TWI288787B - A metal-oxide and the preparation method of the same - Google Patents

Abstract

A metal-oxide of formula (I): M11-xM2xM31-yM4yO3, and the preparation method thereof is disclosed, wherein M1, M2, M3, M4 are independently selected from a group consisting of: calcium, barium, bismuth, cadmium, lead, titanium, tantalum, hafnium, tungsten, niobium, zirconium, yttrium, lanthanum, antimony, chromium and thallium; 0 < x < 1 and 0 <= y <= 1.

Description

1288787 玖, the invention description: [Technical field of the invention] The present invention relates to a multi-component metal oxide with adjustable dielectric constant and low dielectric loss and a preparation method thereof, in particular, a method suitable for adjustable dielectric constant 5 Thin film multi-metal oxide and preparation method thereof. [Prior Art] Perovskite ferroelectric materials have the ability to modulate the dielectric constant under electric field (Tmiability): T = (C〇- CE) / C〇 * 100 〇 / 〇, where c 〇 10 represents The applied voltage is the dielectric constant of 〇; 仏 represents the dielectric constant at a given fixed voltage), and there is a significant change in the dielectric constant under high electric field (100 &gt; kv/cm). Dozens of percent. It can therefore be used as the resonant frequency of a variable valley tuned circuit without the upper limit of the frequency. At present, the variable capacitor is mostly made of PIN diode or GaAs_MMIC, and belongs to the method of 15 active τ, which has disadvantages such as attenuation of microwave signal, narrow bandwidth, high process integration cost, etc.; if prepared by perovskite ferroelectric film Variable capacitance, in addition to improving component performance (semiconductor variable capacitor adjustable ratio is usually less than 30%, and Q value is only about 1 )), but also because of its passive component manufacturing method with low price and low power loss. In the application of microwave components, the function of the phase shifter is to take advantage of the linearity of the change in capacitance, while others such as mixers and parametric amplifiers take advantage of the nonlinearity. Such applications utilizing voltage modulation frequency and phase are also bandpass/band rejection filters and Q resonators. Since the dielectric properties and adjustability of the perovskite ferroelectric thin film are related to the composition, how to optimize the composition is the most fundamental and critical issue. The film formation methods mentioned in 1288787 include pulsed laser deposition (PLD), radio frequency magnetron sputtering, organic metal vapor deposition (MOCVD), and sol-gel or chemical solution methods. Among them, the chemical solution method has attracted extensive attention in the past three years. Because of its better composition control and composition uniformity, the crystallization temperature is low, it can be coated in a large area of 5, the process control is easy and the cost is low, and the dielectric displacement varies with composition. , there is a lot of room for component development. In addition, in the material film formation process, in addition to compositional control and uniformity must be considered, the orientation of the crystal structure itself is also significant for electrical influence. The final application form of the preparation of perovskite ferroelectric materials by solution method can be divided into 10 nanometer powders, bulk materials and thin films; many of the patents in this aspect are mainly powder and ceramic bulk materials, and the application development of capacitors is relatively high. Mature field; recently, the application of high-frequency components has gradually received attention, especially high-frequency components such as phase shifters mainly composed of AB〇3 perovskite ferroelectric ceramics, including ceramic powder particle size and composition control. And ceramic block forming technology, even 15 to high-frequency components based on ceramic blocks. However, the biggest disadvantage of high-frequency components based on ceramic blocks is that the ferroelectric effect cannot be effectively used, and the bulk of the bulk material requires a high operating power M, so it does not (4) simultaneously reduce the trend of reducing components and reducing costs; In response to the need for functionalization and miniaturization of the mobile communication component office, thin filming is an inevitable trend. Because the raw materials used in the precursor of the titanium dioxide ferroelectric thin film are metal salts, the g &amp; base and anti-conditions of the ^ class will affect the coupling of the complex components and the subsequent microstructure of the film. Orientation; at the same time, having a specific structural function: gold, the film usually requires a relatively high preparation temperature, thus limiting the degree of compatibility of the semiconductor semiconductor process. 1288787 U.S. Patent No. 6,096,127 discloses a low loss dielectric. The preparation method of the electric film reduces the loss of the grain caused by the grain boundary and the point defect by increasing the size of the crystal grain, but it does not mention the chemical solution method in detail. 6,071,555 discloses a ferroelectric composite material composed of BSTO (barium strontium titanate) and additive MgO (magnesium oxide), which is produced by decomposition of an organic metal. However, the chemical solution reaction is not discussed in detail. A method for producing a strontium-containing metal oxide ceramic is disclosed in Patent No. 6,210,752, the precursor of which is a strontium neo-pentoxid dissolved in an amine solvent. e is admixed with at least one metal alkoxide dissolved in a solvent which is a reaction system in which the starting material is completely alkoxide. 15 U.S. Patent No. 5,468,679 discloses a multi-step sol-gel process for preparing a Wei-gel process. Metal oxides are used as layered superlattices, and the precursor used is titanium 2-methoxyethoxide. This patent discloses short-chain metal alkoxides, such as ethoxides. Propoxides usually hydrolyze too quickly, making the reaction difficult to control and products difficult to store. Long-chain alkoxides are difficult. Water-soluble and containing too much organic matter is not easy to obtain a high-quality film. Therefore, only a medium chain length alkoxide such as 2-methoxyethoxides can meet the required requirements. [1] The main purpose of the present invention is Providing a multi-metal oxide capable of producing a capacitor having a variable dielectric constant and a low dielectric loss from the multi-metal oxide. Another object of the present invention is to provide a method for preparing a multi-metal oxide solution 5 liquid,俾 can provide a multi-metal oxide solution having a low crystallization temperature and good coating quality. Provided is a method for fabricating a dielectric film, such that the dielectric film has characteristics such as a variable dielectric constant and a low dielectric loss. 10 For the above purpose, the multi-metal oxide of the present invention has a formula (I) Chemical formula:

