Formation Energies Of Point Defects Research Articles

Interactions between displacement cascades and grain boundaries in NiFe single-phase concentrated solid solution alloys

Single-phase concentrated solid solution alloys (SP-CSAs) are promising structural materials with excellent irradiation resistance. It is very important for their application in nuclear reactor structures to understand the interactions between their grain boundaries (GBs) and irradiation-induced defects. With molecular dynamics (MD) simulations, the displacement cascades in NiFe SP-CSAs with Σ5(210) symmetrical tilt GB were studied. Compared with pure Ni, NiFe has higher sink strength of GB for vacancies but has little effect on the interstitial absorption of GB. The formation energies of interstitials and vacancies near the GB are more dispersed, so that the point defects are more difficult to aggregate, which is beneficial for the recombination of interstitials and vacancies near the GB. Both the formation energies of point defects and the sink strengths of GB for point defects could be changed with the SP-CSA compositions. When the Fe atom concentration is higher than 30 at.%, the point defects are easier to annihilate. Both the effects of the PKA energy and the PKA-GB distance on the displacement cascades damage can be explained with the size of overlapping region between the cascade region and GB. In addition, the formation of SP-CSAs helps to annihilate the vacancies in NiFe with Σ37(750) symmetrical tilt GB and Σ5 twist GB.

First-principles calculations for the effect of energetic point defect formation on electronic properties of the Weyl MX family (M = Nb, Ta; X = P, As)

• The unfolding technique was used for the first time to highlight the impact of point defects on the electronic band structure. • The transition metal Nb and Ta vacancies are energetically nearer to stability in the cases of NbAs and TaAs. • The pnictide P vacancy is energetically favorable among four possible point defects in both NbP and TaP. • For TaAs, the Ta vacancy concentration is significantly higher than all other types of defect concentrations. • All four of these compounds are thermodynamically, dynamically, and mechanically stable. By the first-principles of the density functional theory (DFT) approach, the structural parameters, elastic, vibrational, electronic properties, and enthalpies of formation of four stoichiometric Weyl semimetal compounds were evaluated. Besides, we calculated point defect formation energies and electronic band structures of defect-containing supercells by using an unfolding technique to highlight the effects of point defects (vacancies and anti-sites) on Weyl points in the electronic structure of these compounds. The transition metal Nb and Ta vacancies are energetically nearer to stability in the cases of NbAs and TaAs, but the pnictide P vacancy is energetically favorable among four possible point defects in both NbP and TaP. The band structure results, obtained from the unfold method, agree with defect formation energies at the ground state. Moreover, a true and accurate description of defects is based on the well-ordered compounds (NbAs, TaAs, NbP, and TaP). A relationship between temperature (K based on defect formation energies) and defect concentrations for these Weyl compounds was derived. In particular, for TaAs, the Ta vacancy concentration is significantly higher than all other types of defect concentrations.

Effects of proton irradiation-induced point defects on Shockley–Read–Hall recombination lifetimes in homoepitaxial GaN p–n junctions

This work examined the intentional generation of recombination centers in GaN p–n junctions on freestanding GaN substrates. Irradiation with a 4.2 MeV proton beam was used to create a uniform distribution of vacancies and interstitials across GaN p+/n− and p−/n+ junctions through anode electrodes. With increasing proton dose, the effective doping concentrations were found to be reduced. Because the reduction in the doping concentration was much higher than the hydrogen atom concentration, this decrease could not be attributed solely to carrier compensation resulting from interstitial hydrogen atoms. In fact, more than half of the electron and hole compensation was caused by the presence of point defects. These defects evidently served as Shockley–Read–Hall (SRH) recombination centers such that the SRH lifetimes were reduced to several picoseconds from several hundred picoseconds prior to irradiation. The compensation for holes in the p−/n+ junctions was almost double that for electrons in the p+/n− junctions. Furthermore, the SRH lifetimes associated with p−/n+ junctions were shorter than those for p+/n− junctions for a given proton dose. These differences can be explained by variations in the charge state and/or the formation energy of intrinsic point defects in the p-type and n-type GaN layers. The results of the present work indicate the asymmetry of defect formation in GaN based on the fact that intrinsic point defects in p-type GaN readily compensate for holes.

