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In this work, we show the feasibility of extreme ultraviolet (EUV) patterning on an HF-treated silicon (100) surface in the absence of a photoresist. EUV lithography is the leading lithography technique in semiconductor manufacturing due to its high resolution and throughput, but future progress in resolution can be hampered because of the inherent limitations of the resists. We show that EUV photons can induce surface reactions on a partially hydrogen-terminated silicon surface and assist the growth of an oxide layer, which serves as an etch mask. This mechanism is different from the hydrogen desorption in scanning tunneling microscopy-based lithography. We achieve silicon dioxide/silicon gratings with 75-nanometer half-pitch and 31-nanometer height, demonstrating the efficacy of the method and the feasibility of patterning with EUV lithography without the use of a photoresist. Further development of the resistless EUV lithography method can be a viable approach to nanometer-scale lithography by overcoming the inherent resolution and roughness limitations of photoresist materials., Science Advances, 9 (16), ISSN:2375-2548

Germanium has emerged as an exceptionally promising material for spintronics and quantum information applications, with significant fundamental advantages over silicon. However, efforts to create atomic-scale devices using donor atoms as qubits have largely focussed on phosphorus in silicon. Positioning phosphorus in silicon with atomic-scale precision requires a thermal incorporation anneal, but the low success rate for this step has been shown to be a fundamental limitation prohibiting the scale-up to large-scale devices. Here, we present a comprehensive study of arsine (AsH3 ) on the germanium (001) surface. We show that, unlike any previously studied dopant precursor on silicon or germanium, arsenic atoms fully incorporate into substitutional surface lattice sites at room temperature. Our results pave the way for the next generation of atomic-scale donor devices combining the superior electronic properties of germanium with the enhanced properties of arsine/germanium chemistry that promises scale-up to large numbers of deterministically-placed qubits.

Dopant impurity species can be incorporated into the silicon (001) surface via the adsorption and dissociation of simple precursor molecules. Examples include phosphine (PH3), arsine (AsH3), and diborane (B2H6) for the incorporation of phosphorus, arsenic, and boron, respectively. Through exploitation of precursor surface chemistry, the spatial locations of these incorporated dopants can be controlled at the atomic scale via the patterning of a hydrogen lithographic resist layer using scanning tunneling microscopy (STM). There is strong interest in the spatial control of bismuth atoms incorporated into silicon for quantum technological applications; however, there is currently no known precursor for the incorporation of bismuth that is compatible with this STM-based lithographic method. Here, we explore the precursor chemistry (adsorption, diffusion, and dissociation) of bismuth trichloride (BiCl3) on Si(001). We show atomic-resolution STM images of BiCl3 exposed Si(001) surfaces at low coverage and combine this with density functional theory calculations to produce a model of the surface processes and the observed features. Our results show that, at room temperature, BiCl3 completely dissociates to produce bismuth ad-atoms, ad-dimers, and surface-bound chlorine, and we explain how BiCl3 is a strong candidate for a bismuth precursor compound compatible with lithographic patterning at the sub-nanometer scale.

The coverage-dependent behavior of p-methoxyacetophenone on the clean Si(001) surface was followed using X-ray photoelectron spectroscopy and supporting density functional theory calculations. Unlike other multifunctional organic molecules, this compound exhibits a high selectivity of adsorbate species formation by forming only two distinct adsorbate structures at low coverage, with a third configuration forming at high coverages. At low coverage, surface chemisorption is driven by methoxy group dissociation. However, at high coverage, the surface footprint required for this process is no longer available, leading to the formation of less thermodynamically stable adsorbates that are datively bonded to the surface with a smaller footprint. This coverage-dependent but well-defined behavior is promising in designing functional organic–inorganic interfaces on silicon.

The adsorption configurations of a technologically relevant model organic adsorbate on the silicon (001) surface were studied using energy scanned x-ray photoelectron diffraction (PhD). Previous work has established the existence of an interesting vertically-aligned (‘flagpole’) configuration, where the acetophenone attaches to Si(001) via the acetyl group carbon and oxygen atoms. Density functional theory calculations have predicted two energetically similar variants of this structure, where the phenyl ring is orientated parallel or perpendicular to the rows of silicon dimers on this reconstructed surface. However, previously published experimental measurements, including scanning tunnelling microscopy, x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure investigations were unable to distinguish between these two configurations. Here, we apply the unique experimental capabilities of the PhD technique to this system and demonstrate that the dominant adsorption configuration has the phenyl ring parallel to the dimer rows (the end-bridge structure). This information in turn facilitates the determination of the dominant reaction pathway for acetophenone on Si(001), which has remained elusive until now. Information about subtle preferences in reaction pathways that affect the alignment and orientation of organic adsorbates such as acetophenone on technologically-relevant semiconductor surfaces such as Si(001) is critical for the fabrication of future atomically-precise atomic and molecular-scale electronic devices utilising the organic-silicon interface, and this work demonstrates the unique and complementary capabilities of PhD for providing this information.

Nominally-pure black phosphorus (BP) is commonly found to be a p-type semiconductor, suggesting the ubiquitious presence of impurity species or intrinsic, charged defects. Moreover, scanning tunnelling microscopy (STM) images of black phosphorus reveal the presence of long-ranged double-lobed defect features superimposed onto the surface atomic lattice. We show that both the p-type doping of BP and the defect features observed in STM images can be attributed to substitutional tin impurities. We show that black phosphorus samples produced through two common synthesis pathways contain tin impurities, and we demonstrate that the ground state of substitutional tin impurities is negatively charged for a wide range of Fermi level positions within the BP bandgap. The localised negative charge of the tin impurities induces hydrogenic states in the bandgap and it is the 2p level that sits at the valence band edge that gives rise to the double-lobed features observed in STM images., Comment: 19 pages, 4 figures

Nano letters 212(13), 5516–5521 (2021). doi:10.1021/acs.nanolett.1c00677, We present the discovery of a charge density wave (CDW) ground state in heavily electron-doped molybdenum disulfide (MoS$_2$). This is the first observation of a CDW in any d$^2$ (column 6) transition metal dichalcogenide (TMD). The band structure of MoS$_2$ is distinct from the d$^0$ and d$^1$ TMDs in which CDWs have been previously observed, facilitating new insight into CDW formation. We demonstrate a metal–insulator transition at 85 K, a 25 meV gap at the Fermi level, and two distinct CDW modulations, (2√3 × 2√3) R30° and 2 × 2, attributable to Fermi surface nesting (FSN) and electron–phonon coupling (EPC), respectively. This simultaneous exhibition of FSN and EPC CDW modulations is unique among observations of CDW ground states, and we discuss this in the context of band folding. Our observations provide a route toward the resolution of controversies surrounding the origin of CDW modulations in TMDs., Published by ACS Publ., Washington, DC

In this work, we present a novel resistless patterning technique on hydrogen-terminated Si (100) using EUV-induced surface reaction. We has successfully demonstrated a direct Si pattern transfer of half-pitch 75 nm Si gratings using the EUV resistless patterning technique. The EUV-induced surface reactions could achieve direct patterning on functionalized Si surface and potentially overcome the resolution limitations of conventional photoresists in the semiconductor industry. Moreover, this approach can be used for better understanding of EUV exposure mechanisms by preparing simple molecular systems and studying the EUV-induced reactions.

The growth of multi-layer germanium-tin (GeSn) quantum wells offers an intriguing pathway towards the integration of lasers in a CMOS platform. An important step in growing high quality quantum well interfaces is the formation of an initial wetting layer. However, key atomic-scale details of this process have not previously been discussed. We use scanning tunneling microscopy combined with density functional theory to study the deposition of Sn on Ge(1 0 0) at room temperature over a coverage range of 0.01 to 1.24 monolayers. We demonstrate the formation of a sub-2% Ge content GeSn wetting layer from three atomic-scale characteristic ad-dimer structural components, and show that small quantities of Sn incorporate into the Ge surface forming two atomic configurations. The ratio of the ad-dimer structures changes with increasing Sn coverage, indicating a change in growth kinetics. At sub-monolayer coverage, the least densely packing ad-dimer structure is most abundant. As the layer closes, forming a two-dimensional wetting layer, the more densely packing ad-dimer structure become dominant. These results demonstrate the capability to form an atomically smooth wetting layer at room temperature, and provide critical atomic-scale insights for the optimization of growth processes of GeSn multi-quantum-wells to meet the quality requirements of optical GeSn-based devices.

