Optimizing the NIR Fluence Threshold for Nanobubble Generation by Controlled Synthesis of 10 - 40 nm Hollow Gold Nanoshells.

The laser fluence to trigger nanobubbles around hollow gold nanoshells (HGN) with near infrared light was examined through systematic modification of HGN size, localized surface plasmon resonance (LSPR), HGN concentration, and surface coverage. Improved temperature control during silver template synthesis provided monodisperse, silver templates as small as 9 nm. 10 nm HGN with < 2 nm shell thickness were prepared from these templates with a range of surface plasmon resonances from 600 - 900 nm. The fluence of picosecond near infrared (NIR) pulses to induce transient vapor nanobubbles decreased with HGN size at a fixed LSPR wavelength, unlike solid gold nanoparticles of similar dimensions that require an increased fluence with decreasing size. Nanobubble generation causes the HGN to melt with a blue shift of the LSPR. The nanobubble threshold fluence increases as the irradiation wavelength moves off the nanoshell LSPR. Surface treatment did not influence the threshold fluence. The threshold fluence increased with decreasing HGN concentration, suggesting that light localization through multiple scattering plays a role. The nanobubble threshold to rupture liposomes is 4 times smaller for 10 nm than for 40 nm HGN at a given LSPR, allowing us to use HGN size, LSPR, laser wavelength and fluence to control nanobubble generation.

Tunable optical chirality in a metamaterial platform with off-resonantly coupled metal-dielectric components.

Here we present a tunable chiral metamaterial platform that incorporates both metal and dielectric components, where the sign and magnitude of the circular dichroism (CD) response depend on the refractive index of the dielectric component. Using finite-difference time-domain simulations, we show that non-resonant scattering interactions between the components of the system reverse the sign of the CD signal by changing the dissymmetry in absorption of circularly polarized light by the individual plasmonic components of the system. The platform exhibits tunable CD signal regardless of the shape and dimension of the dielectric scatterer, and the magnitude of the CD signal is enhanced by improving the scattering cross section of the dielectric structure. Finally, we show that the structure can be modified to incorporate other materials without diminishing the reversal in dissymmetry in transmission. These results indicate that controlled, off-resonant interactions between different materials in chiral metamaterials may be used to create tailored and tunable chiral platforms.

Imaging Intra- and Interparticle Acousto-plasmonic Vibrational Dynamics with Ultrafast Electron Microscopy.

We report real-space, time-resolved imaging of coherently excited acoustic phonon modes in plasmonic nanoparticles via femtosecond electron imaging with an ultrafast electron microscope. The particles studied were cetyl trimethylammonium bromide stabilized Au nanorods (40 × 120 nm), and the particular specimen configurations for which photoinduced vibrational modes were visualized consisted of a single, isolated nanocrystal and a cluster of four irregularly arranged and randomly oriented particles, all supported on an amorphous Si3N4 membrane. In both configurations, we are able to resolve discrete intraparticle acoustic phonon modes via diffraction-contrast modulation with bright-field femtosecond electron imaging. For the single nanorod, we spatiotemporally mapped the intraparticle vibrational energy distribution and decay times. With Fourier filtering, acoustic phonons ranging from 4 to 30 GHz (250 to 33 ps periods, respectively) were visualized, corresponding to bending, extensional, and higher-order modes. Furthermore, heterogeneously distributed intraparticle decay times, ranging from 3 to 10 ns, were spatially mapped, indicating a strong dependence on coupling of the mode to the underlying substrate. For a cluster of four randomly oriented nanorods, we are able to image acoustic phonon modes that are strongly localized to particular particle-particle contact regions within the aggregate. A vibrational mode occurring at 27 GHz (37 ps period) was observed to occur at a 10 nm side-to-end contact region, with other intraparticle points at distances of 20 and 50 nm from the region showing no such dynamics, although the initial few-picosecond diffraction-contrast response was observed changing sign in moving from the end to the center of the particle. Excellent agreement is found between the spatiotemporally mapped vibrational-mode symmetries and finite-element simulations of supported modes in a polymer-coated Au nanorod supported on a Si3N4 membrane. This experiment resolves both the structure and dynamic properties of the plasmonic assembly, providing insight into the characteristics of complex plasmonic assemblies that ultimately determine their response to ultrafast excitation.

Circular Dichroism in Off-Resonantly Coupled Plasmonic Nanosystems.

