Nonreciprocal transmission in a nonlinear coupled heterostructure.

A nonlinear coupled heterostructure, metal-nonlinear-metal-insulator-metal, is proposed. The heterostructure is a non-Hermitian system that possesses reciprocal and nonreciprocal optical transmission characteristics. With low incident power, linear optical characteristic is observed whereas at high incident power, nonlinear optical characteristics is observed. Under the low incident power there is no nonlinear effect, the forward and backward transmission are reciprocal. With appropriate geometric parameters, for forward propagation two exceptional points where the reflection coefficients equal zero can be obtained simultaneously. With high power incident nonlinear effect becomes significant, leading to reciprocity broken and optical bistability observed. We investigated the behaviours of forward and backward transmission as well as the optical bistability under different incident powers using nonlinear coupled mode theory. There is excellent agreement between the simulation results and theoretical modelling. The theoretical study of proposed heterostructure shows it has several novel optical responses under different incident conditions. The proposed heterostructure is relatively simple to fabricate and therefore can be experimentally verified with ease. These unique optical characteristics allow more possibilities for the design of multifunctional devices.

Double exceptional points in grating coupled metal-insulator-metal heterostructure.

In this work we theoretically study the exceptional points and reflection spectra characteristics of a grating coupled metal-insulator-metal heterostructure, which is a non-Hermitian system. Our results show that by selecting suitable geometrical parameters with grating periodicity @150 nm, that satisfy zero reflection condition, double exceptional points appear in a mode bifurcation regime. Furthermore, the thickness of partition metal layer between two cavities plays an important role in controlling the reflection properties of the heterostructure. There is a clear mode splitting when the partition layer allows strong coupling between the two cavity modes. Conversely, in weak coupling regime the mode splitting becomes too close to be distinguished. Moreover, the vanishing of reflection leads to unidirectional reflectionless propagation, which is also known as unidirectional invisibility. With grating periodicity ≥400nm, the transmissions for forward and backward incident directions are no longer the same due to the generation of diffraction. High contrast ratio (≈1) between the two incident directions leads to asymmetric transmission. This work lays the basis for designing double exceptional points and asymmetric transmission in coupled non-Hermitian photonics system. The proposed heterostructure can be a good candidate for new generation optical communications, optical sensing, photo-detection, and nano-photonic devices.

Frequency-Upconverted Stimulated Emission by Up to Six-Photon Excitation from Highly Extended Spiro-Fused Ladder-Type Oligo(p-phenylene)s.

Frequency-upconverted fluorescence and stimulated emission induced by multiphoton absorption (MPA) have attracted much interest. As compared with low-order MPA processes, the construction of high-order MPA processes is highly desirable and rather attractive, yet remains a formidable challenge due to its inherent low transition probability. We report the observation of the first experimental frequency-upconverted fluorescence and stimulated emission by simultaneous six-photon excitation in an organic molecular system. The well-designed organic conjugated system based on cross-shaped spiro-fused ladder-type oligo(p-phenylene)s (SpL-z, z=1-3) manifests reasonably high MPA cross-sections and brilliant luminescence emission simultaneously. The six-photon absorption cross-section of SpL-3 with an extended π-conjugation was evaluated as 8.67×10-169  cm12 s5 photon-5 . Exceptionally efficient 2- to 6-photon excited stimulated emission was achieved under near-infrared laser excitation.

Gigantic electric-field-induced second harmonic generation from an organic conjugated polymer enhanced by a band-edge effect.

Electric-field-induced second harmonic generation (EFISH), a third-order nonlinear process, arises from the interaction between the electric field of an external bias and that of two incident photons. EFISH can be used to dynamically control the nonlinear optical response of materials and is therefore promising for active nonlinear devices. However, it has been challenging to achieve a strong modulation with EFISH in conventional nonlinear materials. Here, we report a large tunability of an EFISH signal from a subwavelength-thick polymer film sandwiched between a transparent electrode and a metallic mirror. By exploiting the band-edge-enhanced third-order nonlinear susceptibility of the organic conjugated polymer, we successfully demonstrate a gigantic EFISH effect with a modulation ratio up to 422% V- 1 at a pumping wavelength of 840 nm. The band-edge-enhanced EFISH opens new avenues for modulating the intensity of SHG signals and for controlling nonlinear electro-optic interactions in nanophotonic devices.

Thermally Activated Delayed Fluorescence Host for High Performance Organic Light-Emitting Diodes.

Thermally activated delayed florescence (TADF) materials can be an efficient host in organic LED (OLED). It is because it is possible to couple energetically the emission energy level of a dopant to the energy levels in the TADF material. In this work fluorescent emitters 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5 H,11H-10-(2-benzothiazolyl)quinolizino-9,9a,1gh coumarin (c545t) and 5,6,11,12-tetraphenyltetracene (rubrene) were used as dopants in a blended TADF host; tris(4-carbazoyl-9-ylphenyl)amine (TCTA) with 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine (Tm3PyBPZ). The blended TADF host has an energy difference between the singlet and triplet excited states (ΔEST) around 27 meV with the yield of reverse intersystem crossing (ФRISC) nearly 100%. This high ФRISC yield enhances the OLED performance with the c545t doped OLED having 11.9% external quantum efficiency and 10% for the rubrene doped OLED.

Quantitative Analysis of Charge Distribution in Bi-Emissive layer White Organic Light-Emitting Diodes with Two Fluorescent Dopants.

This work seeks to establish a quantitative method which can estimate the holes and electrons ratio in the emission zones. We fabricated multilayered white organic light-emitting diodes (WOLEDs) with the device structure of ITO/NPB(80 nm)/MADN:BUBD-1(7%)(20 nm)/MADN:DCJTB(0.3%)(20 nm)/TPBi(X nm)/LiF(2 nm)/Al as a case study on the charge recombination distribution in the emissive layer. The result shows a trend in the charge recombination ratio depending on the electron transport layer thickness. We obtained an empirical relationship between electron transport layer thicknesses and emission ratio in EML. In addition, the electroluminescent spectra were analyzed by fitting a Gaussian distribution for the two emissive layers to calculate the intensity ratio of the energy transitions. The arrival time of hole and electrons from each electrode was determined using the thickness and mobility of TPBi as electron transport layer. From these initial results, we derived an empirical mechanism to meet with a linear relationship that can allow us to design custom- made WOLEDs.

Ruthenium(II) Complex Incorporated UiO-67 Metal-Organic Framework Nanoparticles for Enhanced Two-Photon Fluorescence Imaging and Photodynamic Cancer Therapy.

Ruthenium(II) tris(bipyridyl) cationic complex (Ru(bpy)32+) incorporated UiO-67 (Universitetet i Oslo) nanoscale metal-organic frameworks (NMOFs) with an average diameter of ∼92 nm were developed as theranostic nanoplatform for in vitro two-photon fluorescence imaging and photodynamic therapy. After incorporation into porous UiO-67 nanoparticles, the quantum yield, luminescence lifetime, and two-photon fluorescence intensity of Ru(bpy)32+ guest molecules were much improved owing to the steric confinement effect of MOF pores. Benefiting from these merits, the as-synthesized nanoparticles managed to be internalized by A549 cells while providing excellent red fluorescence in cytoplasm upon excitation with 880 nm irradiation. Photodynamic therapeutic application of the Ru(bpy)32+-incorporated UiO-67 NMOFs was investigated in vitro. The Ru(bpy)32+-incorporated UiO-67 NMOFs exhibited good biocompatibility without irradiation while having good cell-killing rates upon irradiation. In view of these facts, the developed Ru(bpy)32+-incorporated NMOFs give a new potential pathway to achieve enhanced two-photon fluorescence imaging and photodynamic therapy.

Highly Efficient Multiphoton-Pumped Frequency-Upconversion Stimulated Blue Emission with Ultralow Threshold from Highly Extended Ladder-Type Oligo(p-phenylene)s.

