A precursor‐annealing process based on a Cu‐rich precursor that has a maximum power conversion efficiency of 7.5% for pure selenide kesterite cells is presented. The Cu‐rich step is beneficial for the transport properties. Nanometer‐sized domains of ZnSe are found in all films.
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.
Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gasphase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.Control of alkali doping is crucial for a range of technologically relevant chalcogenide materials, from photovoltaics (CdTe, Cu(In,Ga)Se 2 , Cu 2 ZnSn(S,Se) 4 ) 1-5 and thermoelectricity (Pb(S,Se,Te)) 6-9 potentially to superconductivity (KFeSe 2 ) 10,11 and quantum computing (Bi 2 Te 3 12 , MoS 2 and WSe 2 13 ). In the case of Cu(In,Ga)Se 2 (CIGSe) solar cell material, the current alkali metal doping procedures are overwhelmingly based on condensed state reactions. Two common approaches are taken. Either by indirect control of the diffusion from a sodium-containing substrate or back contact [14][15][16][17] , or by deliberate doping from the precursor surface through a post deposition treatment (PDT), e.g. by NaF or KF evaporation onto the surface of the absorber to form a tens of nanometer thick layer, followed by annealing [18][19][20] . Control of the sodium content in the former case is difficult as substrates are never identical 21 , and in the latter case at least one extra step is required to add the alkali metal. The subject has been extensively reviewed by Salomé et al. 22. CIGSe thin films are always grown in a controlled atmosphere containing a certain pressure of selenium. The semiconductor requires selenium for its formation and to prevent its decomposition, given that the reaction is ruled by a solid/gas-phase equilibrium 23,24 . The question arises, are any other gas-phase chemical species involved in the equilibrium? All the main binary compounds of CIGSe have low vapour pressures; however, usually CIGSe contains also a considerable amount of sodium incorporated in the film. Is the vapour pressure of sodium or its
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