Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble&nbsp;layers

Lu, Di; Baek, David J.; Hong, Seung Sae; Kourkoutis, Lena F.; Hikita, Yasuyuki; Hwang, Harold Y.

doi:10.1038/nmat4749

Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble layers

Journal Article · Mon Sep 12 00:00:00 EDT 2016 · Nature Materials

DOI:https://doi.org/10.1038/nmat4749· OSTI ID:1326981

Lu, Di ^[1]; Baek, David J. ^[2]; Hong, Seung Sae ^[3]; Kourkoutis, Lena F. ^[4]; Hikita, Yasuyuki ^[5]; Hwang, Harold Y. ^[3]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Cornell Univ., Ithaca, NY (United States). Baker Lab.
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Cornell Univ., Ithaca, NY (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

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 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^{13, 14}.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1326981

Report Number(s):: SLAC-PUB--16802; nmat4749

Journal Information:: Nature Materials, Journal Name: Nature Materials; ISSN 1476-1122

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Two-Dimensional Dielectric Nanosheets: Novel Nanoelectronics From Nanocrystal Building Blocks Osada, Minoru; Sasaki, Takayoshi Advanced Materials, Vol. 24, Issue 2, p. 210-228 https://doi.org/10.1002/adma.201103241	journal	October 2011
Application of hydrogen ion beams to Silicon On Insulator material technology Bruel, Michel Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 108, Issue 3 https://doi.org/10.1016/0168-583X(95)01056-4	journal	February 1996
High-quality and efficient transfer of large-area graphene films onto different substrates Chen, Xu-Dong; Liu, Zhi-Bo; Zheng, Chao-Yi Carbon, Vol. 56 https://doi.org/10.1016/j.carbon.2013.01.011	journal	May 2013
Mechanisms of cement hydration Bullard, Jeffrey W.; Jennings, Hamlin M.; Livingston, Richard A. Cement and Concrete Research, Vol. 41, Issue 12 https://doi.org/10.1016/j.cemconres.2010.09.011	journal	December 2011
Review on microfabricated micro-solid oxide fuel cell membranes Evans, Anna; Bieberle-Hütter, Anja; Rupp, Jennifer L. M. Journal of Power Sources, Vol. 194, Issue 1 https://doi.org/10.1016/j.jpowsour.2009.03.048	journal	October 2009
Single-Crystalline SrRuO ₃ Nanomembranes: A Platform for Flexible Oxide Electronics Paskiewicz, Deborah M.; Sichel-Tissot, Rebecca; Karapetrova, Evguenia Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b04176	journal	December 2015
Graphene-Like Two-Dimensional Materials Xu, Mingsheng; Liang, Tao; Shi, Minmin Chemical Reviews, Vol. 113, Issue 5, p. 3766-3798 https://doi.org/10.1021/cr300263a	journal	January 2013
Tristrontium dialuminum hexaoxide: an intricate superstructure of perovskite Alonso, J. A.; Rasines, I.; Soubeyroux, J. L. Inorganic Chemistry, Vol. 29, Issue 23 https://doi.org/10.1021/ic00348a035	journal	November 1990
Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene Butler, Sheneve Z.; Hollen, Shawna M.; Cao, Linyou ACS Nano, Vol. 7, Issue 4, p. 2898-2926 https://doi.org/10.1021/nn400280c	journal	March 2013
Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors Nomura, Kenji; Ohta, Hiromichi; Takagi, Akihiro Nature, Vol. 432, Issue 7016, p. 488-492 https://doi.org/10.1038/nature03090	journal	November 2004
Chiral magnetic order at surfaces driven by inversion asymmetry Bode, M.; Heide, M.; von Bergmann, K. Nature, Vol. 447, Issue 7141 https://doi.org/10.1038/nature05802	journal	May 2007
Electric field control of the LaAlO3/SrTiO3 interface ground state Caviglia, A. D.; Gariglio, S.; Reyren, N. Nature, Vol. 456, Issue 7222 https://doi.org/10.1038/nature07576	journal	December 2008
Large-scale pattern growth of graphene films for stretchable transparent electrodes Kim, Keun Soo; Zhao, Yue; Jang, Houk Nature, Vol. 457, Issue 7230 https://doi.org/10.1038/nature07719	journal	January 2009
Ultrathin compound semiconductor on insulator layers for high-performance nanoscale transistors Ko, Hyunhyub; Takei, Kuniharu; Kapadia, Rehan Nature, Vol. 468, Issue 7321 https://doi.org/10.1038/nature09541	journal	November 2010
Synthesis, assembly and applications of semiconductor nanomembranes Rogers, J. A.; Lagally, M. G.; Nuzzo, R. G. Nature, Vol. 477, Issue 7362, p. 45-53 https://doi.org/10.1038/nature10381	journal	September 2011
