journal article·2007-09

Charging and discharging of single conjugated-polymer nanoparticles

Rodrigo E. Palacios, Fu-Ren F. Fan, John K. Grey, Jungdon Suk, Allen J. Bard, Paul F. Barbara

Nature Materials· Volume 6· Issue 9
Publisher page

Abstract

Despite intense, long-term interest in organic semiconductors from both an applied and fundamental perspective, key aspects of the electronic properties of these materials remain poorly defined. A particularly challenging problem is the molecular nature of positive charge carriers, that is, holes or oxidized species in organics. Here, the unique ability of single-molecule spectroelectrochemistry (SMS-EC) to unravel complex electrochemical process in heterogeneous media is used to study the oxidation of nanoparticles of the conjugated polymer poly(9,9-dioctylfluorene-co-benzothiadiazole). A reversible hole-injection charging process has been observed that occurs primarily by initial injection of shallow (untrapped) holes, but soon after the injection, a small fraction of the holes becomes deeply trapped. Good agreement between experimental data and simulations strongly supports the presence of deep traps in the studied nanoparticles and highlights the ability of SMS-EC to study energetics and dynamics of deep traps in organic materials at the nanoscale.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Conducting polymers and applications · Electrochemical Analysis and Applications · Organic Electronics and Photovoltaics

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (27)

Show source-provided references
1. Campbell, A. J., Bradley, D. D. C. & Antoniadis, H. Dispersive electron transport in an electroluminescent polyfluorene copolymer measured by the current integration time-of-flight method. Appl. Phys. Lett. 79, 2133–2135 (2001).10.1063/1.1406143 ↗
2. Chang, J. B. & Subramanian, V. Effect of active layer thickness on bias stress effect in pentacene thin-film transistors. Appl. Phys. Lett. 88, 233513 (2006).10.1063/1.2210791 ↗
3. Gomes, H. L. et al. Bias-induced threshold voltages shifts in thin-film organic transistors. Appl. Phys. Lett. 84, 3184–3186 (2004).10.1063/1.1713035 ↗
4. Lang, D. V., Chi, X., Siegrist, T., Sergent, A. M. & Ramirez, A. P. Bias-dependent generation and quenching of defects in pentacene. Phys. Rev. Lett. 93, 076601 (2004).10.1103/PhysRevLett.93.076601 ↗
5. Matters, M., De Leeuw, D. M., Herwig, P. T. & Brown, A. R. Bias-stress induced instability of organic thin film transistors. Synth. Met. 102, 998–999 (1999).10.1016/S0379-6779(98)01162-X ↗
6. Salleo, A. & Street, R. A. Light-induced bias stress reversal in polyfluorene thin-film transistors. J. Appl. Phys. 94, 471–479 (2003).10.1063/1.1581352 ↗
7. Seeley, A. J. A. B., Friend, R. H., Kim, J.-S. & Burroughes, J. H. Trap-assisted hole injection and quantum efficiency enhancement in poly(9,9′ dioctylfluorene-alt-benzothiadiazole) polymer light-emitting diodes. J. Appl. Phys. 96, 7643–7649 (2004).10.1063/1.1818350 ↗
8. Muller, E. M. & Marohn, J. A. Microscopic evidence for spatially inhomogeneous charge trapping in pentacene. Adv. Mater. 17, 1410–1414 (2005).10.1002/adma.200401174 ↗
9. Inzelt, G. Mechanism of charge transport in polymer-modified electrodes. Electroanal. Chem. 18, 89–241 (1994).
10. Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications (Wiley, New York, 2001).
11. Grey, J. K., Kim, D. Y., Norris, B. C., Miller, W. L. & Barbara, P. F. Size dependent spectroscopic properties of conjugated polymer nanoparticles. J. Phys. Chem. B 110, 25568–25572 (2006).10.1021/jp065990a ↗
12. Szymanski, C. et al. Single molecule nanoparticles of the conjugated polymer MEH-PPV, preparation and characterization by near-field scanning optical microscopy. J. Phys. Chem. B 109, 8543–8546 (2005).10.1021/jp051062k ↗
13. Halls, J. J. M. et al. Photodiodes based on polyfluorene composites: Influence of morphology. Adv. Mater. 12, 498–502 (2000).10.1002/(SICI)1521-4095(200004)12:7<498::AID-ADMA498>3.0.CO;2-H ↗
14. Palacios, R. E., Fan, F.-R. F., Bard, A. J. & Barbara, P. F. Single-molecule spectroelectrochemistry (SMS-EC). J. Am. Chem. Soc. 128, 9028–9029 (2006).10.1021/ja062848e ↗
15. Barbara, P. F., Gesquiere, A. J., Park, S.-J. & Lee, Y. J. Single-molecule spectroscopy of conjugated polymers. Acc. Chem. Res. 38, 602–610 (2005).10.1021/ar040141w ↗
16. Grey, J. K. et al. Effect of temperature and chain length on the bimodal emission properties of single polyfluorene copolymer molecules. J. Phys. Chem. B 110, 18898–18903 (2006).10.1021/jp057361r ↗
17. Lammi, R. K. & Barbara, P. F. Influence of chain length on exciton migration to low-energy sites in single fluorene copolymers. Photochem. Photobio. Sci. 4, 95–99 (2005).10.1039/b417753n ↗
18. Gesquiere, A. J., Park, S.-J. & Barbara, P. F. F-V/SMS: A new technique for studying the structure and dynamics of single molecules and nanoparticles. J. Phys. Chem. B 108, 10301–10308 (2004).10.1021/jp049583f ↗
19. Yu, J., Song, N. W., McNeill, J. D. & Barbara, P. F. Efficient exciton quenching by hole polarons in the conjugated polymer MEH-PPV. Isr. J. Chem. 44, 127–132 (2004).10.1560/PHGE-RR3P-5P7V-DGCM ↗
20. Arkhipov, V. I., Heremans, P., Emelianova, E. V. & Bassler, H. Effect of doping on the density-of-states distribution and carrier hopping in disordered organic semiconductors. Phys. Rev. B 71, 045214 (2005).10.1103/PhysRevB.71.045214 ↗
21. Davids, P. S., Campbell, I. H. & Smith, D. L. Device model for single carrier organic diodes. J. Appl. Phys. 82, 6319–6325 (1997).10.1063/1.366522 ↗
22. Rudolph, M. Reply to L.K. Bieniasz’s comments on my paper Digital simulations on unequally spaced grids. Part 1. Critical remarks on using the point method by discretisation on transformed grid [J. Electroanal. Chem. 529 (2002) 97]. J. Electroanal. Chem. 558, 171–176 (2003).10.1016/S0022-0728(03)00379-6 ↗
23. Rudolph, M. Digital simulations on unequally spaced grids. Part 2. Using the box method by discretization on a transformed equally spaced grid. J. Electroanal. Chem. 543, 23–39 (2003).10.1016/S0022-0728(02)01257-3 ↗
24. Rudolph, M. Digital simulations on unequally spaced grids. Part 3. Attaining exponential convergence for the discretisation error of the flux as a new strategy in digital simulations of electrochemical experiments. J. Electroanal. Chem. 571, 289–307 (2004).10.1016/j.jelechem.2004.05.017 ↗
25. Rudolph, M. Attaining exponential convergence for the flux error with second- and fourth-order accurate finite-difference equations. Part 3. Application to electrochemical systems comprising second-order chemical reactions. J. Comput. Chem. 26, 1193–1204 (2005).10.1002/jcc.20256 ↗
26. Rudolph, M. Attaining exponential convergence for the flux error with second- and fourth-order accurate finite-difference equations. II. Application to systems comprising first-order chemical reactions. J. Comput. Chem. 26, 633–641 (2005).10.1002/jcc.20201 ↗
27. Rudolph, M. Attaining exponential convergence for the flux error with second-and fourth-order accurate finite-difference equations. I. Presentation of the basic concept and application to a pure diffusion system. J. Comput. Chem. 26, 619–632 (2005).10.1002/jcc.20200 ↗