DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Band-like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface

Abstract

Organic photovoltaic cells possess desirable practical characteristics, such as the potential for low-cost fabrication on flexible substrates, but they lag behind their inorganic counterparts in performance due in part to fundamental energy loss mechanisms, such as overcoming the charge transfer (CT) state binding energy when photogenerated charge is transferred across the donor/acceptor interface. However, recent work has suggested that crystalline interfaces can reduce this binding energy due to enhanced CT state delocalization. Solar cells based on rubrene and C60 are investigated as an archetypal system because it allows the degree of crystallinity to be moldulated from a highly disordered to highly ordered system. Using a postdeposition annealing method to transform as-deposited amorphous rubrene thin films into ones that are highly crystalline, it is shown that the CT state of a highly crystalline rubrene/C60 heterojunction undergoes extreme delocalization parallel to the interface leading to a band-like state that exhibits a linear Stark effect. This state parallels the direct charge formation of inorganic solar cells and reduces energetic losses by 220 meV compared with 12 other archetypal heterojunctions reported in the literature.

Authors:
 [1];  [1];  [2];  [3];  [1];  [4];  [1];  [5];  [2];  [1]; ORCiD logo [5]
  1. Princeton Univ., NJ (United States). Dept. of Electrical Engineering
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
  3. Princeton Univ., NJ (United States). Dept. of Chemical and Biological Engineering
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  5. Princeton Univ., NJ (United States). Dept. of Electrical Engineering, Andlinger Center for Energy and the Environment
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE); Princeton Univ., NJ (United States); Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Department of Defense (DoD); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1470430
Alternate Identifier(s):
OSTI ID: 1412584; OSTI ID: 1595406
Grant/Contract Number:  
SC0001088; SC0012458; SC0012365; DMR‐1332208; DMR‐1420541; AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 9; Related Information: CE partners with Massachusetts Institute of Technology (lead); Brookhaven National Laboratory; Harvard University; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 42 ENGINEERING; solar (photovoltaic); solid state lighting; photosynthesis (natural and artificial); charge transport; optics; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); charge transfer state; crystal; delocalized; rubrene; solar cells

Citation Formats

Fusella, Michael A., Brigeman, Alyssa N., Welborn, Matthew, Purdum, Geoffrey E., Yan, Yixin, Schaller, Richard D., Lin, YunHui L., Loo, Yueh-Lin, Voorhis, Troy Van, Giebink, Noel C., and Rand, Barry P. Band-like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface. United States: N. p., 2017. Web. doi:10.1002/aenm.201701494.
Fusella, Michael A., Brigeman, Alyssa N., Welborn, Matthew, Purdum, Geoffrey E., Yan, Yixin, Schaller, Richard D., Lin, YunHui L., Loo, Yueh-Lin, Voorhis, Troy Van, Giebink, Noel C., & Rand, Barry P. Band-like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface. United States. https://doi.org/10.1002/aenm.201701494
Fusella, Michael A., Brigeman, Alyssa N., Welborn, Matthew, Purdum, Geoffrey E., Yan, Yixin, Schaller, Richard D., Lin, YunHui L., Loo, Yueh-Lin, Voorhis, Troy Van, Giebink, Noel C., and Rand, Barry P. Fri . "Band-like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface". United States. https://doi.org/10.1002/aenm.201701494. https://www.osti.gov/servlets/purl/1470430.
@article{osti_1470430,
title = {Band-like Charge Photogeneration at a Crystalline Organic Donor/Acceptor Interface},
author = {Fusella, Michael A. and Brigeman, Alyssa N. and Welborn, Matthew and Purdum, Geoffrey E. and Yan, Yixin and Schaller, Richard D. and Lin, YunHui L. and Loo, Yueh-Lin and Voorhis, Troy Van and Giebink, Noel C. and Rand, Barry P.},
abstractNote = {Organic photovoltaic cells possess desirable practical characteristics, such as the potential for low-cost fabrication on flexible substrates, but they lag behind their inorganic counterparts in performance due in part to fundamental energy loss mechanisms, such as overcoming the charge transfer (CT) state binding energy when photogenerated charge is transferred across the donor/acceptor interface. However, recent work has suggested that crystalline interfaces can reduce this binding energy due to enhanced CT state delocalization. Solar cells based on rubrene and C60 are investigated as an archetypal system because it allows the degree of crystallinity to be moldulated from a highly disordered to highly ordered system. Using a postdeposition annealing method to transform as-deposited amorphous rubrene thin films into ones that are highly crystalline, it is shown that the CT state of a highly crystalline rubrene/C60 heterojunction undergoes extreme delocalization parallel to the interface leading to a band-like state that exhibits a linear Stark effect. This state parallels the direct charge formation of inorganic solar cells and reduces energetic losses by 220 meV compared with 12 other archetypal heterojunctions reported in the literature.},
doi = {10.1002/aenm.201701494},
journal = {Advanced Energy Materials},
number = 9,
volume = 8,
place = {United States},
year = {Fri Dec 08 00:00:00 EST 2017},
month = {Fri Dec 08 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes
journal, December 2013


