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On-surface metalation of metal-free π-conjugated planar molecules, such as metal-free tetraphenylporphyrin (2HTPP), using 3d transition metals prepared in ultrahigh vacuum (UHV), attracted signific...

Crown-ether (CR) ring molecules are known as host molecules for capturing guest species inside the ring. So far CR molecular films have only been grown by drop-casting a CR solution on an inert sub...

We report that the occurrence of a Kondo effect in magnetic molecules crucially depends on the point symmetry and oxidation state of the adsorbed species. Two different transition metal acetylacetonate (acac) compounds [$M{(\mathrm{acac})}_{3}$, with $M=\mathrm{Cr}(\mathrm{III})$ or Co(III)] adsorbed on a Cu(111) single crystal were investigated to demonstrate the interplay. After deposition, $\mathrm{Cr}{(\mathrm{acac})}_{3}$ molecules formed threefold symmetric $\mathrm{Cr}{(\mathrm{acac})}_{3}$ and twofold symmetric $\mathrm{Cr}{(\mathrm{acac})}_{2}$ by releasing a ligand, while $\mathrm{Co}{(\mathrm{acac})}_{3}$ molecules only formed twofold symmetric $\mathrm{Co}{(\mathrm{acac})}_{2}$. Threefold symmetric $\mathrm{Cr}{(\mathrm{acac})}_{3}$ molecules with a total electron spin $S=\frac{3}{2}$ exhibited no Kondo effect, while a clear Kondo resonance was observed in twofold $\mathrm{Cr}{(\mathrm{acac})}_{2}$ molecules. $\mathrm{Co}{(\mathrm{acac})}_{2}$ molecules surprisingly showed no Kondo resonance, even in the case of twofold symmetry, which is explained by a low-spin state of $S$ = 0. To analyze the results, a simple model is proposed based on the total electron spin and the symmetry of magnetic molecule. The present approach provides a feasible design strategy for single molecule magnets on metallic surfaces.

We report an ultra-high-vacuum low-temperature (4.6 K) scanning tunneling microscopy study of the molecular structure and dynamics of a carbon monoxide (CO) monolayer adsorbed at 20 K on Cu(111). We observe the well-known 1.4 × 1.4 phase of CO/Cu(111) for the first time in real-space imaging. At 4.6 K, the hexagonal symmetry of the monolayer is locally broken by the formation of stripes made of single and double CO rows of different apparent heights. Using density functional theory calculations, we assign the high rows to CO molecules adsorbed mostly at off-center top sites and the low rows to bridge sites. Groups of three or four very high molecules appear randomly and are assigned to nearest-neighbor, titled top site molecules. We observe simultaneous hopping of a few CO molecules between adjacent top and bridge sites, which produces the apparent motion of the stripe pattern.

Oxidative vaporization in air using a flame with a temperature range of 1950–2300 K was employed for controlling the tip shape made from a nipper-cut metal molybdenum (Mo) wire edge. An extremely high vapor pressure of MoO3 generated on the Mo surface in flame is a driving force behind the tip shape formation. Since the MoO3 vaporization rate follows the flame temperature gradient, we could control the tip apex shape by selecting the proper flame etching condition. The best condition to obtain a sharp tip apex based on statistical tests of dozens of Mo tips was obtained by Mo wire edge insertion into the 2100 K flame from the side for one second. This was repeated twice, which reproducibly provided a tip apex with a radius of 50–100 nm and a cone angle of 20–30 degrees. The present Mo tips, fabricated without aqueous solutions, were examined for their suitability as probe tips through air-scanning tunneling microscopy (STM), ultrahigh vacuum STM, field emission spectroscopy, and conductance measurements.

In this combined experimental and theoretical work, we report on the evolution of the skyrmion radius and its destruction in the system Co/Ru(0001) when an out-of-plane magnetic field is applied. At low fields, skyrmions are metastable and display an elliptical instability in which along the short axis, the spin texture approaches that of the spin-spiral phase and the long axis expands in order to go back to the spin-spiral ground state. At high fields, we observe round skyrmions of finite size up to the collapse field Bc, where they are destroyed and the topological charge is annihilated. We estimate Bc via numerical methods based on magnetization dynamics simulations parametrized by density functional theory calculations and compare it to experimental scanning tunneling microscopy observations obtained at ≈ 30 mK.

