Reversible photo- and thermal-effects on the luminescence of gold nanoclusters: implications for nanothermometry.

The optical properties of colloidal near-infrared (NIR) emitting gold nanoclusters (AuNCs) are thoroughly investigated at variable temperatures and excitation powers. Both absorption and photoluminescence (PL) excitation spectra reveal optical transitions expected from literature models of thiolated AuNCs - with the exception of the lowest energy transition which has the form of a featureless absorption tail partially overlapping with the PL band. The absorption cross section is determined via the PL saturation and PL modulation techniques to be in the range of 2-3 × 10-14 cm2 for excitation at 405 nm (relatively large value for such small clusters) and decreases ∼20 times toward 633 nm. Slow transient quenching (perfectly reversible) of PL is observed when the excitation power exceeds the saturation threshold, i.e. when the probability of achieving the second absorption in an excited AuNC before its relaxation is significant. A stable PL quenched level is reached within a fraction of a minute or a few minutes after the start of the excitation. Similar time intervals are needed for AuNCs to relax back to the original state in the dark. By comparing thermally-induced and light-induced PL decreases and PL kinetics speed up, we conclude that the transient quenching is due to heating caused by the dissipated excitation power. The light-induced PL amplitude reduction is much stronger (up to ∼80% under 405 nm, 60 W cm-2 excitation) than changes in PL decay time (∼20%), which is due to PL blinking and PL switching-off in a fraction of the AuNC ensemble. The potential application of these AuNCs in nanothermometry is discussed.

Power-dependent photoluminescence decay kinetics of silicon nanocrystals under continuous and pulsed excitation.

Power-dependent photoluminescence (PL) decay kinetics of silicon nanocrystals (Si NCs) in solid and liquid samples were studied under cw and pulsed excitation. The lifetime distribution and, consequently the measured PL kinetics are shown to depend on the excitation pulse duration until it is not sufficiently short (pulsed limit) or long (cw limit). These two excitation limits, however, are proven to excite different distributions of lifetime components and cannot be directly compared. We derive and experimentally confirm the equality of lifetimes averaged over amplitude and intensity for cw and pulsed excitation, accordingly. The absorption cross section (ACS) of Si NCs in solid and liquid samples is assessed and compared by two approaches under cw-excitation based on the treatment of power-modulated PL kinetics or PL amplitude saturation curves under low and moderate excitation powers, respectively. The discrepancy in extracted ACS values as well as the long-debated phenomena of incomplete PL saturation of matrix-embedded Si NCs is explained by a proposed model that is based on saturation of various components in an ensemble distribution at different excitation powers. The model finally allows us to explain the mystery of average decay lifetime dependence on excitation power in the non-linear power regime. By varying the excitation from cw to pulsed, we showed the reduction of average decay lifetime in the later case and attribute this to the increased relative PL contribution of fast lifetime components that results in at least one order of magnitude lower ACS values. Finally, exciting the solid sample with very high excitation powers, we detected a PL intensity decrease region that allowed us to extract the Auger lifetime which is about 170 ns.

Two-step light conversion with quantum dots inside non-linear crystals.

Up-conversion of infrared (IR) to visible light is demonstrated via an unconventional two-step process combining second harmonic generation with photoluminescence. This is achieved in a composite material formed by single crystals of KH2PO4 (KDP), in which CdTe/CdS quantum dots (QDs) are embedded during a crystal growth. The second harmonic generation from the IR laser frequency in KDP takes place, and then, generated light is absorbed by QDs and luminescence is emitted. Compared to the most common up-converting materials based on lanthanide ions, our novel composites use only abundant elements and have several other properties with application potential: the excitation and emission can cover a broader spectral range, and the response is much faster (ns compared to ms) and is strongly dependent on the direction of the incident beam.

Relations between Structural and Luminescence Properties of Novel Lanthanide Nitrate Complexes with Bis-phosphoramidate Ligands.

