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ABSTRACT: Graphene and monolayer transition metal dichalcogenides (TMDs) are promising materials for next-generation ultrathin optoelectronic devices. Although visually transparent, graphene is an excellent sunlight absorber achieving 2.3% visible light absorbance in just 3Å thickness. TMD monolayers also hold potential as sunlight absorbers, and may enable ultrathin photovoltaic (PV) devices due to their semiconducting character. In this work, we show that the three TMD monolayers MoS2, MoSe2, and WS2 can absorb up to 5-10% incident sunlight in a thickness of less than 1 nm, thus achieving one order of magnitude higher sunlight absorption than GaAs and Si. We further study PV devices based on just two stacked monolayers: 1) a Schottky barrier solar cell between MoS2 and graphene, and 2) an excitonic solar cell based on a MoS2/WS2 bilayer. We demonstrate that such 1 nm thick active layers can attain power conversion efficiencies of up to ~1%, corresponding to 100-1,000 times higher power densities than the best existing ultrathin solar cells. Our work shows that two-dimensional monolayer materials hold yet untapped potential for solar energy absorption and conversion at the nanoscale.
Nano Letters 06/2013; · 13.20 Impact Factor
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ABSTRACT: Although the stoichiometry of bulk lead sulfide (PbS) is exactly 1∶1, that of quantum dots (QDs) can be considerably different from this crystalline limit. Employing first-principles calculations, we show that the impact of PbS QD stoichiometry on the electronic structure can be enormous, suggesting that control over the overall stoichiometry in the QD will play a critical role for improving the efficiency of optoelectronic devices made with PbS QDs. In particular, for bare PbS QDs, we find that: (i) stoichiometric PbS QDs are free from midgap states even without ligand passivation and independent of shape, (ii) off stoichiometry in PbS QDs introduces new states in the gap that are highly localized on certain surface atoms, and (iii) further deviations in stoichiometry lead to QDs with "metallic" behavior, with a dense number of energy states near the Fermi level. We further demonstrate that this framework holds for the case of passivated QDs by considering the attachment of ligand molecules as stoichiometry variations. Our calculations show that an optimal number of ligands makes the QD stoichiometric and heals unfavorable electronic structure, whereas too few or too many ligands cause effective off stoichiometry, resulting in QDs with defect states in the gap.
Physical Review Letters 05/2013; 110(19):196802. · 7.37 Impact Factor
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ABSTRACT: Reduced graphene oxide (rGO) is a promising material for a variety of thin-film optoelectronic applications. Two main barriers to its widespread use are the lack of (1) fabrication protocols leading to tailored functionalization of the graphene sheet with oxygen-containing chemical groups, and (2) understanding of the impact of such functional groups on the stability and on the optical and electronic properties of rGO. We carry out classical molecular dynamics and density functional theory calculations on a large set of realistic rGO structures to decompose the effects of different functional groups on the stability, work function, and photoluminescence. Our calculations indicate the metastable nature of carbonyl-rich rGO and its favorable transformation to hydroxyl-rich rGO at room temperature via carbonyl-to-hydroxyl conversion reactions near carbon vacancies and holes. We demonstrate a significant tunability in the work function of rGO up to 2.5 eV by altering the composition of oxygen-containing functional groups for a fixed oxygen concentration, and of the photoluminescence emission by modulating the fraction of epoxy and carbonyl groups. Taken together, our results guide the application of tailored rGO structures in devices for optoelectronics and renewable energy.
ACS Nano 01/2013; · 10.77 Impact Factor
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ABSTRACT: The recent advent of two-dimensional monolayer materials with tunable optical properties and high carrier mobility offers renewed opportunities for efficient, ultrathin excitonic solar cells alternative to those based on conjugated polymer and small molecule donors. Using first-principles density functional theory and many-body calculations, we demonstrate that monolayers of hexagonal BN and graphene (CBN) combined with commonly used acceptors such as PCBM fullerene or semiconducting carbon nanotubes can provide excitonic solar cells with tunable absorber gap, donor-acceptor interface band alignment, and power conversion efficiency, as well as novel device architectures. For the case of CBN-PCBM devices, we predict power conversion efficiency limits in the 10-20% range depending on the CBN monolayer structure. Our results demonstrate the possibility of using monolayer materials in tunable, efficient, ultrathin solar cells in which unexplored exciton and carrier transport regimes are at play.
ACS Nano 10/2012; · 10.77 Impact Factor
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ABSTRACT: We present an approach to calculation of point defect optical and thermal
ionization energies based on the highly accurate quantum Monte Carlo methods.