MlUxM\M3UyM\〇3 (I) 15 where Μ1, M2 is selected from the group consisting of: calcium, barium, strontium, bismuth and lead; M3, The M4 line is selected from the group consisting of: titanium, bismuth, cadmium, lead, tantalum, hafnium, 20 tungsten, niobium, Zirconium, tin, manganese, iron, yttrium, lanthanum, antimony, chromium, and thallium; 0 &lt;χ&lt;1; and OS 1. Meanwhile, the preparation method of the multi-metal oxide solution of the present invention comprises: dissolving the alkoxide of M3 and M4 in an organic solvent 1288787 to form a precursor liquid, and dissolving M1 and Μ2 in the precursor liquid to form A multi-metal oxide solution. In addition, the method for manufacturing a dielectric film of the present invention comprises: providing a multi-metal oxide acetate solution; providing a multi-metal oxide 5-alcoholamine solution; providing a substrate, the substrate is by Shi Xi, Forming and heating at least one layer of a multi-metal oxide acetate film on the surface of the substrate, wherein the multi-metal oxide acetate film is composed of the multi-component oxide acetate solution And coating and heating at least one layer of the multi-element metal oxide alcohol amine film on the multi-gold 10 acetate film, the Beans in the Beans open for the winter to prepare ν Λ; ^, /, the 兀 兀 metal The oxide alcohol amine film is composed of the multicomponent metal oxide alcohol amine solution. The multi-metal oxide provided by the invention has the characteristics of low crystallization temperature ★, adjustable dielectric constant and low dielectric loss, and is especially a precursor for an adjustable dielectric film. The resulting dielectric material composition is suitable for applications such as variable capacitance for high frequency components, or applications of other high order microwave components such as shifters, mixers, parametric amplifiers, bandpass/band rejection choppers, and 9 spectra. Vibrator. The dielectric material composition of the present invention is mainly applied as a film in application 2 . The invention mainly adopts an amine alcohol solvent with μ3, μ4 metal alkoxide and Μ/, 20 Μ; Meng gen raw materials, the focus is on the amine alcohol solvent two-end functional groups can be respectively associated with ruthenium metal alkoxide and Μ 1, Μ 2 atom Bonding, so the mechanism of action of various agents other than traditional chelating agents. The traditional chelating agent solvent acts on Lai 3, the heart alkoxide, in order to mix and combine with other metal salts, to increase the force: solubility. This novel reaction mechanism can take into account the reaction and solubility between different elements to achieve uniform composition, reduce process temperature, reduce side reactions, and optimize the structural orientation of 1288787. Further, it is possible to further improve the film forming quality and improve the dielectric properties by further matching with a solvent additive for improving the coating quality and a precursor system using a film forming property as a buffer layer to promote structural orientation optimization.

