Valence photoionization of the N2 molecule in the region of the N 1s→Rydberg excitations

The intensities of the X and A valence photoelectron lines of N2 have been found to display Fano line shapes as a function of photon energy around the N 1s→ Rydberg excitations. The vibrational intensity distributions of these photoelectron lines change at the N 1s→3sσ and 3pπ resonances. These effects indicate interference between direct and resonant photoionization channels. Our numerical simulations reproduce quite well the experimental results.

Optoelectronic Properties of InAlN/GaN Distributed Bragg Reflector Heterostructure Examined by Valence

High-resolution monochromated electron energy loss spectroscopy (EELS) at subnanometric spatial resolution and <200 meV energy resolution has been used to assess the valence band properties of a distributed Bragg reflector multilayer heterostructure composed of InAlN lattice matched to GaN. This work thoroughly presents the collection of methods and computational tools put together for this task. Among these are zero-loss-peak subtraction and nonlinear fitting tools, and theoretical modeling of the electron scattering distribution. EELS analysis allows retrieval of a great amount of information: indium concentration in the InAlN layers is monitored through the local plasmon energy position and calculated using a bowing parameter version of Vegard Law. Also a dielectric characterization of the InAlN and GaN layers has been performed through Kramers-Kronig analysis of the Valence-EELS data, allowing band gap energy to be measured and an insight on the polytypism of the GaN layers.

Thermodynamics of zinc insertion in CuGaS2:Ti, used as a modulator agent in an intermediate-band photovoltaic material

An intermediate-bandphotovoltaicmaterial, which has an isolated metallic band located between the top of the valence band and bottom of the conduction band of some semiconductors, has been proposed as third generation solar cell to be used in photovoltaic applications. Density functional theory calculations of Zn in CuGaS2:Ti have previously shown that, the intermediate-band position can be modulated in proportion of Zn insertion in such a way that increasing Zn concentration can lead to aband-gap reduction, and an adjustment of the intermediate-band position. This could be interesting in the formation of an intermediate-bandmaterial, that has the maximum efficiency theoretically predicted for the intermediate-band solar cell. In this work, the energetics of several reaction schemes that could lead to the decomposition of the modulated intermediate-bandphotovoltaicmaterial, CuGaS2:Ti:Zn, is studied in order to assess the thermodynamic stability of this material. Calculations of the total free energy and disorder entropy have been taken into account, to get the reaction energy and free energy of the compound decomposition, which is found to be thermodynamically favorable

Radiative thermal escape in intermediate band solar cells

To achieve high efficiency, the intermediate band (IB) solar cell must generate photocurrent from sub-bandgap photons at a voltage higher than that of a single contributing sub-bandgap photon. To achieve the latter, it is necessary that the IB levels be properly isolated from the valence and conduction bands. We prove that this is not the case for IB cells formed with the confined levels of InAs quantum dots (QDs) in GaAs grown so far due to the strong density of internal thermal photons at the transition energies involved. To counteract this, the QD must be smaller.

Modelling of quantum dot solar cells for concentrator PV applications

An equivalent circuit model is applied in order to describe the operation characteristics of quantum dot intermediate band solar cells (QD-IBSCs), which accounts for the recombination paths of the intermediate band (IB) through conduction band (CB), the valence band (VB) through IB, and the VB-CB transition. In this work, fitting of the measured dark J-V curves for QD-IBSCs (QD region being non-doped or direct Si-doped to n-type) and a reference GaAs p-i-n solar cell (no QDs) were carried out using this model in order to extract the diode parameters. The simulation was then performed using the extracted diode parameters to evaluate solar cell characteristics under concentration. In the case of QDSC with Si-doped (hence partially-filled) QDs, a fast recovery of the open-circuit voltage (Voc) was observed in a range of low concentration due to the IB effect. Further, at around 100X concentration, Si-doped QDSC could outperform the reference GaAs p-i-n solar cell if the current source of IB current source were sixteen times to about 10mA/cm2 compared to our present cell.

