Spectroscopic properties and energy transfer in Er–Tm co-doped bismuth silicate glass

In this paper, we investigate the spectroscopic properties of and energy transfer processes in Er–Tm co-doped bismuth silicate glass. The Judd–Ofelt parameters of Er³⁺ and Tm³⁺ are calculated, and the similar values indicate that the local environments of these two kinds of rare earth ions are almost the same. When the samples are pumped at 980 nm, the emission intensity ratio of Tm:³F₄ → ³H₆ to Er:⁴I_13/2 → ⁴I_15/2 increases with increased Er³⁺ and Tm³⁺ contents, indicating energy transfer from Er:⁴I_13/2 to Tm:³F₄. When the samples are pumped at 800 nm, the emission intensity ratio of Er:⁴I_13/2 → ⁴I_15/2 to Tm:³H₄ → ³F₄ increases with increased Tm₂O₃ concentration, indicating energy transfer from Tm:³H₄ to Er:⁴I_13/2. The rate equations are given to explain the variations. The microscopic and macroscopic energy transfer parameters are calculated, and the values of energy transfer from Er:⁴I_13/2 to Tm:³F₄ are found to be higher than those of the other processes. For the Tm singly-doped glass pumped at 800 nm and Er–Tm co-doped glass pumped at 980 nm, the pumping rate needed to realize population reversion is calculated. The result shows that when the Er₂O₃ doping level is high, pumping the co-doped glass by a 980 nm laser is an effective way of obtaining a low-threshold ∼2 μm gain.     

Upconversion emission in antimony–germanate double-clad optical fiber co-doped with Yb3+/Tm3+ ions

In the paper upconversion luminescence properties in Yb³⁺/Tm³⁺ co-doped antimony–germanate glass and double-clad optical fiber were studied. The concentration of lanthanides, which has shown the highest upconversion emission intensity at 478 nm (¹G₄ → ³H₆) and 650 nm (¹G₄ → ³F₄), is 1Yb₂O₃/0.1Tm₂O₃ (mol%) as a result of exciting with a laser diode (976 nm). The lifetime of ²F_5/2 (Yb³⁺) level decreases from 781 μs to 71 μs in the presence of Tm³⁺ 0.1–0.75 mol% respectively. Luminescence decay curve of glass co-doped with 1Yb₂O₃/0.75Tm₂O₃ suggests donor–donor fast migration followed by Tm³⁺ → Yb³⁺ energy transfer. Glass characterized by highest intensity of upconversion luminescence (1Yb₂O₃/0.1Tm₂O₃ mol%) was used as core of double-clad optical fiber made by modified rod-in-tube method. Mechanisms influencing differences in upconversion amplified spontaneous emission of the fabricated optical fiber and bulk glass were discussed. Reabsorption of the amplified spontaneous emission signal along the fibre resulting from Tm³⁺:³H₆ → ¹G₄, transition was observed.     

Tm3+ doped Ga–As–S chalcogenide glasses and fibers

Tm³⁺ doped Ga–As–S chalcogenide glass samples were produced using As₂S₃ pure glass as starting materials. Their photoluminescence properties were characterized and strong emission bands were observed at 1.2 μm (¹H₅ → ³H₆), 1.4 μm (³H₄ → ³F₄) and 1.8 μm (³F₄ → ³H₆) under excitation wavelengths of 698 nm and 800 nm. The thulium and gallium concentrations were optimized to achieve the highest photoluminescence efficiency. From the optimal composition, a Tm³⁺ doped Ga–As–S fiber was drawn and its optical properties were studied.     

