CN112390534A - Low-temperature co-fired low-voltage anodically-bonded microcrystalline glass material for airtight packaging and preparation method and application thereof - Google Patents
Low-temperature co-fired low-voltage anodically-bonded microcrystalline glass material for airtight packaging and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/0032—Packages or encapsulation
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/15—Ceramic or glass substrates
Abstract
The invention relates to a low-temperature co-fired low-voltage anodically bondable microcrystalline glass material for airtight packaging, and a preparation method and application thereof, wherein the low-temperature co-fired anodically bondable microcrystalline glass material is LAS-based microcrystalline glass, and the LAS-based microcrystalline glass comprises the following raw materials: 40 to 67 wt% of SiO216 to 24 wt% of Al2O32.7 to 7 wt% of Li2O, 0 to 5 wt% of B2O30 to 5 wt% of P2O50 to 4 wt% of TiO2、0～6 wt% of ZrO20 to 4 wt% of Na2O, 0 to 5 wt% of K2O, 0 to 4 wt% of Bi2O3And 0 to 4 wt% of RxOy(ii) a Wherein, R isxOyIn the formula, R is a rare earth element or/and an alkaline earth metal element, preferably at least one of Ce, Y, Ba, Mg and La, x = 1-2, and Y = 2-5.
Description
Technical Field
The invention relates to a microcrystalline glass electronic packaging material, a preparation method and application thereof, in particular to a low-temperature co-fired low-voltage anodically bondable microcrystalline glass material for airtight packaging, and a preparation method and application thereof.
Background
Micro Electro-mechanical systems (MEMS) refers to a device or System that integrates Micro sensors, microcontrollers, Micro actuators, and signal processing, which can be manufactured in a large number, and is widely used in various industrial fields, and is generally distinguished by inert-, Optical-, Chemical-, Bio-, RF-, Power-, etc. before MEMS internationally according to its application field. After decades of development, a large number of MEMS products, such as oscillators, gyroscopes, and acceleration sensors in mobile phones, consumer electronics products such as array nozzles in inkjet printers, and automotive electronics products such as tire pressure detection system sensors, have been put into mass production. Generally, for these MEMS products to be realized by packaging, the integration level of these products in practical applications is severely limited by the larger package volume and the lower package yield, which increases the production cost. At present, the integration level of a device is improved mainly by reducing the volume of the device and increasing the number of package pins in chip packaging, however, with the continuous improvement of the requirement of practical application on the integration level of the package, the traditional packaging technology based on a two-dimensional plane cannot effectively improve the integration level of the package, and thus the three-dimensional integration technology receives very extensive attention. As a three-dimensional integration technology, a Multi-Chip Module (MCM) technology can mount a plurality of semiconductor integrated circuit elements in a bare Chip state on a conventional thick-film and Low-Temperature Co-fired Ceramic (LTCC) multilayer wiring substrate, thereby realizing high-density vertical interconnection and greatly improving the packaging integration of MEMS devices.
In MEMS, silicon has been developed as a mainstream material for MEMS systems due to its special electrical and good mechanical properties and strong microelectronics infrastructure. The anodic bonding technology can bond glass containing alkali metal ions and silicon together to realize heterogeneous integration of the silicon chip and the wiring substrate. The specific process is that after glass containing alkali metal ions is heated to a certain temperature, silicon and glass are stacked together, and a direct current voltage of about 500V-1000V is applied to two ends of the glass, wherein the silicon end is connected with a positive electrode of a direct current power supply, the glass end is connected with a negative electrode of the direct current power supply, under the combined action of a direct current electric field and a thermal field, the alkali metal ions in the glass start to move and form non-bridge oxygen ions in the glass, the non-bridge oxygen ions form strong electrostatic attraction with the silicon and are mutually combined at the interface of the silicon and the glass to form a very strong silicon-oxygen chemical bond, and therefore the silicon and the glass are bonded. The anodic bonding technology is widely applied to integrated packaging of a micro-electro-mechanical system, and the bonding process does not need any medium such as an adhesive and the like, so that the packaging process can be greatly simplified, and the influence of parasitic effect in the packaging process is reduced. However, when bonding and packaging are performed by using glass and silicon, the glass substrate must be capable of realizing through wiring, so that the electrode leads in the MEMS device can be led out from the back surface of the packaging substrate and signals in the MEMS chip can be conducted out. In order to realize the functions, a certain size and number of holes must be punched on the glass, the size and the hole spacing of the through holes are strictly limited when the holes are punched on the glass, and in addition, when the number of the holes is large, the subsequent polishing of the glass is also strictly limited by the process. In addition, the through-wiring has relatively strict requirements on the quality and shape of the through-hole, and therefore, the through-hole must be treated for a long time by a deep reactive ion etching apparatus, which is very expensive.
For the above reasons, when the anode bonding is performed using glass and silicon, the bonding process is very complicated and costly, and the degree of freedom of design is very low. The LTCC material has excellent through wiring capacity, can realize multilayer wiring in the vertical direction, and meanwhile, capacitors, inductors, filters and other passive devices are embedded in the substrate, so that the developed anode-bonding LTCC material can obtain higher through hole wiring density (compared with glass), the three-dimensional integration density is improved, the through hole cost is reduced, the packaging design freedom is improved, and the application range of the anode bonding technology is greatly expanded.
Currently, there are two types of anodically bondable LTCC materials available internationally. Patent 1(WO 2005/042426) reports a glass/ceramic mixture characterized by compounding 60 to 70 wt% of a soda borosilicate glass having a sodium content of not more than 2.6 wt%, 10 to 20 wt% of alumina, and 8 to 25 wt% of cordierite/silica to form a composite material having a total sodium content of less than 1.5 wt%, the material having a coefficient of thermal expansion of about 3.5 to 3.65 ppm/c, and the anodic bonding of the material to silicon is achieved under a bonding condition of 800VDC at 400 ℃. Patent 2(US 2011/0108931) discloses a new Li-Mg-Al-Si-Bi ceramic system that successfully lowers the bonding temperature of the material by replacing the conductive ions in the material from sodium ions to lithium ions, enabling successful bonding at 360 ℃, 600 VDC. However, a single reduction in bonding temperature may not be meaningful in practical applications, particularly when anodic bonding materials are used in wafer-level hermetic packages. In the vacuum wafer level packaging process, in order to keep the vacuum degree in the device unchanged for a long time, a getter is often introduced into the cavity of the LTCC packaging material, and the activation temperature of the getter is generally 350-500 ℃, so that when the bonding temperature is 350-500 ℃, the getter can be activated while bonding packaging is often realized, the bonding packaging process is reduced, and the packaging efficiency of the device is greatly improved. In practical application, too high bonding voltage often brings about a series of problems such as breakdown failure of the device, and practical research shows that when the bonding voltage is lower than 500V, the effects such as device breakdown caused by too high bonding voltage can be obviously reduced.
Disclosure of Invention
In a first aspect, the present invention provides a low-temperature co-fired anodizable bonding microcrystalline glass material, wherein the low-temperature co-fired anodizable bonding microcrystalline glass material is LAS-based microcrystalline glass, and the LAS-based microcrystalline glass comprises the following raw material components: 40 to 67 wt% of SiO216 to 24 wt% of Al2O32.7 to 7 wt% of Li2O, 0 to 5 wt% of B2O30 to 5 wt% of P2O50 to 4 wt% of TiO20 to 6 wt% of ZrO20 to 4 wt% of Na2O, 0 to 5 wt% of K2O, 0 to 4 wt% of Bi2O3And 0 to 4 wt% of RxOy(ii) a Wherein, R isxOyIn the formula, R is a rare earth element or/and an alkaline earth metal element, preferably at least one of Ce, Y, Ba, Mg and La, x is 1-2, and Y is 2-5.
Preferably, B is2O3、P2O5And Bi2O3The total content of the TiO is more than or equal to 1.5wt percent2And ZrO2The total content of the Na is more than or equal to 2wt percent, and the Na is2O、K2O and RxOyThe total content of the glass-ceramic material is less than or equal to 6 wt%, and the microcrystalline glass material obtained under the condition can easily realize the matching of the thermal expansion coefficient with materials such as silicon, KOVAR alloy, silicon carbide and the like.
Further, preferably, Na is mentioned2O、K2O、RxOy、B2O3、P2O5And Bi2O3The sum of the total content of the components is 2-15 wt%, the sintering temperature of the microcrystalline glass material obtained under the condition is easy to control between 800-950 ℃, and the microcrystalline glass substrate material, the silver electrode and the like are easier to realizeAnd co-firing and matching.
Further, preferably, Na is mentioned2O、K2O and RxOyTotal weight of (A) and (B)2O3、P2O5And Bi2O3The ratio of the total weight of the glass ceramics is less than or equal to 1, and the microcrystalline glass obtained under the condition has better chemical stability.
Preferably, the particle size D of the low-temperature co-fired anodically bondable glass ceramic material50＝1～3μm。
In a second aspect, the invention provides a preparation method of a low-temperature co-fired anodically bondable microcrystalline glass material, which comprises the following steps:
(1) weighing and mixing the raw materials according to the composition of the LAS-based microcrystalline glass to obtain mixed powder;
(2) heating the mixed powder to a molten state to obtain a glass melt;
(3) and quenching and crushing the obtained glass melt to obtain the low-temperature co-fired anodically-bonded glass ceramic material.
Preferably, in the step (2), the heating temperature is 1400-1650 ℃, and the time is 30-360 minutes. It should be noted that the raw materials used in the present invention are not limited to the above oxides, but may include all compounds that can be decomposed at high temperature into the above oxides and mixtures thereof, and even minerals, etc.
Preferably, in step (2), the glass melt is introduced into deionized water for quenching treatment.
In a third aspect, the invention provides a preparation method of a substrate material of a microcrystalline glass electronic packaging machine, which comprises the following steps:
(1) mixing the low-temperature co-fired anodically bondable microcrystalline glass material, a binder and an organic solvent to obtain slurry;
(2) carrying out tape casting on the obtained slurry to obtain a ceramic blank sheet;
(3) and (3) subjecting the obtained ceramic blank sheet to a glue removing stage, a crystal nucleus nucleation stage and a ceramic stage to obtain the low-temperature co-fired anodically bonded glass ceramic material.
Preferably, in the step (1), the binder is at least one selected from the group consisting of acrylate, polyvinyl butyral and polyvinyl alcohol, and the organic solvent is at least one selected from the group consisting of methyl ethyl ketone, ethanol, ethyl acetate and xylene.
Preferably, the slurry further comprises a plasticizer which is at least one of phthalate, polyethylene glycol, butyl benzyl phthalate and dioctyl phthalate, or/and a dispersant which is at least one of triolein, fish oil and oleic acid.
Preferably, in the step (2), the thickness of the ceramic blank sheet is 20 to 200 μm.
In addition, preferably, before the glue discharging stage, the obtained ceramic blank sheet is subjected to punching, printing, laminating and static pressure forming; preferably, the temperature of the static pressure forming is 40-70 ℃, and the pressure is 100-500 kg/cm2。
Preferably, in the step (3), the temperature of the glue discharging stage is 400-550 ℃, and the time is 30-120 minutes. Wherein, the glue discharging temperature is too low, and the glue discharging time is too short, so that the glue discharging is incomplete; if the binder removal temperature is too high and the binder removal time is too long, the material may form crystal nuclei in advance.
