Optical Measurement of the Stoichiometry of Thin-Film Compounds Synthetized From Multilayers: Example of Cu(In,Ga)Se2.

The properties of centimeter-sized thin-film compound semiconductors depend upon the morphology and chemical composition of the multiple submicrometer-thick elemental and alloy precursor layers from which they are synthesized. The challenge is to characterize the individual precursor layers over these length scales during a multistep synthesis without altering or contaminating them. Conventional electron and X-ray-based morphological and compositional techniques are invasive, require preparation, and are thus incompatible with in-line synthesis processes. In a proof-of-concept study, we applied confocal laser scanning microscopy (CLSM) as a noninvasive optical imaging technique, which measures three-dimensional surface profiles with nanoscale resolution, to this challenge. Using an array of microdots containing Cu(In,Ga)Se2 semiconductor layers for solar cells as an example, we performed CLSM correlative studies to quantify morphological and layer thickness changes during four stages of a thin-film compound synthesis. Using simple assumptions, we measured the micrometer-scale spatially resolved chemical composition of stacked precursor layers to predict the final material phases formed and predict relative device performance. The high spatial resolution, coupled with the ability to measure sizeable areas without influencing the synthesis at high speed, makes CLSM an excellent prospect for research and quality control tool for thin films.

Waste- and Cd-Free Inkjet-Printed Zn(O,S) Buffer for Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells.

Thin film semiconductors grown using chemical bath methods produce large amounts of waste solvent and chemicals that then require costly waste processing. We replace the toxic chemical bath deposited CdS buffer layer from our Cu(In,Ga)(S,Se)2 (CIGS)-based solar cells with a benign inkjet-printed and annealed Zn(O,S) layer using 230 000 times less solvent and 64 000 times less chemicals. The wetting and final thickness of the Zn(O,S) layer on the CIGS is controlled by a UV ozone treatment and the drop spacing, whereas the annealing temperature and atmosphere determine the final chemical composition and band gap. The best solar cell using a Zn(O,S) air-annealed layer had an efficiency of 11%, which is similar to the best conventional CdS buffer layer device fabricated in the same batch. Improving the Zn(O,S) wetting and annealing conditions resulted in the best device efficiency of 13.5%, showing the potential of this method.

Micro-sized thin-film solar cells via area-selective electrochemical deposition for concentrator photovoltaics application.

Micro-concentrator solar cells enable higher power conversion efficiencies and material savings when compared to large-area non-concentrated solar cells. In this study, we use materials-efficient area-selective electrodeposition of the metallic elements, coupled with selenium reactive annealing, to form Cu(In,Ga)Se2 semiconductor absorber layers in patterned microelectrode arrays. This process achieves significant material savings of the low-abundance elements. The resulting copper-poor micro-absorber layers' composition and homogeneity depend on the deposition charge, where higher charge leads to greater inhomogeneity in the Cu/In ratio and to a patchy presence of a CuIn5Se8 OVC phase. Photovoltaic devices show open-circuit voltages of up to 525 mV under a concentration factor of 18 ×, which is larger than other reported Cu(In,Ga)Se2 micro-solar cells fabricated by materials-efficient methods. Furthermore, a single micro-solar cell device, measured under light concentration, displayed a power conversion efficiency of 5% under a concentration factor of 33 ×. These results show the potential of the presented method to assemble micro-concentrator photovoltaic devices, which operate at higher efficiencies while using light concentration.

Chemical instability at chalcogenide surfaces impacts chalcopyrite devices well beyond the surface.

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe2 solar cells.

Continuous-wave laser annealing of metallic layers for CuInSe2 solar cell applications: effect of preheating treatment on grain growth.

Ultra-fast thermal annealing of semiconductor materials using a laser can be revolutionary for short processing times and low manufacturing costs. Here we investigate Cu-In-Se thin films as precursors for CuInSe2 semiconductor absorber layers via laser annealing. The reaction mechanism of laser annealed metal stacks is revealed by measuring ex situ X-ray diffractograms, Raman spectra and composition. It is shown that the formation of CuInSe2 occurs via the formation of Cu x Se/In x Se y binary phases as in conventional annealing routes, despite the entirely different annealing time scale. Pre-alloying the Cu and In metals prior to laser annealing significantly enhances the selenisation reaction rate. Laser annealing for six seconds approaches a near phase-pure material, which exhibits similar crystalline quality to the reference material annealed for ninety minutes in a tube furnace. The estimated quasi Fermi level splitting deficit for the laser annealed material is only 60 meV lower than the reference sample, which implies a high optoelectronic quality.

Sodium enhances indium-gallium interdiffusion in copper indium gallium diselenide photovoltaic absorbers.

Copper indium gallium diselenide-based technology provides the most efficient solar energy conversion among all thin-film photovoltaic devices. This is possible due to engineered gallium depth gradients and alkali extrinsic doping. Sodium is well known to impede interdiffusion of indium and gallium in polycrystalline Cu(In,Ga)Se2 films, thus influencing the gallium depth distribution. Here, however, sodium is shown to have the opposite effect in monocrystalline gallium-free CuInSe2 grown on GaAs substrates. Gallium in-diffusion from the substrates is enhanced when sodium is incorporated into the film, leading to Cu(In,Ga)Se2 and Cu(In,Ga)3Se5 phase formation. These results show that sodium does not decrease per se indium and gallium interdiffusion. Instead, it is suggested that sodium promotes indium and gallium intragrain diffusion, while it hinders intergrain diffusion by segregating at grain boundaries. The deeper understanding of dopant-mediated atomic diffusion mechanisms should lead to more effective chemical and electrical passivation strategies, and more efficient solar cells.

