Up-conversion Technique Research Articles

Solvent effect on multiple emission and ultrafast dynamics of higher excited states

We present ultrafast-depopulation-dynamics of higher-lying-excited-states using femtosecond fluorescence up-conversion techniques for two near-infrared (NIR) tricarbocyanine dyes (IR144 and IR140) in primary alcohols. With visible excitation wavelengths, such dyes show two distinct emission-bands with large peak wavelength difference: one at the visible region: S2 → S0, and the other at NIR region: S1 → S0. We show that exact band-positions, intensities, and fluorescence-decay-timescales (τ) depend strongly on viscosity and polarity of solvents. Interestingly, though the faster component of τ increased for IR144 with increasing viscosity and chain-length of alcohols, the reverse was seen for IR140, indicating the possible formation of ion-pair of IR140 with alcohols.

Effect of Microheterogeneity of Different Aqueous Binary Mixtures on the Proton Transfer Dynamics of [2,2'-Bipyridyl]-3,3'-diol: A Femtosecond Fluorescence Upconversion Study.

In this article, we have investigated the excited-state intramolecular double proton transfer dynamics of [2,2′-bipyridyl]-3,3′-diol, BP(OH)2, in three alcohol–water binary mixtures, namely, ethanol (EtOH)–water, n-propanol (PrOH)–water, tert-butyl alcohol (TBA)–water, and dimethyl sulfoxide (DMSO)–water utilizing the femtosecond fluorescence upconversion technique. We have found that in alcohol–water binary mixtures the proton transfer (PT) pathway of BP(OH)2 is sequential and the anomalous slowdown in PT dynamics is observed in mole fraction (χ) ranges χEtOH = 0.04–0.07, χEtOH = 0.23–0.28, χPrOH = 0.17–0.30, χTBA = 0.12–0.21, and χTBA = 0.40–0.46. Our study sheds light on the involvement of water network in the PT dynamics. Reduction in water accessibility due to the involvement of water molecules in cluster formation results in hindered PT dynamics, and this retardation is more for the TBA–water binary mixture compared to that for the other two mixtures. Additionally, we have found two anomalous regions for the DMSO–water binary mixture in ranges χDMSO = 0.12–0.16 and χDMSO = 0.26–0.34. However, most interestingly, beyond χDMSO = 0.40, we do not find any growth component in the femtosecond fluorescence upconversion trace, which may be due to the change in the PT mechanism from a sequential water-mediated pathway to a concerted intramolecular pathway.

Ultrafast fluorescence dynamics of DNA-based silver clusters.

Atomic-level understanding of the nature of the electronically excited states in ligand-stabilized metal nanoclusters (NCs) is a prerequisite for the design of new NCs with desired properties. In this study, we investigate the emission dynamics of a Ag-DNA complex using the fluorescence up-conversion technique. We show that most of the relaxation from the Franck-Condon state to the emissive state takes place in less than 100 fs, in spite of a relatively large Stokes shift of 4500 cm-1. This relaxation is much faster than typical solvent/DNA relaxation rates. A further small relaxation occurs with time constants ranging from a few to hundreds of picoseconds. We also calculate the Stokes shift for model complexes of a small three-atom Ag3+ cluster with cytosine and guanine. The results of our calculations show that a substantial geometry change of the Ag3+ cluster is observed in the S1 state of both complexes, which results in Stokes shifts comparable with the experimental value. We conclude that the Stokes shift in the Ag-DNA complex arises mostly due to the change in the geometry of the Ag cluster in the excited state rather than to the solvent/DNA reorganization. Also, a different structure of the Ag-DNA complex ("dark cluster"), the excited state of which decays in 200 fs, is observed. The nature of this ultrafast deactivation is unclear, which requires further investigations.

Electric field feedback for Magneto(elasto)Electric magnetometer development

Magneto(elasto)Electric (ME) sensors based on magnetostrictive-piezoelectric composites have been investigated to evaluate their performances to sense a magnetic signal. Previous results have shown that the dielectric loss noise in the piezoelectric layer exhibits as the dominant intrinsic noise at low frequencies, which limits the sensor performances. Also, it has intrinsically no DC capability. To avoid a part of this limitation, modulation detection methods are evaluated through a frequency up-conversion technique [1-4]. Moreover, classical magnetic field feedback techniques can be used to increase the dynamic range, the sensing stability and the system linearity, too. In this paper, we propose a new method to feedback the system by using both the magneto-capacitance modulation and an electric field feedback technique. Our development shows the feasibility of the method and the results match with the theoretical description and material properties. Even if the present results are not totally satisfactory, they give the proof of concept and yield a way for the development of very low power magnetometers.