Barium Strontium Titanate (BST) films have many potential applications such as DRAM, pyroelectric detectors, hydrogen detectors, and adjustable microwave components. The preparation methods mentioned in the literature include M〇c VD, pulsed(10) by deposition, sputtering and chemical solution (or s〇1_gel). Among them, the chemical liquid method has low cost and excellent composition control; however, most of the chemical solution method produces a polycrystalline structure which will form a mesophase with fine grains, and 10 too small grains have a poor structural orientation. The dielectric constant is made smaller, and the formation of the mesophase tends to inhibit the formation of the perovskite structure, so the formation of the perovskite structure often requires subsequent heat treatment. The main cause of this phenomenon is that the chemical structure of the starting materials of each component only plays a role of chelation and mixing. If the reaction between different elements can be increased while taking into account the solubility and the surface tension of the coating 15 solution, low crystallization can be obtained. Temperature, good coating quality, optimized structural orientation and precursor dielectric plate with adjustable dielectric constant and low dielectric loss

1 The invention adopts an amine alcohol solvent with titanium (M3) metal alkoxide and strontium (M1), and 2) metal raw materials, focusing on two kinds of amine alcohol solvents:; energy 2 (V soil can be separately combined with titanium (M3) Mechanism of action of metal alkoxides and strontium (M1) and pin (M2) atomic bonds. Traditional integrators: agents _, θ people are stable titanium (Μ3) metal alkoxides, in order to interact with other metal salts ^Homogeneous sentence, increase solubility. This novel reaction mechanism can take into account different reactions, solubility 'to achieve the composition of the sentence, reduce the process temperature 11 1288787 degrees, reduce side reactions, optimize structural orientation, etc. As disclosed in the first embodiment The coating precursor composition using this novel reaction mechanism is heat-treated after coating, and has better dielectric properties at the same thickness as compared with the conventional acetate-based precursor system (comparative example). The crystallization temperature has a tendency to decrease by 5. The amine alcohol solvent system adopted in the present invention belongs to a reactive precursor and is distinguished from the conventional non-reactive precursor. The effect is explained in the BST 躬 矿 矿 铁 铁 铁 , , , , , , , One principle Appropriately applied to a wide range of ferroelectric materials, including AB〇3 perovskite materials, layered perovskite materials, tungsten bronze ferroelectric materials, and ferroelectric materials of ΥΜη〇3 structure. Oxidized by three-component metal at 10 When the material is expanded into a four-component metal oxide, the BanSrxTi^yTayC^ composition obtained by the reactive precursor preparation method is better than the three-component Bai xSrxTii yTay〇3* body prepared by the non-reactive or reactive precursor. The electrical characteristics, and the four-component precursor prepared by the non-reactive method destroys the coating of the original system due to the mixing of the fourth element, and the good coating is obtained by the method. This result also proves the reaction type indirectly. The precursor system can effectively promote the bonding of metal components and produce orientation effects, as disclosed in Example 4. In addition, the literature indicates dielectric properties such as dielectric constant, loss, leakage current 20, etc. and film formation, composition, and doping. , electrodes, microstructure (grain size, grain shape, internal stress), strain, precursor concentration, tempering conditions and thickness, etc. have considerable dependence. The biggest factor is because the deformation during film formation affects the structural orientation. If a lattice-matched substrate is selected for the film growth process, it is easy to obtain a polycrystalline structure similar to that of the substrate. The bulk of the body is uniform in composition. Therefore, if the substrate 12 1288787 has a lattice mismatch, it is easy to form fine crystal grains due to homogeneous nucleation. The process of improving the film properties by the process—7^^^^^ It consists of spin coating of dozens of layers with a very rare precursor solution; the precursors used in the multilayer coating are different in T-degrees, which are gradient concentration gradients; or precursors with the same composition or different components. The upper layer of the film serves as a buffer layer. The processing temperature of each of the above layers may be lower than or higher than the crystallization temperature, and the precursors of different concentrations or not (four) points belong to the same precursor reaction system and non-reactive precursor ίο body composition. The purpose of this treatment is mainly to promote the stress caused by the mismatch between the heterogeneous crystal and the relaxation due to the lattice. For the film damaged by the chemical solution method, it is necessary to achieve a multi-layered film