Multicolor upconversion of Er3+/Tm3+/Yb3+ doped oxyfluoride glass ceramics

Er³⁺/Tm³⁺/Yb³⁺ tridoped oxyfluoride glass ceramics was synthesized in a general way. Under 980 nm LD pumping, intense red, green and blue upconversion was obtained. And with those primary colors, multicolor luminescence was observed in oxyfluoride glass ceramics with various dopant concentrations. The red and green upconversion is consistent with ⁴F_9/2 → ⁴I_15/2 and ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺ respectively. While the blue upconversion originates from ¹G₄ → ³H₆ transition of Tm³⁺. This is similar to that in Er³⁺/Yb³⁺ and/or Tm³⁺/Yb³⁺ codoped glass ceramics. However the upconversion of Tm³⁺ is enhanced by the energy transfer between Er³⁺ and Tm³⁺.     

Crystallization and spectroscopic properties investigations of Er3+ doped transparent glass ceramics containing CaF2

Transparent oxyfluoride glass ceramics with composition of 45SiO₂–25Al₂O₃–5CaCO₃–10NaF–15CaF₂–0.5ErF₃ (in mol%) were developed through controlled crystallization of melt-quenched glass. Non-isothermal crystallization kinetics investigation showed that the average apparent activation energy E_a and Avrami exponent n are about 283 kJ/mol and 2.22, respectively, indicating the crystallization a three dimensional crystal growth process controlled by the diffusion with a decreasing nucleation rate. X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) observation revealed the precipitation of CaF₂ crystallites sized about 15 nm among the glass matrix after heat-treatment at 650 °C for 2 h. For as-made glass, no upconversion signals were detected when excited with a 30 mW diode laser at 980 nm, while strong upconversion emissions at 545, 660 and 800 nm were obtained for transparent glass ceramic under similar excitation condition.     

Influence of Yb3+ content on microstructure and fluorescence of oxyfluoride glass ceramics containing LaF3 nano-crystals

The influence of Yb³⁺ content on structural evolution and fluorescence properties of oxyfluoride glass ceramics containing LaF₃ nano-crystals were systematically investigated. Differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) experiments indicated that Yb³⁺ ions acted as nucleating agent to facilitate LaF₃ crystallization. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) results verified the incorporation of Yb³⁺ into LaF₃ nano-crystal lattice. The absorption, emission spectra and fluorescence decays were measured. The infrared emission intensity of ⁴F_5/2 → ⁴F_7/2 transition under 980 nm excitation enhanced, while the measured lifetime reduced due to the increase of non-radiative transition probability, with the increase of Yb³⁺ content in glass ceramic. However, when Yb³⁺ doping reached 4.0 mol% the concentration quenching effect appeared.     

Fluorescence property investigations on Er-doped oxyfluoride glass ceramics containing LaF3 nanocrystals

The fluorescence properties of oxyfluoride glass ceramics containing nanosized LaF₃ crystals with different ErF₃ doping level were investigated. The spectroscopy analysis indicated that a dominant fraction of ErF₃ had been incorporated into the crystal phase. Broad 1.5 μm emission spectra with full width at half maximum (FWHM) value ranging from about 40–100 nm were obtained, which increased accordingly with ErF₃ doping level. Noteworthily, intense green and red upconversion emissions from samples with high ErF₃ doping level were observed when excited even with a 30 mW diode laser at 976 nm. An overall increment of the upconversion emissions intensity, and, a relative increase in intensity of the red emission with respect to that of the green one were also identified with increasing ErF₃ concentration. The possible upconversion mechanisms were proposed.     

