CN112811901B - High-mesomorphic-boundary-layer ceramic material and preparation method of grain boundary-layer ceramic substrate - Google Patents
High-mesomorphic-boundary-layer ceramic material and preparation method of grain boundary-layer ceramic substrate Download PDFInfo
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Abstract
The invention discloses a high-mesomorphic boundary layer ceramic material and a preparation method of a grain boundary layer ceramic substrate, wherein the ceramic material comprises the following components in parts by weight: main material: strontium titanate; donor material: la 2 O 3 And Nb 2 O 5 (ii) a Sintering aid: siO 2 2 And Li 2 CO 3 (ii) a Acceptor material: bi 2 O 3 One or more of CuO, and ZnO; the sintering aid is used for reducing the sintering temperature of the porcelain and promoting the crystal grain development; the acceptor material is used as a grain boundary insulating coating material for oxidation sintering; the preparation of the grain boundary layer ceramic substrate is finished by secondary sintering based on the ceramic material, namely reduction semiconduction sintering and oxidation grain boundary layer insulation sintering. According to the invention, the ceramic material is doped with the sintering aid, and the ceramic substrate is prepared by adopting a secondary sintering mode, so that on one hand, energy is saved, on the other hand, a larger size grain diameter can be obtained at a lower sintering temperature, and the dielectric constant is favorably improved; meanwhile, znO is added in the process of grain boundary insulation, so that the insulation resistance and the insulation strength of the product are improved.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a high-mesomorphic boundary layer ceramic material and a preparation method of a grain boundary layer ceramic substrate.
Background
The miniaturization trend of electronic devices requires capacitors with smaller size and larger energy storage density, and the grain boundary layer ceramic has ultrahigh dielectric constant and meets the requirement of the capacitors, so that the ceramic is widely used as a dielectric material of the capacitors.
At present, the research and development and mass production capacity of the high-dielectric-constant grain boundary layer ceramic material at home are far away from the foreign similar products, and the foreign related ceramic dielectric constant can reach 10000-60000 and is produced in mass; the reliability, the mass production capability and the maturity of domestic similar products have certain differences from foreign countries.
In the technical aspect, the preparation of the grain boundary layer ceramic substrate comprises two preparation methods of primary sintering and secondary sintering; the primary sintering is mostly in the research and development stage of a laboratory, and because the reduction and oxidation reactions are completed in the primary temperature rise and drop process, the process control difficulty is high, and the product performance stability is poor; the commercial product mainly adopts secondary sintering as a main material, firstly carries out high-temperature reduction sintering, and then carries out oxidation heat treatment in the air, so that the product performance is stable, the reliability is high, but the reduction sintering temperature is too high (about 1450 ℃).
In conclusion, the main problems of preparing the high mesomorphic interface layer ceramic substrate are that the reduction sintering temperature is high, the ceramic substrate is easy to curl and crack, and the insulating property is poor; the product of the final product has low consistency and reliability.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-mesomorphic boundary layer ceramic material with the dielectric constant of 10000-15000, better performance consistency, better reliability and mass production and a preparation method of a grain boundary layer ceramic substrate.
The invention discloses a high-mesomorphism boundary layer ceramic material, which comprises the following components:
main material: strontium titanate;
donor material: la 2 O 3 And Nb 2 O 5 ；
Sintering aid: siO 2 2 And Li 2 CO 3 ；
Acceptor material: bi 2 O 3 One or more of CuO and ZnO; the acceptor material is used as a grain boundary insulated coating material for oxidation sintering.
As a further improvement of the invention, the La 2 O 3 The addition amount of (B) is (0.1-1) wt% of the strontium titanate, and the Nb is 2 O 5 The addition amount of (B) is 0.1-1 wt% of the strontium titanate.
As a further development of the invention, the SiO 2 The addition amount of (A) is 0.2 to 1 wt% of the sum of the host material and the donor material, and the Li is 2 CO 3 The addition amount of (A) is 0.5-5 wt% of the sum of the main material and the donor material.
As a further improvement of the invention, the acceptor material is mixed with a PVA solution when in use, and the prepared mixed solution is 50-100 g/L.
As a further improvement of the invention, the acceptor material is Bi 2 O 3 CuO and ZnO, said Bi 2 O 3 The mass ratio of CuO to ZnO is (0.1-100): (0.1-100): (0 to 20).
