Indium Antimonide Nanowires: Synthesis and Properties
© Shafa et al. 2016
Received: 25 January 2016
Accepted: 12 March 2016
Published: 24 March 2016
This article summarizes some of the critical features of pure indium antimonide nanowires (InSb NWs) growth and their potential applications in the industry. In the first section, historical studies on the growth of InSb NWs have been presented, while in the second part, a comprehensive overview of the various synthesis techniques is demonstrated briefly. The major emphasis of current review is vapor phase deposition of NWs by manifold techniques. In addition, author review various protocols and methodologies employed to generate NWs from diverse material systems via self-organized fabrication procedures comprising chemical vapor deposition, annealing in reactive atmosphere, evaporation of InSb, molecular/ chemical beam epitaxy, solution-based techniques, and top-down fabrication method. The benefits and ill effects of the gold and self-catalyzed materials for the growth of NWs are explained at length. Afterward, in the next part, four thermodynamic characteristics of NW growth criterion concerning the expansion of NWs, growth velocity, Gibbs–Thomson effect, and growth model were expounded and discussed concisely. Recent progress in device fabrications is explained in the third part, in which the electrical and optical properties of InSb NWs were reviewed by considering the effects of conductivity which are diameter dependent and the applications of NWs in the fabrications of field-effect transistors, quantum devices, thermoelectrics, and detectors.
The fifteenth anniversary of indium antimonide nanowires (InSb NWs) synthesis was recently monumentalized a good opportunity to review, try to discuss and compile few of its imperative aspects of synthesis, of the growth thermodynamics, of optical properties, and electrical characterizations. The proclamation of a fifteenth anniversary invoked from the synthesis of S.V. Z. Zotov et al.  indium antimonide structure which, as far as we know, shows the earliest communication on InSb NWs synthesis, in which the authors declare effective growth of NWs having 50 Å diameter and 1 mm long. This growth technique has been deduced from the vapor–liquid–solid (VLS) mode which was introduced in the 1960s–1970s for large whisker growth [2, 3]. During that period, the terminology of whisker was commonly used for fiber-like grown structures corresponding to silicon crystals in the dimension of micrometer (see, e.g., the magnificently long wires shown in ). Furthermore, nomenclatures of nanorods have also been utilized instead of terms whisker . Classical name whisker has not been exploited throughout this communication, even though previous studies of these nanostructures were reviewed. Alternatively, the term InSb NWs will be used corresponding to the diameter of wire that was even smaller than a tenth of nanometers. During a generalized way of descriptions, we will use the renowned term NWs which is not limited to a specific size. We will confine our self to the said nomenclature, although not with extreme strictness.
Methods and Materials for InSb NW Growth
Nanowire Growth Techniques
Before exploring NW growth in depth, a concise summary of the various growth techniques is described in the following section.
Chemical Vapor Deposition
Like other synthesis techniques, the word chemical vapor deposition (CVD) comprises of three words, chemical, vapor, and deposition; it means that first precursors are converted into vapor phase, of course at high temperature, and then it is deposited under the flow of carrier gas. In CVD, during growth of InSb NWs, gaseous indium antimonide precursors, such as trimethylindium (TMIn) and trimethylantimony (TMSb) [15, 24], play the role of source materials. It is transported with the help of some carrier gas to the substrate surface at which these source materials react chemically, and it distributes itself into their ingredients as demonstrated in Fig. 2a. Basically, highly crystalline thin films are grown form CVD. To enhance the growth process, gold particles were used as catalyst; however, it may cause anisotropic growth of InSb NWs. CVD permits epitaxial synthesis of InSb NWs, where the growth velocity varies with molar fraction of III/V ratios from 5 to 12  depending on what type of III/V precursors and growth temperature utilized. Furthermore, CVD offers a broad possibility of modifying the properties of the NWs in a controlled manner . A large variety of CVD methods exist which can be categorized by different parameters such as the treatment of the precursor as well as base and operating pressure or since it is a well-known fact that precursors are oxidize quickly which is major issue needed to be resolved first before growth of crystalline InSb NWs starts. Complete removal of oxygen is impossible, but it can be reduced. Specially, it is worth noticing that oxygen-sensitive catalyst materials are advantageous to use for the growth of NWs; due to this significant property, growth can be carried out without exposing growth chamber to ambient during synthesis . To reduce the oxidation significantly during growth, we have to have ultra-high or very high vacuum which facilitates the growth process at elevated temperatures as well as lessens the role of unwanted contaminations .
