CA2263357A1 - Semiconductor supercapacitor system, method for making same and articles produced therefrom - Google Patents
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Abstract
The invention relates to a nanostructured BaTiO3 film, plate or array that has from 1,000 to 10,000 times the storage capacity of conventional capacitors.
The barium titanates are of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is 2.5 to about 5Ø The barium titanates may further be doped with a material, "M", selected from Au, is Au, Cu, Ni3Al, Ru or InSn. The resulting titanate may be represented by the formula MdBaaTibOc wherein d is about 0.01 to 0.25, a is about 0.75 to about 1.25, b is about 0.75 to about 1.25 and c is about 2.5 to about 5Ø X-ray diffraction results illustrate that the crystal structure of the thin films changed from predominantly cubic to tetragonal phase and crystallite size increased with increasing concentration of "M".
The barium titanates are of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is 2.5 to about 5Ø The barium titanates may further be doped with a material, "M", selected from Au, is Au, Cu, Ni3Al, Ru or InSn. The resulting titanate may be represented by the formula MdBaaTibOc wherein d is about 0.01 to 0.25, a is about 0.75 to about 1.25, b is about 0.75 to about 1.25 and c is about 2.5 to about 5Ø X-ray diffraction results illustrate that the crystal structure of the thin films changed from predominantly cubic to tetragonal phase and crystallite size increased with increasing concentration of "M".
Description
. CA 02263357 1999-02-12 W O 98/07167 PCT~B97/00985 APPLICATIC)N FOR PATENT
TITLE: SEMICONDUCTOR SUPE~RCAPACITOR SYSTEM, METHOD FOR MAKING SAME AND ARTICLES
PRODUCED THEREFROM
SPECIFICATION
Field of the invention The invention relates to barium titanate thin films and plates and to semiconductor devices such as microminiature, large capacitance capacitors usingsuch films. The invention further relates to barium titanate thin films and plates incorporating a non-reactive electroconductive material, "M". The storage capacity of the thin films and plates of the invention is at least 1 farad/cm3. The invention further relates to a method of preparing the thin films. Such crystalline thin films are characterized by a perovskite structure and have utility in the manufacture of a wide variety of ferroelectric, dielectric, pyroelectric, piezoelectric and electro-optic devices, such as nonvolatile semiconductor memories, thin-film capacitors, 1û pyroelectric (IR) detectors, sensors, surface acoustic wave substrates, optical waveguides, optical memories, spatial light modulators as well as frequency doublers for diode lasers.
Sl~ JTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO98/07167 PCT~B97/00985 Background of the Invention In the past years, there has been extended efforts in the development of high capacitance electrochemical energy storage devices, especially capacitors and batteries, for use in reduced volumetric areas. Both capacitors and batteries store energy by the separation of positive and negative charges. The need to store greater amounts of energy in a smaller package continues to drive new research.
Barium titanate (BaTiO3) has been studied for use in such microelectronic applications. Such studies have included the different forms of barium titanate including powder, bulk, thin film and multilayer owing to their excellent electronic and optical characteristics including high dielectric constant, transparency in visible wavelength, and high non-tinear optical susceptibility.
The use of barium titanates in electric vehicles is further highly desired.
Presently, automotive internal combustion engines are increasingly being challenged by environmental concerns, favoring an increased role for electric 1~ vehicles. Thus, supercapacitors, as well as batteries, play a major role in this developing market.
Supercapacitors having capacitances in the range of miili-Farads to Farads have suffered from slow charging and discharging cycles in light of their high series resistance (i.e., large RC time constants). In addition, they often rely on corrosive and environmentally unfriendly electrolytes. For instance, the BaTiO3 thin films set forth in T. Hayashi, Jpn. J. Appl. Phys., 32 4092 (1993) have a capacitance unacceptable for use in electric vehicles as well as other industries. Alternative SU~ JTE S~IEET ~RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 nanosized capacitors are -onstantly being sought.
Need exists therefore for an electrical energy storage device that combines the desirable features of conventional capacitors yet can store much iarger amounts of energy in a smaller package and can be manufactured at reasonable costs.
Summary of the Invention The invention relates to a nanostructured BaTiO3 thin film composite that has from 1,000 to 10,000 times the area and storage capacity of conventional BaTiO3 thin fiims, plates and arrays. The BaTiO3 thin films and plates of the invention can also exhibit a variable discharge rate controlled by optical iliumination (pumping) .
The barium titanates comprising the coating of the thin films or plates of the invention exhibit dielectric, ferroelectric and/or paraelectric properties. The barium titanates are of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is 2.5 to about 5Ø The thin film composites of the invention exhibit a storage capacity of at least 1 to 100 farads per cubic centimeter.
In another embodiment of the invention, the thin fiims comprise barium titanate incorporating a non-reactive electroconductive material, "M", capable of forming a microstructure with the thin film. The resulting titanate is of the formula MdBaaTibOc wherein d is about 0.01 to about Q.25, a is about 0.75 to about 1.25,b is about 0.75 to about 1.25 and c is about 2.5 to about 5Ø Thin film SU~ ~ TE SHEET (RULE 26) CA 022633~7 l999-02-l2 W O 98/07167 PCT~B97/00985 composites containing the incorporated material have a storage capacity of a magnitude between 10 to 1,000 times higher than the storage capacity of the composite materials without incorporated "M" (BaaTibOc).
The thin film composites of the invention have particular applicabiiity in the production of microminiature capacitors.
Lastly, the invention relates to a process of preparing and using a barium titanate film composite, optionally incorporating particles of "M".
Brief Description of the Drawings FIG. 1 is a sample preparation of a planar capacitor made by the sol-gel process.
FIG. 2 is a perspective view of the substrate of the thin film composite of the invention having macropores.
FIG. 3 is a side view of the substrate of FIG. 2.
FIG. 4 is a perspective view of the substrate of the thin film composite of the invention having trenches.
FIG. 5 is a side view of the substrate of FIG. 4.
FIG. 6 is a perspective view of the substrate of the thin film composite of the invention having depressions.
Z0 FIG. 7 is a side view of the substrate of FIG. 6.
FIG. 8 is a side view of a substrate of the thin film composite of the inventionhaving projections extending from the surface.
SUBSTITUTE SHEET (RUEE 26) CA 022633~7 1999-02-12 W O 981~7167 PCT~B97tO~985 FIG. 9 is an internal structure of a thin film composite of the inv~ntion as seen using a scanning electron microscope.
FIG. 10 is the x-ray diffraction pattern of a barium titanate composite prepared in accordance with the invention.
FIG. 11 illustrates the morphology of a nanocrystalline BaTiO3 film composite prepared in accordance with the invention.
Detailed Description of Preferred Embodiments The thin film composites of the invention comprise a thin iayer, plate or array (collectively termed "thin film") of the formula Ba~TibOc wherein a and b are independentty between 0.7~ and 1.25 and c is between about 2.5 and about 5.0 deposited onto a substrate. In a preferred embodiment, both a and b are 1 and c is about 3 of the formula BaaTi,,Oc .
The thin film composites of the invention exhibit an extremely high energy density. As such, thin film composites of the invention have particular applicability in the production of microminiature capacitors.
In addition. the BaTiO~ thin film composites of the invention exhibit a variable discharge rate controlled optically. This permits the capacitance of an article composed of such composites to be tunable for applications where a specific capacitance is desired. In addition, this facilitates designing variable 2~ electric series resistance devices for controlled power delivery.
The substrate of the thin film composites of the invention typically are SIJ~S 1 I ~ ~JTE SHEET (RULE 26) CA 022633~7 1999-02-12 composed of silicon, fused silica, Pt-coated silicon, alumina, sapphire, Pt-coated sapphire, metallized foil, such as a copper foil, or a single crystal SrTiO3 substrate.
In addition, the substrate may consist of any electroconductive metat ha~ing a melting point of at least 850 C. The substrate shouid not meit or undergo a phase transition under typical annealing conditions or react or diffuse with the othercomponents of the composite (or laminate as described herein) so as to diminish the properties of the resultant product. Thus, for example, Al would be unsuitable as it would melt at 850~C, a typical annealing temperature.
Suitable for use as the silicon layer are rapidly thermally processed silicon layers crystalli~ed by a lamp based annealling system. Alternatively, silicon whose crystallization has been induced by a laser, such as an excimer laser, may also be used. Alternatively, the substrate may comprise an oxide layer which is rapidly thermally processed using a lamp-based annealing system or laser annealing with a laser such as an excimer or carbon dioxide laser or electron-beam processing.
Still further, the substrate of the invention offering increased surface areas may include anisotropically etched substrates as well as locally patterned substrates by laser ablation.
The thin film of the composite comprises an inorganic oxide of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is between about 2.5 and about 5Ø In preferred embodiment, a and b are approximately 1 and c is about 3Ø In a most preferred embodiment, the inor~anic oxides exhibit a tetragonal or perovskite crystalline lattice . During the process SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 described herein, oxygen vacancies and internal stress contribute to the crystailite growth and phase transformation of the oxide. For larger grain sizes of the barium titanate, the material tends to assume a tetragonal crystal structure.
The thin film may further contain a non-reactive component capable of inducing internal strain. Suitable for use as non-reactive components include europium, silicon nitride, boron nitride, magnesium oxide, alumina, tungsten carbide as well as diamond particles. While amounts as high as 50 volume percent of the non-reactive ~omponent may be employed, the preferred amount is less than 10 volume percent. Typically, the amount of non-reactive component is between from about 0.01 to about 1 volume percent of the thin film.
The thin film composites exhibit excellent dielectric properties, as evidenced by their energy storage capacity. The thin film composites may further exhibit excellent ferroelectric or paraelectric properties.
The thin film composites of the invention have particular applicability in the production of capacitors. A capacitor containing the thin film composites of theinvention having an area approximating three stacked 25 cent pieces renders an equivalent energy density as that of a one quart juice which contains the thin film composites of the prior art.
Such capacitors may be two-dimensional (planar) or three-dimensional (having substrates characterized by trenches, depressions or macropores). The latter enhance the performance of the capacitors. These capacitors provide greater plate area and thus greater capacitance.
SUBSTITUTE SHEET (RULE 26~
CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 FIG. 1 is a schematic design of a (planar style) capacitor made by the sol-gel process described below. FIGS. 2-8 show alternative substrate surfa~es having increased specific areas between from about 100 to about 1 0,Q00 times the surface area of the planar styie capacitor of FIG. 1. In FIG. 2 and 3, discrete macropores define the upper surface of the substrate. In FIG. 4 and 5, trenches are formed in the substrate. This greatly increases the surface area of the substrate surface.
The dielectric material of the invention is coated over the surface of the pores or depressions of the substrates. Especially desirable results are obtained where the substrate is composed of silicon. Pores or depressions are typically created in the substrate by anodic etching. For instance, where silicon is the substrate, the p+ (or n+) monocrystalline silicon substrate may be sub~ected to anodic etching.
FIGS. 6 and 7 illustrate the substrate of the thin fiim composites of the invention wherein the substrate is characterized by depressions. Substrates of the planar capacitor may be formed from a n+ or p+ silicon substrate.
Capacitors in accordance with the invention are those exemplified in FIG.
1. Such substrates may be formed from for example n+ silicon substrate or it maybe formed from a polysilicon layer which lines the trench end in the n+ (or p+) silicon substrate. Upper plate and lower plate are electrica!ly insulated with the dielectric layer.
It is important not to fill the depressions, pores or trenches with the dielectric Sll~ 111 ~ITE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98107167 PCTnB97/00985 material since this creates high energy pockets and further may generate heat orraise the electric series resistance (ESR) of the capacitor. Rather, it is essentiai to conformly coat the depressions, pores or trenches.
The subsL, ~te may further be treated by methods defined in the art to exhibit projections which extend from its surface as set forth in FiG. 8.
Anodic etching is performed by submerging the silicon wafer or other substrate in a container of electrolytic solution of hydrofluoric acid and then subjecting the wafer to an electrolytic current. Such procedures are further described in U.S. Patent No. 5,508,542, herein incorporated by reference.
Further, note the techniques set forth in V. Lehmann, W. Honlein, H. Reisinger, H.
