Switchable Photoelectric Response in High-Temperature Leadless Molecular Ferroelectric [C4N2H14][BiI5].

Lead-free molecular ferroelectrics have garnered considerable attention for their promising potential, but such species with narrow band gap and sensitive photoelectric response are yet inadequate. Herein, we demonstrated the bulk ferroelectric photovoltaic effect in a novel lead-free molecular ferroelectric [C4N2H14][BiI5] with a Curie temperature (Tc) of 366 K and a narrow band gap (Eg) of 1.92 eV. The transformation of the crystal structure from the polar space group P21 to the nonpolar space group P21/m was elucidated using single-crystal X-ray diffraction. Room-temperature (RT) hysteresis loop reveals the intrinsic ferroelectricity of [C4N2H14][BiI5] with a relative small coercive field (Ec ∼ 0.27 kV/cm), saturation polarization (Ps ∼ 1.87 µC/cm2), and remanent polarization (Pr ∼ 1.61 µC/cm2). [C4N2H14][BiI5]-based solar device exhibits significant PV effects with a steady-state photocurrent (Jsc) of 3.54 µA/cm2 and a photovoltage (Voc) of 0.34 V under AM 1.5 G illumination, which can be significantly improved by adjusting the ferroelectric polarization, reaching a maximum Jsc of 140 µA/cm2 and Voc of 0.51 V. This work offers a promising avenue for lead-free molecular ferroelectric materials in the field of optoelectronic devices.

Switchable Photovoltaic Effect and Robust Nonlinear Optical Response in a High-Temperature Molecular Ferroelectric [C8N2H22][PbI4].

Hybrid organic-inorganic molecular ferroelectrics (HOIMFs) have garnered significant attention for their potential applications in nonvolatile memory and spintronic devices. However, few efforts have been devoted to the photoelectric properties of lead halide molecular ferroelectrics, despite the fact that robust ferroelectricity and flexibility are desirable for thin-film photoelectric devices. Herein, we present a novel lead halide molecular ferroelectric [C8N2H22][PbI4] (1) synthesized hydrothermally. A polar monoclinic structure of 1 was solved by single-crystal X-ray diffraction and second-harmonic generation (SHG) tests. A direct band gap of 2.36 eV was confirmed by UV-vis spectrum and theoretical calculation. Hysteresis measurements demonstrated inherent room-temperature (RT) ferroelectricity in 1 with a spontaneous polarization (Ps) of 3.2 µC/cm2. The 1-based photoelectric device shows a notable photovoltaic (PV) effect with Voc ∼ 0.27 V, Jsc ∼ 38 nA/cm2 under AM 1.5 G illumination, and a rapid response time of ∼1.5 ms. A considerable enhancement in PV performance has been achieved by adjusting the ferroelectric polarization, resulting in a maximum Voc ∼ 0.75 V, Jsc ∼ 2.28 µA/cm2. Notably, 1 exhibits a rather large SHG signal, which is approximately 2.61-fold higher than that of KH2PO4 (KDP) upon a 1064 nm laser radiation. This study offers a bright avenue for lead halide molecular ferroelectrics as promising optoelectronic devices and SHG materials.

Crystal Field-Engineered Cr3+-Doped Gd3(MgxGa5-2xGex)O12 Phosphors for Near-Infrared LEDs and X-ray Imaging Applications.

Inorganic materials doped with chromium (Cr) ions generate remarkable and adjustable broadband near-infrared (NIR) light, offering promising applications in the fields of imaging and night vision technology. However, achieving high efficiency and thermal stability in these broadband NIR phosphors poses a significant challenge for their practical application. Here, we employ crystal field engineering to modulate the NIR characteristics of Cr3+-doped Gd3Ga5O12 (GGG). The Gd3MgxGa5-2xGexO12 (GMGG):7.5% Cr3+ (x = 0, 0.05, 0.15, 0.20, and 0.40) phosphors with NIR emission are developed through the cosubstitution of Mg2+ and Ge4+ for Ga3+ sites. This cosubstitution strategy also effectively reduces the crystal field strength around Cr3+ ions, which results in a significant enhancement of the photoluminescence (PL) full width at half-maximum (fwhm) from 97 to 165 nm, alongside a red shift in the PL peak and an enhancement of the PL intensity up to 2.3 times. Notably, the thermal stability of the PL behaviors is also improved. The developed phosphors demonstrate significant potential in biological tissue penetration and night vision, as well as an exceptional scintillation performance for NIR scintillator imaging. This research paves a new perspective on the development of high-performance NIR technology in light-emitting diodes (LEDs) and X-ray imaging applications.

