Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host.

We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. It also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core-shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na2Se2 (hcp) and Na2Se (fcc). A nanoscale fracture of terminally sodiated Na-Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na+ diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their "free" counterparts.

Nanoscale Modulation of Friction and Triboelectrification via Surface Nanotexturing.

Nanoscale contact electrification (CE) of elastomer surfaces and the resulting tribocharge formation are important in many branches of nanotechnology but their mechanism is not fully clarified. In this Letter, we investigate the mechanism using the recently discovered phenomenon of replica molding-induced nanoscale CE. By generating tribocharge distributions patterned in close correlation with the interfacial nanotextures, the phenomenon provides well-defined targets for the investigation. By applying a variety of scanning probe microscopy techniques (AFM/KPFM/EFM) and finite element modeling (FEM) to the tribocharge distributions, we extract a process model that can explain how their patterns are formed and affected by the interfacial nanotexture's morphology. It turns out that the cumulative distance of the elastomer's tangential sliding during the interfacial separation plays the key role in shaping the tribocharge's distribution pattern. The model proves remarkably universal, staying valid to nanotextures all the way down in the sub-10 nm regime. This replica molding-induced CE also turns out to be an effective tool for sculpting nanoscale tribocharge distributions into unconventional forms, such as rings, partial eclipses, and dumbbells. Both the model and the technique will prove useful in many areas of nanotechnology.

Photoluminescence Enhancement of CuInS2 Quantum Dots in Solution Coupled to Plasmonic Gold Nanocup Array.

A strong plasmonic enhancement of photoluminescence (PL) decay rate in quantum dots (QDs) coupled to an array of gold-coated nanocups is demonstrated. CuInS2 QDs that emit at a wavelength that overlaps with the extraordinary optical transmission (EOT) of the gold nanocup array are placed in the cups as solutions. Time-resolved PL reveals that the decay rate of the QDs in the plasmonically coupled system can be enhanced by more than an order of magnitude. Using finite-difference time-domain (FDTD) simulations, it is shown that this enhancement in PL decay rate results from an enhancement factor of ≈100 in electric field intensity provided by the plasmonic mode of the nanocup array, which is also responsible for the EOT. The simulated Purcell factor approaches 86 at the bottom of the nanocup and is ≈3-15 averaged over the nanocup cavity height, agreeing with the experimental enhancement result. This demonstration of solution-based coupling between QDs and gold nanocups opens up new possibilities for applications that would benefit from a solution environment such as biosensing.

Light management in perovskite solar cells and organic LEDs with microlens arrays.

We demonstrate enhanced absorption in solar cells and enhanced light emission in OLEDs by light interaction with a periodically structured microlens array. We simulate n-i-p perovskite solar cells with a microlens at the air-glass interface, with rigorous scattering matrix simulations. The microlens focuses light in nanoscale regions within the absorber layer enhancing the solar cell. Optimal period of ~700 nm and microlens height of ~800-1000 nm, provides absorption (photocurrent) enhancement of 6% (6.3%). An external polymer microlens array on the air-glass side of the OLED generates experimental and theoretical enhancements >100%, by outcoupling trapped modes in the glass substrate.

Reducing optical losses in organic solar cells using microlens arrays: theoretical and experimental investigation of microlens dimensions.

The performance of organic photovoltaic devices is improving steadily and efficiencies have now exceeded 10%. However, the incident solar spectrum still largely remains poorly absorbed. To reduce optical losses, we employed a microlens array (MLA) layer on the side of the glass substrate facing the incident light; this approach does not interfere with the processing of the active-layer. We observed up to 10% enhancement in the short circuit current of poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl}):(6,6)-phenyl C71-butyric acid methyl ester (PTB7:PC71BM) OPV cells. Theoretically and experimentally investigating several MLA dimensions, we found that photocurrent increases with the ratio of the height to the pitch size of MLA. Simulations reveal the enhancement mechanisms: MLA focuses light, and also increases the light path within the active-layer by diffraction. Photocurrent enhancements increase for a polymer system with thinner active-layers, as demonstrated in poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT):PC71BM OPVs with 17% improvement in short circuit current.

Nano-photonic light trapping near the Lambertian limit in organic solar cell architectures.

