Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

Simultaneous dual-wavelength oscillation at 1357 nm and 1444 nm in a Kr-flashlamp pumped Nd:YAG laser

A Nd:YAG laser pumped by a Kr-flashlamp with simultaneous dual-wavelength operation at 1357 nm (⁴F_3/2 → ⁴I_13/2(R₁ → X₄)) and 1444 nm (⁴F_3/2 → ⁴I_13/2(R₁ → X₇)) is demonstrated and its characteristics was analyzed. The output energy of 82 mJ at 1357 nm and 138 mJ at 1444 nm were achieved simultaneously with the maximum electrical input energy of 44 J. Stability of the output energy in the dual-wavelength operation was 1.41% at the maximum input energy of 44 J. However, the stabilities at each wavelength in the dual-wavelength operation showed much lower stability.     

Synthesis and optical properties of KZnLa0.99Nd0.01(VO4)2 triple vanadate(V)—New promising laser materials

In an attempt to find a neodymium-vanadate system with long lifetime of ⁴F_3/2 level and relatively strong ⁴F_3/2→⁴I_11/2 emission for laser applications, the optical properties of Nd³⁺ in a new KZnLa(VO₄)₂ host is reported. The crystalline samples were obtained at 900 °C in air. The samples were crystallized in monoclinic system and were isostructural with KZnLa(PO₄)₂. KZnLa_0.99Nd_0.01(VO₄)₂ strongly emits in the near infrared range with the maxima at 871.6 and 1057 nm upon excitation through the ⁴F_5/2 level (808 nm) or by the charge transfer bands of VO₄³⁻. The lifetime of ⁴F_3/2 level of Nd³⁺ ion is larger than that observed in other neodymium-vanadates systems.     

Diode pumped Nd:GSAG and Nd:YGG laser at 942 and 935 nm

Two new Nd³⁺ doped crystals show laser activity between the ⁴F_3/2 and ⁴I_9/2 levels. Diode pumped emission of Nd:GSAG at 942 nm wavelength with 950 mW output power and 14% optical to optical efficiency as well as laser emission of Nd:YGG at 935 nm with 700 mW output power and 11% efficiency have been obtained. These wavelengths are useful for water vapour absorption measurements.     

High-efficiency direct-pumped Nd:YVO4-LBO laser operating at 671 nm

The continuous-wave high-efficiency laser emission from Nd:YVO₄ at the fundamental wavelength of 1342 nm and its 671 nm second harmonic obtained by intra-cavity frequency doubling in an LBO nonlinear crystal are investigated under pumping by diode laser at 880 nm (on the ⁴F_3/2→⁴I_13/2 transition). The end-pumped Nd:YVO₄ crystal yielded a continuous-wave output power of 9.6 W at 1342 nm for 18.9 W of absorbed pump power. The slope efficiency measured with respect to the absorbed pump power is 60%. An output of 5.5 W at 671 nm was obtained by frequency doubling, resulting in an optical-to-optical efficiency with respect to the absorbed pump power of 29%. Comparative results obtained for the pump with a diode laser at 808 nm (on the ⁴F_5/2→⁴I_13/2 transition) are given in order to prove the advantages of the 880 nm wavelength pumping.     

Diode-pumped passively mode-locked Nd:GdVO4 laser at 912 nm

We have demonstrated the stable mode-locked Nd:GdVO₄ laser operating on the ⁴F_3/2-⁴I_9/2 transition at 912 nm. With a four-mirror-folded cavity and a semiconductor saturable absorber mirror for passive mode-locking, we have gained 6.5 ps laser pulses at a repetition rate of 178 MHz. The laser is diode-end-pumped, and the total output power from the out coupler is 128 mw at an incident pump power of 19.7 W.     

