Two-photon Excited Luminescence Research Articles

Temporal Dynamics of Collective Resonances in Periodic Metasurfaces.

Temporal dynamics of confined optical fields can provide valuable insights into light-matter interactions in complex optical systems, going beyond their frequency-domain description. Here, we present a new experimental approach based on interferometric autocorrelation (IAC) that reveals the dynamics of optical near-fields enhanced by collective resonances in periodic metasurfaces. We focus on probing the resonances known as waveguide-plasmon polaritons, which are supported by plasmonic nanoparticle arrays coupled to a slab waveguide. To probe the resonant near-field enhancement, our IAC measurements make use of enhanced two-photon excited luminescence (TPEL) from semiconductor quantum dots deposited on the nanoparticle arrays. Thanks to the incoherent character of TPEL, the measurements are only sensitive to the fundamental optical fields and therefore can reveal clear signatures of their coherent temporal dynamics. In particular, we show that the excitation of a high-Q collective resonance gives rise to interference fringes at time delays as large as 500 fs, much greater than the incident pulse duration (150 fs). Based on these signatures, the basic characteristics of the resonances can be determined, including their Q factors, which are found to exceed 200. Furthermore, the measurements also reveal temporal beating between two different resonances, providing information on their frequencies and their relative contribution to the field enhancement. Finally, we present an approach to enhance the visibility of the resonances hidden in the IAC curves by converting them into spectrograms, which greatly facilitates the analysis and interpretation of the results. Our findings open up new perspectives on time-resolved studies of collective resonances in metasurfaces and other multiresonant systems.

Two-photon excited luminescence of sulfur quantum dots for heavy metal ion detection.

Spectrally-resolved third-order nonlinear optical properties of water-dispersed sulfur quantum dots (SQDs) were investigated in the wavelength range from 740 nm to 820 nm with the two-photon excited emission technique using a tunable femtosecond laser system. The maximum value of the two-photon absorption (TPA) cross-section (σ2) for ∼5.4 nm size SQDs was found to be 185 GM (Goeppert-Mayer unit), while the two-photon brightness (σ2 × η) was found to be 1.5 GM at 780 nm, the wavelength being in the first biological transmittance window. The TPA properties are presented here as appropriate cross-sections normalized per molecular weight which enables meaningful comparison of the nonlinear factors of the studied quantum dots with those of various nanomaterials. The optimized TPA properties of these hydrophilic colloidal SQDs may be potentially useful for detection of Fe3+ metal ions. The experimentally determined limit of Fe3+ detection for both one- and two-photon regime was 10 μmol L-1 (0.6 μg mL-1). Förster resonance energy transfer between SQDs as donors and Fe3+ metal ions as acceptors was confirmed as one of the possible detection mechanisms using a time-correlated single photon counting technique.

Two-photon excited luminescence of structural light enhancement in subwavelength SiO2 coating europium ion-doped paramagnetic gadolinium oxide nanoparticle and application for magnetic resonance imaging

BackgroundOxides of lanthanide rare-earth elements show great potential in the fields of imaging and therapeutics due to their unique electrical, optical and magnetic properties. Oxides of lanthanide-based nanoparticles enable high-resolution imaging of biological tissues by magnetic resonance imaging (MRI), computed tomography (CT) imaging, and fluorescence imaging. In addition, they can be used to detect, treat, and regulate diseases by fine-tuning their structure and function. It remains challenging to achieve safer, efficient, and more sensitive nanoparticles for clinical applications through the structural design of functional and nanostructured rare-earth materials.ResultIn this study, we designed a mesoporous silica-coated core–shell structure of europium oxide ions to obtain near-infrared two-photon excitation fluorescence while maintaining high contrast and resolution in MRI. We designed enhanced 800 nm photoexcitation nanostructures, which were simulated by the finite-difference method (FDM) and finite-difference time-domain method (FDTD). The nanoparticle structure, two-photon absorption, up-conversion fluorescence, magnetic properties, cytotoxicity, and MRI were investigated in vivo and in vitro. The nanoparticle has an extremely strong optical fluorescence response and multiple excitation peaks in the visible light band under the 405 nm continuous-wave laser excitation. The nanoparticle was found to possess typical optical nonlinearity induced by two-photon absorption by ultrafast laser Z-scan technique. Two-photon excited fluorescence of visible red light at wavelengths of 615 nm and 701 nm, respectively, under excitation of the more biocompatible near-infrared (pulsed laser at 800 nm). In an in vitro MRI study, a T1 relaxation rate of 6.24 mM−1 s−1 was observed. MRI in vivo showed that the nanoparticles could significantly enhance the signal intensity in liver tissue.ConclusionsThese results suggest that this sample has applied potential in visible light fluorescence imaging and MRI.

