Room temperature oxygen sensors

Abstract

Highly accurate oxygen sensors made of graphene and titanium dioxide hybrid material are provided. With UV illumination, the disclosed sensors are capable of detecting O2 gas at room temperature and ambient pressure. The sensors are able to detect oxygen at concentrations ranging from about 0.2% to about 10% by volume under 365 nm UV light, and at concentrations ranging from 0.4% to 20% by volume under short wave UV light. The disclosed sensors have fast response and recovery times and can also be used to detect ozone.

Description

FIELD

Provided herein are graphene and titanium dioxide oxygen sensors capable of detecting O₂ gas at room temperature and ambient pressure. The disclosed sensors may be used for environmental monitoring, medical applications, food processing, steel and cement production, ink-jet, and laboratory safety, and they can be easily prepared from solution-phase synthesized graphene and titanium oxide hybrid materials for mass production.

BACKGROUND

Oxygen (O₂) gas sensors measure the proportion of oxygen in gas and are widely used for combustion engine and environmental monitoring, medical applications, food processing, steel and cement production, and laboratory safety. Oxygen sensors are usually made of metal-oxides, such as In₂O₃, SnO₂, ZnO, or yttria-stabilized zirconia. Traditional O₂ gas sensors were based on the principles of potentiometric equilibrium or limiting current amperometry. Different technologies are now used to measure oxygen, including zirconia, electrochemical, infrared, ultrasonic, paramagnetic and laser methods. Semiconducting gas sensors experience changes in resistance when exposed to certain gases.

Graphene is a two-dimensional monolayer of sp²-bonded carbon atoms, and it is an ideal material to use as a gas sensor because of its high surface area-to-volume ratio, high carrier mobility and low electrical noise. Graphene experiences a change in resistance when gas molecules are adsorbed on its surface. The magnitude and direction of these resistance changes depend on the type of gas and its concentration. Types of graphene include mechanically exfoliated graphite, reduced graphene oxide (rGO), and graphene grown by chemical vapor deposition (CVD). Graphene sensors have shown remarkable sensitivity to some gases, such as NO₂ and NH₃. Furthermore, rGO is very sensitive to certain chemical warfare agents, such as dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES). However, graphene is not inherently sensitive to O₂ gas.

Titanium dioxide (TiO₂) is an n-type semiconducting material and, similar to graphene, its electrical resistance changes upon adsorption of an analyte gas. Titanium dioxide has wide use in air-fuel sensors for automobiles since it is inexpensive, non-toxic, and very stable. However, the use of titanium dioxide as a gas sensor is limited, because TiO₂ is only functional at very high temperatures (about 300° C.).

Graphene-TiO₂ hybrids exhibit fast and efficient charge separation at the interface and have desirable photocatalytic properties under UV light. However, the development of graphene-TiO₂ hybrids is a very expensive process, and it is not suitable for mass production. Cost-effective methods of producing graphene-TiO₂ hybrids are therefore needed.

SUMMARY

The present application presents a solution to the aforementioned challenges by providing a cost-effective and easily scalable technique for producing graphene-TiO₂ oxygen sensors. The methods provided herein make use of solution-phase synthesized graphene-TiO₂ hybrid materials that are ultrasonicated and drop-casted onto a series of inter-digitated electrodes (IDE). The disclosed methodology, which is cost-effective and easy to scale up for mass production, is able to produce accurate and reliable oxygen sensors that, unlike traditional metal-oxide sensors, are functional at room temperature and can be integrated into wearable-size IoT devices. The oxygen sensors provided herein thus require little energy and may be used for environmental monitoring, medical applications, food processing, steel and cement production, and laboratory safety. Oxygen sensors that are functional at room temperature and ambient pressure, and methods for producing the disclosed sensors and for accurate determination of oxygen and ozone in gaseous samples are provided.

Thus, in some embodiments, provided herein is a gas sensor that detects oxygen gas at room temperature. The disclosed sensor comprises titanium dioxide nanoparticles attached to graphene nanoplatelets.

The graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio from about 55:45 to about 75:25. In some embodiments, the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio of about 70:30.

The disclosed sensor may be integrated into an artificial intelligence device.

In some embodiments, the disclosed oxygen sensor has a resistance that changes in oxygen's presence upon exposure to UV light.

Also provided herein is a method of producing a gas sensor that detects oxygen at room temperature. The disclosed method comprises: (i) mixing graphene nanoplatelets and titanium dioxide (TiO₂) nanoparticles to obtain a dispersion; (ii) ultrasonicating the dispersion to obtain a homogeneous graphene-TiO₂ dispersion; and (iii) drop-casting the homogeneous graphene-TiO₂ dispersion onto an integrated electronics (IDE) channel on a printed circuit board (PCB) sensor chip.

The graphene nanoplatelets may have an average surface area of 600 to 750 m²/g, a thickness of about 5-10 nm, and a diameter of 1-5 μm. The titanium dioxide nanoparticles may have an average particle size of about 5 nm to about 15 nm.

The graphene nanoplatelets and the titanium dioxide nanoparticles may be mixed in a weight ratio from about 55:45 to about 75:25. In some embodiments, the graphene nanoplatelets and the titanium dioxide nanoparticles are mixed in a weight ratio of about 70:30.

In some embodiments, the disclosed method comprises mass-producing the sensor by wafer fabrication, and it may further comprises integrating the sensor into an artificial intelligence device.

The sensors produced by the disclosed method change resistance in oxygen's presence upon exposure to a UV light source.

Additionally provided herein is a method of detecting an analyte in a gaseous sample at room temperature and ambient pressure. The disclosed method comprises: (i) exposing a gas sensor to a gaseous sample, wherein the gas sensor comprises titanium oxide nanoparticles attached to graphene nanoplatelets; (ii) exposing the sensor to UV irradiation at room temperature; and (iii) measuring a change in the sensor's resistance in response to UV irradiation, wherein magnitude of the change in the sensor's resistance is dependent upon the analyte's concentration, thereby detecting the analyte in the gaseous sample.

The disclosed method may further comprise determining the concentration of the analyte in the sample according to the logarithmic formula: S=0.0107 ln C+0.0321, wherein S is the change in the sensor's resistance in response to UV irradiation defined as: S=(R-R₀)/R₀, wherein R₀ is the sensor's base resistance and R is the sensor's resistance measured during gas exposure, and C is the concentration of the analyte in the gaseous sample.

In some embodiments, the disclosed method may further comprise purging the sensor with nitrogen for a time period from about 1 minute to about 20 minutes to decrease the sensor's resistance to baseline after each exposure to UV light.

In some embodiments, the sensor's change in resistance time in response to UV irradiation is about 250 seconds, and the sensor's recovery time is about 640 seconds.

In some embodiments, the UV irradiation is long wave UV light, and the analyte is oxygen. The long wave UV light may be a 365 nm UV light, and upon UV irradiation the sensor's resistance increases with an increase in oxygen concentration in the gaseous sample.

In some embodiments, the sensor may detect an oxygen concentration in the gaseous sample that is in a range from about 0.06% to about 15% (v/v).

In some embodiments, the UV irradiation is short wave UV light, and the analyte is oxygen and/or ozone. The short wave UV light may be a 254 nm UV light, and upon UV irradiation the sensor's resistance decreases with an increase in oxygen concentration in the gaseous sample.

In some embodiments, the sensor may detect an oxygen concentration in the gaseous sample that is in a range from about 0.4% to about 21.5% (v/v).

In some embodiments, the gas flow is kept constant at 400 sc/cm.

The graphene nanoplatelets and the titanium dioxide nanoparticles in the disclosed sensors may be in a weight ratio from about 55:45 to about 75:25. In some embodiments, the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio of about 70:30.

In some embodiments, the disclosed method may comprise alternatively irradiating the sensor with a long wave UV light source and a short wave UV light source in order to detect both oxygen and ozone in the surrounding environment. The long wave UV light may be a 365 nm UV light, and the short wave UV light may be a 254 nm UV light. In some embodiments, the UV light source is a light emitting diode (LED).

In some embodiments, the sensor is integrated into an artificial intelligence device.

In some embodiments, the gaseous sample is a spacecraft sample, a spacesuit sample, a food processing sample, a steel or cement production sample, an ink jet sample, a solution casting sample, a spin-coating sample, a laboratory sample, an electronic fuel injection or emission sample, a medical sample, or a pharmaceutical sample.

The foregoing and other features of the disclosure will become more apparent from the following detailed description of several embodiments, which proceeds with reference to the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the system used to measure oxygen sensing at room temperature and atmospheric pressure.

FIG. 2 is a diagram showing the procedural steps in oxygen sensing assays.

FIG. 3 shows sensor chips on which graphene-TiO₂ material was deposited. Each channel consisted of a pattern of gold electrodes having 80 μm finger width and 115 μm gap width. The inset shows an optical microscope image of an IDE channel on the sensor chip on which graphene-TiO₂ material had been deposited.

FIG. 4A shows a SEM image of a graphene nanoplatelet used in a sensor.

FIG. 4B is a TEM image of hybrid graphene-TiO₂ material showing individual TiO₂ nanoparticles attached to graphene surface.

FIG. 5 shows Raman spectra for TiO₂ (bottom curve), graphene (middle curve) and graphene-TiO₂ hybrids (top curve).

FIG. 6 is a graph depicting the effect of the graphene: TiO₂ weight ratio on sensors' base resistance of the sensor and relative resistance change upon UV exposure.

FIG. 7 shows current-voltage characteristic curves for various sensors having different graphene to TiO₂ weight ratios. The samples were tested under ambient air with no UV light. The linear relationship between current and applied voltage that was obtained for each sample indicated Ohmic contact between the graphene and the electrodes.

FIG. 8 shows current-voltage characteristic curves for sensors having a 70:30 graphene:TiO₂ weight ratio, that were tested in N₂ and air under the presence or absence of 365 nm UV light.

FIG. 9 shows the effect of different oxygen concentrations on sensors' resistance response upon exposure to 365 nm UV light.

FIG. 10 is a calibration curve used to determine detection limits.

FIG. 11 shows a single sensing cycle curve of 21% v/v O₂ used to determine response and recovery time.

FIG. 12 shows the effect of different oxygen concentrations on sensors' resistance response upon exposure to 254 nm UV light.

FIG. 13 is a calibration curve derived from the resistance response curve shown in FIG. 12.

FIG. 14 is a graph comparing the resistance response of graphene and graphene-TiO₂ sensors.

FIG. 15 shows ozone effect on graphene sensors and graphene-TiO₂ sensors.

FIG. 16 shows carbon dioxide effect on graphene-TiO₂ sensors.

FIG. 17 shows the effect of increasing concentrations of oxygen on graphene-TiO₂ sensors from which 365 nm UV light irradiation is blocked. The lack of changes in resistance by the sensors indicates that 365 nm UV light does not produce ozone gas.

DETAILED DESCRIPTION

The following explanations of terms and methods are provided to better describe the present disclosure and to guide those of ordinary skill in the art in the practice of the present disclosure. As used herein, “comprising” means “including” and the singular forms “a” or “an” or “the” include plural references unless the context clearly dictates otherwise. The term “or” refers to a single element of stated alternative elements or a combination of two or more elements, unless the context clearly indicates otherwise. For example, the phrase “A or B” refers to A, B, or a combination of both A and B. Furthermore, the various elements, features and steps discussed herein, as well as other known equivalents for each such element, feature or step, can be mixed and matched by one of ordinary skill in this art to perform methods in accordance with principles described herein.

Unless explained otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. The materials, methods, and examples are illustrative only and not intended to be limiting.

In some examples, the numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, used to describe and claim certain embodiments are to be understood as being modified in some instances by the term “about” or “approximately.” For example, “about” or “approximately” can indicate +/−20% variation of the value it describes. Accordingly, in some embodiments, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties for a particular embodiment. The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. To facilitate review of the various embodiments of this disclosure, the following explanations of specific terms are provided:

Analog: A compound having a structure similar to another, but differing from it, for example, in one or more atoms, functional groups, or substructure.

