CN116947481A - Giant dielectric constant dielectric material and preparation method and application thereof - Google Patents
Giant dielectric constant dielectric material and preparation method and application thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 77
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 239000003990 capacitor Substances 0.000 claims abstract description 12
- 230000015654 memory Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 75
- 238000005245 sintering Methods 0.000 claims description 69
- 238000000498 ball milling Methods 0.000 claims description 36
- 239000012188 paraffin wax Substances 0.000 claims description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 229910052709 silver Inorganic materials 0.000 claims description 27
- 239000004332 silver Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 75
- 229910010413 TiO 2 Inorganic materials 0.000 description 46
- 238000005303 weighing Methods 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 23
- 238000007873 sieving Methods 0.000 description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 15
- 238000003825 pressing Methods 0.000 description 15
- 229910052726 zirconium Inorganic materials 0.000 description 15
- 238000004321 preservation Methods 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
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- 238000004377 microelectronic Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of dielectric materials, and particularly relates to a giant dielectric constant dielectric material, a preparation method and application thereof. The preparation method of the giant dielectric constant dielectric material provided by the invention selects La 3+ And Ta 5+ As doping ion, the TiO is regulated and controlled by combining heat treatment in nitrogen or mixed gas atmosphere of hydrogen and nitrogen and controlling doping content 2 The dielectric property of the base dielectric material is provided, so that the dielectric material with giant dielectric constant, low dielectric loss and good frequency stability is provided, and the dielectric constant and the dielectric loss are obviously improved along with the stability of frequency while the giant dielectric constant and the low dielectric loss of the dielectric material are realized, thereby meeting the requirement of high frequencyApplication requirements in the fields of performance dielectric capacitors or dynamic memories and the like.
Description
Technical Field
The invention belongs to the technical field of dielectric materials, and particularly relates to a giant dielectric constant dielectric material, a preparation method and application thereof.
Background
In recent years, the development of microelectronic technology has put higher demands on miniaturization, large capacity and high reliability of electronic components. Dielectric capacitors are used as "foundation stones" in the microelectronics industry and are widely used in dynamic random access memory, filtering, coupling and decoupling circuits in the fields of wearable devices, mobile communications, artificial intelligence, cloud computing, and the like. To meet the development demands of microelectronics, dielectric capacitors are required to have smaller space volumes and greater storage densities. The key to the fabrication of high performance capacitors is the dielectric properties of the dielectric material that is filled within them. Giant dielectric constant dielectric materials exhibit great potential for high performance capacitor applications by virtue of their ultra-high dielectric constant. Therefore, research and preparation of giant dielectric constant dielectric materials have important promotion effect on development of electronic information industry.
At present, the research system of giant dielectric constant dielectric materials mainly comprises BaTiO 3 Material system, caCu 4 Ti 4 O 12 Material system and TiO 2 A material system. Wherein the acceptor co-doping TiO is applied 2 The system utilizes the super high dielectric constant>10 4 ) And good temperature stability, and has great application potential in the field of high-performance dielectric capacitors.
For example, the prior art discloses a method for preparing an ion-doped titania-based composite ceramic using a general formula (A) 0.5 Nb 0.5 ) 0.005 Ti 0.995 O 2 Representing the material composition, the technology optimizes the performance of the ceramic material system by adopting the addition of novel trivalent elements A (such as Bi, al, ga, Y, sc, yb, dy, sm, gd, pr and the like) and pentavalent elements Nb, and has higher dielectric constant and lower dielectric loss, so that the ceramic material system has the advantages of high-performance and low-performance ceramic materialThe capacitor, the dynamic memory and other electronic device fields have wider application space.
However, it is important for practical application to realize the stability of dielectric constant with frequency while realizing the giant dielectric constant and low dielectric loss of dielectric materials. This is because the higher the frequency stability, the higher the application value, and the field generally requires that the fluctuation of dielectric constant is within 15%, otherwise the stability of the device is directly affected, which is to be applied with co-doped TiO 2 The preparation of base dielectric materials presents new challenges.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of large fluctuation, instability and the like of the dielectric constant along with the change of frequency while realizing the giant dielectric constant and low dielectric loss of the dielectric material in the prior art, thereby providing the giant dielectric constant dielectric material and the preparation method and the application thereof.
