A study of the kinetics and mechanism of rapid self- assembly in block copolymer thin films during “solvo-microwave” annealing

Typeset version

 

TY  - JOUR
  - Mokarian-Tabari, P.; Cummins, C.; Rasappa, S.; Simão, C.; Sotomayor-Torres, C.; Holmes, J. D.; Morris, M. A.
  - 2014
  - September
  - Langmuir
  - A study of the kinetics and mechanism of rapid self- assembly in block copolymer thin films during “solvo-microwave” annealing
  - Published
  - Altmetric: 2 ()
  - 30
  - 35
  - 10728
  - 10739
  - Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high-χ lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during “solvomicrowave” annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 °C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during “solvo-microwave” annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.
  - Washington, DC, USA
  - http://pubs.acs.org/journal/langd5
  - 10.1021/la503137q
DA  - 2014/09
ER  - 
@article{V274158549,
   = {Mokarian-Tabari, P. and  Cummins, C. and  Rasappa, S. and  Simão, C. and  Sotomayor-Torres, C. and  Holmes, J. D. and  Morris, M. A.},
   = {2014},
   = {September},
   = {Langmuir},
   = {A study of the kinetics and mechanism of rapid self- assembly in block copolymer thin films during “solvo-microwave” annealing},
   = {Published},
   = {Altmetric: 2 ()},
   = {30},
   = {35},
  pages = {10728--10739},
   = {{Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high-χ lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during “solvomicrowave” annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 °C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during “solvo-microwave” annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.}},
   = {Washington, DC, USA},
   = {http://pubs.acs.org/journal/langd5},
   = {10.1021/la503137q},
  source = {IRIS}
}
AUTHORSMokarian-Tabari, P.; Cummins, C.; Rasappa, S.; Simão, C.; Sotomayor-Torres, C.; Holmes, J. D.; Morris, M. A.
YEAR2014
MONTHSeptember
JOURNAL_CODELangmuir
TITLEA study of the kinetics and mechanism of rapid self- assembly in block copolymer thin films during “solvo-microwave” annealing
STATUSPublished
TIMES_CITEDAltmetric: 2 ()
SEARCH_KEYWORD
VOLUME30
ISSUE35
START_PAGE10728
END_PAGE10739
ABSTRACTMicrowave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high-χ lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during “solvomicrowave” annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 °C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during “solvo-microwave” annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.
PUBLISHER_LOCATIONWashington, DC, USA
ISBN_ISSN
EDITION
URLhttp://pubs.acs.org/journal/langd5
DOI_LINK10.1021/la503137q
FUNDING_BODY
GRANT_DETAILS