RELATED APPLICATION

This application claims benefits and priority of U.S. provisional application serial No. 61/397,981 filed June 18, 2010, the

disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to replacement electrodes comprised of alternative non-metallic electrode materials for the metal thin film electrodes conventionally used in nanoelectromechanical systems (NEMS) . By replacing thin metal film electrodes, the use of these non-metallic electrodes greatly improves device robustness by suppressing or eliminating failure modes currently prevalent in NEMS employing metal electrodes.

BACKGROUND OF THE INVENTION

The term 'nanoelectromechanical systems' or 'NEMS' describes nanoscale devices with combined electrical and mechanical

functionality. NEMS have diverse applications in memory devices, electrical relays and switches, oscillators, communications, sensors, and actuators.

This invention pertains in particular to NEMS in which a

nanostructure makes physical contact with another element of the device in response to an applied force (e.g., an electrostatic force) . This contact, and the resulting coupled electrical, mechanical, and thermal response, can lead to failure of the device. For example, NEMS are known which comprise one or multiple freestanding nanostructures (e.g., carbon nanotubes [references 1- 3], nanowires [references 4-6], or other fabricated freestanding structures [reference 7]) that make contact with an electrode to change the state of the device (e.g., an electrical switch, relay, or memory device) . Prior NEMS devices ubiquitously use electrodes made from metal thin film structures. As described below, this leads to a number of common failure modes.

For example, when these nanostructures make contact with the electrode, electrical charges stored as the result of an electrical potential between the nanostructure and electrode dissipate rapidly from the nanostructure to the electrode (or vice versa) . This results in Joule heating that can damage the nanostructure and/or electrode, ultimately leading to failure of the device. To slow the charge dissipation and thus reduce Joule heating, this invention provides electrode materials which have a higher electrical contact resistance with the nanostructure as compared to conventional metal electrodes used heretofore.

In addition to failure by Joule heating, the nanostructure can stick irreversibly to the electrode upon contact, preventing reversal of the device state. As compared to conventional metal electrodes, the nanostructures adhere less strongly to the

electrode materials provided by this invention, reducing the likelihood of failure by irreversible stiction.

SUMMARY OF THE INVENTION

The present invention provides for replacement of conventionally- used metal electrodes in NEMS devices with electrodes that include on-metallic materials that have a greater electrical contact resistance and lower adhesion with the nanostructure. This reduces Joule heating and stiction, improving device reliability. An illustrative embodiment of the invention provides a NEMS device having one or more electrodes comprised of diamond-like carbon (DLC) material. DLC in general has less adhesive interaction with nanostructures such as carbon nanotubes, as well as a larger electrical contact resistance to reduce transient current spikes. Preferably, the tetrahedral amorphous form of DLC (known as ta-C) is used. This ta-C material is doped with nitrogen or other

suitable element to make it electrically conductive.

Another illustrative embodiment of the invention provides a NEMS device having one or more composite electrodes comprised of a thin metallic film having a thin, outer dielectric layer or coating thereon for contacting the nanostructure . Preferably, the thin dielectric layer or coating comprises A1 ₂ 0 ₃ , Ti0 ₂ or other metal oxide. As in the case of DLC electrodes, the dielectric electrode layer generally has less adhesion with nanostructures. In addition, this dielectric layer prevents direct Ohmic contact between the metal electrode and the nanostructure, limiting the charge

transport to a higher resistance tunneling mechanism.

Practice of the invention thus is advantageous to provide NEMS device electrodes that provide increased resistance to

nanostructure-to-electrode charge dissipation, and decreased nanostructure-electrode adhesive energy.

Other advantages and benefits of the present invention will become more apparent from the following detailed description taken with the following drawings. BRIEF DESCRIPTION OF THE DRAWINGS

Figures la and lb are respective schematic sectional and

perspective views of a switch consisting of a CNT cantilever disposed over an electrode of the NEMS device, while Figure lc shows an equivalent lumped-element circuit for the device.

Figure 2 shows a comparison of characteristic I-V behavior for.

devices exhibiting irreversible stiction (with gold electrodes) , and those in which the stiction has been corrected through the use of DLC electrodes pursuant to the invention.

Figure 3a shows a characteristic I _t o _t ai~V curve of a device with a DLC electrode showing well-defined ON/OFF behavior with

significantly less stiction than devices with a gold electrode and thus reduced failure modes using diamond-like carbon electrodes. The inset of Fig. 3a shows detail of the pull-out event, after which the current is slightly negative due to discharging of the capacitances, C ₀ and C _CNT - Figure 3b shows the current profile for 100 successive actuation cycles driven by ramping applied voltage in a 0-35 V triangle wave. The inset of Figure 3b shows a detail of cycles 46-50. The numbered data points correspond to the numbered positions in the I _tot ai ^_ V curve in Fig. 3a.

Figure 4a shows a comparison of onset of irreversible stiction in the L-H design space for devices with gold electrodes and DLC electrodes. Figure 4b shows a comparison of onset of ablation in the L-H design space for devices with gold electrodes and DLC electrodes. Figure 4c shows a map of failure modes for devices with gold electrodes. Figure 4d shows a map of failure modes for devices with DLC electrodes. Figure 5a compares electromechanical response of devices using gold electrodes and DLC electrodes where CNT-electrode gap (H) versus time is shown in response to a step in voltage applied at t = 0. Figure 5b shows current through the CNT (I C _N T) versus time for devices using gold electrodes and DLC electrodes.

Figure 6a and 6b show experimentally-tested cases plotted in the length-gap design space for devices with gold electrodes, Figure 6a, and DLC electrodes, Figure 6b.

Figure 7 shows a dielectric layer on a metal electrode pursuant to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention for improving the robustness of NEMS will now be described for purposes of illustration and not limitation with respect to an electrostatically-actuated carbon nanotube (CNT) switch of the type described in references 3, 10, and 12-16 listed below. This NEMS architecture is chosen because it shares operating principles, and failure modes, with numerous NEMS devices [see references 9-11] . Thus, while the remainder of the detailed

description of the invention relates to the application of the invention to this particular NEMS device architecture, the

invention has broader applicability to all NEMS devices in which a nanostructure (e.g. carbon nanotubes, nanowires, or other

fabricated freestanding nanostructure) makes surface contact with another element of the device. Such other applications include, but are not limited to, devices consisting of beams ( cantilevered, suspended, or other shapes) made from thin films that bend or resonate in close proximity to an electrode, or switches or

resonators constructed from nanowires and one or more electrodes used to apply electrostatic forces to the nanowires. An illustrative electrostatically-actuated CNT switch is

schematically shown in Figure la and comprises a carbon nanotube

(CNT) cantilever of length L that is fixed at one end and

cantilevered a distance H above an electrode E. In prior MEMS swtiches (see for example reference 16 listed below), this

electrode is typically made from a thin metal film such as

palladium, platinum, or gold [see references 1, 3-5, 17] . The electrical circuit is completed by a voltage source, V, and an external resistor, R _FI Figure la. When the applied bias exceeds a critical "pull-in voltage" (V > V _PI ) , the end of the CNT cantilever accelerates toward the electrode E, closing the switch. The switch remains in this "closed" state until the applied bias is dropped sufficiently such that the combined attractive electrostatic energy and adhesive energy between the CNT cantilever and the electrode

(e.g., van der Waals interactions) are overcome by the elastic energy stored in the deformed cantilever nanomember, which acts to re-open the switch.

The electrical domain of this electrostatically-actuated CNT switch device can be represented by an equivalent lumped-element circuit, Figure lb, comprised of the voltage source and an external

resistor, R _f , in series with, in parallel, the parasitic capacitance of the system Co, the capacitance of the CNT cantilever relative to the electrode C _C NT, and the tunneling/contact resistance, RC _N T, when the CNT approaches and makes contact with the electrode. The total current is denoted as. I _tot ai while the current through the CNT is ICN _T - is the potential across the CNT cantilever, where U = V when -Z total = 0.

While the electrostatically-actuated CNT switch device of Figure la used herein as an illustrative example to describe the invention comprises a single CNT nanomember cantilevered over a single electrode E, there are numerous other architectures which are applicable. For example, some devices employ a single or multiple nanomembers fixed at both ends and suspended over an electrode [see references 2, 17, 19-20]. Others use a single nanomember

cantilevered over two electrodes rather than one [see references 1, 21] . Still others use CNTs oriented vertically to the substrate

[see references 22-23]. The advantages of this invention are applicable to all of these device geometries as it addresses two modes of failure common to this class of devices, specifically:

1. Irreversible stiction between the nanomember or other

nanostructure and the electrode, preventing reversal of the state of the device, and;

2. Thermal ablation of the nanomember or other nanostructure resulting in its partial or complete loss.

The stiction is the result of large adhesive energy (e.g. due to van der Waals interactions) between the nanostructure and the electrode when they make contact. If this adhesive energy exceeds the elastic energy stored in the deformed nanostructure (which acts to break the stiction and re-open the switch) , then the switch will not re-open, even when the applied electrical bias is completely removed. The adhesive energy between the nanostructure and

conventionally-used metallic electrodes is typically large, making it more difficult to overcome by stored elastic energy. The non- metallic electrode materials pursuant to this invention in place of conventional metal electrodes have, in general, weaker interaction with the nanomembers, thereby reducing the adhesive energy to be overcome to re-open the switch.

Ablation occurs as a result of Joule heating. Above a critical current density, the heating can become sufficient to ablate the CNT cantilever or damage the electrode. While devices may be designed such that their steady-state current density is well below the critical value required to cause ablation, transient spikes in current (e.g., during actuation) can still be orders of magnitude greater, resulting in device failure. The non-metallic electrode materials pursuant to this invention used in place of conventional metal electrodes increase the electrical resistance to these transient current spikes, thereby reducing Joule heating.

The present invention provides for replacing conventionally-used metal electrodes in NEMS with alternative non-metallic materials that provide increased resistance to nanostructure-to-electrode charge dissipation, and decreased nanostructure-electrode adhesive energy. In particular, the invention involves the following

embodiments with similar benefits by which to overcome the above- described failure modes:

1. One embodiment of the invention uses diamond-like carbon

(DLC) electrode material in place of conventional metal thin film electrode E, Figure la. DLC in general has less adhesive interaction with nanostructures such as carbon nanotubes, as well as a larger electrical contact resistance to reduce transient current spikes. DLC electrode material includes, but is not limited to, the tetrahedral amorphous form of DLC known as ta-C and other forms of DLC that comprises a mixture of sp ² and sp ³ bonded or coordinated carbon atoms. Preferably, the amorphous tetrahedral form (ta-C) of DLC containing at least some, preferably

predominant, fraction of tetrahedrally coordinated carbon atoms is used. This ta-C is doped with nitrogen to make it electrically conductive as described in reference 29, the teachings of which are incorporated herein by reference. 2. An alternative embodiment of the invention involves coating the existing conventional metal electrode (s) with a thin dielectric layer (e.g., A1 ₂ 0 ₃ or other metal oxide) using atomic layer deposition (ALD) as shown in Figure 7 with similar effect to lessen adhesive interaction with

nanomembers such as carbon nanotubes, as well as a provide larger electrical contact resistance to reduce transient current spikes. The ALD coating can have a thickness of 1 Angrstrom to about 10 nanometers. As in the case of DLC electrode material, the dielectric material in the electrode layer generally has less adhesion with nanostructures . In addition, the dielectric layer prevents direct Ohmic contact between the metal electrode and the nanomember, limiting the charge transport to a higher resistance tunneling mechanism.

EXAMPLES

The following Examples illustrate reduction in failures for NEMS devices pursuant to the invention. In the Examples, devices of varying CNT cantilever length (L) and CNT-elect rode gap ( H) , Figure la, were tested using gold electrodes pursuant to prior practice and DLC electrodes pursuant to an embodiment of the invention.

These results demonstrate elimination of failure by ablation and greatly suppressed onset of irreversible stiction.

Before testing, gold electrodes were fabricated by depositing a 100-nm film of gold (with a 10 nm chromium adhesion layer) on a 200-nm silicon nitride-coated silicon wafer by thermal evaporation.

Nitrogen-doped ta-C electrodes pursuant to the invention were fabricated by depositing a 140-nm-thick film of ta-C by pulsed laser deposition on a silicon nitride-coated ( 200-nm-thick) silicon wafer. The pulsed laser deposition of the electrically conductive electrodes was carried out pursuant to US Patent 5,935,639, 5,821,680; and 6,103,305, the teachings of which are incorporated herein by reference to this end.

The deposited ta-C electrode is comprised predominantly of sp ³ coordinated carbon atoms and possibly some sp ² coordinated carbon and has a resistivity of 10 ⁴ Ω-cm. To define the desired shape (Figure la) of the electrode, a 70-nm aluminum film (with a 10-nm titanium adhesion layer) was deposited by evaporation over the ta-C and patterned by photolithography and liftoff. This was used as an etch mask to define the ta-C electrode shape. The exposed ta-C was etched through to the silicon nitride by reactive ion etching (RIE) using CF4/O2. The aluminum etch mask was then stripped by RIE using BCl3/Cl ₂ /He to re-expose the ta-C electrodes.

REDUCING STICTION

Figure 2 shows, for gold electrode switches, an irreversible stiction; i.e., a sharp increase in current is observed at pull-in as expected. However, as the applied voltage is subsequently lowered, the current returns linearly back to zero, which is characteristic of maintained Ohmic contact. Repeated ramping of the voltage after this initial stiction results in continued linear Ohmic I-V response.

As described above, strong van der Waals interaction between the CNT cantilever ( nanostructure ) and the electrode can prevent reopening of the switch. The electromechanical characterization of the devices with gold electrodes exhibiting irreversible stiction shows a characteristic I-V behavior in which a sharp, well-defined increase in current is observed upon pull-in (closing of the switch) , followed by a linear decrease to zero as the applied voltage is reduced, Figure 2. In contrast, for devices with DLC electrodes pursuant to the invention, a similar sharp jump in current is observed, Figure 2. However, a well-defined pull-out is observed as the applied voltage is subsequently reduced, signifying successful re-opening of the switch .

This Example illustrates that by replacing the gold electrodes with DLC electrodes, the I-V response exhibits a well-defined pull-out (opening of the switch) as the applied voltage is reduced, Figure 2 and 3a. This operation of repeated pull-in and pull-out by ramping the voltage up and down was demonstrated 100 times without

observation of irreversible stiction (Figure 3b).

The efficacy of the invention in reducing stiction is further highlighted in Figure 4a, which summarizes experimental

characterization of devices with incrementally varying L and H using electrodes made from gold and DLC pursuant to the invention and compares the onset of failures modes such as the onset of irreversible stiction and ablation. The curves shown were then fit to the experimental data to separate cases in which irreversible stiction was and was not observed [complete data sets are shown in Figure 6a, 6b] In general, stiction occurs for devices with

relatively long CNTs and smaller CNT-electrode gaps (above the curve in Figure 4a) due to reduced elastic restoring force after pull-in. However, due to reduced CNT-electrode adhesion in the DLC electrodes as compared to the gold electrodes, the onset of

irreversible stiction in the design space (CNT length and CNT- electrode gap) is greatly suppressed in the design space. This can be attributed to the significantly lower surface energy of DLC as compared to gold and other commonly-used metals, although applicants do not wish or intend to be bound by any theory in this regard .

ELIMINATING ABLATION FAILURES

As mentioned above, large current densities can result in failure of the devices by Joule heating. While the device may be designed such that the steady-state current density is well below the critical current density required to cause damage, transient currents (e.g., during actuation) can still cause spikes orders of magnitude greater that can ablate the CNT or damage the electrode.

One potential source of these spikes can be seen by looking at the equivalent lumped element circuit of the device, Figure lb. · During actuation, the CNT cantilever accelerates toward the electrode, closing the gap H. Figure 5a shows the results of a dynamic

multiphysics finite element simulation of device pull-in. As the gap closes (Figure 5b), the resistance _ _CNT drops exponentially (J _CNT = R _c exp(KH) , where R _c is the Ohmic contact resistance between the CNT and electrode, see Figure lb. Consequently, charges stored in the capacitances, C ₀ and C _CNT , Figure lb, rapidly dissipate to the electrode causing a spike in current through the CNT cantilever that approaches the milliamp range (Figure 5b) . The corresponding current density is more than sufficient to ablate the CNT

cantilever. In fact, similar observations of incremental loss have been reported in CNT field emitters operated at similar current densities, as well as other NEMS devices. During the initial

discharge, I _C N _T >> Itota _l (Figure 5b) . Once the stored charges have been fully depleted and the switch is fully closed, the system reaches a significantly lower steady-state current flow

dtotai = -TCNT = U/ (RcuT+Ri) , see Figure lb). Examining the equivalent circuit more closely (Figure lb) , increasing R _CNT (specifically the contact resistance R within the ■RCNT ⁼ -Rc exp(AH) expression) would moderate the detrimental current spike by increasing the time constant for the charge dissipation. However, the contact resistance between CNT cantilevers and gold or other conventional metallic electrodes is generally low (measured to be in the kQ range in our experiments), resulting in an

extremely high current spike at contact. Note that simply

increasing the external resistor R _F would not have a similar effect as it is outside the R _CNT C _O loop and thus does not affect the time constant of the discharge.

The above Examples demonstrate that for devices with gold

electrodes, ablation was observed in cases with relatively short CNT cantilevers and larger CNT-electrode gaps, Figure 4b. For devices with DLC electrodes pursuant to the invention, failure by ablation was never observed, even up to the geometric limits of the device (the CNT-electrode gap cannot exceed the length CNT as switch closure would not be possible) , Figure 4b.

