Tunable Adsorption and Wetting

Abstract

A device having a semiconductor nanomaterial surface, formed on a dielectric layer, having a conductive material under the dielectric layer, wherein a potential across the dielectric modified an absorption property of the semiconductor nanomaterial. A method of controlling a property of surface is provided, comprising: providing a device having a semiconductor nanomaterial having the surface, formed on a dielectric layer, having a conductive material under the dielectric layer; and controlling an electrostatic field at the semiconductor nanomaterial to modify at least one property of the surface with respect to molecules. The property may be absorption or wetting, for example.

Claims

1. A device having a controlled property with respect to surrounding molecules, comprising: a substrate having a conductive surface; a dielectric layer formed on the conductive surface; and a semiconductor nanomaterial, formed on the dielectric layer, wherein an electrostatic field from the conductive material modifies a property of the semiconductor nanomaterial with respect to the surrounding molecules.

2. The device according to claim 1, wherein the dielectric layer is an insulator, and the conductive material is a metal.

3. The device according to claim 1, wherein the surrounding molecules comprise polar molecules, and the property comprises an absorption or wetting of the semiconductor nanomaterial surface with the polar molecules.

4. The device according to claim 3, wherein the polar molecules comprise water.

5. The device according to claim 1, wherein the semiconductor nanomaterial is graphene.

6. The device according to claim 1, wherein the semiconductor nanomaterial is MoS.sub.2.

7. The device according to claim 1, wherein the semiconductor nanomaterial is a boron compound.

8. The device according to claim 1, further comprising a nanoporous material over the semiconductor nanomaterial.

9. The device according to claim 1, further comprising a metal organic framework over the semiconductor nanomaterial.

10. The device according to claim 1, further comprising a zeolite over the semiconductor nanomaterial.

11. The device according to claim 1, further comprising catalytic nanoparticles proximate to the semiconductor nanomaterial.

12. The device according to claim 1, further comprising a porous membrane, wherein a transport across the porous membrane is dependent on the electrostatic field.

13. The device according to claim 1, further comprising an electronic control configured to establish the electrostatic field.

14. The device according to claim 1, wherein the surrounding molecules are physiosorbed or chemisorbed.

15. The device according to claim 1, further comprising an electronic sensor configured to sense electrical conductivity through the semiconductor nanomaterial.

16. A method of controlling a surface property, comprising: providing a device having a semiconductor nanomaterial having a surface, formed on a dielectric layer, having a conductive material under the dielectric layer configured to impose an electric field on the semiconductor nanomaterial; and controlling an electrostatic field on the semiconductor nanomaterial to modify the property of the surface with respect to surrounding molecules.

17. The device according to claim 16, wherein the dielectric layer is an insulator, the conductive material is a metal, and the semiconductor nanomaterial is a 2D material selected from the group consisting of graphene, molybdenum disulfide, and a boron compound.

18. The method according to claim 16, wherein at least one of a nanoporous material, a metal organic framework, a zeolite, catalytic nanoparticles, a surfactant, and a liquid crystal is provided over the semiconductor nanomaterial.

19. The method according to claim 16, wherein a porous membrane is provided, wherein a transport of molecules across the porous membrane is dependent on the electrostatic field.

20. A system, comprising: a conductive substrate; a dielectric material on the conductive substrate; a semiconductor nanomaterial, formed on the dielectric material; and an automated control, configured to control an electrostatic field surrounding the material, to thereby alter a surface property of the semiconductor nanomaterial.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0333] FIG. 1A shows schematic of the water molecules orientation vs the gate voltage position when V.sub.GS>V.sub.CNP.

[0334] FIG. 1B shows schematic of the water molecules orientation vs the gate voltage position when V.sub.GS<V.sub.CNP.

[0335] FIG. 1C shows interdependency of water molecules orientation and the doping status of graphene. Where the graphene is electrically n-doped, water molecule adsorbs with the OH band downward resulting in a slight p-doping of graphene.

[0336] FIG. 1D shows interdependency of water molecules orientation and the doping status of graphene. Where the graphene is electrically p-doped, water molecule adsorbs with the OH band upward resulting in a slight n-doping of graphene.

[0337] FIG. 2 shows a schematic overview of a graphene field effect transistor on a quartz crystal microbalance (QCM) preparation process.

[0338] FIG. 3A shows schematic band structure of graphene upon changing the gate voltage for originally undoped-graphene.

[0339] FIG. 3B shows schematic band structure of graphene upon changing the gate voltage for intrinsically p-doped graphene

[0340] FIG. 3C shows schematic band structure of graphene upon changing the gate voltage for intrinsically n-doped graphene

[0341] FIG. 4A shows adsorption isotherms of water on graphene at three different gate voltage: 0V, +20V, −20V. The isotherms show higher uptakes for non-zero gate voltages where the gate voltage induces electrons/holes to the graphene. The IV curves prior to water adsorption shows no hysteresis after annealing.

[0342] FIG. 4B shows the corresponding IV curve of each test prior to the water adsorption (at high vacuum).

[0343] FIG. 5 shows the IV curves measured at high vacuum by sweeping in both directions.

[0344] FIG. 6A shows the IV curves measured after water vapor exposure for the adsorption tests with the gate voltage at +20V. The sweep direction was from +20V to −20V.

[0345] FIG. 6B shows the IV curves measured after water vapor exposure for the adsorption tests with the gate voltage at −20V. The sweep direction was from −20V to +20V.

[0346] FIG. 6C shows the IV curves measured after water vapor exposure for the adsorption tests with the gate voltage at 0V. The sweep direction was from +20V to −20V.

