Low Excitation Power Research Articles

Surface plasmon polariton–enhanced upconversion luminescence for biosensing applications

Abstract Upconversion luminescence (UCL) has great potential for highly sensitive biosensing due to its unique wavelength shift properties. The main limitation of UCL is its low quantum efficiency, which is typically compensated using low-noise detectors and high-intensity excitation. In this work, we demonstrate surface plasmon polariton (SPP)-enhanced UCL for biosensing applications. SPPs are excited by using a gold grating. The gold grating is optimized to match the SPP resonance with the absorption wavelength of upconverting nanoparticles (UCNPs). Functionalized UCNPs conjugated with antibodies are immobilized on the surface of the fabricated gold grating. We achieve an UCL enhancement up to 65 times at low excitation power density. This enhancement results from the increase in the absorption cross section of UCNPs caused by the SPP coupling on the grating surface. Computationally, we investigated a slight quenching effect in the emission process with UCNPs near gold surfaces. The experimental observations were in good agreement with the simulation results. The work enables UCL-based assays with reduced excitation intensity that are needed, for example, in scanning-free imaging.

Polymer-Based Room-Temperature Phosphorescence Materials Exhibiting Emission Lifetimes up to 4.6 s under Ambient Conditions.

The long-emission-lifetime nature of room-temperature phosphorescence (RTP) materials lays the foundation of their applications in diverse areas. Despite the advantage of mechanical property, processability and solvent dispersity, the emission lifetimes of polymer-based room-temperature phosphorescence materials remain not particularly long because of the labile nature of organic triplet excited states under ambient conditions. Specifically, ambient phosphorescence lifetime (τP) longer than 2 s and even 4 s have rarely been reported in polymer systems. Here, luminescent compounds with small phosphorescence rate on the order of approximately 10-1 s-1 are designed, ethylene-vinyl alcohol copolymer (EVOH) as polymer matrix and antioxidant 1010 to protect organic triplets are employed, and ultralong phosphorescence lifetime up to 4.6 s under ambient conditions by short-term and low-power excitation are achieved. The resultant materials exhibit high afterglow brightness, long afterglow duration, excellent processability into large area thin films, high transparency and thermal stability, which display promising anticounterfeiting and data encryption functions.

Enhancement of Vibrant Up-Conversion in (Ca,Sr)F2:Er,Yb,Al Phosphors via Energy Transfer, Localized Interstitial Distortion, and Au Nanostructures.

A remarkable increase in the luminescent intensity of Er3+-doped CaF2 up-conversion phosphors was achieved, showing an approximate enhancement of over 1100-fold. This enhancement was realized by incorporating Yb3+, Al3+, Sr2+, and gold nanospheres and nanorods. The substantial improvement in up-converting luminescence effectively enhances sensitivity and efficiency at low excitation power densities. The up-conversion phosphors, consisting of (Ca,Sr)F2:Er,Yb,Al, were easily prepared using excess NH4F flux at 950 °C for 30 min. The structural confirmation of interstitial Al3+ ions within the CaF2 lattice was achieved through synchrotron powder X-ray powder diffraction. The significant enhancement of up-conversion emission and their mechanisms in the phosphors were vividly represented through energy transfer, interstitials and local distortions, and localized surface plasmon resonances when excited with a 980 nm diode laser.

Enhanced trapping properties of coupled plasmonic tweezers via plasmon-exciton interaction

Excited plasmonic nanoantennas enable the manipulation of photons coupled with quantum emitters or the trapping of particles as plasmonic tweezers, leveraging the strong evanescent gradient fields at the nanoscale. However, the ohmic loss of metals presents a significant challenge for the stable and high-precision manipulation of nanoparticles without causing damage. In this study, we investigated the enhanced trapping properties induced by plasmon-exciton interaction for coupled plasmonic tweezers. Through the coupling between plasmons and excitons, dynamic particle trapping is achievable under low excitation power conditions of 0.45 mW, with the trapping stiffness increasing by nearly 20 times. Furthermore, the trapping stiffness can be fine-tuned by modulating the quantity of excitons to regulate the coupling strength. Coupled plasmonic tweezers offer an effective strategy to mitigate the influence of ohmic loss on trapping performance, by manipulating particles with minimal laser power. These findings provide insights into enhancing trapping performance through plasmon-exciton coupling, with potential applications in biomedicine and quantum information science.

Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light

AbstractCurrently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm.

