具有高机械强度的掺Er3+∶TeO2-Nb2O5玻璃的光谱性质研究

熔制了掺铒碲铌玻璃样品(100-XTeO2-XNb2O5(X=5,10,15,20 mol%),测试了其密度、折射率、转变温度、析晶温度、维氏机械强度、吸收光谱、荧光光谱、荧光寿命等参量。利用Judd-Ofelt和McCumber理论分别计算了铒离子强度参量Ωt (t=2, 4, 6)和受激发射截面σemi的大小,研究了掺铒碲铌玻璃样品光谱参量对Nb2O5成分的依赖性,并与典型的碲锌钠玻璃（75TeO2-20ZnO-5Na2O）在热学、机械强度、光谱性质和放大品行四个方面进行了比较.     

Combined 17O NMR and 11B-31P double resonance NMR studies of sodium borophosphate glasses

17O enriched sodium borophosphate glasses were prepared from isotopically enriched NaPO3 and H3BO3. These glasses have been studied by 17O, 11B and 31P NMR including 17O and 11B multiple quantum magic angle sample spinning (MQMAS), 11B-31P heteronuclear correlation (HETCOR) NMR and 11B{31P} rotational echo double resonance (REDOR). For comparison, the crystalline borophosphates BPO4 and Na5B2P3O13 were included in the investigations. The latter compound shows three sharp 31P resonances at -0.2, -2 and -8 ppm and two BO4 sites that can only be resolved by MQMAS. The 17O NMR spectra were recorded using both the static echo method at medium magnetic field (9.4 T) as well as MAS and MQMAS methods at high field (17.6 T). In total, five oxygen sites were identified in these borophosphate glasses: P-O-P, Na...O-P, P-O-B, B-O-B, Na...O-B. However, these five sites are not present simultaneously in any of the glasses. The 17O MQMAS spectra prove that P-O-B links play a major role in borophosphate glasses. These results are confirmed by the complementary 11B MAS spectra that show the presence of asymmetric and symmetric trigonal groups BO3a and BO3s and two tetrahedral BO4 units. 11B{31P} REDOR NMR is used to give independent information to assign the 11B lines to structural units present in the glasses. These REDOR measurements reveal that B-O-P bonds are present for each borate unit, including the BO3 groups. Particularly, a structural proposal for the two different BO4 resonances is given in terms of a different number of bonded phosphate tetrahedra. The 31P MAS spectra are usually broad and not well resolved. It is shown by 11B-31P HETCOR NMR that a possible structural assignment of a 31P signal at about -20 ppm to Q2 units as in binary sodium phosphate glasses is wrong and that the phosphate tetrahedron belonging to this resonance must be connected to borate groups.     

Non-bridging oxygens in borate glasses: characterization by 11B and 17O MAS and 3QMAS NMR

The concentrations of non-bridging oxygens (NBO) in oxide glasses has major effects on their properties and on those of their precursor glass melts. In borate and borosilicate glasses, the presence of NBO bonded to boron has generally been inferred from 11B NMR spectra and mass balance considerations. Here we report the direct observation of such NBO using 17O MAS and 3QMAS techniques, and compare estimates of their populations with those derived from high-resolution 11B MAS spectra. For the latter, two independent methods are used, based on the ratios of trigonal to tetrahedral boron and on the concentrations of trigonal boron sites with large quadrupolar asymmetry parameters. We include data on crystalline sodium pyroborate (Na4B2O5) and sodium metaborate (NaBO2), and several sodium and barium borate glasses. 17O chemical shifts and quadrupolar coupling constants for NBO bonded to boron vary considerably depending on their coordination environment. In borosilicates, peaks for this species may be hidden by overlap with B-O-Si or Si-O-Si resonances.     

