Ultra-sensitive gas sensors based on tellurium-single walled carbon nanotube hybrid nanostructures
09632057 ยท 2017-04-25
Assignee
Inventors
Cpc classification
C25D7/00
CHEMISTRY; METALLURGY
C25D3/54
CHEMISTRY; METALLURGY
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y15/00
PERFORMING OPERATIONS; TRANSPORTING
C25D15/00
CHEMISTRY; METALLURGY
International classification
G01N27/12
PHYSICS
B82Y15/00
PERFORMING OPERATIONS; TRANSPORTING
C25D3/54
CHEMISTRY; METALLURGY
C25D15/00
CHEMISTRY; METALLURGY
C25D7/00
CHEMISTRY; METALLURGY
Abstract
A gas sensor operable at ambient conditions, the sensor includes functionalized feather-like tellurium (Te) nanostructures on single-walled carbon nanotube (SWNTs) networks.
Claims
1. A gas sensor operable at ambient conditions, the sensor comprising: feather-like tellurium (Te) nanostructures functionalized on single-walled carbon nanotube (SWNTs) networks; and tailoring a morphology and a density of the feather-like Te nanostructures to a response and a recovery time of approximately 36 sec and 7 min to 100 ppb.sub.v NO.sub.2 gas at room temperature, respectively.
2. The sensor of claim 1, comprising: a silicon wafer substrate configured to receive the functionalized feather-like tellurium (Te) nanostructures on the single-walled carbon nanotube (SWNTs) networks.
3. The sensor of claim 2, comprising: a plurality of working electrodes on the silicon wafer substrate; and a sensing cell having a gas inlet and a gas outlet.
4. A method of fabricating a gas sensor, the method comprising: electrodepositing a tellurium (Te) solution on aligned single-walled carbon nanotubes (SWNTs); and controlling deposition charge density during the electrodeposition of the tellurium (Te) solution on the aligned single-walled carbon nanotubes (SWNTs) to form feather-like tellurium (Te) nanostructures.
5. The method of claim 4, comprising: preparing a carbon nanotube suspension of carboxylated single-walled carbon nanotubes in a solution of N, N-dimethylformamide; sonicating the solution until a uniform suspension is obtained; centrifuging the suspension and collecting a supernatant; placing the supernatant into a Teflon cell with a chip for SWNT alignment; and obtaining alignment of the single-walled carbon nanotubes (SWNTs) across the microelectrodes.
6. The method of claim 5, comprising: obtaining alignment by applying 2 peak to peak voltage (V.sub.pp) and 4 MHz frequency for approximately 4 seconds.
7. The method of claim 6, comprising: rinsing the synthesized sensor with nanopure water; drying the sensor with ultra-pure N.sub.2 gas; and annealing the sensor.
8. The method of claim 7, wherein the annealing is at 300 C. for 2 hours in forming gas.
9. The method of claim 4, wherein the electrodeposition of the tellurium (Te) solution comprises: electrodepositing Te from an acidic nitric bath containing HTeO.sub.2.sup.+.
10. The method of claim 5, comprising: rinsing the sensor with nanopure water; and drying the sensor with nitrogen gas.
11. The method of claim 5, comprising: configuring the sensor to sense nitrogen dioxide (NO.sub.2).
12. The method of claim 11, comprising: tailoring the morphology and density of the feather-like Te nanostructures to a response and a recovery time of approximately 36 sec and 7 min to 100 ppb.sub.v NO.sub.2 gas at room temperature, respectively.
13. The method of claim 4, comprising: forming the feather-like tellurium (Te) nanostructures at a charge density of about 94.5 mC/cm.sup.2 to about 189 mC/cm.sup.2.
14. The method of claim 9, wherein the acidic nitric bath containing HTeO.sub.2.sup.+ comprises: 10 mM (millimolar) of HTeO.sub.2.sup.+.
