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Crystal formation in tetracyanoquinodimethane on the nanoscale: polymorphism and progression of self-assembly

Published online by Cambridge University Press:  25 July 2011

Maki Nishida
Affiliation:
Department of Physics, Georgetown University, Washington, District of Columbia 20057
Edward R. Van Keuren*
Affiliation:
Department of Physics, Georgetown University, Washington, District of Columbia 20057
*
Address all correspondence to Edward R. Van Keuren atvankeu@physics.georgetown.edu
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Abstract

Molecules self-assembling in solution may pass through multiple phases and morphologies before reaching a thermodynamically stable state. Here we demonstrated this effect in tetracyanoquinodimethane (TCNQ), an organic molecule often used as an electron acceptor in charge transfer complex compounds. We showed that it self-assembles in a wide range of crystal habits, from nanocoils to polyhedral crystals. Scanning electron microscopy imaging on freeze-dried samples revealed the crystal growth of TCNQ starting from seed-shaped nucleation sites, progressing through flower-like structures and finally forming polyhedral micro-crystals. These results are supplemented by absorption spectroscopy as well as x-ray powder diffraction (XRPD) characterization of a powder sample.

Type
Rapid Communications
Copyright
Copyright © Materials Research Society 2011

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References

1.Ostwald, W.: Studies on formation and transformation of solid materials. Z. Phys. Chem. 22, 289 (1897).Google Scholar
2.Threlfall, T.: Structural and thermodynamic explanations of Ostwald's rule. Org. Process Res. Dev. 7, 1017 (2003).CrossRefGoogle Scholar
3.Chung, S., Kim, Y., Kim, J., and Kim, Y.: Multiphase transformation and Ostwald's rule of stages during crystallization of a metal phosphate. Nature Phys. 5, 68 (2009).Google Scholar
4.Kashchiev, D. and Sato, K.: Kinetics of crystallization preceded by metastable-phase formation. J. Chem. Phys. 109, 8530 (1998).CrossRefGoogle Scholar
5.Claudio, D., Gonzalez-Hernandez, J., Licea, O., Laine, B., Prokhorov, E., and Trapaga, G.J.: An analytical model to represent crystallization kinetics in materials with metastable phase formation. Non-Cryst. Solids 352, 51 (2006).Google Scholar
6.Prokhorov, E., Trapaga, G., and Kovalenko, Y.: Crystallization kinetics in materials with a two-phase formation from an amorphous phase. J. Optoelectron. Adv. Mater. 8, 2066 (2006).Google Scholar
7.Borchert, C., Nere, N., Ramkrishna, D., Voigt, A., and Sundmacher, K.: On the prediction of crystal shape distributions in a steady-state continuous crystallizer. Chem. Eng. Sci. 64, 686 (2009).Google Scholar
8.Kasai, H., Nalwa, H.S., Oikawa, H., Okada, S., Matsuda, H., Minami, N., Kakuda, A., Ono, K., Mukoh, A., and Nakanishi, H.: A novel preparation method of organic microcrystals. Jpn. J. Appl. Phys. 31, L1132 (1992).CrossRefGoogle Scholar
9.Drain, C. M., Varotto, A., and Radivojevic, I.: Self-organized porphyrinic materials. Chem. Rev. 109, 1630 (2009).CrossRefGoogle ScholarPubMed
10.Echlin, P.: Handbook of Sample Preparation for Scanning Electron Microscopy and X-Ray Microanalysis Springer, New York, 2009).Google Scholar
11.Thiberge, S., Zik, O., and Moses, E.: An apparatus for imaging liquids, cells, and other wet samples in the scanning electron microscopy. Rev. Sci. Instrum. 75, 2280 (2004).Google Scholar
12.Liu, H., Li, J., Lao, C., Huang, C., Li, Y., Wang, Z.L., and Zhu, D.: Morphological tuning and conductivity of organic conductor nanowires. Nanotechnology 18, 495704 (2007).Google Scholar
13.Cao, G., Fang, F., Ye, C., Xing, X., Xu, H, Sun, D., and Chen, G.: Microscopy investigation of Ag-TCNQ micro/nanostructures synthesized via two solution routes. Micron 36, 285 (2005).Google Scholar
14.Melinger, J.S., Laman, N., Harsha, S.S., Cheng, S., and Grischkowsky, D.: High-resolution waveguide terahertz spectroscopy of partially oriented organic polycrystalline films. J. Phys. Chem. A 111, 10977 (2007).Google Scholar
15.Li, J., Liu, W., and Xue, Z.: Chiral pattern formation: Combined transmission electron microscopy and atomic force microscopy study of tetracyanodimethane thin film grown by vacuum evaporation. J. Vac. Sci. Technol., B 20, 673 (2002).Google Scholar
16.Vainshtein, B.K., Fridkin, V.M., and Indenbom, V.L.: Modern Crystallography: Structure of Crystals, 3rd ed.Springer, Berlin, 2000).CrossRefGoogle Scholar
17.Higo, M., Futagawa, T., Mitsushio, M., Yoshidome, T., and Ozono, Y.: Adsorption state and morphology of tetracyanoquinodimethane deposited from solution onto the atomically smooth native oxide surface of Al(111) films studied by x-ray photoelectron spectroscopy and atomic force microscopy. J. Phys Chem. B 107, 5871 (2003).Google Scholar
18.Lindquist, J. and Hemminger, J.: High-energy resolution x-ray photoelectron spectroscopy studies of tetracyanoquinodimethane charge-transfer complexes with copper, nickel, and lithium. Chem. Mater. 1, 72 (1989).CrossRefGoogle Scholar
19.Van Keuren, E., Georgieva, E., and Adrian, J.: Kinetics of the formation of organic molecular nanocrystals. Nano Lett. 1, 141 (2001).CrossRefGoogle Scholar
20.Van Keuren, E. and Nishida, M.: Synthesis of nanocomposite materials using the reprecipitation method. CMC 14, 61 (2009).Google Scholar
21.Mori, J., Miyashita, Y., Oliveira, D., Kasai, H., Oikawa, H., and Nakanishi, H.: Stopped-flow analysis on the mechanism of perylene nanoparticle formation by the reprecipitation method. J. Cryst. Growth 311, 553 (2009).Google Scholar
22.Oliveira, D., Baba, K., Mori, J., Miyashita, Y., Kasai, H., Oikawa, H., and Nakanishi, H.: Nanocrystallization mechanism of organic compounds in the reprecipitation method by stopped-flow analysis. Jpn. J. Appl. Phys. 49, 105003 (2009).Google Scholar
23.Johnson, B. and Prud'homme, R.: Mechanism for rapid self-assembly of block copolymer nanoparticles. Phys. Rev. Lett. 91, 118302 (2003).Google Scholar
24.Van Keuren, E., Bone, A., and Ma, C.: Phthalocyanine nanoparticle formation in supersaturated solutions. Langmuir 24, 6079 (2008).CrossRefGoogle ScholarPubMed
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