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Title: Is there such a thing as a molecular organic alloy?

Abstract

In inorganic materials, an alloy is a mixture of two or more substances that generally exhibits electronic and/or physical properties that differ from those of its constituents. In organic systems, the formation of a “molecular alloy” comprising mixtures of molecular organic materials has also been proposed. We test the validity of this concept via the study of the optoelectronic properties of a ternary system that has previously been identified to form a molecular acceptor alloy, namely a blend of a poly(3-hexylthiophene) (P3HT) donor, with two acceptors indene-C 60 bisadduct (ICBA) and phenyl-C 61-butyric acid methyl ester (PC 61BM) [R. A. Street, et al., J. Am. Chem. Soc., 2013, 135, 986–989]. Using photoelectron spectroscopy, we find that the ICBA:PC 61BM blend shows the same highest occupied molecular orbital and exciton energies as that of ICBA, indicating the absence of a new exciton state in the blend. Furthermore, charge transfer state spectra of ternary blends are found to comprise a simple linear superposition of the corresponding binaries. From these results, no evidence of new, emergent electronic states is found to support the existence of a molecular alloy in this system. To our knowledge there is as yet no clear evidence of themore » existence of an alloy in any organic semiconductor system. Finally, we discuss the criteria that should be met by a molecular organic alloy and procedures needed for their unambiguous identification.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4]
  1. Univ. of Michigan, Ann Arbor, MI (United States). Applied Physics Program
  2. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Electrical Engineering and Computer Science
  3. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Physics
  4. Univ. of Michigan, Ann Arbor, MI (United States). Applied Physics Program, Dept. of Electrical Engineering and Computer Science, Dept. of Physics, and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Univ. of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1573355
Grant/Contract Number:  
EE0008561
Resource Type:
Accepted Manuscript
Journal Name:
Materials Horizons
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2051-6347
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Huang, Xinjing, Liu, Xiao, Ding, Kan, and Forrest, Stephen R. Is there such a thing as a molecular organic alloy?. United States: N. p., 2019. Web. doi:10.1039/C9MH01351B.
Huang, Xinjing, Liu, Xiao, Ding, Kan, & Forrest, Stephen R. Is there such a thing as a molecular organic alloy?. United States. doi:10.1039/C9MH01351B.
Huang, Xinjing, Liu, Xiao, Ding, Kan, and Forrest, Stephen R. Tue . "Is there such a thing as a molecular organic alloy?". United States. doi:10.1039/C9MH01351B.
@article{osti_1573355,
title = {Is there such a thing as a molecular organic alloy?},
author = {Huang, Xinjing and Liu, Xiao and Ding, Kan and Forrest, Stephen R.},
abstractNote = {In inorganic materials, an alloy is a mixture of two or more substances that generally exhibits electronic and/or physical properties that differ from those of its constituents. In organic systems, the formation of a “molecular alloy” comprising mixtures of molecular organic materials has also been proposed. We test the validity of this concept via the study of the optoelectronic properties of a ternary system that has previously been identified to form a molecular acceptor alloy, namely a blend of a poly(3-hexylthiophene) (P3HT) donor, with two acceptors indene-C60 bisadduct (ICBA) and phenyl-C61-butyric acid methyl ester (PC61BM) [R. A. Street, et al., J. Am. Chem. Soc., 2013, 135, 986–989]. Using photoelectron spectroscopy, we find that the ICBA:PC61BM blend shows the same highest occupied molecular orbital and exciton energies as that of ICBA, indicating the absence of a new exciton state in the blend. Furthermore, charge transfer state spectra of ternary blends are found to comprise a simple linear superposition of the corresponding binaries. From these results, no evidence of new, emergent electronic states is found to support the existence of a molecular alloy in this system. To our knowledge there is as yet no clear evidence of the existence of an alloy in any organic semiconductor system. Finally, we discuss the criteria that should be met by a molecular organic alloy and procedures needed for their unambiguous identification.},
doi = {10.1039/C9MH01351B},
journal = {Materials Horizons},
number = 1,
volume = 7,
place = {United States},
year = {2019},
month = {9}
}

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Works referenced in this record:

Organic alloy systems suitable for the investigation of regular binary and ternary eutectic growth
journal, September 2004


Molecular motions and lattice stability of a disordered organic alloy: Binary solid solutions of 1,4‐dihalonaphthalenes
journal, December 1977

  • Bellows, James C.; Prasad, Paras N.
  • The Journal of Chemical Physics, Vol. 67, Issue 12
  • DOI: 10.1063/1.434787

Tuning of Multi-Instabilities in Organic Alloy, [(EDO-TTF) 1− x (MeEDO-TTF) x ] 2 PF 6
journal, May 2010

  • Murata, Tsuyoshi; Shao, Xiangfeng; Nakano, Yoshiaki
  • Chemistry of Materials, Vol. 22, Issue 10
  • DOI: 10.1021/cm100051b

Engineered doping of organic semiconductors for enhanced thermoelectric efficiency
journal, May 2013

  • Kim, G-H.; Shao, L.; Zhang, K.
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3635

Physicochemical studies on organic eutectics and the 1:1 addition compound: benzidine-α-naphthol system
journal, February 1992

  • Rai, U. S.; George, Santhi
  • Journal of Materials Science, Vol. 27, Issue 3
  • DOI: 10.1007/BF02403884

Origin of the Tunable Open-Circuit Voltage in Ternary Blend Bulk Heterojunction Organic Solar Cells
journal, January 2013

  • Street, Robert A.; Davies, Daniel; Khlyabich, Petr P.
  • Journal of the American Chemical Society, Vol. 135, Issue 3
  • DOI: 10.1021/ja3112143

New BEDT-TTF Radical Cation Salt with Mixed Anions: α'-[BEDT-TTF]2[CuBr2]0.4[CuCl2]0.6
journal, April 2012


A Supramolecular Approach to Organic Alloys: Cocrystals and Three- and Four-Component Solid Solutions of 1,4-Diazabicyclo[2.2.2]octane and 4-X-Phenols (X=Cl, CH3, Br)
journal, May 2007

  • Dabros, Marta; Emery, Paul R.; Thalladi, Venkat R.
  • Angewandte Chemie International Edition, Vol. 46, Issue 22
  • DOI: 10.1002/anie.200604830

Controlled doping of phthalocyanine layers by cosublimation with acceptor molecules: A systematic Seebeck and conductivity study
journal, November 1998

  • Pfeiffer, M.; Beyer, A.; Fritz, T.
  • Applied Physics Letters, Vol. 73, Issue 22
  • DOI: 10.1063/1.122718

Metal–insulator transition of alloyed radical cation salts, (MexEDO-TTF)2PF6
journal, June 2010


Doping of organic semiconductors
journal, December 2012


Structural Origins for Tunable Open-Circuit Voltage in Ternary-Blend Organic Solar Cells
journal, August 2015

  • Khlyabich, Petr P.; Rudenko, Andrey E.; Thompson, Barry C.
  • Advanced Functional Materials, Vol. 25, Issue 34
  • DOI: 10.1002/adfm.201502287

Thermodynamic description and unidirectional solidification of eutectic organic alloys: I. Succinonitrile-(d)camphor system
journal, September 2004


Glass Forming Acceptor Alloys for Highly Efficient and Thermally Stable Ternary Organic Solar Cells
journal, January 2018

  • de Zerio, Amaia Diaz; Müller, Christian
  • Advanced Energy Materials, Vol. 8, Issue 28
  • DOI: 10.1002/aenm.201702741

Status and prospects for ternary organic photovoltaics
journal, July 2015


Conjugated Polymer–Small Molecule Alloy Leads to High Efficient Ternary Organic Solar Cells
journal, June 2015

  • Zhang, Jianqi; Zhang, Yajie; Fang, Jin
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b03449

Efficient Ternary Blend Bulk Heterojunction Solar Cells with Tunable Open-Circuit Voltage
journal, September 2011

  • Khlyabich, Petr P.; Burkhart, Beate; Thompson, Barry C.
  • Journal of the American Chemical Society, Vol. 133, Issue 37
  • DOI: 10.1021/ja205977z

Highly Efficient Organic Devices Based on Electrically Doped Transport Layers
journal, April 2007

  • Walzer, K.; Maennig, B.; Pfeiffer, M.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr050156n

Application of organic bathocuproine-based alloy film to organic light-emitting diodes
journal, March 2008


Tuning the Ionization Energy of Organic Semiconductor Films: The Role of Intramolecular Polar Bonds
journal, October 2008

  • Salzmann, Ingo; Duhm, Steffen; Heimel, Georg
  • Journal of the American Chemical Society, Vol. 130, Issue 39
  • DOI: 10.1021/ja804793a

Postchemistry of Organic Particles: When TTF Microparticles Meet TCNQ Microstructures in Aqueous Solution
journal, May 2010

  • Xiao, Jinchong; Yin, Zongyou; Li, Hong
  • Journal of the American Chemical Society, Vol. 132, Issue 20
  • DOI: 10.1021/ja102154b

Design Rule for Improved Open-Circuit Voltage in Binary and Ternary Organic Solar Cells
journal, October 2017

  • Felekidis, Nikolaos; Melianas, Armantas; Kemerink, Martijn
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 42
  • DOI: 10.1021/acsami.7b08276

Alloy Acceptor: Superior Alternative to PCBM toward Efficient and Stable Organic Solar Cells
journal, June 2016


Optical Study of Electronic Structure and Photoinduced Dynamics in the Organic Alloy System [(EDO-TTF)0.89(MeEDO-TTF)0.11]2PF6
journal, March 2019

  • Ishikawa, Tadahiko; Urasawa, Yohei; Shindo, Taiki
  • Applied Sciences, Vol. 9, Issue 6
  • DOI: 10.3390/app9061174

Solidification behaviour of binary organic eutectic alloys
journal, January 1994


Formation of Organic Alloys in Ternary-Blend Solar Cells with Two Acceptors Having Energy-Level Offsets Exceeding 0.4 eV
journal, August 2017


Band structure engineering in organic semiconductors
journal, June 2016


Fullerene alloy formation and the benefits for efficient printing of ternary blend organic solar cells
journal, January 2015

  • Angmo, Dechan; Bjerring, Morten; Nielsen, Niels Chr.
  • Journal of Materials Chemistry C, Vol. 3, Issue 21
  • DOI: 10.1039/c5tc00781j

Influence of Polymer Compatibility on the Open-Circuit Voltage in Ternary Blend Bulk Heterojunction Solar Cells
journal, June 2014

  • Khlyabich, Petr P.; Rudenko, Andrey E.; Street, Robert A.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 13
  • DOI: 10.1021/am502122a

Physical Chemistry of Organic Eutectic and Monotectic:  Hexamethylbenzene−Succinonitrile System
journal, November 1999

  • Rai, U. S.; Rai, R. N.
  • Chemistry of Materials, Vol. 11, Issue 11
  • DOI: 10.1021/cm9806937

Organic Ternary Solar Cells: A Review
journal, May 2013


Microstructural and Electronic Origins of Open-Circuit Voltage Tuning in Organic Solar Cells Based on Ternary Blends
journal, September 2015

  • Mollinger, Sonya A.; Vandewal, Koen; Salleo, Alberto
  • Advanced Energy Materials, Vol. 5, Issue 23
  • DOI: 10.1002/aenm.201501335

Multicomponent Organic Alloys Based on Organic Layered Crystals
journal, November 2005

  • Sada, Kazuki; Inoue, Katsunari; Tanaka, Tomoyuki
  • Angewandte Chemie International Edition, Vol. 44, Issue 43
  • DOI: 10.1002/anie.200501678

Complex assembly from planar and twisted π-conjugated molecules towards alloy helices and core-shell structures
journal, October 2018


Organic Semiconducting Alloys with Tunable Energy Levels
journal, February 2019

  • Dou, Jin-Hu; Yu, Zhi-Ao; Zhang, Jun
  • Journal of the American Chemical Society, Vol. 141, Issue 16
  • DOI: 10.1021/jacs.8b13471