Dielectrics, capacitive elements, and methods for manufacturing dielectrics

Abstract

To provide a dielectric suitable for manufacturing a capacitative element having high relative permittivity and resistivity and high capacity, and a manufacturing method thereof.SOLUTION: A dielectric includes a dielectric composition and a conductor filler, the conductor filler is dispersed in the dielectric composition, the dielectric composition contains SiO(N)-based amorphous, and the conductor filler contains MN metal particles, M is one or more selected from Ti, Nb, and Cr.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a dielectric, a capacitor element, and a method for manufacturing a dielectric.

Background Art

[0002] Patent Document 1 describes an invention related to a method for manufacturing a ceramic capacitor in which fine metal particles are dispersed in a dielectric layer. Examples of dispersing titanium particles having a particle size of 45 μm or less in the dielectric layer and examples of dispersing nickel particles having a particle size of 2 to 3 μm in the dielectric layer are described.

[0003] Patent Document 2 describes an invention related to an electronic component including a dielectric. Examples of dispersing various metal powders (for example, Pd metal powder, etc.) having a particle size of 1 μm in the dielectric and examples of dispersing permalloy powder having an average particle size of 0.3 μm are described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a dielectric suitable for manufacturing a high-capacity capacitor element having a high relative permittivity and resistivity, and a method for manufacturing the same.

Means for Solving the Problems

[0006] The dielectric according to the first aspect of the present invention has a dielectric composition and a conductor filler, the conductor filler is dispersed in the dielectric composition, The dielectric composition comprises an SiO(N)-based amorphous material. The conductive filler contains MN metal particles, M is one or more elements selected from Ti, Nb, and Cr.

[0007] The Si content in the dielectric may be 40% or more in atomic ratio relative to the total content of Si and M.

[0008] The average particle size of the MN metal particles may be 10 nm or less.

[0009] A dielectric according to a second aspect of the present invention comprises a dielectric composition and a conductive filler, The conductive filler is dispersed in the dielectric composition, The dielectric composition comprises an SiO-based amorphous material. The aforementioned conductive filler contains M' metal particles, M' is one or more elements selected from Fe, Co, Ni, and Cu.

[0010] The Si content in the dielectric may be 40% or more in atomic ratio relative to the total content of Si and M'.

[0011] The average particle size of the M' metal particles may be 10 nm or less.

[0012] The capacitive element according to the present invention comprises a dielectric according to a first aspect of the present invention or a dielectric according to a second aspect of the present invention, and a pair of electrodes.

[0013] A first method for manufacturing a dielectric according to a first aspect of the present invention comprises the steps of forming a (Si,M)(O,N) amorphous material, The process includes a step of incorporating the SiO(N) amorphous material and the MN metal particles into the dielectric material by performing an annealing treatment on the (Si,M)(O,N) amorphous material, The annealing temperature in the aforementioned annealing process is 700°C or higher and 800°C or lower.

[0014] The annealing treatment may be performed in an NH3 atmosphere.

[0015] The second manufacturing method of the dielectric according to the first aspect of the present invention includes a step of forming an (Si, M)(O, N)-based amorphous material in which the content of M is 45% or more in atomic ratio with respect to the total content of Si and M.

[0016] The first manufacturing method of the dielectric according to the second aspect of the present invention includes a step of forming an (Si, M')O-based amorphous material, and a step of including the SiO-based amorphous material and the M' metal particles in the dielectric by performing an annealing treatment on the (Si, M')O-based amorphous material, where the annealing temperature in the annealing treatment is 700°C or higher and 800°C or lower.

[0017] The second manufacturing method of the dielectric according to the second aspect of the present invention includes a step of forming an (Si, M')O-based amorphous material in which the content of M' is 45% or more in atomic ratio with respect to the total content of Si and M'.

Brief Description of the Drawings

[0018] [Figure 1] It is a schematic diagram of a thin film capacitor according to an embodiment of the present invention.