A comprehensive study on the processing of Co:ZnO nanostructured ceramics: Defect chemistry engineering and grain growth kinetics

• Co:ZnO samples were prepared from different Co precursor (Co3O4, CoO, and metallic Co) in different sintering atmosphere (oxygen and argon). • First-principles calculations were performed to give support to the defect chemical analysis and insight into the mechanisms of the Co incorporation in the ZnO. • A detailed structural characterization was employed to determine the Co apparent incorporation activation energy and the grain growth kinetic parameters. • The Ar sintering atmosphere promotes an incongruent decomposition of the ZnO, leading to a higher Zn i density and a higher Co solubility. • To achieve high grain growth and densities the Co3O4 demonstrated to be a good additive for the w -ZnO sintering. • In the Ar sintering atmosphere the metallic Co precursor, due to its higher solubility into the w -ZnO, leads to a high Co homogeneous distribution over the w -ZnO grain. • CoO present the lowest solubility into w -ZnO and final grain size, being the best choice for top-down approach in processing of Co-doped w -ZnO nanopowders. In this report, we present a systematic study on the preparation of Co:ZnO ceramics via a standard solid-state route from different Co precursors (Co 3 O 4 , CoO, and metallic Co) and atmospheres (O 2 and Ar). Particular emphasis is given to defect chemistry engineering and the sintering growth kinetics. First-principles calculations based on density functional theory are employed to determine the formation energy of the main point defects in ZnO and Co:ZnO systems. Based on the theoretical results, a set of chemical reactions is proposed. Detailed microstructural characterization is also performed to determine the degree of Co incorporation into the ZnO lattice. The samples prepared in Ar atmosphere and metallic Co present the highest Co solubility limit (lower apparent Co incorporation activation energy) due to the incongruent ZnO decomposition. Determination of the parameters of the sintering growth kinetics reveals that Co 3 O 4 is the best sintering additive to achieve larger grain sizes, and possible higher densities, in both sintering atmospheres, while metallic Co is the best to achieve the smallest grain size with higher Co concentration and homogeneous spatial distribution for a subsequent reduction of dimensionality. The results show that the sintering in O 2 effectively promotes zinc vacancies in the ZnO structure, while the sintering in Ar promotes zinc interstitial defects. Our findings contribute to understanding the preparation of Co-doped ZnO ceramics and the sintering growth kinetics, which may improve the state of the art in processing the material at both bulk and nanometric scales.

Thermodynamics of native defects in Li2O: A first-principles study

The crystals are used in deuterium-tritium fusion reactors and batteries, and crystal defects can increase the electrical conductivity. Therefore, the stability of the native point defects in Li2O has been examined in the work while taking vibration entropy into account. By calculations, we can obtain the defect formation energies including vacancies (VO, VLi), interstitials (Oi, Lii) and antisites (OLi, LiO), and the relationship between native point defect formation energy in Li2O versus Fermi level EF, oxygen partial pressure and temperature. The results indicate that the majority of the donors and acceptors are deep defect transition levels. The stable states of the vacancy-type defects, interstitial-type defects, and antisite defects are the fully charged state except antisite defects OLi. It is possible to predict that the acceptor defects are more likely to form under low oxygen partial pressure and high temperature, whereas the donor defects are more likely to form under high oxygen partial pressure and low temperature. Our work is aimed to provide the growth conditions for effectively adjusting the main type of defects and provide insightful guidance for the production and application of lithium oxide.

A machine-learned spin-lattice potential for dynamic simulations of defective magnetic iron

A machine-learned spin-lattice interatomic potential (MSLP) for magnetic iron is developed and applied to mesoscopic scale defects. It is achieved by augmenting a spin-lattice Hamiltonian with a neural network term trained to descriptors representing a mix of local atomic configuration and magnetic environments. It reproduces the cohesive energy of BCC and FCC phases with various magnetic states. It predicts the formation energy and complex magnetic structure of point defects in quantitative agreement with density functional theory (DFT) including the reversal and quenching of magnetic moments near the core of defects. The Curie temperature is calculated through spin-lattice dynamics showing good computational stability at high temperature. The potential is applied to study magnetic fluctuations near sizable dislocation loops. The MSLP transcends current treatments using DFT and molecular dynamics, and surpasses other spin-lattice potentials that only treat near-perfect crystal cases.

Influence of self-doping on band-edges and Fermi energy of CsPbBr3

The electronic properties of CsPbBr 3 thin films cast through a solution route are known to depend on the stoichiometry of the precursors. In this work, with the aid of Kelvin probe force microscopy (KPFM) and scanning tunneling spectroscopy (STS) studies, a complete energy landscape has been derived for the all-inorganic perovskite formed with a wide range of precursor stoichiometries. While the optical band gap of the perovskite is known to remain unchanged with a variation in the stoichiometry, we show the manner in which their Fermi energy, valence band (VB), and conduction band (CB) edges shift. The variation in the energy levels has been correlated to the presence of defects. Since the formation energy of different intrinsic point defects depends on the growth environment, the nature of defects has depended on the precursor stoichiometry used during the formation of the perovskites. The presence of defects has thereby tuned the Fermi energy and the type of electronic conductivity in CsPbBr 3 as well. Here, the CB and VB edges have responded due to the self-doping process. Finally, we have presented the energy landscape of the perovskite with a variation in the precursor stoichiometry, since the energy levels are indeed crucial in designing any optoelectronic devices based on CsPbBr 3 . • Fermi level and band edges of CsPbBr 3 are affected by the precursor stoichiometry. • Energy landscape of the perovskite derived from a combination of KPFM and STS. • CsPbBr 3 formed with CsBr-rich precursors has p -type conductivity. • CsPbBr 3 formed with PbBr 2 -rich growth condition exhibits an n -type behavior. • Bands moved away from vacuum level in perovskites formed in PbBr 2 -rich environment.

Effect of cationic chemical disorder on defect formation energies in uranium–plutonium mixed oxides

At the atomic scale, uranium–plutonium mixed oxides (U,Pu)O2 are characterized by cationic chemical disorder, which entails that U and Pu cations are randomly distributed on the cation sublattice. In the present work, we study the impact of disorder on point defect formation energies in (U,Pu)O2 using interatomic-potential and density functional theory (DFT + U) calculations. We focus on bound Schottky defects (BSD) that are among the most stable defects in these oxides. As a first step, we estimate the distance RD around the BSD up to which the local chemical environment significantly affects their formation energy. To this end, we propose an original procedure in which the formation energy is computed for several supercells at varying levels of disorder. We conclude that the first three cation shells around the BSD have a non-negligible influence on their formation energy (RD≃7.0Å). We apply then a systematic approach to compute the BSD formation energies for all the possible cation configurations on the first and second nearest neighbor shells around the BSD. We show that the formation energy can range in an interval of 0.97 eV, depending on the relative amount of U and Pu neighboring cations. Based on these results, we propose an interaction model that describes the effect of nominal and local composition on the BSD formation energy. Finally, the DFT + U benchmark calculations show a satisfactory agreement for configurations characterized by a U-rich local environment and a larger mismatch in the case of a Pu-rich one. In summary, this work provides valuable insights on the properties of BSD defects in (U,Pu)O2 and can represent a valid strategy to study point defect properties in disordered compounds.

Frenkel pair formation energy for cubic Fe3O4 in DFT + U calculations

The cubic phase of magnetite is stabilized above the Verwey transition temperature of about 120 K via a complex electron–phonon interaction that is still not very well understood. In this work using the DFT + U method we describe our attempt to calculate point defect formation energies for this cubic phase in the static approximation. The electronic structure calculations and atomic relaxation peculiarities are discussed in this context. Only the cubic phase model with a small band gap and charge disproportionation (Fe2+/Fe3+) gives an adequate point defect formation energies, not the semi-metallic model. The relaxation of the local defect atomic structure and the relaxation of the surrounding crystal matrix are analyzed. Point defects cause only local perturbations of atomic positions and charge-orbital order. After analysis of the supercell size effects for up to 448 atoms, we justify the use of small supercells with 56 atoms to make calculations for the cubic phase. The extensive experimental results of Dieckmann et al on defects in magnetite at high temperature are deployed for comparison of our DFT + U results on Frenkel pair formation energies.

