High-Verdet Constant and Low-Optical Loss Tb3+ Doped Magnetite Nanoparticles.

Magneto-optical (MO) polymer nanocomposites have emerged as alternatives to conventional MO crystals, particularly in nanophotonics applications, thanks to their better processing flexibility and superior Verdet constants. However, a higher Verdet constant commonly comes with excessive optical loss due to increased absorption and scattering, resulting in a constant or reduced figure-of-merit (FOM) defined as the Verdet constant over optical loss. By doping magnetite (Fe3O4) nanoparticles with Tb3+ ions, we report a new strategy to enhance the Verdet constant without increasing the optical loss. The Fe3O4:Tb3+ nanocomposite is one of a kind that simultaneously achieves a state-of-the-art Verdet constant of 5.6 × 105 °/T·m and a state-of-the-art FOM of 31°/T in the near-infrared region.

On-chip mid-infrared optical sensing with GeSbSe waveguides and resonators.

We fabricated single mode Ge28Sb12Se60 waveguides and resonators using e-beam lithography and achieved a propagation loss of 3.88 dB/cm at 3.66 µm. We compared BCl3 and CHF3 etch chemistries and determined CHF3 produced 1.5 dB/cm higher propagation losses at 3.6 µm due to C-H bond absorption. We use fabricated waveguides to detect an aromatic aldehyde dissolved in a non-polar solvent with a limit of detection of 1.09 µmol/mL. We then reduce this detection limit to 0.25 µmol/mL using the enhancement produced by a chalcogenide ring resonator.

Fabrication and characterization of high quality GeSbSe reflowed and etched ring resonators.

We demonstrate the fabrication of high Q Ge28Sb12Se60 ring resonators in an all chalcogenide platform through electron-beam lithography, lift-off and thermal reflow. We achieve a Q factor of (3.9 ± 0.2) × 105 in the reflowed ring resonators and (2.5 ± 0.2) × 105 in the reactive ion etched ring resonators at 1550 nm. We measure the line roughness of these devices to estimate the scattering loss. We determine the material and scattering losses of the waveguide and find an additional 1.1 dB/cm excess loss from surface absorption. We fabricate Ge23Sb7S70 waveguides with 0.6 dB/cm of losses and show that Ge23Sb7S70 waveguides do not experience the same kind of excess loss when fabricated under the same conditions. This indicates the excess loss is related to the chemical composition of Ge28Sb12Se60 compound.

Selective excitation of plasmon resonances with single V-point cylindrical vector beams.

We use a rigorous group theoretical method to identify a class of cylindrical vector beams that can selectively excite the plasmon modes of axially symmetric plasmonic structures. Our choice of the single V-point cylindrical vector beams as the basis to decompose cylindrical beams dramatically simplifies the symmetry analysis in the group theory framework. With numerical simulations, we demonstrate that any plasmon eigenmodes, bright or dark, can be selectively excited individually or jointly. A straightforward protocol to get access to the desired plasmon mode using symmetry coupling is presented.

Third-harmonic generation enhancement in an ITO nanoparticle-coated microresonator.

We report a ∼3-fold enhancement of third-harmonic generation (THG) conversion efficiency using indium tin oxide (ITO) nanoparticles on the surface of an ultra-high-Q silica microsphere. This is one of the largest microcavity-based THG enhancements reported. Phase-matching and spatial mode overlap are explored numerically to determine the microsphere radius (∼29 µm) and resonant mode numbers that maximize THG. Furthermore, the ITO nanoparticles are uniformly bonded to the cavity surface by drop-casting, eliminating the need for complex fabrication. The significant improvement in THG conversion efficiency establishes functionalized ITO microcavities as a promising tool for broadband frequency conversion, nonlinear enhancement, and applications in integrated photonics.

Enhancement of third-order nonlinearity of thermally evaporated GeSbSe waveguides through annealing.

Chalcogenides are a promising platform for infrared nonlinear optics but are susceptible to structural changes during fabrication that affect their linear and nonlinear optical properties. We analyze the structure and optical properties of thermally evaporated and annealed chalcogenide films. Thermally evaporated Ge28Sb12Se60 has an increased selenium content, bandgap, and concentration of heteropolar bonds. The concentration of heteropolar bonds can be reduced by annealing above the glass transition temperature, resulting in improved optical nonlinearity. We demonstrate a 4-fold enhancement of third-order nonlinearity in Ge28Sb12Se60 chalcogenide waveguides by thermal annealing and a decrease in propagation loss from 2.5 dB/cm to 1 dB/cm as an added benefit.

Anti-EGFR Affibodies with Site-Specific Photo-Cross-Linker Incorporation Show Both Directed Target-Specific Photoconjugation and Increased Retention in Tumors.

A significant challenge for solid tumor treatment is ensuring that a sufficient concentration of therapeutic agent is delivered to the tumor site at doses that can be tolerated by the patient. Biomolecular targeting can bias accumulation in tumors by taking advantage of specific interactions with receptors overexpressed on cancerous cells. However, while antibody-based immunoconjugates show high binding to specific cells, their low dissociation constants ( KD) and large Stokes radii hinder their ability to penetrate deep into tumor tissue, leading to incomplete cell killing and tumor recurrence. To address this, we demonstrate the design and production of a photo-cross-linkable affibody that can form a covalent bond to epidermal growth factor receptor (EGFR) under near UV irradiation. Twelve cysteine mutations were created of an EGFR affibody and conjugated with maleimide-benzophenone. Of these only one exhibited photoconjugation to EGFR, as demonstrated by SDS-PAGE and Western blot. Next this modified affibody was shown to not only bind EGFR expressing cells but also show enhanced retention in a 3D tumor spheroid model, with minimal loss up to 24 h as compared to either unmodified EGFR-binding affibodies or nonbinding, photo-cross-linkable affibodies. Finally, in order to show utility of photo-cross-linking at clinically relevant wavelengths, upconverting nanoparticles (UCNPs) were synthesized that could convert 980 nm light to UV and blue light. In the presence of UCNPs, both direct photoconjugation to EGFR and enhanced retention in tumor spheroids could be obtained using near-infrared illumination. Thus, the photoactive affibodies developed here may be utilized as a platform technology for engineering new therapy conjugates that can penetrate deep into tumor tissue and be retained long enough for effective tumor therapy.

DNA-Assembled Core-Satellite Upconverting-Metal-Organic Framework Nanoparticle Superstructures for Efficient Photodynamic Therapy.

DNA-mediated assembly of core-satellite structures composed of Zr(IV)-based porphyrinic metal-organic framework (MOF) and NaYF4 ,Yb,Er upconverting nanoparticles (UCNPs) for photodynamic therapy (PDT) is reported. MOF NPs generate singlet oxygen (1 O2 ) upon photoirradiation with visible light without the need for additional small molecule, diffusional photosensitizers such as porphyrins. Using DNA as a templating agent, well-defined MOF-UCNP clusters are produced where UCNPs are spatially organized around a centrally located MOF NP. Under NIR irradiation, visible light emitted from the UCNPs is absorbed by the core MOF NP to produce 1 O2 at significantly greater amounts than what can be produced from simply mixing UCNPs and MOF NPs. The MOF-UCNP core-satellite superstructures also induce strong cell cytotoxicity against cancer cells, which are further enhanced by attaching epidermal growth factor receptor targeting affibodies to the PDT clusters, highlighting their promise as theranostic photodynamic agents.

Direct modeling of near field thermal radiation in a metamaterial.

The study of near field thermal radiation is gaining renewed interest thanks in part to their great potential in energy harvesting applications. It is well known that plasmonic or polaritonic materials exhibit strongly enhanced fields near the surface, but it is not trivial to quantitatively predict their impact on thermal radiation intensity in the near field. In this paper, we present a case study for a metamaterial that supports a surface plasmon mode in the terahertz region and consequently exhibits strongly enhanced near field thermal radiation at the plasmon resonance frequency. We implemented a finite-difference time-domain method that thermally excites the metamaterial with randomly fluctuating dipoles according to the fluctuation-dissipation theorem. The calculated thermal radiation from the metamaterial was then compared with the case of optical excitation by the plane wave incident on the metamaterial surface. The optical excitation couples only to the mode that satisfies the momentum matching condition while thermal excitation is not bound by it. As a result, the near field thermal radiation exhibits substantial differences compared to the optically excited surface plasmon modes. Under thermal excitation, the near field intensity at 1 µm away from metal surface of the metamaterial reaches a maximum enhancement of 43 fold over the far field at the frequency of the Brillouin zone boundary mode while the near field intensity under optical excitation reaches a maximum enhancement of 24 fold at the frequency of the Brillouin zone center mode. In addition, the peak near field intensity under thermal excitation shows a 4-fold enhancement over blackbody radiation with linear polarization radiation in the far field. The ability to precisely predict the local field intensity under thermal excitation is critical to the development of advanced energy devices that take advantage of this near field enhancement and could lead to the development of new generation of novel energy technology.

