阅读说明：本技术 一种高温共烧填孔浆料 (High-temperature co-fired hole filling slurry ) 是由 张建益 孙社稷 王要东 崔国强 王雒瑶 张亚鹏 曾艳艳 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种高温共烧填孔浆料,该浆料由微米级金属粉末、无机添加剂和有机载体组成,其中有机载体中含有邻苯二甲酸酯。本发明的浆料能与生料带在1800℃匹配共烧,烧结后填孔金属致密完整,与生瓷片匹配。(the invention relates to a high-temperature co-fired pore-filling slurry, which consists of micron-sized metal powder, an inorganic additive and an organic carrier, wherein the organic carrier contains phthalate. The slurry can be matched with a raw material belt and co-fired at 1800 ℃, and the pore-filling metal is compact and complete after sintering and is matched with a raw ceramic chip.)

1. A pore-filling slurry for high-temperature co-fired ceramics is characterized by comprising metal powder, inorganic additives and an organic carrier, wherein the organic carrier contains phthalate.

2. The pore-filling slurry of claim 1, wherein, in the pore-filling slurry,

The content of the metal powder is 85-95% of the total weight of the pore-filling slurry; and/or

The content of the inorganic additive is 0.5-5% of the total weight of the pore-filling slurry; and/or

The content of the phthalate ester is 1.5-3% of the total weight of the pore-filling slurry.

3. The pore-filling slurry of claim 1,

The phthalate is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate or any combination thereof; and/or

The metal is tungsten, molybdenum, manganese or any combination thereof; and/or

The inorganic additive is metal oxide, non-metal oxide, metal nitride, silicate, metal oxide precursor or any combination thereof, preferably alumina, yttria, aluminum nitride or any combination thereof.

4. The pore-filling slurry of claim 3, wherein the phthalate ester is butyl benzyl phthalate and/or dicyclohexyl phthalate; preferably, the content of the butyl benzyl phthalate and/or the dicyclohexyl phthalate is 2-3% of the total weight of the pore-filling slurry.

5. The pore-filling slurry of claim 3, wherein the metal is tungsten and the phthalate is butyl benzyl phthalate and/or dicyclohexyl phthalate.

6. The pore-filling slurry of claim 1, wherein the organic vehicle of the pore-filling slurry further comprises a thickener and an organic solvent; preferably, the organic vehicle is present in an amount of 5% to 15% by weight of the total pore-filling slurry.

7. The pore-filling slurry of claim 6, wherein, in the pore-filling slurry,

The thickening agent is selected from any one or combination of more of ethyl cellulose, nitrocellulose, acrylic resin, butyraldehyde resin and maleic resin; preferably, the thickener is present in an amount of 1% to 3%, preferably 1.5% to 2.5%, by weight of the total pore-filling slurry; and/or

The organic solvent is selected from any one or combination of more of terpineol, butyl carbitol acetate, ethylene glycol ethyl ether acetate and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate; preferably, the organic solvent is present in an amount of 1% to 10%, preferably 2% to 8%, by weight of the total pore-filling slurry.

8. A method of making the pore-filling slurry of any one of claims 1-7, comprising:

(1) Weighing all components of the organic carrier, and fully stirring at the temperature of 60-90 ℃ to obtain the organic carrier; and

(2) Adding metal powder and inorganic additives into the organic carrier obtained in the step (1), and performing roll dispersion to obtain the pore-filling slurry.

9. The application of phthalate in improving the hole-filling printing effect of the hole-filling slurry or in preparing the hole-filling slurry with the improved hole-filling printing effect; preferably, the phthalate is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate or any combination thereof; more preferably, the phthalate is butyl benzyl phthalate and/or dicyclohexyl phthalate.

10. A high temperature co-fired ceramic made from a ceramic green body by pore-filling with the pore-filling slurry of any one of claims 1-7.

Technical Field

The invention belongs to the technical field of microelectronic manufacturing, and particularly relates to high temperature co-fired (HTCC) hole filling slurry and a preparation method of the hole filling slurry.

