Directed Assembly of Tungsten Nanoparticles for Interconnects

As computer chip manufacturing has scaled down, a key issue that has yet to be resolved is connecting transistors. These interconnects are vital components of circuits and tungsten is often used because of its high conductivity and low permeability. The scale-down of current tungsten deposition methods leaves voids along the center of the interconnect that degrade conductivity and disrupt device performance. Consequently, a new fabrication method needs to be developed and directed assembly is a promising solution. Electric field directed assembly has been shown to successfully manipulate nanoparticles onto semiconducting substrates. Adapting existing processes to work suitably with tungsten nanoparticles and to produce nanorods would be a crucial step towards the development of a new interconnect fabrication technique.

Though they are still being developed and are not yet fully understood, nanoparticles possess immense potential for applications in a multitude of disciplines. The assembly of nanoparticles into nanowires or nanotubes yields one-dimensional structures that have lower melting points and increased strength when compared to their bulk materials, as well as the ability to attain semi-conducting properties. [1] Thus far, much research has been directed towards carbon nanotubes, which have demonstrated the potential for applications as energy storage and conversion devices, sensors, field emitters, and components of electrical systems. [2] The present research focuses on nanotubes and their applications in the latter, specifically investigating the assembly of tungsten nanoparticles for use as interconnects in integrated circuits. As chips have continued to decrease in size, interconnection has become one of the primary hindrances to further development. [3] [4] With new devices seeking to limit power loss, signal degradation, and interconnection delays, the International Technology Roadmap for Semiconductors 2009 report on interconnects has stated that the future challenges for interconnection include developing new materials with sufficient conductivity and low permittivity, developing efficient methods to manufacture interconnects, developing reliable structures, and developing three-dimensional control of interconnects. [5] Tungsten is used at the local level of

interconnection for wiring and for contact with microprocessors, memory units, and flash devices. Additionally, it is used on a more global level to fill vias connecting other interconnect layers. Tungsten nanoparticles are easily manipulated, as prior research has demonstrated the ability to produce tungsten oxide nanowires, [6] [7] [8] nanowires primarily composed of tungsten,
[9] [10] [11]

and pure tungsten nanowires.

[12] [13] [14] [15] [16]

Bien, et al. have stated that tungsten

containing nanowires have potential applications as smart coatings, lithium-ion battery catalysts, electrochromatic materials, and nanostructured sensors
[10]

and Broadbent, et al. found that

tungsten was specifically suitable for interconnect applications because of its high resistance to electromigration, its high median time to failure, and its high melting temperature. [17] Likewise, Kikuchi, et al. demonstrated the ability of tungsten to uniformly fill narrow vias as components of 3D integrated circuits. [18] From a conductive standpoint, tungsten shows desirable electrical properties. Though further calculations for tungsten nanowires are desired, reported values of one to two orders of magnitude higher than the bulk resistivity (5 cm) for 3-7nm diameter wires, [13] 200 cm for 19nm diameter nanowires, [11] 50 cm for 40nm diameter wires, [19] 23 cm for 40nm wide lines, [20] 40 cm for 50nm diameter wires, [10] and 218 cm for 300nm diameter wires
[21]

have been made. It should be noted that existing studies have had considerably more success

fabricating tungsten interconnect films with resistivities more comparable to its bulk resistivity.
[10] [17] [22]

The present investigation will not determine the electrical properties of tungsten

nanostructures, but will seek to fabricate them and notes that tungsten nanowires of diameter 1050nm, [14] 20nm [12], 7-10nm, [16] and even 3-7nm [13] have all been produced.

Tungsten and tungsten containing nanowires have been assembled through a variety of techniques, among them being vapor phase synthesis, thermal-evaporation,
[23] [15]

hydrothermal mechanisms,
[12] [16]

[6] [7]

electron-beam-induced deposition,
[9] [10] [11] [14]

field emission,

[13]

and

chemical vapor deposition.

