Luminescence sensitization in Nd-Cr-Ce doped yttrium aluminates

Energy transfer from Ce to Cr in YAG is radiative and relatively inefficient. If excited below 500 nm, the opposite transfer is dominant. YAP: Ce, Cr showed relatively efficient CeCr transfer only. The sensitization of Nd³⁺ luminescence by Ce³⁺ ions depends on the overlap of the Ce³⁺ emission band with Nd³⁺ absorption lines. Cr³⁺Nd³⁺ transfer is characterized by an expressive non-radiative portion. It is inefficient in YAG but very efficient in YAP. No UV-induced colour centres were found in YAG: Nd, Cr grown under Ar-H₂ atmosphere and doped with 10^–3 wt. % Cr, but at a higher Cr concentration anomalous absorption between UV absorption edge and 650 nm was stabilized. Ce³⁺ admixture in YAG:Nd, Cr and/or reducing treatment of the crystals facilitate the decomposition of the centres. The decomposition is accompanied with a strong Nd³⁺ luminescence. Therefore, YAG: Nd, Ce, Cr is an advisable active laser material. On the other hand the same centre in YAP: Nd, Cr seemed to be more stable even in the presence of cerium ions.     

Luminescence properties of highly Cr co-doped Nd:YAG powder produced by sol-gel method

We examined luminescence properties of highly chromium co-doped Nd:YAG powders fabricated by the sol-gel method. Though the maximum luminescence intensity of Cr:YAG was at 3.0 mol% of Cr³⁺ concentration, we found that the enhancement effect on Nd:YAG by co-doping Cr³⁺ was continued until 6.0 mol% of Cr³⁺ concentration. This phenomenon is well-explained by a simple energy transfer model derived from the rate equations between Cr³⁺ and Nd³⁺. The enhancement of sensitization for Nd³⁺ activator by high co-doped Cr³⁺ is very effective for making a miniaturized or thin film-type solar laser.     

The optical properties and laser characteristics of Cr and Nd co-doped Y3Al5O12 ceramics

We have fabricated Cr³⁺ and Nd³⁺ co-doped YAG (Cr;Nd:YAG) ceramics, and investigated their optical properties and laser characteristics. The Cr;Nd:YAG has two broad absorption bands at around 440 nm (⁴A₂→⁴T₁) and 600 nm (⁴A₂→⁴T₂) respectively, caused by Cr³⁺ ions. In the case of pumping at 440 nm, the maximum effective lifetime of the Cr;Nd:YAG was 737 μs with a 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG sample. Cr³⁺ ions take a role of an effective sensitizer to convert the UV light of flashlamp. For single-shot laser operation, a 10.4 J output energy at 1064 nm was obtained with 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG ceramic rod with a laser efficiency of 4.9%. The laser efficiency was found to be more than twice that of a 1.0 at % Nd³⁺:YAG ceramic rod.     

Fluorescence decays and lifetimes of Nd3+, Ce3+ and Cr3+ in YAG

The present paper summarizes results of detailed studies of fluorescence decays and lifetimes of Nd³⁺, Ce³⁺ and Cr³⁺ carried out on a large group of YAC.: Nd, Ce and YAC.: Nd, Ce, Cr single crystals. The average and local lifetimes (mainly for⁴F_3/2 state of Nd³⁺) of these ions are given and an influence of various processes (energy transfers, cross-relaxation, nonequivalent centres etc.) on their decays are qualitatively discussed.The authors are grateful to J. Kvapil of Monokrystaly Turnov for supplying them with the samples and for many fruitful discussions.     

Absorption background and laser properties of YAP:Nd

YAP:Nd laser crystals suffer to a greater extent than YAG:Nd from colour centres formation. Stable brownish-yellow or green colourations are evoked by non-oxidizing treatment at high (>1500 °C) temperature. The former colouration may be attributed to holes in the oxygen neighbourhood of Y³⁺ at Al sites, the latter to the F⁺ centres. Brownish-red colouration of less stability is induced by optical pumping of Nd³⁺ containing crystals. It may be attributed to holes in oxygen neighbourhood of Nd³⁺.Dependences of the colourations on the preparation methods are described. YAP:Nd,Zr laser rods, oxygen annealing of which was followed by medium (1100–1400 °C) temperature treatment in vacuum or hydrogen showed no anomalous colouration and extremely low losses at Nd³⁺ emission wavelength independent of pumping power. Using such rods, an overall efficiency of 2·5% and a slope efficiency of 3·0% in CW lasers were reached.     

