TW202031935A - Layered body, and layered body manufacturing method - Google Patents

Layered body, and layered body manufacturing method Download PDF

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TW202031935A
TW202031935A TW108137396A TW108137396A TW202031935A TW 202031935 A TW202031935 A TW 202031935A TW 108137396 A TW108137396 A TW 108137396A TW 108137396 A TW108137396 A TW 108137396A TW 202031935 A TW202031935 A TW 202031935A
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layer
metal
aforementioned
plating layer
metal plating
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古谷聰健
白髮潤
深澤憲正
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日商Ｄｉｃ股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The present invention provides a layered body having: an insulating layer (A) that has a surface in which a trench is formed; a metal particulate layer (B) that is layered on the trench; and a metal plating layer (C) that is layered within the trench and on the metal particulate layer (B). The present invention also provides a layered body having a barrier metal plating layer (E) between the metal particulate layer (B) and the metal plating layer (C). The present invention further provides a layered body having a primer layer (D) between the insulating layer (A) and the metal particulate layer (B). These layered bodies can be manufactured according to a simple method without the use of large-scale vacuum equipment or similar, and allow a metal layer to be formed on a trench.

Description

積層體、及積層體之製造方法Laminated body and method for manufacturing laminated body

本發明係關於積層體、及積層體之製造方法。The present invention relates to a laminate and a method of manufacturing the laminate.

近年，由於轉向半導體元件的小型化、因高積體化而配線高密度化、多層配線化、晶圓級封裝(WLP)、面板級封裝(PLP)，而有銅、鈦等的配線及再配線之微細化的要求。In recent years, due to the shift to the miniaturization of semiconductor components, the increase in wiring density due to high integration, multi-layer wiring, wafer level packaging (WLP), panel level packaging (PLP), and copper, titanium and other wiring and re Requirements for miniaturization of wiring.

非專利文獻1中揭示，於高解析度之感光性材料形成溝槽圖案，於所得到的圖案上進行濺鍍藉此形成晶種層，其後，藉由進行電解鍍敷，而形成配線層。 [先前技術文獻] [非專利文獻]Non-Patent Document 1 discloses that a groove pattern is formed on a high-resolution photosensitive material, sputtering is performed on the obtained pattern to form a seed layer, and then electrolytic plating is performed to form a wiring layer . [Prior Technical Literature] [Non-Patent Literature]

[非專利文獻1] 滿倉一行、和其他4名，「2/2μm以下之絕緣可靠性優異之微細配線層的開發」、Mate2018(2018年1月30-31日、橫濱)，論文集，p.169-174[Non-Patent Document 1] Mancang and his party, and 4 others, "Development of a fine wiring layer with excellent insulation reliability below 2/2μm", Mate2018 (January 30-31, 2018, Yokohama), Proceedings, p .169-174

[發明欲解決之課題][The problem to be solved by the invention]

然而，就以濺鍍法在絕緣性樹脂層上形成晶種層之方法而言，為了形成晶種層而有需要大型真空設備，而有在設計上、基板大小被限定等問題。However, with regard to the method of forming a seed layer on an insulating resin layer by sputtering, large-scale vacuum equipment is required to form the seed layer, and there are problems such as limited design and substrate size.

本發明係鑒於上述課題而完成者，其目的係提供一種於溝槽形成金屬層之積層體，該積層體可不使用大型真空設備而以簡便的方法製造。此外，本發明提供該積層體之製造方法。 [用以解決課題之手段]The present invention was made in view of the above-mentioned problems, and its object is to provide a laminate in which a metal layer is formed in a trench, which can be manufactured by a simple method without using a large-scale vacuum equipment. In addition, the present invention provides a method of manufacturing the laminate. [Means to solve the problem]

本發明者們為了解決上述課題而進行專心研討的結果，發現藉由採用下述構成，可解決上述課題，進而完成本發明。As a result of intensive research in order to solve the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by adopting the following configuration, and completed the present invention.

亦即，本發明之積層體，其特徵在於具有： 具有經形成溝槽的面之絕緣層(A)、 積層於前述溝槽之金屬粒子層(B)、及 積層於前述溝槽內且前述金屬粒子層(B)上之金屬鍍敷層(C)。That is, the laminated body of the present invention is characterized by having: The insulating layer (A) with the grooved surface, The metal particle layer (B) laminated on the aforementioned groove, and The metal plating layer (C) laminated in the groove and on the metal particle layer (B).

本發明之積層體，係可藉由下述而得，例如：於形成於絕緣層(A)之溝槽上，塗布含有金屬粒子之分散液(b)而形成金屬粒子層(B)，其後，進行鍍敷處理，於前述金屬粒子層(B)上形成金屬鍍敷層(C)。The laminate of the present invention can be obtained by, for example, coating a dispersion liquid (b) containing metal particles on a trench formed in the insulating layer (A) to form a metal particle layer (B), which After that, a plating process is performed to form a metal plating layer (C) on the metal particle layer (B).

如此，本發明之積層體，由於於溝槽上形成金屬層(金屬鍍敷層)，故可不使用大型真空設備而以簡便的方法製造。In this way, the laminate of the present invention has a metal layer (metal plating layer) formed on the trench, so that it can be manufactured by a simple method without using a large-scale vacuum equipment.

此外，本發明之積層體之製造方法，其特徵在於具有： 準備具有經形成溝槽的面之絕緣層(A)之步驟(1)； 於前述溝槽塗布含有金屬粒子之分散液(b)，形成金屬粒子層(B)之步驟(2)；及 進行鍍敷處理，於前述溝槽內且前述金屬粒子層(B)上形成金屬鍍敷層(C)之步驟(3)。In addition, the manufacturing method of the laminated body of the present invention is characterized by having: Step (1) of preparing an insulating layer (A) having a surface on which grooves are formed; The step (2) of applying the dispersion liquid (b) containing metal particles to the aforementioned groove to form the metal particle layer (B); and Perform a plating process to form a metal plating layer (C) in the groove and on the metal particle layer (B) (3).

根據本發明之積層體之製造方法，由於於溝槽塗布含有金屬粒子之分散液(b)，而形成金屬粒子層(B)，其後，藉由鍍敷處理形成為金屬層之金屬鍍敷層(C)，因於溝槽形成金屬層(金屬鍍敷層)，故可不使用大型真空設備而以簡便的方法製造。此外，由於於溝槽塗布含有金屬粒子之分散液(b)，而形成金屬粒子層(B)，故於溝槽之底面與側壁兩者可形成比較均一厚度之金屬粒子層(B)。其結果，可於溝槽內形成均勻的金屬鍍敷層(C)。 [發明之效果]According to the manufacturing method of the laminated body of the present invention, the metal particle layer (B) is formed by coating the dispersion liquid (b) containing metal particles on the trench, and thereafter, metal plating is formed into the metal layer by plating treatment The layer (C) has a metal layer (metal plating layer) formed in the trench, so it can be manufactured by a simple method without using a large vacuum equipment. In addition, since the dispersion liquid (b) containing metal particles is applied to the trench to form the metal particle layer (B), a relatively uniform thickness of the metal particle layer (B) can be formed on both the bottom surface and the sidewall of the trench. As a result, a uniform metal plating layer (C) can be formed in the trench. [Effects of Invention]

根據本發明，可不使用大型真空設備而以簡便的方法製造，而可提供一種於溝槽形成金屬層之積層體。此外，可提供一種該積層體之製造方法。According to the present invention, it is possible to manufacture by a simple method without using a large-scale vacuum equipment, and it is possible to provide a laminate in which a metal layer is formed in a trench. In addition, a method for manufacturing the laminate can be provided.

[用以實施發明的形態][Form to implement the invention]

以下，針對本發明之實施態樣，參照圖面進行說明。以下，首先，針對本實施態樣的積層體之積層構成進行說明。Hereinafter, the embodiments of the present invention will be described with reference to the drawings. Hereinafter, first, the laminated structure of the laminated body of this embodiment will be described.

本發明之積層體具有：具有經形成溝槽的面之絕緣層(A)、積層於前述溝槽之金屬粒子層(B)、及積層於前述溝槽內且前述金屬粒子層(B)上之金屬鍍敷層(C)。The laminate of the present invention has an insulating layer (A) having a surface on which a groove is formed, a metal particle layer (B) laminated on the groove, and a metal particle layer (B) laminated in the groove and on the metal particle layer (B) The metal plating layer (C).

本說明書中，所謂的溝槽係指在一個表面側上形成，而不貫穿至另一面之線狀之溝槽。本說明書中，從一個表面側貫穿至另一面之貫穿孔(例如：通孔)並不相當於溝槽。亦即，即使具有前述貫穿孔，但不具有前述溝槽之積層體則不相當於本發明之積層體。另外，本發明之積層體，除了溝槽以外，亦可具備前述貫穿孔等。In this specification, the so-called groove refers to a linear groove formed on one surface side without penetrating to the other surface. In this specification, a through hole (for example, a through hole) that penetrates from one surface side to the other surface does not correspond to a groove. That is, even if it has the said through-hole, the laminated body which does not have the said groove does not correspond to the laminated body of this invention. In addition, the laminate of the present invention may be provided with the aforementioned through holes and the like in addition to the grooves.

本發明之積層體可在至少一部分之溝槽上形成金屬鍍敷層(C)，亦可在全部的溝槽上形成金屬鍍敷層(C)。此外，本發明之積層體亦可於全部的溝槽上形成金屬鍍敷層(C)。In the laminate of the present invention, the metal plating layer (C) may be formed on at least a part of the trenches, or the metal plating layer (C) may be formed on all the trenches. In addition, in the laminate of the present invention, a metal plating layer (C) may be formed on all trenches.

本說明書中，金屬鍍敷層(C)之上表面，可與絕緣層(A)之上表面成為同一平面，亦可高於絕緣層(A)之上表面，也可低於絕緣層(A)之上表面。也就是說，金屬鍍敷層(C)可形成於溝槽內全體，亦可僅形成於溝槽內之一部分。然而，從利用作為配線的觀點來看，金屬鍍敷層(C)之上表面較佳為與絕緣層(A)之面成為同一平面(例如：參照圖1)。又，本發明之積層體存在複數條溝槽，亦可存在平行配置複數條的溝槽之處(例如：參照圖1)。以下，就具體例進行說明。In this specification, the upper surface of the metal plating layer (C) can be the same plane as the upper surface of the insulating layer (A), or higher than the upper surface of the insulating layer (A), or lower than the insulating layer (A). ) The upper surface. In other words, the metal plating layer (C) may be formed in the entire trench, or may be formed only in a part of the trench. However, from the viewpoint of use as wiring, the upper surface of the metal plating layer (C) is preferably the same plane as the surface of the insulating layer (A) (for example, refer to FIG. 1). In addition, the laminate of the present invention has a plurality of grooves, and there may be a place where a plurality of grooves are arranged in parallel (for example, refer to FIG. 1). Hereinafter, a specific example will be described.

