Side-chain effects on the capacitive behaviour of ionic liquids in microporous electrodes

Classical density functional theory (cDFT) is used to investigate electrosorption of ionic liquids in porous electrodes within the framework of a coarse-grained model. The purpose of this study is to clarify the influence of the side alkyl chains of imidazolium cations on the electric double layer (EDL) capacitance that was studied in a number of recent investigations but with contradictory trends. For an ionic liquid near a planar electrode, cDFT predicts that the capacitance falls by extending the alkyl chain length of cations because neutral segments reduce the packing density of counterions thus the charge density. The side-chain effect is more complicated for ionic liquids in micropores owing to space-charge competition. Adding neutral segments to imidazolium cations always reduces the capacitance in cases where the surface electrical potential of micropores is sufficiently large. However, the capacitance shows a nonmonotonic dependence on the alkyl chain length at intermediate surface potentials. Surprisingly, addition of neutral segments to the cations has the most pronounced effect on the EDL capacitance in cases when the surface potential is positively charged. These findings challenge the conventional assumption that the alkyl side chains of imidazolium ions only negatively impact ionic liquid performance in charge storage.     

微量子腔结边电荷极化结构中的线性和二阶非线性动态电导性质的研究

采用有效哈密顿量和有相互作用的分立势模型，利用格林函数和耦合参量得出了量子点(腔)在有结边电荷积累极化时的线性和二阶非线性交流电导虚部(emittance)的明确表达式.发现在经典情况下，电导虚部和电化学电容都等于经典的几何电容.在非经典情况下，如果发生全反射，电导虚部和电化学电容相等，但两者皆不等于经典的几何电容.在有隧穿的情况下，电导虚部和电化学电容以及经典电容三者都不相等.该结果对于量子器件中的电容测量具有指导作用. 关键词： 格林函数 交流电导 电化学电容     

Nonclassical behavior in the capacitance of a nanojunction

The capacitance of a nanojunction formed by a scanning tunneling microscope (STM) tip and a two-dimensional gold cluster was measured through the single electron tunneling spectroscopy of a double-barrier tunnel junction. By decreasing the STM tip-cluster separation, it was observed that the capacitance first increases and then decreases at short separation. This characteristic clearly deviates from the classical behavior and provides evidence for potential quantum effects on the capacitance.     

Capacitance spectroscopy of compressible and incompressible stripes in a narrow electron channel

We study the capacitance of single electron wires in high quantizing magnetic fields. The capacitance spectra obtained on 300 nm wide electron channels are interpreted with a simple model considering the geometry of the incompressible stripes in the electron channel as function of filling factor. The capacitance spectra directly reflect the potential form of the wire edge. This is experimentally demonstrated by the dependence on the confinement potential as well as by a clear asymmetry of the capacitance minimum at filling factor v=2 that can be well explained with the model. For comparison we present capacitance spectra obtained on very narrow, but otherwise similar quantum wires, in which quantization into one-dimensional subbands dominates the behavior.     

Quantum capacitance of the armchair-edge graphene nanoribbon

The quantum capacitance, an important parameter in the design of nanoscale devices, is derived for armchair-edge single-layer graphene nanoribbon with semiconducting property. The quantum capacitance oscillations are found and these capacitance oscillations originate from the lateral quantum confinement in graphene nanoribbon. Detailed studies of the capacitance oscillations demonstrate that the local channel electrostatic potential at the capacitance peak, the height and the number of the capacitance peak strongly depend on the width, especially a few nanometres, of the armchair-edge graphene nanoribbon. It implies that the capacitance oscillations observed in the experiments can be utilized to measure the width of graphene nanoribbon. The results also show that the capacitance oscillations are not seen when the width is larger than 30 nm.     

Influence of density inhomogeneity on the quantum capacitance of graphene nanoribbon field effect transistors

A semi-analytical model for the capacitance–voltage characteristics of graphene nanoribbon field-effect transistors (GNR-FETs), in the quantum capacitance limit, is presented. The model incorporates the presence of electron–hole puddles induced by local potential fluctuations assuming a Gaussian distribution associated with these puddles. Our numerical results show that the multi-peaks in the non-monotonic quantum capacitance–voltage characteristics are broadened as the potential fluctuation strength increases and the broadening effect is much more pronounced in wide GNRs. The influence of both gate-insulator thickness and dielectric constant scaling on the total gate-capacitance characteristics is also explored. Gate capacitance has non-monotonic behavior with ripples for thin gate-insulators. However, as we go beyond the quantum capacitance limit by increasing insulator thickness or decreasing dielectric constant, the ripples are suppressed and smooth monotonic characteristics are obtained.     

Electrical capacitance of dielectric coated metallic parallelepiped and closed cylinder isolated in free space

This paper presents a method for the evaluation of the capacitance and the charge distribution of a dielectric coated metallic parallelepiped and a dielectric coated metallic hollow cylinder with the top and bottom cover plates using the method of moments (MoM) based on the pulse basis function and the point matching. Boundary conditions for the potential on the conductor surfaces and continuity of the normal component of the displacement density at the dielectric-free space interface is used to generate two integral equations. Two sets of simultaneous equations are formed from the two integral equations using the MoM. The total charge on the conductor surface is found from the solution for the set of simultaneous equations. The validity of the analysis has been justified by comparing the data on the capacitance available in the literature for metallic cube and hollow cylinder with top and bottom cover plates with the data on capacitance, computed by the present method for similar structures considering a very low dielectric constant as well as a very thin dielectric coating.     

Capacitance of anisotropic quantum dots

The many-electron ground states in anisotropic parabolic quantum dots are investigated, by means of an unrestricted Hartree–Fock method. From the total energy, both the chemical potential and the differential capacitance of quantum dots are calculated. The effect of the shell structure due to quantization appears clearly in the chemical potential and the capacitance. The difference of the calculated differential capacitance from the classical one is caused by both the exchange interaction and the quantization. As the vertical extent of a dot increases from two-dimensional limit, the change of capacitance is small owing to cancellation between changes of Hartree term and exchange term, except at special number of electrons.     

Measuring the parameters of dielectric layers by periodically charging the surface

It is shown that the parameters and characteristics of a dielectric layer can be determined by the periodic dosed deposition of a charge on the layer surface combined with the synchronous measurement of the accumulated charge and surface potential, as well as by measuring the surface potential when the layer is both freely discharged and discharged when exposed to light. The measurements data are used to plot the surface potential of the layer versus the charge density, as well as to find the dependences of the effective capacitance, differential capacitance, and leakage resistance on the surface potential. It is demonstrated that the characteristics thus obtained may provide an insight into the physics of processes occurring in the layer; determine time parameters, such as the half-value periods of the potential in the dark and under exposure to light; and find the capacitance, limiting value of the surface potential, permittivity, leakage resistance, and photosensitivity of the layer.     

Capacitance dispersion in electrochemical impedance spectroscopy measurements of iodide adsorption on Au(1 1 1)

Electrochemical interfaces that display dispersive characteristics do not present the purely capacitive behaviour predicted by the theory of ideally polarised interfaces. For interfaces involving solid electrodes, capacitance dispersion phenomena in the double layer region are usually attributed to the structural characteristics of the electrode surface as well as to the interfacial region. This paper presents a study of the dispersive characteristics, in the double layer potential region, related to the iodide adsorption on an Au(1 1 1) electrode. The study was performed by using electrochemical impedance spectroscopy, and the corresponding spectra fitted with an equivalent circuit containing a constant phase element (CPE). The fitting results are compared with capacitance curves obtained by chronocoulometry, in order to analyse the relationship between the CPE and the interfacial capacitance. It was observed the occurrence of dispersive behaviour in the potential regions associated with phase transition processes in the adsorbed layer and to the potential induced reconstruction phenomena. On the other hand, in the potential regions where such phenomena do not occur, the interface presents almost pure capacitive behaviour. These observations provide evidence of the strong contribution of the solution properties to the capacitance dispersion.     

The influence of excluded volume and excess ion polarisability on the capacitance of the electric double layer

ABSTRACT

We apply a modified Poisson–Boltzmann theory which permits ions of different sizes and excess polarisabilities to the study of these properties’ effects on the differential capacitance of the electric double layer. For a planar electrode, we find an analytical expression for the differential capacitance, which is examined in the limits of low- and high-applied potential. In the low potential limit, a reduction of the solution relative permittivity caused by the ion polarisability causes the differential capacitance to decrease above a certain concentration, relative to the Gouy–Chapman–Stern theory. A similar effect is observed for the excluded volume, but only if the ions are of different sizes. In the high potential limit, the differential capacitance decreases inversely with the square root of the applied voltage. In a mixed electrolyte, asymmetries in both ion size and excess polarisability alter the surface adsorption of species: at high potentials, smaller ions displace larger ions and less polarisable ions displace more polarisable ions. The extent of the displacement agrees favourably with experimental data. A further consequence of this displacement is the appearance of a second peak in the differential capacitance, which is enhanced by excess ion polarisability.     

Moment method analysis of charge distribution & capacitance for the dielectric coated tilted plates isolated in free space

This paper presents a method for the evaluation of the capacitance of the dielectric coated metallic plates forming a corner using the method of moments based on the pulse basis function and the point matching. Two integral equations are formed based on the boundary conditions for the potential on the conductor surface and continuity of the normal component of the displacement flux density at the dielectric-free space interface. A set of simultaneous equations are formed from the two integral equations using the method of moments. The total free charge on the conductor surface is found from the solution of the set of simultaneous equations. Numerical data on the capacitance and the charge distribution are presented. The validity of the analysis has been justified by comparing the data on the capacitance that is available in the literature for a metallic structure with the data on the capacitance computed with the present method for a similar structure considering a very low dielectric constant as well as a very thin dielectric coating. Further validation has been carried out by comparing the capacitance data of the specific case when the angle between two metallic plates is 180° forming a dielectric coated metallic rectangular plate for which the capacitance data are available in the literature.     

Magnetocapacitance: probe of spin-dependent potentials

The magnetic field dependence of the capacitance of Pd-AlOx-Al thin-film structures has been measured. The observed quadratic dependence of capacitance on the magnetic field is consistent with a theoretical model that includes the effect of a spin-dependent electrochemical potential on electron screening in the paramagnetic Pd. This spin-dependent electrochemical potential is related to the Zeeman splitting of the narrow d bands in Pd. The quantitative details depend on the electronic band structure at the surface of Pd.     

电化学阴极沉积制备氧化镍/碳纳米管复合电极的准电容特性

采用催化裂解的方法制备了碳纳米管,其比容量为12F/g.采用碳纳米管作为电极基体,采用阴极电化学还原Ni(NO3)2的方法在碳纳米管基体表面均匀的沉积了纳米氧化镍颗粒并由此制备了氧化镍碳纳米管复合电极材料.采用循环伏安、恒流充放电、交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征.实验表明复合电极具有良好的电化学特性,碳纳米管基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在6mol/LKOH电解液中比容量达到25F/g且表现了良好的电化学可逆性.与碳纳米管基电容器相比,采用氧化镍复合电极材料组装的电容器具有较低的自放电率.     

Study of the electric capacitance spectra on symmetric quantum-dot pattern

We have calculated the ground-state energy of the symmetric quantum-dot pattern by the ab initio calculation method, i.e. unrestricted Hartree-Fock-Roothaan (UHFR) method based on the Gaussian basis, and studied their electric capacitance spectra, assuming each quantum dot of quantum-dot pattern to be confined in a three-dimensional spherical potential well of finite depth. For the systems in question, our results show that our method and theoretical model not only give the electric capacitance peaks similar to s-shell and p-shell atom-like quantum dot, but also show some new fine-structure of electric capacitance in the symmetric quantum-dot pattern system. This method might be a feasible tool to study few-electron problems on the symmetric quantum-dot pattern system.     

AlGaN/AlN/GaN高电子迁移率器件的电容电压特性的经验拟合

利用蓝宝石衬底的AlGaN/AlN/GaN 高电子迁移率器件(HEMT)的电容电压(C-V)特性,对电子费米能级与二维电子气面密度的经验关系进行表征,其结果对器件电荷控制模型的建立,跨导及电容表达式的简化有重要意义.文章创新性地提出参数α用于表征二维势阱对沟道电子限制能力,并认为α越小则二维势阱的沟道电子限制能力越强.利用上述经验关系来拟合电容,可以获得与实测电容很好的一致性. 关键词： HEMT 费米能级 C-V特性')" href="#">C-V特性 二维势阱的电子限制能力     

GaN发光二极管表观电容极值分析

利用正向交流(ac)小信号方法对GaN发光二极管的电容-电压特性进行测量,可以观察到GaN发光二极管中的负电容现象。正向偏压越大,测试频率越低,负电容现象越明显。测量到的负电容现象是表象,不存在负电容;提出GaN发光二极管p-n结的结电容在特定的正向电压范围内等效于可变电容。分析可变电容对正向交流小信号响应得到:特定参数的可变电容使结电容电流相位落后于交流小信号电压相位π/2,使得在测量中表现为负电容。发现表观电容-正向电压曲线的极值点与理论模型相吻合,证明了该理论模型的正确性。     

Effect of dielectric layer on ferroelectric responses of P(VDF-TrFE) thin films

The dielectric layer in the sandwich structural device plays a very important role in determining the electrical properties of the ferroelectric film. In this paper, we investigate the effect of the dielectric layers with different thicknesses on switching performance of ferroelectric P(VDF-TrFE) thin films. The hysteresis loops become slanting with increasing thickness of the dielectric layer. A negative slope of the ‘real’ hysteresis loop is apparently observed which demonstrates negative capacitance effect caused by the dielectric layer. This behavior is simulated qualitatively by the Weiss mean field model considering an interfacial dielectric layer in series with a ferroelectric layer. The agreement between experiments and simulations supports that negative capacitance results from the positive feedback among electric dipoles. Furthermore, the switching time of the ferroelectric film increases with the increase of dielectric layer thickness. This study shows that the ferroelectric sandwich structure provides great potential towards low power negative capacitance devices.     

Structural characterization of Mg substituted on A/B sites in $$\hbox {NiFe}_2\hbox {O}_4$$ nanoparticles using autocombustion method

A compact quantitative model based on oxide semiconductor interface density of states (DOS) is proposed for Al_0.25Ga_0.75N/GaN metal oxide semiconductor high electron mobility transistor (MOSHEMT). Mathematical expressions for surface potential, sheet charge concentration, gate capacitance and threshold voltage have been derived. The gate capacitance behaviour is studied in terms of capacitance–voltage (CV) characteristics. Similarly, the predicted threshold voltage (V _T) is analysed by varying barrier thickness and oxide thickness. The positive V _T obtained for a very thin 3 nm AlGaN barrier layer enables the enhancement mode operation of the MOSHEMT. These devices, along with depletion mode devices, are basic constituents of cascode configuration in power electronic circuits. The expressions developed are used in conventional long-channel HEMT drain current equation and evaluated to obtain different DC characteristics. The obtained results are compared with experimental data taken from literature which show good agreement and hence endorse the proposed model.     

Electric polarization and dielectric behaviour in dc electric fields of fused KNO2 in phase II at room temperature

On application of dc electric fields to a sample of KNO₂ (99.9% pure) fused between two heavily nickel plated copper plates the sample does not acquire the potential difference equal to the applied emf even though there is no external potential drop in the circuit. Also a very large capacitance of the order of 3000μF is obtained for this sample which is attributed to interfacial polarization effect. An equivalent circuit is given to explain the dc electrical behaviour of the sample. The idea of solid state battery does not seem to be applicable in the case of fused KNO₂. The large value of the capacitance for dc fields in series with large voltage-dependent resistance is the cause of the slow discharge of the condenser.