Point defects,diffusion processes,and swirl defect formation in silicon

The paper consists of three parts. In the first part we review the basic experimental and theoretical results which shaped our present knowledge on point defects and diffusion processes in silicon. These results concern on one side oxidation effects which established that silicon self-interstitials and vacancies coexist in silicon and on the other side diffusion of gold into dislocation-free silicon which allowed to determine the self-interstitial contribution to silicon self-diffusion and to estimate the corresponding vacancy contribution. In the second part we discuss topics for which an understanding is just emerging within the framework of coexisting self-interstitials and vacancies: reaching of local dynamical equilibrium between self-interstitials and vacancies; rough estimates of the thermal equilibrium concentrations of self-interstitials and vacancies and their respective diffusivities, and finally, various possibilities to generate an undersaturation of self-interstitials. In the third part we examine swirl defect formation in silicon in terms of vacancies and self-interstitials.     

铝中氦原子行为的密度泛函研究

用密度泛函理论计算了大量He原子存在时He在金属铝中不同位置的能量,并在理论上预测了铝中的氦原子行为。结果表明,铝晶胞内He原子择优占位区是空位,而在整个晶体范围,最有利于容纳He原子的区域是晶界,其次是空位和位错。在fcc-铝的两种间隙位中,He原子优先充填四面体间隙位。间隙He原子的迁移能很小,易于通过迁移在晶内聚集,或被空位、晶界、位错等缺陷束缚。     

铝中氦原子行为的密度泛函研究

用密度泛函理论计算了大量He原子存在时He在金属铝中不同位置的能量,并在理论上预测了铝中的氦原子行为.结果表明,铝晶胞内He原子择优占位区是空位,而在整个晶体范围,最有利于容纳He原子的区域是晶界,其次是空位和位错.在fcc-铝的两种间隙位中,He原子优先充填四面体间隙位.间隙He原子的迁移能很小,易于通过迁移在晶内聚集,或被空位、晶界、位错等缺陷束缚.     

Self-interstitial in germanium

Low-temperature radiation damage in n- and p-type Ge is strikingly different, reflecting the charge-dependent properties of vacancies and self-interstitials. We find, using density functional theory, that in Ge the interstitial is bistable, preferring a split configuration when neutral and an open cage configuration when positively charged. The split configuration is inert while the cage configuration acts as a double donor. We evaluate the migration energies of the defects and show that the theory is able to explain the principal results of low-temperature electron-irradiation experiments.     

Hydrogen complexes and their vibrations in undoped crystalline silicon

Geometry, relative stability, and vibration frequencies of hydrogen complexes — with and without the presence of vacancies and self-interstitials — are calculated. Assignments proposed by various experimental investigators for hydrogen related vibrational bands are discussed based on the relation between Si-H bond-character and stretching mode frequency.     

Atomic diffusion in strain fields near solutes

Annihilation reactions between mobile self-interstitial defects and complexes of vacancies with¹¹¹In probe solutes in Au were studied. Measurements were made using the technique of perturbed angular correlations of gamma rays (PAC). Au samples were doped with complexes and plastically deformed at a low temperature to generate fluxes of self-interstitials. Changes in the concentrations of monovacancy (1V) to tetravacancy (4V) complexes induced by annihilation reactions were measured. These are now analysed using a system of coupled first-order equations in order to obtain interstitial annihilation cross sections of the complexes and the fractional amounts of different interstitial clusters in the flux. Relative cross sections obtained for Au are 1.0(1), 3.3(3), 1.2(2) and 7.5(2.5), respectively, for 1V to 4V complexes. The large increase in the cross sections with vacancy number is attributed to a progressive relaxation of the dilatational strain surrounding the oversized In solute as more vacancies are trapped. Also obtained from the analysis are values 0.34(5), 0.66(7), 0.0(1) and 0.0(2), respectively, for the fractions of mobile 1I to 4I clusters in deformed Au, indicating that di-interstitials are produced more readily than mono-interstitials during plastic deformation.     

