CN101488461A - Circuit board without the need of photoresist and precious metal sensitizing compound and seed layer manufacturing method thereof - Google Patents
Circuit board without the need of photoresist and precious metal sensitizing compound and seed layer manufacturing method thereof Download PDFInfo
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- CN101488461A CN101488461A CNA2009100374973A CN200910037497A CN101488461A CN 101488461 A CN101488461 A CN 101488461A CN A2009100374973 A CNA2009100374973 A CN A2009100374973A CN 200910037497 A CN200910037497 A CN 200910037497A CN 101488461 A CN101488461 A CN 101488461A
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- copper
- wiring board
- vacuum ultraviolet
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Abstract
The invention discloses a circuit board without photoresist and noble metal activating agent and a method for manufacturing a seed layer thereof. The method comprises the following steps: vacuum ultraviolet light source is used to penetrate a mask, in an environment containing reducing substances, copper compounds attached to the surface of base material is irradiated to activate the irradiated copper compounds to restore, a copper wire pattern seed layer is formed on the surface of the base material; then the copper wire pattern is obtained by chemical coppering or electrochemical coppering. The invention is a method which can ensure that the insulated base material surface can be selectively metallized without using photoresist, palladium activating agent and platinum activating agent and provides a low-cost novel technique used for producing the copper wire pattern seed layer and copper lead on the surface of the base material.
Description
Technical field
The invention belongs to wiring board (printing circuit board PCB) technical field, be specifically related to the manufacture method of full addition wiring board.
Background technology
Wiring board (printing circuit board PCB) is one of topmost parts in the semiconductor electronic device, it is applied to nearly all electronic product, little of electronic watch, calculator, PC, arrive electromechanical equipment control assembly, data handling machine, communication electronic equipment and military armament systems greatly.As long as the place of integrated circuit and other electronic devices and components is arranged, just need use wiring board.
The main effect one of wiring board is the electric interconnection of realizing between integrated circuit and the various electronic devices and components; The 2nd, load chip and other various electronic devices and components, the mechanical support of mount is provided; In addition, it the desired electrical characteristic of product electric insulation such as impedance, withstand voltage, dielectric etc. also need be provided and the components and parts assembling be provided, check, identification character and figure that maintenance is required.The technology quality index of wiring board directly has influence on the function and the performance of electronic product.
Wiring board is many with conductor and organic substrate be combined into.Along with the development of electronics industry, conductor develops into Copper Foil from electrically conductive ink, and conductor width drops to tens microns from the millimeter level; Base material has also experienced by cardboard, has strengthened the transition of phenolic aldehyde/epoxy resin to high performance engineering plastics; Wiring board also expands to high density flexible and toughness wiring board from rigid plate, to satisfy the needs of mobile communication product and flat-panel screens development.People wish that not only base material has high thermomechanical property and electrical insulation properties, wish that also it has low dielectric constant, reduce between circuit impedance and to the influence of high frequency electrical signal; Wish that simultaneously copper conductor has little spacing, wiring board reaches electrode as much as possible in unit length, obtains high I/O value.
At present, high performance wiring board is many is that raw material is made with Copper Foil and organic substrate.Manufacture craft can be divided into and subtracts layer method or semi-additive process.In manufacturing process, Copper Foil changes into required copper cash figure line by applying light-sensitive emulsion, exposure, development, etching and removing the photoetching process that glue cleans.The also useful so-called fully-additive process of highdensity flexible circuit board is made.Its typical technology is at first to use sputter Cr/Cu or other method, at surface of polymer substrates formation metal film as thin as a wafer,, the metallized polymer surfaces of major part is covered then by photoresist and photoetching process, stay small part and contact, by electroplating thickening with electroplate liquid.After removing photoresist layer, dissolve away the thin copper layer of polymer surfaces, constitute required copper cash figure line.Fully-additive process will be used the equipment or the specific process of semiconductor manufacturing usefulness, complex process, and cost is higher.Photoetching process consumes a large amount of chemical solutions and water, produces many accessory substances.These contain the easy contaminated environment of waste liquid of heavy metal ion, and its influence more and more receives publicity.