InN/GaN heterojunction electrical behavior

Indium nitride (InN) has been the subject of intense research in recent years. Some of its most attractive features are its excellent transport properties such as its small band edge electron effective mass, high electron mobilities and peak drift velocities, and high frequency transient drift velocity oscillations [1]. These suggest enormous potential applications for InN in high frequency electronic devices. But to date the high unintentional bulk electron concentration (n~1018 cm-3) of undoped InN samples and the surface electron accumulation layer make it a hard task to create a reliable metalsemiconductor Schottky barrier. Some attempts have been made to overcome this problem by means of material oxidation [2] or deposition of insulators [3]. In this work we present a way to obtain an electrical rectification behaviour by means of heterojunction growth. Due to the big band gap differences among nitride semiconductors, it’s possible to create a structure with high band offsets. In InN/GaN heterojunctions, depending on the GaN doping, the magnitude of conduction and valence band offset are critical parameters which allow distinguishing among different electrical behaviours. The earliest estimate of the valence band offset at an InN–GaN heterojunction in a wurtzite structure was measured to be ~0.85 eV [4], while the Schottky barrier heights were determined to be ~ 1,4 eV [5].We grew In-face InN layer with varying thickness (between 150 nm and 1 mm) by plasma assisted molecular beam epitaxy (PA-MBE) on GaNntemplates (GaN/Al2O3), with temperatures ranging between 300°C and 450°C. The different doping in GaN template (Si doping, Fe doping and Mg doping) results in differences in band alignments of the two semiconductors changing electrical barriers for carriers and consequently electrical conduction behaviour. The processing of the devices includes metallization of the ohmic contacts on InN and GaN, for which we used Ti/Al/Ni/Au. Whereas an ohmic contact on InN is straightforward, the main issue was the fabrication of the contact on GaN due to the very low decomposition temperature of InN. A standard ohmic contact on GaN is generally obtained by high temperature rapid thermal annealing (RTA), typically done between 500ºC and 900ºC[6]. In this case, the limitation due to the presence of In-face InN imposes an upper limit on the temperature for the thermal annealing process and ohmic contact formation of about 450°C. We will present results on the morphology of the InN layers by X-Ray diffraction and SEM, and electrical measurements, in particular current-voltage and capacitance-voltage characteristics.

Nanotechnology for more efficient photovoltaics: the quantum dot intermediate band solar cell

The intermediate band solar cell [1] has been proposed as a concept able to substantially enhance the efficiency limit of an ordinary single junction solar cell. If a band permitted for electrons is inserted within the forbidden band of a semiconductor then a novel path for photo generation is open: electron hole pairs may be formed by the successive absorption of two sub band gap photons using the intermediate band (IB) as a stepping stone. While the increase of the photovoltaic (PV) current is not a big achievement —it suffices to reduce the band gap— the achievement of this extra current at high voltage is the key of the IB concept. In ordinary cells the voltage is limited by the band gap so that reducing it would also reduce the band gap. In the intermediate band solar cell the high voltage is produced when the IB is permitted to have a Quasi Fermi Level (QFL) different from those of the Conduction Band (CB) and the Valence Band (VB). For it the cell must be properly isolated from the external contacts, which is achieved by putting the IB material between two n- and p-type ordinary semiconductors [2]. Efficiency thermodynamic limit of 63% is obtained for the IB solar cell1 vs. the 40% obtained [3] for ordinary single junction solar cells. Detailed information about the IB solar cells can be found elsewhere [4].

O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitation

Research on intermediate band solar cells and development of experimental techniques for their characterization under concentrated illumination

