WO2004077564A1 - 薄膜容量素子ならびにそれを含んだ電子回路および電子機器 - Google Patents
薄膜容量素子ならびにそれを含んだ電子回路および電子機器 Download PDFInfo
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- WO2004077564A1 WO2004077564A1 PCT/JP2004/001977 JP2004001977W WO2004077564A1 WO 2004077564 A1 WO2004077564 A1 WO 2004077564A1 JP 2004001977 W JP2004001977 W JP 2004001977W WO 2004077564 A1 WO2004077564 A1 WO 2004077564A1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
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- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing bismuth, with or without oxygen or hydrogen, and containing two or more other elements
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D1/00—Resistors, capacitors or inductors
- H10D1/60—Capacitors
- H10D1/68—Capacitors having no potential barriers
- H10D1/682—Capacitors having no potential barriers having dielectrics comprising perovskite structures
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/787—Oriented grains
Definitions
- the present invention relates to a thin film capacitor, and an electronic circuit and an electronic device including the same
- the present invention relates to a thin film capacitor, and an electronic circuit and an electronic device including the same, and more particularly, to a thin film capacitor which can be thinned, can be easily manufactured, and has excellent temperature compensation characteristics.
- the present invention relates to an element, an electronic circuit and an electronic device including the element. Conventional technology.
- the temperature dependence of the electronic circuit included in the electronic device is small.
- the temperature dependence of the electronic circuit is reduced by controlling the capacitance temperature coefficient of the capacitance element included in the electronic circuit. There have been many attempts to do so.
- Japanese Unexamined Patent Application Publication No. 2000-2849462 Japanese Unexamined Patent Application Publication No.
- the capacitance temperature coefficient was controlled as desired by forming a plurality of dielectric layers composed of dielectrics having different capacitance temperature coefficients between the lower electrode and the upper electrode. Thin film capacitive elements have been proposed.
- the capacitance temperature coefficient of a thin film capacitor is controlled by forming a plurality of dielectric layers made of dielectric materials having different capacitance temperature coefficients, the manufacturing process of the thin film capacitor becomes complicated. In addition to the inevitable increase in the thickness of the thin film capacitor, the thickness of each dielectric layer must be controlled in order to control the temperature coefficient of capacitance of the thin film capacitor as desired. Has to be controlled accurately. Disclosure of the invention
- the present invention provides a thin-film capacitive element which can be thinned, can be easily manufactured, and has excellent temperature compensation characteristics, and a thin-film capacitive element including the same. It is an object to provide an electronic circuit and an electronic device.
- the present inventor has conducted intensive studies to achieve the object of the present invention. As a result, surprisingly, the inventor has a specific stoichiometric composition and contains bismuth in excess of the stoichiometric ratio.
- the capacitance temperature coefficient of the thin-film capacitive element on which the dielectric layer is formed by the dielectric material containing the bismuth layered compound is the [01] orientation of the bismuth layered compound contained in the dielectric layer.
- the degree of orientation that is, the degree of orientation in the c-axis direction
- the degree of orientation in the c-axis direction is controlled by controlling the degree of orientation of the bismuth layered compound contained in the dielectric layer in the c-axis direction. It has been found that the coefficients can be controlled as desired.
- the present invention is based on this finding, according to the present invention, the object of the present onset Ming, stoichiometric composition formula: (B i 2 0 2) 2+ ⁇ A m _ x B m O z m + 1 ) 2 — or B i 2 A m — ⁇ m O 3ra + 3 (symbol 222 is a positive integer, symbol ⁇ 4 is sodium (Na), At least one member selected from the group consisting of potassium (K), lead (Pb), barium (Ba), stonium (Sr), calcium (Ca) and bismuth (Bi).
- the symbols are iron (F e), copart (C o), chromium (C r), gallium (G a), titanium (T i), niobium (N b), tantalum (T a), At least one element selected from the group consisting of antimony (Sb), manganese (Mn), vanadium (V), molybdenum (Mo), and tungsten (W)
- Symbols A and / or ⁇ are two or more elements Composed of In such cases, their ratios are arbitrary.)
- Bismuth is contained in excess of the stoichiometric ratio, and the excess content of bismuth is 0, Bi, and 0 in Bismuth (Bi) conversion.
- a thin-film capacitor comprising a dielectric layer formed of a dielectric material containing a bismuth layered compound in a range of 5 5 ⁇ mole between a first electrode layer and a second electrode layer. Achieved by
- the dielectric material containing the bismuth layer compound may contain unavoidable impurities.
- an invitation to form a dielectric layer is provided.
- the degree of orientation of the [01] orientation of the bismuth layered compound contained in the dielectric material that is, the degree of orientation in the c-axis direction
- the temperature coefficient of capacitance of the thin film capacitor including the dielectric layer is controlled. Can be determined to be a desired value. Therefore, the temperature coefficient of an electronic circuit incorporating a thin-film capacitive element and the temperature coefficient of an electronic device incorporating an electronic circuit incorporating a thin-film capacitive element can be determined. Can be controlled as desired.
- the degree of c-axis orientation of the bismuth layered compound is controlled by the excess amount of bismuth with respect to the stoichiometric ratio, the type of substrate used, the type of electrode, the process of forming the dielectric layer, and the conditions for forming the dielectric layer. be able to.
- the control can be performed by controlling the conditions of the application when forming the dielectric layer and the calcination and calcination conditions.
- the degree of orientation of the bismuth layered compound in the c-axis direction is defined by the following formula (1).
- each of h and k zo can take any integer value of 0 or more.
- Bismuth layer compounds each stack, and configured (one 1) Bae Ropusukai bets grating continuous layered base Robusukai coat layer in AB 0 3, alternately and (B i 2 0 2) 2+ layer It has a layered structure.
- the symbol in in the stoichiometric composition formula is not particularly limited as long as it is a positive integer, but is preferably an even number. If the value of the symbol is an even number, the dielectric layer has a mirror plane parallel to the C plane, and the C axis component of spontaneous polarization cancels out from the mirror plane, and the dielectric layer becomes It has no polarization axis in the C-axis direction. For this reason, the paraelectric property of the dielectric layer is maintained, the temperature characteristics of the dielectric constant are improved, and low loss is realized. If the value of the symbol in is large, an improvement in the dielectric constant of the dielectric layer can be expected. .
- the symbol in the stoichiometric composition formula is 2,
- the dielectric layer comprises a bismuth layered compound in which the excess content of bismuth is in the range of 0.4 ⁇ B i to 0.5 X mol in terms of bismuth (B i). Contains.
- the bismuth layered compound further comprises scandium (S c), yttrium (Y), lanthanum (L a). Cerium (C e), praseodymium (P r), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Eupium Pium (Eu), Gadolium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (H) o), contains at least one rare earth element selected from the group consisting of erbium (E r), thulium (Tm), ytterbium (Y b) and lutetium (L u).
