WO2002048701A9 - Nanosensors - Google Patents
NanosensorsInfo
- Publication number
- WO2002048701A9 WO2002048701A9 PCT/US2001/048230 US0148230W WO0248701A9 WO 2002048701 A9 WO2002048701 A9 WO 2002048701A9 US 0148230 W US0148230 W US 0148230W WO 0248701 A9 WO0248701 A9 WO 0248701A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nanowire
- article
- analyte
- sample
- nanowires
- Prior art date
Links
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- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
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- G11C2213/81—Array wherein the array conductors, e.g. word lines, bit lines, are made of nanowires
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Definitions
- Another method for detecting an analyte comprises contacting a nanowire with a sample and determining a property associated with the nanowire. A change in the property of the nanowire indicates the presence or quantity of the analyte in the sample.
- nanowire sensor device comprising a semiconductor nanowire and a binding partner having a specificity for a selected moiety.
- the nanowire has an exterior surface formed thereon to form a gate electrode.
- the nanowire also has a first end in electrical contact with a conductor to form a source electrode and a second end in contact with a conductor to form a drain electrode.
- an analyte-gated field effect transistor having a predetermined current- voltage characteristic and adapted for use as a chemical or biological sensor.
- Fig. 8c shows current-voltage (I-V) measurements for a single-walled carbon nanotube device of Fig. 8b in CrClx.
- Fig. 9c show the relative conductance of the nanosensors with changes in pH levels.
- Fig. lOe shows the conductance of a Biotin modified nanosensor exposed to a blank buffer solution, then to a solution containing Sfreptavidin, and then again to a blank buffer solution.
- Fig. 15 is a schematic view of an InP nanowire.
- Fig. 15b shows the change in luminescence of a nanowire of Fig. 15a over time as pH varies.
- a “nanowire” is an elongated nanoscale semiconductor which, at any point along its length, has at least one cross-sectional dimension and, in some embodiments, two orthogonal cross-sectional dimensions less than 500 nanometers, preferably less than 200 nanometers, more preferably less than 150 nanometers, still more preferably less than 100 nanometers, even more preferably less than 70, still more preferably less than 50 nanometers, even more preferably less than 20 nanometers, still more preferably less than 10 nanometers, and even less than 5 nanometers.
- the cross-sectional dimension can be less than 2 nanometers or 1 nanometer.
- electrically coupled when used with reference to a nanowire and an analyte, or other moiety such as a reaction entity, refers to an association between any of the analyte, other moiety, and the nanowire such that electrons can move from one to the other, or in which a change in an electrical characteristic of one can be determined by the other. This can include electron flow between these entities, or a change in a state of charge, oxidation, or the like that can be determined by the nanowire.
- electrical coupling can include direct covalent linkage between the analyte or other moiety and the nanowire, indirect covalent coupling (e.g.
- polypeptide polypeptide
- peptide protein
- protein protein
- amino acid polymers in which one or more amino acid residue is an artificial chemical analogue of a corresponding naturally occurring amino acid, as well as to naturally occurring amino acid polymers.
- amino acid polymers in which one or more amino acid residue is an artificial chemical analogue of a corresponding naturally occurring amino acid, as well as to naturally occurring amino acid polymers.
- the term also includes variants on the traditional peptide linkage joining the amino acids making up the polypeptide.
- nanowires can be grown on and/or applied to surfaces in patterns useful for electronic devices in a manner similar to techniques described herein involving nanowires, without undue experimentation.
- the nanowires should be able to be formed of at least one micron, preferably at least three microns, more preferably at least five microns, and more preferably still at least ten or twenty microns in length, and preferably are less than about 100 nanometers, more preferably less than about 75 nanometers, and more preferably less than about 50 nanometers, and more preferably still less than about 25 nanometers in thickness (height and width).
- nanowire ropes can be used in the invention, individual nanowires are preferred.
- the invention may utilize metal-catalyzed CVD to synthesize high quality individual nanowires such as nanotubes for molecular electronics.
- CVD synthetic procedures needed to prepare individual wires directly on surfaces and in bulk form are known, and can readily be carried out by those of ordinary skill in the art. See, for example, Kong, et al, “Synthesis of Individual Single- Walled Carbon Nanotubes on Patterned Silicon Wafers", Nature 395, 878-881 (1998); Kong, et al, “Chemical Vapor Deposition of Methane for Single- Walled Carbon Nanotubes” Chem. Phys. Lett.
- the catalyst is not limited to Au only.
- a wide rage of materials such as (Ag, Cu, Zn, Cd, Fe, Ni, Co...) can be used as the catalyst.
- any metal that can form an alloy with the desired semiconductor material, but doesn't form more stable compound than with the elements of the desired semiconductor can be used as the catalyst.
