Multi-Site Cation Control of Ultra-Broadband Near-Infrared Phosphors for Application in Light-Emitting Diodes.

Near-infrared (NIR) phosphors are fascinating materials that have numerous applications in diverse fields. In this study, a series of La3Ga5GeO14:Cr3+ phosphors, which was incorporated with Sn4+, Ba2+, and Sc3+, was successfully synthesized using solid-state reaction to explore every cationic site comprehensively. The crystal structures were well resolved by combining synchrotron X-ray diffraction and neutron powder diffraction through joint Rietveld refinements. The trapping of free electrons induced by charge unbalances and lattice vacancies changes the magnetic properties, which was well explained by a Dyson curve in electron paramagnetic resonance. Temperature and pressure-dependent photoluminescence spectra reveal various luminescent properties between strong and weak fields in different dopant centers. The phosphor-converted NIR light-emitting diode (pc-NIR LED) package demonstrates a superior broadband emission that covers the near-infrared (NIR) region of 650-1050 nm. This study can provide researchers with new insight into the control mechanism of multiple-cation-site phosphors and reveal a potential phosphor candidate for practical NIR LED application.

Broadband NaK2Li[Li3SiO4]4:Ce Alkali Lithosilicate Blue Phosphors.

Phosphors with a rigid and symmetrical structure are urgently needed. The alkali lithosilicate family (A[Li3SiO4]) has been extensively studied with a narrow emission band due to its unique cuboid-coordinated environment and rigid structure. However, here we demonstrate for the first time Ce-doped NaK2Li[Li3SiO4]4 phosphors with a broad emission band, a high internal quantum efficiency (85.6%), and excellent thermal stability. Photoluminescence indicates the Ce's preference to occupy the Na+ site, leading to a strong blue color emission with peak maxima at 417 and 450 nm. Temperature- and pressure-dependent photoluminescence reveals thermal stability and a phase transition. Moreover, the X-ray absorption near-edge structure reveals the mixing of Ce3+ and Ce4+ in the materials; this result differs from that of Eu2+-doped A[Li3SiO4] phosphors. The charge compensation process is then proposed to explain this difference. This study not only provides insights into Ce-doped UCr4C4-type phosphors but also explains the charge compensation mechanism of the aliovalent doping process.

Efficient Luminescence from CsPbBr3 Nanoparticles Embedded in Cs4PbBr6.

Cs4PbBr6 is regarded as an outstanding luminescent material with good thermal stability and optical performance. However, the mechanism of green emission from Cs4PbBr6 has been controversial. Here we show that isolated CsPbBr3 nanoparticles embedded within a Cs4PbBr6 matrix give rise to a "normal" green luminescence while superfluorescence at longer wavelengths is suppressed. High-resolution transmission electron microscopy shows that the embedded CsPbBr3 nanoparticles are around 3.8 nm in diameter and are well-separated from each other, perhaps by a strain-driven mechanism. This mechanism may enable other efficient luminescent composites to be developed by embedding optically active nanoparticles epitaxially within inert host lattices.

Study of persistent luminescence and thermoluminescence in SrSi2N2O2:Eu2+,M3+ (M = Ce, Dy, and Nd).

The process of persistent luminescence or glow-in-the-dark, the delayed emission of light of irradiated substances, has long fascinated researchers, who have made efforts to explain the underlying physical phenomenon as well as put it to practical use. However, persistent luminescence is an elusive and difficult process, both in terms of controlling or altering its properties, as well as providing a quantitative description. In this paper, we used SrSi2N2O2:Eu2+ as a model persistent phosphor, characterized by the broad distribution of structural defects and exhibiting long-lasting Eu2+ luminescence that is visible for a few minutes after switching off UV light. We investigated the persistent luminescence process by two complementary methods, namely, thermoluminescence and temperature-dependent persistent luminescence decay measurements. Analysis of experimental data allowed us to determine the depth distribution of traps, and allowed us to distinguish two different mechanisms by which the emission is delayed. The first, the temperature-dependent mechanism, is related to trap activation, while the second, temperature-independent mechanism is related to carrier migration. Finally, we employed the strategy of the co-doping of the phosphor SrSi2N2O2:Eu2+,M3+ (M = Ce, Nd, Dy) to modify the persistent luminescence properties.

Thermally Stable and Deep Red Luminescence of Sr1-xBax[Mg2Al2N4]:Eu2+ (x = 0-1) Phosphors for Solid State and Agricultural Lighting Applications.

