Iodine as a donor in CdS

Iodine doped single crystals of CdS were grown from the vapor phase. High temperature Hall effect measurements for the crystals equilibrated with Cd and S₂ vapors at temperatures between 700 and 1000°C gave the free electron concentration as a function of p_Cd or p_S2 and temperature. The results can be explained on the basis of a model in which the CdS is saturated with iodine at low p_Cd (=high p_S2) but unsaturated at high p_Cd.The solubility of iodine in CdS is given by c_t=1·73×10²²p_S2^?1/8 exp (?1·045 eV/kT) cm^?3 atm^?1/8=4·62×10¹⁹p_Cd^1/4 exp (?0·195 eV/kT) cm^?3 atm^1/4The formation of pairs (I_SV_Cd)′ from I_S^· and V_Cd″ is governed by the equilibrium constant K_{P(I, V)}=4 exp (≤1·1 eV/kT)If Cd diffusion occurs primarily by free vacancies, the Cd^* tracer self diffusion leads to a vacancy mobility of (1·2±0·5)×10^?5 cm² sec^?1 at 900°C, in agreement with results reported by Woodbury [12], but (7±3) times larger than reported by Kumar and Kroger [10].     

EPR study of Fe3+ and Mn2+ in CeO2 and ThO2

Attempts were made to grow CeO₂ and ThO₂ single crystals doped with transition metal ions. Only Fe³⁺ and Mn²⁺ could be detected by the EPR technique. The EPR spectrum of Fe³⁺ in CeO₂ exhibits the well-known fine structure in cubic fields. The parameters areg=2.0044(1) anda=15.6(1)·10^?4 cm^?1. The hyperfine constantA for⁵⁷Fe in hexahedral coordination was found to be 8.9(1)·10^?4 cm^?1. The EPR spectrum of Mn²⁺ in CeO₂ reveals two cubic Mn²⁺ centers. The parameters for center 1 areg=1.9999(1) andA=86.9(1)·10^?4 cm^?1 and for center 2g=1.9984(1) andA=87.0(1)·10^?4 cm^?1. Heating the Mn doped CeO₂ samples in hydrogen, the Mn²⁺ centers transform from cubic into trigonal centers with approximate values ofg=1.9988(2),A=84.5(6)·10^?4 cm^?1 andD=203(1)·10^?4 cm^?1. The two observed Mn²⁺ centers in ThO₂ exhibita priori axial symmetry with approximate values ofg=2.0006(2),A=88.9(4)·10^?4 cm^?1 andD=33(3)·10^?4 cm^?1.     

Doping mechanism of a conducting polymer: Iodine-doped polyacetylene

We have achieved a technique for determining the diffusion profiles of impurities in the polymers by using a radio-tracer and a microslicing method. We describe the diffusion profiles of iodine in polyacetylene in the temperature range ?60 +20°C. The results show that: (1) iodine penetrates through the interfibril spaces; (2) there is a simultaneous chemical reaction of the first order on the fibrils between polyacetylene and iodine. When the dopant is in solution in pentane, the liquid state interfibril diffusion obeys the Arrhenius law: D = 1.73 × 10^?3 exp[$\text{?0.122(eV)}\text{kT}$] cm² · sec^?1. The kinetic constant of the reaction obeys the similar equation: k = 0.754 exp[$\text{?0.0867(eV)}\text{kT}$] sec^?1.     

