The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials
Abstract
In order to increase computation power and efficiency, the semiconductor industry continually strives to reduce the size of features written using lithographic techniques. The planned switch to a shorter wavelength extreme ultraviolet (EUV) source presents a challenge for the associated photoresists, which in their current manifestation show much poorer photoabsorption cross sections for the same dose. Here we consider the critical role that an inner-shell electronic structure might play in enhancing photoabsorption cross sections, which one can control by the choice of substituent elements in the photoresist. In order to increase the EUV sensitivity of current photoresists, it is critical to consider the inner-shell atomic structure of the elements that compose the materials. We validate this hypothesis using a series of halogenated organic molecules, which all have similar valence structures, but differ in the character of their semi-core and deep valence levels. Using various implementations of time-dependent density functional theory, the absorption cross sections are computed for the model systems of CH3X, X = H, OH, F, Cl, Br, I, as well as a representative polymer fragment: 2-methyl-phenol and its halogenated analogues. Iodine has a particularly high cross section in the EUV range, which is due to delayed absorption bymore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
- OSTI Identifier:
- 1476485
- Alternate Identifier(s):
- OSTI ID: 1361838
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 146; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
Citation Formats
Closser, Kristina D., Ogletree, D. Frank, Naulleau, Patrick, and Prendergast, David. The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials. United States: N. p., 2017.
Web. doi:10.1063/1.4981815.
Closser, Kristina D., Ogletree, D. Frank, Naulleau, Patrick, & Prendergast, David. The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials. United States. https://doi.org/10.1063/1.4981815
Closser, Kristina D., Ogletree, D. Frank, Naulleau, Patrick, and Prendergast, David. Thu .
"The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials". United States. https://doi.org/10.1063/1.4981815. https://www.osti.gov/servlets/purl/1476485.
@article{osti_1476485,
title = {The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials},
author = {Closser, Kristina D. and Ogletree, D. Frank and Naulleau, Patrick and Prendergast, David},
abstractNote = {In order to increase computation power and efficiency, the semiconductor industry continually strives to reduce the size of features written using lithographic techniques. The planned switch to a shorter wavelength extreme ultraviolet (EUV) source presents a challenge for the associated photoresists, which in their current manifestation show much poorer photoabsorption cross sections for the same dose. Here we consider the critical role that an inner-shell electronic structure might play in enhancing photoabsorption cross sections, which one can control by the choice of substituent elements in the photoresist. In order to increase the EUV sensitivity of current photoresists, it is critical to consider the inner-shell atomic structure of the elements that compose the materials. We validate this hypothesis using a series of halogenated organic molecules, which all have similar valence structures, but differ in the character of their semi-core and deep valence levels. Using various implementations of time-dependent density functional theory, the absorption cross sections are computed for the model systems of CH3X, X = H, OH, F, Cl, Br, I, as well as a representative polymer fragment: 2-methyl-phenol and its halogenated analogues. Iodine has a particularly high cross section in the EUV range, which is due to delayed absorption by its 4d electrons. The computational results are compared to standard database values and experimental data when available. Generally we find that the states that dominate the EUV oscillator strength are generated by excitations of deep valence or semi-core electrons, which are primarily atomic-like and relatively insensitive to the specific molecular structure.},
doi = {10.1063/1.4981815},
journal = {Journal of Chemical Physics},
number = 16,
volume = 146,
place = {United States},
year = {Thu Apr 27 00:00:00 EDT 2017},
month = {Thu Apr 27 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Attosecond vacuum UV coherent control of molecular dynamics
journal, January 2014
- Ranitovic, P.; Hogle, C. W.; Riviere, P.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 3
Atomic radiative and radiationless yields for K and L shells
journal, April 1979
- Krause, M. O.
- Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2
Extreme ultraviolet lithography: A review
journal, January 2007
- Wu, Banqiu; Kumar, Ajay
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 25, Issue 6
A hybrid polymeric material bearing a ferrocene-based pendant organometallic functionality: synthesis and applications in nanopatterning using EUV lithography
journal, January 2014
- Satyanarayana, V. S. V.; Singh, Vikram; Kalyani, Vishwanath
- RSC Adv., Vol. 4, Issue 104
Time-dependent density functional theory: Past, present, and future
journal, August 2005
- Burke, Kieron; Werschnik, Jan; Gross, E. K. U.
