Graphene nanoelectronic heterodyne sensor for rapid and sensitive vapor detection

Abstract

An improved sensing method is provided for rapid analyte detection. The method includes: applying an AC excitation signal to the channel region of the transistor; applying an AC drive signal to the transistor; delivering an analyte of interest to a channel region of a transistor; and monitoring a mixing current of the excitation signal and the drive signal through the transistor, where a change in the mixing current is indicative of the concentration of the analyte of interest.

Claims

1. A method of rapid analyte detection, comprising: delivering an analyte of interest to a channel region of a nanotransistor; exciting dipoles of molecules of the analyte of interest by applying an excitation signal to the channel region of the nanotransistor and applying a drive signal to the nanotransistor, where the excitation signal is an alternating current with a frequency range of kilohertz to megahertz and the drive signal is an alternating current with a frequency range of kilohertz to megahertz; and monitoring a mixing current of the excitation signal and the drive signal through the nanotransistor, where a change in the mixing current is indicative of concentration of the analyte of interest.

2. The method of claim 1 wherein monitoring the mixing current further comprises measuring mixing current before delivery of the analyte to the channel region and determining a change in the mixing current after the delivery of the analyte to the channel region of the nanotransistor.

3. The method of claim 1 further comprises applying the excitation signal to at least one of a source electrode or a drain electrode of the nanotransistor and applying the drive signal to a gate electrode of the nanotransistor.

4. The method of claim 1 further comprises applying the excitation signal to a gate electrode of the nanotransistor and applying the drive signal to at least one of a source electrode or a drain electrode of the nanotransistor.

5. The method of claim 1 further comprises adding a modulation signal to one of the excitation signal or the drive signal.

6. The method of claim 1 wherein frequency of the excitation signal is the same as frequency of the drive signal.

7. The method of claim 1 wherein frequency of the excitation signal is different from frequency of the drive signal.

8. The method of claim 1 further comprises delivering the analyte of interest in one of a gas form or a liquid form to the channel region of the nanotransistor.

9. The method of claim 1 further comprises applying the excitation signal at resonance frequency of analyte of interest.

10. The method of claim 1 further comprises delivering the analyte of interest using gas chromatography.

11. A method of rapid analyte detection, comprising: delivering an analyte of interest to a channel region of a nanotransistor; exciting dipoles of molecules of the analyte of interest by applying an excitation signal to the channel region of the nanotransistor and applying a drive signal to the nanotransistor, where the excitation signal is an alternating current and the drive signal is an alternating current and frequency of the excitation signal and the drive signal is in range of kilohertz to megahertz; and detecting a heterodyne current through the nanotransistor, where a change in the heterodyne mixing current is indicative of concentration of the analyte of interest.

12. The method of claim 11 further comprises applying the excitation signal to at least one of a source electrode or a drain electrode of the nanotransistor and applying the drive signal to a gate electrode of the nanotransistor.

13. The method of claim 11 further comprises applying the excitation signal to a gate electrode of the nanotransistor and applying the drive signal to at least one of a source electrode or a drain electrode of the nanotransistor.

14. The method of claim 11 further comprises adding a modulation signal to one of the excitation signal or the drive signal.

15. The method of claim 11 wherein frequency of the excitation signal is the same as frequency of the drive signal.

16. The method of claim 11 wherein frequency of the excitation signal is different from frequency of the drive signal.

17. The method of claim 11 further comprises delivering the analyte of interest in one of a gas form or a liquid form to the channel region of the nanotransistor.

18. The method of claim 11 further comprises applying the excitation signal at resonance frequency of analyte of interest.

Description

DRAWINGS

(1) The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.