People are exploring the new technology that can make the surface of polymer material selective metallization always, directly make copper cash figure line on insulating body, save traditional photoetching process.Physical vapour deposition (PVD), chemical vapour deposition (CVD) or plated film can make surface metallation of insulator, but can not satisfy optionally requirement.Photochemical method is a main direction of exploring selective metallization.People are desirably under the help of mask, can optionally introduce the copper-plated Seed Layer of catalytic chemistry at surface of polymer substrates, produce copper cash figure line through electroless copper again.
M.Setta and H.Nawafune etc. [J.Mater.Chem., V11 (2001), pp2919] research is with ultraviolet light (UV) selective reduction pd
+ 2Ion is also made lead figure line on polyimides (PI) film.They introduce carboxyl earlier with the hydrolysis under alkali condition of PI film at film surface, immerse PdCl then
2Solution absorption Pd
+ 2Ion and sodium formate are again with 35mW/cm
2High-pressure mercury lamp (365nm UV) irradiation, at room temperature with Pd
+ 2Be reduced to Metal Palladium.Remove unreduced Pd by optical mask and pickling
+ 2Ion carries out electrochemistry copper facing or electroless copper again, and they successfully produce thin extremely several microns the copper conductor of live width on the PI film.H.Nawafune etc. [pp 487 for Appl.Surface Sci., V109-110 (1997)] research GuSO
4Replace expensive PdCl
2, on the PI film, directly make copper cash figure line.Although the photon energy of 365nm has only 3.4eV, reduction Cu
+ 2Speed slower, at colloid TiO
2Sensibilization under, through radiation in two hours, can form the Seed Layer of electroless copper, produce copper cash figure line at the PI film surface.
U.Kogelschatz etc. [Proc.SPIE, V5483 (2004), pp272] study with the higher Excimer UV light modulation reduction Pd of photon energy
+ 2With making copper cash figure line on insulating material.They use Ar
2 ※Lamp (126nm), Xe
2 ※Lamp (172nm), KrCl
※Lamp (222nm) or XeCl
※Lamp (308nm) reduction palladium or acetylacetone,2,4-pentanedione platinum, and bring out electroless copper or nickel plating with the palladium, the platinum nanometer film that generate, at Al
2O
3, make plain conductor on AlN, Si, quartz, glass reinforced epoxy, polyimides, the Polyetherimide.The near ultraviolet radiation that their vacuum ultraviolet that studies show that 172nm is longer than wavelength is more effective, just can form Pd or Pt Seed Layer through 1-5 minute radiation at substrate surface, bring out electroless copper plating, produce the copper cash of about one micron of live width on the insulating substrate surface.The company of Japan, Korea S adopts similar technology to process the low dielectric flexible circuit board of high density in the laboratory.Yet, because metallic compounds such as palladium, platinum are very expensive, the production cost of this technology can't with the comparing of existing technology.
In integrated circuit is made, U.S. Pat 6,972,257 propose by light radiation and mask, with the reduction of the cupric oxide membrane portions on silicon chip or the insulating barrier, make copper cash; US 6,348,125 and US 7,084,067 point out that after the high-intensity vacuum UV-irradiation, the cupric oxide plated film can change copper conductor into.
Summary of the invention
The objective of the invention is to use precious metal chemical complexs such as palladium, platinum in order to overcome existing photochemistry selectivity activation insulating substrate, the shortcoming that cost is high, provide that a kind of low cost, technology are simple, environmental protection not with photoresist with the wiring board and the seed layer manufacturing method thereof thereof of precious metal sensitizing.The present invention is achieved through the following technical solutions:
The present invention's vacuum ultraviolet light source sees through contact mask, and in containing the environment of reducing substances, irradiation invests the copper compound of substrate surface, excites reduced by the copper compound of illumination, forms copper cash figure line Seed Layer at substrate surface.On this basis, electroless copper through utilizing present technology maturation or electrochemistry copper electroplating method are made copper cash figure line again.