All of these techniques have successfully yielded

tungsten nanowires, but certain techniques are more suitable to interconnect applications and mass production than others. Moreover, there exist additional methods for assembling nanoparticles that have not yet been examined with tungsten nanoparticles. Vaddiraju, et al. successfully manufactured tungsten nanowires but did so at temperatures ranging from 1200-2000 oC,
[15]

suggesting that the vapor phase synthesis method would be

inefficient for high-rate manufacturing. The hydrothermal mechanisms mentioned above were developed specifically for use as an anode in a lithium-ion battery
[6]

and for use as a

photocatalyst to purify air. [7] Baek, et al. used their thermal-evaporation approach to fabricate a novel three dimensional structure of tungsten nanothorns on tungsten trioxide nanowires, [23] but current technology is not yet suited for the integration of the three dimensional structures that the experiment produced. Furthermore, though electron-beam-induced deposition has been shown to be a highly controllable way of manufacturing tungsten nanowires of very small diameter, [12] [16] the process is inherently slow for nanowire manufacture on a large scale. Oon, et al. manufactured the smallest reported tungsten nanowires (3-7nm) that this study has found, using a novel field emission approach by which field emission of electrons broke down precursor molecules and led to wire formation.
[13]

Though their investigation was

successful and was made for interconnect applications, it is not currently efficient enough to be considered for large-scale manufacturing because of the fact that the production mechanism only yielded one wire per iteration. Yet it is a promising method, especially because the follow-up

investigation performed by You, et al. used the same method to produce larger nanowires (40nm) with decreased resistivity (50 cm). [19] Chemical vapor deposition (CVD) is the most widely used mechanism for the fabrication of tungsten nanowires. Additionally, it is the most widely used method for uniformly filling vias in integrated circuits. Put simply, CVD is the technique of releasing a gas precursor onto a heated substrate. In the process, a solid deposit forms. Some processes induce the reaction by shooting a focused ion beam at the substrate, but this fabricates wires that are not pure tungsten
[9] [11]

and,

according to Li, et al., this impurity is the root cause of the nanowires having a resistivity higher than tungstens bulk resistivity. [11] Bien, et al. produced tungsten nanowires of low resistivity using CVD, but developed a technique that deposited the tungsten over a polysilicon core. [10] It should be investigated further if pure tungsten nanowires would possess an even lower resistivity. The work of Lee, et al. differed from the others in that a tungsten film was laid down and then CVD was used to manipulate the film into an array of nanowires. Though the experiment tested the nanowires for application as an electron field emission source, the method produced uniform nanowires of 10-50nm and demonstrated potential for large-scale manufacture. [14] As a potential application to electrical interconnects, the electrical properties of these nanowires should be investigated. The technique of manipulating nanoparticles using electric fields has never been implemented with tungsten, despite the fact that electrophoresis, [24] dielectrophoresis, [25] [26] [27]
[28]

or a combination of both [29] [30]

[31]

have been shown to be highly controllable and efficient

methods for manipulating nanoparticles and manufacturing nanowires. Electrophoretic assembly of nanoparticles involves the use of a DC current to produce a uniform electric field that allows for the manipulation of charged particles. Dielectrophoretic assembly involves the use of an AC

current to create an alternating field that forces nanoparticles to move either along the gradient of the field or in the direction opposite to it. The voltage and frequency of the electric field, the electrode geometry and gap width, the particle concentration, the pH of the solution, and the exposure time are all factors that can be tuned to achieve precise manipulation of nanoparticles.
[25] [32] [31]

Liu, et al., Hermanson, et al., and Bhatt, et al., all successfully used dielectrophoresis to fabricate nanowires in similar experiments. These techniques involved placing electrodes in a nanoparticle suspension, inducing an AC voltage in the system, and manipulating the aforementioned properties to achieve growth. All three experiments observed nanoparticle nucleation on one or both electrodes and growth along the gradient of the field. Nanoparticles continued to agglomerate at the tip of the nucleation, elongating the wires until the gap between the electrodes had been linked. [26]
[27] [28]

The present study will explore a different approach to

dielectrophoretic assembly of tungsten nanowires but suggests that these methods be extended to tungsten nanoparticles as well. Template-based electric-field-directed assembly has been shown to be a highly efficient and controllable means of nanomanufacturing, as well as one that can be conducted at room temperature and pressure.
[29] [30]

Yilmaz, et al. demonstrated a simple means of fabricating

nanorods. This method involved etching vias into a template using electron beam lithography, submerging the template and another electrode into a colloidal suspension of nanoparticles, and inducing an AC current with a DC offset to assemble the nanostructures.
[30]

This process is

material independent, possesses an array of parameters that can be modified for precise manipulation, and would be suitable for large-scale production of tungsten nanowires.