Wendt and ~I. Willer, Sol. State Technol., Nov., pp.99-10~(1995) directed to macropore substrates, likewise incorporated by reference. Further, as an alternative method, the surface enhancement may also be realized by producing substrate with textured surfaces and incorporating thin film dielectrics on saidtextured surfaces with an objective to increase the total surface area (by a factor greater than 1 where 1 corresponds to the planar surface) of the substrate.
Such substrates may further include lithographically patterned or anodically etched pores, naturaily occurring structures such as those occurring in zeolites and aerogels, anisotropically etched substrates as well as laser ablated locally patterned substrates.
Methods suitable for conformly coating the structured substrates of the - invention include procedures known in the art such as physical andlor reactive SlJts:, 111 UTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO 98/07167 PCT~B97/00985 evaporation, radio-frequency or microwave or electron cyclotron resonance methods inciuding sputtering, chemical vapor deposition including metallorganic chemical vapor deposition, hydride vapor phase deposition, liquid phase epitaxy and electro-epitaxy.
When produced by the methods recited herein, two-dimensional planar thin film composites have a capacitance generally up to 1.0, typically greater than 0.3, most typically beh,veen about 0.4 to about 0.5 farads/cm3. When produced by the methods described herein, thin film composites containing an increased specific area substrate surface have a capacitance generally up to 10Q, typically at least 1, more typically at least 50, most typically at least 100, farads per cubic centimeter. Since capacitance of the composites of the invention is increased exponentially when the area of the substrate is effectively enhanced as in the three-dimensional trench, depression or macroporous configuration, capacitance measurements greater than 1,000 farads/cm3 may be obtained. Capacitance measurements of the thin films in an enhanced area (of the three dimensional structure) have been calculated to be as high as 82.2 farad/cm3 in a 2,000 timesenhanced area and an energy density in excess of 13,000 joules/cm3.
(Capacitance measurements as recited herein are based on 6 to 10 nF
(nanofarads) per 1.3 mm diameter x 110 (nanometers) nm thick test samples.) Crystallization and increased energy storage capacity of the composites is further enhanced by the presence of additive "M" In the thin film. Suitable as additive "M" are those non-reactive electroconductive materials which form a SUBSTITUTE SHEET (RUI E 26) CA 022633~7 1999-02-12 W O98/07167 PCT~B97/00985 microstructure with the thir-l film. The resulting titanate may be represented by the formula MdBaaTibOc wherein d is about 0.01 to 0.25, a is about 0.7~ to about 1.Z~, b is about 0.7~ to about 1.25 and c is about 2.5 to about 5Ø X-ray diffraction of the material with "M" illustrates that a crystal structure which changes from predominantly cubic to tetragonal or perovskite and a crystallite size which increases with increasing concentration of "M" in the coating.
Preferred as "M" are gold, copper, intermetallic compounds such as Ni3AI, Ru and InSn. Particles of "M" should be electroconductive up to the melting point of the substrate and should neither react or diffuse through the substrate. As such, the particles wiil not degrade the properties of the resulting product. Particles of "M" should preferably be chosen such that they will form a specific microstructure.
Preferred results are obtained from particles characterized as accicular precipitates, feathered microstructures, dendritic precipitates or lamellar or eutectic-type structures. Most preferably, "M" is selected so as to cause internal strain in the film or plate that would promote crystallinity with desired crystal structure.
Enhancement of the capacitance with the "M'1 additive in barium titanate is likeiy caused by additional internal stress (compression~ by particles of"M".
Incorporation of particles of "M" further create strong local electric fields around the oxides which likely assists in electron transfer from the barium titanate matrix to the "M" particles. This in turn contributes to weakening of the bonds between the oxygen atoms and the cations in the barium titanates. At high temperatures during SUBSTITUTE SI~EET (RULE 26) =
CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 annealing, atomic migration is therefore facilitated. Thin films or ptates containing the oxides with additives have optimal energy storage capacities. In fact, the ra~ge is at least 10 times higher when additions of "M" are employed. Particles of "M"further enhance the dielectric, paraelectric andlor ferroelectric characteristics of the oxides.
Representative of such oxides are those of the formula MdBaaTibOc wherein a and b are independently about 0.75 to about 1.25, c is about 2.~ to about 5.0 and d is about 0.01 to 0.25. A particularly preferred inorganic oxide is of the formula MdBaaTibOc wherein a and b are both 1, c is 3 and d is 0.01 to 0.25. Especially preferred are those inorganic oxides of the stated formula wherein M is Au.
In general, a deposited inorganic oxide film is only partially crystalline. Since the dielectric properties are enhanced by film crystallinity, a post deposition thermal treatment is often used. This can be accompiished by rapid thermal annealing using quartz halogen lamps, laser-assisted annealing using for example an excimer or carbon dioxide laser, or using electron beam annealing.
The thin film composites of the invention may be prepared by depositing them on an appropriate substrate by such suitable deposition techniques as sol-gel [M. Kuwabara, S. Takahashi and T. Kuroda, Appl. Phys. Lett., 62, 3372(1993)], physical and/or reactive evaporation [Y. Yoneda, H. Kasatani, H. Terauchi, Y.
Yano, T. Terashima and Y. Bando, J. Phys. Soc. Jap., 62, 1840(1993)], radio-frequency or microwave or electron cyclotron resonance based techniques inciuding sputtering [S. Yamamishi, T. Sakuma, K. Takemura, Y. Miyasaka, Jap.
SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 J. Appl. Phys., 30, 2197(1991)], laser ablation and other laser-based depositiontechniques ~G.M. Davis and M.C Gower, Appl. Phys. Lett., 55, 112(1989)~, chemical vapour deposition including metalorganic chemical vapor deposition ~T.
Kimura, H. Yamauchi, H. Mashida, H. Kokubun and M. Yamada, Jap. J. Appl.
Phys., 33, 51 19(1994)], hydride vapor phase deposition, or liquid phase epitaxyand electro-epitaxy.
In the sol-gel process, a non-aqueous solution of titanium alkoxide is reacted with the cationic precursor at the desired stoichiometry and controllably hydrolyzed with a solvenVwater solution. A thin, adherent film of the hydrolyzedalkoxide solution (or "sol") is then applied to the substrate by either dip-coating or spin-coating at 1,000 to 3,000 rpm. I\Aultiple coatings may be required for increased film thicknesses; the hlms are heated to between 300~ to about 600~ C
for about 5 to 10 minutes to volatize the organic species and to render the dried "gel" film.
While the majority of the organic matter and water is removed from the films by annealing at 500 C; the barium titanate films are still only partially crystalline.
The product is then annealed for a period of time to remove volatile organic materials. A desirable annealing temperature is about 650~C for approximately one hour. The product is preferably further annealed to improve the film's crystallinity. The latter step involves heating the film at a rate of about 200~C/hr under dry nitrogen to a final annealing temperature of between 600~C and 900~C, preferably about 850~C until the desired crystallization is met.
SU~STITUTESHEET~RULE26~
CA 022633~7 l999-02-l2 W O 98/07167 PCT~B97/00985 Preferred as the titanium alkoxide is titanium isopropoxide. The "cationic precursor" is typically the reaction product of a glycol and barium oxide. Typical glycols are ethylene glycol and propylene glycol. The glycol-barium oxide reaction product is typically diluted with an alcohol prior to the addition of the titanium alkoxide. Suitable alcohols for use as diluents include ethanol, isopropyl alcohol and methanol.
During the soi-gel process, the thickness of the composite is a function of the rotation rate and the viscosity of the solution. Typically, the thickness of the composite is about ~00 nm at a minimum. The maximum thickness, for instance of a planar thin film composite, may be determined by the number of sol-gel layers deposited onto the substrate.
An alternative method to the sol-gel method is a spin-coating method. Here, a fine powder of i~arium oxide is added to the glycol. The reaction is exothermic and the reaction mixture is continuously stirred. The reaction mixture is then diluted with an alkanol, such as 2-propanol. In addition, the titanium alkoxide is then added. To avoid rapid precipitation the saturated glycol solution is kept at an elevated temperature, preferably about 70~C. The solution is then spun coated onto a suitable substrate. In the first stage of spin coating, the solution is added at approximateiy 2000 rpm for a short duration. In the second stage, the rotation is increased to about 4000 rpm for a time sufficient to achieve uniform deposition of film. The film is then dried for at a temperature between about 80 to about 100 C, preferably at 90~C. The product is then subjected to a similar annealing stage Sl~ TE SHEET (RULE 26~
CA 022633~7 1999-02-12 W O 98/07167 PCT~97/00985 as described for the sol-gel process.
The dielectric constant of the thin film comp~sites of the invention is between about 20 to about 80. With uniform polycrystalline thin films, the dielectric constants are in the range of about 4Q0 to about 800 . For bulk samples, however, the dielectric constants are usually higher, about 1800.
To obtain the desired high values of dielectric constant for the thin films, a ferroelectric, dielectric and/or paraelectric phase transition is induced. The onset of this transition depends on the annealing temperature. Thus, the product is annealed at elevated temperature until crystallization. Generally, the annealingtemperature is between from about 600CC to about 950 Z. Higher annealing temperatures tend to increase the average grain sizes in the films (ty~ically from about 20 nm at 650~C to about 12G nm at 950~C).
In a second embodiment of the invention, the coating of the substrate is prepared by first dissolving a reaction mixture of alcohol, barium diacetate andtitanium alkoxide in ambient atmosphere. The solution of alkanol, acetic acid glycerol is then continuously stirred. Bariurn acetate is then dissolved in the mixed solution. Titaniurn alkoxide, such as titanium butoxide is then added to the solution. The solution is continuously stirred for at least a couple of hours. The solution is then diluted with anhydrous alcohol, such as anhydrous methanol acetic acid and glycerol in the approximate weight ratio of 5:5 1. The solution is then spun coated onto a suitable substrate. The spinning is preferably done at - multiple stages. In the first stage, the solution is applied orto the substrate at SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 approximately 2000 rpm for about 10 secs. In the second stage, the solution is applied at a speed of about 4000 rpm for a period of time to achieve uniform deposition. Generally, this is for about ten seconds.
Alternatively, the substrate may be dipped into the solution at an average speed of about 10 to about 15 cm/min, preferably about 11.5 cm/min. The coating is then dried onto the substrate at a temperature of from about 300~C to about 500~C; typically films are first dried at 200~C for 2 hrs, and then baked at 400~C for about 20 mins to remove volatile organic materials. Films are then annealed at the temperature range of about 600~C to about 800~C to improve crystallinity. Typically the duration of annealing is about one hour.
It is most preferably that all reactants used in each of the alternative processes be of high purity. Generally, the level of purity is greater than 90%,preferably greater than 95%, most preferabiy greater than 99%. In addition, it is preferred that the individual steps of the invention be conducted in a nitrogen-free 1 5 atmosphere.
Inorganic oxides of the formuia AUdBaTiboc wherein a and b are independently about 0.75 to about 1.25, c is about 2.5 to about 5.0 and d is about 0.01 to 0.25 may be produced in accordance with any of the above procedures with the addition of an aqueous solution of M to the titanium containing solution prior to the latter being deposited onto the substrate. Where M is Au, an aqueous solution of HAuCI4 is preferably added to the solution containing the titanium. The HAuCI4 is preferably diluted with an alcohol prior to the addition of the HAuCI4 to SU~ ITE SHEET (RUI E 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 the other reactants.
In a typical process, a mixed solution of alkanol, such as methanol or ethanol, acetic acid and glycerol is mixed with continuous stirring at room temperature. Suitable mixing is achieved in about one hour. Barium acetate is then dissolved in the mixed solution. Titanium alkoxide, such as titanium butoxide, is added to the solution. The resulting solution is then stirred, typically for an additional two hours. HMCI4.xH20, such as HAuCI4.3H20 is then added to the solution. The solution is then diluted with an alkanol, such as methanol or ethanol, prior to spin coating. The solution is then spun coated onto a suitable substrate for a suitable time to achieve uniform deposition of coating. Typically, the spin coating proceeds through two stages. In the first stage, the solution is spin coated at a speed of about 2000 rpm, typically for about 10 seconds. In the second stage, the solution is spin coated onto the substrate at a speed of approximately 4000 rpm,typically for about 10 secs.