Chemical Sensor: A measurement device that converts a chemical or physical property of a specific analyte into a measurable signal, whose magnitude is proportional to the concentration of the analyte. Chemical sensors can use capacitive readout cantilevers and electronics to analyze a transmitted signal and change one or more electrical characteristics, such as resistance, upon absorbing a gas molecule.

Contacting: Placing a substance in direct physical association with a material in solid, liquid, or gas form.

Control: A reference standard of a known value or range of values.

Graphene: An allotrope of carbon consisting of a single layer of atoms arranged in two-dimensional honeycomb lattice. Among its uses are anti-corrosion coatings and paints, sensors, electronics, displays, solar panels, drug delivery and DNA sequencing.

Hybrid Material: A composite consisting of two or more components that are combined into a matrix at nanometer or molecular level. In some cases, one component is inorganic, and one component is organic. Hybrid nanocomposites can include technological platforms used in photovoltaic cells and light-emitting devices, lithium ion batteries, supercapacitors and sensors.

Metal Oxide: A crystalline solid catalyst that contains a metal cation and an oxide anion, and reacts with water to form a base, or with an acid to form a salt. Metal oxides include, but are not limited to, carbon oxide, iron oxide, nitrogen oxide, silicon oxide, titanium oxide and aluminum oxide. Metal oxides can be used for example in sensor and biosensor applications, and their surface properties determine sensor's sensitivity.

Microchip: A unit of an integrated circuit made of silicon, germanium or other semiconducting material and used for program logic and computer memory.

Oxygen Sensor: An electronic device that measures the properties of oxygen in a gas or in a liquid.

Resistance: An electrical property that can be used to indicate a decrease in electric current flow through a device or material. Electrical resistance is defined as the ratio between the voltage applied to the electric current and the electric current that flows through it. If the resistance is constant over a considerable range of voltage, Ohm's law, I=V/R can be used to predict a behavior of a material. An electric current flows when electrons move through a conductor. Factors that affect resistance include the type of material, length and thickness of the resistor and the temperature of the conductor.

Semiconductor: A material that has a conductivity between the conductivity of an insulator and the conductivity of most metals. The resistance of a semiconductor decreases as its temperature rises. Electronic devices that use semiconductors include, but are not limited to, diodes, transistors and integrated circuits.

Titanium Dioxide: The naturally occurring oxide of titanium found in ilmenite, and the minerals rutile and anatase. It is used for example in paint, paper, plastic, cosmetics, sunscreen and food coloring. Naosized titanium dioxide exhibits photocatalytic activity under UV irradiation.

Wafer Fabrication: A technology producing electrical or photonic circuits from semiconductor wafers. Examples include, but are not limited to, production of radio frequency amplifiers, LEDs, and computer components. The process may involve photomasking photoresist patterns onto the wafer's surface, exposing the wafers to UV light, cleaning away the unexposed area, depositing chemical vapors and heating at high temperatures.

Room Temperature Oxygen Sensors and Methods of Production and Detection

Oxygen sensors find use in a wide array of applications, including electronic fuel injection and emissions control in the automotive industry, oxygen monitoring for medical and pharmaceutical applications, environment control in spacecraft and spacesuits technology, food processing, steel and cement production, ink jetting, solution casting, spin-coating, and laboratory safety. Traditional oxygen sensors, including potentiometric and amperometric sensor designs, have significant drawbacks, as metal oxide gas sensors require a temperature of about 300° C. and suffer from high power consumption. Graphene sensors, including mechanically exfoliated graphite, reduced graphene oxide, and graphene grown by chemical vapor deposition, have recently been explored as alternatives to address these drawbacks. However, while graphene sensors are sensitive to a variety of gases, such as nitrogen dioxide and ammonia, they are not suitable for detecting oxygen. Moreover, their expensive production makes graphene sensors unsuitable for mass production.

The present application overcomes these drawbacks by providing low-cost, low-power, mass-producible oxygen sensors with a small footprint that are capable of detecting oxygen gas at room temperature, and an efficient and inexpensive process for producing the disclosed sensors. The disclosed oxygen sensors have a footprint that is one-tenth the size of currently available commercial O₂ sensors, and may be integrated into wearable-size internet of things (IoT) devices. Accordingly, the disclosed oxygen sensors provide significant advantages over large-size traditional sensors that require high operating temperatures requirements and power of operation.

Since graphene is not intrinsically responsive to O₂, and TiO₂ is not responsive to oxygen at room temperature, the oxygen sensors provided herein are made of hybrid material produced by modifying graphene nanoplatelets with titanium dioxide nanoparticles by solution-phase synthesis. The graphene and the titanium dioxide may be present in the composite material in different ratios to ensure maximal oxygen detection. A suitable graphene: TiO₂ ratio range may vary from about 55:45 to about 75:25. In some embodiments, the graphene and the titanium dioxide are present in the composite material in a ratio of about 70:30.

In some embodiments, the synthesized graphene-TiO₂ hybrid material is ultrasonicated and then drop-casted onto a series of interdigitated electrodes (IDE). Ultrasonication ensures effective charge transfer at the graphene-TiO₂ interphase. This approach is cost-effective, easy to scale-up into mass production, and yields a semiconducting material whose resistance changes upon absorption of an analyte gas, such as oxygen. In addition, since the disclosed sensors are chip-based, they can be manufactured by wafer fabrication. The ability to produce a multitude of chips on a single wafer reduces costs significantly, and lends itself to automated manufacturing processes, which may reduce costs even further.

The sensors thus produced are exposed to UV light for gas detection.

