Andrew Fairbrother

Development of a Selective Chemical Etch To Improve the Conversion Efficiency of Zn-Rich Cu2ZnSnS4 Solar Cells

Improvement of the efficiency of Cu(2)ZnSnS(4) (CZTS)-based solar cells requires the development of specific procedures to remove or avoid the formation of detrimental secondary phases. The presence of these phases is favored by the Zn-rich and Cu-poor conditions that are required to obtain device-grade layers. We have developed a selective chemical etching process based on the use of hydrochloric acid solutions to remove Zn-rich secondary phases from the CZTS film surface, which are partly responsible for the deterioration of the series resistance of the cells and, as a consequence, the conversion efficiency. Using this approach, we have obtained CZTS-based devices with 5.2% efficiency, which is nearly twice that of the devices we have prepared without this etching process.

Multiwavelength excitation Raman scattering study of polycrystalline kesterite Cu2ZnSnS4 thin films

This work presents a complete analysis of all Raman active modes of Cu2ZnSnS4 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.

ZnSe Etching of Zn‐Rich Cu2ZnSnSe4: An Oxidation Route for Improved Solar‐Cell Efficiency

Cu2ZnSnSe4 kesterite compounds are some of the most promising materials for low-cost thin-film photovoltaics. However, the synthesis of absorbers for high-performing devices is still a complex issue. So far, the best devices rely on absorbers grown in a Zn-rich and Cu-poor environment. These off-stoichiometric conditions favor the presence of a ZnSe secondary phase, which has been proved to be highly detrimental for device performance. Therefore, an effective method for the selective removal of this phase is important. Previous attempts to remove this phase by using acidic etching or highly toxic organic compounds have been reported but so far with moderate impact on device performance. Herein, a new oxidizing route to ensure efficient removal of ZnSe is presented based on treatment with a mixture of an oxidizing agent and a mineral acid followed by treatment in an aqueous Na2S solution. Three different oxidizing agents were tested: H2O2, KMnO4, and K2Cr2O7, combined with different concentrations of H2SO4. With all of these agents Se(2-) from the ZnSe surface phase is selectively oxidized to Se(0), forming an elemental Se phase, which is removed with the subsequent etching in Na2S. Using KMnO4 in a H2SO4-based medium, a large improvement on the conversion efficiency of the devices is observed, related to an improvement of all the optoelectronic parameters of the cells. Improvement of short-circuit current density (J(sc)) and series resistance is directly related to the selective etching of the ZnSe surface phase, which has a demonstrated current-blocking effect. In addition, a significant improvement of open-circuit voltage (V(oc)), shunt resistance (R(sh)), and fill factor (FF) are attributed to a passivation effect of the kesterite absorber surface resulting from the chemical processes, an effect that likely leads to a reduction of nonradiative-recombination states density and a subsequent improvement of the p-n junction.

Inhibiting the absorber/Mo-back contact decomposition reaction in Cu2ZnSnSe4 solar cells: the role of a ZnO intermediate nanolayer

This work reports a process based on the use of an ultrathin (10 nm) ZnO intermediate layer for the improvement of the absorber/back contact interface region in Cu2ZnSnSe4 (CZTSe) kesterite solar cells. Raman microprobe measurements performed directly on the substrate surface after mechanical removal of the absorber layer indicate the occurrence of a decomposition reaction of Cu2ZnSnSe4 in contact with the Mo substrate. This leads to a significant degradation of the quality of the absorber/back contact interface, with the formation of a high density of voids. The presence of an intermediate ZnO layer on the Mo coated substrates inhibits the decomposition reaction, because it prevents interaction between the CZTSe and Mo layers during the annealing process. This leads to a significant improvement in the interface morphology as observed by detailed cross-section scanning electron microscopy. It also correlates with the observed increase of the device conversion efficiency from 2.5% up to 6.0%. The improvement in the optoelectronic characteristics of the cells could be related to a significant decrease of the device series resistance due to the formation of a smoother interface with low density of voids, resulting from the effective inhibition of the CZTSe decomposition reaction at the Mo back contact layer.

Impact of Sn(S,Se) secondary phases in Cu2ZnSn(S,Se)4 solar cells: a chemical route for their selective removal and absorber surface passivation.

The control and removal of secondary phases is one of the major challenges for the development of Cu2ZnSn(S,Se)4 (CZTSSe)-based solar cells. Although etching processes have been developed for Cu(S,Se), Zn(S,Se), and CuSn(S,Se) secondary phases, so far very little attention has been given to the role of Sn(S,Se). In this paper, we report a chemical route using a yellow (NH4)2S solution to effectively remove Sn(S,Se). We found that Sn(S,Se) can form on the surface either because of stoichiometric deviation or by condensation. After etching, the efficiency of devices typically increases between 20 and 65% relative to the before etch efficiencies. We achieved a maximum 5.9% efficiency in Se-rich CZTSSe-based devices. It is confirmed that this feature is related not only to the removal of Sn(S,Se) but also to the unexpected passivation of the surface. We propose a phenomenological model for this passivation, which may open new perspectives for the development of CZTSSe-based solar cells.