Preferably, in the step (3), the temperature of the nucleation stage of the crystal nucleus is 600-800 ℃ and the time is more than or equal to 5 minutes. Wherein, the nucleation of the crystal nucleus is incomplete due to the excessively low temperature and the excessively short time; the nucleation temperature of the crystal nucleus is too high, so that the crystal nucleus is over-developed and is not beneficial to sintering.
Preferably, in the step (3), the sintering temperature of the ceramic stage is 760-1000 ℃, the time is more than or equal to 5 minutes, and the sintering temperature of the ceramic stage is more than the temperature of the nucleation stage; preferably, the sintering temperature in the ceramic stage is 800-950 ℃, and the sintering is favorable for realizing the co-sintering with electrode materials such as silver and the like at the temperature.
In a fourth aspect, the invention also provides a microcrystalline glass electronic packaging machine substrate material prepared by the preparation method, which comprises the following steps: the beta-spodumene solid solution or/and beta-quartz, wherein the total volume content of the beta-spodumene solid solution or/and the beta-quartz is more than or equal to 50 vol%; preferably also includes at least one of beta eucryptite, chrysolite, and zirconia.
In the invention, the content of beta-spodumene solid solution crystal phase in the microcrystalline glass electronic packaging machine substrate material is more than or equal to 50vol%, the dielectric constant of the obtained material is less than 10(1MHz), and the room-temperature dielectric loss is less than 8 x 10-3(1 MHz). The substrate material can select metals such as gold, silver, copper, platinum, palladium, even aluminum and the like as electrode materials, and low-temperature co-firing with the circuit substrate is realized.
Preferably, the LAS-based glass ceramic further comprises no more than 10vol% of a glass phase.
Preferably, the substrate material of the glass ceramic electronic packaging machine has a thermal expansion coefficient of 1.5 to 5 ppm/DEG C within 25 to 500 ℃, preferably 2.4 to 4.0 ppm/DEG C; the dielectric constant of the substrate material of the microcrystalline glass electronic packaging machine is less than 10, and the dielectric loss at room temperature is less than 8 multiplied by 10-3(ii) a The density of the substrate material of the microcrystalline glass electronic packaging machine is more than or equal to 95 percent, and the breaking strength is not lower than 120 MPa.
Preferably, when the substrate material of the microcrystalline glass electronic packaging machine is bonded with the semiconductor material, when the bonding temperature is 350 ℃, the bonding voltage is less than 500V; the semiconductor material is one of silicon, KOVAR alloy and silicon carbide. When the bonding temperature is 350 ℃, the bonding voltage is less than 500V, which shows that the bonding voltage of the substrate material of the microcrystalline glass electronic packaging machine prepared by the invention is lower than that of the reported anodically bondable LTCC material.
In a fifth aspect, the invention provides an application of the substrate material of the microcrystalline glass electronic packaging machine in wafer level packaging.
Has the advantages that:
(1) in the invention, the low-temperature co-fired anodically-bonded glass ceramic material (LAS glass ceramic material) can replace the traditional borosilicate glass to prepare the substrate material of the glass ceramic electronic packaging machine, and the electrical interconnection and heterogeneous integration with common semiconductor materials (such as silicon, KOVAR alloy, silicon carbide and the like) are realized through the anodic bonding technology, so that the low-temperature co-fired anodically-bonded glass ceramic material can be applied to wafer-level packaging;
(2) in the invention, the LAS glass ceramic material can be added with an organic binder and used for preparing a circuit substrate by a tape casting process;
(3) according to the invention, the low-temperature co-fired anodically-bonded microcrystalline glass material can realize multilayer interconnection and wiring through the technologies of through holes, hole filling, printing and the like;
(4) the invention provides a low-voltage anodically bondable LTCC material (namely LAS microcrystalline glass material) for airtight packaging, which can realize the anodic bonding with semiconductor materials such as silicon and the like under the conditions of 350 ℃ and 200V, breaks through the situation that the existing anodically bondable LTCC material is monopolized abroad for a long time, and has important significance for the development of domestic advanced integration technology.
Drawings
Fig. 1 is an XRD pattern of the microcrystalline glass electronic packaging substrate material prepared in example 1, from which it can be seen that the obtained microcrystalline glass electronic packaging substrate material forms a composition of β -spodumene solid solution, β -quartz solid solution, cristobalite, zirconia, etc., the material is substantially completely crystallized, and a small amount of glass phase remains;
fig. 2 is an XRD pattern of the microcrystalline glass electronic package substrate material prepared in example 2, from which it can be seen that the phase composition of the microcrystalline glass electronic package substrate material comprises β -spodumene solid solution, β -quartz solid solution, zirconia, etc., the material is substantially completely crystallized, and a small amount of glass phase remains;
fig. 3 is an XRD pattern of the microcrystalline glass electronic package substrate material prepared in example 3, from which it can be seen that the phase composition of the microcrystalline glass electronic package substrate material comprises a β -spodumene solid solution, the material is substantially completely crystallized, and a small amount of glass phase remains;
FIG. 4 is SEM pictures of microcrystalline glass electronic package substrate materials prepared in examples 1-3, wherein (a) is example 1, (b) is example 2, and (c) is example 3, and it can be seen that all the examples achieve good sintering compactness and meet the practical requirements;
FIG. 5 is an XRD pattern of a microcrystalline glass electronic package substrate material prepared in comparative example 1;
fig. 6 is an XRD pattern of the microcrystalline glass electronic package substrate material prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the basic component of the low-temperature co-fired anodizable bonding microcrystalline glass material (abbreviated as a microcrystalline glass material) is LAS (Li-Al-Si) -based microcrystalline glass. Based on 100 wt% of total composition of LAS (Li-Al-Si) based microcrystalline glass, the raw material composition comprises: 40 to 67 wt% of SiO2(ii) a 16-24 wt% of Al2O3(ii) a 2.7 to 7 wt% of Li2O (only in accordance with the crystallization range of spodumene solid solution); 0 to 5 wt% of B2O3(ii) a 0 to 5 wt% of P2O5(ii) a 0 to 4 wt% of TiO2(ii) a 0 to 6 wt% of ZrO2(ii) a 0 to 4 wt% of Na2O; 0 to 5 wt% of K2O; 0 to 4 wt% of Bi2O3(ii) a 0 to 4 wt% of RxOy. Wherein R isxOyIn the formula, R can be a rare earth element or/and an alkaline earth metal element, preferably at least one of Ce, Y, Ba, Mg and La, x is 1-2, and Y is 2-5. Wherein, B2O3、P2O5And Bi2O3May be at least 1.5 wt%, TiO2And ZrO2Can be at least 2 wt% in total, Na2O、K2O and RxOyIn a total amount of less than about 6 wt%. The Na is2O、K2O and RxOyAnd B2O3、P2O5And Bi2O3And about 2 to about 15 wt%. The Na is2O、K2O and RxOyTotal weight of (B)2O3、P2O5And Bi2O3The weight ratio of the total weight of (A) is about < 1.
