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

Title: Two-dimensional inorganic molecular crystals

Abstract

Two-dimensional molecular crystals, consisting of zero-dimensional molecules, are very appealing due to their novel physical properties. However, they are mostly limited to organic molecules. The synthesis of inorganic version of two-dimensional molecular crystals is still a challenge due to the difficulties in controlling the crystal phase and growth plane. Here, we design a passivator-assisted vapor deposition method for the growth of two-dimensional Sb 2O 3 inorganic molecular crystals as thin as monolayer. The passivator can prevent the heterophase nucleation and suppress the growth of low-energy planes, and enable the molecule-by-molecule lateral growth along high-energy planes. Using Raman spectroscopy and in situ transmission electron microscopy, we show that the insulating α-phase of Sb 2O 3 flakes can be transformed into semiconducting β-phase under heat and electron-beam irradiation. Our findings can be extended to the controlled growth of other two-dimensional inorganic molecular crystals and open up opportunities for potential molecular electronic devices.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [3];  [2]; ORCiD logo [4]; ORCiD logo [1]
  1. Huazhong Univ. of Science and Technology (HUST), Wuhan (China). State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering
  2. Shenzhen Univ., Guangdong (China). Shenzhen Key Lab. of Flexible Memory Materials and Devices, College of Electronic Science and Technology
  3. Huazhong Univ. of Science and Technology (HUST), Wuhan (China). State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering; Stanford Univ., Stanford, CA (United States). Dept. of Material Science and Engineering
  4. Stanford Univ., Stanford, CA (United States). Dept. of Material Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1575222
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Han, Wei, Huang, Pu, Li, Liang, Wang, Fakun, Luo, Peng, Liu, Kailang, Zhou, Xing, Li, Huiqiao, Zhang, Xiuwen, Cui, Yi, and Zhai, Tianyou. Two-dimensional inorganic molecular crystals. United States: N. p., 2019. Web. doi:10.1038/s41467-019-12569-9.
Han, Wei, Huang, Pu, Li, Liang, Wang, Fakun, Luo, Peng, Liu, Kailang, Zhou, Xing, Li, Huiqiao, Zhang, Xiuwen, Cui, Yi, & Zhai, Tianyou. Two-dimensional inorganic molecular crystals. United States. doi:10.1038/s41467-019-12569-9.
Han, Wei, Huang, Pu, Li, Liang, Wang, Fakun, Luo, Peng, Liu, Kailang, Zhou, Xing, Li, Huiqiao, Zhang, Xiuwen, Cui, Yi, and Zhai, Tianyou. Thu . "Two-dimensional inorganic molecular crystals". United States. doi:10.1038/s41467-019-12569-9. https://www.osti.gov/servlets/purl/1575222.
@article{osti_1575222,
title = {Two-dimensional inorganic molecular crystals},
author = {Han, Wei and Huang, Pu and Li, Liang and Wang, Fakun and Luo, Peng and Liu, Kailang and Zhou, Xing and Li, Huiqiao and Zhang, Xiuwen and Cui, Yi and Zhai, Tianyou},
abstractNote = {Two-dimensional molecular crystals, consisting of zero-dimensional molecules, are very appealing due to their novel physical properties. However, they are mostly limited to organic molecules. The synthesis of inorganic version of two-dimensional molecular crystals is still a challenge due to the difficulties in controlling the crystal phase and growth plane. Here, we design a passivator-assisted vapor deposition method for the growth of two-dimensional Sb2O3 inorganic molecular crystals as thin as monolayer. The passivator can prevent the heterophase nucleation and suppress the growth of low-energy planes, and enable the molecule-by-molecule lateral growth along high-energy planes. Using Raman spectroscopy and in situ transmission electron microscopy, we show that the insulating α-phase of Sb2O3 flakes can be transformed into semiconducting β-phase under heat and electron-beam irradiation. Our findings can be extended to the controlled growth of other two-dimensional inorganic molecular crystals and open up opportunities for potential molecular electronic devices.},
doi = {10.1038/s41467-019-12569-9},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Orientational order controls crystalline and amorphous thermal transport in superatomic crystals
journal, September 2016

  • Ong, Wee-Liat; O’Brien, Evan S.; Dougherty, Patrick S. M.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4739

Room-temperature current blockade in atomically defined single-cluster junctions
journal, August 2017

  • Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.
  • Nature Nanotechnology, Vol. 12, Issue 11
  • DOI: 10.1038/nnano.2017.156

Breaking the Landauer limit
journal, July 2017


Molecular diodes with rectification ratios exceeding 105 driven by electrostatic interactions
journal, July 2017


Peltier cooling in molecular junctions
journal, December 2017


Activating the molecular spinterface
journal, April 2017

  • Cinchetti, Mirko; Dediu, V. Alek; Hueso, Luis E.
  • Nature Materials, Vol. 16, Issue 5
  • DOI: 10.1038/nmat4902

Humidity-controlled rectification switching in ruthenium-complex molecular junctions
journal, December 2017

  • Atesci, Huseyin; Kaliginedi, Veerabhadrarao; Celis Gil, Jose A.
  • Nature Nanotechnology, Vol. 13, Issue 2
  • DOI: 10.1038/s41565-017-0016-8

Bottom-up organic integrated circuits
journal, October 2008

  • Smits, Edsger C. P.; Mathijssen, Simon G. J.; van Hal, Paul A.
  • Nature, Vol. 455, Issue 7215
  • DOI: 10.1038/nature07320

