Eric K. Lin

Significant dependence of morphology and charge carrier mobility on substrate surface chemistry in high performance polythiophene semiconductor films

The authors report a significant dependence of the morphology and charge carrier mobility of poly(2,5-bis(3-dodecylthiophene-2-yl)thieno[3,2-b]thiophene) (pBTTT) films on the substrate surface chemistry upon heating into its liquid crystal phase. In contrast with films on bare silicon oxide surfaces, pBTTT films on oxide functionalized with octyltrichlorosilane exhibit substantial increases in the lateral dimensions of molecular terraces from nanometers to micrometers, increased orientational order, and higher charge carrier mobility. The large-scale crystallinity of this polymer plays an important role in the high carrier mobility observed in devices, but renders it more sensitive to substrate surface chemistry than other conjugated polymers.

Properties of nanoporous silica thin films determined by high-resolution x-ray reflectivity and small-angle neutron scattering

A new methodology based on a novel combination of a high-resolution specular x-ray reflectivity and small-angle neutron scattering has been developed to evaluate the structural properties of low-dielectric-constant porous silica thin films about one micrometer thick supported on silicon wafer substrates. To complement these results, film composition was determined by high-energy ion scattering techniques. For the example thin film presented here, the overall film density was found to be (0.55±0.01) g/cm3 with a pore wall density of (1.16±0.05) g/cm3 and a porosity of (53±1)%. The characteristic average dimension for the pores was found to be (65±1) A. It was determined that (22.1±0.5)% of the pores had connective paths to the free surface. The mass fraction of water absorption was (3.0±0.5)% and the coefficient of thermal expansion was (60±20)×10−6/°C from room temperature to 175 °C. Lastly, model fitting of the specular x-ray reflectivity data indicated the presence of a thin surface layer with an increa...

Small angle x-ray scattering metrology for sidewall angle and cross section of nanometer scale line gratings

High-volume fabrication of nanostructures requires nondestructive metrologies capable of measuring not only the pattern size but also the pattern shape profile. Measurement tool requirements will become more stringent as the feature size approaches 50nm and tolerances of pattern shape will reach a few nanometers. A small angle x-ray scattering (SAXS) based technique has been demonstrated to have the capability of characterizing the average pitch size and pattern width to subnanometer precision. In this study, we report a simple, modeling-free protocol to extract cross-section information such as the average sidewall angle and the pattern height of line grating patterns from the SAXS data. Diffraction peak intensities and reciprocal space positions are measured while the sample is rotated around the axis perpendicular to the grating direction. Linear extrapolations of peak positions in reciprocal space allow a precise determination of both the sidewall angle and the pattern height.

Small angle x-ray scattering for sub-100 nm pattern characterization.

Characterization of sub-100 nm photolithographic patterns with nanometer scale resolution is demonstrated using small angle x-ray scattering. The transmission scattering geometry employed potentially enables high throughput measurements for future technology nodes of the semiconductor industry, organic and inorganic nanoscale devices, and three-dimensional structures. The method is demonstrated through the characterization of a series of polymer photoresist gratings using a synchrotron x-ray source. Quantities, such as periodicity and line width, are extracted using minimal modeling. Additional quantities and the potential of a laboratory-based x-ray system are briefly discussed.

Structural characterization of porous low-k thin films prepared by different techniques using x-ray porosimetry

Three different types of porous low-k dielectric films, with similar dielectric constants, are characterized using x-ray porosimetry (XRP). XRP is used to extract critical structural information, such as the average density, wall density, porosity, and pore size distribution. The materials include a plasma-enhanced-chemical-vapor-deposited carbon-doped oxide film composed of Si, C, O, and H (SiCOH) and two spin cast silsesquioxane type films—methylsilsesquioxane with a polymeric porogen (porous MSQ) and hydrogensilsesquioxane with a high boiling point solvent (porous HSQ). The porous SiCOH film displays the smallest pore sizes, while porous HSQ film has both the highest density wall material and porosity. The porous MSQ film exhibits a broad range of pores with the largest average pore size. We demonstrate that the average pore size obtained by the well-established method of neutron scattering and x-ray reflectivity is in good agreement with the XRP results.

