Probing the Relative Photoinjection Yields of Monomer and Aggregated Dyes into ZnO Crystals.

Cyanine dyes, often used in dye-sensitized solar cells (DSSCs), form a range of molecular species from monomers to large H and J aggregates in both solution and when adsorbed at a photoelectrode surface. To determine the relative capability of the different dye species to inject photoexcited electrons into a wideband gap oxide semiconductor, sensitization at a single-crystal zinc oxide surface was studied by simultaneous attenuated reflection (ATR) ultraviolet-visible (UV-vis) absorption and photocurrent spectroscopy measurements. ATR measurements enable identification of the dye species populating the surface with simultaneous photocurrent spectroscopy to identify the contribution of the various dye forms to photocurrent signal. We study the dye 2,2'-carboxymethylthiodicarbocyanine bromide that is particularly prone to aggregation both in solution and at the surface of sensitized oxide semiconductors.

Preparation, applications, and digital simulation of carbon interdigitated array electrodes.

Carbon interdigitated array (IDA) electrodes with features sizes down to 1.2 µm were fabricated by controlled pyrolysis of patterned photoresist. Cyclic voltammetry of reversible redox species produced the expected steady-state currents. The collection efficiency depends on the IDA electrode spacing, which ranged from around 2.7 to 16.5 µm, with the smaller dimensions achieving higher collection efficiencies of up to 98%. The signal amplification because of redox cycling makes it possible to detect species at relatively low concentrations (10(-5) molar) and the small spacing allows detection of transient electrogenerated species with much shorter lifetimes (submillisecond). Digital simulation software that accounts for both the width and height of electrode elements as well as the electrode spacing was developed to model the IDA electrode response. The simulations are in quantitative agreement with experimental data for both a simple fast one electron redox reaction and an electron transfer with a following chemical reaction at the IDAs with larger gaps whereas currents measured for the smallest IDA electrodes, that were larger than the simulated currents, are attributed to convection from induced charge electrokinetic flow.

Sensitization of ZnO single crystal electrodes with CdSe quantum dots.

CdSe quantum dots (QDs) were attached to single crystal ZnO(0001) and ZnO(1100) substrates using capping groups, 4-mercaptobenzoic acid, 2-mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 11-mercaptoundecanoic acid, as bifunctional linker molecules. The spectral response and photosensitization yields of the adsorbed QDs were studied with photocurrent spectroscopy. Atomic force microscopy (AFM) was used to verify the surface structure of the ZnO crystals and to examine the coverage and arrangement of the QDs on the single crystal surface. The inner-sphere aqueous redox couple Sx(2-)/S(2-), often used as a regenerator for chalcogenide-based QDs, as well as outer-sphere redox couples such as ferrocene, were able to regenerate the photoexcited CdSe QDs and suppress their photocorrosion. Differences in the binding of the QDs to different ZnO crystal faces are also reported.

Simultaneous measurement of absorbance and quantum yields for photocurrent generation at dye-sensitized single-crystal ZnO electrodes.

It is often assumed that the photoresponse or incident photon-to-current conversion efficiency (IPCE) spectrum of a sensitized semiconductor electrode is directly correlated with the amount of sensitizing species present on the semiconductor surface. In reality, the various forms of adsorbed species, such as dye aggregates or dye molecules bound to different adsorption sites, such as terrace edges, can have significantly different electron injection yields and carrier recombination rates. To provide information about the amounts of the various adsorbed dye species and their effectiveness as sensitizers, we report the simultaneous acquisition of IPCE and attenuated total reflectance (ATR) UV-vis spectra for a thiacyanine dye bound to a single-crystal oxide semiconductor electrode surface. ZnO single crystals were fashioned into internal-reflection elements to act both as a waveguide for the internally reflected probe beam for UV-vis spectra and as the substrate for dye sensitization using dyes with distinct spectral signatures for monomers and aggregates. Strong agreement was observed between the quantum efficiency and ATR UV-vis spectra, suggesting that, under the conditions employed, both monomers and aggregates of the dye studied generate photocurrent with the same efficiency.

Influence of the aggregation of a carbazole thiophene cyanoacrylate sensitizer on sensitized photocurrents on ZnO single crystals.

Dye sensitization of zinc oxide single crystals by a carbazole thiophene cyanoacrylate (MK-2) sensitizer deposited from THF and mixtures of THF and water was investigated. AFM images show the formation of larger aggregates, with the maximum size of 20-30 nm from mixtures of THF and water, compared with 8-12 nm from pure THF. Sensitized photocurrent spectra were correlated with the morphological results from AFM imaging and indicate that aggregation in water results in less efficient sensitization of the ZnO substrate. The presence of the aggregation in solution due to water content was confirmed by absorbance and fluorescence spectroscopies.

Dye sensitization of four low index TiO2 single crystal photoelectrodes with a series of dicarboxylated cyanine dyes.

Four dicarboxylated cyanine dyes were used to sensitize single-crystal anatase (001), anatase (101), rutile (001), and rutile (100) surfaces. Incident photon to current efficiencies (IPCE) spectra and isotherms were gathered for the different combination of dyes and surfaces. The maximum coverage of the surface-bound dyes on the TiO2 crystal surfaces was determined by photochronocoulometric measurements. The IPCE spectra of the surface-bound dyes revealed that both the dye monomers and H-aggregates were both present and generated photocurrent. The relative abundance of dye monomers and H-aggregates was found to be strongly dependent on the crystallographic face used as the substrate for sensitization. The ratio of dye monomer to H-aggregate was quantified by fitting the IPCE spectra with a sum of the dye monomer and H-aggregate solution spectra. The trends in surface coverage were explained using a simple "lattice matching" model where the distance between the coordinatively unsaturated Ti binding sites on the various TiO2 crystallographic surfaces was compared with the distance between the carboxylate groups on the dyes. The rutile (100) surface had the highest coverage for all the dyes in agreement with the predictions of the lattice-matching model. Absorbed photon-to-current-efficiencies (APCEs) were calculated from the incident photon current efficiencies, the extinction coefficients and the measured surface coverages. The factors that affect the APCE values such as the relative injection yield for monomers and aggregate, the relative surface coverage values for monomers and aggregates, and semiconductor doping levels are discussed.

Controlling the electronic coupling between CdSe quantum dots and thiol capping ligands via pH and ligand selection.

Comparison of the UV-vis absorption spectra of CdSe quantum dots (QDs) capped with various mercaptocarboxylic acid capping ligands reveals that only 4-mercaptobenzoic acid (MBzA) capping ligands lower the apparent optical band gap. We propose that the delocalization of the excitons in the CdSe QDs is extended onto the ligands via electronic coupling to the π system of the 4-mercaptobenzoic acid molecules through the Cd-S bond. Furthermore, we demonstrate that the electronic coupling between the QDs and the (MBzA) thiol ligands is influenced by the strength of the Cd-S bond that can be changed by protonating the S atom.

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. We report the direct solution-phase synthesis and characterization of Cu(2)ZnSn(S(1-x)Se(x))(4) nanocrystals (0 ≤ x ≤ 1) with the aim of probing the role of Se incorporation into CZTS. Our results indicate that increasing the amount of Se increases the lattice parameters, slightly decreases the band gap, and most importantly increases the electrical conductivity of the nanocrystals without a need for annealing.

Photooxidation of chloride by oxide minerals: implications for perchlorate on Mars.

We show that highly oxidizing valence band holes, produced by ultraviolet (UV) illumination of naturally occurring semiconducting minerals, are capable of oxidizing chloride ion to perchlorate in aqueous solutions at higher rates than other known natural perchlorate production processes. Our results support an alternative to atmospheric reactions leading to the formation of high concentrations of perchlorate on Mars.

The adsorption energy and diffusion of a pentacene molecule on a gold surface.