Mode for Carrying Out the Invention

[0019] (First Embodiment) Hereinafter, the first embodiment of the present invention will be described with reference to the drawings.

[0020] Figure 1 shows a schematic diagram of a thin-film capacitor, which is a type of capacitive element including a dielectric and a pair of electrodes according to this embodiment. The thin-film capacitor 1 shown in Figure 1 is formed on a substrate 11 in the order of a lower electrode 12 and a thin film 13 made of a dielectric, and an upper electrode 14 is provided on the surface of the thin film 13 made of the dielectric. In the following description, the thin film made of a dielectric may be simply referred to as a dielectric thin film.

[0021] In this embodiment, a thin film refers to a thin film formed when the raw material compounds used in the manufacturing process are separated or excited at the atomic or molecular level and then re-formed. Therefore, compounds formed by coating with slurries, etc., are not included in the definition of a thin film in this embodiment.

[0022] There are no particular restrictions on the substrate 11. For example, a Si single crystal substrate can be used. Also, the lower electrode 12, which will be described later, may also serve as the substrate 11. When the lower electrode 12 also serves as the substrate 11, for example, a Ta foil can be used.

[0023] There are no particular restrictions on the material of the lower electrode 12 and the upper electrode 14; any material that functions as an electrode is acceptable. Examples include Ta, Pt, Ag, Ni, etc. The thickness of the lower electrode 12 is preferably 0.01 to 10 μm. The thickness of the upper electrode 14 is preferably 0.01 to 10 μm.

[0024] The dielectric of this embodiment contained in the dielectric thin film 13 has a dielectric composition and a conductive filler. The conductive filler is dispersed in the dielectric composition, The dielectric composition comprises an SiO(N)-based amorphous material. The conductive filler contains MN metal particles, The dielectric is one or more elements selected from Ti, Nb, and Cr. Alternatively, M may be replaced with Ti.

[0025] Because the dielectric contained in the dielectric thin film 13 has the above configuration, even if the dielectric thin film 13 is thin, specifically less than 100 nm thick, it will have a high relative permittivity and high resistivity. A thin-film capacitor 1 containing such a dielectric thin film 13 will be a high-capacitance thin-film capacitor 1. There is no particular lower limit to the thickness of the dielectric thin film 13; for example, it can be 5 nm or more.

[0026] The SiO(N)-based amorphous material contained in the dielectric composition contains at least Si, O, and N, where Si is SiO2 or SiO x N y This refers to amorphous material that is included as such. In SiO(N) amorphous material, the total content of Si, O, and N is considered to be 100 at%, and the Si content in SiO(N) amorphous material may be 30 at% or more and 40 at% or less.

[0027] The dielectric composition may contain elements other than SiO(N) amorphous materials, such as unavoidable impurities, including M, which exists in a state other than MN metal particles. The content of elements other than Si, O, and N in the dielectric composition may be 20 mass% or less.

[0028] A conductive filler is dispersed in the dielectric composition. The conductive filler contains MN metal particles. There are no particular restrictions on the particle size of the MN metal particles, but it may be 10 nm or less on average, or 3 nm or less. The small particle size of the MN metal particles makes it easier for the dielectric thin film 13 to have a high dielectric constant and high resistivity.

[0029] The content of elements other than M and N in the conductive filler may be 10 mass% or less.

[0030] Furthermore, the Si content in the dielectric may be 30% or more in atomic ratio relative to the total Si and M content. It is preferable that it be 40% or more. The insulating properties of the dielectric are ensured by the SiO(N)-based amorphous material included in the dielectric composition. To sufficiently increase the resistivity of the dielectric, it is preferable that the SiO(N)-based amorphous material content be relatively high. There is no particular upper limit to the Si content, however, for example, the Si content may be 80% or less in atomic ratio relative to the total Si and M content.

[0031] The following describes the method for analyzing the composition of the dielectric material contained in the dielectric thin film 13.

[0032] There are no particular restrictions on the method for analyzing the composition of dielectrics. Examples include X-ray fluorescence analysis (XRF) and X-ray photoelectron spectroscopy (XPS).

[0033] XRF and XPS are both well-known methods for analyzing the composition of dielectric materials and can be used, for example, for dielectric thin films. XRF is primarily used for analyzing the composition of dielectric materials. XPS is also preferably used when evaluating the uniformity of the dielectric composition in the thickness direction. When evaluating the uniformity of the dielectric composition in the thickness direction using XPS, the dielectric composition is analyzed while performing Ar etching on the dielectric material.

[0034] Both XRF and XPS can calculate composition using the internal standards of the measuring instrument. For high-precision analysis, a sample with a known composition is prepared as a reference sample, a calibration curve is created using the reference sample, and the composition is calculated using the created calibration curve.

[0035] The following describes how to determine the presence or absence of MN metal particles.

[0036] Whether or not a dielectric material contains MN metal particles can be confirmed using a transmission electron microscope (TEM). The particle size of the MN metal particles can also be determined using TEM.

[0037] A simpler method for confirming the presence or absence of MN metal particles than using a TEM is to evaluate the diffraction pattern using an X-ray diffractometer (XRD). The following explanation describes the case where M is Ti, but the method is the same when M is Nb or Cr, except that the diffraction pattern differs.

[0038] For example, when obtaining a diffraction pattern in the range of 2θ < 70° using XRD with a CuKα source, peaks representing TiN metal particles appear at diffraction angles 2θ = 37°, 43°, and 62°. However, the above diffraction angle 2θ may change if the dielectric contains TiN metal particles with partial N defects and / or Ti metal particles with partial Ti defects.

[0039] Because the particle size of TiN metal particles is small, on the order of a few nanometers, the peaks representing TiN metal particles do not appear clearly. The peaks representing TiN metal particles appear as slight bulges. Furthermore, when TiN metal particles are present in the dielectric, slight bulges appear simultaneously at the three diffraction angles mentioned above. Therefore, even if the peaks representing TiN metal particles do not appear clearly, it is possible to sufficiently determine whether or not the dielectric contains TiN metal particles. Another method for confirming the presence or absence of TiN metal particles, besides using XRD, is to use Raman spectroscopy.

[0040] Furthermore, when the dielectric material contains TiN metal particles, the absorption edge shifts slightly to lower wavelengths compared to the case where the dielectric material composition is the same but does not contain TiN metal particles.

[0041] The following describes the manufacturing method for thin-film capacitors, a type of capacitive element shown in Figure 1. The manufacturing method for dielectrics will be explained in the section on thin-film capacitor manufacturing methods.

[0042] First, prepare the substrate. There are no particular restrictions on the material of the substrate. For example, a Si single crystal substrate can be used. Alternatively, a metal foil, such as Ta foil, can also be used as the substrate. When using a metal foil as the substrate, the substrate may also serve as the electrode.

[0043] Next, electrodes are formed on the substrate. There are no particular restrictions on the material of the electrodes; they just need to function as electrodes. Examples include Ta, Pt, Ag, Ni, etc. There are no particular restrictions on the thickness of the electrodes. When forming electrodes on a substrate, the thickness may be 0.01 to 10 μm. There are no particular restrictions on the method of forming the electrodes. Examples include sputtering and vapor deposition.

[0044] Next, a dielectric thin film is formed on the electrode. In this process, a dielectric thin film made of (Si,M)(O,N) amorphous material is deposited.

[0045] (Si,M)(O,N) amorphous material is an amorphous material containing Si, M, O, and N. The ratio of Si to M is controlled to ultimately obtain the desired dielectric material.

[0046] First, a target for depositing the dielectric thin film described above is fabricated. Specifically, a composite target made of M and Si is fabricated.

