P-incorporation scales with nanocrystal size, luminescence spectra indicate that even nanocrystals with several P-atoms still emit light. Current-voltage measurements demonstrate that majority carriers must be generated by field emission to overcome the P-ionization energies of 110-260 meV. In absence of electrical fields at room temperature, no significant free carrier densities are present, which disproves the concept of luminescence quenching via Auger recombination. Instead, we propose non-radiative recombination via interstitial-P induced states as quenching mechanism. Since only substitutional-P provides occupied states near the Si conduction band, we use the electrically measured carrier density to derive formation energies of ∼400 meV for P-atoms on Si nanocrystal lattice sites. Based on these results we conclude that ultrasmall Si nanovolumes cannot be efficiently P-doped