Chemisorption of indium on (111) silicon substrates: II. Adsorption by flash desorption technique — Adsorption energy

The adsorption of indium on clean (111) silicon surfaces is studied by flash desorption. Two adsorption phases are found: a $\text{59.5}\text{kcal}\text{mole}$ constant-energy phase which saturates at $\text{7 × 10}{}^{13}\text{atoms}\text{cm}{}^2$ and a second phase which increases with the adatom population n. The temperature of the desorption peak of this phase decreases when n increases. The adsorption energy of In on (111) Si is calculated by the Gyftopoulos theory, and the calculated and experimental results are compared. A very small charge transfer between the adatoms and the surface, equal to or smaller than 0.02 electron per adatom, is found.     

Reactive scattering of small molecules from platinum crystal surfaces: D2CO,CH3OH,HCOOH, and the nonanomalous kinetics of hydrogen atom recombination

The decomposition of D₂CO, CH₃OD and HCOOH on Pt(110) and of D₂CO on Pt(S)-[9(111) × (100)] was studied by molecular beam relaxation spectroscopy. D₂CO and CH₃OD evolved CO and H₂ via a desorption limited sequence of elementary steps. The rate constant for CO desorption from Pt(110) was 6 × 10¹⁴exp(? 35.5 $\text{kcal}\text{gmol}$ · RT) s^?1, and from Pt(S)-[9(111) × (100)] it was 1 × 10¹⁵ exp(?36.2 $\text{kcal}\text{gmol}\text{·RT}$) s^?1. On Pt(110) the rate constant for hydrogen formation was 10^{0 ± 1}exp(?24 $\text{kcal}\text{gmol}\text{·RT}$) $\text{m}\text{?}{}^2\text{atom}$ · s. On Pt(S)-[9(111) × (100)] two pathways for H₂ formation existed with rate constants of 8.7 × 10^?2exp( ?24.9 $\text{kcal}\text{gmol}\text{· RT}$) $\text{cm}{}^2\text{atom}$· s and 3.2 × 10^?3 exp(?19.5 $\text{kcal}\text{gmol}\text{·RT}$) $\text{cm}{}^2\text{atom}\text{·}$ s. These pre-exponential factors are in order of magnitude agreement with values typical of hydrogen recombination on other metals. When a small amount of sulfur ( ~ 0.1 ML) was adsorbed on the stepped Pt surface, only one pathway for H₂ formation existed due to blockage of stepped sites. A similar result was obtained when a beam of CO was impinged on the surface. Formic acid decomposed via a branched process to form primarily CO₂ and H₂.     

A study of valency changes of vanadium ions in Al2O3 by γ irradiation

The effect of γ irradiation at 300 K on the concentrations of vanadium ions V³⁺, V⁴⁺ and V²⁺ in Al₂O₃ has been studied quantitatively, using three techniques: optical absorption (V³⁺), low temperature thermal conductivity measurements (V⁴⁺) and EPR (V²⁺). Several single crystals of Al₂O₃ doped with vanadium in a large range of concentration $\text{(2.8 × 10}{}^{18}\text{? 1.3 × 10}{}^{20}\text{at.}\text{cm}{}^3\text{)}$ have been measured. The evolution of the respective concentrations by γ irradiation as a function of the total vanadium content C is quite different in the two regions $\text{C< 1.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ and C larger than this value. A consistent analysis of the results has nevertheless been achieved, leading to the determination of the absolute concentrations of the three ions in the as-received and γ irradiated states for all samples with $\text{C<4.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ (room temperature annealing is observed above this value). The concentrations of V⁴⁺ and V²⁺ ions are always small, but V⁴⁺ ions are more stable: they are present in the as-received state at a level of 1% of the total concentration and a maximum value of $\text{/}\text{?}\text{2.3 × 10}{}^{18}\text{at.}\text{cm}{}^3$ is observed in the γ irradiated state; on the other hand there are less than 4.7 × 10¹⁵V²⁺ ions per cm³ in the as-received state and the maximum value is only $\text{4.2 × 10}{}^{17}\text{at.}\text{cm}{}^3$. Charge transfer between V ions only is not sufficient to explain the experimental results and other defects must be involved in the γ irradiation effect.     

