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Frontiers of Optoelectronics

Front Optoelec    2013, Vol. 6 Issue (4) : 386-412     DOI: 10.1007/s12200-013-0357-3
REVIEW ARTICLE |
Review on one-dimensional ZnO nanostructures for electron field emitters
Meirong SUI1, Ping GONG1, Xiuquan GU2()
1. School of Medical Image, Xuzhou Medical College, Xuzhou 221004, China; 2. School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou 221116, China
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Abstract

The emission of electrons from the surface of a solid caused by a high electric field is called field emission (FE). Electron sources based on FE are used today in a wide range of applications, such as microwave traveling wave tubes, e-beam evaporators, mass spectrometers, flat panel of field emission displays (FEDs), and highly efficient lamps. Since the discovery of carbon nanotubes (CNTs) in 1991, much attention has been paid to explore the usage of these ideal one-dimensional (1D) nanomaterials as field emitters achieving high FE current density at a low electric field because of their high aspect ratio and “whisker-like” shape for optimum geometrical field enhancement. 1D metal oxide semiconductors, such as ZnO and WO3 possess high melting point and chemical stability, thereby allowing a higher oxygen partial pressure and poorer vacuum in FE applications. In addition, unlike CNTs, in which both semiconductor and metallic CNTs can co-exist in the as-synthesized products, it is possible to prepare 1D semiconductor nanostructures with a unique electronic property. Moreover, 1D semiconductor nanostructures generally have the advantage of a lower surface potential barrier than that of CNTs due to lower electron affinity and the conductivity could be enhanced by doping with certain elements. As a consequence, there has been increasing interest in the investigation of 1D metal oxide nanostructure as an appropriate alternative FE electron source to CNT for FE devices in the past few years. This paper provides a comprehensive review of the state-of-the-art research activities in the field. It mainly focuses on FE properties and applications of the most widely studied 1D ZnO nanostructures, such as nanowires (NWs), nanobelts, nanoneedles and nanotubes (NTs). We begin with the growth mechanism, and then systematically discuss the recent progresses on several kinds of important nano-structures and their FE characteristics and applications in details. Finally, it is concluded with the outlook and future research tendency in the area.

Keywords field emission (FE)      nanostructure      metal oxide     
Corresponding Authors: GU Xiuquan,Email:xqgu@cumt.edu.cn   
Issue Date: 05 December 2013
 Cite this article:   
Meirong SUI,Ping GONG,Xiuquan GU. Review on one-dimensional ZnO nanostructures for electron field emitters[J]. Front Optoelec, 2013, 6(4): 386-412.
 URL:  
http://journal.hep.com.cn/foe/EN/10.1007/s12200-013-0357-3
http://journal.hep.com.cn/foe/EN/Y2013/V6/I4/386
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Fig.1  Schematic diagram of typical chemical vapor deposition (CVD) system
Fig.2  Schematic illustration of vapor- liquid-solid (VLS) NW growth mechanism. (a) Metal deposition; (b) metal NPs formation; (c) absorption and nucleation; (d) epitaxial growth. Adapted from: Li et al. (2004) []
Fig.3  Schematic representation of basic steps of the growth modes of wires with Au at the roots (a) and at the tips (b). Adapted from: Kim et al. (2008) []
Fig.4  Field emission scanning electron microscope (FESEM) photographs for (a) Au and (b) Cu catalyzed ZnO NW arrays synthesized on p-type Si (100) substrate. Adapted from: Li et al. (2004) []
Fig.5  Perpendicular growth of NRs on plane of ZnO microrods by a simple thermal evaporation process using Sn as catalyst. (a) 500 nm; (b) 200 nm; (c) 100 nm; (d) 30 nm. Adapted from: Gao et al. (2003) []
Fig.6  Variation of density (left-hand vertical axis) and width (right-hand vertical axis) of aligned ZnO NWs with the thickness of Au catalyst layer. Inset: Top-view SEM image of aligned ZnO NWs used for calculation, the sale bar represents 200 nm. Adapted from: Wang et al. (2007) []
