CN114334444A - Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof - Google Patents
Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof Download PDFInfo
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- CN114334444A CN114334444A CN202111668230.1A CN202111668230A CN114334444A CN 114334444 A CN114334444 A CN 114334444A CN 202111668230 A CN202111668230 A CN 202111668230A CN 114334444 A CN114334444 A CN 114334444A
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- 239000002356 single layer Substances 0.000 title claims abstract description 21
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 20
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 16
- 239000010410 layer Substances 0.000 title claims abstract description 16
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 6
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Abstract
The invention relates to a single-layer ceramic capacitor grain boundary layer semiconductor ceramic material which is prepared from the following raw materials in percentage by weight: SrCO3 60～69％，TiO230-38% of additive and 0.2-3% of additive; wherein the additive is ZnO or CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2And Bi2O3One or more combinations of. The invention also relates to a preparation method of the material and a single-layer ceramic capacitor made of the material. The semiconductor ceramic material of the grain boundary layer of the single-layer ceramic capacitor does not contain heavy metals such as cadmium, lead and the like, and has the advantages of less environmental pollution, high dielectric constant and the like.
Description
Technical Field
The invention relates to the technical field of resistance materials, in particular to a single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and a preparation method thereof.
Background
In the development of modern electronic field, miniaturization and multi-functionalization of electronic devices have become development trends, and the demand of chip electronic components in the electronic field is increasing day by day, thereby driving the rapid development of the chip electronic components. The grain boundary layer semiconductor ceramic material has the advantages of good temperature characteristic, high dielectric constant, good frequency characteristic and the like, and occupies an important position in a single-layer chip semiconductor ceramic material.
The existing manufacturing process of the grain boundary layer semiconductor ceramic material generally comprises the following steps: material proportioning → mixing with deionized water → drying → crushing → calcining → sieving → adding additive → mixing → casting film → discharging glue → reducing in hydrogen-nitrogen mixed gas → coating oxidant, oxidizing in air atmosphere → sintering → single layer capacitor substrate. However, the grain boundary layer prepared by the process is mostly added with heavy metals such as cadmium, lead and the like, and the pollution to the environment is great in the production and use processes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a semiconductor ceramic material of a grain boundary layer of a single-layer ceramic capacitor, which does not contain heavy metals such as cadmium, lead and the like and has the advantages of less environmental pollution, high dielectric constant and the like.
The technical scheme adopted by the invention is as follows:
a semiconductor ceramic material of a grain boundary layer of a single-layer ceramic capacitor is prepared from the following raw materials in percentage by weight:
SrCO3 60～69％
TiO2 30～38％
0.2-3% of an additive;
wherein, ZnO and CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2And Bi2O3One or more combinations thereof. Too low or too high an additive can affect the sintered structure of the ceramic body and thus the electrical properties of the capacitor.
Further, the additive is made of ZnO and CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2And Bi2O3And (4) forming.
Further, the additive comprises the following components in percentage by weight:
further, the material is composed of SrCO3、TiO2Mixing with additive, and sintering at high temperature.
Furthermore, the dielectric constant k value of the material is 30000-50000.
The invention also provides a preparation method of the material, which comprises the following steps:
(1) mixing SrCO according to the proportion3With TiO2Preparing materials, mixing, ball-milling, drying and crushing;
(2) calcining the powder obtained in the step (1), then crushing and sieving;
(3) adding an additive into the powder obtained in the step (2) according to the proportion, then mixing, ball-milling, drying, crushing and sieving;
(4) pressing the powder obtained in the step (3) into a spindle, and sintering to obtain a ceramic body;
(5) the ceramic body was sliced to obtain a single-layer ceramic substrate for capacitors.
Further, the mixing and ball milling in the step (1) and the step (3) adopt the following process conditions: mixing and ball-milling by adopting a planetary ball mill, wherein the weight ratio of powder, grinding balls and deionized water in the ball-milling slurry is 1: 5: (1-1.5) and the ball milling time is 2-4 hours.
Further, the conditions of the calcination in the step (2) are as follows: calcining for 3-4 hours at 1200-1300 ℃.
