Nanostructuring Germanium Nanowires by In Situ TEM Ion Irradiation

Once nanomaterials have been synthesized, inducing further structural modifications is challenging. However, being able to do so in a controlled manner is crucial. In this context, germanium nanowires are irradiated in situ within a transmission electron microscope (TEM) by a 300 keV xenon ion beam at temperatures ranging from room temperature (RT) to 500 °C. The ion irradiation is performed in situ and the evolution of nanowires during irradiation is monitored. At 300 °C and below, where the temperature is low enough to allow amorphization, the ion beam causes the formation of nanostructures within the nanowires. Formation of nanopores and swelling of nanowires is observed for a very low fluence of 2.2 × 10¹⁴ and up to 4.2 × 10¹⁵ ions cm⁻². At higher fluences, the thickness of the nanowires decreases, the nanowires lose their wire-like cylindrical shape and the nanostructuring caused by the ion beam becomes more complex. The nanostructures are observed to be stable upon crystallization when the nanowires are annealed at 530 °C. Furthermore, in situ imaging allows the growth of nanopores during irradiation to be followed at RT and at 300 °C providing valuable insights into the mechanism responsible for the nanostructuring.     

Annealing behaviour of arsenic implants in silicon

Abstract

The annealing behaviour of 80 keV room temperature arsenic implants in silicon below the amorphization dose has been studied by comparing the physical profile and the electrical profiles following different isochronal anneals.

It is shown that the electrically active fraction, which is about 0.4 after 30 min annealing at 600°C, increases continuously until 100% electrical activation of the arsenic ions is reached at about 900°C.

The activation energy for the annealing process has been found equal to 0.4 eV. A tentative interpretation of the mechanism involved is given.

From the analysis of the physical profiles obtained after isochronal annealing, an effective diffusion coefficient at 900°C equal to 5 × 10^?16 cm² s^?1 has been calculated.     

Analysis of phase transition behavior of BaCeO3 with thermal analyses and high temperature X-ray diffraction

Structural phase transitions in BaCeO₃ have been investigated with combination of differential scanning calorimetry (DSC), dilatometry and high temperature X-ray diffraction with high sensitivity and resolution. In DSC curve at heating procedures, baseline shift, endothermic peak and another baseline shift were observed at 260 °C, 385 °C and 895 °C, respectively. From DSC curve at cooling procedure, it was revealed that all the baseline shifts and peak were reversible. No hysteresis was observed in the both baseline shifts indicating second order phase transition at 260 °C and 895 °C with variation of specific heat capacity, ΔC_p, of 10 J/mol K and 7 J/mol K, respectively; whereas the order of the phase transition at 385 °C was revealed to be the first since hysteresis was detected around 370–385 °C. Variation of enthalpy, ΔH, at the phase transition was 45 J/mol. High temperature X-ray diffraction measurements have revealed that the crystal structure of BaCeO₃ changes from primitive orthorhombic perovskite through body-centered one, rhombohedral distorted one to cubic one around 280 °C, 400 °C and 900 °C, showing correspondence with DSC curves. Dependence of molar volume on temperature estimated from high temperature X-ray diffraction showed agreement with thermal expansion behavior observed with dilatometry.     

In-situ and ex-situ study of crystallization behaviour of magnetron sputtered Ni63Zr37 amorphous thin film

ABSTRACT

The stages of crystallization of magnetron sputter-deposited Ni₆₃Zr₃₇ film with mostly amorphous structure have been investigated by differential scanning calorimetry (DSC) and in-situ annealing at 300°C by use of heating stage on a high-resolution transmission electron microscope (HRTEM). These results have been further confirmed by grazing incidence X-ray diffraction analyses of thin film specimens annealed ex-situ at 300°C for various durations. The temperature for crystallization found by DSC has been found to increase from 371°C to 434°C with an increase in heating rate from 3°C/min to 10°C/min, and the apparent activation energy for amorphous to crystalline transformation has been found as ～260.2?kJ/mol from the Kissinger plot. Studies on HRTEM using in-situ heating stage have shown the crystallization to occur on annealing at 300°C for ～10?min. Crystallization at a temperature lower than that found by DSC is attributed to structural relaxation with reduction of free volume due to thermal activation. It has been observed that Ni₃Zr forms first due to its large negative enthalpy of formation, and is followed by the formation of Ni-rich solid solution (Ni_ss) grains. HRTEM studies have shown grain rotation with the formation of partial dislocations at Ni₃Zr-Ni_ss interfaces as well as twinning followed by detwinning with dislocation formation in the Ni_ss matrix possibly to reduce the interfacial energy.     

