Preparation,Structure, and Up‐Conversion Luminescence of Yb3+/Er3+ Codoped SrIn2O4 Phosphors

SrIn₂O₄, which shows lower phonon energy than CaIn₂O₄, is not only a good photocatalyst but also can be an excellent up‐conversion (UC) host to exhibits UC luminescence. In this work, Yb³⁺ and/or Er³⁺ doped SrIn₂O₄ phosphors were synthesized, and their UC luminescence properties were studied and compared with those in the CaIn₂O₄ host. The structure of SrIn₂O₄: 0.01Er³⁺ and SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ samples were refined by the Rietveld method and found to that SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ showed increasing unit cell parameters and cell volume, indicating In³⁺ sites were substituted successfully by Yb³⁺ and/or Er³⁺ ions. From the UC luminescence spectra and diffuse reflection spectra, Er³⁺‐doped SrIn₂O₄ showed very weak luminescence due to ground state absorption of Er³⁺; Yb³⁺/Er³⁺ codoped SrIn₂O₄ presented strong green (550 nm) and red (663 nm) UC emissions which were assigned to energy transfer from Yb³⁺ transition ²F_7/2→²F_5/2 to the Er³⁺ transition ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2. Comparing with CaIn₂O₄, Yb³⁺/Er³⁺ codoped SrIn₂O₄ showed obvious advantages with higher UC luminescent intensity. The pumping powers study showed that UC emissions in Yb³⁺/Er³⁺ codoped SrIn₂O₄ were attributed to energy transfer of Yb³⁺→Er³⁺ with a two‐photon process. The possible UC luminescent mechanism of Yb³⁺/Er³⁺‐doped SrIn₂O₄ was discussed.     

Near‐Infrared Quantum Cutting via Downconversion Energy Transfers in Ho3+/Yb3+ Codoped Tellurite Glass Ceramics

The different concentration of Ho³⁺/Yb³⁺ codoped tellurite glasses were prepared by high‐temperature melting‐quenching method. On excitation of Ho³⁺ ions with blue photon at 449 nm as well as ultraviolet (UV) photon at 360 nm, the near infrared emission at 977 nm from Yb³⁺ and 981, 1020 nm from Ho³⁺, which could be absorbed by silicon and enhance the efficiency of the silicon‐based solar cell, were observed. The energy‐transfer process of Ho³⁺ and Yb³⁺ ions and involved mechanism have been investigated and discussed. The first‐order energy transfer (ET) through cross relaxation and a back ET from Yb³⁺ to Ho³⁺ occurred in the near‐infrared quantum cutting (NIR QC) system are proposed and verified. The NIR quantum efficiency achieved 166% when Yb³⁺ doping concentration is 20 mol%.     

Color‐Tunable Up‐Conversion Emission and Infrared Photoluminescence and Dielectric Relaxation of Er3+/Yb3+ Co‐Doped Bi2Ti2O7 Pyrochlore Thin Films

The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi₂Ti₂O₇ can be stabilized by Er³⁺/Yb³⁺ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.     

Optical Thermometry Based on Up‐Conversion Luminescence Behavior of Er3+ ‐Doped Transparent Sr2YbF7 Glass‐Ceramics

Transparent novel glass‐ceramics containing Sr₂YbF₇:Er³⁺ nanocrystals were successfully fabricated by melt‐quenching technique. Their structural and up‐conversion luminescent properties were systemically investigated by XRD, HRTEM, and a series of spectroscopy methods. The temperature‐dependent up‐conversion spectra prove that ²H_11/2 and ⁴S_3/2 levels of Er³⁺ are thermally coupled energy levels (TCEL). Consequently, the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 emissions of Er³⁺ in Sr₂YbF₇:Er³⁺ glass‐ceramics can be used as optical thermometry based on fluorescence intensity ratio (FIR) technique. Combined with low phonon energy and high thermal stability, Er³⁺ ions in Sr₂YbF₇ glass‐ceramics present broad operating temperature range (300–500 K), large energy gap of TCEL (786 cm^?1) and high theoretical maximum value of relative sensitivity (62.14 × 10^?4 K^?1 at 560 K), which suggests that Sr₂YbF₇:Er³⁺ glass‐ceramics may be excellent candidates for optical temperature sensors.     

Enhanced Sunlight Excited 1‐μm Emission in Cr3+–Yb3+ Codoped Transparent Glass‐Ceramics Containing Y3Al5O12 Nanocrystals

Cr³⁺–Yb³⁺ codoped transparent glass‐ceramics containing Y₃Al₅O₁₂ nanocrystals were prepared by heat treatment of as‐prepared glass sample and characterized by X‐ray diffraction and transmission electron microscopy. The efficient energy transfer from Cr³⁺ to Yb³⁺ ions through multi‐phonon‐assisted process was confirmed by the luminescence spectrum and fluorescent lifetime measurements. When excited by the lights from a solar simulator in the wavelength region of 400–800 nm, greatly enhanced near‐infrared emission around 1 μm was achieved from Cr³⁺–Yb³⁺ codoped glass ceramic compared with that from as‐prepared glass and Ce³⁺–Yb³⁺ codoped glass ceramic. These results demonstrate that the Cr³⁺–Yb³⁺ codoped glass ceramic is a promising material for enhancement of the efficiency of solar energy utilization.     

