United States

Defects can occur during the growth of two-dimensional (2D) transition metal dichalcogenide (TMD) crystals. Exposure to these defects in 2D TMD to air and harsh conditions initiates the reaction of exposed transition metal atoms with active species such as O2 and H2O molecules, triggering an oxidation process. Understanding the oxidation behavior of 2D TMDs is crucial for their practical applications in electronics, optoelectronics, and electro-/photocatalysis because any structural deformation under ambient conditions directly affects their unique properties. As 2D semiconductor, 2H-MoTe2 is highly susceptible to air, it has the potential to control the conversion between p- and n-type characteristics. Nevertheless, previous research has been conducted on macroscopic scale oxidation, there is limited understanding of the oxidation behavior at the atomic level. It is imperative to explore the oxidation behavior of 2H-MoTe2 in greater detail to effectively modify its properties. In this study, we provide a detailed investigation on the oxidation of 2H-MoTe2 under various environmental conditions and insights for oxidation control. Exposure of synthesized 2H-MoTe2 flakes to air at room temperature for 17 months led to two striking morphological changes: 1) Hexagonal or triangular etching was observed from defects such as screw dislocations, crystal edges, and grain boundaries, resulting in the preferential oxidation and formation of pits with an average lateral size of several micrometers. 2) After a relatively slow reaction, triangular protruding oxide layer consisting of a stable MoO2 hillocks were formed on the basal plane of MoTe2, as confirmed by surface and structure characterization using scanning electron microscope (SEM), transmission electron microscope (TEM) and Raman. Experiments monitoring at the oxidation process at 230 °C for 3 h and TEM analysis showed that the substrates and active species have a significant effect on oxidation mechanism. Interestingly, under an O2 atmosphere, MoO2 layers was formed on the entire surface of 2H-MoTe2, while in a H2O atmosphere, most of the surface remained intact but oxidation etching occurred at defects in the basal plane. Furthermore, using theoretical calculations, we investigated the reaction of the surface Te atoms of defective 2H-MoTe2 with O2 and H2O molecules, which provide volatile TeO2 and H2Te and create a Te vacancy in the 2H-MoTe2 basal plane. It was found that, although O2 dissociation in the basal plane of 2H-MoTe2 with a Te vacancy is energetically favored over H2O dissociation, the subsequent reaction involving H is a dominant mechanism in forming Te vacancies than reactions involving an O atom. More importantly, when TeO2 volatilizes, the additional adsorbed O atom suppresses the lattice reconstruction around TeO2, resulting in an increased kinetic barrier (∼2.22 eV) to volatile TeO2. This finding is consistent with the TEM analysis results of the monitoring experiment, which demonstrated the formation of a stable oxide film under an O2 atmosphere. Our study provides valuable insight into the oxidation dynamics of 2H-MoTe2 at the atomic level and can inspire a new approach to improve the reliability and durability of TMD-based 2D devices.

EMC 2023

Oxidation Mechanism of 2H-MoTe2 at the Atomic Scale

atomic scale

oxidation

transition metal dichalcogenides

The Electronic Materials Conference (EMC) is the premier annual forum on the preparation, characterization and use of electronic materials. This year’s event will feature a plenary session, topical sessions, a poster session and more.

EMC is coordinated with the Device Research Conference (DRC), which will be held during the same week, from June 20-23. This recognizes the strong interaction between device and electronic materials research and provides fruitful exchange of information between attendees of both Conferences.

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EMC 2021

technical paper

The Electronic Materials Conference (EMC) is the premier annual forum on the preparation, characterization and use of electronic materials. This year’s event will feature a plenary session, topical sessions, a poster session and more.

EMC is coordinated with the Device Research Conference (DRC). This recognizes the strong interaction between device and electronic materials research and provides fruitful exchange of information between attendees of both Conferences.

The Electronic Materials Conference (EMC) is the premier annual forum on the preparation, characterization and use of electronic materials. 