[0347] FIG. 6D shows the IV curves measured after water vapor exposure for the adsorption tests with the gate voltage at 0V. The sweep direction was from +20V to −20V.

[0348] FIG. 7A shows the highest occupied molecular orbital of H.sub.2O.

[0349] FIG. 7B shows the lowest unoccupied molecular orbital of H.sub.2O.

[0350] FIG. 8A shows the shift in the charge neutral point on the left and the doping density on the right upon water exposure at four different gate voltages: +20V (triangle up), −20V (triangle down), 0V with +20V as the starting sweep voltage (circle), and 0V with −20V as the starting sweep voltage (square).

[0351] FIG. 8B shows the Fermi level shift induced by water adsorption at four different gate voltages: +20V (triangle up), −20V (triangle down), 0V with +20V as the starting sweep voltage (circle), and 0V with −20V as the starting sweep voltage (square).

[0352] FIG. 9A shows the effect of gate voltage on the doping rate as a function of exposure time tested at four different gate voltages: +20V (triangle up), −20V (triangle down), 0V with +20V as the starting sweep voltage (circle), and 0V with −20V as the starting sweep voltage (square).

[0353] FIG. 9B shows the effect of gate voltage on the doping rate as a function of exposure pressure tested at four different gate voltages: +20V (triangle up), −20V (triangle down), 0V with +20V as the starting sweep voltage (circle), and 0V with −20V as the starting sweep voltage (square).

[0354] FIG. 10 (see U.S. Pat. No. 7,702,660), expressly incorporated herein by reference), shows a block diagram that illustrates a computer system.

[0355] FIG. 11A shows a device with a surfactant molecule underneath the surface controlled by the gate voltage.

[0356] FIG. 11B shows a device with surfactant on top of the device controlled by the gate voltage.

[0357] FIG. 11C shows a liquid crystal underneath the 2D material controlled by the gate voltage.

[0358] FIG. 11D shows a liquid crystal above the 2D material controlled by the gate voltage.

[0359] FIG. 11E shows an adsorbent underneath a nanoporous 2D material, where adsorption selectivity, isotherms, and kinetics are tuned by the gate voltage.

[0360] FIG. 12A shows an application where a gradient in surface properties is generated laterally by a changing voltage difference spatially between the 2D material and the gate.

[0361] FIG. 12B shows an application where a temporally changing 2D material-gate voltage changes the wetting in time. This can allow transition from more hydrophilic to hydrophobic, and vice-versa.

[0362] FIG. 12C shows filmwise condensation being converted to dropwise via an applied 2D material-gate voltage.

[0363] FIG. 12D shows an array of surface property tunable regions actuated via separately applied voltages.

[0364] FIG. 13 shows potential manufacturing method including potential materials and techniques.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0365] Experimental Methods

[0366] Apparatus

[0367] An apparatus with the ability to measure the adsorption isotherms under different gases, and the electronic properties of 2D materials, was designed and constructed. The environmental vacuum chamber was equipped with a custom sample holder to measure the IV curve (Keithley SMU 2614B) and a dry pumping station (Pfeiffer HiCube 80 Eco) that reaches a base pressure of 1×10.sup.−6 Torr (MKS 390 Micro-Ion® ATM). The chamber was temperature controlled via a recirculation bath (Haake K20, Glass Encapsulated Thermistors 55004). Deionized water (DI) (Sigma-Aldrich 38796) was degassed through multiple freeze-pump-thaw cycles and was used as the vapor source for water adsorption. A modified 5 MHz AT-cut Quartz Crystal Microbalance (QCM) (Stanford Research Systems QCM200) was implemented for the adsorption uptake measurements. Vapor pressure was measured using two heated capacitance manometers (Kurt J. Lesker HCG045-OT-1-1 and HCG045-FT-1-1). All the sensors were monitored via MATLAB and a data acquisition logger (Keithley DAQ6510).

[0368] Sample Preparation

[0369] A back gated Graphene Field Effect Transistor (GFET) was fabricated on top of a 5 MHz AT cut QCM. The top electrode of the QCM also serves as the back gate for the transistor. The gate dielectric was a 100 nm Al.sub.2O.sub.3 deposited via Atomic Layer Deposition (ALD) with Trimethylaluminium (TMA) and Oxygen plasma at 200° C. (Oxford Flex AL). Prior to the ALD deposition, the samples were sonicated for 15 min in acetone, methanol and isopropyl alcohol, respectively. QCMs with Au electrodes were used to avoid the back electrodes degradation during the GFET fabrication process. For a better adhesion between the dielectric and the back gate, 100 nm of Ti was deposited on the top electrode of the QCM via E-beam evaporation (AJA International).

[0370] After the dielectric deposition, Poly Methyl Methacrylate (PMMA) backed Chemical Vapor Deposited (CVD) graphene (Graphenea Monolayer Graphene on Polymer Film) was transferred onto the QCM. The samples were dried in air for 30 min, followed by baking on a hotplate at 150° C. for 1 hr. Then, the samples were kept under low vacuum (0.1 Torr) for 24 hours to remove the trapped water between the substrate and graphene. This results in a better bond between the dielectric and the graphene, and also minimizes the effect of trapped water on the interaction of adsorbates with graphene. To remove PMMA from the graphene, the samples were soaked in acetone at 50° C. for lhr followed by soaking in isopropyl alcohol for another hour and then dried with N.sub.2. To further remove PMMA trace residuals, the samples were annealed at 300° C. and 1×10.sup.−8 Torr for 2 hours with a ramping temperature of 5° C./min. After the graphene deposition, the source and drain (5 nm Cr+100 nm Au) were deposited on top of graphene via E-beam evaporation (AJA International), creating a 0.24 inch by 0.24 inch channel that overlaps with the top electrode of the QCM. The entire fabrication process was conducted in a class 100 clean room.

[0371] Before each test, the sample was annealed (ex-situ) at 150° C. for lhr under 95%Ar-5%H.sub.2 at 0.1 mbar. Then, it was transferred to the test chamber and was pumped down for 18 hr under high vacuum before each adsorption test. This procedure was done to help the graphene to return to its original Charge Neutral Point (CNP). Although it would be ideal to anneal the sample in-situ, i.e. without exposing to air after annealing, the limitations in the electronics of the custom QCM holder prevented reaching an annealing temperature more than 120° C., which was not sufficient to restore the original CNP. Besides the external heating, current annealing was also adapted, where a high current was applied between the source and the drain to heat up the graphene and desorb water. This technique was initially effective, however, using a gate voltage to enhance the source-drain current results in breaking the dielectric after multiple tests.

[0372] Results and Discussions

[0373] The graphene IV curve from a GFET device is a characterization of the doping level. The gate voltage with the minimum conductance represents the CNP, which indicates whether the graphene is p or n doped. A pristine (undoped) graphene has its minimum conductance at the zero-gate voltage where its mobility is maximum, and the carrier density is zero (the Dirac Point). In a back gated GFET, an applied gate voltage greater than V.sub.CNP (the voltage at the minimum conductance, i.e., the charge neutral point) inserts electrons into the conduction band (V.sub.GS-V.sub.CNP>0, the red line), shifts the Fermi level upward and n-dopes the graphene. Conversely, an applied gate voltage smaller than V.sub.CNP (V.sub.GS-V.sub.CNP<0, the blue line), extracts electrons from the valence band and creates holes, which results in shifting the Fermi level downward and p-doping the graphene as shown in FIGS. 3A-3C. Thus, in the case of no applied gate voltage, a p-doped graphene has a V.sub.CNP>0 and a n-doped graphene has a V.sub.CNP<0.

[0374] Adsorption Isotherms at Different Gate Voltages

[0375] The GFET was successfully made on a QCM in order to measure the mass of adsorbed water at different gate voltages. In this set of experiments, graphene was exposed to water vapor while the gate voltage was kept at a constant value during water adsorption. The fabrication is shown in FIG. 2. The quartz crystal microbalance (QCM) is prepared as follows. The quartz crystal is prepared by sonication in acetone (15 min.), methanol (15 min.) and isopropyl alcohol (IPA 15 min.). A 100 nm titanium film is deposited on the prepared crystal. A 100 nm layer of aluminum oxide (Al.sub.2O.sub.3) dielectric is deposited over the titanium layer. A graphene layer is transferred onto the dielectric by providing a graphene layer on a substrate coated with poly methyl methacrylate (PMMA), which is released from the substrate in water and the PMMA-graphene layer transferred on the dielectric, dried 30 min. in air, 1 hr. on a hot plate at 150C, and 24 hr under low vacuum. The PMMA is removed by immersing 1 hr in 50C acetone, 1 hr in IPA, and 2 hr under high vacuum at 300C. Source and drain are deposited at the edge of the graphene layer as 5 nm Cr and 100 nm Au.

[0376] FIGS. 4A and 4B show adsorption isotherms of water onto graphene at three different gate voltages: 0V, +20V, −20V. FIG. 4A shows that the isotherms show higher uptakes for non-zero-gate voltages than zero-gate voltage. FIG. 4B shows the corresponding IV curves prior to each test while under high vacuum. The IV curves prior to water adsorption show no hysteresis after annealing.

[0377] IV curves were only measure at the beginning (high vacuum) and at the end of the experiment. FIG. 4A. shows the adsorption isotherms of water on graphene at three different gate voltages, 0V, +20V, and −20V. It is shown that non-zero gate voltages result in higher uptakes as the pressure increases. However, there is no significant change in the uptake depending on the polarity of the gate. The reasoning behind this observation will be later discussed by a new set of experiments.

[0378] The water adsorption onto graphene increased ˜15% and the doping levels increased by a factor of three with a gate-to-graphene voltage of +20 or −20V compared to 0V for sub-monolayer adsorption. This change in uptake is attributed to the increase in density of state of graphene upon electrical-doping, which changes the Coulombic and van der Waals interactions. The water adsorption onto graphene is either n- or p-doping depending on the applied gate-to-graphene voltage. The ambi-doping nature of water onto graphene is due to the polar nature of water molecules, so the doping depends on the orientation of the water molecules.

[0379] Note that the sample was annealed before each experiment to return graphene to its original charge neutral point. FIG. 4B. shows the IV curves measured prior to each experiment at high vacuum. It can be seen that the no hysteresis exists in the charge neutral point. With the charge neutral point at zero gate voltage, the three applied gate voltages during water adsorption, 0V, +20V, and −20V, will induce no doping, n-doping, and p-doping, respectively. Note that this could be changed as water induces doping.

[0380] Hysteresis in IV Curves

[0381] In a pristine graphene, the Fermi level is at the Dirac point where the number of carriers (electrons and holes) are equal i.e., the total charge of graphene at this point is zero. A negative applied gate voltage will move the electrons from the graphene to the gate (create holes within graphene) and a positive applied gate voltage will move the electrons from the gate to the graphene. Thus, sweeping the gate voltage from a negative value to a positive value will change the doping type from p-doping to n-doping, and vice-versa for a positive gate voltage.