- the object of the present invention is also stoichiometric set Narushiki: x S r B i 4 T i 4 0 1 5 _ (1 -) MB i 4 T i 4 0 5
- M is at least one element selected from calcium, barium and lead, and 0 ⁇ 1
- the bismuth is in excess of the stoichiometric ratio
- the dielectric layer formed of a dielectric material containing a bismuth layered compound in which the excess content of bismuth is in the range of 0 to B i and 2.0 moles in terms of bismuth (B i) Have been provided between the first electrode layer and the second electrode layer.
- the dielectric layer is, the stoichiometric composition formula contains S r B i 4 T i 4 O 5 bismuth layer compound expressed by.
- the bismuth layered compound further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium ( N d), promethium (Pm), samarium (Sm), europium (Pu) (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), It contains at least one rare earth element selected from the group consisting of erbium (E r), thulium (Tm), ytterbium (Y b) and lutetium (L u).
- the object of the present invention is also to provide a stoichiometric formula: S r B i 4 T i 4 0 15 — (1 -x) MB i 4 T i 4 0 15
- M is at least one element selected from calcium, barium and lead, and 0 ⁇ X ⁇ 1
- the bismuth is in excess of the stoichiometric ratio
- Bismuth (Bi) and titanium (Ti) are formed by a dielectric material containing a bismuth layered compound in which the molar ratio of bismuth (B i) to titanium (T i) is in the range of 1 ⁇ B i / ⁇ i ⁇ 1.5
- the dielectric layer has a stoichiometry Composition formula: containing
- the bismuth layered compound further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium ( Nd), promethium (Pm), samarium (Sm), euphyllium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) , Contains at least one rare earth element selected from the group consisting of erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (shiu).
- the object of the present invention is also stoichiometric set Narushiki: (B i 2 0 2) 2 + ( ⁇ ⁇ , ⁇ ⁇ , ⁇ ,) 2 -, or, B i 2 4 m
- a thin film comprising a dielectric layer formed of a dielectric material containing a bismuth layer compound in the range of 0.5 0 ⁇ mole between the first electrode layer and the second electrode layer. It has been found that this can be achieved by an electronic circuit characterized by including a capacitive element.
- a thin film having a dielectric layer formed by a dielectric material having the above stoichiometric composition and containing a bismuth layered compound containing bismuth in excess of stoichiometric ratio The temperature coefficient of capacitance of the capacitive element is The degree of orientation in the [001] direction of the bismuth layered compound contained in the dielectric layer, that is, the degree of orientation in the c-axis direction, depends on the c-axis direction of the bismuth layered compound contained in the dielectric layer.
- the temperature coefficient of capacitance of the thin film capacitor can be controlled as desired by controlling the degree of orientation of the thin film capacitor
- a thin film capacitor formed of a dielectric material containing such a bismuth layered compound can be used. By incorporating it into an electronic circuit, the temperature coefficient of the electronic circuit can be controlled as desired.
- the dielectric layer comprises a bismuth layered compound in which the excess content of bismuth is in the range of 0.4 B i to 0.5 X i3 ⁇ 4mol in terms of bismuth (B i). Contains.
- the bismuth layered compound further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium. (Nd), promethium (Pm), samarium (Sm), europium (Pu) (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy-), holmium (Ho) ), Erbium (E r), thulium (Tm), ytterbium (Y b), and lutetium (L u) containing at least one rare earth element.
- the object of the present invention is also to provide a stoichiometric formula: XS r B i 4 T i 4 0 15 — (1 ⁇ B i 4 T i 4 O 5 (The symbol M is at least one element selected from calcium, barium, and lead, and 0 ⁇ 1), and the bismuth is in excess of the stoichiometric ratio.
- the dielectric layer is, the stoichiometric composition formula contains S r B i 4 T i 4 Oi bismuth layer compound expressed by 5.
- the bismuth layered compound further comprises scandium (S c), yttrium (Y), lanthanum (La), cerium (C e), praseodymium (P r), neodymium.
- Nd promethium (Pm), samarium (Sm), europium (Pu) (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (H o), contains at least one rare earth element selected from the group consisting of erbium (E r), thulium (Tm), ytterbium (Y b) and lutetium (L u).
- the object of the present invention is also to provide a stoichiometric composition formula: S r B i 4 T i 4 0 15 — (l ⁇ x) MB i 4 T i 4 O 5 (The symbol is at least one element selected from calcium, barium and lead, and 0 ⁇ ' ⁇ 1), and bismuth is more than stoichiometric.
- an electronic circuit characterized by including a thin film capacitor provided between the first electrode layer and the second electrode layer. I have.
- the dielectric layer is, the stoichiometric composition formula contains S r B i 4 T i 4 5 bismuth layered compound represented by.
- the bismuth layered compound further comprises scandium (S c yttrium (Y), lanthanum (L a). Cerium (C e), praseodymium (P r), neodymium (N d), Promethium (Pm), Summary (Sm), Eupium Pium (Eu), Gadolium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (H o), at least one rare earth element selected from the group consisting of Erbium (Er), Thulium (Tm), Ytterbium (Yb) and Lutetium (Lu).
- the object of the present invention is: Composition formula: (B i 2 0 2 ) 2+ ⁇ A m ⁇ x B m O Z m + 1 ) 2 — or a composition represented by B i 2 1 ⁇ 0 3 m + 3 (the symbol ⁇ 2 is Is a positive integer and the symbol ⁇ is for sodium (Na), potassium (K), lead (Pb), norium (Ba), strontium (Sr), calcium (Ca) and It is at least one element selected from the group consisting of bismuth (B), and symbol 5 is iron (Fe), cobalt (Co), chromium (Cr), gallium (Ga), and titanium.
- the dielectric layer formed of a dielectric material containing a bismuth layered compound having an excess bismuth content in the range of 0 to B i ⁇ 0.5 mol in terms of bismuth (B i) is It has been found that this can be achieved by an electronic device characterized by including a thin-film capacitive element provided between the electrode layer and the second electrode layer.
- a thin film having a dielectric layer formed by a dielectric material having the above stoichiometric composition and containing a bismuth layered compound containing bismuth in excess of stoichiometric ratio The temperature coefficient of capacitance of the capacitance element depends on the degree of orientation in the [001] direction of the bismuth layered compound contained in the dielectric layer, that is, the degree of orientation in the c-axis direction, and is included in the dielectric layer. By controlling the degree of orientation of the bismuth layered compound in the c-axis direction, the capacitance temperature coefficient of the thin film capacitance element can be controlled as desired.
- a thin-film capacitive element formed of a dielectric material into an electronic circuit makes it possible to control the temperature coefficient of the electronic circuit as desired, and thus the force, the dielectric containing the bismuth layered compound
- the temperature coefficient of an electronic device including electronic circuitry thin film capacity element formed of a material is incorporated, it is possible to a desired manner of control.
- the dielectric layer is made of bismuth.
- the excess content of bismuth (B i) is 0.4 B i
- the bismuth layered compound further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium. (Nd), Promethium (Pm), Summary (Sm), Eupitum, (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (H o), contains at least one rare earth element selected from the group consisting of erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
- the object of the present invention is also stoichiometric set Narushiki: S r B i 4 T i 4 0 1 5 _ (1 - x) MB i 4 T i 4 O 1 5 (the symbol M is at least one element selected from calcium, balium and lead, and 0 ⁇ ⁇ 1), and bismuth has a stoichiometric ratio.
- a dielectric material containing a bismuth layered compound in which the bismuth excess content is in the range of 0 and B i ⁇ 2.0 mol in terms of bismuth (B i). It has been found that this is achieved by an electronic device characterized by including a thin-film capacitive element provided with a dielectric layer between the first electrode layer and the second electrode layer.
- the dielectric layer is, the stoichiometric composition formula contains S r B i 4 T i 4 O 1 5 bismuth layered compound represented by.
- the bismuth layered compound further comprises scandium (S c), yttrium (Y), lanthanum (L a), cerium (C e;), praseodymium (P r), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Euphyllium Pium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium It contains at least one rare earth element selected from the group consisting of (H o), erbium (E r), thulium (T m), ytterbium (Y b) and lutetium (L u).
- the object of the present invention is also stoichiometric set Narushiki: x S r B i 4 T i 4 0 15 - (1 one X) MB i 4 T i 4 0 15 (The symbol kf is at least one element selected from calcium, barium and lead, and 0 ⁇ 1), and bismuth is more than stoichiometric.
- Dielectric material containing bismuth layered compound which is excessively contained and whose bismuth excess content is such that the molar ratio of bismuth (B i) to titanium (T i) is in the range of 1 ⁇ B i / T i ⁇ 1.5 Has been found to be achieved by an electronic device characterized by including a thin-film capacitor provided between the first electrode layer and the second electrode layer with the dielectric layer formed by the method.
- the dielectric layer is, the stoichiometric compositional formula: S r B i 4 T i 4 O! It contains the bismuth layered compound represented by 5 .
- the bismuth layered compound further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium ( Nd), promethium (Pm), samarium (Sm), europium (Pu) (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) , Erbium (E r), thulium (T m), ytterbium (Y b) and lutetium (L u) containing at least one rare earth element.
- Sc scandium
- the material for forming the first electrode layer on which the dielectric layer is formed is not particularly limited, and platinum (Pt), ruthenium (Ru), rhodium ( R h), palladium (P d), iridium (I r), gold (Au), silver (A g), copper (Cu), nickel (N i), and alloys containing these as main components
- the first electrode layer on which a dielectric layer is formed is formed by a vacuum evaporation method, a sputtering method, a pulse laser evaporation method (PLD), a metal-organic vapor deposition method.
- a vacuum evaporation method e.g., a vacuum evaporation method, a sputtering method, a pulse laser evaporation method (PLD), a metal-organic vapor deposition method.
- Chemical vapor deposition (MOCVD), metal-organic decomposition (MOD) and sol-gel methods, and other liquid-phase methods (CSD methods) can be used to form the thin film.
- the first electrode layer on which the dielectric layer is formed on the surface is oriented in the [011] direction, that is, even if it is oriented in the c-axis direction, it is not in the [011] direction. It may be oriented in an azimuthal direction, and may be amorphous or non-oriented.
- the dielectric layer is formed by a vacuum deposition method, a sputtering method, a pulse laser deposition method (PLD), a metal-organic chemical vapor deposition method (MOCVD), (metal-organic decomposition: MOD) ⁇ It can be formed using various thin film forming methods such as a liquid phase method (CSD method) such as a sol-gel method. It is formed on the electrode layer by a liquid phase method.
- a liquid phase method such as a sol-gel method.
- the liquid phase method refers to a method of forming a thin film including one or more application steps, one or more preliminary firing steps, and one or more firing steps.
- MOD organic decomposition
- the sol-gel method the case where a thin film is formed using an inorganic acid salt solution.
- the organometallic decomposition method is most preferred and used.
- the dielectric material containing the bismuth layered compound is applied to the composition of the bismuth layered compound and the conditions for forming the dielectric layer on the first electrode layer. Therefore, the [001] orientation, that is, the degree of orientation of the bismuth layered compound in the c-axis direction is determined.
- a thin film capacitor containing a bismuth layer compound containing bismuth in excess of the stoichiometric ratio A solution of the element composition is applied on the first electrode layer to form a coating film, and the coating film on the first electrode is baked to form a dielectric layer.
- the coating film is dried, and the coating film is pre-fired at a temperature at which the coating film does not crystallize. Baking to form a dielectric layer.
- a step of forming a coating film on the first electrode layer, drying the coating film, forming a new coating film on the dried coating film, and drying the new coating film May be repeated to form a coating film having a desired thickness, and thereafter, the coating film may be baked to form a dielectric layer.
- the application and drying steps may be repeated two or more times, followed by preliminary firing, and finally, the applied film may be fired to form a dielectric layer.
- a coating film is formed on the first electrode layer, the coating film is dried, and the coating film is pre-baked, and then a new coating film is formed on the coating film, and the new coating film is dried. Then, the step of calcination may be repeated to form a coating film having a desired film thickness, and thereafter, the coating film may be baked. In this case, the application and pre-baking steps may be repeated without drying the applied film, and finally, the film may be fired to form a dielectric layer.
- a step of forming a coating film on the first electrode layer, drying the coating film, temporarily firing the coating film, and thereafter firing the coating film is repeated to obtain a coating film having a desired thickness.
- a dielectric layer may be formed.
- the coating, pre-baking, and baking steps may be repeated without drying the coating film to form a dielectric layer.
- the steps of drying and firing may be repeated to form a dielectric layer.
- the first electrode layer is formed on the first electrode layer by a spin coating method or a dip coating method, preferably by a spin coating method.
- the coating film formed on the first electrode layer is preferably baked at a crystallization temperature of the bismuth layered compound of 700 to 900 ° C.
- the coating film formed on the first electrode layer is preferably dried at room temperature to 400 ° C., more preferably at 50 to 300 °.
- the coating film formed on the first electrode layer is preferably pre-baked at a temperature of 300 to 500 ° C.
- the second electrode layer is formed on the dielectric layer.
- the material for forming the second electrode layer is not particularly limited as long as it has conductivity, and platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), gold (Au), silver (Ag), copper (Cu), nickel (Ni), and other metals and alloys, N d O, N b O , R E_ ⁇ 2, Rh 0 2, O s O.
- the second electrode layer can do.
- the material for forming the second electrode layer does not need to consider the lattice matching with the material forming the dielectric layer, and can be formed at room temperature. Therefore, the second electrode layer can be formed using a base metal such as iron (Fe) or copart (Co) or an alloy such as WSi or MoSi.
- the thickness of the second electrode layer is not particularly limited as long as the function as one electrode of the thin film capacitor can be ensured. It can be set to about 100 nm.
- the method for forming the second electrode layer is not particularly limited.