Hofstadter’s butterfly and the fractal quantum Hall effect in moiré superlattices Dean, C. R.; Wang, L.; Maher, P. Nature, Vol. 497, Issue 7451 https://doi.org/10.1038/nature12186	journal	May 2013
Van der Waals heterostructures Geim, A. K.; Grigorieva, I. V. Nature, Vol. 499, Issue 7459, p. 419-425 https://doi.org/10.1038/nature12385	journal	July 2013
Emergent phenomena at oxide interfaces Hwang, H. Y.; Iwasa, Y.; Kawasaki, M. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3223	journal	January 2012
Direct measurement of strain effects on magnetic and electrical properties of epitaxial SrRuO3 thin films Gan, Q.; Rao, R. A.; Eom, C. B. Applied Physics Letters, Vol. 72, Issue 8 https://doi.org/10.1063/1.120603	journal	February 1998
Damage-free separation of GaN thin films from sapphire substrates Wong, W. S.; Sands, T.; Cheung, N. W. Applied Physics Letters, Vol. 72, Issue 5 https://doi.org/10.1063/1.120816	journal	February 1998
Mechanical Properties of Thin Single‐Crystal Gold Films Catlin, Avery; Walker, Walter P. Journal of Applied Physics, Vol. 31, Issue 12 https://doi.org/10.1063/1.1735513	journal	December 1960
Extreme selectivity in the lift‐off of epitaxial GaAs films Yablonovitch, Eli; Gmitter, T.; Harbison, J. P. Applied Physics Letters, Vol. 51, Issue 26, p. 2222-2224 https://doi.org/10.1063/1.98946	journal	December 1987
Microscopic origins for stabilizing room-temperature ferromagnetism in ultrathin manganite layers Kourkoutis, L. F.; Song, J. H.; Hwang, H. Y. Proceedings of the National Academy of Sciences, Vol. 107, Issue 26 https://doi.org/10.1073/pnas.1005693107	journal	June 2010
Interface-Induced High-Temperature Superconductivity in Single Unit-Cell FeSe Films on SrTiO ₃ Wang, Qing-Yan; Li, Zhi; Zhang, Wen-Hao Chinese Physics Letters, Vol. 29, Issue 3 https://doi.org/10.1088/0256-307X/29/3/037402	journal	March 2012
Influence of strain on the magnetization and magnetoelectric effect in La 0.7 A 0.3 Mn O 3 ∕ PMN − PT ( 001 ) ( A = Sr , Ca ) Thiele, C.; Dörr, K.; Bilani, O. Physical Review B, Vol. 75, Issue 5 https://doi.org/10.1103/PhysRevB.75.054408	journal	February 2007
Growth of Face-Centered-Cubic Metals on Sodium Chloride Substrates Matthews, J. W. Journal of Vacuum Science and Technology, Vol. 3, Issue 3 https://doi.org/10.1116/1.1492465	journal	May 1966
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S. Science, Vol. 306, Issue 5696, p. 666-669 https://doi.org/10.1126/science.1102896	journal	October 2004
Piezoelectric Nanogenerators Based on Zinc Oxide Nanowire Arrays Wang, Z. L. Science, Vol. 312, Issue 5771 https://doi.org/10.1126/science.1124005	journal	April 2006
Oxide Interfaces--An Opportunity for Electronics Mannhart, J.; Schlom, D. G. Science, Vol. 327, Issue 5973, p. 1607-1611 https://doi.org/10.1126/science.1181862	journal	March 2010
Tuning the Dimensionality of the Heavy Fermion Compound CeIn3 Shishido, H.; Shibauchi, T.; Yasu, K. Science, Vol. 327, Issue 5968 https://doi.org/10.1126/science.1183376	journal	February 2010
Experimental Observation of the Quantum Anomalous Hall Effect in a Magnetic Topological Insulator Chang, C. -Z.; Zhang, J.; Feng, X. Science, Vol. 340, Issue 6129 https://doi.org/10.1126/science.1234414	journal	March 2013
Interface Effect and Its Doping Dependence in La _{1- x} Sr _x MnO ₃ /SrTiO ₃ Superlattices Izumi, Makoto; Ogimoto, Yasushi; Manako, Takashi Journal of the Physical Society of Japan, Vol. 71, Issue 11 https://doi.org/10.1143/JPSJ.71.2621	journal	November 2002
Ultrathin compound semiconductor on insulator layers for high performance nanoscale transistors Ko, Hyunhyub; Takei, Kuniharu; Kapadia, Rehan arXiv https://doi.org/10.48550/arxiv.1108.1127	text	January 2011
Interface induced high temperature superconductivity in single unit-cell FeSe films on SrTiO3 Wang, Qing-Yan; Li, Zhi; Zhang, Wen-Hao arXiv https://doi.org/10.48550/arxiv.1201.5694	text	January 2012
Experimental Observation of the Quantum Anomalous Hall Effect in a Magnetic Topological Insulator Chang, Cui-Zu; Zhang, Jinsong; Feng, Xiao arXiv https://doi.org/10.48550/arxiv.1605.08829	text	January 2016
Electric Field Effect in Atomically Thin Carbon Films Novoselov, K. S.; Geim, A. K.; Morozov, S. V. arXiv https://doi.org/10.48550/arxiv.cond-mat/0410550	text	January 2004