Therefore, the invention provides the following technical scheme:
the invention provides a preparation method of a giant dielectric constant dielectric material, which comprises the following steps:
s1, tiO is added according to the mole ratio 2 ：Ta 2 O 5 ：La 2 O 3 ＝0.97～0.99:0.0025～0.0075:0.0025～0.0075
Mixing to obtain mixed powder;
s2, mixing and granulating the mixed powder with a binder, and tabletting and forming to obtain a blank;
s3, discharging glue from the obtained blank, and sintering to obtain a matrix material;
s4, carrying out heat treatment on the base material for 0.5-1.0h at 900-1100 ℃ in the atmosphere of the mixed gas of hydrogen and nitrogen, coating silver paste, and burning silver to obtain the giant dielectric constant dielectric material.
Typically, but not by way of limitation, tiO in step S1 2 ：Ta 2 O 5 ：La 2 O 3 May be in a molar ratio of 0.98:0.005:0.005,0.98:0.0025:0.0075,0.98:0.0075:0.0025,0.98:0.006:0.004,0.98:0.004:0.006,0.97:0.0075:0.0075,0.97:0.005:0.005,0.97:0.0025:0.0075,0.97:0.0075:0.0025,0.97:0.006:0.004,0.97:0.004:0.006,0.99:0.0025:0.0075,0.99:0.0075:0.0025,0.99:0.0064:0.0045 or 0.99:0.0045:0.0065, etc.
Typically, but not by way of limitation, the temperature of the heat treatment may be 900 ℃,920 ℃,940 ℃,950 ℃,960 ℃,980 ℃,1000 ℃,1030 ℃,1050 ℃,1070 ℃,1090 ℃, 1100 ℃, or the like; 0.5h,35min,36min,38min,40min,42min,45min,48min,50min,52min,55min,57min or 1h, etc.
Optionally, in the step S1, ball milling is adopted to mix materials, a ball milling medium is deionized water, and the materials are dried after ball milling;
and/or controlling the particle size of the mixed powder below 40 meshes.
Optionally, in step S2, the binder is paraffin;
and/or the addition amount of the binder accounts for 6-8% of the mass of the mixed powder. Typically, but not limited to, the binder may be added in an amount of 6%,6.3%,6.5%,6.8%,7%,7.2%,7.5%,7.8% or 8% by mass of the powder mix, etc.
Optionally, in step S2, the particle size is controlled below 80 mesh in the step of mixing and granulating;
and/or the pressure of the tabletting and forming step is 2MPa-4MPa. Typically, without limitation, the pressure of the tablet forming step may be 2MPa,2.2MPa,2.4MPa,2.5MPa,2.7MPa,2.9MPa,3MPa,3.3MPa,3.5MPa,3.6MPa,3.8MPa, 4MPa, or the like.
Optionally, in step S3, the step of removing the adhesive includes: heating to 400-600 ℃ at a heating rate of 2-3 ℃/min. Typically, but not limited to, the temperature rise rate of the glue removal step may be 2 ℃/min,2.2 ℃/min,2.4 ℃/min,2.5 ℃/min,2.6 ℃/min,2.8 ℃/min or 3 ℃/min, etc.; the glue discharging temperature in the glue discharging step can be 400 ℃,420 ℃,440 ℃,450 ℃,460 ℃,480 ℃,500 ℃,520 ℃,540 ℃,550 ℃,560 ℃,580 ℃, 600 ℃ or the like.
Optionally, in the step S3, the temperature of the sintering step is 1300-1440 ℃, and the temperature is kept for 4-10 h. Typically, but not by way of limitation, the sintering step may be at a temperature of 1300 ℃,1320 ℃,1340 ℃,1350 ℃,1360 ℃,1380 ℃,1400 ℃,1420 ℃, 1440 ℃, or the like.
Optionally, in step S4, the volume of hydrogen in the mixed gas of hydrogen and nitrogen is 0.5% -5%. Typically, but not limited to, the hydrogen and nitrogen mixture may have a hydrogen concentration of 0.5%,1%,1.2%,1.5%,1.8%,2%,2.2%,2.5%,2.8%,3%,3.2%,3.5%,3.8%,4%,4.2%,4.5%,4.8% or 5% by volume.