Mixed valence manganese oxides (MnOx) have attracted significant interest in recent years due to the easily reversible redox reactions between manganese oxidation states (Mn+2, Mn+3, and Mn+4)1, which has enabled applications in catalysis2, energy storage3, and gas sensing4. Manganese dioxide (MnO2), in particular, has demonstrated tunable structural properties, due to its wide variety of synthesizable structural polymorphs ((α, β) tunnel5, (γ) spinel5, and (δ) layered5) which allow for control over its available surface area and the reactive properties. Among these structural polymorphs, the α and δ phases exhibit strongly mixed-valence character, with Mn+3 defects found throughout the crystal structure5, which is desirable due to it being a highly active site6. Water-stabilized hexagonal δ-MnO2 (HMnO2) contains many Mn+3 ions as the interlayer contains Mn+2/+3 ions to neutralize the layer charge from Mn+3 lattice defects7. However, the direct synthesis of HMnO2 has not been reported extensively in the literature, as most synthesis routes rely on permanganate salts1, which leads to the synthesis of ion intercalated δ-MnO2 and a reduction in Mn+3 defects in the lattice9. In our previous work, we presented the synthesis of high Mn+3 content HMnO2 via electrodeposition on epitaxial graphene/silicon carbide (EG/SiC) substrates4. In this work, we extend upon this by transforming also these as-grown films via intercalating with ions to form alternate birnessites and controlling the growth via patterning. The electrodeposition was carried out by a three-pulse deposition in a three-electrode electrochemical cell, as described previously4. The resulting δ-MnO2 thin films were then characterized through Raman spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy(AFM). Raman spectroscopy confirmed the formation of δ-MnO2 as the peaks were consistent with the literature4,8. The AFM indicated that the surface was made up of nanofibrous nanoparticles, which SEM confirmed and indicated that the deposition on EG/SiC was made up of microplates larger than 40 μm x 40 μm in size. After this characterization, the resulting films were exfoliated mechanically and analyzed with AFM to determine if the films were epitaxial. This exfoliation generated 6-layer MnO2 nanoplates, indicating we can reach the 2D limit and confirm epitaxial growth. The resulting films were intercalated with alkali metals (Na+) via cyclic voltammetry in a similar three-electrode cell to the deposition, using a 2 M metal nitrate solution. Optical Analysis of the film indicated two distinct regions formed in the film, large multicolored regions, and small blue and black islands. Raman analysis of these regions found that the islands were unintercalated MnO2 but the colored regions were Na-type birnessite due to their Raman shifts which are consistent with the literature8. Believing ion diffusion resistance to be impeding the intercalation we patterned δ-MnO2 into 100 μm ribbons and attempted additional intercalation. Optical analysis of the film post patterned intercalation revealed two regions, a brown and blue region. Raman spectroscopy of these two regions indicated that both were Na-type birnessite. However, differing peak intensities indicate the crystallinity of the two regions is different. This demonstrates that we have successfully grown and transformed the H-type birnessite to Na-type birnessite with 100% efficiency on EG/SiC, allowing for additional fine-tuning of its properties and expanding its application in energy storage to Na+ and K+ chemistries. References: [1]L. Spinelle et al. Sensors 17(7), 2017 [2] F. Cheng et al. Chem. Mater 22(3), 2010 [3] Y.J. Huang et al. Electrochim Acta 99, 2013 [4] M. Pedowitz et al. J. Microelectromech Syst 29(5), 2020 [5] Z. Chang et al. Proc Natl Acad Sci USA 115(23), 2018 [6] Julien et al. Spectrochim Acta A 60, 2004 [7] Drits et al. Am Mineralogist 82, 1997 [8] Julien et al. Solid State Ionics 159, 2003

Transformation to Alkali Birnessites via Simple Intercalation of Electrochemically Grown 2D-Layered H-Type Manganese Dioxide on Epitaxial Graphene

