Showing papers by "Nathan S. Lewis published in 2008"

Photovoltaic Measurements in Single-Nanowire Silicon Solar Cells

Abstract: Single-nanowire solar cells were created by forming rectifying junctions in electrically contacted vapor-liquid-solid-grown Si nanowires. The nanowires had diameters in the range of 200 nm to 1.5 microm. Dark and light current-voltage measurements were made under simulated Air Mass 1.5 global illumination. Photovoltaic spectral response measurements were also performed. Scanning photocurrent microscopy indicated that the Si nanowire devices had minority carrier diffusion lengths of approximately 2 microm. Assuming bulk-dominated recombination, this value corresponds to a minimum carrier lifetime of approximately 15 ns, or assuming surface-dominated recombination, to a maximum surface recombination velocity of approximately 1350 cm s(-1). The methods described herein comprise a valuable platform for measuring the properties of semiconductor nanowires, and are expected to be instrumental when designing an efficient macroscopic solar cell based on arrays of such nanostructures.

A Comparison Between the Behavior of Nanorod Array and Planar Cd(Se, Te) Photoelectrodes

Abstract: Analysis of the full device generation, transport, and recombination equations has shown that nanorod junction arrays can potentially offer improved photovoltaic performance relative to planar junctions for a carrier-collection limited absorber material not characterized by an excessively high rate of depletion-region recombination. To test this hypothesis, we have characterized planar and nanorod array photoelectrodes prepared by electrodeposition of Cd(Se, Te). The photoelectrochemical behavior of each type of photoelectrode was measured in contact with a liquid electrolyte consisting of aqueous 1 M S_2^(2-)/S^(2-), 1 M NaOH. The open-circuit photovoltage, V_(oc), short-circuit current density, J_(sc), fill factor, and overall energy conversion efficiency for both types of electrodes was measured under simulated 100 mW cm^(-2), Air Mass 1.5 conditions. V_(oc), J_(sc), and overall efficiencies were lower, on average, for nanorod array Cd(Se,Te) photoelectrodes, while the fill factors of the nanorod array photoelectrodes were generally superior to those of the planar junction devices. Importantly, the spectral response of the nanorod array photoelectrodes exhibited better quantum yields for collection of near-IR photons relative to collection of high-energy photons than did the planar photoelectrodes, in agreement with predictions of the theoretical model. The effects of surface recombination and junction area for both electrode designs have also been evaluated relative to planar photoelectrode junctions, using the Cd(Se,Te) electrode as a model system for the properties of nanorod array photoelectrodes.

Repeated epitaxial growth and transfer of arrays of patterned, vertically aligned, crystalline Si wires from a single Si(111) substrate

Abstract: Multiple arrays of Si wires were sequentially grown and transferred into a flexible polymer film from a single Si(111) wafer. After growth from a patterned, oxide-coated substrate, the wires were embedded in a polymer and then mechanically separated from the substrate, preserving the array structure in the film. The wire stubs that remained were selectively etched from the Si(111) surface to regenerate the patterned substrate. Then the growth catalyst was electrodeposited into the holes in the patterned oxide. Cycling through this set of steps allowed regrowth and polymer film transfer of several wire arrays from a single Si wafer.

Secondary ion mass spectrometry of vapor-liquid-solid grown, Au-catalyzed, Si wires.

Abstract: Knowledge of the catalyst concentration within vapor-liquid-solid (VLS) grown semiconductor wires is needed in order to assess potential limits to electrical and optical device performance imposed by the VLS growth mechanism. We report herein the use of secondary ion mass spectrometry to characterize the Au catalyst concentration within individual, VLS-grown, Si wires. For Si wires grown by chemical vapor deposition from SiCl_4 at 1000 °C, an upper limit on the bulk Au concentration was observed to be 1.7 x 10^16 atoms/cm^3, similar to the thermodynamic equilibrium concentration at the growth temperature. However, a higher concentration of Au was observed on the sidewalls of the wires.

