EL 407 FABRICATION PRESENTATION REPORT Cem Alper 10333 Carbon Nanotube: Properties and Applications

Supervised by: Cem ztrk Fall 2009-2010 Sabanci University

1. Carbon Nanotube History and Structure Carbon Nanotube has been the new wonder material for many due to its extraordinary mechanical, electrical and thermal properties. The carbon nanotube is an allotrope of carbon like graphite, graphene and diamond. The C bonds in the structure of the CNTs are all sp2 bonds, from which many properties of the material stem from (O'Connell, 2006).

Figure 1 - Carbon Nanotube

Basically a CNT can be considered as a graphene, which is a sheet of sp2 carbons, rolled up in a certain orientation. The so-called chirality of the CNT, i.e. the way the graphene sheet is wrapped is the most important factor that affects the electrical properties. The chirality of the carbon nanotube is determined by its wrapping vector which is a linear combination of two basis vectors (O'Connell, 2006). A sample figure which illustrates the wrapping vector C and basis vectors a1,a2 is below:

Figure 2 - CNT wrapping vector

Another important classification factor of carbon nanotubes is the number of walls in a CNT. Depending on the number of walls, all the properties of CNT change. There are basically two types: Single-walled and multi-walled. As the name suggests, the SWCNT consists of a single wrapped sheet, whereas MWCNT consists of more than one wrapped carbon sheets. A MWCNT illustration is below:

Figure 3 - MWCNT

This unique structure of carbon nanotubes is the underlying reason of the exceptional mechanical, thermal and electrical properties. The carbon nanotube is known as having extraordinarily high

Youngs modulus (modulus of elasticity) and tensile strength, which is a measure of mechanical strength, it is an excellent thermal conductor as well as having a low density compared to steel, the mainstream load carrying material used in various applications (O'Connell, 2006). The mechanical superiority of the CNTs is caused by the powerful C-C covalent bonds between carbon atoms. 2.1. Carbon Nanotube Electronics Carbon nanotube has seriously been considered as the next Si by many research groups and thus many efforts are being made in order to design an effective device to use the full capability of the CNTs as well as coming up with a solid, well established fabrication process of CNT devices as in the CMOS technology. 2.1.1. Carbon Nanotube Electrical Properties The carbon nanotube is a cylindrical allotrope of carbon with sp2 bonds, one might consider it as a graphene sheet rolled up. The carbon nanotube has been the focus of many researches from various areas owing to its unique structure and chemical properties. Carbon Nanotubes have been discovered by Ijima in 1991, when his group observed and identified multi walled carbon nanotubes (MWCNT)s. However, the first encounter with carbon nanotube, albeit accidental, happened in 1960 when Bacon was working on carbon arc research (O'Connell, 2006). The electrical properties of carbon nanotubes greatly depend on the tube diameter and the chirality of the carbon nanotube. The figure showing the classification the nanotubes is below:

Figure 4 - Carbon Nanotube Types

The CNTs are classifed as zig-zag, armchair and chiral with respect to their wrapping vectors (O'Connell, 2006). The armchair type shows metallic behavior whereas zigzag and chiral ones are

either metallic or semiconducting depending on their wrapping vector (Avouris, 2001). Wrapping vector is a vector associated with the way that the graphene sheet is wrapped, and it is usually denoted as a linear combination of two basis vectors of graphite (O'Connell, 2006). When n=m or n-m=3i the carbon nanotube is metallic, else it is semiconducting with a finite band gap. Another interesting aspect about the CNTs is that, the band gap of the CNT is inversely proportional to its diameter (O'Connell, 2006), which may provide another design parameter for circuit designers in IC applications. Also they are considered as 1-D ballistic transport conductors up to a few microns, which greatly enhance the carrier saturation velocity. Mobilities on the order of ten thousand cm2 /Vs have been foreseen and measured (Javey & Kong, Carbon Nanotube Electronics, 2007). The powerful C-C bonds between the carbon atoms also provide a superior resistance against electromigration which is a serious issue in contemporary via and interconnect materials such as copper and tungsten. 2.1.2. Carbon Nanotube Electronic Applications The CNTs are projected to be used at transistor structures as well as interconnects in the ICs. The high carrier mobility is the main attraction which lures the attention of device researchers. Up to date, the MOSFET-like CNT Field Effect Transistor (CNTFET) have been realized with single walled carbon nanotubes. As can be seen from the figure below, the structure is identical to Si MOSFETs except the channel material is now SWCNT.

Figure 5 - CNTFET structure (Javey et al, 2004)

Although the future looks promising, there are various challenges to be overcome if CNTs are to pose a serious threat to Si. First of all, the metal-to-CNT, CNT-to-Oxide contacts have to be reliably modeled and produced. The major problem with the contacts was to obtain ohmic contacts for source and drain regions of the CNT transistors until Javey et al successfully fabricated a CNTFET with

ohmic contacts using palladium as the contact metal which has the desired work function to form ohmic contact with the CNTs. Another interesting device structure is the SB-MOSFET, which utilizes the band-to-band tunneling phenomenon that occurs between conduction and valence bands of a semiconductor. The device schematic realized by Appenzeller et. al. is below:

Figure 6 - SB-MOSFET structure

The structure is operated by two independent gates, one aluminum gate and one silicon gate. The reason for this two gate structure is to increase the control over the channel to better control the conduction. The basic principle behind the transistor is to modulate the conductance of the channel by altering the bandgap width at the channel, thus effectively controlling the tunneling rate.

Figure 7 - Working modes of SB-CNTFET

As can be seen from the diagrams above when the aluminum gate voltage is low, the device works effectively as a normal field effect device with the same substhreshold swing limitations (i. e. 60mV/dec) however, when the Vgs-Al is high (+0.2 V) the bending occurring due to the voltage difference will allow the holes to travel through the channel with tunneling. This conduction

mechanism is not related with the conventional field effect conductance, and thus it is not bounded with the 60mV/dec sub-threshold swing. The actual fabricated device has shown a sub-threshold swing of 45mV/dec. For voltages in between -1.1 V +0.2 V the device is in OFF state, no current passes through the channel.

Figure 8 - Id vs Vgs graph for both operating modes

2.2.3. Carbon Nanotube Electronic Fabrication The main prerequisites for production of CNTs are: (i) A source of carbon (ii) energy (iii) an active catalyst. There are mainly three different production methods for fabrication of CNTs: Arc discharge, Laser ablation and Chemical Vapor Deposition (CVD) (O'Connell, 2006). In the arc discharge method, the energy source is the electrical arc discharge caused between the voltage difference between the two electrodes which evaporate a portion of the carbon source; which then forms CNTs and gets collected in the cathode. In the laser ablation method, we have an Nd YAG laser which is shined on the carbon source. Consequently, the surface of the graphite evaporates and gets collected on the collector. Arc discharge and laser ablation are two similar methods that evaporates a carbon source (usually graphite) and then collecting it on a collector. Although these both processes can be realized with relatively cheap costs, there are major issues in terms of purity and yield.

Figure 9 - Arc discharge and laser ablation methods

The most promising method for CNT growth seems to be CVD and its derivatives, which is underlined by the fact that most efforts are being made on CVD synthesis improvements. CVD process basically enables CNT growth on a substrate by using catalytic nano-particle metals such as cobalt, iron etc. The carbon source gas is usually a hydrocarbon such as methane. An important advantage of CVD over the other two methods is that patterned growth on Si/SiO2wafers (Franklin, Li, Chen, Javey, & Daia, 2001) which may mean direct integration with semiconductor fabrication processes. However, the CVD process requires a temperature of around 800oC which renders it incompatible with contemporary process steps (O'Connell, 2006).

Figure 10 - CVD process

An important improvement for process temperature is achieved with the use of plasma. Plasma enhanced CVD (PECVD) reduces the required temperature to around 450oC, a temperature acceptable for the other process steps (O'Connell, 2006). 3. Future Prospects The CNTs are already widely used in non-electronic industries, especially in load carrying duties where the number of walls and chirality of the CNT is not a major concern. However, in microelectronics, the idea of using CNTs is currently considered as far-fetched. This is mainly caused by the instabilities in process technologies and the lack of contact formation knowledge, which has great impact on device performance. The main candidate to replace the contemporary CMOS seems to be the FINFET and Gate-All-Around structures, according to IRTS roadmap 2009 (IRTS, 2009). The reason why CNT technology is not feasible to migrate is the fact that performance gain from such a radical technology change is not worth its cost yet. Faster designs have to be proposed and more reliable methods to fabricate such devices have to be developed.

References Avouris, P. (2001). Carbon Nanotube Eletronics. Chemical Physics . Appenzeller, J., Lin,Y.-M., Knoch, J. & Avouris, Ph. (2004). Band-to-Band Tunneling in Carbon Nanotube Field-Effect Transistors. Franklin, N. R., Li, Y., Chen, R. J., Javey, A., & Daia, H. (2001). Patterned growth of single-walled carbon nanotubes on full 4-inch wafers. Applied Physics Letters . Huang, X., Lee, W., Kuo, C., Hisamoto, D., Chang, L., J, K., et al. (1999). Sub 50-nm FinFET: PMOS. IEEE Trans. on Electron Devices . IRTS. (2009). 2009 IRTS. Retrieved January 10, 2010, from IRTS Website: http://www.itrs.net/Links/2009ITRS/2009Chapters_2009Tables/2009_ExecSum.pdf Javey, A., & Kong, J. (2007). Carbon Nanotube Electronics. Springer. Javey, A., Guo, J., Wang, Q., Lundstrom, M., & Dai, H. (2004). Ballistic carbon nanotube field-effect transistors. Nature . O'Connell, M. J. (2006). Carbon Nanotubes Properties and Applications. New York: Taylor & Francis.