WO2017016395A1 - 一种聚酰亚胺无胶柔性印刷线路板的制备方法 - Google Patents

一种聚酰亚胺无胶柔性印刷线路板的制备方法 Download PDF

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Publication number
WO2017016395A1
WO2017016395A1 PCT/CN2016/090073 CN2016090073W WO2017016395A1 WO 2017016395 A1 WO2017016395 A1 WO 2017016395A1 CN 2016090073 W CN2016090073 W CN 2016090073W WO 2017016395 A1 WO2017016395 A1 WO 2017016395A1
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Prior art keywords
flexible printed
polyimide
preparing
metal salt
wiring board
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PCT/CN2016/090073
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English (en)
French (fr)
Inventor
孟月东
常鹏
蔡刚强
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苏州卫鹏机电科技有限公司
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Priority to US15/558,189 priority Critical patent/US10182501B2/en
Priority to KR1020177001466A priority patent/KR102032624B1/ko
Priority to JP2017501411A priority patent/JP6704600B2/ja
Priority to EP16829761.2A priority patent/EP3261418B1/en
Publication of WO2017016395A1 publication Critical patent/WO2017016395A1/zh

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    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • H05K3/0041—Etching of the substrate by chemical or physical means by plasma etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • 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
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
    • H05K3/16—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation by cathodic sputtering
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0277—Bendability or stretchability details
    • H05K1/028—Bending or folding regions of flexible printed circuits
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/09—Treatments involving charged particles
    • H05K2203/095—Plasma, e.g. for treating a substrate to improve adhesion with a conductor or for cleaning holes

Definitions

  • the invention belongs to the technical field of preparation of microelectronic circuit boards, and particularly relates to a surface treatment method of polyimide and a preparation method of the circuit substrate.
  • Ultra-thin glueless flexible printed circuit boards are the development trend of the microelectronics industry.
  • the flexible circuit board can be divided into a flexible flexible circuit board and a non-adhesive flexible circuit board. If classified according to structure, it can be divided into single-sided flexible circuit board, double-sided flexible board, multi-layer soft board, soft and hard board.
  • the price of the flexible flexible circuit board is much higher than that of the flexible flexible board, its flexibility, the bonding strength of the copper foil and the substrate, the flatness of the pad and the like are better than those of the flexible flexible board, and the copper foil is good. The thinner the thickness, the better the folding resistance will be, which will facilitate the placement of bare chips (COF) on the flexible board.
  • COF bare chips
  • FPCB flexible plastic printed circuit board
  • Sputtering/Plating This method uses a polyimide (PI) film as a substrate, and a metal layer is plated on the PI film by vacuum sputtering, and then electroplated (Electroplating). Increase the thickness of the copper layer.
  • PI polyimide
  • electroplated Electroplated
  • Coating method uses a copper foil as a substrate, and the synthesized polyimide resin is extrusion-coated on a roll of copper foil by a die, dried in an oven and imidized. After the (Imidization), a two-layer type soft board is formed. This method is mostly used for single-sided flexible boards, and it is difficult to manufacture double-sided soft board substrates.
  • Lamination This method uses a non-thermoplastic PI film as the base film, a thermoplastic PI film as the base film, and then a copper foil. After a short hot roll, the imidization is high. The laminate is treated to form a two-layer flexible board.
  • both the coating method and the hot pressing method require a copper foil as a substrate, and the thickness of the copper foil is difficult to be 5 ⁇ m or less, and it is difficult to meet the requirements of the microelectronics industry for the ultra-thin FPC.
  • Sputtering/electroplating enables ultra-thin FPC, but due to the surface roughness of polyimide film Low and chemically inert, sputter deposited copper films often have low peel strength and the technical threshold of the process is high and are still in the research stage.
  • the ion-adsorbing ink as a connecting layer between the resin substrate and the conductive copper plating merely replaces the glue (adhesive) in the process of the flexible flexible circuit board, and essentially requires a flexible flexible circuit board.
  • Patent document CN 101684554A discloses an electroless copper plating solution of a polyimide film and an electroless copper plating method thereof.