(2) FIG. 1 is a schematic showing a graphene transistor configured as a high-frequency mixer for hererodyne vapour sensing;

(3) FIG. 2 is a flowchart further illustrates the sensing technique using the heterodyne sensor;

(4) FIG. 3 is a diagram of an experimental setup showing a gas chromatography (GC) injector connected to the heterodyne sensor and a flame ionization detector through a GC separation column;

(5) FIG. 4 is a graph depicting the mixing current response of the heterodyne sensor to injections of various masses of (1) pentane, (2) hexane, (3) benzene, (4) chlorobenzene, (5) dichloromethane, (6) chloroform, (7) N,N-dimethylformamide (DMF), (8) DMMP and (9) acetone;

(6) FIGS. 5A-5H are graphs depicting temporal response of the FID and the heterodyne sensor to the same injected mass of dichloromethane, ethanol, chloroform, chlorobenzene, 2-propanol, acetone, 1,4-dioxane and DMF, respectively;

(7) FIG. 6 is a graph depicting temporal response of the FID and the heterodyne sensor to 205 pg injected mass of DMMP;

(8) FIG. 7 is a graph depicting chromatographic response of the heterodyne sensor to repeated pulses of DMMP at varying mass injections;

(9) FIG. 8 is a graph depicting the measured relative mixing current change of the heterodyne sensor to DMMP mass injections from FIG. 7;

(10) FIG. 9 is a graph depicting the measured relative mixing current response at varying mass injections for nine different analytes;

(11) FIG. 10 is a graph depicting the measured relative current response to a pair of cis- and trans-isomers, 1,2-dichloroethne, with the same injected mass of 1.28 g;

(12) FIG. 11 are graphs depicting sensor response of select analytes;

(13) FIG. 12 is a graph depicting GC chromatograms obtained simultaneously from the FID and the heterodyne sensor; and

(14) FIGS. 13A and 13B depict top and bottom substrates, respectively, of a micro gas chromatography device with an integrated heterodyne sensor.

(15) Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.

DETAILED DESCRIPTION

(16) A dipole-detection-based nanoelectronic heterodyne sensor is developed by exploiting the fourth term in equation 1. Different from all existing nanoelectronic-sensing technologies, this approach utilizes a field-effect-transistor (FET) as a high-frequency (e.g., >100 kHz) mixer with surface-adsorbed molecules functioning as an oscillating gate. The oscillating molecular dipole (excited by AC-driving voltage) induces a conductance modulation on the channel region of the transistor; this conductance fluctuation is frequency-mixed with the AC excitation, thus generating a heterodyne mixing current. Importantly, by using higher frequencies, the slow sensing response hindering the conventional nanoelectronic sensor can be overcome when the AC field switching outpaces the slow dynamics of interface states. Therefore, the proposed prototype sensor can achieve simultaneously rapid (down to 0.1 s) and sensitive (down to 1 ppb) detection of a wide range of analytes, representing orders of magnitude improvement in both response time and sensitivity over state-of-the-art nanoelectronic sensors.

(17) FIG. 1 illustrates an example device design and working principle of the proposed nanoelectronic heterodyne sensor 10. In an example embodiment, the field effect transistor is comprised of a source electrode 12, a channel region 13, a drain electrode 14 and a gate electrode 15 disposed on an underside of a substrate 16. In this embodiment, the channel region 13 is comprised of graphene although other generic semiconductors, such carbon nanotube, silicon, metal oxides, III-V semiconductors, or transition metal dichalcogenides, are contemplated by this disclosure. The substrate 16 is comprised of silicon dioxide (SiO2) or another common dielectric. Likewise, the source electrode 12, the drain electrode 14 and the gate electrode 15 may be comprised of various types of semiconductor materials. Other types of transistors are also contemplated within the scope of this disclosure.

(18) FIG. 2 illustrates an improved sensing technique using the nanoelectronic heterodyne sensor 10. An AC excitation signal is applied at 22 to the channel region of the transistor. For example, an AC voltage at frequency w, {tilde over (V)}.sup.w, is applied to the source electrode 12 of a FET through a bias tee while the DC bias at source and gate electrodes are held at ground (V.sub.sd, V.sub.g=0 V). The excitation signal may also be applied via the drain electrode. It is contemplated that the excitation signal can be either a single frequency or a mixture of multiple frequencies. In an example embodiment, the AC excitation signal, {tilde over (V)}.sup.w, was applied with a typical amplitude of |{tilde over (V)}.sup.w|=20 mV and frequency of 100 kHz by a HP 8648 signal generator (Santa Clara, Calif., USA). {tilde over (V)}.sup.w is then amplitude modulated at

(19) $\frac{w_m}{2}=1.4342\mathrm{kHz}$
KHz using me reference signal from a SR830 lock-in amplifier (Stanford Research Systems, Sunnyvale, Calif., USA), before it was delivered to the source terminal of the heterodyne sensor 10 via a bias tee.

