Oxygen diffusion and thermal donor formation in silicon

The information available on the diffusion of oxygen and on the formation of thermal donors in silicon is critically reviewed. In this context the effects of intrinsic point defects on the diffusion-controlled growth of oxygen precipitates is investigated in some detail. Seemingly contradictory experimental results on the diffusivity of oxygen in silicon at temperatures around 400° C are explained in terms offast-diffusing gas-like molecular oxygen in silicon. The concept of molecular oxygen is also invoked in a newly suggested model of thermal donor formation in silicon. The diffusivity of molecular oxygen in silicon is estimated to be around 10^–9cm²s^–1 at 450° C, almost nine orders of magnitude higher than the diffusivity of atomic oxygen in interstitial position.     

High-temperature thermal evolution of SiAs precipitates in silicon

The thermal evolution of monoclinic SiAs precipitates at 1050° C in silicon samples implanted with 1 and 1.5×10¹⁷ As/cm² was followed by transmission electron microscopy (TEM) and secondary neutral mass spectrometry (SNMS). These experiments show, for the first time, the coexistence of two different states of As in silicon, i.e., the electrically active and the inactive mobile dopant, in equilibrium with monoclinic SiAs precipitates. Moreover, they provide, for the saturation concentration of As in silicon, which includes both these states, a value of 3×10²¹ cm^–3 at 1050° C.     

Small angle neutron scattering from oxygen precipitates in silicon

The formation of silicon oxide precipitates from Czochralski grown silicon depends on the time and temperature of the heat treatment as well as on the initial content of interstitially dissolved oxygen. Samples containing between 5×10¹⁷ O_i/cm³ and 13×10¹⁷ O_i/cm³ have been heated at 750° C for 96 h. SiO₂ precipitates of various shape and size have been obtained and investigated by means of small angle neutron scattering (SANS) in the Q-range 0.05 Å^–1<Q<0.2 Å^–1. The obtained SANS patterns reveal a typical anisotropy of their intensity distribution, which splits into a central peak at Q<0.1 Å^–1 due to the shape of the individual particles and a number of weak intensities for large Q-values, originating from a correlation between defects, possibly between the precipitates. While these correlation peaks in the SANS patterns are seen best for rather low values of about (5–7)×10¹⁷ O_i/cm³ oxygen content, the central peak anisotropy is most pronounced for higher values of ca 10×10¹⁷ O_i/cm³. The integrated intensity of the central peak increases with increasing initial oxygen content. For comparison, untreated samples of the same initial oxygen content do not reveal any anisotropic SAN scattering or a broadened central peak beam.     

Energetics of Ge nucleation on SiO2 and implications for selective epitaxial growth

We have measured the time evolution of Ge nucleation density on SiO₂ over a temperature range of 673–973 K and deposition rates from 5.1 × 10¹³ atoms/cm² s (5 ML/min) to 6.9 × 10¹⁴ atoms/cm² s (65 ML/min) during molecular beam epitaxy. The governing equations from mean-field theory that describe surface energetics and saturation nucleation density are used to determine the size and binding energy of the critical Ge nucleus and the activation energy for Ge surface diffusion on SiO₂. The critical nucleus size is found to be a single Ge atom over substrate temperatures from 673 to 773 K, whereas a three-atom nucleus is found to be the critical size over substrate temperatures from 773 to 973 K. We have previously reported 0.44 ± 0.03 eV for the Ge desorption activation energy from SiO₂. This value, in conjunction with the saturation nucleation density as a function of substrate temperature, is used to determine that the activation energy for surface diffusion is 0.24 ± 0.05 eV, and the binding energy of the three-atom nucleus is 3.7 ± 0.1 eV. The values of the activation energy for desorption and surface diffusion are in good agreement with previous experiments of metals and semiconductors on insulating substrates. The small desorption and surface diffusion activation barriers predict that selective growth occurring on window-patterned samples is by direct impingement of Ge onto Si and ready desorption of Ge from SiO₂. This prediction is confirmed by the small integral condensation coefficient for Ge on SiO₂ and two key observations of nucleation behavior on the window-patterned samples. The first observation is the lack of nucleation exclusion zones around the windows, and second is the independence of the random Ge nucleation density on patterned versus unpatterned oxide surfaces. We also present the Ge nucleation density as a function of substrate temperature and deposition rate to demarcate selective growth conditions for Ge on Si with a window-patterned SiO₂ mask.     

