CN108342754A - Substrate plating composition and the coating method for utilizing the composition - Google Patents
Substrate plating composition and the coating method for utilizing the composition Download PDFInfo
- Publication number
- CN108342754A CN108342754A CN201810052395.8A CN201810052395A CN108342754A CN 108342754 A CN108342754 A CN 108342754A CN 201810052395 A CN201810052395 A CN 201810052395A CN 108342754 A CN108342754 A CN 108342754A
- Authority
- CN
- China
- Prior art keywords
- substrate
- plating
- composition
- hole
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The present invention provides substrate plating composition and the coating method using the composition, the substrate plating include with composition：Alkyl ammonium halide；And selected from formaldehyde and SYNPERONIC PE/F68 (EO PO copolymer) more than one.
Description
Technical field
The present invention relates to a kind of substrate plating composition and the substrate coating methods of utilization the composition.
Background technology
With including printed circuit board (printed circuit board：PCB the lightweight of electronic equipment), small-sized
With and densification, the manufacturing method as multilayer board use increasing layer (build-up) technique.In increasing layer work
In skill, one of part and parcel is to fill through-hole using metal and realize interlayer and be powered.(via fill) is filled for via
The representative metal of plating is copper, in general, via filling plating depends on plating mode.
Since when carrying out via filling plating by plating mode, substrate surface is also plated together, so surface is plated
The thickness of coating can increase.Via filling plating efficiencies are lower, and the thickness increase degree of coating surface layer can be higher.For via
For filling plating plating solution, it is added as filler usually in the plating solution and fills the organic of plating efficiencies for adjusting via
Substance.The organic substance added is conveniently referred to as inhibitor, flat dose (leveler), urges according to major function
Agent or brightener etc..
With the gradual slimming of substrate, it is desirable that realize the thickness of relatively thin coating surface layer.It is plated requiring relatively thin surface
In the case of the thickness of coating, if the thickness for only pressing required degree carries out plating, it is likely that because via fills plating
Defect not exclusively occurs when manufacturing printed circuit board.Therefore, following mode is used：Plating is filled until completing via
Until carry out plating, make the thickness for the coating surface layer for being more than thinning again later.In the thickness more than target surface coating layer
In the case of, usually increase the process that etching or grinding (grinding) etc. keep the thickness of coating surface layer thinning.Therefore, printing electricity
The manufacture efficiency of road plate is lower, and thickness uniformity can also be deteriorated.
[existing technical literature]
[patent document]
(patent document 1) Korean Patent Publication No. 10-1072338
Invention content
The present invention relates to a kind of following substrate plating composition and the coating methods of utilization the composition：Including alkyl
Ammonium halide (Alkylammonium Halide) and from formaldehyde and ethylene oxide-propylene oxide copolymer (EO-PO
Copolymer) more than one middle selected, to maximize the electro-deposition inhibition on substrate surface, so that inside through-hole
Precipitation (separating) it is relatively active, be not plated to reach substrate surface and through-hole only made effectively to obtain uniformly
Via fills the effect of plating.
According to an aspect of the present invention, a kind of substrate plating composition is provided, wherein including：Alkyl ammonium halide；With
And selected from formaldehyde and ethylene oxide-propylene oxide copolymer (EO-PO copolymer) more than one.
An embodiment according to the present invention, the substrate plating composition can be acidic copper liquid composite.
An embodiment according to the present invention, the substrate plating may include with composition：Acid, mantoquita and chlorion
Close object.
An embodiment according to the present invention, the alkyl ammonium halide can be the compounds of following chemical formula 1：
[chemical formula 1]
(NR4)+X-,
Wherein, R=CnH(2n+1),
N=1~30,
X=Cl, Br or I.
An embodiment according to the present invention, the alkyl ammonium halide can utilize 10~30 carbon atoms to constitute.
An embodiment according to the present invention, the alkyl ammonium halide can be selected from N (CH3)3(C4H9)+X-、N(CH3)3
(C8H17)+X-、N(CH3)3(C12H25)+X-、N(CH3)3(C16H33)+X-、N(CH3)3(C20H41)+X-、N(C2H5)3(C4H9)+X-、N
(C2H5)3(C8H17)+X-、N(C2H5)3(C12H25)+X-、N(C2H5)3(C16H33)+X-、N(CH3)4 +X-、N(C2H5)4 +X-、N(C3H7)4 +
X-、N(C4H9)4 +X-And N (C7H15)4 +X-More than one, and X be Cl, Br or I.
An embodiment according to the present invention, the alkyl ammonium halide can be selected from cetyl trimethylammonium bromide
(Cetyltrimethylammonium bromide；CTAB), hexadecyltrimethylammonium chloride
(Cetyltrimethylammonium chloride；CTAC), dodecyl trimethyl ammonium chloride
(Dodecyltrimethylammonium chloride；) and dodecyl trimethyl ammonium bromide DTAC
(Dodecyltrimethylammonium bromide；DTAB) more than one.
An embodiment according to the present invention may include big relative to the overall weight of the substrate plating composition
In 0.0003 parts by weight and less than the alkyl ammonium halide of 0.01 parts by weight.
An embodiment according to the present invention, relative to the substrate plating composition overall weight and with 0.0001 to
0.5 parts by weight include more than one selected from the formaldehyde and ethylene oxide-propylene oxide copolymer.
An embodiment according to the present invention, the molecular weight of the ethylene oxide-propylene oxide copolymer can be 1,000 to
100,000。
An embodiment according to the present invention, the ethylene oxide-propylene oxide copolymer can be the epoxies in copolymer
Ethane part divides rate to be 1/3 copolymer.
An embodiment according to the present invention, the plating composition can also include：Surface modifier.
The molecular weight of an embodiment according to the present invention, the surface modifier can be 50 to 1500.
An embodiment according to the present invention can include 0.0001 relative to the overall weight of substrate plating composition
The surface modifier of~1 parts by weight.
According to another aspect of the present invention, a kind of substrate is provided, including：First insulating layer；First copper foil layer is formed in institute
State the upper surface of the first insulating layer；Second insulating layer is formed in the upper surface of first copper foil layer；And through-hole, penetrate through institute
It states second insulating layer and is formed to the upper surface of first copper foil layer, wherein the through-hole is filled in plating, however institute
The surface for stating the substrate around through-hole is not plated substantially.
An embodiment according to the present invention, when the through-hole essentially completes filling, the surface of the substrate can be several
It is not plated, or can be plated with 1 μm of thickness below.
An embodiment according to the present invention, the through-hole are filled out by above-mentioned substrate plating according to the present invention with composition
It fills.
An embodiment according to the present invention, the thickness a of the coating surface layer of the substrate and the bottom to surface from via
Thickness b until coating layer can meet a/b<0.02 relationship.
An embodiment according to the present invention can also include the coating surface layer of the substrate.
An embodiment according to the present invention can also include the seed layer for the upper surface for being formed in the second insulating layer.
An embodiment according to the present invention, the substrate may include the first copper foil layer；Second copper foil layer；Insulating layer, folder
Between first copper foil layer and the second copper foil layer；And via, it penetrates through second copper foil layer and insulating layer and is formed
To the upper surface of first copper foil layer.
According to another aspect of the invention, a kind of substrate plating composition is provided, wherein including：Ethylene oxide-epoxy
Propane copolymer (EO-PO copolymer), and the substrate plating is acidic copper liquid composite with composition.
According to another aspect of the invention, a kind of substrate coating method is provided, wherein include the following steps：In substrate shape
At through-hole；And the substrate for being formed with the through-hole is made to contact it with composition with above-mentioned substrate plating according to the present invention
After-applied electric current and fill through-hole, carry out plating in a manner of inhibiting the growth of coating surface layer at this time.
An embodiment according to the present invention can also include as follows before the step of filling through-hole carries out plating
Step：Seed layer is formed in the upper surface of substrate surface and through-hole.
An embodiment according to the present invention can also include as follows after the step of filling through-hole carries out plating
Step：Plating is carried out to the substrate surface with composition using the second plating.
An embodiment according to the present invention, the substrate are copper-clad laminate (Copper Clad Laminate；
CCL)。
An embodiment according to the present invention, because of the coating surface layer growth inhibitory effect, the thickness of coating surface layer can
It is suppressed to 1 μm or less.
An embodiment according to the present invention, by providing a kind of maximized substrate plating of coating surface layer growth inhibitory effect
Cover and use composition, in a period of fill through-hole, the plating layer thickness of substrate surface will not a logical increase, therefore can be most
It is bad caused by smallization coating layer thickness deviation.It is therefore not necessary to the flat chemical industry such as etching or grinding of the coating surface layer of substrate
Sequence, so as to effectively manufacture printed circuit board.
An embodiment according to the present invention additionally carries out the coating surface for substrate after filling through-hole, to
It is free to adjust the plating layer thickness of substrate.Due to being not necessarily to consider that via is filled out when selecting substrate surface plating composition
Characteristic is filled, so need to only select the composition for being most suitable for improving thickness deviation, there is no need to special effort can also be significantly
Reduce the coating layer thickness deviation of substrate surface.Caused by improving the thickness deviation by the coating surface layer of substrate
Impedance matching (Impedance matching) bad, sealing of hole (tenting) product do not etch with over etching it is bad, stacking
It is bad, bending (warpage) is bad etc..
Description of the drawings
Fig. 1 is the plating composition schematically shown using an embodiment according to the present invention, without substrate
Coating surface in the case of be only filled with the plating of through-hole (zero thickness fill plating (Zero thickness fill
(ZTF) plating)) later to the sectional view of the substrate of the situation of the surface of substrate progress plating.
The coating surface layer of substrate when Fig. 2 is for illustrating that the via of an embodiment according to the present invention fills plating
The sectional view of the substrate of the relationship between thickness b until thickness a and bottom to coating surface layer from via.
Fig. 3 is the section for the substrate coating method including seed layer for schematically showing an embodiment according to the present invention
Figure.
Fig. 4 is formation dry film pattern (the dry film on substrate for schematically showing an embodiment according to the present invention
Pattern the sectional view of the substrate coating method in the state of).
Fig. 5 is to schematically show an embodiment according to the present invention and to copper-clad laminate (Copper Clad
Laminate；CCL the sectional view of the method for plating) is carried out after progress through-hole processing to through-hole.
Fig. 6 be show using a diameter of 90 μm, depth for 80 μm through-hole and to an embodiment according to the present invention carry out
Via fills the section of the via after the coating surface with substrate and the section according to the via after the plating of prior art progress
The cross sectional photograph being compared.
Fig. 7 is show an embodiment according to the present invention a diameter of 90 μm, the filling plating for the through-hole that depth is 80 μm
The cross sectional photograph of the through-hole of process.
Fig. 8 be show to a diameter of 90 μm, depth to be that 80 μm of through-hole is filled according to an embodiment of the invention, and
It additionally carries out the plating of substrate surface and controls the cross sectional photograph of the situation of thickness.
Fig. 9 is according to an embodiment of the invention and obtains the planar picture of the substrate of via filling plating.The photo is pair
The photo that position is shot at 25 in substrate, it can be seen that overall region is equably filled out without occurring bad
It fills.
Figure 10 be according to an embodiment of the invention using the formaldehyde including 50ppm and include various concentration alkylammonium halogen
The substrate plating composition of compound fills via the planar picture of the substrate of plating.3ppm's or less or 100ppm or more
Under the conditions of, it may be occurred according to plating conditions bad.Understand that the concentration ranges that can steadily use are very wide.
Figure 11 is comparative example according to the present invention and utilizes the base for only including alkyl ammonium halide in acidic copper electrolytes
Plate plating carries out the planar picture of the substrate of plating with composition.It is such as indicated in photo, it is difficult to obtain uniform surface.
Figure 12 to Figure 15 is to show an embodiment according to the present invention and utilize the substrate plating for being added to surface modifier
The cross sectional photograph of the through-hole of filling plating is obtained with composition.
Figure 16 is an embodiment according to the present invention and carries out through-hole processing to CCL substrates, and is formed kind using chemical copper
The cross sectional photograph of the via of via filling plating is carried out after sublayer.
Figure 17 is to show that the via for obtaining the etching line of the via of via filling plating according to an embodiment of the invention cuts open
Face photo.Etching line is that the line of plating and coating surface is filled for dividing via.The position of etching line can be by adjusting
It fills plating amount and is formed in the arbitrary position of vias inside in hole.
Figure 18 is will to utilize the substrate plating for only not including formaldehyde including alkyl ammonium halide in acidic copper electrolytes
Form (left side) after carrying out plating with composition with using the substrate plating composition comprising alkyl ammonium halide and formaldehyde into
Form (right side) after row plating compares and the planar picture that shows.
Figure 19 is the form for showing the plating solution VR used as the JCU companies of the prior art and carrying out via filling plating
Cross sectional photograph.
Figure 20 is the form shown using the acidic copper solution progress via filling plating for not including organic additive
Cross sectional photograph.
Figure 21 is to show an embodiment according to the present invention and utilize comprising alkyl ammonium halide (CTAB) and ethylene oxide-
The substrate plating of epoxy propane copolymer (EO-PO copolymer) carries out the plane that via fills the form of plating with composition
Photo.
Figure 22 is to show to utilize the substrate for including alkyl ammonium halide (DTAB) and EO-PO copolymers according to an embodiment
Plating carries out the photo that via fills the form of plating with composition.
Figure 23 is to show to utilize in acidic copper solution not including alkylammonium halogenation according to an embodiment of the invention
Object and include the ethylene oxide-propylene oxide copolymer (EO-PO copolymer) of various concentration substrate plating combination
Object and carry out via filling plating substrate planar picture.
Figure 24 is to show to combine using the weaker substrate plating of overlay coating growth inhibitory effect according to prior art
Object and the figure for simulating the result of (simulation) based on Plating times increased coating growth.
Figure 25 is to show to plate using the stronger substrate of overlay coating growth inhibitory effect of an embodiment according to the present invention
Cover with composition and simulate the figure of the result based on the increased coating growth of Plating times.
Figure 26 is shown in the embodiment of Figure 25 using the overlay coating that the amount of overlay coating inhibitor is excessively increased
The very strong substrate plating composition of growth inhibitory effect and simulate the result based on Plating times increased coating growth
Figure.
Symbol description
10：First insulating layer 12：Second insulating layer
20、310：First copper foil layer 22,310'：Second copper foil layer
24：Coating surface layer 26：Seed layer
28：Dry film 100：Substrate
300：Copper-clad laminate 322：Third copper foil layer
Specific implementation mode
The term or word used in present specification and claims should not be construed as the meaning on common, dictionary,
And the original for the concept that can should suitably define term based on inventor in order to illustrate the invention of oneself in optimal method
Then, it is only construed to meet the meaning and concept of the technological thought of the present invention.
Term used herein is merely illustrative specific embodiment, and purpose does not lie in the restriction present invention.Odd number
Be expressed in there is no specific antisense in article in the case of include plural number statement.
