CN114334444B - 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
- Publication number
- CN114334444B CN114334444B CN202111668230.1A CN202111668230A CN114334444B CN 114334444 B CN114334444 B CN 114334444B CN 202111668230 A CN202111668230 A CN 202111668230A CN 114334444 B CN114334444 B CN 114334444B
- Authority
- CN
- China
- Prior art keywords
- ball milling
- mixing
- sintering
- layer
- ceramic capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 21
- 239000002356 single layer Substances 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 title claims abstract description 17
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 16
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 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 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000919 ceramic Substances 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
- 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
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 238000010298 pulverizing process Methods 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
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 2
- 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
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 235000012431 wafers Nutrition 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
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: 30-38% of SrCO 360～69％,TiO2 and 0.2-3% of additive; wherein the additive is one or more of ZnO、CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2 and Bi 2O3. The invention also relates to a preparation method of the material and a single-layer ceramic capacitor manufactured by using the material. The single-layer ceramic capacitor grain boundary layer semiconductor ceramic material 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 the modern electronic field, miniaturization and multifunctionality of electronic devices have become a development trend, and the requirements of the electronic field on chip electronic components are increasingly increasing, so as to drive 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 plays an important role in the single-layer chip semiconductor ceramic material.
The existing process for manufacturing the crystal boundary layer semiconductor ceramic material generally comprises the following steps: proportioning materials, mixing with deionized water, drying, crushing, calcining, sieving, adding additives, mixing, casting to form a film, discharging glue, reducing in hydrogen-nitrogen mixed gas, coating an oxidant, oxidizing in air atmosphere, and sintering to obtain the substrate for the single-layer capacitor. 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 extremely large in the production and use processes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a single-layer ceramic capacitor grain boundary layer semiconductor ceramic material 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:
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 to 3 percent of additive;
Wherein ,ZnO、CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2 and Bi 2O3 are combined. Too low or too high additives can affect the structure of the ceramic body after sintering and thus the electrical performance of the capacitor.
Further, the additive consists of ZnO、CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2 and Bi 2O3.
Further, the weight percentage of each component in the additive to the material is as follows:
Further, the material is prepared by mixing SrCO 3、TiO2 and an additive and then sintering at a high temperature.
Further, the dielectric constant k value of the material is 30000 to 50000.
The invention also provides a preparation method of the material, which comprises the following steps:
(1) Mixing SrCO 3 and TiO 2 according to a certain proportion, then mixing, ball milling, drying and pulverizing;
(2) Calcining the powder obtained in the step (1), then crushing and sieving;
(3) Adding additives into the powder obtained in the step (2) according to the proportion, 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 process conditions adopted by the mixing and ball milling in the step (1) and the step (3) are as follows: mixing and ball milling are carried out by adopting a planetary ball mill, and 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 calcination in step (2) are: calcining at 1200-1300 deg.c for 3-4 hr.
Further, the sintering conditions in the step (4) are as follows: firstly, sintering for 4 to 5 hours at 1300 to 1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000+/-50 ℃, and introducing air to perform heat preservation and sintering for 3 to 6 hours.
The invention also provides a single-layer ceramic capacitor manufactured by using 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 little pollution to the environment, does not need to adopt a secondary sintering method for coating insulating oxide in the production and preparation process, reduces the production cost, and accords with the development trend of miniaturization and high capacity of ceramic capacitors so as to meet the increasingly higher 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 to 3 percent of additive;
Wherein the additive is one or more of ZnO、CaCO3、Li2CO3、B2O3、CuO、La2O3、SiO2 and Bi 2O3, more preferably the additive consists of ZnO、CaCO3、Li2CO3、B2O3、CuO、La2O3、SiO2 and Bi 2O3.
As a further preference, the weight percentage of each component in the additive to the material is:
the material is prepared and a single-layer ceramic capacitor is manufactured by the following steps:
(1) After SrCO 3 and TiO 2 are mixed according to the proportion, deionized water is added, a planetary ball mill is adopted for mixing and ball milling, and the weight ratio of powder, grinding balls and deionized water in ball milling slurry is 1:5: (1-1.5), ball milling for 2-3 hours, then drying and crushing.
(2) Calcining the powder obtained in the step (1) for 3-4 hours at 1200-1300 ℃, then crushing and sieving.
(3) Adding an additive into the powder obtained in the step (2) according to the proportion, adding deionized water, mixing and ball milling by adopting a planetary ball mill, wherein the weight ratio of the powder, the grinding balls and the deionized water in the ball milling slurry is 1:5: (1-1.5), ball milling for 3-4 hours, then 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 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 to 5 hours at 1300 to 1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000+/-50 ℃, and introducing air to perform heat preservation and sintering for 3 to 6 hours.
(5) The ceramic body is sliced according to the required thickness to obtain a single-layer ceramic substrate for the capacitor.
(6) And (3) carrying out metallization treatment on the ceramic substrate obtained in the step (5) by 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 precise dicing saw to obtain a single-layer ceramic capacitor with the size specification of 0.2-0.8 mm;
(8) The performance test is carried out on the single-layer ceramic capacitor, and the dielectric constant (K) is 30000-50000, the loss is less than 0.025, and the insulation resistance is more than 10 9 omega.
The following table shows the ceramic material formulations of examples 1 to 3 of the present invention and the characteristics of the individual ceramic capacitors fabricated therefrom.
