Structures, photoluminescence, and principles of self-activated phosphors.

Self-activated phosphors without any luminescent dopants, usually display excellent optical properties, such as high oscillator strength, large Stokes shift, and strong luminescence efficiency, and thus have been widely investigated by researchers for several decades. However, their recent advancements in scintillators, white-light illumination, displays and optical sensors compel us to urgently understand the basic principles and significant technological relevance of this worthy family of materials. Herein, we review the structures, photoluminescence principles, and applications of state-of-the-art self-activated phosphors, such as borate, gallate, niobate, phosphate, titanate, vanadate, tungstate, nitrides, oxyfluoride, perovskite, metal halides, and carbon dots. The photoluminescence principles of self-activated phosphors are mainly summarized as transitions between energy levels of rare-earth and transition metal ions, charge transfer transitions of some oxide compounds, and luminescence in all-inorganic semiconductors. The different self-activated phosphors exhibit various structures and site-dependent spectra. Additionally, we discuss the application prospect and main challenges of self-activated phosphors.

Ratiometric optical thermometer based on the use of manganese(II)-doped Cs3Cu2I5 thermochromic and fluorescent halides.

The inconsistent thermal quenching performance of manganese(II)-doped Cs3Cu2I5 microparticles is exploited in a highly sensitive noninvasive optical thermometer. The ratio of the emissions of Cu(II) and Mn(II) ions in the microparticles is highly temperature dependent in the range from 298 to 498 K. The best absolute and relative sensitivities are 0.547 K-1 and 0.525% K-1, respectively. The emission spectrum, under 300-nm photoexcitation, has emission peaks at 448 and 556 nm. This is the result of energy transfer between the Cu(II) and Mn(II) ions whose efficiency can reach up to 57% when the Mn(II) ion concentration is 2 mol%. The emission color of the microparticles changes from cyan to green when increasing the temperature from 298 to 498 K. Graphical abstract Synthesis of novel Mn(II)-doped Cs3Cu2I5 thermochromic halides with admirable luminescent behaviors for high sensitive ratiometric thermometry and safety sign in high temperature environment.

Optical Thermometry Based on Vibration Sidebands in Y2MgTiO6:Mn4+ Double Perovskite.

Mn4+-doped Y2MgTiO6 phosphors are synthesized by the traditional solid-state method. Powder X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectrometer are employed to characterize the samples. The Mn4+-doped Y2MgTiO6 phosphors show the far-red emission at ∼715 nm, which is assigned to the 2Eg → 4A2 spin-forbidden transition of Mn4+. The temperature-dependent luminescent dynamics of Mn4+ is described by a complete model associated with electron-lattice interaction and spin-orbit coupling. The noncontact optical thermometry of Y2MgTiO6:Mn4+ is discussed based on the fluorescence intensity ratio of thermally coupled anti-Stokes and Stokes sidebands of the efficient ∼715 nm far-red emission in the temperature range of 10-513 K. The maximum sensor sensitivity of Y2MgTiO6:Mn4+ is determined to be as high as 0.001 42 K-1 at 153 K, which demonstrates potential applications for the optical thermometry at low-temperature environments.

Excitation power dependent optical temperature behaviors in Mn4+ doped oxyfluoride Na2WO2F4.

A Mn4+ doped Na2WO2F4 phosphor was synthesized through a two-step wet chemical method. The relationship between crystal structure and luminescence properties is discussed and unusual strong intense zero phonon lines (ZPLs) have been found in a distorted octahedral environment. The power dependent luminescence spectra exhibit the existence of down conversion luminescence intensity saturation under a high pumping power limit. The fluorescence intensity ratios of anti-Stokes bands to the ZPL and Stokes bands reveal an obvious temperature dependent relationship based on thermal de-population from the low states to the upper states of an intrinsic Mn4+ 2Eg → 4A2g transition. The temperature dependent emission intensity of Mn4+ is investigated by changing the excitation power, and an optical temperature sensitivity as high as 0.00658 K-1 is achieved at 193 K with the intensity ratio of anti-Stokes bands to the ZPL under 488 nm excitation by a Xenon lamp. This work presents a new method to realize optical thermometry at low temperature by controlling the intensity ratio of the anti-Stokes bands to the ZPL.

Excitation powder dependent optical temperature behavior of Er3+ doped transparent Sr0.69La0.31F2.31 glass ceramics.

The knowledge of the pump power for which the population of thermally coupled energy levels (TCL) changes with power increase is of valuable importance for optical temperature sensors. In this paper, novel Er3+ doped transparent Sr0.69La0.31F2.31 glass ceramics was fabricated successfully, and its structure is studied by XRD, TEM and HRTEM analyses. The 2H11/2/4S3/2, 4F9/2(1)/4F9/2(2), and 4I9/2(1)/4I9/2(2) levels of Er3+ are proved as TCL by analyzing the temperature dependent fluorescence intensity ratios. The spectrum split, thermal quenching ratio, population stability, and temperature sensitivity from three TCL are observed to be dependent on the pump power. A new fitting method has been developed to establish the relation between fluorescence intensity ratios and temperature. It is found that the combined use of 2H11/2/4S3/2 and 4F9/2(1)/4F9/2(2) as thermally coupled energy levels will get a more precise temperature reading from 62.7 K to 800 K with the help of low excitation power at 66.8 mW/mm2.

Detecting the origin of luminescence in Er3+-doped hexagonal Na1.5Gd1.5F6 phosphors.

Understanding site-selective fluorescence is one of valuable importance for spectrum modulation. In this Letter, we observed the existence of two non-equivalent Gd-activated crystallographic sites in an Er3+-doped hexagonal Na1.5Gd1.5F6 phosphor. It is proved that two green emissions from the S3/24 level separately originate from the Gd1 (540 nm) and Na2/Gd2 (550-555 nm) crystallographic sites, and the 657 nm red emission from the F9/24 level only originates from Na2/Gd2 site through using the time-resolved luminescence spectra. The 142.2% absolute enhancement of the red emission is realized through the synergistic effect of ultraviolet downconversion and infrared upconversion induced by the 370 nm and 1.54 µm dual-mode excitation.

Photoluminescence properties of Eu(3+)-doped glaserite-type orthovanadates CsK(2)Gd[VO(4)](2).

Undoped and Eu(3+)-doped glaserite-type orthovanadates CsK2Gd1-xEux[VO4]2 with various Eu(3+) concentrations of x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1.0 were synthesized via the solid-state reaction. The formation of a single phase compound was verified through the X-ray diffraction studies. The photoluminescence (PL) and PL excitation (PLE) spectra, PL decay curves, and absolute quantum efficiency (QE) were investigated. Unlike the conventional Eu(3+)-doped vanadates, these Eu(3+)-doped samples showed not only several sharp emission lines due to Eu(3+) but also a broad emission band with a maximum at 530 nm due to the [VO4](3-) host. The intensities of the host and Eu(3+) emissions increased when the Eu(3+) concentration was increased from x = 0 to x = 0.6 and decreased above x = 0.6. Similar concentration dependence was observed for QE. The host emission, even if in the Eu(3+)-condensed host of CsK2Eu(VO4), was never quenched indicating inefficient energy transfer from the host [VO4](3-) to Eu(3+). This inefficient energy transfer is understood by suppression of the energy transfer by the V-O-Eu bond angle deviated from 180° and the separation of Eu(3+) ions at the Gd(3+) site from [VO4](3-). Like the 530 nm charge transfer [VO4](3-) emission, two broad and intense PLE bands with maxima at 330 and 312 nm were observed for the Eu(3+) emission. A maximum QE of 38.5% was obtained from CsK2Gd1-xEux[VO4]2 (x = 0.6). A white-colored emission was obtained by the combination of the broad 530 nm emission band and the intense sharp lines due to Eu(3+) at 590-620 nm.

Synthesize magnetic ZnFe2O4@C/Cd0.9Zn0.1S catalysts with S-scheme heterojunction to achieve extraordinary hydrogen production efficiency.

Suppressing the electron-hole recombination rate of catalyst legitimately is one of the effective strategies to improve photocatalytic hydrogen evolution. Herein, carbon-coated metal oxide, ZnFe2O4@C (ZFO@C), nanoparticles were synthesized and employed to couple with quadrupedal Cd0.9Zn0.1S (CZS) via an ordinary ultrasonic self-assembly method combined with calcination to form a novel ZFO@C/CZS catalyst with step-scheme (S-scheme) heterojunction. The photocatalytic hydrogen evolution reaction (HER) was conducted to verify the enhanced photoactivity of ZFO@C/CZS. The optimal ZFO@C/CZS exhibits an extraordinary photocatalytic HER rate of 111.3 ± 0.9 mmol g-1 h-1 under visible-light irradiation, corresponding to an apparent quantum efficiency as high as (76.2 ± 0.9)% at 450 nm. Additionally, the as-synthesized ZFO@C/CZS composite exhibits high stability and recyclability. The excellent photocatalytic hydrogen evolution performance should arise from the formed S-scheme heterojunction and the unique ZFO@C core-shell structure, which inhibit electron hole recombination as well as provide more reactive sites. The pathway of S-scheme charge transfer was validated through density functional theory calculations and electrochemical measurements. This work provides a rational strategy for the synthesis of unique magnetic S-scheme heterojunction photocatalysts for water splitting under visible light irradiation.

Enhanced piezo-photocatalytic performance in ZnIn2S4/BiFeO3 heterojunction stimulated by solar and mechanical energy for efficient hydrogen evolution.

An emerging approach that employs both light and vibration energy on binary photo-/piezoelectric semiconductor materials for efficient hydrogen (H2) evolution has garnered considerable attention. ZnIn2S4 (ZIS) is recognized as a promising visible-light-activated photocatalyst. However, its effectiveness is constraint by the slow separation dynamics of photoexcited carriers. Density functional theory (DFT) predictions have shown that the integration of piezoelectric BiFeO3 (BFO) is conducive to the reduction of the H2 adsorption free energy (ΔGH*) for the photocatalytic H2 evolution reaction, thereby enhancing the reaction kinetics. Informed by theoretical predictions, piezoelectric BFO polyhedron particles were successfully synthesized and incorporated with ZIS nanoflowers to create a ZIS/BFO heterojunction using an ultrasonic-assisted calcination method. When subjected to simultaneous ultrasonic treatment and visible-light irradiation, the optimal ZIS/BFO piezoelectric enhanced (piezo-enhanced) heterojunction exhibited a piezoelectric photocatalytic (piezo-photocatalytic) H2 evolution rate approximately 6.6 times higher than that of pristine ZIS and about 3.0 times greater than the rate achieved under light-only conditions. Moreover, based on theoretical predictions and experimental results, a plausible mechanism and charge transfer route for the enhancement of piezo-photocatalytic performance were studied by the subsequent piezoelectric force microscopy (PFM) measurements and DFT calculations. The findings of this study strongly confirm that both the internal electric field of the step-scheme (S-Scheme) heterojunction and the alternating piezoelectric field generated by the vibration of BFO can enhance the transportation and separation of electron-hole pairs. This study presents a concept for the multipath utilization of light and vibrational energy to harness renewable energy from the environment.

S-scheme heterojunction of hollow corncob-like ZnIn2S4/LaFeO3 for water splitting and tetracycline degradation.

Reasonable design of heterojunction photocatalysts with high-quality interfacial coupling is an effective way to improve the photocatalytic activity of semiconductors. Herein, we successfully decorated Zinc indium sulfide (ZnIn2S4, ZIS) on perovskite Lanthanum ferrite (LaFeO3, LFO) with more active sites by a pre-hydrothermal combined post-calcination method, and constructed S-scheme heterojunction photocatalyst with a unique hollow corncob-like morphology for efficient photocatalytic hydrogen production and tetracycline (TC) degradation. When the mass ratio of LFO is 35% and 15%, the ZIS/LFO photocatalyst exhibits the best hydrogen evolution rate and TC photodegradation performance, respectively. Notably, the optimum hydrogen production rate is 6 times that of pure ZIS with excellent cycling stability. The enhanced photoactivity can be explained by the hollow corncob-like morphology and the formed S-scheme heterojunction with close interface contact between ZIS and LFO, which significantly improves the spatial separation and migration efficiency of photoexcited carriers, while maintaining a high redox potential. Finally, it provides an effective support for the photocatalytic mechanism through calculation results of density functional theory. This work not only provides a novel construction strategy of photocatalysts for efficient photocatalytic hydrogen evolution and organic pollutant degradation, but also opens up a new insight for perovskite-modified S-scheme heterojunction.

In-situ preparation of mossy tile-like ZnIn2S4/Cu2MoS4 S-scheme heterojunction for efficient photocatalytic H2 evolution under visible light.

The reasonable design and fabrication of heterojunction could regulate the photocatalytic performance to some extent, yet it is still a great challenge to construct the S-scheme heterostructure with the stable as well as tight interface on the surface of semiconductor photocatalysts. Herein, the ZnIn2S4/Cu2MoS4 (ZIS/CMS) S-scheme heterostructure was fabricated by in-situ assembling ZIS nanosheets on the CMS plates, obtaining a mossy tile-like morphology. Owing to the compact interface resulting from in-situ growth, this unique architecture efficiently facilitated the separation and transfer of light-induced charges, guaranteed the larger interface area, and enriched the active sites for photocatalytic redox reactions. After adjusting the mass ratio of CMS in ZIS/CMS, S-scheme heterostructure exhibited the remarkable performance with an optimal H2 producing rate up to 1298 µmol·h-1 g-1, about 13.8 times than that of pristine ZIS. The mechanism and driving force of charge transfer and separation in S-scheme heterostructure photocatalysts were explained and discussed. This investigation will provide new insight into design and construction of S-scheme heterojunction photocatalysts for H2 evolution.

A novel SnIn4S8/ZnFe2O4 S-scheme heterojunction with excellent magnetic properties and photocatalytic degradation activity for tetracycline.

The development of efficient and economical photocatalysts is considered a promising strategy for pollution remediation. Magnetically separable SnIn4S8/ZnFe2O4 composites (SIS/ZFO) were prepared by combining SIS with ZFO. The composite with a 30% ZFO mass ratio (SIS/ZFO-30) was the most effective and achieved 60% removal of tetracycline (TC) in 120 min. It has a rate constant of 7.94 × 10-3 min-1, which is 6.3 and 27.2 times higher than those of pure SIS and pure ZFO, respectively. The improved photocatalytic performance can be attributed to the formation of S-scheme heterojunctions between SIS and ZFO, which results in the strong absorption of visible light, the enhanced separation of electron-hole pairs, and the higher redox ability of photoinduced charges. Additionally, SIS/ZFO composites have excellent magnetic properties and high stability, and the recovered samples still retained good photocatalytic degradation performances after four cycles of experiments. Thus, the coupling of SIS with ZFO provides a valuable strategy for enhancing photocatalytic potential and offers a promising pathway for water remediation.

Highly efficient flower-like ZnIn2S4/CoFe2O4 photocatalyst with p-n type heterojunction for enhanced hydrogen evolution under visible light irradiation.

The construction of a p-n heterojunction structure is considered to be an effective method to improve the separation of electron-hole pairs in photocatalysts. A series of ZnIn2S4/CoFe2O4 (ZIS/CFO) photocatalysts with p-n heterojunctions were prepared via a method involving ultrasonication and calcination. The synthesized photocatalysts were tested and analyzed via various testing techniques, and their hydrogen evolution rates were evaluated. Compared with pure ZIS, ZIS/CFO with different mass ratios of CFO to ZIS showed improved photocatalytic hydrogen production performance, and the optimal photoactivity showed a nearly 12-fold increase, which can be attributed to the formation of p-n junctions and the formed internal electric field, accelerating the separation of electron-hole pairs and effectively improving the photocatalytic hydrogen evolution rate. The excellent stability of the ZIS/CFO composite was proven by three cycle experiments. In addition, the ZIS/CFO composite also possessed excellent magnetic properties to realize facial magnetic recoverability. This work paves the way for the design and preparation of magnetically recoverable p-n heterojunction photocatalysts.

Achieving improved full-spectrum responsive 0D/3D CuWO4/BiOBr:Yb3+,Er3+ photocatalyst with synergetic effects of up-conversion, photothermal effect and direct Z-scheme heterojunction.

The key to obtain effective photocatalysts is to increase the efficiency of light energy conversion, and thus the design and implementation of full-spectrum photocatalysts is a potential approach to solve this problem especially by extending the absorption range to near-infrared (NIR) light. Herein, the improved full-spectrum responsive CuWO4/BiOBr:Yb3+,Er3+ (CW/BYE) direct Z-scheme heterojunction was prepared. The CW/BYE with CW mass ratio of 5% had the best degradation performance, and the removal rate of tetracycline reached 93.9% in 60 min and 69.4% in 12 h under visible (Vis) and NIR light, respectively, which were 5.2 and 3.3 times of BYE. According to the outcome of experimental, the reasonable mechanism of improved photoactivity was put forward on the basis of (i) the up-conversion (UC) effect of Er3+ ion to convert NIR photon to ultraviolet or visible light, which can be used by CW and BYE, (ii) the photothermal effect of CW to absorb the NIR light, increasing the local temperature of photocatalyst particle to accelerate the photoreaction, and (iii) the formed direct Z-scheme heterojunction between BYE and CW to boost the separation of photogenerated electron-hole pairs. Additionally, the excellent photostability of the photocatalyst was verified by cycle degradation experiments. This work opens up a promising technique for designing and synthesizing full-spectrum photocatalysts by utilizing synergetic effects of UC, photothermal effect and direct Z-scheme heterojunction.

Bilayer phosphine oxide modification toward efficient and large-area pure-blue perovskite quantum dot light-emitting diodes.

Blue emissive halide perovskite light-emitting diodes (LEDs) are gaining increasing attention. Reducing defects in halide perovskites to improve the performance of the resulting LEDs is a main research direction, but there are limited passivation methods for achieving efficient and spectrally-stable pure-blue LEDs based on mixed-halide perovskites. In this work, double modification layers containing phosphine oxides, i.e., diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide (TSPO1) and 2,7-bis(diphenylphosphoryl)-9,9'-spirobifluorene (SPPO13), are developed to passivate mixed-halide perovskite quantum dot (QD) films. The comprehensive spectroscopic and structural characterization results indicate the presence of strong interactions between TSPO1/SPPO13 and the QDs. Besides, the combination of the bilayer exhibits a synergistic hole-blocking effect, improving the charge balance of the LEDs. LEDs based on the QD/TSPO1/SPPO13 films deliver stable electroluminesence at 469 nm and present a maximum external quantum efficiency (EQE) and luminance of 4.87% and 560 cd m-2, respectively. Benefiting from the uniform QD/TSPO1/SPPO13 film over a large area, LEDs with an area of 64 mm2 show a maximum EQE of 3.91%, which represents the first efficient large-area mixed-halide perovskite LED with stable pure-blue emission. This work provides a method to improve the perovskite QDs-based film quality and optoelectronic properties, and is a step toward the fabrication of highly-efficient large-area blue perovskite LEDs.

Room-Temperature Synthesis of Highly-Efficient Eu3+-Activated KGd2F7 Red-Emitting Nanoparticles for White Light-Emitting Diode.

Luminescent materials with high thermal stability and quantum efficiency are extensively desired for indoor illumination. In this research, a series of Eu3+-activated KGd2F7 red-emitting nanoparticles were prepared at room temperature and their phase structure, morphology, luminescence properties, as well as thermal stability, have been studied in detail. Excited by 393 nm, the resultant nanoparticles emitted bright red emissions and its optimal status was realized when the Eu3+ content was 30 mol%, in which the concentration quenching mechanism was triggered by electric dipole-dipole interaction. Through theoretical analysis via the Judd-Ofelt theory, one knows that Eu3+ situates at the high symmetry sites in as-prepared nanoparticles. Moreover, the internal and extra quantum efficiencies of designed nanoparticles were dependent on Eu3+ content. Furthermore, the studied nanoparticles also had splendid thermal stability and the corresponding activation energy was 0.18 eV. Additionally, via employing the designed nanoparticles as red-emitting constituents, a warm white light-emitting diode (white-LED), which exhibits low correlated color temperature (4456 K), proper luminous efficiency (17.2 lm/W) and high color rendering index (88.3), was developed. Our findings illustrate that Eu3+-activated KGd2F7 nanoparticles with bright red emissions are able to be used to promote the performance of white-LED.

Decoupling the Positive and Negative Aging Processes of Perovskite Light-Emitting Diodes Using a Thin Interlayer of Ionic Liquid.

A positive aging phenomenon, that is, enhancement of the electroluminescence performance at the beginning of electrical aging, is commonly observed for the state-of-the-art perovskite light-emitting diodes (PeLEDs). The origins of positive aging could fundamentally interfere with those of the operational deterioration processes of PeLEDs (namely negative aging), bringing difficulty in analyzing the degradation mechanisms. This work decouples the positive and negative aging processes of PeLEDs by inserting a thin ionic liquid interlayer between the hole-injection layer and the perovskite layer. This interlayer inhibits ions migration by passivating the halogen vacancies of perovskite films and suppresses interfacial exciton quenching, enabling us to decouple the positive and negative aging processes of PeLEDs while increasing the device efficiency. Inserting an ionic liquid interlayer is also demonstrated to be effective for iodide-based PeLEDs and applicable with the use of other ionic liquids. Our work provides an ideal system for fundamental studies on the degradation mechanisms of PeLEDs.

Anti-Stokes Ultraviolet Luminescence and Exciton Detrapping in the Two-Dimensional Perovskite (C6H5C2H4NH3)2PbCl4.

Recently, it has been found that low-dimensional organometallic halide perovskites can be adopted as nonlinear monolayer emitters because of their efficient spontaneous anti-Stokes visual luminescence under visual or near-infrared laser excitation. Herein, we demonstrate a luminescence up-conversion process from the visible self-trapped exciton (STE) to an ultraviolet (UV) free exciton (FE) in the two-dimensional perovskite (C6H5C2H4NH3)2PbCl4 quantum wells excited by nanosecond pulse laser excitation. An ultraviolet 347 nm near-band-edge FE emission is obtained under the excitation of 579 nm dye laser at 10 K by a two-step, two-photon absorption process from the real intermediate exciton state. In addition, the decay rise time of higher-laying states of STE indicates the excitonic detrapping procedure could occur by the annihilation of phonons. Our results suggest that the low-dimensional halide perovskites with deformable structure are able to be applied in visible light-pumped UV-emitting devices.

Luminescence, energy transfer and optical thermometry of a novel narrow red emitting phosphor: Cs2WO2F4:Mn4.

A novel red emitting Cs2WO2F4:Mn4+ phosphor was successfully synthesized by a two-step wet chemical method. The crystal structure, morphology, and elemental composition were confirmed by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The luminescence properties were investigated from emission, excitation and luminescence decay curves in the temperature region of 10-500 K. The application of non-contact optical thermometry of Cs2WO2F4:Mn4+ based on the fluorescence intensity ratio (FIR) of the two coupled anti-Stokes and Stokes sidebands is discussed. The as-prepared Cs2WO2F4:Mn4+ phosphor shows a bright narrow red emission at 632 nm under excitation by a blue lamp at 470 nm and it also presents a broad and yellow-white intrinsic tungstate emission (∼520 nm) under UV excitation. The mechanism of energy transfer from [WO2F4]2- (the sensitizer) to Mn4+ (the activator) is discussed.

Influence of Doping and Excitation Powers on Optical Thermometry in Yb3+-Er3+ doped CaWO4.

Optical thermometry has been widely studied to achieve an inaccessible temperature measurement in submicron scale and it has been reported that the temperature sensitivity depends mainly on host types. In this work, we propose a new method to improve the optical temperature sensitivity of Yb3+-Er3+ co-doped CaWO4 phosphors by doping with Li+, Sr2+, and Mg2+ ions and by controlling excitation powers of 980 nm laser. It is found that the thermometric parameters such as upconversion emission intensity, intensity ratio of green-to-red emission, fluorescence color, emission intensity ratios of thermally coupled levels (2H11/2/4S3/2), and relative and absolute temperature sensitivity can be effectively controlled by doping with Li+, Sr2+, and Mg2+ ions in the Yb3+-Er3+ co-doped CaWO4 system. Moreover, the relative sensitivity SR and the absolute sensitivity SA are proved to be dependent on the pump power of 980 nm laser. The sensitivities of SR and SA in Yb3+-Er3+ co-doped CaWO4 increase about 31.5% and 12%, respectively, by doping with 1 mol% Sr2+.