Remote Plasma-enhanced Chemical Vapor Deposition Research Articles

Remote plasma-enhanced chemical vapor deposition of GeSn on Si (100), Si (111), sapphire, and fused silica substrates

GeSn films were simultaneously deposited on Si (100), Si (111), c-plane sapphire (Al2O3), and fused silica substrates to investigate the impact of the substrate on the resulting GeSn film. The electronic, structural, and optical properties of these films were characterized by temperature-dependent Hall-effect measurements, x-ray diffractometry, secondary ion mass spectrometry, and variable angle spectroscopic ellipsometry. All films were polycrystalline with varying degrees of texturing. The film on Si (100) contained only GeSn (100) grains, 40.4 nm in diameter. The film deposited on Si (111) contained primarily GeSn (111) grains, 36.4 nm in diameter. Both films deposited on silicon substrates were fully relaxed. The layer deposited on Al2O3 contained primarily GeSn (111) grains, 41.3 nm in diameter. The film deposited on fused silica was not textured, and the average grain size was 35.0 nm. All films contained ∼5.6 at. % Sn throughout the layer, except for the film deposited on Al2O3, which contained 7.5% Sn. The films deposited on Si (111), Al2O3, and fused silica exhibit p-type conduction over the entire temperature range, 10–325 K, while the layer deposited on the Si (100) substrate shows a mixed conduction transition from p-type at low temperature to n-type above 220 K. From ∼175 to 260 K, both holes and electrons contribute to conduction. Texturing of the GeSn film on Si (100) was the only characteristic that set this film apart from the other three films, suggesting that something related to GeSn (100) crystal orientation causes this transition from p- to n-type conduction.

X-ray photoelectron spectroscopy surface oxidation study of remote plasma-enhanced chemical vapor deposition-grown Ge1−xSnx/Si alloys

Recent progress in the remote plasma-enhanced chemical vapor deposition of Ge1−xSnx grown directly on Si substrates has improved crystal structure quality. To understand the impact of postgrowth storage, we study oxidation states of Ge1−xSnx alloys, for x values of 7.5%, 8.8%, 12.5%, and 19.3%. A surface oxidation layer formed naturally at room temperature over five months is quantified using angle-resolved x-ray photoelectron spectroscopy. The GeSn alloys exhibit a high surface oxide concentration with a minimum of 77% in Sn 3d peak analysis. Ge is less susceptible to oxidation than Sn, with oxidation percentages ranging from 25% to 86%. The Sn dopant enhances the oxidation features associated with the Ge 3p peak, aiding surface oxidation and penetrating further into the film. It is feasible that the 4+ state Sn from the precursor readily oxidizes postgrowth resulting in an oxide-rich surface layer.

Comparison of GeSn alloy films prepared by ion implantation and remote plasma-enhanced chemical vapor deposition methods

Thin films of germanium-tin (GeSn) alloy with Sn content well above its equilibrium solubility limit in Ge are produced using both remote plasma-enhanced chemical vapor deposition (RPECVD) directly on silicon substrates and ion implantation of Sn into Ge. For RPECVD, the growth temperature of 302 °C resulted in fully relaxed GeSn alloys with high defect density, principally threading dislocations related to the large lattice mismatch between Si and GeSn. For the implantation case, pulsed laser melting was used to melt and crystallize the GeSn layer on a time scale of a few tens of nanoseconds. The resulting GeSn layers were also relaxed and defective, presumably again as a result of lattice mismatch with the underlying Ge lattice. However, the nature of the defects was quite different to the RPECVD method, whereby the line defects were not threading dislocations but stackinglike defects, which developed into arrays of these defects in the high Sn content region close to the surface. For the purpose of comparing RPECVD and ion-implantation methods, alloy films of similar thickness (400–450 nm) and Sn content (4.5–6.5 at. %) were examined. Film parameters (thickness, Sn content, Sn solubility, and segregation), as well as film quality and defect structures, were examined for both fabrication methods using several analytical techniques. This comparison provided us with a better physical understanding of our GeSn films and will help inform future growth/fabrication strategies targeted at minimizing defects formed in the GeSn films for the realization of optoelectronic devices.

