Nicholas C. Strandwitz

Interfacial band-edge energetics for solar fuels production

Photoelectrochemical (PEC) water splitting has received growing attention as a potential pathway to replace fossil fuels and produce a clean, renewable, and sustainable source of fuel. To achieve overall water splitting and the associated production of solar fuels, complex devices are needed to efficiently capture light from the sun, separate photogenerated charges, and catalyze reduction and oxidation reactions. To date, the highest performing solar fuels devices rely on multi-component systems, which introduce interfaces that can be associated with further performance loss due to thermodynamic and kinetic considerations. In this review, we identify several of the most important interfaces used in PEC water splitting, summarize methods to characterize them, and highlight approaches to mitigating associated loss mechanisms.

Increased efficiency in multijunction solar cells through the incorporation of semimetallic ErAs nanoparticles into the tunnel junction

We report the molecular beam epitaxy growth of Al0.3Ga0.7As∕GaAs multijunction solar cells with epitaxial, semimetallic ErAs nanoparticles at the interface of the tunnel junction. The states provided by these nanoparticles reduce the bias required to pass current through the tunnel junction by three orders of magnitude, and therefore drastically reduce the voltage losses in the tunnel junction. We have measured open-circuit voltages which are 97% of the sum of the constituent cells, which result in nearly double the efficiency of our multijunction cell with a conventional tunnel junction.

In Situ Photopolymerization of Pyrrole in Mesoporous TiO2

We examined mesoporous TiO(2) as a photosensitizer and template for creating hybrid TiO(2)-polypyrrole materials. Optical excitation of mesoporous TiO(2) was used to generate the electronic potential necessary for the oxidation and polymerization of the pyrrole monomer. The photopolymerization process was monitored by the quartz crystal microbalance, nitrogen sorption, and thermogravimetric techniques. In situ generation of polypyrrole was observed to be self-limiting after approximately 20-30% filling of the mesoporous TiO(2) network. In situ generation of a complementary phase by means of charge transfer from an active host phase represents an alternative means of assembling hybrid inorganic-organic materials with potential applications ranging from electrocatalysis to photovoltaics.

Photoelectrochemical Behavior of n‑Type Si(111) Electrodes Coated With a Single Layer of Graphene

The behavior of graphene-coated n-type Si(111) photoanodes was compared to the behavior of H-terminated n-type Si(111) photoanodes in contact with aqueous K3[Fe(CN)6]/K4[Fe(CN)6] as well as in contact with a series of outer-sphere, one-electron redox couples in nonaqueous electrolytes. The n-Si/Graphene electrodes exhibited stable short-circuit photocurrent densities of over 10 mA cm(-2) for >1000 s of continuous operation in aqueous electrolytes, whereas n-Si-H electrodes yielded a nearly complete decay of the current density within ~100 s. The values of the open-circuit photovoltages and the flat-band potentials of the Si were a function of both the Fermi level of the graphene and the electrochemical potential of the electrolyte solution, indicating that the n-Si/Graphene did not form a buried junction with respect to the solution contact.

Blood Clot Initiation by Mesocellular Foams : Dependence on Nanopore Size and Enzyme Immobilization

Porous silica materials are attractive for hemorrhage control because of their blood clot promoting surface chemistry, the wide variety of surface topologies and porous structures that can be created, and the potential ability to achieve high loading of therapeutic proteins within the silica support. We show that silica cell-window size variation in the nanometers to tens of nanometers range greatly affects the rate at which blood clots are formed in human plasma, indicating that window sizes in this size range directly impact the accessibility and diffusion of clotting-promoting proteins to and from the interior surfaces and pore volume of mesocellular foams (MCFs). These studies point toward a critical window size at which the clotting speed is minimized and serve as a model for the design of more effective wound-dressing materials. We demonstrate that the clotting times of plasma exposed to MCF materials are dramatically reduced by immobilizing thrombin in the pores of the MCF, validating the utility of enzyme-immobilized mesoporous silicas in biomedical applications.

One- and Two-Photon Induced Polymerization of Methylmethacrylate Using Colloidal CdS Semiconductor Quantum Dots

The development of one- and two-photon induced polymerization using CdS semiconductor quantum dots (QDs) and amine co-initiators to promote radical generation and subsequent polymerization is presented. Two-photon absorption (TPA) cross-section measurements, linear absorption, and transmission electron microscopy are used to characterize the QDs. The effectiveness of the co-initiators in increasing the efficiency of photopolymerization (polymer chains formed per excitation) is examined. Triethylamine was observed to be most effective, yielding quantum efficiencies of initiation of >5%. The interactions between the co-initiators and QDs are investigated with steady-state photoluminescence and infrared spectroscopies. Possible initiation mechanisms are discussed and supported by electrochemical data. Making use of the surface chemistry developed here and the large QD TPA cross-sections, two-photon induced polymerization is demonstrated. The large TPA cross-sections coupled with modest quantum efficiencies for initiation reveal the unique potential of molecularly passivated QDs as efficient two-photon photosensitizers for polymerization.

