JP2014067976A - Process of manufacturing multilayer wiring board - Google Patents
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- JP2014067976A JP2014067976A JP2012214156A JP2012214156A JP2014067976A JP 2014067976 A JP2014067976 A JP 2014067976A JP 2012214156 A JP2012214156 A JP 2012214156A JP 2012214156 A JP2012214156 A JP 2012214156A JP 2014067976 A JP2014067976 A JP 2014067976A
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- plating
- wiring board
- multilayer wiring
- degreasing
- hypochlorous acid
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 78
- 238000005238 degreasing Methods 0.000 claims abstract description 36
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010306 acid treatment Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 36
- 238000009713 electroplating Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010410 layer Substances 0.000 abstract description 29
- 239000002344 surface layer Substances 0.000 abstract description 20
- 238000004140 cleaning Methods 0.000 abstract description 14
- 238000002203 pretreatment Methods 0.000 abstract description 6
- 230000000149 penetrating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000007772 electroless plating Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- Production Of Multi-Layered Print Wiring Board (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は、めっき前処理に特徴を有する多層配線基板の製造方法に関するものであり、特には、多層配線基板の表層から内層に到る非貫通穴を電気的に接続するためのめっき前処理方法に特徴を有する多層配線基板の製造方法に関するものである。 The present invention relates to a method for manufacturing a multilayer wiring board characterized by pretreatment for plating, and in particular, a plating pretreatment method for electrically connecting non-through holes from the surface layer to the inner layer of the multilayer wiring board. The present invention relates to a method for manufacturing a multilayer wiring board having the characteristics described above.
電子機器の高密度化に伴い、電子機器に用いられる多層配線基板に対しても高密度化が求められており、必要な層間のみを接続可能な、いわゆるＩＶＨ（インタースティシャルバイアホール）を有する構造の多層配線基板が主流となっている。 Along with the increase in the density of electronic devices, there is a demand for higher density also for multilayer wiring boards used in electronic devices, and so-called IVH (interstitial via holes) that can connect only necessary layers are provided. A multilayer wiring board having a structure has become mainstream.
多層配線基板にＩＶＨを形成する場合は、エッチングによって表層の銅箔にコンフォーマルマスクとなる窓孔を設け、この窓孔にレーザを照射して表層と内層の間に配置された絶縁樹脂を除去することで、表層から内層に到る非貫通穴（非貫通穴）を形成した後、この非貫通穴内に対して、レーザの加工残渣であるスミアを除去するデスミア処理を行い、さらに無電解めっきや電気めっきを行って表層と内層とを電気的に接続する。 When forming IVH on a multilayer wiring board, a window hole serving as a conformal mask is provided in the copper foil on the surface layer by etching, and this window hole is irradiated with a laser to remove the insulating resin disposed between the surface layer and the inner layer. After forming a non-through hole (non-through hole) from the surface layer to the inner layer, the non-through hole is subjected to a desmear treatment that removes smear as a laser processing residue, and further electroless plating The surface layer and the inner layer are electrically connected by performing electroplating.
多層配線基板表層の汚れ等による銅皮膜の剥れやざら、異常析出といった不良を防ぐためには通常デスミア処理あるいは無電解めっきの前処理で汚れの除去を行う。しかし無電解めっきで析出する金属銅に強く結びつく物質が含まれる場合、前記多層配線基板表面に電気めっきを行なう際、本来正常な金属銅表面には発生し得ないめっきピットと表現されるめっき不析出が起こる場合がある。特にパネルめっき法といわれる表層に何らパターン形成を行なわず、無電解めっき直後に電気めっきを行なう場合は、その影響が出易い場合がある。 In order to prevent defects such as peeling of the copper film due to dirt on the surface of the multilayer wiring board, rough deposition, and abnormal deposition, the dirt is usually removed by a desmear treatment or a pretreatment of electroless plating. However, when a material that strongly binds to metallic copper deposited by electroless plating is included, when electroplating is performed on the surface of the multilayer wiring board, plating failure expressed as plating pits that cannot be generated on the normal metallic copper surface. Precipitation may occur. In particular, in the case where electroplating is performed immediately after electroless plating without forming any pattern on the surface layer, which is referred to as a panel plating method, the influence may easily occur.
