(19)
(11)EP 2 712 885 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
12.07.2017 Bulletin 2017/28

(21)Application number: 13186582.6

(22)Date of filing:  30.09.2013
(51)Int. Cl.: 
C08J 7/04  (2006.01)
C23C 18/16  (2006.01)
C08G 12/00  (2006.01)
C09D 179/02  (2006.01)
C23C 18/18  (2006.01)
C23C 18/40  (2006.01)

(54)

A method for electroless metallization

Verfahren zur stromlosen Metallisierung

Procédé de métallisation autocatalytique


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 30.09.2012 US 201261708030 P

(43)Date of publication of application:
02.04.2014 Bulletin 2014/14

(73)Proprietor: Rohm and Haas Electronic Materials LLC
Marlborough, MA 01752 (US)

(72)Inventors:
  • Rzeznik, Maria Anna
    Shrewsbury, Massachusetts 01545 (US)
  • Knudsen, Philip D.
    Marlborough, MA 01752 (US)
  • Wang, Xuesong
    Marlborough, MA 01752 (US)
  • Bayes, Martin W.
    Hopkinton, Massachusetts 01748 (US)
  • Tsai, Yuhsin
    30073 Hsinchu City (CN)

(74)Representative: McLean, Craig Sutherland et al
Patent Outsourcing Limited 1 King Street
Bakewell, Derbyshire DE45 1DZ
Bakewell, Derbyshire DE45 1DZ (GB)


(56)References cited: : 
US-A1- 2008 149 566
US-A1- 2012 145 554
US-A1- 2010 021 748
  
  • H. LEE ET AL: "Mussel-Inspired Surface Chemistry for Multifunctional Coatings", SCIENCE, vol. 318, no. 5849, 19 October 2007 (2007-10-19), pages 426-430, XP055037063, ISSN: 0036-8075, DOI: 10.1126/science.1147241
  • DAVIS J ET AL: "Modification of catechol polymer redox properties during electropolymerization in the presence of aliphatic amines", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 43, no. 3-4, 1 January 1998 (1998-01-01), pages 291-300, XP004098034, ISSN: 0013-4686, DOI: 10.1016/S0013-4686(97)00086-8
  • NITHIANANDAM V S ET AL: "Quinone-amine polymers: 10. Use of calcium hypochlorite in the syntheses of polyamine-quinone (PAQ) polymers", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 32, no. 6, 1 January 1991 (1991-01-01), pages 1146-1149, XP024122422, ISSN: 0032-3861, DOI: 10.1016/0032-3861(91)90606-J [retrieved on 1991-01-01]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Field of the Invention



[0001] The presently disclosed embodiments relate generally to a method for forming a polymerized film on a surface of a non-conductive material and subsequently forming a metallic film on the surface without the aid of a traditional conditioner. More particularly, the embodiments relate to a method for forming an electrolessly plated metal film with strong adhesion on a smooth surface of non-conductive material without the aid of a traditional conditioner, using the polymerized film.

Background of the Invention



[0002] Electroless metallization (or electroless plating) is a method for obtaining a thin metallic film on materials such as metals, ceramics or plastics by a series of process steps, including the use of a conditioner, microetch, catalyst (activation) and electroless plating bath. The mostly popular catalysts for electroless plating during the past 30 years are Pd/Sn colloids in which palladium colloidal particles are stabilized by tin chloride. Prior to electroless plating, the surface charge of a dielectric substrate is typically negative. Due to electrostatic repulsion, the negative charge on the substrate will typically inhibit the adsorption of catalyst which is a negative charged colloid. The initiation of electroless metallization can be difficult if there is insufficient catalyst adsorption. In order to improve catalyst adsorption, a traditional conditioner step is often used. Typical constituents of a traditional conditioner include cationic surfactants, which provide positively-charged groups to change the substrate from negatively to partially positively charged, so that the adsorption of the catalyst can be improved. In other words, the interaction between the substrate and the catalyst is enhanced by a traditional conditioner via electrostatic attraction.

[0003] The reliability of circuits relies heavily on the adhesion between the deposited metal layer and the dielectric substrate. Poor adhesion may lead to unacceptable failures, such as "peel-off" or blistering. The electrostatic attraction from the traditional conditioner may not be strong enough to build up sufficient adhesion between the deposited metal layer and the dielectric substrate. Roughening the surface of dielectric substrates, for example by using a de-smear process, is often performed before electroless plating to increase the metal adhesion. Sufficient adhesion between the deposited metal layer and the dielectric substrates is then provided by the roughness of the dielectric substrate. Good adhesion is more difficult to obtain on a smooth surface using such process flows.

[0004] As L/S for next generation chip carriers get smaller, there is a need for smoother surfaces to etch fine lines. As the width and space of signal traces continue to shrink, and the frequency of the signals continues to increase, the surface of the insulating materials need to be smoother. Achieving high adhesion of a metalized layer on low profile insulating materials becomes increasingly difficult. Traditional etching-type processes to improve adhesion are no longer feasible, thus an alternative method is needed to improve the adhesion of fine patterned circuits on insulating materials. There is a need for improvements on traditional roughening processes and development of novel approaches to attain high adhesion of metal to polymer on a smooth surface for finer line chip carriers. In order to meet the requirements of the electronics industry for fine line circuits, a conditioner needs to be capable of providing high adhesion to a smooth (low profile) surface, as well as modifying the surface charge of dielectric substrates to improve the adsorption of a negatively charged catalyst.

[0005] Marine mussel organisms are known for their ability to bind strongly to such varied surfaces as rocks, pilings, and ship hulls. The adhesive characteristics of mussel adhesive proteins are believed to be due to the presence of 3,4-dihydroxyphenylalamine (DOPA). P. B. Messersmith et al. SCIENCE, 2007, Vol 318, page 426-430 discloses the use of dopamine to mimic the ability of mussel's adhesive protein to adhere to a surface of materials. Via a self-polymerization process, a thin, surface-adherent polydopamine film can be formed onto a wide range of inorganic and organic substrates through simple dip-coating of these substrates in an aqueous solution of dopamine at room temperature for 24 hours. Electroless silver or copper deposition was performed on the polydopamine coated surfaces to form a layer of silver or copper. CN10182678A discloses a polydopamine-assisted electroless silver process, in which dip coating of dopamine for 0 to 48 hours at room temperature was used. US2010/0021748A discloses a process comprising the steps of treating a substrate with a catecholamine solution including dopamine, to form a polycatecholamine layer followed by electroless plating. US2008/0149566A1 discloses a method of modifying a substrate surface by contacting at least a portion of the substrate with an alkaline solution containing a surface modifying agent under oxidative conditions.

[0006] Reviewing the prior art for dopamine-aided electroless plating, it can be found that the dopamine self-polymerization process typically requires room temperature treatment for about 24 hours. Coupled with the relatively high cost of dopamine, the long dwell time of dopamine treatment is a barrier to commercial application. In addition, the pH range that is suitable for the self-polymerization of dopamine is quite narrow (6.5 - 9.5). Outside this pH range, the self-polymerization rate of dopamine becomes extremely low.

Summary of the Invention



[0007] The inventors of this invention have found a method to form a multi-functional polymer film on a smooth surface through simple dip-coating of a material in a solution comprising two specific chemicals. The resulting film allows for electroless metallization, without the aid of a traditional conditioner, with enhanced adhesion between the deposited metal layer and the material. This is especially suitable for a dielectric substrate with a smooth surface.

[0008] According to aspects illustrated herein, there is provided a method for forming a metallic film on a surface of a non-conductive material, the method comprising the steps of:
  1. (i) contacting the surface of the material with a solution comprising (A) a diamine compound of formula

            H2N-R1-NH2

    wherein R1 is selected from the group consisting of C1 to C24 linear or branched alkylene and aromatic alkylene, and (B) a di-hydroxyl phenyl compound of formula

    wherein R8 is selected from the group consisting of H, CH3, OH, phenyl, CN, NO2, propanoic acid group, ethylamine group, formic acid group and formaldehyde group, and R9 and R10 are independently selected from H and OH, one of R8, R9 and R10 being OH, wherein the mole ratio of (A) to (B) is from 4:1 to 1:1; and (ii) conducting electroless metal plating of the surface of the material using a Pd/Sn colloidal catalyst.

Brief Description of the Drawings



[0009] 

Fig 1 is a series of standard images for back light rating assessment.

Fig 2 is a photomicrograph of backlight test for Example 19.

Fig 3 is a photomicrograph of backlight test for Example 21.


Detailed Description of the Invention



[0010] As used throughout this specification, the abbreviations given below have the following meanings, unless the content clearly indicates otherwise: g=gram; mg=milligram; mL=milliliter; L=liter; m=meter; min. =minute; s=second; h. =hr. =hours; ppm=parts per million; mol=mole; mmol/L= milli-mole per liter; g/L=grams per liter; R.O. =Reverse Osmosis; RT=room temperature; Ex. No.=Example number; lb/in=pound per inch. As used throughout this specification, the word "deposition" and "plating" are used interchangeably. As used throughout the specification, the word "plating bath" and "plating solution" are used interchangeably.

[0011] The method includes the steps of:
  1. (i) contacting a surface of a non-conductive material with a solution comprising (A) a diamine compound of formula

            H2N-R1-NH2

    wherein R1 is selected from the group consisting of C1 to C24 linear or branched alkylene and aromatic alkylene, and (B) a di-hydroxyl phenyl compound of formula

    wherein R8 is selected from the group consisting of H, CH3, OH, phenyl, CN, NO2, propanoic acid group, ethylamine group, formic acid group and formaldehyde group, and R9 and R10 are independently selected from H and OH, one of R8, R9 and R10 being OH, wherein the mole ratio of (A) to (B) is from 4:1 to 1: 1; and
  2. (ii) conducting electroless metal plating of the surface of the material using a Pd/Sn colloidal catalyst.

(A) Diamine compounds



[0012] Diamine compounds can be aliphatic compounds or aromatic compounds. When flexibility is required, an alkyl diamine having longer carbon chain such as hexamethylene diamine (HMDA) is preferably used.

[0013] Diamine compounds can be used as a mixture of two or more kinds of diamine compounds. The amount of (A) diamine compounds in the solution is 2 mmol/L to 2000 mmol/L, preferably 10 mmol/L to 400 mmol/L.

(B) Di-hydroxy phenyl compounds



[0014] The di-hydroxy phenyl compounds have two hydroxyl groups connected to phenyl ring. Preferably, the di-hydroxy phenyl compounds have two hydroxyl groups at ortho or para position to each other. Preferably, the di-hydroxy phenyl compound is catechol.

[0015] While not wishing to be bound by theory, it is believed that a hydroxyl group connected to an aromatic ring such as catechol is oxidized and the aromatic compound is converted to a quinone. Since the oxygen atom of quinone is an electron-withdrawing group, quinone has activated carbon atoms on the aromatic ring. Michael Addition may occur at the activated carbon atoms on the aromatic ring with the amino group of the amine compound, and the amine compound and the aromatic compound are combined. The inventors have found that the copolymerization rate of diamine with resorcinol with two hydroxyl groups at meta-position or phenol with one hydroxyl group at room temperature is slower than that of catechol or hydroquinone with two hydroxyl groups at ortho-position and para-position, respectively. Therefore, it is believed that compounds with two hydroxyl groups at the ortho- or para-position may be easier to form ketone groups and undergo a Michael Addition reaction with amine compounds than that with two hydroxyl groups at meta-position.

[0016] A mixture of di-hydroxyl phenyl compounds can be used. The amount of (B) di-hydroxyl phenyl compounds in the solution is 2 mmol/L to 2000 mmol/L, preferably 10 mmol/L to 400 mmol/L. The medium of the solution is preferably water. RO water or de-ionized water can be used. A mixture of water with organic solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, propylene glycol or tetrahydrofuran may also be used as the medium of this invention.

[0017] When dipping a material in a solution including (A) and (B), a film is formed on the surface of the material. It is believed that the film is a copolymerized film of (A) with (B) via Michael Addition between (A) and (B), as well as coupling between (B) and (B) or (B) and (A). In the case of organic materials, chemical bonds between the organic surfaces and the copolymer(A+B) film might be formed via free radical or Michael Addition reactions. In the case of inorganic material, coordination bonds between the inorganic surfaces with the copolymer(A+B) film might be built up via coordination reaction.