The effects of Li on the near-infrared luminescence properties of Nd/ Li codoped Y2O3 nanocrystals

Nd³⁺/ Li⁺ codoped Y₂O₃ nanocrystals were synthesized by glycine combustion method. The codoping of Li⁺ ions can lead to about twice enhancement of the near-infrared luminescence for the three spectral regions, which correspond to the ⁴F_3/2 → ⁴I_9/2, ⁴F_3/2 → ⁴I_11/2 and ⁴F_3/2 → ⁴I_13/2 channels of Nd³⁺. The enhancement could be attributed to the improved morphology, the modification of the local symmetry around Nd³⁺ ions and the reducing number of OH⁻ groups by codoping with Li⁺ ions.     

Highly efficient Nd:GdVO4/BiBO laser at 456 nm under direct 880 nm diode laser pumping

The continuous-wave high-efficiency laser emission of Nd:GdVO₄ at the second-harmonic of 456 nm obtained by intracavity frequency doubling with an BiB₃O₆(BiBO) nonlinear crystal is investigated under pumping by diode laser at 880 nm into emitting level ⁴F_3/2. About 3.8 W at 456 nm with M² = 1.4 was obtained from a 5 mm-thick 0.4 at.% Nd:GdVO₄ laser medium and a 12 mm-long BiBO nonlinear crystal in a Z-type cavity for 13.9 W absorbed pump power. An optical-to-optical efficiency with respect to the absorbed pump power was 0.274. Comparative results obtained for the pump with diode laser at 808 nm, into the highly-absorbing ⁴F_5/2 level, are given in order to prove the advantages of the 880 nm wavelength pumping.     

Efficient blue upconversion emission due to confined radiative energy transfer in Tm-Nd co-doped Ta2O5 waveguides under infrared-laser excitation

Intense blue upconversion emission at 480 nm has been obtained at room temperature in Tm³⁺-Nd³⁺ co-doped Ta₂O₅ channel waveguides fabricated on a Si substrate, when the sample is excited with an infrared laser at 793 nm. The upconversion mechanism is based on the radiative relaxation of the Nd³⁺ ions (⁴F_3/2 → ⁴I_11/2) at about 1064 nm followed by the absorption of the emitted photons by Tm³⁺ ions in the ³H₄ excited state. A coefficient of energy transfer rate as high as 3 × 10⁻¹⁶ cm³/s has been deduced using a rate equation analysis, which is the highest reported for Tm-Nd co-doped systems. The confinement of the 1064 nm emitted radiation in the waveguide structure is the main reason of the high energy transfer probability between Nd³⁺ and Tm³⁺ ions.     

Conversion of infrared radiation into visible emission in NaY(WO4)2:Yb, Ho crystal

The spectroscopic characteristics and fluorescence dynamics for Yb³⁺/Ho³⁺:NaY(WO₄)₂ crystal were investigated. The parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the stimulated emission cross sections have been calculated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The energy transfer efficiency from Yb³⁺ to Ho³⁺ was 65.85%. The green emission (530-570 nm) corresponding to (⁵F₄, ⁵S₂)→⁵I₈ transition, red emission (640-670 nm) due to ⁵F₅→⁵I₈ transition and NIR emission (740-770 nm) attributed to (⁵F₄, ⁵S₂)→⁵I₇ transition were observed on 974 nm excitation at room temperature. Under low pump power, the intensity of green light emission is weaker than that of the red light, while under high pump power, the case is on the contrary. The upconversion is based on the two-photon process either the energy transfer from Yb³⁺ ions or by the excited state absorption. The proposed mechanisms of upconversion emissions were provided.     

Experimental investigation on the upconversion mechanism of 754 nm NIR luminescence of Ho/Yb:Y2O3, Gd2O3 under 976 nm diode laserexcitation

Upconversion (UC) spectra of Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics were obtained under the excitation of a 976 nm diode laser. Systematic experimental studies, including power dependence, luminescence lifetime, and the intensity ratio σ for the green to NIR emissions, were carried out in order to confirm the UC mechanism of Ho³⁺ ions. Our results demonstrated that the NIR emission was associated with the ⁵F₄/⁵S₂→⁵I₇ transition of Ho³⁺ ions without the contribution of the ⁵I₄→⁵I₈ transition for Ho³⁺/Yb³⁺ codoped Y₂O₃ and Gd₂O₃ bulk ceramics. Additionally, population saturation in the ⁵I₇ energy level had been observed in Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics. All experimental observations can be well explained by the steady-state rate equations.     

