Cl Incorporation Research Articles

Insight into the Influence of Cl Incorporation into Lead-Halide Perovskite Materials: A Review

Insight into the Influence of Cl Incorporation into Lead-Halide Perovskite Materials: A Review

Effects of Mn, Cl co-doping on the structure and photoluminescence properties of novel walnut-shape MAPb0.95Mn0.05I3-xClx films

The novel walnut shape MAPb0.95Mn0.05I3-xClx film was successfully synthesized by a one-step method followed by chlorobenzene anti-solvent treatment. The bandgap energy and PL intensity of perovskite film can be effectively tuned by Mn and Cl co-doping. The enlarged bandgap energy is mainly attributed to the synergistic effect of strengthened Pb-I interaction, Cl incorporation and smaller electronegativity of Mn dopants. The stronger coupling between the Mn d- and Pb p-bands, extended carriers diffusion length and more emitting defect-associated states caused by Mn and Cl co-doping are the main reasons for the enhancing PL intensity of MAPb0.95Mn0.05I3-xClx walnut shape film. This work not only helps to in-depth understand the correlation between co-doping elements and optical properties of nanostructured perovskite films, but also provides important strategy for future designing the lower-toxic nanostructured perovskite materials with enhanced electrical and optical properties.

In situ XPS study of low temperature atomic layer deposition of B2O3 films on Si using BCl3 and H2O precursors

In this study, atomic layer deposition (ALD) of nanoscale boron oxide (B2O3) films on Si using BCl3/H2O precursors at room temperature was investigated using in situ x-ray photoelectron spectroscopy (XPS). B2O3 thin films are of considerable interest in ultra-shallow Si doping applications, including high aspect ratio FinFET structures, where film conformality and precise thickness control are crucial. ALD is therefore of particular interest for such applications. XPS data demonstrate that initial BCl3 exposures on Si at room temperature are self-limiting and are accompanied by partial B-Cl dissociation and Cl-Si formation. H2O exposures >1.7 × 108 Langmuir at room temperature removed Cl from B sites, but failed to remove Cl from the Cl-Si species. ALD-type growth of B2O3 was observed with an average growth rate of ∼2.5 Å/cycle and without further increase in the Cl content. The initial Cl contamination was due to Cl-Si bond formation at the interface, without Cl incorporation into the oxide film. The role of Cl in the inhibition of oxide film growth was further investigated by the reactions of BCl3/O2 on SiO2 at room temperature and 650 K. BCl3/O2 precursors exhibit negligible B2O3 growth at room temperature. At 650 K, B2O3 growth was observed with a decreasing growth rate per BCl3/O2 cycle, corresponding to an increase in the Cl:B atomic ratio. These data indicate that room temperature ALD using BCl3/H2O precursors is a potential route toward the formation of uniform B2O3 films for shallow Si doping applications, but that Cl-Si formation significantly impacts initial oxide nucleation and growth.

Theoretical and Experimental Investigation of Mixed Pb–In Halide Perovskites

Hybrid halide perovskites have been supposed to be a versatile class of visible light absorbers because of their high absorption coefficient, long charge carrier lifetime, and diffusion length. However, little is known about their charge transport mechanism and analysis of microstructure. Herein, we systematically investigate the structural, electronic, and optical properties of the mixed Pb–In halide perovskites based on the first-principles calculation using density functional theory in detail. Furthermore, we verify that In ions play an important role in thin-film crystallization and quality. Our calculated results reveal that the mixed Pb–In halide perovskites exhibit excellent electronic properties because of the impurity bands induced by the In dopant, and the doped perovskite phase can be stabilized by Cl incorporation as revealed by the lower formation energy. More interestingly, it is unexpected that the peak intensities of mixed Pb–In halide perovskites are stronger in the UV region, and their a...