Spectral properties of Ho3+/Tm3+ co-doped β′-Gd2(MoO4)3 crystal as laser gain medium around 2.0 μm

Ho³⁺/Tm³⁺ co-doped β′-Gd₂(MoO₄)₃ single crystal was investigated as gain medium for Ho³⁺ laser around 2.0 μm. Polarized absorption and fluorescence spectra of the crystal were measured. Polarized spectral parameters of Ho³⁺ ions in the crystal were calculated and the gain curves around 2.0 μm were estimated. The fluorescence decay curves for Tm³⁺ and Ho³⁺ ions related to the 2.0 μm laser were measured and analyzed. The distinct coupled decay behavior for the Ho³⁺/Tm³⁺ co-doped system embodies the existence of energy transfer between Tm³⁺ and Ho³⁺ ions.     

Spectroscopic properties of Tm3+/Al3+ co-doped sol–gel silica glass

Tm³⁺/Al³⁺ co-doped silica glass was prepared by sol–gel method combined with high temperature sintering. Glasses with compositions of xTm₂O₃–15xAl₂O₃–(100 − 16x) SiO₂ (in mol%, x = 0.1, 0.3, 0.5, 0.8 and 1.0) were prepared. The high thulium doped silica glass was realized. Their spectroscopic parameters were calculated and analyzed by Judd–Ofelt theory. Large absorption cross section (4.65 × 10⁻²¹ cm² at 1668 nm) and stimulated emission cross section (6.00 × 10⁻²¹ cm² at 1812 nm), as well as low hydroxyl content (0.180 cm⁻¹), long fluorescence lifetime (834 μs at 1800 nm), large σ_em × τ_rad (30.05 × 10⁻²¹ cm² ms) and large relative intensity ratio of the 1.8 μm (³F₄ → ³H₆) to 1.46 (³H₄ → ³F₄) emissions (90.33) are achieved in this Tm³⁺/Al³⁺ co-doped silica glasses. According to emission characteristics, the optimum thulium doping concentration is around 0.8 mol%. The cross relaxation (CR) between ground and excited states of Tm³⁺ ions was used to explain the optimum thulium doping concentration. These results suggest that the sol–gel method is an effective way to prepare Tm³⁺ doped silica glass with high Tm³⁺ doping and prospective spectroscopic properties.     

Optical characterization of YAl3(BO3)4:Dy3+–Tm3+ phosphors under near UV excitation

Dy³⁺ and Tm³⁺ co-doped YAl₃(BO₃)₄ (YAB) phosphors were prepared by solid-state reaction method at 1200 °C/3 h. The average crystallite size was determined as 52.09 nm from the X-ray diffraction measurements. Upon 352 and 359 nm near ultra violet excitation, the YAB:Dy³⁺–Tm³⁺ phosphors exhibit Dy³⁺:⁴F_9/2 → ⁶H_J (J = 15/2, 13/2, 11/2) and Tm³⁺:¹D₂ → ³F₄ transitions with different luminescence intensity. The photoluminescence emission and decay measurements revealed the energy transfer from Dy³⁺ to Tm³⁺ ions under 359 nm excitation only. The energy transfer between Dy³⁺ and Tm³⁺ takes place in Dy³⁺–Tm³⁺ clusters through exchange interaction mechanism. The Commission International de I’Eclairage chromaticity coordinates of YAB:Tm³⁺ phosphor (λ_ex = 359 nm) were found very close to the European Broadcasting Union and National Television Standard Committee illuminants. The emission color of the studied phosphors could be tuned from blue-to-white as a function of excitation wavelength. The YAB:Dy³⁺–Tm³⁺ phosphors can be used as potential candidates in display technology.     

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⁺.     

Upconversion luminescence of Ba(MoO4)h(WO4)1−h:Yb3+/Er3+ nanocrystals synthesized through hydrothermal method