Bibliography
[1] Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim and H. Yan, "One-Dimensional Nanosctructures: Synthesis, Characteristics, and Applications," Advanced Materials, vol. 15, no. 4, pp. 353-89, 2003. [2] R. H. Baughman, A. A. Zakhidov and W. A. de Heer, "Carbon Nanotubes--The Route toward Applications," Science, vol. 297, pp. 787-92, 2002. [3] A. C. Cangellaris, "The Interconnect Bottleneck in Multi-GHz Processors," IEEE Computer Society, pp. 98-103, 1998. [4] K. Critchley, B. P. Khanal, M. L. Gorzny, L. Vigdermin, S. D. Evans, E. R. Zubarev and N. A. Kotov, "Near-Bulk Conductivity of Gold Nanowires as Nanoscale Interconnects and the Role of Atomically Smooth Interface," Advanced Materials, vol. 22, no. 21, pp. 2338-42, 2010. [5] International Technology Roadmap for Semiconductors, "Interconnect," 2009. [6] Z. Gu, H. Li, T. Zhai, W. Yang, Y. Xia, Y. Ma and J. Yao, "Large-scale synthesis of single-crystal hexagonal tungsten trioxide nanowires and electrochemical lithium intercalation into the nanocrystals," Journal of Solid State Chemistry, vol. 180, no. 1, pp. 98-105, 2007. [7] Advanced Industrial Science and Technology , "Successful Synthesis of Tungsten Oxide Nanotubes by a Simple Method," 2008. [8] H. Rui, Z. Jing and Y. Rong, "Synthesis and Electrical Characterization of Tungsten Oxide Nanowires," Chinese Physics B, vol. 18, no. 7, pp. 3024-30, 2009. [9] J. Choi and J. Kim, "Highly sensitive hydrogen sensor based on suspended, functionalized single tungsten nanowire bridge," Sensors and Actuators B: Chemical, vol. 136, no. 1, pp. 92-98, 2009. [10] D. C. Bien, R. M. Saman, S. A. M. Badaruddin and H. W. Lee, "Selective formation of tungsten nanowires," Nanoscale Research Letters, vol. 6, no. 1, p. 543, 2011. [11] W. Li, J. C. Fenton, C. Gu and P. A. Warburton, "Superconductivity of ultra-fine tungsten nanowires grown by focused-ion-beam direct-writing," Microelectric Engineering, vol. 88, no. 8, pp. 2636-8, 2001. [12] C. L. Chen, K. Arakawa and H. Mori, "Two-dimensional metallic tungsten nanowire network fabricated by electron-beam-induced deposition," Nanotechnology, vol. 21, no. 28, 2010. [13] C. H. Oon and J. T. L. Thong, "In situ nanowire growth for electrical interconnects," Nanotechnology, vol. 15, no. 5, 2004. [14] Y.-H. Lee, C.-H. Choi, Y.-T. Jang, E.-K. Kim, B.-K. Ju, N.-K. Min and J.-H. Ahn, "Tungsten nanowires and their field electron emission properties," Applied Physics Letters, vol. 81, no. 4, p. 745, 2002. [15] S. Vaddiraju, H. Chandrasekaran and M. K. Sunkara, "Vapor Phase Synthesis of Tungsten Nanowires," Journal of American Chemistry Society , vol. 125, pp. 10792-10793, 2003. [16] Z. Q. Liu, K. Mitsuishi and K. Furuya, "Features of self-supporting tungsten nanowire deposited with high-energy electrons," Journal of Applied Physics, vol. 96, no. 1, pp. 619-23, 2004. [17] E. K. Broadbent, J. M. Flanner, W. G. M. Van den Hoek and I.-W. H. Connick, "High-Density HighReliability Tungsten Interconnection by Filled Interconnect Groove Metallization," IEEE Transactions on Electron Devices, vol. 35, no. 7, pp. 952-6, 1988. [18] H. Kikuchi, Y. Yamada, A. M. Ali, J. Liang, T. Fukushima, T. Tanaka and M. Koyanagi, "Tungsten Through-Silicon Via Technology for Three-Dimensional LSIs," Japanese Journal of Applied Physics, vol. 47, no. 4, pp. 2801-6, 2008.

