CN105777112A - Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic and preparation method thereof - Google Patents

Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic and preparation method thereof Download PDF

Info

Publication number
CN105777112A
CN105777112A CN201610225867.6A CN201610225867A CN105777112A CN 105777112 A CN105777112 A CN 105777112A CN 201610225867 A CN201610225867 A CN 201610225867A CN 105777112 A CN105777112 A CN 105777112A
Authority
CN
China
Prior art keywords
acceptor
srtio
doped
ceramic material
dielectric ceramic
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.)
Granted
Application number
CN201610225867.6A
Other languages
Chinese (zh)
Other versions
CN105777112B (en
Inventor
曹明贺
王娜娜
何子晨
刘韩星
郝华
尧中华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201610225867.6A priority Critical patent/CN105777112B/en
Publication of CN105777112A publication Critical patent/CN105777112A/en
Application granted granted Critical
Publication of CN105777112B publication Critical patent/CN105777112B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

The invention belongs to the technical field of dielectric ceramic materials, and particularly relates to a Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic and a preparation method thereof. The Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic material is characterized by being formed by replacing Ti4+ with a donor Nb5+ and an acceptor Al3+, and being expressed through a formula of Sr(Nb0.5Al0.5)xTi(1-x)O3, wherein x is larger than or equal to 0.08 and smaller than or equal to 0.10; a Ti element in a SrTiO3 base system obtained after donor-acceptor co-doping exists in a Ti3+ and Ti4+. The Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic is high in dielectric constant and low in dielectric loss. According to the preparation method, air atmosphere sintering is adopted, the atmosphere can be obtained and controlled, the technology is simple, and industrial production is easy.

