Ion bombardment induced phase transformations and inert gas mobility in the semiconductors Ge,Si, and GaAs

Abstract

The present study contributes some new aspects to the general understanding of the ion implantation behaviour of 3 common semiconductor materials, and of diffusion processes in these materials. Single crystals of Si, Ge, and GaAs were bombarded with Kr- or Xe-ions at energies of 40 or 500 keV and doses between 10¹¹ and 2 × 10¹⁶ ions/cm². Gas release measurements and Rutherford scattering of 1 MeV He⁺-ions combined with channeling were used to study bombardment damage (amorphization) and inert gas diffusion. At low bombardment doses (10¹¹ ions/cm²) and energy (40 keV), no damage was observed and the gas release was compatible with volume diffusion resembling Group I and VIII behaviour. Hence, the pre-exponential terms, D ₀, were low (range 10-^5±1 cm² sec^?1) and the activation enthalpies, Δ H, were much lower than those of self-diffusion or of diffusion of Group III and V elements. The Δ H's for gas diffusion followed the relation Δ H = (1.05±0.1) × 10^?3 T_m eV with the melting point, T_m , in °K. The mechanism of gas mobility might be the Turnbull dissociative mechanism. Rutherford scattering and channeling data indicated that part of the gas occupied lattice sites.

At higher doses, the bombarded layers turned amorphous. Channeling experiments showed a coincidence in temperatures for a gas release process different from the above one of volume diffusion, and recrystallization of the disordered layer to the single crystalline state. Both processes occurred in the temperature range 0.60 to 0.65 T_m . The gas release indicated a (partial) single jump character with implied Δ H's following the relation Δ H = (2.1±0.1) × 10^?3 T_m eV. Contrary to previous results on oxides, this new gas release occurred at temperatures near to those or even above those of volume diffusion of the gas.

Due to the easy formation of an amorphous layer it was difficult to observe the retarded release (trapping of gas) that has been found in many materials at high gas and damage concentrations. However, in a separate series of experiments with 500 keV Kr-ions, a release retarded with respect to volume diffusion of the gas was observed in Si and Ge.     

Pressure-induced activation and pressure-tolerance of mutated thermolysin at 119

Abstract

The pressure activation of thermolysin substitution at the 119th site was studied for four mutants and the wild type (Q119Q. Q119N, Q119R, Q119E and Q119D). The highest activation recorded over 30 fold and the activation volumes (ΔV?) were about -75ml/mol for Q119Q, Q119N and Q119R, while Q119E and Q119D showed only a10 fold activation and ΔV? of around -6Oml/mol. The pressure-tolerance of these enzymes were investigated through the in situ observation of their intrinsic fluorescence. Q119E and Q119D showed smaller ΔG _app and ΔG _app of transition than the wild type.     

Chemical hardness-based prediction of the surface tension and enthalpy changes of sublimation for alkali halides

A new theoretical route employing the concept of chemical hardness has been developed to predict the surface tension γ and the changes of the standard enthalpies (CSEs) of sublimation Δ_sH⁰ of alkali halides. The values of these quantities have been calculated by means of the ratios η_M/V^1/3_m where η_M and V_m are the molecular hardness and molecular volume, respectively. The obtained results have been compared with those of previous theoretical models as well as with experimental data.     

4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate

The values of the enthalpy (53.3; 51.3; 20.0 kJ mol^?1), entropy (?106; ?122; ?144 J mol^?1K^?1), and volume of activation (?29.1; ?31.0; ?cm³ mol^?1), the reaction volume (?25.0; ?26.6; ?cm³ mol^?1) and reaction enthalpy (?155.9; ?158.2; ?150.2 kJ mol^?1) have been obtained for the first time for the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione 1 , with cyclohexene 4 , 1‐hexene 6 , and with 2,3‐dimethyl‐2‐butene 8 , respectively. The ratio of the values of the activation volume to the reaction volume (?V^≠_corr/ΔV_{r ? n}) in the ene reactions under study, 1 + 4 → 5 and 1 + 6 → 7 , appeared to be the same, namely 1.16. The large negative values of the entropy and the volume of activation of studied reactions 1 + 4 → 5 and 1 + 6 → 7 better correspond to the cyclic structure of the activated complex at the stage determining the reaction rate. The equilibrium constants of these ene reactions can be estimated as exceeding 10¹⁸ L mol^?1, and these reactions can be considered irreversible. Copyright © 2014 John Wiley & Sons, Ltd.     

