TY - JOUR
T1 - Electronic Mechanism of in Situ Inversion of Rectification Polarity in Supramolecular Engineered Monolayer
AU - Kong, Gyu Don
AU - Byeon, Seo Eun
AU - Jang, Jiung
AU - Kim, Jeong Won
AU - Yoon, Hyo Jae
N1 - Funding Information:
This research was supported by the NRF of Korea (NRF-2021M3F3A2A03017999, NRF-2019R1A2C2011003, NRF-2019R1A6A1A11044070, NRF-2019M3D1A1078296).
Publisher Copyright:
©
PY - 2022
Y1 - 2022
N2 - This Communication describes polarity inversion in molecular rectification and the related mechanism. Using a supramolecular engineered, ultrastable, binary-mixed self-assembled monolayer (SAM) composed of an organic molecular diode (SC11BIPY) and an inert reinforcement molecule (SC8), we probed a rectification ratio (r)-voltage relationship over an unprecedentedly wide voltage range (up to |3.5 V|) with statistical significance. We observed positive polarity in rectification at |1.0 V| (r = 107), followed by disappearance of rectification at ∼|2.25 V|, and then eventual emergence of new rectification with the opposite polarity at ∼|3.5 V| (r = 0.006; 1/r = 162). The polarity inversion occurred with a span over 4 orders of magnitude in r. Low-temperature experiments, electronic structure analysis, and theoretical calculations revealed that the unusually wide voltage range permits access to molecular orbital energy levels that are inaccessible in the traditional narrow voltage regime, inducing the unprecedented in situ inversion of polarity.
AB - This Communication describes polarity inversion in molecular rectification and the related mechanism. Using a supramolecular engineered, ultrastable, binary-mixed self-assembled monolayer (SAM) composed of an organic molecular diode (SC11BIPY) and an inert reinforcement molecule (SC8), we probed a rectification ratio (r)-voltage relationship over an unprecedentedly wide voltage range (up to |3.5 V|) with statistical significance. We observed positive polarity in rectification at |1.0 V| (r = 107), followed by disappearance of rectification at ∼|2.25 V|, and then eventual emergence of new rectification with the opposite polarity at ∼|3.5 V| (r = 0.006; 1/r = 162). The polarity inversion occurred with a span over 4 orders of magnitude in r. Low-temperature experiments, electronic structure analysis, and theoretical calculations revealed that the unusually wide voltage range permits access to molecular orbital energy levels that are inaccessible in the traditional narrow voltage regime, inducing the unprecedented in situ inversion of polarity.
UR - http://www.scopus.com/inward/record.url?scp=85130003452&partnerID=8YFLogxK
U2 - 10.1021/jacs.2c02391
DO - 10.1021/jacs.2c02391
M3 - Article
C2 - 35500106
AN - SCOPUS:85130003452
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -