CN114031424A - Surface metallization method of microwave dielectric ceramic material and microwave dielectric ceramic device - Google Patents
Surface metallization method of microwave dielectric ceramic material and microwave dielectric ceramic device Download PDFInfo
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- CN114031424A CN114031424A CN202111538799.6A CN202111538799A CN114031424A CN 114031424 A CN114031424 A CN 114031424A CN 202111538799 A CN202111538799 A CN 202111538799A CN 114031424 A CN114031424 A CN 114031424A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 148
- 239000000919 ceramic Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000001465 metallisation Methods 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 70
- 238000007747 plating Methods 0.000 claims abstract description 64
- 239000010953 base metal Substances 0.000 claims abstract description 63
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000010970 precious metal Substances 0.000 claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 13
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 12
- 230000008313 sensitization Effects 0.000 claims abstract description 12
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- 238000007788 roughening Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 106
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
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- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
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- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims description 3
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- ZKODLPLYXXUCHB-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;hydrate Chemical compound O.[Na+].OCS([O-])=O ZKODLPLYXXUCHB-UHFFFAOYSA-M 0.000 claims description 3
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- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 8
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Abstract
The application belongs to the technical field of materials, and particularly relates to a surface metallization method of a microwave dielectric ceramic material and a microwave dielectric ceramic device. The surface metallization method of the microwave dielectric ceramic material comprises the following steps: roughening the surface of the microwave dielectric ceramic material, and sequentially carrying out sensitization treatment and activation reduction treatment on the microwave dielectric ceramic material with the roughened surface; and placing the microwave dielectric ceramic material with the precious metal simple substance deposited on the surface in a base metal plating solution for chemical plating, and then sintering to obtain the microwave dielectric ceramic material with the base metal layer formed on the surface. The surface treatment method improves the consistency and uniformity of the surface metallization layer and improves the bonding tightness of the metallization layer and the surface of the ceramic material. In addition, the base metal layer is adopted to replace the noble metal layer, so that the cost is reduced, and the problem that the conductivity of the product is poor due to electron migration of the noble metal in a use environment is avoided.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a surface metallization method of a microwave dielectric ceramic material and a microwave dielectric ceramic device.
Background
The microwave dielectric ceramic filter is a filter made of microwave dielectric ceramic material, and has the characteristics of low loss, stable frequency temperature coefficient, small thermal expansion coefficient, high power capacity, small volume and the like, so that the microwave dielectric ceramic filter is widely applied to the fields of mobile communication, microwave base stations, military radars, satellite systems and the like. The 5G communication adopts higher microwave and even millimeter wave frequency bands, which brings new technical requirements for passive devices such as ceramic filters and the like, and the metallization process is of great importance to the performance of the ceramic filters. The metallization of microwave dielectric ceramics is a key technology in the manufacture of microwave dielectric devices, and directly influences key performance indexes of the devices, such as quality factors (Q values), reliability and the like. At present, most metallization processes adopted for ceramic filters are to coat high-temperature silver paste on the surface of ceramic by means of screen printing, silver spraying or silver dipping and the like and then sinter the ceramic. The silver paste sintering method for screen printing is a method of high-temperature sintering after the silver paste is screen printed on the surface of the ceramic, and the difference of the formula of the conductive silver paste and the sintering process of the silver paste easily causes the unsmooth silver layer sintered on the surface of the ceramic and low effective conductivity, and influences parameters such as the Q value, the adhesive force of the metal film layer, the surface roughness and the like of the product. The silver spraying or silver dipping process has high requirements, the current resistance and temperature resistance of the product are poor, and the metal film layer is easy to foam and fall off under high current and high temperature.
Although the technology of taking noble metal silver as the conductive filler is mature, and the product has better conductivity, the silver as the noble metal has the defects of scarce resources, high cost and the like, and the thickness, adhesion and weldability of the silver layer coated on the surface of the ceramic have poor consistency and the like in the silk-screen, silver-spraying or silver-dipping process due to the uniformity of the silver paste and the reliability of equipment, so that the metallized ceramic filter has poor performance stability.
Disclosure of Invention
The application aims to provide a surface metallization method of a microwave dielectric ceramic material and a microwave dielectric ceramic device, and aims to solve the problems of poor consistency, poor stability and high cost of the existing surface metallization of the microwave dielectric ceramic material to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for metallizing a surface of a microwave dielectric ceramic material, comprising the steps of:
obtaining a microwave dielectric ceramic material, and roughening the surface of the microwave dielectric ceramic material to obtain a microwave dielectric ceramic material with a roughened surface;
sequentially carrying out sensitization treatment and activation reduction treatment on the microwave dielectric ceramic material with the roughened surface to obtain a microwave dielectric ceramic material with a precious metal elementary substance deposited on the surface;
and placing the microwave medium ceramic material with the surface deposited with the precious metal simple substance in a base metal plating solution for chemical plating, and then sintering to obtain the microwave medium ceramic material with the base metal layer formed on the surface.
Further, the step of sensitizing comprises: and (3) placing the microwave dielectric ceramic material with the roughened surface in a silver-ammonia solution and/or a palladium chloride solution for mixing treatment.
Further, the step of activating reduction treatment comprises: and (3) placing the sensitized product in a reducing activating agent for mixing treatment to obtain the microwave dielectric ceramic material with the surface deposited with the noble metal simple substance.
Further, the preparation of the silver ammonia solution comprises the steps of: and adding ammonia water into the silver salt solution with the concentration of 5-7 g/L until the solution is precipitated and dissolved to obtain the silver-ammonia solution.
Further, the reducing activator comprises: at least one of sodium dihydrogen phosphite, sodium hypophosphite and glyoxylic acid.
Furthermore, the concentration of the reducing activator is 25-35 g/L.
Further, the base metal plating solution comprises: copper salt, reducing agent and complexing agent.