- vacuum deposition sputtering, pulsed laser deposition (PLD), metal-organic chemical vapor deposition (MOCVD), and metal-organic decomposition ) ⁇ ⁇ ⁇
- PLD pulsed laser deposition
- MOCVD metal-organic chemical vapor deposition
- metal-organic decomposition ⁇ ⁇ ⁇ It can be formed using various thin film forming methods such as liquid phase method (CSD method) such as sol-genole method. Of these, the sputtering method is preferred from the viewpoint of the deposition rate.
- FIG. 1 is a schematic sectional view of a thin film capacitor according to a preferred embodiment of the present invention.
- FIG. 2 shows the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitors manufactured according to Examples 1 to 10 and the dielectric layer constituting the thin film capacitor.
- 4 is a graph showing the relationship between the bismuth layered compound contained and the degree of orientation (%) in the c-axis direction.
- FIG. 1 is a schematic sectional view of a thin film capacitor according to a preferred embodiment of the present invention.
- the thin-film capacitor 1 includes a support substrate 2, and a barrier layer 3, a lower electrode layer 4, a dielectric layer 5, and an upper electrode layer 6 forces are stacked in this order.
- the support substrate 2 of the thin-film capacitive element 1 is formed of a silicon single crystal having excellent lattice matching.
- the thickness of the support substrate 2 is, for example, about 100 to 100 m.
- the thin-film capacitive element 1 includes an insulating layer 3 formed of silicon oxide on a supporting substrate 2.
- the insulating layer 3 made of silicon oxide is formed, for example, by thermal oxidation of silicon.
- a lower electrode layer 4 is formed on the insulating layer 3.
- the lower electrode layer 4 is formed of platinum.
- the lower electrode layer 4 may be oriented in the [001] direction, may be oriented in a direction other than the [001] direction, and may be amorphous or not oriented. .
- the lower electrode layer 4 made of platinum for example, argon gas is used as a sputtering gas, and the temperature of the support substrate 2 and the insulating layer 3 is maintained at 300 ° C. or higher, preferably 500 ° C. or higher. Then, it is formed on the insulating layer 3 by a sputtering method.
- the thickness of the lower electrode layer 4 is not particularly limited, and is about 10 to 100 nm, preferably about 50 to 200 nm. In the present embodiment, the lower electrode layer 4 is formed with a thickness of 100 nm.
- the thin film capacitor 1 includes a dielectric layer 5 formed on a lower electrode layer 4.
- Dielectric is represented by S r B i 4 T i 4 0 i 5, including bis mass layered compound having excellent characteristics as a capacitor material:
- the dielectric layer 5 the stoichiometric compositional formula It is formed by body material.
- the bismuth layered compound contains an excess of bismuth such that the molar ratio of bismuth (B i) to titanium (T i) is 1 and B i / T i ⁇ 1.5.
- the bismuth layered compound preferably further comprises scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and promethium.
- the dielectric layer 5 is formed on the lower electrode layer 4 by a metal-organic decomposition (MOD) method.
- MOD metal-organic decomposition
- a solution of strontium 2-ethylhexanoate in toluene, a solution of bismuth 2-ethylhexanoate in 2-ethylhexanoic acid, and a solution of titanium 2-ethylhexanoate in toluene are mixed with 2-ethyl
- strontium hexanoate is mixed at 1 mol
- bismuth 2-ethylhexanoate is (4 + a) mol
- titanium 2-ethylhexanoate is 4 mol at a stoichiometric ratio.
- these solutions are mixed and diluted with toluene so that the amount of bismuth added increases by ⁇ mol, thereby preparing a raw material solution.
- a is selected such that B i ZT i is between 1.1 and 1.5.
- the raw material solution thus obtained is applied onto the lower electrode layer 4 by a spin coating method so that the film thickness becomes, for example, 100 nm, to form a coating film.
- the film is dried at a temperature from room temperature to about 400 ° C. to evaporate the solvent in the coating film.
- the coating film is calcined in an oxygen atmosphere at about 200 to 700 ° C.
- the calcination is performed at a temperature at which the bismuth layered compound in the coating film is not crystallized.
- the raw material solution is applied again on the pre-baked coating film by a spin coating method so that the film thickness becomes, for example, 100 nm, a coating film is formed, and after drying, Approximately 200 to 7
- the raw material solution is further applied on the pre-baked coating film by a spin coating method so that the film thickness becomes, for example, 100 nm, to form a coating film, and after drying,
- the coating film is pre-baked in an oxygen atmosphere at about 200 to 700 ° C.
- the temporarily fired coating film is fired in an oxygen gas atmosphere at about 700 to 900 ° C. to crystallize the bismuth layered compound in the coating film.
- a dielectric layer 5 having a thickness of 300 nm is formed.
- the dielectric layer 5 obtained by it this, chemical stoichiometric composition formula. Include S r B i 4 T i 4 0 15 bismuth layer compound represented by the bismuth layer compound, Excess bismuth is contained with respect to the stoichiometric ratio, and the molar ratio of bismuth (B i) to titanium (T i) is in the range of 1 / B i / T i ⁇ 1.5.
- the bismuth layer compound grows epitaxially and is oriented in the [001] direction, that is, in the c-axis direction.
- the degree of orientation (%) of the bismuth layered compound in the c-axis direction can be determined by controlling the excess amount of bismuth with respect to the stoichiometric ratio, and the conditions of coating, pre-firing, and firing for forming the dielectric layer. '' It is known that it can be controlled, but according to the research of the present inventor, by controlling the degree of orientation (%) of the bismuth layered compound contained in the dielectric layer 5 in the c-axis direction, the thin film is controlled.
- the dielectric layer 5 is, the stoichiometric compositional formula: Table in S r B i 4 T i 4 0 15
- the bismuth layered compound containing excess bismuth is contained so that the molar ratio of bismuth (B i) to titanium (T i) becomes 1 and B i / T i is 1.5
- the degree of orientation (%) of the bismuth layered compound in the c-axis direction By controlling the degree of orientation (%) of the bismuth layered compound in the c-axis direction, the electrostatic capacity of the thin film capacitor 1 can be controlled. It has been found that the temperature coefficient of capacitance can be greatly varied between a positive value and a negative value.
- an excess amount of bismuth with respect to the stoichiometric ratio, application at the time of forming the dielectric layer, calcination, and calcination are performed so that the thin film capacitor 1 has a desired capacitance temperature coefficient. Is controlled, the degree of orientation F (%) of the bismuth layered compound contained in the dielectric layer 5 in the c-axis direction is determined.
- the top of the dielectric layer 6 is The electrode layer 6 is formed.
- the upper electrode layer 6 made of platinum, for example, argon gas is used as a sputtering gas, and the temperature of the support substrate 2, the insulating layer 3, the lower electrode layer 4, and the dielectric layer 5 is set to room temperature (25 ° C.). Is formed on the dielectric layer 5 by a sputtering method.
- the thin film capacitor 1 As described above, according to the study of the present inventors, by controlling the degree of orientation F (%) of the bismuth layered compound contained in the dielectric layer 5 in the c-axis direction, the thin film capacitor 1 It has been found that the capacitance temperature coefficient can be varied.