另外，以下說明之實施態樣係針對積層體具備基材、絕緣層(A)、底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)、及金屬鍍敷層(C)的情形進行說明，但本發明之積層體亦可至少具有絕緣層(A)、金屬粒子層(B)、及金屬鍍敷層(C)。In addition, the embodiment described below is for a laminate with a substrate, an insulating layer (A), a primer layer (D), a metal particle layer (B), a barrier metal plating layer (E), and metal plating The case of the layer (C) will be described, but the laminate of the present invention may have at least an insulating layer (A), a metal particle layer (B), and a metal plating layer (C).

圖1為本發明之一實施態樣的積層體之剖面模式圖。如圖1所示，積層體10具有基材12、絕緣層14、底漆層16、金屬粒子層18、位障金屬鍍敷層20、及金屬鍍敷層22。作為基材12並沒有特別限定，但較佳為成為形成絕緣層14時之支撐體者，可列舉例如：矽晶圓(silicon wafer)、晶片(chip)等。此外，基材12亦可具有可撓性。Fig. 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention. As shown in FIG. 1, the laminate 10 has a base material 12, an insulating layer 14, a primer layer 16, a metal particle layer 18, a barrier metal plating layer 20, and a metal plating layer 22. The base material 12 is not particularly limited, but it is preferably used as a support when the insulating layer 14 is formed, and examples thereof include silicon wafers and chips. In addition, the substrate 12 may also have flexibility.

於絕緣層14之上表面14a形成溝槽15。於溝槽15之底面15a上及溝槽15之側壁15b上形成底漆層16。底面15a上之底漆層16的厚度、與側壁15b上之底漆層16的厚度係成為相同程度。A trench 15 is formed on the upper surface 14a of the insulating layer 14. A primer layer 16 is formed on the bottom surface 15a of the trench 15 and on the sidewall 15b of the trench 15. The thickness of the primer layer 16 on the bottom surface 15a is the same as the thickness of the primer layer 16 on the side wall 15b.

於底漆層16上，沿者底漆層16形成金屬粒子層18。底面15a上之金屬粒子層18的厚度、與側壁15b上之金屬粒子層18的厚度係成為相同程度。On the primer layer 16, a metal particle layer 18 is formed along the primer layer 16. The thickness of the metal particle layer 18 on the bottom surface 15a is the same as the thickness of the metal particle layer 18 on the side wall 15b.

於金屬粒子層18上，沿著金屬粒子層18形成位障金屬鍍敷層20。底面15a上之位障金屬鍍敷層20的厚度、與側壁15b上之位障金屬鍍敷層20的厚度係成為相同程度。On the metal particle layer 18, a barrier metal plating layer 20 is formed along the metal particle layer 18. The thickness of the barrier metal plating layer 20 on the bottom surface 15a is the same as the thickness of the barrier metal plating layer 20 on the sidewall 15b.

於位障金屬鍍敷層20上，形成金屬鍍敷層22使填充溝槽15內。就本實施態樣而言，金屬鍍敷層22之上表面係成為與絕緣層14之上表面14a成為同一平面。On the barrier metal plating layer 20, a metal plating layer 22 is formed to fill the trench 15. In the present embodiment, the upper surface of the metal plating layer 22 becomes the same plane as the upper surface 14a of the insulating layer 14.

絕緣層14相當於本發明之絕緣層(A)。底漆層16相當於本發明之底漆層(D)。金屬粒子層18相當於本發明之金屬粒子層(B)。位障金屬鍍敷層20相當於本發明之位障金屬鍍敷層(E)。金屬鍍敷層22相當於本發明之金屬鍍敷層(C)。The insulating layer 14 corresponds to the insulating layer (A) of the present invention. The primer layer 16 corresponds to the primer layer (D) of the present invention. The metal particle layer 18 corresponds to the metal particle layer (B) of the present invention. The barrier metal plating layer 20 corresponds to the barrier metal plating layer (E) of the present invention. The metal plating layer 22 corresponds to the metal plating layer (C) of the present invention.

溝槽15之大小可因應積層體之用途而適宜設定。例如：從將複數的溝槽15(金屬鍍敷層22)高積體化的觀點來看，在可作為配線使用之範圍內小者為佳。另一方面，要求可耐高電壓、高電流的情形下，變得需要某程度的大尺寸。 從以上的觀點來看，溝槽15的深度d，較佳為0.5μm以上1000μm以下、更佳為0.5μm以上500μm以下、進一步較佳為0.5μm以上100μm以下。此外，溝槽15之寬w較佳為0.5μm以上1000μm以下、更佳為0.5μm以上500μm以下、進一步進較佳為0.5μm以上100μm以下。The size of the groove 15 can be appropriately set according to the purpose of the laminate. For example, from the viewpoint of high integration of the plurality of trenches 15 (metal plating layer 22), the smaller one is better within the range that can be used as wiring. On the other hand, when it is required to withstand high voltage and high current, a certain degree of large size becomes necessary. From the above viewpoints, the depth d of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and still more preferably 0.5 μm or more and 100 μm or less. In addition, the width w of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and still more preferably 0.5 μm or more and 100 μm or less.

如積層體10，存在複數條溝槽15的情形，複數的溝槽15間之距離a沒有特別限定，較佳為0.5μm以上1000μm以下、更佳為0.5μm以上500μm以下、進一步較佳為0.5μm以上100μm以下。特別是，如本實施態樣，具有位障金屬鍍敷層20的情形，位障金屬鍍敷層20可防止金屬鍍敷層22之金屬擴散到絕緣層14。此從實施例亦可清楚明白。因此，即使溝槽15間之距離a變小也不破壞絕緣，可防止溝槽15間短路。從以上的觀點來看，複數的溝槽15間的距離a，較佳為0.5μm以上1000μm以下、更佳為0.5μm以上500μm以下、進一步較佳為0.5μm以上100μm以下。此外，溝槽15之寬w較佳為0.5μm以上1000μm以下、更佳為0.5μm以上500μm以下、進一步進較佳為0.5μm以上100μm以下。 另外，本說明書中，所謂的溝槽15間的距離a，係指從一邊的溝槽15的側壁15a至最近的另一個溝槽15之側壁15a的距離。For the laminate 10, when there are a plurality of grooves 15, the distance a between the plurality of grooves 15 is not particularly limited, and is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and still more preferably 0.5 Above μm and below 100 μm. In particular, as in the present embodiment, when the barrier metal plating layer 20 is provided, the barrier metal plating layer 20 can prevent the metal of the metal plating layer 22 from diffusing to the insulating layer 14. This can be clearly understood from the examples. Therefore, even if the distance a between the trenches 15 becomes smaller, the insulation is not broken, and a short circuit between the trenches 15 can be prevented. From the above viewpoints, the distance a between the plurality of trenches 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and still more preferably 0.5 μm or more and 100 μm or less. In addition, the width w of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and still more preferably 0.5 μm or more and 100 μm or less. In addition, in this specification, the so-called distance a between the trenches 15 refers to the distance from the side wall 15 a of the trench 15 on one side to the side wall 15 a of the nearest trench 15.

積層體10的用途，沒有特別限定，但例如：可利用金屬鍍敷層22作為配線之配線層。The use of the laminate 10 is not particularly limited, but for example, the metal plating layer 22 can be used as a wiring layer for wiring.

積層體10係可藉由如後述而得，於形成於絕緣層(A)之溝槽上，塗布含有金屬粒子之分散液(b)而形成金屬粒子層(B)，其後，進行鍍敷處理，於前述金屬粒子層(B)上形成金屬鍍敷層(C)。也就是說，積層體10由於於溝槽上形成金屬層(金屬鍍敷層(C))，故無需大型真空設備。此外，形成金屬層前無需進行反濺鍍處理。此外，由於具有位障金屬鍍敷層20，故可防止溝槽15間之金屬擴散，即使距離a變狹窄亦可防止溝槽15間之短路。此從實施例亦可清楚明白。The laminate 10 can be obtained by coating the metal particle-containing dispersion (b) on the trench formed in the insulating layer (A) as described later to form the metal particle layer (B), and then plating Processing, forming a metal plating layer (C) on the aforementioned metal particle layer (B). That is, since the laminated body 10 forms a metal layer (metal plating layer (C)) on the trench, large-scale vacuum equipment is not required. In addition, there is no need to perform a back sputtering treatment before forming the metal layer. In addition, since the barrier metal plating layer 20 is provided, the metal diffusion between the trenches 15 can be prevented, and the short circuit between the trenches 15 can be prevented even if the distance a becomes narrow. This can be clearly understood from the examples.

以上，針對本實施態樣的積層體之積層構成的一個例子進行說明。In the foregoing, an example of the laminated structure of the laminated body of this embodiment has been described.

接著，針對本實施態樣的積層體所具備之各層進行說明。Next, each layer included in the laminate of this embodiment will be described.