The invention also discloses a preparation method of the high-mesomorphism boundary layer ceramic substrate, which comprises the following steps:
step 3, placing the membrane on a zirconia plate and laminating; at H 2 /N 2 Reducing and sintering at 1200-1300 ℃ for 2-6 hours under the reducing atmosphere condition of 5-20 percent; after the furnace temperature is cooled to room temperature, the semi-conductor of the membrane is completed, and a semi-conductor substrate is prepared;
step 4, mixing the acceptor material and the PVA solution into a suspension, and stirring to uniformly disperse the solid particles in the suspension; uniformly coating the suspension on the surface of the semi-conductive substrate by using screen printing;
step 5, after coating, carrying out oxidation heat treatment on the semiconductive substrate, and carrying out oxidation sintering at the temperature of 900-1150 ℃ for 1-2 hours; and after the furnace temperature is cooled to room temperature, preparing the crystal boundary layer ceramic substrate.
As a further improvement of the present invention, in said step 1,
mixing, ball milling for 5-8 hours, discharging, drying, and sieving by a 60-mesh sieve, wherein the particle size of the mixture is d 50 ＜3μm。
As a further improvement of the present invention, in said step 2,
the PVA solution accounts for (20-30) wt% of the mixture.
As a further improvement of the present invention, in said step 3,
in the low-temperature section of less than 1000 ℃, the heating rate is 5 ℃/min; in the high temperature section of more than 1000 ℃, the heating rate is 2 ℃/min until the temperature is raised to the reduction sintering temperature.
As a further improvement of the present invention, in said step 5,
the heating rate is more than 7 ℃/min until the temperature is raised to the oxidation sintering temperature.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts Li 2 CO 3 With SiO 2 The composite sintering aid can reduce the reduction sintering temperature from 1450 ℃ to 1200-1300 ℃; in the above composite sintering aid, an appropriate amount of Li 2 CO 3 Can reduce the reduction sintering temperature to 1200-1300 ℃, and utilizes SiO 2 High viscosity in molten state, and low Li content 2 CO 3 Rapid volatilization at high temperature to ensure the processThe control is carried out;
2. the reduction sintering process adopts a laminated sintering process, so that deformation, bending and crushing of a thin-layer (0.24 mm) ceramic substrate caused by internal stress generated by grain growth and high-temperature contraction of a membrane in the sintering process can be avoided, the surface of the prepared substrate is flat and has no curl, the electrical property is consistent, and the reliability is high;
3. the grain boundary insulation coating material selected by the invention comprises ZnO, so that the insulation resistance and the insulation strength of the material can be further improved on the basis that other properties meet the requirements.
Drawings
FIG. 1 is a flowchart illustrating a method for fabricating a grain boundary layer ceramic substrate according to an embodiment of the present invention;
FIG. 2 is a schematic view of a stack sintered according to an embodiment of the present invention;
FIG. 3a is a schematic diagram of a conventional sintered diaphragm;
FIG. 3b is a schematic view of a laminated sintered diaphragm according to an embodiment of the present invention;
FIGS. 4 a-4 f are metallographic micrographs of semiconductor substrates after reduction sintering of samples 1-6 according to one embodiment of the disclosure.
In the figure:
1. a zirconia plate; 2. a membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention is described in further detail below with reference to the attached drawing figures:
in order to solve the problems of high reduction sintering temperature, easy curling and cracking of the ceramic substrate, poor insulating property, and low consistency and reliability of the final product performance existing in the conventional preparation of the high-mesomorphic-grain-boundary-layer ceramic substrate, the invention redesigns the formula of the high-mesomorphic-grain-boundary-layer ceramic material and prepares the grain-boundary-layer ceramic substrate by a laminated secondary sintering mode (firstly reduction sintering and then oxidation sintering), so that the sintering temperature is reduced, the process is easy to control, and the substrate performance is excellent. The method mainly comprises the following steps: according to the invention, the sintering aid is added into the ceramic material, and the ceramic substrate is prepared by adopting a secondary sintering mode, so that on one hand, energy is saved, on the other hand, a larger size grain diameter can be obtained at a lower sintering temperature, and the improvement of the dielectric constant is facilitated; meanwhile, znO is added in the process of grain boundary insulation, so that the insulation resistance and the insulation strength of the product are improved. Specifically, the method comprises the following steps:
the invention provides a high-mesomorphic boundary layer ceramic material, which comprises the following components:
main material: strontium titanate;
donor material: la 2 O 3 And Nb 2 O 5 ；
Sintering aid: siO 2 2 And Li 2 CO 3 (ii) a The sintering aid is used for reducing the sintering temperature of the porcelain and promoting the crystal grain development;
acceptor material: bi 2 O 3 One or more of CuO and ZnO.
