Direct Writing of Copper Film Patterns by Laser-Induced Decomposition of Copper Acetate

Direct writing of patterns is being widely attempted in the field of microelectronic circuit/device manufacture. Use of this technique eliminates the need for employing photolithographic process. Laser induced direct writing can be achieved by (i) Photochemical reaction [i] , (ii) Evaporation from target material [2], and (iii) decomposition.Micron size features of palladium and copper through decomposition of palladium acetate and copper formate respectively on quartz and silicon using Argon ion laser have been reported [3,4] .In this commuication we report a technique for both single line and large area depositon of copper through decomposition of copper acetate,(CH3COO)2Cu, on alumina substrates.Nd:YAG laser known for its reliability and low maintenance cost as compared to excimer and other gas lasers is used. This technique offers an attractive and economical alternative for manufacture of thin film microcircuits.

Photoinduced DNA and Protein Cleavage Activity of Ferrocene-Conjugated Ternary Copper(II) Complexes

Ferrocene-conjugated ternary copper(II) complexes [Cu(L)(B)](ClO4)(2), where L is FcCH(2)N(CH2Py)(2) (Fc = (eta(5)-C5H4)Fe-II(eta(5)-C5H5)) and B is a phenanthroline base, viz., 2,2'-bipyridine (bpy, 1), 1, 10-phenanthroline (phen, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz, 4), have been synthesized and characterized by various spectroscopic and analytical techniques. The bpy complex 1, as its hexafluorophosphate salt, has been structurally characterized by X-ray crystallography. The molecular structure shows the copper(II) center having an essentially square-pyramidal coordination geometry in which L with a pendant ferrocenyl (Fc) moiety and bpy show respective tridentate and bidentate modes of binding to the metal center. The complexes are redox active, showing a reversible cyclic voltammetric response of the Fc(+)-Fc couple near 0.5 V vs SCE and a quasi-reversible Cu(II)-Cu(I) couple near 0.0 V. Complexes 2-4 show binding affinity to calf thymus (CT) DNA, giving binding constant (K-b) values in the range of 4.2 x 10(4) to 2.5 x 10(5) M-1. Thermal denaturation and viscometric titration data suggest groove binding and/or a partial intercalative mode of binding of the complexes to CT DNA. The complexes show good binding propensity to the bovine serum albumin (BSA) protein, giving K-BSA values of similar to 10(4) M-1 for the bpy and phen complexes and similar to 10(5) M-1 for the dpq and dppz complexes. Complexes 2-4 exhibit efficient chemical nuclease activity in the presence of 3-mercapto-propionic acid (MPA) as a reducing agent or hydrogen peroxide (H2O2) as an oxidizing agent. Mechanistic studies reveal formation of hydroxyl radicals as the reactive species. The dpq and dppz complexes are active in cleaving supercoiled (SC) pUC19 DNA on photoexposure to visible light of different wavelengths including red light using an argon-krypton mixed gas ion laser. Mechanistic investigations using various inhibitors reveal the fort-nation of hydroxyl radicals in the DNA photocleavage reactions. The dppz complex 4, which shows efficient photoioduced BSA cleavage activity, is a potent multifunctional model nuclease and protease in the chemistry of photodynamic therapy (PDT) of cancer.

Copper(II) Complexes of l-Arginine as Netropsin Mimics Showing DNA Cleavage Activity in Red Light

Copper(II) complexes [Cu(L-arg)(2)](NO3)(2) (1) and [Cu(L-arg)(B)Cl]Cl (2-5), where B is a heterocyclic base, namely, 2,2'-bipyridine (bpy, 2), 1,10-phenanthroline (phen, 3), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 4), and dipyrido[3,2-a:2',3'-c)phenazine (dppz, 5), are prepared and their DNA binding and photoinduced DNA cleavage activity studied. Ternary complex 3, structurally characterized using X-ray crystallography, shows a square-pyramidal (4 + 1) coordination geometry in which the N,O-donor L-arginine and N,N-donor 1,10-phenanthroline form the basal plane with one chloride at the elongated axial site. The complex has a pendant cationic guanidinium moiety. The one-electron paramagnetic complexes display a metal-centered d-d band in the range of 590-690 nm in aqueous DMF They show quasireversible cyclic voltammetric response due to the Cu(II)/Cu(I) couple in the range of -0.1 to -0.3 V versus a saturated calomel electrode in a DMF-Tris HCl buffer (pH 7.2). The DNA binding propensity of the complexes is studied using various techniques. Copper(II) bis-arginate 1 mimics the minor groove binder netropsin by showing preferential binding to the AT-rich sequence of double-strand (ds) DNA. DNA binding study using calf thymus DNA gives an order: 5 (L-arg-dppz) >= 1 (biS-L-arg) > 4 (L-arg-dpq) > 3 (L-arg-phen) >> 2 (L-arg-bpy). Molecular docking calculations reveal that the complexes bind through extensive hydrogen bonding and electrostatic interactions with ds-DNA. The complexes cleave supercoiled pUC19 DNA in the presence of 3-mercaptopropionic acid as a reducing agent forming hydroxyl ((OH)-O-center dot) radicals. The complexes show oxidative photoinduced DNA cleavage activity in UV-A light of 365 nm and red light of 647.1 nm (Ar-Kr mixed-gas-ion laser) in a metal-assisted photoexcitation process forming singlet oxygen (O-1(2)) species in a type-II pathway. All of the complexes, barring complex 2, show efficient DNA photocleavage activity. Complexes 4 and 5 exhibit significant double-strand breaks of DNA in red light of 647.1 nm due to the presence of two photosensitizers, namely, L-arginine and dpq or dppz in the molecules.

