The invention relates to solid state resistive devices used for memory storage.
Resistive random-access memories (RRAMs) have generated significant interest recently as a potential candidate for ultra-high density non-volatile information storage. A typical RRAM device consists of an insulator layer sandwiched between a pair of electrodes and exhibits electrical pulse induced hysteretic resistance switching effects.
The resistance switching has been explained by the formation of conductive filaments inside the insulator due to Joule heating and electrochemical processes in binary oxides (e.g. NiO and TiO2) or redox processes for ionic conductors including oxides, chalcogenides and polymers. Resistance switching has also been explained by field assisted diffusion of ions in TiO2 and amorphous silicon (a-Si) films.
In the case of a-Si structures, voltage-induced diffusion of metal ions into the silicon leads to the formation of conductive filaments that reduce the resistance of the a-Si structure. These filaments remain after the biasing voltage is removed, thereby giving the device its non-volatile characteristic, and they can be removed by reverse diffusion of the ions back to the metal electrode under the motive force of a reverse polarity applied voltage.
Resistive devices formed by an a-Si structure sandwiched between two metal electrodes have been shown to exhibit this controllable resistive characteristic. However, such devices typically have micron sized filaments which may prevent them from being scaled down to the sub-100 nanometer range. Such devices may also require high forming voltages that can lead to device damage and can limit production yields.
In one aspect, a crossbar memory array includes a first array of parallel nanowires of a first material and a second array of parallel nanowires of a second material. The first and the second array are oriented at an angle with each other. The array further includes a plurality of nanostructures of non-crystalline silicon, with a nanostructure disposed between a nanowire of the first material and a nanowire of the second material at each intersection of the two arrays. The nanostructures form a resistive memory cell together with the nanowires of the first and second materials.
In another aspect, a method for fabricating an array of resistive memory devices includes forming a first array of parallel nanowires of a first material on a substrate. A plurality of non-crystalline silicon nanostructures are formed on the first array of parallel nanowires. The method further includes forming a second array of parallel nanowires of a second material on the plurality of non-crystalline silicon nanostructures. The second array is oriented at an angle with the first array such that each intersection of the first array and the second array includes one of the non-crystalline silicon nanostructures disposed between a nanowire of the first material and a nanowire of the second material to form a resistive memory cell.
In still another aspect, a non-volatile solid state resistive device is presented. The device includes a substrate, a first electrode and an n-type silicon second electrode on the substrate. A p-type silicon body is vertically stacked between the first electrode and the n-type silicon electrode and in contact with the n-type silicon second electrode, forms a PN diode. The device further includes a non-crystalline silicon nanostructure vertically stacked between the first electrode the a p-type silicon body.
Implementations of the crossbar memory can include one or more of the following features. The first material of the crossbar memory array may be chosen from one of the following metals: silver (Ag), gold (Au), nickel (Ni), aluminum (Al), chromium (Cr), iron (Fe), manganese (Mn), tungsten (W), vanadium (V) and cobalt (Co). At least one of the plurality of non-crystalline silicon nanostructures may be a nanoscale pillar providing a contact point between the first and second arrays at exactly one intersection. At least one of the plurality of non-crystalline silicon nanostructures may be a nanowire providing contact points between the first and second arrays at a plurality of intersections. An angle between the first and second parallel arrays may be substantially equal to a right angle. An insulator or dielectric material, such as spin-on-glass (SOG), may at least partially separate the two arrays. The crossbar memory array may be used either as a resistive random access memory (RRAM) or as read only memory (ROM). Each of the plurality of non-crystalline silicon nanostructures may exhibit variable resistance that can be adjusted based on an amplitude of a voltage or current and/or a duration of the voltage or current which is applied across the resistive memory cell.