In this talk I will describe a variant of molecular-beam epitaxy (MBE)—“suboxide MBE”—that makes it possible to deposit many oxide materials with excellent structural perfection at relatively low deposition temperature compared with other epitaxial methods. Examples include: -type oxide Semiconductors—b-Ga2O3, a-(Al,Ga)2O3, In2O3, BaSnO3, SrSnO3 -type oxide Semiconductors—SnO, PbO, SnTa2O6, SnWO4, Bi2BaTaO6 proposed high-Tc Superconductors—Ban+1InnO2.5n+1 with n=1, 2, ∞ Of these, b-Ga2O3, In2O3, SnO, PbO, Sr3SnO, and SnWO4 can all be grown epitaxially at back end of line temperatures. In suboxide MBE the molecular beams consist of pre-oxidized elements (suboxides) that help navigate kinetic pathways. For example, supplying a molecular beam of gallium suboxide (Ga2O) eliminates the rate limiting step of conventional MBE to the growth of b-Ga2O3—the oxidation of gallium to its suboxide—and by skipping this step growth rates exceeding 1 μm/hr with excellent crystallinity, surface smoothness, and at a low growth temperature are achieved. In addition to extensive structural characterization, electrical characterization and working transistors will also be shown. *This work was performed in collaboration with coauthors from the groups of: K. Ahadi, K. Chabak, K. Cho, S. Datta , R. Engel-Herbert, C.B. Eom, F. Giustino, V. Gopalan, A.J. Green, C. Guguschev, R.T. Haasch, G. Hautier, F.V.E. Hensling, J.T. Heron, A. Hock, D. Jena, M. Jeong, Y. Kim, D. Klimm, K. Lee, Z.K. Liu, S. Mou, D.A. Muller, H.P. Nair, A.T. Neal, T. Onuma, H. Paik, X.Q. Pan, L.F.J. Piper, N.J. Podraza, S. Salahuddin, D.G. Sangiovanni, K.M. Shen, Y.E. Suyolcu, M.O. Thompson, T.E. Tiwald, R. Uecker, P.A. van Aken, P. Vogt, M.D. Williams, C.H. Winter, H.G. Xing, and Q. Zheng.

Suboxide Molecular-Beam Epitaxy

Integrating III-V semiconductors on silicon has been a long desire to realize the advanced electronics and photonics application for the future ‘extended’ Moore’s Law regime. Transfer methods have been developed to integrate the III-V layer onto silicon, which is limited by the costive epitaxial wafer and alignment issue. Direct growth is, an alternative method to realize heterogeneous integration, which is necessary to use lattice-matching buffer layers. This imposes a significant growth challenge: thick lattice-matching buffer layers for each material must be grown with nanometer spacing, a significant challenge considering. As such, enabling high-quality growth without the use of lattice matching layers would provide a clear path toward direct growth of III-V CMOS. Here, we propose a defect-filtering growth technique to enable high-quality III-V growth on silicon by combining conventional growth with templated liquid phase growth to ensure the quality and uniformity of the grown material. Critically, this approach enables the growth and manufacturing of high-quality crystalline materials on silicon without requiring a nearly lattice-matched substrate, potentially impacting a wide range of fields, including electronics, photonics, and energy devices.

Defect Filtering at the Interface of MOCVD/TLP Heterogenous Epitaxial III-V on Silicon

The bandgap of germanium-tin (Ge1-xSnx) alloys can vary from ~0.8 eV into the far-IR as the Sn composition increases, and transition from indirect to direct bandgaps between 6 and 17 at% Sn depending on strain. Consequently they are being developed for a range of thermal and multijunction photovoltaic (PV) cells, thermal imaging, and photonic data transmission applications. However, at useful Sn contents these alloys are metastable and require low epitaxial growth temperatures and can only be grown to limited thickness; otherwise films may experience Sn segregation and defect formation. Growing below ideal temperatures for Ge can also induce defects, reducing electrical conductivity. PV cell design is harder to optimize for performance if the absorbing layer is limited in thickness by material considerations. One mitigation strategy for non-optimal growth conditions is to deposit and maintain on the growth surface a thin coverage of an additional atomic species, which acts as a surfactant to modify adatom interactions. Surfactants change the surface energy of the growth front, which controls the mobility of adatoms and affects the rate of positional exchange between buried and surface layers. A surfactant that preferentially moves to the growth surface could thus increase the incorporation of Sn into deeper layers and reduce defects due to growth at low temperatures. Additionally, the filling of partial growth layers by surfactant atoms tends to reduce islanding and therefore suppresses surface roughness. In this work, antimony is applied as an n-type dopant and surfactant in the growth of GeSn alloys to potentially improve the crystallinity of Ge and GeSn films grown by molecular beam epitaxy. Sb has a high vapor pressure at low temperatures, which is ideal for minimizing radiative heating of the substrate during low-temperature growths. Pairs of GeSn samples are deposited without and with the codeposition of Sb. The growth temperature, film thickness, and Sn content are varied to investigate the impact of Sb on Sn incorporation and film critical thickness. Depending on growth conditions, varying amounts of Sb will be incorporated into the growing film, so this study also provide data on the retention of Sb as a dopant during low-temperature GeSn growth. Sn content and film quality are characterized by X-ray diffraction, photoluminescence spectroscopy, Raman spectroscopy, spectroscopic ellipsometry, and optical microscopy. Electrical properties are determined by Hall effect measurement. Results will be discussed in terms of how the Sb surfactant has modified the kinetics of the growth process and considered with design of a GeSn based photodiodes and thermophotovoltaic (TPV) cells in mind.

