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Zinc Oxide Nanostructures: Synthesis and Properties

Zhiyong Fan and Jia G. Lu*
Department of Chemical Engineering and Materials Science & Department of Electrical Engineering and Computer Science University of California, Irvine, CA 92697, USA

This article provides a comprehensive review of the current research activities that focus on the ZnO nanostructure materials and their physical property characterizations. It begins with the synthetic methods that have been exploited to grow ZnO nanostructures. A range of remarkable characteristics are then presented, organized into sections describing the mechanical, electrical, optical, magnetic and chemical sensing properties. These studies constitute the basis for developing versatile applications of ZnO nanostructures. Keywords: wide band gap semiconductor; nanostructure; UV emission; field effect transistors, chemical sensing; spintronics

Submission: 7 January, 2005

Revised/Accepted: 22 April, 2005

CONTENTS 1. 2. Introduction Synthesis of ZnO Nanostructures 2.1 Vapor Transport Synthesis 2.2 Patterned Growth and Vertical Alignment of ZnO Nano-Array 2.3 Other Growth methods 3. Physical Properties of ZnO Nanostructures 3.1 Mechanical Properties 3.2 Piezoelectric effect and polar surfaces 3.3 Electrical Properties 3.4 Optical Properties 3.5 Magnetic Doping 3.6 Chemical Sensing 4. Conclusions *Author to whom correspondence should be addressed. Email: jglu@uci.edu

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such as nanowires. In such a process. This leads to a reduced UV lasing threshold and yields higher UV emitting efficiency at room temperature. and ferromagnetic doping studies. optical. thermal evaporation.1-10 Invisible thin film transistors (TFTs) using ZnO as an active channel have achieved much higher field effect mobility than amorphous silicon TFTs. UV emission. Decomposition of ZnO is a direct and simple method. It has been observed that the change of this ratio contributes to a large variation on the morphology of nanostructures. electrical. Zn and oxygen or oxygen mixture vapor are transported and react with each other.14 Surface acoustic wave filters using ZnO films have already been used for video and radio frequency circuits. and electrodeposition. nanotubes. Introduction Zinc oxide (ZnO).23.35.37-41 Also in the widely used carbothermal method. Issues of synthesis methods. magnetic and gas sensing properties are summarized. 2. gas sensing. piezoelectric devices. At about 800-1100 °C. has a stable wurtzite structure with lattice spacing a = 0. and considerable progresses have been achieved.4 eV) II-VI compound semiconductor. in which organometallic Zn compound. It has attracted intensive research effort for its unique properties and versatile applications in transparent electronics. large effort has been focused on the synthesis. ZnO has been proposed to be a more promising UV emitting phosphor than GaN because of its larger exciton binding energy (60 meV). There are several ways to generate Zn and oxygen vapor. it is limited to very high temperatures (~1400°C). ultraviolet (UV) light emitters. The advantages of 1 . nanorings.1. chemical sensors and spin electronics.42-69 ZnO powder is mixed with graphite powder as source material. characterization and device applications of ZnO nanomaterials. Piezoelectric ZnO thin film has been fabricated into ultrasonic transducer arrays operating at 100 MHz. 23-32 These nanostructures have been subjected to electrical transport.21 Vanadium doped n-type ZnO films also demonstrate a Curie temperature above room temperature. a wide bandgap (3. structural.15 Bulk and thin films of ZnO have demonstrated high sensitivity for toxic gases. graphite reduces ZnO to form Zn and CO/CO2 vapors. etc.14. forming ZnO nanostructures.35 The indirect methods to provide Zn vapor include metal-organic vapor phase epitaxy. but the ratio between the Zn vapor pressure and oxygen pressure needs to be carefully controlled in order to obtain desired ZnO nanostructures. Synthesis of ZnO Nanostructures 2. and nano-tetrapods have been successfully grown via a variety of methods including chemical vapor deposition.33 This review presents recent advances on ZnO nanostructures. diethyl-zinc for example. however.11-13 These transistors can be widely used for display applications.16-19 Furthermore. Zn and CO/CO2 later react and result in ZnO nanocrystals.325 nm and c = 0.22 Based on these remarkable physical properties and the motivation of device miniaturization.36 This method facilitates relative low growth temperature (500~700°C). An assortment of ZnO nanostructures.1 Vapor Transport Synthesis The most common method to synthesize ZnO nanostructures utilizes a vapor transport process.34 Another direct method is to heat up Zn powder under oxygen flow. hole mediated ferromagnetic ordering in bulk ZnO by introducing Mn as dopant has been predicted theoretically 20 and reported recently. is used under appropriate oxygen or N2O flow.521 nm.

