CN102983270B - Polymer function device - Google Patents

Polymer function device Download PDF

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CN102983270B
CN102983270B CN201210472738.9A CN201210472738A CN102983270B CN 102983270 B CN102983270 B CN 102983270B CN 201210472738 A CN201210472738 A CN 201210472738A CN 102983270 B CN102983270 B CN 102983270B
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piezoelectric
function device
ion
electrode
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CN102983270A (en
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梅欣
张俊
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LIYANG PRODUCTIVITY PROMOTION CENTER
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LIYANG PRODUCTIVITY PROMOTION CENTER
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Abstract

The invention discloses a polymer function device which comprises a first electrode layer, a first piezoelectric layer, a first transition layer, an ion exchange enhancement layer, a second transition layer, a second piezoelectric layer and a second electrode layer, wherein the first electrode layer, the first piezoelectric layer, the first transition layer, the ion exchange enhancement layer, the second transition layer, the second piezoelectric layer and the second electrode layer are stacked sequentially. The first electrode layer and the second electrode layer have different work functions. The ion exchange enhancement layer comprises ion exchange enhancement materials and nanometer conductive particles. The first transition layer and the second transition layer are polytrifluorohloroethylene, polytetrafluoroethylene or polyvinyl alcohol. A novel piezoelectric polymer material is used for forming the piezoelectric layer, and the electrostriction strain is increased by 5-7% compared with that of piezoelectric elements of common piezoelectric polymers in the prior art.

