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

Title: Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy

Abstract

Abstract In organic solar cells, the resulting device efficiency depends strongly on the local morphology and intermolecular interactions of the blend film. Optical spectroscopy was used to identify the spectral signatures of interacting chromophores in blend films of the donor polymer PM6 with two state‐of‐the‐art nonfullerene acceptors, Y6 and N4, which differ merely in the branching point of the side chain. From temperature‐dependent absorption and luminescence spectroscopy in solution, it is inferred that both acceptor materials form two types of aggregates that differ in their interaction energy. Y6 forms an aggregate with a predominant J‐type character in solution, while for N4 molecules the interaction is predominantly in a H‐like manner in solution and freshly spin‐cast film, yet the molecules reorient with respect to each other with time or thermal annealing to adopt a more J‐type interaction. The different aggregation behavior of the acceptor materials is also reflected in the blend films and accounts for the different solar cell efficiencies reported with the two blends.

Authors:
 [1];  [2];  [1];  [1];  [3];  [4];  [5];  [1];  [6];  [5];  [2];  [3]; ORCiD logo [7]
  1. Soft Matter Optoelectronics Experimentalphysik II University of Bayreuth 95440 Bayreuth Germany
  2. Dynamik und Strukturbildung‐Herzig Group Physikalisches Institut Universität Bayreuth Universitätsstr. 30 95447 Bayreuth Germany
  3. Soft Matter Physics and Optoelectronics Institute of Physics and Astronomy University of Potsdam Karl‐Liebknecht‐Str. 24‐25 14476 Potsdam‐Golm Germany
  4. NSLS‐II Brookhaven National Laboratory Upton NY 11973 USA
  5. College of Chemistry and Chemical Engineering Central South University Chansha 410083 P. R. China
  6. School of Chemistry Bio21 Institute The University of Melbourne 30 Flemington Road Parkville VIC 3010 Australia
  7. Soft Matter Optoelectronics Experimentalphysik II University of Bayreuth 95440 Bayreuth Germany, Bayreuth Institute of Macromolecular Research (BIMF) and Bavarian Polymer Institute (BPI) University of Bayreuth 95447 Bayreuth Germany
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1883261
Alternate Identifier(s):
OSTI ID: 1895513
Resource Type:
Published Article
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials Journal Volume: 32 Journal Issue: 44; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Kroh, Daniel, Eller, Fabian, Schötz, Konstantin, Wedler, Stefan, Perdigón‐Toro, Lorena, Freychet, Guillaume, Wei, Qingya, Dörr, Maximilian, Jones, David, Zou, Yingping, Herzig, Eva M., Neher, Dieter, and Köhler, Anna. Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy. Germany: N. p., 2022. Web. doi:10.1002/adfm.202205711.
Kroh, Daniel, Eller, Fabian, Schötz, Konstantin, Wedler, Stefan, Perdigón‐Toro, Lorena, Freychet, Guillaume, Wei, Qingya, Dörr, Maximilian, Jones, David, Zou, Yingping, Herzig, Eva M., Neher, Dieter, & Köhler, Anna. Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy. Germany. https://doi.org/10.1002/adfm.202205711
Kroh, Daniel, Eller, Fabian, Schötz, Konstantin, Wedler, Stefan, Perdigón‐Toro, Lorena, Freychet, Guillaume, Wei, Qingya, Dörr, Maximilian, Jones, David, Zou, Yingping, Herzig, Eva M., Neher, Dieter, and Köhler, Anna. Tue . "Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy". Germany. https://doi.org/10.1002/adfm.202205711.
@article{osti_1883261,
title = {Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy},
author = {Kroh, Daniel and Eller, Fabian and Schötz, Konstantin and Wedler, Stefan and Perdigón‐Toro, Lorena and Freychet, Guillaume and Wei, Qingya and Dörr, Maximilian and Jones, David and Zou, Yingping and Herzig, Eva M. and Neher, Dieter and Köhler, Anna},
abstractNote = {Abstract In organic solar cells, the resulting device efficiency depends strongly on the local morphology and intermolecular interactions of the blend film. Optical spectroscopy was used to identify the spectral signatures of interacting chromophores in blend films of the donor polymer PM6 with two state‐of‐the‐art nonfullerene acceptors, Y6 and N4, which differ merely in the branching point of the side chain. From temperature‐dependent absorption and luminescence spectroscopy in solution, it is inferred that both acceptor materials form two types of aggregates that differ in their interaction energy. Y6 forms an aggregate with a predominant J‐type character in solution, while for N4 molecules the interaction is predominantly in a H‐like manner in solution and freshly spin‐cast film, yet the molecules reorient with respect to each other with time or thermal annealing to adopt a more J‐type interaction. The different aggregation behavior of the acceptor materials is also reflected in the blend films and accounts for the different solar cell efficiencies reported with the two blends.},
doi = {10.1002/adfm.202205711},
journal = {Advanced Functional Materials},
number = 44,
volume = 32,
place = {Germany},
year = {Tue Aug 23 00:00:00 EDT 2022},
month = {Tue Aug 23 00:00:00 EDT 2022}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/adfm.202205711

