CN116462500A - X7R characteristic thin-layer BME ceramic dielectric material and preparation method thereof - Google Patents
X7R characteristic thin-layer BME ceramic dielectric material and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 239000003989 dielectric material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 18
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000007873 sieving Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 14
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- 230000008569 process Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 230000001680 brushing effect Effects 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
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- 238000013035 low temperature curing Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003985 ceramic capacitor Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an X7R characteristic thin-layer BME ceramic dielectric material which is characterized by comprising the following components in parts by mole: 100 parts of a base material; 0.2 to 4.5 parts of modified additive MYS;0.01 to 0.6 part of CaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.05 to 2.0 parts of MnCO 3 The method comprises the steps of carrying out a first treatment on the surface of the 0.5 to 6.0 parts of ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the 0.01 to 0.5 part V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the 0.05 to 1.0 part of BaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the substrate is BaTiO 3 . The beneficial effects of the invention are as follows: the 7R characteristic thin-layer BME ceramic dielectric material is suitable for the thinning of an MLCC, has simple and adjustable formula design, easy control of preparation and sintering processes, can reduce the production cost of the MLCC, and has high dielectric constant, low dielectric loss, excellent temperature stability and excellent insulation resistance.
Description
Technical Field
The invention relates to the technical field of BME ceramic dielectric materials, in particular to an X7R characteristic thin layer BME ceramic dielectric material and a preparation method thereof.
Background
The miniaturization, high performance and low power consumption of electronic products such as mobile phones and computers have become major trends, and the integration and miniaturization of passive chip components such as capacitors, inductors and resistors used in these devices have become urgent demands. Multilayer ceramic capacitors (MLCCs) have become the dominant capacitor products at present, in place of single-layer ceramic capacitors, due to their high capacitance, high reliability, wide operating temperature, and excellent high frequency characteristics.
The multilayer ceramic capacitor (Multilayer ceramic capacitor, MLCC) is one of the most rapid-growing paster elements in the 21 st century, and mainly comprises three parts of dielectric materials, internal electrodes and terminal electrodes. The ceramic dielectric material is stacked with the inner electrode in a certain manner and connected with the terminal electrode in a parallel manner. With the rapid development of electronic information technology, the performance requirements of people on novel electronic components are more and more strict, and MLCC (metal-dielectric ceramic) has higher requirements on temperature stability, base metal internal polarization, high reliability and the like while developing to dielectric thinness.
The traditional inner electrode material of the MLCC is generally silver palladium (Ag-Pd) electrode, which is expensive, resulting in high production cost of the MLCC; and the base metal internal electrode (BME) such as nickel (Ni) or copper (Cu) is adopted to replace noble metal as the internal electrode material, so that the production cost of the MLCC can be greatly reduced.
According to the international electronic industry association EIA (Electronic Industries Association) standard, the X7R temperature-stable MLCC refers to a temperature range of-55-125 ℃ with a capacitance value of 25 ℃ as a reference, wherein the capacitance temperature change rate (TCC) is less than or equal to + -15% and the dielectric loss (DF) is less than or equal to 2.5%. The X7R type MLCC with high K value and excellent temperature stability has wide application prospect.
Problems and disadvantages of the prior art:
(1) The MLCC of the noble metal inner electrode has high production cost and limits the wide application of the MLCC;
(2) The use of Ni, cu and other base metal internal electrodes (BME) requires BaTiO 3 The matrix is subjected to inert or reducing atmosphere (mainly H 2 、N 2 ) The lower part is co-fired with the BME, otherwise, the BME is oxidized in the sintering process, and the inner electrode loses the conductive effect to cause the failure of the MLCC; but the barium titanate material is reduced by sintering under a reducing atmosphere,the semiconducting occurs, resulting in a decrease in insulation resistance. Therefore, the addition of the additive to barium titanate increases the BaTiO 3 The reduction resistance of the base ceramic dielectric material can obtain a multilayer ceramic capacitor with high insulation resistance and high reliability.