Further, the sintering conditions in the step (4) are as follows: firstly, sintering for 4-5 hours at 1300-1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000 +/-50 ℃, and introducing air for sintering for 3-6 hours.
The invention also provides a single-layer ceramic capacitor made of the material.
Compared with the prior art, the grain boundary layer semiconductor ceramic material designed by the invention does not contain cadmium and lead, has high dielectric constant, has less pollution to the environment, does not need a secondary sintering method for coating insulating oxide in the production and preparation process, reduces the production cost, and conforms to the development trend of miniaturization and high capacity of ceramic capacitors so as to meet the increasingly improved technical requirements.
Detailed Description
The single-layer ceramic capacitor grain boundary layer semiconductor ceramic material is prepared from the following raw materials in percentage by weight:
SrCO3 60～69％
TiO2 30～38％
0.2-3% of an additive;
wherein the additive is ZnO or CaCO3、Li2CO3、B2O3、CuO、La2O3、SiO2And Bi2O3More preferably, the additive is made of ZnO, CaCO3、Li2CO3、B2O3、CuO、La2O3、SiO2And Bi2O3And (4) forming.
Preferably, the additive comprises the following components in percentage by weight:
the material and the single-layer ceramic capacitor are prepared by the following steps:
(1) mixing SrCO according to the proportion3With TiO2After the materials are prepared, adding deionized water, and mixing and ball milling by adopting a planetary ball mill, wherein the weight ratio of powder, grinding balls and the deionized water in the ball milling slurry is 1: 5: (1-1.5), ball milling for 2-3 hours, drying and crushing.
(2) Calcining the powder obtained in the step (1) at 1200-1300 ℃ for 3-4 hours, then crushing and sieving.
(3) Adding an additive into the powder obtained in the step (2) according to the proportion, adding deionized water, and mixing and ball-milling by adopting a planetary ball mill, wherein the weight ratio of the powder to the grinding balls to the deionized water in the ball-milling slurry is 1: 5: (1-1.5), ball milling for 3-4 hours, drying, crushing, and sieving with a 60-mesh sieve.
(4) Pressing the powder obtained in the step (3) into a spindle with the size of 50mm x 50mm under the pressure of 20-30 MPa, and sintering to obtain a ceramic body, wherein the sintering conditions are as follows: firstly, sintering for 4-5 hours at 1300-1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000 +/-50 ℃, and introducing air for sintering for 3-6 hours.
(5) And slicing the ceramic body according to the required thickness to obtain the single-layer ceramic substrate for the capacitor.
(6) And (4) carrying out metallization treatment on the ceramic substrate obtained in the step (5) by means of silver printing or sputtering, and forming a metal electrode on the ceramic substrate.
(7) Cutting the ceramic substrate obtained in the step (6) by using a precision dicing saw to obtain a single-layer ceramic capacitor with the size specification of 0.2-0.8 mm;
(8) the performance test of the prepared single-layer ceramic capacitor shows that the dielectric constant (K) is 30000-50000, the loss is less than 0.025, and the insulation resistance is more than 109Ω。
The following table shows the ceramic material formulations of examples 1 to 3 of the present invention and the properties of the single layer ceramic capacitors respectively fabricated therefrom.
In the grain boundary layer semiconductor ceramic material designed by the invention, ZnO and CaCO are used3、Li2CO3、B2O3、CuO、La2O3、SiO2And Bi2O3The additives are reasonably proportioned to form a stable grain boundary layer with good insulation on a grain boundary, so that the same insulation performance can be achieved without coating an insulation oxide. Furthermore, the invention sinters the semiconductor ceramic material with excellent performance at one time by adjusting the sintering process, does not need to adopt a secondary sintering method of coating insulating oxide, reduces the production cost, and conforms to the development trend of miniaturization and high capacity of the ceramic capacitor so as to meet the increasingly improved technical requirements.
The method manufactures the semiconductor ceramic capacitor with the compact structure of the grain boundary layer of the ceramic capacitor by the process mode of the wafer (ingot pressing, ingot burning, slicing, metalizing and scribing), and is not the traditional tape casting method and the extrusion film method.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. A semiconductor ceramic material of a grain boundary layer of a single-layer ceramic capacitor is characterized by being prepared from the following raw materials in percentage by weight:
SrCO3 60～69％
TiO2 30～38％
0.2-3% of an additive;
wherein the additive is ZnO or CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2And Bi2O3One or more combinations thereof.
2. The material of claim 1, wherein the additive is selected from the group consisting of ZnO, CaCO, and mixtures thereof3、CuO、La2O3、Li2CO3、B2O3、SiO2And Bi2O3And (4) forming.
3. The material according to claim 2, wherein the additive comprises the following components in percentage by weight:
4. a material as claimed in any one of claims 1 to 3, characterised by being composed of SrCO3、TiO2Mixing with additive, and sintering at high temperature.
5. A method for the preparation of a material according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) mixing SrCO according to the proportion3With TiO2Preparing materials, mixing, ball-milling, drying and crushing;
(2) calcining the powder obtained in the step (1), then crushing and sieving;
(3) adding an additive into the powder obtained in the step (2) according to the proportion, then mixing, ball-milling, drying, crushing and sieving;
(4) pressing the powder obtained in the step (3) into a spindle, and sintering to obtain a ceramic body;
(5) the ceramic body was sliced to obtain a single-layer ceramic substrate for capacitors.
6. The preparation method according to claim 5, wherein the mixing and ball milling in steps (1) and (3) are carried out under the following process conditions: mixing and ball-milling by adopting a planetary ball mill, wherein the weight ratio of powder, grinding balls and deionized water in the ball-milling slurry is 1: 5: (1-1.5) and the ball milling time is 2-4 hours.
7. The method according to claim 5, wherein the calcination in the step (2) is carried out under the following conditions: calcining for 3-4 hours at 1200-1300 ℃.
8. The production method according to claim 5, wherein the conditions for sintering in the step (4) are: firstly, sintering for 4-5 hours at 1300-1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000 +/-50 ℃, and introducing air for sintering for 3-6 hours.
9. A single layer ceramic capacitor made from the material of any of claims 1-4.
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| CN202111668230.1A CN114334444A (en) | 2021-12-31 | 2021-12-31 | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof |
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| CN202111668230.1A CN114334444A (en) | 2021-12-31 | 2021-12-31 | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314545A (en) * | 2008-07-02 | 2008-12-03 | 广东风华高新科技股份有限公司 | Spray coating method for producing dielectric ceramic powder body and obtained products thereof |
| CN103508732A (en) * | 2013-10-08 | 2014-01-15 | 江苏大学 | Low temperature coefficient crystal boundary layer ceramic capacitor medium and preparation method thereof |
| CN105084892A (en) * | 2015-08-11 | 2015-11-25 | 电子科技大学 | High-medium single-layer miniature ceramic capacitor substrate material and preparation method thereof |
| CN105314980A (en) * | 2014-07-31 | 2016-02-10 | 中国振华集团云科电子有限公司 | Preparation method for low-temperature-one-time-sintered grain-boundary-layer ceramic substrate |
-
2021
- 2021-12-31 CN CN202111668230.1A patent/CN114334444A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314545A (en) * | 2008-07-02 | 2008-12-03 | 广东风华高新科技股份有限公司 | Spray coating method for producing dielectric ceramic powder body and obtained products thereof |
| CN103508732A (en) * | 2013-10-08 | 2014-01-15 | 江苏大学 | Low temperature coefficient crystal boundary layer ceramic capacitor medium and preparation method thereof |
| CN105314980A (en) * | 2014-07-31 | 2016-02-10 | 中国振华集团云科电子有限公司 | Preparation method for low-temperature-one-time-sintered grain-boundary-layer ceramic substrate |
| CN105084892A (en) * | 2015-08-11 | 2015-11-25 | 电子科技大学 | High-medium single-layer miniature ceramic capacitor substrate material and preparation method thereof |
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