Cited By (41)

Nanostructural Tailoring to Induce Flexibility in Thermoelectric Ca₃Co₄O₉ Thin Films Paul, Biplab; Lu, Jun; Eklund, Per ACS Applied Materials & Interfaces, Vol. 9, Issue 30 https://doi.org/10.1021/acsami.7b06301	journal	July 2017
Heteroepitaxial vertical perovskite hot-electron transistors down to the monolayer limit Kim, Brian S. Y.; Hikita, Yasuyuki; Yajima, Takeaki Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13290-3	journal	November 2019
Two-dimensional limit of crystalline order in perovskite membrane films Hong, Seung Sae; Yu, Jung Ho; Lu, Di Science Advances, Vol. 3, Issue 11 https://doi.org/10.1126/sciadv.aao5173	journal	November 2017
Erasable and recreatable two-dimensional electron gas at the heterointerface of SrTiO ₃ and a water-dissolvable overlayer Han, Kun; Hu, Kaige; Li, Xiao Science Advances, Vol. 5, Issue 8 https://doi.org/10.1126/sciadv.aaw7286	journal	August 2019
Nanoporous Films and Nanostructure Arrays Created by Selective Dissolution of Water-Soluble Materials. Kim, Yoon Seo; Song, Jaejung; Hwang, Chihyun Wiley https://doi.org/10.17863/cam.48726	journalarticle	January 2018
Bienenstock, Cooper, and Munro Learning Rules Realized in Second-Order Memristors with Tunable Forgetting Rate Xiong, Jue; Yang, Rui; Shaibo, Jamal Advanced Functional Materials, Vol. 29, Issue 9 https://doi.org/10.1002/adfm.201807316	journal	January 2019
Hydrogenation Dynamics of Electrically Controlled Metal–Insulator Transition in Proton‐Gated Transparent and Flexible WO ₃ Transistors Xu, Dong‐Dong; Deng, Xing; Zhao, Yi‐Feng Advanced Functional Materials, Vol. 29, Issue 34 https://doi.org/10.1002/adfm.201902497	journal	June 2019
Synergetic Behavior in 2D Layered Material/Complex Oxide Heterostructures Kang, Kyeong Tae; Park, Jeongmin; Suh, Dongseok Advanced Materials, Vol. 31, Issue 34 https://doi.org/10.1002/adma.201803732	journal	December 2018
Ferroelectric Domain Wall Motion in Freestanding Single‐Crystal Complex Oxide Thin Film Bakaul, Saidur R.; Kim, Jaegyu; Hong, Seungbum Advanced Materials, Vol. 32, Issue 4 https://doi.org/10.1002/adma.201907036	journal	December 2019
Conductive Oxide Interfaces for Field Effect Devices Kornblum, Lior Advanced Materials Interfaces, Vol. 6, Issue 15 https://doi.org/10.1002/admi.201900480	journal	June 2019
Stimulating Oxide Heterostructures: A Review on Controlling SrTiO ₃ ‐Based Heterointerfaces with External Stimuli Christensen, Dennis Valbjørn; Trier, Felix; Niu, Wei Advanced Materials Interfaces, Vol. 6, Issue 21 https://doi.org/10.1002/admi.201900772	journal	August 2019
Atomic Scale Understanding of the Epitaxy of Perovskite Oxides on Flexible Mica Substrate Lu, Lu; Dai, Yanzhu; Du, Hongchu Advanced Materials Interfaces, Vol. 7, Issue 2 https://doi.org/10.1002/admi.201901265	journal	December 2019
Giant Uniaxial Strain Ferroelectric Domain Tuning in Freestanding PbTiO ₃ Films Han, Lu; Fang, Yanhan; Zhao, Yunqi Advanced Materials Interfaces, Vol. 7, Issue 7 https://doi.org/10.1002/admi.201901604	journal	April 2020
Epitaxial Liftoff of Wafer‐Scale VO ₂ Nanomembranes for Flexible, Ultrasensitive Tactile Sensors Li, Xingxing; Yin, Zhigang; Zhang, Xingwang Advanced Materials Technologies, Vol. 4, Issue 7 https://doi.org/10.1002/admt.201800695	journal	April 2019
