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.     

Iron contamination in ion implanted silicon,as revealed by x-ray and electron diffraction

A surface contamination effect was detected by double-crystal x-ray diffraction analysis of silicon wafers implanted with silicon ions at different doses and energies after annealing at 700 °C.The hypothesis of recoiled oxygen from the native oxide, as the impurity responsible for surface strain, was excluded by x-ray characterization of a series of samples implanted through thermally grown silicon oxides. The surface positions of the strain, resulting from x-ray analysis after 700 °C annealing and the analysis of the electron diffraction patterns, taken on particles originated from precipitation of the impurity by 1000 °C heating, allowed to conclude that the contamination phenomenon is due to iron atoms coming from the ion implanter.     

Evidence of formation of tetravacancies in uniformly oxygen irradiated n-type silicon

High purity n-type silicon single crystal with resistivity in the order of 4000 Ω cm has been irradiated with high-energy oxygen ions at room temperature up to a fluence of 5E15 ions/cm². The energy of the beam was varied from 3 to 140 MeV using a rotating degrader to achieve a depthwise near-uniform implantation profile. Radiation induced defects and their dynamics have been studied using positron annihilation spectroscopy along with isochronal annealing up to 700 °C in steps of 50 °C for 30 min. After annealing the sample at 200 °C for 30 min, formation of silicon tetravacancies has been noticed. The formation of the tetravacancies was found to be due to agglomeration of divacancies present in the irradiated sample. An experimentally obtained positron lifetime value of 338±10 ps has been reported for silicon tetravacancies, which has a very close agreement with the value obtained from recent theoretical calculations. The tetravacancies were found to dissociate into trivacancy clusters upon further annealing. The trivacancies thus obtained were observed to agglomerate beyond 400 °C to form larger defect clusters. Finally, all the defects were found to anneal out after annealing the sample at 650 °C.     

Slow positron beam study of nitrogen implanted CZ-Si subjected to rapid thermal processing

In this experiment, nitrogen ions were implanted into CZ-silicon wafer at 100 keV at room temperature with the fluence of 5 × 10¹⁵ N₂⁺/cm², followed by rapid thermal processing (RTP) at different temperatures. The single detector Doppler broadening and coincidence Doppler broadening measurements on slow positron beam were carried out to characterize the defects in the as-implanted silicon and RTP-treated samples. It is found that both nitrogen-vacancy complexes (N-Vsi) and oxygen-vacancy complexes (O-Vsi) produced by nitrogen implantation diffuse back to the sample surface upon annealing. But the N-Vsi and the O-Vsi complete with each other and give a summed effect on positron annihilation characteristics. It is shown that the N-Vsi win out the O-Vsi in as-implanted sample and by RTP at 650 °C, 750 °C, which make the S-parameter increase; O-Vsi plays a dominant role after annealing above 850 °C, which makes the S parameter decrease.     

Interaction between rare-earth ions and amorphous silicon nanoclusters produced at low processing temperatures

Temperatures of 1000 °C and higher are a significant problem for the incorporation of erbium-doped silicon nanocrystal devices into standard silicon technology, and make the fabrication of contacts and reflectors in light emitting devices difficult. In the present work, we use energy-filtered TEM imaging techniques to show the formation of size-controlled amorphous silicon nanoclusters in SiO films annealed between 400 and 500 °C. The PL properties of such films are characteristic of amorphous silicon, and the spectrum can be controlled via a statistical size effect—as opposed to quantum confinement—that has previously been proposed for porous amorphous silicon. Finally, we show that amorphous nanoclusters sensitize the luminescence from the rare-earth ions Er, Nd, Yb, and Tm with excitation cross-sections similar in magnitude to erbium-doped silicon nanocrystal composites, and with a similar nonresonant energy transfer mechanism.     

Microstructural evolution upon annealing in Ar-implanted Si

The annealing effects of crystalline silicon (Si) implanted with argon (Ar) ions at a dose of 2 × 10¹⁶ Ar⁺/cm² at room temperature and subsequently annealed at 400-1100 °C for 30 min were investigated. The samples were analyzed by transmission electron microscopy and Raman spectroscopy. Before and after annealing up to 600 °C, an amorphous layer is formed but Ar bubbles are not observed in the damage layer. After annealing at 800 °C, argon bubbles are observed together with extended defects. The damage layer evolves into a polycrystalline structure. After annealing at 1100 °C; exfoliation occurs on the sample surface, and microtwin lamellas form in the damage layer. Raman scattering revealed that a strong recrystallization occurs from 600 °C to 800 °C. The results were compared with the case of helium implantation, with particular focus on bubble formation mechanisms.     

Gold diffusion in silicon by Rapid Optical Annealing

Gold diffusion in silicon is investigated using Rapid Optical Annealing at temperatures in the range of 800°C to 1200°C and annealing times from 300 s down to 1 s. The resulting content of substitutional gold is determined by spreading resistance measurements and analyzed by comparison with extensive numerical simulations.The profiles obtained show a broader spectrum as compared to the U-shapes after long time diffusion. The cooling process affects the profiles significantly, since they depend on the wafer thickness. An unexpected penetration depth was found after 1200°C diffusion in thick wafers, which are subject to small cooling rates. This phenomenon is due to a special combination of reverse kick-out, deep diffusion of highly supersaturated interstitial gold, and again an incorporation in lattice sites, termed the RDI effect.Numerical calculations allow us to reproduce the experimentally observed profiles only if a sensitive balance between the different temperature dependencies is obeyed. These investigations, therefore, yield new information about the equilibrium concentration and diffusion of silicon interstitials. A best set of parameters is presented. The time constant of the kick-out process is quantified for the first time.     

Model of the pair phosphorus atom-interstitial silicon atom

Interstitial defects in silicon implanted with P and Si ions are investigated by x-ray diffraction. It is established that the interstitial complexes formed by implantation and in subsequent heat treatment do not contain a P atom. A model is proposed for the pair PI: P atom-institial Si atom. The pair PI consists of P and Si atoms at the same interstice which are not bound to one another by a covalent bond. The pair model accounts for the characteristic features of the diffusion of implanted phosphorus in silicon. Fiz. Tverd. Tela (St. Petersburg) 40, 1995–1998 (November 1998)     

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.     

Modeling of the transient interstitial diffusion of implanted atoms during low-temperature annealing of silicon substrates

It has been shown that many of the phenomena related to the formation of “tails” in the low-concentration region of ion-implanted impurity distribution are due to the anomalous diffusion of nonequilibrium impurity interstitials. These phenomena include boron implantation in preamorphized silicon, a “hot” implantation of indium ions, annealing of ion-implanted layers et cetera. In particular, to verify this microscopic mechanism, a simulation of boron redistribution during low-temperature annealing of ion-implanted layers has been carried out under different conditions of transient enhanced diffusion suppression. Due to the good agreement with the experimental data, the values of the average migration length of nonequilibrium impurity interstitials have been obtained. It has been shown that for boron implanted into a silicon layer preamorphized by germanium ions the average migration length of impurity interstitials at the annealing temperature of 800 °C can be reduced from 11 nm to approximately 6 nm due to additional implantation of nitrogen. The further shortening of the average migration length is observed if the processing temperature is reduced to 750 °C. It is also found that for implantation of BF₂${\mathrm{BF}}_2$ ions into silicon crystal, the value of the average migration length of boron interstitials is equal to 7.2 nm for thermal treatment at a temperature of 800 °C.     

Optimization of nickel adsorption from aqueous solution by using activated carbon prepared from waste apricot by chemical activation

Waste apricot supplied by Malatya apricot plant (Turkey) was activated by using chemical activation method and K₂CO₃ was chosen for this purpose. Activation temperature was varied over the temperature range of 400-900 °C and N₂ atmosphere was used with 10 °C/min heat rate. The maximum surface area (1214 m²/g) and micropore volume (0.355 cm³/g) were obtained at 900 °C, but activated carbon was predominantly microporous at 700 °C. The resulting activated carbons were used for removal of Ni(II) ions from aqueous solution and adsorption properties have been investigated under various conditions such as pH, activation temperature, adsorbent dosage and nickel concentration. Adsorption parameters were determined by using Langmuir model. Optimal condition was determined as; pH 5, 0.7 g/10 ml adsorbent dosage, 10 mg/l Ni(II) concentration and 60 min contact time. The results indicate that the effective uptake of Ni(II) ions was obtained by activating the carbon at 900 °C.     