[0047] There are no particular restrictions on the method for fabricating the composite target. For example, it can be fabricated by arranging Si chips on a film deposition target made of M (hereinafter referred to as the M target). There are no particular restrictions on the shape of the individual Si chips. For example, they may be rectangular prisms with the two largest faces being squares of 3 mm to 10 mm on each side and a thickness of about 0.5 mm. When fabricating a composite target using this method, the ratio of Si to M in the film deposition target can be easily changed by changing the number of Si chips, and the ratio of Si to M in the resulting dielectric thin film can be easily controlled.

[0048] Next, a dielectric thin film consisting of (Si,M)(O,N) amorphous material is deposited by RF sputtering using a composite target as the target for film deposition.

[0049] There are no particular limitations on the conditions for RF sputtering. By appropriately controlling the type of sputtering gas, the pressure of the sputtering gas, the magnitude of the high-frequency power, and the sputtering time, a dielectric thin film consisting of the desired (Si,M)(O,N) amorphous material is deposited.

[0050] The following sections will explain separately the cases in which annealing at temperatures above 700°C is required and the cases in which annealing at temperatures above 700°C is not required.

[0051] (When annealing at temperatures above 700°C) The resulting dielectric thin film, consisting of (Si,M)(O,N) amorphous material, is subjected to annealing. By performing annealing, the M contained in the (Si,M)(O,N) amorphous material is bonded with N to generate MN metal particles, which can then be dispersed and deposited within the dielectric. This results in a dielectric thin film containing SiO(N) amorphous material as the dielectric composition and MN metal particles as conductive fillers. Furthermore, the dielectric thin film has conductive fillers dispersed within the dielectric composition. Note that the state in which conductive fillers are dispersed within the dielectric composition refers to a state in which individual conductive filler particles are not continuous but isolated within the dielectric composition.

[0052] The atmosphere used during annealing is not particularly restricted as long as it has a very low O2 content. Examples include an N2 atmosphere, an Ar atmosphere, an NH3 atmosphere, or a vacuum. When annealing is performed in an NH3 atmosphere, nitrogen is supplied from the atmosphere, making it easier to generate MN metal particles and deposit them inside the dielectric. The following describes the case of annealing in an NH3 atmosphere.

[0053] There are no particular restrictions on the flow rate of NH3 gas during the annealing process. For example, it may be between 30 mL / min and 100 mL / min. There are no particular restrictions on the annealing temperature other than that it must be 700°C or higher. For example, it may be between 700°C and 900°C, or between 700°C and 800°C. If the annealing temperature is too low, the MN metal particles will not grow well. There are no particular restrictions on the annealing time. For example, it may be between 0.5 hours and 10 hours.

[0054] Higher annealing temperatures tend to yield more uniform dielectric thin films. However, when using dielectrics as capacitive elements, sufficiently uniform dielectric thin films can be obtained at annealing temperatures of 900°C or lower, or even 800°C or lower. Dielectric thin films annealed at excessively high temperatures are expensive to manufacture, but their relative permittivity and resistivity do not increase. Furthermore, using dielectric thin films annealed at excessively high temperatures as capacitive elements does not increase capacitance. Moreover, dielectric thin films tend to have worse dielectric properties, specifically electrical resistance, as the annealing temperature increases.

[0055] Furthermore, if the annealing temperature is too high, the electrodes may detach from the substrate. This is especially true when forming electrodes on a Si single crystal substrate. For example, when forming electrodes made of Pt on a Si single crystal substrate, the electrodes may detach from the substrate if the annealing temperature exceeds 800°C.

[0056] When metal foil is used as both a substrate and an electrode, the above-mentioned delamination does not occur. However, warping may occur if the annealing temperature is too high.

[0057] (When annealing at temperatures above 700°C is not required) In a dielectric thin film made of the above-mentioned (Si,M)(O,N) amorphous material, if the M content is 45% or more in atomic ratio relative to the total Si and M content, MN metal particles may be generated and dispersed and deposited within the dielectric even without annealing at 700°C or higher. Specifically, during and / or after the generation of the (Si,M)(O,N) amorphous material, M and N contained in the (Si,M)(O,N) amorphous material may combine to generate MN metal particles, which may be dispersed and deposited within the dielectric. This results in a dielectric thin film containing SiO(N) amorphous material as the dielectric composition and MN metal particles as a conductive filler. Furthermore, the conductive filler is dispersed within the dielectric composition.

