I. A study of the dynamics of triplet excitons in molecular crystals. II. An investigation of delayed light emission from Chlorella pyrenoidosa

I. PREAMBLE AND SCOPE

Brief introductory remarks, together with a definition of the scope of the material discussed in the thesis, are given.

II. A STUDY OF THE DYNAMICS OF TRIPLET EXCITONS IN MOLECULAR CRYSTALS

Phosphorescence spectra of pure crystalline naphthalene at room temperature and at 77˚ K are presented. The lifetime of the lowest triplet ³B_1u state of the crystal is determined from measurements of the time-dependence of the phosphorescence decay after termination of the excitation light. The fact that this lifetime is considerably shorter in the pure crystal at room temperature than in isotopic mixed crystals at 4.2˚ K is discussed, with special importance being attached to the mobility of triplet excitons in the pure crystal.

Excitation spectra of the delayed fluorescence and phosphorescence from crystalline naphthalene and anthracene are also presented. The equation governing the time- and spatial-dependence of the triplet exciton concentration in the crystal is discussed, along with several approximate equations obtained from the general equation under certain simplifying assumptions. The influence of triplet exciton diffusion on the observed excitation spectra and the possibility of using the latter to investigate the former is also considered. Calculations of the delayed fluorescence and phosphorescence excitation spectra of crystalline naphthalene are described.

A search for absorption of additional light quanta by triplet excitons in naphthalene and anthracene crystals failed to produce any evidence for the phenomenon. This apparent absence of triplet-triplet absorption in pure crystals is attributed to a low steady-state triplet concentration, due to processes like triplet-triplet annihilation, resulting in an absorption too weak to be detected with the apparatus used in the experiments. A comparison of triplet-triplet absorption by naphthalene in a glass at 77˚ K with that by naphthalene-h₈ in naphthalene-d₈ at 4.2˚ K is given. A broad absorption in the isotopic mixed crystal triplet-triplet spectrum has been tentatively interpreted in terms of coupling between the guest ³B_1u state and the conduction band and charge-transfer states of the host crystal.

III. AN INVESTIGATION OF DELAYED LIGHT EMISSION FROM Chlorella Pyrenoidosa

An apparatus capable of measuring emission lifetimes in the range 5 X 10^-9 sec to 6 X 10^-3 sec is described in detail. A cw argon ion laser beam, interrupted periodically by means of an electro-optic shutter, serves as the excitation source. Rapid sampling techniques coupled with signal averaging and digital data acquisition comprise the sensitive detection and readout portion of the apparatus. The capabilities of the equipment are adequately demonstrated by the results of a determination of the fluorescence lifetime of 5, 6, 11, 12-tetraphenyl-naphthacene in benzene solution at room temperature. Details of numerical methods used in the final data reduction are also described.

The results of preliminary measurements of delayed light emission from Chlorella Pyrenoidosa in the range 10^-3 sec to 1 sec are presented. Effects on the emission of an inhibitor and of variations in the excitation light intensity have been investigated. Kinetic analysis of the emission decay curves obtained under these various experimental conditions indicate that in the millisecond-to-second time interval the decay is adequately described by the sum of two first-order decay processes. The values of the time constants of these processes appear to be sensitive both to added inhibitor and to excitation light intensity.

Nuclear hyperfine interactions in W^(182), W^(183), and Pt^(195) as studies by the Mossbauer effect

The Mössbauer technique has been used to study the nuclear hyperfine interactions and lifetimes in W¹⁸² (2⁺ state) and W¹⁸³ (3/2^- and 5/2^- states) with the following results: g(5/2^-)/g(2⁺) = 1.40 ± 0.04; g(3/2^- = -0.07 ± 0.07; Q(5/2^-)/Q(2⁺) = 0.94 ± 0.04; T_1/2(3/2^-) = 0.184 ± 0.005 nsec; T_1/2(5/2^-) >̰ 0.7 nsec. These quantities are discussed in terms of a rotation-particle interaction in W¹⁸³ due to Coriolis coupling. From the measured quantities and additional information on γ-ray transition intensities magnetic single-particle matrix elements are derived. It is inferred from these that the two effective g-factors, resulting from the Nilsson-model calculation of the single-particle matrix elements for the spin operators ŝ_z and ŝ₊, are not equal, consistent with a proposal of Bochnacki and Ogaza.

