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Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyance-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions. The following are the research progress in the past two years. In-situ monitoring of partial pressure by optical absorption technique and visual observation of the growing crystal were performed during vapor growth of ZnSe. Low-temperature photoluminescence (PL) spectra and glow discharge mass spectroscopy (GDMS) were measured on ZnSe starting materials provided by various vendors and on bulk crystals grown from these starting materials by physical vapor transport (PVT) to study the effects of purification and contamination during crystal growth process. Optical characterization was performed on wafers sliced from the grown crystals of ZnSe, ZnTe and ZnSe(1-x),Te(x), (0<x<0.4). Energy band gaps at room temperature were determined from optical transmission measurements and a best fit curve to the band gap vs. composition, x, data gives a bowing parameter of 1.45. Low-temperature photoluminescence (PL) spectra of ZnSe and ZnTe were dominated by near band edge emissions and no deep donor-acceptor pairs were observed. The PL spectrum exhibited a broad emission for the ZnSe(1-x),Te(x), samples, 0.09<x<0.39. The single broad PL emission spectra and the spectra measured as a function of temperature were interpreted as being associated with the exciton bound to Te clusters because of the high Te content in these samples. To validate numerical codes, in-situ monitoring during the PVT of HgI2 was designed. Optical absorption spectra of the vapor phase over HgI2 were measured for wavelengths between 200 and 600nm at sample temperatures between 349 and 610K. The Beer's Law constants for 15 wavelengths between 200 and 440 nm were determined. From these constants the vapor pressure of HgI2 was established as a function of temperature for the liquid and the solid Beta-phases To characterize the growth conditions during the PVT growth of In-doped ZnSe the optical absorbance of the vapor phase over the In-Se system were measured and were used to obtain the partial pressures of Se2(g) and In2Se(g).

Su, Ching-Hua↗

Vapor Growth of Indium Monoiodide

Indium (I) iodide, InI, is part of a group of heavy metal iodides that can be used as room temperature radiation detectors. Other examples are HgI2, PbI2, BiI3, or TlPbI3. InI has several advantages, such as low toxicity, no solid phase transition (such as in HgI2), and no tendency to form polytypes (PbI2, BiI3 ). All binary iodides have layered structures and are quite soft, but InI is also the mechanically most stable compound of the binary compounds. Table 1 shows the main properties of InI in comparison with the other iodides and the most common room temperature radiation detector material, (Cd, Zn)Te. InI is typically grown by the unseeded Bridgman method using a nucleation tip, but Czochralski (CZ) growth has also been demonstrated. The resulting crystals have been used successfully for radiation detection, but both resistivity and mobility are usually well below theoretically predicted values. Physical vapor transport (PVT), although much slower than melt growth, is an alternative method and has been used to grow e.g. HgI2, PbI2, BiI3, CdTe. PVT growth should eliminate or reduce inclusions and impurities since it is based on sublimation, reduce intrinsic defects due to the lower growth temperature, and reduce dislocation densities due to reduced thermal and mechanical stress. As an example, PVT-grown CdTe showed a much improved structural quality compared to Bridgman- or THM-grown material.

Cröll, Arne↗

Performance of room temperature mercuric iodide /HgI2/ detectors in the ultralow-energy X-ray region

Experiments have been done to study the performance of mercuric iodide (HgI2) detectors in the ultralow-energy X-ray region. Energy resolution values of 245 eV (FWHM) for the Mg K-alpha X-ray line at 1.25 keV and 225 eV (FWHM) for the electronic noise linewidth have been obtained for an HgI2 detector with painted carbon contacts using a pulsed-light feedback preamplifier; the whole system was operated at room temperature. The resolution values in the ultralow-energy region are still limited by electronic noise of the system. In an attempt to minimize X-ray attenuation in the front contact, detectors were prepared with thin evaporated Pd contacts. These detectors show a pronounced low-energy tailing of the photopeak below a few keV, in contrast to the spectra obtained by detectors with carbon contact. An attempt has been made to explain the tailing effect starting with models wich have been proposed to describe similar effects in Ge detectors.

