Spectrophotometric and polarographic methods for the determination of silicon at ng/g levels in gallium arsenide

Summary Spectrophotometric and differential pulse polarographic determinations of silicon in gallium arsenide as heteropoly acid have been established. The analysis comprises decomposition with a mixture of hydrochloric acid and bromine in a PTFE vessel, elimination of matrix elements by evaporation of arsenic as arsenic trichloride and extraction of gallium as gallium tetrachloro-complex anion by di-isopropyl ether, and finally spectrophotometric determination of silicomolybdenum blue or polarographic determination of -silicomolybdic acid. Optimization of sample pretreatment procedures and instrumental determination have been carefully elaborated. The detection limits of the developed methods were found to be 7 ppb and 5 ppb, respectively, for spectrophotometry and polarography. The proposed methods have been practically applied to the analysis of various Si-doped samples. The results obtained by the chemical methods are compared with those from the electrical measurement and the discrepancies found are discussed.

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Spektralphotometrische und polarographische Bestimmung von Silicium in Galliumarsenid im ng/g-Bereich

Zusammenfassung Die beschriebenen Verfahren beruhen auf der Si-Bestimmung als Heteropolysäure. Sie umfassen den Aufschluß der Probe mit Salzsäure und Brom im PTFE-Gefäß, Eliminierung der Matrixelemente (Verdampfung von Arsen als Arsentrichlorid und Extraktion von Ga als Tetrachlorokomplex mit Diisopropylether) sowie anschließende spektralphotometrische Bestimmung als Silicomolybdänblau oder polarographische Bestimmung als -Silicomolybdänsäure. Die Optimierung der Vorbehandlungstechnik sowie der instrumentellen Analysenparameter wird beschrieben. Die Nachweisgrenzen liegen bei 7 ppb bzw. 5 ppb. Die vorgeschlagenen Methoden wurden auf verschiedene Sidotierte Proben angewendet. Die Ergebnisse werden verglichen und Unterschiede diskutiert.

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Presented at the Colloquium Spectroscopicum Internationale XXIV, September 15–20, 1985, Garmisch-Partenkirchen, FRG     

On the formation of the crystalline phases and nanostructure of silicon carbonitride layers grown on gallium arsenide substrates

The crystallization of thin silicon carbonitride layers obtained by chemical vapor deposition from silicon organic precursors on gallium arsenide substrates at 973 K in the presence of liquid gallium drops is studied. The layers grown by the vapor-liquid-solid method are studied by IR, Raman, and energy dispersive spectroscopy, scanning electron microscopy, and X-ray diffraction using synchrotron radiation in order to determine their chemical and phase composition, crystal structure, and surface morphology. Their morphology is supposed to be associated with the formation of nuclei in a gallium drop located at the surface of the gallium arsenide substrate.     

Instrumental neutron activation analysis of high-purity gallium,arsenic, and gallium arsenide

Instrumental neutron activation analysis (INAA) has been applied to obtain useful data on impurity concentrations in ultra-pure materials whose matrix elements are strongly activated and create severe interference for several weeks after irradiation. An analytical procedure has been developed and used to determine Sc, Fe, Co, Zn, Se, Zr, Ag, In, Sn, Sb, Te, and Hg in high-purity gallium, arsenic, and gallium arsenide. Detection limits ranged from 50 ng/g for iron to 0.001 ng/g for scandium. Problems of contamination control, blank level, and standardization are discussed.     

Determination of iron in high purity gallium arsenide, gallium and arsenic as the bathophenanthroline complex

Summary A spectrophotometric method is described for the determination of iron in high purity GaAs and As or Ga, having a limit of detection of 3.5×10^–5% and 7×10^–5% Fe, resp. After sample dissolution and pre-reduction of Fe³⁺ to the bivalent state with hydroxylammonium chloride the red iron(II)-bathophenanthroline complex is formed in the presence of sodium citrate, ascorbic acid and perchlorate. It is extracted into chloroform and optical density of the resulting extract is measured at 533 nm. The effect of copper is discussed. The procedure is stated to be rapid and applicable not only to Ga, As and GaAs, but also to other materials.

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Zusammenfassung Es wird eine spektralphotometrische Methode zur Eisenbestimmung in Ga oder As und GaAs mit Nachweisgrenzen von 3,5 · 10^–5% bzw. 7,0 · 10^–5% Fe beschrieben. Nach Lösung der Probe und Vorreduktion des Eisens mit Hydroxylammoniumchlorid wird in Anwesenheit von Natriumcitrat, Ascorbinsäure und Perchlorat ein roter Komplex von Eisen(II)-bathophenanthrolin gebildet, der mit Chloroform extrahiert wird und dessen optische Dichte bei 533 nm gemessen wird. Der Einfluß des Kupfers wird diskutiert. Die vorgeschlagene Methode ist schnell durchfÜhrbar und kann nicht nur fÜr Ga, As und GaAs, sondern auch fÜr andere Materialien angewendet werden.

