Investigation of bulk indium antimonide as heterodyne detector for the submillimeter wavelength region

Bulk n-lnSb is investigated at a heterodyne detector for the submillimeter wavelength region. Two modes or operation are investigated: (1) the Rollin or hot electron bolometer mode (zero magnetic field), and (2) the Putley mode (quantizing magnetic field). The highlight of the thesis work is the pioneering demonstration or the Putley mode mixer at several frequencies. For example, a double-sideband system noise temperature of about 510K was obtained using a 812 GHz methanol laser for the local oscillator. This performance is at least a factor or 10 more sensitive than any other performance reported to date at the same frequency. In addition, the Putley mode mixer achieved system noise temperatures of 250K at 492 GHz and 350K at 625 GHz. The 492 GHz performance is about 50% better and the 625 GHz is about 100% better than previous best performances established by the Rollin-mode mixer. To achieve these results, it was necessary to design a totally new ultra-low noise, room-temperature preamp to handle the higher source impedance imposed by the Putley mode operation. This preamp has considerably less input capacitance than comparably noisy, ambient designs.

In addition to advancing receiver technology, this thesis also presents several novel results regarding the physics of n-lnSb at low temperatures. A Fourier transform spectrometer was constructed and used to measure the submillimeter wave absorption coefficient of relatively pure material at liquid helium temperatures and in zero magnetic field. Below 4.2K, the absorption coefficient was found to decrease with frequency much faster than predicted by Drudian theory. Much better agreement with experiment was obtained using a quantum theory based on inverse-Bremmstrahlung in a solid. Also the noise of the Rollin-mode detector at 4.2K was accurately measured and compared with theory. The power spectrum is found to be well fit by a recent theory of non- equilibrium noise due to Mather. Surprisingly, when biased for optimum detector performance, high purity lnSb cooled to liquid helium temperatures generates less noise than that predicted by simple non-equilibrium Johnson noise theory alone. This explains in part the excellent performance of the Rollin-mode detector in the millimeter wavelength region.

Again using the Fourier transform spectrometer, spectra are obtained of the responsivity and direct detection NEP as a function of magnetic field in the range 20-110 cm^-1. The results show a discernable peak in the detector response at the conduction electron cyclotron resonance frequency tor magnetic fields as low as 3 KG at bath temperatures of 2.0K. The spectra also display the well-known peak due to the cyclotron resonance of electrons bound to impurity states. The magnitude of responsivity at both peaks is roughly constant with magnet1c field and is comparable to the low frequency Rollin-mode response. The NEP at the peaks is found to be much better than previous values at the same frequency and comparable to the best long wavelength results previously reported. For example, a value NEP=4.5x10^-13/Hz^1/2 is measured at 4.2K, 6 KG and 40 cm^-1. Study of the responsivity under conditions of impact ionization showed a dramatic disappearance of the impurity electron resonance while the conduction electron resonance remained constant. This observation offers the first concrete evidence that the mobility of an electron in the N=0 and N=1 Landau levels is different. Finally, these direct detection experiments indicate that the excellent heterodyne performance achieved at 812 GHz should be attainable up to frequencies of at least 1200 GHz.

Radio frequency studies of surface resistance and critical magnetic field of type I and type II superconductors

The surface resistance and the critical magnetic field of lead electroplated on copper were studied at 205 MHz in a half-wave coaxial resonator. The observed surface resistance at a low field level below 4.2°K could be well described by the BCS surface resistance with the addition of a temperature independent residual resistance. The available experimental data suggest that the major fraction of the residual resistance in the present experiment was due to the presence of an oxide layer on the surface. At higher magnetic field levels the surface resistance was found to be enhanced due to surface imperfections.

The attainable rf critical magnetic field between 2.2°K and T_c of lead was found to be limited not by the thermodynamic critical field but rather by the superheating field predicted by the one-dimensional Ginzburg-Landau theory. The observed rf critical field was very close to the expected superheating field, particularly in the higher reduced temperature range, but showed somewhat stronger temperature dependence than the expected superheating field in the lower reduced temperature range.

The rf critical magnetic field was also studied at 90 MHz for pure tin and indium, and for a series of SnIn and InBi alloys spanning both type I and type II superconductivity. The samples were spherical with typical diameters of 1-2 mm and a helical resonator was used to generate the rf magnetic field in the measurement. The results of pure samples of tin and indium showed that a vortex-like nucleation of the normal phase was responsible for the superconducting-to-normal phase transition in the rf field at temperatures up to about 0.98-0.99 T_c' where the ideal superheating limit was being reached. The results of the alloy samples showed that the attainable rf critical fields near T_c were well described by the superheating field predicted by the one-dimensional GL theory in both the type I and type II regimes. The measurement was also made at 300 MHz resulting in no significant change in the rf critical field. Thus it was inferred that the nucleation time of the normal phase, once the critical field was reached, was small compared with the rf period in this frequency range.

Magnetic behavior of basic iron(III) compounds. I. Magnetic behavior of the basic iron sulphates and basic iron chromate. II. Magnetic behavior of delta ferric oxide hydroxide

I. The thermomagnetic behavior and infrared spectroscopic features of KFe₃(SO₄)₂(OH)₆ (jarosite), (H₃O)Fe₃(SO₄)₂ (OH)₆ (hydronium jarosite), KFe₃(CrO₄)₂ (OH)₆, Fe(OH)SO₄ (basic iron sulfate), and Fe(OH)CrO₄ (basic iron chromate) are reported. Fe(OH)CrO₄ and KFe₃(CrO₄)₂ (OH)₆ are shown to be weak ferro magnets with Curie temperatures of 73 and 71 °K, respectively. This unusual magnetic behavior is rationalized in terms of the ionic spin configurations of the phases. Exchange coupling through chromate bridging groups is shown to be weak.

II. The magnetic behavior and the influence of preparative history on the magnetic behavior of δFeO(OH) is reported. δFeO(OH) is shown to be a fine-particulate, uniaxial, magnetic species. Magnetization data for this species are shown to be consistent with the existence of magnetically inactive layers surrounding magnetic particles.

I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.

Sputtering of the gallium-indium eutectic alloy in the liquid phase

We have measured sputtering yields and angular distributions of sputtered atoms from both the solid and liquid phases of gallium, indium, and the gallium-indium eutectic alloy. This was done by Rutherford backscattering analysis of graphite collector foils. The solid eutectic target shows a predominance of indium crystallites on its surface which have to be sputtered away before the composition of the sputtered atoms equals the bulk target composition. The size of the crystallites depends upon the conditions under which the alloy is frozen. The sputtering of the liquid eutectic alloy by 15 keV Ar⁺ results in a ratio of indium to gallium sputtering yields which is 28 times greater than would be expected from the target stoichiometry. Furthermore, the angular distribution of gallium is much more sharply peaked about the normal to the target surface than the indium distribution. When the incident Ar⁺ energy is increased to 25 keV, the gallium distribution broadens to the same shape as the indium distribution. With the exception of the sharp gallium distribution taken from the liquid eutectic at 15 keV, all angular distributions from liquid targets fit a cos² θ function. An ion-scattering-spectroscopy analysis of the liquid eutectic alloy reveals a surface layer of almost pure indium. A thermodynamic explanation for this highly segregated layer is discussed. The liquid eutectic alloy provides us with a unique target system which allows us to estimate the fraction of sputtered material which comes from the first monolayer of the surface.

Thermodynamic and kinetic behavior of an argon plasma jet. Decomposition of nitric oxide between 1300 - 1750 degrees K in an argon plasma

In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.

Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.

The temperatures, T, and the electron densities, n_e , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, v_z, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 10¹² ˂ n_e ˂ 10¹⁵ particles/cm³, 3500 ˂ T ˂ 11000 °K, and 200 ˂ v_z ˂ 1200 cm/sec.

The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and n_e was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.

Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.

In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by x_NO were determined gas-chromatographically and varied between 0.0012 ˂ x_NO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.

Electrical and optical investigations of beta-gallium oxide

An experimental investigation of the optical properties of β–gallium oxide has been carried out, covering the wavelength range 220-2500 nm.

The refractive index and birefringence have been determined to about ± 1% accuracy over the range 270-2500 nm, by the use of a technique based on the occurrence of fringes in the transmission of a thin sample due to multiple internal reflections in the sample (ie., the "channelled spectrum" of the sample.)

The optical absorption coefficient has been determined over the range 220 - 300 nm, which range spans the fundamental absorption edge of β – Ga₂O₃. Two techniques were used in the absorption coefficient determination: measurement of transmission of a thin sample, and measurement of photocurrent from a Schottky barrier formed on the surface of a sample. Absorption coefficient was measured over a range from 10 to greater than 10⁵, to an accuracy of better than ± 20%. The absorption edge was found to be strongly polarization-dependent.

Detailed analyses are presented of all three experimental techniques used. Experimentally determined values of the optical constants are presented in graphical form.