Photoluminescence Peak Wavelength Research Articles

Carbon dots with high brightness and stability towards efficient Cr(Ⅵ) and l-arginine sensors

To create fluorescent sensors for Cr (VI) and l-arginine detection, blue-emitting carbon dots (CDs, named as M-CDs) were prepared via a solvothermal synthesis by using m-phenylenediamine. The introduction of sulfuric acid changed the blue-emitting of CDs into green-emitting (named as S-CDs), in which the photoluminescence (PL) peak wavelengths of samples M-CDs and S-CDs were 450 and 540 nm, while their PL efficiencies were 21.7 and 84.2 % respectively. Sulfuric acid resulted in the average fluorescent lifetime of the CDs was prolonged into 8.19 from 4.65 ns. The photo and thermal stable tests demonstrated that theses CDs revealed excellent stability. Meanwhile, CDs flexible films with bright blue- and green-emitting were prepared utilizing the favorable solubility of CDs in polar solvents. Mono-dispersed CDs as luminescent materials demonstrated it promising prospects in luminescent devices field. Furthermore, M-CDs exhibited excellent selectivity towards Cr(Ⅵ) and l-arginine. The detected limit (0.86 μM for Cr(Ⅵ) and 0.43 μM for l-arginine) was determined by assessing the response of M-CDs to various concentrations of Cr(Ⅵ) ion and l-arginine solutions. These bright CDs revealed great potential for accurate detection of Cr(Ⅵ) and l-arginine.

Surface-controlled carbon dots with high brightness and tunable emission towards fluorescent anti-counterfeiting and pH sensors

Compared with luminescent semiconductor nanocrystals, nontoxic and metal-free carbon dots (CDs) are advantages for the significant applications in displaying and various sensors. In this paper, blue- and green-emitting CDs with high brightness and stability were created via solvothermal synthesis using m-phenylenediamine and terephthalic acid. Solvents were adjusted to control the surface of CDs attaining high brightness. The blue-emitting CDs with a photoluminescence (PL) peak wavelength of 480 nm revealed PL quantum yields (PLQYs) of 30.4% while the green-emitting one revealed a PL peak wavelength of 500 nm and a PLQY of 55.1%. The PL properties of these CDs exhibited excellent pH dependence. The effects of solvents, synthetic parameters, and pH values on the structure and PL properties of CDs were tested. These CDs were used for pH sensors and multi-stage anti-counterfeiting ink. The blue-emitting CDs revealed high stability in a broad pH range while green-emitting CDs were sensitive to aqueous solution in the pH region of 10.00–10.78 with a sensitivity of 0.99/pH and pKa value of 10.34 ± 0.51. Because of the high stability, fluorescent inks were prepared using these multi-color CDs via direct dispersion in water, in which the inks showed high stability after 6 months of storage time.

Graphene Quantum Dots Based on Mechanical Exfoliation Methods: A Simple and Eco-Friendly Technique.

Graphene quantum dots (GQDs) are very precious, widely used, and face significant challenges in preparation methods. In this study, three mechanical methods are investigated for the preparation of GQDs. All of these methods are green, cost-effective, and simple. In fact, Graphite, as a main source of GQDs, is exfoliated and fragmented under mechanical forces by sonication and ball milling. This mechanical exfoliation method is effective for converting large flakes of graphite into quantum dots. Additionally, the proposed methods are simple and faster than other top-down GQD fabrication methods. High-power sonication is applied to graphene flakes by using the liquid-phase exfoliation method. The liquid phase consists of ethanol and water, which are completely eco-friendly. Exfoliation and fragmentation of graphene flakes are performed using different sonication and ball-milling times. The obtained results from the analysis of the synthesized GQDs exhibit pristine graphene's distinct structural, chemical, and optical properties. Several analyses, such as X-ray diffraction (XRD) and Fourier transform infrared spectroscopy, were applied to study the product structure. Dynamic light scattering (DLS) and field emission scanning electron microscopy (FESEM) were used to examine product size and morphology, which confirmed the nanosize of GQDs. The smallest observed size of GQDs is approximately 23 nm. It is estimated that 95% of the nanoparticles are between 0.001 and 0.1 μm in size (41 nm). The optical properties of GQDs were investigated by using ultraviolet-visible and photoluminescence (PL) techniques. The PL peak wavelength is approximately 610 nm. Eventually, the results proved that the combined use of two methods, ultrasonication and ball milling during liquid-phase exfoliation, will be a simple, cheap, and suitable method for the production of GQDs.