In some embodiments, the disclosed sensors may be used to detect low concentrations of oxygen. Oxygen gas detection is performed by exposing the disclosed sensors to long wave UV light at room temperature. A long wave UV light of 365 nm excites the graphene-TiO₂ sensors and causes the sensors' resistance to increase upon exposure to O₂ gas. Gas flow may be varied or kept constant. In some embodiments, the gas flow may be kept constant at 400 sc/cm. As shown in FIG. 10, the magnitude of the response signal under 365 nm UV light exposure is dependent upon the concentration of O₂ gas. Under such conditions, the disclosed sensors can detect O₂ gas according to the logarithmic formula: S=0.0107 In C+0.0321, wherein S is the response signal, and C is the oxygen concentration. The response signal, which is the relative resistance change of the sensor, is defined as: S=(R-R₀)/R₀, where R₀ is the base resistance of the sensor measured during the initial N₂ purge and R is the resistance measured during oxygen exposure. Thus, the disclosed sensors may detect oxygen at room temperature upon irradiation with 365 nm UV light in concentrations from about 0.06% v/v to about 21% v/v. Higher oxygen concentration may cause the sensor to become saturated with oxygen, and thus unresponsive.

In some embodiments, the disclosed sensors may be used to separately detect oxygen at high concentrations and ozone. Gas detection is performed by exposing the disclosed sensors to short wave UV light at room temperature. A short wave UV light of 254 nm causes the sensors' resistance to decrease upon exposure to O₂ gas in graphene and graphene-TiO₂ hybrid sensors. Under such conditions, the disclosed sensors can detect O₂ gas according to the logarithmic formula: S=0.0107 ln C+0.0321. Thus, the disclosed sensors may detect oxygen at room temperature upon irradiation with 254 nm UV light in concentrations above about 2.1% v/v and up to about 20% v/v. Furthermore, the disclosed sensors may detect ozone gas that is emitted by the short wave UV light.

For gas detection, a UV source may be connected to a chamber containing an oxygen sensor as described herein, and the chamber is connected to a gas inlet. Exposure to a UV source may be through an opening, such as a circular opening of about 0.5 cm in diameter. The UV source and the gas inlet may be at a distance from about 1 cm to about 10 cm from the sensor to prevent heat emanated from the lamp from affecting the sensor. The temperature of the sensor surface y be kept constant at about 25° C. with an infrared thermometer.

The disclosed oxygen sensors may be purged with nitrogen after each exposure to UV light. Purging time may vary from about 1 minute to about 20 minutes. In some embodiments, purging time may be 15 minutes long. Sensor exposure to oxygen gas increases resistance, and sensors purging with N₂ gas causes the disclosed sensors to recover and their resistance decreases to initial baseline levels.

The disclosed sensors exhibit fast response times and fast recovery time. In some embodiment, their response time is about 250 seconds and their recovery time is about 640 seconds.

The disclosed graphene-TiO₂ sensors detect O₂ with high precision at volume concentrations below about 2.1% v/v upon exposure to 365 nm UV light, and at concentrations above about 2.1% v/v upon exposure to 254 nm UV light. Therefore, the disclosed sensors can be used with long wave and short wave UV light sources, which can be alternatively switched to increase the measurement range. Light emitting diodes are suitable because of their smaller size, lower power consumption, and better control over the emitted wavelength. Thus, the disclosed sensors are highly precise and reliable, provide effective oxygen detection at room temperature with low power, have a wide range of detection, a low detection limit, fast response times and recovery times, and can be mass-produced by cost-effective technology. In addition, the oxygen sensors provided herein have small size, can be integrated into artificial intelligence devices, and may be used for a wide spectrum of applications, including, but not limited to, environmental control in spacecraft and spacesuits, food processing, steel and cement production, ink jetting, solution casting, spin-coating, laboratory safety, electronic fuel injection and emissions control, and oxygen monitoring for medical and pharmaceutical applications.

Thus, unlike traditional existing technologies, the disclosed sensors and methodology allows accurate determination of oxygen gas in one simple assay, and particularly attractive to industry in applications that demand room-temperature operation, a very small footprint, and low production costs at scale.

EXAMPLES

Example 1: Sample Preparation and Sonication

Graphene nanoplatelets were purchased commercially in dry powder form and used as received. The nanoplatelets had an average surface area of 600 to 750 m²/g, a thickness of 8 nm, and a diameter of 2 μm. Titanium dioxide nanoparticles were purchased from U.S. Research Nanomaterials and had an average particle size of 5 to 15 nm. The anatase form of TiO₂ was chosen because of its increased photocatalytic activity over the rutile form. The materials were mixed with deionized (DI) water in a vial at a concentration of 1 mg/ml with a total solvent volume of 4 ml. Several different weight ratios of graphene to TiO₂ were tested, including a sample without any TiO₂. A probe ultrasonicator operating at output wattage of 5 was used to sonicate the dispersion. The vial was placed inside a cold water bath at a temperature of 15° C., and the tip of the sonicator probe was submerged halfway into the vial. Each sample was sonicated for 5 minutes. Homogeneity of the dispersion increased after sonication, as evidenced by a visible increase in color opacity. The increase in opacity was due to the breaking of nanoparticle aggregates by acoustic cavitation during ultrasonication. The hybrid dispersion thus obtained was then drop-casted using a micropipette onto an integrated electronics (IDE) channel on a printed circuit board sensor chip.

Other deposition methods were also tested, in which the graphene and TiO₂ were drop-casted in two separate steps. The graphene was drop-casted first to provide a stable electrical connection with the surface of the sensor chip and the metal electrodes. Then the TiO₂ layer was drop-casted above the graphene layer for greater exposure to incident light. These sensors were tested by exposure to O₂ gas under 365 nm UV light, but they gave no response. Lack of response was likely due to ineffective charge transfer between the graphene layer and the TiO₂ layer following layer-by-layer deposition method. In contrast, sonicated samples successfully functioned as sensors, as ultrasonic synthesis caused strong physisorption between graphene and TiO₂.

To further define sonication parameters, several graphene-TiO₂ hybrid materials were synthesized by low-power bath sonication or mixing using a magnetic stirrer. The sensors developed by low-power sonication or by mixing did not show significant response to O₂ gas. These results indicated that sonication of graphene and TiO₂ together is vital for creating effective O₂ sensors. Sonication was then further optimized by determining the effects of power, time, and different solvents on O₂ sensor production.