Implementations of the method for fabricating the array of resistive memory devices may include one or more of the following features. The first material and second materials may be acceptor doped silicon and a metal, respectively. The first material may be a metal and the second material may be acceptor doped silicon. Both the first and the second materials may be metals different from one another. The acceptor used in the acceptor doped silicon may be Boron. The removing step may include reactive ion etching (RIE). The insulator may be spin-on-glass (SOG) and may be deposited via spin coating and thermal curing methods. The method may includes the use of one or more micro-fabrication techniques such as e-beam lithography, chemical vapor decomposition (CVD) and lift-off.
Potential advantages can include the following. The crossbar memory arrays described herein can exhibit excellent switching characteristics in terms of yield, speed, endurance and retention and can be used as a medium for ultra-high density non-volatile information storage. Probability based bias and time dependent switching characteristics of the a-Si based memory arrays can facilitate applications of the crossbar memory arrays in new applications such as artificial intelligence and simulation of biologically inspired systems.
The details of one or more embodiments are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.
Exemplary embodiments will hereinafter be described in conjunction with the appended drawings, wherein like designations denote like elements, and wherein:
a) is a diagrammatic view of one embodiment of a single cell a-Si resistive device;
b) is an SEM image of a top view of a partially-constructed a-Si structure such as shown in
c) is a graph showing resistance switching characteristic of a typical a-Si structure, such as shown in
d) is a waveform showing the programming response for an a-Si device such as shown in
e) is a waveform showing the results of endurance testing of an a-Si device such as shown in
a)-2(c) depict histograms of the switching response of a typical a-Si device for different bias voltages;
d) is a three-part diagram showing the metal ion diffusion at different conductive states of an a-Si device such as shown in
e) is a graph depicting the relationship between switching time and bias voltage for an a-Si device such as shown in
a) shows the result of programming a typical a-Si device using different series-connected control resistors or different programming current provided by other means;
b) depicts the correlation between the final resistance of the programmed a-Si device and the selected control resistance used to program the device;
c) is a graph of the probability of a single, discrete resistance switching event over time for a typical a-Si device when applying a given bias voltage without any series connected control resistor;
d) is a graph of the probability of having at least one resistance switching event over time for a typical a-Si device when applying a given bias voltage without any series connected control resistor;
e) is a graph of the probability of a single, discrete resistance switching event over time for a typical a-Si device when using a series connected control resistor;
a) is a plot of the wait time for an ON-to-OFF resistance transition when no bias voltage is applied to an a-Si device such as shown in
b) is a graph of the wait time for an ON-to-OFF resistance transition versus temperature;
a) shows a schematic diagrams illustrating how multi-level resistance can be used in circuits for storing multiple bits in a single cell;
b) shows a schematic diagram illustrating how a transistor may be used to control the resistance of the memory cell;
a) and 6(b) are schematic diagrams of two embodiments of crossbar memory arrays;
a) is a scanning electron microscope (SEM) image of a top view of a 16×16 array;
b) shows an array of p-Si nanowires;
a) shows a result of an initial step according to an embodiment of a method for fabricating a crossbar memory array;
b) illustrates a result of a step of forming contact pads and traces according to embodiments of the present invention;
c) illustrates a result of a step of depositing one or more layers of material according to embodiments of the present invention;
d) illustrates a result of a step of patterning the one or more layers of material according to embodiments of the present invention;
e) illustrates a result of a step of etching one or more layers of material according to embodiments of the present invention;
f) illustrates a result of a step of removing a mask layer according to embodiments of the present invention;
g) illustrates a result of a step of depositing a layer of material according to embodiments of the present invention;
h) illustrates a result of a step of pattering a layer of material according to embodiments of the present invention;
i) illustrates a result of a step of fabricating a mask according to embodiments of the present invention;
j) illustrates a result of a step of etching one or more layers of material according to embodiments of the present invention;
k) illustrates a result of a step of depositing one or more layers of material according to embodiments of the present invention;
l) illustrates a result of a step of depositing one or more layers of material according to embodiments of the present invention;
m) illustrates a result of a step of patterning one or more layers of material according to embodiments of the present invention;
n) illustrates a result of a step of patterning one or more layers of material according to embodiments of the present invention;
a) shows a result of an initial step according to another embodiment of a method for fabricating a crossbar memory array;
b) illustrates a result of a step of forming contact pads and traces according to embodiments of the present invention;
c) illustrates a result of a step of depositing one or more layers of material according to embodiments of the present invention;
d) illustrates a result of a step of patterning the one or more layers of material according to embodiments of the present invention;
e) illustrates a result of a step of etching one or more layers of material according to embodiments of the present invention;
f) illustrates a result of a step of removing a mask layer according to embodiments of the present invention;
g) illustrates a result of a step of depositing one or more layers of material according to embodiments of the present invention;
h) illustrates a result of a step of patterning one or more layers of material according to embodiments of the present invention; and
i) illustrates a result of a step of patterning one or more layers of material according to embodiments of the present invention.
