CN108305947A - Sensor, composite material and its manufacturing method - Google Patents
Sensor, composite material and its manufacturing method Download PDFInfo
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- CN108305947A CN108305947A CN201711334995.5A CN201711334995A CN108305947A CN 108305947 A CN108305947 A CN 108305947A CN 201711334995 A CN201711334995 A CN 201711334995A CN 108305947 A CN108305947 A CN 108305947A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
A kind of sensor of present invention offer, composite material and its manufacturing method.The sensor includes first electrode, second electrode and sensing element.First electrode is separated from each other with the second electrode.Sensing element is between the first electrode and the second electrode and covers the first electrode and the second electrode.The sensing element includes the composite material comprising conducting polymer and metal oxide.Conducting polymer has water-wet side.Metal oxide connects the water-wet side of conducting polymer.The metal oxide includes metallic oxide precursor object.
Description
Technical field
The present invention relates to a kind of sensor, composite material and its manufacturing methods.
Background technology
Recently as industrial development, since people increase the attention of own health and environmental protection year by year, because
This associated sensed technology (such as gas sensing technology, ultraviolet light sensing technology, temperature sensing techniques, humidity technology) just by
In gradually developing.Area in order to reduce sensor is passed through with sensing sensitivity, existing sensor is improved frequently with fourchette type electrode,
However, by taking the sensor with 100 pairs of fourchette type electrodes as an example, the resistance value of sensor is still excessively high (about hundreds of M Ω grades),
And then cause the sensing sensitivity of sensor bad.Therefore, how effectively to reduce the resistance value of sensor and promote the spirit of sensor
Sensitivity, actually current research staff one of subject under discussion urgently to be resolved hurrily.
Invention content
The present invention provides a kind of composite material of the sensing element suitable for sensor, can be effectively reduced sensor
Resistance value and promote the sensitivity of sensor.
A kind of sensor of present invention offer includes first electrode, second electrode and sensing element.Second electrode and the
One electrode is separated from each other.Sensing element is between first electrode and second electrode and covers first electrode and second electrode.
Sensing element includes conducting polymer and metal oxide.Conducting polymer has water-wet side.Metal oxide connection is led
The high molecular water-wet side of electricity.The metal oxide includes metallic oxide precursor object.
The present invention provides a kind of composite material of the sensing element suitable for sensor comprising conducting polymer and
Metal oxide.Conducting polymer has water-wet side and forms colloidal solid in a solvent.Metal oxide connects conductive polymer
The water-wet side of son.
The present invention provides a kind of manufacturing method of composite material, and its step are as follows.Conductive polymer with water-wet side is provided
Son.Metal oxide is added so that the metal oxide connects the water-wet side of the conducting polymer.The metal oxygen
Compound is by metallic oxide precursor object via obtained by dehydration, polymerisation, condensation reaction or combinations thereof.
Include conducting polymer and metal oxide, wherein metal oxide based on above-mentioned, of the invention composite material
It is connect with the water-wet side of conducting polymer.Therefore, composite material of the invention is in addition to good electrical conductivity, due to metal oxygen
Compound cover conducting polymer water-wet side, can make the water-wet side of conducting polymer be not easy in environment aqueous vapor and oxygen it is anti-
It answers, and then avoids the problem that conducting polymer deteriorates and coating is inconvenient.In addition, the composite material of the present invention can be applicable to sensing
In the sensing element of device, the resistance value of sensor can be effectively reduced and promote the sensitivity of sensor.
To make the foregoing features and advantages of the present invention clearer and more comprehensible, special embodiment below, and it is detailed to coordinate attached drawing to make
Carefully it is described as follows.
Description of the drawings
Figure 1A is according to a kind of schematic diagram of composite material shown in some embodiments of the invention.
Figure 1B is the close-up schematic view according to composite material shown in figure 1A.
Fig. 2A is according to a kind of schematic diagram of composite material shown in other embodiments of the invention.
Fig. 2 B are the close-up schematic views according to composite material shown in Fig. 2A.
Fig. 3 is that the section according to a kind of composite material shown in some embodiments of the invention for solar cell is illustrated
Figure.
Fig. 4 is the diagrammatic cross-section that sensor is used for according to a kind of composite material shown in some embodiments of the invention.
Fig. 5 is the bar chart of the resistance value of experimental example 1-3 and comparative example 1-3.
Fig. 6 A to Fig. 6 D are the optical microscope photograph of comparative example 1 and experimental example 1-3 respectively.
Specific implementation mode
Figure 1A is according to a kind of schematic diagram of composite material shown in some embodiments of the invention.Figure 1B is according to Figure 1A institutes
The close-up schematic view of the composite material shown.