Over the last two decades, prototype devices for future classical and quantum computing technologies have been fabricated, by using scanning tunneling microscopy and hydrogen resist lithography to position phosphorus atoms in silicon with atomic-scale precision. Despite these successes, phosphine remains the only donor precursor molecule to have been demonstrated as compatible with the hydrogen resist lithography technique. The potential benefits of atomic-scale placement of alternative dopant species have, until now, remained unexplored. In this work, we demonstrate successful fabrication of atomic-scale structures of arsenic-in-silicon. Using a scanning tunneling microscope tip, we pattern a monolayer hydrogen mask to selectively place arsenic atoms on the Si(001) surface using arsine as the precursor molecule. We fully elucidate the surface chemistry and reaction pathways of arsine on Si(001), revealing significant differences to phosphine. We explain how these differences result in enhanced surface immobilization and in-plane confinement of arsenic compared to phosphorus, and a dose-rate independent arsenic saturation density of $0.24{\pm}0.04$ ML. We demonstrate the successful encapsulation of arsenic delta-layers using silicon molecular beam epitaxy, and find electrical characteristics that are competitive with equivalent structures fabricated with phosphorus. Arsenic delta-layers are also found to offer improvement in out-of-plane confinement compared to similarly prepared phosphorus layers, while still retaining >80% carrier activation and sheet resistances of $

This study investigates the adsorption and thermal transformations of a bicyclic tertiary amine, triethylenediamine, on the clean Si(100)-2 × 1 surface. Below room temperature, triethylenediamine adsorption leads to the formation of a strong dative bond between one of the nitrogen atoms of this compound and the silicon surface. In contrast to previously studied amines, the datively adsorbed triethylenediamine features a second tertiary amine entity that is not bonded to the surface, with a lone pair orbital that is directed away from the surface and is available for further reactions. The thermal chemistry and electronic properties of triethylenediamine on silicon are studied using thermal desorption spectroscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy. Near-edge X-ray absorption fine structure measurements are utilized to clarify the geometry of the adsorbates at room temperature. Density functional theory calculations are used to describe the binding geometry and electronic properti...

It is now well established that an isolated C-defect on the Si(001) surface corresponds to a dissociated water molecule with the H and OH species bonded to silicon atoms on the same side of two adjacent surface dimers. In this paper we show that there are two distinct types of such C-defects at both low temperature (∼100 K) and room temperature. These defects differ in the buckling orientation of the Si–Si dimers adjacent to the defect and/or the distribution of their localized electron spins. Changes in the buckling configuration of the bare Si–Si dimers neighboring the defect modifies the interaction between its dangling bonds and the surface and leads to significant variations in the defect charge density distributions.

Control of dopants in silicon remains the most important approach to tailoring the properties of electronic materials for integrated circuits, with Group V impurities the most important n-type dopants. At the same time, silicon is finding new applications in coherent quantum devices, thanks to the magnetically quiet environment it provides for the impurity orbitals. The ionization energies and the shape of the dopant orbitals depend on the surfaces and interfaces with which they interact. The location of the dopant and local environment effects will therefore determine the functionality of both future quantum information processors and next-generation semiconductor devices. Here we match observed dopant wavefunctions from low-temperature scanning tunnelling microscopy (STM) to images simulated from first-principles density functional theory (DFT) calculations. By this combination of experiment and theory we precisely determine the substitutional sites of neutral As dopants between 5 and 15A below the Si(001):H surface. In the process we gain a full understanding of the interaction of the donor-electron state with the surface, and hence of the transition between the bulk dopant (with its delocalised hydrogenic orbital) and the previously studied dopants in the surface layer., 12 pages; accepted for publication in Phys. Rev. B

The attachment of organic molecules to semiconductor surfaces and their measurement using scanning tunneling microscopy and spectroscopy (STM/STS) is considered to be a potential route toward conductance measurements of single molecules with known structural and electronic configuration. Here, we investigate a model system—acetophenone on Si(001)—and demonstrate that this adsorbate can be manipulated using the STM such that it adopts a configuration where it stands upright with a free-standing phenyl ring and strong Si–O linkage to the substrate. For the structural identification we combine STM imaging with density functional theory (DFT) calculations to describe the adsorbate structures that were observed in our experiments and the reaction pathways that link them; of these the upright configuration is the most thermodynamically stable. The chemical structure of the upright configuration suggests that π-conjugation within the adsorbate extends to the silicon surface resulting in strong hybridization of t...