Wherein the content of the first and second substances,
of the donor material, la 2 O 3 The addition amount of (B) is 0.1-1 wt% of strontium titanate, nb 2 O 5 The addition amount of the strontium titanate is 0.1-1 wt percent of the strontium titanate. Substituting La in the donor material for Sr in the titanic acid and substituting Nb in the donor material for Ti in the titanic acid to realize semiconductorization of the material after reduction sintering;
further, the invention adopts La 2 O 3 And Nb 2 O 5 The principle of the donor material is as follows:
from the above, it is known that the ceramic substrate semiconductorization generates oxygen vacancy and weakly bonded (Ti) in the material system by the combined action of valence substitution and reducing atmosphere sintering 4+ E) ions, lowering the system resistivity.
Among the sintering aids, siO 2 The addition amount of (2) is 0.2-1 wt% of the total of the main material and the donor material, and Li 2 CO 3 The addition amount of (2) is 0.5-5 wt% of the sum of the main material and the donor material. The design principle is as follows: the invention adopts Li 2 CO 3 With SiO 2 The composite sintering aid can reduce the reduction sintering temperature from 1450 ℃ to 1200-1300 ℃; in the composite sintering aid, a proper amount of Li 2 CO 3 Can reduce the reduction sintering temperature to 1200-1300 ℃, and utilizes SiO 2 High viscosity in molten state, and low Li content 2 CO 3 The volatile oil can be quickly volatilized at high temperature, so that the process is controllable;
further, the present invention employs Li 2 CO 3 With SiO 2 The principle of the composite sintering aid as the grain boundary layer ceramic material is as follows:
Li 2 CO 3 low melting point, can be melted into liquid phase at 720 deg.C, srO, tiO 2 Soluble in Li 2 Formation of Li in O 2 O-SrO-TiO 2 And the liquid phase is completely infiltrated with the crystal grains, and the crystal grains grow up to be an evaporation-condensation process under the liquid phase sintering. However, strict control of Li is required 2 CO 3 The addition amount is as follows:
(1) If the liquid phase content is too high, the mass transfer distance in the grain growth process is increased, and the grain growth is not facilitated;
(2)Li + li has an acceptor function to a certain extent, can reduce oxygen vacancy and free electron in the system, and is not beneficial to semiconductorization 2 CO 3 The mixing amount should be controlled at (0.5 to 5) wt%.
(3)SiO 2 Can react with Li 2 O generates eutectic phase to promote the growth of crystal grains; simultaneous SiO 2 The liquid phase has high viscosity and can reduce Li 2 CO 3 Volatilize in the sintering process to control the sintering process of the system, so Li 2 CO 3 And SiO 2 The composition has a synergistic effect of combustion assistance. SiO 2 2 The content is controlled within (0.2-1) wt%.
The acceptor material is used as a grain boundary insulation coating material for oxidation sintering, and when the acceptor material is used, the acceptor material is mixed with a PVA (polyvinyl alcohol) solution, and the prepared mixed solution is 50-100 g/L. When in use, 0 to 100 wt percent of Bi can be adopted as the acceptor oxide 2 O 3 (0-100) wt% CuO and (0-20) wt% ZnO are coated compositely or singly; bi is preferred 2 O 3 CuO and ZnO composite coating; further, bi 2 O 3 The mass ratio of CuO to ZnO is (0.1-100): (0.1 to 100): (0 to 20), preferably Bi 2 O 3 And the mass ratio of CuO to ZnO is 1.
The invention adopts Bi 2 O 3 The principle of using CuO and ZnO as acceptor materials is as follows:
Bi 3+ ，Cu 2+ ，Zn 2+ can accept free electrons to coordinate in the system, play the role of an acceptor, improve the resistivity of the system, and because Bi 2 O 3 The diffusion rate of CuO and ZnO in molten state along the grain boundary is much higher than that in the interior of the crystal grain, so that the grain boundary can be insulated, and the crystal grain can be kept in a semiconductor state, so as to form a grain boundary layer ceramic structure.
