Sebastian Siol

Band Alignment Engineering at Cu2O/ZnO Heterointerfaces

Energy band alignments at heterointerfaces play a crucial role in defining the functionality of semiconductor devices, yet the search for material combinations with suitable band alignments remains a challenge for numerous applications. In this work, we demonstrate how changes in deposition conditions can dramatically influence the functional properties of an interface, even within the same material system. The energy band alignment at the heterointerface between Cu2O and ZnO was studied using photoelectron spectroscopy with stepwise deposition of ZnO onto Cu2O and vice versa. A large variation of energy band alignment depending on the deposition conditions of the substrate and the film is observed, with valence band offsets in the range ΔEVB = 1.45-2.7 eV. The variation of band alignment is accompanied by the occurrence or absence of band bending in either material. It can therefore be ascribed to a pinning of the Fermi level in ZnO and Cu2O, which can be traced back to oxygen vacancies in ZnO and to metallic precipitates in Cu2O. The intrinsic valence band offset for the interface, which is not modified by Fermi level pinning, is derived as ΔEVB ≈ 1.5 eV, being favorable for solar cell applications.

Combinatorial Reactive Sputtering of In2S3 as an Alternative Contact Layer for Thin Film Solar Cells

High-throughput computational and experimental techniques have been used in the past to accelerate the discovery of new promising solar cell materials. An important part of the development of novel thin film solar cell technologies, that is still considered a bottleneck for both theory and experiment, is the search for alternative interfacial contact (buffer) layers. The research and development of contact materials is difficult due to the inherent complexity that arises from its interactions at the interface with the absorber. A promising alternative to the commonly used CdS buffer layer in thin film solar cells that contain absorbers with lower electron affinity can be found in β-In2S3. However, the synthesis conditions for the sputter deposition of this material are not well-established. Here, In2S3 is investigated as a solar cell contact material utilizing a high-throughput combinatorial screening of the temperature-flux parameter space, followed by a number of spatially resolved characterization techniques. It is demonstrated that, by tuning the sulfur partial pressure, phase pure β-In2S3 could be deposited using a broad range of substrate temperatures between 500 °C and ambient temperature. Combinatorial photovoltaic device libraries with Al/ZnO/In2S3/Cu2ZnSnS4/Mo/SiO2 structure were built at optimal processing conditions to investigate the feasibility of the sputtered In2S3 buffer layers and of an accelerated optimization of the device structure. The performance of the resulting In2S3/Cu2ZnSnS4 photovoltaic devices is on par with CdS/Cu2ZnSnS4 reference solar cells with similar values for short circuit currents and open circuit voltages, despite the overall quite low efficiency of the devices (∼2%). Overall, these results demonstrate how a high-throughput experimental approach can be used to accelerate the development of contact materials and facilitate the optimization of thin film solar cell devices.

PVD of copper sulfide (Cu2S) for PIN-structured solar cells

Thin layers of chalcocite (Cu2S) have been deposited via physical vapour deposition using various pre- and post-treatment parameters. The electrical and morphological properties have been investigated by in situ XPS, SEM and XRD measurements. Calibrated photoluminescence experiments were performed to investigate the materials suitability as an absorber layer in thin-film solar cells. Measurements of annealed Cu2S layers on glass without any surface passivation showed an optical band gap of 1.25 eV as well as a splitting of the quasi-Fermi levels of 710 meV. This value exceeds the highest reported open-circuit voltage for Cu2S-based devices so far, which leads to the assumption that Cu2S has not been brought to its full potential yet. The band alignments for ZnO/Cu2S as well as Cu2S/Cu2O interfaces have been determined using in situ XPS interface experiments to suggest a novel device structure according to the favourable PIN-layout. First devices have been built, but show no efficiency due to shunting caused by the inferior morphology of the absorber layers.

Novel phase diagram behavior and materials design in heterostructural semiconductor alloys

Theoretically predicted metastable phases are realized in thin-film synthesis of Mn1−xZnxO and Sn1−xCaxS alloys. Structure and composition control the behavior of materials. Isostructural alloying is historically an extremely successful approach for tuning materials properties, but it is often limited by binodal and spinodal decomposition, which correspond to the thermodynamic solubility limit and the stability against composition fluctuations, respectively. We show that heterostructural alloys can exhibit a markedly increased range of metastable alloy compositions between the binodal and spinodal lines, thereby opening up a vast phase space for novel homogeneous single-phase alloys. We distinguish two types of heterostructural alloys, that is, those between commensurate and incommensurate phases. Because of the structural transition around the critical composition, the properties change in a highly nonlinear or even discontinuous fashion, providing a mechanism for materials design that does not exist in conventional isostructural alloys. The novel phase diagram behavior follows from standard alloy models using mixing enthalpies from first-principles calculations. Thin-film deposition demonstrates the viability of the synthesis of these metastable single-phase domains and validates the computationally predicted phase separation mechanism above the upper temperature bound of the nonequilibrium single-phase region.