15. The method of claim 9, comprising: fixing an applied potential during electrodeposition at 0.75 V to 1.28 V.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings,
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DETAILED DESCRIPTION
(13) One-dimensional (1-D) nanostructures, such as nanowires and nanotubes have received great attention for fabrication of gas sensors due to their unique size-dependent properties. For example, there has been growing interest in carbon nanotubes (CNTs) owing to their unique electrical, physical, mechanical and chemical properties to develop devices with simplicity, reliability, reproducibility, and low cost. Various electronic devices including supercapacitors, electrodes, field emission devices, and sensors have been synthesized based on single carbon nanotubes, carbon nanotube networks or carbon nanotube films.
(14) SWNT based chemiresistors/chemical field effect transistors (ChemFETs) have been widely used as gas sensors due to their sensitivity to charge transfer and chemical doping effect by various gaseous molecules. However, pristine SWNT based gas sensors have limitations such as low sensitivity to some analytes, lack of selectivity as well as long response and recovery times that hinder their use as stand-alone sensing elements. Therefore, effort has been devoted to surface functionalization of SWNT to modify the sensor properties. The incorporation of typical metal or metal oxide catalysts such as Pd, Au, TiO.sub.2 and SnO.sub.2 for enhancement of both sensitivity and selectivity toward analyte gases have been discussed. Furthermore, reports have demonstrated improved performance at lower operating temperatures with respect to their thin film counterparts.
(15) Tellurium is a p-type semiconductor with band gap energy of 0.35 eV at room temperature. Tetragonal-Te (t-Te) due to its hexagonal crystal structure that contains six spiral chains in the corner and one in the center. Based on its unique lattice structure, t-Te shows some interesting properties such as photoconductivity, thermoelectric effect, and catalytic activity and has been used in various devices such as thin film transistors, infrared detectors, and gas sensors. For example, polycrystalline Te thin films fabricated by vacuum thermal evaporation can be used as promising NO.sub.2 sensors at room temperature. Moreover, Te nanotubes and nanorods made from vacuum or atmospheric thermal evaporation has been reported to detect Cl.sub.2, NO and other gases. These Te based sensors exhibited ppm range sensitivity to various gases with response times of around several minutes at room temperature.
(16) In accordance with an exemplary embodiment, Te nanostructure decorated SWNT devices were synthesized by electrodeposition of Te nanostructure on aligned SWNTs. Linear sweep voltammetry (LSV) was utilized to understand the electrochemistry and Te growth. Tunable Te morphologies, including porous beaded structures, needle or blade like geometries, rice shaped particles and extended feather growths, were demonstrated through control over the electrolyte concentration, applied potential and deposition charge density. Decorated SWNT devices were challenged with NO.sub.2 gas and the sensing performance was correlated to the Te nanostructure. In accordance with an exemplary embodiment, highly faceted Te feather structures yielded the highest sensitivity with a room temperature ppb.sub.v detection limit with fast rapid response/recovery times. Selectivity of the nanosensors was also demonstrated by measuring its response towards various gases such as NH.sub.3, H.sub.2S, H.sub.2 and H.sub.2O.
