Ultradense and planarized antireflective vertical silicon nanowire array using a bottom-up technique
© Dupré et al.; licensee Springer. 2013
Received: 11 January 2013
Accepted: 27 February 2013
Published: 9 March 2013
The production and characterization of ultradense, planarized, and organized silicon nanowire arrays with good crystalline and optical properties are reported. First, alumina templates are used to grow silicon nanowires whose height, diameter, and density are easily controlled by adjusting the structural parameters of the template. Then, post-processing using standard microelectronic techniques enables the production of high-density silicon nanowire matrices featuring a remarkably flat overall surface. Different geometries are then possible for various applications. Structural analysis using synchrotron X-ray diffraction reveals the good crystallinity of the nanowires and their long-range periodicity resulting from their high-density organization. Transmission electron microscopy also shows that the nanowires can grow on nonpreferential substrate, enabling the use of this technique with universal substrates. The good geometry control of the array also results in a strong optical absorption which is interesting for their use in nanowire-based optical sensors or similar devices.
KeywordsSilicon nanowires Vapor–liquid-solid High density Nanoporous alumina Universal substrate Light trapping
Semiconductor nanowires are now widely implemented as active elements in devices for various applications such as energy harvesting [1, 2], microelectronics , or sensors [4, 5]. In order to achieve high performances, high densities of nanowires are required to increase efficiency or sensitivity of devices [6, 7]. In this purpose, top-down etching of a semiconductor wafer is the most commonly used technique [7–9]. However, the requirement of a bulk wafer prevents the realization of cost-effective devices. Some groups therefore choose to use bottom-up techniques and produce nanowires using catalytic processes such as chemical vapor deposition (CVD) [10–12], allowing the growth of nanowires on noncrystalline substrates [13, 14]. However, the production of high-density arrays of aligned nanowires is challenging with this technique because it requires a control of the density and localization of the metallic catalyst seeds. Furthermore, if the substrate is not oriented in the preferential growth direction, it is impossible to achieve arrays with aligned nanowires because of their random orientations on the substrate. Various solutions are investigated to create high-density networks of nanowires using a bottom-up approach. For instance, dense networks of gold droplets can be realized by dewetting a thin layer of gold deposited on the surface of a substrate , but the density is not as high as with top-down techniques, and the size of the catalyst particles is hardly controlled. Another interesting solution is to lithographically pattern a substrate with catalyst particles [16, 17], which is time and money consuming in the case of e-beam lithography to achieve nanoscale dimensions.
We describe a new bottom-up method to produce silicon nanowire arrays which present a very high density and height homogeneity. Nanowires are grown by gold-catalyzed CVD in the vapor–liquid-solid (VLS) mode using an anodic aluminum oxide (AAO) membrane with cylindrical nanopores as growth template. This guided nanowire growth is used to create arrays of vertically aligned nanowires with densities up to 1010 cm−2 on substrates oriented in another direction than the preferential one [18, 19]. It is usually admitted that in this case, growth has to be stopped before the nanowires reach the surface of the AAO template. It indeed prevents any structural anomalies such as kinks and increases of the nanowires’ diameter due to the catalyst getting out of the template. This leads to a difficult control and inhomogeneities in the length of the nanowires depending on the size of the initial gold catalyst. However, a planarized silicon nanowire matrix is of great interest to achieve reproducible and homogeneous top contacts or structural processing . In this paper, we show that a combination of ultrasonic agitation, gold-chemical etching, and silicon plasma etching enables the achievement of high-density arrays of silicon nanowires with a very good length control and homogeneity on a silicon substrate. The nanowires have a good crystalline quality, and the array features good antireflective properties that could be useful for their implementations in devices such as detectors.
Structural characterizations were carried out using a Zeiss Ultra 55 SEM (Carl Zeiss, Inc., Oberkochen, Germany) and a Jeol 3010 transmission electron microscope (TEM, JEOL Ltd., Akishima-shi, Japan). Grazing incidence X-ray diffraction (GIXD) was performed at the BM2-D2AM beamline of the European Synchrotron Radiation Facility (ESRF), Grenoble, France. Reflectivity measurements were carried out with a homemade optical setup.
Results and discussion
SEM pictures of Figure 2 clearly show the very high density of individualized nanowires. Based on the number of nanowires counted on SEM images, we estimate the density to around 8×109 nanowires cm−2 for a sample in which growth template was made at 40 V. It is also clear that nanowires were guided in the nanopores during their growth as revealed by the roughness of their surface: the morphology of the nanopores’ sidewalls was transferred to the growing nanowires which were thoroughly filling them (Figure 2e,f). The combination of standard microelectronics processes with the confined VLS growth of silicon nanowires therefore enabled the production of arrays of nanowires presenting similar features than with top-down techniques: their density is very high and every single nanowire is well individualized.