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S1 state is the only significant product of the radiationless decay of the S2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

New Insight into the Origin of the Red/Near-Infrared Intense Fluorescence of a Crystalline 2-Hydroxychalcone Derivative: A Comprehensive Picture from the Excited-State Femtosecond Dynamics.

Fluorescence upconversion and transient absorption techniques are used to explain the source of the intense red/near-infrared emission of crystalline 4-dimethylamino-2'-hydroxychalcone. We found that the initially excited enol form undergoes tautomerization in 3 ps to form the keto tautomer. The latter is stable in the ground state as a consequence of J-type aggregation in the crystal packing and is manifested in an absorption peak at 550 nm that spectrally overlaps with the short-lived enol emission, leading to self-reabsorption and adding a factor to the complete depletion of the enol emission. Relaxation of the keto tautomer takes place in the form of intense fluorescence (600-750 nm) with 1.7 ns lifetime. The different spectroscopy in solution is due to vibrational cooling (300 fs), followed by solvation dynamics (5 ps in methanol) and twisting of the hydroxyphenyl ring (16 ps), before relaxation of the enol tautomer in the form of weak green fluorescence with 350 ps lifetime.

Expanding Anti-Stokes Shifting in Triplet-Triplet Annihilation Upconversion for In Vivo Anticancer Prodrug Activation.

A strategy to expand anti-Stokes shifting from the far-red to deep-blue region in metal-free triplet-triplet annihilation upconversion (TTA-UC) is presented. The method is demonstrated by in vivo titration of the photorelease of an anticancer prodrug. This new TTA system has robust brightness and the longest anti-Stokes shift of any reported TTA system. TTA core-shell-structured prodrug delivery capsules that benefit from these properties were developed; they can operate with low-power density far-red light-emitting diode light. These capsules contain mesoporous silica nanoparticles preloaded with TTA molecules as the core, and amphiphilic polymers encapsulating anticancer prodrug molecules as the shell. When stimulated by far-red light, the intense TTA upconversion blue emission in the system activates the anticancer prodrug molecules and shows effective tumor growth inhibition in vivo. This work paves the way to new organic TTA upconversion techniques that are applicable to in vivo photocontrollable drug release and other biophotonic applications.

Expanding Anti‐Stokes Shifting in Triplet–Triplet Annihilation Upconversion for In Vivo Anticancer Prodrug Activation

AbstractA strategy to expand anti‐Stokes shifting from the far‐red to deep‐blue region in metal‐free triplet–triplet annihilation upconversion (TTA‐UC) is presented. The method is demonstrated by in vivo titration of the photorelease of an anticancer prodrug. This new TTA system has robust brightness and the longest anti‐Stokes shift of any reported TTA system. TTA core–shell‐structured prodrug delivery capsules that benefit from these properties were developed; they can operate with low‐power density far‐red light‐emitting diode light. These capsules contain mesoporous silica nanoparticles preloaded with TTA molecules as the core, and amphiphilic polymers encapsulating anticancer prodrug molecules as the shell. When stimulated by far‐red light, the intense TTA upconversion blue emission in the system activates the anticancer prodrug molecules and shows effective tumor growth inhibition in vivo. This work paves the way to new organic TTA upconversion techniques that are applicable to in vivo photocontrollable drug release and other biophotonic applications.

Detection of Black Plastics in the Middle Infrared Spectrum (MIR) Using Photon Up-Conversion Technique for Polymer Recycling Purposes.