Molecular dynamics simulation of homogeneous nucleation of KBr cluster

We perform molecular dynamics simulations to study the homogeneous nucleation in the freezing of molten potassium bromide clusters. The nucleation rates tend to decrease with increasing cluster size and temperature. The solid-liquid interfacial free energy σ_sl of 42.4-52.3 mJ/m² is close to the values predicted by Turnbull's relation and comparable to the experimental observation by Buckle and Ubbelohde. It is interesting to find that there is no cluster size effect on the critical nucleus size. Critical nucleus sizes inferred from classical nucleation theory are of 6.5-20.7 K⁺Br⁻ ionic pairs in the temperature range of 400-600 K. The critical nucleus size at bulk MD freezing temperature obtained by extrapolation is about 45 K⁺Br⁻ ionic pairs, which is comparable to the experimental value of NaCl.     

Anisotropy and temperature dependence of small angle neutron scattering from silicon-oxide precipitates in silicon

Czochralski grown silicon crystals contain interstitially dissolved oxygen which diffuses on heating to form precipitates of silica. We have examined these precipitates by small angle neutron scattering (SANS) in the Q-range 0.05 Å^–1<Q<0.4 Å^–1. The obtained SANS patterns reveal pronounced anisotropic intensity distributions which resemble the symmetry of the host crystal. The SANS spectra show an anisotropic central peak at Q<0.1 Å^–1 due to the single particle shape and a number of weak intensities for larger Q-values. These weak side maxima are considered correlation peaks or quasi-elastic interference peaks. They show, however, an unexpected and distinct temperature dependence: with decreasing temperature below values of 220 K their intensity is lost slowly, but reversibly. At T = 50 K only the central peak from the single-particle scattering remains unchanged. Upon heating, the correlation peaks regain their former value of intensity and Q-position without any evidence of thermal hysteresis.     

TEM characterization of yttrium silicide layers synthesized by ion implantation

The structure of Si implanted with high doses of yttrium has been investigated by varying implantation doses and energies. As implantation doses increase into the low 10¹⁷ cm^–2 range, silicide precipitates form. The precipitates are thin and long and lie parallel to {111} planes in the Si matrix. As dopant concentrations increase, the precipitates themselves become more equiaxed, aspect ratios decrease, and precipitates densities increase until the precipitates coalesce to form a continuous buried layer of yttrium silicide within the Si matrix. The layer thickness is relatively uneven. As implant doses increase to 4×10¹⁷ cm^–2, the layer thicknesses become more uniform although there are still defects present. As the implant doses increase further, the precipitate bands on either side of the continuous layer decrease due to gettering of yttrium to the layer. As the energy of the implant is increased, the appearance of the sample is similar to that of the lower energy implants except that the layer is buried deeper in the Si matrix. Observations of the silicide are consistent with its having the AlB₂ structure with ordered vacancies on the Si sublattice.Address from July 1, 1992: Arizona State University, Tempe, AZ     

Distinctive features of creep in silicon whiskers

The phenomenon of creep in silicon whiskers has been studied in the temperature range 300–1100°K at stresses (0.1–5)·10⁸ N·m^–2. On the basis of the tests, analysis of the fine structure of the creep curves, and studies on the crystal structure, the conclusion is drawn that the creep observed in silicon whiskers is due to the heterogeneous nucleation of dislocations at stress concentration sites with the participation of thermal fluctuations.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 31–35, October, 1981.     

Energy model for the Zr-based metallic glass alloy melt with clusters

An energy model for the melt of bulk metallic glass (BMG) with clusters was established, the Gibbs free energy and interfacial energy for the Zr-Al-Ni ternary alloy melt with Zr2Ni clusters were calculated, and the effects of the clusters on the Gibbs free energy, interfacial energy and nucleation rate were analyzed. The results showed that the existence of the clusters in the Zr-Al-Ni ternary alloy melt enables the Gibbs free energy to decrease in the composition range where bulk metallic glass forms easily, makes the interfacial energy increase and changes the distribution of the interfacial energy with the alloy composition. Because of the clusters in the melt, the Gibbs free energy of the Zr66Al8Ni26 alloy melt decreases about 0.3-1 kJ/mol and the interfacial energy between the melt and crystal nucleus increases about 0.016 J/m2. The nucleation rate of the undercooled Zr66Al8Ni26 alloy melt decreases evidently under the influence of the clusters on Gibbs free energy and the interfacial energy, and the maximum of the nucleation rate in the melt with the Zr2Ni clusters is only about 107 mol-1·s-1.     