Ultraviolet upconversion luminescence in Er-doped Y2O3 excited by 532 nm CW compact solid-state laser

Ultraviolet upconversion emissions at 262, 276, 308 and 320 nm were observed from Er³⁺-doped Y₂O₃ with a 532 nm continuous wave compact solid-state laser excitation. Power-dependence analysis demonstrates that two-photon upconversion process populates the ⁴D_5/2, ²H_9/2 and ²P_3/2 states. The energy transfer upconversion (ETU) plays an important role in populating ⁴D_5/2 and ²P_3/2 states. It appears that ²P_3/2 state population originates from ETU ²H_11/2+²H_11/2→⁴I_13/2+²P_3/2, moreover, a subsequent excited state absorption (ESA) from the ⁴I_9/2 level.     

Simultaneous dual-wavelength laser operation at 1342 and 946 nm in two laser crystals and their sum-frequency mixing

A sum-frequency yellow-green laser at 554.9 nm is reported by this paper, 946 nm wavelength is obtained from ⁴F_3/2-⁴I_9/2 transition in Nd:YAG and 1342 nm wavelength is obtained from ⁴F_3/2-⁴I_13/2 transition in Nd:YVO₄. Using a doubly folded-cavity type-II critical phase matching KTP crystal intra cavity to make 946 nm laser from Nd:YAG and 1342 nm laser from Nd:YVO₄ frequency summed, with incident pumped power of 30 W in Nd:YAG and 20 W in Nd:YVO₄, TEM₀₀ mode yellow-green laser at 554.9 nm at 1.15 W is obtained and its M² factor is less than 1.22. The experimental results show that the Nd:YAG and Nd:YVO₄ crystals intra-cavity sum-frequency mixing is an effective method for yellow-green laser and it can be applied to other two laser crystals to obtain more all-solid-state lasers with different wavelengths.     

Upconversion luminescence and kinetics in Er:YAlO3 under 652.2 nm excitation

Ultraviolet and visible upconversion properties of Er³⁺ in YAlO₃ were investigated following 652.2 nm excitation of the multiples ⁴F_9/2. The luminescence and excitation spectra were recorded. Ultraviolet (326-342 and 354-359 nm), violet (405-420 nm), blue (436-442 nm) and green (525-575 nm) upconversion and infrared downconversion luminescence were simultaneously observed. The intense green luminescence corresponds to the emissions from the thermal coupled ⁴S_3/2 and ²H_11/2 bands and ²G_9/2 level. Energy transfer upconversion processes were proposed to explain the upconversion phenomena. The luminescence kinetics was discussed in detail by the analyses of fluorescence decay curves.     

Optical absorption and emission properties of Nd in TeO2-WO3 and TeO2-WO3-CdO glasses

Effects of WO₃ and CdO on the spectroscopic properties of Nd³⁺ doped tellurite glasses were investigated. The optical band gaps and Urbach energies of the samples were determined using the dependence of the absorption coefficient on the photon energy. The Urbach energies were found to vary from 0.18 to 0.25 eV as the WO₃ content in the binary glasses decreased from 20.0 to 10.0 mol% while the optical band gap of the same glasses did not show an appreciable dependence on the glass composition. Judd-Ofelt (Ω_t) parameters were calculated from the optical absorption spectra measured at room temperature. In all the glasses the J-O parameters follow the same trend as Ω₂>Ω₆>Ω₄. The J-O intensity parameters were used to compute the radiative properties such as the radiative transition probabilities (A_ed), branching ratios (β) and radiative lifetimes (τ_r) for all the possible fluorescence bands. The fluorescence spectra obtained upon 805.2 nm excitation exhibited an intense emission band centered at 1064 nm (⁴F_3/2→⁴I_11/2) and two weak bands at 910 nm (⁴F_3/2→⁴I_9/2), and 1340 nm (⁴F_3/2→⁴I_13/2). The stimulated emission cross-section for the 1064 nm emission was determined using the emission spectra. The highest gain bandwidth (σ_e×Δλ_P) was determined to be 155.4 for the 0.79TeO₂-0.15WO₃-0.05CdO ternary glass composition, which could be more useful as promising material for the design and development of fiber amplifiers and lasers.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

