双极性半导体钝化膜空间电荷电容分析(II)

将双极性半导体钝化膜空间电荷电容等效为钝化膜/溶液界面处电容和内层钝化膜/外层钝化膜界面处的np结电容的串联, 根据前期研究建立的半导体富集态、耗尽态以及反型态空间电荷电容的统一计算公式, 给出了双极性钝化膜Mott-Schottky(M-S)曲线的非线性拟合方法. 并将这一方法应用于镍基合金G3高温高压H2S/CO2腐蚀后的钝化膜半导体特征研究. M-S曲线非线性拟合结果显示, 温度升高外层p型半导体钝化膜多数载流子浓度明显增高, 而内层n型半导体钝化膜的多数载流子浓度基本未变. 通过非线性拟合, 证明本文所给出的M-S曲线非线性拟合方法能够同时给出钝化膜内外层多个半导体性质参数,为揭示钝化膜形成及破坏机制提供更多信息. 结合X射线光电子能谱(XPS)分析, 讨论了钝化膜结构变化机制及np结在抑制腐蚀过程中的作用.     

双极性半导体钝化膜空间电荷电容分析（Ⅱ）

将双极性半导体钝化膜空间电荷电容等效为钝化膜,溶液界面处电容和内层钝化膜/外层钝化膜界面处的np结电容的串联,根据前期研究建立的半导体富集态、耗尽态以及反型态空间电荷电容的统一计算公式,给出了双极性钝化膜Mott-SchoRky(M-S)曲线的非线性拟合方法.并将这一方法应用于镍基合金G3高温高压H2S/CO2腐蚀后的钝化膜半导体特征研究.M-S曲线非线性拟合结果显示,温度升高外层P型半导体钝化膜多数载流子浓度明显增高,而内层n型半导体钝化膜的多数载流子浓度基本未变.通过非线性拟合,证明本文所给出的M-S曲线非线性拟合方法能够同时给出钝化膜内外层多个半导体性质参数,为揭示钝化膜形成及破坏机制提供更多信息.结合X射线光电子能谱(XPS)分析,讨论了钝化膜结构变化机制及np结在抑制腐蚀过程中的作用.     

镁合金在含F－的NaOH溶液中钝化行为的电化学研究

采用极化曲线、电容-电位曲线、Mott-Schottky分析以及电化学阻抗(EIS)等电化学方法研究了镁合金在含F^－ NaOH溶液中的阳极钝化行为. 结果表明, 在－1.2～1.8 V的电位范围内, 镁合金在含F^－的NaOH溶液中发生阳极钝化. 所形成的钝化膜表现出n型半导体的导电特性. 在0.7～1.8 V的电位范围内, 随着F^－浓度增大, 镁合金的阳极极化电流密度呈现出随着电位升高而逐渐增大的趋势, 随着F^－浓度增大这一趋势逐渐减弱. 并且F^－浓度的增大使得镁合金表面空间电荷层电容和钝化膜的载流子密度都不断减小. 通过极化曲线和电化学阻抗共同说明, 在5%的Na₂SO₄溶液中, NaOH溶液中阳极钝化后的镁合金随着钝化体系中F^－浓度的增加其耐蚀性逐渐减弱.     

N80油套管钢钝化膜的光电化学性能

采用电容测试法研究了N80油套管钢在浓度为0.5 mol/L NaHCO3溶液中形成钝化膜的半导体性能,结合Mott-Schottky方程分析了测试频率,成膜电位和C l-浓度对钝化膜半导体性能的影响。电容测试结果表明,钝化膜呈n型半导体特性,Mott-Schottky曲线的斜率随着测试频率的增加、成膜电位的正移和溶液中氯离子浓度的增加而增加,相应地膜内的施主密度减小。光电化学实验结果表明,光电流强度随成膜电位的正移及成膜时间的延长而增加,这主要归功于高电位和长时间下所成的钝化膜具有比较均匀的组成,光激发所成的空位或电子在膜内的迁移率的增加。     

n-InP/Fe3+, Fe2+界面在小信号电流阶跃下的暂态行为

应用小信号电流阶跃法研究了光照下n-InP/Fe~(3+), Fe~(2+)界面, 此时电位变化符合双指数规律, 这和理论推导是一致的。在时间很短时, 电位与时间成线性关系, 从直线斜率可求出空间电荷区电容。     

环氧树脂/碳钢电极在硫酸溶液中的半导体导电行为

采用电位-电容测试和Mott-Schottky分析技术研究了环氧树脂/碳钢电极在0.5 mol·L-1硫酸中腐蚀失效过程中的半导体导电行为. 环氧树脂在刚刚浸入溶液时(10 min)为绝缘体, 随着浸泡时间延长, 由于离子的腐蚀,环氧树脂外层逐渐转变为n 型半导体. 半导体层中的载流子密度随着浸泡时间的延长而增大,载流子由浸泡7 h约1010 cm-3增大到48 h的约1012 cm-3数量级, 浸泡48 h 以内涂层没有完全转变为半导体, 碳钢表面包括环氧树脂层在浸泡7-48 h 期间为MIS(metal-insulator-semiconductor)结构. 此MIS 结构空间电荷层在-0.5 - 0.5 V内处于反型状态, 反型层内的载流子为空穴. 在较低频率下测得空间电荷层电容为反型层电容和耗尽层电容的串联电容, 随电位升高而减小;较高频率下测得空间电荷层电容仅为耗尽层电容, 不随极化电位变化. 该MIS结构的电位-电容特性曲线与理想MIS结构相比发生了阳极漂移.     

碳钢/醇酸涂层在5%NaCl溶液中的极化及半导体行为

摘要 采用电位-电容测试和Mott-Schottky分析技术研究了碳钢/醇酸涂层在5%NaCl溶液侵蚀下腐蚀失效过程中的极化及半导体行为. 浸泡2h, 电极形成了MIS结构, 涂层半导体为n型导电, 半导体载流子密度为4.99×109cm-3, 腐蚀仅受水和离子在涂层中的扩散控制;浸泡1d和2d时, 涂层在电场下发生偶极极化, 偶极电场阻碍载流子的迁移, 偶极弛豫效应使微分电容随外加电位绝对值增大而减小, 并造成电位-电容行为的频率依赖性;浸泡7d~17d涂层发生空间电荷极化, 碳钢与涂层形成了金属/半导体接触, 随着浸泡时间延长, 涂层载流子密度逐渐增加, 平带电位正移, 功函数逐渐减小, 对电子束缚能力减弱, 随外加电位的增加, 金属/醇酸涂层界面势垒升高, 空间电荷层成为阻挡层, 电极载流子输运受涂层孔隙电阻, 空间电荷层, 金属基底反应动力学三重控制.     

不同浓度比的硫酸根和氯离子溶液中钝化膜的半导体特性转变机制研究

800合金作为核电站蒸汽发生器的一种关键材料,服役环境下其表面钝化膜的特性一直是人们研究的热点.本文用Mott-Schottky方法研究了800合金在不同硫酸根离子和氯离子浓度比的溶液中钝化膜的半导体特性,并结合电化学阻抗谱(EIS)、扫描电镜(SEM)、扫描电化学显微镜(SECM)研究了钝化膜的耐蚀性和表面活性.Mott-Schottky结果表明,800合金表面钝化膜的半导体特性与溶液中硫酸根、氯离子的浓度比有关,随硫酸根与氯离子浓度比的降低,半导体特性发生转变.当硫酸根与氯离子的浓度比较高时,钝化膜为p型半导体;而当硫酸根与氯离子的浓度比较低时,钝化膜为n型半导体.EIS、SECM、SEM结果表明,随浓度比的降低钝化膜由过钝化溶解转为明显的点蚀特征,钝化膜表面活性增加.钝化膜特性的改变与其半导体类型的转变密切相关,而半导体特性的转变由氯离子、硫酸根离子在800合金钝化膜表面的竞争吸附所致,其在表面的竞争吸附直接影响钝化膜表面发生的化学反应,改变电极/溶液界面电势差,使钝化膜中的空位类型改变,最终决定半导体类型.     

铬对碳钢在NaHCO3/NaCO3缓冲溶液中所成钝化膜半导体性能的影响

应用电化学阻抗谱技术研究铬对碳钢钝化膜半导体性能的影响.实验表明,在碳酸氢钠/碳酸钠缓冲溶液中碳钢形成的钝化膜具n型半导体特性,而含有3%铬的碳钢钝化膜则呈n-p型半导体特性,随着成膜电位的增加,以上两种钝化膜之Mott-Schottky直线部分的斜率均呈增大的趋势,表明成膜电位升高,膜内的杂质密度减小,但铬的加入使得碳钢钝化膜的施主密度增加约一个数量级,从而增加了碳钢点蚀发生的趋势.EIS分析表明:铬的加入降低了钝化膜的传递电阻R1和膜电阻R2,特别是膜电阻R2下降达3个数量级,这就有可能增加碳钢在高pH值环境中的腐蚀.     

不同浓度比的硫酸根和氯离子溶液中钝化膜的半导体特性转变机制研究

800合金作为核电站蒸汽发生器的一种关键材料,服役环境下其表面钝化膜的特性一直是人们研究的热点. 本文用Mott-Schottky方法研究了800合金在不同硫酸根离子和氯离子浓度比的溶液中钝化膜的半导体特性,并结合电化学阻抗谱（EIS）、扫描电镜（SEM）、扫描电化学显微镜（SECM）研究了钝化膜的耐蚀性和表面活性. Mott-Schottky结果表明,800合金表面钝化膜的半导体特性与溶液中硫酸根、氯离子的浓度比有关,随硫酸根与氯离子浓度比的降低,半导体特性发生转变. 当硫酸根与氯离子的浓度比较高时,钝化膜为p型半导体;而当硫酸根与氯离子的浓度比较低时,钝化膜为n型半导体. EIS、SECM、SEM结果表明,随浓度比的降低钝化膜由过钝化溶解转为明显的点蚀特征,钝化膜表面活性增加. 钝化膜特性的改变与其半导体类型的转变密切相关,而半导体特性的转变由氯离子、硫酸根离子在800合金钝化膜表面的竞争吸附所致,其在表面的竞争吸附直接影响钝化膜表面发生的化学反应,改变电极/溶液界面电势差,使钝化膜中的空位类型改变,最终决定半导体类型.     

Influence of deep energetic levels on charge densities and capacitance of semiconductor/electrolyte interface

Charge density and space charge layer capacitance of semiconductor/electrolyte interface are determined by computational method in the case of crystalline, polycrystalline and amorphous semiconductors with multiple deep energetic levels. These determinations are performed as a function of the difference of potential between the potential in the bulk of the electrode and the potential at a point x and especially at x = 0 which correspond to the potential at the SC/electrolyte interface. The investigation of the results allows proposing new and original relations describing the charge density for polycrystalline and amorphous semiconductors. The variation of the charge density is manifested by the existence of different regions where the ionization phenomenon of the donor states relative to the discrete and continuous levels is exhibited. The space charge layer capacitance determined from the charge density using Poisson’s equation is also analyzed as a function of the potential difference through the space charge layer for the different parameters characterizing the discrete and continuous levels in the case of the different semiconductors. For amorphous semiconductors, the charge density and the space charge layer capacitance are analyzed for two models of the density of states. The representation of the inverse square capacity shows a linear variation where straight lines with different slopes appear in low and high potential range indicating Mott-Schottky behaviour.     

A critical assessment of the Mott-Schottky analysis for the characterisation of passive film-electrolyte junctions

The widespread use of the Mott-Schottky plots to characterize the energetics of passive film/electrolyte junction is critically reviewed in order to point out the limitation of such approach in describing the electronic properties of passive film as well in deriving the correct location of the characteristic energy levels of the junction. The frequency dependency of M-S plots frequently observed in the experimental data gathered in a sufficiently large range of frequency is extensively discussed for a relatively thick (160 nm) thermally aged amorphous niobia (α-Nb₂O₅) film immersed in electrolytic solution. The relatively simple equivalent electrical circuit describing an ideally blocking behaviour of the junction allows a direct comparison of the experimental data analysis based on the use of Mott-Schottky or amorphous semiconductor Schottky barrier interpretative models. Moreover the theoretical simulations of the M-S plots based on the theory of crystalline semiconductor suggest an electronic structure of the investigated passive film containing a distribution of localized electronic states deep lying in energy in agreement with the model of amorphous semiconductor Schottky barrier.     

Barrier and semiconducting properties of thin anodic films on chromium in an acid solution

The study of barrier and semiconducting properties of anodically formed oxide films on chromium in an acid solution was carried out using the Cr-quartz crystal electrode. The oxide film formation and growth occur through an anion vacancies transport via a low-field-assisted mechanism (H = 10⁶ V cm⁻¹). The anion diffusion coefficient, which quantitatively describes the transport of point defects within the growing film, was calculated from capacitance data using the Nernst-Planck equation for low-field limit approximation and Mott-Schottky analysis. The depletion region in the passive film, close to the film|electrolyte interface, dominates the semiconducting properties. The passive film on Cr in an acid solution behaves as an n-type semiconductor. An energy-band structure model of the passive film is given.     

电容测量研究铬表面氧化膜的半导体性能

利用电容测量技术,基于Mott-Sckottky分析,研究了在0.5 mol•L－1 H2SO4溶液中铬表面氧化膜的半导体性质,以及膜形成条件的影响.结果表明,铬在钝化电位区内所形成的表面氧化膜具有p-型半导体特性,膜的厚度约(1.2±0.3) nm.膜的阻抗响应表现出低频弥散行为,可以用介电弛豫普适定律来描述.膜的掺杂浓度NA随成膜电位及极化时间的延长而增大,溶液pH值则通过改变膜的表面电荷而影响膜的平带电位EFB.     

TiO2薄膜光电极能带结构和催化活性的初探

以阳极氧化法制得的TiO₂薄膜光电极为工作电极,铂环为对电极,饱和甘汞电极为参比电极,组成光电催化降解苯酚体系.运用电化学阻抗图谱(EIS),测得光电催化过程中TiO₂薄膜光电极的空间电荷层电容,计算出半导体能带结构参数——空间电荷层宽度W.结果证明:当空间电荷层宽度W随阳极偏压增加而增大时,TiO₂薄膜电极光催化活性提高;当其等于薄膜厚度时,光催化活性最好,此时出现最佳偏压值;继续增加偏压,活性反而有所下降.     

The capacity of thin passive films

The capacity of thin passive films on metal electrodes is investigated. Two contributions are reported: one from the space charge in the film and one from the surface charge on the underlying metal. In the usual Schottky-Mott plot such films also exhibit a linear region, but this cannot ordinarily be used to obtain the carrier concentration and the flat-band potential. These calculations agree well with experimental data.     

不锈钢载波钝化膜的半导体性质

运用交流阻抗法和光电化学法研究了不锈钢载波钝化膜层的半导体性质。讨论了交流阻抗测试中扰动频率的变化对Mott-Schottky曲线的影响，讨论了不锈钢载波钝化膜的n/p型、杂质施主密度和平带电位等半导体性质，同时结合光电化学法对交流阻抗测试结果进行了验证分析，实验结果认为不锈钢载波钝化膜层具有与直流钝化膜层相似的半导体性质，并通过膜层的组成结构对其半导体性质作了分析。     

Oxidizing valve metals: effect of electronic properties of the oxide films

Photocurrents emerging during the formation of anodic oxide films (AOF) on such valve metals as W, Ti, Zr, Nb, Ta are measured during an increase (direct run) and a decrease (reverse run of voltammetric curves) in the anodic potential. Capacitances of AOF formed at certain potentials are measured at potentials below the AOF formation potential. Effect of semiconductor properties on the AOF growth is considered through the formation of a Schottky barrier at the oxide/electrolyte interface. Calculated thicknesses of AOF and the depleted layer are compared. The donor-concentration drop in AOF with the distance from the metal/oxide interface is a condition for the growth of thick semiconductor oxide films. The measured potential dependence of the semiconductor-film capacitance is used to plot the donor concentration drop as a function of the distance from the Nb₂O₅/Nb interface in the oxide layer on a niobium electrode. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth.