Ultrathin ZrOx-Organic Hybrid Dielectric (EOT 3.2 nm) via Initiated Chemical Vapor Deposition for High-Performance Flexible Electronics.

A one-step synthesis method is introduced and used to form an ultrathin, homogeneous organic-inorganic hybrid dielectric film with a high dielectric constant (high-k), based on initiated chemical vapor deposition. The hybrid dielectric is synthesized from tetrakis-dimethyl-amino-zirconium and 2-hydroxyethyl methacrylate, which are a high-k inorganic material and a soft organic material, respectively. A detailed material analysis on the synthesized ZrOx-organic hybrid (Zr-hybrid) is performed. The Zr-hybrid dielectric has a high dielectric constant of nine, leading to a film equivalent oxide thickness (EOT) as low as 3.2 nm, which is the lowest EOT obtained from a flexible dielectric layer to date. The leakage current density (J) is no larger than 6 × 10-7 A/cm2 at 2 MV/cm, and the breakdown field (Ebreak) was ∼3.3 MV/cm. The J of the Zr-hybrid dielectric remains almost constant even under the 2.5% strain condition, while that of the ZrO2 dielectric breaks down electrically at a tensile strain of less than 1.0%. The Zr-hybrid dielectric shows an energy band gap in the range of 5.2-5.4 eV and exhibits a sufficient valence band offset of around 3.0 eV with a pentacene organic semiconductor. The gate stack of the Zr-hybrid dielectric/pentacene semiconductor shows decent metal-oxide-semiconductor field-effect transistor performance even under a tensile strain of 1.67%, indicating that the Zr-hybrid is a promising gate dielectric for advanced flexible electronic applications.

Spontaneous Generation of a Molecular Thin Hydrophobic Skin Layer on a Sub-20 nm, High-k Polymer Dielectric for Extremely Stable Organic Thin-Film Transistor Operation.

Polymer dielectric materials with hydroxyl functionalities such as poly(4-vinylphenol) and poly(vinyl alcohol) have been utilized widely in organic thin-film transistors (OTFTs) because of their excellent insulating performance gained by hydroxyl-mediated cross-linking. However, the polar hydroxyl functionality also deleteriously affects the performance of OTFTs and significantly impairs the device stability. In this study, a sub-20 nm, high-k copolymer dielectric with hydroxyl functionality, poly(2-hydroxyethyl acrylate-co-di(ethylene glycol) divinyl ether), was synthesized in the vapor phase via initiated chemical vapor deposition. The inherently dry environment offered by the vapor-phase polymer synthesis prompted the snuggling of polar hydroxyl functionalities into the bulk polymer film to form a molecular thin hydrophobic skin layer at its surface, verified by near-edge X-ray absorption fine structure analysis. The chemical composition of the copolymer dielectric was optimized systematically to achieve high dielectric constant (k ≈ 6.2) as well as extremely low leakage current densities (less than 3 × 10-8 A/cm2 in the range of ±2 MV/cm) even with sub-20 nm thickness, leading to one of the highest capacitance (higher than 300 nF/cm2) achieved by a single polymer dielectric to date. Exploiting the structural advantage of the cross-linked high-k polymer dielectric, high-performance OTFTs were obtained. Notably, the spontaneously formed molecular thin, hydrophobic skin layer in the copolymer film substantially suppressed the hysteresis in the transistor operation. The trap analysis also suggested the formation of bulk trap with a high energy barrier and sufficiently low trap densities at the semiconductor/dielectric interface, owing to the surface skin layer. Furthermore, the OTFTs with the -OH-containing copolymer dielectric showed an unprecedentedly excellent operational stability. No apparent OTFT degradation was observed up to 50 000 s of high constant voltage stress (corresponding to the applied electric field of 1.4 MV/cm) because of the markedly suppressed interfacial trap density by the hydrophobic skin layer, together with the current compensation by the bulk hydroxyl functionalities. We believe that the surface modification-free, one-step polymer dielectric synthetic strategy will provide a new insight into the design of polymer dielectric materials for high-performance, low-power soft electronic devices with high operational stability.

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.

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.

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.

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.

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.