Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

Ferron, Thomas J.; Thelen, Jacob L.; Bagchi, Kushal; Deng, Chuting; Gann, Eliot; de Pablo, Juan J.; Ediger, M. D.; Sunday, Daniel F.; DeLongchamp, Dean M.

doi:10.1021/acsami.1c19948

Title: Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

Journal Article · 04 January 2022 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.1c19948 · OSTI ID:1972709

^[1]; Thelen, Jacob L. ^[2];

^[3];

^[4];

^[2];

^[4];

^[3];

^[2];

^[2]

National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); University of Wisconsin - Madison
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Univ. of Wisconsin, Madison, WI (United States)
Univ. of Chicago, IL (United States)

The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution. To overcome these challenges, we use polarized resonant soft X-ray reflectivity (pRSoXR) to measure nanometer-resolved, molecular orientation depth profiles of vapor-deposited thin films of an organic semiconductor Tris(4-carbazoyl-9-ylphenyl)amine (TCTA). Our depth profiling approach characterizes the vertical distribution of molecular orientation and reveals that molecules near the inorganic substrate and free surface have a different, nearly isotropic orientation compared to those of the anisotropic bulk. Comparison of pRSoXR results with near-edge X-ray absorption fine structure spectroscopy and optical spectroscopies reveals that TCTA molecules away from the interfaces are predominantly planar, which may contribute to their attractive charge transport qualities. Buried interfaces are further investigated in a TCTA bilayer (each layer deposited under separate conditions resulting in different orientations) in which we find a narrow interface between orientationally distinct layers extending across ≈1 nm. Coupling this result with molecular dynamics simulations provides additional insight into the formation of interfacial structure. This study characterizes the local molecular orientation at various types of buried interfaces in vapor-deposited glasses and provides a foundation for future studies to develop critical structure–function relationships.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0002161

OSTI ID:: 1972709

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 2 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

