CN103325754A - Enhanced polymer composite material adapter plate based on carbon nano tube and preparation method thereof - Google Patents
Enhanced polymer composite material adapter plate based on carbon nano tube and preparation method thereof Download PDFInfo
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- CN103325754A CN103325754A CN2013101928304A CN201310192830A CN103325754A CN 103325754 A CN103325754 A CN 103325754A CN 2013101928304 A CN2013101928304 A CN 2013101928304A CN 201310192830 A CN201310192830 A CN 201310192830A CN 103325754 A CN103325754 A CN 103325754A
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Abstract
The invention provides an enhanced polymer composite material adapter plate based on a carbon nano tube and a preparation method of the enhanced polymer composite material adapter plate based on the carbon nano tube. The enhanced polymer composite material adapter plate based on the carbon nano tube comprises metal columns, side-wall insulating film, carbon nano tube network structures and polymers. The side-wall insulating film is used for covering the side walls of the metal columns to form metal column arrays which are regularly distributed on an adapter plate base body composed of the carbon nano tube network structures and the polymers, and gaps in the carbon nano tube network structures and gaps between the carbon nano tube network structures and the metal columns are filled with the polymers. Due to the facts that polymer materials are low in price and low in weight, and the carbon nano tube has good heat-conducting property and mechanical property, the heat-conducting property of the adapter plate is improved, the service life of the adapter plate is prolonged, the requirements of low cost and low weight are achieved, and industrial application can be achieved conveniently.
Description
Technical field
The present invention relates to the microelectronic packaging technology field, particularly, relate to a kind of polymer composites keyset that strengthens based on carbon nano-tube and preparation method thereof.
Background technology
In the integrated antenna package technical field, chip need to be connected with the PCB substrate, the quality of encapsulation technology directly has influence on the self performance of chip and the design of the PCB substrate that is attached thereto, it not only can fix, protect chip, the increased thermal conductivity energy, and chip and external circuit played the conducting effect; The chip live width is generally tens nanometers, and PCB substrate live width can reach the hundreds of micron, therefore will realize the interconnected of chip and PCB substrate, requires keyset substrate high-k, arrives heat conductivility, low thermal coefficient of expansion, the characteristics such as high rigidity.
The silica-based keyset of TSV technique is main developing direction, can satisfy the switchover capability of high rigidity, but through hole generally adopts deep reaction ion etching, and the formation of through hole is difficult, forms efficient lower; In addition, the imporosity of high aspect ratio vias is filled also and is difficult to, and rate of finished products is not high.
Since Iijima in 1991 found carbon nano-tube, carbon nano-tube material was known gradually, and the good physicochemical properties such as its specific area is large, good heat conductivity, mechanical strength height make it be used for multiple occasion.
A difficult problem that faces in order to overcome the silicon keyset the present invention proposes a kind of polymer composites keyset that strengthens based on carbon nano-tube.This polymer keyset can guarantee overall performance, has reduced again process costs, and quality is light, can be used for suitability for industrialized production.
Summary of the invention
For defective of the prior art, the purpose of this invention is to provide a kind of polymer composites keyset that strengthens based on carbon nano-tube and preparation method thereof, because the polymeric material price is low, quality is light, carbon nano-tube has good heat conductivility and mechanical performance simultaneously, can improve the heat conductivility of keyset, and prolong its useful life, thereby realize the requirement low-cost, that quality is light, be convenient to realize commercial application.
According to an aspect of the present invention, a kind of polymer composites keyset that strengthens based on carbon nano-tube is provided, comprise metal column, carbon nanotube network and polymer, wherein: the sidewall of metal column has dielectric film, metal column is array and is arranged in regularly in the polymer that carbon nanotube network strengthens, and vertically through the keyset matrix; Space and the space between carbon nanotube network and metal column in the carbon nanotube network are complete by polymer-filled.
Preferably, the array of metal column formation is vertically through the keyset matrix that is comprised of carbon nanotube network and polymer.
Preferably, the rectangular structure keyset matrix that carbon nanotube network and polymer consist of, its height is consistent with the height of metal column.
Preferably, metal column adopts a kind of of chromium, copper, gold, titanium, nickel or alloy.
Preferably, polymer adopts a kind of among electrophoretic paint, polyimides, epoxy resin, the SU-8.
According to a further aspect in the invention, a kind of preparation method of above-mentioned keyset is provided, in substrate, to carry out first graphically, form the metal column array by electroplating, form dielectric film at the metal column sidewall, prepare again carbon nanotube network, then make the space between carbon nano tube network be packed into polymer by electrophoresis or spin coating mode, the insulated metal post is surrounded, surface grinding is processed the metal column top is exposed from polymer, thereby forms the polymer composites keyset that a kind of carbon nano-tube strengthens.
Described method specifically may further comprise the steps:
The first step, the photoresist that gets rid of one deck 5 micron thick at glass substrate be as sacrifice layer, sputtering seed layer on sacrificial layer surface, and repeatedly again photoetching of whirl coating is carried out graphical treatment to substrate surface, forms the metal column array by electroplating, and highly is 100～300 microns;
Second step, remove the photoresist that graphically stays, the photoresist that gets rid of 5 micron thick protects the part beyond the metal column, as an electrode, as another electrode, two electrodes are put into electrophoretic paint with stainless steel or carbon plate or titanium plate with the metal column array, and link to each other with constant voltage source and to carry out electrodeposition coated film, the thickness of metal column side wall insulating film is 5～10 microns, uses deionized water ultrasonic cleaning metal column array after finishing, and carries out drying and processing at 120～150 ℃;
The 3rd step, there be not the part electrophoresis carbon nanotube network of metal column array, by electrophoresis or spin coating proceeding with polymer-filled in the carbon nano tube network gap, heating, drying, then surface grinding is processed the metal column top is exposed from polymer, go photoresist that keyset is discharged, and the another side and expose metal column of polishing, thereby the polymer composites keyset that carbon nano-tube strengthens obtained.
Carbon nano-tube is carried out preliminary treatment, be made into carbon nano tube suspension with surfactant, water or ethanol, as electrophoresis liquid, electrophoretic deposition forms carbon nanotube network in the substrate that deposits insulated metal post array after ultrasonic dispersion.
Compared with prior art, the present invention has following beneficial effect:
The present invention as strengthening body, has greatly improved the thermal conductivity of polymer keyset and mechanical strength by carbon nanotube network, has enlarged the scope of application of keyset, has prolonged the useful life of keyset; The present invention can guarantee overall performance, has reduced again process costs, and quality is light, can be used for suitability for industrialized production.
Description of drawings
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the polymer composites adapter plate structure cutaway view that the present embodiment strengthens based on carbon nano-tube;
Fig. 2 is the polymer composites adapter plate structure vertical view that the present embodiment strengthens based on carbon nano-tube.
Among the figure: 1 is that metal column, 2 is that side wall insulating film, 3 is that carbon nanotube network, 4 is polymer.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.Following examples will help those skilled in the art further to understand the present invention, but not limit in any form the present invention.Should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Embodiment 1
As shown in Figure 1 and Figure 2, the present embodiment provides a kind of polymer composites keyset that strengthens based on carbon nano-tube, comprise: metal column 1, side wall insulating film 2, carbon nanotube network 3 and polymer 4, wherein: side wall insulating film 2 is enclosed in the sidewall of metal column 1, and form metal column 1 array, in the keyset matrix that is arranged in carbon nanotube network 3 and polymer 4 compositions of this metal column 1 array rule, the space that the space in the carbon nanotube network 3 and carbon nanotube network 3 and metal column are 1 is filled complete by polymer 4.
In the present embodiment, the array that metal column 1 forms is vertically through the keyset matrix that is comprised of carbon nanotube network 3 and polymer 4.
In the present embodiment, the diameter of metal column 1 is the 10-100 micron, highly is the 100-300 micron.
In the present embodiment, the rectangular structure keyset matrix that carbon nanotube network 3 and polymer 4 consist of, its height is consistent with the height of metal column 1, is the 100-300 micron.
In the present embodiment, the thickness of side wall insulating film 2 is the 5-10 micron.
In the present embodiment, metal column 1 adopts a kind of of chromium, copper, gold, titanium, nickel or alloy.
In the present embodiment, polymer 4 adopts a kind of among electrophoretic paints, polyimides, epoxy resin, the SU-8.
The present embodiment forms the metal column array by electroplating, metal column is carried out lateral wall insulation, then prepare carbon nanotube network, make the gap-fill in the carbon nanotube network enter polymer by electrophoresis or spin coating proceeding at last, thereby form a kind of polymer composites keyset that strengthens based on carbon nano-tube.
The present embodiment provides a kind of polymer composites keyset preparation method who strengthens based on carbon nano-tube, and idiographic flow is as follows:
1, the photoresist that gets rid of 5 micron thick at glass substrate is as sacrifice layer, in photoresist surface sputtering Cr/Cu Seed Layer, wherein: Cr thickness 20 nanometers, Cu thickness 80 nanometers;
2, at above-mentioned Cr/Cu Seed Layer surface spin coating photoresist and photoetching offset plate figure, electroplate Cu under the electroplating technical conditions of routine, thickness is the 100-300 micron;
3, remove the photoresist that graphically stays, the photoresist that gets rid of again 5 micron thick protects the part beyond the metal column 1; With the metal column array as an electrode, with stainless steel or carbon plate or titanium plate as another electrode, two electrodes are put into the electrophoresis liquid that contains the 10-30wt% electrophoretic coating, electrophoretic coating is polyurethane modified epoxy or acrylic resin modified or modified acroleic acid polyurethane or acrylic modified epoxy resin, two electrodes are linked to each other with constant voltage source carry out electrodeposition coated film, the thickness of the side wall insulating film 2 of metal column 1 is 5～10 microns; Then use deionized water ultrasonic cleaning metal column array, and carry out drying and processing at 120-150 ℃;
4, prepare carbon nanotube network 3 in the part that does not have the metal column array by electrophoretic deposition process: first to the mixture of sulfuric acid and nitric acid at 60-70 ℃ of lower reflow treatment 1-3 hour, repeatedly clean to neutrality with deionized water after the cooling, magnesium nitrate or the cationic surfactant of water, ethanol or propyl alcohol, 1-20g/L are made into carbon nano tube suspension, wherein the concentration of carbon nano-tube is 2-10g/L, after ultrasonic dispersion as electrophoresis liquid, electrophoretic voltage is 3-20V, temperature is 5-40 ℃, and electrophoretic deposition forms carbon nanotube network 3;
5, by electrophoresis or spin coating proceeding polymer 4 is filled in carbon nano tube network 3 gaps, and at 120-150 ℃ of heating, drying;
6. utilize mechanical means to carry out grinding, the top of metal column 1 is exposed from polymer 4, go photoresist that keyset is discharged, and the another side and expose metal column 1 of polishing, thereby the polymer composites keyset that carbon nano-tube strengthens obtained.
It is to be noted, it is one embodiment of the invention that above-described embodiment adopts micro-processing method, can also change the kind of polymer, the size of metal structure and kind etc., not only be confined to the description of above-mentioned example, as long as in claim record scope of the present invention, all can realize purpose of the present invention.
The present embodiment is simple in technological process, on the not high basis of cost, by the enhancing body of carbon nano-tube as the keyset matrix, the thermal conductivity of keyset and mechanical strength are had greatly improved, enlarge the scope of application of keyset, prolonged the useful life of keyset; The present embodiment can guarantee overall performance, has reduced again process costs, and quality is light, can be used for suitability for industrialized production.
To sum up, the polymer composites keyset that strengthens based on carbon nano-tube of the present invention, because the polymeric material price is low, quality is light, carbon nano-tube has good heat conductivility and mechanical performance simultaneously, can improve the heat conductivility of keyset, and prolong its useful life, thereby the keyset in this invention can be realized low cost, the requirement that quality is light.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. polymer composites keyset that strengthens based on carbon nano-tube, it is characterized in that, comprise metal column, carbon nanotube network and polymer, wherein: the sidewall of metal column has dielectric film, metal column is array and is arranged in regularly in the polymer that carbon nanotube network strengthens, and vertically through the keyset matrix; Space and the space between carbon nanotube network and metal column in the carbon nanotube network are complete by polymer-filled.
2. a kind of polymer composites keyset that strengthens based on carbon nano-tube according to claim 1 is characterized in that, the array that described metal column forms is vertically through the keyset matrix that is comprised of carbon nanotube network and polymer.
3. a kind of polymer composites keyset that strengthens based on carbon nano-tube according to claim 2 is characterized in that, the diameter of described metal column is the 10-100 micron, highly is the 100-300 micron.
4. a kind of polymer composites keyset that strengthens based on carbon nano-tube according to claim 3, it is characterized in that, the rectangular structure keyset matrix that described carbon nanotube network and polymer consist of, its height is consistent with the height of metal column, is the 100-300 micron.
5. each described a kind of polymer composites keyset that strengthens based on carbon nano-tube is characterized in that according to claim 1-4, and described metal column adopts a kind of of chromium, copper, gold, titanium, nickel or alloy.
6. each described a kind of polymer composites keyset that strengthens based on carbon nano-tube is characterized in that according to claim 1-4, and the thickness of described side wall insulating film is the 5-10 micron.
7. each described a kind of polymer composites keyset that strengthens based on carbon nano-tube is characterized in that according to claim 1-4, and described polymer adopts a kind of among electrophoretic paint, polyimides, epoxy resin, the SU-8.