The internal magnetic fields at the tungsten nucleus were determined for substitutional solid solutions of tungsten in iron, cobalt, and nickel. With g(2⁺) = 0.24 the results are: |H_eff(W-Fe)| = 715 ± 10 kG; |H_eff(W-Co)| = 360 ± 10 kG; |H_eff(W-Ni)| = 90 ± 25 kG. The electric field gradients at the tungsten nucleus were determined for WS₂ and WO₃. With Q(2⁺) = -1.81b the results are: for WS₂, eq = -(1.86 ± 0.05) 10¹⁸ V/cm²; for WO₃, eq = (1.54 ± 0.04) 10¹⁸ V/cm² and ƞ = 0.63 ± 0.02.

The 5/2^- state of Pt¹⁹⁵ has also been studied with the Mössbauer technique, and the g-factor of this state has been determined to be -0.41 ± 0.03. The following magnetic fields at the Pt nucleus were found: in an Fe lattice, 1.19 ± 0.04 MG; in a Co lattice, 0.86 ± 0.03 MG; and in a Ni lattice, 0.36 ± 0.04 MG. Isomeric shifts have been detected in a number of compounds and alloys and have been interpreted to imply that the mean square radius of the Pt¹⁹⁵ nucleus in the first-excited state is smaller than in the ground state.

Photochemical electron transfer at fixed distance : a synthetic model of the photosynthetic primary process

A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x10⁹sec^-1 in N,N-dimethylformamide to 1.15x10¹⁰ Sec^-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κ_ET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG^0'(R)| ≤ 1.0 eV until a maximum is reached (κ_ET = 3 x 10⁸ sec^-1 rising to 1.15 x 10¹⁰ sec^-1 in acetonitrile). The rate remains insensitive to ΔG⁰ for ~ 300 mV from 1.0 eV≤ |ΔG^0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κ_ET = 5 x 10⁹ sec^-1).

Heteroepitaxy of Group IV and Group III-V semiconductor alloys for photovoltaic applications

Photovoltaic energy conversion represents a economically viable technology for realizing collection of the largest energy resource known to the Earth -- the sun. Energy conversion efficiency is the most leveraging factor in the price of energy derived from this process. This thesis focuses on two routes for high efficiency, low cost devices: first, to use Group IV semiconductor alloy wire array bottom cells and epitaxially grown Group III-V compound semiconductor alloy top cells in a tandem configuration, and second, GaP growth on planar Si for heterojunction and tandem cell applications.

Metal catalyzed vapor-liquid-solid grown microwire arrays are an intriguing alternative for wafer-free Si and SiGe materials which can be removed as flexible membranes. Selected area Cu-catalyzed vapor-liquid solid growth of SiGe microwires is achieved using chlorosilane and chlorogermane precursors. The composition can be tuned up to 12% Ge with a simultaneous decrease in the growth rate from 7 to 1 μm/min^-1. Significant changes to the morphology were observed, including tapering and faceting on the sidewalls and along the lengths of the wires. Characterization of axial and radial cross sections with transmission electron microscopy revealed no evidence of defects at facet corners and edges, and the tapering is shown to be due to in-situ removal of catalyst material during growth. X-ray diffraction and transmission electron microscopy reveal a Ge-rich crystal at the tip of the wires, strongly suggesting that the Ge incorporation is limited by the crystallization rate.

Tandem Ga_1-xIn_xP/Si microwire array solar cells are a route towards a high efficiency, low cost, flexible, wafer-free solar technology. Realizing tandem Group III-V compound semiconductor/Si wire array devices requires optimization of materials growth and device performance. GaP and Ga_1-xIn_xP layers were grown heteroepitaxially with metalorganic chemical vapor deposition on Si microwire array substrates. The layer morphology and crystalline quality have been studied with scanning electron microscopy and transmission electron microscopy, and they provide a baseline for the growth and characterization of a full device stack. Ultimately, the complexity of the substrates and the prevalence of defects resulted in material without detectable photoluminescence, unsuitable for optoelectronic applications.

Coupled full-field optical and device physics simulations of a Ga_0.51In_0.49P/Si wire array tandem are used to predict device performance. A 500 nm thick, highly doped "buffer" layer between the bottom cell and tunnel junction is assumed to harbor a high density of lattice mismatch and heteroepitaxial defects. Under simulated AM1.5G illumination, the device structure explored in this work has a simulated efficiency of 23.84% with realistic top cell SRH lifetimes and surface recombination velocities. The relative insensitivity to surface recombination is likely due to optical generation further away from the free surfaces and interfaces of the device structure.