Crystal-Site Engineering of Novel Na3KMg7(PO4)6-x(BO3)x:Eu2+ Phosphors for Full-Spectrum Lighting.

The "cyan gap" is the bottleneck problem in violet-driven full-spectrum white-light-emitting diodes (wLEDs) in healthy lighting. Accordingly, we develop a novel broadband-blue-cyan emission Na3KMg7(PO4)6-x(BO3)x:Eu2+ (NKMPB:Eu2+) phosphor via crystal-site engineering. This phosphor is derived from the Na3KMg7(PO4)6:Eu2+ phosphor, which shows desired abundant cyan emissive components. A comparative study is conducted to reveal the microstructure-property relationship and the key influential factors to its spectrum distribution. It can be found that the introduced (BO3)3- units can manipulate the site-selective occupation of Eu2+ activators, asymmetrically broadening the emission spectrum in NKMPB:Eu2+. Considering detailed luminescence performance analysis and the density functional theory calculations, a new substitution pathway of Eu2+ is created by substituting (PO4)3- with (BO3)3- units, making partial Eu2+ ions enter the Mg2+ (CN = 5, CN = 6) crystallographic sites, and yielding an extra emission band at 600 nm (16667 cm-1) and especially 501 nm (19960 cm-1). Meanwhile, a high-color-quality full-spectrum-emitting wLEDs was fabricated, upon 100 mA forward-bias current driven. Due to the achieved extra cyan emissive components of NKMPB:Eu2+, the constructed NKMPB:Eu2+-based wLEDs show better color rendering ability (∼90.9) than that of Na3KMg7(PO4)6:Eu2+-based wLEDs (∼86.3), and also demonstrate its great potential in full-spectrum healthy lighting.

Rational Design of Nitride Phosphor-In-Glass with Robust Stability and Photoluminescence Performance.

Phosphor-in-glass represents a promising avenue for merging the luminous efficiency of high-quality phosphor and the thermal stability of a glass matrix. Undoubtedly, the glass matrix system and its preparation are pivotal factors in achieving high stability and preserving the original performance of embedded phosphor particles. In contrast to the well-established commercial Y3Al5O12:Ce3+ oxide phosphor, red nitride phosphor, which plays a critical role in high-quality lighting, exhibits greater structural instability during the high-temperature synthesis of inorganic glasses. A telluride glass with a refractive index (RI = 2.15@615 nm) akin to that of nitride phosphor (∼2.19) has been devised, demonstrating high efficiency in photon utilization. The lower glass-transition temperature plays a crucial role in safeguarding phosphor particles against erosion resulting from exposure to high-temperature melts. Phosphor-in-glass retains 93% of the quantum efficiency observed for pure phosphor. The assembled white light-emitting diodes module has precise color tuning capabilities, achieving an optimal color rendering index of 93.7, a luminous efficacy of 80.4 lm/W, and a correlated color temperature of 5850 K. These outcomes hold potential for advancing the realm of inorganic package and high-quality white light illumination.

Intense green light emission in Sr2 ZnGe2 O7 :Mn2+ phosphors by the design of high symmetry melilite structure.

A green phosphor Sr2 ZnGe2 O7 :Mn2+ with a melilite structure was prepared using a high-temperature solid-state reaction. When the 535 nm emission was monitored, the excitation spectrum of the Sr2 ZnGe2 O7 :Mn2+ was found to contain two excitation bands in the ultraviolet (UV) region. When excited by UV light, the sample shows bright green emission at 535 nm, which corresponds to the distinctive transition of Mn2+ (4 T1 →6 A1 ). Moreover, the quantum efficiency of Sr2 ZnGe2 O7 :Mn2+ could reach 67.6%. Finally, a high-performance white-light-emitting diode (WLED) with a low correlated colour temperature of 4632 K and a high colour rendering index (CRI) of 92.3 were packaged by coating commercial blue and red phosphors with an optimized Sr2 ZnGe2 O7 :Mn2+ sample on a 310 nm UV chip. This indicated that Sr2 ZnGe2 O7 :Mn2+ has the potential application as a green component in the WLED lighting field.