- The Journal of Chemical Physics, Vol. 123, Issue 6
Absolute oscillator strengths for photoabsorption (6–360 eV) and ionic photofragmentation (10–80 eV) of methanol
journal, November 1992
- Burton, Gordon R.; Chan, Wing Fat; Cooper, Glyn
- Chemical Physics, Vol. 167, Issue 3
turboTDDFT 2.0—Hybrid functionals and new algorithms within time-dependent density-functional perturbation theory
journal, July 2014
- Ge, Xiaochuan; Binnie, Simon J.; Rocca, Dario
- Computer Physics Communications, Vol. 185, Issue 7
Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption
journal, August 2012
- Lopata, K.; Van Kuiken, B. E.; Khalil, M.
- Journal of Chemical Theory and Computation, Vol. 8, Issue 9
Absolute photoabsorption and photoionization studies of methyl bromide using dipole electron impact and synchrotron radiation PES techniques
journal, May 1997
- Olney, Terry N.; Cooper, Glyn; Fat Chan, Wing
- Chemical Physics, Vol. 218, Issue 1-2
Active control of chemical bond scission by site-specific core excitation
journal, March 2003
- Wada, Shin-ichi; Sumii, Ryohei; Isari, Kouji
- Surface Science, Vol. 528, Issue 1-3
Optical lithography: Introduction
journal, January 1997
- Chiu, G. L. -T.; Shaw, J. M.
- IBM Journal of Research and Development, Vol. 41, Issue 1.2
Core-level spectroscopy and dynamics of free molecules
journal, January 2011
- Feifel, R.; Piancastelli, M. N.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 183, Issue 1-3
Electron scattering from CH3I. Total cross section measurements
journal, July 1993
- Szmytkowski, Czesław; Krzysztofowicz, Andrzej M.
- Chemical Physics Letters, Vol. 209, Issue 5-6
octopus: a tool for the application of time-dependent density functional theory
journal, September 2006
- Castro, Alberto; Appel, Heiko; Oliveira, Micael
- physica status solidi (b), Vol. 243, Issue 11
Time-dependent density functional theory calculations of the spectroscopy of core electrons
journal, January 2010
- Besley, Nicholas A.; Asmuruf, Frans A.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 38
Turbo charging time-dependent density-functional theory with Lanczos chains
journal, April 2008
- Rocca, Dario; Gebauer, Ralph; Saad, Yousef
- The Journal of Chemical Physics, Vol. 128, Issue 15
Photoabsorption spectra in the continuum of molecules and atomic clusters
journal, February 2001
- Nakatsukasa, Takashi; Yabana, Kazuhiro
- The Journal of Chemical Physics, Vol. 114, Issue 6
The time‐dependent Schrödinger equation: Application of absorbing boundary conditions
journal, April 1989
- Neuhasuer, Daniel; Baer, Michael
- The Journal of Chemical Physics, Vol. 90, Issue 8
Near and Above Ionization Electronic Excitations with Non-Hermitian Real-Time Time-Dependent Density Functional Theory
journal, September 2013
- Lopata, Kenneth; Govind, Niranjan
- Journal of Chemical Theory and Computation, Vol. 9, Issue 11
Photolithographic properties of tin-oxo clusters using extreme ultraviolet light (13.5nm)
journal, September 2014
- Cardineau, Brian; Del Re, Ryan; Marnell, Miles
- Microelectronic Engineering, Vol. 127
Time-Dependent Density Functional Theory Study of the X-ray Absorption Spectroscopy of Acetylene, Ethylene, and Benzene on Si(100)
journal, January 2007
- Besley, Nicholas A.; Noble, Adam
- The Journal of Physical Chemistry C, Vol. 111, Issue 8
Environmentally stable chemical amplification positive resist: principle, chemistry, contamination resistance, and lithographic feasibility.
journal, January 1994
- Ito, Hiroshi; Breyta, Greg; Hofer, Don
- Journal of Photopolymer Science and Technology, Vol. 7, Issue 3
Quantitative studies of the photoabsorption (4.5–488 eV) and photoionization (9–59.5 eV) of methyl iodide using dipole electron impact techniques
journal, June 1998
- Olney, Terry N.; Cooper, Glyn; Brion, C. E.
- Chemical Physics, Vol. 232, Issue 1-2
TD-DFT benchmarks: A review
journal, April 2013
- Laurent, Adèle D.; Jacquemin, Denis
- International Journal of Quantum Chemistry, Vol. 113, Issue 17
Time-Dependent Density Functional Response Theory for Molecules
book, November 1995
- Casida, Mark E.