[0058] The following steps are common to both cases where annealing at 700°C or higher is performed and cases where annealing at 700°C or higher is not required.

[0059] Next, dielectric thin film electrodes (upper electrodes) are formed as needed to fabricate a thin-film capacitor. There are no particular restrictions on the material or formation method of the electrodes.

[0060] The dielectric thin film contained in the thin-film capacitor fabricated by the above method has high relative permittivity and resistivity. Furthermore, thin-film capacitors with a dielectric thin film thickness of 100 nm or less fabricated by the above method have higher capacitance compared to conventional thin-film capacitors with a dielectric thin film thickness of 100 nm or less.

[0061] It is known that materials with a high dielectric constant, such as BaTiO3, are used to fabricate dielectrics with a high dielectric constant. However, when BaTiO3 is used as the dielectric, the dielectric constant decreases as the thickness of the dielectric decreases.

[0062] Materials that can obtain a relatively high relative permittivity even with a small dielectric thickness include materials used for diode gate films, such as SiO2. However, when SiO2 is used as the dielectric, the relative permittivity is less than 10, and a sufficiently high relative permittivity cannot be obtained.

[0063] It is known that dielectrics with conductive fillers dispersed in the dielectric composition exhibit improved dielectric constant compared to dielectrics without conductive fillers. Furthermore, it is known that capacitive elements fabricated using dielectrics with dispersed conductive fillers can be fabricated with higher capacitance compared to those fabricated using dielectrics without conductive fillers. On the other hand, it is known that the higher the packing density of conductive fillers, the lower the resistivity and the lower the insulation properties. Moreover, conventionally, the size of the metal particles contained in the conductive fillers is several micrometers or larger, which is about the same particle size as the dielectric particles in the dielectric composition, and this can cause leakage that reduces dielectric constant, resistivity, and insulation properties.

[0064] Conventionally, a method for dispersing conductive fillers in a dielectric composition is to knead the conductive fillers into the dielectric composition. Then, the dielectric material is produced by firing the kneaded dielectric composition.

[0065] Here, by setting the size of the metal particles contained in the conductive filler to a few nanometers, percolation of the conductive filler can be suppressed without reducing the packing density of the conductive filler, thereby maintaining resistivity and insulation properties.

[0066] However, if the size of the metal particles is several nanometers, attempting to disperse the conductive filler in the dielectric composition using the above method will result in grain growth of the metal particles during firing. Alternatively, the metal particles may easily diffuse and disappear during firing. If firing is not performed, the dielectric will not have sufficiently high properties.

[0067] The dielectric material according to this embodiment has high relative permittivity and resistivity, especially when the dielectric thickness is small, making it suitable for fabricating high-capacitance capacitive elements.

[0068] In this embodiment, the case where the capacitive element is a thin-film capacitor has been described, but the capacitive element does not have to be a thin-film capacitor. That is, the dielectric does not have to be a dielectric thin film. For example, a dielectric made of (Si,M)(O,N) amorphous material may be fabricated by coating a slurry onto an electrode and removing the binder. The manufacturing method after fabricating the dielectric made of (Si,M)(O,N) amorphous material is the same as the manufacturing method when the dielectric is a dielectric thin film.

[0069] (Second Embodiment) A second embodiment of the present invention will be described below. Unless otherwise specified, the second embodiment is the same as that of the first embodiment.

[0070] The dielectric of this embodiment contained in the dielectric thin film 13 has a dielectric composition and a conductive filler. The conductive filler is dispersed in the dielectric composition, The dielectric composition comprises an SiO-based amorphous material. The aforementioned conductive filler contains M' metal particles, M' is a dielectric material where one or more elements are selected from Fe, Co, Ni, and Cu.