Research and Design of Aggregation-Induced Phosphorescent Materials for Time-Resolved Two-Photon Excited Luminescence Imaging.

Pure organic two-photon excited room temperature phosphorescent (RTP) materials have attracted great attention for time-resolved imaging due to their long emission lifetime and high resolution. The materials with an aromatic carbonyl group exhibit aggregation-induced emission (AIE) and RTP characteristics simultaneously. Here, we deeply explored the nature of aggregation-induced phosphorescence (AIP), especially the relationship between molecular configuration and optical properties. It was found that aggregation effect can suppress geometrical vibrations and regulate energy difference between S1 and T1. The aromatic carbonyl group plays significant roles in changing electronic configuration, resulting in large Stokes shift and spin-orbit coupling. It also leads to small transition dipole moment, decreasing two-photon absorption cross section and radiative decay rate. To improve two-photon absorption properties, we further designed a π-conjugated compound with large two-photon absorption cross section in the biological window (36.40 GM/656 nm) and AIP characteristics, which is a potential material in the application of time-resolved two-photon excited imaging.

Large third-order optical nonlinearities of two-dimensional CsPbBr3 nanoplatelets

Metal halide perovskites show considerable optical nonlinearity and could be used for cost-effective nonlinear optical devices if their nonlinear susceptibilities can be improved. Here, we report large optical nonlinearity, including third-order nonlinear absorption, refraction, and two-photon absorption excited luminescence, of CsPbBr3 nanoplatelets with a thickness of two or three atomic layers and a plane size of about 60 nm. Specifically, the nonlinear absorption was mainly induced by two-photon absorption at low incident powers, and the nonlinear absorption cross section reached 2.15 × 107 GM. It is two orders of magnitude larger than that of CsPbBr3 nanocrystals, which makes them an ideal optical limiting material. Furthermore, the nanoplatelets exhibited large self-phase modulation-induced nonlinear refraction, and the figures of merit W and T satisfied W >1 and T <1, which allow for optical switching. The large optical nonlinearity of CsPbBr3 nanoplatelets provides a basis for multifunctional applications in nonlinear optical devices.

Plasmonic Enhancement of Two-Photon Excited Luminescence of Gold Nanoclusters.

Plasmonic-enhanced luminescence of single molecules enables imaging and detection of low quantities of fluorophores, down to individual molecules. In this work, we present two-photon excited luminescence of single gold nanoclusters, Au18(SG)14, in close proximity to bare gold nanorods (AuNRs). We observed 25-times enhanced emission of gold nanoclusters (AuNCs) in near infrared region, which was mainly attributed to the resonant excitation of localized surface plasmon resonance (LSPR) of AuNRs and spectral overlap of LSPR band with photoluminescence of AuNCs. This work is an initial step in application of combined nanoparticles: gold nanorods and ultrasmall nanoclusters in a wide range of multiphoton imaging and biosensing applications.