[0382] FIG. 5 shows the IV curves measured for a sample under high vacuum by sweeping the gate voltage in both directions, +20V to −20V and −20V to +20V while the source-drain voltage was kept at 0.1V. The sweeping direction should not affect the position of the charge neutral point, however, there is a hysteresis in the charge neutral point. This hysteresis comes from the charge transfer by nearby adsorbates, such as water, or charge injection into the trap sites on the dielectric substrate.sup.150. Although GFETs normally create a uniform electric field through the gate, impurities could result in the hysteresis. The hysteresis changes subject to the sweeping voltage range/rate and the surrounding condition.sup.150-153. Although both mechanisms cause the hysteresis affect graphene on the seconds time scale, a higher sweep rate decreases the hysteresis caused by the charge transfer while a slower rate decreases the hysteresis caused by the capacitive gating.sup.150.

[0383] In all the IV measurements, the gate voltage was swept with a 0.1V increment/decrement at a ˜8V/sec rate (the maximum achievable by the source meter). This rate gave the minimum hysteresis which shows that the first mechanism causing the hysteresis was more dominant.

[0384] Effect of Water Vapor Exposure on Doping

[0385] The effect of a gate voltage on the water adsorption onto graphene was investigated by analysis of the IV curves. In each test, the gate voltage was kept at a constant value (+20V, −20V, and 0V) during water adsorption. IV scans were conducted every minute during water vapor exposure. To avoid further adsorption/desorption during the voltage sweep, the chamber was evacuated for 1 minute before each IV measurement (pressure minimum of 5 mTorr). Since it was shown that the voltage sweep direction could affect the charge neutral point for the adsorption tests with an applied +20V gate voltage, the voltage for the IV measurements was swept from +20V to −20V and then back to +20V. Conversely, for the −20V adsorption test, the voltage was swept from −20V to +20V, then back to −20V. Two adsorption tests were performed for the zero-gate voltage: One with a +20V to −20V to +20V sweep and the other one with a −20V to +20V to −20V sweep. The purpose of running two tests at zero gate voltage was to see if the first sweep direction affects the water adsorption on graphene. For all measurements, the source-drain voltage was kept at 0.1V.

[0386] FIGS. 6A-6B show the IV curves, upon water vapor exposure, for tests with different applied gate voltages. In the test with an applied gate voltage of +20V during the adsorption the graphene was initially n-doped, and the adsorption of water molecules made the graphene less n-doped, eventually leading to p-doping (FIG. 6A). On the other hand, when the applied gate voltage was kept at −20V during the adsorption where the graphene was initially p-doped, the adsorption of water molecules induce n-doping and making the graphene less p-doped (FIG. 6B).

[0387] FIGS. 6A-6D shows 3 IV curves measured under vacuum after x minutes (x=0, 1, 2, . . . , 20) of water vapor exposure with the gate voltage at (FIG. 6A) +20V, (FIG. 6B) −20V, and (FIGS. 6C and 6D) 0V. The gate voltage sweep in FIG. 6A and 6C was +20V.fwdarw.−20V.fwdarw.+20V, and in FIGS. 6B and 6D) was −20V.fwdarw.+20V.fwdarw.−20V. The chemical doping due to adsorption of water vapor is larger for the +20V and −20V tests (FIGS. 6A and 6B) than the 0V tests (FIGS. 6C and 6D), as indicated by their greater shift of their charge neutral. It is also noted that the direction of the charge neutral point shift is opposite for the +20V and −20V tests (FIGS. 6A and 6B), demonstrating that water can ambi-dope graphene. The 0V tests also demonstrate small and opposite shifts in the change neutral point due to hysteresis from the vacuum applied gate sweep voltage.

[0388] Tests with a larger absolute applied gate voltage show more doping (|V.sub.GS-V.sub.CNP|), which is proportional to the water uptake. Water molecules consist of one oxygen atom covalently bonded with two hydrogen atoms in a tetrahedral structure. The higher electronegativity in oxygen creates an electrical dipole moment in water molecules with negative charges on the oxygen atom and positive charges on the hydrogen atoms. This dipole moment in the water molecules affects its adsorption on a surface.

[0389] Many dopants clearly fall in two categories, electron-donor molecules that n-dope graphene and electron-acceptor molecules that p-dope.sup.58,154, however the doping induced by water adsorption onto graphene depends on the orientation of the adsorbed water molecule which is controlled by the electric field at the supporting substrate.sup.155,156. Density-functional theory (DFT) calculations showed the orientation of water molecules with one O—H bond parallel to the surface and the other one pointing towards the surface is the most energy favorable orientation for water adsorption on a perfect graphene.sup.154. However, this orientation can be altered on a supported graphene. Depending on the orientation of the adsorbed water molecule, it can either p-dope or n-dope graphene. In a water molecule, the HOMO (Highest Occupied Molecular Orbital) is completely located on the O atom and the LUMO (Lowest Unoccupied Molecular Orbital) is mostly located on the H atoms (FIG. 7A). Due to the relative position of the HOMO and the LUMO of a water molecule with respect to the Dirac point, if the O atom points to graphene (O—H bond pointing up), the HOMO plays the dominant role and donates some charges from water to graphene through a small mixing with graphene orbitals above the Fermi level (creating n-doping). If the H atom points to graphene (O—H bond pointing down), there is a small charge transfer to the water molecule from graphene through small mixing with the graphene orbitals below the Dirac point (creating p-doping).sup.154.

