First principles study of Bi dopen CdTe thin film solar cells: electronic and optical properties

Nowadays, efficiency improvement of solar cells is one of the most important issues in photovoltaic systems and CdTe is one of the most promising thin film photovoltaic materials we can found. CdTe reported efficiencies in solar energy conversion have been as good as that found in polycrystalline Si thin film cell [1], besides CdTe can be easily produced at industrial scale

Intermediate band position modulated by Zn addition in Ti doped CuGaS2

Many works have been done recently with the aim of obtaining intermediate band semiconductors, due to the significant importance of improving solar cell efficiency. Intermediate band materials based on CuGaS2 chalcopyrite semiconductor are one of the proposed materials and specifically Ti doped CuGaS2 is a promising structure to form the intermediate band. Here we present an ab-initio study using the density functional theory in this type of intermediate band chalcogens. Several concentrations of Ti and Zn substituting Ga atoms have been studied and their electronic densities of states were obtained. Results demonstrate a chalcopyrite semiconductor band-gap shortening and intermediate band position modulation inside this band-gap by Zn addition

Obtaining an intermediate band photovoltaic material through the Bi insertion in CdTe

Defect interaction can take place in CdTe under Te and Bi rich conditions. We demonstrate in this work through first principles calculations, that this phenomenon allows a Jahn Teller distortion to form an isolated half-filled intermediate band in the host semiconductor band-gap. This delocalized energy band supports the experimental deep level reported in the host band-gap of CdTe at a low bismuth concentration. Furthermore, the calculated optical absorption of CdTe:Bi in this work shows a significant subband-gap absorption that also supports the enhancement of the optical absorption found in the previous experimental results

Effect of van der Waals interaction on the properties of SnS2 layered semiconductor

Nowadays, dispersion correction applied on layered semiconductors is a topic of interest. Among the known layered semiconductors, SnS2 polytypes are wide gap semiconductors with a van der Waals interaction between their layers, which could form good materials to be used in photovoltaic applications. The present work gives an approach to the SnS2 geometrical and electronic characterization using an empirical dispersion correction added to the Perdew–Burke–Ernzerhof functional and subsequent actualization of the electronic charge density using the screened hybrid Heyd–Scuseria–Ernzerhof functional using a density functional code. The obtained interlayer distance and band-gap are in good agreement with experimental values when van der Waals dispersion forces are included

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

Separation of an aqueous mixture of 6-kestose/sucrose with zeolites: A molecular dynamics simulation

[EN] Extra-large pore zeolites are a small subset (21) among the whole list of 253 zeolites available. The discovery of new low-glycemic sugars is very attractive as new healthy additives in the food field. This is the case of the 6-kestose. In the present case, it appears in a mixture in aqueous solution together with sucrose, the separation of the mixture being necessary. For this, we have focused on using certain zeolites with adequate pore sizes that allow the separation of this mixture, considering that since the molecular size of 6-kestose is greater than sucrose, it is necessary to promote the sorption of the latter, so that the first can be purified. After a computational screening of micropores of the 253 IZA zeolites, 11 zeolites were selected. Of these, 3 extra-large pore zeolites (AET, DON, ETR) have been proposed, which were analyzed in-depth through a molecular dynamics study considering the external surface. The results show that DON presents the most promising theoretical results for a selective sucrose/6-kestose separation.We thank MICINN of Spain for funding through projects RTI2018101784-B-I00, RTI2018-101033-B-I00, SEV-2016-0683 as well as ASICUPV and CESGA for computational facilities. IBL and PGI gratefully acknowledge CSIC for a JAE-Intro fellowship. AM thanks Generalitat Valenciana for the predoctoral fellowship GRISOLIAP/2019/084.Bolaño Losada, I.; Grobas-Illobre, P.; Misturini, A.; Polaina, J.; Seminóvski, Y.; Sastre Navarro, GI. (2021). Separation of an aqueous mixture of 6-kestose/sucrose with zeolites: A molecular dynamics simulation. Microporous and Mesoporous Materials. 319:1-10. https://doi.org/10.1016/j.micromeso.2021.111031S11031

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued

Sulfuros fotocatalizadores que utilizan ampliamente el espectro de luz visible

Cuando se usa fotocatálisis, tanto para procesos de descontaminación como para síntesis química específica y (especialmente) para aprovechamiento de energía solar, importa aprovechar un rango muy amplio de luz visible. Para ello se estudian hoy principalmente óxidos (con o sin adición de aniones que disminuyen el gap como el nitrógeno); los sulfuros, como el bien conocido CdS, tienen estabilidad limitada, sobre todo para procesos de fotooxidación en presencia de agua en los que sufren corrosión. Aquí se presentan estudios sobre sulfuros como el In2S3 y el SnS2 (con bandgaps respectivos de 2.0 y 2.2 eV [1]) cuyos metales tienen mayor valencia y coordinación octaédrica, y en los que por ambos factores cabe suponer que su red cristalina, más compacta, tendrá mayor estabilidad. Se muestra también que mediante un dopado importante con vanadio se puede extender su rango espectral de fotoactividad, lo que se atribuye a la formación de una banda intermedia que posibilita el uso de dos fotones con energía inferior al bandgap para conseguir una excitación completa en el semiconductor; este proceso ha sido propuesto últimamente para aumentar el rendimiento de las células fotovoltaicas

New materials for intermediate band photovoltaic cells. A theoretical and experimental approach

Density functional theory calculations of certain transition-metal doped semiconductors show a partially occupied relatively narrow band located between valence band and conduction band. These novel systems, containing the metallic band, are called intermediate-band materials. They have enhanced optoelectronic properties which allow an increase in solar energy conversion efficiency of conventional solar cells. We previously proposed III-V, chalcopyrite and sulfide derived compounds showing desirable characteristics to produce the intermediate band of interest inside the band-gap. In order to obtain further intermediate-band material proposals, this work focuses on studing other compounds constituted mainly by tetravalent elements. The first proposal is vanadium substituting Sn atoms in SnS2 , the second one is composed by type II silicon clathrate with two possibilities: vanadium substituting Si and Ag occluded in the intra-crystalline cavities. UV-Vis-NIR spectra of some of these systems experimentally synthesized show an agreement with previous theoretical prediction

Ab-Initio calculations including Van der Waals interactions: the SnS2 layered material

Tin disulfide SnS2 was recently proposed as a high efficiency solar cell precursor [1]. The aim of this work is a deep study of the structural disposition of the most important polytipes of this layered material, not only describing the electronic correlation but also the interatomic Van der Waals interactions that is present between the layers. The two recent implementations to take Van der Waals interactions into account in the VASP code are the self-consistent Dion et al. [2] functional optimized for solids by Michaelides et al [3] and the Grimme [4] dispersion correction that is applied after each autoconsistent PBE electronic calculation. In this work these two methods are compared with DFT PBE functional. The results we will presented at this Conference, demonstrates the enhancement of the geometric parameters by the use of the Van der Waals interactions in agreement with the experimental values