Single-atom spectroscopy of phosphorus dopants implanted into graphene
Toma Susi, Trevor P. Hardcastle, Hans Hofsäss, Andreas Mittelberger, Timothy J. Pennycook, Clemens Mangler, Rik Drummond-Brydson, Andrew J. Scott, Jannik C. Meyer, Jani Kotakoski
One of the keys behind the success of the modern semiconductor technology has been the ion implantation of silicon, which allows its electronic properties to be tailored. For similar purposes, heteroatoms have been introduced into carbon nanomaterials both during growth and using post-growth methods. However, due to the nature of the samples, it has been challenging to determine whether the heteroatoms have been incorporated into the lattice as intended, with direct observations so far being limited to N and B dopants, and incidental Si impurities. Furthermore, ion implantation of these materials is more challenging due to the requirement of very low ion energies and atomically clean surfaces. Here, we provide the first atomic-resolution imaging and electron energy loss spectroscopy (EELS) evidence of phosphorus atoms incorporated into the graphene lattice by low-energy ion irradiation. The measured P L-edge response of an single-atom EELS spectrum map shows excellent agreement with an ab initio spectrum simulation, conclusively identifying the P in a buckled substitutional configuration. Our results demonstrate the viability of phosphorus as a lattice dopant in $sp^2$-bonded carbon structures and provide its unmistakeable fingerprint for further studies.
This work reports an ESR study of low energy, low fluence phosphorus ion implantation into silicon in order to observe the activation of phosphorus donors placed in close proximity to the Si-SiO2 interface. Electrical measurements, which were used to estimate donor activation levels, reported high implant recoveries when using 14 keV phosphorus ions however, it was not possible to correlate the intensity of the hyperfine resonance signal with the electrical measurements in the presence of an SiO2 interface due to donor state ionisation (i.e. compensation effects). Comparative measurements made…
Transition metals (TMs) implanted in oxides with rock-salt crystal structures (for example MgO and BaO) are assumed to substitute cations (Mg in case of MgO) from the lattice sites. We show that not all implanted TMs substitute cations but can be stable in interstitial sites as well. Stability of TM (Sc--Zn) dopants in various charge states in MgO and BaO has been investigated in the framework of density functional theory. We propose an effective way to calculate stability of implanted metals that let us predict site preference (interstitial or substitution) of the dopant in the host. We find …
We have used scanning tunneling microscopy to identify individual phosphorus dopant atoms near the clean silicon (100)-(2x1) reconstructed surface. The charge-induced band bending signature associated with the dopants shows up as an enhancement in both filled and empty states and is consistent with the appearance of n-type dopants on compound semiconductor surfaces and passivated Si(100)-(2x1). We observe dopants at different depths and see a strong dependence of the signature on the magnitude of the sample voltage. Our results suggest that, on this clean surface, the antibonding surface state…
Atomic-level structural changes in materials are important but challenging to study. Here, we demonstrate the dynamics and the possibility of manipulating a phosphorus dopant atom in graphene using scanning transmission electron microscopy (STEM). The mechanisms of various processes are explored and compared with those of other dopant species by first-principles calculations. This work paves the way for designing a more precise and optimized protocol for atomic engineering.
