Electrically Controlled Dimensionality of Magnetic Systems in Organic Materials

Electrically controlling charge density in materials using electronic device structures shows various interesting phenomena, such as electrically induced ferromagnetism and superconductivity, owing to strong charge interactions. However, electrically controlled dimensionality of magnetic systems has not yet been fully investigated. Here we report electrically controlled magnetic interactions and dimensionality of magnetic systems in organic materials from a microscopic viewpoint, which were revealed by electron spin resonance (ESR) spectroscopy using ionic liquid-gated devices. The ESR investigation demonstrated that the magnetic systems’ dimensionality of electrically accumulated charges varied from zero dimensional to two dimensional in a regioregular polymer, regioregular poly(3-hexylthiophene) (RR-P3HT), by increasing charge densities. This phenomenon is in contrast to those in a small molecule pentacene and a regiorandom polymer, regiorandom poly(3-hexylthiophene) (RRa-P3HT), where it varied from zero to three dimensional when their charge densities increased. Moreover, the formation of the complete spinless states of electrically induced charges was observed. Our investigation demonstrates the novel magnetic systems based on electrically induced charges.     

Synthesis of spin-labelled poly(acrylic acid)s and their segmental motion study

Understanding the segmental dynamics of polymer chains is cardinal to decipher the microscopic behaviour in order to modulate the bulk properties of polymers. The study of electron spin resonance (ESR) spectroscopy of spin-labelled polymers is useful to understand the segmental dynamics of polymer chains in solution. In this paper, poly(acrylic acid)s (PAAs) were spin labelled with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl radicals. Spin-labelled PAAs (SL-PAAs) were characterised by Fourier-transform infrared spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, differential scanning calorimetry, cyclic voltammetry (CV), and ESR analyses. The polyelectrolyte complexes of SL-PAAs were prepared by employing poly(diallyldimethylammonium chloride) (PDADMAC) as the polycation and analysed by transmission electron microscopy, dynamic light scattering (DLS), and ESR spectroscopies. The effect of molar mass on the segmental dynamics of SL-PAAs in pristine as well as in the form of polyelectrolyte complexes (PECs) was studied. The results indicated that SL-PAAs show a differential complexation behaviour with PDADMAC in the PECs depending on their molar mass.     

ESR of exchange coupled Cr3+ pairs in the dimer Di-μ-Diphenylphosphinatoacetyl-Acetonatochromium(III) (DPACr)

DPACr is a dimeric phosphinate in which the pairs of Cr³⁺ ions are superexchange coupled via -OPO- bridges. The consequences of site anisotropy and inequivalence are demonstrated in the ESR spectra and can be derived using a perturbation scheme on the appropriate Hamiltonian. First and second order fine structure, multiplet shifts, g-shifts and g-anisotropies are discussed. This dimeric system is the simplest member of a class of poly(chromium phosphinates).     

ESR and ENDOR studies of solitons and polarons in conjugated polymers

Nonlinear excitations such as solitons and polarons in conjugated polymers carry spins. In this case electron spin resonance (ESR) and electron-nuclear double resonance (ENDOR) provide unique methods to determine their wave functions. In this review article, the case of solitons in polyacetylene, CH_x, and polarons in an electroluminescent polymer, poly(paraphenylene vinylene) (PPV) are discussed as typical examples. High-resolution proton ENDOR spectra, obtained with stretch-oriented samples, yield the half extension of the excitations of 18 carbon atoms and 4 phenyl rings for CH_x and PPV, respectively. These extensions are well described by the theories in the case of finite electron correlation. In addition, light-induced ESR technique is shown to be useful in obtaining site-selective information of spin distribution in the case of PPV derivatives, as well as the excitation spectra of polarons.     

掺杂纳米硅薄膜中电子自旋共振研究

研究了掺杂纳米硅薄膜(nc∶Si∶H)中的电子自旋共振(ESR)及与之相关的缺陷态.样品是用等离子体增强化学气相沉积方法制成,为两相结构,即纳米晶粒镶嵌于非晶本体之中.对掺磷的nc-Si∶H样品,测量出其ESR信号的g值为1.9990—1.9991,线宽ΔH_pp为(40—42)×10^-4T,ESR密度Nss为10¹⁷cm^-3数量级.对掺硼的nc-Si∶H样品,其ESR信号的g值为2.0076—2.0078,ΔH_{关键词： 纳米硅薄膜 微结构 电子自旋共振}     

L波段三维ESR成像系统的研制（Ⅱ）——L波段三维ESR成像系统

叙述了一个L波段（1.05 GHz）用于ESR和ESR成像的装置，用这套自制装置实现了3D ESR成像. 该装置由L波段ESR谱仪、三组梯度场线圈及控制单元和PC机数据采集系统组成. 样品腔是一个3-环2-缝再进入式谐振腔，可放入直径为20 mm、 长30 mm的H₂O样品，空谐振腔的频率是1.05 GHz. 微波振荡频率用自动频率控制（AFC）的方法自动锁在有载腔的频率上. 梯度场线圈沿X-，Y-和Z-轴产生线性梯度场，在中心40 mm球形范围内梯度场强度为2 mT/cm. 依照Lauterbur's方法进行3D ESR 图像重建. 用该系统检测了样品中TEMPO氮氧自由基的3D空间分布. 得到了TEMPO的2D、3D ESR图像、用像素灰度表示的自旋密度分布图及3D ESR-CT图像.     

3dZ2基态铜(Ⅱ)冠醚配合物的粉末ESR谱

制备了两种不同基质的掺杂3d_Z²基态铜(Ⅱ)苯并15冠5配合物(Cu(Ⅱ)B15C5)的粉末样品,ESR测定结果表明,以B15C5为基质时,Cu(Ⅱ)B15C5的轴向配体是H₂O;而以Mg(Ⅱ)B15C5为基质时的轴向配体则是CIO₄^-.不同的轴向配体对ESR谱的线型有着较大的影响。利用Bleaney公式,计算了键参数,并对成键特性进行了讨论和比较。     

Identification of free radicals in irradiated MA-AMPS copolymer

Methacrylamide-2-acrylamido-2-methylpropanesulphonic acid (MA-AMPS) (80:20) is subjected to n -irradiation and the generated free radicals are identified by the electron spin resonance (ESR) technique. The ESR spectrum "obser"ved for MA-AMPS (80:20) has shown a complex line shape, indicating the presence of more than one free radical. Computer simulations are employed to unravel the radicals responsible for the ESR spectrum. Radical "identification has been done with the magnetic parameters employed during computer simulation. The observed ESR spectrum of the copolymer is simulated to be a superposition of component quartet, quintet and singlet spectra. The component spectra are assigned to ～CH 2 - . (CONH 2 )-CH 2 ～ or ～CH 2 - . H-CH 2 ～, . H 3 radicals, "respectively. The possibility of formation of such radicals in the sample material has been discussed.     

RCCo_3(CO)_9的电化学和RCCo_3(CO)_9~-的ESR谱研究

本文对三种RCCo_3(CO)_9及相应的自由基进行了电化学和ESR谱研究.电化学研究表明,RCCo_3(CO)_9被还原为自由基的难易与R的性质有关,RCCo_3(CO)_9在室温下可以稳定存在.在对分子轨道对称性分析的基础上对簇合物自由基的ESR谱进行了讨论.确定了超精细偶合常数的符号和未成对电子占据轨道的性质,计算了Co的3d轨道和4s轨道的自旋密度.     

Relevance of ferromagnetic correlations for the electron spin resonance in Kondo lattice systems

Electron spin resonance (ESR) measurements of the ferromagnetic (FM) Kondo lattice system CeRuPO show a well defined ESR signal which is related to the Ce3+ magnetism. In contrast, no ESR could be observed in the antiferromagnetic (AFM) homologue CeOsPO. Additionally, we detect an ESR signal in ferromagnetic YbRh while it was absent in a number of Ce or Yb intermetallic compounds with dominant AFM exchange. Thus, the observation of an ESR signal in a Kondo lattice is neither specific to Yb nor to the proximity to a quantum critical point, but seems to be connected to the presence of FM fluctuations. These conclusions not only provide a basic concept to understand the ESR in Kondo lattice systems even well below the Kondo temperature (as observed in YbRh2Si2) but point out ESR as a prime method to investigate directly the spin dynamics of the Kondo ion.     

Multifrequency ESR Characterization of Paramagnetic Point Defects in Semiconducting Cubic BN Crystals

Low-frequency (X-band) electron spin resonance (ESR) investigations on commercially available large-grained cubic boron nitride (cBN) superabrasive powders of various coloration, combined with high-frequency (W-band) ESR measurements on oriented submillimeter-size single crystallites selected from the same powder samples, resulted in a clear identification of several types of paramagnetic point defects. The resulting spin Hamiltonian parameters describing the ESR spectra observed in the 3–293 K temperature range and the photosensitivity of the paramagnetic defects observed in amber-colored cBN samples are reported. It is shown that the nature of the paramagnetic centers depends on the color of the investigated samples and that, in many cases, uncontrolled impurities seem to be involved in their structure.     

连续波电子自旋共振的二维相关谱

在数学相关分析的基础上,建立了获得连续波电子自旋共振（continuous-wave electronspin resonance, CW-ESR）的二维相关谱的方法. 对光照产生的2-甲基-2-亚硝基-丙烷(2-methyl-2-nitrosopropane, MNP)的自捕捉自由基的一系列CW-ESR谱进行相关分析处理,首次得到了同步和异步的二维电子自旋共振（2D ESR）相关谱. 这种利用数学相关分析方法所得到的2D ESR相关谱将为扩大CW ESR的应用领域及获取更多的有用信息开拓新的途径.     

Low temperature electron spin resonance of the Kondo ion in a heavy fermion metal: YbRh2Si2

We report an electron spin resonance (ESR) study on single crystals of the heavy fermion metal YbRh2Si2 which shows pronounced non-Fermi liquid behavior related to a close antiferromagnetic quantum critical point. It is shown that the observed ESR spectra can be ascribed to a bulk Yb3+ resonance. This is the first observation of ESR of the Kondo ion itself in a dense Kondo lattice system. The ESR signal occurs below the Kondo temperature (T(K)) which thus indicates the existence of large unscreened Yb3+ moments below T(K). We observe the spin dynamics as well as the static magnetic properties of the Yb3+ spins to be consistent with the results of nuclear magnetic resonance and magnetic susceptibility.     

Electron Spin Resonance–Native Signal in Thermally Treated Dental Tissue

Although the dosimetric Electron Spin Resonance (ESR) signal of hard tissues, particularly enamel, has been extensively studied, little attention has been paid to the native signal. This signal is known to be affected by the health of the tissue, as well as by socio–economic factors. In dental applications several clinical procedures, including the use of laser irradiation, can heat the tissue locally with side effects that must be studied. The purpose of the present work is to study the ESR signals in enamel and dentin tissues after thermal treatment with temperatures in the range of 100°C–300°C. Non‐irradiated permanent bovine teeth were studied. ESR measurements were performed with a Varian E‐4 ESR spectrometer operating in the X band range. Progressively larger ESR signals were produced in dentin tissues previously heat treated at and above 100°C. No detectable signals were observed in similarly treated enamel. The signal shows partial decay at four and six months after thermal treatment. The experimental data for dentin show a correlation with the Arrhenius function with an activation energy of (41 ± 2)10³ J/mol. After six months, the ESR signal shows a higher activation energy (67 ± 3)10³ J/mol and the decay shows a activation energy of (38 ± 2)10³ J/mol. A possible assignment of the signal origin in dentin is difficult. The water lost during thermal treatment and reincorporated during the following six months correlates with the signal gain and subsequent decay. The water lost can produce point defects in the hydroxyapatite, or structural changes in the collagen structure. The results observed here are useful for understanding the thermal effects produced in dentin by infrared laser irradiation, and provides a cautionary warning that annealing conditions in ESR studies of biological tissues should be standardized.     

Electron spin resonance in Ge0.99Mn0.01 nanowires

Electron spin resonance (ESR) is measured in arrays of Ge_0.99Mn_0.01 nanowires (NWs). We show that the ESR spectrum comprises four lines corresponding to the different magnetic subsystems. Two lines are attributed to spin-wave excitations in the Mn⁺³ ion subsystem. The third component corresponds to the resonance in the Mn⁺² ions. The last component has an asymmetric Dyson form and characterizes the resonance in the mobile paramagnetic centers. We demonstrate that temperature dependences of ESR parameters are correlated in subsystems of the localized magnetic centers (Mn⁺³ and Mn⁺² ions) and delocalized band carriers. It implies the presence of exchange interactions between the localized Mn ions and spin-polarized carriers.     