Indentation studies of alkali halides at elevated temperatures

The hardness of NaCl and KCl crystals has been estimated from the lengths of dislocation rosette formed around indentation at various temperatures up to 400°C. The hardness decreases with increasing temperature. This is due to the softening of the crystals at elevated temperatures which results in the easy movement of dislocations. The results are discussed using a few available relations which connect hardness to temperature. Arms of indentation dislocation rosette are well defined up to 300°C but around 400°C the rosette pattern is spread over a circular region. A possible mechanism is discussed.     

Investigating the optical properties of a near-surface layer in silicon implanted by zinc after thermal annealing

Changes in the optical properties of a Si layer broken as a result of implantation by Zn ions are investigated during thermal annealing. The investigations are performed by Raman scattering (RS), ellipsometry, and cathodoluminescence (CL). The implanted samples show a broken area with a thickness of about 60 nm with partial amorphization. Thermal treatment at 400°C results in the partial annealing of a radiation point defect while reducing the thickness of the broken layer to 40 nm. The broken layer was completely restored after high-temperature annealing at 700°C.     

Preparation,structural characterization and conductivity of LiZr2(PO4)3

Amorphous LiZr₂(PO₄)₃ has been prepared at room temperature starting from aqueous solutions of ZrOCl₂, H₃PO₄, and LiOH and then crystallized by heating at temperatures between 600 and 900°C. The material obtained at 900°C has been characterized by X-ray powder diffractometry, DSC analysis, and ac conductivity. It is monoclinic from 20 up to about 300°C and orthorhombic at higher temperatures. A change in the activation energy for conduction (from 0.79 to 0.43 eV) and a weak endothermic effect (0.9–1.7 cal/g) are associated with the phase transition. The ac conductivity of sintered pellets is, on average, 7×10⁻⁴ S cm⁻¹ at 300°C.     

Phase transformations in the Mn-Ge system and in Ge x Mn1 ? x diluted semiconductors

Results of an X-ray diffraction study as well as magnetic and electrical measurements of the solid-state reactions in Ge/Mn polycrystalline films of an 80/20 atomic composition have been presented. It has been shown that the ferromagnetic Mn₅Ge₃ phase is formed first on the Ge/Mn interface after annealing at ??120°C. The further increase in the annealing temperature to 300°C leads to the beginning of the synthesis of the Mn₁₁Ge₈ phase, which becomes dominating at 400°C. The existence of new structural transitions in the Mn-Ge system in the region of ??120 and ??300°C has been predicted on the basis of the presented results and results obtained earlier when studying solid-state reactions in different film structures. The supposition about the general chemical mechanisms of the synthesis of the Mn₅Ge₃ and Mn₁₁Ge₈ phases during the solid-state reactions in the Ge/Mn films of the 80/20 atomic composition and the phase separation in Ge _x Mn_{1 ? x} (x > 0.95) diluted semiconductors has been substantiated.     

Effect of thermal annealing on spectral properties of electrodeposited carbon films

The effect of thermal annealing on properties of carbon films deposited on nickel electrodes by the electrodeposition method was studied. It has been shown that annealing at a temperature of 300°C results in the formation of nanosize diamond clusters. With an increase in the annealing temperature, the size of diamond clusters diminishes. At an annealing temperature of 900°C, all of the carbon enters into reaction with nickel, thus forming nickel carbide.     

