In all implantations into crystalline targets, quite a few ions find a path along a crystal channel or plane, so called channeling, and these ions travel deep into the crystal. This paper treats aluminum (Al) implantation in 4H-SiC and show how the crystal lattice will guide incoming ions deep into the target and modify the final dopant distribution. 4H-SiC samples have been implanted with 100 keV Al-ions, in a “random” direction using the wafer miscut angle of 4°, as well as with the impact beam aligned anti-parallel to the [0001] direction. Aluminium concentration versus depth profiles has been recorded by secondary ion mass spectrometry (SIMS). To track the most probable ion paths during stopping process, SIIMPL, a Monte Carlo simulation code based on the binary collision approximation (MC-BCA) has been used. In addition, the remaining ion energy has been extracted from SIIMPL at various depth along the ion path. Our results show that, independent of the used impact angle, some ions will be steered by crystal planes predominantly into the direction and also along the six directions. The energy loss is smaller along these low index axes. Therefore, at a depth of 1.2 μm, some Al ions along a path may still have kinetic energy, more than 40% of the original 100 keV, and continues to move deep into the SiC sample. The mean projected range of 100 keV ions in 4H-SiC is about 120 nm.
Ion implantation is performed in 4H-SiC with 11B, 27Al, 31P, 51V, 71Ga, and 75As ions using energies between 40 and 300 keV at various fluences along the [000-1] or the ⟨11-2-3⟩ axes. Secondary ion mass spectrometry is utilized to determine the depth distribution of the implanted elements. A Monte Carlo binary collision approximation (MC-BCA) code for crystalline targets is then applied to explain the influence of the electronic shell structure on electronic stopping and the obtained channeled ion depth distributions. The results show that, as the atomic number increases in a row of the periodic table, i.e., as the ionic radius decreases and the electron clouds densify, the interaction with the target electrons increases and the range is reduced. The decreased range is particularly pronounced going from 27Al to 31P. The reduction in channeling depth is discussed in terms of electronic shells and can be related to the ionic radii, as defined by Kohn–Sham. It is shown that these shell effects in channeled implantations can easily be included in MC-BCA simulations simply by modifying the screening length used in the local treatment of electronic stopping in channels. However, it is also shown that, for vanadium ions with an unfilled d-shell, this simple model is insufficient to predict the electronic stopping in the channels.
Self-diffusion of carbon (12C and 13C) and silicon (28Si and 30Si) in 4H silicon carbide has been investigated by utilizing a structure containing an isotope purified 4H-28Si12C epitaxial layer grown on an n-type (0001) 4H-SiC substrate, and finally covered by a carbon capping layer (C-cap). The 13C and 30Si isotope profiles were monitored using secondary ion mass spectrometry (SIMS) following successive heat treatments performed at 2300–2450∘C in Ar atmosphere using an inductively heated furnace. The 30Si profiles show little redistribution within the studied temperature range, with the extracted diffusion lengths for Si being within the error bar for surface roughening during annealing, as determined by profilometer measurements. On the other hand, a significant diffusion of 13C was observed into the isotope purified layer from both the substrate and the C-cap. A diffusivity of D=8.3×106e−10.4/kBT cm2/s for 13C was extracted, in contrast to previous findings that yielded lower both pre-factors and activation energies for C self-diffusion in SiC. The discrepancy between the present measurements and previous theoretical and experimental works is ascribed to the presence of the C-cap, which is responsible for continuous injection of C interstitials during annealing, and thereby suppressing the vacancy mediated diffusion.
Channeling phenomena during ion implantation have been studied for 50 keV 11B, 100 keV 27Al and 240 keV 71Ga in 4H-SiC by secondary ion mass spectrometry and medium energy ion backscattering. The same projected range are expected for the used energies while the channeling tails are shown to be substantially different, for example, channeled 71Ga ions may travel 5 times as deep as 11B. Ion implantation has been performed both at room temperature (RT) and 400 °C, where channeling effects are reduced for the 400 °C implantation compared to that of the RT due to thermal vibrations of lattice atoms. The temperature effect is pronounced for 71Ga but nearly negligible for 11B at the used energies. The channeling phenomena are explained by three-dimensional Monte Carlo simulations. For standard implantations, i.e. 4° off the c-direction, it is found that a direction in-between the [000-1] and the <11-2-3> crystal channels, results in deep channeling tails where the implanted ions follow the [000-1] and the <11-2-3> directions.