Phosphor‐in‐Silica‐Glass: Filling the Gap between Low‐ and High‐Brightness Solid‐State Lightings

AbstractHigh‐brightness phosphor‐converted solid‐state light (SSL) sources based on blue light‐emitting diodes (LEDs) or laser diodes (LDs) will enable versatile optical applications other than general illumination. However, luminescence ceramics/crystals are too expensive for widespread use, while phosphor‐in‐glass converters suffer from low conversion efficiency at high‐power‐density excitation and poor chemical and thermal stabilities of low‐melting glasses. Herein, an ultrathin interface (<50 nm) is reported in Lu3Al5O12:Ce3+ phosphor‐in‐silica‐glass (LuAG:Ce‐PiSG) despite being sintered at 1250 °C, endowing them with high internal quantum efficiency (>95%) and excellent stabilities. Combined experimental results and first‐principles calculations reveal that the large formation energy of SiAl point defects makes the undesired interfacial reaction between aluminate garnets and silica glass intrinsically suppressed. Phosphor‐converted LEDs/LDs fabricated by LuAG:Ce‐PiSG exhibit high luminous efficiency (195 lm W−1 @ 20 mA) and high brightness (1914 lm @ 13.4 W mm−2), approaching the performances of their ceramic counterparts. The results not only provide a way to balance the brightness and the price for SSL sources but also unleash the potential of silica glass as an inorganic matrix for emerging optical applications.

Study of thermoelectric performance and intrinsic defect of promising n-type half-Heusler FeGeW

Half-Heusler (HH) compounds are considered promising thermoelectric materials for high-temperature power generation due to their good electrical properties and thermal stability. Some new HHs with excellent thermoelectric properties are found to be p-type, the discovery of competitive n-type HH materials has been extremely challenging. Here, we report a new HH compound FeGeW through first-principles calculation, which exhibits a high ZT of 2.36 at 1000 K. Systematically studied its thermoelectric performance indicates that a large dispersion or small band effective mass of conduction band can efficiently improve the electrical conductivity of n-type FeGeW. From the calculated formation energy of intrinsic point defects, we find that positive charged Fe interstitial are found to be the dominant defect at Fe-rich/Ge-poor condition, which account for the n-type conduction. Moreover the transition levels of Fe interstitial defect is shallow, which means that this donor defect does not damage electrical conductivity and thermoelectric performance. These results not only find a new n-type HH compound FeGeW, but also are helpful for understanding the roles of point defects in FeGeW, which is expected to encourage more experimental and theoretical investigations to study this kind of n-type HH thermoelectric material and seek out strategies to optimize thermoelectric performance using intrinsic point defect.

Molecular dynamics simulations of displacement cascade near precipitate in zirconium alloys

Precipitates play an important role in the evolution of irradiation-induced defects and mechanical property of irradiated metals. In this work, the effects of a Zr2Cu precipitate on the production and subsequent evolution of cascade-induced point defects (vacancies and interstitials) in ZrCu alloy were investigated by molecular dynamics simulations at room temperature. The simulation results show that the precipitate increases the number of residual point defects at the end of cascade. However, most of the residual defects reside in the precipitate and near precipitate boundary. In the matrix, more interstitials survive than vacancies. In addition, a defect-free region is seen in matrix and near precipitate boundary, indicating that the precipitate boundary traps vacancies/interstitials in matrix and retains them in the precipitate. To explain these observations, the formation energy and migration energy of point defects are calculated. The formation energies of both vacancy and interstitial decrease as they are moving to the precipitate boundary from matrix and precipitate, indicating that they can be absorbed by precipitate boundary and result in the defect-free region. However, the migration barrier of vacancy is lower than that of interstitial. Therefore, more vacancies in matrix are absorbed. The current work provides new insights into understanding the irradiation effects in zirconium alloys.

Potential accident tolerant fuel candidate: Investigation of physical properties of the ternary phase U2CrN3

In the present study, physical properties of the ternary phase U2CrN3 are evaluated experimentally and by modeling methods. High density pellets containing the ternary phase were prepared by spark plasma sintering (SPS). The microstructural and crystallographic analyses of the composite pellets were performed using scanning electron microscopy (SEM), standardised energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD). Evaluation of the mechanical properties was performed by nanoindentation test. The impact of temperature on lattice properties was evaluated using high temperature X-ray diffraction (XRD) coupled with modeling. Progressive change in the lattice parameters was obtained from room temperature (RT) to 673 K, and the result was used to calculate average linear thermal expansion coefficients, as well as an input for the density functional theory (DFT) modeling to reassess the degradation of the mechanical properties. The ab-initio calculation provides an initial assessment of electronic configuration of this ternary phase in a direct comparison with one of UN phase. For this goal, modeling was also employed to evaluate point defect formation energies and electronic charge distribution in the ternary phase. Results indicate that the U2CrN3 phase has similar mechanical properties to UN (Young's, bulk, shear moduli, hardness). No preferential crystallographic orientation was observed in the composite pellet. However, charge electron density distribution highlights the significant directionality of chemical bonds, which is in agreement with the anisotropy and non-linear behaviour of the obtained thermal expansion (α¯(aa) = 9.12 × 10−6/K, α¯(ab) = 5.81 × 10−6/K and α¯(ac) = 6.08 × 10−6/K). As a consequence, uranium was found to be more strongly bound in the ternary structure which may delay diffusion and vacancy formation, promising an acceptable performance as nuclear fuel.

