Reducing Dynamic Disorder in Small-molecule Organic Semiconductors by Suppressing Large-amplitude Thermal Motions

Overview

Journal Nat Commun

Specialty Biology

Date 2016 Feb 23

PMID 26898754

Citations 33

Authors

Steffen Illig

Alexander S Eggeman

Alessandro Troisi

Lang Jiang

Chris Warwick

Mark Nikolka

Guillaume Schweicher

Stephen G Yeates

Yves Henri Geerts

John E Anthony

Henning Sirringhaus

Affiliations

Soon will be listed here.

Abstract

Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder.

Citing Articles

Dielectric polymers with mechanical bonds for high-temperature capacitive energy storage.

Wang R, Zhu Y, Huang S, Fu J, Zhou Y, Li M Nat Mater. 2025; .

PMID: 39953246 DOI: 10.1038/s41563-025-02130-z.

Visualizing stepwise evolution of carbon hybridization from sp to sp and to sp.

Xiong W, Zhang G, Bao D, Lu J, Gao L, Li Y Nat Commun. 2025; 16(1):690.

PMID: 39814741 PMC: 11735776. DOI: 10.1038/s41467-024-55719-4.

Probing Out-Of-Plane Charge Transport in Organic Semiconductors Using Conductive Atomic Force Microscopy.

Gicevicius M, Gong H, Turetta N, Wood W, Volpi M, Geerts Y Adv Mater. 2024; 37(7):e2418694.

PMID: 39726079 PMC: 11837897. DOI: 10.1002/adma.202418694.

Two Isomeric Thienoacenes in Thin Films: Unveiling the Influence of Molecular Structure and Intermolecular Packing on Electronic Properties.

Gatsios C, Dreher M, Amsalem P, Opitz A, Jouclas R, Geerts Y J Phys Chem C Nanomater Interfaces. 2024; 128(49):21228-21236.

PMID: 39691904 PMC: 11648078. DOI: 10.1021/acs.jpcc.4c06741.

On the importance of crystal structures for organic thin film transistors.

Schweicher G, Das S, Resel R, Geerts Y Acta Crystallogr C Struct Chem. 2024; 80(Pt 10):601-611.

PMID: 39226426 PMC: 11451017. DOI: 10.1107/S2053229624008283.

References

Subramanian S, Park S, Parkin S, Podzorov V, Jackson T, Anthony J . Chromophore fluorination enhances crystallization and stability of soluble anthradithiophene semiconductors. J Am Chem Soc. 2008; 130(9):2706-7. DOI: 10.1021/ja073235k. View

Troisi A, Orlandi G . Dynamics of the intermolecular transfer integral in crystalline organic semiconductors. J Phys Chem A. 2006; 110(11):4065-70. DOI: 10.1021/jp055432g. View

Keen D, Goodwin A . The crystallography of correlated disorder. Nature. 2015; 521(7552):303-9. DOI: 10.1038/nature14453. View

Schweicher G, Lemaur V, Niebel C, Ruzie C, Diao Y, Goto O . Bulky end-capped [1]benzothieno[3,2-b]benzothiophenes: reaching high-mobility organic semiconductors by fine tuning of the crystalline solid-state order. Adv Mater. 2015; 27(19):3066-72. DOI: 10.1002/adma.201500322. View

Payne M, Parkin S, Anthony J, Kuo C, Jackson T . Organic field-effect transistors from solution-deposited functionalized acenes with mobilities as high as 1 cm2/V x s. J Am Chem Soc. 2005; 127(14):4986-7. DOI: 10.1021/ja042353u. View

Wang Y, Parkin S, Gierschner J, Watson M . Highly fluorinated benzobisbenzothiophenes. Org Lett. 2008; 10(15):3307-10. DOI: 10.1021/ol8003468. View

Jurchescu O, Meetsma A, Palstra T . Low-temperature structure of rubrene single crystals grown by vapor transport. Acta Crystallogr B. 2006; 62(Pt 2):330-4. DOI: 10.1107/S0108768106003053. View

Woodley S, Catlow R . Crystal structure prediction from first principles. Nat Mater. 2008; 7(12):937-46. DOI: 10.1038/nmat2321. View

Payne M, Odom S, Parkin S, Anthony J . Stable, crystalline acenedithiophenes with up to seven linearly fused rings. Org Lett. 2004; 6(19):3325-8. DOI: 10.1021/ol048686d. View

10.

Minder N, Lu S, Fratini S, Ciuchi S, Facchetti A, Morpurgo A . Tailoring the molecular structure to suppress extrinsic disorder in organic transistors. Adv Mater. 2013; 26(8):1254-60. DOI: 10.1002/adma.201304130. View

11.

Chang J, Sakanoue T, Olivier Y, Uemura T, Dufourg-Madec M, Yeates S . Hall-effect measurements probing the degree of charge-carrier delocalization in solution-processed crystalline molecular semiconductors. Phys Rev Lett. 2011; 107(6):066601. DOI: 10.1103/PhysRevLett.107.066601. View

12.

Llorente G, Dufourg-Madec M, Crouch D, Pritchard R, Ogier S, Yeates S . High performance, acene-based organic thin film transistors. Chem Commun (Camb). 2009; (21):3059-61. DOI: 10.1039/b901448a. View

13.

Takimiya K, Shinamura S, Osaka I, Miyazaki E . Thienoacene-based organic semiconductors. Adv Mater. 2011; 23(38):4347-70. DOI: 10.1002/adma.201102007. View

14.

Troisi A . Dynamic disorder in molecular semiconductors: charge transport in two dimensions. J Chem Phys. 2011; 134(3):034702. DOI: 10.1063/1.3524314. View

15.

Giri G, Verploegen E, Mannsfeld S, Atahan-Evrenk S, Kim D, Lee S . Tuning charge transport in solution-sheared organic semiconductors using lattice strain. Nature. 2011; 480(7378):504-8. DOI: 10.1038/nature10683. View

16.

Eggeman A, Illig S, Troisi A, Sirringhaus H, Midgley P . Measurement of molecular motion in organic semiconductors by thermal diffuse electron scattering. Nat Mater. 2013; 12(11):1045-9. DOI: 10.1038/nmat3710. View

17.

Ebata H, Izawa T, Miyazaki E, Takimiya K, Ikeda M, Kuwabara H . Highly soluble [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives for high-performance, solution-processed organic field-effect transistors. J Am Chem Soc. 2007; 129(51):15732-3. DOI: 10.1021/ja074841i. View

18.

Coropceanu V, Cornil J, da Silva Filho D, Olivier Y, Silbey R, Bredas J . Charge transport in organic semiconductors. Chem Rev. 2007; 107(4):926-52. DOI: 10.1021/cr050140x. View

19.

Uemura T, Rolin C, Ke T, Fesenko P, Genoe J, Heremans P . On the Extraction of Charge Carrier Mobility in High-Mobility Organic Transistors. Adv Mater. 2015; 28(1):151-5. DOI: 10.1002/adma.201503133. View