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Title: Advancing next generation nanolithography with infiltration synthesis of hybrid nanocomposite resists

Abstract

Organic–inorganic hybrid resists are emerging as an effective way of addressing stringent process requirements for aggressive down-scaling of semiconducting devices. Yet, hybrid resists generally require complex chemical synthesis while being predominantly negative-tone with high dose requirements. For positive-tone processes and high-aspect-ratio pattern transfers, resist choices are limited to costly, non-hybrid alternatives, whose etch resistance is still inferior compared with hybrid resists. In this work, we demonstrate a novel hybrid positive-tone resist platform utilizing simple ex situ vapor-phase inorganic infiltration into standard resist materials. A model system based on poly(methyl methacrylate) (PMMA) thin film hybridized with aluminum oxide has been demonstrated for electron-beam lithography patterning, featuring a fully controllable critical exposure dose, contrast, and etch resistance. The hybrid resist not only achieves contrast as high as ~30, six-fold enhancement over standard PMMA, but also enables Si nanostructures with resolution down to ~30 nm and an aspect ratio as high as ~17, owing to enhancement of the Si etch selectivity to ~70, with an estimated achievable maximum of ~300, far exceeding known commercial positive-tone resist systems. The easy implementabilility, combined with versatile ex situ control of resist characteristics, makes this hybrid resist synthesis method uniquely suited for addressing the resist performance andmore » high throughput required for advanced nanolithography techniques, such as extreme ultraviolet lithography, possibly.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [3];  [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Univ. of Texas-Dallas, Richardson, TX (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1561253
Alternate Identifier(s):
OSTI ID: 1542528
Report Number(s):
BNL-212064-2019-JAAM; BNL-213624-2020-JAAM
Journal ID: ISSN 2050-7526; JMCCCX
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 7; Journal Issue: 29; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY AND ECONOMY; 36 MATERIALS SCIENCE

Citation Formats

Tiwale, Nikhil, Subramanian, Ashwanth, Kisslinger, Kim, Lu, Ming, Kim, Jiyoung, Stein, Aaron, and Nam, Chang-Yong. Advancing next generation nanolithography with infiltration synthesis of hybrid nanocomposite resists. United States: N. p., 2019. Web. doi:10.1039/C9TC02974E.
Tiwale, Nikhil, Subramanian, Ashwanth, Kisslinger, Kim, Lu, Ming, Kim, Jiyoung, Stein, Aaron, & Nam, Chang-Yong. Advancing next generation nanolithography with infiltration synthesis of hybrid nanocomposite resists. United States. https://doi.org/10.1039/C9TC02974E
Tiwale, Nikhil, Subramanian, Ashwanth, Kisslinger, Kim, Lu, Ming, Kim, Jiyoung, Stein, Aaron, and Nam, Chang-Yong. Mon . "Advancing next generation nanolithography with infiltration synthesis of hybrid nanocomposite resists". United States. https://doi.org/10.1039/C9TC02974E. https://www.osti.gov/servlets/purl/1561253.
@article{osti_1561253,
title = {Advancing next generation nanolithography with infiltration synthesis of hybrid nanocomposite resists},
author = {Tiwale, Nikhil and Subramanian, Ashwanth and Kisslinger, Kim and Lu, Ming and Kim, Jiyoung and Stein, Aaron and Nam, Chang-Yong},
abstractNote = {Organic–inorganic hybrid resists are emerging as an effective way of addressing stringent process requirements for aggressive down-scaling of semiconducting devices. Yet, hybrid resists generally require complex chemical synthesis while being predominantly negative-tone with high dose requirements. For positive-tone processes and high-aspect-ratio pattern transfers, resist choices are limited to costly, non-hybrid alternatives, whose etch resistance is still inferior compared with hybrid resists. In this work, we demonstrate a novel hybrid positive-tone resist platform utilizing simple ex situ vapor-phase inorganic infiltration into standard resist materials. A model system based on poly(methyl methacrylate) (PMMA) thin film hybridized with aluminum oxide has been demonstrated for electron-beam lithography patterning, featuring a fully controllable critical exposure dose, contrast, and etch resistance. The hybrid resist not only achieves contrast as high as ~30, six-fold enhancement over standard PMMA, but also enables Si nanostructures with resolution down to ~30 nm and an aspect ratio as high as ~17, owing to enhancement of the Si etch selectivity to ~70, with an estimated achievable maximum of ~300, far exceeding known commercial positive-tone resist systems. The easy implementabilility, combined with versatile ex situ control of resist characteristics, makes this hybrid resist synthesis method uniquely suited for addressing the resist performance and high throughput required for advanced nanolithography techniques, such as extreme ultraviolet lithography, possibly.},
doi = {10.1039/C9TC02974E},
url = {https://www.osti.gov/biblio/1561253}, journal = {Journal of Materials Chemistry C},
issn = {2050-7526},
number = 29,
volume = 7,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 4 works
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Works referenced in this record:

