Special preparation techniques have to be applied for trans-mission electron microscope (TEM) failure analysis of ULSI devices as well as for technology characterization of non-periodic test patterns to obtain information from volumes as small as 1 × 1× 1 μm3. These regions may be prepared either as thin cross sections or as planview specimens by making use of a well established precision polishing technique. In this article strategical preparation steps are described which have to be thought of and carried out depending on the specific problem before the specimen is actually thinned. This comprises the choice of localization and marking techniques for the area of interest and the consideration whether layers which cover the surface of the Si substrate and impede TEM observation should be removed by either chemical or mechanical means. Precise ion milling of planview specimens becomes necessary to remove thin residual polycrystalline layers on the Si substrate which disturb TEM observation of defects in the silicon near-surface zone due to diffraction contrast. Particular problems require specimens a few micrometers thick, to be studied in an 1 MV TEM first in order to locate the exact position of the interesting features. Further ion milling may then provide a thin specimen usable for characterization by imaging and composition analysis. The varoius approaches and procedures will be illustrated by numerous examples taken from memory and logic device technology.

For via hole filling in very- and ultra-large-scale integrated application, a CVD-W process with an additional, intermediate chemical vapor deposited WSi(x) layer between Al and W was successfully applied. The approximately 150 nm thick WSi(x) layer was characterized in detail by analytical transmission electron microscopy. After various heat-treatments, the crystalline fraction of the mainly amorphous WSi(x) consists predominantly of beta-W and/or hexagonal W(Si, Al)2. With increasing thermal load Al diffuses into the WSi(x) resulting in the formation of Kirkendall pores.

By crystallization from aqueous solution or heating aqueous suspensions of the corresponding monohydrates in a vacuum, single crystals of Sr(BrO 3 ) 2 , Sr(ClO 3 ) 2 , Ba(BrO 3 ) 2 , Pb(ClO 3 ) 2 , and Pb(BrO 3 ) 2 have been obtained for the first time.

The i.r. and Raman spectra including Raman single crystal measurements of the isostructural series Ba(ClO3)2 · H2O, Ba(BrO3)2 · H2O, Sr(BrO3)2 · H2O and Sr(IO3)2 · H2O and of deuterated samples are presented for the range 200–700 cm−1 at 90 and 295 K and assigned to the unit cell group modes of both H2O librational and XO3 bending vibrations. The spectra reveal strong mixing of the H2O, HDO and D2O librational modes (Rr,Rt, Ry) with the XO3 bending vibrations ν2 and ν4. This coupling, which can be used for assignment of the librational modes, causes intensity transfers and frequency shifts up to 30 cm−1 compared to the unmixed modes. The strong temperature dependence of halfwidth and intensity of the H2O librational modes is probably due to orientational disorder of the water molecules. The intensity of the H2O twisting modes in both the Raman and i.r. spectra are discussed in terms of site symmetry (C2 or C1 in the case of orientational disorder) and bonding structure of the water molecules.

AbstractDurch Kristallisation aus wässeriger Lösung bzw. durch Erhitzen einer wässerigen Aufschlämmung der entsprechenden Hydrate auf 95, 185, 130 und 105°C im Vakuum konnten erstmals Einkristalle der bisher nur sehr unvollständig charakterisierten wasserfreien Halogenate Sr(ClO3)2, Sr(BrO3)2, Ba(BrO3)2, Pb(ClO3)2 und Pb(BrO3)2 dargestellt werden. Die Halogenate kristallisieren in der orthorhombischen Raumgruppe Fdd2‐C (Z = 8) mit Ausnahme des Sr(BrO3)2, welches monoklin verzerrt ist (Raumgruppe CcC, Z = 4). Von Sr(ClO3)2 und Sr(BrO3)2 wurde eine Röntgenstrukturanalyse durchgeführt. In beiden Verbindungen liegen verzerrte, über vier Ecken zu einem dreidimensionalen Netzwerk verknüpfte SrO8‐Bisphenoide (Dodekaeder) vor. Die Chlorationen sowie eines der beiden kristallographisch nicht äquivalenten Bromationen sind relativ stark verzerrt. Die Strukturen dieser Verbindungen sowie die des Ba(IO3)2 und des Ba(ClO3)2 · 1 H2O‐Typs lassen sich auf eine hypothetische AB2‐Struktur mit diamantartiger Anordnung der Metallionen in der gemeinsamen Übergruppe Fddd–D zurückführen. Die IR‐ und Ramanspektren werden mitgeteilt und mit dem Ergebnis der Strukturanalyse verglichen.

