Synthesis and characterization of high-spin organic materials: prototypes for the polaronic ferromagnet

The design, synthesis and magnetic characterization of thiophene-based models for the polaronic ferromagnet are described. Synthetic strategies employing Wittig and Suzuki coupling were employed to produce polymers with extended π-systems. Oxidative doping using AsF_5 or I_2 produces radical cations (polarons) that are stable at room temperature. Magnetic characterization of the doped polymers, using SQUID-based magnetometry, indicates that in several instances ferromagnetic coupling of polarons occurs along the polymer chain. An investigation of the influence of polaron stability and delocalization on the magnitude of ferromagnetic coupling is pursued. A lower limit for mild, solution phase I_2 doping is established. A comparison of the variable temperature data of various polymers reveals that deleterious antiferromagnetic interactions are relatively insensitive to spin concentration, doping protocols or spin state. Comparison of the various polymers reveals useful design principles and suggests new directions for the development of magnetic organic materials. Novel strategies for solubilizing neutral polymeric materials in polar solvents are investigated.

The incorporation of stable bipyridinium spin-containing units into a polymeric high-spin array is explored. Preliminary results suggest that substituted diquat derivatives may serve as stable spin-containing units for the polaronic ferromagnet and are amenable to electrochemical doping. Synthetic efforts to prepare high-spin polymeric materials using viologens as a spin source have been unsuccessful.

Advanced density functional theory methods for materials science

In this work we chiefly deal with two broad classes of problems in computational materials science, determining the doping mechanism in a semiconductor and developing an extreme condition equation of state. While solving certain aspects of these questions is well-trodden ground, both require extending the reach of existing methods to fully answer them. Here we choose to build upon the framework of density functional theory (DFT) which provides an efficient means to investigate a system from a quantum mechanics description.

Zinc Phosphide (Zn₃P₂) could be the basis for cheap and highly efficient solar cells. Its use in this regard is limited by the difficulty in n-type doping the material. In an effort to understand the mechanism behind this, the energetics and electronic structure of intrinsic point defects in zinc phosphide are studied using generalized Kohn-Sham theory and utilizing the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional for exchange and correlation. Novel 'perturbation extrapolation' is utilized to extend the use of the computationally expensive HSE functional to this large-scale defect system. According to calculations, the formation energy of charged phosphorus interstitial defects are very low in n-type Zn₃P₂ and act as 'electron sinks', nullifying the desired doping and lowering the fermi-level back towards the p-type regime. Going forward, this insight provides clues to fabricating useful zinc phosphide based devices. In addition, the methodology developed for this work can be applied to further doping studies in other systems.

Accurate determination of high pressure and temperature equations of state is fundamental in a variety of fields. However, it is often very difficult to cover a wide range of temperatures and pressures in an laboratory setting. Here we develop methods to determine a multi-phase equation of state for Ta through computation. The typical means of investigating thermodynamic properties is via ’classical’ molecular dynamics where the atomic motion is calculated from Newtonian mechanics with the electronic effects abstracted away into an interatomic potential function. For our purposes, a ’first principles’ approach such as DFT is useful as a classical potential is typically valid for only a portion of the phase diagram (i.e. whatever part it has been fit to). Furthermore, for extremes of temperature and pressure quantum effects become critical to accurately capture an equation of state and are very hard to capture in even complex model potentials. This requires extending the inherently zero temperature DFT to predict the finite temperature response of the system. Statistical modelling and thermodynamic integration is used to extend our results over all phases, as well as phase-coexistence regions which are at the limits of typical DFT validity. We deliver the most comprehensive and accurate equation of state that has been done for Ta. This work also lends insights that can be applied to further equation of state work in many other materials.