A step towards environmental benign Mg/Pb based binary metal mixed halide perovskite material

Today's the best performing perovskite solar cells utilise Pb2+ as a major bivalent cation source, however, the presence of toxic Pb is major issue that put its commercialization in dire straits. In this report, we unveiled the chemical synthesis and characterisation of Mg/Pb binary metal mixed halide perovskite with chemical formula CH3NH3PbxMg1−xI3−yCly using MgCl2 as a compositional gradient with nominal value of x from 0.1 to 0.9. The FESEM images of compositions corresponding to higher proportion of Cl- (or MgCl2) demonstrate improved particle (or grain) size of ∼ 8–12 μm. There is a close resemblance of stoichiometric ratio of Pb:Mg obtained from EDX analysis with that of incorporated stoichiometric ratio of Pb:Mg. Further, Mg and Cl incorporation is strengthened by the characteristic spectral peak for core level electron of Mg(2p) and Cl(2p) other than Pb(4f) and I(3d) in the XPS survey spectrum of composition x = 0.5. These binary Mg/Pb Perovskite with bandgap in the range 1.57–1.59 eV behave as comparatively less toxic potential candidate for the single junction module. The IR studies at room temperature show observable shift in peak positions on comparing two extreme compositions i.e., x = 0.1 and x = 1.0. It is noticeable that both standard CH3NH3PbI3 and binary Mg/Pb Perovskite with nominal value x = 0.7 have comparable thermal stability, however, the composition x = 0.1 have lower thermal stability than x = 0.7. The carrier lifetimes measurements by Microwave Detected Photoconductivity (MDP) showed an improvement of lifetime to 142 μs for nominal value x = 0.9 compared to 76 μs in case of MAPbI3 film. Correspondingly we see a 160 mV improvement in open-circuit voltage (VOC) in the solar cells fabricated with nominal value x = 0.9 (VOC = 1.07 V) as compared to standard MAPbI3 cells (VOC = 0.90 V). The champion cell with nominal value x = 0.9 shows PCE of 14.2% where as the best PCE of MAPbI3 cell is 14.50% under a reverse scan.

The computational probing of carrier transport in MAPbI3−xClx

MAPbI3−xClx (MA) perovskite has attracted much research attention because of its remarkable carrier transport performance. However, the influence of Cl incorporation in MAPbI3−xClx perovskite on the carrier transport performance still remains unclear. With the first-principles calculations, we found that with the incorporation of the small ionic radius of Cl−, it forces the orientation of MA molecule turning from diagonal direction to axial direction. As a result, this induced lattice polarization enhances the carrier transport along the axial direction. In the light doping direction, we confirmed that the carrier transports for both electrons and holes are suppressed due to a large lattice scattering. However, in the heavy doping direction, we found that the decrease of carrier mobility is mainly caused by the energy states up-shift because of the Pb position deviation for electrons and the strong localization of Cl 3p states for holes.

Major Element and Halogen (F, Cl) Mineral–Melt–Fluid Partitioning in Hydrous Rhyodacitic Melts at Shallow Crustal Conditions

Twenty-four internally heated pressure vessel experiments were conducted at 810–860°C, 1·5–4·05 kbar, and oxygen fugacities (fO2) = NNO –0·5 to NNO +2 log units (where NNO is the nickel–nickel oxide buffer), using hydrous rhyodacitic starting glasses from Mt Usu, Japan. Aqueous solutions were added to experimental charges such that the volatile phase(s) coexisting with the crystalline phases (amphibole, plagioclase, and clinopyroxene) at run conditions buffered the F, Cl, S, and CO2 concentrations in the melt. The resultant phenocryst phases and glass chemistries were analysed by electron microprobe and Fourier transform infrared spectroscopy, and final fluid Cl– contents by chloridometer. All experiments produced homogeneous glasses and large euhedral phenocrysts with minimal compositional zonation. The results of the crystal–melt partitioning data are applicable to understanding the geochemical evolution of rhyodacitic melts at fluid-saturated shallow crustal levels, the composition of fluid phases later exsolved owing to second boiling, and the effects of halogens on amphibole crystal chemistry. The residual glasses from these experiments span the dacite–rhyolite compositional join, and are hydrous (>5 wt % H2O) with F concentrations from ≤100 ppm to 0·63 wt % and Cl from ∼130 ppm to 0·72 wt %. Measured final fluid Cl contents show that Cl strongly prefers the fluid phase over the melt phase in all experiments, with DClfluid/melt ranging from 3·5 to 22·7. Amphibole compositions are calcic, Mg-rich, and typical of those found in natural calc-alkaline arc magmas. They are particularly sensitive to changes in melt halogen chemistry, with maximum amphibole F contents of 2·59 wt % (maximum DFamph/melt values of ≥15) and maximum Cl contents of 0·12 wt % (maximum DClamph/melt values of 0·40). Integration of the amphibole data with other experimental data shows that Cl incorporation is a strong function of the Mg–Cl crystallographic avoidance principle, and that addition of F to the melt strongly decreases Cl partitioning at equivalent Mg# (DClamph/melt = 0·10 ± 0·02 in experiments that were not F-doped, compared with DClamph/melt = 0·05 ± 0·01 in F-doped experiments). Plagioclase compositions are relatively restricted, with anorthite contents An59–An39, and clinopyroxene is similarly calcic, containing a significant enstatite component (Wo49–Wo30). The behaviour of Fe in the glass and crystalline phases is most significantly affected by the fO2 of the experiment. Higher total Fe contents are found in amphibole and clinopyroxene from experiments with fO2 < NNO +1, but with little effect on the absolute DFeOmineral/melt. Plagioclase, however, shows relatively decreased DFeOplag/melt reflecting its preferential incorporation of Fe3+, and less Fe3+ expected in melts crystallized at lower fO2 conditions. Comparison of the data with recently formulated amphibole geothermometers, barometers, and plagioclase hygrometers shows calculated results that are consistent with the actual experimental conditions but discrepancies arise owing to halogen-induced major element variations in amphibole, indicating the importance of routinely measuring F and Cl in both natural and experimental amphibole.

Impact of Electroplating at Lower Leveler Content on the Formation of Low Resistivity Narrow Cu Interconnects

This paper evaluates the resistivity, crystal grain structure and grain size distribution in 50 nm wide and 150 nm deep Cu interconnects electroplated using less leveler-containing high purity electrolyte. Resistivity of these sized Cu interconnects electroplated using 60 μL leveler-containing electrolyte is found to be 25% lower than that of Cu interconnect electroplated using the 600 μL (standard) leveler-containing electrolyte. The reduction of leveler content in electrolyte suppresses the Cl and Fe atom incorporation into the Cu interconnects and the formation of ClO and Fe(ClO) clusters at the grain boundary which reduces the grain growth in narrow Cu interconnects due to their pinning effect. The reduction of leveler content in electrolyte can also promote the formation of the as-electroplated Cu interconnects with very fine grain structure. When annealing these Cu interconnects electroplated using less leveler-containing electrolyte, the crystal grains can be considered to coarsen significantly due to the fewer numbers of ClO and Fe(ClO) clusters at the grain boundary and their large grain boundary energy. As a consequence of the significant grain coarsening, the numbers of crystal grains with less than 40 nm diameter are considered to diminish, resulting in low resistivity Cu interconnects.

Spatially Heterogeneous Chlorine Incorporation in Organic–Inorganic Perovskite Solar Cells

Spatial heterogeneities in the chemical makeup of thin film photovoltaic devices are pivotal in determining device efficiency. We report the in-plane spatial distribution and degree of chlorine incorporation in organic–inorganic lead halide perovskite absorbers by means of nondestructive synchrotron-based nanoprobe X-ray fluorescence. The presence of chlorine is positively identified in CH3NH3PbI3 films synthesized with Cl-containing precursors and as an impurity in some films synthesized with nominally Cl-free precursors. The impurity may be introduced from precursors or as contaminants during film synthesis. The films formed from Cl-containing precursors contain roughly an order of magnitude higher amount of chlorine, with Cl:I values greater than 0.02 found whether Cl is present in either the organic or the inorganic precursor for both one- and two-step fabrication processes. A spatial variation in the Cl incorporation is observed within single particles and as well as between particles within a given ...

Investigation of chlorine-mediated microstructural evolution of CH3NH3PbI3(Cl) grains for high optoelectronic responses

An organic-inorganic hybrid perovskite is considered as a next generation solar energy harvester due to the high power conversion efficiency. The starting precursor solution for the organolead halide perovskite is of significant interests because the ionic components in the precursor can critically affect the nanostructures and thereby the optoelectronic properties. In this work, the basic and well-known precursor solution for CH3NH3PbI3(Cl) comprised of CH3NH3I and PbCl2, is specifically analyzed to unravel the phenomena in the Cl-mediated solutions. The shift in equilibrium between lead-halide complex and the solvent results into the CH3NH3PbI3(Cl) grain evolution with Cl incorporation, which is confirmed through x-ray fluorescence and diffraction. The effects of Cl on the optoelectronic properties are further verified by conductive atomic force microscopy, and the existing Cl leads to the 30-times-increased and inhomogeneously distributed photocurrent for CH3NH3PbI3(Cl) grains compared with CH3NH3PbI3. Moreover, photocurrent noise from the mixed-halide perovskite is reduced than that from the triiodide perovskite phase. Combining the microstructural evolution with the optoelectronic properties of mixed-halide perovskite, it is concluded that additional Cl reduces the defects of recombination centers resulting high photocurrent.

Mediation of Valence Band Maximum of BiOI by Cl Incorporation for Improved Oxidation Power in Photocatalysis

Cl-incorporated BiOI nanostructures with different Cl/I molar ratios have been successfully fabricated via a facile room-temperature method in H2O/EG mixture solvent. Combined with FT-IR, Raman spectrum, XRD Rietveld refinements, and DFT calculation, the incorporated Cl ions are found mainly occupied on I sites, resulting in a hybrid valence band consisting of I 5p, O 2p, and Cl 3p orbitals, which deepens the valence band location of the materials and induces photogenerated holes with higher oxidation power. The incorporated Cl ions into the lattice also change the evolution of photogenerated electrons and holes, inducing the broadening of the bandgap but efficient production of photogenerated carriers. The enhanced oxidation power of Cl-incorporated BiOI products was evaluated by photocatalysis degradation of methylene blue, an organic dye for which pure BiOI shows negligible direct oxidation efficiency. Ascribed to the relatively low valence band maximum (VBM) and efficient generation of photoinduced el...

Chlorine Incorporation for Enhanced Performance of Planar Perovskite Solar Cell Based on Lead Acetate Precursor.

We show the effects of chlorine incorporation in the crystallization process of perovskite film based on a lead acetate precursor. We demonstrate a fabrication process for fast grain growth with highly preferred {110} orientation upon only 5 min of annealing at 100 °C. By studying the correlation between precursor composition and morphology, the growth dynamic of perovskite film in the current system is discussed. In particular, we found that both lead acetate precursor and Cl incorporation are beneficial to perovskite growth. While lead acetate allows fast crystallization process, Cl improves perovskite crystallinity. Planar perovskite solar cells with optimized parameters deliver a best power conversion efficiency of 15.0% and average efficiency of 14.0% with remarkable reproducibility and good stability.

Chlorine-Enriched Tourmalines In Hydrothermally Altered Diorite Porphyry From the Biely Vrch Porphyry Gold Deposit (Slovakia)

Chlorine-enriched tourmaline was found in a hydrothermally altered Miocene diorite porphyry at the Biely Vrch porphyry gold deposit (Central Slovakia) as a relatively rare alteration mineral forming radial aggregates composed of thin prismatic crystals in the central part of quartz veinlets filled by calcite. Zoned tourmaline with Cl-enriched central zones is accompanied by allanite-(Ce) to epidote, fluorapatite, Al-rich titanite, magnetite, rutile, ilmenite, and pyrite. The tourmaline chemical composition is controlled by exchange of Fe 2+ for Al at relatively constant Mg content. It produces a trend from the earliest X -site vacant Al-rich oxy-tourmaline in the central part of tourmaline aggregates to the latest feruvite on their margins. Tourmalines belong to three groups: X -site vacant (“ vacancy-Mg-O root name” tourmaline, magnesio-foitite, and foitite), alkali (oxy-schorl, schorl), and calcic (feruvite) tourmaline. The variation in Al and Fe content is the result of concomitant action of AlOFe −1 OH) −1 , Al X □Fe −1 Na −1 , and FeCaAl −1 Na −1 substitutions. Enrichment in Ca likely results from FeCaAl −1 Na −1 substitution. The Cl content in tourmaline from Biely Vrch attains 0.45 wt.%, which is equivalent to 0.126 apfu . The chlorine content increases with decreased Fe and increased octahedral Al and X -site vacancy. Bond-length calculations yield six bond-valence and bond-length probable local structural arrangements with W Cl, and these are all characterized by dominance of Al at the Y sites and O at the V sites. Based on the analytical data and bond-length calculations, the chemical composition of Cl-enriched tourmaline is a result of crystallographic factors as well as petrologic environmental conditions. The enrichment in Cl is most likely related to the unusually Cl-rich hot hydrothermal fluid responsible for the origin of the host Biely Vrch porphyry gold deposit. The Cl incorporation in tourmaline is influenced by Fe availability in the genetic environment; increased Fe 2+ substitution for Al reduces the ability of tourmaline to incorporate Cl.

Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes

Multi-valent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage ($\sim$ 3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static first-principles calculations and $ab\; initio$ molecular dynamics, we perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg$^{2+}$ and Cl$^-$ dissolved in liquid tetrahydrofuran (THF). Our findings not only provide a picture of the stable species at the interface, but also explain how this system can support reversible Mg deposition and as such we provide insights in how to design other electrolytes for Mg plating and stripping. The active depositing species are identified to be (MgCl)$^+$ monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl$_2$ complexes). Upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge-transfer is shown to be small ($\sim$ 61 $-$ 46.2 kJ mol$^{-1}$ to remove 3 THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)$^+$ complexes appear favorable for charge-transfer. Finally, observations of Mg-Cl dissociation at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction.

A combined ToF-SIMS and XPS study for the elucidation of the role of water in the performances of a Post-Plasma Process using LaMnO3+δ as catalyst in the total oxidation of trichloroethylene

LaMnO3+δ which is an environment-friendly and inexpensive material has been previously used as catalyst in Post-Plasma Catalysis (PPC) in the total oxidation of trichloroethylene (TCE) which is a solvent widely used in dry cleaning and degreasing processes. It has been shown that the process efficiency increases in moist air (RH=18%).The issue we want to address herein is the effect of water on the location of chlorine at the surface of the catalyst as chlorine is able to alter the catalyst structure, activity and stability. Therefore, a combined Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) study has been carried out on the fresh LaMnO3+δ catalyst (LM) and used catalysts after performing PPC with TCE diluted in dry synthetic air (LM0) or with industrial air containing water (LM18; 18 stands for the Relative Humidity) and CO2 (about 560ppmv) at a temperature of 150°C. XPS and ToF-SIMS results both show the presence of chlorine on the tested catalysts whose amount increases by exposure of the catalyst to the reactive mixture in dry synthetic air. XPS results reveal that chlorine is present as both chloride ion and covalent chlorine on LM0 while organic chlorinated residues are absent on LM18 catalyst. ToF-SIMS study indicates that lanthanum excess as oxide(hydroxide) partially covering the perovskite mainly transforms into LaOCl and to a minor extent into LaCl3. Extent of Mn chlorination seems to be favored over LM0 having a higher MnClx±/MnOCl± ionic ratio compared to LM18. Furthermore ToF-SIMS clearly identifies C1 chlorinated organic ions, mainly CH2Cl+ and CHCl2−, on LM0 which may contribute to the XPS Cl organic component. From the combined ToF-SIMS and XPS results it is found that water delays the surface degradation extent of the perovskite into related (oxy)(hydroxy)chlorinated inorganic phases by less molecular chlorine and related chlorine species on the catalyst surface. A reaction scheme of Cl removal over LaMnO3+δ emphasing the role of water is given taking into account the detection of ToF-SIMS ions representative of the successive Mn intermediate states. As a consequence water allows tuning the degradation pathways of the main intermediate of the reaction, dichloroacetyl chloride (DCAC), which decomposes to give phosgene, HCCl3 and CCl4 by a successive Cl incorporation over (oxy)(hydroxy)chorinated perovskite or/and Mn species while COx species are likely formed over the perovskite.