(20) An AC drive signal is also applied to the transistor as indicated at 23. In this example, the drive signal is applied to the gate electrode 15. The electrostatic coupling between the channel region and the gate electrode leads to a gate-induced charge density modulation at w,

(21) ${\tilde{Q}}_g^w=C_g{\tilde{V}}_g^w=C_g\left(-\frac{1}{2}{\tilde{V}}^w\right),$
with C.sub.g being the gate capacitance per unit area and assuming perfect metal/graphene contacts. In the presence of a surface-adsorbed molecule, the oscillating molecular dipole can also lead to dipole-induced charge density modulation at w, {tilde over (Q)}.sub.m.sup.w. In other examples, the drive signal is applied to through the source/drain electrode; whereas, the excitation signal is applied to the gate electrode.

(22) The frequency mixing between {tilde over (V)}.sup.w and {tilde over (Q)}.sup.w through the transistor yields a heterodyne mixing current:

(23) $\begin{array}{cc}{I}_{\mathrm{mix}}={\tilde{G}}^w{\tilde{V}}^w=\frac{W}{L}[\left(C_g\left(-\frac{1}{2}{\tilde{V}}^w\right)+{\tilde{Q}}_m^w\right]{\tilde{V}}^w,& \left(2\right)\end{array}$
where is the carrier mobility, and W and L are the length and width of the device, respectively. For molecule sensing, the change in the mixing current is monitored at 24 as the sensing signal:

(24) $\begin{array}{cc}{I}_{\mathrm{mix}}=\frac{W}{L}{\tilde{Q}}_m^w{\tilde{V}}^w.& \left(3\right)\end{array}$
such that a change in the mixing current correlates to a quantitative measure of molecule concentration. In the example embodiment, the mixing current was measured at w_m/2 using the lock-in amplifier, and used as the sensing signal in response to the vapour analytes. A modulation signal can be added onto either the AC excitation or the AC drive signals to improve the sensor's signal-to-noise ratio. In this case, the sensing signal will be measured at the modulation frequency, or the higher harmonics of the modulation frequency. It is envisioned that the signal modulation can be amplitude modulation (AM), phase modulation (PM), or frequency modulation (FM).

(25) During sensing, the mixing current is measured before delivery of an analyte of interest. The analyte of interest is then delivered at 25 to a channel region of the transistor. The molecule can be delivered in gas or liquid form using various types of delivery mechanisms (e.g., gas chromatography, syringe, etc.). A change in the mixing current is then determined some time after the delivery of the analyte. From the change in mixing current, a quantitative determination is made at 26 of the concentration of the analyte of interest.

(26) The sensing model for the nanoelectric heterodyne sensor is further described below. The DC current-voltage relation for a transistor is given as:

(27) $\begin{array}{cc}I=\frac{W}{L}\left[C_g\left(V_g-\frac{1}{2}\right)V\right],& \left(4\right)\end{array}$
where C.sub.g is the gate capacitance, V.sub.g is the DC gate voltage, V is the DC bias voltage, and

(28) $C_g\left(V_g-\frac{1}{2}V\right)$
gives the charge per unit area within the graphene channel induced by the effective gate voltage, V.sub.g.sup.eff=V.sub.gV. When molecules are adsorbed on a graphene surface, they induce additional charge in the graphene channel and thus modify the transistor current:

(29) $\begin{array}{cc}I=\frac{W}{L}\left[C_g\left(V_g-\frac{1}{2}V\right)+Q_m\right].Math.V,& \left(5\right)\end{array}$
where Q.sub.m is the molecule induced charge per unit area inside the graphene channel. Importantly, since vapour molecules are charge neutral, Q.sub.m is zero unless there is charge transfer between molecule and graphene or under imperfect screening. This is the fundamental reason why pristine graphene DC sensors have low sensitivity toward most vapour molecules.

