Temperature-dependent EXAFS analysis of embedded Pt nanocrystals.

The vibrational and thermal properties of embedded Pt nanocrystals (NCs) have been investigated with temperature-dependent extended x-ray absorption fine structure (EXAFS) spectroscopy. NCs of diameter 1.8-7.4 nm produced by ion implantation in amorphous SiO(2) were analysed over the temperature range 20-295 K. An increase in Einstein temperature (∼194 K) relative to that of a Pt standard (∼179 K) was evident for the smallest NCs while those larger than ∼2.0 nm exhibited values comparable to bulk material. Similarly, the thermal expansion of interatomic distances was lowest for small NCs. While the amorphous SiO(2) matrix restricted the thermal expansion of interatomic distances, it did not have a significant influence on the mean vibrational frequency of embedded Pt NCs. Instead, the latter was governed by finite-size effects or, specifically, capillary pressure.

The structure of ultrathin Langmuir-Blodgett films of cadmium behenate.

Grazing incidence x-ray-diffraction investigations of the structures of Langmuir-Blodgett films of cadmium behenate with 1, 2, 3, 5, and 21 monolayers are reported. The single monolayer film, deposited on a hydrophilic substrate, showed a hexagonal structure, whereas the bilayer film, deposited on a hydrophobic substrate, had a rectangular structure with herringbone orientation of the acyl chains. With multilayer films formed on a hydrophilic substrate, it was possible to detect that the hexagonal structure of the first layer was retained when additional layers were deposited and that the additional layers had the same rectangular structure as the bilayer.

An eight-position capillary sample spinning stage for the diffractometer at BL20B at the Photon Factory.

An eight-position capillary sample spinning stage has been developed for use in conjunction with the versatile vacuum diffractometer (BIGDIFF) at BL20B at the Photon Factory. BIGDIFF is often used in its powder diffraction mode using powders mounted in capillaries and up to eight imaging plates to record the diffraction pattern from the sample. Using the multiple spinning stage a number of diffraction patterns can be recorded on the imaging plates if the imaging-plate cassette is moved behind the Weissenberg screen to a new position after exposure of the sample to the beam. Not only is this system more efficient in terms of time saved in the pumping-down process, but also it has the advantage of allowing the diffraction patterns of standards to be recorded, thereby calibrating both the angle scale of the diffractometer and the intensity scales of the imaging plates absolutely.

Focusing monochromator and imaging-plate camera for grazing-incidence diffraction studies of thin films.

A multiple-imaging-plate detector system and focusing monochromator have been developed and successfully applied to the time-resolved study of phase transitions in Langmuir-Blodgett films by grazing-incidence X-ray diffraction (GIXD). The monochromator described here combines fixed-exit-beam height with sagittal focusing of the second crystal. The design is similar to that of Matsushita et al. [Matsushita, Ishikawa & Oyanagi (1986). Nucl. Instrum. Methods, A246, 377-379], with the exception that the motion of the first crystal is achieved via a computer-controlled X-Y translation table rather than a set of cams. The second crystal is a ribbed Si(111) wafer mounted in a four-point bending mechanism. The first reported application of imaging plates to a GIXD study was carried out by our group and proved to be very successful in the determination of thin-film structure [Foran, Peng, Steitz, Barnes & Gentle (1996). Langmuir, 12, 774-777]. To extend the capabilities of this system, an imaging-plate camera was designed and built which can accommodate up to 13 imaging plates (40 x 20 cm) inside the vacuum chamber of the main diffractometer at the Australian Beamline at the Photon Factory.

Time-resolved grazing-incidence diffraction studies of thin films using an imaging-plate camera and focusing monochromator.