Identification of trace impurities in pure and doped YAlO3 and Y3Al5O12 crystals by their fluorescence and by the EMA method

Trace uncontrolled impurities as Ce³⁺, Cr³⁺, Eu³⁺ and Nd³⁺ were detected in YAlO₃ and YAlO₃: Cr crystals from their fluorescence by high sensitive photon counting detection. The concentrations of Ce, Cr, Eu, Nd and some other impurities (Tm, Ho, Mn, Mg, Fe) were also determined by electron beam excited X-ray microanalysis (abbr. EMA) in YAlO₃ and Y₃Al₅O₁₂ crystals (pure or doped). Both the methods (fluorescence detection and EMA) are compared, fluorescence properties of some trace impurities were determined and their influence on local distribution and transfer processes (Ce³⁺Nd³⁺, Cr³⁺ Nd³⁺) in these crystals are discussed.The authors are grateful to J. Kvapil, Jos. Kvapil and K. Blaek from Preciosa a.s., Division Monokrystaly, Turnov, Czech Republic, for supplying us with YAlO₃ and Y₃Al₅O₁₂ single crystals.     

Luminescence enhancement in (Nd+Ce) doped SiO2 : Al2O3 sol–gel glasses

An enhancement in NIR luminescence from Nd³⁺-doped Ce³⁺ co-doped SiO₂+Al₂O₃ sol–gel glasses has been observed. The lasing transition (⁴F_3/2→⁴I_11/2) at 1072 nm from the dual rare-earth Nd³⁺+Ce³⁺-doped glasses has shown an emission strength of about five times that of the single rare-earth ion Nd³⁺-doped glass. From the measurement of lifetimes of the transition at 1072 nm, the transfer rate (W_tr), critical distance (R₀) and energy transfer efficiency (η) of the neodymium glasses have been calculated.     

Passively Q-switched self-frequency doubling Nd:Ca4GdO(BO3)3 laser with Cr:YAG saturable absorber

Nd³⁺ : Ca₄GdO(BO₃)₃, known as Nd : GdCOB, is a new self-frequency doubling laser crystal. Using Cr⁴⁺ : YAG as passive Q-switch, we have realized the Q-switched laser running at 0.53 μm with an Nd : GdCOB crystal. Meanwhile, the pulse width, the single pulse energy and the repetition rate under different small-signal transmission of Cr⁴⁺ : YAG and different pump conditions are measured and the numerical solutions of the coupling wave rate equations agree with the experimental results.     

Optical characteristics of Cr and Nd codoped Y3Al5O12 ceramics

The optical characteristics of Cr³⁺ and Nd³⁺ codoped Y₃Al₅O₁₂ (YAG) ceramics are measured. These measurements are done using two pumping sources, a 808 nm laser diode (LD) and a Xe short-arc lamp, to simulate solar radiation. The specimens used are 0.1%Cr³⁺/1.0%Nd³⁺ and 3.0%Cr³⁺/1.0%Nd³⁺ (atomic%) codoped YAG ceramics. A Nd:YAG crystal doped with 1.0%Nd³⁺ is used as a reference. The saturation intensities of the Cr/Nd:YAG ceramics pumped by the LD are the same as that of the Nd:YAG crystal, while they are higher when they are pumped by the Xe lamp. The saturation intensities are for the 0.1% Cr-doped ceramic and for the 3.0%Cr-doped ceramic. The small signal gains of the 0.1%Cr-doped and 3.0%Cr-doped ceramics are measured and found to be 1.8 times and 7.0 times higher than that of Nd:YAG for the same intensity of solar pumping, respectively. The quantum efficiency of energy transfer from Cr³⁺ to Nd³⁺ is estimated to be 0.88±0.09 for the 0.1%Cr-doped ceramic and 0.67±0.08 for the 3.0%Cr-doped ceramic.     