The photon energy that the present invention is based on ultra-violet radiation reduces and increases with radiation wavelength, thereby has the stronger potential that excites chemical reaction; Wavelength is lower than the vacuum-ultraviolet light of 200nm, its photon energy is greater than 6.2eV, the bond energy that is higher than most chemical bonds, energy splitting chemical compound lot, discharge high-octane reactive hydrogen atom and atomic group, simultaneously also can excite the valence electron of copper compound to transit to conduction band from valence band, the reduction of stirred copper compound under normal temperature condition generates the Seed Layer of facilitating electroless copper.
The scheme that the present invention further improves is to utilize the vacuum-ultraviolet light of wavelength 100 to 200nm, in containing the environment of reducing substances, see through mask (contact or noncontact mask), irradiation invests the copper compound of substrate surface, excite the reduction of copper compound, form copper cash figure line Seed Layer at substrate surface,, make copper cash figure line thereafter again through electroless copper.
Described vacuum ultraviolet (VUV) only by the wavelength of quasi-molecule ultraviolet source or semiconductor ultraviolet emitting device emission at 100 to 200nm ultraviolet light, its photon energy about 6.2 to 12.4eV, near the black light of wavelength 254nm and 365nm of launching than common high pressure or low pressure mercury lamp has the stronger photochemically reactive ability that excites, photolytic reduction material and activated copper compound are facilitated the copper compound reduction simultaneously.The vacuum ultraviolet (VUV) luminous energy output of described ultraviolet source needs at 10mW/cm
2More than, to obtain practical reaction speed and production efficiency.
Described Excimer UV light modulation is xenon excimer vacuum ultraviolet (VUV) light modulation (Xe
2 ※172nm), krypton quasi-molecule vacuum ultraviolet (VUV) light modulation (Kr
2 ※146nm).Independent one or more of described ultraviolet source merge the copper compound that irradiation together invests substrate surface, as the excitation source of copper compound reduction, provide many selectivity.
Described base material is polymeric material or clear glass, as polytetrafluoroethylene, polyimides, polyphenylene oxide, polyester, epoxy plastics, ito glass.Polymeric material can be the polymeric material of not enhancing or the polymeric material of enhancing.Described substrate surface is with the layer of copper compound.Copper compound is the mixture of independent certain copper compound or two or more copper compounds.Copper compound imposes on substrate surface through any way, and as dip-coating, showering, spraying, rolling method, chemistry shifts.
Described base material can be through surface modification before coating, introduces carboxyl, amido or other groups at substrate surface, improve substrate surface to the wettability of copper-containing compound and with the adsorptivity of copper.The thickness of copper compound is mainly determined by the requirement of follow-up copper-plating technique and final products, but also to consider the photon energy of used vacuum ultraviolet light source and the size of luminous flux, the copper compound of coating can be reduced into fully metallic copper and have good bonding with base material to guarantee vacuum-ultraviolet light.As with xenon excimer ultraviolet lamp (Xe
2 ※172nm) be excitation source, the THICKNESS CONTROL of copper compound is in 10 nanometers to 5 micron, and it is 25 to 500 nanometers that first-selection is controlled at.
Described vacuum ultraviolet light source is the environment that is filled with nitrogen or rare gas to the space of substrate surface.Nitrogen or rare gas are optically transparent to the vacuum ultraviolet of used ultraviolet source emission, and like this, the decay of vacuum-ultraviolet light in reactor is few.
Described reducing substances is the gaseous material that has protium in the molecule, as hydrogen, ammonia, hydrazine, methane.Described reducing substances also can be the condensed state matter that invests on the copper compound, as formic acid or formic acid esters (salt).But water and hydrogen peroxide are not included within the reproducibility thing.Described reducing substances can absorb the vacuum ultraviolet of used ultraviolet lamp emission.After reducing substances is subjected to the vacuum ultraviolet (VUV) optical excitation, can discharge hydrogen atom and other gaseous material of upper state.Described vacuum-ultraviolet light also can be the valence electron of copper compound from the valence to the conduction band, and oxygen atom is overflowed, so by hydrogen atom or other atomic group is captured and for the carrier gas band from substrate surface.Like this, when the irradiation of vacuum ultraviolet (VUV) light transmission contact mask invested the copper compound of substrate surface, irradiated copper compound promptly in-situ reducing was a metallic copper, formed copper film figure line at substrate surface.The new copper film that forms is the effective catalyst of electroless copper, can cause electroless copper plating in the copper-plated solution of general chemistry, and copper film figure line grows up to copper cash figure line.