[絕緣層(A)] 絕緣層(A)係藉由絕緣樹脂形成，並具有形成溝槽之面。作為前述絕緣樹脂，只要具有電絕緣性，則無特別限定，可列舉例如：聚醯亞胺、聚醯胺醯亞胺、聚醯胺、聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯、丙烯腈-丁二烯-苯乙烯(ABS)樹脂、ABS與聚碳酸酯之聚合物摻合物、聚(甲基)丙烯酸甲酯等之丙烯酸樹脂、聚四氟乙烯、聚偏二氟乙烯、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、聚乙烯、聚丙烯、聚胺基甲酸酯、液晶聚合物(LCP)、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、聚苯碸(PPSU)、環氧樹脂、纖維素奈米纖維等。 此外，前述絕緣樹脂亦可為感光性樹脂，可列舉例如：聚苯并

Figure 108137396-A0304-12-0059-1
唑前驅物樹脂、聚苯并
Figure 108137396-A0304-12-0059-1
唑樹脂、聚醯胺樹脂、聚醯亞胺前驅物樹脂、聚醯亞胺樹脂、酚醛樹脂、可溶酚醛樹脂、羥基苯乙烯樹脂等。此等感光性樹脂可為正型亦可為負型。此外，藉由對感光性樹脂照射圖案光，而可形成經圖案化之前述絕緣層(A)。再者，從可使前述絕緣層(A)更強韌來看，較佳為圖案化後使之熱硬化。[Insulating layer (A)] The insulating layer (A) is formed of an insulating resin and has a groove-forming surface. The aforementioned insulating resin is not particularly limited as long as it has electrical insulating properties, and examples include polyimide, polyimide imide, polyamide, polyethylene terephthalate, and polyethylene naphthalate. Ester, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, polymer blend of ABS and polycarbonate, acrylic resin such as poly(meth)acrylate, polytetrafluoroethylene, Polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyphenylene Sulfide (PPS), polystyrene (PPSU), epoxy resin, cellulose nanofiber, etc. In addition, the aforementioned insulating resin may also be a photosensitive resin, for example: polybenzo
Figure 108137396-A0304-12-0059-1
Azole precursor resin, polybenzo
Figure 108137396-A0304-12-0059-1
Azole resin, polyimide resin, polyimide precursor resin, polyimide resin, phenol resin, resol resin, hydroxystyrene resin, etc. These photosensitive resins may be positive or negative. In addition, by irradiating the photosensitive resin with patterned light, the patterned insulating layer (A) can be formed. Furthermore, in view of making the aforementioned insulating layer (A) stronger, it is preferable to heat-harden it after patterning.

作為前述絕緣層(A)，從實現使用該積層體所得之最終製品的輕量化及薄型化的觀點來看，較佳為使用1μm以上200μm以下左右之厚度者。As the aforementioned insulating layer (A), from the viewpoint of achieving weight reduction and thinning of the final product obtained by using the laminate, it is preferable to use a thickness of about 1 μm or more and 200 μm or less.

[底漆層(D)] 於前述溝槽之底面上及前述溝槽之側壁上，亦可設置底漆層(D)。前述底漆層(D)係以提高前述絕緣層(A)與金屬粒子層(B)之密著性作為目的而設置之層。[Primer layer (D)] A primer layer (D) can also be provided on the bottom surface of the groove and the side wall of the groove. The primer layer (D) is a layer provided for the purpose of improving the adhesion between the insulating layer (A) and the metal particle layer (B).

作為構成前述底漆層(D)之材料，可列舉例如：胺基甲酸酯樹脂、丙烯酸樹脂、將胺基甲酸酯樹脂作為殼將丙烯酸樹脂作為核之核・殼型複合樹脂、環氧樹脂、醯亞胺樹脂、醯胺樹脂、三聚氰胺樹脂、酚樹脂、脲甲醛樹脂、使多異氰酸酯與酚等之封端化劑反應而得之經封端異氰酸酯聚乙烯醇、聚乙烯吡咯啶酮(polyvinyl pyrrolidone)等。另外，將胺基甲酸酯樹脂作為殼將丙烯酸樹脂作為核之核・殼型複合樹脂，可藉由例如：於胺基甲酸酯樹脂存在下將丙烯酸單體聚合而得。此外，此等之樹脂係可使用1種亦可併用2種以上。Examples of the material constituting the primer layer (D) include: urethane resin, acrylic resin, core-shell composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin Resin, imine resin, amide resin, melamine resin, phenol resin, urea-formaldehyde resin, blocked isocyanate polyvinyl alcohol, polyvinylpyrrolidone ( polyvinyl pyrrolidone) and so on. In addition, a core-shell composite resin having a urethane resin as a shell and an acrylic resin as a core can be obtained by, for example, polymerizing an acrylic monomer in the presence of a urethane resin. In addition, one type of these resin systems may be used, or two or more types may be used in combination.

前述底漆層(D)係可藉由將用以形成前述底漆層(D)之底漆組成物(d)進行塗布、乾燥等而形成。The primer layer (D) can be formed by coating, drying, etc., the primer composition (d) used to form the primer layer (D).

作為前述底漆組成物(d)，可使用含有前述材料及溶媒者。As the aforementioned primer composition (d), those containing the aforementioned materials and solvents can be used.

作為前述溶媒，可使用各種有機溶劑、水性媒體。As the aforementioned solvent, various organic solvents and aqueous media can be used.

前述底漆層(D)係根據使用該積層體之用途等而異，較佳為例如：0.01μm以上300μm以下之厚度、更佳為0.01μm以上20μm以下之厚度。The aforementioned primer layer (D) varies depending on the application for which the laminate is used. For example, a thickness of 0.01 μm or more and 300 μm or less is preferable, and a thickness of 0.01 μm or more and 20 μm or less is more preferable.

[金屬粒子層(B)] 金屬粒子層(B)可直接積層在前述絕緣層(A)上、或隔著前述底漆層(D)而積層在前述絕緣層(A)上。作為構成前述金屬粒子層(B)之金屬可列舉例如：銅、銀、金、鎳、鈀、白金、鈷等。此等之中，從粒子表面不易被氧化、作為無電解鍍敷觸媒之高活性、高導電性之金屬、容易形成金屬鍍敷層(C)來看，較佳為銀。[Metal particle layer (B)] The metal particle layer (B) may be laminated directly on the insulating layer (A) or may be laminated on the insulating layer (A) via the primer layer (D). Examples of the metal constituting the metal particle layer (B) include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these, in view of the fact that the surface of particles is not easily oxidized, is a highly active and highly conductive metal as an electroless plating catalyst, and is easy to form a metal plating layer (C), silver is preferred.

[位障金屬鍍敷層(E)] 於前述金屬粒子層(B)上亦可設置位障金屬鍍敷層(E)。前述位障金屬鍍敷層(E)係以防止金屬鍍敷層(C)之金屬擴散作為目的而設置之層。作為構成前述位障金屬鍍敷層(E)之金屬，可列舉鎳、鎳-鉬、鎳-鉬-硼、鎳-鉬-磷、鉻、鈷、鈷-磷、鉬、鈷-鎢-磷、鈷-鎢-硼等。[Position barrier metal plating layer (E)] A barrier metal plating layer (E) can also be provided on the aforementioned metal particle layer (B). The aforementioned barrier metal plating layer (E) is a layer provided for the purpose of preventing metal diffusion of the metal plating layer (C). Examples of the metal constituting the barrier metal plating layer (E) include nickel, nickel-molybdenum, nickel-molybdenum-boron, nickel-molybdenum-phosphorus, chromium, cobalt, cobalt-phosphorus, molybdenum, cobalt-tungsten-phosphorus , Cobalt-tungsten-boron, etc.

[金屬鍍敷層(C)] 金屬鍍敷層(C)可直接積層於前述金屬粒子層(B)上、或隔著前述位障金屬鍍敷層(E)而積層在前述金屬粒子層(B)上。作為構成前述金屬鍍敷層(C)之金屬，可列舉銅、金、銀、鎳、鉻、鈷、錫等。此等之中，將前述金屬鍍敷層(C)作為配線用途使用的情形，從比較低成本、高導電性來看，較佳為銅。[Metal plating layer (C)] The metal plating layer (C) may be laminated directly on the metal particle layer (B) or may be laminated on the metal particle layer (B) via the barrier metal plating layer (E). Examples of the metal constituting the metal plating layer (C) include copper, gold, silver, nickel, chromium, cobalt, tin, and the like. Among these, when the aforementioned metal plating layer (C) is used for wiring purposes, from the viewpoint of relatively low cost and high conductivity, copper is preferred.

[金屬粒子層(B)與底漆層(D)之組合] 作為具有底漆層(D)之構成的情形，就金屬粒子層(B)與底漆層(D)之組合而言，較佳為作為金屬粒子層(B)係採用含有化合物(b1)及金屬粒子(b2)之層，其中化合物(b1)具有含有鹼性氮原子之基，作為底漆層(D)係採用含有具有官能基[X]之化合物(d1)之層。藉由作為此種構成，於金屬粒子層(B)中所含之前述化合物(b1)所具有之含有鹼性氮原子之基、與於前述底漆層(D)中所含之前述化合物(d1)所具有之官能基[X]反應而生成鍵結，可更加提高絕緣層(A)與金屬鍍敷層(C)之間的密著性。[Combination of metal particle layer (B) and primer layer (D)] In the case of a configuration having a primer layer (D), in terms of the combination of the metal particle layer (B) and the primer layer (D), it is preferable that the metal particle layer (B) adopts the compound (b1) and A layer of metal particles (b2), wherein the compound (b1) has a group containing a basic nitrogen atom, and as the primer layer (D), a layer containing a compound (d1) having a functional group [X] is used. With such a configuration, the basic nitrogen atom-containing group of the compound (b1) contained in the metal particle layer (B) and the compound (b1) contained in the primer layer (D) The functional group [X] contained in d1) reacts to form a bond, which can further improve the adhesion between the insulating layer (A) and the metal plating layer (C).

作為前述化合物(b1)所具有之含有鹼性氮原子之基，可列舉例如：亞胺基、1級胺基、2級胺基等。Examples of the group containing a basic nitrogen atom contained in the compound (b1) include an imino group, a primary amino group, and a secondary amino group.

使用於分子中具有複數個含有鹼性氮原子之基者作為前述化合物(b1)的情形，前述含有鹼性氮原子之基係一方面於形成前述金屬粒子層(B)時，參與與於底漆層(D)中所含之化合物(d1)的官能基[X]鍵結，另一方面，有助於與金屬粒子層(B)中之銀等的金屬粒子(b2)之相互作用，而在提升前述金屬粒子層(B)與前述底漆層(D)之密著性方面是較佳的。When used in the molecule with a plurality of groups containing basic nitrogen atoms as the aforementioned compound (b1), the aforementioned basic nitrogen atom-containing groups are involved in the formation of the aforementioned metal particle layer (B). The functional group [X] of the compound (d1) contained in the paint layer (D) is bonded, and on the other hand, it contributes to the interaction with the metal particles (b2) such as silver in the metal particle layer (B), It is preferable to improve the adhesion between the metal particle layer (B) and the primer layer (D).

作為前述金屬粒子(b2)，可列舉例如：銅、銀、金、鎳、鈀、白金、鈷等。此外，此等之中，銅、銀及金因導電性高故較佳，再者銀由於比較便宜、粒子表面不易被氧化、作為無電解鍍敷觸媒之活性高故更佳。As said metal particle (b2), copper, silver, gold, nickel, palladium, platinum, cobalt, etc. are mentioned, for example. In addition, among these, copper, silver, and gold are preferred because of their high electrical conductivity. Furthermore, silver is better because it is relatively inexpensive, the particle surface is not easily oxidized, and has high activity as an electroless plating catalyst.

作為前述官能基[X]，可列舉酮基、環氧基、羧酸基、羧酸酐基、烷醇醯胺基、異氰酸酯基、乙烯基、鹵化烷基、丙烯醯基、氰胺基(cyanamide)、脲鍵、鹵化醯基等。前述酮基係指源自酮之羰基。從防止於常溫下反應的觀點來看，前述異氰酸酯基亦可藉由封端化劑而被封端。Examples of the functional group [X] include ketone groups, epoxy groups, carboxylic acid groups, carboxylic acid anhydride groups, alkanol amide groups, isocyanate groups, vinyl groups, halogenated alkyl groups, acrylamide groups, and cyanamide groups. ), urea bond, halogenated acyl group, etc. The aforementioned ketone group refers to a carbonyl group derived from a ketone. From the viewpoint of preventing the reaction at room temperature, the aforementioned isocyanate group may be blocked by a blocking agent.

其中，就官能基[X]而言，與前述化合物(b1)之含有鹼性氮原子之基反應時，從防止鹵素、酸、胺等副產物生成的觀點來看，較佳為使用自包含酮基、環氧基、酸基、烷醇醯胺基及異氰酸酯基之群組中選出之1種以上。Among them, as for the functional group [X], when reacting with the basic nitrogen-containing group of the aforementioned compound (b1), from the viewpoint of preventing the generation of by-products such as halogen, acid, amine, etc., it is preferable to use self-contained One or more selected from the group of ketone group, epoxy group, acid group, alkanol amine group, and isocyanate group.

作為前述具有官能基[X]之化合物(d1)，可使用例如具有前述官能基[X]之樹脂。作為具有前述官能基[X]之樹脂，具體而言，可使用具有前述官能基[X]之胺基甲酸酯樹脂、具有前述官能基[X]之乙烯系樹脂、具有前述官能基[X]之胺基甲酸酯-乙烯系複合樹脂、具有前述官能基[X]之環氧樹脂、具有前述官能基[X]之醯亞胺樹脂、具有前述官能基[X]之醯胺樹脂、具有前述官能基[X]之三聚氰胺樹脂、具有前述官能基[X]之酚樹脂、具有前述官能基[X]之聚乙烯醇、具有前述官能基[X]之聚乙烯吡咯啶酮等。其中，較佳為使用自包含具有前述官能基[X]之胺基甲酸酯樹脂、具有前述官能基[X]之乙烯系樹脂、及具有前述官能基[X]之胺基甲酸酯-乙烯系複合樹脂之群組中選出之1種以上。As the compound (d1) having the aforementioned functional group [X], for example, a resin having the aforementioned functional group [X] can be used. As the resin having the aforementioned functional group [X], specifically, a urethane resin having the aforementioned functional group [X], a vinyl resin having the aforementioned functional group [X], and the aforementioned functional group [X] can be used. ] Urethane-vinyl composite resin, epoxy resin with the aforementioned functional group [X], amide resin with the aforementioned functional group [X], amide resin with the aforementioned functional group [X], Melamine resin having the aforementioned functional group [X], phenol resin having the aforementioned functional group [X], polyvinyl alcohol having the aforementioned functional group [X], polyvinylpyrrolidone having the aforementioned functional group [X], etc. Among them, it is preferable to use a urethane resin having the aforementioned functional group [X], a vinyl resin having the aforementioned functional group [X], and a urethane resin having the aforementioned functional group [X]- One or more selected from the group of vinyl composite resins.

前述底漆層(D)係藉由使前述化合物(d1)之官能基[X]與前述金屬粒子層(B)中所含的前述化合物(b1)之含有鹼性氮原子之基反應而形成鍵結，其中前述化合物(d1)之官能基[X]係存在於藉由將含有具有官能基[X]之化合物(d1)的底漆組成物(d)於支撐體的表面，進行塗布、乾燥等所形成之塗膜中。The primer layer (D) is formed by reacting the functional group [X] of the compound (d1) with the basic nitrogen-containing group of the compound (b1) contained in the metal particle layer (B) Bonding, wherein the functional group [X] of the aforementioned compound (d1) is present by applying the primer composition (d) containing the compound (d1) having the functional group [X] on the surface of the support, In the coating film formed by drying etc.

前述底漆層(D)，於其表面接觸含有前述具有含有鹼性氮原子之基的化合物(b1)及金屬粒子(b2)等之分散液(b)時，藉由經過乾燥、加熱等之步驟，使前述化合物(b1)所具有之含有鹼性氮原子之基與前述塗膜中所含之前述化合物(d1)所具有之官能基[X]反應而形成鍵結，藉此形成由前述金屬粒子層(B)與底漆層(D)所構成之積層構造。When the primer layer (D) is in contact with the dispersion (b) containing the compound (b1) and metal particles (b2) having a group containing a basic nitrogen atom on its surface, it is dried, heated, etc. Step of reacting the basic nitrogen-containing group of the compound (b1) with the functional group [X] of the compound (d1) contained in the coating film to form a bond, thereby forming a bond A laminated structure composed of a metal particle layer (B) and a primer layer (D).

藉此，可以得到於前述金屬粒子層(B)與底漆層(D)之界面具備優異之密著性的積層體。Thereby, it is possible to obtain a laminate having excellent adhesion at the interface between the metal particle layer (B) and the primer layer (D).

前述底漆層(D)係可藉由將含有具有官能基[X]之化合物(d1)的底漆組成物(d)進行塗布、乾燥等而形成者。前述塗膜所含之化合物(d1)，具有與前述金屬粒子層(B)中所含的前述化合物(b1)之含有鹼性氮原子之基反應的官能基[X]。The aforementioned primer layer (D) can be formed by coating, drying, etc., a primer composition (d) containing a compound (d1) having a functional group [X]. The compound (d1) contained in the coating film has a functional group [X] that reacts with the basic nitrogen atom-containing group of the compound (b1) contained in the metal particle layer (B).

更詳細來說，金屬粒子層(B)與底漆層(D)之組合，係揭示於例如：國際公開第2013/146195號等。In more detail, the combination of the metal particle layer (B) and the primer layer (D) is disclosed in, for example, International Publication No. 2013/146195.

接著，針對本實施態樣的積層體10(參照圖1)之製造方法進行說明。圖2～圖5係用以說明本實施態樣的積層體之製造方法之剖面模式圖。Next, the manufacturing method of the laminated body 10 (refer FIG. 1) of this embodiment is demonstrated. 2 to 5 are schematic cross-sectional views for explaining the manufacturing method of the laminated body of this embodiment.

[積層體之製造方法] 本實施態樣的積層體之製造方法中，如圖2所示，首先，準備具有經形成溝槽15之面14a的絕緣層14(步驟(1))。所準備的絕緣層14除溝槽15以外亦可形成貫穿孔等。另外，絕緣層14亦可形成於圖2所示之基材12上，亦可為絕緣層14單一物體。[Method of manufacturing laminated body] In the manufacturing method of the laminated body of this embodiment, as shown in FIG. 2, first, the insulating layer 14 having the surface 14a on which the trench 15 is formed is prepared (step (1)). In addition to the trench 15, the prepared insulating layer 14 may form a through hole or the like. In addition, the insulating layer 14 may also be formed on the substrate 12 shown in FIG. 2, or may be a single object of the insulating layer 14.

經形成溝槽15之絕緣層14，係可藉由準備未形成溝槽之絕緣層，於此絕緣層上形成溝槽而得。作為對未形成溝槽之絕緣層形成溝槽之方法，係可採用例如：奈米壓印法(亦稱「壓紋加工法」。)、網版印刷法。此外，使用感光性樹脂作為絕緣層(A)之材料的情形，前述溝槽係可藉由下述方式而得，例如：藉由於使感光性樹脂硬化前的未硬化層，通過所欲之圖案遮罩曝光、顯影，作為經形成溝槽之未硬化層，進一步使前述未硬化層熱硬化。另外，前述感光性樹脂可為正型感光性，亦可為負型感光性。The insulating layer 14 where the trench 15 is formed can be obtained by preparing an insulating layer without a trench and forming a trench on the insulating layer. As a method for forming trenches on the insulating layer without trenches, for example, nanoimprinting method (also called "embossing method") and screen printing method can be used. In addition, when a photosensitive resin is used as the material of the insulating layer (A), the aforementioned grooves can be obtained by the following method, for example, by making the uncured layer before curing the photosensitive resin pass the desired pattern The mask is exposed and developed to serve as an unhardened layer in which grooves are formed, and the unhardened layer is further thermally hardened. In addition, the aforementioned photosensitive resin may be positively photosensitive or negatively photosensitive.

接著，因應需要，藉由於絕緣層14上塗布底漆組成物(d)，將底漆組成物(d)中所含之溶媒藉由乾燥等去除，而形成底漆層16(參照圖3)(步驟(1-1))。具體而言，沿著溝槽15之底面15a及側壁15b形成絕緣層14。 另外，採用上述說明之特定的組合作為金屬粒子層18及底漆層16的情形，底漆層16係藉由於絕緣層14上塗布底漆組成物(d)，因應需要進行乾燥等，而設置底漆層16，並藉由於前述塗膜之表面上，塗布含有前述具有含有鹼性氮原子之基的化合物(b1)及前述金屬粒子(b2)的分散液(b)後，經燒製等之加熱步驟而可製造。Then, as required, by coating the primer composition (d) on the insulating layer 14, the solvent contained in the primer composition (d) is removed by drying or the like, thereby forming the primer layer 16 (see FIG. 3) (Step (1-1)). Specifically, the insulating layer 14 is formed along the bottom surface 15a and the sidewalls 15b of the trench 15. In addition, when the specific combination described above is used as the metal particle layer 18 and the primer layer 16, the primer layer 16 is provided by coating the primer composition (d) on the insulating layer 14 and drying as required. The primer layer 16 is coated with a dispersion (b) containing the compound (b1) containing a basic nitrogen atom-containing group and the metal particles (b2) on the surface of the coating film, and then fired, etc. The heating step can be manufactured.

作為將前述底漆組成物(d)塗布於絕緣層14之表面的方法，可列舉例如：照相凹版法、膠版印刷法(offset method)、柔版法、移印印刷法(pad printing method)、照相凹版膠版印刷法(gravure offset method)、凸版法、反轉印刷法、網版法、微接觸法、背面印刷法(reverse method)、空氣刮刀塗布法(air doctor coater method)、刮刀塗布法(blade coater method)、氣動刮刀塗布法(air knife coater method)、擠壓塗布法(squeeze coater method)、含浸塗布法、轉印輥塗布法、輕觸塗布法(kiss coater method)、流延塗布法、噴霧塗布法、噴墨法、模頭塗布法、旋轉塗布法、棒式塗布法、浸漬塗布法等之方法。As a method of coating the aforementioned primer composition (d) on the surface of the insulating layer 14, for example, gravure method, offset method, flexographic method, pad printing method, Gravure offset method, relief printing method, reverse printing method, screen method, micro contact method, reverse method, air doctor coater method, doctor blade coating method ( blade coater method), air knife coater method, squeeze coater method, immersion coating method, transfer roll coating method, kiss coater method, cast coating method , Spray coating method, inkjet method, die coating method, spin coating method, bar coating method, dip coating method and other methods.

接著，於溝槽15上塗布含有金屬粒子之分散液(b)，形成金屬粒子層18(參照圖4)(步驟(2))。形成底漆層16的情形，沿著底漆層16形成金屬粒子層18。未形成底漆層16的情形，沿著絕緣層14(溝槽15的底面15a及側壁15b)形成金屬粒子層18。Next, a dispersion liquid (b) containing metal particles is applied on the trench 15 to form a metal particle layer 18 (see FIG. 4) (step (2)). When the primer layer 16 is formed, a metal particle layer 18 is formed along the primer layer 16. When the primer layer 16 is not formed, the metal particle layer 18 is formed along the insulating layer 14 (the bottom surface 15a and the side walls 15b of the trench 15).

於金屬粒子層18之形成上所使用的前述金屬粒子之形狀較佳為粒狀或纖維狀者。此外，前述金屬粒子的大小較佳為奈米尺寸。具體而言，前述金屬粒子的形狀為粒狀的情形，由於可形成微細圖案，可進一步降低電阻值，故平均粒徑較佳為1nm以上100nm以下、更佳為1nm以上50nm以下。另外，前述「平均粒徑」，係將前述金屬粒子以良好分散溶媒稀釋，藉由動態光散射法測定之體積平均值。此測定係可使用Microtrac公司製「Nanotrac UPA-150」。The shape of the aforementioned metal particles used in the formation of the metal particle layer 18 is preferably granular or fibrous. In addition, the size of the aforementioned metal particles is preferably a nanometer size. Specifically, when the shape of the aforementioned metal particles is granular, since a fine pattern can be formed and the resistance value can be further reduced, the average particle size is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less. In addition, the aforementioned "average particle size" is the volume average value measured by the dynamic light scattering method after diluting the aforementioned metal particles with a good dispersion solvent. For this measurement system, "Nanotrac UPA-150" manufactured by Microtrac Corporation can be used.

另一方面，前述金屬粒子的形狀為纖維狀的情形，由於可形成微細圖案，可進一步降低電阻值，故纖維之直徑較佳為5nm以上100nm以下、更佳為5nm以上50nm以下。此外，纖維的長度較佳為0.1μm以上100μm以下、更佳為0.1μm以上30μm以下。On the other hand, when the shape of the metal particles is fibrous, since a fine pattern can be formed and the resistance value can be further reduced, the diameter of the fiber is preferably 5 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. In addition, the length of the fiber is preferably 0.1 μm or more and 100 μm or less, more preferably 0.1 μm or more and 30 μm or less.

前述分散液(b)中前述金屬粒子的含有率，較佳為1質量%以上90質量%以下、更佳為1質量%以上60質量%以下、進一步更佳為1質量%以上10質量%以下。The content of the metal particles in the dispersion (b) is preferably 1% by mass to 90% by mass, more preferably 1% by mass to 60% by mass, and still more preferably 1% by mass to 10% by mass. .

作為於前述分散液(b)中所摻合之成分，可列舉用於將前述金屬粒子分散於溶媒中之分散劑或溶媒、或因應需要，後述之界面活性劑、調平劑、黏度調整劑、成膜助劑、消泡劑、防腐劑等。As the components blended in the aforementioned dispersion (b), a dispersant or solvent used to disperse the aforementioned metal particles in a solvent, or as required, surfactants, leveling agents, and viscosity regulators described later , Film forming aids, defoamers, preservatives, etc.

為了使前述金屬粒子分散於溶媒中，較佳為使用低分子量或高分子量之分散劑。作為前述分散劑，可列舉例如：十二烷硫醇、1-辛烷硫醇、三苯基膦、十二胺、聚乙二醇、聚乙烯吡咯啶酮、聚伸乙亞胺、聚乙烯吡咯啶酮；肉豆蔻酸、辛酸、硬脂酸等之脂肪酸；膽酸、甘草酸、樅酸等之具有羧基的多環式烴化合物等。於此等之中，從能提高前述金屬粒子層(B)與前述金屬鍍敷層(C)之密著性來看，較佳為高分子分散劑，作為此高分子分散劑，聚伸乙亞胺、聚伸丙亞胺等之聚伸烷亞胺、前述聚伸烷亞胺加成有聚氧化烯之化合物、胺基甲酸酯樹脂、丙烯酸樹脂、前述胺基甲酸酯樹脂或前述丙烯酸樹脂中含有磷酸基之化合物等。In order to disperse the aforementioned metal particles in a solvent, it is preferable to use a low-molecular-weight or high-molecular-weight dispersant. As the aforementioned dispersant, for example, dodecyl mercaptan, 1-octane mercaptan, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyethylene Pyrrolidone; fatty acids such as myristic acid, caprylic acid, and stearic acid; polycyclic hydrocarbon compounds with carboxyl groups such as cholic acid, glycyrrhizic acid, and abietic acid. Among these, from the viewpoint of improving the adhesion between the metal particle layer (B) and the metal plating layer (C), a polymer dispersant is preferred. As the polymer dispersant, polyethylene Polyalkyleneimines such as polyimine, polypropyleneimine, the aforementioned polyalkyleneimine compound with polyoxyalkylene added, urethane resin, acrylic resin, the aforementioned urethane resin, or the aforementioned Acrylic resin contains phosphoric acid-based compounds, etc.

相對於前述金屬粒子100質量份，為了使前述金屬粒子分散所需要的前述分散劑的使用量較佳為0.01質量份以上50質量份以下、更佳為0.01質量份以上10質量份以下。The amount of the dispersant required to disperse the metal particles is preferably 0.01 parts by mass or more and 50 parts by mass or less, and more preferably 0.01 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the metal particles.

作為前述分散液(b)中所使用的溶媒，可使用水性媒體、有機溶劑。作為前述水性媒體可列舉例如：蒸餾水、離子交換水、純水、超純水等。此外，作為前述有機溶劑可列舉醇化合物、醚化合物、酯化合物、酮化合物等。As the solvent used in the aforementioned dispersion (b), an aqueous medium and an organic solvent can be used. Examples of the aforementioned aqueous medium include distilled water, ion-exchanged water, pure water, ultrapure water, and the like. In addition, examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

作為前述醇化合物，可列舉例如：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、庚醇、己醇、辛醇、壬醇、癸醇、十一醇、十二醇、十三醇、十四醇、十五醇、硬脂醇、烯丙醇、環己醇、萜品醇、松油醇、二氫松油醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、二乙二醇單乙基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、四乙二醇單丁基醚、丙二醇單甲基醚、二丙二醇單甲基醚、三丙二醇單甲基醚、丙二醇單丙基醚、二丙二醇單丙基醚、丙二醇單丁基醚、二丙二醇單丁基醚、三丙二醇單丁基醚等。Examples of the aforementioned alcohol compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, heptanol, hexanol, octanol, and nonanol. , Decyl alcohol, undecyl alcohol, dodecanol, tridecyl alcohol, myristyl alcohol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, two Propylene glycol monobutyl ether, tripropylene glycol monobutyl ether, etc.

此外，前述分散液(b)中，除了前述金屬粒子、溶媒之外，因應需要亦可使用乙二醇、二乙二醇、1,3-丁二醇、異戊二醇等。In addition, in the aforementioned dispersion liquid (b), in addition to the aforementioned metal particles and solvent, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol, etc. can also be used as needed.

作為前述界面活性劑，可使用一般的界面活性劑，可列舉例如：二-2-乙基己基磺酸基琥珀酸鹽、十二基苯磺酸鹽、烷基二苯基醚二磺酸鹽、烷基萘磺酸鹽、六偏磷酸鹽等。As the aforementioned surfactant, general surfactants can be used, for example, di-2-ethylhexylsulfonate succinate, dodecylbenzenesulfonate, alkyl diphenyl ether disulfonate , Alkyl naphthalene sulfonate, hexametaphosphate, etc.

作為前述調平劑，可使用一般的調平劑，可列舉例如：聚矽氧系化合物、炔二醇系化合物、氟系化合物等。As the aforementioned leveling agent, a general leveling agent can be used, and examples thereof include polysiloxane-based compounds, acetylene glycol-based compounds, and fluorine-based compounds.

作為前述黏度調整劑，可使用一般的增黏劑，可列舉例如：藉由調整至鹼性而可增黏的丙烯酸聚合物或合成橡膠乳膠、藉由分子締合而可增黏的胺基甲酸酯樹脂、羥乙基纖維素、羧甲基纖維素、甲基纖維素、聚乙烯醇、氫化蓖麻油、醯胺蠟、氧化聚乙烯、金屬皂、二亞苄基山梨醇等。As the aforementioned viscosity modifier, general thickeners can be used, for example, acrylic polymers or synthetic rubber latexes that can be thickened by adjusting to alkaline, and urethanes that can be thickened by molecular association. Ester resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, etc.

作為前述成膜助劑，可使用一般的成膜助劑，可列舉例如：陰離子系界面活性劑(磺酸基琥珀酸二辛酯鈉鹽等)、疏水性非離子系界面活性劑(山梨糖醇酐單油酸酯等)、聚醚改質矽氧烷、聚矽氧油等。As the aforementioned film-forming aids, general film-forming aids can be used, such as anionic surfactants (dioctyl sulfosuccinate sodium salt, etc.), hydrophobic nonionic surfactants (sorbose Alcohol anhydride monooleate, etc.), polyether modified silicone, polysiloxane oil, etc.

作為前述消泡劑，可使用一般的消泡劑，可列舉例如：聚矽氧系消泡劑、非離子系界面活性劑、聚醚、高級醇、聚合物系界面活性劑等。As the aforementioned defoaming agent, general defoaming agents can be used, and examples thereof include silicone-based defoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer-based surfactants.