Quantum critical Kondo quasiparticles probed by ESR in β-YbAlB₄

Electron spin resonance (ESR) can probe conduction electrons (CE) and local moment (LM) spin systems in different materials. A CE spin resonance (CESR) is observed in metallic systems based on light elements or with enhanced Pauli susceptibility. LM ESR can be seen in compounds with paramagnetic ions and localized d or f electrons. Here we report a remarkable and unprecedented ESR signal in the heavy-fermion superconductor β-YbAlB? [S. Nakatsuji et al., Nature Phys. 4, 603 (2008)] which behaves as a CESR at high temperatures and acquires characteristics of the Yb3? LM ESR at low temperature. This dual behavior strikes as an in situ unique observation of the Kondo quasiparticles in a quantum critical regime. The proximity to a quantum critical point may favor the appearance of this dual character of the ESR signal in β-YbAlB?.     

MgF2单晶中位错缺陷的ESR谱——含有130多条谱线

在室温条件下的激光晶体MgF2单晶中，实验发现含有130多条峰的电子自旋共振(ESR)波谱。两个样品分别取自MgF2单晶生长放肩的尖锥部位和MgF2:Co晶体.两个样品都没有经过任何辐照处理。两个样品具有相同的各向异性谱，说明掺入的Co2+离子引发了与MgF2单晶放肩部位相同的位错缺陷，产生了相同的多核固体自由基。这些顺磁固体自由基稳定且寿命长，产生的ESR信号是各向异性的。经初步计算拟合，谱线是由三种不同的多核自由基产生的。当磁场方向与晶体的[100]或[010]方向平行时，样品的ESR信号出现在磁场从0.2292特斯拉（T）到0.4654T的0.2362T范围内（相当于能带宽度为0.233eV）。最窄的线宽DH约为0.00128特斯拉，DH相当于相邻的能级差,是非常小的，仅有1.85×10-7eV 或1.46×10-3cm-1。这一事实表明其基态简并度是相当高的，在不太高的直流磁场下几乎是一个由准连续的能级组成的能带。这有可能成为可调谐的固体激光介质的新基点。     

脉冲强磁场高频电子自旋共振装置的研制

国内第一套脉冲强磁场高频电子自旋共振(ESR)装置由武汉国家脉冲强磁场科学中心研制成功.该装置的频率范围为210-370 GHz,样品温度范围为2-300 K, 磁场强度为0-50 T.在脉冲强磁场ESR装置上进行了红宝石ESR实验,获得了Cr³⁺ 离子的ESR谱.     

Modelling of multifrequency ESR spectra of Fe3+ ions in crystalline and amorphous materials: A Simplified approach to determine statistical distributions of spin-spin coupling parameters

Focussed on the understanding of the complex Fe³⁺ electron spin resonance (ESR) spectra in crystalline and amorphous systems, the simulation program ESR-MAKRO-1 was developed, which allows the calculation of powder spectra of paramagnetic centers with 1/2 ≤S ≤7/2. For the reproduction of the ESR spectra of amorphous systems Gaussian distributions of the zero-field-splitting parameters of second and fourth order (D, E, a, F) were implemented into the program. Applications of ESR-MAKRO-l are given both for crystalline powders and for glassy systems. A stepwise analysis of the ESR spectra, allowing an approach to Fe³⁺ ESR spectra of amorphous matrices and showing the influence ofD, E, a, andF as well as their distributions, is given.     

时间域电子自旋共振

时间域电子自旋共振(ESR)是研究顺磁弛豫机理和动力学过程不可缺少的方法,也是提高检测信号的灵敏度和分辨率的重要途径之一。然而,目前在ESR技术中较常用的还是频率域,而时间域ESR(包括付里叶变换法)却远远不如脉冲付里叶变换核磁共振(PFT-NMR)那样迅速的发展。本文对此进行了讨论,认为:如采用与PFT-NMR稍为不同的方法,并在微波技术、快速脉冲电路和电子计算技术等不断改善的基础上,时间域ESR势将成为今后发展的大方向。近年来,在时间域ESR技术方面,最引人重视的是:饱和恢复法和电子自旋回波(ESE)法。本文着重对这两种方法的基本原理、实验方法、应用场合及其优越性和局限性进行了评述。例如,用付里叶变换法(包括二维付里叶变换)把电子自旋回波调制的包络自时间域变换成频率域,从而获得高分辨率的频谱,则可分析出取向或无规取向样品的微弱超精细结构。又如,ENDOR(电子-核双共振)自旋回波与通常的ENDOR相比,前者具有较高的灵敏度以及可检测较低的ENDOR频率等独特之处。此外,文中对瞬态顺磁中间产物的时间分辨ESR和三重态分子在零场中的ESR也分别进行了简短的评介。最后,对时间域ESR发展的远景作了预计。