Epitaxial twin coupled microstructure in GeSn films prepared by remote plasma enhanced chemical vapor deposition

Growth of GeSn films directly on Si substrates is desirable for integrated photonics applications since the absence of an intervening buffer layer simplifies device fabrication. Here, we analyze the microstructure of two GeSn films grown directly on (001) Si by remote plasma-enhanced chemical vapor deposition (RPECVD): a 1000 nm thick film containing 3% Sn and a 600 nm thick, 10% Sn film. Both samples consist of an epitaxial layer with nano twins below a composite layer containing nanocrystalline and amorphous. The epilayer has uniform composition, while the nanocrystalline material has higher levels of Sn than the surrounding amorphous matrix. These two layers are separated by an interface with a distinct, hilly morphology. The transition between the two layers is facilitated by formation of densely populated (111)-coupled nano twins. The 10% Sn sample exhibits a significantly thinner epilayer than the one with 3% Sn. The in-plane lattice mismatch between GeSn and Si induces a quasi-periodic misfit dislocation network along the interface. Film growth initiates at the interface through formation of an atomic-scale interlayer with reduced Sn content, followed by the higher Sn content epitaxial layer. A corrugated surface containing a high density of twins with elevated levels of Sn at the peaks begins forming at a critical thickness. Subsequent epitaxial breakdown at the peaks produces a composite containing high levels of Sn nanocrystalline embedded in lower level of Sn amorphous. The observed microstructure and film evolution provide valuable insight into the growth mechanism that can be used to tune the RPECVD process for improved film quality.

Temperature-dependent morphology and composition of ultra-thin GeSn epilayers prepared by remote plasma enhanced chemical vapor deposition

Two distinct ultra-thin Ge1−xSnx (x ≤ 0.1) epilayers were deposited on (001) Si substrates at 457 and 313 °C through remote plasma-enhanced chemical vapor deposition. These films are considered potential initiation layers for synthesizing thick epitaxial GeSn films. The GeSn film deposited at 313 °C has a thickness of 10 nm and exhibits a highly epitaxial continuous structure with its lattice being compressed along the interface plane to coherently match Si without mismatch dislocations. The GeSn film deposited at 457 °C exhibits a discrete epitaxial island-like morphology with a peak height of ∼30 nm and full-width half maximum (FWHM) varying from 20 to 100 nm. GeSn islands with an FWHM smaller than 20 nm are defect free, whereas those exceeding 25 nm encompass nanotwins and/or stacking faults. The GeSn islands form two-dimensional modulated superlattice structures at the interface with Si. The GeSn film deposited at 457 °C possesses a lower Sn content compared to the one deposited at lower temperature. The potential impact of using these two distinct ultra-thin layers as initiation layers for the direct growth of thicker GeSn epitaxial films on (001) Si substrates is discussed.

Controllable Fabrication of Vertical Graphene with Tunable Growth Nature by Remote Plasma-Enhanced Chemical Vapor Deposition.

As an important member of the graphene family, vertical graphene (VG) has broad applications like field emission, energy storage, and sensors owing to its fascinating physical and chemical properties. Among various fabrication methods for VG, plasma enhanced chemical vapor deposition (PECVD) is most employed because of the fast growth rate at relatively low temperature for the high-quality VG. However, to date, relations between growth manner of VG and growth parameters such as growth temperature, dosage of gaseous carbon source, and electric power to generate plasma are still less known, which in turn hinder the massive production of VG for further applications. In this study, the growth behavior of VG was studied as functions of temperature, plasma power, and gas composition (or chamber pressure). It was found that the growth behavior of VG is sensitive to the growth conditions mentioned above. Although conditions with high growth temperature, large flow rate of mixed gas of methane and carrier gases, and high plasma power may be helpful for the fast growth of VG, brunching of VG is simultaneously enhanced, which in turn decreases the vertical growth nature of VG. High-quality VG can be achieved by optimizing the growth parameters. It was revealed that the vertical growth nature of VG is governed by the electric field at the interfacial layer between VG and the substrate, for which its strength is influenced by the density of plasma. These findings are important for the general understanding of the VG growth and provided a feasible way for the controllable fabrication of VG using the remote PECVD method which is usually believed to be unsuitable for the fabrication of VG.