Description

A kind of Ti position is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof
Technical field
The invention belongs to dielectric ceramic material technical field, be specifically related to a kind of Ti position and execute acceptor and be co-doped with SrTiO3Base high dielectric is made pottery Porcelain and preparation method thereof.
Background technology
Along with microelectric technique market is to practical device miniaturization, integrated, intelligence such as ceramic capacitor and microwave-medium components and parts The demand of energyization, to having the research of the good dielectric ceramic of high-k, low-dielectric loss and temperature/frequency stability more More getting more and more people's extensive concerning, particularly it is as the dielectric material of dynamic RAM electric capacity and cmos fet The gate medium aspect of pipe logic device has a wide range of applications.At present, the material system being applied to develop high-k is main There is following a few class: complex phase giant dielectric material, transition metal oxide, rare earth oxide and the ceramic material of perovskite structure.? In single-phase giant dielectric material, there is perovskite structure ceramic material and studied the most widely, ferroelectric and relaxor ferroelectric Body such as BaTiO3Series ceramic material, dielectric constant is typically larger than 1000, but its high-k to be mainly derived from curie point attached Near ferroelectric phase transition, owing to ferroelectric occurs ferroelectric phase to the transformation of paraelectric phase at Curie temperature so that the dielectric of ferroelectric material Constant is the most affected by temperature, thus causes the bad stability of device.And containing right in lead system perovskite high dielectric material The Element Lead of bad environmental, volatile during high temperature, it is unfavorable for environmental conservation.Another kind of Ca-Ti ore type CaCu3Ti4O12(it is called for short CCTO) ceramic material is one of high dielectric material of receiving publicity in recent years, not only has high dielectric constant (> 104), And dielectric constant can keep constant within the scope of comparatively wide temperature, but, research finds that CCTO material has Gao Jie While electric constant, dielectric loss is the highest, is difficult to be widely used in capacitor, memorizer etc. and needs the electronics device of high-k In part.So, find and a kind of both there is high dielectric constant, there is again low dielectric loss, the temperature also having had and frequency The material of stability just has obvious practical significance.
SrTiO3Being at room temperature a cube paraelectric phase structure, Curie temperature is the lowest, does not has phase transformation, and temperature more than Curie temperature Stability is fine, and compared with CCTO high-permitivity ceramics, dielectric loss is the lowest and excellent in stability, compared with Barium metatitanate. system not Fatigue and problem of aging can be caused, in dielectric ceramic field by concern for many years.But pure SrTiO3The dielectric of ceramic material Constant only has about 300, can be effectively improved SrTiO by the way of doping vario-property3The dielectric properties of pottery.Donor doping Being two kinds of effective non-equivalence doping vario-property modes with acceptor doping, donor doping is primarily referred to as the valence state of substitution ion higher than being taken For a kind of doped forms of ionic valence condition, electronics can be discharged by donor doping and form ionizing, irremovable positive electricity Lotus center, doping result is to significantly improve the carrier concentration in material, makes material semiconducting；And acceptor doping is mainly Referring to that the valence state of substitution ion is less than a kind of doped forms being replaced ionic valence condition, acceptor doping has electronics and defect compensating effect, SrTiO can be improved3In dielectric loss and leakage problem.Therefore, use herein and execute mode that acceptor is co-doped with and at air In be sintered, it is intended to introduce electronics and defect compensating while carrier providing, make carrier local at dipole defect bunch In group, it is impossible to carry out long-range and move, thus while improving dielectric constant, reduce leakage conductance electric current and dielectric loss.
Summary of the invention
A technical problem to be solved by this invention is to provide a kind of and has high-k, low-dielectric loss and good The Ti position of temperature stability and frequency stability is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material.
Another technical problem to be solved by this invention is that providing a kind of Ti position to execute acceptor is co-doped with SrTiO3Base high dielectric ceramic The preparation method of material.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
There is provided a kind of Ti position to execute acceptor and be co-doped with SrTiO3Base high dielectric ceramic material, by alms giver Nb5+, acceptor Al3+Replace Ti4+ And obtain, with formula Sr (Nb0.5Al0.5)xTi1-xO3Represent, 0.08≤x≤0.10 in formula, execute the SrTiO after acceptor is co-doped with3Matrix In system, Ti element is mainly with Ti3+And Ti4+Presented in.
By such scheme, described Ti position is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material is by SrCO3、Nb2O5、 Al2O3、TiO2By formula Sr (Nb0.5Al0.5)xTi1-xO3Stoichiometric proportion 1:x/4:x/4:(1-x) pottery that is mixed Porcelain base substrate in air 1560～1620 DEG C of heat preservation sinterings and obtain.