Point defect formation energies in graphene from diffusion quantum Monte Carlo and density functional theory

Density functional theory (DFT) is widely used to study defects in monolayer graphene with a view to applications ranging from water filtration to electronics to investigation of radiation damage in graphite moderators. To assess the accuracy of DFT in such applications, we report diffusion quantum Monte Carlo (DMC) calculations of the formation energies of some common and important point defects in monolayer graphene: monovacancies, Stone-Wales defects, and silicon substitutions. We find that standard DFT methods underestimate monovacancy formation energies by around 1 eV. The disagreement between DFT and DMC is somewhat smaller for Stone-Wales defects and silicon substitutions. We examine vibrational contributions to the free energies of formation for these defects, finding that vibrational effects are non-negligible. Finally, we compare the DMC atomization energies of monolayer graphene, monolayer silicene, and bulk silicon, finding that bulk silicon is significantly more stable than monolayer silicene by 0.7522(5) eV per atom.

Effect of native point defects on the photocatalytic performance of ZnIn2S4

Understanding of materials at atomic scale is mandatory for improving their physical properties in the desired way. Here, first-principles calculations with the most accurate hybrid functional are performed to investigate one of the most attractive photocatalyst ZnIn2S4. The electronic structures of perfect and defective cubic-ZnIn2S4 are examined as a representative of other ZnIn2S4 polymorphs. The influence of growth conditions on the photocatalytic activity of ZnIn2S4 is elucidated by considering the formation energy of native point defects under different growth conditions. Our results reveal that undoped ZnIn2S4 is a native n-type material owning to the high pinned Fermi-level under all growth conditions. The source of electron carriers in undoped ZnIn2S4 is the InZn antisite defect and its photocatalytic performance is declined by the formation of dominant compensating Zn vacancy defect. The S-poor growth condition of undoped ZnIn2S4 is unveiled to provide the best photocatalytic performance due to the highest pinned Fermi-level.

The exchange between anions and cations induced by coupled plasma and thermal annealing treatment for room-temperature ferromagnetism.

Two-dimensional (2D) materials, with outstanding magnetic properties at room temperature, are highly desirable for the future spintronic and nanoscale electronic industry. However, most of the 2D systems are not of magnetic nature due to thermal fluctuations. Herein, we propose a novel strategy to induce robust room-temperature ferromagnetism in the originally nonmagnetic 2D ReS2 by the exchange between anions and cations. The vacancies are created by argon plasma treatment, which lowers the formation energy of point defects. The subsequent annealing facilitates the movement of the cations into the anion sites, giving rise to antisite defects, which leads to a significant increase in the magnetization. First-principles calculations demonstrate that the point defect with respect to the antisite substitution from Re to S is responsible for the extraordinary room-temperature ferromagnetism. This work opens a new door to the design of spin electronic structures by controllable antisite defects.

First-principles calculations of defects in metal halide perovskites: A performance comparison of density functionals

Metal halide perovskite semiconductors have outstanding optoelectronic properties. Although these perovskites are defect-tolerant electronically, defects hamper their long-term stability and cause degradation. Density functional theory (DFT) calculations are an important tool to unravel the microscopic structures of defects, but results suffer from the different approximations used in the DFT functionals. In the case of metal halide perovskites, qualitatively different results have been reported with different functionals, either predicting vacancy or interstitial point defects to be most dominant. Here, we conduct a comprehensive comparison of a wide range of functionals for calculating the equilibrium defect formation energies and concentrations of point defects in the archetype metal halide perovskite, ${\mathrm{MAPbI}}_{3}$. We find that it is essential to include long-range van der Waals interactions in the functional, and that it is vital to self-consistently optimize structure and volume of all compounds involved in the defect formation. For calculating equilibrium formation energies of point defects in ${\mathrm{MAPbI}}_{3}$ and similar metal halide perovskites, we argue that the exact values of the chemical potentials of the species involved, or of the intrinsic Fermi level, are not important. In contrast to the simple Schottky or Frenkel pictures, we find that the dominant defects are MA and I interstitials, and Pb vacancies.

