Theory of near-gap second harmonic generation in centrosymmetric magnetic semiconductors: Europium chalcogenides

Second harmonic generation is strictly forbidden in centrosymmetric materials, within the electric dipole approximation. Recently, it was found that the centrosymmetric magnetic semiconductors EuTe and EuSe can generate near-gap second harmonics, if the system is submitted to an external magnetic field. Here, a theoretical model is presented, which well describes the observed phenomena. The model shows that second harmonic generation becomes efficient when the magnetic dipole oscillations between the band-edge excited states of the system, induced by the excitation light, enter the in-phase regime, which can be achieved by applying a magnetic field to the material.

Solvothermal synthesis of one-dimensional chalcogenides containing group 13 elements

The solvothermal synthesis and characterisation of [C6H16N2][GaS2]2 (1), [C6H16N2][Ga2Se3(Se2)] (2), and mixed-metal phases with composition [C6H16N2][Ga2–xInxSe3(Se2)] (0 < x < 2)(3–5), is described. These materials have been characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis and UV/Vis diffuse reflectance spectroscopy. The materials contain one-dimensional anionic chains. In 1, these chains consist of edge-linked GaS4 tetrahedra, whilst in 2–5, the chains contain perselenide (Se2)2– units and comprise alternating four-membered [M2Se2] and five-membered [M2Se3] rings (where M = Ga, In). Compounds 3–5 represent the first examples of ternary mixed-metal [M2Se3(Se2)]2– chains.

MAGNETO-OPTICAL ABSORPTION AND PHOTOMAGNETISM IN EUROPIUM CHALCOGENIDES

The absorption threshold in EuTe and EuSe was investigated as a function of applied magnetic field in the Faraday geometry. A well-resolved doublet of sharp dichroic lines was observed when the magnetic field induced ferromagnetic alignment of the spins in the crystal lattice. In contrast, at zero magnetic field only a broad and featureless absorption onset is seen. These results are fully explained in terms of a model of electronic transitions between localized states at the Eu lattice site and a tight-binding conduction band, which incorporates the formation of spin domains. Based on this model, predictions are made concerning the possibility of inducing magnetization of the spin lattices by illuminating the material with circularly polarized light.

Metallic chalcogenolates mediated modular Michael-aldol cascade reaction: an easy route to multi-functionalized chalcogenides and Morita-Baylis-Hillman adducts

Chalcogenolate mediated Michael-aldol cascade reactions consists of a very efficient route to multi-functionalized gamma-hydroxichalcogenides. Although, when selenolates are employed, these gamma-hydroxichalcogenides can be readily converted into the corresponding Morita-Baylis-Hillman adducts by oxidative elimination of the selenium moiety. In this context, herein we present a complete study on the scope and limitations of this reaction. (C) 2012 Elsevier Ltd. All rights reserved.

Thin films of Cu, In and Sb chalcogenides as photovoltaic absorbers

Many different photovoltaic technologies are being developed for large-scale solar energy conversion such as crystalline silicon solar cells, thin film solar cells based on a-Si:H, CIGS and CdTe. As the demand for photovoltaics rapidly increases, there is a pressing need for the identification of new visible light absorbing materials for thin-film solar cells. Nowadays there are a wide range of earth-abundant absorber materials that have been studied around the world by different research groups. The current thin film photovoltaic market is dominated by technologies based on the use of CdTe and CIGS, these solar cells have been made with laboratory efficiencies up to 19.6% and 20.8% respectively. However, the scarcity and high cost of In, Ga and Te can limit in the long-term the production in large scale of photovoltaic devices. On the other hand, quaternary CZTSSe which contain abundant and inexpensive elements like Cu, Zn, Sn, S and Se has been a potential candidate for PV technology having solar cell efficiency up to 12.6%, however, there are still some challenges that must be accomplished for this material. Therefore, it is evident the need to find the alternative inexpensive and earth abundant materials for thin film solar cells. One of these alternatives is copper antimony sulfide(CuSbS2) which contains abundant and non-toxic elements which has a direct optical band gap of 1.5 eV, the optimum value for an absorber material in solar cells, suggesting this material as one among the new photovoltaic materials. This thesis work focuses on the preparation and characterization of In6Se7, CuSbS2 and CuSb(S1-xSex)2 thin films for their application as absorber material in photovoltaic structures using two stage process by the combination of chemical bath deposition and thermal evaporation.

A new application for transition metal chalcogenides:WS2 catalysed esterification of carboxylic acids

The first application of WS2, a well-known graphene analogue, as a solid acid catalyst for carboxylic acid esterification is reported. WS2 exhibits excellent specific activities and high conversion to methyl esters of (65–90%) for C2–C16 carboxylic acid esterification with methanol under mild conditions, with Turnover Frequencies between 80 and 180 h−1, and outstanding water tolerance even under equimolar water spiking. WS2 also exhibits good stability towards methyl propanoate in the continuous esterification of propanoic acid, and is a promising candidate for biofuels production.

Optical third-harmonic spectroscopy of the magnetic semiconductor EuTe

EuTe possesses the centrosymmetric crystal structure m3m of rocksalt type in which the second-harmonic generation is forbidden in electric dipole approximation but the third-harmonic generation (THG) is allowed. We studied the THG spectra of this material and observed several resonances in the vicinity of the band gap at 2.2-2.5 eV and at higher energies up to 4 eV, which are related to four-photon THG processes. The observed resonances are assigned to specific combinations of electronic transitions between the ground 4f(7) state at the top of the valence band and excited 4f(6)5d(1) states of Eu(2+) ions, which form the lowest energy conduction band. Temperature, magnetic field, and rotational anisotropy studies allowed us to distinguish crystallographic and magnetic-field-induced contributions to the THG. A strong modification of THG intensity for the 2.4 eV band and suppression of the THG for the 3.15 eV band was observed in applied magnetic field. Two main features of the THG spectra were assigned to 5d(t(2g)) and 5d(e(g)) subbands at 2.4 eV and 3.15 eV, respectively. A microscopic quantum-mechanical model of the THG response was developed and its conclusions are in qualitative agreement with the experimental results.