Optical and fluorescence spectroscopy of Eu2O3-doped P2O5-K2O-KF-MO-Al2O3 (M = Mg, Sr and Ba) glasses

Fluorophosphate glasses of composition, P₂O₅ + K₂O + KF + MO + Al₂O₃ + xEu₂O₃ (M = Mg, Sr and Ba; x = 0.01, 0.05, 0.1, 1.0, 2.0, 4.0 and 6.0 mol%) were prepared and characterized their optical properties. Crystal-field (CF) analysis revealed a relatively weak CF strength around Eu³⁺ ions in the Ba based fluorophosphate glasses. The Judd-Ofelt parameters have been estimated from the oscillator strengths of ⁷F₀ → ⁵D₂, ⁷F₀ → ⁵D₄ and ⁷F₀ → ⁵L₆ absorption transitions of Eu³⁺ ions and were used to evaluate the radiative properties of the ⁵D₀ → ⁷F_J (J = 0-4) transitions. Considerable variation has been observed in the relative intensity ratio of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ transitions of Eu³⁺ ions due to change in the alkaline earth metal ions. The decay of the ⁵D₀ level shows single exponential and less sensitive to Eu³⁺ ions concentration as well as MgO/SrO/BaO modifiers.     

Strong infrared-to-visible frequency upconversion in Er-doped Sr2CeO4 powders

Efficient upconversion (UC) luminescence is demonstrated in Er³⁺:Sr₂CeO₄ powders prepared by combustion synthesis and exposed to near-infrared (∼975 nm) radiation. The UC emission lines observed at ∼530, ∼550 and ∼665 nm correspond, respectively, to ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 4f-4f transitions of Er³⁺. X-ray powder diffraction data showed that the SrCO₃ phase (impurity) is dramatically reduced when Sr²⁺ is partially substituted by Mg²⁺ ions. The UC phenomenon was investigated by use of continuous wave and pulsed laser excitation and the UC mechanism was attributed to energy transfer between excited Er³⁺ ions.     

Diode-pumped passively Q-switched 912 nm Nd:GdVO4 laser and pulsed deep-blue laser by intracavity frequency-doubling

A diode-end-pumped passively Q-switched 912 nm Nd:GdVO₄/Cr⁴⁺:YAG laser and its efficient intracavity frequency-doubling to 456 nm deep-blue laser were demonstrated in this paper. Using a simple V-type laser cavity, pulsed 912 nm laser characteristics were investigated with two kinds of Cr⁴⁺:YAG crystal as the saturable absorbers, which have the different initial transmissivity (T_U) of 95% and 90% at 912 nm. When the T_U = 95% Cr⁴⁺:YAG was used, as much as an average output power of 2.8 W 912 nm laser was achieved at an absorbed pump power of 34.0 W, and the pulse width and the repetition rate were ∼ 40.5 ns and ∼ 76.6 kHz, respectively. To the best of our knowledge, this is the highest average output power of diode-pumped passively Q-switched Nd³⁺-doped quasi-three-level laser. Employing a BiBO as the frequency-doubling crystal, 456 nm pulsed deep-blue laser was obtained with a maximum average output power of 1.2 W at a repetition rate ∼ 42.7 kHz.