Background

With the development and automation level improvement of the industries such as communication, aerospace, automobiles, electronic consumer goods and the like, the requirements on the size, the function and the stability of electronic circuits and devices are higher and higher. In order to meet the requirements of miniaturization, high reliability, low power consumption and the like of electronic circuits and devices, the co-fired ceramic technology is rapidly developed. The High-temperature co-fired ceramic (HTCC) is a material prepared by printing resistance slurry containing High-melting point metals such as tungsten, molybdenum, manganese and the like on a ceramic green body according to the requirements of circuit design, laminating a plurality of layers and co-firing the ceramic green body at High temperature into a whole, has the advantages of corrosion resistance, High temperature resistance, long service life, High efficiency, energy conservation, uniform temperature, good heat conduction performance, High heat compensation speed and the like, does not contain harmful substances such as lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers and the like, and meets the environmental protection requirements of the European Union RoHS and the like.

The solvent used by the conventional slurry is common solvents such as terpineol, and the organic carrier prepared by dissolving cellulose by the solvents has good fluidity, so that the slurry has leveling property. When the printing thickness is relatively thin (the wet film is about 30 μm), the influence of gravity on the printing thickness is small due to the support of the substrate, and the collapse phenomenon cannot occur. However, in the preparation of HTCC, a hole-filling printing process is required, the hole-filling printing has a thickness of about 100 μm and no substrate support, and slurry having good flatness under gravity causes sagging, which may cause disconnection of upper and lower layers at a later stage.

In general, the solvent used for the printed conductor paste for the thick film process is generally a good leveling agent. For example, in patent application CN102270513A, the main solvent used is terpineol, which can make the conductor paste have good printing leveling performance, but for the hole-filling paste, too good fluidity can make the paste flow out from the holes of the green tiles under the action of gravity, so that the filled holes are sunk and not full. Patent CN200480030069.3 has studied the matching between glass powder and green ceramic chip in the co-fired pore-filling slurry, and proposed the high temperature viscosity range of glass powder, but did not study the pore-filling effect of the pore-filling slurry.

the hole filling printing is used as a basic process for manufacturing the HTCC substrate, and the conducting performance of the HTCC substrate is directly influenced by the hole filling effect. The patent application CN102314957A needs to perform more than two times of hole-filling printing to ensure full filling, which increases the complexity of the process and is not suitable for industrial production.

Therefore, there remains a need in the art for a HTCC tungsten conductor via-filling paste that improves the effectiveness of via-filling printing.

Disclosure of Invention

In order to solve the above problems, the present invention provides a pore-filling slurry, wherein the pore-filling slurry contains a metal powder and a phthalate.

In one or more embodiments, the pore-filling slurry contains or consists of metal powder, inorganic additive and organic carrier, wherein the organic carrier contains phthalate ester.

In one or more embodiments, the metal powder is a mixture of one or more of tungsten powder, molybdenum powder, manganese powder; preferably, the metal powder is tungsten powder.

In one or more embodiments, the pore-filling slurry is a tungsten conductor pore-filling slurry.

In one or more embodiments, the metal powder is present in the pore-filling slurry in an amount ranging from 85% to 95%, preferably from 85% to 94.5%, and more preferably from 88% to 92% by weight of the total weight of the pore-filling slurry.

In one or more embodiments, the inorganic additive is a metal oxide, a non-metal oxide, a metal nitride, a silicate, a metal oxide precursor, or a combination thereof; preferably alumina, yttria, aluminum nitride or mixtures thereof.

In one or more embodiments, the inorganic additive is present in the pore-filling slurry in an amount of 0.5% to 5%, preferably 1% to 4%, by weight of the total pore-filling slurry.

In one or more embodiments, the phthalate ester is present in the pore-filling slurry in an amount of 1.5% to 3%, such as 1.5% to 2.5%, 1.5% to 2%, 2% to 3%, 2% to 2.5%, 2.5% to 3% by weight of the total pore-filling slurry.