Chiral plasmonic systems have been shown to exhibit large chiroptical responses, much larger than those found in molecular or solid state systems. In this Letter, we investigate the role of resonant coupling in such systems and whether the formation of collective plasmonic modes in a chiral assembly of metallic nanostructures is a necessary condition for chiroptical response. We show in experiment and simulation that off-resonant coupling between spectrally detuned nanostructures arranged with structural chirality leads to a clear but weak chiroptical response. We interpret our results in the framework of scattering between the individual constituents that in turn leads to a chiroptical farfield response. We envision that our results will allow further tuning and manipulation of chiroptical responses in plasmonic systems for tailored chiral light matter interaction.

Reversible Aptamer-Au Plasmon Rulers for Secreted Single Molecules.

Plasmon rulers, consisting of pairs of gold nanoparticles, allow single-molecule analysis without photobleaching or blinking; however, current plasmon rulers are irreversible, restricting detection to only single events. Here, we present a reversible plasmon ruler, comprised of coupled gold nanoparticles linked by a single aptamer, capable of binding individual secreted molecules with high specificity. We show that the binding of target secreted molecules to the reversible plasmon ruler is characterized by single-molecule sensitivity, high specificity, and reversibility. Such reversible plasmon rulers should enable dynamic and adaptive live-cell measurement of secreted single molecules in their local microenvironment.

Dielectric core-shell optical antennas for strong solar absorption enhancement.

We demonstrate a new light trapping technique that exploits dielectric core-shell optical antennas to strongly enhance solar absorption. This approach can allow the thickness of active materials in solar cells lowered by almost 1 order of magnitude without scarifying solar absorption capability. For example, it can enable a 70 nm thick hydrogenated amorphous silicon (a-Si:H) thin film to absorb 90% of incident solar radiation above the bandgap, which would otherwise require a thickness of 400 nm in typical antireflective coated thin films. This strong enhancement arises from a controlled optical antenna effect in patterned core-shell nanostructures that consist of absorbing semiconductors and nonabsorbing dielectric materials. This core-shell optical antenna benefits from a multiplication of enhancements contributed by leaky mode resonances (LMRs) in the semiconductor part and antireflection effects in the dielectric part. We investigate the fundamental mechanism for this enhancement multiplication and demonstrate that the size ratio of the semiconductor and the dielectric parts in the core-shell structure is key for optimizing the enhancement. By enabling strong solar absorption enhancement, this approach holds promise for cost reduction and efficiency improvement of solar conversion devices, including solar cells and solar-to-fuel systems. It can generally apply to a wide range of inorganic and organic active materials. This dielectric core-shell antenna can also find applications in other photonic devices such as photodetectors, sensors, and solid-state lighting diodes.

Design of nanostructured solar cells using coupled optical and electrical modeling.

Nanostructured light trapping has emerged as a promising route toward improved efficiency in solar cells. We use coupled optical and electrical modeling to guide optimization of such nanostructures. We study thin-film n-i-p a-Si:H devices and demonstrate that nanostructures can be tailored to minimize absorption in the doped a-Si:H, improving carrier collection efficiency. This suggests a method for device optimization in which optical design not only maximizes absorption, but also ensures resulting carriers are efficiently collected.

Optimized spatial correlations for broadband light trapping nanopatterns in high efficiency ultrathin film a-Si:H solar cells.

Nanophotonic structures have attracted attention for light trapping in solar cells with the potential to manage and direct light absorption on the nanoscale. While both randomly textured and nanophotonic structures have been investigated, the relationship between photocurrent and the spatial correlations of random or designed surfaces has been unclear. Here we systematically design pseudorandom arrays of nanostructures based on their power spectral density, and correlate the spatial frequencies with measured and simulated photocurrent. The integrated cell design consists of a patterned plasmonic back reflector and a nanostructured semiconductor top interface, which gives broadband and isotropic photocurrent enhancement.

Sonosensitizer-Functionalized Graphene Nanoribbons for Adhesion Blocking and Sonodynamic Ablation of Ovarian Cancer Spheroids.