The amount of precursors transported to the growth surface usually depends upon the cracking probability at the surface of catalyst and source temperature. Synthesis of InSb NWs, must not be but it can be executed at significantly low pressures where highly pure hydrogen gas is used as carrier gas and antioxidant [35, 36] with molar fraction of 1.1 × 10−5 for TMIn and 3.4 × 10−3 for TMSb . Growth can be modified by controlling the precursor before depositing on the substrate surface just by regulation of growth temperature. The situations where droplets must be highly supersaturated or the thermal load is vital, NW synthesis can be enhanced by using metal-organic CVD (MOCVD) [17, 23, 30, 38, 39]. Bottom-up synthesis mechanism is another superiority of CVD in which its variability can be enhanced concerning the intended NW dimensions whereas NW diameter vary from below 10 nm [40–42] up to tens of micrometers in length. In the CVD chamber, the surface diffusions play minor role during the growth of NWs so length of the NWs can be easily tunable simply by increasing or decreasing growth time. Thus, to summarize, CVD is a very effective technique which is used for the synthesis of NWs with tuned diameter and length configurations in a wide range  as well as properties of these grown NWs can also be controlled with the help of this technique. A phenomenon of controlled doping can also be carried out with the help of CVD; for intentionally introducing additional doping materials as well as by switching doping precursors, we can generate doping profiles in any direction. A major drawback of CVD for the growth of InSb NWs is the growth direction which cannot be tuned, as several studies have shown that InSb NWs normally grow in a <111>B direction , depending upon the available direction of those on substrate . To overcome this hurdle, template such as anodic aluminum oxide (AAO)  is used for the growth of InSb NWs where the pore of the templates is filled with catalyst materials to stimulate the NW growth only inside the pores. In this way, NW growth is controlled especially epitaxial growth oriented at (200) which is impossible for free standing growth to be achieved by using this template method. After the growth is done, the template in which these NWs are grown can be washed out with the solution of sodium hydroxide; as a result, standing NWs obtained can be shifted for further characterizations .
Annealing in Reactive Atmosphere
Before 2003, a technique to grow InSb whisker microcrystal free crystallization from a gaseous phase  with the initial iodine pressure of 375 Torr heated source up to 760 °C is already pioneered; at growth temperature, the carrier gases can react in the growth chamber with the precursors that can be doped with several impurities simultaneously (Sn, Al, and Cr) during their growth . This kind of addition of impurity as metal droplet acts as seed to start the synthesis of NWs also observed in the conventional CVD. Being cheap and technically simple are major superiorities of this mechanism, which is surly the logic why it was adopted for InSb microcrystal growth elongated along the (111), (110), and (211) with the dimension of (10 × 0.06 × 0.02) mm . In some sense, this technique can be recognized as the ancestor of NW synthesis by traditional CVD. Nowadays, a modification in this technique is only hot-filament CVD which is schematically demonstrated in Fig. 2b .
Evaporation of Indium Antimonide
To vapor the indium antimonide powder is the cost-effective technique for the growth of InSb NWs on a massive scale whose schematic diagrams are shown in Fig. 2c. Simplistic way to vaporize precursors is a use of multiple-zone tube furnace supplied with inert gas (helium or argon), and precursors in the form of InSb powder are the primary requirements for the growth of NWs. Temperature gradient is a critical factor which generally varies from growth temperature of about 1100 to 400 °C along the furnace tube for vaporization of precursor. InSb powder is placed at high source temperature of 550 °C and evaporated under the flow of gas stream towards seeded substrates placed at significantly low temperature of 470 °C which is called growth temperature in downstream, where precursors undergo a nucleation reaction; as a result, NWs are synthesized [47, 48].