Orientation Control of Linear-Shaped Molecules in Vacuum-Deposited Organic Amorphous Films and Its Effect on Carrier Mobilities Yokoyama, Daisuke; Setoguchi, Yousuke; Sakaguchi, Akio Advanced Functional Materials, Vol. 20, Issue 3 https://doi.org/10.1002/adfm.200901684	journal	February 2010
Extreme Elasticity Anisotropy in Molecular Glasses Cang, Yu; Wang, Zuyuan; Bishop, Camille Advanced Functional Materials, Vol. 30, Issue 23 https://doi.org/10.1002/adfm.202001481	journal	April 2020
Thermally stable multilared organic electroluminescent devices using novel starburst molecules, 4,4′,4″-Tri(N-carbazolyl)triphenylamine (TCTA) and 4,4′,4″-Tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), as hole-transport materials Kuwabara, Yoshiyuki; Ogawa, Hiromitsu; Inada, Hiroshi Advanced Materials, Vol. 6, Issue 9, p. 677-679 https://doi.org/10.1002/adma.19940060913	journal	September 1994
Microstructural Characterization and Charge Transport in Thin Films of Conjugated Polymers Salleo, Alberto; Kline, R. Joseph; DeLongchamp, Dean M. Advanced Materials, Vol. 22, Issue 34 https://doi.org/10.1002/adma.200903712	journal	July 2010
Graded Donor-Acceptor Heterojunctions for Efficient Organic Photovoltaic Cells Pandey, Richa; Holmes, Russell J. Advanced Materials, Vol. 22, Issue 46 https://doi.org/10.1002/adma.201002454	journal	September 2010
Progress in Understanding Degradation Mechanisms and Improving Stability in Organic Photovoltaics Mateker, William R.; McGehee, Michael D. Advanced Materials, Vol. 29, Issue 10 https://doi.org/10.1002/adma.201603940	journal	December 2016
X-Ray Interactions: Photoabsorption, Scattering, Transmission, and Reflection at E = 50-30,000 eV, Z = 1-92 Henke, B. L.; Gullikson, E. M.; Davis, J. C. Atomic Data and Nuclear Data Tables, Vol. 54, Issue 2, p. 181-342 https://doi.org/10.1006/adnd.1993.1013	journal	July 1993
Understanding Energy Loss in Organic Solar Cells: Toward a New Efficiency Regime Menke, S. Matthew; Ran, Niva A.; Bazan, Guillermo C. Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.09.020	journal	January 2018
Molecular orientation and thermal stability of thin-film organic semiconductors Yang, Han-Nan; He, Shou-Jie; Zhang, Tao Organic Electronics, Vol. 88 https://doi.org/10.1016/j.orgel.2020.106014	journal	January 2021
Anisotropic Vapor-Deposited Glasses: Hybrid Organic Solids Ediger, M. D.; de Pablo, Juan; Yu, Lian Accounts of Chemical Research, Vol. 52, Issue 2 https://doi.org/10.1021/acs.accounts.8b00513	journal	January 2019
Molecular Orientation Depth Profiles in Organic Glasses Using Polarized Resonant Soft X-ray Reflectivity Thelen, Jacob L.; Bishop, Camille; Bagchi, Kushal Chemistry of Materials, Vol. 32, Issue 15 https://doi.org/10.1021/acs.chemmater.0c02044	journal	July 2020
Triarylamine: Versatile Platform for Organic, Dye-Sensitized, and Perovskite Solar Cells Wang, Jiayu; Liu, Kuan; Ma, Lanchao Chemical Reviews, Vol. 116, Issue 23 https://doi.org/10.1021/acs.chemrev.6b00432	journal	November 2016
Molecular Orientation for Vapor-Deposited Organic Glasses Follows Rate-Temperature Superposition: The Case of Posaconazole Bishop, Camille; Li, Yuhui; Toney, Michael F. The Journal of Physical Chemistry B, Vol. 124, Issue 12 https://doi.org/10.1021/acs.jpcb.0c00625	journal	March 2020
Stable Glasses of Organic Semiconductor Resist Crystallization Bagchi, Kushal; Fiori, Marie E.; Bishop, Camille The Journal of Physical Chemistry B, Vol. 125, Issue 1 https://doi.org/10.1021/acs.jpcb.0c09925	journal	December 2020
Exploring the Importance of Surface Diffusion in Stability of Vapor-Deposited Organic Glasses Samanta, Subarna; Huang, Georgia; Gao, Gui The Journal of Physical Chemistry B, Vol. 123, Issue 18 https://doi.org/10.1021/acs.jpcb.9b01012	journal	April 2019
Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy Urquhart, Stephen G.; Martinson, Mercedes; Eger, Shaylin The Journal of Physical Chemistry C, Vol. 121, Issue 39 https://doi.org/10.1021/acs.jpcc.7b07143	journal	September 2017
Mechanical Properties of Structure-Tunable, Vapor-Deposited TPD Glass Tangpatjaroen, Chaiyapat; Bagchi, Kushal; Martínez, Rafael A. The Journal of Physical Chemistry C, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpcc.8b09718	journal	November 2018
Controlling Structure and Properties of Vapor-Deposited Glasses of Organic Semiconductors: Recent Advances and Challenges Bagchi, Kushal; Ediger, M. D. The Journal of Physical Chemistry Letters, Vol. 11, Issue 17 https://doi.org/10.1021/acs.jpclett.0c01682	journal	July 2020