8. the preparation method of any described polymer composites keyset that strengthens based on carbon nano-tube of a claim 1-7 is characterized in that, described method specifically may further comprise the steps:
The first step, the photoresist that gets rid of one deck 5 micron thick at glass substrate be as sacrifice layer, sputtering seed layer on sacrificial layer surface, and repeatedly again photoetching of whirl coating is carried out graphical treatment to substrate surface, forms the metal column array by electroplating, and highly is 100～300 microns;
Second step, remove the photoresist that graphically stays, the photoresist that gets rid of 5 micron thick protects the part beyond the metal column, as an electrode, as another electrode, two electrodes are put into electrophoretic paint with stainless steel or carbon plate or titanium plate with the metal column array, and link to each other with constant voltage source and to carry out electrodeposition coated film, the thickness of metal column side wall insulating film is 5～10 microns, uses deionized water ultrasonic cleaning metal column array after finishing, and carries out drying and processing at 120～150 ℃;
The 3rd step, there be not the part electrophoresis carbon nanotube network of metal column array, by electrophoresis or spin coating proceeding with polymer-filled in the carbon nano tube network gap, oven dry, then surface grinding is processed the metal column top is exposed from polymer, go photoresist that keyset is discharged, and the another side and expose metal column of polishing, thereby the polymer composites keyset that carbon nano-tube strengthens obtained.
9. a kind of polymer composites keyset that strengthens based on carbon nano-tube according to claim 8, it is characterized in that, described carbon nano-tube is carried out first preliminary treatment, be made into carbon nano tube suspension with surfactant, water or ethanol, as electrophoresis liquid, electrophoretic deposition forms carbon nanotube network in the substrate that deposits insulated metal post array after ultrasonic dispersion.
10. according to claim 8 or 9 described a kind of polymer composites keysets that strengthen based on carbon nano-tube, it is characterized in that, described the 3rd step, be specially: prepare carbon nanotube network in the part that does not have the metal column array by electrophoretic deposition process, first to the mixture of sulfuric acid and nitric acid at 60-70 ℃ of lower reflow treatment 1-3 hour, repeatedly clean to neutrality with deionized water after the cooling, water, ethanol or propyl alcohol, magnesium nitrate or the cationic surfactant of 1-20g/L are made into carbon nano tube suspension, wherein the concentration of carbon nano-tube is 2-10g/L, after ultrasonic dispersion as electrophoresis liquid, electrophoretic voltage is 3-20V, temperature is 5-40 ℃, and electrophoretic deposition forms carbon nanotube network.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810347A (en) * | 2015-03-18 | 2015-07-29 | 上海交通大学 | Silicon carbide whisker/polymer composite material patch panel and preparation method thereof |
| CN110461558A (en) * | 2017-03-31 | 2019-11-15 | 日立造船株式会社 | Filler-resin composite body, filler-resin composite body preparation method, filler-resin compounded layer and filler-resin composite body application method |
| CN112875639A (en) * | 2021-01-25 | 2021-06-01 | 上海交通大学 | Composite flexible substrate and manufacturing method thereof |
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| US20110115121A1 (en) * | 2007-06-18 | 2011-05-19 | Samsung Electro-Mechanics Co., Ltd. | Method of manufacturing heat radiation substrate having metal core |
| WO2011125546A1 (en) * | 2010-03-31 | 2011-10-13 | 京セラ株式会社 | Interposer and electronic device using same |
| CN102709255A (en) * | 2012-06-14 | 2012-10-03 | 上海交通大学 | Metal structure sequentially-enhanced polymer composite material adapter plate |
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| US20110115121A1 (en) * | 2007-06-18 | 2011-05-19 | Samsung Electro-Mechanics Co., Ltd. | Method of manufacturing heat radiation substrate having metal core |
| WO2011125546A1 (en) * | 2010-03-31 | 2011-10-13 | 京セラ株式会社 | Interposer and electronic device using same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810347A (en) * | 2015-03-18 | 2015-07-29 | 上海交通大学 | Silicon carbide whisker/polymer composite material patch panel and preparation method thereof |
| CN104810347B (en) * | 2015-03-18 | 2017-12-15 | 上海交通大学 | Silicon carbide whisker/polymer composite material adapter plate and preparation method |
| CN110461558A (en) * | 2017-03-31 | 2019-11-15 | 日立造船株式会社 | Filler-resin composite body, filler-resin composite body preparation method, filler-resin compounded layer and filler-resin composite body application method |
| CN110461558B (en) * | 2017-03-31 | 2021-12-31 | 日立造船株式会社 | Filler-resin composite, method for producing same, filler-resin composite layer, and method for using filler-resin composite |
| CN112875639A (en) * | 2021-01-25 | 2021-06-01 | 上海交通大学 | Composite flexible substrate and manufacturing method thereof |
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