CN1772948A - Laser induced selective chemical plating process for polyimide film - Google Patents
Laser induced selective chemical plating process for polyimide film Download PDFInfo
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- CN1772948A CN1772948A CN 200510110438 CN200510110438A CN1772948A CN 1772948 A CN1772948 A CN 1772948A CN 200510110438 CN200510110438 CN 200510110438 CN 200510110438 A CN200510110438 A CN 200510110438A CN 1772948 A CN1772948 A CN 1772948A
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Abstract
The present invention discloses one kind of laser induced selective chemical plating process for polyimide film. Polyimide film is first modified into one with bond silver ion in the surface, and the modified polyimide film is then selectively irradiated with focused laser beam, dilute acid solution treated and high temperature treated, and finally plated chemically to form micron level patterns of chemical plating on the surface of polyimide film. The process is simple and less pollutant, the pattern is computer controllable and has high resolution and selectivity, and the plating has well combination to the substrate. The present invention has excellent application foreground in circuit board manufacture, integrated circuit and other electronic industry fields.
Description
Technical field: the invention belongs to the metallized method of a kind of polymer surface, particularly silver is planted in the activation of laser induced selective deposition on polyimide surface, carries out the method for electroless plating then.
Background technology: polyimide material has good insulation performance and stopping property, and also have other outstanding properties such as the thermostability height, can be high temperature resistant and utmost point low temperature, have good mechanical property, thermal expansivity is low, nontoxic, especially it has low specific inductivity, can reduce current interference and energy consumption between the lead.So polyimide has vast application prospect at microelectronic.Electroless plating technology is subjected to wider application owing to having cheapness and normal-temperature operation in electronics industry and microelectronics industry.But traditional chemical coating technology complex steps, operation inconvenience and consuming time more is polluted greatlyyer, and difficulty is carried out granular production and has been limited its certain applications.Along with development of integrated circuits, electroless plating technology develops to microminiaturization, simplification and pollution-freeization direction.And the introducing of laser technology not only can reduce operation, reduce to pollute, and improves the resolving power and the bonding force of coating, and can realize microcomputer control, the various line patterns that utilize the track while scan of computer controlled controlling laser beam to obtain expecting.People such as K.Kord á s have delivered the research work of inducing electroless plating with laser on polyimide on magazines such as thin solid films and applied surface science, they are placed on polyimide in special chemical plating fluid or the palladium solution, carry out carrying out electroless plating behind direct chemical plating or the generation spike with laser radiation, but their method or coating are not thick, use palladium metal to do spike, cost is higher.In electroless plating, committed step is to plant spike on the non-metallic material, and coating only can be grown on spike.Spike is generally selected heavy metal gold, palladium, platinum etc., costs an arm and a leg.The application report of relatively cheap argent is less.And present method is utilized the deposition of induced with laser spike silver to carry out electroless plating on polyimide surface also not have relevant report at present.
Summary of the invention: the objective of the invention is the Kapton surface chemical modification and fetter silver ions, go out silver with laser focusing radiation selective reduction then, carry out selective chemical plating at last, obtain the patterned chemical plating of micron order on the Kapton surface.