The content of described reducing substances in atmosphere can not be too high, in order to avoid the reducing substances interception does not have vacuum-ultraviolet light to arrive at substrate surface from all vacuum ultraviolets that ultraviolet source sends, activates copper compound.Suitably control the content of reducing substances in atmosphere, the speed of balance photolysis reducing substances and optical excitation copper compound, making has maximum oxygen atom to overflow and combine with the hydrogen atom or the atomic group of upper state in the unit interval, and is taken away by carrier gas, obtains the effect of best reduction copper compound.With hydrogen or ammonia is that reducing substances is an example, and the content of reducing substances in nitrogen generally is controlled at 0.2% to 20%, preferentially is controlled at 1% to 5%.
Described copper compound can the preferably copper oxide or mantoquita etc.The irradiation time of described ultraviolet excitation reduction copper compound should be adjusted according to factors such as base material, intensity of illumination, reducing atmospheres.Reducing fully under the prerequisite of copper compound, reducing light application time, enhancing productivity.Be that reducing agent is in 15mW/cm with hydrogen or ammonia
2Xenon excimer ultraviolet lamp (Xe
2 ※Irradiation 172nm) is an example, and the time for exposure is controlled at and is lower than 30 minutes, preferentially is controlled to be lower than 3 minutes.The described thickness of going back native copper does not need too thick, can catalytic chemistry copper facing greater than 5nm.But can be according to technology and product needed, adjust the thickness to 5 micron of reduction copper seed layer.The metallic copper activity that produces through the vacuum ultraviolet (VUV) photo-reduction is very high, can need not further acid-wash activation immediately as the Seed Layer of electroless copper.If but in air the storage period long, then need acid-wash activation.The copper compound that is adsorbed on substrate surface can clean with dilute acid soln.
The present invention in containing the environment of reducing substances, sees through the copper compound that the mask irradiation invests substrate surface with the vacuum-ultraviolet light of Excimer UV light modulation output.The vacuum-ultraviolet light of high energy is exciting reducing substances to decompose, and when producing upper state hydrogen atom and atomic group, also excites copper compound, and oxygen atom is overflowed, by hydrogen atom or other atomic group is captured and for the carrier gas band from.Like this, under ambient temperature conditions, reduced by light-struck copper compound, on base material, form thin copper film figure line.In chemical copper plating solution, bring out heavy copper with the copper film of fresh generation, make copper film thickening becoming copper conductor.Like this, not with photoresist and precious metal sensitizing, make the copper cash figure line close with mask hollow out decorative pattern at substrate surface.
Wiring board manufacture method provided by the invention is full addition wiring board manufacture method, except above-mentioned advantage and effect, also have following advantage with respect to prior art: (1) the present invention uses copper compound as the preceding body of selectivity copper facing activator but not use expensive palladium or platinum compounds, has the low characteristics of cost; (2) the present invention need not to make with photoresist and photoetching process, has the production stage characteristic of simple; (3) the present invention does not have the inhomogeneous quality problems that cause of photosensitive film thickness not with photoresist, has the characteristics of easy operating.(4) the present invention need not molten copper etch step, and waste of material is few, and the heavy metal waste liquid is few, has the characteristics of environmental protection.
Embodiment
Below in conjunction with embodiment concrete enforcement of the present invention is described further, but the present invention is not limited to this, the various raw materials in the technical scheme provided by the present invention have replaceability, only enumerate typical example at this.And electroless copper and electrochemistry copper facing are existing mature technology, also do not do too much giving unnecessary details at this.