Investigation of Exciton Dynamics to Confirm Coupling Effects Using a Comparison between Ensemble and Single Laterally‐Coupled GaAs Quantum Dot Molecules

Herein, time‐integrated and time‐resolved photoluminescence (PL) measurement experiments are performed on coupled GaAs quantum dot (QD) molecules with larger laser spot size and a single‐coupled QD molecule to investigate the dynamics of exciton states. A linearly polarized laser along the coupled direction of a laterally‐coupled GaAs QD molecule [10] is used to determine the coupling effects of the different exciton states. For the ensemble of coupled QD molecules, the exciton PL peak shifts to lower energy (≈70 meV) and shows a linear increase in the PL intensity, demonstrating the properties of exciton states as a function of the laser excitation power. In addition, a power‐dependent redshift is observed in the single‐coupled GaAs QD molecule as a function of the excitation power; however, the two distinguished exciton states become resolved and show different power factors when the laser excitation power is linearly increased. This result clearly indicates the presence of energy transfer between the two different exciton states, X1 and X2. Furthermore, when the polarized laser excitation power is increased, a coupled biexciton consisting of two different localized exciton states (X1 and X2) is clearly observed, and a power‐dependent spectral redshift is detected in the exciton and biexciton states. At a high excitation power (15 I0), the decay times of the two different localized exciton states clearly show different lifetimes; and the decay time difference due to the size difference can be ignored at a low excitation power. Theoretically, the decay times of the two different exciton states, wherein the size deviation can be ignored, should be the same. Based on the results of the time‐integrated and time‐resolved PL measurements and the comparison between the ensemble and single exciton PL peaks, it is concluded that the coupling process in laterally‐coupled GaAs QD molecules is strongly supported against long‐range separation.

Triplet-triplet annihilation photon upconversion-mediated photochemical reactions.

Photon upconversion is a method for harnessing high-energy excited states from low-energy photons. Such photons, particularly in the red and near-infrared wavelength ranges, can penetrate tissue deeply and undergo less competitive absorption in coloured reaction media, enhancing the efficiency of large-scale reactions and in vivo phototherapy. Among various upconversion methodologies, the organic-based triplet-triplet annihilation upconversion (TTA-UC) stands out - demonstrating high upconversion efficiencies, requiring low excitation power densities and featuring tunable absorption and emission wavelengths. These factors contribute to improved photochemical reactions for fields such as photoredox catalysis, photoactivation, 3D printing and immunotherapy. In this Review, we explore concepts and design principles of organic TTA-UC-mediated photochemical reactions, highlighting notable advancements in the field, as well as identify challenges and propose potential solutions. This Review sheds light on the potential of organic TTA-UC to advance beyond the traditional photochemical reactions and paves the way for research in various fields and clinical applications.

Development of excitation power-responsive anti-stokes emission wavelength switching and their energy saving induced by localized surface plasmon resonance

We designed an external stimulus-responsive anti-Stokes emission switching using dual-annihilator-based triplet–triplet annihilation upconversion systems. This system, which was constructed by incorporating a palladium porphyrin derivative as a sensitizer and 9,10-diphenylanthracene (DPA) and 9,10-bis(triisopropylsilyl)ethynylanthracene (TIPS) as annihilators into polymer thin films, produced TIPS- and DPA-based anti-Stokes emission under low and high excitation powers, respectively. The mechanism involves the following: under low excitation power, triplet energy transfer from triplet-excited PdOEP to DPA is induced, followed by relay to TIPS. This results in the generation of triplet-excited TIPS, and the subsequent triplet–triplet annihilation between them produces TIPS-based anti-Stokes emission. Conversely, under high excitation power, the high-density triplet-excited DPA, generated through triplet energy transfer from PdOEP, undergoes triplet–triplet annihilation among themselves, resulting in the generation of DPA-based anti-Stokes emission. Additionally, we achieved energy savings by reducing the required excitation power for switching through the utilization of plasmonic metal nanoparticles. The strong local electromagnetic fields associated with the localized surface plasmon resonance of metal nanoparticles enhance the photoexcitation efficiency of PdOEP, subsequently increasing the density of triplet-excited DPA. As a result, anti-Stokes emission switching becomes feasible at lower excitation powers.