Save / Share:

Works referenced in this record:

Altering the Positions of Chlorine and Bromine Substitution on the End Group Enables High‐Performance Acceptor and Efficient Organic Solar Cells
journal, October 2020

  • Luo, Zhenghui; Ma, Ruijie; Chen, Zhanxiang
  • Advanced Energy Materials, Vol. 10, Issue 44
  • DOI: 10.1002/aenm.202002649

n-Type Molecular Photovoltaic Materials: Design Strategies and Device Applications
journal, May 2020

  • Yue, Qihui; Liu, Wuyue; Zhu, Xiaozhang
  • Journal of the American Chemical Society, Vol. 142, Issue 27
  • DOI: 10.1021/jacs.0c04084

Understanding the Role of Order in Y‐Series Non‐Fullerene Solar Cells to Realize High Open‐Circuit Voltages
journal, February 2022

  • Perdigón‐Toro, Lorena; Phuong, Le Quang; Eller, Fabian
  • Advanced Energy Materials, Vol. 12, Issue 12
  • DOI: 10.1002/aenm.202103422

A universal method for constructing high efficiency organic solar cells with stacked structures
journal, January 2021

  • Wei, Yanan; Yu, Jianwei; Qin, Linqing
  • Energy & Environmental Science, Vol. 14, Issue 4
  • DOI: 10.1039/D0EE03490H

Adding a Third Component with Reduced Miscibility and Higher LUMO Level Enables Efficient Ternary Organic Solar Cells
journal, August 2020


Excitons Dominate the Emission from PM6:Y6 Solar Cells, but This Does Not Help the Open-Circuit Voltage of the Device
journal, January 2021


Influence of Alkyl Chain Branching Positions on the Hole Mobilities of Polymer Thin-Film Transistors
journal, September 2012


Effects of Short‐Axis Alkoxy Substituents on Molecular Self‐Assembly and Photovoltaic Performance of Indacenodithiophene‐Based Acceptors
journal, October 2019

  • Li, Xiaojun; Huang, He; Angunawela, Indunil
  • Advanced Functional Materials, Vol. 30, Issue 3
  • DOI: 10.1002/adfm.201906855

Tuning Aggregation Behavior of Polymer Donor via Molecular‐Weight Control for Achieving 17.1% Efficiency Inverted Polymer Solar Cells
journal, June 2021


Single-junction organic solar cells with over 19% efficiency enabled by a refined double-fibril network morphology
journal, May 2022


Organic Solar Cells with 18% Efficiency Enabled by an Alloy Acceptor: A Two‐in‐One Strategy
journal, May 2021


Non-fullerene acceptor fibrils enable efficient ternary organic solar cells with 16.6% efficiency
journal, February 2020


A Non-fullerene Acceptor with Enhanced Intermolecular π-Core Interaction for High-Performance Organic Solar Cells
journal, August 2020

  • Lin, Francis; Jiang, Kui; Kaminsky, Werner
  • Journal of the American Chemical Society, Vol. 142, Issue 36
  • DOI: 10.1021/jacs.0c07083

Disorder vs Delocalization: Which Is More Advantageous for High-Efficiency Organic Solar Cells?
journal, October 2019

  • Athanasopoulos, Stavros; Bässler, Heinz; Köhler, Anna
  • The Journal of Physical Chemistry Letters, Vol. 10, Issue 22
  • DOI: 10.1021/acs.jpclett.9b02866

Realizing 19.05% Efficiency Polymer Solar Cells by Progressively Improving Charge Extraction and Suppressing Charge Recombination
journal, February 2022


The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates
journal, March 2010

  • Spano, Frank C.
  • Accounts of Chemical Research, Vol. 43, Issue 3
  • DOI: 10.1021/ar900233v

Crystallography, Morphology, Electronic Structure, and Transport in Non-Fullerene/Non-Indacenodithienothiophene Polymer:Y6 Solar Cells
journal, July 2020

  • Zhu, Weigang; Spencer, Austin P.; Mukherjee, Subhrangsu
  • Journal of the American Chemical Society, Vol. 142, Issue 34
  • DOI: 10.1021/jacs.0c05560

What is the role of planarity and torsional freedom for aggregation in a π-conjugated donor–acceptor model oligomer?
journal, January 2020

  • Wedler, Stefan; Bourdick, Axel; Athanasopoulos, Stavros
  • Journal of Materials Chemistry C, Vol. 8, Issue 14
  • DOI: 10.1039/D0TC00217H

Concurrent Cooperative J-Aggregates and Anticooperative H-Aggregates
journal, April 2018

  • Cai, Kang; Xie, Jiajun; Zhang, Di
  • Journal of the American Chemical Society, Vol. 140, Issue 17
  • DOI: 10.1021/jacs.8b01463

Watching Paint Dry: The Impact of Diiodooctane on the Kinetics of Aggregate Formation in Thin Films of Poly(3-hexylthiophene)
journal, August 2016


Heating induced aggregation in non-fullerene organic solar cells towards high performance
journal, March 2021


Achieving 16.68% efficiency ternary as-cast organic solar cells
journal, January 2021


Tandem Organic Solar Cell with 20.2% Efficiency
journal, January 2022


Preaggregation in Solution Producing Multiple Crystal Forms of Y6 Corresponding to a Variation of Miscibility in PM6-Based Ternary Solar Cells
journal, January 2022


Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates
journal, September 1963


Material insights and challenges for non-fullerene organic solar cells based on small molecular acceptors
journal, July 2018


Reducing Voltage Losses in the A-DA′D-A Acceptor-Based Organic Solar Cells
journal, September 2020


Effect of doping on the density-of-states distribution and carrier hopping in disordered organic semiconductors
journal, January 2005


Over 16.7% efficiency of ternary organic photovoltaics by employing extra PC71BM as morphology regulator
journal, November 2019


Influence of Aggregation on the Performance of All-Polymer Solar Cells Containing Low-Bandgap Naphthalenediimide Copolymers
journal, January 2012

  • Schubert, Marcel; Dolfen, Daniel; Frisch, Johannes
  • Advanced Energy Materials, Vol. 2, Issue 3
  • DOI: 10.1002/aenm.201100601

A History and Perspective of Non‐Fullerene Electron Acceptors for Organic Solar Cells
journal, January 2021

  • Armin, Ardalan; Li, Wei; Sandberg, Oskar J.
  • Advanced Energy Materials, Vol. 11, Issue 15
  • DOI: 10.1002/aenm.202003570

Fine-tuning of side-chain orientations on nonfullerene acceptors enables organic solar cells with 17.7% efficiency
journal, January 2021

  • Chai, Gaoda; Chang, Yuan; Zhang, Jianquan
  • Energy & Environmental Science, Vol. 14, Issue 6
  • DOI: 10.1039/D0EE03506H

Synergistic Effect of Alkyl Chain and Chlorination Engineering on High-Performance Nonfullerene Acceptors
journal, June 2020

  • Mo, Daize; Chen, Hui; Zhu, Yulin
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 25
  • DOI: 10.1021/acsami.0c07856

Nanographene–Osmapentalyne Complexes as a Cathode Interlayer in Organic Solar Cells Enhance Efficiency over 18%
journal, June 2021


Intramolecular Charge Transfer Assisted by Conformational Changes in the Excited State of Fluorene-dibenzothiophene- S,S -dioxide Co-oligomers
journal, October 2006

  • Dias, Fernando B.; Pollock, Sam; Hedley, Gordon
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp0643653

An Order–Disorder Transition in the Conjugated Polymer MEH-PPV
journal, July 2012

  • Köhler, Anna; Hoffmann, Sebastian T.; Bässler, Heinz
  • Journal of the American Chemical Society, Vol. 134, Issue 28
  • DOI: 10.1021/ja302408a

The exciton model in molecular spectroscopy
journal, January 1965

  • Kasha, M.; Rawls, H. R.; Ashraf El-Bayoumi, M.
  • Pure and Applied Chemistry, Vol. 11, Issue 3-4
  • DOI: 10.1351/pac196511030371

Observing long-range non-fullerene backbone ordering in real-space to improve the charge transport properties of organic solar cells
journal, January 2021

  • Bi, Zhaozhao; Chen, Kai; Gou, Lu
  • Journal of Materials Chemistry A, Vol. 9, Issue 31
  • DOI: 10.1039/D1TA04623C

Volatilizable Solid Additive‐Assisted Treatment Enables Organic Solar Cells with Efficiency over 18.8% and Fill Factor Exceeding 80%
journal, September 2021


Temperature Induced Order–Disorder Transition in Solutions of Conjugated Polymers Probed by Optical Spectroscopy
journal, December 2016

  • Panzer, Fabian; Bässler, Heinz; Köhler, Anna
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
  • DOI: 10.1021/acs.jpclett.6b01641

Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells
journal, November 2014

  • Liu, Yuhang; Zhao, Jingbo; Li, Zhengke
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6293

New Phase for Organic Solar Cell Research: Emergence of Y-Series Electron Acceptors and Their Perspectives
journal, April 2020


Alkyl‐Chain Branching of Non‐Fullerene Acceptors Flanking Conjugated Side Groups toward Highly Efficient Organic Solar Cells
journal, October 2021

  • Zhang, Jianquan; Bai, Fujin; Angunawela, Indunil
  • Advanced Energy Materials, Vol. 11, Issue 47
  • DOI: 10.1002/aenm.202102596

Entropy and Disorder Enable Charge Separation in Organic Solar Cells
journal, October 2016


Effect of Molecular Packing and Charge Delocalization on the Nonradiative Recombination of Charge-Transfer States in Organic Solar Cells
journal, September 2016

  • Chen, Xian-Kai; Ravva, Mahesh Kumar; Li, Hong
  • Advanced Energy Materials, Vol. 6, Issue 24
  • DOI: 10.1002/aenm.201601325

Control of π–π Stacking via Crystal Engineering in Organic Conjugated Small Molecule Crystals
journal, December 2017


Elucidating Aggregation Pathways in the Donor–Acceptor Type Molecules p-DTS(FBTTh 2 ) 2 and p-SIDT(FBTTh 2 ) 2
journal, September 2018

  • Bourdick, Axel; Reichenberger, Markus; Stradomska, Anna
  • The Journal of Physical Chemistry B, Vol. 122, Issue 39
  • DOI: 10.1021/acs.jpcb.8b06283

Non-fullerene acceptors for organic solar cells
journal, February 2018


Fibril Network Strategy Enables High‐Performance Semitransparent Organic Solar Cells
journal, May 2020

  • Xie, Yuanpeng; Cai, Yunhao; Zhu, Lei
  • Advanced Functional Materials, Vol. 30, Issue 28
  • DOI: 10.1002/adfm.202002181

Single-crystal field-effect transistors based on a fused-ring electron acceptor with high ambipolar mobilities
journal, January 2020

  • Xiao, Chengyi; Li, Cheng; Liu, Feng
  • Journal of Materials Chemistry C
  • DOI: 10.1039/D0TC00587H