Dielectronic satellite spectra from dense laser-produced plasmas

The Lyman-α and adjacent dielectronic satellite lines have been observed in the spectra from laser-irradiated solid targets. In a carbon plasma from a planar target, the relative intensity of the $\text{2p}{}^2{}^3\text{P?1s2p}{}^3\text{P}$ satellite line of C(V) increases as a function of electron density in the range 8 × 10¹⁹ to 2 × 10²⁰ cm^?3. As analysis of a series of imploded microballoon experiments indicates that the $\text{2p}{}^2{}^3\text{P?1s2p}{}^3\text{P}$ and $\text{2s2p}{}^3\text{P?1s2s}{}^3\text{S}$ satellite radiation of Si(XIII) increases for electron densities 1 × 10²²?2 × 10²³ cm^?3. The satellite intensity distributions have been numerically simulated using a rate equation model. It is shown that the carbon and silicon satellite data may be interpreted in a consistent manner, and the extension to higher atomic numbers Z and higher electron densities is considered.     

Electron paramagnetic resonance of 61Ni+ in CuGaS2

EPR of ⁶¹Ni⁺ doped CuGaS₂ at 4.2 K leads to the following experimental data: $\text{g = 1.918 ± 0.006 A  < 12 × 10}{}^{-4}\text{cm}{}^{-1}\text{, g}{}_{\mathrm{\perp }}\text{= 2.328±0.006 A}{}_{\mathrm{\perp }}\text{= (65±2) × 10}{}^{-4}\text{cm}{}^{-1}$. High axial field splitting of ²T₂ state stabilizes the center against Jahn-Teller interaction. Covalency reduction factor k is 0.76.     

X-ray compressibility measurements of the graphite intercalates KC8 and KC24

The isothermal compressibilities of pristine graphite and stages 1 and 2 potassium-graphite have been measured at room temperature. Diamond anvil X-ray diffraction techniques were employed to determine the c-axis lattice constant as a function of hydrostatic pressure up to 12 kbar. The compressibilities $\text{k}{}_{\mathrm{c}}\text{?}\text{1}\text{C}{}_{33}$ were found to be (2.73±0.09)×10^-12, (2.13±0.09)×10^-12, (5.3±0.8)×10^-12 and $\text{(1.6±0.2)×10}{}^{-12}\text{cm}{}^2\text{dyn}$ for graphite, KC₈, stage 2 KC₂₄ and stage 3 KC₂₄, respectively. The compressibility of KC₈ was comparable to that of RbC₈ deduced from neutron scattering experiments.     

Surface cyclotron resonance in Si under uniaxial stress

The cyclotron resonance of inversion-layer electrons on (100)p-type Si is found to depend sensitively on an externally applied compressive stress. At low temperatures (T ? 10 K) we observe a considerable increase of the cyclotron mass m¹_c with stress S along the [001] direction. The effect is most strongly observed at low electron densities n_s. For $\text{S～1.5 × 10}{}^9\text{dyne}\text{cm}{}^2$ and n_s～2 × 10¹¹cm^-2 we obtain $\text{m}{}^1{}_{\mathrm{c}}\text{～0.4 m}{}_0$ instead of the expected 0.2m₀. Along with this change of $\text{m}{}^1{}_{\mathrm{c}}$ a strong narrowing of the resonance is noted. Raising the temperature gives an additional n_s- dependent increase of $\text{m}{}^1{}_{\mathrm{c}}$.     

Polarization spectroscopy of the E0g+-B0u+ band system of Br2

The E-B (0_g⁺-0_u⁺) band system of Br₂ has been investigated at Doppler-limited resolution using polarization labeling spectroscopy. Merged E state data for the three naturally occurring isotopes in the range v_E = 0–16, expressed in terms of the constants for ⁷⁹Br₂, are (in cm^?1) Y_0,0 = 49 777.962(54), Y_1,0 = 150.834(22), Y_2,0 = ?0.4182(28), Y_3,0 = 6.6(11) × 10^?4, Y_0,1 = 4.1876(28) × 10^?2, Y_1,1 = ?1.607(16) × 10^?4, and Y_0,2 = 1.39(39) × 10^?8. The bond distance is $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.194}\text{A}\text{?}$, and the diabatic dissociation energy to $\text{Br}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_2\text{) +}\text{Br}{}^{\mathrm{?}}\text{(}{}^1\text{S}{}_0\text{)}\text{is 34 700 cm}{}^{\mathrm{?1}}$.     