By separately carrying out Bi 2 O 3 Doping, high dielectric constant of the system, small loss value less than 1 percent and poor breakdown strength; but when CuO is doped, the dielectric constant of the system is low, the loss value is more than 1 percent and less than 2 percent, and the breakdown strength is high; after ZnO is added compositely, the insulation resistivity of the system can be further improved; therefore, the grain boundary layer ceramic material with excellent comprehensive performance can be obtained by compounding the three materials.
As shown in fig. 1, the present invention provides a method for preparing a high mesomorphic grain boundary layer ceramic substrate, which completes the preparation of a grain boundary layer ceramic substrate by secondary stacking sintering, namely, reduction semi-conductor sintering and oxidation grain boundary layer insulation sintering, and specifically comprises:
the method specifically comprises the following steps:
weighing strontium titanate main material and La according to preset adding amount 2 O 3 、Nb 2 O 5 、SiO 2 、Li 2 CO 3 Adding the mixture into a ball mill, mixing and ball-milling for 5 to 8 hours, drying the mixture after discharging, and sieving the dried mixture with a 60-mesh sieve to obtain the product with the particle size d 50 A mix of < 3 μm.
the method comprises the following specific steps:
and (3) uniformly mixing the mixture with (20-30) wt% PVA solution, and performing casting, laminating, cutting and molding to obtain the 38mm-0.24mm membrane.
Step 3, placing the membrane on a zirconia plate, and laminating; then, reducing and sintering under the condition of reducing atmosphere; after the furnace temperature is cooled to room temperature, a semi-conductive substrate is prepared;
the method comprises the following specific steps:
after the formed diaphragm is subjected to glue removal, the diaphragm 2 is placed on the zirconia plate 1 and laminated, as shown in fig. 2; then, at H 2 /N 2 Reduction-firing at 1200 to 1300 ℃ for 2 to 6 hours (more preferably 2 to 4 hours) under a reducing atmosphere condition of 5 to 20% (more preferably 5 to 10%, more preferably 5%); after the furnace temperature is cooled to room temperature, the semi-conductor of the membrane is completed, and a semi-conductor substrate is prepared;
further, in order to avoid the curling of the membrane in the sintering process, the heating rate is 4-6 ℃/min, preferably 5 ℃/min at the low-temperature stage of less than 1000 ℃; in the high-temperature section of more than 1000 ℃, the heating rate is 2-3 ℃/min, preferably 2 ℃/min; heating to the reduction sintering temperature of 1200-1300 ℃ and preserving heat for 2-4 hours, preferably heating to the reduction sintering temperature of 1250 ℃ and preserving heat for 2 hours;
further, H in the atmosphere is noted during the reduction sintering process 2 The content should not be too high, otherwise, the sintered ceramic body lattice will be distorted, and the final substrate performance will be affected, as shown in fig. 3a and 3 b; in order to avoid the deformation of the substrate caused by the internal stress in the high-temperature reduction sintering process, the invention adopts a laminated sintering mode to prevent the deformation of the substrate caused by the internal stress to a certain extent and ensure the flatness of the substrate.
Step 4, mixing an acceptor material and a PVA solution into a suspension, stirring and ensuring that solid particles are uniformly dispersed in the suspension to obtain a suspension with the viscosity of 50-100 g/L; and uniformly coating the suspension on the surface of the semiconductive substrate by screen printing, and controlling the coating thickness to be the same each time.
Step 5, after coating, carrying out oxidation heat treatment on the semiconductive substrate in a muffle furnace, and carrying out oxidation sintering for 1-2 hours at the temperature of 900-1150 ℃; after the furnace temperature is cooled to room temperature, preparing a grain boundary layer ceramic substrate;
further, in order to reduce Bi 2 O 3 The temperature rise rate of the heat treatment is accelerated (more than 7 ℃/min), the temperature is kept for 2 hours at the heat treatment temperature, the grain boundary layer is insulated slowly, and then the sample is cooled along with the furnace, so that the preparation of the grain boundary layer ceramic substrate is completed.
After the preparation of the grain boundary layer ceramic substrate is completed based on the steps 1-5, the ceramic substrate is cleaned, sprayed with gold and scribed to prepare a 0303 50V chip, and the electrical performance test is carried out.
Example (b):
the invention provides a high-mesomorphic-boundary-layer ceramic material, wherein the formula of a reduction sintering material is shown in table 1, the formula of an oxidation sintering coating material is shown in table 2, and the unit is g:
TABLE 1
| Sample numbering | 1 | 2 | 3 | 4 | 5 | 6 |
| SrTiO 3 | 900 | 900 | 900 | 900 | 900 | 900 |
| La 2 O 3 | 3.3 | 3.3 | 3.3 | 3.3 | 3.3 | 3.3 |
| Nb 2 O 5 | 4 | 4 | 4 | 4 | 4 | 4 |
| Li 2 CO 3 | / | 9.2 | 9.2 | 9.2 | 9.2 | 9.2 |
| SiO 2 | / | / | 1.8 | 1.8 | 1.8 | 1.8 |
| Sintering temperature | 1450℃ | 1250℃ | 1250℃ | 1250℃ | 1250℃ | 1250℃ |
TABLE 2
The invention provides a preparation method of a grain boundary layer ceramic substrate based on the ceramic materials of the samples 1 to 6, which comprises the following steps:
step 3, placing the membrane on a zirconia plate, and laminating 1-The sintering temperature of sample No. 6 is shown in Table 1, and the reducing atmosphere H 2 /O 2 =5%; in order to avoid the diaphragm from curling in the sintering process, the heating rate is 5 ℃/min at a low temperature (less than 1000 ℃) and 2 ℃/min at a high temperature (more than 1000 ℃), the temperature is raised to the sintering temperature and kept for 2 hours, and then the sample is cooled to the room temperature along with the furnace to finish the reduction sintering;
step 4, mixing the materials according to the formula shown in the table 2, preparing 50g/L suspension with the PVA solution with the content of 20 percent, and uniformly stirring; coating the prepared coating material on a substrate discharged from a furnace by reduction sintering by using a screen printing process;
step 5, carrying out heat treatment on the coated substrate, wherein the temperature is shown in a table 2; to reduce Bi 2 O 3 The temperature rise rate of the heat treatment is accelerated (more than 7 ℃/min), the heat is preserved for 2 hours at the heat treatment temperature, and then the sample is cooled along with the furnace, thus finishing the preparation of the grain boundary layer ceramic substrate.
The grain boundary layer ceramic substrate is scribed into 0303-50V chips for testing, and the test results are shown in Table 3:
TABLE 3
The effect of the lamination sintering process is shown in fig. 3a and 3b, and the flatness of the substrate sintered by adopting the lamination is greatly improved under the same sintering process condition.
After the reduction sintering, the metallographic microscopic morphology of the semiconductor substrate is shown in FIGS. 4a to 4 f;
the dielectric constant of the high-mesogenic-boundary-layer ceramic material can be calculated by the following formula:
ε r ≈K i (d g /d i )
in the formula, epsilon r Is the apparent dielectric constant; k i The dielectric constant of the grain boundary layer; d is a radical of g Indicates the grain size; d i The thickness of the grain boundary layer is shown.
From the above formula, the dielectric constant is proportional to the crystal grain size, and the larger the crystal grain size, the higher the dielectric constant. Generally, the grain size is less than 20 μm, and the dielectric constant is 10000 to 15000.
As shown in FIGS. 4a to 4f, the grains of the material prepared by the 6 formulations are all smaller than 20 μm, so that the dielectric constant of the prepared material is 10000 to 15000.
Combined with the results of the electrical property tests, li 2 CO 3 And SiO 2 Has good sintering effect, can obtain the required grain size at lower temperature (1250 ℃), and has better size distribution uniformity than an undoped sample. However, it should also be noted that Li, a sintering aid, is added singly 2 CO 3 No burning aid effect, and its melting point is low, and it begins to volatilize at 700 ℃, so Li is required 2 CO 3 Intermediate composite SiO 2 Slow down Li 2 CO 3 And volatilization is carried out, so that the combustion assisting effect of the composite combustion assisting agent is obviously improved.
