Monolayer Doping Research Articles

Exploring conductivity in ex-situ doped Si thin films as thickness approaches 5 nm

Silicon (Si) has been scaled below 10 nm in multigate and silicon-on-insulator (SOI) device technologies, but clearly Si thickness cannot be reduced indefinitely, as we will run out of atoms eventually. As thickness approaches 5 nm, surfaces and interfaces will significantly impact the electrical behavior of Si, and surface physics cannot be discounted. Below that, bulk material properties will be altered considerably in the few-monolayer limit. One of the most basic defining properties of a semiconductor is its conductivity. To improve conductivity, while inducing a channel by appropriate biasing, it is necessary to define an accurate impurity doping strategy to reduce parasitic resistance. In this paper, we investigated the changing electrical conductivity of SOI films as a function of the Si thickness, in the range of 3–66 nm. SOI films were ex situ doped using three different approaches: liquid/vapor phase monolayer doping of phosphorus using allyldiphenylphosphine, gas-phase doping of arsenic using arsine (AsH3), and room-temperature beam-line ion implantation of phosphorus. The circular transfer length method and micro-four-point probe measurements were used to determine the resistivity of the Si films, mitigating the contribution from contact resistance. The resistivity of the Si films was observed to increase with decreasing Si film thickness below 20 nm, with a dramatic increase observed for a Si thickness at 4.5 nm. This may drastically impact the number of parallel conduction paths (i.e., nanowires) required in gate-all-around devices. Density functional theory modeling indicates that the surface of the Si film with a thickness of 4.5 nm is energetically more favorable for the dopant atom compared to the core of the film.

Carbon doping of WS2 monolayers: Bandgap reduction and p-type doping transport.

Chemical doping constitutes an effective route to alter the electronic, chemical, and optical properties of two-dimensional transition metal dichalcogenides (2D-TMDs). We used a plasma-assisted method to introduce carbon-hydrogen (CH) units into WS2 monolayers. We found CH-groups to be the most stable dopant to introduce carbon into WS2, which led to a reduction of the optical bandgap from 1.98 to 1.83 eV, as revealed by photoluminescence spectroscopy. Aberration corrected high-resolution scanning transmission electron microscopy (AC-HRSTEM) observations in conjunction with first-principle calculations confirm that CH-groups incorporate into S vacancies within WS2. According to our electronic transport measurements, undoped WS2 exhibits a unipolar n-type conduction. Nevertheless, the CH-WS2 monolayers show the emergence of a p-branch and gradually become entirely p-type, as the carbon doping level increases. Therefore, CH-groups embedded into the WS2 lattice tailor its electronic and optical characteristics. This route could be used to dope other 2D-TMDs for more efficient electronic devices.

Magnetism induced by Mn atom doping in SnO monolayer

The structural, magnetic properties, and mechanism of magnetization of SnO monolayer doped with 3d transition metal Mn atom were studied using first-principles calculations. The calculated results show that the substitution doping is easier to realize under the condition of oxygen enrichment. Numerical results reveal that the spin-splitting defect state of the Mn doped system is produced in the band gap and the magnetic moment of 5.0 μB is formed. The induced magnetic moment by Mnsub is mostly derived from the 3d orbital of the doped Mn atom. The magnetic coupling between magnetic moments caused by two Mn atoms in SnO monolayer is a long-range ferromagnetic, which is due to the hole-mediated p–p and p–d interactions. The calculated results suggest that room-temperature ferromagnetism in a SnO monolayer can be induced after substitutional doping of a Mn atom.

Spatially selective reversible charge carrier density tuning in WS2 monolayers via photochlorination

Chlorine-doped tungsten disulfide monolayer (1L-WS2) with tunable charge carrier concentration has been realized by pulsed laser irradiation of the atomically thin lattice in a precursor gas atmosphere. This process gives rise to a systematic shift of the neutral exciton peak towards lower energies, indicating reduction of the crystal’s electron density. The capability to progressively tune the carrier density upon variation of the exposure time is demonstrated; this indicates that the Fermi level shift is directly correlated to the respective electron density modulation due to the chlorine species. Notably, this electron withdrawing process enabled the determination of the trion binding energy of the intrinsic crystal, found to be as low as 20 meV, in accordance to theoretical predictions. At the same time, it is found that the effect can be reversed upon continuous wave laser scanning of the monolayer in air. Scanning auger microscopy (SAM) and x-ray photoelectron spectroscopy (XPS) are used to link the actual charge carrier doping to the different chlorine configurations in the monolayer lattice. The spectroscopic analyses, complemented by density functional theory calculations, reveal that chlorine physisorption is responsible for the carrier density modulation induced by the pulsed laser photochemical reaction process. Such bidirectional control of the Fermi level, coupled with the capability offered by lasers to process at pre-selected locations, can be advantageously used for spatially resolved doping modulation in 1L-WS2 with micrometric resolution. This method can also be extended for the controllable doping of other TMD monolayers.

Diversification of Device Platforms by Molecular Layers: Hybrid Sensing Platforms, Monolayer Doping, and Modeling.

Inorganic materials such as semiconductors, oxides, and metals are ubiquitous in a wide range of device technologies owing to the outstanding robustness and mature processing technologies available for such materials. However, while the important contribution of inorganic materials to the advancement of device technologies has been well established for decades, organic-inorganic hybrid device systems, which merge molecular functionalities with inorganic platforms, represent a newer domain that is rapidly evolving at an increasing pace. Such devices benefit from the great versatility and flexibility of the organic building blocks merged with the robustness of the inorganic platforms. Given the overwhelming wealth of literature covering various approaches for modifying and using inorganic devices, this feature article selectively highlights some of the advances made in the context of the diversification of devices by surface chemistry. Particular attention is given to oxide-semiconductor systems and metallic surfaces modified with organic monolayers. The inorganic device components, such as semiconductors, metals, and oxides, are modified by organic monolayers, which may serve as either active, static, or sacrificial components. We portray research directions within the broader field of organic-inorganic hybrid device systems that can be viewed as specific examples of the potential of such hybrid device systems given their comprehensive capabilities of design and diversification. Monolayer doping techniques where sacrificial organic monolayers are introduced into semiconducting elements are reviewed as a specific case, together with associated requirements for nanosystems, devices, and sensors for controlling doping levels and doping profiles on the nanometric scale. Another series of examples of the flexibility provided by the marriage of organic functional monolayers and inorganic device components are represented by a new class of biosensors, where the organic layer functionality is exploited in a functioning device for sensing. Considerations for relying on oxide-terminated semiconductors rather than the pristine semiconductor material as a platform both for processing and sensing are discussed. Finally, we cover aspects related to the use of various theoretical and computational approaches to model organic-inorganic systems. The main objectives of the topics covered here are (i) to present the advances made in each respective domain and (ii) to provide a comprehensive view of the potential uses of organic monolayers and self-assembly processes in the rapidly evolving field of molecular-inorganic hybrid device platforms and processing methodologies. The directions highlighted here provide a perspective on a future, not yet fully realized, integrated approach where organic monolayers are combined with inorganic platforms in order to obtain versatile, robust, and flexible systems with enhanced capabilities.

Monolayer doping of germanium by phosphorus-containing molecules

The DPP (diethyl 1-propylphosphonate) and ODPA (octadecylphosphonic acid) molecules are studied as precursors for the monolayer doping (MLD) of germanium. Their adsorption behaviour is investigated, revealing different physicochemical interactions between the phosphorus-containing molecules and the Ge surfaces. It is discovered that DPP adsorption occurs after the oxidation of Ge surface, while the ODPA undergoes chemisorption on –H terminated surfaces. Quantitative phosphorus analysis demonstrates that in the first case more than one monolayer is formed (from 2 to 4), while in the second a single monolayer is formed. Moreover, the analysis of phosphorus diffusion from the surface layers into the Ge matrix reveals that conventional thermal annealing processes are not suitable for Ge injection due to a higher activation energy of the process in comparison with silicon. On the contrary, pulsed laser melting is effective in forming a doped layer, owing to the precursor’s decomposition under UV light.

Hole doping in epitaxial MoSe2 monolayer by nitrogen plasma treatment

Many transition-metal dichalcogenides, such as MoSe2, are direct-gap semiconductors at monolayer thickness, which hold potentials in nano-electronics, optoelectronics, and some new concept spin- and valley-electronic applications. For device application, however, controllable doping of the materials is essential. Here we report hole doping of epitaxial MoSe2 by nitrogen (N) plasma treatment with the aim of understanding the defect structure and its electronic characteristics. Examinations by annular dark field scanning transmission electron microscopy clearly reveal substitutional doping of N by replacing Se atoms in MoSe2 monolayer upon N-plasma treatment, though creation of Se vacancies are also possible. Interestingly, we note an unexpectedly high concentration of ‘dual defects’, where both Se atoms in the top and bottom Se layers of MoSe2 at the same lattice site are substituted by N and/or become vacant, suggesting a catalytic effect of defect formation. X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirm the presence of N–Mo bonds. Photoemission spectroscopy reveals an impurity band as well as the Fermi level shift, confirming the p-type doping effect in MoSe2 monolayer by N-plasma treatment. Consistent with the PES results, scanning tunneling spectroscopy measurement also reveal defect states peaked at 0.6–0.7 eV above the valance band maximum. The effectiveness of N-doping is discussed.

Strain-tunable p-type Ag doping in the native n-type InSe monolayer

As a new hopeful two-dimensional (2D) layered semiconductor material in nanoscaled electronic devices, 2D InSe nanosheet has been constructed successfully and identified to be a native n-type semiconductor. In this work, we provide theoretical studies that Ag substituting In atom can generate p-type carriers in the InSe monolayer, and its formation energy is lower under Se-rich condition, which shows that the p-type Ag-doped InSe system can be fabricated experimentally. More importantly, compressive strain makes the impurity states move toward the valence band edge, and thus p-type conducting characteristics are further improved. These findings show that for native n-type 2D InSe nanosheet, the properties of p-type carriers and band gap can be tuned, which will be useful to design 2D InSe material-based electronic devices in the future.

Phosphorus monolayer doping (MLD) of silicon on insulator (SOI) substrates.

This paper details the application of phosphorus monolayer doping of silicon on insulator substrates. There have been no previous publications dedicated to the topic of MLD on SOI, which allows for the impact of reduced substrate dimensions to be probed. The doping was done through functionalization of the substrates with chemically bound allyldiphenylphosphine dopant molecules. Following functionalization, the samples were capped and annealed to enable the diffusion of dopant atoms into the substrate and their activation. Electrical and material characterisation was carried out to determine the impact of MLD on surface quality and activation results produced by the process. MLD has proven to be highly applicable to SOI substrates producing doping levels in excess of 1 × 1019 cm−3 with minimal impact on surface quality. Hall effect data proved that reducing SOI dimensions from 66 to 13 nm lead to an increase in carrier concentration values due to the reduced volume available to the dopant for diffusion. Dopant trapping was found at both Si–SiO2 interfaces and will be problematic when attempting to reach doping levels achieved by rival techniques.

Mechanism of Phosphorus Transport Through Silicon Oxide During Phosphonic Acid Monolayer Doping

Monolayer doping (MLD) is a relatively new method to incorporate shallow dopants from an adsorbed organic monolayer. To prevent evaporation of the dopant-containing organic layer during thermal pro...

Effect of surface states on monolayer doping: Crystal orientations, crystallinities, and surface defects

Monolayer doping (MLD) has been regarded as the most suitable doping method for future semiconductor devices. MLD based on surface functionalization can be seriously affected by the surface states, including the orientations, crystallinities, and defects. We report for the first time the effect of surface states on boron-MLD (B-MLD) process and discuss the applicability of MLD for a fin structures. Depending on the surface states, the monolayer formation reaction is restricted, which causes more than five-fold differences in the doping level. Therefore, the surface states should be gravely considered before applying MLD and are crucial constraints in the MLD process on non-planar structures that have different surface states depending on its structural position. The B-MLD process on as-cleaned (100) and (110) silicon surfaces provides doping levels of 4.69 × 1020 and 2.48 × 1020 atoms/cm3, respectively. The MLD efficiency on the (110) orientation is degraded by insufficient reaction sites for the hydrosilylation reaction on the monohydride-terminated (110) silicon surface. Additionally, the surface damage interrupts the formation of a dopant-containing monolayer, causing a poor doping level and dose uniformity. Our research provides new insights into the development of wet-chemical doping methods for non-planar devices by studying the effect of surface states on MLD efficiency.

Diagnosis of phosphorus monolayer doping in silicon based on nanowire electrical characterisation

The advent of high surface-to-volume ratio devices has necessitated a revised approach to parameter extraction and process evaluation in field-effect transistor technologies. In this work, active doping concentrations are extracted from the electrical analysis of Si nanowire devices with high surface-to-volume ratios. Nanowire resistance and Si resistivity are extracted, by first extracting and subtracting out the contact resistance. Resistivity (ρ) is selected as the benchmark parameter to compare different doping processes with each other. The impacts of nanowire diameter scaling to 10 nm and of nanowire spacing scaling to <20 nm are extracted for monolayer doping and beam-line ion implantation. Despite introducing significant crystal damage, P beam-line ion implantation beats allyldiphenylphosphine (ADP) P monolayer doping with a SiO2 cap in terms of lower Si resistivity and higher dopant activation, with dependencies on the nanowire width greater than on nanowire spacing. Limitations in ADP P monolayer doping with a SiO2 cap are due to the difficulties in dopant incorporation, as it is based on in-diffusion, and P atoms must overcome a potential barrier on the Si surface.

Understanding Thermal Evolution and Monolayer Doping of Sulfur-Passivated GaAs(100)

Monolayer doping (MLD) is an attractive method to precisely tailor dopant profiles for nanoelectronic semiconductor devices. The approach has been demonstrated for a number of different dopant/subs...

Tuning magnetic properties of two-dimensional MoTe2 monolayer by doping 3d transition metals: Insights from first principles calculations

Report on systematic study of the effect of transition metal atom doping in MoTe2 monolayer on electronic and magnetic properties using first principles calculations within the density functional theory method including onsite coulomb interaction. The material with Mo vacancy can induce spin polarization with large magnetic moments. Moreover, the results demonstrate that the transition metal atoms doped MoTe2 monolayer induce spin polarization and subsequent polarized charges from the localized 3d electrons of transition metal atoms. Magnetism is not observed in Ni-doped MoTe2. Magnetic moments are characterized by transition metal dopant spin density distribution including Mo and Te atoms. This work suggests that the MoTe2 monolayer has considerable potential for application in spintronic devices.

Direct n- to p-Type Channel Conversion in Monolayer/Few-Layer WS2 Field-Effect Transistors by Atomic Nitrogen Treatment.

We present a method for substitutional p-type doping in monolayer (1L) and few-layer (FL) WS2 using highly reactive nitrogen atoms. We demonstrate that the nitrogen-induced lattice distortion in atomically thin WS2 is negligible due to its low kinetic energy. The electrical characteristics of 1L/FL WS2 field-effect transistors (FETs) clearly show an n-channel to p-channel conversion with nitrogen incorporation. We investigate the defect formation energy and the origin of p-type conduction using first-principles calculations. We reveal that a defect state appears near the Fermi level, leading to a shallow acceptor level at 0.24 eV above the valence band maximum in nitrogen-doped 1L/FL WS2. This doping strategy enables a substitutional p-type doping in intrinsically n-type 1L/FL transition metal dichalcogenides (TMDCs) with tunable control of dopants, offering a method for realizing complementary metal-oxide-semiconductor FETs and optoelectronic devices on 1L/FL TMDCs by overcoming one of the major limits of TMDCs, that is, their n-type unipolar conduction.

Shallow Si N + P junction diodes realized via molecular monolayer doping

A conformal and controlled semiconductor doping is needed for applications in next generation nanoscale devices, low contact resistivity metal semiconductor junctions such as selective emitters in solar cells. Molecular monolayer doping (MLD) in silicon is a novel technique based on the formation of self-assembled monolayer of dopant – containing molecules on surface of crystalline silicon, followed by rapid thermal anneal. The technique is capable of forming ultra-shallow junctions with high atomic accuracy and minimum defects in silicon. A container and process was developed which successfully doped 6in. diameter silicon wafers using MLD for the in-house CMOS fabrication facility. The phosphorus monolayer is grafted on hydrogen terminated p-type silicon followed by rapid thermal anneal. Average sheet resistance ~670Ω/sq. and junction depth ~25nm are achieved. N+P junctions are fabricated using MLD and current-voltage characteristics are measured and analyzed using unified diode model.

Tunable excitonic emission of monolayer WS2 for the optical detection of DNA nucleobases

Two-dimensional transition metal dichalcogenides (2D TMDs) possess a tunable excitonic light emission that is sensitive to external conditions such as electric field, strain, and chemical doping. In this work, we reveal the interactions between DNA nucleobases, i.e., adenine (A), guanine (G), cytosine (C), and thymine (T) and monolayer WS2 by investigating the changes in the photoluminescence (PL) emissions of the monolayer WS2 after coating with nucleobase solutions. We found that adenine and guanine exert a clear effect on the PL profile of the monolayer WS2 and cause different PL evolution trends. In contrast, cytosine and thymine have little effect on the PL behavior. To obtain information on the interactions between the DNA bases and WS2, a series of measurements were conducted on adenine-coated WS2 monolayers, as a demonstration. The p-type doping of the WS2 monolayers on the introduction of adenine is clearly shown by both the evolution of the PL spectra and the electrical transport response. Our findings open the door for the development of label-free optical sensing approaches in which the detection signals arise from the tunable excitonic emission of the TMD itself rather than the fluorescence signals of label molecules. This dopant-selective optical response to the DNA nucleobases fills the gaps in previously reported optical biosensing methods and indicates a potential new strategy for DNA sequencing.

Deep level transient spectroscopic investigation of phosphorus-doped silicon by self-assembled molecular monolayers

It is known that self-assembled molecular monolayer doping technique has the advantages of forming ultra-shallow junctions and introducing minimal defects in semiconductors. In this paper, we report however the formation of carbon-related defects in the molecular monolayer-doped silicon as detected by deep-level transient spectroscopy and low-temperature Hall measurements. The molecular monolayer doping process is performed by modifying silicon substrate with phosphorus-containing molecules and annealing at high temperature. The subsequent rapid thermal annealing drives phosphorus dopants along with carbon contaminants into the silicon substrate, resulting in a dramatic decrease of sheet resistance for the intrinsic silicon substrate. Low-temperature Hall measurements and secondary ion mass spectrometry indicate that phosphorus is the only electrically active dopant after the molecular monolayer doping. However, during this process, at least 20% of the phosphorus dopants are electrically deactivated. The deep-level transient spectroscopy shows that carbon-related defects are responsible for such deactivation.

Functionalization of SiO2 Surfaces for Si Monolayer Doping with Minimal Carbon Contamination.

Monolayer doping (MLD) involves the functionalization of semiconductor surfaces followed by an annealing step to diffuse the dopant into the substrate. We report an alternative doping method, oxide-MLD, where ultrathin SiO2 overlayers are functionalized with phosphonic acids for doping Si. Similar peak carrier concentrations were achieved when compared with hydrosilylated surfaces (∼2 × 1020 atoms/cm3). Oxide-MLD offers several advantages over conventional MLD, such as ease of sample processing, superior ambient stability, and minimal carbon contamination. The incorporation of an oxide layer minimizes carbon contamination by facilitating attachment of carbon-free precursors or by impeding carbon diffusion. The oxide-MLD strategy allows selection of many inexpensive precursors and therefore allows application to both p- and n-doping. The phosphonic acid-functionalized SiO2 surfaces were investigated using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy, whereas doping was assessed using electrochemical capacitance voltage and Hall measurements.

Magnetism induced by 3d transition metal atom doping in InSe monolayer

Based on density functional theory, we study the electronic structures and magnetism of 3d transition metal (TM)-doped two-dimensional (2D) InSe monolayer by means of first-principles methods. The results show that all the doping cases can be easily realized under Se-rich experimental environments. For the Sc- and Cu-doped InSe monolayers, the nonmagnetic semiconducting properties can be retained. The Ti-, Cr- and Ni-doped InSe monolayers possess the half-metal behavior. Moreover, the diluted magnetic semiconductor characteristics can be found in the V-, Mn-, Co-, Fe- and Zn-doped cases. Interestingly, the Ti-, V-, Cr- and Fe-doped 2D InSe systems exhibit ferromagnetic ground states, while antiferromagnetic ground states occur in the Mn-, Co- and Ni-doped InSe monolayers.