In the application, the terms such as " comprising " or " having " are used to specify feature described in specification, number, step, dynamic
The presence of work, inscape, component or combination thereof, should not be construed as excluding in advance other more than one features or
Number, step, action, inscape, component or combination thereof there is a possibility that or it is additional.
In the application, when mentioning a certain inscape of some part " comprising ", in the not special feelings recorded on the contrary
Under condition, however not excluded that other inscapes, and it can also includes other inscapes to mean.Also, in the specification,
" on being located at ... " indicates to be located above or below object part, is not offered as on the basis of gravity direction to be located at upper
Side.
The present invention can apply a variety of transformation, and can have various embodiments, and specific embodiment is shown in the accompanying drawings
And it is described in detail in illustrating.It will be appreciated, however, that the invention is not limited thereto specific implementation form, and
It is the thought and the technical scope all transformation, equivalent and the substitute that are included for including the present invention.It is carried out to the present invention
When illustrating, be judged as to related known technology illustrate be possible to spirit of the invention can be made to fog in the case of,
Description is omitted.
Hereinafter, the present invention is described in more detail.
Substrate plating composition
According to an aspect of the present invention, a kind of following substrate plating composition is provided：Including alkyl ammonium halide with
And selected from formaldehyde and ethylene oxide-propylene oxide copolymer (EO-PO copolymer) more than one.
The alkyl ammonium halide can be the compound of chemical formula 1 below：
[chemical formula 1]
(NR4)+X-,
Wherein, R=CnH(2n+1),
N=1~30,
X=Cl, Br or I.
The carbon atom number for constituting the alkyl chain of the alkyl ammonium halide is preferably 10 or more and 30 hereinafter, still not
It is limited to this.When constituting the carbon atom number of alkyl chain of the alkyl ammonium halide less than 10 or more than 30, for plating
The limitation of condition can become larger.In general, in the case where carbon atom number is less than 10, since overlay coating growth inhibitory effect does not fill
Point, so being filled only with the characteristic of through-hole can die down, and in the case where carbon atom number is more than 30, occur on the surface of the substrate
The case where abnormal plating of non-uniform form, increases, so being limited there is plating conditions and being difficult to carry out asking for process management
Topic.
The alkyl ammonium halide can be selected from N (CH3)3(C4H9)+X-、N(CH3)3(C8H17)+X-、N(CH3)3
(C12H25)+X-、N(CH3)3(C16H33)+X-、N(CH3)3(C20H41)+X-、N(C2H5)3(C4H9)+X-、N(C2H5)3(C8H17)+X-、N
(C2H5)3(C12H25)+X-、N(C2H5)3(C16H33)+X-、N(CH3)4 +X-、N(C2H5)4 +X-、N(C3H7)4 +X-、N(C4H9)4 +X-And
N(C7H15)4 +X-More than one, and X be Cl, Br or I.However it is not limited thereto.
The alkyl ammonium halide can be selected from cetyl trimethylammonium bromide (Cetyltrimethylammonium
bromide；CTAB), hexadecyltrimethylammonium chloride (Cetyltrimethylammonium chloride；CTAC), 12
Alkyl trimethyl ammonium chloride (Dodecyltrimethylammonium chloride；) and trimethyl bromine DTAC
Change ammonium (Dodecyltrimethylammonium bromide；DTAB) more than one, and most suitable can be CTAB.
However it is not limited thereto.
The alkyl ammonium halide can relative to the substrate plating composition overall weight and to be more than
0.0003 parts by weight and less than 0.01 parts by weight, be more than 0.0003 parts by weight and 0.007 parts by weight or less, be more than 0.0003 weight
Part and 0.005 parts by weight below, 0.0005 or more parts by weight and less than 0.01 parts by weight, more than 0.001 parts by weight and 0.007 weight
Part or less, 0.001 parts by weight are measured less than more than 0.01 parts by weight, 0.001 parts by weight and 0.007 parts by weight model below
It encloses and includes, and be suitble to more than 0.001 parts by weight and 0.005 parts by weight range below includes that but not limited to this.Institute
It is 0.0003 parts by weight or less or 0.01 weight that alkyl ammonium halide, which is stated, relative to the overall weight of substrate plating composition
Part or more in the case of, the surface of substrate may also can be plated.In this application, parts by weight indicate weight %.
More than one selected from formaldehyde and ethylene oxide-propylene oxide copolymer (EO-PO copolymer)
It is suitable relative to the overall weight of the substrate plating composition to include with 0.0001 to 0.5 parts by weight, but it is unlimited
In this.Described formaldehyde etc. relative to the overall weight of the substrate plating composition and be less than 0.0001 parts by weight or
In the case of including more than 0.5 parts by weight, the surface of substrate may also can be plated.
The molecular weight of the ethylene oxide-propylene oxide copolymer (EO-PO copolymer) can be 1,000 to 100,
000, but not limited to this.It is less than 1 in the molecular weight of the ethylene oxide-propylene oxide copolymer (EO-PO copolymer),
000 or more than in the case of 100,000, the surface of substrate may also can be plated.
Ethylene oxide moiety in the copolymer of the ethylene oxide-propylene oxide copolymer (EO-PO copolymer)
Point rate (fraction) be preferably 1/3 or more, but not limited to this.Rate is being divided to be less than 1/3 using ethylene oxide moiety
In the case of ethylene oxide-propylene oxide copolymer (EO-PO copolymer), coating surface bad phenomenon may increase.
The substrate plating composition of the present invention can be the composition of acidic copper solution.
The composition of the acid shape cupric electrolysis solution may include acid, mantoquita and chlorion compound.
The acid is electrolyte, and electric conductivity when to be electroplated needs the acid.Acid can be selected from sulfuric acid (H2SO4), salt
Sour (HCl), acetic acid (CH3) and fluoboric acid (HBF COOH4One or more of), and be suitble to use sulfuric acid, but be not limited to
This.Sulfuric acid concentration is higher, then provides lower liquid resistance, therefore electric conductivity is good, but if improves copper sulphate simultaneously
Content is then prone to be precipitated；If sulfuric acid concentration is low, plating property can reduce.The acid is with respect to base of the invention
The overall weight of plate plating composition and be suitble to account for 0.05 parts by weight to 8 parts by weight, but not limited to this.It is combined as plating solution
The acid of the main component of object should be supplemented by regularly analyzing.
The mantoquita can be from by copper sulphate (CuSO4·5H2O), copper nitrate (Cu (NO3)2), copper formate (Cu (HCOO)2)
And dichloride copper (CuCl2·2H2O more than one) are selected in the group formed, but not limited to this.
The concentration of the mantoquita is higher, is more conducive to fill plating, but plating property may reduce.In the mantoquita
Copper content includes that but not limited to this with 0.05 to 5 parts by weight relative to coating composition overall weight.If the mantoquita
The amount of interior copper is accounted for relative to coating composition overall weight less than 0.05 parts by weight, then has hair in high current density part
The tendency of raw burnt deposit (Burnt Deposit) phenomenon, and if it exceeds 5 parts by weight, then have and precipitation phenomenon occur
Tendency.
The chlorion compound can be used selected from sodium chloride and hydrochloric acid, and but not limited to this.It is dense when chlorion
When degree is higher, it is likely to form passive state (passive state) film in anode and causes the dissolving of anode and the reduction of powered,
And precipitation spot may be will produce.The chlorion with respect to the present invention substrate plating composition overall weight
And it is suitble to account for 0.0002 weight point to 0.02 weight point, but not limited to this.