The identification of black polymers which contain about 0.5 to 3 mass percent soot or black master batch is still an essential problem in recycling sorting processes. Near infrared spectroscopy (NIRS) of non-black polymers offers a reliable and fast identification, and is therefore suitable for industrial application. NIRS is consequently widely used in polymer sorting plants. However, this method cannot be used for black polymers because small amounts of carbon black or soot absorb all light in the NIR spectral region. Spectroscopy in the mid infrared spectral region (MIR) offers a possibility to identify black polymers. MIR spectral measurements carried out with Fourier-transform infrared spectrometers (FTIR) are not fast enough to meet economic requirements in sorting plants. By contrast, spectrometer systems based on the photon up-conversion technique are fast and sensitive enough and can be applied to sort black polymer parts. Such a system is able to measure several thousand spectra per second hence is suitable for industrial applications. The results of spectral measurements of black polymers are presented.

Role of Dispersive Fluorous Interaction in the Solvation Dynamics of the Perfluoro Group Containing Molecules.

Perfluoro group containing molecules possess an important self-aggregation property through the fluorous (F···F) interaction which makes them useful for diverse applications such as medicinal chemistry, separation techniques, polymer technology, and biology. In this article, we have investigated the solvation dynamics of coumarin-153 (C153) and coumarin-6H (C6H) in ethanol (ETH), 2-fluoroethanol (MFE), and 2,2,2-trifluoroethanol (TFE) using the femtosecond upconversion technique and molecular dynamics (MD) simulation to understand the role of fluorous interaction between the solute and solvent molecules in the solvation dynamics of perfluoro group containing molecules. The femtosecond upconversion data show that the time scales of solvation dynamics of C6H in ETH, MFE, and TFE are approximately the same whereas the solvation dynamics of C153 in TFE is slow as compared to that of ETH and MFE. It has also been observed that the time scale of solvation dynamics of C6H in ETH and MFE is higher than that of C153 in the same solvents. MD simulation results show a qualitative agreement with the experimental data in terms of the time scale of the slow components of the solvation for all the systems. The experimental and simulation studies combined lead to the conclusion that the solvation dynamics of C6H in all solvents as well as C153 in ETH and MFE is mostly governed by the charge distribution of ester moieties (C═O and O) of dye molecules whereas the solvation of C153 in TFE is predominantly due to the dispersive fluorous interaction (F···F) between the perfluoro groups of the C153 and solvent molecules.

Hot-Carrier-Mediated Photon Upconversion in Metal-Decorated Quantum Wells

Manipulating the frequency of electromagnetic waves forms the core of many modern technologies, ranging from imaging and spectroscopy to radio and optical communication. The process of converting photons from higher to lower energy is easily accomplished and technologically widespread. However, upconversion, which is the process of converting lower-energy photons into higher-energy photons, is still a growing field of study with nascent applications and burgeoning interest. Here, we experimentally demonstrate a new photon upconversion technique mediated by hot carriers in plasmonic nanostructures. Hot holes and hot electrons generated via plasmon decay in illuminated metal nanoparticles are injected into an adjacent semiconductor quantum well where they radiatively recombine to emit higher-energy photons. Using GaN/InGaN quantum wells decorated with gold and silver nanoparticles, we show photon upconversion from 2.4 to 2.8 eV. The process scales linearly with illumination power and enables both geometry- and polarization-based tunability. The conversion of plasmonic losses into upconverted optical emission has the potential to impact bioimaging, on-chip wavelength conversion, and high-efficiency photovoltaics.

A fresh look into the time-resolved fluorescence of 8-hydroxy-1,3,6-pyrenetrisulfonate with the use of the fluorescence up-conversion technique

Abstract Steady-state and time-resolved fluorescence techniques were used to study the excited-state-proton-transfer (ESPT) process of 8-hydroxy-1,3,6-pyrenetrisulfonate (HPTS) in H 2 O and D 2 O. In this contribution we use the fluorescence up-conversion technique with a time resolution of ∼100 fs to monitor the short-time components of HPTS ROH (protonated) and RO − (deprotonated) signals. The ESPT rate constant, k PT , for HPTS in H 2 O and D 2 O is rather small 10 10 s −1 and 3.3 × 10 9 s −1 , respectively. In the time-resolved fluorescence signal of the deprotonated form we find a rise-component of 2.5 ps which we assign to slow charge rearrangement as was already suggested by Spry and Fayer [Spry, D. B.; Fayer, M. D. Charge Redistribution and Photoacidity: Neutral Versus Cationic Photoacids. J. Chem. Phys . 2008 , 128, 084508-1–084508-9]. Already in the time-window of 0.2–1.2 ns, the proton geminate recombination (GR) fluorescence tail of the ROH form decays as t −α where α ≈ 3/2, as predicted by the diffusion-assisted GR model, but for much longer times ( t > 5 ns). We also found that the rotation-relaxation time of the ROH form is about τ or = 80 ps in H 2 O, shorter than previously reported, whereas in methanol solution, with much lower viscosity, it is much larger – τ or = 190 ps. We explain this large difference of τ or by counter-ion association on all the three sulfonate groups of HPTS.