無電解銅めっきを行なわないで導体上にパターン形成を行い、その後電解銅めっきを行なうパターンめっき法では電気めっきの前処理として脱脂処理の後に３０℃から７０℃の水洗処理を行う方法（特許文献１）、及び脱脂処理の前にｐＨ５以上１０以下の水性溶液に浸漬する方法（特許文献２）が開示されている。また無電解めっきを行なった後にパターン形成を行い、その後電気めっきを行なうパターンめっき法には電気めっきの前処理として脱脂処理を行った後に、シランカップリング剤水溶液に浸漬する方法が開示されている（特許文献３）。 In a pattern plating method in which pattern formation is performed on a conductor without performing electroless copper plating, and then electrolytic copper plating is performed, a water washing treatment at 30 ° C. to 70 ° C. is performed after a degreasing treatment as a pretreatment for electroplating (Patent Document) 1) and a method of immersing in an aqueous solution having a pH of 5 to 10 before degreasing (Patent Document 2) is disclosed. In addition, a pattern plating method in which pattern formation is performed after electroless plating is performed and then electroplating is performed, a method of degreasing treatment as a pretreatment of electroplating and then immersing in an aqueous silane coupling agent solution is disclosed. (Patent Document 3).
一方、多層配線基板のＩＶＨに対して電気めっきを行うためのめっき液として銅化合物、特定のキレート化剤及び二価の硫黄を含有する有機化合物等を含有するめっき液が提案されている（特許文献４）。 On the other hand, a plating solution containing a copper compound, a specific chelating agent and an organic compound containing divalent sulfur has been proposed as a plating solution for performing electroplating on IVH of a multilayer wiring board (patent) Reference 4).
特許文献１及び２に開示される方法では無電解めっき工程が含まれておらず、無電解めっきが起因であるめっきピットには対応できない。また特許文献３で開示される方法はめっきレジストを親水化して気泡の付着を防ぐものであり、めっきレジストがないパネルめっき法には有効ではない。 The methods disclosed in Patent Documents 1 and 2 do not include an electroless plating step and cannot deal with plating pits caused by electroless plating. Further, the method disclosed in Patent Document 3 is to make the plating resist hydrophilic to prevent the adhesion of bubbles, and is not effective for the panel plating method without the plating resist.
また、特許文献４に開示された方法ではめっき液添加剤の種類が決まってしまい、フィルドビアめっき等多様な電気めっきに対するめっきピット対策としては適用が困難である。 The method disclosed in Patent Document 4 determines the type of plating solution additive, and is difficult to apply as a plating pit countermeasure for various electroplating such as filled via plating.
本発明は、上記問題に鑑みなされたものであり、多層配線基板の表層から内層に到る非貫通穴を電気的に接続するための電気めっきを行う際に、めっきピットの発生を抑制するめっき前処理方法を提供するものである。 The present invention has been made in view of the above problems, and suppresses the generation of plating pits when performing electroplating for electrically connecting non-through holes from the surface layer to the inner layer of a multilayer wiring board. A pre-processing method is provided.
上記課題を解決するために本発明は、以下に示す構成を備える。
１． 絶縁層を貫通して内層に配置された導体回路に到る非貫通穴を設け、この非貫通穴内に下地めっきと電気めっきとを形成する多層配線基板の製造方法であって、前記下地めっきを形成する工程と電気めっきを形成する工程との間に、脱脂工程と、次亜塩素酸処理工程と、酸洗浄工程と、を有する多層配線基板の製造方法。
２． 項１において、脱脂工程で用いる脱脂液が、アルカリ性の脱脂液である多層配線基板の製造方法。
３． 項１又は２において、次亜塩素酸処理工程で用いる次亜塩素酸水溶液が、１２質量％次亜塩素酸ナトリウム溶液にして０．３〜１．２ｍＬ／Ｌの次亜塩素酸を含有する多層配線基板の製造方法。
４． 項１から３のいずれかにおいて、電気めっきをフィルドビアめっきとする多層配線基板の製造方法。
In order to solve the above problems, the present invention has the following configuration.
1. A method of manufacturing a multilayer wiring board, wherein a non-through hole is formed through an insulating layer to reach a conductor circuit disposed in an inner layer, and a base plating and an electroplating are formed in the non-through hole. The manufacturing method of the multilayer wiring board which has a degreasing process, a hypochlorous acid treatment process, and an acid washing process between the process of forming and the process of forming electroplating.