Five new bisphosphoramide-based LnIII nitrate complexes [La2(NO3)6L3I] n (1), [Ce2(NO3)6L3I] n (2), [Sm2(NO3)6L3II] n (3), Sm2(NO3)6L3III (4), and Er(NO3)3L2III (5) [LI = piperazine-1,4-diylbis(diphenyl phosphine oxide), LII = N, N'-(ethane-1,2-diyl)bis( N-methyl- P, P-diphenylphosphinic amide, and LIII = N, N'-(ethane-1,2-diyl)bis( P, P-diphenylphosphinic amide)] have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single crystal X-ray and powder diffractions. The results of the X-ray diffraction analysis revealed the new polymorph of LIII, and the structural diversity of the synthesized complexes in the solid state. Complexes 1-3 display two-dimensional coordination polymers (2D-CP), containing layers with honeycomb (6, 3) topology. In these 2D-CPs, each Ln center (La, Ce, and Sm in 1, 2, and 3, respectively) could be considered as a triconnected node, linked by three bridging bisphosphoramide ligands as two-connecting linkers. In contrast, 4 is a discrete binuclear complex, in which bidentate LIII ligand has two entirely different conformations: the syn chelating and the anti bridging. Cationic complex 5 shows the monomeric structure, where bidentate LIII adopts the syn-chelating conformation. A comprehensive luminescence investigation has been performed on free ligands and their corresponding complexes as well. The synthesized compounds display a variety of luminescence behavior, including the ligand-centered fluorescence in 1, 2, and 5, two distinct emission peaks in 1 and 2, characteristic Sm-centered f-f emission in 3 and 4, and excitation-dependent emission in LIII, 1, and 2. Furthermore, the time-dependent density functional theory (TD-DFT) study was carried out on the reported compounds to understand the nature of the emission peaks and the observed luminescence properties. The solid-state emission quantum yields of lanthanide complexes were also determined at different excitation wavelengths.

Probing silicon quantum dots by single-dot techniques.

Silicon nanocrystals represent an important class of non-toxic, heavy-metal free quantum dots, where the high natural abundance of silicon is an additional advantage. Successful development in mass-fabrication, starting from porous silicon to recent advances in chemical and plasma synthesis, opens up new possibilities for applications in optoelectronics, bio-imaging, photovoltaics, and sensitizing areas. In this review basic physical properties of silicon nanocrystals revealed by photoluminescence spectroscopy, lifetime, intensity trace and electrical measurements on individual nanoparticles are summarized. The fabrication methods developed for accessing single Si nanocrystals are also reviewed. It is concluded that silicon nanocrystals share many of the properties of direct bandgap nanocrystals exhibiting sharp emission lines at low temperatures, on/off blinking, spectral diffusion etc. An analysis of reported results is provided in comparison with theory and with direct bandgap material quantum dots. In addition, the role of passivation and inherent interface/matrix defects is discussed.

Detection of Sugars via Chirality Induced in Europium(III) Compounds.

Detection and resolution of simple monosaccharides are difficult tasks because their structure is quite similar. The present study shows that circularly polarized luminescence (CPL) induced in europium complexes provides very specific spectral patterns for fructose, mannose, glucose, and galactose. Differences were also observed between bare Eu(3+) ion and its complexes, when interacting with these sugars. The CPL spectra were measured on a Raman optical activity (ROA) spectrometer, which ensured high fluorescence intensity owing to the strong 532 nm laser excitation. The induced fluorescence was recorded in the same spectrum as the vibrational Raman bands. On the basis of the ligand field theory, most fluorescence spectral peaks could be assigned to f-shell europium transitions. Additional information on the interaction of the lanthanide with the sugar component was provided by measurement of time-dependent fluorescence, as formation of different complexes led to variations in fluorescence decay times. In nuclear magnetic resonance (NMR), the paramagnetic metal ion interacting with the sugars caused specific changes in (13)C chemical shifts. The spectroscopic data and molecular dynamics modeling showed that the interaction between the monosaccharides and Eu ion is rather weak due to the competition of the OH sugar groups with water molecules. However, multiple binding modes are possible, which contributes to the complexity and specificity of the spectra. The induced chirality and fluorescence spectra thus appear to be convenient means for monosaccharide detection and identification.

Real-time luminescence microspectroscopy monitoring of singlet oxygen in individual cells.

A new setup for direct microspectroscopic monitoring of singlet oxygen ((1)O2) has been developed in our laboratory using a novel near-infrared sensitive InGaAs 2D-array detector. An imaging spectrograph has been inserted in front of the 2D-array detector, which allows us to acquire spectral images where one dimension is spatial and the other is spectral. The work presents a detailed examination of sensitivity and noise characteristics of the setup and its ability to detect (1)O2. The (1)O2 phosphorescence-based images and near-infrared luminescence spectral images recorded from single TMPyP-containing fibroblast cells reflecting spectral changes during irradiation are demonstrated. The introduction of spectral images addresses the issue of a potential spectral overlap of (1)O2 phosphorescence with near-infrared-extended luminescence of the photosensitizer and provides a powerful tool for distinguishing and separating them, which can be applied to any photosensitizer manifesting near-infrared luminescence.

