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Journal ArticleDOI

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

TL;DR: In this paper, the formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides (In 2 O 3, SnO 2, and ZnO) were computed using a hybrid quantum mechanical/molecular mechanical embedded cluster approach.
Abstract: The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In 2 O 3 , SnO 2 , and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In 2 O 3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO 2 , the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In 2 O 3 , but also in SnO 2 and ZnO.
Citations
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Journal ArticleDOI
TL;DR: In this article, the authors provide a detailed account on the rational engineering of the electrodes, electrolytes and separators for improving the charge storage performance with a future perspective to achieving high energy density and long cycling stability and large-scale production for practical application.
Abstract: The growing demand for the renewable energy storage technologies stimulated the quest for efficient energy storage devices. In recent years, the rechargeable aqueous zinc-based battery technologies are emerging as a compelling alternative to the lithium-based batteries owing to safety, eco-friendliness, and cost-effectiveness. Among the zinc-based energy devices, rechargeable zinc-ion batteries (ZIBs) are drawing considerable attention. However, they are plagued with several issues, including cathode dissolution, dendrite formation, etc.. Despite several efforts in the recent past, ZIBs are still in their infant stages and have yet to reach the stage of large-scale production. Finding stable Zn2+ intercalation cathode material with high operating voltage and long cycling stability as well as dendrite-free Zn anode is the main challenge in the development of efficient zinc-ion storage devices. This Review discusses the various strategies, in terms of the engineering of cathode, anode and electrolyte, adopted for improving the charge storage performance of ZIBs and highlights the recent ZIB technological innovations. A brief account on the history of zinc-based devices and various cathode materials tested for ZIB fabrication in the last five years are also included. The main focus of this Review is to provide a detailed account on the rational engineering of the electrodes, electrolytes, and separators for improving the charge storage performance with a future perspective to achieving high energy density and long cycling stability and large-scale production for practical application.

46 citations

Journal ArticleDOI
TL;DR: In this paper, a consistent interatomic force field for indium sesquioxide (In2O3) and tin dioxide (SnO2) was derived to reproduce lattice energies and, consequently, the oxygen vacancy formation energies in the respective binary compounds.
Abstract: We present a consistent interatomic force field for indium sesquioxide (In2O3) and tin dioxide (SnO2) that has been derived to reproduce lattice energies and, consequently, the oxygen vacancy formation energies in the respective binary compounds. The new model predicts the dominance of Frenkel-type disorder in SnO2 and In2O3, in good agreement with ab initio defect calculations. The model is extended to include free electron and hole polarons, which compete with charged point defects to maintain charge neutrality in a defective crystal. The stability of electrons and instability of holes with respect to point defect formation rationalises the efficacy of n-type doping in tin doped indium oxide (ITO), a widely employed transparent conducting oxide in optoelectronic applications. We investigate the clustering of Sn substitutional and oxygen interstitial sites in ITO, finding that the dopants substitute preferentially on the cation crystallographic d site in the bixbyite unit cell, in agreement with experiment. The force field described here provides a useful avenue for the investigation of the defect properties of extended transparent conducting oxide systems, including solid solutions.

43 citations

Journal ArticleDOI
TL;DR: In this article, the nonlinear optical properties of defect-rich ZnO single crystals were studied in details within the excitation of the continuous wave (CW) and pulsed laser radiation at 532 nm (2.33

43 citations

Journal ArticleDOI
TL;DR: In this article, the authors investigate the effects of point defects on the electrical and optical properties of point-depletion devices and find that donor defects are in general more favorable than acceptor defects, except near O-rich conditions.
Abstract: Using hybrid density-functional calculations we investigate the effects of native point defects on the electrical and optical properties of ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$. We analyze formation energies, transition levels, and local lattice relaxations for all native point defects. We find that donor defects are in general more energetically favorable than acceptor defects, except near O-rich conditions, where oxygen interstitials and indium vacancies have low formation energy in $n$-type ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$. The oxygen vacancy is the lowest-energy donor defect with transition level $(2+/+)$ slightly below and $(+/0)$ slightly above the conduction-band minimum (CBM), with a predicted luminescence peak at 2.3 eV associated with the transition ${V}_{\mathrm{O}}^{0}\phantom{\rule{4pt}{0ex}}\ensuremath{\rightarrow}\phantom{\rule{4pt}{0ex}}{V}_{\mathrm{O}}^{+}$. Despite being a shallow donor, the oxygen vacancy becomes electrically inactive for Fermi levels at or higher than $\ensuremath{\sim}0.1$ eV above the CBM. This indicates that conductivity due to oxygen vacancies will saturate at rather low carrier concentrations when compared to typical carrier concentrations required for transparent conducting oxides in many device applications.

