Wide band-gap tuning Cu2ZnSn1-xGexS4 single crystals: Optical and vibrational properties

The linear optical properties of Cu2ZnSn1-xGe x S4 high quality single crystals with a wide range of Ge contents (x=0.1, 0.3, 0.5, 0.7, 0.9 and 1) have been investigated in the ultraviolet and near infrared range using spectroscopic ellipsometry measurements. From the analysis of the complex dielectric function spectra it has been found that the bandgap E 0 increases continuously from 1.49eV to 2.25eV with the Ge content. Furthermore, the evolution of the interband transitions E 1A and E 1B has been also determined. Raman scattering using three different excitation wavelengths and its analysis have been performed to confirm the absence of secondary phases in the samples, and to distinguish between stannite, wurtzite, wurzstannite and kesterite structures. Additionally, the analysis of the high resolution Raman spectra obtained in samples with different [Ge]/([Ge]+[Sn]) ratios allows describing a bimodal behavior of the dominant A modes. The understanding of the incorporation of Ge into the Cu2ZnSnS4 lattice is fundamental in order to develop efficient bandgap engineering of these compounds towards the fabrication of kesterite based solar cells with enhanced performanceThis work was supported by the Marie Curie-ITN project (KESTCELL, GA: 316488), Marie Curie-IRSES project (PVICOKEST, GA: 269167), AMALIE (TEC2012-38901-C02-01) and SUNBEAM (ENE2013-49136-C4-3-R) project funded by the Spanish Ministry of Economy and Competitiveness. RC acknowledges financial support from Spanish MINECO within the Ramón y Cajal program (RYC-2011-08521

Towards the growth of Cu2ZnSn1-xGexS4 thin films by a single-stage process: Effect of substrate temperature and composition

Cu2ZnSn1-xGexS4 (CZTGS) thin films prepared by flash evaporation of a Zn-rich Cu2ZnSn0.5Ge0.5S4 bulk compound in powder form, and a subsequent thermal annealing in S containing Ar atmosphere are studied. The effect of the substrate temperature during evaporation and the initial composition of the precursor powder on the growth mechanism and properties of the final CZTGS thin film are investigated. The microstructure of the films and elemental depth profiles depend strongly on the growth conditions used. Incorporation of Ge into the Cu2ZnSnS4 lattice is demonstrated by the shift of the relevant X-ray diffraction peaks and Raman vibrational modes towards higher diffraction angles and frequencies respectively. A Raman mode at around 348-351 cm-1 is identified as characteristic of CZTGS alloys for x = [Ge]/([Sn]+[Ge]) = 0.14-0.30. The supply of Ge enables the reduction of the Sn loss via a saccrifical Ge loss. This fact allows increasing the substrate temperature up to 350º C during the evaporation, forming a high quality kesterite material and therefore, reducing the deposition process to one single stageRC acknowledges financial support from Spanish MINECO within the Ramón y Cajal programme (RYC-2011-08521) and VIR for the Juan de la Cierva fellowship (JCI-2011-10782). GB also acknowledges the CSIC-JAE pre-doctoral program, co-funded by the European Social Fund. This work was supported by the Marie Curie-IRSES project (PVICOKEST, GA: 269167), Marie Curie-ITN project (KESTCELL, GA: 316488), DAAD project (INTERKEST, Ref: 57050358), and MINECO projects (SUNBEAM, ENE2013-49136-C4-3-R) (TEC2012-38901-C02-01). A. Scheu is acknowledged for GDOES measurement

Towards the growth of Cu2ZnSn1 xGexS4 thin films by a single-stage process: Effect of substrate temperature and composition

9 págs.; 7 figs.; 2 tabs.Cu2ZnSn1-xGexS4 (CZTGS) thin films prepared by flash evaporation of a Zn-rich Cu2ZnSn0.5Ge0.5S4 bulk compound in powder form, and a subsequent thermal annealing in S containing Ar atmosphere are studied. The effect of the substrate temperature during evaporation and the initial composition of the precursor powder on the growth mechanism and properties of the final CZTGS thin film are investigated. The microstructure of the films and elemental depth profiles depend strongly on the growth conditions used. Incorporation of Ge into the Cu2ZnSnS4 lattice is demonstrated by the shift of the relevant X-ray diffraction peaks and Raman vibrational modes towards higher diffraction angles and frequencies respectively. A Raman mode at around 348-351 cm-1 is identified as characteristic of CZTGS alloys for x = [Ge]/([Sn]+[Ge]) = 0.14-0.30. The supply of Ge enables the reduction of the Sn loss via a saccrifical Ge loss. This fact allows increasing the substrate temperature up to 350º C during the evaporation, forming a high quality kesterite material and therefore, reducing the deposition process to one single stage & 2015 Elsevier B.V. All rights reserved.RC acknowledges financial support from Spanish MINECO within the Ramón y Cajal programme (RYC-2011-08521) and VIR for the Juan de la Cierva fellowship (JCI-2011-10782). GB also acknowledges the CSIC-JAE Pre-doctoral Program, co-funded by the European Social Fund. This work was supported by the Marie Curie-IRSES Project (PVICOKEST, GA: 269167), Marie Curie-ITN project (KESTCELL, GA: 316488), DAAD project (INTERKEST, Ref: 57050358), and MINECO projects (SUNBEAM, ENE2013-49136-C4-3-R) (TEC2012- 38901-C02-01). A. Scheu is acknowledged for GDOES measurements.Peer Reviewe