Abstract This work is a contribution to the research and development of the intermediate band solar cell (IBSC), a high efficiency photovoltaic concept that features the advantages of both low and high bandgap solar cells. The resemblance with a low bandgap solar cell comes from the fact that the IBSC hosts an electronic energy band -the intermediate band (IB)- within the semiconductor bandgap. This IB allows the collection of sub-bandgap energy photons by means of two-step photon absorption processes, from the valence band (VB) to the IB and from there to the conduction band (CB). The exploitation of these low energy photons implies a more efficient use of the solar spectrum. The resemblance of the IBSC with a high bandgap solar cell is related to the preservation of the voltage: the open-circuit voltage (VOC) of an IBSC is not limited by any of the sub-bandgaps (involving the IB), but only by the fundamental bandgap (defined from the VB to the CB). Nevertheless, the presence of the IB allows new paths for electronic recombination and the performance of the IBSC is degraded at 1 sun operation conditions. A theoretical argument is presented regarding the need for the use of concentrated illumination in order to circumvent the degradation of the voltage derived from the increase in the recombi¬nation. This theory is supported by the experimental verification carried out with our novel characterization technique consisting of the acquisition of photogenerated current (IL)-VOC pairs under low temperature and concentrated light. Besides, at this stage of the IBSC research, several new IB materials are being engineered and our novel character¬ization tool can be very useful to provide feedback on their capability to perform as real IBSCs, verifying or disregarding the fulfillment of the “voltage preservation” principle. An analytical model has also been developed to assess the potential of quantum-dot (QD)-IBSCs. It is based on the calculation of band alignment of III-V alloyed heterojunc-tions, the estimation of the confined energy levels in a QD and the calculation of the de¬tailed balance efficiency. Several potentially useful QD materials have been identified, such as InAs/AlxGa1-xAs, InAs/GaxIn1-xP, InAs1-yNy/AlAsxSb1-x or InAs1-zNz/Alx[GayIn1-y]1-xP. Finally, a model for the analysis of the series resistance of a concentrator solar cell has also been developed to design and fabricate IBSCs adapted to 1,000 suns. Resumen Este trabajo contribuye a la investigación y al desarrollo de la célula solar de banda intermedia (IBSC), un concepto fotovoltaico de alta eficiencia que auna las ventajas de una célula solar de bajo y de alto gap. La IBSC se parece a una célula solar de bajo gap (o banda prohibida) en que la IBSC alberga una banda de energía -la banda intermedia (IB)-en el seno de la banda prohibida. Esta IB permite colectar fotones de energía inferior a la banda prohibida por medio de procesos de absorción de fotones en dos pasos, de la banda de valencia (VB) a la IB y de allí a la banda de conducción (CB). El aprovechamiento de estos fotones de baja energía conlleva un empleo más eficiente del espectro solar. La semejanza antre la IBSC y una célula solar de alto gap está relacionada con la preservación del voltaje: la tensión de circuito abierto (Vbc) de una IBSC no está limitada por ninguna de las fracciones en las que la IB divide a la banda prohibida, sino que está únicamente limitada por el ancho de banda fundamental del semiconductor (definido entre VB y CB). No obstante, la presencia de la IB posibilita nuevos caminos de recombinación electrónica, lo cual degrada el rendimiento de la IBSC a 1 sol. Este trabajo argumenta de forma teórica la necesidad de emplear luz concentrada para evitar compensar el aumento de la recom¬binación de la IBSC y evitar la degradación del voltage. Lo anterior se ha verificado experimentalmente por medio de nuestra novedosa técnica de caracterización consistente en la adquisicin de pares de corriente fotogenerada (IL)-VOG en concentración y a baja temperatura. En esta etapa de la investigación, se están desarrollando nuevos materiales de IB y nuestra herramienta de caracterizacin está siendo empleada para realimentar el proceso de fabricación, comprobando si los materiales tienen capacidad para operar como verdaderas IBSCs por medio de la verificación del principio de preservación del voltaje. También se ha desarrollado un modelo analítico para evaluar el potencial de IBSCs de puntos cuánticos. Dicho modelo está basado en el cálculo del alineamiento de bandas de energía en heterouniones de aleaciones de materiales III-V, en la estimación de la energía de los niveles confinados en un QD y en el cálculo de la eficiencia de balance detallado. Este modelo ha permitido identificar varios materiales de QDs potencialmente útiles como InAs/AlxGai_xAs, InAs/GaxIni_xP, InAsi_yNy/AlAsxSbi_x ó InAsi_zNz/Alx[GayIni_y]i_xP. Finalmente, también se ha desarrollado un modelado teórico para el análisis de la resistencia serie de una célula solar de concentración. Gracias a dicho modelo se han diseñado y fabricado IBSCs adaptadas a 1.000 soles.

Deep levels in a-plane, high Mg-content MgxZn1-xO epitaxial layers grown by molecular beam epitaxy

Deep level defects in n-type unintentionally doped a-plane MgxZn1−xO, grown by molecular beam epitaxy on r-plane sapphire were fully characterized using deep level optical spectroscopy (DLOS) and related methods. Four compositions of MgxZn1−xO were examined with x = 0.31, 0.44, 0.52, and 0.56 together with a control ZnO sample. DLOS measurements revealed the presence of five deep levels in each Mg-containing sample, having energy levels of Ec − 1.4 eV, 2.1 eV, 2.6 V, and Ev + 0.3 eV and 0.6 eV. For all Mg compositions, the activation energies of the first three states were constant with respect to the conduction band edge, whereas the latter two revealed constant activation energies with respect to the valence band edge. In contrast to the ternary materials, only three levels, at Ec − 2.1 eV, Ev + 0.3 eV, and 0.6 eV, were observed for the ZnO control sample in this systematically grown series of samples. Substantially higher concentrations of the deep levels at Ev + 0.3 eV and Ec − 2.1 eV were observed in ZnO compared to the Mg alloyed samples. Moreover, there is a general invariance of trap concentration of the Ev + 0.3 eV and 0.6 eV levels on Mg content, while at least and order of magnitude dependency of the Ec − 1.4 eV and Ec − 2.6 eV levels in Mg alloyed samples.