Perturbed γ−γ angular correlations: A spectroscopy for point defects in metals and alloys

Atomic defects which migrate and trap at impurity probe atoms can be labelled by the changes they induce in the hyperfine interactions of the probe nuclei. Many studies have been made using perturbed γ−γ angular correlations (PAC) and the¹¹¹In probe because of the excellent resolution of different sites. Identification of the bound states is the key problem in applying hyperfine interactions methods to point defects studies. In this study three structure-sensitive methods are applied to help identify the atomic structures of various multivacancy complexes in Pt and Au: (1) Quadrupole interaction parameters are compared with results of point-charge calculations of electric-field gradients for 20 structures containing 1–4 vacancies in the fcc lattice. (2) Hyperfine interactions induced by decorating vacancy complexes with hydrogen atoms are measured and interpreted with the assistance of point-charge calculations. (3) Transformations between complexes observed by annihilation of vacancies by mobile self-interstitials are used to test the consistency of the identifications. Using these methods in conjunction with analysis of the trapping behavior which occurs during annealing of damaged samples, structural models are presented for divacancy (2V), 3V and 4V complexes in Pt, and 3V and 4V complexes in Au. The activation temperatures of the 3V defect in Au and Pt are determined to be 162 K and 390 K, respectively, and activation temperatures of defects in Ni, Cu, Pt and Au are compared. For Pt, trapping of H at 1V and 2V complexes is observed to lead to small changes in the quadrupole interactions, consistent with well shielded protonic charges. However, trapping at 3V and 4V complexes leads to very large changes which we attribute to atomic restructuring to the defect complexes. Finally, the application of the same methodology to interpret recent experiments on NiAl, an ordered alloy, is described.     

Ab initio study of palladium and silicon carbide

Ab initio methods have been used to investigate the properties of Pd as impurity in bulk SiC at five charged states within the framework of density functional theory using the local spin density approximation. It was found that Pd interstitials and substitutionals have similar energy to their intrinsic counterparts. In addition, Pd substitutes for a vacancy, di-vacancy, and tri-vacancy with similar energies. Pd diffuses through SiC via an interstitial mechanism employing the tetrahedral sites and Pd can substitute for Si and C at positive charged states. Removing electrons (p-type doping) from SiC lowers the formation and migration energies of Pd defects in SiC for most configurations.     

Gold and platinum diffusion: The key to the understanding of intrinsic point defect behavior in silicon

The study of gold and platinum diffusion is found to allow the separate observation of the intrinsic point defects, i.e., of silicon self-interstitials and of vacancies. The diffusion of gold in float zone (FZ) silicon is found to be dominated by the kick-out mechanism for temperatures of 800° C and higher. The diffusion of platinum in FZ silicon is described by the kick-out mechanism for temperatures above approximately 900° C, whereas for temperatures below approximately 850° C the dissociative mechanism governs platinum diffusion. As a result of numerical simulations, we suggest a complete and consistent set of parameters which describes the diffusion of platinum in silicon in the temperature range from 700° C to 950° C and the diffusion of gold in the temperature range from 800° C to 1100° C. The generation or recombination of self-interstitials and vacancies is found to be ineffective at least below 850° C. The concentration of substitutional platinum is determined by the initial concentration of vacancies at diffusion temperatures below 850° C. Platinum diffusion below 850°C can be used to measure vacancy distributions in silicon quantitatively.     

Hyperfine interaction of rare earth impurities in ferromagnetic metals

The present knowledge concerning rare earth impurities implanted in iron and nickel is reviewed. New Mössbauer spectra on the isotopes¹⁶¹Dy,¹⁶⁶Er and¹⁶⁹Tm are presented. In the case of¹⁶¹DyFe and¹⁶¹DyNi both the annealing behaviour and the temperature dependence have been studied. It is shown that in almost all cases about half of the rare earth impurities end up in substitutional sites, whereas the other part probably is associated with vacancies. The temperature dependence for these systems is in accordance with the generally accepted local moment picture, with fast relaxation behaviour on the electronic moment at the substitutional sites. For the iron host the exchange interaction dominates the cubic crystalline electric field, but for nickel both interactions are of comparable magnitude, leading to a considerable decrease of the hyperfine interaction.     