Resonant Raman scattering of ZnS_xSe_1-x solid solutions:role of S and Se electronic states

A combined theoretical and experimental study of the enhancement in the Raman mode intensities of ZnSSe compounds, under various resonant conditions, is presented, leading to more detailed insights into the role of chalcogen electronic states in the photon–matter interaction.</p

Secondary crystalline phases identification in Cu2ZnSnSe4 thin films: contributions from Raman scattering and photoluminescence

In this work, we present the Raman peak positions of the quaternary pure selenide compound Cu2ZnSnSe4 (CZTSe) and related secondary phases that were grown and studied under the same conditions. A vast discussion about the position of the X-ray diffraction (XRD) reflections of these compounds is presented. It is known that by using XRD only, CZTSe can be identified but nothing can be said about the presence of some secondary phases. Thin films of CZTSe, Cu2SnSe3, ZnSe, SnSe, SnSe2, MoSe2 and a-Se were grown, which allowed their investigation by Raman spectroscopy (RS). Here we present all the Raman spectra of these phases and discuss the similarities with the spectra of CZTSe. The effective analysis depth for the common back-scattering geometry commonly used in RS measurements, as well as the laser penetration depth for photoluminescence (PL) were estimated for different wavelength values. The observed asymmetric PL band on a CZTSe film is compatible with the presence of CZTSe single-phase and is discussed in the scope of the fluctuating potentials’ model. The estimated bandgap energy is close to the values obtained from absorption measurements. In general, the phase identification of CZTSe benefits from the contributions of RS and PL along with the XRD discussion.info:eu-repo/semantics/publishedVersio

Multiwavelength excitation Raman scattering study of polycrystalline kesterite Cu2ZnSnS4 thin films

This work presents a complete analysis of all Raman active modes of Cu 2ZnSnS4 measuring with six different excitation wavelengths from near infrared to ultraviolet. Simultaneous fitting of spectra allowed identification of 18 peaks from device grade layers with composition close to stoichiometry that are attributed to the 27 optical modes theoretically expected for this crystalline structure, including detection of 5 peaks not observed previously, but theoretically predicted. Resonance effects are assumed to explain the observed increase in intensity of weak modes for near infrared and ultraviolet excitations. These results are particularly relevant for experimental discrimination of Raman modes related to secondary phases

Resonant Raman scattering of ZnS_xSe_1-x solid solutions:role of S and Se electronic states

A comprehensive Raman resonance scattering study of ZnSxSe1-x (ZnSSe) solid solutions over the whole compositional range (0 ≤ x ≤ 1) has been made using 325 and 455 nm excitation wavelengths. The Raman scattering intensities of the LO ZnS-like and ZnSe-like phonon modes, corresponding to pure S and Se vibrations, respectively, are revealed to be significantly enhanced when excited with 325 nm excitation in the case of S vibrations, and with 455 nm in the case of the Se vibrations. This behavior is explained with the interaction of the excitation photons with the corresponding S or Se electronic states in the conduction band, and further confirmed with first principle simulations. These findings advance the fundamental understanding of the coupling between the electronic transitions and photons in the case of Raman resonance effects, and provide inputs for further studies of lattice dynamics, especially in the case of chalcogenide materials. Additionally, the coexistence of modes corresponding to only S vibrations and only Se vibrations in the ZnSSe alloys makes these results applicable for the compositional assessment of ZnSSe compounds

Multiwavelength excitation Raman scattering study of polycrystalline kesterite Cu2ZnSnS4 thin films

This work presents a complete analysis of all Raman active modes of Cu 2ZnSnS4 measuring with six different excitation wavelengths from near infrared to ultraviolet. Simultaneous fitting of spectra allowed identification of 18 peaks from device grade layers with composition close to stoichiometry that are attributed to the 27 optical modes theoretically expected for this crystalline structure, including detection of 5 peaks not observed previously, but theoretically predicted. Resonance effects are assumed to explain the observed increase in intensity of weak modes for near infrared and ultraviolet excitations. These results are particularly relevant for experimental discrimination of Raman modes related to secondary phases

Impact of electronic defects on the Raman spectra from electrodeposited Cu(In,Ga)Se 2 solar cells: Application for non-destructive defect assessment

International audienc

Wide band-gap tuning Cu2ZnSn1-xGexS4 single crystals: optical and vibrational properties

The linear optical properties of Cu2ZnSn1-xGexS4 high quality single crystals with a wide range of Ge contents (x = 0.1, 0.3, 0.5, 0.7, 0.9 and 1) have been investigated in the ultraviolet and near infrared range using spectroscopic ellipsometry measurements. From the analysis of the complex dielectric function spectra it has been found that the bandgap E0 increases continuously from 1.49 eV to 2.25 eV with the Ge content. Furthermore, the evolution of the interband transitions E1A and E1B has been also determined. Raman scattering using three different excitation wavelengths and its analysis have been performed to confirm the absence of secondary phases in the samples, and to distinguish between stannite, wurtzite, wurzstannite and kesterite structures. Additionally, the analysis of the high resolution Raman spectra obtained in samples with different [Ge]/([Ge]+[Sn]) ratios allows describing a bimodal behavior of the dominant A modes. The understanding of the incorporation of Ge into the Cu2ZnSnS4 lattice is fundamental in order to develop efficient bandgap engineering of these compounds towards the fabrication of kesterite based solar cells with enhanced performanc