Dabrowski, A. J.↗

Fluid Dynamics and Thermodynamics of Vapor Phase Crystal Growth

The ground-based research effort under this program is concerned with systematic studies of the effects of variations: (1) of the relative importance of buoyancy-driven convection, and (2) of diffusion and viscosity conditions on crystal properties. These experimental studies are supported by thermodynamic characterizations of the systems, based on which fluid dynamic parameters can be determined. The specific materials under investigation include: the GeSe-GeI4, Ge-GeI4, HgTe-HgI2, and Hg sub (1-x)Cd sub (x) Te-HgI2 systems. Mass transport rate studies of the GeSe-GeI system as a function of orientation of the density gradient relative to the gravity vector demonstrated the validity of flux anomalies observed in earlier space experiments. The investigation of the effects of inert gases on mass flux yielded the first experimental evidence for the existence of a boundary layer in closed ampoules. Combined with a thorough thermodynamic analysis, a transport model for diffusive flow including chemical vapor transport, sublimation, and Stefan flow was developed.

Wiedemeier, H.↗

High resolution, low energy avalanche photodiode X-ray detectors

Silicon avalanche photodiodes have been fabricated, and their performance as X-ray detectors has been measured. Photon sensitivity and energy resolution were measured as a function of size and operating parameters. Noise thresholds as low as 212 eV were obtained at room temperature, and backscatter X-ray fluorescence data were obtained for aluminum and other light elements. It is concluded that the results with the X-ray detector are extremely encouraging, and the performance is challenging the best available proportional counters. While not at the performance level of either cryogenic silicon or HgI2, these device operate at room temperature and can be reproduced in large numbers and with much larger areas than typically achieved with HgI2. In addition, they are rugged and appear to be indefinitely stable.

Farrell, R.↗

Mercury iodide crystal growth

The purpose of the Mercury Iodide Crystal Growth (MICG) experiment is the growth of near-perfect single crystals of mercury Iodide (HgI2) in a microgravity environment which will decrease the convection effects on crystal growth. Evaporation and condensation are the only transformations involved in this experiment. To accomplish these objectives, a two-zone furnace will be used in which two sensors collect the temperature data (one in each zone).

Cadoret, R.↗

Epitaxial growth of Hg/1-x/Cd/x/Te by chemical vapor transport

The chemical vapor transport technique was applied for the first time to the growth of Hg(1-x)Cd(x)Te epitaxial layers on CdTe substrates using a preannealed source material of Hg(0.8)Cd(0.2)Te. The experiment took place in a pretreated ampoule loaded with source material, HgI2 transport agent, and substrate and sealed under a residual pressure of about 10 to the -5th torr. The temperature of the source region was 590 C and that of the deposition zone 535 C with a nearly sigmoidal shaped profile between the end temperatures. The change in appearance of the substrate surface during the experiment is described, and the structures of the surface of the Hg(1-x)Cd(x)Te layer and of the layer itself as revealed by Nomarski contrast illumination and Laue X-ray diffraction, respectively, are discussed.

Wiedemeier, H.↗

Room-temperature mercuric iodide spectrometry for low-energy X-rays

A discussion of the limits of energy resolution in different energy ranges is given. The energy resolution of a spectrometer is analyzed in terms of the parameters characterizing the crystal, the detector, and the amplification electronics. A high-resolution room-temperature HgI2 spectrometry system was used to measure low-energy X-ray fluorescence spectra. For the MgK-alpha X-ray line the measured resolution was 245 eV (fwhm); the electronic noise linewidth of the system was 225 eV. Alpha-particles were used to excite X-ray fluorescence from low-Z elements separately or in combination. The shape of the photopeaks in the spectra is discussed.