Homo‐Diels–Alder reaction of a very inactive diene,bicyclo[2,2,1]hepta‐2,5‐diene,with the most active dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione. Solvent,temperature, and high pressure influence on the reaction rate

Solvent, temperature, and high pressure influence on the rate constant of homo‐Diels–Alder cycloaddition reactions of the very active hetero‐dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta‐2,5‐diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95^.10^?3 for reaction (1+2) to 12200 L mol^?1 s^?1 for reaction of 1 with 9,10‐dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k₂) and the heat of reactions (?_r‐nH) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is ?218 ± 2 kJ mol^?1, of 1 with 9,10‐dimethylanthracene ?117.8 ± 0.7 kJ mol^?1, and of 1 with 9,10‐dimethoxyanthracene ?91.6 ±0.2 kJ mol^?1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3‐butadiene. However, the heat of reaction of 9,10‐dimethylanthracene with 1 (?117.8 kJ mol^?1) is nearly the same as that found for the reaction with the structural C=C counterpart, N‐phenylmaleimide (?117.0 kJ mol^?1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels–Alder cycloaddition reaction with 1. Linear correlation (R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (?V^≠) and the volume of reaction (?V_r‐n) of the homo‐Diels–Alder reaction (1+2) is considered as “normal”: ?V^≠/?V_r‐n = ?25.1/?30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd.     

V替代Mn对La_(0.45)Ca_(0.55)MnO_3电荷有序相及自旋玻璃态的影响

用固相反应法制备了La0.45Ca0.55Mn1-xVxO3(x=0.00,0.10)多晶样品.通过X射线衍射谱、质量磁化强度-温度曲线、电子自旋共振谱,研究了V5+替代Mn3+/Mn4+对La0.45Ca0.55MnO3电荷有序相和自旋玻璃态的影响.实验结果表明,当x=0.10时,不仅母体的电荷有序相基本破坏,而且母体在40K左右出现的自旋玻璃态也被融化.电荷有序相被破坏的主要原因是用V5+替代Mn3+/Mn4+后,增加了Mn3+与Mn4+的比例,使铁磁双交换作用优于反铁磁超交换作用;自旋玻璃态的融化是由于V替代Mn后破坏了反铁磁背景下有少量铁磁成分的自旋玻璃态的形成条件.     

Swift heavy ions-induced degradation on the electrical characteristics of silicon NPN power transistors

ABSTRACT

The pre- and post-irradiation effects on the DC electrical characteristics of 100?MeV Phosphorous (P⁷⁺) and 80?MeV Nitrogen (N⁶⁺) ion-irradiated NPN transistors were studied in the dose range from 600?krad (Si) to 100?Mrad (Si). The different electrical characteristics, such as Gummel characteristics, excess base current (ΔI_B?=?I_B-Post?–?I_B-Pre), current gain (h_FE), damage constant (K) and output characteristics, were measured in situ after ion irradiation. The considerable increase in the base current (I_B) at lower V_BE and slight decrease in the collector current (I_C) at higher V_BE were observed after ion irradiation. The C–V measurements revealed that the doping concentration (N_d) was found decreased, while the built-in potential (V_bi) increased after irradiation. The ion-irradiated results are compared with ⁶⁰Co gamma-irradiated results in the same dose range. The SRIM simulation was performed to understand the range of ions and energy loss in the transistor structure. The SRIM simulation showed that 100?MeV P⁷⁺ and 80?MeV N⁶⁺ ions can easily pass through the active region of transistors by creating ionization and displacement damages in the device structure. The irradiation results showed that ions induce more degradation in the electrical characteristics when compared to ⁶⁰Co gamma radiation at the same dose range.     

