US20130307520A1 - Microelectrode array and method for modifying carbon nanotube electrode interface of the same array - Google Patents
Microelectrode array and method for modifying carbon nanotube electrode interface of the same array Download PDFInfo
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Images
Classifications
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- C01B31/0273—
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
- A61N1/0502—Skin piercing electrodes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
- A61N1/0551—Spinal or peripheral nerve electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
Definitions
- the present invention relates to a method for modifying a carbon nanotube electrode interface, particularly to a method for modifying a carbon nanotube electrode interface, which can increase the affinity of neuron cells to the electrodes and improve the quality of neural signals.
- the present invention also relates to a microelectrode array using the carbon nanotube modified by the abovementioned method.
- a probe can easily puncture the skin to detect the electrophysiological signals in vivo.
- a probe may also function as an intermediary between analog physiological signals and digital signal analysis.
- FIG. 1 shows a microelectrode array 10 for detecting neural signals.
- the microelectrode array 10 comprises a base 11 and a plurality of probes 12 connected to the base 11 .
- Each probe 12 has a plurality of electrodes 13 .
- each probe 12 has four electrodes 13 in FIG. 1 .
- Each electrode 13 is electrically connected to a metal pad 15 of the base 11 via a wire 14 .
- Each wire 14 is insulated from the environment.
- the neural signals detected by the electrode 13 is transmitted to the base 11 via the wire 14 and then processed by the succeeding devices.
- Carbon nanotube which was found by S. Iijima in 1991, has a superior electric conductivity because of its special structure. Thus, carbon nanotube has been widely used in the nanometric electronic elements.
- the electrode interfaces of the conventional probes are usually made of a metal having better biocompatibility, such as gold, platinum, titanium, or platinum black.
- the interfacial resistance of the metal electrode increases when the size of a metal electrode is reduced to a very small scale. Thus, the efficiency of the entire circuit decreases.
- Carbon nanotube has very large surface area, high electrical conductivity, better physicochemical properties, better chemical inertness and better biocompatibility. Therefore, more and more applications use carbon nanotube as the interface of neural electrodes, for example, “Carbon Nanotubes for Neural Interfaces” by David Ricci; “Carbon Nanotube Coating Improves Neuronal Recording” by Edward, et al., Nature Nanotech., 2008; “Neural Stimulation with a Carbon Nanotube Microelectrode Array” by Ke Wang, Nano Lett., 2006; “Carbon Nanotube Substrates Boost Neuronal Electrical Signaling” by Viviana Lovat, et al., Nano Lett., 2005; “Carbon Nanotube Micro-Electrodes for Neuronal Interfacing” by E. Ben-Jacob, et al., J. Mater. Chem., 2008.
- the abovementioned technologies are only the rudimentary carbon nanotube applications in the neural electrode interface.
- the present invention further modifies the carbon nanotube electrode interface and forms the functional groups, which neuron cells prefer to adhere to. Therefore, neural signals were enhanced with the use of this modified CNT electrode.
- One objective of the present invention is to provide a method for modifying a carbon nanotube electrode interface to improve the adherence of neuron cells, decrease the impedance between the electrode interface and the biological tissues, and promote the signal intensity and quality of measurement.
- the present invention proposes a method for modifying a carbon nanotube electrode interface, which modifies carbon nanotubes used as a neuron-electrode interface by performing three stages of modifications, including a carboxylation process, an acyl-chlorination process, and an amination process.
- Surfaces of the carbon nanotubes have carboxyl functional groups after the carboxylation process.
- the hydroxyl functional groups of the carboxyl functional groups are replaced by chlorine atoms of thionyl chloride in the acyl-chlorination process.
- the amination process replaces the chlorine atoms with the amine functional groups, which were favored by neuron cells.
- the carbon nanotubes of the neuron-electrode interface are modified directly.
- the carboxylation process is carried out by a H 2 O plasma process.
- the acyl-chlorination and amination are performed in a reflux system.
- the present invention also provides a microelectrode array, which comprises a base and at least one probe connected to the base. Each probe has at least one electrode.
- the electrode uses the carbon nanotubes as the neuron-electrode interface thereof, and the carbon nanotubes is modified with the abovementioned method.
- FIG. 1 is a diagram schematically showing a microelectrode array for detecting neural signals according to the present invention
- FIG. 2 is a flowchart of a method for modifying a carbon nanotube electrode interface according to the present invention
- FIG. 3 is a diagram schematically showing a method for modifying a carbon nanotube electrode interface according to the present invention
- FIG. 4 is a diagram schematically a reflux system according to the present invention.
- FIG. 5A is a diagram showing the impedance variation of a neural electrode before and after the modification of carbon nanotubes according to the present invention.
- FIG. 5B is a diagram showing neural signals detected before and after the modification of carbon nanotubes according to the present invention.
- FIG. 6 is a cross-section view of a carbon nanotube electrode interface according to one embodiment of the present invention.
- the present invention proposes a method for modifying a carbon nanotube electrode interface, which modifies carbon nanotubes used as a neuron-electrode interface to increase the adherence of neuron cells to the carbon nanotube electrode interface, improve the biocompatibility of neuronal, and promote the quality of electrophysiological signals.
- FIG. 2 and FIG. 3 respectively a flowchart and a schematic diagram of a method for modifying a carbon nanotube electrode interface according to the present invention.
- the method of the present invention comprises a carboxylation process (Step a), an acyl-chlorination process (Step b) and an amination process (Step c).
- the carbon nanotubes are carboxylated to form a plurality of carboxyl functional groups “O ⁇ C—OH” on surfaces of the carbon nanotubes (as shown in FIG. 3 ) to improve the hydrophilicity of the carbon nanotubes.
- a microelectrode array used the carbon nanotubes as the neuron-electrode interface is washed with deionized water and then dried.
- the microelectrode array is processed with a H 2 O plasma to generate the carboxyl functional groups “O ⁇ C—OH” on the carbon nanotubes.
- the H 2 O plasma process is performed at a temperature of 25-150° C., under a pressure of 1-100 Ton, with a power of 25-100 W, for 10-300 seconds.
- the amount of the carboxyl functional groups correlates with the processing time of the H 2 O plasma. If the processing time is too short, it results in insufficient carboxyl functional groups. If the processing time is too long, the carbon nanotubes will be damaged.
- the carboxylation process is carried out by an O 2 plasma process or via immersing the carbon nanotubes into an acidic solution at an ambient temperature.
- the acidic solutions include but are not limited to nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), and hydrogen peroxide (H 2 O 2 ).
- the carboxylated carbon nanotubes are further acyl-chlorinated to replace the hydroxyl functional groups of the carboxyl functional groups with chlorine atoms and form “O ⁇ C—Cl” functional groups.
- the carboxylated carbon nanotubes react with thionyl chloride (SOCl 2 ), phosphorus trichloride (PCl 3 ), phosphorus pentachloride (PCl 5 ), Oxalyl dichloride (COCl) 2 , or cyanuric chloride (C 3 N 3 Cl 3 ), and the hydroxyl functional groups thereof are thus replaced by the chlorine atoms.
- the acyl-chlorination process is carried out with a chemical synthesis method, wherein the carboxylated carbon nanotubes react with the thionyl chloride in a reflux system, and the reaction formula thereof is expressed by Formula (I).
- FIG. 4 a diagram schematically shows a reflux system.
- the microelectrode array 20 is immersed in the thionyl chloride solution, and an inert gas, such as argon, is pumped into the reflux system to implement the acyl-chlorination reaction.
- the product gases sulfur dioxide (SO 2 ) and hydrogen chloride (HCl) are taken away via a condensation tube.
- the acyl-chlorination process is undertaken at a temperature of 25-80° C. for 10-20 hours.
- a magnet 21 is placed on the bottom of the reflux system and used to agitate the solution to accelerate the reaction.
- the microelectrode array 20 is placed on a supporter 22 , whereby the microelectrode array 20 is immersed in the thionyl chloride solution and exempted from the interference of the magnet 21 . After the acyl-chlorination process, the microelectrode array 20 is dried for the succeeding treatment.
- the acyl-chlorinated nanotubes are aminated, whereby the chlorine of the “O ⁇ C—Cl” functional groups are replaced by an amine to form an amine derivative having “O ⁇ C— ⁇ NH 3 + ” functional groups at the terminals thereof, as shown in FIG. 3 .