High quality chalcogenide-silica hybrid wedge resonator.

Chalcogenide glasses, with high nonlinearity and low loss, have captured research interest as an integrated device platform for near- and mid-infrared nonlinear optical devices. Compared to silicon-based microfabrication technologies, chalcogenide fabrication processes are less mature and a major challenge is obtaining high quality devices. In this paper, we report a hybrid resonator design leveraging a high quality silica resonator to achieve high Q factors with chalcogenide. The device is composed of a thin chalcogenide layer deposited on a silica wedge resonator. The hybrid resonators exhibit loaded Q factors up to 1.5 x 105 in the near-infrared region. We also measured the effective thermo-optic coefficient of the device to be 5.5x10-5/K, which agreed well with the bulk value. Thermal drift of the device can be significantly reduced by introducing a titanium dioxide cladding layer with a negative thermo-optic coefficient.

Plasmon enhancement of luminescence upconversion.

Frequency conversion has always been an important topic in optics. Nonlinear optics has traditionally focused on frequency conversion based on nonlinear susceptibility but with the recent development of upconversion nanomaterials, luminescence upconversion has begun to receive renewed attention. While upconversion nanomaterials open doors to a wide range of new opportunities, they remain too inefficient for most applications. Incorporating plasmonic nanostructures provides a promising pathway to highly efficient upconversion. Naturally, a plethora of theoretical and experimental studies have been published in recent years, reporting enhancements up to several hundred. It is however difficult to make meaningful comparisons since the plasmonic fields are highly sensitive to the local geometry and excitation condition. Also, many luminescence upconversion processes involve multiple steps via different physical mechanisms and the overall output is often determined by a delicate interplay among them. This review is aimed at offering a comprehensive framework for plasmon enhanced luminescence upconversion. We first present quantum electrodynamics descriptions for all the processes involved in luminescence upconversion, which include absorption, emission, energy transfer and nonradiative transitions. We then present a bird's eye view of published works on plasmon enhanced upconversion, followed by more detailed discussion on comparable classes of nanostructures, the effects of spacer layers and local heating, and the dynamics of the plasmon enhanced upconversion process. Plasmon enhanced upconversion is a challenging and exciting field from the fundamental scientific perspective and also from technological standpoints. It offers an excellent system to study how optical processes are affected by the local photonic environment. This type of research is particularly timely as the plasmonics is placing heavier emphasis on nonlinearity. At the same time, efficient upconversion could make a significant impact on many applications including solar energy conversion and biomedical imaging. The marriage of luminescent materials research with nanophotonics currently being initiated with plasmon enhanced upconversion research explores a new frontier in photonics that could potentially spawn many exciting new fields.

Nonlinear characterization of Ge28Sb12Se60 bulk and waveguide devices.

Single-mode Ge28Sb12Se60 strip waveguides, fabricated with thermal evaporation and lift-off, were demonstrated at 1.03 µm. The linear and nonlinear optical properties of these waveguides were shown to be similar to bulk samples, with differences attributed to small variations in composition of ~4 atomic % or less. From z-scan measurements at 1.03 µm using circularly polarized, ~200 fs pulses at 374 kHz, Ge28Sb12Se60 was found to have a nonlinear refractive index ~130 x fused silica and a two-photon absorption coefficient of 3.5 cm/GW. Given the large two-photon absorption coefficient, this material shows promise for optical limiting applications at 1 µm.

Template synthesis of gold nanoparticles with an organic molecular cage.

We report a novel strategy for the controlled synthesis of gold nanoparticles (AuNPs) with narrow size distribution (1.9 ± 0.4 nm) through NP nucleation and growth inside the cavity of a well-defined three-dimensional, shape-persistent organic molecular cage. Our results show that both a well-defined cage structure and pendant thioether groups pointing inside the cavity are essential for the AuNP synthesis.