- the buffer gas can be Ar, N2, and others inert gases. Sometimes, a mixture of H2 and buffer gas is used to avoid undesired oxidation by residue oxygen. Reactive gas can also be introduced when desired (e.g. ammonia for GaN). The key point of this process is laser ablation generates liquid nanoclusters that subsequently define the size and direct the growth direction of the crystalline nanowires.
- nanowires with uniform size (diameter) distribution can be produced, where the diameter of the nanowires is determined by the size of the catalytic clusters, as illustrated in Fig. 4.
- nanowires with different lengths can be grown.
- C-CVD catalytic chemical vapor deposition
- the reactant molecules e.g., silane and the dopant
- the doping element e.g. diborane and phosphane for p-type and n-type doped nanowire.
- the doping concentration can be controlled by controlling the relative amount of the doping element introduced in the composite target.
- ZnO/ZnS/ZnSe/ZnTe CdS/CdSe/CdTe, HgS/HgSe/HgTe, BeS/BeSe/BeTe/MgS/MgSe
- the reaction entity is positioned relative to the nanowire to cause a detectable change in the nanowire.
- the reaction entity may be positioned within 100 nanometers of the nanowire, preferably with in 50 nanometers of the nanowire, and more preferably with in 10 nanometers of the nanowire, and the proximity can be determined by those of ordinary skill in the art.
- the reaction entity is positioned less than 5 nanometers from the nanoscopic wire.
- the reaction entity is positioned with 4 nm, 3 nm, 2 nm, and 1 nm of the nanowire.
- the reaction entity is attached to the nanowire through a linker.
- attached to in the context of a species relative to another species or to a surface of an article, means that the species is chemically or biochemically linked via covalent attachment, attachment via specific biological binding (e.g., biotin/streptavidin), coordinative bonding such as chelate/metal binding, or the like.
- specific biological binding e.g., biotin/streptavidin
- coordinative bonding such as chelate/metal binding, or the like.
- the detector can be constructed for measuring a change in an electronic or magnetic property (e.g. voltage, current, conductivity, resistance, impedance, inductance, charge, etc.) can be used.
- the detector typically includes a power source and a voltmeter or amp meter.
- a conductance less than 1 nS can be detected.
- a conductance in the range of thousandths of a nS can be detected.
- the concentration of a species, or analyte may be detected from less than micromolar to molar concentrations and above.
- amine groups may be attached by first making the nanoscale detector device hydrophilic by oxygen plasma, or an acid and/or oxidizing agent and the immersing the nanoscale detector device in a solution containing amino silane.
- DNA probes may be attached by first attaching amine groups as described above, and immersing the modified nanoscale detector device in a solution containing bifunctional crosslinkers, if necessary, and immersing the modified nanoscale detector device in a solution containing the DNA probe.
- the process may be accelerated and promoted by applying a bias voltage to the nanowire, the bias voltage can be either positive or negative depending on the nature of reaction species, for example, a positive bias voltage will help to bring negatively charged DNA probe species close to the nanowire surface and increase its reaction chance with the surface amino groups.
- Figs. 5a and 5b show the conductance for a single silicon nanowire, native and coated, respectively, as a function of pH. As seen in Fig. 4, the conductance of the silicon nanowire changes from 7 to 2.5 when the sample is changed.
- the silicon nanowire of Fig. 5 has been modified to expose amine groups at the surface of the nanowire.
- Fig. 5 shows a change in response to pH when compared to the response in Fig. 4.
- the modified nanowire of Fig. 5 shows a response to milder conditions such as, for example, those present in physiological conditions in blood.
- Fig. 6 shows the conductance for a silicon nanowire having a surface modified with an oligonucleotide agent reaction entity. The conductance changes dramatically where the complementary oligonucleotide analyte binds to the attached oligonucleotide agent.
- Fig. 10a shows an increase in conductance of a silicon nanowire(SiNW) modified with a reaction entity BSA Biotin, as it is exposed first to a blank buffer solution, and then to a solution containing an analyte, 250 nM Streptavidin.
- Fig. 10b shows an increase in conductance of a SiNW modified with BSA Biotin, as it is exposed first to a blank buffer solution, and then to a solution containing 25 pM Streptavidin.
- Fig. 10c shows no change in conductance of a bare SiNW as it is exposed first to a blank buffer solution, and then to a solution containing Streptavidin.
- Fig. 10a shows an increase in conductance of a silicon nanowire(SiNW) modified with a reaction entity BSA Biotin, as it is exposed first to a blank buffer solution, and then to a solution containing an analyte, 250 nM Streptavidin.
- Fig. 10b shows
- Amine modified SiNW may also detect the presence of metal ions.
- Fig. 12a shows the change in conductance of an amine modified SiNW when alternately exposed to a blank buffer solution and a solution containing ImM Cu(II).
- Fig. 12b shows the increases in conductance as the amine modified SiNW is exposed to concentrations of Cu(II) from 0.1 mM to ImM.
- Fig. 12c shows the increase in conductance verses Cu(II) concentration.
- Fig. 12d shows no change in conductance of an unmodified SiNW when exposed first to a blank buffer solution and then to ImM Cu(II).
- Fig. 12a shows the change in conductance of an amine modified SiNW when alternately exposed to a blank buffer solution and a solution containing ImM Cu(II).
- Fig. 12b shows the increases in conductance as the amine modified SiNW is exposed to concentrations of Cu(II) from 0.1 mM to ImM.
- Fig. 13a shows the conductance of a silicon nanowire modified with calmodulin, a calcium binding protein.
- region 1 shows the conductance of the calmodulin modified silicon when exposed to a blank buffer solution.
- Region 2 shows the drop in conductance of the same nanowire when exposed to a solution containing calcium ions noted in fig. 3 with a downward arrow.
- Region 3 shows the increase in conductance of the same nanowire is again contacted with a blank buffer solution, indicated with an upward arrow. The subsequent return of conductance to its original level indicates that the calcium ion is reversible bound to the calmodulin modified nanowire.
- Fig. 13b shows no change in conductance of an unmodified nanowire when exposed first to a blank buffer solution, and then to a solution containing calcium ions.
- the invention provides a nanoscale electrically based sensor for determining the presence or absence of analytes suspected of being present in a sample.
- the nanoscale provides greater sensitivity in detection than that provided by macroscale sensors.
- Fig. 14a shows a calculation of sensitivity for detecting up to 5 charges compared to the doping concentration and nanowire diameter.
- the sensitivity of the nanowire may be controlled by changing the doping concentration or by controlling the diameter of the nanowire. For example, increasing the doping concentration of a nanowire increases the ability of the nanowire to detect more charges. Also, a 20 nm wire requires less doping than a 5 nm nanowire for detecting the same number of charges.
- Fig. 14b shows a calculation of a threshold doping density for detecting a single charge compared to the diameter of a nanowire. Again, a 20 nm nanowire requires less doping than a 5 nm nanowire to detect a single charge.
- the nanowire of Fig. 16a defines the left-hand side as the source and the right hand side as the drain.
- Fig. 16a also show that the nanowire device is disposed upon and electrically connected to two conductor elements 54.
- Figs. 16a and 16b illustrate an example of a chemical /or ligand-gated Field Effects Transistor (FET).
- FETs are well know in the art of electronics. Briefly, a FET is a 3 -terminal device in which a conductor between 2 electrodes, one connected to the drain and one connected to the source, depends on the availability of charge carriers in a channel between the source and drain.
- the nanowire device illustrated in Figure A provides an FET device that may be contacted with a sample or disposed within the path of a sample flow. Elements of interest within the sample can contact the surface of the nanowire device and, under certain conditions, bind or otherwise adhere to the surface.
- the exterior surface of the device may have reaction entities, e.g., binding partners that are specific for a moiety of interest. The binding partners will attract the moieties or bind to the moieties so that moieties of interest within the sample will adhere and bind to the exterior surface of the nanowire device.
- An example of this is shown in Fig. 16c where there is depicted a moiety of interest 60 (not drawn to scale) being bound to the surface of the nanowire device.
- one or more nanowires may be positioned in a microfluidic channel.
- One or more different nanowires may cross the same microchannel at different positions to detect a different analyte or to measure flow rate of the same analyte.
- one or more nanowires positioned in a microfluidic channel may form one of a plurality of analytic elements in a micro needle probe or a dip and read probe. The micro needle probe is implantable and capable of detecting several analytes simultaneously in real time.
- one or more nanowires positioned in a microfluidic channel may form one of the analytic elements in a microarray for a cassette or a lab on a chip device.
Abstract
Description
Claims
Priority Applications (8)
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DE60135775T DE60135775D1 (en) | 2000-12-11 | 2001-12-11 | DEVICE CONTAINING NANOSENSORS FOR THE DETECTION OF AN ANALYTE AND METHOD FOR THE PRODUCTION THEREOF |
EP01990181A EP1342075B1 (en) | 2000-12-11 | 2001-12-11 | Device contaning nanosensors for detecting an analyte and its method of manufacture |
AU2002229046A AU2002229046B2 (en) | 2000-12-11 | 2001-12-11 | Nanosensors |
CA2430888A CA2430888C (en) | 2000-12-11 | 2001-12-11 | Nanosensors |
KR1020087027974A KR100984603B1 (en) | 2000-12-11 | 2001-12-11 | Nanosensors |
AU2904602A AU2904602A (en) | 2000-12-11 | 2001-12-11 | Nanosensors |
KR10-2003-7007723A KR20030055346A (en) | 2000-12-11 | 2001-12-11 | Nanosensors |
JP2002549958A JP4583710B2 (en) | 2000-12-11 | 2001-12-11 | Nano sensor |
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AT (1) | ATE408140T1 (en) |
AU (2) | AU2904602A (en) |
CA (1) | CA2430888C (en) |
DE (1) | DE60135775D1 (en) |
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