The present invention relates to Schottky diodes, and more particularly, to Schottky diodes using semi-conducting single-walled nanotubes (s-SWNTs) with dissimilar contacts for high-frequency applications.
For high-frequency applications in the range of 30 gigahertz (GHz) to 3 terahertz (THz), (i.e., microwave to sub-millimeter wave region), diodes are of particular interest as detectors, mixers, and frequency multipliers. In particular, solid-state Schottky diodes (rectifying metal-semiconductor junctions) are employed because of their higher switching speeds and their inherent suitability for low-voltage, high-current applications. The state-of-the-art utilizes solid-state Schottky diode detectors for room temperature sensor systems and Schottky diode multipliers for sub-millimeter wave power generation. However, above a few hundred GHz, the inherent parasitic capacitance (proportional to semiconductor junction area) and resistance (inversely proportional to electron mobility) of these devices severely limit the achievable sensitivity for detection, (direct detector noise equivalent power (NEP)˜10−12 W/square-root (√) Hz, heterodyne NEP˜10−17 W/√Hz for cooled operation at 4 K), and generated power at THz frequencies (generally only microwatts of power up to 1.5 THz). Such limitations are due, in part, because of the limitations of the fabrication process and the material properties. From the material point of view, carbon nanotubes offer an excellent alternative to their solid-state counterparts because of their small junction areas due to their physical dimensions (<1 to 2 nm diameter), high electron mobilities (up to 200,000 cm2/Vs as reported in the art) and low estimated capacitances (tens of aF/μm), leading to predicted cut-off frequencies in the THz range.
The electronic properties of single-walled carbon nanotubes (SWNTs) have been studied in detail. The synthesis of SWNTs results in tubes that are either metallic (m-SWNTs) or semiconducting (s-SWNTs) depending on their chirality. Semiconducting SWNTs typically exhibit p-type conductivity for measurements done in the air. Earlier studies have employed s-SWNTs to develop Schottky-barrier-contact field effect transistors (FETs) and to rectify junctions based on carbon nanotube (CNT) defects, double gates, or crossed m- and s-SWNTs. Others have studied in detail, the AC response of s-SWNT-FETs using phenomenological models and through measurements at 2.6 GHz. Interestingly, a significantly decreased AC impedance (when compared to DC impedance) of the device (at 4 K) has been shown, resulting from of a possible capacitive coupling between the nanotube and the contact pads. In fact, in m-SWNT circuits, studies have measured AC impedances (˜1.7 kΩ) much lower than the quantum limited resistance for a one-dimensional (1-D) system (h/4e2˜6.25 kΩ, where h is Planck's constant and e is the charge of an electron). While, this is encouraging, a further reduction in parasitics that hinder the AC performance of an electronic device can be achieved by employing a Schottky diode design in which a substrate-less membrane architecture can be employed similar to an earlier reported monolithic membrane diode (MoMED) design for a 2.5 THz receiver system. A theoretical study concluded that unlike in planar junction Schottky diodes, the Fermi level pinning in carbon nanotube Schottky diodes does not control the device properties and, as a result, the threshold may be tuned for optimal device performance. The theoretical study showed that for these devices, the Schottky barrier height is controlled by the metal work function, unaffected by the Fermi level pinning, which offers the possibility of controlling the barrier height by the choice of the metal.
However, nothing previously devised has incorporated nanotubes into a Schottky diode. Thus, a continuing need exists for a Schottky diode using a nanotbue that maintains performance at frequencies above 500 GHz.
The present invention relates to a nanotube Schottky diode. The nanotube Schottky diode comprises a nanotube formed of a semi-conductive material. A first conductive contact is attached with the nanotube. Additionally, a second conductive contact is attached with the nanotube. The first conductive contact and the second conductive contact are formed of dissimilar materials and each of the conductive contacts is attached with the nanotube such that they are separated.
In one aspect, the first conductive contact is formed of a material that has a lower work function than that of the nanotube to form a Schottky contact and the second conductive contact is formed of a material that has a higher work function than that of the nanotube to form an Ohmic contact.
In yet another aspect, the present invention further comprises a substrate with an insulating layer formed on the substrate. The nanotube is attached with the insulating layer.
In another aspect, the nanotube has a length with two ends and the first conductive contact is attached proximate one of the two ends of the nanotube while the second conductive contact is attached proximate the other of the two ends of the nanotube.
Additionally, the Schottky contact is formed of at least one material selected from a group consisting of titanium and aluminum. Further, the Ohmic contact is formed of at least one material selected from a group consisting of platinum and palladium.