Further, the step of electroless plating comprises: and placing the microwave medium ceramic material with the surface deposited with the precious metal simple substance in the base metal plating solution, and mixing at the temperature of 50-70 ℃ and the pH value of 11-12 to obtain the microwave medium ceramic material with the base metal layer formed on the surface.
Further, the base metal layer is a copper layer.
Further, the thickness of the base metal layer is 10-30 microns.
Further, the copper salt includes copper sulfate pentahydrate.
Further, the reducing agent includes: formaldehyde, hypophosphite, dimethylamino borane, glyoxylic acid, sodium hydroxymethanesulfinate hydrate and thiourea dioxide.
Further, the complexing agent comprises: at least one of EDTA, tartaric acid, triethanolamine and citric acid.
Further, in the base metal plating solution, the concentration of the copper salt is 15-30 g/L, the concentration of the reducing agent is 12-18 mL/L, and the concentration of the complexing agent is 20-60 g/L.
Further, the conditions of the sintering treatment include: and preserving the heat for 2 to 4 hours at the temperature of 900 to 1000 ℃.
Further, the coarsening process includes: and etching the surface of the microwave dielectric ceramic material by adopting an acid solution.
Further, the preparation of the microwave dielectric ceramic material comprises the following steps: the metal oxide or metal salt is used as a raw material and is prepared by a solid-phase sintering process.
Further, the acidic solution comprises: at least one of hydrochloric acid, concentrated sulfuric acid and hydrofluoric acid with the mass percentage concentration of 10-20%.
Further, the etching treatment time is 3-5 minutes.
Furthermore, the relative dielectric constant of the microwave dielectric ceramic material is 4-50, the quality factor is not lower than 30000GHz, and the temperature coefficient of the resonant frequency is 0 +/-10 ppm/DEG C.
Further, the metal oxide includes: at least one of zinc oxide, silicon dioxide, magnesium oxide, manganese dioxide, lanthanum oxide, samarium oxide, aluminum oxide and titanium dioxide.
Further, the metal salt includes: at least one of barium carbonate, strontium carbonate and calcium carbonate.
In a second aspect, the present application provides a microwave dielectric ceramic device, which is prepared by the above surface metallization method of the microwave dielectric ceramic material, and includes a microwave dielectric ceramic substrate and a base metal layer bonded to the surface of the microwave dielectric ceramic substrate.
According to the surface metallization method of the microwave dielectric ceramic material, the surface of the microwave dielectric ceramic material is coarsened to improve the roughness of the surface of the microwave dielectric ceramic material, then sensitization and activation reduction are carried out to enable precious metal simple substance particles to be deposited on the surface of the microwave dielectric ceramic material, and then chemical plating and sintering are carried out in base metal plating solution to form a high-quality base metal layer with high density, uniform thickness and good adhesive force consistency on the surface of the microwave dielectric ceramic material. On one hand, the consistency and the uniformity of a metallized layer on the surface of the microwave dielectric ceramic material are improved, and the bonding tightness between the metallized layer and the surface of the ceramic material is improved, so that the bonding and the performance stability of the microwave dielectric ceramic material subjected to surface metallization treatment are improved. On the other hand, the base metal layer is adopted to replace the noble metal layer, so that the cost is reduced and the product conductivity deterioration caused by electron migration of the noble metal in the use environment is avoided on the premise of ensuring the material conductivity.
The microwave dielectric ceramic device provided by the second aspect of the application is prepared by the surface metallization method of the microwave dielectric ceramic material, and comprises a microwave dielectric ceramic substrate and a base metal layer combined on the surface of the microwave dielectric ceramic substrate, wherein the metallization layer has good consistency and uniformity, and is tightly combined with the surface of the ceramic material, so that the performance stability of the microwave dielectric ceramic device is improved. In addition, the base metal is adopted to replace the precious metal, so that the cost is reduced, the product conductivity deterioration caused by silver electron migration of precious metal such as silver in an application environment is avoided, and the performance requirement of the ceramic filter for 5G communication is met.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for metallizing a surface of a microwave dielectric ceramic material provided in an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of the surface topography of the microwave dielectric ceramic device provided in example 1 of the present application;
fig. 3 is a scanning electron microscope of a cross section of the microwave dielectric ceramic device provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for metallizing a surface of a microwave dielectric ceramic material, including the following steps:
s10, obtaining a microwave dielectric ceramic material, and roughening the surface of the microwave dielectric ceramic material to obtain a surface-roughened microwave dielectric ceramic material;
s20, sequentially carrying out sensitization treatment and activation reduction treatment on the microwave dielectric ceramic material with the roughened surface to obtain a microwave dielectric ceramic material with a precious metal elementary substance deposited on the surface;
s30, placing the microwave medium ceramic material with the precious metal elementary substance deposited on the surface in a base metal plating solution for chemical plating, and then sintering to obtain the microwave medium ceramic material with the base metal layer formed on the surface.
According to the surface metallization method of the microwave dielectric ceramic material provided by the embodiment of the application, the surface of the microwave dielectric ceramic material is roughened firstly, so that the roughness of the surface of the microwave dielectric ceramic material is improved, the subsequent adhesion and combination of metal salt, metal ions, metal simple substances and the like on the surface of the ceramic material are facilitated, and the combination stability and the compactness of a metallization layer and the ceramic material are improved. Then carrying out sensitization treatment and activation reduction treatment to enable the surface of the microwave dielectric ceramic material to deposit noble metal simple substance particles, wherein the noble metal simple substance particles have high activity and can provide catalytic activity centers for subsequent chemical plating. And then carrying out chemical plating treatment in a base metal plating solution to form a catalytic active center taking a precious metal simple substance on the surface of the microwave medium ceramic material as a center, replacing the precious metal on the surface of the ceramic material with a base metal through an oxidation-reduction reaction, and forming a base metal layer on the surface of the microwave medium ceramic material. The method of forming the base metal layer in situ on the surface of the ceramic material is beneficial to improving the bonding force between the base metal layer and the ceramic material. And then the metallized layer is diffused through sintering treatment, the compactness of the metallized layer and the binding force with the ceramic material are enhanced, and thus a high-quality metallized base metal layer with high compactness, uniform thickness and good adhesive force consistency is formed on the surface of the microwave medium ceramic material. According to the surface metallization method of the microwave dielectric ceramic material, on one hand, the consistency and uniformity of the metallization layer on the surface of the microwave dielectric ceramic material are improved, and the bonding tightness between the metallization layer and the surface of the ceramic material is improved, so that the bonding and performance stability of the microwave dielectric ceramic material subjected to surface metallization treatment is improved. On the other hand, the base metal layer is adopted to replace the noble metal layer, so that the cost is reduced and the product conductivity deterioration caused by electron migration of the noble metal in the use environment is avoided on the premise of ensuring the material conductivity.
In some embodiments, in the step S10, the step of performing the coarsening process includes: and etching the surface of the microwave dielectric ceramic material by adopting an acid solution. According to the embodiment of the application, the surface of the microwave dielectric ceramic material is etched by the acidic solution, the surface micro-morphology of the microwave dielectric ceramic material is changed by etching, the roughness of the surface of the ceramic material is improved, the metal ions can successfully nucleate and grow on the surface of the microwave dielectric ceramic material in the subsequent chemical plating process, and meanwhile, the combination between the metallization layer and the microwave dielectric ceramic is improved, so that the uniformity and the compactness of the metallization layer are improved, and the combination with the ceramic material is tight.
In some embodiments, the acidic solution comprises: at least one of hydrochloric acid, concentrated sulfuric acid and hydrofluoric acid with the mass percentage concentration of 10-20%; the acid solutions can effectively etch the surface of the ceramic material and improve the surface roughness of the ceramic material. In some preferred embodiments, the surface of the microwave dielectric ceramic material is etched by using a hydrochloric acid solution with the mass percentage concentration of 10-20%, and the acid solution has better etching efficiency on the surface of the microwave dielectric ceramic material, so that excessive etching can be avoided, and the formation of a surface with uniform roughness is facilitated. In some embodiments, the hydrochloric acid is present at 10%, 12%, 15%, 18%, 20%, etc. by mass.
In some embodiments, the etching treatment time is 3-5 minutes; the etching time duration has a good etching effect on the surface of the microwave dielectric ceramic material, if the etching time duration is too long, the surface of the ceramic material is excessively etched, and if the etching time duration is too short, the etching effect is not obvious, so that the bonding tightness between the metallization layer and the ceramic material is not improved. In some embodiments, the duration of the etching process includes, but is not limited to, 3 minutes, 4 minutes, 5 minutes, and the like.
In some embodiments, in step S10, the preparing of the microwave dielectric ceramic material includes: the metal oxide or metal salt is used as a raw material and is prepared by a solid-phase sintering process. In some embodiments, after the raw material components such as metal oxide or metal salt are uniformly mixed, the raw material components are firstly calcined, then the calcined powder is pressed and formed into a green body, and then the green body is sintered to obtain the microwave dielectric ceramic material. The embodiment of the application does not specifically limit the specific preparation steps, conditions and the like of the microwave dielectric ceramic material and the preparation method thereof, and a suitable microwave dielectric ceramic material can be selected according to the actual application requirements in specific applications.
In some embodiments, the microwave dielectric ceramic material has a relative dielectric constant of 4-50, a quality factor of not less than 30000GHz, and a temperature coefficient of resonance frequency of 0 + -10 ppm/DEG C. The ceramic material with the proper dielectric constant, the high-quality factor and the near-zero adjustable resonant frequency temperature coefficient is preferably adopted in the embodiment of the application, and the application requirement in the field of 5G communication can be better met.
In some embodiments, the metal oxide comprises: at least one of zinc oxide, silicon dioxide, magnesium oxide, manganese dioxide, lanthanum oxide, samarium oxide, aluminum oxide and titanium dioxide. In some embodiments, the metal salt comprises: at least one of barium carbonate, strontium carbonate and calcium carbonate. The raw materials such as the metal oxide and the metal salt adopted in the embodiment of the application can be used for preparing the microwave dielectric ceramic material, and the dielectric property, the temperature stability, the quality factor and the like of the microwave dielectric ceramic material can be adjusted by selecting the raw materials and the mixture ratio. In some embodiments, the raw material components of the microwave dielectric ceramic material, such as the metal oxide, the metal salt, and the like, are high-purity materials, such as raw materials with a purity of not less than 99%, and further materials with a purity of 99.9%, so that impurities are prevented from being introduced, and the performance stability of the microwave dielectric ceramic material is improved.
In some embodiments, in the step S20, the step of sensitizing includes: and placing the microwave dielectric ceramic material with the roughened surface in a silver ammonia solution and/or a palladium chloride solution for mixing treatment, forming a silver ammonia and/or palladium chloride sensitized layer on the surface of the microwave dielectric ceramic material with the roughened surface, and enabling silver ions and palladium ions to be combined to the surface of the microwave dielectric ceramic material with the roughened surface. In some specific embodiments, the microwave dielectric ceramic material with the roughened surface is placed in a silver-ammonia solution and/or a palladium chloride solution for mixing treatment for 1-2 hours, and then is washed with deionized water for 2-3 times, so that the sensitized microwave dielectric ceramic material is obtained. In some preferred embodiments, the step of sensitizing comprises: and placing the microwave dielectric ceramic material with the roughened surface in a silver ammonia solution for mixing treatment, forming a silver ammonia sensitized layer on the surface of the microwave dielectric ceramic material with the roughened surface, and bonding silver ions to the surface of the microwave dielectric ceramic material with the roughened surface.