Deep reactive ion etching of commercial PMMA in O 2 /CHF 3 , and O 2 /Ar-based discharges
journal, March 2004


Directed self-assembly of block copolymers for nanocircuitry fabrication
journal, January 2015


Infiltrated Zinc Oxide in Poly(methyl methacrylate): An Atomic Cycle Growth Study
journal, December 2016


Sub-10-nm high aspect ratio patterning of ZnO in a 500 μm main field
journal, January 2006

  • Saifullah, M. S. M.; Subramanian, K. R. V.; Anderson, D.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 24, Issue 3
  • https://doi.org/10.1116/1.2192545

Boehmite filled hybrid sol–gel system as directly writable hard etching mask for pattern transfer
journal, August 2011


Platinum and palladium oxalates: positive-tone extreme ultraviolet resists
journal, October 2015


Chemical and Structural Investigation of High-Resolution Patterning with HafSOx
journal, February 2014


High-index nanocomposite photoresist for 193-nm lithography
conference, March 2009


Organosilicate polymer e-beam resists with high resolution, sensitivity and stability: Organosilicate polymer e-beam resists
journal, October 2013


Enhanced Lithographic Imaging Layer Meets Semiconductor Manufacturing Specification a Decade Early
journal, April 2012


High sensitive negative silylation process for 193nm lithography
journal, June 2000


Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films
journal, January 2019


Low temperature development of PMMA for sub-10-nm electron beam lithography
conference, January 2003


Novel polymeric anionic photoacid generators (PAGs) and corresponding polymers for 193 nm lithography
journal, January 2006


Imaging results for resist films exposed to EUV radiation
journal, July 2002


Photo-induced Fragmentation of a Tin-oxo Cage Compound
journal, January 2018


Ultrahigh Elastic Strain Energy Storage in Metal-Oxide-Infiltrated Patterned Hybrid Polymer Nanocomposites
journal, November 2017


Ultrathin photoresists for 193-nm lithography
conference, June 2003


Antimony photoresists for EUV lithography: mechanistic studies
conference, March 2017


A Top Surface Imaging Method Using Area Selective ALD on Chemically Amplified Polymer Photoresist Films
journal, January 2006


Approaches to deep ultraviolet photolithography utilizing acid hardened resin photoresist systems
journal, November 1989

  • Thackeray, James W.; Orsula, George W.; Bohland, John F.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 7, Issue 6, Article No. 1620
  • https://doi.org/10.1116/1.584502

Chemical Semi-Amplified positive E-beam Resist (CSAR 62) for highest resolution
conference, October 2013


Extreme ultraviolet resist materials for sub-7 nm patterning
journal, January 2017


Sub-10 nm electron and helium ion beam lithography using a recently developed alumina resist
journal, June 2018


Negative hybrid sol–gel resist as hard etching mask for pattern transfer with dry etching
journal, October 2012


Optimized surface silylation of chemically amplified epoxidized photoresists for micromachining applications
journal, April 2010


Chemical Modification Mechanisms in Hybrid Hafnium Oxo-methacrylate Nanocluster Photoresists for Extreme Ultraviolet Patterning
journal, August 2018


Surface imaging techniques
journal, March 1991


Sub-10 nm High-Aspect-Ratio Patterning of ZnO Using an Electron Beam
journal, July 2005


Systematic studies of functionalized calixarenes as negative tone electron beam
journal, March 1998


Review of Recent Advances in Applications of Vapor-Phase Material Infiltration Based on Atomic Layer Deposition
journal, September 2018


Negative resist image by dry etching: a novel surface imaging resist scheme
journal, June 2003


High resolution spin-on electron beam lithography resist with exceptional dry etching resistance
journal, November 2015


Directed self-assembly of block copolymers for use in bit patterned media fabrication
journal, November 2013


