Hae-A-Seul Shin

Fast Synthesis of High-Performance Graphene Films by Hydrogen-Free Rapid Thermal Chemical Vapor Deposition

The practical use of graphene in consumer electronics has not been demonstrated since the size, uniformity, and reliability problems are yet to be solved to satisfy industrial standards. Here we report mass-produced graphene films synthesized by hydrogen-free rapid thermal chemical vapor deposition (RT-CVD), roll-to-roll etching, and transfer methods, which enabled faster and larger production of homogeneous graphene films over 400 × 300 mm(2) area with a sheet resistance of 249 ± 17 Ω/sq without additional doping. The properties of RT-CVD graphene have been carefully characterized by high-resolution transmission electron microscopy, Raman spectroscopy, chemical grain boundary analysis, and various electrical device measurements, showing excellent uniformity and stability. In particular, we found no significant correlation between graphene domain sizes and electrical conductivity, unlike previous theoretical expectations for nanoscale graphene domains. Finally, the actual application of the RT-CVD films to capacitive multitouch devices installed in the most sophisticated mobile phone was demonstrated.

Measurement of stresses in Cu and Si around through-silicon via by synchrotron X-ray microdiffraction for 3-dimensional integrated circuits

Through-silicon via (TSV) has been used for 3-dimentional integrated circuits. Mechanical stresses in Cu and Si around the TSV were measured using synchrotron X-ray microdiffraction. The hydrostatic stress in Cu TSV went from high tensile of 234 MPa in the as-fabricated state, to � 196 MPa (compressive) during thermal annealing (in situ measurement), to 167 MPa in the post-annealed state. Due to this stress, the keep-away distance in Si was determined to be about 17 lm. Our results suggest that Cu stress may lead to reliability as well as integration issues, while Si stress may lead to device performance concerns.

Microstructure Evolution and Defect Formation in Cu Through-Silicon Vias (TSVs) During Thermal Annealing

The microstructural evolution of Cu through-silicon vias (TSVs) during thermal annealing was investigated by analyzing the Cu microstructure and the effects of twin boundaries and stress in the TSV. The Cu TSV had two regions with different grain sizes between the center and the edge with a random Cu texture before and after annealing. The grain size of large grains was almost unchanged after annealing, and the abrupt grain growth was restricted by the twin boundaries due to their structural stability. However, microvoids and cracks in the Cu TSV were observed after annealing. These defects were formed by the stress concentration among Cu grains. After defects were formed, the stress level of the TSV was decreased after annealing.

Highly Reliable Ag Nanowire Flexible Transparent Electrode with Mechanically Welded Junctions

Deformation behavior of the Ag nanowire flexible transparent electrode under bending strain is studied and results in a novel approach for highly reliable Ag nanowire network with mechanically welded junctions. Bending fatigue tests up to 500,000 cycles are used to evaluate the in situ resistance change while imposing fixed, uniform bending strain. In the initial stages of bending cycles, the thermally annealed Ag nanowire networks show a reduction in fractional resistance followed by a transient and steady-state increase at later stages of cycling. SEM analysis reveals that the initial reduction in resistance is caused by mechanical welding as a result of applied bending strain, and the increase in resistance at later stages of cycling is determined to be due to the failure at the thermally locked-in junctions. Based on the observations from this study, a new methodology for highly reliable Ag nanowire network is proposed: formation of Ag nanowire networks with no prior thermal annealing but localized junction formation through simple application of mechanical bending strain. The non-annealed, mechanically welded Ag nanowire network shows significantly enhanced cyclic reliability with essentially 0% increase in resistance due to effective formation of localized wire-to-wire contact.

Fatigue-Free, Electrically Reliable Copper Electrode with Nanohole Array

Design and fabrication of reliable electrodes is one of the most important challenges in flexible devices, which undergo repeated deformation. In conventional approaches, mechanical and electrical properties of continuous metal films degrade gradually because of the fatigue damage. The designed incorporation of nanoholes into Cu electrodes can enhance the reliability. In this study, the electrode shows extremely low electrical resistance change during bending fatigue because the nanoholes suppress crack initiation by preventing protrusion formation and damage propagation by crack tip blunting. This concept provides a key guideline for developing fatigue-free flexible electrodes.

