Stochastic incorporation kinetics can be a limiting factor in the scalability of semiconductor fabrication technologies using atomic-precision techniques. While these technologies have recently been extended from donors to acceptors, the extent to which kinetics will impact single-acceptor incorporation has yet to be assessed. To identify the precursor molecule and dosing conditions that are promising for deterministic incorporation, we develop and apply an atomistic model for the single-acceptor incorporation rates of several recently demonstrated molecules: diborane (B2H6), boron trichloride (BCl3), and aluminum trichloride in both monomer (AlCl3) and dimer forms (Al2Cl6). While all three precursors can realize single-acceptor incorporation, we predict that diborane is unlikely to realize deterministic incorporation, boron trichloride can realize deterministic incorporation with modest heating (50 °C), and aluminum trichloride can realize deterministic incorporation at room temperature. We conclude that both boron and aluminum trichloride are promising precursors for atomic-precision single-acceptor applications, with the potential to enable the reliable production of large arrays of single-atom quantum devices.
Thin, high-density layers of dopants in semiconductors, known as δ-layer systems, have recently attracted attention as a platform for exploration of the future quantum and classical computing when patterned in plane with atomic precision. However, there are many aspects of the conductive properties of these systems that are still unknown. Here we present an open-system quantum transport treatment to investigate the local density of electron states and the conductive properties of the δ-layer systems. A successful application of this treatment to phosphorous δ-layer in silicon both explains the origin of recently-observed shallow sub-bands and reproduces the sheet resistance values measured by different experimental groups. Further analysis reveals two main quantum-mechanical effects: 1) the existence of spatially distinct layers of free electrons with different average energies; 2) significant dependence of sheet resistance on the δ-layer thickness for a fixed sheet charge density.
Atomically precise ultradoping of silicon is possible with atomic resists, area-selective surface chemistry, and a limited set of hydride and halide precursor molecules, in a process known as atomic precision advanced manufacturing (APAM). It is desirable to expand this set of precursors to include dopants with organic functional groups and here we consider aluminium alkyls, to expand the applicability of APAM. We explore the impurity content and selectivity that results from using trimethyl aluminium and triethyl aluminium precursors on Si(001) to ultradope with aluminium through a hydrogen mask. Comparison of the methylated and ethylated precursors helps us understand the impact of hydrocarbon ligand selection on incorporation surface chemistry. Combining scanning tunneling microscopy and density functional theory calculations, we assess the limitations of both classes of precursor and extract general principles relevant to each.
We present an efficient self-consistent implementation of the Non-Equilibrium Green Function formalism, based on the Contact Block Reduction method for fast numerical efficiency, and the predictor-corrector approach, together with the Anderson mixing scheme, for the self-consistent solution of the Poisson and Schrödinger equations. Then, we apply this quantum transport framework to investigate 2D horizontal Si:P δ-layer Tunnel Junctions. We find that the potential barrier height varies with the tunnel gap width and the applied bias and that the sign of a single charge impurity in the tunnel gap plays an important role in the electrical current.
The atomic precision advanced manufacturing (APAM) enabled vertical tunneling field effect transistor (TFET) presents a new opportunity in microelectronics thanks to the use of ultra-high doping and atomically abrupt doping profiles. We present modeling and assessment of the APAM TFET using TCAD Charon simulation. First, we show, through a combination of simulation and experiment, that we can achieve good control of the gated channel on top of a phosphorus layer made using APAM, an essential part of the APAM TFET. Then, we present simulation results of a preliminary APAM TFET that predict transistor-like current-voltage response despite low device performance caused by using large geometry dimensions. Future device simulations will be needed to optimize geometry and doping to guide device design for achieving superior device performance.
Ultradoping introduces unprecedented dopant levels into Si, which transforms its electronic behavior and enables its use as a next-generation electronic material. Commercialization of ultradoping is currently limited by gas-phase ultra-high vacuum requirements. Solvothermal chemistry is amenable to scale-up. However, an integral part of ultradoping is a direct chemical bond between dopants and Si, and solvothermal dopant-Si surface reactions are not well-developed. This work provides the first quantified demonstration of achieving ultradoping concentrations of boron (∼1e14 cm2) by using a solvothermal process. Surface characterizations indicate the catalyst cross-reacted, which led to multiple surface products and caused ambiguity in experimental confirmation of direct surface attachment. Density functional theory computations elucidate that the reaction results in direct B−Si surface bonds. This proof-of-principle work lays groundwork for emerging solvothermal ultradoping processes.
A materials synthesis method that we call atomic-precision advanced manufacturing (APAM), which is the only known route to tailor silicon nanoelectronics with full 3D atomic precision, is making an impact as a powerful prototyping tool for quantum computing. Quantum computing schemes using atomic (31P) spin qubits are compelling for future scale-up owing to long dephasing times, one- and two-qubit gates nearing high-fidelity thresholds for fault-tolerant quantum error correction, and emerging routes to manufacturing via proven Si foundry techniques. Multiqubit devices are challenging to fabricate by conventional means owing to tight interqubit pitches forced by short-range spin interactions, and APAM offers the required (Å-scale) precision to systematically investigate solutions. However, applying APAM to fabricate circuitry with increasing numbers of qubits will require significant technique development. Here, we provide a tutorial on APAM techniques and materials and highlight its impacts in quantum computing research. Finally, we describe challenges on the path to multiqubit architectures and opportunities for APAM technique development. Graphic Abstract: [Figure not available: see fulltext.]
The adsorption of AlCl3 on Si(100) and the effect of annealing the AlCl3-dosed substrate were studied to reveal key surface processes for the development of atomic-precision, acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl3 readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing the AlCl3-dosed substrate at temperatures below 450 °C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 °C and above, and Cl desorption was observed for temperatures beyond 450 °C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 1020 cm-3 across a ∼2.7 nm-thick δ-doped region. The Al concentration achieved here and the processing parameters utilized promote AlCl3 as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.
Diborane (B2H6) is a promising molecular precursor for atomic precision p-type doping of silicon that has recently been experimentally demonstrated [ Škereň et al. Nat. Electron. 2020 ]. We use density functional theory (DFT) calculations to determine the reaction pathway for diborane dissociating into a species that will incorporate as electrically active substitutional boron after adsorbing onto the Si(100)-2×1 surface. Our calculations indicate that diborane must overcome an energy barrier to adsorb, explaining the experimentally observed low sticking coefficient (<1 × 10-4 at room temperature) and suggesting that heating can be used to increase the adsorption rate. Upon sticking, diborane has an ≈50% chance of splitting into two BH3 fragments versus merely losing hydrogen to form a dimer such as B2H4. As boron dimers are likely electrically inactive, whether this latter reaction occurs is shown to be predictive of the incorporation rate. The dissociation process proceeds with significant energy barriers, necessitating the use of high temperatures for incorporation. Using the barriers calculated from DFT, we parameterize a Kinetic Monte Carlo model that predicts the incorporation statistics of boron as a function of the initial depassivation geometry, dose, and anneal temperature. Our results suggest that the dimer nature of diborane inherently limits its doping density as an acceptor precursor and furthermore that heating the boron dimers to split before exposure to silicon can lead to poor selectivity on hydrogen and halogen resists. This suggests that, while diborane works as an atomic precision acceptor precursor, other non-dimerized acceptor precursors may lead to higher incorporation rates at lower temperatures.
The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with subnanometer precision, typically for quantum physics experiments. This process, which we call atomic precision advanced manufacturing (APAM), dopes silicon beyond the solid-solubility limit and produces electrical and optical characteristics that may also be useful for microelectronic and plasmonic applications. However, scanned probe lithography lacks the throughput required to develop more sophisticated applications. Here, we demonstrate and characterize an APAM device workflow where scanned probe lithography of the atomic layer resist has been replaced by photolithography. An ultraviolet laser is shown to locally and controllably heat silicon above the temperature required for hydrogen depassivation on a nanosecond timescale, a process resistant to under- and overexposure. STM images indicate a narrow range of energy density where the surface is both depassivated and undamaged. Modeling that accounts for photothermal heating and the subsequent hydrogen desorption kinetics suggests that the silicon surface temperatures reached in our patterning process exceed those required for hydrogen removal in temperature-programmed desorption experiments. A phosphorus-doped van der Pauw structure made by sequentially photodepassivating a predefined area and then exposing it to phosphine is found to have a similar mobility and higher carrier density compared with devices patterned by STM. Lastly, it is also demonstrated that photodepassivation and precursor exposure steps may be performed concomitantly, a potential route to enabling APAM outside of ultrahigh vacuum.