The substrate plating composition of the present invention can also include surface modifier.
The surface modifier is used to realize the top for the through-hole after filling in the case where only needing to fill through-hole
The planarization of exposure and homogenization.
The molecular weight of the surface modifier is suitably for 50 or more and 1500 hereinafter, but not limited to this.On the surface
In the case that the molecular weight of modifying agent is less than 50 or more than 1500, surface is modified improvement and may reduce.Preferably, institute
The molecular weight for stating surface modifier can be 100 to 500, and but not limited to this.
The concentration of the surface modifier can be by general technical staff of the technical field of the invention according to via
Size and current condition etc. and suitably adjust and use.Substrate plating of the concentration of the surface modifier compared to the present invention
0.0001 parts by weight or more can be accounted for composition overall weight and 1 parts by weight are hereinafter, but not limited to this.
The surface modifier can be selected from triarylmethane dye, azole, azole derivatives, pyrimidine, pyrimidine derivates
One or more of object and brightener (brightner) series, but not limited to this.The surface modifier can be by the present invention
Person of an ordinary skill in the technical field selects according to the size of via and current condition etc. and combines optimal substance simultaneously
It uses.
The triarylmethane dye can be selected from crystal violet (methyl violet) 2B, methyl violet 6B, crystal violet 10B,
Pararosaniline (Pararozaniline), pinkish red (hydrochloride), New Fuchsine (New fuchsine, As oxide), acid product
Red (Fuchsine acid), phenolphthalein, phenol red (Phenol red), chlorophenol red (Chlorophenol red), cresol red
(Cresol red), bromocresol purple (Bromocresol purple), bromocresol green (Bromocresol green), malachite
Green (Malachite green), brilliant green (dyestuff) (Brilliant Green (dye)), brilliant blue FCF (Brilliant Blue
FCF), victoria blue B (Victoria Blue B), Victoria blue FBR (Victoria Blue FBR), Victoria blue
BO (Victoria Blue BO), Victoria blue FGA (Victoria Blue FGA), victoria blue 4R (Victoria
Blue 4R) and victoria blue R (Victoria Blue R), but not limited to this.
The azole can be selected from imidazoles, pyrazoles, 1,2,3- triazoles, 1,2,4- triazoles, tetrazolium, pentazole, oxazole, different evil
Azoles, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, furazan (1,2,5- oxadiazoles), 1,3,4- oxadiazoles, thiazole, isothiazole, 1,2,
3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles and 1,3,4- thiadiazoles, but not limited to this.
The azole derivatives can be selected from imidazoles, 1- methylimidazoles, 1- ethyl imidazol(e)s, 1- isopropylimdazoles, 1- butyl
Imidazoles, benzimidazole, 1- vinyl imidazoles, 1,2,4- triazoles, benzotriazole, pyrazoles, benzoxazoles and benzothiazole, still
It is without being limited thereto.
The pyrimidine derivatives can be selected from cytimidine, thiamine and uracil, and but not limited to this.
The brightener (brightener) can be selected from 3- sulfydryl -1- propane sulfonic acid, bis- (sodium sulfopropyl)-disulphide with
And bipyridyl etc., but not limited to this.
Substrate
Fig. 1 is the plating composition schematically shown using an embodiment according to the present invention, without being directed to
Plating (zero thickness filling plating (the Zero thickness fill of through-hole are only filled in the case of the coating surface of substrate
(ZTF) plating)) later to the sectional view (seed layer is not shown) of the substrate of the situation of the surface of substrate progress plating.
Referring to Fig.1, according to another aspect of the present invention, a kind of following substrate is provided：Including the first insulating layer 10；It is formed
The first copper foil layer 20 in 10 upper surface of the first insulating layer；It is formed in the second insulation of 20 upper surface of the first copper foil layer
Layer 12；And penetrate through the second insulating layer 12 and formed to the through-hole of the upper surface of first copper foil layer 20, wherein is described
Through-hole is filled when carrying out plating, but the surface of the substrate around the through-hole is substantially without being plated.
In the present invention, the surface of so-called substrate refers to following state substantially without being plated：Although through-hole is real
It is filled in matter, but the surface of substrate, almost without being plated, there is no need to carry out the planarization for substrate surface and thickness
Spend the etching or grinding of adjustment.In the present invention, this is referred to as zero thickness and fills (Zero thickness fill (ZTF)).
For example, when through-hole has essentially completed filling, indicate that substrate surface is hardly formed plated film or with 1 μm of thickness quilt below
The state of plating, but not limited to this.
The through-hole is characterized in that, is filled with composition by above-mentioned substrate plating according to the present invention.
In the present invention, the substrate can be printed circuit board or semiconductor substrate, be suitably for printed circuit board.But
It is not limited to this.
In the present invention, the through-hole will be formed in the blind hole (Blind via hole) of substrate, groove (Trench) with
And through hole includes all.
(a) referring to Fig.1, the substrate 100 be the first insulating layer 10, the first copper foil layer 20 and second insulating layer 12 continuously
The substrate 100 being laminated.In 12 part of second insulating layer of the printed circuit board through-hole is formed using laser etc..
(b) referring to Fig.1 fills the substrate plating composition of an embodiment according to the present invention and forms the second copper foil
Layer 22.
As described above, substrate plating composition according to the present invention becomes maximum due to overlay coating growth inhibitory effect
Change, so as to realize the ZTF only effectively and uniformly being filled to through-hole in the case that substrate surface is not plated
Plating.
Therefore, in a period of filling through-hole, the plating layer thickness on surface will not increase together, thus can minimize by
It is bad caused by increased plating layer thickness.Also, etching or grinding due to that need not carry out coating surface etc. are flat
Chemical industry sequence, so the second copper foil layer 22 can be effectively formed.
Also, according to existing substrate plating composition, in the case where substrate surface is by plating together, it is easy to be formed
The entrance of through-hole empty (void) made of blocking, but if using substrate plating composition according to the present invention,
As shown in (b) of Fig. 1, the surface of substrate will not be plated, therefore cavity is not easily formed in through-hole.
In turn, since overlay coating growth inhibitory effect becomes to maximize, so as to what is be not plated in substrate surface
In the case of only through-hole is effectively and uniformly filled, therefore the electric current used is few, to cost-effective.
(c) of Fig. 1 indicates that the substrate plating using the present invention is formed with composition after the second copper foil layer 22 and utilizes second
Plating forms the situation of coating surface layer 24 with composition.The second plating composition can improve the uniformity
Bath composition.Common well known combination can be used as the plating composition that can improve the uniformity as described above
Object, hereby it is possible to minimize coating layer thickness deviation.The well known plating composition that the uniformity can be improved for example may be used
To be the ST-2000 of this happy chemical (Enthone) company.
Therefore, it is possible to freely adjust the plating layer thickness of substrate surface without additional etching or grinding process,
And the coating layer thickness deviation of substrate surface can be significantly improved.Therefore, it is possible to improve the plating layer thickness of substrate surface
Impedance matching caused by deviation is bad, sealing of hole (tenting) product does not etch and over etching is bad, stacking is bad, curved
Bent (warpage) is bad etc..
The coating surface layer of substrate when Fig. 2 is for illustrating that the via of an embodiment according to the present invention fills plating
The sectional view of the substrate 100 of the relationship between thickness b until thickness a and bottom to coating surface layer from via.
With reference to Fig. 2, if carrying out plating, the table of substrate to substrate with composition using substrate plating according to the present invention
Thickness b until the thickness a of face coating layer and the bottom to coating surface layer from via meets a/b<0.02 relationship.At this point,
The thickness a and b is the thickness in addition to seed layer.
