Abstract The relationship between hole density and conductivity in electrochemically gated polythiophene films is examined. The films are integrated into electrolyte‐gated transistors (EGTs), so that hole accumulations can be electrochemically modulated up to ≈0.4 holes per thiophene ring (hpr). Polythiophenes include poly(3‐alkylthiophenes) (P3ATs) with four different side chain lengths – butyl (P3BT), hexyl (P3HT), octyl (P3OT), or decyl (P3DT) – and poly[2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) and poly(3,3′′′‐didodecyl[2,2′:5′,2′′:5′′,2′′′‐quaterthiophene]‐5,5′′′‐diyl) (PQT). Analysis of the drain current – gate voltage (ID–VG) and gate current – gate voltage (IG–VG) characteristics of the EGTs reveals that all six polythiophene semiconductors exhibited reversible conductivity peaks at 0.12 – 0.15 hpr. Conductivity is suppressed beyond ≈0.4 hpr.The maximum carrier mobilities of the P3AT semiconductors increase, and hysteresis of the conductivity peaks decreases, with increasing alkyl side‐chain length. PBTTT and PQT with reduced side chain densities exhibit the largest hysteresis but have higher hole mobilities. The results suggest that at ≈0.4 hpr, a polaronic sub‐band is filled in all cases. Filling of the sub‐band correlates with a collapse in the hole mobility. The side‐chain dependence of the peak conductivity and hysteresis further suggests that Coulombic ion‐carrier interactions are important in these systems. Tailoring ion‐carrier correlations is likely important for further improvements in transport properties of electrochemically doped polythiophenes.
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Raman and Electrical Transport Properties of Few-Layered Arsenic-Doped Black Phosphorus
Black phosphorus (b-P) is an allotrope of phosphorus whose properties have attracted great attention. In contrast to other 2D compounds, or pristine b-P, the properties of b-P alloys have yet to be explored. In this report, we present a detailed study on the Raman spectra and on the temperature dependence of the electrical transport properties of As-doped black phosphorus (b-AsP) for an As fraction x = 0.25. The observed complex Raman spectra were interpreted with the support of Density Functional Theory (DFT) calculations since each original mode splits in three due to P-P, P-As, and As-As bonds. Field-effect transistors (FET) fabricated from few-layered b-AsP exfoliated onto Si/SiO 2 substrates exhibit hole-doped like conduction with a room temperature ON/OFF current ratio of ~10 3 and an intrinsic field-effect mobility approaching ~300 cm 2 /Vs at 300 K which increases up to 600 cm 2 /Vs at 100 K when measured via a 4-terminal method. Remarkably, these values are comparable to, or higher, than those initially reported for pristine b-P, indicating that this level of As doping is not detrimental to its transport properties. The ON to OFF current ratio is observed to increase up to 10 5 at 4 K. At high gate voltages b-AsP displays metallic behavior with the resistivity decreasing with decreasing temperature and saturating below T ∼ 100 K, indicating a gate-induced insulator to metal transition. Similarly to pristine b-P, its transport properties reveal a high anisotropy between armchair (AC) and zig-zag (ZZ) directions. Electronic band structure computed through periodic dispersion-corrected hybrid Density Functional Theory (DFT) indicate close proximity between the Fermi level and the top of the valence band(s) thus explaining its hole doped character. Our study shows that b-AsP has potential for optoelectronics applications that benefit from its anisotropic character and the ability to tune its band gap as a function of the number of layers and As content.
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- PAR ID:
- 10118826
- Date Published:
- Journal Name:
- Nanoscale
- ISSN:
- 2040-3364
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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