2. Item 2. The method for producing a multilayer wiring board according to Item 1, wherein the degreasing liquid used in the degreasing step is an alkaline degreasing liquid.
3. Item 11 or 2 is a multilayer in which the hypochlorous acid aqueous solution used in the hypochlorous acid treatment step contains 0.3 to 1.2 mL / L of hypochlorous acid in a 12% by mass sodium hypochlorite solution. A method for manufacturing a wiring board.
4). Item 4. The method for manufacturing a multilayer wiring board according to any one of Items 1 to 3, wherein the electroplating is filled via plating.
本発明によれば、多層配線基板の表層から内層に到る非貫通穴を電気的に接続するための電気めっきを行う際に、めっきピットによる不良が少ない高品質の多層配線板を製造することが可能になる。 According to the present invention, when performing electroplating for electrically connecting non-through holes extending from the surface layer to the inner layer of a multilayer wiring board, a high-quality multilayer wiring board with few defects due to plating pits is produced. Is possible.
本発明は、絶縁層を貫通して内層に配置された導体回路に到る非貫通穴を設け、この非貫通穴内に下地めっきとフィルドビアめっきとを形成する多層配線基板の製造方法であり、図１に示すように、前記下地めっきを形成する工程と電気めっきを形成する工程との間に、脱脂工程と、次亜塩素酸処理工程と、酸洗浄工程と、を有する。 The present invention is a method for manufacturing a multilayer wiring board in which a non-through hole is formed which penetrates an insulating layer and reaches a conductor circuit disposed in an inner layer, and a base plating and a filled via plating are formed in the non-through hole. As shown in FIG. 1, a degreasing step, a hypochlorous acid treatment step, and an acid cleaning step are provided between the step of forming the base plating and the step of forming electroplating.
絶縁層を貫通して内層に配置された導体回路に到る非貫通穴とは、表層に配線された導体回路と内層に配置された導体回路とを電気的に接続する層間接続を形成するために用いるものである。ここで、表層又は内層は、多層配線基板の製品としての最終形態の表層又は内層には限定されず、多層配線基板の製造プロセスの途中における表層又は内層を含む。非貫通穴の形成方法は、多層配線基板において用いられる形成方法であれば、特に限定なく用いることができ、金属箔をマスクとしてレーザ加工を行うコンフォーマルマスク法や、金属箔と絶縁層を同時にレーザ加工するダイレクトレーザ法等が挙げられる。 The non-through hole that penetrates through the insulating layer and reaches the conductor circuit arranged in the inner layer is to form an interlayer connection that electrically connects the conductor circuit wired in the surface layer and the conductor circuit arranged in the inner layer. It is used for. Here, the surface layer or the inner layer is not limited to the surface layer or the inner layer in the final form as a product of the multilayer wiring board, but includes a surface layer or an inner layer in the course of the manufacturing process of the multilayer wiring board. The formation method of the non-through hole can be used without particular limitation as long as it is a formation method used in a multilayer wiring board. The conformal mask method in which laser processing is performed using a metal foil as a mask, or the metal foil and the insulating layer are simultaneously formed. Examples include a direct laser method for laser processing.
下地めっきとは、非貫通穴に電気めっきを形成する際の給電層となるものであり、無電解銅めっき、無電解ニッケルめっき等を用いて形成することができる。下地めっきの厚みは、めっき膜が連続膜を形成する厚み以上あればよいが、０．３〜１．０μｍが一般的である。 The base plating serves as a power feeding layer when electroplating is formed in the non-through hole, and can be formed using electroless copper plating, electroless nickel plating, or the like. The thickness of the base plating may be equal to or greater than the thickness at which the plating film forms a continuous film, but is generally 0.3 to 1.0 μm.
電気めっきとは、非貫通穴が層間接続として機能するために必要な導電層としての厚みを形成するためのものであり、電気銅めっき、電気ニッケルめっき等を用いて形成することができる。導電性が優れる点から、電気銅めっきを用いるのが好ましく、また、非貫通穴内をめっきで充填して平坦化し、非貫通穴の直上に非貫通穴が形成可能な点で、電気銅めっきによるフィルドビアめっきを用いるのがさらに好ましい。 The electroplating is for forming a thickness as a conductive layer necessary for the non-through hole to function as an interlayer connection, and can be formed using electrolytic copper plating, electrolytic nickel plating, or the like. It is preferable to use electrolytic copper plating because of its excellent electrical conductivity. Also, it is possible to form a non-through hole directly above the non-through hole by filling the inside of the non-through hole with plating. More preferably, filled via plating is used.