In view of these results, and because some slight precipitation of the dispersion occurs over time, drop-casting was performed immediately after sonication. A set volume of 0.5 μl, determined to be the optimal volume for achieving a measurable resistance, was deposited onto each sensing channel. The sensor was then heated in a vacuum oven at 80° C. and under 40 mm Hg pressure for 10 minutes to completely evaporate the solvent.

Example 2: Hybrid Material Characterization

Optical microscope images of the sensor were taken, and surface characterization was done with a field emission scanning electron microscope (SEM) operating at an accelerating voltage of 5 kV. As shown in FIG. 3, a portion of the channel was covered with the graphene-TiO₂ hybrid material. This confirmed that the electrodes were bridged and the resistance of the hybrid material could be measured upon voltage application to the sensor chip.

High magnification images were taken with a transmission electron microscope (TEM). Prior to TEM imaging, the dispersed material was drop-casted onto a copper mesh grid sample holder and heated. Raman spectra were obtained using a spectrometer with a 514.5 nm argon laser. For Raman and SEM characterization, the dispersed material was drop-casted onto a silica wafer shard and then heated in a vacuum oven to evaporate the solvent. Current-voltage (I-V) characteristic curve measurements were obtained using a semiconductor parameter analyzer. The SEM image in FIG. 4A shows an unmodified multilayer graphene nanoplatelet having an overall smooth surface with some irregular areas.

TEM imaging was performed on a graphene-TiO₂ hybrid material having a 50:50 graphene to TiO₂ weight ratio. FIG. 4B shows a graphene nanoplatelet with TiO₂ nanoparticles evenly scattered through the graphene. The presence of TiO₂ on the graphene validates the feasibility of the ultrasonication procedure for synthesizing graphene-TiO₂ hybrid materials. Furthermore, the random distribution of the TiO₂ nanoparticles increases the surface area for UV excitation and O₂ adsorption. Raman spectroscopy was performed on the raw TiO₂ nanoparticles, the graphene nanoplatelets, and a hybrid material having a 25:75 graphene to TiO₂ weight ratio. The spectra shown in FIG. 2C show the position of the 2D peak at 2708 cm⁻¹. This data indicated that the graphene nanoplatelet had about six layers. The high intensity of the D band with respect to the G band suggested the presence of inherent defects in the graphene nanoplatelets and supported the findings from SEM imaging that an unmodified multilayer graphene nanoplatelet has an overall smooth surface with some irregular areas.

Comparative analysis of the raw TiO₂ spectra showed no peaks within the tested wave range. Addition of TiO₂ to graphene decreased the intensity ratio of the 2D band over the G band, and increased the intensity of the D band. These effects were attributed to electron doping of the graphene caused by addition of TiO₂.

Example 3: Gas Sensing Experiments

Gas sensing experiments were performed using the system shown in FIG. 1, using two different ultraviolet lamps: a long-wave lamp with a primary wavelength of 365 nm, and a short-wave lamp with a primary wavelength of 254 nm. One lamp at a time was each connected to a chamber with an interior volume of about 15 cm³, which in turn was connected to a gas inlet. Exposure to each UV lamp was through a circular opening of about 0.5 cm in diameter. A distance of 5 cm from the lamp and gas inlet to the sensor was set to prevent heat emanated from the lamp from affecting the sensor. The temperature of the sensor surface was measured with an infrared thermometer and never exceeded 30° C. during the tests, such that any thermoelectric effects on sensor's resistance could be considered negligible. Keeping the gas inlet at a distance from the sensor also minimized the flow effect and resistance changes caused by the strain sensitivity of graphene. A gas outlet was located at the bottom of the chamber to prevent the pressure inside the chamber from exceeding atmospheric pressure.

FIG. 2 shows a flow diagram of the gas sensing assays. A sensor chip on which the sensing material was deposited (FIG. 3) was placed inside the chamber and attached to a circuit board. The circuit board was then connected to a digital multimeter via an electrical connector with a ribbon cable. Resistance measurements were recorded onto a computer with a customized data acquisition program. A mass flow controller was used to blend gases and adjust the gas flow. To establish a baseline, pure nitrogen (N₂) gas was flowed into the chamber for 15 minutes to purge the sensor. Varying concentrations of dry air diluted in N₂ were then introduced over time with pure N₂ purging in between. Air was used to simulate O₂ in order to obtain lower concentrations of O₂ from the mass flow controller and to ensure that the sensor could operate in normal atmosphere without interference. The effects of carbon dioxide (CO₂) gas in air were ruled out by determining that sensor's exposure to increasing concentrations of CO₂ did not cause any resistance changes (FIG. 16). Gas flow was kept constant at 400 sc/cm and each UV lamp was turned on throughout each experiment.

Example 4: Exposure to 365 nm UV Light

The resistance of each sample produced as described above was measured prior to and following 5-minute exposure to 365 nm UV light in ambient air. The results summarized in Table 1 show a direct correlation between TiO₂ amount and resistance for each sample.

TABLE 1
Effect of 5-Minute Exposure to 365 nm UV Light
on Sensors' Resistance in Ambient Air
		Resistance
	Initial	after	Resistance	Percent
Graphene:TiO2	resistance	exposure to	change	resistance
Weight Ratio	(Ω)	UV light (Ω)	(Ω)	change
100:0	1534	1554	20	1.30%
75:25	6550	7650	1100	16.79%
70:30	10610	12840	2230	21.02%
65:45	12030	15060	3030	25.19%
60:40	27320	34270	6950	25.44%
55:35	119000	155000	36000	30.25%

Increasing the ratio of TiO₂ in the samples further augmented the relative resistance increase upon UV exposure. When the data presented in Table 1 was plotted as shown in FIG. 6, the relative resistance induced by exposure to 365 nm UV light for each sample increased exponentially with TiO₂ increase, suggesting that further increasing the amount of TiO₂ in the hybrid material would significantly increase the base resistance.

A base resistance of about 10 kΩ is considered optimal for measuring electrical properties of a sensor (data not shown), as higher base resistance may cause drifting and lead to an unstable sensor. A base resistance greater than 10 MΩ is also not measurable with a multimeter. Therefore, when sensors with equal or more TiO₂ amount than graphene by weight were produced, their high resistance at room temperature rendered them unsuitable for sensor applications. Pure TiO₂ could also not be tested as a sensor, as the discontinuity between the nanoparticles prevented resistance measurements. Based on these findings, it was determined that sensor optimal graphene: TiO₂ weight ratio is about 70 graphene nanoplatelets: 30 TiO₂ nanoparticles. Consequently, all graphene-TiO₂ hybrid materials were then synthesized using a 70:30 graphene to TiO₂ weight ratio.

FIG. 7 shows current-voltage characteristic curves of several samples obtained under ambient air with no UV light. The linear relationship between current and applied voltage that was obtained for each sample indicated Ohmic contact between the graphene and the electrodes. Tests were also performed on graphene-TiO₂ sensors under either N₂ or air flow in the presence or absence of exposure to 365 nm UV light, as shown in FIG. 8. No noticeable differences were detected between exposure to N₂ and exposure to air in the absence of UV light. These results confirmed that the sensors are insensitive to O₂ in the absence of UV illumination. Switching the UV light on caused a 3% decrease in current in samples kept under N₂ purging. This change was attributed to the presence of some residual O₂ inside the chamber, since vacuum pumping was not utilized. Switching the UV light on caused a 12% decrease in current in samples exposed to air. These results indicated that the sensors are sensitive to O₂ gas while under UV illumination.

Example 5: Oxygen Detection

To test the ability of the sensors produced as described herein to detect O₂ gas, the sensors were exposed to O₂ gas emitted from a dry air cylinder in increasing concentrations. Each exposure to O₂ lasted five minutes, with ten minutes of purging with N₂ gas after each exposure. To set a baseline resistance measurement, the UV lamp was switched on and the sensor was purged with N₂ gas for 15 minutes before starting exposure to O₂. O₂ concentrations ranging from 0.21 to 10.5% v/v were tested. FIG. 9 shows the resulting gas sensing response curve, which was obtained by plotting response signal against time.

The response signal, which is the relative resistance change of the sensor, is defined as: S=(R-R₀)/R₀, where R₀ is the base resistance of the sensor measured during the initial N₂ purge and R is the resistance measured during oxygen exposure. Sensor exposure to O₂ gas increased resistance, and sensor purging with N₂ gas caused the sensors to recover and decreased sensor resistance to initial baseline levels. As shown in FIG. 10, the magnitude of the response signal was dependent upon the concentration of O₂ gas. For O₂ concentrations of 0.21 to 21% v/v, a logarithmic trend that relates the O₂ concentration (C) to the response signal (S) was calculated as: S=0.0107 In C+0.0321.

The response signal stopped following this trend once O₂ concentration was above 21% v/v. These results indicated that the sensors became likely saturated with O₂ molecules. For determination of the detection limits of the disclosed sensors, the minimum true signal was set to be three times the standard deviation of the baseline resistance. Addition of this value to the fitting curve equation resulted in an O₂ concentration value of 0.06% v/v, which is the detection limit for the sensors.

Example 6: Sensors' Response and Recovery Time

The sensors produced as disclosed herein were exposed to 21% v/v O₂ gas between N₂ purges to determine their response and recovery times. A concentration of 21% v/v O₂ gas was selected, as this is the maximal concentration of oxygen that can be obtained from an air source. This concentration was also used to ensure that the sensors would rapidly reach an equilibrium resistance. The response and recovery times were defined as the times needed for the response signal to reach 90% of the equilibrium resistance. As shown in FIG. 11, the sensors showed a response time of 250 seconds and a recovery time of 640 seconds. These response and recovery times are fast for room temperature sensors and could even be improved significantly by heating the sensors.

These response and recovery times were used to set the exposure and purging times for a gas sensing experiment. Sensors that were created using only graphene without the addition of TiO₂ did not exhibit any O₂ sensitivity even during exposure to 365 nm UV illumination. When graphene and graphene-TiO₂ sensors were exposed to O₂ without UV illumination, no response was detected. These results confirmed that graphene is not intrinsically responsive to O₂, and that UV light is necessary for the graphene-TiO₂ sensors to detect O₂.

Example 7: Sensors' Sensitivity

Photoexcitation of TiO₂ is responsible for sensors' sensitivity to O₂, as ultraviolet light excites TiO₂ electrons to the conduction band. Electron excitation is brought about by the band gap of anatase TiO₂, which is 3.2 eV and corresponds to a peak excitation wavelength of about 385 nm. Electron excitation would increase the conductivity of the sensors under vacuum conditions. However, in the presence of O₂ molecules, O₂ molecules act as an electron trap when they are adsorbed onto the surface of TiO₂ and the reaction O₂+e⁻→O₂⁻occurs. Therefore, sensors' resistance increases as a function of the concentration of O₂, as shown above. Surface defects on the TiO₂ further increases absorption of O₂ molecules. As more O₂ molecules adsorb onto the surface, an electron depletion region forms, lowering the conductivity of TiO₂. Because of its inherently high carrier mobility and low electrical noise, graphene is sensitive to the changes in conductivity brought about by oxygen adsorption, and since graphene acts as an electron transporter in graphene-TiO₂ hybrid materials, excited TiO₂ electrons can migrate to graphene through a percolation mechanism.

The results presented herein demonstrate that the overall resistance of the disclosed graphene-TiO₂ hybrid sensors increases upon exposure to O₂ under 365 nm UV illumination.

Example 8: Exposure to 254 nm UV Light

To compare the effect of different length UV lights on sensors' oxygen detection, relative resistance changes of various samples were measured prior to and following 5-minute exposure of the sensors to 254 nm UV illumination in ambient air. FIG. 6 shows that the weight ratio of graphene to TiO₂ had no effect on resistance changes. Graphene samples free of TiO₂ and graphene-TiO₂ hybrid samples showed similar resistance patterns, which suggests that graphene is responsible for resistance changes. Gas sensing was then tested under exposure to 254 nm UV illumination. Graphene sensors were exposed to O₂ at concentrations ranging from 0.42 to 21% v/v. FIGS. 12 and 13 show that the resistance of the sensors decreased as O₂ concentration increased, according to the logarithmic equation: S=−0.34 In C −0.0334.