Study of cation tracer diffusion in NaF

Cation tracer diffusion coefficients were measured in pure NaF crystals in the intrinsic ionic conductivity range (876–970 °C). The results can be rationalized satisfactorily in terms of contributions to the observed Na tracer diffusivities arising from both free vacancies and neutral vacancy pairs, the latter contribution amounting to about 53 per cent of the total Na diffusion at the highest measuring temperature. The best-fit defect parameters derived in an earlier conductivity study [21] from this laboratory on similar NaF crystals give for the free vacancy contribution D_v^*(Na) = 4·25 exp (?2·21 eV/kT) cm²s^?1. A combination of these D_v^*(Na) values with the present diffusion data yields for the vacancy-pair contribution D_p^*(Na) = 1·15 × 10⁸exp (?4·04 eV/kT) cm²s^?1. Comparison of the present findings with published values of the anion tracer diffusion coefficient in NaF showed that D_p^* (F) is 2·3 to 4·4 times larger than D_p^*(Na) over the temperature range of our observations, the difference between the two contributions increasing with decreasing temperature. When approximate account is taken of the temperature-dependence of the two pair correlation factors, this last result indicates that the anion jumps into the vacancy pair occur with a higher frequency, and increasingly so at lower temperatures, than do those involving the cations.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10^?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D_∥ for this direction has roughly the same value for all investigated surfaces: D_∥=7.8×10^?2 cm²s^?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.     

Effect of the ionic radius on jump frequencies of alkaline earth cations in NaCl crystals

By comparing diffusion coefficientsD of bivalent cations Ba²⁺, Ca²⁺, Sr²⁺ in NaCl crystals it was shown that in the temperature range above 550 °CD (Ba²⁺)>D (Sr²⁺)>D (Ca²⁺) is valid. Temperature dependences of jump frequenciesw ₂ of these cations are described byw ₂ (Ba²⁺)=(2·15±0·55) × 10¹² × exp {?(0·817±0.007)/kT};w ₂ (Sr²⁺)=(2·9±1·1) × 10¹² × exp {?(0·84±0.02)/kT} andw ₂ (Ca²⁺)=(5·5±6·5) × 10¹⁰ × exp {?(0·51±0·07)/kT}. It was demonstrated that in NaCl crystals the activation enthalpy and the preexponential factor of the jump frequencyw ₂ increase with increasing ionic radius and mass of the bivalent alkaline earth cation.     

Nuclear magnetic relaxation by self-diffusion in solid lithium:T 1-frequency dependence

We report on measurements of the⁷Li nuclear spin relaxation timeT ₁ in solid lithium as a function of temperature (?170°C≦T≦+180°C) and Larmor frequency (450kHz≦v _Li≦31.5 MHz). Using a relaxation model developed by Wolf and Cavelius and combining it with Seeger's diffusion formalism, the diffusion parameters for mono-and divacancy migration were evaluated by a least squares fit to the newly obtainedT ₁ data as well as to previousT _1? measurements. The result for the self-diffusion coefficientD ^SD is given byD ^SD=D ₁₀·exp(?Q ₁/RT)·[1+D ₂₁·exp(?Q ₂₁/RT)], withD ₁₀=0.038 cm²s^?1,Q ₁=12.0 kcal mol^?1,D ₂₁=250,Q ₂₁=4 kcal mol^?1 andR=1.98₅·10^?3 kcal mol^?1 degree^?1. Due to the flexibility of Seeger's formula, which contrasts with the standard Arrhenius interpretation of diffusion, discrepancies between earlier high- and low-frequency NMR investigations were eliminated. Furthermore, an excellent agreement with available results from tracer experiments was achieved by taking into account the theoretical predictions of the isotope effect and the vacancy correlation factor.     

Zeitliches Abklingen und Anisotropie von p-Terphenyl- undp-Terphenyl-Anthrazen-Mischkristallen bei Beschuß mit α-Teilchen

The time dependence of scintillation intensity from single crystals ofp-terphenyl and mixed crystals ofp-terphenyl and anthracene after bombarding with α-particles was investigated at the two temperaturesT=296 °K andT=92 °K. For the crystals ofp-terphenyl the time dependence of the scintillation anisotropy was also measured. Using the formulas given byKing andVoltz the decay curves ofp-terphenyl were decomposed into two components. Good agreement between experiment and theory was found. The ratio of the prompt intensity to the delayed intensity was determined to be 1∶2 atT=296 °K and 1∶3 atT=92 °K. The diffusion constants for triplet excitons were calculated to beD _T(296 °K)≈10^?5 cm² sec^?1 andD _T(92 °K)≈ 2×10^?6 cm² sec^?1, and the triplet-triplet interaction rate constantsχ _tt(296 °K)≈ 2.5×10^?11 cm³ sec^?1 andχ _tt(92 °K)≈0.5×10^?11 cm³ sec^?1.     