Cluster-Assembled Materials
journal, January 2009

  • Claridge, Shelley A.; Castleman, A. W.; Khanna, Shiv N.
  • ACS Nano, Vol. 3, Issue 2
  • DOI: 10.1021/nn800820e

A molecular spin-photovoltaic device
journal, August 2017


Molecular behavior of zero-dimensional perovskites
journal, December 2017

  • Yin, Jun; Maity, Partha; De Bastiani, Michele
  • Science Advances, Vol. 3, Issue 12
  • DOI: 10.1126/sciadv.1701793

Two-dimensional quasi-freestanding molecular crystals for high-performance organic field-effect transistors
journal, October 2014

  • He, Daowei; Zhang, Yuhan; Wu, Qisheng
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6162

Transforming C60 molecules into graphene quantum dots
journal, March 2011

  • Lu, Jiong; Yeo, Pei Shan Emmeline; Gan, Chee Kwan
  • Nature Nanotechnology, Vol. 6, Issue 4
  • DOI: 10.1038/nnano.2011.30

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template
journal, April 2018

  • Lee, Kihong; Choi, Bonnie; Plante, Ilan Jen-La
  • Angewandte Chemie International Edition, Vol. 57, Issue 21
  • DOI: 10.1002/anie.201800953

Robust epitaxial growth of two-dimensional heterostructures, multiheterostructures, and superlattices
journal, August 2017


One-pot growth of two-dimensional lateral heterostructures via sequential edge-epitaxy
journal, January 2018

  • Sahoo, Prasana K.; Memaran, Shahriar; Xin, Yan
  • Nature, Vol. 553, Issue 7686
  • DOI: 10.1038/nature25155

A library of atomically thin metal chalcogenides
journal, April 2018


Vapour–liquid–solid growth of monolayer MoS2 nanoribbons
journal, April 2018


Evolutionary selection growth of two-dimensional materials on polycrystalline substrates
journal, March 2018

  • Vlassiouk, Ivan V.; Stehle, Yijing; Pudasaini, Pushpa Raj
  • Nature Materials, Vol. 17, Issue 4
  • DOI: 10.1038/s41563-018-0019-3

Preparation of Single-Crystalline Heterojunctions for Organic Electronics
journal, February 2017


Structural and vibrational study of cubic Sb 2 O 3 under high pressure
journal, May 2012


Thermal behaviour of chlorine-antimony fire-retardant systems
journal, January 1990


Refinement of the crystal structure of cubic antimony trioxide, Sb 2 O 3
journal, August 1975

  • Svensson, C.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 31, Issue 8
  • DOI: 10.1107/S0567740875006759

Raman scattering, luminescence, and absorption edge under hydrostatic pressures of layered BiI3 and SbI3
journal, January 2007

  • Saitoh, A.
  • Journal of Raman Spectroscopy, Vol. 38, Issue 5
  • DOI: 10.1002/jrs.1676

From Bulk to Monolayer MoS2: Evolution of Raman Scattering
journal, January 2012

  • Li, Hong; Zhang, Qing; Yap, Chin Chong Ray
  • Advanced Functional Materials, Vol. 22, Issue 7
  • DOI: 10.1002/adfm.201102111

Phase-selective synthesis of 1T′ MoS2 monolayers and heterophase bilayers
journal, October 2018


Self-Limited Epitaxial Growth of Ultrathin Nonlayered CdS Flakes for High-Performance Photodetectors
journal, March 2018


Halide-Induced Self-Limited Growth of Ultrathin Nonlayered Ge Flakes for High-Performance Phototransistors
journal, September 2018

  • Hu, Xiaozong; Huang, Pu; Jin, Bao
  • Journal of the American Chemical Society, Vol. 140, Issue 40
  • DOI: 10.1021/jacs.8b07383

The electronic structure of the antimony chalcogenide series: Prospects for optoelectronic applications
journal, May 2014


Electronic Structures of Antimony Oxides
journal, July 2013

  • Allen, Jeremy P.; Carey, John J.; Walsh, Aron
  • The Journal of Physical Chemistry C, Vol. 117, Issue 28
  • DOI: 10.1021/jp4026249

Thermal phase transitions in antimony (III) oxides
journal, September 2007


Vibrational spectroscopic and quantum chemical study of antimony(III) oxide
journal, February 2009

  • Voit, E. I.; Panasenko, A. E.; Zemnukhova, L. A.
  • Journal of Structural Chemistry, Vol. 50, Issue 1
  • DOI: 10.1007/s10947-009-0008-0

Synthesis and purple-blue emission of antimony trioxide single-crystalline nanobelts with elliptical cross section
journal, February 2009


Strong In-Plane Anisotropies of Optical and Electrical Response in Layered Dimetal Chalcogenide
journal, September 2017


Structural phase transition in monolayer MoTe2 driven by electrostatic doping
journal, October 2017


Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2
journal, April 2014

  • Lin, Yung-Chang; Dumcenco, Dumitru O.; Huang, Ying-Sheng
  • Nature Nanotechnology, Vol. 9, Issue 5
  • DOI: 10.1038/nnano.2014.64

Definition of a Transcendental Order Parameter for Reconstructive Phase Transitions
journal, May 1988


Sub-nanometre channels embedded in two-dimensional materials
journal, December 2017

  • Han, Yimo; Li, Ming-Yang; Jung, Gang-Seob
  • Nature Materials, Vol. 17, Issue 2
  • DOI: 10.1038/nmat5038

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011