  • the example results of this patent did not test the peel strength of the most critical parameter, the copper film and the polyimide film. In fact, if only the polyimide film is cleaned, whether it is vacuum sputtering or electroless plating, the peeling strength of the metal film and the polyimide film is not up to standard.
  • the technical bottleneck of the preparation of the ultra-thin polyimide (PI) non-gel flexible printed wiring board substrate is the peeling strength of the polyimide film and the copper film (sputtering method or electroless plating). The problem, and the technical bottleneck has not been well resolved.
  • the present invention provides a method for preparing a substrate of an ultra-thin polyimide (PI) non-adhesive flexible printed wiring board (FPCB, also referred to as a soft board), which is applied to a polyimide film.
  • Plasma surface modification treatment followed by vacuum sputtering or electroless plating (also known as copper sinking), plating a copper film with a thickness of 100 nm or less, and finally plating the copper film to a desired thickness of the copper film.
  • An ultra-thin glueless flexible printed circuit board substrate having high peel strength is produced.
  • the surface treatment method of the polyimide provided by the present invention includes:
  • Polyimide film is placed in a low vacuum environment, using organic amine capacitive coupling discharge The plasma is processed and the polyimide film is treated;
  • step 2) placing the polyimide film obtained in the step 1) in a low vacuum environment, and pretreating the polyimide film using a plasma formed by a nitrogen capacitive coupling discharge bubbling with a metal salt solution;
  • the body power density of the low vacuum capacitive coupling discharge (power output power / (electrode area ⁇ spacing of two electrodes)) > 0.1 W / cm 3
  • the discharge voltage satisfies the electric field strength of the discharge region (discharge voltage / electrode spacing >5.0kV/m
  • the pressure range of the capacitive coupling discharge is 30Pa ⁇ 80Pa, which can ensure the etching and grafting effect.
  • the surface of the plasma-treated polyimide produced by the organic amine gas coupling discharge can realize surface grafting of the amino group and achieve surface etching and roughening thereof.
  • the organic amine is a fatty amine. More preferably, the organic amine is methylamine, ethylamine, propylamine, butylamine, pentylamine or hexylamine, and the isomers of the above amines are equally suitable for use in the present invention.
  • the plasma treatment time in step 1) is 5 to 10 s.
  • the surface of the plasma-treated polyimide formed by the capacitive coupling of nitrogen gas bubbled by the metal salt solution may further graft a reactive group such as a hydroxyl group or a sulfonate on the surface of the polyimide film while depositing metal element.
  • the gas is nitrogen. The reason for selecting nitrogen is to consume the hydrogen bond donor of polyimide, reduce the outgas of hydrogen during electroless plating, and improve the adhesion of the coating.
  • the plasma treatment time in step 2) is 10-30 s.
  • the pressure of the background vacuum environment of steps 1) and 2) is not more than 20 Pa.
  • the metal salt is a copper salt, a palladium salt or a nickel salt, and the metal salt is soluble in water.
  • the metal salt may be a nitrate, a sulfate or a chloride.
  • the concentration of the solution may be a saturated solution or a dilute solution of the corresponding metal salt, and the concentration thereof is preferably as large as possible; the metal salt forms a crystal nucleus in a similar crystallization process which is subsequently treated on the surface of the polyimide during the treatment. Therefore, those skilled in the art can select an appropriate concentration as needed.
  • the metal salt solution is a solution prepared from the corresponding metal salt and deionized water.
  • step 2) is injected with nitrogen gas bubbling with a copper sulfate solution (copper sulfate: deionized water hydrazine 1:2) for plasma discharge treatment for 10 to 30 seconds.
  • a copper sulfate solution copper sulfate: deionized water hydrazine 1:2
  • the copper, hydroxyl, and sulfonate reactive groups are derived from a copper sulfate solution.
  • step 2) injecting nitrogen gas bubbling with deionized water-diluted palladium solution (palladium solution: deionized water hydrazine 1:7) for plasma discharge treatment for 10 to 30 s.
  • the palladium solution is a palladium sulfate solution having a palladium concentration of 4000 mg/liter.
  • step 2) injecting nitrogen gas bubbling with a nickel chloride solution (nickel chloride: deionized water hydrazine 1:5) diluted with deionized water for plasma discharge treatment for 10 to 30 s.