Recrystallization of pure and strontium-doped KCl crystals

The kinetics of microstructure transformations are studied during annealing of deformed single crystals of KCl and KCl:0.05wt %Sr²⁺ at temperatures of (0.35–0.55)T _m (where T _m is the melting temperature) and during storage at room temperature. The effect of deformation rates ranging from 0.01 mm/min to 0.1 mm/min at a deformation temperature T _d=0.5T _m on the crystal structure and on the recrystallization kinetics is noted. It is found experimentally that the incubation period for static recrystallization in single-crystal KCl:0.05wt%Sr²⁺ is shortened and recrystallization takes place at room temperature after deformation in this temperature range. Here, during the new recrystallization grains have a twinned orientation with respect to the initial single crystal during the first stage and to the subgrains of the deformed crystal. As the annealing temperature is raised, the stage in which twins grow in KCl:0.05wt%Sr²⁺ crystals is shortened and it is displaced by recrystallization through migration of high-angle grain boundaries of the common type. Deformation conditions which ensure prolonged (at least three months) stability of the post-deformation hardening of single crystals are found experimentally for Sr²⁺-doped deformed single crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 259–264 (February 1999)     

On the electronic structure of N,N′-ethylenebis(acetylacetonatiminato)Co(II), Co(II)acacen

Single crystal E.P.R. and cobalt ENDOR measurements on N,N′-ethylenebis(acetylacetonatiminato)Co(II), Coacacen, diluted in Niacacen·1/2 H₂O are reported. Forbidden Δm _Co = 1,2 transitions in the E.P.R. spectra have been observed. The g-tensor (E.P.R.) and the cobalt hyperfine and quadrupole tensors (ENDOR) have been determined. The g- and cobalt hyperfine tensors are discussed. They support the |² A ₂,yz? groundstate proposed for four coordinated low-spin Schiff base complexes of cobalt(II). The measured quadrupole coupling is also compatible with a |² A ₂,yz? groundstate, if anisotropic contraction of the cobalt 3d orbitals is taken into consideration.     

Surface modifications of crystalline SiO2 and Al2O3 induced by energetic heavy ions

Abstract

Glasses with composition × CoO.(0.25-x) CaO.0.75 B₂O₃ have been prepared over the range 0 ≤ x ≤ 0.25 containing 2 mol% of V₂O₅. Electron paramagnetic Resonance spectra of VO²⁺ of these glasses has been measured at X-band (ν ≈ 9.15 GHz) at room temperature and at liquid nitrogen temperature. Spin Hamiltonian parameters of the VO²⁺ ions have been calculated. It is found that for x ≤ 0.12 the octahedral symmetry of the V⁴⁺ site is improved. A part of these glasses were annealed at 473 K for 24 hours and EPR spectra were recorded and analysed.     

Nucleation and stability of defect clusters: New energetic model in the case of substituted wustites

Abstract

For wüstite Fe_1?z O (z < 0.08) an energetic model accounts for the stability of cubic defect clusters (m/n) which are partly ordered in the crystal. The Gibbs energy G_T (N) associated with clusters, including their distorted envelope, is expressed as a sum of a volume term in N ³ and of surface terms in N ⁴; N is the number of bonds characteristic of the cluster size. In the case of a (10/4) type cluster, this energy is negative and minimum for N_m ranging between 4 and 5, when the volume and surface energies range between specific values. Using simple assumptions, a volume energy ?0.80 eV per vacancy is found in accordance with the value of stabilization energy calculated by theorists for the (10/4) cluster. The substitution of Fe²⁺ by Ca²⁺ should lead to a decrease of cluster size; this has been recently suggested by neutron diffraction studies.     

Correlation study between DKI and conventional DWI in brain and head and neck tumors

PurposeTo investigate the relationship between the Diffusion Kurtosis Imaging (DKI) parameters and conventional metrics provided by Diffusion-weighted imaging (DWI) in patients affected by Brain or Head and Neck (HN) cancer.MethodsTen patients affected by brain tumor and nine patients with HN tumor underwent a pre-treatment MR examination at 3 T. The largest tumor section was manually contoured by two expert neuroradiologists. The apparent diffusion coefficient (D_app) and apparent diffusional kurtosis (K_app) parameters were determined at the voxel level by using the DKI model, and compared to the apparent diffusion coefficient (ADC) and the tissue diffusion coefficient (D_mono) obtained from mono-exponential fitting methods. The Akaike Information Criteria (AIC) was calculated to assess the quality of the fitting methods. Cross-correlations between all the variables were assessed using the Spearman rank test.ResultsIncreased K_app values were found in each lesion. All parameters were strongly related, in particular an inverse relationship emerged between median values of K_app and D_app/D_mono/ADC in both patient groups, while D_app showed positive correlations with D_mono and ADC. From the analysis at the voxel level, significant inverse associations were found between K_app and D_mono within the lesions, while a weak or moderate association emerged between K_app and ADC or D_app.ConclusionsA significant association between the apparent diffusional kurtosis K_app and the tissue diffusion coefficient D_mono emerged for both brain and HN tumors at 3 T, suggesting that both variables may consistently reflect deeper insight into the microstructural characteristics of tumors.     

A quasi-classical trajectory study of the Cl + H<Subscript>2</Subscript> (D<Subscript>2</Subscript>) reaction on a new BW3 potential energy surface

Molecular reaction dynamics of Cl + H₂ (D₂) has been studied on the latest analytical potential energy surface called BW3 using the Monte Carlo quasi-classical trajectory method. Excitation functions, differential cross sections and angular distributions of HCl and DCl products have been calculated. The excitation functions of the Cl (²P_3/2) + n-H₂ and Cl(²P_3/2) + n-D₂ reactions are also studied. The results are compared with those of quasi-classical trajectory [M. Alagia et al.: Phys. Chem. Chem. Phys. 2 (2000); F. J. Aoiz et al.: J. Phys. Chem. 100 (1996)], quantum mechanical (QM) calculations [F. J. Aoiz et al.:J. Chem. Phys. 115 (2001)] and experimental data [S. H. Lee et al.: J. Chem. Phys. 110 (1999); F. Dong et al.: J. Chem. Phys. 115 (2001)]. Discussions are given to some new results.     

Local structure of the trigonal defect center for Cr3+ ions in KMgF3 crystals

Abstract

The zero-field splitting D, the anisotropic g-factors g _∥, Δg(=g _∥ ? g _⊥) and the first excited state splitting Δ(² E) for the trigonal Cr³⁺–V_K center in KMgF₃: Cr³⁺ crystals have been studied from Macfarlane's high-order perturbation formulas. From the studies, the local structure of the trigonal center is obtained. The local lattice distortions (i.e., the displacement directions of the ions in the center) are consistent with the expectation based on the electrostatic interaction.     

Viscosity and excess molar volume of binary mixtures of methanol with n-butylamine and di-n-butylamine at 303.15, 313.15 and 323.15 K. Characterization in terms of ERAS model

The excess molar volume V_m^E, viscosity deviation Δη, and excess Gibbs energy of activation ΔG^?E of viscous flow have been investigated from the density ρ and viscosity η measurements of binary mixtures of methanol with n-butylamine and di-n-butylamine over the entire range of mole fractions at 303.15, 313.15, and 323.15 K. The systems studied exhibit very strong cross association through strong O–H…N bonding between –OH and –NH– groups. As a consequence of this strong intermolecular association, both the systems have very large negative V_m^E and positive Δη and ΔG^?E over entire range of composition and at all the temperatures of investigation. V_m^E of the studied mixtures is consistently described by the ERAS model. The values of cross association constants K_AB illustrate that cross-associates are more pronounced in primary amine mixtures than that in secondary amine.     