Alternatively, substrates may be dipped into the solution for coating of the thin film at an average speed of about 10 to about 15 cm/min, preferably about 11.5 cm/min. The thin film is then dried onto the substrate at a temperature of from about 300~C to about 500~C; typically films are first dried at approximately 200~ C
for about 2 hours, and then baked at about 400~ C for about 20 minutes to removevolatile organic materials. The films are then annealed at a temperature range of about 600~C to about 800~ C for a sufficient period of time tc improve crystaltinity.
Typically, the annealing time is for about one hour.
SIJ~ JTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO 98/07167 PCT~B97/0098 The purity of HMCI4 added to the titanium isopropoxide/reaction product is at least 90, preferably 95, most pre~erably 99, per cent.
Thin films of BaaTi~Oc and MdBaaTibOc may further be prepared by mixing titanium tetraacetate with an aqueous solution of alcohol. When Md BaaTibOc is the desired oxide, particles of M may be present in the aqueous alcohol solution. The titanium tetraacetate, in turn, may be prepared by reacting barium diacetate andacetic acid in the presence of an alcohol and a glycol The resultant solution isthen spun onto a substrate. Spinning may be effectuated at speeds approximating ~00 rpm. The speeds may be increased to about 1,000 to about 4,000 rpm until a uniform distribution is obtained. The coated substrate is then dried by heating to a temperature of from about 1 50~C to about 200~C. In a final heating step, the product may be heated at a temperature between about 360~C to about 400~C to remove volatile organic materials. The product is then annealed at a temperatureof about 500~C to about 850"C until crystallization is complete. The product is then isolated. As in the procedure recited above. the alternative procedure usesreactants of high purity and is conducted in a dry nitrogen-rich atmosphere.
Additives of "M" in the process enhance crystallization in the resulting thin films. In addition, they induce the phase transition of the barium titanate from cubic to tetragonal structure. The enhancement of the particles of M in the cryst~ tion process can be attributed to the structure of the thin film as well as by the substitutional additives, oxidation of metal particles, liquid-phase mediation, internal stress, electric-field, and heterogeneous nucleation.
SUBSTITUTE SHEET (RULE 26 CA 022633~7 1999-02-12 W O98/07167 PCTnB97/00985 In a preferred embodiment, the composites are employed in the production of capacitors wherein the thin film composites are interposed between two substrate iayers having a planar face. The substrate layers may be composed of various materials such as ceramic, glass, plastic or metal or metallized foil, such as copper foil. Preferably, the substrate layers are thin, flat, relatively stiff and have a planar face. The substrate layer(s) can be nonconductive, but in the casewhere the substrate is conductive it also can function as a current collector.
Especially preferred results are obtained where the top and/or bottom substrate layer of the capacitor is selected from silicon, copper, gold, aluminum, nickel or another electroconductive material having a melting point of at least 850~C.
Such capacitors may be prepared by depositing the thin film composite of the invention onto the substrate iayer having planar face. The thin film composites may be deposited onto a substrate by conventional techniques, such as dip coating, spin coating, doctor blading or spray coating. The resulting structure may then be annealed by conventional means such as thermal annealing, rapid thermal annealing, laser annealing or electron beam annealing. Annealing proceeds at a temperature of from about 500~C to about 850~ C. Generally, the annealing conditions will be selected to increase the grain size of the substrate comprising the thin film composite as well as to induce a textured condition in the substrate.
Subsequent annealing, in turn, enhances the texture and degree of crystallinity of the barium titanate thin film.
The composites of the invention have particular applicability as silicon SUBSTITUTE SI~EET (RULE 26 CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/0098S
nanostructure based supercapacitors. Since they are of nano size, the compositesof the invention provide a portable power source. Primary applications of the invention are in DC voltage energy storage systems such as batteries for watches, cellular phones, portable entertainment equipment, electric vehicles. In particular, power sources to electric vehicles may be provided from a single battery which may be charged in a matter of minutes.
Further, the thin films exhibit ferroelectric properties and thus the composites of the invention find particular utility as electrical energy storagedevices as well as non-volatile field effect transistors. The latter preferably contains a serniconductor as substrate. A buffer layer typically separates the thin film composite from the semiconductor substrate.
Conventional means may be electrically coupled to the dielectric and the planar substrate layers forming the sandwich with the dielectric.
In addition to high energy storage materials, the thin film composites of the invention may be used in energy transmission and/or sensing systems. Particular applicability of the invention is in portable radios, stereos, personal entertainment equipment, toys, flashlights, cellular phones as well as electric vehicles including but not limited to automobiles, boats, ships, submarines, motorcycles, forklifts, wheelchairs and airplanes. In addition, the invention may be employed in the production of aerospace systems such as rockets, satellites, lasers, orbiting plafforms and defense systems.
Conventional MOS capacitors based on SiO2 have dielectric constants near ~o SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 about 2 compared with capacitors comprising the thin films or plates of the invention which have about 3040 t;mes higher values and thus capacitances 30-40 times higher. In fact, the amount of energy stored in a battery or capacitor which contains the dielectric of the prior art and having a volume of 1000 ounces may be stored in a volume the size of a one ounce container when the barium titanate of the invention is used as dielectric. A capacitance of 40 millifarads (mfl per cubic centimeter has been obtained for a typical thin film cell using the barium titanates of the invention and with a planar structure (superficial area increase of 1). A superficial area increase of 1,000 to 10,000 would render a cell with a storage capacity of 40 to 400 farads/cm3 The composites of the invention may be used in the production of a number of semiconductor applications, especially Dynamic Random Access Memcries (DRAM), Static Random Access Memories (SRAM~ as well Metal Oxide Semiconductor (MOS) capacitors in Ultra Large Scale Integrated ~ULSI) circuits.
Large amounts of charge can be stored for a given gate voltage swing or logic pulse in light of the dielectric properties of the thin films. In particular, barium titanate capacitors of the invention significantly reduce the cost of manufacturing advanced DRAMs by reducing the complexity of the capacitor cell in 1-Gb DRAMs.
Large scale integration of DRAMs further require dielectrics with low leakage currents and low defect densities. Although multilayer silicon oxide-nitride-oxide (ONO) represent the present state of the art, charge trapping is an inevitable feature of such systems. However, in DRAMs, the device stability is seriously SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCTnB97/00985 affected by the associated shifts in the flatband potential and threshold voltage.
With the higher value single layer dielectrics of the invention, such problems are alleviated. The thin film composites of the invention exhibit very low leakage exhibited by tan o values (under 0.1%) and a Curie-Von Schweidler n value of about unity to 1.1. This permits long term storage capabilities.
Thus, the invention may be used to reduce capacitor and/or battery size for greater energy containment in equivalent volume, up to 1000 times the energy density over existing commercially available systems. The supercapacitors may beused in the isolation of DC potential delivery/harnessing systems where it is employed as a mediator in parallel configurations.
Secondary applications include AC delivery from a DC to AC converter to supply 120/240 vac to residences and businesses.
The invention may further be applied as a reasonable sized high current, short duration, discharge device for powering other devices that have short term, high energy requirements.
In fact, energy densities on the order of 1,000 to 10~000 times the energy density of a normal lead acid battery and charging rate of a conventional capacitor would be feasible with the present materials.
The supercapacitors have particular applicability in the semiconductor industry especially in the construction and manufacturing of integrated circuits. In addition, it may be used by hybrid semiconductor manufacturers using discrete dielectrics and storage systems on or off the hybrid template. It may be further be SUt~S 1 l l UTE SHEET ~RULE 26) CA 022633~7 1999-02-12 W O 98tO7167 PCT~97/00985 used by printed circuit board manufacturers for the purposes of embedding large value capacitance in multilayer boards. Still further it may be used by (i.) communications industry in portal~le, cellular phones and critical systems powerbackup (such as emergency generators); (ii.) military sector usage in advanced guidance systems, controls, targeting and tracking systems or any application requiring backup power sources or highly condensed electronics; or (iii.~ electric vehicles, land, sea, air and/or space as the primary, backup or initiating powersource.
Examples Example 1. One mol of Ba(CH3COO)2 was dissolved in a mixed solution of 20 mol C2H5OH, 25 mol CH3COOH and 1 mol gylcerol and then the solution was stirred for 2 hours. After stirring, 1 mol of Ti[O(C~12)3CH3]4 was added to the solution followed by stirring for 2 hours. Then, a mixed solution of HAuCI4-3H2Owith 0.05 mol and 4.1 mol of C21 IsOH was added to the solution. Finally, to form a Au-dispersed BaTiO3 film, the final solution was spin-coated onto two different kinds of p-type Si (p = 5 - 7 ncm) wafers which have been dipped into hydrofluoric acid (HF) to remove the native Si oxide films prior to spin-coating. The conditions for the spin-coating were 2000 rpm for 45 sec. After spin-coating on the solution, both of the sampies were annealed first at 1 75~C for 1 hour in N2 atmosphere, and then at 400~C for 1 hour. The final annealing termperatures were 700~C for 1 hour for one sample and 850~C for 1 hour in air for the other sample.
SUts~ UTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCT~B97/00985 A metal-insulator-semiconductor or MIS structure was fabricated for the capacitance measurements as shown in Fig. 1. Prior to evaporation of the lower (backside) aluminum electrode the samples were immersed into HF to remove the native silicon oxide. After evaporation they were annealed at 450~C to ensure good ohmic contact with the silicon substrate. The etch rate of BaTiO3 films for the sample annealed at 850~C during the fabrication process of the MIS structure wasmuch lower (slower) than that for the sample annealed at 700~C. This means that the former film should be much denser than the latter.
Example 2. One mol of Ba(CH3COO)2 was dissolved in a mixed solution of 20 mol C2H5OH, 25 mol CH3COOH and 1 mol glycerol. The solution was then stirred for 2 hours. After stirring, 1 mol of Ti[O(CH2)3CH3]4 was added to the solution followed by stirring for 2 hours. A mixed solution with various specified ~uantities of HAuCI~-3H20 and 1 mol of C2H5OH was then added. To form Au-dispersed BaTiO3films, the solution was spin-coated onto two different kinds of p-type Si (p = 0.5~0.7 ohms/cm and 5~7 ohms/ cm) wafers which had been dipped into hydrofluoric acid prior to spin-coating to remove the native Si oxide. The conditions for the spin coating were 2û00 rpm for 45 sec. After spin-coating thesolution, all the samples were annealed at 170~C for 1 hour in a nitrogen atmosphere, followed by two steps of successive annealing of 400~C for 1 hour and 700~C for 1 hour in air. The thickness of all the samples prepared in this way were around 110 nm as measured by a surface profilemeter and by using cross-sectional Field-Emission scanning electron microscopy.
~4 S~ TE SHE~T(RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 Both the highest annealing temperature (700~C) and thickness of the films (110 nm) were fixed. Only the gold ccncentration in the solution, and hence in the films, was varied. Table I summarizes the sample preparation conditions.
Structural evaluation of the films was carried out using x-ray diffraction (XR[)) on a Siemens D5000 system.
FIG.9 shows the XRD results for the four different samples. In the sample with no gold (i5t1 107A)~ only a small and broad peak is observed around 44.5~, which can be assigned to the (200) plane of cubic BaTiO3. On the other hand, forthe sample with the highest gold concentration (#11 07B), two sharp peaks at 22.3~
and 45.5~ were observed. These two peaks are due to the reflections from the (100) and (200) planes of BaTiO3, the latter peak was in fact not from the cubicphase but the tetragonal phase (or perovskite) of BaTiO3. Also from the XRD
pattern of sample #11 07B, it is clear that the film has a larger average grain size and is highly oriented along the ~111] direction, in spite of the use of a (100) Si wafer as a substrate which has a substantially different crystal structure. By adding a small amount of gold (0.005mols, #1107D) to the BaTiO3 film, the peak intensity for the (200) plane of cubic BaTiO3 increases, but the peak is still weak and broad. The cubic (200) peak intensity appears to weaken with further additions of gold (0.01 mols, #1107C) . From the above results, it may be concluded that adding gold to undoped BaTiO3 enhances crystallization in these films.
SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCT~Bg7/00985 Table I Summary of the sample preparation conditions Sample Code 1107A 1107B 1107C ' 107D
HAuCI4.3H,0 Content (mol) per 1mol Ba(CH?~CO0)7 0 0.05 0.01 ~ 05 Annealing Temperature (~C) 700 700 700 ' ~0 Thickness (nm) 110 110 110 1'0 Figure 10 is the X-ray diffraction pattern of the four samples above. The Figureshows a phase change from cubic to tetragonal and grain growth with increasing Au concentration.
Example 2. Barium titanate glycolate was prepared as follows. Six grams of barium oxide (99.5% purity) fine powder was added to 30 ml of ethylene glycol using vigorous stirring. The reaction was exothermic, and the reaction mixture was continuously stirred over 30 minutes. The reaction mixture was then dilute with 40 ml of 2--propanol. In addition, 9.0 ml of titanium isopropoxide was added with vigorous stirring. To avoid rapid precipitation the saturated ethylene glycol solution as kept hot (70~C). The morphology of the nanocrystaliine BaTiO3 film prepared is set forth in FIG.11 after annealing at 650~C for 1 hour. The coated samples were then dried under vacuum at 90~C for 2 hours. They were then heated at a rate of 20~~C/hour under dry flowing air up to the temperatures required to initiate calcination of the films, i.e., between 600 and 900~C. Elemental analysis using energy dispersive X-ray analysis on a scanning electron microscope showed that these films were BaTiO3 ~ilms. The spectra also showed the presence of elements from the glass substrate and Al contacts (Si, K, Na, and Al) and some impuritiescoming from the solution (Zn and Ca). Rapid thermal annealing of the films at SUBSTITUTE SHEET ~RULE 26) WO 98/07167 PCT~B97/00985 800~C can be used to improve the crystallinity of the films and to increase the dielectric constant from about 20 to about 80.
Various modifications may be made in the nature, composition, operation and arrangement of the various elements, steps and procedures described herein without departing from the spirit and scope of the invention as defined in the following claims.
SUBSTITUTE SHEET (RULE 26)
TITLE: SEMICONDUCTOR SUPE~RCAPACITOR SYSTEM, METHOD FOR MAKING SAME AND ARTICLES
PRODUCED THEREFROM
SPECIFICATION
Field of the invention The invention relates to barium titanate thin films and plates and to semiconductor devices such as microminiature, large capacitance capacitors usingsuch films. The invention further relates to barium titanate thin films and plates incorporating a non-reactive electroconductive material, "M". The storage capacity of the thin films and plates of the invention is at least 1 farad/cm3. The invention further relates to a method of preparing the thin films. Such crystalline thin films are characterized by a perovskite structure and have utility in the manufacture of a wide variety of ferroelectric, dielectric, pyroelectric, piezoelectric and electro-optic devices, such as nonvolatile semiconductor memories, thin-film capacitors, 1û pyroelectric (IR) detectors, sensors, surface acoustic wave substrates, optical waveguides, optical memories, spatial light modulators as well as frequency doublers for diode lasers.
Sl~ JTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO98/07167 PCT~B97/00985 Background of the Invention In the past years, there has been extended efforts in the development of high capacitance electrochemical energy storage devices, especially capacitors and batteries, for use in reduced volumetric areas. Both capacitors and batteries store energy by the separation of positive and negative charges. The need to store greater amounts of energy in a smaller package continues to drive new research.
Barium titanate (BaTiO3) has been studied for use in such microelectronic applications. Such studies have included the different forms of barium titanate including powder, bulk, thin film and multilayer owing to their excellent electronic and optical characteristics including high dielectric constant, transparency in visible wavelength, and high non-tinear optical susceptibility.
The use of barium titanates in electric vehicles is further highly desired.
Presently, automotive internal combustion engines are increasingly being challenged by environmental concerns, favoring an increased role for electric 1~ vehicles. Thus, supercapacitors, as well as batteries, play a major role in this developing market.
Supercapacitors having capacitances in the range of miili-Farads to Farads have suffered from slow charging and discharging cycles in light of their high series resistance (i.e., large RC time constants). In addition, they often rely on corrosive and environmentally unfriendly electrolytes. For instance, the BaTiO3 thin films set forth in T. Hayashi, Jpn. J. Appl. Phys., 32 4092 (1993) have a capacitance unacceptable for use in electric vehicles as well as other industries. Alternative SU~ JTE S~IEET ~RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 nanosized capacitors are -onstantly being sought.
Need exists therefore for an electrical energy storage device that combines the desirable features of conventional capacitors yet can store much iarger amounts of energy in a smaller package and can be manufactured at reasonable costs.
Summary of the Invention The invention relates to a nanostructured BaTiO3 thin film composite that has from 1,000 to 10,000 times the area and storage capacity of conventional BaTiO3 thin fiims, plates and arrays. The BaTiO3 thin films and plates of the invention can also exhibit a variable discharge rate controlled by optical iliumination (pumping) .
The barium titanates comprising the coating of the thin films or plates of the invention exhibit dielectric, ferroelectric and/or paraelectric properties. The barium titanates are of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is 2.5 to about 5Ø The thin film composites of the invention exhibit a storage capacity of at least 1 to 100 farads per cubic centimeter.
In another embodiment of the invention, the thin fiims comprise barium titanate incorporating a non-reactive electroconductive material, "M", capable of forming a microstructure with the thin film. The resulting titanate is of the formula MdBaaTibOc wherein d is about 0.01 to about Q.25, a is about 0.75 to about 1.25,b is about 0.75 to about 1.25 and c is about 2.5 to about 5Ø Thin film SU~ ~ TE SHEET (RULE 26) CA 022633~7 l999-02-l2 W O 98/07167 PCT~B97/00985 composites containing the incorporated material have a storage capacity of a magnitude between 10 to 1,000 times higher than the storage capacity of the composite materials without incorporated "M" (BaaTibOc).
The thin film composites of the invention have particular applicabiiity in the production of microminiature capacitors.
Lastly, the invention relates to a process of preparing and using a barium titanate film composite, optionally incorporating particles of "M".
Brief Description of the Drawings FIG. 1 is a sample preparation of a planar capacitor made by the sol-gel process.
FIG. 2 is a perspective view of the substrate of the thin film composite of the invention having macropores.
FIG. 3 is a side view of the substrate of FIG. 2.
FIG. 4 is a perspective view of the substrate of the thin film composite of the invention having trenches.
FIG. 5 is a side view of the substrate of FIG. 4.
FIG. 6 is a perspective view of the substrate of the thin film composite of the invention having depressions.
Z0 FIG. 7 is a side view of the substrate of FIG. 6.
FIG. 8 is a side view of a substrate of the thin film composite of the inventionhaving projections extending from the surface.
SUBSTITUTE SHEET (RUEE 26) CA 022633~7 1999-02-12 W O 981~7167 PCT~B97tO~985 FIG. 9 is an internal structure of a thin film composite of the inv~ntion as seen using a scanning electron microscope.
FIG. 10 is the x-ray diffraction pattern of a barium titanate composite prepared in accordance with the invention.
FIG. 11 illustrates the morphology of a nanocrystalline BaTiO3 film composite prepared in accordance with the invention.
Detailed Description of Preferred Embodiments The thin film composites of the invention comprise a thin iayer, plate or array (collectively termed "thin film") of the formula Ba~TibOc wherein a and b are independentty between 0.7~ and 1.25 and c is between about 2.5 and about 5.0 deposited onto a substrate. In a preferred embodiment, both a and b are 1 and c is about 3 of the formula BaaTi,,Oc .
The thin film composites of the invention exhibit an extremely high energy density. As such, thin film composites of the invention have particular applicability in the production of microminiature capacitors.
In addition. the BaTiO~ thin film composites of the invention exhibit a variable discharge rate controlled optically. This permits the capacitance of an article composed of such composites to be tunable for applications where a specific capacitance is desired. In addition, this facilitates designing variable 2~ electric series resistance devices for controlled power delivery.
The substrate of the thin film composites of the invention typically are SIJ~S 1 I ~ ~JTE SHEET (RULE 26) CA 022633~7 1999-02-12 composed of silicon, fused silica, Pt-coated silicon, alumina, sapphire, Pt-coated sapphire, metallized foil, such as a copper foil, or a single crystal SrTiO3 substrate.
In addition, the substrate may consist of any electroconductive metat ha~ing a melting point of at least 850 C. The substrate shouid not meit or undergo a phase transition under typical annealing conditions or react or diffuse with the othercomponents of the composite (or laminate as described herein) so as to diminish the properties of the resultant product. Thus, for example, Al would be unsuitable as it would melt at 850~C, a typical annealing temperature.
Suitable for use as the silicon layer are rapidly thermally processed silicon layers crystalli~ed by a lamp based annealling system. Alternatively, silicon whose crystallization has been induced by a laser, such as an excimer laser, may also be used. Alternatively, the substrate may comprise an oxide layer which is rapidly thermally processed using a lamp-based annealing system or laser annealing with a laser such as an excimer or carbon dioxide laser or electron-beam processing.
Still further, the substrate of the invention offering increased surface areas may include anisotropically etched substrates as well as locally patterned substrates by laser ablation.
The thin film of the composite comprises an inorganic oxide of the formula BaaTibOc wherein a and b are independently between 0.75 and 1.25 and c is between about 2.5 and about 5Ø In preferred embodiment, a and b are approximately 1 and c is about 3Ø In a most preferred embodiment, the inor~anic oxides exhibit a tetragonal or perovskite crystalline lattice . During the process SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 described herein, oxygen vacancies and internal stress contribute to the crystailite growth and phase transformation of the oxide. For larger grain sizes of the barium titanate, the material tends to assume a tetragonal crystal structure.
The thin film may further contain a non-reactive component capable of inducing internal strain. Suitable for use as non-reactive components include europium, silicon nitride, boron nitride, magnesium oxide, alumina, tungsten carbide as well as diamond particles. While amounts as high as 50 volume percent of the non-reactive ~omponent may be employed, the preferred amount is less than 10 volume percent. Typically, the amount of non-reactive component is between from about 0.01 to about 1 volume percent of the thin film.
The thin film composites exhibit excellent dielectric properties, as evidenced by their energy storage capacity. The thin film composites may further exhibit excellent ferroelectric or paraelectric properties.
The thin film composites of the invention have particular applicability in the production of capacitors. A capacitor containing the thin film composites of theinvention having an area approximating three stacked 25 cent pieces renders an equivalent energy density as that of a one quart juice which contains the thin film composites of the prior art.
Such capacitors may be two-dimensional (planar) or three-dimensional (having substrates characterized by trenches, depressions or macropores). The latter enhance the performance of the capacitors. These capacitors provide greater plate area and thus greater capacitance.
SUBSTITUTE SHEET (RULE 26~
CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 FIG. 1 is a schematic design of a (planar style) capacitor made by the sol-gel process described below. FIGS. 2-8 show alternative substrate surfa~es having increased specific areas between from about 100 to about 1 0,Q00 times the surface area of the planar styie capacitor of FIG. 1. In FIG. 2 and 3, discrete macropores define the upper surface of the substrate. In FIG. 4 and 5, trenches are formed in the substrate. This greatly increases the surface area of the substrate surface.
The dielectric material of the invention is coated over the surface of the pores or depressions of the substrates. Especially desirable results are obtained where the substrate is composed of silicon. Pores or depressions are typically created in the substrate by anodic etching. For instance, where silicon is the substrate, the p+ (or n+) monocrystalline silicon substrate may be sub~ected to anodic etching.
FIGS. 6 and 7 illustrate the substrate of the thin fiim composites of the invention wherein the substrate is characterized by depressions. Substrates of the planar capacitor may be formed from a n+ or p+ silicon substrate.
Capacitors in accordance with the invention are those exemplified in FIG.
1. Such substrates may be formed from for example n+ silicon substrate or it maybe formed from a polysilicon layer which lines the trench end in the n+ (or p+) silicon substrate. Upper plate and lower plate are electrica!ly insulated with the dielectric layer.
It is important not to fill the depressions, pores or trenches with the dielectric Sll~ 111 ~ITE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98107167 PCTnB97/00985 material since this creates high energy pockets and further may generate heat orraise the electric series resistance (ESR) of the capacitor. Rather, it is essentiai to conformly coat the depressions, pores or trenches.
The subsL, ~te may further be treated by methods defined in the art to exhibit projections which extend from its surface as set forth in FiG. 8.
