Near-Infrared Mechanoluminescence from Cr3+-Doped Spinel Nanoparticles for Potential Oral Diseases Detection.

Mechanoluminescence (ML) phosphors have found various promising utilizations such as in non-destructive stress sensing, anti-counterfeiting, and bio stress imaging. However, the reported NIR MLs have predominantly been limited to bulky particle size and weak ML intensity, hindering the further practical applications. For this regard, a nano-sized ZnGa2O4: Cr3+ NIR ML phosphor is synthesized by hydrothermal method. By improving the synthesis method and regulating the chemical composition, the NIR ML (600-1000 nm) intensity of such nano-materials has been further enhanced about four times. The reasons for the ML performance difference between micro-/nano- sized phosphors also have been preliminarily analyzed. Additionally, this work probes into the ML mechanism deeply in traps' aspect from band structure and defect formation energy, which can supply significant references for a new approach to develop efficient NIR ML nanoparticles. Finally, due to excellent tissue penetration capability, nano-sized ZnGa2O4:Cr3+ NIR ML phosphor shows great potential applications in biomedical fields such as for the detection of clinical oral diseases.

Highly Emissive Lanthanide-Based 0D Metal Halide Nanocrystals for Efficient Ultraviolet Photodetector.

Recently, lanthanide-based 0D metal halides have attracted considerable attention for their applications in X-ray imaging, light-emitting diodes (LEDs), sensors, and photodetectors. Herein, lead-free 0D gadolinium-alloyed cesium cerium chloride (Gd3+-alloyed Cs3CeCl6) nanocrystals (NCs) are introduced as promising materials for optoelectronic application owing to their unique optical properties. The incorporation of Gd3+ in Cs3CeCl6 (CCC) NCs is proposed to increase the photoluminescence quantum yield (PLQY) from 57% to 96%, along with significantly enhanced phase and chemical stability. The structural analysis is performed by density functional theory (DFT) to confirm the effect of Gd3+ in Cs3Ce1- xGdxCl6 (CCGC) alloy system. Moreover, the CCGC NCs are applied as the active layer in UVPDs with different Gd3+ concentration. The excellent device performance is shown at 20% of Gd3+ in CCGC NCs with high detectivity (7.938 × 1011 Jones) and responsivity (0.195 A W-1) at -0.1 V at 310 nm. This study paves the way for the development of lanthanide-based metal halide NCs for next-generation UVPDs and other optoelectronic applications.

Large-Scale Mechanochemical Synthesis of Cesium Lanthanide Chloride for Radioluminescence.

Cesium lanthanide chloride (Cs3LnCl6), a recently developed class of lanthanide-based zero-dimensional metal halides, has garnered a significant amount of interest because of its potential applications in scintillators, light-emitting diodes, and photodetectors. Although cesium lanthanide chloride demonstrates exceptional scintillator properties, conventional synthesis methods involving solid-state and solution-phase techniques are complex and limited on the reaction scale. This study presents a facile mechanochemical synthesis method for producing Cs3CeCl6, Cs3TbCl6, and Cs3EuCl6 metal halides on a 5 g scale. These materials exhibit intense blue-violet, green, and red emissions upon ultraviolet excitation, with high photoluminescence quantum yields ranging from 54% to 93%. Furthermore, Cs3CeCl6, Cs3TbCl6, and Cs3EuCl6 metal halides exhibit intense radioluminescence spanning from the ultraviolet to the visible region. This research shows the potential of the scalable mechanochemical synthesis of lanthanide-based metal halides for the advancement of luminescent materials for scintillators.

Synthesis of Thermally Stable and Highly Luminescent Cs5 Cu3 Cl6 I2 Nanocrystals with Nonlinear Optical Response.

Low-dimensional Cu(I)-based metal halide materials are gaining attention due to their low toxicity, high stability and unique luminescence mechanism, which is mediated by self-trapped excitons (STEs). Among them, Cs5 Cu3 Cl6 I2 , which emits blue light, is a promising candidate for applications as a next-generation blue-emitting material. In this article, an optimized colloidal process to synthesize uniform Cs5 Cu3 Cl6 I2 nanocrystals (NCs) with a superior quantum yield (QY) is proposed. In addition, precise control of the synthesis parameters, enabling anisotropic growth and emission wavelength shifting is demonstrated. The synthesized Cs5 Cu3 Cl6 I2 NCs have an excellent photoluminescence (PL) retention rate, even at high temperature, and exhibit high stability over multiple heating-cooling cycles under ambient conditions. Moreover, under 850-nm femtosecond laser irradiation, the NCs exhibit three-photon absorption (3PA)-induced PL, highlighting the possibility of utilizing their nonlinear optical properties. Such thermally stable and highly luminescent Cs5 Cu3 Cl6 I2 NCs with nonlinear optical properties overcome the limitations of conventional blue-emitting nanomaterials. These findings provide insights into the mechanism of the colloidal synthesis of Cs5 Cu3 Cl6 I2 NCs and a foundation for further research.

Mechanoluminescent, Air-Dielectric MoS2 Transistors as Active-Matrix Pressure Sensors for Wide Detection Ranges from Footsteps to Cellular Motions.

Tactile pressure sensors as flexible bioelectronic devices have been regarded as the key component for recently emerging applications in electronic skins, health-monitoring devices, or human-machine interfaces. However, their narrow range of sensible pressure and their difficulty in forming high integrations represent major limitations for various potential applications. Herein, we report fully integrated, active-matrix arrays of pressure-sensitive MoS2 transistors with mechanoluminescent layers and air dielectrics for wide detectable range from footsteps to cellular motions. The inclusion of mechanoluminescent materials as well as air spaces can increase the sensitivity significantly over entire pressure regimes. In addition, the high integration capability of these active-matrix sensory circuitries can enhance their spatial resolution to the level sufficient to analyze the pressure distribution in a single cardiomyocyte. We envision that these wide-range pressure sensors will provide a new strategy toward next-generation electronics at biomachine interfaces to monitor various mechanical and biological phenomena at single-cell resolution.

A zero-thermal-quenching phosphor.

Phosphor-converted white light-emitting diodes (pc-WLEDs) are efficient light sources used in lighting, high-tech displays, and electronic devices. One of the most significant challenges of pc-WLEDs is the thermal quenching, in which the phosphor suffers from emission loss with increasing temperature during high-power LED operation. Here, we report a blue-emitting Na3-2xSc2(PO4)3:xEu2+ phosphor (λem = 453 nm) that does not exhibit thermal quenching even up to 200 °C. This phenomenon of zero thermal quenching originates from the ability of the phosphor to compensate the emission losses and therefore sustain the luminescence with increasing temperature. The findings are explained by polymorphic modification and possible energy transfer from electron-hole pairs at the thermally activated defect levels to the Eu2+ 5d-band with increasing temperature. Our results could initiate the exploration of phosphors with zero thermal quenching for high-power LED applications.

Engineering the Lattice Site Occupancy of Apatite-Structure Phosphors for Effective Broad-Band Emission through Cation Pairing.

A series of britholite compounds were synthesized by simultaneous introduction of trivalent La3+ and Si4+ ions into an apatite structure. The variations in the average structure, electronic band structure, and microstructural properties resulting from the introduction of cation pairs were analyzed as a function of their concentration. The effects of the structural variance and microstructural properties on the broad-band-emitting activator ions were studied by introducing Eu2+ ions as activators. For the resulting compound, which had dual emission bands in the blue and yellow regions of the spectrum, the emission peak position and strength were dependent upon the concentration of La3+-Si4+ pairs. By engineering the relative sizes of the two possible activator sites in the structure, 4f and 6h, through the introduction of a combination of trivalent La3+ and a polyanion, the preferential site occupancy of the activator ions was favorably altered. Additionally, the activator ions responsible for the lower-Stokes-shifted blue component of the emission functioned as a sensitizer of the larger-Stokes-shifted yellow-emitting activators, and predominantly yellow-emitting phosphors were achieved. The feasibility of developing a white light-emitting solid-state device using the developed phosphor was also demonstrated.

A Phosphosilicate Compound, NaCa3PSiO8: Structure Solution and Luminescence Properties.

NaCa3PSiO8 was synthesized in a microwave-assisted solid-state reaction. The crystal structure of the synthesized compound was solved using a least-squares method, followed by simulated annealing. The compound was crystallized in the orthorhombic space group Pna21, belonging to Laue class mmm. The structure consisted of two layers of cation planes, each of which contained three cation channels. The cation channels in each of the layers ran antiparallel to that of the adjacent layer. All the major cations together constituted four distinct crystallographic sites. The Rietveld refinement of the powder X-ray diffraction data, followed by the maximum-entropy method analysis, confirmed the obtained structure solutions. The electronic band structure of the compound was analyzed through density function theory calculations. Luminescence properties of the compound, upon activating with Eu2+ ions, were analyzed through photoluminescence measurements and decay profile analysis. The compound was found to exhibit green luminescence centered at ∼502 nm, with a typical broadband emission due to the transition from the crystal-field split 4f65d to 4f7 levels.