a) depicts a non-volatile solid state resistive device 100 comprising a nanoscale a-Si structure 101 that exhibits a resistance that can be selectively set to various values, and reset, all using appropriate control circuitry. Once set, the resistance value can be read using a small voltage that is sufficient in magnitude to determine the resistance without causing it to change. Although the illustrated embodiment uses a-Si as the resistive element, it will be appreciated that other non-crystalline silicon (nc-Si) structures can be used, such as amorphous poly-silicon (sometimes called nanocrystalline silicon, an amorphous phase that includes small grains of crystalline silicon). Thus, as used herein and in the claims, noncrystalline silicon (nc-Si) means either amorphous silicon (a-Si), amorphous poly-silicon (poly-Si) that exhibits controllable resistance, or a combination of the two. Furthermore, although much of the discussion herein applies also to larger scale a-Si structures such as those having one or more dimensions in the micron range, the illustrated embodiment is an a-Si nanostructure 101 that exhibits certain characteristics unique to its small scale. The term nanostructure, as used herein, refers to a structure having at least two dimensions in the nanoscale range; for example, structures having a diameter or plural cross-sectional dimensions within the general range of 0.1 to 100 nanometers. This includes structures having all three spatial dimensions in the nanoscale; for example, a cylindrical nanocolumn or nanopillar having a length that is on the same order as its nanoscale diameter. Nanostructures can include the various nanoscale structures known to those skilled in the art; for example, nanotubes, nanowires, nanorods, nanocolumns, nanopillars, nanoparticles, and nanofibers. One such structure 101 is the embodiment depicted in
The a-Si structure of
To fabricate the a-Si device of
A single a-Si device 100 as shown in
c) shows the resistance switching characteristics of a typical a-Si pillar 101 such as shown in
The switching in an a-Si structure 101 can be explained by the formation and retrieval of a nanoscale Ag filament upon the application of the programming voltage, schematically illustrated in
The well-defined active switching area in the a-Si pillar structure 101 along with the fine control offered by the CMOS compatible fabrication process enables detailed studies to explore the unique characteristics offered by the resistive switching devices. One direct consequence of the filament formation model is that the switching rate will be bias dependent, since unlike electron tunneling, the hopping of the Ag particles 210 is a thermally activated process and the rate is determined by the bias-dependent activation energy Ea′(V):
Γ=1/τ=νe−E
where kB is Boltzmann's constant, T is the absolute temperature, τ is the characteristic dwell time and ν is the attempt frequency. As indicated in
This effect has been verified through a study of the wait time for the first transition (i.e., the first current step in
The histograms in
τ(V)=τ0e−V/V
It is interesting to note the physical meaning of V0 in Equation 3. From
The bias-dependent switching characteristics have important implications on the device operation. First, the switching essentially does not have a “hard” threshold voltage even though the switching can be very sharp (e.g.
a) shows a schematic diagram illustrating how the multi-level resistance can be used to store a plurality of bits in a same memory cell. In some embodiments, a memory cell 520 is connected in series with an array 525 of resistors 530a-530h (530 in general), and decoding circuitry 535 controls which resistor 530 from the array 525 is connected to the memory cell 520. The resistance R 510 in this case is the resistance due to the non-crystalline or a-Si in the memory cell 520.
In some embodiments, a p-type silicon structure may be vertically stacked between the two electrodes of the device thereby forming a PN diode between the electrodes. The integrated PN diode may then act as a voltage tunable resistor to replace the series control resistor used for achieving multi-bit storage. In such cases, multi-level storage can be achieved with a single PN diode (vs. an array of control resistors 525) in series with the resistive memory device by adjusting an amplitude of a programming pulse.
In other embodiments, a transistor may be used to control the resistance R 510 of the memory cell, as illustrated in
Various approaches can be used to implement the selective programming of multi-level numbers into the a-Si device. As used herein, a multi-level number is a number having more than two (binary) levels or values, such as a base-three digit or number, base-four number, etc. Multi-level number storage can be used to store multiple bits of binary information; for example, a four-level a-Si storage cell can store two bits of binary data in a single a-Si cell, and an eight-level cell can store three bits of binary data. When used in a digital circuit device, the memory cell can include a suitable control circuit to program a binary or other number into the a-Si device. Such circuitry is within the level of skill in the art and an exemplary diagram of one such control circuit is shown in
A control circuit such as in
The a-Si structure can be used as a memory cell of a digital non-volatile memory device having a number of a-Si memory cells arranged in an array or other suitable structure. Rather than being used for bit or multi-level number storage, the a-Si structure can be operated via a method that switches it between the ON and OFF states. This can be done by applying a voltage across the a-Si structure, wherein the applied voltage has a magnitude and duration that are selected so as to achieve a predetermined probability of the a-Si device switching from the OFF state to the ON state. The predetermined probability of successful switching can be, for example, 95% or can be any other percentage desired or required for a particular application of the a-Si device.
As indicated above, the successful operation of the a-Si device depends not only on the amplitude, but also on the duration time of the bias. The requirements also depend on whether digital switching (e.g. as single-bit memories) or analog operations (e.g. as interconnects) are desired. For the Poissonian processes discussed above,
where τ1=3.36 μs and τ2=1.30 s corresponding to the switching rates when the voltages across the device are 4V (before the first switching event and R>>RS) to 2V (after the first switching event and RS=R) respectively, as a result of the voltage divider effect after the first switching event. A much higher success rate of greater than 99% can now be achieved for 5τ1<tpulse<0.01τ2 (about 13 ms time margin at 4 V bias) to limit the switching to the 1st event only. In addition, similar exhibited characteristics are expected from other resistive switching devices since many of them involve some sort of activation energy process, e.g. the diffusion of ions and the redox processes.
The activation energy of the barriers can be extracted from temperature dependence of the wait time from Equation 1.
When incorporated into memory arrays such as described below or when otherwise necessary or desirable for a particular application, the a-Si device can be constructed with an intrinsic diode in the form of a p-n junction. This can be incorporated during fabrication by further including an n-type layer between the p-type poly-Si electrode and the second metal (e.g., platinum) electrode. When used in a memory array of the crossbar type, this construction can be used to prevent cross-talk between adjacent devices since forward conducting current flowing out of one cell through its diode will be blocked by the (now reverse biased) diode of the adjacent cell.
Referring now to
A parallel array of metallic nanowires 610 serve as the top electrodes. The array of metallic nanowires 610 is oriented at an angle with respect to the p-Si nanowire 605 array. The array of metallic nanowires 610 may include metals capable of supplying filament-forming ions such as silver (Ag), gold (Au), nickel (Ni), aluminum (Al), chromium (Cr), iron (Fe), manganese (Mn), tungsten (W), vanadium (V) and cobalt (Co). In some embodiments, the array of metallic nanowires 610 are perpendicular (or oriented at a right angle) to the array of p-Si nanowires 605. In other embodiments, the two arrays may be oriented at any angle with respect to one another. The metallic nanowires 610 can have a width and pitch in nanometer scale. For example, the metallic nanowires can have a width of about 60 nm and pitch of about 150 nm.