Relationship as described above indicates, for substrate plating composition according to the present invention, due to the surface of substrate
The maximization of coating growth inhibitory effect, can realize in the case where substrate surface is not plated only to through-hole carry out effectively and
The ZTF plating uniformly filled.
Therefore, for the substrate formed according to the present invention, the case where being processed and etch in the section to through-hole
Under, there may be etching line (referring to Fig.1 6 laterally or longitudinally between through-hole coating section and the coating surface layer of substrate
And Figure 17).
Fig. 3 is the section for the substrate coating method including seed layer for schematically showing an embodiment according to the present invention
Figure.
With reference to (a) of Fig. 3, the substrate can also include the seed layer for being formed in 12 upper surface of the second insulating layer
26.The seed layer 26 makes when the coating surface layer 24 to the second copper foil layer 22 and substrate in through-hole carries out plating from substrate
The external electric current introduced be successfully flowed into inside the entirety and through-hole of substrate surface.The seed layer 26 can utilize from
Selected in the conductive metals such as gold, silver, copper and mickel more than one and formed, but not limited to this.Also, the seed layer 26
It can be formed by electroless plating or sputtering, but not limited to this.(b) of Fig. 3, (b) of (c) process and Fig. 1, (c) work
Sequence is identical.
Fig. 4 is the formation dry film pattern (dry on substrate for schematically showing an embodiment according to the present invention
Filmpattern the sectional view of the substrate coating method in the state of).
With reference to (a) of Fig. 4, the substrate plating group of the present invention is utilized in the state of forming through-hole and 28 pattern of dry film
It closes object and fills through-hole, utilize well known plating composition later, at the thickness less than dry film 28 and flatly by thickness control
The surface of plated substrate.(b) of Fig. 4 and the process of process with (b) of Fig. 1 and (c) (c) are identical.With reference to (d) of Fig. 4, if
Dry film 28 is removed after completing the coating surface for substrate, then can provide and be formed flatly metal surface plating on substrate
The substrate of 24 pattern of coating.
Fig. 5 is to schematically show an embodiment according to the present invention and in copper-clad laminate (Copper Clad
Laminate；CCL) 300 the sectional view that through-hole later carries out through-hole the method for plating is formed.
With reference to (a) of Fig. 5, the CCL300 includes：First copper foil layer 310；Second copper foil layer 310'；Insulating layer 312, folder
Between the first copper foil layer 310 and the second copper foil layer 310'；And through-hole, penetrate through the second copper foil layer 310' and insulating layer
312 and formed to the upper surface of the first copper foil layer 310.
With reference to (b) of Fig. 5, third can be formed with composition by filling plating according to the present invention to the through-hole
Copper foil layer 322.
At this point, plating composition according to the present invention is since overlay coating growth inhibitory effect becomes to maximize, to
It can realize that substrate surface is not plated and is only effectively and uniformly filled to through-hole, therefore as second copper foil
The copper foil layer that layer 310' can use thickness relatively thick.Therefore, compared to the plating simultaneously realized for through-hole and surface
Existing substrate can significantly improve the uniformity of substrate surface.
With reference to (b) of described Fig. 5, the substrate manufactured according to the present embodiment, can be logical when being etched to its section
Longitudinal etching line is formed between hole coating section and substrate surface coating layer.
Via fills coating method
According to another aspect of the invention, a kind of substrate coating method is provided, is included the following steps：It is formed in substrate logical
Hole；And the substrate for being formed with the through-hole is made to be filled out with plating according to the present invention with the after-applied electric current that composition contacts
Through-hole is filled, carries out plating in a manner of the growth for inhibiting overlay coating at this time.
More specifically, substrate can be immersed in plating according to the present invention and used by substrate coating method according to the present invention
Composition and in 0.01~5.0A/dm2Current density operating environment and 20~60 DEG C of temperature condition under carry out plating.
At this point, environment in working site be less than 20 DEG C in the case of, there are problems for the dissolubility between the composition, and
Environment in working site be more than 60 DEG C in the case of, within the scope of the burning point of the composition, therefore temperature includes
Dangerous property.
Before the step of filling through-hole carries out plating, the upper surface of substrate surface and through-hole can also be included in
The step of forming seed layer.
It, can also be including the use of the second plating composition to institute after the step of filling through-hole carries out plating
State the step of substrate surface carries out plating.
The second plating composition can be the plating composition that can improve the uniformity.As described above
The plating composition of the uniformity, which can be improved, can use well known composition, therefore it is inclined to minimize plating layer thickness
Difference.The well known plating composition that the uniformity can be improved for example can be the ST- of this happy chemical (Enthone) company
2000.The plating composition that coarse surface can be alleviated for example can be the VR of JCU companies.If simple elevation surface
Situation can also then use the plating solution for being not added with organic additive and being constituted merely with inorganic component.
The thickness that the growth of the overlay coating can be suppressed to coating surface layer is 1 μm or less.
In following embodiments, the present invention is described in more detail.However, following embodiments is only
Exemplary illustration the embodiment of the present invention, present disclosure are not limited to following embodiments.
[embodiment]
It machined the through-hole (via hole) with 90 μm of diameter and 80 μm of depth to printed circuit board.Later, lead to
Cross electroless copper and to imparting electric conductivity inside substrate surface and through-hole.Then, with following examples 1 to 16 and ratio
In coating bath (bath) compared with the electro-coppering composition of the component in example 1 to 6, at room temperature, with 0.5A/dm2Current density with
And plating is carried out to the through-hole under 22 DEG C of temperature condition, it confirmed the section or the plane that are filled the through-hole of plating later.
It is shown in following tables 1 according to the component of embodiment 1 to 16 and the substrate plating composition of comparative example 1 to 6
In.
[table 1]
Fig. 6 be show will using a diameter of 90 μm, depth for 80 μm through-hole and an embodiment according to the present invention carry out
Via fills and for the section of the via after the coating surface of substrate and cutting according to the via after prior art progress plating
The cross sectional photograph that face is compared.
It cannot be complete when carrying out plating in a manner of so that the thickness of coating surface layer is become 20 μm according to the prior art
Fill the through-hole that a diameter of 90 μm and depth are 80 μm in ground.In order to completely fill through-hole, additional implementation plating, therefore table are needed
The thickness of face coating layer can become thicker.
For the purpose of the present invention, it after being only filled with through-hole with composition using the filling plating of the present invention, executes secondary
Plating and plating is carried out to surface with required thickness, therefore groove can not be formed and realize relatively thin coating surface
The thickness of layer.Due to occurring dividing the etching line of a plating and secondary plating in profile image, so appearance can be passed through
It is confined to the feature around through-hole in the position of the etching line of section to distinguish the coating method and the prior art of the present invention.
Fig. 7 is show an embodiment according to the present invention a diameter of 90 μm, the filling plating for the through-hole that depth is 80 μm
The cross sectional photograph of the through-hole of process.
As shown in fig. 7, surface will not similarly occur during plating for filling plating composition according to the present invention
Plating and plating only occurs in through-hole.
Fig. 8 be show to a diameter of 90 μm, depth to be that 80 μm of through-hole is filled according to an embodiment of the invention, and
Additionally carry out the cross sectional photograph of the plating of substrate surface and the situation of the plating layer thickness on control base board surface.
By Fig. 8 it has been confirmed that in the present invention, after filling through-hole with composition using the filling plating, in profit
The thickness of coating layer can be controlled when carrying out plating with composition with common well known plating, and can be with relatively thin
The mode of the thickness of coating surface layer fills through-hole.