脱脂工程は、被めっき体である多層配線基板から油脂汚れ等を除去する工程である。脱脂は、めっき前処理用の脱脂液として一般に用いられる溶剤、アルカリ性水溶液、酸性水溶液等を用いることができる。無電解めっき上に付着した有機化合物を除去することを目的とする場合にはアルカリ性水溶液であることがより望ましい。脱脂処理の条件としては、脱脂液の種類等によって一般的に用いられる条件を用いればよく、例えば、３０〜４０℃の温度で、４分〜６分の条件を用いることができる。 The degreasing step is a step of removing oil and fat stains and the like from the multilayer wiring board that is the object to be plated. For degreasing, a solvent generally used as a degreasing solution for plating pretreatment, an alkaline aqueous solution, an acidic aqueous solution, or the like can be used. An alkaline aqueous solution is more desirable for the purpose of removing organic compounds adhering to the electroless plating. As conditions for the degreasing treatment, conditions generally used depending on the type of the degreasing liquid and the like may be used. For example, a condition of 4 to 6 minutes can be used at a temperature of 30 to 40 ° C.
水洗Ａ工程は、脱脂に用いた脱脂液を前記多層配線基板から洗浄除去する工程である。前工程で多層配線基板に付着した脱脂液を十分に洗浄可能なように、多層配線基板の表層ビアのアスペクト比や搬送速度等に応じて、洗浄時間や流水洗の流水量等が設定される。このような条件としては、例えば、流水量１Ｌ／分以上、５Ｌ／分以下、洗浄時間５分以上が挙げられる。また脱脂処理後の急激な温度変化を防ぐことを目的に脱脂処理後の水洗槽の温度を３０〜５０℃にしてもよい。 The water washing step A is a step of washing and removing the degreasing liquid used for degreasing from the multilayer wiring board. In order to be able to sufficiently clean the degreasing liquid adhering to the multilayer wiring board in the previous process, the cleaning time, the amount of running water, etc. are set according to the aspect ratio of the surface layer via of the multilayer wiring board, the conveyance speed, etc. . Examples of such conditions include a flow rate of 1 L / min to 5 L / min and a washing time of 5 minutes or more. Moreover, you may make the temperature of the water-washing tank after a degreasing process into 30-50 degreeC in order to prevent the rapid temperature change after a degreasing process.
次亜塩素酸処理工程は、無電解めっき表面に強く吸着した無電解めっき添加剤を除去する工程である。次亜塩素酸処理によって、下地めっき（無電解銅めっき）の添加剤が除去され、フィルドビアめっきの析出阻害によるめっきピットの発生を防ぐことができる。次亜塩素酸処理工程で用いる次亜塩素酸処理液としては次亜塩素酸ナトリウム水溶液が挙げられる。次亜塩素酸カルシウムは後工程の酸洗浄工程に持ち込まれた場合、沈殿を生じやすいために適用は困難である。次亜塩素酸ナトリウムは一般に水溶液として販売される。次亜塩素酸処理液の組成・処理条件としては１２質量％次亜塩素酸ナトリウム水溶液０．３〜２．０ｍＬ／Ｌ、２０℃〜３０℃、３０〜１８０秒であることが望ましい。１２質量％次亜塩素酸ナトリウム濃度が０．３ｍＬ／Ｌ未満であれば所望とする効果を得にくく、２．０ｍＬ／Ｌを超えると次亜塩素酸ナトリウムが過剰に無電解めっきを酸化してしまうために電気めっき後に無電解めっき表面への析出不良が増加してしまう。次亜塩素酸処理液の温度制御は、所定範囲の温度制御が可能であれば特に限定はないが、例えば、加温用のヒータと冷却用のチラーを水洗槽Ａ内に設けることにより行うことができる。ヒータとしては、電気ヒータ、蒸気ヒータ、温水ヒータ、オイルヒータ等が挙げられ、チラーとしては、水冷チラー、空冷チラー、オイルチラー等が挙げられる。これらのうち、熱交換器を使用するものは、熱交換器が次亜塩素酸処理槽に設置される。次亜塩素酸処理槽内の処理液温度をより均一にするには、循環ポンプを備えるのが望ましい。 The hypochlorous acid treatment step is a step of removing the electroless plating additive strongly adsorbed on the electroless plating surface. By the hypochlorous acid treatment, the additive of the base plating (electroless copper plating) is removed, and the generation of plating pits due to the deposition inhibition of filled via plating can be prevented. Examples of the hypochlorous acid treatment liquid used in the hypochlorous acid treatment step include a sodium hypochlorite aqueous solution. Calcium hypochlorite is difficult to apply because it tends to precipitate when it is brought into the subsequent acid cleaning step. Sodium hypochlorite is generally sold as an aqueous solution. As composition and processing conditions of a hypochlorous acid processing liquid, it is desirable that they are 12 mass% sodium hypochlorite aqueous solution 0.3-2.0 mL / L, 20 to 30 degreeC, and 30 to 180 second. If the 12 mass% sodium hypochlorite concentration is less than 0.3 mL / L, it is difficult to obtain the desired effect. If it exceeds 2.0 mL / L, sodium hypochlorite excessively oxidizes the electroless plating. Therefore, the deposition failure on the electroless plating surface increases after electroplating. The temperature control of the hypochlorous acid treatment liquid is not particularly limited as long as the temperature control within a predetermined range is possible. For example, a heater for heating and a chiller for cooling are provided in the washing tank A. Can do. Examples of the heater include an electric heater, a steam heater, a hot water heater, and an oil heater. Examples of the chiller include a water-cooled chiller, an air-cooled chiller, and an oil chiller. Among these, those using a heat exchanger are installed in a hypochlorous acid treatment tank. In order to make the treatment liquid temperature in the hypochlorous acid treatment tank more uniform, it is desirable to provide a circulation pump.
水洗Ｂ工程は、次亜塩素酸処理工程に用いた次亜塩素酸処理液を多層配線基板から洗浄除去する工程である。水洗槽Ｂでの洗浄条件は、前工程で多層配線基板に付着した次亜塩素酸処理液を十分に洗浄可能なように、多層配線基板の表層ビア（表層から内層に到る層間接続用のビア）のアスペクト比や搬送速度等に応じて、洗浄時間や流水洗の流水量等が設定される。このような条件としては、例えば、流水量１Ｌ／分以上、５Ｌ／分以下、洗浄時間５分以上が挙げられる。 The water washing step B is a step of washing and removing the hypochlorous acid treatment liquid used in the hypochlorous acid treatment step from the multilayer wiring board. The cleaning condition in the water rinsing tank B is that the surface layer via (for the interlayer connection from the surface layer to the inner layer) of the multilayer wiring board is sufficient so that the hypochlorous acid treatment liquid adhering to the multilayer wiring board in the previous step can be sufficiently cleaned. In accordance with the aspect ratio of the via), the conveyance speed, etc., the cleaning time, the amount of running water, etc. are set. Examples of such conditions include a flow rate of 1 L / min to 5 L / min and a washing time of 5 minutes or more.
酸洗浄工程は、水洗Ｂ工程以前で発生した上記多層配線基板の表面に発生した酸化銅を除去する工程である。酸洗浄工程で使用される酸洗浄液としては硫酸水溶液が挙げられる。硫酸処理液の組成としては濃度１〜２０質量％であることが望ましい。硫酸濃度が１質量％未満であれば表面に析出した酸化銅を除去する効果を得にくく、２０質量％を超えると電気めっき槽への持込により電気めっき液の組成変動が大きくなる。 The acid cleaning step is a step of removing copper oxide generated on the surface of the multilayer wiring board generated before the water washing B step. Examples of the acid cleaning solution used in the acid cleaning step include an aqueous sulfuric acid solution. The composition of the sulfuric acid treatment liquid is preferably 1 to 20% by mass. If the sulfuric acid concentration is less than 1% by mass, it is difficult to obtain the effect of removing the copper oxide deposited on the surface, and if it exceeds 20% by mass, the composition variation of the electroplating solution increases due to being brought into the electroplating tank.