In some embodiments, the preparation of the silver ammonia solution comprises the steps of: and adding ammonia water into the silver salt solution with the concentration of 5-7 g/L until the solution is precipitated and dissolved to obtain the silver-ammonia solution. In some embodiments, ammonia water is added into silver nitrate solution with the concentration of 5-7 g/L until brown precipitate is dissolved and disappears, and silver ammonia solution is obtained.
In some embodiments, the step of activating the reduction treatment comprises: and placing the sensitized product in a reducing activating agent for mixing treatment, directly reducing silver ions and palladium ions on the surface of the ceramic material into a silver simple substance and a palladium simple substance respectively through the reducing activating agent, forming a silver simple substance and palladium simple substance particle layer on the surface of the microwave medium ceramic material, and obtaining the microwave medium ceramic material with the surface deposited with the precious metal simple substances, wherein the precious metal simple substances deposited on the surface have very high activity and can provide neutral catalytic activity for subsequent chemical plating. In some specific embodiments, the sensitized product is placed in a reducing activator and mixed for 5-7 minutes, and the microwave dielectric ceramic material with the surface deposited with the noble metal simple substance can be obtained.
In some embodiments, the reducing activator comprises: at least one of sodium dihydrogen phosphite, sodium hypophosphite and glyoxylic acid; the reducing activators can directly reduce silver ions and palladium ions on the surface of the microwave dielectric ceramic material into silver elementary substance particles, and silver elementary substance and palladium elementary substance layers are formed on the surface of the microwave dielectric ceramic material. In some preferred embodiments, sodium dihydrogen phosphite is used as the reducing activator.
In some embodiments, the concentration of the reducing activator is 25-35 g/L, and the reducing activator with the concentration has better reduction efficiency on silver ions and palladium ions on the surface of the microwave dielectric ceramic material. In some embodiments, the concentration of reducing activator includes, but is not limited to, 25g/L, 28g/L, 30g/L, 33g/L, 35g/L, and the like.
According to the microwave medium ceramic material with the roughened surface, silver ammonia solution and/or palladium chloride solution are/is adopted for sensitization treatment to enable silver ions and palladium ions to be combined to the surface of the ceramic material, then reduction activating agent is adopted for activation reduction treatment, and the silver ions and the palladium ions on the surface of the microwave medium ceramic material are directly reduced into silver and palladium elementary substance particles in situ, so that a layer of precious metal elementary substance with uniform thickness, uniform distribution and compactness is formed on the surface of the microwave medium ceramic material. And silver ions and palladium ions on the surface of the microwave dielectric ceramic material are directly reduced into simple substances in an in-situ reduction mode, so that the introduction of other metal ions can be effectively avoided, the purity of a subsequently prepared metallized layer is ensured, and the improvement of the combination stability of the metallized layer and the microwave dielectric ceramic material is facilitated.
In some embodiments, in the step S30, the step of electroless plating includes: placing the microwave medium ceramic material with the surface deposited with the precious metal elementary substance in a base metal plating solution, mixing at the temperature of 50-70 ℃ and the pH value of 11-12 to form a catalytic active center with the precious metal elementary substance on the surface of the microwave medium ceramic material as the center, reducing the base metal in the base metal plating solution through an oxidation-reduction reaction to form a base metal plating layer to replace the precious metal elementary substance deposited on the surface of the ceramic material, and combining the base metal plating layer with the surface of the microwave medium ceramic material to form a base metal layer to obtain the microwave medium ceramic material with the base metal layer formed on the surface. Wherein, the conditions of 50-70 ℃ of temperature and 11-12 of pH value fully ensure the reduction and replacement capability of the base metal plating solution, so that the base metal has better reduction, replacement and deposition efficiency. If the pH value is too high, the deposition rate of base metal on the surface of the microwave dielectric ceramic material is too high, so that the disproportionation reaction is accelerated, and the stability of the plating solution is reduced. If the temperature is too low, the chemical plating rate is too slow, and even a base metal plating layer is difficult to form; if the temperature is too high, the plating solution is easy to decompose and lose efficacy, and the side reactions are more.
In some embodiments, the base metal plating solution comprises: copper salt, reducing agent and complexing agent. The base metal plating solution in the embodiment of the application adopts the plating solution containing copper ions, the conductivity of copper is close to that of silver, and the conductivity of a formed metallization layer can be effectively ensured, so that the conductivity of the microwave dielectric ceramic material after surface treatment is ensured.
In some embodiments, the copper salt comprises copper sulfate pentahydrate; the copper salt has better deposition efficiency on the surface of the microwave dielectric ceramic material, thereby improving the formation efficiency of the copper metallization layer.
In some embodiments, the base metal layer is a copper layer, and the copper metal layer effectively ensures the conductive performance of the microwave medium ceramic material.
In some embodiments, the reducing agent comprises: formaldehyde, hypophosphite, dimethylamino borane, glyoxylic acid, sodium hydroxymethanesulfinate hydrate and thiourea dioxide. In some preferred embodiments, the reducing agent is formaldehyde, and formaldehyde is used as the reducing agent, so that the reducing agent is low in price and wide in source, and is beneficial to improving the deposition rate of copper, improving the mass and atomic percentage of copper in a coating and reducing the introduction of the copper and impurity components.
The chemical plating needs to ensure the reducing capability of the plating solution under the condition of higher pH value, but the base metal ions such as copper ions and the like can react to generate hydroxide precipitates under the alkaline condition, so that the base metal plating layer is not easy to generate. In order to avoid the generation of precipitated impurities, a complexing agent needs to be added to the plating solution, and the complexing agent is coordinated with metal ions such as free copper ions to form a complex compound. In some embodiments, the complexing agent comprises: at least one of EDTA, tartaric acid, triethanolamine and citric acid, and the complexing agents have good complexing effect on base metal ions such as copper ions and the like, can effectively prevent the metal ions from generating hydroxide precipitates under the condition of alkaline chemical plating, and ensure the formation efficiency of a metal plating layer. And the stability of the base metal plating solution and the deposition rate of the metal on the surface of the ceramic material are improved. In some preferred embodiments, the complexing agent adopts two types of EDTA and tartaric acid, and the two types of EDTA and tartaric acid are compounded, so that a higher and more stable deposition speed can be kept, the cost is reduced, and the environmental pollution is reduced.
In some embodiments, the concentration of the copper salt is 15-30 g/L, the concentration of the reducing agent is 12-18 mL/L, and the concentration of the complexing agent is 20-60 g/L in the base metal plating solution, so that the base metal plating solution has better deposition efficiency under the concentration condition.
In some embodiments, the step of configuring the base metal plating solution comprises: mixing copper sulfate pentahydrate (CuSO)4·5H2O) is dissolved in deionized water to form a solution with the concentration of 15-30 g/L; dissolving disodium ethylene diamine tetraacetate (EDTA-2Na) in deionized water to form a solution with the concentration of 20-40 g/L; mixing potassium sodium tartrate (NaKC)4H4O6·4H2O) dissolving in deionized water to form a solution with the concentration of 10-20 g/L; adding the disodium ethylene diamine tetraacetate solution and the potassium-sodium tartrate solution into the copper sulfate solution and stirring to form a mixed solution; and adding a sodium hydroxide solution into the mixed solution to adjust the pH value to be 12, keeping the temperature at 60 ℃, and adding formaldehyde to make the concentration of the formaldehyde be 12-18 mL/L to obtain the copper plating solution.
In some embodiments, in the step S30, the conditions of the sintering process include: the heat preservation is carried out for 2-4 hours under the vacuum condition with the temperature of 900-1000 ℃, on one hand, the diffusion of metal in base metal plating layers such as copper and the like on the surface of a microwave medium ceramic material is promoted, the binding force between the metal plating layers and the surface of the ceramic is increased, and the performances of oxidation resistance, electric conduction, heat conduction and the like of the plating layers are improved; on the other hand, the microwave dielectric ceramic and the gas in the surface metallization layer are promoted to escape from the air holes by sintering under the vacuum condition, so that the product does not contain the air holes, and the density of the metallization layer and the product is improved. If the sintering temperature is too high or the sintering time is too long, copper is melted, and the consistency and other electrochemical properties of the metallization layer are adversely affected; if the sintering temperature is too low or the sintering time is too short, the diffusion of the metal coating is not favorably improved, the bonding force between the metal coating and the ceramic surface is not favorably improved, and the performances of oxidation resistance, electric conduction, heat conduction and the like are not favorably improved.
The thickness of the base metal layer in the embodiment of the application can be adjusted by factors such as the chemical plating treatment time and the base metal plating solution formula, and can be flexibly adjusted according to specific application requirements, so that various application requirements are met. In some embodiments, the thickness of the base metal layer is 10-30 microns, and the metalized layer with the thickness not only ensures the conductivity, but also ensures the comprehensive properties of the material, such as dielectric property, stability, quality factor and the like.
The second aspect of the embodiments of the present application provides a microwave dielectric ceramic device, which is prepared by the above surface metallization method of the microwave dielectric ceramic material, and includes a microwave dielectric ceramic substrate and a base metal layer bonded on the surface of the microwave dielectric ceramic substrate.
The microwave dielectric ceramic device provided by the second aspect of the embodiment of the application is prepared by the surface metallization method of the microwave dielectric ceramic material, and comprises a microwave dielectric ceramic substrate and a base metal layer combined on the surface of the microwave dielectric ceramic substrate, wherein the metallization layer has good consistency and uniformity, and is tightly combined with the surface of the ceramic material, so that the performance stability of the microwave dielectric ceramic device is improved. In addition, the base metal is adopted to replace the noble metal, so that the cost is reduced, and the product conductivity deterioration caused by silver electron migration of noble metals such as silver in an application environment is avoided. The microwave dielectric ceramic device in the embodiment of the application meets the performance requirement of the ceramic filter for 5G communication.
The microwave dielectric ceramic device of the embodiment of the present application includes, but is not limited to, a microwave dielectric ceramic filter.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the advanced performance of the surface metallization method of the microwave dielectric ceramic material and the microwave dielectric ceramic device apparent in the embodiments of the present application, the above technical solutions are illustrated by the following embodiments.
Example 1
A microwave dielectric ceramic device is prepared by the following steps:
1) preparing a microwave dielectric ceramic filter mature blank: zinc oxide (ZnO), silicon dioxide (SiO)2) Starting material according to chemical expression Zn2SiO4Charging xMO, wherein M represents at least one of 2/3Al, Mg and 1/2Ti, and adding alumina (Al) according to a molar ratio x of 0.005-0.032O3) Magnesium oxide (MgO) and titanium dioxide (TiO)2) At least one of (1). This practice employs Zn2SiO4—0.005Al2O3—0.03Ti1/2And the chemical composition percentage of O, wherein the purities of the zinc oxide, the silicon dioxide, the aluminum oxide and the titanium dioxide are all more than 99%. The raw materials are uniformly mixed and then calcined for 4 hours at 1000 ℃, then powder dry pressing forming equipment is adopted to press a ceramic filter green body, and the green body is sintered for 4 hours at 1200 ℃, so that a ceramic filter cooked blank is obtained.
2) And (3) placing the ceramic filter blank obtained in the step (1) into a hydrochloric acid solution with the mass percentage concentration of 20%, stirring for 5 minutes, performing roughening treatment, and then washing for 3 times by using deionized water to remove hydrochloric acid on the surface.