Y.50. Phys. 50. Inset: structure model of the nanobelt. 1625 (2003) with permission from American Chemical Society. as shown in Fig. (d) Needle-like ZnO rods. then under Ar carrier gas. nanostructures were deposited onto an alumina substrate at a low temperature zone (400-500 °C).34 (Fig. A simplified method to achieve nanowires. Scale bar: 10 µm. (a) (b) (d) Fig. were grown by heating mixed powder of ZnO. 34. Kong et al. 81. B. complex ZnO nanostructures such as nanohelixes and nanobelts were synthesized by Kong et al. 1d shows the needle-like ZnO rods. Fig. nanorods. After cooling down. nanostructures were found to form on the wall of the furnace. including nanowires.63 hierarchical ZnO nanostructures. 1c. D. According to the difference on nanostructure formation mechanisms. Reprint from ref. ZnO powder was decomposed into Zn2+ and O2. Y.. (a) A SEM micrograph of ZnO nanohelix structures grown via VS process. (b) A TEM image of ZnO nanobelt grown via VLS process.at ~1350 °C. 2 . Lett. 1a & b).34.this method lie in that the existence of graphite significantly lowers the decomposition temperature of ZnO. the extensively used vapor transport process can be categorized into the catalyst free vapor-solid (VS) process and catalyst assisted vapor-liquid-solid (VLS) process. Synthesis utilizing VS process is usually capable of producing a rich variety of nanostructures.52. Nano. X.. (c) Hierachical ZnO nanostructures synthesized by vapor transport and condensation technique. In2O3 and graphite to 820-870 °C. 52.50-64 In a typical VS process. in which ZnO powder was mixed with graphite and heated to 1100 °C. In this process. Lao et al. 2.. In a similar vapor transport and condensation process reported by Ren et al. nanoribbons and nanorods was reported by Yao et al. Lett. 1287 (2002) with permission from American Chemical Society. 757 (2002) with permission from American Institute of Physics. Yao et al. Nano. nanobelts and other complex structures. Reprint from ref.51. Reprint from ref. Appl.29-31. Lett.. 1. J. 3.

Zn and ZnO powder were mixed together and heated up to 1300 °C in Ar flow with an appropriate amount of water held in a glass vessel upstream of the source materials.54. followed by the nucleation and growth of solid ZnO nanowire due to the supersaturation of the liquid droplet. The source and substrate were heated up to 700 °C accompanied with appropriate O2 flow. 2b. The formation of eutectic alloy droplet occurs at each catalyst site. 58.47-49.72 In a VLS synthesis process using Zn power as the source material. Reprint from ref.43 Co 70. R. Their electron field emission and magnetic properties have been studied58.66 and nano-tetrapods45.53 Fig. (b) ZnO nano-tetrapod formed by rapid heating zinc pellet at 900 °C. 5.46. (a) SEM image of ZnO nanotubes grown from wet-oxidation. (b) Fig.67. The high resolution transmission electron microscopy (HRTEM) reveals tube wall thickness of 4-10 nm.42. this method obviously provides less control on the geometry. 2253 (2003) with permission from American Institute of Physics. the nanostructures are produced by condensing directly from vapor phase. Controlled growth of ZnO nanowires/nanorods/nanotubes has been achieved by catalyst assisted VLS process. Q.76 Cu.65. Phys. 2. M. 53.68 also attract considerable research interests. nanobelts and nanorods. In the VS process.55-59. alignment and precise location of ZnO nanostructures. 3a shows a schematic of a typical VLS process.. several methods for growing ZnO nanotubes have been reported. Fig. 2a shows the as-synthesized ZnO nanotubes with diameter of 30-100 nm. New J. Wan et al. such as Au. Although diverse nanostructures can be obtained. 115. 3 . Lett.53.17..58 The obtained ZnO tetra-pods are demonstrated in Fig. such growth method inherently provides site-specific nucleation at each catalytic site.44. Wang et al. etc.76 the sample collecting substrate was deposited with Au nanoparticles of diameter ~30 nm and placed adjacent to the source.68 and will be discussed in section 3.35.Besides nanowires. Phys. Since the discovery of carbon nanotube. various nanoparticles or nanoclusters have been used as catalysts.14. other complex ZnO nanostructures such as nanotubes44. reported a method of rapid heating zinc pellet at 900 °C in air ambient. Thus. 83.59. Reprint from ref. resulting in high quality ZnO nanowires. Appl. Incremental growth of the nanowire taking place at the droplet interface constantly pushes the catalyst upwards. Wan et al. and Sn 49.69.1 (2003) with permission from IOP publishing Ltd.43. The growth of nano-tetrapod was also found in a catalyst free process.69-76 In this process. In a wet-oxidation process.

where the epitaxy energy is minimized. With photolithography technique. HRTEM study (Fig. These issues will be further discussed in the next section.The SEM image of the as-synthesized nanowires with uniform diameters is shown in Fig. Inset: a ZnO nanowire with diameter of 35 nm and terminated with an Au nanoparticle. As mentioned above. To control the locations of ZnO nanowires.14 In addition. 3. 3b. alignment and packing density. which is a clear indication of the VLS process. then small diameter ZnO nanowires were grown from the patterned 4 . (c) High resolution TEM image of a ZnO nanowire shows growth direction along [0001]. they have been achieved by catalyst assisted VLS synthesis process. the diameter of nanowires can be tuned by using different sizes of nanoparticles or nanocluster catalysts. 2. (a) Schematic of VLS process.2 Patterned Growth and Vertical Alignment of ZnO Nano-Array The application prospect of ZnO nanostructures largely relies on the ability to control their location. The inset SEM micrograph demonstrates that a ZnO nanowire terminates with a Au nanoparticle. Based on the VLS mechanism. (b) SEM image of mesh of ZnO nanowires grown via VLS process. the control of nanowire growth location and alignment has been realized by using patterning techniques and choosing proper epitaxy substrates. 3c) suggests that the nanowires grow along the [0001] direction.73 square and hexagonal catalytic gold dot array was generated on sapphire substrate. both lithographic and non-lithographic patterning techniques have been utilized. Catalyst nanoparticle (a) Alloy with Zinc Zn vapor O2 O2 Nanowire growth ZnO precipitation upon supersaturation (b) (c) Fig.

It is out of question that well-ordered and high density ZnO nanowires array can be obtained using advanced lithographic technique such as electron beam lithography. a 500 nm thick AAM was carefully attached to a GaN substrate. as shown in Fig. For example.74 Fig. this objective can be also realized by simply using non-lithographic shadow mask. (a) (b) (c) 5 .72 In this work. In fact. hexagonal catalyst dot array functioned as nanowire growth sites and resulted in the highly ordered ZnO nanowires array as shown in Fig. 4a. TEM grids were used to pattern square Au matrix. After evaporation of Au. 4c. 4b shows the resulting ZnO nanowire array. have successfully fabricated hexagonal ZnO nanorod array by using anodic aluminum oxide membranes (AAM) as a mask to pattern Au catalyst on GaN substrate. A simple way to create patterned catalysts array is to use shadow masks for catalyst deposition.catalysts via a typical VLS process. Chik et al.

This implies the potential of fabricating n-ZnO/p-GaN nanoscale heterojunctions.. 6 demonstrates the corresponding results. Table 1 gives the crystal structures.74 GaN.14. this structure has been implemented in ZnO nanorod electroluminescence device. Using AAM to fabricate metallic and semiconducting nanowire/nanotube array has been widely investigated. 1348 (2004) with permission from Wiley-VCH Verlag GMBH & Co.72 Another unique non-lithographic method to grow vertical aligned ZnO nanowire array combines monolayer self-assembly and VLS nanostructure growth.48. Vertical aligned ZnO nanowires/nanorods have promising applications such as electron field emitter. (b) Square ZnO nanowires array created using TEM grids. Reprint from ref. Lett.37. the substrate was placed in a thermal furnace and undergone a VLS synthesis with ZnO powder and graphite powder as source. J.72.71 SiC 47 and Si substrate. 73. Vertical aligned ZnO nanowires were observed to grow from lithographically patterned Au spots (Fig.37 6 .. Reprint from ref. thus have attracted enormous attention. Chik et al. After etching away the polystyrene spheres using toluene.37.80 in most cases. Though sapphire has been widely used as the epitaxy substrate for vertical growth of ZnO nanowires. 74.77-79 Ng et al.. The nanowires grown on GaN epilayer show better vertical alignment than those on sapphire. The additional advantage of employing GaN as epilayer instead of sapphire and ZnO rests in the fact that GaN has much better electrical property than Al2O3 and it is much easier to be doped to p-type than ZnO. Greyson et al. as shown in Fig.47.Fig. Phys. demonstrated ZnO nanowire based vertical field effect transistor with surround gate.60. then they functioned as a shadow mask for evaporation of catalytic metal (Au). In fact. 84.61. 4. 5a.74 in which both the sapphire a-plane and GaN (0001) plane were used as epitaxy layer for ZnO nanowire growth. 72. the alignment is realized by lattice matching between ZnO and the substrate. yielding a highly ordered hexagonal array of gold spots. vertical transistor and UV laser. submicron polystyrene spheres were self-assembled on sapphire (2 1 1 0) substrate to form a monolayer.48 In this method. H. Fig. Supperlattice Microst.. (a) Hexagonal ZnO nanowire array generated by lithographically patterned Au catalysts. Appl.47 In their work. H. Fan et al. the positions of nanowires were controlled via lithographic patterning technique. 16. Adv. including sapphire.74 ZnO film coated substrate. 3376 (2004) with permission from American Institute of Physics.66. This has been confirmed by the work of Fan et al. (c) Hexagonal ZnO nanorod array with diameter ~60 nm and spacing ~110 nm. Although the vertical alignment of ZnO nanostructures can be assisted by an electric field. 5b. Apparently the quality of vertical alignment is mainly determined by the lattice mismatch between ZnO and the supporting substrate. These nanowires were later surrounded with SiO2 and Cr which function as the gate oxide and gate electrode. Mater. E.48. Reprint from ref. lattice parameters and mismatch between ZnO (0001) plane and several epitaxy substrates. It was shown above that the highly ordered vertical ZnO nanowire array had been obtained by a non-lithographic AAM based second-order self-assembly of ZnO nanorods. 5a). The photoluminescence and lasing property of the nanowires array were investigated. C..81-84 Yang et al. Several types of epitaxy substrates have been utilized. as depicted in the inset of Fig. it can be seen that GaN could be an even better candidate since it has the same crystal structure and similar lattice constants to that of ZnO. 95 (2004) with permission from Elsevier. have grown vertical aligned ZnO nanowires array on sapphire (1120) plane. 36.14.

Reprint from ref. 1247 (2004) with permission from American Chemical Society. T. 5. P.6% [67] (a) (b) Fig. J.3 Other Synthesis Methods 7 . 4. Vertical aligned ZnO nanowires array on (a) sapphire a-plane (b) GaN (0001) plane.. 6.5% [47] Si Diamond a=b=c =0.543 (100) 18.521 (0001) 0 GaN Wurtzite a=0. 323 (2002) with permission from Wiley-VCH Verlag GMBH & Co. 95 (2004) with permission from Elsevier. 47. Reprint from ref. Material Crystal structure Lattice constant (nm) Epitaxial plane Lattice Mismatch ZnO Wurtzite a=0. 74. Ng et al. 12.319 c=0. Mater. Table 1.08% [70] SiC Wurtzite a=0. Lattice parameters of several epitaxy substrates.. Nano.299 (1120) 0. H. Supperlattice Microst.519 (0001) 1.512 (0001) 5. Scale bar: 1 µm. Yang et al. Adv. 2.(a) (b) Fig. 36. Lett.. Reprint from ref..325 c=0.475 c=1. Fan et al. 14. (b) Vertical aligned ZnO nanowires array on sapphire substrate. Inset: zoom in view of vertical ZnO nanowires on GaN substrate. (a) 45° view of an array of individual ZnO nanowires grown from Au catalyst spots. Inset: schematic of a ZnO nanowire vertical transistor.309 c=1.9% [70] Sapphire Hexagonal a=0. H.

Physical Properties of ZnO Nanostructures Table 2 lists the basic physical properties of bulk ZnO. in an electrodeposition method. This sol-gel process was further improved by an electrochemical method in order to obtain nanorods with diameter smaller than 50 nm. 3. etc.86 AAM was also used as the template and immersed into a suspension containing zinc acetate for 1 minute. optical. which has been confirmed by photoluminescence. including mechanical. then the nanowire array was oxidized at 300 °C for 2 hours and ZnO nanowire array was obtained. ZnO nanofibers were eventually obtained after removing the AAM template. some of their physical properties undergo changes known as the “quantum size effects”. as suggested from nanowire chemical sensing studies. and also employ less rigorous synthesis conditions and provide great potential for device applications.Although the vapor transport process is the dominant synthesis method for growing semiconducting nanostructures such as ZnO. have been developed in parallel. forming zinc nanowires array.95 X-ray absorption spectroscopy and scanning photoelectron microscopy reveal the enhancement of surface states with the downsizing of ZnO nanorods.97-99 Understanding the fundamental physical properties is crucial to the rational design of functional devices. polymer assisted growth. In a sol-gel synthesis method.85. quantum confinement increases the band gap energy of quasi-one-dimensional (Q1D) ZnO. electrical. 8 . Investigation of the properties of individual ZnO nanostructures is essential for developing their potential as the building blocks for future nanoscale devices. This section will review the up-to-date research progress on the physical properties of ZnO nanostructures. other growth methods such as electrodeposition.87 These methods are complementary to the vapor transport synthesis of ZnO nanostructure.93 It is worth noting that as the dimension of the semiconductor materials continuously shrinks down to nanometer or even smaller scale.86-92 These methods provide the possibility of forming ZnO nanostructures at low temperature.96 In addition. magnetic and chemical sensing properties.85 AAM with highly ordered nanopores was used as a template.72. zinc nanowires were fabricated into the nanopores via electrodeposition.94 Bandgap of ZnO nanoparticles also demonstrates such size dependence. piezoelectric. For example. sol-gel. For example. the carrier concentration in Q1D systems can be significantly affected by the surface states. then heated in air at 120 °C for 6 hours. GaN and Si nanowires.

52069 nm 5. Hughes et al. 7. 100 In this method.66 3.101 This shows the prospect of its application as a highly sensitive atomic force microscopy (AFM) cantilever. and resonant oscillation was achieved by tuning the driving frequency. Based on an electric-field-induced resonant excitation. Following the classical elasticity theory.Table 2.606 g/cm3 2248 K 8. Physical properties of wurtzite ZnO Properties Lattice constants (T = 300 K) a0 c0 Density Melting point Relative dielectric constant Gap Energy Intrinsic carrier concentration Exciton binding Energy Electron effective mass Electron mobility (T = 300 K) Hole effective mass Hole mobility (T = 300 K) 0.24 200 cm2/V s 0. direct < 106 cm-3 60 meV 0. bending modulus was calculated. This electric field drove the vibration of the nanobelt. a special TEM sample holder was made to apply an oscillating electric field between a ZnO nanobelt and a fixed electrode. Bai et al. ZnO nanobelt demonstrates to be a promising material as nanoresonator and nanocantilever. characterized the bending modulus of ZnO nanobelts using TEM.1 Mechanical Properties Direct measurement of the mechanical behavior of individual nanostructures is rather challenging since the traditional measurement method for bulk material does not apply. Its small size renders improved sensitivity compared with conventional cantilever fabricated by microtechnology. as depicted in Fig.4 eV.32469 nm 0.59 5-50 cm2/V s Value 3. 9 . reported manipulation of ZnO nanobelt to desired length and position.