Ion implantation is a commonly used process step in 4H-SiC device manufacturing to implement precise concentrations of dopant atoms in selected areas and depths. This paper reports on vanadium (V) implantation into 4H-SiC(0001) and how the crystal lattice, with preferential directions, channels, for the ions, will influence the final dopant distribution. Concentration versus depth profiles of V-ions, intentionally and unintentionally channelled, has been recorded by secondary ion mass spectrometry. Ion implantations have been performed between 50 and 300 keV at various impact angles and fluence at room temperature as well as at elevated temperatures. Before ion implantation, the samples were aligned utilizing the blocking pattern of 100 keV backscattered protons. In addition to the aligned implantations, our standard beam line for ion implantation has been used for implantations in a 'random' direction using the wafer miscut angle of 4 degrees. The electronic stopping has been determined from these 'random' cases and the values have been used in 3D simulations to predict preferential crystallographic directions using SIIMPL, a Monte Carlo simulation code based on the binary collision approximation. The results show that, independent of the used impact angle there is always a probability that the vanadium ions will be steered into the [000-1] and the family of < 11-2-3 > crystal directions and therefore penetrate deep into the sample, resulting in unwanted 'spikes'. If the implantation is performed at elevated temperatures, a larger degree of dechanneling is present due to increased thermal vibrations and the penetration depth of vanadium is slightly reduced.
The effect of lattice thermal vibrations on the channeling of 100 keV Al ions in 4H-SiC is investigated. By implanting at room temperature in the direction, the depth distribution of the incident ions is shown to be about 7 times deeper than for random implantations. At higher implantation temperatures, the channeling is reduced by the lattice vibrations and, for instance, at 600 °C implantation the distribution is about 3-4 times deeper than for a RT random implantation. The results are of technological interest for further development of implantation technology for 4H-SiC device manufacturing.
We present the most recent upgrades of the time-of-flight medium energy ion scattering (TOF-MEIS) system in Uppsala. The experimental chamber features a 6-axis goniometer with a sample annealing stage and two delay line detectors for composition analysis with high depth resolution and depth-resolved crystallography. The first detector has a large solid angle and can be moved circularly around the target position which allows to detect backscattered or transmitted ions. The second detector features increased flight distance from sample to detector resulting in enhanced energy resolution. A reduction from 1.4 keV to 0.4 keV is achieved for 100 keV He scattered from an Au surface for 1 ns time resolution, equivalent to a depth resolution of 6 angstrom. This detector is equipped with an electrostatic electrode in order to deflect charged particles, which allows to study the charge state for scattered ions in the medium energy regime.
Channeling of B and Al ions in 4H-SiC(0001), has been investigated by secondary ion mass spectrometry (SIMS). Ion implantations have been performed between room temperature (RT) and 600 °C at various fluences. Before implantation, the major crystal axes were determined and the sample was aligned using the blocking pattern of backscattered protons. As expected, the depth distribution of the implanted ions along a crystal direction penetrates much deeper compared to non-channeling directions. At elevated temperatures, the channeling depth for 100 keV Al-ions is decreased due to lattice vibrations. For 50 keV B-ions, the temperature effect is minor, indicating a smaller interaction between target atoms and B. Simulations has been performed using SIIMPL, a Monte Carlo simulation code based on the binary collision approximation, to predict experimental data and get a deeper insight in the channeling process.
Ion implantation is an important technique in semiconductor processing and has become a key technology for 4H-SiC devices. Today, aluminum (Al) implantations are routinely used for p-type contacts, p + -emitters, terminations and many other applications. However, in all crystalline materials, quite a few ions find a path along a crystal channel, so-called channeling, and these ions travel deep into the crystal. This paper reports on the channeling phenomenon during Al implantation into 4H-SiC, and in particular, the influence of a thin native oxide will be discussed in detail. The effects of thermal lattice vibrations for implantations performed at elevated temperatures will also be elucidated. 100 keV Al ions have been implanted along the [000-1] direction employing samples with 4° miscut. Before implantation, the samples have been aligned using the blocking pattern of backscattered protons. Secondary ion mass spectrometry has been used to record the Al depth distribution. To predict implantation profiles and improve understanding of the role of crystal structure, simulations were performed using the Monte-Carlo binary collision approximation code SIIMPL. Our results show that a thin surface layer of native oxide, less than 1 nm, has a decisive role for de-channeling of aligned implantations. Further, as expected, for implantations at elevated temperatures, a larger degree of de-channeling from major axes is present due to increased thermal vibrations and the penetration depth of channeled aluminum ions is reduced. The values for the mean-square atomic displacements at elevated temperatures have been extracted from experimental depth profiles in combination with simulations.