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) 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.

High-speed electrodeposition of copper-tin-zinc stacks from liquid metal salts for Cu2ZnSnSe4 solar cells.

Cu2ZnSnSe4-based solar cells with 5.5% power conversion efficiency were fabricated from Cu/Sn/Zn stacks electrodeposited from liquid metal salts. These electrolytes allow metal deposition rates one order of magnitude higher than those of other deposition methods.

Tuning the gallium content of metal precursors for Cu(In,Ga)Se2 thin film solar cells by electrodeposition from a deep eutectic solvent.

Controlling the Ga incorporation of Cu-In-Ga metal precursors for Cu(In,Ga)Se2 (CIGS) solar cells is one of the main challenges for low cost electrodeposition processes, mainly due to the difficulty in electrodepositing metallic Ga from aqueous electrolytes. In this work we use the deep eutectic solvent (DES) Choline Chloride : Urea (ChCl : U - 1 : 2) to efficiently codeposit In-Ga on Cu and Mo electrodes. We control the Ga/(Ga+In) (Ga/III) ratio of the films via the mass fluxes. The electrochemical behavior of ChCl : U containing GaCl3 and InCl3 is studied by rotating disk electrode cyclic voltammetry (CV) on Mo and Cu electrodes. CV revealed on both Mo and Cu electrodes that the electrochemical behavior of the ChCl : U-GaCl3-InCl3 system is the superposition of the individual In and Ga electrochemistry. On a Cu electrode the morphology, crystal structure and element distribution of the deposits were a function of the Ga/III ratio. We demonstrate the precise control of Ga incorporation over a large composition range from 0.1 ≤ Ga/III ≤ 0.9 and proved that ED from DES is a straightforward, robust and efficient process. First solar cells based on Mo/Cu/In-Ga metal stacks achieved efficiencies as high as 7.9% with a Voc of 520 mV.

Thermodynamic aspects of the synthesis of thin-film materials for solar cells.

A simple and useful thermodynamic approach to the prediction of reactions taking place during thermal treatment of layers of multinary semiconductor compounds on different substrates has been developed. The method, which uses the extensive information for the possible binary compounds to assess the stability of multinary phases, is illustrated with the examples of Cu(In,Ga)Se(2) and Cu(2)ZnSnSe(4) as well as other less-studied ternary and quaternary semiconductors that have the potential for use as absorbers in photovoltaic devices.

The consequences of kesterite equilibria for efficient solar cells.

Copper-zinc-tin-chalcogenide kesterites, Cu(2)ZnSnS(4) and Cu(2)ZnSnSe(4) (CZTS(e)) are ideal candidates for the production of thin film solar cells on large scales due to the high natural abundance of all constituents, a tunable direct band gap ranging from 1.0 to 1.5 eV, a large absorption coefficient, and demonstrated power conversion efficiencies close to 10%. However, Sn losses through desorption of SnS(e) from CZTS(e) at elevated temperatures (above 400 °C) impede the thorough control of film composition and film homogeneity. No robust and feasible fabrication process is currently available. Here we show that understanding the formation reaction of the kesterite absorber is the key to control the growth process and to drastically improve the solar cell efficiency. Furthermore, we demonstrate that this knowledge can be used to simplify the four-dimensional parameter space (spanned by the four different elements) to an easy and robust two-dimensional process. Sufficiently high partial pressures of SnS(e) and S(e) (a) prevent the decomposition reaction of the CZTS(e) at elevated temperatures and (b) introduce any missing Sn into a Sn-deficient film. This finding enables us to simplify the precursor to a film containing only Cu and Zn, whereas Sn and S(e) are introduced from the gas phase by a self-regulating process.

Controlled electrodeposition of Cu-Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells.

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.

Small-angle neutron scattering studies of an adsorbed non-ionic surfactant (C12E24) on hydrophobised silica particles in water.

Small-angle neutron scattering (SANS) studies of aqueous dispersions of Stöber silica particles (which have been hydrophobised by having 1-octadecanol grafted to their surface), carrying an adsorbed layer of the nonionic surfactant C12E24, in water, have been performed as a function of temperature. Using mixtures of D2O and H2O, the composition of the continuous phase was adjusted to have the same scattering length density as the silica particles. Hence, only the scattering from the 1-octadecanol and C12E24 layers was detected. The data have been analyzed using both a surface Guinier analysis and a two-layer structure model. It has been found that a step profile best describes the inner combined adsorbed layer (1-octadecanol grafted chains, plus the penetrating alkyl chains from the surfactant) and a semi-Gaussian profile the extended poly(ethylene oxide) outer layer. Both analyses demonstrated that the combined surface layer contracted with increasing temperature.

Adsorption of non-ionic surfactants on hydrophobic silica particles and the stability of the corresponding aqueous dispersions.

The temperature stability of aqueous dispersions of hydrophobic monodisperse silica particles stabilized with nonionic surfactants has been investigated. Adsorption isotherms in conjunction with surface tension measurements showed that the surfactant formed a monolayer on the surface of the particles, where the adsorbed amount depended on the molecular weight of the ethylene oxide headgroup. The temperature stability of these dispersions has been measured by a standard turbidimetric technique and visual observations in terms of their critical flocculation temperature (CFT). Parameters controlling the CFT of the individual dispersions stabilized with a monolayer of surfactant include the thickness of the steric layer, the particle size, and the volume fraction of the particles. Calculations show that the van der Waals attraction between the particles with adsorbed polymer layers increases as the temperature of the dispersion increases, and this largely accounts for the observed CFT behavior.