Precise control of organic molecule deposition on a substrate is quite important for fabricating single-molecule-based devices. In this study, we demonstrate whether a quartz-crystal microbalance (QCM) widely used for a film growth calibration has the ability to precisely measure the number of organic molecules adsorbed on a substrate. The well-known Sauerbrey’s equation is extended to formulate the relation between QCM resonant frequency shift and the number of adsorbed molecules onto the QCM surface. The formula is examined by QCM measurements of sublimation of π-conjugated organic molecules and direct counting of the deposited molecules one by one onto metal substrates, using ultrahigh vacuum low-temperature scanning tunneling microscopy (STM). It is revealed that the number of adsorbed molecules evaluated by QCM (NQCM) show good agreement with those counted from the STM images (NSTM) within the error of ±25%. The results ensure the QCM capability for controlling the deposition number of organic molecu...

Spin-polarized scanning tunneling microscopy (SP-STM) is a powerful tool to visualize spin-polarization vectors of sample surface atoms.

Band gap opening of a single-layer graphene nanoribbon (sGNR) sitting on another sGNR, fabricated by drop casting GNR solution on Au(111) substrate in air, was studied by means of scanning tunneling microscopy and spectroscopy in an ultra-high vacuum at 78 K and 300 K. GNRs with a width of ~45 nm were prepared by unzipping double-walled carbon nanotubes (diameter ~15 nm) using the ultrasonic method. In contrast to atomically-flat GNRs fabricated via the bottom-up process, the drop cast sGNRs were buckled on Au(111), i.e., some local points of the sGNR are in contact with the substrate (d ~ 0.5 nm), but other parts float (d ~ 1–3 nm), where d denotes the measured distance between the sGNR and the substrate. In spite of the fact that the nanoribbons were buckled, dI/dV maps confirmed that each buckled sGNR had a metallic character (~3.5 Go) with considerable uniform local density of states, comparable to a flat sGNR. However, when two sGNRs crossed each other, the crossed areas showed a band gap between −50 and +200 meV around the Fermi energy, i.e., the only upper sGNR electronic property changed from metallic to p-type semiconducting, which was not due to the bending, but the electronic interactions between the up and down sGNRs.

An important step toward molecule-based electronics is to realize a robust and well-ordered molecular network at room temperature. To this end, one key challenge is tuning the molecule–substrate electronic interactions that influence not only the molecular selfassembly but also the stability of the resulting structures. In this study, we investigate the film formation of π-conjugated metal-free phthalocyanine molecules on a 3d-bcc-Fe(001) whisker substrate at 300 K by using ultra-high-vacuum scanning tunneling microscopy. On bare Fe(001), hybridization between the molecular π and the Fe(001) d-states prevents the molecular assembly, resulting in the disordered patchy structures. The second- and third-layer molecules form densely packed films, while the morphologies show clear difference. The second-layer molecules partially form p(5 × 5)-ordered films with the rectangular edges aligned along the [100] and [010] directions, while the edges of the third-layer films are rounded. Remarkably, such film morphologies are stable even at 300 K. These findings suggest that the molecular self-assembly and the resulting morphologies in the second and third layers are affected by the substrate bcc(001), despite that the Fe-d states hybridize only with the first-layer molecules. The possible mechanism is discussed with the kinetic Monte Carlo simulation.

One-nm-size single organic molecules have attracted interest as a key material to realize ultra-small spintronic devices such as single-molecule giant magnetoresistance memory. The origin of such magnetic phenomena is spin polarization vector in the single molecules induced by contacting magnetic electrodes. Atomically resolved spin-polarized STM has been used to measure quantitatively the spin polarization; however, in this study we point out that the reported method includes crucial ambiguity. By using the normalized differential conductance (dI/dV)/T, the true spin polarization of the single molecules on magnetic domains is revealed.

A tungsten (W) tip has been used as a standard tip probe because of its robustness at the highest boiling temperature; the use cases include a field emission (FE) electron source for scanning electron microscopy (SEM) and a scanning probe microscopy tip. The W tip probe has generally been fabricated through a chemical etching process with aqueous solutions. In this study, we propose a new method—flame etching. Without using aqueous solutions, a W tip probe was successfully fabricated within 3 s in air, which is very fast and convenient, and beneficial for mass production (additionally, no expensive setup is necessary). A W tip probe was obtained simply by putting a W wire into an oxygen-liquefied petroleum (O2+LP) gas flame (giving the highest temperature of ∼2300 K) through a microtorch for a few seconds. The obtained W tip provided atomically resolved scanning tunneling microscopic images. Also, since FE electrons were detected by applying ∼106 V/m, the tip can be used as an FE-SEM source. Generation and vaporization of WO3 on the W surface are important processes to form a tip shape.

