skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 » 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.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1476485
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
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. doi: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. doi: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},
issn = {0021-9606},
number = 16,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}

Works referenced in this record:

Design, development, EUVL applications and nano mechanical properties of a new HfO 2 based hybrid non-chemically amplified resist
journal, January 2016

  • Reddy, Pulikanti Guruprasad; Mamidi, Narsimha; Kumar, Pawan
  • RSC Advances, Vol. 6, Issue 71
  • DOI: 10.1039/c6ra10575k

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
  • DOI: 10.1073/pnas.1321999111

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
  • DOI: 10.1063/1.555594

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
  • DOI: 10.1116/1.2794048

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
  • DOI: 10.1039/c4ra10648b

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
  • DOI: 10.1063/1.1904586

Absolute oscillator strengths for photoabsorption (6–360 eV) and ionic photofragmentation (10–80 eV) of methanol
journal, November 1992


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
  • DOI: 10.1016/j.cpc.2014.03.005

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
  • DOI: 10.1021/ct3005613

Active control of chemical bond scission by site-specific core excitation
journal, March 2003


Optical lithography: Introduction
journal, January 1997

  • Chiu, G. L. -T.; Shaw, J. M.
  • IBM Journal of Research and Development, Vol. 41, Issue 1.2
  • DOI: 10.1147/rd.411.0003

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
  • DOI: 10.1016/j.elspec.2010.04.011

Interaction of Maxima in the Absorption of Soft X Rays
journal, December 1964


Electron scattering from CH3I. Total cross section measurements
journal, July 1993


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
  • DOI: 10.1002/pssb.200642067

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
  • DOI: 10.1039/c002207a

Nanolithography in microelectronics: A review
journal, August 2011


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
  • DOI: 10.1063/1.2899649

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
  • DOI: 10.1063/1.1338527

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
  • DOI: 10.1063/1.456646

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
  • DOI: 10.1021/ct400569s

Photolithographic properties of tin-oxo clusters using extreme ultraviolet light (13.5nm)
journal, September 2014


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
  • DOI: 10.1021/jp065160x

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
  • DOI: 10.2494/photopolymer.7.433

TD-DFT benchmarks: A review
journal, April 2013

  • Laurent, Adèle D.; Jacquemin, Denis
  • International Journal of Quantum Chemistry, Vol. 113, Issue 17
  • DOI: 10.1002/qua.24438

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


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
  • DOI: 10.1063/1.555523

Fluorescence yields and Coster–Kronig probabilities for the atomic L subshells. Part II: The L1 subshell revisited
journal, January 2009


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
  • DOI: 10.1021/acs.jctc.6b00693

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
  • DOI: 10.1021/jp049358y

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
  • DOI: 10.1016/j.cpc.2011.04.020

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
  • DOI: 10.1021/cr0505627

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
  • DOI: 10.1117/12.813551

Inner-shell photoemission from the iodine atom in CH 3 I
journal, July 1984


Progress in Time-Dependent Density-Functional Theory
journal, May 2012


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
  • DOI: 10.1039/a910321j

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
  • DOI: 10.1063/1.3651239

The valence shell photoabsorption of the linear alkanes, CnH2n+2 (n=1–8): absolute oscillator strengths (7–220 eV)
journal, June 1993


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
  • DOI: 10.1063/1.4802058

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
  • DOI: 10.2494/photopolymer.26.697

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
  • DOI: 10.1021/acs.jpca.6b00692

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
  • DOI: 10.1006/adnd.1993.1013

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
  • DOI: 10.1021/ct500943m

Review on Micro- and Nanolithography Techniques and their Applications
journal, January 2012


Molecular dynamics in electronically excited states using time-dependent density functional theory
journal, March 2005


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
  • DOI: 10.1021/acs.jpca.5b04402

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
  • DOI: 10.1063/1.4926396

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
  • DOI: 10.1063/1.4952646

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
  • DOI: 10.2494/photopolymer.27.655

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
  • DOI: 10.1021/ct200485x

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
  • DOI: 10.1140/epjb/e2015-50808-0

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
  • DOI: 10.1063/1.1774980

The iterative calculation of a few of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices
journal, January 1975


Density-Functional Theory for Time-Dependent Systems
journal, March 1984


octopus: a first-principles tool for excited electron–ion dynamics
journal, March 2003


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
  • DOI: 10.1021/acs.jpca.5b04415

Time-Dependent Density Functional Theory
journal, June 2004


Electron energy loss and inelastic x-ray scattering cross sections from time-dependent density-functional perturbation theory
journal, August 2013


Time-dependent local-density approximation in real time: Application to conjugated molecules
journal, January 1999