表层氟化温度对聚乙烯中空间电荷积累的影响

在实验室反应釜中于不同的温度(35 ℃, 55 ℃和70 ℃) 下, 以氟气体积浓度为12.5%的氟/氮混合气对热压制备的聚乙烯(PE) 片状试样(厚约0.8 mm) 进行了相同时间(2 h) 的表层氟化改性. 利用压力波法研究了氟化温度对PE中空间电荷积累的影响. 结果显示, 随着氟化温度的提高直流高压作用下的氟化试样中的空间电荷积累明显减少, 这个70 ℃的氟化试样中几乎没有空间电荷. 衰减全反射红外分析表明, 氟化引起了试样表层化学组成的本质变化及氟化度随氟化温度的明显提高. 接触角测量与表面能计算间接地表明了这些氟化层有显著增大的介电常数. 开路热刺激放电电流测量进一步揭示了这些氟化层 不同的电荷捕获特性, 及随着氟化温度的提高氟化层对化学杂质从半导性电极向PE扩散的增强的阻挡特性, 因此表明氟化层中自由体积的相应减小. 表层自由体积的减小对抑制空间电荷的积累, 比介电常数的增大和电荷陷阱的变化起到更加显著的作用.     

孔洞聚丙烯驻极体膜中空间电荷与孔洞击穿电荷的俘获特性

对孔洞聚丙烯(PP)驻极体膜系统的研究结果表明：孔洞PP膜中空间电荷的俘获特性随注入的空间电荷量或试样表面电位而变化,注入的电荷量较少时空间电荷主要被俘获在表面深陷阱和近表面次深陷阱中,较多的注入电荷量时空间电荷在进一步填充表层(表面和近表面)陷阱的同时,还将填充体内浅陷阱;这三类陷阱中心所对应的电荷脱阱温度分别约为160℃,138℃和92℃.而孔洞击穿电荷不仅被俘获在与试样表层空间电荷陷阱相似的孔洞表层陷阱中,还有相当的量穿过孔洞表层进入体内、成为浅阱俘获孔洞击穿电荷. 关键词： 孔洞聚丙烯膜 空间电荷 孔洞击穿电荷 俘获特性     

电荷俘获存储器数据保持特性第一性原理研究

本文研究HfO₂掺入Al替位Hf杂质和氧空位共同掺杂对电荷俘获型存储器存储特性的影响. HfO₂作为高介电常数材料由于具有缩小器件尺寸、提高器件性能等优势, 被广泛用于CTM的俘获层. 采用MS和VASP研究了HfO₂俘获层中掺入Al对氧空位形成能的影响. 同时计算了两种缺陷在不同距离下的相互作用能. 计算结果表明在HfO₂中掺入Al使得氧空位的形成能降低, 并且三配位氧空位的形成能比四配位氧空位的形成能降低的更多. 通过研究Al和三配位氧空位两种缺陷间不同距离的三种情况, 计算结果表明当缺陷间距为2.107 Å时, 体系的电荷俘获能最大; 量子态数最多; 布居数最小、Al–O键最长. 通过研究三种体系写入空穴后键长的变化, 得出当缺陷间距为2.107 Å时, 写入空穴后体系的Al–O键长变化最小. 以上研究结果表明, 掺入Al后可以有效提高电荷俘获型存储器的数据保持能力. 因而本文的研究为改善电荷俘获型存储器数据保持特性提供一定的理论指导.     

HfO_2中影响电荷俘获型存储器的氧空位特性第一性原理研究

随着器件尺寸进一步等比例缩小,高k材料HfO2作为俘获层的电荷俘获型存储器展现了较好的耐受性和较强的存储能力,且工艺相对简单,与传统半导体工艺完全兼容,因此得到了广泛的研究.为研究HfO2中氧空位引入的缺陷能级对电荷俘获型存储器存储特性的影响,运用第一性原理计算分析了HfO2中的氧空位缺陷.通过改变缺陷超胞中的电子数模拟器件的写入和擦除操作,发现氧空位对电荷的俘获基本上不受氧空位之间距离的影响,而氧空位个数则影响对电子的俘获,氧空位数多,俘获电子的能力就强.此外,四价配位的氧空位俘获电子的能力比三价配位的氧空位大.态密度分析发现四价配位的氧空位引入深能级量子态数大,并且受氧空位之间的距离影响小,对电子的俘获概率大.结果表明,HfO2中四价配位的氧空位缺陷有利于改善电荷俘获型存储器的存储特性.     