Influence of compositionally induced defects on the vibrational properties of device grade Cu2ZnSnSe4 absorbers for kesterite based solar cells

This work presents a detailed analysis of the impact of compositionally induced defects on the vibrational properties of Cu2ZnSnSe4 absorbers for kesterite based solar cells. Systematic changes in the intensity of the E and B modes located around the 170, 220, and 250 cm−1 frequency regions, which involve mostly cation vibrations, were observed and analyzed in relation to the occurrence of different kinds of defect clusters involving VCu, ZnCu, ZnSn, CuZn, and SnZn point defects. Additional changes are also interpreted in terms of the appearance of SnSe, ZnSe, and CuSe-like contributions at the 185 and 250 cm−1 spectral regions, respectively. The sensitivity of the Raman measurements to the presence of these kinds of defects corroborates the potential of Raman scattering for point defect assessment in these systems.

ZnS grain size effects on near-resonant Raman scattering: optical non-destructive grain size estimation

Near-resonant Raman scattering measurements of zinc sulfide nanoparticles and thin films have been made and correlated to grain and particle size, respectively, using a 325 nm wavelength excitation source. The area ratios between the first, second, and third order peaks of ZnS identified as the T2(LO) mode decrease with increasing ZnS grain size. This is an effect attributed to changes in the bandgap energy from quantum confinement due to the varying grain size between the films/particles, as noted by a shift in the room temperature photoluminescence emission corresponding to the free exciton emission energy. While Raman scattering spectroscopy is typically limited to identification of phases and their crystalline properties, it is possible to attain more than such straightforward information by calibrating the spectral features to variations between sets of samples. These results open the possibility of making a quantitative grain size estimation in ZnS thin films and nanostructures, as well as in other material systems where ZnS may be expected as a secondary phase, such as Cu2ZnSnS4. Additionally, more commonly used excitation wavelengths for Raman scattering, such as 514 and 532 nm, are shown to be of limited use in characterizing ZnS thin films due to the extremely low Raman scattering efficiency of ZnS in films with sub-micron thicknesses.

Multiwavelength excitation Raman scattering of Cu2ZnSn(SxSe1−x)4 (0 ≤ x ≤ 1) polycrystalline thin films: Vibrational properties of sulfoselenide solid solutions

In this work, Raman spectroscopy and X-ray diffraction were applied together to evaluate the crystal structure and the phonon modes of photovoltaic grade Cu2ZnSn(SxSe1−x)4 thin films, leading to a complete characterization of their structural and vibrational properties. Vibrational characterization has been based on Raman scattering measurements performed with different excitation wavelengths and polarization configurations. Analysis of the experimental spectra has permitted identification of 19 peaks, which positions are in good accord with theoretical predictions. Besides, the observation of Cu2ZnSnS4-like A symmetry peaks related to S vibrations and Cu2ZnSnSe4-like A symmetry peaks related to Se vibrations, additional Raman peaks, characteristic of the solid solution and previously not reported, are observed, and are attributed to vibrations involving both S and Se anions.

Single-Step Sulfo-Selenization Method to Synthesize Cu2ZnSn(SySe1−y)4 Absorbers from Metallic Stack Precursors

Pentenary Cu2ZnSn(S(y)Se(1-y))4 (kesterite) photovoltaic absorbers are synthesized by a one-step annealing process from copper-poor and zinc-rich precursor metallic stacks prepared by direct-current magnetron sputtering deposition. Depending on the chalcogen source--mixtures of sulfur and selenium powders, or selenium disulfide--as well as the annealing temperature and pressure, this simple methodology permits the tuning of the absorber composition from sulfur-rich to selenium-rich in one single annealing process. The impact of the thermal treatment variables on chalcogenide incorporation is investigated. The effect of the S/(S+Se) compositional ratio on the structural and morphological properties of the as-grown films, and the optoelectronic parameters of solar cells fabricated using these absorber films is studied. Using this single-step sulfo-selenization method, pentenary kesterite-based devices with conversion efficiencies up to 4.4 % are obtained.

Impact of electronic defects on the Raman spectra from electrodeposited Cu(In,Ga)Se2 solar cells: Application for non-destructive defect assessment

This work reports on the electrical and Raman scattering analysis of Cu(In,Ga)Se2 cells synthesised with different densities of Se and Cu related point defects. The analysis of the Raman spectra from the surface region of the absorbers shows a direct correlation between the spectral features of the main Raman peak and the density of Se vacancies detected by admittance spectroscopy, being sensitive to the presence of vacancy densities higher than 1015 cm−3. These results corroborate the potential of Raman scattering for the non-destructive detection of electronic defects with potential impact on the characteristics of the solar cells.