Enhanced Up‐Conversion Luminescence in Er3+‐Doped 25GeS2·35Ga2S3·40CsCl Chalcogenide Glass–Ceramics

Enhanced luminescence in rare‐earth‐doped chalcogenide glass–ceramics is of great interest for the potential integrated optoelectronic devices. However, fundamental mechanism on the enhancement of luminescence upon crystallization remains largely unknown. We report the fabrication and characterization of wide transmission chalcogenide glass and glass–ceramics based on the 25GeS₂·35Ga₂S₃·40CsCl:0.3Er glass composition, and discuss the mechanism of enhanced luminescence. By monitoring the ⁴I_9/2–⁴I_15/2 of Er³⁺ transition, up‐conversion luminescence of 12 times higher was observed in glass–ceramics compared with that in base glass. Electron paramagnetic resonance (EPR) and Raman scattering spectroscopies were employed to obtain the information of selective environment of Er³⁺ ions and microstructural evolution with the crystallization progress. Both of them evidenced that the enhanced up‐conversion luminescence was mainly related to the local environmental evolution from a mixed chlorine‐sulfur coordination to a low phonon energy chlorine coordination in the residual glassy matrix of glass–ceramics.     

Green Up‐Conversion Photoluminescence and Dielectric Relaxation of Ho3+/Yb3+‐Codoped Bi2Ti2O7 Pyrochlore Thin Films

Ho³⁺/Yb³⁺‐codoped Bi₂Ti₂O₇ pyrochlore thin films were prepared by a chemical solution deposition method, and their visible up‐conversion (UC) photoluminescence and dielectric relaxation were studied. Ho and Yb can be doped into Bi₂Ti₂O₇ lattice and single pyrochlore phase is maintained. Intense visible UC photoluminescence can be observed under the excitation of a 980‐nm diode laser. Two UC emission bands centered at 551 nm and 665 nm in the spectra can be assigned to ⁵F₄, ⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transitions of Ho³⁺ ions, respectively. The dependence of their UC emission intensity on pumping power indicates that both the green and red emissions of the thin films are two‐photon process. In addition, a Stokes near‐infrared emission centered at 1200 nm can be detected, which is due to ⁵I₆→⁵I₈ transition of Ho³⁺ ions. The thin films prepared on indium tin oxide–coated glass substrates exhibit a relatively high dielectric constant and a low dielectric loss as well as a good bias voltage stability. The dielectric relaxation of the thin films was also analyzed based on the temperature‐ and frequency‐dependent dielectric properties. This study suggests that Ho³⁺/Yb³⁺‐codoped Bi₂Ti₂O₇ thin films are promising materials for developing multifunctional optoelectronic thin film devices.     

Visible green upconversion luminescence of Er3+/Yb3+/Li+ co-doped CaWO4 particles

The upconversion (UC) luminescence of Li⁺/Er³⁺/Yb³⁺ co-doped CaWO₄ phosphors is investigated in detail. Single crystallized CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor can be obtained, co-doped up to 25.0/5.0/20.0 mol% (Li⁺/Er³⁺/Yb³⁺) by solid-state reaction. Under 980 nm excitation, CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor exhibited strong green UC emissions visible to the naked eye at 530 and 550 nm induced by the intra-4f transitions of Er³⁺ (²H_11/2,⁴S_3/2→⁴I_15/2). The optimum doping concentrations of Yb³⁺/Li⁺ for the highest UC luminescence were verified to be 10/15 mol%, and a possible UC mechanism that depends on the pumping power is discussed in detail.     

Fabrication and Upconversion Luminescent Properties of Er3+‐Doped and Er3+/Yb3+ Codoped La2O2CN2 Nanofibers

La₂O₂CN₂:Er³⁺and La₂O₂CN₂:Er³⁺/Yb³⁺ upconversion (UC) luminescence nanofibers were successfully fabricated via cyanamidation of the respective relevant La₂O₃:Er³⁺ and La₂O₃:Er³⁺/Yb³⁺ nanofibers which were obtained by calcining the electrospun composite nanofibers. The morphologies, structures, and properties of the nanofibers are investigated. The mean diameters of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are 179.46 ± 12.58 nm and 198.85 ± 17.07 nm, respectively. It is found that intense green and weak red emissions around 524, 542, and 658 nm corresponding to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_l5/2 energy levels transitions of Er³⁺ ions are observed for La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers under the excitation of a 980‐nm diode laser. Moreover, the emitting colors of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are all located in the green region. The upconversion luminescent mechanism and formation mechanism of the nanofibers are also proposed.     

