Cu-Ag Nanocomposite Pastes for Low Temperature Bonding and Flexible Interlayer-Interconnections.

Cu-Ag composite pastes consisting of carboxylate-capped Ag nanoparticles, spray-pyrolyzed Ag submicron particles, and copper formate were developed in this study for low-temperature low-pressure bonding. The joints between the Cu, Ni/Au, and Ag finished substrates can be well formed at temperatures as low as 160 °C under a load pressure of 1.6 MPa. The joints with Cu substrates possess 18.0 MPa bonding strength, while those with Ag surface finish could be enhanced to 23.3 MPa. When subject to sintering under 10 MPa at 160 °C, the electrical resistivity of the sintered structure on metal-coated polymeric substrates was around 11~17 µΩ-cm and did not differ too much when subjected to harsh reliability tests such as mechanical bending and thermal cycling tests, as well as electrical current stressing. This low-temperature, low-pressure nanocomposite paste shows great potential as interconnect materials for microelectronics or flexible device assembly.

Plasma-Modified PI Substrate for Highly Reliable Laser-Sintered Copper Films Using Cu2O Nanoparticles.

Plasma modification of polyimide (PI) substrates upon which electrical circuits are fabricated by the laser sintering of cuprous oxide nanoparticle pastes was investigated systematically in this study. Surface properties of the PI substrate were investigated by carrying out atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Experimental results show that surface characteristics of PI substrates, including surface energy, surface roughness, and surface binding significantly affected the mechanical reliability of the sintered copper structure. Among the plasma gases tested (air, O2, Ar-5%H2, and N2-30%H2), O2 plasma caused the roughest PI surface as well as the most C=O and C-OH surface binding resulting in an increased polar component of the surface energy. The combination of all those factors caused superior bending fatigue resistance.

Optimization of Piezoresistive Strain Sensors Based on Gold Nanoparticle Deposits on PDMS Substrates for Highly Sensitive Human Pulse Sensing.

In this study, highly-sensitive piezoresistive strain sensors based on gold nanoparticle thin films deposited on a stretchable PDMS substrate by centrifugation were developed to measure arterial pulse waveform. By controlling carbon chain length of surfactants, pH value and particle density of the colloidal solutions, the gauge factors of nanoparticle thin film sensors can be optimized up to 677 in tensile mode and 338 in compressive mode, and the pressure sensitivity up to 350. Low pH and thin nanoparticle films produce positive influences to superior gauge factors. It has been demonstrated that nanoparticle thin film sensors on PDMS substrates were successfully applied to sense arterial pulses in different body positions, including wrist, elbow crease, neck, and chest.

Low-Thermal-Budget Photonic Sintering of Hybrid Pastes Containing Submicron/Nano CuO/Cu2O Particles.

Copper oxide particles of various sizes and constituent phases were used to form conductive circuits by means of photonic sintering. With the assistance of extremely low-energy-density xenon flash pulses (1.34 J/cm2), a mixture of nano/submicron copper oxide particles can be reduced in several seconds to form electrical conductive copper films or circuits exhibiting an average thickness of 6 µm without damaging the underlying polymeric substrate, which is quite unique compared to commercial nano-CuO inks whose sintered structure is usually 1 µm or less. A mixture of submicron/nano copper oxide particles with a weight ratio of 3:1 and increasing the fraction of Cu2O in the copper oxide both decrease the electrical resistivity of the reduced copper. Adding copper formate further improved the continuity of interconnects and, thereby, the electrical conductance. Exposure to three-pulse low-energy-density flashes yields an electrical resistivity of 64.6 µΩ·cm. This study not only shed the possibility to use heat-vulnerate polymers as substrate materials benefiting from extremely low-energy light sources, but also achieved photonic-sintered thick copper films through the adoption of submicron copper oxide particles.

Geometrical Effects on Ultrasonic Al Bump Direct Bonding for Microsystem Integration: Simulation and Experiments.