Brillouin optical time domain reflectometry for fast detection of dynamic strain incorporating double-edge technique

For the first time, to the best of our knowledge, a direct detection Brillouin optical time-domain reflectometry (BOTDR) is demonstrated for fast distributed dynamic strain sensing incorporating double-edge technique, time-division multiplexing technique and upconversion technique. In order to guarantee the robust stability of the system, the double-edge technique is implemented by using a convert single-channel FPI and a fiber-coupled upconversion single-photon detector, incorporating a time-division multiplexing method. The upconversion single-photon detector is adopted to upconvert the backscattering photons from 1548.1nm to 863nm, which is subsequently detected by a Silicon avalanche photodiode (Si-APD). In the experiment, dynamic strain disturbance up to 1.9mε over 1.5km of a polarization maintaining fiber is detected at a sampling rate of 30Hz. An accuracy of ±30με and spatial resolution of 0.6m are realized.

Ultra-broadband mid-wave-IR upconversion detection.

In this Letter, we demonstrate efficient room temperature detection of ultra-broadband mid-wave-infrared (MWIR) light with an almost flat response over more than 1200 nm, exploiting an efficient nonlinear upconversion technique. Black-body radiation from a hot soldering iron rod is used as the IR test source. Placing a 20 mm long periodically poled lithium niobate crystal in a compact intra-cavity setup (>20 W CW pump at 1064 nm), MWIR wavelengths ranging from 3.6 to 4.85 μm are upconverted to near-infrared (NIR) wavelengths (820-870 nm). The NIR light is detected using a standard low-noise silicon-based camera/grating spectrometer. The proposed technique allows high conversion efficiency over a wider bandwidth without any need for a shorter crystal length. Different analytical predictions and numerical simulations are performed a priori to support the experimental demonstrations.

An XPolM-Based All-Optical SSB Frequency Up-Conversion Technique in an SOA

A radio-over-fiber (RoF) downlink using a cross-polarization modulation (XPolM)-based all-optical single sideband (SSB) frequency up-conversion method in a semiconductor optical amplifier is experimentally demonstrated. A 10-Gb/s 16QAM orthogonal frequency division multiplexing signal at a carrier frequency of 60 GHz is transmitted. This RoF downlink shows a negligible power penalty associated with the chromatic dispersion of a single-mode fiber for a fiber length up to 20 km. The RoF downlink shows almost flat bit-error-rate performance for an optical IF signal wavelength range from 1550 to 1570 nm.

Enabling valley selective exciton scattering in monolayer WSe2 through upconversion

Excitons, Coulomb bound electron–hole pairs, are composite bosons and their interactions in traditional semiconductors lead to condensation and light amplification. The much stronger Coulomb interaction in transition metal dichalcogenides such as WSe2 monolayers combined with the presence of the valley degree of freedom is expected to provide new opportunities for controlling excitonic effects. But so far the bosonic character of exciton scattering processes remains largely unexplored in these two-dimensional materials. Here we show that scattering between B-excitons and A-excitons preferably happens within the same valley in momentum space. This leads to power dependent, negative polarization of the hot B-exciton emission. We use a selective upconversion technique for efficient generation of B-excitons in the presence of resonantly excited A-excitons at lower energy; we also observe the excited A-excitons state 2s. Detuning of the continuous wave, low-power laser excitation outside the A-exciton resonance (with a full width at half maximum of 4 meV) results in vanishing upconversion signal.