Er3+/Yb3+共掺碲钨酸盐玻璃的热稳定性和1.5μm波段的光谱性质

制备了Er³⁺/Yb³⁺共掺的碲钨酸盐玻璃样品,TeO₂-WO₃-R_mO_n(R_mO_n=PbO,BaO,La₂O₃,Bi₂O₃),研究了样品的热稳定性和1.5μm波段的光谱性质。碲酸盐中引入WO₃的目的是为提高基质的声子能量,使Er³⁺离子⁴I_13/2→⁴I_15/2的多声子弛豫速率增加,从而提高⁴I_13/2能级上的Er³⁺离子数,这对提高1.5μm处的荧光强度有利,另外加入WO₃也能提高碲酸盐玻璃的抗析晶能力。测试了样品的FT-IR光谱,发现碲钨酸盐玻璃样品中存在着TeO₄、TeO₃、WO₄和WO₆结构体。周围环境的不对称性导致Er³⁺在1.5μm处的光谱有非均匀的展宽和大的受激发射截面。Er³⁺在70TeO₂-20WO₃-10Bi₂O₃玻璃中⁴I_13/2→⁴I_15/2能级发射的荧光半峰全宽(FWHM)为77nm,应用McCumber理论计算的受激发射截面(σ^peak)为1.03×10^-20cm²。其FWHM×σ_peak乘积远大于掺Er³⁺的铋酸盐、磷酸盐、碲酸盐和硅酸盐玻璃,说明碲钨酸盐玻璃是一种制备宽带光纤放大器优良基质材料。     

TeO2-Nb2O5-YF3 玻璃系统的形成区及性质研究

制备了一种新型的氧卤碲酸盐玻璃:TeO2-Nb2O5-YF3,给出并研究了TeO2-Nb2O5-YF3三元系统的玻璃形成范围。测试了玻璃的密度、折射率、差热(DTA)、拉曼光谱、红外透射光谱以及紫外吸收光谱,通过光谱分析研究了组分含量的变化对玻璃结构及红外透射特性的影响。实验结果表明,TeO2-Nb2O5-YF3玻璃系统具有优良的成玻璃性能和热稳定性等特性,而且在2.8~3.3μm区域内无明显的[OH]基团吸收,在中红外3~5μm区域具有优良透射性能,因此在中红外透射方面具有潜在应用价值。     

Upconversion Fluorescence of Er_2O_3 Doped BaF_2-TeO_2 and PbF_1-TeO_2 Oxyhalide Tellurite Glasses

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稀土掺杂P2O5-Al2O3-BaO玻璃的制备及其结构研究

稀土掺杂磷酸盐玻璃具有优异的光学和光谱特性,在激光介质、有色滤光材料等领域中有着重要的应用。在P2O5_Al2O3_BaO_Sm2O3(PABS)玻璃形成能力研究的基础上,借助MAS NMR、红外光谱等分析手段,研究了玻璃的结构、玻璃组成与热处理等对玻璃结构的影响。结果表明:不同组成PAB(S)玻璃的31P MAS NMR谱在-20ppm~-25ppm范围内均存在单一的特征信号峰,对应于磷氧多面体[PO4]的Q2型结构;在18ppm、-12ppm和-36ppm处27Al的MAS NMR谱的三个特征信号峰分别对应于27Al的[AlO5][、AlO6]、[AlO6]配位结构,稀土离子的掺入以及热处理均使得[AlO6]向[AlO5]转变;玻璃的网络结构主要由Q2型[PO4]、[AlO5]和[AlO6]构成,并P_O_P、P_O_Al的形式相连接。玻璃在1383 cm-1处出现的吸收峰可能是玻璃结构中形成了P_O_Sm键所致。     

Spectroscopic properties of Yb~(3+)-doped TeO_2–BaO–BaF_2–Nb_2O_5-based oxyfluoride tellurite glasses

A series of oxyfluoride glasses with the compositions of 75 mol% TeO2, 10 mol% Nb2O5,(15 mol%-x) BaO, x BaF2(x = 0 mol%, 5 mol%, 10 mol%, 15 mol%) doped with Yb2O3 were prepared by the melt-quenching method. Their emission cross-sections, fluorescence lifetimes, and gain properties were investigated by using the absorption spectra and the fluorescence decay curves. The results show that by substituting BaF2 for BaO, the emission cross-section decreases from 1.37 pm2 to 1.21 pm2, and the fluorescence lifetime increases from 0.71 ms to 0.96 ms. These properties indicate that this oxyfluoride tellurite glass may have potential uses as the Yb2O3-doped gain medium in a solid laser.     

