skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Growth of ordered and disordered ZnSnN 2

Abstract

A series of ZnSnN2 films has been grown by plasma assisted molecular beam epitaxy in order to investigate the possibility of controlled cation sublattice disorder as well as its effects on physical and electronic properties of the material. By varying the growth conditions, specifically either the metal to nitrogen flux ratio or the substrate temperature, the authors have confirmed the existence of both the hexagonal and orthorhombic phases of the material via synchrotron x-ray diffraction and in situ reflection high energy electron diffraction measurements. Here, the authors report the results of an initial mapping and analysis of the growth parameter space, as part of continuing efforts to improve material quality.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1355050
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Vacuum Science and Technology. B, Nanotechnology and Microelectronics; Journal Volume: 35; Journal Issue: 2
Country of Publication:
United States
Language:
ENGLISH
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Makin, Robert Allen, Senabulya, Nancy, Mathis, James, Feldberg, N., Miska, P., Clarke, Roy, and Durbin, Steven M.. Growth of ordered and disordered ZnSnN 2. United States: N. p., 2017. Web. doi:10.1116/1.4978021.
Makin, Robert Allen, Senabulya, Nancy, Mathis, James, Feldberg, N., Miska, P., Clarke, Roy, & Durbin, Steven M.. Growth of ordered and disordered ZnSnN 2. United States. doi:10.1116/1.4978021.
Makin, Robert Allen, Senabulya, Nancy, Mathis, James, Feldberg, N., Miska, P., Clarke, Roy, and Durbin, Steven M.. Tue . "Growth of ordered and disordered ZnSnN 2". United States. doi:10.1116/1.4978021.
@article{osti_1355050,
title = {Growth of ordered and disordered ZnSnN 2},
author = {Makin, Robert Allen and Senabulya, Nancy and Mathis, James and Feldberg, N. and Miska, P. and Clarke, Roy and Durbin, Steven M.},
abstractNote = {A series of ZnSnN2 films has been grown by plasma assisted molecular beam epitaxy in order to investigate the possibility of controlled cation sublattice disorder as well as its effects on physical and electronic properties of the material. By varying the growth conditions, specifically either the metal to nitrogen flux ratio or the substrate temperature, the authors have confirmed the existence of both the hexagonal and orthorhombic phases of the material via synchrotron x-ray diffraction and in situ reflection high energy electron diffraction measurements. Here, the authors report the results of an initial mapping and analysis of the growth parameter space, as part of continuing efforts to improve material quality.},
doi = {10.1116/1.4978021},
journal = {Journal of Vacuum Science and Technology. B, Nanotechnology and Microelectronics},
number = 2,
volume = 35,
place = {United States},
year = {Tue Mar 21 00:00:00 EDT 2017},
month = {Tue Mar 21 00:00:00 EDT 2017}
}
  • We examine ZnSnN{sub 2}, a member of the class of materials contemporarily termed “earth-abundant element semiconductors,” with an emphasis on evaluating its suitability for photovoltaic applications. It is predicted to crystallize in an orthorhombic lattice with an energy gap of 2 eV. Instead, using molecular beam epitaxy to deposit high-purity, single crystal as well as highly textured polycrystalline thin films, only a monoclinic structure is observed experimentally. Far from being detrimental, we demonstrate that the cation sublattice disorder which inhibits the orthorhombic lattice has a profound effect on the energy gap, obviating the need for alloying to match the solarmore » spectrum.« less
  • ZnSnN{sub 2} is regarded as a promising photovoltaic absorber candidate due to earth-abundance, non-toxicity, and high absorption coefficient. However, it is still a great challenge to synthesize ZnSnN{sub 2} films with a low electron concentration, in order to promote the applications of ZnSnN{sub 2} as the core active layer in optoelectronic devices. In this work, polycrystalline and high resistance ZnSnN{sub 2} films were fabricated by magnetron sputtering technique, then semiconducting films were achieved after post-annealing, and finally Si/ZnSnN{sub 2} p-n junctions were constructed. The electron concentration and Hall mobility were enhanced from 2.77 × 10{sup 17} to 6.78 × 10{sup 17 }cm{sup −3} and frommore » 0.37 to 2.07 cm{sup 2} V{sup −1} s{sup −1}, corresponding to the annealing temperature from 200 to 350 °C. After annealing at 300 °C, the p-n junction exhibited the optimum rectifying characteristics, with a forward-to-reverse ratio over 10{sup 3}. The achievement of this ZnSnN{sub 2}-based p-n junction makes an opening step forward to realize the practical application of the ZnSnN{sub 2} material. In addition, the nonideal behaviors of the p-n junctions under both positive and negative voltages are discussed, in hope of suggesting some ideas to further improve the rectifying characteristics.« less
  • Na-ion batteries are appealing alternatives to Li-ion battery systems for large-scale energy storage applications in which elemental cost and abundance are important. Although it is difficult to find Na-ion batteries which achieve substantial specific capacities at voltages above 3 V (vs Na⁺/Na), the honeycomb-layered compound Na(Ni 2/3Sb 1/3)O₂ can deliver up to 130 mAh/g of capacity at voltages above 3 V with this capacity concentrated in plateaus at 3.27 and 3.64 V. Comprehensive crystallographic studies have been carried out in order to understand the role of disorder in this system which can be prepared in both “disordered” and “ordered” forms,more » depending on the synthesis conditions. The average structure of Na(Ni 2/3Sb 1/3)O₂ is always found to adopt an O3-type stacking sequence, though different structures for the disordered (R3¯ m, #166, a = b = 3.06253(3) Å and c = 16.05192(7) Å) and ordered variants ( C2/m, #12, a = 5.30458(1) Å, b = 9.18432(1) Å, c = 5.62742(1) Å and β = 108.2797(2)°) are demonstrated through the combined Rietveld refinement of synchrotron X-ray and time-of-flight neutron powder diffraction data. However, pair distribution function studies find that the local structure of disordered Na(Ni 2/3Sb 1/3)O₂ is more correctly described using the honeycomb-ordered structural model, and solid state NMR studies confirm that the well-developed honeycomb ordering of Ni and Sb cations within the transition metal layers is indistinguishable from that of the ordered phase. The disorder is instead found to mainly occur perpendicular to the honeycomb layers with an observed coherence length of not much more than 1 nm seen in electron diffraction studies. When the Na environment is probed through ²³Na solid state NMR, no evidence is found for prismatic Na environments, and a bulk diffraction analysis finds no evidence of conventional stacking faults. The lack of long range coherence is instead attributed to disorder among the three possible choices for distributing Ni and Sb cations into a honeycomb lattice in each transition metal layer. It is observed that the full theoretical discharge capacity expected for a Ni³⁺/²⁺ redox couple (133 mAh/g) can be achieved for the ordered variant but not for the disordered variant (~110 mAh/g). The first 3.27 V plateau during charging is found to be associated with a two-phase O3 ↔ P3 structural transition, with the P3 stacking sequence persisting throughout all further stages of desodiation.« less