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Synthetic Methods and Applications of Silicon Nanowire: a Review J. Chosun Natural Sci. Vol. 10, No. 2 (2017) pp. 65 − 73 https://doi.org/10.13160/ricns.2017.10.2.65 Synthetic Methods and Applications of Silicon Nanowire: A Review Md Hasanul Haque and Honglae Sohn† Abstract In this review paper, we will discuss about the methods of synthesizing Si nanowires by Top-down and Bottom-up. Silicon nanowires have a lot of application on various fields such as Li ion batteries, solar cells, chemical and biological sensors. We will address some of the applications of silicon Nanowires. Keywords: Silicon Nanowires, Metal Assisted Chemical Etching, Lithium Battery, Electroless Metal Deposition 1. Introduction growth (OAG), laser ablation, chemical etching, molec- ular beam epitaxy (MBE) are some of commonly used Silicon is a bio-compatible material and has some techniques for synthesizing Si NWs. Here we will benefit than other elements such as low processing cost mainly discuss about metal assisted Chemical etching and high production yields. Silicon nanowires are one (MACE) from top –down and Vapor-Liquid-solid of the most important materials for current semiconduc- growth (VLS) from bottom-up method. tor industry show unique and superior optical, thermal, electronic and chemical properties. Nanowires are 2.1. Metal Assisted Chemical Etching important class of one dimensional material with a Metal assisted Chemical etching (MACE) is the most diameter of less than 100 nm. It results in a large surface economical and simple technique for synthesizing Sili- to volume ratio[1]. Including conductor, semiconductor, con nanowires. Besides, other methods often require and insulator, there exits various types of nanowires. difficult reaction condition like high temperature, com- The properties which nanowires have that are not avail- plex equipment. Moreover these are very expensive and able in bulk or 3D materials. For future nano electronics slow growth of Si NWs. Whereas various parameters the 1D Nanowires can be employed as the building like diameter, length, doping type and doping level can blocks. Due to their ready application in modern indus- be controlled by using MACE[5]. To produce larger sur- try Silicon Nanowires are one of the most essential face to volume ratio structures MACE can be used 1Dsemiconductor. SN are attracting interest being their because it is more adjustable[6]. Etching temperature, surface dependent properties and promising application solution concentration[7], the space between metal par- in the fields of nano electronics[2,3], solar cells, lithium ticles[8] are the important parameters to obtain microm- battery , bio- and chemical sensors[4]. eters on the surface of silicon substrates. Brahiti and co- workers reported the reaction time of noble metal depo- 2. Synthesis Methods of Si NWs sition and etching[9]. The most widely used noble metal (silver, nickel, There are a lot of different approaches for fabricating platinum and gold) can be deposited on Si wafer. Depo- silicon nanowire such as top-down and bottom-up. It is sition of these metals on silicon wafers in HF solution totally depend on target of application. Vapor-liquid- has been broadly studied via various method such as solid growth (VLS), thermal evaporation, oxide-assisted thermal evaporation[10], electroless deposition[11], focused- ion-bean (FIB) assisted deposition[12] or spin-coating of Department of Chemistry, Chosun University, Gwangju, 501-759, Korea particles via other method[13]. † Corresponding author : [email protected] The electroless metal deposition does not need exter- (Received : June 1, 2017, Revised : June 15, 2017, Accepted : June 25, 2017) nal electrical power source. It also describes a galvanic − 65 − 66 Md Hasanul Haque and Honglae Sohn Fig. 1. Metal-assisted chemical etching is tentatively described here. In (a),deposition of silver nanoparticle on Si surface, and forming holes via the oxidation of silicon and by the etching of HF. (b) Generation of Si NWs arrays leads to silver nanoparticle sinking and new Si NWs are formed. (c) Cross-section of synthesized Si NWs. In the process of electro chemical deposition of Ag in AgNO3/HF solution, the electro chemical potential of the system Ag+/Ag lies well below the Si valence band, the reduction Ag ions and the oxidation of Si atoms occurs simultaneously. While the Si atoms are being oxidized, silver ions are able to capture electron from valence band of silicon atom and being reduced. From Ag+ to the valence band of silicon holes were injected[14] and silver ion reduced to elemental silver forming nuclei (Fig. 2A). Moreover Ag nuclei become large with the time. The HF solution will etch it away and into the hole Ag particle sinks when Si Oxide from below the silver nanoparticle. However silver is more electronegative to Si, so it continuously capture elec- trons from silicon atoms and Ag- ions formed will attract