Piezoelectric energy reclamation based on frequency up-conversion technique for digital actuator autonomous additional functions

A piezoelectric vibration energy harvester aiming at collecting energy from the operation of an electromagnetic digital actuator is presented. It is based on the frequency up-conversion and can simultaneously obtain the information of discrete position location. The objective is an improved reliability of such digital actuators ensuring sample controls of the actuator positions. The considered electromagnetic digital actuator is capable of achieving two-dimensional in-plane movements by switching a mobile permanent magnet among four discrete positions. The demonstration of a first step toward integrated additional autonomous functions scavenging a part of the mechanical energy of the mobile permanent magnet is achieved. The vibration energy harvester consists of a piezoelectric cantilever beam magnetically attached to the mobile permanent magnet. The limited magnetic interaction force allows a frequency up-conversion strategy to be set. The frequency up-conversion technique that is used here consists of a “low frequency” excitation that drives a much higher natural frequency oscillator. Indeed, once the energy harvester separates from the mobile permanent magnet, a free oscillation occurs and the induced mechanical energy is harvested. This design concept is numerically analyzed and experimentally validated. Harvested energy of 4.7 µJ is obtained from preliminary experiments using a simple out-of-plane cantilever beam with 9 N/m stiffness and 16 mN magnetic attraction between the vibration energy harvester and the mobile permanent magnet when they contact each other. This energy is in accordance with the requirements for wireless communication of simple information. Finally, an L-shaped cantilever beam optimized design is proposed for future in-plane integration.

An ultrafast pre-organization of the [2 + 2] photocycloaddition of styryl dyes in 1:2 host-guest complexes with cucurbit[8]urils

The photocycloaddition of styryl dyes 1, mediated by 1:2 hostguest complexes with cucurbit[8]urils (CB[8]), was studied by fluorescence upconversion techniques. The lifetime of 14.5ps for photoexcited 1 in aqueous solution and 3.8ps for that inside the complexes were gained from the fluorescence decay, the rate constant of quenching being obtained within the diffusion control limit. Calculations confirmed that unexcited pairs of 1 inside CB[8] does not fit the topochemical principles. So a translational movement is required to produce a reaction-ready structure that is in agreement with the timeresolved fluorescence anisotropy measured in the range of 5ps.

Complete ultrafast charge carrier dynamics in photo-excited all-inorganic perovskite nanocrystals (CsPbX3).

Understanding the nature and dynamics of the photo-induced transients of all-inorganic perovskite nanocrystals (NCs) is key to their exploitation in potential applications. In order to determine the nature of charge carriers, their deactivation pathways and dynamics, the photo-induced transients of CsPbBr3, CsPbBr2I, CsPbBr1.5I1.5 and CsPbI3 NCs are spectrally and temporally characterized employing a combination of femtosecond transient absorption (TA) and photoluminescence (PL) up-conversion techniques and global analysis of the data. The results provide distinct identities of the excitons and free charge carriers and distinguish the hot charge carriers from the cold ones. The carrier trapping is attributed to the electrons and their dynamics is unaffected in mixed halide perovskites. The excitation energy dependence of the TA dynamics suggests that the trap states are shallow in nature and mainly limited near the band-edge level. In mixed halide perovskites, an increase in the iodine content leads to hole trapping in a short time scale (<5 ps). The insights obtained from this study are likely to be helpful for tuning the photo-response of these substances and their better utilization in light-based applications.

Detection and upconversion of three-dimensional MMW/THz images to the visible

We present an inexpensive technique to obtain a three-dimensional (3D) millimeter wave (MMW) and terahertz (THz) image using upconversion. In this work we describe and demonstrate a method for upconversion of MMW/THz radiation to the visual band using a very inexpensive miniature glow discharge detector (GDD) and a silicon photodetector. We present MMW/THz upconversion images based on measuring the visual light emitting from the GDD rather than its electrical current. The results show better response time and better sensitivity compared to the electronic detection performed previously. Furthermore, in this work we perform frequency modulation continuous wave (FMCW) radar detection based on this method using a GDD lamp, with a photodetector to measure GDD light emission. By using FMCW detection, the range in addition to the intensity at each pixel can be obtained, thus yielding the 3D image. The GDD acts as a heterodyne mixer not only electronically but also optically. The suggested 3D upconversion technique using the GDD is simple and inexpensive and has better performance compared to other MMW/THz imaging systems suggested in the literature. This method provides minimum detectable signal power that is about 6 orders of magnitude better than similar plasma systems due to the very large internal signal gain deriving from the much smaller electrode separation and resulting in much higher plasma electric field.