The nature of the chemical bonding of a pentacene molecule to a gold surface is studied. The calculations are carried out using two very different methodologies, the ab inito gaussian molecular orbital method and a numerical atomic orbital method, developed from the well tested SIESTA approach. Using the GAUSSIAN 09 package, we employ both local density B3LYP, and long-range correlated functionals CAM-B3LYP, ωB97, and ωB97X. For comparison, we also calculate the adsorption energy using the ATOMISTIX TOOLKIT with the revised PBE functional. Within computational and experimental errors we find that the best description of the binding energies can be obtained from GAUSSIAN calculations using long-range ωB97 and ωB97X exchange functionals. Thus the nature of chemical bonding of a pentacene to gold is a van der Waals type. To understand the large variation in the geometries computed by different methods, we calculate energy profiles in both X- and Y-directions. The energy barriers appear to be very small and comparable with the value of room temperature. Thus a pentacene molecule moves on a gold surface with almost no friction at room temperatures. An estimation of the work function is often obtained from a simple electrostatic approach. We test this estimation and find that this approach cannot be used because it significantly underestimates the work function. This investigation gives insights into the structure and bonding of pentacene to a gold surface and provides ideas for the improvement of methodologies for computing the properties of van der Waals adsorbates.

CdSe/ZnS core/shell quantum dot sensitization of low index TiO(2) single crystal surfaces.

Quantum dots (QDs) are actively explored as alternative sensitizers to inorganic complexes in sensitized solar cells (SSC) due to their interesting physical, optical, and electronic properties. It is thought that the inorganic nature of QDs should provide enhanced stability over the entirely organic or inorganic complex dyes, yet the long-term stability of laboratory QD-SSC devices has not been investigated in detail. A general approach to synthesize high stability QDs involves coating the core material with a wide band gap inorganic shell material (type-I CS QD). However, the electronic structure of the resulting core/shell (CS) structure has potential barriers for both electron and hole transfer, suggesting inefficient charge carrier separation for type-I CS QDs. Herein we demonstrate that type-I CdSe/ZnS CS QDs can effectively sensitize single crystal TiO(2) electrodes and continue to operate in a regenerative mode in an aerated iodide electrolyte for more than 20 h. Core CdSe QDs degrade rapidly in the same electrolyte presumably due to CdI(2) formation. The possibility of exploring new core/shell nanomaterials in a variety of electrolyte/mediator combinations may result in more efficient and stable QD-SSCs.

Dye sensitization of single crystal semiconductor electrodes.

Even though investigations of dye-sensitized nanocrystalline semiconductors in solar cells has dominated research on dye-sensitized semiconductors over the past two decades, single crystal electrodes represent far simpler model systems for studying the sensitization process with a continuing train of studies dating back more than 40 years. Even today single crystal surfaces prove to be more controlled experimental models for the study of dye-sensitized semiconductors than the nanocrystalline substrates. This Account analyzes the scientific advances in the model sensitized single crystal systems that preceded the introduction of nanocrystalline semiconductor electrodes. It then follows the single crystal research to the present, illustrating both their striking simplicity of use and clarity of interpretation relative to nanocrystalline electrodes. Researchers have employed many electrochemical, photochemical, and scanning probe techniques for studying monolayer quantities of sensitizing dyes at specific crystallographic faces of different semiconductors. These methods include photochronocoulometry, electronic spectroscopy, and flash photolysis of dyes at potential-controlled semiconductor electrodes and the use of total internal reflection methods. In addition, we describe the preparation of surfaces of single crystal SnS(2) and TiO(2) electrodes to serve as reproducible model systems for charge separation at dye-sensitized solar cells. This process involves cleaving the SnS(2) electrodes and a photoelectrochemical surface treatment for TiO(2) that produces clean surfaces for sensitization (as verified by AFM) resulting in near unity yields for electron transfer from the molecular excited dyes into the conduction band. In recent experiments with ruthenium complexes at TiO(2) and with carboxylated cyanine dyes, we demonstrate the promise of this simple model for understanding dye-sensitized solar cells. In each of these systems, we can observe and analyze the complex photochemistry in a quantitative manner. Molecules of the well-known N3 ruthenium complex attach to four different crystallographic faces of anatase and rutile TiO(2) at different rates and to a different extent. With carboxylated cyanine dye sensitizers on these surfaces, molecular aggregation on the surface is a function of molecular structure and crystallographic face. In contrast with the N3 sensitizer these organic dyes undergo a photoinduced dimerization and desorption reaction when hydroquinone regenerators are present. With both classes of sensitizers, we demonstrate a new photochronocoulometric technique that quantifies the amount of attached dye on the electrode surface. We have completed initial experiments examining quantum dot sensitization of TiO(2) crystals, which could eventually lead to sensitizers with higher stability and absorption coefficients. Although these single crystal electrode models show promise for providing insights and predictive value in understanding the sensitization process, more sophisticated models will be needed to fully understand the charge transfer from the localized electronic states of the sensitizer to the extended states of the semiconductor.