Optionally, in step S4, the silver burning temperature is 800-840 ℃ and the silver burning time is 1.5-2 h. Typically, but not limited to, the temperature of the burned silver may be 800 ℃,805 ℃,810 ℃,815 ℃,820 ℃,825 ℃,830 ℃,835 ℃, 840 ℃, or the like; the silver burning time can be 1.5h,95min,100min,105min,110min,115min or 2h, etc.
The invention also provides the giant dielectric constant dielectric material prepared by the preparation method.
The invention also provides application of the giant dielectric constant dielectric material in a dielectric capacitor or a dynamic memory.
The invention provides a preparation method of a giant dielectric constant dielectric material, which comprises the following steps:
s1, tiO is added according to the mole ratio 2 ：Ta 2 O 5 ：La 2 O 3 ＝0.97～0.99:0.0025～0.0075:0.0025～0.0075
Mixing to obtain mixed powder;
s2, mixing and granulating the mixed powder with a binder, and tabletting and forming to obtain a blank;
s3, performing glue discharging sintering on the obtained blank to obtain a matrix material;
s4, performing primary heat treatment on the substrate material in a nitrogen atmosphere, and then performing secondary heat treatment for 0.5-1.0h at 900-1100 ℃ in a mixed gas atmosphere of hydrogen and nitrogen, coating silver paste, and burning silver to obtain the giant dielectric constant dielectric material.
Another giant dielectric constant provided by the inventionPreparation method of digital medium material by selecting La 3+ And Ta 5+ As doping ions, the substrate material after the adhesive discharging sintering is combined with the primary heat treatment under the nitrogen atmosphere, so that the dielectric loss of the material can be obviously reduced, and then the secondary heat treatment is carried out under the mixed atmosphere of hydrogen and nitrogen, so that the stability of the dielectric constant along with the frequency can be obviously improved. The dielectric loss (1 kHz,25 ℃) of the obtained giant dielectric constant dielectric material can be lower than 0.1, more preferably, the dielectric loss can be lower than 0.09, and meanwhile, the fluctuation of the dielectric constant along with the frequency change (1 kHz, 25-1 MHz,25 ℃) is within 15 percent, so that the giant dielectric constant material is relatively stable.
Optionally, the temperature of the primary heat treatment is 900-1000 ℃ and the treatment time is 0.5-1h.
Typically, but not limited to, the temperature and time of the primary heat treatment step and the secondary heat treatment step may be the same or different, as long as the heat treatment temperature and time are within the above-defined ranges. For example, the temperature of the primary and/or secondary heat treatments may be 900 ℃,920 ℃,940 ℃,950 ℃,960 ℃,980 ℃,1000 ℃,1030 ℃,1050 ℃,1070 ℃,1090 ℃, 1100 ℃, or the like; the time of the primary heat treatment and/or the secondary heat treatment can be 0.5h,35min,36min,38min,40min,42min,45min,48min,50min,52min,55min,57min or 1h, etc.
The technical scheme of the invention has the following advantages:
the preparation method of the giant dielectric constant dielectric material provided by the invention selects La 3+ And Ta 5+ As doping ion, combining with heat treatment in the atmosphere of mixed gas of hydrogen and nitrogen, regulating and controlling TiO by controlling doping content 2 The dielectric property of the base dielectric material is improved, the dielectric constant is obviously improved along with the stability of frequency, the fluctuation range is within 15%, and the application requirements of the fields of high-performance dielectric capacitors or dynamic memories and the like are met.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a reducing atmosphere furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thereby preparing hugeA sample of a dielectric constant material.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 2
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding paraffin with the mass percentage of 7% into the dried powder, fully mixing and parching, and granulating by sieving with a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the wafer green body, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the donor-acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 3
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
first, select an electronBalance as weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.99:0.0025:0.0025, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by sieving with a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the wafer green body, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the donor-acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 4
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas for heat treatment is 900 ℃ and the sintering time is 0.6h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 5
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base dielectric material is placed in a sintering furnace for heat treatment,the atmosphere in the sintering furnace is H with hydrogen volume concentration of 1% 2 /N 2 The sintering temperature of the mixed gas is 1000 ℃ and the sintering time is 0.8h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 6
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 5 percent 2 /N 2 The temperature of the mixed gas for heat treatment is 1100 ℃, and the sintering time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 7
