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Title: In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials

To elucidate the details of film morphology/order evolution during spin-coating, solvent and additive effects are systematically investigated for three representative organic solar cell (OSC) active layer materials using combined in situ grazing incidence wide angle x-ray scattering (GIWAXS) and optical reflectance. Two archetypical semiconducting donor (p-type) polymers, P3HT and PTB7, and semiconducting donor small-molecule, p-DTS(FBTTh 2) 2 are studied using three neat solvents (chloroform, chlorobenzene, 1,2-dichlorobenzene) and four processing additives (1-chloronaphthalene, diphenyl ether, 1,8-diiodooctane, and 1,6-diiodohexane). In situ GIWAXS identifies several trends: 1) for neat solvents, rapid crystallization occurs that risks kinetically locking the material into multiple crystal structures or crystalline orientations; and 2) for solvent + additive processed films, morphology evolution involves sequential transformations on timescales ranging from seconds to hours, with key divergences dependent on additive/semiconductor molecular interactions. When π-planes dominate the additive/semiconductor interactions, both polymers and small molecule films follow similar evolutions, completing in 1–5 min. When side chains dominate the additive/semiconductor interactions, polymer film maturation times are up to 9 h, while initial crystallization times <10 s are observed for small-molecule films. In conclusion, this study offers guiding information on OSC donor intermediate morphologies, evolution timescales, and divergent evolutions that can inform OSC manufacture.
Authors:
 [1] ;  [2] ;  [1] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and the Argonne-Northwestern Solar Energy Research (ANSER) Center; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-Ray Science Division
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry and the Argonne-Northwestern Solar Energy Research (ANSER) Center
Publication Date:
Grant/Contract Number:
AC02-06CH11357; SC0001059; FG02-08ER46536; 7-286-1-046; 0960140
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 23; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Qatar NPRP
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; additives; in situ GIWAXS; organic solar cells; polymer; spin-coating
OSTI Identifier:
1471497
Alternate Identifier(s):
OSTI ID: 1439115

Manley, Eric F., Strzalka, Joseph, Fauvell, Thomas J., Marks, Tobin J., and Chen, Lin X.. In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials. United States: N. p., Web. doi:10.1002/aenm.201800611.
Manley, Eric F., Strzalka, Joseph, Fauvell, Thomas J., Marks, Tobin J., & Chen, Lin X.. In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials. United States. doi:10.1002/aenm.201800611.
Manley, Eric F., Strzalka, Joseph, Fauvell, Thomas J., Marks, Tobin J., and Chen, Lin X.. 2018. "In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials". United States. doi:10.1002/aenm.201800611.
@article{osti_1471497,
title = {In Situ Analysis of Solvent and Additive Effects on Film Morphology Evolution in Spin-Cast Small-Molecule and Polymer Photovoltaic Materials},
author = {Manley, Eric F. and Strzalka, Joseph and Fauvell, Thomas J. and Marks, Tobin J. and Chen, Lin X.},
abstractNote = {To elucidate the details of film morphology/order evolution during spin-coating, solvent and additive effects are systematically investigated for three representative organic solar cell (OSC) active layer materials using combined in situ grazing incidence wide angle x-ray scattering (GIWAXS) and optical reflectance. Two archetypical semiconducting donor (p-type) polymers, P3HT and PTB7, and semiconducting donor small-molecule, p-DTS(FBTTh2)2 are studied using three neat solvents (chloroform, chlorobenzene, 1,2-dichlorobenzene) and four processing additives (1-chloronaphthalene, diphenyl ether, 1,8-diiodooctane, and 1,6-diiodohexane). In situ GIWAXS identifies several trends: 1) for neat solvents, rapid crystallization occurs that risks kinetically locking the material into multiple crystal structures or crystalline orientations; and 2) for solvent + additive processed films, morphology evolution involves sequential transformations on timescales ranging from seconds to hours, with key divergences dependent on additive/semiconductor molecular interactions. When π-planes dominate the additive/semiconductor interactions, both polymers and small molecule films follow similar evolutions, completing in 1–5 min. When side chains dominate the additive/semiconductor interactions, polymer film maturation times are up to 9 h, while initial crystallization times <10 s are observed for small-molecule films. In conclusion, this study offers guiding information on OSC donor intermediate morphologies, evolution timescales, and divergent evolutions that can inform OSC manufacture.},
doi = {10.1002/aenm.201800611},
journal = {Advanced Energy Materials},
number = 23,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}

Works referenced in this record:

When Function Follows Form: Effects of Donor Copolymer Side Chains on Film Morphology and BHJ Solar Cell Performance
journal, November 2010
  • Szarko, Jodi M.; Guo, Jianchang; Liang, Yongye
  • Advanced Materials, Vol. 22, Issue 48, p. 5468-5472
  • DOI: 10.1002/adma.201002687