in accordance with the required thickness, and a thin film with a very rare precursor solution can obtain a film with good compactness because the chemical solution There is no problem of uneven composition of the 15 parts of the bureau caused by the law, and the remaining problem to be overcome is the problem of structural orientation after the reaction. Coating with a very thin precursor solution is a gas phase or liquid phase epitaxy method that optimizes the structural orientation. Despite this, the process of up to dozens of coatings is very difficult, and the advantages of the original chemical solution method are lost. This is because the surface of the film or the surface is prone to micropores after heat treatment, resulting in poor surface flatness, and the residual stress of the film accumulated by multiple high-temperature treatments is likely to cause thin film cracks, and too many interfaces represent an increase in interface defects. Subsequent coatings will be difficult to control. Therefore, the use of excessive number of spin coatings has the negative effects of complicated process and low yield; in addition, the number of coating layers and the essence of the precursor must be optimized, and dozens of extremely rare body solution coatings are not able to ensure the obtained film. Quality. 13 1288787 Since the quality of the film is related to the effect of the precursor solution and the surface of the substrate, the precursor system must have a good adhesion to the substrate (here, the pt metal electrode) in the coating process. A layer of heat treated film also has good affinity and is indispensable. If the coating properties of the precursor 5-body solution and the electrode substrate or dielectric film are not good, the above-mentioned multilayer coating method will result in a significant reduction in film quality. The comparative example in the present invention is a conventional acetate non-reactive precursor system, which is characterized in that the coating property is good, and the electrode substrate or the dielectric film has good adhesion, because the metal components are only The existence of a mixture of 10 uniform forms does not affect the bond between the molecules in the precursor and the substrate or the dielectric film, but because the components are only in a homogeneous mixed state, the existence of excessive phases cannot be avoided. The crystallization temperature is higher and the resulting film is inferior in properties. On the contrary, in the first embodiment of the present invention, since there is a bond between the metal components, the bond between the molecules and the substrate in the precursor is affected, so that the coating quality can be improved by adding a solvent additive for improving the quality of the coating, but in the precursor. The bonding between the molecule and the dielectric film is better than the conventional acetate non-reactive precursor system, so the crystallization temperature can be lower and the dielectric properties are better. Using this concept, the traditional acetate non-reactive precursor system can be used as a buffer layer in the comparative example, and the coating property is good. After the formation of the dielectric film, the basic alcohol of the first embodiment is used. As the precursor of the subsequent coating, the amine system adds solvent to improve the coating, and has the advantage of bonding between the complexes to produce the orientation function, which promotes the stress caused by the mismatch between the non-fourth and the (10) lattice mismatch. Optimization, it is expected to further improve the dielectric properties of the film, as disclosed in the second embodiment. For example, in 1288787, the essential difference between the non-reactive precursor and the reactive precursor is utilized, and the staggered coating can be used to further optimize the structural orientation and improve the electrical performance. See Example 3. 5 [Embodiment] It should be noted that the multi-metal oxide 1^11_#2^\431-7]\4%03 used in the present invention,]\41,]^2,]\43,]\ 44 is not limited, wherein, Μ, M2 is selected from the group consisting of: calcium, barium, strontium, bismuth and lead; M3, M4 is selected from a group The 10 groups include titanium, bismuth, cadmium, lead, tantalum, hafnium, tungsten (tungsten), niobium, zirconium, Tin, manganese, iron, yttrium, lanthanum, antimony, chromium, and thallium; 0 &lt; χ &lt;1; and i. Preferably, the tetra 15 component metal oxide is BakSrxTi^yTayO; χ and y are preferably in the range of 0·3$χ$0·7, and 〇.〇i&lt;y&lt;(K()5; the present invention In the preparation method of the multi-metal oxide solution, in the alcohol amine salt solution of m3, m4, the molar number of Μ3, Μ, 4 is preferably 99:1~9:1; the molar number of Μ1, Μ2 is compared Preferably, the solvent additive is added in order to increase the wettability of the solution and to improve the coating property. The solvent additive is preferably selected from the group consisting of: 2-methoxyl. Ethanol and 3-methoxy-1β-butanol; the organic solvent for preparing the M3, M4 alcoholamine salt solution is preferably selected from the group consisting of: N,N-dimethylethanolamine, ethanolamine, methylethanolamine, 15 1288787 Isopropanolamine, 3-amino-2-butanol, and 2-amino-2-methylpropanol. In the method for producing a dielectric film provided by the present invention, the thickness of the dielectric film is not limited, and is preferably Between 2〇〇〇_4〇〇〇(Angstr〇m) 5 In order to enable the reviewing committee to better understand the technical content of the present invention, the fourth preferred embodiment and a comparative example are described as follows . Example 1 Preparation of a BST film having a composition ratio of BaQ5Sr()5Ti〇3. 