A scalable fabrication method for gold nanodisk-upconverting nanoparticle hybrid nanostructures.

Plasmonic nanostructures can be used to enhance the efficiency of upconversion nanoparticles (UCNPs) and enable new functionalities. However, the fabrication of these hybrid plasmon-UCNP nanostructures has traditionally relied on either wet chemistry or nanolithography routes that are difficult to control, scale up, or both. In this work, we present a scalable nanofabrication process, capable of producing a massive array of gold-UCNP hybrid nanostructures over a few mm2 area and with excellent uniformity in the photoluminescence intensity. This new approach combines the scalability of the bottom-up self-assembly method and the precision of the top-down nanolithography approach. It provides an efficient alternative route for the production of plasmonically enhanced UCNPs. A detailed discussion on the optimization of the UCNP self-assembly, the gold nanodisk lithography, and the nanopattern transfer processes is presented here. Additionally, we showcase the potential of this new approach for fabricating mechanical force sensors based on the selective plasmonic enhancement of the UCNP emission. This new approach holds great potential in facilitating the production of plasmonically enhanced UCNPs that can be deployed for both imaging and sensing applications.

Optical force sensor based on plasmon modulated upconversion luminescence.

We report a novel force sensor exploiting the interaction between plasmonic nanostructures and upconversion nanoparticles (UCNPs). The nanosensor is composed of a gold nanodisk and UCNPs separated by a flexible polymer layer. The gold nanodisk is designed to exhibit a plasmon resonance that selectively enhances one of the emission bands of the UCNPs while leaving the other ones largely unaffected. As the nanosensor is compressed or stretched by an external force, the polymer layer thickness changes, modulating the plasmon-UCNP coupling. The resulting changes in the luminescence intensity provides the basis for sensing. Furthermore, the nanosensor employs ratiometric sensing which makes it highly robust against any environmental variations. Our nanosensors exhibit two orders of magnitude higher responsivity than previously reported UCNP-based force sensors. They can be prepared as an on-chip sensor array or in a colloidal solution, making them suitable for a variety of applications in biology and robotics.

Scattering reduction at near-infrared frequencies using plasmonic nanostructures.

Novel fabrication, detection and analysis approaches were employed to experimentally demonstrate scattering reduction by a plasmonic nanostructure operating at 1550 nm. The nanostructure consisted of a silicon nanorod surrounded by a plasmonic metamaterial cover comprised of eight gold nanowires and was fabricated by a combination of electron beam lithography, focused ion beam milling and dry and wet etching. The optical standing wave pattern of the device in the near-field was obtained using heterodyne near-field scanning optical microscopy. It was found that the spatial curvature of the interference fringes of the optical standing wave pattern was directly related to the scattering reduction of the device. The experiments were in excellent agreement with the theoretical predictions and suggested that the device reduced the scattering by 9.5 dB when compared to a bare silicon nanorod of diameter 240 nm and by 6 dB when compared to a bare silicon nanorod of diameter 160 nm.

True FRET-based sensing of pH via Separation of FRET and Photon Reabsorption.

Förster Resonance Energy Transfer (FRET)-based devices have been extensively researched as potential biosensors due to their highly localized responsivity. In particular, dye-conjugated upconverting nanoparticles (UCNPs) are among the most promising FRET-based sensor candidates. UCNPs have a multi-modal emission profile that allows for ratiometric sensing, and by conjugating a biosensitive dye to their surface, this profile can be used to measure localized variations in biological parameters. However, the complex nature of the UCNP energy profile as well as reabsorption of emitted photons must be taken into account in order to properly sense the target parameters. To our knowledge, no proposed UCNP-based sensor has accurately taken care of these intricacies. In this article, we account for these complexities by creating a FRET-based sensor that measures pH. This sensor utilizes Thulium ( Tm 3 + )-doped UCNPs and the fluorescent dye Fluorescein Isothiocyanate (FITC). We first demonstrate that photon reabsorption is a serious issue for the 475 nm Tm 3 + emission, thereby limiting its use in FRET-based sensing. We then show that by taking the ratio of the 646 and 800 nm emissions rather than the more popular 475 nm one, we are able to measure pH exclusively through FRET.

