skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enhancement in Organic Photovoltaic Efficiency through the Synergistic Interplay of Molecular Donor Hydrogen Bonding and -Stacking

Journal Article · · Advanced Functional Materials

For organic photovoltaic (OPV) cells based on the bulk heterojunction (BHJ) structure, it remains challenging to rationally control the degree of phase separation and percolation within blends of donors and acceptors to secure optimal charge separation and transport. Reported is a bottom-up, supramolecular approach to BHJ OPVs wherein tailored hydrogen bonding (H-bonding) interactions between π-conjugated electron donor molecules encourage formation of vertically aligned donor π-stacks while simultaneously suppressing lateral aggregation; the programmed arrangement facilitates fine mixing with fullerene acceptors and efficient charge transport. The approach is illustrated using conventional linear or branched quaterthiophene donor chromophores outfitted with terminal functional groups that are either capable or incapable of self-complementary H-bonding. When applied to OPVs, the H-bond capable donors yield a twofold enhancement in power conversion efficiency relative to the comparator systems, with a maximum external quantum efficiency of 64%. H-bond promoted assembly results in redshifted absorption (in neat films and donor:C 60 blends) and enhanced charge collection efficiency despite disparate donor chromophore structure. Both features positively impact photocurrent and fill factor in OPV devices. Film structural characterization by atomic force microscopy, transmission electron microscopy, and grazing incidence wide angle X-ray scattering reveals a synergistic interplay of lateral H-bonding interactions and vertical π-stacking for directing the favorable morphology of the BHJ.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1286904
Journal Information:
Advanced Functional Materials, Vol. 25, Issue 32; ISSN 1616-301X
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

References (73)

