Near-infrared Photoluminescence Research Articles

X-ray photoelectron spectroscopy and NIR self-quenching emission behavior in Ho3+ doped YOF and V-YOF

Stoichiometric (YOF) and non-stoichiometric yttrium oxyfluoride (Y7O6F9) also known as the vernier phase (V-YOF) were investigated for possible optical applications. Both structures were prepared from a single source through the pyrolysis method. The V-YOF and YOF structures decomposed at 900 °C and 950 °C, respectively. X-ray photoelectron spectroscopy revealed four different yttrium sites in the V-YOF structure. The visible holmium ions emission doped in both consisted of three regions due to the 5S2,5F4 → 5I8, 5F5 → 5I8, and 5S2,5F4 → 5I7 transitions. The YOF structure's visible lifetime was also longer than in the V-YOF structure. The near-infrared photoluminescence emission originated from 5S2,5F4 → 5I6, 5I6 → 5I8 in both structures. The 5S2,5F4 → 5I6 near-infrared lifetimes for both decreased, indicating an energy transfer process. The 5I6 → 5I8 lifetime in both fluctuated due to the possibility of self-quenching through photon-trapping processes. The lifetimes were in the microseconds range.

Pseudohalogen Ammonium Salt-Assisted Syntheses of Large-Sized Indium Phosphide Quantum Dots with Near-Infrared Photoluminescence.

The development of indium phosphide (InP)-based quantum dots (QDs) with a near-infrared (NIR) emission area still lags behind the visible wavelength region and remains problematic. This study describes a one-step in situ pseudohalogen ammonium salt-assisted approach to generate NIR-emitted InP-based QDs with high photoluminescence quantum yields (PLQYs). The coexistence of NH4+ and PF6- ions from NH4PF6 may in situ synchronously etch and passivate the surface oxides and impede the creation of traps under the whole growth process of InP QDs. Experimental findings demonstrated that the in situ pseudohalogen ammonium salt-assisted syntheses technique may feature emission at a full width at half-maximum (fwhm) peak as fine as ∼45 nm and broaden the emission range to around ∼780 nm. A two-step approach for ZnS shells was developed to further improve the PLQY of NIR-emitted InP QDs. Furthermore, the constructed high-power intrinsically stretchable NIR color-conversion film employing the InP-based QDs/polymer composites presented excellent luminescence conversion ability and stretchability.

Trap-Mediated Sensitization Governs Near-Infrared Emission from Yb3+-Doped Mixed-Halide CsPbClxBr3-x Perovskite Nanocrystals.

Understanding the photosensitization mechanisms in Yb3+-doped perovskite nanocrystals is crucial for developing their anticipated photonic applications. Here, we address this question by investigating near-infrared photoluminescence of Yb3+-doped mixed-halide CsPbClxBr3-x nanocrystals as a function of temperature and revealing its strong dependence on the stoichiometry of the host perovskite matrix. To explain the observed experimental trends, we developed a theoretical model in which energy transfer from the perovskite matrix to Yb3+ ions occurs through intermediate trap states situated beneath the conduction band of the host. The developed model provides an excellent agreement with experimental results and is further validated through the measurements of emission saturation at high excitation powers and near-infrared photoluminescence quantum yield as a function of the anion composition. Our findings establish trap-mediated energy transfer as a dominant photosensitization mechanism in Yb3+-doped CsPbClxBr3-x nanocrystals and open up new ways of engineering their optical properties for light-emitting and light-harvesting applications.

(Benzimidazolium)2GeI4: A layered two-dimensional perovskite with dielectric switching and broadband near-infrared photoluminescence

Two-dimensional (2D) lead halide perovskites have attracted tremendous attention due to their outstanding physical properties. However, the presence of toxic lead is a major problem for large-scale applications. Here, we report the synthesis, phase transition, dielectric and photoluminescence (PL) properties of a lead-free 2D Ge-based perovskite (BIM)2GeI4 (BIM = benzimidazolium) which experiences a phase transition at 405 K accompanied by an order-disorder change of organic spacer. Moreover, the step-like dielectric transition near the phase transition temperature makes it suitable for dielectric switching. Meanwhile, (BIM)2GeI4 has a direct bandgap of 2.23 eV and broadband emission from 550 to 1000 nm, implying its unique optical property for potential near-infrared lighting and displaying. This work provides a fresh example for the development of lead-free 2D Ge-based perovskite with potential applications in the fields of optoelectronics and high temperature dielectric switching.