This study employed finite element analysis to simulate ultrasonic metal bump direct bonding. The stress distribution on bonding interfaces in metal bump arrays made of Al, Cu, and Ni/Pd/Au was simulated by adjusting geometrical parameters of the bumps, including the shape, size, and height; the bonding was performed with ultrasonic vibration with a frequency of 35 kHz under a force of 200 N, temperature of 200 °C, and duration of 5 s. The simulation results revealed that the maximum stress of square bumps was greater than that of round bumps. The maximum stress of little square bumps was at least 15% greater than those of little round bumps and big round bumps. An experimental demonstration was performed in which bumps were created on Si chips through Al sputtering and lithography processes. Subtractive lithography etching was the only effective process for the bonding of bumps, and Ar plasma treatment magnified the joint strength. The actual joint shear strength was positively proportional to the simulated maximum stress. Specifically, the shear strength reached 44.6 MPa in the case of ultrasonic bonding for the little Al square bumps.

Can Copper Nanostructures Sustain High-Quality Plasmons?

Silver, king among plasmonic materials, features low inelastic absorption in the visible-infrared (vis-IR) spectral region compared to other metals. In contrast, copper is commonly regarded as too lossy for actual applications. Here, we demonstrate vis-IR plasmons with quality factors >60 in long copper nanowires (NWs), as determined by electron energy-loss spectroscopy. We explain this result by noticing that most of the electromagnetic energy in these plasmons lies outside the metal, thus becoming less sensitive to inelastic absorption. Measurements for silver and copper NWs of different diameters allow us to elucidate the relative importance of radiative and nonradiative losses in plasmons spanning a wide spectral range down to <20 meV. Thermal population of such low-energy modes becomes significant and generates electron energy gains associated with plasmon absorption, rendering an experimental determination of the NW temperature. Copper is therefore emerging as an attractive, cheap, abundant material platform for high-quality plasmonics in elongated nanostructures.

Template-Free and Surfactant-Free Synthesis of Selective Multi-Oxide-Coated Ag Nanowires Enabling Tunable Surface Plasmon Resonance.

Without using templates, seeds and surfactants, this study successfully prepared multi-oxide-layer coated Ag nanowires that enable tunable surface plasmon resonance without size or shape changes. A spontaneously grown ultra-thin titania layer onto the Ag nanowire surface causes a shift in surface plasmon resonance towards low energy (high wavelength) and also acts as a preferential site for the subsequent deposition of various oxides, e.g., TiO2 and CeO2. The difference in refractive indices results in further plasmonic resonance shifts. This verifies that the surface plasma resonance wavelength of one-dimensional nanostructures can be adjusted using refractive indices and shell oxide thickness design.

Relationship between Nanomechanical Responses of Interfacial Intermetallic Compound Layers and Impact Reliability of Solder Joints.

This study aims to evaluate solder joint reliability under high speed impact tests using nanoindentation properties of intermetallic compounds (IMCs) at the joint interface. Sn-Ag based solder joints with different kinds of interfacial IMCs were obtained through the design of solder alloy/substrate material combinations. Nanoindentation was applied to investigate the mechanical properties of IMCs, including hardness, Young's modulus, work hardening exponent, yield strength, and plastic ability. Experimental results suggest that nanoindentation responses of IMCs at joint interface definitely dominates joint impact performance. The greater the plastic ability the interfacial IMC exhibits, the superior impact energy the solder joints possess. The concept of mechanical and geometrical discontinuities was also proposed to explain brittle fracture of the solder joints with bi-layer interfacial IMCs subject to impact load.

Magnetism and plasmonic performance of mesoscopic hollow ceria spheres decorated with silver nanoparticles.

We investigate the role of interfaces and surfaces in the magnetic and surface enhanced Raman spectroscopy (SERS) properties of CeO2 hollow spheres decorated with Ag nanoparticles (H-CeO2@Ag). The composites, H-CeO2@Ag, were synthesized using a newly developed two-step process. The CeO2 hollow sphere diameter ranges from 100 nm to 2 µm and the grafted Ag nanoparticle (NP) size varies from 5 to 50 nm with a controllable coverage ratio. Spectroscopic and microscopic characterization confirms the formation of an interface between the Ag and ceria and shows different charge rearrangements occurring at both the interface and the surface. Room temperature ferro-magnetism was observed in all composites, and is associated mostly with ceria surface defects. A strong SERS effect was reported with a detection limit down to 10-14 M for the rhodamine 6G analyte. Scanning transmission electron microscopy and electron energy loss spectroscopy investigation reveals that hot-spots are associated with the silver NP surfaces and also with the Ag/CeO2 interface. This interfacial hot spot occurs for metallic particles above 30 nm and is strongly red shifted with respect to the Ag surface plasmon. The strong SERS activity is then attributed to the presence of several types of hot-spots and the geometrical features (buoyant hollow sphere and size dispersion) of the composite.

