WO2017098852A1 - 酸化物誘電体及びその製造方法、並びに固体電子装置及びその製造方法 - Google Patents

酸化物誘電体及びその製造方法、並びに固体電子装置及びその製造方法 Download PDF

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WO2017098852A1
WO2017098852A1 PCT/JP2016/083113 JP2016083113W WO2017098852A1 WO 2017098852 A1 WO2017098852 A1 WO 2017098852A1 JP 2016083113 W JP2016083113 W JP 2016083113W WO 2017098852 A1 WO2017098852 A1 WO 2017098852A1
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layer
atoms
oxide
bismuth
precursor
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PCT/JP2016/083113
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English (en)
French (fr)
Japanese (ja)
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下田　達也
井上　聡
智紀 有賀
慎治 竹内
瀬川　茂俊
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国立大学法人北陸先端科学技術大学院大学
アダマンド株式会社
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Priority to JP2017554982A priority Critical patent/JP6716602B2/ja
Priority to TW105139027A priority patent/TWI710527B/zh
Publication of WO2017098852A1 publication Critical patent/WO2017098852A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • 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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • 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
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to an oxide dielectric and a manufacturing method thereof, and a solid-state electronic device and a manufacturing method thereof.
  • oxide layers composed of various compositions having functionality have been developed. Further, as an example of a solid-state electronic device including the oxide layer, a device including a ferroelectric thin film that can be expected to operate at high speed has been developed. Further, BiNbO 4 has been developed as an oxide layer that does not contain lead (Pb) and can be baked at a relatively low temperature as a dielectric material used in the solid-state electronic device. As for this BiNbO 4 , the dielectric properties of BiNbO 4 formed by the solid phase growth method have been reported (Non-patent Document 1). In addition, the patent document discloses an oxide layer made of bismuth (Bi) and niobium (Nb) having a relative dielectric constant of 60 or more at 1 kHz (Patent Document 1). ⁇ 3).
  • capacitors In the industry, in order to realize high performance of solid-state electronic devices including capacitors or capacitors (hereinafter collectively referred to as “capacitors”), semiconductor devices, or microelectromechanical systems, only a high relative dielectric constant is required. However, there is a need for oxide dielectrics and oxide dielectric layers with low dielectric loss (tan ⁇ ) electrical properties. In addition, in the process of manufacturing an oxide dielectric having such characteristics, particularly when the degree of freedom regarding the heating temperature is high, it is possible to manufacture an oxide dielectric that can realize more stable and high reliability. It becomes.
  • the present invention solves at least one of the above-described problems, thereby improving the performance of a solid-state electronic device using an oxide as a dielectric or an insulator (hereinafter collectively referred to as “dielectric”).
  • dielectric oxide as a dielectric or an insulator
  • the manufacturing process of such a solid-state electronic device can be simplified and energy can be saved.
  • the present invention greatly contributes to the provision of an oxide dielectric excellent in industriality or mass productivity and a solid-state electronic device including the oxide dielectric.
  • BNO oxides composed of bismuth (Bi) and niobium (Nb) having a relatively high dielectric constant.
  • BNO oxides bismuth (Bi) and niobium (Nb) having a relatively high dielectric constant.
  • the inventors have not only focused on the BNO oxide alone, but also realized further improvement in the electrical properties of the oxide dielectric (especially very low dielectric loss) in consideration of other elements I thought it was important.
  • the inventors have also found that an inexpensive and simple manufacturing process can be realized by adopting a method that does not require a high vacuum state in the manufacturing method of the oxide dielectric.
  • a typical one is a “printing” processing method also called a screen printing method or “nanoimprint”.
  • the inventors have also found that the oxide layer made of the oxide dielectric can be patterned by the above-described methods that are inexpensive and simple.
  • the inventors have realized the formation of the oxide dielectric, and consequently the formation of the oxide dielectric by a process that is greatly simplified or energy-saving compared to the conventional technology and easy to increase in area as well as realizing a high-performance oxide.
  • the present inventors have found that it is possible to manufacture a solid-state electronic device including the oxide dielectric.
  • the present invention has been created based on the above viewpoints.
  • One oxide dielectric of the present invention includes an oxide (which may include unavoidable impurities) of bismuth (Bi), niobium (Nb), and titanium (Ti) having a crystal phase of a pyrochlore type crystal structure,
  • the number of atoms of the bismuth (Bi) is 1, the number of atoms of the niobium (Nb) is 0.5 or more and less than 1.7, and the number of atoms of the bismuth (Bi) is 1,
  • the number of atoms of the titanium (Ti) is more than 0 and less than 1.3.
  • This oxide dielectric can achieve very low dielectric loss (tan ⁇ ) values (typically less than 0.001 at 1 kHz) while retaining a relatively high dielectric constant.
  • an oxide composed of bismuth (Bi), niobium (Nb) and titanium (Ti) (which may contain unavoidable impurities. The same applies to all oxides in the present application). It has a crystal phase with a pyrochlore crystal structure.
  • the oxide described above is temporarily heated at a high temperature (for example, 600 ° C. to 800 ° C., typically more than 620 ° C. and 800 ° C. or less).
  • one oxide dielectric manufacturing method of the present invention includes a precursor solution containing a precursor containing bismuth (Bi), a precursor containing niobium (Nb), and a precursor containing titanium (Ti) as a solute.
  • the bismuth (Bi) A step of forming an oxide dielectric layer in which the number of atoms of the titanium (Ti) is more than 0 and less than 1.3 when the number of atoms is 1.
  • oxide dielectric manufacturing method a very low dielectric loss (tan ⁇ ) value (typically less than 0.001 at a frequency of 1 kHz) is maintained while maintaining a relatively high dielectric constant.
  • realizing oxide dielectrics can be produced.
  • the oxide dielectric manufactured by this manufacturing method it is possible to include an oxide composed of bismuth (Bi), niobium (Nb) and titanium (Ti). The same as for the above) has a crystal phase of a pyrochlore crystal structure.
  • a high temperature for example, 600 ° C. or higher and 800 ° C. or lower, typically more than 620 ° C. and 800 ° C.
  • an oxide layer is formed by a relatively simple process that does not use a photolithography method (for example, an inkjet method, a screen printing method, an intaglio / letter printing method, or a nanoimprint method). Can be done. This eliminates the need for relatively long and / or expensive equipment such as a process using a vacuum process. As a result, the manufacturing method of each above-mentioned oxide layer is excellent in industrial property or mass productivity.
  • a photolithography method for example, an inkjet method, a screen printing method, an intaglio / letter printing method, or a nanoimprint method.
  • the state in which the precursor layer is heated at 80 ° C. to 250 ° C. in an oxygen-containing atmosphere before forming the oxide dielectric layer eliminates the need for relatively long and / or expensive equipment such as a process using a vacuum process. From the viewpoint of making it, this is a preferred embodiment that can be adopted.
  • in an oxygen-containing atmosphere means in an oxygen atmosphere or in the air.
  • layer in the present application is a concept including not only a layer but also a film.
  • film in the present application is a concept including not only a film but also a layer.
  • One oxide dielectric of the present invention can achieve a very low dielectric loss (tan ⁇ ) value while maintaining a relatively high dielectric constant.
  • an oxide dielectric that achieves a very low dielectric loss (tan ⁇ ) value while maintaining a relatively high relative dielectric constant is manufactured. be able to.
  • FIG. 1 shows the whole structure of the thin film capacitor which is an example of the solid-state electronic device in the 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor in the 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor in the 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor in the 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor in the 1st Embodiment of this invention.
  • X-ray diffraction showing the crystal structure of the oxide according to the difference in the heating temperature of the oxide composed of bismuth (Bi), niobium (Nb) and titanium (Ti) and the difference in the firing time in the reference example. It is a graph which shows the change of the measurement result. It is a graph which shows the change of the measurement result of the X-ray diffraction (XRD) which shows the crystal structure of this oxide by the difference in the heating temperature of the oxide in the 1st Embodiment of this invention, and the difference in baking time.
  • XRD X-ray diffraction
  • FIG. 1 It is a figure which shows the whole structure of the thin film capacitor which is an example of the solid-state electronic device in the 3rd Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor which is an example of the solid-state electronic device in the 3rd Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor which is an example of the solid-state electronic device in the 3rd Embodiment of this invention. It is a cross-sectional schematic diagram which shows one process of the manufacturing method of the thin film capacitor which is an example of the solid-state electronic device in the 3rd Embodiment of this invention.
  • FIG. 1 is a diagram showing an overall configuration of a thin film capacitor 100 that is an example of a solid-state electronic device according to the present embodiment.
  • a thin film capacitor 100 is formed on a substrate 10 from the substrate 10 side, a lower electrode layer 20 and an oxide dielectric layer (hereinafter also referred to as “oxide layer” for short. The same applies hereinafter). 30 and the upper electrode layer 40.
  • the substrate 10 for example, high heat-resistant glass, SiO 2 / Si substrate, an alumina (Al 2 O 3) substrate, through an STO (SrTiO) substrate, SiO 2 layer and the Ti layer on the surface of the Si substrate STO (SrTiO) Insulating substrate in which layers are formed, insulating substrate in which SiO 2 layer and TiO X layer are laminated in this order on the surface of Si substrate, semiconductor substrate (for example, Si substrate, SiC substrate, Ge substrate, resin substrate, etc.) ) Can be used.
  • a metal material such as a refractory metal such as platinum, gold, silver, copper, aluminum, molybdenum, palladium, ruthenium, iridium, tungsten, or an alloy thereof is used. .
  • the oxide dielectric layer (oxide layer 30) includes a precursor containing bismuth (Bi), a precursor containing niobium (Nb), and a precursor containing titanium (Ti) as a solute.
  • This precursor solution is formed by heating a precursor starting from the precursor solution in an oxygen-containing atmosphere (hereinafter, the production method according to this step is also referred to as “solution method”).
  • the solute in the precursor solution in this embodiment for example, bismuth 2-ethylhexanoate, niobium 2-ethylhexanoate, and titanium 2-ethylhexanoate can be employed.
  • an oxide composed of bismuth (Bi), niobium (Nb), and titanium (Ti) by employing a precursor layer (simply referred to as “precursor layer”) that uses the precursor solution described above as a starting material. 30 is obtained. More specifically, as will be described later, the oxide layer 30 of the present embodiment obtained by heat treatment at least at 800 ° C. or lower (more preferably at 700 ° C. or lower) is formed from a crystal phase having a pyrochlore crystal structure. Containing oxides. This is a finding based on an interesting analysis result that a peak derived from a ⁇ -BiNbO 4 type crystal structure is not observed by X-ray diffraction (XRD) measurement. Note that the oxide layer 30 of the present embodiment may include a microcrystalline phase.
  • the general pyrochlore crystal structure known so far has been observed in an oxide composed of bismuth (Bi), niobium (Nb), and zinc (Zn).
  • the oxide layer 30 of this embodiment made of bismuth (Bi), niobium (Nb), and titanium (Ti) has a pyrochlore crystal structure. It is not clear at this time why the oxide layer 30 develops a pyrochlore crystal structure.