(30) A time varying AC excitation at , {tilde over (V)}.sup., will modulate the channel potential and generate charge density modulation due to electrostatic coupling with gate. In addition, {tilde over (V)}.sup., can also excite the adsorbed molecules, which in turn produce a dipole-induced charge density modulation at , {tilde over (Q)}.sub.m.sup.. Thus, the heterodyne mixing current (the fourth term in Eq. (1)) can be expressed as:

(31) $\begin{array}{cc}{I}_{\mathrm{mix}}=\frac{W}{L}\left[C_g\left(-\frac{1}{2}{\tilde{V}}^{}\right)+{\tilde{Q}}_m^{}\right].Math.{\tilde{V}}^{}.& \left(6\right)\end{array}$
The first term inside the square bracket is the contribution from the inherent gate response and is accounted as the background current. The second term, however, is related to the molecular dipole-induced charge perturbation in graphene. Hence, the changes in mixing current due to molecular absorption can be measured as the sensor signal:

(32) ${\mathrm{AI}}_{\mathrm{mix}}=\frac{W}{L}{\tilde{Q}}_m^{}{\tilde{V}}^{}.$

(33) To calculate {tilde over (Q)}.sub.m.sup., first examine a single molecule with a dipole moment, p, adsorbed on the centre of graphene surface. For simplicity, assume the molecule-graphene vertical distance is h, and the dipole moment is perpendicular to the graphene surface. The electric field on graphene due to the molecular dipole can be expressed as

(34) 0$\begin{array}{cc}{\stackrel{.fwdarw.}{E}}_{\mathrm{Gr}}=\frac{1}{4{\mathrm{.Math.}}_0}\left[\frac{3\left(\stackrel{.fwdarw.}{p}.Math.\hat{r}\right)\hat{r}-\stackrel{.fwdarw.}{p}}{r^3}\right],& \left(7\right)\end{array}$
where {right arrow over (r)} is a point on graphene from {right arrow over (p)}, {circumflex over (r)} is its unit vector, and the angle between {right arrow over (r)} and {right arrow over (p)} is . This local electric field polarizes graphene:

(35) $\begin{array}{cc}{\stackrel{.fwdarw.}{P}}_{\mathrm{Gr}}={}_{\mathrm{Gr}}{\stackrel{.fwdarw.}{E}}_{\mathrm{Gr}}=\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\left[\frac{3\left(\stackrel{.fwdarw.}{p}.Math.\hat{r}\right)\hat{r}-\stackrel{.fwdarw.}{p}}{r^3}\right],& \left(8\right)\end{array}$
where .sub.Gr is graphene's polarizability and {right arrow over (P)}.sub.Gr is the molecular dipole induced graphene dipole moment at {right arrow over (r)}. The macroscopic polarization normal to graphene surface, {right arrow over (P)}.sub.Gr.sup.Z, can be obtained by integrating {right arrow over (P)}.sub.Gr over the entire graphene lattice. The unit area can be calculated as

(36) $\mathrm{dA}=2r\sin \frac{-h}{{\cos }^2}d,$
while the number of carbon atoms within this unit area is given by

(37) $\frac{2\mathrm{dA}}{A_{\mathrm{uc}}},$
with A.sub.uc=0.051 nm.sup.2 being the unit cell area of graphene. Hence:

(38) $\begin{array}{c}{\stackrel{.fwdarw.}{P}}_{\mathrm{Gr}}^Z=\frac{1}{WLt}{}_{}^{-{\cos }^{-1\left(\frac{2h}{W}\right)}}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\left[\frac{3\left(\stackrel{.fwdarw.}{p}.Math.\hat{r}\right)\hat{r}-\stackrel{.fwdarw.}{p}}{r^3}\right]\frac{2}{A_{\mathrm{uc}}}2r\sin \frac{-h}{{\cos }^2}d\\ =\frac{1}{WLt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{4}{A_{\mathrm{uc}}}\frac{p}{h}{}_{}^{n-{\cos }^{-1\left(\frac{2h}{W}\right)}}-\sin \left(3{\cos }^2-1\right)d\\ \frac{1}{WLt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{4}{A_{\mathrm{uc}}}\frac{p}{h}\frac{2h}{W}\\ =\frac{1}{W^{2}Lt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{8}{A_{\mathrm{uc}}}p\end{array}$
with t being the thickness of the graphene film. For simplicity, add up all atoms within the radius of W/2 (assuming W<L) in the integration.