Microwave microscopy enables three-dimensional characterization of atomically thin semiconductor structures with nanometer precision., It is now possible to create atomically thin regions of dopant atoms in silicon patterned with lateral dimensions ranging from the atomic scale (angstroms) to micrometers. These structures are building blocks of quantum devices for physics research and they are likely also to serve as key components of devices for next-generation classical and quantum information processing. Until now, the characteristics of buried dopant nanostructures could only be inferred from destructive techniques and/or the performance of the final electronic device; this severely limits engineering and manufacture of real-world devices based on atomic-scale lithography. Here, we use scanning microwave microscopy (SMM) to image and electronically characterize three-dimensional phosphorus nanostructures fabricated via scanning tunneling microscope–based lithography. The SMM measurements, which are completely nondestructive and sensitive to as few as 1900 to 4200 densely packed P atoms 4 to 15 nm below a silicon surface, yield electrical and geometric properties in agreement with those obtained from electrical transport and secondary ion mass spectroscopy for unpatterned phosphorus δ layers containing ~1013 P atoms. The imaging resolution was 37 ± 1 nm in lateral and 4 ± 1 nm in vertical directions, both values depending on SMM tip size and depth of dopant layers. In addition, finite element modeling indicates that resolution can be substantially improved using further optimized tips and microwave gradient detection. Our results on three-dimensional dopant structures reveal reduced carrier mobility for shallow dopant layers and suggest that SMM could aid the development of fabrication processes for surface code quantum computers.

In this work we combine scanning tunneling microscopy, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission spectroscopy and density functional theory to resolve a long-standing confusion regarding the adsorption behaviour of benzonitrile on Si(001) at room temperature. We find that a trough-bridging structure is sufficient to explain adsorption at low coverages. At higher coverages when steric hindrance prevents the phenyl ring lying flat on the surface, the 2+2 cycloaddition structure dominates.

We characterize the incorporation of Ba adatoms into the Ge(001) surface, resulting in the formation of one-dimensional structures with an internal 2×3 periodicity, after the deposition of Ba atoms at 970 K or at room temperature followed by a 770 K anneal. Scanning tunneling microscopy (STM) data were compared with theoretically simulated STM images generated by density functional theory electronic structure calculations. Excellent agreement between experiment and simulation was found when using an adopted structural model that assumes partial removal of the surface Ge dimers in the [1–10] surface direction and subsequent addition of a single Ba atom to the substrate second layer. Structural assignments for a number of defects observed within regions of the 2×3 reconstruction were also obtained.

Quantum confinement effects on the electronic structure of thin Ge(001) slabs with one clean and one H-terminated surface are discussed based on density functional theory calculations for periodic ...

The adsorption of acetone [(CH 3 ) 2 CO] on the Si(0 0 1) surface has been investigated using density functional theory (DFT) and scanning tunneling microscopy (STM). Three distinct features have been observed in the experimental STM images – one single-dimer and two two-dimer wide features. We have considered 32 different possible adsorbate configurations corresponding to the [2 + 2] cycloaddition, dative bonded, α-Hydrogen cleavage, C H bond cleavage, methyl cleavage, cross-dimer bridging, O-dimer insertion, OH cleavage, alcohol-like, end-bridging and dimer-bridging structures. The optimised geometry, binding energy, and simulated filled- and empty-state STM images for each of these possible configurations are presented. These results have facilitated the identification of the three experimentally-observed acetone adsorbate structures.

We present the results of a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) of the interaction of acetone [(CH3)2CO] with the Si(0 0 1) surface. Three distinct adsorbate features were observed using atomic-resolution STM. One of the features appears as a bright protrusion located above a Si–Si dimer, while the other two are asymmetric about the dimer row and involve a second neighboring Si–Si dimer. One of the two asymmetric features has a protrusion located between the two dimers, while the other has a protrusion which is located at the site of a single dimer and exhibits a dimer sized depression on the adjacent dimer. DFT calculations have been performed for two structures; the four-membered ring structure and dissociation structure. Our calculations show that the bright single-dimer sized feature observed in the STM images could be attributed to either of these two calculated structures. However, neither of the two calculated structures can explain the appearance of the two-dimer wide asymmetric features observed in the experiment.

The ability to covalently attach organic molecules to semiconductor surfaces in a controllable and selective manner is currently receiving much attention due to the potential for creating hybrid silicon-organic molecular-electronic devices. Here we use scanning tunneling microscopy (STM) and density functional theory calculations to study the adsorption of a simple ketone [acetone; (CH(3))(2)CO] to the silicon (001) surface. We show both bias and time-dependent STM images and their agreement with total energy DFT calculations, simulated STM images, and published spectroscopic data. We investigate the stability of the resulting adsorbate structures with respect to temperature and applied STM tip bias and current. We demonstrate the ability to convert from the kinetically favored single-dimer alpha-H cleavage adsorbate structure to thermodynamically favored bridge-bonded adsorbate structures. This can be performed for the entire surface using a thermal anneal or, for individual molecules, using the highly confined electron beam of the STM tip. We propose the use of the carbonyl functional group to tether organic molecules to silicon may lead to increased stability of the adsorbates with respect to current-voltage characterization. This has important implications for the creation of robust single-molecule devices.