Characteristic diffusion constants of cadmium in silicon

This investigation was devoted to experimental determination and analysis of curves describing the diffusive distribution of cadmium in silicon at different levels of prealloying of the silicon with phosphorus and different temperatures of isothermal diffusion, with allowance for the characteristic exponential relation between the pre-exponent D₀ and the activation energy Q. Numerical values of D_k and Q₀ were found. They are equal to 4·10^–8 cm² · sec^–1 and 0.22 eV, respectively.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 65–68, November, 1984.     

Optical characterization of laser-induced crystallized silicon films

Optical absorption coefficient spectra of thin silicon films were precisely investigated using a simple reflectance system with total reflectance mirrors placed on the rear side of samples in order to cancel an interference effect in a range between 1.1 eV and 3 eV. The absorption coefficient decreased according to crystallization as the laser energy increased and it got similar to that of single crystalline silicon in the range of 1.7 eV 3 eV. However, the absorption coefficient was higher than 10² cm^–1 in the photon energy lower than 1.3 eV. This probably results from band tail states caused by defect states localized at grain boundaries in the crystallized films. 2.5%-phosphorus doped laser crystallized silicon films had a high optical absorption coefficient ( > 10⁴ cm^–1) in the low photon energy range (1.1 eV 1.7 eV) caused by free carriers produced from the dopant atoms activated in the silicon films. The experimental results gave the carrier density of 1.3 × 10²¹ cm³ and the carrier mobility of 20 cm²/Vs.     

Effect of deep dislocation levels in silicon on the properties of p-n junctions

We present the results of studies on the influence of deep levels, due to dislocations in electronic-grade silicon, on the lifetime of minority carriers and on the current-voltage and capacitance-voltage characteristics of p-n junctions. The parameters of the deep levels were determined by means of dynamic spectroscopy. The carrier lifetime in the high-resistance region of the p-n junction correlates well with the dislocation density and varies from 10^–7 sec to 3 · 10^–8 sec when the dislocation density N_d varies from 10⁷ cm^–2 to 5 · 10³ cm^–2. The voltage across the p-n junction at a high level of injection varies 1.6 to 6.2 v as a function of N_d. The ionization energy of deep levels associated with dislocation in silicon is 0.44 and 0.57 eV, measured from the bottom of the conduction band.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 81–84, January, 1988.     

The kinetics of barium precipitation at dislocations in NaCl monocrystals

The kinetics of barium precipitation at dislocations in NaCl monocrystals has been studied in thermally and mechanically treated NaCl + 4 ppm BaCl₂ samples by investigating the isothermic variation of ionic conductivity as a function of time. The course of precipitation which takes place at dislocations located at grain boundaries can be divided into three time regions characterized by diffusion of impurities to dislocation cores at grain boundaries, nucleation, formation of new grain boundaries, etc. At higher number of dislocations an interruption of the precipitation appears due to a local free energy of nucleation minimum at radiusr ₀=6·92×10^–8 cm.     

Luminescence of CsPbBr3-like quantum dots in CsBr single crystals

Luminescence and decay kinetics of the Pb²⁺ aggregates in CsBr host crystals were measured in the 4–300 K temperature interval and in 10⁻¹⁰–10⁻³ time scale. Their emission properties are similar to those of CsPbBr₃ bulk crystal showing a subnanosecond free exciton emission in the 520–540 nm spectral region and slower trapped exciton emission in the 530–580 nm spectral region. An efficient energy exchange between the free and trapped exciton states is shown by the temperature dependencies of emission spectra. The quantum size effect is demonstrated in the high energy shift and broadening of the absorption and emission spectra and an estimate of the size of the CsPbBr₃-like aggregates is provided. Independent evidence of the presence of the CsPbBr₃ and Cs₄PbBr₆ aggregated phases in the CsBr host was obtained by X-ray structural studies.     

Ground state of aD − ion in semiconductors

The mechanisms that feature in the formation ofD ^– ions in spherical band semiconductors are discussed. Analogies are drawn with H^– formation (a proton binding two electrons). The variational method is applied in calculating the binding energy of the extra electron in the absence of external magnetic field. The binding energies obtained with different trial functions are compared with that extrapolated from experimental measurements. From such a comparison it is clear that a simple trial function with only one variational parameter involving the screening of the positive charge of the nucleus gives good results.     