[0018] To synthesize a film on a surface of a material, the mole ratio of the functional groups within (A) to the functional groups within (B) in the solution may vary such as 10:1 to 1:10. However, when the polymerized film is used for electroless plating techniques, the preferable mole ratio depends on the required properties of the film and the functionality on (A) and (B).

[0019] Amino groups potentially possess positive charges, whereas hydroxyl groups on aromatic rings potentially possess negative charges. By control of the mole ratio of amino groups to hydroxyl groups, the charge distribution of the polymerized film can be modified. For example, when a negative charged catalyst such as a Pd/Sn colloid is used in the process of electroless deposition, a positively charged copolymer(A+B) film is preferred because of better adsorption of a negatively charged catalyst. Therefore, when the polymerized film is used for an electroless plating process using a Pd/Sn colloid catalyst such as in the current industrial electroless plating techniques, and when (A) is a diamine compound and (B) is a di-hydroxyl phenyl compound such as catechol, the mole ratio of (A) to (B) varies from 4:1 to 1:1, more preferably is 2:1.

[0020] When the process of electroless plating does not have a catalyzing step and metal deposition is conducted directly, the key influence of the copolymer(A+B) film on the electroless plating process will be its reducibility, rather than its electric charge. Higher reducibility of the copolymer(A+B) film will result in shorter time to initiate electroless plating. Therefore, when the polymerized film is used for an electroless plating process without a catalyzing step, (A) and (B) should be selected so that the reducibility of the film becomes higher, consequently, the adhesion between the deposited metal and the dielectric substrate will be improved by the existence of the copolymer(A+B) film.

[0021] The step of contacting a surface of a material with a solution comprising (A) and (B) is conducted via any kind of methods, such as dipping or spraying.

[0022] The temperature range for contacting a material with the solution is from 5 to 99 degrees C. The dwell time of contacting a material with the solution depends on the temperature of the solution. When the temperature is around room temperature, the time for contacting a material with the solution is preferably 3 hours to 3 days, more preferably 0.5 day to 1 day. When the temperature is about 80 degree C, the time is preferably 0.1 hour to 8 hours, more preferably 0.5 hour to 4 hours.

[0023] The method of this invention optionally comprises the step of: contacting the surface of the material with a solution comprising a free radical initiator prior to the step of contacting the surface of the material with a solution comprising (A) and (B).

[0024] It is known that catechol oxidizes enzymes, present in mussels-adhesive-protein secretions, convert the dihydroxyphenyl group of DOPA into highly reactive o-quinone functionalities. Michael Addition of side-chain amino groups from lysine residues to DOPA-quinone residues can be expected. There are also chances to generate free radical o-semiquinones by half oxidization of dihydroxyphenyl groups. It is expected that free radical species might build covalent bonds between o-semiquinones to increase cohesion (cross-links) and enable coupling to organic materials to enhance interfacial adhesion (adhesive reaction).

[0025] The inventors found that the step of contacting a surface of a material with a free radical initiator solution prior to contacting with the solution comprising (A) and (B) increases the electroless metal coverage on dielectric substrate such as glass fibers, which indicates that the adhesion between the dielectric substrate and the deposited metal film may be improved. As the temperature of the solution comprising (A) and (B) is increased from 20°C to 80°C, the oxidization rate of hydroxyphenyl group increases greatly. When (B) is catechol, the generation of o-quinine becomes rapid, while the concentration of free radical o-semiquinone (half oxidized dihydroxyphenyl) may fall. Since free radicals are believed to play a key role in both adhesive (coupling) and cohesive (cross-link) reactions, lower levels of free radical may reduce improvements in adhesive strength. In order to gain higher electroless metal coverage and higher adhesion between dielectric substrate and deposited metal, a free radical initiator is introduced by contacting the material with an organic solution of free-radical initiator.

[0026] Preferable free radical initiators are organic-soluble free radical initiators with limited water-solubility, because such free radical initiators are compatible with the surface of the dielectric material and can remain on the surface after contacting with an aqueous solution comprising (A) and (B). Examples of such free radical initiators include, but are not limited to, 2,2'-Azobis(2-methylbutyronitrile), Dimethyl 2,2'-azobis(2-methylpropionate), AIBN (2,2-azobisisobutyronitrile), ADMVN (2,2'-Azobis (2,4- dimethyl) valeronitrile)), and 2,2'-Azobis(4-methoxy-2.4-dimethyl valeronitrile).Their structural formulae, CAS numbers, molecular weights, solubility, as well as 10 hour half life decomposition temperatures are listed in Table 1.
Table 1. Examples of organic soluble free radical initiators with limited water-solubility
Chemical NameStructure FormulaSolubility10 Hour half-life decomposition temperature
2,2'-Azobis(2-methylbutyronitrile)

freely soluble in toluene, methanol, IPA or ethyl acetate insoluble in water 67°C (in toluene)
CAS NO. 13472-08-7
Molecular weight = 192.26
Dimethyl 2,2'-azobis(2-methylpropionate)

freely soluble in toluene, methanol, IPA or ethyl acetate very insoluble in water 66°C (in toluene)
CAS NO. 2589-57-3
Molecular weight = 230.26
2,2'-Azobisisobutyronitrile (AIBN)

soluble in methanol and ethanol, but is insoluble in water 65 °C (in toluene)
CAS Number 78-67-1
Molecular Weight 164.21
2,2'-Azobis(2.4-dimethyl valeronitrile) (ADMVN)

soluble in toluene, methanol, acetone, or styrene insoluble in water 51°C (in toluene)
CAS NO. 4419-11-8
Molecular weight = 248.37
2,2'-Azobis(4-methoxy-2.4-dimethyl valeronitrile)

soluble in toluene or acetone very slightly soluble in methanol insoluble in water 30°C (in toluene)
CAS NO. 15545-97-8
Molecular weight = 308.42


[0027] Preferable medium of the solution is an organic solvent such as toluene, PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropyl alcohol), ethyl acetate, acetone, or methanol, depending on the specific free radical initiator selected.

