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Title: Synthesis of Freestanding Single-crystal Perovskite Films and Heterostructures by Etching of Sacrificial Water-soluble Layers

Abstract

The ability to create and manipulate materials in two-dimensional (2D) form has repeatedly had transformative impact on science and technology. In parallel with the exfoliation and stacking of intrinsically layered crystals, atomic-scale thin film growth of complex materials has enabled the creation of artificial 2D heterostructures with novel functionality and emergent phenomena, as seen in perovskite heterostructures. However, separation of these layers from the growth substrate has proven challenging, limiting the manipulation capabilities of these heterostructures with respect to exfoliated materials. Here we present a general method to create freestanding perovskite membranes. The key is the epitaxial growth of water-soluble Sr 3Al 2O 6 on perovskite substrates, followed by in situ growth of films and heterostructures. Millimetre-size single-crystalline membranes are produced by etching the Sr 3Al 2O 6 layer in water, providing the opportunity to transfer them to arbitrary substrates and integrate them with heterostructures of semiconductors and layered compounds.

Authors:
 [1];  [2];  [3];  [4];  [5];  [3]
  1. Stanford Univ., CA (United States). Dept. of Physics; SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
  2. Cornell Univ., Ithaca, NY (United States). School of Electrical and Computer Engineering
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences; Stanford Univ., CA (United States). Dept. of Applied Physics
  4. Cornell Univ., Ithaca, NY (United States). School of Applied and Engineering Physics; Cornell Univ., Ithaca, NY (United States). Kavli Inst. at Cornell for Nanoscale Science
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Inst. for Materials and Energy Sciences
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Gordon and Betty Moore Foundation (United States); National Science Foundation (NSF)
OSTI Identifier:
1310026
Report Number(s):
SLAC-PUB-16802
DOE Contract Number:
AC02-76SF00515
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; CHEM, MATSCI

Citation Formats

Lu, Di, Baek, David J., Hong, Seung Sae, Kourkoutis, Lena F., Hikita, Yasuyuki, and Hwang, Harold Y.. Synthesis of Freestanding Single-crystal Perovskite Films and Heterostructures by Etching of Sacrificial Water-soluble Layers. United States: N. p., 2016. Web. doi:10.2172/1310026.
Lu, Di, Baek, David J., Hong, Seung Sae, Kourkoutis, Lena F., Hikita, Yasuyuki, & Hwang, Harold Y.. Synthesis of Freestanding Single-crystal Perovskite Films and Heterostructures by Etching of Sacrificial Water-soluble Layers. United States. doi:10.2172/1310026.
Lu, Di, Baek, David J., Hong, Seung Sae, Kourkoutis, Lena F., Hikita, Yasuyuki, and Hwang, Harold Y.. 2016. "Synthesis of Freestanding Single-crystal Perovskite Films and Heterostructures by Etching of Sacrificial Water-soluble Layers". United States. doi:10.2172/1310026. https://www.osti.gov/servlets/purl/1310026.
@article{osti_1310026,
title = {Synthesis of Freestanding Single-crystal Perovskite Films and Heterostructures by Etching of Sacrificial Water-soluble Layers},
author = {Lu, Di and Baek, David J. and Hong, Seung Sae and Kourkoutis, Lena F. and Hikita, Yasuyuki and Hwang, Harold Y.},
abstractNote = {The ability to create and manipulate materials in two-dimensional (2D) form has repeatedly had transformative impact on science and technology. In parallel with the exfoliation and stacking of intrinsically layered crystals, atomic-scale thin film growth of complex materials has enabled the creation of artificial 2D heterostructures with novel functionality and emergent phenomena, as seen in perovskite heterostructures. However, separation of these layers from the growth substrate has proven challenging, limiting the manipulation capabilities of these heterostructures with respect to exfoliated materials. Here we present a general method to create freestanding perovskite membranes. The key is the epitaxial growth of water-soluble Sr3Al2O6 on perovskite substrates, followed by in situ growth of films and heterostructures. Millimetre-size single-crystalline membranes are produced by etching the Sr3Al2O6 layer in water, providing the opportunity to transfer them to arbitrary substrates and integrate them with heterostructures of semiconductors and layered compounds.},
doi = {10.2172/1310026},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 8
}