Fig. 8 be in a manner of the thickness with 8 μm, 12 μm, 16 μm and 20 μm of coating surface layer since substrate into
The photo of the embodiment of the present invention of row control.As shown in figure 8, the present invention can provide it is not only flat but also being capable of easily control table
The through-hole plating composition of face plating layer thickness.
Fig. 9 is according to an embodiment of the invention and obtains the planar picture of the substrate of via filling plating.The photo is pair
The photo that position is shot at 25 in substrate, it can be seen that overall region is equably filled out without occurring bad
It fills.
That is, with reference to Fig. 9, the characteristic of via filling characteristic of the invention and non-locality, but the entire of substrate can be run through
Region and the characteristic generated.Therefore, it can be confirmed and plating do not occur on a surface of a substrate, and only through-hole is filled plating.
Figure 10 be according to an embodiment of the invention using the formaldehyde including 50ppm and include various concentration alkylammonium halogen
The substrate plating of compound is filled via with composition the planar picture of the substrate of plating.
Referring to Fig.1 0, it is known that in the situation (ratio of table 1 of a concentration of 3ppm or less or 100ppm or more of alkyl ammonium halide
Compared with example 1 and 2) under, plating can also occur on the surface of the substrate.However, in a concentration of 10 to 70ppm feelings of alkyl ammonium halide
Under condition (embodiment 1 to 4 of table 1), it can be confirmed that substrate surface is not plated and only through-hole is filled plating.Therefore, described
Alkyl ammonium halide is suitble to include more than 3ppm and less than the concentration of 100ppm, and be more suitable for 10ppm less than
The concentration of 100ppm includes.Suitable concentration may become not according to the molecular weight or carbon atom number of alkyl ammonium halide
Together.According to the type of halide, that is, according to being Cl-Or Br-, suitable concentration section can also move, it is therefore preferred that with suitable
Suitable concentration section is evaluated in the mode of used halide species and plating conditions and is used.
Figure 11 is comparative example according to the present invention and utilizes the base for only including alkyl ammonium halide in acidic copper electrolytes
Plate plating carries out the planar picture that via fills the substrate of plating with composition.
1 the second row and the third line with suitable amount (for example, 10ppm and 30ppm) it has been confirmed that even if wrapped referring to Fig.1
Containing alkyl ammonium halide, if not including formaldehyde or ethylene oxide-propylene oxide copolymer (EO-PO copolymer) completely
(comparative example 3 and 4 of table 1), then can be abnormal plating on a surface of a substrate.However, including being selected from formaldehyde and epoxy second
It, as shown in Figure 9 and Figure 10, can be true in the case of one or more of alkane-epoxy propane copolymer (EO-PO copolymer)
Recognize overlay coating growth inhibition characteristic to be further first-class under control.
Figure 12 to Figure 15 is to show an embodiment according to the present invention and utilize the substrate plating for being added to surface modifier
The cross sectional photograph of the via of filling plating is obtained with composition.
Referring to Fig.1 2 to Figure 15, containing the table as triarylmethane dye, azole, pyrimidine derivatives or brightener
Under the case where face modifying agent (embodiment 5 of table 1 to embodiment 8), it is known that filling plating exposure can be formed uniformly.
As a result it has been confirmed that the embodiment of the present invention and comparative example differently, can be in the feelings that substrate surface is not plated
Only through-hole is effectively filled under condition.And it is possible to confirm, it can be with the generation of the non-uniform plating zones in control base board.
Figure 16 is an embodiment according to the present invention and carries out hole to the CCL substrates on the surface with arbitrary thickness and add
Work, and the cross sectional photograph that carries out via fill the via of plating is formed using chemical copper after seed layer.It is characterized in that, due to
Copper foil and via filling coating layer are separated and are formed, therefore longitudinal etching line is presented on the surface of the substrate.Referring to Fig.1 6, it is known that
If, can be in the case where copper foil surface be plated only to logical using substrate plating composition according to the present invention
Hole is filled plating, and can be applicable to through hole.
If being laminated has the copper foil of the thickness corresponding to target thickness of coating, and is plated using the composition of the present invention
Circuit etching work procedure or sealing of hole process are covered and then carried out, then can form the higher circuit of thickness uniformity.
Figure 17 is to show that the via for obtaining the etching line of the via of via filling plating according to an embodiment of the invention cuts open
Face figure.Etching line is to divide the line of via filling plating and coating surface.The position of etching line can be by adjusting via filling
Plating amount and the arbitrary position for being formed in vias inside.
Referring to Fig.1 7, led to using the substrate plating composition and common well known plating composition of the present invention
Respectively different step is crossed to form via filling coating and overlay coating, to observe cuing open for substrate after completing plating
Face.Plating is filled to carry out via according to an embodiment of the invention, therefore is characterized in that being able to observe that and crosses vias inside
Etching line.The position of etching line can be adjusted according to demand, and the centre of itself and insulating layer can also be made accordingly to arrange.
Even if via it is rough during carrying out coating surface if can be capped, therefore it is another in the thickness of coating surface layer
It is outer it is fixed in the case of need not excessively lie in the management of surface shape.However if via filling plating do not fill
Point, then through-hole is possible to not complete to be filled (lower right side of Figure 17) in coating surface, it is therefore desirable to be suitable for product specification
And position appropriate is selected, at this point, preferably plating is to surface.
Figure 18 is will to utilize the substrate plating for only not including formaldehyde including alkyl ammonium halide in acidic copper electrolytes
Form (left side) after carrying out plating with composition with using the substrate plating composition comprising alkyl ammonium halide and formaldehyde into
Form (right side) after row coating compares and the planar picture that shows.
That is, the left photo of Figure 18 shows not including alkyl ammonium halide in acidic copper substrate plating composition
And the form after the via filling plating under the case where including individually only formaldehyde (comparative example 5 of table 1)；Right photograph is to show to lead to
The comparison photo for the state that hole is filled.As shown in the left photo of Figure 18, in acidic copper substrate plating composition
In only comprising in the case of formaldehyde, identically as the result of plating is only carried out with composition using acidic copper substrate plating,
It is presented without via filling effect.Thus it is confirmed that only including the substrate plating of formaldehyde and alkyl ammonium halide at the same time
Via filling effect is generated in the case of composition.
Figure 19 is the form that via filling plating is carried out using the plating solution VR of JCU companies for being shown as the prior art
Cross sectional photograph.The left photo of Figure 19 shows to carry out the result of 30 minutes plating with 1.5ASD；Intermediate photo show with
1.5ASD carries out the result of 45 minutes plating；Right photograph is shown with the plating of 1.5ASD progress 90 minutes as a result, via
Size is 80 μm of 90 μm of diameter and depth.
Referring to Fig.1 9, via filling is cannot achieve in the case of relatively thin thickness of coating, and if increasing plating amount,
Then in the thickness for can increase while via filling coating surface layer.Moreover, if plating amount increases, groove
(Dimple) depth is reduced.Carry out 90 minutes plating as a result, the thickness of coating surface layer increases 30 μm, and groove
Depth is still 9 μm.
Figure 20 is the form shown using the acidic copper solution progress via filling plating for not including organic additive
Cross sectional photograph (via size：50 μm of diameter；25 μm of depth).
With reference to Figure 20, if molten using the acidic copper according to prior art not comprising alkyl ammonium halide and formaldehyde
Liquid (comparative example 6 of table 1) fills plating to carry out via, even if then Plating times increase, through-hole will not be filled.