Gate-Tunable van der Waals Photodiodes with an Ultrahigh Peak-to-Valley Current Ratio.

Photodetectors and imagers based on 2D layered materials are currently subject to a rapidly expanding application space, with an increasing demand for cost-effective and lightweight devices. However, the underlying carrier transport across the 2D homo- or heterojunction channel driven by the external electric field, like a gate or drain bias, is still unclear. Here, a visible-near infrared photodetector based on van der Waals stacked molybdenum telluride (MoTe2 ) and black phosphorus (BP) is reported. The type-I and type-II band alignment can be tuned by the gate and drain voltage combined showing a dynamic modulation of the conduction polarity and negative differential transconductance. The heterojunction devices show a good photoresponse to light illumination ranging from 520-2000 nm. The built-in potential at the MoTe2 /BP interface can efficiently separate photoexcited electron-hole pairs with a high responsivity of 290 mA W-1 , an external quantum efficiency of 70%, and a fast photoresponse of 78 µs under zero bias.

Nano Ball-Milling Using Titania Nanoparticles to Anchor Cesium Lead Bromine Nanocrystals and Energy Transfer Characteristics in TiO2 @CsPbBr3 Architecture.

Recently, all-inorganic halide perovskite (CsPbX3 , (X = Cl, Br, and I)) nanocrystals (NCs) based hybrid architectures have attracted extensive attention owing to their distinct luminescence characteristics. However, due to stress and lattice mismatch, it is still a challenge to construct heterojunctions between perovskite NCs and the nanostructures with different lattice parameters and non-cubic contour. In this work, a room temperature mechanochemical method is presented to construct TiO2 @CsPbBr3 hybrid architectures, in which TiO2 nanoparticles (NPs) with a hard lattice as nano "balls" mill off the angles and anchor to the CsPbBr3 NCs with a soft lattice. On the contrary, to ball-mill without TiO2 or with conventional ceramics balls replacing TiO2 , CsPbBr3 NCs still maintain cubic contour deriving from their cubic crystal structures. Moreover, the TiO2 @CsPbBr3 architectures display distinct improvement of photoluminescence quantum yields and more excellent thermal stability in contrast with pristine CsPbBr3 owing to the passivation of surface defect, small surface area, and energy transfer from CsPbBr3 to TiO2 . Meanwhile, there is distinct luminous decay characteristic under the radiation of UV and visible light due to the "on" and "off" TiO2 response. The method provides an alternative strategy to acquire other anchoring heterojunctions based on perovskite NCs for further regulating their luminescent characteristics.

Asterisk-shaped microstructured fiber for an octave coherent supercontinuum in a sub-picosecond region.

We selected two thermally matched silicate glasses with fair refractive index contrast and developed an asterisk-shaped all-solid microstructured optical fiber. The fiber presents a low, ultra-flat, and all-normal dispersion in a wide wavelength range, allowing for the generation of an octave-spanning coherent supercontinuum (SC) in a 20 dB dynamic range with 0.5 ps pump pulses at 1.55 µm. This result improves pump pulse duration that is only ∼100 fs, related to the broadband and highly coherent SC generation in fibers with all-normal dispersion. This enables broadband SC sources with all-fiber, high-power, and highly coherent properties.

Ion-Exchangeable Microporous Polyoxometalate Compounds with Off-Center Dopants Exhibiting Unconventional Luminescence.

The synthesis of luminescent polyoxometalates (POMs) typically relies on the assembly of POM ligands with rare earth or transition metals, placing significant constraints on the composition, structure, and hence the luminescence properties of the resultant systems. Herein, we show that the ion-exchange strategy can be used for the synthesis of novel POM-based luminescent materials. We demonstrate that introducing bismuth ions into an ion-exchangeable, microporous POM compound yields an unconventional system luminescing in the near-infrared region. Experimental characterization, coupled with quantum chemical calculations, confirms that bismuth ions site-specifically occupy an off-center site in the lattice, and have an asymmetric coordination geometry unattainable by other means, thus giving rise to peculiar emission. Our findings offer an effective strategy for the synthesis of POM-based luminescent materials, and the design concept may potentially be adapted to the creation of POM-based systems with other functionalities.

Unconventional Luminescent Centers in Metastable Phases Created by Topochemical Reduction Reactions.

A low-temperature topochemical reduction strategy is used herein to prepare unconventional phosphors with luminescence covering the biological and/or telecommunications optical windows. This approach is demonstrated by using Bi(III)-doped Y2O3 (Y(2-x)Bi(x)O3) as a model system. Experimental results suggest that topochemical treatment of Y(2-x)Bi(x)O3 using CaH2 creates randomly distributed oxygen vacancies in the matrix, resulting in the change of the oxidation states of Bi to lower oxidation states. The change of the Bi coordination environments from the [BiO6] octahedra in Y(2-x)Bi(x)O3 to the oxygen-deficient [BiO(6-z)] polyhedra in reduced phases leads to a shift of the emission maximum from the visible to the near-infrared region. The generality of this approach was further demonstrated with other phosphors. Our findings suggest that this strategy can be used to explore Bi-doped or other classes of luminescent systems, thus opening up new avenues to develop novel optical materials.

Structure modification and luminescence regulation in new violet light excitable Sr(2-y)BayY4La4(SiO4)6O2:xEu2+ phosphors via cation substitution.

Cyan-emitting phosphors are urgently needed to address the "cyan gap" in artificial full-spectrum lighting. In this research, a series of Sr(2-y)BayY4La4(SiO4)6O2:xEu2+ (0.005 ≤ x ≤ 0.08, 0.0 ≤ y ≤ 2.0) phosphors with tunable luminescence was synthesized. Through cation regulation, the luminescence color of Sr(2-y)BayY4La4(SiO4)6O2:xEu2+ can be adjusted from yellow to cyan. Crystal structure analysis revealed that Eu2+ ions simultaneously occupy [Sr1/Ba1Y1La1] and [Sr2/Ba2Y2La2] sites, resulting in multiple luminescence centers and a broadened emission spectrum. With increasing Ba2+ ion concentration, the PLE spectrum was red-shifted from 337 nm to 372 nm, and the excitation intensity in the violet region was significantly enhanced, making it more compatible with violet LED chips. Meanwhile, the PL spectrum was blue-shifted from 543 nm to 496 nm with increasing Ba2+ concentration, accompanied by an increase of about 10 times in the excitation and emission intensity. The optimized Ba2Y4La4(SiO4)6O2:0.02Eu2+ phosphor can be excited by violet light and emits bright cyan light effectively, which can be used to fill the "cyan gap". Eventually, a series of white LED devices was manufactured by combining the as-prepared luminescence-tunable phosphors with commercial phosphors. Among them, the 410 nm violet LED chip-based WLED(Ba2) device comprising Ba2Y4La4(SiO4)6O2:0.02Eu2+ exhibited the best electroluminescence performance, increasing the color rendering index from 82.0 to 98.6, verifying the compensation effect of the Ba2Y4La4(SiO4)6O2:Eu2+ phosphor on cyan light.

Development of a novel Eu2+ activated oxonitridosilicate cyan phosphor for enhancing the color quality of a violet-chip-based white LED.

Cyan phosphors are urgently needed to fill the cyan gap and improve the spectral continuity of white light-emitting diodes (LEDs) to cater to the high demand for high-quality lighting. Here, a series of new Eu2+-activated La3Si6.5Al1.5N9.5O5.5 (LSANO) cyan phosphors were prepared, and their luminescence properties and color centers were analyzed through fluorescence spectral measurements from 7 K to 475 K. At 300 K, the photoluminescence excitation (PLE) spectrum monitored at 483 nm presents a broadband of 200-460 nm with a peak at 398 nm, matching well with commercial violet LED chips. When excited by 398 nm violet light, the photoluminescence emission (PL) spectrum of LSANO:0.01Eu2+ exhibits a cyan emission band at about 483 nm. At 7 K, the emission spectrum clearly shows an asymmetric emission band and the emission peak wavelength changes from 483 nm (300 K) to 500 nm (7 K), indicating that there are two possible color centers in the LSANO:Eu2+ phosphor. Moreover, the maximum emission value can be adjusted from 480 to 499 nm by adjusting the doping content of Eu2+. Finally, a violet-chip-based white LED with the optimized color quality of Ra = 91.4, Rf = 90.1, and Rg = 93.6 was fabricated by adding the prepared cyan phosphor, verifying the potential application of the prepared cyan phosphor LSANO:Eu2+ in high-quality white LEDs.