Self-organization of the structure in the Cu60Fe40 composite during deformation-thermal treatment

The deformation-thermal stability of a clusterized amorphous-crystalline structure prepared from a Cu₆₀Fe₄₀ powder mixture at a logarithmic strain e = 4.6 and subjected to isochronous (40 min) annealings at T _a = 200–800°C has been investigated. Periodic changes (ΔT = 300°C) in the order and disorder with a maximum ordering at T _a = 300 and 600°C and a maximum disordering at T _a = 400 and 700°C have been observed. The periodicity of the dominant crystallographic order with a period ΔT = 400°C in the annealing temperature has been revealed for face-centered cubic copper phase planes separated by a singular point at T = 500°C characterized by the dominant body-centered cubic iron phase ordering. It has been shown that the sawtooth shape of the size distribution of strain clusters formed within the crystal structure of deformed samples slowly changes with increasing annealing temperature from exponential (T _a = 200–700°C) to linear (T _a = 800°C). This indicates a high density of internal local distortions in structural units.     

Characterization of silicon doped with sodium upon high-voltage implantation

The depth distribution profiles of sodium atoms in silicon upon high-voltage implantation (ion energy, 300 keV; implantation dose, 5 × 10¹⁴ and 3 × 10¹⁵ cm ^?2) are investigated before and after annealing at temperatures in the range T _ann = 300–900°C (t _ann = 30 min). Ion implantation is performed with the use of a high-resistivity p-Si (ρ= 3–5 kΩ cm) grown by floating-zone melting. After implantation, the depth distribution profiles are characterized by an intense tail attributed to the incorporation of sodium atoms into channels upon their scattering from displaced silicon atoms. At an implantation dose of 3 × 10¹⁵ ions/cm², which is higher than the amorphization threshold of silicon, a segregation peak is observed on the left slope of the diffusion profile in the vicinity of the maximum after annealing at a temperature T _ann = 600°C. At an implantation dose of 5 × 10¹⁴ ions/cm², which is insufficient for silicon amorphization, no similar peak is observed. Annealing at a temperature T _ann = 700°C leads to a shift of the profile toward the surface of the sample. Annealing performed at temperatures T _ann ≥ 800°C results in a considerable loss of sodium atoms due to their diffusion toward the surface of the sample and subsequent evaporation. After annealing, only a small number of implanted atoms that are located far from the region of the most severe damages remain electrically active. It is demonstrated that, owing to the larger distance between the diffusion source and the surface of the sample, the superficial density of electrically active atoms in the diffusion layer upon high-voltage implantation of sodium ions is almost one order of magnitude higher than the corresponding density observed upon low-voltage implantation (50–70 keV). In this case, the volume concentration of donors near the surface of the sample increases by a factor of 5–10. The measured values of the effective diffusion parameters of sodium at annealing temperatures in the range T _ann = 525–900°C are as follows: D ₀ = 0.018 cm²/s and E _a = 1.29 eV/kT. These parameters are almost identical to those previously obtained in the case of low-voltage implantation.     

Variable-Temperature and High-Pressure Micro-Raman Spectra of Inorganic Artists' Pigments: Crystalline Wulfenite,Lead(II) Molybdate(VI), PbMoO4

Variable-temperature (?150°C to 600°C) and high-pressure (up to ～5 GPa) micro-Raman spectra have been obtained for the mineral wulfenite [lead(II) molybdate(VI), PbMoO₄], a main constituent of the artists' pigment, orange molybdate. The spectra were quite similar in both the temperature and the pressure studies, except for broadening and shifting of some peaks. No phase changes were detected, although there is possibly some amorphization beginning at ～600°C. The photoacoustic IR spectrum in the 1950–450 cm^?1 region is reported for characterization purposes. The long-term stability of PbMoO₄ with respect to extreme changes in both temperature and pressure illustrates the importance of orange molybdate in artwork and protective coatings.     

