Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures.

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2 ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100 ps) and electron (∼1 ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Phosphorescence in Mn4+-Doped R+/R2+ Germanates (R+ = Na+ or K+, R2+ = Sr2+).

Single crystals of three new compounds, Na0.36Sr0.82Ge4O9 (1, proposed composition), Na2SrGe6O14 (2), and K2SrGe8O18 (3), were obtained and characterized using single-crystal X-ray diffraction. Their structures contain three-dimensional (3D) anionic frameworks built from GeO4 and GeO6 polyhedra. The presence of octahedral Ge4+ sites makes the new phases suitable for Mn4+ substitution to obtain red-emitting phosphors with a potential application for light conversion. Photoluminescence properties of Mn4+-substituted Na2SrGe6O14 (2) and K2SrGe8O18 (3) samples were studied over a range of temperatures, and red light photoluminescence associated with the electronic transitions of tetravalent manganese was observed. The Na2SrGe6O14 (2) phase was also substituted with Pr3+ on the mixed Na-Sr site similar to the previously studied Na2CaGe6O14:Pr3+. The red emission peak of the Pr3+ activator occurs at a shorter wavelength (610 nm) compared to that of Mn4+ (662-663 nm). Additionally, second harmonic generation (SHG) data were collected for the noncentrosymmetric Na2SrGe6O14 (2) phase, indicating weak SHG activity. Diffuse reflectance spectroscopy and density of states calculations were performed to estimate the band gap values for pristine Na2SrGe6O14 (2) and K2SrGe8O18 (3) phases.

Sensitive and Reliable Fluorescent Thermometer Based on a Red-Emitting Li2MgHfO4:Mn4+ Phosphor.

Contactless fluorescent thermometers are rapidly gaining popularity due to their sensitivity and flexibility. However, the development of sensitive and reliable non-rare-earth-containing fluorescent thermometers remains a significant challenge. Here, a new rare-earth-free, red-emitting phosphor, Li2MgHfO4:Mn4+, was developed for temperature sensing. An experimental analysis combined with density functional theory and crystal field calculations reveals that the sensitive temperature-dependent luminescence arises from nonradiative transitions induced by lattice vibration. Li2MgHfO4:Mn4+ also exhibits reliable recovery performance after 100 heating-cooling cycles due to the elimination of surface defects, which is rare but vital for practical application. This study puts forward a new design strategy for fluorescent thermometers and sheds light on the fundamental structure-property relationships that guide sensitive temperature-dependent luminescence. These considerations are crucial for developing next-generation fluorescence-based thermometers.

The Deep Eutectic Solvent Precipitation Synthesis of Metastable Zn4V2O9.

A precipitation method involving a deep eutectic solvent (DES)─a mixture of hydrogen bond donor and acceptor─is used to synthesize a ternary metal oxide. Without toxic reagents, precipitates consisting of Zn3(OH)2V2O7·nH2O and Zn5(OH)6(CO3)2 are obtained by simply introducing deionized H2O to the DES solution containing dissolved ZnO and V2O5. Manipulation of the synthetic conditions demonstrates high tunability in the size/morphology of the two-dimensional nanosheets precipitated during the dynamic equilibrium process. According to differential scanning calorimetry and high-temperature powder X-ray diffraction, Zn3V2O8 and ZnO obtained by the annealing of the precipitate are intermediates in the reaction pathway toward metastable Zn4V2O9. Intimate mixing of the metal precursors achieved by the precipitation method allows access to the metastable zinc-rich vanadate with unusually rapid heat treatment. The UV-vis and surface photovoltage spectra reveal the presence of sub-band gap states, stemming from the reduced vanadium (V4+) center. Photoelectrochemical measurements confirm weak photoanodic currents for water and methanol oxidation. For the first time, this work shows the synthesis of a metastable oxide with the DES-precipitation route and provides insight into the structure-property relationship of the zinc-rich vanadate.

Spectral Design of Phosphor-Converted LED Lighting Guided by Color Theory.

In the race to develop new luminescent materials for the next generation of light-emitting-diode (LED)-based solid-state lighting and display applications, it is often forgotten that color theory and human perception should be some of the principal factors guiding materials design. In this Viewpoint, we explore some of the antiquated colorimetrics established originally for incandescent and fluorescent lighting and discuss how they are still widely applied in the literature today to interpret the color quality of luminescent materials, like inorganic phosphors and quantum dots, and to analyze prototype devices, despite their shortcomings. We then shift our analysis toward contemporary ideas in color theory that more accurately describe the color quality of modern LED light bulbs and flat-panel displays. Finally, the perspective examines the opportunities and challenges of applying these new concepts to guide the design of luminescent materials used in LED-based applications.

Advancing Human-Centric LED Lighting Using Na2MgPO4F:Eu2.