(39) An AC driving voltage at will cause the molecular dipole to oscillate at the same frequency, introducing charge density fluctuation on graphene. Here a proportional quantity, ({tilde over (V)}.sup., ), is included to account for the degree of dipole excitation, ({tilde over (V)}.sup., )p. The amount of dipole perturbation at would depend on the strength of the AC drive voltage compared with the binding strength between molecule and graphene. If the molecule is in free space, then one would expect the entire molecule to flip following {tilde over (V)}.sup., i.e., =cos t. Hence the oscillating molecular dipole induced charge density fluctuation on graphene can be estimated by:

(40) $\begin{array}{cc}{\tilde{Q}}_m^{}=\left({\tilde{V}}^{},\right){\stackrel{.fwdarw.}{P}}_{\mathrm{Gr}}^Z=\left({\tilde{V}}^{},\right)\frac{1}{W^{2}Lt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{8}{A_{\mathrm{uc}}}p.& \left(9\right)\end{array}$
Note that since graphene is not an ideal metal, equation (9) only serves for order of magnitude calculation. From equations (6) and (9), the sensing signal for a single molecule obtained is:

(41) $\begin{array}{cc}{I}_{\mathrm{mix}}=\frac{W}{L}\left({\tilde{V}}^{},\right)\frac{1}{W^{2}Lt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{8}{A_{\mathrm{uc}}}p{\tilde{V}}^{}=\frac{\left({\tilde{V}}^{},\right)}{W{L}^{2}t}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{8}{A_{\mathrm{uc}}}p{\tilde{V}}^{}.& \left(10\right)\end{array}$
If

(42) $n=\frac{N}{\mathrm{WL}}$
is the real density of the surface adsorbed molecules, then:

(43) $\begin{array}{cc}{I}_{\mathrm{mix}}=\frac{\left({\tilde{V}}^{},\right)}{Lt}\frac{{}_{\mathrm{Gr}}}{4{\mathrm{.Math.}}_0}\frac{8}{A_{\mathrm{uc}}}\mathrm{np}{\tilde{V}}^{},& \left(11\right)\end{array}$
for quantitative measurement of analyte concentration in the vicinity of graphene sensor. For better noise rejection, use AM modulation and measure the mixing current change at the modulation frequency.

(44) An estimation of the sensor detection limit is obtained using equation (10). For a typical device, use L=W=1 m, t=0.34 nm, =1000 cm.sup.2V.sup.1s.sup.1, and .sub.Gr=0.9 .sup.3 (in CGS unit). A single DMMP molecule with p=3.62 Debye is adsorbed on graphene surface. For simplicity, assume the molecular dipole is partially excited at {tilde over (V)}.sup.=20 mV, with =0.1cos t. Using equation (10), estimate a sensor signal on the order of 3 fA for a single DMMP molecule. Using a 3 noise floor of 0.12 nA, estimate a detection limit of 10.sup.4 molecules for the proof-of-principle devices.

(45) This number can also be compared with the estimation from concentration calculation. Using the molecule weight of 124 g/mol and the mass density of 1.145 g/mL (liquid), estimate that the inter-molecule distance is approximately 0.57 nm for liquid DMMP. Therefore, the maximal number of DMMP molecules adsorbed and closely packed on a 1 m (W)1 m (L) graphene surface is approximately 310.sup.6. Further assume that 23.2 ng of injected DMMP molecules saturate the graphene surface and form a liquid layer, which generates a sensing signal of approximately 6 nA. Using a 3 noise floor of 0.12 nA, estimate that the upper limit of detectable DMMP molecules on the graphene sensor surface is approximately 610.sup.4, agreeing with the detection limit estimated from equation (10). It should be noted that this detection limit can be readily improved to 100 molecules by reducing the device channel length from 1 m to 0.1 m. Furthermore, by reducing the noise floor through better design of measurement circuitry, coupled with the adoption of higher quality graphene transistor or carbon nanotube transistor, one could push the detection limit into single molecule regime.