以下、本発明を実施例により説明するが，本発明はこれに限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
（実施例１）
エッチングによって表層の銅箔にコンフォーマルマスクとなる窓孔を設け、この窓孔にレーザ光を照射して表層と内層の間に配置された絶縁樹脂を除去することで、表層から内層に到る非貫通穴（非貫通穴）を形成した後、この非貫通穴内に対して、レーザの加工残渣であるスミアを除去するデスミア処理、及び表層と内層を接続する下地めっきとして無電解銅めっきを行った多層配線基板を、５枚準備した。この多層配線基板は、板厚が０．２ｍｍ、サイズが３００ｍｍ×５００ｍｍ、配線層が４層である。無電解銅めっきはＩＶＨ（Ｉｎｔｅｒｓｔｉｔｉａｌ Ｖｉａ Ｈｏｌｅ）用の非貫通穴内部及び多層配線基板表面にパラジウムコロイド触媒であるＨＳ２０１Ｂ（日立化成工業株式会社製、商品名）を使用して触媒核を付与後、ＣＵＳＴ２０００（日立化成工業株式会社製、商品名。「ＣＵＳＴ」は登録商標。）を使用して厚さ０．５μｍの下地無電解めっき層を形成した。
Example 1
A window hole serving as a conformal mask is formed in the copper foil of the surface layer by etching, and the insulating resin disposed between the surface layer and the inner layer is removed by irradiating the window hole with a laser beam to reach the inner layer from the surface layer. After forming a non-through hole (non-through hole), desmear treatment to remove smear, which is a laser processing residue, and electroless copper plating as a base plating to connect the surface layer and the inner layer are performed in the non-through hole Five multilayer wiring boards were prepared. This multilayer wiring board has a plate thickness of 0.2 mm, a size of 300 mm × 500 mm, and four wiring layers. Electroless copper plating is applied to the inside of non-through holes for IVH (Interstitial Via Hole) and the surface of the multilayer wiring board using HS201B (trade name, manufactured by Hitachi Chemical Co., Ltd.) which is a palladium colloid catalyst, A ground electroless plating layer having a thickness of 0.5 μm was formed using CUST2000 (trade name, manufactured by Hitachi Chemical Co., Ltd., “CUST” is a registered trademark).
この多層配線基板に対して、図１に示すように、被めっき体である多層配線基板の脱脂を行う脱脂工程と、脱脂に用いた脱脂液を多層配線基板から洗浄除去する水洗Ａ工程と、多層配線板表面の無電解銅めっきに含まれる添加剤を除去する次亜塩素酸処理工程と、次亜塩素酸処理に用いた次亜塩素酸処理液を多層配線基板から洗浄除去する水洗Ｂ工程と、多層配線基板表面の無電解銅めっきに発生した酸化銅を洗浄除去する酸洗浄工程とを備えるめっき前処理により、めっき前処理を行った後、電気フィルドビアめっきを行なった。 For this multilayer wiring board, as shown in FIG. 1, a degreasing process for degreasing the multilayer wiring board as the object to be plated, and a water washing A process for cleaning and removing the degreasing liquid used for degreasing from the multilayer wiring board, Hypochlorous acid treatment step for removing the additive contained in the electroless copper plating on the surface of the multilayer wiring board, and water washing step B for washing and removing the hypochlorous acid treatment solution used for the hypochlorous acid treatment from the multilayer wiring board Then, the pre-plating treatment was performed by the pre-plating treatment including the acid washing step of washing and removing the copper oxide generated in the electroless copper plating on the surface of the multilayer wiring board, and then the electrofilled via plating was performed.
脱脂工程を行う脱脂槽の脱脂液としては、アルカリ水溶液であるＰＣ−４５３（メルテックス株式会社製、商品名）を用い、４０℃、５分の条件で脱脂を行った。 As a degreasing liquid in a degreasing tank for performing the degreasing process, PC-453 (trade name, manufactured by Meltex Co., Ltd.), which is an alkaline aqueous solution, was used and degreasing was performed at 40 ° C. for 5 minutes.
水洗Ａ工程を行う水洗槽Ａは、第１水洗〜第３水洗までの３段に設けられ、第３水洗に新しい水洗水が供給され、液面の差によって、搬送方向とは逆方向に、第２水洗、第１水洗へとオーバーフローし、その後排水口から排水される。第１水洗Ａには、ヒータ及びチラーの熱交換器が設けられ、水洗水の温度を所定範囲に制御する。水洗水の温度（実際の温度）は、直前の脱脂工程に用いる脱脂液の設定温度と連動して制御される。本実施例では、脱脂液の設定温度（４０℃）に対して、第１水洗の水洗水の設定温度を４０℃とした。また、洗浄時間は各槽１分である。 The washing tank A for performing the washing A step is provided in three stages from the first washing to the third washing, and new washing water is supplied to the third washing, and due to the difference in liquid level, in the direction opposite to the conveying direction, It overflows to the 2nd water washing and the 1st water washing, and is drained from a drain outlet after that. The first washing A is provided with a heater and a chiller heat exchanger, and controls the temperature of the washing water within a predetermined range. The temperature of the washing water (actual temperature) is controlled in conjunction with the set temperature of the degreasing liquid used in the previous degreasing process. In this example, the set temperature of the first rinse was 40 ° C. with respect to the set temperature (40 ° C.) of the degreasing liquid. The washing time is 1 minute for each tank.
次亜塩素酸処理工程は、１２質量％次亜塩素酸ナトリウム溶液を０．６ｍＬ／Ｌ含有する次亜塩素酸処理液を用い、設定温度２５℃、１分の条件で行った。 The hypochlorous acid treatment process was performed using a hypochlorous acid treatment solution containing 0.6 mL / L of a 12% by mass sodium hypochlorite solution at a set temperature of 25 ° C. for 1 minute.
水洗Ｂ工程は、水洗Ａ工程と同様に、第１水洗〜第３水洗までの３段に設けた。洗浄条件は、常温で洗浄時間各段１分である。 The water washing B process was provided in three stages from the first water washing to the third water washing in the same manner as the water washing A process. The cleaning conditions are a normal cleaning time of 1 minute for each stage.
酸洗浄工程に用いる酸洗浄処理溶液は３質量％硫酸水溶液を常温で処理時間５分の条件で酸洗浄工程を行った。 The acid cleaning treatment solution used in the acid cleaning step was a 3% by weight sulfuric acid aqueous solution at room temperature and a processing time of 5 minutes.
上記のようにして、めっき前処理を行った多層配線基板に対して、厚さ２０μｍの電気めっきを形成した。電気めっきは、めっきレジストを形成しないパネルめっきである。電気めっき処理条件は添加剤としてマイクロフィルＶＦ−Ｎ（メルテックス株式会社製、商品名。「マイクロフィル」は登録商標。）を用い、処理温度２３℃で行なった。 As described above, electroplating with a thickness of 20 μm was formed on the multilayer wiring board that had been subjected to the plating pretreatment. Electroplating is panel plating that does not form a plating resist. The electroplating treatment conditions were as follows. Microfil VF-N (trade name, manufactured by Meltex Co., Ltd., “Microfil” is a registered trademark) was used at a treatment temperature of 23 ° C.
（実施例２）
実施例１と同様の多層配線基板を準備し、実施例１と同様のめっき前処理装置を用いて、めっき前処理を行った。めっき前処理のうち、次亜塩素酸処理液は、０．３ｍＬ／Ｌの１２質量％次亜塩素酸ナトリウム水溶液を用い、設定温度２５℃、５分の条件で次亜塩素酸処理を行った。これ以外は、実施例１と同様である。
(Example 2)
A multilayer wiring board similar to that of Example 1 was prepared, and a plating pretreatment was performed using the same plating pretreatment apparatus as that of Example 1. Of the plating pretreatment, the hypochlorous acid treatment solution was 0.3 mL / L of 12% by mass sodium hypochlorite aqueous solution, and hypochlorous acid treatment was performed at a set temperature of 25 ° C. for 5 minutes. . Except this, it is the same as the first embodiment.
（実施例３）
実施例１と同様の多層配線基板を準備し、実施例１と同様のめっき前処理装置を用いて、めっき前処理を行った。めっき前処理のうち、次亜塩素酸処理液は、１．２ｍＬ／Ｌの１２質量％次亜塩素酸ナトリウム水溶液を用い、設定温度２５℃、５分の条件で次亜塩素酸処理を行った。これ以外は、実施例１と同様である。
(Example 3)
A multilayer wiring board similar to that of Example 1 was prepared, and a plating pretreatment was performed using the same plating pretreatment apparatus as that of Example 1. Among the plating pretreatments, the hypochlorous acid treatment solution was 1.2 mL / L of 12% by mass sodium hypochlorite aqueous solution and was subjected to hypochlorous acid treatment at a set temperature of 25 ° C. for 5 minutes. . Except this, it is the same as the first embodiment.
（比較例１）
実施例１と同様の多層配線基板を準備し、実施例１と同様のめっき前処理装置を用いて、めっき前処理を行った。めっき前処理のうち、次亜塩素酸処理工程及び水洗Ｂ工程を行わず、水洗Ａ工程の後に酸洗浄工程を行った。これ以外は実施例１と同様である。
(Comparative Example 1)
A multilayer wiring board similar to that of Example 1 was prepared, and a plating pretreatment was performed using the same plating pretreatment apparatus as that of Example 1. Among the plating pretreatments, the hypochlorous acid treatment step and the water washing B step were not performed, and the acid washing step was performed after the water washing A step. The rest is the same as in the first embodiment.
（参考例１）
実施例１と同様の多層配線基板を準備し、実施例１と同様のめっき前処理装置を用いて、めっき前処理を行った。めっき前処理のうち、脱脂工程に酸性脱脂液ＰＣ−３１６（メルテックス株式会社製、商品名）を使用し、設定温度４０℃、処理時間５分で処理を行った。これ以外は、実施例１と同様である。
(Reference Example 1)
A multilayer wiring board similar to that of Example 1 was prepared, and a plating pretreatment was performed using the same plating pretreatment apparatus as that of Example 1. Among the plating pretreatments, acidic degreasing liquid PC-316 (trade name, manufactured by Meltex Co., Ltd.) was used in the degreasing step, and the treatment was performed at a set temperature of 40 ° C. and a treatment time of 5 minutes. Except this, it is the same as the first embodiment.
（参考例２）
実施例１と同様の多層配線基板を準備し、実施例１と同様のめっき前処理装置を用いて、めっき前処理を行った。めっき前処理のうち、次亜塩素酸処理液は、２．０ｍＬ／Ｌの１２質量％次亜塩素酸ナトリウム水溶液を用い、設定温度２５℃、５分の条件で次亜塩素酸処理を行った。これ以外は、実施例１と同様である。
(Reference Example 2)
A multilayer wiring board similar to that of Example 1 was prepared, and a plating pretreatment was performed using the same plating pretreatment apparatus as that of Example 1. Among the plating pretreatments, the hypochlorous acid treatment solution was 2.0 mL / L of 12% by mass sodium hypochlorite aqueous solution and was subjected to hypochlorous acid treatment at a set temperature of 25 ° C. for 5 minutes. . Except this, it is the same as the first embodiment.
表１に、各実施例及び各参考例において、本発明のめっき前処理装置を用いて、多層配線基板のめっき前処理を行った際の単位面積当たりのピット発生数をまとめた。実施例１〜３では、ピット発生数が１０個／ｃｍ２以下に制御することができた。一方、比較例１では、単位面積当たりのピット発生数が２５個／ｃｍ２と多い結果であった。参考例１でも、単位面積当たりのピット発生数が２５個／ｃｍ２と多い結果が得られた。次亜塩素酸濃度を２．０ｍＬ／Ｌとした参考例２では比較例１と比較するとピット個数は低減したが実施例と比較すると増加した。 Table 1 summarizes the number of pits generated per unit area when the pre-plating treatment of the multilayer wiring board was performed using the pre-plating treatment apparatus of the present invention in each example and each reference example. In Examples 1 to 3, the number of pits generated could be controlled to 10 pieces / cm 2 or less. On the other hand, in Comparative Example 1, the number of pits generated per unit area was as large as 25 / cm 2 . In Reference Example 1, the number of pits generated per unit area was as large as 25 / cm 2 . In Reference Example 2 in which the concentration of hypochlorous acid was 2.0 mL / L, the number of pits was reduced compared to Comparative Example 1, but increased compared to Example.
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| JP2021163825A (en) * | 2020-03-31 | 2021-10-11 | 味の素株式会社 | Method for manufacturing printed wiring board |
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| JP2007107074A (en) * | 2005-10-17 | 2007-04-26 | Okuno Chem Ind Co Ltd | Acidic copper electroplating solution and copper electroplating method |
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| JP2021077786A (en) * | 2019-11-11 | 2021-05-20 | 旭化成株式会社 | Printed circuit board containing polyphenylene ether |
| JP7462399B2 (en) | 2019-11-11 | 2024-04-05 | 旭化成株式会社 | Polyphenylene ether-containing printed wiring board |
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