Showing papers on "Heterojunction published in 2008"

Multi-quantum-well nanowire heterostructures for wavelength-controlled lasers.

Abstract: Rational design and synthesis of nanowires with increasingly complex structures can yield enhanced and/or novel electronic and photonic functions. For example, Ge/Si core/shell nanowires have exhibited substantially higher performance as field-effect transistors and low-temperature quantum devices compared with homogeneous materials, and nano-roughened Si nanowires were recently shown to have an unusually high thermoelectric figure of merit. Here, we report the first multi-quantum-well (MQW) core/shell nanowire heterostructures based on well-defined III-nitride materials that enable lasing over a broad range of wavelengths at room temperature. Transmission electron microscopy studies show that the triangular GaN nanowire cores enable epitaxial and dislocation-free growth of highly uniform (InGaN/GaN)n quantum wells with n=3, 13 and 26 and InGaN well thicknesses of 1-3 nm. Optical excitation of individual MQW nanowire structures yielded lasing with InGaN quantum-well composition-dependent emission from 365 to 494 nm, and threshold dependent on quantum well number, n. Our work demonstrates a new level of complexity in nanowire structures, which potentially can yield free-standing injection nanolasers.

Controlling Morphology in Polymer–Fullerene Mixtures

Abstract: In the past several years, polymer–fullerene mixtures have been intensely studied for use in organic solar cells because they can be deposited from solution, are compatible with lowcost roll-to-roll fabrication technology, and have shown high power conversion efficiency (g), up to 4–5%. The best devices consist of a single bulk-heterojunction active layer, in which the polymer (donor) and fullerene (acceptor) are deposited from a common solvent. As the solvent dries the donor and acceptor components separate into domains. The final efficiency of the solar cell has been shown to be extremely sensitive to the size, composition, and crystallinity of the formed domains. Improvement of the morphology in devices fabricated with a mixture of [6,6]-phenyl C61-butyric acid methyl ester (PCBM) and regioregular poly(3-hexylthiophene) (P3HT) has been achieved by using heat-treatment techniques and long-time solvent curing, with resulting record efficiencies. More recently, a method for increasing the crystallinity of the P3HT component has been introduced which involves filtering preformed nanofibers of P3HT out of solution and mixing the prepared nanofiber dispersion with PCBM to increase the efficiency of as-cast devices. Interestingly, the best device performance was achieved by mixing lower-molecular-weight (MW) amorphous P3HT back into the solution to reduce the crystalline content of the active layer and, thereby, to increase connection between crystalline domains. Studies of the MW impact on P3HT/PCBM solar cells have indicated that a large polydispersity and number-average molecular weight (Mn) over 19000 g mol -1 leads to improved efficiency. Morphology studies of organic field-effect transistor (OFET) devices indicate that the increased MW leads to better network formation between crystalline domains. The morphology of these improved devices has been studied using transmission electron microscopy (TEM), grazing-angle X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), NMR, and a variety of other optical and electrical techniques. The morphology studies give a picture of a device in which the P3HT forms aligned/crystalline domains, between which are amorphous segments of P3HT and PCBM. These domains form with larger size and crystallinity for higher heat-treatment temperatures and longer solvent soaking times. Depending on the fabrication and measurement techniques, the aligned domains of P3HT are depicted as fibers or as shapeless masses. The majority of these studies do not, however, allow quantification of the percentage of the P3HT that is agglomerated/ crystalline in the final device. Only by making use of the nanofiber filtration technique have the authors been given the ability to control the crystalline content of the P3HT in solution and in the final device. The disadvantages of this technique are the necessity of more complicated preparation, and filtered P3HT is restricted to a fibrous form that requires the addition of amorphous P3HT to provide connections between crystalline domains. We present here a simple method to determine the agglomerated–amorphous ratio of the P3HT and to control the degree of agglomeration/crystallinity of the P3HT in the final device by using a solvent mixing method and no further heat-treatment or prepreparation of the polymer. The most obvious change that heat-treatment and solvent soaking yield on a P3HT:PCBM layers is the change in color. It has been widely reported that the P3HT absorption red-shifts and a series of vibronic peaks become visible at k ∼ 600 nm, 550 nm, and 510 nm. This red-shift has been assigned to increased planarization and stabilization of the P3HT chains that accompanies self-stacking of the polymer. The crystal structure for these self-stacking domains has been solved by using XRD and TEM, and shows a herringbone interconnection of the alkyl chains and an a-dimension stacking distance of 1.6 nm. The p–p chain stacking of the P3HT chains in crystallites has been measured to be 0.38 nm. The herringbone structure and planarization of the P3HT with heating has been confirmed using heteronuclear solid-state NMR measurements. The red-shift in the UV-vis spectrum occurs proportionally to the degree of agglomeration of the P3HT. The pure amorphous electronic spectrum of P3HT or a mixture of P3HT and PCBM is simple to measure. A solution UV-vis spectrum can also be measured in the liquid state. If C O M M U N IC A TI O N