Example one
The PI thin slice of 80mm * 20mm is immersed 10% KOH solution, and that the PI sheet is become is hydrophilic; Immerse CuSO after hydrophilic PI sheet crossed water
4Saturated solution, taking-up is dried; Dry again with half of the wetting PI film of 0.5% formic acid solution, place xenon excimer ultraviolet lamp (Xe
2 ※172nm) in effective radiation area of reactor sample stage, and push down the two ends of PI sheet with slide.Effectively the area of radiation area is 225mm * 104mm, the about by force 10mW/cm of illumination
2Feed 0.5 liter/minute nitrogen and 0.5 liter/minute hydrogeneous 5% H toward reactor
2/ N
2Mist, Continuous irradiation formed copper cash figure line Seed Layer after 15 minutes on the surface, sample is immersed in the chemical copper plating solution immediately, and after five hours, the part that scribbles formic acid in the middle part of the PI thin slice has the copper film of even metallic luster.There is the zone of metallic luster to have conductivity after the pickling drying, and do not remain electric insulation with the moistening end of formic acid.
Example two
At xenon excimer ultraviolet lamp (Xe
2 ※Be in the photo catalysis reactor of vacuum ultraviolet light source 172nm), pack into the sample of copper oxide film.Vacuum ultraviolet light source has the optical window of 150mm * 150mm and 15mW/cm is arranged
2Vacuum ultraviolet export from optical window.Sample has two kinds of wide 55mm of long 100mm and the wide 8mm of long 80mm.Cu oxide is CuO/Cu (OH)
2Mixture, about 2 microns of oxide thickness.The copper oxide film of sample faces optical window, places the centre under the optical window, sample surfaces to the distance adjustment on optical window surface to about 2mm.After driving air in ultraviolet source and the reactor cavity away with 4 liters/minute nitrogen, import hydrogeneous 5% H in the reactor cavity
2/ N
2Mist.The vent valve of conditioned reaction device is kept flow about 0.2 liter/minute, starts the xenon excimer ultraviolet lamp after one minute.Continuous irradiation is closed the xenon excimer ultraviolet lamp after 30 minutes, form copper cash figure line Seed Layer on the surface.Small sample is transferred to the seal of vessel that is full of nitrogen again and does surface analysis, large sample is transferred to and does the electroless copper experiment in the copper plating solution.
After the vacuum ultraviolet (VUV) optical processing, the copper oxide film of sample becomes orange-yellow from darkviolet.Photoelectron spectroscopy (XPS) demonstration CuLMM Auger moves in the peak, and the binding energy of Cu2P3/2 electronics is displaced downwardly to the 932.4eV of metallic copper from the 935.1eV of aqua oxidation copper.Through the part of UV-irradiation, can in the common chemical copper plating solution, bring out heavy copper (commonly used chemical copper plating solution as shown in table 1), copper facing thickness can as electroless copper equally control by adjusting copper plating solution and technology.And the part of masked covering still is a darkviolet, can not bring out heavy copper.
Table 1
| Form | I | II | III |
| Copper sulphate (g/L) | 14 | 10 | 16 |
| Sodium potassium tartrate tetrahydrate (g/L) | 40 | — | 15 |
| EDTA disodium salt (g/L) | — | 40 | 20 |
| NaOH (g/L) | 20 | 12 | 15 |
| Thiocarbamide (g/L) | 0.5 | / | / |
| Potassium ferrocyanide (g/L) | / | 0.1 | 0.05 |
| Duplex pyridine (g/L) | / | 0.01 | 0.02 |
| Formaldehyde (ml/L) | 15 | 10 | 15 |
| Working temperature (℃) | 25 | 60 | 40 |
Claims (10)
1, not with photoresist with the wiring board seed layer manufacturing method thereof of precious metal sensitizing, it is characterized in that using vacuum ultraviolet light source, see through mask, in containing the environment of reducing substances, irradiation invests the copper compound of substrate surface, excite reduced by the copper compound of illumination, form copper cash figure line Seed Layer, promptly make described wiring board Seed Layer at substrate surface.
2, not with photoresist with the wiring board manufacture method of precious metal sensitizing, it is characterized in that using vacuum ultraviolet light source, see through mask, in containing the environment of reducing substances, irradiation invests the copper compound of substrate surface, excite reduced by the copper compound of illumination, form copper cash figure line Seed Layer at substrate surface; And then, make copper cash figure line through electroless copper or electrochemistry copper facing, promptly make described wiring board.
