TWI651349B - Sensor, composite material and method of manufacturing the same - Google Patents

Abstract

The invention provides a sensor, a composite material and a method of manufacturing the same. The sensor includes a first electrode, a second electrode, and a layer of sensing material. The first electrode is separated from each other by the first electrode. A sensing material layer is between the first electrode and the second electrode and covers the first electrode and the second electrode. The layer of sensing material includes the composite material comprising a conductive polymer and a metal oxide. The conductive polymer has a hydrophilic end. The metal oxide is bonded to the hydrophilic end of the conductive polymer. The metal oxide includes a metal oxide precursor.

Description

Sensor, composite material and manufacturing method thereof

The present invention relates to a sensor, a composite material, and a method of fabricating the same.

In recent years, with the development of industry, people's attention to their own health and environmental protection has increased year by year, so relevant sensing technologies (such as gas sensing technology, ultraviolet light sensing technology, temperature sensing technology, humidity sensing technology, etc.) will be Gradually developing. In order to reduce the area of the sensor and improve the sensing sensitivity, current sensors often use an interdigitated electrode. However, taking a sensor with one hundred pairs of interdigitated electrodes as an example, the resistance of the sensor is still Too high (about a few hundred MΩ level), which in turn leads to poor sensing sensitivity of the sensor. Therefore, how to effectively reduce the resistance of the sensor and improve the sensitivity of the sensor is one of the issues that the current research and development personnel urgently need to solve.

The present invention provides a composite material suitable for a sensing material layer of a sensor that effectively reduces the resistance of the sensor and increases the sensitivity of the sensor.

The invention provides a sensor comprising a first electrode, a second electrode and a layer of sensing material. The second electrode and the first electrode are separated from each other. The sensing material layer is located between the first electrode and the second electrode and covers the first electrode and the second electrode. The sensing material layer includes a conductive polymer and a metal oxide. The conductive polymer has a hydrophilic end. The metal oxide is bonded to the hydrophilic end of the conductive polymer. The metal oxide includes a metal oxide precursor.

The present invention provides a composite material suitable for a sensing material layer of a sensor, comprising a conductive polymer and a metal oxide. The conductive polymer has a hydrophilic end and forms colloidal particles in a solvent. The metal oxide is bonded to the hydrophilic end of the conductive polymer.

The present invention provides a method of producing a composite material, the steps of which are as follows. A conductive polymer having a hydrophilic end is provided. A metal oxide is added such that the metal oxide is bonded to the hydrophilic end of the conductive polymer. The metal oxide is obtained from a metal oxide precursor via a dehydration reaction, a polymerization reaction, a condensation reaction, or a combination thereof.

Based on the above, the composite material of the present invention comprises a conductive polymer and a metal oxide, wherein the metal oxide is bonded to the hydrophilic end of the conductive polymer. Therefore, in addition to the good electrical conductivity of the composite material of the present invention, since the metal oxide shields the hydrophilic end of the conductive polymer, the hydrophilic end of the conductive polymer is less likely to react with moisture and oxygen in the environment, thereby avoiding the conductive polymer. Deterioration and problems of coating inconvenience. Furthermore, the composite of the present invention can be applied in the sensing material layer of the sensor, which can effectively reduce the resistance value of the sensor and increase the sensitivity of the sensor.

The above described features and advantages of the invention will be apparent from the following description.

1A is a schematic illustration of a composite material in accordance with some embodiments of the present invention. FIG. 1B is a partially enlarged schematic view of the composite material according to FIG. 1A.

Referring to FIG. 1A and FIG. 1B, the composite material 100 of the present invention includes a conductive polymer 110 and a metal oxide 120. Details are as follows:

The conductive polymer 110 may be a polymer having positive and negative charges. In other words, the conductive polymer 110 has a hydrophilic end and a hydrophobic end. In some embodiments, the long carbon chain of the conductive polymer 110 (which has hydrophobicity) has a plurality of functional groups of the hydrophilic end 112, such as a carboxyl group, a hydroxyl group, or a sulfonic acid group. Group), an amino group or a combination thereof, but the invention is not limited thereto. For example, in some embodiments, the conductive polymer 110 is composed, for example, of a conductive polymer having a hydrophobic long carbon chain with a plurality of hydrophilic ends 112 and a hydrophilic end 112 with a metal oxide 120. connection. In other embodiments, the conductive polymer 110 is composed, for example, of two conductive polymers, wherein the long carbon chain is composed of a conductive polymer having a plurality of hydrophilic ends 112 on the side chain, and the hydrophilic end 112 can have The other conductive polymer of the plurality of hydrophobic ends 114 may be connected to the metal oxide 120, but the invention is not limited thereto.

Specifically, the conductive polymer 110 includes a conjugated polymer and an acidic co-solvent. In one embodiment, the conjugated polymer is a main conductive structure, which may be, for example, poly(3,4-ethylenedioxythiophene; PEDOT), polyphenylene sulfide (PPS). , polypyrrole (PPy), polythiophene (PT), polyaniline (PANI) or a combination thereof. Additionally, the acidic cosolvent may be, for example, poly(styrensulfonate; PSS), acetic acid, propionic acid, butyric acid, benzoic acid, or a combination thereof. In some embodiments, the conjugated polymer (eg, PEDOT) is not readily soluble in a solvent (eg, water), but after the addition of the acidic co-solvent (eg, PSS), the conductive polymer 110 (eg, PEDOT: PSS) is dispersed in an aqueous solution in the form of a colloid.

In some embodiments, the conductive polymer 110 is dispersed in a solvent to form colloidal particles. The solvent includes a polar solvent, which may be, for example, water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, or a combination thereof. The diameter of the colloidal particles formed by the conductive polymer 110 is, for example, between 10 nm and 500 nm. In some embodiments, the weight-average molecular weight (Mw) of the conductive polymer 110 is, for example, between 20,000 g/mole (g/mol) and 500,000 g/mol.

In a specific embodiment, the conductive polymer 110 is, for example, PEDOT:PSS. In this embodiment, PEDOT is the primary conductive structure. The PSS is p-type doping, and the hydrophilic end 112 on the side chain is a negatively charged sulfonic acid group (SO ₃ ^- ). The negatively charged sulfonic acid group of PSS causes PEDOT to be positively charged (S ⁺ ) and is coupled to positively charged sulfur (S ⁺ ) on PEDOT or to metal oxide 120. In this embodiment, the ratio of PEDOT:PSS is, for example, between 1:1 and 1:10, but the invention is not limited thereto.

The metal oxide 120 can shield the hydrophilic end 112 of the conductive polymer 110. In some embodiments, metal oxide 120 is attached to hydrophilic end 112 of conductive polymer 110 to shield hydrophilic end 112. In some embodiments, the metal oxide 120 has a smaller size (diameter or length) than the conductive polymer 110. Metal oxide 120 such as titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ), zinc oxide (ZnO), tungsten trioxide (WO ₃ ), iron oxide (Fe ₂ O ₃ ), antimony pentoxide (Nb ₂ O) ₅ ), indium tin oxide (ITO), indium trioxide (In ₂ O ₃ ), barium titanate (SrTiO ₃ ), nickel monoxide (NiO), vanadium oxide (V ₂ O ₅ ), oxidation Molybdenum (MoO ₃ ), magnesium oxide, aluminum oxide or a combination thereof.

In one embodiment, the metal oxide 120 is obtained by dehydrating a metal oxide precursor, a polymerization reaction, a condensation reaction, or a combination thereof. In an embodiment, the metal oxide precursor may be in the form of a solution comprising at least one metal ion and a ligand. Specifically, the metal ion (for example, titanium) and the metal oxide precursor of the ligand (for example, isopropoxide) (for example, titanium isopropoxide) may be dissolved in a solvent containing an auxiliary agent (auxiliary agent). For example, an acid, a base, an oxidizing agent, or a combination thereof, and a solvent such as water) to form a metal oxide precursor solution (for example, a titanium isopropoxide solution). Next, a heating process is performed to dehydrate and polymerize the metal oxide precursor to a metal oxide (e.g., titanium oxide). In one embodiment, taking water as an example, the heating process has a temperature of 20 ° C to 90 ° C; and the heating process has a time of 0.5 hours to 96 hours. However, the invention is not limited thereto, and in an alternative embodiment, the parameters (time or temperature) of the heating process depend on the type of solvent.

In one embodiment, the ligand comprises bidentate ligands or alkoxide ligands. The metal ion is selected from at least one element selected from the group consisting of Ba, Co, Cu, Fe, In, Ti, Sn, Sr, V, W, Zn, Mo, Nb, Ni, Mg, and Al. The bidentate ligand is selected from at least one ligand selected from the group consisting of acetate, acetylacetonate, carbonate, and oxalate. The alkoxylated ligand is selected from the group consisting of methoxide, ethoxide, propoxide, isopropoxide, butoxide At least one of the ligands.

