Single Phosphorus Atom Research Articles

Functionalization of Tetraphosphido Ligands by Heterocumulenes.

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P-P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P-C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

Exploiting Atomic Control to Show When Atoms Become Molecules

AbstractPrecision‐placed atom qubits in silicon offer a unique means to confine electrons and control their spins with extreme accuracy, which can be leveraged to construct powerful quantum computers. To date atom qubits in silicon have been successfully realized using electrons hosted either on a single phosphorus atom or on a multi‐donor quantum dot. Here, a novel molecular regime is explored in which electrons are bound to two donor dots separated by ≈8 nm in a natural silicon substrate. The molecular state, provided by these spatially separated donors, is used to study with exquisite precision the impact of confinement potential on the electronic and spin properties of qubits. Unique spin filling measurements, performed on up to five electrons, confirm how electrons are shared between both sites of the molecule, forming hybridized molecular states. The precise atomic locations of the donor atoms in the silicon lattice are determined by combining the experimental electron spin resonance spectra and the state‐of‐the‐art atomistic modeling of multi‐electron wave‐functions in presence of realistic electric fields. The donor molecule studied in this work exhibits excellent qubit properties and addresses the impact that the confinement potential has, at the atomic scale, on the desired properties of electron spin qubits.

Arena: Rapid and Accurate Reconstruction of Full Atomic RNA Structures From Coarse-grained Models

RNA tertiary structures from experiments or computational predictions often contain missing atoms, which prevent analyses requiring full atomic structures. Current programs for RNA reconstruction can be slow, inaccurate, and/or require specific atoms to be present in the input. We present Arena (Atomic Reconstruction of RNA), which reconstructs a full atomic RNA structure from residues that can have as few as one atom. Arena first fills in missing atoms and then iteratively refines their placement to reduce nonideal geometries. We benchmarked Arena on a dataset of 361 RNA structures, where Arena achieves high accuracy and speed compared to other structure reconstruction programs. For example, Arena was used to reconstruct full atomic structures from a single phosphorus atom per nucleotide to, on average, within 3.63 Å RMSD of the experimental structure, while virtually removing all clashes and running in <3 s, which is 353× and 46× faster than state-of-the-art programs PDBFixer and C2A, respectively. The Arena source code is available at https://github.com/pylelab/Arena and the webserver at https://zhanggroup.org/Arena/.

Formation of the elusive tetrahedral P3N molecule.

The tetrahedral 1,2,3-triphospha-4-azatricyclo [1.1.0.02,4] butane (P3N) molecule—an isovalent species of phosphorus (P4)—was prepared in low-temperature (5 K) phosphine-nitrogen ices and was identified in the gas phase through isomer-selective, tunable, soft photoionization reflectron time-of-flight mass spectrometry. Theoretical calculations reveal that the substitution of a single phosphorus atom by nitrogen in the P4 molecule results in enhanced spherical aromaticity while simultaneously increasing the strain energy from 74 to 195 kJ mol−1. In P3N, the P─P bond is shortened compared to those in P4 by 3.6 pm, while the P─N─P bond angle of 73.0° is larger by 13.0° compared to the P─P─P bond angle of 60.0° in P4. The identification of tetrahedral P3N enhances our fundamental understanding of the chemical bonding, electronic structure, and stability of binary, interpnictide tetrahedral molecules and reveals a universal route to prepare ring strained cage molecules in extreme environments.

Valley population of donor states in highly strained silicon

Strain is extensively used to controllably tailor the electronic properties of materials. In the context of indirect band-gap semiconductors such as silicon, strain lifts the valley degeneracy of the six conduction band minima, and by extension the valley states of electrons bound to phosphorus donors. Here, single phosphorus atoms are embedded in an engineered thin layer of silicon strained to 0.8% and their wave function imaged using spatially resolved spectroscopy. A prevalence of the out-of-plane valleys is confirmed from the real-space images, and a combination of theoretical modelling tools is used to assess how this valley repopulation effect can yield isotropic exchange and tunnel interactions in the xy-plane relevant for atomically precise donor qubit devices. Finally, the residual presence of in-plane valleys is evidenced by a Fourier analysis of both experimental and theoretical images, and atomistic calculations highlight the importance of higher orbital excited states to obtain a precise relationship between valley population and strain. Controlling the valley degree of freedom in engineered strained epilayers provides a new competitive asset for the development of donor-based quantum technologies in silicon.

Spin thermoelectric effects on aluminum or phosphorus doped zigzag silicene nanoribbons

Based on the density-functional theory (DFT) combined with nonequilibrium Green’s function (NGF), this paper investigates the effects of either single aluminum (Al) or single phosphorus (P) atom substitutions at different edge positions of zigzag-edged silicene nanoribbons (ZGNRs) in the ferromagnetic state on the spin-dependent transport properties and spin thermoelectric effects. It has been found that the spin polarization at the Fermi level can reach 100% or –100% in the doped ZSiNRs. Meanwhile, the spin-up Seebeck effect (for -100% case) and spin-down Seebeck effect (for 100% case) are also enhanced. Moreover, the spin Seebeck coefficient is much larger than the corresponding charge Seebeck coefficient at a special doping position and electron energy. Therefore, the study shows that the Al or P doped ZSiNRs can be used to prepare the ideal thermospin devices.

Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P4 fragmentation.

Oxidative addition of the P–P single bond of an ortho-carborane-derived 1,2-diphosphetane (1,2-C2(PMes)2B10H10) (Mes = 2,4,6-Me3C6H2) to cobalt(−i) and nickel(0) sources affords the first heteroleptic complexes of a carborane-bridged bis(phosphanido) ligand. The complexes also incorporate labile ligands suitable for further functionalisation. Thus, the cobalt(i) complex [K([18]crown-6)][Co{1,2-(PMes)2C2B10H10}(cod)] (cod = 1,5-cyclooctadiene) bearing a labile cyclooctadiene ligand undergoes facile ligand exchange reactions with isonitriles and tert-butyl phosphaalkyne with retention of the bis(phosphanido) ligand. However, in the reaction with one equivalent of P4, the electron-rich bis(phosphanido) moiety abstracts a single phosphorus atom with formation of a new P3 chain, while the remaining three P atoms derived from P4 form an η3-coordinating cyclo-P3 ligand. In contrast, when the same reaction is performed with two equivalents of the cobalt(i) complex, a dinuclear product is formed which features an unusual P4 chain in its molecular structure.

Dynamic Conformational Behavior in Stable Pentaorganosilicates

Silicates with five organic groups are conformationally dynamic even with two bidentate ligands. Symmetry breaking by incorporating a single nitrogen or phosphorus atom provides insight into their dynamic behavior. N‐containing silicates with bidentate 2‐phenylpyridine, biphenyl, and a Me (8), Et (9) or Ph (10) ligand were studied comprehensively by NMR spectroscopy and DFT theory to reveal two isoenergetic conformers with a barrier of ca. 10 kcal mol–1. P‐containing silicate 14 with bidentate triphenylphosphane, biphenyl, and Me ligands is subject to multiple Berry pseudorotations, turnstile rotations, and conformational flexibility of the P‐center. The stability increased by masking the P‐center with a BH3 group (16). DFT and NMR modeling reveal two isoenergetic conformers for 16 with a barrier of ca. 19 kcal‧mol–1 for a complex interconversion pathway. This barrier bodes well for the design of configurationally stable chiral‐at‐metal transition metal catalysts.

Solvent-Dependent Sensitization of Ytterbium and Neodymium via an Intramolecular Excimer.

We report the synthesis of a di(1-pyrenyl)phosphoryl acetophenone ligand containing two pyrenyl moieties linked by a single phosphorus atom. The ligand exhibits solvent-dependent emission: in nonpolar solvents, typical monomeric pyrene emission is observed, whereas in polar solvents, an additional broad and structureless emission appears. The emission in polar solvents is concentration independent and is attributed to the emission of an intramolecular excimer. The coordination of the di(1-pyrenyl)phosphoryl acetophenone ligand as well as the corresponding deprotonated anionic di(1-pyrenyl)phosphoryl acetophenonate ligand was studied with the near-infrared emitting lanthanides, neodymium and ytterbium. Solvent-dependent sensitization of both lanthanides was observed and correlates with the presence of the excimer emission. Sensitization of ytterbium is more efficient than neodymium, and the overall quantum yields were found to be 12.8 and 1.9% for ytterbium and neodymium, respectively.

Bowl Shaped Monodentate Phosphines by Condensation of Imidazole Units with Boranes

The condensation of imidazole moieties with boranes leading to molecular units with N–BR2–N bridges was accomplished by attaching three imidazole units to a single phosphorus atom. In this way, boron bridged trisimidazolylphosphines 3–7 were synthesized in good yields. The chiral derivatives 5a, 5d, 6, and 7 are C3 symmetric, whereas 5b and 5c carry no symmetry element (C1). The steric bulk of the ligands can easily be tuned by introduction of different substituents at the three bridging boron atoms. All phosphines feature small CPC angles between 91–93° leading to a s‐type lone pair donor at the phosphorus atom combined with reasonable π‐accepting properties. Ni (8) and Au metal complexes (9, 10) with very short metal phosphorus bonds were synthesized. The short metal–phosphorus distance is a consequence of the pronounced s‐character of the phosphine lone pair.

Single-electron transistor with an island formed by several dopant phosphorus atoms

We present the results of an experimental study of electron transport through individual phosphorus dopants implanted into a silicon crystal. We developed an original technique for single-electron transistor fabrication from silicon-on-insulator material with an island formed by single phosphorus atoms. The proposed method is based on well-known CMOS compatible technological processes that are standard in semiconductor electronics and may be used in most research groups. The large Coulomb blockade energy value of the investigated single-electron transistor (∼20 meV) allows one to observe single-electron effects in a wide temperature range up to 77 K. We measured and analyzed stability diagrams of fabricated experimental structures. We demonstrated a single-electron transistor with controllable electron transport through two to three phosphorus dopants only.

Enhancing coherence in molecular spin qubits via atomic clock transitions.

Quantum computing is an emerging area within the information sciences revolving around the concept of quantum bits (qubits). A major obstacle is the extreme fragility of these qubits due to interactions with their environment that destroy their quantumness. This phenomenon, known as decoherence, is of fundamental interest. There are many competing candidates for qubits, including superconducting circuits, quantum optical cavities, ultracold atoms and spin qubits, and each has its strengths and weaknesses. When dealing with spin qubits, the strongest source of decoherence is the magnetic dipolar interaction. To minimize it, spins are typically diluted in a diamagnetic matrix. For example, this dilution can be taken to the extreme of a single phosphorus atom in silicon, whereas in molecular matrices a typical ratio is one magnetic molecule per 10,000 matrix molecules. However, there is a fundamental contradiction between reducing decoherence by dilution and allowing quantum operations via the interaction between spin qubits. To resolve this contradiction, the design and engineering of quantum hardware can benefit from a 'bottom-up' approach whereby the electronic structure of magnetic molecules is chemically tailored to give the desired physical behaviour. Here we present a way of enhancing coherence in solid-state molecular spin qubits without resorting to extreme dilution. It is based on the design of molecular structures with crystal field ground states possessing large tunnelling gaps that give rise to optimal operating points, or atomic clock transitions, at which the quantum spin dynamics become protected against dipolar decoherence. This approach is illustrated with a holmium molecular nanomagnet in which long coherence times (up to 8.4 microseconds at 5 kelvin) are obtained at unusually high concentrations. This finding opens new avenues for quantum computing based on molecular spin qubits.

Bell's inequality violation with spins in silicon.

Bell's theorem proves the existence of entangled quantum states with no classical counterpart. An experimental violation of Bell's inequality demands simultaneously high fidelities in the preparation, manipulation and measurement of multipartite quantum entangled states, and provides a single-number benchmark for the performance of devices that use such states for quantum computing. We demonstrate a Bell/ Clauser-Horne-Shimony-Holt inequality violation with Bell signals up to 2.70(9), using the electron and the nuclear spins of a single phosphorus atom embedded in a silicon nanoelectronic device. Two-qubit state tomography reveals that our prepared states match the target maximally entangled Bell states with >96% fidelity. These experiments demonstrate complete control of the two-qubit Hilbert space of a phosphorus atom and highlight the important function of the nuclear qubit to expand the computational basis and maximize the readout fidelity.

A tight-binding study of single-atom transistors.

A detailed theoretical study of the electronic and transport properties of a single atom transistor, where a single phosphorus atom is embedded within a single crystal transistor architecture, is presented. Using a recently reported deterministic single-atom transistor as a reference, the electronic structure of the device is represented atomistically with a tight-binding model, and the channel modulation is simulated self-consistently with a Thomas-Fermi method. The multi-scale modeling approach used allows confirmation of the charging energy of the one-electron donor charge state and explains how the electrostatic environments of the device electrodes affects the donor confinement potential and hence extent in gate voltage of the two-electron charge state. Importantly, whilst devices are relatively insensitive to dopant ordering in the highly doped leads, a ∼1% variation of the charging energy is observed when a dopant is moved just one lattice spacing within the device. The multi-scale modeling method presented here lays a strong foundation for the understanding of single-atom device structures: essential for both classical and quantum information processing.

Imaging of buried phosphorus nanostructures in silicon using scanning tunneling microscopy

We demonstrate the locating and imaging of single phosphorus atoms and phosphorus dopant nanostructures, buried beneath the Si(001) surface using scanning tunneling microscopy. The buried dopant nanostructures have been fabricated in a bottom-up approach using scanning tunneling microscope lithography on Si(001). We find that current imaging tunneling spectroscopy is suited to locate and image buried nanostructures at room temperature and with residual surface roughness present. From these studies, we can place an upper limit on the lateral diffusion during encapsulation with low-temperature Si molecular beam epitaxy.