Self-diffusion of potassium in potassium azide

The tracer sectioning technique was used to study the diffusion of potassium ions in melt grown single crystals of potassium azide. The temperature dependence of the diffusion coefficients in the range 85–254°C can be represented by D=(0·19±0·03) exp [(?0·80±0·06) eV/kT] cm²/sec. It appears that the cations are the predominant mobile species and that they diffuse by a vacancy mechanism with an enthalpy of migration of 0·80±0·06 eV.     

Simultaneous diffusion of calcium and strontium in KCl single crystals

Concentration dependent diffusion coefficients for ⁴⁵Ca²⁺ and ⁸⁵Sr²⁺ in purified KCl were measured using a sectioning method. KCl was purified by an ion exchange — Cl₂?HCl process and the crystals grown under $\text{1}\text{6}$ atmosphere of HCl. The tracers were purified on small disposable ion exchange columns to remove precessor and daughter impurities prior to use in a diffusion anneal. Isothermal diffusion anneals were made in the temperature range from 451% to 669%C. At temperatures above 580%C (the lowest melting eutectic in this system) diffusion was from a vapor source: below 580%C surface depositied sources were used. The saturation diffusion coefficients. enthalpies and entropies of impurity-vacancy associations were calculated using the common ion model for simultaneous diffusion of divalent ions in alkali halides. In KCl the saturation diffusion coefficients D_S(ca) and D_s(Sr) are given by

$\text{D}{}_{\mathrm{s}}\text{(Ca) = 9.93 × 10}{}^{\mathrm{?5}}\text{exp(?0.592}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(1) and

$\text{D}{}_{\mathrm{s}}\text{(Sr) = 1.20 × 10}{}^{\mathrm{?3}}\text{exp(?0.871}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(2) for calcium and strontium, respectively. The Gibbs free energy of association of the impurity vacancy complex in KCl for calcium can be represented by

$\text{Δg(Ca) = ?-0.507 eV + (2.25 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

(3) and that for strontium by

$\text{Δg(Sr) = ?0.575 eV + (2.90 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

. (4)     

Thermoelectric power of (Me4N)2Ag13I15 and (Et4N)2Ag13I15

Thermoelectric power using reversible silver electrodes and electrical conductivity on the compressed pellets of (Me₄N)₂Ag₁₃I₁₅, and (Et₄N)₂Ag₁₃I₁₅ have been measured between room temperature and below 160°C. The results of θ can be expressed by the equations:?θ = 0.115 (10³/T)+0.2905VK^?1 and ?θ = 0.150 (10³/T) + 0.305mV K^?1; and those of conductivity by the equations; σ = 28.7 exp (?0.17eV/kT) ohm^?1cm^?1 and $\text{σ = 216.6 exp (?0.24e}\text{V}\text{kT}\text{)}$ ohm^?1cm^?1; respectively for Me- and Et-electrolytes. The results are discussed and compared with those of previous authors.     

Evaluation of zinc self-diffusion at the interface between homoepitaxial ZnO thin films and (0001) ZnO substrates

Isotopic ZnO thin films were deposited on the c-plane of ZnO single crystals by pulsed laser deposition. The isotopic abundance of Zn in the films was determined with a secondary ion mass spectrometry before and after the films was diffusion annealed. The diffusion profiles across the film/substrate interface behaved smooth features. The zinc diffusion coefficient (D_Zn) was obtained by analyzing the slope of the profile in the annealed sample. The temperature dependence of D_Zn was determined to be D_Zn(cm²/s)=8.0×10⁴exp(?417[kJ/mol])/RT, where R and T are gas constant and temperature. The zinc ion diffusion coefficients were of the same order as that in a ZnO single crystal. A comparison of the experimental and theoretical values indicated that the zinc ions diffused in the thin film and the single crystal through a vacancy mechanism.     

Proton spin-lattice relaxation in iron fluosilicate

Proton T₁ of FeSiF₆·6H₂O is proportional to exp (Δ/kT)at liquid helium temperatures, with Δ ≈ D - 3E. We find the crystal field splitting of the Fe²⁺ ion in this salt to be D = (12.2 ± 1.0) cm^-1 using E = 0.54 cm^-1.     

Anregung metastabiler Zustände von Barium und Thallium durch Atomstöße im Stoßwellenrohr

It is shown that relaxation times for the excitation of metastable levels of Ba and Tl by collisons of the ground state atoms with carrier gases Ne and Ar can be measured with good accuracy behind reflected shock waves (2700≦T≦3300 °K) by means of two-channel atomic line absorption spectroscopy. Quenching cross-sections, which thus can be derived, cover in principle the range 10^?14 cm²<Q<10^?21 cm². In collisions with Ar one finds for the deactivation of Ba(¹ D ₂)Q=1.2 · 10^?19cm², of Ba(³ D ₁)Q=0.95 · 10^?19 cm² and of Tl(² P _3/2)Q<5 · 10^?21 cm² without noticeable temperature dependence. From this follows a) (on the basis of the Landau-Zener formula) that the pseudo-crossing of the potential energy curves of Ba-Ar takes place within 0.25 eV of the Ba(D) levels and b) that spin-orbit coupling is not rate controlling in the Ba(³ D ₁ →¹ S ₀) transition. The ratio of cross-sections for quenching of Ba(¹ D ₂) by Ar and Ne is about 3, suggesting that the polarizabilities of the noble gas collision partners play a major rôle in the transition probabilities. The mean self-quenching cross-sectionQ=5 · 10^?16 cm² of Tl(² P _3/2) at 3000 °K is about the same as the one reported for 1000 °K and it exceeds the self-quenching cross-section of metastable Ba by at least one order of magnitude.     

Diffusion of 55Fe in Fe2O3 single crystals

The diffusion of ⁵⁵Fe has been measured parallel to the c axis of Fe₂O₃ single crystals at temperatures in the range 708–1303°C and at an oxygen activity of unity. The tracer penetration profiles were determined using sectioning techniques. For temperatures above 900°C the tracer diffusion coefficient is given byD¹(Fe) = 1.6 × 10⁹ exp[?6.0 (eV)/kT] cm² s^?1 and below 900°C by 2.8 × 10^?9 exp[?1.8 (eV)kT]. The high-temperature behaviour is probably characteristic of pure Fe₂O₃, whereas diffusion at lower temperatures may be influenced by impurities. The most likely defects responsible for diffusion of Fe are iron interstitials and, for oxygen, oxygen vacancies, and the observed activation energies are discussed in terms of the properties of these defects. The diffusion data and defect models have been used to predict the rate of growth of Fe₂O₃ and indicate that outward Fe diffusion is the dominant transport process. Previously published data for Fe₂O₃ growth in a variety of experimental situations have been corrected to a single rate constant using a model for multilayer growth. The corrected data are all in good agreement but are approximately two orders of magnitude greater than predicted from diffusion data, which suggests that grain boundary diffusion controls the growth of Fe₂O₃ in practice.     