The method of Kapton laser induced selective chemical plating of the present invention is as follows:
(1) surface modification of Kapton: Kapton is immersed in the strong base solution of 0.5～2mol/L, soaking temperature is 20～80 ℃, soak time is 1～50 minute, takes out and uses washed with de-ionized water, cleans Kapton surface, back and generates imide salts; Immerse then in the silver nitrate solution of 1～15g/L, soaking temperature is 20～80 ℃, and soak time is 5～120 minutes, takes out and uses washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions, and wherein highly basic is sodium hydroxide or potassium hydroxide;
(2) Kapton of dissimulated electricity silver ions carries out laser radiation: the Kapton of dissimulated electricity silver ions is placed on the sample table of laser aid, with laser focusing, moving of computer program control bundle or sample table, Wavelength of Laser is in 133～400nm scope, and the energy after the focusing is 0.05～10mJ/cm
2, sweep velocity is 0.01～10mm/s, obtains the Kapton after the laser radiation, the silver ions at radiation zone after the laser radiation is reduced into metallic silver corpuscle, and the silver ions of radiation areas is not kept intact;
(3) formation again of the cleaning of the unnecessary silver ions in the Kapton after laser radiation surface and Kapton surface imide ring: it is in 0.05%～10% the dilute acid soln that the Kapton after the laser radiation is immersed volume ratio, soaking temperature is 10～50 ℃, soak time is 1～80 minute, take out then and use washed with de-ionized water, exchanged by hydrogen ion at the silver ions of radiation areas not like this, the surface of radiation areas does not generate polyimide acid, carry out pyroprocessing then, temperature is 150～250 ℃, storing time is 0.5～3 hour, the imide acid of baking back is closed into imide ring again, obtain the Kapton of surperficial selective depositing silver, wherein diluted acid is a dilute sulphuric acid, dilute formic acid, acetic acid,diluted; rare propionic acid; or rare nitric acid;
(4) electroless plating: the Kapton of the selective depositing silver in surface put in commodity or homemade electroless copper, nickel plating or the silver plated plating bath carry out electroless plating, the temperature of electroless plating is controlled at 20～60 ℃, time is 25～45 minutes, plated the back and cleaned, obtained the patterned chemical plating of micron order on the Kapton surface with clear water.
The used Kapton of the present invention is the polymkeric substance that contains imide ring in the molecular structure.
The method of Kapton laser induced selective chemical plating of the present invention is to have adopted the laser selective radiating surface to have the Kapton of silver ions constraint to reach subsequently selective chemical plating, finally obtains the patterned chemical plating of micron order on the Kapton surface.The invention process is simple, it is little to pollute, but the figure computer is controlled in real time, and coating and Kapton bonding force are good, and coating has passed through the test of standard GB 4677.7-84 adhesive tape method at the sticking power of Kapton.Graphics resolution and selectivity height, the live width of the electroless copper that employing the inventive method obtains can reach 25 microns, and line is thick to can reach 2 microns.
Description of drawings
Fig. 1 is the synoptic diagram of embodiment 1 laser aid.
Fig. 2 is the sem photograph behind embodiment 1 electroless copper.
Fig. 3 is the sem photograph behind embodiment 2 electroless coppers.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
(1) surface modification of Kapton: Kapton is immersed in the potassium hydroxide solution of 1mol/L, soaking temperature is 50 ℃, soak time is 10 minutes, take out and use washed with de-ionized water, immerse then in the silver nitrate solution of 6g/L, soaking temperature is 30 ℃, and soak time is 50 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton of dissimulated electricity silver ions carries out laser radiation: the Kapton of dissimulated electricity silver ions is placed on the sample table of laser aid, Fig. 1 is the synoptic diagram of laser aid, laser focusing to 20 microns of spot diameters, is used moving of computer time variable control sample table.Wavelength of Laser is selected 266nm, and the energy after the focusing is controlled at 1.0mJ/cm
2, sweep velocity is 0.1mm/s, thereby obtains the Kapton after the laser radiation;
(3) formation again of the cleaning of the unnecessary silver ions in the Kapton after laser radiation surface and Kapton surface imide ring: it is in 2% the dilution heat of sulfuric acid that the Kapton after the laser radiation is immersed volume ratio, soaking temperature is 20 ℃, soak time is 5 minutes, take out and use washed with de-ionized water, carry out pyroprocessing then, temperature is 200 ℃, storing time is 2.5 hours, the imide acid of baking back is closed into imide ring again, obtains the Kapton of surperficial selective depositing silver;
(4) electroless plating: the Kapton of the selective depositing silver in surface is dropped in the chemical bronze plating liquid, and the composition of plating bath is: five water blue vitriol 10g/L, sodium hydroxide 15g/L, formaldehyde solution (37.2wt.%) 12mL, Seignette salt 24g.The temperature of electroless plating is controlled at 35 ℃, and the time of electroless plating is 30 minutes, has plated the back and has cleaned with clear water, obtains the patterned chemical plating of micron order on the Kapton surface.Fig. 2 is the sem photograph behind the electroless copper.
Embodiment 2
(1) surface modification of Kapton: Kapton is immersed in the potassium hydroxide solution of 1mol/L, soaking temperature is 40 ℃, soak time is 40 minutes, take out and use washed with de-ionized water, immerse then in the silver nitrate solution of 2g/L, soaking temperature is 25 ℃, and soak time is 100 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton of dissimulated electricity silver ions carries out laser radiation: the Kapton of dissimulated electricity silver ions is placed on the sample table of laser aid, laser focusing to 20 microns of spot diameters, is used moving of computer time variable control sample table.Wavelength of Laser is selected 266nm, and the energy after the focusing is controlled at 0.8mJ/cm
2, sweep velocity is 0.2mm/s, thereby obtains the Kapton after the laser radiation;
(3) formation again of the cleaning of the unnecessary silver ions in the Kapton after laser radiation surface and Kapton surface imide ring: it is in 5% the dilution heat of sulfuric acid that the Kapton after the laser radiation is immersed volume ratio, soaking temperature is 30 ℃, soak time is 2 minutes, take out and use washed with de-ionized water, carry out pyroprocessing then, temperature is 220 ℃, storing time is 2.0 hours, the imide acid of baking back is closed into imide ring again, obtains the Kapton of surperficial selective depositing silver;
(4) electroless plating: the Kapton of the selective depositing silver in surface is dropped in the chemical bronze plating liquid, and the composition of plating bath is: five water blue vitriol 10g/L, sodium hydroxide 15g/L, formaldehyde solution (37.2wt.%) 12mL, Seignette salt 24g.The temperature of electroless plating is controlled at 40 ℃, and the time of electroless plating is 30 minutes, has plated the back and has cleaned with clear water, obtains the patterned chemical plating of micron order on the Kapton surface.Fig. 3 is the sem photograph behind the electroless copper.
Embodiment 3
(1) surface modification of Kapton: Kapton is immersed in the potassium hydroxide solution of 1.5mol/L, soaking temperature is 40 ℃, soak time is 20 minutes, take out and use washed with de-ionized water, immerse then in the silver nitrate solution of 4g/L, soaking temperature is 20 ℃, and soak time is 120 minutes, take out and use washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions;
(2) Kapton of dissimulated electricity silver ions carries out laser radiation: the Kapton of dissimulated electricity silver ions is placed on the sample table of laser aid, laser focusing to 20 microns of spot diameters, is used moving of computer time variable control sample table.Wavelength of Laser is selected 355nm, and the energy after the focusing is controlled at 4.0mJ/cm
2, sweep velocity is 0.5mm/s, thereby obtains the Kapton after the laser radiation;
(3) formation again of the cleaning of the unnecessary silver ions in the Kapton after laser radiation surface and Kapton surface imide ring: it is in 5% the dilution heat of sulfuric acid that the Kapton after the laser radiation is immersed volume ratio, soaking temperature is 25 ℃, soak time is 8 minutes, take out and use washed with de-ionized water, carry out pyroprocessing then, temperature is 250 ℃, storing time is 1.5 hours, the imide acid of baking back is closed into imide ring again, obtains the Kapton of surperficial selective depositing silver;
(4) electroless plating: the Kapton of the selective depositing silver in surface is dropped in the chemical bronze plating liquid, and the composition of plating bath is: five water blue vitriol 10g/L, sodium hydroxide 15g/L, formaldehyde solution (37.2wt.%) 12mL, Seignette salt 24g.The temperature of electroless plating is controlled at 40 ℃, and the time of electroless plating is 30 minutes, has plated the back and has cleaned with clear water, obtains the patterned chemical plating of micron order on the Kapton surface.