Remote plasma-enhanced chemical vapor deposition of GeSn on Si: Material and defect characterization

Germanium–tin (GeSn) alloys at sufficiently high Sn concentration, above several atomic percent, are the only group IV semiconductor exhibiting a direct bandgap and have generated much recent interest for optoelectronic applications into the mid-infrared region. Because the large lattice mismatch between GeSn and Si results in considerable strain for thin layers and a high defect density for thicker strain-relaxed layers, most reported GeSn growths incorporate a Ge buffer layer rather than depositing directly on Si substrates. Published reports of GeSn growth directly on Si utilize specialized precursors such as higher order germanes (Ge2H6, Ge3H8, or Ge4H10) or SnD4. In this paper, we report GeSn films with up to 10.6% Sn grown directly on Si substrates by remote plasma-enhanced chemical vapor deposition using GeH4 and SnCl4 precursors. These alloys have been characterized in detail using x-ray diffraction (XRD), transmission electron microscopy (TEM), and Rutherford backscattering spectrometry with channeling (RBS-C), as well as Raman spectroscopy (RS) and optical microscopy. The films studied are almost fully relaxed, with small residual strain observed, particularly in thinner films, and contain a high interface density of misfit dislocations that increases with Sn concentration. The defect density decreases toward the surface. Good agreement is found between the various characterization methods for the Sn content (XRD and RBS-C), lattice parameter measurement (XRD and TEM), and defect characterization (RBS-C, TEM, and RS). Such characterization of GeSn grown directly on Si substrates is essential to allow growth parameters to be optimized for the realization of the attractive optoelectronic properties of these alloys.

High-Performance Graphene Nanowalls/Si Self-Powered Photodetectors with HfO2 as an Interfacial Layer.

Graphene/silicon (Si) heterojunction photodetectors are widely studied in detecting of optical signals from near-infrared to visible light. However, the performance of graphene/Si photodetectors is limited by defects created in the growth process and surface recombination at the interface. Herein, a remote plasma-enhanced chemical vapor deposition is introduced to directly grow graphene nanowalls (GNWs) at a low power of 300 W, which can effectively improve the growth rate and reduce defects. Moreover, hafnium oxide (HfO2) with thicknesses ranging from 1 to 5 nm grown by atomic layer deposition has been employed as an interfacial layer for the GNWs/Si heterojunction photodetector. It is shown that the high-k dielectric layer of HfO2 acts as an electron-blocking and hole transport layer, which minimizes the recombination and reduces the dark current. At an optimized thickness of 3 nm HfO2, a low dark current of 3.85 × 10-10, with a responsivity of 0.19 AW-1, a specific detectivity of 1.38 × 1012 as well as an external quantum efficiency of 47.1% at zero bias, can be obtained for the fabricated GNWs/HfO2/Si photodetector. This work demonstrates a universal strategy to fabricate high-performance graphene/Si photodetectors.

Epitaxial growth of trilayer graphene moiré superlattice

The graphene-based moiré superlattice has been demonstrated as an exciting system for investigating strong correlation phenomenon. However, the fabrication of such moiré superlattice mainly relies on transfer technology. Here, we report the epitaxial growth of trilayer graphene (TLG) moiré superlattice on hexagonal boron nitride (hBN) by a remote plasma-enhanced chemical vapor deposition method. The as-grown TLG/hBN shows a uniform moiré pattern with a period of ∼ 15 nm by atomic force microscopy (AFM) imaging, which agrees with the lattice mismatch between graphene and hBN. By fabricating the device with both top and bottom gates, we observed a gate-tunable bandgap at charge neutral point (CNP) and displacement field tunable satellite resistance peaks at half and full fillings. The resistance peak at half-filling indicates a strong electron–electron correlation in our grown TLG/hBN superlattice. In addition, we observed quantum Hall states at Landau level filling factors ν = 6, 10, 14, …, indicating that our grown trilayer graphene has the ABC stacking order. Our work suggests that epitaxy provides an easy way to fabricate stable and reproducible two-dimensional strongly correlated electronic materials.

Experimental Study of the Influence of CH4 and H2 on the Conformation, Chemical Composition, and Luminescence of Silicon Quantum Dots Inlaid in Silicon Carbide Thin Films Grown by Remote Plasma-Enhanced Chemical Vapor Deposition.

