WO2003033759A1 - The surface reforming method of a piezoelectric or pyroelectric material using an ion-beam - Google Patents
The surface reforming method of a piezoelectric or pyroelectric material using an ion-beam Download PDFInfo
- Publication number
- WO2003033759A1 WO2003033759A1 PCT/KR2001/001768 KR0101768W WO03033759A1 WO 2003033759 A1 WO2003033759 A1 WO 2003033759A1 KR 0101768 W KR0101768 W KR 0101768W WO 03033759 A1 WO03033759 A1 WO 03033759A1
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- WO
- WIPO (PCT)
- Prior art keywords
- piezoelectric
- pyroelectric
- polymer material
- ion
- ion beam
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010884 ion-beam technique Methods 0.000 title claims abstract description 23
- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title description 6
- 239000002861 polymer material Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000005468 ion implantation Methods 0.000 claims abstract description 6
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 9
- -1 polytrifluorethylene Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000011365 complex material Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229940117958 vinyl acetate Drugs 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000001659 ion-beam spectroscopy Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0872—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using ion-radiation, e.g. alpha-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/30—Electron or ion beam tubes for processing objects
- H01J2237/31—Processing objects on a macro-scale
- H01J2237/3156—Curing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
Definitions
- the reactive gas is injected to the high polymer, thus generating a new hydrophilic functional group on the high-polymer surface.
- the high-polymer material and the electrode material are physically and chemically combined so that precious metals such as Pt, Au, etc. can have excellent adhesiveness.
- FIG. 2 graphically shows a change in the contact angle of the water and the
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Disclosed is a method for reforming a surface of a piezoelectric or pyroelectric high-polymer material used for manufacture of a piezoelecttric or pyroelectric device by using an ion beam, including the steps of putting the piezoelectric or pyroelectric high-polymer material on a vacuum chamber; generating an ion beam from an ion implantation energy and irradiating the ion beam on the surface of the piezoelectric or pyroelectric high-polymer material; and injecting a given amount of a reactive gas through a gas injection tube of the vacuum chamber thus generating a hydrophilic functional group on the piezoelectric or pyroelectric high-polymer material.
Description
THE SURFACE REFORMING METHOD OF A PIEZOELECTRIC OR PYROELECTRIC MATERIAL USING AN ION-BEAM
BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to a method of reforming the surface of a piezoelectric or pyroelectric high-polymer material by using an ion beam. More particularly, the present invention relates to a method of reforming the surface of a piezoelectric or pyroelectric high-polymer material by ion supporting reaction, thus enhancing adhesiveness and durability.
(b) Description of the Related Art
Conventionally, piezoelectric and pyroelectric materials including ceramic substances such as quartz crystal, barium titanate have been generally used, and recently, studies of various devices and common use thereof employing piezoelectric or pyroelectric high-polymer materials including polyvinyliden fluoride (PVDF) are being made. The piezoelectric and pyroelectric high-polymer materials are more pliable and lighter in weight than the conventional materials, and each of them has a wide vibration area. Thus, replacement of the conventional piezoelectric or pyroelectric materials with these high-polymer materials and development of new devices by means of the high-polymer materials have been carried out in full activity.
By way of example, a film loudspeaker using the PVDF was developed a few years ago. However, the piezoelectric/pyroelectric high-polymer materials that are going to be commonly used do not easily adhere to electrode materials because of low surface energy, which makes the formation of a device impossible and shortens the device's life.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method of reforming the surface of a piezoelectric or pyroelectric high-polymer material by using an ion beam, thus manufacturing piezoelectric or pyroelectric devices with high durability and devices of new concept.
In order to achieve the above object, the present invention is a method of reforming the surface of a piezoelectric or pyroelectric high-polymer material used for manufacture of a piezoelectric or pyroelectric device by using an ion beam, including the steps of putting the piezoelectric or pyroelectric high-polymer material on a vacuum chamber; generating an ion beam from an ion gun by a given ion implantation energy and irradiating the ion beam on the surface of the piezoelectric or pyroelectric high-polymer material; and injecting a given amount of a reactive gas through a gas injection tube of the vacuum chamber, thus generating a hydrophilic functional group on the piezoelectric or pyroelectric high-polymer material.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal-sectional view of an ion-beam surface-finishing equipment for carrying out a method of reforming a surface of a piezoelectric or pyroelectric high-polymer material by using an ion beam according to the present invention;
FIG. 2 graphically shows a change in the contact angle of the water and the PVDF surface-finished by the inventive surface reforming method; FIG. 3 graphically shows results from an analysis on an XPS Cls core level spectra of the PVDF surface-finished by the inventive surface reforming method;
FIG. 4 graphically shows results from an analysis on an XPS Ols core level spectra of the PVDF surface-finished by the inventive surface reforming method;
FIG. 5 graphically depicts a change in the surface energy of the PVDF surface-finished by the inventive surface reforming method;
FIGS. 6a to 6d each depict results of a boiling test of the Pt electrode
deposited on the PVDF, and In FIG. 6a, the PVDF is not surface-finished, and FIGS. 6b to 6d depict the results of the PVDF surface-finished at 5 x 1014Ar+/cm2, 1 x 10 Ar /cm , and 1 x 10 Ar /cm , respectively; and
FIG. 7 graphically depicts a change in the sheet resistance and transmittance in response to the thickness of the ITO thin film deposited on the high-polymer substrate according to an embodiment applying the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiment of the present invention is now fully described referring to the attached drawings.
The present invention uses an ion supporting reaction to reform a surface of a piezoelectric or pyroelectric high-polymer material.
FIG. 1 is a longitudinal sectional view of an ion-beam surface finishing equipment for carrying out a method of reforming the surface of the piezoelectric or pyroelectric high-polymer material by using an ion beam.
As shown in FIG. 1, a sample 2 is put over an ion gun 3 in a vacuum chamber 1 that is keeping its vacuum by a vacuum pump 5, and the ion gun 3 produces an ion beam to the sample 2. Preferably, the vacuum in the vacuum chamber 1 is in the range of 1 x 10"1 torr to 1 x IO"6 torr, and the ion implantation energy for the ion beam is in the range of 10 to lOOOOeV. Preferably, the amount of the ion beam implanted to the surface of the sample 2 is 1 x IO12 to 1 x IO20 ions /cm2.
The sample 2 is a piezoelectric or pyroelectric high-polymer material, and this piezoelectric or pyroelectric high-polymer material is a piezoelectric or pyroelectric high-polymer and its co-polymer such as PVDF, VDF-TrFE (vinylydene fluoride-trifluoroethylene), odd nylon (nylon7, nylon 11), VDCN (vinylidene cyanide), P(VDCN-VAcpoly(vinylidene cyanine-vinylacetate)), P(TBTM-MMA) (poly(methyl methacrylate-polytributyline methacrylate)), PtrFE
(polytrifluorethylene), PVF (poly(vinyl fluoride)), or a complex material including a
piezoelectric ceramic such as PZT, PbTiO3, Ca-PbTiO3. Ions are generated by injecting a reactive gas through a gas injection tube 4 outside of the vacuum chamber 1.
The reactive gas may be anyone of oxygen, air, ammonia, hydrogen, CO, CO2, nitrogen, nitrous oxide, and hydrocarbon. A non-active gas such as helium, argon, nitrogen, neon, xenon, krypton, etc. can be used instead of the reactive gas. Preferably, the amount of the reactive gas is 1 to 500sccm.
According to the ion supporting reaction, simultaneously with applying the low-energy ion beam of O.lkeV to lOkeV to the surface of the high-polymer, the reactive gas is injected to the high polymer, thus generating a new hydrophilic functional group on the high-polymer surface. When applying an electrode material onto the piezoelectric or pyroelectric high-polymer material, the high-polymer material and the electrode material are physically and chemically combined so that precious metals such as Pt, Au, etc. can have excellent adhesiveness. FIG. 2 graphically shows a change in the contact angle of the water and the
PVDF surface-finished by the inventive surface reforming method. The graph shows the change in the contact angle of the water and the PVDF surface-finished by using the ion supporting reaction in response to the ion exposure. The PVDF has a high value of 75° due to the minority before the surface finishing by the ion reaction method. After applying the reactive gas O2 to its surface and surface-finished at 1 x 10 ions/cm , the PVDF has a value of 31° minimally. The reason why its contact angle is decreased after the surface finishing is the hydrophilic property that is newly created on the PVDF's surface by the ion supporting reaction.
FIG. 3 graphically shows results from an analysis on an XPS Cls core level spectra of the PVDF surface-finished by the inventive surface reforming method. The graph shows a comparison in the XPS Cls core level spectra before and after the surface finishing.