A deep level transient spectroscopy (DLTS) study of defects created by low-fluence, low-energy ion implantation for development of ion-implanted silicon field-effect transistors for spin-dependent transport experiments is presented. Standard annealing strategies are considered to activate the implanted dopants and repair the implantation damage in test metal-oxide-semiconductor (MOS) capacitors. Fixed oxide charge, interface trapped charge and the role of minority carriers in DLTS are investigated. A furnace anneal at 950 $\rm ^{o}$C was found to activate the dopants but did not repair the imp…
We simulated and experimentally investigated the sputter yield of ZnO and GaAs nanowires, which were implanted with energetic Mn ions at room temperature. The resulting thinning of the nanowires and the dopant concentration with increasing Mn ion fluency were measured by accurate scanning electron microscopy (SEM) and nano-X-Ray Fluorescence (nanoXRF) quantification, respectively. We observed a clear enhanced sputter yield for the irradiated nanowires compared to bulk, which is also corroborated by iradina simulations. These show a maximum if the ion range matches the nanowire diameter. As a c…
We present the results of electrically-detected magnetic resonance (EDMR) experiments on silicon with ion-implanted phosphorus nanostructures, performed at 5 K. The devices consist of high-dose implanted metallic leads with a square gap, into which Phosphorus is implanted at a non-metallic dose corresponding to 10^17 cm^-3. By restricting this secondary implant to a 100 nm x 100 nm region, the EDMR signal from less than 100 donors is detected. This technique provides a pathway to the study of single donor spins in semiconductors, which is relevant to a number of proposals for quantum informati…
Explosive crystallization (EC) is often observed when using nanosecond-pulsed melt laser annealing (MLA) in amorphous silicon (Si) and germanium (Ge). The solidification velocity in EC is so fast that a diffusion-less crystallization can be expected. In the contacts of advanced transistors, the active level at the metal/semiconductor Schottky interface must be very high to achieve a sub-10^{-9} ohm.cm2 contact resistivity, which has been already demonstrated by using the dopant surface segregation induced by MLA. However, the beneficial layer of a few nanometers at the surface may be easily co…
Annealing Mg-implanted homoepitaxial GaN at temperatures at or above 1400 °C eliminates the formation of inversion domains and leads to improved dopant activation efficiency. Extended defects in the form of inversion domains contain electrically inactive Mg after post-implantation annealing at temperatures as high as 1300 °C (one GPa N2 overpressure), which results in a low dopant activation efficiency. Triple axis X-ray data show that the implant-induced strain is fully relieved after annealing at 1300 °C for 10 min, indicating that the strain-inducing point defects formed during implantation…
Using first-principles modelling based on density functional theory we show that oxides implanted with transition metal can act as support for Au single atoms, which are stable against agglomeration. In our previous work we have shown that implanted transition metal, doped in BaO is stable as interstitial in various charge states by transferring the excess charge to an acceptor level close to VBM. Taking Nb as an example we show that single atom Au has its Fermi level close to the VBM of BaO and hence is able to accept charge from the dopant. This charge transfer process between Nb and Au help…
To simulate the transient enhanced diffusion near the surface or interface, a set of equations describing the impurity diffusion and quasichemical reactions of dopant atoms and point defects in ion-implanted layers is proposed and analyzed. The diffusion equations obtained take into account different charge states of mobile or immobile species and drift the mobile species in the built-in electric field and field of elastic stresses. The absorption of self-interstitials on the surface and drift of the defects due to elastic stresses result in the nonuniform distributions of point defects. It wa…
The influence of implantation conditions on dopant activation in Al-implanted 4H-SiC: A MD study applying an Al potential fitted to DFT barriers
CDL for Multi-Scale Process Modeling of Semiconductor Devices and Sensors, at the Institute for Microelectronics, TU Wien（维也纳工业大学微电子研究所多尺度半导体器件与传感器工艺建模中心）；Silvaco Europe Ltd.（Silvaco欧洲有限公司）
Implantation and diffusion of Zn dopant into bulk InP:S were performed. Zn concentration profiles were investigated by secondary ion mass spectrometry and capacitance-voltage method. We find that thermodynamic conditions of annealing influence diffusion mechanism of Zn atoms. Excess phosphorus vacancies generation causes diffusion of Zn dopant by the complex [V_{P}-Zn_{In}-V_{P}] producing characteristic diffusion profile with the sharp slope. Such electrically inactive Zn configuration cause lower diffusion coefficient than that in the generally known interstitial-substitutional mechanism.
We simulate dopant profiles for phosphorus implantation into silicon using a new model for electronic stopping power. In this model, the electronic stopping power is factorized into a globally averaged effective charge Z1*, and a local charge density dependent electronic stopping power for a proton. There is only a single adjustable parameter in the model, namely the one electron radius rs0 which controls Z1*. By fine tuning this parameter, we obtain excellent agreement between simulated dopant profiles and the SIMS data over a wide range of energies for the channeling case. Our work provides …
Advanced hydrogen lithography techniques and low-temperature epitaxial overgrowth enable patterning of highly phosphorus-doped silicon (Si:P) monolayers (ML) with atomic precision. This approach to device fabrication has made Si:P monolayer systems a testbed for multiqubit quantum computing architectures and atomically precise 2-D superlattice designs whose behaviors are directly tied to the deterministic placement of single dopants. However, dopant segregation, diffusion, surface roughening, and defect formation during the encapsulation overgrowth introduce large uncertainties to the exact do…
Dopants in silicon have been studied for many decades using optical and electron spin resonance (ESR) spectroscopy. Recently, new features have been observed in the spectra of dopants in isotopically enriched 28Si since the reduced inhomogeneous linewidth in this material improves spectral resolution. With this in mind, we measured ESR on exchange coupled phosphorus dimers in 28Si and report two results. First, a new fine structure is observed in the ESR spectrum arising from state mixing by the hyperfine coupling to the 31P nuclei, which is enhanced when the exchange energy is comparable to t…
Dopants in crystalline silicon such as phosphorus (Si:P) have electronic and nuclear spins with exceptionally long coherence times making them promising platforms for quantum computing and quantum sensing. The demonstration of single-spin single-shot readout brings these ideas closer to implementation. Progress in fabricating atomic-scale Si:P structures with scanning tunnelling microscopes offers a powerful route to scale up this work, taking advantage of techniques developed by the computing industry. The experimental and theoretical sides of this emerging quantum technology are reviewed wit…
Molecular Nitrogen Formation in Nitrogen-Implanted (100) $β-Ga_2O_3$ Revealed by Temperature-Dependent $N$ $K$-edge XANES
The Centre for Advanced Materials and Technologies, CEZAMAT at the Warsaw University of Technology（华沙理工大学先进材料与技术中心）；Institute of Plasma Physics and Laser Microfusion（等离子体物理与激光微聚变研究所）；Institute of Microelectronics and Optoelectronics, Warsaw University of Technology（华沙理工大学微电子与光电子研究所）；Institute of Fundamental Technological Research Polish Academy of Sciences（波兰科学院基础技术研究所）；National Center for Nuclear Research（国家核研究中心）；Institute of Physics, Maria Curie-Sklodowska University（玛丽亚·居里-斯克沃多夫斯卡大学物理研究所）；Helmholtz-Zentrum Dresden-Rossendorf（德累斯顿-罗森多夫亥姆霍兹中心）；Institute of Physics PAS（波兰科学院物理研究所）；National Synchrotron Radiation Centre SOLARIS, Jagiellonian University（雅盖隆大学SOLARIS国家同步辐射中心）；Faculty of Chemistry, University of Warsaw（华沙大学化学系）；Institute of High Pressure Physics Polish Academy of Sciences（波兰科学院高压物理研究所）；Leibniz-Institut für Kristallzüchtung（莱布尼茨晶体生长研究所）
To explain the effect of electron density saturation at high phosphorus concentrations the model of negatively charged phosphorus clusters was compared with the experimental data. A number of negatively charged clusters incorporating a point defect and phosphorus atoms were investigated at temperatures of 920 and 1000 Celsius degrees. It was established that for clusters incorporating more than one phosphorus atom calculated electron density reached a maximum value and then monotonically and slowly decreased with increasing the total dopant concentration. If the cluster incorporates 3-4 phosph…
Special point defects in semiconductors have been envisioned as suitable components for quantum-information technology. The identification of new deep centers in silicon that can be easily activated and controlled is a main target of the research in the field. Vacancy-related complexes are suitable to provide deep electronic levels but they are hard to control spatially. With the spirit of investigating solid state devices with intentional vacancy-related defects at controlled position, here we report on the functionalization of silicon vacancies by implanting Ge atoms through single-ion impla…
Phosphorus has received recent attention in the context of high-capacity and high-rate anodes for lithium and sodium-ion batteries. Here, we present a first principles structure prediction study combined with NMR calculations which gives us insights into its lithiation/sodiation process. We report a variety of new phases phases found by AIRSS and the atomic species swapping methods. Of particular interest, a stable Na$_5$P$_4$-C2/m structure and locally stable structures found less than 10 meV/f.u. from the convex hull, such as Li$_4$P$_3$-P2$_1$2$_1$2$_1$, NaP$_5$-Pnma and Na$_4$P$_3$-Cmcm. T…
We implanted ultra low doses (2x10^11 cm-2) of 121Sb ions into isotopically enriched 28Si and find high degrees of electrical activation and low levels of dopant diffusion after rapid thermal annealing. Pulsed Electron Spin Resonance shows that spin echo decay is sensitive to the dopant depths, and the interface quality. At 5.2 K, a spin decoherence time, T2, of 0.3 ms is found for profiles peaking 50 nm below a Si/SiO2 interface, increasing to 0.75 ms when the surface is passivated with hydrogen. These measurements provide benchmark data for the development of devices in which quantum informa…
This work reports on the effect of high temperature annealing on the electrical properties of p-type implanted 4H-SiC. Ion implantations of Aluminium (Al) at different energies (30 - 200 keV) were carried out to achieve 300 nm thick acceptor box profiles with a concentration of about 1020 at/cm3. The implanted samples were annealed at high temperatures (1675-1825 °C). Morphological analyses of the annealed samples revealed only a slight increase of the surface roughness RMS up to 1775°C, while this increase becomes more significant at 1825°C (RMS=1.2nm). Room temperature Hall measurements resu…
The kinetics of intrinsic and dopant-enhanced solid phase epitaxy (SPE) is stud- ied in amorphous germanium (a-Ge) layers formed by ion implantation on <100> Ge substrates. The SPE rates were measured with a time-resolved reflectivity (TRR) system between 300 and 540 degC and found to have an activation energy of (2.15 +/- 0.04) eV. To interpret the TRR measurements the refractive indices of the a-Ge layers were measured at the two wavelengths used, 1.152 and 1.532 μm. For the first time, SPE rate measurements on thick a-Ge layers (>3 μm) have also been performed to distinguish between bulk an…
Incorporating heteroatoms into the graphene lattice may be used to tailor its electronic, mechanical and chemical properties. Direct substitutions have thus far been limited to incidental Si impurities and P, N and B dopants introduced using low-energy ion implantation. We present here the heaviest impurity to date, namely $^{74}$Ge$^+$ ions implanted into monolayer graphene. Although sample contamination remains an issue, atomic resolution scanning transmission electron microscopy imaging and quantitative image simulations show that Ge can either directly substitute single atoms, bonding to t…
We have performed the numerical modeling of Ge(111)-(2x1) surface electronic properties in vicinity of P donor impurity atom located near the surface. We have found a notable increase of surface $LDOS$ around surface dopant near the bottom of empty surface states band $π^*$, which we called split state due to its limited spatial extent and energetic position inside the band gap. We show, that despite of well established bulk donor impurity energy level position at the very bottom of conduction band, surface donor impurity on Ge(111)-(2x1) surface might produce energy level below Fermi energy, …
A nonequilibrium Green's function technique combined with density functional theory is used to study the spin-dependent electronic band structure and transport properties of zigzag silicene nanoribbons (ZSiNRs) doped with aluminum (Al) or phosphorus (P) atoms. The presence of a single Al or P atom induces quasibound states in ZSiNRs that can be observed as new dips in the electron conductance. The Al atom acts as an acceptor whereas the P atom acts as a donor when it is placed at the center of the ribbon. This behavior is reversed when the dopant is placed on the edges. Accordingly, an accepto…
In amorphous materials, acceptor and donor impurities rarely dope the system (shift the Fermi level). We find out why in a-Si:H. We report simulations on B and P doping of a-Si:H and a-Si. We analyze the Electronic Density of States (EDOS) with concentrations ranging from 1.6% to 12.5% of B or P in a-Si. The results indicate that tetrahedral B and P are effective doping configurations in a-Si, but high impurity concentrations introduce defect states. Clustered B or P also introduced mid-gap states. For a-Si:H, we report that both B(3,1) and P(3,1) (B or P atom bonded with three Si atoms and on…