3) The preparation method of the silver ammonia solution comprises the following steps: dissolving a proper amount of silver nitrate by using deionized water to obtain a silver nitrate solution with the concentration of 5g/L, adding an ammonia water solution into the silver nitrate solution, and stirring until brown precipitates completely disappear to obtain a silver ammonia solution. And (3) adding the ceramic filter blank subjected to the roughening treatment obtained in the step (2) into a silver-ammonia solution, stirring for 1.5 hours for sensitization treatment, and then washing for 3 times by using deionized water.
4) Sensitizing treatment obtained in step 3Adding the calcined blank of the ceramic filter into sodium dihydrogen phosphite (NaH) with the concentration of 25g/L2PO3) Stirring the solution for 7 minutes to carry out activation reduction treatment, then washing the solution for 3 times by using deionized water, and finally drying the solution in a drying oven at 110 ℃ to obtain a microwave dielectric ceramic filter blank with silver elementary substance deposited on the surface.
5) The step of preparing the chemical plating solution comprises the following steps: mixing copper sulfate pentahydrate (CuSO)4·5H2O) is dissolved in deionized water to form a solution with the concentration of 15 g/L; dissolving disodium ethylene diamine tetraacetate (EDTA-2Na) in deionized water to form a solution with the concentration of 20 g/L; mixing potassium sodium tartrate (NaKC)4H4O6·4H2O) is dissolved in deionized water to form a solution with the concentration of 10 g/L; adding the disodium ethylene diamine tetraacetate solution and the potassium-sodium tartrate solution into the copper sulfate solution and stirring to form a mixed solution; and adding a sodium hydroxide solution into the mixed solution to adjust the pH value so as to stabilize the pH value at 12, keeping the temperature at 60 ℃, and adding a formaldehyde solution so as to make the concentration of the formaldehyde solution be 12ml/L, thereby obtaining the chemical plating solution. And (4) adding the ceramic filter mature blank obtained in the step (4) after the activation reduction treatment into chemical plating solution, keeping the temperature constant at 60 ℃, keeping the pH value at 12, continuously stirring, and completing the chemical plating when the solution is changed from blue to colorless. Washed 3 times with deionized water and dried in an oven at 60 ℃.
6) And (5) preserving the temperature of the ceramic filter blank subjected to chemical plating in the step (5) in a vacuum quartz tube at 900 ℃ for 2 hours to obtain the microwave dielectric ceramic device.
Example 2
A microwave dielectric ceramic device is prepared by the following steps:
1) preparing a microwave dielectric ceramic filter mature blank: magnesium oxide MgO and calcium carbonate CaCO3Titanium oxide TiO2MgTiO is used as a starting material according to a chemical expression (1-x)3—xCaTiO3(x is 0.04-0.07) in a molar ratio. The implementation adopts 0.95MgTiO3—0.05CaTiO3Wherein the purities of the magnesium oxide, the calcium carbonate and the titanium dioxide are all more than 99%. The raw materials are evenly mixed and then calcined for 5 hours at 1150 ℃, and thenAnd then pressing the ceramic filter green body by adopting powder dry pressing equipment, and sintering the green body at 1360 ℃ for 4 hours to obtain a ceramic filter green body.
2) And (3) placing the ceramic filter blank obtained in the step (1) into a hydrochloric acid solution with the mass percentage concentration of 20%, stirring for 5 minutes, performing roughening treatment, and then washing for 3 times by using deionized water to remove hydrochloric acid on the surface.
3) The preparation method of the silver ammonia solution comprises the following steps: dissolving a proper amount of silver nitrate by using deionized water to obtain a silver nitrate solution with the concentration of 6g/L, adding an ammonia water solution into the silver nitrate solution, and stirring until brown precipitates completely disappear to obtain a silver ammonia solution. And (3) adding the ceramic filter blank subjected to the roughening treatment obtained in the step (2) into a silver-ammonia solution, stirring for 1.5 hours for sensitization treatment, and then washing for 3 times by using deionized water.
4) Adding the ceramic filter clinker obtained in the step 3 after the sensitization treatment into sodium dihydrogen phosphite (NaH) with the concentration of 30g/L2PO3) Stirring the solution for 5 minutes to carry out activation reduction treatment, then washing the solution for 3 times by using deionized water, and finally drying the solution in a drying oven at 130 ℃ to obtain a microwave dielectric ceramic filter cooked blank with silver elementary substance deposited on the surface.
5) The step of preparing the chemical plating solution comprises the following steps: mixing copper sulfate pentahydrate (CuSO)4·5H2O) is dissolved in deionized water to form a solution with the concentration of 25 g/L; dissolving disodium ethylene diamine tetraacetate (EDTA-2Na) in deionized water to form a solution with the concentration of 30 g/L; mixing potassium sodium tartrate (NaKC)4H4O6·4H2O) is dissolved in deionized water to form a solution with the concentration of 15 g/L; adding the disodium ethylene diamine tetraacetate solution and the potassium-sodium tartrate solution into the copper sulfate solution and stirring to form a mixed solution; and adding a sodium hydroxide solution into the mixed solution to adjust the pH value so as to stabilize the pH value at 12, keeping the temperature at 60 ℃, and adding a formaldehyde solution so as to enable the concentration to be 18ml/L, thereby obtaining the chemical plating solution. And (4) adding the ceramic filter mature blank obtained in the step (4) after the activation reduction treatment into chemical plating solution, keeping the temperature constant at 60 ℃, keeping the pH value at 12, continuously stirring, and completing the chemical plating when the solution is changed from blue to colorless. Washing the glass substrate with deionized water for 3 times,and dried in an oven at 60 ℃.
6) And (4) preserving the temperature of the ceramic filter blank subjected to chemical plating obtained in the step (5) in a vacuum quartz tube at 950 ℃ for 3 hours to obtain the microwave dielectric ceramic device.