Finally, GaP has been grown free of antiphase domains on Si (112) oriented substrates using metalorganic chemical vapor deposition. Low temperature pulsed nucleation is followed by high temperature continuous growth, yielding smooth, specular thin films. Atomic force microscopy topography mapping showed very smooth surfaces (4-6 Å RMS roughness) with small depressions in the surface. Thin films (~ 50 nm) were pseudomorphic, as confirmed by high resolution x-ray diffraction reciprocal space mapping, and 200 nm thick films showed full relaxation. Transmission electron microscopy showed no evidence of antiphase domain formation, but there is a population of microtwin and stacking fault defects.

Spontaneous and stimulated light emission due to radiative recombination in forward biased lead telluride P-N junctions

Since the discovery in 1962 of laser action in semiconductor diodes made from GaAs, the study of spontaneous and stimulated light emission from semiconductors has become an exciting new field of semiconductor physics and quantum electronics combined. Included in the limited number of direct-gap semiconductor materials suitable for laser action are the members of the lead salt family, i.e . PbS, PbSe and PbTe. The material used for the experiments described herein is PbTe . The semiconductor PbTe is a narrow band- gap material (E_g = 0.19 electron volt at a temperature of 4.2°K). Therefore, the radiative recombination of electron-hole pairs between the conduction and valence bands produces photons whose wavelength is in the infrared (λ ≈ 6.5 microns in air).

The p-n junction diode is a convenient device in which the spontaneous and stimulated emission of light can be achieved via current flow in the forward-bias direction. Consequently, the experimental devices consist of a group of PbTe p-n junction diodes made from p –type single crystal bulk material. The p - n junctions were formed by an n-type vapor- phase diffusion perpendicular to the (100) plane, with a junction depth of approximately 75 microns. Opposite ends of the diode structure were cleaved to give parallel reflectors, thereby forming the Fabry-Perot cavity needed for a laser oscillator. Since the emission of light originates from the recombination of injected current carriers, the nature of the radiation depends on the injection mechanism.

The total intensity of the light emitted from the PbTe diodes was observed over a current range of three to four orders of magnitude. At the low current levels, the light intensity data were correlated with data obtained on the electrical characteristics of the diodes. In the low current region (region A), the light intensity, current-voltage and capacitance-voltage data are consistent with the model for photon-assisted tunneling. As the current is increased, the light intensity data indicate the occurrence of a change in the current injection mechanism from photon-assisted tunneling (region A) to thermionic emission (region B). With the further increase of the injection level, the photon-field due to light emission in the diode builds up to the point where stimulated emission (oscillation) occurs. The threshold current at which oscillation begins marks the beginning of a region (region C) where the total light intensity increases very rapidly with the increase in current. This rapid increase in intensity is accompanied by an increase in the number of narrow-band oscillating modes. As the photon density in the cavity continues to increase with the injection level, the intensity gradually enters a region of linear dependence on current (region D), i.e. a region of constant (differential) quantum efficiency.

Data obtained from measurements of the stimulated-mode light-intensity profile and the far-field diffraction pattern (both in the direction perpendicular to the junction-plane) indicate that the active region of high gain (i.e. the region where a population inversion exists) extends to approximately a diffusion length on both sides of the junction. The data also indicate that the confinement of the oscillating modes within the diode cavity is due to a variation in the real part of the dielectric constant, caused by the gain in the medium. A value of τ ≈ 10^-9 second for the minority- carrier recombination lifetime (at a diode temperature of 20.4°K) is obtained from the above measurements. This value for τ is consistent with other data obtained independently for PbTe crystals.

Data on the threshold current for stimulated emission (for a diode temperature of 20. 4°K) as a function of the reciprocal cavity length were obtained. These data yield a value of J’_th = (400 ± 80) amp/cm² for the threshold current in the limit of an infinitely long diode-cavity. A value of α = (30 ± 15) cm^-1 is obtained for the total (bulk) cavity loss constant, in general agreement with independent measurements of free- carrier absorption in PbTe. In addition, the data provide a value of n_s ≈ 10% for the internal spontaneous quantum efficiency. The above value for n_s yields values of t_b ≈ τ ≈ 10^-9 second and t_s ≈ 10^-8 second for the nonradiative and the spontaneous (radiative) lifetimes, respectively.

The external quantum efficiency (n_d) for stimulated emission from diode J-2 (at 20.4° K) was calculated by using the total light intensity vs. diode current data, plus accepted values for the material parameters of the mercury- doped germanium detector used for the measurements. The resulting value is n_d ≈ 10%-20% for emission from both ends of the cavity. The corresponding radiative power output (at λ = 6.5 micron) is 120-240 milliwatts for a diode current of 6 amps.

