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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Immunomodulatory Potential of Differently-Terminated Ultra-Small Silicon Carbide Nanoparticles.

Ultra-small nanoparticles with sizes comparable to those of pores in the cellular membrane possess significant potential for application in the field of biomedicine. Silicon carbide ultra-small nanoparticles with varying surface termination were tested for the biological system represented by different human cells (using a human osteoblastic cell line as the reference system and a monocyte/macrophage cell line as immune cells). The three tested nanoparticle surface terminations resulted in the observation of different effects on cell metabolic activity. These effects were mostly noticeable in cases of monocytic cells, where each type of particle caused a completely different response ('as-prepared' particles, i.e., were highly cytotoxic, -OH terminated particles slightly increased the metabolic activity, while -NH2 terminated particles caused an almost doubled metabolic activity) after 24 h of incubation. Subsequently, the release of cytokines from such treated monocytes and their differentiation into activated cells was determined. The results revealed the potential modulation of immune cell behavior following stimulation with particular ultra-small nanoparticles, thus opening up new fields for novel silicon carbide nanoparticle biomedical applications.

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.

Room-Temperature Defect Qubits in Ultrasmall Nanocrystals.

There is an urgent quest for room-temperature qubits in nanometer-sized, ultrasmall nanocrystals for quantum biosensing, hyperpolarization of biomolecules, and quantum information processing. Thus far, the preparation of such qubits at the nanoscale has remained futile. Here, we present a synthesis method that avoids any interaction of the solid with high-energy particles and uses self-propagated high-temperature synthesis with a subsequent electrochemical method, the no-photon exciton generation chemistry to produce room-temperature qubits in ultrasmall nanocrystals of sizes down to 3 nm with high yield. We first create the host silicon carbide (SiC) crystallites by high-temperature synthesis and then apply wet chemical etching, which results in ultrasmall SiC nanocrystals and facilitates the creation of thermally stable defect qubits in the material. We demonstrate room-temperature optically detected magnetic resonance signal of divacancy qubits with 3.5% contrast from these nanoparticles with emission wavelengths falling in the second biological window (1000-1380 nm). These results constitute the formation of nonperturbative bioagents for quantum sensing and efficient hyperpolarization.

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.

Gold nanoclusters with bright near-infrared photoluminescence.

The increase in nonradiative pathways with decreasing emission energy reduces the luminescence quantum yield (QY) of near-infrared photoluminescent (NIR PL) metal nanoclusters. Efficient surface ligand chemistry can significantly improve the luminescence QY of NIR PL metal nanoclusters. In contrast to the widely reported but modestly effective thiolate ligand-to-metal core charge transfer, we show that metal-to-ligand charge transfer (MLCT) can be used to greatly enhance the luminescence QY of NIR PL gold nanoclusters (AuNCs). We synthesized water-soluble and colloidally stable NIR PL AuNCs with unprecedentedly high QY (∼25%) upon introduction of triphenylphosphonium moieties into the surface capping layer. By using a combination of spectroscopic and theoretical methods, we provide evidence for gold core-to-ligand charge transfer occurring in AuNCs. We envision that this work can stimulate the development of these unusually bright AuNCs for promising optoelectronic, bioimaging, and other applications.

Thermally stimulated exciton emission in Si nanocrystals.

Increasing temperature is known to quench the excitonic emission of bulk silicon, which is due to thermally induced dissociation of excitons. Here, we demonstrate that the effect of temperature on the excitonic emission is reversed for quantum-confined silicon nanocrystals. Using laser-induced heating of silicon nanocrystals embedded in SiO2, we achieved a more than threefold (>300%) increase in the radiative (photon) emission rate. We theoretically modeled the observed enhancement in terms of the thermally stimulated effect, taking into account the massive phonon production under intense illumination. These results elucidate one more important advantage of silicon nanostructures, illustrating that their optical properties can be influenced by temperature. They also provide an important insight into the mechanisms of energy conversion and dissipation in ensembles of silicon nanocrystals in solid matrices. In practice, the radiative rate enhancement under strong continuous wave optical pumping is relevant for the possible application of silicon nanocrystals for spectral conversion layers in concentrator photovoltaics.

Changes of the absorption cross section of Si nanocrystals with temperature and distance.

The absorption cross section (ACS) of silicon nanocrystals (Si NCs) in single-layer and multilayer structures with variable thickness of oxide barriers is determined via a photoluminescence (PL) modulation technique that is based on the analysis of excitation intensity-dependent PL kinetics under modulated pumping. We clearly demonstrate that roughly doubling the barrier thickness (from ca. 1 to 2.2 nm) induces a decrease of the ACS by a factor of 1.5. An optimum separation barrier thickness of ca. 1.6 nm is calculated to maximize the PL intensity yield. This large variation of ACS values with barrier thickness is attributed to a modulation of either defect population states or of the efficiency of energy transfer between confined NC layers. An exponential decrease of the ACS with decreasing temperature down to 120 K can be explained by smaller occupation number of phonons and expansion of the band gap of Si NCs at low temperatures. This study clearly shows that the ACS of Si NCs cannot be considered as independent on experimental conditions and sample parameters.

Boron-Incorporating Silicon Nanocrystals Embedded in SiO2: Absence of Free Carriers vs. B-Induced Defects.

Boron (B) doping of silicon nanocrystals requires the incorporation of a B-atom on a lattice site of the quantum dot and its ionization at room temperature. In case of successful B-doping the majority carriers (holes) should quench the photoluminescence of Si nanocrystals via non-radiative Auger recombination. In addition, the holes should allow for a non-transient electrical current. However, on the bottom end of the nanoscale, both substitutional incorporation and ionization are subject to significant increase in their respective energies due to confinement and size effects. Nevertheless, successful B-doping of Si nanocrystals was reported for certain structural conditions. Here, we investigate B-doping for small, well-dispersed Si nanocrystals with low and moderate B-concentrations. While small amounts of B-atoms are incorporated into these nanocrystals, they hardly affect their optical or electrical properties. If the B-concentration exceeds ~1 at%, the luminescence quantum yield is significantly quenched, whereas electrical measurements do not reveal free carriers. This observation suggests a photoluminescence quenching mechanism based on B-induced defect states. By means of density functional theory calculations, we prove that B creates multiple states in the bandgap of Si and SiO2. We conclude that non-percolated ultra-small Si nanocrystals cannot be efficiently B-doped.