The realization of single molecular electronics is considered the next frontier to addressing and sustaining the storage needs of the future. In order to realize a single molecular device working at 300 K, two conditions must be satisfied: first, there must be no molecular diffusion, i.e., robust bonding between molecules and the contacting electrode, and second, stable electronic interface states. In this study, using a combination of 7-K and 300-K ultrahigh vacuum scanning tunneling microscopy/spectroscopy experiments and theoretical ab initio calculations, we investigated the adsorption of $\ensuremath{\pi}$-conjugated metal-free phthalocyanine (Pc) single molecules onto an Fe(001) whisker single crystal along with the resulting electronic interface structures. The Pc/Fe(001) system was found to prevent molecular diffusion even at 300 K, due to strong adsorption as well as the presence of a larger diffusion barrier than that of the Pc/Ag(001) system, in which molecules are known to diffuse at 300 K. The origin of such a robust bonding was studied by recovering the sample local density of states (LDOS) with the normalized $(dI/dV)/T$ curves, where the LDOS peaks are successfully explained by theoretical calculations.

A clean tungsten (W) tip apex with a robust atomic plane is required for producing a stable tunneling electron emission under strong electric fields. Because a tip apex fabricated from a wire by aqueous chemical etching is covered by impurity layers, heating treatment in ultra-high vacuum is experimentally known to be necessary. However, strong heating frequently melts the tip apex and causes unstable electron emissions. We investigated quantitatively the tip apex and found a useful method to prepare a tip with stable tunneling electron emissions by controlling electron-bombardment heating power. Careful characterizations of the tip structures were performed with combinations of using field emission I-V curves, scanning electron microscopy, X-ray diffraction (transmitted Debye-Scherrer and Laue) with micro-parabola capillary, field ion microscopy, and field emission microscopy. Tips were chemically etched from (1) polycrystalline W wires (grain size ∼1000 nm) and (2) long-time heated W wires (grain size larger than 1 mm). Heating by 10-40 W (10 s) was found to be good enough to remove oxide layers and produced stable electron emission; however, around 60 W (10 s) heating was threshold power to increase the tip radius, typically +10 ± 5 nm (onset of melting). Further, the grain size of ∼1000 nm was necessary to obtain a conical shape tip apex.

Magneto-electric coupling offers a new pathway to information storage in magnetic memory devices. This phenomenon has been observed in various materials ranging from insulators to semiconductors. In bulk metallic systems, magneto-electric coupling has been disregarded as the electric field cannot enter bulk metals. In this work, we show that a substantial magneto-electric coupling exists in metallic Fe nano-islands grown on Cu(111). Using the electric field in the tunnel junction of a scanning tunneling microscope, the magnetic order parameter and the crystal structure of Fe was changed on the nanometer scale. This allows high density nonvolatile information storage by means of magneto-electric coupling in a simple metallic system.

Magnetoelectric coupling at metal surfaces opens up a new possibility for metallic non-volatile magnetic data-storage devices, in which the magnetic bits are controlled by an electric field. We studied the atomic and magnetic order in bilayer Fe nano-islands grown on a Cu(111) substrate with a scanning tunneling microscopy setup in ultra-high vacuum at 4.5 K. Electric field pulses (108-109 V/m) were found to be able to cause a displacement of the Fe atoms, switching simultaneously the crystalline and the magnetic order, which is the prove of magnetoelectric coupling at the metallic Fe surface. We also succeeded in controlling the direction of the switching by the polarity of the electric field.

Understanding the interactions between a tip apex and a target atom or molecule is crucial for the manipulation of individual molecules with precise control by using scanning tunnelling microscopy (STM) and atomic force microscopy. Herein, we demonstrate the manipulation of target CO molecules on a Cu(111) substrate using a CO-functionalized W tip with atomic-scale accuracy. All experiments were performed in a home-built ultra-high vacuum STM system at 5 K. The CO-tip was fabricated by picking up a single CO molecule from a Cu(111) surface. In contrast to a metal tip, repulsive interactions occur between the CO-tip and the target CO molecule. This repulsive interaction promises perfect lateral hopping without any vertical hopping. Hopping events were directly monitored as sudden current drops in the simultaneously measured I-z curves. A larger barrier height between the CO-tip and the target CO (∼9.5 eV) was found from the slope of the I-z curve, which decreases the electron tunnelling probability between the tip and sample. Therefore, electron-driven manipulation cannot be a major trigger for the CO-CO repulsive manipulation. The CO-tip is able to manipulate only the target CO molecule, even when another CO molecule was located ∼0.5 nm away. Statistical measurements revealed that the nearest neighbour atop site is the energetically stable position after hopping. However, if the CO target has another CO molecule in a neighbouring position (denoted as a 'pair'), the target CO hops more than twice as far. This means that the CO-tip experiences a larger repulsive interaction from the pair. These observations of CO-tip manipulation are useful for the design of two-dimensional artificial molecular networks as well as for developing a better understanding of catalytic oxidation processes.

Hexagonal-pillar shaped pure Fe single crystal whiskers with six {1 1 0} side planes were obtained by means of chemical vapor deposition. Atomically resolved scanning tunneling microscopy images obtained on the {1 1 0} surface showed a quasi-hexagonal atomic array with mesoscopic-range periodic height modulation of about 1/3 of an atomic step. This height modulation was found to be a result of an interference between the quasi-hexagonal top-layer and the sub-surface bcc-Fe{1 1 0} layer. Unit vectors of the mesoscopic-range modulation turned out to be expressed as p 1 → p 2 → = 13 1 - 2 14 u 1 → u 2 → = 12 1 - 3 15 s 1 → s 2 → , where u 1 → u 2 → and s 1 → s 2 → are the primitive vectors of the two-dimensional atomic array in the top-layer and those in the sub-surface layer, respectively. The two-dimensional density of atoms in the top-layer is slightly higher by 0.46% than that in the sub-surface layer.

One feature of the alpha3-peptide, which has the amino acid sequence of (Leu-Glu-Thr-Leu-Ala-Lys-Ala)(3), that distinguishes it from many other alpha-helix-forming peptides is its ability to form fibrous assemblies that can be observed by transmission electron microscopy. In this study, the effects of Ala-->Gln substitution at the e (5th) or g (7th) position in the above heptad sequence of the alpha3-peptide on the formation of alpha-helix and fibrous assemblies were investigated by circular dichroism spectral measurement and atomic force microscopy. The 5Qalpha3-peptide obtained by Ala-->Gln substitution at the e position of the alpha3-peptide was found to form very short fibrils with long-elliptical shape, whereas the 7Qalpha3-peptide with Gln residues at the g position lost its ability to form such assemblies, in spite of alpha-helix formation in both peptides; the stabilities of both peptides decreased. These results indicate that Ala residues at the g position in the heptad sequence of the alpha3-peptide are key residues for the formation of fibrous assemblies, which may be due to hydrophobic interactions between alpha-helical bundle surfaces.

A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs.

A simple method for fabricating single-layer graphene nanoribbons (sGNRs) from double-walled carbon nanotubes (DWNTs) was developed. A sonication treatment was employed to unzip the DWNTs by inducing defects in them through annealing at 500 °C. The unzipped DWNTs yielded double-layered GNRs (dGNRs). Further sonication allowed each dGNR to be unpeeled into two sGNRs. Purification performed using a high-speed centrifuge ensured that more than 99% of the formed GNRs were sGNRs. The changes induced in the electrical properties of the obtained sGNR by the absorption of nanoparticles of planar molecule, naphthalenediimide (NDI), were investigated. The shape of the I-V curve of the sGNRs varied with the number of NDI nanoparticles adsorbed. This was suggestive of the existence of a band gap at the narrow-necked part near the NDI-adsorbing area of the sGNRs.

Intermixing, growth, geometric and electronic structures of gold films grown on antiferromagnetic stacking body-centered-tetragonal manganese (0 0 1) films were studied by means of scanning tunneling microscopy/spectroscopy at room temperature in ultra-high vacuum. We found stable ordered c(2 × 2)-MnAu(0 0 1) alloy layers after depositing Au on pure Mn layers. Since at the fourth layer (5 × 23)-like Au reconstruction appears instead of the c(2 × 2) structure and local density of states peaks obtained on the c(2 × 2)-MnAu surface disappear, pure Au layers likely grow from the fourth layer.

To elucidate the magnetic properties of a magnetic multilayer film, an understanding of the local geometry, electronic structure, and possible intermixing at the interfaces is of utmost importance. By gradually increasing the Fe coverage on the Mn(001) film, we obtained this information on the interface region by means of Auger spectroscopy and scanning tunneling microscopy/spectroscopy. Intermixed atoms and various geometries and density of states are found to exist in this system.

Normalized differential tunneling conductivities obtained with Fe-coated W tips show a spin-polarized peak around +0.8 V on ultrathin bct Mn films grown on Fe(001)-whiskers. This spin-polarized peak results in a clear magnetic contrast in spectroscopic images. Our normalization removes the influence of the tunneling probability and makes the spectroscopic curves most reliable for a derivation of the spin-resolved sample density of states (DOS) at positive voltages. From this analysis we conclude that the magnetic contrast in our spectroscopic maps is caused by a highly polarized DOS. Furthermore, a tip polarization of about 15% is found.

The growth of ultrathin Mn films on an Fe(0 0 1) whisker at 370 K is studied by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy at room temperature in ultrahigh vacuum. Atomically and chemically resolved STM images show that the Mn film grows with the same in-plane lattice constant as Fe(0 0 1) and that Fe atoms intermix with the first (14%), the second (4%), and the third Mn layer (2%), while a negligible amount of Fe atoms is found above the third layer. The growth mode changes from layer-by-layer to layer-plus-island at a coverage of 3 ML Mn. dI/dV curves which are normalized by voltage-dependent tunneling probability functions show clear peaks on each Mn layer. These peaks are tentatively ascribed to surface states. On the first Mn layer, peaks are found at +0.35 eV on pure Mn areas and at +0.28 eV on mixed MnFe areas. The second and the third Mn layer show peaks at +0.20 and +0.8 eV, respectively. Mn films thicker than three layers reveal besides a strong peak at +0.8 eV a weaker peak at −0.6 eV. Our apparent step height measurements show that the Mn film relaxes at the third layer: the interlayer spacing is ∼0.16 nm for the first two layers, and it increases to ∼0.18 nm at the third layer. Starting from the fourth layer the interlayer spacings are geometrically equivalent (∼0.165 nm).

The submonolayer growth of Mn on Fe(0 0 1) in the temperature range between 50 and 200 °C is studied by scanning tunneling microscopy and scanning tunneling spectroscopy. For growth temperatures above 100 °C, atomically resolved STM images with chemical contrast clearly reveal the incorporation of Mn atoms in the Fe(0 0 1) substrate. The fraction of place exchanged Mn atoms is observed to increase with growth temperature. Although on islands a c(2×2) structure forms locally which is attributed to an ordered MnFe surface alloy, long range order could not be obtained for the growth temperatures and coverages studied. Spectroscopy results are presented for clean Fe(0 0 1), pure Mn ad-islands, single incorporated Mn atoms and c(2×2)-ordered MnFe areas. In contrast to embedded Cr atoms in the Fe(0 0 1) surface [Phys. Rev. Lett. 76 (1996) 4175], isolated embedded Mn atoms do not lead to double peak structures in d I /d V curves. Nevertheless, on the ordered c(2×2) MnFe structure and the pure Mn monoatomic islands surface states are detected as peaks in the d I /d V and (d I /d V )/( I / V ) curves. However, due to the strong influence of a tip-dependent background on these peaks, the corresponding surface state energies cannot be found directly from those curves. The real surface state energies were recovered by normalizing the measured d I /d V curves by fitted quadratic backgrounds. Thus, surface state energies of about +0.35 and +0.25 eV are estimated for pure Mn islands and alloyed MnFe areas, respectively.

Giant magnetoresistance (GMR) through a single phthalocyanine molecule (H2Pc) was studied by means of a spin-polarized scanning tunneling microscopy (STM) technique. Spin-polarized STM shows surface electronic spin and quantum structures of nano materials, such as single atoms, single molecules, nano-clusters, with an atomic resolution. Single molecular magnetic junction was fabricated by contacting a ferromagnetic STM tip to a single molecule adsorbed on nano magnets. We measured GMR of +60% and -50% through [Co/H2Pc/Co(111)] and [Fe/H2Pc/Mn(001)] junctions, respectively, in ultra-high vacuum at 4.6K. Single organic molecules can be a new material for spintronics.

Various surface configurations of Cs/p-GaAs(1 1 0) have been studied by scanning tunneling microscopy and scanning tunneling spectroscopy with an interest in relation to the photoelectron emission. The local work function is found to be 4.8, 3.3, and 3.3 eV from clean p-GaAs(1 1 0), Cs one-dimensional (1D) lines (Cs coverage of 0.23 ML), and partially-ordered Cs polygons (Cs coverage of 0.5 ML), respectively. It is understood that only a coherently c(4×4)-ordered Cs-polygon surface (Cs coverage of 0.6 and 0.7 ML) can emit photoelectrons due to a sufficient reduction of the local work function down to 1.3 eV to get the negative electron affinity state. The local work function image shows that the boundary of Cs atoms has a lower local work function than at the top of Cs atoms.

The control of atomically flat interfaces between iron (Fe) and insulating oxide films, such as the Fe/MgO(001) interface, is crucial for tunnel-magnetoresistance (TMR) devices. However, the realization of an ideal atomically flat and clean interface is rather difficult since iron easily binds to impurities such as oxygen. Atomic step defects and iron oxide at the interface could reduce TMR. In this study, the oxidization of an atomically flat and clean Fe(001)-whisker single crystal at different substrate and annealing temperatures was investigated with an ultrahigh-vacuum scanning tunneling microscope (STM). Annealing up to a temperature of 850 K was required to obtain ordered and atomically flat Fe(001)-p(1×1)O terraces after the oxidization with the coexistence of Fe–O nanoislands (∼1 nm in height, ∼50 nm in size). We found that the growth of such nanoislands, which enhances interface roughness, strongly depends on the substrate temperature (T S) during the oxidization. A T S lower than 300 K reduces the coverage by the nanoislands to less than 10%.

The present letter describes a method to make a spin-polarized scanning tunneling microscopy tip by applying voltage pulses between a W tip and a magnetic sample. This spin-polarized tip has the similar characteristics as an Fe-coated W tip, which was confirmed by observations of antiferromagnetically coupled ferromagnetic Mn(001) layers (>3 ML) grown on an Fe(001) whisker at 370 K. Furthermore, we demonstrate that these voltage pulses can vary the tip magnetization direction.

The magnetoresistance of a hydrogen-phthalocyanine molecule placed on an antiferromagnetic Mn(001) surface and contacted by a ferromagnetic Fe electrode is investigated using density functional theory based transport calculations and low-temperature scanning tunneling microscopy. A large and negative magnetoresistance ratio of ∼50% is observed in combination with a high conductance. The effect originates from a lowest unoccupied molecular orbital (LUMO) doublet placed almost in resonance with the Fermi energy. As a consequence, irrespective of the mutual alignment of magnetizations, electron transport is always dominated by resonant transmission of Mn-majority charge carries going through LUMO levels.

We demonstrate that with the help of Scanning Tunneling Microscopy (STM), spintronic functions can be realized with single molecules.

A nanoscale molecular switch can be used to store information in a single molecule. Although the switching process can be detected electrically in the form of a change in the molecule's conductance, adding spin functionality to molecular switches is a key concept for realizing molecular spintronic devices. Here we show that iron-based spin-crossover molecules can be individually and reproducibly switched between a combined high-spin, high-conduction state and a low-spin, low-conduction state, provided the individual molecule is decoupled from a metallic substrate by a thin insulating layer. These results represent a step to achieving combined spin and conduction switching functionality on the level of individual molecules.

Magnetoresistance is a change in the resistance of a material system caused by an applied magnetic field. Giant magnetoresistance occurs in structures containing ferromagnetic contacts separated by a metallic non-magnetic spacer, and is now the basis of read heads for hard drives and for new forms of random access memory. Using an insulator (for example, a molecular thin film) rather than a metal as the spacer gives rise to tunnelling magnetoresistance, which typically produces a larger change in resistance for a given magnetic field strength, but also yields higher resistances, which are a disadvantage for real device operation. Here, we demonstrate giant magnetoresistance across a single, non-magnetic hydrogen phthalocyanine molecule contacted by the ferromagnetic tip of a scanning tunnelling microscope. We measure the magnetoresistance to be 60% and the conductance to be 0.26G(0), where G(0) is the quantum of conductance. Theoretical analysis identifies spin-dependent hybridization of molecular and electrode orbitals as the cause of the large magnetoresistance.

We have studied the magnetic configuration in ultrathin antiferromagnetic Mn films grown around monoatomic steps on an Fe(001) surface by spin-polarized scanning tunneling microscopy/spectroscopy and ab-initio-parametrized self-consistent real-space tight binding calculations in which the spin quantization axis is independent for each site thus allowing noncollinear magnetism. Mn grown on Fe(001) presents a layered antiferromagnetic structure. In the regions where the Mn films overgrows Fe steps the magnetization of the surface layer is reversed across the steps. Around these defects a frustration of the antiferromagnetic order occurs. Due to the weakened magnetic coupling at the central Mn layers, the amount of frustration is smaller than in Cr and the width of the wall induced by the step does not change with the thickness, at least for coverages up to seven monolayers., 10 pages, 5 figures

Spin-polarized scanning tunneling microscopy and spectroscopy (SP-STM/STS) opens up new real atomic scale magnetism. Interlayer exchange coupling of ultrathin Fe(001) films grown on the antiferromagnetically stacked bct-Mn(001) layers have been studied. The ordered c(2x2)-MnAu(001) surface alloy films were studied and found a high magnetic moment for Mn spins (>4 Bohr magneton), an antiferromagnetic coupling between layers, and a ferromagnetic coupling in the same layer.

In this work we explore by means of spin-polarized scanning tunneling microcopy/spectroscopy (SP-STM/STS) and ab initio calculations the magnetic and electronic properties of thin MnAu alloyed films. The MnAu films are produced by deposition of small amounts of Au at RT on a Mn(001) surface. On the scanning tunneling microscopy images the surface of the AuMn alloy presents a $c(2\ifmmode\times\else\texttimes\fi{}2)$ reconstruction. From the SP-STM/STS measurements we find out that the MnAu alloy layers are coupled antiferromagnetically with the layers above and below. Comparing the result from the ab initio calculations with the spin-polarized measurements we found that the origin of the magnetic contrast is due to a spin-polarized peak at $0.15\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ above the Fermi level spatially placed on the Mn sites. In the calculations we also found that the magnetic moments of the Mn atoms are higher in the alloy layers than in the pure Mn films.

Spin-polarized scanning tunneling microscopy has produced a great amount of images presenting magnetic contrast between different magnetic domains with an unsurpassed spatial resolution but getting values like the surface polarization has proven to be a difficult task. We will discuss in detail how to extract this information for the case of manganese layers grown on Fe(001) whiskers. Mn layers adopt a body-centered-tetragonal (bct) structure when they are grown on the Fe(001) surface at room temperature. The Mn layers show an antiferromagnetic coupling between the layers. Comparing our spin-polarized scanning tunneling spectra measured with Fe-coated W tips with spin-resolved band structure calculations, we are able to find the value of the sample surface polarization. Also discussed is a method to change the tip magnetization. Finally, the magnetic structure around a screw dislocation on the surface is reviewed. Microsc. Res. Tech. 66:93–104, 2005. © 2005 Wiley-Liss, Inc.

Holographic transmission electron microscopy showed that magnetic flux does not diverge from the top of an Fe-coated W tip indicating the in-plane magnetization at the apex of successful spin-polarized tips. A dependence of differential conductivities of GaAs with Fe-coated W tips on the helicity of illuminating laser light was confirmed at negative sample bias where partially spin-polarized electrons in the conduction band of p-GaAs tunnel into spin-dependent Fe empty states while no dependence of those with nonmagnetic W tips.

Scanning tunneling microscopy measurements show that the growth of about half a monolayer Au on Fe(001) at a temperature of $170\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$ leads after a postanneal at $700\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$ to an island free and homogeneously alloyed surface layer. The surface alloying is in contrast to the bulk where Au and Fe are immiscible. Strong chemical contrast in the images allows us to analyze the short-range order of this surface alloy. Two independent methods are considered: the first method extracts pair occupation probabilities directly from digitized images, the second method makes use of the autocorrelation of filtered images. Both methods lead to the same conclusion: only for the nearest-neighbor sites a strong preference for unlike species is found; for further sites the probabilities follow a random distribution. Scanning tunneling spectroscopy measurements on the alloyed AuFe surface are used to corroborate the interpretation of the chemical contrast. Furthermore, the spectroscopy results show that the Fe(001) surface state shifts to higher energies on areas where pure Fe patches are confined by Au atoms.

Scanning tunneling spectroscopy study of surface states of 3d metals: Chemical identification, magnetic contrast and orbital Kondo resonance states