  • the oxide layer 30 of the present embodiment has an amorphous phase and a Bi 3 NbO 7 type crystal structure depending on the composition ratio and / or the heating temperature. It was confirmed that it also has a crystal phase (third crystal phase). (However, in the case of an Nb-rich oxide layer, Bi 3 NbO 7- type crystals do not appear.) Thus, the presence of various crystal phases and amorphous phases is due to the formation of unnecessary grain boundaries. This is a preferred embodiment from the viewpoint of accurately preventing deterioration or variation in electrical characteristics.
  • FIG. 2 are cross-sectional schematic views showing one process of the method of manufacturing the thin film capacitor 100, respectively.
  • the lower electrode layer 20 is formed on the substrate 10.
  • the oxide layer 30 is formed on the lower electrode layer 20, and then the upper electrode layer 40 is formed on the oxide layer 30.
  • FIG. 2 is a diagram showing a process of forming the lower electrode layer 20.
  • the lower electrode layer 20 of the thin film capacitor 100 is formed of platinum (Pt)
  • a layer for example, 200 nm thick
  • platinum (Pt) is formed on the substrate 10 by a known sputtering method.
  • the oxide layer 30 is formed on the lower electrode layer 20.
  • the oxide layer 30 is formed in the order of (A) formation of a precursor layer and preliminary baking, and (B) main baking.
  • 3 and 4 are diagrams showing a process of forming the oxide layer 30.
  • the oxide layer 30 in the manufacturing process of the thin film capacitor 100 is formed of an oxide composed of bismuth (Bi), niobium (Nb), and titanium (Ti) having a crystal phase of a pyrochlore crystal structure. An example will be described.
  • precursor solution having a precursor containing (Nb) (also referred to as precursor B) and a precursor containing titanium (Ti) (also referred to as precursor C) as a solute.
  • precursor layer also referred to as “precursor layer” 30a is formed.
  • examples of the precursor A for the oxide layer 30 include bismuth octylate, bismuth chloride, bismuth nitrate, or various bismuth alkoxides (for example, bismuth isopropoxide) in addition to the bismuth 2-ethylhexanoate described above.
  • bismuth butoxide, bismuth ethoxide, bismuth methoxyethoxide may be employed.
  • Examples of the precursor B in the present embodiment include niobium octylate, niobium chloride, niobium nitrate, or various niobium alkoxides (for example, niobium isopropoxide, niobium butoxide, niobium 2-ethylhexanoate, and the like). Niobium ethoxide, niobium methoxyethoxide) may be employed.
  • Examples of the precursor C in this embodiment include titanium octylate, titanium chloride, titanium nitrate, or various titanium alkoxides (for example, titanium isopropoxide, titanium butoxide, Titanium ethoxide, titanium methoxyethoxide) may be employed.
  • the solvent of the precursor solution is at least one alcohol solvent selected from the group consisting of ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol, or acetic acid, propionic acid, octyl
  • the solvent is preferably a solvent that is at least one carboxylic acid selected from the group of acids and 2-ethylhexanoic acid. Therefore, in the solvent of the precursor solution, a mixed solvent of the above-described two or more alcohol solvents or a mixed solvent of the above-described two or more carboxylic acids is an embodiment that can be employed.
  • the precursor solution of this embodiment mixes the 1st solution shown in the following (1), the 2nd solution shown in the following (2), and the 3rd solution shown in the following (3).
  • Is manufactured by. A first solution obtained by mixing a solution obtained by diluting bismuth 2-ethylhexanoate with 1-butanol and a solution obtained by diluting bismuth 2-ethylhexanoate with 2-methoxyethanol, or bismuth 2-ethylhexanoate First solution (2) diluted with 2-ethylhexanoic acid (2) A solution obtained by diluting niobium 2-ethylhexanoate with 1-butanol was mixed with a solution obtained by diluting niobium 2-ethylhexanoate with 2-methoxyethanol.
  • Second solution or second solution obtained by diluting niobium ethoxide with 2-ethylhexanoic acid (3) A solution obtained by diluting titanium 2-ethylhexanoate with 1-butanol, and titanium 2-ethylhexanoate with 2-methoxyethanol Third solution obtained by mixing diluted solution or third solution obtained by diluting titanium 2-ethylhexanoate with 2 ethylhexanoic acid
  • the precursor solution was prepared to be .5.
  • preliminary baking is performed in an oxygen-containing atmosphere for a predetermined time in a temperature range of 80 ° C. or higher and 250 ° C. or lower.
  • the solvent typically, the main solvent
  • the organic chain remains).
  • Forming such a gel state makes it easier to form a film by an embossing method or a screen printing method, which is one method of a film forming process described later.
  • the pre-baking temperature is preferably 80 ° C. or higher and 250 ° C. or lower.
  • the desired thickness of the oxide layer 30 can be obtained by repeating the formation and preliminary baking of the precursor layer 30a by the above-described spin coating method a plurality of times.
  • an oxygen atmosphere for example, 100% by volume, but not limited thereto
  • a heating step is performed in which heating is performed at a temperature in the range of 550 ° C. to 800 ° C. (first temperature).
  • an oxide layer (oxide layer 30) for example, 170 nm thick) made of bismuth (Bi), niobium (Nb), and titanium (Ti) is formed on the electrode layer. Is done.
  • the range of the thickness of the oxide layer 30 is preferably 30 nm or more. If the thickness of the oxide layer 30 is less than 30 nm, it is not preferable to apply it to a solid-state electronic device due to an increase in leakage current and dielectric loss accompanying a decrease in the thickness.
  • FIG. 5 is a diagram illustrating a process of forming the upper electrode layer 40.
  • the upper electrode layer 40 of the thin film capacitor 100 is formed of platinum (Pt)
  • a layer for example, 150 nm thick
  • platinum (Pt) is formed on the oxide layer 30 by a known sputtering method, similarly to the lower electrode layer 20.
  • the main firing temperature (first temperature) when forming the oxide layer 30 is set to 550 ° C. or higher and 800 ° C. or lower, but the first temperature is not limited to the above temperature range.
  • the inventors have a temperature range of 550 ° C. or higher and 800 ° C. or lower, particularly 600 ° C. or higher and 800 ° C. or lower (typically more than 620 ° C. and 800 ° C. or lower, or 650 ° C. or higher and 800 ° C. or lower).
  • the oxide layer precursor solution may be heated in an oxygen-containing atmosphere without using a vacuum process.
  • the area can be easily increased, and the industrial property or mass productivity can be remarkably improved.
  • the temperature for heating the precursor layer 30a to the oxide layer 30 (the temperature for main firing) is from 550 ° C. It has been clarified that the crystal phase of the pyrochlore crystal structure appears more clearly as the temperature increases toward 800 ° C. and as the heating time is longer at least within a predetermined time range. Furthermore, interestingly, the crystal structure of ⁇ -BiNbO 4 that has been confirmed to be present in the case of BNO oxide formed by heat treatment at 590 ° C. or higher is 600 ° C. or higher and 800 ° C. or lower, particularly 650 ° C. or higher. It turned out that it does not appear in the oxide layer 30 of this embodiment formed by heat processing below 800 degreeC.
  • the oxide layer 30 of the present embodiment can achieve a very low dielectric loss value particularly when any one of the conditions shown in (X1) and (Y1) described later is satisfied. confirmed. Below, the results of our analysis will be described in more detail.
  • 6 to 8 show the difference in heating temperature of the oxide (oxide layer 30) made of bismuth (Bi), niobium (Nb), and titanium (Ti) and the firing time in this embodiment. It is a graph which shows the change of the measurement result of the X-ray diffraction (XRD) using CuK (alpha) characteristic X-ray which shows the crystal structure of this oxide.
  • 6A to 8A show the results measured after the heating for 20 minutes at the first temperature as the main baking.
  • FIGS. 6 to 8 (b) were measured after the main calcination and after the oxide layer 30 was additionally heated at the same temperature for 20 minutes as a post-annealing treatment. Results are shown. 7 and 8 are disclosed as examples of the present embodiment, and FIG. 6 is disclosed as a reference example.
  • the atomic ratio of bismuth (Bi), niobium (Nb), and titanium (Ti) in the oxide 30 (sample to be measured) employed in FIGS. 6 to 8 is as follows (sample a) to As shown in (Sample c).
  • bismuth (Bi): niobium (Nb): titanium (Ti) 1.5: 1.5: 1
  • bismuth (Bi): niobium (Nb): titanium (Ti) 1.5: 1: 1.5: 1.5
  • ⁇ -BiNbO 4 type One characteristic fact is that no peak derived from the crystal structure is observed. This suppresses or prevents the expression of the ⁇ -BiNbO4 crystal structure having a relatively low relative dielectric constant in the manufacturing process of the oxide 30 including the main firing, and greatly expands the temperature range in which the pyrochlore crystal structure is expressed. It means you can.
  • FIG. 9 is a graph showing the correlation between the value of dielectric loss (tan ⁇ ) and the heating temperature (° C.) for the above-described sample a, sample b, and sample c after the main firing and the post-annealing treatment. It is.
  • FIG. 10 is a graph showing the correlation between the relative dielectric constant and the heating temperature (° C.) for the sample a, the sample b, and the sample c after the main baking and the post annealing treatment.
  • a BNO oxide having a relatively high relative dielectric constant specifically, the number of atoms of niobium (Nb) is about 1.7 when the number of atoms of bismuth (Bi) is 1.
  • BNO oxide was adopted. 9 and 10, the sample a is displayed as a reference example, the sample b is displayed as Example 1, and the sample c is displayed as Example 2. In addition, in FIGS. 9 and 10, the heating temperatures of the main firing and the post-annealing process are the same.
  • the relative dielectric constant was measured by applying a voltage of 0.1 V and an AC voltage of 1 kHz between the lower electrode layer and the upper electrode layer.
  • a 1260-SYS type broadband dielectric constant measurement system manufactured by Toyo Corporation was used.
  • the dielectric loss (tan ⁇ ) was measured by applying a voltage of 0.1 V and an alternating voltage of 1 kHz between the lower electrode layer and the upper electrode layer at room temperature.
  • a 1260-SYS type broadband dielectric constant measurement system manufactured by Toyo Corporation was used.
  • X1 When the number of atoms of bismuth (Bi) is 1.5, the number of atoms of niobium (Nb) is 1 or more and less than 2, or when the number of atoms of bismuth (Bi) is 1.5 The number of (Ti) atoms is more than 0.5 and 1.5 or less. Further, in the condition of X1, in addition to the above-described conditions, the sum of the number of atoms of niobium (Nb) and the number of atoms of titanium (Ti) is 1.5 or more and 3.9 or less. This is a more preferable condition.
  • Y1 When the number of atoms of bismuth (Bi) is 1.5, the number of atoms of niobium (Nb) is 1 or more and 2 or less, and the number of atoms of titanium (Ti) is 0.5 or more and 1.5 or less. In addition, when titanium (Ti) is set to 1, niobium (Nb) is less than 4.
  • the value of the dielectric loss (tan ⁇ ) of the reference example is inferior to each value of Example 1 and Example 2, it is 0.01 when the value of the dielectric loss (tan ⁇ ) of the reference example is 600 ° C. or more. Therefore, it can be said that the value of dielectric loss (tan ⁇ ) of this reference example is also a good value.
  • a relatively high relative dielectric constant can be obtained by heat treatment at least at 600 ° C. or higher.
  • a relatively high dielectric constant could be obtained by heat treatment at 550 ° C. or higher.
