Donovan N. Leonard

Surface plasmon resonance in conducting metal oxides

We report the initial observation of surface plasmon resonance (SPR) in a conducting metal oxide thin film. The SPR phenomenon has been observed by attenuated total reflection of near-infrared radiation and is in agreement with electron energy loss spectroscopy measurements. To date, only metals are known to exhibit surface plasmon resonance and only noble metals have practical application. According to theory SPR should be observable in any conductor. This theoretical prediction is verified in the present study. The compositions of many conducting metal oxides are systematically variable, suggesting a significant advance in thin film characterization and innovative possibilities for versatile and sensitive chemical sensing applications.We report the initial observation of surface plasmon resonance (SPR) in a conducting metal oxide thin film. The SPR phenomenon has been observed by attenuated total reflection of near-infrared radiation and is in agreement with electron energy loss spectroscopy measurements. To date, only metals are known to exhibit surface plasmon resonance and only noble metals have practical application. According to theory SPR should be observable in any conductor. This theoretical prediction is verified in the present study. The compositions of many conducting metal oxides are systematically variable, suggesting a significant advance in thin film characterization and innovative possibilities for versatile and sensitive chemical sensing applications.

Correlated optical measurements and plasmon mapping of silver nanorods.

Plasmonics is a rapidly growing field, yet imaging of the plasmonic modes in complex nanoscale architectures is extremely challenging. Here we obtain spatial maps of the localized surface plasmon modes of high-aspect-ratio silver nanorods using electron energy loss spectroscopy (EELS) and correlate to optical data and classical electrodynamics calculations from the exact same particles. EELS mapping is thus demonstrated to be an invaluable technique for elucidating complex and overlapping plasmon modes.

Interfacial reactions of Sn-Ag-Cu solders modified by minor Zn alloying addition

The near-ternary eutectic Sn-Ag-Cu alloys have been identified as leading Pb-free solder candidates to replace Pb-bearing solders in microelectronic applications. However, recent investigations on the processing behavior and solder joints reliability assessment have revealed several potential reliability risk factors associated with the alloy system. The formation of large Ag3Sn plates in Sn-Ag-Cu joints, especially when solidified in a relatively slow cooling rate, is one issue of concern. The implications of large Ag3Sn plates on solder joint performance and several methods to control them have been discussed in previous studies. The minor Zn addition was found to be effective in reducing the amount of undercooling required for tin solidification and thereby to suppress the formation of large Ag3Sn plates. The Zn addition also caused the changes in the bulk microstructure as well as the interfacial reaction. In this paper, an in-depth characterization of the interfacial reaction of Zn-added Sn-Ag-Cu solders on Cu and Au/Ni(P) surface finishes is reported. The effects of a Zn addition on modification of the interfacial IMCs and their growth kinetics are also discussed.

Synergistic Effects Between Phosphonium-Alkylphosphate Ionic Liquids and Zinc Dialkyldithiophosphate (ZDDP) as Lubricant Additives

Unique synergistic effects between phosphonium-alkylphosphate ionic liquids (ILs) and zinc dialkyldithiophosphate (ZDDP) are discovered when used together as lubricant additives, resulting in significant friction and wear reduction along with distinct tribofilm composition and mechanical properties. The synergism is attributed to the remarkably 30-70× higher-than-nominal concentrations of hypothetical new compounds (via anion exchange between IL and ZDDP) on the fluid surface/interface.

Focused ion beam fabrication of metallic nanostructures on end faces of optical fibers for chemical sensing applications

Focused ion beam (FIB) fabrication of fiber optic sensors, mainly chemical sensors, which are based on plasmonics-active nanostructures formed on the cleaved tips of optical fibers, is reported. The nanostructures fabricated included nanoholes in optically thick metallic films as well as metallic nanopillars and nanorods. The sensing mechanism is based on detecting shifts in surface plasmon resonances (SPRs) associated with nanoholes in metallic films and localized SPRs of metallic nanopillars and nanorods, when the refractive index of the medium surrounding the nanostructures is changed. These sensors can be employed for the detection of chemical agents in air as well as liquid media surrounding the sensors. FIB milling was employed to fabricate ordered arrays of nanoholes in optically thick (100–240nm) metallic films deposited on cleaved end faces of multimode, four-mode, and single-mode optical fibers. Separately, metallic nanorods and nanopillars were formed by first depositing a metallic (gold or sil...

Atomic-level sculpting of crystalline oxides: toward bulk nanofabrication with single atomic plane precision

The atomic-level sculpting of 3D crystalline oxide nanostructures from metastable amorphous films in a scanning transmission electron microscope (STEM) is demonstrated. Strontium titanate nanostructures grow epitaxially from the crystalline substrate following the beam path. This method can be used for fabricating crystalline structures as small as 1-2 nm and the process can be observed in situ with atomic resolution. The fabrication of arbitrary shape structures via control of the position and scan speed of the electron beam is further demonstrated. Combined with broad availability of the atomic resolved electron microscopy platforms, these observations suggest the feasibility of large scale implementation of bulk atomic-level fabrication as a new enabling tool of nanoscience and technology, providing a bottom-up, atomic-level complement to 3D printing.