Figure 21 is to show an embodiment according to the present invention and utilize comprising alkyl ammonium halide (CTAB) and ethylene oxide-
The substrate plating of epoxy propane copolymer (EO-PO copolymer) carries out the plane that via fills the form of plating with composition
Photo.
With reference to Figure 21, the case where using formaldehyde instead of EO-PO copolymers under (embodiment 9 of table 1), surface does not have
It is plated and through-hole is filled plating.Here, the characteristic of ethylene oxide-propylene oxide copolymer (EO-PO copolymer)
How much there is change according to molecular weight, therefore those of ordinary skill in the art can be adapted to through-hole specification and select using being suitble to
Molecular weight.
Figure 22 is to show to utilize the substrate for including alkyl ammonium halide (DTAB) and EO-PO copolymers according to an embodiment
Plating carries out the photo that via fills the form of plating with composition.
With reference to Figure 22, as alkyl ammonium halide and by CTAB instead of DTAB, and formaldehyde is copolymerized instead of EO-PO
Object and the case where use under (embodiment 10 of table 1), surface is not plated and through-hole is filled plating.
Figure 23 is to show to utilize in acidic copper solution not including alkylammonium halogenation according to an embodiment of the invention
Object and include the ethylene oxide-propylene oxide copolymer (EO-PO copolymer) of various concentration substrate plating combination
Object and carry out via filling plating substrate planar picture.
With reference to Figure 23, it is confirmed as even if only adding ring using alkyl ammonium halide is not added in acidic copper solution
The substrate plating composition of oxidative ethane-epoxy propane copolymer (EO-PO copolymer), can not also increase coating surface
In the case of be only filled with through-hole.Further, it is possible to using ethylene oxide-propylene oxide copolymer (EO-PO copolymer) with
The substrate plating that various concentration of 2.5ppm to 50ppm includes realizes ZTF with composition (embodiment 11 to 16 of table 1).
However, compared to alkyl ammonium halide and ethylene oxide-propylene oxide copolymer (EO-PO copolymer) together by comprising
Substrate plating composition, the uniformity may not be high, and solvable concentration range may not be wide.
Figure 24 is to show to combine using the weaker substrate plating of overlay coating growth inhibitory effect according to prior art
Object and the figure for simulating the result of (simulation) based on Plating times increased coating growth.
With reference to Figure 24, the bright spot inside the copper of coating growth is that overlay coating inhibitor is attached at copper surface and inhibits surface
The position of plating is indicated the position using point.According to the type of overlay coating inhibitor, it is embedded in or by anti-
It answers and is fallen in liquid after losing coating surface function, or moved along surface, herein used as basic model
Embedment model.It can be seen that less overlay coating inhibitor is distributed with inside through-hole.Although there is overlay coating growth suppression
Effect processed, but the reduction of copper can not be blocked completely, therefore plated in such a way that through-hole while surface is grown also is filled
It covers.It shows the deposit characteristics of the allusion quotation of previous filling plating solution.
Figure 25 is to show to plate using the stronger substrate of overlay coating growth inhibitory effect of an embodiment according to the present invention
Cover with composition and simulate the figure of the result based on the increased coating growth of Plating times.
With reference to Figure 25, the growth of overlay coating is repressed while vias inside is filled.It further acknowledges, in overlay coating
Hole surface is crossed in the case that growth inhibitory effect is strong cursorily to be grown.At plating initial stage, even if carrying out on the surface on a small quantity
Plating will not then be plated again on the surface as long as its surface is blocked during carrying out plating by the completion of coating inhibitor
Layer growth, and plating can be only carried out inside through-hole.Therefore, if the concentration of overlay coating growth inhibitor is insufficient, nothing
Method blocks whole surface, therefore the situation of a concentration of 3ppm such as the alkyl ammonium halide in Figure 10, it may occur that surface
Coating is grown.It, as shown in figure 11 can be if the covering uniformity is poor also, even if the concentration of alkyl ammonium halide is sufficiently high
Plating is abnormal on surface.However, as shown in figure 25, the embodiment of the present invention had both had the effect for blocking coating surface completely
Fruit, it may have uniform spreadability is a kind of via filling plating of filling through-hole while inhibiting the growth of overlay coating
Use composition.Therefore, Figure 25 indicate, by can inhibit coating surface and can realize through-hole filling composition, it can be achieved that
Following technology：The growth of overlay coating is completely inhibited, and through-hole is filled in the case where surface abnormalities plating does not occur.
Figure 26 is shown in the embodiment of Figure 25 using the overlay coating that the amount of overlay coating inhibitor is excessively increased
The very strong substrate plating composition of growth inhibitory effect and simulate the result based on Plating times increased coating growth
Figure.
With reference to Figure 26, since overlay coating growth inhibitory effect is strong, so the forcefully inhibition table since plating initial stage
The growth of face coating.Since the inside of intercommunicating pore during carrying out plating is also suppressed agent covering, so inside through-hole
Coating growth also stopped.In the case where actually carrying out plating, due to being the situation for constantly applying electric current, so and mould
Quasi- situation is different, and plating does not stop, but the situation of a concentration of 100ppm such as the alkyl ammonium halide of Figure 10, and meeting exists
Any part of substrate is abnormal plating.
More than, the specific part of the content of present invention is described in detail, it is understood that, for knowing substantially for this field
For the personnel of knowledge, such specific description is only preferred implementation form, and the scope of the invention is not limited to this.This
The range of the essence of invention is determined by the record and its equivalent of claims.
Claims (20)
1. a kind of substrate plating composition, wherein including：
Alkyl ammonium halide；And
Selected from formaldehyde and ethylene oxide-propylene oxide copolymer more than one.
2. substrate plating composition as described in claim 1, wherein
The substrate plating is acidic copper liquid composite with composition.
3. substrate plating composition as claimed in claim 2, wherein including：
Acid, mantoquita and chlorion compound.
4. the substrate plating composition as described in any one in claims 1 to 3, wherein
The alkyl ammonium halide is the compound of following chemical formula 1：
[chemical formula 1]
(NR4)+X-,
Wherein, R=CnH(2n+1),
N=1~30,
X=Cl, Br or I.
5. substrate plating composition as claimed in claim 4, wherein
The alkyl ammonium halide is constituted using 10~30 carbon atoms.
6. substrate plating composition as described in claim 4 or 5, wherein
The alkyl ammonium halide is to be selected from N (CH3)3(C4H9)+X-、N(CH3)3(C8H17)+X-、N(CH3)3(C12H25)+X-、N
(CH3)3(C16H33)+X-、N(CH3)3(C20H41)+X-、N(C2H5)3(C4H9)+X-、N(C2H5)3(C8H17)+X-、N(C2H5)3(C12H25
)+X-、N(C2H5)3(C16H33)+X-、N(CH3)4 +X-、N(C2H5)4 +X-、N(C3H7)4 +X-、N(C4H9)4 +X-And N (C7H15)4 +X-'s
More than one, and X is Cl, Br or I.
7. the substrate plating composition as described in any one in claim 4 to 6, wherein
The alkyl ammonium halide can be selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, 12
More than one of alkyl trimethyl ammonium chloride and dodecyl trimethyl ammonium bromide.
8. the substrate plating composition as described in any one in claim 1 to 7, wherein
Relative to the overall weight of the substrate plating composition, including more than 0.0003 parts by weight and being less than 0.01 parts by weight
Alkyl ammonium halide.
9. the substrate plating composition as described in any one in claim 1 to 8, wherein
Relative to the substrate plating composition overall weight and with 0.0001 to 0.5 parts by weight include from the formaldehyde and
Ethylene oxide-propylene oxide copolymer selection more than one.