[0071] The SiO-based amorphous material included in the dielectric composition is an amorphous material containing at least Si and O. The SiO-based amorphous material may also contain N. Furthermore, the Si in the SiO-based amorphous material may be SiO2 or SiO2. x N y It is included as follows. The total content of Si, O, and N in the SiO-based amorphous material is 100 at%, and the Si content in the SiO-based amorphous material may be 30 at% or more and 40 at% or less.

[0072] The dielectric composition may contain elements other than SiO-based amorphous materials, such as unavoidable impurities, including M' that exist in a state other than metal particles. The content of elements other than Si, O, and N in the dielectric composition may be 20 mass% or less.

[0073] A conductive filler is dispersed in the dielectric composition. The conductive filler contains M' metal particles. There are no particular restrictions on the particle size of the M' metal particles, but it may be 10 nm or less on average, or 3 nm or less. The smaller the particle size of the M' metal particles, the more likely the dielectric thin film 13 is to have a high relative permittivity and high resistivity.

[0074] The content of elements other than M' in the conductive filler may be 10 mass% or less.

[0075] Furthermore, the Si content in the dielectric may be 30% or more in atomic ratio relative to the total Si and M' content. It is preferable that it be 40% or more. In other words, it is preferable that the content of SiO-based amorphous material in the dielectric is relatively high. The insulating properties of the dielectric are ensured by the SiO-based amorphous material included in the dielectric composition. To sufficiently increase the resistivity of the dielectric, it is preferable that the content of SiO-based amorphous material is relatively high. There is no particular upper limit on the Si content, however, for example, the Si content may be 80% or less in atomic ratio relative to the total Si and M' content.

[0076] The method for determining the presence or absence of M' metal particles is the same as the method for determining the presence or absence of TiN metal particles, except that the diffraction pattern is different.

[0077] The following describes the formation of the dielectric thin film and the annealing process in the second embodiment. Unless otherwise specified, the process is the same as in the first embodiment.

[0078] A dielectric thin film is formed on the electrode. In this process, a dielectric thin film made of (Si,M')O-based amorphous material is deposited.

[0079] (Si,M')O amorphous material is an amorphous material containing at least Si, M', and O. (Si,M')O amorphous material may also contain N. The ratio of Si to M' is controlled to ultimately obtain the desired dielectric material.

[0080] First, a target for depositing the dielectric thin film described above is fabricated. Specifically, a composite target made of M' and Si is fabricated.

[0081] There are no particular restrictions on the method of fabricating the composite target. For example, it can be fabricated by arranging Si chips on a film deposition target made of M'. There are no particular restrictions on the shape of the individual Si chips. For example, they may be rectangular prisms with the two largest faces being squares of 3 mm to 10 mm on each side and a thickness of about 0.5 mm. When fabricating a composite target using this method, the ratio of Si to M' in the film deposition target can be easily changed by changing the number of Si chips, and the ratio of Si to M' in the resulting dielectric thin film can be easily controlled.

[0082] Next, a dielectric thin film made of (Si,M')O amorphous material is deposited by RF sputtering using a composite target as the target for film deposition.

[0083] There are no particular limitations on the conditions for RF sputtering. By appropriately controlling the type of sputtering gas, the pressure of the sputtering gas, the magnitude of the high-frequency power, and the sputtering time, a dielectric thin film made of the desired (Si,M')O amorphous material is deposited.

[0084] The following sections will explain separately the cases in which annealing at temperatures above 700°C is required and the cases in which annealing at temperatures above 700°C is not required.

[0085] (When annealing at temperatures above 700°C) The resulting dielectric thin film made of (Si,M')O amorphous material is subjected to annealing. By performing annealing, the M' contained in the (Si,M')O amorphous material can be dispersed and deposited within the dielectric in the form of M' metal particles. This results in a dielectric thin film containing SiO amorphous material as the dielectric composition and M' metal particles as conductive fillers. Furthermore, the conductive fillers are dispersed within the dielectric composition.