I. Phosphorescence and the true lifetime of triplet states in fluid solutions. II. Why is condensed oxygen blue?

I. PHOSPHORESCENCE AND THE TRUE LIFETIME OF TRIPLET STATES IN FLUID SOLUTIONS

Phosphorescence has been observed in a highly purified fluid solution of naphthalene in 3-methylpentane (3-MP). The phosphorescence lifetime of C₁₀H₈ in 3-MP at -45 °C was found to be 0.49 ± 0.07 sec, while that of C₁₀D₈ under identical conditions is 0.64 ± 0.07 sec. At this temperature 3-MP has the same viscosity (0.65 centipoise) as that of benzene at room temperature. It is believed that even these long lifetimes are dominated by impurity quenching mechanisms. Therefore it seems that the radiationless decay times of the lowest triplet states of simple aromatic hydrocarbons in liquid solutions are sensibly the same as those in the solid phase. A slight dependence of the phosphorescence lifetime on solvent viscosity was observed in the temperature region, -60° to -18°C. This has been attributed to the diffusion-controlled quenching of the triplet state by residual impurity, perhaps oxygen. Bimolecular depopulation of the triplet state was found to be of major importance over a large part of the triplet decay.

The lifetime of triplet C₁₀H₈ at room temperature was also measured in highly purified benzene by means of both phosphorescence and triplet-triplet absorption. The lifetime was estimated to be at least ten times shorter than that in 3-MP. This is believed to be due not only to residual impurities in the solvent but also to small amounts of impurities produced through unavoidable irradiation by the excitation source. In agreement with this idea, lifetime shortening caused by intense flashes of light is readily observed. This latter result suggests that experiments employing flash lamp techniques are not suitable for these kinds of studies.

The theory of radiationless transitions, based on Robinson's theory, is briefly outlined. A simple theoretical model which is derived from Fano's autoionization gives identical result.

Il. WHY IS CONDENSED OXYGEN BLUE?

The blue color of oxygen is mostly derived from double transitions. This paper presents a theoretical calculation of the intensity of the double transition (a ¹Δ_g) (a ¹Δ_g)←(X ³Σ_g^-) (X ³Σ_g^-), using a model based on a pair of oxygen molecules at a fixed separation of 3.81 Å. The intensity enhancement is assumed to be derived from the mixing (a ¹Δ_g) (a ¹Δ_g) _~~~ (X ³Σ_g^-) (X ³Σ_u^-) and (a ¹Δ_g) (¹Δ_u) _~~~ (X ³Σ_g^-) (X ³Σ_g^-). Matrix elements for these interactions are calculated using a π-electron approximation for the pair system. Good molecular wavefunctions are used for all but the perturbing (B ³Σ_u^-) state, which is approximated in terms of ground state orbitals. The largest contribution to the matrix elements arises from large intramolecular terms multiplied by intermolecular overlap integrals. The strength of interaction depends not only on the intermolecular separation of the two oxygen molecules, but also as expected on the relative orientation. Matrix elements are calculated for different orientations, and the angular dependence is fit to an analytical expression. The theory therefore not only predicts an intensity dependence on density but also one on phase at constant density. Agreement between theory and available experimental results is satisfactory considering the nature of the approximation, and indicates the essential validity of the overall approach to this interesting intensity enhancement problem.

K9玻璃薄膜对离子交换磷酸盐玻璃波导表面保护的优化研究

采用镀K9玻璃薄膜方法来解决离子交换掺铒磷酸盐玻璃波导表面的侵蚀问题,对K9玻璃薄膜的厚度进行了优化研究。测量分析了样品的荧光光谱和荧光寿命,采用光学显微镜和棱镜耦合技术对不同K9玻璃薄膜厚度下制备波导的表面形貌和导光特性进行了表征和测试。结果表明,与掺铒磷酸盐玻璃原材料相比,镀K9玻璃薄膜后荧光光谱保持不变,荧光寿命稍有下降(约0.2 ms);K9玻璃薄膜的厚度在60~80 nm的范围内保护效果最佳。为下一步制备掺铒有源玻璃光波导器件奠定了良好的实验基础。

Paths Towards High Efficiency Silicon Photovoltaics

While photovoltaics hold much promise as a sustainable electricity source, continued cost reduction is necessary to continue the current growth in deployment. A promising path to continuing to reduce total system cost is by increasing device efficiency. This thesis explores several silicon-based photovoltaic technologies with the potential to reach high power conversion efficiencies. Silicon microwire arrays, formed by joining millions of micron diameter wires together, were developed as a low cost, low efficiency solar technology. The feasibility of transitioning this to a high efficiency technology was explored. In order to achieve high efficiency, high quality silicon material must be used. Lifetimes and diffusion lengths in these wires were measured and the action of various surface passivation treatments studied. While long lifetimes were not achieved, strong inversion at the silicon / hydrofluoric acid interface was measured, which is important for understanding a common measurement used in solar materials characterization.