Narsarsukite-structure fluorosilicate as a blue component for white LEDs: structural and optical properties.

A new blue-emitting phosphor, K2ScSi4O10F:Eu>2+ (KSSOF:Eu2+), was synthesized through a solid-state reaction. The structural and optical properties of KSSOF:Eu2+ phosphor, in addition to its thermal quenching and fabrication of white LEDs (WLEDs), were investigated for the first time. The phosphor showed broad blue emission, with a maximum at ∼434 nm under near-ultraviolet excitation due to 5d→4f transition of the Eu2+ ion. The critical distance was calculated to be 12 Šusing the critical concentration of Eu2+ and Dexter's theory for energy transfer. WLEDs were fabricated by blending KSSOF:Eu2+, commercial Lu3Al5O12:Ce3+, and (Sr,Ca)AlSiN3:Eu2+ phosphors, showed a high color rendering index of 88 at a correlated color temperature of 4134 K under a forward bias current of 100 mA.

Smart design to resolve spectral overlapping of phosphor-in-glass for high-powered remote-type white light-emitting devices.

The white light-emitting diode (WLED) is a state-of-the-art solid state technology, which has replaced conventional lighting systems due to its reduced energy consumption, its reliability, and long life. However, the WLED presents acute challenges in device engineering, due to its lack of color purity, efficacy, and thermal stability of the lighting devices. The prime cause for inadequacies in color purity and luminous efficiency is the spectral overlapping of red components with yellow/green emissions when generating white light by pumping a blue InGaN chip with yellow YAG:Ce³âº phosphor, where red phosphor is included, to compensate for deficiencies in the red region. An innovative strategy was formulated to resolve this spectral overlapping by alternatively arranging phosphor-in-glass (PiG) through cutting and reassembling the commercial red CaAlSiN3:Eu²âº and green Lu3Al5O12:Ce³âº PiG. PiGs were fabricated using glass frits with a low softening temperature of 600°C, which exhibited excellent thermal stability and high transparency, improving life time even at an operating temperature of 200°C. This strategy overcomes the spectral overlapping issue more efficiently than the randomly mixed and patented stacking design of multiple phosphors for a remote-type WLED. The protocol for the current design of PiG possesses excellent thermal and chemical stability with high luminous efficiency and color purity is an attempt to make smarter solid state lighting for high-powered remote-type white light-emitting devices.

Control of chromaticity by phosphor in glasses with low temperature sintered silicate glasses for LED applications.

Phosphor-in-glass (PiG) color converters for LED applications were fabricated with a mixture of phosphors, Y3Al5O12:Ce³âº (yellow) and CaAlSiN3:Eu²âº (red). The low sintering temperature (550°C) of SiO2-Na2O-RO (R=Ba, Zn) glass powder enabled the inclusion of CaAlSiN3:Eu²âº (red) phosphor which cannot be embedded with conventional glass powders for PiGs. By simply varying the mixing ratio of glass to phosphors as well as the ratio of yellow to red phosphors, the facile control of the CIE chromaticity coordinates and correlated color temperature of the LED following the Planckian locus has been achieved. Phosphors were well distributed within the glass matrix without noticeable reactions, preserving the enhanced thermal quenching property of the PiG compared to those with silicone resins, for LEDs.

Tunable emission from blue to white light in single-phase Na(0.34)Ca(0.66-x-y)Al(1.66)Si(2.34)O8:xEu2+,yMn2+ (x = 0.07) phosphor for white-light UV LEDs.

A series of single-phased emission-tunable Na(0.34)Ca(0.66)Al(1.66)Si(2.34)O(8):Eu(2+),Mn(2+) phosphors were successfully synthesized by a wet-chemical synthesis method. Photoluminescence excitation (PLE) spectra indicate that the phosphor can be efficiently excited by UV radiation from 250 to 420 nm. Also, NCASO:Eu(2+),Mn(2+) phosphor exhibit a broad blue emission band at 440 nm and an orange emission band at 570 nm, which originate from Eu(2+) and Mn(2+) ions, respectively. Therefore, overall emission color can be tuned from blue to white by increasing the concentration of Mn(2+) ions in the host lattice utilizing energy transfer from Eu(2+) to Mn(2+) ions. This energy transfer phenomenon was demonstrated to be a resonant type through dipole-dipole interaction determined with the help of PL spectra, decay time measurement, and energy transfer efficiency of the phosphor. These results indicate that NCASO:Eu(2+),Mn(2+) can be a promising single-phased white-emitting phosphor for white-light UV LEDs.

Robust moisture and thermally stable phosphor glass plate for highly unstable sulfide phosphors in high-power white light-emitting diodes.

Potential white light-emitting diode (LED) phosphor SrGa2S4, which remains superfluous due to its unstable nature in the presence of moisture, was successfully integrated in a high-power white LED system by developing a glass-based phosphor plate. A glass system with softening temperature at around 600°C, which lies far below the possible decomposition temperature of the sulfide phosphor, provides a stable shield. Physical properties such as thermal stability, transparency, and lower porosity along with chemical stability under operating conditions of the LEDs ensure long-term operability. H2S emission due to the decomposition of sulfide phosphors, which leads to corrosion of LED electrodes, was contained using the developed plate. Higher thermal resistivity of the developed glass system in comparison with conventional resins ensures lower thermal quenching of the luminescence and better color purity.

Energy transfer in Sr2MgSi2O7:Eu2+ phosphors in nano scale and their application to solid state lighting with excellent color rendering.

On the basis of structural information of its host material which shows excellent stability and absorption efficiency in ultra-violet (UV) region, a blue-emitting Sr2MgSi2O7:Eu2+ (SMS:Eu2+) phosphor was synthesized, and its photoluminescence (PL) performance was systematically optimized. In order to enhance its PL properties, Ce3+ was added as a sensitizer based on the energy transfer from the absorption energy of Ce3+ to Eu2+. It was due to the spectral overlap between the photoluminescence excitation spectrum of Ce3+ and the PL spectrum of Eu2+. Moreover, the energy transfer rate from Ce3+ to Eu2+ is generally faster than the emission rate of Ce3+ in the dipole-dipole interaction. Depending upon the amount of Ca2+ substituted into Sr site, their maximum wavelength was varied from -460 to -540 nm in terms of the crystal field effect confirmed by the structural analysis via Rietveld refinement method. Finally, the optimized blue-emitting SMS:Eu2+ and Ca(2+)-substituted yellowish green-emitting SMS:Eu2+ phosphors were applied with Eu(2+)-sensitized red-emitting Ca3Mg3(PO4)4:Mn2+ phosphor introduced in our previous research to UV light emitting diode (LED)-pumped white LEDs. The fabricated white LEDs showed a natural white light with the color coordinate of (0.3298, 0.3280) and the excellent color rendering index of 94.

Preparation of electrospun pyrochlore-structure KGdTa2O7:Eu3+ phosphor: the optical and structural properties for white light emitting diode applications.

Red emitting nanofibers, KGdTa2O7:Eu3+ were synthesized by electrospinning technique followed by heat treatment. As-prepared uniform fiber precursor with diameter ranging from about 700 nm to about 900 nm were calcined after removing organic species by calcination. The fiber surface become rough and diameter decreased to about 250-340 nm range due to decomposition of organic species and formation of inorganic phase. Morphology, structural and photoluminescent properties of fibers were analyzed using thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL). TG-DTA analysis indicates that KGdTa2O7:Eu3+ began to crystalize at 520 degrees C. Fibers annealed at 900 degrees C formed well crystallized uniform fibers. Under ultraviolet excitation KGdTa2O7:Eu3+ exhibits red emission due to transitions in 4f states of Eu3+. The excitation band is dominated by the Eu(3+)--O2-charge transfer band peaked at 289 nm. The emission peak is in the region that is ideal for red light emission.

Intense Hydrochromic Photon Upconversion from Lead-Free 0D Metal Halides For Water Detection and Information Encryption.

Hydrochromic materials that change their luminescence color upon exposure to moisture have attracted considerable attention owing to their applications in sensing and information encryption. However, the existing materials lack high hydrochromic response and color tunability. This study reports the development of a new and bright 0D Cs3 GdCl6 metal halide as the host for hydrochromic photon upconversion in the form of polycrystals (PCs) and nanocrystals. Lanthanides co-doped cesium gadolinium chloride metal halides exhibit upconversion luminescence (UCL) in the visible-infrared region upon 980 nm laser excitation. In particular, PCs co-doped with Yb3+ and Er3+ exhibit hydrochromic UCL color change from green to red. These hydrochromic properties are quantitatively confirmed through the sensitive detection of water in tetrahydrofuran solvent via UCL color changes. This water-sensing probe exhibits excellent repeatability and is particularly suitable for real-time and long-term water monitoring. Furthermore, the hydrochromic UCL property is exploited for stimuli-responsive information encryption via cyphertexts. These findings will pave the way for the development of new hydrochromic upconverting materials for emerging applications, such as noncontact sensors, anti-counterfeiting, and information encryption.