  • nickel chloride solution nickel chloride: deionized water hydrazine 1:5
  • the vacuum sputtering or electroless plating is to deposit a copper film having a thickness of 50 to 100 nm on the surface of the polyimide.
  • the pH of the solution when electrolessly plating the copper film is less than 6, preferably 5-6.
  • the method of the invention not only does not require a binder (no glue), but also simplifies the process, reduces manpower investment and costs, and can reduce environmental pollution, and can be used for manufacturing ultra-thin glueless flexible printed circuit boards.
  • FIG. 1 is a schematic view of the preparation of an ultra-thin glueless flexible printed wiring board according to the present invention.
  • Reference numerals 1, plasma chamber; 2, polyimide film; 3, unwinding; 4, winding; 5, anode; 6, cathode electrode.
  • FIG. 1 a schematic diagram of an ultra-thin glueless flexible printed circuit board prepared by the present invention.
  • a polyimide film is placed in a plasma chamber, and a winding device includes a winding 4 and a unwinding 3, and a winding speed control of the winder The discharge treatment time of the polyimide film 2.
  • the polyimide film roll (thickness of 12.5, 25, 50 ⁇ m) produced by China Wanda Group is installed in the winding device of the low vacuum plasma generator cavity, and the vacuum is drawn below 20Pa.
  • the methanamine gas discharge generates plasma to etch and graft the amino acid on the polyimide film, and controls the speed of the winder to make the polyimide film pass through the plasma discharge zone for 5 to 10 seconds.
  • the bulk power density of the plasma discharge (power output power / (electrode area ⁇ pitch of two electrodes)) > 0.1 W / cm 3 , the discharge voltage satisfies the electric field strength (discharge voltage / electrode pitch) of the discharge region > 5.0 kV / m.
  • the alkali-resistant polyimide is treated with an alkaline methylamine gas discharge, and the discharge gas pressure ranges from 30 Pa to 80 Pa.
  • a plasma-treated polyimide film was subjected to vacuum sputtering copper plating using a commercial vacuum sputtering coater.
  • the vacuum sputtering copper plating film is required to have high density, and it is preferable that the thickness of the sputtering copper plating film is 50 to 100 nm.
  • the sputter-plated copper layer is thickened by electroplating, and the thickness of the plating layer of the copper film is controlled by adjusting the electroplating time to prepare a copper film of any thickness.
  • Table 1 is the surface roughness after plasma treatment of the PI film. It can be seen from the average roughness (Ra) value that the surface roughness of the plasma-treated PI film is significantly increased compared with the plasma-free sample, and increases with the treatment time, and the plasma treatment time increases. Above 10s, the average roughness increased by 40% to 65%. The improvement of the surface roughness of the PI film is very advantageous as to increase the bonding force of the sputter plating/electroless copper plating film.
  • Table 2 is a measure of the peel strength of a sputter-plated copper film after three different thicknesses of the PI film after different plasma treatment times. From the measurement results, it was found that the thickness of the PI film did not affect the treatment effect.
  • the PI film without plasma treatment cannot be plated with a copper film.
  • the copper film coated has good adhesion to PI, and the peel strength is >8.0 N/cm, which is higher than the industry standard ( ⁇ 7.5 N/cm).
  • the plasma treatment time is preferably 5 to 20 s.
  • Table 3 is a measure of the peel strength for different copper film thicknesses. The plasma treatment time was 10 s, and the thickness was increased by sputtering and plating. The results show that the thickness of the copper film of the flexible plate prepared by this technique does not affect the bonding force.
  • the plasma-treated polyimide film is directly subjected to electroless plating (sinking), and since the polyimide film is not resistant to alkali, it is stable to dilute acid.
  • the pH of the electroless plating solution of the conventional copper sinking process The value is in the range of 12.5 to 13.
  • an electroless plating solution having a low pH for example, a pH of about 5.
  • the electroless copper plating film is required to have high density, and the electroless copper plating film preferably has a thickness of 50 to 100 nm.
  • step (4) of the first embodiment Same as step (4) of the first embodiment.
  • Example 2 The flexible sheet prepared in Example 2 was comparable in quality to Example 1, but the manufacturing cost was further lowered.