[0390] Therefore, in the case of an applied gate voltage greater than the voltage at the charge neutral point (V.sub.G>V.sub.CNP), where graphene is n-doped and electrons are the dominant charge carriers in graphene, water molecules tend to adsorb on graphene with the positive side of the dipole (H atoms towards graphene) which transfers charge from the graphene to the water molecules and creates p-doping in graphene. This is aligned with moving the CNP in FIG. 6A. in the positive direction where V.sub.GS=+20V, which is greater than V.sub.CNP. Inversely, when V.sub.GS<V.sub.CNP, the graphene is p-doped and holes are the dominant charge carriers. Consequently, water molecules adsorb on graphene with the OH bonds upward and the charge transfers from the water to the graphene, n-doping the graphene. This agrees with FIG. 6B, where V.sub.GS=−20V, which is less than V.sub.CNP, and the CNP moves in the negative direction.

[0391] FIGS. 1A-1E illustrate the mechanism for water molecules changing the doping. In the two adsorption tests where the gate voltage was kept at zero potential during water exposure, the graphene is affected by the last voltage applied during the IV measurements. This is probably due to adsorbed water molecules that were aligned according to the last applied gate voltage. Although both cases showed smaller shift of the CNP, the initial doping was aligned with its prior test. In the zero gate voltage test with +20V starting/ending sweep, water molecules adsorbed with the OH bonds downward, resulting in p-doping graphene and in the other zero gate voltage test where the voltage was swept from −20V and ended at −20V, water molecules adsorbed with the oxygen atoms pointing to graphene, creating n-doping. This larger shift of the CNP during the tests with non-zero gate voltages shows that an applied gate voltage can enhance the water adsorption on graphene, however, due to the dipolar nature of the water molecules, the polarity of the gate does not affect the adsorption significantly.

[0392] Effect of the Gate Voltage on Doping Upon Water Exposure

[0393] Although IV curves provide a simple visualization of the CNP position, other useful information such as the carrier density and the mobility of graphene can be derived from the IV curves. The doping density corresponds to the extent of adsorbed water on graphene. The graphene carrier density induced by the gate voltage can be derived through

n=(c.sub.g/e)(V.sub.GS-V.sub.CNP)   (5)

[0394] where c.sub.g=C.sub.g/A, is the gate capacitance per unit area and e is the elementary charge.sup.58. The gate capacitance, C.sub.g, for 100 nm of Al.sub.2O.sub.3 was measured to be 86 nF (Keithley 4200-SCS). Therefore, the doping density induced by the water adsorption is

Δn(t)=(c.sub.g/e)ΔV.sub.CNP(t)   (6)

[0395] where ΔV.sub.CNP(t)=V.sub.CNP(t)−V.sub.CNP,0 and V.sub.CNP,0 is the voltage of the CNP before water exposure. Moreover, the Fermi level shift induced by the adsorption can be calculated through,

ΔE.sub.f(t)=Δn(t)/|Δn(t)|.Math.h.sub.vν.sub.f√{square root over (π|Δn(t)|/e)}  (7)

[0396] where h.sub.b and ν.sub.f are the reduced Plank constant and the Fermi velocity of graphene, respectively. FIGS. 8A and 8B show the shift in the charge neutral point, the corresponding doping density, and the shift in the Fermi level upon water vapor exposure to graphene.

[0397] FIGS. 8A-8B show the difference between the applied gate voltage and the charge neutral point versus water vapor exposure time for gate voltages of +20V (Δ), −20V (∇), 0V (∘), and 0V (□).The shift of the V.sub.CNP upon water exposure at the different gate voltages is shown in FIG. 8A. FIG. 8B shows the shift of the Fermi level due to water adsorption. The IV curves were measured under vacuum. The IV gate-graphene voltage was swept +20V.fwdarw.−20V.fwdarw.+20V for Δ and ∘ measurements, and swept −20V.fwdarw.+20V.fwdarw.−20V for ∇ and □ measurements. The doping densities and Fermi level shifts were greater for the +20V and −20V tests than those at 0V. The chemical doping due to adsorption was opposite for the +20V and −20V tests. The doping difference between the two 0V tests was due to hysteresis from the gate sweep.

[0398] GFET IV curves illustrate the current through a graphene channel as function of the gate-graphene voltage (FIG. 1). The gate-graphene voltage (V.sub.GS) with the minimum conductance represents the charge neutral point (V.sub.CNP). A pristine (undoped) graphene has its minimum conductance at zero-gate voltage, where its mobility is maximum and the carrier density is minimum (the Dirac Point). For V.sub.GS-V.sub.CNP>0, the Fermi level shifts upward, and n-dopes graphene. Conversely, when V.sub.GS-V.sub.CNP<0, the applied electric field extracts electrons from the valence band to create holes, which results in shifting the Fermi level downward, p-doping the graphene.

[0399] To measure the mass of adsorbed water vs the applied gate voltage, i.e., as a function of shifting the Fermi level, the GFETs were fabricated on QCMs. Adsorption isotherms were measured in an environmental vacuum chamber using the shift in the resonance frequency of the QCM upon water vapor exposure. In a temperature-controlled environment, the resonance frequency of a QCM depends on the magnitude of the adsorbed mass, the effect of the hydrostatic pressure on the elastic modulus of quartz, and the viscoelastic coupling to the gas. Corrections for pressure and viscoelastic coupling were made to calculate the mass adsorbed.