- the “O ⁇ C— ⁇ NH 3 + ” functional group has very high affinity and excellent adherence to the neuron cells and is exempt from the adherence of glial cells. Therefore, the “O ⁇ C— ⁇ NH 3 + ” functional groups can prevent from the glial cells aggregation and inhibit the formation of the sheaths, which will isolate the electrodes from the biological tissue and impair the signal measurement.
- the amine derivatives could be, but not limited to, 1,4-diaminobutane, ethylenediamine and EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide).
- the amination is realized with a chemical synthesis method, wherein the acyl-chlorinated carbon nanotubes react with 1,4-diaminobutane in a reflux system.
- the 1,4-diaminobutane is dissolved in a solvent by a concentration of 0.1-10 wt %.
- An appropriate amount of a basic compound is added into the solution to neutralize the acidity.
- the solvent is, but not limited to, toluene.
- Triethylamine may function as the basic compound to neutralize the acidic products of the reaction, but the basic compound is not limited to triethylamine.
- the chlorine atom is replaced by “—NH—C 4 —NH 3 + —”, which has an amine functional group at the terminal thereof.
- the neural electrode containing the modified carbon nanotubes has lower impedance than the neural electrode containing the as-grown carbon nanotubes.
- the horizontal axis represents the concentration of 1,4-diaminobutane in the Step c.
- the amine functional groups With the increasing concentration of 1,4-diaminobutane, the amine functional groups also increase, and the impedance of the electrode decreases.
- FIG. 5B after modifying the carbon nanotubes, the potential of the signals detected by the neural electrodes is much greater than before the modification. As shown in FIG. 5B , the electric potential and signal-to-noise ratio also increase after the modification.
- the present invention also includes the case: independent carbon nanotubes are modified firstly, and the modified carbon nanotubes are formed on the neural electrodes via a coating method, a printing method, or another method.
- the present invention also proposes a microelectrode array, which comprises a base and at least one probe connected to the base. Each probe has at least one electrode using the carbon nanotubes as the interface thereof. Each electrode is connected to the base via a wire.
- the carbon nanotubes are modified with the above-mentioned method to contain amine functional groups.
- the microelectrode array of the present invention is fabricated from the combination of a silicon wafer and a complementary metal-oxide-semiconductor (CMOS) in the semiconductor processing techniques.
- CMOS complementary metal-oxide-semiconductor
- FIG. 6 a sectional view schematically showing an electrode 30 using the carbon nanotubes as the interface thereof.
- the electrode 30 includes a carbon nanotube layer 37 , a conductive layer 34 and a catalytic layer 36 .
- the carbon nanotube layer 37 is the measurement interface of the electrode 30 .
- the conductive layer 34 (such as a gold layer shown in FIG. 6 ) is deposited on a first adhesion layer 33 (such as a chromium layer shown in FIG. 6 ) and over the silicon wafer 31 , and a position and dimensions of the electrode 30 are thus defined.
- an insulating layer 32 (such as a silicon dioxide layer shown in FIG. 6 ) is formed between the conductive layer 34 and the wafer 31 .
- the catalytic layer 36 is formed over the conductive layer 34 , and the carbon nanotube layer 37 is catalytically formed on the catalytic layer 36 .
- the catalytic layer 36 is made of iron, cobalt, or nickel.
- the catalytic layer 36 is a nickel layer having a thickness of about 5 nm.
- the catalytic layer 36 is formed on a second adhesion layer 35 and over the conductive layer 34 , and the second adhesion layer 35 is a titanium layer having a thickness of about 10-30 nm in FIG. 6 .
- the carbon nanotube layer 37 is synthesized at a temperature of 350-400° C.
- the modified carbon nanotube interfaces of the electrodes of the microelectrode array can obviously increase the adherence of neuron cells to the electrodes.
- the microelectrode array can be implanted into the biological tissue to perform a long-time measurement.
- the microelectrode array of the present invention can perform intracellular recording to obtain higher-intensity signals.
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Abstract
Description
- The present invention relates to a method for modifying a carbon nanotube electrode interface, particularly to a method for modifying a carbon nanotube electrode interface, which can increase the affinity of neuron cells to the electrodes and improve the quality of neural signals. The present invention also relates to a microelectrode array using the carbon nanotube modified by the abovementioned method.
- Since a planar multi-electrode array was proposed to study the transmission mechanism of neural signals in 1972, microelectrode arrays have been extensively used in the biomedical engineering. The brain or a neural network is a complicated network consisting of many neurons interconnecting each other. Understanding the operation of the neural network is very important to diagnose or treat neural diseases or fabricate neural prostheses. A probe can easily puncture the skin to detect the electrophysiological signals in vivo. A probe may also function as an intermediary between analog physiological signals and digital signal analysis.
-
FIG. 1 shows amicroelectrode array 10 for detecting neural signals. Themicroelectrode array 10 comprises abase 11 and a plurality ofprobes 12 connected to thebase 11. Eachprobe 12 has a plurality ofelectrodes 13. For example, eachprobe 12 has fourelectrodes 13 inFIG. 1 . Eachelectrode 13 is electrically connected to ametal pad 15 of thebase 11 via awire 14. Eachwire 14 is insulated from the environment. The neural signals detected by theelectrode 13 is transmitted to thebase 11 via thewire 14 and then processed by the succeeding devices. - Carbon nanotube, which was found by S. Iijima in 1991, has a superior electric conductivity because of its special structure. Thus, carbon nanotube has been widely used in the nanometric electronic elements. The electrode interfaces of the conventional probes are usually made of a metal having better biocompatibility, such as gold, platinum, titanium, or platinum black. However, the interfacial resistance of the metal electrode increases when the size of a metal electrode is reduced to a very small scale. Thus, the efficiency of the entire circuit decreases.
- Carbon nanotube has very large surface area, high electrical conductivity, better physicochemical properties, better chemical inertness and better biocompatibility. Therefore, more and more applications use carbon nanotube as the interface of neural electrodes, for example, “Carbon Nanotubes for Neural Interfaces” by David Ricci; “Carbon Nanotube Coating Improves Neuronal Recording” by Edward, et al., Nature Nanotech., 2008; “Neural Stimulation with a Carbon Nanotube Microelectrode Array” by Ke Wang, Nano Lett., 2006; “Carbon Nanotube Substrates Boost Neuronal Electrical Signaling” by Viviana Lovat, et al., Nano Lett., 2005; “Carbon Nanotube Micro-Electrodes for Neuronal Interfacing” by E. Ben-Jacob, et al., J. Mater. Chem., 2008.
- The abovementioned technologies are only the rudimentary carbon nanotube applications in the neural electrode interface. The present invention further modifies the carbon nanotube electrode interface and forms the functional groups, which neuron cells prefer to adhere to. Therefore, neural signals were enhanced with the use of this modified CNT electrode.
- One objective of the present invention is to provide a method for modifying a carbon nanotube electrode interface to improve the adherence of neuron cells, decrease the impedance between the electrode interface and the biological tissues, and promote the signal intensity and quality of measurement.
- To achieve the abovementioned objective, the present invention proposes a method for modifying a carbon nanotube electrode interface, which modifies carbon nanotubes used as a neuron-electrode interface by performing three stages of modifications, including a carboxylation process, an acyl-chlorination process, and an amination process. Surfaces of the carbon nanotubes have carboxyl functional groups after the carboxylation process. Next, the hydroxyl functional groups of the carboxyl functional groups are replaced by chlorine atoms of thionyl chloride in the acyl-chlorination process. Next, the amination process replaces the chlorine atoms with the amine functional groups, which were favored by neuron cells.
- In one embodiment, the carbon nanotubes of the neuron-electrode interface are modified directly. In one embodiment, the carboxylation process is carried out by a H2O plasma process. In one embodiment, the acyl-chlorination and amination are performed in a reflux system.
- The present invention also provides a microelectrode array, which comprises a base and at least one probe connected to the base. Each probe has at least one electrode. The electrode uses the carbon nanotubes as the neuron-electrode interface thereof, and the carbon nanotubes is modified with the abovementioned method.
- Below, the technical contents of the present invention are described in detail with the embodiments and drawings.
-
FIG. 1 is a diagram schematically showing a microelectrode array for detecting neural signals according to the present invention; -
FIG. 2 is a flowchart of a method for modifying a carbon nanotube electrode interface according to the present invention; -
FIG. 3 is a diagram schematically showing a method for modifying a carbon nanotube electrode interface according to the present invention; -
FIG. 4 is a diagram schematically a reflux system according to the present invention; -
FIG. 5A is a diagram showing the impedance variation of a neural electrode before and after the modification of carbon nanotubes according to the present invention; -
FIG. 5B is a diagram showing neural signals detected before and after the modification of carbon nanotubes according to the present invention; and -
FIG. 6 is a cross-section view of a carbon nanotube electrode interface according to one embodiment of the present invention. - The present invention proposes a method for modifying a carbon nanotube electrode interface, which modifies carbon nanotubes used as a neuron-electrode interface to increase the adherence of neuron cells to the carbon nanotube electrode interface, improve the biocompatibility of neuronal, and promote the quality of electrophysiological signals.
- Refer to
FIG. 2 andFIG. 3 respectively a flowchart and a schematic diagram of a method for modifying a carbon nanotube electrode interface according to the present invention. - The method of the present invention comprises a carboxylation process (Step a), an acyl-chlorination process (Step b) and an amination process (Step c).
- In the Step a, the carbon nanotubes are carboxylated to form a plurality of carboxyl functional groups “O═C—OH” on surfaces of the carbon nanotubes (as shown in
FIG. 3 ) to improve the hydrophilicity of the carbon nanotubes. In one embodiment, a microelectrode array used the carbon nanotubes as the neuron-electrode interface is washed with deionized water and then dried. Next, the microelectrode array is processed with a H2O plasma to generate the carboxyl functional groups “O═C—OH” on the carbon nanotubes. The H2O plasma process is performed at a temperature of 25-150° C., under a pressure of 1-100 Ton, with a power of 25-100 W, for 10-300 seconds. The amount of the carboxyl functional groups correlates with the processing time of the H2O plasma. If the processing time is too short, it results in insufficient carboxyl functional groups. If the processing time is too long, the carbon nanotubes will be damaged. - In other embodiment, the carboxylation process is carried out by an O2 plasma process or via immersing the carbon nanotubes into an acidic solution at an ambient temperature. The acidic solutions include but are not limited to nitric acid (HNO3), sulfuric acid (H2SO4), and hydrogen peroxide (H2O2).
- In the Step b, the carboxylated carbon nanotubes are further acyl-chlorinated to replace the hydroxyl functional groups of the carboxyl functional groups with chlorine atoms and form “O═C—Cl” functional groups. In the acyl-chlorination process, the carboxylated carbon nanotubes react with thionyl chloride (SOCl2), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), Oxalyl dichloride (COCl)2, or cyanuric chloride (C3N3Cl3), and the hydroxyl functional groups thereof are thus replaced by the chlorine atoms.
- In one embodiment, the acyl-chlorination process is carried out with a chemical synthesis method, wherein the carboxylated carbon nanotubes react with the thionyl chloride in a reflux system, and the reaction formula thereof is expressed by Formula (I).
-
R—COOH+SOCl2(l)→R—COCl+SO2(g)+HCl(g) (1) - Refer to
FIG. 4 a diagram schematically shows a reflux system. Themicroelectrode array 20 is immersed in the thionyl chloride solution, and an inert gas, such as argon, is pumped into the reflux system to implement the acyl-chlorination reaction. The product gases sulfur dioxide (SO2) and hydrogen chloride (HCl) are taken away via a condensation tube. The acyl-chlorination process is undertaken at a temperature of 25-80° C. for 10-20 hours. Amagnet 21 is placed on the bottom of the reflux system and used to agitate the solution to accelerate the reaction. Themicroelectrode array 20 is placed on asupporter 22, whereby themicroelectrode array 20 is immersed in the thionyl chloride solution and exempted from the interference of themagnet 21. After the acyl-chlorination process, themicroelectrode array 20 is dried for the succeeding treatment. - In the Step c, the acyl-chlorinated nanotubes are aminated, whereby the chlorine of the “O═C—Cl” functional groups are replaced by an amine to form an amine derivative having “O═C—˜NH3 +” functional groups at the terminals thereof, as shown in
FIG. 3 . The “O═C—˜NH3 +” functional group has very high affinity and excellent adherence to the neuron cells and is exempt from the adherence of glial cells. Therefore, the “O═C—˜NH3 +” functional groups can prevent from the glial cells aggregation and inhibit the formation of the sheaths, which will isolate the electrodes from the biological tissue and impair the signal measurement. The amine derivatives could be, but not limited to, 1,4-diaminobutane, ethylenediamine and EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide). - In one embodiment, the amination is realized with a chemical synthesis method, wherein the acyl-chlorinated carbon nanotubes react with 1,4-diaminobutane in a reflux system. The 1,4-diaminobutane is dissolved in a solvent by a concentration of 0.1-10 wt %. An appropriate amount of a basic compound is added into the solution to neutralize the acidity. The solvent is, but not limited to, toluene. Triethylamine may function as the basic compound to neutralize the acidic products of the reaction, but the basic compound is not limited to triethylamine. After the carbon nanotubes are modified by 1,4-diaminobutane, the chlorine atom is replaced by “—NH—C4—NH3 +—”, which has an amine functional group at the terminal thereof.
- Refer to
FIG. 5A . The neural electrode containing the modified carbon nanotubes has lower impedance than the neural electrode containing the as-grown carbon nanotubes. InFIG. 5A , the horizontal axis represents the concentration of 1,4-diaminobutane in the Step c. With the increasing concentration of 1,4-diaminobutane, the amine functional groups also increase, and the impedance of the electrode decreases. Refer toFIG. 5B , after modifying the carbon nanotubes, the potential of the signals detected by the neural electrodes is much greater than before the modification. As shown inFIG. 5B , the electric potential and signal-to-noise ratio also increase after the modification. - In the abovementioned embodiments, what are modified are the carbon nanotubes that have been formed on the electrodes of a microelectrode array. However, the present invention also includes the case: independent carbon nanotubes are modified firstly, and the modified carbon nanotubes are formed on the neural electrodes via a coating method, a printing method, or another method.
- The present invention also proposes a microelectrode array, which comprises a base and at least one probe connected to the base. Each probe has at least one electrode using the carbon nanotubes as the interface thereof. Each electrode is connected to the base via a wire. The carbon nanotubes are modified with the above-mentioned method to contain amine functional groups.
- The microelectrode array of the present invention is fabricated from the combination of a silicon wafer and a complementary metal-oxide-semiconductor (CMOS) in the semiconductor processing techniques. Refer to
FIG. 6 a sectional view schematically showing anelectrode 30 using the carbon nanotubes as the interface thereof. Theelectrode 30 includes acarbon nanotube layer 37, aconductive layer 34 and acatalytic layer 36. Thecarbon nanotube layer 37 is the measurement interface of theelectrode 30. The conductive layer 34 (such as a gold layer shown inFIG. 6 ) is deposited on a first adhesion layer 33 (such as a chromium layer shown inFIG. 6 ) and over thesilicon wafer 31, and a position and dimensions of theelectrode 30 are thus defined. In one embodiment, an insulating layer 32 (such as a silicon dioxide layer shown inFIG. 6 ) is formed between theconductive layer 34 and thewafer 31. Thecatalytic layer 36 is formed over theconductive layer 34, and thecarbon nanotube layer 37 is catalytically formed on thecatalytic layer 36. Thecatalytic layer 36 is made of iron, cobalt, or nickel. InFIG. 6 , thecatalytic layer 36 is a nickel layer having a thickness of about 5 nm. In one embodiment, thecatalytic layer 36 is formed on asecond adhesion layer 35 and over theconductive layer 34, and thesecond adhesion layer 35 is a titanium layer having a thickness of about 10-30 nm inFIG. 6 . In one embodiment, thecarbon nanotube layer 37 is synthesized at a temperature of 350-400° C. - In the present invention, the modified carbon nanotube interfaces of the electrodes of the microelectrode array can obviously increase the adherence of neuron cells to the electrodes. Thus, the microelectrode array can be implanted into the biological tissue to perform a long-time measurement. Further, the microelectrode array of the present invention can perform intracellular recording to obtain higher-intensity signals.
- The embodiments described above are only to exemplify the present invention but not to limit the scope of the present invention. Any equivalent modification or variation according to the spirit of the present invention is to be also included within the scope of the present invention.
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