室温下磁场对基于Alq3的有机电致发光器件的影响

制备了ITO/NPB/LiF/Alq₃/LiF/Al的器件,测量了该组器件效率和亮度的磁效应.结果表明,在50 mT磁场中,当LiF缓冲层厚度为0.8 nm时,器件的效率最大增加了12.4%,磁致亮度最大变化率17%.同时,制备的磷光器件ITO/NPB/LiF/CBP:6 wt% Ir(ppy)₃/BCP/Alq₃/ LiF/Al,在50mT磁场作用下,当LiF缓冲层的厚度为0.8 nm时,器件的效率最大增加12.1%.在Alq_{3 关键词： 有机发光 磁场 效率 磁致亮度}     

基于Alq3的有机发光二极管的磁电导效应

制备了结构为 ITO/CuPc/NPB/Alq₃/LiF/Al 的有机发光二极管,并在300,260,220和180 K 四个温度测量了器件在恒压偏置下注入电流的磁场效应(磁电导效应).在注入电流从双极电流过渡到单极电流的过程中,随电流减小,器件的磁电导呈现先上升后下降的变化趋势.当温度降低,磁电导的值下降.但在任何测量条件下,器件的磁电导始终为正,没有出现如文献报道的磁电导从正到负的变化.实验结果表明,有机发光二极管中正负磁电导现象的产生,并非仅取决于注入电流是单极电流还是双极电流,它还与有机材料、器件结构等密切相关.利用受磁场调控的“电子-空穴对”机理与“双极化子”模型,分别解释了器件双极电流和单极电流的正磁电导效应. 关键词： 有机发光二极管 磁电导 双极化子     

Transport and recombination in organic light-emitting diodes studied by electrically detected magnetic resonance

We have used electrically detected magnetic resonance (EDMR) to study a series of multilayer organic devices based on aluminum (III) 8-hydroxyquinoline (Alq₃). These devices were designed to identify the microscopic origin of different spin-dependent processes, i.e. hopping and exciton formation. The EDMR signal in organic light-emitting diodes (OLEDs) based on Alq₃ is only observed when the device is electroluminescent and is assigned to spin-dependent exciton formation. It can be decomposed in at least two Gaussians: one with peak-to-peak line ( ΔH_PP) of 1.6 mT and another with ΔH_PP of 2.0 to 3.4 mT, depending on bias and temperature. The g-factors of the two components are barely distinguishable and close to 2.003. The broad line is attributed to the resonance in Alq₃ anions, while the other line is attributed to cationic states. These attributions are supported by line shape and its electrical-field dependence of unipolar Alq₃-based diodes, where hopping process related to dication and dianion formation is observed. In these unipolar devices, it is shown that the signal coming from spin-dependent hopping occurs close to organic semiconductor/metal interfaces. The sign of the magnetic-resonance-induced conductivity change is dominated by charge injection rather than charge mobility. Our results indicate that the probability of singlet exciton formation in our OLEDs is smaller than 25%.     

有机发光器件的磁电导效应

制备了基于三(8-羟基喹啉)铝(tris-(8-hydroxyquinoline) aluminum (III), Alq₃) 的有机发光二极管, 并在不同偏压下测量了器件的室温磁电导效应.在小偏压下, 发光器件展示出明显的负磁电导效应.偏压增加后, 磁电导由负值变为正值, 出现了正负转变的现象. N, N'-二苯基-N, N'-(1-萘基)-1, 1'-联苯-4, 4'-二胺(N, N′-Di(naphthalen-1-yl)-N, N′ diphenyl-benzidine, NPB) 与铜酞菁 (Copper phthalocyanine, CuPc) 单极器件磁电导的测量结果表明, 发光器件在小偏压下的负磁电导效应来源于器件中的CuPc层. 双极电流的磁电导效应可用电子-空穴对模型进行解释, 而单极电流的磁电导效应可归因于器件中的极化子-双极化子转变. 在注入电流的变化过程中, 发光器件的正负磁电导转变是两种机理共同作用的结果.     

ESR study of exchange coupled pairs in copper diethyldithiocarbamate—explanation of the low temperature hyperfine anomaly

A study of the hyperfine interaction in the ESR of Cu-Cu pairs in single crystals of copper diethyldithiocarbamate as a function of temperature has shown distinct differences in the hyperfine structure in the two fine structure transitions at 20 K, the spectrum not having the same hyperfine intensity pattern in the low field fine structure transition in contrast to that of the high field transition. The details of the structure of both the fine structure transitions in the 20 K spectrum have now been explained by recognizing the fact that the mixing of the nuclear spin states caused by the anisotropic hyperfine interaction affects the electron spin states | + 1 > and | −> differently. This has incidentally led to a determination of the sign ofD confirming the earlier model. The anomalous hyperfine structure is found to become symmetric at 77 K and 300 K. It is proposed that the reason for this lies in the dynamics of spin-lattice interaction which limits the lifetime of the spin states in each of the electronic levels | − 1 >, | 0 > and | + 1 > The estimate of spin-lattice relaxation time agrees with those indicated from other studies. The model proposed here for the hyperfine interaction of pairs in the electronic triplet state is of general validity.     