[0400] The three applied gate voltages during water adsorption, 0V, +20V, and −20V, induced no doping, n-doping, and p-doping, respectively. The non-zero-gate voltages led to higher uptakes. However, switching the gate voltage polarity resulted in similar uptakes. For example, at ˜3 Torr where approximately a monolayer of adsorbed water was expected, the uptake was ˜15% higher at gate voltages of +20V and −20V than at 0V. DFT calculations have shown higher adsorption energy of gases, including water vapor, on doped graphene compared to undoped graphene, where according to the Langmuir model, the higher adsorption energy should result in higher adsorption uptake. This change in uptake for the doped graphene is attributed to the change in the Coulombic and van der Waals interactions due to the increase in density of state (DOS) of graphene upon doping.

[0401] To gain insight into the doping of graphene due to water adsorption under an applied electric field, an additional set of experiments measured the electronic properties of graphene during adsorption. In these experiments, the gate voltage was kept at a constant value (+20V, −20V, or 0V), while IV scans were periodically conducted after x minutes of water vapor exposure (x=0, 1, 2, . . . , 20). To avoid further adsorption/desorption during IV scans, the chamber was evacuated for 1 min prior to each scan (maximum pressure of 5 mTorr). The gate voltage during IV scans started and ended at the adsorption gate voltage. For the adsorption tests with an applied +20V gate, the IV gate voltage was swept from +20V to −20V and then back to +20V. Conversely, for the −20V adsorption test, the gate voltage was swept from −20V to +20V, then back to −20V. Adsorption tests were performed for the zero-gate voltage with both sweep procedures (+20V.fwdarw.−20V.fwdarw.+20V and −20V.fwdarw.+20V.fwdarw.−20V). The purpose of running two adsorption tests at zero-gate voltage was to see how the sweep direction affects water adsorption onto graphene and if the graphene-water interface remembers the last applied gate voltage. For all measurements, the drain-source voltage was kept at 0.1V, which is in the ohmic region.

[0402] FIGS. 6A-6D show the IV curves after water vapor exposure with different applied gate voltages. During the adsorption with an applied gate voltage of +20V, the graphene was initially n-doped due to the applied gate voltage; however, the adsorption of water molecules shifted the V.sub.CNP in the positive direction and made the graphene less n-doped (FIG. 6A), i.e., water adsorption induced holes in graphene. On the other hand, when the applied gate voltage was kept at −20V during adsorption, the graphene was initially p-doped due to the applied gate voltage; however, the adsorption of water molecules moved the V.sub.CNP in the negative direction and made the graphene less p-doped (FIG. 6B), i.e., water adsorption induced electrons in graphene. FIGS. 6C and 6D show the IV curves after water vapor exposure while the gate voltage was kept at 0V during adsorption. In FIG. 6C, the sweeps started and ended at +20V and in FIG. 6D they started and ended at −20V.

[0403] FIGS. 8A and 8B shows the voltage driving electrical doping, the shift in the V.sub.CNP, the induced doping, and the shift in the Fermi level versus water vapor exposure time. For these calculations, the IV curves were fit to an asymmetric Lorentzian. The shift in the Fermi level was calculated based on:

ΔE.sub.F(t)=(−Δn(t))/|Δn(t)|.Math.ℏv.sub.f√(π|(Δn(t)|)   (1)

[0404] where ℏ and ν.sub.f are the reduced Planck's constant and the Fermi velocity of graphene, respectively. The doping induced by the molecular adsorption at time t, Δn(t), is equal to:

Δn(t)=(c.sub.g/e)[V.sub.CNP(t)−V.sub.CNP(0)]  (2)

[0405] where c.sub.g is the gate capacitance per unit area, e is the elementary charge, and V.sub.CNP(t) represent the charge neutral point voltage at time t.

[0406] It is observed that a larger applied gate voltage during water adsorption results in higher doping density, Δn, which is proportional to the water uptake. Nonetheless, the polarity of the gate does not significantly change the amount of adsorbed water, but it does affect the carrier type. This observation demonstrates that electrically doping graphene can result in more hydrophilic surfaces. Moreover, an applied gate voltage at V.sub.CNP will make the graphene as hydrophobic as possible. This agrees with the numerical and experimental contact angle measurements of water on electrically doped graphene, where an undoped graphene results in greater water contact angle.

[0407] Many dopants fall clearly into one of these two categories: electron-donor molecules that n-dope graphene and electron-acceptor molecules that p-dope; however, the doping induced by water adsorption onto graphene depends on the orientation of the adsorbed water molecule, which is controlled by the electric field at the supporting substrate. The higher electronegativity of oxygen compared to hydrogen in water molecules creates an electrical dipole moment with partial negative charge on the oxygen atom and partial positive charges on the hydrogen atoms. This dipole moment in water molecules affects its adsorption onto graphene.

[0408] Depending on the orientation of the adsorbed water molecule, it can either p-dope or n-dope graphene. In a water molecule, the HOMO (Highest Occupied Molecular Orbital) is completely located on the O atom and the LUMO (Lowest Unoccupied Molecular Orbital) is mostly located on the H atoms. Due to the relative positions of the HOMO and the LUMO of a water molecule with respect to the Dirac point, if the O atom points to graphene (O—H bond pointing up), the HOMO plays the dominant role and donates charge from water to graphene through a small mixing with graphene orbitals above the Fermi level, inducing n-doping. If the H atoms point to graphene (O—H bond pointing down), there is a small charge transfer from graphene to the water molecule through a small mixing with the graphene orbitals below the Dirac point that induces p-doping. When the applied gate voltage is greater than the V.sub.CNP (V.sub.GS>V.sub.CNP) the graphene is n-doped and electrons are the dominant charge carriers in graphene, so that water molecules tend to adsorb onto graphene with the positive side of the dipole (H atoms towards graphene), which induces p-doping. Conversely, when the gate voltage is less than the V.sub.CNP, the water molecules adsorb onto graphene with the OH bonds upward, which n-dopes graphene.

[0409] It is observed that a larger applied gate voltage during water adsorption results in adsorbing more water molecules, i.e., makes the surface more hydrophilic. Nonetheless, the polarity does not significantly change the amount of adsorbed water, but it does affect the carrier type. When the applied gate voltage was bigger than the voltage at the charge neutral point, it created more holes in the valence band (and reduced the number of free electrons in the conduction band) of graphene. On the other hand, when the applied gate voltage was smaller than the voltage at the charge neutral point, it led to more electrons in the conduction band (and less holes in the valance band) of graphene. This observation shows that doping graphene can result in creating more hydrophilic surfaces. In other words, an applied gate voltage closer to V.sub.CNP can make graphene more hydrophobic. This agrees with the contact angle measurements of water on electrically doped graphene where an undoped graphene results in larger contact angle of water.sup.65.

[0410] Effect of the Gate Voltage on Doping Rate

[0411] FIGS. 9A and 9B capture the effect of a gate voltage on the kinetics of water adsorption onto graphene in terms of the doping rate vs time (FIG. 9A) and vs pressure (FIG. 9B) upon water exposure. When the gate voltage is larger in magnitude compared to V.sub.CNP, i.e., a bigger |V.sub.GS-V.sub.CNP|, it results in a faster adsorption of water on graphene. This shows that when the Fermi level is further from the Dirac point (either direction), it is more likely for a water molecule to adsorb on graphene because more carriers, independent of the type, will attract more water molecules.

[0412] FIG. 9A shows the doping rate versus exposure time for different gate voltages. FIG. 9B shows the change in doping per change in water vapor pressure. Symbols for different gate voltages are the same as in FIGS. 8A and 8B. The kinetics of adsorption are larger in magnitude for the +20V and −20V than the 0V tests.

[0413] Conclusions

[0414] That electrical doping of graphene can tune water adsorption has been demonstrated. A back-gate graphene field effect transistor was fabricated on a QCM to induce p-doping/n-doping to the graphene by an applied gate voltage. Water adsorption on graphene was studied through adsorption isotherms and IV characterizations. The adsorption isotherms showed an increase in the water uptake for electrically doped graphene. However, the uptake was insensitive to the polarity of the gate. The IV curves measured prior and after water adsorption showed the same trend in the uptake, however, the polarity of the gate changed the type of the induced doping caused by water adsorption. For the gate voltages greater than V.sub.CNP, water molecules adsorbed with hydrogen legs down and induced p-doping to the graphene. On the other hand, for voltages less than V.sub.CNP, water adsorption tends to induce n-doping in graphene by adsorbing with the hydrogen legs up. Moreover, the calculated induced doping rate by water adsorption showed that an applied electric field can accelerate water adsorption on graphene.

[0415] Alternate embodiments of electric field control of surface energetics and kinetics can add an additional material on top of the 2D material, that can further refine the control of adsorption of different molecules. This can be via a surfactant molecule that will align with different functional groups facing outward depending on the applied voltage.

[0416] Alternatively, a nanoporous film can coat the surface, and adsorption in that material can be controlled via the adsorbed film.

[0417] Alternatively, pores through the device combined with the applied electric field tunability could modify membrane filtration transport. Droplets could also be electrically converted from filmwise to droplets to get a desirable effect, like droplet shedding, or motion of droplets. An array of individually gated regions on a surface, could provide motion control of droplets, as the droplets want to move to more hydrophobic surfaces. In this way, droplets for biomedical or other applications can be steered depending on different conditions. This could be useful for cell sorting or mixing reagents in microfluidics, for instance.

[0418] These devices were demonstrated using clean room processes, but alternative embodiments could incorporate liquid/solution-based device fabrication. The dielectrics and 2D material layers could be deposited via spray coated, chemical vapor deposited, or solution casting, for instance. Subsequent films of surfactant can be sprayed, or exist in the solution of interest. Small pinholes from the 2D material to gate can be tolerated if only the wetting properties of interest, though in the experiments discussed above, these were not tolerated because electrical properties were of interest, which would be interfered with in case of pinhole shorts across the dielectrics. The conductive gate electrode could itself be made of a 2D material.

[0419] The device formed by the electrical field modulated 2D material film may be interfaced with a computational device. The device may have an electrical field defined by an analog to digital converter or similar driver with an amplifier to achieve the desired voltage range. In devices where an array of film regions, or with spatially modulated patterns, the conductor below the dielectric may be pattered as a set of lines or pads, to define an array or addressable array. For example, the dielectric may be a planarized oxide dielectric over as an integrated circuit which generates fields which influence the 2D material.

[0420] The 2D material is preferably graphene, but may also be other types of 2D materials, such as Graphyne, Borophene, Germanene, Silicene, Si2BN, Stanene, Plumbene, Phosphorene, Antimonene, Bismuthene, Metals, Sodium Chloride (NaCl), 2D alloys, 2D supracrystals, Graphane, Hexagonal boron nitride, Borocarbonitrides, Germanane, Transition metal dichalcogenides (TMDs), and MXenes.