室温下稳定的多波长掺铒光纤激光器的研究

通过在线形谐振腔中引入一段缠绕在压电陶瓷上的单模光纤作为正弦相位调制器，使得激射波长的损耗不固定，抑制由于掺铒光纤的均匀展宽效应引起的模式竞争，从而避免了在室温下不稳定的单波长激射，实现了多波长掺铒光纤激光器的稳定输出。为了获得平坦的多波长输出，在谐振腔里使用了一个损耗峰位于1530nm处的长周期光纤光栅，以获得较为平坦的增益谱。通过两个3dB耦合器制成的反射型梳状滤波器的滤波作用，实验中观察到稳定的多波长激射，相邻波长间隔约为0．45nm。中心9个波长的输出功率平坦度为10dB，边模抑制比大于25dB。

Superionic Noble Metal Chalcogenide Thermoelectrics

Measurements and modeling of Cu₂Se, Ag₂Se, and Cu₂S show that superionic conductors have great potential as thermoelectric materials. Cu₂Se and Ag₂Se are predicted to reach a zT of 1.2 at room temperature if their carrier concentrations can be reduced, and Cu-vacancy doped Cu₂S reaches a maximum zT of 1.7 at 1000 K. Te-doped Ag₂Se achieves a zT of 1.2 at 520 K, and could reach a zT of 1.7 if its carrier concentration could be reduced. However, superionic conductors tend to have high carrier concentrations due to the presence of metal defects. The carrier concentration has been found to be difficult to reduce by altering the defect concentration, therefore materials that are underdoped relative to the optimum carrier concentration are easier to optimize. The results of Te-doping of Ag₂Se show that reducing the carrier concentration is possible by reducing the maximum Fermi level in the material.

Two new methods for analyzing thermoelectric transport data were developed. The first involves scaling the temperature-dependent transport data according to the temperature dependences expected of a single parabolic band model and using all of the scaled data to perform a single parabolic band analysis, instead of being restricted to using one data point per sample at a fixed temperature. This allows for a more efficient use of the transport data. The second involves scaling only the Seebeck coefficient and electrical conductivity. This allows for an estimate of the quality factor (and therefore the maximum zT in the material) without using Hall effect data, which are not always available due to time and budget constraints and are difficult to obtain in high-resistivity materials. Methods for solving the coherent potential approximation effective medium equations were developed in conjunction with measurements of the resistivity tensor elements of composite materials. This allows the electrical conductivity and mobility of each phase in the composite to be determined from measurements of the bulk. This points out a new method for measuring the pure-phase electrical properties in impure materials, for measuring the electrical properties of unknown phases in composites, and for quantifying the effects of quantum interactions in composites.

Nonvolatile holograms in LiNbO3 : Fe : Cu by use of the bleaching effect

We report our observation of a bleaching effect under an ultraviolet exposure in LiNbO3:Fe:Cu crystals. Two three-step recording-transferring-fixing schemes are proposed to record nonvolatile photorefractive holograms in such crystals. In the schemes two red laser beams and an ultraviolet illumination are used selectively to write the charge grating in the shallow-level Fe centers, to develop the charge grating in the deep-level Cu centers by transferring the charge grating in the Fe centers, and to fix only the charge grating in the Cu centers for unerasable read-out. Experimental results, verifications, and an optimal recording scheme are given. A comparison of the lithium niobate crystals of the same double-doping system of Fe:Mn, Ce:Mn, Ce:Cu, and Fe:Cu is outlined. (C) 2002 Optical Society of America.

Prescription for optimizing holograms in LiNbO3 : Fe : Mn

The photorefractive holographic dynamics of grating formation in photochromic doubly doped LiNbO3:Fe:Mn crystal is studied numerically and analytically in terms of the two-center model of Kukhtarev Et al. [Ferroelectrics 22, 949 (1979)]. The relations among the recorded and fixed space-charge fields and the doping densities, the oxidation-reduction states of the fields, and the intensities of UV-sensitizing and red recording beams are studied. Important conditions and effects are feued, and an optimal prescription for material doping and oxidation-reduction processing is suggested in which the crystal can be strongly oxidized and the Mn-doping density is smaller than the Fe-doping density. (C) 2000 Optical Society of America. OCIS codes: 050.7330, 190.5330, 090.2900.