聚丙烯孔洞铁电驻极体膜的电极化及其电荷动态特性

根据栅控恒压电晕充电组合反极性电晕补偿充电法的实验结果计算出铁电驻极体的极化强度.结果说明，伴随着薄膜内孔洞气体的Paschen击穿，该铁电体的极化强度随栅压增加而显著上升.利用上述充电方法和热刺激放电(TSD)谱的分析讨论了这类空间电荷型宏观电偶极子，及与其补偿的空间电荷热退极化的电荷动态特性；阐明了这两类俘获电荷的能阱分布，即构成宏观电偶极子的位于孔洞上下介质层内的等值异号空间电荷分别被俘获在深、浅两种能值陷阱内，而位于薄膜表面层的注入空间电荷则被俘获在中等能值陷阱中. 关键词： 反极性电晕补偿充电法 铁电驻极体 充电电流 热刺激放电     

氟化时间对环氧树脂绝缘表面电荷积累的影响

为抑制环氧树脂绝缘的表面电荷积累、研究处理时间对表面电荷积累的影响, 使用氟/氮混合气在实验室反应釜中对环氧试样进行了不同时间(10 min, 30 min和60 min)的表面氟化处理. 衰减全反射红外分析与SEM断面和表面观察表明随氟化时间的增加, 氟化层的氟化度和厚度增大, 表面微观粗糙度降低、表面组织变得致密. 与开路热刺激放电电流测量所表明的、未氟化(原)试样有深的表面电荷陷阱和稳定的表面电荷相比, 这些氟化试样的表面不能存储电荷. 沉积在它们表面上的电晕电荷于室温下分别约在2 min, 10 min和15 min内快速衰减为零, 展现随氟化时间的延长而减慢的电荷释放速率. 表面电导率和接触角测量及表面能计算表明氟化引起表面电导率和表面润湿性与极性的显著增加, 但它们随氟化时间的延长而减小. 氟化试样表面电导率的显著增大归因于表面电荷陷阱的非常可能的实质变浅和表面吸附的水分. 表面充电电流测量进一步地表明, 与原试样几乎为零的稳态表面电流相比, 这些氟化试样在连续充电期间显现大的稳态表面电流. 这意味着这些氟化试样在充电期间比原试样有少得多的表面电荷积累.     

缺陷对电荷俘获存储器写速度影响

基于密度泛理论的第一性原理以及VASP软件,研究了电荷俘获存储器(CTM)中俘获层HfO2在不同缺陷下(3价氧空位(VO3)、4价氧空位(VO4)、铪空位(VHf)以及间隙掺杂氧原子(IO))对写速度的影响.对比计算了HfO2在不同缺陷下对电荷的俘获能、能带偏移值以及电荷俘获密度.计算结果表明:VO3,VO4与VHf为单性俘获,IO则是双性俘获,HfO2在VHf时俘获能最大,最有利于俘获电荷;VHf时能带偏移最小,电荷隧穿进入俘获层最容易,即隧穿时间最短;同时对电荷俘获密度进行对比,表明VHf对电荷的俘获密度最大,即电荷被俘获的概率最大.通过对CTM的写操作分析以及计算结果可知,CTM俘获层m-HfO2在VHf时的写速度比其他缺陷时的写速度快.本文的研究将为提高CTM操作速度提供理论指导.     

CC双键对氟化非晶碳薄膜I-V特性的影响

研究了电子回旋共振等离子体技术沉积的氟化非晶碳 (a_C :F)薄膜的电学性质 .发现对于不同C_Fx 含量的薄膜 ,CC含量的增大对薄膜的导电行为具有不同的影响 .薄膜的直流I_V特性呈现I =aV bVn规律 ,是低场强区的欧姆导电和高场强区的空间电荷限流 (SCLC)组成的导电过程 .由于非晶材料的空间电荷限流与带尾态密度的分布密切相关 ,而a_C :F薄膜中CC的含量决定带尾态密度的分布 ,因此a_C :F薄膜在高场下的空间电荷限流是由薄膜中 CC 决定的导电过程 .     

密度泛函理论研究氧空位对HfO2晶格结构和电学特性影响?