Utilizing VO2 as a Hole Injection Layer for Efficient Charge Injection in Quantum Dot Light-Emitting Diodes Enables High Device Performance.

Quantum dot light-emitting diodes (QLEDs) are promising devices for display applications. Polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) is a common hole injection layer (HIL) material in optoelectronic devices because of its high conductivity and high work function. Nevertheless, PEDOT:PSS-based QLEDs have a high energy barrier for hole injection, which results in low device efficiency. Therefore, a new strategy is needed to improve the device efficiency. Herein, we have demonstrated a bilayer-HIL using VO2 and a PEDOT:PSS-based QLED that exhibits an 18% external quantum efficiency (EQE), 78 cd/A current efficiency (CE), and 25,771 cd/m2 maximum luminance. In contrast, the PEDOT:PSS-based QLED exhibits an EQE of 13%, CE of 54 cd/A, and maximum luminance of 14,817 cd/m2. An increase in EQE was attributed to a reduction in the energy barrier between indium tin oxide (ITO) and PEDOT:PSS, caused by the insertion of a VO2 HIL. Therefore, our results could demonstrate that using a bilayer-HIL is effective in increasing the EQE in QLEDs.

Bredigite-structure orthosilicate phosphor as a green component for white LED: the structural and optical properties.

A green-emitting phosphor, Ca14-xEuxMg2[SiO4]8 (CMS:Eu²âº), has been synthesized as a component of white light emitting diodes (WLEDs). The emission spectrum is broad, with a maximum at about 505 nm under 400 nm excitation due to the transition from the 4f65d excited state to the 4f7-ground state of a Eu²âº ion. The dipole-dipole interaction was a dominant energy transfer mechanism of the electric multipolar character of CMS:Eu²âº. The critical distance was calculated as 12.9 Å and 14.9 Å using a critical concentration of Eu²âº and Dexter's theory for energy transfer. When CMS:Eu²âº and red phosphor are incorporated with an encapsulant on an ultraviolet (λmax = 395 nm) light emitting diodes (LEDs), white light with a color rendering index of 91 under a forward bias current of 20 mA was obtained. The structural and optical characterization of the phosphor is described.

Phosphor in glasses with Pb-free silicate glass powders as robust color-converting materials for white LED applications.

Phosphor-in-glass (PiG) typed robust color converters were fabricated using Pb-free silicate glasses for high-power white LED applications. SiO2-B2O3-RO(R=Ba,Zn) glass powder showed good sintering behavior and high visible transparency under the sintering condition of 750 °C for 30 min without noticeable interaction with phosphors. By simply changing the thickness of the PiG plate or mixing ratio of glass to Y3Al5O12:Ce3+ phosphor, CIE chromaticity coordinates of the LED can be easily controlled. Enhanced thermal quenching property of PiG compared to phosphor with conventional silicone resin suggests its prominent feasibility for high-power/high-brightness white LEDs.

Novel blue-emitting Na(x)Ca(1-x)Al(2-x)Si(2+x)O8:Eu2+ (x = 0.34) phosphor with high luminescent efficiency for UV-pumped light-emitting diodes.

A novel blue-emitting phosphor, Na(0.34)Ca(0.66)Al(1.66)Si(2.34)O(8):Eu(2+) (NCASO:Eu(2+)), was prepared by a wet chemical synthesis method based on the hydrolysis of tetraorthosiliate (TEOS) and confirmed the formation of NCASO:Eu(2+) from Rietveld analysis. Photoluminescence (PL) results showed that the phosphor can be efficiently excited by UV light from 250 to 420 nm, and emitted bright broad blue emission, which has maximum intensity at around 445 nm. Under 365 nm excitation, the PL emission intensity area of optimized NCASO:Eu(2+) was found to be 99.72% of that of a commercial BaMgAl(10)O(17):Eu(2+) (BAM:Eu(2+)) phosphor. Moreover, the optical absorbance, internal quantum efficiency, and external quantum efficiency of NCASO:Eu(2+) were calculated to be 112%, 94%, and 105% of that of the commercial BAM:Eu(2+) phosphor, respectively. The WLEDs were fabricated using the blue NCASO:Eu(2+) phosphor, a green-emitting ß-SiAlON:Eu(2+), and a red-emitting CaAlSiN(3):Eu(2+) phosphors with a near-UV chip. The WLED device exhibited an excellent color-rendering index R(a) of 94 at a correlated color temperature of 5956 K with CIE coordinates of x = 0.323, y = 0.335. These results suggest that NCASO:Eu(2+) is a promising blue-emitting phosphor for UV LED applications.