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The head and wake waves of filtration combustion of calcium hydride in a flow of a mixture of silicon tetrafluoride and hydrogen at silicon tetrafluoride weight fractions of 0.8, 0.85, 0.9, and 0.98 were studied. The spatial profiles of the combustion waves were constructed. With their aid, the thermal structure of the head and wake waves was found, and the width of each zone in the combustion wave for different compositions of the gas phase was determined. With increasing concentration of the reagent gas in the flow, the reaction zone width increases in the head wave and decreases in the wake wave. The structure of the head wave corresponds to the intermediate combustion wave, and the structure of the wake wave, to the normal combustion wave.

In order to study the isotopic effects in semiconductor materials, single crystals of high chemical and isotopic purity are required. The reliability of the obtained data on the magnitude and the direction of isotopic shifts depends on the accuracy of determining the concentration of all stable isotopes. In the isotopic analysis of enriched “silicon-28” with a high degree of enrichment ( 99.99%), it is necessary to determine the impurities of 29Si and 30Si isotopes at the level of 10-3 ¸ 10-5 at. %. At this concentration level, these isotopes can be considered as impurities. It is difficult to achieve high measurement accuracy with simultaneous registration of the main and “impurity” isotopes in such a wide range of concentrations. The registration of analytical signals of silicon isotopes must be carried out in the solutions with different matrix concentrations. The use of the solutions with the high concentration of the matrix element requires the introduction of corrections for matrix noise and the drift of the instrument sensitivity during the measurement. It is possible to reduce the influence of the irreversible non-spectral interference and sensitivity drift by using the method of internal standardization. The inconsistency of the literature data on the selection criteria for the internal standard required studying the behavior of the signals of the “candidates for the internal standard” for the ELEMENT 2 single-collector high-resolution inductively coupled plasma mass spectrometer on the matrix element concentration and the nature of the solvent, as well as on the solution nebulizing time. Accounting for the irreversible non-spectral matrix noise and instrumental drift in isotopic analysis of enriched “silicon-28” and initial 28SiF4 by inductively coupled plasma mass spectrometry had allowed us to reduce by 3-5 times the random component and by more than an order of magnitude the systematic component of the measurement error in comparison with the external standard method. This made it possible to carry out, with sufficient accuracy, the operational control of the isotopic composition of enriched “silicon-28”, both in the form of silicon tetrafluoride and polycrystalline silicon obtained from it, using a single serial device in the range of isotopic concentrations 0.0001–99.999%.Key words: high-resolution inductively coupled plasma mass spectrometry, isotope analysis, isotopically enriched silicon, internal standard DOI: http://dx.doi.org/10.15826/analitika.2021.25.2.009P.A. Otopkova, A.M. Potapov, A.I. Suchkov, A.D. Bulanov, A.Yu. Lashkov G.G. Devyatykh Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences (IChHPS RAS), 49 Tropinina St., Nizhny Novgorod, 603951, Russian Federation, Для изучения изотопических эффектов в полупроводниковых материалах требуются монокристаллы с высокой химической и изотопной чистотой. Надежность полученных данных о величине и направлении изотопических сдвигов зависит от точности определения концентрации всех стабильных изотопов. При изотопном анализе обогащенного “кремния-28” с высокой степенью обогащения (более 99.99 %) необходимо определять примеси изотопов 29Si и 30Si на уровне 10-3 ¸ 10-5 ат. %. На таком уровне концентраций указанные изотопы можно рассматривать как примеси. Достижение высокой точности измерений при одновременной регистрации основного и “примесных” изотопов в таком широком интервале концентраций затруднительно. Регистрацию аналитических сигналов изотопов кремния приходится проводить на растворах с разной концентрацией матрицы. Использование растворов с высокой концентрацией матричного элемента требует введения поправок на матричные помехи и дрейф чувствительности прибора в процессе измерения. Снизить влияние необратимых неспектральных помех и дрейфа чувствительности можно при использовании метода внутренней стандартизации. Противоречивость литературных данных о критериях выбора внутреннего стандарта потребовала исследования поведения сигналов элементов “кандидатов во внутренний стандарт“ для одноколлекторного масс-спектрометра высокого разрешения с индуктивно связанной плазмой ELEMENT 2 от концентрации матричного элемента и природы растворителя, а также от времени распыления раствора. Учет необратимых неспектральных матричных помех и аппаратного дрейфа при изотопном анализе обогащенного “кремния-28” и исходного 28SiF4 методом масс-спектрометрии с индуктивно связанной плазмой позволил снизить в 3-5 раз случайную составляющую и более чем на порядок систематическую составляющую погрешности измерения по сравнению с методом внешнего стандарта. Это позволило проводить с достаточной точностью оперативный контроль изотопного состава обогащенного “кремния-28”, как в виде тетрафторида кремния, так и получаемого из него поликристаллического кремния с помощью одного серийного прибора в интервале изотопных концентраций 0.0001–99.999 ат. %.Ключевые слова: масс-спектрометрия высокого разрешения с индуктивно связанной плазмой, изотопный анализ, изотопнообогащенный кремний, внутренний стандартDOI: http://dx.doi.org/10.15826/analitika.2021.25.2.009

High-purity isotopically enriched germanium has been prepared by a hydride method, and the main factors capable of reducing the germanium yield in the monogermane pyrolysis process have been identified. To raise the germanium yield, we have optimized pyrolysis conditions in a laboratory-scale flow apparatus. At a monogermane flow rate at the reactor inlet of 30 mL/min, the optimal monogermane decomposition temperature is 420–450°C. Such conditions ensure a decomposition rate of ~6 g/h and a high product yield and make it possible to obtain most of the germanium in polycrystalline form. Using isotopically enriched monogermane pyrolysis, we have obtained high-purity isotopically enriched germanium samples in the form of polycrystalline ingots with a yield above 95%. The ingots are n-type and range in resistivity from 25 to 50 Ω cm. The content of regulated impurities in the 72Ge-,73Ge-, 74Ge-, and 76Ge-enriched germanium ingots thus prepared does not exceed 0.01 to 1 ppm by weight.

This paper presents a mathematical model for the ultrapurification of substances via distillation in a closed vaporization–condensation system, where vapor condenses on a flowing down liquid film. We jointly analyze the mechanisms behind vaporization, vapor transport, condensation, condensate motion, and impurity diffusion in vaporizing liquid. Examining the removal of cobalt impurities from iron pentacarbonyl as an example, we assess the degree of purification as a function of vaporization and condensation temperatures, vaporization area, the fraction of liquid vaporized, and the radius and height of the condensation tube. Using experimentally determined temperature-dependent effective separation coefficients and the mathematical model, we find diffusion coefficients and equilibrium separation coefficients of cobalt, tungsten, and chromium impurities in iron pentacarbonyl.

Chromatography-mass-spectrometry was used to examine the stability of admixtures of C1−C7 hydrocarbons, fluorine and chlorinated derivatives of hydrocarbons, alkyl derivatives of silane, homologs of monosilane, and siloxanes in monosilane in its storage in molybdenum-glass ampules and stainless-steel cylinders. It was found that, in the case of storage in glass ampules, the concentration of ethylene and tetrafluoroethylene admixtures decreases and that of ethyl silane and disilane increases. When monosilane is stored in a stainless steel cylinder, the concentration of the acetylene admixture it contains changes.

It is for the first time that the method of gas chromatography was used for the determination of silicon fluoride-chlorides SiСl n F 4-n ( n = 0 ÷ 4) which are the initial, intermediate and final substances while producing silicon tetrachloride from silicon tetrachloride and aluminum chloride (III). The analysis of samples taken during this reaction was carried out using the "Tsvet - 800" gas chromatographer. The samples were injected into the instrument using a vacuum dosing system. To separate the components, a chromatographic column made of molybdenum glass with a length of 5 m and an internal diameter of 3 mm was used. It was filled with a Chromatone N-AW-HMDS (grain size 0.250-0.315 mm) with 15% methylsilicon elastoplastic E-301. The registration of silicon fluoride-chlorides was implemented using a thermal conductivity detector. The identification of SiF 4 and SiCl 4 in the mixture was conducted by comparing the times of holding the chromatographic peaks with the times of holding these individual substances. The times of holding not available for SiClF 3 , SiCl 2 F 2 , SiCl 3 F in the individual states were determined using the dependence of the logarithm of the corrected holding time on their molecular mass. The concentrations of silicon fluoride-chlorides were determined using the internal normalization method. The data were obtained on the changes in the concentrations of these substances during the synthesis of silicon tetrachloride. The confirmation of the correctness of the analysis results was made using the method of varying the size of the sample. Key words: silicon fluoride-chlorides, gas chromatography, identification, calibration factor, correctness (Russian) DOI: http://dx.doi.org/10.15826/analitika.2019.23.4.011 Т .G. Sorochkina, О .Yu. Chernova, О .Yu. Troshin, А .Yu. Sozin, А .D. Bulanov, А . А . Ermakov G.G. Devyatykh Institute of Chemistry of High-Purity Substances of the Russian Academy of Sciences, ul. Tropinina 49, Nizhny Novgorod, 603950, Russian Federation

An international comparison study on the accurate determination of the molar mass M(Si) of silicon artificially enriched in 28Si (x(28Si) > 0.9999 mol mol−1) has been completed. The measurements were part of the high level CCQM-P160 pilot study assessing the ability of National Metrology Institutes (NMIs) and Designated Institutes (DIs) to make such measurements at the lowest possible levels of measurement uncertainty and to identify possible difficulties when measuring this kind of sample. This study supports the molar mass measurements critical to disseminating the silicon route to realizing the new definitions for the kilogram and the mole. Measurements were also made by one external research institute and an external company. The different institutes were free to choose their experimental (mass spectrometric) set-ups and equipment, thereby enabling also the comparison of different techniques. The investigated material was a chemically pure, polycrystalline silicon material. The subsequent modified single crystalline secondary product of this material was intended for the production of silicon which was used for two additional spheres in the context of the redetermination of the Avogadro constant NA, required for the revision of the International System of Units (SI) via fundamental constants which came into force from May 2019. The CCQM pilot study was organized by Physikalisch-Technische Bundesanstalt (PTB). Aqueous silicon solutions were shipped to all participating institutions. The data analysis as well as the uncertainty modelling and calculation of the results was predefined. The participants were provided with an uncertainty budget as a GUM Workbench® file as well as a free software license for the duration of the comparison. The agreement of the values of the molar mass (M(Si) = 27.976 942 577 g mol−1) was excellent with ten out of 11 results reported within the range of relative uncertainty of 1 × 10−8 required for the revision of the SI.

This paper examines sources of carbon impurities in polycrystalline monoisotopic 28Si prepared by a hydride method. Analytical data on the concentrations of carbon-containing impurities in volatile silicon compounds (28SiH4 and 28SiH4), process gases (Ar and H2), and polycrystalline 28Si are used to identify the major sources of carbon in the polycrystalline 28Si prepared by the hydride method. These are the starting 28SiH4 and calcium hydride used in 28SiH4 conversion into 28SiH4. The rate of carbon intake into polycrystalline silicon from the apparatus material during the monosilane pyrolysis process does not exceed 9 × 1011 cm–2 h–1. Polycrystalline silicon has been precipitated from monosilane with different concentrations of hydrocarbon impurities. At hydrocarbon concentrations in the range 10–4 to 10–3 mol %, the carbon concentration in the monosilane correlates with that in the silicon obtained from it. High-purity monosilane has been used to prepare polycrystalline 28Si samples with concentrations of carbon impurities in the range (0.8–2.3) × 1015 cm–3. Based on calculations of the carbon impurity distribution along the length of a zone-refined ingot, we examine the effect of the initial carbon concentration in the starting polycrystal on the yield of single-crystal monoisotopic 28Si. Requirements are formulated for the carbon concentration in polycrystalline 28Si which ensure a high yield of single crystals with parameters suitable for metrological applications.

