Luminescence Mechanism Research Articles

Luminescent Tactile Sensor System for Robots: Enhancing Human-Computer Interaction in Complex Dark Environments.

In order to achieve interaction and collaboration with humans, robots need to have the ability for tactile perception of simulating human. Traditional methods use electrically connected sensors with complex arrays, leading to intricate wiring, high manufacturing costs, and demanding current environments. A flexible sensor with simple structure, easy preparation process, and low cost based on triboluminescence effect is proposed in this paper, which avoids the complex array and wiring of traditional sensors. The study discusses the relationship between luminescent intensity and factors such as luminescent particle content, luminescent layer thickness, encapsulation layer thickness, and friction layer thickness. It also analyzes the mechanism of luminescence. A micro charge-coupled device is configured for the luminescent unit to collect optical information and is integrated with the robot's manipulator for testing. A simple sensing system is constructed to demonstrate environmental perception, acquiring, and feeding back shape and size information of contact objects in the dark. The system successfully identifies and judges target objects in complex dark environments, offering insights for applications such as unmanned assembly lines. It overcomes the challenge of intricate electrical connections, paving new avenues for intelligent object recognition research in human-computer interaction.

Manipulating Electron-Phonon Coupling for Efficient Tin Halide Perovskite Blue LEDs.

Low-dimensional perovskites have opened up a new frontier in light-emitting diodes (LED) due to their excellent properties. However, concerns regarding the potential toxicity of Pb limited their commercial development. Sn-based perovskites are regarded as a promising candidate to replace Pb-based counterparts, while they generally exhibit strong electron-phonon coupling and consequently blue emission quenching at room temperature (RT), thus the Sn-based perovskite blue LED devices have not yet been reported. Herein, the luminescence properties are regulated by assembling a rigid organic skeleton within perovskite structure, and the protonated 4-bromobenzylamine (BrPMA+ = C7H9BrN+) is employed as A site cation to synthesize a 100-oriented 2D perovskite (BrPMA)2SnBr4, which exhibits a strong lattice rigidity via strong intermolecular interaction and consequently weak electron-phonon coupling, achieving the excellent blue PL emission at RT. The high quality (BrPMA)2SnBr4 perovskite thin films are obtained by further inhibiting oxidation and promoting crystallization. Finally, the Sn-based perovskite blue emission LED is successfully fabricated for the first time at 467nm with a champion EQE of 1.3% and a maximum brightness of 800cdm-2. This work gives insights into the luminescence mechanism of Sn-based perovskites and provides a new theoretical basis for the development of lead-free blue LEDs.

Synthesis and luminescence characterizations of Ag and Na doped LiAlO2 for OSL dosimetry

Optically Stimulated Luminescence (OSL) materials are advanced technology materials widely used in critical applications from radiation dosimetry, biomedicine, and optical data storage to archaeometry. These materials store energy by trapping charge carriers and convert this energy back into light by optical stimulation. However, there are significant challenges such as control of trap distribution and complete understanding of luminescence mechanisms. This study aims to overcome these challenges by comprehensively investigating the luminescence characteristics of lithium aluminate (LiAlO2) pellet materials produced by the sol-gel method and enabling the development of a new OSL dosimetric material. The crystal structures of the synthesized materials were confirmed by X-Ray Diffraction (XRD) method and their morphologies were investigated by Scanning Electron Microscope (SEM). Detailed discussions on defect concentrations and lattice parameters of LiAlO2 are presented. To obtain promising luminescence signals for passive dosimetry, LiAlO2 were doped with various lanthanides (Ce and Gd) and metals (Cu, Ag, Na, Mg and Ca). Especially, the co-doping of Ag and Na ions provided a significant increase in Thermoluminescence (TL) and OSL signals. The effects of dopant elements on TL and OSL signals were investigated comprehensively, and the OSL components and lifetimes were analyzed in detail. As a result, it was determined that TL traps of the developed LiAlO2:Ag,Na pellets at 100 °C were the main source of OSL signals. The reusable OSL signals and almost linear dose-response ratio up to 2 Gy of this material make it a candidate for radiation dosimetry applications. While the developed LiAlO2:Ag,Na material exhibits promising OSL sensitivity and low fading over 2 weeks, the signal stability is dependent on an initial preheat treatment at 100 °C, which reduces around 80 % of the initial OSL signal associated with shallow traps. This characteristic supports the material’s application in dosimetry but may limit sensitivity in low-dose contexts.