Tunable Sn structures in porosity-controlled carbon nanofibers for all-solid-state lithium-ion battery anodes

Volumetric expansion of active materials during lithium (Li) insertion is a critical drawback of Li-alloy anodes and a major bottleneck for their wide adoption in rechargeable batteries. Here, we report on a novel fabrication method of a tin (Sn) fully embedded one-dimensional (1D) carbon (C) matrix which results in minimal volumetric expansion. The 1D C matrix contributes to the buffer role and electron conduction path. This optimized Sn/C structure is enabled by confining the Sn nucleation site and minimizing the outward Sn diffusion originating from stress relaxation. The difference of thermal expansion coefficient between Sn and C derives the stress. The porosity of C nanofibers is a key parameter to modulate the Sn size and dispersion. It is controlled by stabilization and gas–solid reactions between CO (g), CO2 (g), and C nanofibers. The calcination under an Ar environment, which induced the lowest surface area and total pore volume (10.46 m2 g−1 and 0.0217 cm3 g−1), creates an ideal structure of 15 nm sized uniform Sn nanoparticle embedded C nanofibers. It displays a superior anode performance in all-solid-state Li-ion batteries with a capacity of 762 mA h g−1 and coulombic efficiency greater than 99.5% over 50 cycles. Our scheme provides a fundamental impact on anode materials of Li-ion batteries.

Effect of cyclic outer and inner bending on the fatigue behavior of a multi-layer metal film on a polymer substrate

The electrical reliability of a multi-layer metal film on a polymer substrate during cyclic inner bending and outer bending is investigated using a bending fatigue system. The electrical resistance of a Cu film on a polymer substrate during cyclic outer bending increases due to fatigue damage formation, such as cracks and extrusion. Cyclic inner bending also leads to fatigue damage and a similar increase in the electrical resistance. In a sample having a NiCr under-layer, however, the electrical resistance increases significantly during outer bending but not during inner bending mode. Cross-sectional observations reveal that brittle cracking in the hard under-layer results in different fatigue behaviors according to the stress mode. By applying an Al over-layer, the fatigue resistance is improved during both outer bending and inner bending by suppressing fatigue damage formation. The effects of the position, materials, and thickness of the inter-layer on the electrical reliability of a multi-layer sample are also investigated. This study can provide meaningful information for designing a multi-layer structure under various mechanical deformations including tensile and compressive stress.

Influences of semiconductor morphology on the mechanical fatigue behavior of flexible organic electronics

The influence of crystalline morphology on the mechanical fatigue of organic semiconductors (OSCs) was investigated using 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) as a crystalline OSC and poly(triarylamine) (PTAA) as an amorphous OSC. During cyclic bending, resistances of the OSCs were monitored using the transmission-line method on a metal-semiconductor-metal structure. The resistance of the TIPS-pentacene increased under fatigue damage in tensile-stress mode, but no such degradation was observed in the PTAA. Both OSCs were stable under compressive bending fatigue. The formation of intergranular cracks at the domain boundaries of the TIPS-pentacene was responsible for the degradation of its electrical properties under tensile bending fatigue.

Improvements of mechanical fatigue reliability of Cu interconnects on flexible substrates through MoTi alloy under-layer

The mechanical fatigue of Cu films and lines on flexible substrates was investigated, and an improvement in the structures through the use of a MoTi alloy under-layer was proposed. Fatigue reliability was decreased by 3-fold in lines compared with films in the tensile condition and by 6-fold in the compressive condition. Crack formation was observed to be more detrimental for lines than for films. With a MoTi under-layer, the fatigue limit was increased by 2 times that of a structure without MoTi in the tensile condition and by 15 times in the compressive bending condition. The suppression of delamination through the use of a MoTi under-layer improved the fatigue reliability under compressive bending.

Electrical failure and damage analysis of multi-layer metal films on flexible substrate during cyclic bending deformation

The electrical resistance Cu film on flexible substrate was investigated in cyclic bending deformation. The electrical resistance of 1 µm thick Cu film on flexible substrate increased up to 120 % after 500,000 cycles in 1.1 % tensile bending strain. Crack and extrusion were observed due to the fatigue damage of metal film. Low bending strain did not cause any damage on metal film but higher bending strain resulted in severe electrical and mechanical damage. Thinner film showed higher fatigue resistance because of the better mechanical property of thin film. Cu film with NiCr under-layer showed poorer fatigue resistance in tensile bending mode. Ni capping layer did not improve the fatigue resistance of Cu film, but Al capping layer suppressed crack formation and lowered electrical resistance change. The NiCr under layer, Ni capping layer, and Al capping layer effect on electrical resistance change of Cu film was compared with Cu only sample.