Kyuyoung Heo

Bending-stress-driven phase transitions in pentacene thin films for flexible organic field-effect transistors

The effects of bending strain on the structure and electrical characteristics of pentacene films in flexible devices were investigated. It was found that the volume fraction of bulk phase in the pentacene film increases from 10.7% to 27.7% under 1.1% of tensile strain but decreases to 3.5% under 1.0% of compressive strain. These bending-stress-driven phase transitions between the bulk phase and the thin-film phase in the pentacene film resulted in the changes in field-effect mobility, and were driven by the differences between the in-plane dimensions of the crystal unit cells of the two phases to reduce the external bending stress.

Imprinting well-controlled closed-nanopores in spin-on polymeric dielectric thin films

The use of low dielectric constant (low-k) interdielectrics in multilevel structure integrated circuits (ICs) can lower line-to-line noise in interconnects and alleviate power dissipation issues by reducing the capacitance between the interconnect conductor lines. Because of these merits, low-k interdielectric materials are currently in high demand in the development of advanced ICs. This article reviews recent developments in the imprinting of closed nanopores into spin-on materials to produce low-k nanoporous interdielectrics for the production of advanced ICs.

Order-order and order-disorder transitions in thin films of an amphiphilic liquid crystalline diblock copolymer.

In this study, we quantitatively investigated the temperature-dependent phase transition behaviors of thin films of an interesting amphiphilic diblock copolymer, poly(ethylene oxide)-b-poly(11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate) (p(EO)-b-p(MAAZ)) and the resulting morphological structures by using synchrotron grazing incidence X-ray scattering (GIXS) and differential scanning calorimetry. The quantitative GIXS analysis showed that the diblock copolymer in the homogeneous, isotropic melt state undergoes phase-separation near 190 degrees C and then forms a body-centered cubic (BCC) structure of spherical p(EO) domains in the p(MAAZ) matrix, at which point the p(EO) domains and the p(MAAZ) matrix are both in amorphous, liquid states. The BCC structure of spherical p(EO) domains is converted to a hexagonal cylinder structure near 120 degrees C, which is induced by the transformation of the isotropic phase of the p(MAAZ) matrix to the smectic A phase, which is composed of a laterally ordered structure of p(MAAZ) blocks with fully extended side groups. The resulting hexagonal cylinder structure is very stable below 120 degrees C. This microscopic hexagonal cylinder structure is retained as the smectic A phase of the p(MAAZ) matrix undergoes further transitions to smectic C near 104 degrees C and to a smectic X phase near 76 degrees C, while the amorphous, liquid phase of the p(EO) cylinders undergoes crystallization near -15 degrees C. These complicated temperature-dependent disorder-order and order-order phase transitions in the films were found to take place reversibly during the heating run. A face-centered orthorhombic structure of p(EO) domains was also found during the heating run and is an intermediate structure in the hexagonal cylinder structure to BCC structure transformation. We use these structural analysis results to propose molecular structure models at various temperatures for thin films of the diblock polymer.

Nondestructive quantitative synchrotron grazing incidence x-ray scattering analysis of cylindrical nanostructures in supported thin films.

Nondestructive nanostructural analysis is indispensable in the development of nanomaterials and nanofabrication processes for use in nanotechnology applications. This paper demonstrates a quantitative, nondestructive analysis of nanostructured thin films supported on substrates and their templated nanopores by using grazing incidence X-ray scattering and data analysis with a derived scattering theory. The analysis disclosed that vertically oriented nanodomain cylinders had formed in 20–100 nm thick films supported on substrates, which consisted of a mixture of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) and PMMA homopolymer, and that the PMMA nanodomain cylinders were selectively etched out by ultraviolet light exposure and a subsequent rinse with acetic acid, resulting in a well ordered nanostructure consisting of hexagonally packed cylindrical nanopores.

Structural evolution in microbial polyesters.

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry. The polyesters were found to undergo primary crystallization as well as secondary crystallization. In the primary crystallization, the thicknesses of the lamellar crystals were sensitive to the crystallization temperature, but no thickening was observed throughout the entire crystallization at a given temperature. The thickness of the lamellar crystals in the PHB homopolymer was always larger than that of the amorphous layers. In the copolymers, by contrast, the randomly distributed HHx comonomer units were found to be excluded from the lamellar crystals into the amorphous regions during the isothermal crystallization process. This interrupted the crystallization of the copolymer chains, resulting in the formation of lamellar crystals with thicknesses smaller than those of the amorphous layers. The lamellar crystals in the copolymers had lower electron densities compared to those formed in the PHB homopolymer. On the other hand, secondary crystallization favorably occurred during the later stage of isothermal crystallization in competition with the continuous primary crystallization, forming secondary crystals in amorphous regions, in particular in the amorphous layers between the primarily formed lamellar crystal stacks. Compared to the primarily formed lamellar crystals, the secondary crystals had short-range-ordered structures of smaller size, a broader size distribution, and a lower electron density.

Detailed analysis of gyroid structures in diblock copolymer thin films with synchrotron grazing-incidence X-ray scattering

In this study, a grazing-incidence X-ray scattering (GIXS) formula was derived for gyroid structures formed in thin films supported on substrates. Two-dimensional GIXS patterns were measured for gyroid structures formed in polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer nanometre-scale thin films supported on silicon substrates, and a quantitative analysis of the obtained two-dimensional GIXS data was conducted with the scattering formula. This analysis provided details (lattice parameter, width of the PS phase, positional distortion factor, orientation and orientation distribution) of the gyroid structures developed in the diblock copolymer thin films that are not easily obtained using conventional techniques. Moreover, it was possible to simulate complete and detailed two-dimensional GIXS patterns with the determined structure parameters.

Polystyrene‐b‐polyisoprene thin films with hexagonally perforated layer structure: quantitative grazing‐incidence X‐ray scattering analysis

Grazing-incidence X-ray scattering (GIXS) formulas for hexagonally perforated layer (HPL) structures with ABC and AB stacking sequences were derived, and used in the quantitative analysis of the two-dimensional GIXS patterns of polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer thin films supported on silicon substrates. This quantitative analysis provided detailed information (shape, size and size distribution, packing order, layer packing sequence, and orientation) about the HPL structure of the diblock copolymer films that cannot be easily obtained with conventional X-ray and neutron scattering techniques or with conventional microscopic methods.

Polymer chain/nanocrystal ordering in thin films of regioregular poly(3- hexylthiophene) and blends with a soluble fullerene{

Here we report a study of the polymer chain/nanocrystal ordering in thin films (nanolayers) of regioregular poly(3-hexylthiophene) (P3HT) and blends of P3HT with a soluble fullerene derivative. A detailed analysis has been made of two dimensional (2D) grazing incidence X-ray diffraction (GIXRD) measurements with synchrotron radiation. P3HT samples with three different levels of regioregularity (RR) were synthesized and used to investigate the influence of RR on the chain ordering in thin films. Blend films were also prepared to investigate the influence of fullerene molecule addition on chain ordering. For the analysis, one dimensional (1D) GIXRD patterns were extracted from the 2D images for varying azimuthal angles, allowing information to be obtained for chain ordering in both the out-of-plane (OOP) and in-plane (IP) directions. These results show that the degree of P3HT chain ordering is strongly affected by RR, and that thermal annealing improves chain ordering in the OOP direction. This observation is in good agreement with high resolution transmission electron microscope measurements of film nanomorphology.

Two-Dimensionally Well-Ordered Multilayer Structures in Thin Films of a Brush Polypeptide

In this study, we report the first production of two-dimensionally well-ordered molecular multilayers (i.e., with a well-defined molecular lamellar structure) based on the antiparallel beta-sheet chain conformation in thin films of a brush polypeptide, poly(S-n-hexadecyl-dl-homocysteine) (PHHC), through the use of a simple spin-coating process and the quantitative structural and property analysis of the thin films using a grazing incidence X-ray scattering technique combined with Fourier transform infrared spectroscopy and differential scanning calorimetry. These analyses provide detailed information about the structure and molecular conformation of the self-assembled lamellae in the PHHC thin film, which is not easily obtained using conventional techniques. Moreover, we used the in situ measurements carried out at various temperatures and the data analyses to establish mechanisms for the evolution of the self-assembled lamellar structures in the film and for their melting. In addition, we propose molecular structure models of the PHHC polymer molecules in the thin film at various temperatures.

X-ray scattering study of thermal nanopore templating in hybrid films of organosilicate precursor and reactive four-armed porogen

The miscibility and the mechanism for thermal nanopore templating in films prepared from spin-coating and subsequent drying of homogenous solutions of curable polymethylsilsesquioxane dielectric precursor and thermally labile, reactive triethoxysilyl-terminated four-armed poly(epsilon-caprolactone) porogen were investigated in detail by in situ two-dimensional grazing incidence small-angle x-ray scattering analysis. The dielectric precursor and porogen components in the film were fully miscible. On heating, limited aggregations of the porogen, however, took place in only a small temperature range of 100-140 degrees C as a result of phase separation induced by the competition of the curing and hybridization reactions of the dielectric precursor and porogen; higher porogen loading resulted in relatively large porogen aggregates and a greater size distribution. The developed porogen aggregates underwent thermal firing above 300 degrees C without further growth and movement, and ultimately left their individual footprints in the film as spherical nanopores.