Anodic etching is performed by submerging the silicon wafer or other substrate in a container of electrolytic solution of hydrofluoric acid and then subjecting the wafer to an electrolytic current. Such procedures are further described in U.S. Patent No. 5,508,542, herein incorporated by reference.
Further, note the techniques set forth in V. Lehmann, W. Honlein, H. Reisinger, H.
Wendt and ~I. Willer, Sol. State Technol., Nov., pp.99-10~(1995) directed to macropore substrates, likewise incorporated by reference. Further, as an alternative method, the surface enhancement may also be realized by producing substrate with textured surfaces and incorporating thin film dielectrics on saidtextured surfaces with an objective to increase the total surface area (by a factor greater than 1 where 1 corresponds to the planar surface) of the substrate.
Such substrates may further include lithographically patterned or anodically etched pores, naturaily occurring structures such as those occurring in zeolites and aerogels, anisotropically etched substrates as well as laser ablated locally patterned substrates.
Methods suitable for conformly coating the structured substrates of the - invention include procedures known in the art such as physical andlor reactive SlJts:, 111 UTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO 98/07167 PCT~B97/00985 evaporation, radio-frequency or microwave or electron cyclotron resonance methods inciuding sputtering, chemical vapor deposition including metallorganic chemical vapor deposition, hydride vapor phase deposition, liquid phase epitaxy and electro-epitaxy.
When produced by the methods recited herein, two-dimensional planar thin film composites have a capacitance generally up to 1.0, typically greater than 0.3, most typically beh,veen about 0.4 to about 0.5 farads/cm3. When produced by the methods described herein, thin film composites containing an increased specific area substrate surface have a capacitance generally up to 10Q, typically at least 1, more typically at least 50, most typically at least 100, farads per cubic centimeter. Since capacitance of the composites of the invention is increased exponentially when the area of the substrate is effectively enhanced as in the three-dimensional trench, depression or macroporous configuration, capacitance measurements greater than 1,000 farads/cm3 may be obtained. Capacitance measurements of the thin films in an enhanced area (of the three dimensional structure) have been calculated to be as high as 82.2 farad/cm3 in a 2,000 timesenhanced area and an energy density in excess of 13,000 joules/cm3.
(Capacitance measurements as recited herein are based on 6 to 10 nF
(nanofarads) per 1.3 mm diameter x 110 (nanometers) nm thick test samples.) Crystallization and increased energy storage capacity of the composites is further enhanced by the presence of additive "M" In the thin film. Suitable as additive "M" are those non-reactive electroconductive materials which form a SUBSTITUTE SHEET (RUI E 26) CA 022633~7 1999-02-12 W O98/07167 PCT~B97/00985 microstructure with the thir-l film. The resulting titanate may be represented by the formula MdBaaTibOc wherein d is about 0.01 to 0.25, a is about 0.7~ to about 1.Z~, b is about 0.7~ to about 1.25 and c is about 2.5 to about 5Ø X-ray diffraction of the material with "M" illustrates that a crystal structure which changes from predominantly cubic to tetragonal or perovskite and a crystallite size which increases with increasing concentration of "M" in the coating.
Preferred as "M" are gold, copper, intermetallic compounds such as Ni3AI, Ru and InSn. Particles of "M" should be electroconductive up to the melting point of the substrate and should neither react or diffuse through the substrate. As such, the particles wiil not degrade the properties of the resulting product. Particles of "M" should preferably be chosen such that they will form a specific microstructure.
Preferred results are obtained from particles characterized as accicular precipitates, feathered microstructures, dendritic precipitates or lamellar or eutectic-type structures. Most preferably, "M" is selected so as to cause internal strain in the film or plate that would promote crystallinity with desired crystal structure.
Enhancement of the capacitance with the "M'1 additive in barium titanate is likeiy caused by additional internal stress (compression~ by particles of"M".
Incorporation of particles of "M" further create strong local electric fields around the oxides which likely assists in electron transfer from the barium titanate matrix to the "M" particles. This in turn contributes to weakening of the bonds between the oxygen atoms and the cations in the barium titanates. At high temperatures during SUBSTITUTE SI~EET (RULE 26) =
CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 annealing, atomic migration is therefore facilitated. Thin films or ptates containing the oxides with additives have optimal energy storage capacities. In fact, the ra~ge is at least 10 times higher when additions of "M" are employed. Particles of "M"further enhance the dielectric, paraelectric andlor ferroelectric characteristics of the oxides.
Representative of such oxides are those of the formula MdBaaTibOc wherein a and b are independently about 0.75 to about 1.25, c is about 2.~ to about 5.0 and d is about 0.01 to 0.25. A particularly preferred inorganic oxide is of the formula MdBaaTibOc wherein a and b are both 1, c is 3 and d is 0.01 to 0.25. Especially preferred are those inorganic oxides of the stated formula wherein M is Au.
In general, a deposited inorganic oxide film is only partially crystalline. Since the dielectric properties are enhanced by film crystallinity, a post deposition thermal treatment is often used. This can be accompiished by rapid thermal annealing using quartz halogen lamps, laser-assisted annealing using for example an excimer or carbon dioxide laser, or using electron beam annealing.
The thin film composites of the invention may be prepared by depositing them on an appropriate substrate by such suitable deposition techniques as sol-gel [M. Kuwabara, S. Takahashi and T. Kuroda, Appl. Phys. Lett., 62, 3372(1993)], physical and/or reactive evaporation [Y. Yoneda, H. Kasatani, H. Terauchi, Y.
Yano, T. Terashima and Y. Bando, J. Phys. Soc. Jap., 62, 1840(1993)], radio-frequency or microwave or electron cyclotron resonance based techniques inciuding sputtering [S. Yamamishi, T. Sakuma, K. Takemura, Y. Miyasaka, Jap.
SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 J. Appl. Phys., 30, 2197(1991)], laser ablation and other laser-based depositiontechniques ~G.M. Davis and M.C Gower, Appl. Phys. Lett., 55, 112(1989)~, chemical vapour deposition including metalorganic chemical vapor deposition ~T.
Kimura, H. Yamauchi, H. Mashida, H. Kokubun and M. Yamada, Jap. J. Appl.
Phys., 33, 51 19(1994)], hydride vapor phase deposition, or liquid phase epitaxyand electro-epitaxy.
In the sol-gel process, a non-aqueous solution of titanium alkoxide is reacted with the cationic precursor at the desired stoichiometry and controllably hydrolyzed with a solvenVwater solution. A thin, adherent film of the hydrolyzedalkoxide solution (or "sol") is then applied to the substrate by either dip-coating or spin-coating at 1,000 to 3,000 rpm. I\Aultiple coatings may be required for increased film thicknesses; the hlms are heated to between 300~ to about 600~ C
for about 5 to 10 minutes to volatize the organic species and to render the dried "gel" film.
While the majority of the organic matter and water is removed from the films by annealing at 500 C; the barium titanate films are still only partially crystalline.
The product is then annealed for a period of time to remove volatile organic materials. A desirable annealing temperature is about 650~C for approximately one hour. The product is preferably further annealed to improve the film's crystallinity. The latter step involves heating the film at a rate of about 200~C/hr under dry nitrogen to a final annealing temperature of between 600~C and 900~C, preferably about 850~C until the desired crystallization is met.
SU~STITUTESHEET~RULE26~
CA 022633~7 l999-02-l2 W O 98/07167 PCT~B97/00985 Preferred as the titanium alkoxide is titanium isopropoxide. The "cationic precursor" is typically the reaction product of a glycol and barium oxide. Typical glycols are ethylene glycol and propylene glycol. The glycol-barium oxide reaction product is typically diluted with an alcohol prior to the addition of the titanium alkoxide. Suitable alcohols for use as diluents include ethanol, isopropyl alcohol and methanol.
During the soi-gel process, the thickness of the composite is a function of the rotation rate and the viscosity of the solution. Typically, the thickness of the composite is about ~00 nm at a minimum. The maximum thickness, for instance of a planar thin film composite, may be determined by the number of sol-gel layers deposited onto the substrate.
An alternative method to the sol-gel method is a spin-coating method. Here, a fine powder of i~arium oxide is added to the glycol. The reaction is exothermic and the reaction mixture is continuously stirred. The reaction mixture is then diluted with an alkanol, such as 2-propanol. In addition, the titanium alkoxide is then added. To avoid rapid precipitation the saturated glycol solution is kept at an elevated temperature, preferably about 70~C. The solution is then spun coated onto a suitable substrate. In the first stage of spin coating, the solution is added at approximateiy 2000 rpm for a short duration. In the second stage, the rotation is increased to about 4000 rpm for a time sufficient to achieve uniform deposition of film. The film is then dried for at a temperature between about 80 to about 100 C, preferably at 90~C. The product is then subjected to a similar annealing stage Sl~ TE SHEET (RULE 26~
CA 022633~7 1999-02-12 W O 98/07167 PCT~97/00985 as described for the sol-gel process.
The dielectric constant of the thin film comp~sites of the invention is between about 20 to about 80. With uniform polycrystalline thin films, the dielectric constants are in the range of about 4Q0 to about 800 . For bulk samples, however, the dielectric constants are usually higher, about 1800.
To obtain the desired high values of dielectric constant for the thin films, a ferroelectric, dielectric and/or paraelectric phase transition is induced. The onset of this transition depends on the annealing temperature. Thus, the product is annealed at elevated temperature until crystallization. Generally, the annealingtemperature is between from about 600CC to about 950 Z. Higher annealing temperatures tend to increase the average grain sizes in the films (ty~ically from about 20 nm at 650~C to about 12G nm at 950~C).
In a second embodiment of the invention, the coating of the substrate is prepared by first dissolving a reaction mixture of alcohol, barium diacetate andtitanium alkoxide in ambient atmosphere. The solution of alkanol, acetic acid glycerol is then continuously stirred. Bariurn acetate is then dissolved in the mixed solution. Titaniurn alkoxide, such as titanium butoxide is then added to the solution. The solution is continuously stirred for at least a couple of hours. The solution is then diluted with anhydrous alcohol, such as anhydrous methanol acetic acid and glycerol in the approximate weight ratio of 5:5 1. The solution is then spun coated onto a suitable substrate. The spinning is preferably done at - multiple stages. In the first stage, the solution is applied orto the substrate at SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 approximately 2000 rpm for about 10 secs. In the second stage, the solution is applied at a speed of about 4000 rpm for a period of time to achieve uniform deposition. Generally, this is for about ten seconds.
Alternatively, the substrate may be dipped into the solution at an average speed of about 10 to about 15 cm/min, preferably about 11.5 cm/min. The coating is then dried onto the substrate at a temperature of from about 300~C to about 500~C; typically films are first dried at 200~C for 2 hrs, and then baked at 400~C for about 20 mins to remove volatile organic materials. Films are then annealed at the temperature range of about 600~C to about 800~C to improve crystallinity. Typically the duration of annealing is about one hour.
It is most preferably that all reactants used in each of the alternative processes be of high purity. Generally, the level of purity is greater than 90%,preferably greater than 95%, most preferabiy greater than 99%. In addition, it is preferred that the individual steps of the invention be conducted in a nitrogen-free 1 5 atmosphere.
Inorganic oxides of the formuia AUdBaTiboc wherein a and b are independently about 0.75 to about 1.25, c is about 2.5 to about 5.0 and d is about 0.01 to 0.25 may be produced in accordance with any of the above procedures with the addition of an aqueous solution of M to the titanium containing solution prior to the latter being deposited onto the substrate. Where M is Au, an aqueous solution of HAuCI4 is preferably added to the solution containing the titanium. The HAuCI4 is preferably diluted with an alcohol prior to the addition of the HAuCI4 to SU~ ITE SHEET (RUI E 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 the other reactants.
In a typical process, a mixed solution of alkanol, such as methanol or ethanol, acetic acid and glycerol is mixed with continuous stirring at room temperature. Suitable mixing is achieved in about one hour. Barium acetate is then dissolved in the mixed solution. Titanium alkoxide, such as titanium butoxide, is added to the solution. The resulting solution is then stirred, typically for an additional two hours. HMCI4.xH20, such as HAuCI4.3H20 is then added to the solution. The solution is then diluted with an alkanol, such as methanol or ethanol, prior to spin coating. The solution is then spun coated onto a suitable substrate for a suitable time to achieve uniform deposition of coating. Typically, the spin coating proceeds through two stages. In the first stage, the solution is spin coated at a speed of about 2000 rpm, typically for about 10 seconds. In the second stage, the solution is spin coated onto the substrate at a speed of approximately 4000 rpm,typically for about 10 secs.
