Depth profile analyses of films grown at different temperatures

Cu(In,Ga)Se2films are used as absorber layers in chalcopyrite thin filmsolar cells. As the gallium concentration in the absorber can be used to control the band gap, there have been many efforts to vary the gallium concentration in depth to gain an optimum balance of light absorption, carrier collection, and recombination at different depths of the absorber film, leading to improved quantum efficiency. In this study, we investigate the effect of the maximum substrate temperature during film growth on the depth dependent gallium concentration. For the in-depth gallium concentration analyses, we use two techniques, covering complementary depth ranges. Angle dependent soft x-ray emission spectroscopy provides access to information depths between 20 and 470 nm, which covers the depth range of the space charge region, where most of the photoexcited carriers are generated. Therefore, this depth range is of particular interest. To complement this investigation we use secondary neutral mass spectrometry, which destructively probes the whole thickness of the absorber (≈2 μm). The two methods show increasingly pronounced gallium and indium gradients with decreasing maximum substrate temperature. The probing of the complementary depth ranges of the absorbers gives a consistent picture of the in-depth gallium distribution, which provides a solid basis for a comprehensive discussion about the effect of a reduced substrate temperature on the formation of gallium gradients in Cu(In,Ga)Se2 and the device performance of the corresponding reference solar cells

Assessment of Chemical and Electronic Surface Properties of the Cu2ZnSn(SSe)4 after Different Etching Procedures by Synchrotron-based Spectroscopies

Kesterite Cu2ZnSn(S,Se)4 absorber layers with different [S]/([S]+[Se]) ratios were studied using XPS, UPS, Hard X-ray (HIKE) photoemission and the Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS). The samples were prepared by IREC using sequentially sputtered metallic precursor stacks with metal ratios of [Cu]/([Zn]+[Sn])=0.80, [Zn]/[Sn]=1.20 followed by annealing under S+Se+Sn atmosphere. Different etching procedures were used depending on the sample's composition. It is shown that the surface composition varies from that of the bulk, especially for the Se-rich samples. Contamination with sulfur is detected after using a Na2S etching solution for the pure Se kesterite. A Cu-depleted surface was found for all samples before and after etching. HIKE measurements show a higher [Zn]/[Sn] ratio in the near surface region than on the very surface. This is explained by the fact, the etching procedure removes secondary phases from the very few surface layers, while some of ZnS(e) is still buried underneath. In order to investigate the band gap transition from the pure sulfide (1.5 eV) to the pure selenide (1eV), the valence and conduction band of the respective absorbers were probed. According to UPS and HIKE measurements, the relative distance between Fermi level (Ef) and valance band maximum (VBM) for sulfide sample was 130 meV larger than for selenide. Using NEXAFS on the copper, zinc and tin edges, the development of the conduction band with increasing [S]/([S]+[Se]) ratios was studied. Stoichiometric powder samples were used as reference materials. © 2015 Published by Elsevier Ltd.Peer ReviewedPostprint (published version

Gallium gradients in chalcopyrite thin films: Depth profile analyses of films grown at different temperatures

The following article appeared in Journal of Applied Physics 110.9 (2011): 093509 and may be found at http://scitation.aip.org/content/aip/journal/jap/110/9/10.1063/1.3656986Cu(In,Ga)Se2 films are used as absorber layers in chalcopyrite thin film solar cells. As the gallium concentration in the absorber can be used to control the band gap, there have been many efforts to vary the gallium concentration in depth to gain an optimum balance of light absorption, carrier collection, and recombination at different depths of the absorber film, leading to improved quantum efficiency. In this study, we investigate the effect of the maximum substrate temperature during film growth on the depth dependent gallium concentration. For the in-depth gallium concentration analyses, we use two techniques, covering complementary depth ranges. Angle dependent soft x-ray emission spectroscopy provides access to information depths between 20 and 470 nm, which covers the depth range of the space charge region, where most of the photoexcited carriers are generated. Therefore, this depth range is of particular interest. To complement this investigation we use secondary neutral mass spectrometry, which destructively probes the whole thickness of the absorber (≈2 µm). The two methods show increasingly pronounced gallium and indium gradients with decreasing maximum substrate temperature. The probing of the complementary depth ranges of the absorbers gives a consistent picture of the in-depth gallium distribution, which provides a solid basis for a comprehensive discussion about the effect of a reduced substrate temperature on the formation of gallium gradients in Cu(In,Ga)Se2 and the device performance of the corresponding reference solar cells.The authors acknowledge the support of the European Commission in the framework of the ATHLET-project (Project No. 019670)

