A Solvent-Free, Thermally Curable Low-Temperature Organic Planarization Layer for Thin Film Encapsulation.

Thin film encapsulation (TFE) is an essential component to ensure reliable operation of environmentally susceptible organic light-emitting diode-based display. In order to integrate defect-free TFE on display with complex surface structures, additional planarization layer is imperative to planarize the surface topography. The thickness of conventional planarization layer is as high as tens of µm, but the thickness must be reduced substantially to minimize the light leakage in smaller devices such as micro light-emitting diodes. In this study, a thin-less than 2 µm-planarization is achieved via solvent-free process, initiated chemical vapor deposition (iCVD). By adapting copolymer from two soft, but curable monomers, glycidyl acrylate (GA) and 2-(dimethylamino)ethyl methacrylate, excellent planarization performance is achieved on various nano-grating patterns. With only 1.5 µm-thick iCVD planarization layer, a 600 nm-deep trench polyurethane acrylate pattern is flattened completely. The TFE fabricated on planarized pattern exhibits excellent barrier property as fabricated on flat glass substrate, which strongly suggests that iCVD planarization layer can serve as a promising planarization layer to fabricate TFE on various types of complicated device surfaces.

Vapor-phase synthesis of a reagent-free self-healing polymer film with rapid recovery of toughness at room temperature and under ambient conditions.

A rapidly self-healable polymer is highly desirable but challenging to achieve. Herein, we developed an elastomeric film with instant self-healing ability within 10 s at room temperature. For this purpose, a series of copolymers of poly(glycidyl methacrylate-co-2-hydroxyethyl acrylate) (poly(GMA-co-HEA), or pGH) were synthesized in the vapor phase via an initiated chemical vapor deposition (iCVD) process. The elastomer includes a large amount of hydroxyl groups in the 2-hydroxyethyl acrylate (HEA) moiety capable of forming rapid, reversible hydrogen bonding at room temperature, while glycidyl methacrylate (GMA) with a rigid methacrylic backbone chain in the copolymer provides mechanical robustness to the elastic copolymer. With the optimized copolymer composition, pGH indeed showed instant recovery of the toughness within a minute; a completely divided specimen could be welded within a minute at room temperature and under ambient conditions simply by placing the pieces in close contact, which showed the outstanding recovery performance of elastic modulus (93.2%) and toughness (15.6 MJ m-3). The rapid toughness recovery without supplementing any external energy or reagents (e.g. light, temperature, or catalyst) at room temperature and under ambient conditions will be useful in future wearable electronics and soft robotics 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.

Solvent-Free Deposition of Ultrathin Copolymer Films with Tunable Viscoelasticity for Application to Pressure-Sensitive Adhesives.

A new fabrication method for an ultrathin (500 nm thick) pressure-sensitive adhesive (PSA) was demonstrated by utilizing a series of in situ cross-linked viscoelastic copolymer films. Viscoelastic films composed of poly(2-hydroxyethyl acrylate- co-2-ethylhexyl acrylate) were synthesized successfully in a one-step manner by an initiated chemical vapor deposition (iCVD) process, where free-radical polymerization is triggered in the vapor phase either by heat or UV, or a combination of both. In particular, the photoinitiated chemical vapor deposition method generated a highly cross-linked polymer film, whereas cross-linking of the copolymer film was suppressed greatly in the conventional thermal iCVD method. A combination of thermal and photoinitiated chemical vapor deposition could regulate the cross-linking density of the copolymer films. We controlled the cross-linking density of the copolymer films to exhibit a viscoelastic property so that they would readily adhere to various kinds of substrates with only 500 nm thick copolymer PSA. The adhesion performance of the PSA was systematically optimized by tuning the copolymer composition as well as the cross-linking density, and consequently a high shear strength of more than 85.2 ± 5 N/cm2 was achieved despite the 500 nm thickness. In addition, the PSA was completely transparent. We expect that the ultrathin PSAs developed in this work will be utilized widely for the realization of various soft electronic devices, which usually require strong adhesion, tunable viscoelastic properties, and optical transparency.