Ultra-stable nano-micro bubbles in a biocompatible medium for safe delivery of anti-cancer drugs

We conducted a series of experimental investigations to generate laser-stimulated millimeter bubbles (MBs) around silver nanoparticles (AgNPs) and thoroughly examined the mechanism of bubble formation within this nanocomposite system. One crucial aspect we explored was the lifetime and kinetics of these bubbles, given that bubbles generated by plasmonic nanoparticles are known to be transient with short durations. Surprisingly, our findings revealed that the achieved lifetime of these MBs extended beyond seven days. This impressive longevity far surpasses what has been reported in the existing literature. Further analysis of the experimental data uncovered a significant correlation between bubble volume and its lifetime. Smaller bubbles demonstrated longer lifetimes compared to larger ones, which provided valuable insights for future applications. The experimental results not only confirmed the validity of our model and simulations but also highlighted essential characteristics, including extended lifetime, matching absorption coefficients, adherence to physical boundary conditions, and agreement with simulated system parameters. Notably, we generated these MBs around functionalized AgNPs in a biocompatible nanocomposite medium by utilizing low-power light excitation. By readily binding potent cancer drugs to AgNPs through simple physical mixing, these medications can be securely encapsulated within bubbles and precisely guided to targeted locations within the human body. This capability to deliver drugs directly to the tumor site, while minimizing contact with healthy tissues, can lead to improved treatment outcomes and reduced side effects, significantly enhancing the quality of life for cancer patients.

Diagnosis of multiple gases using a multi-pass ring cavity to enhance Raman scattering

Spontaneous Raman scattering is widely used to enable simultaneous concentration measurements of all relevant species with overcomes whose signal is weak and susceptible to fluorescence interference. A multi-pass ring-cavity scheme is proposed to enhance Raman scattering signal. The Raman spectra of CO2, N2, O2 and H2O in the air are acquired under condition of low excitation power which is 200 mW laser of 532 nm. Compared with the results obtained by single collection without ring cavity, the Raman signal level is enhanced 40 times and the signal-to-noise ratio is improved by 43 times at maximum. Power of pump is taken into consideration to analyze its impact on signal. A limit of detection (3σ criterion standard) of 83 ppm for CO2 is calculated for the multi-pass ring-cavity. The limit of detection of 14 ppm for CH4 is also estimated by the theoretical ratio of cross section values of CO2 and CH4. When power of excitation is low, high level of signal of multi-species gases is acquired with fine detection sensitivity through ring cavity.

Radiative‐Recombination Thermodynamics in Boron‐Doped Diamond

AbstractBoron‐doped diamond is a wide‐bandgap semiconductor with excellent semiconductor properties, which is widely utilized in various applications. Till now, the thermodynamic rules governing the carrier transitions in this material have not been fully understood. In this research, the different luminescence behaviors of boron‐doped diamond under 193 nm pulse laser with high‐ and low‐ power density excitation are analyzed. Under high‐power density excitation (@≈63 kW cm−2), the emission intensity of excitons is nearly ten times higher than that of defect luminescence. Conversely, under low‐power density excitation (@≈1.4 kW cm−2, different emission peaks exhibit similar intensities, indicating a competitive relationship among them. Based on experimental and theoretical analyses, the difference is attributed to the thermodynamic distribution of carriers at varying excitation powers. Specifically, high excitation power brings an independent behavior of each emission peak, and the exciton emission is described by a phonon‐assisted radiation model; different from that, the competition among different emission centers under the condition of low excitation power cannot be neglected, and now the thermodynamic evolution of each emission peak is described by a carrier trapping‐dissociation model.

An efficiently excited Eu3+ luminescent site formed in Eu,O-codoped GaN

For the development of III-nitride-semiconductor-based monolithic micro-light-emitting diode (LED) displays, Eu,O-codoped GaN (GaN:Eu,O) is a promising material candidate for the red LEDs. The luminescence efficiency of Eu-related emission strongly depends on the local atomic structure of Eu ions. Our previous research has revealed that post-growth thermal annealing is an effective method for reconfiguring luminescent sites, leading to a significant increase in light output. We observed the preferential formation of a site with a peak at ∼2.004 eV by the annealing process. In this study, we demonstrate that it is a previously unidentified independent site (OMVPE-X) using combined excitation–emission spectroscopy and time-resolved photoluminescence measurements. In addition, we perform excitation power-dependent photoluminescence measurements and show that this OMVPE-X site dominates the emission at a low excitation power region despite its small relative abundance, suggesting a high excitation efficiency. Most importantly, applying our annealing technique to an LED exhibits a reasonably increased electroluminescence intensity associated with OMVPE-X, confirming that this site has a high excitation efficiency also under current injection. These results demonstrate the importance of OMVPE-X as a notable luminescent site for brighter and more efficient GaN:Eu,O-based LEDs.