In the oxidation sintering stage, bi 2 O 3 The material obtained by single doping has the highest dielectric constant and low dielectric loss; the material doped with CuO has insulation resistance higher than that of Bi 2 O 3 One order of magnitude higher; thus, use of Bi 2 O 3 The dielectric ceramic with better comprehensive performance can be obtained by compounding with CuO. The addition of ZnO can continuously improve the insulation resistance and the breakdown strength of the material, but has a certain effect of reducing the dielectric constant.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A high-mesogenic-boundary-layer ceramic material, comprising:
main material: strontium titanate;
donor material: la 2 O 3 And Nb 2 O 5 ；
Sintering aid: siO 2 2 And Li 2 CO 3 ；
Acceptor material: the acceptor material is Bi 2 O 3 CuO and ZnOIn a mixture of (A) and (B), said Bi 2 O 3 The mass ratio of CuO to ZnO is (0.1-100): (0.1-100): (0.1 to 20); the acceptor material is used as a grain boundary insulated coating material for oxidation sintering;
the La 2 O 3 The addition amount of (B) is (0.1-1) wt% of the strontium titanate, and the Nb is 2 O 5 The addition amount of the strontium titanate is (0.1-1) wt%;
the SiO 2 The addition amount of (A) is 0.2-1 wt% of the sum of the main material and the donor material, and the Li 2 CO 3 The addition amount of (2) is 0.5-5 wt% of the sum of the main material and the donor material;
when the acceptor material is used, the acceptor material is mixed with PVA solution, and the prepared mixed solution is 50-100 g/L;
the preparation method of the grain boundary layer ceramic substrate of the high mesomorphic boundary layer ceramic material comprises the following steps:
step 1, mixing and ball-milling a main material, a donor material and a sintering aid, drying and sieving to prepare a mixture;
step 2, mixing the mixture with a PVA solution, and carrying out tape casting, laminating, cutting and forming to obtain a membrane;
step 3, placing the membrane on a zirconium oxide plate, and laminating; at H 2 /N 2 Reducing and sintering at 1200-1300 ℃ for 2-6 hours under the condition of 5-20% of reducing atmosphere; after the furnace temperature is cooled to room temperature, the semi-conductor of the membrane is completed, and a semi-conductor substrate is prepared;
step 4, mixing the acceptor material and the PVA solution into a suspension, and stirring to uniformly disperse the solid particles in the suspension; uniformly coating the suspension on the surface of the semi-conductive substrate by using screen printing;
step 5, after the coating is finished, carrying out oxidation heat treatment on the semi-conductive substrate, and carrying out oxidation sintering at the temperature of 1000-1150 ℃ for 1-2 hours; after the furnace temperature is cooled to room temperature, a crystal boundary layer ceramic substrate is prepared;
in the step 1, mixing and ball milling are carried out for 5-8 hours, the mixture is discharged, dried and sieved by a 60-mesh sieve, and the particle size of the mixture is d 50 ＜3μm。
2. A method for preparing an intergranular layer ceramic substrate based on the high mesogenic layer ceramic material as claimed in claim 1, comprising:
step 1, mixing and ball-milling a main material, a donor material and a sintering aid, drying and sieving to prepare a mixture;
step 2, mixing the mixture with a PVA solution, and carrying out tape casting, laminating, cutting and forming to obtain a membrane;
step 3, placing the membrane on a zirconium oxide plate, and laminating; at H 2 /N 2 Reducing and sintering at 1200-1300 ℃ for 2-6 hours under the condition of 5-20% of reducing atmosphere; after the furnace temperature is cooled to room temperature, the semi-conductor of the membrane is completed, and a semi-conductor substrate is prepared;
step 4, mixing the acceptor material and the PVA solution into a suspension, and stirring to uniformly disperse the solid particles in the suspension; uniformly coating the suspension on the surface of the semiconductor substrate by using screen printing;
step 5, after coating, carrying out oxidation heat treatment on the semiconductive substrate, and carrying out oxidation sintering at the temperature of 1000-1150 ℃ for 1-2 hours; after the furnace temperature is cooled to room temperature, a crystal boundary layer ceramic substrate is prepared;
in the step 1, mixing and ball milling are carried out for 5-8 hours, the mixture is discharged, dried and sieved by a 60-mesh sieve, and the particle size of the mixture is d 50 ＜3μm。
3. The method according to claim 2, wherein in step 2, the PVA solution is (20 to 30) wt% of the mix.
4. The method according to claim 2, wherein in the step 3, in a low temperature section of < 1000 ℃, the temperature rise rate is 5 ℃/min; in the high temperature section of more than 1000 ℃, the heating rate is 2 ℃/min until the temperature is raised to the reduction sintering temperature.
5. The method of claim 2, wherein in step 5, the temperature ramp rate is greater than 7 ℃/min until the temperature is raised to the oxidizing sintering temperature.
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