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Title: Exciton photoluminescence and benign defect complex formation in zinc tin nitride

Emerging photovoltaic materials need to prove their viability by demonstrating excellent electronic properties. In ternary and multinary semiconductors, disorder and off-stoichiometry often cause defects that limit the potential for high-efficiency solar cells. We report on Zn-rich ZnSnN 2 (Zn/(Zn + Sn) = 0.67) photoluminescence, high-resolution X-ray diffraction, and electronic structure calculations based on Monte-Carlo structural models. The mutual compensation of Zn excess and O incorporation affords a desirable reduction of the otherwise degenerate n-type doping, but also leads to a strongly off-stoichiometric and disordered atomic structure. It is therefore remarkable that we observe only near-edge photoluminescence from well-resolved excitons and shallow donors and acceptors. Based on first principles calculations, this result is explained by the mutual passivation of Zn Sn and O N defects that renders both electronically benign. The calculated bandgaps range between 1.4 and 1.8 eV, depending on the degree of non-equilibrium disorder. The experimentally determined value of 1.5 eV in post-deposition annealed samples falls within this interval, indicating that further bandgap engineering by disorder control should be feasible via appropriate annealing protocols.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [1] ;  [2] ; ORCiD logo [4] ;  [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Colorado School of Mines, Golden, CO (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States). Applied Energy Programs
Publication Date:
Report Number(s):
NREL/JA-5J00-71244
Journal ID: ISSN 2051-6347; MHAOAL
Grant/Contract Number:
30302; AC02-76SF00515; AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Materials Horizons
Additional Journal Information:
Journal Volume: 5; Journal Issue: 5; Journal ID: ISSN 2051-6347
Publisher:
Royal Society of Chemistry
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Solar Energy Technologies Office (EE-4S); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1476311

Fioretti, Angela N., Pan, Jie, Ortiz, Brenden R., Melamed, Celeste L., Dippo, Patricia C., Schelhas, Laura T., Perkins, John D., Kuciauskas, Darius, Lany, Stephan, Zakutayev, Andriy, Toberer, Eric S., and Tamboli, Adele C.. Exciton photoluminescence and benign defect complex formation in zinc tin nitride. United States: N. p., Web. doi:10.1039/c8mh00415c.
Fioretti, Angela N., Pan, Jie, Ortiz, Brenden R., Melamed, Celeste L., Dippo, Patricia C., Schelhas, Laura T., Perkins, John D., Kuciauskas, Darius, Lany, Stephan, Zakutayev, Andriy, Toberer, Eric S., & Tamboli, Adele C.. Exciton photoluminescence and benign defect complex formation in zinc tin nitride. United States. doi:10.1039/c8mh00415c.
Fioretti, Angela N., Pan, Jie, Ortiz, Brenden R., Melamed, Celeste L., Dippo, Patricia C., Schelhas, Laura T., Perkins, John D., Kuciauskas, Darius, Lany, Stephan, Zakutayev, Andriy, Toberer, Eric S., and Tamboli, Adele C.. 2018. "Exciton photoluminescence and benign defect complex formation in zinc tin nitride". United States. doi:10.1039/c8mh00415c.
@article{osti_1476311,
title = {Exciton photoluminescence and benign defect complex formation in zinc tin nitride},
author = {Fioretti, Angela N. and Pan, Jie and Ortiz, Brenden R. and Melamed, Celeste L. and Dippo, Patricia C. and Schelhas, Laura T. and Perkins, John D. and Kuciauskas, Darius and Lany, Stephan and Zakutayev, Andriy and Toberer, Eric S. and Tamboli, Adele C.},
abstractNote = {Emerging photovoltaic materials need to prove their viability by demonstrating excellent electronic properties. In ternary and multinary semiconductors, disorder and off-stoichiometry often cause defects that limit the potential for high-efficiency solar cells. We report on Zn-rich ZnSnN2 (Zn/(Zn + Sn) = 0.67) photoluminescence, high-resolution X-ray diffraction, and electronic structure calculations based on Monte-Carlo structural models. The mutual compensation of Zn excess and O incorporation affords a desirable reduction of the otherwise degenerate n-type doping, but also leads to a strongly off-stoichiometric and disordered atomic structure. It is therefore remarkable that we observe only near-edge photoluminescence from well-resolved excitons and shallow donors and acceptors. Based on first principles calculations, this result is explained by the mutual passivation of ZnSn and ON defects that renders both electronically benign. The calculated bandgaps range between 1.4 and 1.8 eV, depending on the degree of non-equilibrium disorder. The experimentally determined value of 1.5 eV in post-deposition annealed samples falls within this interval, indicating that further bandgap engineering by disorder control should be feasible via appropriate annealing protocols.},
doi = {10.1039/c8mh00415c},
journal = {Materials Horizons},
number = 5,
volume = 5,
place = {United States},
year = {2018},
month = {6}
}

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