Direct Synthesis and Characterization of Hydrophilic Cu-Deficient Copper Indium Sulfide Quantum Dots.

Copper indium sulfide (CIS) nanocrystals constitute a promising alternative to cadmium- and lead-containing nanoparticles. We report a synthetic method that yields hydrophilic, core-only CIS quantum dots, exhibiting size-dependent, copper-deficient composition and optical properties that are suitable for direct coupling to biomolecules and nonradiative energy transfer applications. To assist such applications, we complemented previous studies covering the femtosecond-picosecond time scale with the investigation of slower radiative and nonradiative processes on the nanosecond time scale, using both time-resolved emission and transient absorption. As expected for core particles, relaxation occurs mainly nonradiatively, resulting in low, size-dependent photoluminescence quantum yield. The nonradiative relaxation from the first excited band is wavelength-dependent with lifetimes between 25 and 150 ns, reflecting the size distribution of the particles. Approximately constant lifetimes of around 65 ns were observed for nonradiative relaxation from the defect states at lower energies. The photoluminescence exhibited a large Stokes shift. The band gap emission decays on the order of 10 ns, while the defect emission is further red-shifted, and the lifetimes are on the order of 100 ns. Both sets of radiative lifetimes are wavelength-dependent, increasing toward longer wavelengths. Despite the low radiative quantum yield, the aqueous solubility and long lifetimes of the defect states are compatible with the proposed role of CIS quantum dots as excitation energy donors to biological molecules.

Microstructure and physical properties of black-aluminum antireflective films.

The microstructure and physical properties of reflective and black aluminum were compared for layers of different thicknesses deposited by magnetron sputtering on fused silica substrates. Reflective Al layers followed the Volmer-Weber growth mechanism classically observed for polycrystalline metal films. On the contrary, the extra nitrogen gas used to deposit the black aluminum layers modified the growth mechanism and changed the film morphologies. Nitrogen cumulated in the grain boundaries, favoring the pinning effect and stopping crystallite growth. High defect concentration, especially vacancies, led to strong columnar growth. Properties reported for black aluminum tend to be promising for sensors and emissivity applications.

Towards site-specific emission enhancement of gold nanoclusters using plasmonic systems: advantages and limitations.

Photoluminescent gold nanoclusters are widely seen as a promising candidate for applications in biosensing and bioimaging. Although they have many of the required properties, such as biocompatibility and photostability, the luminescence of near infrared emitting gold nanoclusters is still relatively weak compared to the best available fluorophores. This study contributes to the ongoing debate on the possibilities and limitations of improving the performance of gold nanoclusters by combining them with plasmonic nanostructures. We focus on a detailed description of the emission enhancement and compare it with the excitation enhancement obtained in recent works. We prepared a well-defined series of gold nanoclusters attached to gold nanorods whose plasmonic band is tuned to the emission band of gold nanoclusters. In the resultant single-element hybrid nanostructure, the gold nanorods control the luminescence of gold nanoclusters in terms of its spectral position, polarization and lifetime. We identified a range of parameters which determine the mutual interaction of both particles including the inter-particle distance, plasmon-emission spectral overlap, dimension of gold nanorods and even the specific position of gold nanoclusters attached on their surface. We critically assess the practical and theoretical photoluminescence enhancements achievable using the above strategy. Although the emission enhancement was generally low, the observations and methodology presented in this study can provide a valuable insight into the plasmonic enhancement in general and into the photophysics of gold nanoclusters. We believe that our approach can be largely generalized for other relevant studies on plasmon enhanced luminescence.

Microscopic origin of the fast blue-green luminescence of chemically synthesized non-oxidized silicon quantum dots.

The microscopic origin of the bright nanosecond blue-green photoluminescence (PL), frequently reported for synthesized organically terminated Si quantum dots (Si-QDs), has not been fully resolved, hampering potential applications of this interesting material. Here a comprehensive study of the PL from alkyl-terminated Si-QDs of 2-3 nm size, prepared by wet chemical synthesis is reported. Results obtained on the ensemble and those from the single nano-object level are compared, and they provide conclusive evidence that efficient and tunable emission arises due to radiative recombination of electron-hole pairs confined in the Si-QDs. This understanding paves the way towards applications of chemical synthesis for the development of Si-QDs with tunable sizes and bandgaps.

Coexistence of 1D and quasi-0D photoluminescence from single silicon nanowires.