Nanoscale control of an interfacial metal–insulator transition at room temperature

Abstract: Experimental and theoretical investigations have demonstrated that a quasi-two-dimensional electron gas (q-2DEG) can form at the interface between two insulators: non-polar SrTiO3 and polar LaTiO3 (ref. 2), LaAlO3 (refs 3-5), KTaO3 (ref. 7) or LaVO3 (ref. 6). Electronically, the situation is analogous to the q-2DEGs formed in semiconductor heterostructures by modulation doping. LaAlO3/SrTiO3 heterostructures have recently been shown to exhibit a hysteretic electric-field-induced metal-insulator quantum phase transition for LaAlO3 thicknesses of 3 unit cells. Here, we report the creation and erasure of nanoscale conducting regions at the interface between two insulating oxides, LaAlO3 and SrTiO3. Using voltages applied by a conducting atomic force microscope (AFM) probe, the buried LaAlO3/SrTiO3 interface is locally and reversibly switched between insulating and conducting states. Persistent field effects are observed using the AFM probe as a gate. Patterning of conducting lines with widths of approximately 3 nm, as well as arrays of conducting islands with densities >10(14) inch(-2), is demonstrated. The patterned structures are stable for >24 h at room temperature.

High-performance polymer heterojunction solar cells of a polysilafluorene derivative

Abstract: High-performance polymer heterojunction solar cells fabricated from an alternating copolymer of 2,7-silafluorene (SiF) and 4,7-di(2′-thienyl)-2,1,3-benzothiadiazole (DBT) (PSiF-DBT) as the electron donor blended with [6,6]-phenyl-C61-butyric acid methyl ester as the electron acceptor were investigated. A power-conversion efficiency up to 5.4% with an open-circuit voltage of 0.90V, a short-circuit current of 9.5mAcm−2, and a fill factor of 50.7% was achieved under the illumination of AM 1.5G from a calibrated solar simulator (800Wm−2). The field-effect transistors fabricated from PSiF-DBT showed a high hole mobility of ∼1×10−3cm2V−1s−1.

Highly efficient inverted polymer solar cell by low temperature annealing of Cs2CO3 interlayer

Abstract: We demonstrate a highly efficient inverted bulk heterojunction polymer solar cell based on regioregular poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester with a low temperature annealed interfacial buffer layer, cesium carbonate (Cs2CO3). This approach improves the power conversion efficiency of the inverted cell from 2.3% to 4.2%, with short-circuit current of 11.17mA∕cm2, open-circuit voltage of 0.59V, and fill factor of 63% under AM1.5G 100mW∕cm2 irradiation. This result is comparable to the previous regular structure device on the same system. Ultraviolet photoelectron spectroscopy shows that the work function of annealed Cs2CO3 layer decreases from 3.45to3.06eV. Further x-ray photoelectron spectroscopy results reveal that Cs2CO3 can decompose into low work function, doped cesium oxide Cs2O upon annealing, which is accountable for the work-function reduction and device efficiency improvement.

High quantum efficiency InGaN/GaN solar cells with 2.95 eV band gap

Abstract: We report on III-nitride photovoltaic cells with external quantum efficiency as high as 63%. InxGa1−xN/GaN p-i-n double heterojunction solar cells are grown by metal-organic chemical vapor deposition on (0001) sapphire substrates with xIn=12%. A reciprocal space map of the epitaxial structure showed that the InGaN was coherently strained to the GaN buffer. The solar cells have a fill factor of 75%, short circuit current density of 4.2 mA/cm2, and open circuit voltage of 1.81 V under concentrated AM0 illumination. It was observed that the external quantum efficiency can be improved by optimizing the top contact grid.