[19] G. F. You, H. Gong and J. T. L. Thong, "Improving the morphological stability of a polycrystalline tungsten nanowire with a carbon shell," Nanotechnology, vol. 21, no. 19, 2010. [20] M. Traving, G. Schindler and M. Engelhardt, "Damascene and subtractive processing of narrow tungsten lines: Resistivity and size effect," Journal of Applied Physics, vol. 100, no. 9, 2006. [21] E. Horvath, P. L. Neumann, A. L. Toth, E. Vazsonyi, A. A. Koos, Z. E. Horvath, P. Furjes, C. Ducso and L. P. Birol, "Electrical Characterization of Tungsten Nanowires Deposited by Focused Ion Beam (FIB)," Nanopages, vol. 1, no. 2, pp. 255-262, 2006. [22] W. Steinhogl, G. Steinlesberger, M. Perrin, G. Scheinbacher, G. Schindler, M. Traving and M. Engelhardt, "Tungsten Interconnects in the Nano-scale Regime," Microelectronic Engineering, vol. 82, no. 3-4, pp. 266-272, 2005. [23] Y. Baek, Y. Song and K. Yong, "A Novel Heteronanostructure System: Hierarchical W Nanothorn Arrays on WO3 Nanowhiskers," Advanced Materials, vol. 18, no. 23, pp. 3105-3110, 2006. [24] S. Siavoshi, C. Yilmaz, S. Somu, T. Musacchio, J. R. Upponi, V. P. Torchilin and A. Busnaina, "SizeSelective Template-Assisted Electrophoretic Assembly of Nanoparticles for Biosensing Applications," Langmuir, vol. 27, no. 11, pp. 7301-6, 2011. [25] X. Xiong, A. Busnaina, S. Selvarasah, S. Somu, M. Wei, J. Mead, C.-L. Chen, J. Aceros, M. Prashanth and M. R. Dokmeci, "Directed assembly of gold nanoparticle nanowires and networks," Applied Physics Letters, vol. 91, 2007. [26] Y. Liu, J.-H. Chung, W. K. Liu and R. S. Ruoff, "Dielectrophoretic Assembly of Nanowires," Journal of Physical Chemistry, vol. 110, no. 29, pp. 14098-106, 2008. [27] K. D. Hermanson, S. O. Lumsdon, J. P. Williams, E. W. Kaler and O. D. Velev, "Dielectrophoretic Assembly of Electrically Functional Microwires from Nanoparticle Suspensions," Science, vol. 294, no. 5544, pp. 1082-6, 2001. [28] K. H. Bhatt and O. D. Velev, "Control and modeling of the dielectrophoretic assembly of on-chip nanoparticle wires," Langmuir, vol. 20, no. 2, pp. 467-76, 2004. [29] X. Xiong and A. Busnaina, "Direct assembly of nanoparticles for large-scale fabrication," Journal of Nanoparticle Research, vol. 10, pp. 947-54, 2008. [30] C. Yilmaz, T.-H. Kim, S. Somu and A. Busnaina, "Large-Scale Nanorods Nanomanufacturing by Electric-Field-Directed Assembly for Nanoscale Device Applications," IEEE Transactions on Nanotechnology, vol. 9, no. 5, pp. 653-8, 2010. [31] R. J. Barsotti, M. Vahey, R. Wartena, Y. Chiang, J. Voldman and F. Stellacci, "Assembly of Metal Nanoparticles into Nanogaps," Small, vol. 3, no. 3, pp. 488-99, 2007. [32] O. D. Velev and K. H. Bhatt, "On-chip micromanipulation and assembly of colloidal particles by electric fields," Soft Matter, vol. 2, pp. 736-50, 2008.