The effect of exposure to 254 nm UV illumination on oxygen detection was then determined in graphene-TiO₂ sensors, and compared to graphene sensors. The results, which are shown in FIG. 14, indicated no discernible differences in the shape of the response curve and in the relative response between the two types of sensors.

Unlike exposure to 365 nm UV illumination, which caused positive changes in sensors' resistance, exposure of the sensors to 254 nm UV illumination caused negative changes in resistance. These results indicated that an alternate mechanism takes place upon exposure of the sensors to 254 nm UV light, and the addition of TiO₂ to graphene does not affect the response of the sensors under 254 nm UV light.

Example 9: Effect of Ozone Production on Sensors' Response

Shortwave mercury vapor UV lamps emit primary light with wavelength of 254 nm, and emit smaller light at 185 nm. This shortwave light generates small concentrations of ozone (O₃) from O₂ gas. Although unstable atomic oxygen is also generated in this process, atomic oxygen immediately recombines with molecular oxygen or another atomic oxygen to form O₃ or molecular oxygen. Therefore, atomic oxygen was not considered a factor affecting sensors' sensitivity.

To determine whether the effect of exposure to 254 nm UV light on the disclosed sensors was related to ozone (O₃) generation and detection, an assay was designed to separate the effects of UV light on O₂ molecules from those on sensors. Graphene and graphene-TiO₂ sensors were tested. Air was flown into a chamber in which a black filter capable of adsorbing UV light and allowing gas flow was placed between the UV lamp and each sensor. The UV light generated O₃ from O₂, and O₃ passed through the filter. Because the sensors were not exposed to UV light, the response was solely due to O₃ effect. The results, shown in FIG. 15, indicated no significant differences in the shape of the response curve between graphene sensors and graphene-TiO₂ sensors. Compared to the results shown in FIG. 14, sensors' response in the absence of UV light irradiation was 10% to 20% lower in magnitude depending on O₂ concentration, and the sensors' ability to recover during N₂ purging was significantly reduced. These results confirmed that UV irradiation enhances sensors' response and recovery through photo-excitation of TiO₂, and also indicated that the disclosed sensors can be used to detect ozone.

Graphene sensors showed no detectable decrease in resistance when tested in the presence of a black filter under 365 nm UV light (FIG. 17). These results demonstrated that the black filter was effective at absorbing incident light, and 365 nm UV light did not generate a measurable quantity of O₃.

Example 10: Effect of Carbon Dioxide on Sensors' Activity

Carbon dioxide (CO₂) is present in air at a volume fraction of about 400 ppm. To determine the effects of carbon dioxide on the disclosed sensors, the sensors were exposed to increasing concentrations of CO₂ (50 ppm, 200 ppm, 500 ppm balanced with air) with air purge under 365 nm UV light. As shown in FIG. 16, graphene-TiO₂ sensors exhibited no detectable response to CO₂. Resistance drift was caused by O₂ adsorption onto the sensors. Argon in air is inert, and the other gases present in air were assumed to have a negligible effect on the sensor because of their presence in minute concentrations. These data confirmed that O₂ present in air was the sole gas being detected.

Example 10: Practical Applications

The results presented herein clearly demonstrate that the graphene-TiO₂ sensors detect O₂ with high precision at volume concentrations below 2.1% v/v upon exposure to 365 nm UV light, and at concentrations above 2.1% v/v upon exposure to 254 nm UV light. Therefore, the disclosed sensors can be used with long wave and short wave UV light sources, which can be alternatively switched and wider range of oxgen can be detected. Light emitting diodes are suitable because of their smaller size, lower power consumption, and better control over the emitted wavelength. Thus, the disclosed sensors have a wide range of detection, a low detection limit, and are produced by cost-effective technology.

It should be recognized that illustrated embodiments are only examples of the disclosed product and methods and should not be considered a limitation on the scope of the invention. Rather, the scope of the invention is defined by the following claims. We therefore claim as our invention all that comes within the scope and spirit of these claims.

EXEMPLARY EMBODIMENTS

Exemplary embodiments provided in accordance with the disclosed subject matter include, but are not limited to, the following:

A gas sensor detecting oxygen gas at room temperature and comprising titanium oxide nanoparticles attached to graphene nanoplatelets.

The gas sensor according to embodiment 1, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio from about 55:45 to about 75:25.

The gas sensor according to any of the preceding embodiments, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio of about 70:30.

The gas sensor according to any of the preceding embodiments, wherein the sensor is integrated into an artificial intelligence device.

The gas sensor according to any of the preceding embodiments, wherein the sensor has a resistance that changes in oxygen's presence upon exposure to UV light.

A method of producing a gas sensor that detects oxygen gas at room temperature, wherein the method comprises: (i) mixing graphene nanoplatelets and titanium dioxide (TiO₂) nanoparticles to obtain a dispersion; (ii) ultrasonicating the dispersion to obtain a homogeneous graphene-TiO₂ dispersion; and (iii) drop-casting the homogeneous graphene-TiO₂ dispersion onto an integrated drive electronics (IDE) channel on a circuit board sensor chip.

The method according to the preceding embodiment, wherein the graphene nanoplatelets have an average surface area of 600 to 750 m²/g, a thickness of about 5-10 nm, and a diameter of 1-5 μm, and wherein the titanium dioxide nanoparticles have an average particle size of about 5 nm to about 15 nm.

The method according to any of the preceding embodiments, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are mixed in a weight ratio from about 55:45 to about 75:25.

The method according to any of the preceding embodiments, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are mixed in a weight ratio of about 70:30.

The method according to any of the preceding embodiments, wherein the method comprises mass-producing the sensor by wafer fabrication.

The method according to any of the preceding embodiments, wherein the sensor changes resistance in oxygen's presence upon exposure to a UV light source.

The method according to any of the preceding embodiments, wherein the method further comprises integrating the sensor into an artificial intelligence device.