Figure 1A and Figure 1B are please referred to, composite material 100 of the invention includes conducting polymer 110 and metal oxide
120.Details are as follows：
Conducting polymer 110 can be a kind of macromolecule with positive electricity and negative electricity, in other words, conducting polymer 110
With water-wet side and hydrophobic side.In some embodiments, with more on the Long carbon chain (it is with hydrophobicity) of conducting polymer 110
The functional group of a water-wet side 112, such as carboxyl (carboxylgroup), hydroxyl (hydroxyl group), sulfonic group
(sulfonic acid group), amido (amino group) or combinations thereof, however, the present invention is not limited thereto.For example, exist
In some embodiments, conducting polymer 110 is, for example, to be made of a kind of conducting polymer, on hydrophobic Long carbon chain
With multiple water-wet sides 112, water-wet side 112 can be connect with metal oxide 120.In further embodiments, conducting polymer
110 be, for example, to be made of two kinds of conducting polymers, and wherein Long carbon chain is by the conduction with multiple water-wet sides 112 on side chain
Macromolecule forms, and water-wet side 112 can be connect with another conducting polymer with multiple hydrophobic sides 114, also can be with metal oxygen
Compound 120 connects, however, the present invention is not limited thereto.
Specifically, conducting polymer 110 includes conjugated polymer and acid cosolvent.In one embodiment, described total
Yoke macromolecule is main conductive structure, can be for example poly- ethylenedioxythiophene (poly (3,4-
ethylenedioxythiophene)；PEDOT), polyphenylene sulfide (polyphenylene sulfide；PPS), polypyrrole
(polypyrrole；PPy), polythiophene (polythiophene；PT), polyaniline (polyaniline；PANI) or combinations thereof.
In addition, the acidity cosolvent can be for example polystyrolsulfon acid (poly (styrensulfonate)；PSS), acetic acid, propionic acid,
Butyric acid, benzoic acid or combinations thereof.In some embodiments, the conjugated polymer (such as PEDOT) be not readily dissolved in solvent (such as
Water) in, but it is added after the acid cosolvent (such as PSS), then may make (such as the PEDOT of conducting polymer 110:PSS)
It is scattered in aqueous solution in the form of colloidal solid (colloid).
In some embodiments, the dispersion of conducting polymer 110 can form colloidal solid in a solvent.The solvent includes pole
Property solvent, can be for example water, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, ethylene glycol, diethylene glycol (DEG), glycerine, propylene glycol, dipropyl
Glycol, tripropylene glycol or combinations thereof.Conducting polymer 110 be formed by colloidal solid diameter be, for example, between 10 nanometers extremely
Between 500 nanometers.In some embodiments, the weight average molecular weight (weight-average of conducting polymer 110
molecular weight；Mw) e.g. between 20000 grams/mol (g/mol) between 500000g/mol.
In one embodiment, conducting polymer 110 is, for example, PEDOT:PSS.In this embodiment, based on PEDOT
Want conductive structure.PSS is that p-type adulterates (p-type doping), and the water-wet side 112 on side chain is electronegative sulfonic group
(SO3 -).The electronegative sulfonic group of PSS makes the positively charged (S of PEDOT+), and with sulphur (S positively charged on PEDOT+) connection,
It can be connect with metal oxide 120.In this embodiment, PEDOT:The ratio of PSS is, for example, between 1：1 to 1：Between 10, but
The invention is not limited thereto.
Metal oxide 120 can cover the water-wet side 112 of conducting polymer 110.In some embodiments, metal aoxidizes
Object 120 is connected on the water-wet side 112 of conducting polymer 110, to cover water-wet side 112.In some embodiments, metal oxide
120 size (diameter or length) is smaller than conducting polymer 110.Such as titanium dioxide (the TiO of metal oxide 1202), dioxy
Change tin (SnO2), zinc oxide (ZnO), tungstic acid (WO3), iron oxide (Fe2O3), niobium pentaoxide (Nb2O5), tin indium oxide
(indiumtin oxide；ITO), indium sesquioxide (In2O3), strontium titanates (SrTiO3), nickel monoxide (NiO), vanadium oxide
(V2O5), molybdenum oxide (MoO3), magnesia, aluminium oxide or combinations thereof.
In one embodiment, metal oxide 120 be by metallic oxide precursor object via dehydration, polymerisation,
Obtained by condensation reaction or combinations thereof.In one embodiment, the metallic oxide precursor object can be solution form comprising
At least one metal ion and ligand.It specifically, can be (such as different by the metal ion (such as titanium) and the ligand
Propylate) metallic oxide precursor object (such as isopropyl titanate) be dissolved in solvent (auxiliary agent such as acid, alkali, oxidation containing auxiliary agent
Agent or combinations thereof, and solvent such as water) in, to form metallic oxide precursor object solution (such as titanium isopropoxide solution).Then,
Heating processing is carried out, by the dehydration of metallic oxide precursor object, is polymerized to metal oxide (such as titanium oxide).In an embodiment
In, by taking water as an example, the temperature of the heating processing is 20 DEG C to 90 DEG C；The time of the heating processing is 0.5 hour to 96 small
When.But invention is not limited thereto, and in alternative embodiments, the parameter (time or temperature) of heating processing depends on the kind of solvent
Class.