Highly efficient tunable mid-infrared luminescence achieved by crystal field modulation of CsPb1-xHoxBr3 halide perovskite AlF3-based fluoride glass

Mid-infrared (MIR) light sources have gained significant importance across various applications in spectroscopy, sensing, astronomy, communications and medical surgery. The diverse spectral characteristics of rare earth ions, particularly lanthanide ions, stemming from their distinctive 4f intershell transitions, offer a multitude of potential transitions spanning the UV-visible-infrared spectrum. Despite recent advancements in MIR gain luminescence, the investigation of tunable MIR luminescence mechanisms remains a major technical challenge. Herein, an effective mechanism to modulate the local crystal field of rare earth ions by altering its crystal structure has been revealed, resulting in tunable broad-spectrum emission in the MIR luminescence range of 2800-3000 nm and multi-peak emission in the near-infrared band of Ho3+. Notably, the local crystal field of Ho3+ is adjusted by manipulating the lattice symmetry of CsPb1-xHoxBr3 perovskite through the incorporation of fluoride glass reticulation to control the crystal size of the perovskite and thereby modify the lattice symmetry of CsPb1-xHoxBr3 perovskite. The energy level transition of Ho3+ is influenced by adjusting the crystal field asymmetry, resulting in the splitting of the 5I6 energy level depending on the crystal field. This cleavage affects the transitions from the 5I5 level to 5I6 at 1480 nm and from 5I6 to 5I7 at 2880 nm. As 5I6 acts as the common upper level for the two emission peaks, the infrared peaks at 1480 nm and 2880 nm widen and develop into a dual-peak emission phenomenon. The infrared luminescence produced aligns closely with the distinctive infrared absorption peaks of carbon dioxide, leading to the development of a convenient, high-precision device for monitoring of CO2 concentration in hydrogen energy in real time. These findings are anticipated to pave the way for extensive utilization of novel tunable MIR luminescence.

Exploring the potential of Tb and Bi-doped LaF3 as a UV absorber

Lanthanide-based nanophosphors are finding significant applicability in various fields such as LED, solar spectral convertors, lasers, and biological sensors, owing to their superior stability and luminescence properties. However, their function as a UV protector has not evolved, possibly because of their limited absorption cross-section in the UV spectral region. Hence, to overcome this limitation, in this work, a strategy to utilize Bi3+ ion as a co-dopant in LaF3:Tb3+ nanophosphor has been devised. These nanophosphors with an uniform morphology and narrow particle size distribution were synthesized using the hydrothermal method. Luminescence mechanism involving energy transfer from Bi3+ to Tb3+ was investigated. The excitation spectrum of a LaF3 nanophosphor, co-doped with Bi and Tb, reveals distinct absorption bands. Absorption ascribed to Bi3+ characterizes the UV range between 220 and 275 nm, whereas Tb3+ is associated with absorption in another UV range spanning 280 to 380 nm. This shows the potential applicability of the Bi and Tb co-doped LaF3 nanophosphors as a UV absorber. The cytotoxicity of these nanophosphors was tested on HaCaT cells, indicating their potential applicability in the healthcare field.

Three‐Photon Upconversion Luminescence of Gd2O2S: Ho3+, Er3+ for High‐Sensitivity FIR Thermometer and Multimode Anti‐Counterfeiting