Effect of Ag Templates on the Formation of Au-Ag Hollow/Core-Shell Nanostructures.

Au-Ag alloy nanostructures with various shapes were synthesized using a successive reduction method in this study. By means of galvanic replacement, twined Ag nanoparticles (NPs) and single-crystalline Ag nanowires (NWs) were adopted as templates, respectively, and alloyed with the same amount of Au(+) ions. High angle annular dark field-scanning TEM (HAADF-STEM) images observed from different rotation angles confirm that Ag NPs turned into AuAg alloy rings with an Au/Ag ratio of 1. The shifts of surface plasmon resonance and chemical composition reveal the evolution of the alloy ring formation. On the other hand, single-crystalline Ag NWs became Ag@AuAg core-shell wires instead of hollow nanostructure through a process of galvanic replacement. It is proposed that in addition to the ratio of Ag templates and Au ion additives, the twin boundaries of the Ag templates were the dominating factor causing hollow alloy nanostructures.

Spontaneous growth of ultra-thin titanium oxides shell on Ag nanowires: an electron energy loss spectroscope observation.

Ag nanowires with a spontaneous ultra-thin TiO2 shell (∼0.5 nm) can be grown on TiO2 substrate. STEM/EELS results demonstrate that this oxygen-deficient TiO2 layer is formed through the oxidation of Ti which is released from the substrate and segregated to the nanowire surface simultaneously with crystal growth of the nanowires.

An in situ study on the coalescence of monolayer-protected Au-Ag nanoparticle deposits upon heating.

The structural evolution of thiolate-protected nanoparticles of gold, silver, and their alloys with various Au/Ag ratios (3:1, 1:1, and 1:3) upon heating was investigated by means of in situ synchrotron radiation X-ray diffraction. The relationships between the coalescence and composition of nanoparticles, as well as the surfactant reactions, were clarified. Experimental results show that there existed a critical temperature ranging from 120°C to 164°C, above which the tiny broad X-ray diffraction peaks became sharp and strong due to particle coalescence. The coalescence temperatures for alloy nanoparticle deposits were clearly lower than those for pure metals, which can be ascribed to the rivalry between the thermodynamic effect due to alloying and the interactions between surface-assembled layers and the surface atoms of the nanoparticles. The strong affinity of thiolates to Ag and thus complex interactions give rise to a greater energy barrier for the coalescence of nanoparticles into the bulk and subsequent high coalescence temperature. The influences of particle coalescence on the optical and electrical properties of the nanoparticle deposits were also explored.

Passivation ability of graphene oxide demonstrated by two-different-metal solar cells.

The study on graphene oxide (GO) grows rapidly in recent years. We find that graphene oxide could act as the passivation material in photovoltaic applications. Graphene oxide has been applied on Si two-different-metal solar cells. The suitable introduction of graphene oxide could result in obvious enhancement on the efficiency. The simple chemical process to deposit graphene oxide makes low thermal budget, large-area deposition, and fast production of surface passivation possible. The different procedures to incorporate graphene oxide in Si two-different-metal solar cells are compared, and 21% enhancement on the efficiency is possible with a suitable deposition method.

Cu(In(1-x)Ga(x))S2 nanocrystals and films: low-temperature synthesis with size and composition control.

We demonstrate a single-step X-ray irradiation process that yields high-quality Cu(In1-xGax)S2 nanocrystals in colloidal solutions, with complete control of size and composition. Thin films produced by drop-casting exhibit high-quality photoresponse, confirming that our process is suitable for microelectronics applications.

Shape-controlled synthesis of silver nanocrystals by X-ray irradiation for inkjet printing.

A suite of silver (Ag) nanocrystals have been synthesized using a rapid water radiolysis approach via X-ray irradiation. Various shapes including spheroidal, prism, rod, and multifaceted nanoparticles can be produced by varying the initial concentration of polyvinylpyrrolidone (PVP) relative to silver nitrate (AgNO3). UV-visible spectroscopy and transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED) have been used to characterize these Ag products. At an optimized reagent ratio, a mixture of high-aspect-ratio rods (tunable to ∼50) and spheroidal particles result. Such a mixture is proven to have highly beneficial melting point and dispersive properties suited to inkjet printing of conductive Ag lines. The resistivity of the printed lines decreases to 77.7 µΩ and 33.1 µΩ after heating to 200 and 350 °C.