(46) To demonstrate vapour sensing, a graphene FET (GrFET) sensor 10 was fabricated on silicon wafer 31 with thermal oxide using chemical vapour deposition-grown graphene. A single-layer graphene film was first grown on copper foils using the chemical vapour deposition method. After growth, 950 PMMA (poly(methyl methacrylate)) A2 (Microchem) was spin-coated on one side of the copper substrate and baked at 180 C. for 1 min. Graphene on the uncoated side was removed by 25 s of O.sub.2 plasma etch and then the sample was placed in 0.1 M ammonium persulfate (Sigma-Aldrich) overnight to etch away the copper. Next, the PMMA-coated graphene was transferred from solution onto a thermal oxide substrate and allowed to dry for a day. The PMMA was removed by placing the die in acetone and then isopropyl alcohol (IPA) for 15 min each. Through photolithography, metal deposition and bilayer lift-off processes using LOR 3A (Microchem) and SPR 220-3.0 (Shipley), 0.5 nm titanium/100 nm gold source-drain electrodes were patterned. The graphene channel was patterned using photolithography and 25 s of O.sub.2 plasma etch. A typical device has a graphene characterized by DC electrical transport measurements before sensing experiments. The graphene channel was p-doped with a hole carrier mobility of 900 cm.sup.2V.sup.1s.sup.1. During all vapour sensing experiments carried out in this disclosure, the gate voltage was kept at 0V.

(47) The graphene FET 10 was integrated with a standard GC system 32 as seen in FIG. 3. The GC system 32 includes an inlet of a carrier gas, a sample injector and a separator column. In this example system, the GrFET sensor 10 is placed at an outlet of the separator column and serves as the detector. For demonstration purposes, the GrFET sensor die was capped with a 400-m depth400-m width-etched silicon-flow channel 33, before connecting to a 70-cm long GC guard column. The flow channel was carefully aligned to the center of the die to ensure all the graphene sensors were exposed to the vapour flow. Analytes were injected using a syringe at the injection port and delivered to the graphene sensor 10. Connection of the graphene sensor module to a GC system was achieved by using a 70-cm long guard column (part no. 10029, inner diameter 250 m, from Restek, Bellefonte, Pa. USA). Injected mass for each analyte was calibrated using a flame ionization detector (FID) 39.

(48) FIG. 4 shows the mixing current response of a typical graphene heterodyne sensor to nine different analytes including: (1) pentane, (2) hexane, (3) benzene, (4) chlorobenzene, (5) dichloromethane, (6) chloroform, (7) N,N-dimethylformamide, (8) DMMP and (9) acetone. Rapid detections of six out of nine analytes were successfully demonstrated. Furthermore, initial results indicate that our graphene sensor was highly selective to polar molecules: three nonpolar molecules (pentane, hexane and benzene) showed no signal, while the remaining polar ones showed strong response. In addition, the sensing signal also appeared to have different signs for different molecules.

(49) Next, the temporal response of a GrFET sensor to pulsed injections of varying masses of common volatile organic compounds is investigated in detail. Some of the examples are shown in FIGS. 5A-5H. Significantly, fast sensor response with a sub-second full-width-half-maximum (t.sub.1/2) was observed for dichloromethane (t.sub.1/2=0.61 s), ethanol (t.sub.1/2=0.92 s), chloroform (t.sub.1/2=0.69 s), 2-propanol (t.sub.1/2=0.98 s), and acetone (t.sub.1/2=0.75 s), which were similar to FID response times. Even for relatively high boiling point vapours-chlorobenzene, dioxane and N,N-dimethylformamide, whose boiling point is over 100 C., the graphene heterodyne sensor still showed impressive response times of 0.9 s, 1.65 s and 1.8 s, respectively, which was comparable with the FID response. These results suggest that the temporal broadening that was observed is owing to the retentive effect of the GC column, and the intrinsic speed of the graphene heterodyne detector is better than 0.1 s, limited by the rise time of the lock-in amplifier.