EPR in LiTbF4 using an HCN laser

The Tb³⁺ electron paramagnetic resonances of a spherically shaped LiTbF₄ single crystal were measured with the static magnetic field along the c-axis, using an HCN laser at 890.8 and 964.3 GHz. At 4.2 K the measured spectrum consists of four hyperfine lines which have a spacing of 25.0± 0.2 mT and a width of roughly 10 mT. The g-factor is 17.75 ± 0.1 at both frequencies. In each hyperfine line of the spectrum at 4.2 K a superimposed structure is seen. This structure is explained by changes in the dispersion of the LiTbF₄ crystal.     

Theoretical investigations on the Stark-Zeeman effect of the 2p~{}^{\mathsf 2}P3/2-level in 6Li for perpendicularly crossed fields

The splitting behaviour of the P_3/2 hyperfine structure levels is investigated in ⁶Li for homogeneous crossed electric and magnetic fields (Stark-Zeeman effect). This is done by diagonalizing the perturbation matrix comprising the hyperfine interaction, the electronic and nuclear magnetic interaction and the effective electric interaction obtained by transforming the quadratic Stark effect to a first order perturbation interaction. Symmetries are used to find analytic formulae for level shifts and crossing points if only one external field is present. A reflection symmetry unbroken with all three interactions present permits the decomposition of the 12 ×12 matrix into two 6 ×6 submatrices. The structure of energy eigenvalue surfaces epsilon_{F,M F}(B,E) of the two subsystems is found by numeric diagonalization of the perturbation matrix and is displayed in the ranges |B|< 1 mT kV/cm. The total angular momentum F = J + I  (J = 3/2, electronic angular momentum, I = 1, nuclear spin) and the magnetic quantum number M_F provide labels for all surfaces. All crossing points of the energy surfaces have been found. Adiabatic level transfer occurring in atoms traversing a sequence of crossed magnetic and electric fields is explained. Berry phases occur for cycles around some crossing points. Their presence or absence is explained.     

激子复合区厚度对有机磁效应的影响

在常规型有机发光二极管的基础上, 通过改变发光层tri-(8-hydroxyquinoline) aluminum (III) (Alq₃)厚度, 研究了激子复合区厚度对有机发光二极管磁效应的影响.测量了器件在不同温度及偏压下电致发光及注入电流在外加磁场作用下的变化, 着重研究了低温下的有机磁电导效应和有机磁电致发光效应.实验发现, 低温(50 K)高磁场 (500 mT)下, 器件表现出随Alq₃厚度的减薄, 磁电导值由正到负再到正的非单调变化.利用磁场调控的超精细相互作用、 磁场抑制的三重态激子-电荷反应以及激子在界面的淬灭效应, 对有机磁电导在低温下表现出的现象进行了定性的解释.实验结果表明, 通过改变激子复合区的厚度, 可以实现对激子浓度的有效调节, 进而实现对有机磁电导和磁电致发光效应的调节. 该研究进一步丰富了有机磁效应的实验现象, 同时提供了一种调控有机磁效应的手段. 关键词： 激子复合区 激子浓度 有机磁电导 有机磁电致发光     

Infrared and EPR Spectroscopic Studies of 2-C(2)H(2)F and 1-C(2)H(2)F Radicals Isolated in Solid Argon

2-fluorovinyl radicals were generated in solid argon by solid-state chemical reactions of mobile F atoms with acetylene and its deuterated analogues. Highly resolved EPR spectra of the stabilized radicals CHF&dbond;(*)CH, CDF&dbond;(*)CD, CHF&dbond;(*)CD, and CDF&dbond;(*)CH were obtained for the first time. The observed spectra were assigned to cis-2-fluorovinyl radical based on excellent agreement between the measured (a(F) = 6.50, a(betaH) = 3.86, a(alphaH) = 0.25 mT) hyperfine constants and those calculated using density functional (B3LYP) theory. Analogous experiments carried out using infrared spectroscopy yielded a complete assignment of the vibrational frequencies. An unusual reversible photochemical conversion is observed in which cis-2-fluorovinyl radicals can be partially converted to 1-fluorovinyl radicals by pulsed laser photolysis at 532 nm. Photolysis at 355 nm converts 1-fluorovinyl back to cis-2-fluorovinyl. High-resolution EPR and infrared spectra of 1-fluorovinyl were obtained for the first time. The measured hyperfine constants (a(F) = 13.71, a(H1) = 4.21, a(H2) = 1.16 mT) are in good agreement with calculated values. Copyright 2001 Academic Press.     

Resistive switching in Ag–TiO2 contacts

We study the electric pulse induced resistance switching of TiO₂–Ag contacts at room temperature, exploring both unipolar and bipolar switching modes. Initially we observed unipolar response. After hundred pulsing cycles the unipolar switching response vanishes but the device can still be operated in bipolar switching regime. The underlying mechanism for resistance switching is modeled in terms of formation and rupture of filament, and movement of oxygen vacancies.     

The temperature dependence of the magnetic hyperfine field of tantalum in dysprosium

The temperature dependence of the magnetic and electric hyperfine interactions at the site of ¹⁸¹Ta impurities in polycrystalline Dy has been measured between 4.2 and 178 K using the time differential perturbed angular correlation technique. The value of the magnetic hyperfine field at 4.2 K is: |H_hf(TaDy)| = 212(9) kG The temperature dependence of the magnetic hyperfine field follows closely the prediction of the molecular field model.     

磁场对基于Co铁磁薄膜的有机发光器件效率和电流的影响

制备结构为ITO/Co/NPB/Alq₃/LiF/Al的有机发光器件,测量了室温下磁场对器件发光效率和电流的影响.发现磁场强度小于80 mT时,器件发光效率随磁场强度的增加而增大,最大为18.8%,随磁场强度的继续增加发光效率的增强趋于饱和.效率的增加是Co的自旋极化的注入和磁场效应共同作用的结果,其中自旋极化注入起主要作用.在磁场强度小于60 mT时电流随磁场增强而增加,最大为6.9%,随磁场强度的进一步增加电流的增加有所减弱.产生这种现象的原因可归结为磁场相关的单线态极化子对的解 关键词： 有机电致发光 自旋极化 磁场效应     

Effect of cation and anion defects on the resistive switching polarity of ZnO x thin films

In this paper, we achieve the resistive switching (RS) polarity from unipolar to bipolar in a simple Al/ZnO _x /Al structure by moderating the oxygen content in the ZnO sputtering process. In a pure Ar sputtering, Al/ZnO _x /Al shows unipolar behavior, as oxygen partial pressure increases, the RS polarity changes to bipolar, and the switch current decreases by about five orders of magnitude. The current transport properties of unipolar device show ohmic behavior under both high resistance (HRS) and low resistance states (LRS), but the bipolar device shows Schottky barrier modulated current transport properties. We study the defect types in the unipolar and bipolar devices through photoluminescence (PL) spectra. The PL results show that the interstitial zinc (Zn_i) and interstitial oxygen (O_i) are dominant in unipolar and bipolar devices, respectively. We attribute this phenomenon to Zn_i and O_i playing important role in unipolar (URS) and bipolar resistive switching (BRS), respectively.     

Magnetic anisotropy of Ni modified by extreme lattice expansion

The induced magnetism of isolated (Cd) adatoms, soft-landed onto ultrathin Ni layers grown pseudo-morphologically on Pd(001) (a_Pd = 3.8907 Å), was studied using the perturbed angular correlation (PAC) technique. The magnitude of the induced magnetic response (magnetic hyperfine field of |5.2| T) was found to be ca. 30% smaller than on bulk Ni (a_Ni = 3.524 Å) surfaces. This result is compared to ab initio calculations. Additionally, the magnetic anisotropy of the induced response was found to be modified as compared to bulk Ni surfaces and the induced hyperfine field was observed to emerge from the plane at an angle of 50(5)^○ to the surface normal. This canted magnetic anisotropy is attributed to the large lattice expansion of the ultrathin Ni film on Pd(001).     

Effect of solvent nature on spin exchange in rigid nitroxide biradicals

Intramolecular electron spin exchange as a function of temperature and solvent viscosity and polarity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two rigid nitroxide biradicals existing in one spatial conformation only. Temperature variations of the isotropic hyperfine splitting constanta and exchange integral value |J/a| were measured from EPR spectra and subsequently analyzed. The interaction of polar solvent molecules with >N-O fragments of nitroxide groups led to a slight decrease of the |J/a| value with the increase of temperatureT. In contrast, the interaction of polar solvent molecules with functional groups inside the bridge resulted in a noticeable increase of |J/a| vs.T. In the last case, a coverse relationship between the values of |J/a| and the hyperfine splitting constanta has been observed for solvents with different polarity.     

Low temperature pressure dependence of the muon hyperfine fields in iron,cobalt and nickel

The pressure dependence of the μ⁺ local magnetic fields in polycrystalline Fe and Ni and a Co single crystal has been measured at 77 K, up to 0.7 GPa, using a He gas high pressure setup. The pressure derivatives dlnB_μ/dP in units of mT/GPa are +4.4±1.0 (Fe), -0.7±1.1 (Co) and +0.63±0.10 (Ni). From these values the hyperfine field volume derivatives are deduced. Using these values together with previously determined room temperature derivatives the thermal expansion part of the temperature dependence of the hyperfine field can be calculated. The remaining explicit temperature dependence below 300 K, which deviates markedly from the temperature dependence of the bulk magnetization, is discussed.     

有机发光二极管的光致磁电导效应

制备了结构为ITO/CuPc/NPB/Alq₃/LiF/Al的常规有机发光二极管, 之后对器件采用波长为442 nm和325 nm的激光线进行照射产生激子, 并在小偏压下(保证器件没有开启)对激子的演化过程进行控制, 同时测量器件的光致磁电导(photo-induced magneto-conductance, PIMC). 实验发现, 不同于电注入产生激子的磁电导效应, PIMC在正、反小偏压下表现出明显不同的磁响应结果. 当给器件加上正向小偏压时, 器件的PIMC在0-40 mT范围内迅速上升; 随着磁场的进一步增大, 该PIMC增加缓慢, 并逐渐趋于饱和. 反向小偏压时, 器件的PIMC随着磁场也是先迅速增大(0-40 mT), 但达到最大值后却又逐渐减小. 通过分析外加磁场对器件光生载流子微观过程的影响, 采用'电子-空穴对'模型和超精细相互作用理论对正向偏压下的PIMC进行了解释; 反向偏压下因各有机层的能级关系, 为激子与电荷相互作用提供了必要条件, 运用三重态激子与电荷的反应机制可以解释PIMC出现高场下降的实验现象.     

Radical cations of n-alkanes in irradiated solutions as studied by time-resolved magnetic field effects

The time-resolved magnetic field effect in the recombination fluorescence of spin-correlated radical ion pairs has been measured to study n-alkane radical cations in irradiated solutions at room temperature. The magnetic field effect was recorded as a ratio of fluorescence decay curves in the 0.1 T and zero magnetic fields for solutions of C₈, C₉, C₁₀, C₁₂, and C₁₆ n-alkanes in n-hexane with addition of 3 × 10^?5 M p-terphenyl-d ₁₄. A distinct maximum at 10–30 ns followed by a slowly decaying plateau was observed for all the solutions. Simulation shows that the maximum corresponds to an unresolved ESR spectrum with the peak-to-peak line-width ranging from about 1.6mT to 0.5mT for C₈ to C₁₆ radical cations. The unresolved structure is believed to result from the hyperfine couplings with many protons of the radical cation, the increase in the number of interacting protons compared with low temperature matrices being caused by the methyl group rotation and conformational motion of the carbon chain. With increase in concentration of dissolved n-alkane, the maximum in the curves first moves to longer times and finally disappears; this was attributed to the narrowing of ESR spectrum contour due to degenerate electron exchange.     

Mössbauer effect measurement in ferromagnetic CuCr2Te3I

Mössbauer effect measurement of the internal fields at ¹²⁹I impurities in the ferromagnetic halo-chalcogenide spinel CuCr₂Te₃I was performed. The magnetic hyperfine field was found to be |34±2| kOe. The results are compared with those measured in the spinel CuCr₂Te₄.     

Suppression of back-to-back hadron pairs at forward rapidity in d+Au collisions at √s(NN)=200 GeV

Back-to-back hadron pair yields in d+Au and p+p collisions at √s(NN)=200 GeV were measured with the PHENIX detector at the Relativistic Heavy Ion Collider. Rapidity separated hadron pairs were detected with the trigger hadron at pseudorapidity |η|<0.35 and the associated hadron at forward rapidity (deuteron direction, 3.0<η<3.8). Pairs were also detected with both hadrons measured at forward rapidity; in this case, the yield of back-to-back hadron pairs in d+Au collisions with small impact parameters is observed to be suppressed by a factor of 10 relative to p+p collisions. The kinematics of these pairs is expected to probe partons in the Au nucleus with a low fraction x of the nucleon momenta, where the gluon densities rise sharply. The observed suppression as a function of nuclear thickness, p(T), and η points to cold nuclear matter effects arising at high parton densities.