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. The ex situ ligand exchange method, whereby MPA-capped QDs are synthesized and directly adsorbed onto bare TiO(2) single crystals, resulted in both reproducible sensitized photocurrents and surface coverages that are verified with atomic force microscopy (AFM). Purification of the nanocrystals and adjustment of the pH of the sensitization solution to >10.2 was found to prevent QD agglomeration and takes advantage of the dual chemical functionality of MPA to directly link the QDs to the TiO(2) surface. The spectral response of the incident photon to current efficiencies of CdSe QDs was directly compared to the commonly used sensitizer cis-di(thiocyanato)-bis(4,4;-dicarboxy-2,2'-bipyridine)ruthenium(II) (N3) on the same single crystals.

Photochronocoulometric measurement of the coverage of surface-bound dyes on titanium dioxide crystal surfaces.

Atomically flat terraced single-crystal anatase and rutile surfaces can be prepared allowing for the reproducible adsorption of covalently attached sensitizing dyes. Once reproducible surfaces and dye coverages are achieved, a photochronocoulometric technique is developed to measure the surface coverage of the dyes, an important parameter in determining the efficiency of sensitization. The surface-bound dyes are irreversibly oxidized by exposure to a light pulse with the n-type oxide semiconductor electrode held in depletion. A double-exponential decay of the subsequent photocurrent is then measured, where the integration of the faster decay is associated with the adsorbed dye coverage and the second much slower decay is attributed to trace regenerators, including water, in the nonaqueous electrolyte. The ruthenium-based N3 dye shows the expected linear dependence of the rate constant on light intensity whereas a dicarboxylated thiacyanine dye shows a square root dependence of its photooxidation rate on light intensity. The sublinear response of the thiacyanine dye is discussed in terms of the more complex surface chemistry that is known for this family of sensitizing dyes.

Photosensitization of ZnO Crystals with Iodide-Capped PbSe Quantum Dots.

Lead selenide (PbSe) quantum dots (QDs) are an attractive material for application in photovoltaic devices due to the ability to tune their band gap, efficient multiple exciton generation, and high extinction coefficients. However, PbSe QDs are quite unstable to oxidation in air. Recently there have been multiple studies detailing postsynthetic halide treatments to stabilize lead chalcogenide QDs. We exploit iodide-stabilized PbSe QDs in a model QD-sensitized solar cell configuration where zinc oxide (ZnO) single crystals are sensitized using cysteine as a bifunctional linker molecule. Sensitized photocurrents stable for >1 h can be measured in aqueous KI electrolyte that is usually corrosive to QDs under illumination. The spectral response of the sensitization extended out to 1700 nm, the farthest into the infrared yet observed. Hints of the existence of multiple exciton generation and collection as photocurrent, as would be expected in this system, are speculated and discussed.

Physical Models for Charge Transfer at Single Crystal Oxide Semiconductor Surfaces as Revealed by the Doping Density Dependence of the Collection Efficiency of Dye Sensitized Photocurrents.

The doping density dependence of photocurrents has been experimentally measured at single crystal rutile TiO2 electrodes sensitized with the N3 chromophore and a trimethine dye. As the doping density of the electrodes was varied from 10(15) to 10(20) cm(-3), three different regimes of behavior were observed for the magnitude and shape of the dye sensitized current-voltage curves. Low-doped crystals produced current-voltage curves with a slow rise of photocurrent with potential. At intermediate doping levels, Schottky barrier behavior was observed producing a photocurrent plateau at electrode bias in the depletion region. At highly doped electrodes, tunneling currents played a significant role especially in the recombination processes. These different forms of the current-voltage curves could be fit to an Onsager-based model for charge collection at a semiconductor electrode. The fitting revealed the role of the various physical parameters that govern photoinduced charge collection in sensitized systems.