Technical Report:

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  • Here, the ability to create and manipulate materials in two-dimensional (2D) form has repeatedly had transformative impact on science and technology. In parallel with the exfoliation and stacking of intrinsically layered crystals 1, 2, 3, 4, 5, atomic-scale thin film growth of complex materials has enabled the creation of artificial 2D heterostructures with novel functionality 6, 7, 8, 9 and emergent phenomena, as seen in perovskite heterostructures 10, 11, 12. However, separation of these layers from the growth substrate has proved challenging, limiting the manipulation capabilities of these heterostructures with respect to exfoliated materials. Here we present a general methodmore » to create freestanding perovskite membranes. The key is the epitaxial growth of water-soluble Sr 3Al 2O 6 on perovskite substrates, followed by in situ growth of films and heterostructures. Millimetre-size single-crystalline membranes are produced by etching the Sr 3Al 2O 6 layer in water, providing the opportunity to transfer them to arbitrary substrates and integrate them with heterostructures of semiconductors and layered compounds 13, 14.« less
  • The crystallization, transformation, and partitioning of amorphous PbO-ZrO2-TiO2 powders produced by pyrolytic decomposition of mixed alkoxide precursors were investigated. Materials have the general formulation Pb1+xTi1/(1+PHI)ZrPHI/(1+PHI)O3+x, where {minus}0.2{le}x{le}0.2 is the fraction PbO excess/deficiency and 0{le}phi{le}1 is the Zr/Ti molar ratio. Most compositions first crystallized as a metastable fluorite structure with varying degrees of pyrochlore-like cation ordering, which transformed to a single perovskite phase upon additional heat treatment. Higher Zr/Ti ratios enhanced the retention of fluorite and reduced the incidence of cation ordering. Compositions with off-stoichiometric amounts of PbO often yielded extended solid solutions prior to partitioning. For example, metastable perovskites withmore » as much as 20% PbO deficiency (x = {minus}0.2) could be prepared for 0{le}phi{le}1, but only 10% PbO excess could be incorporated in solution for 0.33{le}phi{le}1. Increasing PbO content was found to promote crystallization, suggesting that this oxide acts as a network modifier enhancing mobility within the initial amorphous precursor powder. Higher PbO was also noted to favor cation ordering in the metastable phase and to accelerate the transformation to perovskite, as well as to promote partitioning for hyperstoichiometric compositions. The findings are discussed in light of structural relationships between the fluorite, pyrochlore and perovskite phases, as well as current understanding of the thermodynamics of the system.« less
  • Slip band configurations, cleavage lines, slip planes, and orientatiens of the dislocations in lithium fluoride single crystals are illustrated. Origin of the indentation figure for slip planes at a point is shown. (J.S.R.)
  • 'The first objective of this research is to develop rapid discovery and optimization approaches to new water-soluble chelating polymers. A byproduct of the development approach will be the new, selective, and efficient metal-binding agents. The second objective is to evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. The technology under development, Polymer Filtration (PF), is a technique to selectively remove or recover hazardous and valuable metal ions and radionuclides from various dilute aqueous streams. Not only can this technology be used to remediate contaminated soils and solid surfaces and treat aqueousmore » wastes, it can also be incorporated into facilities as a pollution prevention and waste minimization technology. Polymer Filtration uses water-soluble metal-binding polymers to sequester metal ions in dilute solution. The water-soluble polymers have a sufficiently large molecular size that they can be separated and concentrated using commercial ultrafiltration technology. Water, small organic molecules, and unbound metals pass freely through the ultrafiltration membrane while concentrating the metal-binding polymer. The polymers can then be reused by changing the solution conditions to release the metal ions. The metal-ions are recovered in concentrated form for recycle or disposal using a diafiltration process. The water-soluble polymer can be recycled for further aqueous-stream processing. To advance Polymer Filtration technology to the selectivity levels required for DOE needs. fixture directions in Polymer Filtration must include rapid development, testing, and characterization of new metal-binding polymers. The development of new chelating molecules can be equated to the process of new drugs or new materials discovery. Thus, the authors want to build upon and adapt the combinatorial chemistry approaches developed for rapid molecule generation for the drug industry to the rapid development of new chelating polymers.'« less