Alternatively, substrates may be dipped into the solution for coating of the thin film at an average speed of about 10 to about 15 cm/min, preferably about 11.5 cm/min. The thin film is then dried onto the substrate at a temperature of from about 300~C to about 500~C; typically films are first dried at approximately 200~ C
for about 2 hours, and then baked at about 400~ C for about 20 minutes to removevolatile organic materials. The films are then annealed at a temperature range of about 600~C to about 800~ C for a sufficient period of time tc improve crystaltinity.
Typically, the annealing time is for about one hour.
SIJ~ JTE SHEET (RULE 26) CA 022633~7 1999-02-12 WO 98/07167 PCT~B97/0098 The purity of HMCI4 added to the titanium isopropoxide/reaction product is at least 90, preferably 95, most pre~erably 99, per cent.
Thin films of BaaTi~Oc and MdBaaTibOc may further be prepared by mixing titanium tetraacetate with an aqueous solution of alcohol. When Md BaaTibOc is the desired oxide, particles of M may be present in the aqueous alcohol solution. The titanium tetraacetate, in turn, may be prepared by reacting barium diacetate andacetic acid in the presence of an alcohol and a glycol The resultant solution isthen spun onto a substrate. Spinning may be effectuated at speeds approximating ~00 rpm. The speeds may be increased to about 1,000 to about 4,000 rpm until a uniform distribution is obtained. The coated substrate is then dried by heating to a temperature of from about 1 50~C to about 200~C. In a final heating step, the product may be heated at a temperature between about 360~C to about 400~C to remove volatile organic materials. The product is then annealed at a temperatureof about 500~C to about 850"C until crystallization is complete. The product is then isolated. As in the procedure recited above. the alternative procedure usesreactants of high purity and is conducted in a dry nitrogen-rich atmosphere.
Additives of "M" in the process enhance crystallization in the resulting thin films. In addition, they induce the phase transition of the barium titanate from cubic to tetragonal structure. The enhancement of the particles of M in the cryst~ tion process can be attributed to the structure of the thin film as well as by the substitutional additives, oxidation of metal particles, liquid-phase mediation, internal stress, electric-field, and heterogeneous nucleation.
SUBSTITUTE SHEET (RULE 26 CA 022633~7 1999-02-12 W O98/07167 PCTnB97/00985 In a preferred embodiment, the composites are employed in the production of capacitors wherein the thin film composites are interposed between two substrate iayers having a planar face. The substrate layers may be composed of various materials such as ceramic, glass, plastic or metal or metallized foil, such as copper foil. Preferably, the substrate layers are thin, flat, relatively stiff and have a planar face. The substrate layer(s) can be nonconductive, but in the casewhere the substrate is conductive it also can function as a current collector.
Especially preferred results are obtained where the top and/or bottom substrate layer of the capacitor is selected from silicon, copper, gold, aluminum, nickel or another electroconductive material having a melting point of at least 850~C.
Such capacitors may be prepared by depositing the thin film composite of the invention onto the substrate iayer having planar face. The thin film composites may be deposited onto a substrate by conventional techniques, such as dip coating, spin coating, doctor blading or spray coating. The resulting structure may then be annealed by conventional means such as thermal annealing, rapid thermal annealing, laser annealing or electron beam annealing. Annealing proceeds at a temperature of from about 500~C to about 850~ C. Generally, the annealing conditions will be selected to increase the grain size of the substrate comprising the thin film composite as well as to induce a textured condition in the substrate.
Subsequent annealing, in turn, enhances the texture and degree of crystallinity of the barium titanate thin film.
The composites of the invention have particular applicability as silicon SUBSTITUTE SI~EET (RULE 26 CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/0098S
nanostructure based supercapacitors. Since they are of nano size, the compositesof the invention provide a portable power source. Primary applications of the invention are in DC voltage energy storage systems such as batteries for watches, cellular phones, portable entertainment equipment, electric vehicles. In particular, power sources to electric vehicles may be provided from a single battery which may be charged in a matter of minutes.
Further, the thin films exhibit ferroelectric properties and thus the composites of the invention find particular utility as electrical energy storagedevices as well as non-volatile field effect transistors. The latter preferably contains a serniconductor as substrate. A buffer layer typically separates the thin film composite from the semiconductor substrate.
Conventional means may be electrically coupled to the dielectric and the planar substrate layers forming the sandwich with the dielectric.
In addition to high energy storage materials, the thin film composites of the invention may be used in energy transmission and/or sensing systems. Particular applicability of the invention is in portable radios, stereos, personal entertainment equipment, toys, flashlights, cellular phones as well as electric vehicles including but not limited to automobiles, boats, ships, submarines, motorcycles, forklifts, wheelchairs and airplanes. In addition, the invention may be employed in the production of aerospace systems such as rockets, satellites, lasers, orbiting plafforms and defense systems.
Conventional MOS capacitors based on SiO2 have dielectric constants near ~o SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 about 2 compared with capacitors comprising the thin films or plates of the invention which have about 3040 t;mes higher values and thus capacitances 30-40 times higher. In fact, the amount of energy stored in a battery or capacitor which contains the dielectric of the prior art and having a volume of 1000 ounces may be stored in a volume the size of a one ounce container when the barium titanate of the invention is used as dielectric. A capacitance of 40 millifarads (mfl per cubic centimeter has been obtained for a typical thin film cell using the barium titanates of the invention and with a planar structure (superficial area increase of 1). A superficial area increase of 1,000 to 10,000 would render a cell with a storage capacity of 40 to 400 farads/cm3 The composites of the invention may be used in the production of a number of semiconductor applications, especially Dynamic Random Access Memcries (DRAM), Static Random Access Memories (SRAM~ as well Metal Oxide Semiconductor (MOS) capacitors in Ultra Large Scale Integrated ~ULSI) circuits.
Large amounts of charge can be stored for a given gate voltage swing or logic pulse in light of the dielectric properties of the thin films. In particular, barium titanate capacitors of the invention significantly reduce the cost of manufacturing advanced DRAMs by reducing the complexity of the capacitor cell in 1-Gb DRAMs.
Large scale integration of DRAMs further require dielectrics with low leakage currents and low defect densities. Although multilayer silicon oxide-nitride-oxide (ONO) represent the present state of the art, charge trapping is an inevitable feature of such systems. However, in DRAMs, the device stability is seriously SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCTnB97/00985 affected by the associated shifts in the flatband potential and threshold voltage.
With the higher value single layer dielectrics of the invention, such problems are alleviated. The thin film composites of the invention exhibit very low leakage exhibited by tan o values (under 0.1%) and a Curie-Von Schweidler n value of about unity to 1.1. This permits long term storage capabilities.
Thus, the invention may be used to reduce capacitor and/or battery size for greater energy containment in equivalent volume, up to 1000 times the energy density over existing commercially available systems. The supercapacitors may beused in the isolation of DC potential delivery/harnessing systems where it is employed as a mediator in parallel configurations.
Secondary applications include AC delivery from a DC to AC converter to supply 120/240 vac to residences and businesses.
The invention may further be applied as a reasonable sized high current, short duration, discharge device for powering other devices that have short term, high energy requirements.
In fact, energy densities on the order of 1,000 to 10~000 times the energy density of a normal lead acid battery and charging rate of a conventional capacitor would be feasible with the present materials.
The supercapacitors have particular applicability in the semiconductor industry especially in the construction and manufacturing of integrated circuits. In addition, it may be used by hybrid semiconductor manufacturers using discrete dielectrics and storage systems on or off the hybrid template. It may be further be SUt~S 1 l l UTE SHEET ~RULE 26) CA 022633~7 1999-02-12 W O 98tO7167 PCT~97/00985 used by printed circuit board manufacturers for the purposes of embedding large value capacitance in multilayer boards. Still further it may be used by (i.) communications industry in portal~le, cellular phones and critical systems powerbackup (such as emergency generators); (ii.) military sector usage in advanced guidance systems, controls, targeting and tracking systems or any application requiring backup power sources or highly condensed electronics; or (iii.~ electric vehicles, land, sea, air and/or space as the primary, backup or initiating powersource.
Examples Example 1. One mol of Ba(CH3COO)2 was dissolved in a mixed solution of 20 mol C2H5OH, 25 mol CH3COOH and 1 mol gylcerol and then the solution was stirred for 2 hours. After stirring, 1 mol of Ti[O(C~12)3CH3]4 was added to the solution followed by stirring for 2 hours. Then, a mixed solution of HAuCI4-3H2Owith 0.05 mol and 4.1 mol of C21 IsOH was added to the solution. Finally, to form a Au-dispersed BaTiO3 film, the final solution was spin-coated onto two different kinds of p-type Si (p = 5 - 7 ncm) wafers which have been dipped into hydrofluoric acid (HF) to remove the native Si oxide films prior to spin-coating. The conditions for the spin-coating were 2000 rpm for 45 sec. After spin-coating on the solution, both of the sampies were annealed first at 1 75~C for 1 hour in N2 atmosphere, and then at 400~C for 1 hour. The final annealing termperatures were 700~C for 1 hour for one sample and 850~C for 1 hour in air for the other sample.
SUts~ UTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCT~B97/00985 A metal-insulator-semiconductor or MIS structure was fabricated for the capacitance measurements as shown in Fig. 1. Prior to evaporation of the lower (backside) aluminum electrode the samples were immersed into HF to remove the native silicon oxide. After evaporation they were annealed at 450~C to ensure good ohmic contact with the silicon substrate. The etch rate of BaTiO3 films for the sample annealed at 850~C during the fabrication process of the MIS structure wasmuch lower (slower) than that for the sample annealed at 700~C. This means that the former film should be much denser than the latter.
Example 2. One mol of Ba(CH3COO)2 was dissolved in a mixed solution of 20 mol C2H5OH, 25 mol CH3COOH and 1 mol glycerol. The solution was then stirred for 2 hours. After stirring, 1 mol of Ti[O(CH2)3CH3]4 was added to the solution followed by stirring for 2 hours. A mixed solution with various specified ~uantities of HAuCI~-3H20 and 1 mol of C2H5OH was then added. To form Au-dispersed BaTiO3films, the solution was spin-coated onto two different kinds of p-type Si (p = 0.5~0.7 ohms/cm and 5~7 ohms/ cm) wafers which had been dipped into hydrofluoric acid prior to spin-coating to remove the native Si oxide. The conditions for the spin coating were 2û00 rpm for 45 sec. After spin-coating thesolution, all the samples were annealed at 170~C for 1 hour in a nitrogen atmosphere, followed by two steps of successive annealing of 400~C for 1 hour and 700~C for 1 hour in air. The thickness of all the samples prepared in this way were around 110 nm as measured by a surface profilemeter and by using cross-sectional Field-Emission scanning electron microscopy.
~4 S~ TE SHE~T(RULE 26) CA 022633~7 1999-02-12 W O 98/07167 PCT~B97/00985 Both the highest annealing temperature (700~C) and thickness of the films (110 nm) were fixed. Only the gold ccncentration in the solution, and hence in the films, was varied. Table I summarizes the sample preparation conditions.
Structural evaluation of the films was carried out using x-ray diffraction (XR[)) on a Siemens D5000 system.
FIG.9 shows the XRD results for the four different samples. In the sample with no gold (i5t1 107A)~ only a small and broad peak is observed around 44.5~, which can be assigned to the (200) plane of cubic BaTiO3. On the other hand, forthe sample with the highest gold concentration (#11 07B), two sharp peaks at 22.3~
and 45.5~ were observed. These two peaks are due to the reflections from the (100) and (200) planes of BaTiO3, the latter peak was in fact not from the cubicphase but the tetragonal phase (or perovskite) of BaTiO3. Also from the XRD
pattern of sample #11 07B, it is clear that the film has a larger average grain size and is highly oriented along the ~111] direction, in spite of the use of a (100) Si wafer as a substrate which has a substantially different crystal structure. By adding a small amount of gold (0.005mols, #1107D) to the BaTiO3 film, the peak intensity for the (200) plane of cubic BaTiO3 increases, but the peak is still weak and broad. The cubic (200) peak intensity appears to weaken with further additions of gold (0.01 mols, #1107C) . From the above results, it may be concluded that adding gold to undoped BaTiO3 enhances crystallization in these films.