A series of Yb³⁺/Er³⁺ co-doped Ba(MoO₄)_h(WO₄)_1−h upconversion nanocrystals (UCNCs) were prepared via hydrothermal method. The effects of different concentration ratios of Yb³⁺/Er³⁺ and Mo₄O²⁻/WO₄²⁻ on the upconversion luminescence were investigated, and the optimum doping concentrations of Yb³⁺ and Er³⁺ in the Ba(MoO₄)_0.5(WO₄)_0.5 host were found to be 3 mol% and 1 mol%, respectively. Structure of Ba(MoO₄)_0.5(WO₄)_0.5:0.03Yb³⁺/0.01Er³⁺ was identified as the tetragonal in the X-ray diffraction (XRD) results and the particle size observed in the scanning electron microscope (SEM) was about 40 nm. Under excitation of 980 nm semiconductor laser, three emission bands centered at 528, 550 and 660 nm, originating from ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ion, respectively, were observed for Ba(MoO₄)_0.5(WO₄)_0.5:0.03Yb³⁺/0.01Er³⁺. The pump power dependence research suggested that these bands arise due to two-photon absorption. The variation of CIE coordinate at different excitation powers was observed.     

Comparative study of Er3+ and Tm3+ co-doped YOF and Y2O3 powders as red spectrally pure upconverters

We prepared Er³⁺ and Tm³⁺ co-doped yttrium oxyfluoride (YOF) powder by combustion synthesis and we observed that under near-infrared (λ = 980 nm) laser excitation the characteristic green (²H_11/2, ⁴S_3/2 → ⁴I_15/2) emission of Er³⁺ was suppressed by energy transfer (ET) mechanisms between Tm³⁺ and Er³⁺. The ET process observed in YOF was much more efficient than that observed in standard Y₂O₃ powder prepared under similar conditions. YOF combines the superior mechanical and thermal properties of oxides with low phonon energy of fluorides. Our results show that this material is a serious candidate for use as a red upconversion phosphor.     

Preparation,spectroscopic characterization and energy transfer investigation of iron-chromium diffusion co-doped ZnSe for mid-IR laser applications

The spectroscopic characterization and energy transfer mechanism of iron-chromium co-doped ZnSe polycrystalline (Cr,Fe:ZnSe) were reported with dimension of 15 mm × 15 mm × 2 mm obtained by controlled post-growth thermal diffusion method. The infrared absorption is characterized by a strong broad-band centered at 1770 nm which can be attributed to the only spin-allowed transition ⁵T₂ → ⁵E within the 3d⁴ shell of Cr²⁺ ions. Photoluminescence spectrum shows a relatively strong broad emission band centered at 4.1 μm with a width of 0.8 μm (FWHM) under 1770 nm excitation at room temperature and reveals effective Cr²⁺ → Fe²⁺ energy transfer process. Room temperature photoluminescence decay about 8 μs was measured. All the results indicate that Cr,Fe:ZnSe could achieve laser operation at 3.7–4.5 μm via Cr²⁺ → Fe²⁺ energy transfer using a more convenient laser pump source in the near IR region.     

Spectroscopic analysis of a novel Nd3+-activated barium borate glass for broadband laser amplification

Spectroscopic parameters of a novel Nd³⁺-activated barium borate (BBONd) glass have been analyzed for broadband laser amplification. The Judd–Ofelt (JO) intensity parameters were determined through a systematic analysis of the absorption spectrum of Nd³⁺ ions in the BBONd glass. High values of the JO intensity parameters reveal a great centro-symmetrical loss of the Nd³⁺ sites and high covalency degree of the ligand field. The very high Ω₆ intensity parameter value makes evident both a great structural distortion of the Nd³⁺ sites and a strong electron–phonon coupling between Nd³⁺ and free OH⁻ ions, which is consistent with the phonon energy maximum (3442.1 cm⁻¹) recorded by Raman spectroscopy. This strong electron–phonon coupling favors high effective bandwidth and gain bandwidth values of the laser emission (⁴F_3/2 → ⁴I_11/2) of Nd³⁺ ions. The electric-dipole oscillator strengths of all the Nd³⁺ absorption transitions, and in particular that of the hypersensitive transition (⁴I_9/2 → ⁴G_5/2), are enhanced by this great structural distortion of the host. Broadband laser amplification of the ⁴F_3/2 → ⁴I_11/2 emission (1062 nm) of Nd³⁺ ions in the BBONd glass pumped at 805 nm (⁴I_9/2 → ⁴F_5/2 + ²H_9/2) is evaluated through the main fluorescent parameters in competition with non-radiative processes. In general, the BBONd glass exhibits spectroscopic parameters comparable with those reported in the literature for broadband laser amplification into the IR region.     