Doping and Surfactant Behavior of Antimony in Molecular Beam Epitaxy Grown Germanium-Tin

The incorporation of small size boron into conventional III-V alloys provides a method for strain engineering of near-infrared, direct-bandgap alloys that can be lattice-matched to silicon1 and other2,3 substrates. In other highly-mismatched alloys (HMAs) such as dilute-nitrides and dilute-bismides, dilute amount of nitrogen or bismuth changes the lattice constant and perturbs the host band structure, reducing the bandgap though often at the expense of degraded optical properties. The advantage of incorporating boron is a higher predicted solid solubility, which suggests that less degradation of material properties can be expected than for other HMAs.4 However, B-III-V alloys remain underexplored in both theory and experiment. Thermal treatment is often employed to recover the optical properties of HMAs, but is typically accompanied by an undesirable blueshift in emission wavelength from changes in the nearest-neighbor bonding configuration.5 A blueshift in emission wavelength and modest improvement in photoluminescence (PL) has been observed with in situ and ex situ thermal annealing of BGaInAs films,2 while the converse is observed from BGaAs.6 Here we report the effects of atomic rearrangement on the band structure and optical properties of B-III-V alloys to understand this dichotomy. BGa(In)As films were grown by solid-source molecular beam epitaxy on (100) semi-insulating GaAs substrates. Samples were progressively annealed by rapid thermal annealing for 1 minute in 50°C steps from 550°C to 900°C and then characterized by room-temperature PL. Experimental results were then compared to ab initio simulations obtained with the density functional theory (DFT) package VASP using HSE06 hybrid functionals. A set of BGaInAs structures were simulated varying numbers of In atoms in the first group-III nearest neighbor positions around B atom, as well as BGaAs structures with varying distances between B atoms. We found an increase in bandgap with increasing numbers of B-In bonds and the most energy-favorable B0.037Ga0.663In0.3As structure was that with the highest number of B-In bonds. This suggests In atoms tend to be in the first nearest neighbor position of B under thermally stable conditions, contributing to a blueshift during annealing. We used an elevated In concentration for BGaInAs calculations compared with experimental data to both sweep a larger number of B-In bonds and investigate bandgap energies closer to the technologically significant 1.3 and 1.55 µm emission wavelengths. Further studies of rearrangement in BGaInAs with low In concentration are in progress. In contrast, the calculated bandgap differences, and energetic driving force due to different B-B distances in B0.03Ga0.97As were much smaller than for In-containing alloys, suggesting BGaAs alloys are not likely to show a strong blueshift upon annealing. This is consistent with the minimal, ~5 meV shift in peak PL energy observed experimentally from B0.03Ga0.97As with annealing. While the intrinsic matrix element strength of BGaInAs increased by about 30% from no B-In bonds to most B-In bonds in our calculations, it can explain a portion of the improvement in optical quality observed with annealing. Since improvement in PL intensity was observed from both BGaAs and BGaInAs, we suspect the removal of the defects played a significant role. Studies of the In concentration on the magnitude of blueshifting in BGaInAs, specifically targeting 1.3 and 1.55µm emitters, are in progress and will be reported at the conference. This work was supported by the National Science Foundation (Award Nos. ECCS-1933836, DMR-1508646, and CBET-1438608). The authors also acknowledge the LEAP cluster at Texas State University for computing resources. 1 McNicholas et al. Cryst. Growth. Des. (2021) 2 El-Jaroudi et al. Appl. Phys. Lett. (2020) 3 El-Jaroudi et al. Cryst. Growth. Des. (2022) 4 Hart et al. Phys. Rev. B. (2000) 5 Lordi et al. Phys. Rev. B. (2003) 6 White et al. 62nd EMC (2020)

