Qingfeng Zeng

Phase stability, chemical bonding and mechanical properties of titanium nitrides: a first-principles study

We have performed first-principles evolutionary searches for stable Ti-N compounds and have found, in addition to the well-known rock-salt TiN, new ground states Ti3N2, Ti4N3, Ti6N5 at atmospheric pressure, and Ti2N and TiN2 at higher pressures. The latter nitrogen-rich structure contains encapsulated N2 dumbbells with a N-N distance of 1.348 Å at 60 GPa. TiN2 is predicted to be mechanically stable and quenchable. Our calculations on the mechanical properties (bulk modulus, shear modulus, Youngs modulus, Poissons ratio, and hardness) are in excellent agreement with the available experimental data. Further analyses of the electronic density of states, crystal orbital Hamilton population and the electron localization function reveal that the hardness is enhanced by strengthening directional covalent bonds and disappearance of Ti-Ti metallic bonding.

First-principles study of vibrational and dielectric properties of β-Si3N4

First-principles calculations have been conducted to study the structural, vibrational, and dielectric properties of -Si3N4. Calculations of the zone-center optical-mode frequencies including longitudinal-optical/ transverse-optical splittings , Born effective charge tensors for each atom, and dielectric constants, using density functional perturbation theory, are reported. The fully relaxed structural parameters are found to be in good agreement with experimental data. All optic modes are identified and agreement of theory with experiment is excellent. The static dielectric tensor is decomposed into contributions arising from individual infraredactive phonon modes. It is found that high-frequency modes mainly contribute to the lattice dielectric constant.

Evolutionary search for new high-k dielectric materials: methodology and applications to hafnia-based oxides

High-k dielectric materials are important as gate oxides in microelectronics and as potential dielectrics for capacitors. In order to enable computational discovery of novel high-k dielectric materials, we propose a fitness model (energy storage density) that includes the dielectric constant, bandgap, and intrinsic breakdown field. This model, used as a fitness function in conjunction with first-principles calculations and the global optimization evolutionary algorithm USPEX, efficiently leads to practically important results. We found a number of high-fitness structures of SiO2 and HfO2, some of which correspond to known phases and some of which are new. The results allow us to propose characteristics (genes) common to high-fitness structures--these are the coordination polyhedra and their degree of distortion. Our variable-composition searches in the HfO2-SiO2 system uncovered several high-fitness states. This hybrid algorithm opens up a new avenue for discovering novel high-k dielectrics with both fixed and variable compositions, and will speed up the process of materials discovery.

Prediction of stable hafnium carbides: Stoichiometries, mechanical properties, and electronic structure

Hafnium carbides are studied by a systematic search for possible stable stoichiometric compounds in the Hf-C system at ambient pressure using variable-composition ab initio evolutionary algorithm implemented in the USPEX code. In addition to well-known HfC, we predicted two additional compounds Hf3C2 and Hf6C5. The structure of Hf6C5 with space group C2/m contains 11 atoms in the primitive cell and this prediction revives the earlier proposal by A. I. Gusev. The stable structure of Hf3C2 also has space group C2/m, and is more energetically favorable than the Immm, P-3m1, P2 and C2221 structures put forward by A. I. Gusev. Dynamical and mechanical stability of the newly predicted structures have been verified by calculations of their phonons and elastic constants. The bulk and shear moduli of Hf3C2 are 195.8 GPa and 143.1 GPa, respectively, while for Hf6C5 they are 227.9 GPa and 187.2 GPa, respectively. Their mechanical properties are inferior to those of HfC due to the presence of structural vacancies. Chemical bonding, band structure, and Bader charge are presented and discussed.

Designing expert system with artificial neural networks for in situ toughened Si3N4

Abstract Artificial neural networks (ANN) were applied to develop an in situ toughened Si3N4 expert design system in this paper. Mainly depending on experiments and tests, traditional research in materials science is costly and time-consuming. ANN belongs to a new kind of artificial intelligence technique, which can surmount difficulties in data analysis and model development, so it is suitable for non-linear and unstructured information processing in materials research. Four ANN models were developed to reciprocally predict the microstructure, sintering processing and mechanical properties of this material. Software with user-friendly graphical interface was developed with matlab language, which can help to easily and quickly realize the applications mentioned above.

Evaluation of the Thermodynamic Data of CH3SiCl3 Based on Quantum Chemistry Calculations

CH3SiCl3 (methyltrichlorosilane) (MTS) is one of the most important precursors for manufacturing both an oxidation resistant SiC coating and a functional SiC film by chemical vapor deposition (CVD). In order to analyze the decomposition products of MTS with a thermodynamic calculation, correct thermodynamic data must be obtained from the authoritative data sources. G3(MP2) has been applied to evaluate the thermodynamic data of MTS(gas). The calculated value of the Gibbs energy of formation, ΔfGm0(298.15K)=−490.13kJ∙mol−1, compares with a value, ΔfGm0(298.15K)=−468.02kJ∙mol−1 from the 4th edition of the NIST-JANAF Thermochemical Tables. Further analyses have been conducted: (1) by using G3, G3//B3LYP, and G3(MP2)//B3LYP theories; (2) by using variable scale factors for G3(MP2) theory; and (3) by investigating the accuracy of both experimental and calculated thermodynamic data. The calculated values can provide ΔfGm0 values for MTS above 1500K. The final fitted equation for MTS(gas) is: ΔfGm0=7.5763×10−6T2+...