In the semiconductor ceramic material with the grain boundary layer, through reasonable proportion of the additives such as ZnO、CaCO3、Li2CO3、B2O3、CuO、La2O3、SiO2, bi 2O3 and the like, a stable and well-insulated grain boundary layer is formed on the grain boundary, so that the same insulating performance can be achieved without coating insulating oxide. In addition, the invention sinters the semiconductor ceramic material with excellent performance of the ceramic capacitor crystal boundary layer at one time by adjusting the sintering process, does not need to adopt a secondary sintering method for coating insulating oxide, reduces the production cost, and accords with the development trend of miniaturization and high capacity of the ceramic capacitor so as to meet the increasingly higher technical requirements.
The invention prepares the semiconductor ceramic capacitor with compact crystal boundary layer of the ceramic capacitor by the process mode of wafers (ingot pressing, ingot burning, slicing, metallization and scribing), rather than the traditional tape casting method and film extrusion method.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (7)
1. The single-layer ceramic capacitor grain boundary layer semiconductor ceramic material is characterized by being prepared from the following raw materials in percentage by weight:
SrCO3 60～69％
TiO2 30～38％
0.2 to 3 percent of additive;
wherein the additive consists of ZnO、CaCO3、CuO、La2O3、Li2CO3、B2O3、SiO2 and Bi 2O3;
The weight percentage of each component in the additive in the material is as follows:
2. The material of claim 1, wherein the material is formed by high temperature sintering after mixing SrCO 3、TiO2 with additives.
3. A method of preparing a material according to any one of claims 1 to 2, comprising the steps of:
(1) Mixing SrCO 3 and TiO 2 according to a certain proportion, then mixing, ball milling, drying and pulverizing;
(2) Calcining the powder obtained in the step (1), then crushing and sieving;
(3) Adding additives into the powder obtained in the step (2) according to the proportion, 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.
4. A method according to claim 3, wherein the mixing and ball milling in step (1) and step (3) are carried out under the following process conditions: mixing and ball milling are carried out by adopting a planetary ball mill, and 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.
5. A method according to claim 3, wherein the conditions for calcination in step (2) are: calcining at 1200-1300 deg.c for 3-4 hr.
6. A method according to claim 3, wherein the sintering conditions in step (4) are: firstly, sintering for 4 to 5 hours at 1300 to 1400 ℃ in a hydrogen-nitrogen mixed atmosphere, then cooling to 1000+/-50 ℃, and introducing air to perform heat preservation and sintering for 3 to 6 hours.
7. A single layer ceramic capacitor fabricated using the material of any one of claims 1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111668230.1A CN114334444B (en) | 2021-12-31 | 2021-12-31 | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111668230.1A CN114334444B (en) | 2021-12-31 | 2021-12-31 | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114334444A CN114334444A (en) | 2022-04-12 |
| CN114334444B true CN114334444B (en) | 2024-06-04 |
Family
ID=81020002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111668230.1A Active CN114334444B (en) | 2021-12-31 | 2021-12-31 | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114334444B (en) |
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/CN114334444B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114334444A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106673642B (en) | Giant dielectric low-loss CCTO-based ceramic material and preparation method thereof | |
| CN111908914B (en) | Grain boundary layer ceramic material, preparation method and application of grain boundary layer ceramic substrate | |
| CN111302775B (en) | Ceramic material with high quality factor and low dielectric constant and preparation method thereof | |
| CN111302787A (en) | Microwave dielectric ceramic material with high Qf and high strength and preparation method thereof | |
| CN111925187A (en) | Lead-free high-pressure medium-temperature sintered strontium bismuth titanium-based dielectric material and preparation method thereof | |
| CN113666738A (en) | Barium titanate-based X9R dielectric material for multilayer ceramic capacitor and preparation method thereof | |
| CN114334444B (en) | Single-layer ceramic capacitor grain boundary layer semiconductor ceramic material and preparation thereof | |
| CN111635227B (en) | High-frequency ceramic dielectric material, preparation method thereof and multilayer ceramic capacitor | |
| CN113248252A (en) | Stable dielectric material for MLCC and preparation method thereof | |
| CN110903085A (en) | TiO2Microwave-based ceramic substrate material, preparation method and application | |
| CN107739204B (en) | Ceramic dielectric material with excellent bias characteristic and preparation method thereof | |
| CN112266238B (en) | Low dielectric constant ceramic material for microwave device and preparation method thereof | |
| CN113307622B (en) | High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof | |
| CN112811901B (en) | High-mesomorphic-boundary-layer ceramic material and preparation method of grain boundary-layer ceramic substrate | |
| CN105669199B (en) | A kind of microwave-medium ceramics and preparation method thereof | |
| CN111574213B (en) | Low-dielectric-constant LTCC material and preparation method thereof | |
| JP2009126754A (en) | Production method for dielectric ceramic composition | |
| CN112174665A (en) | Filter ceramic with accurately controllable dielectric constant for 5G base station and preparation method thereof | |
| CN114591079B (en) | High-voltage low-loss ceramic capacitor medium and preparation method thereof | |
| CN115108825B (en) | (Sr,Ca)（Ti,Ga）O 3 -LaAlO 3 Composite microwave dielectric ceramic material and preparation method thereof | |
| CN115159977B (en) | Wide-temperature low-loss dielectric ceramic material and preparation method thereof | |
| CN115010488B (en) | Low-firing low-dielectric high-Q high-stability microwave porcelain for capacitor | |
| CN115093220B (en) | Low-temperature sintered Mg 0.5 Ti 0.5 TaO 4 Microwave-based dielectric ceramic material and preparation method thereof | |
| JP2004203626A (en) | Dielectric composition | |
| CN108585835B (en) | High-voltage ceramic capacitor medium and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |