# DFT modelling of the edge dislocation in 4H-SiC

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## Abstract

We have presented ab initio study, based on density functional theory methods, of full-core edge dislocation impact on basic properties of 4H-SiC semiconductor. To enable calculations in periodic boundary conditions, we have proposed geometry with two dislocations with opposite Burgers vectors. For this geometry, which determines the distance between dislocations, we have estimated the creation energy per unit length of a single-edge dislocation. The radial distribution function has been used to assess the effect of the dislocations on the local crystal structure. The analysis of the electronic structure reveals mid-gap *p* states induced by broken atomic bonds in the dislocation core. The maps of charge distribution and electrostatic potential have been calculated, and the significant decrease in the electrostatic barriers in the vicinity of the dislocation cores has been quantified. The obtained results have been discussed in the light of previous findings and calculations based mainly on phenomenological models.

## Introduction

The silicon carbide (SiC), a wide band gap semiconductor, is a promising material for high-voltage and high-frequency nanoelectronic devices [1, 2]. Very good operational quality of SiC results from high values of breakdown voltage (\(\approx 10^6\, \hbox {V/cm}\)), high charge carrier mobility, high temperature stability and high thermal conductivity [3]. Additionally, this material has very good mechanical properties and resistance to radiation damage. Unfortunately, the electronic properties of epitaxial layers strongly depend on the material’s quality. The presence of intrinsic defects and impurities which arise during crystal growth process substantially limit applications of SiC.

Dislocations are the main crystal defects in SiC. They deteriorate the performance of high electric field devices such as Shottky and *p*–*n* diodes [4, 5]. Two typical components of dislocations with the direction along \([0\,0\,0\,1]\) are the screw and edge dislocations with Burgers vectors \([0\,0\,0\,1]\) and \(\frac{1}{3}[\bar{2}\,1\,1\,0]\), respectively. The standard density of dislocations observed in the good quality 4H-SiC epilayers reaches \(10^{3}\, \hbox {cm}^{-2}\) [6]. In the last decade, different dislocation formation mechanisms were examined [7] and impact on important properties was studied. The electrical characteristics of 4H-SiC photodiodes reveal that the screw and edge dislocations reduce the breakdown voltage by \(3.5\%\) and \(2\%\), respectively, and increase the leakage currents compared to systems without crystal defects [8]. Dislocations also influence transport properties of 4H-SiC by increasing recombination activity [9] and reducing the diffusion length in the material [10].

Various mechanisms are responsible for modifications of electronic structure in the presence of dislocations. In the dislocation core, the broken bonds give rise to acceptor levels within the band gap and make this region electrically active [11, 12]. Dislocations also act as trapping centres and sources for point defects [13]. In the vicinity of the core, the strain field may induce additional states located near the conduction band edge [14]. In epitaxially grown SiC, several gap levels have been detected using the deep-level transient spectroscopy (DLTS) and their connection with the intrinsic defects have been analysed [15, 16].

The structural properties of dislocations have been previously studied theoretically in very few materials using both empirical potentials [17] and ab initio methods based on the density functional theory (DFT) [18, 19, 20, 21]. The DFT provides tools that allow one to study changes in electronic structure induced by dislocations [22]. Such computations revealed that the dislocation core in GaN induces deep-gap states [23, 24], which influence strongly the electronic and optical properties of this semiconductor [25]. The point defects such as vacancies and oxygen dopants can be easily trapped at the core of the edge dislocations providing additional mid-gap states [23, 26]. The influence of partial dislocations on the structural and electronic properties has been investigated in the pure SiC [27] and crystals doped with impurity atoms [28]. However, to our best knowledge, electronic properties of the full-edge dislocation have not been studied with ab initio methods yet.

In this work, we study the changes in the crystal structure and electronic properties of 4H-SiC induced by the edge dislocation. We analyse in detail the local lattice distortion by means of the radial distribution function (RDF)—the density of atoms in the spherical shell around given atom averaged over whole structure [29, 30, 31]. The calculations reveal significant redistribution of charges and electrostatic potential in the region of the dislocation core. The electronic states located in the insulating gap, arising from the dislocation core atoms, show a very weak dispersion in the perfect correlation with the distribution of charges in the distorted region. Estimated minimal electrostatic barriers for ideal and distorted systems throw a new light on the decrease in the breakdown voltage in the defected 4H-SiC crystal.

## Methods

All presented calculations have been executed with the Vienna Ab initio Simulation Package (VASP) [32, 33] using the full-potential projector augmented-wave method [34, 35] with the generalised-gradient approximation (GGA) to the exchange-correlation functional in the PBE form [36, 37, 38]. The following valence base configurations have been included: Si \(3s^23p^2\) and C \(2s^22p^2\). The integration over the **k**-point space has been performed over the \(2\times 2\times 2\) Monkhorst-Pack mesh [39], and the energy cut-off for the plane waves expansion was equal to 500 eV.