- Recent Advances in Density Functional Methods
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014
- Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny
- Molecular Physics, Vol. 113, Issue 2
Atomic form factors, incoherent scattering functions, and photon scattering cross sections
journal, July 1975
- Hubbell, J. H.; Veigele, Wm. J.; Briggs, E. A.
- Journal of Physical and Chemical Reference Data, Vol. 4, Issue 3
Absolute photoabsorption (6–350 eV) and photoionization (11–80 eV) of methyl chloride using dipole electron scattering and synchrotron radiation spectroscopies
journal, May 1996
- Olney, Terry N.; Cooper, Glyn; Chan, Wing Fat
- Chemical Physics, Vol. 205, Issue 3
Fluorescence yields and Coster–Kronig probabilities for the atomic L subshells. Part II: The L1 subshell revisited
journal, January 2009
- Campbell, J. L.
- Atomic Data and Nuclear Data Tables, Vol. 95, Issue 1
Accelerating Real-Time Time-Dependent Density Functional Theory with a Nonrecursive Chebyshev Expansion of the Quantum Propagator
journal, October 2016
- Williams-Young, David; Goings, Joshua J.; Li, Xiaosong
- Journal of Chemical Theory and Computation, Vol. 12, Issue 11
Multiconfigurational Self-Consistent Field Study of the Excited State Properties of 4-Thiouracil in the Gas Phase
journal, September 2004
- Shukla, M. K.; Leszczynski, Jerzy
- The Journal of Physical Chemistry A, Vol. 108, Issue 35
turboTDDFT – A code for the simulation of molecular spectra using the Liouville–Lanczos approach to time-dependent density-functional perturbation theory
journal, August 2011
- Malcıoğlu, Osman Barış; Gebauer, Ralph; Rocca, Dario
- Computer Physics Communications, Vol. 182, Issue 8
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules
journal, November 2005
- Dreuw, Andreas; Head-Gordon, Martin
- Chemical Reviews, Vol. 105, Issue 11
Statistical simulation of photoresists at EUV and ArF
conference, March 2009
- Biafore, John J.; Smith, Mark D.; Mack, Chris A.
- SPIE Advanced Lithography, SPIE Proceedings
Inner-shell photoemission from the iodine atom in I
journal, July 1984
- Lindle, D. W.; Kobrin, P. H.; Truesdale, C. M.
- Physical Review A, Vol. 30, Issue 1
Progress in Time-Dependent Density-Functional Theory
journal, May 2012
- Casida, M. E.; Huix-Rotllant, M.
- Annual Review of Physical Chemistry, Vol. 63, Issue 1
Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post- d group 16–18 elements
journal, December 2003
- Peterson, Kirk A.; Figgen, Detlev; Goll, Erich
- The Journal of Chemical Physics, Vol. 119, Issue 21
On the determination of excitation energies using density functional theory
journal, January 2000
- Tozer, David J.; Handy, Nicholas C.
- Physical Chemistry Chemical Physics, Vol. 2, Issue 10
All-electron time-dependent density functional theory with finite elements: Time-propagation approach
journal, October 2011
- Lehtovaara, Lauri; Havu, Ville; Puska, Martti
- The Journal of Chemical Physics, Vol. 135, Issue 15
The valence shell photoabsorption of the linear alkanes, CnH2n+2 (n=1–8): absolute oscillator strengths (7–220 eV)
journal, June 1993
- Au, Jennifer W.; Cooper, Glynn; Burton, Gordon R.
- Chemical Physics, Vol. 173, Issue 2
UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C–Y (Y = halogen) and O–H bond fission
journal, April 2013
- Sage, Alan G.; Oliver, Thomas A. A.; King, Graeme A.
- The Journal of Chemical Physics, Vol. 138, Issue 16
EUV Extendibility: Challenges Facing EUV at 1x and beyond
journal, January 2013
- Naulleau, Patrick P.; Anderson, Christopher N.; Bhattarai, Suchit
- Journal of Photopolymer Science and Technology, Vol. 26, Issue 6
Where Is the Electronic Oscillator Strength? Mapping Oscillator Strength across Molecular Absorption Spectra
journal, March 2016
- Zheng, Lianjun; Polizzi, Nicholas F.; Dave, Adarsh R.
- The Journal of Physical Chemistry A, Vol. 120, Issue 11
X-Ray Interactions: Photoabsorption, Scattering, Transmission, and Reflection at E = 50-30,000 eV, Z = 1-92
journal, July 1993
- Henke, B. L.; Gullikson, E. M.; Davis, J. C.