Enzyme Prodrug Therapy with Photo-Cross-Linkable Anti-EGFR Affibodies Conjugated to Upconverting Nanoparticles.

In this work, we demonstrate that a photo-cross-linkable conjugate of upconverting nanoparticles and cytosine deaminase can catalyze prodrug conversion specifically at tumor sites in vivo. Non-covalent association of proteins and peptides with cellular surfaces leads to receptor-mediated endocytosis and catabolic degradation. Recently, we showed that covalent attachment of proteins such as affibodies to cell receptors yields extended expression on cell surfaces with preservation of protein function. To adapt this technology for in vivo applications, conjugates were prepared from upconverting nanoparticles and fusion proteins of affibody and cytosine deaminase enzyme (UC-ACD). The affibody allows covalent photo-cross-linking to epidermal growth factor receptors (EGFRs) overexpressed on Caco-2 human colorectal cancer cells under near-infrared (NIR) light. Once bound, the cytosine deaminase portion of the fusion protein converts the prodrug 5-fluorocytosine (5-FC) to the anticancer drug 5-fluorouracil (5-FU). NIR covalent photoconjugation of UC-ACD to Caco-2 cells showed 4-fold higher retention than observed with cells that were not irradiated in vitro. Next, athymic mice expressing Caco-2 tumors showed 5-fold greater UC-ACD accumulation in the tumors than either conjugates without the CD enzyme or UC-ACDs in the absence of NIR excitation. With oral administration of 5-FC prodrug, tumors with photoconjugated UC-ACD yielded 2-fold slower growth than control groups, and median mouse survival increased from 28 days to 35 days. These experiments demonstrate that enzyme-decorated nanoparticles can remain viable after a single covalent photoconjugation in vivo, which can in turn localize prodrug conversion to tumor sites for multiple weeks.

Selective enhancement of upconversion luminescence for enhanced ratiometric sensing.

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted widespread interest in bioimaging and sensing due to their photostability, low excitation energy, and good tissue penetration. Plasmonic nanostructures, on the other hand, can enhance the luminescence of UCNPs by concentrating electric fields into a nanoscale volume. While the enhanced luminescence intensity is in principle beneficial to sensing, intensity-based sensing has limitations in absolute measurements. This deficiency can be overcome by employing ratiometric sensing in which intensity ratio, rather than intensity itself, is used to quantitatively determine the presence of analytes. The ratiometric sensing is advantageous because the intensity ratio is much less sensitive to the variations in the environment and the number of probe materials in the sensing volume. Here, we demonstrate a plasmonic nanostructure with upconversion nanoparticles for an enhanced ratiometric sensing platform. The plasmonic nanostructure is composed of UCNPs, an indium tin oxide (ITO) spacer layer and an Au nanodisk. The nanostructure is designed such that the plasmon resonance selectively enhances the red luminescence of NaYGdF4:Yb3+, Er3+ UCNPs while leaving the green luminescence unaffected, thereby increasing the dynamic range and achievable sensitivity of the red-to-green (R/G) intensity ratio. We observed a 4-fold enhancement in the R/G ratio and also a drastic reduction in the signal uncertainty. This work advances our knowledge of the optical interaction between UCNPs and plasmonic nanostructures and also provides a foundation for improved ratiometric sensing in biomedical applications.

High-Efficiency Solar Vapor Generation Boosted by a Solar-Induced Updraft with Biomimetic 3D Structures.

Sunlight-based desalination is one of the most environment-friendly, low-cost methods for obtaining freshwater on the planet. We implemented a biomimetic three-dimensional (3D) solar evaporator, improved by a solar-induced air-flow updraft. A carbon-coated polyvinyl alcohol (PVA) foam allowed us to achieve perfect absorption of ultrabroadband sunlight and continuously provide water to tall 3D structures. Integrating the convection flower (Amorphophallus titanum) and solar chimney structure, we proposed a bio-inspired 3D solar evaporator system that generates an updraft airflow. This updraft replaces saturated vapor between neighboring PVA foams with dry air, resulting in a significant increase in the effectiveness of dry air-water contact interfaces. Under the 1 sun condition (1 kW m-2), we achieve a high solar-vapor conversion efficiency of 95.9%.