The invention provides two similar embodiments to mitigate the current spike through control of R _CNT - First, diamond-like carbon (DLC) can be used in place of metals for the electrodes. DLC has a large contact resistance with nanostructures such as carbon

nanotubes (measured to be approximately 0.6 GQ, 5 orders of

magnitude greater than for gold) . This slows the charge dissipation upon actuation, decreasing the current and thus mitigating the current spike. Before implementing experimentally, this was tested using the same dynamic multiphysics finite element model described above. A device of the same geometry was re-simulated with an increased value of contact resistance (¾ T = 0.6 GQ) . The resulting mechanics of the switch closing are nearly identical. Figure 5a shows the tip-electrode gap as a function of time in which the cases using gold and DLC electrodes follow nearly identical paths. By contrast, the spike in current through the CNT drops

dramatically as expected in the case of the DLC electrode. Figure 5b compares the current profile through the CNT using the gold and DLC electrodes. Here we see that the magnitude of .the current spike is less than 2.5 μΑ (as compared to > 300 μΑ for gold), dropping the resulting current density well below the critical value for burning. As the CNT accelerates toward the electrode (point #3 in Figure 5a, 5b), a small spike in I _CN T is still observed due to the rapidly increasing capacitance with decreasing gap before contact which results in charges being pumped into the CNT. However, because of the increased time constant for capacitance discharge, the charge is dissipated over a significantly longer time,

resulting in a peak I _CN T current closer to the steady-state measured current. Thus ablation of the CNT should not be observed with this increased contact resistance.

This was confirmed through experimental characterization. For devices with gold electrodes, ablation was observed in cases with shorter CNT cantilevers and larger CNT-electrode gaps (Figure 4b) . However, for devices with DLC electrodes, no ablation was observed, even in devices approaching the basic geometric constraint in which the CNT-electrode gap cannot be larger than the length of the CNT itself (Figure 4b). As mentioned previously, devices with DLC electrodes were actuated 100 times without observation of

irreversible stiction or ablation (Figure 3b) .

The second embodiment of the invention involves the use of

dielectric ALD (atomic layer deposition) coatings over conventional metal electrodes, Figure 7, and has a similar effect on the current spike. The dielectric layer can have a thickness of 1 Angstrom to 10 nanometers. Such a coating prevents direct Ohmic contact between the nanostructure and electrode during pull-in. Instead, when the nanomember such as CNT cantilever comes into contact with the dielectric coating, charges must tunnel through the dielectric to reach the electrode. Going back to the gap-dependent resistance expression (Rem ⁼ R _c exp (KH) ) , this effectively sets a minimum CNT- electrode gap H equivalent to the thickness of the dielectric layer. As a result, a similarly large value of J _C NT is achieved.

Note that in the case of DLC electrodes, a large i¾ _NT was achieved by increasing R _Cf whereas for the ALD coating, this is achieved by setting a lower bound on H.

Examples of ALD films include, but are not limited to, oxides (e.g. A1 ₂ 0 ₃ , Ti0 ₂ , Sn0 _2/ ZnO, Hf0 ₂ ) , metal nitrides (e.g. TiN, TaN, WN, NbN) , metals (e.g. Ru, Ir, Pt) , and metal sulfides (e.g. ZnS) . ALD is commonly used in the microelectronics industry to deposit gate oxides for transistors or to deposit dielectrics for dynamic random access memory (DRAM) capacitors.

Figures 4c and 4d show maps of failure modes for devices with gold electrodes and with DLC electrodes, respectively. The Examples demonstrate that for devices tested using DLC electrodes, there is robust region in which neither mode of stiction nor ablation

failure is expected and is expanded dramatically, Figure 4d, as compared to devices with gold electrodes where there is only a highly limited region, Figure 4c, in which neither mode of failure is expected to occur. This leaves a significantly larger region in the L-H design space in which NEMS devices can be manufactured robustly. The design space for devices employing dielectric ALD coatings on the electrode will have a similarly large robust region as the coating has a similar impact on the nanost ructure-elect rode adhesion and transient current spikes. The present invention will have uses in the micro electronics and nanoelect ronics ^' as well as telecommunicatons industries as a result.

Although the invention has been described in connection with certain embodiments thereof, those skilled in the art will appreciate that various changes and modifications can be made therein within the scope of the invention as set forth in the appended claims.

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