Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm(-1) on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis

Raman microprobe characterization of electrodeposited S-rich CuIn(S,Se)2 for photovoltaic applications: Microstructural analysis

This article reports a detailed Raman scattering and microstructural characterization of S-rich CuIn(S,Se)2 absorbers produced by electrodeposition of nanocrystalline CuInSe2 precursors and subsequent reactive annealing under sulfurizing conditions. Surface and in-depth resolved Raman microprobe measurements have been correlated with the analysis of the layers by optical and scanning electron microscopy, x-ray diffraction, and in-depth Auger electron spectroscopy. This has allowed corroboration of the high crystalline quality of the sulfurized layers. The sulfurizing conditions used also lead to the formation of a relatively thick MoS2 intermediate layer between the absorber and the Mo back contact. The analysis of the absorbers has also allowed identification of the presence of In-rich secondary phases, which are likely related to the coexistence in the electrodeposited precursors of ordered vacancy compound domains with the main chalcopyrite phase, in spite of the Cu-rich conditions used in the growth. This points out the higher complexity of the electrodeposition and sulfurization processes in relation to those based in vacuum deposition techniques

Kesterite thin films of Cu2ZnSnS4 obtained by spray pyrolysis

Thin films of Cu2ZnSnS4 CZTS were deposited using the spray pyrolysis method as relatively fast and vacuum free method. Obtained samples were analyzed using the X Ray Fluorescence, grazing incidence X Ray Diffraction and Raman Spectroscopy techniques. Analysis showed close to stoichiometry composition of the films with kesterite type structure but poor crystalline quality and possible existence of secondary phases. To improve the quality of the films, the as prepared layers were annealed in the presence of elemental Sn and S. Comparison of the results before and after annealing showed a strong improvement of the crystalline quality and a significant reduction of concentration of secondary phases of the films without significant change of composition. The measured optical band gap is equal to 1.52 and 1.55 eV in the as prepared and annealed films, respectively. The optical absorption coefficient is found to be gt; 10 4 cm

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

Impact of the selenisation temperature on the structural and optical properties of CZTSe absorbers

We present structural and optical spectroscopy studies of thin films of Cu2ZnSnSe4 (CZTSe) with strong copper deficiency deposited on Mo/Glass substrates and selenised at 450, 500 or 550 °C. Solar cells fabricated from these films demonstrated efficiencies up to 7.4% for selenisation at 500 °C. Structural analysis based on X-ray diffraction and Raman spectroscopy revealed the presence of SnSe2 in the film selenised at 450 °C but not detected in the films selenised at higher temperatures. A progressive decrease of the Sn and Se content was observed as the selenisation temperature increased. Photoluminescence excitation was used to determine the bandgaps at 4.2 K. Detailed measurements of the temperature and excitation intensity dependencies of the photoluminescence spectra allow the recombination mechanisms of the observed emission bands to be identified as band-to-impurity and band-to-band transitions, and their evolution with selenisation temperature changes to be analysed. The strongest band-to-band transition is recorded in the PL spectra of the film selenised at 500 °C and can be observed from 6 K to room temperature. The compositional and structural changes in the films and their influence on the optoelectronic properties of CZTSe and solar cells are discussed

Cu2ZnSnS4 thin film solar cells grown by fast thermal evaporation and thermal treatment

Cu2ZnSnS4 thin films have been produced via rapid thermal evaporation of off-stoichiometric kesterite powder followed by annealing in an Ar atmosphere. Different heating rates were applied during the thermal treatments. The chemical composition and structural properties of the deposited layers as well as the distribution of the elements through the kesterite thin film have been investigated. The initial growth of a SnS secondary phase during evaporation led to the formation of this secondary phase next to the Mo back contact. Solar cell power conversion efficiencies were limited to values about 3 % due to this secondary phase. Furthermore, an increased open circuit voltage was demonstrated by using a Zn(O,S) buffer layerThis work was supported by DAAD project (INTERKEST, Ref: 57050358), Marie Curie-ITN (KESTCELLS, GA: 316488) and MINECO project (SUNBEAM, ENE2013-49136-C4-3-R). RC and ES acknowledge financial support from Spanish MINECO within the Ramón y Cajal program (RYC-2011-08521) and (RYC-2011-09212) respectively. SG also thanks the Government of Spain for the FPI fellowship (BES-2014-068533)

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

The importance of back contact modification in Cu2ZnSnSe4 solar cells: The role of a thin MoO2 layer

Cu2ZnSn(SxSe1-x)4 (CZTSSe) photovoltaic absorbers could be the earth-abundant and low toxicity replacement for the already commercialized CuIn1-xGaxSe2 (CIGS) thin film technology. In order to make this possible, specific research efforts applied to the bulk, front and back interfaces must be performed with the aim of improving CZTSSe performance. In this paper the importance of back contact modification to obtain high efficiency Cu2ZnSnSe4 (CZTSe) solar cells and to increase a paramount and limiting parameter such as VOC is highlighted. Several Mo configurations (monolayer, bi-layer and tri-layer) with different electrical and morphological properties are investigated in CZTSe solar cells. An optimum tri-layer configuration in order to minimize overselenization of the back contact during thermal annealing while keeping reasonable electrical features is defined. Additionally, a thin intermediate MoO2 layer that results in a very effective barrier against selenization and innovative way to efficiently assist in the CZTSe absorber sintering is introduced. The use of this layer enhances grain growth and subsequently the efficiency of solar cells increases via major VOC and FF improvement. An efficiency increase from 7.2% to 9.5% is obtained using a Mo tri-layer with a 20 nm intermediate MoO2 layerThis research was supported by the Framework 7 program under the project KESTCELLS (FP7-PEOPLE-2012-ITN-316488), by MINECO (Ministerio de Economía y Competitividad de España) under the SUNBEAM project (ENE2013-49136-C4-1-R), and by European Regional Development Founds (ERDF, FEDER Programa Competitivitat de Catalunya 2007–2013). Authors from IREC and the University of Barcelona belong to the M-2E (Electronic Materials for Energy) Consolidated Research Group and the XaRMAE Network of Excellence on Materials for Energy of the “Generalitat de Catalunya”. M.E-R. thanks the MINECO for the FPI-MINECO (BES-2011-045774), Y.S. for the PTA fellowship (PTA2012-7852-A), SG for the FPI fellowship (BES-2014-068533), M.P. for the MINECO postdoctoral fellow (FPDI-2013-18968), E.S. and R.C. for the “Ramon y Cajal” fellowship (RYC-2011-09212) and (RYC-2011-08521) respectively, and H.X. thanks the “China Scholarship Council” fellowship (CSC Nº 201206340113

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

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