[0086] The atmosphere during the annealing process is not particularly limited as long as it has a very low O2 content. Examples include an N2 atmosphere, an Ar atmosphere, an NH3 atmosphere, or a vacuum. Unlike the first embodiment, an NH3 atmosphere is not particularly preferred because N does not participate in the formation of M' metal particles.

[0087] (When annealing at temperatures above 700°C is not required) If the M' content in the dielectric thin film made of the above-mentioned (Si,M')O amorphous material is 45% or more in atomic ratio relative to the total content of Si and M', then M' metal particles may be dispersed and deposited inside the dielectric even without annealing at 700°C or higher. Specifically, during and / or after the formation of the (Si,M')O amorphous material, the M' contained in the (Si,M')O amorphous material may be dispersed and deposited inside the dielectric in the form of M' metal particles. This results in a dielectric thin film containing SiO amorphous material as the dielectric composition and M' metal particles as a conductive filler. Furthermore, the conductive filler is dispersed within the dielectric composition. [Examples]

[0088] The present invention will be described below based on more detailed examples, but the present invention is not limited to these examples.

[0089] (Examples 1-3) A thoroughly cleaned and dried Ta foil was prepared. The Ta foil serves as both the substrate and the lower electrode. The thickness of the Ta foil was set to 50 μm.

[0090] Next, a dielectric thin film made of (Si,Ti)(O,N) amorphous material was deposited on the Ta foil.

[0091] A composite target made of Ti and Si was fabricated as a film deposition target for depositing dielectric compositions consisting of (Si,Ti)(O,N) amorphous materials.

[0092] The following describes the method for creating composite targets.

[0093] First, a Ti target was prepared. Next, Si chips were arranged on the Ti target. Each Si chip had a rectangular prism shape with the two largest faces being 5mm square and a thickness of approximately 0.5mm. The Ti target with the Si chips arranged on it is a composite target.

[0094] By controlling the Si content relative to the total Si and Ti content in the composite target, the Si content relative to the total Si and Ti content in the dielectric thin film can be controlled. If the Si content relative to the total Si and Ti content in the composite target is 60% in terms of atomic ratio, the Si content relative to the total Si and Ti content in the dielectric thin film will be approximately 75-85% in terms of atomic ratio.

[0095] The dielectric thin film was deposited using RF sputtering with a composite target as the deposition target.

[0096] During film deposition, N2 gas was supplied as the sputtering gas into the chamber, and the sputtering gas pressure was set to 2 Pa. Then, 100 W of high-frequency power was applied to the composite target. The film deposition time was 2 hours. The substrate temperature during film deposition was room temperature. The thickness of the obtained dielectric thin film was 0.45 μm.

[0097] The composition of the obtained dielectric thin films was analyzed by XRF, and it was confirmed that the Si content relative to the total Si and Ti content was 67 at% in Example 1, 40 at% in Example 2, and 30 at% in Example 3.

[0098] Next, the obtained dielectric thin film was subjected to an annealing treatment to deposit TiN metal particles onto the dielectric thin film, thereby fabricating a dielectric thin film containing SiO(N)-based amorphous material and TiN metal particles.

[0099] The annealing process was carried out at 700°C for 5 hours while supplying NH3 gas at a rate of 50 mL / min.

[0100] The presence of TiN metal particles in the obtained dielectric thin film and the dispersion of TiN metal particles within the dielectric thin film were confirmed by TEM. Table 1 shows the Si content in the dielectric thin film relative to the total Si and Ti content in the dielectric thin film.