A method of detecting an analyte in a gaseous sample at room temperature and ambient pressure, wherein the method comprises: (i) exposing a gas sensor to a gaseous sample, wherein the gas sensor comprises titanium oxide nanoparticles attached to graphene nanoplatelets; (ii) exposing the sensor to UV irradiation at room temperature; and (iii) measuring a change in the sensor's resistance in response to UV irradiation, wherein magnitude of the change in the sensor's resistance is dependent upon the analyte's concentration, thereby detecting the analyte in the gaseous sample.

The method according to the preceding embodiment, wherein the method further comprises determining the concentration of the analyte in the sample according to the logarithmic formula: S=0.0107 In C+0.0321, wherein S is the change in the sensor's resistance in response to UV irradiation defined as: S=(R-R₀)/R₀, wherein R₀ is the sensor's base resistance and R is the sensor's resistance measured during gas exposure, and C is the concentration of the analyte in the gaseous sample.

The method according to any of the preceding embodiments, wherein the method further comprises purging the sensor with nitrogen for a time period from about 1 minute to about 20 minutes to decrease the sensor's resistance to baseline after each exposure to UV light.

The method according to any of the preceding embodiments, wherein the sensor's change in resistance time in response to UV irradiation is about 250 seconds, and wherein the sensor's recovery time is about 640 seconds.

The method according to any of the preceding embodiments, wherein UV irradiation is long wave UV light, and wherein the analyte is oxygen.

The method according to any of the preceding embodiments, wherein the long wave UV light is 365 nm UV light, and wherein the sensor's resistance increases with an increase in oxygen concentration in the gaseous sample.

The method according to any of the preceding embodiments, wherein the oxygen concentration in the gaseous sample is in a range from about 0.06% to about 15% (v/v).

The method according to any of the preceding embodiments, wherein UV irradiation is short wave UV light, and wherein the analyte is oxygen and/or ozone.

The method according to any of the preceding embodiments, wherein the short wave UV light is 254 nm UV light, and wherein the sensor's resistance decreases with an increase in oxygen concentration in the gaseous sample.

The method according to any of the preceding embodiments, wherein the oxygen concentration in the gaseous sample is in a range from about 0.4% to about 21.5% (v/v).

The method according to any of the preceding embodiments, wherein gas flow is kept constant at 400 sc/cm.

The method according to any of the preceding embodiments, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio from about 55:45 to about 75:25.

The method according to any of the preceding embodiments, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio of about 70:30.

The method according to any of the preceding embodiments, wherein the method comprises alternatively irradiating the sensor with a long wave UV light source and a short wave UV light source.

The method according to any of the preceding embodiments, wherein the long wave UV light is 365 nm UV light, and the short wave UV light is 254 nm UV light, and wherein the UV light source is a light emitting diode (LED).

The method according to any of the preceding embodiments, wherein the sensor is integrated into an artificial intelligence device.

The method according to any of the preceding embodiments, wherein the gaseous sample is a spacecraft sample, a spacesuit sample, a food processing sample, a steel or cement production sample, an ink jet sample, a solution casting sample, a spin-coating sample, a laboratory sample, an electronic fuel injection or emission sample, a medical sample, or a pharmaceutical sample.

Claims

1. A method of detecting an analyte in a gaseous sample at room temperature and ambient pressure, wherein the method comprises: (i) exposing a gas sensor to a gaseous sample, wherein the gas sensor comprises titanium oxide nanoparticles attached to graphene nanoplatelets;(ii) exposing the sensor to UV irradiation at room temperature; and(iii) measuring a change in the sensor's resistance in response to UV irradiation, wherein magnitude of the change in the sensor's resistance is dependent upon the analyte's concentration, thereby detecting the analyte in the gaseous sample.

2. The method of claim 1, wherein the method further comprises determining the concentration of the analyte in the sample according to the logarithmic formula: S=0.0107 ln C+0.0321,

3. The method of claim 2, wherein the method further comprises purging the sensor with nitrogen for a time period from about 1 minute to about 20 minutes to decrease the sensor's resistance to baseline after each exposure to UV light.

4. The method of claim 3, wherein the sensor's change in resistance time in response to UV irradiation is about 250 seconds, and wherein the sensor's recovery time is about 640 seconds.

5. The method of claim 4, wherein UV irradiation is long wave UV light, and wherein the analyte is oxygen.

6. The method of claim 5, wherein the long wave UV light is 365 nm UV light, and wherein the sensor's resistance increases with an increase in oxygen concentration in the gaseous sample.

7. The method of claim 6, wherein the oxygen concentration in the gaseous sample is in a range from about 0.06% to about 15% (v/v).

8. The method of claim 4, wherein UV irradiation is short wave UV light, and wherein the analyte is oxygen and/or ozone.

9. The method of claim 8, wherein the short wave UV light is 254 nm UV light, and wherein the sensor's resistance decreases with an increase in oxygen concentration in the gaseous sample.

10. The method of claim 9, wherein the oxygen concentration in the gaseous sample is in a range from about 0.4% to about 21.5% (v/v).

11. The method of claim 4, wherein gas flow is kept constant at 400 sc/cm.

12. The method of claim 11, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio from about 55:45 to about 75:25.

13. The method of claim 12, wherein the graphene nanoplatelets and the titanium dioxide nanoparticles are in a weight ratio of about 70:30.

14. The method of claim 13, wherein the method comprises alternatively irradiating the sensor with a long wave UV light source and a short wave UV light source.

15. The method of claim 14, wherein the long wave UV light is 365 nm UV light, and the short wave UV light is 254 nm UV light, and wherein the UV light source is a light emitting diode (LED).

16. The method of claim 15, wherein the sensor is integrated into an artificial intelligence device.

17. The method of claim 16, wherein the gaseous sample is a spacecraft sample, a spacesuit sample, a food processing sample, a steel or cement production sample, an ink jet sample, a solution casting sample, a spin-coating sample, a laboratory sample, an electronic fuel injection or emission sample, a medical sample, or a pharmaceutical sample.