CN105693097A

CN105693097A - High-thermal-conduction low-temperature sealing glass powder

Info

Publication number: CN105693097A
Application number: CN201510138343.9A
Authority: CN
Inventors: 王双喜; 张丹; 王文君; 刘高山
Original assignee: 王双喜
Current assignee: FOSHAN BAIRUI NEW MATERIAL TECHNOLOGY Co.,Ltd.
Priority date: 2015-03-26
Filing date: 2015-03-26
Publication date: 2016-06-22
Anticipated expiration: 2035-03-26
Also published as: CN105693097B

Abstract

The invention discloses a high-thermal-conduction low-temperature sealing glass powder which is composed of the components by the volume percentage: 5-35% of one-dimension materials and 65-95% of low-melting-point glass. The low-melting-point glass has the melting temperature of not higher than 900 DEG C. One or more one-dimensional high-thermal-conduction materials are added in the glass powder, the one-dimensional materials are evenly distributed in the glass and are mutually overlapped to form thermal conduction channels, and the thermal conduction property of a sealed glass layer after sealing is improved. In addition, in the sealing process, glass slurry prepared by the glass powder has good fluidity, has high allowable solid content, and has good application prospect in the fields of sealing of integrated circuits and LED chips.

Description

A kind of high heat conduction low meiting sealing frils

Technical field

The present invention relates to a kind of high heat conduction low meiting sealing frils, belong to microelectronic packaging material field。

Background technology

Low temperature sealing glass refers to intermediate layer glass glass, pottery, metal and composite etc. sealed up each other, refers mainly to fusing point and is substantially less than the seal glass of simple glass。Development along with modern science and technology, especially the made rapid progress in vacuum electronics technology, microelectric technique, laser and the field such as infrared technique, electric light source and high-energy physics and aerospace industry, the energy, auto industry, chemical industry, industrial test, the miniaturization of device, structural detail precise treatment degree improve constantly, the kind of electronic devices and components gets more and more, article shape becomes increasingly complex, they are more and more higher to the air-tightness of sealing-in goods and the requirement of reliability, and the requirement of working environment is also more and more higher。Glass-like materials is as the one of seal, sealing materials, owing to it is better than high-molecular organic material in air-tightness and thermostability, is better than again metal material, thus seal glass has a wide range of applications field in electrical insulation capability。

The sealing temperature of seal glass is key process parameter and the index of this class material。The reduction of sealing temperature is conducive to the optimization of electronic device preparation technology。Low-temperature sealing can prevent deformation and the oxidation of metal parts, and sealing glass powder melting temperature is too high, by the mobility of glass melt when being unfavorable for sealing-in so that vitreous body can not be covered with whole sealed space, thus affecting the air-tightness of closure。

At present, the research of low temperature glass is concentrated mainly on reduction glass transformation temperature, thus reducing sealing temperature。Chinese patent CN103319097A discloses a kind of low-temperature lead-free glass dust, and the glass transition temperature of this glass dust is between 400-600 DEG C。Chinese patent CN103951189A discloses a kind of barium crown sealed glass powder and preparation method thereof, and the feature of this seal glass is to have very low transition temperature, is suitable for ultralow temperature without leaded joint。But, in electronic integrated circuit and LED encapsulation field, except the requirement to sealing temperature, the heat conductivility of seal glass be it is also proposed requirement。Die junction temperature is one of major reason affecting LED life。When LED chip sealing-in, the seal glass of good heat conductivity can conduct the heat that chip produces, and reduces luminescence chip junction temperature, improves the service life of LED。At present, the correlation technique improving low meiting sealing frils heat conductivility by adding high heat conduction one-dimensional material is had no report。The present invention proposes a kind of high heat conduction low-temperature leadless sealed glass powder and preparation technology thereof。

Summary of the invention

The problem that the present invention is directed to seal glass sealing-in poor thermal conductivity, provide a kind of high heat conduction low meiting sealing frils, it is made up of one-dimensional material and low-melting glass, it is characterized in that, comprising one or more high heat conduction one-dimensional materials in low-melting glass, one-dimensional material mutually overlaps in glass basis and forms network。

In order to reach foregoing invention purpose, the technical solution used in the present invention is a kind of high heat conduction low meiting sealing frils, and wherein the percent by volume of one-dimensional material and low-melting glass is: 5-35%:65-95%。

Wherein, described low-melting glass melting temperature is not higher than 900 DEG C。

