CN1119837C - Silicon-based ferroelectric sandwich structure for electronic element and device and its manufacture - Google Patents
Silicon-based ferroelectric sandwich structure for electronic element and device and its manufacture Download PDFInfo
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- CN1119837C CN1119837C CN00105549.6A CN00105549A CN1119837C CN 1119837 C CN1119837 C CN 1119837C CN 00105549 A CN00105549 A CN 00105549A CN 1119837 C CN1119837 C CN 1119837C
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004528 spin coating Methods 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001259 photo etching Methods 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 28
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940046892 lead acetate Drugs 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004377 microelectronic Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract 2
- 238000004544 sputter deposition Methods 0.000 abstract 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 34
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The present invention relates to a preparation method of a silicone base ferroelectric sandwich structure used for electronic components. Firstly, PZT precursor collosol and PT precursor collosol are prepared and are fetched out for use; silicon dioxide is grown on a monocrystal silicon substrate; secondly, a metal Pt/Ti layer is formed by sputtering and is used as a bottom layer electrode; a layer of PT collosol is formed on the bottom layer electrode by spin coating; then a layer of PTZ collosol is formed on the bottom layer electrode by spin coating; finally, a layer of positive glue is formed on the surface of a ferroelectric film by spin coating; a metal Pt/Ti layer is formed by photoetching and sputtering; a top layer electrode is formed by stripping the positive glue, and a sandwich structure used for electronic components in the present invention is obtained. The method of the present invention reduces the annealing temperature of ferroelectric films, and enhances the compatibility of the preparation technology of ferroelectric films and the preparation method of micro-electronics.
Description
Technology contents the present invention relates to a kind of silicon-based ferroelectric sandwich structure that is used for electronic devices and components and preparation method thereof, belongs to field of semiconductor devices.
Background technology in recent years, ferroelectric thin film has a wide range of applications at aspects such as microsensor, microactrator, memory and photoelectric devices because of good dielectric that it had, piezoelectricity, ferroelectric and photoelectric characteristic.Lead titanate-zirconate (Pb wherein
x(Zr
yTi
1-y) O
3, hereinafter to be referred as PZT) and be a kind of ferroelectric material of studying at most.Microelectronic technique has developed into very ripe degree, if can the PZT ferroelectric thin film is more widely used with preparing the good PZT ferroelectric thin film of quality with the method for microelectronic technique compatibility.Usefulness sol-gel processes (sol-gel) such as Rao Yunhua have prepared a kind of Silicon PZT ferroelectric thin film structure, this structure is preparation PZT ferroelectric thin film on silicon-based substrate directly, see Fig. 1, consult document " preparation of lead titanate-zirconate ferroelectric thin film and performance study ", " membrane science and technology ", 1995,15 (4): 55-59.Though the processing step of preparation is fairly simple, the annealing temperature in the preparation process is difficult to and the microelectronic technique compatibility up to 900 ℃.And the ferroelectric thin film in this traditional structure is because through high annealing, quality can be subjected to very big influence, is difficult to obtain perfect performance.The direct like this ferroelectric thin film structure for preparing on silicon substrate just is difficult to be applied in the semiconductor device such as memory, transducer, has limited the development of PZT ferroelectric material.
Summary of the invention the objective of the invention is to propose a kind of silicon-based ferroelectric PT/PZT/PT sandwich structure that is used for electronic devices and components, and (PT wherein is PbTiO
3, hereinafter to be referred as PT) and preparation method thereof.PZT ferroelectric thin film in this structure has the good ferroelectric characteristic, and its preparation method can be relatively easy to same ic process compatibility, makes the PZT ferroelectric thin film can be applied to semiconductor components and devices such as memory, transducer.
The preparation method of the silicon-based ferroelectric sandwich structure that is used for electronic devices and components of the present invention's design comprises following each step;
(1) preparation PZT pioneer colloidal sol, make wherein x=0.9～1.1, y=0.4～0.6, take by weighing the lead acetate of respective amount according to the PZT component, zirconium nitrate and butyl titanate are dissolved in the appropriate amount of organic EGME, butyl titanate also can select for use isopropyl titanate etc. to contain titanium salt in the raw material, solvent can the spent glycol ether etc. other organic solvent.
(2) preparation PT pioneer colloidal sol, the content that makes Pb wherein is between 0.9～1.1, the lead acetate and the butyl titanate that take by weighing respective amount according to the PT component are dissolved in an amount of EGME, butyl titanate also can select for use isopropyl titanate etc. to contain titanium salt in the raw material, solvent can the spent glycol ether etc. other organic solvent.
(3) silicon dioxide of thermal oxide growth one deck 5000 on monocrystalline substrate, oxidizing process was made up of dried oxygen-wet oxygen-dried three steps of oxygen.