Above-mentioned Ti position is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material Sr (Nb0.5Al0.5)xTi1-xO3Preparation method, will SrCO3、Nb2O5、Al2O3、TiO2By formula Sr (Nb0.5Al0.5)xTi1-xO3Stoichiometric proportion 1:x/4:x/4:(1-x) Ball milling after mixing, dries, pre-burning, and then secondary ball milling obtains pre-burning powder body, pre-burning powder body is added binding agent pelletize and sieves, Molding, then binder removal obtains ceramic body, then by ceramic body 1560～1620 DEG C of heat preservation sinterings in air, with after through program The ceramic material of sintering is obtained after cooling.
In such scheme, described ball milling is wet ball-milling, adds ball-milling medium and dispersant dehydrated alcohol, and ball milling 20～30 is little Shi Hou, separates ball-milling medium, is then put in drying baker by the raw mixture after ball milling and dry.
In such scheme, described drying temperature is 100～150 DEG C, and drying time is 10～15 hours.
In such scheme, described calcined temperature is 1150～1180 DEG C, and burn-in time is 2～3 hours.
In such scheme, described pelletize sticks with glue the poly-vinyl alcohol solution that agent is 5wt%.
In such scheme, described compression molding is: under the pressure of 10～15MPa, composite granule is pressed into a diameter of 12mm, Thickness is the disk of 1～1.5mm.
In such scheme, the heat preservation sintering time of described ceramic body is 2～4 hours.
The invention has the beneficial effects as follows:
The present invention is by SrTiO3Carry out Ti position execute acceptor's equivalent be co-doped with replace, utilize alms giver Nb5+At Ti4+Replacement formed Ti4+E, utilizes acceptor Al3+At Ti4+Replacement formedTi4+E andIt is internally formed a considerable number of at potteryPolaron cluster, it is possible to make electronic localization, reduces leakage conductance electric current and dielectric loss, shape simultaneously The a large amount of disfigurement model become can improve polarizability, and then improves dielectric constant, thus obtains high-k and low dielectric damage The SrTiO of consumption3Base ceramic material.When Nb, Al amount of being co-doped with is too low, it is impossible to form substantial amounts of disfigurement model, often rise not To the purpose of raising dielectric constant, and when the amount of being co-doped with is too high, free electron number increases, and dielectric loss is significantly increased.
The Ti position that the present invention provides is executed acceptor and is co-doped with replacing SrTiO3High dielectric ceramic dielectric constant is high, and dielectric loss is low.Such as x Value when being 0.10, ceramic material dielectric constant under 1kHz when room temperature is 8078, and dielectric loss is 0.026, and is situated between Electric constant varies less in wider frequency and temperature range, and test frequency is that dielectric loss during 1kHz is at 25 DEG C simultaneously ～within the temperature range of 60 DEG C≤0.03.
The Ti position that the present invention provides is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material Sr (Nb0.5Al0.5)xTi1-xO3Preparation side Method uses air atmosphere sintering, and atmosphere can obtain controlled, and technique is simple, it is easy to industrialized production.
For the material powder of the present invention, granularity and particle diameter are had no special requirements, therefore can reduce production cost.
Accompanying drawing explanation
Fig. 1 is the Sr (Nb sintered in air in the embodiment of the present invention 10.5Al0.5)0.08Ti0.92O3High dielectric constant ceramic material XRD figure is composed.
Fig. 2 is the Sr (Nb sintered in air in the embodiment of the present invention 10.5Al0.5)0.08Ti0.92O3In high dielectric constant ceramic material Nb (a) and the XPS collection of illustrative plates of Ti (b) element.
Fig. 3 is the Sr (Nb sintered in air in the embodiment of the present invention 10.5Al0.5)0.08Ti0.92O3The friendship of high dielectric constant ceramic material Flow impedance collection of illustrative plates, illustration is the enlarged drawing of high band AC impedance.
Fig. 4 is the Sr (Nb sintered in air in the embodiment of the present invention 10.5Al0.5)0.08Ti0.92O3Jie of high dielectric constant ceramic material Electricity thermogram.
Fig. 5 is to sinter SrTiO in comparative example 1 of the present invention in air3The dielectric thermogram of ceramic material.
Fig. 6 is nitrogen assisted sintering Sr (Nb in comparative example 4 of the present invention0.5 Al0.5)0.08Ti0.92O3The dielectric thermogram of ceramic material.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment and accompanying drawing, but the present invention Content is not limited solely to the following examples.
Embodiment 1
The present embodiment provides Sr (Nb0.5Al0.5)0.08Ti0.92O3The preparation method of represented ceramic material, specifically comprises the following steps that
1) oxide composite powder is prepared
By Sr (Nb0.5Al0.5)0.08Ti0.92O3Stoichiometric proportion be equipped with raw material compound gross weight be 25g, by raw material SrCO3、 Nb2O5、Al2O3、TiO2Mixture loads in ball grinder, adds zirconium ball and dehydrated alcohol.After ball milling 24 hours, separating zirconium Ball, puts into mixture slurry in drying baker and dries, and drying baker temperature is set to 100 DEG C and is dried 12 hours, after drying Compound manually grind and be placed in Muffle furnace in 1150 DEG C of pre-burnings 2 hours, naturally cool to room temperature.Powder after calcining Body need to carry out secondary ball milling, and mechanical milling process is consistent with primary mechanical milling process.
