TY - JOUR
T1 - Supramolecular tunnelling junctions with robust high rectification based on assembly effects
AU - Roemer, Max
AU - Chen, Xiaoping
AU - Li, Yuan
AU - Wang, Lejia
AU - Yu, Xiaojiang
AU - Cazade, Pierre André
AU - Nickle, Cameron
AU - Akter, Romena
AU - Del Barco, Enrique
AU - Thompson, Damien
AU - Nijhuis, Christian A.
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2024/9/11
Y1 - 2024/9/11
N2 - The performance of large-area molecular diodes can in rare cases approach the lower limit of commercial semiconductor devices but predictive structure-property design remains difficult as the rectification ratio (R) achieved by self-assembled monolayer (SAM) based diodes depends on several intertwined parameters. This paper describes a systematic approach to achieve high rectification in bisferrocenyl-based molecular diodes, HSCnFc-C 00000000000000000 00000000000000000 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 00000000000000000 00000000000000000 C-Fc (n = 9-15) immobilised on metal surfaces (Ag, Au and Pt). Experiments supported by molecular dynamics simulations show that the molecular length and bottom electrode influence the SAM packing, which affects the breakdown voltage (VBD), the associated maximum R (Rmax), and the bias at which the Rmax is achieved (Vsat,R). From the electrical characterisation of the most stable Pt-SCnFc-C C-Fc//GaOx/EGaIn junctions, we found that VBD, Vsat,R, and Rmax all scale linearly with the spacer length of Cn, and that Rmax for all the SAMs consistently exceeds the “Landauer limit” of 103. Our data shows that the robust switching of M-SCnFc-C C-Fc//GaOx/EGaIn junctions is the result of the combined optimisation of parameters involving the molecular structure, the type of metal substrate, and the applied operating conditions (bias window), to create stable and high-performance junctions.
AB - The performance of large-area molecular diodes can in rare cases approach the lower limit of commercial semiconductor devices but predictive structure-property design remains difficult as the rectification ratio (R) achieved by self-assembled monolayer (SAM) based diodes depends on several intertwined parameters. This paper describes a systematic approach to achieve high rectification in bisferrocenyl-based molecular diodes, HSCnFc-C 00000000000000000 00000000000000000 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 01111111111111110 00000000000000000 00000000000000000 00000000000000000 C-Fc (n = 9-15) immobilised on metal surfaces (Ag, Au and Pt). Experiments supported by molecular dynamics simulations show that the molecular length and bottom electrode influence the SAM packing, which affects the breakdown voltage (VBD), the associated maximum R (Rmax), and the bias at which the Rmax is achieved (Vsat,R). From the electrical characterisation of the most stable Pt-SCnFc-C C-Fc//GaOx/EGaIn junctions, we found that VBD, Vsat,R, and Rmax all scale linearly with the spacer length of Cn, and that Rmax for all the SAMs consistently exceeds the “Landauer limit” of 103. Our data shows that the robust switching of M-SCnFc-C C-Fc//GaOx/EGaIn junctions is the result of the combined optimisation of parameters involving the molecular structure, the type of metal substrate, and the applied operating conditions (bias window), to create stable and high-performance junctions.
UR - http://www.scopus.com/inward/record.url?scp=85204719276&partnerID=8YFLogxK
U2 - 10.1039/d4nr01514b
DO - 10.1039/d4nr01514b
M3 - Article
AN - SCOPUS:85204719276
SN - 2040-3364
VL - 16
SP - 19683
EP - 19691
JO - Nanoscale
JF - Nanoscale
IS - 42
ER -