8.νy= 691 KHz. its piezoelectricity has been extensively studied for various applications in force sensing. acousto-optic modulator. 7 . (d) Resonance peak of a ZnO nanobelt. X. Phys.110 The piezoelectric coefficient of ZnO nanobelts was measured by AFM with conductive tips. thus a macroscopic dipole moments appears over the whole crystal. νx= 622 KHz. In such a non-centrosymmetric structure. Reprint from ref. 3. ZnO nanobelts were deposited on a conductive substrate.103 The piezoelectric property of ZnO nanostructures was also investigated for their potential applications in nano-electromechanical systems. then the whole substrate was coated with 5 nm thick Pd serving as top electrode on the nanobelt. etc. (c) the first harmonic resonance in y (width) direction. D.2 Piezoelectric effect and polar surfaces As one of the important properties of ZnO. Bai et al. 100. acoustic wave resonator. This displacement results in local dipole moments. among the tetrahedrally bonded semiconductors.102-109 The origin of the piezoelectricity lies in its crystal structure. In fact. Lett. ZnO has the highest piezoelectric tensor which provides a large electro-mechanical coupling.TEM images of a ZnO nanobelt at (a) stationary (b) the first harmonic resonance in x (thickness) direction. Appl. After the 10 . the center of positive charge and negative charge can be displaced due to external pressure induced lattice distortion (Fig.Fig.6. 4806 (2003) with permission from American Institute of Physics. 8a).. 82.110 As depicted in Fig.34. in which the oxygen atoms and zinc atoms are tetrahedrally bonded.

. (c) Schematic of using AFM to measure the ZnO nanobelt piezoelectric coefficient. the position of positive charge is displaced from that of negative charge and the direction of displacement is also [0001]. the charged (0001) surface results in unique nano-ring and nano-coil structure. Wang et al. These tetrahedrons stack along [0001] direction.. 11 . In order to achieve minimized energy. Zhao et al. Nano Lett. Reprint from ref. Another interesting result of the non-centrosymmetric ZnO crystal structure is its spontaneous polarization and polar face dominated nanostructures. as shown in Fig. Funct. 110.. d33. 8. The net result of this spontaneous polarization is a charged (0001) ZnO surface. 4. M. (a) Schematics showing the piezoelectric effect in a tetrahedrally coordinated cation-anion unit.34. As the result. Adv.112 As mentioned before. 14. for ZnO nanobelt and its comparison with that of bulk. 8b). (b) Measured piezoelectric coefficient. Reprint from ref.nanobelt was located by AFM.6. Mater. Due to spontaneous polarization. Z. 943 (2004) with permission from Wiley-VCH Verlag GMBH & Co. the effective piezocoefficient of nanobelt is observed to be frequency dependent and much larger than that of the bulk (0001) surface (Fig. the crystal structure of ZnO can be visualized in a way that oxygen atoms and zinc atoms are tetrahedrally bonded. 6. (a) (b) (c) Fig. 587 (2004) with permission from American Chemical Society.111. L. H. piezoresponse force microscopy was used to measure the effective piezocoefficient of the (0001) surface of the nanobelt. 9.

113-117 Single ZnO nanowire was configured as field effect transistor (FET) following several procedures. Adv. the electrical properties of ZnO nanowire FETs were studied using conductive AFM. 14. a scanning tip was capable to switch on and off the conductance periodically (Fig. Long range electrostatic force between the polar surfaces induces formation of b) nanorings.35. 10d).Fig. The schematic of the structure of a fabricated nanowire FET combined with the measurement circuit is depicted in Fig.. and d) nanohelixes of ZnO. Furthermore. 10c and carrier concentration and mobility are estimated. Due to the native defects such as oxygen vacancies and zinc interstitials. ZnO nanowires are reported to show n-type semiconductor behavior. Fig. Well defined transfer characteristics are shown in Fig.c and d are SEM images of these nanorings. 6. (a) Model of a polar nanobelt with top and bottome surface ±(0001) planes. 3. indicating the potential application for a nano-electro-mechanical system. The bottom graph of b. 9. rendering them superior 12 . Reprint from ref. nanospiral and nanohelixes. 10a. Furthermore. then deposited onto a SiO2/Si substrate.10b shows I-V characteristics under different back gate voltages.3 Electrical Properties The fundamental study of the electrical properties of ZnO nanostructures is crucial for developing their future applications in nanoelectronics. L.. The CVD grown ZnO nanostructures are single crystalline.72 They were first dispersed in isopropanol alcohol to form nanowire suspension. Funct. 943 (2004) with permission from Wiley-VCH Verlag GMBH & Co. Wang et al.72. Photolithography was utilized to define contact electrode array and degenerately doped Si substrate functioned as a back gate electrode. Mater. c) nanospiral. Electrical transport measurements have been performed on individual ZnO nanowires and nanorods.118 the local electrical potential was mapped and the uniformity of nanowire electrical property was demonstrated. Z.

0 100 50 0 Vg (V) Time (s) 13 .35 And Park et al. electrically driven nanowire laser can be potentially implemented. an electron field effect mobility of 7 cm2/V·s is regarded quite high for ZnO thin film transistors. with a Ga and N codoping method. P-type and n-type ZnO nanowires can serve as p-n junction diodes and light emitting diodes (LED).5 1. For example.35 The major impediment of ZnO for wide-ranging applications in electronics and photonics rests with the difficulty of p-type doping. Combined with their optical cavity effect. Consequently. single crystalline ZnO nanowires show mobility as high as 80 cm2/V·s.0 1. And field effect transistors (FET) fabricated from them can constitute complementary logic circuits. Furthermore. Several p-type doping efforts have been reported. using a uniquely designed synthesis setup. An effort to fabricate intramolecular p-n junction on ZnO nanowires was made by Liu et al. the I-V characteristics demonstrated rectifying behavior due to the p-n junction within the nanowire. anodic aluminum membrane was used as a porous template with average pore size around 40 nm. low resistivity (0.electrical property than polycrystalline thin film.120 Kim et al. providing a way to modify the electrical property. A two step vapor transport growth was applied and boron was introduced as the p-type dopant. 10c). had reported an electron mobility of 1000 cm2/Vs after coating the nanowires with polyimide to reduce the electron scattering and trapping at surface. one can tune the carrier concentration and mobility of the nanowires (Fig. reported nitrogen-doped p-type ZnO obtained by molecular beam epitaxy with a hole mobility of 2 cm2/V·s.121 Successful p-type doping for ZnO nanostructures will greatly enhance their future applications in nanoscale electronics and optoelectronics. reported phosphorus-doped p-type ZnO with a thermal activation process.12 However.5 Ω·cm) p-type ZnO thin film was obtained.5 2.0 0.113 In this case. (a) 400 0 (b) Vg=-6 V Vg=-4 V Vg=-2 V Vg= 0 V Vg= 2 V Vg= 4 V Vg= 6 V I (nA) -400 -800 -1200 -1600 -4 -2 0 2 4 Vds (V) 200 150 (c) A 14 12 (d) Vds Vtg I (nA) I (nA) B -20 -10 0 10 20 10 8 6 4 2 0 0.117 These results indicate that the ZnO nanostructure based device can achieve a faster operation speed than their thin film counterpart.119 Look et al.

11b. and the emission current reached 1 mA/cm2 at 11 V/µm. 11a. reported better results for ZnO nanowire synthesized at low temperature. These nanowires were subject to field emission measurement. 122 The as-grown nanowires showed well-aligned vertical structure as shown in Fig.122-128 Tseng et al. 10. electric field emission from vertically-aligned ZnO nanowire/nanorod has also been extensively investigated.Fig. Interestingly. Quasi-one-dimensional (Q1D) nanomaterial with sharp tip is a natural candidate for electron field emission. which could provide sufficient brightness as flat panel display. In addition to electrical transport studies. as shown in Fig.01 µA/cm2. (a) AFM image of a ZnO nanowire FET combined with the schematic of the measurement circuit.58. This improved emission performance was attributed to the higher aspect ratio of tetrapod structure than that of nanowires.59 a low turn-on field of 1. (b)I-V curves of a ZnO nanowire FET from Vg = -6V to 6V.6 V/µm at current density of 1 µA/cm2 was reported. (d) A demonstration of periodic modulation of the nanowire conductance by a scanning probe. The inset is a schematic of the measurement set up.66 A turn-on field of 6 V/µm at a current density of 0.62. (a) (b) 14 . field emission from vertically-aligned ZnO nanoneedles and nanowires have been investigated by many groups. and nanowire B has a mobility of 22 cm2/V·s and carrier concentration ~107 cm-1. In fact. the turn-on field was found to be ~18 V/µm at a current density of 0. Nanowire A has a mobility of 80 cm2/V·s and carrier concentration ~106 cm-1. grew needle-like ZnO nanowires on Ga-doped ZnO film at 550 °C.66. in the electron emission from ZnO nano-tetrapod. Lee et al.1 µA/cm2 was obtained. and the emission current could reach 0.1 mA/cm2 at 24 V/µm. (c) Change of the transfer characteristics of two nanowires grown in different synthesis conditions.

Y.-K. 13. and Liu et al.Fig. Interestingly. ZnO nanowire/nanorod is a natural candidate for optical waveguide.143 Optically pumped light emission was guided by ZnO nanowire and coupled into SnO2 nanoribbon (Fig.141 Recently. ZnO nanowires were reported as sub-wavelength optical waveguide. Optical waveguiding using dielectric nanowire also achieved considerable progress. Adv.129-138 Excitonic emissions have been observed from the photoluminescence spectra of ZnO nanorods. 11. PL spectra show that ZnO nanowire is a promising material for UV emission. Besides UV emitting and lasing.4 Optical Properties Intrinsic optical properties of ZnO nanostructures are being intensively studied for implementing photonic devices. (b) Emission I-V characteristics of ZnO nanowires. 811 (2003) with permission from Wiley-VCH Verlag GMBH & Co.14. These findings show that ZnO nanostructures can be potential building blocks for integrated optoelectronic circuits. This behavior is one of the characteristics of Q1D systems and renders them promising application in high contrast polarizer.79 Huang et al. These results are consistent with those of bulk ZnO. Reprint from ref. red luminescence band was reported.0). (a) Vertically-aligned ZnO nanowires on Ga-doped ZnO film. as one of the characteristics of nanoscale systems. which was attributed to doubly ionized oxygen vacancies. Photoluminescence (PL) spectra of ZnO nanostructures have been extensively reported. quantum confinement was observed to cause a blue shift in the near UV emission peak in ZnO nanobelts..77. From the photoconductivity measurements of ZnO nanowires. the green emission intensity increases with decreasing nanowires diameter.c).94 as illustrated in Fig.144 Defect state related visible wavelength detection and polarized photodetection of ZnO nanowires were also observed (Fig. 3.112.140 Strong emission peak at 380 nm due to band-to-band transition and green-yellow emission band related to oxygen vacancy are observed. This observation is attributed to the larger surface-to-volume ratio of thinner nanowires favoring a higher level of defects and surface recombination. Funct.14. The well-facetted nanowires also form promising optical resonance cavities which greatly facilitate highly directional lasing at room temperature in well aligned ZnO nanowires.. Tseng et al. 12d).14.78 Lasing power threshold of 40 kW/cm2 ~ 100 kW/cm2 was reported and it was suggested that higher crystal quality confers lower threshold. reported room temperature UV lasing from ordered ZnO nanowires array. while its UV lasing property is of more significance and interest. it is found that the presence of O2 has an 15 . 12a. The additional advantages of ZnO nanowire lasers are that the excitonic recombination lowers the threshold of lasing. 12b.142 Photocurrent is maximized when the electric field component of the incident light is polarized parallel to the nanowire long axis.139 It is shown that quantum size confinement can significantly enhance the exciton binding energy. effort on utilizing ZnO nanowires for UV photodetection and optical switching have been reported by Kind et al.142 In addition. Due to its near-cylindrical geometry and large refractive index (~2. Recently. Mater. 122. and quantum confinement yields a substantial density of states at the band edges and enhances radiative efficiency.

while the photogenerated electrons significantly increase the conductivity. 85. B 108. O2 surface adsorption on the nanowires could significantly expedite the photocurrent relaxation rate. When illumination is switched off. Wang et al. 1269 (2004) with permission from American Association for the Advancement of Science. Science 305. (a) (b) ZnO nanowire ZnO/SnO2 junction SnO2 nanowire (c) 1600 1400 (d) With halogen light 28 24 (e) Current (nA) 80 Turn off laser 60 40 20 0 Turn on laser 0 20 40 60 Time (min) Vds=0. Reprint from ref. 142. Z. 16 . (d) Polarized photodetection of both UV (365 nm) and visible light show that nanowire conductance is maximized when incident light is polarized parallel to the nanowire axis. Chem.145 i. 12. (e) Nanowire photoresponse to 633 nm laser in air compared to that in vacuum (inset). It was found that the desportion-adsorption process of O2 affects the photoresponse of ZnO nanowire. M. Reprint from ref. Fan et al. Appl. 8773 (2004) with permission from American Chemical Society. J.important effect on the photoresponse. 143. As shown in Fig. Upon illumination. O2 molecules re-adsorb onto nanowire surface and reduce the conductivity. Phys. Phys.. (a) PL spectra of 6 and 200 nm wide ZnO nanobelts show a blue shift of the emission peak..25V 150 200 Polarization Angle (degree) Time (s) Fig. the photocurrent relaxation time is around 8 s in air but hours in vacuum. X. Lett. (b) A PL image of a ZnO nanowire guiding light into a SnO2 nanoribbon and (c) a SEM image of the wire-ribbon junction.. 94. Reprint from ref. 6128 (2004) with permission from American Institute of Physics. 12e.115.e. photogenerated holes discharge surface chemisorbed O2 through surface electron-hole recombination.25V Current (nA) Current (nA) 1200 20 16 Vds= 5 V 1000 800 600 0 30 60 90 120 With 365 nm UV E NW With 633 nm 12 8 80 E NW Vds= 2 V 150 180 4 0 50 100 Vds=0.142. Law et al.