  • the sum of the number of atoms of niobium (Nb) and the number of atoms of titanium (Ti) is 1 or more and 2.6 or less. It is a condition.
  • FIG. 11 is a graph showing the correlation between the value of dielectric loss (tan ⁇ ) and the heating temperature (° C.) for the above-mentioned sample d after the main firing and the post-annealing treatment.
  • FIG. 12 is a graph showing the correlation between the relative dielectric constant and the heating temperature (° C.) for the sample d after the main firing and the post-annealing treatment.
  • the sample d is displayed as Example 3.
  • the measurement conditions are the same as those of (Sample a) to (Sample c).
  • the value of dielectric loss (tan ⁇ ) of Example 3 is extremely low (typically 0.002 or less), particularly by adopting a heating temperature of 700 ° C. or higher. It became clear. Therefore, extremely low dielectric loss (tan ⁇ ) can be realized when at least one selected from the group of conditions (X1) and (Y1) described above is satisfied.
  • Example 3 a relatively high dielectric constant can be obtained by heat treatment at least at 600 ° C. or higher.
  • the relative dielectric constant is 120 or more. (In particular, at about 700 ° C., the relative dielectric constant is 160 or more.)
  • the number of atoms of bismuth (Bi) is 1, the number of atoms of niobium (Nb) is 0.5 or more and less than 1.7, and the bismuth (Bi) ) Is 1 and the number of atoms of the titanium (Ti) is more than 0 and less than 1.3 (more preferably 0.08 or more and less than 1.3, still more preferably 0.3 or more and 1.3 Less), an oxide (or oxide dielectric) capable of achieving a very low dielectric loss value while maintaining a relatively high relative dielectric constant can be manufactured.
  • the accuracy is higher and a relatively high dielectric constant is maintained.
  • An oxide (or oxide dielectric) that can achieve very low dielectric loss values can be produced.
  • the sum of the number of niobium (Nb) atoms and the number of titanium (Ti) atoms dominates the physical properties of the oxide of the present embodiment (that is, the relative dielectric constant and dielectric loss).
  • an oxide capable of realizing a very low dielectric loss value while maintaining a relatively high relative dielectric constant with high accuracy. (Or oxide dielectric) is considered difficult to obtain.
  • the post-annealing process is performed as described above.
  • the post-annealing process is not necessarily performed in order to achieve the effect of the present embodiment. do not do.
  • the post-annealing process is a preferable aspect that can be adopted.
  • a post-annealing process can be performed after the embossing process is performed and the patterning is completed.
  • the oxide layer 30 of the first embodiment is formed by the main baking step at the first temperature (for example, 650 ° C.), about 20 minutes further. It is formed by heating at a second temperature not higher than the first temperature (typically 350 ° C. or higher and 650 ° C. or lower) in an oxygen-containing atmosphere.
  • the crystal phase of the pyrochlore crystal structure in the oxide 30 in the thin film capacitor 100 can be expressed with higher accuracy.
  • the effect which further improves the adhesiveness of the oxide layer 30 and its base layer (namely, lower electrode layer 20) and / or the upper electrode layer 40 may be created.
  • the second temperature in the post-annealing process is preferably a temperature equal to or lower than the first temperature. This is because if the second temperature is higher than the first temperature, the second temperature is likely to affect the physical properties of the oxide layer 30a. Therefore, it is preferable to select a temperature at which the second temperature does not dominate the physical properties of the oxide layer 30a.
  • the lower limit value of the second temperature in the post-annealing process is determined from the viewpoint of further improving the adhesion with the base layer (that is, the lower electrode layer 20) and / or the upper electrode layer 40 as described above.
  • the leakage current value of the sample b described above was 10 ⁇ 8 A / cm 2 to 10 ⁇ 7 A / cm 2 .
  • the leakage current was measured by applying the voltage described above between the lower electrode layer and the upper electrode layer.
  • Agilent Technologies 4156C type was used for this measurement.
  • a leakage current value as low as the result of the typical leakage current value described above was obtained.
  • the sample c can have the same effect as the sample b.
  • the oxide (oxide layer 30) made of bismuth (Bi), niobium (Nb), and titanium (Ti) according to the present embodiment is relatively high by adopting an atomic ratio within a predetermined range.
  • a low dielectric loss value can be realized while maintaining the relative dielectric constant. Therefore, it is particularly preferable to apply to various solid-state electronic devices (for example, a capacitor, a semiconductor device, or a microelectromechanical system, or a composite device including at least two of a high-frequency filter, a patch antenna, and an RCL). confirmed.
  • a multilayer capacitor 200 that is an example of a solid-state electronic device will be described. Note that at least a part of the multilayer capacitor 200 is formed by a screen printing method.
  • an oxide composed of bismuth (Bi), niobium (Nb), and titanium (Ti) is the same as the oxide layer 30 in the first embodiment. is there. Therefore, the description which overlaps with 1st Embodiment may be abbreviate
  • FIG. 13 is a schematic cross-sectional view showing the structure of the multilayer capacitor 200 in the present embodiment.
  • the multilayer capacitor 200 of this embodiment partially includes a structure in which a total of five electrode layers and a total of four dielectric layers are alternately stacked. Further, in a portion where the electrode layers and the dielectric layers are not alternately stacked, the lower electrode layer (for example, the first-stage electrode layer 220a) and the upper electrode layer (for example, the fifth-stage electrode layer) Each electrode layer is formed so as to be electrically connected to the electrode layer 220e).
  • each electrode layer 220a, 220b, 220c, 220d, 220e, and the material or composition of each of the oxide layers 230a, 230b, 230c, 230d, which are dielectric layers, are described in the multilayer capacitor of this embodiment described later. It is disclosed in the description of 200 manufacturing methods.