A Mechanistic Understanding of Processing Additive-Induced Efficiency Enhancement in Bulk Heterojunction Organic Solar Cells journal October 2013
Supramolecular Chemistry and Self-Assembly in Organic Materials Design journal September 2013
6H-Pyrrolo[3,2-b:4,5-b′]bis[1,4]benzothiazines: facilely synthesized semiconductors for organic field-effect transistors journal January 2008
H-Bonding Tuned Self-Assembly of Phenylene–Thiophene–Thiophene–Phenylene Derivatives at Surfaces: Structural and Electrical Studies journal April 2011
A Crystal-Engineered Hydrogen-Bonded Octachloroperylene Diimide with a Twisted Core: An n-Channel Organic Semiconductor journal October 2009
Grooved Nanowires from Self-Assembling Hairpin Molecules for Solar Cells journal February 2012
Investigation of Phase Separation in Bulk Heterojunction Solar Cells via Supramolecular Chemistry journal April 2013
Fluorine Substituents Reduce Charge Recombination and Drive Structure and Morphology Development in Polymer Solar Cells journal January 2013
Perspectives on Organic Photovoltaics journal October 2010
Organic solar cells: Their developments and potentials journal May 2013
N-heteroquinones: quadruple weak hydrogen bonds and n-channel transistors journal January 2010
Polymer solar cells with enhanced open-circuit voltage and efficiency journal November 2009
Photoluminescence and Conductivity of Self-Assembled π–π Stacks of Perylene Bisimide Dyes journal January 2007
Rational Design of Small Molecular Donor for Solution-Processed Organic Photovoltaics with 8.1% Efficiency and High Fill Factor via Multiple Fluorine Substituents and Thiophene Bridge journal May 2015
Enhancement of efficiency in organic photovoltaic devices containing self-complementary hydrogen-bonding domains journal January 2013
A Versatile Fluoro-Containing Low-Bandgap Polymer for Efficient Semitransparent and Tandem Polymer Solar Cells journal July 2013
Influence of intermolecular interactions of electron donating small molecules on their molecular packing and performance in organic electronic devices journal January 2013
A Hybrid Planar-Mixed Molecular Heterojunction Photovoltaic Cell journal January 2005
Hydrogen-Bonding-Facilitated Layer-by-Layer Growth of Ultrathin Organic Semiconducting Films journal July 2013
In Situ Morphology Studies of the Mechanism for Solution Additive Effects on the Formation of Bulk Heterojunction Films journal September 2014
Development and testing of a general amber force field journal January 2004
Donor–acceptor–donor (D–A–D) molecules based on isoindigo as active material for organic solar cells journal January 2013
Synthesis of Fluorinated Polythienothiophene- co -benzodithiophenes and Effect of Fluorination on the Photovoltaic Properties journal February 2011
Significant Improved Performance of Photovoltaic Cells Made from a Partially Fluorinated Cyclopentadithiophene/Benzothiadiazole Conjugated Polymer journal June 2012
Effect of fluorine substitution on photovoltaic performance of DPP-based copolymer journal May 2015
Hydrogen-bonded diketopyrrolopyrrole (DPP) pigments as organic semiconductors journal December 2014
NIH Image to ImageJ: 25 years of image analysis journal June 2012
Ambipolar Behavior of Hydrogen-Bonded Diketopyrrolopyrrole–Thiophene Co-oligomers Formed from Their Soluble Precursors journal June 2012
Organic Semiconductors and their Applications in Photovoltaic Devices journal January 2012
Indigo - A Natural Pigment for High Performance Ambipolar Organic Field Effect Transistors and Circuits journal November 2011
Effects of Solvent Additives on Morphology, Charge Generation, Transport, and Recombination in Solution-Processed Small-Molecule Solar Cells journal January 2014
Post-Deposition Activation of Latent Hydrogen-Bonding: A New Paradigm for Enhancing the Performances of Bulk Heterojunction Solar Cells journal September 2014
Intermolecular hydrogen-bonded organic semiconductors—Quinacridone versus pentacene journal July 2012
Mixed donor-acceptor molecular heterojunctions for photovoltaic applications. I. Material properties journal December 2005
Disentangling the impact of side chains and fluorine substituents of conjugated donor polymers on the performance of photovoltaic blends journal January 2013
The Effect of Fluorination in Manipulating the Nanomorphology in PTB7:PC 71 BM Bulk Heterojunction Systems journal October 2014
Synthesis and n-Type Field-effect Transistor Characteristics of Dioxopyrrolopyrrole Derivatives journal August 2011
Hydrogen-Bonded Dihydrotetraazapentacenes journal January 2012
Fluorination of Polythiophene Derivatives for High Performance Organic Photovoltaics journal July 2014
Fluorinated Polymer Yields High Organic Solar Cell Performance for a Wide Range of Morphologies journal February 2013
Hydrogen bond directed assembly of oligothiophene/fullerene superstructures on Au(111) journal April 2015
Correlation between oxidation potential and open-circuit voltage of composite solar cells based on blends of polythiophenes/ fullerene derivative journal March 2004
Enhancing the Performance of Solution-Processed Bulk-Heterojunction Solar Cells Using Hydrogen-Bonding-Induced Self-Organization of Small Molecules journal November 2013
Small Molecule Organic Semiconductors on the Move: Promises for Future Solar Energy Technology journal February 2012
25th Anniversary Article: Bulk Heterojunction Solar Cells: Understanding the Mechanism of Operation journal December 2013
Fluorinated Copolymer PCPDTBT with Enhanced Open-Circuit Voltage and Reduced Recombination for Highly Efficient Polymer Solar Cells journal August 2012
Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects journal February 1981
Supramolecular Liquid Crystals. Self-Assembly of a Trimeric Supramolecular Disk and Its Self-Organization into a Columnar Discotic Mesophase journal September 1998
Hierarchical Assembly of a Phthalhydrazide-Functionalized Helicene journal March 2011
Hydrogen-bonded Supramolecular π-Functional Materials journal February 2011
X-ray crystal structure and vibrational spectra of hydrazides and their metal complexes. Part II. Hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate journal November 2007
Supramolecular Engineering of Oligothiophene Nanorods without Insulators: Hierarchical Association of Rosettes and Photovoltaic Properties journal October 2014
Homo- and Heteroassemblies of Lactim/Lactam Recognition Patterns on Highly Ordered Pyrolytic Graphite:  An STM Investigation journal August 2006
Organic Single Crystal Field-effect Transistors Based on 6H-pyrrolo[3,2-b:4,5-b´]bis[1,4]benzothiazine and its Derivatives journal June 2010
Improving Solar Cell Efficiency through Hydrogen Bonding: A Method for Tuning Active Layer Morphology journal February 2015
Fluorinated Zinc Phthalocyanine as Donor for Efficient Vacuum-Deposited Organic Solar Cells journal November 2011
Recent progress in organic photovoltaics: device architecture and optical design journal January 2014
Herringbone to cofacial solid state packing via H-bonding in diketopyrrolopyrrole (DPP) based molecular crystals: influence on charge transport journal January 2015
Interconvertible Oligothiophene Nanorods and Nanotapes with High Charge-Carrier Mobilities journal September 2009
The future of organic photovoltaics journal January 2015
The case for organic photovoltaics journal January 2013
Two-Dimensional Self-Assembly of 1-Pyrylphosphonic Acid:  Transfer of Stacks on Structured Surface journal May 2006
Estimating the shape and size of supramolecular assemblies by variable temperature diffusion ordered spectroscopy journal January 2014
Hydrogen-Bonded Semiconducting Pigments for Air-Stable Field-Effect Transistors journal December 2012
Stepwise self-assembly to improve solar cell morphology journal January 2013
Consequences of hydrogen bonding on molecular organization and charge transport in molecular organic photovoltaic materials journal January 2014
Effect of Fluorination on the Properties of a Donor–Acceptor Copolymer for Use in Photovoltaic Cells and Transistors journal January 2013
Solid-solid phase interconversion in an organic conductor crystal: hydrogen-bond-mediated dynamic changes in π-stacked molecular arrangement and physical properties journal January 2014
Bulk Heterojunction Solar Cells: Morphology and Performance Relationships journal May 2014
Comparison of Two D−A Type Polymers with Each Being Fluorinated on D and A Unit for High Performance Solar Cells journal October 2014
Size analysis of single fullerene molecules by electron microscopy journal January 2004
Molden: a pre- and post-processing program for molecular and electronic structures* journal February 2000
Hydrogen bonding in bulk heterojunction solar cells: A case study journal July 2014