(17) In accordance with an exemplary embodiment, Pt microelectrodes for 15 sensor arrays were fabricated via a photolithography process. Si wafer with 300 nm of oxidation layer was applied as the substrate (
(18) The carbon nanotube suspension was prepared by adding 0.2 mg of commercially available carboxylated single-walled carbon nanotubes (SWNTs, Carbon Solution, Inc. Riverside, Calif.) in 20 mL of N,N-dimethylformamide (DMF, Sigma Aldrich, Mo.), followed by sonicating the contents for 90 minutes until a uniform suspension was obtained. The suspension was then centrifuged at 15000 RPM for 90 min and the supernatant was subsequently collected. Afterwards, 200 L of the supernatant was placed into the Teflon cell with chip held for SWNT alignment (
(19) SWNT functionalization was carried out by the electrodeposition of Te from an acidic nitric bath containing HTeO.sub.2.sup.+. In accordance with an exemplary embodiment, the effects of tellurium precursor concentration, applied potential as well as charge density on the morphology and the electrical properties of the Te-SWNT hybrid nanostructures was investigated. The concentration effect was examined by applying 500 L solutions of 0.1, 1 and 10 mM HTeO.sub.2.sup.+ (99+%, Acros Organics) in 1 M nitric acid (Certified ACS Plus, Fisher Chemical) to the system. In accordance with an exemplary embodiment, the deposition potential and charge density were maintained at 1 V and 18.9 mC/cm.sup.2, respectively. The effect of deposition potential was investigated by varying the potential from 0.8 to 1.4 V with the same charge density applied. Finally, the charge density was varied from about 1.89 to 189 mC/cm.sup.2 at 1 V to study the influence of charge density on the morphology of deposited Te. After deposition, the sensors were rinsed with nanopure water and dried with nitrogen gas.
(20) Morphologies and compositions of the obtained hybrid Te decorated SWNTs were investigated using field emission-scanning electron microscopy (FE-SEM, Leo model II 1550, Peabody, Mass.) and energy-dispersive X-ray spectroscopy (EDX). Back-gated FET properties were measured by sweeping the gate voltage from 20 V to 20 V while fixing the source-drain potential at 1 V. Furthermore, the sensing performance of the Te-SWNT hybrid structure was studied by installing the sensing chip in a sealed Teflon sensing cell with gas inlet and outlet ports for gas flow and then clipping the chip to a Keithley 236 source measurement to obtain electrical connection (
(21) The effect of HTeO.sub.2.sup.+ concentration, applied potential and charge density on the Te growth was investigated with both Linear Sweep Voltammetry (LSV) and scanning electron microscopy of Te nanostructure deposits.
HTeO.sub.2.sup.++3H.sup.++4e.sup..fwdarw.Te+2H.sub.2O
E.sup.O=+0.551 V versus NHE(Eq. 1)
HTeO.sub.2.sup.+=5H.sup.++6e.sup..fwdarw.H.sub.2Te(aq)+2H.sub.2O
E.sup.O=0.121V versus NHE(Eq. 2)
2H.sub.2Te+HTeO.sub.2.sup.+.fwdarw.2H.sub.2O+H.sup.+
G.sub.f.sup.0=498.118Kj mol.sup.1(Eq. 3)
(22) The effects of HTeO.sub.2.sup.+ concentration on Te electrodeposition was examined by conducting LSV with various of HTeO.sub.2.sup.+ concentration from 0.1 to 10 mM (
(23) In accordance with exemplary embodiment, the effect of electrolyte concentration on the morphology of Te grown potentiostatically at 1 V is shown in
(24) Morphologies of Te nanoparticles obtained at different deposition potentials but with a fixed charge density (18.9 mC/cm.sup.2) and HTeO.sub.2.sup.+ concentration (10 mM) are shown in
(25) Furthermore, the disparity in particle size can suggest a progressive nucleation mechanism, which would be consistent with defect site mediated nucleation and growth at low overpotentials. A slightly more negative deposition potential, 1 V, produced SWNTs covered with coalesced rice-like Te nodules described above. For example, at more cathodic potentials, 1.2 V, both the size and coverage of the deposits decreased, which would be attributable to HER and the formation H.sub.2Te according to the Eq. (3). The slightly more spherical shape of these particles can also be a consequence of these parasitic reactions and the resulting decreased Te nucleation and growth. In accordance with an exemplary embodiment, hydrogen evolution reaction (HER) was expected to be quite significant when the applied potential reached 1.4 V, leading to the drastically decreased deposition efficiency and size diminution of Te particles.