A critical step to achieving higher efficiency solar cells is the broad band harvesting of solar photons. Although considerable progress has recently been achieved in improving the power conversion efficiency of organic solar cells, these cells still do not absorb upto ~50% of the solar spectrum. We have designed and developed an organic solar cell architecture that can boost the absorption of photons by 40% and the photo-current by 50% for organic P3HT-PCBM absorber layers of typical device thicknesses. Our solar cell architecture is based on all layers of the solar cell being patterned in a conformal two-dimensionally periodic photonic crystal architecture. This results in very strong diffraction of photons- that increases the photon path length in the absorber layer, and plasmonic light concentration near the patterned organic-metal cathode interface. The absorption approaches the Lambertian limit. The simulations utilize a rigorous scattering matrix approach and provide bounds of the fundamental limits of nano-photonic light absorption in periodically textured organic solar cells. This solar cell architecture has the potential to increase the power conversion efficiency to 10% for single band gap organic solar cells utilizing long-wavelength absorbers.

Relativistic DFT Calculations of Cadmium and Selenium Solid-State NMR Spectra of CdSe Nanocrystal Surfaces.

Solid-state NMR spectra have been used to probe the structure of CdSe nanocrystals and propose detailed models of their surface structures. Density functional theory (DFT)-optimized cluster models that represent probable molecular structures of carboxylate-coordinated surface sites have been proposed. However, to the best of our knowledge, 113Cd and 77Se chemical shifts have not been calculated for these surface models. We performed relativistic DFT calculations of cadmium and selenium magnetic shielding tensors on model compounds with previously measured solid-state NMR spectra with (i) the four-component Dirac-Kohn-Sham (DKS) Hamiltonian and (ii) the scalar and (iii) spin-orbit levels within the ZORA Hamiltonian. Molecular clusters with Cd and Se sites in varying bonding environments were used to model CdSe (100) and CdSe(111) surfaces capped with carboxylic acid ligands. Our calculations identify the observed 113Cd isotropic chemical shifts δ(iso) of -465, -318, and -146 ppm arising from CdSeO3, CdSe2O2, and CdSe3O surface groups, respectively, with very good agreement with experimental measurements. The 113Cd chemical shifts linearly decrease with the number of O-neighbors. The calculated spans (δ11 - δ33) encompass the experimental values for CdSe3O and CdSe2O2 clusters but are slightly larger than the measured value for CdSeO3 clusters. Relativistic DFT calculations predicted a one-bond 113Cd-77Se scalar coupling of 258 Hz, which is in good agreement with the experimental values of 250 Hz. With a dense coverage of carboxylic acid ligands, the CdSe (100) surface shows a distribution of Cd-Se bond lengths and J-couplings. Relativistic DFT simulations thus aid in interpretation of NMR spectra of CdSe nanocrystals and related nanomaterials.

Nano-crystalline silicon solar cell architecture with absorption at the classical 4n(2) limit.

We develop a periodically patterned conformal photonic-plasmonic crystal based solar architecture for a nano-crystalline silicon solar cell, through rigorous scattering matrix simulations. The solar cell architecture has a periodic array of tapered silver nano-pillars as the back-reflector coupled with a conformal periodic structure at the top of the cell. The absorption and maximal current, averaged over the entire range of wavelengths, for this solar cell architecture is at the semi-classical 4n(2) limit over a range of common thicknesses (500-1500 nm) and slightly above the 4n(2) limit for a 500 nm nc-Si cell. The absorption exceeds the 4n(2) limit, corrected for reflection loss at the top surface. The photonic crystal cell current is enhanced over the flat Ag back-reflector by 60%, for a thick 1000 nm nc-Si layer, where predicted currents exceed 31 mA/cm(2). The conformal structure at the top surface focuses light within the absorber layer. There is plasmonic concentration of light, with intensity enhancements exceeding 7, near the back reflector that substantially enhances absorption.

High Light Outcoupling Efficiency from Periodically Corrugated OLEDs.

Organic light-emitting diodes (OLEDs) suffer from poor light outcoupling efficiency (ηout < 20%) due to large internal waveguiding in the high-index layers/substrate, and plasmonic losses at the metal cathode interface. A promising approach to enhance light outcoupling is to utilize internal periodic corrugations that can diffract waveguided and plasmonic modes back to the air cone. Although corrugations can strongly diffract trapped modes, the optimal geometry of corrugations and limits to ηout are not well-established. We develop a general rigorous scattering matrix theory for light emission from corrugated OLEDs, by solving Maxwell's equations in Fourier space, incorporating the environment-induced modification of the optical emission rate (Purcell effect). We computationally obtain the spectrally emissive power inside and outside the OLED. We find conformally corrugated OLEDs, where all OLED interfaces are conformal with a photonic crystal substrate, having triangular lattice symmetry, exhibit high light outcoupling ηout ∼60-65%, and an enhancement factor exceeding 3 for optimal pitch values between 1 and 2.5 µm. Waveguided and surface plasmon modes are strongly diffracted to the air cone through first-order diffraction. ηout is insensitive to corrugation heights larger than 100 nm. There is a gradual roll-off in ηout for a larger pitch and sharper decreases for small pitch values. Plasmonic losses remain below 10% for all corrugation pitch values. Our predicted OLED designs provide a pathway for achieving very high light outcoupling over the full optical spectrum that can advance organic optoelectronic science and solid-state lighting.