(4) rf magnetron sputtering layer of metal Pt/Ti layer is made hearth electrode on silicon dioxide layer, and the Pt layer thickness is 1000-2000 , and the Ti layer thickness is 50～100 , 120 ℃ of sputter ambient temperatures, sputter frequency 13.56MHz.
(5) at Pt/Ti/SiO
2Spin coating one deck PT layer on the/Si substrate, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, and heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, and the thickness of PT layer is at 0.01～0.1 μ m.
(6) spin coating PZT colloidal sol on above-mentioned PT layer, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, repeated steps such as spin coating and The pre-heat treatment and made pzt thin film thickness reach 0.15～2 μ m.
(7) at pzt thin film surface spin coating one deck PT layer, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, and heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, and the thickness of PT layer is at 0.01～0.1 μ m.
(8) can obtain crystallization good ferroelectric film to the heat treatment in 700 ℃ of environment of the above-mentioned PT/PZT/PT of acquiring film in 30 minutes.
(9) at the positive glue of ferroelectric thin film surface spin coating one deck, according to the photoetching selectively of top layer electrode position, the Pt/Ti of sputter layer of metal again layer, sputter temperature is 46 ℃, sputter frequency 13.56MHz, positive glue is peeled off and is formed the top layer electrode, and wherein the Pt layer thickness is 800～1000 , the Ti layer thickness is 50～100 , promptly gets the silicon-based ferroelectric sandwich structure that is used for electronic devices and components of the present invention.
The silicon-based ferroelectric sandwich structure that is used for electronic devices and components of the present invention's design, comprise top layer Pt/Ti electrode, PZT ferroelectric thin film, bottom Pt/Ti electrode, silicon dioxide layer, silicon substrate, above-mentioned each layer is arranged in order, also comprise the PT layer, described PT layer bring to Front between Pt/Ti electrode and the PZT ferroelectric thin film respectively and PZT ferroelectric thin film and bottom Pt/Ti electrode between.PZT layer thickness wherein is 0.15～2 μ m, and the PT layer thickness is 0.01～0.1 μ m, and the PZT layer with the ratio of PT layer thickness is: 10～30.The Pt layer thickness is 1000～2000 in the bottom electrode wherein, and the Ti layer thickness is 50～100 .The Pt layer thickness is 800～1000 in the top layer electrode wherein, and the Ti layer thickness is 50～100 .
Adopt the PT/PZT/PT sandwich structure of design of the present invention significantly to reduce the annealing temperature of ferroelectric thin film, thereby improved the preparation technology of ferroelectric thin film and the compatibility of microelectronic technique, test result shows that the PZT ferroelectric thin film shows good dielectric and ferroelectric properties simultaneously.This ferroelectric sandwich structure and preparation method thereof is applied to field of semiconductor devices such as memory, transducer possibility is provided for ferroelectric thin film.
Description of drawings
Fig. 1 is existing silicon-based ferroelectric membrane structure.
Fig. 2 is a ferroelectric sandwich structure of the present invention.
Among Fig. 1-Fig. 2: 1 is top layer Pt/Ti electrode; 2 is the PZT ferroelectric thin film; 3 is bottom Pt/Ti electrode; 4 is silicon dioxide layer; 5 is silicon substrate; 6 is the PT layer.
Embodiment
The principle of institute of the present invention foundation is: the lead titanates ferroelectric has the lattice structure similar to PZT, and its crystallization temperature is than PZT low (about 600 ℃), after the upper and lower surface of pzt thin film respectively adds one deck PT layer, the PT layer can provide nucleus for the crystallization of PZT from both direction, thereby significantly reduce the crystallization temperature of PZT, improve the crystallization quality of pzt thin film.And by controlling the concentration and the even glue speed of PT colloidal sol, can make the thickness of the thickness of PT layer much smaller than pzt thin film, thereby make the adding of PT layer can ignore the influence of pzt thin film apparent property, can not cause the decline of pzt thin film apparent property.
The silicon-based ferroelectric sandwich structure that is used for electronic devices and components of the present invention's design, as shown in Figure 1, comprise top layer Pt/Ti electrode 1, PZT ferroelectric thin film 2, bottom Pt/Ti electrode 3, silicon dioxide layer 4, silicon substrate 5, above-mentioned each layer is arranged in order, also comprise PT layer 6, described PT layer 6 bring to Front between Pt/Ti electrode 1 and the PZT ferroelectric thin film 2 respectively and PZT ferroelectric thin film 2 and bottom Pt/Ti electrode 3 between.
Embodiments of the invention are:
Embodiment 1: the PT/PZT/PT sandwich structure of preparation 0.02/0.2/0.02 μ m.
