Structural variability and dynamics of the P3HT/PCBM interface and its effects on the electronic structure and the charge-transfer rates in solar cells

Tao Liu, David Cheung, Alessandro Troisi

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

Using a range of realistic interface geometries obtained from a molecular dynamics simulation we study the effects of different microscopic atomic arrangements on the electronic structure and charge transfer rates of the prototypical photovoltaic interface between P3HT (poly(3-hexylthiophene)) and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). The electronic structures of charge-transfer (CT) states belong to two groups that can be denoted as “charge-separated” and “charge-bridging” states. For the former group of structures, which may lead to fully separated charges, the ranges and the average values of internal reorganization energy, the electronic coupling and the charge separated states energy are evaluated. A range and distribution of absolute charge separation (CS) and recombination (CR) rates are computed using the Marcus–Levich–Jortner rate equation. Due to the variety of P3HT/PCBM interface structures, a very broad range of CS (7.7 × 109–1.8 × 1012 s−1) and CR (2.5 × 105–1.1 × 1010 s−1) “instantaneous” rates are computed. However, the energetic parameters affecting the rate evolve in time due to the dynamic nature of the interface with a characteristic timescale of about 10 ns. For this reason the slowest CR instantaneous rates are not observed and the minimum CR rate observed is determined by the rate of conformational rearrangement at the interface. The combination of these observations provides a more general framework for the interpretation of experimental spectroscopic data, suggesting that the analysis based on simple first order rates may be insufficient to describe charge transfer in organic solar cell interfaces.
LanguageEnglish
Pages21461-21470
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume13
Issue number48
Early online date2 Nov 2011
DOIs
Publication statusPublished - 28 Dec 2011

Fingerprint

butyric acid
Electronic structure
Charge transfer
esters
Solar cells
solar cells
charge transfer
electronic structure
Electron energy levels
Interfaces (computer)
Molecular dynamics
polarization (charge separation)
Geometry
Computer simulation
(6,6)-phenyl C61-butyric acid methyl ester
internal energy
molecular dynamics

Keywords

  • solar cell interfaces
  • spectroscopic data
  • molecular dynamics simulation
  • solar cells

Cite this

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title = "Structural variability and dynamics of the P3HT/PCBM interface and its effects on the electronic structure and the charge-transfer rates in solar cells",
abstract = "Using a range of realistic interface geometries obtained from a molecular dynamics simulation we study the effects of different microscopic atomic arrangements on the electronic structure and charge transfer rates of the prototypical photovoltaic interface between P3HT (poly(3-hexylthiophene)) and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). The electronic structures of charge-transfer (CT) states belong to two groups that can be denoted as “charge-separated” and “charge-bridging” states. For the former group of structures, which may lead to fully separated charges, the ranges and the average values of internal reorganization energy, the electronic coupling and the charge separated states energy are evaluated. A range and distribution of absolute charge separation (CS) and recombination (CR) rates are computed using the Marcus–Levich–Jortner rate equation. Due to the variety of P3HT/PCBM interface structures, a very broad range of CS (7.7 × 109–1.8 × 1012 s−1) and CR (2.5 × 105–1.1 × 1010 s−1) “instantaneous” rates are computed. However, the energetic parameters affecting the rate evolve in time due to the dynamic nature of the interface with a characteristic timescale of about 10 ns. For this reason the slowest CR instantaneous rates are not observed and the minimum CR rate observed is determined by the rate of conformational rearrangement at the interface. The combination of these observations provides a more general framework for the interpretation of experimental spectroscopic data, suggesting that the analysis based on simple first order rates may be insufficient to describe charge transfer in organic solar cell interfaces.",
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Structural variability and dynamics of the P3HT/PCBM interface and its effects on the electronic structure and the charge-transfer rates in solar cells. / Liu, Tao; Cheung, David; Troisi, Alessandro.

In: Physical Chemistry Chemical Physics, Vol. 13, No. 48, 28.12.2011, p. 21461-21470.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Structural variability and dynamics of the P3HT/PCBM interface and its effects on the electronic structure and the charge-transfer rates in solar cells

AU - Liu, Tao

AU - Cheung, David

AU - Troisi, Alessandro

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N2 - Using a range of realistic interface geometries obtained from a molecular dynamics simulation we study the effects of different microscopic atomic arrangements on the electronic structure and charge transfer rates of the prototypical photovoltaic interface between P3HT (poly(3-hexylthiophene)) and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). The electronic structures of charge-transfer (CT) states belong to two groups that can be denoted as “charge-separated” and “charge-bridging” states. For the former group of structures, which may lead to fully separated charges, the ranges and the average values of internal reorganization energy, the electronic coupling and the charge separated states energy are evaluated. A range and distribution of absolute charge separation (CS) and recombination (CR) rates are computed using the Marcus–Levich–Jortner rate equation. Due to the variety of P3HT/PCBM interface structures, a very broad range of CS (7.7 × 109–1.8 × 1012 s−1) and CR (2.5 × 105–1.1 × 1010 s−1) “instantaneous” rates are computed. However, the energetic parameters affecting the rate evolve in time due to the dynamic nature of the interface with a characteristic timescale of about 10 ns. For this reason the slowest CR instantaneous rates are not observed and the minimum CR rate observed is determined by the rate of conformational rearrangement at the interface. The combination of these observations provides a more general framework for the interpretation of experimental spectroscopic data, suggesting that the analysis based on simple first order rates may be insufficient to describe charge transfer in organic solar cell interfaces.

AB - Using a range of realistic interface geometries obtained from a molecular dynamics simulation we study the effects of different microscopic atomic arrangements on the electronic structure and charge transfer rates of the prototypical photovoltaic interface between P3HT (poly(3-hexylthiophene)) and PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). The electronic structures of charge-transfer (CT) states belong to two groups that can be denoted as “charge-separated” and “charge-bridging” states. For the former group of structures, which may lead to fully separated charges, the ranges and the average values of internal reorganization energy, the electronic coupling and the charge separated states energy are evaluated. A range and distribution of absolute charge separation (CS) and recombination (CR) rates are computed using the Marcus–Levich–Jortner rate equation. Due to the variety of P3HT/PCBM interface structures, a very broad range of CS (7.7 × 109–1.8 × 1012 s−1) and CR (2.5 × 105–1.1 × 1010 s−1) “instantaneous” rates are computed. However, the energetic parameters affecting the rate evolve in time due to the dynamic nature of the interface with a characteristic timescale of about 10 ns. For this reason the slowest CR instantaneous rates are not observed and the minimum CR rate observed is determined by the rate of conformational rearrangement at the interface. The combination of these observations provides a more general framework for the interpretation of experimental spectroscopic data, suggesting that the analysis based on simple first order rates may be insufficient to describe charge transfer in organic solar cell interfaces.

KW - solar cell interfaces

KW - spectroscopic data

KW - molecular dynamics simulation

KW - solar cells

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T2 - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 48

ER -