Energy transfer in YAlG:Nd codoped with Ce

Laser excited luminescence has been used to study an energy transfer between Ce³⁺ and Nd³⁺ ions in YAlG:Nd,Ce laser crystal with varying small Ce concentrations. Radiative Ce³⁺Nd³⁺ energy transfer dominates in the studied single crystal samples but this process can also be accompanied by multistep transfer mechanisms (for example by (Ce³⁺Ce³⁺)_n Nd³⁺ transfer mechanism). The Ce³⁺Nd³⁺ radiative energy transfer improves pumping of green and yellow excitation lines in YAlG:Nd,Ce laser rods because the contribution of the additional transfer pumping of Nd³⁺ ions from Ce³⁺ ions is more than three times greater than should be expected from concentration differences between Nd and Ce. This favourable behaviour is explained from high quantum efficiency of Ce³⁺ emission and higher Ce³⁺ absorption cross sections in comparison with the Nd³⁺ ones (more than one order of magnitude difference).This work was done in cooperation with Monokrystaly Turnov, Research Institute for Single Crystals. The author is grateful to Jos. Kvapil and J. Kubelka for supplying him with samples used in this work. He would like to acknowledge many fruitful discussions with J. Kvapil and K. Blaek of Monokrystaly Turnov.     

Laser and absorption saturation measurements of Cr crystals, pumped by broadband pulsed 940 nm radiation

The characteristics of a 940 nm pumped Cr⁴⁺:forsterite laser have been investigated using a pulsed colour centre laser as the excitation source. Laser threshold, slope efficiency and temporal behaviour have been determined for high and low Cr⁴⁺ doped material. 940 nm pumping is found to be more efficient than 532 and 730–770 nm excitation. Discrepancies with 1064 nm pumping are attributed to excited state absorption. Absorption saturation measurements have been used to assess the potential applications of Cr⁴⁺:forsterite, Cr⁴⁺:YAG and Cr⁴⁺: Lu₃A1₅O₁₂ (LuAG) as passive Q-switches for Nd lasers in the 940 nm region.     

Gamma-ray irradiation effect on the absorption and luminescence spectra of Nd:GGG and Nd:GSGG laser crystals

Laser crystals Nd³⁺:Gd₃Ga₅O₁₂ (Nd:GGG) and Nd³⁺:Gd₃Sc₂Ga₃O₁₂ (Nd:GSGG) were grown by Czochralski method. The influence of gamma-ray irradiation on their absorption and luminescence spectra has been investigated. Two additional absorption (AA) bands induced by gamma-ray irradiation appear in the spectra of Nd:GGG crystal while only a very weak AA band appears for the Nd:GSGG crystal. This indicated that Nd:GSGG crystal has stronger ability to resist the color center formation by irradiation. The intensity of the excitation and emission spectra of Nd:GGG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, a luminescence strengthening effect was observed in Nd:GSGG crystal after exposure to the same irradiation dose. The results showed that the Nd:GSGG crystal is a promising candidate used under radiation environments such as in outer space.     

The luminescence efficiency of YAG: Ce phosphors

The luminescence intensity of Yttrium aluminium garnet activated by the Ce³⁺ (YAGCe³⁺) under cathode-ray excitation depends on the preparation method and content of some dopants. Samples containing Fe, Pt, Ir or some colour centre, respectively, show relatively low luminescence. The maximum luminescence intensity was obtained with the Czochralski method grown single crystals in 98% Ar+2% H₂ atmosphere which were sensitized by oxygen annealing followed by treatment at 1500 °C in molybdenum container using a wet hydrogen atmosphere.     

Angular dependence of the superexchange interaction Fe3+-O2−-Cr3+

The super-exchange interaction parametersI(Fe, Cr) of Fe³⁺ and Cr³⁺ in iron doped rate-earth orthochromitesRCr_0.99Fe_0.01 O₃ (R=La, La_0.5Nd_0.5, Nd, Sm, Gd, Dy, Y, Er, Yb or Lu) have been obtained from⁵⁷Fe magnetic hyperfine structure measurementsvia the Mössbauer effect.The dependence of the experimental valuesI(Fe, Cr) on the Fe–O–Cr average superexchange angle (depending upon the relative size of the rare-earth (RE) ionR ³⁺) is well described by the equationI(d⁵, d ^N ) = _N + _N cos + _N cos² .Within the accessible range of super-exchange angles 142°156°, the Fe³⁺–O^2––Cr³⁺ interaction is negative (antiferromagnetic). However, a theoretical analysis predicts a sign reversal forI(Fe, Cr.) at about 162° and thus ferromagnetic character of the interaction between 162° and 180°.The spin-only super-exchange interaction integrals fore _g andt _2g electrons, separately, are also calculated. Their angular dependence is accounted for by the behaviour of the antiferromagnetic kinetic and ferromagnetic potential exchange which are of different character when passing from 180° to 90° super-exchange geometry. The magnitude and the sign of the spin-only super-exchange integral for an arbitrary 3d cation, pair is predicted.     