Macroporous Silicon as a Model for Silicon Wire Array Solar Cells

Abstract: Macroporous silicon samples have been investigated in photoelectrochemical cells, and their behavior has been compared to that of conventional, planar, Si/liquid junctions. The liquid electrolyte junction provided a conformal contact to the macroporous Si and allowed assessment of the trade-offs between increased surface area and decreased carrier collection distances in such systems relative to the behavior of planar semiconductor/liquid photoelectrochemical junctions. The electrolyte contained the dimethylferrocene/dimethylferrocenium redox system in methanol because this system has been shown previously to produce bulk recombination-diffusion-limited contacts at planar Si(100) electrodes under 100 mW cm-2 of simulated air mass 1.5 illumination. Introduction of a network of ∼2−3 μm diameter, ∼80 μm long pores into the Si was found to slightly reduce the short-circuit photocurrent density and the open-circuit voltage of the system, but energy-conversion efficiencies in excess of 10% were nevertheless obt...

Structures of ordered arrays of semiconductors

Abstract: A device having arrays of semiconductor structures with dimensions, ordering and orientations to provide for light absorption and charge carrier separation. The semiconductor structures are formed with relatively high aspect ratios, that is, the structures are long in the direction of received light, but have relatively small radii to facilitate efficient radial collection of carriers.

Single-nanowire Si solar cells

Abstract: Solar cells based on arrays of CVD-grown Si nano- or micro-wires are being considered as a potentially low-cost route to implementing a vertical multijunction cell design via radial p-n junctions. This geometry has been predicted to enable efficiencies competitive with planar multicrystalline Si designs, while reducing the materials and processing costs of solar cell fabrication [1]. To further assess the potential efficiency of cells based on this design, we present here experimental measurements of minority carrier diffusion lengths and surface recombination rates within nanowires via fabrication and characterization of single-wire solar cell devices. Furthermore, we consider a potential Si wire array-based solar cell design, and present device physics modeling of single-wire photovoltaic efficiency. Based on experimentally observed diffusion lengths within our wires, we model a radial junction wire solar cell capable of 17% photovoltaic energy conversion efficiency.

Near-Ideal Photodiodes from Sintered Gold Nanoparticle Films on Methyl-Terminated Si(111) Surfaces

Abstract: We report photocurrent-voltage data for improved n-Si/metal devices using CH_3-terminated n-Si(111) and Au nanoparticles (NPs). CH_3-terminated Si(111) surfaces maintain good electronic properties throughout device assembly, while the use of Au NPs as precursors to metal films circumvents the standard issues associated with interfacial reactivity of metals in Schottky barrier formation. Such devices demonstrate excellent photovoltaic properties, with photovoltages that approach the maximum values predicted for photodiodes that are limited by Si bulk diffusion/recombination processes rather than interfacial processes. These devices are compared to standard n-Si/Au devices made via thermally evaporated Au films which are well-known to be limited by junction-based recombination.

Passivation and Secondary Functionalization of Allyl-Terminated Si(111) Surfaces

Abstract: Synthesis of passivated silicon surfaces with tunable properties requires formation of a monolayer that includes a synthetically useful functional group, such as an alkene. Thus, Si(111) surfaces have been chemically and electrically passivated by attachment of an allyl monolayer. The structure of the monolayer was confirmed using infrared spectroscopy. The allyl-functionalized surface exhibited resistance to oxidation and had a low density of surface trap states. Metal-catalyzed reactions, in particular, Heck coupling and ruthenium-catalyzed olefin cross-metathesis, allowed attachment of small molecules despite the steric constraints of the dense surface-bound layer. Allyl-terminated silicon surfaces thus offer a means of attaching a variety of chemical moieties to a silicon surface through a short linking group, enabling applications in energy conversion, catalysis, and sensing.