Description

A kind of polymers function device
Technical field
The present invention relates to a kind of function element.
Background technology
Function element obtains the increasing research of people and uses.Piezoelectric element is as a kind of common function device, and it is converted to pressure the element of the signal of telecommunication, and it comprises piezoelectric material layer and is positioned at the electrode layer of these piezoelectric material layer both sides.In the time exerting pressure on this piezoelectric element surface, can corresponding signal of telecommunication output be detected at this two electrode layer.This piezoelectric material layer is made up of the material with piezoelectric effect, and in prior art, comparatively conventional piezoelectric is piezoelectric ceramic, as barium titanate, lead titanates and pick lead titanates etc., and piezopolymer, as Kynoar (PVDF) etc.
Kynoar and copolymer thereof are as modal organic piezopolymer.Because they have good pliability and easily make large-area film, thereby there is important application prospect in audio frequency and sonac, biomedical transducer, electromechanical transducer and pyroelectricity and optics.But its actuation capability is low, under 150MV/m electric field, its Electrostrictive strain is only 7%.Therefore, this area researcher wishes to find the piezopolymer that can replace Kynoar that improves Electrostrictive strain, improves the performance of piezoelectric device.
Summary of the invention
The invention discloses a kind of polymers function device, it comprises the first electrode layer, the first piezoelectric layer, the First Transition layer that stack gradually, ion-exchange enhancement layer, the second transition zone, the second piezoelectric layer and the second electrode lay, wherein,
The first electrode layer has different work functions from the second electrode lay, and ion-exchange enhanced layer packets is containing ion-exchange reinforcing material and conductive nano particle; Ion-exchange reinforcing material is polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol, and conductive nano particle is carbon nano-tube, Graphene or metal nanoparticle; First Transition layer and the second transition zone are polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol;
Piezoelectric layer is mixed to form by piezopolymer and binding agent;
This piezopolymer is for having the material of chemical structural formula (I);
Wherein
N and m are respectively for being greater than 1 integer;
P is 0 or is greater than 1 integer;
X and Z be the C for being substituted or being unsubstituted respectively 4-C 60aromatic series unit or aliphat unit;
Y is the C that is substituted or is unsubstituted 2-C 40aliphat unit; With
G 1, G 2, G 3and G 4the respectively C for being substituted or being unsubstituted 1-C 12fatty group.
The invention has the beneficial effects as follows: form piezoelectric layer with novel polymeric piezoelectric material, prepared novel piezoelectric element.This piezoelectric element is mutually stacked by having metal and the piezopolymer of different work functions, does the used time when being under pressure, and this piezoelectric layer has different Schottky contacts from the first electrode layer and the second electrode lay, thereby produces electrical potential difference.The Electrostrictive strain of this piezoelectric element improves 5～7% than the piezoelectric element using Kynoar as piezopolymer.
Brief description of the drawings
Fig. 1 is the structural representation of polymers function device of the present invention.
Embodiment
In order to make those skilled in the art more clearly understand technical scheme of the present invention, describe polymers function device of the present invention and manufacture method thereof in detail below with reference to accompanying drawing.
As shown in Figure 1, polymers function device of the present invention comprises the first electrode layer 1, the first piezoelectric layer 2, First Transition layer 3, ion-exchange enhancement layer 4, the second transition zone 5, the second piezoelectric layer 6 and the second electrode lay 7 that stack gradually.Ion-exchange enhancement layer 4 is arranged between First Transition layer 3 and the second transition zone 5, First Transition layer 3, the first piezoelectric layer 2 and the first electrode layer 1 from inside to outside successively from a surface of ion-exchange enhancement layer 4, be the second transition zone 5, the second piezoelectric layer 6 and the second electrode lay 7 from inside to outside successively from another surface of ion-exchange enhancement layer 4, form seven laminatings and close the stacked structure that arranges.
The material of the first piezoelectric layer 2 and the second piezoelectric layer 6 includes the have chemical structural formula material of (I);
N and m are respectively for being greater than 1 integer;
P is 0 or is greater than 1 integer;
X and Z be the C for being substituted or being unsubstituted respectively 4-C 60aromatic series unit or aliphat unit;
Y is the C that is substituted or is unsubstituted 2-C 40aliphat unit; And G 1, G 2, G 3and G 4the respectively C for being substituted or being unsubstituted 1-C 12fatty group.
Preferably, n and m are respectively 5 to 600 integer, and more preferably n and m are respectively 10 to 300 integer.
Preferably, p is 0 or 1 to 300 integer, and more preferably p is 5 to 150 integer.
Preferably, the respectively C for being substituted or being unsubstituted of X and Z 6-C 40aromatic series unit or aliphat unit.
Preferably, Y is the C that is substituted or is unsubstituted 3-C 20aliphat unit; Preferably, Y is the C that is substituted or is unsubstituted 4-C 12hydrocarbon chain or C 4-C 12dioxygen alkyl, more preferably, Y is dioxygen butyl.
Preferably, G 1, G 2, G 3and G 4the respectively C for being substituted or being unsubstituted 1-C 6fatty group, the methyl that is more preferably substituted or is unsubstituted, ethyl, propyl group, butyl, methoxyl group, ethyoxyl or propoxyl group, more preferably methyl.
The first piezoelectric layer 2 and the second piezoelectric layer 6 can also comprise a small amount of binding agent, and piezoelectric layer is better combined with electrode layer and ion-exchange enhancement layer and moulding.This polymeric piezoelectric material accounts for the more than 90% of piezoelectric layer 2 gross masses, is preferably more than 95%.
In one embodiment, this piezoelectric layer 2 comprises and accounts for total weight than 97% polymeric piezoelectric material, and accounts for total weight than 3% binding agent.
In one embodiment, this binding agent is PAN.The thickness of this piezoelectric polymer layer 2 is 10～300 microns, is preferably 100～200 microns.In one embodiment, the thickness of this piezoelectric polymer layer 2 is about 150 microns.
Ion-exchange enhancement layer 4 is to adopt ion-exchange reinforcing material to obtain solution curing molding to make, and it is in ion-exchange reinforcing material, evenly to add conductive nano particle that ion-exchange strengthens solution;
Ion-exchange reinforcing material is preferably polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol.Conductive nano particle is carbon nano-tube, Graphene or metal nanoparticle.
First Transition layer 3 and the second transition zone 5 are polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol.Its thickness is preferably 15～20 microns.
The work function of metal that forms the first electrode layer 1 is unequal with the work function of metal that forms the second electrode lay 5.Preferably, the work function difference of the metal of the work function of the metal of the first electrode layer 1 and the second electrode lay 5 is larger, more than preferably differing 0.5eV.First electrode layer 1 with different work functions and the second electrode lay 5 and the first piezoelectric layer 2 and the second piezoelectric layer 4 are mutually stacked, do the used time when being under pressure, the inner separation of charge that produces of piezoelectric layer, because this polymeric piezoelectric material has different Schottky contacts from the metal of different work functions, thereby produce electrical potential difference and electric current.The first electrode layer 1 is larger with the work function difference of the metal of the second electrode lay 5, and the electrical potential difference producing is larger.Owing to being provided with ion-exchange enhancement layer 3 between the first piezoelectric layer 2 and the second piezoelectric layer 4, can significantly improve electrical potential difference and electric current.
Preferably, the first electrode layer 1 can be aluminium/copper (Al/Cu) with the material of the second electrode lay 3, the combination of aluminium/nickel (Al/Ni), aluminium/gold (Al/Au), zinc/gold (Zn/Au).In one embodiment, the material of the first electrode layer 1 is Al, its work function 4.28eV, and the material of the second electrode lay 3 is Au, its work function 5.1eV.
The first electrode layer 1 and the second electrode lay 3 can be tinsel or metallic film, or are respectively tinsel and metallic film.This tinsel can with these piezoelectric polymer layer 2 phase pressings, this metallic film can be by electroplating or the method such as deposition is directly formed at the surface of this piezoelectric polymer layer 2.The thickness of this tinsel is preferably 200～1000 microns.The thickness of this metallic film is preferably 10～200 microns.In one embodiment, the first electrode layer 1 and the second electrode lay 3 are the tinsel that thickness is about 0.5 millimeter.
First embodiment of the invention provides a kind of polymers function device, the especially manufacture method of polymer piezo element, and it comprises the following steps:
The first, prepare polymeric piezoelectric material, and this polymeric piezoelectric material is heated 1 hour to 5 hours at 160～190 DEG C, make its decomposes.Preferably, heating-up temperature is 180 DEG C, and be 3 hours heating time.
The second, this piezopolymer and binding agent and volatile solvent are formed to a slurry.This piezopolymer mixes as the ratio of 90: 10 to 99: 1 taking mass ratio with this binding agent, is preferably 97: 3.This volatile solvent makes this slurry have certain mobility, is easy to film.This volatile solvent can be ethanol, methyl alcohol or acetone and other organic solvent.In the present embodiment, by 9.7 grams of these piezopolymers and 0.3 gram of acrylonitrile, and add 10 milliliters of dimethyl formamides, in mortar, fully mix.
The 3rd, this slurry is coated on to the first electrode layer 1 surface, form the first piezoelectric layer 2.The thickness of this piezoelectric layer 2 is preferably 10～300 microns.In the present embodiment, can use scraper that described slurry is coated on to aluminium foil surface, the thickness of the first piezoelectric layer 2 forming is about 150 microns.
The 4th, dry this first piezoelectric layer 2, makes solvent evaporates.Particularly, the first electrode layer 1 can be positioned over to heat drying in a baking oven together with this first piezoelectric layer 2.The temperature of this baking oven can be 40 DEG C～80 DEG C, and can be 2～5 hours drying time.In the present embodiment, baking temperature is 50 DEG C, and be 4 hours drying time.
The 5th, at the first piezoelectric layer 2 surface-coated First Transition layers 3, the material of First Transition layer 3 is polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol.Particularly, after being mixed with to solution, polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol be coated in the first piezoelectric layer 2 surfaces, and dry.
The 6th, at these the first piezoelectric layer 2 surface-coated ion-exchange enhancement layers 4.The method of preparation ion-exchange enhancement layer is: by ion-exchange reinforcing material and solvent, solvent is preferably ethanol or water, the ion-exchange reinforcing material solution that to obtain to mass percent concentration be 25～50%, the bubble in solution is removed in ultrasonic concussion, conductive nano particle is added in solution, the shared mass percent of conductive nano particle wherein adding is preferably 6～10%, ultrasonic concussion is uniformly dispersed and obtains ion-exchange enhancing solution, and wherein the ultrasonic concussion time is preferably 200～500 minutes.
Seven, be polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol at the material of ion-exchange enhancement layer 4 surface-coated the second transition zone 5, the second transition zones 5.Particularly, after being mixed with to solution, polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol be coated in ion-exchange enhancement layer 4 surfaces, and dry.
The 8th, the slurry mixing in above-mentioned second step is coated on to the second transition zone 5 surfaces, form the second piezoelectric layer 6.The thickness of this second piezoelectric layer 6 is preferably 10～300 microns.In the present embodiment, can use scraper that described slurry is coated on to aluminium foil surface, the thickness of the second piezoelectric layer 6 forming is about 150 microns.
The 9th, dry this second piezoelectric layer 6, makes solvent evaporates.Particularly, above-mentioned laminated construction can be positioned over to heat drying in a baking oven.The temperature of this baking oven can be 40 DEG C～80 DEG C, and can be 2～5 hours drying time.In the present embodiment, baking temperature is 50 DEG C, and be 4 hours drying time.
The tenth, the second electrode lay 7 is covered in to these the second piezoelectric layer 6 surfaces and is laminated.In the present embodiment, the second electrode lay 7 is goldleaf.Particularly, the second electrode lay 7 can be covered behind these the second piezoelectric layer 6 surfaces, use roll that the first electrode layer 1, the first piezoelectric layer 2, First Transition layer 3, ion-exchange enhancement layer 4, the second transition zone 5, the second piezoelectric layer 6 and the second electrode lay 7 are fitted tightly.
The piezoelectric element that method by the first embodiment is formed accesses the piezoelectric effect of testing this piezoelectric element in a loop, and wherein, the load resistance R in this loop is 4.0 × 10 6ohm (Ω), the size of this piezoelectric element is 20 × 20 millimeters.When the pressure being subject to when this piezoelectric element surface increases in time gradually, the magnitude of voltage that can record this load resistance R two ends constantly increases, and concrete data are as shown in table 1.After this pressure continues for some time, this magnitude of voltage declines very slowly, and sustainable reach a few hours more than.In the time that pressure increases or reduces, this voltage changes rapidly with the variation of pressure.Be respectively 4,000 Ns and 60,000 Ns during when being under pressure, the power output of this piezoelectric element is 0.9nW and 8nw.
Table 1
This device is mutually stacked by having metal and the piezoelectric polymer layer of different work functions, do the used time when being under pressure, the inner separation of charge that produces of this piezopolymer, because it has different Schottky contacts from the metal of different work functions, thereby produces electrical potential difference and electric current.Through measuring, the Electrostrictive strain of this piezoelectric element improves 5～7% than the piezoelectric element using Kynoar as piezopolymer.
Polymer piezo device of the present invention can, for sonac, biomedical transducer and transducer etc., have broad application prospects aspect machinery, medical treatment, completion.
Be appreciated that; be only the preferred embodiments of the present invention; can not limit scope of the invention process with this; those skilled in the art in spirit of the present invention can to its make various modification or; the variation that these are done according to spirit of the present invention, all should be included in the present invention's scope required for protection.

Claims (6)

1. a polymers function device, is characterized in that, described polymers function device comprises the first electrode layer, the first piezoelectric layer, the First Transition layer that stack gradually, ion-exchange enhancement layer, the second transition zone, the second piezoelectric layer and the second electrode lay, wherein,
The first electrode layer has different work functions from the second electrode lay, more than the work function of the first electrode layer and the second electrode lay work function differ 0.5eV;
Ion-exchange enhanced layer packets is containing ion-exchange reinforcing material and conductive nano particle; Ion-exchange reinforcing material is polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol, and conductive nano particle is carbon nano-tube, Graphene or metal nanoparticle;
First Transition layer and the second transition zone are polytrifluorochloroethylene, polytetrafluoroethylene or polyvinyl alcohol;
Piezoelectric layer is mixed to form by piezopolymer and binding agent; Polymeric piezoelectric material accounts for the more than 90% of piezoelectric layer gross mass;
This piezopolymer is for having the material of chemical structural formula (I);
Wherein
N and m are respectively for being greater than 1 integer;
P is 0 or is greater than 1 integer;
X and Z be the C for being substituted or being unsubstituted respectively 4-C 60aromatic series unit or aliphat unit;
Y is the C that is substituted or is unsubstituted 2-C 40aliphat unit; With
G 1, G 2, G 3and G 4the respectively C for being substituted or being unsubstituted 1-C 12fatty group.
2. polymers function device as claimed in claim 1, is characterized in that, n and m are respectively 10 to 300 integer.
3. polymers function device as claimed in claim 1, is characterized in that, p is 5 to 150 integer.
4. polymers function device as claimed in claim 1, is characterized in that, X and Z are the C that is substituted or is unsubstituted 4-C 12hydrocarbon chain or C 4-C 12dioxygen alkyl.
5. polymers function device as claimed in claim 1, is characterized in that, Y is dioxygen butyl.
6. polymers function device as claimed in claim 1, is characterized in that G 1, G 2, G 3and G 4respectively methyl, ethyl, propyl group, butyl, methoxyl group, ethyoxyl or the propoxyl group for being substituted or being unsubstituted.
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