Site-selective substitutional doping with atomic precision on stepped Al (111) surface by single-atom manipulation
© Chen et al.; licensee Springer. 2014
Received: 12 February 2014
Accepted: 25 April 2014
Published: 13 May 2014
In fabrication of nano- and quantum devices, it is sometimes critical to position individual dopants at certain sites precisely to obtain the specific or enhanced functionalities. With first-principles simulations, we propose a method for substitutional doping of individual atom at a certain position on a stepped metal surface by single-atom manipulation. A selected atom at the step of Al (111) surface could be extracted vertically with an Al trimer-apex tip, and then the dopant atom will be positioned to this site. The details of the entire process including potential energy curves are given, which suggests the reliability of the proposed single-atom doping method.
KeywordsSingle-atom doping Substitutional Single-atom manipulation Atomic precision Metal surface
Single-atom manipulation, which was first introduced by Eigler et al. and realized experimentally on Ni (111) surface with a scanning tunneling microscope (STM) tip, provides a way to fabricate nanostructures with atomic precision [1–7]. Besides the STM tip, for nonconductive surface, the tip of an atomic force microscope (AFM) has also been applied to achieve various single-atom manipulations [8–10]. Studies show that merely by the mechanical interaction force acting between the tip and atom, complex manipulations can still be accomplished besides the primary lateral and vertical manipulations. For instance, on Al (111) surface, a reversible modification of the configuration of supported nanoclusters with atomic precision by tip was demonstrated in our previous simulations . Also, the work on Si (111) surface given by Sugimoto et al. shows that an atom from the AFM tip can interchange with a surface adatom in a reversible exchange procedure . Through this vertical manipulation, a single Si atom can be precisely positioned into or extracted from the Sn layer. As the size of devices shrinks to nanoscale or even to atomic scale, besides configuration of nanostructure, the number of isolated atoms of certain species and their location could modify their functionality and performance [12, 13]. Therefore, it is sometimes demanded to position dopants at certain sites precisely. For example, by STM-based hydrogen lithography, a single-atom transistor in which an individual P dopant atom has been placed within a silicon device with a spatial accuracy of one lattice site was demonstrated recently . In another work, by Cs atom doping with a STM tip, spin of individual magnetic molecules as basis of quantum computer was successfully controlled .
On metal surfaces, influences of tip structure on the manipulation were intensively investigated in our previous work , and it was shown that the trimer-apex tip, a model of blunt tip in the experiment, is capable of transforming the configuration of the Al nanocluster reversibly . The specific manipulation procedure also shows that the trimer-apex tip combined with the single-apex tip has potential to achieve single-atom substitutional doping in the edge of the cluster and to change its composition, which is the motivation of the present work. Usually, the edge of the Al nanocluster is modeled by stepped Al (111) surface. The extraction and position processes are studied, wherein the mechanism is the mechanical interaction force acting between the tip apex and surface. An individual atom at the step is extracted first by the tip, and then single Ag or Au dopant is positioned to this site. Based on the first-principles simulation, details of the doping process are given and its reliability is discussed.
In manipulations, the tip is moved along the X or Z direction in a certain step by changing the corresponding components of accordingly. Manipulations are simulated by molecular statics method: after each step, all atoms except the ones in the bottom layer of the slab and the top layer of the tip are fully relaxed until the forces are smaller than 0.01 eV/Å. Simulations are based on density functional theory (DFT) employing the Vienna ab initio simulation program (VASP) . The exchange-correlation potential is described by the generalized gradient approximation . Ultrasoft pseudopotentials are used for the electron-ion interactions with a cutoff energy of 129 eV . The Brillouin zone is sampled with 2 × 4 × 1 k points of a Monkhorst-Pack grid. With these parameters, the obtained lattice parameter of Ag is 4.049 Å, which compares well with the experimental value of 4.05 Å.
As shown in Figure 4a, the tip is initially placed above the vacancy site with the tip height of 8 Å at which the tip-surface interaction is almost negligible. As the tip approaches the surface step by step, the tip apex atom, i.e., the dopant atom, relaxes toward the up terrace due to the strong attraction. When the tip reaches the height of 7.1 Å, as demonstrated in Figure 4b, the dopant atom shows an obvious movement toward the up terrace since the attraction is strong enough. At this moment, two up-terrace atoms are pulled up slightly and in contact with the dopant atom (see Figure 4b). After that, we move the tip laterally in the X direction in a step of 0.2 Å at a constant height. As the tip moves forward, as shown in Figure 4c, the dopant atom drops gradually because of the decreasing vertical attraction from the tip. In the end, the dopant atom is released successfully from the tip and adsorbed at the step site (see Figure 4d). So far, the substitutional doping of the single atom is completed.
In our doping, both extraction and reposition processes only rely on the mechanical interaction force acting between the tip apex and the surface. It means that our doping scheme, in principle, can be performed with STM or AFM. For the STM tip, the electric field is inessential. Certainly, the specific parameters need to be further confirmed in the experiments. In addition, we find that the tip orientation has almost no influence on the doping process; as a result, using the tip rotated by 180° around the Z axis, we can still achieve the same results. The insensitivity to the tip orientation is beneficial to the practical experiment.
Based on first-principles simulation, we theoretically investigate the substitutional single-atom doping on stepped Al (111) surface via atomic manipulation. An effective method is proposed in which a trimer-apex tip is adopted to extract the surface atom and then a single-apex one is used to position the single dopant atom. In the positioning process, the tip moves first in the vertical direction and then in a lateral one. Both Ag and Au dopants are successfully positioned to the specific site in atomic precision, which indicates that the method owns a potential of general application. The corresponding energy curves show that both extraction and doping processes have a high reliability against thermal disturbances. Additionally, the manipulation processes are insensitive to the tip orientation, which is beneficial to the realization of such doping approach in practice.
This work is supported by the National Basic Research Program of China (973 Program) under Grant No. 2012CB934200 and Chinese NSF under Grant No. 11074042 and No. 51071048.
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