Formation of thermal vacancies in highly As and P doped Si

Using positron annihilation measurements we observed the formation of thermal vacancies in highly As and P doped Si. The vacancies start to form at temperatures as low as 650 K and are mainly undecorated at high temperatures. Upon cooling the vacancies form stable vacancy-impurity complexes such as V-As3. We determine the vacancy formation energy of E(f)=1.1(2) eV and the migration energy of E(m)=1.2(1) eV in highly doped Si. By associating these values with the vacancy-impurity pair, we get an estimate of 2.8(3) eV for the formation energy of an isolated neutral monovacancy in intrinsic Si.     

Positron annihilation study of alpha-irradiated stainless steel SS 302 and Cobalt

Abstract

Positron lifetime and Doppler broadening measurements have been done to study the α-induced defects in stainless steel SS 302 and polycrystalline cobalt. For stainless steel the samples have been thin and the effect of the presence of helium on defect kinetics has been avoided by allowing the 30 MeV alpha particles to pass through the samples. The presence of impurity (carbon) atoms in steel is found to play an important role in the trapping and detrapping of vacancies in the temperature range 200°C to 450°C. Formation of vacancy-impurity complexes and their dissociation around 500°C have been observed. A steady decrease of the positron parameters has been seen beyond 700°C and they attain those of the reference sample around 1000°C. While annealing alpha irradiated cobalt we find migration of vacancies and rearrangement of dislocation loops below 650 K and then dissolution around 900 K. Helium-vacancy complexes form in the region 600 to 1000 K, leading to the growth of the He-bubble above 1000 K. The trapping model analysis shows strong interaction between He and vacancy clusters in the temperature region 600 to 1000 K.     

Muon trapping at vacancies in pure and doped iron

This paper gives a summary of the results obtained by the Konstanz group on electron-irradiated iron. The main achievement was the observation of a number of different frequencies in Fe, which could be assigned to isolated vacancies and to vacancy-impurity pairs. The annealing behaviour of these frequencies was studied. In the present paper, the framework for the analysis of the data and the main conclusions are reviewed.     

Investigation of electron irradiated iron alloys and nickel

SR experiments were performed on electron-irradiated magnetic samples. In dilute iron alloys, the isolated vacancy (30 MHz line) was observed up toT _A (annealing temperature) = 200 K. Above this temperature a new line (30 MHz +v), assigned to vacancy-impurity pairs, was found in some alloys. The frequency shiftv and the annealing behaviour of the new line are characteristic for each impurity. In electron-irradiated Nino newSR line was observed.The financial support of the Bundesministerium für Forschung und Technologie is gratefully acknowledged.     

Heat transport over nonmagnetic lithium chains in LiCuVO<Subscript>4</Subscript>, a new one-dimensional superionic conductor

The thermal conductivity of three single-crystal samples of the quasi-one-dimensional spin system of LiCuVO₄ with different concentrations of defects (primarily, vacancies on the lithium sublattice) was measured along the crystallographic a axis (along the nonmagnetic lithium chains) in the temperature interval 5–300 K. An increase in thermal conductivity from that of the crystal lattice was revealed for T>150–200 K. This increase can be accounted for only by assuming LiCuVO₄ to be a superionic conductor. This assumption was confirmed by measuring its electrical conductivity in the temperature interval 300–500 K. Li⁺ ions move over vacancies on the lithium sublattice (conducting channels) and act as charge carriers in LiCuVO₄. It is shown that LiCuVO₄ is a fairly good superionic conductor with application potential.     

Perturbation de l'echange electronique rapide par les lacunes cationiques dans Fe3−xO4(x ⩽ 0,09)

As most previous work on non-stoichiometric magnetite Fe_3−xO₄ has been carried out with fine powders prepared in the metastable domain, with the inherent uncertainties, we have prepared small crystals by quenching from the high temperature stability range.With increasing x, the cell parameter decreases, the Verwey temperature falls below 4.2 K for x = 0.09, the thermal stability decreases (disproportionation occurs at ~550K for x = 0.09), the saturation magnetization at 125 K varies as (4.1 – 2x) suggesting that the vacancies are mainly octahedral; this is confirmed by the Mössbauer effect at 150 K and 5 Teslas. At 4.2 K with 8 T, the Mössbauer spectrum is very complex but displays a mixed-valence signal involving a fraction (~ 10%) of the octahedral sites. This signal is evidence for electron tunnelling. The conductivity, at 295 K, decreases more rapidly than (1 − 3x); the conductivity of stoichiometric magnetite is described by the dynamic correlation model applied to short-range ordering; for x = 0.09 an activation energy of 0.077 eV is deduced between 39 and 120K.These results are interpreted as evidence that the tunnel effect at low temperature is limited to domains separated by vacancies, associated with 5 times more electron holes, and by regions where short-range order prevails.     