SUBSTITUTE SHEET (RULE 26) CA 022633~7 1999-02-12 W O98/07167 PCT~Bg7/00985 Table I Summary of the sample preparation conditions Sample Code 1107A 1107B 1107C ' 107D
HAuCI4.3H,0 Content (mol) per 1mol Ba(CH?~CO0)7 0 0.05 0.01 ~ 05 Annealing Temperature (~C) 700 700 700 ' ~0 Thickness (nm) 110 110 110 1'0 Figure 10 is the X-ray diffraction pattern of the four samples above. The Figureshows a phase change from cubic to tetragonal and grain growth with increasing Au concentration.
Example 2. Barium titanate glycolate was prepared as follows. Six grams of barium oxide (99.5% purity) fine powder was added to 30 ml of ethylene glycol using vigorous stirring. The reaction was exothermic, and the reaction mixture was continuously stirred over 30 minutes. The reaction mixture was then dilute with 40 ml of 2--propanol. In addition, 9.0 ml of titanium isopropoxide was added with vigorous stirring. To avoid rapid precipitation the saturated ethylene glycol solution as kept hot (70~C). The morphology of the nanocrystaliine BaTiO3 film prepared is set forth in FIG.11 after annealing at 650~C for 1 hour. The coated samples were then dried under vacuum at 90~C for 2 hours. They were then heated at a rate of 20~~C/hour under dry flowing air up to the temperatures required to initiate calcination of the films, i.e., between 600 and 900~C. Elemental analysis using energy dispersive X-ray analysis on a scanning electron microscope showed that these films were BaTiO3 ~ilms. The spectra also showed the presence of elements from the glass substrate and Al contacts (Si, K, Na, and Al) and some impuritiescoming from the solution (Zn and Ca). Rapid thermal annealing of the films at SUBSTITUTE SHEET ~RULE 26) WO 98/07167 PCT~B97/00985 800~C can be used to improve the crystallinity of the films and to increase the dielectric constant from about 20 to about 80.
Various modifications may be made in the nature, composition, operation and arrangement of the various elements, steps and procedures described herein without departing from the spirit and scope of the invention as defined in the following claims.
SUBSTITUTE SHEET (RULE 26)
Claims (76)
1. A thin film composite of a substrate and a thin film, wherein the thin film comprises Ba a Ti b O c wherein a and b are independently between 0.75 and 1.25 and c is between about 2.5 and about 5.0, and further wherein the thin film composite has a storage capacity of at least 0.3 farad/cm3.
2. The thin film composite of Claim 1, wherein a and b are 1 and c is 3.
3. The thin film composite of Claim 1, wherein the energy storage capacity is at least 10 farads/cm3.
4. The thin film composite of Claim 3, wherein the energy storage capacity is at least 50 farads/cm3.
5. The thin film composite of Claim 1, wherein the substrate is silicon, alumina, sapphire or an electroconductive metal having a melting point of at least 850°C.
6. The thin film composite of Claim 5, wherein the substrate is silicon or Pt-coated silicon.
7. A thin film composite of substrate and a thin film, wherein the thin film comprises M d Ba a Ti b O c wherein "M" is Au, Cu, Ni3AI, Ru or InSn, a and b are independently from about 0.75 to about 1.25, c is about 2.5 to about 5.0 and d is about 0.01 to 0.25, and further wherein the thin film composite has a storage capacity of at least 0.3 farad/cm3.
8. The thin film composite of Claim 7, wherein a and b are about 1, c is about 3 and d is from about 0.01 to 0.25.
9. The thin film composite of Claim 7, wherein "M" is Au.
10. The thin film composite of Claim 7, wherein the energy storage capacity is at least 10 farads/cm3.
11. The thin film composite of Claim 7, wherein the energy storage capacity is at least 50 farads/cm3.
12. The thin film composite of Claim 7, wherein the energy storage capacity is at least 100 farads/cm3.
13. The thin film composite of Claim 7, where the substrate further contains a non-reactive component in an amount sufficient to induce strain in the thin film or plate.
14. The thin film composite of Claim 7, wherein the substrate is silicon, alumina, sapphire or an electroconductive metal having a melting point of at least 850°C.
15. The thin film composite of Claim 14, wherein the substrate is silicon or Pt-coated silicon.
16. A thin film composite comprising a thin film, wherein the thin film comprises Ba a Ti b O c wherein a and b are independently between 0.75 and 1.25 and c is between about 2.5 and about 5.0, and further wherein the thin fim contains a sufficient amount of a component which induces Internal strain in the thin film of thin film composite.
17. The thin film composite of Claim 15, wherein the energy storage capacity of the thin film composite is at least 1 farad/cm3.
18. The thin film composite of Claim 15, wherein the substrate is silicon, alumina, sapphire or an electroconductive metal having a melting point of at least 850°C.
19 The thin film composite of Claim 17, wherein the substrate is silicon or Pt-coated silicon.
20. An electrical energy storage device having an energy storage capacity of at least 0.3 farad/cm3 and comprising:
first and second substrates each having a planar face; and the thin film composite of Claim 16 interposed between the first and second substrates.
first and second substrates each having a planar face; and the thin film composite of Claim 16 interposed between the first and second substrates.
21. The electrical energy storage device of Claim 20, wherein the components which induces internal strain in the thin film are selected from the group consisting of europium, siliccn nitride, boron nitride, magnesium oxide, alumina, tungsten carbide or diamond particles.
22. The electrical energy storage device of Claim 20 wherein a and b are both 1.0 and c is 3Ø
23. The electrical energy storage device of Claim 20, wherein the substrate of the thin film of the thin film composite is alumina, sapphire or an electroconductive metal having a melting point of at least 850°C.
24. The electrical energy storage device of Claim 20, wherein the oxide of the thin film composite exhibits a perovskite structure.
25. The electrical energy storage device of Claim 20, wherein the thin film composite is ferroelectric and wherein the electrical energy storage device further comprises means electrically coupled to the first and second substrates and dielectric for applying a predetermined voltage for reversing polarization of the thin film composite.
26. An electrical energy storage device having an energy storage capacity of at least 0.3 farad/cm3 and comprising:
a first (top) and second (bottom) substrate each having a planar face; and the thin film composite of Claim 1 interposed between the first and second substrates.
a first (top) and second (bottom) substrate each having a planar face; and the thin film composite of Claim 1 interposed between the first and second substrates.
27. The electrical energy storage device of Claim 26, wherein both substrates are an electroconductive material having a melting point of at least 850°C.
28. The electrical energy storage device of Claim 27, wherein the top substrate is silicon, copper, gold, aluminum, nickel or another electroconductive material having a melting paint of at least 850°C.
29. The electrical energy storage device of Claim 27 wherein the bottom substrate is silicon, copper, gold, aluminum, nickel or another electroconductive material having a melting point of at least 850°C.
30. The electrical energy storage device of Claim 27, wherein a and b are both 1 and c is 3Ø
31. The electrical energy storage device of Claim 27, wherein the substrate of the thin film composite is alumina, sapphire or an electroconductive metal having a melting point of at least 850°C.
32. The electrical energy storage device of Claim 27, wherein the dielectic oxide of the thin film composite exhibits a perovskite structure.
33. The electrical energy storage device of Claim 27, wherein the thin film composite is ferroelectric and wherein the electrical energy storage device further comprises means electrically coupled to the first and second substrates and dielectric for applying a predetermined voltage for reversing polarization of the thin film composite.
34. A ferroelectric energy storage device having an energy storage capacity of at least 0.3 farad/cm3 and which comprises:
a semiconductor substrate;
the thin film composite of Claim 1 which exhibits ferroelectric hysteresis; and means electrically coupled to the thin film coating and the substrate for applying a predetermined voltage for reversing polarization of the thin film composite.
a semiconductor substrate;
the thin film composite of Claim 1 which exhibits ferroelectric hysteresis; and means electrically coupled to the thin film coating and the substrate for applying a predetermined voltage for reversing polarization of the thin film composite.
35. The ferroelectric energy storage device of Claim 34, further comprising a buffer layer between the thin film composite and semiconductor substrate.
36. A ferroelectric energy storage device having an energy storage capacity of at least 0.3 farad/cm3 and which comprises:
a semiconductor substrate;
the thin film composite of Claim 7 which exhibits ferroelectric hysteresis; and means electrically coupled to the thin film coating and the substrate for applying a predetermined voltage for reversing polarization of the thin film composite.
a semiconductor substrate;
the thin film composite of Claim 7 which exhibits ferroelectric hysteresis; and means electrically coupled to the thin film coating and the substrate for applying a predetermined voltage for reversing polarization of the thin film composite.
37. The ferroelectric energy storage device of Claim 35, further comprising a buffer layer between the thin film composite and semiconductor substrate.
38. A ferroelective non-volatile field effect transistor, comprising:
a semiconductor substrate of one type of conductivity;
spaced-charged regions of the opposite type of conductivity formed in the surface of the semiconductor substrate;
the thin film composite of Claim 1 which exhibits ferroelectric hysteresis; and means for establishing a potential across the thin film composite and the semiconductor substrate for effecting the spontaneous polarization of the thin film composite.
a semiconductor substrate of one type of conductivity;
spaced-charged regions of the opposite type of conductivity formed in the surface of the semiconductor substrate;
the thin film composite of Claim 1 which exhibits ferroelectric hysteresis; and means for establishing a potential across the thin film composite and the semiconductor substrate for effecting the spontaneous polarization of the thin film composite.
39. The ferroelectric non-volatile field effect transistor of Claim 38, further comprising a buffer layer between the thin film composite and the semiconductor substrate.
40. A ferroelectric non-volatile field effect transistor, comprising:
a semiconductor substrate of one type of conductivity, spaced-charged regions of the opposite type of conductivity formed in the surface of the semiconductor substrate;
the thin film composite of Claim 7 which exhibits ferroelectric hysteresis; and means for establishing a potential across the thin film composite and the semiconductor substrate for effecting the spontaneous polarization of the thin film composite.
a semiconductor substrate of one type of conductivity, spaced-charged regions of the opposite type of conductivity formed in the surface of the semiconductor substrate;
the thin film composite of Claim 7 which exhibits ferroelectric hysteresis; and means for establishing a potential across the thin film composite and the semiconductor substrate for effecting the spontaneous polarization of the thin film composite.
41. The ferroelectric non-volatile field effect transistor of Claim 40, further comprising a buffer layer between the thin film composite and the semiconductor substrate.
42. A high energy density storage material comprising the thin film composite of Claim 1.
43. A high energy density storage material of Claim 42, wherein the substrate of the thin film composite contains lithographically patterned or anodically etched pores, zeolites or aeorogels.
44. The high energy density storage material of Claim 42, wherein the substrate of the thin film composite is anisotropically etched or locally patterned by laser ablation.
45. A high energy density storage material comprising the thin film composite of Claim 7.
46. The high energy density storage material of Claim 45, wherein the substrate of the thin film composite contains lithographically patterned or anodically etched pores, zeolites, or aerogels.
47. An energy transmission and/or sensing system comprising the thin film composite of Claim 1.
48. The energy transmission and/or sensing system of Claim 47, wherein the substrate of the thin film composite contains lithographically patterned or anodically etched pores, trenches, depressions or textured protusions on the suface.
49. The energy transmission and/or sensing system of Claim 47, wherein the substrate of the thin film composite is anisotropially etched or locally patterned by laser ablation.
50. An energy transmission and/or sensing system comprising the thin film composite of Claim 7.
51. The energy transmission and/or sensing system of Claim 50, wherein the substrate of the thin film composite contains lithographically patterned or anodically etched pores, trenches, depressions or textured protrusions on the surface.
52. The energy transmission and/or sensing system of Claim 50, or wherein the substrate of the thin film composite is anisotropically etched substrates or locally patterned by laser ablation.