In another aspect, each of the conductive contacts further comprises a contact pad attached with the conductive contact.
In yet another aspect, the substrate is formed of silicon and the insulating layer is formed of at least one material selected from a group consisting of silicon dioxide and silicon nitride.
In another aspect, each of the conductive contacts includes an axis that is approximately parallel to the other axis and that runs approximately perpendicular to the nanotube. The substrate is etched-out as an etched-out portion between each of the axes, such that the insulating layer and the nanotube span across the etched-out portion. In another aspect, a gap exists in the substrate and in the insulating layer between each of the axes, such that the nanotube is suspended across and bridges the gap.
Furthermore, the nanotube is a single-walled carbon nanotube, or in another aspect, a multi-walled carbon nanotube.
In another aspect, the present invention comprises a method for forming the nanotube Schottky diode described herein. Finally, the present invention includes a diode produced by the aforementioned method.
The objects, features and advantages of the present invention will be apparent from the following detailed descriptions of the various aspects of the invention in conjunction with reference to the following drawings, where:
The present invention relates to Schottky diodes and, more particularly, to Schottky diodes using semi-conducting single-walled nanotubes (s-SWNTs) with dissimilar contacts (e.g., a titanium Schottky contact and a platinum Ohmic contact) for high-frequency applications. The following description is presented to enable one of ordinary skill in the art to make and use the invention and to incorporate it in the context of particular applications. Various modifications, as well as a variety of uses in different applications will be readily apparent to those skilled in the art and the general principles defined herein may be applied to a wide range of embodiments. Thus, the present invention is not intended to be limited to the embodiments presented, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced without necessarily being limited to these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present invention.
The reader's attention is directed to all papers and documents which are filed concurrently with this specification and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference. All the features disclosed in this specification, (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
Furthermore, any element in a claim that does not explicitly state “means for” performing a specified function, or “step for” performing a specific function, is not to be interpreted as a “means” or “step” clause as specified in 35 U.S.C. Section 112, Paragraph 6. In particular, the use of “step of” or “act of” in the claims herein is not intended to invoke the provisions of 35 U.S.C. 112, Paragraph 6.
Before describing the invention in detail, a description of various principal aspects of the present invention is provided. Subsequently, an introduction provides the reader with a general understanding of the present invention. Finally, details of the invention are presented to give an understanding of the specific aspects.
(1) Principal Aspects
The present invention has two “principal” aspects. The first is a Schottky diode having a nanotube and dissimilar contacts for use in high-frequency applications. The second principal aspect is a method for forming the Schottky diode. These aspects will be described in more detail below.
(2) Introduction
The present invention comprises Schottky diodes created by depositing two dissimilar conductive materials (e.g., metals) at the two ends of p-type s-single-walled carbon nanotubes (SWNTs). One of the metals has a lower work function (Φ) than that of the SWNT (ΦNT˜4.9 eV) to make a Schottky contact and the other metal has a higher Φ than that of the SWNT to make an Ohmic contact. The present invention also includes a method for forming the Schottky diodes. The performances of these diodes as detectors at high-frequencies is shown below by calculating their voltage responsivity and noise equivalent power (NEP) using analytical models.
(4) Details of the Invention
As described above, the present invention relates to a Schottky diode having a nanotube connecting two dissimilar metals. For clarity, various versions of the nanotube Schottky diode will be described first. Second, methods for forming the Schottky diodes will be described. Third, experimental results using a Schottky diode are provided.
(4.1) Nanotube Schottky Diodes
As shown in
Using a catalyst 106, a nanotube 108 is grown on the insulating layer 104, with the resulting nanotube 108 having a certain length 109 and two opposing ends. Two contacts of dissimilar conductive materials (e.g., metals) are formed on the nanotube 108 with a gap therebetween. In one non-limiting example, one of the contacts is formed proximate one of the opposing ends while the other contact is formed proximate the other opposing end. Additionally, one of the contacts is an Ohmic contact 110 while the other contact is a Schottky contact 112. An Ohmic contact is a region on a device that has been prepared so that the current-voltage (I-V) curve of the device is linear and symmetric. If the I-V characteristic is non-linear and asymmetric, the contact can instead be termed a blocking or Schottky contact.
To enable connection of various devices to the Schottky diode 100, a contact pad 114 is attached with each of the metal contacts 110 and 112. The contact pad 114 is formed of a conductive material, a non-limiting example of which includes gold (Au).
It should be noted that although the nanotube 108 has been described as being grown on a substrate (e.g., insulating layer 104) of the diode 100, the present invention is not limited thereto. As can be appreciated by one skilled in the art, the nanotube 108 can be grown separately and subsequently placed on the substrate (e.g., the spin-coated nanotubes produced by Nantero, Inc., which is located at 25-D Olympia Avenue, Woburn, Mass. 01801).
The nanotube 108 is formed of any semi-conductive material, a non-limiting example of which includes carbon. More specifically, the nanotube 108 can be a s-single-walled carbon nanotubes (SWNTs). However, as can be appreciated by one skilled in the art, multi-walled carbon nanotubes can also be used, as long as they are completely semi-conducting. Additionally, although depicted as a single nanotube 108, actual formation and usage of the nanotubes typically results in and requires multiple nanotubes. Furthermore, as stated above, although the Schottky diode 100 is illustrated for a carbon nanotube, it can be applied to any other type of semi-conducting material nanotubes or nanowires.
The material for the Schottky contact 112 is a material (e.g., metal) that has a lower work function (Φ) than that of the SWNT, non-limiting examples of which include titanium (Ti) or aluminum (Al). Alternatively, the material for the Ohmic contact 110 is a material that has a higher Φ than that of the SWNT, non-limiting examples of which include platinum (Pt) and palladium (Pd). In one non-limiting example, the choice of metals used are Ti for the Schottky contact 112 (ΦTi=4.33 eV<ΦNT; ΦNT˜4.9 eV) and Pt for the Ohmic contact 110 (ΦPt=5.65 eV>ΦNT)
(4.2) Formation of a Schottky Diode having a Nanotube with Dissimilar Contacts
The present invention also comprises a method for forming the Schottky diodes having a nanotube with tow dissimilar contacts. Although the process described below applies primarily to the angled evaporation technique (as shown in
As shown in
The distribution of nanoparticle diameters was 5.8±2.0 nm as determined by transmission electron microscopy (TEM) using an Akashi EM-002b electron microscope at 100 kilovolts (kV). As described previously, monolayers of FeNPs were patterned onto oxidized silicon substrates using 350 nm thick polymethyl methacrylate (PMMA) (produced by MicroChem Corp., 950K molecular weight, 4% in chlorobenzene). MicroChem Corp. is located at 1254 Chestnut Street, Newton, Mass., 02462.
All the growths were done at 850° C. using methane (CH4 at 1500 standard cubic centimeters per minute (sccm)) and hydrogen (H2 at 50 sccm) at a pressure of 780 torr. The resulting SWNTs were characterized by atomic force microscopy (AFM) using a Digital Instruments (DI) Nanoscope III with silicon probes in Tapping Mode. The DI Nanoscope III is produced by Veeco Instruments, located at 112 Robin Hill Rd., Santa Barbara, Calif., 93111. The tube diameters were measured to be between 1 and 3 nm. TEM studies revealed that most of the nanotubes produced were single-walled, although there is the possibility of occasional double walled nanotubes.
The Schottky diode fabrication involved patterning the electrodes directly over the nanotubes 202 using three masking layers stacked as follows: 700 nm thick 950,000 (K) molecular weight PMMA; 15 nm thick Ti; and 1.4 micrometer (μm) thick photoresist 200, with PMMA being the bottom-most layer used to protect the nanotube 202 during further processing. The photoresist 200 was patterned to create an “isolation block” between the two opposing ends of the nanotube 202 followed by the removal of the Ti layer in CF4/O2 plasma. The isolation block facilitates selective coating of the ends of the nanotube 202 with dissimilar metals through angled evaporation. The electrode patterns were transferred into PMMA with ˜1 μm undercut. At this stage, the portion of the nanotube 202 (i.e., SWNT) that lies between the electrode patterns was still covered by the PMMA protective layer. Finally, as shown in Acts 2 through 4 (shown in
(4.3) Exemplary Experimental Results
As can be appreciated by one skilled in the art, the experimental results herein are provided for illustrative purposes only and the invention is not intended to be limited thereto. The first set of devices produced mostly contained a single SWNT bridging the gap between the metal pads in each device. As each device may have either a metallic or a semi-conducting tube, the diodes were identified by gating with the substrate.
These factors pose a significant challenge for impedance-matching in high-frequency applications. Effective impedance-matching requires decreasing both the individual tube impedance as well as the total device impedance. The former can be accomplished to a certain extent by annealing the contact pads, by improved wetting properties of the deposited metal, and by decreasing the lengths of the SWNTs (thus making it a ballistic transport device). The total device impedance can be decreased by using many nanotubes in parallel per device.