A series of highly extended π-conjugated ladder-type oligo(p-phenylene)s containing up to 10 phenyl rings with (L)-Ph(n)-NPh (n=7-10) or without diphenylamino endcaps (L)-Ph(n) (n=7 and 8) were synthesized and investigated for their multiphoton absorption properties for frequency upconverted blue ASE/lasing. Extremely large two-photon absorption (2PA) cross-sections and highly efficient 2PA ASE/lasing with ultralow threshold were achieved. (L)-Ph(10)-NPh exhibits the highest intrinsic 2PA cross-section of 3643 GM for a blue emissive organic fluorophore reported so far. The record-high 2PA pumped ASE/lasing efficiency of 2.06 % was obtained by un-endcapped oligomer, (L)-Ph(8) rather than that with larger σ2 , suggesting that a molecule with larger σ2 is not guaranteed to exhibit higher η2 . All of these oligomers exhibit exceptionally ultralow 2PA pumped ASE/lasing thresholds, among which the lowest 2PA pumped threshold of circa 0.26 µJ was achieved by (L)-Ph(10)-NPh.

Self-Assembly of Electron Donor-Acceptor-Based Carbazole Derivatives: Novel Fluorescent Organic Nanoprobes for Both One- and Two-Photon Cellular Imaging.

In this study, we report fluorescent organic nanoprobes with intense blue, green, and orange-red emissions prepared by self-assembling three carbazole derivatives into nanorods/nanoparticles. The three compounds consist of two or four electron-donating carbazole groups linked to a central dicyanobenzene electron acceptor. Steric hindrance from the carbazole groups leads to noncoplanar 3D molecular structures favorable to fluorescence in the solid state, while the donor-acceptor structures endow the molecules with good two-photon excited emission properties. The fluorescent organic nanoprobes exhibit good water dispersibility, low cytotoxicity, superior resistance against photodegradation and photobleaching. Both one- and two-photon fluorescent imaging were shown in the A549 cell line. Two-photon fluorescence imaging with the fluorescent probes was demonstrated to be more effective in visualizing and distinguishing cellular details compared to conventional one-photon fluorescence imaging.

Giant Nonlinear Optical Activity of Achiral Origin in Planar Metasurfaces with Quadratic and Cubic Nonlinearities.

3D chirality is shown to be unnecessary for introducing strong circular dichroism for harmonic generations. Specifically, near-unity circular dichroism for both second-harmonic generation and third-harmonic generations is demonstrated on suitably designed ultrathin plasmonic metasurfaces with only 2D planar chirality. The study opens up new routes for designing chip-type biosensing platform, which may allow for highly sensitive detection of bio- and chemical molecules with weak chirality.

Efficient Organic Light-Emitting Diode through Triplet Exciton Reharvesting by Employing Blended Electron Donor and Acceptor as the Emissive Layer.

A blended bimolecular exciplex formation was demonstrated between two individual donor and acceptor molecules, which are tris(4-carbazoyl-9-ylphenyl)amine (TCTA) and 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine (Tm3PyBPZ). The photoluminescence spectrum of the exciplex in the solid state showed an emission with a peak around 514 nm (∼2.49 eV). By applying this exciplex as an emitting layer, a highly efficient all-fluorescent organic lighting emitting diode with maximum efficiencies of 13.1% and 53.4 lm/W can be realized under an extremely low turn-on voltage of only 2.4 V. The thermally activated delayed fluorescence (TADF) process is believed to be responsible for the excellent device performance.

Helicity multiplexed broadband metasurface holograms.

Metasurfaces are engineered interfaces that contain a thin layer of plasmonic or dielectric nanostructures capable of manipulating light in a desirable manner. Advances in metasurfaces have led to various practical applications ranging from lensing to holography. Metasurface holograms that can be switched by the polarization state of incident light have been demonstrated for achieving polarization multiplexed functionalities. However, practical application of these devices has been limited by their capability for achieving high efficiency and high image quality. Here we experimentally demonstrate a helicity multiplexed metasurface hologram with high efficiency and good image fidelity over a broad range of frequencies. The metasurface hologram features the combination of two sets of hologram patterns operating with opposite incident helicities. Two symmetrically distributed off-axis images are interchangeable by controlling the helicity of the input light. The demonstrated helicity multiplexed metasurface hologram with its high performance opens avenues for future applications with functionality switchable optical devices.

Bioorthogonal Labeling, Bioimaging, and Photocytotoxicity Studies of Phosphorescent Ruthenium(II) Polypyridine Dibenzocyclooctyne Complexes.

The synthesis, characterization, photophysics, lipophilicity, and cellular properties of new phosphorescent ruthenium(II) polypyridine complexes functionalized with a dibenzocyclooctyne (DIBO) or amine moiety [Ru(N^N)2 (L)](PF6 )2 are reported (L=4-(13-N-(3,4:7,8-dibenzocyclooctyne-5-oxycarbonyl) amino-4,7,10-trioxa-tridecanyl-aminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-DIBO, N^N=2,2'-bipyridine bpy (1 a), 1,10-phenanthroline phen (2 a); L=4-(13-amino-4,7,10-trioxa-tridecanylaminocarbonyl-oxy-methyl)-4'-methyl-2,2'-bipyridine bpy-NH2 , N^N=bpy (1 b), phen (2 b)). The strain-promoted alkyne-azide cycloaddition (SPAAC) reaction of the DIBO complexes 1 a and 2 a with benzyl azide were studied. Also, the DIBO complexes 1 a and 2 a can selectively label N-azidoglycans located on the surface of CHO-K1 and A549 cells that were pretreated with 1,3,4,6-tetra-O-acetyl-N-azidoacetyl-D-mannosamine (Ac4 ManNAz). Additionally, the intracellular trafficking and localization of these biomolecules were monitored using laser-scanning confocal microscopy. Interestingly, the biolabeling and cellular uptake efficiency of the DIBO complexes 1 a and 2 a were cell-line dependent, as revealed by flow cytometry and ICP-MS. Furthermore, the complexes showed good biocompatibility toward the Ac4 ManNAz-pretreated cells in the dark, but exhibited photoinduced cytotoxicity due to the generation of singlet oxygen.

Continuous control of the nonlinearity phase for harmonic generations.

The capability of locally engineering the nonlinear optical properties of media is crucial in nonlinear optics. Although poling is the most widely employed technique for achieving locally controlled nonlinearity, it leads only to a binary nonlinear state, which is equivalent to a discrete phase change of π in the nonlinear polarizability. Here, inspired by the concept of spin-rotation coupling, we experimentally demonstrate nonlinear metasurfaces with homogeneous linear optical properties but spatially varying effective nonlinear polarizability with continuously controllable phase. The continuous phase control over the local nonlinearity is demonstrated for second and third harmonic generation by using nonlinear metasurfaces consisting of nanoantennas of C3 and C4 rotational symmetries, respectively. The continuous phase engineering of the effective nonlinear polarizability enables complete control over the propagation of harmonic generation signals. Therefore, this method seamlessly combines the generation and manipulation of harmonic waves, paving the way for highly compact nonlinear nanophotonic devices.

Study of sequential dexter energy transfer in high efficient phosphorescent white organic light-emitting diodes with single emissive layer.

In this study, we report our effort to realize high performance single emissive layer three color white phosphorescent organic light emitting diodes (PHOLEDs) through sequential Dexter energy transfer of blue, green and red dopants. The PHOLEDs had a structure of; ITO(1500 Å)/NPB(700 Å)/mCP:Firpic-x%:Ir(ppy)3-0.5%:Ir(piq)3-y%(300 Å)/TPBi(300 Å)/Liq(20 Å)/Al(1200 Å). The dopant concentrations of FIrpic, Ir(ppy)3 and Ir(piq)3 were adjusted and optimized to facilitate the preferred energy transfer processes attaining both the best luminous efficiency and CIE color coordinates. The presence of a deep trapping center for charge carriers in the emissive layer was confirmed by the observed red shift in electroluminescent spectra. White PHOLEDs, with phosphorescent dopant concentrations of FIrpic-8.0%:Ir(ppy)3-0.5%:Ir(piq)3-0.5% in the mCP host of the single emissive layer, had a maximum luminescence of 37,810 cd/m(2) at 11 V and a luminous efficiency of 48.10 cd/A at 5 V with CIE color coordinates of (0.35, 0.41).