In one or more embodiments, the phthalate is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, or a combination thereof.

in one or more embodiments, the phthalate is butyl benzyl phthalate and/or dicyclohexyl phthalate; preferably, the content of the butyl benzyl phthalate and/or the dicyclohexyl phthalate is 2-3% of the total weight of the pore-filling slurry.

In one or more embodiments, the metal is tungsten and the phthalate is butyl benzyl phthalate and/or dicyclohexyl phthalate.

In one or more embodiments, the organic vehicle of the pore-filling slurry contains or consists of a thickener, an organic solvent, and the phthalate ester.

In one or more embodiments, the organic vehicle is present in the pore-filling slurry in an amount ranging from 5% to 15%, preferably from 5% to 14.5%, and more preferably from 5% to 10% by weight of the total weight of the pore-filling slurry.

In one or more embodiments, the thickener is selected from the group consisting of any one or more of ethyl cellulose, nitrocellulose, acrylic resins, butyral resins, maleic resins, preferably ethyl cellulose; preferably, the thickener is present in an amount of 1% to 3%, preferably 1.5% to 2.5% by weight of the total pore-filling slurry.

In one or more embodiments, the organic solvent is selected from the group consisting of terpineol, butyl carbitol acetate, ethylene glycol ethyl ether acetate, and a mixture of any one or more of 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate, preferably terpineol; preferably, the organic solvent is present in an amount of 1% to 10%, preferably 2% to 8%, by weight of the total pore-filling slurry.

The present invention also provides a method of making a pore-filling slurry according to any of the embodiments of the present invention, comprising:

(1) Weighing all components of the organic carrier, and fully stirring at the temperature of 60-90 ℃ to obtain the organic carrier; and

(2) Adding metal powder and inorganic additives into the organic carrier in the step (1), and rolling and dispersing to obtain the pore-filling slurry.

In one or more embodiments, the step (2) includes dispersing the mixture of metal powder, inorganic additive, and organic vehicle of step (1) with a three roll mill.

The invention also provides the application of the phthalate in improving the hole-filling printing effect of the hole-filling slurry or in preparing the hole-filling slurry with improved hole-filling printing effect; preferably, the pore-filling slurry is tungsten conductor pore-filling slurry; preferably, the phthalate is dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate or a combination thereof; more preferably, the phthalate is butyl benzyl phthalate and/or dicyclohexyl phthalate.

The invention also provides a high temperature co-fired ceramic (HTCC) prepared from a ceramic green body by pore-filling with the pore-filling slurry according to any of the embodiments of the invention; preferably, the pore-filling slurry is a tungsten conductor pore-filling slurry.

Detailed Description

to make the features and effects of the present invention obvious to those skilled in the art, the terms and words used in the specification and claims are generally described and defined below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.

All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.

Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.

In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.

The pore-filling slurry is a paste formed by rolling and uniformly mixing solid powder and an organic carrier by three rollers and is used for filling pores in ceramic green bodies (also called green ceramic sheets, green tapes and substrates). The solid powder in the pore-filling slurry generally includes metal powder and inorganic additives. The organic vehicle typically includes an organic solvent and a thickener, and optionally may include adjuvants such as defoamers, dispersants, stabilizers, surfactants, and the like.

The metal powder typically comprises more than 80% of the total weight of the pore-filling slurry. The common metal powder used for the pore-filling slurry can be any one or a mixture of tungsten powder, molybdenum powder and manganese powder. For tungsten conductor pore-filling slurry, the metal powder contained in the slurry is mainly tungsten powder. The tungsten powder suitable for the present invention includes spherical tungsten powder and flaky tungsten powder, and the two can be mixed in any proportion for use. The metal powder is typically present in an amount of 85% to 95%, for example 85% to 94.5%, preferably 88% to 92%, such as 90%, of the total weight of the pore-filling slurry. The average particle diameter of the metal powder used for preparing the slurry is usually 0.5 μm to 5 μm, preferably 0.6 μm to 3 μm. When the average particle size is less than 0.5 μm or more than 5 μm, the slurry sintering shrinkage does not match with the green ceramic sheet.