Spin readout and addressability of phosphorus-donor clusters in silicon

The spin states of an electron bound to a single phosphorus donor in silicon show remarkably long coherence and relaxation times, which makes them promising building blocks for the realization of a solid-state quantum computer. Here we demonstrate, by high-fidelity (93%) electrical spin readout, that a long relaxation time T1 of about 2 s, at B=1.2 T and T≈100 mK, is also characteristic of electronic spin states associated with a cluster of few phosphorus donors, suggesting their suitability as hosts for spin qubits. Owing to the difference in the hyperfine coupling, electronic spin transitions of such clusters can be sufficiently distinct from those of a single phosphorus donor. Our atomistic tight-binding calculations reveal that when neighbouring qubits are hosted by a single phosphorus atom and a cluster of two phosphorus donors, the difference in their electron spin resonance frequencies allows qubit rotations with error rates ≈10(-4). These results provide a new approach to achieving individual qubit addressability.

A single-atom electron spin qubit in silicon

A single atom is the prototypical quantum system, and a natural candidate for a quantum bit, or qubit--the elementary unit of a quantum computer. Atoms have been successfully used to store and process quantum information in electromagnetic traps, as well as in diamond through the use of the nitrogen-vacancy-centre point defect. Solid-state electrical devices possess great potential to scale up such demonstrations from few-qubit control to larger-scale quantum processors. Coherent control of spin qubits has been achieved in lithographically defined double quantum dots in both GaAs (refs 3-5) and Si (ref. 6). However, it is a formidable challenge to combine the electrical measurement capabilities of engineered nanostructures with the benefits inherent in atomic spin qubits. Here we demonstrate the coherent manipulation of an individual electron spin qubit bound to a phosphorus donor atom in natural silicon, measured electrically via single-shot read-out. We use electron spin resonance to drive Rabi oscillations, and a Hahn echo pulse sequence reveals a spin coherence time exceeding 200 µs. This time should be even longer in isotopically enriched (28)Si samples. Combined with a device architecture that is compatible with modern integrated circuit technology, the electron spin of a single phosphorus atom in silicon should be an excellent platform on which to build a scalable quantum computer.

Influence of the structure of the diphosphine ligand on the copper fluoride and copper hydride complexes

The influence of the structure of diphosphine ligands on copper fluoride and copper (I) hydride complexes has been investigated by a theoretical DFT study. For both complexes, two stable structures appear. A near “symmetric” one, with both phosphorus lone pairs coordinated to the copper atom, and an “asymmetric” with a single phosphorus atom linked to the copper atom. Three interactions influence the stability of one situation over the other. Although the higher ligand deformation energy observed for the near symmetric complexes is compensated by the increased stability due to the second metal-phosphorus bond, a supplementary hydrogen bond interaction observed for the copper fluoride complexes, leads to a more important stabilization of the asymmetric complexes. The presence of multiple stable catalytic structures is most likely of importance for the reactivity of the catalytic reactions involving copper hydride or copper fluoride catalysts.

Structural, magnetic, and transport properties of substitutionally doped graphene nanoribbons from first principles

We present a study of the electronic properties of narrow zigzag and armchair nanoribbons substitutionally doped with a single boron, nitrogen, or phosphorus atom. Using density-functional calculations, we analyze the formation energy, electronic band structure, magnetic, and quantum conductance properties of these nanoribbons with doping sites ranging from the edge to the center of the ribbon. Substitutional doping is found to be most favorable at the ribbon edge in all the cases except for the boron-doped armchair ribbon, which has the lowest formation energy in the three-coordinated site next to the edge. Boron-doped zigzag nanoribbons exhibit spin-dependent donorlike states when the dopant is on the ribbon edge, and acceptor states as the dopant is moved toward the ribbon center. Nitrogen-doped zigzag nanoribbons show the opposite effect, while phosphorus-doped nanoribbons exhibit both donorlike and acceptorlike states. The band structure and local density of states indicate that dips in conductance occur from either the presence of a localized state or the opening of mini band gaps around a particular energy value. The variations in conductance arising from different doping profiles could be useful for tailoring the properties of graphene-based nanoelectronic devices.

Diffusion pathways of phosphorus atoms on silicon (001)

Using density-functional theory and a combination of growing string and dimer method transition state searches, we investigate the interaction of phosphorus atoms with the silicon (001) surface. We report reaction pathways for three technologically important processes: diffusion of phosphorus adatoms on the surface, incorporation of the phosphorus adatom into the surface, and diffusion of the incorporated phosphorus atom within the surface. These reactions have direct relevance to nanoscale lithographic schemes capable of positioning single phosphorus atoms on the silicon surface. Temperatures of activation for the various processes are calculated and, where possible, compared with experiment.