Different interface orientations of pentacene and PTCDA induce different degrees of disorder
© Poschlad et al.; licensee Springer. 2012
Received: 11 January 2012
Accepted: 17 April 2012
Published: 14 May 2012
Organic polymers or crystals are commonly used in manufacturing of today‘s electronically functional devices (OLEDs, organic solar cells, etc). Understanding their morphology in general and at the interface in particular is of paramount importance. Proper knowledge of molecular orientation at interfaces is essential for predicting optoelectronic properties such as exciton diffusion length, charge carrier mobility, and molecular quadrupole moments. Two promising candidates are pentacene and 3,4:9,10-perylenetetracarboxylic dianhydride (PTCDA). Different orientations of pentacene on PTCDA have been investigated using an atomistic molecular dynamics approach. Here, we show that the degree of disorder at the interface depends largely on the crystal orientation and that more ordered interfaces generally suffer from large vacancy formation.
KeywordsOrganic interfaces Organic electronic devices Interface disorder Molecular dynamics PTCDA Pentacene
Organic light emitting diodes (OLEDs), organic solar cells, organic thin films transistors, etc. are made of organic polymers or crystals[1–3]. The effect of the disorder in organic devices on optoelectronic properties was analyzed by Rim et al.. They showed an increased photocurrent generation with improved molecular order. It occurs due to the influence of the stacking on the exciton diffusion length. Hu et al. measured a strong dependence of the conductance across highly oriented pentacene nanocrystals on the packing orientation. The influence of packing on charge transport in organic solids was also analyzed using Monte Carlo methods. Kwiatkowski et al. were able to predict the mobilities of electron and holes for ordered and disordered Alq3. Different functional organic materials were reviewed by Ishii et al.. They highlighted the energy level alignment and electronic structures at organic/inorganic and organic/organic interfaces of, for example, Alq3, 3,4:9,10-perylenetetracarboxylic dianhydride (PTCDA) and 1,4,5,8-tetrathiafulvalene (TTF).
Molecular orientation at interfaces is decisive for predicting optoelectronic properties such as exciton diffusion length, charge carrier mobility, and molecular quadrupole moments. Verlaak et al. analyzed the impact of the molecular quadrupole moments, influenced by e. g., material and crystal orientation on the interface energetics. An insight on models of electronic processes across organic interfaces is given by Beljonne et al., while a review of the corresponding theoretical approaches is presented by Brédas.
Our study of organic-organic pentacene/PDCDA interfaces is organized as follows: after a brief introduction presented above, we proceed with the presentation of the methods followed by the results and some conclusive remarks.
Comparison of calculated and experimental relevant parameters
Bonds in pentacene
Angles in pentacene
The systems were simulated with a step size of 0.5 fs for more than 3 ns at a temperature of 300 K using a Berendsen thermostat for temperature control. The van der Waals cut-off was set to 1.2 nm, the Coulomb cut-off to 5 nm and the relative permittivity was set to four which was taken from Wang et al.. No periodic boundary conditions were used owing to the different crystal lattices.
Results and discussion
Analysis of PTCDA/pentacene interfaces was performed with two emerging messages: there seems to be two competing effects, one coming from intermolecular interaction, which leads to disordered interfaces, while the other coming from the preservation of bulk properties results in large interfacial vacancies. Both of the effects would lead to dramatically diminished transport properties. Namely, increased disorder would cause greater energy disorder of the interfacial hopping sites, while interfacial vacancies would lead to diminished intermolecular overlaps, or hopping matrix elements. Whether which of the competing effects is influencing more the hopping transport properties is the focus of our ongoing research. Our second observation is that pentacene seems to be, in general, a more flexible material, which can be observed from the fact that the disordered regions are predominantly pentacene-rich.
AP carried out the molecular dynamics calculations, the setup of the initial system and helped in drafting of the manuscript, and revisions. VM helped in analysis and interpretation of data, and drafted the manuscript and revisions. RM provided the calculation of the partial charges. WW participated in the design of the study, formulated the original scientific question and helped in analysis and interpretation of data. All authors read and approved the final manuscript.
AP is Ph.D. student, VM and RM have Ph.D. degree in physics, and WW is an associate professor at Karlsruhe Institute of Technology.
This work was supported by bwGRiD resources and the FP7 project MINOTOR. bwGRiD is the central collection of computing power within the state of Baden-Wuerttemberg operated by eight universities, providing access for local researchers. Further thanks go to Ivan Kondov from SCC/KIT.
- Yun C, Cho H, Kang H, Lee Y: Electron injection via pentacene thin films for efficient inverted organic light-emitting diodes. Appl Phys Lett 2009, 95: 053301. 10.1063/1.3192361View ArticleGoogle Scholar
- Roncaliu J: Molecular bulk heterojunctions: an emerging approach to organic solar cells. Acc Chem Res 2009, 42: 1719–1730. 10.1021/ar900041bView ArticleGoogle Scholar
- Reese Bao: Organic single-crystal field-effect transistors. Mat Today 2007, 10: 20–27.View ArticleGoogle Scholar
- Rim S, Fink R, Schöneboom J, Erk P, Peumans P: Effect of molecular packing on the exciton diffusion length in organic solar cells. Appl Phys Lett 2007, 91: 173504. 10.1063/1.2783202View ArticleGoogle Scholar
- Hu W-S, Tao Y-T, Chen Y-F, Chang C-S: Orientation-dependent conductance study of pentacene nanocrystals by conductive atomic force microscopy. Appl Phys Lett 2008, 93: 053304. 10.1063/1.2960343View ArticleGoogle Scholar
- Kwiatkowski J, Nelson J, Li J, Brédas J, Wenzel W, Lennartz C: Simulating charge transport in tris (8-hydroxyquinoline) aluminium (Alq3). Phys Chem Chem Phys 2008, 10: 1852–1858.View ArticleGoogle Scholar
- Ishii H, Sugiyama K, Ito E, Seki K: Energy level alignment and interfacial electronic structures at organic/metal and organic/organic Interfaces. Adv Mater 1999, 11: 8.View ArticleGoogle Scholar
- Yoneya M, Kawasaki M, Ando M: Molecular dynamics simulations of pentacene thin films: The effect of surface on polymorph selection. J Mater Chem 2010, 20: 10397–10402. 10.1039/c0jm01577fView ArticleGoogle Scholar
- Ogawa T, Kuwamoto K, Isoda S, Kobayashi T, Karl N: 3,4:9,10-Perylenetetracarboxylic dianhydride (PTCDA) by electron crystallography. Acta Cryst B 1999, 55: 123–130. 10.1107/S0108768198009872View ArticleGoogle Scholar
- Najafov H, Lee B, Zhou Q, Feldman L, Podzorov V: Observation of long-range exciton diffusion in highly ordered organic semiconductors. Nat Mater 2010, 9: 938–943. 10.1038/nmat2872View ArticleGoogle Scholar
- Vehoff T, Baumeier B, Troisi A, Andrienko D: Charge transport in organic crystals: role of disorder and topological connectivity. J Am Chem Soc 2010, 13: 11702–11708.View ArticleGoogle Scholar
- Verlaak S, Beljonne D, Cheyns D, Rolin C, Linares M, Castet F, Cornil J, Heremans P: Electronic structure and geminate pair energetics at organic–organic interfaces: the case of pentacene/C60 heterojunctions. Adv Func Mat 2009, 19: 3809–3814. 10.1002/adfm.200901233View ArticleGoogle Scholar
- Beljonne D, Cornil J, Muccioli L, Zannoni CJ, Castet F: Electronic processes at organic-organic interfaces: insight from modeling and implications for opto-electronic devices. Chem Mater 2011, 23: 591–609. 10.1021/cm1023426View ArticleGoogle Scholar
- Brédas J, Norton J, Cornil J, Coropceanu V: Molecular understanding of organic solar cells: the challenges. Acc Chem Res 2009, 42: 1691–1699. 10.1021/ar900099hView ArticleGoogle Scholar
- Lindahl E, Hess B, van der Spoel D: GROMACS 3.0: a package for molecular simulation and trajectory analysis. J of Mol Model 2001, 7: 306–317.Google Scholar
- Wang J, Wolf R, Caldwell J, Kollman P, Case D: Development and testing of a general amber force field. J Comput Chem 2004, 25: 1157. 10.1002/jcc.20035View ArticleGoogle Scholar
- Singh UC, Kollman PA: An approach to computing electrostatic charges for molecules. J Comp Chem 1983, 5: 129–145.View ArticleGoogle Scholar
- Stewart JJP: Optimization of parameters for semiempirical methods V: modification of NDDO approximations and application to 70 elements. J Mol Modeling 2007, 13: 1173–1213. 10.1007/s00894-007-0233-4View ArticleGoogle Scholar
- Sousa da Silva A, Vranken W, Laue E: ACPYPE - Antechamber python parser interface. [http://code.google.com/p/acpype/] 
- Ramalho TC, França TC, Cortopassi WA, Gonçalves AS, da Silva AW, da Cunha EF: Topology and dynamics of the interaction between 5-nitroimidazole radiosensitizers and duplex DNA studied by a combination of docking, molecular dynamic simulations and NMR spectroscopy. J Mol Struc 2011, 992: 65–71. 10.1016/j.molstruc.2011.02.042View ArticleGoogle Scholar
- Punkvang A, Saparpakorn P, Hannongbuam S, Wolschann P, Beyer A, Pungpo P: Investigating the structural basis of arylamides to improve potency against M. tuberculosis strain through molecular dynamics simulations. Europ J Med Chem 2010, 45: 5585–5593. 10.1016/j.ejmech.2010.09.008View ArticleGoogle Scholar
- Balajee R, Rajan MSD: Molecular docking and simulation studies of farnesyl trasnferase with the potential inhibitor theflavin. J Appl Pharm Sci 2011, 8: 141–148.Google Scholar
- ACPYPE Wiki: Testing ACPYPE amb2gmx function [http://code.google.com/p/acpype/wiki/TestingAcpypeAmb2gmx] 
- Campbell RB, Robertson MJ, Trotter J: The crystal and molecular structure of pentacene. Acta Cryst 1961, 14: 705. 10.1107/S0365110X61002163View ArticleGoogle Scholar
- Endres RG, Fong CY, Yang LH, Witte G, Wöll C: Structural and electronic properties of pentacene molecule and molecular pentacene solid. Comp Mat Sci 2004, 29: 362–370. 10.1016/j.commatsci.2003.09.006View ArticleGoogle Scholar
- Berendsen HJC, Postma JPM, van Gunsteren W F, DiNola A, Haak JR: Molecular dynamics with coupling to an external bath. J Chem Phys 1984, 81: 3684. 10.1063/1.448118View ArticleGoogle Scholar
- Wang Y, Chengb H, Wanga Y, Hub T, Hob J, Leeb C, Leia T, Yeha C: Influence of measuring environment on the electrical characteristics of pentacene-based thin film transistors. Thin Solid Films 2004, 467: 215–219. 10.1016/j.tsf.2004.04.001View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License(http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.