Er3+/Yb3+ codoped oxyfluoride borosilicate glass ceramic containing NaYF4 nanocrystals for amorphous silicon solar cells

Transparent oxyfluoride borosilicate glass ceramic containing cubic NaYF₄ nanocrystals were successfully fabricated. The cubic NaYF₄ nanocrystals with average size of 30 nm were precipitated in the glass matrix, which was confirmed by the X-ray diffraction and TEM results. In comparison with the as-made glass, significant enhancement of upconversion luminescence is observed in the Er³⁺/Yb³⁺ codoped transparent glass ceramic, which may be due to the variation of coordination environment of Er³⁺ and Yb³⁺ ions after crystallization. The high transparency, intense upconversion luminescence and the simple, low-cost fabrication process make this material exhibiting potential applications in the fields of amorphous silicon solar cells.     

Structure and optical band gap study of transparent oxyfluoride glass-ceramics containing CaF2 nanocrystals

Oxyfluoride glass-ceramics containing CaF₂ nanocrystals were prepared by one-step crystallization of SiO₂–Al₂O₃–CaO–CaF₂ glasses at different temperatures. X-ray diffraction (XRD) results have revealed that CaF₂ was the only precipitated crystalline phase in glass-ceramic samples. Fourier transform infrared spectroscopy (FT-IR) study of the samples showed the effect of crystallization temperature on the structure. According to DTA and XRD results, suitable glass and its associated glass-ceramics were selected as the best sample in order to study the effect of crystallization on the optical properties. UV–Vis spectra of samples were recorded to determine optical properties. Fermi energy level decreased for glass-ceramics due to the increment of semiconducting behavior. Urbach energy, optical band of the specimens have been reduced by increasing of nanocrystals in glassy matrix which could be attributed to increasing of the order of the structural and formation of crystals and dangling bonds, respectively.     

Crystallization and spectroscopic properties in Er3+ doped oxyfluorogermanate glass ceramics containing Na

The Er³⁺ doped oxyfluorogermanate glasses, with a composition containing Na element, were synthesized by the conventional melting–quenching technique. When Na element was introduced into the composition of oxyfluorogermanate glass, the crystals behavior was investigated in details. Depending on the annealing procedure supplied, thermal annealing of precursor glasses in the system GeO₂/BaF₂/AlF₃/Na₂O/NaF/ZnO/GdF₃/ErF₃ led to the precipitation of different crystal phase nanocrystals. It was confirmed the nanocrystals in GC600 is orthorhombic NaBaAlF₆ which led to enhance obviously in the UC luminescence of Er³⁺. However, the nanocrystals in G585 led to decrease in the UC luminescence, which indicated few Er ions enter into the lattice of this nanocrystal phase. The reason of the decrease in UC emission intensity of GC585 was analyzed.     

White light emission of Dy3+-doped and Dy3+:Yb3+-codoped oxyfluoride glass ceramics under 388-nm excitation

Dy³⁺-doped and Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics have been prepared by high-temperature solid phase sintering method. The micrographs of scanning electron microscope show that a lot of nanorods are formed on the surface of Dy³⁺:Yb³⁺-codoped sample. The excitation spectra and emission spectra are measured, respectively, and intense photoluminescence peaks at 482 and 575 nm corresponding to the transitions of Dy³⁺ ions are found in single-doped samples under 388-nm excitation. For Dy³⁺:Yb³⁺-codoped oxyfluoride glass ceramics, the intensities at blue and green bands become weaker whereas the intensity at 695 nm gets stronger. The indirect sensitization is detailedly discussed and Commission Internationale de l′E-clairage chromaticity coordinates exhibit that two kinds of oxyfluoride glass ceramics are available candidates for the solid-state white light emission.     

Ultraviolet upconversion luminescence of Gd3+ and Eu3+ in nano-structured glass ceramics

Ultraviolet multiphoton upconversion emissions of Eu³⁺ (⁵H_3–7, ⁵G_2–6, ⁵L₆ → ⁷F₀) and Gd³⁺ (⁶I_J, ⁶P_J → ⁸S_7/2) are studied in the Eu³⁺ (or Gd³⁺) doped SiO₂–Al₂O₃–NaF–YF₃ precursor glasses and glass ceramics containing β-YF₃ nanocrystals, under continuous-wavelength 976 nm laser pumping. It is experimentally demonstrated that energy transfer from Yb³⁺ to Tm³⁺, then further to Eu³⁺ or Gd³⁺ is responsible for the upconversion process. Compared to those in the precursor glasses, the upconversion emission intensities in the glass ceramics are greatly enhanced, owing to the participation of rare earth ions into the low-phonon-energy environment of β-YF₃ nanocrystals. Hopefully, the studied glass ceramics may find potential applications in the field of ultraviolet solid-state lasers.     