Cu2ZnSn(S,Se)4 from CuxSnSy nanoparticle precursors on ZnO nanorod arrays

Solar cells with Cu2ZnSnS4 absorber thin films have a potential for high energy conversion efficiencies with earth-abundant and non-toxic elements. In this work the formation of CZTSSe from CuxSnSy nanoparticles (NPs) deposited on ZnO nanorod (NR) arrays as precursors for zinc is investigated. The NPs are prepared using a chemical route and are dispersed in toluene. The ZnO NRs are grown on fluorine doped SnO2 coated glass substrates by electro deposition method. A series of samples are annealed at different temperatures between 300 °C and 550 °C in selenium containing argon atmosphere. To investigate the products of the reaction between the precursors the series is analyzed by means of X-ray diffraction (XRD) and Raman spectroscopy. The morphology is recorded by scanning electron microscopy (SEM) images of broken cross sections. The XRD measurements and the SEM images show the disappearing of ZnO NRs with increasing annealing temperature. Simultaneously the XRD and Raman measurements show the formation of CZTSSe. The formation of secondary phases and the optimum conditions for the preparation of CZTSSe is discusse

Stability of surfaces in the chalcopyrite system

It has been observed previously that the stable surfaces in chalcopyrites are the polar 112 surfaces. We present an electron microscopy study of epitaxial films of different compositions. It is shown that for both CuGaSe2 and CuInSe2 the 001 surfaces form 112 facets. With increasing Cu excess the faceting is suppressed, indicating a lower surface energy of the 001 surface than the energy of the 112 surface in the Cu rich regime, but the 001 surface is higher in energy than the 112 surface in the Cu poor regime. As both surfaces are polar the stabilization is attributed to defect formatio

Detection of vortex tubes in solar granulation from observations with Sunrise

We have investigated a time series of continuum intensity maps and corresponding Dopplergrams of granulation in a very quiet solar region at the disk center, recorded with the Imaging Magnetograph eXperiment (IMaX) on board the balloon-borne solar observatory Sunrise. We find that granules frequently show substructure in the form of lanes composed of a leading bright rim and a trailing dark edge, which move together from the boundary of a granule into the granule itself. We find strikingly similar events in synthesized intensity maps from an ab initio numerical simulation of solar surface convection. From cross sections through the computational domain of the simulation, we conclude that these `granular lanes' are the visible signature of (horizontally oriented) vortex tubes. The characteristic optical appearance of vortex tubes at the solar surface is explained. We propose that the observed vortex tubes may represent only the large-scale end of a hierarchy of vortex tubes existing near the solar surface.Comment: Astrophysical Journal Letters: Sunrise Special Issue, reveived 2010 June 16; accepted 2010 August

Formation of the physical vapor deposited CdS Cu In,Ga Se2 interface in highly efficient thin film solar cells

We report on the buffer absorber interface formation in highly efficient 14.5 , AM1.5 ZnO CdS Cu In,Ga Se2 solar cells with a physical vapor deposited CdS buffer. For Se decapped Cu In,Ga Se2 CIGSe absorbers we observe sulfur passivation of the CIGSe grain boundaries during CdS growth and at the interface a thermally stimulated formation of a region with a higher band gap than that of the absorber bulk, determining the height of the potential barrier at the CdS CIGSe interface. For air exposed CIGSe samples the grain boundary passivation is impeded by a native oxide adsorbate layer at the CIGSe surface determining the thermal stability of the potential barrier heigh

Temperature Dependence of the Exciton Gap in Monocrystalline CuGaS2

Single crystals of CuGaS2 have been grown by chemical vapour transport. Their near-band gap photoluminescence properties were investigated in the temperature range of 10-300 K. The variation of the exciton gap energy with temperature was studied by means of a three-parameter thermodynamic model, the Einstein model and the Pässler model. Values of the band gap at T=0 K, of a dimensionless constant related to the electron-phonon coupling, and of an effective and a cut-off phonon energy have been estimated. It has also been found that the major contribution of phonons to the shift of Eg as a function of T in CuGaS2 is mainly from optical phonons

Phase transitions during formation of Ag nanoparticles on In2S3 precursor layers

Phase transitions have been investigated for silver deposition onto In2S3 precursor layers by spray chemical vapor deposition from a trimethylphosphine (hexafluoroacetylacetonato) silver (Ag(hfacac)(PMe3)) solution. The formation of Ag nanoparticles (Ag NPs) on top of the semiconductor layer set on concomitant with the formation of AgIn5S8. The increase of the diameter of Ag NPs was accompanied by the evolution of orthorhombic AgInS2. The formation of Ag2S at the interface between Ag NPs and the semiconductor layer was observed. Surface photovoltage spectroscopy indicated charge separation and electronic transitions in the ranges of corresponding band gaps. The phase transition approach is aimed to be applied for the formation of plasmonic nanostructures on top of extremely thin semiconducting layers