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 0.5 percent 2 /N 2 The temperature of the mixed gas for heat treatment is 1100 ℃, and the sintering time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Example 8
The embodiment provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of (0.98:0.005:0.005), placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, and adding 8% of the mass percentage into the dried powderFully mixing and parching, sieving with 80 mesh sieve, granulating to obtain powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 240 minutes, removing paraffin from the wafer green body, continuously heating to 1400 ℃, preserving heat for 6 hours, and fully sintering to obtain the donor-acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a reducing atmosphere furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 1
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the wafer green body, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to prepare the giant dielectric constant medium material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 2
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the wafer green body, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the donor-acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, the atmosphere in the sintering furnace is pure nitrogen, the heat treatment temperature is 1100 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 3
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, the atmosphere in the sintering furnace is air, the heat treatment temperature is 1100 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 4
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Accurately weighing 0.5g of powder material, pressing the granulated powder material into a wafer green body with the diameter of phi 10 multiplied by 2mm under the condition of the pressure of 2MPa,then heating from room temperature to 550 ℃ for 210 minutes, removing paraffin wax in the wafer green compact, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to prepare the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a sintering furnace for heat treatment, the atmosphere in the sintering furnace is pure nitrogen, the heat treatment temperature is 1200 ℃, and the sintering time is 3 hours; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 5
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 Placing the base medium material in a sintering furnace for heat treatment, wherein the atmosphere in the sintering furnace is pure nitrogen, the heat treatment temperature is 1300 ℃, and the sintering time is 5 hours; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 6
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Nb 2 O 5 ：La 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the volume ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a reducing atmosphere furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Comparative example 7
The comparative example provides a preparation method of a giant dielectric constant dielectric material, which comprises the following specific steps and operation parameters:
firstly, an electronic balance is selected as a weighing tool according to TiO 2 ：Ta 2 O 5 ：Ce 2 O 3 Accurately weighing the molar ratio of 0.98:0.005:0.005, placing deionized water, zirconium balls and powder in a ball milling tank according to the ratio of 2:1:1, ball milling for 12 hours by using a planetary ball mill, drying, sieving with a 40-mesh sieve, adding 8% paraffin by mass into the dried powder, fully mixing and parching, and granulating by using a 80-mesh sieve to obtain the powder material.
Precisely weighing 0.5g of powder material, pressing the granulated powder material into a green disc with the diameter of phi of 10 multiplied by 2mm under the pressure of 2MPa, heating to 550 ℃ from room temperature for 210 minutes, removing paraffin from the green disc, continuously heating to 1440 ℃, preserving heat for 10 hours, and fully sintering to obtain the acceptor co-doped TiO 2 A base dielectric material.
The donor obtained is co-doped with TiO 2 The base medium material is placed in a reducing atmosphere furnace for heat treatment, and the atmosphere in the sintering furnace is H with the hydrogen volume concentration of 1 percent 2 /N 2 The temperature of the mixed gas is 1100 ℃, the temperature rising rate is 3 ℃/min, and the heat preservation time is 0.5h; thus preparing a giant dielectric constant dielectric material sample.
The upper and lower surfaces of the obtained product are uniformly coated with silver paste, electrodes are prepared by sintering and infiltrating for 2 hours at 840 ℃, samples to be tested are prepared, the dielectric properties are tested, and the test results are shown in Table 1.
Test case
The dielectric property test is carried out on the samples to be tested obtained by the embodiment and the comparative example, and the specific test method and the detection equipment are as follows:
1. dielectric Property test (test frequency 1kHz, voltage 1.0V; test frequency 1MHz, voltage 1.0V)
Capacitance (C) and dielectric loss (tan δ) of the sample were measured using an agilent 4294a precision impedance analyzer, and the dielectric loss of the sample was calculated using formula (1-1):
wherein epsilon represents the dielectric constant of the sample to be measured, C represents the capacitance of the sample to be measured, D represents the thickness of the sample to be measured, and D represents the diameter of the sample to be measured.