In principle, growth with and without a metal catalyst are the two permissible growth methods. It is generally observed that NW growth is rapid in the presence of a catalyst  in accordance with the fact of vapor–liquid–solid synthesis mechanism where the radius of NWs is measured by the size of the catalyst particle; although compared to conventional CVD growth, the interplay between the NWs and metallic catalysts seems to be more complicated. Due to the phenomenon of nucleation reaction, diametric ratio of NW crystalline core and the shell residing on the top remains constant [10, 49].
Catalyst-free growth, second phenomena for NW growth via tip-led process of individual NW, is necessary for avoiding contaminations in metal-organic chemical vapor depositions [24, 50, 51], where it was observed that NWs can be grown by using antimony cluster as catalyst on their tip. Remarkable about this layer-assisted growth is that the yield of the final amount of InSb NW length as well as diameter is sufficiently high  compared to metal-assisted growth . For several micrometer-long crystalline InSb NWs with diameters varying from about 300 to 500 nm and 4–5 μm in length, the growth process should be carried out for a longer time which may also increase the diameter of the NWs, enclosed with amorphous coating of precursors up to few 10 nm .
Molecular Beam Epitaxy
In this technique, a highly pure solid indium and antimony sources are heated until it start to evaporate. Figure 2d schematically represents a molecular beam epitaxy (MBE) configuration. During growth, controlled gaseous beams of indium and antimony atoms are targeted at the substrate, on which the precursor’s atoms crystallize as well as adsorb. Base pressure should be kept at ultra-high vacuum during the growth, to diminish the effect of contamination, while reflection high-energy electron diffraction monitor the growth of thin films  or low-energy electron-beam diffraction to investigate the surface structure. Analogous to CVD, this technique was also designed for layer by layer epitaxial growth only. With the passage of time, metal contamination was introduced on substrate to cause NW growth similar with CVD, due to nucleation of precursor gases at the surface of the liquid metal–alloy. Hence, in the recent ages, this technique becomes very conventional and can be used as a traditional seed particle to stimulate the growth. In the chamber, two fluxes have been used for the growth of InSb NWs. First, the indium is vaporized from the solid source; and the other one is the antimony in vapor state which comes out from solid sources in growth chamber equipped with ultra-high vacuum. The NWs fabricated by MBE—generally grown on InP(111)B substrates—are epitaxially oriented at (111) . MBE provides magnificent flexibility to limit incoming flux, such that pure InSb NWs or heterostructures [52, 53] can be synthesized just by changing the flux of sources. In fact, MBE could be used to grow high-quality ultrathin InAs NWs . Very recently, thin InSb NWs with diameter down to 30 nm in a heterostructure with an InAs NWs are realized by MBE , which seems to be a consequence of the Gibbs–Thomson effect, and the fact that only small supersaturation are attainable by MBE. Major drawback of MBE growth is the very slow growth rate of NWs, that is, we can grow only few nanometers of NWs in length per minute .
Chemical Beam Epitaxy
In this synthesis mechanism, a highly pure solid antimony source and gaseous Indium sources are used as shown in the Fig. 2e. The InSb NWs grown by chemical beam differ in many aspects from the NWs grown by MBE, as CBE have digital mass flow controller with a high growth rate, while in contrast to MOVPE, the temperature window is significantly broad  and there is no need for carrier gas . In CBE, metal-organic precursors are directly induced into a chamber without use of carrier gas. TMIn and TESb are used as precursors, where TESb is pre-cracked at 625 °C to get homogenous compositions . TMIn, in contrast, is introduced into the growth chamber through an injector held at about 70 °C. The decomposition of TMIn starts at temperatures around 300 °C . Following the VLS growth technique, just after supersaturation of the catalyst with InSb atoms, NWs start to grow and this growth proceeds as long as liquid phase of catalyst remains. NWs grown by CBE method have a lot of advantages: first, there is a high growth rate, and due to low pressure a ballistic mass is transported to substrate. Second, the ingredients of the grown NWs can be adjusted with the help of digital mass controller . Ex situ high-resolution transmission electron microscopy (HRTEM) used to investigate the defects in NWs that are grown by CBE .