Claims (1)
1. the method for Kapton laser induced selective chemical plating is characterized in that its method is as follows:
(1) surface modification of Kapton: Kapton is immersed in the strong base solution of 0.5～2mol/L, soaking temperature is 20～80 ℃, soak time is 1～50 minute, takes out and uses washed with de-ionized water, cleans Kapton surface, back and generates imide salts; Immerse then in the silver nitrate solution of 1～15g/L, soaking temperature is 20～80 ℃, and soak time is 5～120 minutes, takes out and uses washed with de-ionized water, thereby obtain the Kapton of dissimulated electricity silver ions, and wherein highly basic is sodium hydroxide or potassium hydroxide;
(2) Kapton of dissimulated electricity silver ions carries out laser radiation: the Kapton of dissimulated electricity silver ions is placed on the sample table of laser aid, with laser focusing, moving of computer program control bundle or sample table, Wavelength of Laser is in 133～400nm scope, and the energy after the focusing is 0.05～10mJ/cm
2, sweep velocity is 0.01～10mm/s, obtains the Kapton after the laser radiation, the silver ions at radiation zone after the laser radiation is reduced into metallic silver corpuscle, and the silver ions of radiation areas is not kept intact;
(3) formation again of the cleaning of the unnecessary silver ions in the Kapton after laser radiation surface and Kapton surface imide ring: it is in 0.05%～10% the dilute acid soln that the Kapton after the laser radiation is immersed volume ratio, soaking temperature is 10～50 ℃, soak time is 1～80 minute, take out then and use washed with de-ionized water, exchanged by hydrogen ion at the silver ions of radiation areas not like this, the surface of radiation areas does not generate polyimide acid, carry out pyroprocessing then, temperature is 150～250 ℃, storing time is 0.5～3 hour, the imide acid of baking back is closed into imide ring again, obtain the Kapton of surperficial selective depositing silver, wherein diluted acid is a dilute sulphuric acid, dilute formic acid, acetic acid,diluted; rare propionic acid; or rare nitric acid;
(4) electroless plating: the Kapton of the selective depositing silver in surface put in commodity or homemade electroless copper, nickel plating or the silver plated plating bath carry out electroless plating, the temperature of electroless plating is controlled at 20～60 ℃, time is 25～45 minutes, plated the back and cleaned, obtained the patterned chemical plating of micron order on the Kapton surface with clear water.
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| CN101469075B (en) * | 2007-12-28 | 2011-03-16 | 北京化工大学 | Method for preparing two-sided polyimide / silver compound film |
| CN102196660A (en) * | 2010-03-05 | 2011-09-21 | 欣兴电子股份有限公司 | Circuit structure |
| US8288662B2 (en) | 2009-10-26 | 2012-10-16 | Unimicron Technology Corp. | Circuit structure |
| CN102031505B (en) * | 2009-09-25 | 2013-01-09 | 比亚迪股份有限公司 | Treating fluid for coarsening and activating polyimide and method for coarsening and activating surface of polyimide |
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| US5104734A (en) * | 1988-06-03 | 1992-04-14 | International Business Machines Corporation | Method for improving adhesion between a polyimide layer and a metal and the article obtained |
| JP2002064252A (en) * | 2000-08-22 | 2002-02-28 | Kanegafuchi Chem Ind Co Ltd | Polyimide film, laminate using the same, and multilayered wiring board |
| JP4517564B2 (en) * | 2002-05-23 | 2010-08-04 | 住友金属鉱山株式会社 | 2-layer copper polyimide substrate |
| JP2004035996A (en) * | 2002-07-03 | 2004-02-05 | Tao:Kk | Manufacturing method for and manufacturing line of plated and coated product |
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| CN101654001B (en) * | 2008-08-21 | 2015-05-13 | 比亚迪股份有限公司 | Metallized film, preparation method thereof and circuit board containing same |
| CN102031505B (en) * | 2009-09-25 | 2013-01-09 | 比亚迪股份有限公司 | Treating fluid for coarsening and activating polyimide and method for coarsening and activating surface of polyimide |
| US8288662B2 (en) | 2009-10-26 | 2012-10-16 | Unimicron Technology Corp. | Circuit structure |
| CN102196660A (en) * | 2010-03-05 | 2011-09-21 | 欣兴电子股份有限公司 | Circuit structure |
| CN102196660B (en) * | 2010-03-05 | 2013-09-11 | 欣兴电子股份有限公司 | Circuit structure |
| CN103173724A (en) * | 2011-12-26 | 2013-06-26 | 深圳光启高等理工研究院 | Microstructure processing method |
| CN103173724B (en) * | 2011-12-26 | 2016-01-06 | 深圳光启高等理工研究院 | Method for processing microstructure |
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| CN106544655A (en) * | 2016-10-13 | 2017-03-29 | 上海交通大学 | A kind of preparation method of polyimide surface patterned conductive Ag films |
| CN106544655B (en) * | 2016-10-13 | 2019-10-08 | 上海交通大学 | A kind of preparation method of polyimide surface patterned conductive Ag films |
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