Effect of copolymer composition on acid-catalyzed deprotection reaction kinetics in model photoresists

Shuhui H. Kang; Vivek M. Prabhu; Bryan D. Vogt; Eric K. Lin; Wen li Wu; Karen Turnquest

doi:10.1016/j.polymer.2006.07.003

Effect of copolymer composition on acid-catalyzed deprotection reaction kinetics in model photoresists

Shuhui H. Kang, Vivek M. Prabhu, Bryan D. Vogt, Eric K. Lin, Wen li Wu, Karen Turnquest

Chemical Engineering

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41 Scopus citations

Abstract

The kinetics of the deprotection reaction in model photoresist materials was measured as a function of copolymer composition with Fourier transform infrared (FTIR) spectroscopy. A mathematical model was developed to analyze the deprotection kinetics in terms of the coupled reaction rate and acid-diffusion processes. The first-order reaction rate constant decreases as the non-reactive comonomer content increased. Additionally, the extent of reaction appears to saturate to different levels as a function of reaction temperature. The resulting composition-dependent reaction constant arises from a dramatically reduced acid transport rate due to a strong interaction of the acid with the increasing polar resist matrix. The reduced acid transport is consistent with the observed hydrogen bonding between the photoacid and methacrylic acid reaction product. These results provide important insight into the effect of the changing polymer composition on the acid-catalyzed reaction kinetics.

Original language	English (US)
Pages (from-to)	6293-6302
Number of pages	10
Journal	Polymer
Volume	47
Issue number	18
DOIs	https://doi.org/10.1016/j.polymer.2006.07.003
State	Published - Aug 23 2006

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Materials Chemistry

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10.1016/j.polymer.2006.07.003

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@article{11bbc3c391404cce897ed25fd2a33fcd,

title = "Effect of copolymer composition on acid-catalyzed deprotection reaction kinetics in model photoresists",

abstract = "The kinetics of the deprotection reaction in model photoresist materials was measured as a function of copolymer composition with Fourier transform infrared (FTIR) spectroscopy. A mathematical model was developed to analyze the deprotection kinetics in terms of the coupled reaction rate and acid-diffusion processes. The first-order reaction rate constant decreases as the non-reactive comonomer content increased. Additionally, the extent of reaction appears to saturate to different levels as a function of reaction temperature. The resulting composition-dependent reaction constant arises from a dramatically reduced acid transport rate due to a strong interaction of the acid with the increasing polar resist matrix. The reduced acid transport is consistent with the observed hydrogen bonding between the photoacid and methacrylic acid reaction product. These results provide important insight into the effect of the changing polymer composition on the acid-catalyzed reaction kinetics.",

author = "Kang, {Shuhui H.} and Prabhu, {Vivek M.} and Vogt, {Bryan D.} and Lin, {Eric K.} and Wu, {Wen li} and Karen Turnquest",

note = "Funding Information: This work was supported by SEMATECH under Agreement #: 309841 OF. The authors acknowledge M. Padmanaban and Ralph Dammel at AZ Electronics and Jim Sounik and Michael Sheehan at DuPont Electronic Polymers for providing the polymers used in this study. ",

year = "2006",

month = aug,

day = "23",

doi = "10.1016/j.polymer.2006.07.003",

language = "English (US)",

volume = "47",

pages = "6293--6302",

journal = "Polymer",

issn = "0032-3861",

publisher = "Elsevier B.V.",

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T1 - Effect of copolymer composition on acid-catalyzed deprotection reaction kinetics in model photoresists

AU - Kang, Shuhui H.

AU - Prabhu, Vivek M.

AU - Vogt, Bryan D.

AU - Lin, Eric K.

AU - Wu, Wen li

AU - Turnquest, Karen

N1 - Funding Information: This work was supported by SEMATECH under Agreement #: 309841 OF. The authors acknowledge M. Padmanaban and Ralph Dammel at AZ Electronics and Jim Sounik and Michael Sheehan at DuPont Electronic Polymers for providing the polymers used in this study.

PY - 2006/8/23

Y1 - 2006/8/23

N2 - The kinetics of the deprotection reaction in model photoresist materials was measured as a function of copolymer composition with Fourier transform infrared (FTIR) spectroscopy. A mathematical model was developed to analyze the deprotection kinetics in terms of the coupled reaction rate and acid-diffusion processes. The first-order reaction rate constant decreases as the non-reactive comonomer content increased. Additionally, the extent of reaction appears to saturate to different levels as a function of reaction temperature. The resulting composition-dependent reaction constant arises from a dramatically reduced acid transport rate due to a strong interaction of the acid with the increasing polar resist matrix. The reduced acid transport is consistent with the observed hydrogen bonding between the photoacid and methacrylic acid reaction product. These results provide important insight into the effect of the changing polymer composition on the acid-catalyzed reaction kinetics.

AB - The kinetics of the deprotection reaction in model photoresist materials was measured as a function of copolymer composition with Fourier transform infrared (FTIR) spectroscopy. A mathematical model was developed to analyze the deprotection kinetics in terms of the coupled reaction rate and acid-diffusion processes. The first-order reaction rate constant decreases as the non-reactive comonomer content increased. Additionally, the extent of reaction appears to saturate to different levels as a function of reaction temperature. The resulting composition-dependent reaction constant arises from a dramatically reduced acid transport rate due to a strong interaction of the acid with the increasing polar resist matrix. The reduced acid transport is consistent with the observed hydrogen bonding between the photoacid and methacrylic acid reaction product. These results provide important insight into the effect of the changing polymer composition on the acid-catalyzed reaction kinetics.

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U2 - 10.1016/j.polymer.2006.07.003

DO - 10.1016/j.polymer.2006.07.003

M3 - Article

AN - SCOPUS:33746885532

SN - 0032-3861

VL - 47

SP - 6293

EP - 6302

JO - Polymer

JF - Polymer

IS - 18

ER -

Effect of copolymer composition on acid-catalyzed deprotection reaction kinetics in model photoresists

Abstract

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