In one embodiment, the ligand includes that double tooth ligands (bidentate ligands) or alkoxide are matched
Position body (alkoxide ligands).The metal ion be selected from by Ba, Co, Cu, Fe, In, Ti, Sn, Sr, V, W, Zn, Mo,
At least one of the group that Nb, Ni, Mg, Al are formed element.Double tooth ligands are selected from by acetate
(acetate), acetyl pyruvate (acetylacetonate), carbonate (carbonate), oxalates (oxalate) institute group
At at least one of group ligand, the alkoxide ligand is selected from by methoxide (methoxide), ethylate
(ethoxide), propylate (propoxide), isopropoxide (isopropoxide), butylate (butoxide) are formed
At least one of group ligand.
The shape of metal oxide 120 is for example including graininess or fiber (fiber) shape.In some embodiments, please join
According to Figure 1A, the shape of metal oxide 120 is, for example, graininess.In metal oxide 120 is granular embodiment, metal
The diameter of oxide 120 is, for example, between 1 nanometer to 20 nanometers.In some embodiments, conducting polymer 110 is formed
The ratio of the diameter of colloidal solid and the diameter of metal oxide 120 is, for example, between 5：1 to 500：Between 1.In other realities
It applies in example, the ratio of the diameter for the colloidal solid that conducting polymer 110 is formed and the diameter of metal oxide 120 is, for example, 10：
1.That is, the diameter for the colloidal solid that conducting polymer 110 is formed is more than the diameter of metal oxide 120.In some realities
It applies in example, the diameter for the colloidal solid that conducting polymer 110 is formed can be more than 10 times or more of the diameter of metal oxide 120,
However, the present invention is not limited thereto.In one embodiment, conducting polymer 110 is, for example, PEDOT:PSS, the colloid formed
For example, about 33 nanometers of the diameter of grain, metal oxide 120 are, for example, titanium oxide, tungsten oxide, molybdenum oxide or vanadium oxide, diameter example
Such as from about 3 nanometers.That is, in this embodiment, the diameter for the colloidal solid that conducting polymer 110 is formed is aoxidized more than metal
10 times or more of the diameter of object 120, however, the present invention is not limited thereto.
Figure 1B is please referred to, the metal oxide 120 in composite material 100 of the invention connects the parent of conducting polymer 110
Water end (W.E.) 112.That is, by connecting metal oxide 120, the water-wet side 112 of conducting polymer 110 can be shielded
(block).In some embodiments, metal oxide 120 can cover all water-wet sides 112 of conducting polymer 110 and exposed
Hydrophobic side.In further embodiments, metal oxide 120 can connect the part water-wet side 112 of conducting polymer 110, conductive
Another part water-wet side 112 of macromolecule 110 is exposed, however, the present invention is not limited thereto.Conducting polymer 110 and metal oxide
120 molar ratio can according to demand (for example, contiguity of metal oxide 120 and the water-wet side of conducting polymer 110)
To adjust.For example, in some embodiments, the ratio of both conducting polymer 110 and metal oxide 120 weight percent
E.g. between 0.01：1 to 250：Between 1.In one embodiment, conducting polymer 110 is, for example, PEDOT:PSS, gold
It is, for example, vanadium oxide to belong to oxide 120, in this embodiment, in order to make the water-wet side of conducting polymer 110 all be aoxidized with metal
Object 120 connects, and with this condition, the ratio of both conducting polymer 110 and metal oxide 120 weight percent is, for example,
0.01：1 to 250：1, however, the present invention is not limited thereto.
Metal oxide 120 can be connect with the water-wet side of conducting polymer 110 112 in various ways, conductive high with masking
The water-wet side 112 of molecule 110.In some example embodiments, metal oxide 120 is, for example, to pass through hydrogen bond or chemical bonded refractory
(such as covalent bond) connects the water-wet side 112 of conducting polymer 110.In one embodiment, 120 (example of metal oxide
Such as, [- the V=O] on vanadium oxide) with the water-wet side of conducting polymer 110 (for example, the [- SO on PSS3 -]) generate covalent bond (example
Such as, [- V-O-SO2 -]) so that the water-wet side 112 of conducting polymer 110 is shielded (block), and reduce or can not with it is extraneous
Aqueous vapor and oxygen reaction.In other words, the metal oxide 120 of the present embodiment can prevent conducting polymer 110 and extraneous aqueous vapor
It is reacted with oxygen, and then avoids the problem that conducting polymer 110 deteriorates and coating is inconvenient.