Bonding and composition diagrams for sputtered a-Si : H

The combined influence of H partial pressure (p_H) and deposition rate (R_D) on Si-H bonding and total H content in diode-sputtered a-Si : H is presented in two simple graphs for the case of substrate temperature (T_s) equal to 225°C. Similar to a phase diagram, the graphs predict the H content and Si-H bonding that will result if a deposition is carried out with any prescribed pair of values (p_H, R_D), where 0.04 < p_H < 10 Paand 0.01 < R_D < 1 nm/sec. Well defined regions of Si-H bonding represented by dominant infrared stretching absorptions at 2000, 2090 and 2150 cm^?1 are obvious in the bonding diagram. The absorption at 2090 cm^?1 is the most commonly observed and is obtainable over a wide range of intermediate values of p_H and R_D. The absorption at 2000 cm^?1 is dominant only for the lowest p_H and the highest R_D. The absorption at 2150 cm^?1 is dominant in films deposited at high p_H and low R_D. The composition diagram shows that highest total H content is obtained for low R_D and high p_H, and lowest total H content results for high R_D and low p_H     

On the thermal conductivity of glasses

We estimate the numerical contribution of the interaction between like defects in glasses for the linewidth (? T^?1₂) obtained in acoustical experiments. This interaction gives origin to a diffusion process with a very large diffusion constant (D = 10^?5 cm² sec^?1). The thermal conductivity due to this diffusion process is calculated. Its temperature dependence is also obtained.     

Etude de l'autodiffusion dans la phase cubique centree de l'europium et du gadolinium

The self-diffusion coefficient follows a relation of the form : D = (1,0_?0.4^+0.7)exp (?shape=case>34400RT±700)

$\text{cm}{}^2\text{sec}$

for b.c.c. europium D = (1,0_?0.3^+0.5) × 10^?2 exp(?

$\text{32700 ±4000}\text{RT}\text{)}$

$\text{cm}{}^2\text{sec}$

for β-b.c.c. gadolinium.Whereas europium has normal self-diffusion parameters, β-b.c.c. gadolinium must be set in the class of the anomalous b.c.c. rare-earth metals.From these results we conclude that there exists no evident connexion between the instability of the 4f shell and the activation energies anomalously low in the b.c.c. phases of the rare-earth metals.     

Collisional transition probability in gaseous and liquid carbontetrachloride

In gaseous CCl₄ at 20 to 30 °C, the probability that a binary collision effects an energy transfer between the translational and the vibrational degrees of freedom is 3.8 · 10^?3, in liquid CC1₄ at the same temperature it is close to 2.6 · 10^?3. The ratio of these experimental values corresponds exactly to that predicted from the theoretical relationship:P _liquid/P_gas = (1 +S _η/T) · exp(??/kT).     

Über Kristallstruktur und elektrische Eigenschaften der Wismutselenide Bi2Se2 und Bi2Se3

The properties of bismuth triselenide (Bi₂Se₃) are already known to a certain extent through the work of several authors, while it was still an open question whether there exists an individual solid phase of BiSe. Further information on this subject could be obtained by the successful growth and investigation of single crystals of both Bi₂Se₃ and Bi₂Se₂. X-ray analysis by means of goniometry, Weißenberg, Laue, and Debye-Scherrer diagrams confirmed the known crystal structure of Bi₂Se₃ (ditrigonal scalenohedral;D _3d ⁵ ?R—m; with the hexagonal axes:a=4·15 Å andc=28·55 Å, and 3 molecules per unit cell). As to Bi₂Se₂ it can be shown that it belongs to the same class but to a different space group (D _3d ¹ ?P— 1m orD _3d ³ ?P—m 1; hexagonal axes:a=4·15 Å,c=22·84 Å, unit cell: 3 molecules, if the formula Bi₂Se₂ is adopted). Common to both is a subcell with the dimensions:a′=a=4·15 Å andc′=5·71 Å. The temperature dependence of electrical conductivity and Hall coefficient was measured on several specimens having different crystal orientations. The most striking difference is the high anisotropy of Bi₂Se₃ (σ _a σ _c =10) as compared with Bi₂Se₂ (σ _a /σ _c <2). All specimens turned out to ben-type. The room temperature carrier concentration observed was:n (Bi₂Se3)=8·10¹⁸ cm^?3 andn (Bi₂Se₂)=4·10²⁰ cm^?3, the carrier mobility:μ(Bi₂Se3)=2·10³ cm²/V·s andμ(Bi₂Se₃)=20 cm²/V·s.