Fig.7  (a) Cross-sectional FESEM image of the well aligned ZnO nanoneedle arrays; (b) FESEM image of the obvious growth steps observed in the experiments; (c) schematic plane of the growth model. Adapted from: Zhang et al. (2006) []
Fig.8  FE-SEM images of ZnO NTs. (a) Low-magnification top view; (b) one ZnO NT with single-wall; and (c) double-walls. Adapted from: Xu et al. (2005) []
Fig.9  RT PL spectra of ZnMgO NRs with varying in the range of 0-0.32. Inset shows the UV luminescence energy as a function of Mg contents. Adapted from: Lu et al. (2007) []
Fig.10  Schematic showing PLD synthesis apparatus. Laser energy is directed through a treated glass window to a pressed target. Vapors are released and re-condensed as 1D nanostructures nucleated on Au catalyst []
Fig.11  Wire length against diameter with (circles) and without (triangle) PEI added to the growth bath. Lines are least-square fits to the data, and the error bars represent one standard deviation. Adapted from: Law et al. (2005) []
Fig.12  ZnO NW array on a four-inch silicon wafer. At the center is a photograph of a coated wafer, surrounded by SEM images of the array at different location and magnifications. These images are representative of the entire surface. Scale bars, clockwise from the upper left: 2 μm, 1 μm, 500 nm and 200 nm. Adapted from: Greene et al. (2003) []
Fig.13  Schematic model of ZnO NW dye-sensitized cells. Light is incident through bottom electrode. Adapted from: Law et al. (2005) []
Fig.14  Transmission electron microscope (TEM) images of ZnO NRs synthesized via hydrothermal methods at 180°C. Adapted from: Yang et al. (2002) []
Fig.15  Schematic illustration of evolving morphologies of Zn- and O-terminated Zn-polar (0001) surfaces under the present hydrothermal growth conditions. Adapted from: Liu and Zeng (2003) []
Fig.16  SEM (a) and TEM (b) and HRTEM (c) images of ZnO NT arrays. The inset of (c) shows the corresponding electron diffraction patterns. Adapted from: Sun et al. (2006) []
Fig.17  Typical SEM images of ZnO NR arrays on Zn foil (a, b) and Ti substrate (c) as well as the corresponding energy dispersive spectroscopy (EDS) pattern (d). Adapted from: Wang et al. (2008) []
Fig.18  (a) TEM images of self-assembled 2 nm diameter ZnO NRs (inset: higher resolution image showing the oriented stacking); (b) selected area electron diffraction pattern of NRs. Adapted from: Yin et al. (2004) []
Fig.19  (a) SEM and (b) HRTEM characterization of cobalt-doped ZnO NWs. Cobalt content is about 11.34 atom. %. Adapted from: Yuhas et al. (2006) []
Fig.20  SEM images of (a, b) ZnO nanopillars and (c, d) nanowalls electro- deposited on InO-coated PET substrates. The insets in (a, c) show the corresponding photographs of the as-deposited samples, and the inset in (b) shows a magnified image depicting the hexagonal shape of the nanopillars. Adapted from: Pradhan et al. (2008) []
Fig.21  Schematic drawing of electrospinning apparatus. Adapted from: Wu and Pan (2006) []
Fig.22  SEM images of ZnO nanofibers. (a) Zinc acetate/ polyvinyl alcohol composite fibers with 50 wt% of zinc acetate; (b) calcined at 500°C for 6 h; (c) calcined at 500°C for 8 h; (d) calcined at 500°C for 10 h. Adapted from: Wu and Pan (2006) []
Fig.23  (a) FE-SEM image of the precursor fibers collected in random orientation; (b) ZnO nanofibers prepared by calcination of the precursor fibers at 500°C; (c) TEM image of a single ZnO nanofiber. Inset: the selected area electron diffraction pattern; (d) HRTEM image of the sample, indicating the polycrystalline structure of the calcined fiber. Adapted from: Wu et al. (2008) []
Fig.24  (a) Low-magnification image of aligned ZnO NTs; (b) tilted view of ZnO NT arrays. Adapted from: Shen et al. []
Fig.25  SEM images of In-doped ZnO NRs grown on p-GaN substrates with various magnifications and tilting angles. (a) 5 μm; (b) 1 μm; (c) 300 nm; (d) 200 nm. Adapted from: Zhou et al. (2008) []
Fig.26  Schematic sketch for the field emission measurements. Adapted from: Yang et al. (2005) []