Combinatorial chemical bath deposition of CdS contacts for chalcogenide photovoltaics

Contact layers play an important role in thin film solar cells, but new material development and optimization of its thickness is usually a long and tedious process. A high-throughput experimental approach has been used to accelerate the rate of research in photovoltaic (PV) light absorbers and transparent conductive electrodes, however the combinatorial research on contact layers is less common. Here, we report on the chemical bath deposition (CBD) of CdS thin films by combinatorial dip coating technique and apply these contact layers to Cu(In,Ga)Se2 (CIGSe) and Cu2ZnSnSe4 (CZTSe) light absorbers in PV devices. Combinatorial thickness steps of CdS thin films were achieved by removal of the substrate from the chemical bath, at regular intervals of time, and in equal distance increments. The trends in the photoconversion efficiency and in the spectral response of the PV devices as a function of thickness of CdS contacts were explained with the help of optical and morphological characterization of the CdS thin films. The maximum PV efficiency achieved for the combinatorial dip-coating CBD was similar to that for the PV devices processed using conventional CBD. The results of this study lead to the conclusion that combinatorial dip-coating can be used to accelerate the optimization of PV device performance of CdS and other candidate contact layers for a wide range of emerging absorbers.

Using heterostructural alloying to tune the structure and properties of the thermoelectric Sn1−xCaxSe

We grow and kinetically stabilize the isotropic rocksalt phase of SnSe thin films by alloying SnSe with CaSe. Thin polycrystalline films of the metastable heterostructural alloy Sn1−xCaxSe are synthesized by pulsed laser deposition on amorphous SiO2 over the entire composition range 0 < x < 1. We observe the theoretically-predicted, composition-driven change from a layered, orthorhombic structure to an isotropic, cubic structure near x = 0.18, in reasonable agreement with the theoretical value of x = 0.13 calculated from first principles. The optical band gap is highly non-linear in x and the trend agrees with theory predictions. Compared to the layered end-member SnSe, the isotropic alloy near the orthorhombic-to-rocksalt transition has a p-type electrical resistivity three orders of magnitude lower, and a thermoelectric power factor at least ten times larger. Thus manipulation of the structure of a functional material like SnSe via alloying may provide a new path to enhanced functionality, in this case, improved thermoelectric performance.

Highly conductive grain boundaries in copper oxide thin films

High conductivity in the off-state and low field-effect mobility compared to bulk properties is widely observed in the p-type thin-film transistors of Cu2O, especially when processed at moderate temperature. This work presents results from in situ conductance measurements at thicknesses from sub-nm to around 250 nm with parallel X-ray photoelectron spectroscopy. An enhanced conductivity at low thickness is explained by the occurrence of Cu(II), which is segregated in the grain boundary and locally causes a conductivity similar to CuO, although the surface of the thick film has Cu2O stoichiometry. Since grains grow with an increasing film thickness, the effect of an apparent oxygen excess is most pronounced in vicinity to the substrate interface. Electrical properties of Cu2O grains are at least partially short-circuited by this effect. The study focuses on properties inherent to copper oxide, although interface effects cannot be ruled out. This non-destructive, bottom-up analysis reveals phenomena which are commonly not observable after device fabrication, but clearly dominate electrical properties of polycrystalline thin films.

Detailed photoluminescence studies of thin film Cu2S for determination of quasi-Fermi level splitting and defect levels

We have studied chalcocite (Cu2S) layers prepared by physical vapor deposition with varying deposition parameters by calibrated spectral photoluminescence (PL) and by confocal PL with lateral resolution of Δ x≈0.9 μm. Calibrated PL experiments as a function of temperature T and excitation fluxes were performed to obtain the absolute PL-yield and to calculate the splitting of the quasi-Fermi levels (QFLs) μ=Ef,n−Ef,p at an excitation flux equivalent to the AM 1.5 spectrum and the absorption coefficient α(ℏω), both in the temperature range of 20 K≤T≤400 K. The PL-spectra reveal two peaks at E#1=1.17 eV and E#2=1.3 eV. The samples show a QFL-splitting of μ>700 meV associated with a pseudo band gap of Eg=1.25 eV. The high-energy peak shows an unexpected temperature behavior, namely, an increase of PL-yield with rising temperature at variance with the behavior of QFL-splitting that decreases with rising T. Our observations indicate that, contrary to common believe, it is not the PL-yield, but rather the QFL-sp...

Solubility limits in quaternary SnTe-based alloys

The controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn1−yMnyTe1−xSex phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn1−yMnyTe1−xSex indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.

Photocorrosion-resistant Sb2Se3 photocathodes with earth abundant MoSx hydrogen evolution catalyst

The poor stability of high efficiency photoabsorber materials in aqueous media is one factor holding back the realization of photoelectrochemical (PEC) water splitting for large scale, practical solar fuels generation. Here, we demonstrate that highly efficient thin film Sb2Se3 – fabricated by a simple, low temperature selenization of electrodeposited Sb – is intrinsically stable towards photocorrosion in strongly acidic media (1 M H2SO4). Coupling with a photoelectrodeposited MoSx hydrogen evolution catalyst gives high photocurrents (5 mA cm−2 at 0 V vs. RHE) and high stability without protective layers. A low temperature sulfurization of the Sb2Se3–MoSx stack dramatically improved the onset potential, resulting in high photocurrent densities up to ∼16 mA cm−2 at 0 V vs. RHE. The simplicity with which these photocathodes are fabricated, combined with the high photocurrents and stability, make Sb2Se3 a strong candidate for scalable PEC cells.