2) ceramic body is prepared
Pre-burning powder body after secondary ball milling need to add binding agent to carry out pelletize and sieves, and obtains having the spherical of certain particle size grating Powder.Specifically comprising the following steps that of this process uses the poly-vinyl alcohol solution that concentration is 5wt% prepared as binding agent, presses The ratio adding 3 binding agents according to 1g powder is ground in three times, and the powder after grinding is had after crossing the sieve of 80 mesh The spherical powder of certain particle size grating.
Weighing 0.4g granulation powder every time, put in mould, through dry-pressing formed obtaining a diameter of 12mm, thickness is 1～1.5mm Disk.Ceramic body after molding need to get rid of polyvinyl alcohol colloid before sintering, and the actual temp system of binder removal is as follows: in horse After not stove rising to 600 DEG C according to the heating rate of 1 DEG C/min and is incubated 120min, naturally cool to room temperature.
3) porcelain is sintered into
The ceramic body being drained through glue is placed in high temperature furnace the process that is sintered, and the actual temp system of sintering is: first with The heating rate of 5 DEG C/min is warming up to 1000 DEG C, is then warming up to 1590 DEG C with the heating rate of 2 DEG C/min and is incubated 3 hours, Then it is cooled to 1000 DEG C so that 2 DEG C/min is per minute, then is cooled to 300 DEG C with 5 DEG C/min, finally naturally cool to room with stove Temperature.
Sr(Nb0.5Al0.5)0.08Ti0.92O3The XRD figure of ceramics sample is as shown in Figure 1.As seen from Figure 1, high temperature in air Sr (the Nb of sintering0.5Al0.5)0.08Ti0.92O3Ceramics sample is complete cubic perovskite structure, dephasign does not occur, illustrate Nb, A cube SrTiO is entered in Al solid solution completely3In crystal.
Sr(Nb0.5Al0.5)0.08Ti0.92O3In ceramics sample, the XPS spectrum figure of Nb and Ti element is respectively as shown in Fig. 2 (a), 2 (b). As seen from Figure 2, the 3d of Nb5/2With 3d3/2The combination energy difference of energy level is 2.8eV, and at the 3d of Nb5/2At energy level Other energy level peak does not occur, illustrates that in this ceramic material, the valence state of Nb is+5 valencys, and Ti element is mainly with Ti3+And Ti4+ Presented in, Ti3+/Ti4+Atomic percent～25.3%.
Sr(Nb0.5Al0.5)0.08Ti0.92O3The impedance spectrogram of ceramic material is as shown in Figure 3.Sr(Nb0.5Al0.5)0.08Ti0.92O3Pottery material The dielectric temperature of material is composed as shown in Figure 4.As seen from the figure, the Sr (Nb of high temperature sintering in air0.5Al0.5)0.08Ti0.92O3Ceramic Like Product are in the range of 25～140 DEG C, in the frequency range of 100Hz～1MHz, dielectric constant>5000 simultaneously dielectric loss<0.1, its In when room temperature (25 DEG C) dielectric constant under 1kHz be 6134, dielectric loss is 0.018.
Embodiment 2
The present embodiment provides Sr (Nb0.5Al0.5)0.10Ti0.90O3The preparation method of represented ceramic material, in addition to following difference, Remaining step is same as in Example 1:
Step 1 in embodiment 1) in, by Sr (Nb0.5Al0.5)0.10Ti0.90O3Stoichiometric proportion be equipped with raw material compound gross weight For 30g.After ball milling 30 hours, separating zirconium ball, mixture slurry to be put in drying baker and dries, drying baker temperature sets Being 100 DEG C and be dried 15 hours, the compound after drying manually grinds and is placed in Muffle furnace in 1150 DEG C of pre-burnings 3 hours, Naturally cool to room temperature.
Step 3 in embodiment 1) in, sintering temperature is set to 1560 DEG C and is incubated 4 hours.
Sr (the Nb of preparation0.5Al0.5)0.10Ti0.90O3Ceramics sample, has high-k and low-dielectric loss, when 25 DEG C Dielectric constant and dielectric loss under 1kHz are respectively 8203 and 0.025.
Embodiment 3
The present embodiment provides Sr (Nb0.5Al0.5)0.08Ti0.92O3The preparation method of represented ceramic material, in addition to following difference, Remaining step is same as in Example 1:
Step 1 in embodiment 1) in, ball milling is after 20 hours, separating zirconium ball, is then put in drying baker by mixture slurry Drying, drying baker temperature is set to 150 DEG C and is dried 10 hours.Compound after drying manually grinds and is placed on Muffle Calcine 2.5 hours in 1150 DEG C in stove, naturally cool to room temperature.
Step 3 in embodiment 1) in, it is incubated 2 hours at 1620 DEG C during sintering.
Sr (the Nb of preparation0.5Al0.5)0.08Ti0.92O3When room temperature (25 DEG C), the dielectric constant under 1kHz is 6047, dielectric loss It is 0.023.
Comparative example 1
By SrCO3And TiO2According to SrTiO3Stoichiometric proportion proportioning mixing, with dehydrated alcohol as dispersant, use wet type ball 24 hours post-dryings of mill method mixing and ball milling, then calcine 2 hours in 1150 DEG C of air.Powder after calcining is little through 24 Time secondary ball milling process post-drying, add 5wt% poly-vinyl alcohol solution pelletize and also sieve.Through dry-pressing formed prepared a diameter of 12mm, thickness are the ceramic body of 1～1.5mm.By its 1600 DEG C of heat preservation sinterings 3 hours in atmosphere, obtain sintering SrTiO3Ceramic material, in whole preparation process, NM part is all identical with the condition of embodiment 1.To preparation SrTiO3Pottery carries out dielectric properties test, and its dielectric temperature is composed as shown in Figure 6, figure obtain: 25 DEG C, under the conditions of 1kHz, Its dielectric constant and dielectric loss are respectively 319 and 0.005, and dielectric properties are co-doped with significantly lower than Nb, Al of the present invention SrTiO3High dielectric ceramic material.