Cited By (4)

Self-Assembly of Chiral-at-End Diketopyrrolopyrroles: Symmetry Dependent Solution and Film Optical Activity and Photovoltaic Performance journal August 2018
Tuning the polarity and surface activity of hydroxythiazoles – extending the applicability of highly fluorescent self-assembling chromophores to supra-molecular photonic structures journal January 2016
Enhancing the supramolecular stability of monolayers by combining dipolar with amphiphilic motifs: a case of amphiphilic push–pull-thiazole journal January 2019
Noncovalent Interactions in the Catechol Dimer journal September 2017

Similar Records

Charge transport and exciton dissociation in organic solar cells consisting of dipolar donors mixed with C70
Journal Article · Thu Aug 06 00:00:00 EDT 2015 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1286904

Systematic Merging of Nonfullerene Acceptor π-Extension and Tetrafluorination Strategies Affords Polymer Solar Cells with >16% Efficiency
Journal Article · Tue Apr 13 00:00:00 EDT 2021 · Journal of the American Chemical Society · OSTI ID:1286904

Every Atom Counts: Elucidating the Fundamental Impact of Structural Change in Conjugated Polymers for Organic Photovoltaics
Journal Article · Thu Apr 19 00:00:00 EDT 2018 · Chemistry of Materials · OSTI ID:1286904

Related Subjects