Optical properties of rotationally twinned InP nanowire heterostructures.

Abstract: We have developed a technique so that both transmission electron microscopy and microphotoluminescence can be performed on the same semiconductor nanowire over a large range of optical power, thus allowing us to directly correlate structural and optical properties of rotationally twinned zinc blende InP nanowires. We have constructed the energy band diagram of the resulting multiquantum well heterostructure and have performed detailed quantum mechanical calculations of the electron and hole wave functions. The excitation power dependent blue-shift of the photoluminescence can be explained in terms of the predicted staggered band alignment of the rotationally twinned zinc blende/wurzite InP heterostructure and of the concomitant diagonal transitions between localized electron and hole states responsible for radiative recombination. The ability of rotational twinning to introduce a heterostructure in a chemically homogeneous nanowire material and alter in a major way its optical properties opens new possibilities for band-structure engineering.

Vertically Aligned p-Type Single-Crystalline GaN Nanorod Arrays on n-Type Si for Heterojunction Photovoltaic Cells

Abstract: Vertically aligned Mg-doped GaN nanorods have been epitaxially grown on n-type Si substrate to form a heterostructure for fabricating p-n heterojunction photovoltaic cells. The p-type GaN nanorod/n-Si heterojunction cell shows a well-defined rectifying behavior with a rectification ratio larger than 10(4) in dark. The cell has a high short-circuit photocurrent density of 7.6 mAlcm2 and energy conversion efficiency of 2.73% under AM 1.5G illumination at 100 mW/cm2. Moreover, the nanorod array may be used as an antireflection coating for solar cell applications to effectively reduce light loss due to reflection. This study provides an experimental demonstration for integrating one-dimensional nanostructure arrays with the substrate to directly fabricate heterojunction photovoltaic cells.

Silicon quantum dot/crystalline silicon solar cells.

Abstract: Silicon (Si) quantum dot (QD) materials have been proposed for 'all-silicon' tandem solar cells. In this study, solar cells consisting of phosphorus-doped Si QDs in a SiO2 matrix deposited on p-type crystalline Si substrates (c-Si) were fabricated. The Si QDs were formed by alternate deposition of SiO2 and silicon-rich SiOx with magnetron co-sputtering, followed by high-temperature annealing. Current tunnelling through the QD layer was observed from the solar cells with a dot spacing of 2 nm or less. To get the required current densities through the devices, the dot spacing in the SiO2 matrix had to be 2 nm or less. The open-circuit voltage was found to increase proportionally with reductions in QD size, which may relate to a bandgap widening effect in Si QDs or an improved heterojunction field allowing a greater split of the Fermi levels in the Si substrate. Successful fabrication of (n-type) Si QD/(p-type) c-Si photovoltaic devices is an encouraging step towards the realization of all-silicon tandem solar cells based on Si QD materials.

Direct Growth of Highly Mismatched Type II ZnO/ZnSe Core/Shell Nanowire Arrays on Transparent Conducting Oxide Substrates for Solar Cell Applications

Abstract: A number of nanometer-scale photovoltaic (PV) concepts based on semiconductor nanowires have been developed or proposed in recent years, with either inorganic/organic hybrid or all-inorganic approaches. The quasi-one-dimensional (quasi-1D) structure is perhaps the optimized choice for optoelectronic devices such as solar cells and photodetectors, because it allows for maximal advantage to be taken of reduced dimensionality whilst retaining the last and only needed conduction channel. Besides the possibility of exploring quantum effects at the nanoscopic scale, the quasi-1D system could be superior to the bulk material even at the mesoscopic scale, where the lateral size falls below the carrier diffusion length, for instance, by reducing the nonradiative recombination and carrier scattering loss through elimination of the unnecessary lateral transport and the resulting recombination loss. Additionally, a nanowire array constitutes a natural architecture, such as a photonic crystal, for light trapping. The charge separation of the electron and hole is a key step in the generation of solar power in a PV device. In a conventional solar cell, it is typically achieved by a planar p–n homojunction along the path of the current flow or longitudinally. In nanometer-architecture PV devices, however, the charge separation is often facilitated by a type II or staggered energy alignment of a heterojunction, constructed from two materials for which both the valance and conduction bands of one component lie lower in energy than the corresponding bands of the other component. Such heterojunctions have been intensively investigated for solar cell applications, including dyesensitized solar cells (DSSCs), quantum-dot-sensitized solar

A ZnO Nanorod Inorganic/Organic Heterostructure Light-Emitting Diode Emitting at 342 nm

Abstract: An inorganic/organic heterostructure light-emitting diode consisting of the hole-transporting layer N,N′-di(naphth-2-yl)-N,N′-diphenylbenzidine (NPB) and n-type ZnO nanorods fabricated by hydrothermal decomposition is reported. Poly(methyl methacrylate) was used to form a smooth surface on top of ZnO nanorod array with ZnO nanorod tops exposed for subsequent NPB deposition. An unusual ultraviolet emission at 342 nm was observed in the electroluminescence spectrum. Compared to band gap energy of ZnO (3.37 eV), the excitonic emission is blue-shifted and broadened. The mechanism of the blue shift is discussed in terms of the energy band diagram of the heterostructure.

Photocurrent generation in nanostructured organic solar cells.

Abstract: Photocurrent generation in nanostructured organic solar cells is simulated using a dynamical Monte Carlo model that includes the generation and transport properties of both excitons and free charges. Incorporating both optical and electrical properties, we study the influence of the heterojunction nanostructure (e.g., planar vs bulk junctions) on donor-acceptor organic solar cell efficiencies based on the archetype materials copper phthalocyanine (CuPc) and C(60). Structures considered are planar and planar-mixed heterojunctions, homogeneous and phase-separated donor-acceptor (DA) mixtures, idealized structures composed of DA pillars, and nanocrystalline DA networks. The thickness dependence of absorption, exciton diffusion, and carrier collection efficiencies is studied for different morphologies, yielding results similar to those experimentally observed. The influences of charge mobility and exciton diffusion length are studied, and optimal device thicknesses are proposed for various structures. Simulations show that, with currently available materials, nanocrystalline network solar cells optimize both exciton diffusion and carrier collection, thus providing for highly efficient solar energy conversion. Estimations of achievable energy conversion efficiencies are made for the various nanostructures based on current simulations used in conjunction with experimentally obtained fill factors and open-circuit voltages for conventional small molecular weight materials combinations.

P-type Cu--Ti--O nanotube arrays and their use in self-biased heterojunction photoelectrochemical diodes for hydrogen generation.

Abstract: Copper and titanium remain relatively plentiful in the earth's crust; hence, their use for large-scale solar energy conversion technologies is of significant interest. We describe fabrication of vertically oriented p-type Cu-Ti-O nanotube array films by anodization of copper rich (60% to 74%) Ti metal films cosputtered onto fluorine doped tin oxide (FTO) coated glass. Cu-Ti-O nanotube array films 1 mum thick exhibit external quantum efficiencies up to 11%, with a spectral photoresponse indicating that the complete visible spectrum, 380 to 885 nm, contributes significantly to the photocurrent generation. Water-splitting photoelectrochemical pn-junction diodes are fabricated using p-type Cu-Ti-O nanotube array films in combination with n-type TiO 2 nanotube array films. With the glass substrates oriented back-to-back, light is incident upon the UV absorbing n-TiO 2 side, with the visible light passing to the p-Cu-Ti-O side. In a manner analogous to photosynthesis, photocatalytic reactions are powered only by the incident light to generate fuel with oxygen evolved from the n-TiO 2 side of the diode and hydrogen from the p-Cu-Ti-O side. To date, we find under global AM 1.5 illumination that such photocorrosion-stable diodes generate a photocurrent of approximately 0.25 mA/cm (2), at a photoconversion efficiency of 0.30%.