The shape of the metal oxide 120 includes, for example, a granular shape or a fiber shape. In some embodiments, referring to FIG. 1A, the shape of the metal oxide 120 is, for example, granular. In embodiments where the metal oxide 120 is particulate, the diameter of the metal oxide 120 is, for example, between 1 nm and 20 nm. In some embodiments, the ratio of the diameter of the colloidal particles formed by the electrically conductive polymer 110 to the diameter of the metal oxide 120 is, for example, between 5:1 and 500:1. In other embodiments, the ratio of the diameter of the colloidal particles formed by the electrically conductive polymer 110 to the diameter of the metal oxide 120 is, for example, 10:1. That is, the diameter of the colloidal particles formed by the conductive polymer 110 is larger than the diameter of the metal oxide 120. In some embodiments, the diameter of the colloidal particles formed by the conductive polymer 110 may be greater than 10 times the diameter of the metal oxide 120, but the invention is not limited thereto. In a specific embodiment, the conductive polymer 110 is, for example, PEDOT:PSS, which forms colloidal particles having a diameter of, for example, about 33 nm, and the metal oxide 120 is, for example, titanium oxide, tungsten oxide, molybdenum oxide or vanadium oxide, and the diameter thereof. For example, about 3 nm. That is, in this embodiment, the diameter of the colloidal particles formed by the conductive polymer 110 is more than 10 times the diameter of the metal oxide 120, but the invention is not limited thereto.

Referring to FIG. 1B, the metal oxide 120 in the composite material 100 of the present invention is connected to the hydrophilic end 112 of the conductive polymer 110. That is, by connecting the metal oxide 120, the hydrophilic end 112 of the conductive polymer 110 can be blocked. In some embodiments, the metal oxide 120 can mask all of the hydrophilic ends 112 of the conductive polymer 110 while exposing the hydrophobic ends. In other embodiments, the metal oxide 120 may be connected to a portion of the hydrophilic end 112 of the conductive polymer 110, and the other portion of the hydrophilic end 112 of the conductive polymer 110 may be exposed, but the invention is not limited thereto. The molar ratio of the conductive polymer 110 to the metal oxide 120 can be adjusted according to requirements (for example, the degree of connection of the metal oxide 120 to the hydrophilic end of the conductive polymer 110). For example, in some embodiments, the ratio by weight of both the conductive polymer 110 and the metal oxide 120 is, for example, between 0.01:1 and 250:1. In one embodiment, the conductive polymer 110 is, for example, PEDOT:PSS, and the metal oxide 120 is, for example, vanadium oxide. In this embodiment, in order to connect the hydrophilic ends of the conductive polymer 110 to the metal oxide 120, Under this condition, the ratio by weight of both the conductive polymer 110 and the metal oxide 120 is, for example, 0.011 to 250:1, but the invention is not limited thereto.

The metal oxide 120 may be connected to the hydrophilic end 112 of the conductive polymer 110 in various ways to shield the hydrophilic end 112 of the conductive polymer 110. In some exemplary embodiments, metal oxide 120 is bonded to hydrophilic end 112 of conductive polymer 110, for example, by hydrogen bonding or chemical bonding (eg, covalent bonding). In one embodiment, metal oxide 120 (eg, [-V=O] on vanadium oxide) and the hydrophilic end of conductive polymer 110 (eg, [-SO ₃ ^- ] on PSS) form a covalent bond (For example, [-VO-SO ₂ ^- ]), the hydrophilic end 112 of the conductive polymer 110 is blocked, and is reduced or unable to react with external moisture and oxygen. In other words, the metal oxide 120 of the present embodiment can prevent the conductive polymer 110 from reacting with the outside water and oxygen, thereby avoiding the problem of deterioration of the conductive polymer 110 and inconvenience in coating.

2A is a schematic view of a composite material according to further embodiments of the present invention. 2B is a partial enlarged view of the composite material according to FIG. 2A.

2A and 2B, the composite material 200 includes a conductive polymer 210 having a hydrophilic end 212 and a hydrophobic end 214, and a metal oxide 220 connected to the hydrophilic end 212 of the conductive polymer 210. In this embodiment, the difference from the above embodiment is that the shape of the metal oxide 220 is fibrous. In some embodiments, the ratio of the diameter of the colloidal particles formed by the conductive polymer 210 to the length of the metal oxide 220 is, for example, between 3:1 and 100:1. In some example embodiments, the length of the metal oxide 220 is, for example, between 5 nm and 500 nm. In some embodiments, the conductive polymer 210 forms a colloidal particle having a diameter greater than the length of the metal oxide 220. In an exemplary embodiment, the colloidal particles formed by the conductive polymer 210 may have a diameter greater than 10 times the length of the metal oxide 220, but the invention is not limited thereto. In a specific embodiment, the conductive polymer 210 is, for example, PEDOT:PSS, which forms colloidal particles having a diameter of, for example, about 33 nm, and the metal oxide 220 is, for example, titanium oxide, tungsten oxide, molybdenum oxide or vanadium oxide, and the length thereof. For example, about 14 nm. That is, in this embodiment, the diameter of the colloidal particles formed by the conductive polymer 210 is, for example, 2.5 times or more the length of the metal oxide 220, but the present invention is not limited thereto.