The inorganic additive is typically selected from a metal oxide, a non-metal oxide, a metal nitride, a silicate, a metal oxide precursor, or a combination thereof. During sintering, chemical reactions occur between the inorganic additives and the matrix material or the particles themselves, thereby adhering the metal particles to the substrate. Inorganic additives suitable for use in the present invention may be, for example, include, but are not limited to, alumina, yttria, aluminum nitride, or mixtures thereof. The inorganic additive is typically present in an amount of from 0.5% to 5%, preferably from 1% to 4%, more preferably from 1.5% to 2.5%, such as 2%, by weight of the total pore-filling slurry. The inorganic additive is typically a powder. The average particle diameter of the inorganic additive suitable for the present invention is usually 0.5 μm to 10 μm, preferably 1 μm to 6 μm.

The amount of organic vehicle in the pore-filling slurry may be an amount conventionally used in the art. Typically, the organic vehicle comprises 5% to 15% of the total weight of the pore-filling slurry, such as 5% to 14.5%, 5% to 10%, 6% to 10%, 7% to 9%, 8%, and the like.

The organic solvent is generally a relatively viscous organic liquid, generally contains polar groups in its molecule, and is capable of dissolving a thickener such as cellulose, and generally has a high boiling point and is not easily volatile at normal temperature. The organic solvent contained in the slurry of the present invention is not particularly limited, and may be, for example, any one or a mixture of more of terpineol, butyl carbitol acetate, ethylene glycol ethyl ether acetate, and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol). The organic solvent is generally present in an amount of 1% to 10%, preferably 2% to 8%, more preferably 3% to 6% by weight of the total pore-filling slurry. In certain embodiments, the present invention employs terpineol and/or Texanol as the organic solvent; preferably, the present invention employs terpineol as the organic solvent.

Thickeners (also known as organic binder phases) are used to impart a viscosity to the slurry, usually high molecular weight organic polymers. The organic binder phase contained in the slurry of the present invention is not particularly limited, and may be any one or a combination of plural kinds of ethyl cellulose, nitrocellulose, acrylic resin, butyral resin, and maleic resin, for example. The thickener is typically present in an amount of 1% to 3%, preferably 1.5% to 2.5%, such as 2%, by weight of the total pore-filling slurry.

and auxiliary agents such as a dispersing agent, a defoaming agent and the like can be added into the slurry according to the needs, so that the slurry has better rheological property. The dispersing agent may be, for example, one or more of lecithin, acrylic dispersing agent. The defoaming agent may be, for example, one or more of polyethylene glycol, polyoxypropylene propylene glycol ether, and glycerin fatty acid ester. The amount of the aid may be 0-5%, such as 0-2.5%, 0-2%, 0-1%, etc., based on the total weight of the pore-filling slurry.

The invention discovers that the addition of the phthalate ester compound into the organic carrier of the high-temperature co-fired pore-filling slurry can improve the pore-filling printing effect of the HTCC pore-filling slurry.

Phthalate esters suitable for use in the present invention include, but are not limited to, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisononyl phthalate, and the like.

In certain embodiments, the pore-filling slurries of the present invention comprise a combination of one or more of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dioctyl phthalate, and dicyclohexyl phthalate. In certain embodiments, the pore-filling slurry of the present invention comprises diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, or any combination thereof.

In the present invention, the content of the phthalate ester is generally 1.5% to 3.0% of the total weight of the pore-filling slurry, and for example, may be in a range defined by any two weight percentage values selected from 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4% and 3.5%, and for example, may be 1.5% to 2.5%, 1.5% to 2.0%, 2.0% to 2.5%, 2.0% to 3.0%, 2.5% to 3.0%, and the like. When the content of the phthalate ester is less than 1.5%, the assistance to the pore-filling printing is small; when the content of the phthalate ester is more than 3.0%, the pore-filling paste is not easily printed.