[0028] The concentration of the free radical initiator solution is preferably 0.003 to 0.3 mol/L, more preferably 0.02 to 0.2 mol/L. The temperature of contacting a material with the free radical initiator solution is, preferably -10 to 40 degree C, more preferably, around room temperature. The time of contacting a material with the free radical initiator solution is preferably 0.1 second to 0.5 hour, more preferably, 3 seconds to 3 minutes.

[0029] When contacting a material with a free radical initiator solution prior to contacting with the solution comprising (A) and (B), the conditions of the following step should match with the kind of free radical initiator so that the temperature and dwell time of contacting with the solution comprising (A) and (B) should be determined from the half-life of each initiator. For example, if AIBN is used as a free radical initiator followed by the step of contacting with the solution comprising (A) and (B), the temperature and dwell time of the following step matches at 80 degree C for 2 to 4 hours, but if ADMVN is used, it should be carried out at 65 degree C for 2 to 4 hours.

[0030] The method of this invention is a method for forming a metallic film on a non-conductive surface of a material, which comprises the following steps;

Step 1 contacting a surface of a material with a solution comprising (A) and (B) described above,

Step 2 conducting electroless metal plating of the material surface using a Pd/Sn colloidal catalyst.



[0031] Step 1 has been described above, so the description is incorporated here. As described before, the step of contacting with a free radical initiator can be conducted before step 1.

[0032] Between the step 1 and step 2, a step for applying a Pd/Sn colloid catalyst solution is conducted. For the condition of applying the catalyst solution, such as concentration, temperature and time, conventional technologies could be applied. For example, CATAPOSIT™ 44 Catalyst (Pd/Sn colloidal catalyst) in combination with CATAPREP™ 404 Pre-dip (protection salt for Pd/Sn catalyst) commercially available from Dow Electronics Materials can be used. For example, a material is dipped in 270 g/L of CATAPREP™ 404 Pre-dip aqueous bath at 20 to 35 degree C for 0.5 to 3.0 minutes to protect the catalyst from harmful drag-in. The material is then dipped in an aqueous solution containing 15 to 30 mL/L CATAPOSIT™ 44 Catalyst and 270 g/L of CATAPREP™ 404 Pre-dip at 32 to 52 degree C for 4 to 5 minutes.

[0033] Step 2 is an electroless metal plating step on the surface of a material on which a polymerized film has been formed. The surface of the material is electrolessly plated with one or more metallic layers, such as copper, using an electroless metal plating bath. Conventional electroless metal plating baths may be used. Such baths are well known in the art. Metals which may be deposited on the surface of the material include, but are not limited to, copper, nickel, gold, silver and copper/nickel alloys. Preferably, nickel or copper is deposited on the surface of the materials. For example, CIRCUPOSIT™ 880ELECTROLESS COPPER, CUPOSIT™ 253 ELECTROLESS COPPER, CIRCUPOSIT™ 3350 ELECTROLESS COPPER all commercially available from Dow Electronics Material can be used. Conventional electroless processes may be applied. For example, when a copper electroless plating bath is used, a material is dipped in an electroless plating bath including 45 mL/L CIRCUPOSIT™ 880 E, 10 mL/L CIRCUPOSIT™ 880 A, 28 mL/L CUPOSIT™ Z, 25 mL/L CIRCUPOSIT™ 880 C, and 15 mL/L CUPOSIT™ Y at 30 to 34 degree C for 15 to 45 minutes.

[0034] After the electroless plating step, the material may undergo further processing. Further processing may include additional electroless or electrolytic metal plating on the material, for example, copper, gold, silver, tin and alloys thereof. Conventional electrolytic metal baths may be used. Such baths are well known in the art.

[0035] After each step described above, the material is optionally rinsed with water.

[0036] The method of this invention provides good electroless metal coverage on treated surface and better adhesion between a non-conductive surface of a material and a deposited metallic film without the use of a traditional conditioner. While the mechanism of adhesion building up is not fully understood, it is believed that chemical bonds, such as coordination bonds or covalent bonds, may be formed during the treatment disclosed by this invention, which contribute to the better adhesion results.

Examples



[0037] The present invention may be better understood from the examples that follow. The examples are shown for illustration purposes only, and are not intended to limit the invention in any way.

[0038] Of the following Examples, Examples 1, 2, 4, 5 and 6 are inventive examples, while the others are reference or comparative examples provided to aid those skilled in the art in understanding the invention.

[0039] In the following examples, the pH of dopamine solution is buffered with 0.010 mol/L tris(hydroxymethyl)aminomethane and HCl, and the pH of aqueous solution of monomer pairs is either buffered with K2HPO4/ Citric Acid in the pH range of 3.0 to 8.0, or with H3BO3 / KCl /NaOH in the pH range of 8.0 to 10.0.

Examples 1-12



[0040] Examples 1 to 12 provide some monomer-pair examples that are capable of in-situ polymerization in an aqueous solution and are capable of forming a water insoluble copolymer(A+B) film on a dielectric substrate. These copolymer(A+B) films show conditioner functionality, which increase the electroless copper coverage on glass cloth coupons without the use of a traditional conditioner.

Example 1


(1) Pretreatment



[0041] Glass cloth coupons were obtained from glass-fiber reinforced bare epoxy laminates S1141 (Size: 50mm*150mm*1mm, Supplier: Shengyi Technology Co. Ltd., Glass transition temperature: 140 ∼ 150 degree C, Abbreviated as bare laminates). The bare laminate coupons were first immersed in 98% H2SO4 for 1 day to dissolve the epoxy resin and expose the glass cloth, then water rinsed for 5 minutes to clean the surface of glass cloth. This treatment was then repeated at least once to minimize epoxy residues. After final rinsing, the glass cloth coupons were oven dried at 120°C for 4 hours.

(2) Free Radical Initiator Treatment



[0042] The dried glass cloth coupon was contacted with a free radical initiator solution. The glass coupon was dipped in a free radical initiator solution comprising 0.2 mol/L of AIBN (Azobisisobutyronitrile) in toluene at room temperature for 1 minute, and then dried in a fume hood at room temperature for 5 minutes.