Elastic constants of LaB6 at room temperature

Measurements have been made of the transit times of pulses of longitudinal and transverse ultrasonic waves propagating in single crystal LaB₆ at room temperature. A unique set of values for the three independent elastic constants has been calculated from the resultant velocities and is; C₁₁ = (45.33 ± 0.11) × 10¹¹dynecm^-2, $\text{C}{}_{12}\text{= (1.82 ± 0.17) × 10}{}^{11}\text{dyne}\text{cm}{}^2$ and C₄₄ = (9.01 ± 0.05) × 10¹¹dyne/cm². The Debye temperature of LaB₆ from these measurements is 773 K, which agrees relatively well with the X-ray Debye temperature, however, differs much from the calorimetric and electrical resistance Debye temperatures.     

Excitation intensity dependence of shallow donor bound exciton luminescence in n-GaAs

Luminescence measurements were performed on high purity epitaxial n-GaAs $\text{(}\text{1 × 10}{}^{14}\text{cm}{}^3\text{< n <}\text{3 × 10}{}^{15}\text{cm}{}^3\text{)}$ for various excitation intensities I₀ in the range $\text{8 mW}\text{cm}{}^2\text{< I}{}_0\text{<}\text{4 W}\text{cm}{}^2$. The luminescence line corresponding to the radiative decay of the shallow donor bound exciton, (D⁰, X), broadens with increasing I₀ and appears as a doublet for $\text{I}{}_0\text{? 1}\text{W}\text{cm}{}^2$, while the two-electron replica of the (D⁰, X) remains a single narrow line. The doublet structure of the (D⁰, X) at elevated excitation levels is due to missing luminescence intensity in the center of the line as a consequence of low (D⁰, X) concentration in a layer extending 1–2 μm from the sample surface into the bulk. The low concentration of (D⁰, X) is attributed to capture of (D⁰, X) quanta into surface states, extending to lower energies from the Fermi level fixed by the shallow donors. Comparison of the present results with luminescence spectra obtained by various authors reveals, that unexplained spectral features in the (D⁰, X) region of n-GaAs reported in the literature are a consequence of high excitation intensity and correspond to the effect reported here. In partly compensated p-GaAs with donor concentrations as given above, the (D⁰, X) did not transform into a doublet structure even at $\text{W}\text{cm}{}^2$ excitation intensity.     

The rotational spectrum of the X 2Σ+ state of the SrF radical using laser microwave optical double resonance

The pure rotational spectrum of the $\text{X}{}^2\text{Σ}{}^{\mathrm{+}}$ state of the gaseous SrF radical has been measured using microwave optical double resonance (MODR) techniques. The analysis fully confirms the recent dye laser excitation spectrum and rotational assignment of the $\text{B}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Σ}{}^{\mathrm{+}}$ system. Transitions were measured in both the v″ = 0 and v″ = 1 states to give values of B_e″ = 0.250533 cm^?1, α_e″ = 1.546 × 10^?3 cm^?1 and γ″ (spin-rotation) = 2.49 × 10^?3 cm^?1. General qualitative features of MODR in ²Σ⁺ states are treated and suggested improvements for obtaining experimental hyperfine constants are discussed. The more precise ground state constants are merged with the B-X optical analysis to obtain a more accurate set of constants for both states.     

