Kwanyong Pak

Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators

We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.

Flexible, Low-Power Thin-Film Transistors Made of Vapor-Phase Synthesized High-k, Ultrathin Polymer Gate Dielectrics

A series of high-k, ultrathin copolymer gate dielectrics were synthesized from 2-cyanoethyl acrylate (CEA) and di(ethylene glycol) divinyl ether (DEGDVE) monomers by a free radical polymerization via a one-step, vapor-phase, initiated chemical vapor deposition (iCVD) method. The chemical composition of the copolymers was systematically optimized by tuning the input ratio of the vaporized CEA and DEGDVE monomers to achieve a high dielectric constant (k) as well as excellent dielectric strength. Interestingly, DEGDVE was nonhomopolymerizable but it was able to form a copolymer with other kinds of monomers. Utilizing this interesting property of the DEGDVE cross-linker, the dielectric constant of the copolymer film could be maximized with minimum incorporation of the cross-linker moiety. To our knowledge, this is the first report on the synthesis of a cyanide-containing polymer in the vapor phase, where a high-purity polymer film with a maximized dielectric constant was achieved. The dielectric film with the optimized composition showed a dielectric constant greater than 6 and extremely low leakage current densities (<3 × 10-8 A/cm2 in the range of ±2 MV/cm), with a thickness of only 20 nm, which is an outstanding thickness for down-scalable cyanide polymer dielectrics. With this high-k dielectric layer, organic thin-film transistors (OTFTs) and oxide TFTs were fabricated, which showed hysteresis-free transfer characteristics with an operating voltage of less than 3 V. Furthermore, the flexible OTFTs retained their low gate leakage current and ideal TFT characteristics even under 2% applied tensile strain, which makes them some of the most flexible OTFTs reported to date. We believe that these ultrathin, high-k organic dielectric films with excellent mechanical flexibility will play a crucial role in future soft electronics.

Vapor-phase deposition of the fluorinated copolymer gate insulator for the p-type organic thin-film transistor

ABSTRACT A copolymer-based gate insulator was synthesized from 1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane (V3D3) and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate (PFDMA) via initiated chemical vapor deposition. The synthesis of the random copolymer of poly(V3D3-co-PFDMA) was confirmed by Fourier transform infrared, X-ray photoelectron spectroscopy, and water contact angle analysis. No phase segregation and pinhole formation were observed in the atomic force microscopy images of the copolymer film. The ultra-thin copolymer film showed an extremely low leakage current density (J < 10−9 A/cm2 in the range of ±2 MV/cm) even with a 70 nm thickness. Pentacene organic thin-film transistors (OTFTs) were fabricated with the copolymer gate insulator and showed excellent operational stability. An up to 95% initial drain current was maintained, and a negligible shift in threshold voltage (VT) was observed even after applying a constant gate bias stress of −12 V and a corresponding electric field of 1.7 MV/cm to the OTFT for 3 ks.

Surface-Localized Sealing of Porous Ultralow-k Dielectric Films with Ultrathin (<2 nm) Polymer Coating

Semiconductor integrated circuit chip industries have been striving to introduce porous ultralow-k (ULK) dielectrics into the multilevel interconnection process in order to improve their chip operation speed by reducing capacitance along the signal path. To date, however, highly porous ULK dielectrics (porosity >40%, dielectric constant (k) <2.4) have not been successfully adopted in real devices because the porous nature causes many serious problems, including noncontinuous barrier deposition, penetration of the barrier metal, and reliability issues. Here, a method that allows porous ULK dielectrics to be successfully used with a multilevel interconnection scheme is presented. The surface of the porous ULK dielectric film (k = 2.0, porosity ∼47%) could be completely sealed by a thin (<2 nm) polymer deposited by a multistep initiated chemical vapor deposition (iCVD) process. Using the iCVD process, a thin pore-sealing layer was localized only to the surface of the porous ULK dielectric film, which could minimize the increase of k; the final effective k was less than 2.2, and the penetration of metal barrier precursors into the dielectric film was completely blocked. The pore-sealed ULK dielectric film also exhibited excellent long-term reliability comparable to a dense low-k dielectric film.

A High-Performance Top-Gated Graphene Field-Effect Transistor with Excellent Flexibility Enabled by an iCVD Copolymer Gate Dielectric

A high-performance top-gated graphene field-effect transistor (FET) with excellent mechanical flexibility is demonstrated by implementing a surface-energy-engineered copolymer gate dielectric via a solvent-free process called initiated chemical vapor deposition. The ultrathin, flexible copolymer dielectric is synthesized from two monomers composed of 1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane and 1-vinylimidazole (VIDZ). The copolymer dielectric enables the graphene device to exhibit excellent dielectric performance and substantially enhanced mechanical flexibility. The p-doping level of the graphene can be tuned by varying the polar VIDZ fraction in the copolymer dielectric, and the Dirac voltage (VDirac ) of the graphene FET can thus be systematically controlled. In particular, the VDirac approaches neutrality with higher VIDZ concentrations in the copolymer dielectric, which minimizes the carrier scattering and thereby improves the charge transport of the graphene device. As a result, the graphene FET with 20 nm thick copolymer dielectrics exhibits field-effect hole and electron mobility values of over 7200 and 3800 cm2 V-1 s-1 , respectively, at room temperature. These electrical characteristics remain unchanged even at the 1 mm bending radius, corresponding to a tensile strain of 1.28%. The formed gate stack with the copolymer gate dielectric is further investigated for high-frequency flexible device applications.

Novel Vapor-Phase Synthesis of Flexible, Homogeneous Organic–Inorganic Hybrid Gate Dielectric with sub 5 nm Equivalent Oxide Thickness

Organic-inorganic hybrid dielectrics have attracted considerable attention for improving both the dielectric constant ( k) and mechanical flexibility of the gate dielectric layer for emerging flexible and wearable electronics. However, conventional solution-based hybrid materials, such as nanocomposite and self-assembled nanodielectrics, have limitations in the dielectric quality when the thickness is deep-scaled, which is critical to realizing high-performance flexible devices. This study proposes a novel vapor-phase synthesis method to form an ultrathin, homogeneous, high- k organic-inorganic hybrid dielectric. A series of hybrid dielectrics is synthesized via initiated chemical vapor deposition (iCVD) in a one-step manner, where 2-hydroxyethyl methacrylate and trimethylaluminum are used as the monomer and inorganic precursor, respectively. The thickness and composition are effectively controlled to form a uniform, defect-free hybrid dielectric. As a result, the synthesized hybrid dielectric has a high- k value as high as 7 and exhibits a low leakage current density of less than 3 × 10-7 A/cm2 at 2 MV/cm, even with an equivalent oxide thickness of less than 5 nm. Furthermore, the dielectric layer shows exceptional chemical stability without any degradation in its dielectric performance and a smooth surface morphology. The dielectric layer also has good flexibility, maintaining its excellent dielectric performance under a tensile strain of up to 2.6%. Organic thin-film transistors with the developed hybrid dielectric as the gate dielectric achieved hysteresis-free transfer characteristics, with an operating voltage of up to 4 V and excellent mechanical flexibility as well. The hybrid dielectric synthesized via the iCVD process is a promising candidate for high-performance, low-power flexible electronics.