Bulk Photovoltaic Effect in High-Temperature Lead-Halide Molecular Ferroelectric [C4N2H14][PbI4].

Hybrid organic-inorganic molecular ferroelectrics (HOIMFs) have garnered significant attention owing to their potential applications in optoelectronic and spintronic devices. However, HOIMFs with high Curie temperature (Tc), narrow bandgap (Eg), excellent stability, and high breakdown voltage are still very rare. Herein, we present a novel lead-halide molecular ferroelectric, (1,4-butanediammonium)PbI4 (1), synthesized hydrothermally. 1 exhibits a ferroelectric-to-paraelectric phase transition with a high Curie temperature of 485 K, a room temperature ferroelectric hysteresis loop with a robust saturation polarization of 3.9 µC/cm2 and strong coercivity of 33 kV/cm, and a typical semiconductor behavior with a direct bandgap of 2.28 eV. Switchable photovoltaic effect was observed in 1-based device with a fast response time of ∼2 ms and high breakdown electric field of 80 kV/cm. Dramatically enhanced photovoltaic performance has been achieved by manipulating the ferroelectric polarization, resulting in a maximum photovoltage of Voc ∼ 0.84 V and a photocurrent of Jsc ∼ 33.31 nA/cm2 under standard AM 1.5 G illumination. This study offers a bright avenue for advancing high-Tc lead-halide molecular ferroelectrics with promising potentials in photodetectors, data storage, and logical switching devices.

Cs2MnCl4:Eu2+: A Near-Violet Light-Triggered Single-Component White Light Emitter.

Single-component white-light luminescent materials are considered an economical and facile choice for phosphor-converted white light-emitting diodes (pc-WLEDs). Here, a new single-component white-light-emitting material Cs2MnCl4:Eu2+ based on the combination of a lead-free halide structure and a rare-earth ion is first reported. Benefiting from the smart dilution-sensitization design strategy, white light composed of dual broad emission originating from Eu2+ (blue light, 444 nm, 4f65d1 → 4f7) and Mn2+ (yellow light, 566 nm, 4T1g → 6A1g) was successfully realized under near-ultraviolet light (404 nm) radiation with a high photoluminescence quantum yield of 66%. Based on the single-source Cs2MnCl4:Eu2+ phosphor, a pc-WLEDs device with "eye-friendly" white light production was successfully fabricated. The pc-WLEDs exhibit suitable color coordinates of (0.3294, 0.2746) and a high color rendering index of 82.3, demonstrating the potential in the future health-conscious illumination application by reducing the risk of eye strain and high-energy blue-light damage. This work achieves a new single-component white-light-emitting Mn-based halide phosphor and provides a new path for the design of single-component white light sources in Mn-based halides.

A graphene-like hollow sphere anode for lithium-ion batteries.

We report a flash Joule heating method for the rapid preparation of graphene-like materials. The L-GHS exhibited a uniform diameter of 200 nm and an ideal specific surface area of 670 m2 g-1. Meanwhile, the specific capacity of L-GHS remained at 942 mA h g-1 after 600 cycles (1 A g-1), which shows excellent electrochemical performance.

Continuous-flow synthesis of CsPbI3/TiO2 nanocomposites with enhanced water and thermal stability.

The inherent poor stability of CsPbI3 nanocrystals hinders the practical application of this material. Therefore, it is still a challenge to improve the stability of CsPbI3 nanocrystals and realize their large-scale continuous preparation. In this work, we report the preparation of CsPbI3/TiO2 nanocomposites with high stability by a microfluidic method. After the combination of CsPbI3 nanorods with TiO2, the PL intensity increased by 1.3 times under excitation at 577 nm due to the passivating effect of TiO2 on the surface of CsPbI3 nanorods and its carrier transport characteristics. Meanwhile, due to the coating of TiO2, the surface exposure area of CsPbI3 nanorods is reduced, which blocks external environmental effects to some extent and effectively improves the stability of CsPbI3 nanorods. Finally, an LED with a color gamut of 142% NTSC and a color temperature (CCT) of 3952 K was obtained by combining CsPbI1.5Br1.5/TiO2 and CsPbBr3/TiO2 nanocomposites with a blue light chip (455 nm). This study shows that the continuous and controllable synthesis of all inorganic halide perovskite nanocrystals by a microfluidic method is of great significance in the fabrication of high-performance optoelectronic materials and display devices.

Heterojunctions of Mercury Selenide Quantum Dots and Halide Perovskites with High Lattice Matching and Their Photodetection Properties.

Heterojunction semiconductors have been extensively applied in various optoelectronic devices due to their unique carrier transport characteristics. However, it is still a challenge to construct heterojunctions based on colloidal quantum dots (CQDs) due to stress and lattice mismatch. Herein, HgSe/CsPbBrxI3-x heterojunctions with type I band alignment are acquired that are derived from minor lattice mismatch (~1.5%) via tuning the ratio of Br and I in halide perovskite. Meanwhile, HgSe CQDs with oleylamine ligands can been exchanged with a halide perovskite precursor, acquiring a smooth and compact quantum dot film. The photoconductive detector based on HgSe/CsPbBrxI3-x heterojunction presents a distinct photoelectric response under an incident light of 630 nm. The work provides a promising strategy to construct CQD-based heterojunctions, simultaneously achieving inorganic ligand exchange, which paves the way to obtain high-performance photodetectors based on CQD heterojunction films.

Preparation of a novel Bi9O7.5S6/SnS composite film with improved photoelectric properties.

Atomically thin two-dimensional (2D) bismuth oxychalcogenides have been considered as promising candidates for high-speed and low-power photoelectronic devices due to their high charge carrier mobility and excellent environmental stability. However, the photoelectric performance of their bulk materials still falls short of expectations. Herein, a novel Bi9O7.5S6/SnS composite film with a type-II heterojunction was successfully prepared by combining hydrothermal and knife-coating techniques. The crystal structure, morphology, and optical properties were systematically investigated. Under 1 V bias voltage, the photocurrent of the Bi9O7.5S6/SnS composite film can be obtained as 107 µA cm-2, which is about 29.9 times and 93.9 times higher than that of bare Bi9O7.5S6 and SnS, respectively. The type-II heterojunction has played a significant role in improving the photoelectric performance of the Bi9O7.5S6/SnS composite film by facilitating the separation and transfer of photo-generated carriers. This work sheds light on the design and development of new bismuth-based composite materials for advanced photoelectric and photocatalytic applications.

Three-dimensional Ti3C2Tx and MnS composites as anode materials for high performance alkalis (Li, Na, K) ion batteries.

Exploring capable and universal electrode materials could promote the development of alkalis (Li, Na, K) ion batteries. 2D MXene material is an ideal host for the alkalis (Li, Na, K) ion storage, but its electrochemical performance is limited by serious re-stacking and aggregation problems. Herein, we cleverly combined electrostatic self-assembly with gas-phase vulcanization method to successfully combine Ti3C2Tx-MXene with ultra-long recyclability and high conductivity with MnS, which presents high specific capacity but poor conductivity. The as-prepared 3D hierarchical Ti3C2Tx/MnS composites have an unique sandwich-like constituent units. The tiny MnS nanoparticles are restricted between the Ti3C2Tx layers and play a key role in expanding the Ti3C2Tx interlayer spacing. As a result, the 3D Ti3C2Tx/MnS composites as the anode of LIBs exhibits a superior capacities of 826 and 634 mAh/g after 1000 and 3000 cycles at 0.5 and 1.0 A/g, respectively. More importantly, we reveal the reaction mechanism that the specific capacity first increases and then gradually stabilizes with the increase of charge and discharge cycle times when the as-prepared 3D Ti3C2Tx/MnS was used as the anode of LIBs. In addition, we have also used this material in SIBs and PIBs and achieved remarkable electrochemical capability, with a specific capacity of 107 mAh/g after 2500 cycles at 0.5 A/g or 127 mAh/g after the 2000th cycle at 0.2 A/g, respectively.