(3) The grain size of the prior MLCC after sintering is often more than 500nm, so that the single-layer dielectric thickness is more than 8um, and the method is not suitable for the development direction of the MLCC ultrathin dielectric layer, miniaturization, multi-stacking layer number and high capacity; MLCC with a medium thickness of less than 5um is also usually made of barium titanate by hydrothermal method. The hydrothermal barium titanate production process is complex and has high cost. And the crystal has the defects of hydroxyl residue, air holes and the like, so that the MLCC has unstable performance and poor reliability.
(4) With the rapid update iteration of new electronic components, higher demands are put on MLCCs. The BME porcelain is required to have high dielectric constant, excellent capacity temperature stability, good insulation resistance and reliability, and can adapt to the development direction of an MLCC ultrathin medium layer and miniaturization while having reduction resistance. This is a difficulty in preparing BME ceramic dielectric materials today, and is also a problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the following technical scheme:
the present invention aims to solve the problems and disadvantages of the prior art and to provide a solid phase BaTiO 3 The thin-layer BME ceramic capacitor ceramic material is suitable for thinning of an MLCC, has simple and adjustable formula design, easy control of preparation and sintering processes, can reduce the production cost of the MLCC, has high dielectric constant, low dielectric loss, excellent temperature stability and excellent insulation resistance (the K value is between 2500 and 2920, the loss is lower than 2 percent, the capacity-temperature characteristic deviation of-55 ℃ to +125 ℃ is lower than 15 percent), and has the insulation resistance of over 650GΩ, and the whole ceramic material is high in K value, low in dielectric loss, high in insulation resistance and excellent in temperature characteristic, and can be sintered in a reducing atmosphere.
An X7R characteristic thin layer BME ceramic dielectric material comprises the following components in parts by mole:
100 parts of a base material;
0.2 to 4.5 parts of modified additive MYS;
0.01 to 0.6 part of CaCO 3 ；
0.05 to 2.0 parts of MnCO 3 ；
0.5 to 6.0 parts of ZrO 2 ；
0.01 to 0.5 part V 2 O 5 ；
0.05 to 1.0 part of BaCO 3 ；
Wherein the substrate is BaTiO 3 。
As a further improvement of the scheme, the modified additive MYS material consists of the following materials in percentage by mass: 20 to 25wt% of MgCO 3 、30～40wt％Y 2 O 3 、25～35wt％SiO 2 。
As a further improvement of the scheme, the material components in the modified additive MYS material are as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2
As a further improvement of the present solution, baTiO in the substrate 3 Synthesized by a solid phase method, and the granularity range is 150-300 nm.
The preparation method of the thin-layer BME ceramic dielectric material with X7R characteristics comprises the following preparation steps:
s1 preparation of modified additive MYS
S2 primary ball milling
Adding 700-1200 g of 2.5mm zirconium balls into a ball milling tank, taking absolute ethyl alcohol as a dispersion medium, adding 0.2-4.5 mol parts of MYS and 0.01-0.6 mol parts of CaCO 3 0.05 to 2.0 mole parts of MnCO 3 ZrO 0.5-6.0 mol parts 2 0.01 to 0.5 molar part of V 2 O 5 0.05 to 1.0 mole part of BaCO 3 The mixture is used as an additive and proportioned, and the ball milling time of the ball mill is 2-5 hours;
s3 secondary ball milling
After one ball milling is stopped, 100 mole parts of BaTiO 3 Adding into a ball milling tank for primary ball milling as a main base material, mixing with the additive for primary ball milling, and ball millingBall milling for 4-8 h, drying and granulating;
s4 tabletting and adhesive discharging
Pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 300-600 ℃ for 2-5 h, and discharging organic matters;
s5 sintering and cooling
Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1180-1350 ℃, preserving heat for 2-6 h, then cooling to 1020 ℃ and preserving heat for 1h, and then cooling along with the furnace, thus obtaining the thin-layer BME ceramic dielectric material with X7R characteristics.
As a further improvement of the scheme, in the S1, the modified additive MYS is prepared by MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 And (3) after the ingredients are mixed, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, and grinding again and sieving with a 100-mesh sieve.
As a further improvement of the scheme, in the step S3, after grinding and dispersing, the slurry is placed into an oven, the slurry is dried by heat preservation for 12 hours at 80 ℃, then the dried block material is crushed and passes through a 100-mesh standard sieve, PVA solution is added as a binder for granulation, and then the 100-mesh standard sieve is passed again.
As a further improvement of the scheme, in the step S4, the granulated powder is pressed into a wafer green body with the diameter of 1.5mm under the pressure of 2-5 t, and the wafer green body is preserved for 2-5 h in a muffle furnace at the temperature of 300-600 ℃ to discharge organic matters.
As a further improvement of the present solution, in S5,
wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h;
when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into be introduced intoPure N2, the gas flow is controlled to be 1.5-2.5L/h;
the atmosphere and the flow rate in the atmosphere furnace are kept unchanged until the temperature is reduced to the room temperature along with the furnace.
Compared with the prior art, the invention has the beneficial effects that:
1. the BME ceramic dielectric material obtained by the invention has excellent reduction resistance. By directing BaTiO at 3 The modified additive MYS synthesized by adding the base porcelain powder fully plays the acceptor role of Mg and Y elements in the calcining process of the porcelain medium, and the concentration of the oxygen vacancies caused by the addition of the modified additive MYS is larger than that formed by oxygen volatilization, thereby improving BaTiO 3 To make Ti 4+ Is not easy to be reduced to Ti in a high-temperature reducing atmosphere 3+ . So that the barium titanate can maintain high insulation resistance even when sintered in a reducing atmosphere. The insulation resistance of the examples with MYS added was much higher than that of comparative example 1 without MYS added. The insulation resistance of the sintered sample obtained in example 2 reached about 1200gΩ, an order of magnitude higher than that of comparative example 1.
2. The BME ceramic dielectric material obtained by the invention has excellent reduction resistance, good dielectric property and excellent dielectric temperature stability. Compared with comparative example 1, the incorporation of MYS in the examples is advantageous in forming a liquid phase upon sintering, lowering the sintering temperature, and at the same time, further flattening the capacity-temperature characteristic, improving the temperature characteristic. The temperature change rate TCC of examples 1-5 at-55-125 ℃ is less than or equal to + -15%, and meets the characteristic standard of X7R.
3. The BME ceramic dielectric material obtained by the invention is suitable for preparing a thinned MLCC. BaTiO used in the present invention 3 The granularity of the base material is only 150-300 nm, the granularity of the sintered crystal grains is 300-400 nm, a thin layer MLCC with the single-layer dielectric layer thickness of 3-4 um level can be prepared, and each layer has at least 6-8 overlapped crystal grains, so that the voltage resistance of the dielectric layer is improved, and the stability and reliability of the dielectric layer are also ensured;
4. the invention controls the ball milling time, the mixture ratio of the additives and BaTiO by ball milling the additives for one time in advance 3 Particle size of the base material, etc. to realize the additive and BaTiO 3 All of the substrates are mutuallyUniformly diffusing to form a uniform core-shell structure, inhibiting the growth of crystal grains, and further ensuring that the MLCC material has higher dielectric constant and excellent temperature stability.
5. The preparation process is simple and convenient, the formula design is simple and adjustable, the sintering process is easy to control, the material uniformity is good, the dielectric constant is high, the dielectric loss is low, the temperature stability and the insulation resistance are excellent, the production cost of the MLCC can be effectively reduced, and the thin layer MLCC with the single-layer dielectric layer thickness reaching 3-4 um level can be prepared.
6. No RoHS instruction limited substances and no metal elements such as lead, cadmium, chromium and the like are added, so that the material is an environment-friendly dielectric material.
Drawings
FIG. 1 is an XRD pattern for the modified additive MYS of the invention.
FIG. 2 shows BaTiO of 200nm average particle size used in the present invention 3 Microcosmic topography of the powder substrate;
FIG. 3 is a graph of the microscopic morphology of the sintered ceramic of the sample of example 3 (300-400 nm) of the present invention.
FIG. 4 is a graph of the microscopic morphology of the sintered ceramic of the sample of comparative example 2 (1.5-4 um) of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to examples:
the invention is further described below by means of specific embodiments.