Thermal expansion measurements for estimating vacancy concentration in X-ray irradiated KCl single crystals

A sensitive capacitance technique is used for measuring changes in length (Δl) of KCl single crystals with temperature in the region 30–300°C. These measurements have been taken on KCl in (i) as-cleaved (ii) X-ray irradiated (iii) quenched and X-ray irradiated conditions (X-ray irradiation was always done at room temperature (≈ 30°C). The linear coefficient of thermal expansion (α) of the as-cleaved sample is 40.8 × 10^-6°C^-1. Variation of Δl with temperature in X-ray irradiated crystal shows two regions: (a) 30–180°C where α is 48.1 × 10^-6°C^-1, (b) 180–300°C where α is 40.4 × 10^-6°C^-1. Similar behaviour is exhibited by quenched and later X-ray irradiated KCl the first region is up to 140°C, beyond which the second region takes over. From these data, concentration of vacancies in X-ray irradiated KCl at room temperature is calculated to be 3.4 × 10¹⁷ cm^-3 which is in fairly good agreement with the value obtained from F-band absorption measurements on the sample. An attempt has been made to understand these results.     

Temperature dependence of positron parameters in voids and loops in Mo

The temperature dependence of positron lifetime parameters has been measured in the temperature interval from ?196°C to 300°C for two Mo samples containing voids? and loops. Both samples show an increased intensity of positrons annihilating in voids with increasing temperature. Strongly temperature dependent trapping into a loop bound defect is consistent with the experimental observations. It is shown that this trapping rate then decreases by approximately a factor 3 in the temperature range from ?196°C to 300°C. On basis of experimental data it can be ruled out that detrapping takes place from this defect.     

Shape evolution of gold nanoparticles

The tetraoctylammonium bromide-stabilized gold nanoparticles have been successfully fabricated. The shape evolution of these nanoparticles under different annealing temperatures has been investigated using high-resolution transmission electron microscopy. After an annealing at 100 °C for 30 min, the average diameters of the gold nanoparticles change a little. However, the shapes of gold nanoparticles change drastically, and facets appear in most nanoparticles. After an annealing at 200 °C for 30 min, not only the size but also the shape changes a lot. After an annealing at 300 °C for 30 min, two or more gold nanoparticles coalesce into bigger ones. In addition, because of the presence of Cu grid during the annealing, some gold particles become the nucleation sites of Cu₂O nanocubes, which possess a microstructure of gold-particle core/Cu₂O shell. These Au/Cu₂O heterostructure nanocubes can only be formed at a relatively high temperature (≥300 °C). The results can provide some insights on controlling the shapes of gold nanoparticles.     

Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

STM study of structural changes on Si(100)2×1-Sb surface induced by atomic hydrogen

Using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED), we have studied the structural changes of the Si(100)2×1-Sb surface caused by hydrogen adsorption at both room temperature (RT) and 300°C. We have found that the ordering of a 2×1-Sb surface is more stable against atomic hydrogen exposure at 300°C than at RT, and that some Sb atoms desorb during atomic hydrogen exposure at 300°C. However, upon hydrogen exposure at both temperatures, we have observed neither three-dimensional islands nor the hydrogen terminated Si substrate which were reported for hydrogen interaction with the other metal/Si systems. On the 2×1-Sb surface exposed to atomic hydrogen of 1000 L at RT followed by 550°C annealing, long bright lines similar to those reported for the Bi/Si(100) system have also been found.     

Interaction of oxygen and hydrogen with Pd-Au alloys: An AES and XPS study

Pd-Au alloys of three different concentrations have been studied with Auger Electron Spectroscopy and Photoelectron Spectroscopy. A quantitative method shows that the decontaminated surfaces possess the same composition as the bulk. Interaction of oxygen up to 600°C with gold rich alloys (>85%) is very weak. It starts around 300°C on the other two alloys and results in a significant palladium surface enrichment. On the 60 at% Pd-Au alloy, at 500–580°C, the surface may be completely covered with PdO. A hydrogen treatment at 350°C leads to a complete reduction of the oxide without reequilibration of the surface.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001