Free Energy Control of Charge Photogeneration in Polythiophene/Fullerene Solar Cells: The Influence of Thermal Annealing on P3HT/PCBM Blends

Abstract: The function of organic solar cells is based upon charge photogeneration at donor/acceptor heterojunctions. In this paper, the origin of the improvement in short circuit current of poly(3-hexylthiophene)/6,6-phenyl C 61 -butyric acid methyl ester (P3HT/ PCBM) solar cells with thermal annealing is examined. Transient absorption spectroscopy is employed to demonstrate that thermal annealing results in an approximate two-fold increase in the yield of dissociated charges. The enhanced charge generation is correlated with a decrease in P3HT's ionization potential upon thermal annealing. These observations are in excellent quantitative agreement with a model in which efficient dissociation of the bound radical pair into free charges is dependent upon the bound radical state being thermally hot when initially generated, enabling it to overcome its coulombic binding energy. These observations provide strong evidence that the lowest unoccupied molecular orbital (LUMO) level offset of annealed P3HT/PCBM blends may be only just sufficient to drive efficient charge generation in polythiophene-based solar cells. This has important implications for current strategies to optimize organic photovoltaic device performance based upon the development of smaller optical bandgap polymers.

Design of Tunneling Field-Effect Transistors Using Strained-Silicon/Strained-Germanium Type-II Staggered Heterojunctions

Abstract: Heterojunction tunneling field-effect transistors (HTFETs) that use strained-silicon/strained-germanium type-II staggered band alignment for band-to-band tunneling (BBT) injection are simulated using a nonlocal quantum tunneling model. The tunneling model is first compared to measurements of gate- controlled BBT in previously fabricated strained SiGe diodes and is shown to produce good agreement with the measurements. The simulation of the gated diode structure is then extended to study HTFETs with an effective energy barrier of 0.25 eV at the strained-Si/strained-Ge heterointerface. As the band alignment, particularly the valence band offset, is critical to modeling HTFET operation, analysis of measured characteristics of MOS capacitors fabricated in strained-Si/strained-Ge/relaxed Si0.5Ge0.5 hetero- junctions is used to extract a valence band offset of 0.64 eV at the strained-Si/strained-Ge heterointerface. Simulations are used to compare HTFETs to MOSFETs with similar technology parameters. The simulations show that HTFETs have potential for low-operating-voltage (Vdd < 0.5 V) application and exhibit steep subthreshold swing over many decades while maintaining high ON-state currents.

Simultaneous Use of Small‐ and Wide‐Angle X‐ray Techniques to Analyze Nanometerscale Phase Separation in Polymer Heterojunction Solar Cells

Abstract: Using grazing-incidence small-angle X-ray scattering and wide-angle X-ray diffraction techniques to analyze the nanoscale phase separation of P3HT and PCBM after annealing, the effects of the sizes of the PCBM clusters and P3HT crystallites on the power conversion efficiency of bulk heterojunction solar cells is studied. This approach allowed us to investigate the effects of the sizes of the PCBM clusters and P3HT crystallites on the power conversion efficiencies of bulk heterojunction solar cells. It appears that improved power conversion efficiency requires the value of Rg of the PCBM clusters to be greater than 20nm and the value of D100 of the P3HT crystallites to be greater than 16nm for an active layer thickness of ca. 100nm.

Transparent and conductive electrodes based on unpatterned, thin metal films

Abstract: Transparent electrodes composed of ultrathin, unpatterned metal films are investigated in planar heterojunction (PHJ) and bulk heterojunction organic photovoltaic (OPV) cells. Optimal electrode composition and thickness are deduced from electrical and optical models and experiments, enabling a PHJ-OPV cell to be realized using a silver anode, achieving power conversion efficiency parity with an analogous cell that uses an indium tin oxide anode. Beneficial aspects of smooth, unpatterned metal films as transparent electrodes in OPV cells are also discussed in the text.

Analytical model for the open-circuit voltage and its associated resistance in organic planar heterojunction solar cells

Abstract: We derive an analytical formula for the open-circuit voltage Voc of organic planar heterojunction solar cells under standard operating conditions. We find that the type of free carrier recombination at the interface between the donor and acceptor materials controls the slope of Voc vs incident light intensity. By using the same derivation, an equation for the resistance around Voc is obtained. From this, we investigate two parameters in more detail and compare them to experiments. The first is the work function of the cathode metal. We show that, within our model, Voc does not depend on this work function, while the cell resistance around Voc is strongly dependent on it. Second, we find that the asymptotic resistance around Voc is a third-order power function of the thickness of the organic layers acceptor or donor. The model provides insights to achieve low-resistivity high open-circuit voltage organic solar cells.