Synthesis of NWs can also be done within liquid media for which vapor phase is not necessary. The major drawbacks with the abovementioned techniques are of a fundamental difficulty in achieving a controllable stoichiometric growth of InSb NWs which are a narrow range of temperature processing, formation of the thin In2O3 layer on the surface of NWs, and differences in vapor pressure of In and Sb [59, 60]. To avoid all these complications, solution methods for synthesis of InSb NWs with controlled stoichiometry and high crystallinity are desirable. As one of the promising alternative strategies to avoid these problems and synthesize high crystalline InSb NWs, the electrochemical deposition inside nanoporous anodic aluminum oxide (AAO) templates has been considered [8, 40, 61–63]. These solution-based synthesis methods are preferred for high-yield InSb NWs. Such kind of methods utilizes supercritical organic fluids which are highly pressurized, enriched with a liquid indium and antimony as precursors, such as antimony trichloride and indium(III) chloride, and nanoparticles of metal catalyst [44, 64], as shown in Fig. 2f. In this phase diagram, at temperatures over the metal–InSb eutectic, the precursors decompose and form composite with gold that act as a working electrode. By comparing this method with VLS growth technique, the composite seed catalysts in this supercritical–fluid–liquid–solid (SFLS) mechanism originate the growth of InSb NWs once the composite droplet acquired supersaturated phase with indium antimonide . Using this approach, one can synthesized crystalline NWs with diameters up to 50 nm and several micrometers long . Identical to the VSS synthesis technique, growth of InSb NWs via a metallic seed particle has also been indicated for the liquid-based technique in which micrometer-long NWs were grown at a temperature of merely 550 °C under pressure of 15 kbar using gold as catalysts . Solution–liquid–solid (SLS) method is another high-yielding NW production method. By using this method, under atmospheric pressure, an organic solvent is used for the synthesis of micrometer-long crystalline NWs with 50 nm in diameter, which has been demonstrated . This cost-effective techniques for NW production, as it can be carried out with a sufficiently less expensive apparatus.
Top-Down Fabrication Methods
In the preceding section, a lot of discussions have been made for bottom-up growth mechanism while several attractive top-down synthesis methods also exist for the growth of single crystalline InSb NWs. Due to the diversity in the growth techniques, one should easily differentiate between the fabrications of horizontal NWs, that is, NWs lying in the substrate plane with the growth of vertical NWs, that is, NWs oriented perpendicular to the substrate. During the top-down fabrication method, InSb NWs are mostly fabricated by focused ion beam irradiation of InSb wafer [65, 66] or by lithography and then etching steps, with the help of reactive ion etching after electron-beam lithography . This phenomenon of lithography is simply described here because the detail of it is far from the contents of this article. The interested reader is referred to the well-renowned articles of J. H. Wu and R. S. Goldman  and the references therein. In most cases, on irradiation of InSb surface, cone-shaped nanorods evolved are capped with In islands. During irradiation, with the diameter of nanorods increasing in ion energy, the cone-shaped nanorods transformed to capless nanorods with a truncated cone shape. These results suggest a growth mechanism in which both the nanorod cap and body are supplied by redeposition of atoms sputtered from the InSb substrate using 3–30 KeV ion beam energy during irradiation [65, 66]. Lithography step can also be defined as the diameter of NWs/nanorods which varies from 200 to 400 nm followed by reactive ion etching. Numerous nanofabrication techniques, such as nanosphere lithography , electron-beam lithography , colloidal dispersion , are also used for the fabrication of NWs.
