Carl E. Larson

Chemical vapor deposition of copper from 1,5‐cyclooctadiene copper(I) hexafluoroacetylacetonate

We have studied the chemical vapor deposition of copper from 1,5‐cyclooctadiene Cu(I) hexafluoroacetylacetonate, a moderately volatile yellow cystalline solid. It yields pure copper by pyrolytic decomposition at 150–250 °C, produces copper films with near bulk resistivity, and has the advantage of being air stable at room temperature.

Laser‐induced chemical vapor deposition of aluminum

The laser‐induced deposition of high‐purity aluminum metal has been achieved by pyrolytic decomposition of trimethylamine aluminum hydride. The chemical structure of the precursor affords a high ambient vapor pressure which results in rapid rates of aluminum film formation. In addition, the precursor is nonpyrophoric, in contrast to other trialkylaluminum precursors. These combined chemical and physical properties make trimethylamine aluminum hydride an ideal precursor for laser‐induced chemical vapor deposition of aluminun films.

Effect of resist components on image spreading during postexposure bake of chemically amplified resists

The ultimate feature size achievable using a chemically amplified resist is determined by chemical and physical processes occurring during the post-exposure bake process. Using a combined experimental-modelling procedure we previously have developed a physically accurate, predictive description of coupled deprotection and diffusion in poly(p- tert-butyloxycar-bonyloxystyrene) (PTBOCST) resist containing a diaryliodonium perfluorobutanesulfonate salt as photoacid generator (PAG). In the present work we extend that study to quantify the impact of anion size and of added base on resist reaction diffusion kinetics. Our results show that both short and long range mobility of the PAG anion influence image spreading; the small triflate counterion leads to acid diffusion larger by a factor of 9 - 70 than that observed with the larger perfluoro-butanesulfonate counterion. The addition of tetra-n-butylammonium hydroxide leads to an overall suppression of image spreading in the exposed resist. This effect can be analyzed quantitatively using a proportional neutralization model, which reveals that base addition can lead to an overall sharpening of the developable latent image of deprotection even in the absence of acid diffusion.

Carbon nanotube scanning probe for profiling of deep-ultraviolet and 193 nm photoresist patterns

The continual scaling down of complementary metal–oxide semiconductor feature size to 100 nm and below necessitates a characterization technique to resolve high-aspect-ratio features in the nanoscale regime. We report the use of atomic force microscopy coupled with high-aspect-ratio multiwalled carbon nanotube (MWCNT) scanning probe tip for the purpose of imaging surface profile of photoresists. MWCNT tips of 5–10 nm in diameter and about a micron long are used. Their exceptional mechanical strength and ability to buckle reversibly enable resolution of steep, deep nanoscale features. Images of photoresist patterns generated by 257 nm interference lithography as well as 193 nm lithography are presented to demonstrate MWCNT scanning probe tips for applications in metrology.

Liquid immersion lithography: evaluation of resist issues

We address in this report a set of key questions tied to the implementation of liquid immersion lithography, from the perspective of the resist materials. We discuss the broad question of whether chemically amplified resists are capable of achieving the spatial resolution that ultimately will be required for the most advanced immersion scenario. Initial studies undertaken using model 193 nm resist materials provide some insight into how an aqueous liquid immersion process can affect the resist material.

Chemical Vapor Deposited Copper from Alkyne Stabilized Copper (I) Hexafluoroacetylacetonate Complexes

High-purity copper films were deposited at substrate temperatures between 150 and 225 o C via pyrolytic decomposition of a series of alkyne stabilized copper(I) hexafluoroacetylacetonate complexes. The copper-alkyne complexes display varying chemical and physical properties which are dependent upon the identity of the alkyne species used to stabilize the reactive copper(I) moiety. The relationship of precursor structure towards the observed partial pressure and film growth rate are highlighted under transport-limited reactor conditions

