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DOI:10.1021/acs.nanolett.6b0320310.1021/acs.nanolett.6b03203

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Citation for published version (APA):Kinoshita, Y., Turanský, R., Brndiar, J., Naitoh, Y., Li, Y. J., Kantorovich, L., ... Štich, I. (2016). Promoting Atomsinto Delocalized Long-Living Magnetically Modified State Using Atomic Force Microscopy. Nano Letters, 16(12),7490-7494. https://doi.org/10.1021/acs.nanolett.6b03203, https://doi.org/10.1021/acs.nanolett.6b03203

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Download date: 08. May. 2019

Promoting atoms into delocalized long-livingmagnetically modified state

using Atomic Force Microscopy

Y. Kinoshita,† R. Turansky,‡ J. Brndiar,‡ Y. Naitoh,† Y. J. Li,† L. Kantorovich,¶

Y. Sugawara,† and I. Stich∗,‡,§

† Dept. of Applied Physics, Osaka University, Japan‡ Inst. of Physics, CCMS, Slovak Academy of Sciences, Bratislava, Slovakia

¶ Dept. of Physics, King’s College London, U.K.§ Ruprecht A. Institute of Technology, Bratislava, Slovakia

E-mail: ivan.stich@savba.sk

Abstract

We report on a low-temperature AFM manip-ulation of Co atoms in UHV on an oxidizedcopper surface in which the manipulated atomis kept delocalized above several surface unitcells over macroscopic times. The manipulationemployed, in addition to the ubiquitous short-range tip-generated chemical forces, also long-range forces generated via Friedel oscillationsof the metal charge density due to Co nanos-tructures prearranged on the surface by lateralmanipulation. We show that our manipulationprotocol requires mechanical control of the spinstate of the Co atom.

Keywords: AFM manipulation, magneticatoms, mechanical control of spin, Friedel os-cillations.

Scanning probe microscopies (SPM), such asscanning tunneling microscopy (STM) and non-contact atomic force microscopy (NC-AFM),have played a key role in constructing nanos-tructures with atomic dimensions. STM andNC-AFM have a number of unique abilitiessuch as scanning surfaces with atomic reso-lution,1 providing information on the chemi-cal identity of the scanned atoms,2 and per-haps the most fascinating ability of perform-ing nano-manipulations.3–5 Both lateral6,7 and

vertical8–10 atomic manipulations have beenperformed to build bottom-up nanostructureson surfaces either by moving the manipu-lated atoms directly6,11 or by exchanging pairsof atoms.9,12 All these manipulations havebeen performed with non-magnetic atoms onhigh-symmetry (111) and (001) substrates andhave strongly relied on short-range site-specificchemical interactions.4 Here we show that byharnessing both short- (≤5A) and long-range(≈ 5 - 40 A) interactions exerted on magneticatoms, novel manipulation protocols can be de-signed whereby in a controlled way the manipu-lated atoms can be kept in a magnetically mod-ified state which is imaged over macroscopictimes as delocalized above several surface unitcells.

Friedel oscillations13,14 of metal surfacecharge density due to adatoms or adatom su-perstructures adsorbed on it may provide anatural mechanism of long-range interactionforces exerted on an adatom which is manip-ulated by an SPM tip. However, combiningthese rather weak (in the range of meV 13,14)interactions with the short range chemical in-teraction of the adatom with the substrate(and possibly the tip) is challenging as the lat-ter interaction is rather strong (typically inthe eV range). Existence of strong short-range

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forces is essential in trapping the adatoms inthe desired positions when building nanostruc-tures, as otherwise they would be undesirablyhighly mobile at finite temperatures and beeasily moved by the tip. However, as will bedemonstrated here, if the short-range inter-action provides a highly corrugated potentialenergy surface (PES), which contains smoothplateaus separated by deep minima, then thelong-range interaction due to the surroundingadatoms provided by the Friedel oscillations,may have profound implications on the manip-ulated adatom.

One example of such a system with the re-quired form of the PES is a cobalt adatom ad-sorbed on the p(2 × 1) phase of the oxidizedCu(110) surface (p(2 × 1)Cu(110):O). The p(2× 1) surface shown in Fig. 1 has an alternatingrow/missing row conformation18,19 in the [110]direction, while along the [001] lie alternatingrows of Cu and O atoms.

All experiments were carried out with a home-built NC-AFM operating under ultrahigh vac-uum condition at 78 K. Manipulation experi-ments were performed by decreasing ∆f by -2Hz before a manipulation was attempted andswitching back to the imaging mode afterwards.We have performed two types of manipulation.While the standard lateral manipulation hasan activation barrier of ≈1 eV, the novel de-localization manipulation has a barrier twiceas large (see below). Therefore we have beenable to perform only a handful of such manip-ulations and discuss here the most illustrativeones. More experimental details can be foundin supporting information (SI).

A large-scale NC-AFM image of a p(2 × 1)terrace is shown in the right panel of Fig. 1.From the image of the c(6 × 2) phase, seenat the bottom of the figure, we can safely con-clude that both imaging and manipulation havebeen performed with an O-terminated tip,21,22

which remained stable over many hours. TheO-terminated tip images Cu atoms as brightspots,22 clearly visible in Fig. 1. The brightestspots in Fig. 1 are Co atoms which appear toadsorb preferentially in the between-O bondedpositions along the [110] direction (between twoneighboring Cu-O rows). The Co atoms in the

Figure 1: Left panel: Ball model of the p(2× 1)Cu(110):O surface, where red, yellow, andbrown balls depict O, added Cu, and bulk Cuatoms, respectively. The on-top-Cu, on-top-O,between-Cu, and between-O positions are in-dicated by yellow, blue, green, and pink cir-cles, respectively. The Co atoms, depicted ingreen, highlight the delocalization and lateralmanipulations, see the text. The inset showsthe calculated band structure around the Y-point in the Brillouin zone, see the SI, of thep(2 × 1)Cu(110):O surface projected onto p-orbitals of the oxygen-copper row. Shown fromthe top to the bottom are the unoccupied S1

surface state (pz on Cu, py on O) at ≈+0.5eV along with photoemission spectra15 (blackempty circles), the broad satellite (pz on O) de-limited from above by violet and from below byblue parabolas, experimentally detectable as abroad feature at ≈-0.2 eV16 (blue empty cir-cle), and two strong antibonding surface statesSx (px)/Sz (pz) strongly localized on the oxy-gen atoms at ≈-0.6/-0.8 eV clearly detectableexperimentally.16 The lower border of the pro-jected bulk band gap is shown by black dashedline, the upper border, not shown, is around 4eV above it. Right panel: Large-scale topo-graphic image showing Co atoms deposited onthe p(2 × 1) terrace. At the bottom of the im-age a stripe of the c(6 × 2) phase is seen. Thesquare box shows the manipulation area withfour Co atoms prearranged at suitable positionssome distance away from each other.

square box in Fig. 1 have been prearrangedin positions deemed suitable for demonstratingthe peculiar manipulation mechanism as dis-cussed below.

The atomic rearrangements in the manipu-lation area are shown in Figs. 2(a - f). The

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Figure 2: NC-AFM manipulation of Co atoms labeled 1 - 4 in panel (a). (a) - (f) sequence of imagestaken in chronological order, but not necessarily one after the other, showing the delocalizationmanipulation, (b), (e), and (f) of atoms 2, 1, and of both 1 and 2, respectively, and an ordinarylateral manipulation of atom 1 successively by two lattice parameters, (c) and (d). In (f) extractionof atom 3 by vertical manipulation is also seen. (g), (i), and (k) show three large-scale models ofthe delocalization processes from panels (b), (e), (f) and the corresponding Friedel PESs, Umod

(truncated above +25 meV close to the atomic positions), in (h), (j) and (l), calculated with 11Co atoms in the range of ≈40 A from the actual position of the manipulation event. An ellipticalFermi edge is assumed when applying Eq. (2) to predict the azimuthal dependence of the Friedelinteraction17 using m?

[001] = 0.44 me, m?[110] = 0.57 me, E0 = 0.2 eV, and δ0 ≈ π/2 as fitting

parameters. Arrows indicate the delocalized Co atoms positions in the AFM images and thecorresponding minima on the Friedel PESs. The grey grids correspond to positions of substrate Cuatoms in the AFM images. The Friedel PESs in the simple form outlined in panels h), j), l) areonly valid at high symmetry points in the surface unit cell, i.e. in the on-top-Cu (grey grids), thebetween-oxygen, and the between-Cu sites, see SI.

four relevant Co atoms are numbered in Fig.2(a). First a ”delocalization” manipulation canbe seen in Fig. 2(b), where Co atom 2 is foundspontaneously delocalized over roughly six sub-strate Cu atoms, see schematics in Fig. 1. Afterthat, a sequence of two consecutive lateral ma-nipulations of Co atom 1 in the [001] directionis seen in Figs. 2(c, d), while the Co atom 2becomes localized again. Another delocaliza-tion manipulation, this time of Co atom 1, isseen in Fig. 2(e). Finally, extraction of atom 3by a vertical manipulation shown in Fig. 2(f) isfollowed by the delocalization of atom 2 again,leaving now both atoms 1 and 2 in a delocal-ized state. While removal of atom 3 does notchange the nature of the delocalization manip-ulation, as explained below, removal of one Coatom modifies the details of the PES for atom1. Importantly, as it follows from the observedimages, the delocalization pattern remains sta-ble over macroscopic times. The experimental

life-time of the delocalization manipulation is≈1 minute for atom 2 and in excess of 20 min-utes for atom 1. The differences in life-timeof atoms 1 and 2 reflect the statistical nature ofthe manipulation process and/or the differencesin surrounding Co atoms that create a differentpotential well around these two positions.

The lateral manipulations represent a fairlystandard type of a manipulation customarilyobserved in the past.6,7 The vertical manipu-lation appears similar to that observed on thep(2 × 1) surface for Cu atoms.10 However, tothe best of our knowledge, the observed delo-calization of atoms over the regions comprisedof the multiple substrate atoms, represents anovel type of manipulation induced, as we ar-gue below, by the activation of the long-rangeforces in the manipulation process triggered bythe Co atom spin change.

To rationalize the observed long-lived delocal-ized state of the Co atoms during their manip-

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Figure 3: Top panel: Experimental images (a-c) of the atom lateral, from a) to b), and de-localization, c), manipulations, placed on topof the DFT calculated (U = 0) adiabatic PES,Usr, d), of the Co atom in the [Ar]d8 state onthe p(2 × 1)Cu(110):O surface. The circularcharacter of the image of the Co atom in thedelocalized state is clearly seen in c). Bottompanel: Detailed representation of PESs, in eV,along on-top-Cu – on-top-O – on-top-Cu ([001]direction, red lines) and on-top-Cu – betweenCu – on-top-Cu ([110] direction, blue lines) di-rections in [Ar]d7 (full lines) and [Ar]d8 (dashedlines) local Co spin configurations for U = 9 eV(dark color) and for U = 7 (light color). Notethat the PESs in the [Ar]d7 state for U = 9 eVand U = 7 eV are barely distinguishable on thescale of the figure (half shown in red and half inpink); the main difference being that the [Ar]d7

configuration is unstable in the on-top-O posi-tion for U = 7 eV and transforms into [Ar]d8

(depicted by arrows). For details see SI.

ulation, we performed extensive density func-tional theory (DFT) calculations for [Ar]d7 and[Ar]d8 Co configurations. A series of U = 0eV calculations was run first for the entire PESwhich is shown in the upper panel of Fig. 3.Only the [Ar]d8 Co configuration was found sta-ble over the entire PES. The U = 0 eV calcu-lations were followed by test calculations withU ∈ (4-9) eV. The effect of U is to localize thed electrons spatially and thus make them lessreactive. Increasing the value of U leads to aless corrugated PES with larger plateaus overthe on-top-Cu positions; it does not, however,modify qualitatively the form of the PES as be-comes clear from the potential energy curvescalculated along two particular directions onthe surface and shown in the lower panel ofFig. 3 (more details are in the SI).

The calculated adiabatic PES for a single Coatom over the p(2 × 1)Cu(110):O surface iscorrelated with the manipulation processes ob-served experimentally, see Fig. 3. The PES ofthe [Ar]d8 state depicts only the short-rangepart, Usr, of the interaction potential actingon a Co atom due to the surface. The PESis highly unusual, featuring very large (≈2×3A2) barely corrugated plateaus over added rowCu atoms (blue areas on the PES) connected byvery shallow (0.1 - 0.2 eV) minima in the [001]direction along the Cu-O-Cu added row (redline) and [110] direction (blue line) in-between-Cu atoms. On the contrary, the PES is highlycorrugated (≈ 1 eV, brown areas) in-between(green line) and across (the brown line) the oxy-gen atoms where the absolute minima at thebetween-O bonded sites lie. Hence, while thebetween-O bonded sites are able to firmly an-chor the Co atoms in [Ar]d8 state, they canbe laterally manipulated by the tip betweenthese sites along the [001] direction, the processshown in Fig. 2(c, d).

The spin state of the delocalized Co atom ispredicted to assume the less reactive atomic-like [Ar]d7 configuration, Fig. 3. The delocal-ization manipulation, Figs. 2(b, e, f), requiresfirst for the manipulated Co atom to assume anon-top-Cu atom position, which clearly meanssurmounting a large barrier of ∼2 eV and the[Ar]d8 → [Ar]d7 local spin modification. This

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process is stochastic and has a fairly small prob-ability. However, once the Co atom is promotedonto the plateau over the added row Cu atom,it accepts the lower energy [Ar]d7 state, andthen the tiny minima separating the plateaus(see the bottom panel in Fig. 3) can be eas-ily bridged by the tip. Hence the atom may,with a high probability, remain in the weaklycorrugated part of the PES for a long time atsmall enough temperatures. The flatness of thePES along the smeared out manipulation tra-jectory is supported also by the absence of asignal from the dissipation channel. Contrary,assuming that the Co atom retains its [Ar]d8

ground-state spin configuration means that itwould have to surmount a huge energy barrierof ≈ 1.2 eV, Fig. 3, on passing between theexperimentally visited on-top-Cu positions viathe between-Cu position, in clear disagreementwith the manipulation images in Fig. 2. Notethat by promoting Co atom into the metastableon-top-Cu [Ar]d7 state, the NC-AFM tip effec-tively performs a mechanical control of the localCo spin configuration.

The potential Usr in Fig. 3(d) predicts onlymanipulation of atoms along straight lines. Inorder for the trajectory to assume a smearedout circular path, as observed experimentally,an additional modulation potential, Umod, isneeded to localize the Co atom on the plateau.Since the manipulation was observed on severalsites, Umod could not be generated by surfacedefects. Also, it cannot be caused by the sur-face stress28 induced by adsorbed Co atoms asit decays monotonically from them. We pro-pose that Umod is generated by the long-rangeinteraction between the Co adatoms caused byFriedel charge density oscillations around themdue to an effective surface state. Indeed, a p(2× 1)Cu(110):O photoemission spectrum showsan unoccupied parabolic surface state at around+0.4 eV15,16 along the [001] direction, S1 inFig. 1, and a broad occupied surface oxygenstate at ≈-0.2 eV with respect to Fermi energy,Ss, see Fig. 1, forming effectively a satellite tothe S1 state. The S1 state, with a similar dis-persion along the [110] direction, was also foundin DFT calculations.20 However, to the bestof our knowledge, the Ss feature has not been

identified by DFT calculations as yet.Our DFT calculations, see left panel of Fig. 1

and SI, show an occupied band of surfacestates on the pristine p(2 × 1) surface able toscreen the interaction between Co atoms via theFriedel oscillation mechanism. These surfacestates are further lowered in energy by ≈0.15eV upon adsorption of a Co atom, see SI. Weapproximate that band of states by an effectivesurface state Seff with an asymmetric parabolicdispersion

E(~k) =h2k2

x

2m?[001]

+h2k2

y

2m?[110]

− E0 , (1)

with E0 being the minimum energy offset.In the simplest approximation the pairwise

interaction between two adatoms placed rela-tively to each other by a vector ~r due to theFriedel oscillation mechanism is 13,14

Umod(~r) ∝sin(2 ~kF · ~r + 2δ0)

( ~kF · ~r)2, (2)

where kF is the Fermi wave vector of the surfacestate electrons and δ0 is the phase shift describ-ing the scattering properties of the Co atom.For a generalization to an elliptical Fermi edgeactually used in our modeling, see SI.

The plots in Figs. 2 (h, j, l) show Umod(~r) sim-ulated by summing up pair-wise contributionsfrom all Co atoms within a circle of ≈40 A ra-dius taken around the Co atom(s) of interest,as shown in our images of the delocalizationprocesses in Fig. 2 (b, e, f), respectively. De-spite approximations made (pair-wise interac-tions, neglect of the structural relaxation uponCo atom adsorption, the fitting procedure) theyindeed predict minima at positions correspond-ing to the delocalization pattern observed ex-perimentally. All the minima of Umod experi-mentally observed correspond to the first min-ima of the Friedel oscillating interaction gener-ated mainly by atoms 1 - 4, and azimuthallymodulated by other atoms surrounding them.The only exception being the minimum corre-sponding to atom 1 in Fig 2 (l) which, due toremoval of atom 3, now features a much weakersecond minimum. In this case, though, the

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minimum is circularly surrounded by four max-ima and hence forms a spatially well distinctentity. While relatively weak, the Umod maystill provide a restricting potential sufficient toconstrain the Co atom on the plateau. More-over, due to very small energy barriers within it(small corrugation of Usr), the Co atom will behighly mobile there. This high mobility withina small lateral region is manifested itself in thecircularly shaped smeared out NC-AFM imagestaken by a relatively slowly moving tip duringthe scan.

As evident from Fig. 2, the delocalization pat-tern may be controlled by specific pre-definedpositions of the surrounding Co atoms, ad-justable by ordinary lateral manipulation, thatwould provide the desirable long-range con-straining potential Umod, which, in general,need not limit the delocalization pattern to sixsubstrate atoms, see also SI. In principle, themanipulated magnetic atom could be encapsu-lated into a “Friedel cage”and kept localizedaround the on-top-Cu position.

In summary, we have performed manipulationof Co atoms on a lower-symmetry substrate, thep(2 × 1)Cu(110):O surface, under the combinedaction of short-range chemical forces inducedby the tip of the microscope and the surface,and long-range forces induced via Friedel os-cillations of charge density due to other adsor-bates. We have observed a novel manipulationof Co atoms that could be kept, over macro-scopic times, delocalized above several surfaceatoms. We demonstrate that the manipulationis possible due to the modification of the spinstate of the manipulated atom, and hence wealso demonstrate the possibility of mechanicalcontrol over the spin state of the atom as aresult of the manipulation. This may be ofimportance for spintronics applications.29 Simi-larly the d8↔ d7 “control”of the magnetic stateof the Co atom on graphene was achieved byIr(111) ↔ Ru(0001) substrate modification.30

Methods. In our experiments the deflectionof the cantilever was detected by optical in-terferometer. The frequency-modulation tech-nique was used to detect the tip-sample inter-action. Commercially available Si cantilevers(n-type, Nanoworld NCL, 40 Nm−1, 150 kHz)

were used. The tip apex was cleaned in situ byAr ion bombardment at an energy of 0.6 keV.The frequency shift of the oscillating cantileverwas measured by using phase-locked-loop-basedcommercial electronics (easyPLL plus detectorand controller, Nanosurf, Liestal, Switzerland).The Cu(110):O surface was prepared by clean-ing using repeated Ar ion sputtering and sub-sequently annealing at 550◦C, followed by ex-posure of oxygen at 300◦C. The set point offrequency shift was selected in the range of -30Hz to -37 Hz. Weak low pass image filteringwas used.

In our calculations the surface was modelledusing a five layer Cu-slab with the upper threeatomic layers allowed to relax.21,22 Calculationsof the energies and forces were performed us-ing DFT with projector augmented-wave pseu-dopotentials23 and 500 eV plane wave cut-off asimplemented in the VASP code.24 Since van derWaals interactions were found to be essentialfor the O-terminated Cu surfaces,25 this inter-action was accounted for here using the vdW-DF2 scheme.26 The effect of electronic correla-tion of localized Co d electrons was taken intoaccount by DFT+U method with U between 7and 9 eV.27 All calculations were performed inglobal spin quartet multiplicity. More simula-tion details can be found in SI.

Acknowledgement Work supported bythe Grant-in-Aid for Scientific Research ofJapan, by APVV-0207-11, VEGA (2/0007/12,2/0162/15) projects. We also gratefully ac-knowledge use of the Hitachi SR16000/M1 su-percomputer system at CCMS/IMR, TohokuUniversity, Japan.

Supporting Information Available: Fur-ther experimental and computational details,such as additional AFM images, computedshort-range PESs, and discussion of generaliza-tion of the Friedel PESs for off-zone center sur-face states are summarized in SI. This mate-rial is available free of charge via the Internetat http://pubs.acs.org/.

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Graphical TOC Entry

AFM delocalization manipulation of a Co atom on p(2 × 1)Cu(110):Osurface (left arrow) and its explanation by long-range Friedel forces ex-erted by the other Co adsorbates on the surface (right arrow).

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