## Results

### Crystal structure

The pure 4H-SiC crystal structure has been reproduced correctly with the lattice constants \(a=3.095\) Å and \(c=10.132\) Å, which are very close to experimental values that amount to 3.073 Å and 10.053 Å, respectively. To fulfil the periodic boundary conditions, we consider two full-core edge dislocations with opposite Burgers vectors \(\frac{1}{3}[\bar{2}\,1\,1\,0]\) and \(\frac{1}{3}[2\,\bar{1}\,\bar{1}\,0]\), inserted into the system using VECDs package [46]. The procedure involves removal of 38 selected atoms (19 SiC molecules) changing the total number of atoms in the system. This has been taken into account in all comparisons to the ideal structure. Despite decreased atom count in the distorted structure, the relaxed crystal volume noticeably increases (by about 1%) due to the local destruction of hexagonal close-packed structure. However, since the supercell is big enough, the elongation of the average nearest neighbour bond is below 0.5% in comparison with its length in the ideal system.

*E*is the energy of the system with a pair of dislocations (346 atoms) and \(E'_0\) is the ground state energy of the undisturbed system normalised to the same number of formula units. For the relative distance between the cores equal to 6.73 Å, we have obtained \(e=2.17\,\hbox {eV}/\AA {}\) per supercell. Additionally, it has been found—in agreement with [42]—that due to attractive force between dislocations of opposite sign, they easily annihilate. Otherwise, if they repel each other, they would create a stable grid in the periodic boundary conditions, which does not happen. It proves that the Peierls energy barrier between two states of dislocation core at adjacent lattice nodes along the common glide plane is very low. Therefore, to prevent the annihilation of defects during optimisation process, we have trapped both dislocations by pinning their cores at different glide planes.

The parameters of Gaussian functions (positions and FWHM) and calculated peak areas of two-component fit of RDF presented in Fig. 2. u and d parts corresponds to the undisturbed and distorted regions, respectively

Nearest neighbour | Next nearest neighbour | |||
---|---|---|---|---|

| | | | |

Position | 1.911 | 1.896 | 3.115 | 3.121 |

Area | 0.321 | 0.387 | 0.154 | 0.560 |

FWHM | 0.034 | 0.101 | 0.024 | 0.185 |

### Band structure

Next, we analyse the influence of edge dislocations on the band structure of the 4H-SiC. The general observation is that the positions of the main bands in the electron density of states (eDOS) remain mostly unchanged (see Fig. 3). The characteristic peaks in the valence and conduction bands of the ideal structure become broadened and smeared out in the system with dislocations. The strongest changes are found inside the energy gap of the pure 4H-SiC crystal,^{1} where additional localised states appear. One can find sharp deep states delivered by atoms with broken nearest neighbours bonds and broadened shallow bands close to the top of the valence band and the bottom of the conduction band. The presence of shallow bands effectively reduces the magnitude of the insulating gap. The states located in the range \(\sim 0.2{-}0.6\, \hbox {eV}\) below the conduction band have also been found in the SiC systems with the stacking faults [47, 48, 49] and Shockley partial dislocations [27]. The latter may also induce the occupied states about 0.4 eV above the valence band. Furthermore, the defects generated by relaxations around the dislocation may also introduce defect states into the gap [49, 50, 51].

*spd*states has been modified. For the conduction band, where in the perfect 4H-SiC

*d*states dominate, as well as for the localised states inside the gap, the main contribution for distorted system stems from

*p*states.

### Electric charge distribution

The charge density is a well-defined, primary quantity in the DFT. Fig. 4a presents the charge distribution around edge dislocations. In particular, one can see the elongated structures with a very low charge density (outlined with dotted line in Fig. 4a) in the slice plane crossing both dislocation cores. On the other hand, the neighbouring atoms visible in Fig. 4a have increased density of carriers connected with broken interatomic bonds. The effect is more pronounced for the dislocation I, marked with the thick solid line in the figure. The electrostatic potential derived from the charge distribution and averaged over *c* direction is presented in the top-view projection (Fig. 4b). The decreased charge density regions exhibit lowered energy barriers which allow for easier flow of the carriers. Again, the effect is much stronger for the dislocation I with the bigger disorder around its edge. Additionally, panel (c) shows the electrostatic potential along the *c* direction in three different locations of distorted system. Its periodicity reflects ABCB stacking in the 4H-SiC structure. In agreement with the intuition, electric charges encounter the highest barriers along the atomic chain (curve P3 in Fig. 4c) and the lowest barriers through the dislocation core (curve P1 - note different vertical scales on upper an lower panels).