Contrasting electrogenerated chemiluminescence for a dissolved and surface-attached carbazole thiophene cyanoacrylate dye.

The electrogenerated chemiluminescence (ECL) of a carbazole thiophene cyanoacrylate dye ((2-cyano-3-[5"'-(9-ethyl-9H-carbazol-3-yl)-3',3",3"',4-tetra-n-hexyl-[2,2',5',2",5",2"']-quarter-thiophenyl-5yl]acrylate) = MK-2) has been investigated in solution, where the maximum ECL wavelength occurs at 640 nm, and in a thin film on an ITO surface, where the ECL is substantially red-shifted to 730 nm. The ECL intensity for the solution annihilation reaction is relatively weak, whereas a much higher ECL intensity is measured with oxalate as a co-reactant. This result is attributed to the two Nernstian reversible oxidation waves of the thiophene moiety of MK-2, whereas the reduction is stabilized by the unblocked carbazole and cyanoacrylate groups.

Templated homoepitaxial growth with atomic layer deposition of single-crystal anatase (101) and rutile (110) TiO2.

Homoepitaxial growth of highly ordered and pure layers of rutile on rutile crystal substrates and anatase on anatase crystal substrates using atomic layer deposition (ALD) is reported. The epilayers grow in a layer-by-layer fashion at low deposition temperatures but are still not well ordered on rutile. Subsequent annealing at higher temperatures produces highly ordered, terraced rutile surfaces that in many cases have fewer electrically active defects than the substrate crystal. The anatase epitaxial layers, grown at 250 °C, have much fewer electrically active defects than the rather impure bulk crystals. Annealing the epilayers at higher temperatures increased band gap photocurrents in both anatase and rutile.

Combinatorial discovery through a distributed outreach program: investigation of the photoelectrolysis activity of p-type Fe, Cr, Al oxides.

We report the identification of a semiconducting p-type oxide containing iron, aluminum, and chromium (Fe2-x-yCrxAlyO3) with previously unreported photoelectrolysis activity that was discovered by an undergraduate scientist participating in the Solar Hydrogen Activity research Kit (SHArK) program. The SHArK program is a distributed combinatorial science outreach program designed to provide a simple and inexpensive way for high school and undergraduate students to participate in the search for metal oxide materials that are active for the photoelectrolysis of water. The identified Fe2-x-yCrxAlyO3 photoelectrolysis material possesses many properties that make it a promising candidate for further optimization for potential application in a photoelectrolysis device. In addition to being composed of earth abundant elements, the FeCrAl oxide material has a band gap of 1.8 eV. Current-potential measurements for Fe2-x-yCrxAlyO3 showed an open circuit photovoltage of nearly 1 V; however, the absorbed photon conversion efficiency for hydrogen evolution was low (2.4 × 10(-4) at 530 nm) albeit without any deposited hydrogen evolution catalyst. X-ray diffraction of the pyrolyzed polycrystalline thin Fe2-x-yCrxAlyO3 film on fluorine-doped tin oxide substrates shows a hexagonal phase (hematite structure) and scanning electron microscope images show morphology consisting of small crystallites.

Combinatorial search for improved metal oxide oxygen evolution electrocatalysts in acidic electrolytes.

A library of electrocatalysts for water electrolysis under acidic conditions was created by ink jet printing metal oxide precursors followed by pyrolysis in air to produce mixed metal oxides. The compositions were then screened in acidic electrolytes using a pH sensitive fluorescence indicator that became fluorescent due to the pH change at the electrode surface because of the release of protons from water oxidation. The most promising materials were further characterized by measuring polarization curves and Tafel slopes as anodes for water oxidation. Mixed metal oxides that perform better than the iridium oxide standard were identified.