In-beam implantation of iron into germanium,silicon and diamond studied by the Mössbauer effect

The Mössbauer effect of⁵⁷Fe implanted into diamond structure semiconductors, Ge, Si and C, has been studied by in-beam implantation of⁵⁷Fe ions, which were excited to the 14 keV state by a³⁵Cl beam from a tandem Van de Graaff accelerator. The time between the stopping of the⁵⁷Fe nucleus and the emission of the 14 keV -ray is determined by the lifetime (140 ns) of the 14 keV state. In each material the Mössbauer spectrum exhibits a doublet with velocity coordinates (in mm/s) at room temperature, relative to a sodium ferrocyanide absorber, as follows: diamond (–0.99, 1.10), silicon (–0.80, 0.21), and germanium (–0.88, –0.02). In silicon and germanium crystals the spectra were observed over the temperature range between 13 K and 870 K. The relative line intensities changed dramatically and the positions of the lines shifted systematically with temperature. In addition, channelling studies were made on iron that had been implanted into silicon.     

Defects in pulsed laser and thermal processed ion implanted silicon

The evolution of the nature and concentration of the defects produced by 100 or 300 keV As ions at fluences 1 to 4×10^–12 cm^–2 inn-type, Fz Silicon doped with 10¹⁵ to 10¹⁶ cm^–3 has been studied as function of thermal treatments (in the range 500°–900 °C) and of the energy density (in the range 0.3–0.6 J cm^–2) of a light pulse from a ruby laser (15 ns, 0.69 m). Deep-level transient spectroscopy (DLTS) combined with capacitance — voltage (C-V) measurements were used to get the characteristics (energy level, crosssection for the capture of majority carriers) of the defects and theirs profiles. The difficulties encountered in the analysis of the results, due to the large compensation of free carriers in the implanted region and to the abrupt defect and free carrier profiles, are discussed in detail and the corrections to apply on the C-V characteristics and the DLTS spectra are described. The defects resulting from the two types of treatments are found to be essentially the same. Only, for laser energies higher than 0.5 J cm^–2, the laser treatment appears to introduced new defects (atE0.32 eV) which should result from a quenching process. The fact that a laser energy smaller than the threshold energy for melting and recrystallization is able to anneal, at least partially, the defects produced by the implantation, demonstrates that the annealing process induced by the laser pulse is not a purely thermal process but is enhanced by a mechanism involving ionization.     

Donor states in tellurium-doped silicon

Hall effect and conductivity measurements are performed on Te-doped silicon in the temperature range 30KT800K. A Hall equipment suited for high temperatures up to 800 K has been constructed. The temperature dependence of the free electron concentration is analyzed for Te-doped silicon including one double-donor and several monovalent donor species. A deep level with an electrical activation energy of 200 meV is determined from the saturation of the free electron concentration at temperatures above 400 K. This level represents the first ionization stage of the Te double-donor. The second ionization stage is estimated to have an activation energy of 440 meV. The maximum electrically active Te concentration obtained is 5×10¹⁶cm^–3. Three different shallow donor states are resolved in the low-temperature range. The concentrations of these shallow donors are partially sensitive to a subsequent heat-treatment.     

The study of the interaction of indium with tellurium in silicon

The perturbed γ–γ angular correlation method has been employed to study indium-impurity pairs in silicon, consisting of the probe atom (¹¹¹In/¹¹¹Cd) and several group-VI donors. Such pairs can be identified via the interaction between the quadrupole moments of the probe nucleus and the electric field gradient (EFG) associated with the formed defect complex. A new quadrupole interaction frequency (QIF) of ν_Q=444(1) MHz (η=0) is measured at T=293 K in Te implanted silicon after annealing the sample above 700 K. The complex is attributed to the In-Te pair along 〈100〉-crystal axis in silicon. In addition, the temperature dependence of the QIF characterizing the pair has also been studied. The implantations of S and Se could not lead to the formation of observable complexes despite similar treatment of all samples. PACS 61.72.-y; 76.80.+y; 61.72.Cc     

Diffusion of silicon in titanium nitride films. Efficiency of TiN barrier layers

Two kinds of reactively evaporated titanium nitride films with columnar (B ₀ films) and fine-grained film structure (B ₊ films) have been examined as diffusion barriers, preventing the silicon diffusion in silicon devices. The silicon diffusion profiles have been investigated by 2 MeV ⁴He⁺ Rutherford backscattering spectrometry (RBS) after annealing at temperatures up to 900° C, in view of application of high-temperature processes. The diffusivity from 400 to 900° C: D (m² s^–1)=2.5×10^–18 exp[–31 kJ/mol/(RT)] in B ₀ layers and D (m² s^–1)=3×10^–19 exp[–26 kJ/mol/(RT) in B ₊ TiN layers. The diffusivities determined correspond to grain boundary diffusion, the difference being due to the different microstructure. The very low diffusivity of silicon in B ₊ TiN layer makes it an excellent high-temperature barrier preventing silicon diffusion.