Gold as Catalyst
As the prior declaration of Wagner and Ellis  in which gold has been used as catalyst for NW growth, it is still no doubt that gold have been used as catalyst materials on a large scale. Of course, gold as catalyst is well renowned and most commonly used as seed particles to enhance the growth of low-dimensional structure, or at least easily available, and directly be used for NW growth; but the question that arises here is that, why Au catalyst is flawless remains unanswered. We will also discuss afterwards that it is productive to take deep scrutiny of the Au–InSb system; as a result, we will determine the standard method that can be used for the metallic catalysts.
First of all, from a purely practical point of view, we will demonstrate few advantages in favor of using gold as catalyst. Availability of Au catalysts makes it more famous as well the due to the extremely low resistance of the gold which makes it attractive for its application during device fabrication especially for electrical contacts. Many research institutes have evaporation systems equipped with gold nanoparticles. Thus, it is easy to deposit thin layer of gold film on sample substrate. Alternatively, one could use colloid nanoparticles with diameters ranging from 1 to 250 nm, which in the case of gold, are easily available (for example see, ref. ). High chemical stability and non-hazardous in nature are silent features of gold which make it an ideal candidate for electrode material . Although seemingly trivial, the handling of samples is a most important issue. It is worth noticing to use such catalyst materials that cannot easily oxidize when exposed to ambient, when the regrowth processing of a sample is necessary. Furthermore, the excellent chemical stability of gold nanoparticles  decreases many mechanical modifications of the growth chamber, particularly with regard to reducing the background pressure of oxygen. Moreover, for the use of gold as catalyst, the safety requirements are low as gold is comparatively less poisonous .
To conclude this section on the phase diagram comprehensively, the major influence of the gold as catalyst is that it is nontoxic, chemically inert, and easily available; low melting point and hence vapor pressure also need to be considered, and solubility of gold in the InSb as well is also considered a lot as it results to a sufficiently high surface tension . Unfortunately, the major drawback of the gold is that it is considered as an impurity in NWs [77, 78], when these NWs are used for further device fabrication. Here, a thorough list that used gold as a catalyst material for the synthesis of InSb NWs has been reported [8, 10–16, 30, 37, 39–41, 44, 52, 53, 55, 56, 62, 68, 79–109].
Alternative Catalyst Materials
Thermodynamics of Nanowire Growth
Expansion of the Nanowire
During the initial phase of growth, in the VLS growth mechanism, expansion of the NW base offers a model role for the interaction between seed catalyst and NWs. However, before starting the growth topic, some background knowledge like surface free energy, surface tension, and stress is needed because these terms generally root misperception. These confusions arise because, unlike in liquid crystals, the surface free energy and surface tension or surface stress are not essentially equal. This said statement has already been revealed by Gibbs  and later analyzed also by Shuttleworth . The work of creating a new area is called surface free energy; for example by piercing, surface fatigue is related to elastic deformation that is the also known as extension in the surface dimensions . To investigate the properties of this increase in surface area, surface stress tensor can also be used. For isotropic surfaces, this tensor is converted into scalar called surface stress. The author will ignore that distinction by randomly assigning it as the surface tension of the crystalline solids. In addition, the brief overview of line tension was also first revealed by Gibbs in which he discloses  that τ line tension must be allocated to isolating lines among diverse phases that are completely matched to the theory of surface tension. In focused research work, this describes the dimension of catalyst with indium antimonide interface, where liquid, vapor, and solid phases are associated. At equilibrium conditions, after introducing, the line tension plays a leading role for understanding the term “t/r” where r represents radius of connected line. Limitation of the line expansion is generally assessed in the range 1 × 10−11–1 × 10−9 Jm−1 . So it can be realized that in comparison with surface tension which is commonly 1 Jm−2, line tension can be ignored as the radius is too small of a nanometer; even then, it is still not clear that how much line tension plays their role!