13. 3. Q1D ZnO. These vacancies function as n-type donors. Lett. is expected to be superior to its thin 17 . Y. Because of its wide band gap. Room temperature hole mediated ferromagnetic ordering in ZnO by introducing manganese (Mn) as dopant has been predicted theoretically20. electrons are effectively depleted from the conduction band. From the aspect of sensing performance. such as CO and H2. Most metal-oxide gas sensors operate based on this principle. 83 4020 (2003) with permission from American Institute of Physics. NH3 17. Reprint from ref. 13. often significantly increase the conductivity of oxide. 151.3.150 were used as dopants.5 Magnetic Doping Dilute magnetic semiconductors (DMS) are attracting increasing research interests because spin-polarized DMS can accomplish efficient spin injection as well as overcome the conductance mismatch associated with semiconductor devices. It has been found that ZnO is a promising host material for ferromagnetic doping. leading to a reduced conductivity of the n-type oxide. molecules.146 and reported experimentally by Sharma et al. Phys. The effort of growing ferromagnetic Zn1-xMnxO (x=0.13) nanowires with Curie temperature of 37 K was reported by Chang et al. ferromagnetic ZnO is regarded as an excellent material for short wavelength magneto-optical devices.153 Fig. Chang et al. in ZnO thin film.. would react with surface adsorbed oxygen and consequently remove it.148 and Fe 149. such as nanowires and nanorods.152 These studies enable the use of magnetic ZnO nanowires as nanoscale spin-based devices. Q. bulk and thin films of ZnO have been proposed for CO 16. On the other hand. such as NO2 and O2. Upon adsorption of charge accepting molecules at the vacancy sites.21 Ferromagnetism in ZnO was also observed when Co 147. alcohol 18 and H2 19 sensing under elevated temperature (~400 °C). Appl. As one of the major materials for solid state gas sensor. leading to an increase of conductivity. Inset: Magnetization-Field hysteresis loop obtained at 5 K demonstrates ferromagnetism by Mn doping.6 Chemical Sensing Oxygen vacancies on metal-oxide surfaces are electrically and chemically active. 151 and shown in Fig. Temperature dependent magnetization curve of Zn1-xMnxO (x=0.13) nanowire at 500 Oe field shows Curie temperature of 37K. The nanowires were synthesized via a vapor phase evaporation method.

14a).83 wt% was achieved at a pressure of 3.114 Fan et al. Under an operation temperature of 300 °C.98 Since their diameter is small and comparable to the Debye length. Wan et al. This implies that the gate voltage can be used to adjust the sensitivity range. but also facilitates potential hydrogen storage property. above gate threshold voltage of FET. Electrical transport studies show that O2 ambient has considerable effect on the ZnO nanowires.97 As demonstrated in Fig. 14b.0 0.e. The gas selectivity for NO2 and NH3 using ZnO nanowire FET was also investigated under the gate refresh process.4 -0. Massive nanowires were placed between Pt interdigitating electrodes. Furthermore. 14a inset). thus confer Q1D ZnO higher sensitivity than thin film. It was suggested that hydrogen storage was due to not only surface adsorption but also the incorporation of H2 into the crystal interstitial sites. Recently. investigated hydrogen storage characteristics under room temperature. discussed the relationship between oxygen pressure and ZnO nanowire FET performance. it is observed that the sensitivity is a function of back gate potential. the resistance of nanowires significantly decreases upon exposure to ethanol.03 MPa. Wan et al.4 600 10 ppm NO2 (b) T = 300 K 450 I (nA) 300 150 0 -150 -200 0 200 400 600 800 Vg= 0 V Vg= -60 V 1000 1200 1400 1600 Time (s) 18 .2 0..76 It is shown that ZnO nanowires have fairly good sensitivity to O2 (Fig.76. The large surface-to-volume ratio of nanowires not only results in their enhanced gas sensing performance. the conductance of nanowire can be recovered by using a negative gate potential larger than the threshold voltage.2 Vg (V) 4 6 8 Vds (V) 0.film counterpart. exhibiting a gas distinguishability function. i. sensitivity increases with decreasing gate voltage (Fig. In addition.155 The highest storage of 0.154 fabricated ZnO nanowire chemical sensor using microelectromechanical system technology. a gate-refresh mechanism was proposed. In addition. 10 5 10ppm 25ppm 50ppm (a) I (nA) 0 -5 Vg= 0 V Sensitivity (%) 60 45 30 15 0 -2 0 2 -10 -15 -0. chemisorption induced surface states effectively affect the electronic structure of the entire channel. ZnO nanowires and nanorods can be configured as either two terminal sensing devices or as FETs in which a transverse electric field can be utilized to tune the sensing property.

(a) I-V curves of a ZnO nanowire under 50 ppm O2. The authors thank Mr. Fan et al. Continuous effort is dedicated to achieve large arrays of programmable structures for building reconfigurable architectures.. Lett. Encouraging progress on the research of nanostructured ZnO materials have been accomplished as reviewed in this article. 85. and magnetoelectronic devices. P. There are still important issues waiting to be further investigated.. Acknowledgement This work is supported by National Science Foundation. Appl. Z. Integration of ZnO nanostructure building blocks for large scale device applications is another important issue. Phys. Lett. Reprint from ref. Inset: gate potential dependence of sensitivity under 10 ppm O2. Phys.-C. optoelectronic. Last but not the least. 4. Conclusions ZnO offers tremendous potential in future applications of electronic.Fig. Z. obtaining room temperature ferromagnetism and demonstrating spin-polarized transport in ZnO nanostructures will greatly advance future research on spin-based nanoscale devices. One key area is the growth of p-type ZnO nanowires and fabrication of nanoscale p-n junctions for electrically driven nano LED or laser. Fan et al. Chang for helpful discussions. 14. 86. Appl. 19 .5923 (2004) with permission from American Institute of Physics. 76. 97. 123510 (2005) with permission from American Institute of Physics. Reprint from ref. (b) The nanowire sensing response to 10 ppm NO2 and the conductance recovery process assisted by a -60 V gate voltage pulse.

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