Visible upconversion emission of Pr3+ doped gadolinium gallium garnet nanocrystals

The luminescence properties of a Pr3+-doped gadolinium gallium garnet (GGG, Gd3Ga5O12) nanocrystalline host were investigated. Dominant blue/green emission was observed emanating from the 3P0 --> 3H4 transition after excitation using a wavelength of 457.9 nm. Continuous wave excitation into the 1D2 level of the Pr3+ ion at 606.9 nm transition produced blue upconversion luminescence spectra, ascribed to emission from the 3P1 --> 3H4 and 3P0 --> 3H4 transitions. The increase in the decay times of the observed transitions following excitation with 606.9 nm is indicative of the dominance of an energy transfer upconversion (ETU) mechanism relative to excited state absorption (ESA). Furthermore, blue, green and red upconversion emission was observed from the 3P0, 3P1 and 1D2 states following excitation into the 1G4 energy level with 980 nm. No change in the decay times of the emitting states was observed following excitation with a wavelength of 980 or 457.9 nm; hence, upconversion was determined to primarily occur through ESA. The luminescence properties of the nanocrystals are compared to a single crystal of GGG:Pr3+ (bulk) with an identical Pr3+ concentration (1%).     

Structure and luminescence properties of Eu/Tb codoped oxyfluoride glass ceramics containing Sr2GdF7 nanocrystals

Eu/Tb codoped transparent oxyfluoride borosilicate glass ceramics containing Sr₂GdF₇ nanocrystals were fabricated under a reductive atmosphere and the conversion of Eu³⁺ ions to Eu²⁺ ions was observed. The Sr₂GdF₇ nanocrystals with an average size of 32 nm were homogeneously precipitated in the oxyfluoride borosilicate glass matrix, which could be evidenced by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. The enhancement of photoluminescence emission intensity, reduction of the relative emission intensities between ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁, and long fluorescence lifetimes of Eu²⁺, Eu³⁺, and Tb³⁺ ions revealed that more rare earth ions were partitioned into the low phonon energy environment Sr₂GdF₇ nanocrystals. Under ultraviolet excitation, pure and bright white light emission was obtained in the oxyfluoride borosilicate glass ceramic, which may be a potential blue, green and red-emitting phosphor for white LEDs.     

Direct observation of Nd3 + and Tm3 + ion distributions in oxy-fluoride glass ceramics containing PbF2 nanocrystals

Nd^3 + and Tm^3 +, doped oxy-fluoride glasses and glass ceramics were prepared by conventional melt-quenching and subsequent heat-treatment, respectively. β-PbF₂ nanocrystals with diameter 50 –100 nm formed in the glass matrix after heat treatment. The Stark splitting in absorption peaks, enhanced photoluminescence and prolonged lifetimes that β-PbF₂ nanocrystal formation increased the luminescence of rare earth ions. Both Nd^3 + and Tm^3 + ions were incorporated into nanocrystals that were enriched in lead and fluorine, and deficient in oxygen.     

Microstructure and environment dependence of 2H11/2 --> 4I15/2 upconversion emission in YVO4:Er3+, Yb3+ nanocrystals

Upconversion emission of different nanocrystalline YVO4:Er3+, Yb3+ synthesized by a hydrothermal process at low temperature was studied under 980 nm excitation where green [(2H11/2, 4S3/2) --> 4I15/2] and red (4F9/2 --> 4I15/2) emissions demonstrate sensitivity to the local environments of Er3+. Small particle size, high Yb3+ concentration, or high temperature favors the emission of the 2H11/2 --> 4I15/2 transition. Both XRD patterns and Raman spectra have confirmed that crystal lattice distortion of YVO4:Er3+, Yb3+ nanocrystals is more serious when the nanoparticle size is decreasing or Yb3+ concentration is increasing. This distortion is thought to play a key role in the observed spectral properties, which might lead to a new route to improve the monochromatic upconversion emission efficiency in these nanocrystals.     

Er3+单掺与Er3+/Yb3+共掺Y2SiO5的上转换发光

报道了一种新的上转换发光材料X2型Y2SiO5:Er, Yb并研究了Yb3 浓度和泵浦功率对样品的上转换发光特性的影响:(1)随着Yb3 浓度的增加,绿、红光发射均呈先增强后减弱的变化,但相对于绿光发射,红光发射受Yb3 浓度的影响更剧烈,并且当12%(摩尔分数)Yb3 时,可以得到很纯的红光发射;(2)上转换发光强度与泵浦功率的关系表明,双光子吸收贡献样品的上转换发射.此外,讨论了可能的上转换机制.认为随着Yb3 浓度增加,Er3 的激发态吸收、Yb3 到Er3 的能量传递和Er3 的交叉弛豫对上转换发光的作用依次逐渐加强.     

Study of fluorine losses and spectroscopic properties of Er doped oxyfluoride silicate glasses and glass ceramics

The fluorine losses during synthesis of Er³⁺ doped transparent glasses in the SiO₂–PbO–PbF₂ system were investigated. The final fluorine contents of the glasses were detected by using a fluorine ion selective electrode. The results show that high fluorine losses are occured in the normal preparation processes. With the increase of initial PbF₂ contents or melting time resulted in the increase of the fluorine losses. The thermal and spectroscopic properties of the glasses and the corresponding glass ceramics were investigated through the analysis of the differential scanning calorimetry (DSC), absorption and upconversion luminescence spectra. The effects of fluorine contents show a decrease of the glass transition temperatures (Tg) of the glasses and an enhancement of upconversion intensity of the corresponding glass ceramics.     

Broadband emission from Ce3+/Mn2+/Yb3+ tri-doped oxyfluoride glasses for glass greenhouse

In this work, a kind of oxyfluoride glasses tri-doped with Ce³⁺/Mn²⁺/Yb³⁺ ions was prepared by a simple and fast high temperature melting method. Under excitation with 300 nm light, two meaningful broad band emissions (ranged from 340 to 500 nm and 510–700 nm) were obtained, which matched well with the absorption of the chlorophylls. Under near-infrared (980 nm) excitation, an abnormal up-conversion luminescence was demonstrated in the oxyfluoride glasses by the energy transfer from Yb³⁺ to Mn²⁺. In addition, the up-conversion emission has a red shift along with the increase of the doping concentration of Mn²⁺, which would contribute to match the action spectrum of photosynthesis better. Our materials will be favored to extend the utilization of solar energy in glass greenhouse for plant cultivation.     

Ultraviolet upconversion fluorescence of Er3+ in Yb3+/Er3+-codoped Gd2O3 nanotubes

Under 980 nm excitation, room-temperature ultraviolet (UV) upconversion (UC) emissions of Er3+ from the 4G(9/2), 2K(13/2), and 2P(3/2) states were observed in Gd2O3:Yb3+/Er3+ nanotubes, which were synthesized via a simple wet-chemical route at low temperature and ambient pressure followed by a subsequent heat treatment at 800 degrees C. The experimental results exhibited that these UV emissions came from four-photon UC processes. In the Gd2O3:Yb3+/Er3+ nanocrystals, the energy transfers (ETs) from Yb3+ to Er3+ played important roles in populating the high-energy states of Er3+ ions. This material provides a possible candidate for building UV compact solid-state lasers or fiber lasers.