Since the nanowires’ diffraction peak appears at a lower scattering vector than the substrate one, the silicon lattice parameter is slightly dilated in the nanowires compared to bulk silicon. The calculated strain using Equation 3 is Δa/a = 1.9 × 10− 3 which is one order of magnitude greater than for gold-catalyzed silicon nanowires which grew freely . This increased strain could be explained by the forced growth in the nonpreferential  crystallographic direction or by the effects at the interface between the growing nanowires and their Al2O3 growth template, but this still needs further investigation.
Two types of nanowires therefore grew in the AAO template, one in epitaxy with the (100) substrate and another one with no crystalline relation with it, each type being clearly detected with a separate technique. Using SEM pictures such as the one of Figure 2e, it is not possible to visually differentiate between the two types of wires since they are all well individualized and fully guided in the nanopores. The most likely cause for the nonepitaxial nanowire growth is a partial deoxidation of the silicon substrate during the vapor HF step before catalyst electrodeposition. If the silicon surface at the bottom of a pore is only partially deoxidized, the remaining native oxide would disturb the initial growth steps by screening the substrate and therefore preventing a good epitaxy. This effect is known and described in the case of copper electrodeposition in nanoporous alumina . In the opposite case of a thorough deoxidation of the nanopore, the resulting nanowires would grow in epitaxy with the silicon substrate.
Silicon nanowire arrays were produced presenting top-down features but using a bottom-up CVD process. A very high density was reached with a planarized overall surface and long-range periodicity leading to interesting optical behavior such as an increased light absorption. Silicon nanowires are monocrystalline and grew on a nonpreferential (100) silicon substrate, opening the way to the use of this technique on noncrystalline universal substrates such as glass or metals.
The authors would like to thank Marc Zelsmann for his help in the deposition of thick aluminum. Special thanks go to the BM2-D2AM beamline staff of ESRF for their technical support. This work was financially supported by the French Ministère de la Défense-Direction Générale de l’Armement and by the Region Rhône-Alpes Scientific Research Department via Clusters de Micro et Nanotechnologies.
- Tian B, Zheng X, Kempa TJ, Fang Y, Yu N, Yu G, Huang J, Lieber CM: Coaxial silicon nanowires as solar cells and nanoelectronic power sources. Nature 2007, 449: 885–889. 10.1038/nature06181View ArticleGoogle Scholar
- Hochbaum AI, Chen R, Delgado RD, Liang W, Garnett EC, Najarian M, Majumdar A, Yang P: Enhanced thermoelectric performance of rough silicon nanowires. Nature 2008, 451: 163. 10.1038/nature06381View ArticleGoogle Scholar
- Goldberger J, Hochbaum AI, Fan R, Yang P: Silicon vertically integrated nanowire field effect transistors. Nano Lett 2006, 6(5):973. 10.1021/nl060166jView ArticleGoogle Scholar
- Kim DR, Lee CH, Zheng X: Probing flow velocity with silicon nanowire sensors. Nano Lett 2009, 9(5):1984–1988. 10.1021/nl900238aView ArticleGoogle Scholar
- Talin AA, Hunter LL, Léonard F, Rokad B: Large area, dense silicon nanowire array chemical sensors. Appl Phys Lett 2006, 89: 153102. 10.1063/1.2358214View ArticleGoogle Scholar
- Kelzenberg MD, Putnam MC, Turner-Evans DB, Lewis NS, Atwater HA: Predicted efficiency of Si wire array solar cells. In Proceedings of the 34th IEEE Photovoltaic Specialists Conference: June 7–12 2009. Philadelphia: Piscataway: IEEE; 2009:001948–001953.View ArticleGoogle Scholar
- In HJ, Field CR, Pehrsson PE: Periodically porous top electrodes on vertical nanowire arrays for highly sensitive gas detection. Nanotechnology 2011, 22: 355501. 10.1088/0957-4484/22/35/355501View ArticleGoogle Scholar
- Hsu C-M, Connor ST, Tang MX, Cui Y: Wafer-scale silicon nanopillars and nanocones by langmuir-blodgett assembly and etching. Appl Phys Lett 2008, 93: 133109. 10.1063/1.2988893View ArticleGoogle Scholar
- Peng K, Hu J, Yan Y, Wu Y, Fang H, Xu Y, Lee SST, Zhu J: Fabrication of single-crystalline silicon nanowires by scratching a silicon surface with catalytic metal particles. Adv Func Mater 2006, 16: 387–394. 10.1002/adfm.200500392View ArticleGoogle Scholar
- Wagner RS, Ellis WC: Vapor–liquid–solid mechanism of single crystal growth. Appl Phys Lett 1964, 4(5):89–90. 10.1063/1.1753975View ArticleGoogle Scholar
- Hoffman S, Ducati C, Neill RJ, Piscanec S, Ferrari AC, Geng J, Dunin-Borkowski RE, Robertson J: Gold catalyzed growth of silicon nanowires by plasma enhanced chemical vapour deposition. J Appl Phys 2003, 94(9):6005–6012. 10.1063/1.1614432View ArticleGoogle Scholar
- Chia ACE, LaPierre RR: Contact planarization of ensemble nanowires. Nanotechnology 2011, 22: 245304. 10.1088/0957-4484/22/24/245304View ArticleGoogle Scholar
- Chakrapani V, Rusli F, Filler MA, Kohl PA: Silicon nanowire anode: improved battery life with capacity-limited cycling. J Power Sources 2012, 205: 433–438.View ArticleGoogle Scholar
- Xie X, Zeng X, Yang P, Wang C, Wang Q: In situ formation of indium catalysts to synthesize crystalline silicon nanowires on flexible stainless steel substrates by PECVD. J Cryst Growth 2012, 347: 7–10. 10.1016/j.jcrysgro.2012.03.011View ArticleGoogle Scholar
- Muller CM, Mornaghini FCF, Spolenak R: Ordered arrays of faceted gold nanoparticles obtained by dewetting and nanosphere lithography. Nanotechnology 2008, 19: 485306. 10.1088/0957-4484/19/48/485306View ArticleGoogle Scholar
- Kayes BM, Filler MA, Putnam MC, Kelzenberg MD, Lewis NS, Atwater HA: Growth of vertically aligned Si wire arrays over large areas with Au and Cu catalysts. Appl Phys Lett 2007, 91: 103110. 10.1063/1.2779236View ArticleGoogle Scholar
- Kendrick CE, Yoon HP, Yuwen YA, Barber GD, Shen H, Mallouk TE, Dickey EC, Mayer TS, Redwing JM: Radial junction silicon wire array solar cells fabricated by gold-catalyzed vapor–liquid–solid growth. Appl Phys Lett 2010, 97: 143108. 10.1063/1.3496044View ArticleGoogle Scholar
- Shimizu T, Xie T, Nishikawa J, Shingubara S, Senz S, Gösele U: Synthesis of vertical high-density epitaxial Si(100) nanowire arrays on a Si(100) substrate using an anodic aluminum oxide template. Adv Mater 2007, 19: 917–920. 10.1002/adma.200700153View ArticleGoogle Scholar
- Buttard D, David T, Gentile P, Den Hertog M, Baron T, Ferret P, Rouvière JL: A new architecture for self-organized silicon nanowire growth integrated on a <100> silicon substrate. Phys Stat Sol (a) 2008, 205(7):1606–1614. 10.1002/pssa.200723522View ArticleGoogle Scholar
- Masuda H, Satoh M: Fabrication of gold nanodot array using anodic porous alumina as an evaporation mask. Jpn J Appl Phys 1996, 35: L126-L129. 10.1143/JJAP.35.L126View ArticleGoogle Scholar
- Kustandi TS, Loh WW, Gao H, Low HY: Wafer-scale near-perfect ordered porous alumina on substrates by step and ash imprint lithography. ACS Nano 2010, 4(5):2561–2568. 10.1021/nn1001744View ArticleGoogle Scholar
- Lew K-K, Redwing JM: Growth characteristic of silicon nanowires synthesized by vapour-liquid–solid growth in nanoporous alumina templates. J Cryst Growth 2003, 254: 14–22. 10.1016/S0022-0248(03)01146-1View ArticleGoogle Scholar
- Gentile P, Solanki A, Pauc N, Oehler F, Salem B, Rosaz G, Baron T, den Hertog M, Calvo V: Effect of HCl on the doping and shape control of silicon nanowires. Nanotechnology 2012, 23: 215702. 10.1088/0957-4484/23/21/215702View ArticleGoogle Scholar
- Buttard D, Gentile P, Renevier H: Grazing incidence X-ray diffraction investigation of strains in silicon nanowires obtained by gold catalytic growth. Surf Sci 2011, 605: 570–576. 10.1016/j.susc.2010.12.019View ArticleGoogle Scholar
- Tapfer L, La Rocca GC, Lage H, Brandt O, Heitmann D, Ploog K: X-ray diffraction study of corrugated semiconductor surfaces, quantum wires and quantum boxes. Appl Surf Sci 1992, 60/61: 517–521.View ArticleGoogle Scholar
- Gailhanou M, Baumbach T, Marti U, Silva PC, Reinhart FK, Ilegems M: X-ray diffraction reciprocal space mapping of GaAs surface grating. Appl Phys Lett 1993, 62(14):1623–1625. 10.1063/1.108606View ArticleGoogle Scholar
- Descarpentries J, Buttard D, Dupré L, Gorisse T: Highly conformal deposition of copper nanocylinders uniformly electrodeposited in nanoporous alumina template for ordered catalytic applications. Micro Nano Lett 2012, 7(12):1241–1245. 10.1049/mnl.2012.0754View ArticleGoogle Scholar
- Hu L, Chen G: Analysis of optical absorption in silicon nanowire arrays for photovoltaic applications. Nano Lett 2007, 7(11):3249–3252. 10.1021/nl071018bView ArticleGoogle Scholar
- Lin C, Povinelli ML: Optical absorption enhancement in silicon nanowire arrays with a large lattice constant for photovoltaic applications. Opt Express 2009, 17(22):19371–19381. 10.1364/OE.17.019371View ArticleGoogle Scholar
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