Delocalization of exciton and electron wavefunction in non-fullerene acceptor molecules enables efficient organic solar cells
journal, August 2020


Eco‐Compatible Solvent‐Processed Organic Photovoltaic Cells with Over 16% Efficiency
journal, August 2019


Layer‐by‐Layer Processed Ternary Organic Photovoltaics with Efficiency over 18%
journal, February 2021


Temperature‐Dependent Aggregation Donor Polymers Enable Highly Efficient Sequentially Processed Organic Photovoltaics Without the Need of Orthogonal Solvents
journal, June 2019

  • Arunagiri, Lingeswaran; Zhang, Guangye; Hu, Huawei
  • Advanced Functional Materials, Vol. 29, Issue 33
  • DOI: 10.1002/adfm.201902478

Single-Junction Organic Solar Cell with over 15% Efficiency Using Fused-Ring Acceptor with Electron-Deficient Core
journal, April 2019


Charge‐Transfer States at Organic–Organic Interfaces: Impact of Static and Dynamic Disorders
journal, February 2019

  • Zheng, Zilong; Tummala, Naga Rajesh; Wang, Tonghui
  • Advanced Energy Materials, Vol. 9, Issue 14
  • DOI: 10.1002/aenm.201803926

Molecular packing of non-fullerene acceptors for organic solar cells: Distinctive local morphology in Y6 vs. ITIC derivatives
journal, September 2021


Controlling aggregate formation in conjugated polymers by spin-coating below the critical temperature of the disorder-order transition
journal, December 2017

  • Reichenberger, Markus; Kroh, Daniel; Matrone, Giovanni M. M.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 6
  • DOI: 10.1002/polb.24562

Cold‐Aging and Solvent Vapor Mediated Aggregation Control toward 18% Efficiency Binary Organic Solar Cells
journal, August 2021

  • Guo, Chuanhang; Li, Donghui; Wang, Liang
  • Advanced Energy Materials, Vol. 11, Issue 39
  • DOI: 10.1002/aenm.202102000

Single‐Junction Organic Photovoltaic Cell with 19% Efficiency
journal, August 2021


The Impact of Polydispersity and Molecular Weight on the Order–Disorder Transition in Poly(3-hexylthiophene)
journal, July 2014

  • Panzer, Fabian; Bässler, Heinz; Lohwasser, Ruth
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
  • DOI: 10.1021/jz5009938

Universal and versatile morphology engineering via hot fluorous solvent soaking for organic bulk heterojunction
journal, November 2020


Impact of alkyl chain branching positions on molecular packing and electron transport of dimeric perylenediimide derivatives
journal, August 2019


Over 17% efficiency ternary organic solar cells enabled by two non-fullerene acceptors working in an alloy-like model
journal, January 2020

  • Zhan, Lingling; Li, Shuixing; Lau, Tsz-Ki
  • Energy & Environmental Science, Vol. 13, Issue 2
  • DOI: 10.1039/C9EE03710A

Over 17.7% efficiency ternary-blend organic solar cells with low energy-loss and good thickness-tolerance
journal, January 2022


Spectroscopic Signature of Two Distinct H-Aggregate Species in Poly(3-hexylthiophene)
journal, February 2015


Revealing structure formation in PCPDTBT by optical spectroscopy
journal, July 2015

  • Scharsich, Christina; Fischer, Florian S. U.; Wilma, Kevin
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 20
  • DOI: 10.1002/polb.23780

Electronic Processes in Organic Semiconductors: An Introduction
book, March 2015


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

A Generally Applicable Approach Using Sequential Deposition to Enable Highly Efficient Organic Solar Cells
journal, September 2020


Low-Bandgap Non-fullerene Acceptors Enabling High-Performance Organic Solar Cells
journal, January 2021


Alkyl Chain Tuning of Small Molecule Acceptors for Efficient Organic Solar Cells
journal, December 2019


Wide Energy-Window View on the Density of States and Hole Mobility in Poly( p -Phenylene Vinylene)
journal, October 2004