Detection of organic vapors and NH3(g) using thin-film carbon black–metallophthalocyanine composite chemiresistors

Abstract: Thin-film chemiresistive vapor sensors have been fabricated using composites of carbon black (CB) and metallophthalocyanines. The resulting sensors exhibited large, rapid, and reversible relative differential resistance changes upon exposure to a series of test organic vapors. The individual sensor responses, and collective sensor array properties for classification of a series of test organic vapors, were comparable to those of chemiresistor arrays made from composites of conductors and insulating organic polymers. In addition to displaying resistance responses to volatile organic compounds, the CB/metallophthalocyanine composite sensors exhibited a high sensitivity towards trace levels of NH_3(g) under ambient temperature and pressure conditions. No degradation in sensor response was observed after nearly 12 h of repeated exposure to 30 parts per million of NH_3(g) in air. Chemiresistors formed from composites of CB and zinc phthalocyanines demonstrated responses that were comparable to those of commercial NH_3(g) sensors. The CB/metallophthalocyanine composites thus broaden the types of materials that can be used for this type of low-power chemiresistive gas sensing, and broaden the types of analytes that can be sensitively detected to include inorganic gases as well as organic vapors.

Radial PN junction, wire array solar cells

Abstract: Radial pn junctions are of interest in photovoltaics because of their potential to reduce the materials costs associated with cell fabrication. However, devices fabricated to date based on Au-catalyzed vapor-liquid-solid growth have suffered from low open-circuit voltages (to our knowledge the highest reports are 260 mV in the solid state and 389 mV in solid-liquid junctions). Herein we report on the potential of low-cost catalysts such as Cu and Ni to fabricate Si wire arrays with potentially higher minority-carrier lifetimes than is possible with a Au catalyst, as well as on the use of reactive ion etching to fabricate high-purity analogs to vapor-liquid-solid grown arrays.

Polymer-embedded semiconductor rod arrays

Abstract: A structure consisting of well-ordered semiconductor structures embedded in a binder material which maintains the ordering and orientation of the semiconductor structures. Methods for forming such a structure include forming the semiconductor structures on a substrate, casting a binder material onto the substrate to embed the semiconductor structures in the binder material, and separating the binder material from the substrate at the substrate. These methods provide for the retention of the orientation and order of highly ordered semiconductor structures in the separated binder material.

STRUCTURES OF AND METHODS FOR FORMING VERTICALLY ALIGNED Si WIRE ARRAYS

Abstract: A structure consisting of vertically aligned wire arrays on a Si substrate and a method for producing such wire arrays. The wire arrays are fabricated and positioned on a substrate with an orientation and density particularly adapted for conversion of received light to energy. A patterned oxide layer is used to provide for wire arrays that exhibit narrow diameter and length distribution and provide for controlled wire position.

Effect of the Presence of Iodide on the Electron Injection Dynamics of Dye-Sensitized TiO2-Based Solar Cells

Abstract: The electron injection dynamics of dye-sensitized TiO_2-based solar cells have been investigated to determine the effects of replacing the I_3^−/I^− redox system by non-redox-active supporting electrolytes. TiO-2 films were sensitized with Ru(dcbpy)_2(NCS)_2, where dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine (the “N3” dye), and placed in contact with either M(ClO_4) or M(I_3−/I−) solutions (M = Li^+ or (n-C_4H_9)_4N^+); cells that contained I_3−/I− were fully functional solar cells whose steady-state photocurrents were directly measured. In (n-C_4H_9)_4N^+-containing solutions, significant differences were observed between the measured kinetics when ClO_4^− was replaced by the redox-active I3^−/I^− system. In particular, a ps time scale loss of the metal-to-ligand charge-transfer excited-state of the N3 dye, associated with electron injection, that was observed in cells containing either LiClO_4 or [(n-C_4H_9)4N]ClO_4 was absent in fully functional solar cells that contained [(n-C_4H_9)_4N]I/I_2. These results underscore the importance of performing kinetics measurements on this class of solar cells under operational conditions if one is to obtain reliable correlations between the dynamics data and the steady-state performance metrics of the solar cell devices.

The Role of Band Bending in Affecting the Surface Recombination Velocities for Si(111) in Contact with Aqueous Acidic Electrolytes

Abstract: The role of band bending in affecting surface recombination velocity measurements has been evaluated by combining barrier height data with charge-carrier lifetime measurements for Si(111) surfaces in contact with a variety of acidic aqueous electrolytes. Charge-carrier lifetimes and thus surface recombination velocities have been measured by contactless radio frequency photoconductivity decay techniques for long bulk lifetime n-Si(111) samples in contact with 11 M (40% by weight) NH_4F(aq), buffered (pH = 5) HF(aq), 27 M (48% by weight) HF(aq), or concentrated 18 M H_2SO_4. Regardless of the sample history or surface condition, long charge-carrier lifetimes were observed for n-Si(111) surfaces in contact with 11 M NH_4F(aq) or buffered HF(aq). On the basis of previous barrier height measurements, this behavior is consistent with the formation of an electrolyte-induced surface accumulation layer that reduces the rate of steady-state surface recombination even in the presence of a significant density of surface trap sites. A straightforward evaluation of the surface trap state density from the measured surface recombination velocities, S, is thus precluded for such Si/liquid contacts. In contrast, a wide range of S values, depending on the history of the sample and the state of the surface, were observed for n-Si(111) surfaces in contact with 27 M HF(aq). These results in conjunction with previously measured barrier height data indicate that the charge-carrier lifetimes measured for n-Si(111) in contact with 27 M HF(aq) can be directly correlated with the surface condition and the effective surface-state trap density. These conclusions were confirmed by measurements of the apparent S values of n-Si(111) surfaces in contact with various solutions in the presence of the known deep trap, Cu. For Si(111)/HF(aq) contacts, very high (≥920 ± 270 cm s^(-1)) surface recombination velocities were observed when 0.16 mM (10 ppm) Cu^(2+) was in the solution and/or adsorbed onto the Si(111) surface as Cu^0 deposits, whereas low (100 ± 75 or 225 ± 20 cm s^(-1)) apparent surface recombination velocities were measured for Cu-contaminated Si(111) samples in contact with 0.16 mM (10 ppm) Cu^(2+)-containing 11 M NH_4F(aq) or BHF(aq) solutions, respectively.

Passivation of GaAs nanocrystals by chemical functionalization.

Abstract: The effective use of nanocrystalline semiconductors requires control of the chemical and electrical properties of their surfaces. We describe herein a chemical functionalization procedure to passivate surface states on GaAs nanocrystals. Cl-terminated GaAs nanocrystals have been produced by anisotropic etching of oxide-covered GaAs nanocrystals with 6 M HCl(aq). The Cl-terminated GaAs nanocrystals were then functionalized by reaction with hydrazine or sodium hydrosulfide. X-ray photoelectron spectroscopic measurements revealed that the surfaces of the Cl-, hydrazine-, and sulfide-treated nanocrystals were As-rich, due to significant amounts of As^0. However, no As^0 was observed in the photoelectron spectra after the hydrazine-terminated nanocrystals were annealed at 350° C under vacuum. After the anneal, the N 1s peak of hydrazine-exposed GaAs nanocrystals shifted to 3.2 eV lower binding energy. This shift was accompanied by the appearance of a Ga 3d peak shifted 1.4 eV from the bulk value, consistent with the hypothesis that a gallium oxynitride capping layer had been formed on the nanocrystals during the annealing process. The band gap photoluminescence (PL) was weak from the Cl- and hydrazine- or sulfide-terminated nanocrystals, but the annealed nanocrystals displayed strongly enhanced band-edge PL, indicating that the surface states of GaAs nanocrystals were effectively passivated by this two-step, wet chemical treatment.

Phosphine Functionalization of GaAs(111)A Surfaces

Abstract: Phosphorus-functionalized GaAs surfaces have been prepared by exposure of Cl-terminated GaAs(111)A surfaces to triethylphosphine (PEt3) or trichlorophosphine (PCl3), or by the direct functionalization of the native-oxide terminated GaAs(111)A surface with PCl3. The presence of phosphorus on each functionalized surface was confirmed by X-ray photoelectron spectroscopy. High-resolution, soft X-ray photoelectron spectroscopy was used to evaluate the As and Ga 3d regions of such surfaces. On PEt3 treated surfaces, the Ga 3d spectra exhibited a bulk Ga peak as well as peaks that were shifted to 0.35, 0.92 and 1.86 eV higher binding energy. These peaks were assigned to residual Cl-terminated Ga surface sites, surficial Ga2O and surficial Ga2O3, respectively. For PCl3-treated surfaces, the Ga 3d spectra displayed peaks ascribable to bulk Ga(As), Ga2O, and Ga2O3, as well as a peak shifted 0.30 eV to higher binding energy relative to the bulk signal. A peak corresponding to Ga(OH)3, observed on the Cl-terminated surface, was absent from all of the phosphine-functionalized surfaces. After reaction of the Cl-terminated GaAs(111)A surface with PCl3 or PEt3, the As 3d spectral region was free of As oxides and As0. Although native oxide-terminated GaAs surfaces were free of As oxides after reaction with PCl3, such surfaces contained detectable amounts of As0. Photoluminescence measurements indicted that phosphine-functionalized surfaces prepared from Cl-terminated GaAs(111)A surfaces had better electrical properties than the native-oxide capped GaAs(111)A surface, while the native-oxide covered surface treated with PCl3 showed no enhancement in PL intensity.

Use of Alkane Monolayer Templates To Modify the Structure of Alkyl Ether Monolayers on Highly Ordered Pyrolytic Graphite

Abstract: Scanning tunneling microscopy (STM) has been used to investigate the structure of pure and mixed monolayers formed by adsorption of long-chain alkanes and/or ethers on highly ordered pyrolytic graphite. Application of a pure phenyloctane solution of simple alkanes, such as tritriacontane, CH3(CH2)31CH3, produced a monolayer within which the individual molecular axes were oriented perpendicular to the lamellar axes. In contrast, a pure solution of symmetrical long-chain ethers, such as di-n-hexadecyl ether, CH3(CH2)15O(CH2)15CH3, produced a monolayer within which the molecular axes were oriented at an angle of ≈65° relative to the lamellar axes. The compositions of the overlying solutions were then gradually changed either from pure alkanes to nearly pure ethers or from pure ethers to nearly pure alkanes. When ethers replaced alkanes in the monolayer, the ethers conformed to the orientation within the existing alkane layer, rather than adopting the characteristic orientation of pure ether monolayers. Howev...

Method for reuse of wafers for growth of vertically-aligned wire arrays

Abstract: Reusing a Si wafer for the formation of wire arrays by transferring the wire arrays to a polymer matrix, reusing a patterned oxide for several array growths, and finally polishing and reoxidizing the wafer surface and reapplying the patterned oxide.

Scanning tunneling microscopy studies of monolayer templates: alkylthioethers and alkylethers.