Control of the nanoscale crystallinity and phase separation in polymer solar cells

Abstract: Grazing-incidence x-ray diffraction and atomic force microscopy were performed on bulk heterojunction regioregular poly(3-hexylthiophene) (RR-P3HT) [6,6]-phenyl-C71-butyric acid methyl esters spin-cast films with different film processing conditions to correlate the crystalline nanostructure of P3HT with the corresponding solar cell performance. The increase in long wavelength absorption for solvent annealed films is related to highly conjugated crystal structure of RR-P3HT phase-separated in the active layer. Upon thermal annealing, the solvent annealed 50-nm-thick device shows high solar cell performance with fill factor up to 73% and power conversion efficiency of 3.80%.

Charge recombination in organic photovoltaic devices with high open-circuit voltages.

Abstract: A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.

Synthesis, Structure, and Multiply Enhanced Field-Emission Properties of Branched ZnS Nanotube−In Nanowire Core−Shell Heterostructures

Abstract: We report on the synthesis of a novel core-shell metal-semiconductor heterostructure where In forms the core nanowire and wurtzite ZnS forms the shell nanotube. In addition, controlled reaction conditions result in the growth of secondary quasi-aligned ZnS nanowires as numerous branches on the shell nanotubes. These hierarchical architectures are attractive for two reasons: (i) the sharp and quasi-aligned ZnS tips of the nanostructures are potential field-emitters and (ii) since In in bulk form is superconducting the synthesis of core In nanowires should now pave the way for further investigations on magnetic versus transport behavior in type-1 superconductors at the nanoscale. The synthesis could be achieved by employing a rapidly heating carbothermal chemical vapor deposition technique and a high reaction temperature. Transmission electron microscopy reveals that the core In nanowires are single crystals, whereas, within a hierarchical shell, the stem and the branches are separated with a crystalline interface. Field-emission measurements demonstrate remarkably large field enhancement which is explained on the basis of a sequential stepwise enhancement mechanism involving the consecutive stem and branch contributions. The present new nanoarchitectures are envisaged to be an important candidate for potential nanoelectronic devices.

Structure and cathodoluminescence of individual ZnS/ZnO biaxial nanobelt heterostructures.

Abstract: We report on a controlled synthesis of two novel semiconducting heterostructures: heterocrystalline-ZnS/single-crystalline-ZnO biaxial nanobelts and side-to-side single-crystalline ZnS/ZnO biaxial nanobelts via a simple one-step thermal evaporation method. In the first heterostructure, a ZnS domain is composed of the heterocrystalline superlattice (3C-ZnS) N /(2H-ZnS) M [111]-[0001] with the atomically smooth interface between wurtzite and zinc blende ZnS fragments. High-spatial resolution cathodoluminescence studies on individual heterostructures for the first time reveal a new ultraviolet emission peak ( approximately 355 nm), which is not observed in separate ZnS or ZnO nanostructures. The present hererostructures are expected to become valuable not only with respect to fundamental research but also for a design of new broad-range ultraviolet nanoscale lasers and sensors.

Two Novel Cyclopentadithiophene-Based Alternating Copolymers as Potential Donor Components for High-Efficiency Bulk-Heterojunction-Type Solar Cells

Abstract: Polymer/fullerene bulk heterojunctions have recently generated a lot of scientific interest due to their potential in low-cost photovoltaic applications. In this paper we detail the synthesis and characterization of two new low-band-gap polythiophenes, poly[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-4,7-bis(2-thienyl)-2,1,3-benzothiadiazole-5′,5′′-diyl] (PCPDTTBTT) and poly[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-2,3-dioctylquinoxaline-5,8-diyl] (PCPDTQ), for use in these applications. The PCPDTQ polymer did not produce efficient solar cells. A high power efficiency of 2.1% under one sun was found for a PCPDTTBTT/fullerene mixture. The high efficiency was achieved by alteration of the morphology using a solvent additive. Analysis of atomic force microscopy phase images shows that material phases with distinct mixing ratios are formed and altered with the addition of the solvent additive.

Determination of band offsets in heterostructured colloidal nanorods using scanning tunneling spectroscopy.