Comparative example 1
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Ball milling for the first time: 800g of 2.5mm zirconium balls are added into a ball milling tank, and 0.1 molar part of CaCO is added by taking absolute ethyl alcohol as a dispersion medium 3 0.12 molar part of MnCO 3 1.2 molar parts of ZrO 2 V0.18 molar parts 2 O 5 0.89 molar parts of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 4 hours by a ball mill;
(2) Two (II)Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 200nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 4 hours by a ball mill, and drying and granulating the mixture;
(3) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 400 ℃ for 4 hours, and discharging organic matters;
(4) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1240 ℃, preserving heat for 2 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Comparative example 2
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 1000g of 2.5mm zirconium balls are added into a ball milling tank, and 0.97 mole part of MYS and 0.26 mole part of CaCO are added by taking absolute ethyl alcohol as a dispersion medium 3 0.95 molar parts of MnCO 3 3.59 molar parts of ZrO 2 V0.3 molar parts 2 O 5 0.41 molar part of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 5 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 200nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 8 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 450 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1240 ℃, preserving heat for 4 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Example 1
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 800g of 2.5mm zirconium balls are added into a ball milling tank, 1.4 mole parts of MYS and 0.1 mole part of CaCO are added by taking absolute ethyl alcohol as a dispersion medium 3 0.12 molar part of MnCO 3 1.2 molar parts of ZrO 2 V0.18 molar parts 2 O 5 0.89 molar parts of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 4 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 200nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 4 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 400 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1240 ℃, preserving heat for 2 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Example 2
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 900g of 2.5mm zirconium balls were added to a ball mill pot, and 2.13 mol parts of MYS and 0.35 mol part of CaCO were added to the ball mill pot with absolute ethyl alcohol as a dispersion medium 3 0.2 molar parts of MnCO 3 0.69 molar parts of ZrO 2 V0.12 molar parts 2 O 5 0.59 molar parts of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 3 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average particle diameter of 250nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 4 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 500 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1200 ℃, preserving heat for 3 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Example 3
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 1000g of 2.5mm zirconium balls are added into a ball milling tank, and 0.97 mole part of MYS and 0.26 mole part of CaCO are added by taking absolute ethyl alcohol as a dispersion medium 3 0.95 molar parts of MnCO 3 3.59 molar parts of ZrO 2 V0.3 molar parts 2 O 5 0.41 molar part of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 5 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 200nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 4 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 450 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1240 ℃, preserving heat for 4 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. Then brushing low-temperature curing conductive silver paste on the ceramic wafer, and putting the ceramic wafer into an oven at 90-150 DEG CAnd baking for 30min to obtain the silver electrode, and testing various electrical properties.
Example 4
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 950g of 2.5mm zirconium balls are added into a ball milling tank, 1.54 mole parts of MYS and 0.05 mole part of CaCO are added by taking absolute ethyl alcohol as a dispersion medium 3 0.65 molar part of MnCO 3 2.21 molar parts of ZrO 2 0.08 molar part of V 2 O 5 0.12 molar part of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 5 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 300nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 4 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 450 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1220 ℃, preserving heat for 2 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 Gas flow control1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Example 5
The invention relates to a preparation method of an X7R characteristic thin-layer BME ceramic dielectric material, which comprises the following steps:
(1) Preparation of modification additive MYS: according to MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 Mixing materials, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, grinding again, sieving with a 100-mesh sieve, and obtaining the modified additive MYS.
(2) Ball milling for the first time: 750g of 2.5mm zirconium balls are added into a ball milling tank, and 0.58 mol part of MYS and 0.16 mol part of CaCO are added by taking absolute ethyl alcohol as a dispersion medium 3 1.32 molar parts of MnCO 3 2.71 molar parts of ZrO 2 V0.05 molar parts 2 O 5 0.27 molar part of BaCO 3 Mixing materials according to the proportion as additives, and ball milling for 3 hours by a ball mill;
(3) Secondary ball milling: after the one-time ball milling is stopped, 100 mole parts of BaTiO with the average grain diameter of 200nm synthesized by a solid phase method 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with the additive for primary ball milling, ball milling the mixture for 6 hours by a ball mill, and drying and granulating the mixture;
(4) Tabletting and adhesive discharging: pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 450 ℃ for 4 hours, and discharging organic matters;
(5) Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1260 ℃, preserving heat for 2 hours, and then cooling to 1020 ℃ and preserving heat for 1 hour. Wafer green compact at N 2 /H 2 During sintering in a tubular atmosphere furnace, the atmosphere furnace is kept warm from the beginning of heating to the beginning of cooling to 1020 DEG CIs filled with 1.5% H 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h; when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h; and then keeping the atmosphere in the atmosphere furnace and the flow unchanged until the temperature is reduced to room temperature along with the furnace, and obtaining the thin-layer BME ceramic dielectric material with X7R characteristics. And brushing low-temperature curing conductive silver paste on the ceramic wafer, and baking in a baking oven at 90-150 ℃ for 30min to obtain a silver electrode, and testing various electrical properties.
Table 1 example formulation (molar parts)
The performance of each of the above comparative examples and examples 1 to 5 was measured by taking 3 samples after firing and brushing silver, and the performance parameters thereof are shown in Table 2
Table 2 comparative examples and results of performance tests of examples 1 to 5
From Table 2, comparison of the properties of the products obtained in comparative example 1 and examples 1 to 5 shows that:
the X7R characteristic thin BME ceramic dielectric material prepared by the specific formula and the technology has the K value of 2500-2920, the loss of less than 2 percent, the capacity-temperature characteristic deviation of minus 55 ℃ to +125 ℃ of less than 15 percent, and the insulation resistance of over 650GΩ, and the whole performance of high K value, low dielectric loss, high insulation resistance and excellent temperature characteristic. Compared with comparative example 1, the BME ceramic dielectric material has the advantages of reduced sintering temperature, and obviously improved temperature characteristics and reduction resistance.
Characteristic peak analysis was performed on the modified additive MYS shown in FIG. 1, and the modified additive MYS formed a main crystal phase of MgY 4 Si 3 O 13 。
As can be seen from FIG. 2, the BaTiO 3 The average granularity of the base material is 200nm, the grain size of the powder is small and uniform, and the shape is regular. Selecting nano-scale BaTiO 3 The substrate is beneficial to controlling the grain size of the MLCC after sintering, and compact fine-grain ceramic is formed in the sintering process.
From a comparison of fig. 3 and 4, and a comparison of the properties of the products prepared in comparative example 2 and example 3 in table 2, it can be seen that comparative example 2 is identical to example 3 in formulation and the rest of the process conditions, except that comparative example 2 is subjected to secondary ball milling for 8 hours and example 3 is subjected to secondary ball milling for 4 hours. The grain size of the sample of comparative example 2 after sintering into porcelain grows to 1.5-4 um, the grain is excessively large, and the core-shell structure is damaged. The grain size is not uniform, and the requirement of thinning the MLCC is not met; the time of the secondary ball milling in the embodiment 3 is shortened to 4 hours, the grain size is only 300-400 nm after sintering into porcelain, and the grain size is uniform. The thin-layer requirements of the MLCC are met, and meanwhile, the loss, the TCC and the insulation resistance are obviously improved, so that the characteristic requirements of X7R are met. Description by selecting nano-sized BaTiO 3 The invention effectively inhibits the further growth of crystal grains under the grain refining action of MYS, and is beneficial to preparing the MLCC of the thin dielectric layer. And realize additive and BaTiO 3 The matrixes are uniformly diffused mutually to form a uniform core-shell structure, so that the MLCC material has higher dielectric constant and excellent temperature stability and anti-reduction property.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the present invention are within the scope of the invention.
Claims (9)
1. A thin layer BME ceramic dielectric material of X7R character, characterized by comprising the following components in molar parts:
wherein the base isThe material is BaTiO 3 。
2. The thin layer BME ceramic dielectric material with X7R characteristics according to claim 1, wherein the modified additive MYS material is composed of the following materials in percentage by mass: 20 to 25wt% of MgCO 3 、30～40wt％Y 2 O 3 、25～35wt％SiO 2 。
3. The thin layer BME ceramic dielectric material of claim 2, wherein the modified additive MYS material comprises the following components: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 。
4. The thin layer BME ceramic dielectric material of claim 1, wherein BaTiO in the substrate 3 Synthesized by a solid phase method, and the granularity range is 150-300 nm.
5. A method for preparing the thin BME ceramic dielectric material with X7R characteristics according to any one of claims 1 to 4, comprising the following steps:
s1 preparation of modified additive MYS
S2 primary ball milling
Adding 700-1200 g of 2.5mm zirconium balls into a ball milling tank, taking absolute ethyl alcohol as a dispersion medium, adding 0.2-4.5 mol parts of MYS and 0.01-0.6 mol parts of CaCO 3 0.05 to 2.0 mole parts of MnCO 3 ZrO 0.5-6.0 mol parts 2 0.01 to 0.5 molar part of V 2 O 5 0.05 to 1.0 mole part of BaCO 3 The mixture is used as an additive and proportioned, and the ball milling time of the ball mill is 2-5 hours;
s3 secondary ball milling
After one ball milling is stopped, 100 mole parts of BaTiO 3 Adding the mixture into a ball milling tank for primary ball milling as a main base material, mixing the mixture with an additive for primary ball milling, ball milling the mixture for 4 to 8 hours by a ball mill, and drying and granulating the mixture;
s4 tabletting and adhesive discharging
Pressing the granulated powder into a wafer green body, preserving heat in a muffle furnace at 300-600 ℃ for 2-5 h, and discharging organic matters;
s5 sintering and cooling
Placing the wafer green body after glue discharge in N 2 /H 2 Sintering in a tubular atmosphere furnace, wherein the sintering temperature is 1180-1350 ℃, preserving heat for 2-6 h, then cooling to 1020 ℃ and preserving heat for 1h, and then cooling along with the furnace, thus obtaining the thin-layer BME ceramic dielectric material with X7R characteristics.
6. The method for preparing a thin BME ceramic dielectric material with X7R characteristics according to claim 5, wherein in S1, the modified additive MYS is MgCO 3 、Y 2 O 3 、SiO 2 The weight percentage is as follows: 25wt% MgCO 3 、40wt％Y 2 O 3 、35wt％SiO 2 And (3) after the ingredients are mixed, putting into a ball mill, drying after ball milling for 6-12 hours, grinding, sieving with a 100-mesh sieve, heating to 850-1100 ℃, sintering, preserving heat for 2-6 hours, cooling, and grinding again and sieving with a 100-mesh sieve.
7. The method for preparing the thin BME ceramic dielectric material with X7R characteristics according to claim 5, wherein in S3, after grinding and dispersing, the slurry is put into an oven, the slurry is dried by heat preservation at 80 ℃ for 12 hours, then the dried block material is crushed and passes through a 100-mesh standard sieve, then PVA solution is added as a binder for granulation, and then the 100-mesh standard sieve is passed again.
8. The method for preparing a thin BME ceramic dielectric material with X7R characteristics according to claim 5, wherein in the step S4, the granulated powder is pressed into a wafer green body with the diameter of 1.5mm under the pressure of 2-5 t, and the wafer green body is preserved for 2-5 hours in a muffle furnace at the temperature of 300-600 ℃ to discharge organic matters.
9. The method for preparing a thin BME ceramic dielectric material having X7R characteristics according to claim 5, wherein, in S5,
wafer green compact at N 2 /H 2 Tubular gasDuring sintering in an atmosphere furnace, 1.5% H is introduced into the atmosphere furnace from the beginning of heating to the beginning of heat preservation when the temperature is reduced to 1020 DEG C 2 、98.5％N 2 The gas flow is controlled to be 1-4L/h;
when the heat preservation at 1020 ℃ is started, stopping introducing N 2 /H 2 The mixed gas is changed into pure N 2 The gas flow is controlled to be 1.5-2.5L/h;
the atmosphere and the flow rate in the atmosphere furnace are kept unchanged until the temperature is reduced to the room temperature along with the furnace.
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