27Al and 23Na double-rotation NMR of sodalites.

The 27Al NMR spectra of calcium tungstate aluminate sodalite (CAW), Ca8[Al12O24](WO4)2, and the 23Na NMR spectra of sodium aluminosilicate sodalites of general composition Na9[Si6Al6O24]A2 with A = B(OH)4- (SBS), SCN- (SRS) and A2 = SO4(2-) (SSS), MoO4(2-) (SMS) have been measured using magic-angle spinning (MAS) and double-rotation (DOR) techniques. Rotor synchronized pulse excitation is applied in the DOR experiments. Dramatic line narrowing is observed in the DOR spectra of all samples. The 27Al DOR NMR spectra of CAW measured at 9.4 and 11.7 T and spinning rates of 800-1150 Hz of the outer and 5 kHz of the inner rotor show seven sharp central lines accompanied by a manifold of spinning sidebands. These lines correspond to the seven crystallographically inequivalent Al sites of the CAW framework derived from X-ray structure analysis. From the difference of the line positions in the 9.4 and 11.7 T spectra the quadrupole coupling constant, QCC, quadrupole induced shift, sigma qs, and isotropic chemical shift, delta cs, of each Al site have been calculated. QCC values in the range of 5 to 9 MHz are obtained which reflect the strong tetragonal distortion of the AlO4 tetrahedra in CAW. delta cs shows only small changes in the range between 74.4 and 77.2 ppm. A tentative assignment of all lines to the distinct Al sites is derived from the correlation between QCC and a "shear strain parameter" describing quantitatively the distortion of the AlO4 tetrahedra.(ABSTRACT TRUNCATED AT 250 WORDS)     

Strategies for extracting NMR parameters from 23Na MAS, DOR and MQMAS spectra. A case study for Na4P2O7

The 23Na magic-angle spinning (MAS), double rotation (DOR) and multiple-quantum magic-angle spinning (MQMAS) NMR spectra of anhydrous sodium pyrophosphate, Na4P2O7, measured at five different Larmor frequencies (nuL) ranging from 105.8 MHz (corresponding to 400 MHz 1H frequency) to 211.6 MHz (800 MHz) are analysed and the complete set of NMR parameters (C(qcc), etaQ and delta(iso)) of the four crystallographically inequivalent sodium sites were determined with high accuracy. Different approaches of spectra evaluation are discussed and their results are compared. The most reliable results are obtained from a combined evaluation of five DOR and three MQMAS spectra but also from two DOR and one MAS spectra or even from a single MQMAS spectrum all data can be derived. It is shown that Na4P2O7 may serve as a useful reference material for experimental set-up and reliability tests of the various NMR experiments.     

Enhancement of upconversion luminescence due to the formation of nanocrystals in Er3+-doped tellurite glasses

Optically transparent Er3+-doped tellurite-based nanocrystallized glasses with the composition of 70TeO2·15Lie2O·0·15Nb2O5·0.5Er2O3(mol)have been perpared by a conventional melting quenching and the subsequent heat treatment porcesses.The sizes of grown nanocrystals in glass matrix appear to be35-50 nm from the X-ray diffraction (XRD) measurement. The microhardness measurement shows that the Vickers hardness values of the nanocrystallized tellurite glasses are larger (33%-62%) than those inthe base glass. The Raman spectra imply that the maximum phonon energy of the based glass decreases and shifts from 668 to 638 cm-1 after heat-treatment. Visible upconversion luminescence and infrared luminescence of the base glass and heat-treated glasses under 980-nm laser diode (LD) excitation are investigated. The 524-, 546- and 656-nm upconversion intensities by 980-nm pumping increase significantly.     