Cryogenic deep reactive ion etching was then explored as a method for fabricating high quality wires and improved lifetimes were measured. As another way to reach high efficiency, growth of silicon-germanium alloy wires was explored as a substrate for a III-V on Si tandem device. Patterned arrays of wires with up to 12% germanium incorporation were grown. This alloy is more closely lattice matched to GaP than silicon and allows for improvements in III-V integration on silicon.

Heterojunctions of silicon are another promising path towards achieving high efficiency devices. The GaP/Si heterointerface and properties of GaP grown on silicon were studied. Additionally, a substrate removal process was developed which allows the formation of high quality free standing GaP films and has wide applications in the field of optics.

Finally, the effect of defects at the interface of the amorphous silicon heterojuction cell was studied. Excellent voltages, and thus efficiencies, are achievable with this system, but the voltage is very sensitive to growth conditions. We directly measured lateral transport lengths at the heterointerface on the order of tens to hundreds of microns, which allows carriers to travel towards any defects that are present and recombine. This measurement adds to the understanding of these types of high efficiency devices and may aid in future device design.

CP and the three pion decay of the K°

The time distribution of the decays of an initially pure K° beam into π+π-π° has been analyzed to determine the complex parameter W (also known as Ƞ^+-° and (x + iy)). The K° beam was produced in a brass target by the interactions of a 2.85 GeV/c π- beam which was generated on an internal target in the Lawrence Radiation Laboratory (LRL) Bevatron. The counters and hodoscopes in the apparatus selected for events with a neutral (K°) produced in the brass target, two charged secondaries passing through a magnet spectrometer and a ɣ-ray shower in a shower hodoscope.

From the 275K apparatus triggers, 148 K → π+π-π° events were isolated. The presence of a ɣ-ray shower in the optical shower chambers and a two-prong vee in the optical spark chambers were devices used to isolate the events. The backgrounds were further reduced by reconstructing the momenta of the two charged secondaries and applying kinematic constraints.

The best fit to the final sample of 148 events distributed between .3 and 7.0 K_S lifetimes gives:

ReW = -.05 ±.17

ImW = +.39 +.35/-.37

This result is consistent with both CPT invariance (ReW = 0) and CP invariance (W = 0). Backgrounds are estimated to be less than 10% and systematic effects have also been estimated to be negligible.

An analysis of the present data on CP violation in this decay mode and other K° decay modes has estimated the phase of ɛ to be 45.3 ± 2.3 degrees. This result is consistent with the super weak theories of CP violation which predicts the phase of ɛ to be 43°. This estimate is in turn used to predict the phase of Ƞ°° to be 48.0 ± 7.9 degrees. This is a substantial improvement on presently available measurements. The largest error in this analysis comes from the present limits on W from the world average of recent experiments. The K → πuʋ mode produces the next largest error. Therefore further experimentation in these modes would be useful.

Nd3+螯合物的含氢有机溶液光谱性能研究

Tris-thenoyltrifluroacetonate of Nd3+ has been prepared and dissolved in DMF solation with very high concentration, and the contained hydrogen has not been substituted by deuterium. The absorption spectrum, emission spectrum, and fluorescence lifetime of the solution were measured. Very obvious characteristic fluorescence peaks were observed at 898 and 1058 nm. Based on Judd-Ofelt theory, three intensity parameters were obtained: Omega(2) = 4.9 x 10(-20) cm(2), Omega(4) = 5.1 x 10(-20) cm(2) and Omega(6) = 2.5 x 10(-20) cm(2). Line strengths S-cal, oscillator strengths f(cal), radiative transition probabilities A(ed), radiative lifetimes tau(r) and branch ratios beta were calculated too. The measured lifetime tau of 1058 nm peak is 460 mu s, and that of 898 nm 505 mu s. Comparison between theoretically computed radiative lifetime tau(r)(682 mu s) and the measured lifetime indicates that the non-radiative transition probability of the solution is very low and the fluorescence quantum efficiency very high. High values of three intensity parameters prove the high asymmetric surroundings of Nd3+, which is important for Nd3+ to absorb the excitation energy. Spectropic quality factor Omega(4)/Omega(6) > 1 makes radiation at 898 nm stronger than at 1058 nm.

新型掺铒离子氧氟碲酸盐玻璃的光谱性质

探求新的具有优良的热学和光学性能的基质玻璃系统，是获得具有宽带宽和增益平坦的掺Er^3＋光纤放大器（EDFA）的一种有效途径。制备了一种新型氧氟碲酸盐玻璃TeO2-BaF2-LaF3，并对其热学性能和光学性质进行了测试。应用乍得-奥菲尔特（Judd-Ofelt）理论计算了Er^3＋离子的J-O理论参量和荧光寿命r。探讨了氟化物的引入对碲酸盐玻璃结构的改变的影响，并分析了其对玻璃的热学性质和光学性质的影响。实验发现，获得的氧氟碲酸盐玻璃具有优良的热学稳定性（△T=156.6C），宽的荧光半峰全宽（72nm）

掺铒碲酸盐玻璃的热力学稳定性和光谱性质的研究

分析了掺Er^3+碲酸盐玻璃的热力学稳定性能，研究了掺Er^3+碲酸盐玻璃的吸收和荧光光谱性质；应用Judd-Ofelt理论计算了碲酸盐玻璃中Er^3+离子的强度参数Ω(Ω2=4．79×10^-20cm^2,Ω4=1．52×10^-20cm^2，Ω6=0．66×10^-20cm^2)，计算了离子的自发跃迁几率，荧光分支比；应用McCumber理论计算了Er^3+的受激发射截面(σe=10．40×10^-21cm^2)、Er^3+离子^4I13／2→^4I15／2发射谱的荧光半高宽(FWHM=65．5nm)

一种新型掺铒碲酸盐玻璃的光谱性质研究

研究了一种新型掺Er^3+碲酸盐玻璃的光谱性质；应用Judd-Ofelt理论计算了碲酸盐玻璃中Er^3+离子的强度参数Ω(Ω2=4．79×10^-20cm^2，Ω4=1．52×10^-20cm^2，Ω6=0．66×10^-20cm^2)，计算了离子的自发跃迁概率，荧光分支比；应用McCumber理论计算了Er^3+的受激发射截面(σe=10．40×10^-21cm^2)，Er^3+离子^4I13/2→^4I15/2发射谱的荧光半高宽(FWHM=65．5nm)及各能级的荧光寿命(^4I13/2能级为τrad

Upconversion emissions in Yb3+-Tm3+-doped tellurite glasses excited at 976 nm

Intense Tm3+ blue upconversion emission has been observed in Tm3+-Yb3+ codoped oxyfluoride tellurite glass under excitation with a diode laser at 976 nm. Three emission bands centered at 475, 650 and 796 nm corresponding to the transitions (1)G(4) -> H-3(6), (1)G(4) -> H-3(4) and F-3(4) -> H-3(6), respectively, simultaneously occur. The dependence of upconversion intensities on Tm3+ ions concentration and excitation power are investigated. For fixed Yb2O3 concentrations of 5.0 mol%, the maximum upconversion intensity was obtained with Tm2O3 concentration of about 0.1 mol%. The blue upconversion luminescence lifetimes of the Tm3+ transitions (1)G(4) -> H-3(6) are measured. The results are evaluated by the possible upconversion mechanisms.

Spectroscopic properties of neodymium doped high silica glass and aluminum codoping effects on the enhancement of fluorescence emission

Nd3+ -codoped and Al3+-Nd3+-codoped high silica glasses have been prepared by sintering nanoporous glasses impregnated with Nd3+ stop and Al3+ ions. The Judd-Ofelt intensity parameters Omega(2,4,6) of Nd3+-doped high silica glasses were obtained and used to analyze aluminum codoping effects. Fluorescence properties of Nd3+-doped high silica glasses strongly depend on the Al3+ concentration. While Nd3+ ion absorption and emission intensities of obviously increase when aluminum is added to Nd3+-doped high silica glasses, fluorescence lifetimes decrease and aluminum codoping has almost no influence on the radiative quantum efficiencies. This indicates that aluminum codoping is responsible for an anti-quenching effect through a local modification of rare-earth environments rather than through physical cluster dispersion.