作為前述防腐劑，可使用一般的防腐劑，可列舉例如：異噻唑啉系防腐劑、三

Figure 108137396-A0304-12-0000-4
系防腐劑、咪唑系防腐劑、吡啶系防腐劑、唑系防腐劑、吡啶硫酮(pyrithione)系防腐劑等。As the aforementioned preservative, general preservatives can be used, for example, isothiazoline-based preservatives, three
Figure 108137396-A0304-12-0000-4
Preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, pyrithione preservatives, etc.

前述分散液(b)之黏度(於25℃使用B型黏度計測定之值)，較佳為0.1mPa・s以上500,000mPa・s以下、更佳為0.2mPa・s以上10,000mPa・s以下。此外，將前述分散液(b)藉由後述之噴墨印刷法、凸版反轉印刷等之方法進行塗布的情形，其黏度較佳為5mPa・s以上20mPa・s以下。The viscosity of the dispersion (b) (value measured at 25°C with a B-type viscometer) is preferably 0.1 mPa·s or more and 500,000 mPa·s or less, more preferably 0.2 mPa·s or more and 10,000 mPa·s or less. In addition, when the dispersion liquid (b) is applied by a method such as an inkjet printing method or a letterpress reverse printing method described later, the viscosity thereof is preferably 5 mPa·s or more and 20 mPa·s or less.

作為將前述分散液(b)塗布於底漆層16上的方法，可列舉例如：照相凹版法、膠版印刷法、柔版法、移印印刷法、照相凹版膠版印刷法、凸版法、反轉印刷法、網版法、微接觸法、背面印刷法、空氣刮刀塗布法、刮刀塗布法、氣動刮刀塗布法、擠壓塗布法、含浸塗布法、轉印輥塗布法、輕觸塗布法、流延塗布法、噴霧塗布法、噴墨法、模頭塗布法、旋轉塗布法、棒式塗布法、浸漬塗布法等之方法。As a method of coating the aforementioned dispersion liquid (b) on the primer layer 16, for example, gravure, offset printing, flexo, pad printing, gravure offset, relief, and reverse Printing method, screen method, micro contact method, back printing method, air knife coating method, knife coating method, pneumatic knife coating method, extrusion coating method, impregnation coating method, transfer roll coating method, light touch coating method, flow Methods such as spread coating method, spray coating method, inkjet method, die coating method, spin coating method, bar coating method, dip coating method, etc.

於此等之塗布方法中，當以實現電子電路等之高密度化時所要求之0.01以上100μm以下左右之細線狀形成圖案化之金屬粒子層18的情形，較佳為使用噴墨法、反轉印刷法。In these coating methods, when the patterned metal particle layer 18 is formed in fine lines of about 0.01 to 100 μm, which are required to achieve high density of electronic circuits, etc., it is preferable to use an inkjet method or reverse Transfer printing method.

作為前述噴墨印刷法，可使用一般稱為噴墨印表機者。具體而言，可列舉：Konica-Minolta EB100、XY100(Konica-Minolta IJ股份有限公司製)、Dimatix Materials Printer DMP-3000、Dimatix Materials Printer DMP-2831(富士軟片股份有限公司製)等。As the aforementioned inkjet printing method, what is generally called an inkjet printer can be used. Specifically, Konica-Minolta EB100, XY100 (manufactured by Konica-Minolta IJ Co., Ltd.), Dimatix Materials Printer DMP-3000, Dimatix Materials Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), etc. can be cited.

此外，作為反轉印刷法，已知有凸版反轉印刷法、凹版反轉印刷法，可列舉例如：於各種橡皮布(blanket)之表面塗布前述分散液(b)、使與非圖線部突出的版接觸、使對應前述非圖線部之分散液(b)選擇性地轉印至前述版的表面，藉此於前述橡皮布等之表面形成前述圖案，接著，將前述圖案轉印至前述支撐體(A)上(表面)的方法。In addition, as the reversal printing method, the relief reversal printing method and the gravure reversal printing method are known. For example, the dispersion liquid (b) is applied to the surface of various blankets and the NAND pattern is applied. The protruding plate contacts and selectively transfers the dispersion (b) corresponding to the non-patterned portion to the surface of the plate, thereby forming the pattern on the surface of the blanket, etc., and then transferring the pattern to The above-mentioned support (A) on (surface) method.

金屬粒子層18之每單位面積的質量宜為1mg/m2 以上30,000mg/m2 以下、較佳為1mg/m2 以上5,000mg/m2 以下。金屬粒子層18的厚度，係可藉由控制金屬鍍敷層22形成時之鍍敷處理步驟中的處理時間、電流密度、鍍敷用添加劑的使用量等來調整。Mass per unit area of the metal particle layer 18 is suitably 1mg / m 2 or more 30,000mg / m 2 or less, preferably 1mg / m 2 or more 5,000mg / m 2 or less. The thickness of the metal particle layer 18 can be adjusted by controlling the treatment time, the current density, the usage amount of the plating additive, and the like in the plating treatment step when the metal plating layer 22 is formed.

前述步驟(2)之後，因應需要，於金屬粒子層18上進行位障金屬鍍敷處理，而形成位障金屬鍍敷層20(圖5參照)(步驟(2-1))。具體而言，沿著金屬粒子層18之底面及側壁1形成位障金屬鍍敷層20。After the aforementioned step (2), as required, barrier metal plating is performed on the metal particle layer 18 to form a barrier metal plating layer 20 (refer to FIG. 5) (step (2-1)). Specifically, a barrier metal plating layer 20 is formed along the bottom surface of the metal particle layer 18 and the sidewall 1.

位障金屬鍍敷層20可藉由無電解鍍敷處理、或者電解鍍敷處理而形成。無電解鍍敷處理，例如：係藉由使金屬粒子層18與鎳、鉻、鈷等之無電解鍍敷液接觸，使無電解鍍敷液中所含之金屬析出，形成由位障金屬金屬皮膜構成之無電解鍍敷層(皮膜)的方法。The barrier metal plating layer 20 can be formed by an electroless plating process or an electrolytic plating process. Electroless plating treatment, for example, by contacting the metal particle layer 18 with an electroless plating solution such as nickel, chromium, cobalt, etc., the metal contained in the electroless plating solution is precipitated to form a barrier metal A method of electroless plating (film) composed of a film.

作為位障金屬鍍敷處理之還原劑，其係藉由使用次磷酸、次磷酸鈉、胺硼烷作為還原劑，而可得到於前述鎳、鉻、鈷等之金屬中包含磷、硼之合金膜。此外，於前述金屬之無電解鍍敷液中，進一步藉由使用經添加鎢、鉬、錸、釕等之鹽的無電解鍍敷液，可以形成經共析此等金屬之位障金屬鍍敷層20。As a reducing agent for barrier metal plating treatment, it can be obtained by using hypophosphorous acid, sodium hypophosphite, amine borane as reducing agents to obtain alloys containing phosphorus and boron in the aforementioned metals such as nickel, chromium, and cobalt membrane. In addition, in the electroless plating solution for the aforementioned metals, further by using an electroless plating solution added with salts of tungsten, molybdenum, rhenium, ruthenium, etc., barrier metal plating can be formed by eutectoids of these metals Layer 20.

位障金屬鍍敷處理係如上述，亦可為電解鍍敷處理。電解鍍敷處理可使用鎳、鉻、鈷等之電解鍍敷。The barrier metal plating process is as described above, and it may also be an electrolytic plating process. Electrolytic plating of nickel, chromium, cobalt, etc. can be used for electrolytic plating.

接著，進行鍍敷處理，於溝槽15內填充，於溝槽15內且金屬粒子層18上形成金屬鍍敷層22(參照圖1)(步驟(3))。形成位障金屬鍍敷層20的情形，於位障金屬鍍敷層20上進行鍍敷處理，形成金屬鍍敷層22。此外，未形成位障金屬鍍敷層20的情形，於金屬粒子層18上進行鍍敷處理，而形成金屬鍍敷層22。Next, a plating process is performed to fill the trench 15 to form a metal plating layer 22 in the trench 15 and on the metal particle layer 18 (refer to FIG. 1) (step (3)). When the barrier metal plating layer 20 is formed, a plating process is performed on the barrier metal plating layer 20 to form the metal plating layer 22. In addition, when the barrier metal plating layer 20 is not formed, a plating process is performed on the metal particle layer 18 to form the metal plating layer 22.

作為金屬鍍敷層22的形成方法，較佳為藉由鍍敷處理形成之方法。作為此鍍敷處理，可列舉可簡便地形成金屬鍍敷層22之電解鍍敷法、無電解鍍敷法等之濕式鍍敷法。此外，亦可組合此等鍍敷法。例如：實施無電解鍍敷後，亦可實施電解鍍敷，形成金屬鍍敷層22。As a method of forming the metal plating layer 22, a method of forming by plating treatment is preferable. As this plating treatment, a wet plating method such as an electrolytic plating method and an electroless plating method that can easily form the metal plating layer 22 can be cited. In addition, these plating methods can also be combined. For example, after electroless plating is performed, electrolytic plating may be performed to form the metal plating layer 22.

上述無電解鍍敷法係例如：藉由使金屬粒子層18、或位障金屬鍍敷層20與無電解鍍敷液接觸，而使無電解鍍敷液中所含之銅等的金屬析出，形成由金屬皮膜構成之無電解鍍敷層(皮膜)的方法。The above-mentioned electroless plating method is, for example, by bringing the metal particle layer 18 or the barrier metal plating layer 20 into contact with the electroless plating solution to precipitate metals such as copper contained in the electroless plating solution. A method of forming an electroless plating layer (film) composed of a metal film.

作為前述無電解鍍敷液，可列舉例如：含有銅、銀、金、鎳、鉻、鈷、錫等之金屬、與還原劑、與水性媒體、有機溶劑等之溶媒者。此外，使用金屬鍍敷層20作為導電層的情形，作為前述無電解鍍敷液之金屬種，較佳為導電性高的金屬之銀、銅、金，更佳為比較便宜的銅。Examples of the electroless plating solution include those containing metals such as copper, silver, gold, nickel, chromium, cobalt, and tin, and solvents such as reducing agents, aqueous media, and organic solvents. In addition, when the metal plating layer 20 is used as a conductive layer, the metal species of the aforementioned electroless plating solution is preferably silver, copper, and gold, which are highly conductive metals, and more preferably relatively inexpensive copper.

作為前述還原劑，可列舉例如：二甲基胺基硼烷、次磷酸、次磷酸鈉、肼、甲醛、硼氫化鈉、酚等。As said reducing agent, dimethylamino borane, hypophosphorous acid, sodium hypophosphite, hydrazine, formaldehyde, sodium borohydride, phenol etc. are mentioned, for example.

此外，作為前述無電解鍍敷液，因應需要，可使用含有乙酸、甲酸等之單羧酸；丙二酸、琥珀酸、己二酸、馬來酸、延胡索酸等之二羧化合物；蘋果酸、乳酸、羥乙酸、葡萄糖酸、檸檬酸等的羥基羧酸化合物；甘胺酸、丙胺酸、亞胺基二乙酸、精胺酸、天冬胺酸、麩胺酸等之胺基酸化合物；亞胺基二乙酸、氮基三乙酸(Nitrilotriacetic acid)、乙二胺二乙酸、乙二胺四乙酸、二伸乙三胺五乙酸等之胺基多羧酸化合物等之有機酸、或此等的有機酸之可溶性鹽(鈉鹽、鉀鹽、銨鹽等)、乙二胺、二伸乙三胺、三伸乙四胺等之胺化合物等的錯合劑者。In addition, as the aforementioned electroless plating solution, monocarboxylic acids containing acetic acid, formic acid, etc.; dicarboxylic compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid can be used as needed; Hydroxycarboxylic acid compounds such as lactic acid, glycolic acid, gluconic acid, and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamine; Organic acids such as amino polycarboxylic acid compounds such as aminodiacetic acid, Nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc., or these Soluble salts of organic acids (sodium salts, potassium salts, ammonium salts, etc.), complexing agents such as amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine.

前述無電解鍍敷液較佳為於20℃以上98℃以下使用。The aforementioned electroless plating solution is preferably used at 20°C or higher and 98°C or lower.

前述電解鍍敷法係例如：於金屬粒子層18、藉由前述無電解處理形成的無電解鍍敷層(皮膜)、或位障金屬鍍敷層20之表面，於接觸電解鍍敷液的狀態下通電，藉此使前述電解鍍敷液中所含的銅等之金屬在設置於陰極之層(金屬粒子層18、藉由前述無電解處理形成的無電解鍍敷層(皮膜)、或位障金屬鍍敷層20)的表面上析出，而形成電解鍍敷層(金屬皮膜)的方法。The aforementioned electrolytic plating method is, for example, on the surface of the metal particle layer 18, the electroless plating layer (film) formed by the aforementioned electroless treatment, or the barrier metal plating layer 20, in a state in which it is in contact with the electrolytic plating solution The lower energization causes metals such as copper contained in the electrolytic plating solution to be placed on the cathode layer (metal particle layer 18, the electroless plating layer (film) formed by the electroless treatment, or the position A method of depositing on the surface of the barrier metal plating layer 20) to form an electrolytic plating layer (metal film).

作為前述電解鍍敷液，可列舉例如：銅、銀、金、鎳、鉻、鈷、錫等之電解鍍敷液。此外，使用金屬鍍敷層22作為導電層的情形，作為前述電解鍍敷液之金屬種，較佳為導電性高的金屬之銀、銅、金，更佳為比較便宜的銅。此外，使用金屬鍍敷層22作為導電層的情形，鍍敷金屬較佳為無共析物、高純度者。Examples of the electrolytic plating solution include electrolytic plating solutions of copper, silver, gold, nickel, chromium, cobalt, and tin. In addition, when the metal plating layer 22 is used as the conductive layer, as the metal species of the electrolytic plating solution, silver, copper, and gold, which are highly conductive metals, are preferable, and relatively inexpensive copper is more preferable. In addition, when the metal plating layer 22 is used as the conductive layer, the plating metal is preferably one having no eutectoid and having high purity.

前述電解鍍敷液較佳為於20℃以上98℃以下使用。The aforementioned electrolytic plating solution is preferably used at 20°C or higher and 98°C or lower.

作為金屬鍍敷層22的形成方法，為了於溝槽15內適宜地形成金屬鍍敷層22，可適宜地選擇或組合無電解鍍敷法及電解鍍敷法。特別是，於前述溝槽內全體地填充金屬鍍敷層(C)的情形，較佳為實施無電解鍍敷後，實施電解鍍敷之方法。另外，當形成金屬鍍敷層22時，於絕緣層(A)之整個表面上，形成金屬鍍敷層。此情形，因應需要，亦可將在形成溝槽的部分以外的表面上所形成之金屬鍍敷層去除，而使絕緣層(A)露出。金屬鍍敷層的去除方法，可採用過去周知之方法，例如：化學機械研磨(CMP；Chemical Mechanical Polishing)。 [實施例]As a method of forming the metal plating layer 22, in order to appropriately form the metal plating layer 22 in the trench 15, an electroless plating method and an electrolytic plating method can be appropriately selected or combined. In particular, when the metal plating layer (C) is filled in the entire trench, it is preferable to perform electroless plating after electroless plating. In addition, when the metal plating layer 22 is formed, a metal plating layer is formed on the entire surface of the insulating layer (A). In this case, if necessary, the metal plating layer formed on the surface other than the portion where the trench is formed may be removed to expose the insulating layer (A). The method for removing the metal plating layer can be a well-known method in the past, such as chemical mechanical polishing (CMP; Chemical Mechanical Polishing). [Example]

以下，關於本發明係使用實施例進行詳細地說明，本發明只要不超出其要旨，並不限於以下之實施例。Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as it does not exceed the gist.

[金屬粒子之分散液(b)的調製] 於乙二醇30質量份、與離子交換水70質量份之混合溶媒中，使用在聚伸乙亞胺中附加聚氧乙烯的化合物作為分散劑，使平均粒徑30nm之銀粒子分散，藉此調製金屬粒子分散液，該金屬粒子分散液含有金屬粒子、與具有作為反應性官能基之含有鹼性氮原子之基的高分子分散劑。接著，於所得到的金屬粒子分散液中，添加離子交換水、乙醇及界面活性劑，將其黏度調整至10mPa・s，藉此調製金屬粒子之分散液(b)。[Preparation of metal particle dispersion (b)] In a mixed solvent of 30 parts by mass of ethylene glycol and 70 parts by mass of ion-exchange water, a compound obtained by adding polyoxyethylene to polyethyleneimine is used as a dispersing agent to disperse silver particles with an average particle diameter of 30 nm, thereby A metal particle dispersion liquid is prepared, which contains metal particles and a polymer dispersant having a basic nitrogen atom-containing group as a reactive functional group. Next, ion-exchanged water, ethanol, and a surfactant are added to the obtained metal particle dispersion to adjust the viscosity to 10 mPa·s, thereby preparing a metal particle dispersion (b).

[底漆層(D)用樹脂之製造] 於具備攪拌機、回流冷卻管、氮氣導入管、溫度計的反應容器中，藉由使聚碳酸酯多元醇(使1,4-環己烷二甲醇與碳酸酯反應所得之酸基當量1,000g/當量的聚碳酸酯二醇)100質量份、2,2-二羥甲基丙酸9.7質量份、1,4-環己烷二甲醇5.5質量份、二環己基甲烷二異氰酸酯51.4質量份，於甲基乙基酮111質量份之混合溶劑中反應，得到在分子末端具有異氰酸酯基的胺基甲酸酯預聚物之有機溶劑溶液。[Manufacturing of resin for primer layer (D)] In a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, and a thermometer, the polycarbonate polyol (the acid group equivalent of 1,4-cyclohexanedimethanol and carbonate ester is reacted with 1,000 g/equivalent Polycarbonate diol) 100 parts by mass, 9.7 parts by mass of 2,2-dimethylolpropionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, 51.4 parts by mass of dicyclohexylmethane diisocyanate, and The reaction was carried out in 111 parts by mass of a mixed solvent of ethyl ketone to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.

接著，藉由於前述胺基甲酸酯預聚物之有機溶劑溶液中，添加三乙胺7.3質量份，藉由將前述胺基甲酸酯樹脂所具有之羧基的一部分或全部中和，進一步添加水355質量份充分攪拌，得到胺基甲酸酯預聚物之水性分散液。Next, by adding 7.3 parts by mass of triethylamine to the organic solvent solution of the aforementioned urethane prepolymer, by neutralizing part or all of the carboxyl groups of the aforementioned urethane resin, further adding 355 parts by mass of water was sufficiently stirred to obtain an aqueous dispersion of urethane prepolymer.

接著，藉由於前述水性分散液中，添加25質量%的乙二胺水溶液4.3質量份，並進行攪拌，而將粒狀之胺基甲酸酯預聚物予以鏈伸長，接著，藉由熟成‧脫溶劑，得到固體含量濃度30質量%之胺基甲酸酯樹脂的水性分散液。Then, by adding 4.3 parts by mass of a 25% by mass ethylenediamine aqueous solution to the aforementioned aqueous dispersion, and stirring, the granular urethane prepolymer is chain-extended, and then matured by ‧ The solvent was removed to obtain an aqueous dispersion of a urethane resin with a solid content concentration of 30% by mass.

於具備攪拌機、回流冷卻管、氮氣導入管、溫度計、單體混合物滴下用滴液漏斗、聚合觸媒滴下用滴液漏斗之反應容器中，加入去離子水140質量份、前述所得到之胺基甲酸酯樹脂的水分散液100質量份，一邊吹入氮氣一邊升溫至80℃。於升溫至80℃之反應容器內，攪拌下，將反應容器內溫度一邊保持在80±2℃，一邊耗費120分鐘從各個滴液漏斗滴下含有甲基丙烯酸甲酯60質量份、丙烯酸正丁酯10質量份、N-正丁氧基甲基丙烯醯胺30質量份之單體混合物、與過硫酸銨水溶液(濃度：0.5質量%)20質量份，並予以聚合。Into a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping the monomer mixture, and a dropping funnel for dropping the polymerization catalyst, 140 parts by mass of deionized water and the amine group obtained above were added With 100 parts by mass of the aqueous dispersion of the formate resin, the temperature was raised to 80°C while blowing in nitrogen. In the reaction vessel heated to 80°C, while stirring, the temperature in the reaction vessel was kept at 80±2°C while it took 120 minutes to drip from each dropping funnel containing 60 parts by mass of methyl methacrylate and n-butyl acrylate A monomer mixture of 10 parts by mass, 30 parts by mass of N-n-butoxymethacrylamide, and 20 parts by mass of ammonium persulfate aqueous solution (concentration: 0.5% by mass) were polymerized.