Influence of Molecular Shape on the Thermal Stability and Molecular Orientation of Vapor-Deposited Organic Semiconductors Walters, Diane M.; Antony, Lucas; de Pablo, Juan J. The Journal of Physical Chemistry Letters, Vol. 8, Issue 14, p. 3380-3386 https://doi.org/10.1021/acs.jpclett.7b01097	journal	July 2017
Enhanced Electrical Properties and Air Stability of Amorphous Organic Thin Films by Engineering Film Density Esaki, Yu; Komino, Takeshi; Matsushima, Toshinori The Journal of Physical Chemistry Letters, Vol. 8, Issue 23 https://doi.org/10.1021/acs.jpclett.7b02808	journal	November 2017
Surface Diffusion of Polymer Glasses Zhang, Wei; Yu, Lian Macromolecules, Vol. 49, Issue 2 https://doi.org/10.1021/acs.macromol.5b02294	journal	January 2016
Self-Assembly of ABC Bottlebrush Triblock Terpolymers with Evidence for Looped Backbone Conformations Sunday, Daniel F.; Chang, Alice B.; Liman, Christopher D. Macromolecules, Vol. 51, Issue 18 https://doi.org/10.1021/acs.macromol.8b01370	journal	September 2018
Over What Length Scale Does an Inorganic Substrate Perturb the Structure of a Glassy Organic Semiconductor? Bagchi, Kushal; Deng, Chuting; Bishop, Camille ACS Applied Materials & Interfaces, Vol. 12, Issue 23 https://doi.org/10.1021/acsami.0c06428	journal	May 2020
Dependence of Organic Interlayer Diffusion on Glass-Transition Temperature in OLEDs McEwan, Jake A.; Clulow, Andrew J.; Nelson, Andrew ACS Applied Materials & Interfaces, Vol. 9, Issue 16 https://doi.org/10.1021/acsami.7b01450	journal	April 2017
Isolating Degradation Mechanisms in Mixed Emissive Layer Organic Light-Emitting Devices Bangsund, John S.; Hershey, Kyle W.; Holmes, Russell J. ACS Applied Materials & Interfaces, Vol. 10, Issue 6 https://doi.org/10.1021/acsami.7b16643	journal	February 2018
Interface Engineering: An Effective Approach toward High-Performance Organic Field-Effect Transistors Di, Chong-an; Liu, Yunqi; Yu, Gui Accounts of Chemical Research, Vol. 42, Issue 10 https://doi.org/10.1021/ar9000873	journal	October 2009
Molar Volumes of Ethylcyclohexane and Butyronitrile Glasses Resulting from Vapor Deposition: Dependence on Deposition Temperature and Comparison to Alkylbenzenes Nakayama, Hideyuki; Omori, Kio; Ino-u-e, Katsunobu The Journal of Physical Chemistry B, Vol. 117, Issue 35 https://doi.org/10.1021/jp404256r	journal	August 2013
Essential Differences of Organic Films at the Molecular Level via Vacuum Deposition and Solution Processes for Organic Light-Emitting Diodes Xing, Xing; Zhong, Luwei; Zhang, Lipei The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp410547w	journal	November 2013
Surface Segregation Studies of Fluorine-Containing Diblock Copolymers ^† Iyengar, Dhamodharan R.; Perutz, Susanne M.; Dai, Chi-An Macromolecules, Vol. 29, Issue 4 https://doi.org/10.1021/ma950544z	journal	January 1996
Tailored exciton diffusion in organic photovoltaic cells for enhanced power conversion efficiency Menke, S. Matthew; Luhman, Wade A.; Holmes, Russell J. Nature Materials, Vol. 12, Issue 2 https://doi.org/10.1038/nmat3467	journal	November 2012
Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics Jailaubekov, Askat E.; Willard, Adam P.; Tritsch, John R. Nature Materials, Vol. 12, Issue 1 https://doi.org/10.1038/nmat3500	journal	December 2012
Ultrastable monodisperse polymer glass formed by physical vapour deposition Raegen, Adam N.; Yin, Junjie; Zhou, Qi Nature Materials, Vol. 19, Issue 10 https://doi.org/10.1038/s41563-020-0723-7	journal	July 2020
Photo- and electroactive amorphous molecular materials—molecular design, syntheses, reactions, properties, and applications Shirota, Yasuhiko J. Mater. Chem., Vol. 15, Issue 1 https://doi.org/10.1039/b413819h	journal	January 2005
Thickness dependence of the elastic modulus of tris(8-hydroxyquinolinato)aluminium Torres, Jessica M.; Bakken, Nathan; Stafford, Christopher M. Soft Matter, Vol. 6, Issue 22 https://doi.org/10.1039/c0sm00364f	journal	January 2010
Molecular orientation in small-molecule organic light-emitting diodes Yokoyama, Daisuke Journal of Materials Chemistry, Vol. 21, Issue 48 https://doi.org/10.1039/c1jm13417e	journal	January 2011
Thickness dependent modulus of vacuum deposited organic molecular glasses for organic electronics applications Bakken, Nathan; Torres, Jessica M.; Li, Jian Soft Matter, Vol. 7, Issue 16 https://doi.org/10.1039/c1sm05732d	journal	January 2011
Flash-evaporated small molecule films toward low-cost and flexible organic light-emitting diodes Wang, Bo; Wang, Zhao-Kui; Liang, Jian J. Mater. Chem. C, Vol. 5, Issue 41 https://doi.org/10.1039/c7tc03529b	journal	January 2017
All-atom simulation of molecular orientation in vapor-deposited organic light-emitting diodes Youn, Yong; Yoo, Dongsun; Song, Hochul Journal of Materials Chemistry C, Vol. 6, Issue 5 https://doi.org/10.1039/c7tc05278b	journal	January 2018
Generic packing motifs in vapor-deposited glasses of organic semiconductors Bagchi, Kushal; Gujral, Ankit; Toney, M. F. Soft Matter, Vol. 15, Issue 38 https://doi.org/10.1039/c9sm01155b	journal	January 2019
Surface diffusion in glasses of rod-like molecules posaconazole and itraconazole: effect of interfacial molecular alignment and bulk penetration Li, Yuhui; Zhang, Wei; Bishop, Camille Soft Matter, Vol. 16, Issue 21 https://doi.org/10.1039/d0sm00353k	journal	January 2020
Enhanced hole mobility in ambipolar rubrene thin film transistors on polystyrene Park, Byoungnam; In, Insik; Gopalan, Padma Applied Physics Letters, Vol. 92, Issue 13 https://doi.org/10.1063/1.2904964	journal	March 2008
The Current Performance of the Wide Range (90–2500 eV) Soft X-ray Beamline at the Australian Synchrotron Cowie, B. C. C.; Tadich, A.; Thomsen, L. SRI 2009, 10TH INTERNATIONAL CONFERENCE ON RADIATION INSTRUMENTATION, AIP Conference Proceedings https://doi.org/10.1063/1.3463197	conference	January 2010
Soft x-ray scattering facility at the Advanced Light Source with real-time data processing and analysis Gann, E.; Young, A. T.; Collins, B. A. Review of Scientific Instruments, Vol. 83, Issue 4 https://doi.org/10.1063/1.3701831	journal	April 2012
Density and birefringence of a highly stable α,α,β-trisnaphthylbenzene glass Dalal, Shakeel S.; Sepúlveda, A.; Pribil, Greg K. The Journal of Chemical Physics, Vol. 136, Issue 20 https://doi.org/10.1063/1.4719532	journal	May 2012
Near-edge X-ray absorption fine-structure spectroscopy of naphthalene diimide-thiophene co-polymers Gann, Eliot; McNeill, Christopher R.; Szumilo, Monika The Journal of Chemical Physics, Vol. 140, Issue 16 https://doi.org/10.1063/1.4871463	journal	April 2014
Thermal stability of vapor-deposited stable glasses of an organic semiconductor Walters, Diane M.; Richert, Ranko; Ediger, M. D. The Journal of Chemical Physics, Vol. 142, Issue 13 https://doi.org/10.1063/1.4916649	journal	April 2015
Orientational anisotropy in simulated vapor-deposited molecular glasses Lyubimov, Ivan; Antony, Lucas; Walters, Diane M. The Journal of Chemical Physics, Vol. 143, Issue 9 https://doi.org/10.1063/1.4928523	journal	September 2015
Quantitative resonant soft x-ray reflectivity of ultrathin anisotropic organic layers: Simulation and experiment of PTCDA on Au Capelli, R.; Mahne, N.; Koshmak, K. The Journal of Chemical Physics, Vol. 145, Issue 2 https://doi.org/10.1063/1.4956452	journal	July 2016
Long-range correlated dynamics in ultra-thin molecular glass films Zhang, Yue; Glor, Ethan C.; Li, Mu The Journal of Chemical Physics, Vol. 145, Issue 11 https://doi.org/10.1063/1.4962734	journal	September 2016
Exploring the broadening and the existence of two glass transitions due to competing interfacial effects in thin, supported polymer films Glor, Ethan C.; Angrand, Gabriel V.; Fakhraai, Zahra The Journal of Chemical Physics, Vol. 146, Issue 20 https://doi.org/10.1063/1.4979944	journal	May 2017
Perspective: Highly stable vapor-deposited glasses Ediger, M. D. The Journal of Chemical Physics, Vol. 147, Issue 21 https://doi.org/10.1063/1.5006265	journal	December 2017
Effect of substrate interactions on the glass transition and length-scale of correlated dynamics in ultra-thin molecular glass films Zhang, Yue; Woods, Connor N.; Alvarez, Mauricio The Journal of Chemical Physics, Vol. 149, Issue 18 https://doi.org/10.1063/1.5038174	journal	November 2018
Effect of molecular size and hydrogen bonding on three surface-facilitated processes in molecular glasses: Surface diffusion, surface crystal growth, and formation of stable glasses by vapor deposition Chen, Yinshan; Chen, Zhenxuan; Tylinski, Michael The Journal of Chemical Physics, Vol. 150, Issue 2 https://doi.org/10.1063/1.5079441	journal	January 2019
Quantitative resonant soft x-ray reflectivity from an organic semiconductor single crystal Capelli, R.; Da Como, E.; Kociok-Köhn, G. The Journal of Chemical Physics, Vol. 150, Issue 9 https://doi.org/10.1063/1.5080800	journal	March 2019
Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement Schweizer, Kenneth S.; Simmons, David S. The Journal of Chemical Physics, Vol. 151, Issue 24 https://doi.org/10.1063/1.5129405	journal	December 2019
Internal molecular conformation of organic glasses: A NEXAFS study Zuhaib, Amara; Urquhart, Stephen G. The Journal of Chemical Physics, Vol. 155, Issue 3 https://doi.org/10.1063/5.0054442	journal	July 2021
Tunable molecular orientation and elevated thermal stability of vapor-deposited organic semiconductors Dalal, Shakeel S.; Walters, Diane M.; Lyubimov, Ivan Proceedings of the National Academy of Sciences, Vol. 112, Issue 14 https://doi.org/10.1073/pnas.1421042112	journal	March 2015
Effects of microstructure formation on the stability of vapor-deposited glasses Moore, Alex R.; Huang, Georgia; Wolf, Sarah Proceedings of the National Academy of Sciences, Vol. 116, Issue 13 https://doi.org/10.1073/pnas.1821761116	journal	March 2019
Vapor deposition of a nonmesogen prepares highly structured organic glasses Bishop, Camille; Thelen, Jacob L.; Gann, Eliot Proceedings of the National Academy of Sciences, Vol. 116, Issue 43 https://doi.org/10.1073/pnas.1908445116	journal	September 2019
Surface equilibration mechanism controls the molecular packing of glassy molecular semiconductors at organic interfaces Fiori, Marie E.; Bagchi, Kushal; Toney, Michael F. Proceedings of the National Academy of Sciences, Vol. 118, Issue 42 https://doi.org/10.1073/pnas.2111988118	journal	October 2021
Emitter Orientation as a Key Parameter in Organic Light-Emitting Diodes Schmidt, Tobias D.; Lampe, Thomas; Sylvinson M. R., Daniel Physical Review Applied, Vol. 8, Issue 3 https://doi.org/10.1103/PhysRevApplied.8.037001	journal	September 2017
Molecular orientation in soft matter thin films studied by resonant soft x-ray reflectivity Mezger, Markus; Jérôme, Blandine; Kortright, Jeffrey B. Physical Review B, Vol. 83, Issue 15 https://doi.org/10.1103/PhysRevB.83.155406	journal	April 2011
Structural and electronic properties of anisotropic ultrathin organic films from dichroic resonant soft x-ray reflectivity Pasquali, Luca; Mukherjee, Subhrangsu; Terzi, Fabio Physical Review B, Vol. 89, Issue 4 https://doi.org/10.1103/PhysRevB.89.045401	journal	January 2014
refnx : neutron and X-ray reflectometry analysis in Python Nelson, Andrew R. J.; Prescott, Stuart W. Journal of Applied Crystallography, Vol. 52, Issue 1 https://doi.org/10.1107/S1600576718017296	journal	February 2019
Quick AS NEXAFS Tool ( QANT ): a program for NEXAFS loading and analysis developed at the Australian Synchrotron Gann, Eliot; McNeill, Christopher R.; Tadich, Anton Journal of Synchrotron Radiation, Vol. 23, Issue 1 https://doi.org/10.1107/S1600577515018688	journal	January 2016
Metal–organic interface and charge injection in organic electronic devices Scott, J. Campbell Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 21, Issue 3 https://doi.org/10.1116/1.1559919	journal	May 2003
High-performance organic light-emitting diodes comprising ultrastable glass layers Ràfols-Ribé, Joan; Will, Paul-Anton; Hänisch, Christian Science Advances, Vol. 4, Issue 5 https://doi.org/10.1126/sciadv.aar8332	journal	May 2018
Organic Glasses with Exceptional Thermodynamic and Kinetic Stability Swallen, S. F.; Kearns, K. L.; Mapes, M. K. Science, Vol. 315, Issue 5810 https://doi.org/10.1126/science.1135795	journal	January 2007

Similar Records

Influence of Molecular Shape on the Thermal Stability and Molecular Orientation of Vapor-Deposited Organic Semiconductors

Dataset · 2017 · OSTI ID:1372474

Walters, Diane M; Antony, Lucas; de Pablo, Juan; +1 more

Over What Length Scale Does an Inorganic Substrate Perturb the Structure of a Glassy Organic Semiconductor?

Journal Article · 2020 · ACS Applied Materials and Interfaces · OSTI ID:1647596

Bagchi, Kushal; Deng, Chuting; Bishop, Camille; +6 more

Link between hopping models and percolation scaling laws for charge transport in mixtures of small molecules

Journal Article · 2016 · AIP Advances · OSTI ID:1262288

Ha, Dong -Gwang; Kim, Jang -Joo; Baldo, Marc A.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
NEXAFS spectroscopy
amorphous materials
buried interface
coarse-grained simulations
deposition
layers
molecules
optical properties
organic semiconductor
polarized resonant soft X-ray reflectivity
thin films

Title: Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

Citation Formats

References (68)

Similar Records

Related Subjects