"supersaturated" self-assembled charge-selective interfacial layers for organic solar cells

Charles Kiseok Song, Kyle A. Luck, Nanjia Zhou, Li Zeng, Henry M. Heitzer, Eric F. Manley, Samuel Goldman, Lin X. Chen, Mark A Ratner, Michael J. Bedzyk, Robert P. H. Chang, Mark C Hersam, Tobin J Marks

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

To achieve densely packed charge-selective organosilane-based interfacial layers (IFLs) on the tin-doped indium oxide (ITO) anodes of organic photovoltaic (OPV) cells, a series of Ar2N-(CH2)n-SiCl3 precursors with Ar = 3,4-difluorophenyl, n = 3, 6, 10, and 18, was synthesized, characterized, and chemisorbed on OPV anodes to serve as IFLs. To minimize lateral nonbonded -NAr2···Ar2N- repulsions which likely limit IFL packing densities in the resulting self-assembled monolayers (SAMs), precursor mixtures having both small and large n values are simultaneously deposited. These "heterogeneous" SAMs are characterized by a battery of techniques: contact angle measurements, X-ray reflectivity, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), cyclic voltammetry, and DFT computation. It is found that the headgroup densities of these "supersaturated" heterogeneous SAMs (SHSAMs) are enhanced by as much as 17% versus their homogeneous counterparts. Supersaturation significantly modifies the IFL properties including the work function (as much as 16%) and areal dipole moment (as much as 49%). Bulk-heterojunction OPV devices are fabricated with these SHSAMs: ITO/IFL/poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b?]dithiophene-2,6-diyl][2-[[(2-ethylhexyl)oxy]carbonyl]-3-fluorothieno[3,4-b]thiophenediyl]]:phenyl-C71-butyric acid methyl ester (PTB7:PC71BM)/LiF/Al. OPVs having SHSAM IFLs exhibit significantly enhanced performance (PCE by 54%; Voc by 35%) due to enhanced charge selectivity and collection, with the PCE rivaling or exceeding that of PEDOT:PSS IFL devices -7.62%. The mechanism underlying the enhanced performance involves modified hole collection and selectivity efficiency inferred from the UPS data. The ITO/SAM/SHSAM surface potential imposed by the dipolar SAMs causes band bending and favorably alters the Schottky barrier height. Thus, interfacial charge selectivity and collection are enhanced as evident in the greater OPV Voc.

Original languageEnglish
Pages (from-to)17762-17773
Number of pages12
JournalJournal of the American Chemical Society
Volume136
Issue number51
DOIs
Publication statusPublished - Dec 24 2014

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Photoelectron Spectroscopy
Self assembled monolayers
Ultraviolet photoelectron spectroscopy
Electrodes
Equipment and Supplies
Anodes
Butyric Acid
Butyric acid
Tin
Photovoltaic cells
Supersaturation
Dipole moment
Esters
Surface potential
Angle measurement
X-Rays
Discrete Fourier transforms
Indium
Cyclic voltammetry
Contact angle

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

"supersaturated" self-assembled charge-selective interfacial layers for organic solar cells. / Song, Charles Kiseok; Luck, Kyle A.; Zhou, Nanjia; Zeng, Li; Heitzer, Henry M.; Manley, Eric F.; Goldman, Samuel; Chen, Lin X.; Ratner, Mark A; Bedzyk, Michael J.; Chang, Robert P. H.; Hersam, Mark C; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 136, No. 51, 24.12.2014, p. 17762-17773.

Research output: Contribution to journalArticle

Song, CK, Luck, KA, Zhou, N, Zeng, L, Heitzer, HM, Manley, EF, Goldman, S, Chen, LX, Ratner, MA, Bedzyk, MJ, Chang, RPH, Hersam, MC & Marks, TJ 2014, '"supersaturated" self-assembled charge-selective interfacial layers for organic solar cells', Journal of the American Chemical Society, vol. 136, no. 51, pp. 17762-17773. https://doi.org/10.1021/ja508453n
Song, Charles Kiseok ; Luck, Kyle A. ; Zhou, Nanjia ; Zeng, Li ; Heitzer, Henry M. ; Manley, Eric F. ; Goldman, Samuel ; Chen, Lin X. ; Ratner, Mark A ; Bedzyk, Michael J. ; Chang, Robert P. H. ; Hersam, Mark C ; Marks, Tobin J. / "supersaturated" self-assembled charge-selective interfacial layers for organic solar cells. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 51. pp. 17762-17773.
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AU - Song, Charles Kiseok

AU - Luck, Kyle A.

AU - Zhou, Nanjia

AU - Zeng, Li

AU - Heitzer, Henry M.

AU - Manley, Eric F.

AU - Goldman, Samuel

AU - Chen, Lin X.

AU - Ratner, Mark A

AU - Bedzyk, Michael J.

AU - Chang, Robert P. H.

AU - Hersam, Mark C

AU - Marks, Tobin J

PY - 2014/12/24

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N2 - To achieve densely packed charge-selective organosilane-based interfacial layers (IFLs) on the tin-doped indium oxide (ITO) anodes of organic photovoltaic (OPV) cells, a series of Ar2N-(CH2)n-SiCl3 precursors with Ar = 3,4-difluorophenyl, n = 3, 6, 10, and 18, was synthesized, characterized, and chemisorbed on OPV anodes to serve as IFLs. To minimize lateral nonbonded -NAr2···Ar2N- repulsions which likely limit IFL packing densities in the resulting self-assembled monolayers (SAMs), precursor mixtures having both small and large n values are simultaneously deposited. These "heterogeneous" SAMs are characterized by a battery of techniques: contact angle measurements, X-ray reflectivity, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), cyclic voltammetry, and DFT computation. It is found that the headgroup densities of these "supersaturated" heterogeneous SAMs (SHSAMs) are enhanced by as much as 17% versus their homogeneous counterparts. Supersaturation significantly modifies the IFL properties including the work function (as much as 16%) and areal dipole moment (as much as 49%). Bulk-heterojunction OPV devices are fabricated with these SHSAMs: ITO/IFL/poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b?]dithiophene-2,6-diyl][2-[[(2-ethylhexyl)oxy]carbonyl]-3-fluorothieno[3,4-b]thiophenediyl]]:phenyl-C71-butyric acid methyl ester (PTB7:PC71BM)/LiF/Al. OPVs having SHSAM IFLs exhibit significantly enhanced performance (PCE by 54%; Voc by 35%) due to enhanced charge selectivity and collection, with the PCE rivaling or exceeding that of PEDOT:PSS IFL devices -7.62%. The mechanism underlying the enhanced performance involves modified hole collection and selectivity efficiency inferred from the UPS data. The ITO/SAM/SHSAM surface potential imposed by the dipolar SAMs causes band bending and favorably alters the Schottky barrier height. Thus, interfacial charge selectivity and collection are enhanced as evident in the greater OPV Voc.

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