  • FIG. 14 to 18 are schematic cross-sectional views showing one process of the manufacturing method of the multilayer capacitor 200.
  • FIG. 15, FIG. 16, FIG. 17, and FIG. 18 show a part of the structure of the multilayer capacitor 200 shown in FIG. 13 for convenience of explanation.
  • the display of the temperature in this application represents the preset temperature of the heater.
  • Electrode Layer 220a Formation of First Stage Electrode Layer 220a
  • lanthanum (La) is formed on the substrate 10 by screen printing.
  • the electrode layer precursor layer 221a is used as a starting material.
  • pre-baking it heats to 150 to 250 degreeC for about 5 minutes. This pre-baking is performed in an oxygen-containing atmosphere.
  • the pre-baked gel is preferable for sufficiently evaporating the solvent (typically, the main solvent) in the electrode layer precursor layer 221a and exhibiting characteristics that enable future plastic deformation.
  • a state (presumed to be a state in which organic chains remain before thermal decomposition) can be formed.
  • the pre-baking temperature is preferably 80 ° C. or higher and 250 ° C. or lower. As a result, a first electrode layer precursor layer 221a having a layer thickness of about 2 ⁇ m to about 3 ⁇ m is formed.
  • the first-layer electrode layer precursor layer 221a is heated to 580 ° C. in an oxygen atmosphere for about 15 minutes, so that lanthanum ( First-stage electrode layer oxide layer made of La) and nickel (Ni) (however, inevitable impurities may be included. The same applies hereinafter. Also referred to simply as “first-stage electrode layer”) 220a is formed.
  • An electrode oxide layer (including not only the first-stage electrode oxide layer but also other electrode oxide layers) made of lanthanum (La) and nickel (Ni) is also called an LNO layer. .
  • an example of a precursor containing lanthanum (La) for the first-stage electrode layer 220a in the present embodiment is lanthanum acetate.
  • lanthanum nitrate, lanthanum chloride, or various lanthanum alkoxides for example, lanthanum isopropoxide, lanthanum butoxide, lanthanum ethoxide, lanthanum methoxyethoxide
  • Ni nickel
  • nickel nitrate, nickel chloride, or various nickel alkoxides for example, nickel isopropoxide, nickel butoxide, nickel ethoxide, nickel methoxyethoxide
  • the first electrode layer 220a made of lanthanum (La) and nickel (Ni) is employed, but the first electrode layer 220a is not limited to this composition.
  • a first-stage electrode layer made of antimony (Sb) and tin (Sn) can also be employed.
  • the precursor containing antimony (Sb) include antimony acetate, antimony nitrate, antimony chloride, or various antimony alkoxides (for example, antimony isopropoxide, antimony butoxide, antimony ethoxide, antimony methoxyethoxide). Can be employed.
  • Examples of the precursor containing tin (Sn) include tin acetate, tin nitrate, tin chloride, or various tin alkoxides (eg, tin isopropoxide, tin butoxide, tin ethoxide, tin methoxyethoxide).
  • tin alkoxides eg, tin isopropoxide, tin butoxide, tin ethoxide, tin methoxyethoxide.
  • an oxide composed of indium (In) and tin (Sn) can also be employed.
  • examples of the precursor containing indium (In) include indium acetate, indium nitrate, indium chloride, or various indium alkoxides (for example, indium isopropoxide, indium butoxide, indium ethoxide, indium methoxyethoxide). Can be employed.
  • the example of the precursor containing tin (Sn) is the same as the above-mentioned example.
  • the pre-baking allows the solvent (typically, the main solvent) in the precursor layer to evaporate sufficiently, and at the same time favorably develops a gel state (thermal decomposition) to develop characteristics that enable plastic deformation. It is considered that the organic chain remains in the front).
  • the pre-baking temperature is preferably 80 ° C. or higher and 250 ° C. or lower.
  • the precursor layer is formed and pre-fired by the above-described screen printing method.
  • the precursor layer of the oxide layer 230a is heated at 650 ° C. in an oxygen atmosphere for a predetermined time (for example, about 20 minutes), as shown in FIG.
  • a patterned oxide layer (oxide layer 230a) made of bismuth (Bi), niobium (Nb), and titanium (Ti) is formed on the substrate 10 and the first electrode layer 220a.
  • Electrode layers and dielectric layers patterned by a screen printing method are alternately stacked.
  • the second-stage electrode layer patterned by the screen printing method on the oxide layer 230a and the first-stage electrode layer 220a.
  • the precursor layer for forming is formed in the same manner as the first-layer electrode layer precursor layer 221a.
  • a patterned second-stage electrode layer 220b is formed.
  • the second-stage dielectric layer patterned by screen printing on the second-stage electrode layer 220b and the first-stage dielectric layer 230a.
  • a body layer 230b is formed.
  • the multilayer capacitor 200 of the present embodiment has each electrode layer and each dielectric layer (oxide layer) formed of a metal oxide.
  • each electrode layer and each dielectric layer (oxide layer) are formed by heating various precursor solutions in an oxygen-containing atmosphere, compared with the conventional method. Therefore, the area can be easily increased, and the industrial property or mass productivity can be remarkably improved.
  • ⁇ Third Embodiment> 1 Overall Configuration of Thin Film Capacitor of this Embodiment
  • embossing is performed in the formation process of all layers of a thin film capacitor that is an example of a solid-state electronic device.
  • the overall configuration of a thin film capacitor 300 which is an example of a solid-state electronic device in the present embodiment, is shown in FIG.
  • the lower electrode layer, the oxide layer, and the upper electrode layer are the same as those in the first embodiment except that the embossing process is performed. Therefore, the description which overlaps with 1st Embodiment is abbreviate
  • the thin film capacitor 300 of the present embodiment is formed on the substrate 10 as in the first embodiment.