Comparative example 2
By SrCO3、Al2O3、TiO2According to SrAl0.05Ti0.95O3Stoichiometric proportion proportioning mixing, with dehydrated alcohol for dispersion Agent, by 24 hours post-dryings of wet ball-milling method mixing and ball milling, then calcines 2 hours in 1150 DEG C of air atmospheres.After calcining Powder process post-drying through the secondary ball milling of 24 hours, add 5wt% poly-vinyl alcohol solution pelletize and also sieve.Become through dry-pressing The ceramic body that type prepares a diameter of 12mm, thickness is 1～1.5mm.By its in air 1560 DEG C sinter 3 hours, SrAl to sintering0.05Ti0.95O3Ceramic material, in whole preparation process NM part all with the condition phase of embodiment 1 With.SrAl to preparation0.05Ti0.95O3Pottery carries out dielectric properties test, obtains: 25 DEG C, under the conditions of 1kHz, it is situated between Electric constant and dielectric loss are respectively 286 and 0.003, and it is common that dielectric constant and dielectric loss are below Nb, Al of the present invention Mix SrTiO3High dielectric ceramic material.
Comparative example 3
By SrCO3、Nb2O3、TiO2According to SrNb0.05Ti0.95O3Stoichiometric proportion proportioning mixing, with dehydrated alcohol for dispersion Agent, by 24 hours post-dryings of wet ball-milling method mixing and ball milling, then calcines 2 hours in 1150 DEG C of air atmospheres.After calcining Powder process post-drying through the secondary ball milling of 24 hours, add 5wt% poly-vinyl alcohol solution pelletize and also sieve.Become through dry-pressing The ceramic body that type prepares a diameter of 12mm, thickness is 1～1.5mm.By its 1600 DEG C of heat preservation sinterings 3 hours in atmosphere, Obtain the SrNb of sintering under air0.05Ti0.95O3Ceramic material, in whole preparation process NM part all with embodiment 1 Condition identical.SrNb to preparation0.05Ti0.95O3Pottery carries out dielectric properties test, obtains: 25 DEG C, 1kHz condition Under, its dielectric constant and dielectric loss are respectively 2297 and 0.435, and dielectric constant is common significantly lower than Nb, Al of the present invention Mix SrTiO3High dielectric ceramic material, and dielectric loss is co-doped with SrTiO apparently higher than Nb, Al of the present invention3High dielectric ceramic Material.
Comparative example 4
By SrCO3、Al2O3、Nb2O5、TiO2According to Sr (Nb0.5Al0.5)0.08Ti0.92O3Stoichiometric proportion proportioning mixing, with Dehydrated alcohol is dispersant, by 24 hours post-dryings of wet ball-milling method mixing and ball milling, then calcines in 1150 DEG C of air atmospheres 2 hours.Powder after calcining processes post-drying through the secondary ball milling of 24 hours, adds 5wt% poly-vinyl alcohol solution pelletize also Sieve.The ceramic body that a diameter of 12mm, thickness are 1～1.5mm is prepared through dry-pressing formed.By it in nitrogen atmosphere 1590 DEG C sinter 3 hours, obtain the Sr (Nb of sintering in nitrogen0.5Al0.5)0.08Ti0.92O3Ceramic material.And it is carried out dielectric Performance test, its dielectric temperature composes as shown in Figure 6, figure obtains: 25 DEG C, under the conditions of 1kHz, its dielectric constant and dielectric Loss is respectively 29946 and 0.13, and dielectric loss is co-doped with SrTiO far above Nb, Al of the present invention3High dielectric ceramic material, When dielectric loss is excessive, when pottery uses as device, it may occur that thermal breakdown or conductance puncture, it is impossible to stable use.
Comparative example 5
By SrCO3、Al2O3、Nb2O5、TiO2Respectively according to Sr (Nb0.5Al0.5)0.04Ti0.96O3With Sr (Nb0.5Al0.5)0.2Ti0.8O3 The mixing of stoichiometric proportion proportioning, with dehydrated alcohol as dispersant, by 24 hours post-dryings of wet ball-milling method mixing and ball milling, so After in 1150 DEG C of air atmospheres calcine 2 hours.Powder after calcining processes post-drying through the secondary ball milling of 24 hours, adds Add 5wt% poly-vinyl alcohol solution pelletize and sieve.The pottery that a diameter of 12mm, thickness are 1～1.5mm is prepared through dry-pressing formed Base substrate.By its in atmosphere 1590 DEG C sinter 3 hours, respectively obtain in air the Sr (Nb of sintering0.5Al0.5)0.04Ti0.96O3With Sr(Nb0.5Al0.5)0.2Ti0.8O3Ceramic material.25 DEG C, under 1kHz test condition, Sr (Nb0.5Al0.5)0.04Ti0.96O3Pottery material Dielectric constant and the dielectric loss of material are respectively 2738 and 0.06, and dielectric constant is co-doped with far below Nb, Al of the present invention SrTiO3High dielectric ceramic material, Sr (Nb0.5Al0.5)0.2Ti0.8O3Dielectric constant and the dielectric loss of ceramic material are respectively 8880 With 0.10, dielectric loss is co-doped with SrTiO far above Nb, Al of the present invention3High dielectric ceramic material.
The present invention is by whether be doped, and uses which kind of component doping, uses which kind of calcination atmosphere, to the pottery prepared respectively Ceramic material has carried out the investigation of dielectric properties, and experimental result contrast shows: the present invention is by using Nb, Al to be co-doped with, and controls Each auto-doping amount and control sintering atmosphere, it is ensured that final Nb, Al obtained is co-doped with SrTiO3The dielectric properties of ceramics sample (high-k and low-dielectric loss), and its be also superior in same component nitrogen sintering Nb or Al mono-adulterate SrTiO3The dielectric properties of ceramics sample.