  • the plasma discharge gas of the step (2) in the present embodiment is nitrogen gas which is bubbled with deionized water (palladium liquid: deionized water hydrazine 1:7), and subjected to plasma discharge treatment for 10 to 30 s.
  • the palladium solution was a palladium sulfate solution having a palladium concentration of 4000 mg/liter, and the rest was the same as in Example 1.
  • the plasma discharge gas of the step (2) in the present embodiment is a nitrogen gas bubbled with a nickel chloride solution (nickel chloride: deionized water hydrazine 1:5) diluted with deionized water, and subjected to plasma discharge treatment 10 to 30s, the rest is the same as in the first embodiment.
  • a nickel chloride solution nickel chloride: deionized water hydrazine 1:5

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  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

一种聚酰亚胺无胶柔性印刷线路板的制备方法，该方法包括如下步骤：1)聚酰亚胺薄膜置于低真空环境内，使用有机胺电容耦合放电产生的等离子体对其进行处理；2)将步骤1)得到的聚酰亚胺薄膜置于低真空环境内，使用经金属盐溶液鼓泡的氮气电容耦合放电形成的等离子体对其进行预处理；3)采用真空溅射镀或化学镀预镀处理步骤2)得到的聚酰亚胺薄膜，得到厚度小于100纳米的致密铜膜；4)通过电镀法将铜膜加厚到所需要厚度。该方法不仅不需要粘接剂，而且能简化工艺、减少人力投入和降低成本，并能减少环境污染，能用于制造超薄无胶柔性印刷线路板。

Description

一种聚酰亚胺无胶柔性印刷线路板的制备方法 技术领域
本发明属于微电子电路板材的制备技术领域，具体涉及一种聚酰亚胺的表面处理方法和线路基材的制备方法。
背景技术
超薄无胶柔性印刷线路板是微电子行业发展的趋势。按照柔性线路板的基材和铜箔的结合方式，柔性线路板可分为有胶柔性线路板和无胶柔性线路板。若按结构分类，其可以分为单面柔性线路板、双面柔性板、多层软板、软硬结合板等。虽然无胶柔性线路板的价格比有胶的柔性板要高得多，但它的柔韧性、铜箔和基材的结合力、焊盘的平面度等参数比有胶柔性板好，铜箔的厚度越薄其耐折性能会越好，利于柔性板上贴装裸露芯片(COF)。
当前无胶柔性印刷线路板(FPCB)基材的制造方法有三种：
1、溅射/电镀法(Suttering/Plating)：该方法以聚酰亚胺(PI)膜为基材，利用真空溅射镀膜在PI膜上镀上一层金属后，再进行电镀(Electroplating)增加铜层厚度。此法的优势是能生产超薄的二层型软板，铜膜厚度可达3～12微米薄，另外还可以生产双面不同厚度的软板。
2、涂布法(Casting)：该方法以铜箔为基材，将合成好的聚酰亚胺树脂用模头挤压涂布在成卷的铜箔上，经烘箱干燥及酰亚胺化(Imidization)后形成二层型软板。该方法多用于单面软板，对双面软板基材制造有困难。
3、热压法(Lamination)：该方法以非热塑性的PI薄膜为芯层基膜，以热塑性PI薄膜为表层基膜，再覆上铜箔，经过短时热辊压，酰亚胺化高温层压处理而形成二层型软板。
上述方法中涂布法和热压法都需要铜箔做基材，而铜箔的厚度难以做到5微米以下，难以满足微电子行业发展趋势对FPC超薄化的要求。
溅射/电镀法能够实现超薄的FPC，但由于受聚酰亚胺薄膜表面粗糙度 低及化学惰性的影响，溅射沉积的铜膜常常剥离强度低且该方法的技术门槛高，目前仍处于研究阶段。
2014年科技日报及各大网站转载报道了复旦大学材料科学系的杨振国教授的团队新近研发的一种制造双面柔性印制电路板的“印刷-吸附-催化加成法”新工艺。这种新工艺的核心是自主开发了专有的离子吸附油墨。作为树脂基板与导电镀铜之间的连接层，这种离子吸附油墨可催化化学镀反应，其中的胺基、羧基、羟基等特殊基团可以显著提高电路板基材和镀层间的界面粘附力，其可以为绿色、低成本、大规模、卷对卷制造柔性印制电路提供新途径。但这种离子吸附油墨作为树脂基板与导电镀铜之间的连接层的做法只是取代了有胶柔性线路板工艺中的胶(粘接剂)，本质上还需要胶柔性线路板。
专利文献CN 101684554A公开了一种聚酰亚胺薄膜的化学镀铜液及其化学镀铜方法。但是该专利的实例结果没有对最关键的一个参数——铜膜与聚酰亚胺薄膜的剥离强度进行测试。事实上，如果仅仅对聚酰亚胺薄膜进行清洗处理，无论是真空溅射镀还是化学镀，其金属膜与聚酰亚胺薄膜的剥离强度都不达标。
基于以上技术背景分析可以确认，超薄聚酰亚胺(PI)无胶柔性印刷线路板基材的制备的技术瓶颈是聚酰亚胺薄膜与铜膜(溅射法或化学镀)的剥离强度问题，而该技术瓶颈一直并未得到很好的解决。
发明内容
针对这一技术瓶颈，本发明提供了一种制备超薄聚酰亚胺(PI)无胶柔性印刷线路板(FPCB，也称软板)基材的方法，该方法对聚酰亚胺薄膜进行等离子体表面改性处理，然后进行真空溅射镀或化学镀(也称沉铜)，镀上致密厚度100纳米以下的铜膜，最后对铜膜进行电镀加厚到所需要的铜膜厚度，制造出剥离强度高的超薄无胶柔性印刷电路板基材。
本发明提供的聚酰亚胺的表面处理方法包括：
1)聚酰亚胺薄膜置于低真空环境下，使用有机胺电容耦合放电产生的 等离子体对其进行处理，并对聚酰亚胺薄膜进行处理；
2)将步骤1)得到的聚酰亚胺薄膜置于低真空环境内，使用经金属盐溶液鼓泡的氮气电容耦合放电形成的等离子体对聚酰亚胺薄膜其进行预处理；
3)采用真空溅射镀或化学镀预镀处理步骤2)得到的聚酰亚胺薄膜，得到厚度小于100纳米的致密铜膜；
4)通过电镀法将铜膜加厚到所需要厚度。
优选的，所述低真空电容耦合放电的体功率密度(电源输出功率/(电极面积×两电极的间距))>0.1W/cm3，放电电压满足放电区的电场强度(放电电压/电极间距)>5.0kV/m，电容耦合放电的气压范围是30Pa～80Pa，这样可以保证刻蚀和接枝效果。
所述有机胺气体耦合放电产生的等离子体处理聚酰亚胺的表面可以实现其表面接枝氨基并实现其表面刻蚀及粗糙化。
优选的，所述有机胺为脂肪胺。更优选的，所述有机胺为甲胺、乙胺、丙胺、丁胺、戊胺或己胺，前述胺类的异构体同样适用于本发明。
优选的，步骤1)中等离子体处理时间为5～10s。所述经金属盐溶液鼓泡的氮气电容耦合放电形成的等离子体处理聚酰亚胺的表面，可以在所述聚酰亚胺薄膜的表面进一步接枝羟基、磺酸根等活性基团，同时沉积金属元素。所述气体为氮气。选择氮气的原因为将聚酰亚胺的氢键供体消耗掉，减少化学镀时氢的出气，提高镀膜的结合力
优选的，步骤2)中等离子体处理时间为10-30s。
优选的，步骤1)和步骤2)的本底真空环境的压力不大于20Pa。
优选的，所述金属盐为铜盐、钯盐或镍盐，所述金属盐溶于水。所述的金属盐可以为硝酸盐、硫酸盐、氯化物。所述溶液的浓度可以为相应的金属盐的饱和溶液或者稀溶液，其浓度越大越好；所述的金属盐在处理时在聚酰亚胺的表面形成后续处理的类似结晶过程中的晶核，故本领域技术人员可以根据需要选择合适的浓度。
优选的，所述金属盐溶液为相应的金属盐和去离子水配制而成的溶液。
在本发明的一个实施例中，步骤2)注入经硫酸铜溶液(硫酸铜：去离子水≧1:2)鼓泡的氮气进行等离子体放电处理10～30s。铜元素、羟基、磺酸根活性基团来源于硫酸铜溶液。