40 citations

Journal ArticleDOI
TL;DR: In this paper, the effect of point defects on the semiconducting behavior and optoelectronic response of gallium nitride has been investigated using hybrid quantum mechanical/molecular mechanical simulations.
Abstract: The semiconducting behaviour and optoelectronic response of gallium nitride is governed by point defect processes, which, despite many years of research, remain poorly understood. The key difficulty in the description of the dominant charged defects is determining a consistent position of the corresponding defect levels, which is difficult to derive using standard supercell calculations. In a complementary approach, we take advantage of the embedded cluster methodology that provides direct access to a common zero of the electrostatic potential for all point defects in all charge states. Charged defects polarise a host dielectric material with long-range forces that strongly affect the outcome of defect simulations; to account for the polarisation, we couple embedding with the hybrid quantum mechanical/molecular mechanical approach and investigate the structure, formation and ionisation energies, and equilibrium concentrations of native point defects in wurtzite GaN at a chemically accurate hybrid-densityfunctional-theory level. N vacancies are the most thermodynamically favourable native defects in GaN, which contribute to the n-type character of as-grown GaN but are not the main source, a result that is consistent with experiment. Our calculations show no native point defects can form thermodynamically stable acceptor states. GaN can be easily doped n-type, but, in equilibrium conditions at moderate temperatures acceptor dopants will be compensated by N vacancies and no significant hole concentrations will be observed, indicating non-equilibrium processes must dominate in p-type GaN. We identify spectroscopic signatures of native defects in the infrared, visible and ultraviolet luminescence ranges and complementary spectroscopies. Crucially, we calculate the effective-mass-like-state levels associated with electrons and holes bound in diffuse orbitals. These levels may be accessible in competition with more strongly-localised states in luminescence processes and allow the attribution of the observed 3.46 and 3.27eV UV peaks in a broad range of GaN samples to the presence of N vacancies.

39 citations

References
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Journal ArticleDOI
TL;DR: An efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set is presented and the application of Pulay's DIIS method to the iterative diagonalization of large matrices will be discussed.
Abstract: We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order ${\mathit{N}}_{\mathrm{atoms}}^{3}$ operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ``metric'' and a special ``preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order ${\mathit{N}}_{\mathrm{atoms}}^{2}$ scaling is found for systems containing up to 1000 electrons. If we take into account that the number of k points can be decreased linearly with the system size, the overall scaling can approach ${\mathit{N}}_{\mathrm{atoms}}$. We have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable. \textcopyright{} 1996 The American Physical Society.

81,985 citations

Journal ArticleDOI
Peter E. Blöchl1
TL;DR: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way and can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function.
Abstract: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.

61,450 citations

Journal ArticleDOI
TL;DR: In this article, a method for generating sets of special points in the Brillouin zone which provides an efficient means of integrating periodic functions of the wave vector is given, where the integration can be over the entire zone or over specified portions thereof.
Abstract: A method is given for generating sets of special points in the Brillouin zone which provides an efficient means of integrating periodic functions of the wave vector. The integration can be over the entire Brillouin zone or over specified portions thereof. This method also has applications in spectral and density-of-state calculations. The relationships to the Chadi-Cohen and Gilat-Raubenheimer methods are indicated.

51,059 citations

Journal ArticleDOI
TL;DR: A detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set is presented in this article. But this is not a comparison of our algorithm with the one presented in this paper.

47,666 citations

Journal ArticleDOI
TL;DR: In this paper, the authors present an ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local density approximation.
Abstract: We present ab initio quantum-mechanical molecular-dynamics calculations based on the calculation of the electronic ground state and of the Hellmann-Feynman forces in the local-density approximation at each molecular-dynamics step. This is possible using conjugate-gradient techniques for energy minimization, and predicting the wave functions for new ionic positions using subspace alignment. This approach avoids the instabilities inherent in quantum-mechanical molecular-dynamics calculations for metals based on the use of a fictitious Newtonian dynamics for the electronic degrees of freedom. This method gives perfect control of the adiabaticity and allows us to perform simulations over several picoseconds.

32,798 citations