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Title: Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers

Abstract

Metastable inorganic materials with unique properties are vital in many practical applications, but their synthesis is often challenging. In physics, epitaxial stabilization, also known as pseudomorphic growth, is used to synthesize metastable polymorphs, but usually only as very thin films and on expensive single-crystal substrates. In chemistry, the templated growth of inorganic solid-state materials on self-assembled monolayers of organic molecules is reported. Bridging these two fields, here, we show that the synthesis of metastable polymorphs is possible up to large film thickness on amorphous substrates covered with thin inorganic seed layers that serve as templates. The stabilization of a 500-nm-thick metastable wurtzite (WZ) MnTe film by a 5-nm-thick ZnTe seed layer sputtered on amorphous glass substrates is experimentally demonstrated. Theoretical calculations explain this experimental observation by the small WZ polymorph energy relative to that of the ground-state nickeline (NC) structure of MnTe and a large lattice constant difference of the two. The resulting metastable WZ-MnTe polymorph exhibits a wide band gap of 2.7 eV and a low hole density of 10 12cm -3, which is relevant to optoelectronic applications. These properties are in sharp contrast to those of the narrow-band-gap highly doped NC-MnTe with 1.3 eV band gap and 10more » 19cm -3 hole density. The difference in hole density is due to the calculated difference in the formation energy of manganese vacancy acceptor defects. Overall, these results suggest that templated growth on amorphous substrates with seed layers can be used to synthesize metastable polymorphs of other materials, without the need for expensive single-crystal substrates.« less

Authors:
 [1];  [2];  [3];  [4];  [3];  [2]; ORCiD logo [3];  [5];  [6];  [7]; ORCiD logo [3]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Fudan Univ., Shanghai (China); ZhengZhou Univ. (China)
  2. Univ. of Colorado, Boulder, CO (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States); Oregon State Univ., Corvallis, OR (United States)
  5. Oregon State Univ., Corvallis, OR (United States)
  6. Fudan Univ., Shanghai (China)
  7. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1598128
Report Number(s):
NREL/JA-5K00-75602
Journal ID: ISSN 2331-7019; PRAHB2
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Applied
Additional Journal Information:
Journal Volume: 13; Journal Issue: 1; Journal ID: ISSN 2331-7019
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; thin film sputtering; Hall effect measurement; metastable polymorph; wide-bandgap p-type semiconductors; first principles defect calculations; epitaxial growth; pseudomorphic stabilization

Citation Formats

Han, Yanbing, Trottier, Ryan, Siol, Sebastian, Matthews, Bethany, Young, Matthew R., Musgrave, Charles B., Lany, Stephan, Tate, Janet, Zhang, Qun, Holder, Aaron M, and Zakutayev, Andriy. Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers. United States: N. p., 2020. Web. doi:10.1103/PhysRevApplied.13.014012.
Han, Yanbing, Trottier, Ryan, Siol, Sebastian, Matthews, Bethany, Young, Matthew R., Musgrave, Charles B., Lany, Stephan, Tate, Janet, Zhang, Qun, Holder, Aaron M, & Zakutayev, Andriy. Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers. United States. doi:10.1103/PhysRevApplied.13.014012.
Han, Yanbing, Trottier, Ryan, Siol, Sebastian, Matthews, Bethany, Young, Matthew R., Musgrave, Charles B., Lany, Stephan, Tate, Janet, Zhang, Qun, Holder, Aaron M, and Zakutayev, Andriy. Wed . "Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers". United States. doi:10.1103/PhysRevApplied.13.014012.
@article{osti_1598128,
title = {Templated Growth of Metastable Polymorphs on Amorphous Substrates with Seed Layers},
author = {Han, Yanbing and Trottier, Ryan and Siol, Sebastian and Matthews, Bethany and Young, Matthew R. and Musgrave, Charles B. and Lany, Stephan and Tate, Janet and Zhang, Qun and Holder, Aaron M and Zakutayev, Andriy},
abstractNote = {Metastable inorganic materials with unique properties are vital in many practical applications, but their synthesis is often challenging. In physics, epitaxial stabilization, also known as pseudomorphic growth, is used to synthesize metastable polymorphs, but usually only as very thin films and on expensive single-crystal substrates. In chemistry, the templated growth of inorganic solid-state materials on self-assembled monolayers of organic molecules is reported. Bridging these two fields, here, we show that the synthesis of metastable polymorphs is possible up to large film thickness on amorphous substrates covered with thin inorganic seed layers that serve as templates. The stabilization of a 500-nm-thick metastable wurtzite (WZ) MnTe film by a 5-nm-thick ZnTe seed layer sputtered on amorphous glass substrates is experimentally demonstrated. Theoretical calculations explain this experimental observation by the small WZ polymorph energy relative to that of the ground-state nickeline (NC) structure of MnTe and a large lattice constant difference of the two. The resulting metastable WZ-MnTe polymorph exhibits a wide band gap of 2.7 eV and a low hole density of 1012cm-3, which is relevant to optoelectronic applications. These properties are in sharp contrast to those of the narrow-band-gap highly doped NC-MnTe with 1.3 eV band gap and 1019cm-3 hole density. The difference in hole density is due to the calculated difference in the formation energy of manganese vacancy acceptor defects. Overall, these results suggest that templated growth on amorphous substrates with seed layers can be used to synthesize metastable polymorphs of other materials, without the need for expensive single-crystal substrates.},
doi = {10.1103/PhysRevApplied.13.014012},
journal = {Physical Review Applied},
number = 1,
volume = 13,
place = {United States},
year = {2020},
month = {1}
}

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