The systematic substitution of Ba in the Sr site of Sr[Mg2Al2N4]:Eu2+ generates a deep-red-emitting phosphor with enhanced thermal luminescence properties. Gas pressure sintering (GPS) of all-nitride starting materials in Molybdenum (Mo) crucibles yields pure-phase red-orange-colored phosphors. Peaks in the synchrotron X-ray diffraction (SXRD) data show a systematic shift toward smaller angles due to the introduction of the larger Ba cation in the same crystal structure. The photoluminescence property reveals that Ba substitution shifts the original emission wavelength of Sr[Mg2Al2N4]:Eu2+ (625 nm) toward ∼690 nm for Ba[Mg2Al2N4]:Eu2+. Thermal stability measurement of Sr1-xBax[Mg2Al2N4] indicates a systematic increase in stability from x = 0 to x = 1. X-ray absorption near-edge spectroscopy (XANES) results demonstrate the coexistence of Eu2+ and Eu3+. The red-shift and the enhanced thermal stability reveals that the distance of the emitting 5d level to the conduction band of Ba[Mg2Al2N4]:Eu2+ is large. The ionic size mismatch of Eu occupying a Ba site reduces the symmetry, thereby further splitting the degenerate emitting 5d level and lowering the energy of the emitting center. The development of deep-red phosphors emitting at 670-690 nm (x = 0.8-1.0) offers possible candidates for plant lighting applications.

Chromium(III)-Doped Fluoride Phosphors with Broadband Infrared Emission for Light-Emitting Diodes.

Two types of infrared fluoride phosphors, Cr3+-doped K3AlF6 and K3GaF6, were developed in this research. The K3Al1-xF6:xCr3+ and K3Ga1-yF6:yCr3+ fluoride phosphors were proven to be pure phase via X-ray diffraction refinement, which demonstrated that the procedure can be applied to large-scale production. Electron paramagnetic resonance measurements indicated that Cr3+ ions in cubic with respect to noncubic are coupled better with K3GaF6 than with K3AlF6. The main differences between these two phosphors, the site symmetry and pressure behavior of the spectra, were obtained in temperature- and pressure-dependent spectra. According to the calculation results, Cr3+ in fluorine coordination at ambient pressure indicates an intermediate crystal field. For the phosphor-converted light-emitting diodes (LEDs) fabricated from these two phosphors, the spectral range is from 650 to 1000 nm, which resulted in a radiant flux of 7-8 mW with an input power of 1.05 W. The research reveals detailed luminous properties, which will lead to a new way of studying Cr3+-doped fluoride phosphors and their application in LEDs.

Influence of Al3+ co-doping on the spectral properties of europium doped Ca9Y(PO4)7.

A series of luminescent materials based on a calcium yttrium phosphate matrix doped with europium and different concentrations of aluminum ions (0, 5, 10% of mole) was synthesized using the Pechini method. A two-step strategy of synthesis was applied. Phase composition analysis and spectroscopic measurements were performed to characterize the obtained phosphors. The XRD patterns show that in all cases the obtained materials consist of a pure phase of Ca9Y(PO4)7. Emission spectra of the materials obtained after the first step of the synthesis consist of narrow bands attributed to 5D0-7FJ transitions in Eu3+ ions. Independently of the aluminum concentration, europium ions are incorporated into at least two different cationic sites. Considering the asymmetric ratio (R), the sites are characterized by the presence/absence of inversion symmetry. The emission intensity of Eu3+ introduced into the more symmetric site decreases with increasing aluminum concentration. The emission spectra of the materials after the reduction process are characterized by intensive broad bands located at 420 and 488 nm attributed to the d-f transitions in Eu2+; however, the line shape of the spectra depends on the aluminum concentration. Moreover, incorporation of aluminum ions causes the stabilization of the Eu3+ ions under a reductive atmosphere.

Structural Evolution and Effect of the Neighboring Cation on the Photoluminescence of Sr(LiAl3 )1-x (SiMg3 )x N4 :Eu2+ Phosphors.

In this study, a series of Sr(LiAl3 )1-x (SiMg3 )x N4 :Eu2+ (SLA-SSM) phosphors were synthesized by a solid-solution process. The emission peak maxima of SLA-SSM range from 615 nm to 680 nm, which indicates structural differences in these materials. 7 Li solid-state NMR spectroscopy was utilized to distinguish between the Li(1)N4 and Li(2)N4 tetrahedra in SLA-SSM. Differences in the coordination environments of the two Sr sites were found which explain the unexpected luminescent properties. Three discernible morphologies were detected by scanning electron microscopy. Temperature-dependent photoluminescence and decay times were used to understand the diverse environments of europium ions in the two strontium sites Sr1 and Sr2, which also support the NMR analysis. Moreover, X-ray absorption near-edge structure studies reveal that the Eu2+ concentration in SLA-SSM is much higher than that in in SrLiAl3 N4 :Eu2+ and SrSiMg3 N4 :Eu2+ phosphors. Finally, an overall mechanism was proposed to explain the how the change in photoluminescence is controlled by the size of the coordinated cation.

