First-Principles Studies of the Electronic and Optical Properties of Zinc Titanium Nitride: The Role of Cation Disorder

Cation disorder is an established feature of heterovalent ternary nitrides, a promising class of semiconductor materials. A recently synthesized wurtzite-family ternary nitride, ZnTiN2, shows potential for durable photoelectrochemical applications with a measured optical absorption onset of 2 eV, which is 1.4 eV lower than previously predicted, a large difference attributed to cation disorder. Here, we use first-principles calculations based on density functional theory to establish the role of cation disorder in the electronic and optical properties of ZnTiN2. We compute antisite defect arrangement formation energies for one hundred 128-atom supercells and analyze their trends and their effect on electronic structures, rationalizing experimental results. We demonstrate that charge imbalance created by antisite defects in Ti and N local environments, respectively, broadens the conduction and valence bands near the band edges, reducing the band gap relative to the cation-ordered limit, a general mechanism relevant to other multivalent ternary nitrides. Charge-imbalanced antisite defect arrangements that lead to N-centered tetrahedral motifs fully coordinated by Zn are the most energetically costly and introduce localized in-gap states; cation arrangements that better preserve local charge balance have smaller formation energies and have less impact on the electronic structure. Our work provides insights into the nature of cation disorder in the newly synthesized semiconductor ZnTiN2, with implications for its performance in energy applications, and provides a baseline for the future study of controlling cation order in ZnTiN2 and other ternary nitrides

Coalescence of GaP on V‑Groove Si Substrates

Here, we study the morphology and dislocation dynamics of metalorganic vapor phase epitaxy (MOVPE)-grown GaP on a V-groove Si substrate. We show that Si from the substrate stabilizes the (0 0 1) GaP facet, which is critical for achieving coalescence. The SiNx caps covering the (0 0 1) tops of the V-grooves must be sufficiently small for the 3 × 1 GaP surface reconstruction caused by Si to continue to influence the GaP coalescence while the V-grooved sidewalls are covered. If the SiNx caps are too large, (1 1 1) diamond faceting develops in the GaP, and coalescence does not occur. On samples where coalescence is successful, we measure a root-mean-square roughness of 0.2 nm and a threading dislocation density of 5 × 107 cm–2. Dislocation glide was found to begin during coalescence through transmission electron microscopy. With further TDD reduction, these GaP on V-groove templates will be suitable for III-V optoelectronic device growth

Nucleation and Growth of GaAs on a Carbon Release Layer by Halide Vapor Phase Epitaxy

We couple halide vapor phase epitaxy (HVPE) growth of III–V materials with liftoff from an ultrathin carbon release layer to address two significant cost components in III–V device - epitaxial growth and substrate reusability. We investigate nucleation and growth of GaAs layers by HVPE on a thin amorphous carbon layer that can be mechanically exfoliated, leaving the substrate available for reuse. We study nucleation as a function of carbon layer thickness and growth rate and find island-like nucleation. We then study various GaAs growth conditions, including V/III ratio, growth temperature, and growth rate in an effort to minimize film roughness. High growth rates and thicker films lead to drastically smoother surfaces with reduced threading dislocation density. Finally, we grow an initial photovoltaic device on a carbon release layer that has an efficiency of 7.2%. The findings of this work show that HVPE growth is compatible with a carbon release layer and presents a path toward lowering the cost of photovoltaics with high throughput growth and substrate reuse

Synthesis and Calculations of Wurtzite Al_1–<i>x</i>Gd_<i>x</i>N Heterostructural Alloys