HfO2因高k值、热稳定性良好和相对Si导带偏移良好等特点,作为电荷俘获型存储器栅介质材料得到了广泛研究。为了明确高k俘获层提高CTM电荷俘获效率的原因,运用基于密度泛函理论的第一性原理计算,研究了氧空位引起HfO2的晶格变化及其影响计算结果显示优化后氧空位最近邻氧原子间距明显减小,次近邻O与Hf间距变化稍小。优化后氧空位明显改变局部晶格,而对较远晶格影响逐渐减弱,即引起了局部晶格变化深能级和导带电子态密度主要是Hf原子贡献,而价带则是O原子贡献。优化后各元素局部电子态密度和总电子态密度都明显大于未优化体系,局部电子态密度之和比总电子态密度小。优化后俘获电荷主要在氧空位周围和相邻氧原子上,而未优化时电荷遍布整个体系。优化后缺陷体系电荷局域能增大,电荷量增加时未优化体系电荷局域能明显减小,即晶格变化无饱和特性对电荷局域影响大。说明晶格变化对电荷的俘获能力较强,有利于改善存储器特性。     

红外光谱法研究XeF2表面氟化丁腈橡胶动力学

丁腈橡胶表面氟化可以在橡胶表面生成类似氟橡胶结构的保护膜,在保留基体高弹性、耐寒性等优良性能的基础上,可以使丁腈橡胶的抗摩擦、耐介质和抗老化性能得到增强,使用范围增大.用红外光谱法进行了丁腈橡胶氟化反应动力学探索,得到了实验反应速率方程,丁腈橡胶表面氟化反应表观上为1.5级反应.由于反应生成的氟化层对后续反应的影响,实验反应级数存在随氟化时间增加而减小的趋势,速率常数则随着反应温度升高而减小.     

Experiment and simulation of space charge suppression in LDPE/MgO nanocomposite under external DC electric field

In this paper, space charge dynamics under DC electric field of −100 kV/mm in low-density polyethylene (LDPE) and its nanocomposite containing a small amount of MgO nanoparticles were measured using an improved pulsed electro-acoustic (PEA) system. Unlike negative packet-like space charge accumulating in LDPE films, no remarkable space charge was observed in LDPE/MgO nanocomposite films, which indicated that the introduction of MgO nanoparticles played a key role on the space charge suppression. Different with current qualitative models, this paper describes space charge suppression on the basis of simulation using the bipolar charge transport model, which featured bipolar charges injection, transport, trapping, recombination, and extraction process. It was shown from the simulation that trap depth, trap concentration, local electric field and charge injection barrier height were all significant factors on the space charge suppression process. A deeper trap depth in LDPE/MgO nanocomposites made it easier for traps to capture mobile carriers. And a larger trap concentration effectively slowed down the whole carrier movement although there seemed a trap concentration threshold less than 30 Cm⁻³, above which this effect became slight. In addition, both the high permittivity of LDPE/MgO nanocomposites and low local electric field in the vicinity of cathode led to a larger injection barrier height based on the Schottky injection law, which would tremendously block the charge injection. At last, the suppression mechanism of space charge formation in the LDPE/MgO nanocomposites is presented.     

以能带理论诠释直流聚乙烯绝缘中空间电荷的形成和抑制机理

高压直流塑料交联聚乙烯电缆的研发难点是消除其中的空间电荷效应. 目前, 国内外学者普遍通过添加纳米粒子在聚乙烯体内形成深陷阱捕获电荷的机理来抑制电荷积聚, 但此抑制机理违背了电场的基本理论. 以能带理论全面阐述聚合物介质中空间电荷的形成和抑制机理, 从一级陷阱模型出发, 应用电荷入陷和脱陷动力方程, 推导了聚合物介质中空间电荷的形成过程. 在聚合物介质中引入深陷阱后, 介质Fermi能级位移, 电极与介质之间界面接触由Ohm接触转变为阻塞接触. 考虑到无定形相中大量的陷阱密度, 电荷耗尽区宽度小于100 Å, 电极与介质之间的界面对电子变得透明, 形成中性接触, 在电压作用下, 这种聚乙烯介质中不再可能形成空间电荷. 最后, 在纯聚乙烯和纳米改性后含有深陷阱的聚乙烯两种试样上, 分别测量了电导与电场强度的关系和空间电荷分布曲线, 实验结果符合理论推导. 关键词： 直流绝缘 能带理论 空间电荷 抑制机理     

Fluorinated nanocarbons using fluorinating agent: Strategies of fluorination and applications

The fluorination method strongly influences the physical properties of the resulting fluorinated carbon materials. Two fluorination ways, direct fluorination under pure fluorine gas and controlled fluorination by the decomposition of TbF₄, have been used for the fluorination of particular nanocarbons: carbon nanofibers and a mixture of carbon nanodiscs and nanocones. Then, fluorocarbon matrix structures have been determined owing to solid state ¹⁹F NMR for MAS conditions at a spinning speed of 30 kHz. It reveals that the fluorination mechanism depends on the fluorination conditions but not on the starting nanocarbons morphology, i.e. tubular or planar. Finally, the electrochemical properties of carbon nanofibers fluorinated by the two ways are detailed. Controlled fluorination allows an increase of the power densities of fluorinated carbon nanofibers used as electrode in primary lithium batteries.     

Lattice Boltzmann equation method in electrohydrodynamic problems

A consistent lattice Boltzmann equation (LBE) model for simulating different electrohydrodynamic (EHD) phenomena is developed. The model includes fluid dynamics, electric charge transport via advection and conduction currents, and action of electric forces upon space charges in liquid. Problems with different thermodynamic phases (liquid and gaseous) and phase transitions, and with inhomogeneous and density-dependent electric permittivity and conductivity can also be simulated, as well as charge injection and recombination. Deformations and breakup of conductive vapor bubbles, bubble deformation due to electrostriction, dynamics of drops with different electric permittivity were simulated. Simulations show the great potential of the method especially for problems with free boundaries (systems with vapor bubbles and multiple components with different electric properties).     

Modelling of diffusion and conductivity relaxation of oxide ceramics

A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.     

Effect of fluorination on electrical properties of single walled carbon nanotubes and C60 peapods in networks

We present a comparative study of fluorinated single wall carbon nanotubes and C₆₀ peapods. The fluorination was carried out by xenon difluoride treatment at moderate temperature (100 °C). The fluorination level was determined by EDX. In empty nanotubes a fluorination level of 0.8 at.% was obtained, whereas the same treatment leads to 18 at.% in peapods (corresponding to a gross stoichiometry of C₄F). TEM images show that this fluorination procedure does not affect the peapod structure. The elemental mapping carried out by EELS reveals homogenous distribution of fluorine along the carbon nanotube bundle. This chemical treatment is found to change the electrical properties of carbon nanotubes in bucky papers. Four-probe measurements indicate a conductivity decrease by up to two orders of magnitude at room temperature. The temperature dependence of the conductivity indicates a significant change in the charge carrier density of this system. Moreover, a non-linear behavior of the I–V characteristic is observed below 50 K in fluorinated peapods.     

掺杂含量对环氧纳米复合电介质陷阱与空间电荷的影响

环氧纳米复合电介质具有抑制空间电荷积聚、高电阻率、高击穿强度等优异性能,对直流电力设备的发展具有重要的作用.但纳米粒子含量对纳米复合电介质陷阱、电导率和空间电荷的影响机理尚不清楚.本文在纳米复合电介质交互区结构模型的基础上提出了计算交互区浅陷阱和深陷阱密度的方法,得到了浅陷阱和深陷阱密度随纳米粒子含量的变化关系.随着纳米粒子含量的增加,浅陷阱密度逐渐增大,深陷阱先增加然后由于交互区重叠的影响而逐渐减少.研究了纳米粒子含量对浅陷阱控制载流子迁移率的影响,发现随着纳米粒子的增多,浅陷阱大幅增多,浅陷阱之间的平均间距迅速减小,导致载流子更容易在浅陷阱间跳跃迁移,浅陷阱控制载流子迁移率增大.建立了纳米复合电介质的电荷输运模型,采用电荷输运模型计算研究了环氧/二氧化钛纳米复合电介质的空间电荷分布、电场分布和电导率特性.发现在纳米粒子添加量较小时,交互区的深陷阱对电导的影响起主导作用;纳米粒子添加量进一步增加,浅陷阱对电导的影响将起到主要作用.     

The model oxidation catalyst α-V2O5: insights from contactless in situ microwave permittivity and conductivity measurements

The in situ microwave cavity perturbation technique was used to study the complex permittivity and conductivity of polycrystalline α-V₂O₅ in a tubular reactor under reactive high-temperature conditions with a TM₁₁₀ cavity resonating at 9.2 GHz. The sample was investigated at 400 °C in flowing air and air/n-butane mixtures while simultaneously measuring the total oxidation products CO and CO₂ by gas chromatography. The V₂O₅ powder was identified as an n-type semiconductor and the dynamic microwave conductivity correlated well with the near-infrared (NIR) absorption assigned to V3d¹ band gap states. Correlations between catalytic performance, real and imaginary parts of the permittivity, and NIR absorption allowed the differentiation between bulk and surface contributions to the charge transport in reactive atmospheres. The stability of the crystalline bulk phase was proven by in situ powder X-ray diffractometry for all applied testing conditions.