Abstract: The ability to tailor the properties of semiconductor nanocrystals through creating core/shell heterostructures is the cornerstone for their diverse application in nanotechnology. The band-offsets between the heterostructure components are determining parameters for their optoelectronic properties, dictating for example the degree of charge-carrier separation and localization. So far, however, no method was reported for direct measurement of these factors in colloidal nanocrystals and only indirect information could be derived from optical measurements. Here we demonstrate that scanning tunneling spectroscopy along with theoretical modeling can be used to determine band-offsets in such nanostructures. Applying this approach to CdSe/CdS quantum-dot/nanorod core/shell nanocrystals portrays its type I band structure where both the hole and electron ground state are localized in the CdSe core, in contrast to previous reports which predicted electron delocalization. The generality of the approach is further demonstrated in ZnSe/CdS nanocrystals where their type II band alignment, leading to electron-hole separation, is manifested.

Electronic structures of interfacial states formed at polymeric semiconductor heterojunctions

Abstract: Understanding how excited states behave at heterojunctions between polymers in blends is fundamental to designing better organic solar cells and light-emitting diodes. A quantum-mechanical molecular-scale model of how excitations behave at heterojunctions has been developed, showing an unexpectedly wide but specific range of excitonic states.

Photodeposition of Pt on Colloidal CdS and CdSe/CdS Semiconductor Nanostructures

Abstract: Photodeposition of Pt on Colloidal CdS and CdSe/CdS Semiconductor Nanostructures Gordana Dukovic, Maxwell G. Merkle, James H. Nelson, Steven M. Hughes, and A. Paul Alivisatos* Department of Chemistry, University of California, Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA Semiconductor photocatalysis has been identified as a promising avenue for the conversion of solar energy into environmentally friendly fuels, most notably by the production of hydrogen from water.[1–5] Nanometer-scale materials in particular have attracted considerable scientific attention as the building blocks for light-harvesting applications.[6,7] Their desirable attributes include tunability of the optical properties with size, amenability to relatively inexpensive low-temperature processing, and a high degree of synthetic sophistication leading to increasingly complex and multi-functional architectures. For photocatalysis in particular, the high surface- to- volume ratios in nanoscale materials should lead to an increased availability of carriers for redox reactions on the nanoparticle surface. Recombination of photoexcited carriers directly competes with photocatalytic activity.[3] Charge separation is often achieved with multi-component heterostructures. An early example is the case of TiO2 powders functionalized with Pt and RuO2 particles, where photoexcited electrons are transferred to Pt (the reduction site) and holes to RuO2 (the oxidation site).[8] More recently, many colloidally synthesized nanometer-scale metal–semiconductor heterostructures have been reported.[7,9,10] A majority of these structures are made by thermal methods.[7,10] We have chosen to study photochemical formation of metal–semiconductor heterostructures. The detailed understanding of the mechanisms involved in photodeposition of metals on nanometer-scale semiconductors is necessary to enable a high degree of synthetic control. At the same time, because the results of metal deposition can be directly observed by electron microscopy, it can be used to understand how factors such as nanocrystal composition, shape, carrier dynamics, and surface chemistry influence the photochemical properties of semiconductor nanocrystals. In this communication, we report on the photodeposition of Pt on colloidal CdS and CdSe/CdS core/shell nanocrystals. Among the II–VI semiconductors, CdS is of particular interest because it has the correct band alignment for water photolysis[2] and has been demonstrated to be photocatalytically active.[11–16] We have found that the photoexcitation of CdS and CdSe/CdS in the presence of an organometallic Pt precursor leads to deposition of Pt nanoparticles on the semiconductor surface. Stark differences are observed in the Pt nanoparticle location on the two substrates, and the photodeposition can be completely inhibited by the modification of the semiconductor surface. Our results suggest that tuning of the semiconductor band structure, spatial organization and surface chemistry should be crucial in the design of photocatalytic nanostructures.

Origin of the open-circuit voltage in multilayer heterojunction organic solar cells

Abstract: From temperature dependent studies of pentacene/C60 solar cells in the dark, the reverse saturation current is found to be thermally activated with a barrier height that corresponds to the difference in energy between the highest occupied molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor corrected for vacuum level misalignments and the presence of charge-transfer states. From the reverse saturation current in the dark and the short-circuit current under illumination, the open-circuit voltage can be predicted. Examination of several donor materials supports the relationship between reverse saturation current, this barrier height, and open-circuit voltage.