Electronic absorption spectra of Sm(II) and Yb(II) ions in a LiCl-KCl eutectic melt at 450 °C

We have measured the absorption spectra of Sm(II) and Yb(II) ions in LiCl-KCl eutectic at 450 °C. The UV spectra of Sm(II) and Yb(II) exhibited intense and broad peaks at around ∼260 nm, which is attributable to the 4f-5d transitions. With the aid of the UV-vis spectroscopic method, in-situ identification of spontaneous reduction of trivalent Sm and Yb ions to divalent ions was achieved.     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

Polymer compatibility, phase separation and high ambient conductivity in low — dimensional polymer electrolyte blends with lithium salts

AC and DC conductivities of complexes of Li salts with the amphiphilic helical polyether poly[2,5,8,11,14-pentaoxapentadecamethylene(5-hexadecyloxy-1,3-phenylene)] (I) (Type A complexes) and blends of I with copolymers of poly(tetramethylene oxide) oligomer coupled with either — (CH₂-)- (polymer IIC1) or — (CH₂)₁₂ — (IIC12) (Type C complexes) are reported. Whereas Type A complexes give reversible AC impedance plots log σ vs. 1/T plots which are ca. 10⁻⁷ S cm⁻¹ at ambient, the Type C blends rise to ca. 10⁻³ S cm⁻¹ at 100 °C and on cooling to ambient maintain this high level. In Type C systems with IIC12 this transformation is stable and permanent. Optical microscopy reveals phase separation of extensive well-organised lamellae of the Type A phase from the Type C blend following heating. Polymer II resides in thin layers in the interlamellar spaces serving to transfer ions between them. DC data at ambient temperatures for Li | I : II : Li salt | Li cells indicate conductivities 10⁻³ to 10⁻² S cm⁻¹ over extended periods (24 hours). Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Annealing behavior ot trap-centers in silicon containing A-swirl defects

The annealing behavior of trap-centers was studied in float-zone silicon wafers containing A-swirl defects. Samples from areas of high and low A-swirl density were annealed in nitrogen ambient between 100° and 900 °C, and analysed using the Deep Level Transient Spectroscopy. The results indicate, that two levels atE _c }-0.07 eV, _n=4.6×10^–16 cm², andE _c–0.49eV, _n=6.6×10^–16cm² are caused by one defect, for which the silicon di-selfinterstitial is a likely interpretation. A level atE _c }-0.11 eV was assigned to interstitial carbon. Both defects annealed out at about 170 °C. After 600 °C annealing an additional level atE _c–0.2 eV was detected, which was attributed to an interstitial silicon carbon complex. Heat treatment at 800 °C generated a new level atE _c–0.49 eV, _n=2.9×10^–16cm² only in the area of high A-swirl defect density. This level was also observed after oxidation and subsequent annealing of silicon.     

Copper donors in silicon

The temperature dependences of the resistivity and of the Hall constant were measured for dislocation-free p-type silicon saturated with copper under different conditions at temperatures round 1000°C. The analysis of the results and their discussion led to the conclusion that the copper donors form complexes the dimension and physical characteristics of which depend on the way the sample is prepared.     