The generation of the hydrophilic functional group on the PVDF's surface can be recognized by comparing the chemical structure of the PVDF's surface before the surface finishing with that of the PVDF's surface after the surface finishing by
using the XPS analysis. In the Cls core level spectra of the PVDF not surface- finished yet, native peaks of -CH -(286.2eV) and -CF2-(290.8eV) are produced. However, in the spectra of the PVDF surface-finished with the reactive gas by using the ion supporting reaction, a -CF2-peak is abruptly decreased, and peaks of -C-O- (286. leV), -(C=O)-O-(289.0eV), etc. are newly produced or increased. The above couplings have hydrophilic properties, and the contact angle is decreased, as shown in FIG. 2.
FIG. 4 graphically shows results from an analysis on an XPS 01 s core level spectra of the PVDF surface-finished by the inventive surface reforming method. As depicted in FIG. 4, in the 01 s core level spectra there is little oxygen in the PVDF not surface-finished yet. In the PVDF reformed at 5 x 1014ions/cm2 the coupling of the oxygen is increased, which agrees with FIG. 3's results.
FIG. 5 graphically depicts a change in the surface energy of the PVDF surface-finished by the inventive surface reforming method. The graph shows a change in the surface energy of the PVDF processed in response to the ion exposure. A contact angle of water and formamide, two polar solids is measured, and after a dispersion force and a polar force are calculated by using the value of the contact angle, a value of the dispersion force is added to a value of the polar force to calculate a surface energy value. If a smface-finishing at 1 x 1015ions/cm2is carried out as depicted in FIG. 5, the surface energy that was 36 erg/cm2 is increased to 64 erg/cm2 maximum. The creation of the hydrophilic functional group causes the increase in the surface energy. Such a hydrophilic functional group is physically and chemically coupled to the electrode material deposited on the PVDF, thus greatly increasing the adhesive force. Various electrode materials (precious metals: Pt, Au, Ag, etc., conductive oxides: indium tin oxide (ITO), SnO2, ZnO, CeO2, etc. & their doped conductive oxides, doped polyacetylene (PA), polyethylene dioxythiophene polystyrene sulphonate (PEDT), polyaniline (PAN), poly(p-phenylene)(PPV), poly(p- phenylenevinylene(PPP), polypyrrole(PPy), polythiophene(PT), their inductors, conductive high polymer (π - conjugate high polymer) and organic molecules) that
poorly adhere to electrodes and have been hitherto limited to the manufacture of devices as well as metal electrodes used now (Pt, Au, Ag, Al, Ni, Ti, Cu, etc.) can be used for the manufacture of devices.
FIGS. 6a to 6d each depict results of a boiling test of the Pt electrode deposited on the PVDF.
In FIG. 6a, the PVDF is not surface-finished, and FIGS. 6b to 6d depict the results of the PVDF surface-finished at 5 x 1014Ar+/cm2, 1 x 1015Ar+/cm2, and 1 x 1017Ar+/cm2, respectively. In these tests, Ar+ ions are used, and another ions can be used for the surface finishing. As depicted in FIG. 6a, a buckling is broadly generated in the Pt thin film deposited on the PVDF not surface-finished. As shown in FIGS. 6b, 6c and 6d, the buckling is significantly decreased on the Pt thin film of the PVDF surface-finished with Ar+ ions, and cracks are created on the Pt thin film instead of the buckling after the ion implantation at 1 x 10 ions/cm . The stress generated by a difference in the coefficient of the thermal expansion when the adhesive force is excellent at the interface is solved by the creation of the cracks instead of the buckling, and the PVDF's adhesion with the Pt electrode is enhanced. One of embodiments applying the present invention is a round PVDF film loudspeaker using a transparent conductive oxide, an ITO thin film, as an electrode.
In addition, since it is impossible to heat the PVDF with a low melting point at high temperature, the PVDF should be heated at low temperature. In this occasion, attaining low resistance corresponding to the metal electrode is difficult, and if using a conventional sputtering method, the PVDF directly contacts the plasma, and collision of high-energy particles abruptly decreases the PVDF's surface-finishing effect.
Accordingly, the present invention employs an ion-beam sputtering as a method of depositing the ITO electrode, instead of the conventional sputtering. As the ion-beam sputtering separates the plasma from the substrate, a thin film with superior properties at low temperature can be deposited, minimizing damage to the substrate.
FIG. 7 graphically depicts a change in the sheet resistance and transmittance at 550nm in response to the thickness of the ITO thin film deposited at 50°C by the inventive ion-beam sputtering. This ITO thin film has the low sheet resistance of 20Ω /square and high transmittance of 82% at 2000A, and can serve as an electrode because its sheet resistance is decreased by less than 10 times in comparison with a case of depositing the Pt film to 500A.
Accordingly, the present invention can be used for the manufacture of loudspeakers of TV cathode ray tubes, computer monitors, projection TVs, PDAs, mobile phones, etc. by using the ITO, transparent conductive high-polymer or doped organic monolayer as an electrode material.
The present invention can be applied to the manufacture of speaker built-in display devices (monitors) and micro pumps used for ink-jet printer heads employing high-polymer piezoelectric materials, and is applicable to another fields. In addition, the piezoelectric or pyroelectric high-polymer materials that were surface-finished by the ion supporting reaction to enhance the adhesiveness to electrodes can be used for the manufacture of microphones, piezoelectric transducers, acting sensors, infrared- ray image sensors, optical sensors, hydrogen sensors, ultrasonic vibration devices, etc.
According to the surface reforming method of the present invention, the adhesiveness between the electrodes of the piezoelectric or pyroelectric devices can be enhanced by reforming the surface of the piezoelectric or pyroelectric high- polymer film, and piezoelectric or pyroelectric devices with high durability and devices of new concept can be manufactured. The enhancement of the adhesiveness can lengthen the piezoelectric or pyroelectric device's life. Besides, according to the present invention, several electrode materials that have been hitherto limited to the use can be employed for the manufacture of devices.
Claims
1. A method of reforming a surface of a piezoelectric or pyroelectric high- polymer material used for manufacture of a piezoelectric or pyroelectric device by using an ion beam, comprising the steps of: putting the piezoelectric or pyroelectric high-polymer material on a vacuum chamber; generating an ion beam from an ion gun by a given ion implantation energy and irradiating the ion beam on the surface of the piezoelectric or pyroelectric high- polymer material; and injecting a given amount of a reactive gas through a gas injection tube of the vacuum chamber thus generating a hydrophilic functional group on the piezoelectric or pyroelectric high-polymer material.
2. A method according to claim 1, wherein the reactive gas is anyone of of oxygen, air, ammonia, hydrogen, CO, CO2, nitrogen, nitrous oxide, and hydrocarbon.
3. A method according to claim 1, wherein the ion implantation energy for the ion beam is 100 to lOOOOeV.
4. A method according to claim 1, wherein the ion beam is implanted on the piezoelectric or pyroelectric high-polymer material at 1 x IO12 to 1 x IO20 ions/cm2.
5. A method according to claim 1, wherein the amount of the injected reactive gas is 1 to 500 seem.
6. A method according to claim 1, wherein a vacuum of the vacuum chamber is 1 x 10"1 torr to 1 x 10"6 torr.
7. A method according to claim 1, wherein the piezoelectric or pyroelectric high-polymer material is a piezoelectric or pyroelectric high-polymer and its co- polymer such as PVDF, VDF-TrFE (vinylydene fluoride-trifluoroethylene), odd nylon, VDCN (vinylidene cyanide), P(VDCN-VAcpoly(vinylidene cyanine- vinylacetate)), P(TBTM-MMA) (poly(methyl methacrylate-polytributyline methacrylate)), PtrFE (polytrifluorethylene), PVF (poly(vinyl fluoride)).
8. A method according to claim 1, wherein the piezoelectric or pyroelectric high-polymer material is a complex material including a piezoelectric ceramic such as PZT, PbTiO3, and Ca-PbTiO3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2001/001768 WO2003033759A1 (en) | 2001-10-19 | 2001-10-19 | The surface reforming method of a piezoelectric or pyroelectric material using an ion-beam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2001/001768 WO2003033759A1 (en) | 2001-10-19 | 2001-10-19 | The surface reforming method of a piezoelectric or pyroelectric material using an ion-beam |
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| WO2003033759A1 true WO2003033759A1 (en) | 2003-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/KR2001/001768 WO2003033759A1 (en) | 2001-10-19 | 2001-10-19 | The surface reforming method of a piezoelectric or pyroelectric material using an ion-beam |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000065896A (en) * | 1999-04-10 | 2000-11-15 | 성재갑 | Method of modificating surface of polymeric materials |
| KR100316586B1 (en) * | 1995-04-19 | 2002-02-28 | 박호군 | Method of modification of material surface and material having surface modified by the method |
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2001
- 2001-10-19 WO PCT/KR2001/001768 patent/WO2003033759A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100316586B1 (en) * | 1995-04-19 | 2002-02-28 | 박호군 | Method of modification of material surface and material having surface modified by the method |
| KR20000065896A (en) * | 1999-04-10 | 2000-11-15 | 성재갑 | Method of modificating surface of polymeric materials |
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