Atom Rearrangement in BGa(In)As Alloys Under Annealing

Exceptional properties of ultra-wide band gap (UWBG) materials in chemical/thermal stability, spontaneous electric polarization, low dielectric permittivity, high sound velocity, high biocompatibility, and high mechanical flexibility cause increasing attention to UWBG materials as great candidates for wide range of piezoelectric applications. However, compared to those of currently dominant piezoelectric materials such as lead zirconate titanate (PZT), the piezoelectric coefficients of III-N materials are relatively low. Nevertheless, these lead-free materials have a great potential to replace the PZT because of their operational performance in high temperature and pressure conditions. Also, the biocompatibility of III-N materials makes them a promising candidate to overcome the critical limitation of PZT in epidermic and implantable sensors and electronics. Therefore, we introduce a hybrid chemical vapor deposition (HybCVD) as a new thin-film growth technique for Group-IIIa-Group-IIIb-Nitride alloy to significantly improve the piezoelectric properties in group-IIIa-N (III-N) materials such as wurtzite AlN, by group-IIIb transition metals including scandium (Sc) and yttrium (Y). In this study, we focus on the thermodynamic analysis of precursor reaction chemistry and solid-phase formation, including growth temperatures, input V/III ratios, and input carrier gas ratios in different parts of source zones and mixing/growth zone. The main reason for our calculations comes from the necessity of control on the alloy composition depending on various precursors and deposition conditions. For YGaN alloys, there is not a linear relationship between the input cation precursor ratio, RY, and composition, xY: the xY is always higher than RY, indicating significantly higher driving force for the formation of YN in the ternary phase. Also, higher growth temperature (700 → 900 ○C), more H2 in the carrier gas (0 → 100 Pa), and lower V/III ratio (200 → 100) result in higher xY by further decrease in driving force of GaN deposition. In contrast, RY vs. xY is nearly linear for YAlN alloys. When the effects of temperature, carrier gas mixture, and V/III ratio on xY are marginal, ScAlN showed the same trend as YAlN in different growth parameters’ changes. The new growth technique offers the potential to produce well-controlled, uniform, and high-quality piezoelectric films based on transition-metal-alloyed III-N materials which is critical to obtain high performance piezoelectric devices based on this material.

Composition Control of Ternary Group-IIIa-IIIb-Nitride Alloy by Hybrid Chemical Vapor Deposition—A Thermodynamic Analysis

Silicon Carbide (SiC) is a wide bandgap semiconductor, which has been widely applied to power electronics due to its excellent properties of wide band gap, high break down voltage and thermal stability. However, defects, such as threading edge dislocations (TEDs), threading screw dislocations (TSDs) and basal plane dislocations (BPDs), can limit the performance of the devices [1,2], so characterization of those defects becomes a critical aspect to improve the quality of 4H-SiC wafers. Synchrotron monochromatic beam X-ray topography (SMBXT) is a powerful technique to characterize the defects with the advantages of large field of view and clear contrast of the defects. SMBXT in 11-28 reflection has been widely used, however, the penetration depth, around 17um [3], appears to be shallow to characterize device with deep PN junction. Therefore, a new reflection with deeper X-ray penetration depth and clear contrast on the defects has been sought for. 22-4 16 reflection, the harmonic reflection of 11-28, shows better contrast on the defects, higher strain sensitivity and deeper X-ray penetration. Contrasts from the same defect of 4H-SiC with 24 um epilayer in 11-28 and 22-4 16 reflections are compared as shown in Fig. 1. From 11-28 SMBXT, BPD segments near the surface of the wafer can be observed, as shown in the blue arrows in Fig 1(a), but contrasts of the segments lying deeper in the crystal are blurred as shown in the green boxes. On the other hand, in 22-4 16 SMBXT (Fig 1(b)), the contrasts of the full BPDs can be clearly seen and the contrasts of BPD segments lying deeper in the crystal are highlighted in green boxes to compare with contrasts in 11-28 reflection. This result also proves that the penetration depth of 22-4 16 SMBXT is deeper than that of 11-28 SMBXT. Previously we have simulated images of defects in 11-28, 0008 and 000 12 using the principle of ray tracing, showing good correlation with the topograph[4,5]. In this paper, we apply the ray tracing principle to simulate defect images in the 22-4 16 topograph and compare and discuss the contrast for the different defect types. Reference: [1] K. Konishi, R. Fujita, Y. Mori and A. Shima, Semiconductor Science and Technology 2018 Vol. 33 Issue 12 [2] W. Gao, G. Yang, Y. Qian, X. Han, C. Cui, Xi. Pi, D. Yang and R. Wang, Frontiers in Materials, Jan 2023, DOI:10.3389/fmats.2023.1022878 [3] Q. Cheng, H. Peng, S. Hu, Z. Chen, Y. Liu, B. Raghothamachar and M. Dudley, Materials Science Forum 1062, 366-370 [4] H. Peng, Z. Chen, Y. Liu, B. Raghothamachar, X. Huang, L. Assoufid and M. Dudley, J. Appl. Crystallogr. 55 (2022) 544-550. [5] H. Peng, Z. Chen, Y. Liu, Q. Cheng, S. Hu, X. Huang, L. Assoufid, B. Raghothamachar and M. Dudley

Ray Tracing Simulation of Defects of 4H-SiC in 22-4 16 Reflection of Synchrotron Monochromatic Beam X-Ray Topography in Grazing Incident Geometry

Nano Fourier Transform InfraRed (nanoFTIR) spectroscopy is a powerful non-destructive characterization technique offering nanoscale spatial resolution combined with spectroscopic information. In this work we apply the combination of nanoFTIR and finite dipole modeling to characterize and identify the polytype of in-grown stacking faults (IGSF) in 4H silicon carbide. The results of stacking fault identification are verified using the established techniques of confocal Raman spectroscopy and ultraviolet photoluminescence spectroscopy. Results from one IGSF consisting of a double layered 3C inclusion will be reported. Results from additional IGSF exhibiting other polytypes are expected as the work continues in upcoming months, with the goal of identifying an IGSF with 8H polytype and extracting the dielectric function using nanoFTIR. 8H stacking faults are common, but the dielectric function of 8H is yet unmeasured due to the lack of commercially available 8H wafers.

Nanoscale Spectroscopy of Extended Defects in 4H Silicon Carbide

Ion implantation is the most useful technology for doping of 4H silicon carbide to fabricate power devices. For n-type doping, nitrogen is the most common element used in device fabrication due to its low atomic mass and proven applicability in epitaxial n-type SiC. Phosphorus can be an alternative to nitrogen (N) for providing a lower sheet resistance, although the research on phosphorus as a dopant is limited [1-3] in range of doping and activation temperatures. A rigorous study comprising different doping concentrations would help to verify the activation percentage and ionization energies and will lead to a better understanding of the properties of dopants other than N, to take advantage of any underlying benefits. In this work, phosphorus is implanted in different concentrations on 150 mm Si-face 4H SiC (0001) of 4 degree off-axis wafers and activated above 1600 oC. To study the electrical characteristics, circular van der Pauw structures were made. Deep p-well implants were performed to isolate the phosphorus doped region from the n-type substrate. Nickel contacts were deposited using evaporation and post-annealed at high temperature to get ohmic contacts. The samples were then placed on a 1cm x 1cm PCB board with 4 contacts at the corners, and wire bonding from sample to board was performed. Following that, 4-point probe resistance and Hall measurements were conducted to obtain resistivity, carrier concentration, and Hall mobility for different doping levels. Thereafter, dopant activation percentage and ionization energy levels are calculated. Figure 1 shows typical IV characteristics of the fabricated van der Pauw samples that indicate linear or ohmic behavior of the contacts. Figure 2 shows the temperature-dependent variation of resistivity for different doping levels. From 150 to 300 K the resistivity drops as temperature increases, while above room temperature a small increase of resistivity can be observed. An increase in the carrier concentration versus temperature is shown in Fig. 3, for doping less than 9x1019 cm-3. The sample with a doping concentration of 9x1019 cm-3 behaves like a semimetal for which the carrier concentration is almost constant with changing temperature. A small upshoot in carrier concentration at very low temperature (~150 K) might be caused either by a change of effective implant thickness with temperature, or p-well dopant freeze out effects underneath the n-wells. Figure 4 shows mobility versus temperature for different Phosphorus implanted concentrations. At lower temperatures mobility drops due to increased ionized impurity scattering. Mobility reaches a peak value near room temperature and drops again as temperature increases due to increased phonon scattering owing to enhanced lattice vibrations. Figure 5 shows the carrier concentrations as modeled in hexagonal and cubic lattice sites (50:50 distribution assumed) with assigned specific ionization energies. For example, for the sample with implanted doping concentration of 4x1018 cm-3, the ionization energies are extracted to be 48 and 110 meV for hexagonal and cubic lattice positions from the model fit. The values of activated dopants are also calculated here from this analysis and plotted as a function of doping concentrations as shown in figure 6. It is clear that the phosphorus activation is well below 100%. The extracted activation percentages and dopant ionization levels will be shown for all samples, and compared to literature values, in the full manuscript. The activation percentages and ionization energies, extracted from the data, will be useful for calibration of Technology Computer Aided Design (TCAD) models for electrical simulations of 4H-SiC based devices. [1] M.A. Capano et al., J. Electron. Mater. 29, 210 (2000). [2] J. Gardner et al., J. Appl. Phys. 83, 5118 (1998). [3] T. Kimoto, J.A. Cooper, Fundamentals of Silicon Carbide Technology (2014).

Study of Dopant Activation and Ionization for Phosphorus in 4H-SiC

Motivation To reduce the device cost, body diode is expected as the freewheeling diode for commercial trench SiC power MOSFETs in the high frequency applications. Therefore, it is necessary to investigate the reliability of body diodes. This study compares the body diode degradation of commercial 1.2 kV planar and trench SiC power MOSFETs from several vendors listed in Table 1. Besides, 1.2 kV planar SiC power MOSFETs are fabricated with the nominal and deep JFET. The deep JFET extends down from the nominal JFET into the drift layer, and part of the additional n+ layer is in contact with p-body. We assume that the deep JFET enhances the recombination of the injected minority carriers from p-body. This leads to the suppression of body degradation by reducing the recombination energy provided to expand SFs. These two different JFET structures are presented in Fig. 1. Results Fig. 2 compares the average degradation ratio of VF, RON, and forward leakage current in the blocking mode (IL) on the commercial 1.2 kV planar SiC power MOSFETs from Vendors E, I, and C. Decline in device performance from body diode degradation is at negligible or acceptable levels for all these three vendors. It can be concluded that body diode degradation is not a big issue in most commercial 1.2 kV planar SiC power MOSFETs. In Fig. 3, commercial trench DUTs from Vendor K have more significant average body diode degradation than planar DUTs. Trench DUTs from Vendor D have no obvious degradation. However, the influence of body diode degradation on IL is not reflected as expected. This may be due to the fact that devices are breaking down in the termination area where no SFs exist, as opposed to the active area. As shown in Fig. 4, 7 of 10 DUTs from Vendor K have reached the degradation criterion while there’s no significant body diode degradation in 8 DUTs, apart from the 2 dead devices, for Vendor D. This can be explained in Fig. 5 that the deep p+ contact by the Al implantation with high dose and energy is required to shield the electric-field-crowded corner of the trench gate, which creates many BPDs around the p+ contact in the trench structure from Vendor K. Although the p+ contact with the heavy dose is still needed for Vendor D, it is implanted after the dummy trench formed by RIE. That means the p+ contact can be shallow which significantly reduces the new BPDs. In the planar structure, high density of new BPDs around the implanted regions is hard to create because of light-dose and shallow p-type contact, as well as many improved designs and processes that have already minimized the BPDs arising from the SiC substrate wafer and epitaxial growth. In addition, Vendor D not only has the Gen 3 trench structure mentioned above, but also has the Gen 4 trench structure as shown in Fig. 6. In the Gen 4 trench structure, the Al implantation with the high energy and dose for the deep p+ contact is performed before the RIE for the trench dummy. Therefore, this new trench structure is expected to have significant body diode degradation as that of Vendor K. The body diode degradation test on the Gen 4 DUTs from Vendor D is still in progress. Furthermore, Fig. 7 compares the body diode degradation of the fabricated 1.2 kV SiC power MOSFETs with the nominal and deep JFET. It can be observed that there is increasing average body diode degradation in the DUTs with the nominal JFET during the stress. However, for the DUTs with the deep JFET under the same process, there is no average body diode degradation during the stress. It is also reflected that the breakdown voltage of the DUTs with the nominal JFET decreases due to the increasing leakage current while there is no variation for the DUTs with the deep JFET. This confirms the assumption that body diode degradation in commercial 1.2 kV SiC power MOSFETs, especially in the trench devices, is mainly caused by the new BPDs around the p-type contacts introduced by the deep Al implantation with heavy dose.

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Transformation to Alkali Birnessites via Simple Intercalation of Electrochemically Grown 2D-Layered H-Type Manganese Dioxide on Epitaxial Graphene

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