It is worth mentioning that in the composite material of the present invention, the conductive polymers 110, 210 have a function of providing a desired conductivity in the overall composite material 100, 200. For example, in some embodiments, the conductive polymers 110, 210 can increase the conductivity of the overall composite 100, 200. In one embodiment, the sheet resistance of the conductive polymer 110, 210 is, for example, between 200 ohm/□ and 3000 ohm/□, and the sheet resistance of the metal oxide 120, 220 is, for example, 200K ohm/ Between □ and 200 M ohm/□, the sheet resistance of the entire composite material 100, 200 is, for example, between 30 ohm/□ and 600 Ω/□, but the invention is not limited thereto.

On the other hand, in the composite materials 100, 200 of the present invention, the conductive polymers 110, 210 have a function of maintaining or adjusting a work function in the overall composite materials 100, 200. For example, in some embodiments, the conductive polymers 110, 210 can maintain the work function of the overall composite 100, 200. In some embodiments, the work function of the conductive polymers 110, 210 is, for example, between 4.8 eV and 5.2 eV, and the work function of the metal oxides 120, 220 is, for example, between 5.2 eV and 5.7 eV, and the overall composite The work function of the materials 100, 200, for example, may be somewhere in between, for example between 5.0 eV and 5.6 eV, although the invention is not limited thereto. In other words, the metal oxides 120, 220 can also adjust the work function of the overall composite 100, 200 to a desired value.

The method for forming the composite materials 100 and 200 is, for example, a metal oxide or a precursor thereof and a conductive polymer are uniformly mixed in a solvent in the above-described ratio to produce a conductive polymer-metal oxide composite material. In some embodiments, the solvent includes a polar solvent, which may be, for example, water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol. Or a combination thereof. The mixing method includes shaking and stirring, and may further include applying warming or ultrasonic waves to assist mixing. Specifically, the solution-like metal oxide is uniformly mixed with the solution-like conductive polymer. In one embodiment, the mixing may include vortex mixing with a vortex mixer, rotary mixing with a rotator mixer, roller mixing with a tube roller mixer, and linearity/ The linear/orbital shaker or the rock shaker is oscillated and mixed, stirred by a DC stirrer (DC-Stirrer), or stirred by a magnet. In one embodiment, the mixing time is at least 1 second; the mixing temperature is between 4 ° C and 80 ° C.

Further, in the composite material of the present invention, since the metal oxide shields the hydrophilic end of the conductive polymer, the hydrophilic end of the conductive polymer is less likely to react with moisture and oxygen in the environment, thereby preventing deterioration of the conductive polymer and coating. Inconvenience. Moreover, since the hydrophilic end of the conductive polymer is shielded, the composite material as a whole is more hydrophobic than the original conductive polymer, thereby improving the adhesion of the composite material of the present invention to the hydrophobic material. Further, in the composite material of the present invention, the conductive polymer is located between the metal oxides. That is, the metal oxide is dispersed between the conductive polymers, so that the metal oxide is not easily aggregated. Therefore, problems due to aggregation of metal oxides can be avoided. In detail, since the phenomenon of metal oxide physicochemical agglomeration is reduced, the film forming property of the overall composite material can be improved, thereby reducing surface roughness, reducing surface pores, and the like, thereby avoiding leakage or tip discharge when an electric field is applied. problem.

Based on the above, the composite material of the present invention can be used in a wet process 3D printing technique such as ink-jet or aerosol-jet, and can be applied in the form of a conductive material or a sensing material. Plastic substrates, including, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimine (PI), polyvinyl chloride (PVC), polypropylene (PP) A substrate such as a cycloolefin polymer (COP) or polyethylene (PE).

Further, the composite material of the present invention can also be applied to an organic optoelectronic semiconductor device such as an organic solar cell, an organic light emitting diode or the like. For example, the composite of the present invention can be used as an electron or hole buffer layer for solar cells. The embodiment in which the composite material of the present invention is applied to a solar cell will be described in detail below, but the application of the composite material of the present invention is not limited thereto.

3 is a cross-sectional view of a composite material for use in a solar cell, in accordance with some embodiments of the present invention.

Referring to FIG. 3 , the solar cell 300 may sequentially include a substrate 310 , a first conductive layer 320 , an active layer 330 , and a second conductive layer 340 . The first conductive layer 320 further includes an electrode layer 322 and a buffer layer 324 . In detail, the first surface 310a of the substrate 310 is an incident surface of the light 302, and the first conductive layer 320 (including the electrode layer 322 and the buffer layer 324), the active layer 330, and the second conductive layer 340 are sequentially disposed on the substrate. The first surface 310a of the 310 is opposite the second surface 310b.

In some embodiments, substrate 310 is, for example, a transparent substrate. The material of the substrate 310 includes, for example, glass, a transparent resin, or other suitable materials. With continued reference to FIG. 3, the active layer 330 is located on the buffer layer 324. In some embodiments, the material of the active layer 330 includes, for example, poly(3-hexylthiophene; P3HT), ([6,6]-phenyl-C61-butyric acid method ester; PCBM), and the like. The second conductive layer 340 is located on the active layer 330. In some embodiments, the material of the second conductive layer 340 includes, for example, a metal. The metal is, for example, gold, silver, copper, aluminum, titanium, or the like, but the invention is not limited thereto.

The first conductive layer 320 is located between the substrate 310 and the active layer 330. The first conductive layer 320 includes an electrode layer 322 and a buffer layer 324. That is, in this embodiment, the electrode layer 322 is located on the second surface 310b of the substrate 310, and the buffer layer 324 is located between the electrode layer 322 and the active layer 330. The material of the electrode layer 322 includes, for example, indium tin oxide (ITO), indium zinc oxide (IZO), or the like, but the present invention is not limited thereto. The material of the buffer layer 324 in this embodiment may be the composite material 100 or 200 in the above embodiment of the present invention (please refer to FIG. 1A or FIG. 2A). The method of forming the buffer layer 324 may be, for example, by a spin coating method. Applying the composite of the present invention to the buffer layer 324 of the solar cell 300 provides good electrical conductivity and a desired work function suitable for transferring holes (or electrons). On the other hand, since the metal oxide in the composite material shields the hydrophilic end of the conductive polymer, the material stability can be improved, the coating can be facilitated, and the adhesion of the buffer layer 324 to the hydrophobic material can be improved. Further, since the metal oxide in the composite material is dispersed between the conductive polymers, problems such as electric leakage or tip discharge due to aggregation of the metal oxide can be avoided.

The above embodiment is a method in which the composite material of the present invention is applied to a conductive polymer layer of a solar cell, but the present invention is not limited thereto. The composite of the present invention can also be used in a sensor.

4 is a cross-sectional view of a composite material for a sensor, in accordance with some embodiments of the present invention.

Referring to FIG. 4 , the sensor 400 of the embodiment includes a substrate SUB, a first electrode 402 , a second electrode 404 , and a sensing material layer 406 . In one embodiment, the substrate SUB may be a germanium substrate, a glass substrate, a germanium-on-insulator (SOI) substrate, a wiring substrate, the aforementioned plastic substrate, or a combination thereof.

As shown in FIG. 4, the first electrode 402 and the second electrode 404 are disposed on the substrate SUB. In detail, the first electrode 402 and the second electrode 404 are separated from each other and are not in contact with each other. In the present embodiment, the first electrode 402 and the second electrode 404 may be configured as a finger-type electrode, but the present invention does not limit the shape of the first electrode 402 and the second electrode 404 as long as the first electrode 402 and the second electrode 404 It is within the scope of the invention to be separated by a predetermined distance, separated from each other and not in contact with each other. In an alternative embodiment, the first electrode 402 and the second electrode 404 may also be, for example, stacked electrodes. The arrangement of the three-dimensional stacked electrodes can effectively increase the density of the sensor and reduce the overall component volume. In detail, the stacked electrodes may be formed by vertically and alternately stacking a plurality of electrode layers with a plurality of dielectric layers (not shown) on the substrate SUB. That is, at least one dielectric layer is disposed between two adjacent electrode layers to electrically isolate adjacent two electrode layers. In an embodiment, the electrode layer comprises a conductor material. The conductor material can be a doped or undoped polysilicon material, a metal material, or a combination thereof. The material of the above dielectric layer may be tantalum oxide, tantalum nitride or a combination thereof.