The i.r. and Raman spectra including Raman single crystal measurements of the isostructural Ba(ClO3)2·H2O, Ba(BrO3)2·H2O, Sr(BrO3)2·H2O, and Sr(IO3)2·H2O and of Ba(ClO3)2·H2O-Ba(BrO3)2·H2O solid solutions are presented in the water band and the XO stretching mode region at 90 and 295 K. Assignment of the XO stretching modes to the intramolecular vibrations v1 and v3 of the halate ions and the species of the unit cell group C2h is performed and discussed in terms of the relative intensity of the i.r. and Raman bands, the frequency shifting among the halate monohydrates, the single crystal Raman spectra and the spectra of matrix isolated ClO−3 and BrO−3 ions. The effective XO stretching force constants are in the order ClO−3 > lO−3 > BrO−3. The order of v1 and v3 is v1 < v3 for ClO−3 and v1 > v3 for BrO−3 and IO−3·.33Cl/37Cl isotopic splitting of the ClO stretching modes, as discussed formerly, can be excluded. The spectra of matrix isolated ClO3−3 and BrO−3 ions (site symmetry C1) show three XO stretching bands (one v1 and two v3). The frequency shifting of the OH stretching modes resembles that of other isostructural solid hydrates with weak hydrogen bonds. It can be correlated to the repulsion potential of the lattice and the metal—water interaction.

High-temperature Raman spectra are used for studying the thermal decomposition of ZnSO3·2 H2O, MgSO3·6 H2O and MgSO3·3 H2O.

Die wasserfreien Sulfite (I)‐(IV) werden durch Gelkristallisation in einem Kieselsäuregel erstmals einkristallin erhalten.

AbstractDurch Gelkristallisation in einem Kieselsäuregel konnten erstmals Einkristalle der wasserfreien Sulfite BaSO3, CdSO3‐I, PbSO3 und Na2Cd3(SO3)4 sowie der bisher nicht bekannten Sulfite CdSO3‐II und CdSO3‐III erhalten werden. Die Gitterdaten folgender Sulfite wurden anhand von Einkristallmessungen bestimmt: SrSO3 und BaSO3 (P21/m): a = 634,4(1), b = 526,7(1), c = 443,3(1) pm, β = 106,51(1)° und a = 664,9(1), b = 549,0(1), c = 464,7(1) pm, β = 106,25(1)°, Z = 2, PbSO3 (Pnma): a = 790,3(1), b = 548,8(1), c = 680,2(1) pm, Z = 4, CdSO3‐I (P21/c): a = 443,9(1), b = 860,8(1), c = 718,3(1) pm, β = 94,53(1)°, Z = 4, CdSO3‐II (P21/c): a = 554,7(1), b = 1254,2(1), c = 849,9(1) pm, β = 100,00(1)°, Z = 8, CdSO3‐III (R3): a = 814,5(1) pm, α = 109,04(1)°, Z = 6, Na2Cd3(SO3)4 (C2/c, Cc): a = 1612,8(2), b = 537,2(1), c = 1293,6(1) pm, β = 90,17(1)°, Z = 4. Die IR‐ und Ramanspektren sowie das Ergebnis thermoanalytischer Messungen (DTA, TG, DTG, Röntgenheizaufnahmen) werden diskutiert. Von den drei polymorphen Cadmiumsulfiten ist CdSO3‐I die bei Raumtemperatur thermodynamisch stabile Form.

AbstractDurch Kristallisation aus natriumhaltigen wässerigen Sulfitlösungen wurden bisher nicht bekannte Hydroxidsulfite des Typs NaM2OH(SO3)2 · 1 H2O mit M = Mg, Mn, Fe, Co, Ni und Zn erhalten. Die Kristallstruktur, die IR‐ und Ramanspektren sowie das Ergebnis thermoanalytischer Untersuchungen werden mitgeteilt und diskutiert. Die Verbindungen zeigen aufgrund ihrer Schichtenstruktur eine stark anisotrope thermische Ausdehnung. Sie besitzen eine für Hydrate ungewöhnlich große thermische Stabilität. Die Magnesiumverbindung zersetzt sich z. B. erst oberhalb von 355°C. Die Verbindungen des Typs NaM2OH(SO3)2 · 1 H2O kristallisieren triklin (P1, Z = 2) mit folgenden Gitterdaten: M = Mg: a = 890,5(1), b = 784,5(1), c = 631,5(1) pm, α = 113,28(2)°, β = 110,41(1)°, γ = 98,00(2)°, M = Mn: a = 907,6(1), b = 795,7(1), c = 648,7(1) pm, α = 112,71(1)°, β = 109,34(1)°, γ = 99,23(1)°, M = Fe: a = 898,8(1), b = 789,0(1), c = 634,8(1) pm, α = 112,06(1)°, β = 109,59(1)°, γ = 99,76(1)°, M = Co: a = 888,0(1), b = 783,7(1), c = 631,6(1) pm, α = 112,61(1)°, β = 109,85(1)°, γ = 98,93(1)°, M = Ni: a = 878,4(2), b = 777,0(3), c = 626,3(1) pm, α = 112,54(2)°, β = 109,84(2)°, γ = 99,47(3)°, M = Zn: a = 887,4(1), b = 785,2(1), c = 629,9(1) pm, α = 112,27(1)°, β = 109,67(1)° und γ = 99,66(1)°.

AbstractDie durch Kristallisation aus natriumhaltigen wäßrigen Sulfitlösungen dargestellten, bislang unbekannten Titel‐Sulfite (genaue experimentelle Angaben) zeigen aufgrund ihrer Schichtstruktur eine stark anisotrope thermische Ausdehnung und besitzen eine für Hydrate ungewöhnlich große thermische Stabilität. Die Mg‐Verbindung zersetzt sich beispielsweise erst bei 355°C. Die Hydroxidsulfite kristallisieren in der Raumgruppe P1 mit Z=2.

The i.r. and Raman spectra of the anhydrous perchlorates KClO4, RbClO4, and CsClO4 have been recorded in the temperature range 90—600 K, i.e. in both the orthorhombic baryte-type low-temperature modifications and the cubic NaCl-type high-temperature forms with orientationally disordered ClO−4 ions. The perchlorates under investigation exhibit unusually fast cation exchange in alkaline halide discs. The assignment of the modes was made with the help of Raman single crystal measurements. From site group and unit cell group splitting of the internal ClO−4 modes it is shown that in the baryte-type perchlorates deviation from Td symmetry of the ClO−4 ions is considerably smaller and interionic interaction of the vibrations significantly larger than in the anhydrite-type sodium perchlorate [20]. The frequency shifts of the internal ClO−4 modes within the series KClO4, RbClO4, and CsClO4 and of ClO−4 ions trapped in KBr and RbBr matrixes are discussed in terms of the repulsion potential of the lattice. The spectra of the cubic high-temperature modifications indicate full Td symmetry of the ClO−4 ions in these compounds.

The vibrational frequency of free OH− ions, which cannot be directly measured, has been claimed to be 3700 cm−1. In solid hydroxides the OH stretching frequency has been found in the range from 3690 to 3100 cm−1. The decrease of the vibrational frequency has been interpreted to be caused by hydrogen bridges or the increase of the metal oxygen bond strength. We suggest an alternative explanation. The vibrational frequency of unperturbed OH− ions is 3570 ± 10 cm−1. In ionic hydroxides this frequency is increased due to repulsion effects of the lattice or decreased if hydrogen bonds are present, to a large extent (up to 400 cm−1) in the case of common OH−….X bridges and only up to 70 cm−1 in the case of XH….OH− bonds.

From rehydration experiments the hydrates Ba(OH)2 · 8 H2O, Ba(OH)2 · 3 H2O β-Ba(OH)2, · 1 H2O, and γ-Ba(OH)2 · 1 H2O have been found in the system Ba(OH)2-H2O. Thermoanalytical measurements (DTA, TG, DTG, high temperature X-ray diffraction, high temperature Raman scattering) on these hydrates are reported. Thermal decomposition of Ba(OH)2 · 8 H2O and Ba(OH)2 · 3 H2O always results in the formation of β-Ba(OH)2 · 1 H2O, the stable form of the monohydrates at ambient temperature. Dehydration of β- and γ-Ba(OH)2 · 1 H2O, both of which form anhydrous β-Ba(OH)2 as the first product of decomposition, starts at 105 and 115°C, respectively. Single crystals of Ba(OH)2 · 3 H2O and γ-Ba(OH)2 · 1 H2O were prepared from Ba(OH)2 · 8 H2O meltings and from ethanolic solutions of Ba(OH)2 , respectively. The crystal data are: Ba(OH)2 · 3 H2O (orthorhombic, Pnma): a = 764.0(2), b = 1140,3(5), c = 596.5(1) pm, Z = 4; γ-Ba(OH)2 · 1 H2O (monoclinic, P21/m or P21): a = 704.9(2), b = 418.4(1), c = 633.3(1) pm, β = 111.45(2)°, Z = 2.

AbstractIm Verlauf von Rehydratisierungsexperimenten werden im System Ba(OH)2‐ H2O die Hydrate (I)‐(IV) gefunden und thermoanalytisch (DTA, TG, DTG, HT‐ Röntgen‐Beugung und HT‐Raman‐Streuung) untersucht.

AbstractIn den Systemen FeSO3H2O und NiSO3H2O konnten folgende Hydrate erhalten werden: α‐FeSO3 · 3H2O, γ‐FeSO3 · 3H2O, FeSO3 · 2,5 H2O, FeSO3 · 2 H2O, NiSO3 · 6 H2O, NiSO3 · 3 H2O, NiSO3 · 2,5 H2O und NiSO3 · 2 H2O. Die Gitterdaten der folgenden Hydrate wurden anhand von Einkristallmessungen bestimmt: γ‐FeSO3 · 3 H2O: a = 965,9(1), b = 557,1(1), c = 944,7(1) pm, Z = 4, FeSO3 · 2 H2O (P21/n): a = 645,6(1), b = 863,1(1), c = 761,2(1) pm, β = 99,84(1)°, Z = 4, NiSO3 · 3 H2O: a = 945,0(1), b = 547,2(1), c = 932,5(1) pm, Z = 4, NiSO3 · 2,5 H2O (P41212): a = b = 935,3(1), c = 1016,6(1) pm, Z = 8, NiSO3 · 2 H2O (P21/n): a = 631,4(1), b = 851,0(1), c = 744,7(1) pm, β = 98,91(1)°, Z = 4. Die IR‐ und Raman‐Spektren sowie das Ergebnis thermoanalytischer Messungen (DTA, DTG, Röntgenheizaufnahmen) werden mitgeteilt. Die bei Sulfiten und Sulfithydraten zweiwertiger Metalle bisher beobachteten Strukturtypen werden diskutiert.Sulfites and Sulfite Hydrates of Iron and Nickel. X‐ray, Thermoanalytical, I.R., and Raman DataIn the systems FeSO3H2O and NiSO3H2O the following hydrates have been found: α‐FeSO3 · 3H2O, γ‐FeSO3 · 3H2O, FeSO3 · 2,5 H2O, FeSO3 · 2 H2O, NiSO3 · 6 H2O, NiSO3 · 3 H2O, NiSO3 · 2,5 H2O and NiSO3 · 2 H2O. The following crystal data have been determined by single crystal measurements: γ‐FeSO3 · 3 H2O: a = 965,9(1), b = 557,1(1), c = 944,7(1) pm, Z = 4, FeSO3 · 2 H2O (P21/n): a = 645,6(1), b = 863,1(1), c = 761,2(1) pm, β = 99,84(1)°, Z = 4, NiSO3 · 3 H2O: a = 945,0(1), b = 547,2(1), c = 932,5(1) pm, Z = 4, NiSO3 · 2,5 H2O (P41212): a = b = 935,3(1), c = 1016,6(1) pm, Z = 8, NiSO3 · 2 H2O (P21/n): a = 631,4(1), b = 851,0(1), c = 744,7(1) pm, β = 98,91(1)°, Z = 4. IR, Raman, and thermoanalytical (DTA, DTG, high temperature X‐ray) data are presented. The structure types found for sulfites and sulfite hydrates of bivalent metals are discussed.

The Raman and i.r. spectra of the barium and strontium hydroxides and hydroxide hydrates Ba(OH)2·8H2O, Ba(OH)2·3H2O, β- and γ-Ba(OH)2·1H2O, α- and β-Ba(OH)2, Sr(OH)2·8H2O, Sr(OH)2·1 H2O and Sr(OH)2 are reported and structural and bonding features are discussed. The Raman spectra of the lower hydrates of barium and strontium hydroxide, viz. Ba(OH)2·3H2O, Sr(OH)2·1H2O, and β- and γ-Ba(OH)2·1H2O, do not show any water band, either as stretching or bending modes. This behaviour is probably due to the strong hydrogen bonding of the water of crystallization in the barium and strontium hydroxide hydrates. The hydroxide ions of most compounds under investigation, however, are not hydrogen bonded. This is shown from the small negative temperature shift of the OH (or OD) stretching modes in isotopically dilute samples. A positive temperature shift of the uncoupled stretching modes, as found for some of the hydroxide ions in Sr(OH)2 and α- and β-Ba(OH)2, is an unfailing indicator that hydrogen bridges are present. The stretching vibrations of non-hydrogen-bonded hydroxide ions have been found to vary from 3690 to 3500 cm−1. The possible reason for these large frequency shifts, i.e., weakening or hardening of the stretching frequency of free OH ions by the lattice potential, is discussed. Some rotatory modes of hydroxide ions and water molecules have been observed at unusually high frequencies above 1000 cm−1.