Symmetry-selective third-harmonic generation from plasmonic metacrystals.

Nonlinear processes are often governed by selection rules imposed by the symmetries of the molecular configurations. The most well-known examples include the role of centrosymmetry breaking for the generation of even harmonics, and the selection rule related to the rotational symmetry in harmonic generation for fundamental beams with circular polarizations. While the role of centrosymmetry breaking in second harmonic generation has been extensively studied in plasmonic systems, the investigation of selection rules pertaining to circular polarization states of harmonic generation is limited to crystals, i.e., symmetries at the atomic level. In this Letter we demonstrate the rotational symmetry dependent third harmonic generation from nonlinear plasmonic metacrystals. We show that the selection rule can be imposed by the rotational symmetry of metacrystals embedded into an isotropic organic nonlinear thin film. The results presented here may open new avenues for designing symmetry-dependent nonlinear optical responses with tailored plasmonic nanostructures.

Efficient energy exchange between plasmon and cavity modes via Rabi-analogue splitting in a hybrid plasmonic nanocavity.

Plasmonic analogues of Rabi-splitting have been extensively studied in various metallic nanosystems hybridized with semiconductor quantum dots, nanocrystals and organic molecules, with a focus on the splitting energy gap where surface plasmon polaritons (SPPs) strongly couple with excitons. Similar strong coupling also occurs for individual metallic nanoparticles locating inside a photonic microcavity or nearby a waveguide due to the strong interaction between localized surface plasmons and photonic modes in the near-infrared wavelength range. In this work we study experimentally and theoretically the strong coupling between propagating SPPs and the Fabry-Perot (F-P) cavity mode in a metallic nanoparticle array-nanocavity hybrid system in the visible spectral range. The strong modal hybridization created giant modal anti-crossing which can be considered as the classical phenomenon of Rabi splitting i.e. a Rabi-analogue. In addition to the observation of a giant Rabi-analogue splitting energy of 148 meV at the strong coupling regime, we also reveal highly-efficient energy exchange between SPP and F-P modes at the low frequency dispersion branch through detailed numerical near-field studies and experimental phase delay analysis. The observed efficient mode conversion in the investigated plasmonic nanocavity is useful for designing novel nanophotonic devices, in which conventional photonic components need to be integrated with miniaturized plasmonic devices or vice versa.

Two-photon fluorescence probes for imaging of mitochondria and lysosomes.

Novel biocompatible cyanines show not only a very large two-photon cross-section of up to 5130 GM at 910 nm in aqueous medium for high-contrast and -brightness two-photon fluorescence live cell imaging but also highly selective subcellular localization properties including localization of mitochondria and lysosomes.

Star-shaped ladder-type ter(p-phenylene)s for efficient multiphoton absorption.

Star-shaped ladder-type ter(p-phenylene)s exhibit remarkably efficient multiphoton absorption properties with 2PA cross-section up to 2579 GM at 700 nm and 3PA cross-section up to 3.35 × 10(-76) cm(6) s(2) in the femtosecond regime for a blue-emissive molecule despite having such a short π-conjugated framework.

Sharp plasmonic resonance on gold gratings in amplitude and phase domains.

In this work, we experimentally studied sharp plasmonic resonance on gold gratings in both amplitude and phase domains using a spectroscopic ellipsometry technique. We used numerical and analytical models to analyze the phase delay of TM and TE waves under a surface plasmon excitation condition, and the calculated result fits well with the experimental observations. In addition, the ellipsometry method used here provides an important tool to characterize the phase information in plasmonic and metamaterial devices.