Single silicon nanowires (Si-NWs) prepared by electron-beam lithography and reactive-ion etching are investigated by imaging optical spectroscopy under variable temperatures and laser pumping intensities. Spectral images of individual Si-NWs reveal a large variability of photoluminescence (PL) along a single Si-NW. The weaker broad emission band asymmetrically extended to the high-energy side is interpreted to be due to recombination of quasi-free 1D excitons while the brighter localized emission features (with significantly variable peak position, width, and shape) are due to localization of electron-hole pairs in surface protrusions acting like quasi-0D centers or quantum dots (QDs). Correlated PL and scanning electron microscopy images indicate that the efficiently emitting QDs are located at the Si-NW interface with completely oxidized neck of the initial Si wall. Theoretical fitting of the delocalized PL emission band explains its broad asymmetrical band to be due to the Gaussian size distribution of the Si-NW diameter and reveals also the presence of recombination from the Si-NW excited state which can facilitate a fast capture of excitons into QD centers.

Blinking statistics of silicon quantum dots.

The blinking statistics of numerous single silicon quantum dots fabricated by electron-beam lithography, plasma etching, and oxidation have been analyzed. Purely exponential on- and off-time distributions were found consistent with the absence of statistical aging. This is in contrast to blinking reports in the literature where power-law distributions prevail as well as observations of statistical aging in nanocrystal ensembles. A linear increase of the switching frequency with excitation power density indicates a domination of single-photon absorption processes, possibly through a direct transfer of charges to trap states without the need for a bimolecular Auger mechanism. Photoluminescence saturation with increasing excitation is not observed; however, there is a threshold in excitation (coinciding with a mean occupation of one exciton per nanocrystal) where a change from linear to square-root increase occurs. Finally, the statistics of blinking of single quantum dots in terms of average on-time, blinking frequency and blinking amplitude reveal large variations (several orders) without any significant correlation demonstrating the individual microscopic character of each quantum dot.

Optically coupled gold nanostructures: plasmon enhanced luminescence from gold nanorod-nanocluster hybrids.

Photoluminescent (PL) gold nanoclusters (AuNCs) show many advantages over conventional semiconductor quantum dots, however, their application potential is limited by their relatively low absorption cross-section and quantum yield. Plasmonic enhancement is a common strategy for improving the performance of weak fluorophores, yet in the case of AuNCs this method is still poorly explored. Here a robust synthetic approach to a compact plasmonic nanostructure enhancing significantly the PL of AuNCs is presented. Two gold nanostructures, AuNCs and plasmonic gold nanorods (AuNRs), are assembled in a compact core-shell nanostructure with tunable geometry and optical properties. The unprecedented degree of control over the structural parameters of the nanostructure allows to study the effects of several parameters, such as excitation wavelength, AuNC-AuNR distance, and relative loading of AuNCs per single AuNR. Consequently, a more general method to measure and evaluate enhancement independently of the absolute particle concentrations is introduced. The highest PL intensity enhancement is obtained when the excitation wavelength matches the strong longitudinal plasmonic band of the AuNRs and when the separation distance between AuNCs and AuNRs decreases to 5 nm. The results presented are relevant for the application of AuNCs in optoelectronic devices and bioimaging.

Enhancing the cooling potential of photoluminescent materials through evaluation of thermal and transmission loss mechanisms.

Photoluminescent materials are advanced cutting-edge heat-rejecting materials capable of reemitting a part of the absorbed light through radiative/non-thermal recombination of excited electrons to their ground energy state. Photoluminescent materials have recently been developed and tested as advanced non-white heat-rejecting materials for urban heat mitigation application. Photoluminescent materials has shown promising cooling potential for urban heat mitigation application, but further developments should be made to achieve optimal photoluminescence cooling potential. In this paper, an advanced mathematical model is developed to explore the most efficient methods to enhance the photoluminescence cooling potential through estimation of contribution of non-radiative mechanisms. The non-radiative recombination mechanisms include: (1) Transmission loss and (2) Thermal losses including thermalization, quenching, and Stokes shift. The results on transmission and thermal loss mechanisms could be used for systems solely relying on photoluminescence cooling, while the thermal loss estimations can be helpful to minimize the non-radiative losses of both integrated photoluminescent-near infrared (NIR) reflective and stand-alone photoluminescent systems. As per our results, the transmission loss is higher than thermal loss in photoluminescent materials with an absorption edge wavelength (λAE) shorter than 794 nm and quantum yield (QY) of 50%. Our predictions show that thermalization loss overtakes quenching in photoluminescent materials with λAE longer than 834 nm and QY of 50%. The results also show that thermalization, quenching, and Stokes shift constitute around 56.8%, 35%, and 8.2% of the overall thermal loss. Results of this research can be used as a guide for the future research to enhance the photoluminescence cooling potential for urban heat mitigation application.

Optimizing plasmon enhanced luminescence in silicon nanocrystals by gold nanorods.

The great application potential of photoluminescent silicon nanocrystals, especially in biomedicine, is significantly reduced due to their limited radiative rate. One of the possible ways to overcome this limitation is enhancing the luminescence by localized plasmons of metallic nanostructures. We report an optimized fabrication of gold nanorod - silicon nanocrystal core-shell nanoparticles with the silica shell as a tunable spacer. The unprecedented structural quality and homogeneity of our hybrid nanoparticles allows for detailed analysis of their luminescence. A strong correlation between dark field scattering and luminescence spectra is shown on a single particle level, indicating a dominant role of the longitudinal plasmonic band in luminescence enhancement. The spacer thickness dependence of photoluminescence intensity enhancement is investigated using a combination of experimental measurements and numerical simulations. An optimal separation distance of 5 nm is found, yielding a 7.2× enhancement of the luminescence intensity. This result is mainly attributed to an increased quantum yield resulting from the Purcell enhanced radiative rate in the nanocrystals. The ease of fabrication, low cost, long-term stability and great emission properties of the hybrid nanoparticles make them a great candidate for bio-imaging or even targeted cancer treatment.

Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters.

Fluorophores functionalized with heavy elements show enhanced intersystem crossing due to increased spin-orbit coupling, which in turn shortens the fluorescence decay lifetime (τPL). This phenomenon is known as the heavy-atom effect (HAE). Here, we report the observation of increased τPL upon functionalisation of near-infrared photoluminescent gold nanoclusters with iodine. The heavy atom-mediated increase in τPL is in striking contrast with the HAE and referred to as inverse HAE. Femtosecond and nanosecond transient absorption spectroscopy revealed overcompensation of a slight decrease in lifetime of the transition associated with the Au core (ps) by a large increase in the long-lived triplet state lifetime associated with the Au shell, which contributed to the observed inverse HAE. This unique observation of inverse HAE in gold nanoclusters provides the means to enhance the triplet excited state lifetime.

Correction: Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters.

Correction for 'Inverse heavy-atom effect in near infrared photoluminescent gold nanoclusters' by Goutam Pramanik et al., Nanoscale, 2021, DOI: 10.1039/d1nr02440j.

Binuclear Lanthanide(III) Complexes with Chiral Ligands: Dynamic Equilibria in Solution and Binding with Nucleotides Studied by Spectroscopic Methods.

Binuclear lanthanide complexes of Eu(III) and Sm(III) were obtained in the presence of chiral ligand 1,2-(R,R+S,S)-N,N'-bis(2-pyridylmethylene),2-diamine. An unusual structure of the Eu(III) compound with two lanthanide atoms connected through two chlorines was determined by X-ray crystallography. In solution, the dimer coexists with a monomeric complex, and the stability of the binuclear form depends on the solvent and concentration. The dimer-monomer equilibrium was monitored by circularly polarized luminescence (CPL) measured on a Raman optical activity (ROA) spectrometer, where both forms provided large CPL anisotropic ratios of up to 5.6×10-2 . Monomer formation was favored in water, whereas the dimer was stabilized in methanol. When mixed with adenosine phosphates, AMP gave much smaller CPL than ADP and ATP, indicating a high affinity of the Eu (III) complex for the phosphate group, which in connection with the ROA/CPL technique can be developed into a bioanalytical probe.

Synthesis of Near-Infrared Emitting Gold Nanoclusters for Biological Applications.

Over the past decade, fluorescent gold nanoclusters (AuNCs) have witnessed growing popularity in biological applications and enormous efforts have been devoted to their development. In this protocol, a recently developed, facile method for preparation of water soluble, biocompatible, and colloidally stable near-infrared emitting AuNCs have been described in detail. This room-temperature, bottom-up chemical synthesis provides easily functionalizable AuNCs capped with thioctic acid and thiol-modified polyethylene glycol in aqueous solution. The synthetic approach requires neither organic solvents or additional ligand exchange nor extensive knowledge of synthetic chemistry to reproduce. The resulting AuNCs offer free surface carboxylic acids, which can be functionalized with various biological molecules bearing a free amine group without adversely affecting the photoluminescent properties of the AuNCs. A quick, reliable procedure for flow cytometric quantification and confocal microscopic imaging of AuNC uptake by HeLa cells also been described. Due to the large Stokes shift, proper setting of filters in flow cytometry and confocal microscopy is necessary for efficient detection of near-infrared photoluminescence of AuNCs.