A multiple imaging-plate (IP) detector system and focusing monochromator have been developed and successfully applied to the time-resolved study of phase transitions in Langmuir-Blodgett (LB) films by grazing-incidence X-ray diffraction (GIXD). The first reported application of imaging plates to a GIXD study was carried out by our group and proved to be very successful in the determination of thin-film structure [Foran, Peng, Steitz, Barnes & Gentle (1996). Langmuir, 12, 774-777]. To extend the capabilities of this system, an IP camera was designed and built which can accommodate up to 13 IPs (40 x 20 cm) inside the vacuum chamber of the main diffractometer at the Australian Beamline at the Photon Factory. The camera allows the enclosed IPs to be successively exposed and stored inside the diffractometer for later scanning. The focusing monochromator employed in this technique combines fixed exit-beam height with sagittal focusing of the second crystal and delivers a gain in flux of >/=20 times when measured through a 0.1 x 0.1 mm aperture. The utility of the system incorporating the IP camera and the focusing monochromator has been demonstrated through the study of temperature-dependent phase transitions in LB films of metal fatty acids.

Determination of the structures of antiinflammatory copper(II) dimers of indomethacin by multiple-scattering analyses of X-ray absorption fine structure data.

Copper K-edge X-ray absorption spectroscopic (XAS) measurements were recorded for the veterinary antiinflammatory Cu(II) complexes of indomethacin (1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid = IndoH), of the general formula [Cu(2)(Indo)(4)L(2)] (L = N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and water), and [Cu(2)(OAc)(4)(OH(2))(2)] at room temperature and 10 K. The bond lengths and bridging O-C-O angles of the dimeric Cu(II) cage (Cu(2)O(10)C(8)) obtained from the multiple-scattering (MS) fitting of the X-ray absorption fine structure (XAFS) using a centrosymmetric model of [Cu(2)(Indo)(4)(DMF)(2)] gave Cu.Cu = 2.62(2) A, mean Cu-O(Ac) = 1.95(2) A, Cu-O(L) = 2.15(2) A, bridging O-C-O = 125(1) degrees, Cu displacement from plane 0.19 A compared with the XRD data Cu.Cu = 2.630(1) A, mean Cu-O(Ac) = 1.959 A, Cu-O(L) = 2.143(5) A, bridging O-C-O angles = 123.2(5) degrees, Cu displacement from plane 0.20 A. The excellent agreement between the XAFS- and XRD-derived data allowed the structures of related [Cu(2)(Indo)(4)L(2)] (L = DMA, NMP) complexes to be determined. All display a similar Cu(2)O(10)C(8) coordination geometry, which is independent of the nature of the axial ligand. While XAFS analysis of [Cu(2)(Indo)(4)(OH(2))(2)] and [Cu(2)(OAc)(4)(OH(2))(2)] indicates a coordination geometry similar to that of [Cu(2)(Indo)(4)L(2)] (L = DMF, DMA, NMP), removal of symmetry restraints in the MS model is required to obtain axial bond lengths comparable to those derived in the XRD structures of the acetate complex. For the Indo complex, the fitted bond lengths with the lower symmetry model give a mean Cu-L(OH2) bond distance within experimental errors of the value for [Cu(2)(Indo)(4)(DMSO)(2)] (2.16(2) A) (XRD). The difficulty in refining the Cu-O(OH2) distance of [Cu(2)(OAc)(4)(OH(2))(2)] and [Cu(2)(Indo)(4)(OH(2))(2)] using a centrosymmetric MS model is attributed to a symmetry reduction due to hydrogen-bonding effects characteristic of the aqua adducts, as is observed in the XRD structure of the acetate complex.

Structure and low-temperature thermal relaxation of ion-implanted germanium.

The structure of implantation-induced damage in Ge has been investigated using high resolution extended X-ray absorption fine structure spectroscopy (EXAFS). EXAFS data analysis was performed with the Cumulant Method. For the crystalline-to-amorphous transformation, a progressive increase in bond-length was observed without the presence of an asymmetry in interatomic distance distribution (RDF). Beyond the amorphization threshold the RDF was dose dependent and asymmetric, where the bond-length and asymmetry increased as functions of ion dose. Such an effect was attributed to the formation of three- and five-fold coordinated atoms within the amorphous phase. Low-temperature thermal annealing resulted in structural relaxation of the amorphous phase as evidenced by a reduction in the centroid, asymmetry and width of the RDF, as consistent with a reduction in the fraction of non four-fold coordinated atoms. The results have been compared to other EXAFS studies of amorphous Ge, and it is suggested that the range of bond-lengths reported therein is related to the sample preparation method and state of relaxation.