Fig. 2A is according to a kind of schematic diagram of composite material shown in other embodiments of the invention.Fig. 2 B are according to Fig. 2A
Shown in composite material close-up schematic view.
Fig. 2A and Fig. 2 B are please referred to, composite material 200 includes conducting polymer 210 and metal oxide 220, conductive height
There is molecule 210 water-wet side 212 and hydrophobic side 214, metal oxide 220 to connect the water-wet side 212 of conducting polymer 210.
In this embodiment, place unlike the embodiments above is, the shape of metal oxide 220 is threadiness.In some embodiments
In, the ratio of the diameter of the colloidal solid of the formation of conducting polymer 210 and the length of metal oxide 220 is, for example, between 3：1
To 100：Between 1.In some example embodiments, the length of metal oxide 220 be, for example, between 5 nanometers to 500 nanometers it
Between.In some embodiments, the diameter for the colloidal solid that conducting polymer 210 is formed is more than the length of metal oxide 220.
In one example embodiment, the diameter for the colloidal solid that conducting polymer 210 is formed can be more than the 10 of the length of metal oxide 220
Times or more, however, the present invention is not limited thereto.In one embodiment, conducting polymer 210 is, for example, PEDOT:PSS is formed
Colloidal solid for example, about 33 nanometers of diameter, metal oxide 220 be, for example, titanium oxide, tungsten oxide, molybdenum oxide or vanadium oxide,
For example, about 14 nanometers of its length.That is, in this embodiment, the diameter example for the colloidal solid that conducting polymer 210 is formed
2.5 times or more of the length of metal oxide 220 in this way, however, the present invention is not limited thereto.
It is noted that the present invention composite material in, conducting polymer 110,210 integral composite 100,
Electrical conductivity needed for providing is provided in 200.For example, in some embodiments, conducting polymer 110,210 can carry
Rise the electrical conductivity of integral composite 100,200.In one embodiment, the sheet resistance values example of conducting polymer 110,210
In this way between 200 ohm/ to 3000 ohm/, the sheet resistance values of metal oxide 120,220 are, for example, between 200K
Between ohm/ to 200M ohm/, the sheet resistance values of integral composite 100,200 be, for example, between 30 ohm/ extremely
Between 600 ohm/, however, the present invention is not limited thereto.
On the other hand, in the composite material 100,200 of the present invention, conducting polymer 110,210 is in integral composite
100, have the function of in 200 maintaining or adjusting work function.For example, in some embodiments, conducting polymer 110,210
It can maintain the work function of integral composite 100,200.In some embodiments, the work content numerical example of conducting polymer 110,210
In this way between 4.8eV between 5.2eV, the work function of metal oxide 120,220 is, for example, between 5.2eV between 5.7eV,
The work function of integral composite 100,200 for example can therebetween, e.g. between 5.0eV between 5.6eV, but this
It invents without being limited thereto.In other words, metal oxide 120,220 can also adjust the work function of integral composite 100,200, make
It reaches desired numerical value.
The forming method of above-mentioned composite material 100,200 is, for example, by metal oxide or its predecessor and conducting polymer
It with aforementioned revealed ratio, is uniformly mixed in solvent, generates conducting polymer-metal oxide composite.At some
In embodiment, the solvent includes polar solvent, can be for example water, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, ethylene glycol,
Diethylene glycol (DEG), glycerine, propylene glycol, dipropylene glycol, tripropylene glycol or combinations thereof.Hybrid mode includes rocking, stirring, and can further include applying
The modes such as heating or ultrasonic wave assist to mix.Specifically, the conduction of the metal oxide of solution shape and solution shape is high
Molecular mixing is uniform.In one embodiment, the hybrid mode may include shaking using vortex blender (vortex mixer)
Mixing is mixed using gyratory shaker (rotator mixer) rotation, utilizes pipe roller mixing machine (tube roller mixer)
Roller bearing mixing, using linear/orbital shaker (linear/orbital shaker) or shaking rock machine (rock shaker) vibrates
Mixing is stirred using DC blenders (DC-Stirrer), or is stirred using magnetite.In one embodiment, it mixes
At least 1 second or more time；Mixing temperature is between 4 DEG C to 80 DEG C.
