SCIENCE CHINA Information Sciences, Volume 62 , Issue 12 : 220407(2019) https://doi.org/10.1007/s11432-019-2653-9

Chemical vapor deposition synthesis of two-dimensional freestanding transition metal oxychloride for electronic applications

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  • ReceivedAug 17, 2019
  • AcceptedSep 16, 2019
  • PublishedNov 12, 2019



This work was supported in part by National Key Basic Research Program of China (Grant No. 2015CB921600), National Natural Science Foundation of China (Grant Nos. 61974176, 61574076), Collaborative Innovation Center of Advanced Microstructures, Natural Science Foundation of Jiangsu Province (Grant Nos. BK20180330, BK20150055), and Fundamental Research Funds for the Central Universities (Grant Nos. 020414380122, 020414380084).


Figures S1–S4.


[1] Novoselov K S, Mishchenko A, Carvalho A. 2D materials and van der Waals heterostructures.. Science, 2016, 353: aac9439 CrossRef PubMed Google Scholar

[2] Geim A K, Grigorieva I V. Van der Waals heterostructures.. Nature, 2013, 499: 419-425 CrossRef PubMed Google Scholar

[3] Sarkar D, Xie X, Liu W. A subthermionic tunnel field-effect transistor with an atomically thin channel. Nature, 2015, 526: 91-95 CrossRef PubMed ADS Google Scholar

[4] Liu C S, Chen H W, Hou X. Small footprint transistor architecture for photoswitching logic and in situ memory. Nat Nanotechnol, 2019, 14: 662-667 CrossRef PubMed ADS Google Scholar

[5] Wang M, Cai S H, Pan C. Robust memristors based on layered two-dimensional materials. Nat Electron, 2018, 1: 130-136 CrossRef Google Scholar

[6] Radisavljevic B, Radenovic A, Brivio J. Single-layer MoS$_{2}$ transistors. Nat Nanotech, 2011, 6: 147-150 CrossRef PubMed ADS Google Scholar

[7] Gao A Y, Lai J W, Wang Y J. Observation of ballistic avalanche phenomena in nanoscale vertical InSe/BP heterostructures. Nat Nanotechnol, 2019, 14: 217-222 CrossRef PubMed ADS arXiv Google Scholar

[8] Yin J B, Tan Z J, Hong H. Ultrafast and highly sensitive infrared photodetectors based on two-dimensional oxyselenide crystals. Nat Commun, 2018, 9: 3311 CrossRef PubMed ADS arXiv Google Scholar

[9] Wang F, Wang Z X, Yin L. 2D library beyond graphene and transition metal dichalcogenides: a focus on photodetection.. Chem Soc Rev, 2018, 47: 6296-6341 CrossRef PubMed Google Scholar

[10] Li X M, Tao L, Chen Z F. Graphene and related two-dimensional materials: Structure-property relationships for electronics and optoelectronics. Appl Phys Rev, 2017, 4: 021306 CrossRef ADS Google Scholar

[11] Wang Q H, Kalantar-Zadeh K, Kis A. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat Nanotech, 2012, 7: 699-712 CrossRef PubMed ADS Google Scholar

[12] Wang J, Han J Y, Chen X Q. Design strategies for two?dimensional material photodetectors to enhance device performance. InfoMat, 2019, 1: 33-53 CrossRef Google Scholar

[13] Li J, Ding Y, Zhang D W, et al. Photodetectors Based on Two-Dimensional Materials and Their van der Waals Heterostructures. Acta Physico-Chimica Sin, 2019, 35: 1058. Google Scholar

[14] Fiori G, Bonaccorso F, Iannaccone G. Electronics based on two-dimensional materials. Nat Nanotech, 2014, 9: 768-779 CrossRef PubMed ADS Google Scholar

[15] Akinwande D, Petrone N, Hone J. Two-dimensional flexible nanoelectronics. Nat Commun, 2014, 5: 5678 CrossRef PubMed ADS Google Scholar

[16] Cai Z Y, Liu B L, Zou X L. Chemical Vapor Deposition Growth and Applications of Two-Dimensional Materials and Their Heterostructures.. Chem Rev, 2018, 118: 6091-6133 CrossRef PubMed Google Scholar

[17] Manzeli S, Ovchinnikov D, Pasquier D. 2D transition metal dichalcogenides. Nat Rev Mater, 2017, 2: 17033 CrossRef ADS Google Scholar

[18] Mak K F, Shan J. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides. Nat Photon, 2016, 10: 216-226 CrossRef ADS Google Scholar

[19] Zhang Y, Yao Y, Sendeku M G. Recent Progress in CVD Growth of 2D Transition Metal Dichalcogenides and Related Heterostructures.. Adv Mater, 2019, 31: 1901694 CrossRef PubMed Google Scholar

[20] Anasori B, Lukatskaya M R, Gogotsi Y. 2D metal carbides and nitrides (MXenes) for energy storage. Nat Rev Mater, 2017, 2: 16098 CrossRef ADS Google Scholar

[21] Khazaei M, Ranjbar A, Arai M, et al. Electronic properties and applications of MXenes: a theoretical review. J Mater Chem C, 2017, 5: 2488. Google Scholar