Microcrystalline Organic Thin-Film Solar Cells
journal, August 2013

  • Verreet, Bregt; Heremans, Paul; Stesmans, Andre
  • Advanced Materials, Vol. 25, Issue 38
  • DOI: 10.1002/adma.201301643

Homoepitaxy of Crystalline Rubrene Thin Films
journal, April 2017


The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004


Reaction field treatment of charge penetration
journal, April 2000

  • Chipman, Daniel M.
  • The Journal of Chemical Physics, Vol. 112, Issue 13
  • DOI: 10.1063/1.481133

Patterning organic single-crystal transistor arrays
journal, December 2006

  • Briseno, Alejandro L.; Mannsfeld, Stefan C. B.; Ling, Mang M.
  • Nature, Vol. 444, Issue 7121, p. 913-917
  • DOI: 10.1038/nature05427

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

  • Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
  • Journal of the American Chemical Society, Vol. 118, Issue 45
  • DOI: 10.1021/ja9621760

Absorption spectroscopy on Ga 0.47 In 0.53 As/ Al 0.48 In 0.52 As multi-quantum-well heterostructures. II. Subband structure
journal, September 1987


The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors
journal, February 2012


Disorder and the molecular packing of C 60 buckminsterfullerene: a direct electron-crystallographic analysis
journal, May 1994

  • Dorset, D. L.; McCourt, M. P.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 50, Issue 3
  • DOI: 10.1107/S0108767393012607

Relating the open-circuit voltage to interface molecular properties of donor:acceptor bulk heterojunction solar cells
journal, March 2010


Room‐temperature excitons in 1.6‐μm band‐gap GaInAs/AlInAs quantum wells
journal, April 1985

  • Weiner, J. S.; Chemla, D. S.; Miller, D. A. B.
  • Applied Physics Letters, Vol. 46, Issue 7
  • DOI: 10.1063/1.95504

Revealing the Full Charge Transfer State Absorption Spectrum of Organic Solar Cells
journal, August 2016

  • Brigeman, Alyssa N.; Fusella, Michael A.; Yan, Yixin
  • Advanced Energy Materials, Vol. 6, Issue 21
  • DOI: 10.1002/aenm.201601001

Morphological Tuning of the Energetics in Singlet Fission Organic Solar Cells
journal, July 2016

  • Lin, YunHui L.; Fusella, Michael A.; Kozlov, Oleg V.
  • Advanced Functional Materials, Vol. 26, Issue 35
  • DOI: 10.1002/adfm.201601125

Quasi-Fermi level splitting and sub-bandgap absorptivity from semiconductor photoluminescence
journal, November 2014

  • Katahara, John K.; Hillhouse, Hugh W.
  • Journal of Applied Physics, Vol. 116, Issue 17
  • DOI: 10.1063/1.4898346

Low-temperature structure of rubrene single crystals grown by vapor transport
journal, March 2006

  • Jurchescu, Oana D.; Meetsma, Auke; Palstra, Thomas T. M.
  • Acta Crystallographica Section B Structural Science, Vol. 62, Issue 2
  • DOI: 10.1107/S0108768106003053

Delocalization and dielectric screening of charge transfer states in organic photovoltaic cells
journal, February 2014

  • Bernardo, B.; Cheyns, D.; Verreet, B.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4245

Solar cell efficiency tables (version 50)
journal, June 2017

  • Green, Martin A.; Hishikawa, Yoshihiro; Warta, Wilhelm
  • Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 7
  • DOI: 10.1002/pip.2909

Influence of disorder on the field-modulated spectra of polydiacetylene films
journal, February 1995


Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers
journal, September 2015


Observation of long-range exciton diffusion in highly ordered organic semiconductors
journal, October 2010

  • Najafov, H.; Lee, B.; Zhou, Q.
  • Nature Materials, Vol. 9, Issue 11
  • DOI: 10.1038/nmat2872

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Charge Photogeneration in Organic Solar Cells
journal, November 2010

  • Clarke, Tracey M.; Durrant, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6736-6767
  • DOI: 10.1021/cr900271s

Efficient charge generation by relaxed charge-transfer states at organic interfaces
journal, November 2013

  • Vandewal, Koen; Albrecht, Steve; Hoke, Eric T.
  • Nature Materials, Vol. 13, Issue 1
  • DOI: 10.1038/nmat3807

Atomically Thin MoS2 A New Direct-Gap Semiconductor
journal, September 2010


Quantification of energy losses in organic solar cells from temperature-dependent device characteristics
journal, December 2013