Effect of chelating agents on high resolution electron beam nanolithography of spin-coatable Al/sub 2/O/sub 3/ gel films
conference, January 1999

  • Saifullah, M. S. M.; Namatsu, H.; Yamaguchi, T.
  • Digest of Papers. Microprocesses and Nanotechnology '99. 1999 International Microprocesses and Nanotechnology Conference
  • https://doi.org/10.1109/IMNC.1999.797526

Water soluble and metal-containing electron beam resist poly(sodium 4-styrenesulfonate)
journal, November 2014


Comparison of MIBK/IPA and water/IPA as PMMA developers for electron beam nanolithography
journal, July 2002


Novel Hybrid Organic-Inorganic Spin-on Resist for Electron- or Photon-Based Nanolithography with Outstanding Resistance to Dry Etching
journal, August 2013


Application of Plasmask R  resist and the DESIRE process to lithography at 248 nm
journal, November 1990


Silylated acid hardened resist process: A deep ultraviolet surface imaging technique
journal, November 1990


Combination photo and electron beam lithography with polymethyl methacrylate (PMMA) resist
journal, October 2017


Sub-10 nm Electron Beam Nanolithography Using Spin-Coatable TiO 2 Resists
journal, November 2003


Aberration-Corrected Electron Beam Lithography at the One Nanometer Length Scale
journal, April 2017


Spin-coatable HfO2 resist for optical and electron beam lithographies
journal, January 2010

  • Saifullah, M. S. M.; Khan, M. Z. R.; Hasko, David G.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 1
  • https://doi.org/10.1116/1.3273536

New Positive EB Resist with Strong Resistance to Plasma Damage
journal, January 1992


Studying the Mechanism of Hybrid Nanoparticle Photoresists: Effect of Particle Size on Photopatterning
journal, July 2015


Electron beam lithography process for T- and Γ-shaped gate fabrication using chemically amplified DUV resists and PMMA
journal, January 1999

  • Chen, Y.; Macintyre, D.; Thoms, S.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 17, Issue 6
  • https://doi.org/10.1116/1.591119

Study of nanometer resolution resist slope for the UVIII chemically amplified resist
journal, May 1999


Lithography and Other Patterning Techniques for Future Electronics
journal, February 2008


Direct e-beam writing of dense and high aspect ratio nanostructures in thick layers of PMMA for electroplating
journal, July 2010


10nm lines and spaces written in HSQ, using electron beam lithography
journal, May 2007


Nanoparticle Photoresists: Ligand Exchange as a New, Sensitive EUV Patterning Mechanism
journal, January 2013


Reactivity of metal-oxalate EUV resists as a function of the central metal
conference, March 2017


New hybrid organic–inorganic sol–gel positive resist
journal, May 2010


New Insight into the Mechanism of Sequential Infiltration Synthesis from Infrared Spectroscopy
journal, October 2014


Improved etch resistance of ZEP 520A in reactive ion etching through heat and ultraviolet light treatment
journal, January 2009

  • Czaplewski, David A.; Tallant, David R.; Patrizi, Gary A.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 27, Issue 2
  • https://doi.org/10.1116/1.3086721

Metal methacrylates as sensitizers for poly methyl methacrylate electron resists
journal, November 1979


PRIME process for deep UV and E-beam lithography
journal, April 1990


Chemically Enhancing Block Copolymers for Block-Selective Synthesis of Self-Assembled Metal Oxide Nanostructures
journal, December 2012


High aspect ratio silicon etch: A review
journal, September 2010


Alternatives to chemical amplification for 193nm lithography
conference, March 2010


Fabrication of Sub-10 nm Metallic Lines of Low Line-Width Roughness by Hydrogen Reduction of Patterned Metal-Organic Materials
journal, June 2010


Electron Beam Nanolithography of  -Ketoester Modified Aluminium Tri-Sec-Butoxide
journal, January 2004


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


Elemental depth profiles and plasma etching rates of positive-tone electron beam resists after sequential infiltration synthesis of alumina
journal, May 2018


Direct writing of ZrO 2 on a sub-10 nm scale using an electron beam
journal, November 2003


Enhanced polymeric lithography resists via sequential infiltration synthesis
journal, July 2011


PRIME process with Shipley SPR505A resist—simulations and experiments
journal, July 2002


Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer
journal, May 2017


Resists for sub-20-nm electron beam lithography with a focus on HSQ: state of the art
journal, July 2009


    Works referencing / citing this record:

    Silylated acid hardened resist process: A deep ultraviolet surface imaging technique
    journal, November 1990


    Application of Plasmask R  resist and the DESIRE process to lithography at 248 nm
    journal, November 1990


    Combination photo and electron beam lithography with polymethyl methacrylate (PMMA) resist
    journal, October 2017


    Spin-coatable HfO2 resist for optical and electron beam lithographies
    journal, January 2010

    • Saifullah, M. S. M.; Khan, M. Z. R.; Hasko, David G.
    • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 1
    • https://doi.org/10.1116/1.3273536

    Extreme ultraviolet resist materials for sub-7 nm patterning
    journal, January 2017


    High aspect ratio silicon etch: A review
    journal, September 2010


    Antimony photoresists for EUV lithography: mechanistic studies
    conference, March 2017


    Chemical Modification Mechanisms in Hybrid Hafnium Oxo-methacrylate Nanocluster Photoresists for Extreme Ultraviolet Patterning
    journal, August 2018


    Improved etch resistance of ZEP 520A in reactive ion etching through heat and ultraviolet light treatment
    journal, January 2009

    • Czaplewski, David A.; Tallant, David R.; Patrizi, Gary A.
    • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 27, Issue 2
    • https://doi.org/10.1116/1.3086721

    Chemical Semi-Amplified positive E-beam Resist (CSAR 62) for highest resolution
    conference, October 2013


    Platinum and palladium oxalates: positive-tone extreme ultraviolet resists
    journal, October 2015


    Negative resist image by dry etching: a novel surface imaging resist scheme
    journal, June 2003


    Direct writing of ZrO 2 on a sub-10 nm scale using an electron beam
    journal, November 2003


    Study of nanometer resolution resist slope for the UVIII chemically amplified resist
    journal, May 1999


    Ultrathin photoresists for 193-nm lithography
    conference, June 2003


    A Top Surface Imaging Method Using Area Selective ALD on Chemically Amplified Polymer Photoresist Films
    journal, January 2006


    New Insight into the Mechanism of Sequential Infiltration Synthesis from Infrared Spectroscopy
    journal, October 2014


    Optimized surface silylation of chemically amplified epoxidized photoresists for micromachining applications
    journal, April 2010


    Surface imaging techniques
    journal, March 1991


    Enhanced polymeric lithography resists via sequential infiltration synthesis
    journal, July 2011


    Organosilicate polymer e-beam resists with high resolution, sensitivity and stability: Organosilicate polymer e-beam resists
    journal, October 2013


    Novel Hybrid Organic-Inorganic Spin-on Resist for Electron- or Photon-Based Nanolithography with Outstanding Resistance to Dry Etching
    journal, August 2013


    Imaging results for resist films exposed to EUV radiation
    journal, July 2002


    PRIME process for deep UV and E-beam lithography
    journal, April 1990


    Studying the Mechanism of Hybrid Nanoparticle Photoresists: Effect of Particle Size on Photopatterning
    journal, July 2015


    Chemical and Structural Investigation of High-Resolution Patterning with HafSOx
    journal, February 2014


    High resolution spin-on electron beam lithography resist with exceptional dry etching resistance
    journal, November 2015


    Directed self-assembly of block copolymers for nanocircuitry fabrication
    journal, January 2015


    Alternatives to chemical amplification for 193nm lithography
    conference, March 2010


    Deep reactive ion etching of commercial PMMA in O 2 /CHF 3 , and O 2 /Ar-based discharges
    journal, March 2004


    Electron beam lithography process for T- and Γ-shaped gate fabrication using chemically amplified DUV resists and PMMA
    journal, January 1999

    • Chen, Y.; Macintyre, D.; Thoms, S.
    • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 17, Issue 6
    • https://doi.org/10.1116/1.591119

    Review of Recent Advances in Applications of Vapor-Phase Material Infiltration Based on Atomic Layer Deposition
    journal, September 2018


    New hybrid organic–inorganic sol–gel positive resist
    journal, May 2010


    Chemically Enhancing Block Copolymers for Block-Selective Synthesis of Self-Assembled Metal Oxide Nanostructures
    journal, December 2012


    High-index nanocomposite photoresist for 193-nm lithography
    conference, March 2009


    Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films
    journal, January 2019


    Directed self-assembly of block copolymers for use in bit patterned media fabrication
    journal, November 2013


    Elemental depth profiles and plasma etching rates of positive-tone electron beam resists after sequential infiltration synthesis of alumina
    journal, May 2018


    Low temperature development of PMMA for sub-10-nm electron beam lithography
    conference, January 2003


    Electron Beam Nanolithography of  -Ketoester Modified Aluminium Tri-Sec-Butoxide
    journal, January 2004


    Reactivity of metal-oxalate EUV resists as a function of the central metal
    conference, March 2017


    Metal methacrylates as sensitizers for poly methyl methacrylate electron resists
    journal, November 1979


    Sub-10 nm High-Aspect-Ratio Patterning of ZnO Using an Electron Beam
    journal, July 2005


    Fabrication of Sub-10 nm Metallic Lines of Low Line-Width Roughness by Hydrogen Reduction of Patterned Metal-Organic Materials
    journal, June 2010


    High sensitive negative silylation process for 193nm lithography
    journal, June 2000


    Enhanced Lithographic Imaging Layer Meets Semiconductor Manufacturing Specification a Decade Early
    journal, April 2012


    Nanoparticle Photoresists: Ligand Exchange as a New, Sensitive EUV Patterning Mechanism
    journal, January 2013


    10nm lines and spaces written in HSQ, using electron beam lithography
    journal, May 2007


    Resists for sub-20-nm electron beam lithography with a focus on HSQ: state of the art
    journal, July 2009


    Sub-10-nm high aspect ratio patterning of ZnO in a 500 μm main field
    journal, January 2006

    • Saifullah, M. S. M.; Subramanian, K. R. V.; Anderson, D.
    • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 24, Issue 3
    • https://doi.org/10.1116/1.2192545

    Direct e-beam writing of dense and high aspect ratio nanostructures in thick layers of PMMA for electroplating
    journal, July 2010


    Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer
    journal, May 2017


    Novel polymeric anionic photoacid generators (PAGs) and corresponding polymers for 193 nm lithography
    journal, January 2006


    Boehmite filled hybrid sol–gel system as directly writable hard etching mask for pattern transfer
    journal, August 2011


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


    Infiltrated Zinc Oxide in Poly(methyl methacrylate): An Atomic Cycle Growth Study
    journal, December 2016


    PRIME process with Shipley SPR505A resist—simulations and experiments
    journal, July 2002


    Comparison of MIBK/IPA and water/IPA as PMMA developers for electron beam nanolithography
    journal, July 2002


    Lithography and Other Patterning Techniques for Future Electronics
    journal, February 2008


    Negative hybrid sol–gel resist as hard etching mask for pattern transfer with dry etching
    journal, October 2012


    Sub-10 nm electron and helium ion beam lithography using a recently developed alumina resist
    journal, June 2018


    New Positive EB Resist with Strong Resistance to Plasma Damage
    journal, January 1992


    Sub-10 nm Electron Beam Nanolithography Using Spin-Coatable TiO 2 Resists
    journal, November 2003


    Effect of chelating agents on high resolution electron beam nanolithography of spin-coatable Al/sub 2/O/sub 3/ gel films
    conference, January 1999

    • Saifullah, M. S. M.; Namatsu, H.; Yamaguchi, T.
    • Digest of Papers. Microprocesses and Nanotechnology '99. 1999 International Microprocesses and Nanotechnology Conference
    • https://doi.org/10.1109/imnc.1999.797526

    Ultrahigh Elastic Strain Energy Storage in Metal-Oxide-Infiltrated Patterned Hybrid Polymer Nanocomposites
    journal, November 2017


    Approaches to deep ultraviolet photolithography utilizing acid hardened resin photoresist systems
    journal, November 1989

    • Thackeray, James W.; Orsula, George W.; Bohland, John F.
    • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 7, Issue 6, Article No. 1620
    • https://doi.org/10.1116/1.584502

    Water soluble and metal-containing electron beam resist poly(sodium 4-styrenesulfonate)
    journal, November 2014


    Systematic studies of functionalized calixarenes as negative tone electron beam
    journal, March 1998


    Photo-induced Fragmentation of a Tin-oxo Cage Compound
    journal, January 2018


    Aberration-Corrected Electron Beam Lithography at the One Nanometer Length Scale
    journal, April 2017


    The chemical physics of sequential infiltration synthesis—A thermodynamic and kinetic perspective
    journal, November 2019