The stability/ erosion of the interface between a C-cap and 4H-SiC have been studied by secondary ion mass spectrometry (SIMS). Aluminum implantation has been used to monitor the position of the moving interface as well as to investigate the influence on the interface stability by the crystal quality of the 4H-SiC. After Al implantation a C-cap has been deposited by pyrolysis of photoresist. Subsequent annealing has been performed at 1900 and 2000 °C with durations between 15 minutes and 1 hour. SIMS measurements have been performed without removal of the C-cap. The surface remains smooth after the heat treatment, but a large amount of SiC material from the uppermost part of the wafer is lost. The amount of lost material is related to for instance annealing temperature, ambient conditions and ion induced crystal damage. This contribution gives a brief account of the processes governing the SiC surface decomposition during C-cap post implant annealing.
The present paper focuses on the investigation of Al2O3/4H-SiC dielectric interface upon annealing, its consequent structural modifications, and the link to electrical properties. For this purpose, the test structures are prepared by depositing Al2O3, using atomic layer deposition (ALD), on low doped n-type 4H-SiC epitaxial layers. The structures are annealed from 300 degrees C to 1100 degrees C for different time duration (from 5 to 60 mins) and ambient such as, low vacuum (10(-1) Torr), N-2, and N2O. The structural studies on these samples are conducted using synchrotron-based high resolution x-ray photoelectron spectroscopy (HR-XPS), lab-based XPS, time of flight elastic recoil detection analysis (ToF-ERDA), and time of flight medium energy ion scattering (ToF-MEIS). The electrical response of capacitive structures is monitored through capacitance voltage (CV) measurements for as-deposited and annealed structures. It is found that the annealing at high temperatures, such as 1100 degrees C, and in N-2 or N2O environment, improves the dielectric properties due to the introduction of a thin layer of about 1 nm stable SiO2 between the Al2O3 and 4H-SiC.
•In this manuscript, we demonstrate a process optimization of atomic layer deposited Al2O3 on 4H-SiC resulting in an improved interface and electrical properties.•These findings clearly indicate that both the pre deposition surface cleaning treatment prior to the dielectric deposition, and the post deposition annealing plays important roles in determining the quality of interface between the 4H-SiC/Al2O3.•The long standing dielectric reliability issues with Al2O3 on 4H-SiC have also been addressed resulting in an improved interface and electrical properties in terms of lower oxide charges, flatband voltage, leakage current and higher breakdown voltage.
Technologies for the growth of 3C-SiC with crystalline quality and crystal size similar to hexagonal counterparts (6H-or 4H-SiC) are still at the laboratory stage. There are several challenges in the control of polytype stability and formation of structural defects which have to be eliminated to reveal the full potential of this material. Nevertheless, 3C-SiC has been explored for various energy, environment and biomedical applications which significantly benefit from the intrinsic semiconductor properties of this material. The future of 3C-SiC and its applications depends on the advances which will be made in improving crystalline quality, enlarging crystal size and controlling doping levels which have not been entirely explored due to the lack of high quality 3C-SiC substrates. This paper reviews recent progress in growth and doping of thick 3C-SiC layers on hexagonal SiC substrates using sublimation epitaxy. It covers the growth process on off-axis substrates and defects occurrence, as well as the issue of obtaining high resistivity material.
The formation of interfacial oxides during heat treatment of dielectric films on 4H-SiC has been studied. The 4H-SiC surface has been carefully prepared to create a clean and abrupt interface to Al2O3. An amorphous, 3 nm thick, Al2O3 film has been prepared on 4H-SiC by atomic layer deposition and rapid thermal annealing was then performed in N2O ambient at 700 degrees C and 1100 degrees C during 1 min. The samples were studied by time-of-flight medium energy ion scattering (ToF-MEIS), with sub-nanometer depth resolution and it is seen that, at both annealing temperatures, a thin SiOx (1 <= x <= 2) is formed at the interface. Our results further indicate that carbon remains in the silicon oxide in samples annealed at 700 degrees C. Additional electrical capacitance voltage measurements indicate that a large concentration of interface traps is formed at this temperature. After 1100 degrees C annealing, both MEIS and XRD measurements show that these features disappear, in accordance with electrical data.
Ion implantation is a key process technique for semiconductor materials, in particular silicon, for local tailoring of the semiconductor properties. The wide bandgap semiconductor silicon carbide (SiC) features outstanding material properties for high power and high temperature electronic devices, but the properties of SiC also make it difficult to manufacture and process the material. The development of implantation technology for SiC has therefore necessitated several changes from mainstream silicon implantation technology. This paper will discuss the difficulties with implantation of SiC for manufacturing of electronic devices and also describe how the problems have been overcome, for instance by implantation at elevated temperatures and using high temperature post-implant annealing.