Magnetic properties of MnO nanocrystals dispersed in a silica matrix

Magnetic nanocrystalline MnO particles have been synthesized in a silica glass matrix by the sol-gel method at calcination temperatures up to 1000 °C. EPR spectra of 0.1 mol% MnO doped silica gel and glasses studied in the temperature range 10-290 K show with the exception of those samples calcined at 900 and 1000 °C 6-line characteristic Mn(II) hyperfine (HF) lines. Additionally five spin-forbidden doublets have been observed at 100 K and below. Small spreads in spin Hamiltonian parameters (D and E) imply that the ligand field environments of Mn(II) ions embedded in the silica glass are nearly uniform. Monotonous decrease in HF linewidth in going from 120 °C gel to 800 °C calcined glass has been interpreted as the continuous decrease in population of isolated Mn²⁺ ions in silica glass matrix resulting in the decrease of magnetic dipolar interactions leading to the observed decrease in HF linewidth. XRD and TEM of sample calcined at 1000 °C shows the presence of nanocrystals of MnO having orthorhombic crystalline phase and sizes about 10 nm. The thermal behavior of magnetization (zero-field-cooled and field-cooled) and magnetic hysteresis of MnO nanocrystals in the 5-300 K temperature interval have demonstrated that the MnO nanocrystals display superparamagnetic-ferromagnetic transition at low temperatures. X-band EPR linewidth data plotted versus inverse of temperature (1/T) for samples calcined at 900 and 1000 °C (EPR recorded in the vicinity of 0.35 T applied field) depict similar transitions.     

Defects formation in the dual B+ and N+ ions implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions (to doses of 1.2×10¹⁴ or 1.2×10¹⁵ cm^–2) and 50 or 100 keV N⁺ ions (to doses from 1.2×10¹⁴ to 1.2×10¹⁵ cm^–2). After implantations, the samples were furnace annealed at temperatures from 100 to 450 °C. The depth profiles of the radiation damages before and after annealing were obtained from random and channeled RBS spectra using standard procedures. Two damaged regions with different annealing behaviour were found for the silicon implanted with boron ions. Present investigations show that surface disordered layer conserves at the annealing temperatures up to 450 °C. The influence of preliminary boron implantation on the concentration of radiation defects created in subsequent nitrogen implantation was studied. It was shown that the annealing behaviour of the dual implanted silicon layers depends on the nitrogen implantation dose.The authors would like to thank the members of the INP accelerator staff for the help during the experiments. The work of two authors (V.H. and J.K.) was partially supported by the Internal Grant Agency of Academy of Science of Czech Republic under grant No. 14805.     

Crystalline quality of 3C-SiC formed by high-fluence C-implanted Si

Carbon ions at 40 keV were implanted into (1 0 0) high-purity p-type silicon wafers at 400 °C to a fluence of 6.5 × 10¹⁷ ions/cm². Subsequent thermal annealing of the implanted samples was performed in a diffusion furnace at atmospheric pressure with inert nitrogen ambient at 1100 °C. Time-of-flight energy elastic recoil detection analysis (ToF-E ERDA) was used to investigate depth distributions of the implanted ions. Infrared transmittance (IR) and Raman scattering measurements were used to characterize the formation of SiC in the implanted Si substrate. X-ray diffraction analysis (XRD) was used to characterize the crystalline quality in the surface layer of the sample. The formation of 3C-SiC and its crystalline structure obtained from the above mentioned techniques was finally confirmed by transmission electron microscopy (TEM). The results show that 3C-SiC is directly formed during implantation, and that the subsequent high-temperature annealing enhances the quality of the poly-crystalline SiC.     

Effects of substrate temperature and oxygen pressure on the magnetic properties and structures of CoFe2O4 thin films prepared by pulsed-laser deposition

CoFe₂O₄ thin films were grown on silicon substrates by pulsed-laser deposition techniques at various temperatures from 350 °C to 700 °C and different pressures from 0.1 Pa to 10 Pa. The CoFe₂O₄ films with highly (1 1 1)-preferred orientation and smooth surfaces were obtained. The high coercivities of the films were attributed to the residual stress in the films, and the saturation magnetizations were mainly dependent on the oxygen pressure. Higher oxygen pressure could decrease the oxygen deficiencies in the films. Sufficient oxygen ions in the films enhanced the exchange interactions between the magnetic ions, as a result, increasing the saturation magnetization.