The aggressive scaling of silicon-based nanoelectronics has reached the regime where device function is affected not only by the presence of individual dopants, but more critically their position in the structure. The quantitative determination of the positions of subsurface dopant atoms is an important issue in a range of applications from channel doping in ultra-scaled transistors to quantum information processing, and hence poses a significant challenge. Here, we establish a metrology combining low-temperature scanning tunnelling microscopy (STM) imaging and a comprehensive quantum treatmen…
The formation of quantum computer test structures in silicon by ion implantation enables the characterization of spin readout mechanisms with ensembles of dopant atoms and the development of single atom devices. We briefly review recent results in the characterization of spin dependent transport and single ion doping and then discuss the diffusion and segregation behaviour of phosphorus, antimony and bismuth ions from low fluence, low energy implantations as characterized through depth profiling by secondary ion mass spectrometry (SIMS). Both phosphorus and bismuth are found to segregate to th…
Using silicon MOSFETs with thin (5nm) thermally grown SiO2 gate dielectrics, we characterize the density of electrically active traps at low-temperature after 16keV phosphorus ion-implantation through the oxide. We find that, after rapid thermal annealing at 1000oC for 5 seconds, each implanted P ion contributes an additional 0.08 plus/minus 0.03 electrically active traps, whilst no increase in the number of traps is seen for comparable silicon implants. This result shows that the additional traps are ionized P donors, and not damage due to the implantation process. We also find, using the roo…
Spins in the `semiconductor vacuum' of silicon-28 ($^{28}$Si) are suitable qubit candidates due to their long coherence times. An isotopically purified substrate of $^{28}$Si is required to limit the decoherence pathway caused by magnetic perturbations from surrounding $^{29}$Si nuclear spins (I=1/2), present in natural Si (nat Si) at an abundance of 4.67%. We isotopically enrich surface layers of nat Si by sputtering using high fluence $^{28}$Si$^-$ implantation. Phosphorus (P) donors implanted into one such $^{28}$Si layer with ~3000 ppm $^{29}$Si, produced by implanting 30 keV $^{28}$Si$^-$…
In this work, we have studied the crystal defectiveness and doping activation subsequent to ion implantation and post-annealing by using various techniques including photoluminescence (PL), Raman spectroscopy and transmission electron microscopy (TEM). The aim of this work was to test the effectiveness of double step annealing to reduce the density of point defects generated during the annealing of a P implanted 4H-SiC epitaxial layer. The outcome of this work evidences that neither the first, 1 hour isochronal annealing at 1650 - 1700 - 1750 °C, nor the second one, at 1500 °C for times betwee…
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 germ…
Optomechanical resonators were fabricated on a silicon-on-insulator (SOI) substrate that had been implanted with phosphorus donors. The resonators' mechanical and optical properties were then measured (at 6 kelvin and room temperature) before and after the substrate was annealed. All measured resonators survived the annealing and their mechanical linewidths decreased while their optical and mechanical frequencies increased. This is consistent with crystal lattice damage from the ion implantation causing the optical and mechanical properties to degrade and then subsequently being repaired by th…
Inspired by a recent experimental and theoretical study [Yang et al., 2017], wherein protrusions in graphene have been proposed as an effective strategy to enhance the performance of sodium ion batteries, a comprehensive study of the effects of phosphorus doping in graphene on adsorption and diffusion behaviour of Li is carried out by using density functional theory. We find that protrusion introduced by P-dopant in graphene enhances the adsorption of a single Li atom onto the anode due to an additional partial covalent bonding character between Li and carbon atoms of the substrate. However, w…
Production of Upgraded Metallurgical Grade (UMG) silicon for a low-cost high-efficiency and reliable PV technology
FerroGlobe；Aurinka PV Group（Aurinka光伏集团）；Instituto de Energía Solar, ETSI Telecomunicación, Universidad Politécnica de Madrid（马德里理工大学电信工程学院太阳能研究所）；ODTÜ-GÜNAM (Center for Solar Energy Research and Applications)（中东技术大学-太阳能源研究与应用中心）；Middle East Technical University（中东技术大学）；Nanophotonics Technology Center – Universidad Politécnica de Valencia（巴伦西亚理工大学纳米光子技术中心）