Judd–Ofelt analysis and energy transfer processes of Er3+ and Nd3+ doped fluoroaluminate glasses with low phosphate content

Spectroscopic property and energy transfer processes of singly doped and codoped Er³⁺ and Nd³⁺ fluoroaluminate glasses with low phosphate content are systematically analyzed. The absorption spectra of these glasses are tested, and the Judd–Ofelt (J–O) and radiative parameters are discussed based on J–O theory and the parameters changes substantially because of the other codoping ions. As for Nd³⁺: the main emission bands at 0.9 and 1.05 μm decrease in the codoped sample under the excitation of an 800 nm laser diode from the emission spectra because the Er³⁺: ⁴I_11/2 level reduces the Nd³⁺: ⁴F_3/2 level effectively through the energy transfer process Nd³⁺: ⁴F_3/2 → Er³⁺: ⁴I_11/2. For Er³⁺, the emission at 1.5 μm is restrained by codoping with Nd³⁺ ions from the energy transfer process Er³⁺: ⁴I_13/2 → Nd³⁺: ⁴I_15/2. The emission at 2.7 μm is enhanced because the Nd³⁺ ions deplete the lower level and exert a positive effect on the upper laser level. The microparameters of the energy transfer between the Er³⁺ and Nd³⁺ ions are calculated and discussed using Forster–Dexter theory. The energy transfer efficiencies of the Nd³⁺: ⁴F_3/2 to the Er³⁺: ⁴I_11/2 and the Er³⁺: ⁴I_13/2 to the Nd³⁺: ⁴I_15/2 are 28.8% and 74.5%, respectively. These results indicate that Nd³⁺ can be an efficient sensitizer for Er³⁺ to obtain Mid-infrared (Mid-IR) emission and the codoped Er³⁺/Nd³⁺ fluoroaluminate glass with low phosphate content is suitable to be used as the fiber optical gain media for 2.7 μm laser generation.     

Effect of Ag nanoparticles on the radiative properties of tellurite glasses doped with Er3+, Yb3+ and Tm3+ ions

The present work is devoted to the characterization of the thermal and spectroscopic properties of tellurite glasses, codoped with Er³⁺, Yb³⁺ and Tm³⁺ rare-earth ions and silver nanoparticles (NPs). The techniques used for this investigation were UV–visible and infrared absorption, time-resolved luminescence and thermal lens. Time-resolved luminescence studies indicate efficient Yb³⁺ → Er³⁺ and Yb³⁺ → Tm³⁺ energy transfers and intense Er³⁺ and Tm³⁺ mid-infrared emissions around 1550 nm and 1860 nm, respectively. The presence NPs is found to increase the thermal diffusivity of the materials and to shorten the mid-infrared emission lifetime of both the Er³⁺ and Tm³⁺ ions.     

Alkaline aluminum phosphate glasses for thermal ion-exchanged optical waveguide

Alkaline aluminum phosphate glasses (NMAP) with excellent chemical durability for thermal ion-exchanged optical waveguide have been designed and investigated. The transition temperature Tg (470 °C) is higher than the ion-exchange temperature (390 °C), which is favorable to sustain the stability of the glass structure for planar waveguide fabrication. The effective diffusion coefficient D_e of K⁺–Na⁺ ion exchange in NMAP glasses is 0.110 μm²/min, indicating that ion exchange can be achieved efficiently in the optical glasses. Single-mode channel waveguide has been fabricated on Er³⁺/Yb³⁺ doped NMAP glass substrate by standard micro-fabrication and K⁺–Na⁺ ion exchange. The mode field diameter is 9.6 μm in the horizontal direction and 6.0 μm in the vertical direction, respectively, indicating an excellent overlap with a standard single-mode fiber. Judd–Ofelt intensity parameter Ω₂ is 5.47 × 10⁻²⁰ cm², implying a strong asymmetrical and covalent environment around Er³⁺ in the optical glasses. The full width at half maximum and maximum stimulated emission cross section of the ⁴I_13/2 → ⁴I_15/2 are 30 nm and 6.80 × 10⁻²¹ cm², respectively, demonstrating that the phosphate glasses are potential glass candidates in developing compact optoelectronic devices. Pr³⁺, Tm³⁺ and Ho³⁺ doped NMAP glasses are promising candidates to fabricate waveguide amplifiers and lasers operating at special telecommunication windows.     

Energy transfer and energy level decay processes of Er3+ in water-free tellurite glass

This report details the fundamental spectroscopic properties of a new class of water-free tellurite glasses studied for future applications in mid-infrared light generation. The fundamental excited state decay processes relating to the ⁴I_11/2 → ⁴I_13/2 transition in singly Er³⁺-doped Tellurium Zinc Lanthanum glass have been investigated using time-resolved fluorescence spectroscopy. The excited state dynamics was analyzed for Er₂O₃ concentrations between 0.5 mol% and 4 mol%. Selective laser excitation of the ⁴I_11/2 energy level at 972 nm and selective laser excitation of the ⁴I_13/2 energy level at 1485 nm has established that in a similar way to other Er³⁺-doped glasses, a strong energy-transfer upconversion by way of a dipole–dipole interaction between two excited erbium ions in the ⁴I_13/2 level populates the ⁴I_11/2 upper laser level of the 3 μm transition. The ⁴I_13/2 and ⁴I_11/2 energy levels emitted luminescence with peaks located at 1532 nm and 2734 nm respectively with luminescence efficiencies of 100% and 8% for the higher (4 mol.%) concentration sample. Results from numerical simulations showed that a population inversion is reached at a threshold pumping intensity of ∼57 kW cm⁻² for a CW laser pump at 976 nm for [Er₂O₃] = 2 mol.%.     

Synthesis and characterization of Yb3+,Tm3+:Ba2YF7 nanocrystalline with efficient upconversion fluorescence

A novel upconversion luminescence nanocrystals Yb³⁺,Tm³⁺:Ba₂YF₇ were synthesized via the hydrothermal method. They have uniform morphology with a mean size of 30 nm even if annealed at 600 °C. Pumped by 980 nm laser diode the as-synthesized powers emit ultraviolet/blue light, which is in the range of the specific upconversion luminescent spectra of Tm³⁺ ions. After post-annealing at 600 °C in an argon atmosphere for 2 h, their upconversion luminescence intensity is 5 multiple improved and the ultraviolet/blue light can even be seen by the naked eyes under a low excitation power of 20 mW. This indicates that Ba₂YF₇ is a very effective luminescent host material. Excitation power dependences of individual upconversion emission intensity are plotted, which partly uncover the upconversion luminescence mechanism of Tm³⁺ ions.     

Color centers and charge state recharge in γ-irradiated Yb:YAP

Gamma-ray irradiation induced color centers and charge state recharge of impurity and doped ion in 10 at.% Yb:YAP have been studied. The change in the additional absorption (AA) spectra is mainly related to the charge exchange of the impurity Fe²⁺, Fe³⁺ and Yb³⁺ ions. Two impurity color center bands at 255 and 313 nm were attributed to Fe³⁺ and Fe²⁺ ions, respectively. The broad AA band centered at 385 nm may be associated with the cation vacancies and F-type center. The transition Yb³⁺ → Yb²⁺ takes place in the process of γ-irradiation. Oxygen annealing and γ-ray irradiation lead to an opposite effect on the absorption properties of the Yb:YAP crystal. In the air annealing process, the transition Fe²⁺ → Fe³⁺ and Yb²⁺ → Yb³⁺ take place and the color centers responsible for the 385 nm band was destroyed.     