[22] Komarek A C, Taetz T, Fernández-Díaz M T. Strong magnetoelastic coupling in VOCl: Neutron and synchrotron powder x-ray diffraction study. Phys Rev B, 2009, 79: 104425 CrossRef ADS arXiv Google Scholar

[23] Seidel A, Marianetti C A, Chou F C. S=1/2 chains and spin-Peierls transition in TiOCl. Phys Rev B, 2003, 67: 020405 CrossRef ADS Google Scholar

[24] Shaz M, van Smaalen S, Palatinus L. Spin-Peierls transition in TiOCl. Phys Rev B, 2005, 71: 100405 CrossRef ADS Google Scholar

[25] Zhao L, Fernández-Díaz M T, Tjeng L H. Oxyhalides: A new class of high-TC multiferroic materials. Sci Adv, 2016, 2: e1600353-e1600353 CrossRef PubMed ADS Google Scholar

[26] Miao N H, Xu B, Zhu L G. 2D Intrinsic Ferromagnets from van der Waals Antiferromagnets.. J Am Chem Soc, 2018, 140: 2417-2420 CrossRef PubMed Google Scholar

[27] Glawion S, Scholz M R, Zhang Y Z. Electronic structure of the two-dimensional Heisenberg antiferromagnet VOCl: A multiorbital Mott insulator. Phys Rev B, 2009, 80: 155119 CrossRef ADS arXiv Google Scholar

[28] Armand M, Coic L, Palvadeau P. The M-0-X transition metal oxyhalides: A new class of lamellar cathode material. J Power Sources, 1978, 3: 137-144 CrossRef ADS Google Scholar

[29] Gao P, Wall C, Zhang L. Vanadium oxychloride as electrode material for sodium ion batteries. Electrochem Commun, 2015, 60: 180-184 CrossRef Google Scholar

[30] Gao P, Zhao X y, Zhao-Karger Z. Vanadium oxychloride/magnesium electrode systems for chloride ion batteries.. ACS Appl Mater Interfaces, 2014, 6: 22430-22435 CrossRef PubMed Google Scholar

[31] Gao P, Reddy M A, Mu X. VOCl as a Cathode for Rechargeable Chloride Ion Batteries.. Angew Chem Int Ed, 2016, 55: 4285-4290 CrossRef PubMed Google Scholar

[32] Sidwick N V. The chemical elements and their compounds. J Chem Educ, 1950, 27: 529 CrossRef ADS Google Scholar

[33] Ji Q Q, Li C, Wang J L. Metallic Vanadium Disulfide Nanosheets as a Platform Material for Multifunctional Electrode Applications. Nano Lett, 2017, 17: 4908-4916 CrossRef PubMed ADS arXiv Google Scholar

[34] Zhou J H, Wang L, Yang M Y. Adv Mater, 2017, 29: 1702061 CrossRef PubMed Google Scholar

[35] Yuan J T, Wu J J, Hardy W J. Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction.. Adv Mater, 2015, 27: 5605-5609 CrossRef PubMed Google Scholar

[36] Phan H D, Kim Y, Lee J. Adv Mater, 2017, 29: 1603928 CrossRef PubMed Google Scholar

[37] Chen Y, Gong X L, Gai J G. Progress and Challenges in Transfer of Large-Area Graphene Films.. Adv Sci, 2016, 3: 1500343 CrossRef PubMed Google Scholar

[38] Park J, Choudhary N, Smith J. Thickness modulated MoS$_{2}$ grown by chemical vapor deposition for transparent and flexible electronic devices. Appl Phys Lett, 2015, 106: 012104 CrossRef ADS Google Scholar

[39] Lin Y C, Zhang W, Huang J K. Wafer-scale MoS$_{2}$ thin layers prepared by MoO$_{3}$ sulfurization. Nanoscale, 2012, 4: 6637-6641 CrossRef PubMed ADS Google Scholar

[40] Cullity B D, Weymouth J W. Elements of X-Ray Diffraction. Am J Phys, 1957, 25: 394-395 CrossRef ADS Google Scholar

[41] Kroemer H. Nobel Lecture: Quasielectric fields and band offsets: teaching electrons new tricks. Rev Mod Phys, 2001, 73: 783-793 CrossRef ADS Google Scholar

[42] Zhao H, Dong Z P, Tian H. Atomically Thin Femtojoule Memristive Device.. Adv Mater, 2017, 29: 1703232 CrossRef PubMed Google Scholar

[43] Tian H, Zhao L F, Wang X F. Extremely Low Operating Current Resistive Memory Based on Exfoliated 2D Perovskite Single Crystals for Neuromorphic Computing. ACS Nano, 2017, 11: 12247-12256 CrossRef Google Scholar

[44] Zhao X L, Liu S, Niu J B. Confining Cation Injection to Enhance CBRAM Performance by Nanopore Graphene Layer.. Small, 2017, 13: 1603948 CrossRef PubMed Google Scholar

[45] Zhao X L, Ma J, Xiao X H. Breaking the Current-Retention Dilemma in Cation-Based Resistive Switching Devices Utilizing Graphene with Controlled Defects.. Adv Mater, 2018, 30: 1705193 CrossRef PubMed Google Scholar

[46] Ge R J, Wu X H, Kim M. Atomristor: Nonvolatile Resistance Switching in Atomic Sheets of Transition Metal Dichalcogenides. Nano Lett, 2018, 18: 434-441 CrossRef PubMed ADS Google Scholar

[47] Qian K, Tay R Y, Nguyen V C. Hexagonal Boron Nitride Thin Film for Flexible Resistive Memory Applications. Adv Funct Mater, 2016, 26: 2176-2184 CrossRef Google Scholar

[48] Jo S H, Chang T, Ebong I. Nanoscale Memristor Device as Synapse in Neuromorphic Systems. Nano Lett, 2010, 10: 1297-1301 CrossRef PubMed ADS Google Scholar

[49] Ohno T, Hasegawa T, Tsuruoka T. Short-term plasticity and long-term potentiation mimicked in single inorganic synapses. Nat Mater, 2011, 10: 591-595 CrossRef PubMed ADS Google Scholar

[50] Shi Y Y, Liang X H, Yuan B. Electronic synapses made of layered two-dimensional materials. Nat Electron, 2018, 1: 458-465 CrossRef Google Scholar

[51] Deng Y, Luo Z, Conrad N J. Black phosphorus-monolayer MoS2 van der Waals heterojunction p-n diode.. ACS Nano, 2014, 8: 8292-8299 CrossRef PubMed Google Scholar

[52] Xu R J, Jang H, Lee M H. Vertical MoS2 Double-Layer Memristor with Electrochemical Metallization as an Atomic-Scale Synapse with Switching Thresholds Approaching 100 mV. Nano Lett, 2019, 19: 2411-2417 CrossRef PubMed ADS Google Scholar

[53] Sangwan V K, Lee H S, Bergeron H. Multi-terminal memtransistors from polycrystalline monolayer molybdenum disulfide. Nature, 2018, 554: 500-504 CrossRef PubMed ADS arXiv Google Scholar

[54] Yang J J, Strukov D B, Stewart D R. Memristive devices for computing. Nat Nanotech, 2013, 8: 13-24 CrossRef PubMed ADS Google Scholar

[55] Zhu J D, Yang Y C, Jia R D. Ion Gated Synaptic Transistors Based on 2D van der Waals Crystals with Tunable Diffusive Dynamics.. Adv Mater, 2018, 30: 1800195 CrossRef PubMed Google Scholar

[56] Yan X, Zhao Q, Chen A P. Small, 2019, 15: 1901423 CrossRef PubMed Google Scholar

[57] Zhou F C, Zhou Z, Chen J W. Optoelectronic resistive random access memory for neuromorphic vision sensors.. Nat Nanotechnol, 2019, 14: 776-782 CrossRef PubMed Google Scholar

  • Figure 1

    (Color online) Chemical vapor deposition of two-dimension single crystal VOCl and their optical images.protectłinebreak (a) Cross-section for atomic configurations of the VOCl lattice; (b) a schematic of VOCl synthesis setup; (c) and (d) optical images of as-grown VOCl on Si/SiO$~_2~$ substrate; (c) optical image of freestanding VOCl transferred to target substrate; protectłinebreak (d) inset, height profiles of VOCl nanosheet, scale bar is 10 $\mu~$m.

  • Figure 2

    (Color online) Characterization of VOCl. (a) X-ray diffraction (XRD) pattern; (b) X-ray photoelectron spectroscopy with full spectrum shown in the inset.

  • Figure 3

    (Color online) (a) Low resolution TEM images of VOCl flakes (scale bar: 0.5 $\mu$m); (b) energy dispersive X-ray spectroscopy (EDS) mapping of the sample area marked in the red box appearing in (a); (c) high resolution TEM image; (d) selected area electron diffraction (SAED) pattern (scale bar: 21 nm$^~{-1}$).

  • Figure 4

    (Color online) Electrical characterizations of VOCl based memristive devices. (a) Top: schematic of the VOCl devices. Bottom: optical image of a simple array of 2 $\mu$m $\times$ 2 $\mu$m VOCl based memristive devices. The top (TE) and bottom (BE) electrodes are Ag/Au and Au, respectively. (b) Typical IV switching curves of the VOCl based devices. The blue line represents the reset process after electroforming step and the red line is the 1st set process. The arrows indicate the switching direction. (c) Measured endurance of the device under DC sweep mode with compliance current of 250 $\mu$A and reset voltage of $-$1.4 V. (d) Measured retention data of on/off resistance states at room temperature with read voltage of 0.1 V. (e) Multilevel resistive switching characteristics of VOCl based memristive device via increasing compliance current (right red lines) and increasing RESET voltage (left blue lines). The arrows indicate the directions of adjusting resistance. (f) Variation of device resistance with consecutive depressing and potentiating pulses. The resistance is measured at 0.1 V after each pulse. Depression ($-$1.15 V, 500 $\mu$s); potentiation (1.6 V, 50 $\mu$s).