掺杂剂对重掺n型直拉硅片的氧化诱生层错生长的影响

对比研究了电阻率几乎相同的重掺锑和重掺磷直拉硅片的氧化诱生层错(OSF)的生长, 以揭示掺杂剂对重掺n型直拉硅片的OSF生长的影响. 研究表明: 在相同的热氧化条件下, 重掺锑直拉硅片的OSF的长度大于重掺磷硅片的. 基于密度泛函理论的第一性原理计算结果表明: 与磷原子相比, 锑原子是更有效的空位俘获中心, 从而抑制空位与自间隙硅原子的复合. 因此, 在经历相同的热氧化时, 氧化产生的自间隙硅原子与空位复合后所剩余的数量在重掺锑硅片中的更多, 从而导致OSF更长.     

The nature of the C-defects in nickel and their rôle in the interpretation of radiation damage in metals

In previous Perturbed-Angular-Correlation (PAC) studies of the - emission of ¹¹¹In probe nuclei in cold-worked or particle-irradiated nickel, it has been found that thermal annealing in the temperature regime of recovery stage III leads to the formation of so-called C-defects (Cubic defects). This is indicated by the occurrence of a new frequency of about 80 Mrad/s, in addition to the frequency (200 Mrad/s) that is due to ¹¹¹In on substitutional sites. Obviously, the C-defects are complexes consisting of ¹¹¹In and the intrinsic point-defect species that migrates freely in recovery stage III. Therefore, they have played an important rôle in the long-standing controversy on whether the recovery-stage-III defects are vacancies (one-interstitial model) or self-interstitials (two-interstitial model). The present paper reports on a novel experimental effort to reveal the nature of the C-defects by combining PAC studies on nickel samples differently pretreated in a systematic way, investigations of the Extended X-ray Absorption Fine Structure (EXAFS) on In-doped nickel, and measurements of the decay rate of ¹¹¹In nuclei in the Electron-Capture-Induced Decay (ECID). On the basis of the results of these experiments it is concluded that the defects trapped by substitutional ¹¹¹In atoms (In_s) in recovery stage III are self-interstitials (I), as expected according to the two-interstitial model. Moreover, there is evidence that the C-defects are In interstitials on tetrahedral sites (In_i) that form exclusively in the vicinity of the specimen surface from In_s – I pairs via the reaction In_s+I In_i.     

Laser spectroscopy of donor-acceptor complexes inβ-CdP2

In p and n type CdP₂ samples (tetragonal modification) narrow symmetric absorption bands with energy maxima at 1.77, 1.69, 1.60, and 1.50 eV were observed using laser spectroscopy. They depend strongly on the mutual orientation of the electric vector of the radiation and the optical c axis of the crystal. The results found experimentally can easily be explained as complexes consisting of deep acceptors which are doubly-charged cadmium vacancies and shallow substitutional donor atoms S, occupying phosphorus sites in the 1-st, 2-nd, 3-rd, and 4-th coordination spheres relative to the cadmium vacancies. Kiev State Pedagogical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 83–88, July, 1998.     

Interaction of Point Defects with Grain Boundaries in fcc Metals

Structures of several symmetrical tilt grain boundaries (GBs) with different tilt axes in Cu and Al and their interaction with vacancies and interstitials are studied using atomistic computer simulations with embedded-atom potentials. The lowest defect formation energy in a GB is found to correlate with the GB energy in both Cu and Al. Importantly, vacancies and self-interstitials in GBs have comparable formation energies, suggesting that both defects are equally important for GB diffusion and other properties. Vacancies in GBs can be either localized at certain sites or be delocalized over several sites. Some GB sites do not support a stable vacancy at all. Self-interstitial atoms can occupy relatively open interatomic positions, form split dumbbell configurations, or give rise to highly delocalized displacement zones. These structural forms of point defects have been observed across the whole set of twelve GBs in Cu and six GBs in Al studied in this paper as well as in our previous work [Interface Science 11, 131–148 (2003)]. It is suggested that these structural forms are general to all GBs in fcc metals. They can be explained by the existence of internal stresses and alternating tension and compression regions in the GB core.     