Al1–xGdxN is one of a series of novel heterostructural alloys involving rare earth cations with potentially interesting properties for (opto)­electronic, magnetic, and neutron detector applications. Using alloy models in conjunction with density functional theory, we explored the full composition range for Al1–xGdxN and found that wurtzite is the ground-state structure up to a critical composition of xc = 0.82. The calculated temperature-composition phase diagram reveals a large miscibility gap inducing spinodal decomposition at equilibrium conditions, with higher Gd substitution (meta)­stabilized at higher temperatures. By depositing combinatorial thin films at high effective temperatures using radio-frequency cosputtering, we have achieved the highest Gd3+ incorporation into the wurtzite phase reported to date, with single-phase compositions at least up to x ≈ 0.25 confirmed by high-resolution synchrotron grazing incidence wide-angle X-ray scattering. High-resolution transmission electron microscopy on material with x ≈ 0.13 and x ≈ 0.24 confirmed a uniform composition polycrystalline film with uniform columnar grains having the wurtzite structure. Spectroscopic ellipsometry and cathodoluminescence spectroscopy measurements are employed to probe the optoelectronic properties, showing that the band gap decreases with increasing Gd content x and that this effect causes the ideal Gd substitution level for cathodoluminescence applications to be low. Expanding our calculations to other rare earth cations (Pr3+ and Tb3+) reveals similar thermodynamic stability and solubility behavior to Gd. From this and previous studies on Al1–xScxN, we elucidate that both smaller ionic radius and higher bond ionicity promote increased incorporation of group IIIB cations into wurtzite AlN. This work furthers the development of design rules for new alloys in this material family

Combinatorial Synthesis of Cation-Disordered Manganese Tin Nitride MnSnN₂ Thin Films with Magnetic and Semiconducting Properties

Magnetic semiconductors may soon improve the energy efficiency of microelectronics, but materials exhibiting these dual properties remain underexplored. Here, we report the computational prediction and realization of a new magnetic and semiconducting material, MnSnN2, via combinatorial sputtering of thin films. Grazing incidence wide-angle X-ray scattering and laboratory X-ray diffraction studies show MnSnN2 exhibits a wurtzite-like crystal structure with cation disorder. This new material has a wide composition tolerance, with a single-phase region ranging from 20% < Mn/(Mn + Sn) < 65%. Spectroscopic ellipsometry identifies an optical absorption onset of 1 eV, consistent with the computationally predicted 1.2 eV bandgap. Resistivity measurements as a function of temperature support the semiconducting nature of MnSnN2. Hall effect measurements show carrier density has a weak inverse correlation with temperature, indicating that the charge transport mechanisms are more complex than in a pristine semiconductor. Magnetic susceptibility measurements reveal a low-temperature magnetic ordering transition (≈10 K) for MnSnN2 and strong antiferromagnetic correlations. This finding contrasts with bulk, cation-ordered MnSiN2 and MnGeN2, which exhibited antiferromagnetic ordering above 400 K in previous studies. To probe the origin of this difference, we perform Monte Carlo simulations of cation-ordered and cation-disordered MnSnN2. They reveal that cation disorder lowers the magnetic transition temperature relative to the ordered phase. In addition to discovering a new compound, this work shows that future efforts could use cation (dis)order to tune magnetic transitions in semiconducting materials for precise control of properties in microelectronics

Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications

Photoelectrochemical fuel generation is a promising route to sustainable liquid fuels produced from water and captured carbon dioxide with sunlight as the energy input. Development of these technologies requires photoelectrode materials that are both photocatalytically active and operationally stable in harsh oxidative and/or reductive electrochemical environments. Such photocatalysts can be discovered based on co-design principles, wherein design for stability is based on the propensity for the photocatalyst to self-passivate under operating conditions and design for photoactivity is based on the ability to integrate the photocatalyst with established semiconductor substrates. Here, we report on the synthesis and characterization of zinc titanium nitride (ZnTiN2) that follows these design rules by having a wurtzite-derived crystal structure and showing self-passivating surface oxides created by electrochemical polarization. The sputtered ZnTiN2 thin films have optical absorption onsets below 2 eV and n-type electrical conduction of 3 S/cm. The band gap of this material is reduced from the 3.36 eV theoretical value by cation-site disorder, and the impact of cation antisites on the band structure of ZnTiN2 is explored using density functional theory. Under electrochemical polarization, the ZnTiN2 surfaces have TiO2- or ZnO-like character, consistent with Materials Project Pourbaix calculations predicting the formation of stable solid phases under near-neutral pH. These results show that ZnTiN2 is a promising candidate for photoelectrochemical liquid fuel generation and demonstrate a new materials design approach to other photoelectrodes with self-passivating native operational surface chemistry