Two-Photon Excited Luminescence of NV-Centers and Stimulated Raman Scattering in Nanodiamonds

Two-Photon Excited Luminescence of NV-Centers and Stimulated Raman Scattering in Nanodiamonds

Methylhydrazinium]2PbBr4, a Ferroelectric Hybrid Organic–Inorganic Perovskite with Multiple Nonlinear Optical Outputs

An expansive library of structurally complex two-dimensional (2D) and three-dimensional (3D) lead halide perovskites has emerged over the past decade, finding applications in various aspects of photon management: photovoltaics, photodetection, light emission, and nonlinear optics. Needless to say, the highest degree of structural plasticity enjoys the former group, offering a rich playground for modifications of relevant optoelectronic parameters such as exciton energy. Structural tailorability is reflected in the ease of modification of the chemistry of the organic layers residing between inorganic slabs. In this vein, we show that the introduction of methylhydrazinium cation (MHy+, CH3NH2NH2+) into 2D perovskite gives a material with a record low separation of the inorganic layers (8.91 Å at 300 K). Optical studies showed that MHy2PbBr4 features the most red-shifted excitonic absorption among all known A2PbBr4 compounds as well as a small exciton binding energy of 99.9 meV. MHy2PbBr4 crystallizes in polar Pmn21 symmetry at room emperature (phase III) and at 351 K undergoes a phase transition to modulated Pmnm phase (II) followed by another phase transition at 371 K to Pmnm phase (I). The ferroelectric property of room-temperature phase III is inferred from switching of the pyrocurrent, dielectric measurements, and optical birefringence results. MHy2PbBr4 exhibits multiple nonlinear optical phenomena such as second-harmonic generation, third-harmonic generation, two-photon excited luminescence, and multiphoton excited luminescence. Analysis of MHy2PbBr4 single-crystal luminescence spectra obtained through linear and nonlinear optical excitation pathways indicates that free exciton emission is readily probed by the ultraviolet excitation, whereas crumpled exciton emission is detected under two- and multiphoton excitation conditions. Overall, our results demonstrate that incorporation of MHy+ into the organic layer is an emergent strategy for obtaining a 2D perovskite with polar character and multifunctional properties.

Self-assembled ultrafine CsPbBr3 perovskite nanowires for polarized light detection

One-dimensional (1D) metal halide perovskite nanowire (NW) arrays with high absorption efficiency, emission yield and dielectric constants, as well as anisotropic optoelectronic properties have found applications in energy harvesting, flexible electronics, and biomedical imaging devices. Here, a modified two-step solvothermal method is developed for the synthesis of self-assembled cubic CsPbBr3 NW arrays. This method provides facile access to continuous and uniform ultrafine perovskite NWs and well-aligned pure perovskite NW arrayed architectures. Under excitation at 365 nm, the CsPbBr3 NWs give a strong blue emission observable to the naked eyes. The CsPbBr3 NWs also exhibit strong two-photon excited luminescence under the irradiation with an 800 nm pulse laser. By rotating the polarization angle of the 800 nm laser, strong polarization dependence with a polarization degree up to ∼0.49 is demonstrated in the self-assembled CsPbBr3 NW array, although the CsPbBr3 NWs have an isotropic cubic structure. Based on density functional theory (DFT) calculations, this polarization-dependent emission is correlated with the anisotropic charge density distribution of the perovskite NWs. These findings suggest that the ultrafine CsPbBr3 NWs with a well-defined self-assembled architecture could be applied as next-generation polarization-sensitive photoelectronic detection materials.

Two-Photon Excited Luminescence in Polyethylene and Polytetrafluoroethylene

Luminescence spectra of polytetrafluoroethylene (Teflon), a Teflon film, and a polyethylene film are registered in wide wavelength range under excitation by radiations with different wavelengths. For the first time, we detect two-photon-excited luminescence in polymers at low intensity of exciting light. In Teflon, we also register luminescence in the blue range under excitation by ruby laser pulses.

Effect of Zinc Atmosphere upon Doping ZnSe : Fe Crystals on the Composition and Distribution of Impurity-Defect Centers

Zinc selenide crystals doped with iron by high-temperature diffusion in zinc and argon atmospheres are studied by the two-photon confocal microscopy. The effect of the atmosphere on the spectra and spatial distribution of two-photon excited luminescence in the range from 425 to 725 nm is studied. It is shown that doping with zinc results in the absence of impurity-defect centers formed in samples doped in an inert argon atmosphere.