Absorption coefficient for the intraband transitions in quantum dot materials

In this paper, we present calculations of the absorption coefficient for transitions between the bound states of quantum dots grown within a semiconductor and the extended states of the conduction band. For completeness, transitions among bound states are also presented. In the separation of variables, single band k·p model is used in which most elements may be expressed analytically. The analytical formulae are collected in the appendix of this paper. It is concluded that the transitions are strong enough to provide a quick path to the conduction band for electrons pumped from the valence to the intermediate band

Understanding intermediate-band solar cells

The intermediate-band solar cell is designed to provide a large photogenerated current while maintaining a high output voltage. To make this possible, these cells incorporate an energy band that is partially filled with electrons within the forbidden bandgap of a semiconductor. Photons with insufficient energy to pump electrons from the valence band to the conduction band can use this intermediate band as a stepping stone to generate an electron-hole pair. Nanostructured materials and certain alloys have been employed in the practical implementation of intermediate-band solar cells, although challenges still remain for realizing practical devices. Here we offer our present understanding of intermediate-band solar cells, as well as a review of the different approaches pursed for their practical implementation. We also discuss how best to resolve the remaining technical issues.

Analysis of the modified optical properties and band structure of GaAs12xSbx-capped InAs/GaAs quantum dots

The origin of the modified optical properties of InAs/GaAs quantum dots (QD) capped with a thin GaAs1−xSbx layer is analyzed in terms of the band structure. To do so, the size, shape, and composition of the QDs and capping layer are determined through cross-sectional scanning tunnelling microscopy and used as input parameters in an 8 × 8 k·p model. As the Sb content is increased, there are two competing effects determining carrier confinement and the oscillator strength: the increased QD height and reduced strain on one side and the reduced QD-capping layer valence band offset on the other. Nevertheless, the observed evolution of the photoluminescence (PL) intensity with Sb cannot be explained in terms of the oscillator strength between ground states, which decreases dramatically for Sb > 16%, where the band alignment becomes type II with the hole wavefunction localized outside the QD in the capping layer. Contrary to this behaviour, the PL intensity in the type II QDs is similar (at 15 K) or even larger (at room temperature) than in the type I Sb-free reference QDs. This indicates that the PL efficiency is dominated by carrier dynamics, which is altered by the presence of the GaAsSb capping layer. In particular, the presence of Sb leads to an enhanced PL thermal stability. From the comparison between the activation energies for thermal quenching of the PL and the modelled band structure, the main carrier escape mechanisms are suggested. In standard GaAs-capped QDs, escape of both electrons and holes to the GaAs barrier is the main PL quenching mechanism. For small-moderate Sb (<16%) for which the type I band alignment is kept, electrons escape to the GaAs barrier and holes escape to the GaAsSb capping layer, where redistribution and retraping processes can take place. For Sb contents above 16% (type-II region), holes remain in the GaAsSb layer and the escape of electrons from the QD to the GaAs barrier is most likely the dominant PL quenching mechanism. This means that electrons and holes behave dynamically as uncorrelated pairs in both the type-I and type-II structures.

Experimental determination of the eutectic temperature in air of the CuO-TiO2 pseudobinary system

Eutectic temperature and composition in the CuO–TiO2 pseudobinary system have been experimentally determined in air by means differential thermal analysis (DTA), thermogravimetry (TG) and hot-stage microscopy (HSM). Samples of the new eutectic composition treated at different temperatures have been characterized by X-ray diffraction (XRD) and X-ray absorption near-edge structural spectroscopy (XANES) to identify phases and to determine the Cu valence state, respectively. The results show that the eutectic temperature in air is higher by 100 °C (∼1000 °C) for a Ti-richer composition (XTiO2=25 mol%) than the one calculated in the literature. The reduction of Cu2+ to Cu+ takes places at about 1030 °C. The existence of Cu2TiO3 and Cu3TiO4 has been confirmed by XRD in the temperature range between 1045 and 1200 °C.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.