A Novel Multifunctional Upconversion Phosphor: Yb3+/Er3+ Codoped La2S3

Yb³⁺/Er³⁺ codoped La₂S₃ upconversion (UC) phosphors have been synthesized using high‐temperature solid‐state method. Under 971‐nm excitation, the maximum luminescence power can reach 0.64 mW at the excitation power density of 16 W/cm² and an absolute power yield of 0.36% was determined by an absolute method at the excitation power density of 3 W/cm², and the quantum yield of La₂S₃:Yb³⁺, Er³⁺ (green ~0.18%, red ~0.03%, integration ~0.21) was comparable to that of NaYF₄:Yb³⁺, Er³⁺ nanocrystals (integration ~0.005–0.30). Frequency upconverted emissions from two thermally coupled excited states of Er³⁺ were recorded in the temperature range 100–900 K. The maximum sensitivity of temperature sensing is 0.0075 K^?1. As the excitation power density increases, the temperature of host materials rapidly rises and the top temperature can reach to 600 K. Given the intense UC emission, high sensitivity, as well as good photothermal stability, La₂S₃:Yb³⁺/Er³⁺ phosphor can become a promising composite material for photothermal ablation of cancer cells possessing the functions of temperature sensing and in vivo imaging.     

REVO4‐Based Nanomaterials (RE = Y,La, Gd,and Lu) as Hosts for Yb3+/Ho3+, Yb3+/Er3+, and Yb3+/Tm3+ Ions: Structural and Up‐Conversion Luminescence Studies

Rare‐earth vanadates of the form REVO₄ (RE = Y, La, Gd, and Lu) doped by Yb³⁺/Ho³⁺, Yb³⁺/Er³⁺_, or Yb³⁺/Tm³⁺ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln³⁺ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO₄ and tetragonal YVO₄, GdVO₄, or LuVO₄ doped by Ln³⁺ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb³⁺ ions and emitting ions.     

基于Er3+/Yb3+掺杂的上转换玻璃陶瓷材料的制备和性能

采用熔融-晶化法在ZnO-Al2 O3-SiO2系玻璃陶瓷的基础上,用GeO2取代部分SiO2成功制备出Er3+/Yb3+共掺ZnO-Al2 O3-GeO2-SiO2系玻璃陶瓷,并通过对样品的硬度及上转换荧光测试分析确定了GeO2的最佳取代量为7.5wt％.研究发现在980 nm波长光的激发下,样品产生了绿色(524 nm、546 nm)和红色(659 nm)上转换发光,且当Er3+/Yb3+掺杂比为2.5:6.5时样品上转换荧光强度最强.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Enhanced and Long‐Lived Near‐Infrared Luminescence of Er3+ Ions in Lead Borate Glass‐Ceramics Containing PbWO4 Nanocrystals

Lead tungstate PbWO₄ nanocrystals in transparent lead borate glass‐ceramics containing Er³⁺ ions were fabricated. Luminescence spectra at about 1530 nm due to main ⁴I_13/2–⁴I_15/2 laser transition of Er³⁺ ions were examined for glass samples before and after heat treatment. Near‐infrared luminescence of Er³⁺ ions in glass‐ceramics is enhanced and long‐lived in comparison to precursor glasses. It suggests that the Er³⁺ ions are partially incorporated into PbWO₄ crystalline phase.     

Enhanced 2.0 μm Emission and Lowered Upconversion Emission in Fluorogermanate Glass‐Ceramic Containing LaF3:Ho3+/Yb3+ by Codoping Ce3+ Ions

Intense 2.0 μm emission of Ho³⁺ has been achieved through Yb³⁺ sensitization in fluorogermanate glass‐ceramic (GC) containing LaF₃ pumped with 980 nm laser diode (LD). The observation of concurrent emissions at 538, 650, and 1192 nm points to the additional deexcitation routes based on infrared‐to‐visible upconversion processes and Ho³⁺:⁵I₆ → ⁵I₈ radiative transition. Comparative investigations of photoluminescent spectra and decay curves have indicated the effective role of Ce³⁺ ions in enhancing the 2.0 μm fluorescence along with suppressing the occurrence of these concurrent emissions. This would offer a promising approach to develop compact and efficient 2.0‐μm laser systems.     