MAPbI3-xClx mixed halide perovskite for hybrid solar cells: the role of chloride as dopant on the transport and structural properties

ABSTRACTHybrid halide perovskites represent one of the most promising solutions toward the fabrication of all solid nanostructured solar cells with improved efficiency and long-term stability. This article aims at investigating the structural properties of the iodide/chloride mixed-halide perovskites and correlating them with the photovoltaic performances of the related sensitized solar cells. We found out that, independently on the components ratio in the precursor solution, Cl incorporation, in a I-based structure, is possible only at relatively low concentration levels (below 3-4%). However, even if the material band-gap remains substantially unchanged, incorporation of Cl as a dopant dramatically improves the charge transport within the perovskite layer, explaining the outstanding performances of meso-superstructured solar cells based on this material.

MAPbI3-xClx Mixed Halide Perovskite for Hybrid Solar Cells: The Role of Chloride as Dopant on the Transport and Structural Properties

Hybrid halide perovskites represent one of the most promising solutions toward the fabrication of all solid nanostructured solar cells, with improved efficiency and long-term stability. This article aims at investigating the structural properties of iodide/chloride mixed-halide perovskites and correlating them with their photovoltaic performances. We found out that, independent of the components ratio in the precursor solution, Cl incorporation in an iodide-based structure, is possible only at relatively low concentration levels (below 3–4%). However, even if the material band gap remains substantially unchanged, the Cl doping dramatically improves the charge transport within the perovskite layer, explaining the outstanding performances of meso-superstructured solar cells based on this material.

Atomic layer deposition of titanium phosphate on silica nanoparticles

Titanium phosphate was deposited on silica nanoparticles by atomic layer deposition (ALD). The precursors were titanium tetrachloride (TiCl4), trimethylphosphate ((MeO)3PO), and water. Depositions were done at 150–300 °C employing a variety of pulse sequences which altered the self-limiting deposition process. Using the pulse sequence TiCl4-H2O-(MeO)3PO-H2O, the process was self-limiting at 200 °C, and ≤0.3 at.% Cl was incorporated into the material. With the pulse sequence TiCl4-H2O-(MeO)3PO, the process was not completely self-limiting at 200 °C and slightly more Cl incorporation occurred. Using the pulse sequence TiCl4-(MeO)3PO, the process was not self-limiting at 175 or 250 °C, and Cl incorporation was 0.2–2 at.%. The surface area of the material decreased from 300 m2/g for uncoated silica to 46 m2/g for silica coated with 60ALD cycles.

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt

We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D Cpx/melt > D Opx/melt > D Grt/melt > D Ol/melt > D Plag/melt, and D mineral/melt is larger than D Cl mineral/melt . Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E 0) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D 0 M 1, D 0 M 2, r 0 M1 , r 0 M2 , E 0 M1 and E 0 M2 .

Ab initio study of isolated chlorine defects in cubic SiC

The electronic properties and formation energy of isolated Cl defects in SiC were investigated by first-principles calculations. Chlorine was studied in a substitutional position, in either a carbon (ClC) or a silicon site (ClSi), and in two interstitial positions (Cli), either tetrahedral or octahedral configurations. Our calculations revealed that ClC is energetically favored and it is a likely candidate to explain the nature of the experimentally observed Cl incorporation reported in SiC epilayers grown by chloride-based chemical vapor deposition.