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Fabrication of semiconductor heterostructures is now so precise that metrology has become a key challenge for progress in science and applications. It is now relatively straightforward to characterize classic III-V and group IV heterostructures consisting of slabs of different semiconductor alloys with thicknesses of $\sim$5 nm and greater using sophisticated tools such as X-ray diffraction, high energy X-ray photoemission spectroscopy, and secondary ion mass spectrometry. However, profiling thin layers with nm or sub-nm thickness, e.g. atomically thin dopant layers ($\delta$-layers), of impurities required for modulation doping and spin-based quantum and classical information technologies is more challenging. Here, we present theory and experiment showing how resonant-contrast X-ray reflectometry meets this challenge. The technique takes advantage of the change in the scattering factor of atoms as their core level resonances are scanned by varying the X-ray energy. We demonstrate the capability of the resulting element-selective, non-destructive profilometry for single arsenic $\delta$-layers within silicon, and show that the sub-nm electronic thickness of the $\delta$-layers corresponds to sub-nm chemical thickness. In combination with X-ray fluorescence imaging, this enables non-destructive three-dimensional characterization of nano-structured quantum devices. Due to the strong resonances at soft X-ray wavelengths, the technique is also ideally suited to characterize layered quantum materials, such as cuprates or the topical infinite-layer nickelates.

Artificial lattices constructed from individual dopant atoms within a semiconductor crystal hold promise to provide novel materials with tailored electronic, magnetic, and optical properties. These custom engineered lattices are anticipated to enable new, fundamental discoveries in condensed matter physics and lead to the creation of new semiconductor technologies including analog quantum simulators and universal solid-state quantum computers. In this work, we report precise and repeatable, substitutional incorporation of single arsenic atoms into a silicon lattice. We employ a combination of scanning tunnelling microscopy hydrogen resist lithography and a detailed statistical exploration of the chemistry of arsine on the hydrogen terminated silicon (001) surface, to show that single arsenic dopants can be deterministically placed within four silicon lattice sites and incorporated with 97$\pm$2% yield. These findings bring us closer to the ultimate frontier in semiconductor technology: the deterministic assembly of atomically precise dopant and qubit arrays at arbitrarily large scales.

In this work, we show the feasibility of extreme ultraviolet (EUV) patterning on an HF-treated Si(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 H-terminated Si surface and assist the growth of an oxide layer, which serves as an etch mask. This mechanism is different from the H-desorption in scanning tunneling microscopy-based lithography. We achieve SiO2/Si gratings with 75 nm half-pitch and 31 nm 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 nm-scale lithography by overcoming the inherent resolution and roughness limitations of photoresist materials., Comment: 15 pages, 7 figures

Two-dimensional dopant layers ($\delta$-layers) in semiconductors provide the high-mobility electron liquids (2DELs) needed for nanoscale quantum-electronic devices. Key parameters such as carrier densities, effective masses, and confinement thicknesses for 2DELs have traditionally been extracted from quantum magnetotransport. In principle, the parameters are immediately readable from the one-electron spectral function that can be measured by angle-resolved photoemission spectroscopy (ARPES). Here, buried 2DEL $\delta$-layers in silicon are measured with soft X-ray (SX) ARPES to obtain detailed information about their filled conduction bands and extract device-relevant properties. This study takes advantage of the larger probing depth and photon energy range of SX-ARPES relative to vacuum ultraviolet (VUV) ARPES to accurately measure the $\delta$-layer electronic confinement. The measurements are made on ambient-exposed samples and yield extremely thin ($\approx 1$ $nm$) and dense ($\approx$ $10^{14}$ $cm^2$) 2DELs. Critically, this method is used to show that $\delta$-layers of arsenic exhibit better electronic confinement than $\delta$-layers of phosphorus fabricated under identical conditions., Comment: Published in Advanced Science as a Research Article

The progress of miniaturisation in integrated electronics has led to atomic and nanometre-sized dopant devices in silicon. Such structures can be fabricated routinely by hydrogen resist lithography, using various dopants such as phosphorous and arsenic. However, the ability to non-destructively obtain atomic-species-specific images of the final structure, which would be an indispensable tool for building more complex nano-scale devices, such as quantum co-processors, remains an unresolved challenge. Here we exploit X-ray fluorescence to create an element-specific image of As dopants in silicon, with dopant densities in absolute units and a resolution limited by the beam focal size (here $\sim1~\mu$m), without affecting the device's low temperature electronic properties. The As densities provided by the X-ray data are compared to those derived from Hall effect measurements as well as the standard non-repeatable, scanning tunnelling microscopy and secondary ion mass spectroscopy, techniques. Before and after the X-ray experiments, we also measured the magneto-conductance, dominated by weak localisation, a quantum interference effect extremely sensitive to sample dimensions and disorder. Notwithstanding the $1.5\times10^{10}$ Sv ($1.5\times10^{16}$ Rad/cm$^{-2}$) exposure of the device to X-rays, all transport data were unchanged to within experimental errors, corresponding to upper bounds of 0.2 Angstroms for the radiation-induced motion of the typical As atom and 3$\%$ for the loss of activated, carrier-contributing dopants. With next generation synchrotron radiation sources and more advanced optics, we foresee that it will be possible to obtain X-ray images of single dopant atoms within resolved radii of 5 nm.

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 (AsH$_3$) 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., Comment: 8 pages, 4 figures, plus 2 pages supplementary information and 1 supplementary figure

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

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, $(2\sqrt{3}\times2\sqrt{3})$R$30^\circ$ and $2\times2$, 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., Comment: 19 pages, 4 figures, supplementary information

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 $<2 k{\Omega}/{\square}$. These excellent characteristics of arsenic represent opportunities to enhance existing capabilities of atomic-scale fabrication of dopant structures in silicon, and are particularly important for three-dimensional devices, where vertical control of the position of device components is critical.

Doping of silicon via phosphene exposures alternating with molecular beam epitaxy overgrowth is a path to Si:P substrates for conventional microelectronics and quantum information technologies. The technique also provides a new and well-controlled material for systematic studies of two-dimensional lattices with a half-filled band. We show here that for a dense ($n_s=2.8\times 10^{14}$\,cm$^{-2}$) disordered two-dimensional array of P atoms, the full field angle-dependent magnetostransport is remarkably well described by classic weak localization theory with no corrections due to interaction effects. The two- to three-dimensional cross-over seen upon warming can also be interpreted using scaling concepts, developed for anistropic three-dimensional materials, which work remarkably except when the applied fields are nearly parallel to the conducting planes., Comment: 9 pages, 4 figures, supplementary information

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., Comment: 12 pages; accepted for publication in Phys. Rev. B

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., Comment: 7 figures, 16 pages

We study sub-surface 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 ionisation when imaged under empty state conditions, similar to previous observations of acceptors in GaAs. Density functional theory (DFT) 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.