The specific test results of the giant dielectric constant dielectric materials provided in each example and comparative example are shown in table 1:
TABLE 1 sample dielectric constant and dielectric loss test results
As can be seen from the data in the above table, la was used in the examples of the present invention 3+ Ions and Ta 5+ Doping ions, and carrying out heat treatment by combining nitrogen-hydrogen mixed atmosphere to obtain TiO 2 Compared with a comparative sample, the giant dielectric constant dielectric material obtained in each embodiment has excellent dielectric properties, and the prepared material has excellent dielectric properties by adjusting doping ions and a preparation process, so that the giant dielectric constant and low dielectric loss of the dielectric material are realized, the stability of the dielectric constant along with frequency is obviously improved, and the fluctuation range is within 15 percent, thereby being expected to be applied to dielectric capacitors and dynamic memories. Specifically, comparative example 1 was lower in dielectric constant and unstable with frequency change if sintering was not performed, compared with example 1; comparative example 2 has a dielectric loss lower than that of example 1, but the dielectric constant fluctuation was about 54%, and the fluctuation was unstable with the frequency; this is mainly due to the fact that the crystal microstructure of the dielectric material is destroyed by heat treatment under nitrogen conditions, resulting in a change in the internal charge distribution and in an unstable state, which is susceptible to frequency. Comparative example 3 is different from example 1 only in the heat treatment atmosphere, and the air is used instead of the mixed gas atmosphere of hydrogen and nitrogen, and comparative examples 4 to 5 are different from example 1 in the temperature and time of the heat treatment step are not within the scope of the present invention, and comparative examples 6 to 7 are compared with example 1The difference is only that the doping elements are different, nb is used in comparative example 6 2 O 5 Instead of Ta 2 O 5 Comparative example 7 uses Ce 2 O 3 Replacing La 2 O 3 From the test results shown in Table 1, the results of comparative examples 3 to 7 are far less susceptible to frequency variation than those of example 1, and particularly dielectric constants, and the fluctuation with frequency is 15% or more, which cannot meet the application requirements in the fields of high-performance dielectric capacitors or dynamic memories.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the giant dielectric constant dielectric material is characterized by comprising the following steps:
s1, tiO is added according to the mole ratio 2 ：Ta 2 O 5 ：La 2 O 3 ＝0.97～0.99:0.0025～0.0075:0.0025～0.0075
Mixing to obtain mixed powder;
s2, mixing and granulating the mixed powder with a binder, and tabletting and forming to obtain a blank;
s3, discharging glue from the obtained blank, and sintering to obtain a matrix material;
s4, carrying out heat treatment on the base material for 0.5-1.0h at 900-1100 ℃ in the atmosphere of the mixed gas of hydrogen and nitrogen, coating silver paste, and burning silver to obtain the giant dielectric constant dielectric material.
2. The method for preparing giant dielectric constant dielectric material according to claim 1, wherein in step S1, ball milling is adopted to mix materials, ball milling medium is deionized water, and drying is carried out after ball milling;
and/or controlling the particle size of the mixed powder below 40 meshes.
3. The method of claim 1, wherein in step S2, the binder is paraffin;
and/or the addition amount of the binder accounts for 6-8% of the mass of the mixed powder.
4. The method for producing a giant dielectric constant dielectric material according to claim 1, wherein in step S2, the particle size is controlled to be 80 mesh or less in the step of mixing granulation;
and/or the pressure of the tabletting and forming step is 2MPa-4MPa.
5. The method of claim 1, wherein in step S3, the step of removing the adhesive comprises: heating to 400-600 ℃ at a heating rate of 2-3 ℃/min.
6. The method for preparing giant dielectric constant dielectric material according to claim 1, wherein in the step S3, the sintering step is performed at 1300-1440 ℃ for 4-10 h.
7. The method of any one of claims 1-6, wherein in step S4, the hydrogen is mixed with nitrogen to form a mixture with a concentration of 0.5% -5% by volume.
8. The method for preparing giant dielectric constant dielectric material according to any one of claims 1 to 6, wherein in the step S4, the temperature of firing silver is 800 ℃ to 840 ℃ and the time of firing silver is 1.5h to 2h.
9. A giant dielectric constant dielectric material prepared by the method of any one of claims 1 to 8.
10. Use of a giant permittivity dielectric material according to claim 9 in a dielectric capacitor or dynamic memory.
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