- Atomic Data and Nuclear Data Tables, Vol. 54, Issue 2, p. 181-342
X-ray Absorption in Insulators with Non-Hermitian Real-Time Time-Dependent Density Functional Theory
journal, January 2015
- Fernando, Ranelka G.; Balhoff, Mary C.; Lopata, Kenneth
- Journal of Chemical Theory and Computation, Vol. 11, Issue 2
Review on Micro- and Nanolithography Techniques and their Applications
journal, January 2012
- Pimpin, Alongkorn; Srituravanich, Werayut
- Engineering Journal, Vol. 16, Issue 1
Molecular dynamics in electronically excited states using time-dependent density functional theory
journal, March 2005
- Tavernelli *, Ivano; Röhrig, Ute F.; Rothlisberger, Ursula
- Molecular Physics, Vol. 103, Issue 6-8
Strong Electronic Selectivity in the Shallow Core Excitation of the CH 2 Cl 2 Molecule
journal, August 2015
- Alcantara, K. F.; Gomes, A. H. A.; Wolff, W.
- The Journal of Physical Chemistry A, Vol. 119, Issue 33
Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method
journal, July 2015
- Ghosh, Aryya; Pal, Sourav; Vaval, Nayana
- The Journal of Chemical Physics, Vol. 143, Issue 2
X-ray Absorption Spectroscopy
book, January 2003
- Penner-Hahn, J. E.
- Comprehensive Coordination Chemistry II
Accuracy and computational efficiency of real-time subspace propagation schemes for the time-dependent density functional theory
journal, May 2016
- Russakoff, Arthur; Li, Yonghui; He, Shenglai
- The Journal of Chemical Physics, Vol. 144, Issue 20
Bismuth Resists for EUV Lithography
journal, January 2014
- Passarelli, James; Sortland, Miriam; Re, Ryan Del
- Journal of Photopolymer Science and Technology, Vol. 27, Issue 5
Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States
journal, October 2011
- Liang, Wenkel; Fischer, Sean A.; Frisch, Michael J.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 11
Quantitative studies of the photoabsorption, photoionization, and ionic photofragmentation of methyl fluoride at VUV and soft X-ray energies (7–250 eV) using dipole electron scattering and synchrotron radiation
journal, December 1994
- Olney, Terry N.; Cooper, Glyn; Chan, Wing Fat
- Chemical Physics, Vol. 189, Issue 3
Modeling electron dynamics coupled to continuum states in finite volumes with absorbing boundaries
journal, March 2015
- De Giovannini, Umberto; Larsen, Ask Hjorth; Rubio, Angel
- The European Physical Journal B, Vol. 88, Issue 3
Propagators for the time-dependent Kohn–Sham equations
journal, August 2004
- Castro, Alberto; Marques, Miguel A. L.; Rubio, Angel
- The Journal of Chemical Physics, Vol. 121, Issue 8
The iterative calculation of a few of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices
journal, January 1975
- Davidson, Ernest R.
- Journal of Computational Physics, Vol. 17, Issue 1
Density-Functional Theory for Time-Dependent Systems
journal, March 1984
- Runge, Erich; Gross, E. K. U.
- Physical Review Letters, Vol. 52, Issue 12
octopus: a first-principles tool for excited electron–ion dynamics
journal, March 2003
- Marques, M.
- Computer Physics Communications, Vol. 151, Issue 1
Highly Selective Dissociation of a Peptide Bond Following Excitation of Core Electrons
journal, May 2015
- Lin, Yi-Shiue; Tsai, Cheng-Cheng; Lin, Huei-Ru
- The Journal of Physical Chemistry A, Vol. 119, Issue 24
Time-Dependent Density Functional Theory
journal, June 2004
- Marques, M. A. L.; Gross, E. K. U.
- Annual Review of Physical Chemistry, Vol. 55, Issue 1
Works referencing / citing this record:
Tuning photoionization mechanisms of molecular hybrid materials for EUV lithography applications
journal, January 2019
- Wu, Lianjia; Tiekink, Martijn; Giuliani, Alexandre
- Journal of Materials Chemistry C, Vol. 7, Issue 1
Fundamental understanding of chemical processes in extreme ultraviolet resist materials
journal, October 2018
- Kostko, Oleg; Xu, Bo; Ahmed, Musahid
- The Journal of Chemical Physics, Vol. 149, Issue 15