Nd3+ near UV and visible fluorescence in YAP:Nd

The present paper summarizes detailed investigations of Nd³⁺ fluorescence spectra in YAP:Nd laser crystal in the broad spectral range of 370–1100 nm at liquid nitrogen temperature. Especially, Nd³⁺ near UV and visible fluorescence spectra were studied for the first time in this crystal. The Nd³⁺ near UV and visible fluorescence spectra of this crystal consist of many narrow lines (up to 50). The Nd³⁺ near UV and visible fluorescence lines arise mainly from⁴D_3/2 and²P_3/2 Nd³⁺ terms (transitions from⁴D_3/2,²P_3/2 to lower lying Nd³⁺ levels are responsible for their appearance). At room temperature the fluorescence spectra consist of broad bands with narrow lines (mainly⁴D_3/2⁴F_3/2,⁴F_5/2 and²H_9/2 transitions).     

Characteristics of a passively Q-switched Nd:NaY(WO4)2 laser with Cr:YAG saturable absorber

By using xenon flash lamp as pump source and Cr⁴⁺:YAG as passive Q-switcher, we have performed the Q-switched laser operation at 1.06 μm with an Nd³⁺:NaY(WO₄)₂ (known as Nd:NYW) crystal. Meanwhile, the pulse width, the single pulse energy and the repetition rate under different small-signal transmissions of Cr⁴⁺:YAG and different reflectivities of output reflector are measured, and the numerical solutions of the coupling wave rate equations agree with the experimental results.     

Near infrared fluorescence and energy transfer in Ce/Nd Co-doped CaxSr1−xS

Novel near infrared (NIR) phosphors Ca_xSr_1−xS:Ce³⁺,Nd³⁺ were synthesized by a solid state reaction. The NIR emission was realized through an efficient absorption by the allowed 4f-5d transition of Ce³⁺ and efficient energy transfer to Nd³⁺ via well-matched energy levels. Ce³⁺ and Nd³⁺ content in CaS/SrS was optimized. It was found that CaS:Ce³⁺,Nd³⁺ gave much stronger NIR emission than that of SrS:Ce³⁺,Nd³⁺. Further studies on Ca_xSr_1−xS:Ce³⁺,Nd³⁺ indicated that both visible emission of Ce³⁺ and NIR emission of Nd³⁺ were observably affected by Ca/Sr ratio. The energy transfer efficiency, which can be estimated from fluorescence lifetime of Ce³⁺, increased from 52% to 74% for the Ca_xSr_1−xS:Ce³⁺,Nd³⁺ (x=0 to 1) series, accompanied with a shift of maximal emission wavelength of Ce³⁺ from 482 to 505 nm. The results showed that overlap between emission spectrum of Ce³⁺ and excitation spectrum of Nd³⁺ plays an important role in the energy transfer efficiency, and Ce³⁺ emitting in green or blue-greenish region sensitized the Nd³⁺ NIR fluorescence emission more efficiently than that in blue region.     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000     

Energy transfer from Ce3+toNd3+ in pentaphosphate crystals

An excitation band at 300 nm corresponding to Ce³⁺absorption is observed in pentaphosphate crystals containing Ce³⁺ and Nd³⁺ when the Nd³⁺ luminescence is monitored. The decay of excitation of Ce³⁺ in crystals of pure cerium pentaphosphate, CeP₅O₁₄, follows single exponential kinetics with a 22 ± 2 nsec lifetime. In Ce_0.5Nd_0.5P₅O₁₄ crystals, the Ce³⁺ lifetime is shortened to 3.8 ± 0.4 nsec as a result of efficient nonradiative energy transfer to the Nd³⁺ ions.     

PbO–Bi2O3–Ga2O3–BaO glasses doped by Er as novel materials for IR emission

Infra-red luminescence (at wavelengths about 1600 and 2500 nm) from Er³⁺ ions embedded in PbO–Bi₂O₃–Ga₂O₃–BaO glass hosts is reported for room and helium liquid temperatures. The substantial influence of energy transfer processes between the host and Er³⁺ ions is shown experimentally through the dependences of photoluminescence on light polarization and excitation wavelength. Only the application of the polarized pumping YAG–Nd laser beam (λ=1060 nm) stimulates substantial luminescence with quantum efficiency up to 24%. The role of phonon-relaxation subsystem in the observed luminescence is discussed.