In an alternative embodiment, the resulting low-temperature co-fired anodizable microcrystalline glass material has a particle size D50＝1～3μm。
The following exemplarily illustrates a preparation method of the low-temperature co-fired anodizable bonding microcrystalline glass material provided by the present invention.
Weighing raw materials according to the basic composition of LAS microcrystalline glass, and mixing the raw materials to obtain mixed powder. The raw material used in the present invention is not limited to the above-mentioned oxides, and may include any compounds or minerals that can be decomposed at high temperature into the above-mentioned oxides and mixtures thereof.
And heating and melting the mixed powder to obtain a glass melt. The mixture of raw materials melts at a temperature of at least about 1400 c and the mixture of raw materials melts at a temperature of less than about 1650 c. After melting is complete, the incubation is continued for a period of time to allow the glass melt to clarify. As an example, it may be desirable to maintain the temperature at the melting temperature for at least 20 minutes to allow the glass raw material mixture to melt and mix well.
And quenching the glass melt (adding the glass melt into deionized water), and then crushing to obtain glass powder (namely the low-temperature co-fired anodically bonded glass ceramic material).
In one embodiment of the invention, the substrate material of the microcrystalline glass electronic packaging machine is prepared by using a low-temperature co-fired anodically-bondable microcrystalline glass material as a raw material. The low-temperature co-fired anodically bonded microcrystalline glass material can realize sintering densification within 760-1000 ℃ (preferably 800-950 ℃). The following exemplarily illustrates a method for preparing a substrate material for a glass ceramic electronic packaging machine provided by the invention.
Mixing a binder, a plasticizer, a dispersant and a low-temperature co-fired anodically bondable microcrystalline glass material, adding a certain amount of organic solvent according to needs, and forming stably dispersed slurry by ball milling. Wherein, the addition amount of the binder such as but not limited to acrylate, polyvinyl butyral, polyvinyl alcohol and the like can be 15-30 wt% of the anodically bonded microcrystalline glass material which is co-fired at low temperature. The plasticizer is not limited to butyl phthalate, polyethylene glycol, butyl benzyl phthalate, dioctyl phthalate and the like, and the addition amount of the plasticizer is 0.5-3 wt% of the low-temperature co-fired anodizable bonding microcrystalline glass material. The dispersing agent is such as but not limited to triolein, fish oil, oleic acid and the like, and the addition amount of the dispersing agent can be 0.5-3 wt% of the low-temperature co-fired anodically-bonded microcrystalline glass material. The organic solvent such as but not limited to butanone, ethanol, ethyl acetate, xylene and the like can be added in an amount of 80-120 wt% of the low-temperature co-fired anodically bondable microcrystalline glass material.
And carrying out tape casting on the obtained slurry to obtain a ceramic blank sheet (or called a green ceramic sheet). The thickness of each green ceramic chip can be 20-200 μm. And further carrying out a series of operations such as punching, printing, laminating, static pressing and the like on the green ceramic chip to prepare a ceramic blank sheet with a certain required shape and thickness.
And (3) subjecting the ceramic blank sheet to a glue removing stage, a crystal nucleus nucleation stage and a ceramic stage to obtain the substrate material of the microcrystalline glass electronic packaging machine. Wherein the temperature of the glue discharging stage is 400-550 ℃, and the time is 30-120 minutes. And then heating to the nucleation temperature range of 600-800 ℃ in the nucleation stage of the crystal nucleus, and preserving the heat for at least 5 minutes. And finally, heating to a ceramization temperature range of 760-1000 ℃ (preferably 800-950 ℃) in the ceramization stage, and keeping the temperature for at least 5 minutes.
In one embodiment of the invention, the microcrystalline glass electronic packaging machine substrate material is used in an anodic bonding technology, and heterogeneous integration of the microcrystalline glass material and a semiconductor material (especially a material such as silicon) is realized. When the bonding temperature is 350 ℃, the bonding voltage is less than 500V (even less than 300V).
In the disclosure, a brand-new anodically bondable LTCC material (microcrystalline glass electronic packaging machine substrate material) is provided, for airtight packaging, when the getter activation temperature (350 ℃) is about, the bonding voltage is about 200V, which is far less than other reported anodically bondable LTCC materials, so that the breakdown of devices in the bonding process can be effectively avoided, and the packaging qualification rate in the anodically bonded packaging process can be greatly improved.
In the invention, the substrate material of the microcrystalline glass electronic packaging machine contains beta-spodumene solid solution or/and beta-quartz as main crystal phases. The crystalline phase of the microcrystalline glass electronic packaging machine substrate material comprises: the total content of β -spodumene solid solution or/and is greater than about 50% volume fraction. The crystalline phase of the microcrystalline glass material of the present invention further comprises: beta-eucryptite, chrysolite, zirconia, and the like. The glass phase and/or other crystal phases with volume fraction less than 10% are contained in addition to the above crystal phases.
In the invention, the Coefficient of Thermal Expansion (CTE) of the substrate material of the glass-ceramic electronic packaging machine in the temperature range of about 25-500 ℃ is about 1.5-5.0 ppm/DEG C measured by a thermal expansion instrument (DIL,402C, Netzsch, Germany), and the preferred CTE is in the range of 2.4-4.0 ppm/DEG C;
the dielectric constant of the substrate material of the glass-ceramic electronic packaging machine is less than 10(1MHz), preferably the dielectric constant (1MHz) is less than 7, measured by a broadband dielectric test system (Alpha-A, Novocontrol, Germany);
the room temperature dielectric loss of the glass-ceramic electronic packaging machine substrate material is less than 8 x 10 measured by a broadband dielectric test system (Alpha-A, Novocontrol, Germany)-3(1MHz), preferably a dielectric loss (1MHz) of less than 5X 10-3；
The bending strength of the substrate material of the microcrystalline glass electronic packaging machine is measured by a three-point bending method to be not lower than 120 MPa;
the relative density of the substrate material of the microcrystalline glass electronic packaging machine measured by an Archimedes drainage method can reach more than 95%.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Examples 1 to 3:
(1) mixing the raw materials according to a certain proportion to obtain mixed powder, so that the raw material mixture is converted into a composition with the mass proportion shown in the table 1 at high temperature;
(2) preserving the temperature of the obtained mixed powder for 30min at 1500 ℃ to obtain uniform glass melt;
(3) then the glass melt is led into deionized water for quenching, and the obtained glass broken slag is treated by ball milling by taking the deionized water or acetone and the like as media. To obtain a particle diameter D502 μm glass powder (low temperature co-fired anodically bondable glass ceramics);
(4) the glass powder was made into a green tape with a thickness of about 150 μm according to the method described in table 1;
(5) punching, slicing, printing, laminating, and heating at 70 deg.C and 150kg/cm2Is subjected to static pressure under the pressure of the pressure to prepare a ceramic blank sheet;
(6) and (3) carrying out glue discharging on the obtained ceramic blank sheet at 500 ℃ for 120 minutes, and carrying out a final crystal nucleus nucleation stage and a ceramic stage according to data in table 1 to ensure that the microcrystalline glass material is sintered and compacted to obtain the microcrystalline glass electronic packaging substrate material (or called as a circuit substrate).
3 basic components which can be sintered and compacted within the temperature range of 800-950 ℃ are given in table 1, and the bonding performance of each group of samples is tested and evaluated on the basis. Each set of circuit substrates prepared according to the compositions in the tables was cut into a size of 25mm by a dicing machine2Then mirror polishing the sample to a thickness of 0.3mm and a surface roughness of less than 5nm Ra, and then bonding silicon to the prepared circuit substrate at 350 ℃. Since the bonding strength of anodic bonding is very large, when the bonding strength is measured by a tensile method, a fracture point is not generally at a bonding interface but always occurs at an internal defect aggregation place of silicon, and thus, quantitative evaluation of the bonding quality is difficult in the conventional method. In the present invention, Scanning Electron Microscopy (SEM) is used to perform qualitative evaluation of the bonding interface. And observing the bonding interface of the LTCC substrate and the silicon by using a scanning electron microscope, wherein if the bonding interface does not have any discontinuous points or defects, the bonding quality is considered to be better and is expressed by Pass, and otherwise, the bonding quality is expressed by Failed. The results of the bond quality evaluation are given in table 1.
Table 1 shows the specific formulation (wt%) of the low-temperature co-fired anodizable bonding microcrystalline glass material obtained in examples 1 to 3, the prepared microcrystalline glass electronic packaging substrate material, and the evaluation table of the bonding quality:
from the above examples 1-3, it can be seen that the novel low voltage anodizable bonding microcrystalline glass material based on LTCC of the present invention has a characteristic sintering temperature of 760 ℃ to 1000 ℃, and further can realize anodic bonding under 200V, and the bonding voltage is much lower than that of the reported anodizable bonding LTCC material, therefore, the present invention has innovativeness and practicability.
In summary, the present invention provides anodic bonding materials that can be used in, but are not limited to, advanced electronic packaging and methods for making the same. The crystalline phase of the substrate material for a crystallized glass electronic packaging machine obtained in the above-mentioned examples 1 to 3 of the present invention contains β -quartz or/and β -spodumene solid solution in an amount of more than about 50% by volume fraction. Other crystalline phases of the present invention may include: beta-eucryptite, chrysolite, zirconia, and the like. Besides the above crystal phases, the microcrystalline glass electronic packaging machine substrate material may also contain other crystal phases and glass phases with volume fractions of less than 10%. The relative sintering compactness of the microcrystalline glass electronic packaging machine substrate material can reach more than 95 percent, the dielectric constant (1MHz) is lower than 10, the preferred dielectric constant (1MHz) is lower than 7, and the dielectric loss (1MHz) is lower than 8 multiplied by 10-3Preferably, the dielectric loss (1MHz) is less than 5X 10-3The thermal expansion coefficient is about 1.5-5.0 ppm/DEG C at 25-500 ℃, the preferred thermal expansion coefficient range is 2.4-4.0 ppm/DEG C, the flexural strength is not lower than 120MPa, the material can successfully realize anodic bonding with silicon under the direct current voltage of 350 ℃ and 200V, and the bonding performance of the material is superior to that of any existing anodic bonding LTCC material system.