53. A method of preparing a thin film composite of Ba a Ti b O c which comprises:
(A) applying onto a substrate a Ba a Ti b O c coating wherein a and b are independently between from about 0.75 to about 1.25 and c is from about from 2.5 to 5.0;
(B) drying the coated substrate at a temperature of from about 300°C to about 500°C;
(C) annealing the dried coated substrate at a temperature from about 600°C to about 800° C until crystallization wherein the substrate and Ba a Ti b O c are of high purity and further wherein steps A - C are conducted in a nitrogen-rich environment.
(A) applying onto a substrate a Ba a Ti b O c coating wherein a and b are independently between from about 0.75 to about 1.25 and c is from about from 2.5 to 5.0;
(B) drying the coated substrate at a temperature of from about 300°C to about 500°C;
(C) annealing the dried coated substrate at a temperature from about 600°C to about 800° C until crystallization wherein the substrate and Ba a Ti b O c are of high purity and further wherein steps A - C are conducted in a nitrogen-rich environment.
54. The method of Claim 53, wherein the Ba a Ti b O c coating is prepared in a nitrogen-rich atmosphere by blending a reaction mixture of alcohol, barium diacetate and titanium alkoxide; and then admixing the resulting product with acetyl acetone and a weak acid; wherein the alcohol, barium diacetate, titanium alkoxide weak acid and acetyl acetone have a purity of at least 90%.
55. The method of Claim 54, which further comprises admixing with the Ba a Ti b O c, prior to step A, a non-reactive solution containing Au, Cu, Ni3AI, Ru or InSn, wherein the purity of the aqueous solution is at least 90%.
56. A method of preparing a thin film composite of Ba a Ti b O c wherein a and b are independently between about 0.75 and about 1.25 and c is about 2.5 to about 5.0 which comprises:
A. dissolving a reaction mixture of alcohol, barium diacetate and titanium alkoxide in ambient atmosphere;
B. forming an aqueous solution comprising the product of step A., weak acid and acetyl acetone, C. dipping a substrate into the solution of step B.;
D. drying the coating of step C at a temperature of from about 300° C
to about 500°C;
E. annealing the product of step D at a temperature of from about 600°C to about 800°C until crystallization;
wherein the alcohol, barium diacetate, titanium alkoxide, weak acid and acetyl acetone have a purity of at least 95% and further wherein steps A through E are conducted in a dry nitrogen-rich atmosphere.
A. dissolving a reaction mixture of alcohol, barium diacetate and titanium alkoxide in ambient atmosphere;
B. forming an aqueous solution comprising the product of step A., weak acid and acetyl acetone, C. dipping a substrate into the solution of step B.;
D. drying the coating of step C at a temperature of from about 300° C
to about 500°C;
E. annealing the product of step D at a temperature of from about 600°C to about 800°C until crystallization;
wherein the alcohol, barium diacetate, titanium alkoxide, weak acid and acetyl acetone have a purity of at least 95% and further wherein steps A through E are conducted in a dry nitrogen-rich atmosphere.
57. The method of Claim 56, wherein the titanium alkoxide is titanium isobutoxide or titanium isoproxide.
58. The method of Claim 56, wherein the weak acid is acetic acid.
59. The method of Claim 56, which further comprises adding a non-reactive solution containing Au, Cu, Ni3AI, Ru or InSn to the product of step B prior to deposition of the substrate and further wherein the purity of the aqueous solution is at least 95 %.
60. The method of Claim 59, wherein the aqueous solution contains HAuCI4.
61. A method of preparing a thin film composite of Ba a Ti b O c which comprises:
(A) applying onto a substrate a coating of Ba a Ti b O c wherein a and b are independently between from about 0.75 to about 1.25 and c is about from 2.5 to 5.0 and between from about 0.01 to about 0.25 mol percent of additive "M";
(B) drying the coated substrate at a temperature of from about 300° C to about 500°C; and (C) annealing the dried coated substrate at a temperature from about 600°C to about 800° C until crystallization wherein the substrate and Ba a Ti b O c are of high purity and further wherein steps A - C are conducted in a nitrogen-rich environment.
(A) applying onto a substrate a coating of Ba a Ti b O c wherein a and b are independently between from about 0.75 to about 1.25 and c is about from 2.5 to 5.0 and between from about 0.01 to about 0.25 mol percent of additive "M";
(B) drying the coated substrate at a temperature of from about 300° C to about 500°C; and (C) annealing the dried coated substrate at a temperature from about 600°C to about 800° C until crystallization wherein the substrate and Ba a Ti b O c are of high purity and further wherein steps A - C are conducted in a nitrogen-rich environment.
62. A method of preparing a thin film composite comprising Md Ba a Ti b O c wherein "M" is Au, Cu, Ni3AI, Ru or InSn, a and b are independently between about 0.75 to about 1.25, c is about 2.5 to about 5.0 and d is about 0.01 to 0.25, which comprises:
A. reacting barium diacetate and acetic acid in the presence of an alcohol and a glycol to produce titanium tetraacetate;
B. mixing the titanium tetraacetate while adding thereto an aqueous solution containing "M";
C. spinning the solution of step B onto a suitabie substrate at 500 rpm and then at about 1,000 to about 4,000 rpm until a uniform distribution is obtained;
D. drying the coated substrate of step C by heating at about 150° C to about 200° C;
E. heating the product of step D at a temperature between about 360°C
to about 400° C to remove volatile organic material therefrom;
F. annealing the product of step E at about 500°C to about 850°C until crystallization is complete wherein the barium diacetate acetic acid, alcohol and solution of "M" have a purity of at least 95% and further wherein steps a through F are preferably conducted in a dry nitrogen-rich atmosphere.
A. reacting barium diacetate and acetic acid in the presence of an alcohol and a glycol to produce titanium tetraacetate;
B. mixing the titanium tetraacetate while adding thereto an aqueous solution containing "M";
C. spinning the solution of step B onto a suitabie substrate at 500 rpm and then at about 1,000 to about 4,000 rpm until a uniform distribution is obtained;
D. drying the coated substrate of step C by heating at about 150° C to about 200° C;
E. heating the product of step D at a temperature between about 360°C
to about 400° C to remove volatile organic material therefrom;
F. annealing the product of step E at about 500°C to about 850°C until crystallization is complete wherein the barium diacetate acetic acid, alcohol and solution of "M" have a purity of at least 95% and further wherein steps a through F are preferably conducted in a dry nitrogen-rich atmosphere.
63. The method of Claim 62, wherein "M" is a solution of HAuCI4 in alcohol.
64. A method of preparing a Md Ba a Ti b O c thin film wherein "M" is Au, Cu, Ni3AI, Ru or InSn, a and b are independently between about 0.75 and about 1.25, c is about 2.5 to about 5.0 and d is about 0.01 to 0.25, which comprises:
A. reacting a glycol with barium oxide under agitation;
B. diluting the reaction mixture of step a with an alcohol;
C. adding titanium isopropoxide to the reaction product of step B with agitation;
D. adding an aqueous solution containing "M" in an alcohol to the product of step C;
E. depositing the mixture of step D. onto a substrate;
F. drying the coating of step E at a temperature of from about 150° C
to about 200° C;
G. annealing the product of step F. at a temperature of from about 600°
C to about 800° C until crystallization;
wherein the glycol, barium oxide, alcohol, titanium isopropoxide and solution containing "M" have a purity of at least 95% and further wherein steps A.
through G. are conducted in a dry nitrogen-rich atmosphere.
A. reacting a glycol with barium oxide under agitation;
B. diluting the reaction mixture of step a with an alcohol;
C. adding titanium isopropoxide to the reaction product of step B with agitation;
D. adding an aqueous solution containing "M" in an alcohol to the product of step C;
E. depositing the mixture of step D. onto a substrate;
F. drying the coating of step E at a temperature of from about 150° C
to about 200° C;
G. annealing the product of step F. at a temperature of from about 600°
C to about 800° C until crystallization;
wherein the glycol, barium oxide, alcohol, titanium isopropoxide and solution containing "M" have a purity of at least 95% and further wherein steps A.
through G. are conducted in a dry nitrogen-rich atmosphere.
65. The method of Claim 64, wherein the glycol is ethylene glycol.
66. The method of Claim 64, wherein "M" is a solution of HAuCI4 in alcohol.
67. The method of Claim 64, wherein the mixture of step D. is deposited onto the substrate by dip coating, spin coating, doctor blading or spray coating.
68. A method of preparing a Ba a Ti b O c thin film composite wherein a and b are independently between about 0.75 and about 1.25 and c is about 2.5 to about 5.0 which comprises:
A. reacting a glycol with barium oxide under agitation;
B. diluting the reaction mixture of step a with an alcohol;
C. adding titanium isopropoxide to the reaction product of step B with agitation;
D. depositing the mixture of step C. onto a substrate;
E. drying the coating of step D at a temperature of from about 150°C to about 200° C;
F. annealing the product of step E at a temperature of from about 600°
C to about 800°C until crystallization; wherein the glycol, barium oxide, alcohol and titanium isopropoxide have a purity of at least 95% and further wherein steps a through F are conducted in a dry nitrogen-rich atmosphere.
A. reacting a glycol with barium oxide under agitation;
B. diluting the reaction mixture of step a with an alcohol;
C. adding titanium isopropoxide to the reaction product of step B with agitation;
D. depositing the mixture of step C. onto a substrate;
E. drying the coating of step D at a temperature of from about 150°C to about 200° C;
F. annealing the product of step E at a temperature of from about 600°
C to about 800°C until crystallization; wherein the glycol, barium oxide, alcohol and titanium isopropoxide have a purity of at least 95% and further wherein steps a through F are conducted in a dry nitrogen-rich atmosphere.
69. The method of Claim 68, which further comprises adding an aqueous solution containing Au, Cu, Ni3AI, Ru or InSn to the product of step C prior to the deposition of the mixture onto the substrate wherein the molar ratio of Ba a Ti b O c:M
in the thin film is 1:1 and further wherein the purity of the aqueous solution is at least 95%.
in the thin film is 1:1 and further wherein the purity of the aqueous solution is at least 95%.
70. The method of Claim 69, wherein the solution is of HAuCI4 in alcohol.
71. A Ba a Ti b O c thin film composite produced by the process of Claim 53.
72. A Ma Ba b Ti c O d thin film composite produced by the process of Claim 61.
73. A Ba a Ti b O c thin film composite produced by the process of Claim 56.
74. A M a Ba b Ti c O d thin film composite produced by the process of Claim 62.
75. A Ba a Ti b O c thin film composite produced by the process of Claim 68.
76. A M a Ba b Ti c O d thin film composite produced by the process of Claim 64.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2383796P | 1996-08-12 | 1996-08-12 | |
| US60/023,837 | 1996-08-12 | ||
| PCT/IB1997/000985 WO1998007167A2 (en) | 1996-08-12 | 1997-08-11 | Semiconductor supercapacitor system, method for making same and articles produced therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2263357A1 true CA2263357A1 (en) | 1998-02-19 |
Family
ID=29581785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002263357A Abandoned CA2263357A1 (en) | 1996-08-12 | 1997-08-11 | Semiconductor supercapacitor system, method for making same and articles produced therefrom |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA2263357A1 (en) |
| IN (1) | IN192416B (en) |
| MY (1) | MY125454A (en) |
| TW (1) | TW356578B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504257A (en) * | 2012-11-02 | 2019-11-26 | 罗姆股份有限公司 | Chip capacitor, circuit unit and electronic equipment |
-
1997
- 1997-08-11 CA CA002263357A patent/CA2263357A1/en not_active Abandoned
- 1997-08-12 MY MYPI9703677 patent/MY125454A/en unknown
- 1997-08-12 IN IN1497CA1997 patent/IN192416B/en unknown
- 1997-09-24 TW TW086113878A patent/TW356578B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504257A (en) * | 2012-11-02 | 2019-11-26 | 罗姆股份有限公司 | Chip capacitor, circuit unit and electronic equipment |
| CN110504257B (en) * | 2012-11-02 | 2023-12-08 | 罗姆股份有限公司 | Chip capacitor, circuit assembly and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| MY125454A (en) | 2006-08-30 |
| IN192416B (en) | 2004-04-24 |
| TW356578B (en) | 1999-04-21 |
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