In addition, in the composite material of the present invention, since metal oxide covers the water-wet side of conducting polymer, can make to lead
The high molecular water-wet side of electricity be not easy in environment aqueous vapor and oxygen react, and then conducting polymer is avoided to deteriorate and be coated with not
Just the problem of.Also, the water-wet side due to conducting polymer is shielded, the whole more original conducting polymer of composite material can be made in thin
It is aqueous, and then improve the adhesion of the composite material and hydrophobic material of the present invention.Furthermore in the composite material of the present invention,
Conducting polymer is between metal oxide.That is, metal oxide dispersion is between conducting polymer, and make metal
Oxide is not easy to assemble.Therefore, it can avoid the problem caused by aggregated metal oxide.Specifically, due to metal oxygen
The phenomenon that materialization is reunited is reduced, and can promote the film-forming quality of integral composite, therefore can be reduced surface roughness, be reduced surface holes
Gap (pinhole) etc., and then can avoid the problems such as electric leakage or point discharge in extra electric field.
It is wet for spray printing (ink-jet), aerosol injection (aerosol-jet) etc. based on above-mentioned, of the invention composite material
The 3D printing technique of formula processing procedure uses, and can be applied to plastic rubber substrate in the form of conductive material or sensing material, such as including
Polyethylene terephthalate (PET), polyimides (PI), polyvinyl chloride (PVC), is gathered at polyethylene naphthalate (PEN)
The substrates such as propylene (PP), cyclic olefin polymer (COP) or polyethylene (PE).
In addition, the composite material of the present invention can also be applied to organic photoelectric semiconductor element, such as organic solar batteries,
Organic Light Emitting Diode etc..For example, composite material of the invention can be used as the electrons or holes buffer layer of solar cell
(buffer layer).It will be described the embodiment that the composite material of the present invention is applied to solar cell, but the present invention below
The application of composite material be not limited to this.
Fig. 3 is that the section according to a kind of composite material shown in some embodiments of the invention for solar cell is illustrated
Figure.
Fig. 3 is please referred to, solar cell 300 can include sequentially substrate 310, the first conductive layer 320, active layer (active
Layer) 330 and second conductive layer 340, wherein the first conductive layer 320 further includes electrode layer 322 and buffer layer 324.In detail
For, the first surface 310a of substrate 310 is the plane of incidence of light 302, the first conductive layer 320 (including electrode layer 322, buffer layer
324), active layer 330 and the second conductive layer 340 are then sequentially arranged second opposite with the first surface 310a of substrate 310
On the 310b of surface.
In some embodiments, substrate 310 is, for example, transparent substrate.The material of substrate 310 is for example including glass, transparent tree
Fat or other suitable materials.Please continue to refer to Fig. 3, active layer 330 is located on buffer layer 324.In some embodiments, active
The material of layer 330 is for example including polythiophene (poly (3-hexylthiophene)；P3HT)、([6,6]-phenyl-C61-
butyric acid method ester；PCBM) etc..Second conductive layer 340 is located on active layer 330.In some embodiments
In, the material of the second conductive layer 340 is for example including metal.Metal is, for example, gold, silver, copper, aluminium, titanium etc., but the present invention is not limited to
This.
First conductive layer 320 is between substrate 310 and active layer 330.First conductive layer 320 include electrode layer 322 with
And buffer layer 324.That is, in this embodiment, electrode layer 322 is located on the second surface 310b of substrate 310, buffer layer
324 between electrode layer 322 and active layer 330.The material of electrode layer 322 is for example including indium tin oxide (indium tin
oxide；ITO), indium-zinc oxide (indium zinc oxide；IZO) etc., however, the present invention is not limited thereto.In the present embodiment
The material of buffer layer 324 may be used the composite material 100 or 200 in the above embodiment of the present invention and (please refer to Figure 1A or figure
2A).The forming method of buffer layer 324, which may be used, e.g. passes through method of spin coating.The composite material of the present invention is applied to
In the buffer layer 324 of solar cell 300, it is possible to provide good electrical conductivity and required work function are suitable for transmitting electric hole (or electricity
Son).On the other hand, since the metal oxide in composite material covers the water-wet side of conducting polymer, material settling out can be promoted
Property, be conducive to coating, and can Promoting Layered Buffer layer 324 and hydrophobic material adhesion.Also, due to the metal oxidation in composite material
Object is scattered between conducting polymer, therefore be can avoid electric leakage or point discharge etc. caused by aggregated metal oxide and asked
Topic.
Above-described embodiment is the electroconductive polymer layer applied to solar cell by the composite material of the present invention, but of the invention
It is without being limited thereto.The composite material of the present invention is also applicable in sensor.
Fig. 4 is the diagrammatic cross-section that sensor is used for according to a kind of composite material shown in some embodiments of the invention.
Please refer to Fig. 4, the sensor 400 of the present embodiment include substrate SUB, first electrode 402, second electrode 404 and
Sensing element 406.In one embodiment, substrate SUB can be silicon substrate, glass substrate, have silicon (SOI) base on insulating layer
Plate, circuit base plate, plastic rubber substrate above-mentioned or combinations thereof.