(1) get 0.0318 mole lead acetate, the butyl titanate of 0.0159 mole zirconium nitrate and 0.0141 mole is dissolved in PZT pioneer's colloidal sol of preparation 0.17 mol in 180 milliliters the EGME.Plumbous composition is excessive 6% among the PZT, and the mol ratio of Zr/Ti is 53/47;
(2) butyl titanate of getting 0.0318 mole lead acetate and 0.03 mole is dissolved in PT pioneer's colloidal sol of preparation 0.05 mol in 600 milliliters the EGME.Lead excessive 6% among the PT;
(3) silicon dioxide of thermal oxide growth one deck 5000 on monocrystalline substrate;
(4) rf magnetron sputtering metal Pt/Ti layer is as hearth electrode on silicon dioxide, and the Pt/Ti layer thickness is 2000/50 ;
(6) the PT colloidal sol of spin coating 0.05 mol on the Pt/Ti hearth electrode is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.02 μ m;
(7) the PZT colloidal sol of spin coating 0.17 mol on above-mentioned PT layer is again removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and triplicate spin coating and The pre-heat treatment step make pzt thin film thickness be about 0.2 μ m;
(8) the PT colloidal sol of spin coating 0.05 mol on above-mentioned pzt thin film is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.02 μ m;
(9) thermal annealing obtained the PT/PZT/PT ferroelectric sandwich structure in 30 minutes in 700 ℃ environment;
(10) rf magnetron sputtering metal Pt/Ti layer (850 /50 ) on ferroelectric thin film at last, positive glue is peeled off the formation top electrode.
This sandwich structure is carried out electric performance test, and the result shows that the relative dielectric constant of ferroelectric thin film is 920, and coercive field is 24KV/cm, and remanent polarization is 17 μ C/cm
2, leakage current is 5 * 10
-9A/cm
2
Embodiment 2: the PT/PZT/PT sandwich structure of preparation 0.04/1/0.04 μ m
(1) get 0.03 mole lead acetate, the butyl titanate of 0.0144 mole zirconium nitrate and 0.0156 mole is dissolved in PZT pioneer's colloidal sol of preparation 0.17 mol in 180 milliliters the EGME.The mol ratio of Zr/Ti is 48/52 among the PZT;
(2) butyl titanate of getting 0.03 mole lead acetate and 0.03 mole is dissolved in PT pioneer's colloidal sol of preparation 0.1 mol in 300 milliliters the EGME;
(3) silicon dioxide of thermal oxide growth one deck 5000 on monocrystalline substrate;
(4) rf magnetron sputtering metal Pt/Ti layer is as hearth electrode on silicon dioxide, and the Pt/Ti layer thickness is 1500/80 ;
(5) the PT colloidal sol of spin coating 0.1 mol on the Pt/Ti hearth electrode is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.04 μ m;
(6) the PZT colloidal sol of spin coating 0.17 mol on above-mentioned PT layer is again removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, repeats eight spin coatings and The pre-heat treatment step and makes pzt thin film thickness reach about 1 μ m;
(7) the PT colloidal sol of spin coating 0.1 mol on the Pt/Ti hearth electrode is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.04 μ m;
(8) thermal annealing obtained the PT/PZT/PT ferroelectric sandwich structure in 30 minutes in 700 ℃ environment;
(9) at last on ferroelectric thin film the positive glue of rf magnetron sputtering metal Pt/Ti layer (900 /80 ) peel off the formation top electrode;
This sandwich structure is carried out electric performance test, and the result shows that the relative dielectric constant of ferroelectric thin film is 900, and coercive field is 20KV/cm, and remanent polarization is 20 μ C/cm
2, leakage current 2 * 10
-9A/cm
2
Embodiment 3: the PT/PZT/PT sandwich structure of preparation 0.1/1.5/0.1 μ m.
(1) gets 0.0282 mole lead acetate, 0.012 the zirconium nitrate of mole and 0.018 mole butyl titanate are dissolved in PZT pioneer's colloidal sol of preparation 0.17 mol in 180 milliliters the EGME, composition plumbous among the PZT is 0.94, and the mol ratio of Zr/Ti is 40/60;
(2) butyl titanate of getting 0.0282 mole lead acetate and 0.03 mole is dissolved in PT pioneer's colloidal sol of preparation 0.1 mol in 300 milliliters the EGME.Composition plumbous among the PT is 0.94;
(3) silicon dioxide of thermal oxide growth one deck 5000 on monocrystalline substrate;
(4) rf magnetron sputtering metal Pt/Ti layer is as hearth electrode on silicon dioxide, and the Pt/Ti layer thickness is 2000/100 ;
(5) the PT colloidal sol of spin coating 0.1 mol on the Pt/Ti hearth electrode is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.1 μ m;
(6) again with 2000 rev/mins, the PZT colloidal sol of 30 seconds condition spin coating 0.17 mol is removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, repeats ten spin coatings and The pre-heat treatment step and makes pzt thin film thickness be about 1.5 μ m;
(7) the PT colloidal sol of spin coating 0.1 mol on above-mentioned pzt thin film is then removed organic component through the The pre-heat treatment of 380 ℃ and 600 ℃, and the thickness of one deck PT is about 0.1 μ m;
(8) thermal annealing obtained the PT/PZT/PT ferroelectric sandwich structure in 30 minutes in 700 ℃ environment;
(9) rf magnetron sputtering metal Pt/Ti layer (1000 /100 ) on ferroelectric thin film at last, positive glue is peeled off the formation top electrode.