Wherein, described high heat conduction one-dimensional material, it is possible to for one or more mixing in the insulation whiskers such as silicon nitride, aluminium nitride, boron nitride and diamond。

Wherein, described high heat conduction one-dimensional material can be one or more mixing in the insulating ceramic fiber such as silicon nitride, aluminium nitride, boron nitride

Wherein, described high heat conduction one-dimensional material can also be one or more mixing that carbon fiber, copper fiber (whisker) etc. have in the fiber of electric conductivity。

Wherein, described low-melting glass is ZnO-B₂O₃-P₂O₅System, is made up of the component of following percent by volume: ZnO30-50%, B₂O₃10-30%, P₂O₅10-30%, Bi₂O₃5-20%, Al₂O₃5-15%, Fe₂O₃0-5%。

Additionally, the preparation technology of described high heat conduction seal glass comprises the following steps:

(1) low temperature glass raw material weighs successively in proportion and is sufficiently mixed in right amount。

(2) batch mixing is incubated at 150-400 DEG C of temperature 30-60min, then melted at 800-1050 DEG C of temperature, it is incubated 2-4h；

(3) in one-dimensional material fusing point temperature once, one-dimensional material is proportionally added in vitreous humour, quickly stirring, finally pours the glass melt containing solid-state one-dimensional material formation glass dregs in plasma water into, is put into by glass dregs in baking oven and be dried 30-60min at 150-200 DEG C。

(4) by dried glass dregs ball milling 3-6h, put into after ball milling in baking oven and be dried 30-60min at 150-200 DEG C, obtain the high heat conduction sealing glass powder containing one-dimensional material。

Wherein, described high heat conduction seal glass preparation technology, it is possible to be first mixed in proportion frit and high heat conduction one-dimensional material, then melten glass, shrend, ball milling under lower than one-dimensional material melting temperature again。

High heat conduction seal glass of the present invention, it has the beneficial effects that: containing a certain amount of high heat conduction one-dimensional material in glass powder with low melting point, the relatively uniform distribution in glass basis of high heat conduction one-dimensional material, overlap joint mutually, heat quickly can be conducted by the network that one-dimensional material is formed, and substantially increases the heat conductivility of seal glass layer after encapsulation；Simultaneously, utilize encapsulation glass paste prepared by the low meiting sealing frils containing high heat conduction one-dimensional material, compared with adding glass dust and one-dimensional material prepares packaged glass slurry simultaneously, the mobility of such slurry is better, the solid content allowed is higher, in integrated circuit and LED chip encapsulation field, there is good application prospect。

Detailed description of the invention

Embodiment 1

Weigh ZnO45 part, B in proportion successively₂O₃10 parts, P₂O₅20 parts, Bi₂O₃10 parts, Al₂O₃15 parts, put into batch mixer and be sufficiently mixed。Then batch mixing is put into electric furnace at 250 DEG C of temperature, is incubated 50min, then melted at 1050 DEG C of temperature, insulation 3h, add 25 parts of boron nitride crystal whiskers after being cooled to 850 DEG C to be sufficiently stirred for melten glass liquid, finally pour formation glass dregs in plasma water into, glass dregs is put into baking oven dry 50min at 160 DEG C。Then by glass dregs ball milling 4.5h, put into baking oven dry 50min at 160 DEG C, obtain the high heat conduction sealing glass powder containing boron nitride crystal whisker。

Embodiment 2

Weigh ZnO36 part, B in proportion successively₂O₃28 parts, P₂O₅10 parts, Bi₂O₃6.5 parts, Al₂O₃4.5 parts, Fe₂O₃5 parts, silicon nitride crystal whisker 10 parts, put into batch mixer and be sufficiently mixed。Then batch mixing is put into electric furnace at 300 DEG C of temperature, is incubated 40min, then melted at 850 DEG C of temperature, it is incubated 3.5h, finally pours formation glass dregs in plasma water into, glass dregs is put into baking oven dry 40min at 180 DEG C。By glass dregs ball milling 4h, it is then placed in baking oven and dries 40min at 180 DEG C, both must contain the high heat conduction sealing glass powder of silicon nitride crystal whisker。

Embodiment 3

Weigh ZnO30 part, B in proportion successively₂O₃10 parts, P₂O₅30 parts, Bi₂O₃20 parts, Al₂O₃6 parts, Fe₂O₃Put into batch mixer for 4 parts to be sufficiently mixed。Then batch mixing is put into electric furnace at 400 DEG C of temperature, is incubated 30min, then melted at 800 DEG C of temperature, it is incubated 4h；Add the vitreous humour that 15 parts short copper fibers are extremely melted is sufficiently stirred for and finally pour formation glass dregs in plasma water into, glass dregs is put into baking oven dry 30min at 200 DEG C。Then by glass dregs ball milling 3h, it is then placed in baking oven and dries 30min at 200 DEG C, both obtain the high heat conduction sealing glass powder of cupric fiber。

Embodiment 4

Weigh ZnO40 part, B in proportion successively₂O₃20 parts, P₂O₅20 parts, Bi₂O₃10 parts, Al₂O₃8 parts, Fe₂O₃2 parts, put into batch mixer and carry out being sufficiently mixed 100min。Then batch mixing is put into electric furnace at 150 DEG C of temperature, is incubated 60min, then melted at 900 DEG C of temperature, it is incubated 2h, adds 33 parts of carbon fibers and be sufficiently stirred for melten glass liquid, finally pour formation glass dregs in plasma water into, glass dregs is put into baking oven dry 60min at 150 DEG C。Then by glass dregs ball milling 5.5h, put into baking oven dry 60min at 150 DEG C, both must contain the high heat conduction sealing glass powder of carbon fiber。

Above embodiments is only that the specific embodiment of the present invention is described, not the scope of the present invention is defined, those skilled in the art also can do numerous modifications and variations on the basis of existing technology, as selected other system glass powder with low melting point, or in glass paste, add cryogenic glass powder and high heat conduction whisker etc. simultaneously。Without departing from the spirit of the invention, various modification that technical scheme is made by this area ordinary skill technical staff and improvement, all should fall in the protection domain that claims of the present invention are determined。

Claims

1. a high heat conduction low meiting sealing frils, is made up of one-dimensional material and low-melting glass, it is characterised in that comprise one or more high heat conduction one-dimensional materials in low-melting glass, and one-dimensional material mutually overlaps in glass basis and forms network。

2. the high heat conduction low meiting sealing frils of one according to claim 1, it is characterised in that described one-dimensional material and the percent by volume of low-melting glass be: 5～35%:65～95%。

3. the high heat conduction low meiting sealing frils of one according to claim 1, it is characterised in that described low-melting glass melting temperature is not higher than 900 DEG C。

4. the high heat conduction low meiting sealing frils of one according to claim 1, it is characterised in that described high heat conduction one-dimensional material can be one or more mixing in the insulation whiskers such as silicon nitride, aluminium nitride, boron nitride and diamond。

5. the high heat conduction low meiting sealing frils of one according to claim 1, it is characterised in that described high heat conduction one-dimensional material can be one or more mixing in the insulating ceramic fiber such as silicon nitride, aluminium nitride, boron nitride。

6. the high heat conduction low meiting sealing frils of one according to claim 1, it is characterised in that described high heat conduction one-dimensional material can be one or more mixing that carbon fiber, copper fiber (whisker) etc. have in the fiber of electric conductivity。

7. a kind of low-melting glass according to claim 3, it is characterised in that described glass is ZnO-B₂O₃-P₂O₅System, is made up of the component of following percent by volume: ZnO30-50%, B₂O₃10-30%, P₂O₅10-30%, Bi₂O₃5-20%, Al₂O₃5-15%, Fe₂O₃0-5%。

8. the preparation technology of one kind high heat conduction sealing glass powder, it is characterised in that its preparation technology comprises the following steps:

(2) compound is incubated at 150-400 DEG C of temperature 30-60min, then melted at 800-1050 DEG C of temperature, it is incubated 2-4h；

(3) in one-dimensional material fusing point temperature below, one-dimensional material is proportionally added in vitreous humour, quickly stirring, finally pours formation glass dregs in plasma water into by the glass melt containing solid-state one-dimensional material, is put into by glass dregs and dries 30-60min in baking oven at 150-200 DEG C。

(4) by dried glass dregs ball milling 3-6h, put into after ball milling and baking oven dries 30-60min at 150-200 DEG C, obtain the high heat conduction sealing glass powder containing one-dimensional material。

9. the preparation technology of a kind of high heat conduction sealing glass powder according to claim 8, it is characterised in that can first be mixed in proportion frit and one-dimensional material, then melted under lower than one-dimensional material melting temperature, shrend again, ball milling。