Mechano-Triboelectric Analysis of Surface Charge Generation on Replica-Molded Elastomeric Nanodomes.

Replica molding-based triboelectrification has emerged as a new and facile technique to generate nanopatterned tribocharge on elastomer surfaces. The "mechano-triboelectric charging model" has been developed to explain the mechanism of the charge formation and patterning process. However, this model has not been validated to cover the full variety of nanotexture shapes. Moreover, the experimental estimation of the tribocharge's surface density is still challenging due to the thick and insulating nature of the elastomeric substrate. In this work, we perform experiments in combination with numerical analysis to complete the mechano-triboelectrification charging model. By utilizing Kelvin probe force microscopy (KPFM) and finite element analysis, we reveal that the mechano-triboelectric charging model works for replica molding of both recessed and protruding nanotextures. In addition, by combining KPFM with numerical electrostatic modeling, we improve the accuracy of the surface charge density estimation and cross-calibrate the result against that of electrostatic force microscopy. Overall, the regions which underwent strong interfacial friction during the replica molding exhibited high surface potential and charge density, while those suffering from weak interfacial friction exhibited low values on both. These multi-physical approaches provide useful and important tools for comprehensive analysis of triboelectrification and generation of nanopatterned tribocharge. The results will widen our fundamental understanding of nanoscale triboelectricity and advance the nanopatterned charge generation process for future applications.

A planar four-port channel drop filter in the three-dimensional woodpile photonic crystal.

A compact planar channel four-port drop filter is developed experimentally and theoretically in the three-dimensional woodpile photonic crystal having a complete band gap. This consists of two waveguides separated by a defect in a single layer of the photonic crystal. Frequencies for channel dropping can be tuned throughout the band gap, by changing the size of the defect. Quality factors of approximately 1000 were measured. Simulations demonstrate directional energy transfer between the input and out put waveguides, through excitation of fields in the defect region. The planar nature of the filter is much more amenable to fabrication at optical length wavelengths.

Replica molding-based nanopatterning of tribocharge on elastomer with application to electrohydrodynamic nanolithography.

Replica molding often induces tribocharge on elastomers. To date, this phenomenon has been studied only on untextured elastomer surfaces even though replica molding is an effective method for their nanotexturing. Here we show that on elastomer surfaces nanotextured through replica molding the induced tribocharge also becomes patterned at nanoscale in close correlation with the nanotexture. By applying Kelvin probe microscopy, electrohydrodynamic lithography, and electrostatic analysis to our model nanostructure, poly(dimethylsiloxane) nanocup arrays replicated from a polycarbonate nanocone array, we reveal that the induced tribocharge is highly localized within the nanocup, especially around its rim. Through finite element analysis, we also find that the rim sustains the strongest friction during the demolding process. From these findings, we identify the demolding-induced friction as the main factor governing the tribocharge's nanoscale distribution pattern. By incorporating the resulting annular tribocharge into electrohydrodynamic lithography, we also accomplish facile realization of nanovolcanos with 10 nm-scale craters.

Nano-Photonic Structures for Light Trapping in Ultra-Thin Crystalline Silicon Solar Cells.

Thick wafer-silicon is the dominant solar cell technology. It is of great interest to develop ultra-thin solar cells that can reduce materials usage, but still achieve acceptable performance and high solar absorption. Accordingly, we developed a highly absorbing ultra-thin crystalline Si based solar cell architecture using periodically patterned front and rear dielectric nanocone arrays which provide enhanced light trapping. The rear nanocones are embedded in a silver back reflector. In contrast to previous approaches, we utilize dielectric photonic crystals with a completely flat silicon absorber layer, providing expected high electronic quality and low carrier recombination. This architecture creates a dense mesh of wave-guided modes at near-infrared wavelengths in the absorber layer, generating enhanced absorption. For thin silicon (<2 µm) and 750 nm pitch arrays, scattering matrix simulations predict enhancements exceeding 90%. Absorption approaches the Lambertian limit at small thicknesses (<10 µm) and is slightly lower (by ~5%) at wafer-scale thicknesses. Parasitic losses are ~25% for ultra-thin (2 µm) silicon and just 1%-2% for thicker (>100 µm) cells. There is potential for 20 µm thick cells to provide 30 mA/cm² photo-current and >20% efficiency. This architecture has great promise for ultra-thin silicon solar panels with reduced material utilization and enhanced light-trapping.

Unusual infrared absorption increases in photo-degraded organic films.

Degradation is among the most pressing problems facing organic materials, occurring through ingress of moisture and oxygen, and light exposure. We determine the nanoscale pathways underlying degradation by light-soaking organic films in an environmental chamber, and performing infrared spectroscopy, to identify atomic bonding changes. We utilize as a prototype the low band gap PTB7-PCBM blend. Films light-soaked in the presence of oxygen show unusual increased absorption at 1727 cm-1 attributable to increased C[double bond, length as m-dash]O modes, and a broad increase at 3240 cm-1 attributable to hydroxyl (O-H) groups bonded within the organic matrix. Films exposed to oxygen in the dark, or light-soaked in an inert atmosphere, do not exhibit significant absorption changes, suggesting simultaneous exposure of oxygen and light that creates singlet excited oxygen is the detrimental factor. Our ab initio electronic structure simulations interpret these by oxidation at the α-C site of the alkyl chains in PTB7, with an irreversible rupture of the alkyl chain and formation of new C[double bond, length as m-dash]O and C-O-H conformations at the α-C. Infrared spectroscopy coupled with ab initio simulation can provide a powerful tool for quantifying photo-structural atomic bonding changes. Understanding nanoscale light-induced structural changes will open avenues to designing more stable organic materials for organic electronics.

Extraordinary optical transmission in nanopatterned ultrathin metal films without holes.

We experimentally and theoretically demonstrate that a continuous gold film on a periodically textured substrate exhibits extraordinary optical transmission, even though no holes were etched in the film. Our film synthesis started by nanoimprinting a periodic array of nanocups with a period of ∼750 nm on a polystyrene film over a glass substrate. A thin non-conformal gold film was sputter-deposited on the polystyrene by angle-directed deposition. The gold film was continuous with spatial thickness variation, the film being thinnest at the bottom of the nanocup. Measurements revealed an extraordinary transmission peak at a wavelength just smaller than the period, with an enhancement of ∼2.5 compared to the classically expected value. Scattering matrix simulations model well the transmission and reflectance measurements when an ultrathin gold layer (∼5 nm), smaller than the skin depth is retained at the bottom of the nanocups. Electric field intensities are enhanced by >100 within the nanocup, and ∼40 in the ultrathin gold layer causing transmission through it. We show a wavelength red-shift of ∼30 nm in the extraordinary transmission peak when the nanocups are coated with a thin film of a few nanometers, which can be utilized for biosensing. The continuous corrugated metal films are far simpler structures to observe extraordinary transmission, circumventing the difficult process of etching the metal film. Such continuous metal films with ultrathin regions are simple platforms for non-linear optics, plasmonics, and biological and chemical sensing.

Nanoscale patterning of biopolymers for functional biosurfaces and controlled drug release.

We compare the rates of drug release from nanopatterned and flat biodegradable polymer surfaces, and observe significantly lower release rates from the nanopatterned surfaces. Specifically, we nanopattern poly(l-lactic acid) (PLLA), a biodegradable polymer frequently used for fabricating drug-eluting coronary stents, through microtransfer molding and solvent casting and investigate the nanopattern's impact on the release of sirolimus, an immunosuppressant agent, coated on the PLLA surface using high performance liquid chromatography/mass spectrometry. We find that PLLA surfaces nanopatterned with 750 nm-pitch nanocup or nanocone arrays exhibit drug release rates significantly lower (25-30%) than that of the flat surface, which is counter-intuitive given the nanopattern-induced increase in their surface areas. Based on diffusion and meniscus curvature minimization analyses, we attribute the decreased drug release rate to the incomplete wetting of the nanopatterned surface. These results provide new insights on how the surface nanopatterning of biomaterials can functionalize the surface and tailor the release kinetics of therapeutic agents coated on it for controlled drug elution.

Extremely efficient indium-tin-oxide-free green phosphorescent organic light-emitting diodes.

This paper demonstrates extremely efficient (η(P,max) = 118 lm W(-1) ) ITO-free green phosphorescent OLEDs (PHOLEDs) with multilayered, highly conductive poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) films as the anode. The efficiency is obtained without any outcoupling-enhancing structures and is 44% higher than the 82 lm W(-1) of similar optimized ITO-anode PHOLEDs. Detailed simulations show that this improvement is due largely to the intrinsically enhanced outcoupling that results from a weak microcavity effect.