To quantify the influence of dislocations on the energy barriers for the electron transport along *c*-axis, we have analysed the local electrostatic potential in the crystal. We have taken into account that the path over minimal barriers does not always follow a straight line parallel to the *c* direction. Therefore, for each pair of positions: \(p_0=(x,y,z_0)\) and \(p_1=(x,y,z_1)\)—where \(z_0\) is at the bottom of the periodic unit, while \(z_1\) is at its top (see Fig. 4a)—we have derived a minimal energy path and the barrier height for this path from \(p_0\) to \(p_1\). The calculation used the basin-filling segmentation algorithm [52] with bisection search for minimal limiting energy level. The results indicate substantial lowering of the barrier in the vicinity of the dislocation cores denoted by P1 in Fig. 4b. The calculated difference between the minimal barrier height in the non-distorted area and in the vicinity of the dislocation core is 0.8 V. This value is much lower than the differences in barrier heights presented in Fig. 4c due to the nonlinear character of the minimal barrier path. The calculated energy barriers are obtained with zero voltage bias and as such are not sufficient to determine quantitatively the charge transport properties of the material but are an important step towards full understanding of charge carriers’ behaviour.

On the basis of the presented results, the following mechanism of the insulating properties weakening and the breakdown voltage decreasing in the 4H-SiC monocrystal may be proposed. In the edge dislocation core, part of interatomic bonds is broken causing the creation of deep states inside the semiconductor gap. Additionally, crystal distortions modify the atomic potential facilitating the shallow states formation and simultaneously narrowing the forbidden gap. Finally, the elongated regions of the reduced charge density with flat electrostatic potential are formed along a dislocation cores. The lack of barriers inside so-created tunnels, in connection with additional empty states in the energy gap, may enhance carrier flow through the distorted areas, significantly influencing decrease in the breakdown voltage. This scenario provides the plausible explanation of the current-voltage characteristics of the 4H-SiC avalanche photodiodes, which show a measurable decrease in the breakdown voltage and increase in leakage currents due to a single-edge dislocation [8]. Our analysis of the mid-gap levels also enables a better understanding of a pronounced impact of dislocations on the carrier lifetime [9] and diffusion length [10] and can be helpful in interpreting the DLTS measurements [15, 16]. Moreover, similarly to other strongly defected systems [53], the changes in the electronic structure may be related to observable effects in the lattice dynamical and optical properties of SiC [54].

## Conclusions

In this work, we have successfully modelled a pair of edge dislocations using ab initio methods. Our results are consistent with experimental findings concerning small but noticeable lattice constants elongation, semiconductor energy gap narrowing and electrostatic barriers reduction. Furthermore, with atomic-scale resolution, we have explained foregoing processes. We have shown that (i) the crystal structure is strongly disturbed in the small vicinity of the dislocation core, (ii) additional energy levels occurring in the energy gap belong to the atoms with broken bonds occupying the core neighbourhood, (iii) existence of spatial tunnels, with atoms delivering localised states to the band structure on its sides, significantly decreases electrostatic barriers and should be considered as one of the primary factors responsible for experimentally observed reduction in breakdown voltage.

The presented research demonstrates the possibility of modelling the extended crystal defects within the DFT approach and periodic boundary conditions. So far, most of the published results employed the models with empirical potentials, focusing on the structural or elastic properties of dislocations. The ab initio approach allows us to study the microscopic properties of the lattice and electronic degrees of freedom on an equal footing. Therefore, it was possible to identify the atoms from the distorted region of the crystal, with the largest contribution to the mid-gap electronic states. Since DFT provides the information about the charge density and potential at each point of space, we could analyse its distribution in the defected crystal and study potential barriers within the dislocation core. These results help to better understand the changes in electronic properties and transport properties induced by extended defects. Such study was performed for the first time and may have a strong impact on further research of edge dislocations and other crystal defects.

The presented work could be extended in different directions. Using larger cells would be beneficial for better understanding of size effects and the dependence of structural and electronic properties on the distance between dislocations. Increasing the supercell size will require extensive computations; however, it may provide relevant information about the interaction between dislocations, allow to determine their formation energies and in perspective explain the mechanism of micropipe creation. Another important step is to study magnetic properties of the localised states induced by the broken bonds. Such local magnetic moments, generated by vacancies, were previously studied experimentally and theoretically in the SiC crystals. The presence of dislocations also modify elastic properties of materials. The total-energy DFT method is a perfect tool to study the changes in elastic constants of defected crystals, and it will be the aim of our future research.

## Footnotes

- 1.
The theoretical gap \(E_g=2.3\) eV is smaller than the measured value (3.2 eV) due to well-known gap underestimation problem in the LDA/GGA approaches.

## Notes

### Acknowledgements

This work was partially supported by the SICMAT Project financed under the European Funds for Regional Development (Contract No. UDA-POIG.01.03.01-14-155/09).

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