Each intersection point 615 of the two arrays produces a resistive memory cell. The memory cell at each intersection 615 includes two electrodes separated by a structure of amorphous silicon (a-Si) 620 or other non-crystalline silicon. In some embodiments, the a-Si structure is fabricated as nanowires 620 disposed on top of the p-Si nanowires 605 as shown in
It should be noted that resistive memory cells can also be fabricated using a metal such as nickel (Ni) or platinum (Pt) in place of p-Si in the bottom electrodes. In one embodiment, an array may comprise one or more Ag/a-Si/Ni memory cell intersections. However, unlike the Ag/a-Si/p-Si structures in which the ON-resistance can be adjusted by tuning the a-Si growth parameters, the Ag/a-Si/Ni devices likely show low RON and high programming currents. In addition, the endurance of the Ag/a-Si/Ni memory cells are typically lower than the Ag/a-Si/p-Si memory cells. In some embodiments, this is due to mechanical stress induced by the high programming current. A high concentration of trapping sites for Ag near the a-Si/metal interface causes the formation of multiple filaments (or filaments with closely spaced Ag trapping sites) thereby increasing the programming current. It should also be noted that the top and bottom electrodes as described above may be interchanged without departing from the scope of the present application.
The crossbar memory array as described above may be fabricated on a silicon substrate 630. In one embodiment, the substrate includes very pure prime grade silicon. In another embodiment, the silicon substrate may be coated with a thin layer of thermal oxide 635. Silicon dioxide (SiO2) may be used as the thermal oxide 635. In other embodiments, III-V type semiconductor compounds (such as Gallium Arsenide GaAs, Gallium Nitride GaN, Boron Nitride BN etc.) or II-VI type semiconductor compounds (such as Cadmium Selenide, Zinc Telluride etc.) may also be used as the substrate 630. The substrate 630 may also be referred to as a wafer.
Electrodes of the two arrays are insulated from one another, and nanowires within the arrays are insulated from each other, using an insulator material 640. In one embodiment a dielectric material such as Spin-On-Glass (SOG) is used for insulating the two arrays. SOG 640 can be applied in a liquid form and thermally cured. SOG 640 fills narrow cavities and spaces and planarizes surfaces. SOG 640 may comprise one or more of the following materials: a silicate, a phosphosilicate and a siloxane. While SOG 640 is used as an example, it should be noted that other insulator and/or dielectric materials may be used for insulating the two arrays of electrodes.
Referring now to
b shows an example how the bottom poly silicon is etched to form the array. In some embodiments, the gaps 720 between the etched poly silicon are reduced to very small dimensions such as less than 25 nm. In some embodiments, the etching of the bottom poly silicon is good for the metal layer in the sense that further processes such as chemical mechanical planarization (CMP) are not required.
Referring again to
Referring now to
Amorphous or non-crystalline (a-Si) based crossbar memory arrays offer many advantages. Besides being compatible with existing CMOS fabrication processes, the large knowledge base accumulated for a-Si thin-film deposition can be used to control the device characteristics. For example, rectifying behavior (diode-like) and non-rectifying (resistor-like) characteristics have been observed in the ON state of the a-Si devices by adjusting the a-Si growth conditions. The rectifying behavior with intrinsic diode characteristics will be desirable in high-density arrays as it reduces crosstalk between adjacent cells. Such a-Si devices are described in U.S. Patent Application Publication No. 2009/0014707 A1 the entire contents of which is hereby incorporated by reference. In addition, a 1D1R (one-diode-one-resistor) structure can be incorporated by the addition of an n-type silicon layer below the p-type silicon nanowire electrode so that a PN junction can be formed in series with the a-Si switch. The cell size in this case will remain at 4F2 where F is the smallest feature size (i.e. electrode linewidth in this case) hence maintaining a clear density advantage compared with other approaches that requires a select transistor (e.g. 1T1R structures).
Referring now to
Referring to
In some embodiments, a layer of poly-silicon (p-Si) 905 is deposited on the substrate. The p-Si is doped with acceptors such as Boron (B) or Aluminium (Al). The acceptor doped p-Si may be deposited on the substrate using chemical vapor deposition (CVD) techniques. In some embodiments, the initial thickness of the P-Si layer 905 may be reduced due to the doping process. This is due to the consumption of Si during the doping. For example, the initial P-Si layer 905 thickness may be 120 nm which is reduced to approximately 65 nm after the doping. In some embodiments, the doping time is controlled to get a desired thickness of the P-Si layer 905. In one embodiment a low pressure chemical vapor deposition (LPCVD) technique may be used for deposition of the acceptor doped Si. However, it should be apparent to one of ordinary skill in the art that other vapor deposition techniques may also be used. Examples of such techniques include but are not limited to atmospheric pressure CVD (APCVD), ultra-high vacuum CVD (UHVCVD), aerosol assisted CVD (AACVD), plasma enhanced CVD (PECVD), microwave plasma assisted CVD (MPCVD), atomic layer CVD (ALCVD) or atomic layer epitaxy, hybrid physical-chemical vapor deposition (HPCVD), hot wire CVD (HWCVD), direct liquid injection CVD (DLICVD) and vapor phase epitaxy (VPE).
Referring to
Referring to
Referring to
Referring to
Referring to
Referring to
Referring now to
j shows the step of SOG etching and
In some embodiments, fabrication of the top electrode nanowires also involves the steps of photoresist removal and a global Pd/Ag lift-off. Thus, in a first lift-off process, the sacrificial lift-off layer is removed along with portions of the metal and passivation layers on it, leaving the deposited metal and passivation layers in the crossbar region and defining wires of Ag layer outside the crossbar region. These steps are illustrated in
Referring now to
Referring now to
Referring to
Referring to
Referring to
Referring to
Referring to
Referring to
h shows contact pads 950 for Ag nanowires that are fabricated on the SOG layer 940. Photolithography and lift-off technique may be used for depositing one or more metallic contact pads 950. In some embodiments, the contact pads 950 may include a combination of nichrome (NiCr) and gold (Au). In one embodiment, fabrication of contact pads 950, along with the Pd contact pads, demarcates the region 925 for fabrication of the crossbar array.
i shows fabrication of top electrodes of the crossbar memory array. In some embodiments, a layer of filament forming ion supplying metal, e.g., Ag, is patterned using E-beam lithography combined with conventional lift-off process. More particularly, a lift-off layer can be deposited over the SOG 940, patterned using E-beam lithograph (with the negative pattern of the Ag nanowires), the ion supply metal can be deposited over the lift-off layer, and the lift-off layer removed so that only the patterned ion supplying metal remains. In addition, the Ag layer extends to existing contact pads for top electrodes. In one embodiments, palladium (Pd) is used over the Ag nanowires for passivation of the Ag nanowires.
A number of embodiments have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, the ordering of layers on the substrate could be reversed, with the metallic nanowires forming the bottom electrodes and the nickel (Ni) or platinum (Pt) or poly-Si nanowires forming the top electrodes. Accordingly, other embodiments are within the scope of the following claims.
This application is a continuation of U.S. patent application Ser. No. 12/582,086 filed Oct. 20, 2009, which claims the benefit of Provisional Application No. 61/106,893 filed Oct. 20, 2008. The entire contents of these prior applications are hereby incorporated by reference.
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Parent | 12582086 | Oct 2009 | US |
Child | 13291094 | US |