Degradation of the transconductance of gate-modulated generation current in nMOSFET

The degradation of transconductance (G) of gate-modulated generation current I_GD in LDD nMOSFET is investigated. The G curve shifts rightward under the single electron-injection-stress (EIS). The trapped electrons located in the gate oxide over the LDD region (Q_L) makes the effective drain voltage minish. Accordingly, the G peak in depletion (G_MD) and that in weak inversion (G_MW) decrease. It is found that Δ G_MD and Δ G_MW each have a linear relationship with the n-th power of stress time (tⁿ) in dual-log coordinate: Δ G_MD ∝ tⁿ, Δ G_MD ∝ tⁿ (n=0.25). During the alternate stress, the injected holes neutralize Q_L induced by the previous EIS. This neutralization makes the effective V_D restore to the initial value and then the I_GD peak recovers completely. Yet the threshold voltage recovery is incomplete due to the trapped electron located over the channel (Q_C). As a result, G_MW only recovers to the circa 50% of the initial value after the hole-injection-stress (HIS). Instead, G_MD is almost recovered. The relevant mechanisms are given in detail.     

Transport and dielectric properties of V2O5-MnO-TeO2 glasses

The frequency (1-10 kHz) and temperature (80-350 K) dependences of the ac conductivity and dielectric constant of the V₂O₅-MnO-TeO₂ system, containing two transition-metal ions, have been measured. The dc conductivity _dc measured in the high-temperature range (200-450 K) decreases with addition of the oxide MnO. This is considered to be due to the formation of bonds such as V--O--Mn and Mn--O--Mn in the glass. The conductivity arises mainly from polaron hopping between V^4+M and V⁵⁺ ions. It is found that a mechanism of adiabatic small-polaron hopping is the most appropriate conduction model for these glasses. This is in sharp contrast with the behaviour of the Mn-free V₂O₅-TeO₂ glass, in which non-adiabatic hopping takes place. High-temperature conductivity data satisfy Mott's small-polaron hopping model and also a model proposed by Schnakenberg in 1968. A power-law behaviour ( _ac = Aω^s , with s < 1) is well exhibited by the ac conductivity σ_ac data of these glasses. Analysis of dielectric data indicates a Debye-type relaxation behaviour with a distribution of relaxation times. The MnO-concentration-dependent σ_ac data follow an overlapping large-polaron tunnelling model over the entire range of temperatures studied. The estimated model parameters are reasonable and consistent with changes in composition.     

Excess molar volumes and isentropic compressibilities of binary liquid mixtures containing n-alkanes at 298.15 K

Excess molar volumes (V ^E) and deviation in isentropic compressibilities (Δβ _s) have been investigated from the density ρ and speed of sound u measurements of six binary liquid mixtures containing n-alkanes over the entire range of composition at 298.15 K. Excess molar volume exhibits inversion in sign in one binary mixture, i.e., n-heptane + n-hexane. Remaining five binary mixtures, n-heptane + toluene, cyclohexane + n-heptane, cyclohexane + n-hexane, toluene + n-hexane and n-decane + n-hexane show negative excess molar volumes over the whole composition range. However, the large negative values of excess molar volume becomes domainant in toluene + n-hexane mixture. Deviation in isentropic compressibility is negative over the whole range of composition in the case of all the six binary mixtures. Existence of specific intermolecular interactions in the mixtures has been analyzed in terms of excess molar volume and deviation in isentropic compressibility.     

Electrical transport in ferroelectric Pb[(Fe1/3Sb2/3) x Ti y Zr z ]O3 ceramics

In this article, the studies of the polarization currents and current–voltage characteristics (J–V) are presented. The measurements of the J–V in low and high temperatures as well as at low and high voltages have permitted to recognize certain details of local energy levels in forbidden gap. It has been possible to calculate energy trap levels and their concentration. Calculated trap energy and concentration, under the condition of single trap energy levels, are equal: E _t = 0.55 eV, N _t = 2.97 · 10²³ m^?3 for the sample y = 0.44 and E _t = 0.59 eV, N _t = 1.5 · 10²³ m^?3 for the sample y = 0.47. Knowing the J–V characteristic and the Seebeck coefficient the carriers concentration and their mobility can also be calculated. The carriers concentration and their mobility are equal: n = 3.8 · 10¹⁸ m^?3, µ = 1.4 · 10^?12 m² V^?1 · s^?1 for sample y = 0.44 and n = 6.9 · 10¹⁶ m^?3, µ = 1.3·10^?11 m² V^?1 · s^?1 for the sample y = 0.47.     

Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.