Aliphatic platforms for the design of 157-nm chemically amplified resists

Our primary platform for 157 nm positive resists is built on a copolymer of t-butyl 2-trifluoromethylacrylate (TBTFMA) and norbornene bearing hexafluoroisopropanol (NBHFA) as an acid group, which is prepared by radical copolymerization. The radical copolymerization of 2-trifluoromethylacrylic monomers with norbornene derivatives has been found through reactivity ratio determination and in situ 1H NMR analysis of kinetics to deviate from the terminal model but to follow the penultimate model. These copolymers typically contain >50 mol% TBTFMA, are lipophilic, and fail to provide good imaging due to poor wettability. Blending a homopolymer of NBHFA (optical density (OD)=1.7/micrometers at 157 nm) into the copolymers (OD=2.5-2.7/micrometers ) increases the hydrophilicity and reduces OD to 2.2-2.0/micrometers , providing high resolution images. Another platform we have identified is a copolymer of TBTFMA with vinyl ethers, which can be prepared by using a common radical initiator. Some of the vinyl ether copolymers are also homogeneously miscible with the NBHFA homopolymer and thus their OD and aqueous base development can be improved by blending.

Ligand-stabilized copper(I) hexafluoroacetylacetonate complexes: NMR spectroscope and the nature of the copper-alkene bond

Abstract Ligand-stabilized copper(I) hexafluoroacetylacetonate complexes display varying degrees of stability to oxidation and thermal decomposition. In an effort to understand the nature of the copper-alkene bond in these complexes better, 1H and 13C nuclear magnetic resonance spectra were obtained and compared to the spectra of the free alkene. In accord with Dewar-Chatt-Duncanson theory, the extent of π and σ bonding contributions can be qualitatively determined by the observed chemical shift changes upon complexation of the alkene to the copper(I) center.

Investigation of the Current Resolution Limits of Advanced Extreme Ultraviolet (EUV) Resists

The past two years has brought tremendous improvements in the crucial area of resists for extreme ultraviolet (EUV) lithography. Nested and isolated line resolutions approaching 30 nm and 25 nm, respectively, have been demonstrated. These advances have been enabled, in large part, by the high-numerical (0.3) EUV imaging capabilities provided by the Berkeley microfield exposure tool (MET). Here we investigate the resolution limits in several advanced EUV resists using the Berkeley MET. Comparisons to aerial-image performance and the use of resolution-enhancing illumination conditions are used to establish the fact that the observed pattern resolution in the best chemically-amplified resists available today are indeed resist limited. Moreover, contrast transfer function (CTF) techniques are used to directly compare various advanced resists. Strong correlation is observed between relative CTF performance and observed resolution limits.

High-resolution 248-nm bilayer resist

Bilayer thin film imaging is one approach to extend 248 nm optical lithography to 150 nm regime and beyond. In this paper, we report our progress in the development of a positive-tone bilayer resist system consisting of a thin silicon containing imaging layer over a recently developed crosslinked polymeric underlayer. The chemically amplified imaging layer resist is based on a novel dual-functional silicon containing monomer, tris(trimethylsilyl)silylethyl methacrylate, which in addition to providing etch resistance, also functions as the acid sensitive functionality. The stabilization of (beta) -silyl carboncation by silicon allows this moiety to serve as an acid sensitive protecting group. Thus high silicon content and high resist contrast are achieved simultaneously. Lithographic evaluation of the bilayer resist with a 0.63 NA and a 0.68 NA 248 nm exposure tool has demonstrated resolution down to 125 nm equal line/space features with a dose latitude of 16 percent and depth of focus (DOF) of 0.6 um. The dose latitude and DOF for 150 nm equal line/space features are 22 percent and 1.2 um, respectively. Finally, residue-free, ultra-high aspect ratio resist features have been obtained by O2 or O2/SO2 reactive ion etching using a high-density plasma etch system. The resist design, deprotection chemistry, lithographic and etch characteristics of the top layer, as well as the design of the new underlay, will be discussed.