(3) (A)+(B) solution treatment



[0043] Next, the glass cloth coupon was contacted with a solution comprising (A) and (B). A solution comprising 0.026 mol/L of hexamethylene diamine and 0.013 mol/L of catechol was prepared using a K2HPO4 / Citric Acid buffer solution. The pH of the solution was 4.5. The glass cloth coupon was then dipped in the above described aqueous solution at 80 degree C for 4 hours. Awater insoluble copolymer(A+B) film was formed on the surface of the treated glass cloth coupon.

(4) Electroless plating without a traditional conditioner step



[0044] Next, the treated glass cloth coupon with the copolymer(A+B) film was treated in an electroless copper plating process without a traditional conditioner step. The coupon was dipped in a Microetch bath at room temperature for 1 minute, which contained 50 g/L of PREPOSIT™ Etch 748 (Dow Electronics Materials) and 20 mL/L 98% H2SO4 (Sigma-Aldrich), and then rinsed with R.O. water for 3 minutes. After that, the coupon was dipped in 270 g/L of CATAPREP™ 404 PreDip (Dow Electronics Materials) at 23 degree C for 1 minute. Next, the glass cloth coupon was dipped in a catalyst bath at 40 degree C for 5 minutes, which contained 20 mL/L of CATAPOSIT™ 44 Catalyst concentrate (Dow Electronics Materials) and 270 g/L of CATAPREP™ 404 PreDip, and then rinsed with R.O. Water for 2 minutes. Next, the coupon was dipped in a CIRCUPOSIT™ 880 Electroless Copper bath (Dow Electronics Materials) at 34 degree C for 30 to 45 minutes, which was prepared using 45 mL/L CIRCUPOSIT™ 880 E, 10 mL/L CIRCUPOSIT™ 880 A, 28 mL/L CUPOSIT™ Z, 25 mL/L CIRCUPOSIT™ 880 C, and 15 mL/L CUPOSIT™ After that, the glass cloth coupon was rinsed with R.O. water for 3 minutes and dried with an air knife for 2 minutes. A uniform electroless copper film was formed on the surface of the glass cloth coupon without the use of a traditional conditioner.

Examples 2-8



[0045] Examples 2 to 8 were processed in the same way as Example 1, except that the monomer pairs ((A)+(B)) and the mole ratio between them within procedure (3) were changed as indicated in Table 2. The basic concentration was 0.013mo1/L. By multiplying the basic concentration 0.013 mol/L by the mole ratio of the indicated monomer shown in table 2, the initial concentration of that monomer in the treatment bath was obtained. In all examples, a water insoluble copolymer(A+B) film was formed on the surface of glass cloth coupon after the "(A)+(B) solution treatment", and an electroless copper plated film was formed after electroless plating without a traditional conditioner step.

Examples 9, 10



[0046] Examples 9 and 10 were processed in the same way as Example 1, except that the chemicals, the mole ratio between them, treatment temperature and dwell time of treatment within procedure (3) were changed as indicated in Table 2 and step (2) was not conducted. The basic concentration was 0.013 mol/L. By multiplying the basic concentration 0.013mol/L by the mole ratio of the indicated monomer shown in Table 2, the initial concentration of that monomer in the treatment bath was obtained. A water insoluble copolymer(A+B) film was formed on the surface of glass cloth coupon after the "(A)+(B) solution treatment", and an electroless copper plated film was formed after electroless plating without a traditional conditioner step.

Example 11



[0047] Example 11 is a blank control of Example 1 to 8. It was processed in the same way as Example 1, except that step (2) was conducted using toluene without the presence of any free radical initiator, and step (3) was conducted using distilled water alone, without any solute. Only a very small amount of electroless copper was deposited on the surface of the glass cloth coupon after electroless plating without a traditional conditioner step. No continuous film of electroless copper film was formed.

Example 12



[0048] Example 12 is a blank control of Example 9 and 10. It was processed in the same way as Example 9 and 10, except that step (3) was conducted using distilled water alone, without any solute. Only a very small amount of electroless copper was deposited on the surface of the glass cloth coupon after electroless plating without a traditional conditioner step. No continuous film of electroless copper film was formed.
Table 2
Ex. No.(A) + (B)Dip in 0.2 mol/L AIBN Toluene SolutionDip in an aqueous solution of (A) + (B)Copolymer (A+B) film formed on the surface of glass cloth couponsElectroless Cu film formed on the surface of glass cloth coupons without the use of a traditional conditioner
Time & TemppHMole Ratio
1

1 min @ RT 4 hours @ 80°C 4.5 2 : 1 Yes Yes
2 3.5 1 : 1
3

1 min @ RT 4 hours @ 80°C 7.5∼ 9.5 2 : 1 Yes Yes
4

1 min @ RT 4 hours @ 80°C 9 1 : 1 : 1 Yes Yes
5

1 min @ RT 4 hours @ 80°C 8 1 : 1 Yes Yes
6

1 min @ RT 4 hours @ 80°C 9 1 : 1 : 1 Yes Yes
7

1 min @ RT 4 hours @ 80°C 8 1 : 1 Yes Yes
8

1 min @ RT 4 hours @ 80°C 8 1 : 1 Yes Yes
9

-- 24 hours @ RT 9 1 : 1 Yes Yes
10 <control>

-- 24 hours @ RT 8.5 1 Yes Yes
11 Blank control after 4 hour 80°C distilled water treatment -- -- 7.0 -- No No
12 Blank control after 24 hour RT distilled water treatment -- -- 7.0 -- No No


[0049] From Examples 1 to 12, it can be seen that all the examples 1 thru 9 monomer pairs ((A)+(B)) were capable of polymerization in an aqueous solution to form a water insoluble polymer film, similar to the behavior of dopamine. Almost no electroless copper can be deposited on a glass cloth coupon without the aid of a traditional conditioner. Only the formation of a very light-pink color with partial coverage is observed for the blank control glass cloth coupon after electroless copper plating (Example 11, 12). Monomer-pair treated or dopamine treated glass cloth coupons show a uniform bright salmon pink appearance indicating continuous copper deposit after electroless copper plating without the aid of a traditional conditioner. It can be said that the copolymer(A+B) films formed by examples 1 thru 9 monomer pairs ((A)+(B)), as well as the polydopamine film formed by dopamine at room temperature, show conditioner functionality. They are capable of increasing copper coverage on glass cloth coupons without the use of a traditional conditioner.

Examples 13 - 17



[0050] There are two aims for Examples 13 to 17. One aim was to compare the conditioner functionality of monomer pair treatment with that of dopamine treatment at 80 degree C for 2 to 4 hours, by the back light test. The other aim was to examine the benefit of free radical initiator treatment to the conditioner functionality of monomer pair treatment.

[0051] By visually checking the coverage of electroless copper on glass cloth coupons, the conditioner functionality of in-situ polymerization film was assessed more directly and more conveniently. A quantitative measurement of electroless copper coverage was a back light test, which measures the degree of electroless copper coverage in plated through holes, which contain areas of resin, glass fiber tips, and transverse glass fibers.

[0052] The back light test was carried out on small sections cut from drilled laminates, containing a number of holes, aligned along the same axis. The diameter of the holes chosen was 1 millimeter. Once the drilled laminates have been processed through the electroless copper plating process, the holes to be evaluated were extracted with a diamond saw. The holes were cut as close as possible to their center axis, while ensuring the holes were free of burrs or other debris and that the thickness of the coupon (from back surface to the middle of the holes) was less than 3 mm to allow light transmission through the sample to allow light to penetrate for the back light test. An optical microscope capable of 50 to 1500 magnifications was used to carry out the back light test. Each of the holes was individually assessed by comparing with a series of standard images shown in Figure 1.

[0053] Transmitted light was visible in any areas within the holes where there was incomplete electroless copper coverage. A numerical scale of 0.0 ∼ 5.0 was used as back light ratings, where 5.0 represents a completely copper coverage on both resin areas and glass fiber areas. Back light ratings equal to or above 4.5 represent substantially complete copper coverage on resin and glass fiber areas. Only occasional glass tip voids were observed. Back light ratings equal to or above 4.0 indicated that the majority of resin and glass fiber areas had copper coverage, but voids were found on some glass tip areas and sometimes on transverse glass fiber areas. A back light rating ranging from 2 to 3.5 represented good copper coverage on resin areas, but poor copper coverage on glass areas (both glass tip and transverse glass fiber area). A back light rating lower than 2 means minimal copper coverage was found either on resin areas or on glass fiber areas. The back light ratings shown in this invention were the average of the values for 10 holes.

Example 13


(1) Pretreatment



[0054] Glass cloth coupons same as in Example 1 were used as samples for film formation test and electroless copper coverage tests, and copper clad laminate S1141 with 1mm diameter drilled holes (Size: 35mm* 100mm* 2mm, 20 holes per coupon, Shengyi Technology Co. Ltd., glass transition temperature: 140 to 150 degree C, abbreviated as drilled laminates) were used as samples for back light tests. Drill laminates were processed through the de-smear process shown below, which included a sweller, an oxidiation, and a neutralizer bath treatment. Glass cloth coupons were not treated in the de-smear process.

[0055] The drill laminates were dipped in a sweller bath at 75 degree C for 5 minutes, which contained 125 mL/L CIRCUPOSIT™ MLB Conditioner 211 (Dow Electronics Materials) and 115 mL/L CUPOSIT™ Z(Dow Electronics Materials), and then rinsed with R.O. water for 3 minutes. The drilled laminates were then dipped in an Oxidiation bath at 80 degree C for 8 minutes, which contained 150 mL/L CUPOSIT™ Z (Dow Electronics Materials) and100 mL/L of CIRCUPOSIT™ MLB Promoter 213 (Dow Electronics Materials), and then rinsed with R.O. water for 3 minutes. After that, the drilled laminates were dipped in 50 mL/L of CIRCUPOSIT™ MLB Neutralizer 216-5 bath (Dow Electronics Materials) at 40 degree C for 5 minutes followed by water rinse for 3 minutes. The drilled laminates were then dried with an air knife for 2 minutes.

(2) Free Radical Initiator treatment



[0056] The dried glass cloth coupons as well as the de-smeared drilled laminates were treated in the same free radical initiator treatment as Example 1. The test sample was dipped in a free radical initiator solution comprising 0.2 mol/L of AIBN in toluene at room temperature for 1 minute. The sample was then dried in a fume hood at room temperature for 5 minutes.

(3) (A)+(B) solution treatment



[0057] Both the glass cloth coupons and the drilled laminates were contacted with a solution comprising (A) and (B) above. As indicated in Table 3, the solution comprising 0.026 mol/L of hexamethylene diamine and 0.013 mol/L of catechol was prepared using a K2HPO4/ Citric Acid buffer solution. The pH of the solution was 4.5. The samples were dipped in the aqueous solution described above at 80 degree C for 2 to 4 hours. A water insoluble copolymer(A+B) film was formed on the surface of the samples.

(4) Electroless Copper Plating without a traditional conditioner step



[0058] Both the glass cloth coupons and the drilled laminates were processed through the same electroless copper plating process as Example 1.

(5) Back Light Test



[0059] After electroless copper plating, drilled laminates samples were cut by diamond saw as described in the previous section. The back light test was carried out on ten holes per sample with 1 mm diameter using a Leica DM6000 light microscope with a magnification: 50X. The back light ratings shown in Table 3 were the average of the values for 10 holes.

Example 14



[0060] Example 14 was processed in the same way as Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator.

Example 15



[0061] Example 15 was a dopamine control example with free radical treatment. It was processed in the same way as for Example 13, except that step (3) was conducted using 0.013 mol/L dopamine aqueous solution buffered with 0.010 mol/L tris(hydroxymethyl) amino methane and HCl to pH 8.5.

Example 16



[0062] Example 16 was a dopamine control example without free radical treatment. It was processed in the same way as for Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted using 0.013 mol/L dopamine aqueous solution buffered with 0.010 mol/L tris(hydroxymethyl) amino methane and HCl to pH 8.5.

Example 17



[0063] Example 17 was a blank control for Example 13 to 16. It was processed in the same way as for Example 13 except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.
Table 3
Ex. No.Free Radical Initiator treatmentDip in an aqueous solution of below listed solutes @ 80°C for 2 ∼ 4 hoursCopolymer(A+B) film formed on the surface of glass cloth couponsElectroless Cu film formed on the surface of glass cloth coupons without the use of a traditional conditionerBack Light Rating (Electroless Cu coverage, Highest rating is 5.0)
13 With

Yes Yes 4.8
14 Without Yes Yes 4.0
@ pH 4.5
15 With 0.013 mol/L Yes No 3.1


16 Without Yes No 3.1
@ pH 8.5
17 Without Blank Control: Distilled water @ pH 7 No No 3.0


[0064] Comparing Example 14 with 17, it can be seen that good copper coverage was only obtained both on glass cloth coupons and in the through holes of drilled laminates that were treated by a monomer pair (HMDA/Catechol) at 80 degree C for 2 ∼ 4 hours without free radical initiator.

[0065] Comparing Example 14 with 13, It can be seen that even better copper coverage was obtained in the through holes of drilled laminates that were treated by the same monomer pair (HMDA/Catechol) at the same temperature (80 degree C) for the same duration (2 ∼ 4 hours) with free radical initiator treatment.

[0066] Example 15 and 16 indicated that poor copper coverage was observed on glass cloth coupons and in the through holes of drilled laminates that were treated by dopamine at 80 degree C for 2 ∼ 4 hours, whether with or without free radical treatment, although there was visible polydopamine film formed on the surface of treated sample. Compared with Example 10 shown in Table 2, the formation temperature of polydopamine affected its conditioner functionality. At room temperature for 24 hours, the polydopamine film formed showed good conditioner functionality. At 80 degree C for 2 ∼ 4 hours, the polydopamine film did not show conditioner functionality, although its appearance was similar to that formed at room temperature for 24 hours. A possible explanation to this phenomenon was that the priority of reactions may have changed with an increase of the treatment temperature. At higher temperatures, a higher rate of oxidation reaction was observed, and a higher rate of Michael Addition reaction was assumed. Under these conditions, more consumption of amine groups was expected, leaving less amine group residues on the surface of polydopamine film, resulting in weaker conditioner function.

Examples 18 - 25



[0067] Examples 18 to 25 were proceeded to examine the multiple functionalities of the copolymer(A+B) film formed by monomer pairs ((A) + (B)) treatment, including the conditioner functionality and the adhesion promoter functionality by Back Light Test and Peel Strength Test.

[0068] Peel Strength Test was conducted on the test coupons using the following conditions:

Equipment: Peel strength tester, Type: Ceco TA 631E

Peel speed: 2 inch/minutes

Width of the copper strip: 10 millimeter

Length of the copper strip: 100 millimeter

Thickness of the copper strip: 34 micron to 38 micron

Testing time per strip: 80 second

Peel strength data for one strip: the average of the peel strength values during 15 second to 75 second

Peel strength data shown in this invention: the average of the peel strength data obtained from 8 ∼ 10 strips


Examples 18-20


(1) Pretreatment



[0069] Drilled laminates S1141 the same as Example 13 were used as samples for back light test, and glass-fiber reinforced bare epoxy laminates S1141 (Size: 50mm*150mm*1mm, Supplier: Shengyi Technology Co. Ltd., Glass transition temperature: 140 to 150 degree C, Abbreviated as bare laminates S1141) were used as test samples for peel strength between dielectric substrate and deposited metal film.

[0070] Bare laminates S1141 and drilled laminates S1141 were processed through the same de-smear process described in Example 13.

(2) Free Radical initiator Treatment



[0071] De-smeared bare laminates S1141 and de-smeared drilled laminates S1141 were processed through the same free radical initiator treatment process described in Example 13.

(3) (A)+(B) solution Treatment



[0072] Next, the sample was processed through the step of contacting with a solution comprising (A) and (B) above. In these experiments, (A) is hexamethylene diamine and (B) is catechol. The basic concentration was 0.013mol/L. By multiplying the basic concentration 0.013 mol/L by the mole ratio of the indicated monomer shown in table 4, the initial concentration of that monomer in the treatment bath was obtained. The sample was treated at 80 degree C for 2 to 4 hours. A water insoluble film was formed on the surface of treated samples.

(4) Electroless plating without a traditional conditioner step



[0073] After (A)+(B) solution treatment, the bare laminates S1141 and drilled laminates S1141 were processed through the same electroless plating process without a traditional conditioner step described in Example 13.

(5) Back Light Test



[0074] After electroless plating, the drilled laminates S1141 were examined using the same back light test process as Example 13.

(6) Electrolytic plating



[0075] The samples of bare laminates S1141 with the electroless copper film were processed through an electrolytic copper plating process. The sample was first dipped in a acid cleaner bath at 40 degree C for 5 minutes, which contained 50 mL/L RONACLEAN™ LP 200 ACIDIC CLEANER (Dow Electronics Materials) and 50 mL/L 98% H2SO4 (Sigma-Aldrich). The sample was then rinsed with R.O. water for 3 minutes. After that, the sample was dipped in a 100 mL/L 98%H2SO4 aqueous solution at 23 degree C for 1 minute. Electrolytic plating was then performed in an aqueous solution comprising 75 g/L copper ion from CuSO4, 100 mL/L 98% H2SO4 (Sigma-Aldrich), 60 ppm chloride ion from 1 mol/L HCl (Sigma-Aldrich), 10 mL/L COPPER GLEAM™ 125T-AB Part B and 5 mL/L COPPER GLEAM™ 125T-AB Part A, at 20 ampere per square feet for 80 minutes.

(7) Baking



[0076] Next, the electrolytic plated sample was baked at 160 degree C for 60 minutes before the peel strength test.

Example 21



[0077] Example 21 was a blank control for Examples 18 to 20. It was processed in the same way as Example 18-20, except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.

Examples 22 - 24



[0078] Examples 22 to 24 were processed in the same way as Example 18-20 except that peel strength test was performed on another type of dielectric substrate, ABF-GX-13 film applied to a laminate substrate (Size: 100mm*100mm, Supplier: Ajinomoto fine-techno Co., Inc,), and that no back light tests were carried out.

Example 25



[0079] Example 25 was a blank control for Examples 22 to 24. It was processed in the same way as Example 22-24, except that step (2) was conducted in toluene without the presence of any free radical initiator, and step (3) was conducted in distilled water alone, without any solute.
Table 4
Ex. No.Dip in 0.2 mol/L AIBN Toluene SolutionDip in an aqueous solution ofBack Light Rating (Electroless Cu coverage, Highest Rating is 5.0)Peel strength (lb/in)Dielectric substrates


Time & TempMole ratio of (A) to (B)pH
18 1 min @ RT 2 ∼ 4 hours @ 80°C 2 : 1 8.5 4.3 5.3 S1141 (Ra < 400nm)
19 1 min @ RT 4.5 4.8 4.0
20 1 min @ RT 1 : 1 3.5 4.6 ---
21 --- --- --- --- 3.0 2.9
22 1 min @ RT 2 ∼ 4 hours @ 80°C 2 : 1 8.5 --- 2.6 ABF-GX13 (Ra < 200nm)
23 1 min @ RT 4.5 --- 3.3
24 1 min @ RT 1 : 1 3.5 --- 2.8
25 --- --- --- --- --- 2.0


[0080] It was observed that the through holes treated with the solutions of Example 18-20 (Figure 2 --- Example 19) showed much better electroless copper coverage than untreated ones (Figure 3 - Example 21), and coupons treated with a solution comprising hexamethylene diamine and catechol (either S1141 - Example 18- 20 or ABF-GX13 - Example 22-24) showed much higher peel strength than the untreated ones (Example 20 or Example 25). The improvement in back light and peel strength varied with mole ratio of (A) to (B) and pH of treatment bath, which showd the performance may be tailored based on requirements.


Claims

1. A method for forming a metallic film on a surface of a non-conductive material, the method comprising the steps of:

(i) contacting the surface of the material with a solution comprising

(A) a diamine compound of formula

        H2N-R1-NH2

wherein R1 is selected from the group consisting of C1 to C24 linear or branched alkylene and aromatic alkylene, and

(B) a di-hydroxyl compound of formula

wherein R8 is selected from the group consisting of H, CH3, OH, phenyl, CN, NO2, propanoic acid group, ethylamine group, formic acid group and formaldehyde group, and R9 and R10 are independently selected from H and OH, one of R8, R9 and R10 being OH,

wherein the mole ratio of (A) to (B) is from 4:1 to 1:1; and

(ii) conducting electroless metal plating of the surface of the material using a Pd/Sn colloidal catalyst.


 
2. The method of claim 1, wherein the mole ratio of (A) to (B) is 2:1.
 
3. The method of claim 1 or 2, wherein (B) is catechol.
 
4. The method of claim 1, wherein the method further comprises the step of contacting the surface of the material with a solution comprising a free radical initiator prior to the step of contacting the surface of the material with a solution comprising (A) and (B).
 


Ansprüche

1. Ein Verfahren zum Bilden eines metallischen Films auf einer Oberfläche eines nicht leitenden Materials, wobei das Verfahren die folgenden Schritte beinhaltet:

(i) In-Kontakt-Bringen der Oberfläche des Materials mit einer Lösung, beinhaltend

(A) eine Diaminverbindung der Formel

        H2N-R1-NH2,

wobei R1 ausgewählt ist aus der Gruppe, bestehend aus linearem oder verzweigtem C1-bis-C24-Alkylen und aromatischem Alkylen, und

(B) eine Dihydroxylverbindung der Formel

wobei R8 ausgewählt ist aus der Gruppe, bestehend aus H, CH3, OH, Phenyl, CN, NO2, Propansäuregruppe, Ethylamingruppe, Ameisensäuregruppe und Formaldehydgruppe, und R9 und R10 unabhängig ausgewählt sind aus H und OH, wobei einer von R8, R9 und R10 OH ist,

wobei das Molverhältnis von (A) zu (B) 4 : 1 bis 1 : 1 beträgt; und

(ii) Durchführen einer stromlosen Metallisierung der Oberfläche des Materials unter Verwendung eines Pd/Sn-Kolloidkatalysators.


 
2. Verfahren gemäß Anspruch 1, wobei das Molverhältnis von (A) zu (B) 2 : 1 beträgt.
 
3. Verfahren gemäß Anspruch 1 oder 2, wobei (B) Brenzcatechin ist.
 
4. Verfahren gemäß Anspruch 1, wobei das Verfahren vor dem Schritt des In-Kontakt-Bringens der Oberfläche des Materials mit einer (A) und (B) beinhaltenden Lösung ferner den Schritt des In-Kontakt-Bringens der Oberfläche des Materials mit einer einen Radikalinitiator beinhaltenden Lösung beinhaltet.
 


Revendications

1. Une méthode pour former un film métallique sur une surface d'un matériau non conducteur, la méthode comprenant les étapes consistant à :

(i) mettre en contact la surface du matériau avec une solution comprenant

(A) un composé diamine de formule

        H2N-R1-NH2

dans laquelle R1 est sélectionné dans le groupe constitué d'un alkylène aromatique et d'un alkylène linéaire ou ramifié en C1 à C24, et

(B) un composé di-hydroxyle de formule

dans laquelle R8 est sélectionné dans le groupe constitué de H, CH3, OH, un phényle, CN, NO2, un groupe acide propanoïque, un groupe éthylamine, un groupe acide formique et un groupe formaldéhyde, et R9 et R10 sont indépendamment sélectionnés parmi H et OH, l'un de R8, R9 et R10 étant OH,

le rapport molaire de (A) à (B) allant de 4/1 à 1/1 ; et

(ii) effectuer un placage autocatalytique de métal de la surface du matériau en utilisant un catalyseur colloïdal Pd/Sn.


 
2. La méthode de la revendication 1, dans laquelle le rapport molaire de (A) à (B) est de 2/1.
 
3. La méthode de la revendication 1 ou de la revendication 2, dans laquelle (B) est du catéchol.
 
4. La méthode de la revendication 1, la méthode comprenant en sus l'étape consistant à mettre en contact la surface du matériau avec une solution comprenant un amorceur radicalaire préalablement à l'étape consistant à mettre en contact la surface du matériau avec une solution comprenant (A) et (B).
 




Drawing












REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description