US-12622239-B2 - Sensor comprising pattern illumination-based annealed coated substrate and one or more functional molecules and process of using same

US12622239B2US 12622239 B2US12622239 B2US 12622239B2US-12622239-B2

Abstract

The present invention relates to sensors comprising pattern illumination-based annealed coated substrate and one or more functional molecules and process of using same. Such process yields components that can have one or more electronic and/or optical functionalities that are integrated on the same substrate or film and to which one or more functional molecules can be attached to yield a sensor. In addition, such process does not require large-scale clean rooms and is easily configurable. Thus, rapid device prototyping, design change and evolution in the lab and on the production side is realized. The resulting sensors provide a sensing capability that is as good as or better than current sensors and can be tailored to sense specific biomaterials and/or chemicals.

Inventors

Nicholas R. Glavin
Christopher Muratore
Melani K. Muratore

Assignees

GOVERNMENT OF THE UNITED STATES, AS REPRESENTED BY THE SECRETARY OF THE AIR FORCE

Dates

Publication Date: 20260505
Application Date: 20210602

Claims (20)

1 . A process of making a sensor, said process comprising; a) applying one or more coatings of electrically conductive material to a substrate, which substrate has a first side and a second side, said one or more coatings of electrically conductive material being applied to at least the first side of said substrate; b) removing a portion of said electrically conductive material to form a pattern of electrically conductive material electrodes on said substrate; c) applying one or more chemical coatings in the form of a continuous film over said patterned electrical conductive material to form a coated substrate, wherein said patterned electrical conductive material comprises a material selected from the group consisting of: poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, poly(pyrrole), polycarbazoles, polyindoles, polyazepines, Cr, Mo, Ti, Sc, Ni, V, Hf, W, Nb, Au, Ag, Cu, and Pt, and mixtures thereof, and said one or more chemical coatings disposed over said one or more coatings of patterned electrical conductive material each independently comprise a transition metal and an element selected from the group consisting of: hydrogen, carbon, nitrogen, oxygen, sulfur, selenium, phosphorous, and mixtures thereof, wherein said one or more chemical coatings each independently comprising at least one of an amorphous, nanocrystalline, microcrystalline or crystalline region; d) pattern illumination-based annealing said coated substrate, said pattern illumination-based annealing comprising using one or more lasers and/or lamps to achieve at least one of a chemical change or a change in crystallization in at least a portion of at least one of said one or more chemical coatings on at least one side of said substrate; and e) attaching one or more types of functional molecules and/or one or more complexes comprising one or more types of functional molecules and one or more target molecules to at least a portion of said pattern illumination-based anneal coated substrate, said one or types of functional molecules being attached by: (i) attaching said one or more functional molecules and/or one or more complexes to an annealed portion on the surface of said pattern illumination-based anneal coated substrate at vacancies in the surface of the chemical coating that create bonding sites for said functional molecules; and/or (ii) bonding a peptide to said pattern illumination-based anneal coated substrate and attaching said one or more functional molecules to said peptide.
2 . A process of making a sensor according to claim 1 wherein said one or more functional molecules are biomaterials that are selected from the group consisting of: peptides, nanozymes, proteins, lipids, carbohydrates and lectins, nucleic acids, and mixtures thereof.
3 . A process of making a sensor according to claim 2 wherein said biomaterial's attachment to said pattern illumination-based anneal coated substrate comprises at least one of a covalent bond, electrostatic bond, or a covalent and electrostatic bond.
4 . A process of making a sensor according to claim 2 wherein said attaching said biomaterials to said pattern illumination-based anneal coated substrate comprises contacting said at least a portion of said pattern illumination-based anneal coated substrate and said one or more types of biomaterials.
5 . A process of making a sensor according to claim 1 wherein: at least one of said one or more chemical coatings comprises, prior to said annealing, two or more regions that are amorphous, nanocrystalline, microcrystalline or crystalline with the proviso that at least two of said regions are not identical with respect to being amorphous, nanocrystalline, microcrystalline or crystalline and said laser or lamp forms on, within or on and within said at least one of said one or more chemical coatings: (i) at least two electronic elements selected from a conductor, semiconductor and an insulator; (ii) two or more different conductors having at least one of the following: different electrical properties or different optical properties; (iii) two or more different semiconductors having at least one of the following: different electrical properties or different optical properties; or (iv) two or more different insulators having at least one of the following: different electrical properties or different optical properties; said process being performed under one of the following conditions: vacuum of less 100 torr, air or under a fluid blanket other than air; and said pattern illumination-based annealing results in at least one of a chemical change or a change in crystallization, or the removal of at least a portion of at least one of said one or more chemical coatings and resulting in an electrical component, an optical component or a combined electrical and optical component being formed on, within or on and within at least a portion of said pattern illumination-based annealed one or more chemical coatings.
6 . The process of claim 1 further comprising performing steps a) to e) on the second side of said substrate as well.
7 . The process of claim 1 wherein said transition metal is selected from the group consisting of molybdenum, tungsten, niobium, tantalum, vanadium, titanium, chromium, iron, rhodium, hafnium, rhenium and mixtures thereof.
8 . A process according to claim 1 wherein said one or types of functional molecules are primarily attached to said pattern illumination-based anneal coated substrate by bonding a peptide to said pattern illumination-based anneal coated substrate and attaching said one or more functional molecules to said peptide.
9 . The process of claim 5 wherein, said electrical and/or optical component is selected from the group consisting of an inductor, a capacitor, a resistor, a diode, a a trace, a battery, an optical filter, a chemical sensor, a biological sensor and a solar cell.
10 . The process of claim 1 wherein said pattern illumination-based annealing in step d) further comprises removal of at least a portion of said chemical coating on at least one side of said substrate, and each of said one or more chemical coatings have an area and a thickness and said removal of said at least a portion of said one or more chemical coating occurs, said removal comprising at least one of: a.) laser ablation removal of from about 0.1% to about 99.9% of at least one of said one or more chemical coatings' area; or b.) laser ablation removal of at least 85% of at least one of said chemical coatings' thickness; or laser ablation removal of about 85% to about 99% of at least one of said chemical coatings' thickness.
11 . The process of claim 1 , said process being a roll process wherein said coated chemically substrate is a rolled coated chemically substrate that is unrolled at least in part, said unrolled chemical coating portion of said coated substrate being at least in part pattern illumination-based annealed.
12 . The process of claim 1 wherein said substrate of said coated substrate is selected from glass, polymer and mixtures thereof.
13 . The process of claim 1 wherein at least a portion of said coated substrate's pattern illumination-based annealed chemical coating is further treated by at least one of the following processes: a.) two or more pattern illumination-based annealings; b.) plasma treatment comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, H 2 , O 2 , SF 6 , CF 4 , N 2 and mixtures thereof; c.) ion beam irradiation comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ion beam, said ion beam comprising an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, H 2 , O 2 , SF 6 , CF 4 , N 2 and mixtures thereof; d.) electron beam illumination comprising at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an electron dose of from about 10 2 electrons/nm 2 to about 10 25 electrons/nm 2 ; e.) thermal annealing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating, said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating's thermal annealing treatment temperature being from about 250° C. to about 1,500° C.; f.) chemically etching said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating comprising contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with an etching composition; g.) electro-chemically treating said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating by contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with a chemical composition comprising an electrolyte and subjecting said contacted at least a portion of said coated substrate's pattern illumination-based annealed chemical coating and said chemical composition comprising an electrolyte to an electrical current; h.) surface physical modification of at least a portion of said coated substrate's pattern illumination-based annealed chemical coating.
14 . The process of claim 1 wherein each target is independently a chemical target or a biological target.
15 . The process of claim 1 wherein said step c) of applying one or more chemical coatings in the form of a continuous film over said patterned electrical conductive material to form a coated substrate comprises applying said one or more chemical coatings using a chemical or physical vapor deposition process.
16 . The process of claim 1 wherein said pattern illumination-based annealing results in a change in the molecular composition in a region of at least one of said materials that results in an electrical component, an optical component or a combined electrical and optical component being formed on, within or on and within said material.
17 . The process of claim 16 wherein the transition metal is Mo, and the element is oxygen, and the process forms different oxide phases MoO 2 and MoO 3 on, within, or on and within said material.
18 . The process of claim 7 wherein said transition metal is selected from the group consisting of: niobium, tantalum, vanadium, titanium, chromium, iron, rhodium, hafnium, rhenium, and mixtures thereof.
19 . The process of claim 1 wherein at least a portion of said coated substrate's pattern illumination-based annealed chemical coating is further treated by at least one of the following processes: a) plasma treatment comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, H 2 , O 2 , SF 6 , CF 4 , N 2 and mixtures thereof; b) ion beam irradiation comprising exposing said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an ion beam, said ion beam comprising an ionized gas derived from the group consisting of He, Ne, Ar, Kr, Xe, H 2 , O 2 , SF 6 , CF 4 , N 2 and mixtures thereof; c) electron beam illumination comprising at least a portion of said coated substrate's pattern illumination-based annealed chemical coating to an electron dose of from about 10 2 electrons/nm 2 to about 10 25 electrons/nm 2 d) chemically etching said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating comprising contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with an etching composition; e) electro-chemically treating said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating by contacting said at least a portion of said coated substrate's pattern illumination-based annealed chemical coating with a chemical composition comprising an electrolyte and subjecting said contacted at least a portion of said coated substrate's pattern illumination-based annealed chemical coating and said chemical composition comprising an electrolyte to an electrical current; and f) surface physical modification of at least a portion of said coated substrate's pattern illumination-based annealed chemical coating.
20 . A process of making a sensor according to claim 1 wherein said one or more functional molecules are biomaterials that are selected from the group consisting of: peptides, nanozymes, lipids, carbohydrates and lectins, nucleic acids, and mixtures thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application is a continuation-in-part of U.S. patent application Ser. No. 17/216,729 filed Mar. 30, 2021, which in turn claims priority to U.S. Provisional Application Ser. No. 63/001,604 filed Mar. 30, 2020, the contents of U.S. patent application Ser. No. 17/216,729 and U.S. Provisional Application Ser. No. 63/001,604 hereby incorporated by reference in its entry. RIGHTS OF THE GOVERNMENT The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty. FIELD OF THE INVENTION The present invention relates to sensors comprising pattern illumination-based annealed coated substrate and one or more functional molecules and process of using same. BACKGROUND OF THE INVENTION Current sensors that are used to sense/detect materials such as viruses, bacteria and chemicals are costly to make and/or use. Thus, the use of such sensors are more limited than desired. What is needed is a sensor that can be made quickly, in large numbers—even in millions per day—and yet still provide a sensor capability that is as good as or better than current sensors. Furthermore, unlike current sensors, it is desirable that any new sensor be more accurate and more specific with respect to the material that is detected. Applicants recognized that the source of the problems associated with current sensors were the processing challenges associated with achieving the required size of the active region of the sensor, sensor chemical and structural uniformity from sensor to sensor that were driven by the complexity of the chemical and physical steps of current production processes. Such recognition led Applicants to develop a process of making the substrate components for sensors that can readily transformed into sensors by attaching a biomaterial there to. Such process employs localization of such material transformations, thereby allowing added flexibility in performing steps for sensor processing, such as application and patterning of electrical contacts prior to application of active electronic material. Importantly, Applicants process can be used to make structural and/or chemical changes within a film or other article that results in an electrical component, an optical component or a combined electrical and optical component being created in such film or article to which a biomaterial is attached to yield a sensor. Such process does not require large-scale clean rooms and is easily configurable. Thus, rapid device prototyping, design change and evolution in the lab and on the production side are realized. SUMMARY OF THE INVENTION The present invention relates to sensors comprising pattern illumination-based annealed coated substrate and one or more functional molecules and process of using same. Such process yields components that can have one or more electronic and/or optical functionalities that are integrated on the same substrate or film and to which one or more functional molecules can be attached to yield a sensor. In addition, such process does not require large-scale clean rooms and is easily configurable. Thus, rapid device prototyping, design change and evolution in the lab and on the production side is realized. The resulting sensors provide a sensing capability that is as good or better than current sensors and can be tailored to sense specific biomaterials and/or chemicals Additional objects, advantages, and novel features of the invention will be set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention. FIG. 1 is a schematic depicting the process of coating MoS2 onto patterned metal contacts followed by laser conversion to 2H-phase MoS2 device. FIG. 2 is an example laser processed device configuration with deposited MoS2 on prepatterned metal contacts and subsequent conversion showing in additional detail Metal electrodes (1), Amorphous MoS2 (2) and Laser crystallized MoS2 (3) FIG. 3A is an example of the first unit operation in a roll-to-roll deposition of MoS2 onto metal patterned substrates with subsequent laser annealing showing Feed roll (1), Main roller (2), Receiving roller (3), MoS2 sputtering target (4), Laser (5), Metal sputtering target (6) and Flexible glass substrate (7). FIG. 3B is an ex