To illustrate this, a second set of devices was developed with multiple SWNTs in parallel per device. Each device typically had 8 to 10 SWNTs, of both metallic and semiconducting in nature, grown in parallel between the contact pads. The presence of m-SWNTs precludes rectification. Therefore, using a previously described procedure (i.e., Collins, P. G.; Arnold, M. S.; Avouris, P. Science, 2001, 292, 706-709), m-SWNTs (metallic tubes) were selectively burnt-out by gating off s-SWNTs by biasing the substrate to +20 V and increasing the total current through the device in a step-wise fashion. After every burn-out step, the I-V curves were recorded until a rectifying curve was observed.
The quality of a diode can be assessed by its ideality factor (n), calculated using the diode equation. Typically, this factor lies between one and two for good diodes with n=1 for an ideal diode. The value of n for the Schottky diodes was computed by fitting the curves using the following diode equation:
where, I=the measured total current, V=corresponding anode-cathode biasing voltage, IS=the reverse saturation current (or the leakage current), Rs=the lumped series resistance of the device (the effective total of the contact resistances and the nanotube resistance), q=the electron charge (1.602×10−19 columbs (C)), k=the Boltzmann constant, and T=the temperature (° K).
In low bias ranges (as shown in the
Using the Rs and the CP parameters, the predicted performance of the d2-II SWNT-Schottky diode as a direct detector at high-frequency ranges during low bias operation was calculated. The analysis used a simplistic noise equivalent circuit 600 as shown in the inset of
These relations are based upon the circuit shown in the inset 600 of
In equation (2), the quantity under the square root tends to unity for Rs>>Rj (which is true as long as Rs is in the range of hundreds of kΩ). In equation (3), I0 is the DC bias current (same as I in equation (1)) corresponding to the optimized DC bias voltage, V0. V0 is calculated iteratively to achieve the least noise power for a given diode and a given detection frequency. V0, in turn, depends on Rs. The voltage responsivity, βV, is calculated as,
βV=γ0βRVT(V/W), (4)
where
and, RCT=Rs+Rj; assuming an infinite load and an antenna-matched source to the diode. The NEP is calculated by dividing the voltage noise density νn, by the voltage responsivity, βV, according to the following:
TD is the diode equivalent noise temperature. As Rs decreases, βV increases at a higher rate than the rate of decrease of νn, thus effectively decreasing the NEP.
The above-mentioned performance parameters have been calculated for the device d2-II using the following values: Rs=640 kΩ/tube (for four tubes in parallel the effective Rs is 160 kΩ; in comparison, Rj is only ˜796 Ω/tube); CP=75 aF, n=1.55; and IS=15 nA. For this device, it was found that the optimized bias voltage, V0, is equal to 0.20 V, which is in a region where the ideality curve fit begins to deviate (see
For high-frequency technological applications of carbon nanotubes, the results suggest that key impedances should be adjusted to improve device performance. It has been observed that the AC resistance in the SWNT device could become considerably lower because of the capacitive coupling between the nanotube and the contact pads. Such observations were made by Li, S; Yu, Z; Yen, S-F; Tang, W. C.; and Burke, P. J., in Nano Lett. 2004, 4, 753-756. In this case, it is indeed possible to bring Rs down to the order of a few kΩ, which then should improve the NEP. Also, growing hundreds of nanotubes in parallel per device allows the effective impedance (series resistance and the kinetic inductance) to be decreased to achieve proper impedance matching. To decrease parasitic capacitances, one can employ the substrate-less dielectric membrane design in which the substrate is relegated to just a frame to support the dielectric membrane upon which the device is fabricated. This is an attractive option for high-frequency applications that cannot be readily achieved in a field effect transistor (FET) design in which a gate is a necessity, either in the substrate form (bottom gate) or as a top gate. In essence, the SWNT Schottky diodes with multiple parallel tubes per device with individually reduced resistances to the order of a few kΩ promise superior performance compared to that of the state-of-the art solid-state Schottky diodes (particularly for applications at high frequencies).
The present application is a non-provisional application, claiming the benefit of U.S. Provisional Application No. 60/683,825, filed on May 23, 2005, titled, “Carbon Nanotube Schottky Diodes for High Frequency Applications.”
The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of Public Law 96-517 (35 USC 202) in which the Contractor has elected to retain title.
Number | Date | Country | |
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60683825 | May 2005 | US |