(26) For example, control over the size, shape and density of the deposits can also be achieved by varying the applied charge density. Small particles (approximately 20 nm) first nucleated along the SWNTs (
(27) Quantitative assessment of the applied potential and charge density on panicle size and number of panicles per SWNT is provided in
(28) The room temperature back-gated FET measurements, shown in
(29) In accordance with an exemplary embodiment,
(30) Sensing responses of the bare SWNT network and three topographically different (
(31) In accordance with an exemplary embodiment, these sensors were also challenged with background analytes to identify potential interferences and demonstrate sensor viability in real life conditions. The selectivity of the gas sensors can be determined by analyzing their response to various gases such as NH.sub.3, H.sub.2S, H.sub.2 (not shown) and H.sub.2O vapor (
(32) The sensitivities for each sensor to each analyte, as well as H.sub.2, can be calculated by taking the slope of the linear part of the sensing calibration curve and compiled in
(33) In accordance with an exemplary embodiment, the sensing mechanism of the Te and SWNT can be explained by the alteration of the transport properties owing to the interaction of adsorbed species to the SWNT and Te surfaces. As a strong electron acceptor, a NO.sub.2 molecule can receive electrons from the valence band of the semiconductors resulting in the enhancement of the hole density in both Te and SWNTs, thus decreasing the resistance. Likewise, when electron donors such as NH.sub.3 and H.sub.2S were introduced to the sensor, the hole concentration decreased leading the resistance to increase. The superior sensing performance by the Te feather-like structure can be due to its larger surface-to-volume ratio and increased crystallinity, which provides for its higher conductivity and field effect carrier mobility. For example, this sensor analyte can directly interact with the Te feathers, the carrier super highways of the device, to strongly impact carrier transport. Similar behavior in both transient profile and sensitivity values between SWNT networks and hybrid devices with smaller Te loadings can be a consequence of a SWNT nanotubes dominated resistance. The breaks in Te coverage can be higher resistance sections and hence sensitivity can be derived from exposed SWNT permitting similar results as the SWNT control.
(34) As disclosed herein, a Te-SWNT hybrid nanostructure based NO.sub.2 sensor can be synthesized by means of AC dielectrophoretic alignment of SWNT followed by Te electrodeposition. Shape, morphology and size of the Te particles can be controlled by adjusting the electrodeposition conditions and electrolyte composition. Te rice-like and feather-like structures can be synthesized by varying the applied charge density (e.g., 18.9 mC/cm.sup.2 and 94.5 mC/cm.sup.2) at a fixed applied potential of 1 V, using an electrolyte containing 10 mM of HTeO.sub.2.sup.+. Te deposition appears to follow instantaneous nucleation of small panicles along SWNTs followed by the growth of the nucleus to form rice-like structures and finally highly crystalline feather-like structures once mass transfer limitations set in. The gating dependent effects of SWNTs can be diminished upon Te decoration owing to transport though the Te particles and their small grains, but enhanced from transport through Te feather suggesting improved crystallinity in Te feathers.
(35) Sensing results indicated the enhancement of the sensitivity by Te functionalization of SWNTs, for example, by the feather-like Te-SWNT hybrid nanostructures. In accordance with an exemplary embodiment, a NO.sub.2 nanosensor can be developed based on Te feather-SWNT structures with a superior selectivity, high sensitivity of 54%/ppm.sub.v and quick response and recovery times of 36 sec and 7 min to 100 ppb.sub.v NO.sub.2 at room temperature. The sensing mechanism can be explained by the change in carrier transport properties induced from the adsorption of analytes. The outstanding sensing performance of the Te feather-like SWNT structures can be due to its large surface-to-volume ratio and higher field carrier mobility. The sensors were tested against background analytes to demonstrate viability (min) in the field.
(36) The invention is not limited, however, to the embodiments and variations described above and illustrated in the drawing figures. Various changes, modifications and equivalents could be effected by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. It is expressly intended that all such changes, modifications and equivalents which fall within the scope of the claims are embraced by the claims.