Comparative examples 1 to 2:
the substrate material of the microcrystalline glass electronic packaging machine obtained in the comparative example 1 adopts the same process conditions as those of the example 1, and the basic composition of the low-temperature co-fired anodically-bondable microcrystalline glass material deviates from the composition range provided by the invention; the low-temperature co-fired anodically bondable microcrystalline glass material of the comparative example 2 has the same basic composition as that of the example 2, and the process conditions of the subsequent microcrystalline glass electronic packaging machine substrate material deviate from the process condition range provided by the invention, and the specific implementation process is as follows:
(1) mixing the raw materials according to a certain proportion to obtain mixed powder, so that the raw material mixture is converted into a composition with the mass proportion shown in the table 2 at high temperature;
(2) keeping the temperature of the obtained mixed powder at 1600 ℃ for 30min to obtain a uniform glass melt;
(3) then the glass melt is led into deionized water for quenching, and the obtained glass broken slag is treated by ball milling by taking the deionized water or acetone and the like as media. To obtain a particle diameter D502 μm glass powder (low temperature co-fired anodically bondable glass ceramics); (4) the glass powder was made into a green tape with a thickness of about 150 μm according to the method described in table 1;
(5) punching, slicing, printing, laminating, and heating at 70 deg.C and 150kg/cm2Is subjected to static pressure under the pressure of the pressure to prepare a ceramic blank sheet; (6) and (3) carrying out glue discharging on the obtained ceramic blank sheet at 500 ℃ for 120 minutes, and carrying out a final crystal nucleus nucleation stage and a ceramic stage according to data in table 1 to ensure that the microcrystalline glass material is sintered and compacted to obtain the microcrystalline glass electronic packaging substrate material (or called as a circuit substrate).
Table 2 shows the specific formulation (wt%) of the low-temperature co-fired anodizable bonding microcrystalline glass material obtained in comparative examples 1-2, the prepared microcrystalline glass electronic packaging substrate material, and the basic properties:
| serial number | Comparative example 1 | Comparative example 2 |
| Li2O | 10.17 | 3.5 |
| Al2O3 | 21.39 | 18 |
| SiO2 | 50.32 | 63 |
| TiO2 | 0 | 2 |
| ZrO2 | 0 | 2 |
| Na2O | 0 | 3 |
| K2O | 0 | 1.5 |
| P2O5 | 0 | 3.5 |
| B2O3 | 18.11 | 2.5 |
| RxOy | 0 | 1(R＝Ce) |
| Total mass of raw material powder/g | 90g | 90g |
| Adhesive/g | Acrylate/20 g | Acrylate/20 g |
| Plasticizer/g | Phthalic acid butyl ester/2 g | Phthalic acid butyl ester/2 g |
| Dispersant/g | Triolein/2 g | Triolein/2 g |
| Organic solvent/g | Butanone 80g | Butanone 80g |
| Rubber discharge stage | 500 ℃ for 120 minutes | 500 ℃ for 120 minutes |
| Nucleation phase of crystal nucleus | 760 ℃ for 30 minutes | 700 ℃ for 0min |
| Ceramic stage | 870 ℃ for 120 minutes | 800 ℃ for 120 minutes |
| Density (g/cm)3) | 2.415g/cm3 | 2.567g/cm3 |
| Density/% | 93.5％ | 92.1％ |
| Dielectric constant (1MHz) | 7.2 | 8.5 |
| Dielectric loss (1MHz) | 51×10-3 | 45×10-3 |
| Coefficient of thermal expansion (ppm/. degree.C.) | 0.9ppm/℃ | 5.1ppm/℃ |
| Flexural strength/MPa | 93MPa | 104MPa |
。
From the above comparative examples 1-2, it can be seen that when the initial raw material composition deviates from the basic composition range proposed by the present invention or the basic heat treatment process of the substrate material deviates, the physical properties of the obtained microcrystalline glass electronic packaging machine substrate material, such as dielectric loss, thermal expansion coefficient, flexural strength, etc., cannot reach the expected values proposed by the present invention, so the basic composition of the microcrystalline glass material proposed by the present invention and the subsequent preparation method of the microcrystalline glass electronic packaging machine substrate material are inventive. The microcrystalline glass electronic packaging substrate materials obtained in the comparative examples 1 and 2 are easy to break down in the bonding process due to lower sintering density, have larger difference between the thermal expansion coefficient and silicon, and have higher bonding failure rate. Therefore, the microcrystalline glass electronic packaging substrate materials obtained in comparative examples 1 and 2 are not suitable for bonding treatment.
Claims (15)
1. The utility model provides a but low temperature cofired anodic bonding microcrystalline glass material which characterized in that, but low temperature cofired anodic bonding microcrystalline glass material is LAS base microcrystalline glass, LAS base microcrystalline glass's raw materials constitution includes: 40 to 67 wt% of SiO216 to 24 wt% of Al2O32.7 to 7 wt% of Li2O, 0 to 5 wt% of B2O30 to 5 wt% of P2O50 to 4 wt% of TiO20 to 6 wt% of ZrO20 to 4 wt% of Na2O, 0 to 5 wt% of K2O, 0 to 4 wt% of Bi2O3And 0 to 4 wt% of RxOy(ii) a Wherein, R isxOyIn the formula, R is a rare earth element or/and an alkaline earth metal element, preferably at least one of Ce, Y, Ba, Mg and La, x = 1-2, and Y = 2-5.