Example 3
A microwave dielectric ceramic device is prepared by the following steps:
1) preparing a microwave dielectric ceramic filter mature blank: with calcium carbonate CaCO3Titanium oxide TiO2Aluminum oxide Al2O3La, lanthanum oxide2O3Starting material is CaTiO according to the chemical expression (1-x)3—xLaAlO3(x is 0.2-0.5) in a molar ratio. This embodiment uses 0.7CaTiO3—0.3LaAlO3The chemical composition percentage of (1), wherein the purities of the calcium carbonate, the titanium dioxide, the aluminum oxide and the lanthanum oxide are all more than 99%. The raw materials are uniformly mixed and then calcined for 10 hours at 1250 ℃, then powder dry pressing forming equipment is adopted to press a ceramic filter green body, and the green body is sintered for 6 hours at 1430 ℃ to obtain a ceramic filter cooked blank.
2) And (3) placing the ceramic filter blank obtained in the step (1) into a hydrochloric acid solution with the mass percentage concentration of 15%, stirring for 5 minutes, performing coarsening treatment, and then washing for 3 times by using deionized water to remove hydrochloric acid on the surface.
3) The preparation method of the silver ammonia solution comprises the following steps: dissolving a proper amount of silver nitrate by using deionized water to obtain a silver nitrate solution with the concentration of 7g/L, adding an ammonia water solution into the silver nitrate solution, and stirring until brown precipitates completely disappear to obtain a silver ammonia solution. And (3) adding the ceramic filter blank subjected to the roughening treatment obtained in the step (2) into a silver-ammonia solution, stirring for 1.5 hours for sensitization treatment, and then washing for 3 times by using deionized water.
4) Adding the ceramic filter clinker obtained in the step 3 after the sensitization treatment into sodium dihydrogen phosphite (NaH) with the concentration of 35g/L2PO3) Stirring the solution for 5 minutes to carry out activation reduction treatment, then washing the solution for 3 times by using deionized water, and finally drying the solution in a drying oven at 150 ℃ to obtain a microwave dielectric ceramic filter blank with silver elementary substance deposited on the surface.
5) The step of preparing the chemical plating solution comprises the following steps: mixing copper sulfate pentahydrate (CuSO)4·5H2O) is dissolved in deionized water to form a solution with the concentration of 30 g/L; dissolving disodium ethylene diamine tetraacetate (EDTA-2Na) in deionized water to form a solution with the concentration of 40 g/L; mixing potassium sodium tartrate (NaKC)4H4O6·4H2O) is dissolved in deionized water to form a solution with the concentration of 20 g/L; adding the disodium ethylene diamine tetraacetate solution and the potassium-sodium tartrate solution into the copper sulfate solution and stirring to form a mixed solution; and adding a sodium hydroxide solution into the mixed solution to adjust the pH value so as to stabilize the pH value at 12, keeping the temperature at 60 ℃, and adding a formaldehyde solution so as to enable the concentration to be 18ml/L, thereby obtaining the chemical plating solution. And (4) adding the ceramic filter mature blank obtained in the step (4) after the activation reduction treatment into chemical plating solution, keeping the temperature constant at 60 ℃, keeping the pH value at 12, continuously stirring, and completing the chemical plating when the solution is changed from blue to colorless. Washed 3 times with deionized water and dried in an oven at 60 ℃.
6) And (4) preserving the temperature of the ceramic filter blank subjected to chemical plating obtained in the step (5) in a vacuum quartz tube for 4 hours at 1000 ℃ to obtain the microwave dielectric ceramic device.
Further, in order to verify the advancement of the embodiments of the present application, the following performance tests were performed on the prepared microwave dielectric ceramic filter blanks and the microwave dielectric ceramic devices prepared in embodiments 1 to 3, respectively:
1. the dielectric constant, the quality factor and the temperature coefficient of the resonant frequency of the microwave dielectric ceramic filter green compact prepared in the embodiments 1 to 3 were respectively tested, and the test results are shown in the following table 1:
TABLE 1
| Dielectric constant εr | Quality factor Q f | Temperature coefficient of resonance frequency tauf | |
| Example 1 | 7.9 | 55000GHz | -0.5ppm/℃ |
| Example 2 | 20.6 | 68000GHz | 0.3ppm/℃ |
| Example 3 | 44.2 | 45600GHz | -1ppm/℃ |
As can be seen from the test results in Table 1, the microwave dielectric ceramic filter blanks prepared in embodiments 1-3 of the present application all have high quality factors, near-zero adjustable resonant frequency temperature coefficients, and appropriate dielectric constants, so that the high stability and high reliability of the microwave dielectric ceramic filter are ensured, and the application requirements in the 5G communication field can be met.
2. The surface morphology of the microwave dielectric ceramic device prepared in example 1 was observed by a scanning electron microscope, and the test result is shown in fig. 2, in which the microstructure of the metallized layer formed on the surface of the microwave dielectric ceramic device was uniform, the density was high, and the average size of the grains was about 15 μm.
3. The cross section of the microwave dielectric ceramic device prepared in example 1 was observed by a scanning electron microscope, and the test result is shown in fig. 3, in which the thickness of the metallization layer formed on the surface of the microwave dielectric ceramic device is uniform and about 15 μm, and the bonding interface between the microwave dielectric ceramic substrate and the surface metallization layer has good fusibility and tight bonding.
