Thermal and acid-catalyzed deprotection kinetics in candidate deep ultraviolet resist materials

Abstract

Articles you may be interested inReal-time Fourier transform infrared spectroscopy study of the kinetics of acid-catalyzed negative-tone resists based on hexamethoxymethylmelamine and phenolic resins Negative electron-beam nanofabrication resist using acid-catalyzed protection of polyphenol provided by phenylcarbinol J.Deep-ultraviolet (UV) chemically amplified (CA) resists are leading candidates for semiconductor lithography manufacturing in the sub-half-micron regime. In this article, we describe in situ, high data rate, accurate measurements of the chemical kinetics that occur in CA resists during the post-exposure bake. The thermal and acid-catalyzed deprotection of two candidate deep-UV resist materials, poly(p-t-butoxycarbonyloxystyrene) (PTBOCST) and poly(t-butylmethacrylate) (PTBMA), was characterized. The thermal deprotection of PTBOCST and PTBMA showed auto-accelerated behavior as the reaction proceeds, while the acid-catalyzed deprotection displayed inhibition as extent of conversion increased. We propose models for the thermal and acid-catalyzed deprotection and extracted rate coefficients using a stochastic kinetics simulator. Excellent agreement between the model and experimental data was obtained.

Photoresist Latent and Developer Images as Probed by Neutron Reflectivity Methods

“…In the case of Houle [ 28 ] the decrease in the diffusivity of the photoacid can be modeled as a reversible reaction between the photoacid and the pendent hydroxyl group of the deprotected monomer. [ 38 ] Houle et al were able to predict the shape and extent of the deprotection front [ 12 , 28 , 38-42 ] as confi rmed through direct measurements by neutron refl ectivity. [ 31 ] trifl ic acid (Tf), perfl uorobutane sulfonic acid (PFBS) and perfl uorooctane sulfonic acid (PFOS).…”

Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals

“…Similar approaches have been previously applied to kinetics modeling of gas-phase aerosol oxidation, 35 combustion, [36][37][38][39] and polymer chemistry. [29][30][31] Because of the symmetry of the molecule, squalane is broken up into a collection of hydrogen reactive sites as shown in Figure 3.. The concentration of each type of hydrogen is set to the initial concentration of squalane multiplied by the number of hydrogens for each type.…”

“…The program used for the simulations is called Kinetiscope and is an enhanced version of the CKS and VSIM codes used in previous work. [29][30][31] This simulation package has been used to successfully describe key aspects of materials chemistry, from rare events controlled by coupled equilibria 32,33 to coupled reaction-diffusion processes on surfaces. 30 The simulations generate an absolute time base, enabling direct comparison of the concentrations and other system properties as a function of time to experimental data.…”

Dual‐Tone Patterned Mesoporous Silicate Films Templated From Chemically Amplified Block Copolymers

“…The reactor was filled first at low temperature and then heated to avoid deactivation of the acid. It is known that photoacids can deactivate after heating or post-exposure baking [43][44][45][46][47]. If the reactor was heated first and pressurized next, then the photoacid, which hydrolyzed PtbA to PAA, would not be available to convert TEOS to silica.…”