[0101] Next, an upper electrode made of Ag was formed on a dielectric thin film. The thickness of the upper electrode was 0.2 μm. The upper electrode was formed by vapor deposition. Then, the relative permittivity ε and resistivity ρ were measured at a frequency of 1 kHz using an LCR meter (Agilent E4980A). An ε of 500 or higher was considered good, and an ε of 1000 or higher was considered even better. ρ was 1 × 10⁻⁶ 4 A value of Ωcm or more is considered good, and 1 × 10 6 If the value is greater than Ωcm, it is considered even better, 1 × 10 8 A value of Ωcm or higher was considered particularly good. The results are shown in Table 1.

[0102] (Comparative Example 1) Comparative Example 1 was carried out under the same conditions as Example 1, except that annealing treatment was not performed. In Comparative Example 1, the Si content was large relative to the total Si and Ti content, and the Ti content was small, so the dielectric thin film of Comparative Example 1 did not contain TiN metal particles. The results are shown in Table 1.

[0103] [Table 1]

[0104] Table 1 shows that Examples 1-3, which had dielectric thin films containing SiO(N) amorphous and TiN metal particles and a pair of electrodes, exhibited good ε and ρ values. In contrast, Comparative Example 1, in which the dielectric thin film did not contain TiN metal particles, showed a significantly lower ε value compared to Examples 1-3. [Explanation of symbols]

[0105] 1. Thin-film capacitor 11... Circuit board 12. Lower electrode 13. Thin films made of dielectric materials (dielectric thin films) 14...Top electrode

Claims

1. Having a dielectric composition and a conductive filler, The conductive filler is dispersed in the dielectric composition, The dielectric composition comprises SiO(N)-based amorphous material, The aforementioned conductive filler contains MN metal particles, M is one or more selected from Ti, Nb, and Cr. A dielectric having an average particle diameter of MN metal particles of 10 nm or less, and a capacitive element having a pair of electrodes, A capacitive element in which the thickness of the dielectric is less than 100 nm.

2. The capacitive element according to claim 1, wherein the Si content in the dielectric is 40% or more in atomic ratio with respect to the total content of Si and M.

3. Having a dielectric composition and a conductive filler, The conductive filler is dispersed in the dielectric composition, The dielectric composition comprises a SiO-based amorphous material. The aforementioned conductive filler contains M' metal particles, M' is one or more selected from Fe, Co, Ni, and Cu. A dielectric having an average particle diameter of the M' metal particles of 10 nm or less, and a capacitive element having a pair of electrodes, A capacitive element in which the thickness of the dielectric is less than 100 nm.

4. The capacitive element according to claim 3, wherein the Si content in the dielectric is 40% or more in atomic ratio with respect to the total content of Si and M'.

5. A method for manufacturing a capacitive element according to claim 1 or 2, A process for forming an (Si,M)(O,N) amorphous material, The process includes a step of incorporating the SiO(N) amorphous material and the MN metal particles into the dielectric by performing an annealing treatment on the (Si,M)(O,N) amorphous material, A method for manufacturing a capacitive element, wherein the annealing temperature in the annealing process is 700°C or higher and 800°C or lower.

6. The annealing process is performed by NH 3 A method for manufacturing a capacitive element according to claim 5, carried out under atmospheric conditions.

7. A method for manufacturing a capacitive element according to claim 1 or 2, A method for manufacturing a capacitive element, comprising the step of forming an (Si,M)(O,N) amorphous material in which the M content is 45% or more in atomic ratio relative to the total content of Si and M.

8. A method for manufacturing a capacitive element according to claim 3 or 4, A process for forming an (Si,M')O amorphous material, The process includes a step of incorporating the SiO-based amorphous material and the M' metal particles into the dielectric material by performing an annealing treatment on the (Si, M')O-based amorphous material, A method for manufacturing a capacitive element, wherein the annealing temperature in the annealing process is 700°C or higher and 800°C or lower.

9. A method for manufacturing a capacitive element according to claim 3 or 4, A method for manufacturing a capacitive element, comprising the step of forming an (Si,M')O-based amorphous material in which the M' content is 45% or more in atomic ratio relative to the total content of Si and M'.

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