Tailorable Multicolor Up‐conversion Emissions in Tm3+/Ho3+/Yb3+ Co‐Doped LiLa(MoO4)2

Using a modified sol–gel method, LiLa(MoO₄)₂: Tm³⁺/Ho³⁺/Yb³⁺ phosphors with tailorable up‐conversion (UC) emission colors were prepared. Under the excitation of a 980 nm laser diode, up‐conversion red and green emissions in Ho³⁺/Yb³⁺ co‐doped and blue emission in Tm³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂ were observed, respectively. The intensities of the RGB (red, green, and blue) emissions could be controlled by varying concentrations of Tm³⁺ or Ho³⁺, and the optimal composition was also determined. In Tm³⁺/Ho³⁺/Yb³⁺ co‐doped LiLa(MoO₄)₂, the UC emission colors could be tuned from blue through white to yellow by adjusting the concentrations of Tm³⁺ or Ho³⁺. The UC excitation mechanisms were also investigated based on the power dependence of UC luminescence intensity.     

An Upconversion Niobium Pentoxide Bulk Glass Codoped with Er3+/Yb3+ Fabricated by Aerodynamic Levitation Method

(82?x)NbO_2.5–17.4LaO_1.5–xZrO₂(NLZ) (x = 7.5, 10, 12.5, 15, 17.5, and 20) bulk glasses codoped with Er³⁺/Yb³⁺ were successfully fabricated by aerodynamic levitation method for the first time. The structure, thermal stability, and luminescent properties of the samples were investigated systemically by XRD, differential scanning calorimetry, and upconversion spectra. Under 980 nm laser excitation, all samples exhibited green and red upconversion emissions centered at 531, 546, and 674 nm. Results showed that the sample with 15 mol% ZrO₂ obtained the most efficient upconversion luminescence and good thermal stability with the glass‐transition temperature as high as 743 °C. The effect of the addition of ZrO₂ on the structure behavior and the phonon density in the glass was investigated by Raman spectra, which are the key factors for the upconversion luminescence intensity.     

Tailoring the Structure and Luminescence of Nanostructured Er3+ and Er3+/Yb3+‐Activated Hafnia‐Based Systems

Nanostructured Er³⁺‐ and Er³⁺/Yb³⁺‐activated hafnium oxide films and nanoparticles were prepared from a stable colloidal suspension and investigated by several techniques such as transmission electron microscopy, X‐ray diffraction, dynamic light scattering, atomic force microscopy, Fourier‐transform infrared spectroscopy, and photoluminescence. Low roughness and crack‐free films were deposited by dip‐coating and spin‐coating techniques on vitreous SiO₂ and Si substrates. Nanostructured particles were also synthesized. Remarkable structural and spectroscopic differences were observed for hafnium oxide‐based materials as a function of the Er³⁺ and Er³⁺/Yb³⁺ concentration. The ⁴I_13/2 → ⁴I_15/2 emission bandwidth and the lifetime of the ⁴I_13/2 metastable state of Er³⁺ was tailored through the rare‐earth concentration. The Er³⁺ emission in HfO₂ can be explored for photonic applications.     

Dy3+/Ce3+ Codoped YAG Transparent Ceramics for Single‐Composition Tunable White‐Light Phosphor

Superior optical, thermal, and mechanical properties of transparent ceramics are very important in the applications of solid lasers, solid‐state lighting, and transparent armors. Herein, a series of (Dy_0.03Ce_xY_0.97?x)₃Al₅O₁₂ transparent ceramics were fabricated using vacuum reactive sintering method. Importantly, these Dy³⁺/Ce³⁺ codoped yttrium aluminum garnet (YAG) transparent ceramics served as single‐composition tunable white‐light phosphors for UV‐LEDs is developed for the first time. By combining with commercially available UV‐LEDs directly, the optimal chromaticity coordinates and correlated color temperature (CCT) are (x = 0.33, y = 0.35) and 5609 K, respectively. Notably, the codoping of Ce³⁺ enhances the luminescent intensity of Dy³⁺ ions while excited at 327 nm. The emission color of YAG transparent ceramics can be tuned from white to yellow through energy transfer between Dy³⁺ and Ce³⁺. These new phosphors, possessing of pure CIE chromaticity and environmentally friendly nature, are promising for applications in white UV‐LEDs.     

Evolution of Strong Red Upconversion Luminescence in Er3+‐Containing Oxy‐Fluoride Glass and Glass‐Ceramics

The Er³⁺ concentration dependencies of upconversion luminescence in oxy‐fluoride glass and glass‐ceramics containing PbF₂ nanocrystals were investigated. Strong red emission from the ⁴F_9/2 → ⁴I_15/2 transition was observed with the addition of ~0.8 mol% Er³⁺ ions, whereas ~10 mol% of Er³⁺ is required to achieve such emission in several other crystalline hosts. Intensities of red emission further increased with the formation of nanocrystals through heat treatment. The Er³⁺ ions enriched in glass and segregated preferentially inside the PbF₂ nanocrystals that decreased the distance among Er³⁺ ions and thereby facilitated energy transfer.