     

Activation analysis for selenium and tellurium trace impurities in gallium, arsenic and gallium arsenide

Destructive and non-destructive activation analysis for selenium and tellurium has been studied. In destructive analysis the selenium and tellurium activities are co-extracted from the irradiated and dissolved matrix elements with dithizone/CCl(4), reagent in a hot-chamber by remote manipulation, then separated from each other by diethylammonium-N,N-diethyldithiocarbamate/CCl(4) extraction, tellurium going into the organic phase and selenium being retained by the aqueous phase. The sensitivity of the method is 10(-8)g for both elements. By non-destructive methods, selenium can be determined down to 10(-6)g on short irradiation, and down to 3 x 10(-8) g on long irradiation and cooling, and tellurium down to 10(-6) g with long irradiation and cooling.     

Use of the ion microanalyzer for the characterization of bulk and epitaxial silicon and gallium arsenide

The ion microanalyzer permits a localized mass spectrometric analysis, i.e. the qualitative and quantitative analysis of the impurities contained in a small selected volume. This procedure makes possible the analysis of very thin epitaxial layers (for example silicon and gallium arsenide). As regards qualitative analysis, the apparatus is designed for the selection of ions. After the recording and analysis of the ion spectrum, a large number of the impurities present in the sample are determined qualitatively. Quantitative analysis can be performed with the equipment, but this requires the analysis of a homogeneous standard sample previously dosed by spark-source mass spectrometry. The quantitative analysis of bulk and epitaxial silicon and gallium arsenide is described and the limits of detection of the principal impurities are given. It is also shown how the possibility of localized analysis was exploited. A correlation was established between the existing impurities and the chemically revealed crystal imperfections. A comparative analysis of the distribution of the impurities in the epitaxial layers was also carried out. The periodic analysis of epitaxial layers makes it possible to follow the deterioration by contamination, if any, under the epitaxial conditions, and to improve the sample quality.     

Atomic absorption spectrometric methods for analysis of high-purity gallium and rhenium and layers of doped ilicon

Atomic absorption spectrometry with electrothermal atomization is used to determine 13 and 15 elements in high-purity rhenium and gallium, respectively. Flame emission is used for K, Na and Li. Improved detection limits are achieved by extraction of the matrix. Thin films (0.01–l μm)of doped silicon are analyzed for As, Sb, In and Tl by a similar atomic absorption method, after chemical or electrochemical stripping of the layers.     

Photochemical functionalization of gallium nitride thin films with molecular and biomolecular layers

We demonstrate that photochemical functionalization can be used to functionalize and photopattern the surface of gallium nitride crystalline thin films with well-defined molecular and biomolecular layers. GaN(0001) surfaces exposed to a hydrogen plasma will react with organic molecules bearing an alkene (C=C) group when illuminated with 254 nm light. Using a bifunctional molecule with an alkene group at one end and a protected amine group at the other, this process can be used to link the alkene group to the surface, leaving the protected amine exposed. Using a simple contact mask, we demonstrate the ability to directly pattern the spatial distribution of these protected amine groups on the surface with a lateral resolution of <12 mum. After deprotection of the amines, single-stranded DNA oligonucleotides were linked to the surface using a bifunctional cross-linker. Measurements using fluorescently labeled complementary and noncomplementary sequences show that the DNA-modified GaN surfaces exhibit excellent selectivity, while repeated cycles of hybridization and denaturation in urea show good stability. These results demonstrate that photochemical functionalization can be used as an attractive starting point for interfacing molecular and biomolecular systems with GaN and other compound semiconductors.     

Comparative evaluation of extraction methods for simultaneous mass-spectrometric analysis of complex lipids and primary metabolites from human blood plasma

Metabolomic results on human blood plasma largely depend on the sample preparation protocols employed for protein precipitation and metabolite extraction. Five different extraction methods were examined, which can be grouped into two categories, liquid-liquid extraction and protein precipitation methods, including long-standing protocols such as the Folch extraction and Bligh-Dyer extraction in comparison to modern methods such as the Matyash protocol and two global metabolite extraction methods. Extracts were subjected to analysis of blood plasma lipids and primary metabolites by using chip-based direct infusion nanoelectrospray tandem mass spectrometry and gas chromatography coupled to time-of-flight mass spectrometry, respectively. Optimal extraction schemes were evaluated based on the number of identified metabolites, extraction efficiency, compound diversity, reproducibility, and convenience for high-throughput sample preparations. Results showed that Folch and Matyash methods were equally valid and robust for lipidomic assessments while primary metabolites were better assessed by the protein precipitation methods with organic solvent mixtures. Graphical Abstract

Schematic workflow of five extraction methods and subsequent mass spectrometry analysis using GC-TOF MS and nanoelectrospray direct-infusion ion trap MS/MS?     