REACTION THERMODYNAMICS IN CHEMICAL VAPOR DEPOSITION OF BORON CARBIDES WITH BCl3–C3H6 (PROPENE)-H2 PRECURSORS

The gas phase reaction thermodynamics in the chemical vapor deposition (CVD) process of preparing boron carbides via the precursors of BCl3–C3H6(propene)–H2 is investigated with a set of 325 gaseous species, in which the data for 135 species are evaluated in this work. The thermochemistry data are calculated with accurate model chemistry at G3(MP2) and G3//B3LYP levels. The concentration distribution of all of the 325 species is obtained with the principle of chemical equilibrium. The thermochemistry data include the heat capacities, entropies, enthalpies of formation, and Gibbs free energies of formation. The heat capacities and entropies at temperatures in 298.15–2000 K are evaluated with the standard statistical thermodynamics. The Gibbs free energies of formation in 298.15–2000 K are calculated with the classical thermodynamics based on the developed heat capacities and entropies. By including the crystal B4C, C(graphite), and B, the results for an example of the 3:1:2 precursors of BCl3:C3H6:H2 show that the crystal B4C can be produced at temperatures higher than 700 K while the graphite has a higher molar value and can be produced at lower temperatures. It is also examined that the production of graphite can be controlled by changing the ratio of the injected reactants or pressure. It is interesting that BHCl2, BCH3Cl2, BH2Cl, and B2Cl4 are found to be the most effective species in the CVD process, which is similar to those in the BCl3–CH4–H2 system. The results predicted in this work are consistent with the experiments.

Diverse Chemistry of Stable Hydronitrogens, and Implications for Planetary and Materials Sciences

Nitrogen hydrides, e.g., ammonia (NH3), hydrazine (N2H4) and hydrazoic acid (HN3), are compounds of great fundamental and applied importance. Their high-pressure behavior is important because of their abundance in giant planets and because of the hopes of discovering high-energy-density materials. Here, we have performed a systematic investigation on the structural stability of N-H system in a pressure range up to 800 GPa through evolutionary structure prediction. Surprisingly, we found that high pressure stabilizes a series of previously unreported compounds with peculiar structural and electronic properties, such as the N4H, N3H, N2H and NH phases composed of nitrogen backbones, the N9H4 phase containing two-dimensional metallic nitrogen planes and novel N8H, NH2, N3H7, NH4 and NH5 molecular phases. Another surprise is that NH3 becomes thermodynamically unstable above ~460 GPa. We found that high-pressure chemistry of hydronitrogens is much more diverse than hydrocarbon chemistry at normal conditions, leading to expectations that N-H-O and N-H-O-S systems under pressure are likely to possess richer chemistry than the known organic chemistry. This, in turn, opens a possibility of nitrogen-based life at high pressure. The predicted phase diagram of the N-H system also provides a reference for synthesis of high-energy-density materials.

Reaction Pathways of Propene Pyrolysis

The gas‐phase reaction pathways in preparing pyrolytic carbon with propene pyrolysis have been investigated in detail with a total number of 110 transition states and 50 intermediates. The structure of the species was determined with density functional theory at B3PW91/6‐311G(d,p) level. The transition states and their linked intermediates were confirmed with frequency and the intrinsic reaction coordinates analyses. The elementary reactions were explored in the pathways of both direct and the radical attacking decompositions. The energy barriers and the reaction energies were determined with accurate model chemistry method at G3(MP2) level after an examination of the nondynamic electronic correlations. The heat capacities and entropies were obtained with statistical thermodynamics. The Gibbs free energies at 298.15 K for all the reaction steps were reported. Those at any temperature can be developed with classical thermodynamics by using the fitted (as a function of temperature) heat capacities. It was found that the most favorable paths are mainly in the radical attacking chain reactions. The chain was proposed with 26 reaction steps including two steps of the initialization of the chain to produce H and CH3 radicals. For a typical temperature (1200 K) adopted in the experiments, the highest energy barriers were found in the production of C3 to be 203.4 and 193.7 kJ/mol. The highest energy barriers for the production of C2 and C were found 174.1 and 181.4 kJ/mol, respectively. These results are comparable with the most recent experimental observation of the apparent activation energy 201.9 ± 0.6 or 137 ± 25 kJ/mol.

Pressure-driven formation and stabilization of superconductive chromium hydrides

Chromium hydride is a prototype stoichiometric transition metal hydride. The phase diagram of Cr-H system at high pressures remains largely unexplored due to the challenges in dealing with the high activation barriers and complications in handing hydrogen under pressure. We have performed an extensive structural study on Cr-H system at pressure range 0 ∼ 300 GPa using an unbiased structure prediction method based on evolutionary algorithm. Upon compression, a number of hydrides are predicted to become stable in the excess hydrogen environment and these have compositions of Cr2Hn (n = 2–4, 6, 8, 16). Cr2H3, CrH2 and Cr2H5 structures are versions of the perfect anti-NiAs-type CrH with ordered tetrahedral interstitial sites filled by H atoms. CrH3 and CrH4 exhibit host-guest structural characteristics. In CrH8, H2 units are also identified. Our study unravels that CrH is a superconductor at atmospheric pressure with an estimated transition temperature (T c) of 10.6 K, and superconductivity in CrH3 is enhanced by the metallic hydrogen sublattice with T c of 37.1 K at 81 GPa, very similar to the extensively studied MgB2.