Nonvolatile photorefractive holograms in LiNbO3 : Cu : Ce crystals

We report experimental and theoretical studies of nonvolatile photorefractive holographic recording in LiNbO3:Cu:Ce crystals with two illumination schemes: (1) UV light for sensitization and a red interfering pattern for recording and (2) blue light for sensitization and a red pattern for recording. The results show that the oxidized LiNbO3:Cu:Ce crystals can provide high, persistent refractive-index modulation with weak lightinduced scattering. The optimal working conditions and the prescription for doping and oxidation-reduction processing that yields the maximum refractive-index modulation are discussed. (C) 2000 Optical Society of America OCIS codes: 050.7330, 190.5330, 090.2900.

Effect of absorption on the diffraction efficiency in Fe : LiNbO3 crystal with 90 degrees recording geometry

In this paper the saturated diffraction efficiency has been optimized by considering the effect of the absorption of the recording light on a crossed-beam grating with 90 degrees recording geometry in Fe:LiNbO3 crystals. The dependence of saturated diffraction efficiency on the doping levels with a known oxidation-reduction state, as well as the dependence of saturated diffraction efficiency on oxidation-reduction state with known doping levels, has been investigated. Two competing effects on the saturated diffraction efficiency were discussed, and the intensity profile of the diffracted beam at the output boundary has also been investigated. The results show that the maximal saturated diffraction efficiency can be obtained in crystals with moderate doping levels and modest oxidation state. An experimental verification is performed and the results are consistent with those of the theoretical calculation.

Frequency upconversion properties of Er3+/Yb3+-codoped lead-germanium-bismuth oxide glasses

The frequency upconversion properties of Er3+/Yb3+-codoped heavy metal oxide lead-germanium-bismuth oxide glasses under 975 mn excitation are investigated. Intense green and red emission bands centered at 536, 556 and 672 run, corresponding to the H-2(1/2) --> I-4(15/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) -->I-4(15/2) transitions of Er3+, respectively, were simultaneously observed at room temperature. The influences of PbO on upconversion intensity for the green (536 and 556 nm) and red (672 nm) emissions were compared and discussed. The optimized rare earth doping ratio of Er3+ and Yb3+, is 1:5 for these glasses, which results in the stronger upconversion fluorescence intensities. The dependence of intensities of upconversion emission on excitation power and possible upconversion mechanisms were evaluated and analyzed. The structure of glass has been investigated by means of infrared (IR) spectral analysis. The results indicate that the Er3+/Yb3+-codoped heavy metal oxide lead-germanium-bismuth oxide glasses may be a potential materials for developing upconversion fiber optic devices. (C) 2006 Published by Elsevier Ltd.

Absorption characteristic and nonvolatile holographic recording in LiNbO3 : Cr : Cu crystals

The absorption characteristic of lithium niobate crystals doped with chromium and copper (Cr and Cu) is investigated. We find that there are two apparent absorption bands for LiNbO3:Cr:Cu crystal doped with 0.14 wt.% Cr2O3 and 0.011 wt.% CuO; one is around 480 nm, and the other is around 660 nm. With a decrease in the doping composition of Cr and an increase in the doping composition of Cu, no apparent absorption band in the shorter wavelength range exists. The higher the doping level of Cr, the larger the absorbance around 660 nm. Although a 633 nm red light is located in the absorption band around 660 nm, the absorption at 633 nm does not help the photorefractive process; i.e., unlike other doubly doped crystals, for example, LiNbO3:Fe:Mn crystal, a nonvolatile holographic recording can be realized by a 633 nm red light as the recording light and a 390 nm UV light as the sensitizing light. For LiNbO3:Cr:Cu crystals, by changing the recording light from a 633 nm red light to a 514 nm green light, sensitizing with a 390 nm UV light and a 488 nm blue light, respectively, a nonvolatile holographic recording can be realized. Doping the appropriate Cr (for example, N-Cr = 2.795 X 10(25)m(-3) and N-Cr/N-Cu = 1) benefits the improvement of holographic recording properties. (c) 2005 Optical Society of America.