Evidence of carrier diffusion between emission states in CdSe/ZnS core-shell quantum dots: a comprehensive investigation combining fluorescence lifetime correlation spectroscopy (FLCS) and single dot photoluminescence studies.

Investigation of carrier dynamics in CdSe/ZnS core-shell quantum dots (QDs) is performed using fluorescence-lifetime-correlation-spectroscopy (FLCS) and single-dot PL blinking studies. The origin of an emitted photon from a QD in an FLCS study is assigned to either an exciton state or trap state based on its excited state lifetime (τfl). Subsequently, two intrastate autocorrelation functions (ACFs) representing the exciton and trap states and one cross-correlation function (CCF) coupling these two states are constructed. Interestingly, the timescales of carrier diffusion (τR) show striking similarities across all three correlation functions, which further correlate with τR of the conventional FCS. However, ACFs notably deviate from the CCF in their μs progression patterns, with the latter showing growth, whereas the former ones display decay. This implies inter-state carrier diffusions leading to the QD blinking. Further study of single particle PL blinking on a surface-immobilized QD indicates shallow trap states near the band edge cause the blinking at low excitation power, while trion recombination becomes an additional contributing factor at higher pump power. Overall, the results highlight not only an excellent correlation between these two techniques but also the potential of our approach for achieving an accurate and comprehensive understanding of carrier dynamics in CdSe/ZnS QDs.

A portable fluorescence detection device based on a smartphone employing carbon nanodots for Mn2+ sensing.

The measurement of fluorescence emission for quantitative analysis is typically based on a traditional spectrofluorometer, which limits an onsite detection approach. Thus, an alternative device should be developed for fulfilling this analysis outside of the laboratory. Therefore, a low-cost, portable, and low-energy consumption fluorescence reader-based smartphone device was developed. An ultraviolet light-emitting diodes (UV-LED) was used to construct the fluorescence device-based smartphone as a low-power excitation light source. The smartphone camera was used as a detector for detecting photons from the fluorescence emission process of the fluorescence probe and was connected to a digital image platform. Transparent acrylic with orange and yellow colors was employed as a filter for reducing the interference from light source intensity. The obtained digital image was converted to red, green and blue (RGB) intensity using a custom-designed smartphone application. N,S-doped carbon nanodots (N,S-CDs) were demonstrated to be a good fluorescence indicator for determining trace quantities of Mn2+ in cosmetics. The approach exhibited high selectivity and sensitivity, detecting and quantifying analytes at 1-5 μM concentrations. Furthermore, the method's detection limit of 0.5 μM reflects its capacity to detect trace amounts of a target analyte. Mn2+ in cosmetic products was successfully analyzed using this device with high accuracy comparable with the results from inductively coupled plasma-optical emission spectroscopy (ICP-OES).

Charge-carrier photogeneration in single-component organic carbazole-based semiconductors via low excitation power triplet-triplet annihilation

Charge-carrier photogeneration in single-component organic carbazole-based semiconductors via low excitation power triplet-triplet annihilation

Photon Pair Source based on PPLN‐Waveguides for Entangled Two‐Photon Absorption

AbstractFluorescence excitation by absorption of entangled photon pairs offers benefits compared to classical imaging techniques, such as the attainment of higher signal levels at low excitation power while simultaneously mitigating phototoxicity. However, current entangled photon pair sources are unreliable for fluorescence detection. In order to address this limitation, there is a need for ultra‐bright entangled photon pair sources. Among the potential solutions, sources utilizing nonlinear waveguides emerge as promising candidates to facilitate fluorescence excitation through entangled photons. In this paper, a source consisting of a periodically poled lithium niobate waveguide is developed and its key characteristics are analyzed. To demonstrate its suitability as key component for imaging experiments, the entangled two‐photon absorption behavior of Cadmium Selenide Zinc Sulfide quantum dot solutions is experimentally investigated.

Giant Light‐Harvesting in Dye‐Loaded Nanoparticles Enhanced by Blank Hydrophobic Salts

AbstractLight‐harvesting is a fundamental process in nature, which inspires researchers to develop artificial systems for photocatalysis, photovoltaics, and biosensing. A previously introduced light‐harvesting nanoantenna, based on polymeric nanoparticles (NPs) loaded with rhodamine dyes and bulky hydrophobic counterions, provides a record‐breaking antenna effect ≈1000. However, the high dye cooperativity of its thousands of encapsulated dyes causes energy losses by traces of self‐quenched dye aggregates. Here, it is found that these imperfections can be suppressed by blank hydrophobic salts (BHS) formed by the same bulky counterion (fluorinated tetraphenylborate) with an optically inactive cation, analogs of ionic liquids. The presence of BHS increases twofold the fluorescence quantum yields and fluorescence lifetimes of NPs and suppresses their fluorescence blinking. This study assumes that BHS provides an excess of bulky counterions that excludes traces of dye aggregates. As a result, an efficient Forster resonance energy transfer (FRET) is achieved from 40 000 dye donors to a single acceptor within a 70 nm particle, leading to the antenna effect of 4800, which is by far the highest value reported to date. Using this nanoantenna, a single‐molecule detection of the FRET acceptor is realized at low excitation power using an RGB camera of a smartphone.

Suhl instabilities in nanoscopic spheroids

We simulate the magnetization dynamics of a permalloy spheroid of nanoscopic size in zero external field, such that both dipolar and exchange interactions are important. Low excitation power is used to obtain the frequencies and mode patterns of many normal modes. At higher power, non-linear three and four mode couplings between magnons carrying orbital angular momentum are observed to give rise to Suhl instabilities. Suhl’s analysis of the selection rules governing the allowed processes is extended to initial states other than uniform precession. These rules are studied and confirmed by the simulations. Both down- and up-conversion are seen as well as three and four-mode processes. General trends are inferred for preferred instabilities among those that are allowed, although the thresholds for some instabilities appear to be very high.

Full‐Landscape Condensation Phases for Long‐Lived Excitons in 2D Tellurium: Crystal‐Field Splitting and Finite‐Momentum Excitons

AbstractThe realization of high‐temperature exciton macroscopic quantum phases in materials still remains challenging due to strict constraints in thermal stabilities and excitonic lifetimes. In this work, by using first‐principles calculations, the exciton dispersions and macroscopic quantum phase transitions of 2D α‐ and β‐Te are investigated. The excitons with lowest eigen energy for both α‐ and β‐Te are dark restricted by the crystal‐field symmetries. The Bose–Einstein condensation (BEC) transition for α‐ and β‐Te can be realized at 165.4 and 32.8 K with low excitation power densities of 0.42 × 1012 and 1.0 × 1012 cm−2, respectively. Furthermore, the phase transitions from insulating free exciton (FE) gas to conducting electron–hole plasma (EHP) and electron–hole liquid (EHL), as well as that from BEC to superfluidity phases are also predicted. Finally, the authors investigate the microscopic dynamics for bright excitons of 2D tellurium and find that they reach thermal equilibrium at 1–50 fs and excitonic lifetimes can reach 1–40 ns, beneficial for experimental observation of quantum condensate states. The findings in this work not only demonstrate the excellent optoelectronic properties of 2D tellurium allotropes, but also provide a promising platform for experimental realization of high‐temperature excitonic macroscopic quantum condensates.

Investigation of variation in fluorescence intensity from rhodamine 6G dye in a trapped and levitated liquid micro-drop

Variation in fluorescence intensity from rhodamine 6 G dye was investigated. A small volume of dye solution, in the form of a trapped and levitated micro-drop, was optically excited with a 400 μW, 532 nm wavelength cw-laser light. The dye was dissolved in methanol and glycerol for a concentration of 10 mg/ml or 21 mMole per liter. With the optical excitation, initially the fluorescence intensity was observed to rise with time, and then it decayed, along with a steady shift of fluorescence peak from 562 nm to 543 nm. The observation of initial enhancement in fluorescence from start to 7 min of excitation, can partly be due to the low excitation power, less dimer formation and gradual rise in molecular population to excited state therefore slower rate of change (increase) of fluorescence intensity was observed with time. Simulation studies indicate that the photo bleaching was taking place from all the energy states of the dye molecules, which is an extension of the concept that the photo bleaching takes place at the excited triplet state whereas the fluorescence takes place due to transition between excited singlet states and ground states. A steady shift in fluorescence peak position, from 562 nm to 543 nm, was observed during the fluorescence life of the dye, at a rate of 0.0113 nm/s during fluorescence enhancement and 0.026 nm/s during photo-bleaching. The steady blue shift of fluorescence indicate insignificant dimer formation.