Low-Temperature Atomic Layer Deposition of CuSbS for Thin-Film Photovoltaics.

Copper antimony sulfide (CuSbS) has been gaining traction as an earth-abundant absorber for thin-film photovoltaics given its near ideal band gap for solar energy conversion (∼1.5 eV), large absorption coefficient (>10 cm), and elemental abundance. Through careful in situ analysis of the deposition conditions, a low-temperature route to CuSbS thin films via atomic layer deposition has been developed.

Water Oxidation by Size-Selected Co Clusters Supported on Fe O.

The complexity of the water oxidation reaction makes understanding the role of individual catalytic sites critical to improving the process. Here, size-selected 27-atom cobalt clusters (Co ) deposited on hematite (Fe O ) anodes were tested for water oxidation activity. The uniformity of these anodes allows measurement of the activity of catalytic sites of well-defined nuclearity and known density.

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications.

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure γ-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase consisting of both γ- and α-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS), allow the derivation of a self-consistent reaction mechanism.

Photoexcited Carrier Dynamics of Cu2S Thin Films.

Copper sulfide is a simple binary material with promising attributes for low-cost thin film photovoltaics. However, stable Cu2S-based device efficiencies approaching 10% free from cadmium have yet to be realized. In this Letter, transient absorption spectroscopy is used to investigate the dynamics of the photoexcited state of isolated Cu2S thin films prepared by atomic layer deposition or vapor-based cation exchange of ZnS.

Atomic layer deposition of metastable β-Fe₂O₃ via isomorphic epitaxy for photoassisted water oxidation.

We report the growth and photoelectrochemical (PEC) characterization of the uncommon bibyite phase of iron(III) oxide (β-Fe2O3) epitaxially stabilized via atomic layer deposition on an conductive, transparent, and isomorphic template (Sn-doped In2O3). As a photoanode, unoptimized β-Fe2O3 ultrathin films perform similarly to their ubiquitous α-phase (hematite) counterpart, but reveal a more ideal bandgap (1.8 eV), a ∼0.

Greenlighting photoelectrochemical oxidation of water by iron oxide.

Hematite (α-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematite's modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form.

Fabrication of transparent-conducting-oxide-coated inverse opals as mesostructured architectures for electrocatalysis applications: a case study with NiO.

Highly ordered, and conductive inverse opal arrays were made with silica and subsequently coated with tin-doped indium oxide (ITO) via atomic layer deposition (ALD). We demonstrate the utility of the resulting mesostructured electrodes by further coating them with nickel oxide via ALD. The NiO-coated arrays are capable of efficiently electrochemically evolving oxygen from water.

Stabilizing Cu2S for photovoltaics one atomic layer at a time.

Stabilizing Cu2S in its ideal stoichiometric form, chalcocite, is a long-standing challenge that must be met prior to its practical use in thin-film photovoltaic (PV) devices. Significant copper deficiency, which results in degenerate p-type doping, might be avoided by limiting Cu diffusion into a readily formed surface oxide and other adjacent layers. Here, we examine the extent to which PV-relevant metal-oxide over- and underlayers may stabilize Cu2S thin films with desirable semiconducting properties.

Phase discrimination through oxidant selection in low-temperature atomic layer deposition of crystalline iron oxides.

Control over the oxidation state and crystalline phase of thin-film iron oxides was achieved by low-temperature atomic layer deposition (ALD), utilizing a novel iron precursor, bis(2,4-methylpentadienyl)iron. This low-temperature (T = 120 °C) route to conformal deposition of crystalline Fe3O4 or α-Fe2O3 thin films is determined by the choice of oxygen source selected for the second surface half-reaction. The approach employs ozone to produce fully oxidized α-Fe2O3 or a milder oxidant, H2O2, to generate the Fe(2+)/Fe(3+) spinel, Fe3O4.

Atomic layer deposition of a submonolayer catalyst for the enhanced photoelectrochemical performance of water oxidation with hematite.

Hematite photoanodes were coated with an ultrathin cobalt oxide layer by atomic layer deposition (ALD). The optimal coating-1 ALD cycle, which amounts to <1 monolayer of Co(OH)2/Co3O4-resulted in significantly enhanced photoelectrochemical water oxidation performance. A stable, 100-200 mV cathodic shift in the photocurrent onset potential was observed that is correlated to an order of magnitude reduction in the resistance to charge transfer at the Fe2O3/H2O interface.

Hematite-based photo-oxidation of water using transparent distributed current collectors.

High specific surface area transparent and conducting frameworks, fabricated by atomic layer deposition (ALD), were used as scaffolds for fabrication of equally high area, ALD-formed hematite structures for photo-oxidation of water to dioxygen. The frameworks offer high transparency to visible light and robust conductivity under harsh annealing and oxidizing conditions. Furthermore, they also make possible the spatially distributed collection of photocurrent from ultrathin coatings of hematite layers, enabling the formation of photoanodes featuring both large optical extinction and a hematite layer thickness nearly commensurate with the hole-collection distance.

Design and implementation of an integral wall-mounted quartz crystal microbalance for atomic layer deposition.

Quartz crystal microbalance (QCM) measurements have played a vital role in understanding and expediting new atomic layer deposition (ALD) processes; however, significant barriers remain to their routine use and accurate execution. In order to turn this exclusively in situ technique into a routine characterization method, an integral QCM fixture was developed. This new design is easily implemented on a variety of chemical vapor deposition (CVD) tools, allows rapid sample exchange, prevents backside deposition, and minimizes both the footprint and flow disturbance.

Compositionally tunable Cu2ZnSn(S(1-x)Se(x))4 nanocrystals: probing the effect of Se-inclusion in mixed chalcogenide thin films.

Nanocrystals of multicomponent chalcogenides, such as Cu(2)ZnSnS(4) (CZTS), are potential building blocks for low-cost thin-film photovoltaics (PVs). CZTS PV devices with modest efficiencies have been realized through postdeposition annealing at high temperatures in Se vapor. However, little is known about the precise role of Se in the CZTS system.

Photoelectrochemical characterization of nanocrystalline thin-film Cu₂ZnSnS₄ photocathodes.

Cu₂ZnSnS₄ (CZTS) nanocrystals, synthesized by a hot injection solution method, have been fabricated into thin films by dip-casting onto fluorine doped tin oxide (FTO) substrates. The photoresponse of the CZTS nanocrystal films was evaluated using absorbance measurements along with photoelectrochemical methods in aqueous electrolytes. Photoelectrochemical characterization revealed a p-type photoresponse when the films were illuminated in an aqueous Eu(3+) redox electrolyte.

Cu2Se nanoparticles with tunable electronic properties due to a controlled solid-state phase transition driven by copper oxidation and cationic conduction.

Stoichiometric copper(I) selenide nanoparticles have been synthesized using the hot injection method. The effects of air exposure on the surface composition, crystal structure, and electronic properties were monitored using X-ray photoelectron spectroscopy, X-ray diffraction, and conductivity measurements. The current-voltage response changes from semiconducting to ohmic, and within a week a 3000-fold increase in conductivity is observed under ambient conditions.

Influence of surface chemistry on the binding and electronic coupling of CdSe quantum dots to single crystal TiO2 surfaces.

Sensitization of mesoporous nanocrystalline TiO(2) solar cells with quantum confined semiconductor nanocrystals (QDs) has some advantages over organic dyes or inorganic complex sensitizers, yet the reported efficiencies of laboratory devices are not currently competitive with those of dye sensitized cells. Several methods previously utilized to bind CdSe QDs to mesoporous TiO(2) films were investigated using low index faces of both anatase and rutile TiO(2) polytypes as model systems. The in situ ligand exchange method, where 3-mercaptopropionic acid (MPA) covered TiO(2) crystal surfaces are treated with trioctylphosphine (TOP)/trioctylphosphine oxide (TOPO) (TOP/TOPO)-capped CdSe QDs, resulted in very irreproducible and usually low sensitized photocurrents.

Solution-based synthesis and characterization of Cu2ZnSnS4 nanocrystals.

Recent advances have been made in thin-film solar cells using CdTe and CuIn(1-x)Ga(x)Se(2) (CIGS) nanoparticles, which have achieved impressive efficiencies. Despite these efficiencies, CdTe and CIGS are not amenable to large-scale production because of the cost and scarcity of Te, In, and Ga. Cu(2)ZnSnS(4) (CZTS), however, is an emerging solar cell material that contains only earth-abundant elements and has a near-optimal direct band gap of 1.