Claims (7)

1. a Ti position is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material, it is characterised in that: by alms giver Nb5+, acceptor Al3+Replace Ti4+And obtain, with formula Sr (Nb0.5Al0.5)xTi1-xO3Represent, 0.08≤x≤0.10 in formula, execute after acceptor is co-doped with SrTiO3In matrix system, Ti element is mainly with Ti3+And Ti4+Presented in.
Ti position the most according to claim 1 is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material, it is characterised in that: institute The Ti position stated is executed acceptor and is co-doped with SrTiO3Base high dielectric ceramic material is by SrCO3、Nb2O5、Al2O3、TiO2By formula Sr(Nb0.5Al0.5)xTi1-xO3Stoichiometric proportion 1:x/4:x/4:(1-x) ceramic body that is mixed is in air 1560～1620 DEG C of heat preservation sinterings and obtain.
3. the Ti position described in claim 1 is executed acceptor and is co-doped with SrTiO3The preparation method of base high dielectric ceramic material, its feature exists In: by SrCO3、Nb2O5、Al2O3、TiO2By formula Sr (Nb0.5Al0.5)xTi1-xO3Stoichiometric proportion 1:x/4:x/4: (1-x) ball milling after mixing, dries, and 1150 DEG C carry out pre-burning, and then secondary ball milling obtains pre-burning powder body, is added by pre-burning powder body Add adhesive pelletize and sieve, molding, then binder removal obtains ceramic body, then by ceramic body in air 1560～1620 DEG C Heat preservation sintering, with after after the programmed cooling.
Ti position the most according to claim 3 is executed acceptor and is co-doped with SrTiO3The preparation method of base high dielectric ceramic material, it is special Levy and be: described ball milling is for adding ball-milling medium and dispersant, and ball milling 20～after 30 hours, separating zirconium ball, then by ball milling After raw mixture put in drying baker and dry.
Ti position the most according to claim 3 is executed acceptor and is co-doped with SrTiO3The preparation method of base high dielectric ceramic material, it is special Levy and be: described drying temperature 100～150 DEG C, drying time 10～15 hours；It is polyvinyl alcohol that described pelletize sticks with glue agent Solution；Described compression molding is: composite granule is pressed under the pressure of 10～15MPa a diameter of 12mm, thickness The disk of 1～1.5mm.
Ti position the most according to claim 3 is executed acceptor and is co-doped with SrTiO3The preparation method of base high dielectric ceramic material, it is special Levy and be: described burn-in time is 2～3 hours.
Ti position the most according to claim 3 is executed acceptor and is co-doped with SrTiO3The preparation method of base high dielectric ceramic material, it is special Levy and be: the heat preservation sintering time of described ceramic body is 2～4 hours.
CN201610225867.6A 2016-04-12 2016-04-12 A kind of Ti is applied acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof Expired - Fee Related CN105777112B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610225867.6A CN105777112B (en) 2016-04-12 2016-04-12 A kind of Ti is applied acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610225867.6A CN105777112B (en) 2016-04-12 2016-04-12 A kind of Ti is applied acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105777112A true CN105777112A (en) 2016-07-20
CN105777112B CN105777112B (en) 2018-10-09