As shown in figure 4, first electrode 402 is configured with second electrode 404 on substrate SUB.In detail, first electrode
402 are separated from each other with second electrode 404 and do not contact with each other.In the present embodiment, first electrode 402 can with second electrode 404
It is configured to fourchette type electrode, but the present invention does not limit the shape of first electrode 402 and second electrode 404, as long as first electrode 402
With second electrode 404 can at a distance of a preset distance, to be separated from each other and do not contact with each other be all scope of the invention.Implement substituting
In example, first electrode 402 also can be for example stack electrode with second electrode 404.The setting of three-dimensional stack electrode can have
Effect increases the density of sensor, and reduces integral member volume.In detail, stack electrode can be by multiple electrodes layer with
Multiple dielectric layer (not shown) are vertical and are alternately stacked on substrate SUB.That is, at least a dielectric layer is configured at adjacent two
Between a electrode layer, to electrically isolate two neighboring electrode layer.In one embodiment, above-mentioned electrode layer includes conductor material.It leads
Body material can be doped or undoped polycrystalline silicon material, metal material or combinations thereof.The material of above-mentioned dielectric layer can be
Silica, silicon nitride or combinations thereof.
In one embodiment, in gap of the sensing element 406 between first electrode 402 and second electrode 404 and
Extend over the top surface of first electrode 402 and second electrode 404.Although sensing element 406 shown in Fig. 4 does not cover completely
The all surface of lid first electrode 402 and second electrode 404, but invention is not limited thereto.In other embodiments, material is sensed
The all surface of first electrode 402 and second electrode 404 can be also completely covered in the bed of material 406 (it includes top surface and side).It is worth
It is noted that when the surface of determinand absorption or sensing contact material layer 406, determinand can be carried out with sensing element 406
Reaction so that the electrical characteristics such as capacitance or resistance value of the sensing element 406 between first electrode 402 and second electrode 404
Change.Then, user can by the electrical characteristics such as the capacitance having changed or resistance value come calculate determinand type or
It is Parameters variation amount.
In one embodiment, sensing element 406 can be gas sensing layer, light sensing layer, humidity layer, temperature sensing
Layer or combinations thereof.In other words, the sensor 400 of the present embodiment can be used to sense gasses, light, humidity, temperature or combinations thereof.
In one embodiment, the forming method of sensing element 406 can be for example contactless print process.In an embodiment
In, contactless print process includes ink jet printing method or aerosol spraying print process.By taking aerosol spraying print process as an example, it is
Using the molten nozzle deposition head of gas (aerosol jet deposition head), to be formed by external sheath stream (outer
Sheath flow) and internal carrier current (the inner aerosol-laden carrier flow) composition molten full of gas
Ring-type propagates nozzle.In the molten injection processing procedure of cyclic annular gas, the molten stream (aerosol stream) of the gas with sensing material is concentrated
And it is deposited on plane or nonplanar substrate SUB.Then, through Overheating Treatment or photochemical treatment, to form sensing element
406.Above-mentioned steps can be described as no mask mesoscale material deposition (Maskless Mesoscale Material
Deposition, M3D), that is to say, that it can be deposited without using mask so that post-depositional material layer
With the line width (linewidth) between 1 micron to 1000 microns.
In one embodiment, the material of sensing element 406 is above-mentioned composite material 100,200.Above-mentioned composite material
100,200 composition and forming step are described in detail in above-mentioned paragraph, are just repeated no more in this.
It is worth noting that, in one embodiment, by above-mentioned composite material 100,200 come as sensing element 406,
Conducting polymer in composite material 100,200 can reduce the resistance value of sensing element 406, to increase the sensitive of sensor 400
Degree.Compared to existing sensor (its only with metal oxide as sensing element, and need to high temperature (such as 200 DEG C extremely
400 DEG C) under could be sensed), the sensor 400 of the present embodiment can be sensed under room temperature (such as 0 DEG C to 50 DEG C).Cause
This, the sensor 400 of the present embodiment can be applied on most electronic product (such as mobile phone), the case where without having overheat simultaneously
The power consumption being greatly decreased simultaneously (it is from high-temperature heating).
On the other hand, in one embodiment, the metal oxide in composite material 100,200 can cover conducting polymer
Water-wet side to prevent conducting polymer from being reacted with extraneous aqueous vapor and oxygen, and then avoids conducting polymer from deteriorating and be coated with
Inconvenient problem.Thus, which the present embodiment can extend the service life of the sensing element with conducting polymer, and can lead to
Sensing element is coated on surface (namely the water-wetted surface or hydrophobic of any material by the content for crossing adjustment metal oxide
Surface) on.Thereby increase the use scope of sensing element.
Hereinafter, enumerating the experimental example of the present invention so that more specifically the present invention will be described.However, not departing from the present invention's
Spirit can suitably change material, application method etc. shown in experimental example below.Therefore, the scope of the present invention
It should not carry out limited interpretation with experimental example as shown below.
Experimental example 1
In experimental example 1, using vortex blender, by PEDOT:PSS (it is bought from Heraeus Inc.) is aoxidized with metal
Object is uniformly mixed, to be coated on fourchette type electrode, wherein the mixed PEDOT:The weight of PSS and the metal oxide
It is 1 to measure percentage:1.It (is, for example, Molybdenyl that the metal oxide, which is by the predecessor of metal oxide,
Acetylacetonate it) is configured to the alcohol solution (being, for example, isopropanol) of a concentration of 0.1-10wt%, and heats 40-80 DEG C,
And sustained response forms for 0.05-96 hours.Then, it is dried, in forming sensing element on the fourchette type electrode.Institute
State drying time 10 seconds to 1800 seconds, and drying temperature is between 20 DEG C to 200 DEG C.Then, the sensing material of experimental example 1 is measured
The resistance value of the bed of material, the results are shown in Figure 5.
Experimental example 2,3
In experimental example 2,3, with the step of above-mentioned experimental example 1 in being respectively formed sensing element on fourchette type electrode.With
Experimental example 1 the difference is that：The PEDOT of experimental example 2:The weight percent of PSS and metal oxide is 2.25:1.Experimental example
3 PEDOT:The weight percent of PSS and metal oxide is 6:1.Then, the sensing element of experimental example 2,3 is measured respectively
Resistance value, the results are shown in Figure 5.
Comparative example 1
In comparative example 1, by the PEDOT of 1.0wt%:PSS (it is bought from Heraeus Inc.) is coated on fourchette type electrode
On.Then, it is dried, in forming sensing element on the fourchette type electrode.The drying time 10 seconds to 1800 seconds,
And drying temperature is between 20 DEG C to 200 DEG C.Then, the resistance value of the sensing element of comparative example 1 is measured, result is as schemed
Shown in 5.
Comparative example 2
In comparative example 2, by metal oxide solution (it is bought from Sigma-Aldrich companies) coating of 1.0wt%
On fourchette type electrode.Then, it is dried, in forming sensing element on the fourchette type electrode.The drying time
10 seconds to 1800 seconds, and drying temperature is between 20 DEG C to 200 DEG C.Then, the resistance of the sensing element of comparative example 2 is measured
Value, the results are shown in Figure 5.
Comparative example 3
In comparative example 3, the metal oxide solution of 1wt% is coated on fourchette type electrode.The metal oxide
Solution is that the predecessor (being, for example, Molybdenyl acetylacetonate) of metal oxide is configured to a concentration of 0.1-
The alcohol solution (being, for example, isopropanol) of 10wt%, and 40-80 DEG C is heated, and sustained response forms for 0.05-96 hours.Then,
It is dried, in forming sensing element on the fourchette type electrode.The drying time 10 seconds to 1800 seconds, and dry temperature
Degree is between 20 DEG C to 200 DEG C.Then, the resistance value of the sensing element of comparative example 3 is measured, the results are shown in Figure 5.
As shown in figure 5, compared to comparative example 2,3, it is added with conducting polymer (PEDOT:PSS)
The sensing element of experimental example 1-3 has lower resistance value.In addition, compared to the only PEDOT of comparative example 1:
The sensing element of PSS, conducting polymer (PEDOT:PSS) have with the combination of metal oxide (molybdenum oxide) plus multiply effect
(synergism), to provide lower resistance value.In addition, in experimental example 1-3, with conducting polymer (PEDOT:PSS)
Content increases, and the electrical conductivity of sensing element also decreases, and then promotes the sensitivity of sensor.
Fig. 6 A to Fig. 6 D are the optical microscope photograph of comparative example 1 and experimental example 1-3 respectively.
As shown in Figure 6A, in comparative example 1, only with metal oxide as sensing element, therefore, comparative example 1
Sensing element is easily molded and easy cracking.By Fig. 6 B to Fig. 6 D it is found that with conducting polymer (PEDOT:PSS content)
Increase, be formed by the easier molding of sensing element and be not easily cracked.That is, being added in sensing element conductive high
Molecule not only facilitates the resistance value for reducing sensing element, can also sensing element be made not to be easily cracked.
In conclusion the composite material of the present invention includes conducting polymer and metal oxide, wherein metal oxide
It is connect with the water-wet side of conducting polymer.Therefore, composite material of the invention is in addition to good electrical conductivity and work function,
Since metal oxide covers the water-wet side of conducting polymer, the water-wet side of conducting polymer can be made to be not easy and the aqueous vapor in environment
It is reacted with oxygen, and then avoids the problem that conducting polymer deteriorates and coating is inconvenient.Furthermore it is hydrophilic due to conducting polymer
Hold shielded, it is in hydrophobicity that can make the whole more original conducting polymer of composite material, and then improves composite material and hydrophobicity material
The adhesion of material.In addition, the combination of the conducting polymer and metal oxide in the composite material of the present invention has plus multiplies effect,
It can be applicable in the sensing element of sensor, to be effectively reduced the resistance value of sensor and promote the sensitive of sensor
Degree.In addition, conducting polymer is added in sensing element, the resistance value for reducing sensing element is not only facilitated, also may be used
So that sensing element is not easily cracked, and then promotes the reliability of sensor.
Although the present invention is disclosed as above with embodiment, however, it is not to limit the invention, any technical field
Middle technical staff, without departing from the spirit and scope of the present invention, when can make a little change with retouching, therefore the present invention protection
Range is when subject to the attached claims institute defender.
Claims (13)
1. a kind of sensor, which is characterized in that including：
First electrode；
Second electrode is separated from each other with the first electrode；And
Sensing element between the first electrode and the second electrode and covers the first electrode and described second
Electrode, wherein the sensing element includes：
Conducting polymer has water-wet side；And
Metal oxide connects the water-wet side of the conducting polymer, wherein the metal oxide includes metal oxidation
Object predecessor.
2. sensor according to claim 1, which is characterized in that the first electrode is configured to refer to the second electrode
Forked type electrode, stack electrode or combinations thereof.
3. sensor according to claim 1, which is characterized in that the sensing element is with contactless print process institute shape
At.
4. sensor according to claim 3, which is characterized in that the contactless print process include ink jet printing method or
Aerosol spraying print process.
5. a kind of composite material, which is characterized in that including：
Conducting polymer forms with water-wet side and in a solvent colloidal solid；And
Metal oxide connects the water-wet side of the conducting polymer.
6. composite material according to claim 5, which is characterized in that the metal oxide includes metallic oxide precursor
Object, the metallic oxide precursor object include at least one metal ion and ligand, and the ligand includes double tooth ligands
Or alkoxide ligand.
7. composite material according to claim 6, which is characterized in that the metal ion be selected from by Ba, Co, Cu, Fe,
At least one of the group that In, Ti, Sn, Sr, V, W, Zn, Mo, Nb, Ni, Mg, Al are formed element, double tooth ligands
It is described selected from least one of the group being made of acetate, acetyl pyruvate, carbonate, oxalates ligand
Alkoxide ligand is selected from by methoxide, ethylate, propylate, isopropoxide, in the group that butylate is formed extremely
A kind of few ligand.
8. composite material according to claim 5, which is characterized in that the conducting polymer includes conjugated polymer and acid
Property cosolvent, the conjugated polymer includes poly- ethylenedioxythiophene, polyphenylene sulfide, polypyrrole, polythiophene, polyaniline or its group
It closes, the acidity cosolvent includes polystyrolsulfon acid, acetic acid, propionic acid, butyric acid, benzoic acid or combinations thereof.
9. composite material according to claim 5, which is characterized in that the metal oxide includes titanium dioxide, dioxy
Change tin, zinc oxide, tungstic acid, iron oxide, niobium pentaoxide, tin indium oxide, indium sesquioxide, strontium titanates, nickel monoxide, oxygen
Change vanadium, molybdenum oxide, magnesia, aluminium oxide or combinations thereof.
10. composite material according to claim 5, which is characterized in that the conducting polymer and the metal oxide
Weight percent between 0.01：1 to 250：Between 1.
11. composite material according to claim 5, which is characterized in that the solvent includes polar solvent, and the polarity is molten
Agent includes water, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, ethylene glycol, diethylene glycol (DEG), glycerine, propylene glycol, dipropylene glycol, 3 the third two
Alcohol or combinations thereof.
12. composite material according to claim 5, which is characterized in that the metal oxide be by hydrogen bond or covalently
Key connects the water-wet side of the conducting polymer.
13. a kind of manufacturing method of composite material, which is characterized in that including：
Conducting polymer is provided, with water-wet side；And
Metal oxide is added so that the metal oxide connects the water-wet side of the conducting polymer, wherein described
Metal oxide is by metallic oxide precursor object via obtained by dehydration, polymerisation, condensation reaction or combinations thereof.
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| CN110564112A (en) * | 2019-09-26 | 2019-12-13 | 河南工程学院 | Oriented nickel oxide/PEDOT composite material and preparation method thereof |
| TWI775327B (en) * | 2021-02-25 | 2022-08-21 | 新唐科技股份有限公司 | Temperature sensitive three-electrode gas sensor |
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