Ferritic Alloys with Extreme Creep Resistance via Coherent Hierarchical Precipitates.

There have been numerous efforts to develop creep-resistant materials strengthened by incoherent particles at high temperatures and stresses in response to future energy needs for steam turbines in thermal-power plants. However, the microstructural instability of the incoherent-particle-strengthened ferritic steels limits their application to temperatures below 900 K. Here, we report a novel ferritic alloy with the excellent creep resistance enhanced by coherent hierarchical precipitates, using the integrated experimental (transmission-electron microscopy/scanning-transmission-electron microscopy, in-situ neutron diffraction, and atom-probe tomography) and theoretical (crystal-plasticity finite-element modeling) approaches. This alloy is strengthened by nano-scaled L21-Ni2TiAl (Heusler phase)-based precipitates, which themselves contain coherent nano-scaled B2 zones. These coherent hierarchical precipitates are uniformly distributed within the Fe matrix. Our hierarchical structure material exhibits the superior creep resistance at 973 K in terms of the minimal creep rate, which is four orders of magnitude lower than that of conventional ferritic steels. These results provide a new alloy-design strategy using the novel concept of hierarchical precipitates and the fundamental science for developing creep-resistant ferritic alloys. The present research will broaden the applications of ferritic alloys to higher temperatures.

Structural and compositional dependence of the CdTexSe1-x alloy layer photoactivity in CdTe-based solar cells

The published external quantum efficiency data of the world-record CdTe solar cell suggests that the device uses bandgap engineering, most likely with a CdTexSe1−x alloy layer to increase the short-circuit current and overall device efficiency. Here atom probe tomography, transmission electron microscopy and electron beam-induced current are used to clarify the dependence of Se content on the photoactive properties of CdTexSe1−x alloy layers in bandgap-graded CdTe solar cells. Four solar cells were prepared with 50, 100, 200 and 400 nm-thick CdSe layers to reveal the formation, growth, composition, structure and photoactivity of the CdTexSe1−x alloy with respect to the degree of Se diffusion. The results show that the CdTexSe1−x layer photoactivity is highly dependent on the crystalline structure of the alloy (zincblende versus wurtzite), which is also dependent on the Se and Te concentrations.

Interfacial reactions, microstructure and mechanical properties of Pb-free solder joints in PBGA laminates

Sn-based alloys have been developed as Pb-free solder candidates to replace the Pb-containing solders used in microelectronic applications. However, their high Sn content and high melting point often cause excessive interfacial reactions, namely, dissolution of surface finish layers and concomitant formation of intermetallic compounds at the soldering interface. These interfacial reactions can therefore influence the microstructure and mechanical properties of the solder joints and eventually their reliability. The choice of a proper surface finish layer in printed circuit boards is an important issue in successfully introducing the Sn-based, Pb-free solders. The effects of surface finish layers and multiple reflows on the BGA solder joints have been investigated. A Pb-free solder alloy, Sn-Ag-Cu has been employed as the solder ball material. Five types of surface finish on opposite sides of the BGA balls, have been investigated. Intermetallic compound formation was measured as a function of reflow cycle. The effects of the interfacial reactions on the microstructure and mechanical properties of the solder joints were also investigated as a function of surface finish and reflow cycle.

Fabrication of nanodot plasmonic waveguide structures using FIB milling and electron beam-induced deposition

Fabrication of metallic Au nanopillars and linear arrays of Au-containing nanodots for plasmonic waveguides is reported in this article by two different processes-focused ion beam (FIB) milling of deposited thin films and electron beam-induced deposition (EBID) of metallic nanostructures from an organometallic precursor gas. Finite difference time domain (FDTD) modeling of electromagnetic fields around metallic nanostructures was used to predict the optimal size and spacing between nanostructures useful for plasmonic waveguides. Subsequently, a multi-step FIB fabrication method was developed for production of metallic nanorods and nanopillars of the size and geometry suggested by the results of the FDTD simulations. Nanostructure fabrication was carried out on planar substrates including Au-coated glass, quartz, and mica slides as well as cleaved 4-mode optical fibers. In the second fabrication process, EBID was utilized for the development of similar nanostructures on planar Indium Tin Oxide and Titanium-coated glass substrates. Each method allows formation of nanostructures such that the plasmon resonances associated with the nanostructures could be engineered and precisely controlled by controlling the nanostructure size and shape. Linear arrays of low aspect ratio nanodot structures ranging in diameter between 50-70 nm were fabricated using EBID. Preliminary dark field optical microscopy demonstrates differences in the plasmonic response of the fabricated structures.