Intrinsic Charge Transport on the Surface of Organic Semiconductors
journal, August 2004


Band-Like Electron Transport in Organic Transistors and Implication of the Molecular Structure for Performance Optimization
journal, December 2011

  • Minder, Nikolas A.; Ono, Shimpei; Chen, Zhihua
  • Advanced Materials, Vol. 24, Issue 4
  • DOI: 10.1002/adma.201103960

Use of an Underlayer for Large Area Crystallization of Rubrene Thin Films
journal, July 2017


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


Beyond Langevin Recombination: How Equilibrium Between Free Carriers and Charge Transfer States Determines the Open-Circuit Voltage of Organic Solar Cells
journal, April 2015

  • Burke, Timothy M.; Sweetnam, Sean; Vandewal, Koen
  • Advanced Energy Materials, Vol. 5, Issue 11
  • DOI: 10.1002/aenm.201500123

Factors Limiting Device Efficiency in Organic Photovoltaics
journal, December 2012


V oc from a Morphology Point of View: the Influence of Molecular Orientation on the Open Circuit Voltage of Organic Planar Heterojunction Solar Cells
journal, November 2014

  • Hörmann, Ulrich; Lorch, Christopher; Hinderhofer, Alexander
  • The Journal of Physical Chemistry C, Vol. 118, Issue 46
  • DOI: 10.1021/jp506180k

Free carrier and many-body effects in absorption spectra of modulation-doped quantum wells
journal, August 1988

  • Livescu, G.; Miller, D. A. B.; Chemla, D. S.
  • IEEE Journal of Quantum Electronics, Vol. 24, Issue 8
  • DOI: 10.1109/3.7098

Thermodynamic efficiency limit of excitonic solar cells
journal, May 2011

  • Giebink, Noel C.; Wiederrecht, Gary P.; Wasielewski, Michael R.
  • Physical Review B, Vol. 83, Issue 19
  • DOI: 10.1103/PhysRevB.83.195326

Re-evaluating the Role of Sterics and Electronic Coupling in Determining the Open-Circuit Voltage of Organic Solar Cells
journal, July 2013

  • Graham, Kenneth R.; Erwin, Patrick; Nordlund, Dennis
  • Advanced Materials, Vol. 25, Issue 42
  • DOI: 10.1002/adma.201301319

Temperature Dependence of Charge Carrier Generation in Organic Photovoltaics
journal, March 2015


Bandlike transport in pentacene and functionalized pentacene thin films revealed by subpicosecond transient photoconductivity measurements
journal, January 2005


Configuration interaction based on constrained density functional theory: A multireference method
journal, October 2007

  • Wu, Qin; Cheng, Chiao-Lun; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 127, Issue 16
  • DOI: 10.1063/1.2800022

Rational identification and characterisation of peptide ligands for targeting polysialic acid
journal, May 2020

  • Shastry, Divya G.; Irudayanathan, Flaviyan Jerome; Williams, Asher
  • Scientific Reports, Vol. 10, Issue 1
  • DOI: 10.1038/s41598-020-64088-z

Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes
conference, January 2014

  • Gelinas, Simon; Rao, Akshay; Kumar, Abhishek
  • 19th International Conference on Ultrafast Phenomena
  • DOI: 10.1364/up.2014.07.mon.c.7

The Role of Driving Energy and Delocalised States for Charge Separation in Organic Semiconductors
text, January 2013


Intrinsic charge transport on the surface of organic semiconductors
text, January 2004


Works referencing / citing this record:

Charge-transfer electronic states in organic solar cells
journal, September 2019

  • Coropceanu, Veaceslav; Chen, Xian-Kai; Wang, Tonghui
  • Nature Reviews Materials, Vol. 4, Issue 11
  • DOI: 10.1038/s41578-019-0137-9

Thousand-atom ab initio calculations of excited states at organic/organic interfaces: toward first-principles investigations of charge photogeneration
journal, January 2018

  • Fujita, Takatoshi; Alam, Md. Khorshed; Hoshi, Takeo
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 41
  • DOI: 10.1039/c8cp05574b

Molecular origin of efficient hole transfer from non-fullerene acceptors: insights from first-principles calculations
journal, January 2019

  • Benatto, Leandro; Marchiori, Cleber F. N.; Araujo, C. Moyses
  • Journal of Materials Chemistry C, Vol. 7, Issue 39
  • DOI: 10.1039/c9tc03563j

Variable charge transfer state energies at nanostructured pentacene/C 60 interfaces
journal, May 2018

  • Lin, YunHui L.; Zhang, Fengyu; Kerner, Ross A.
  • Applied Physics Letters, Vol. 112, Issue 21
  • DOI: 10.1063/1.5030885