Kusmiss, J. H.↗

A mercuric detector system for X-ray astronomy. 2. Results from flight tests of a balloon borne instrument

To establish the expected sensitivity of a new hard X-ray telescope design, an experiment was conducted to measure the background counting rate at balloon altitudes (40 km) of mercuric iodide, a room temperature solid state X-ray detector. The prototype detector consisted of two thin mercuric iodide (HgI2) detectors surrounded by a large bismuth germanate (Bi4Ge3O12) scintillator operated in anticoincidence. The bismuth germanate shield vetoed most of the background counting rate induced by atmospheric gamma-rays, neutrons and cosmic rays. A balloon-borne gondola containing a prototype detector assembly was designed, constructed and flown twice in the spring of 1982 from Palestine, Texas. The second flight of this instrument established a differential background counting rate of 4.2 O.7 x 10-5 counts/sec cm keV over the energy range of 40 to 80 keV. This measurement was within 50% of the predicted value. The measured rate is approx 5 times lower than previously achieved in shielded NaI/CsI or Ge systems operating in the same energy range. The prediction was based on a Monte Carlo simulation of the detector assembly in the radiation environment at float altitude.

Vallerga, J.↗

A mercuric iodide detector system for X-ray astronomy. I - Design considerations and predictions of background and sensitivity

Since the discovery of Sco X-1 initiated X-ray astronomy in 1962, this science has progressed in connection with the placement of X-ray photon detectors above the atmosphere by means of rockets, balloons, and satellites. In the last few years, studies have been conducted regarding the use of mercuric iodide (HgI2) as room temperature X-ray detector for applications in hard X-ray astronomy. These detectors combine a high quantum efficiency with good energy resolution. The sensitivity of an astronomical X-ray telescope is discussed, and a description is presented of a specific design accepted for the HDXT to be flown on Spacelab. Attention is given to predictions of the background counting rate of the detector assembly in this design, taking into account the results of a Monte Carlo simulation of the detector assembly in the radiation environment at balloon altitudes (40 km).

Ricker, G. R.↗

A mercuric iodide detector system for X-ray astronomy. II - Results from flight tests of a balloon borne instrument

To establish the expected sensitivity of a new hard X-ray telescope design, described by Ricker et al., an experiment was conducted to measure the background counting rate at balloon altitudes (40 km) of mercuric iodide, a room temperature solid state X-ray detector. The prototype detector consisted of two thin mercuric iodide (HgI2) detectors surrounded by a large bismuth germanate scintillator operated in anticoincidence. The bismuth germanate shield vetoed most of the background counting rate induced by atmospheric gamma-rays, neutrons and cosmic rays. A balloon-borne gondola containing a prototype detector assembly was designed, constructed and flown twice in the spring of 1982 from Palestine, TX. The second flight of this instrument established a differential background counting rate of 4.2 + or - 0.7 x 10 to the -5th counts/s sq cm keV over the energy range of 40-80 keV. This measurement was within 50 percent of the predicted value. The measured rate is about 5 times lower than previously achieved in shielded NaI/CsI or Ge systems operating in the same energy range.

Vallerga, J. V.↗

Measurement of the characteristic X ray of oxygen and other ultrasoft X rays using mercuric iodide detectors

This letter reports the detection and resolution of the characteristic X-ray of oxygen at 523 eV and other ultrasoft X-rays (photons energy less than 1 keV) using radiation detectors fabricated from the compound semi-insulator mercuric iodide (HgI2). These detectors are capable of operation at room ambient but in these experiments were slightly cooled using a Peltier element to 0 C. A pulsed light feedback preamplifier with a Peltier element cooled (to -30 deg) first stage field-effect transistor was used to amplify signals from the detector. Overall system noise level was 185 eV (full width at half-maximum) limited by the temperature of the first stage field-effect transistor. With optimal cooling of this element the characteristic X-ray of carbon at 282 eV should be measurable. These results would seem to be important in measurement of biological samples in electron column instruments.

Iwanczyk, J. S.↗

X-ray fluorescence analysis of alloy and stainless steels using a mercuric iodide detector

A mercuric iodide detector was used for the XRF analysis of a number of NBS standard steels, applying a specially developed correction method for interelemental effects. It is shown that, using this method and a good peak-deconvolution technique, the HgI2 detector is capable of achieving resolutions and count rates needed in the XRF anlysis of multielement samples. The freedom from cryogenic cooling and from power supplies necessary for an electrically cooled device makes this detector a very good candidate for a portable instrument.

Kelliher, Warren C.↗

Advances in the development of encapsulants for mercuric iodide X-ray detectors

Advances in the development of protective impermeable encapsulants with high transparency to ultra-low-energy X-rays for use on HgI2 X-ray detectors are reported. Various X-ray fluorescence spectra from coated detectors are presented. The X-ray absorption in the encapsulants has been analyzed using characteristic radiation from various elements. Results suggest that low-energy cutoffs for the detectors are not determined solely by the encapsulating coatings presently employed but are also influenced by the front electrode and surface effects, which can affect the local electric field or the surface recombination velocity. An energy resolution of 182 eV (FWHM) has been achieved for Ni L lines at 850 eV. Improved detector sensitivity to X-ray energies under 700 eV is demonstrated.

Iwanczyk, J. S.↗

Miniaturization in x ray and gamma ray spectroscopy

The paper presents advances in two new sensor technologies and a miniaturized associated electronics technology which, when combined, can allow for very significant miniaturization and for the reduction of weight and power consumption in x-ray and gamma-ray spectroscopy systems: (1) Mercuric iodide (HgI2) x-ray technology, which allows for the first time the construction of truly portable, high-energy resolution, non-cryogenic x-ray fluorescence (XRF) elemental analyzer systems, with parameters approaching those of laboratory quality cryogenic instruments; (2) the silicon avalanche photodiode (APD), which is a solid-state light sensitive device with internal amplification, capable of uniquely replacing the vacuum photomultiplier tube in scintillation gamma-ray spectrometer applications, and offering substantial improvements in size, ruggedness, low power operation and energy resolution; and (3) miniaturized (hybridized) low noise, low power amplification and processing electronics, which take full advantage of the favorable properties of these new sensors and allow for the design and fabrication of advanced, highly miniaturized x-ray and gamma-ray spectroscopy systems. The paper also presents experimental results and examples of spectrometric systems currently under construction. The directions for future developments are discussed.

Iwanczyk, Jan S.↗

Vapor transport crystal growth of mercury-cadmium-telluride in microgravity

Two epitaxial growth experiments of Hg(1-x)Cd(x)Te layers on (100) CdTe substrates in closed ampoules using HgI2 as a transport agent have been performed during the USML-1 mission. The characterization results to date demonstrate a considerable improvement of the space-grown epitaxial layers relative to ground-control specimens in terms of morphology, compositional uniformity, and structural micro homogeneity. These results show the effects of microgravity and fluid dynamic disturbances on-ground on the deposition and growth processes. The continued analysis of this technologically important system is designed to further elucidate the observed crystallographic improvements and their relation to mass flow.

Wiedemeier, Heribert↗

Experiment 2: Vapor Transport Crystal Growth of Mercury Cadmium Telluride in Microgravity- USML-2

The new epitaxial growth experiments of Hg(l-x)Cd(x)Te on (100) CdTe substrates by chemical vapor transport (CVT), using HgI2 as a transport agent, were performed in the transient growth regime of this ternary, heteroepitaxial system at normal and reduced gravity during the USML-2 flight. The surface and interface morphology, the compositional and structural uniformity, and carrier mobility of the epitaxial layer and islands grown in microgravity are measurably improved relative to ground specimens. These observations demonstrate the effects of convective flow on the transport, deposition, and growth processes of this solid-vapor system even in the transient growth regime. The properties of the Hg(l-x)Cd(x)Te layer grown in a microgravity environment compare quite favorably to those of layers obtained by other techniques.

Wiedemeier, H.↗