Fig.27  Typical Fowler-Nordheim plot of the field emission current density. Adapted from: Jo et al. (2004) []
Fig.28  Experimental (plot) and exponential simulated (line) relationship between the emission current density and applied electric field in and plots. Adapted from: Liu et al. (2007) []
Fig.29  Field emission - curves from ZnO nanoneedle arrays at different anode-cathode distances: = 520 μm, and = 560 μm. Adapted from: Zhang et al. (2004) []
Fig.30  Characteristic of emission current via change of vacuum chamber. Adapted from: Zhang et al. (2004) []
Fig.31  (a) Patterned growth of high density ZnO NRs; (b) medium patterned density formed from each 0.2 μm via hole. Adapted from: Chang et al. (2005) []
Fig.32  (a) Representive SEM image of aligned ZnO NWs; insert: an SEM image of the FE testing condition; (b) TEM image of typical ZnO NWs; (c) corresponding electron diffraction pattern; (d) SEM image of the highest density ZnO NWs after FE testing; inset: an enlarged SEM image of NW bundles. Adapted from: Wang et al. (2007) []
Fig.33  SEM images of ZnO NR arrays (a) and nanocones (b). The inset in (a) and (b) exhibit the enlarged view of the NRs and nanocones. Adapted from: Ye et al. (2007) []
Fig.34  Typical SEM images of three different ZnO NR arrays. (a) Nanoneedle; (b) nanocavities; (c) bottle shaped. Adapted from: Zhao et al. (2005) []
Fig.35  Measured field emission current density of ZnO NWs grown on carbon cloth as function of macroscopic electric field. Adapted from: Banerjee et al. (2004) []
Fig.36  Field emission characteristic curves of as-grown and plasma-treated ZnO nanoneedle arrays at hydrogen flow rate of 200 sccm. Adapted from: Yoo et al. (2005) []
Fig.37  - plot of field emission from ZnO NRs: (A) as-grown; (B) annealing in O; (C) annealing in air and (D) annealing in NH Inset: the corresponding F-N plots. Adapted from: Zhao et al. (2006) []
Fig.38  Stability of emission current. Voltage was increased from 0 V to 1.18 kV within 84 s and then fixed at 1.18 kV. The inset showed the fluctuations of emission current. Adapted from: Li et al. (2004) []
ZnO emittersynthesis methodturn-on field/(V?μm-1)on field/(V?μm-1)βstabilitytesting timeand fluctuationRef.
NRsthermal evaporation3.611.230 min,<10%[148]
nanoscrewsthermal evaporation3.611.2 at 1.2 mA103930 min,<10%[149]
tetrapod-likethermal evaporation1.8 at 1 μA3.99108 h,<3%[147]
NTshydrothermal method7.0 at 0.1 μA17.841724 h,<10%[127]
microtubesmicrowave heating5.6 at 1 μA6.4 at 11 mA24 h,<10%[150]
Tab.1  Key performance parameters of some 1D ZnO nanostructures field emitters reported in the literature. Turn-on field and on field were obtained at current densities of 10 μA/cm and 10 mA/cm, respectively, unless otherwise stated
Fig.39  Illustration of field electron emission from a tip. Adapted from: Xu and Huq (2005) []
Fig.40  (a) SEM image of single ZnO NW grown on sharp Pt tip; (b) HRTEM image of a single ZnO NW. Inset shows the selective area electronic diffraction (SAED) pattern at the base of the NW. Zone axis of the diffraction pattern is deduced to be [02 ]. Adapted from: Yeong et al. (2007) []
morphologysubstrates(methods)turn-on field/(V?μm-1)on field/(V?μm-1)βRef.
nanosheets/ nanocombs/ nanowires/ nanobelts3.98.91600
Brass foils(thermal evaporation)3.87.64208[85]
3.06.94611
2.05.36720
[66]
ultralong nanobelts2.9 at 1 mA/cm2104-105
NWs[138]
Au sheets
(molten-assisted CVD)
nanoneedles/[150]
NRs/ nanopencilsPt tips
(electrochemical deposition)4.27.22350[127]
NTs6.48.2790
Fe-Co-Ni alloy7.511.31140[101]
(hydrothermal method)
nanoneedles7.0 at 0.1 mA/cm217.0 at 1 mA/cm2910151]
Cu plates[152]
NWs(hydrothermal method)3.0 at 0.1 mA/cm219.0 at 1 mA/cm28504 (L)
1581 (H)[105]
Zinc foils (self-source)
NRs(hydrothermal method)
Tungsten plates/ tips
NRs9.0 at 0.061 mA/ cm22.081 × 103
Aluminum sheets
(thermal evaporation)5.3850-1044
Zinc foils
(self-source)
Tab.2  Key performance parameters of 1D ZnO nanostructures prepared on various substrates reported in the literature. The turn-on field and on field were obtained at current densities of 10 μA/cm and 10 mA/cm, respectively
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