2. The low temperature co-fired anodically bondable microcrystalline glass material of claim 1, wherein B is2O3、P2O5And Bi2O3The total content of the TiO is more than or equal to 1.5wt percent2And ZrO2The total content of the Na is more than or equal to 2wt percent, and the Na is2O、K2O and RxOyThe total content is less than or equal to 6 wt%; preferably, the Na2O、K2O、RxOy、B2O3、P2O5And Bi2O3The sum of the total content of the components is 2-15 wt%; more preferably, the Na2O、K2O and RxOyTotal weight of (A) and (B)2O3、P2O5And Bi2O3The ratio of the total weight of the components is less than or equal to 1.
3. The low-temperature co-fired anodizable microcrystalline glass material according to claim 1 or 2, wherein the particle size D of the low-temperature co-fired anodizable microcrystalline glass material50=1～3μm。
4. A method of preparing a low temperature co-fired anodizable glass ceramic material as claimed in any one of claims 1 to 3, comprising:
(1) weighing and mixing the raw materials according to the composition of the LAS-based microcrystalline glass to obtain mixed powder;
(2) heating the mixed powder to a molten state to obtain a glass melt;
(3) and quenching and crushing the obtained glass melt to obtain the low-temperature co-fired anodically-bonded glass ceramic material.
5. The method according to claim 4, wherein the heating in step (2) is carried out at 1400 to 1650 ℃ for 30 to 360 minutes.
6. A production method according to claim 4 or 5, wherein in the step (3), the glass melt is introduced into deionized water to be quenched.
7. A preparation method of a substrate material of a microcrystalline glass electronic packaging machine is characterized by comprising the following steps:
(1) mixing the low-temperature co-fired anodizable glass ceramic material of any one of claims 1 to 3, a binder and an organic solvent to obtain a slurry;
(2) carrying out tape casting on the obtained slurry to obtain a ceramic blank sheet;
(3) and (3) subjecting the obtained ceramic blank sheet to a glue removing stage, a crystal nucleus nucleation stage and a ceramic stage to obtain the low-temperature co-fired anodically bonded glass ceramic material.
8. The production method according to claim 7, wherein in the step (1), the binder is at least one selected from the group consisting of acrylate, polyvinyl butyral and polyvinyl alcohol, and the organic solvent is at least one selected from the group consisting of methyl ethyl ketone, ethanol, ethyl acetate and xylene; preferably, the slurry further comprises a plasticizer which is at least one of phthalate, polyethylene glycol, butyl benzyl phthalate and dioctyl phthalate or/and a dispersant which is at least one of triolein, fish oil and oleic acid.
9. The preparation method according to claim 7 or 8, wherein in the step (2), the thickness of the ceramic green sheet is 20 to 200 μm; preferably, before the glue discharging stage, the obtained ceramic blank sheet is subjected to punching, printing, laminating and static pressure forming; more preferably, the temperature of the static pressure forming is 40-70 ℃, and the pressure is 110-500 kg/cm2。
10. The preparation method according to any one of claims 7 to 9, wherein in the step (3), the temperature of the rubber discharge stage is 400 to 550 ℃ and the time is 30 to 120 minutes;
the temperature of the nucleation stage of the crystal nucleus is 600-800 ℃, and the time is more than or equal to 5 minutes;
the sintering temperature of the ceramic stage is 760-1000 ℃, the time is more than or equal to 5 minutes, and the sintering temperature of the ceramic stage is higher than the temperature of the crystal nucleus nucleation stage; preferably, the sintering temperature of the ceramic stage is 800-950 ℃.
11. A glass ceramic electronic packaging machine substrate material prepared according to the preparation method of any one of claims 7-10, wherein the glass ceramic electronic packaging machine substrate material comprises: the beta-spodumene solid solution or/and beta-quartz, wherein the total volume content of the beta-spodumene solid solution or/and the beta-quartz is more than or equal to 50 vol%; preferably also includes at least one of beta eucryptite, chrysolite, and zirconia.
12. A glass-ceramic electronic packaging machine substrate material as claimed in claim 11, wherein the LAS-based glass-ceramic further comprises no more than 10vol% glass phase.
13. The microcrystalline glass electronic packaging machine substrate material as claimed in claim 11 or 12, wherein the microcrystalline glass electronic packaging machine substrate material has a coefficient of thermal expansion of 1.5-5 ppm/° c, preferably 2.4-4.0 ppm/° c, within 25-500 ℃; the dielectric constant of the substrate material of the microcrystalline glass electronic packaging machine is less than 10, and the dielectric loss at room temperature is less than 8 multiplied by 10-3(ii) a The density of the substrate material of the microcrystalline glass electronic packaging machine is more than or equal to 95 percent, and the breaking strength is not lower than 120 MPa.
14. The microcrystalline glass electronic packaging machine substrate material according to any of claims 11-13, wherein when the microcrystalline glass electronic packaging machine substrate material and the semiconductor material are bonded, when the bonding temperature is 350 ℃, the bonding voltage is < 500V; the semiconductor material is one of silicon, KOVAR alloy and silicon carbide.