Two-photon excited luminescence and second-harmonic generation in quinacridone microstructures

Nonlinear optical microscopy was employed to investigate the properties of microstructures of quinacridone, a hydrogen-bonded pigment, derivative of quinacridine. Recently, quinacridone hierarchical microstructures (μ-QNC) having different nature-inspired morphologies were reported, e.g. in the shape of hedgehogs formed by self-assembled nano-needles. We find that such microcrystals have structure-dependent linear optical properties and exhibit strong two-photon excited fluorescence when irradiated with a near-infrared femtosecond laser. μ-QNCs exhibit different nonlinear optical properties for different crystal structures, including the emergence of symmetry-forbidden second-harmonic generation.

Two-photon excited luminescence in POPOP under pulse-periodic laser excitation

The spectra of two-photon-excited luminescence were registered in a polycrystalline aromatic compound POPOP. The two-photon luminescence in this substance was excited by the second optical harmonic of a solid-state neodymium-doped yttrium lithium fluoride laser (λ = 527 nm) and a copper vapor laser (λ = 510.6 nm). It is shown that the intensity of two-photon-excited luminescence depends nonlinearly on the intensity of an exciting radiation. It has been established that the intensity of the two-photon-excited luminescence is comparable to the intensity of Raman scattering under certain excitation conditions.

Enhanced one-photon and two-photon excited luminescence of polymer-stabilized AuAg nanoclusters aggregates

Gold and silver nanoclusters aggregates have gained significant attention as their optical properties and chemical stability surpasses those of individual nanoclusters. Here, we present a systematic investigation of aggregation-induced changes of morphology and optical properties of glutathione-stabilized silver-doped gold nanoclusters (AuAg NCs). We show that the silver-doped clusters have the ability to spontaneously aggregate in solution, but in order to stabilize their structure and enhance the one-photon (1 P) and two-photon (2 P) properties we used poly(allylamine hydrochloride) (PAH) matrix. This resulted in obtaining NCs superstructures having narrow size distribution and efficient 1 P and 2 P excited photoluminescence.

Sensing Biomolecular Interactions by the Luminescence of a Planar Gold Film.

We describe the operating principle and performance of a recently developed surface plasmon-enhanced optical sensor that utilizes two-photon excited luminescence of a planar gold film as the reporter signal. The sensor enables direct visualization of nanoscopic binding events near a sensing surface. Light is coupled to the Au/sample interface in an objective-based Kretschmann configuration to excite surface plasmon polariton (SPP) modes at a metal-dielectric interface. The gold luminescence induced by the confined optical field between the particle and the film is detected in the epi-direction by a far-field camera where individual binding events show up as diffraction limited bright spots against a dark background. We study the sensor's emission spectrum and the distance dependence between the target and substrate, which both suggest that the optical signal of the sensor originates from electron-hole pair excitations in the planar Au film. In addition, we show that the well-behaved pointspread function of the sensor enables a straightforward implementation of super-resolution techniques. Finally, we demonstrate the utility of the sensor for detecting DNA binding events, underlining the sensor's usefulness for label-free imaging of nanoscopic particles and biomolecular interactions.

Homochiral Cu(I) Coordination Polymers Based on a Double-Stranded Helical Building Block from Achiral Ligands: Symmetry-Breaking Crystallization, Photophysical and Photocatalytic Properties.

A pair of homochiral coordination polymers, [Cu(DPT)]n (1M and 1P, HDPT = 3,5-di-4-pyridinyl-2H-tetrazole), were assembled from achiral precursors. Crystal structure analysis showed that they are chiral three-dimensional (3D) coordination polymers based on a new double-stranded helical building block that is composed of two different 1D helices. Interestingly, rare symmetry-breaking crystallization was observed, in which the possibility of obtaining enantio-enriched bulk product with excessive M enantiomers (1-A) was obviously higher than that for P enantiomers (1-B) as demonstrated in multiple, repeated experiments with single-crystal diffraction and vibrational circular dichroism (VCD) spectra. Moreover, compound [Cu(DPT)]n shows good chemical stability in water, with pH values ranging from 3 to 13, as well as in many common organic solvents. Photophysical properties, including thermochromic properties and two-photon excited luminescence, were studied, and the potential for applications in temperature sensing was exhibited. In addition, the photocatalytic degradation of methylene blue in water indicated that compound [Cu(DPT)]n can be used as a photocatalyst.

Bi‐Modal Nonlinear Optical Contrast from Si Nanoparticles for Cancer Theranostics

AbstractPresenting a safe alternative to conventional compound quantum dots and other functional nanostructures, nanosilicon can offer a series of breakthrough hyperthermia‐based therapies under near‐infrared, radiofrequency, ultrasound, etc., excitation, but the size range to sensitize these therapies is typically too large (>10 nm) to enable efficient imaging functionality based on photoluminescence properties of quantum‐confined excitonic states. Here, it is shown that large Si nanoparticles (NPs) are capable of providing two‐photon excited luminescence (TPEL) and second harmonic generation (SHG) responses, much exceeding that of smaller Si NPs, which promises their use as probes for bi‐modal nonlinear optical bioimaging. It is finally demonstrated that the combination of TPEL and SHG channels makes possible efficient tracing of both separated Si NPs and their aggregations in different cell compartments, while the resolution of such an approach is enough to obtain 3D images. The obtained bi‐modal contrast provides lacking imaging functionality for large Si NPs and promises the development of novel cancer theranostic modalities on their basis.

Nonlinear plasmonic behavior of nanohole arrays in thin gold films for imaging lipids

We demonstrate linear and nonlinear plasmonic behaviors of periodic nanohole arrays in thin gold (Au) films with varying periodicities. As expected, the linear optical transmission spectra of the nanohole arrays show a red-shift of the resonance wavelength and Wood's anomaly with increasing hole spacing. The optical transmission and electric near-field intensity distribution of the nanohole arrays are simulated using the finite element method. The nonlinear plasmonic behavior of the nanohole arrays is studied by using picosecond pulsed excitation at near-infrared wavelengths. The characteristic nonlinear signals indicating two-photon excited luminescence (TPEL), sum frequency generation, second harmonic generation, and four-wave mixing (FWM) are observed. A maximum FWM/TPEL signal intensity ratio is achieved for nanohole arrays with a periodicity of 500 nm. Furthermore, the significant FWM signal intensity and contrast compared to the background were harnessed to demonstrate the ability of surface-enhanced coherent anti-Stokes Raman scattering to visualize low concentrations of lipids deposited on the nanohole array with a periodicity of 500 nm.

Natural zeolite for adsorbing and release of functional materials.

Using multiphoton microscopy (MPM), we demonstrated that effective inducing of two-photon excited luminescence and second-harmonic generation signals in nano/microparticles of clinoptilolite type of zeolite (CZ) by femtosecond near-infrared laser excitation can be successfully utilized in multiphoton imaging of the drug adsorption processes. Adsorption of photodynamic active dyes (hypericin, chlorin e6, methylene blue, and fluorescein) and their release from CZ pores in the presence of biomolecules, such as collagen from bovine Achilles tendon, albumin, and hemoglobin, were investigated by absorption and fluorescence spectrometry. To quantify the experimental results on hypericin release, here we use a kinetic curves fitting approach and calculate hypericin release rates in different environments. This approach allows to compare various mathematical models and uses more parameters to better characterize drug release profiles. In addition, magnetic CZ particles were fabricated and proposed as a promising material for drug delivery and controlled release in biological systems. Optical spectrometry and MPM are effective approaches that may reveal potential of natural zeolites in controlled drug delivery and biomedical imaging.

Two-Photon Imaging of 3D Organization of Bimetallic AuAg Nanoclusters in DNA Matrix.

We report on two-photon excitation properties of small silver-doped gold nanoclusters (AuAgNCs) and on their three-dimensional arrangement in a hybrid system composed of DNA liquid crystals (LCs) and AuAgNCs. UV-vis and fluorescence spectroscopy, transmission electron microscopy (TEM), and multiphoton excitation spectroscopy were used to characterize the nanoparticles. We show that AuAgNCs exhibit two-photon excited luminescence (2PL) emission and second-harmonic generation (SHG) and that these properties remain the same in liquid crystalline matrix. The results are described in detail and discussed in the context of possible imaging application of AuAgNC and specific AuAgNCs organization induced by liquid crystalline ordering of DNA molecules.