- the dielectric layer 5 is represented by a stoichiometric composition formula: S r B i 4 T i 40 i 5
- the bismuth (B i) and titanium (T i) contain a bismuth layered compound containing an excess of bismuth so that the molar ratio of the bismuth (B i) and titanium (T i) is 1 and B i / ⁇ i ⁇ 1.5
- the degree of orientation (%) of the bismuth layered compound in the c-axis direction By controlling the degree of orientation (%) of the bismuth layered compound in the c-axis direction, the temperature coefficient of capacitance of the thin-film capacitive element 1 can be greatly changed between a positive value and a negative value. It turns out that there is.
- the dielectric layer 5 the stoichiometric composition formula represented by S r B i 4 T i 4 O 5
- moles of bismuth (B i) and titanium (T i) Contains a bismuth layered compound containing excess bismuth so that the ratio is 1 B i / T i 1.5, forming an excess amount of bismuth with respect to the stoichiometric ratio and forming a dielectric layer
- the application, pre-firing, and firing conditions are controlled to determine the degree of orientation (%) of the bismuth layered compound contained in the dielectric layer 5 in the c-axis direction.
- a thin film capacitor 1 having a desired capacitance temperature coefficient can be obtained without providing a layer.Therefore, an electronic circuit incorporating the thin film capacitor 1 can be controlled in temperature dependence as desired, It is possible to reduce the temperature dependence of electronic devices with embedded circuits
- a solution of strontium 2-ethyl hexanoate in toluene and 2-ethyl A solution of bismuth hexahexanoate in 2-ethylhexanoic acid and a solution of titanium 2-ethylhexanoate in toluene are prepared by adding 1 mol of bis (2-ethylethylhexanoate) in bismuth 2-bisethylhexanoate. Is (4 + ⁇ ) mol, 2
- a 0.5 ⁇ m thick silicon oxide film is formed by thermal oxidation on a support substrate made of silicon single crystal, and a lower electrode made of a platinum thin film is formed on the silicon oxide film. It was formed with a thickness of 1 m.
- argon gas at a pressure of 1 pass force (Pa) was used as the sputtering gas
- the temperature of the support substrate and the silicon oxide film was set at 600 ° C
- the power was set at 100 WZ square centimeter.
- the lower electrode was formed by the sputtering method.
- the area of the support substrate is 5 mm x 10 mm, which is 7 mm.
- the supporting substrate was set on the stage of the spin coating apparatus, and about 10 ⁇ L of the raw material solution was dropped on the surface of the lower electrode, and the stage was set at 4000 rpm for 20 seconds. Then, a coating film having a thickness of 100 nm was formed on the surface of the lower electrode.
- the support substrate on which the coating film was formed was set in a constant temperature layer set at 150 ° C., and dried for 10 minutes to evaporate the solvent contained in the coating film.
- the support substrate on which the coating film was formed was put into an annular furnace to which oxygen gas was supplied at a flow rate of 0.3 liter / minute, and the temperature in the annular furnace was increased by 1 The temperature was raised to 400 ° C. for 0 ° KZ, and maintained at 400 ° C. for 10 minutes. Then, the temperature was lowered at a temperature lowering rate of 10 ° KZ, and the coating film was pre-baked.
- the supporting substrate on which the pre-baked coating film is formed is set on the stage of the spin coating device, and about 10 ⁇ L of the raw material is melted.
- the solution was dropped on the surface of the lower electrode, and the stage was rotated at 4000 rpm for 20 seconds to form a coating film having a total thickness of 200 nm.
- the support substrate on which the coating film was formed was set in a constant temperature layer set at 150 ° C., and dried for 10 minutes to evaporate the solvent contained in the coating film.
- the support substrate on which the coating film was formed was put into an annular furnace supplied with oxygen gas at a flow rate of 0.3 liter / minute, and the temperature in the annular furnace was increased by 1 The temperature was raised to 400 ° C. at 0 ° K / min, and maintained at 400 ° C. for 10 minutes, and then the temperature was decreased at a temperature lowering rate of 10 ° KZ, and the coating film was pre-baked.
- the support substrate on which the pre-baked coating film is formed is set on the stage of the Svinco coating device, and about 10 ⁇ L of the raw material solution is dropped on the surface of the lower electrode, and the stage is moved.
- the substrate was rotated at 4000 rpm for 20 seconds to form a coating film having a total thickness of 300 nm.
- the support substrate on which the coating film was formed was set in a constant temperature layer set at 150 ° C., and dried for 10 minutes to evaporate the solvent contained in the coating film.
- the support substrate on which the coating film was formed was put into an annular furnace supplied with oxygen gas at a flow rate of 0.3 liter / min, and the temperature in the annular furnace was increased by 10 ° C.
- the temperature was raised to 400 ° C, and the temperature was maintained at 400 ° C for 10 minutes.
- the temperature was lowered and the coating film was pre-baked.
- the support substrate on which the temporarily-baked coating film is formed is placed at a flow rate of 5 milliliters Z in an annular furnace to which oxygen gas is supplied.
- the temperature inside the furnace was raised to 860 ° C at a heating rate of 80 ° KZ, maintained at 860 ° C for 30 minutes, and then decreased at a cooling rate of 80 ° KZ.
- the coating film was baked to form a dielectric layer. Dielectric layer thickness after firing is 300 nm Met.
- the crystal structure of the dielectric layer thus obtained was measured by the X-ray diffraction method. Based on the measured X-ray diffraction pattern, the degree of orientation (%) of the bismuth layered compound in the c-axis direction was calculated according to equation (1). Was 55%.
- an upper electrode made of a platinum thin film was formed on the surface of the dielectric layer to a thickness of 0.1 ⁇ m.
- argon gas at a pressure of 1 Pascal (Pa) was used as a sputtering gas, and the temperature of the support substrate, silicon oxide film, lower electrode, and dielectric layer was set to room temperature (25 ° C).
- the power was set to 100 W, and the upper electrode was formed by the sputtering method to obtain a thin-film capacitive element.
- the capacitance of the thin-film capacitor thus obtained was set at a reference temperature of 25 ° C, a measurement temperature range of 150 to 150 ° C, and an impedance analyzer (HP 4194A) was used. Measured at a frequency of 100 kHz (applied to AC 20 mV) and average rate of change of capacitance with temperature based on 25 ° C (capacitance temperature coefficient) When ⁇ ⁇ was determined, it was 880 ⁇ pm ⁇ 8.
- the temperature in the annular furnace was raised to 880 ° C., and the temperature was maintained in the same manner as in Example 1 except that the temperature was maintained for 30 minutes. Then, a dielectric layer was formed, and a thin film capacitor was fabricated.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the dielectric layer thus obtained was determined in the same manner as in Example 1, and the degree of orientation of the bismuth layered compound in the c-axis direction _ (%) was 60%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was calculated in the same manner as in Example 1. As a result, it was 810 ppmZK.
- Example 3 Assuming that ⁇ is 0.8, the same procedure as in Example 1 was carried out except that the raw material solution was prepared so that the molar ratio of bismuth (B i) to titanium ( ⁇ i) became 1.2. Then, a dielectric layer was formed, and a thin film capacitor was fabricated.
- the degree of orientation F (%) in the c-axis direction of the bismuth layered compound contained in the dielectric layer thus obtained was determined in the same manner as in Example 1, and the degree of orientation in the c-axis direction of the bismuth layered compound was determined. (%) was 65%. Further, the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was obtained in the same manner as in Example 1, and was found to be 570 ppm / K. Was.
- the temperature in the annular furnace was raised to 900 ° C., and the temperature was maintained in the same manner as in Example 3 except that the temperature was maintained for 30 minutes. Thus, a dielectric layer was formed, and a thin film capacitor was fabricated.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the thus obtained dielectric layer was determined in the same manner as in Example 1. %) was 70%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1. As a result, it was 450 ppm / K. .
- a toluene solution of strontium 2-ethylhexanoate, a 2-ethylhexanoic acid solution of bismuth 2-ethylhexanoate, and a toluene solution of titanium 2-ethylhexanoate in a toluene solution of strontium 2-hexylhexanoate The amount of bismuth added is smaller than that in the case of mixing at a stoichiometric ratio such that bismuth 2-ethoxy / bismuth hexanoate becomes (4 + ⁇ ) monole and titanium 2-ethylhexanoate becomes 4 moles.
- argon gas at a pressure of 1 Pa (Pa) was used as the sputtering gas
- the temperature of the silicon oxide film on the support substrate was set at 400 ° C
- the power was set at 100 WZ cm2.
- a lower electrode was formed by a sputtering method.
- the area of the supporting substrate is 5 mm x 1 Omm.
- the supporting substrate was set on the stage of the spin coating apparatus, and about 10 ⁇ L of the raw material solution was dropped on the surface of the lower electrode, and the stage was set at 400 O rpm for 20 seconds. By rotating, a coating film having a thickness of 100 nm was formed on the surface of the lower electrode.
- the support substrate on which the coating film was formed was set in a thermostatic layer set at 150 ° C., and dried for 10 minutes to evaporate the solvent contained in the coating film.
- the support substrate on which the coating film was formed was put into an annular furnace supplied with oxygen gas at a flow rate of 0.3 liter Z, and the temperature in the annular furnace was increased by 10 ° C.
- the temperature was raised to 400 ° C at ° K / min and held at 400 ° C for 10 minutes, then the temperature was lowered at a rate of 10 ° K / min to temporarily coat the coating film. Fired.
- the support substrate on which the pre-baked coating film is formed is placed at a flow rate of 5 ml / min into a ring furnace supplied with oxygen gas, and the temperature in the ring furnace is raised.
- the temperature was raised to 840 ° C at a rate of 80 ° KZ, held at 840 ° C for 30 minutes, and then lowered at a rate of 80 ° K / min to reduce the temperature of the coating film. Fired.
- the supporting substrate on which the fired coating film is formed is set on a stage of a spin coating apparatus, and about 10 liter of a raw material solution is dropped on the surface of the lower electrode, and the stage is moved to 400 The coating was rotated at 0 rpm for 20 seconds to form a coating film having a total thickness of 200 nm. Then, the support substrate on which the coating film is newly formed is set in a constant temperature layer set at 150 ° C., dried for 10 minutes, and the solvent contained in the coating film is evaporated.
- a constant temperature layer set at 150 ° C. dried for 10 minutes
- the support substrate on which the coating film is newly formed is put into the annular furnace to which oxygen gas is supplied at a flow rate of 0.3 liter Z, and the temperature in the annular furnace is increased at a temperature increasing rate.
- the temperature was raised to 400 ° C, held at 400 ° C for 10 minutes, and then lowered at a rate of 10 ° KZ, and the temperature was lowered.
- the formed coating film was calcined.
- the support substrate on which the calcined coating film is formed is placed in an annular furnace supplied with oxygen gas at a flow rate of 5 ml Z, and the temperature in the annular furnace is increased at a temperature increasing rate.
- the temperature was raised to 840 ° C., held at 840 ° C. for 30 minutes, and then lowered at a rate of 80 ° K / min.
- the formed coating film was fired.
- the supporting substrate on which the fired coating film is formed is set on the stage of the spin coating device, and about 10 ⁇ L of the raw material solution is dropped on the surface of the lower electrode, and the stage is It was spun at 400 rpm for 20 seconds to form a total of 300 rim thick coating.
- the support substrate on which the coating film is newly formed is set in a constant temperature layer set at 150 ° C., dried for 10 minutes, and the solvent contained in the coating film is evaporated.
- a constant temperature layer set at 150 ° C. dried for 10 minutes, and the solvent contained in the coating film is evaporated.
- the support substrate on which the coating film is newly formed is put into the annular furnace supplied with oxygen gas at a flow rate of 0.3 liter / minute, and the temperature in the annular furnace is raised.
- the temperature in the annular furnace is raised.
- the temperature is raised to 400 ° C, and held at 400 ° C for 10 minutes, and then the temperature is lowered at a rate of 10 ° KZ, The newly formed coating film was pre-fired.
- the support substrate on which the calcined coating film is formed is placed in an annular furnace supplied with oxygen gas at a flow rate of 5 ml Z, and the temperature in the annular furnace is increased at a temperature increasing rate.
- the temperature was raised to 840 ° C., held at 840 ° C. for 30 minutes, and then lowered at a rate of 80 ° K.
- the temperature was lowered at a rate of 1 minute, and the newly formed coating film was baked to form a dielectric layer.
- the thickness of the dielectric layer after firing was 300 nm.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the dielectric layer thus obtained was determined in the same manner as in Example 1, and the degree of orientation in the c-axis direction of the bismuth layered compound was determined. (%) was 80%. Further, an upper electrode was formed on the surface of the dielectric layer in exactly the same manner as in Example 1 to obtain a thin film capacitor.
- the average change rate (temperature coefficient of capacitance) ⁇ e of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1, and was found to be 300 ppm / K.
- the temperature in the annular furnace was raised to 860 ° C, and a dielectric layer was formed in exactly the same manner as in Example 5, except that the temperature was maintained for 30 minutes. Then, a thin film capacitor was manufactured.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the dielectric layer thus obtained was determined in the same manner as in Example 1, and the orientation of the bismuth layered compound in the c-axis direction was determined. The degree (%) was 90%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1, and it was 110 ppm / K. .
- the temperature in the annular furnace was raised to 880 ° C., and a dielectric layer was formed in exactly the same manner as in Example 5, except that the temperature was maintained for 30 minutes. Then, a thin film capacitor was manufactured.
- Example 8 The degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the thus obtained dielectric layer was determined in the same manner as in Example 1. %) was 94%.
- Example 8 The average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1. As a result, it was O pp mZK.
- the raw material solution was prepared in the same manner as in Example 6 except that the molar ratio of bismuth (B i) to titanium (T i) was 1.3. Then, a dielectric layer was formed, and a thin film capacitor was manufactured.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the dielectric layer thus obtained was determined in the same manner as in Example 1, and the degree of orientation of the bismuth layered compound in the c-axis direction F (%) was 95%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1. As a result, it was 130 ppmZK.
- the temperature in the annular furnace was raised to 880 ° C., and a dielectric layer was formed in exactly the same manner as in Example 8, except that the temperature was maintained for 30 minutes. Then, a thin film capacitor was manufactured.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the thus obtained dielectric layer was determined in the same manner as in Example 1. (%) was 97%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was found to be 190 ppm / K in the same manner as in Example 1. .
- Example 7 Assuming that ⁇ was 1.6 and the molar ratio between bismuth (B i) and titanium (T i) was 1.4, the same procedure as in Example 7 was carried out except that the raw material solution was prepared. Then, a dielectric layer was formed, and a thin film capacitor was manufactured.
- the degree of orientation (%) in the c-axis direction of the bismuth layered compound contained in the thus obtained dielectric layer was determined in the same manner as in Example 1. %) was 100%.
- the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitor thus obtained was determined in the same manner as in Example 1. As a result, the value was 150 ppm mK. .
- FIG. 2 shows the average change rate (temperature coefficient of capacitance) ⁇ of the dielectric constant with respect to the temperature of the thin film capacitors manufactured according to Examples 1 to 10 and the dielectric layer constituting the thin film capacitor.
- 4 is a graph showing the relationship between the bismuth layered compound contained and the degree of orientation (%) in the c-axis direction.
- the dielectric layer 5 of the thin film capacitor element 1 the stoichiometric composition formula. Represented by S r B i 4 T i 4 0 i 5, bismuth scan (B i) and It is formed of a dielectric material containing a bismuth layered compound containing an excess of bismuth so that the molar ratio of titanium (T i) is 1 and B i / T i ⁇ 1.5.
- the dielectric layer 5 of element 1 is Stoichiometric composition formula: S r B i is represented by 4 T i 5 bismuth (B i) and so that the molar ratio of titanium (T i) is the i rather B i / T i rather 1.5, by the dielectric material containing a bismuth layer compound containing bismuth excessive over -connection, formed to is not necessarily required, stoichiometric composition formula: (B i 2 0 2) 2 +
- the dielectric layer 5 of the thin-film capacitor 1 is formed of a dielectric material containing a bismuth layered compound in the range of (1).
- the excess content of bismuth is 0 in terms of bismuth (B i).
- the dielectric layer 5 of the thin film capacitive element 1 is formed of a dielectric material containing a bismuth layer compound in the range of 4 ⁇ B i ⁇ 0.5 mol.
- the stoichiometric composition formula: x S r B i 4 T i 4 0 1 5 - (1 - x) MB i 4 T i has a composition represented by 4 O 5 (symbols, calcium, barium And at least one element selected from lead and 0 i ⁇ l), bismuth is contained in excess of the stoichiometric ratio, and the bismuth excess content is reduced to bismuth (B i)
- the dielectric layer 5 of the thin-film capacitive element 1 can be formed of a dielectric material containing a bismuth layered compound in the range of 0 to B i and 0.2 mol in terms of conversion.
- the stoichiometric composition formula: XS r B i 4 T i 4 O! 5- (1-x) MB i 4 Ti 4 0 15 has the composition represented by (the symbol M is at least one selected from calcium, nickel and lithium and lead And 0 ⁇ 1. ), Bismuth is contained in excess of the stoichiometric ratio, and the excess content of bismuth is such that the molar ratio of bismuth (B i) to titanium (T i) is 1 and B i / T i
- the dielectric layer 5 of the thin-film capacitive element 1 can also be formed from a dielectric material containing a bismuth layered compound in the range described above.
- the dielectric layer 5 of the thin-film capacitive element 1 can also be formed from a dielectric material containing a bismuth layer compound in the range.
- the coating film is formed by the spin coating method, but the coating film is formed by the spin coating method. It is not always necessary to form the coating film.
- a coating film may be formed by a dip coating method.
- the support substrate 2 of the thin film capacitor 1 is formed of silicon single crystal, but the support substrate 2 of the thin film capacitor 1 is formed of silicon single crystal.
- Rukoto is not necessarily required, S r T i 0 3 single crystal is excellent in lattice matching, Mg O single crystal, L a a 1 0 3 single crystal, such as single crystal, glass, fused quartz, S i O Amorufu Ryosu materials such as 2 / S i, Z r O 2 / S i, can also be used C e O 2 / S i supporting substrate 2 formed by like other materials such as.
- the lower electrode layer 4 of the thin film capacitor 1 is formed of platinum, but the lower electrode layer 4 of the thin film capacitor 1 is formed of platinum. is not necessarily required, S RMo_ ⁇ 3, S r Ru_ ⁇ 3, C a R U_ ⁇ 3, S r V0 3, S r C R_ ⁇ 3, S r C O_ ⁇ 3, L a N i 0 3 , conductive oxides such as N b doped S r T I_ ⁇ 3, ruthenium, gold, palladium, silver, etc. of the precious metal is stomach their alloys, conductive glass, such as I tO, nickel, or copper
- the lower electrode layer 4 of the thin-film capacitive element 1 can be formed of a base metal or an alloy thereof.
- the lower electrode layer 4 When the support substrate 2 is formed using a material excellent in lattice matching, the lower electrode layer 4, C a R u 0 3 and S r conductive oxide such as R uo 3, such as platinum or ruthenium It is preferably formed of a noble metal.
- the lower electrode layer 4 of the thin-film capacitor 1 is formed by a sputtering method. It is not always necessary to form by sputtering, but vacuum deposition, pulsed laser deposition (PLD), metal-organic chemical vapor deposition (MOC VD)
- the lower electrode layer 4 can also be formed by using another thin film forming method such as (CSD method).
- the dielectric layer 5 of the thin film capacitor 1 is formed by a metal-organic decomposition (MOD) method.
- the dielectric layer 5 of the thin film capacitive element 1 it is not always necessary to form the dielectric layer 5 of the thin film capacitive element 1 by an organic metal decomposition method, but a vacuum evaporation method, a sputtering method, a pulsed laser evaporation method (PLD), an organic metal layer method, Method 1, metal-organic chemical vapor deposition (MOC VD), sol-gel method, or other thin film forming methods can be used to form the dielectric layer 5.
- the organic metal decomposition method ⁇ A liquid phase method such as a sol-gel method is preferably used.
- a raw material solution is applied onto the lower electrode layer 4 by spin coating.
- the raw material solution may be applied using another coating method such as a dip coating method or a spray coating method.
- the solution may be applied on the lower electrode layer 4.
- the upper electrode layer 6 of the thin film capacitor 1 is formed of platinum. Not necessarily needed is to form the upper electrode layer 6 of the capacitor element 1 by platinum, N d O, N b O , R E_ ⁇ 2, R H_ ⁇ 2, O s 0 2, I R_ ⁇ 2, Ru0 2, R e 0 3, S rMo 0 3, S r R U_ ⁇ 3, C a Ru_ ⁇ 3, S r V0 3, S r C R_ ⁇ 3, S r C O_ ⁇ 3, L a N i ⁇ 3 , N b doped S r T i O 3 conductive oxide such as ruthenium, gold, palladium, noble metals or alloys thereof such as silver, conducting glass such as I tO, nickel, base metals or their alloys, such as copper Thereby, the upper electrode layer 6 of the thin film capacitor 1 can be formed.
- platinum N d O, N b O , R E_ ⁇ 2, R H_ ⁇ 2, O s 0 2, I R_ ⁇ 2, Ru0 2, R e
- the upper electrode layer 6 of the thin film capacitor 1 is formed by sputtering, but the upper electrode layer 6 of the thin film capacitor 1 is formed by sputtering. It is not always necessary to form the substrate by sputtering, but it is necessary to use vacuum deposition, pulsed laser deposition (PLD), metal-organic chemical vapor deposition (MOC VD), liquid
- the upper electrode layer 6 can also be formed by using another thin film forming method such as a phase method (CSD method). According to the present invention, it is possible to provide a thin-film capacitive element which can be thinned and can be easily manufactured, and has excellent temperature compensation characteristics, and an electronic circuit and an electronic device including the same. become.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Semiconductor Memories (AREA)
- Inorganic Insulating Materials (AREA)
- Ceramic Capacitors (AREA)
Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04713200A EP1598870A1 (en) | 2003-02-26 | 2004-02-20 | Thin-film capacitative element and electronic circuit or electronic equipment including the same |
| JP2005502858A JPWO2004077564A1 (ja) | 2003-02-26 | 2004-02-20 | 薄膜容量素子ならびにそれを含んだ電子回路および電子機器 |
| US10/546,667 US20060186395A1 (en) | 2003-02-26 | 2004-02-20 | Thin-film capacitative element and electronic circuit and electronic equipment including the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-49623 | 2003-02-26 | ||
| JP2003049623 | 2003-02-26 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/165,200 Continuation-In-Part US10561629B2 (en) | 2004-01-14 | 2005-06-24 | Food containing glycine and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004077564A1 true WO2004077564A1 (ja) | 2004-09-10 |
Family
ID=32923313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2004/001977 Ceased WO2004077564A1 (ja) | 2003-02-26 | 2004-02-20 | 薄膜容量素子ならびにそれを含んだ電子回路および電子機器 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060186395A1 (ja) |
| EP (1) | EP1598870A1 (ja) |
| JP (1) | JPWO2004077564A1 (ja) |
| KR (1) | KR20050100699A (ja) |
| CN (1) | CN1754262A (ja) |
| TW (1) | TWI235390B (ja) |
| WO (1) | WO2004077564A1 (ja) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050108366A (ko) * | 2003-02-27 | 2005-11-16 | 티디케이가부시기가이샤 | 박막용량소자용 조성물, 고유전율 절연막, 박막용량소자,박막적층 콘덴서,전자회로 및 전자기기 |
| CN109111222B (zh) * | 2018-09-30 | 2022-03-01 | 陕西科技大学 | 一种Co掺杂的具有奥里维里斯结构的多铁性陶瓷及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925124A (ja) * | 1995-07-10 | 1997-01-28 | Mitsubishi Materials Corp | Bi系強誘電体薄膜形成用組成物並びにBi系強誘電体薄膜及びその製造方法 |
| JPH0931635A (ja) * | 1995-07-18 | 1997-02-04 | Mitsubishi Materials Corp | Bi系強誘電体薄膜形成用ターゲット材及びBi系強誘電体薄膜の製造方法 |
| JPH1056142A (ja) * | 1996-05-30 | 1998-02-24 | Oki Electric Ind Co Ltd | 半導体記憶素子およびその形成方法 |
| JP2000169297A (ja) * | 1998-09-29 | 2000-06-20 | Sharp Corp | 酸化物強誘電体薄膜の製造方法、酸化物強誘電体薄膜及び酸化物強誘電体薄膜素子 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5624707A (en) * | 1991-12-13 | 1997-04-29 | Symetrix Corporation | Method of forming ABO3 films with excess B-site modifiers |
| US6025619A (en) * | 1992-10-23 | 2000-02-15 | Azuma; Masamichi | Thin films of ABO3 with excess A-site and B-site modifiers and method of fabricating integrated circuits with same |
| US6133050A (en) * | 1992-10-23 | 2000-10-17 | Symetrix Corporation | UV radiation process for making electronic devices having low-leakage-current and low-polarization fatigue |
| US6639262B2 (en) * | 1993-12-10 | 2003-10-28 | Symetrix Corporation | Metal oxide integrated circuit on silicon germanium substrate |
| US6876536B2 (en) * | 2002-12-27 | 2005-04-05 | Tdk Corporation | Thin film capacitor and method for fabricating the same |
-
2004
- 2004-02-20 US US10/546,667 patent/US20060186395A1/en not_active Abandoned
- 2004-02-20 CN CNA2004800053770A patent/CN1754262A/zh active Pending
- 2004-02-20 KR KR1020057015636A patent/KR20050100699A/ko not_active Ceased
- 2004-02-20 WO PCT/JP2004/001977 patent/WO2004077564A1/ja not_active Ceased
- 2004-02-20 EP EP04713200A patent/EP1598870A1/en not_active Withdrawn
- 2004-02-20 JP JP2005502858A patent/JPWO2004077564A1/ja active Pending
- 2004-02-23 TW TW093104465A patent/TWI235390B/zh not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925124A (ja) * | 1995-07-10 | 1997-01-28 | Mitsubishi Materials Corp | Bi系強誘電体薄膜形成用組成物並びにBi系強誘電体薄膜及びその製造方法 |
| JPH0931635A (ja) * | 1995-07-18 | 1997-02-04 | Mitsubishi Materials Corp | Bi系強誘電体薄膜形成用ターゲット材及びBi系強誘電体薄膜の製造方法 |
| JPH1056142A (ja) * | 1996-05-30 | 1998-02-24 | Oki Electric Ind Co Ltd | 半導体記憶素子およびその形成方法 |
| JP2000169297A (ja) * | 1998-09-29 | 2000-06-20 | Sharp Corp | 酸化物強誘電体薄膜の製造方法、酸化物強誘電体薄膜及び酸化物強誘電体薄膜素子 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI235390B (en) | 2005-07-01 |
| EP1598870A1 (en) | 2005-11-23 |
| KR20050100699A (ko) | 2005-10-19 |
| TW200425181A (en) | 2004-11-16 |
| CN1754262A (zh) | 2006-03-29 |
| US20060186395A1 (en) | 2006-08-24 |
| JPWO2004077564A1 (ja) | 2006-06-08 |
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