In certain embodiments, the pore-filling slurries of the present invention comprise butyl benzyl phthalate; preferably, butyl benzyl phthalate is present in an amount of 1.5% to 3.0%, preferably 2.0% to 3.0%, more preferably 2.5% to 3.0%, such as 2.5% by weight of the total pore-filling slurry.

In certain embodiments, the pore-filling slurries of the present invention comprise dicyclohexyl phthalate; preferably, the dicyclohexyl phthalate is present in an amount of 1.5% to 3.0%, preferably 2.0% to 3.0%, more preferably 2.5% to 3.0%, such as 3.0% by weight of the total pore-filling slurry.

In certain embodiments, the pore-filling slurries of the present invention comprise dioctyl phthalate; preferably, the dioctyl phthalate is present in an amount of 1.5% to 3.0%, preferably 2.0% to 3.0%, such as 2.7%, by weight of the total pore-filling slurry.

In certain embodiments, the pore-filling slurry of the present invention comprises dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, or any combination thereof; preferably, the dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, or any combination thereof is present in an amount of 1.5% to 3.0%, preferably 1.5% to 2.5%, by weight of the total pore-filling slurry.

In certain embodiments, the pore-filling slurry of the present invention comprises butyl benzyl phthalate and a combination of one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate; preferably, the total content of butyl benzyl phthalate and the combination of one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate is from 1.5% to 3.0%, preferably from 2.0% to 3.0% by weight of the total pore-filling slurry.

In the embodiment where the pore-filling slurry contains two or more phthalic acid esters, the ratio between the phthalic acid esters is not particularly limited, and for example, when dibutyl phthalate and butyl benzyl phthalate are contained in the pore-filling slurry, the mass ratio of dibutyl phthalate to butyl benzyl phthalate may be 5: 1-1: 5, e.g. 1: 1.

The present invention also includes a method of making a pore-filling slurry of the present invention, comprising:

(1) weighing all components (including a thickening agent, an organic solvent and phthalic acid ester) of the organic carrier, and fully stirring at the temperature of 60-90 ℃ to obtain the organic carrier; and

(2) adding metal powder and inorganic additives into the organic carrier obtained in the step (1), and performing roll dispersion to obtain the pore-filling slurry.

The roll dispersion of step (2) can be carried out by means conventional in the art, and can be carried out, for example, by means of a three-roll mill.

The co-firing temperature of the pore-filling slurry is 1400-1800 ℃, can be applied to pore-filling metallization of an aluminum oxide or aluminum nitride HTCC substrate, and has the advantages of high structural strength, good electric heating performance, high wiring density and low cost.

Accordingly, the present invention also includes a high temperature co-fired ceramic made from a ceramic green body (substrate) that has been pore-filled with the pore-filling slurry according to any of the embodiments of the present invention.

The HTCC substrate may be pore-filled with the pore-filling slurry of the present invention by a method conventional in the art, for example, the pore-filling slurry of the present invention may be pore-filled on HTCC green ceramic sheets through a stainless steel plate, dried, and sintered in a reducing atmosphere. The drying condition can be drying for 10min to 15min at 70 ℃ to 100 ℃. The sintering curve can be that the temperature is raised to 400-500 ℃ from the room temperature according to 5-10 ℃/min, the temperature is preserved for 100-150 min, then the temperature is raised to 1400-1800 ℃ (peak value) according to 5-10 ℃/min, the sintering is carried out for 100-150 min, and the temperature is naturally reduced to the room temperature.

the invention has the advantages that: the phthalate compound is added into the hole filling slurry, so that the hole filling printing effect of the hole filling slurry is effectively improved, and the co-fired slurry is well matched with the substrate. Herein, the good matching of the hole-filling slurry and the substrate means that a hole-filling protrusion height test is performed on the sintered substrate, and the protrusion height is regarded as being matched with the green ceramic chip in a range of +/-15 μm.

the present invention will be described in detail with reference to examples. The embodiments in the present description are only for illustrating the present invention, and do not limit the scope of the present invention. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.

The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.