Nanoporous Films and Nanostructure Arrays Created by Selective Dissolution of Water-Soluble Materials Kim, Yoon Seo; Song, Jaejung; Hwang, Chihyun Advanced Science, Vol. 5, Issue 11 https://doi.org/10.1002/advs.201800851	journal	September 2018
Liquid–Solid Interfacial Assemblies of Soft Materials for Functional Freestanding Layered Membrane–Based Devices toward Electrochemical Energy Systems Li, Dongwei; Liang, Kang; Cheng, Wenlong Advanced Energy Materials, Vol. 9, Issue 21 https://doi.org/10.1002/aenm.201804005	journal	April 2019
Rectifying Effect of the Sr ₃ Al ₂ O ₆ /Ga ₂ O ₃ Heterojunction Liu, Zeng; Wang, Xia; Zhi, Yusong physica status solidi (a), Vol. 216, Issue 22 https://doi.org/10.1002/pssa.201900570	journal	September 2019
Strain Tuning in Complex Oxide Epitaxial Films Using an Ultrathin Strontium Aluminate Buffer Layer Lu, Di; Hikita, Yasuyuki; Baek, David J. physica status solidi (RRL) - Rapid Research Letters, Vol. 12, Issue 3 https://doi.org/10.1002/pssr.201700339	journal	January 2018
Assembly and Self-Assembly of Nanomembrane Materials-From 2D to 3D Huang, Gaoshan; Mei, Yongfeng Small, Vol. 14, Issue 14 https://doi.org/10.1002/smll.201703665	journal	January 2018
Freestanding crystalline oxide perovskites down to the monolayer limit Ji, Dianxiang; Cai, Songhua; Paudel, Tula R. Nature, Vol. 570, Issue 7759 https://doi.org/10.1038/s41586-019-1255-7	journal	June 2019
Heterogeneous integration of single-crystalline complex-oxide membranes Kum, Hyun S.; Lee, Hyungwoo; Kim, Sungkyu Nature, Vol. 578, Issue 7793 https://doi.org/10.1038/s41586-020-1939-z	journal	February 2020
Epitaxial growth and layer-transfer techniques for heterogeneous integration of materials for electronic and photonic devices Kum, Hyun; Lee, Doeon; Kong, Wei Nature Electronics, Vol. 2, Issue 10 https://doi.org/10.1038/s41928-019-0314-2	journal	October 2019
Enhanced bending-tuned magnetic properties in epitaxial cobalt ferrite nanopillar arrays on flexible substrates Shen, Lvkang; Liu, Ming; Ma, Chunrui Materials Horizons, Vol. 5, Issue 2 https://doi.org/10.1039/c7mh00939a	journal	January 2018
Damage-free and rapid transfer of CVD-grown two-dimensional transition metal dichalcogenides by dissolving sacrificial water-soluble layers Zhang, Lili; Wang, Chenyu; Liu, Xue-Lu Nanoscale, Vol. 9, Issue 48 https://doi.org/10.1039/c7nr06928f	journal	January 2017
Fabrication of ultralong perovskite structure nanotubes Wu, Xiaofeng; Huang, Keke; Yuan, Long RSC Advances, Vol. 8, Issue 1 https://doi.org/10.1039/c7ra10684j	journal	January 2018
Topochemical synthesis of 2D materials Xiao, Xu; Wang, Hao; Urbankowski, Patrick Chemical Society Reviews, Vol. 47, Issue 23 https://doi.org/10.1039/c8cs00649k	journal	January 2018
Recent progress on flexible inorganic single-crystalline functional oxide films for advanced electronics Zhang, Yong; Ma, Chunrui; Lu, Xiaoli Materials Horizons, Vol. 6, Issue 5 https://doi.org/10.1039/c8mh01598h	journal	January 2019
Development of oxide heteroepitaxy for soft technology Wu, Ping-Chun; Chu, Ying-Hao Journal of Materials Chemistry C, Vol. 6, Issue 23 https://doi.org/10.1039/c8tc00959g	journal	January 2018
A versatile patterning process based on easily soluble sacrificial bilayers Harada, Takayuki; Tsukazaki, Atsushi AIP Advances, Vol. 7, Issue 8 https://doi.org/10.1063/1.4993660	journal	August 2017