In an embodiment, the sensing material layer 406 is located in a gap between the first electrode 402 and the second electrode 404 and extends to cover the top surfaces of the first electrode 402 and the second electrode 404. Although the sensing material layer 406 depicted in FIG. 4 does not completely cover all surfaces of the first electrode 402 and the second electrode 404, the invention is not limited thereto. In other embodiments, the sensing material layer 406 may also completely cover all surfaces of the first electrode 402 and the second electrode 404 (including the top surface and the side surface). It should be noted that when the object to be tested adsorbs or contacts the surface of the sensing material layer 406, the object to be tested may react with the sensing material layer 406 such that the sensing material between the first electrode 402 and the second electrode 404 The capacitance or resistance value of layer 406 changes. Then, the user can calculate the type of the object to be tested or the amount of parameter change by changing the capacitance value or the electrical resistance characteristic of the resistance value.

In an embodiment, the sensing material layer 406 can be a gas sensing layer, a light sensing layer, a humidity sensing layer, a temperature sensing layer, or a combination thereof. In other words, the sensor 400 of the present embodiment can be used to sense gas, light, humidity, temperature, or a combination thereof.

In an embodiment, the method of forming the sensing material layer 406 can be, for example, a non-contact printing method. In an embodiment, the non-contact printing method includes an inkjet printing method or an aerosol spray printing method. An aerosol spray printing method is exemplified by using an aerosol jet deposition head to form an outer sheath flow and an inner gas-filled carrier flow (inner aerosol-laden). Carrier flow) A ring-shaped propagating nozzle. In an annular aerosol spray process, an aerosol stream having a sensing material is concentrated and deposited on a planar or non-planar substrate SUB. Next, heat treatment or photochemical treatment is performed to form the sensing material layer 406. The above steps may be referred to as Maskless Mesoscale Material Deposition (M3D), that is, it may be deposited without using a mask such that the deposited material layer has a size of 1 micrometer to 1000 micrometers. Linewidth between the lines.

In an embodiment, the material of the sensing material layer 406 is the composite material 100, 200 described above. The composition and formation steps of the above composite materials 100, 200 have been described in detail in the above paragraphs and will not be described again.

It should be noted that, in an embodiment, by using the composite materials 100, 200 as the sensing material layer 406, the conductive polymer in the composite materials 100, 200 can reduce the resistance of the sensing material layer 406 to The sensitivity of the sensor 400 is increased. The sensing of the present embodiment is compared to a conventional sensor (which uses only metal oxide as the sensing material layer and needs to be sensed at a high temperature (for example, 200 ° C to 400 ° C)) The device 400 can perform sensing at room temperature (eg, 0 ° C to 50 ° C). Therefore, the sensor 400 of the present embodiment can be applied to most electronic products (such as mobile phones) without overheating and at the same time greatly reducing the power consumption (which comes from high temperature heating).

On the other hand, in an embodiment, the metal oxide in the composite material 100, 200 can shield the hydrophilic end of the conductive polymer to prevent the conductive polymer from reacting with the outside water and oxygen, thereby preventing the conductive polymer from deteriorating and The problem of inconvenience in coating. In this way, the embodiment can extend the service life of the sensing material layer having the conductive polymer, and can adjust the content of the metal oxide to coat the sensing material layer on the surface of any material (ie, hydrophilic). On the surface or on the hydrophobic surface). Thereby increasing the range of use of the sensing material layer.

Hereinafter, the present invention will be more specifically described by exemplifying the experimental examples of the present invention. However, the materials, the methods of use, and the like shown in the following experimental examples can be appropriately changed without departing from the spirit of the invention. Therefore, the scope of the present invention should not be construed as limited by the experimental examples shown below.

Experimental example 1

In Experimental Example 1, PEDOT:PSS (which was purchased from Heraeus) was uniformly mixed with a metal oxide by a vortex mixer to be coated on an interdigitated electrode, wherein the PEDOT:PSS after mixing The weight percentage with the metal oxide is 1:1. The metal oxide is a metal oxide precursor (for example, Molybdenyl acetylacetonate) configured to have an alcohol solution (for example, isopropanol) at a concentration of 0.1 to 10% by weight, and heated at 40 to 80 ° C, and the reaction is continued. Made from 0.05 to 96 hours. Next, drying is performed to form a layer of the sensing material on the interdigitated electrode. The drying time is from 10 seconds to 1800 seconds, and the drying temperature is between 20 ° C and 200 ° C. Next, the resistance value of the sensing material layer of Experimental Example 1 was measured, and the results are shown in FIG. 5.

Experimental example 2 , 3

In Experimental Examples 2 and 3, a sensing material layer was formed on the interdigitated electrodes, respectively, in the procedure of the above Experimental Example 1. The difference from Experimental Example 1 is that the weight percentage of PEDOT:PSS to metal oxide of Experimental Example 2 was 2.25:1. The PEDOT:PSS and metal oxide weight percentage of Experimental Example 3 was 6:1. Next, the resistance values of the sensing material layers of Experimental Examples 2 and 3 were measured, and the results are shown in FIG. 5.

Comparative example 1

In Comparative Example 1, 1.0 wt% of PEDOT:PSS (which was purchased from Heraeus) was coated on an interdigitated electrode. Next, drying is performed to form a layer of the sensing material on the interdigitated electrode. The drying time is from 10 seconds to 1800 seconds, and the drying temperature is between 20 ° C and 200 ° C. Next, the resistance value of the sensing material layer of Comparative Example 1 was measured, and the results are shown in FIG. 5.

Comparative example 2

In Comparative Example 2, a 1.0 wt% metal oxide solution (purchased from Sigma-Aldrich Co.) was coated on the interdigitated electrode. Next, drying is performed to form a layer of the sensing material on the interdigitated electrode. The drying time is from 10 seconds to 1800 seconds, and the drying temperature is between 20 ° C and 200 ° C. Next, the resistance value of the sensing material layer of Comparative Example 2 was measured, and the results are shown in FIG. 5.

Comparative example 3

In Comparative Example 3, a 1 wt% metal oxide solution was coated on the interdigitated electrode. The metal oxide solution is a metal oxide precursor (for example, Molybdenyl acetylacetonate) configured to a concentration of 0.1-10% by weight of an alcohol solution (for example, isopropanol), and heated at 40-80 ° C, and continued The reaction is carried out for 0.05-96 hours. Next, drying is performed to form a layer of the sensing material on the interdigitated electrode. The drying time is from 10 seconds to 1800 seconds, and the drying temperature is between 20 ° C and 200 ° C. Next, the resistance value of the sensing material layer of Comparative Example 3 was measured, and the results are shown in FIG. 5.

As shown in FIG. 5, the sensing material layer of Experimental Example 1-3 to which the conductive polymer (PEDOT: PSS) was added had a lower resistance value than Comparative Examples 2 and 3. In addition, compared with the sensing material layer of PEDOT:PSS of Comparative Example 1, the combination of conductive polymer (PEDOT:PSS) and metal oxide (molybdenum oxide) has a synergy effect to provide a lower resistance. Further, in Experimental Example 1-3, as the content of the conductive polymer (PEDOT:PSS) was increased, the conductivity of the sensing material layer was also lowered, thereby increasing the sensitivity of the sensor.

6A to 6D are optical micrographs of Comparative Example 1 and Experimental Example 1-3, respectively.

As shown in FIG. 6A, in Comparative Example 1, only the metal oxide was used as the sensing material layer, and therefore, the sensing material layer of Comparative Example 1 was not easily molded and was easily cracked. 6B to 6D, as the content of the conductive polymer (PEDOT: PSS) increases, the formed sensing material layer is more easily molded and is less likely to be cracked. That is to say, the conductive polymer is added to the sensing material layer, which not only helps to lower the resistance value of the sensing material layer, but also makes the sensing material layer less susceptible to cracking.

In summary, the composite material of the present invention comprises a conductive polymer and a metal oxide, wherein the metal oxide is connected to the hydrophilic end of the conductive polymer. Therefore, in addition to the good electrical conductivity and work function of the composite material of the present invention, since the metal oxide shields the hydrophilic end of the conductive polymer, the hydrophilic end of the conductive polymer is less likely to react with moisture and oxygen in the environment, thereby avoiding The problem of deterioration of the conductive polymer and inconvenience in coating. Furthermore, since the hydrophilic end of the conductive polymer is shielded, the composite material is more hydrophobic than the original conductive polymer, thereby improving the adhesion of the composite material to the hydrophobic material. In addition, the combination of the conductive polymer and the metal oxide in the composite material of the present invention has a multiplication effect, which can be applied to the sensing material layer of the sensor to effectively reduce the resistance value of the sensor and enhance the sense The sensitivity of the detector. In addition, the conductive polymer is added to the sensing material layer, which not only helps to reduce the resistance value of the sensing material layer, but also makes the sensing material layer not easy to crack, thereby improving the reliability of the sensor.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100, 200‧‧‧ composite materials