Gap at the Fermi level in the intermetallic vacancy system RBiSn(R=Ti,Zr,Hf)

The new class of intermetallic compounds RNiSn(R=Ti,Zr,Hf) may be characterised by the presence of an ordered sublattice of Ni atom vacancies in comparison with normal metals RNi₂Sn with no Ni vacancies. We report unusual transport and optical properties of the RNiSn system. The electrical resistivity of RNiSn is very high (3<p<100) mOhm*cm; the temperature coefficient of resistivity (TCR) is negative and strongly dependent on the annealing conditions. For some samples ZrNiSn and for a single crystal of TiNiSn the resistivity can be described by the Mott's law at temperatures 0.1<T<20 K. A phase transition nearT=100 K without change of crystal structure was deduced from Hall effect data and the temperature dependence of the lattice constant. Preliminary data on transport phenomena in RPtSn and RPdSn(R=Ti,Zr,Hf) compounds are also reported. The unusual properties of RNiSn system might be related to a gap of the electron spectrum near the Fermi energy.     

Behaviour of vacancies in dilute Fe–Re alloys: a positron annihilation study

Positron annihilation lifetime spectroscopy was used in a room temperature study of the influence of heat treatment on behaviour of vacancies in Fe_0.97Re_0.03 and Fe_0.94Re_0.06 alloys. In this experiment, the vacancies were created during the formation and further mechanical processing of the iron systems under consideration so the lifetime spectra of positrons were collected at least twice. The first samples were taken just after the melting process in an arc furnace, and the second ones were taken for the specimens annealed at 1,270 K and then cold-rolled at room temperature. After that, the spectra were measured for all studied samples after annealing at some temperatures gradually increasing from 300 to 1,270 K. It was found that vacancy-Re pairs are the dominant type of structural defects in alloys just after the melting process. In the case of alloys after a cold rolling process, the dominant type of structural defects is vacancies associated with edge dislocations. Moreover, for cold-rolled samples annealed at 473–573 K, the growth of the vacancy clusters associated with edge dislocations is observed by an increase in the mean positron lifetime. Finally, at temperatures above 573 K, vacancy clusters associated with edge dislocations as well as vacancy-Re pairs become unstable, and freely migrating vacancies sink at grain boundaries.     

Positrons and electron-irradiation induced defects in the layered semiconductor InSe

The positron annihilation characteristics of the layered semiconductor InSe have been investigated. No evidence for low temperature positron trapping is found in as-grown and heavily deformed InSe. The temperature dependence of the S-parameter in these sample exhibits an increase rate in good agreement with the linear expansion coefficient along the c-axis. The positron lifetime spectra of electron-irradiated 0.01% Sn-doped InSe show a long-lifetime component of 336 ps which is tentatively attributed to positrons trapped at isolated In vacancies. Isochronal annealing experiments performed on these samples show that the recovery of the positron lifetime measured at 77K is accomplished in two stages. The first, starting after annealing at 150K, could be induced by the formation of complexes (V_In-Sn_In). The second stage, observed at temperatures T375K, is attributed to the dissociation of these complexes and subsequent annealing of the In vacancies.     

Specific heat of Ce x La1 − x B6 in the low cerium concentration limit (x ≤ 0.03)

The specific heat of high-quality Ce _x La_{1 ? x} B₆ (x = 0, 0.01, 0.03) single crystals is studied in the temperature range 0.4–300 K. LaB₆ samples with various boron isotope compositions (¹⁰B, ¹¹B, ^nat B) are analyzed to estimate the effect of boron vacancies. The experimental data are used to take into account the electron component correctly under the renormalization of the density of states at T < 8 K, the contribution of the quasi-local vibrational mode of a rare-earth ion with the Einstein temperature Θ_E ≈ 152 K, the Debye contribution from the rigid cage of boron atoms with the Debye temperature Θ_D ≈ 1160 K, and the low-temperature Schottky contribution related to the presence of 1.5?2.3% boron vacancies in the rare-earth hexaborides. The detected low-temperature anomalies in the specific heat are shown to be interpreted in terms of the formation of two-level systems with an energy ΔE = 92–98 K caused by the displacement of rare-earth ions from their centrosymmetric positions. A scenario of heavy fermion formation that is alternative to the Kondo mechanism is proposed for the systems with a magnetic impurity.     