[0421] Hardware

[0422] FIG. 10 (see U.S. Pat. 7,702,660, expressly incorporated herein by reference), shows a block diagram that illustrates a computer system 400, that may be used to control the surface modification system. Computer system 400 includes a bus 402 or other communication mechanism for communicating information, and a processor 404 coupled with bus 402 for processing information. Computer system 400 also includes a main memory 406, such as a random access memory (RAM) or other dynamic storage device, coupled to bus 402 for storing information and instructions to be executed by processor 404. Main memory 406 also may be used for storing temporary variables or other intermediate information during execution of instructions to be executed by processor 404. Computer system 400 further includes a read only memory (ROM) 408 or other static storage device coupled to bus 402 for storing static information and instructions for processor 404. A storage device 410, such as a magnetic disk or optical disk, is provided and coupled to bus 402 for storing information and instructions. The computer system may also employ non-volatile memory, such as FRAM and/or MRAM.

[0423] The computer system may include a graphics processing unit (GPU), which, for example, provides a parallel processing system which is architected, for example, as a single instruction-multiple data (SIMD) processor. Such a GPU may be used to efficiently compute transforms and other readily parallelized and processed according to mainly consecutive unbranched instruction codes.

[0424] Computer system 400 may be coupled via bus 402 to a display 412, such as a liquid crystal display (LCD), for displaying information to a computer user. An input device 414, including alphanumeric and other keys, is coupled to bus 402 for communicating information and command selections to processor 404. Another type of user input device is cursor control 416, such as a mouse, a trackball, or cursor direction keys for communicating direction information and command selections to processor 404 and for controlling cursor movement on display 412. This input device typically has two degrees of freedom in two axes, a first axis (e.g., x) and a second axis (e.g., y), that allows the device to specify positions in a plane.

[0425] According to one embodiment of the invention, those techniques are performed by computer system 400 in response to processor 404 executing one or more sequences of one or more instructions contained in main memory 406. Such instructions may be read into main memory 406 from another machine-readable medium, such as storage device 410. Execution of the sequences of instructions contained in main memory 406 causes processor 404 to perform the process steps described herein. In alternative embodiments, hard-wired circuitry may be used in place of or in combination with software instructions to implement the invention. Thus, embodiments of the invention are not limited to any specific combination of hardware circuitry and software.

[0426] The term “machine-readable medium” as used herein refers to any medium that participates in providing data that causes a machine to operation in a specific fashion. In an embodiment implemented using computer system 400, various machine-readable media are involved, for example, in providing instructions to processor 404 for execution. Such a medium may take many forms, including but not limited to, non-volatile media, volatile media. Non-volatile media includes, for example, semiconductor devices, optical or magnetic disks, such as storage device 410. Volatile media includes dynamic memory, such as main memory 406. All such media are tangible to enable the instructions carried by the media to be detected by a physical mechanism that reads the instructions into a machine. Common forms of machine-readable media include, for example, hard disk (or other magnetic medium), CD-ROM, DVD-ROM (or other optical or magnetoptical medium), semiconductor memory such as RAM, PROM, EPROM, FLASH-EPROM, any other memory chip or cartridge, a carrier wave as described hereinafter, or any other medium from which a computer can read. Various forms of machine-readable media may be involved in carrying one or more sequences of one or more instructions to processor 404 for execution.

[0427] For example, the instructions may initially be carried on a magnetic disk of a remote computer. The remote computer can load the instructions into its dynamic memory and send the instructions over the Internet through an automated computer communication network. An interface local to computer system 400, such as an Internet router, can receive the data and communicate using an Ethernet protocol (e.g., IEEE-802.X) to a compatible receiver, and place the data on bus 402. Bus 402 carries the data to main memory 406, from which processor 404 retrieves and executes the instructions. The instructions received by main memory 406 may optionally be stored on storage device 410 either before or after execution by processor 404.

[0428] Computer system 400 also includes a communication interface 418 coupled to bus 402. Communication interface 418 provides a two-way data communication coupling to a network link 420 that is connected to a local network 422. For example, communication interface 418 may be a local area network (LAN) card to provide a data communication connection to a compatible LAN. In any such implementation, communication interface 418 sends and receives electrical, electromagnetic or optical signals that carry digital data streams representing various types of information.

[0429] Network link 420 typically provides data communication through one or more networks to other data devices. For example, network link 420 may provide a connection through local network 422 to a host computer 424 or to data equipment operated by an Internet Service Provider (ISP) 426. ISP 426 in turn provides data communication services through the world wide packet data communication network now commonly referred to as the “Internet” 428. Local network 422 and Internet 428 both use electrical, electromagnetic or optical signals that carry digital data streams. The signals through the various networks and the signals on network link 420 and through communication interface 418, which carry the digital data to and from computer system 400, are exemplary forms of carrier waves transporting the information.

[0430] Computer system 400 can send messages and receive data, including memory pages, memory sub-pages, and program code, through the network(s), network link 420 and communication interface 418. In the Internet example, a server 430 might transmit a requested code for an application program through Internet 428, ISP 426, local network 422 and communication interface 418. The received code may be executed by processor 404 as it is received, and/or stored in storage device 410, or other non-volatile storage for later execution.

[0431] The computer system may be an embedded computer system of an additive manufacturing system, or a separate system, and may be located remote or local. In one embodiment, the computer system is a Raspberry Pi 3 Model B+, executing a real time operating system, such as FreeRTOS. The computer system may also be a laptop computer, e.g., an HP Z-Book 17 G5.

[0432] Although the invention(s) have been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the invention. In addition, modifications may be made without departing from the essential teachings of the invention. The invention is described by way of various embodiments and features. This disclosure is intended to encompass all consistent combinations, subcombinations, and permutations of the different options and features, as if expressly set forth herein individually.

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