10 1. Preparation of a precursor First, titanium isopropoxide (9.1 g) was dissolved in n,N-dimethylethanolamine (30 g) to Forming a titanium precursor solution, and then adding metal ruthenium (2·2 g) and metal ruthenium (i · 4 g) to the titanium precursor solution, and after the ruthenium and osmium are dissolved, adding N,N-dimethylethanolamine to Form a 〇·1 M lithium titanate sol-gel solution, and then add 15-methoxyethanol (32 〇g) to the barium titanate sol-gel solution to improve the rotation of the sol-gel solution. Coating characteristics and increasing wettability 2. Film preparation ^ The sol-gel solution was coated on a Si/SiO 2 /Ti/Pt structure substrate using a spin coater at a rotation rate of 500-3000 rpm. When the coater 20 rotates, the volatile solvent will be lost by evaporation. After the coating is completed, the film is heated to 120-350 ° C by a heating plate for 5-10 minutes to complete the drying process, and then by fast The temperature rising device has a temperature of 500-700. When it is a knife-knife' and the calcination process is completed under an oxygen atmosphere. The crystallization temperature is measured by DTA to be 58 〇 1 6 1288787 The first to tenth layers of film follow the above method and have a total thickness of 2000 to 4000 A. When the film of the last layer is completed, the temperature range is in the flowing oxygen atmosphere via a rapid temperature riser. 6〇〇-800°C, time is 10-20 minutes and 5 minutes, complete the tempering process. 3_Electrical measurement of tempered BST film, deposited by shadow masking white gold, plated on a fixed area The electrode makes it a MIM structure. Using the measuring instrument HP 4284A, the measuring frequency is 1 〇〇 kHz, and the voltage range is -15V ～15V. The dielectric constant of the I measurement is 320 (platinum) ~ 415 (gold). The measurement results have a dielectric loss of 0.03-0.05. The measurement result has a modulation capacity of 24 to 26%. 15 Comparative Example 1 A BST film was prepared, the composition ratio of which was Ba〇5Sr()5Ti〇3. 1. Precursor preparation Titanium n-butoxide (27.23 g) was dissolved in 2-methoxyethanol (4 〇 g) to form a titanium precursor solution. Further, cerium acetate (1 〇·22 g) and cerium acetate (8·23 g) were mixed, and propionic acid (160 g) was added to form a cerium-strontium precursor solution. 20 Add the 钡-鳃 precursor solution slowly to the titanium precursor solution, mix well and then add the sol-gel solution. 2. Film preparation A sol-gel solution was coated on a substrate having a Si/Si〇2/Ti/Pt structure using a spin coater at a rotation rate of 5 〇〇 3 rpm. When the coater is rotated 25 turns, the volatile solvent will be lost by evaporation. To be coated, thin 17 1288787 film is heated to 120-35 (TC, time 5-10 minutes, complete the drying process; then by rapid heating device, temperature is 500-700 ° C, time is 5 -10 minutes ^ and the calcination procedure was completed under an oxygen atmosphere. The crystallization temperature was measured by DTA to be 624 ° C. 5 The second to fifth layers of the film were subjected to the above method and the total thickness was 2000 to 4000 A. After the film of the last layer is completed, the tempering process is completed by a rapid temperature rising device under a flowing oxygen atmosphere at a temperature ranging from 600 to 800 ° C for 10-20 minutes. The fire-completed BST film is vapor-deposited with white gold through a shadow mask, and the upper surface of the fixed area is plated to make it a MIM structure. Using the measuring instrument HP 4284A, the measuring frequency is 100 kHz, and the voltage range is -15V~15V. 15 The measurement results have a dielectric constant of 270 (platinum) and 330 (gold). The dielectric loss of the measurement is 0.02 (platinum) and 0.015 (gold). The measurement results have a modulation capacity of 26 to 33%. Example 2: Preparation of BST film, the composition ratio of which is Ba〇.5Sr〇.5Ti03. Preparation The sol-gel solution is coated on a substrate having a Si/SiO 2 /Ti/Pt structure using a spin coater at a rotation rate of 500-3000 rpm. When the coater 25 is rotated, the volatile solvent will be Loss by evaporation. 18 1288787 The first layer was first coated with a propionic acid/2-methoxyethanol system; the second layer was filmed with an N,N-dimethylethanolamine/2-methoxyethanol system. After each layer is coated, the film is heated to 12〇-35 (rc, time 5-10 minutes by the heating plate to complete the drying process; then by the rapid temperature riser, the temperature is 500-700 ° C, the time is 5_1〇 Minutes, and the calcination process is completed under an oxygen atmosphere. The third to tenth layers of the film follow the above method and use N, N_:

The methylethanolamine/2-methoxyethanol solvent system has a total thickness of 2 〇〇〇 to 4000 Å. After the film of the last layer is completed, the temperature is in the range of 6 〇〇 8 经由 in a flowing oxygen atmosphere via a rapid temperature rising device for 1 〇 2 〇 minutes to complete the tempering process. 2·Electrical measurement The tempered BST film was vapor-deposited with white gold through a shadow mask and plated with 15 fixed-area electrodes to make it a MIM structure. Using the measuring instrument HP 4284A, the measuring frequency is 100 kHz and the voltage range is -15V~15V.

The measured dielectric constant is 525. The dielectric loss is 〇.〇7. 20 The measurement results have a modulation capacity of 45%. Example 3, a BST film was prepared, and its composition ratio was BaQ5Sr()5Ti〇3. 25 1. Film preparation 19 Ϊ288787 Using a square twist coater, the rotation rate is 5〇〇-3, and the sol_heg solution is coated on a substrate with Si/Si (VTi/Pt structure. #涂涂When the cloth machine rotates, the volatile solvent will be lost by evaporation. The first layer is first coated with propionic acid/2-methoxyethanol system; the second-by: 'N-methylethanolamine/3_ The methoxybutanol system produces a film.

The mother layer is coated and the film is heated to 12 〇 _350 by a heating plate. 〇, : between 5-10 minutes 'complete the drying procedure; then by rapid heating to install ~ 'temperature at 500-70 (TC, time is 5_1 〇 minutes, and 70% calcination in an oxygen atmosphere. 10 15 The second to tenth layers of the film follow the above method, and the interstitial use of the Cyanwen/2-methoxyethanol system and the N,N-dimethylethanolamine/3_methoxybutanol solvent system are repeated to achieve a total thickness of The thickness of 2〇〇〇~4〇〇〇. When the film of the last layer is completed, the temperature range is 600-800〇c and the time is 1〇_2〇 under the oxygen atmosphere of the flow t through the rapid heating device. Minutes, complete the tempering process. 2 · Electrical measurement

The tempered BST film is vapor-deposited with white gold through a shadow mask, and the upper surface of the fixed area is plated to make it a MIM structure. Using the measuring instrument HP 4284A, the measuring frequency is 100 kHz, and the dielectric constant is 567. The measured dielectric loss was 0.004. The measurement result has a modulation capacity of 50%. 20 25 1288787 Example 4, preparation of BSTT thin film, and its composition ratio is

Ba〇.5Sr〇.5Ti0.98Ta〇.〇2〇3 〇1·Precursor preparation The gasification group (5 g) was dissolved in isopropanol to prepare a solution having a concentration of 6.5×10·4 mol/g 5 . Titanium isopropoxide (8·93 g) was combined with a previously vaporized hydrazine solution (〇92 g) / N,N-dimethylethanolamine (6 〇 g) to form a titanium precursor solution. Metal ruthenium (2.2 g) and metal ruthenium (L4g) are added to the titanium precursor solution. After the ruthenium and ruthenium are dissolved, N,N•dimethylacetamide is added to form sensitized 10 Ο·1 Μtarthotanic acid. Record the sol-gel solution. 2-methoxyethanol (320 g) was added to the barium titanate sol-gel solution to improve the spin coating characteristics of the sol-gel solution and increase the wettability. 2. Film preparation A sol 15 gel solution was coated on a substrate having a Si/SiO 2 /Ti/Pt structure using a spin coater at a rotation rate of 5 〇〇 to 3 rpm. When the coater is rotated, the volatile solvent will be lost by evaporation. Coating the film into a film by heating the plate to 12 〇 _35 〇〇 c for 5-10 minutes to complete the drying process; then using a rapid temperature riser, the temperature is between 5-1 G minutes between 500-7 GGC ' 'And complete the calcination 20 procedure in an oxygen atmosphere. The second to tenth layers of the thinner follow the above method and have a total thickness of up to 2000 to 4000 Å. 21 1288787 After completing the film of the last layer, through the rapid heating device, under the flowing oxygen atmosphere, the temperature range is 600-70 (TC, time is 10-20 minutes, the tempering process is completed. 3. Electrical measurement back The fire-completed BSTT film is vapor-deposited with white gold through a shadow mask, and is plated with an electrode above the solid area to make it a MIM structure. Using a measuring instrument HP 4284A, the measuring frequency is 1 〇〇 kHz, and the voltage range is - 15V~15V. The measurement result has a dielectric constant of 500. The dielectric loss of the measurement result is 〇.〇3. The measurement result has a modulation capacity of 38%. It can be known from the above embodiments that the present invention provides The multi-metal oxide and its preparation method can provide better modulation capability, lower 15 dielectric loss, and deep progress and industrial utilization. 20 The above embodiments are only for the purpose of claiming In the above embodiments, for convenience of description, the scope of the patent application of the present invention shall prevail, and not limited thereto.

twenty two

Claims (1)

1288787 Pickup, patent application scope: 1. A multi-metal oxide, which is of the structure of formula (1): MlUxM2xM3UyM4y03 (I) 5 wherein, Μ1, M2 are independently selected from a group including: ) (calcium), Barium, strontium, bismuth, and lead; M3, M4 are independently selected from the group consisting of: titanium, bismuth, cadmium, and error. Lead, tantalum, hafnium, tungsten, niobium, zirconium, tin, manganese, iron, yttrium, M Lanthanum), antimony, chromium, and thallium; 0&lt;χ&lt;1; and 0 S y $ 1. 2. The multi-metal oxide according to claim 1, wherein the multi-metal oxide is Bai.xSrxTin-yTayC^. 3. For the multi-metal oxides described in the second paragraph of the patent application, 0. 3 € χ $0·7, and O.OlgySO.l. 4. A method of preparing a multi-metal oxide solution, the metal oxide being a compound of formula (I): 20 Μ\.χΜ\Μ\.γΜ\〇3 (I) The method comprises: (a) The alkoxides of Μ3 and Μ4 are dissolved in an organic solvent to form a 25 precursor liquid, wherein Μ3 and M4 are independently selected from titanium 1288787 (titanium), bismuth, cadmium, lead (lead). ), group (tantalum), give (hafnium), tungsten, niobium, It (zirconium), tin (tin), mamantic, iron, yttrium, lanthanum a group consisting of: antimony, chromium 5, and thallium; and (b) dissolving Μ1, M2 in the precursor liquid to form a multi-metal oxide solution, wherein Μ1 The Μ2 lines are each independently selected from the group consisting of: 4 calcium, barium, strontium, bismuth, and lead. The preparation method of claim 4, wherein the organic solvent in the step (a) is N,N-dimercaptoethanolamine, ethanolamine, N-methylethanolamine, isopropanolamine , 3-amino-2-butanol and 2-amino-2-methylpropanol. 6. The preparation method according to claim 4, wherein further comprising a step (c): (c) adding a solvent additive to the multi-metal oxide solution; wherein the solvent additive is selected from the group consisting of The group includes: 2-methoxyethanol and 3-decyloxy-1-butanol. 7. The preparation method according to claim 4, wherein the multi-element metal oxide is Bai.xSrxTibyTayC^. 8. The preparation method according to claim 7, wherein 0.3 S xS 0.7, and 0·01 $ 0_1 〇9. A method for producing a dielectric film, the dielectric film comprising a formula (I) Polymetallic oxides: 1288787 Μ\.χΜ\Μ\.γΜ\〇3 (I) wherein Μ and Μ2 are independently selected from the group consisting of: calcium, barium, and Strontium), bismuth, and 5 lead; M3, M4 are independently selected from the group consisting of: titanium, bismuth, cadmium, lead, and boat ( Tantalum), hafnium, tungsten, niobium, zirconium, tin, manganese, iron, yttrium, M (lanthanum), recorded ( Antimony), chromium 10 (chromium), and imal (thallium); 0&lt;χ&lt;1; and 0 S y $ 1 ; the preparation method comprises: (1) providing a multi-metal oxide acetate solution; (2) Providing a multi-metal oxide alkanolamine solution; (3) providing a substrate consisting of ruthenium, ruthenium dioxide, titanium 15 or platinum; (4) coating and heating to An additional layer of a multi-metal oxide acetate film on the surface of the substrate, wherein the multi-metal oxide acetate film is composed of the multi-component oxide acetate solution; and (5) coating and heating at least one layer A multi-metal oxide alkanolamine 20 film is formed on the multi-metal oxide acetate film, wherein the multi-metal oxide alkanol film is composed of the multi-metal oxide alkanolamine solution. 10. The manufacturing method according to claim 9, wherein the multi-metal oxide acetic acid solution is prepared by the following steps: 1288787 (1A) Dissolving M, M alkoxide in methoxyethanol to form hydrazine M3-M4 precursor solution; (1-B) M!, M2 acid gg, 4: 夂, / liquid into propionic acid, forming Μ precursor solution; and 5 (1 C) mixing The Μ-Μ precursor solution and the Μι_Μ2 precursor solution are used to obtain the multi-metal oxide acetate solution. The manufacturing method according to claim 9, wherein the multi-metal oxide alkanolamine solution is obtained by the following steps: 10 (2-Α) dissolving the alkoxides of cerium 3 and cerium 4 in an organic solvent Forming a hydrazine, Μ4 precursor solution, and the organic solvent is selected from the group consisting of: ν, ν dimethylethanolamine, ethanolamine, Ν-mercaptoethanolamine, isopropanolamine, 3-amino-2-butanol and a group consisting of 2-amino-2-methylpropanol; (2-Β) dissolving Μ1, Μ2 in the precursor solution of μ3·Μ4 to form a multi-metal oxide alkanolamine solution; and 15 (2 - C) adding a solvent additive to the multi-metal oxide solution; wherein the solvent additive is selected from the group consisting of 2-methoxyethanol and 3-methoxy-1-butanol, 12. The method of claim 10, wherein the multi-metal oxide in the multi-metal oxide acetate solution is 20 BahSrxIVyTayOs, wherein 0·3$χ$0.7, and 〇.〇l$y“0·1 〇 </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; The genus 26 1288787 is a BakSrxTibyTayC^, wherein 0·3$χ$0.7, and 0·01 $ y S Ο · 1 0 14. The manufacturing method according to claim 9, wherein the multi-metal oxide The total thickness of the acetic acid film and the multi-metal oxide anlkoxide film is between 2,000 and 4,000 angstroms (Angstrom). 27