Relocation of alkali metals sodium, potassium and cesium during oxidation of 4H-SiC has been studied by secondary ion mass spectrometry. The alkali metal source has been introduced by ion implantation before oxidation into n-and p-type 4H-SiC samples. Dry oxidation of SiC has been performed at 1150 oC during 4, 8 and 16 h. In the formed oxide, the main part of the alkali metals diffuses out via the SiO2 surface. Close to the moving SiO2/SiC interface, a minor amount of alkali metals is retained. In the SiC material, the main amount of implanted alkali atoms is not redistributed during the oxidation, although a minor amount diffuses deeper into the samples. For p-type 4H-SiC, the diffusion deeper into the samples of the studied alkali metals decreases as the mass increases, Na+
There is a strong and growing worldwide research on exploring renewable energy resources. Solar energy is the most abundant, inexhaustible and clean energy source, but there are profound material challenges to capture, convert and store solar energy. In this work, we explore 3C-SiC as an attractive material towards solar-driven energy conversion applications: (i) Boron doped 3C-SiC as candidate for an intermediate band photovoltaic material, and (ii) 3C-SiC as a photoelectrode for solar-driven water splitting. Absorption spectrum of boron doped 3C-SiC shows a deep energy level at ~0.7 eV above the valence band edge. This indicates that boron doped 3C-SiC may be a good candidate as an intermediate band photovoltaic material, and that bulk like 3C-SiC can have sufficient quality to be a promising electrode for photoelectrochemical water splitting.
In this work we present a significant advancement in cubic silicon carbide (3C-SiC) growth in terms of crystal quality and domain size, and indicate its potential use in photovoltaics. To date, the use of 3C-SiC for photovoltaics has not been considered due to the band gap of 2.3 eV being too large for conventional solar cells. Doping of 3C-SiC with boron introduces an energy level of 0.7 eV above the valence band. Such energy level may form an intermediate band (IB) in the band gap. This IB concept has been presented in the literature to act as an energy ladder that allows absorption of sub-bandgap photons to generate extra electron-hole pairs and increase the efficiency of a solar cell. The main challenge with this concept is to find a materials system that could realize such efficient photovoltaic behavior. The 3C-SiC bandgap and boron energy level fits nicely into the concept, but has not been explored for an IB behavior.For a long time crystalline 3C-SiC has been challenging to grow due to its metastable nature. The material mainly consists of a large number of small domains if the 3C polytype is maintained. In our work a crystal growth process was realized by a new approach that is a combination of initial nucleation and step-flow growth. In the process, the domains that form initially extend laterally to make larger 3C-SiC domains, thus leading to a pronounced improvement in crystalline quality of 3C-SiC. In order to explore the feasibility of IB in 3C-SiC using boron, we have explored two routes of introducing boron impurities; ion implantation on un-doped samples and epitaxial growth on un-doped samples using pre-doped source material. The results show that 3C-SiC doped with boron is an optically active material, and thus is interesting to be further studied for IB behavior.For the ion implanted samples the crystal quality was maintained even after high implantation doses and subsequent annealing. The same was true for the samples grown with pre-doped source material, even with a high concentration of boron impurities.We present optical emission and absorption properties of as-grown and boron implanted 3C-SiC. The low-temperature photoluminescence spectra indicate the formation of optically active deep boron centers, which may be utilized for achieving an IB behavior at sufficiently high dopant concentrations. We also discuss the potential of boron doped 3C-SiC base material in a broader range of applications, such as in photovoltaics, biomarkers and hydrogen generation by splitting water. (C) 2015 Elsevier B.V. All rights reserved.
Sodium diffusion has been studied in p-type 4H-SiC. Heat treatments have been performed from 1200 °C to 1800 °C for 1 min to 4 h. Secondary ion mass spectrometry has been used to measure the sodium distribution. We show that sodium has a considerable mobility at 1200 °C in p-type 4H-SiC. On the other hand for sodium atoms trapped at suitable sites the mobility is limited up to 1800 °C. Trap limited diffusion kinetics is suggested and an effective diffusivity has been extracted with an activation energy of 4 eV for sodium diffusion in p-type 4H-SiC.
The thick N-B co-doped epilayers were grown by the fast sublimation growth method and the depth-resolved carrier lifetimes have been investigated by means of the free-carrier absorption (FCA) decay under perpendicular probe-pump measurement geometry. In some samples, we optically reveal in-grown carbon inclusions and polycrystalline defects of substantial concentration and show that these defects slow down excess carrier lifetime and prevent donor-acceptor pair photoluminescence (DAP PL). A pronounced electron lifetime reduction when injection level approaches the doping level was observed. It is caused by diffusion driven non-radiative recombination. However, the influence of surface recombination is small and insignificant at 300 K.