The proliferation of energy-efficient light-emitting diode (LED) lighting has resulted in continued exposure to blue light, which has been linked to cataract formation, circadian disruption, and mood disorders. Blue light can be readily minimized in pursuit of "human-centric" lighting using a violet LED chip (λem ≈ 405 nm) downconverted by red, green, and blue-emitting phosphors. However, few phosphors efficiently convert violet light to blue light. This work reports a new phosphor that meets this demand. Na2MgPO4F:Eu2+ can be excited by a violet LED yielding an efficient, bright blue emission. The material also shows zero thermal quenching and has outstanding chromatic stability. The chemical robustness of the phosphor was also confirmed through prolonged exposure to water and high temperatures. A prototype device using a 405 nm LED, Na2MgPO4F:Eu2+, and a green and red-emitting phosphor produces a warm white light with a higher color rendering index than a commercially purchased LED light bulb while significantly reducing the blue component. These results demonstrate the capability of Na2MgPO4F:Eu2+ as a next-generation phosphor capable of advancing human-centric lighting.

Thermally Robust and Color-Tunable Blue-Green-Emitting BaMgSi4O10:Eu2+,Mn2+ Phosphor for Warm-White LEDs.

The dual emission produced from Mn2+ when codoped with rare earth ions like Eu2+ or Ce3+ in inorganic compounds makes these materials attractive as efficient, color-tunable phosphors for warm-white solid-state lighting. Here, a series of efficient blue-green-emitting BaMgSi4O10:Eu2+,Mn2+ phosphors with thermally robust, tunable luminescence are reported. Steady-state and time-resolved photoluminescence spectroscopy reveal that Eu2+ and Mn2+ each occupy a single crystallographic site and confirm that energy transfer occurs from Eu2+ to Mn2+. The internal and external quantum efficiency of BaMgSi4O10:Eu2+,Mn2+ can reach as high as 69.0 and 47.5%, respectively, upon 360 nm excitation. Moreover, this phosphor possesses nearly zero-thermal quenching up to 440 K due to thermally induced electron detrapping. A fabricated UV-excited white LED device incorporating the blue-green-emitting BaMgSi4O10:Eu2+,Mn2+ and the red-emitting Sr2Si5N8:Eu2+ phosphors exhibits an excellent CRI of 94.3 with a correlated color temperature of 3967 K. These results prove the potential applications of Eu2+,Mn2+ codoped BaMgSi4O10 phosphor for generating warm-white light.

Combining experiment and computation to elucidate the optical properties of Ce3+ in Ba5Si8O21.

Complex alkaline earth silicates have been extensively studied as rare-earth substituted phosphor hosts for use in solid-state lighting. One of the biggest challenges facing the development of new phosphors is understanding the relationship between the observed optical properties and the crystal structure. Fortunately, recent improvements in characterization techniques combined with advances in computational methodologies provide the research tools necessary to conduct a comprehensive analysis of these systems. In this work, a new Ce3+ substituted phosphor is developed using Ba5Si8O21 as the host crystal structure. The compound is evaluated using a combination of experimental and computational methods and shows Ba5Si8O21:Ce3+ adopts a monoclinic crystal structure that was confirmed through Rietveld refinement of high-resolution synchrotron powder X-ray diffraction data. Photoluminescence spectroscopy reveals a broad-band blue emission centered at ∼440 nm with an absolute quantum yield of ∼45% under ultraviolet light excitation (λex = 340 nm). This phosphor also shows a minimal chromaticity-drift but with moderate thermal quenching of the emission peak at elevated temperatures. The modest optical response of this phase is believed to stem from a combination of intrinsic structural complexity and the formation of defects because of the aliovalent rare-earth substitution. Finally, computational modeling provides essential insight into the site preference and energy level distribution of Ce3+ in this compound. These results highlight the importance of using experiment and computation in tandem to interpret the relationship between observed optical properties and the crystal structures of all rare-earth substituted complex phosphors.

Evaluating Thermal Quenching Temperature in Eu3+-Substituted Oxide Phosphors via Machine Learning.

One of society's grand challenges is to reduce energy usage in ways that are cost-effective, sustainable, and environmentally benign. Replacing incandescent and compact fluorescent light bulbs with energy-efficient, solid-state white lighting is one of the easiest and most promising solutions. Eu3+-substituted inorganic oxide phosphors are one class of materials that can serve as the red component in these new light bulbs, allowing the creation of warm white light. Unfortunately, the emission intensity in most of these materials cannot be reliably maintained at elevated temperatures. There is therefore a need to discover entirely novel phosphor materials that are thermally robust; however, this is generally a prolonged and expensive process requiring extensive synthetic effort. In this work, we develop a machine-learning regression algorithm based on 134 experimentally measured temperature-dependent Eu3+ emission data points to rapidly estimate the thermal quenching temperature (T50), which is defined as the temperature when the emission intensity is half of the initial value. The T50 was then predicted for more than 1000 potential oxide Eu3+ phosphor hosts using this model. Five compounds with predicted thermal quenching temperatures >423 K were subsequently selected and synthesized for validation of this approach. The phosphors, Sr2ScO3F, Cs2MgSi5O12, Ba2P2O7, LiBaB9O15, and Y3Al5O12, all exhibit good thermal stability when substituted with Eu3+, suggesting the success of our methodology.