110, 210‧‧‧ Conductive polymer

112, 212‧‧ ‧ hydrophilic end

114, 214‧‧‧ hydrophobic end

120, 220‧‧‧ metal oxides

300‧‧‧ solar cells

302‧‧‧Light

310‧‧‧Substrate

310a‧‧‧ first surface

310b‧‧‧ second surface

320‧‧‧First conductive layer

322‧‧‧electrode layer

324‧‧‧buffer layer

330‧‧‧Active layer

340‧‧‧Second conductive layer

400‧‧‧ sensor

402‧‧‧First electrode

404‧‧‧second electrode

406‧‧‧Sensor material layer

SUB‧‧‧ substrate

1A is a schematic illustration of a composite material in accordance with some embodiments of the present invention. FIG. 1B is a partially enlarged schematic view of the composite material according to FIG. 1A. 2A is a schematic view of a composite material according to further embodiments of the present invention. 2B is a partial enlarged view of the composite material according to FIG. 2A. 3 is a cross-sectional view of a composite material for use in a solar cell, in accordance with some embodiments of the present invention. 4 is a cross-sectional view of a composite material for a sensor, in accordance with some embodiments of the present invention. Fig. 5 is a bar graph of the resistance values of Experimental Example 1-3 and Comparative Example 1-3. 6A to 6D are optical micrographs of Comparative Example 1 and Experimental Example 1-3, respectively.

Claims (12)

A sensor comprising: a first electrode; a second electrode separated from the first electrode; and a sensing material layer between the first electrode and the second electrode and covering the first An electrode and the second electrode, wherein the sensing material layer comprises: a conductive polymer having a hydrophilic end; and a metal oxide connecting the hydrophilic end of the conductive polymer, wherein the metal oxide is Made from a metal oxide precursor comprising at least one metal ion and a ligand, the ligand comprising a bidentate ligand or an alkoxide ligand. The sensor of claim 1, wherein the first electrode and the second electrode are configured as a finger-type electrode, a stacked electrode, or a combination thereof. The sensor of claim 1, wherein the layer of sensing material is formed by a non-contact printing method. The sensor of claim 3, wherein the non-contact printing method comprises an inkjet printing method or an aerosol spray printing method. A composite material comprising: a conductive polymer having a hydrophilic end and forming colloidal particles in a solvent; and a metal oxide connecting the hydrophilic end of the conductive polymer, wherein the metal oxide is composed of a metal oxide Prepared by a precursor, the metal oxide precursor comprising at least one metal ion and a ligand, the ligand comprising a bidentate ligand Or an alkoxide ligand. The composite material according to claim 5, wherein the metal ion is selected from the group consisting of Ba, Co, Cu, Fe, In, Ti, Sn, Sr, V, W, Zn, Mo, Nb, Ni, At least one element selected from the group consisting of Mg and Al, the bidentate ligand being selected from at least one of the group consisting of acetate, acetoacetate, carbonate, and oxalate a monomer, the alkoxide ligand being selected from the group consisting of at least one ligand consisting of a methoxide, an ethanolate, a propoxide, an isopropoxide, and a butoxide. The composite material according to claim 5, wherein the conductive polymer comprises a conjugated polymer and an acidic cosolvent, and the conjugated polymer comprises polydioxyethylthiophene (PEDOT) and polyphenylene sulfide. (PPS), polypyrrole (PPy), polythiophene (PT), polyaniline (PANI) or a combination thereof, the acidic co-solvent comprises polystyrenesulfonic acid (PSS), acetic acid, propionic acid, butyric acid, benzoic acid Or a combination thereof. The composite material according to claim 5, wherein the metal oxide comprises titanium dioxide, tin dioxide, zinc oxide, tungsten trioxide, iron oxide, antimony pentoxide, indium tin oxide, indium trioxide, Barium titanate, nickel monoxide, vanadium oxide, molybdenum oxide, magnesium oxide, aluminum oxide or a combination thereof. The composite material according to claim 5, wherein the weight percentage of the conductive polymer to the metal oxide is between 0.01:1 and 250:1. The composite material according to claim 5, wherein the solvent comprises a polar solvent, and the polar solvent comprises water, methanol, ethanol, propanol, and isopropyl. Alcohol, butanol, ethylene glycol, diethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol or a combination thereof. The composite material according to claim 5, wherein the metal oxide is connected to the hydrophilic end of the conductive polymer by hydrogen bonding or a covalent bond. A method of manufacturing a composite material comprising: providing a conductive polymer having a hydrophilic end; and adding a metal oxide such that the metal oxide is bonded to the hydrophilic end of the conductive polymer, wherein the metal oxide is It is obtained from a metal oxide precursor via a dehydration reaction, a polymerization reaction, a condensation reaction, or a combination thereof.