Combinatorial investigation of structural and optical properties of cation-disordered ZnGeN<sub>2</sub>

Melamed, Celeste L.; Pan, Jie; Mis, Allison; Heinselman, Karen N.; Schnepf, Rekha R.; Woods‐Robinson, Rachel; Cordell, Jacob J.; Lany, Stephan; Toberer, Eric S.; Tamboli, Adele C.

doi:10.1039/d0tc01675f

Cited by 31 publications

(45 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For all compositions, a drop in the reflection-corrected transmission (Fig. 6a) is observed near 2 eV, as expected from a mid-gap semiconductor similar to other II-IV-N2 materials 32,47 and in agreement with prior Heyd-Scuseria-Ernzerhof (HSE) calculations. Conversion to absorptivity (Fig.…”

Section: Optoelectronic Properties Of Cation-disordered Zntin2supporting

confidence: 87%

“…Examples of the experimentally synthesized wurtzite materials in this family include Zn2VN3, 34 MgSnN2, 35,36 Zn2NbN3, 37 Zn3MoN4, 38 Zn2SbN3, 39 Mg2SbN3, 40 Mg2PN3 and Zn2PN3, 41,42 among others. For several well-studied materials in this family, such as wurtzite ZnSnN2 43,44 and ZnGeN2 [45][46][47] as well as rocksalt Mg2NbN3 48 and MgZrN2, [49][50][51] elemental disorder on cation sublattice of the parent structure has been shown to influence both band gap and transport properties, 45,52 although this phenomenon has not been studied across the broader class. [52][53][54] However, none of the above multivalent ternary nitrides have been considered for PEC applications, with research in this space limited to wurtzite oxynitride alloys such as ZnGeN2-ZnO 55 or ZnSnN2-ZnO, 56 despite the potential for integration with GaN (or other III-N), 57,58 and many other theoretical predictions have never been synthesized so their experimental properties remain unknown.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Greenaway

Culman

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

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 such 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 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 0.1 S/cm. The band gap of this material is reduced from the 3.5 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.

show abstract

Section: Optoelectronic Properties Of Cation-disordered Zntin2supporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Greenaway

Culman

et al. 2022

Preprint

Self Cite

View full text Add to dashboard Cite

show abstract

“…However, recent studies have found cation stoichiometry to greatly impact optical behavior; growing Ge-rich films shifts the optical absorption onset to higher energy. 86 In ZnSnN 2 , Zn-rich stoichiometries have been shown to improve electronic properties by lowering carrier concentration and increasing mobility. 87 This tendency for II− IV−N 2 compounds to exhibit crystallinity at off-stoichiometric cation compositions is likely due to the favorability of antisite defects and vacancies in these materials.…”

mentioning

confidence: 99%

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

et al. 2020

Self Cite

View full text Add to dashboard Cite

Controlling site disorder in ternary and multinary compounds enables tuning optical and electronic properties at fixed lattice constants and stoichiometries, moving beyond many of the challenges facing binary alloy systems. Here, we consider possible enhancements to energy-related applications through the integration of disorder-tunable materials in devices such as light-emitting diodes, photonics, photovoltaics, photocatalytic materials, batteries, and thermoelectrics. However, challenges remain in controlling and characterizing disorder. Focusing primarily on II–IV–V2 materials, we identify three metrics for experimentally characterizing cation site disorder. Complementary to these experiments, we discuss simulation methods to understand disordered materials. Nonidealities, such as off-stoichiometry and oxygen incorporation, can occur while synthesizing metastable disordered materials. While nonidealities may seem undesirable, we describe how if harnessed they could provide another knob for tuning disorder and subsequently properties. To illustrate the effects of disorder on device-relevant properties, we provide case examples of disordered materials and their potential in device applications.

show abstract

“…This can conflict with the need to deposit many ternary nitrides at low temperature, driven by the desorption of high vapor pressure elemental sources (e.g., Zn and alkali or alkaline earth metals) (46,146). Zn-containing compounds such as ZnGeN 2 , ZnSnN 2 , and CaZn 2 N 2 must be deposited below 500 • C in order to prevent Zn desorption (17,65,72,88,147). Higher temperatures would be beneficial to improve film morphology and crystallinity, and to reduce defect concentrations.…”

Section: Physical Vapor Depositionmentioning

confidence: 99%

Ternary Nitride Materials: Fundamentals and Emerging Device Applications

Greenaway,

Melamed,

Tellekamp

et al. 2020

Preprint

Self Cite

View full text Add to dashboard Cite

Interest in inorganic ternary nitride materials has grown rapidly over the past few decades, as their diversity of chemistries and structures make them appealing for a variety of applications. Due to synthetic challenges posed by the stability of N 2 , the number of predicted nitride compounds dwarfs those that have been synthesized, offering a breadth of opportunity for exploration. This review summarizes the fundamental properties and structural chemistry of ternary nitrides, leveraging metastability and the impact of nitrogen chemical potential. A discussion of prevalent defects, both detrimental and beneficial, is followed by a survey of synthesis techniques and their interplay with metastability. Throughout the review, we highlight applications (such as solid-state lighting, electrochemical energy storage, and electronic devices) in which ternary nitrides show particular promise.

show abstract

Combinatorial investigation of structural and optical properties of cation-disordered ZnGeN₂

Abstract:
Cation-disordered ZnGeN₂ is found to exhibit structural and optical tunability with cation off-stoichiometry.

Cited by 31 publications

References 57 publications

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

Ternary Nitride Materials: Fundamentals and Emerging Device Applications

Contact Info

Product

Resources

About

Combinatorial investigation of structural and optical properties of cation-disordered ZnGeN2

Abstract: Cation-disordered ZnGeN2 is found to exhibit structural and optical tunability with cation off-stoichiometry.

Cited by 31 publications

References 57 publications

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Co-design of zinc titantium nitride semiconductor towards durable photoelectrochemical applications

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

Ternary Nitride Materials: Fundamentals and Emerging Device Applications

Contact Info

Product

Resources

About

Combinatorial investigation of structural and optical properties of cation-disordered ZnGeN₂

Abstract:
Cation-disordered ZnGeN₂ is found to exhibit structural and optical tunability with cation off-stoichiometry.