Efficient hole transport material formed by atmospheric pressure plasma functionalization of Spiro-OMeTAD

Paheli Ghosh, Aruna Ivaturi, Debabrata Bhattacharya, James Bowen, Tony Nixon, Jan Kowal , Nicholas St. J. Braithwaite, Satheesh Krishnamurthy

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A technique to increase the conductivity of Spiro-OMeTAD using an easily scalable, non-thermal atmospheric pressure plasma jet (APPJ) is reported. An investigation of plasma functionalization demonstrated an enhancement in hole conductivity by over an order of magnitude from 9.4 × 10 −7 S cm −1 for the pristine film to 1.15 × 10 −5 S cm −1 for films after 5 minutes of plasma treatment. The conductivity value after plasma functionalization was comparable to that reported for 10–25% Li-TFSI-doped Spiro-OMeTAD. The increase in conductivity was correlated with a reduction in phase value observed using electrostatic force microscopy. Kelvin probe force microscopy showed an increase in work function after plasma exposure corresponding to the p-type nature of the doping. X-ray photoelectron spectroscopy revealed surface oxidation of plasma-functionalized films, as well as variation in nitrogen chemistry, with the formation of a higher binding energy quaternary nitrogen tail. Oxidation of Spiro-OMeTAD was also confirmed by the appearance of the 500 nm absorption peak using UV–vis spectroscopy. The synergistic contribution of increase in charge density in Spiro-OMeTAD due to the energetic species in the plasma jet coupled with improvement in π-π stacking of the molecules is thought to underlie the conductivity enhancement. The enhancement in positive charges can also be attributed to the formation of quinoid structures with quaternary nitrogen +N=C formed due to loss of methyl groups during plasma surface interaction. This work opens up the possibility of using an atmospheric pressure plasma jet as a simple and effective technique for doping and functionalizing Spiro-OMeTAD thin films to circumvent the detrimental issues associated with chemical dopants.

Original languageEnglish
Article number100321
Number of pages44
JournalMaterials Today Chemistry
Early online date24 Jul 2020
Publication statusPublished - 30 Sept 2020


  • atmospheric pressure plasma jet
  • conductivity
  • hole transport materials
  • perovkite solar cells


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