Silicon carbide (SiC) has become an extraordinary photonic material. Achieving reproducible self-formation of silicon quantum dots (SiQDs) within SiC matrices could be beneficial for producing electroluminescent devices operating at high power, high temperatures, or high voltages. In this work, we use a remote plasma-enhanced chemical vapor deposition system to grow SiC thin films. We identified that a particular combination of 20 sccm of CH4 and a range of 58–100 sccm of H2 mass flow with 600 °C annealing allows the abundant and reproducible self-formation of SiQDs within the SiC films. These SiQDs dramatically increase the photoluminescence-integrated intensity of our SiC films. The photoluminescence of our SiQDs shows a normal distribution with positive skewness and well-defined intensity maxima in blue regions of the electromagnetic spectrum (439–465 nm) and is clearly perceptible to the naked eye.

Semi-insulating GaAs surface modifications and their influence in the response of THz devices

In this work, we use the Metal-Assisted Chemical Etching (MACE) technique together with an NH3 plasma treatment using a Remote Plasma-Enhanced Chemical Vapor Deposition (RPECVD) equipment to modify the surface of semi-insulating GaAs (SI-GaAs) substrates. Using our modified SI-GaAs, we fabricate photoconductive antennas for THz emission to study the modification's influence on the optical and electrical antenna response. We found substantial gaps in the frequency-domain spectra of the devices, whose origin could reside in a change of the substrate's optical absorption due to: (a) a surficial chemical change or (b) a substrate topographic modification or a combination of both. We showed experimentally that slight and reproducible substrate surface modifications could lead to significant variations in the electrical behavior and THz response of SI-GaAs devices.

Design of a remote plasma-enhanced chemical vapor deposition system for growth of tin containing group-IV alloys

Group-IV alloys of Ge and/or Si with Sn are challenging to prepare due to the low solubility of Sn in both of these elements. Herein, we describe a remote plasma-enhanced chemical vapor deposition (RPECVD) system designed to synthesize such group-IV alloys. Thin films of Ge, Ge1−ySiy, Ge1−xSnx, and Ge1−x−ySiySnx were deposited in the range of 280−410 °C on Si (001) substrates utilizing a remote He plasma with downstream injected mixtures of SnCl4, SiH4, and/or GeH4 precursors. The composition and structural properties of these RPECVD films were characterized with x-ray diffraction, transmission electron microscopy, and x-ray photoelectron spectroscopy. They were found to be crystalline, oriented with the substrate, and nearly relaxed due to the formation of an ∼5 nm thick interface layer with a high density of edge dislocations and stacking faults.

FORMATION OF NANO STRUCTURES IN RESULT OF HOMOGENOUS NUCLEATION OF CARBON OBTAINED IN THERMAL PLASMA UNDER ATMOSPHERIC PRESSURE

Thermal plasma processing of carbon sources using a plasma jet with high heat capacity is one of the most promising methods for the synthesis of new materials. This paper describes the low-temperature deposition of carbon nanomaterials by remote plasma-enhanced chemical vapor deposition (PECVD) in the absence of catalysts. The remote PECVD process differs from conventional and direct PECVD process in two ways: (a) only a subset of the process reactants and/or diluents are directly plasma excited; and (b) thin film deposition takes place on a substrate that is outside of the plasma glow region. In conventional CVD methods, carbon is produced from the decomposition of carbon sources such as hydrocarbons, carbon monoxide, alcohols, and so on, over a metal catalyst. The unavoidable metal species remaining in carbon nanomaterials would lead to obvious disadvantages for property characterization and application exploration. Despite sustained efforts, it is still an intractable problem to remove metal catalysts completely from carbon nanomaterials samples without introducing defects and contaminations. Good reactor design allowed to overcome problems of chemical and structural purity, and poor process robustness in terms of phase composition of product from run to run. For the synthesis of graphene materials, carbon black, carbon nanotubes, nanowires we used the thermal plasma generator which is a high current divergent anode-channel DC plasma torch. The experiment involved a simultaneous input of hydrocarbons (methane, propane, butane, acetylene) with the plasma forming gas (helium, argon, nitrogen) into the plasma torch, wherein heating and decompositions occurred in the plasma jet and in the region of the arc discharge, followed by condensation of the synthesis product on metallic surfaces. The deposition rate was varied with distance from the plasma. Consumption of carbon source, plasma forming gas and plasma torch power were changed independently from each other. For the experimental conditions the electric power of plasma torch was set up to 40 kW. Regularities of formation of carbon thread-like nanostructures and graphene in the course of hydrocarbons pyrolysis in thermal plasma without participation of catalytic particles were studied by means of electron microscopy, X-ray diffraction, IR-spectrometry and thermogravimetry. Depending on the pyrolytic synthesis parameters, different proportions of crystal carbon and soot may be obtained. It has been demonstrated that the phase composition is varied by hydrocarbons flow rate, plasma forming gas pressure and dc plasma torch power. It has been established through the experiments that carbon nucleation is volumetric and proceeds according to the model of explosive soot formation.

Electrical contact properties between carbon nanotube ends and a conductive atomic force microscope tip

Understanding the electrical contact properties of carbon nanotube (CNT) ends is important to use the high conductance of CNTs in the CNT on-axis direction in applications such as through-silicon via structures. In this study, we experimentally evaluated the contact resistivity between single-/multi-walled CNT ends and a metal nanoprobe using conductive atomic force microscopy (C-AFM). To validate the measured end contact resistivity, we compared our experimentally determined value with that obtained from numerical calculations and reported values for side contact resistivity. The contact resistivity normalized by the length of the CNT ends was 0.6–2.4 × 106 Ω nm for single-walled CNTs. This range is 1–2 orders of magnitude higher than that determined theoretically. The contact resistivity of a single-walled CNT end with metal normalized by the contact area was 2–3 orders of magnitude lower than that reported for the resistivity of a CNT sidewall/metal contact. For multi-walled CNTs, the measured contact resistivity was one order of magnitude higher than that of a CNT forest grown by remote plasma-enhanced chemical vapor deposition, whereas the contact resistivity of a top metal electrode was similar to that obtained for a single-walled CNT forest.

Interface properties of SiO2/GaN structures formed by chemical vapor deposition with remote oxygen plasma mixed with Ar or He

The impacts of noble gas species (Ar and He) on the formation of a SiO2/GaN structure formed by a remote oxygen plasma-enhanced chemical vapor deposition (ROPE-CVD) method were systematically investigated. Atomic force microscopy revealed that ROPE-CVD with He leads to a smooth SiO2 surface compared with the case of Ar. We found that no obvious oxidations of the GaN surfaces after the SiO2 depositions with the both Ar and He cases were observed. The capacitance–voltage (C–V) curves of the GaN MOS capacitors formed by ROPE-CVD with the Ar and He dilutions show good interface properties with no hysteresis and good agreement with the ideal C–V curves even after post deposition annealing at 800 °C. Besides, we found that the current density–oxide electric field characteristics shows a gate leakage current for the Ar case lower than the He case.

High thermal stability of abrupt SiO2/GaN interface with low interface state density

The effects of postdeposition annealing (PDA) on the interface properties of a SiO2/GaN structure formed by remote oxygen plasma-enhanced chemical vapor deposition (RP-CVD) were systematically investigated. X-ray photoelectron spectroscopy clarified that PDA in the temperature range from 600 to 800 °C has almost no effects on the chemical bonding features at the SiO2/GaN interface, and that positive charges exist at the interface, the density of which can be reduced by PDA at 800 °C. The capacitance–voltage (C–V) and current density–SiO2 electric field characteristics of the GaN MOS capacitors also confirmed the reduction in interface state density (Dit) and the improvement in the breakdown property of the SiO2 film after PDA at 800 °C. Consequently, a high thermal stability of the SiO2/GaN structure with a low fixed charge density and a low Dit formed by RP-CVD was demonstrated. This is quite informative for realizing highly robust GaN power devices.

Inductively coupled remote plasma-enhanced chemical vapor deposition (rPE-CVD) as a versatile route for the deposition of graphene micro- and nanostructures

Multiple layers of graphene thin films with micro-crystalline orientation and vertical graphene nano-sheets were grown on different substrates (i.e., polycrystalline nickel foil, Ni(111), highly oriented pyrolytic graphite) using a single-step process based on low-pressure remote Plasma-Enhanced Chemical Vapor Deposition (rPE-CVD). In contrast to previous studies, a novel basic approach to this technique including a new remote inductively coupled RF plasma source has been used to (i) minimize the orientational effect of the plasma electrical fields during the catalyst-free growth of graphene nano-sheets, (ii) warrant for a low graphene defect density via low plasma kinetics, (iii) decouple the dissociation process of the gas from the growth process of graphene on the substrate, (iv) tune the feedstock gas chemistry in view of improving the graphene growth, and (v) reduce the growth temperature as compared to conventional chemical vapor deposition (CVD). In order to study the various aspects of the rPE-CVD graphene growth modes and to assess the characteristics of the resulting graphene layers, Raman spectroscopy, XPS, SEM, and STM were used. The results give evidence for the successful performance of this new rPE-CVD plasma deposition source, that can be combined with in situ UHV-based processess for the production of, e. g., hybrid metal ferromagnet/graphene systems.

Role of ammonia in depositing silicon nanoparticles by remote plasma enhanced chemical vapor deposition

The optimal development of silicon photonics could improve the current state of microelectronics technology. However due to the multiple parameters involved in the elaboration processes, it is not a simple task to fabricate and reproduce silicon emitting structures. In this paper we discuss the role played by ammonia in depositing silicon nanoparticles (Si-NPs) embedded in silicon nitride matrix by remote plasma enhanced chemical vapor deposition (RPECVD). We found that by varying the ammonia flow, the deposition rate changes. It was observed by high resolution transmission electron microscopy (HRTEM) that higher density and a lower average size of Si-NPs is achieved by increasing the ammonia flow. We recognized a linear behavior between the ammonia flow used to deposit a sample and its maximum photoluminescence (PL) emission peak. Finally we propose a model that allows to predict the maximum PL peak for a given ammonia flow within the range of 403–540nm.

On the intrinsic moisture permeation rate of remote microwave plasma-deposited silicon nitride layers

We report on a low substrate temperature (110°C) remote microwave plasma-enhanced chemical vapor deposition (PECVD) process of silicon nitride barrier layers against moisture permeation for organic light emitting diodes (OLEDs) and other moisture sensitive devices such as organic photovoltaic cells (OPVs). Specifically, the influence of the SiH4/NH3 gas flow ratio on the layer composition and intrinsic moisture barrier performance is investigated, as inferred from Fourier Transform Infrared (FTIR) spectroscopy, Rutherford Back Scattering (RBS) analysis, and the calcium test. Since the presence of extrinsic factors for barrier failure such as pinholes and contamination particles (defects) is largely determined by the substrate conditioning and environment, the focus in this research is on the intrinsic permeability of the silicon nitride films, as measured by monitoring the homogeneous degradation of defect (e.g. pinholes and contamination particles)-free calcium regions. The investigated films have tunable chemical composition and optical properties and moderate residual strain levels varying from tensile to compressive. Despite this variation in film properties, the intrinsic water vapor transmission rate (WVTR) is found to be constant at a level of 1·10−5g/m2day at 20°C/50%RH conditions for films deposited at 0.1–0.5nm/s. When the total gas flow rate is increased in order to achieve higher growth rate processing (0.2–1.0nm/s), a higher permeability is measured at increased SiH4/NH3 ratio. The development of high surface roughness in the silicon nitride layer, as shown by AFM analysis, suggests cluster/dust formation in the plasma and powder inclusion during film deposition. This eventually leads to higher water vapor transmission rate of the deposited layers.

Spectroscopic Detection of Medium Range Order in Device Grade Hydrogenated Amorphous Silicon

This article addresses low defect densities in hydrogenated amorphous silicon, a-Si1-x:Hx with approximately 10 at. % bonded H, x∼0.1. Based low defect densities at mid-gap, ∼0.5 to 1×1016 cm-3, a-Si:H thin films have been integrated into photovoltaic (PV) devices and thin film transistors (TFT's). Amorphous Si (a-Si) thin films with no detectable bonded-H have been used as precursors for polycrystalline gate electrodes in microelectronic applications. PV and TFT alloys have been deposited by glow discharge (GD), remote plasma-enhanced chemical vapor deposition (RPECVD), and reactive magnetron sputtering (RMS) with different bonded-H content determined by deposition precursors and substrate temperatures. Two conditions are required for the lowest Si dangling bond densities: (i) a monohydride, Si–H, concentration of ∼10 at. % H, and (ii) deposition, and/or a post-deposition annealing at 240 to 300 °C.