This subsection is interesting to sketch the way for our growth and methodology of InSb NWs epitaxially grown on InP substrate with (111)B orientation, namely that InSb NW radius increased in that specified location that is at the heterojunction . In fact, expansion in the body of NWs arises if it is grown by VLS technique. Without recommendation of VLS synthesis technique, one might be curious to consider that this diameter increase has been accredited to an increased particle volume due to the uptake of indium and to the rotation of the NW sidewalls [83, 87]; radial growth is precisely controlled by applying the molarity ratio of V/III, and the droplet volume enlarges due to indium uptake and conclusively to an increase of the NW diameter , as phase diagram predicts that AuIn2 is a stable phase . An argument, however, speaks against this, put forward by P. Caroff  that the weak requirement of the diameter on the axial growth rate specifies surface dissemination from the substrate, which does not affect the InSb NW growth. Gibbs–Thomson mechanism effects on the elemental have potential difference within the seed particle . It is also believed that this diametric increase is caused by the addition of antimony . On the other hand, radiuses of the grown wire scale with the expansion. Therefore, Givargizov deduced that “whisker root expansion was due to over growth which is related to the contact angle symmetry” . It is concluded from the above discussion that contact angle—angle between catalysts and substrates—plays a major role to set the dimensions of the NWs for example for the growth of InSb NWs, the droplet on InP substrates. According to Nebolsin and Shchetinin  for stable growth of NWs, contact angle should be greater than 90°. In comparison, as can be realized, for example, in the reported work of S. Vaddiraju , it indicates that the increase in the size of the droplet could be due to the change in the wetting behavior and hence in the contact angle between the underlying crystal and molten metal droplet as the growth proceeds .
Growth Velocity and Gibbs–Thomson Effect
When an atom of the same species is added in the system, an energetic barrier exists known as chemical potential μ which is the minimum energy required for an incoming atom to become a part of the existing system. Thermodynamical effects play their role when surface-to-volume ratio is so large that the system under observation is nanoscale, which means that N the total number of atoms increases and hence surface area also. A catalyst in general when NWs start to grow is in spherical shape having a volume of 4π/3R 3 − NΩ where R is the radius and Ω being the volume per atom (assumed to be constant here), the Gibbs-free energy G can be written as G = μ ∞ N + 4πR 2 δ, with δ being the surface free energy and μ ∞ being the bulk (infinite radius) chemical potential. Using ∂R/∂N = Ω/(4πR 2), one can easily find that the chemical potential μ = ∂G/∂N becomes μ = μ ∞ = 2Ωδ/R. This is the Gibbs–Thomson effect.
Here V eq = J eq Ω S is the steady state desorption rate and ϕ = J/J eq − 1 is the saturation in the current suspension segment w.r.t. the solid state. As described in , our direct and efficient equation comprises the 1/R diffusion span due to the exterior adatoms, while the dissemination of superficial surface adatoms is defined by the 1/R and 1/R 2 relations ascending differently with the radius. Also, the dissemination relationship is altered to demonstrate the significant correct way of diffusion flow rates provisional on the action in the drop. The use of estimation of immediate nucleation permits us to abolish the unknown ζ, thus eluding a difficult technique of balancing the entering physical flux of indium particles by their nucleation-mediated droplet .
Surface Energies and Crystal Structure of Nanowire
Electrical and Optical Properties of InSb NWs
Physical properties of InSb NWs need attention after their successful growth. In this section, optical and electrical properties and hence device fabrication from InSb NWs have been thoroughly discussed. We also review applications of InSb NWs in optoelectronic industry for the fabrication of nanodevices such as infrared detectors and field-effect transistors to explore the basic physics in depth.
A number of the growth mechanisms have been adopted and successful for the growth of InSb NWs; after this successful growth, electrical and optical properties have also been studied a lot [21, 61]. Figure 13 shows the electrical characteristic measured from these grown NWs. It is a very interesting finding that InSb NWs exhibit p-type conduction with mobility of 57 cm2 V−1 s−1 while the thin film of InSb shows n-type behavior with sufficiently high mobility of 1200 cm2 V−1 s−1 grown by electrodeposited method and annealed at 420 °C for few hours . By using the CBE method to grow InSb NWs, these grown NWs with an evaluated resistivity exhibit n-type conduction of 0.3 Ωcm at ambient. Thermally dependent resistivity was attributed to carrier generation across the band gap whose activation energy is equal to the half of the band gap . Based on the synthesis techniques for InSb NWs, the performance of field-effect transistors (FET) based on InSb NW has been evaluated. Device fabrication from these NWs was carried out, and it is revealed from the transport characterization measurement that mobility is sufficiently high than InAs . On the other hand, excellent transport properties of InSb NWs at low temperature (4 K) are observed, with electron concentration of 1 × 1017 cm−3 at field-effect mobility of 35,000 cm2 V−1 s−1 . Coherence length of the order of 260 nm was also observed. It is a fact that the FETs based on InSb NWs are superior in performance than those fabricated from InAs NWs which are due to two major reasons, pinning of surface Fermi level and Schottky barrier. It is noticed that in InAs-based FETs, Fermi level pins into conduction band which results in negligible small resistance . On the other hand, InSb NWs typically show pinning of Fermi level close to the valence band as a result Schottky barriers develop at the contacts .
Band Gaps and Band Alignments
InSb NWs have distinct physical properties revealed by simple optical reflectance measurements and analogy with the identical results from a bulk InSb wafer; it is obvious that antireflection coating can be fabricated from such a NW arrays and could be useful for photon management studies and nanostructured energy harvesting .
Photoluminescence measurements were carried out to investigate the optical properties of antimonide NWs. Band gap of antimonide NWs corresponds to bulk of semiconductor materials while ZB phase dominate in their crystalline structure. Infrared optical absorption spectroscopy revealed the band gap of InSb NW arrays. These NWs with a radius of 40 nm revealed a detection edge of about 170 meV whereas higher edge of 200 meV is observed for those NWs having diameter 60 nm . These decreases in diameters exhibit a blue shift that was attributed to confinement effects. Existence of a lot number of heterojunction in the NW geometry were due to the relaxed constraint of lattice matching, and material integrations such as InAs/InSb, InAs/GaInAs/GaSb, InAs/GaSb, InAs/InP/InSb, and NWs that have already been developed. Bulk synthesis of InSb/InAs heterojunction NWs and related material combinations is difficult. During fabrication of heterojunctions in NWs, band alignment can be changed due to change in phase for example in InAs NWs both ZB and WZ phases are equally possible. Another unique type of heterostructures is created during growth of ZB InAs0.9Sb0.1 on GaSb substrate . During growth of InAsSb NWs, antimony has been incorporated from substrate which may affect electrical properties. Theoretical approximations, for InAsSb NWs, the band structure proposed show a valence band off-set of about 495 meV with a band gap of 270 meV , while the experimental observations in this off-set of energy is quite different, which is impossible to measure due to transport mechanism at low source-drain bias.
Thermoelectric applications of InSb NWs have been investigated due to its low thermal conductivity and the high electron mobility. The major logic for this decrease in thermal conductivity is the reduction in phonon density which may decrease the thermal conductivity of NWs. In this material system, higher than three thermoelectric figures have been predicted . The thermoelectric power can be generated due to difference of temperature known as Seebeck effect, and the Luttinger Liquid Theory has been used to study the conductivity of the these low-dimensional material [174, 175] which proposes power law dependency of conductance on heat. Furthermore, both the Seebeck coefficient and conductance shift strongly on the temperature and changes when temperature changed. Luttinger liquid theory explains transport properties of the InSb NWs which predict that this extraordinary mobility was due to these transitions . Moreover, thicker NWs (radius of 20 nm) exhibit a lower Seebeck coefficient related to thinner (with the radius of 10 nm) NWs. Major causes of the thermopower in these InSb NWs are electron-electron interaction as well as back scattering of impurities.
A chemiresistive FET for the detection of NO2 gas grown by chemical vapor deposition (CVD)-based InSb NWs as it has narrow band gap of 0.18 eV at 300 K has been reported, and scanning electron microscopic image of FET is shown in Fig. 9a, b. When this device operated at room temperature, the fabricated sensor can detect NO2 down to 1 ppm, which is five times smaller than Occupational Safety and Health Administration (OSHA) permissible limit of 5 ppm. The high sensitivity of the sensors corresponding to the working principle of fabricated device in which resistance of device depends on variation in concentrations of NO2 exposures .
The thin band gap for indium antimonide alloy characteristics from the said materials is very attractive for optoelectronic device applications. The strategic purpose for introducing NWs is the possibility for physical incorporation and the choice of different NW combination systems as the limitations of lattice similarity are minimized. The optical features for heterostructured constituents and hence the device fabrication were not demonstrated at the moment. Even many advancements in NW fabrication techniques and diverse applications in many well-developed field were done up to a certain extent. Phase segregation and hence their ordering may play a vital role in the said NWs and this feature requires many development. Integration of lattice-mismatched can be achieved for NWs with typically small diameters, but also the light coupling efficiency decreases at some specific optimized wavelengths for focused fabricated detectors (>5 μm). Svensson et al.  investigated recently on light absorption efficacy of InAsSb NW heterostructures while ternary structures grown on the stem of the InAs NWs having a radius of 25–50 nm which causes elastic strain relaxation, after getting an ideal growth condition, the authors are able to grow sufficiently long NWs with the length of 700 nm.
To sum up, we have noticed that there are numerous techniques to grow InSb NWs using metallic catalysts or self-seeding. Among these catalysts, gold is a promising material due to its inertness with a few drawbacks, as gold is introduced inside NWs that appear as defects which is not desirable. Alloys of InAsSb, GaAsSb, GaInSb, and InPSb NW heterostructures were revealed with their lattice-mismatched having also been recognized. It is expected that advance individual crystalline NWs and doped form of the said NWs will be fabricated soon, which will open a new horizon in the nanotechnology and more detailed studies of the quantum phenomenon. For example, no research studied has been made on fabrication of AlGaSb, AlSb, and AlInSb NWs that is antimonide NWs containing aluminum as a ternary material. Such materials show promising characteristics due to variability in its band gap by introduction of ternary alloy which can be up to 1.62 eV. The introduction of aluminum for heterostructure growth may cause oxidation due to chemical reaction, and as a result, may affect the catalyst activity as result growth rate decreases. Despite these facts, antimonide NWs containing aluminum will be have the scope needed to be explored for future generation optoelectronic devices. Depending upon these applications of antimonide NWs, few major aspects of these materials are promising, and these are large g-factor and investigation of spin-orbit interaction to reveal quantum phenomenon. Particularly, investigation based on NW devices is a unique way to understand low-dimensional systems. Other characteristic features of antimonide NW-based devices are to use as detectors and emitters in the infrared regime of electromagnetic spectrum offered by NW technology. For the realization of its complete potential, further heterostructured NW improvement is, however, essential/prerequisite. Dopants are used to enhance device performance and to control conductivity. In addition, surface passivation methods to decrease surface-related opportunistic recombination and conduction as well as advance contact schemes are required. To decrease the formation of intrinsic imperfections in the material, growth parameters required further optimization; as a result, optical and electrical characteristics improved as well. Two-dimensional InSb also grown by MBE have been reported. These thin films are free standing on the InAs NWs using buffer-layer engineering. The length and width of the grown InSb can be controlled by tuning the Sb/In beam evaporation ratio with ZB single crystals. It is expected that plentiful comprehensive materials reported that united with empirical device applications will continue to push the advancement in InSb NW performance and quality; the heterostructured NWs will provide the opportunity to young scientists to contribute their research in this era which should be helpful to improve the awareness and understanding of these inimitable NWs.
The authors thank the Institute of Fundamental and Frontier Sciences, Faculty of International Center for Artificial Materials (ICAM) of University of Electronic Science and Technology of China (UESTC) for all the support provided. M. Shafa thanks all the colleagues during collaborations at the UESTC who have contributed to the work described here: Dr. Sadaf Akbar, Dr. Lei Gao, Dr. M. Fakhar-e-Alam and Prof. Zhiming Wang. This review is a dedication to all of them.
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