EIT as a tool to observe dual wavelength operation of a semiconductor laser

We propose a simplified technique for dual wavelength operation of an extended cavity semiconductor laser, and its characterization using electromagnetically induced transparency (EIT). In this laser cavity scheme light beam is made converging before it incidences on the cavity grating. The converging angle of the beam creates two longitudinal oscillating modes of resonating cavity. Frequency separation between the longitudinal modes are measured with the help of beat frequency generation in a photodiode and creating pair of EIT spectra in Rb vapor. The pair of EIT dips that are generated due to dual wavelength of this laser (that is used as control laser) can be used to estimate frequency difference between the generated wavelengths. Width of EIT spectra can be used to estimate line width of individual wavelength components.

DNA cleavage in red light promoted by copper(II) complexes of -amino acids and photoactive phenanthroline bases

Ternary copper(II) complexes [Cu(L-trp)(B)(H2O)](NO3) ( 1–3) and [Cu(L-phe)(B)(H2O)](NO3) ( 4–6) of L-tryptophan (L-trp) and L-phenylalanine (L-phe) having phenanthroline bases (B), viz. 1,10-phenanthroline (phen, 1 and 4), dipyrido[3,2-d:2,3-f]quinoxaline (dpq, 2 and 5) and dipyrido[3,2-a:2,3-c]phenazine (dppz, 3 and 6), were prepared and characterized by physico-chemical techniques. Complexes 3 and 6 were structurally characterized by X-ray crystallography and show the presence of a square pyramidal (4 + 1) CuN3O2 coordination geometry in which the N,O-donor amino acid (L-trp or L-phe) and N,N-donor phenanthroline base bind at the equatorial plane with an aqua ligand coordinated at the elongated axial site. Complex 3 shows significant distortion from the square pyramidal geometry and a strong intramolecular – stacking interaction between the pendant indole ring of L-trp and the planar dppz aromatic moiety. All the complexes display good binding propensity to the calf thymus DNA giving an order: 3, 6 (dppz) > 2, 5 (dpq) > 1, 4 (phen). The binding constant (Kb) values are in the range of 2.1 × 104–1.1 × 106 mol-1 with the binding site size (s) values of 0.17–0.63. The phen and dpq complexes are minor groove binders while the dppz analogues bind at the DNA major groove. Theoretical DNA docking studies on 2 and 3 show the close proximity of two photosensitizers, viz. the indole moiety of L-trp and the quinoxaline/phenazine of the dpq/dppz bases, to the complementary DNA strands. Complexes 2 and 3 show oxidative DNA double strand breaks (dsb) of supercoiled (SC) DNA forming a significant quantity of linear DNA along with the nicked circular (NC) form on photoexposure to UV-A light of 365 nm and red light of 647.1 nm (Ar–Kr laser). Complexes 1, 5 and 6 show only single strand breaks (ssb) forming NC DNA. The red light induced DNA cleavage involves metal-assisted photosensitization of L-trp and dpq/dppz base resulting in the formation of a reactive singlet oxygen (1O2) species.

Characterization of a continuous CO2 laser-welded Fe-Cu dissimilar couple

Continuous CO2 laser welding of an Fe-Cu dissimilar couple in a butt-weld geometry at different process conditions is studied. The process conditions are varied to identify and characterize the microstructural features that are independent of the welding mode. The study presents a characterization of the microstructure and mechanical properties of the welds. Detailed microstructural analysis of the weld/base-metal interface shows features that are different on the two sides of the weld. The iron side can grow into the weld with a local change in length scale, whereas the interface on the copper side indicates a barrier to growth. The interface is jagged, and a banded microstructure consisting of iron-rich layers could be observed next to the weld/Cu interface. The observations suggest that solidification initiates inside the melt, where iron and copper are mixed due to convective flow. The transmission electron microscopy (TEM) of the weld region also indicates the occasional presence of droplets of iron and copper. The microstructural observations are rationalized using arguments drawn from a thermodynamic analysis of the Fe-Cu system.

Large low-frequency resistance noise in chemical vapor deposited graphene

We report a detailed investigation of resistance noise in single layer graphene films on Si/SiO2 substrates obtained by chemical vapor deposition (CVD) on copper foils. We find that noise in these systems to be rather large, and when expressed in the form of phenomenological Hooge equation, it corresponds to Hooge parameter as large as 0.1-0.5. We also find the variation in the noise magnitude with the gate voltage (or carrier density) and temperature to be surprisingly weak, which is also unlike the behavior of noise in other forms of graphene, in particular those from exfoliation. (C) 2010 American Institute of Physics. doi:10.1063/1.3493655]

A novel laser direct write technique for fabrication of thin film MICs

A technique for fabrication of thin-film circuits for microwave integrated circuit (MIC) application is presented. This low-cost fabrication technique utilizes laser direct write of copper patterns on alumina substrates. The method obviates the need for photomasks and photolithography. The film deposition mechanism, deposit film analysis, and MIC fabrication sequence are presented. Performance evaluation of MICs fabricated using this technique is also included

Thermal analysis of metalorganic complexes of copper for evaluation as CVD precursors

Metalorganic complexes of copper have been synthesized by modifying the ligand in the beta-diketonate class of compounds. Detailed thermal analysis of several beta-diketonate complexes of copper has been carried out to evaluate their suitability as precursors for chemical vapor deposition (CVD). A comparison of their relative volatilities has been made by determining their sublimation rates at different temperatures. Thermal analyses of these complexes reveal significant differences among their volatilities and decomposition patterns.

Microstructural evolution in laser-ablation-deposited Fe–25 at.% Ge thin film

Films with Fe–25 at.% Ge composition are deposited by the process of laser ablation on single crystal NaCl and Cu substrates at room temperature. Both the vapor and liquid droplets generated in this process are quenched on the substrate. The microstructures of the embedded droplets show size as well as composition dependence. The hierarchy of phase evolution from amorphous to body-centered cubic (bcc) to DO3 has been observed as a function of size. Some of the medium-sized droplets also show direct formation of ordered DO19 phase from the starting liquid. The evolution of disordered bcc structure in some of the droplets indicates disorder trapping during liquid to solid transformation. The microstructural evolution is analyzed on the basis of heat transfer mechanisms and continuous growth model in the solidifying droplets.

Evolution of metastable phases during crystallization of pulsed laser deposited amorphous Al–Fe films

Amorphous thin films of different Al–Fe compositions were produced by plasma/vapor quenching during pulsed laser deposition. The chosen compositions Al72Fe28, Al40Fe60, and Al18Fe82 correspond to Al5Fe2 and B2-ordered AlFe intermetallic compounds and α–Fe solid solution, respectively. The films contained fine clusters that increased with iron content. The sequences of phase evolution observed in the heating stage transmission electron microscopy studies of the pulsed laser ablation deposited films of Al72Fe28, Al40Fe60, and Al18Fe82 compositions showed evidence of composition partitioning during crystallization for films of all three compositions. This composition partitioning, in turn, resulted in the evolution of phases of compositions richer in Fe, as well as richer in Al, compared to the overall film composition in each case. The evidence of Fe-rich phases was the B2 phase in Al72Fe28 film, the L12- and DO3-ordered phases in Al40Fe60 film, and the hexagonal ε–Fe in the case of the Al18Fe82 film. On the other hand, the Al-rich phases were Al13Fe4 for both Al72Fe28 and Al40Fe60 films and DO3 and Al5Fe2 phases in the case of Al18Fe82 film. We believe that this tendency of composition partitioning during crystallization from amorphous phase is a consequence of the tendency of clustering of the Fe atoms in the amorphous phase during nucleation. The body-centered cubic phase has a nucleation advantage over other metastable phases for all three compositions. The amorphization of Al18Fe82 composition and the evolution of L12 and ε–Fe phases in the Al–Fe system were new observations of this work.

A Study of Nanostructures of Thin Films in B–C–N System Produced by Pulsed Laser Deposition and Nitrogen Ion-Beam-Assisted Pulsed Laser Deposition

We report the synthesis of thin films of B–C–N and C–N deposited by N+ ion-beam-assisted pulsed laser deposition (IBPLD) technique on glass substrates at different temperatures. We compare these films with the thin films of boron carbide synthesized by pulsed laser deposition without the assistance of ion-beam. Electron diffraction experiments in the transmission electron microscope shows that the vapor quenched regions of all films deposited at room temperature are amorphous. In addition, shown for the first time is the evidence of laser melting and subsequent rapid solidification of B4C melt in the form of micrometer- and submicrometer-size round particulates on the respective films. It is possible to amorphize B4C melt droplets of submicrometer sizes. Solidification morphologies of micrometer-size droplets show dispersion of nanocrystallites of B4C in amorphous matrix within the droplets. We were unable to synthesize cubic carbon nitride using the current technique. However, the formation of nanocrystalline turbostratic carbo- and boron carbo-nitrides were possible by IBPLD on substrate at elevated temperature and not at room temperature. Turbostraticity relaxes the lattice spacings locally in the nanometric hexagonal graphite in C–N film deposited at 600 °C leading to large broadening of diffraction rings.