Growth of CsPbX3 nanocrystals using sol–gel SiO2 solid powders as reactors without capping agents towards anomalous stable emission membranes

To overcome the poor stability of metal halide perovskite nanocrystals (NCs) prepared in organic solvents, a solid reaction method at high temperature was developed using sol–gel porous SiO2 as a reactor. Sol-gel SiO2 powders were used to encapsulate CsPbX3 NCs at high temperatures (600–800 °C) in air to get SiO2/CsPbX3 glass by dispersing growth cites in advance and no ligands added. After NaOH etching, a thin dense SiO2 shell was remained on the surface of CsPbX3 NCs (named as CsPbX3@SiO2).The photoluminescence (PL) quantum yield of the CsPbX3@SiO2 was 86.7 %, in which their PL peak wavelengths were adjusted from 410-707 nm by changing halogen components. The dense SiO2 shell on CsPbX3 NCs blocked the connection of CsPbX3 cores with water and oxygen in the external environment, resulting in CsPbX3@SiO2 revealed extraordinary high stability. After immersing in water for half year, the PL intensity of CsPbX3@SiO2 composites was remained unchanged and the composites still revealed bright PL after heat-treating in boiling water for 14 h. These highly stable composites were used to fabricate a white light-emitting diode, in which the color coordinates are located at (0.36, 0.33), and the color temperature reaches 5169 K which belongs to the warm white light range.

Highly luminescent CsPbX3@MIL-53(Al) nanoarchitectonics with anomalous stability towards flexible emitting films

The poor stability of perovskite nanomaterials exposed in high temperature, moisture, light radiation, and polar solvent conditions severely restrict their commercial application. To address this issue, the growth in situ of CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) is carried out by using the stable aluminum (Al)-based metal-organic frameworks to create CsPbX3@MIL-53(Al) composites. Compared with pristine CsPbX3 NCs prepared using room temperature ligand assisted re-precipitation synthesis, the CsPbX3@MIL-53(Al) composites exhibit narrow photoluminescence (PL) spectra and greatly improved stability. The green emitting CsPbBr3@MIL-53(Al) composite exhibit narrowed PL spectrum (the full width at half-maximum of PL spectra: 20 nm for the composite and 28 nm for CsPbBr3 NCs) and a blue-shifted PL peak wavelength (517.6 nm for the composite and 527.6 nm for the CsPbBr3 NCs). The relationship of microstructure, components, PL, fluorescence lifetime, and stability are discussed systematically. Anomalous stability against heat-treatment, polar solvent and humidity conditions indicated the composites retained their initial PL intensity after storge more than 4 months in ambient conditions and heat-treated to 120ºC for 5 cycles. The emitting color of CsPbBr3@MIL-53(Al) composites are easily adjusted from blue, green to red by controlling the halide components of precursors. The composite was used to create emitting coating and highly bright flexible emitting films which also reveal high stability, suggesting that in situ encapsulation of CsPbX3 NCs in MIL-53(Al) would supply a novel platform for various emitting devices.

Modulation of optical properties for lighting applications based on CsPbBr3−xIx quantum dot doped glasses

All inorganic halide perovskite quantum dots (PQDs) exhibit excellent optical properties and have been intensively exploited for diverse applications in the field of optoelectronics. However, their inherent frangibility remains an enormous challenge for both practical applications and scientific research. The recently emerged oxide glasses doped with such PQDs exhibit high stability against degradation, which is promising for practical applications. Here, borosilicate glasses doped with CsPbBr3−xIx PQDs were prepared by the traditional melt-quenching and subsequent annealing process. By introducing alkaline metal oxides as the glass network modifier to adjust glass network structure, the optical properties of the precipitated PQDs are significantly enhanced. The photoluminescence (PL) intensity and photoluminescence quantum yield (PLQY) can be enhanced by up to 200 % and 29 % for the sample fabricated under optimal conditions, respectively. By leveraging the strong PL of the developed PQD-doped glasses, we demonstrate the fabrication of phosphor-converted light emitting devices for white light illumination and plant illumination based on samples with PL peak wavelengths at approximately 570 nm and 650 nm, respectively.

Enhancing microstructure and device performance of InGaN quantum dot micro-LEDs through substrate off-cut angle modulation

InGaN quantum dots (QDs) are regarded as a compelling candidate material for the fabrication of high-quality GaN-based micro-LEDs. In this work, to study the impact of a substrate structure on InGaN QDs and QD-based micro-LEDs, GaN-on-sapphire substrates with off-cut angles toward the a-axis of 0.2°, 0.4°, and 0.7° were utilized as templates for the fabrication of InGaN QDs and InGaN QDs-based micro-LEDs. Experimental results show that GaN template with 0.4° off-cut angle exhibits the narrowest terrace width and enables InGaN QDs to be higher and more uniform. The InGaN QD sample grown on 0.4° substrate has a very small wavelength shift of 2.5 nm with temperature increasing and owns the longest photoluminescence peak wavelength implying the highest In content. Furthermore, electroluminescence (EL) spectra demonstrate that QD-based micro-LED array has excellent wavelength stability under various injection currents, and the stability can be improved further on a GaN template with narrower terraces. The results indicate that altering the terrace width of GaN template is a feasible scheme for improving the properties of GaN-based micro-LEDs.

Achieving Long-Wavelength Electroluminescence Using Two-Coordinate Gold(I) Complexes: Overcoming the Energy Gap Law.

Two-coordinate coinage metal complexes have emerged as promising emitters for highly efficient organic light-emitting devices (OLEDs). However, achieving efficient long-wavelength electroluminescence emission from these complexes remains as a daunting challenge. To address this challenge, molecular design strategies aimed at bolstering the photoluminescence quantum yield (Φ) of Au(I) complex emitters in low-energy emission regions are investigated. By varying amido ligands, a series of two-coordinate Au(I) complexes is developed that exhibit photoluminescence peak wavelengths over a broad range of 533-750nm. These complexes, in particular, maintain Φ values up to 10% even in the near-infrared emission region, overcoming the constraints imposed by an energy gap. Quantum chemical calculations and photophysical analyses reveal the action of radiative control, which serves to overcome the energy gap law, becomes more pronounced as the overlap between hole and electron distributions (Sr (r)) in the excited state increases. It is further elucidated that Sr (r) increases with the distance between the hole-distribution centroid and the nitrogen atom in an amido ligand. Finally, multilayer OLEDs involving the Au(I) complex emitters exhibit performances beyond the borderline of the electroluminescence wavelength-external quantum efficiency space set by previous devices of coinage metal complexes.

Blue Emitting CsPbBr3: High Quantum Confinement Effect and Well‐Adjusted Shapes (Nanorods, Nanoplates, and Cubes) toward White Light Emitting Diodes

AbstractControlled nucleation and slow growth endow blue emitting CsPbX3 nanocrystals (NCs) with bright photoluminescence (PL), which is crucial needed in luminescent devices. In this paper, a low‐temperature injection synthesis method is developed to control nucleation and the growth process by decreasing the reaction rate of ions, thereby controlling the morphologies of CsPbX3 NCs in clusters, nanorods (NRs), nanoplates (NPLs), and nanocubes by adjusting precursors, ligands, and injection parameters. CsPbX3 NCs exhibit excellent PL properties such as high quantum confinement effect. The PL peak wavelengths of CsPbBr3 NPLs and NRs are at 451 and 467 nm, respectively, in which their full width at half maximum (FWHM) of PL spectra is 22 and 12 nm, while their PL efficiencies are 65 and 74%, respectively. The method is further used to create CsPbI3 and CsPbCl3. CsPbI3 NPLs and NRs reveal PL peaks at 590 and 600 nm and PL efficiencies of 56% and 60%, respectively. These NCs exhibit excellent stability against ultraviolet light irradiation. A color conversion layer for white light‐emitting diodes is fabricated using these highly bright NCs. A Commission Internationale d'Eclairage color coordinate of (0.31,0.33) is located at the white light region specified by Rec.2020 standard, and the color temperature reaches 6189 K.

Reaction-time-controlled carbon dots nanoarchitectonics with stable and bright photoluminescence for white light emission

It is still a challenge for multicolor carbon dots (CDs) with stable and bright photoluminescence (PL). The controlling of synthesis becomes a hot topic. In this paper, CDs with blue-, green- and red-emitting named as B-CDs, G-CDs, and R-CDs were prepared using three isomers of phenylenediamine as precursors by one-step solvothermal synthesis. Green and red emitting CDs with C, N and O components named as samples G-CDs and R-CDs revealed uniform nanoparticle distribution with average sizes of 7.2 and 5.7 nm, respectively. The PL peak wavelength of three kinds of CDs were 430, 546 and 613 nm, and their average fluorescence lifetime was 5.32, 22.35, 8.74 ns, respectively. The full width at half maximum of PL spectra of the samples was 65.12, 92.63, 83.62 nm, and their PL quantum yields were 8.19, 43.43, and 5.14%, respectively. The brightly luminescent CDs were further embedded in prepared polyvinyl alcohol films to prepare a white emitting layer by adjusting the ratios of CDs with different emitting color. The composite CDs revealed stable and bright white emitting in the film with a Commission Internationale d'Eclairage (CIE) coordinate of (0.28, 0.33). The result suggested that these unique luminescent CDs have potential applications in various luminescence fields.

Ultrahigh porosity photoluminescent silicon aerocrystals with greater than 50% nanocrystal ensemble quantum yields

Three types of mesoporous silicon flakes were fabricated by anodization in methanoic hydrofluoric acid from the same substrates (heavily doped p-type). Even though anodization current density, rinsing, drying method, and storage condition were the same for all three wafers, the resulting porous silicon (PSi) structures had very different properties. They had very different colors. Two of them showed quite high luminescence quantum yields (QYs), confirmed by very long luminescence lifetimes. The highest QY exceeded 50% for a peak photoluminescence wavelength of ∼750 nm. To date, this QY is the highest obtained for PSi and very importantly for silicon with large mesopores, which is typically not highly efficient (as opposed to silicon with small mesopores and microporous silicon). Large mesopores (>15 nm diameter) facilitate impregnation of various substances into luminescent material, such as metals for plasmonics and drugs for theranostics. The differing luminescent properties were correlated to electrolyte temperature during anodization, and evolution of the electrolyte batch (lowering of active fluoride content and buildup of hexafluorosilicate) used to anodize several wafers, whose effects are often overlooked when mass-producing PSi. Supercritical drying and completion of the slow growth of native oxide passivation in the dark leading to different final partially oxidized PSi structures are also important factors for the high QYs obtained. The highest QY was obtained with the structure having the most isolated Si nanocrystals in an amorphous Si oxide tissue.

Top-Down Fabrication of Luminescent Graphene Quantum Dots Using Self-Assembled Au Nanoparticles.

A new graphene quantum dot (GQD) fabrication method is presented, which employs a lithographic approach based on self-assembled Au nanoparticles formed by solid-state dewetting. The GQDs are formed by the patterned etching of a graphene layer enabled by Au nanoparticles, and their size is controllable through that of the Au nanoparticles. GQDs are fabricated with four different diameters: 12, 14, 16, and 27 nm. The geometrical features and lattice structures of the GQDs are determined using transmission electron microscopy (TEM). Hexagonal lattice fringes in the TEM image and G- and 2D-band Raman scattering evidence the graphitic characteristics of the GQDs. The oxygen content can be controlled by thermal reduction under a hydrogen atmosphere. In GQDs, the absorption peak wavelengths in the ultraviolet range tend to decrease as the size of the GQDs decreases. They also exhibit apparent photoluminescence (PL). The PL peak wavelength is approximately 600 nm and becomes shorter as the size of the GQDs decreases. The blue shift in the optical absorption and PL of the smaller GQDs is attributed to the quantum confinement effect. The proposed GQD fabrication method can provide a way to control the physical and chemical properties of GQDs via their size and oxygen content.

Cs-Symmetric, Peripherally Fluorinated Boron Subphthalocyanine–Subnaphthalocyanine Hybrids: Shedding New Light on Their Fundamental Photophysical Properties and Their Functionality as Optoelectronic Materials

Hybridization of boron subphthalocyanine (BsubPc) and boron subnaphthalocyanine (BsubNc) has been modestly explored in the past, and was therefore carried out herein to access a subclass of these chromophores denoted as Ra-FxBsub(Pc3–p-Ncp) hybrids, where Ra is the axial halide substituent (axial chloride, Cl-, or axial fluoride, F-), x = 8, and p = 1. These chromophores were targeted as new candidate materials for organic electronic applications due to their Cs symmetry, in-plane dipole moment, and unique photophysical properties. Cl-/F- F8Bsub(Pc2-Nc1) hybrids were compared to Cl-/F- F8BsubPc hybrids, which are analogous compounds with an identical number of peripheral fluorine atoms but lower degree of π-conjugation. Upon photoexcitation of dilute toluene solutions and doped thin films with polystyrene as a nonemissive host, F8Bsub(Pc2-Nc1) hybrids exhibited distinctively broad absorption spectra and narrow emission profiles with red-shifted peak photoluminescence wavelengths in the 618–623 nm region compared to F8BsubPc hybrids (581–584 nm). Electroluminescence properties were probed in simple solution-cast organic light-emitting diodes (OLEDs) in which all four hybrids were diluted within an F8BT emissive polymer host. Upon electronic excitation, electroluminescence (EL) of Cs-symmetric hybrids followed the same trends as photoluminescence (PL), with OLED devices displaying narrow EL in the orange region (588–592 nm) for F8BsubPc hybrids and in the near-red region for F8Bsub(Pc2-Nc1) hybrids (627–632 nm). The photophysical processes important to OLEDs moderately improved with less π-conjugation in the periphery of the Cs-symmetric hybrids [F8Bsub(Pc2-Nc1) vs F8BsubPc; EQEMax: 0.099% vs 0.129%; luminance: 500 cd/m2 vs 1000 cd/m2 at maximum current density; relative PL quantum yields (QYs) ≈ 17–22% vs ≈ 35–44%]. Electrochemical data showed that Cs symmetry introduces reversibility or quasi-reversibility in the oxidation regime at potentials >1 V, and peripheral fluorination enables reversibility in the reduction process. Overall, F8Bsub(Pc2-Nc1) hybrids embody several unique physical characteristics into one: broad absorption spectra (full width at half-maximum height, FWHMsolabs = 53–55 nm, FWHMfilmabs = 71 nm), narrow near-red electroluminescence (FWHMOLEDEL = 33 nm), and photoluminescence (FWHMsolPL = 25–26 nm, FWHMfilmPL = 32 nm) emission, small energy band gaps (1.95–1.96 eV), high extinction coefficients (ε ≈ (5.65–6.16) × 104 M–1 cm–1), and dual electrochemical versatility. These results provide new physical insights into the material properties of Cs-symmetric macrocycles and advance the consideration of F8Bsub(Pc2-Nc1) and F8BsubPc hybrids for optoelectronic applications.

Bright blue-emitting CsPbBr3 nanoplates for white light emitting

Perovskite nanomaterials with highly stable and bright emission were requested for white light emitting diodes (LEDs). In this paper, superior thin CsPbBr3 nanoplates (NPLs) with an average thickness of 1.9 nm were synthesized via solvothermal reactions. A bright blue-emitting peak at 455 nm with a photoluminescence (PL) quantum yield of 89 % was observed. The high PL efficiency was kept after storing for 90 days at ambient condition. This supplied an efficient approach to solve the problem of low PL efficiency and poor stability of blue-emitting perovskite nanocrystals. The thickness of CsPbBr3 NPLs was adjusted by changing preparation conditions. The PL peak wavelength of CsPbBr3 NPLs was adjusted in a region of 455–465 nm. Through dynamic anion exchange promoted cation exchange reactions, Mn ions were introduced in the lattice of CsPbBr3 NPLs to generate bright orange emitting to create dual-luminescent CsPbBr3:Mn NPLs. A white emitting sample with a color coordinate of (0.304, 0.325) was finally fabricated using bright CsPbBr3:Mn NPLs and green-emitting CsPbBr3 nanocrystals. This work broadened the application of perovskite for display and lighting.

(Digital Presentation) Fabrication of Thick SiGe／Ge Multiple Quantum Wells on Ge-on-Si and Their Optical Properties

Recently, silicon photonics has been attracting increased attention toward the realization of on-chip optical interconnection, which requires high-efficiency light-emitting devices to be integrated on Si substrates. Although Ge is an indirect-band-gap semiconductor like Si, it is expected that strong direct-transition luminescence can be obtained from tensile-strain induced Ge-on-Si. We have previously reported that highly efficient room temperature EL emission can be obtained from strained Ge-on-Si p-i-n diodes[1]. Further increase in luminescence intensity and control of emission wavelengths can be made possible by introducing a quantum well structure in the active layer. Although the fabrication of high-quality strained SiGe layers on Ge is essential for the fabrication of quantum well structures, critical thickness limits the total growth thickness and numbers of strained layers, which makes device applications difficult. We have succeeded in fabricating a strained SiGe layer that is much thicker than the critical thickness by using a patterning method, and this result is very promising for the fabrication of SiGe/Ge multi-quantum well structure[2]. It also makes it possible to increase the number of layers of MQW structure. In this work, we fabricate relatively thick strained SiGe/Ge MQW structures on Ge-on-Si by utilizing the patterning method, and evaluate their crystallinity and optical properties.In experiments, the crystal growth was carried out with solid source molecular beam epitaxy. The Ge-on-Si was fabricated using the so-called two-step method. 40 and 500 nm thick Ge layers were subsequently grown on a Si(100) or Si(111) substrate at 350 and 600℃, respectively, followed by annealing at 800℃ for 10 min. Subsequently we carried out the patterning of the Ge-on-Si(111) substrate by photolithography process. 50nm thick Ge buffer layer ware grown on a Ge-on-Si(100) or Ge-on-Si(111), 6nm thick Si0.1Ge0.9 barrier layer and 10nm thick Ge well layer ware grown with 10-20 cycles at 350℃.Laser microscopic measurements showed no clear roughness on the surface. X ray diffraction measurements show periodic peaks originated from the multi layers of SiGe/Ge, which indicates that the sample has high crystallinity and abrupt interface between the Ge and SiGe layers. TEM observation indicated that no defect was found inside the crystal in the MQW structure. Photoluminescence (PL) measurements were carried out at room temperature and a PL peak originated from the quantum-confinement in the SiGe/Ge MQW was obtained. This PL peak wavelength was also found to shift depending on the Ge concentration of the SiGe. PL intensity of the peak was increased compared with Ge-on-Si without the SiGe/Ge MQW overgrowth. From these results, it is demonstrated that high quality SiGe/Ge multiple quantum structures can be fabricated on Ge-on-Si by utilizing the patterning method and strong room temperature PL was obtained from the MQW, indicating that SiGe/Ge MQW is promising for the applications to light-emitting devices integrated on the Si platform.[1] K.Yamada et al. Appl. Phys. Express 14 045504(2021) [2] Y.Wagatsuma et al. Appl. Phys. Express 14 025502(2021) Figure 1

Near-infrared-red-orange thermally activated delayed fluorescence emitters using a strong tetracoordinated difluoroboronated acceptor

We design two organoboron-based thermally activated delayed fluorescence (TADF) molecules, DMAC-PAPB and m-DMAC-PAPB, containing a strong tetracoordinated difluoroboronated acceptor, a phenyl-linking difluoro[amidopyrazinato-O,N]boron (APB) moiety, named PAPB. Theoretical calculations predict that PAPB has a deep lowest unoccupied molecular orbital (LUMO) energy level. DMAC-PAPB and m-DMAC-PAPB show a low-lying lowest excited singlet state (S1) with small S1 energy (2.04 eV and 1.85 eV, respectively), and small energy gaps (∼0.01 eV) between S1 and the lowest triplet state, which satisfy the critical requisite for constructing red TADF emitters. Experimentally, DMAC-PAPB and m-DMAC-PAPB show red and near-infrared (NIR) luminescence with the peak photoluminescence wavelength at 650 nm and 701 nm in toluene, respectively. The solution-processed doped films both exhibit orange-to-red luminescence and obvious delayed fluorescence. These investigations exemplify the strong electron-accepting ability of PAPB and its potential in developing yellow, orange, red, and NIR organoboron-based TADF emitters.

Platinum(II)-Substituted Phenylacetylide Complexes Supported by Acyclic Diaminocarbene Ligands.

We introduce phosphorescent platinum aryl acetylide complexes supported by tert-butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes cis-[Pt(CNtBu)2(C≡CAr)2] (4a-4f) are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the cis-[Pt(CNtBu)(ADC)(C≡CAr)2] complexes (5a-5f). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe2) or electron-withdrawing groups [3,5-(OMe)2, 3,5-(CF3)2, 4-CN, and 4-NO2] on the aryl acetylide. Experimental HOMO-LUMO gaps, estimated from cyclic voltammetry, span the range of 2.68-3.61 eV and are in most cases smaller than the unsubstituted parent complex, as corroborated by DFT. In the ADC complexes, peak photoluminescence wavelengths span the range of 428 nm (2a, unsubstituted phenylacetylide) to 525 nm (5f, 4-NO2-substituted), with the substituents inducing a red shift in all cases. The phosphorescence E0,0 values and electrochemical HOMO-LUMO gaps are loosely correlated, showing that both can be reduced by either electron-donating or electron-withdrawing substituents on the aryl acetylides. The photoluminescence quantum yields in the ADC complexes are between 0.044 and 0.31 and the lifetimes are between 4.8 and 14 μs, a factor of 1.8-10× higher (for ΦPL) and 1.2-3.6× longer (for τ) than the respective isocyanide precursor (ΦPL = 0.014-0.12, τ = 2.8-8.2 μs).

High Energy Limit of the Size-Tunable Photoluminescence of Hydrogen-Terminated Porous Silicon Nanostructures in HF

The photoluminescence (PL) of various porous silicon (PSi) layers was studied during chemical dissolution in HF. The relative PL quantum efficiency of some layers was also monitored. Typically, the PL increased, reached a maximum and then dropped down to complete extinction, accompanied with a PL blueshift. During PL fall, both the PL intensity and layer quantum efficiency fell sharply, accompanied by a decrease in full width at half maximum and a slowing blueshift. In the final stage, the PL intensity decreased without any further blueshift, the saturated PL peak wavelength being ∼515 nm (∼2.4 eV) for most layers, identifying a high energy limit for the achievable PL of hydrogen-terminated Si nanostructures. Our results show that sudden catastrophic mechanical failure of nanostructure cannot explain the sharp PL drop and saturation of PL blueshift. Rather, they support the idea of a critical size (∼1.5–2 nm) below which the PL quantum efficiency vanishes. The possible reasons were discussed, privileging the emergence of structural non-radiative defects below a certain size, though the decreasing intrinsic quantum efficiency of Si nanocrystals with decreasing size could also play an important role. Maximum PL intensity was generally obtained for a peak wavelength of ∼565 nm (∼2.2 eV).

Internal Referencing Photoluminescence Probes for Simultaneous Sensing of O2 Gas and Temperature Based on Mn:MAPb(Br/Cl)3 Perovskite

The ratiometric photoluminescence (PL)‐based O2 sensitive probes provide built‐in self‐calibration for the correction of various target‐independent influencing factors. They attract particular attention to be used for O2 gas sensing and imaging. Herein, internal referencing ratiometric PL probes are fabricated that not only detect O2 concentration and temperature simultaneously but also remove the destructive effect of temperature on O2 sensing. A dual‐emission thin film of Mn‐doped halide perovskite nanocrystals (PNCs) (Mn:MAPb(Br/Cl)3) with a 50% PL quantum yield is used as the sensing layer, which is synthesized in situ. Through the sensing process, excitonic PL and the PL caused by Mn are used for detecting temperature and O2 partial pressures, respectively. Remarkably, the Mn PL intensity shows 40% decrement with increasing O2 partial pressures from 0% to 20%, while for the excitonic PL, intensity changes are less than 5%. As the temperature undesirably affects the sensing quantity, the O2 PL is used as an internal reference signal to achieve good accuracy and selectivity. Furthermore, the temperature variation is determined by measuring PL peak intensity change and wavelength shift. In addition to the O2 gas sensitivity of 1.55, a relative temperature sensitivity of −9.36% K−1 is also achieved.

Kinetic analysis of the growth of semiconductor nanocrystals from the peak wavelength of photoluminescence

Understanding the rate processes controlling the growth of semiconductor nanocrystals in liquid solutions is of great importance in tailoring the sizes of semiconductor nanocrystals for the applications in optoelectronics, bioimaging and biosensing. In this work, we establish a simple relationship between the photoluminescence (PL) peak wavelength and the growth time of semiconductor nanocrystals under the condition that the contribution of electrostatic interaction to the quantum confinement is negligible. Using this relationship and the data available in the literature for CdSe and CdSe/ZnS nanocrystals, we demonstrate the feasibility of using the PL peak wavelength to analyze the growth behavior of the CdSe and CdSe/ZnS nanocrystals in liquid solutions. The results reveal that the diffusion of monomers in the liquid solution is the dominant rate process for the growth of CdSe/ZnS nanocrystals, and the activation energy for the growth of CdSe nanocrystals in the liquid solution is ∼9 kJ/mol. The feasibility to use this approach in the analysis of the thickness growth of core–shell nanocrystals with and without mechanical stress is also discussed. Such an approach opens a new avenue to in-situ monitor/examine the growth of semiconductor nanocrystals in liquid solutions.