An ordered alkaline-earth submonolayer on a clean $\mathrm{Si}(001)$ surface provides a template for growth of the atomically sharp, crystalline Si-oxide interface that is ubiquitous in the semiconductor device industry. It has been suggested that submonolayers of Sr or Ba on $\mathrm{Ge}(001)$ could play a similar role as on structurally identical $\mathrm{Si}(001)$, overcoming known limitations of the $\mathrm{Ge}(001)$ substrate such as amorphization of its oxidation layers. In this paper the initial stage of the Ba oxidation process, i.e., adsorption and organization of Ba atoms on the $\mathrm{Ge}(001)$ surface as a function of temperature $(270\ensuremath{-}770\phantom{\rule{0.16em}{0ex}}\mathrm{K})$ for coverage 1.0 monolayer (ML) and $0.15\ensuremath{-}0.4\phantom{\rule{0.16em}{0ex}}\mathrm{ML}$, is studied using scanning tunneling microscopy (STM) and density functional theory (DFT). Three types of features have been identified on the Ba-covered $\mathrm{Ge}(001)$ surface. They originate from isolated Ba adatoms, isolated Ba ad-dimers, and the Ba ad-dimers assembled into short-range, randomly distributed chains that run across the Ge dimer rows. We find from both STM measurements and DFT calculations that the latter is the dominant structure on $\mathrm{Ge}(001)$ with increasing coverage.

We present a comparative scanning tunnelling microscopy (STM) study of two features on the Si(0 0 1) surface with a single dangling bond. One feature is the Si–P heterodimer—a single surface phosphorus atom substituted for one Si atom of a Si–Si dimer. The other feature is the Si–Si–H hemihydride—a single hydrogen atom adsorbed to one Si atom of a Si–Si dimer. Previous STM studies of both surface species have reported a nearly identical appearance in STM which has hampered an experimental distinction between them to date. Using voltage-dependent STM we are able to distinguish and identify both heterodimer and hemihydride on the Si(0 0 1) surface. This work is particularly relevant for the fabrication of atomic-scale Si:P devices by STM lithography on the hydrogen terminated Si(0 0 1):H surface, where it is important to monitor the distribution of single P dopants in the surface. Based on the experimental identification, we study the lateral P diffusion out of nanoscale reservoirs prepared by STM lithography.

The ability to identify and control the pathway by which chemical reactions occur at the level of individual atoms will be of enormous benefit in the coming age of nanotechnology. Here, we present a detailed atomic-resolution scanning tunneling microscopy (STM) study of one such pathway: the adsorption, surface diffusion and dissociation of phosphine (PH3) on silicon (001). We show that PH3 dissociates on Si(001) to produce PH2 + H, PH + 2H and P + 3H moieties. In addition, we show that PH2 molecules are readily able to diffuse on Si(001) at room temperature, resulting in the formation of hemihydride dimers on low dosed Si(001) surfaces. In addition we show that control over the processes of diffusion and surface incorporation can be achieved using STM-based hydrogen lithography; a technique that is now used in many STM laboratories. [DOI: 10.1380/ejssnt.2006.609]

We present a review of a detailed fabrication strategy for the realisation of nano and atomic-scale devices in silicon using phosphorus as a dopant and a combination of ultra-high vacuum scanning probe microscopy and silicon molecular beam epitaxy (MBE). In this work we have been able to overcome some of the key fabrication challenges to the realisation of atomic-scale devices including the identification of single P dopants in silicon, the controlled incorporation of P atoms in silicon with atomic precision and the minimisation of P segregation and diffusion during Si encapsulation. Recently, we have combined these results with a novel registration technique to fabricate robust electrical devices in silicon that can be contacted and measured outside the ultra-high vacuum environment. We discuss the importance of our results for the future fabrication of atomic-scale devices in silicon.

We have used scanning tunneling microscopy (STM) to image charged defects on the clean (100)-(2×1) surface of p-type silicon. In the absence of “C”-type defects, band bending can occur during STM imaging, allowing near surface charge to influence the state density contributing to the tunnel current. As in the case of cleavage faces of III–V semiconductor crystals, the charge-induced band bending produces long range enhancements superimposed on the periodic surface lattice. The charged defects observed in this work are of the types commonly observed elsewhere in clean Si(100)-(2×1) STM studies, however, not all defects of a given type appear charged. This would indicate subtle differences in defect structure that are not obvious at higher sample bias. This work demonstrates the ability to observe charged features on the clean Si(100) surface, which will be important for current and future research focused on producing atomic scale electronic structures.