Advanced stage ovarian cancer is challenging to treat due to widespread seeding of tumor spheroids throughout the mesothelial lining of the peritoneal cavity. In this work, a therapeutic strategy using graphene nanoribbons (GNR) functionalized with 4-arm polyethylene glycol (PEG) and chlorin e6 (Ce6), a sonosensitizer, to target metastatic ovarian cancer spheroids is reported. GNR-PEG-Ce6 adsorbs onto the spheroids and disrupts their adhesion to extracellular matrix proteins or LP-9 mesothelial cells. Furthermore, for spheroids that do adhere, GNR-PEG-Ce6 delays spheroid disaggregation and spreading as well as mesothelial clearance, key metastatic processes following adhesion. Owing to the sonodynamic effects of Ce6 and its localized delivery via the biomaterial, GNR-PEG-Ce6 can kill ovarian cancer spheroids adhered to LP-9 cell monolayers when combined with mild ultrasound irradiation. The interaction with GNR-PEG-Ce6 also loosens cell-cell adhesions within the spheroids, rendering them more susceptible to treatment with the chemotherapeutic agents cisplatin and paclitaxel, which typically have difficulty in penetrating ovarian cancer spheroids. Thus, this material can facilitate effective chemotherapeutic and sonodynamic combination therapies. Finally, the adhesion inhibiting and sonodynamic effects of GNR-PEG-Ce6 are also validated with tumor spheroids derived from the ascites fluid of ovarian cancer patients, providing evidence of the translational potential of this biomaterial approach.

Doping- and Strain-Dependent Electrolyte-Gate-Induced Perovskite to Brownmillerite Transformation in Epitaxial La1-xSrxCoO3-δ Films.

Much recent attention has focused on the voltage-driven reversible topotactic transformation between the ferromagnetic metallic perovskite (P) SrCoO3-δ and oxygen-vacancy-ordered antiferromagnetic insulating brownmillerite (BM) SrCoO2.5. This is emerging as a paradigmatic example of the power of electrochemical gating (using, e.g., ionic liquids/gels), the wide modulation of electronic, magnetic, and optical properties generating clear application potential. SrCoO3 films are challenging with respect to stability, however, and there has been little exploration of alternate compositions. Here, we present the first study of ion-gel-gating-induced P → BM transformations across almost the entire La1-xSrxCoO3 phase diagram (0 ≤ x ≤ 0.70), under both tensile and compressive epitaxial strain. Electronic transport, magnetometry, and operando synchrotron X-ray diffraction establish that voltage-induced P → BM transformations are possible at essentially all x, including x ≤ 0.50, where both P and BM phases are highly stable. Under small compressive strain, the transformation threshold voltage decreases from approximately +2.7 V at x = 0 to negligible at x = 0.70. Both larger compressive strain and tensile strain induce further threshold voltage lowering, particularly at low x. The P → BM threshold voltage is thus tunable, via both composition and strain. At x = 0.50, voltage-controlled ferromagnetism, transport, and optical transmittance are then demonstrated, achieving Curie temperature and resistivity modulations of ∼220 K and at least 5 orders of magnitude, respectively, and enabling estimation of the voltage-dependent Co valence. The results are analyzed in the context of doping- and strain-dependent oxygen vacancy formation energies and diffusion coefficients, establishing that it is thermodynamic factors, not kinetics, that underpin the decrease in the threshold voltage with x, that is, with increasing formal Co valence. These findings substantially advance the practical and mechanistic understanding of this voltage-driven transformation, with fundamental and technological implications.

Light trapping in ultrathin plasmonic solar cells.

We report on the design, fabrication, and measurement of ultrathin film a-Si:H solar cells with nanostructured plasmonic back contacts, which demonstrate enhanced short circuit current densities compared to cells having flat or randomly textured back contacts. The primary photocurrent enhancement occurs in the spectral range from 550 nm to 800 nm. We use angle-resolved photocurrent spectroscopy to confirm that the enhanced absorption is due to coupling to guided modes supported by the cell. Full-field electromagnetic simulation of the absorption in the active a-Si:H layer agrees well with the experimental results. Furthermore, the nanopatterns were fabricated via an inexpensive, scalable, and precise nanopatterning method. These results should guide design of optimized, non-random nanostructured back reflectors for thin film solar cells.

Poly(methyl methacrylate) Films with High Concentrations of Silicon Quantum Dots for Visibly Transparent Luminescent Solar Concentrators.

Silicon quantum dots (Si QDs) are attractive, nontoxic luminophores for luminescent solar concentrators (LSCs). Here, we produced Si QD/poly(methyl methacrylate) (PMMA) films on glass by doctor-blading polymer solutions and achieved films with low light scattering at an order of magnitude higher Si QD weight fraction than has been achieved previously in the bulk. We suggest that the fast solidification rate of films as compared to slow bulk polymerization is an enabling factor in avoiding large agglomerates within the nanocomposites. Scanning electron microscopy confirmed that ∼100 nm or larger QD agglomerates exist in light-scattering films, and photoluminescence intensity measurements show that light scattering, if present, significantly reduces waveguiding efficiencies for LSCs. Nonscattering films fabricated in this work exhibit high ultraviolet absorption (>80%) paired with high visible transmission (>87%) and minimal visible haze (∼1%), making them well suited for semitransparent coatings for LSCs realized as solar harvesting windows.

How much can guided modes enhance absorption in thin solar cells?

Absorption enhancement in thin metal-backed solar cells caused by dipole scatterers embedded in the absorbing layer is studied using a semi-analytical approach. The method accounts for changes in the radiation rate produced by layers above and below the dipole, and treats incoherently the subsequent scattering of light in guided modes from other dipoles. We find large absorption enhancements for strongly coupled dipoles, exceeding the ergodic limit in some configurations involving lossless dipoles. An antireflection-coated 100-nm layer of a- Si:H on Ag absorbs up to 87% of incident above-gap light. Thin layers of both strong and weak absorbers show similar strongly enhanced absorption.

Nanoscale Patterning of Colloidal Nanocrystal Films for Nanophotonic Applications Using Direct Write Electron Beam Lithography.

The small size of colloidal nanocrystal quantum dots (QDs) leads to a variety of unique optical properties that are well-suited to nanophotonics, including bright, tunable photoluminescence (PL). However, exploring the properties of solid QD assemblies at the nanoscale has proven challenging because of the limitations in the nanoscale QD patterning methods. Generally, the precise placement of QD solids is difficult to achieve, especially for tall structures with multiple QD layers, and when it is achieved the patterns often cannot withstand the further processing steps required for final device construction. Direct electron beam lithography of QDs has emerged as a straightforward patterning process that does not require ligand exchange and results in structures that retain bright PL. Here, we demonstrate that direct patterning QD films on substrates treated with a self-assembled monolayer of octadecyltrichlorosilane allows us to create feature sizes as thin as 30 nm with heights of multiple layers and characterize the pattern resolution, robustness, and placement accuracy. These structures withstand sonication in a variety of solvents, and the structures are placed within 20 nm of their intended location nearly 100% of the time. We further show how this patterning method can be applied to nanophotonics by measuring the complex refractive index of the QD materials to model the absorption and scattering cross sections of QD structures of various sizes and shapes. These simulations reveal that edge effects arising from the finite shape of the QD nanostructure lead to substantial absorption enhancement when compared to an equivalent volume region taken from a continuous QD film. Finally, we explore more complex structures by patterning QD arrays, multilayer QD structures, and QD disks inside plasmonic resonators.

Intrinsic measurements of exciton transport in photovoltaic cells.

Organic photovoltaic cells are partiuclarly sensitive to exciton harvesting and are thus, a useful platform for the characterization of exciton diffusion. While device photocurrent spectroscopy can be used to extract the exciton diffusion length, this method is frequently limited by unknown interfacial recombination losses. We resolve this limitation and demonstrate a general, device-based photocurrent-ratio measurement to extract the intrinsic diffusion length. Since interfacial losses are not active layer specific, a ratio of the donor- and acceptor-material internal quantum efficiencies cancels this quantity. We further show that this measurement permits extraction of additional device-relevant information regarding exciton relaxation and charge separation processes. The generality of this method is demonstrated by measuring exciton transport for both luminescent and dark materials, as well as for small molecule and polymer active materials and semiconductor quantum dots. Thus, we demonstrate a broadly applicable device-based methodology to probe the intrinsic active material exciton diffusion length.

Circular Dichroism of CdSe Nanocrystals Bound by Chiral Carboxylic Acids.

Chiral semiconductor nanocrystals, or quantum dots (QDs), are promising materials for applications in biological sensing, photonics, and spin-polarized devices. Many of these applications rely on large dissymmetry, or g-factors, the difference in absorbance between left- and right-handed circularly polarized light compared to the unpolarized absorbance. The majority of chiral QDs, specifically CdSe, reported to date have used thiolated amino acid ligands to introduce chirality onto the nanoparticles, but these systems have ultimately reported small g-factors of ∼2 × 10-4. In an effort to realize chiral CdSe QDs with higher g-factors and to expand the set of designer chiral semiconductor nanocrystals, we have employed chiral carboxylic acids as a distinct class of ligands for chiral CdSe nanoparticles. Through this family of chiral carboxylic acid ligands, we performed a direct comparison between carboxylate-bound and thiolate-bound chiral CdSe QDs. Spectral analysis revealed that the resulting circular dichroism shifts originate from the splitting of the exciton by the ligand-nanocrystal interaction. Subsequent examination of a series of chiral carboxylic acid ligands revealed a 30-fold range in g-factor through relatively small changes in the structure of the ligand. Finally, we showed that increasing the number of stereocenters on the ligand can further enhance the dissymmetry factors. This versatile and tunable combination of nanocrystals and ligands will inform future designs of chiral nanomaterials and their applications.

Luminescent solar concentration with semiconductor nanorods and transfer-printed micro-silicon solar cells.

We utilize CdSe/CdS seeded nanorods as a tunable lumophore for luminescent concentration. Transfer-printed, ultrathin crystalline Si solar cells are embedded directly into the luminescent concentrator, allowing the study of luminescent concentrators with an area over 5000 times the area of the solar cell. By increasing the size of the CdS rod with respect to the luminescent CdSe seed, the reabsorption of propagating photons is dramatically reduced. At long luminescence propagation distances, this reduced reabsorption can overcome the diminished quantum yield inherent to the larger semiconductor structures, which is studied with lifetime spectroscopy. A Monte Carlo ray tracing model is developed to explain the performance of the luminescent concentrator and is then used as a design tool to determine the effect of luminescence trapping on the concentration of light using both CdSe/CdS nanorods and a model organic dye. We design an efficient luminescence trapping structure that should allow the luminescent concentrator based on CdSe/CdS nanorods to operate in the high-concentration regime.

Nonmonotonic size dependence in the hole mobility of methoxide-stabilized PbSe quantum dot solids.

We present a facile procedure to fabricate p-type PbSe-based quantum dot solids with mobilities as large as 0.3 cm(2) V(-1)s(-1). Upon partial ligand exchange of oleate-capped PbSe quantum dots with the methoxide ion, we observe a pronounced red shift in the excitonic transition in conjunction with a large increase in conductivity. We show that there is little correlation between these two phenomena and that the electronic coupling energy in PbSe quantum dot solids is much smaller than often assumed. However, we observe for the first time a nonmonotonic size dependence of the hole mobility, illustrating that coupling can nonetheless be dominant in determining the transport characteristics. We attribute these effects to a decrease in charging energy and interparticle spacing, leading to enhanced electronic coupling on one hand and enhanced dipole interactions on the other hand, which is held responsible for the majority of the red shift.

Modeling light trapping in nanostructured solar cells.

The integration of nanophotonic and plasmonic structures with solar cells offers the ability to control and confine light in nanoscale dimensions. These nanostructures can be used to couple incident sunlight into both localized and guided modes, enhancing absorption while reducing the quantity of material. Here we use electromagnetic modeling to study the resonances in a solar cell containing both plasmonic metal back contacts and nanostructured semiconductor top contacts, identify the local and guided modes contributing to enhanced absorption, and optimize the design. We then study the role of the different interfaces and show that Al is a viable plasmonic back contact material.

Broadband polarization-independent resonant light absorption using ultrathin plasmonic super absorbers.

Resonant plasmonic and metamaterial structures allow for control of fundamental optical processes such as absorption, emission and refraction at the nanoscale. Considerable recent research has focused on energy absorption processes, and plasmonic nanostructures have been shown to enhance the performance of photovoltaic and thermophotovoltaic cells. Although reducing metallic losses is a widely sought goal in nanophotonics, the design of nanostructured 'black' super absorbers from materials comprising only lossless dielectric materials and highly reflective noble metals represents a new research direction. Here we demonstrate an ultrathin (260 nm) plasmonic super absorber consisting of a metal-insulator-metal stack with a nanostructured top silver film composed of crossed trapezoidal arrays. Our super absorber yields broadband and polarization-independent resonant light absorption over the entire visible spectrum (400-700 nm) with an average measured absorption of 0.71 and simulated absorption of 0.85. Proposed nanostructured absorbers open a path to realize ultrathin black metamaterials based on resonant absorption.