Family

ID=56397195

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610225867.6A Expired - Fee Related CN105777112B (en) 2016-04-12 2016-04-12 A kind of Ti is applied acceptor and is co-doped with SrTiO3Base high dielectric ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105777112B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108439975A (en) * 2018-05-18 2018-08-24 武汉理工大学 It is a kind of have stablize strontium titanates calcium base energy storage ceramic of defect sturcture and preparation method thereof
CN108530068A (en) * 2017-03-06 2018-09-14 中国科学院福建物质结构研究所 A kind of barium calcium codope substitution La2NiO4Giant dielectric ceramics and preparation method thereof
CN113292340A (en) * 2021-06-02 2021-08-24 哈尔滨工业大学 High-voltage electric low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof
CN114665003A (en) * 2022-03-23 2022-06-24 湘潭大学 Flexible ferroelectric film containing defective dipole and manufacturing method thereof
CN116813331A (en) * 2023-07-10 2023-09-29 清华大学 Strontium titanate ceramic and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH038766A (en) * 1989-06-06 1991-01-16 Matsushita Electric Ind Co Ltd Production of voltage-dependent nonlinear resistor porcelain composition and varistor
CN1472172A (en) * 2003-06-10 2004-02-04 武汉理工大学 Dielectric niobate ceramics and preparing method thereof
CN1719560A (en) * 2005-05-31 2006-01-11 广州翔宇微电子有限公司 Method for mfg. crystal boundary layer ceramic medium material and substrate for single layer capacitor and substrate thereof
CN1800091A (en) * 2005-12-31 2006-07-12 昆明理工大学 Method for producing nanometer doping agent modified SrTiO3 pressure sensitive ceramic material ,resistance and the resistance produced therefrom
CN1850719A (en) * 2006-05-15 2006-10-25 西安交通大学 Strontium titanate pressure-sensitive resistor medium and preparing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH038766A (en) * 1989-06-06 1991-01-16 Matsushita Electric Ind Co Ltd Production of voltage-dependent nonlinear resistor porcelain composition and varistor
CN1472172A (en) * 2003-06-10 2004-02-04 武汉理工大学 Dielectric niobate ceramics and preparing method thereof
CN1719560A (en) * 2005-05-31 2006-01-11 广州翔宇微电子有限公司 Method for mfg. crystal boundary layer ceramic medium material and substrate for single layer capacitor and substrate thereof
CN1800091A (en) * 2005-12-31 2006-07-12 昆明理工大学 Method for producing nanometer doping agent modified SrTiO3 pressure sensitive ceramic material ,resistance and the resistance produced therefrom
CN1850719A (en) * 2006-05-15 2006-10-25 西安交通大学 Strontium titanate pressure-sensitive resistor medium and preparing method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108530068A (en) * 2017-03-06 2018-09-14 中国科学院福建物质结构研究所 A kind of barium calcium codope substitution La2NiO4Giant dielectric ceramics and preparation method thereof
CN108530068B (en) * 2017-03-06 2020-05-05 中国科学院福建物质结构研究所 Barium-calcium co-doped substituted La2NiO4Giant dielectric ceramic and preparation method thereof
CN108439975A (en) * 2018-05-18 2018-08-24 武汉理工大学 It is a kind of have stablize strontium titanates calcium base energy storage ceramic of defect sturcture and preparation method thereof
CN108439975B (en) * 2018-05-18 2021-04-20 武汉理工大学 Strontium calcium titanate-based energy storage ceramic with stable defect structure and preparation method thereof
CN113292340A (en) * 2021-06-02 2021-08-24 哈尔滨工业大学 High-voltage electric low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof
CN113292340B (en) * 2021-06-02 2022-08-26 哈尔滨工业大学 High-piezoelectricity low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof
CN114665003A (en) * 2022-03-23 2022-06-24 湘潭大学 Flexible ferroelectric film containing defective dipole and manufacturing method thereof
CN116813331A (en) * 2023-07-10 2023-09-29 清华大学 Strontium titanate ceramic and preparation method and application thereof