Reply to the 'Comment on "Spectroscopic properties and location of the Ce3+ energy levels in Y3Al2Ga3O12 and Y3Ga5O12 at ambient and high hydrostatic pressure"' by Y. Wang, M. Glowacki, M. Berkowski, A. Kaminska and A. Suchocki, Phys. Chem. Chem. Phys., 2019, 21, DOI.

New results presented by Wang et al. showing the temperature dependence of the Y3Ga5O12:Ce3+ energy bandgap have been taken into account in the calculations of the changes of the energy distance between the lowest 5d state of Ce3+ and the edge of the conduction band. Our calculations show that the diminishing of the band gap energy with temperature has a negligible effect on the difference between the energy of the conduction band and the localized states of the 5d configuration of Ce3+, which means that the new experimental results do not undermine the validity of the conclusions of our previous paper.

Reply to the 'Comment on "Spectroscopic properties and location of the Ce3+ energy levels in Y3Al2Ga3O12 and Y3Ga5O12 at ambient and high hydrostatic pressure"' by Y. Wang, M. Glowacki, M. Berkowski, A. Kaminska and A. Suchocki, Phys. Chem. Chem. Phys., 2019, 21, DOI: 10.1039/C8CP06154H.

New results presented by Wang et al. showing the temperature dependence of the Y3Ga5O12:Ce3+ energy bandgap have been taken into account in the calculations of the changes of the energy distance between the lowest 5d state of Ce3+ and the edge of the conduction band. Our calculations show that the diminishing of the band gap energy with temperature has a negligible effect on the difference between the energy of the conduction band and the localized states of the 5d configuration of Ce3+, which means that the new experimental results do not undermine the validity of the conclusions of our previous paper.

Revisiting Cr3+-Doped Bi2Ga4O9 Spectroscopy: Crystal Field Effect and Optical Thermometric Behavior of Near-Infrared-Emitting Singly-Activated Phosphors.

The increasing interest in the development of ratiometric optical thermal sensors has led to a wide variety of new systems with promising properties. Among them, singly-doped ratiometric thermometers were recently demonstrated to be particularly reliable. With the aim to discuss the development of an ideal optical thermal sensor, a combined experimental and theoretical insight into the spectroscopy of the Bi2Ga4O9:Cr3+ system is reported showing the importance of an insightful analysis in a wide temperature range. Low-temperature photoluminescence analysis (from 10 K) and the temperature dependence of the lifetime investigation, together with the crystal field analysis and the modeling of the thermal quenching process, allow the estimation of key parameters such as the Debye temperature (cutoff frequency), the Huang-Rhys parameter, and the energy barrier between 2Eg and 4T2g. Additionally, by considering the reliable class of singly-doped ratiometric thermometers based on a couple of excited states obeying the Boltzmann law, the important role played by the absolute sensitivity was discussed and the great potential of Cr3+ singly-activated systems was demonstrated. The results may provide new guidelines for the design of reliable optical thermometers with outstanding and robust performances.

Comparison of quenching mechanisms in Gd3Al5-xGaxO12:Ce3+ (x = 3 and 5) garnet phosphors by photocurrent excitation spectroscopy.

In this work we present the results of photocurrent excitation spectroscopy (PCE) of Gd3Al2Ga3O12:Ce3+ (GAGG:Ce3+) and Gd3Ga5O12:Ce3+ (GGG:Ce3+) performed at temperatures ranging from 100 to 500 K supplemented by spectroscopic measurements (steady state and time resolved photoluminescence spectroscopy) performed at temperatures ranging from 10 to 500 K and at high pressure up to 300 kbar. The PCE spectra contain bands related to transitions from the ground state 2F5/2 of the 4f1 electronic configuration to the crystal field split states related to the 5d1 electronic configuration of Ce3+. This implicates the presence of the autoionization process - transfer of electrons from the localized, excited states of Ce3+ to the conduction band (CB), directly linked to luminescence quenching of Ce3+. The mechanism of autoionization of GAGG:Ce3+ and GGG:Ce3+ was determined to be different on the grounds of differences in temperature dependence of photocurrent intensity. The latter system exhibits autoionization, which occurs when all of the 5d excited states are degenerated with the CB, whereas in the former system, the autoionization process is thermally assisted with an activation energy barrier (distance to the edge of the CB) of approximately 1600 cm-1. In GGG:Ce3+ the degeneracy of 5d1 states of Ce3+ was lifted by application of high pressure, shifting the edge of the CB up and exposing Ce3+ luminescence at 20 kbar. Further spectroscopic analyses of the pressure-temperature dependence of the luminescence decay time as well as the temperature dependence of photocurrent intensity of GGG:Ce3+ have independently shown existence of a luminescence quenching state located approximately 600 cm-1 below the CB, attributed to the impurity trapped exciton.

Spectroscopic properties of high-temperature sintered SrS:0.05%Ce3+ under high hydrostatic pressure.

Luminescence properties of SrS:Ce pellets sintered at 1700 °C were investigated under high pressure. Two different Ce3+-related emissions were confirmed to appear in the blue-green and red parts of the spectrum and were shown to shift significantly and linearly to longer wavelengths with increasing pressure. Changes in decay times of both emissions were also thoroughly analyzed. The results confirmed that Ce3+ ion pairing/clustering occurring due to their enhanced mobility at high temperatures is responsible for the appearance of the recently reported red Ce3+ emission in sintered SrS:Ce pellets.

Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn4+ -Activated Narrow Band Fluoride Phosphors.

Mn4+ -doped fluoride phosphors have been widely used in wide-gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na2 (Six Ge1-x )F6 :Mn4+ and Na2 (Gey Ti1-y )F6 :Mn4+ were successfully synthesized to elucidate the behavior of the zero-phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First-principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high-resolution steady-state emission spectra are used to confirm the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.

Temperature effect on the emission spectra of narrow band Mn4+ phosphors for application in LEDs.

Temperature dependence of the luminescence shape and decay time of narrow band Mn4+ fluoride phosphors: Rb2GeF6:Mn4+ and KNaSiF6:Mn4+ was investigated. The temperature changes in the relative intensity between the zero-phonon line and both phonon sidebands were observed in both samples. The sideband spectra consist of three lines related to interaction with three different phonon modes labeled ν3, ν4 and ν6. We present a comprehensive quantum theory which allows calculation of the luminescence intensity and the luminescence lifetime by simultaneously taking into account odd parity crystal fields, odd parity phonon modes and spin-orbit coupling. Since we include all modes, for which the respective interaction strengths and energies of the phonons are known, our approach does not involve any free parameters. We also discuss our results in relation to the temperature dependence of the lifetime of the 2Eg → 4A2g transition, taking into account the quantum efficiency of the system and the migration of the excitation energy. The presented model is applicable to all materials doped with Mn4+ ions and also to any narrow line emitting phosphor, where a zero-phonon line and phonon structure is simultaneously observed in the emission spectrum.

Aluminate Red Phosphor in Light-Emitting Diodes: Theoretical Calculations, Charge Varieties, and High-Pressure Luminescence Analysis.

Searching for a non-rare-earth-based oxide red-emitting phosphor is crucial for phosphor-converted light-emitting diodes (LEDs). In this study, we optimized a blue and UV-light excited Sr4Al14O25:Mn phosphor exhibiting red emission peaked at ∼653 nm, which was successfully synthesized by solid-state reaction. The crystal structure, micromorphology, and luminescent properties of Sr4Al14O25:Mn phosphors were characterized by X-ray Rietveld refinement, high-resolution transmission electron microscopy, and photoluminescence spectra. The band gap and electronic structure of Sr4Al14O25 were analyzed by density functional theory calculations using the hybrid exchange-correlation functional. The crystal field environment effect of Al sites from introducing activator Mn ions was investigated with the aid of Raman 27Al nuclear magnetic resonance spectra and electron spin resonance. The pressure dependent luminescent properties and decay time of this compound were presented. The tricolor display spectrum by combining blue InGaN chips, commercial ß-SiAlON:Eu2+ green phosphor, and Sr4Al14O25:Mn red phosphor were evaluated for commercial applications: using the present Sr4Al14O25:Mn red phosphor converted LED as a backlighting source.

Enhance Color Rendering Index via Full Spectrum Employing the Important Key of Cyan Phosphor.

A new concept called "full-spectrum lighting" has attracted considerable attention in recent years. Traditional devices are usually combined with ultraviolet-light-emitting diode (LED), red, green, and blue phosphors. However, a cyan cavity exists in the 480-520 nm region. Hence, cyan phosphors are needed to compensate for the cavity. (Sr,Ba)5(PO4)3Cl:Eu2+ phosphors feature an extremely unique and tunable photoluminescence spectrum. Nevertheless, the tuning mechanisms of these phosphors remain unclear. In this study, we elucidate the mechanism of the cation size-controlled activator uneven-occupation and reoxidation in (Sr,Ba)5(PO4)3Cl:Eu2+ phosphors. This mechanism could help tune the optical properties of related apatite families and structures with multiple cation sites and strongly uneven occupation of activators and cations. Finally, the package of the LED device is constructed to show that both color rendering index Ra and R9 are higher than 95. Thus, the device could be a potential candidate for full-spectrum lighting.

Structural phase transitions and photoluminescence properties of oxonitridosilicate phosphors under high hydrostatic pressure.

Spectroscopic properties of a series of (Sr0.98-xBaxEu0.02)Si2O2N2 (0 ≤ x ≤ 0.98) compounds has been studied under high hydrostatic pressure applied in a diamond anvil cell up to 200 kbar. At ambient pressure the crystal structures of (Sr0.98-xBaxEu0.02)Si2O2N2 (0 ≤ x ≤ 0.98) are related to the ratio of strontium to barium and three different phases exists: orthorhombic Pbcn(0.78 ≤ x ≤ 0.98), triclinic P1 (0 < x ≤ 0.65) and triclinic P1 (0.65 < x < 0.78). It was found that Eu2+ luminescence reveals abrupt changes under pressure (decay time, energy and shape) which indicate the variation of the local symmetry and crystal field strength in Eu2+ sites. These changes are attributed to the reversible pressure-induced structural phase transitions of triclinic (Sr0.98-xBaxEu0.02)Si2O2N2 into orthorhombic structure. Pressure in which phase transition occurs decreases linearly with increasing of Ba composition in (Sr0.98-xBaxEu0.02)Si2O2N2 series. Additionally, very different pressure shifts of the Eu2+ luminescence in different phases of (Sr0.98-xBaxEu0.02)Si2O2N2:Eu from -40 cm-1/kbar to 0 cm-1/kbar have been observed. This effect is explained by different interaction of the Eu2+ 5d electron with the second coordination sphere around the impurity cations.

Improvement of the Water Resistance of a Narrow-Band Red-Emitting SrLiAl3 N4 :Eu(2+) Phosphor Synthesized under High Isostatic Pressure through Coating with an Organosilica Layer.

A SrLiAl3 N4 :Eu(2+) (SLA) red phosphor prepared through a high-pressure solid-state reaction was coated with an organosilica layer with a thickness of 400-600 nm to improve its water resistance. The observed 4f(6) 5d→4f(7) transition bands are thought to result from the existence of Eu(2+) at two different Sr(2+) sites. Luminescence spectra at 10 K revealed two zero-phonon lines at 15377 (for Eu(Sr1)) and 15780 cm(-1) (for Eu(Sr2)). The phosphor exhibited stable red emission under high pressure up to 312 kbar. The configurational coordinate diagram gave a theoretical explanation for the Eu(2+/3+) result. The coated samples showed excellent moisture resistance while retaining an external quantum efficiency (EQE) of 70 % of their initial EQE after aging for 5 days under harsh conditions. White-light-emitting diodes of the SLA red phosphor and a commercial Y3 Al5 O12 :Ce(3+) yellow phosphor on a blue InGaN chip showed high color rendition (CRI=89, R9=69) and a low correlated color temperature of 2406 K.

Narrow Red Emission Band Fluoride Phosphor KNaSiF6:Mn(4+) for Warm White Light-Emitting Diodes.

Red phosphors AMF6:Mn(4+) (A = Na, K, Cs, Ba, Rb; M = Si, Ti, Ge) have been widely studied due to the narrow red emission bands around 630 nm. The different emission of the zero-phonon line (ZPL) may affect the color rendering index of white light-emitting diodes (WLED). The primary reason behind the emergence and intensity of ZPL, taking KNaSiF6:Mn(4+) as an example, was investigated here. The effects of pressure on crystal structure and luminescence were determined experimentally and theoretically. The increase of band gap, red shift of emission spectrum and blue shift of excitation spectrum were observed with higher applied pressure. The angles of ∠FMnF and ∠FMF(M = Si, Ti, Ge) were found clearly distorted from 180° in MF6(2-) octahedron with strong ZPL intensity. The larger distorted SiF6(2-) octahedron, the stronger ZPL intensity. This research provides a new perspective to address the ZPL intensity problem of the hexafluorosilicate phosphors caused by crystal distortion and pressure-dependence of the luminescence. The efficacy of the device featuring from Y3Al5O12:Ce(3+) (YAG) and KNaSiF6:Mn(4+) phosphor was 118 lm/W with the color temperature of 3455 K. These results reveal that KNaSiF6:Mn(4+) presents good luminescent properties and could be a potential candidate material for application in back-lighting systems.