The construction of a scalable quantum computer in silicon, using single phosphorus atoms as qubits, presents a significant technological challenge. This paper describes recent results from a ‘bottom-up’ strategy to incorporate individual phosphorus atoms in silicon with atomic precision using a combination of advanced scanning tunnelling lithography techniques followed by low temperature silicon molecular beam epitaxial overgrowth. To date we have demonstrated (i) placement of individual phosphorus molecules at predetermined sites in the silicon surface using a hydrogen resist strategy, (ii) spatially controlled phosphorus incorporation into the silicon surface, (iii) minimisation of surface segregation by low temperature silicon encapsulation and (iv) complete electrical activation of the donors. Whilst these results bode well for the fabrication of silicon devices with atomically precise dopant profiles, we discuss the challenges that remain before a few qubit P in Si quantum computer prototype can be realised.

We present recent progress towards the fabrication of a silicon-based quantum computer, via a ‘bottom up’ strategy, which exploits a combination of scanning tunneling microscopy (STM) and molecular beam epitaxy. Following our recent success in the fabrication of an atomic array of P atoms in silicon we now address the critical issues leading to the encapsulation of this array in silicon. Exposing Si(0 0 1) to a low PH 3 dose at room temperature results in the formation of a number of species on the surface. We use bias dependent STM to characterise these species and identify PH x ( x =2,3) moieties and hemihydrides as the dominant surface adsorbates. We show that by controlled annealing we can incorporate single P atoms into the surface layer. We use STM lithography to depassivate regions of a H:Si(0 0 1) surface in order to confine the above adsorption/incorporation processes to nanometer sized areas.

We present three important results relating to the fabrication of a quantum computer in silicon: (i) the interaction of the dopant gas phosphine with Si(001), (ii) a comparison of the morphology of epitaxial Si layers grown on clean and on monohydride-terminated Si(001), and (iii) a direct measure of the segregation/diffusion of incorporated P atoms during Si epitaxial growth and annealing. After low phosphine (PH3) dosing of a Si(001) surface dual bias scanning tunneling microscopy was used to identify the PH x(x = 2, 3) species on the surface. Subsequent annealing to 350°C resulted in the P atom from the PH x molecule being incorporated into the surface to form Si–P heterodimers. The threefold coordination that results from incorporation is expected to be advantageous for phosphorus quantum bit fabrication since it will reduce P segregation and diffusion during Si epitaxial overgrowth. One question to be addressed in the encapsulation process for quantum bits is whether the H resist layer needs to be removed or whether we can grow through the hydrogen layer. We demonstrate that five-monolayer-thick epitaxial Si layers deposited at low temperature (250°C) using molecular beam epitaxy have a significantly lower roughness and defect density when grown on a clean Si(001) surface compared to a H-terminated surface. Attempts to encapsulate phosphorus quantum bits at 260°C and to recover the surface quality of the epitaxial layer resulted in P atoms segregating and diffusing to the surface. These results suggest that the hydrogen layer is desorbed first before the P atoms are encapsulated in epitaxial silicon grown at very low temperature (below 250°C) to minimise phosphorus segregation.

Recognition of the potentially massive computational power of a quantum computer has driven a considerable experimental effort to build such a device. Of the various possible physical implementations, silicon-based architectures are attractive for the long spin relaxation times involved, their scalability, and ease of integration with existing silicon technology. However, their fabrication requires construction at the atomic scale-an immense technological challenge. Here we outline a detailed strategy for the construction of a phosphorus in silicon quantum computer and demonstrate the first significant step towards this goal-the fabrication of atomically precise arrays of single phosphorus bearing molecules on a silicon surface. After using a monolayer hydrogen resist to passivate a silicon surface we apply pulsed voltages to a scanning tunnelling microscope tip to selectively desorb individual hydrogen atoms with atomic resolution. Exposure of this surface to the phosphorus precursor phosphine results in precise placement of single phosphorus atoms on the surface. We also describe preliminary studies into a process to incorporate these surface phosphorus atoms into the silicon crystal at the array sites.

Scanning tunneling microscopy (STM) has been used to image charged defects on the clean Si(100)-(2×1) surface. Previous studies have shown that, in the absence of “C”-type defects, the surface does not pin the Fermi level, allowing near surface charge to influence the state density contributing to the tunneling current. As in the case of cleavage faces of III–V semiconductor crystals, the charge-induced band bending produces long-range enhancements superimposed on the periodic surface lattice. This is observed in empty-state STM images taken on n-type material. No band bending signature is seen in the filled-state images. This can be understood by considering the band structure at the surface, which has surface states within the band gap. The charged defects observed in this work are of the types commonly observed in clean Si(100)-(2×1) STM studies, however, not all defects of a given type appear charged. This would indicate subtle differences in structure or the influence of impurities. Predictions for p...

We investigate the chemical and structural configuration of acetophenone on Si(001) using synchrotron radiation core-level spectroscopy techniques and density functional theory calculations. Samples were prepared by vapour phase dosing of clean Si(001) surfaces with acetophenone in ultrahigh vacuum. Near edge X-ray adsorption fine structure spectroscopy and photoelectron spectroscopy measurements were made at room temperature as a function of coverage density and post-deposition anneal temperature. We show that the dominant room temperature adsorption structure lies flat on the substrate, while moderate thermal annealing induces the breaking of Si-C bonds between the phenyl ring and the surface resulting in the reorientation of the adsorbate into an upright configuration., 7 figures, 16 pages

The extended Brenner potential has been shown to provide a good description of the (001) and (111) surfaces of silicon. In this paper, this empirical potential is employed to study the energetics of steps on the Si(001)2x1 surface. Particular attention has been paid to the dependence of the step energies on the width of the terraces and the number of substrate layers. Formation energies for both the single-layer S-A and S-B steps, and the double layer D-A and D-B steps, have been determined. All of the formation energies are found to be negative. Values of the step-step and surface stress interaction energy coefficients are also determined. The correlation of these results with experiment and previous theoretical calculations is discussed.

We study subsurface arsenic dopants in a hydrogen-terminated Si(001) sample at 77 K, using scanning tunnelling microscopy and spectroscopy. We observe a number of different dopant-related features that fall into two classes, which we call As1 and As2. When imaged in occupied states, the As1 features appear as anisotropic protrusions superimposed on the silicon surface topography and have maximum intensities lying along particular crystallographic orientations. In empty-state images the features all exhibit long-range circular protrusions. The images are consistent with buried dopants that are in the electrically neutral (D0) charge state when imaged in filled states, but become positively charged (D+) through electrostatic ionization when imaged under empty-state conditions, similar to previous observations of acceptors in GaAs. Density functional theory calculations predict that As dopants in the third layer of the sample induce two states lying just below the conduction-band edge, which hybridize with the surface structure creating features with the surface symmetry consistent with our STM images. The As2 features have the surprising characteristic of appearing as a protrusion in filled-state images and an isotropic depression in empty-state images, suggesting they are negatively charged at all biases. We discuss the possible origins of this feature.

We investigate the effect of an external magnetic field on the physical properties of the acceptor hole states associated with single Mn acceptors placed near the (110) surface of GaAs. Crosssectional scanning tunneling microscopy images of the acceptor local density of states (LDOS) show that the strongly anisotropic hole wavefunction is not significantly affected by a magnetic field up to 6 T. These experimental results are supported by theoretical calculations based on a tightbinding model of Mn acceptors in GaAs. For Mn acceptors on the (110) surface and the subsurfaces immediately underneath, we find that an applied magnetic field modifies significantly the magnetic anisotropy landscape. However the acceptor hole wavefunction is strongly localized around the Mn and the LDOS is quite independent of the direction of the Mn magnetic moment. On the other hand, for Mn acceptors placed on deeper layers below the surface, the acceptor hole wavefunction is more delocalized and the corresponding LDOS is much more sensitive on the direction of the Mn magnetic moment. However the magnetic anisotropy energy for these magnetic impurities is large (up to 15 meV), and a magnetic field of 10 T can hardly change the landscape and rotate the direction of the Mn magnetic moment away from its easy axis. We predict that substantially larger magnetic fields are required to observe a significant field-dependence of the tunneling current for impurities located several layers below the GaAs surface., Comment: None

We report that solitary bismuth and antimony atoms, incorporated at Si(111) surfaces, induce either positive or negative charge states depending on the site of the surface reconstruction in which they are located. This is in stark contrast to the hydrogenic donors formed by group V atoms in silicon bulk crystal and therefore has strong implications for the design and fabrication of future highly scaled electronic devices. Using scanning tunnelling microscopy (STM) and density functional theory (DFT) we determine the reconstructions formed by different group V atoms in the Si(111)2 × 1 surface. Based on these reconstructions a model is presented that explains the polarity as well as the location of the observed charges in the surface. Using locally resolved scanning tunnelling spectroscopy we are furthermore able to map out the spatial extent over which a donor atom influences the unoccupied surface and bulk electronic states near the Fermi-level. The results presented here therefore not only show that a dopant atom can induce both positive and negative charges but also reveal the nature of the local electronic structure in the region of the silicon surface where an individual donor atom is present.

Using the acetic acid/Si(001) system as an illustrative example, we discuss the limits and opportunities of "chemical analogy" as a paradigm to rationalize chemisorption processes on surfaces. Recent proposals that acetic acid chemisorption results in a bidentate, single-dehydrogenated product are based on earlier findings for the acetic acid/Ge(001) system. In contrast, the well-characterized reaction of acetone with Si( 001) suggests that acetic acid chemisorption leads to the loss of two hydrogen atoms from the molecule. Density-functional calculations resolve this ambiguity, finding the latter structure model to be thermodynamically preferred and kinetically viable.

Strain induced by antiphase boundaries (APBs) in the Si(111) 2 x 1 surface is investigated using scanning tunneling microscopy (STM), laterally resolved scanning tunneling spectroscopy (STS), and density functional theory (DFT). We determine the structure of all identified APB reconstructions and show that a band shift of states close to the Fermi energy leads to the previously observed electronic contrast. The orientation of the band shift and the observed movement of APBs within the surface are explained by surface strain resulting from the excess free energy of the boundary. We demonstrate that the location of APBs and their associated strain can be precisely manipulated, making them an ideal model system to study and control strain at the atomic scale.

Graphitic systems have an electronic structure that can be readily manipulated through electrostatic or chemical doping, resulting in a rich variety of electronic ground states. Here we report the first observation and characterization of electronic stripes in the highly electron-doped graphitic superconductor, CaC(6), by scanning tunnelling microscopy and spectroscopy. The stripes correspond to a charge density wave with a period three times that of the Ca superlattice. Although the positions of the Ca intercalants are modulated, no displacements of the carbon lattice are detected, indicating that the graphene sheets host the ideal charge density wave. This provides an exceptionally simple material-graphene-as a starting point for understanding the relation between stripes and superconductivity. Furthermore, our experiments suggest a strategy to search for superconductivity in graphene, namely in the vicinity of striped 'Wigner crystal' phases, where some of the electrons crystallize to form a superlattice.

The adsorption of isolated H atoms on the Ge(001) surface is studied using density functional theory (DFT) and scanning tunneling microscopy (STM). Two stable adsorption positions that are found in DFT correspond to H atom attachment to an up-or down-buckled Ge dimer atom, respectively. Surprisingly, in the case where H bonds to the down-buckled Ge atom, we find that there is a redistribution of a unit of charge which leaves the net charge of the doubly occupied dangling bond of the unreacted Ge atom intact. This configuration is found to be the more stable of the two structures. Comparison to filled- and empty-state STM images confirms that this lowest energy structure is observed at room temperature. These results represent a fundamentally different picture of the physics and chemistry of H adsorption to Ge(001) compared with previous work.

Using density functional theory, we report detailed reaction path calculations for the reaction of acetone with the silicon (001) surface. We identify the key reaction intermediates of dissociative adsorption and the transition states between them. This resolves the identity of the one-dimer intermediate observed in STM experiments and its role in the formation of several two-dimer-wide end products of dissociation. Key to the understanding of the dissociation mechanism is the ambiphilic character of the two reactants, that is the simultaneous expression of electrophilic and nucleophilic reactivities in both the surface and the acetone molecule.

The recent literature has now firmly attributed the common C defect on the Si(001) surface to the dissociative adsorption of water. This work, by examining the dynamical properties of the C defect at elevated temperatures (450 K), establishes the missing mechanistic link between. dissociative water adsorption and wet surface oxidation. Scanning tunneling microscopy and density functional theory in combination reveal in detail the various paths by which a water molecule breaks apart on the surface and inserts oxygen atoms into the surface.

The optical, electrical, and chemical properties of semiconductor surfaces are largely determined by their electronic states close to the Fermi level (${E}_{F}$). We use scanning tunneling microscopy and density functional theory to clarify the fundamental nature of the ground state Ge(001) electronic structure near ${E}_{F}$, and resolve previously contradictory photoemission and tunneling spectroscopy data. The highest energy occupied surface states were found to be exclusively back bond states, in contrast to the Si(001) surface, where dangling bond states also lie at the top of the valence band.

Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.