(50) Vapours of a higher boiling point tend to condense more on a surface and thus have longer desorption time. They can be used as a model system to ultimately test the sensor response time and sensitivity. FIG. 6 presents the temporal response of the graphene sensor to 205 pg injection of DMMP (boiling point=181 C.) along with the corresponding FID response time. Comparable response time for graphene sensor (t.sub.1/2=6.1 s) and FID (t.sub.1/2=5.5 s) was observed. However, DMMP desorption time for graphene sensor (response peak to 90% recovery time, t.sub.peak-90%=28 s) was approximately two times that of FID (t.sub.peak-90%=13.2 s), indicative of the slow desorption process of DMMP molecules from the graphene surface.

(51) To investigate the sensitivity of the graphene heterodyne sensor, the sensor response, I.sub.mix, in response to repeated doses of DMMP varying from 205 pg to 23.2 ng was plotted in FIG. 7. It is clear that sensing signal increases with increasing injected mass of DMMP, and that the response is instantaneous and also completely reversible for all the masses under test. Experimentally, the lowest injected mass was 205 g, corresponding to a concentration of approximately 43 ppb. To further estimate the graphene sensor's detection limit, the sensor dosage response is plotted in FIG. 8. The sub-linear response in the log-log scale reflects the transient behavior of vapour pulses interacting with the graphene sensor and is consistent with what has been observed previously with optical sensors. Using a 3 noise floor, the detection limit for DMMP is approximately 3 pg in mass or 0.64 ppb in concentration, which to our knowledge is the lowest for any uncoated, pristine nanoelectronic vapour sensor and similar to the best sensitivities reported on chemically coated nano-electronic vapour sensors. The order of magnitude calculation also suggests that the noise floor corresponds to 10.sup.4 molecules on the graphene surface.

(52) Graphene heterodyne sensors are also capable of detecting a wide range of vapour analytes without the need of chemoselective surface coatings. FIG. 9 plots the graphene sensor dosage response for additional nine analytes. It is observed that all analytes showed linear response on the log-log scale at low concentrations and saturate at higher concentrations. The superior performance of the high-frequency heterodyne detection is further evidenced when contrasting the results in FIGS. 7 and 9, with those using the conventional DC detection method under the identical GC conditions, the GrFET sensor was much less responsive in both response time and sensitivity. The parameters and the experimental results (such as response time and lowest injected mass and so on) of all 13 analytes used in this work are summarized in the table below.

(53) TABLE-US-00001 Concen- FWHM tration at Boil- Smallest (s) minimum Dipole ing injected (averaged injected moment point mass over trip- mass Analyte (D) ( C.) (ng) licates) (ppm) Pentane 0 36 Hexane 0 69 Benzene 0 80 Toluene 0.37 111 172 1.61 210 1,4-Dioxane 0.45 101 52 2.1 50 Chloroform 1.04 61 74 0.68 164 Chlorobenzene 1.54 131 5.5 0.75 12 Dichloromethane 1.6 40 66 1 139 2-Propanol l.66 82 39 1.12 105 Ethanol 1.69 79 15 0.9 65 Acetone 2.88 56 15 0.8 58 DMMP 3.62 181 0.205 6.83 0.043 DMF 3.82 153 0.944 2.54 0.92

(54) It is clear that polar molecules yield a stronger signal, whereas the signal from nonpolar molecules is nearly negligible. This distinct sensor response can be understood by examining {tilde over (Q)}.sub.m.sup.w in equation (3), which is the molecular dipole-induced charge density modulation on graphene, and is proportional to the molecular dipole moment. To further confirm the dipole-detection-based sensing mechanism, the sensor response to a pair of cis- and trans-isomers, cis- and trans-1,2-dichloroethene, is measured with the same injected mass as seen in FIG. 10. It is clear that the polar cis-1,2-dichloroethene (dipole moment=1.9 D) exhibits a strong sensing signal, while the nonpolar trans-1,2-dichloroethene (dipole moment=0 D) only shows minimal response below the 3 noise floor.

(55) Referring to FIG. 11, the graphene heterodyne sensor further exhibits strong bi-polar behavior, where the sensor response can be categorized into three types-zero (left panel), positive (middle panel) and negative (right panel). This characteristic can again be traced to the fact that our sensor is responsive to the dipole moment of the surface-adsorbed molecule. Consequently, nonpolar molecules, such as hexane and benzene, show no sensing signal. On the other hand, for polar molecules adsorbed on top of graphene, opposite dipole orientation can lead to opposite signs in the mixing current signal. This bi-polar response of the graphene heterodyne sensor not only adds an additional degree of selectivity for vapour identification, but also hints at its potential as an excellent test bed for elucidating the fundamental molecule-graphene interaction.

(56) Rapid separation and detection of chemical vapours are of critical importance for on-site vapour monitoring with portable micro-GC systems. To this end, the response of the graphene heterodyne sensor (lower panel) and FID (upper panel) to a mixture of eight analytes is presented in FIG. 12. The analytes were separated using a combination of GC columns and delivered simultaneously to the graphene sensor and FID using a Y-split. It was observed that the graphene sensor not only responds instantaneously to all polar molecules in the same temporal window as the FID, but also switches sign rapidly for electronegative and electropositive species (relative to graphene) eluted one after the other (6-dioxane and 7-toluene in FIG. 12). Pentane and benzene, being nonpolar, were not detected by the graphene sensor. Overall, the proof-of-concept graphene nanoelectronic heterodyne sensor successfully detected all six polar analytes in the mixture with comparable performance as a commercial FID detector. Superior to the bulky destructive FID detector, the graphene sensor is non-destructive, highly compact, and can be readily integrated on-chip with a micro-GC column and read-out circuitry, with zero-dead volume. The different signs of I.sub.mix for 2-propanol in FIGS. 5A-5H and FIG. 12 are noted, although all devices processed (including thermal oxide growth) in one batch show consistent behavior. This is attributed to a substrate effect where end terminations may preferentially orient the molecules through hydrogen bonding, further detailed investigation is needed.

(57) In some embodiments, the heterodyne sensor described above can operate as a stand-alone device. In other embodiments, the heterodyne sensor can be placed along a flow path of a gas and liquid separation device, such as a gas chromatography, a liquid chromatography, a capillary electrophoresis, as well as other types of gas and liquid separation devices. The flow path can be gas (or liquid) separation columns or any channels that connect to the gas (or liquid) separation columns. For example, an array of heterodyne sensor may be integrated into a micro gas chromatography device as seen in FIGS. 13A and 13B. In FIG. 13A, the bottom substrate 91 contains the micro gas chromatography channel 92; whereas, in FIG. 13B, the top silicone substrate 95 contains the graphene sensor array 96 and electrodes 97. The two substrates will be anodically bonded and the sensor array will aligned with the fluidic channel. It will be readily apparent from these teachings how to integrate the heterodyne sensor of this disclosure with other types of separation devices.

(58) Compared with existing nanoelectronic vapour sensor technologies, the graphene nanoelectronic heterodyne sensor presented in this disclosure has a number of distinct advantages. First, it is a dipole-detection-based technique, and does not involve the slow dynamics of interface states and charge-transfer processes. Therefore, the sensing response time can be tremendously improved. Second, unlike impedance sensing-based chemicapacitors, the high carrier mobility of graphene transistor provides in situ intrinsic gain for signal amplification (equation 3). Third, graphene can be synthesized in wafer scale and is fully compatible with existing top-down fabrication technology and on-chip electronic circuitry, making graphene nanoelectronic sensors uniquely suited for practical applications. Fourth, the detection limit of graphene heterodyne sensor can be readily pushed down to <100 molecules by device optimization opening a door for fundamental studies of molecule-nanomaterial interaction with unprecedented precision. Finally, the heterodyne-sensing technique can be adopted in other types of nanomaterial systems, such as in carbon nanotube and semiconductor nanowire-based sensors, thus having the potential to revolutionize electronic sensor technology as a whole.

(59) The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.

(60) The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms a, an and the may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms comprises, comprising, including, and having, are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.

(61) When an element or layer is referred to as being on, engaged to, connected to or coupled to another element or layer, it may be directly on, engaged, connected or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being directly on, directly engaged to, directly connected to or directly coupled to another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., between versus directly between, adjacent versus directly adjacent, etc.). As used herein, the term and/or includes any and all combinations of one or more of the associated listed items.

(62) Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as first, second, and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.