more Ag+ from the solution. Between the inter- face of Si and deposited Ag, the charge transfer process usually happened. Furthermore the needed electrons for reduction of metal ions will come from silicon and the nanoparticle is going larger in size along with the depo- sition process. At the bottom of the etched pores Ag+ was reduced forming Ag particles because no new Ag nuclei emerged. So Ag nuclei grew in dendrite structures (Fig. 2B and C). From a HF–containing plating solution, there are a different look between the morphology of Pt and Cu electroless deposited and the morphology of Ag and Au. Fig. 2. Cross-sectional SEM image of p type <111> substrate, etched with HF/AgNO3 for a) 5 min and b, c) 2.2. Vapor-Liquid-Solid (VLS) Growth on Silicon 30 min, reprinted from reference[15]. Nanowires Wagner and his co-workers[16] introduced in details, displacement process that involves the spontaneous oxi- the vapor-liquid-solid (VLS) mechanism Fig. 3. There dation of Si and reduction of metal ion to metal parti- are many ways to synthesize Si NWS. VLS is one of cles. them to synthesize by gold nanoparticle. Silicon tetra- J. Chosun Natural Sci., Vol. 10, No. 2, 2017 Synthetic Methods and Applications of Silicon Nanowire: A Review 67 Fig. 3. Illustration of Synthesizing silicon nanowire using VLS method via CVD method: Step (i) Deposition of gold nanoparticle. Step (ii) Reduction of silane gas to silicon vapor. Step (iii) Diffusion of silicon vapor via gold nanoparticles. Step (iv) By super-saturation with silicon the formation of Si NWs, reprinted from reference[18]. Fig. 4. VLS process for growing nanowires. a) indicates the catalytic gold particles formed by Sub-nanometer sputter deposition of Au and a following coalescence with a combination of a thermal anneal in H atmosphere at 450oC for 300 s and a following plasma treatment. b) Shows nanowires grown on an oxidized silicon substrate and c) a (100) oriented single crystalline silicon substrate on a close-up of growing nanowires, reprinted from reference[19]. chloride (SiCl4) or silane (SiH4) usually used as the ing and such kind of defects are observed. By thermo- source of silicon which will alloy with Au and melted dynamic basis can predict the growth direction[17]. when heated. At the surface of Au nanoparticle, the Silicon constantly will flow and atom of Si continues silane will decompose when the temperature is higher. to diffuse into Au-Si melt. Nucleation if Si develops at At the time, into the liquid Au particle, Si will dissolve. the footprint layer by layer at the Au-Si catalyst .Thus Then Si will accelerate out from the liquid phase to Nanowire is formed. Fig. 4a presents grown of Si NW form the solid nanowire. The eutectic temperature of Si- on an oxidized Si wafer and b) close look of <110> ori- Au binary alloy is about 363oC[16] basically for synthe- ented Si NW lattice grown on crystalline Si (100) wafer. sizing the Si NWs can be 400oC which is not high. The The size of the gold array characterizes of the diameter dimension of gold particles controlled the size of as- of nanowire except the endless need of lithographic grown Si NWs. Moreover partial pressure and tempera- means. ture are also important for growing rate. To grow Givarginov postulated in 1970, that a basic critical nanowires due to various conditions like kinking, bend- diameter for growth because of thermodynamic atten- J. Chosun Natural Sci., Vol. 10, No. 2, 2017 68 Md Hasanul Haque and Honglae Sohn tion[20]. The growth of silicon nanowires can be done on various substrates. It is one of the advantages of VLS method. The crystal growth direction of nanowire occurs on amorphous substrates. The interaction between diameter and crystal direction is openly noticeable[21]. 3. Application of Si NWs With the advantages of chemical and optical proper- ties of their surface, it may be developed for various fields such as devices, sensors, bio-systems, batteries, and solar cells. 3.1. Lithium Ion Battery Silicon has a low discharge potential and the highest theoretical charge capacity (4200 mAhg-1). Si anodes appearance balanced working potential (~0.5 V vs. Li/ Li+)[22]. Whereas graphite anodes (~0.05 V vs. Li) So that it is an attractive anode material for Lithium bat- teries and it is also cheap and abundant. The drastic vol- ume changes of silicon greater than 300% upon Fig. 5. Illustration of a lithium battery containing a lithium insertion and extraction of lithium. This will lead to the metal oxide cathode and Si anode during a) charging and [25] capacity fading and pulverization[24]. It causes to an b) discharging, reprinted from reference . interruption through the anode for flowing current. To solve this problem fabulous efforts have been pursued tion and stress. For example, Christensen and Newman including methods of inorganic to organic, from chem- worked about swelling and stress[27], during lithiation ical to physical.
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