10. the substrate plating composition as described in any one in claim 1 to 9, wherein
The molecular weight of the ethylene oxide-propylene oxide copolymer is 1,000 to 100,000.
11. the substrate plating composition as described in any one in claims 1 to 10, wherein
Ethylene oxide moiety in the ethylene oxide-propylene oxide copolymer divides rate to be 1/3.
12. the substrate plating composition as described in any one in claim 1 to 11, wherein further include：
Surface modifier.
13. substrate plating composition as claimed in claim 12, wherein
The molecular weight of the surface modifier is 50 to 1500.
14. substrate plating composition as described in claim 12 or 13, wherein
It include the surface modifier of 0.0001~1 parts by weight relative to the overall weight of substrate plating composition.
15. a kind of substrate plating composition, wherein including：
Ethylene oxide-propylene oxide copolymer,
And the substrate plating is acidic copper liquid composite with composition.
16. a kind of substrate coating method, wherein include the following steps：
Through-hole is formed in substrate；And
In the substrate and the substrate plating group according to any one in claim 1 to 15 for making to be formed with the through-hole
It closes the after-applied electric current of object contact and fills through-hole, carry out plating in a manner of inhibiting the growth of coating surface layer at this time.
17. substrate coating method as claimed in claim 16, wherein
Further include following steps before the step of filling through-hole carries out plating：
Seed layer is formed in the upper surface of substrate surface and through-hole.
18. the substrate coating method as described in claim 16 or 17, wherein
Further include following steps after the step of filling through-hole carries out plating：
Plating is carried out to the substrate surface with composition using the second plating.
19. the substrate coating method as described in any one in claim 16 to 18, wherein
The substrate is copper-clad laminate.
20. the substrate coating method as described in any one in claim 16 to 19, wherein
The thickness that the growth of the coating surface layer is suppressed to coating surface layer is 1 μm or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170010018A KR20180086073A (en) | 2017-01-20 | 2017-01-20 | Composition for plating of substrate and plating method using the same |
| KR10-2017-0010018 | 2017-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108342754A true CN108342754A (en) | 2018-07-31 |
Family
ID=62961107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810052395.8A Pending CN108342754A (en) | 2017-01-20 | 2018-01-19 | Substrate plating composition and the coating method for utilizing the composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7056841B2 (en) |
| KR (1) | KR20180086073A (en) |
| CN (1) | CN108342754A (en) |
| TW (1) | TWI750299B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI825648B (en) | 2022-03-31 | 2023-12-11 | 欣興電子股份有限公司 | Circuit board and method of manufacturing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506501A (en) * | 2002-11-21 | 2004-06-23 | 希普雷公司 | Electroplating liquid |
| CN101796221A (en) * | 2007-05-21 | 2010-08-04 | 上村工业株式会社 | Copper electroplating bath |
| CN102286761A (en) * | 2011-08-31 | 2011-12-21 | 上海应用技术学院 | Highly dispersed and bright acidic copper plating additive for printed circuit board, preparation method and application thereof |
| CN104532309A (en) * | 2014-12-31 | 2015-04-22 | 上海新阳半导体材料股份有限公司 | Additive B capable of controlling TSV deep hole copper plating crystallization and growth mode and application of additive B |
| CN105734623A (en) * | 2016-05-06 | 2016-07-06 | 广东利尔化学有限公司 | High-dispersity acidic copper plating additive as well as preparation method and application thereof |
-
2017
- 2017-01-20 KR KR1020170010018A patent/KR20180086073A/en not_active Application Discontinuation
-
2018
- 2018-01-18 TW TW107101777A patent/TWI750299B/en active
- 2018-01-19 CN CN201810052395.8A patent/CN108342754A/en active Pending
- 2018-01-19 JP JP2018007275A patent/JP7056841B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506501A (en) * | 2002-11-21 | 2004-06-23 | 希普雷公司 | Electroplating liquid |
| CN100526517C (en) * | 2002-11-21 | 2009-08-12 | 希普雷公司 | Electroplating liquid |
| CN101796221A (en) * | 2007-05-21 | 2010-08-04 | 上村工业株式会社 | Copper electroplating bath |
| CN102286761A (en) * | 2011-08-31 | 2011-12-21 | 上海应用技术学院 | Highly dispersed and bright acidic copper plating additive for printed circuit board, preparation method and application thereof |
| CN104532309A (en) * | 2014-12-31 | 2015-04-22 | 上海新阳半导体材料股份有限公司 | Additive B capable of controlling TSV deep hole copper plating crystallization and growth mode and application of additive B |
| CN105734623A (en) * | 2016-05-06 | 2016-07-06 | 广东利尔化学有限公司 | High-dispersity acidic copper plating additive as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20180086073A (en) | 2018-07-30 |
| JP7056841B2 (en) | 2022-04-19 |
| JP2018115391A (en) | 2018-07-26 |
| TW201842234A (en) | 2018-12-01 |
| TWI750299B (en) | 2021-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5129642B2 (en) | Surface treated copper foil, copper clad laminate obtained using the surface treated copper foil, and printed wiring board obtained using the copper clad laminate | |
| EP2796019B1 (en) | Method for combined through-hole plating and via filling | |
| KR102274906B1 (en) | Copper foil and copper clad laminate having the same | |
| TWI463038B (en) | Electrolytic copper foil and copper clad laminate | |
| CN107708315A (en) | A kind of ceramic embedded radiating circuit plate and preparation method thereof | |
| CN104769165B (en) | Surface treatment copper foil and use its laminated plates, copper-cover laminated plate, printing distributing board and e-machine | |
| WO2021193863A1 (en) | Surface-treated copper foil for printed wiring boards, and copper-cladded laminate board for printed wiring boards and printed wiring board each using same | |
| WO2017090563A1 (en) | Acidic copper plating solution, acidic copper plated product, and method for producing semiconductor device | |
| US20170044682A1 (en) | High-speed filling method for copper | |
| JP2010171170A (en) | Copper circuit wiring board and method for manufacturing the same | |
| CN108342754A (en) | Substrate plating composition and the coating method for utilizing the composition | |
| CN103911635B (en) | A kind of copper electroplating solution | |
| JP2022545091A (en) | Method for manufacturing high density interconnect printed circuit board containing copper-filled microvias | |
| CN103003473B (en) | Method for etching of copper and copper alloys | |
| KR101832806B1 (en) | Copper foil having carrier, production method for copper foil having carrier, and copper clad laminate sheet and printed wiring board obtained using copper foil having carrier | |
| JP2020183565A (en) | Electrolytic copper foil, surface-treated copper foil using electrolytic copper foil, copper-clad laminate using surface-treated copper foil, and printed circuit board | |
| KR102184414B1 (en) | metallic multi-layer thin film and method thoereof | |
| JP2008308749A (en) | Copper plating method | |
| JP2018165375A (en) | Acidic copper plating liquid, acidic copper plated article, and method of producing semiconductor device | |
| TWI320062B (en) | Composition for copper electroplating solution | |
| JP4472673B2 (en) | Manufacturing method of copper wiring and electrolytic solution for copper plating | |
| Sun et al. | Effects of additives on via filling and pattern plating with simultaneous electroplating | |
| JP2024510819A (en) | Method of electrochemical deposition of copper with different current densities | |
| JP6860933B2 (en) | Electrolytic nickel (alloy) plating solution | |
| JPH04196193A (en) | Manufacture of multilayer printed wiring board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |