Triple NIR light excited up-conversion luminescence in lanthanide-doped BaTiO3 phosphors for anti-counterfeiting

Up-conversion luminescent (UCL) materials are excellent candidate for optical anti-counterfeiting and the exploitation of multi-wavelength NIR light triggered UC phosphors with tunable color emission is essential for reliable anti-counterfeiting technology. Herein, a series of lanthanide ions (Er³⁺, Er³⁺–Ho³⁺, and Yb³⁺–Tm³⁺) doped BaTiO₃ submicrometer particles are synthesized through a modified hydrothermal procedure. XRD and SEM measurements were carried out to identify the structure and morphology of the samples and their UCL properties under 808, 980, and 1550 nm NIR excitation are investigated. Er³⁺ singly doped sample exhibits Er³⁺ concentration-dependent and excitation wavelength-dependent emission color from green to yellow and orange. The corresponding UC mechanisms under three NIR light excitation are clarified. Pure red emission under 1550-nm excitation was obtained by introducing small amount of Ho³⁺ and the fluorescent lifetime test was used to confirm the energy transfer from Er³⁺ to Ho³⁺. In addition, Yb³⁺–Tm³⁺ co-doped sample shows intense blue emission from ¹G₄ → ³H₆ transition of Tm³⁺ under 980-nm excitation. As a proof of concept, the designed pattern using phosphors with red, green, and blue three primary color emissions under 1550, 808, and 980 nm NIR excitation was displayed to demonstrate their anti-counterfeiting application.     

Up-conversion emission color tuning in NaLa(MoO4)2: Nd3+/Yb3+/Ho3+ excited at 808 nm

As alternatives to Yb³⁺-sensitized up-conversion (UC) materials excited at 980 nm, Nd³⁺-sensitized UC phosphors irradiated by 808 nm have been used to decrease the absorption of water and alleviate the overheating effect in vivo biological application. Intense red and green UC emissions from ⁵F₅→⁵I₈ and ⁵F₄/⁵S₂→⁵I₈ transitions of Ho³⁺ appeared in Nd³⁺/Yb³⁺/Ho³⁺ tri-doped NaLa(MoO₄)₂ through successive energy transfer Nd³⁺→Yb³⁺→Ho³⁺ under 808 nm excitation, in which Yb³⁺ ions were proven to be the energy transfer bridge between Nd³⁺ and Ho³⁺ by lifetime measurement. The variable emission color and intensity ratios of red to green emissions were realized by adjusting the doping concentration of Yb³⁺, pulse width of the excitation laser and the addition of Ce³⁺ ion, which depends on the different population pathways to the green and red emitting states of Ho³⁺. The chromaticity modulation mechanisms of these approaches were proposed, which provides a feasible strategy to tune the UC emission color.     

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.     

Preparation,luminescence properties,and application of temperature sensing and anti-counterfeiting of La2MgTiO6:Yb3+/Ln3+/Mn4+

The doping of transition metal ions in the up-conversion (UC) luminescent material doped with Yb³⁺/Ln³⁺ is a facile way to increase their UC luminescence intensities and alter their colors. In this study, La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ (Ln³⁺ = Er³⁺, Ho³⁺, and Tm³⁺) phosphors showing excellent luminescence properties were prepared by a solid-state method. The sensitivity of the La₂MgTiO₆:Yb³⁺/Ln³⁺/Mn⁴⁺ phosphor was double that without Mn⁴⁺, because Mn⁴⁺ affects the UC emissions of Ln³⁺ via energy transfer between these ions. Moreover, Mn⁴⁺ also acts as a down-conversion activator, which can combine with UC ions to achieve multi-mode luminescence at different wavelengths. Under 980 nm excitation, these samples emit green light (from Er³⁺ and Ho³⁺) and blue light (from Tm³⁺). In contrast, under 365 nm excitation, they emit red light (from Mn⁴⁺). Further testing revealed that the La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ phosphors have potential applications in temperature sensing and anti-counterfeiting.     

Optical Temperature Sensing Behavior of High‐Efficiency Upconversion: Er3+–Yb3+ Co‐Doped NaY(MoO4)2 Phosphor

A class of Yb³⁺/Er³⁺ co‐doped NaY(MoO₄)₂ upconversion (UC) phosphors have been successfully synthesized by a facile hydrothermal route with further calcination. The structural properties and the phase composition of the samples were characterized by X‐ray diffraction (XRD). The UC luminescence properties of Yb³⁺/Er³⁺ co‐doped NaY(MoO₄)₂ were investigated in detail. Concentration‐dependent studies revealed that the optimal composition was realized for a 2% Er³⁺ and 10% Yb³⁺‐doping concentration. Two‐photon excitation UC mechanism further illustrated that the green enhancement arised from a novel energy‐transfer (ET) pathway which entailed a strong ground‐state absorption of Yb³⁺ ions and the excited state absorption of Yb³⁺–MoO₄^2? dimers, followed by an effective energy transfer to the high‐energy state of Er³⁺ ions. We have also studied the thermal properties of UC emissions between 303 and 523 K for the optical thermometry behavior under a 980 nm laser diode excitation for the first time. The higher sensitivity for temperature measurement could be obtained compared to the previous reported rare‐earth ions fluorescence based optical temperature sensors. These results indicated that the present sample was a promising candidate for optical temperature sensors with high sensitivity.     

Intense upconversion luminescence and energy‐transfer mechanism of Ho3+/Yb3+ co‐doped SrLu2O4 phosphor

A series of novel SrLu₂O₄: x Ho³⁺, y Yb³⁺ phosphors (x=0.005‐0.05, y=0.1‐0.6) were synthesized by a simple solid‐state reaction method. The phase purity, morphology, and upconversion luminescence were measured by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The doping concentrations and sintering temperature were optimized to be x=0.01, y=0.5 and T=1400°C to obtain the strongest emission intensity. Under 980 nm laser diode excitation, the SrLu₂O₄:Ho³⁺, Yb³⁺ phosphors exhibit intense green upconversion (UC) emission band centered at 541 nm (⁵F₄,⁵S₂→⁵I₈) and weak red emission peaked at 673 nm (⁵F₅→⁵I₈). Under different pump‐power excitation, the UC luminescence can be finely tuned from yellow‐green to green light region to some extent. Based on energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the analysis of pump‐power dependence and luminescence decay curves. The energy‐transfer mechanisms for green and red UC emissions can be determined to be two‐photon absorption processes. Compared with commercial NaYF₄:Er³⁺, Yb³⁺ and common Y₂O₃:Ho³⁺, Yb³⁺ phosphors, the SrLu_1.49Ho_0.01Yb_0.5O₄ sample shows good color monochromaticity and relatively high UC luminescence intensity. The results imply that SrLu₂O₄:Ho³⁺, Yb³⁺ can be a good candidate for green UC material in display fields.     

Color-tunable up-conversion emission from Yb3+/Er3+/Tm3+/Ho3+ codoped KY(MoO4)2 microcrystals based on energy transfer

Tunable up-conversion luminescent material KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) has been synthesized by a typical hydrothermal process. Under 980 nm laser diode (LD) excitation, the emission intensity and the corresponding luminescence colors of KY(MoO₄)₂: Yb³⁺, Ln³⁺ (Ln=Er, Tm, Ho) have been investigated in detail. The energy transfer from the Yb³⁺ sensitizer to Ho³⁺, Er³⁺ and Tm³⁺ activators plays an important role in the development of color-tunable single- phased phosphors. The emission intensity keep balance through control of the Ho³⁺ co-doping concentrations, white light was experimentally shown at KY(MoO₄)₂: 20 mol% Yb³⁺, 0.8 mol% Er³⁺, 0.5 mol% Tm³⁺, 1.0 mol% Ho³⁺ phosphor with further calcination at 800 °C for 4 h under 980 nm laser excitation. The color tunability, high quality of white light and high intensity of the emitted signal make these up-conversion (UC) phosphors excellent candidates for applications in solid-state lighting.     

Synthesis and Up‐conversion Luminescence of Yb3+/Ln3+ (Ln = Er,Tm, Ho) Co‐Doped Strontium Cerate by Pechini Method

Novel up‐conversion (UC) luminescent nanopowders, Sr₂CeO₄:Yb³⁺,Ln³⁺ (Ln = Er, Tm, Ho) were prepared with Pechini method. The Sr₂CeO₄:Yb³⁺,Ln³⁺ (Ln = Er, Tm, Ho) nanopowders had an orthorhombic crystal structure, and showed olive‐like morphology with the length of about 260 nm and width of about 130 nm. Under 980 nm lazer excitation, the Sr₂CeO₄:Yb³⁺/Er³⁺, Sr₂CeO₄:Yb³⁺/Tm³⁺, and Sr₂CeO₄:Yb³⁺/Ho³⁺ nanophosphors exhibit strong green, blue, and green UC luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

Concentration effects on the upconversion luminescence in Ho3+/Yb3+ co-doped NaGdTiO4 phosphor

Ho³⁺/Yb³⁺ co-doped NaGdTiO₄ phosphors were synthesized by a solid-state reaction method. The upconversion (UC) luminescence characteristics excited by 980 nm laser diode were systematically investigated. Bright green UC emission centered at 551 nm accompanied with weak red and near infrared (NIR) UC emissions centered at 652 and 761 nm were observed. The dependence of UC emission intensity on excitation power density showed that all of green, red and NIR UC emissions are involved in two-photon process. The UC emission mechanisms were discussed in detail. Concentration dependence studies indicated that Ho³⁺ and Yb³⁺ concentrations had significant influences on UC luminescence intensity and the intensity ratio of the red UC emission to that of the green one. Rate equations were established based on the possible UC mechanisms and a theoretical formula was proposed to describe the concentration dependent UC emission. The UC luminescence properties of the presented material was evaluated by comparing with commercial NaYF₄:Er³⁺, Yb³⁺ phosphor, and our sample showed a high luminescence efficiency and good color performance, implying potential applications in a variety of fields.     

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.     

Spectral pure RGB up-conversion emissions in self-assembled Gd2O3: Yb3+, Er3+/Ho3+/Tm3+ 3D hierarchical architectures

Self-assembled three-dimensional Yb³⁺(Ln = Er, Ho, Tm) co-doped Gd₂O₃ up-converted (UC) phosphors were synthesized by a facile co-precipitation method, and their morphologies and microstructures were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. Under the excitation at 980 nm, spectral pure three primary colors red, green and blue (RGB) emissions were respectively achieved in Yb³⁺/Er³⁺, Yb³⁺/Ho³⁺ and Yb³⁺/Tm³⁺ co-doped Gd₂O₃ phosphors, in which spectral color purities were tuned by adjusting the doping concentration, annealing temperature, excitation power density and the pulse-width of 980 nm laser. These results provide deeper insights into modulating spectral color purities of up-converted emission, and the potential applications of spectrally pure RGB up-converted materials in fingerprint recognition and multi-color printing were also investigated.     

Warm white-light generation in Ca9MgNa(PO4)7:Sr2+, Mn2+, Ln (Ln=Eu2+, Yb3+, Er3+, Ho3+, and Tm3+) under near-ultraviolet and near-infrared excitation

To obtain warm white-light emission, a series of Ca₉MgNa(PO₄)₇:Sr²⁺, Mn²⁺, Ln (Ln=Eu²⁺, Yb³⁺, Er³⁺, Ho³⁺, and Tm³⁺) phosphors were designed and their photoluminescence properties under near-ultraviolet and near-infrared excitation were studied. For near-ultraviolet excitation, blue-white emission is produced initially in the Eu²⁺ single-doped Ca₉MgNa(PO₄)₇, whose excitation band can well match with the near ultraviolet LED chip. By introducing Sr²⁺ ions into Ca₉MgNa(PO₄)₇:Eu²⁺, the Eu²⁺ emission band beyond 500 nm is enhanced obviously. Correspondingly, the emitting light color is tuned to nearly white. To generate warm white light further, Mn²⁺ is doped into the Ca_8.055MgNa(PO₄)₇:0.045Eu²⁺, 0.9Sr²⁺ and the correlated color temperature is decreased largely. For near-infrared excitation, the green, red, and blue emissions have been obtained in the Yb³⁺-Er³⁺, Yb³⁺-Er³⁺, and Yb³⁺-Er³⁺ co-doped Ca₉MgNa(PO₄)₇ phosphors, respectively. And warm white light is also produced in the Ca₉MgNa(PO₄)₇:Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺ under 980 nm excitation.     

Upconversion Luminescence and Energy‐Transfer Mechanism of NaGd(MoO4)2: Yb3+/Er3+ Microcrystals

Uniform and well‐crystallized NaGd(MoO₄)₂: Yb³⁺/Er^{3 +} microcrystals with tetragonal plate morphology were synthesized by a facile hydrothermal method. The structure and phase purity of the samples were identified by powder XRD analysis. The steady‐state and transient luminescence spectra were measured and analyzed. Under 980 nm excitation, intense green luminescence at 531 and 553 nm, and red luminescence at 657 and 670 nm were observed. The optimum doping concentrations for Yb³⁺ and Er³⁺ are determined to be 20% and 1% in NaGd(MoO₄)₂ tetragonal plate microcrystals. With increasing Yb³⁺ doping concentrations, the total integral emission intensities increase first and then decrease. The red/green intensity ratio of NaGd(MoO₄)₂: Yb³⁺/Er³⁺ microcrystals increases from 0.4 to 1.0 with the increase in Yb³⁺ concentrations. Based on the energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the double logarithmic plot of upconversion intensities versus pump powers. The energy‐transfer mechanisms for green and red upconversion luminescence are ascribed to two‐photon processes at lower Yb³⁺ concentrations, and involve high‐Yb³⁺‐induced one‐photon processes at higher Yb³⁺ concentrations. For the red upconversion luminescence, energy back‐transfer process, that is, ⁴S_3/2 (Er³⁺) + ²F_7/2 (Yb³⁺) → ⁴I_13/2 (Er³⁺) + ²F_5/2 (Yb³⁺), is dominant at higher Yb³⁺ concentrations. Theoretical model of the energy‐transfer mechanisms based on rate equations is established, which agrees well with the experimental results.     

Efficient dual‐mode up‐conversion and down‐shifting emission in β‐NaYF4:Yb3+,Er3+ microcrystals via ion exchange

We report efficient dual‐mode up‐conversion (UC) and down‐shifting (DS) emission in a single Yb³⁺/Er³⁺‐co‐doped β‐NaYF₄ microcrystals with controlled morphology and size via a simple Na⁺ ion‐exchange modification (IEM) method. IEM well preserves the crystal structure and monodispersed morphology of hydrothermal‐synthesized β‐NaYF₄. Meanwhile, IEM gives rise to the significant enhancement of UC emission intensity up to 3800 times and strongly enhanced DS emission intensity of Er³⁺ and Yb³⁺ by several times in β‐NaYF₄:Yb³⁺,Er³⁺ microcrystals. IEM also strongly prolongs the DS emission lifetimes of Er³⁺ and Yb³⁺ in visible and near‐infrared region. The enhanced UC and DS emission intensities and prolonged lifetimes in β‐NaYF₄:Yb³⁺,Er³⁺ are mainly ascribed to the dispersing of localized Yb³⁺ and Er³⁺ clusters during IEM.     

Emission from Mo‐O charge‐transfer state and Yb3+ emission in Eu3+‐doped and nondoped molybdates under UV excitation

Molybdates of Li⁺ and Yb³⁺ are studied to investigate the luminescence under UV excitation. LiYb(MoO₄)₂ and Eu³⁺‐doped LiYb₁‐_xEux(MoO₄)₂ (x=001–1.0) phosphors were synthesized by solid state reaction under mixing of Eu₂O₃, Yb₂O₃, Li₂CO₃ and MoO₂ in air atmosphere. Two broad absorption bands centered at 333 and 236 nm are observed in LiYb(MoO₄)₂ compound. They are attributed to the ¹A₁→¹T₁ and ¹T₂ transitions due to the O^2?→Mo⁶⁺ electron transfers in MoO₄ tetrahedron. An emission band with a peak at about 440 nm is found, which is attributed to the ³T₁→¹A₁ transition of MoO₄. Appearance of near‐infrared (NIR) Yb³⁺ emission observed under UV excitation is understood by the MoO₄→Yb³⁺ Foerster‐Type energy transfer due to spectral overlap between the low‐energy tail of the broad 440 nm emission band and the high‐energy tail of the broad Yb³⁺ absorption band and due to short Yb³⁺‐MoO₄ distance. Yb³⁺ emission observed in LiYb_1?xEu_x(MoO₄)₂ by Eu³⁺ excitation is understood by the Eu³⁺→Yb³⁺ energy transfer by cross‐relaxation (CR) process between the ⁵D₀→⁷F₆ Eu³⁺ transition and the ²F_7/2→²F_5/2 Yb³⁺ transition. The CR efficiency shows maximum efficiency of 0.24 at x=0.15 of higher acceptor Yb³⁺ concentration than donor Eu³⁺ concentration. Three Yb³⁺ emission bands with peaks at 994, 1002, and 1023 nm are observed, depending on the excitation wavelength. This is explained by less‐shielded 4f electrons of Yb³⁺ by the 5s²5p⁶ outermost electron shells, which are also responsible for unusual broadband Yb³⁺ absorption and emission. From appearance of NIR Yb³⁺ emission under excitation by not only UV light but also red light, these compounds are expected to be suitable for efficient photovoltaic application to Si‐based solar cells.     

Transmission electron microscopic and optical spectroscopic studies of Ni2+/Yb3+/Er3+/Tm3+ doped dual‐phase glass‐ceramics

Ni²⁺/Yb³⁺/Er³⁺/Tm³⁺ codoped transparent glass‐ceramics (GCs) containing both hexagonal β‐YF₃ and spinel‐like γ‐Ga₂O₃ dual‐phase nanoparticles (NCs) are synthesized by melt‐quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare‐earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in β‐YF₃, whereas the TMs in γ‐Ga₂O₃ NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3 nm), but it is enhanced between the REs partitioned in the β‐YF₃ NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near‐infrared (NIR) emission in the wavelength region of 1000‐2000 nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980 nm.     

Microwave Sol–Gel Synthesis of CaGd2(MoO4)4:Er3+/Yb3+ Phosphors and Their Upconversion Photoluminescence Properties

CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ phosphors with the doping concentrations of Er³⁺ and Yb³⁺ (x = Er³⁺ + Yb³⁺, Er³⁺ = 0.05, 0.1, 0.2, and Yb³⁺ = 0.2, 0.45) have been successfully synthesized by the microwave sol–gel method, and the crystal structure refinement and upconversion photoluminescence properties have been investigated. The synthesized particles, being formed after heat‐treatment at 900°C for 16 h, showed a well‐crystallized morphology. Under the excitation at 980 nm, CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ particles exhibited strong 525 and 550‐nm emission bands in the green region and a weak 655‐nm emission band in the red region. The Raman spectrum of undoped CaGd₂(MoO₄)₄ revealed about 15 narrow lines. The strongest band observed at 903 cm^?1 was assigned to the ν₁ symmetric stretching vibration of MoO₄ tetrahedrons. The spectra of the samples doped with Er and Yb obtained under 514.5 nm excitation were dominated by Er³⁺ luminescence preventing the recording Raman spectra of these samples. Concentration quenching of the erbium luminescence at ²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions in the CaGd₂(MoO₄)₄:Er³⁺/Yb³⁺ crystal structure was established to be approximately at the 10 at.% doping level.     

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.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.