Positron studies of hydrogen-defect interactions in proton irradiated molybdenum

Molybdenum single crystals are irradiated at 20 K with 6 MeV protons. The radiation damage and lattice defect annealing is studied by positron lifetime spectroscopy in the temperature range from 15 to 720 K. Loss of vacancies due to recombination with mobile interstitials is observed at 40 K (Stage I) in agreement with resistivity measurements. This is the first time Stage I is observed by positrons below 77 K. The implanted hydrogen decorates the vacancies around 100 K, which is consistent with a hydrogen migration energy in molybdenum:E _M ^H = 0.3–0.4 eV. Clustering of spatially correlated vacancies takes place in a wide temperature region below the usual vacancy clustering stage (Stage III). Stage III is observed at rather low temperatures (400–480 K) due to the very high vacancy concentration. Hydrogen bound to vacancies and vacancy clusters is released above 540 K, which puts an upper limit to the hydrogen binding energy:E _B ^H 1.4 eV. The present work emphasizes the advantage of employing a vacancy sensitive technique to study hydrogen in metals, where its intrinsic solubility is low. In such metals (as molybdenum) both the effective solubility and the effective mobility of hydrogen are strongly influenced by the presence of vacancies.     

Thermal conductivity of Zn doped CoFe2O4 ferrites

A series of samples of the type Co_1-xZn_xFe₂O₄ (x = 0.0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8 and 1.0) was prepared as ceramics. The existence of a single phase was confirmed by x-ray studies. The thermal conductivity and specific heat were measured at temperatures ranging from 100°C to 200°C. The thermal conductivity had a minimum value at x = 0.4, caused by maximum scattering of thermal phonons which arose from the change of crystal size and excess of lattice vacancies. The phonon frequency was estimated to have an optimum value at x = 0.4, resulting from maximum porosity which disturbs the propagation of the thermal waves.     

Structure and energy level of native defects in as-grown and electron-irradiated zinc germanium diphosphide studied by EPR and photo-EPR

The properties of defects in as-grown p-type zinc germanium disphosphide (ZnGeP₂) and the influence of electron irradiation and annealing on the defect behavior were studied by means of electron paramagnetic resonance (EPR) and photo-EPR. Besides the well-known three native defects (V_Zn, V_P, Ge_Zn), an S=1/2 EPR spectrum with an isotropic g=2.0123 and resolved hyperfine splitting from four equivalent I=1/2 neighbors is observed in electron-irradiated ZnGeP₂. This spectrum is tentatively assigned to the isolated Ge vacancy. Photo-EPR and annealing treatments show that the high-energy electron irradiation-induced changes in the EPR intensities of the zinc and phosphorus vacancies are caused by the Fermi level shift towards the conduction band. Annealing of the electron-irradiated samples induces a shift of the Fermi level back to its original position, accompanied by an increase of the EPR signal associated with the V_Zn⁻ and a proportional increase of the EPR signal assigned to the V_P⁰ under illumination (λ<1 eV) as well as generation of a new defect. The results indicate that the EPR spectra originally assigned to the isolated V_Zn⁻ and V_P⁰ are in fact associated defects and the new defect is probably the isolated phosphorus vacancy V_Pi.     

Electronic resistivity and deffect structure of β-LiAl as a function of temperature and composition

The electrical resistivity of β-Li_xAl_1?x has been measured from 10 K to 290 K in single crystal samples for four different concentrations, x=0.480, 0.486, 0.500 and 0.525. An anomaly at 100 K is observed for the three lowest Li concentrations. This anomaly is associated with an ordering of constitutional Li vacancies. Above 100 K the temperature dependent part of the resistivity is independent of the Li concentration. However, the residual resistivity increases very rapidly with increasing Li concentration, becoming ～ 75 μΩ-cm for x=0.525. These results suggest that the two defect model of β-LiAl may be incomplete.     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

Temperature dependence of the permittivity of PbWO<Subscript>4</Subscript> crystals in the range 290–550 K

The temperature dependence of the permittivity ε of PbWO₄ crystals is studied in the range T = 290–550 K at a frequency of 1 kHz. The ε(_T) dependences measured on heating and cooling are different. On heating, groups of narrow maxima at 290–330 K and 330–400 K are observed in the ε(_T) curves. The first group of peaks is dominant. High-temperature polarization produces an additional broad peak in the ε (_T) curve at 400 K. A linear ε(_T) dependence is observed in the range 400–470 K. Above 470 K, the variation in ε(_T) closely follows an exponential law. Restoring relaxation of ε in the range 25–30 at 290 K after high-temperature sample heating proceeds exponentially in a few stages. The features of ε(_T) curves are determined by the dipole polarization and the hopping mechanism of charge exchange between complex dipole associates. Such structural defects may be pairs of doubly charged lead and oxygen vacancies (diplons). These defects also form a basis for more complicated defect complexes with localized holes (or electrons) at the corresponding vacancies.     