Photoanodic behavior of vapor-liquid-solid–grown, lightly doped, crystalline Si microwire arrays

Arrays of n-Si microwires have to date exhibited low efficiencies when measured as photoanodes in contact with a 1-1′-dimethylferrocene (Me2Fc+/0)–CH3OH solution. Using high-purity Au or Cu catalysts, arrays of crystalline Si microwires were grown by a vapor-liquid-solid process without dopants, which produced wires with electronically active dopant concentrations of 1 × 1013 cm−3. When measured as photoanodes in contact with a Me2Fc+/0–CH3OH solution, the lightly doped Si microwire arrays exhibited greatly increased fill factors and efficiencies as compared to n-Si microwires grown previously with a lower purity Au catalyst. In particular, the Cu-catalyzed Si microwire array photoanodes exhibited open-circuit voltages of ∼0.44 V, carrier-collection efficiencies exceeding ∼0.75, and an energy-conversion efficiency of 1.4% under simulated air mass 1.5 G illumination. Lightly doped Cu-catalyzed Si microwire array photoanodes have thus demonstrated performance that is comparable to that of optimally doped p-type Si microwire array photocathodes in photoelectrochemical cells.

Chemical Stability of Titania and Alumina Thin Films Formed by Atomic Layer Deposition.

Thin films formed by atomic layer deposition (ALD) are being examined for a variety of chemical protection and diffusion barrier applications, yet their stability in various fluid environments is not well characterized. The chemical stability of titania and alumina thin films in air, 18 MΩ water, 1 M KCl, 1 M HNO3, 1 M H2SO4, 1 M HCl, 1 M KOH, and mercury was studied. Films were deposited at 150 °C using trimethylaluminum-H2O and tetrakis(dimethylamido)titanium-H2O chemistries for alumina and titania, respectively. A subset of samples were heated to 450 and 900 °C in inert atmosphere. Films were examined using spectroscopic ellipsometry, atomic force microscopy, optical microscopy, scanning electron microscopy, and X-ray diffraction. Notably, alumina samples were found to be unstable in pure water, acid, and basic environments in the as-synthesized state and after 450 °C thermal treatment. In pure water, a dissolution-precipitation mechanism is hypothesized to cause surface roughening. The stability of alumina films was greatly enhanced after annealing at 900 °C in acidic and basic solutions. Titania films were found to be stable in acid after annealing at or above 450 °C. All films showed a composition-independent increase in measured thickness when immersed in mercury. These results provide stability-processing relationships that are important for controlled etching and protective barrier layers.

Compositional tunability and high temperature stability of ceria–zirconia hollow spheres

Cerium oxide is a widely used catalyst support due to favorable oxygen storage and release properties. The present investigation was undertaken to improve the thermal stability of hollow ceria shells by incorporation of zirconium. Hollow ceria spheres were doped with zirconium in the range of 1–13 atomic percent by a solvothermal method. In situhigh-temperature XRD revealed that samples with greater than 5% zirconium were significantly more resistant to crystallite growth than pure ceria samples. Additionally, nitrogen adsorption porosimetry showed that doped samples retained their specific surface area to higher temperatures than undoped samples. Transmission electron microscopy was used to confirm high temperature stability (up to 1100 °C) of the hollow sphere morphology.

Use of Mixed CH3-/HC(O)CH2CH2-Si(111) Functionality to Control Interfacial Chemical and Electronic Properties During the Atomic-Layer Deposition of Ultrathin Oxides on Si(111).

Silicon surfaces terminated with a mixed monolayer containing both a propyl aldehyde functionality and methyl groups were prepared and used to control the interfacial chemical and electronic properties of Si(111) surfaces during atomic-layer deposition (ALD) of Al2O3 or MnO. Si(111) surfaces functionalized only with the aldehyde moiety exhibited surface recombination velocities, S, of 2500 ± 600 cm s(-1) whereas the mixed CH3-/HC(O)CH2CH2-Si(111) surfaces displayed S = 25 ± 7 cm s(-1). During the ALD growth of either Al2O3 or MnO, both the HC(O)CH2CH2-Si(111) and CH3-/HC(O)CH2CH2-Si(111) surfaces produced increased metal oxide deposition at low cycle number, relative to H-Si(111) or CH3-Si(111) surfaces. As detected by X-ray photoelectron spectroscopy after the ALD process, the CH3- and mixed CH3-/HC(O)CH2CH2- functionalized Si(111) surfaces exhibited less interfacial SiOx than was observed for ALD of metal oxides on H-Si(111) substrates.