Also Published As

Publication number Publication date
CN105777112B (en) 2018-10-09

Similar Documents

Publication Publication Date Title
CN105777112A (en) Ti-bit donor-acceptor co-doping SrTiO3 base high-dielectric ceramic and preparation method thereof
CN105130421A (en) Ti-position high-valence substituted SrTiO3 giant dielectric ceramic and preparation method thereof
CN109133915A (en) A kind of high energy storage barium phthalate base dielectric material and preparation method thereof
CN109942292B (en) Sodium bismuth titanate-based transparent ceramic material and preparation method and application thereof
CN105732020B (en) A kind of preparation method of giant dielectric, low-loss titanium dioxide base composite ceramic
CN103755339A (en) Preparation method of SrTiO3 ceramic material having giant dielectric constant and low dielectric loss
CN105801112A (en) Nd and Al co-doped substituted Ba0.4Sr0.6TiO3 giant dielectric ceramic and preparation method thereof
CN102515754B (en) Barium zirconate titanate-barium calciate titanate (BZT-BCT) ceramic modified by doping of lanthanum oxide and preparation method for same
CN103011805B (en) BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof
CN104692797B (en) A kind of barium-strontium titanate-based capacitor ceramics and preparation method thereof
CN103693957B (en) Method for preparing microwave dielectric ceramic material
KR20210122225A (en) Doped perovskite barium stannate material and manufacturing method and application thereof
CN109516799B (en) High-dielectric ceramic capacitor material with high temperature stability and preparation method thereof
CN111004030A (en) MgTiO (magnesium-titanium-oxide) powder3Microwave-based dielectric ceramic and preparation method thereof
CN103833351A (en) Microwave dielectric ceramic and preparation method thereof
CN114436643A (en) Giant dielectric constant and low dielectric loss ceramic and preparation method thereof
CN104098330B (en) Post growth annealing is adopted to prepare the method for high-performance barium strontium titanate pyroelectric ceramics
CN107500756A (en) A kind of high-k low-loss SrTiO3Based dielectric material and preparation method thereof
CN109456058B (en) Barium zirconate titanate and barium niobate zincate composite capacitor ceramic material and preparation method thereof
CN107382314A (en) A kind of microwave-medium ceramics of barium base complex perovskite structure
CN101792312A (en) SrTiO3 ceramic dielectric material and preparation method of capacitor thereof
CN105198409A (en) Preparation method of barium-strontium-titanate-based glass composite ceramic with high energy storage density
CN103708826A (en) Low dielectric-loss barium strontium titanate pyroelectric ceramic and preparation method thereof
CN109095920A (en) A kind of high-permitivity ceramics capacitor material of bismuth-sodium titanate base high-temperature stable and preparation method thereof
CN104030685A (en) High-Q-value microwave dielectric ceramic and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181009

Termination date: 20190412

CF01 Termination of patent right due to non-payment of annual fee