Monovacancy and interstitial migration in ion-implanted silicon

The migration of monovacancies (V0) and self-interstitials (I) has been observed in ion-implanted low-doped float-zone silicon by variable-energy positron annihilation spectroscopy. V0 and I were created by the in situ implantation of approximately 20 keV helium ions below 50 K. Monitoring the time evolution of the vacancy response during isothermal heating enabled the measurement of activation energies for I and V(0) [corrected] migration of 0.078(7) and 0.46(28) eV, respectively. In highly As-doped Si, partial V annihilation occurs via free I migration, with a second stage of annealing, probably associated with V-As complexes, above room temperature.     

On the nature of point defects and the effect of oxidation on substitutional dopant diffusion in silicon

An extensive analysis of the substitutional dopant diffusion phenomena in silicon during oxidation is presented. The analysis covers qualitative as well as quantitative aspects of the oxidation-enhanced and -retarded diffusion (OED and ORD) phenomena, and examines three different possible assumptions that can be made on the nature of the silicon thermal equilibrium point defect species: silicon self-interstitials (I) only, vacancies (V) only, coexistence of I and V. The only consistent way to interpret all properly documented OED/ORD data is to assume that I and V coexist under oxidation as well as under thermal equilibrium conditions at high temperatures.     

Combination of emission channeling,photoluminescence and Mössbauer spectroscopy to identify rare earth defect complexes in semiconductors

Implanted radioactive ¹⁶⁷Tm / ¹⁶⁷Er and ¹⁶⁹Yb / ¹⁶⁹Tm impurities in Si and GaN were studied with emission channeling and photoluminescence spectroscopy. The effect of co-doping with oxygen on the rare earth (RE) lattice sites and their luminescence behavior was investigated. Tm and Yb occupy near-tetrahedral sites in Si and substitutional sites in GaN after room temperature implantation and annealing. O-RE complexes are formed upon co-doping with O resulting in modified luminescence signals. RE impurities remain substitutional in O-doped GaN, but are displaced from tetrahedral sites in O-doped Si. We discuss the feasibility of Mössbauer studies using ¹⁵¹Eu, ¹⁶⁹Tm and ¹⁶¹Dy to determine the RE valence state and to identify RE defect complexes.

     

Substitutional-interstitial interactions in niobium-titanium alloys: An internal friction study

The influence of additions of interstitial oxygen and nitrogen on the internal friction spetrum of the niobium-1 at-% titanium alloy was studied. The nature of the various observed relaxation processes introduced by the presence of substitutional titanium is discussed. A thermodynamic analysis was carried out for two pronounced interaction peaks attributed to the stress-induced reorientation of single oxygen or nitrogen atoms around single titanium atoms and the respective binding energies were estimated. It was also found that, over the range of oxygen concentration studied, interstitial oxygen is completely removed from random migration by substitutional titanium atoms acting as trapping centres, whilst nitrogen population is always partitioned between mobile and trapped atoms even at very low relative nitrogen concentrationsC _N/C _Ti. A possible reason for the different behavior of oxygen and nitrogen is suggested.     

Kinetics of self-interstitials reactions in p-type silicon irradiated with alpha particles

New findings on the self-interstitial migration in p-type silicon are presented. They are based on experimental studies of the formation kinetics of defects related to interstitial carbon after irradiation with alpha particles. The main parameters characterizing the interaction rate of silicon self-interstitials with substitutional carbon atoms have been determined. A preliminary interpretation of the experimental data is given. The interpretation takes into account different diffusivities of self-interstitials in their singly and doubly ionized states.     

Infrared-induced emission from silicon quantum wires

We present the first findings of a study of infrared-induced emission from silicon quantum wires, which is due to the formation of a correlation gap in the DOS of the degenerate hole gas. The quantum wires in this case are created by an electrostatic confining potential inside ultra-shallow p–n junctions which are realized using controlled surface injection of self-interstitials and vacancies in the process of non-equilibrium boron diffusion.