The vapor–liquid separation factors of SiCl4–A (A = SiCl4–nFn (n = 1–4) silicon fluorochloride impurities in silicon tetrachloride have been determined experimentally at 298 K by statically balancing phases. The values obtained for the SiCl4–SiCl3F, SiCl4–SiCl2F2, SiCl4–SiClF3, and SiCl4–SiF4 systems are 4.9 ± 0.8, 8.2 ± 1.2, 29.8 ± 6.1, and 42.0 ± 7.5, respectively. In the SiCl4–SiCl3F system, the vapor–liquid separation factor has also been determined by the Rayleigh distillation method: α = 5.0. The experimental data agree with the vapor–liquid separation factors estimated in conformal solution theory using parameters of the Lennard- Jones potential.

Some features of atmospheric-pressure radiofrequency (13.56 MHz) arc discharge and its use for obtaining bulk samples of isotope-enriched silicon carbide via the reaction between SiF4 and methane in a hydrogen medium have been considered. It has been shown that power in this type of discharge is released mainly in the near-electrode regions. The deposition of silicon and graphite occurs in a layer-by-layer mode, so that the product carbide contains up to 40% free carbon; therefore, the process requires optimization. At the same time, the proposed type of RF arc discharge with the product deposition zone localized at the ends of the electrodes makes it possible to avoid not only additional heating of the reactor space and walls, but also the loss of expensive isotope-enriched silicon fluoride.

The impurity composition of 28SiF4 has been studied for the first time by gas chromatography/mass spectrometry using gas-adsorption capillary columns. For identification and determination of impurity substances by gas chromatography/mass spectrometry, we have proposed using cryogenic preconcentration of the impurities from 28SiF4. The presence of C2–C4 hydrocarbon impurities and sulfur hexafluoride has been confirmed. We have identified 35 impurity substances in 28SiF4, including linear and branched C5–C8 saturated hydrocarbons, aromatic hydrocarbons, chlorine- and fluorine-containing hydrocarbons, and silicon- and sulfur-containing substances, of which 28 have been detected for the first time.

A metrological challenge is currently underway to replace the present definition of the kilogram. One prerequisite for this is that the Avogadro constant, N A, which defines the number of atoms in a mole, needs to be determined with a relative uncertainty of better than 2 × 10−8. The method applied in this case is based on the x-ray crystal density experiment using silicon crystals. The first attempt, in which silicon of natural isotopic composition was used, failed. The solution chosen subsequently was the usage of silicon highly enriched in 28Si from Russia. First, this paper reviews previous efforts from the very first beginnings to an international collaboration with the goal of producing a 28Si single crystal with a mass of 5 kg, an enrichment greater than 0.9999 and of sufficient chemical purity. Then the paper describes the activities of a follow-up project, conducted by PTB, to produce a new generation of highly enriched silicon in order to demonstrate the quasi-industrial and reliable production of more than 12 kg of the 28Si material with enrichments of five nines. The intention of this project is also to show the availability of 28Si single crystals as a guarantee for the future realisation of the redefined kilogram.

Silicon-based quantum bits with electron spins in quantum dots or nuclear spins on dopants are serious contenders in the race for quantum computation. Added to process integration maturity, the lack of nuclear spins in the most abundant $^{28}$silicon isotope host crystal for qubits is a major asset for this silicon quantum technology. We have grown $^{28}$silicon epitaxial layers (epilayers) with an isotopic purity greater than 99.992 % on 300mm natural abundance silicon crystals. The quality of the mono-crystalline isotopically purified epilayer conforms to the same drastic quality requirements as the natural epilayers used in our pre-industrial CMOS facility. The isotopically purified substrates are now ready for the fabrication of silicon qubits using a state-of-the-art 300 mm Si CMOS-foundries equipment and processes, Comment: 7 pages, 7 figures

The results of the precise measurement of the refractive index of stable germanium isotopes Ge72, Ge73, Ge74, and Ge76 single crystals with high enrichment and a germanium single-crystal Genat of natural isotopic composition with the Fourier-transform interference refractometry method from 1.94 to 20 μm with 0.1 cm−1 resolution and accuracy of 2×10−5 to 1×10−4 are shown. The content of 72 impurities measured by the mass spectrometric method was below 10−5–10−6 wt. %. Oxygen and carbon concentrations measured by IR spectroscopy in all crystals are within 5×1015 cm−3. All germanium crystals have a hole conductivity with specific electric resistivity of 45–50 Ohm×cm. The coefficients of the generalized Cauchy dispersion function approximating the experimental refractive index values all over the measuring range are given. The transmission and Raman spectra are also given.

We presented the results on the preparation of high-purity monoisotopic varieties of silicon and germanium. The process involves the separation of isotopes in the form of SiF4 and GeH4 by centrifugation, ultrapurification of volatile compounds, and preparation of poly and single crystals. The attained degree of isotopic and chemical purities of single crystals obtained was shown. The content of the main isotope in the single crystals of 28Si is >99.99% and those in the single crystals of 29Si and 30Si are >99.9%. The specific resistivity of the 28Si single crystals is ∼1 kOhm cm and those of 29Si and 30Si are about 100–150 Ohm cm. The samples of the 76Ge single crystals have the main isotope content of >88 at.% and the difference concentration of electrochemically active impurities of 5·1010 cm−3. The main isotope content in the 74Ge polycrystal is 99.93 at.%. The optical and thermophysical properties of the isotope-enriched silicon and germanium single crystals were measured, which suggest a significant effect of the isopotic composition on thermal capacity, thermal conductivity, luminiscence, and light absorption.

Using high-resolution Fourier-transform IR spectroscopy and gas chromatography, we have identified more than 20 impurity species, in concentrations from 10−1 to 10−5 vol %, in GeF4 samples of different isotopic compositions. The germanium tetrafluoride samples are shown to contain C1–C4 hydrocarbons; hydrogen, carbon, silicon, and sulfur fluorides; fluorogermanes; fluorosilanes; and carbon and nitrogen oxides.

We have recently shown that the dramatic reduction in linewidth of many deep luminescence centers in highly enriched 28 Si can lead to the observation of isotopic fingerprints, revealing not only that a specific element is involved in the defect complex, but also the number of atoms of that element. This has led to many surprises regarding the actual constituents of supposedly well known luminescence centers, as well as the discovery of new members of a family of four-atom centers where the constituents can be chosen from Cu, Ag, Au and Li. Obtaining the isotopic fingerprint of Au is problematic, since only 197 Au is stable, but we have now used the relatively long-lived 195 Au to reveal the presence, and the number, of Au atoms in several of these centers. We find a series of four-atom centers containing one Au plus Cu and/or Li. Surprisingly, the Au isotopic fingerprint also reveals a series of five-atom centers containing a single Au plus Cu and/or Li. Further evidence for the ubiquity of these four- and five-atom defects is provided by two previously observed Pt-related centers, with luminescence at 884 and 777 meV, which are present in these samples due to the decay of 195 Au to 195 Pt. In addition to Pt, these centers are found to contain three and four Cu atoms, respectively.

The current status of the problem of obtaining high-purity silicon isotopes 28Si, 29Si, and 30Si is analyzed. The scheme of obtaining monoisotopic silicon includes the stages of isotope separation in the form SiF4, synthesis and deep purification of isotopically enriched silane, obtaining polycrystalline silicon-28,-29, and-30, and growing monocrystals. The basic problems and methods of their solution in the synthesis and deep purification of silane and obtaining poly-and monocrystals of isotopically enriched silicon are discussed. Data characterizing the achieved level of chemical and isotopic purity of high-purity monocrystals of silicon-28 with a main isotope content of more than 99.99% and silicon-29 and silicon-30 with isotopic purity higher than 99% are presented. In monocrystalline 28Si, the boron content was 4.5 × 1013, the phosphorus content was 5 × 1011, the carbon and oxygen contents were

The synthesis of silane by reacting silicon tetrafluoride and calcium hydride is shown to proceed as a propagating wave. The main parameters of the process, namely, the propagation velocity, the reaction front temperature, and calcium conversion, are determined. The mathematical model of wave propagation for an exothermic reaction in a porous medium with purging a gaseous oxidant describes qualitatively the major laws of the process.

We present a study of excitons bound to sulphur- and copper-related isoelectronic centres in highly enriched 28Si. The S-related centre, which has been shown to have two configurations, SA and SB, was believed to consist of a substitutional sulphur atom paired with an interstitial copper atom. High resolution photoluminescence (PL) emissions from the no-phonon S B 0 transition reveal fine structure not observable in natural silicon. In both 28Si:natS and 28Si:34S, low temperature PL reveals at least 18 distinct components of the S B 0 system, including a triplet splitting seen in natSi:natS by optical detection of magnetic resonance. Investigation of the effect of copper isotopic composition on the S B 0 system shows that the centre contains at least three copper atoms. We also present results of the copper isotope effect on the 943.7 meV *Cu00 system in 28Si and show that three Cu atoms contribute to the Cu isotope shift of *Cu00.

The chalcogen deep double donor sulfur (S) has been studied extensively with optical methods in natural silicon ( Si nat ) . Recently, it was shown that the spectroscopic linewidths of absorption transitions from shallow impurities like boron and phosphorus is limited by inhomogeneous broadening due to a Si isotope effect which is removed with the use of highly enriched 28Si. In this work we extend these results to deep centers and show that the true homogeneous linewidths of many transitions can only be revealed in isotopically enriched Si. The S + 1 s ( T 2 ) Γ 7 transition exhibits a full width at half maximum (FWHM) of only 0.008 cm - 1 in 28Si—more than one order of magnitude sharper than in Si nat , and substantially narrower than the sharpest transitions of B and P in 28Si. Hence, it is the narrowest absorption line ever seen for impurity states in semiconductors. We also report dramatically narrower absorption transitions for the neutral S 0 center, together with higher excited states than previously observed. The isotope shifts of S absorption transitions between Si nat , 28Si and 30Si are also reported.

Electron spin resonance (ESR) is used to study the neutron transmutation doping of silicon crystals enriched with 30Si isotope: phosphorus donors and radiation defects produced in the course of transmutational doping are observed. The ESR signals related to the phosphorus uncontrolled impurity in 30Si before transmutational doping (the P concentration is ∼1015 cm−3) and phosphorus introduced by neutron irradiation with doses ∼1 × 1019 cm−2 and ∼1 × 1020 cm−2 (the P concentrations are ∼5 × 1016 and ∼7 × 1017 cm−3, respectively) are studied. As a result of drastic narrowing of the phosphorus ESR lines in 30Si, the intensity of lines increased appreciably, which made it possible to measure the phosphorus concentration in the samples with a small volume (down to 10−6 mm−3). The methods for determining the concentration of P donors from hyperfine structure in the ESR spectra of isolated P atoms, exchange-related pairs, and clusters that consist of three, four, and more P donors are developed. In the region of high concentrations of P donors, in which case the hyperfine structure disappears, the concentration of P donors was estimated from the exchange-narrowed ESR line.

Phosphorus-doped silicon 30Si monoisotope samples with a highly homogeneous impurity distribution at a concentration of 5 × 1016 cm−3 were obtained for the first time by means of neutron transmutation doping.

The impurity contents of different silicon tetrafluoride samples (isotopically unmodified and enriched) are determined by optical emission spectroscopy with the preconcentration of nonvolatile impurities by distilling off SiF4 .

We report the successful isotope separation and bulk single crystal growth of 29Si and 30Si stable isotopes. The isotopic enrichments of the 29Si and 30Si single crystals determined by mass spectrometry are 99.23% and 99.74%, respectively. Both crystals have the electrically active net-impurity concentration less than 1015 cm-3. Thanks to the result of this work and the 28Si crystals we grew previously, high quality single crystals of every stable Si isotope (28Si, 29Si, and 30Si) have been made available for a wide variety of basic research and industrial applications.

Silicon tetrafluoride was obtained by the thermal decomposition of pure-grade sodium hexafluorosilicate and purified by low-temperature distillation. Next, SiF4 was 28Si-enriched by centrifugation and converted to silane by calcium hydride reduction. To remove hydrocarbons, the silane was distilled.

The possibility of the reduction of hexafluorodisiloxane by calcium hydride in the synthesis of silane from silicon tetrafluoride has been studied. This reaction is shown to be not decisive for oxygen contamination of silane. The most likely reason for the appearance of impurity Si2OH6 in “fluoride” silane is the Ca(OH)2-catalyzed reaction of silane with trace water. The concentration of impurity Si2OH6 in silane at the stage of synthesis may be efficiently decreased by the preliminary purging of calcium hydride with a hydrogen (grade A) flow.

We presented the results on the preparation of high-purity monoisotopic varieties of silicon and germanium. The process involves the separation of isotopes in the form of SiF4 and GeH4 by centrifugation, ultrapurification of volatile compounds, and preparation of poly and single crystals. The attained degree of isotopic and chemical purities of single crystals obtained was shown. The content of the main isotope in the single crystals of 28Si is >99.99% and those in the single crystals of 29Si and 30Si are >99.9%. The specific resistivity of the 28Si single crystals is ∼1 kOhm cm and those of 29Si and 30Si are about 100–150 Ohm cm. The samples of the 76Ge single crystals have the main isotope content of >88 at.% and the difference concentration of electrochemically active impurities of 5·1010 cm−3. The main isotope content in the 74Ge polycrystal is 99.93 at.%. The optical and thermophysical properties of the isotope-enriched silicon and germanium single crystals were measured, which suggest a significant effect of the isopotic composition on thermal capacity, thermal conductivity, luminiscence, and light absorption.

Using high-temperature oxidation, the residual carbon content of high-purity sulfur was reduced to 10–5wt %. The effects of the oxidation temperature and duration on the efficiency of the process were studied. The results are used to elucidate the mechanism for the removal of carboniferous impurities in the course of purification.

We report on the growth of 99,9 % enriched 28 Si, dislocation free monocrystals (111- and 100-orientated) with nearly 10 g weight and less than 10 15 foreign atoms/cm 3 .

A gas-chromatographic procedure was developed for the determination of carbon-containing impurities in sulfur with a detection limit of 6 x 10-6%. Carbon-containing substances and elemental carbon can be effectively separated from sulfur samples as CO2 and COS.

The behavior of carboniferous impurities during thermochemical purification of sulfur was studied. The integral absorption coefficient for the IR absorption band at 2920 cm-1, related to aliphatic hydrocarbons, was determined. The detection limit for aliphatic hydrocarbons in sulfur was evaluated to be 2 x 10-5 wt % (3σ criterion).

High-purity isotopically enriched (99.98% 28Si, 99.57% 29Si, and 99.83% 30Si) silane samples are prepared for the first time. The total hydrocarbon content of the samples is no higher than 0.1–0.3 ppm. The concentration of electroactive impurities in the silicon prepared from the purified monoisotopic silane is below 1015 cm–3.

Suspended particles were determined in sulfur by laser ultramicroscopy after transferring the test sample to the liquid state while retaining the spectrum of particle sizes. An automated laser particle analyzer for high-purity liquids is described, and the results of analyses of samples of high-purity sulfur are presented

A procedure was developed for determining impurity arsenic in high-purity sulfur with a detection limit of 1 × 10–7 wt %. The samples of sulfur to be studied were dissolved in nitric acid in an autoclave, and then the arsenic impurity was extracted with toluene and back-extracted with distilled water. Arsenic was determined in the back-extract by electrothermal atomic-absorption spectrometry.

While the first comparison of shallow bound exciton photoluminescence between natural Si and highly enriched $^{28}\text{S}\text{i}$ dramatically demonstrated the importance of inhomogeneous isotope broadening, the transitions in $^{28}\text{S}\text{i}$ were in fact too narrow to be resolved with the then available instrumental resolution of $0.014\text{ }{\text{cm}}^{\ensuremath{-}1}$. We report results for the boron bound exciton transition in highly enriched $^{28}\text{S}\text{i}$ using a novel apparatus for photoluminescence excitation spectroscopy based on a tuneable single-frequency laser source with sub-MHz resolution. Twenty well-resolved doublets, exhibiting a $^{10}\text{B}--^{11}\text{B}$ isotope splitting, are observed in the new spectra for $^{28}\text{S}\text{i}$ with isotopic enrichment $g99.99%$. Linewidths as narrow as $0.0012\text{ }{\text{cm}}^{\ensuremath{-}1}$ (150 neV) full width at half maximum are observed for the most highly enriched sample.

Inhomogeneous broadening due to isotopic randomness in natural Si has been shown to cause a broadening of many of the ground-state to excited-state infrared-absorption transitions of the shallow donor phosphorus and acceptor boron. Previously, it had been thought that the observed linewidths of shallow impurity transitions in silicon were at their fundamental lifetime limit. We report improved high-resolution infrared-absorption studies of these transitions in new samples of isotopically enriched $^{28}\text{S}\text{i}$, $^{29}\text{S}\text{i}$, and $^{30}\text{S}\text{i}$. Some of the transitions in $^{28}\text{S}\text{i}$ show the narrowest linewidths ever reported for shallow donor and acceptor absorption transitions, and many higher excited states are now observed. The improved samples of $^{29}\text{S}\text{i}$ and $^{30}\text{S}\text{i}$ result in revised values for the dependence of shallow donor and acceptor binding energies on the average Si mass.

Karaiskaj et al. showed that the isotopic randomness present in natural Si (natSi) causes inhomogeneous broadening of many of the ground state to excited state infrared absorption transitions of the shallow donor phosphorous and acceptor boron. This was surprising since it was thought that the observed linewidths of shallow impurities in silicon are at their fundamental lifetime limit. We report improved high‐resolution infrared absorption studies of these impurities in isotopically enriched 28Si, 29Si and 30Si. The new data improves on the linewidths of earlier spectra due to reduced concentration broadening. Some of the transitions in 28Si show the narrowest FWHM ever reported for shallow donor and acceptor absorption transitions.

We resolve the remarkably sharp bound exciton transitions of highly enriched 28 Si using a singlefrequency laser and photoluminescence excitation spectroscopy, as well as photocurrent spectroscopy. Well-resolved doublets in the spectrum of the 31 P donor reflect the hyperfine coupling of the electronic and nuclear donor spins. The optical detection of the nuclear spin state, and selective pumping and ionization of donors in specific electronic and nuclear spin states, suggests a number of new possibilities which could be useful for the realization of silicon-based quantum computers.