B. A. Parkinson

Multiple Exciton Collection in a Sensitized Photovoltaic System

Two for One Solar cells often contain materials that absorb a broad spectrum of light above a certain frequency threshold, or band gap. Unfortunately, much of the energy contained in this light is wasted, because any balance exceeding the band gap tends to be dissipated as heat, rather than harnessed into electric current. Recent spectroscopic studies have shown that incident photons with energy several multiples of the band gap can transiently generate more than one current carrier, but the excess carriers tend to collapse before they can be diverted into the circuit. Sambur et al. (p. 63) now show that, when light-absorbing lead sulfide nanoparticles are carefully coupled to smoothly polished titanium dioxide crystalline electrodes, such excess carriers can be transferred into the circuit before collapsing. Generating more than one current carrier per absorbed photon raises prospects for improved solar-cell efficiency. Multiple exciton generation, the creation of two electron-hole pairs from one high-energy photon, is well established in bulk semiconductors, but assessments of the efficiency of this effect remain controversial in quantum-confined systems like semiconductor nanocrystals. We used a photoelectrochemical system composed of PbS nanocrystals chemically bound to TiO2 single crystals to demonstrate the collection of photocurrents with quantum yields greater than one electron per photon. The strong electronic coupling and favorable energy level alignment between PbS nanocrystals and bulk TiO2 facilitate extraction of multiple excitons more quickly than they recombine, as well as collection of hot electrons from higher quantum dot excited states. Our results have implications for increasing the efficiency of photovoltaic devices by avoiding losses resulting from the thermalization of photogenerated carriers.

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 1.45-1.65 eV and a large absorption coefficient. Here we report the direct synthesis of CZTS nanocrystals using the hot-injection method. In-depth characterization indicated that pure stoichiometric CZTS nanocrystals with an average particle size of 12.8 +/- 1.8 nm were formed. Optical measurements showed a band gap of 1.5 eV, which is optimal for a single-junction solar device.

Compositionally Tunable Cu2ZnSn(S1–xSex)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.

Energy level alignment and two-dimensional structure of pentacene on Au(111) surfaces

X-ray photoemission, ultraviolet photoemission spectroscopy (UPS), and scanning tunneling microscopy (STM) have been used to determine the energy level alignment and the molecular ordering of monolayer and submonolayer pentacene films on Au(111) in ultrahigh vacuum. Pentacene evaporated onto the van der Waals surface of SnS2 was used as a noninteracting substrate for comparison. A large interface dipole was measured for pentacene on Au(111) (0.95 eV) whereas pentacene on SnS2 showed a relatively small interface dipole (0.26 eV). The different interface dipoles are related to the different orientations of the pentacene molecules due to different pentacene substrate interaction energies. Differences in the UPS spectra also support changing molecular orientations of the two substrates. STM images of pentacene on Au(111) revealed that the molecules lay flat on the substrate and are oriented parallel to each other, forming striped structures that are commensurate with the Au(111) lattice. The pentacene coverag...

Tin Disulfide—An Emerging Layered Metal Dichalcogenide Semiconductor: Materials Properties and Device Characteristics

Layered metal dichalcogenides have attracted significant interest as a family of single- and few-layer materials that show new physics and are of interest for device applications. Here, we report a comprehensive characterization of the properties of tin disulfide (SnS2), an emerging semiconducting metal dichalcogenide, down to the monolayer limit. Using flakes exfoliated from layered bulk crystals, we establish the characteristics of single- and few-layer SnS2 in optical and atomic force microscopy, Raman spectroscopy and transmission electron microscopy. Band structure measurements in conjunction with ab initio calculations and photoluminescence spectroscopy show that SnS2 is an indirect bandgap semiconductor over the entire thickness range from bulk to single-layer. Field effect transport in SnS2 supported by SiO2/Si suggests predominant scattering by centers at the support interface. Ultrathin transistors show on-off current ratios >10(6), as well as carrier mobilities up to 230 cm(2)/(V s), minimal hysteresis, and near-ideal subthreshold swing for devices screened by a high-k (deionized water) top gate. SnS2 transistors are efficient photodetectors but, similar to other metal dichalcogenides, show a relatively slow response to pulsed irradiation, likely due to adsorbate-induced long-lived extrinsic trap states.

Enhanced photoelectrochemical solar‐energy conversion by gallium arsenide surface modification

In the n‐GaAs/Se=–Se=x–OH−/C liquid junction solar cell, modification of the semiconductor surface by incorporation of ruthenium increases both the fill factor and the open‐circuit voltage and improves the reproducibility of performance. The power conversion efficiency of the modified cell is 12% under ∼100 mW/cm2 sunlight. Surface metal atoms or ions are shown to alter GaAs cell behavior widely; Ru represents a case for which the effect on cell performance is both positive and persisting.

Effects of Cations on the Performance of the Photoanode in the n ‐ GaAs | K 2Se ‐ K 2Se2 ‐ KOH | C Semiconductor Liquid Junction Solar Cell

Cations adsorbed onto the surface of an n-GaAs photoanode have been found to increase the fill factor and open-circuit voltage of the cell, and a conversion efficiency of 12% (under AM1 solar radiation) has been attained by chemisorbing Ru(III) onto the photoanode. The action of the Ru ions on the surface density of the photoanode is explained in detail. 19 references.

Photoemission spectroscopy of LiF coated Al and Pt electrodes

Thin lithium fluoride (LiF) interlayers between the low work function electrode and the electron transport layer in organic light emitting diodes (OLED) result in improved device performance. We investigated the electronic structure of LiF coated Al and Pt electrodes by x-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS). Thin LiF films were grown in several steps onto Ar+ sputtered Al and Pt foils. After each growth step the surfaces were characterized in situ by XPS and UPS measurements. After evaluating band bending, work function and valence band offset for both samples, their band lineups were determined. Our measurements indicate that despite the insulating character of LiF in both samples, band bending is present in the LiF layer. The difference in band bending between the samples allows the conclusion that the driving force for the development of the band bending results from the contact potential between the metal and the LiF overlayer. The band bending is most...

Reduction of GaAs surface recombination velocity by chemical treatment

Chemisorbed ruthenium ions on the surface of n‐GaAs decrease the surface recombination velocity of electrons and holes from 5×105 to 3.5×104 cm/sec. It is shown that the ions, in a one‐third monolayer thickness, are confined to the surface and do not form a new junction by diffusing into the GaAs. This use of Ru appears to be the first observation of the reduction of the surface recombination velocity for GaAs by the simple chemisorption of ions.

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. The effects of CZTS stoichiometry, film thickness, and low-temperature annealing on the photocurrents from front and back illumination suggest that the minority carrier diffusion and recombination at the back contact (via reaction of photogenerated holes with Eu(2+) produced from photoreduction by minority carriers) are the main loss mechanisms in the cell. Low-temperature annealing resulted in significant increases in the photocurrents for films made from both Zn-rich and stoichiometric CZTS nanocrystals.