Infrared bands of 12C2HD

The rotational structure of about 40 bands of ¹²C₂HD observed in the region 6000?600 cm^?1 has been measured and interpreted with the purpose of determining a comprehensive set of molecular constants for this isotopic variety of acetylene. Combining these data with the results for ¹²C₂H₂ and ¹²C₂D₂, a reevaluation of the equilibrium internuclear distances for the acetylene molecule has been made: $\text{r}{}_{\mathrm{e}}\text{(CH) = 1.06215 ± 17 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{e}}\text{(CC) = 1.20257 ± 9 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ were obtained. This paper presents all the molecular constants derived in this study.     

Hole mobility in p-type HgTe

Experimental data concerning the electrical conduction and Hall coefficient in HgTe samples with acceptor states have been collected and analysed. In the analysis three ranges of acceptor concentration have been distinguished: a low concentration range up to about 5 × 10¹⁵ cm^?3 (pure samples), a high concentration range from 10¹⁶ to 10¹⁸ cm^?3 (p-like samples), and an extremely high concentration range above 10¹⁸ cm^?3 (p-type samples). In pure HgTe samples the holes are in the valence band, in p-like samples the “holes” are in the impurity band, and in p-type HgTe samples the holes are in a strong mixing impurity-valence band. The mobility of holes in the valence band is of the order of $\text{10}{}^5\text{cm}{}^2\text{Vs}$. The mobility of “holes” in the impurity band decreases with increasing impurity concentration from about $\text{5 × 10}{}^3\text{cm}{}^2\text{Vs}$ to $\text{125}\text{cm}{}^2\text{Vs}$. The mobility of holes in p-type HgTe samples is independent of the acceptor concentration and is equal to $\text{125}\text{cm}{}^2\text{Vs}$.     

Static structure factor of gaseous helium

The static structure factor of helium gas has been measured at densities of 3.45 × 10^?3, 2.66 × 10^?3 and $\text{1.95 × 10}{}^{\mathrm{?3}}\text{moles}\text{cm}{}^3$ at a temperature of 4.995 K. The results are in qualitative agreement with the limited theoretical work available.     

Electronic conductivity of AgI using D.C. polarization and charge transfer techniques

A Study of electronic conductivity using the d.c. polarization technique has been carried out in α and β-AgI which shows the former is a hole and the latter an electron conductor. Activation energies of undoped and Cu-doped single crystals and polycrystalline β-AgI were found to be 0.46 eV, 0.34 eV and 0.44 eV respectively and can be related to electron trap depths. The electron transference number ($\text{σ}{}_{\mathrm{\theta }}\text{σ}{}_{\mathrm{t}}$) for polycrystalline β-AgI was found to be 0.008 at 306 K. The activation energy for hole conduction in α-AgI was determined to be 0.97 eV in agreement with previous XPS studies.Transient measurements have also been conducted using the charge transfer technique in double cells of polycrystalline β-AgI. The carrier concentration C_θ and electron mobility μ_θ, have thus been estimated to be 1.8 × $\text{10}{}^{15}\text{cm}{}^3$ and 5.14 × 10^?5$\text{cm}{}^2\text{V}$?sec. respectively at 306 K, while the double layer capacitance was 0.496 $\text{μF}\text{cm}{}^2$.     

UV-induced double injection in α-sulfur single crystals

The I–V characteristics of the UV-induced double injection of carriers into sulfur single crystals are reported. These characteristics display a quadratic behavior as a function of the electric field up to E≈7×10³$\text{Volts}\text{cm}$ where it changes to a cubic law dependence. The V² branch can be accounted for by means of the one carrier space charge limited current. The cube law dependence arises as a result of the recombination limited two-carrier injection according to the model of Lampert and Mark. We estimate values for the common lifetime τ = 4.8×10^?3 sec, and the trap modulated mobility of holes $\text{μ}{}_{\mathrm{<mtext>h</mtext>}}\text{θ}{}_{\mathrm{<mtext>h</mtext>}}\text{=8.9×10}{}^{\mathrm{?6}}\text{cm}{}^2\text{V sec}$.     

Ellipsometric investigation of the skeletonization process of langmuir-blodgett films

When Langmuir-Blodgett films, consisting of a mixture of a long chain carboxylic acid and its salt are immersed in benzene, the acid dissolves, while the salt remains as a skeleton. The density of the film is lowered in this way and so is the refractive index. The process can thus be followed by performing ellipsometric measurements as a function of time of skeletonization. It is established that skeletonization is, in first instance, a diffusion-controlled process with a diffusion coefficient of about $\text{5 × 10}{}^{\mathrm{?14}}\text{cm}{}^2\text{sec}$ at room temperature. The salt also slowly dissolves at a rate of about $\text{1.6 × 10}{}^{10}\text{molecules}\text{/}\text{sec}\text{cm}{}^2$.     

Analysis of the Raman spectrum of SF6

The Raman active fundamentals ν₁(A1g), ν₂(Eg), ν₅(F2g), and the overtone 2ν₆ of SF₆ have been investigated with a higher resolution and the band origins were estimated to be: ν₁ = 774.53 cm^?1, ν₂ = 643.35 cm^?1, ν₅ = 523.5 cm^?1, and 2ν₆ = 693.8 cm^?1. Raman and infrared data have been combined for estimation of several anharmonicity constants. The ν₆ fundamental frequency is calculated as 347.0 cm^?1. From the analysis of the ν₂ Raman band, the following rotational constants of both the ground and upper states have been calculated:

$\text{B}{}_0\text{= 0.09111 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_0\text{= (0.16±0.08)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

;

$\text{B}{}_2\text{= 0.09116 ± 0.00005}\text{cm}{}^{\mathrm{?1}}\text{; D}{}_2\text{= (0.18±0.04)10}{}^{\mathrm{?7}}\text{cm}{}^{\mathrm{?1}}$

.     

The ground state of methane 12CH4 through the forbidden lines of the ν3 band

High resolution spectra of the ν₃ band of methane, ¹²CH₄, were recorded by using a “third generation vacuum Fourier interferometer”; a large pressure range (from 0.009 to 10 Torr) with a sample path fixed at eight meters was used, enabling observation of transitions with intensity ratios as low as $\text{1}\text{10 000}$. More than 350 forbidden transitions of the ν₃ band, including about 125 transitions of the Q⁺ branch, were unambiguously identified. Of the 277 transitions retained for computations, one-hundred have 11 ≤ J ≤ 16. From combination difference relations using pairs of transitions having the same upper state energy level (forbidden-allowed and forbidden-forbidden pairs were used), 276 independent differences between ground state energy levels could be determined with uncertainties of about 0.001 cm^?1.These data yielded the following values for the ground state structure constants of ¹²CH₄ along with their standard deviations (in cm^?1): $\text{β}{}^{\mathrm{o}}\text{hc}\text{=5.2410356±0.0000096}$, $\text{γ}{}^{\mathrm{o}}\text{hc}\text{=(?1±0.00074) 10}{}^{\mathrm{?4}}$, $\text{π}{}^{\mathrm{o}}\text{hc}\text{=(5.78±0.18) 10}{}^{\mathrm{?9}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.4485±0.0023) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.768±0.126) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.602±0.067) 10}{}^{\mathrm{?11}}$, Thus, for the first time, the scalar constant π⁰ has been evaluated and ir values have been obtained for the two tetrahedral constants ?⁰ and ξ⁰; furthermore, these values are in very good agreement with the ones recently determined from radiofrequency data, i.e., in cm^?1: $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.45061±0.00014) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.7634±0.0068) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.5432±0.0040) 10}{}^{\mathrm{?11}}$ From these values, the 276 differences can be reproduced with an overall rms deviation equal to 0.0009 cm^?1.Finally, the ground state energies of ¹²CH₄ have been calculated for J ≤ 16.     

Polarizabilities of shallow donors in silicon

Capacitance measurements on N-type As, P, and Sb-doped Si samples have been made between 4.2 and 1.35°K, from 0.3 to 100 kHz as a function of (N_D ? N_A) [high purity to 2.7 × 10¹⁸/cm³]. From the dielectric constant variation with (N_D ? N_A) donor polarizabilities α_AS, α_P, and α_Sb are found respectively to be $\text{1.0±0.1, 2.4±0.4,}\text{and}\text{3.1±0.3 × 10}{}^5\text{A}\text{?}{}^3$.