4. The properties of the surface metallization layer, such as thickness, adhesion, center insertion loss, and the like, of the microwave dielectric ceramic devices prepared in examples 1 to 3 were tested. Wherein the thickness test is by scanning electron microscope; the adhesion test adopts a tension meter to apply force in the vertical direction after a thin copper wire is welded on the surface of the metallized layer until the metallized layer falls off or the metallized layer with the ceramic falls off, and the requirement is more than or equal to 2.0kgf/mm2(ii) a The central insertion loss is measured by respectively assembling the microwave dielectric ceramic devices prepared in the embodiments 1 to 3 into finished products of ceramic filters of 4.9GHz, 3.5GHz and 2.6GHz by an SMT process, and outputting the finished products when indexes of the corresponding ceramic filters are tested. The test results are shown in table 2 below:
TABLE 2
| Thickness of metallization layer | Adhesion of metallized layer | Center insertion loss | |
| Example 1 | About 15 μm | 3.6kgf/mm2 | 0.85dB |
| Example 2 | About 15 μm | 3.6kgf/mm2 | 0.52dB |
| Example 3 | About 15 μm | 3.6kgf/mm2 | 0.70dB |
As can be seen from the test results in Table 2, the metallized layer on the surface of the microwave dielectric ceramic device prepared in the embodiments 1 to 3 of the present application has uniform thickness, strong adhesion with the ceramic substrate, and stable bonding. After the microwave dielectric ceramic device is manufactured into ceramic filter finished products with different frequencies, the measured center insertion loss is small, and the high-performance requirement of the ceramic filter for 5G communication can be well met.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A surface metallization method of a microwave dielectric ceramic material is characterized by comprising the following steps:
obtaining a microwave dielectric ceramic material, and roughening the surface of the microwave dielectric ceramic material to obtain a microwave dielectric ceramic material with a roughened surface;
sequentially carrying out sensitization treatment and activation reduction treatment on the microwave dielectric ceramic material with the roughened surface to obtain a microwave dielectric ceramic material with a precious metal elementary substance deposited on the surface;
and placing the microwave medium ceramic material with the surface deposited with the precious metal simple substance in a base metal plating solution for chemical plating, and then sintering to obtain the microwave medium ceramic material with the base metal layer formed on the surface.
2. A method of surface metallization of a microwave dielectric ceramic material as set forth in claim 1, wherein said step of sensitizing comprises: placing the microwave dielectric ceramic material with the roughened surface in a silver-ammonia solution and/or a palladium chloride solution for mixing treatment;
and/or the step of activating reduction treatment comprises the following steps: and (3) placing the sensitized product in a reducing activating agent for mixing treatment to obtain the microwave dielectric ceramic material with the surface deposited with the noble metal simple substance.
3. A method for metallizing a surface of a microwave dielectric ceramic material as defined in claim 2, wherein said preparing of a silver ammonia solution comprises the steps of: adding ammonia water into a silver salt solution with the concentration of 5-7 g/L until the solution is precipitated and dissolved to obtain the silver-ammonia solution;
and/or, the reductive activator comprises: at least one of sodium dihydrogen phosphite, sodium hypophosphite and glyoxylic acid;
and/or the concentration of the reducing activator is 25-35 g/L.
4. A surface metallization method of a microwave dielectric ceramic material as claimed in any one of claims 1 to 3, wherein said base metal plating solution comprises: copper salt, reducing agent and complexing agent;
and/or the step of electroless plating comprises: and placing the microwave medium ceramic material with the surface deposited with the precious metal simple substance in the base metal plating solution, and mixing at the temperature of 50-70 ℃ and the pH value of 11-12 to obtain the microwave medium ceramic material with the base metal layer formed on the surface.
5. The method for metallizing the surface of a microwave dielectric ceramic material according to claim 4, wherein the base metal layer is a copper layer;
and/or the base metal layer has a thickness of 10-30 microns.
6. A surface metallization method of a microwave dielectric ceramic material as in claim 4, wherein said copper salt comprises copper sulfate pentahydrate;
and/or, the reducing agent comprises: at least one of formaldehyde, hypophosphite, dimethylamino borane, glyoxylic acid, sodium hydroxymethanesulfinate hydrate and thiourea dioxide;
and/or, the complexing agent comprises: at least one of EDTA, tartaric acid, triethanolamine, citric acid;
and/or in the base metal plating solution, the concentration of the copper salt is 15-30 g/L, the concentration of the reducing agent is 12-18 mL/L, and the concentration of the complexing agent is 20-60 g/L.
7. A method for metallizing a surface of a microwave dielectric ceramic material according to any one of claims 1 to 3, 5 or 6, wherein the conditions of the sintering treatment comprise: and preserving the heat for 2-4 hours under the vacuum condition at the temperature of 900-1000 ℃.
8. A method for metallizing a surface of a microwave dielectric ceramic material as defined in claim 7, wherein said roughening step comprises: etching the surface of the microwave dielectric ceramic material by using an acid solution;
and/or the preparation of the microwave dielectric ceramic material comprises the following steps: the metal oxide or metal salt is used as a raw material and is prepared by a solid-phase sintering process.
9. A method for metallizing a surface of a microwave dielectric ceramic material as defined in claim 8 wherein said acidic solution comprises: at least one of hydrochloric acid, concentrated sulfuric acid and hydrofluoric acid with the mass percentage concentration of 10-20%;
and/or the etching treatment time is 3-5 minutes;
and/or the relative dielectric constant of the microwave dielectric ceramic material is 4-50, the quality factor is not lower than 30000GHz, and the temperature coefficient of the resonant frequency is 0 +/-10 ppm/DEG C;
and/or, the metal oxide comprises: at least one of zinc oxide, silicon dioxide, magnesium oxide, manganese dioxide, lanthanum oxide, samarium oxide, aluminum oxide and titanium dioxide;
and/or, the metal salt comprises: at least one of barium carbonate, strontium carbonate and calcium carbonate.
10. A microwave dielectric ceramic device is characterized by being prepared by the surface metallization method of the microwave dielectric ceramic material according to any one of claims 1 to 9, and comprising a microwave dielectric ceramic substrate and a base metal layer combined on the surface of the microwave dielectric ceramic substrate.
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