AbstractThe performance control and multidimensional applications of upconversion phosphor have become the hotspot and difficulty in current research and application due to the complex luminescence mechanism. Based on the efficient Gd2O2S: Er3+ upconversion luminescence of 1550 nm excitation and design strategy for co‐doped materials, the multicolor (light green to red) and multifunctional upconversion phosphor Gd2O2S: Er3+, Ho3+ is successfully prepared. Benefiting from the clear mechanism of three‐photon upconversion and energy transfer after co‐doping, the novel applications of Gd2O2S: Er3+, Ho3+ can greatly be expanded. This phosphor can be well used as a fluorescence thermometer due to the higher sensitivity (2.46% K−1@170 K), wider temperature sensing range (170–267 K, Sr > 1% K−1), and greater color variation (Δx = 0.2416, Δy = 0.2483) relative to Gd2O2S: Er3+ and other same type of material. In addition, multiple patterns and encoded outputs are also effectively achieved by the combination of phosphors under multiple light stimuli response. This shows the greater application potential of phosphor in the fields of anti‐counterfeiting and information encryption. This study can also provide a new view to study the more high‐performance and multifunctional upconversion phosphor.

Luminescence Mechanisms of Quaternary Zn-Ag-In-S Nanocrystals: ZnS:Ag, In or AgInS2:Zn?

Highly emissive Zn-Ag-In-S nanocrystals have attracted attention as derivatives of I-III-VI2-type nanocrystals without the use of toxic elements. The wide tunability of their luminescence wavelengths is attributed to the controllable bandgap of the solid solution between ZnS and AgInS2. However, enhancement of the photoluminescence quantum yield (PL-QY) depending on the chemical composition has not been elucidated. Here, the luminescence mechanisms of Zn-Ag-In-S nanocrystals were studied from the perspective of ZnS doped with Ag and In, although previous research has proposed a hypothesis that Zn is a radiative recombination centre in the AgInS2 host. The Zn-Ag-In-S nanocrystals were synthesized by systematically varying the Zn, Ag, and In contents. The nanocrystals exhibit a structure in which a part of the Zn in the cubic ZnS is substituted with Ag and In. Luminescence was ascribed to a donor-acceptor pair (DAP) recombination between electrons trapped in In donors and holes trapped in Ag acceptors. The composition-dependent enhancement of PL-QYs was attributed to an increase in donor and acceptor concentrations. The DAP characteristics were maintained over a wide range of Ag and In contents because of the localized character of the band edge states dominated by Ag and In orbitals, as suggested formerly by simulation.

Phenoxy-1,2-dioxetane-based activatable chemiluminescent probes: tuning of photophysical properties for tracing enzymatic activities in living cells.

The use of chemiluminophores for tracing enzymatic activities in live-cell imaging has gained significant attention, making them valuable tools for diagnostic applications. Among various chemiluminophores, the phenoxy-1,2-dioxetane scaffold exhibits significant structural versatility and its activation is governed by the chemically initiated electron exchange luminescence (CIEEL) mechanism. This mechanism can be initiated by enzymatic activity, changes in pH, or other chemical stimuli. The photophysical properties of phenoxy-1,2-dioxetanes can be fine-tuned through the incorporation of different substituents on the phenolic ring and by anchoring them with specific triggers. This review discusses the variations in physicochemical properties, including emission maxima, quantum yield, aqueous solubility, and pKa, as influenced by structural modifications, thereby establishing a comprehensive structure-activity relationship. Furthermore, it categorises the probes based on different enzyme classes, such as hydrolase-sensitive probes, oxidoreductase-responsive probes, and transferase-activatable phenoxy-1,2-dioxetanes, offering a promising platform technology for the early diagnosis of diseases and disorders. The summary section highlights key opportunities and limitations associated with applying phenoxy-1,2-dioxetanes in achieving precise and effective enzyme assays.

Redox-switchable multicolor luminescent polymers for theragnosis of osteoarthritis

Nonaromatic and nonconjugated fluorescent materials have garnered increasing attention in recent years. However, most non-classical chromophores are derived from electro-rich nitrogen and oxygen atoms, which suffer from short emission wavelengths, low efficiency, limited responsiveness, and obscure luminescence mechanisms. Here we present an emission mechanism in bioactive polycysteine, an aliphatic polymer that displays polymerization- and aggregation-induced emission, high quantum yield, and multicolor emission properties. We show that the hydrogen atoms bonded to the sulfur atoms play a crucial role in luminescence. This enables reversible modulation of polymer fluorescence under reducing and oxidizing conditions, facilitating specific imaging and quantitative detection of redox species in cells and in vivo. Furthermore, the polymer exhibits better anti-inflammatory and antioxidative activities compared to first-line clinical antioxidants, offering a promising platform for in vivo theragnosis of diseases such as osteoarthritis.

Delayed luminescence and thermoluminescence in laboratory-grown diamonds

The “blue-green” phosphorescence/thermoluminescence is most commonly observed in diamonds following excitation at or above the indirect band gap and has been explained by a substitutional nitrogen-boron donor-acceptor pair recombination model. “Orange” and “red” phosphorescence have also been frequently observed in laboratory-grown near-colorless high-pressure high-temperature diamonds following optical excitation and their luminescence mechanisms are shown to be different from that of the blue-green phosphorescence. The physics of the orange and red luminescence and phosphorescence bands including the optical-excitation dependency (UV-NIR), temperature dependency (20K–573K), and related charge transfer process are investigated by a combination of self-built time-resolved imaging/spectroscopic techniques. In this paper, an alternative model for long-lived phosphorescence based on charge trapping is proposed to explain the orange phosphorescence/thermoluminescence band. Additionally, the red phosphorescence band is attributed to point defect, which possibly has a three-level phosphorescence system. Published by the American Physical Society 2024

Recent Advances in Smart Sensing Based on Excited‐State Intramolecular Proton‐Transfer (ESIPT)‐Inspired Emitters

The optical materials based on excited state intramolecular proton transfer (ESIPT) have garnered significant attention due to their unique photophysical properties and applications in sensors and imaging agents (probes). These materials exhibit an intrinsic four‐level photocycle scheme through the enol (E)–keto (K) phototautomerization process, resulting in a large Stokes shift, environmental sensitivity, and potential for ratiometric sensing. This review primarily focuses on elucidating the luminescence mechanism and structure‐property relationships of recent ESIPT molecules, as well as exploring the sensing applications of phosphorescent functional materials.

Organic Circularly Polarized Room-Temperature Phosphorescence: Strategies, Applications and Challenges.

Organic circularly polarized luminescence (CPL) plays crucial roles in chemistry and biology for the potential in chiral recognition, asymmetric catalysis, 3D displays, and biological probes. The long-lived luminescence, large Stokes shift, and unique chiroptical properties make organic circularly polarized room-temperature phosphorescence (CPP) a new research hotspot in recent years. Nevertheless, achieving high-performance organic CPP is still challenging due to the sensitivity and complexity of integrating triplet excitons and polarization within organic materials. This review summarizes the latest advances in organic CPP, ranging from design strategies and photophysical properties to underlying luminescence mechanisms and potential applications. Specifically, the design strategies for generating CPP are systemically categorized and discussed according to the interactions between chiral units and chromophores. The applications of organic CPP in organic light-emitting diodes, sensing, chiral recognition, afterglow displays, and information encryption are also illustrated. In addition, we present the current challenges and perspectives on developing organic CPP. We expect this review to provide some instructive design principles to fabricate high-performance organic CPP materials, offering an in-depth understanding of the luminescence mechanism and paving the way toward diverse practical applications.

Organic Circularly Polarized Room‐Temperature Phosphorescence: Strategies, Applications and Challenges

AbstractOrganic circularly polarized luminescence (CPL) plays crucial roles in chemistry and biology for the potential in chiral recognition, asymmetric catalysis, 3D displays, and biological probes. The long‐lived luminescence, large Stokes shift, and unique chiroptical properties make organic circularly polarized room‐temperature phosphorescence (CPP) a new research hotspot in recent years. Nevertheless, achieving high‐performance organic CPP is still challenging due to the sensitivity and complexity of integrating triplet excitons and polarization within organic materials. This review summarizes the latest advances in organic CPP, ranging from design strategies and photophysical properties to underlying luminescence mechanisms and potential applications. Specifically, the design strategies for generating CPP are systemically categorized and discussed according to the interactions between chiral units and chromophores. The applications of organic CPP in organic light‐emitting diodes, sensing, chiral recognition, afterglow displays, and information encryption are also illustrated. In addition, we present the current challenges and perspectives on developing organic CPP. We expect this review to provide some instructive design principles to fabricate high‐performance organic CPP materials, offering an in‐depth understanding of the luminescence mechanism and paving the way toward diverse practical applications.

Metal-organic framework-based hybrids with photon upconversion.

Upconversion materials (UCMs) featuring an anti-Stokes type emission establish them as an important category of photoluminescent materials. Metal-organic frameworks (MOFs) are rapidly gaining prominence as a class of versatile materials with favourable physical and chemical properties, including high porosity, controllable pore size, flexible design, and diverse functional sites. To endow MOFs with upconversion capability and improve the properties and performance of UCMs, the hybrids integrating UCMs and MOFs are proven to be successful. This review focuses on the research advancements of upconverting MOF-based hybrids, encompassing classifications, luminescence mechanisms, designs, properties, and applications in energy, catalysis, and biomedical fields. The analyses on the functions of upconversion and MOFs, as well as the advantages and disadvantages of various upconverting MOF-based hybrids, are included. Future research directions spanning from properties and performance to applications are explored. This review will be valuable in highlighting the research accomplishments, inspiring more ideas, facilitating deeper investigations in diverse avenues, and further advancing the research field.

Stable Xanthene Radicals and Their Heavy Chalcogen Analogues Showing Tunable Doublet Emission from Green to Near-infrared.

Organic luminescent radicals, unlike traditional closed-shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand their emission spectra. In this study, we report the synthesis of stable 9-aryl-substituted xanthene radicals and their heavy chalcogen analogues (1 a-c and 2 a-c), which exhibited excellent chemical stability and emission ranging from green to near-infrared (527-714 nm). Notably, the selenium-substituted radical (1 c) demonstrates a significantly enhanced photoluminescence quantum yield of 41 % when doped into its precursor solid. Additionally, the introduction of methoxyphenyl groups has largely enhanced the stability of the radical, showcasing an excellent photostability with the longest half-life of around 1792 h. The high internal quantum efficiency of up to 81 % was further validated in organic light-emitting diode. This study introduces a novel class of stable carbon-centered radicals with high tunability and functionality for photoelectric applications.

Stable Xanthene Radicals and Their Heavy Chalcogen Analogues Showing Tunable Doublet Emission from Green to Near‐infrared

AbstractOrganic luminescent radicals, unlike traditional closed‐shell fluorescent emitters, exhibit distinct luminescence mechanisms, offering promising potential for optoelectronic devices. To date, stable luminescent radicals have predominantly been confined to polychlorinated triphenylmethyl radicals, underscoring the need for new platforms to expand their emission spectra. In this study, we report the synthesis of stable 9‐aryl‐substituted xanthene radicals and their heavy chalcogen analogues (1 a–c and 2 a–c), which exhibited excellent chemical stability and emission ranging from green to near‐infrared (527–714 nm). Notably, the selenium‐substituted radical (1 c) demonstrates a significantly enhanced photoluminescence quantum yield of 41 % when doped into its precursor solid. Additionally, the introduction of methoxyphenyl groups has largely enhanced the stability of the radical, showcasing an excellent photostability with the longest half‐life of around 1792 h. The high internal quantum efficiency of up to 81 % was further validated in organic light‐emitting diode. This study introduces a novel class of stable carbon‐centered radicals with high tunability and functionality for photoelectric applications.

UV-induced coumarin-based spiropyran gradient photodimerization and photoisomerization to construct near-infrared responsive gradient hydrogel actuators in one-step

In recent years, the fabrication process of near-infrared (NIR) light-driven gradient hydrogels remains complex. Furthermore, NIR light-driven hydrogels based on the photothermal conversion mechanism have continued to face challenges in achieving spatio-temporal control of the internal structure due to the diffusive nature of heat. Therefore, it is sensible to develop NIR light-driven gradient hydrogels based on the near-infrared upconversion luminescence mechanism through a simple method. In this study, a novel photoresponsive coumarin-based spiropyran monomer (SPCMA) was designed and synthesized, followed by the fabrication of a series of double gradient hydrogels (MHMs) with rapid NIR light-driven capability and reusability through fast in situ photopolymerization of the precursor comprising SPCMA, upconversion nanoparticles (MUCNPs), and hydroxyethyl acrylate (HEA). MHMs exhibit excellent mechanical properties with fracture stress of 4.4 MPa and fracture elongation of 1282 %. Compared with hydrogel using N, N′-Methylenebis(2-propenamide) as a crosslinker, MHMs possess outstanding NIR light-driven capability and reversible cycling characteristics. MHMs rapidly transform from a three-dimensional spiral tubular to a sheet-like morphology within 30 s of NIR light irradiation and achieve a larger actuating angle of 450° within 120 s. Additionally, MHMs maintain similar driveability to the original samples after 10 cycles of NIR light-driven and UV light-recovery processes. More importantly, cargoes with seven times the mass of the "gripper" are firmly grasped and easily lifted by the "gripper" prepared using MHMs within 60 s of NIR light irradiation, demonstrating its powerful gripping ability. This work offers a new strategy for the development of biomimetic smart gradient materials.

Advances in aggregation-induced emission luminogens for biomedicine: From luminescence mechanisms to diagnostic applications

Advancements in early detection have demonstrated the significance of biomarkers as indicators of health and disease. Traditional detection methods often face limitations, such as low sensitivity and time consumption. Fluorescence-based techniques are considered promising approaches because of their noninvasiveness and rapid response. However, these conventional methods have some drawbacks, such as low quantum yield, photobleaching, and aggregation-caused quenching. Recently, aggregation-induced emission (AIE) has emerged as a potential alternative, characterized by luminous emission upon aggregation, thus improving detection sensitivity and stability. This review explores the recent advancements in AIE luminogens (AIEgens) in biomedical engineering, with a particular focus on their application in biomarker detection. Here, we discuss the different types of AIE mechanisms and their advantages in disease diagnosis and imaging. In addition, we summarize the development of various AIEgen-based probes for the detection of diverse biomarkers. Finally, we address the remaining challenges and future directions for AIE materials in modern biomedical engineering, emphasizing the potential of AIEgens in biomarker detection and disease diagnosis strategies.

Sustainable production of BioAIE materials from biomass

The research of aggregation‐induced emission (AIE) materials has aroused extensive interests during the past 20 years. Until recently, biomass‐inspired AIE (BioAIE) materials have become highly attractive owing to the advantages of natural structural diversity, renewability, biocompatibility, and biodegradability of the biomass. In this concept, we focus on the sustainable production of BioAIE materials from biomass resources (biomacromolecules and small natural products) through extraction, chemical conversion, and physical conversion. Chemical conversion is especially stated, including catalytic conversion, Schiff base reaction, “in water” reaction, and other chemical modifications. The luminescence mechanism of AIE behaviors along with their structure‐property relationships is emphasized, and the applications are addressed as well. An outlook is provided to highlight the challenges and opportunities associated with the future development trend in this field.

Short-Range Coulomb Interaction Is a Key to Switch the Utilization of Higher Triplet Excitons in Multiresonance Thermally Activated Delayed Fluorescence Doped Film.

Multiresonance thermally activated delayed fluorescence (MR-TADF) materials have attracted widespread attention due to ultrahigh definition display standards. However, many MR-TADF materials lack TADF properties in both the solution and solid states. Interestingly, the TADF characteristics appear once these MR-TADF compounds are doped in a suitable host film, but the precise mechanism involved in the host-guest interaction remains uncertain. Herein, we systematically investigated the role of host-guest interactions employing doped films (DABNA-1@mCBP and DABNA-1@DPEPO) with opposite phenomena. The results indicate that mCBP with a V-shape and enhanced rigidity could facilitate the formation of an energy spacing layer by employing short-range Coulomb energy through the MR luminescent core, which could offset the sensitivity of the stacking distance, enhancing the coupling between T1 and T2, and thus switch the reverse internal conversion and the higher T2 reverse intersystem crossing process. This work is a further development of luminescence mechanisms and an update of the host-guest interaction criteria for the targeted design of doped films.