B2O3含量对掺铒碲铌酸盐玻璃光谱性质及热稳定性影响

制备了一系列碲铌酸盐玻璃85TeO₂-(15-x)Nb₂O₅-xB₂O₃-1%Er₂O₃(TNBx=0, 3, 6, 9, 12, 15).根据Judd-Ofelt(J-O)和McCumber理论,讨论和分析了B₂O₃含量对掺铒碲铌酸盐玻璃热稳定性及光谱性质影响.研究发现,玻璃开始析晶温度和玻璃转变温度差值ΔT(T_x-T_g),J-O强度参数,FWHM和峰值受激发射截面的乘积在B₂O₃引入摩尔分数为9%时达到最大值.同时,Er³⁺:⁴I_13/2能级寿命也随着B₂O₃含量的增加而单调增加.结果表明,在掺铒碲铌玻璃中,适量的B₂O₃能较好地提高玻璃的热稳定性能和Er³⁺离子的光谱性质.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO2-ZnO-Na2O的Tm3+离子单掺和Tm3+/Yb3+共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ωt(t=2,4,6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τrad等光谱参量,测量得到了不同Yb3+离子掺杂浓度下玻璃样品的Tm3+离子上转换发光谱.结果显示,在980nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm3+离子上转换发光分析表明,强烈的Tm3+离子近红外上转换发光主要来自于Yb3+/Yb3+离子间的共振能量传递以及基于单声子和双声子辅助的Yb3+/Tm3+离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm3+∶3 F4→3 H6能级间跃迁的1.8μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb3+/Tm3+共掺TeO2-ZnO-Na2O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

125Te NMR chemical-shift trends in PbTe–GeTe and PbTe–SnTe alloys

Complex tellurides, such as doped PbTe, GeTe, and their alloys, are among the best thermoelectric materials. Knowledge of the change in ¹²⁵Te NMR chemical shift due to bonding to dopant or “solute” atoms is useful for determination of phase composition, peak assignment, and analysis of local bonding. We have measured the ¹²⁵Te NMR chemical shifts in PbTe-based alloys, Pb_1−xGe_xTe and Pb_1−xSn_xTe, which have a rocksalt-like structure, and analyzed their trends. For low x, several peaks are resolved in the 22-kHz MAS ¹²⁵Te NMR spectra. A simple linear trend in chemical shifts with the number of Pb neighbors is observed. No evidence of a proposed ferroelectric displacement of Ge atoms in a cubic PbTe matrix is detected at low Ge concentrations. The observed chemical shift trends are compared with the results of DFT calculations, which confirm the linear dependence on the composition of the first-neighbor shell. The data enable determination of the composition of various phases in multiphase telluride materials. They also provide estimates of the ¹²⁵Te chemical shifts of GeTe and SnTe (+970 and +400±150 ppm, respectively, from PbTe), which are otherwise difficult to access due to Knight shifts of many hundreds of ppm in neat GeTe and SnTe.     

Photoinduced stable second-harmonic generation in chalcogenide glasses

We report on photoinduced second-harmonic generation (SHG) in chalcogenide glasses. Fundamental and second-harmonic waves from a nanosecond pulsed Nd:YAG laser were used to induce second-order nonlinearity in chalcogenide glasses. The magnitude of SHG in 20G?20A?60S glass was 10(4) larger than that of tellurite glass with a composition of 15Nb(2)O (5) 85TeO(2) (mol.%). Moreover, no apparent decay of photoinduced SHG in 20G?20A?60S glass was observed after optical poling at room temperature. We suggest that the large and stable value of chi((2)) is due to the induced defect structures and large chi((3)) of the chalcogenide glasses.     

New opportunities for high-resolution solid-state NMR spectroscopy of oxide materials at 21.1- and 18.8-T fields

We present here high-resolution solid state NMR spectra of several oxide and silicate materials that illustrate the improvements obtainable with very high external fields (18.8 and 21.1 T), with probes capable of tuning to a wide frequency range that allow observations of nuclides from high to low magnetogyric ratio. We discuss 27Al MAS spectra for the zeolite scolecite (CaAl2Si3O10 x 3H2O), 17O MAS data for analcime (NaAlSi2O6 x H2O), calcium monoaluminate (CaAI2O4), and titanite (CaTiSiO5), 39K spin-echo spectra for leucite (KAlSi2O6), microline (KAlSiO8), muscovite (KAl2(AlSi3O10)(OH2) and a potassium aluminosolicate glass, and preliminary 73Ge spin-echo MAS spectra for crystalline and glassy germanium dioxide (GeO2).     

Solid-state NMR characterization of a controlled-pore glass and of the effects of electron irradiation

Controlled-pore glasses (CPGs) are silica-based materials which provide an adequate model system for a better understanding of the radiation chemistry of glasses, especially under nanoscopic confinement. This paper presents a characterization of a nanoporous CPG before and after electron irradiation using multinuclear solid-state magnetic resonance (NMR). 1H MAS NMR has been used for studying the surface proton sites and it is observed that the irradiation leads to a dehydration of the material. Accordingly, concerning the silicon sites near the surface, the observed variation of the Q4, Q3 and Q2 species from 1H-29Si CPMAS spectra shows an increase of the surface polymerization under irradiation, implying in majority a Q2 to Q3/Q4 conversion mechanism. Similarly, 1H-17 O CPMAS measurements exhibit an increase of Si-O-Si groups at the expenses of Si-OH groups. In addition, modifications of the environment of the residual boron atoms are also put in evidence from 11B MAS and MQMAS NMR These data show that MAS NMR methods provide sensitive tools for the characterization of these porous glasses and of the tiny modifications occurring under electron irradiation.     

Fabrication and characterization of a water-free mid-infrared fluorotellurite glass

Using a physical and chemical dehydration technique and a high-pressure, ultradry O2 atmosphere in a semiclosed steel-chamber furnace, we fabricated a group of fluorotellurite glasses with a composition of (90-x)TeO2-xZnF2-10Na2O (mol.%, x=0-30). For x=30, no OH absorption was observed in the range of 0.38-6.1?μm. This is the first report of a water-free mid-IR fluorotellurite glass, to our knowledge, offering the common advantages of a robust oxide glass and an IR-transparent fluoride one. Besides optimized linear transmittance and absorption, the nonlinear refractive indices and Raman gain coefficients are reduced. These results are discussed in the context of mid-IR high-power laser generation and transmission.     

掺铒重金属氧氟硅铋酸盐玻璃的光谱性质

研究了重金属氧氟硅铋酸盐玻璃 (50-x)SiO2 xBi2O3 50PbF2(x=0, 3, 5, 8, 10, 13, 15 mol%)中Er3+离子的吸收光谱、荧光光谱、荧光半高宽、荧光 寿命和热稳定性能.应用Judd Ofelt理论计算了玻璃的强度参数Ωt(t=2,4,6)，应用 McCumber计算了能级4I13/2→4I15/2跃迁的受激发射截面. 结果发现荧光半高宽与Ω6有较大联系，Ω6越大，荧光半高宽越宽.对Er3+ 关键词： 重金属氧氟硅铋酸盐玻璃 光谱性质 Er3+离子 Judd Ofelt参数     

Site connectivities in silver borophosphate glasses: new results from 11B{31P} and 31P{11B} rotational echo double resonance NMR spectroscopy

Local and medium range order in the glass system 50Ag2O-50[(B2O3)x-(P2O5)(1-x)] (x=0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6) have been investigated by high-resolution solid state nuclear magnetic resonance (NMR) techniques. The detailed local site distribution has been derived from deconvolution analysis of the 11B and 31P magic-angle spinning (MAS) NMR signals. Quantitative information regarding the extent of boron-oxygen-phosphorus connectivity has been obtained on the basis of 11B[31P} and 31P{11B} rotational echo double resonance experiments. Incorporation of borate into silver metaphosphate glasses produces four-coordinate BO4/2- sites, which crosslink the metaphosphate chains, resulting in a significant increase in the glass transition temperature. Furthermore, the presence of borate favors the disproportionation of P(2) chain-like units into P(1) and P(3) sites, an effect not observed in binary alkali phosphate glasses. Finally, borate incorporation beyond x=0.3 results in the formation of neutral BO3/2 units, indicating some net charge transfer from the borate to the phosphate network former species. This latter result corresponds to the general metal ion scavenging effect observed for phosphate species in other mixed network former glass systems. In the present system, the effect is relatively moderate, however, suggesting that anionic BO4/2- groups are stabilized by the interaction with the phosphate groups.