Lanthanide Doping into All-Inorganic Heterometallic Halide Layered Double Perovskite Nanocrystals for Multimodal Visible and Near-Infrared Emission.

The introduction of lanthanide ions (Ln3+) into all-inorganic lead-free halide perovskites has captured significant attention in optoelectronic applications. However, doping Ln3+ ions into heterometallic halide layered double perovskite (LDP) nanocrystals (NCs) and their associated doping mechanisms remain unexplored. Herein, we report the first colloidal synthesis of Ln3+ (Yb3+, Er3+)-doped LDP NCs utilizing a modified hot-injection method. The resulting NCs exhibit efficient near-infrared (NIR) photoluminescence in both NIR-I and NIR-II regions, achieved through energy transfer down-conversion mechanisms. Density functional theory calculations reveal that Ln3+ dopants preferentially occupy the Sb3+ cation positions, resulting in a disruption of local site symmetry of the LDP lattices. By leveraging sensitizations of intermediate energy levels, we delved into a series of Ln3+-doped Cs4M(II)Sb2Cl12 (M(II): Cd2+ or Mn2+) LDP NCs via co-doping strategies. Remarkably, we observe a brightening effect of the predark states of Er3+ dopant in the Er3+-doped Cs4M(II)Sb2Cl12 LDP NCs owing to the Mn component acting as an intermediate energy bridge. This study not only advances our understanding of energy transfer mechanisms in doped NCs but also propels all-inorganic LDP NCs for a wider range of optoelectronic applications.

Type‐II CdSe/ZnO Core/Shell Nanorods: Nanoheterostructures with A Tunable Dual Emission in Visible and Near‐Infrared Spectral Ranges

AbstractA synthesis and characterization of luminescent nano‐heterostructures consisting of CdSe nanorod (NR) cores and a ZnO shell with up to three monolayers of ZnO is reported. The core/shell heterostructures show a tunable, dual photoluminescence (PL) in visible and Near Infrared (NIR) spectral ranges. Upon shelling the visible PL band attributed to the carrier recombination within the CdSe core shifts to lower energy by ≈0.05 to 0.15 eV relative to the bare CdSe NRs, due to a reduced quantum confinement. A NIR band, observed ≈0.4 – 0.5 eV below the PL energy of the CdSe core, is attributed to a type‐II carrier recombination across the CdSe/ZnO interface. The total PL quantum yield (PLQY) in the brightest heterostructures reaches ≈20%, increasing ≈100‐fold over the PLQY of the corresponding bare CdSe NRs. The average lifetimes of the visible PL in some heterostructures exceeds 100 ns, compared to ≈5 ns lifetime typical for bare CdSe NRs. The average PL lifetimes attributed to the type‐II charge separated states exceed one microsecond. Strong NIR PL, tunable in the 800–900 nm spectral range and the long‐lived charge separated state make the CdSe/ZnO core‐shell NRs appealing materials for exploitation in applications such as bioimaging, photocatalysis and optoelectronics.

Near-infrared two-photon excited photoluminescence from Yb3+-doped CsPbClxBr3-x perovskite nanocrystals embedded into amphiphilic silica microspheres.

Nonlinear absorption of metal-halide perovskite nanocrystals (NCs) makes them an ideal candidate for applications which require multiphoton-excited photoluminescence. By doping perovskite NCs with lanthanides, their emission can be extended into the near-infrared (NIR) spectral region. We demonstrate how the combination of Yb3+ doping and bandgap engineering of cesium lead halide perovskite NCs performed by anion exchange (from Cl- to Br-) leads to efficient and tunable emitters that operate under two-photon excitation in the NIR spectral region. By optimizing the anion composition, Yb3+-doped CsPbClxBr3-x NCs exhibited high values of two-photon absorption cross-section reaching 2.3 × 105 GM, and displayed dual-band emission located both in the visible (407-493 nm) and NIR (985 nm). With a view of practical applications of bio-visualisation in the NIR spectral range, these NCs were embedded into silica microspheres which were further wrapped with amphiphilic polymer shells to ensure their water-compatibility. The resulting microspheres with embedded NCs could be easily dispersed in both toluene and water, while still exhibiting a dual-band emission in visible and NIR under both one- and two-photon excitation conditions.

Near-Infrared Emission of Ag+ Doped CuInSe2 Quantum Dots

Copper-indium-selenide (CISe) quantum dots (QDs) are a class of appealing materials due to their near-infrared (NIR) photoluminescence (PL) and as a non-toxic alternative to lead and cadmium-based QDs. To improve the low photoluminescence quantum yield (PLQY) of CISe core QDs, the zinc sulfide (ZnS) shell was grown to passivate surface defect states on the CISe core. CISe/ZnS core-shell QDs were synthesized with tetrahedral structure and chalcopyrite phase, resulting in an emission wavelength of 992 nm and a PLQY of 90%. Additionally, Ag2+ was doped into the CISe core to redshift the emission wavelength. The combination of electrons in the conduction band and holes in the trap state formed by Ag2+ led to light emission and a red-shifted emission wavelength. By tuning the stoichiometry and shelling time, Ag-doped CISe/ZnS core-shell QDs were successfully synthesized with a PLQY of 18% at an emission wavelength of 1200 nm. This wavelength falls in the NIR-II range, characterized by minimum absorption, biological autofluorescence, reduced scattering, and deep tissue penetration. The tunable emission and high luminescent CISe QDs have great potential in biological labeling, sensing and optoelectronics applications. Figure 1

Net Gain at the Near‐Infrared from CsPbBr3 Quantum Dots Sensitized Nd3+‐activated Tellurite Glass Under Solar Excitation

AbstractLanthanide ions (Ln3+) doped near‐infrared (NIR) phosphors play a critical role in applications requiring a compact, reliable, and economical NIR light source, but as yet they suffer from weak and narrow‐band absorption because of intrinsic photophysical limitations of Ln3+. Here, CsPbBr3 perovskite quantum dots (PQDs) and Nd3+ co‐doped tellurite glassy phosphor is designed to significantly upgrade the NIR photoluminescence (PL) efficiency of Ln3+. Benefiting from the sensitization effect of the PQDs on Nd3+, the PL excitation band of Nd3+ is greatly extended, permitting far more excitation channels that are impossible for conventional Nd3+‐doped glass phosphors. Such glassy phosphors also show a good stability, and when coupled with a commercial UV (or blue) chip, a compact and low‐cost NIR phosphor‐converted LED (pc‐LED) is constructed with a photoelectric conversion efficiency of 2.25% and an output power of 2.55 mW. A proof‐of‐concept demonstration for night vision application is given using the NIR pc‐LED. The excellent overlap with the solar spectrum in the visible portion inspires us to explore the possibility of sunlight excitation, and a net gain of ≈5 dB cm−1 is obtained near the 1064 nm. The implications of the present study are enormous considering diverse combinations of PQDs and Ln3+ in GCs.

Vivid Colored Cooling Structure Managing Full Solar Spectrum via Near-Infrared Reflection and Photoluminescence.

Colored radiative cooling (CRC) offers an attractive alternative for surface and space cooling, while preserving the aesthetics of an object. However, there has been no study on the CRC using phosphors in regard to vivid coloration, sophisticated performance investigation, retention of properties, functionality, and structural flexibility all at once. Thus, to manage the entire solar spectrum, a colored cooling structure comprising a near-infrared (NIR)-reflective bottom layer and a top colored layer with a phosphor-embedded polymer matrix is proposed. The structure is paintable, vividly colored, hydrophobic, and ultraviolet (UV) and water resistant. In the daytime outdoor measurement, the structure with red, orange, and yellow colors exhibited lower temperature than a control group using commercial white paint by 4.7 °C, 7.2 °C, and 7.4 °C, respectively. After precise theoretical and experimental time-tracing temperature validation, the CRC performance enhancement from NIR reflection and photoluminescence effects was thoroughly analyzed, and a temperature reduction of up to 16.1 °C was achieved for the orange-colored structure. Furthermore, experiments of hydrophobicity infusion and exposure to UV and deionized water verified the durability of the colored cooling structure. In addition, flexible-film-type colored cooling structures were demonstrated using different bottom reflective layers, such as a silver thin film and porous aluminum oxide particle-embedded poly(vinylidene fluoride-co-hexafluoropropylene), suggesting the potential applicability of these colored cooling structures for vivid-colored, functional, and durable CRC.

Tailoring Carbon Tails of Ligands on Au52(SR)32 Nanoclusters Enhances the Near-Infrared Photoluminescence Quantum Yield from 3.8 to 18.3.

One of the important factors that determine the photoluminescence (PL) properties of gold nanoclusters pertain to the surface. In this study, four Au52(SR)32 nanoclusters that feature a series of aromatic thiolate ligands (-SR) with different bulkiness at the para-position are synthesized and investigated. The near-infrared (NIR) photoluminescence (peaks at 900-940 nm) quantum yield (QY) is largely enhanced with a decrease in the ligand's para-bulkiness. Specifically, the Au52(SR)32 capped with the least bulky p-methylbenzenethiolate (p-MBT) exhibits the highest PLQY (18.3% at room temperature in non-degassed dichloromethane), while Au52 with the bulkiest tert-butylbenzenethiolate (TBBT) only gives 3.8%. The large enhancement of QY with fewer methyl groups on the ligands implies a nonradiative decay via the multiphonon process mediated by C-H bonds. Furthermore, single-crystal X-ray diffraction (SCXRD) comparison of Au52(p-MBT)32 and Au52(TBBT)32 reveals that fewer methyl groups at the para-position lead to a stronger interligand π···π stacking on the Au52 core, thus restricting ligand vibrations and rotations. The emission nature is identified to be phosphorescence and thermally activated delayed fluorescence (TADF) based on the PL lifetime, 3O2 quenching, and temperature-dependent PL and absorption studies. The 1O2 generation efficiencies for the four Au52(SR)32 NCs follow the same trend as the observed PL performance. Overall, the highly NIR-luminescent Au52(p-MBT)32 nanocluster and the revealed mechanisms are expected to find future applications.

Bandgap Engineering of Erbium-Metallofullerenes toward Switchable Photoluminescence.

Encapsulating photoluminescent lanthanide ions like erbium (Er) into fullerene cages affords photoluminescent endohedral metallofullerenes (EMFs). Few reported photoluminescent Er-EMFs are all based on encapsulation of multiple (two to three) metal atoms, whereas mono-Er-EMFs exemplified by Er@C82 are not photoluminescent due to its narrow optical bandgap. Herein, by entrapping an Er-cyanide cluster into various C82 cages to form novel Er-monometallic cyanide clusterfullerenes (CYCFs), ErCN@C82 (C2 (5), Cs (6), and C2 v (9)), the photoluminescent properties of CYCFs are investigated, and obvious near-infrared (NIR) photoluminescence only is observed for ErCN@C2 (5)-C82 . Combined with a comparative photoluminescence study of three medium-bandgap di-Er-EMFs, including Er2 @Cs (6)-C82 , Er2 O@Cs (6)-C82 , and Er2 C2 @Cs (6)-C82 , this study proposes that the optical bandgap can be used as a simple criterion for switching the photoluminescence of Er-EMFs, and the bandgap threshold is determined to be between 0.83 and 0.74eV. Furthermore, the photoluminescent patterns of these three di-Er-EMFs differ dramatically. It is found that the location of the Er atom within the same Cs (6)-C82 cage is almost fixed and independent on the endo-unit; thus the previous statement on the key role of metal position in photoluminescence of di-Er-EMFs seems erroneous, and the geometric configuration of the endo-unit, especially the bridging mode of two Er ions, is decisive instead.

Multifunctional Nanoparticles with Superparamagnetic Mn(II) Ferrite and Luminescent Gold Nanoclusters for Multimodal Imaging.

Gold nanoclusters (AuNCs) with fluorescence in the Near Infrared (NIR) by both one- and two-photon electronic excitation were incorporated in mesoporous silica nanoparticles (MSNs) using a novel one-pot synthesis procedure where the condensation polymerization of alkoxysilane monomers in the presence of the AuNCs and a surfactant produced hybrid MSNs of 49 nm diameter. This method was further developed to prepare 30 nm diameter nanocomposite particles with simultaneous NIR fluorescence and superparamagnetic properties, with a core composed of superparamagnetic manganese (II) ferrite nanoparticles (MnFe2O4) coated with a thin silica layer, and a shell of mesoporous silica decorated with AuNCs. The nanocomposite particles feature NIR-photoluminescence with 0.6% quantum yield and large Stokes shift (290 nm), and superparamagnetic response at 300 K, with a saturation magnetization of 13.4 emu g-1. The conjugation of NIR photoluminescence and superparamagnetic properties in the biocompatible nanocomposite has high potential for application in multimodal bioimaging.

Tunable broadband near-infrared photoluminescence of Mg2LaTaO6:Cr3+ phosphors for light-emitting diodes

Near-infrared phosphor-converted light-emitting diodes (NIR pc-LED) prepared with near-infrared (NIR) phosphors have potential applications in various aspects. In this paper, Cr3+-activated Mg2LaTaO6 (MLTO: Cr3+) phosphors were prepared by the conventional high-temperature solid-phase method. The structure, morphology, and photoluminescence (PL) spectra of MLTO: Cr3+ phosphor were investigated. There is broadband NIR emission and the emission peak is red-shifted with the increase of doping concentration. The crystal field strengths of the samples were calculated and the relationship between the emission peak positions of the samples and the crystal field strengths was investigated. In addition, the concentration quenching mechanism of the samples was discussed, which is mainly attributed to dipole-dipole interactions. The internal quantum efficiency (IQE) of the MLTO: 0.4 mol% Cr3+ sample was measured with an IQE value of 76.48 %. NIR pc-LED devices were fabricated by combining the prepared MLTO: Cr3+ phosphor and blue-emitting LED chips, which are capable of emitting NIR light.

Near-infrared photoluminescent detection of serum albumin using single-walled carbon nanotubes locally functionalized with a long-chain fatty acid

Serum albumin (SA) is a protein found in biofluids that is useful for diagnosing kidney and liver-related diseases. Single-walled carbon nanotubes (SWCNTs) showing photoluminescence (PL) in the near-infrared (NIR) region are prospective candidates for diagnosis NIR probes. Their NIR PL enhancement has been reported by defect introduction techniques based on local chemical functionalization of SWCNTs. The locally functionalized (lf-)SWCNTs exhibit a bright defect PL (>1000 nm) from the defect sites and its sensitive wavelength shifts in response to surrounding dielectric atmospheres have been reported. Here, we used the sensitive defect PL responses of lf-SWCNTs to establish a NIR sensing system for SA detection. A palmitic acid group that binds to SA strongly and selectively, was functionalized at the defect site of lf-SWCNTs (lf-SWCNTs-p). Compared to typical PL of unmodified SWCNTs, selective defect PL red-shifts (of 2.5 nm max.) were clearly observed according to the addition of SA in phosphate-buffered saline. The defect PL responsiveness could detect different SA from human, bovine, and mouse. The red-shifts of the defect PL occurred by formation of a high dielectric environment based on the specific binding between SA and the palmitic acid groups on the defect sites. The lf-SWCNTs-p detected SA-spiked serum and albuminuria of diabetic mouse in body fluids. The findings show that the lf-SWCNTs-p offer an NIR PL analytical tool for SA in body fluids applicable to a disease diagnosis and expand the bioapplications of lf-SWCNTs based on their molecular design-based defect engineering.

Tm3+-doped Cs2Ag0.6Na0.4In0.9Bi0.1Cl6 microcrystals for thermometry

Lead-free double perovskites have superb luminescence properties for broad applications. However, increasing or improving near-infrared (NIR) photoluminescence (PL) is still a challenge. In this paper, a high-performance microcrystal is designed based on Tm3+ heavily doped Cs2Ag0.6Na0.4In0.9Bi0.1Cl6 (CANIBC), which realize both the self-trapped excitons (STEs) and Tm3+ NIR emission. The emission mechanism and energy transfer (ET) process are studied by steady-state and time-resolved PL spectra. The ET efficiency from STEs to Tm3+ can reach 38.3 %, and the NIR PL quantum yield of Tm3+ can reach 22.7 %. Meanwhile, the PL spectra of Tm3+-doped CANIBC microcrystals (MCs) with different concentrations are used to investigate their temperature sensing properties based on both fluorescence intensity ratio (FIR) and lifetime. Based on the FIR, relative sensitivity (Sr) can reach 2.93 % K−1 at 303 K. Moreover, based on lifetimes, Sr can maintain more than 1.55 % K−1 from 303 to 453 K, and maximum Sr can also achieve 2.38 % K−1 at 360 K. These excellent luminescence and sensing properties offer greater development potential in the field of NIR phosphor and thermometry.

(Invited) Microenvironment Responsiveness of Defect Photoluminescence of Locally Functionalized Single-Walled Carbon Nanotubes and Its Sensing Applications

Photoluminescence (PL) of single-walled carbon nanotubes (SWCNTs) in the near infrared (NIR) region is applicable to advanced optical applications such as bio-imaging and sensing. Local chemical functionalization (slight amount of chemical modification) of SWCNTs has been developed to introduce sp3 carbon defects in the sp2 carbon network of the tube walls for the luminescent defect formation.[1-3] The resultant locally functionalized SWCNTs (lf-SWCNTs) show defect PL (E 11* PL) with red-shifted wavelengths and increased quantum yields compared to original E 11 PL of pristine SWCNTs. For lf-SWCNTs, molecularly designed modifier molecules have enabled the defect PL wavelength modulation[4] and the sensing function creation.[5,6]Recently, we have reported the unique microenvironment responsiveness of defect PL of lf-SWCNTs; namely, the greater wavelength shifts of E 11* PL than E 11 PL by dielectric effects[7] and the PL shifting behavior modulation based on the chemical structure difference of the functionalized sites and the exciton localization effects[8] were observed. The microenvironment responsiveness of the defect PL was applied to the biological sensing application development.[9] To investigate protein detection/recognition functions of lf-SWCNTs, we introduced an avidin-biotin interaction with a selective and strong binding fashion at the functionalized sites of lf-SWCNTs. The lf-SWCNTs tethering biotin groups (lf-SWCNTs-b) were synthesized through diazonium chemistry, followed by its subsequent-modification. When neutravidin was mixed with a lf-SWCNTs-b solution, E 11* PL peak was red-shifted, indicating the higher polarity environment formation by the neutravidin adsorption on lf-SWCNTs-b. When avidin or streptavidin was used, wavelength shifting behaviors of E 11* PL of lf-SWCNTs-b were clearly changed depending on the used avidin derivatives. The results indicate the different polarity environment formation deriving from structural differences of each avidin derivative. Moreover, the detection signal enhancement was observed in a film device using lf-SWCNTs-b. Therefore, lf-SWCNTs have a high potential for development of advanced protein detection/recognition systems using NIR PL.[1] T. Shiraki et al. Acc. Chem. Res., 53, 1846 (2020). [2] S. Tretiak et al., Acc. Chem. Res., 53, 1791(2020) [3] Y. Wang et al. Nat. Rev. Chem., 3, 375 (2019). [4] T. Shiraki et al. ACS Nano, DOI: 10.1021/acsnano.2c09897 (2022). [5] T. Shiraki et al. Chem. Commun., 52, 12972 (2016). [6] S. Kruss et al, Angew. Chem. Int. Ed., 59, 17732 (2020). [7] T. Shiraki et al. Chem. Commun., 55, 3662 (2019). [8] T. Shiraki et al. J. Phys. Chem. C, 125, 12758 (2021). [9] T. Shiraki et al. Nanoscale, 14, 13090 (2022). Figure 1

Understanding Oligonucleotide Hybridization and the Role of Anchoring on the Single-Walled Carbon Nanotube Corona Phase for Viral Sensing Applications

Semiconducting single-walled carbon nanotubes (SWCNTs) with tailored corona phases (CPs), or surface adsorbed molecules, have emerged as a promising interface for sensing applications. The adsorption of an analyte can be specifically transduced as a modulation of their band gap near-infrared (nIR) photoluminescence (PL). One such CP ideal for this purpose is single-stranded DNA (ssDNA), where subsequent sequence dependent hybridization can result in PL emission wavelength shifts. Due to ssDNA adsorption to the SWCNT surface, the resultant non-canonical hybridization and its effect on SWCNT photophysical properties are not well understood. In this work, we study 20- and 21-mer DNA and RNA hybridization on the complementary ssDNA-SWCNT CP in the context of nucleic acid sensing for SARS-CoV-2 sequences as model analytes. We found that the van’t Hoff transition enthalpy of hybridization on SWCNT CP was -11.9 kJ mol-1, much lower than that of hybridization in solution (-707 kJ mol-1). We used SWCNT solvatochromism to calculate the solvent exposed surface area to indicate successful hybridization. We found that having a 30-mer anchor region in addition to the complementary region significantly improved PL response sensitivity and selectivity, with (GT)15 anchor preferred for RNA targets. Coincubation of ssDNA-SWCNT with analyte at 37°C resulted in faster hybridization kinetics without sacrificing specificity. Other methods aimed to improve CP rearrangement kinetics such as bath sonication and surfactant additions were ineffective. We also determined that target sequence choice is important as secondary structure formation in target is negatively correlated with hybridization. Best performing CPs showed detection limits of 11 nM and 13 nM for DNA and RNA targets respectively. Finally, we simulated sensing conditions using saliva environment, showing sensor compatibility in biofluids. In total, this work elucidates key design features and processing to enable sequence specific hybridization on ssDNA-SWCNT CP.

Structural, optical and temperature-sensing properties of LaOF:Yb3+, Tm3+ nanophosphor prepared by microwave-assisted hydrothermal synthesis

Luminescence thermometry forms a unique tool for remote temperature sensing by exploiting the variations in the luminescence properties of the probe. Thermometry based on the fluorescence intensity ratios (FIR) is a widely practiced approach due to them being a self-referenced measure. The quest for efficient temperature probes for thermometry led to the discovery of LaOF:Yb3+,Tm3+ upconversion nanoparticles, which were synthesized using a microwave-assisted hydrothermal synthesis method. Blue and near-infrared upconversion photoluminescence (UCPL) emission was observed under 980 nm laser excitation. The temperature-dependent UCPL was studied for their temperature sensing application. FIR of thermally coupled and non-coupled emission bands were calculated in the temperature range of 303 to 473 K. The thermometric characteristics such as absolute sensitivity, relative sensitivity and temperature uncertainty were also determined. The thermal stability of the UCNPs was established under continuous laser exposure operating at maximum power (2500mW). The reproducibility of the UCNPs was also determined by temperature cycling the UCNPs.

Negative Thermal Quenching in Quantum-Cutting Yb3+-Doped CsPb(Cl1-xBrx)3 Perovskite Nanocrystals.

Ytterbium-doped all-inorganic lead-halide perovskites (Yb3+:CsPb(Cl1-xBrx)3) show broadband absorption and exceptionally high near-infrared photoluminescence quantum yields, providing opportunities for solar spectral shaping to improve photovoltaic power conversion efficiencies. Here, we report that Yb3+:CsPb(Cl1-xBrx)3 NCs also show extremely strong negative thermal quenching of the Yb3+ luminescence, with intensities at room temperature >100 times those at 5 K for some compositions. Analysis of this temperature dependence as a function of x shows that it stems from thermally activated quantum cutting related to the temperature dependence of the spectral overlap between the PL of the perovskite (donor) and the simultaneous-pair absorption of two Yb3+ ions (acceptor). In the Yb3+:CsPbBr3 limit, this spectral overlap goes to zero at 5 K, such that only single-Yb3+ sensitization requiring massive phonon emission occurs. At room temperature, Yb3+ PL in this composition is enhanced ∼135-fold by thermally activated quantum cutting, highlighting the extreme efficiency of quantum cutting relative to single-Yb3+ sensitization. These results advance the fundamental mechanistic understanding of quantum cutting in doped perovskites, with potential ramifications for solar and photonics technologies.