Atomistic modeling of interface strengthening in Al-Si eutectic alloys

Al-Si cast alloys are usually composed of α-Al and Al-Si eutectic. Si flakes and Al matrix generally hold cube-on-cube orientation relationship with the primary interface (111)Al∥(111)Si. Extensive experimental studies demonstrated that Si flakes cannot significantly improve mechanical properties of Al-Si cast alloys. We hypothesize that the weak strengthening effect associated with Si flakes might be attributed to thermomechanical properties of Al-Si interfaces besides their morphologies. To characterize Al-Si interfaces with a large lattice mismatch (> 30%), we proposed the quasi-coincident site lattice (Q-CSL) as reference lattice, and demonstrated that the Q-CSL Al-Si coherent interface has three characteristic coherent structures, one stable and low energy structure and two metastable and high energy structures. The translation vectors for the same type of coherent Q-CSL structures are consistent with three displacement shift complete (DSC) vectors. The two metastable structures can be obtained by shifting the low energy structure with three partial DSC vectors. Semi-coherent interface is composed of the low energy Q-CSL patches and three sets of interface misfit dislocations with Burgers vectors same as the DSC vectors. Atomistic simulations revealed that Al-Si interface exhibits low shear resistance. Ideal shear strength of the Q-CSL coherent interface is 110 MPa and semi-coherent interface is 20 MPa. The low shear resistance is attributed to the glide of interface misfit dislocations. Al-Si interface also exhibits low formation and migration energies of point defects. Owing to low shear strength and low formation and migration energies of point defects, interface sliding or shear readily happen under mechanical loading or during dislocation-interface interactions. Lattice dislocations can cross slip onto or climb along Al-Si interfaces. These reactions decrease the number of accumulated dislocation loops around Si flakes and promote nucleation and emission of lattice dislocations from Al-Si interfaces to matrix, consequently reduce the repulsive force on approaching dislocations and weaken Si flakes strengthening effect. In situ tension and compression tests in a scanning electron microscope reveal relatively weak strengthening effect due to Si flakes, consistent with the computed dislocation interaction with interfaces and shear behavior of interfaces.

Charged vacancy defects in monolayer phosphorene

Two-dimensional semiconductor phosphorene has attracted extensive research interests for potential applications in optoelectronics, spintronics, catalysis, sensors, and energy conversion. To harness phosphorene's potential requires a better understanding of how intrinsic defects control carrier concentration, character, and mobility. Using density functional theory and a charge correction scheme to account for the appropriate boundary conditions, we conduct a comprehensive study of the effect of structure on the formation energy, electronic structure, and charge transition level of the charged vacancy point defects in phosphorene. We predict that the neutral vacancy exhibits a 9-5 ring structure with a formation energy of 1.7 eV and transitions to a negatively charged state at a Fermi level 1.04 eV above the valence band maximum. The corresponding optical charge transitions display sizable Frank-Condon shifts with a large Stokes shift of 0.3 eV. Phosphorene vacancies should become negatively charged in $n$-doped phosphorene, which would passivate the dopants and reduce the charge carrier concentration and mobility.

The formation energy and interaction energy of point defects in ZrC

The formation energies of mono-vacancy and anti-site defect in ZrC have been calculated. The results are all in good agreement with experimental data and other theoretical reports. Then the formation energies of 28 transition metals (TMs) atoms substituting C or Zr atom, and locating at interstitial site have been obtained. Only Hf is energetically favourable to substitute Zr. The site preference of TMs in ZrC has also been investigated by using supercells and near neighbour Bragg Williams approximation. The formation energies of interstitial for 3d, 4d and 5d elements in ZrC indicate that all of the 28 TMs are hardly to locate the interstitial site in ZrC due to the large interstitial energies. A systematic study of interaction between the intrinsic vacancies of ZrC with TM impurity atoms has been performed by using first-principles calculations. The formation enthalpies, binding energies, electronic density of states and bond charge density for various defects and interactive configurations have been calculated. Finally, the results of site preference show that the interaction between the intrinsic defect and TM atom with CVa+TMC, CVa+TMZr, and ZrVa+TMZr configurations are almost attractive. Our results could be helpful in designing and improve the performance of ZrC alloy on demand.