Enhanced emission of 2.7 μm from Er3+/Nd3+-codoped LiYF4 single crystals

An Er³⁺/Nd³⁺ co-doped LiYF₄ single crystal of ～Φ 12 mm × 95 mm size with high quality was grown by a Bridgman method. The luminescent properties of the crystals with different Er³⁺ and Nd³⁺ concentrations were studied. Compared with the Er³⁺ single-doped LiYF₄ crystal extremely enhanced emission at 2.7 μm from the Er³⁺/Nd³⁺ co-doped LiYF₄ was observed upon excitation of an 800 nm laser diode. Meanwhile, the green up-conversion emission and near infrared emission at 1.5 μm from Er³⁺ in the co-doped crystals were effectively restricted. The luminescent mechanisms for the Er³⁺/Nd³⁺ co-doped crystals were analyzed and the possible energy transfer processes were proposed. The energy transfer efficiencies for (Er³⁺:⁴I_13/2, Nd³⁺:⁴I_9/2) → (Er³⁺:⁴I_15/2, Nd³⁺:⁴I_15/2) and (Nd³⁺:⁴F_3/2, Er³⁺:⁴I_15/2) → (Nd³⁺:⁴I_9/2, Er³⁺:⁴I_9/2) were calculated. It was found that Er³⁺/Nd³⁺ co-doped single crystal may be a potential host for 2.7 μm lasers.     

Investigation on the luminescence of RE3+ (RE = Ce,Tb, Eu and Tm) in KMGd(PO4)2 (M = Ca,Sr) phosphates

The VUV excited luminescent properties of Ce³⁺, Tb³⁺, Eu³⁺ and Tm³⁺ in the matrices of KMGd(PO₄)₂ (M = Ca, Sr) were investigated. The bands at about 165 nm and 155 nm in the VUV excitation spectra are attributed to host lattice absorptions of the two matrices. For Ce³⁺-doped samples, the Ce³⁺ 5d levels can be identified. As for Tb³⁺-doped samples, typical 4f–5d absorption bands in the region of 175–250 nm were observed. For Eu³⁺ and Tm³⁺-doped samples, the O²⁻–Eu³⁺ and O²–Tm³⁺ CTBs are observed to be at about 229 nm and 177 nm, respectively. From the standpoints of color purity and luminescent efficiency, KCaGd(PO₄)₂:Tb³⁺ is an attractive candidate of green light PDP phosphor.     

Up-conversion luminescence of the NaYF4:Yb3+,Er3+ nanomaterials prepared with the solvothermal synthesis

Up-converting NaYF₄:Yb³⁺,Er³⁺ (x_Yb: 0.20, x_Er: 0.02) nanomaterials were prepared with a microwave assisted solvothermal synthesis to study how the synthesis parameters affect the structure and up-conversion luminescence of the materials and thus their usability as labels in biomedical applications. The purity of the materials was studied with Fourier transform infra-red (FT-IR) spectroscopy and the particle size and morphology with transmission electron microscopy (TEM). The crystal structure was characterized with X-ray powder diffraction (XPD) and the crystallite sizes were calculated with the Scherrer formula. Up-conversion luminescence and luminescence decays were studied with near infra-red (NIR) laser excitation at 970 nm.The presence of the oleic acid was observed in the FT-IR spectra. The TEM images showed small quasi-spherical nanoparticles as well as long nanorods. The XPD measurements revealed that both cubic and hexagonal forms of NaYF₄ were present in the materials. The crystallite sizes ranged from ca. 20 to over 150 nm for the cubic and hexagonal phases, respectively. The characteristic up-conversion luminescence of Er³⁺ in red (640–685 nm; ⁴F_9/2 → ⁴I_15/2) and green (515–560 nm; ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) wavelengths was observed. The most intense luminescence and the longest luminescence emission lifetime were obtained with the material annealed for 12 h at 177 °C with 1.8 MPa pressure due to the predominance of the well-crystallized hexagonal form of NaRF₄ (R: Y, Yb, Er).