15. Use of the microcrystalline glass electronic packaging machine substrate material according to any of claims 11-14 in wafer level packaging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113504002A (en) * | 2021-06-28 | 2021-10-15 | 福建船政交通职业学院 | Tire gauge part |
| CN114136476A (en) * | 2021-12-06 | 2022-03-04 | 无锡隆盛科技股份有限公司 | Sealing method of high-temperature sensor |
| CN115215553A (en) * | 2022-08-02 | 2022-10-21 | 上海晶材新材料科技有限公司 | Low-temperature co-fired ceramic green tape and substrate easy to match with metal slurry for co-firing and preparation method |
| WO2023092260A1 (en) * | 2021-11-23 | 2023-06-01 | 海南大学 | Directional crystallization-based las microcrystalline glass and preparation method therefor |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072433A (en) * | 1999-09-02 | 2001-03-21 | Asahi Techno Glass Corp | Glass for anodic joining |
| JP2001114531A (en) * | 1999-10-19 | 2001-04-24 | Nippon Sheet Glass Co Ltd | Glass composition, substrate for information recording medium using the same, information recording medium and information recorder |
| JP2002321940A (en) * | 2001-04-24 | 2002-11-08 | Asahi Techno Glass Corp | Crystallized glass for anodic bonding |
| CN102875159A (en) * | 2012-09-20 | 2013-01-16 | 广东风华高新科技股份有限公司 | Method for preparing low-temperature cofired dielectric ceramic and material and sintering aid of low-temperature cofired dielectric ceramic |
| US20130295523A1 (en) * | 2010-11-02 | 2013-11-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Lithium silicate glasses or glass ceramics, method for production thereof and use thereof |
| CN103570336A (en) * | 2013-10-15 | 2014-02-12 | 江苏科技大学 | High-density LTCC (Low Temperature Co-Fired Ceramic) substrate applicable to ultrahigh frequency condition and preparation method thereof |
| CN103951194A (en) * | 2014-04-21 | 2014-07-30 | 哈尔滨工业大学 | Method for preparing MAS (MgO-Al2O3-SiO2) series microcrystal glass electronic substrate in water-based tape-casting mode |
| JP2016141607A (en) * | 2015-02-04 | 2016-08-08 | 日本電気硝子株式会社 | Semiconductor wafer support substrate |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN107572827A (en) * | 2017-10-20 | 2018-01-12 | 桂林电子科技大学 | A kind of crystallite glass substrate material and preparation method thereof |
| CN108395102A (en) * | 2018-03-21 | 2018-08-14 | 中国人民解放军国防科技大学 | L TCC (TCC) substrate material with low thermal expansion coefficient and preparation method thereof |
| CN108529885A (en) * | 2017-03-06 | 2018-09-14 | 中国科学院上海硅酸盐研究所 | One kind can anode linkage LTCC materials and its preparation method and application |
| CN109206015A (en) * | 2018-10-08 | 2019-01-15 | 中国科学院上海硅酸盐研究所 | A kind of low temperature, low-voltage anode linkage baseplate material and preparation method thereof |
-
2019
- 2019-08-12 CN CN201910740118.0A patent/CN112390534A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072433A (en) * | 1999-09-02 | 2001-03-21 | Asahi Techno Glass Corp | Glass for anodic joining |
| JP2001114531A (en) * | 1999-10-19 | 2001-04-24 | Nippon Sheet Glass Co Ltd | Glass composition, substrate for information recording medium using the same, information recording medium and information recorder |
| JP2002321940A (en) * | 2001-04-24 | 2002-11-08 | Asahi Techno Glass Corp | Crystallized glass for anodic bonding |
| US20130295523A1 (en) * | 2010-11-02 | 2013-11-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Lithium silicate glasses or glass ceramics, method for production thereof and use thereof |
| CN102875159A (en) * | 2012-09-20 | 2013-01-16 | 广东风华高新科技股份有限公司 | Method for preparing low-temperature cofired dielectric ceramic and material and sintering aid of low-temperature cofired dielectric ceramic |
| CN103570336A (en) * | 2013-10-15 | 2014-02-12 | 江苏科技大学 | High-density LTCC (Low Temperature Co-Fired Ceramic) substrate applicable to ultrahigh frequency condition and preparation method thereof |
| CN103951194A (en) * | 2014-04-21 | 2014-07-30 | 哈尔滨工业大学 | Method for preparing MAS (MgO-Al2O3-SiO2) series microcrystal glass electronic substrate in water-based tape-casting mode |
| JP2016141607A (en) * | 2015-02-04 | 2016-08-08 | 日本電気硝子株式会社 | Semiconductor wafer support substrate |
| CN106032318A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | A low-temperature co-fired ceramic material and a preparing method thereof |
| CN108529885A (en) * | 2017-03-06 | 2018-09-14 | 中国科学院上海硅酸盐研究所 | One kind can anode linkage LTCC materials and its preparation method and application |
| CN107572827A (en) * | 2017-10-20 | 2018-01-12 | 桂林电子科技大学 | A kind of crystallite glass substrate material and preparation method thereof |
| CN108395102A (en) * | 2018-03-21 | 2018-08-14 | 中国人民解放军国防科技大学 | L TCC (TCC) substrate material with low thermal expansion coefficient and preparation method thereof |
| CN109206015A (en) * | 2018-10-08 | 2019-01-15 | 中国科学院上海硅酸盐研究所 | A kind of low temperature, low-voltage anode linkage baseplate material and preparation method thereof |
Non-Patent Citations (11)
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113504002A (en) * | 2021-06-28 | 2021-10-15 | 福建船政交通职业学院 | Tire gauge part |
| WO2023092260A1 (en) * | 2021-11-23 | 2023-06-01 | 海南大学 | Directional crystallization-based las microcrystalline glass and preparation method therefor |
| CN114136476A (en) * | 2021-12-06 | 2022-03-04 | 无锡隆盛科技股份有限公司 | Sealing method of high-temperature sensor |
| CN115215553A (en) * | 2022-08-02 | 2022-10-21 | 上海晶材新材料科技有限公司 | Low-temperature co-fired ceramic green tape and substrate easy to match with metal slurry for co-firing and preparation method |
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