Ultra-long Pt nanolawns supported on TiO2-coated carbon fibers as 3D hybrid catalyst for methanol oxidation.

In this study, TiO2 thin film photocatalyst on carbon fibers was used to synthesize ultra-long single crystalline Pt nanowires via a simple photoreduction route (thermally activated photoreduction). It also acted as a co-catalytic material with Pt. Taking advantage of the high-aspect ratio of the Pt nanostructure as well as the excellent catalytic activity of TiO2, this hybrid structure has the great potential as the active anode in direct methanol fuel cells. The electrochemical results indicate that TiO2 is capable of transforming CO-like poisoning species on the Pt surface during methanol oxidation and contributes to a high CO tolerance of this Pt nanowire/TiO2 hybrid structure.

Kinetic study of Pt nanocrystal deposition on Ag nanowires with clean surfaces via galvanic replacement.

Without using any templates or surfactants, this study develops a high-yield process to prepare vertical Ag-Pt core-shell nanowires (NWs) by thermally assisted photoreduction of Ag NWs and successive galvanic replacement between Ag and Pt ions. The clean surface of Ag nanowires allows Pt ions to reduce and deposit on it and forms a compact sheath comprising Pt nanocrystals. The core-shell structural feature of the NWs thus produced has been demonstrated via transmission electron microscopy observation and Auger electron spectroscopy elemental analysis. Kinetic analysis suggests that the deposition of Pt is an interface-controlled reaction and is dominated by the oxidative dissolution of Ag atoms. The boundaries in between Pt nanocrystals may act as microchannels for the transport of Ag ions during galvanic replacement reactions.

Fabrication of single crystal CuGaS2 nanorods by X-ray irradiation.

CuGaS(2) nanorods were synthesized by irradiating the precursor solution with intense X-rays. The products are single crystal nanorods with preferential [220] growth and a uniform size distribution. We also report on the photoresponse of drop-cast films of these nanorods.

Direct growth of ultra-long platinum nanolawns on a semiconductor photocatalyst.

A template- and surfactant-free process, thermally assisted photoreduction, is developed to prepare vertically grown ultra-long Pt nanowires (NWs) (about 30-40 nm in diameter, 5-6 µm in length, and up to 80 NWs/100 µm2 in the wire density) on TiO2 coated substrates, including Si wafers and carbon fibers, with the assistance of the photocatalytic ability and semiconductor characteristics of TiO2. A remarkable aspect ratio of up to 200 can be achieved. TEM analytical results suggest that the Pt NWs are single-crystalline with a preferred 〈111〉 growth direction. The precursor adopted and the heat treatment conditions are crucial for the yield of NWs. The photoelectrons supplied by TiO2 gives rise to the formation of nano-sized Pt nuclei from salt melt or solution. The subsequent growth of NWs is supported by the thermal electrons which also generated from TiO2 during the post thermal treatment. The interactions between the ions and the electrons in the Pt/TiO2 junction are discussed in this study.

Observations on PVP-protected noble metallic nanoparticle deposits upon heating via in situ synchrotron radiation X-ray diffraction.

Through monitoring the evolution of the X-ray diffraction peaks, the phase transformation of PVP-protected Ag and Au nanoparticle deposits (NPDs) on electronic substrates of Cu and Ni upon heating in air was investigated via in situ synchrotron radiation X-ray diffraction. With an increasing temperature, the broad diffraction peak of nano-sized Ag and Au particles with the original average diameters of 4.2 nm and 9.6 nm, respectively, became sharp because of particle coarsening and coalescence. Complex phase transitions among Au, Cu, AuCu(3) and CuO(x) were observed, mainly due to the negative enthalpy of mixing between Au and Cu. The interactions between NPDs and the substrates affected the shift of diffraction peaks to lower angles, caused by thermal expansion and also the temperature for the oxide formation. Compared to Au, Ag NPDs did not form intermetallic compounds with Cu and the formation of copper oxides can also be retarded mainly due to the phase separation feature of the Ag-Cu system.