A general approach to obtain soft x-ray transparency for thin films grown on bulk substrates Fohler, Manuel; Frömmel, Stefanie; Schneider, Michael Review of Scientific Instruments, Vol. 88, Issue 10 https://doi.org/10.1063/1.5006522	journal	October 2017
Stressor-layer-induced elastic strain sharing in SrTiO ₃ complex oxide sheets Tilka, J. A.; Park, J.; Ahn, Y. Applied Physics Letters, Vol. 112, Issue 9 https://doi.org/10.1063/1.5019920	journal	February 2018
Strain-induced resistance change in V ₂ O ₃ films on piezoelectric ceramic disks Sakai, Joe; Bavencoffe, Maxime; Negulescu, Beatrice Journal of Applied Physics, Vol. 125, Issue 11 https://doi.org/10.1063/1.5083941	journal	March 2019
Non-Ohmic conduction in exfoliated La _0.7 Ca _0.3 MnO ₃ thin films Park, Jungsik; Shin, Jae Hoon; Song, Kyung Applied Physics Letters, Vol. 116, Issue 2 https://doi.org/10.1063/1.5127355	journal	January 2020
Spark plasma sintering of bulk SrAl ₂ O ₄ -Sr ₃ Al ₂ O ₆ eutectic glass with wide-band optical window Liu, Jiaxi; Lu, Nan; He, Gang Nanotechnology, Vol. 29, Issue 24 https://doi.org/10.1088/1361-6528/aab983	journal	April 2018
Freestanding crystalline YB a 2 C u 3 O 7 − x heterostructure membranes Chen, Zhuoyu; Wang, Bai Yang; Goodge, Berit H. Physical Review Materials, Vol. 3, Issue 6 https://doi.org/10.1103/physrevmaterials.3.060801	journal	June 2019
Extreme tensile strain states in La _0.7 Ca _0.3 MnO ₃ membranes Hong, Seung Sae; Gu, Mingqiang; Verma, Manish Science, Vol. 368, Issue 6486 https://doi.org/10.1126/science.aax9753	journal	April 2020
Super-elastic ferroelectric single-crystal membrane with continuous electric dipole rotation Dong, Guohua; Li, Suzhi; Yao, Mouteng Science, Vol. 366, Issue 6464 https://doi.org/10.1126/science.aay7221	journal	October 2019
A general approach to obtain soft x-ray transparency for thin films grown on bulk substrates Fohler, Manuel; Frömmel, Stefanie; Schneider, Michael Technische Universität Berlin https://doi.org/10.14279/depositonce-10030	text	January 2017
A general approach to obtain soft x-ray transparency for thin films grown on bulk substrates Fohler, Manuel; Frömmel, Stefanie; Schneider, Michael Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2019-03170	text	January 2017
Synergetic Behavior in 2D Layered Material/Complex Oxide Heterostructures Kang, Kyeong Tae; Park, Jeongmin; Suh, Dongseok arXiv https://doi.org/10.48550/arxiv.1905.02930	text	January 2019
Stressor-Layer-Induced Elastic Strain Sharing in SrTiO3 Complex Oxide Sheets Tilka, J. A.; Park, J.; Ahn, Y. arXiv https://doi.org/10.48550/arxiv.2002.11287	text	January 2020

Similar Records

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

Technical Report · Mon Aug 22 00:00:00 EDT 2016 · OSTI ID:1310026

Magnetic La_0.7Sr_0.3MnO₃ Membranes Synthesized by Etching a Sr₃Al₂O₆ Sacrificial Layer Using an Intermediary Manganite Protection Layer

Journal Article · Thu Feb 20 19:00:00 EST 2025 · ACS Applied Electronic Materials · OSTI ID:3001187

Ultrathin epitaxial barrier layer to avoid thermally induced phase transformation in oxide heterostructures

Journal Article · Wed Dec 21 19:00:00 EST 2016 · ACS Applied Materials and Interfaces · OSTI ID:1338292

Related Subjects

36 MATERIALS SCIENCE

Synthesis of freestanding single-crystal perovskite films and heterostructures by etching of sacrificial water-soluble layers

Citation Formats

References (36)

Cited By (41)

Similar Records

Related Subjects