Thermodynamic Interactions in Double-Network Hydrogels

Double-network hydrogels (DN-gels) prepared from the combination of a moderately cross-linked anionic polyelectrolyte (PE) and an uncross-linked linear polymer solution (NP) exhibit mechanical properties such as fracture toughness that are intriguingly superior to that of their individual constituents. The scheme of double-network preparation, however, is not equally successful for all polyelectrolyte/neutral polymer pairs. A successful example is the combination of poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS) cross-linked network and linear polyacrylamide (PAAm), which results in DN-gels with fracture strength under compression approaching that of articular cartilage ( approximately 20 MPa). Small-angle neutron scattering was used to determine the thermodynamic interaction parameters for PAMPS and PAAm in water as a first step to elucidate the molecular origin responsible for this superior property. Measurements on PAMPS/PAAm DN-gels and their solution blend counterparts indicate that the two polymers interact favorably with each other while in water. This favorable PAMPS/PAAm interaction given by the condition chi(PE-NP) < chi(PE-water) <chi(NP-water), where chi is the Flory-Huggins interaction parameter, is consistent with some of the salient features of the DN structure revealed by SANS, and it may also contribute to the ultimate mechanical properties of DN-gels.

Effects of humidity on unencapsulated poly(thiophene) thin-film transistors

The effects of humidity on unencapsulated polymeric thin-film transistors (TFTs) of poly[5,5’-bis(3-dodecyl-2-thienyl)-2,2’-bithiophene] (PQT-12) were investigated. The field effect mobility of PQT-12 TFTs decreases and the rate of trapping of charge carriers increases under increasing humidity. The amount of water absorbed by the PQT-12 films was measured using a quartz crystal microbalance. Thin films of PQT-12 absorb comparable amounts of water to the carrier concentration in TFTs under routine operating conditions (humidity of 30% relative humidity and gate voltage of −30V); the changes in electrical characteristics under humid atmospheres are attributed to the interaction of absorbed water with the carriers in the film.

Molecular Model for Toughening in Double-Network Hydrogels

A molecular mechanism is proposed for the toughness enhancement observed in double-network (DN) hydrogels prepared from poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polyelectrolyte network and poly(acrylamide) (PAAm) linear polymer. It is an extension of the phenomenological model set forth recently by Gong et al. ( Macromolecules 2007, 40, 6658- 6664 ). This mechanism rationalizes the changes in molecular structure of the DN gel constituents observed via in situ neutron scattering measurements, the composition dependence of the solution viscosity, and the thermodynamic interaction parameters of PAMPS and PAAm molecules obtained previously from neutron scattering studies. More specifically, this proposed mechanism provides an explanation for the observed periodic compositional fluctuations in the micrometer range induced by large strain deformation.

Effect of initial resist thickness on residual layer thickness of nanoimprinted structures

Quantification and control of the residual layer thickness is a critical challenge facing nanoimprint lithography. This thickness must be known to within a few nanometers, yet there are very few nondestructive measurement techniques capable of extracting such information. Here we describe a specular x-ray reflectivity technique that can be used to not only quantify the thickness of the residual layer with sub-nm resolution, but also to extract the pattern height, the line-to-space ratio, and relative linewidth variations as a function of the pattern height. This is illustrated through a series of imprints where the initial film thickness is varied. For films with sufficient resist material to fill the mold, complete pattern filling is observed and the residual layer thickness is directly proportional to the initial film thickness. When there is insufficient resist material in the film to completely fill the patterns in the mold, a finite residual layer thickness of approximately 50–100A is still observed.

Resolution limitations in chemically amplified photoresist systems

A variety of experimental evidence suggests that positive-tone chemically amplified photoresists have an intrinsic bias that might limit resolution during high-volume lithographic processing. If this is true, the implications for the semiconductor industry require careful consideration. The design concept of chemical amplification is based on generation of a chemically stable catalytic species in exposed regions of the photoresist film. The catalytic action of the photoproducts on the photoresist polymer causes a change in the dissolution rate in the irradiated regions of the film. Formation of a stable catalyst species is required for chemical amplification, but it has long been recognized that catalyst migration can produce a difference between the initial distribution of exposure energy and the final distribution of photoproducts. This difference, known as diffusion bias, depends on the photoresist chemistry and processing conditions. Diffusion bias is insensitive to exposure conditions, but it is possible to reduce catalyst migration through changes to resist formulation such as increasing the size of the catalyst molecule or processing conditions such as reducing the post exposure bake temperature. Another common approach to limiting diffusion bias is to incorporate base additives into the photoresist formulation to scavenge diffusing acid catalyst. All of these approaches to reducing catalyst migration generally reduce the catalytic efficiency of each photoproduct and therefore increase the total exposure dose required to pattern the film. Increases in required exposure dosage reduce the throughput of the exposure tools and can reduce the profitability of the manufacturing process. In this paper we present experimental results that are suggestive of an intrinsic photoresist bias. This diffusion bias sets a minimum resolution limit for chemically amplified resist systems that can be improved at the cost of reduced throughput and productivity.