Abstract: Scanning tunneling microscopy has been used to determine the molecular ordering in stable, ordered monolayers formed from long-chain normal and substituted alkanes in solution on highly oriented pyrolytic graphite surfaces. Monolayers were initially formed using an overlying solution of either a symmetrical dialkylthioether or a symmetrical dialkylether. Initially pure thioether solutions were then changed to nearly pure solutions of the identical chain-length ether, and vice versa. The direct application of a pure solution of long-chain symmetrical ethers onto graphite produced a lamellate monolayer within which the individual molecular axes were oriented at an angle of ~65° to the lamellar axes. In contrast, a pure solution of long-chain symmetrical thioethers on graphite produced a monolayer within which the molecular axes were oriented perpendicular to the lamellar axes. When ethers were gradually added to solutions overlying pure thioether monolayers, the ethers substituted into the existing monolayer structure. Thus, the ether molecules could be forced to orient in the perpendicular thioether-like manner through the use of a thioether template monolayer. Continued addition of ethers to the solution ultimately produced a nearly pure ether monolayer that retained the orientation of the thioether monolayer template. However, a monolayer of thioether molecules formed by gradual substitution into an ether monolayer did not retain the 65° orientation typical of dialkylethers, but exhibited the 90° orientation typical of dialkylthioether monolayers. The thioethers and ethers were easily distinguished in images of mixed monolayers, allowing both an analysis of the distribution of the molecules within the mixed monolayers and a comparison of the monolayer compositions with those of the overlying solutions. Substitution of molecules into the template monolayer did not proceed randomly; instead, a molecule within a monolayer was more likely to be replaced by a molecule in the overlying solution if it was located next to a molecule that had already been replaced.

Synthesis and surface chemistry of Zn 3 P 2

Abstract: Zinc phosphide (Zn 3 P 2 ) is a promising alternative to traditional materials (e.g. CIGS, CdTe, a-Si) for thin film photovoltaics. Open circuit voltage in Zn 3 P 2 cells has been limited by Fermi-level pinning due to surfaces states and heterojunction interdiffusion, motivating the need to prepare interfaces that are electrically passive and chemically inert. We investigated the surface chemistry of Zn 3 P 2 via etching with bromine in methanol and passivation with ammonium sulfide in t-butanol. The treatment decreases surface oxidation as determined by x-ray photoelectron spectroscopy and provides a stable, low-defect interface as monitored by steady-state photoluminescence. Magnesium Schottky diodes fabricated with sulfur-passivated interfaces show evidence of enhanced barrier heights in comparison to control devices.

The challenge and need for Energy & Environmental Science

Abstract: Progress in transitioning to a globally scalable and sustainable energy system is a world-wide problem and demands contributions from scientists, engineers, economists, policy makers, and decision makers around the world. Rapid progress on this urgent issue depends on the integration of perspectives in all of these areas, which is the underlying and unique charter of Energy & Environmental Science as a leading, interdisciplinary journal.

Extraction of spatiotemporal response information from sorption-based cross-reactive sensor arrays for the identification and quantification of analyte mixtures

Abstract: Linear sensor arrays made from small molecule/carbon black composite chemiresistors placed in a low headspace volume chamber, with vapor delivered at low flow rates, allowed for the extraction of chemical information that significantly increased the ability of the sensor arrays to identify vapor mixture components and to quantify their concentrations. Each sensor sorbed vapors from the gas stream to various degrees. Similar to gas chromatography, species having high vapor pressures were separated from species having low vapor pressures. Instead of producing typical sensor responses representative of thermodynamic equilibrium between each sensor and an unchanging vapor phase, sensor responses varied depending on the position of the sensor in the chamber and the time from the beginning of the analyte exposure. This spatiotemporal (ST) array response provided information that was a function of time as well as of the position of the sensor in the chamber. The responses to pure analytes and to multi-component analyte mixtures comprised of hexane, decane, ethyl acetate, chlorobenzene, ethanol, and/or butanol, were recorded along each of the sensor arrays. Use of a non-negative least squares (NNLS) method for analysis of the ST data enabled the correct identification and quantification of the composition of 2-, 3-, 4- and 5-component mixtures from arrays using only 4 chemically different sorbent films and sensor training on pure vapors only. In contrast, when traditional time- and position-independent sensor response information was used, significant errors in mixture identification were observed. The ability to correctly identify and quantify constituent components of vapor mixtures through the use of such ST information significantly expands the capabilities of such broadly cross-reactive arrays of sensors.