Improvement of sensitivity and refractive-index changes in LiNbO3 : Ce : Cu crystals with UV light

A nonvolatile recording scheme is proposed using LiNbO3:Ce:Cu crystals and modulated UV light to record gratings simultaneously in two centres and using red light to bleach the grating in the shallow centre to realize persistent photorefractive holographic storage. Compared with the normal UV-sensitized nonvolatile holographic system, the amplitude of refractive-index changes is greatly increased and the recording sensitivity is significantly enhanced by recording with UV light in the LiNbO3:Ce:Cu crystals. Based on jointly solving the two-centre material equations and the coupled-wave equations, temporal evolutions of the photorefractive grating and the diffraction effciency are effectively described and numerically analysed. Roles of doping levels and recording-beam intensity are discussed in detail. Theoretical results confirm and predict experimental results.

采用紫外光提高双掺杂铌酸锂晶体中全息记录的灵敏度和光栅强度

提出了一种在双掺杂铌酸锂晶体中用调制的双紫外光进行非挥发全息记录的方法。与通常的用紫外光敏化的非挥发全息记录相比，这种方法可以大幅度地提高光栅强度和记录灵敏度。联立双中心物质方程和双光束耦合波方程，数值分析了光栅强度和衍射效率随时间的变化并讨论了掺杂浓度和记录光强对紫外光非挥发全息记录机制下光折变效应的影响。研究发现，紫外光记录得到的深浅中心的光栅具有相同的相位，总的光栅（深浅中心光栅的叠加）强度为两光栅强度之和，固定过程中深中心的光栅得到增强；增大深浅中心掺杂的浓度可以提高光栅强度，增大记录紫外光的光强

有源波导环形谐振腔滤波特性分析

将掺铒有源波导材料引入环形谐振腔结构，从理论上分析了有源波导环形谐振腔的滤波特性。结果表明由于抽运光提供的增益补偿了腔内损耗，使得环形谐振腔满足临界耦合条件，实现对信号光的最佳陷波，同时发现通过改变抽运光功率，可以对精细度和带宽进行动态调谐。分析了铒离子掺杂浓度、信号光功率以及抽运光耦合系数对最佳陷波抽运功率的影响，为有源波导器件设计制作提供了理论依据。

Optimal recording wavelength for nonvolatile photorefractive holograms in Ce : Cu : LiNbO

Three wavelengths of red, green and blue of recording beams are systemically tested for the UV-assistant recording and optical fixing of holograms in a strongly oxidized Ce:Cu:LiNbO3 crystal. Three different photorefractive phenomena are observed. It is shown that the green beams will optimally generate a critical strong nonvolatile hologram with quick sensitivity and the optimal switching technique could be jointly used to obtain a nearly 100% high diffraction. Theoretical verification is given, and a prescription on the doping densities and on the oxidation/reduction states of the material to match a defined recording wavelength for high diffraction is suggested.

Optical spectroscopy and energy transfer of Er3+/Ce3+ in B2O3-doped bismuth-silicate glasses

Ce3+ and B2O3 are introduced into erbium-doped Bi2O3-SiO2 glass to enhance the luminescence emission and optic spectra characters of Er3+. The energy transfer from Er3+ to Ce3+ will obviously be improved with the phonon energy increasing by the addition of B2O3. Here, the nonradiative rate, the lifetime of the I-4(11/2) -> I-4(3/2) transition, and the emission intensity and bandwidth of the 1.5 mu m luminescence with the I-4(13/2) -> I-4(5/2) transition of Er3+ are discussed in detail. The results show that the optical parameters of Er3+ in this bismuth-borate-silicate glass are nearly as good as that in tellurite glass, and the physical properties are similar to those in silicate glass. With the Judd-Ofelt and nonradiative theory analyses, the multiphonon decay and phonon-assisted energy-transfer (PAT) rates are calculated for the Er3+/Ce3+ codoped glasses. For the PAT process, an optimum value of the glass phonon energy is obtained after B2O3 is introduced into the Er3+/Ce3+ codoped bismuth-silicate glasses, and it much improves the energy-transfer rate between Er3+ I-4(11/2)-I-4(13/2) and Ce3+ F-2(5/2) -> F-2(7/2), although there is an energy mismatch. (c) 2007 Optical Society of America.