3, wiring board manufacture method according to claim 2, it is characterized in that described reducing substances is subjected to the vacuum ultraviolet (VUV) optical excitation after, can discharge the hydrogen atom or the gaseous material of upper state; Described reducing substances is for the gas of band hydrogen or invest formic acid, formic acid esters or formates on the copper compound.
4, full addition wiring board manufacture method according to claim 3, the gas that it is characterized in that described band hydrogen is hydrogen, ammonia, hydrazine or methane; Contain nitrogen or rare gas in the gaseous environment between described vacuum ultraviolet (VUV) light modulation and the base material, the volume content of gas in gaseous environment of band hydrogen is 0.2%～20%.
5, wiring board manufacture method according to claim 2 is characterized in that the vacuum ultraviolet (VUV) optical wavelength of described vacuum ultraviolet light source output is 100～200nm, and photon energy is 6.2～12.4eV.
6, wiring board manufacture method according to claim 5 is characterized in that described vacuum ultraviolet light source is one or more in 172nm xenon excimer ultraviolet lamp, 146nm krypton Excimer UV light modulation, the 100～200nm semiconductor vacuum ultraviolet emitting device; The vacuum ultraviolet (VUV) luminous energy of described vacuum ultraviolet light source output is greater than 10mW/cm
2
7, wiring board manufacture method according to claim 2 is characterized in that described base material is polymeric material or clear glass; Described copper compound is the mixture of a kind of copper compound or two or more copper compounds; Through surface modification, introducing has adsorbing amido, carboxyl or acid amides with copper ion to described surface of polymer material on the surface before applying copper compound.
8, wiring board manufacture method according to claim 7 is characterized in that described copper compound is Cu oxide or mantoquita.
9, wiring board manufacture method according to claim 2, the thickness that it is characterized in that described copper compound are 10 nanometers～5 micron.
10, wiring board manufacture method according to claim 9, the thickness that it is characterized in that described copper cash figure line Seed Layer are 5 nanometers～5 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100374973A CN101488461A (en) | 2009-02-27 | 2009-02-27 | Circuit board without the need of photoresist and precious metal sensitizing compound and seed layer manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100374973A CN101488461A (en) | 2009-02-27 | 2009-02-27 | Circuit board without the need of photoresist and precious metal sensitizing compound and seed layer manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101488461A true CN101488461A (en) | 2009-07-22 |
Family
ID=40891273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100374973A Pending CN101488461A (en) | 2009-02-27 | 2009-02-27 | Circuit board without the need of photoresist and precious metal sensitizing compound and seed layer manufacturing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103338596A (en) * | 2013-06-18 | 2013-10-02 | 华南理工大学 | Manufacturing method of whole addition circuit board without photoresist |
| CN107331599A (en) * | 2017-05-08 | 2017-11-07 | 安徽长青电子机械（集团）有限公司 | A kind of preparation method for plating substrate surface crystal seed layer |
| WO2020236518A1 (en) * | 2019-05-22 | 2020-11-26 | The Board Of Trustees Of The University Of Illinois | Photoresist-free deposition and patterning with vacuum ultraviolet lamps |
| CN115427609A (en) * | 2020-05-29 | 2022-12-02 | 优志旺电机株式会社 | Reduction treatment method |
-
2009
- 2009-02-27 CN CNA2009100374973A patent/CN101488461A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103338596A (en) * | 2013-06-18 | 2013-10-02 | 华南理工大学 | Manufacturing method of whole addition circuit board without photoresist |
| CN107331599A (en) * | 2017-05-08 | 2017-11-07 | 安徽长青电子机械（集团）有限公司 | A kind of preparation method for plating substrate surface crystal seed layer |
| CN107331599B (en) * | 2017-05-08 | 2019-12-20 | 安徽长青电子机械（集团）有限公司 | Preparation method of seed crystal layer on surface of plating substrate |
| WO2020236518A1 (en) * | 2019-05-22 | 2020-11-26 | The Board Of Trustees Of The University Of Illinois | Photoresist-free deposition and patterning with vacuum ultraviolet lamps |
| CN115427609A (en) * | 2020-05-29 | 2022-12-02 | 优志旺电机株式会社 | Reduction treatment method |
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