Optical second harmonic generation in the centrosymmetric magnetic semiconductors EuTe and EuSe

The magnetic europium chalcogenide semiconductors EuTe and EuSe are investigated by the spectroscopy of second harmonic generation (SHG) in the vicinity of the optical band gap formed by transitions involving the 4f and 5d electronic orbitals of the magnetic Eu(2+) ions. In these materials with centrosymmetric crystal lattice the electric-dipole SHG process is symmetry forbidden so that no signal is observed in zero magnetic field. Signal appears, however, in applied magnetic field with the SHG intensity being proportional to the square of magnetization. The magnetic field and temperature dependencies of the induced SHG allow us to introduce a type of nonlinear optical susceptibility determined by the magnetic-dipole contribution in combination with a spontaneous or induced magnetization. The experimental results can be described qualitatively by a phenomenological model based on a symmetry analysis and are in good quantitative agreement with microscopic model calculations accounting for details of the electronic energy and spin structure.

Zero-phonon emission and magnetic polaron parameters in EuTe

A phonon structure in the photoluminescence of EuTe was discovered, with a well-defined zero-phonon emission line (ZPL). The ZPL redshifts linearly with the intensity of applied magnetic field, indicating spin relaxation of the photoexcited electron, and saturates at a lower magnetic field than the optical absorption bandgap, which is attributed to formation of magnetic polarons. From the difference in these saturation fields, the zero-field polaron binding energy and radius are estimated to be 43 meV and 3.2 (in units of the EuTe lattice parameter), respectively. (C) 2011 American Institute of Physics. [doi:10.1063/1.3634030]

Modeling the dichroic absorption band edge and light-induced magnetism in EuTe

The band-edge optical absorption in EuTe is studied in the framework of the 5d conduction band atomic model. Both relaxed antiferromagnetic order, and ferromagnetic order induced by an external magnetic field, were analyzed. For ferromagnetic arrangement, the absorption is characterized by a hugely dichroic doublet of narrow lines. In the antiferromagnetic order, the spectrum is blueshifted, becomes much broader and weaker, and dichroism is suppressed. These results are in excellent qualitative and quantitative agreement with experimental observations on EuTe and EuSe published by us previously [Phys. Rev. B 72, 155337 (2005)]. The possibility of inducing ferromagnetic order by illuminating the material at photon energies resonant with the band gap is also discussed.

Hydroalumination of Thioacetylenes: A Versatile Generation and Reactions of -Aluminate Sulfides Intermediates

Hydroalumination of thioacetylenes using DIBAL-H and lithium di-(isobutyl)-n-(butyl)-aluminate hydride (Zweifel`s reagent), followed by addition of water, furnished exclusively the (Z)- and (E)-vinyl sulfides, respectively. The regio- and stereochemistry of the intermediates generated, (Z)- and (E)-phenylthio vinyl alanates, were determined by capture with iodine, which afforded the corresponding (E)- and (Z)-1-iodo-1-phenylthio-2-organoyl ethenes. Reactions of the (E)-iodo(thio)ketene acetals with n-BuLi followed by addition of hexanal afforded the (Z)-phenylthio allylic alcohol, while the (Z)-iodo(thio)ketene acetals under similar reactions conditions gave the (E)-phenylthio allylic alcohol exclusively.

Growth pressure dependence of Cu2ZnSnSe4 properties

In this work, we show a set of growth conditions, for the two step process, with which the growth of CZTSe is successful and reproducible. The properties of the best CTZSe thin films grown by this method were examined by SEM/EDS, XRD, Raman scattering, AFM/EFM, transmittance and reflectance measurements, photoluminescence (PL) measurements and hot point probe. A broad emission band was observed in the photoluminescence spectrum of the CZTSe thin film. The band gap energy was estimated to be around 1.05 eV at room temperature, using the transmittance and reflectance data, and CZTSe samples show p-type conductivity with the hot point probe. The different characterization techniques show that we could grow single phase CZTSe thin films with our optimized process conditions.

Growth and characterization of Cu2ZnSn(S,Se)4 thin films for solar cells

Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) with their band gap energies around 1.45 eV and 1.0 eV, respectively, can be used as the absorber layer in thin film solar cells. By using a mixture of both compounds, Cu2ZnSn(S,Se)4 (CZTSSe), a band gap tuning may be possible. The latter material has already shown promising results such as solar cell efficiencies up to 10.1%. In this work, CZTSSe thin films were grown in order to study its structure and to establish the best growth precursors. SEM micrographs reveal an open columnar structure for most samples and EDS composition profiling of the cross sections show different selenium gradients. X-ray diffractograms show different shifts of the kesterite/stannite (1 1 2) peak, which indicate the presence of CZTSSe. From Raman scattering analysis, it was concluded that all samples had traces of CZTS and CZTSSe. The composition of the CZTSSe layer was estimated using X-ray diffraction and Raman scattering and both results were compared. It was concluded that Se diffused more easily in precursors with ternary Cu–Sn–S phases and metallic Zn than in precursors with ZnS and/or CZTS already formed. It was also showed that a combination of X-ray diffraction and Raman scattering can be used to estimate the ratio of S per Se in CZTSSe samples.