Abstract
Transition metal dichalcogenides (TMDs) with a two-dimensional layered structure have been considered highly promising materials for next-generation flexible, wearable, stretchable and transparent devices due to their unique physical, electrical and optical properties. Recent studies on TMD devices have focused on developing a suitable doping technique because precise control of the threshold voltage ($V_{TH}$) and the number of tightly-bound trions are required to achieve high performance electronic and optoelectronic devices, respectively. In particular, it is critical to develop an ultra-low level doping technique for the proper design and optimization of TMD-based devices because high level doping (about $10^{12}cm^{-2}$) causes TMD to act as a near-metallic layer. However, it is difficult to apply an ion implantation technique to TMD materials due to crystal damage that occurs during the implantation process. Although safe doping techniques have recently been developed, most of the previous TMD doping techniques presented very high doping levels of ${\sim}10^{12}cm^{-2}$. Recently, low-level n- and p-doping of TMD materials was achieved using cesium carbonate ($Cs_2CO_3$), octadecyltrichlorosilane (OTS), and M-DNA, but further studies are needed to reduce the doping level down to an intrinsic level. Here, we propose a novel DNA-based doping method on $MoS_2$ and $WSe_2$ films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures. The available n-doping range (${\Delta}n$) on the $MoS_2$ by Ln-DNA (DNA functionalized by trivalent Ln ions) is between $6{\times}10^9cm^{-2}$ and $2.6{\times}10^{10}cm^{-2}$, which is even lower than that provided by pristine DNA (${\sim}6.4{\times}10^{10}cm^{-2}$). The p-doping change (${\Delta}p$) on $WSe_2$ by Ln-DNA is adjusted between $-1.0{\times}10^{10}cm^{-2}$ and $-2.4{\times}10^{10}cm^{-2}$. In the case of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions) doping where $Eu^{3+}$ or $Gd^{3+}$ ions were incorporated, a light p-doping phenomenon is observed on $MoS_2$ and $WSe_2$ (respectively, negative ${\Delta}n$ below $-9{\times}10^9cm^{-2}$ and positive ${\Delta}p$ above $1.4{\times}10^{10}cm^{-2}$) because the added $Cu^{2+}$ ions probably reduce the strength of negative charges in Ln-DNA. However, a light n-doping phenomenon (positive ${\Delta}n$ above $10^{10}cm^{-2}$ and negative ${\Delta}p$ below $-1.1{\times}10^{10}cm^{-2}$) occurs in the TMD devices doped by Co-DNA with $Tb^{3+}$ or $Er^{3+}$ ions. A significant (factor of ~5) increase in field-effect mobility is also observed on the $MoS_2$ and $WSe_2$ devices, which are, respectively, doped by $Tb^{3+}$-based Co-DNA (n-doping) and $Gd^{3+}$-based Co-DNA (p-doping), due to the reduction of effective electron and hole barrier heights after the doping. In terms of optoelectronic device performance (photoresponsivity and detectivity), the $Tb^{3+}$ or $Er^{3+}$-Co-DNA (n-doping) and the $Eu^{3+}$ or $Gd^{3+}$-Co-DNA (p-doping) improve the $MoS_2$ and $WSe_2$ photodetectors, respectively.