Dynamics of defects in semiconductors

Hyperfine interaction techniques involving radioactive probe atoms like the perturbed angular correlation technique (PAC) and the Mössbauer effect have, due to their inherent sensitivity, successfully been applied to the study of defects in semiconductors. By probing the characteristic charge distribution around the probe atom interacting with a defect, they contributed to the microscopic understanding of the nature, structure and stability of complexes formed between radioactive dopant atoms and defects present in elemental and compound semiconductors. Moreover, dynamic effects can be studied by hyperfine interaction probe techniques. In this case, dynamics always means the fluctuation of a charge distribution resulting in a time dependent hyperfine interaction within the time scale defined by the lifetime of the isomeric nuclear state used for the measurement. Such fluctuations can either be caused by structural changes like local rearrangements of a defect complex or by electronic transitions in the semiconductor resulting in a change of the charge state of a defect complex. Examples using PAC to monitor such processes will be discussed for the semiconductor silicon.     

Non-intrusive mapping of subsurface defects in semiconductors

We have adapted differential interference contrast Nomarski microscopy in the transmission configuration to the problem of mapping subsurface defects in semiconductors. We have demonstrated the ability to rapidly measure the depth of the precipitate-free-zone in silicon with a reproducibility of ±1 m in whole Si wafers up to 200 nm in diameter, having an extrinsic doping concentration up to 7×10¹⁹ cm^–3 and a nominal, as received, back side roughness. Because our subsurface defect profiler is completely non-destructive, product wafers can be inspected at various stages of processing and immediately returned to the production line.     

Enthalpy of formation of Schottky defects in semiconductors

The enthalpy of formation of Schottky defects in crystals of II–VI, III–V, and IV–VI compounds has been calculated with the use of a method based on Mie-Lennard-Jones pair potentials, whose parameters have been determined from the experimental data on the Debye temperature, Grüneisen parameter, Poisson’s ratio, elastic constants, and bulk modulus. The found values of the enthalpy of formation agree with the known literature data and can be used to calculate the density of these defects in the crystals.     

Direct visualization of structural defects in 2D semiconductors

Direct visualization of the structural defects in two-dimensional (2D) semiconductors at a large scale plays a significant role in understanding their electrical/optical/magnetic properties, but is challenging. Although traditional atomic resolution imaging techniques, such as transmission electron microscopy and scanning tunneling microscopy, can directly image the structural defects, they provide only local-scale information and require complex setups. Here, we develop a simple, non-invasive wet etching method to directly visualize the structural defects in 2D semiconductors at a large scale, including both point defects and grain boundaries. Utilizing this method, we extract successfully the defects density in several different types of monolayer molybdenum disulfide samples, providing key insights into the device functions. Furthermore, the etching method we developed is anisotropic and tunable, opening up opportunities to obtain exotic edge states on demand.     

Electronic structures of impurities and point defects in semiconductors

A brief history of the impurity theories in semiconductors is provided. A bound exciton model is proposed for both donor-and acceptor-like impurities and point defects, which offers a unified understanding for "shallow" and "deep"impurities and point defects. The underlying physics of computational results using different density-functional theorybased approaches are discussed and interpreted in the framework of the bound exciton model.     

Properties of electrically active structural defects in crystalline semiconductors

The internal structures, composite elements, electrophysical properties, and characteristic parameters of impurity clouds, noise supertraps, disordered domains, and stacking defects are compared in crystalline semiconductors. It is shown that the mentioned macrodefects possess common properties: They have a nucleus and an impurity atmosphere, are separated by a potential barrier, are shaped with the participation of Frenkel defects and oxygen ions, have a threshold inclusion, sharply increase the rate of charge carrier generation-recombination as the electrical field grows, etc. It is noted that current channels in non-crystalline semiconductors are characterized by properties close to these after they have been formed. It is assumed that the electrical activity of the structural macrodefects in crystalline semiconductors may be related to the fundamental properties of noncrystalline semiconductors (for instance, the resistance switching effect). Domains adjoining a macrodefect and destroyed by it visibly manifest these properties.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 95–100, April, 1988.     

The DX center and other tin-related defects in AlGaAs semiconductors

Al _x Ga_1-xAs semiconductors doped with both natural and enriched¹¹⁹Sn have been studied by Mössbauer spectroscopy (MS) to help to determine the atomic-scale nature of a deleterious, deep-level defect known as the DX center. Spectra have been acquired in the dark at 76 K and under sub-bandgap illumination at 4 or 10 K to distinguish the DX center from the substitutional shallow donor defect. Although electrical differences are clearly detected in these two states, no difference in the Mössbauer spectra are observed. Unexpected high Sn contents, determined by quantitative MS, demonstrate a large non-electrically active Sn fraction in some samples and this may be obscuring the observation of the DX center by both X-ray absorption spectroscopy and MS. Grinding the single-crystal layers into fine powders leads to an Sn defect that is attributed to a surface-oxidized site.     

High temperature defects in electron irradiated semiconductors HgCdTe,PbSnTe

The peculiarities of defect formation in n- and p-type conductivity HgCdTe and PbSnTe crystals after electron irradiation (2 MeV, 300 K) up to 2 × 10¹⁸ cm^-2 are examined. It has been found that irradiation results in formation of n-type conductivity crystals with final parameters that are determined by the composition of initial samples. The annealing of radiation defects occurs in the 360–470 K temperature range. It has been believed that the change of HgCdTe, PbSnTe properties after electron irradiation at 300 K are connected with formation of radiation defects, including Te vacancies.     

Imaging and spectroscopy of defects in semiconductors using aberration-corrected STEM

The distribution of single dopant or impurity atoms can dramatically alter the properties of semiconductor materials. The sensitivity to detect and localize such single atoms has been greatly improved by the development of aberration correctors for scanning transmission electron microscopes. Today, electron probes with diameters well below 1 Å are available thanks to the improved electron optics. Simultaneous acquisition of image signals and electron energy-loss spectroscopy data provides means of characterization of defect structures in semiconductors with unprecedented detail. In addition to an improvement of the lateral spatial resolution, depth sensitivity is greatly enhanced because of the availability of larger probe forming angles. We report the characterization of an alternate gate dielectric interface structure. Isolated Hf atoms are directly imaged within a SiO₂ thin film formed between an HfO₂ layer and the silicon substrate. Electron energy-loss spectroscopy shows significant changes of the silicon valence state across the interface structure.     

Entropy-driven triple point wetting in hard-rod mixtures

We theoretically study binary mixtures of thin and thick hard rods with diameter ratio more extreme than 1:4. The bulk phase diagram of these systems exhibits a triple point, where an isotropic (I) phase coexists with two nematic phases ( N1 and N2) of different composition. Using density functional theory, we predict that the I-N2 interface is completely wet by N1 upon approach of the the I-N1-N2 triple point. This entropic triple point wetting should be experimentally observable in colloidal suspensions of rodlike particles.     

EPR of defects in semiconductors: Past, present, future

Important physical concepts learned from early EPR studies of defects in silicon are reviewed. Highlighted are the studies of shallow effective-mass-like donors and acceptors by Feher, of deep transition-element impurities by Ludwig and Woodbury, and of vacancies and interstitials by Watkins et al. It is shown that the concepts learned in silicon translate remarkably well to corresponding defects in the other elemental and compound semiconductors. The introduction of sensitive optical and electrical detection methods during the intervening years, and the recent progress in single-defect detection insure the continued vital role of EPR in the future. Fiz. Tverd. Tela (St. Petersburg) 41, 826–830 (May 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Muonium as an experimental model of hydrogen point defects in semiconductors

Hydrogen is an important defect in semiconductors which can significantly alter the electrical and optical properties of the host. Information on isolated interstitial hydrogen is virtually nonexistent. Fortunately, complementary data can be obtained by studying muonium. In this article, we describe recent experimental examples which illustrate how μSR can be used to investigate the electronic structure and dynamics of muonium in semiconductors and discuss the relevance of these measurements for isolated hydrogen.     

Entropy-driven enhanced self-diffusion in confined reentrant supernematics

We present a molecular dynamics study of reentrant nematic phases using the Gay-Berne-Kihara model of a liquid crystal in nanoconfinement. At densities above those characteristic of smectic A phases, reentrant nematic phases form that are characterized by a large value of the nematic order parameter S?1. Along the nematic director these "supernematic" phases exhibit a remarkably high self-diffusivity, which exceeds that for ordinary, lower-density nematic phases by an order of magnitude. Enhancement of self-diffusivity is attributed to a decrease of rotational configurational entropy in confinement. Recent developments in the pulsed field gradient NMR technique are shown to provide favorable conditions for an experimental confirmation of our simulations.