This sandwich structure is carried out electric performance test, and the result shows that the relative dielectric constant of ferroelectric thin film is 920, and coercive field is 18KV/cm, and remanent polarization is 23 μ C/cm
2, leakage current 1 * 10
-9/cm
2
Claims (5)
1, a kind of preparation method who is used for the silicon-based ferroelectric sandwich structure of electronic devices and components is characterized in that, this preparation method comprises following each step:
(1) preparation Pb
x(Zr
yTi
1-y) O
3Be that PZT pioneer's colloidal sol is standby, make wherein x=0.9～1.1, y=0.4～0.6: take by weighing the lead acetate of respective amount according to the PZT component, zirconium nitrate and butyl titanate are dissolved in the organic solvent;
(2) preparation PT pioneer colloidal sol is standby, and the content that makes Pb wherein is between 0.9～1.1: the lead acetate and the butyl titanate that take by weighing respective amount according to the PT component are dissolved in the organic solvent;
(3) silicon dioxide of thermal oxide growth one deck 5000 on monocrystalline substrate, oxidizing process was made up of dried oxygen-wet oxygen-dried three steps of oxygen;
(4) rf magnetron sputtering layer of metal Pt/Ti layer is made bottom electrode on silicon dioxide layer, and the Pt layer thickness is 1000～2000 , and the Ti layer thickness is 50～100 , 120 ℃ of sputter ambient temperatures, sputter frequency 13.56MHz;
(5) at Pt/Ti/SiO
2The PT colloidal sol of above-mentioned the 2nd step preparation of spin coating one deck on the/Si substrate, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, and heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, and the thickness that makes the PT layer at last is at 0.01～0.1 μ m;
(6) the PZT colloidal sol of spin coating one deck the 1st step preparation on above-mentioned PT layer, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, repeated to make pzt thin film thickness reach 0.15～2 μ m after spin coating and the The pre-heat treatment;
(7) at pzt thin film surface spin coating one deck PT layer, The pre-heat treatment was removed organic solvent in 1 minute in 380 ℃ of environment then, and heat treatment was thoroughly removed organic component in 2 minutes in 600 ℃ of environment again, and the thickness of PT layer is at 0.01～0.1 μ m;
(8) the PT/PZT/PT film heat treatment in 700 ℃ of environment with above-mentioned preparation promptly obtained ferroelectric thin film in 30 minutes;
(9) at the positive glue of ferroelectric thin film surface spin coating one deck, according to the photoetching selectively of top layer electrode position, the Pt/Ti of sputter layer of metal again layer, sputter temperature is 46 ℃, sputter frequency 13.56MHz, positive glue is peeled off and is formed the top layer electrode, and wherein the Pt layer thickness is 800～1000 , the Ti layer thickness is 50～100 , promptly gets the silicon-based ferroelectric sandwich structure that is used for electronic devices and components.
2, a kind of silicon-based ferroelectric sandwich structure that is used for electronic devices and components, comprise top layer Pt/Ti electrode, PZT ferroelectric thin film, bottom Pt/Ti electrode, silicon dioxide layer, silicon substrate, above-mentioned each layer is arranged in order, it is characterized in that also comprising two-layer PT layer, described PT layer bring to Front between Pt/Ti electrode and the PZT ferroelectric thin film respectively and PZT ferroelectric thin film and bottom Pt/Ti electrode between.
3, silicon-based ferroelectric sandwich structure as claimed in claim 2 is characterized in that, wherein said PZT layer thickness is 0.15～2 μ m, and the PT layer thickness is 0.01～0.1 μ m, and the PZT layer with the ratio of PT layer thickness is: 10～30.
4, silicon-based ferroelectric sandwich structure as claimed in claim 2 is characterized in that, the Pt layer thickness is 1000～2000 in the wherein said bottom electrode, and the Ti layer thickness is 50～100 .
5, silicon-based ferroelectric sandwich structure as claimed in claim 2 is characterized in that, the Pt layer thickness is 800～1000 in the wherein said top layer electrode, and the Ti layer thickness is 50～100 .
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