  • the thin film capacitor 300 includes a lower electrode layer 320 from the substrate 10 side, an oxide layer 330 made of an oxide of bismuth (Bi), niobium (Nb), and titanium (Ti), and an upper electrode layer 340. Is provided.
  • FIG. 20 to 29 are cross-sectional schematic views showing one process of the method of manufacturing the thin film capacitor 300.
  • the lower electrode layer 320 that has been embossed is formed on the substrate 10.
  • an oxide layer 330 that has been embossed is formed on the lower electrode layer 320.
  • an upper electrode layer 340 that is embossed on the oxide layer 330 is formed. Also in the manufacturing process of the thin film capacitor 300, the description overlapping with the first embodiment is omitted.
  • the lower electrode layer 320 of the thin film capacitor 300 is formed of a conductive oxide layer made of lanthanum (La) and nickel (Ni) will be described.
  • the lower electrode layer 320 is formed in the order of (A) formation of a precursor layer and preliminary baking, (B) stamping process, and (C) main baking process.
  • A Precursor layer formation and pre-baking step First, a lower part having a lanthanum (La) -containing precursor and nickel (Ni) -containing precursor as solutes on the substrate 10 by a known spin coating method.
  • a lower electrode layer precursor layer 320a is formed using the electrode layer precursor solution as a starting material.
  • the precursor layer 320a for the lower electrode layer is heated in a temperature range of 80 ° C. or higher and 250 ° C. or lower for a predetermined time in an oxygen-containing atmosphere.
  • the desired thickness of the lower electrode layer 320 can be obtained by repeating the formation and preliminary baking of the lower electrode layer precursor layer 320a by the spin coating method described above a plurality of times.
  • embossing is performed at a pressure of 0.1 MPa to 20 MPa.
  • the heating method in the embossing process include a method of bringing the substrate into a predetermined temperature atmosphere by using a chamber, an oven, or the like, a method of heating the base on which the substrate is placed from below, or a temperature of 80 ° C. or higher and 300 ° C. in advance.
  • the following is a method of embossing using a heated mold. In this case, it is more preferable in terms of workability to use in combination the method of heating the base with a heater from the bottom and the method of using a mold heated in advance to 80 ° C. or more and 300 ° C. or less.
  • the reason why the heating temperature of the mold is set to 80 ° C. or more and 300 ° C. or less is as follows.
  • the heating temperature during the embossing process is lower than 80 ° C.
  • the plastic deformation ability of the lower electrode layer precursor layer 320a is reduced due to the lower temperature of the lower electrode layer precursor layer 320a. Therefore, the feasibility of molding at the time of molding the embossed structure, or the reliability or stability after molding becomes poor.
  • the heating temperature during the stamping process exceeds 300 ° C., the decomposition (oxidative thermal decomposition) of the organic chain, which is the source of the plastic deformability, proceeds, so that the plastic deformability decreases.
  • the precursor layer 320a for the lower electrode layer is heated within a range of 100 ° C. or more and 250 ° C. or less during the embossing process.
  • the pressure in the die pressing process is a pressure in the range of 0.1 MPa to 20 MPa
  • the lower electrode layer precursor layer 320a is deformed following the surface shape of the die, and a desired die
  • the push structure can be formed with high accuracy.
  • the pressure applied when embossing is performed is set to a low pressure range of 0.1 MPa to 20 MPa (particularly less than 1 MPa). As a result, it is difficult for the mold to be damaged when the stamping process is performed, and it is advantageous for increasing the area.
  • the entire lower electrode layer precursor layer 320a is etched. As a result, as shown in FIG. 21, the lower electrode layer precursor layer 320a is completely removed from the region other than the region corresponding to the lower electrode layer (etching process for the entire surface of the lower electrode layer precursor layer 320a).
  • a mold release treatment for the surface of each precursor layer that will be brought into contact with the stamping surface and / or a mold release treatment for the die pressing surface of the mold is performed. It is preferable that an embossing process is performed on each precursor layer. By applying such treatment, the frictional force between each precursor layer and the mold can be reduced, so that each precursor layer can be embossed with higher accuracy. It becomes.
  • the release agent that can be used for the release treatment include surfactants (for example, fluorine surfactants, silicon surfactants, nonionic surfactants, etc.), fluorine-containing diamond-like carbon, and the like. can do.
  • the heating temperature during the main baking is not less than 550 ° C. and not more than 650 ° C.
  • a lower electrode layer 320 (however, inevitable impurities may be included. The same applies hereinafter) made of lanthanum (La) and nickel (Ni) is formed on the substrate 10.
  • FIG. 2 (2) Formation of Oxide Layer that Becomes Dielectric Layer
  • an oxide layer 330 that becomes a dielectric layer is formed on the lower electrode layer 320.
  • the oxide layer 330 is formed in the order of (A) precursor layer formation and preliminary firing step, (B) embossing step, and (C) main firing step.
  • 23 to 26 are views showing a process of forming the oxide layer 330.
  • Layer 330a is formed.
  • preliminary firing is performed in an oxygen-containing atmosphere while being heated to 80 ° C. or higher and 250 ° C. or lower.
  • the solvent typically, the main solvent
  • embossing process is performed with respect to the precursor layer 330a which performed only preliminary baking. Specifically, in order to perform patterning of the oxide layer, embossing is performed at a pressure of 0.1 MPa or more and 20 MPa or less using the dielectric layer mold M2 while being heated to 80 ° C. or more and 250 ° C. or less. Is done.
  • the entire surface of the precursor layer 330a is etched.
  • the precursor layer 330a is completely removed from the region other than the region corresponding to the oxide layer 330 (etching process for the entire surface of the precursor layer 330a).
  • the etching process of the precursor layer 330a of this embodiment was performed using the wet etching technique which does not use a vacuum process, it does not prevent etching using what is called dry etching technique using plasma. .
  • the etching process for the entire surface of the precursor layer 330a can be performed after the main baking, as described above, the precursor layer is entirely etched between the embossing process and the main baking process. It is a more preferable aspect that the process is included. This is because the precursor layers in unnecessary regions can be removed more easily than etching after each precursor layer is subjected to main firing.
  • a precursor containing lanthanum (La) and a precursor containing nickel (Ni) are formed on the oxide layer 330 in the same manner as the lower electrode layer 320 by a known spin coating method.
  • a precursor layer 340a for the upper electrode layer is formed using a precursor solution as a solute as a starting material.
  • preliminary firing is performed by heating the precursor layer 340a for the upper electrode layer in an oxygen-containing atmosphere in a temperature range of 80 ° C. to 250 ° C.
  • the precursor layer 340a for the upper electrode layer is heated to 80 ° C. or more and 300 ° C. or less.
  • the upper electrode layer precursor layer 340a is embossed at a pressure of 0.1 MPa to 20 MPa. Thereafter, by etching the entire upper electrode layer precursor layer 340a, the upper electrode layer precursor layer 340a is completely removed from regions other than the region corresponding to the upper electrode layer 340, as shown in FIG.
  • the upper electrode layer precursor layer 340a is heated to 520 ° C. to 600 ° C. for a predetermined time in an oxygen atmosphere, thereby being formed on the oxide layer 330.
  • the thin film capacitor 300 of this embodiment includes a lower electrode layer 320, an oxide layer 330 that is an insulating layer, and an upper electrode layer 340 on the substrate 10 from the substrate 10 side.
  • each layer described above is embossed by embossing.
  • a process using a relatively long time and / or expensive equipment such as a vacuum process, a process using a photolithography method, or an ultraviolet irradiation process becomes unnecessary.
  • both the electrode layer and the oxide layer can be easily patterned. Therefore, the thin film capacitor 300 of this embodiment is extremely excellent in industrial property or mass productivity.
  • a lower electrode layer precursor layer 320a that is a precursor layer of the lower electrode layer 320
  • a precursor layer 330a that is a precursor layer of the oxide layer 330
  • main firing is performed. If such a method is employed, in this embodiment, unlike the thin film capacitor 300, it is not possible to form individual stamping structures for each layer alone, but it is possible to reduce the number of stamping processes. Become.
  • the oxide layer in each of the above embodiments is suitable for various solid-state electronic devices that control a large current with a low driving voltage.
  • the solid-state electronic device provided with the oxide layer in each of the above-described embodiments can be applied to many devices other than the above-described thin film capacitor.
  • various capacitors such as variable capacitance thin film capacitors, semiconductor devices such as metal oxide semiconductor junction field effect transistors (MOSFETs) and nonvolatile memories, or MEMS such as micro TAS (Total Analysis System), micro chemical chips, DNA chips, etc.
  • Microelectromechanical system or a device of a microelectromechanical system represented by NEMS (nanoelectromechanical system), or a composite device including at least two of a high frequency filter, a patch antenna, or an RCL, and the oxide in each of the above embodiments Layers can also be applied.
  • FIG. 30 is a diagram illustrating an entire configuration of the thin film transistor 400.
  • a lower electrode layer (gate electrode) 320, an oxide layer (gate insulating layer) 330, a channel 444, a source electrode 458, The drain electrodes 456 are stacked in this order. Since the manufacturing method of the lower electrode layer (gate electrode) 320 and the oxide layer (gate insulating layer) 330 is the same as those manufacturing method of the third embodiment, the description thereof is omitted.
  • the thin film transistor 400 employs a so-called bottom gate structure, but the present embodiment is not limited to this structure. Further, as in the first embodiment, in order to simplify the drawing, description of patterning of the extraction electrode from each electrode is omitted.
  • the channel 444 of this embodiment is made of a channel oxide containing indium (In), zinc (Zn), and zirconium (Zr). In the present embodiment, other known channel materials can also be used.
  • a thin film transistor in which the thickness of the channel 444 is greater than or equal to 5 nm and less than or equal to 80 nm, and the thickness of the channel 444 is greater than or equal to 5 nm and less than or equal to 80 nm is highly accurate and covers the oxide layer (gate insulating layer). This is a preferred embodiment from the viewpoint of facilitating modulation.
  • source electrode 458 and the drain electrode 456 of the present embodiment are made of ITO (Indium Tin Oxide).
  • an oxide made of bismuth (Bi), niobium (Nb), and titanium (Ti) is used as an insulating layer that plays a role other than the oxide layer (gate insulating layer) 330. Can also be used.
  • the pressure at the time of the die-pressing process was set in the range of “0.1 MPa or more and 20 MPa or less” for the following reason.
  • the pressure is less than 1 MPa, the pressure may be too low to emboss each precursor layer.
  • the pressure is 20 MPa, the precursor layer can be sufficiently embossed, so that it is not necessary to apply more pressure.
  • the embossing process is performed at a pressure within a range of 0.1 MPa to 10 MPa in the embossing step.
  • Electrode layer 221a Precursor layer for electrode layer 320a Precursor layer for lower electrode layer 30, 230a, 330 Oxide layer (oxide dielectric layer) 30a, 330a Precursor layer 340a Upper electrode layer precursor layer 40, 340 Upper electrode layer 100, 300 Thin film capacitor which is an example of a solid state electronic device 200 Multilayer capacitor which is an example of a solid state electronic device 400 An example of a solid state electronic device Thin film transistor 444 Channel 456 Drain electrode 458 Source electrode M1 Lower electrode layer type M2 Dielectric layer type M3 Upper electrode layer type

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