Radiation defects in Si of high purity

Abstract

Radiation defects created by γ-irradiation of Co⁶⁰ and fast neutrons in high purity p-Si (p = 5×10³ to 4 × 10⁴ Ω.cm) and n-Si (p = 4 × 10² to 5 × 10³ Ω.cm) are investigated by measurements of Hall effect, resistivity and minority carrier lifetime. The oxygen concentration in the crystals is in the range of 5 × 10¹⁴ to 5 × 10¹⁵ cm^?3.

It is shown that stable γ-defects at 300 °K are divacancies and complexes of vacancies with donor or acceptor impurities. Divacancies introduced by γ-irradiation are the secondary defects. They become predominant after ‘exhaustion’ of the dopant. When divacancies become the predominant defects the Fermi level occupies its boundary position E_v +0.39 eV in the gap. At low doses (Φ<10¹⁶ photons/cm²) vacancy-impurity complexes and at heavy doses (Φ>10¹⁷ photons/cm²) divacancies play the main role in the recombination process.

In neutron irradiation disordered regions are introduced and the level at E_v +0.35 eV is observed. The Fermi level in both n- and p-Si shifts to the middle of the gap. At the annealing of disordered regions in the interval 200 to 250 °C the level at E_v +0.27 eV appears and Fermi level occupies its boundary position at E_v +0.39 eV. This indicates that divacancies become the predominant defects which can be formed as secondary defects at the destruction of the disordered regions.     

Structural,magnetic, and physical properties of La(1–x)MnO3±δ nano-manganite

A detailed structural, magnetic and physics properties of La_1?xMnO_3±δ (LMO) nanomanganites were investigated to find out the role of cationic vacancies (La vacancy with Mn³⁺/Mn⁴⁺) in grain size modulation. Crystal structure and phase analysis of all samples were carried out by Rietveld refinement of high-resolution XRD and neutron diffraction data. We report here, the oxygen content in studied LMO compound decreases with increase in La vacancies in parent site and a parasitic Mn₃O₄ phase has been evolved in the range of 0.9 ≥ La/Mn ≥ 0.7. Para to ferro magnetic transition temperature (T_C) of all nanometric samples (La/Mn < 0.9) was found at high temperature side (≥260 K) whereas, the same for bulk one (La/Mn ≥ 0.9) was around 160 K. The enhancement of T_C (~70 K) with size reduction is attributed to broadening of bandwidth due to compaction of MnO₆ octahedra in system unit cell. In bulk sample, a secondary cluster/spin glassy phase is found below 50 K, whereas the glassy phase has been suppressed in nanoscale. Field-dependent magneto-resistance measurements are also carried out for all samples at different temperatures to get a profound insight of magneto-transport dynamics of the present system.     

Formation of vacancy-impurity complexes by kinetic processes in highly As-doped Si

Positron annihilation experiments have been applied to verify the formation mechanism of electrically inactive vacancy-impurity clusters in highly n-type Si. We show that the migration of V-As pairs at 450 K leads to the formation of V-As2 complexes, which in turn convert to stable V-As3 defects at 700 K. These processes manifest the formation of V-As3 as the dominant vacancy-impurity cluster in highly n-type Si. They further explain the electrical deactivation and clustering of As in epitaxial or ion-implanted Si during postgrowth heat treatment at 700 K.     

Specific features of luminescence of radiation-colored α-Al2O3 single crystals

Results of a comparative study on specific features of luminescence of thermochemical and radiation-colored crystals of aluminum oxide have been described. It is shown that crystals containing oxygen vacancies of different origins have identical main optical properties. A vacancy or vacancy-impurity origin of deep traps has been assumed. Some specific features of thermoluminescence (TL), which are common for both types of crystals, such as the dependence of the TL output on the heating rate and the occupancy of deep traps described by the model of interactive trap system, have been established.