在本发明的一个实施例中，步骤2)注入经去离子水稀释的钯液(钯液：去离子水≧1:7)鼓泡的氮气进行等离子体放电处理10～30s。此处钯液是含钯浓度为4000mg/升的硫酸钯溶液。
在本发明的一个实施例中，步骤2)注入经去离子水稀释的氯化镍溶液(氯化镍：去离子水≧1:5)鼓泡的氮气进行等离子体放电处理10～30s。
优选的，所述真空溅射镀或化学镀预镀在聚酰亚胺表面沉积厚度为50～100纳米的铜膜。
更优选的，化学镀镀铜膜时溶液的pH值小于6，优选5～6。
本发明的方法不仅不需要粘接剂(无胶)，而且能简化工艺、减少人力投入和降低成本，并能减少环境污染，能用于制造超薄无胶柔性印刷线路板。
附图说明
图1为本发明制备制造超薄无胶柔性印刷线路板的示意图。
附图标识：1、等离子体腔体；2、聚酰亚胺薄膜；3、放卷；4、收卷；5、阳电极；6、阴电极。
具体实施方式
如下为本发明实施例，其仅用于对本发明的解释而并非限制。
参见图1，本发明制备超薄无胶柔性印刷线路板的示意图，图1中，聚酰亚胺薄膜位于等离子体腔内，收卷装置包括收卷4和放卷3，收卷机的转速控制聚酰亚胺薄膜2的放电处理时间。
实施例1
(1)将中国万达集团生产的聚酰亚胺薄膜卷(厚度为12.5、25、50μm三种规格)安装到低真空等离子体发生器腔体的收卷装置中，真空抽到20Pa以下，通入甲胺气体放电产生等离子体对聚酰亚胺薄膜进行刻蚀和 接枝氨基处理，控制收卷机转速，使聚酰亚胺薄膜经过等离子体放电区的时间在5～10秒之间。等离子体放电的体功率密度(电源输出功率/(电极面积×两电极的间距))>0.1W/cm3,放电电压满足放电区的电场强度(放电电压/电极间距)>5.0kV/m。为了提高等离子体的刻蚀效率，采用碱性的甲胺气体放电对不耐碱的聚酰亚胺进行处理，放电气压范围是30Pa～80Pa。
(2)停止甲胺供给，继续抽气到真空度低于20Pa，注入经硫酸铜溶液(硫酸铜：去离子水≧1:2)鼓泡的氮气进行等离子体放电处理10～30s。停机进空气，取出聚酰亚胺薄膜卷，密封包装进入下一步工序溅射镀或化学镀。
(3)利用商用真空溅射镀膜机对经等离子体处理好的聚酰亚胺薄膜进行真空溅射镀铜膜。为了在下一步电镀加厚时电解液不损伤聚酰亚胺薄膜，要求真空溅射镀铜膜的致密性高，优选溅射镀铜膜厚度50～100nm。
(4)利用电镀法对溅射镀铜层进行加厚，通过调节电镀时间，控制铜膜的镀层厚度，可制备任意厚度的铜膜。
表格1是等离子体处理PI膜后的表面粗糙度。从平均粗糙度(Ra)值可以看到，与未经等离子体处理的原样相比较，经等离子体处理的PI膜表面粗糙度得到明显增加，随着处理时间的增加而增加，等离子体处理时间10s以上，平均粗糙度增加了40％～65％。PI膜表面粗糙度的提高非常有利与增加溅射镀/化学镀铜膜的结合力。表格2是三种厚度的PI膜经不同等离子体处理时间后溅射镀铜膜的剥离强度测量值。从测量结果发现，PI膜的厚度不影响处理效果。未经等离子体处理的PI膜，镀不上铜膜。经等离子体处理后，镀上的铜膜与PI的结合力好，剥离强度>8.0N/cm,高于行业标准(≥7.5N/cm)。等离子体处理时间大于20秒后，效果虽然也很好，但已有下降的趋势，因此优选等离子体处理时间5～20s。表格3是不同的铜膜厚度的剥离强度测量值。等离子体处理时间10s，经过溅射镀并电镀加厚。结果显示，该技术制备的柔板的铜膜厚度不影响结合力。
表格1.等离子体处理聚酰亚胺薄膜(PI膜)后的表面粗糙度。
Figure PCTCN2016090073-appb-000001
表格2.聚酰亚胺薄膜(PI膜)经不同等离子体处理时间后溅射镀铜膜的剥离强度。
Figure PCTCN2016090073-appb-000002
表格3.不同铜膜厚度的剥离强度。
Figure PCTCN2016090073-appb-000003
实施例2：
同实施例的步骤(1)。
同实施例的步骤(2)。
(3)对经等离子体处理好的聚酰亚胺薄膜直接进行化学镀(沉铜)，由于聚酰亚胺薄膜不耐碱性，对稀酸稳定。而常规沉铜工艺的化学镀液pH 值在12.5～13,为了避免化学镀液对聚酰亚胺薄膜的损伤而导致沉铜膜的剥离强度下降，需要配制低pH值的化学镀液，例如pH值为5左右。为了在下一步电镀加厚时电解液不损伤聚酰亚胺薄膜，要求化学镀铜膜的致密性高，优选化学镀铜膜厚度50～100nm。
(4)同实施例1的步骤(4)。
表格4.是等离子体处理聚酰亚胺薄膜(PI膜)10s后进行化学沉铜并电镀加厚后测得的铜膜与PI膜的剥离强度。实施例2制备的柔板其质量可与实施例1相媲美，但制造成本会进一步降低。
表格4.化学沉铜和电镀加厚的铜膜的剥离强度。
Figure PCTCN2016090073-appb-000004
实施例3
本实施例中步骤(2)的等离子体放电气体为经去离子水稀释的钯液(钯液：去离子水≧1:7)鼓泡的氮气，并进行等离子体放电处理10～30s。钯液是含钯浓度为4000mg/升的硫酸钯溶液，其余同实施例1。
实施例4
本实施例中步骤(2)的等离子体放电气体为经去离子水稀释的氯化镍溶液(氯化镍：去离子水≧1:5)鼓泡的氮气，并进行等离子体放电处理10～30s，其余同实施例1。
以上所述仅为本发明技术方案的较佳实施例而已，并不用以限制本发明申请，凡在本技术方案实质内容上所作的任何修改、等同替换和简单改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种聚酰亚胺无胶柔性印刷线路板的制备方法，包括：
    1)聚酰亚胺薄膜置于低真空环境内，使用有机胺电容耦合放电产生的等离子体对其进行处理；
    2)将步骤1)得到的聚酰亚胺薄膜置于低真空环境内，使用经金属盐溶液鼓泡的氮气电容耦合放电形成的等离子体对其进行预处理；
    3)采用真空溅射镀或化学镀预镀处理步骤2)得到的聚酰亚胺薄膜，得到厚度小于100纳米的致密铜膜；
    4)通过电镀法将铜膜加厚到所需要厚度。
  2. 根据权利要求1所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，步骤1)和步骤2)中所述电容耦合放电的体功率密度>0.1W/cm3,放电电压满足放电区的电场强度>5.0kV/m，电容耦合放电的气压范围是30Pa～80Pa。
  3. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，步骤1)中等离子体处理时间为5～10s。
  4. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，步骤2)等离子体处理时间为10-30s。
  5. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，步骤1)和步骤2)的本底真空环境的压力不大于20Pa。
  6. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，所述有机胺为脂肪胺。
  7. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，所述金属盐为铜盐、钯盐或镍盐，所述金属盐溶于水。
  8. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，所述金属盐溶液为相应的金属盐和去离子水配制而成的溶液。
  9. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法， 其特征在于，所述金属盐溶液为硫酸铜和去离子水配制而成的溶液，两者的质量比大于1：2；或所述金属盐溶液为钯液和去离子水配制而成的溶液，两者的质量比大于1：7；其中钯液是浓度为4000mg/L的硫酸钯溶液；或所述金属盐溶液为氯化镍和去离子水配制而成的溶液，两者的质量比大于1：5。
  10. 根据权利要求1或2所述的聚酰亚胺无胶柔性印刷线路板的制备方法，其特征在于，步骤3)化学镀预镀铜膜时，溶液的pH值为5～6。
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