The use of an inherently many-body theory that directly treats electron
correlation offers many improvements over the typically-employed density
functional theory Kohn-Sham description. In particular, the use of quantum
Monte Carlo methods can help overcome the band gap problem and obviate the need
for ad-hoc corrections. We demonstrate our approach to the calculation of the
optical and thermal ionization energies of the F-center defect in magnesium
oxide, and obtain excellent agreement with experimental and/or other
high-accuracy computational results.
10/2012;
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ABSTRACT: We investigate the effects of two-dimensional (2D) periodic patterns of functional groups on the thermal transport in a graphene monolayer by employing molecular and lattice dynamics simulations. Our calculations show that the use of patterned 2D shapes on graphene reduces the room temperature thermal conductivity, by as much as 40 times lower than that of the pristine monolayer, due to a combination of boundary and clamping effects. Lattice dynamics calculations elucidate the correlation between this large reduction in thermal conductivity and two dynamical properties of the main heat carrying phonon modes: (1) decreased phonon lifetimes by an order of magnitude due to scattering, and (2) direction-dependent group velocities arising from phonon confinement. Taken together, these results suggest that patterned graphene nanoroads provide a method for tuning the thermal conductivity of graphene without the introduction of defects in the lattice, opening an important possibility for thermoelectric applications.
ACS Nano 09/2012; 6(10):9050-7. · 10.77 Impact Factor
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ABSTRACT: Carbon materials are excellent candidates for photovoltaic solar cells: they are Earth-abundant, possess high optical absorption, and maintain superior thermal and photostability. Here we report on solar cells with active layers made solely of carbon nanomaterials that present the same advantages of conjugated polymer-based solar cells, namely, solution processable, potentially flexible, and chemically tunable, but with increased photostability and the possibility to revert photodegradation. The device active layer composition is optimized using ab initio density functional theory calculations to predict type-II band alignment and Schottky barrier formation. The best device fabricated is composed of PC(70)BM fullerene, semiconducting single-walled carbon nanotubes, and reduced graphene oxide. This active-layer composition achieves a power conversion efficiency of 1.3%-a record for solar cells based on carbon as the active material-and we calculate efficiency limits of up to 13% for the devices fabricated in this work, comparable to those predicted for polymer solar cells employing PCBM as the acceptor. There is great promise for improving carbon-based solar cells considering the novelty of this type of device, the high photostability, and the availability of a large number of carbon materials with yet untapped potential for photovoltaics. Our results indicate a new strategy for efficient carbon-based, solution-processable, thin film, photostable solar cells.
ACS Nano 09/2012; 6(10):8896-903. · 10.77 Impact Factor
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ABSTRACT: Surprising Mpemba-like dissipation is observed during computer simulated ring-down of the flexural modes of a single-walled
carbon nanotube resonator. Vibrations are made to decay to zero faster by adding a larger initial excitation. We liken this counterintuitive observation to the well-known Mpemba effect in which hot water freezes
faster that cold water. In both cases, the system seems to pose a memory of its thermal history; a paradoxical result that
is reconciled if the dissipative state of the system is not described uniquely by the system’s average temperature. A vibrational
mode projection algorithm is used to track the dissipation pathway, showing that dissipation is dependent strongly on the
development of an athermal phonon population. The implications of Mpemba-like behavior in more general, and continuously driven,
nanomechanical systems are discussed.
Metallurgical and Materials Transactions A 04/2012; 42(13):3907-3912. · 1.54 Impact Factor
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ABSTRACT: We explain the nature of the electronic band gap and optical absorption
spectrum of Carbon - Boron Nitride (CBN) hybridized monolayers using density
functional theory (DFT), GW and Bethe-Salpeter equation calculations. The CBN
optoelectronic properties result from the overall monolayer bandstructure,
whose quasiparticle states are controlled by the C domain size and lie at
separate energy for C and BN without significant mixing at the band edge, as
confirmed by the presence of strongly bound bright exciton states localized
within the C domains. The resulting absorption spectra show two marked peaks
whose energy and relative intensity vary with composition in agreement with the
experiment, with large compensating quasiparticle and excitonic corrections
compared to DFT calculations. The band gap and the optical absorption are not
regulated by the monolayer composition as customary for bulk semiconductor
alloys and cannot be understood as a superposition of the properties of
bulk-like C and BN domains as recent experiments suggested.
04/2012;
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ABSTRACT: Nanoscale Li and intermetallic Al-Mg metal hydride clusters are investigated as a possible hydrogen storage material using the high-level quantum Monte Carlo computational method. Lower level methods such as density functional theory are qualitatively, not quantitatively accurate for the calculation of the enthalpy of absorption of H(2). At sizes around 1 nm, it is predicted that Al/Mg alloyed nanoparticles are stable relative to the pure compositions and the metal composition can be tuned in tandem with the size to tune the hydrogen absorption energy, making this a promising route to a rechargeable hydrogen storage material.
Physical Chemistry Chemical Physics 03/2012; 14(18):6611-6. · 3.57 Impact Factor
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ABSTRACT: Hyperdoping has emerged as a promising method for designing semiconductors with unique optical and electronic properties, although such properties currently lack a clear microscopic explanation. Combining computational and experimental evidence, we probe the origin of sub-band-gap optical absorption and metallicity in Se-hyperdoped Si. We show that sub-band-gap absorption arises from direct defect-to-conduction-band transitions rather than free carrier absorption. Density functional theory predicts the Se-induced insulator-to-metal transition arises from merging of defect and conduction bands, at a concentration in excellent agreement with experiment. Quantum Monte Carlo calculations confirm the critical concentration, demonstrate that correlation is important to describing the transition accurately, and suggest that it is a classic impurity-driven Mott transition.
Physical Review Letters 01/2012; 108(2):026401. · 7.37 Impact Factor
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ABSTRACT: We demonstrate single-walled carbon nanotube (SWCNT)/P3HT polymer bulk heterojunction solar cells with an AM1.5 efficiency of 0.72%, significantly higher than previously reported (0.05%). A key step in achieving high efficiency is the utilization of semiconducting SWCNTs coated with an ordered P3HT layer to enhance the charge separation and transport in the device active layer. Electrical characteristics of devices with SWCNT concentrations up to 40 wt % were measured and are shown to be strongly dependent on the SWCNT loading. A maximum open circuit voltage was measured for SWCNT concentration of 3 wt % with a value of 1.04 V, higher than expected based on the interface band alignment. Modeling of the open-circuit voltage suggests that despite the large carrier mobility in SWCNTs device power conversion efficiency is governed by carrier recombination. Optical characterization shows that only SWCNT with diameter of 1.3-1.4 nm can contribute to the photocurrent with internal quantum efficiency up to 26%. Our results advance the fundamental understanding and improve the design of efficient polymer/SWCNTs solar cells.
Nano Letters 12/2011; 11(12):5316-21. · 13.20 Impact Factor
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ABSTRACT: We formulate, solve computationally and study experimentally the problem of
collecting solar energy in three dimensions(1-5). We demonstrate that absorbers
and reflectors can be combined in the absence of sun tracking to build
three-dimensional photovoltaic (3DPV) structures that can generate measured
energy densities (energy per base area, kWh/m2) higher by a factor of 2-20 than
stationary flat PV panels, versus an increase by a factor of 1.3-1.8 achieved
with a flat panel using dual-axis sun tracking(6). The increased energy density
is countered by a higher solar cell area per generated energy for 3DPV compared
to flat panel design (by a factor of 1.5-4 in our conditions), but accompanied
by a vast range of improvements. 3DPV structures are steadier sources of solar
energy generation at all latitudes: they can double the number of peak power
generation hours and dramatically reduce the seasonal, latitude and weather
variations of solar energy generation compared to a flat panel design.
Self-supporting 3D shapes can create new schemes for PV installation and the
increased energy density can facilitate the use of cheaper thin film materials
in area-limited applications. Our findings suggest that harnessing solar energy
in three dimensions can open new avenues towards Terawatt-scale generation.
12/2011;
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ABSTRACT: The electronic structure of graphene-graphane superlattices with armchair interfaces is investigated with first-principles density-functional theory. By separately varying the widths, we find that the energy gap Eg is inversely proportional to the width of the graphene strip and that the gap increases as the hydrogenated strip becomes wider due to the enhanced confinement effect. It is further demonstrated that, unlike other graphene nanostructures, the superlattices exhibit both direct and indirect band gaps without external perturbations. This peculiarity in the nature of Eg originates from the different connection structures of the symmetrized wave function at the boundary between adjacent unit cells due to the reflection symmetry of the superlattices. These findings suggest that the optical as well as electronic properties of graphene superlattices can be controlled through selective chemical functionalization.
Phys. Rev. B. 09/2011; 84(11).
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ABSTRACT: Thermostat algorithms in a molecular dynamics simulation maintain an average temperature of a system by regulating the atomic velocities rather than the internal degrees of freedom. Herein, we present a "phonostat" algorithm that can regulate the total energy in a given internal degree of freedom. In this algorithm, the modal energies are computed at each time step using a mode-tracking scheme and then the system is driven by an external driving force of desired frequency and amplitude. The rate and amount of energy exchange between the phonostat and the system is controlled by two distinct damping parameters. Two different schemes for controlling the external driving force amplitude are also presented. In order to test our algorithm, the method is applied initially to a simple anharmonic oscillator for which the role of various phonostat parameters can be carefully tested. We then apply the phonostat to a more realistic (10,0) carbon nanotube system and show how such an approach can be used to regulate energy of highly anharmonic modes.
The Journal of chemical physics 06/2011; 134(21):214117. · 3.09 Impact Factor
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ABSTRACT: We have used scanning tunneling microscopy, Auger electron spectroscopy, and density functional theory calculations to investigate thermal and photoinduced structural transitions in (fulvalene)tetracarbonyldiruthenium molecules (designed for light energy storage) on a Au(111) surface. We find that both the parent complex and the photoisomer exhibit striking thermally induced structural phase changes on Au(111), which we attribute to the loss of carbonyl ligands from the organometallic molecules. Density functional theory calculations support this conclusion. We observe that UV exposure leads to pronounced structural change only in the parent complex, indicative of a photoisomerization reaction.
ACS Nano 05/2011; 5(5):3701-6. · 10.77 Impact Factor
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ABSTRACT: We present molecular and lattice dynamics calculations of the thermal conductivity of nanoporous silicon, and we show that it may attain values 10-20 times smaller than in bulk Si for porosities and surface-to-volume ratios similar to those obtained in recently fabricated nanomeshes. Further reduction of almost an order of magnitude is obtained in thin films with thickness of 20 nm, in agreement with experiment. We show that the presence of pores has two main effects on heat carriers: appearance of non-propagating, diffusive modes and reduction of the group velocity of propagating modes. The former effect is enhanced by the presence of disorder at the pore surfaces, while the latter is enhanced by decreasing film thickness.
ACS Nano 02/2011; 5(3):1839-44. · 10.77 Impact Factor
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Angewandte Chemie International Edition 11/2010; 49(47):8926-9. · 13.45 Impact Factor
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ABSTRACT: Charge transfer at the interface of conjugated polymer and nanoscale inorganic acceptors is pivotal in determining the efficiency of excitonic solar cells. Despite intense efforts, carbon nanotube/polymer solar cells have resulted in disappointing efficiencies (<2%) due in large part to poor charge transfer at the interface. While the interfacial energy level alignment is clearly important, the self-assembly and the interface structure also play a major role in facilitating this charge transfer. To understand and control this effect to our advantage, we study the interface of commonly used conductive polymer poly-3-hexylthiophene (P3HT) and single-walled carbon nanotubes (SWNTs) with a combination of molecular dynamics simulations, absorption spectra experiments, and an analysis of charge transfer effects. Classical molecular dynamics simulations show that the P3HT wraps around the SWNTs in a number of different conformations, including helices, bundles, and more elongated conformations that maximize planar π-π stacking, in agreement with recent experimental observations. Snapshots from the MD simulations reveal that the carbon nanotubes play an important templating role of increasing the π-conjugation in the system, an effect deriving from the π-π stacking interaction at the interface and the 1-dimensional (1D) nature of the SWNTs, and independent of the SWNT chirality. We show how this increase in the system conjugation could largely improve the charge transfer in P3HT-SWNT type II heterojunctions and support our results with absorption spectra measurements of mixtures of carbon nanotubes and P3HT. These findings open possibilities for improved preparation of polymeric solar cells based on carbon nanotubes and on 1D nanomaterials in general.
ACS Nano 10/2010; 4(11):6599-606. · 10.77 Impact Factor
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ABSTRACT: We present an efficient method to find minimum energy structures using energy estimates from accurate quantum Monte Carlo calculations. This method involves a stochastic process formed from the stochastic energy estimates from Monte Carlo calculations that can be averaged to find precise structural minima while using inexpensive calculations with moderate statistical uncertainty. We demonstrate the applicability of the algorithm by minimizing the energy of the H2O-OH- complex and showing that the structural minima from quantum Monte Carlo calculations affect the qualitative behavior of the potential energy surface substantially.
Physical Review Letters 05/2010; 104(21):210201. · 7.37 Impact Factor