Rate constants for the etching of gallium arsenide by atomic chlorine

Known chlorine atom concentrations were prepared in a discharge flow system and used to etch the (100) face of a gallium arsenide single crystal. The etch rate was monitored by mass spectrometry, laser interferometry, and surface proftlometry. In the temperature range from 90 to 160°C the reaction can be described by the rate law $$Etch rate = kP_{Cl} $$ where $$k = 9 \times 10^{(6 \pm 0.5)} \mu m min^{ - 1} Torr^{ - 1} e^{ - 9 \pm 1)kcal/RT} $$      

Characterization of native and heterooxide layers on compound semiconductors by combined use of surface analysis methods

Summary Structure, formation and interface reactions of anodic oxides and SiO₂ on Cd_xHg_1–xTe have been studied by means of SIMS, AES, XPS, TDMS and the electron microprobe as an example for the application of surface analysis to compound and semiconductor passivation systems.

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Charakterisierung von Eigenoxid- und Heterooxidschichten auf Mehrkomponentenhalbleitern durch kombinierten Einsatz oberflächenanalytischer Verfahren

Zusammenfassung Aufbau, Bildungsmechanismus und Grenzflächenreaktionen von anodischen Oxiden und Quarz auf Cd_xHg_1–xTe wurden mit SIMS, AES, XPS, TDMS, SNMS und der Elektronenstrahlmikrosonde untersucht.

     

Some topical applications of plasma atomic spectrochemical methods for the analysis of ceramic powders

The scope of a number of plasma spectrochemical methods for the determination of the main components and impurities in ceramic powders is described. These methods meet the requirements for the analytical characterization of new structural and functional ceramics for modern industrial applications and electronic devices. For ceramic powders, spectrochemical analysis with direct methods as well as analysis subsequent to sample dissolution are discussed. Fusion is a powerful method for the dissolution of ZrO₂ ceramic powders, provided the fluxes are pure enough. For determinations in Al₂O₃, SiC and ZrO₂, it will be shown that ICP-MS is very useful. This is especially true for trace analysis after matrix removal. The latter can easily be performed on-line in the case of the analysis of Al₂O₃ powders. For direct analysis of ceramic powders, the direct insertion of samples into the plasma, spark and arc ablation, laser ablation, electrothermal vaporization and slurry nebulization are discussed. Particular attention is given to the direct analysis of ceramics in powder form (Al₂O₃, SiC, Si₃N₄, B₄, WC) using ICP-OES with slurry nebulization as well as with direct sample insertion (DSI) and with electrothermal vaporization (ETV). For the two latter methods, the use of chemical modifiers for volatile compound formation will be shown to be of great importance, and its features will be explained using thermochemical considerations.     

A two-jet plasmatron for the spectrochemical analysis of geological samples

The analytical possibilities with a two-jet plasmatron with non-consumable electrodes have been investigated. Large amounts of easily ionised additives present in the plasma enhance atom line intensities of trace elements, the effect being greater the lower the ionisation potential of the element but the effect on ion line intensities is not significant. The temperature of the plasma is only slightly affected by the ionisation potential of the substance introduced into the plasma.Analytical errors caused by variations in the matrix and mineralogical composition of samples are of the same order as the random error of analysis. The analysis of different types of rock samples can be made using a single standard procedure giving a relative standard deviation of 4–6 % and detection limits between 10^?5 and 10^?7 %. A feature of the analytical method is the direct analysis of solid samples.     

Some topical applications of plasma atomic spectrochemical methods for the analysis of ceramic powders

The scope of a number of plasma spectrochemical methods for the determination of the main components and impurities in ceramic powders is described. These methods meet the requirements for the analytical characterization of new structural and functional ceramics for modern industrial applications and electronic devices. For ceramic powders, spectrochemical analysis with direct methods as well as analysis subsequent to sample dissolution are discussed. Fusion is a powerful method for the dissolution of ZrO₂ ceramic powders, provided the fluxes are pure enough. For determinations in Al₂O₃, SiC and ZrO₂, it will be shown that ICP-MS is very useful. This is especially true for trace analysis after matrix removal. The latter can easily be performed on-line in the case of the analysis of Al₂O₃ powders. For direct analysis of ceramic powders, the direct insertion of samples into the plasma, spark and arc ablation, laser ablation, electrothermal vaporization and slurry nebulization are discussed. Particular attention is given to the direct analysis of ceramics in powder form (Al₂O₃, SiC, Si₃N₄, B₄, WC) using ICP-OES with slurry nebulization as well as with direct sample insertion (DSI) and with electrothermal vaporization (ETV). For the two latter methods, the use of chemical modifiers for volatile compound formation will be shown to be of great importance, and its features will be explained using thermochemical considerations. Received: 18 February 1998 / Revised: 13 May 1998 / Accepted: 9 June 1998     

Plasmochemical synthesis of thin layers of the sulfur doped silicon dioxide

Plasmochemical synthesis of thin layers of the sulfur atoms doped SiO₂ on the basis of volatile Siorganoelement compounds containing the Si-S fragments was studied. Highly pure trimethyl-ethylthiosilane Me₃SiSEt was used as a precursor for deposition of the sulfur-silicate glass. SiO₂ layers with designated composition and properties required for construction of modern microelectronic devices were obtained.     

Radiofrequency spark source mass spectrometric analysis of oxygen in undoped silicon crystals and of carbon in undoped and carbon doped gallium arsenide crystals

Radiofrequency spark source mass spectrometry is a reliable and precise analytical method to measure the amount of oxygen in silicon grown by the Czochralski technique from SiO₂ crucibles in the common range from 2ppm(atomic) to 20ppm(atomic) and in silicon grown by the floating zone technique below 0.1ppm(atomic). The technique is also excellent for the measurement of the amount of carbon in semi-insulating gallium arsenide grown under low and high pressure N₂ ambient gas by the B₂O₃ encapsulated Czochralski technique from pyrolytic BN crucibles in the common range from 0.02ppm(atomic) to 0.4ppm(atomic). The results are in rather good agreement with concentrations measured by charged particle activation analysis and consistent with those obtained using other methods.     

Trace analysis of gallium arsenide by selective evaporation of the matrix with bromine vapours

Gallium arsenide samples are analyzed by graphite furnace AAS after the selective evaporation of the matrix elements as bromides with bromine vapours in a simple apparatus. The evaporation step is carried out at 280–300 ° C and it is accomplished for 0.5 g sample within 1 h. Reproducibilities of 5 to 20% were obtained. Detection limits (3 s, in ng/g) are 20 (Fe), 5.0 (Ca), 3.0 (Mg), 2.0 (Ni, Cu), 1.0 (Al), 0.5 (Pb, Co), 0.2 (Mn, Cr).     

Rate constants for the reaction of atomic and molecular bromine with gallium arsenide

The reaction of the (100) face of a gallium arsenide single crystal with atomic and molecular bromine has been studied in a discharge flow system at temperatures between 100 and 225°C and pressures between 0.1 and 40 torr. The reaction with Br₂ was found to be first order in Br₂ only at pressures below 1 torr. Temperature dependence studies in the linear range gave the activation energy and preexponential factor for the rate controlling reaction in the low pressure regime. The results are summarized in the following Arrhenius equation: Deviations from linearity at high pressures are discussed in terms of two alternative mechanisms. The reaction of GaAs with atomic bromine was also studied as a function of temperature, and found to have a temperature dependence described by the following Arrhenius equation:      

High-sensitivity transmission IR spectroscopy for the chemical identification and structural analysis of conjugated molecules on gallium arsenide surfaces

We demonstrate the use of high-sensitivity, off-normal transmission IR spectroscopy with s-polarized light to probe the chemical identity and orientation of quaterphenyldithiol (QPDT) molecular assemblies on GaAs as a function of ammonium hydroxide (NH4OH) concentration. NH4OH is added to the assembly solution to convert the thioacetyl groups on the QPDT precursor to thiolates. When assembled at high NH4OH concentrations, the acetyl groups are completely removed, and QPDT is disordered on GaAs. Assembly at low NH4OH concentrations, however, results in QPDT assemblies that are preferentially upright. The molecular orientation is further quantified with near-edge X-ray absorption fine structure spectroscopy.     

A critical review of atomic absorption, spectrochemical, and x-ray fluorescence methods for the determination of the noble metals--II

The review is a continuation of the initial reviews and covers the period of abstracting up to and including April, 1967. Work on the atomic-absorption determination of noble metals is also included.