滴加結束後，於同溫度下攪拌60分鐘，然後，將前述反應容器內之溫度冷卻至40℃，隨後，添加去離子水使不揮發成分成為20質量%後，藉由以200網目濾布過濾，得到含有作為反應性官能基之羧基與N-正丁氧基甲基丙烯醯胺基之底漆層(D)用樹脂。After the dripping is completed, stir at the same temperature for 60 minutes, then cool the temperature in the reaction vessel to 40°C, then add deionized water to make the non-volatile content 20% by mass, and then use a 200-mesh filter cloth It was filtered to obtain a resin for primer layer (D) containing a carboxyl group as a reactive functional group and an N-n-butoxymethacrylamide group.

[含有底漆層(D)用樹脂之底漆組成物(d)的調製] 在前述底漆層(D)用樹脂之製造所得之底漆層(D)用樹脂10質量份中，攪拌混合乙醇90質量份，得到含有底漆層(D)用樹脂之流動體(底漆組成物(d))。[Preparation of primer composition (d) containing resin for primer layer (D)] In 10 parts by mass of the resin for the primer layer (D) obtained from the production of the resin for the primer layer (D), 90 parts by mass of ethanol were stirred and mixed to obtain a fluid (primer paint) containing the resin for the primer layer (D) Composition (d)).

[積層體之製作] (實施例1) 使用旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)，將非感光性之聚醯亞胺前驅物樹脂(東麗股份有限公司製「SEMICOFINE SP-341」)於矽晶圓上塗布後，以加熱板依序於95℃加熱1分30秒、於125℃加熱1分30秒，得到膜厚5μm之絕緣層。 使用旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)，將正型感光性之聚醯亞胺前驅物樹脂(東麗股份有限公司製「PHOTONEECE LT6300」)於前述絕緣層上塗布後，以加熱板於120℃乾燥3分鐘，得到膜厚7μm之塗膜。接著，通過線寬5μm、線間隔5μm、線長1000μm之圖案光罩曝光。另外，所謂的線間隔，係指溝槽間之距離a，且係指一條線與另一條線之間的絕緣層部分的長度。 接著，噴灑2.38質量%之氫氧化四甲銨水溶液的顯影液180秒，接著以純水洗淨30秒後，使用潔淨烘箱，在氮氣環境下，依序於50℃加熱30分鐘、於110℃加熱30分鐘、於200℃加熱60分鐘，使之硬化，藉此得到深度5μm之具有經形成溝槽的面之絕緣層(A)。[Production of multilayer body] (Example 1) Using a spin coating device ("MS-A150" manufactured by MIKASA Co., Ltd.), the non-photosensitive polyimide precursor resin ("SEMICOFINE SP-341" manufactured by Toray Co., Ltd.) was coated on the silicon wafer. , Using a hot plate to sequentially heat at 95°C for 1 minute and 30 seconds and 125°C for 1 minute and 30 seconds to obtain an insulating layer with a thickness of 5 μm. Using a spin coating device (MIKASA Co., Ltd. "MS-A150"), a positive photosensitive polyimide precursor resin (Toray Co., Ltd. "PHOTONEECE LT6300") was coated on the aforementioned insulating layer, It was dried on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 7 μm. Then, exposure was performed through a patterned mask with a line width of 5 μm, a line interval of 5 μm, and a line length of 1000 μm. In addition, the so-called line spacing refers to the distance a between the trenches, and refers to the length of the insulating layer between one line and another line. Next, spray a 2.38% by mass tetramethylammonium hydroxide aqueous solution developer solution for 180 seconds, and then rinse with pure water for 30 seconds, and then use a clean oven to sequentially heat at 50°C for 30 minutes and 110°C in a nitrogen environment. It is heated for 30 minutes and at 200°C for 60 minutes to harden it, thereby obtaining an insulating layer (A) having a grooved surface with a depth of 5 μm.

於所得之具有溝槽之絕緣層(A)上，將經上述調整之金屬粒子之分散液(b)以旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)塗布，使作為金屬粒子層之乾燥後的平均膜厚成為30nm。亦即，將金屬粒子之分散液(b)塗布於絕緣層(A)之底面、及側壁，使作為金屬粒子層之乾燥後的平均膜厚成為30nm。於80℃加熱30分鐘，於前述絕緣層(A)整個表面形成金屬粒子層(B)。On the obtained insulating layer (A) with grooves, the above-mentioned adjusted metal particle dispersion (b) is coated with a spin coater ("MS-A150" manufactured by MIKASA Co., Ltd.) to form a metal particle layer The average film thickness after drying becomes 30 nm. That is, the dispersion liquid (b) of the metal particles is applied to the bottom surface and the side walls of the insulating layer (A) so that the average film thickness after drying as the metal particle layer becomes 30 nm. Heated at 80°C for 30 minutes to form a metal particle layer (B) on the entire surface of the aforementioned insulating layer (A).

將於前述所形成的金屬粒子層(B)於無電解銅鍍敷液(奧野製藥工業股份有限公司製「OIC Copper」、pH12.5)中，以45℃浸漬12分鐘，進行無電解銅鍍敷，於前述絕緣層(A)整個表面形成由無電解鍍敷所致之銅鍍敷層(膜厚0.2μm)。此由無電解鍍敷所致之銅鍍敷層相當於金屬鍍敷層(C)。The metal particle layer (B) formed above is immersed in an electroless copper plating solution ("OIC Copper" manufactured by Okuno Pharmaceutical Co., Ltd., pH 12.5) at 45°C for 12 minutes to perform electroless copper plating To form a copper plating layer (film thickness: 0.2 μm) by electroless plating on the entire surface of the aforementioned insulating layer (A). This copper plating layer caused by electroless plating is equivalent to the metal plating layer (C).

藉由將前述銅鍍敷層設定於陰極側，將含磷銅設定於陽極側，使用含有硫酸銅之電解鍍敷液，以電流密度1.5A/dm2 進行10分鐘電解鍍敷，而於前述絕緣層(A)整個表面形成銅鍍敷膜，使溝槽內填充銅。作為前述電解鍍敷液，係使用硫酸銅70g/L、硫酸200g/L、氯離子50mg/L、添加劑(奧野製藥工業股份有限公司製「Top Lucina SF-M」)5ml/L。此銅鍍敷層(電解鍍敷層)也相當於金屬鍍敷層(C)。By setting the aforementioned copper plating layer on the cathode side and phosphorous copper on the anode side, using an electrolytic plating solution containing copper sulfate, electrolytic plating is performed at a current density of 1.5A/dm 2 for 10 minutes. A copper plating film is formed on the entire surface of the insulating layer (A) to fill the trench with copper. As the electrolytic plating solution, copper sulfate 70 g/L, sulfuric acid 200 g/L, chloride ion 50 mg/L, and additives ("Top Lucina SF-M" manufactured by Okuno Pharmaceutical Co., Ltd.) 5 ml/L were used. This copper plating layer (electrolytic plating layer) also corresponds to the metal plating layer (C).

藉由將前述金屬鍍敷層(C)的表層進行化學機械研磨(CMP；Chemical　Mechanical　Polishing)，去除除了溝槽內所填充以外的銅層。CMP係使用研磨機(SpeedFam股份有限公司製「18GPAW」)，以聚胺基甲酸酯獨立發泡型之研磨墊，研磨壓力30kPa、定盤旋轉數50rpm，並使用膠質氧化矽溶液之研磨劑來進行。The surface layer of the metal plating layer (C) is subjected to chemical mechanical polishing (CMP; Chemical "Mechanical" Polishing) to remove the copper layer except for the filling in the trench. CMP uses a polishing machine (“18GPAW” manufactured by SpeedFam Co., Ltd.), using a polyurethane foamable polishing pad, polishing pressure 30kPa, fixed plate rotation 50rpm, and using colloidal silica solution abrasive To proceed.

藉由以上方法，得到積層體，該積層體係於絕緣層(A)上所形成的溝槽內依序積層金屬粒子層(B)及金屬鍍敷層(C)而成。By the above method, a laminate is obtained. The laminate system is formed by sequentially laminating the metal particle layer (B) and the metal plating layer (C) in the trench formed on the insulating layer (A).

(實施例2) 與實施例1同樣地進行，得到具有經形成溝槽的面之絕緣層(A)。(Example 2) In the same manner as in Example 1, an insulating layer (A) having a surface on which grooves were formed was obtained.

於前述絕緣層(A)上，將含有底漆層(D)用樹脂之底漆組成物(d)以旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)進行塗布，使作為底漆層之乾燥後的膜厚成為100nm。然後於80℃加熱30分鐘，於前述絕緣層(A)整個表面形成底漆層(D)。On the aforementioned insulating layer (A), the primer composition (d) containing the resin for the primer layer (D) is coated with a spin coater ("MS-A150" manufactured by MIKASA Co., Ltd.) to make it a primer The film thickness after drying of the layer becomes 100 nm. Then, it was heated at 80°C for 30 minutes to form a primer layer (D) on the entire surface of the aforementioned insulating layer (A).

於前述底漆層(D)之表面上，與實施例1同樣地進行，形成金屬粒子層(B)與金屬鍍敷層(C)後，與實施例1同樣地進行，以CMP去除除了溝槽內所填充的銅以外之銅層。On the surface of the primer layer (D), it was performed in the same manner as in Example 1. After forming the metal particle layer (B) and the metal plating layer (C), it was performed in the same manner as in Example 1, and the grooves were removed by CMP. The copper layer other than the copper filled in the groove.

藉由以上方法，得到積層體，該積層體係於絕緣層(A))上所形成之溝槽內依序積層底漆層(D)、金屬粒子層(B)及金屬鍍敷層(C)而成。By the above method, a laminate is obtained. The primer layer (D), the metal particle layer (B) and the metal plating layer (C) are sequentially laminated in the groove formed on the insulating layer (A)). Become.

(實施例3) 除了使用無電解鎳-硼鍍敷液，代替於實施例1中所使用之無電解銅鍍敷液，形成無電解鎳-硼鍍敷層以外，藉由與實施例1同樣的方法，得到積層體。此無電解鎳-硼鍍敷層，相當於位障金屬鍍敷層(E)。亦即，於實施例3得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)而成。作為前述無電解鎳-硼鍍敷液，係使用奧野製藥工業股份有限公司製「TOP Chem alloy 66-LF」，於65℃浸漬2分鐘，形成膜厚0.2μm之鎳-硼鍍敷層。(Example 3) Except that an electroless nickel-boron plating solution was used instead of the electroless copper plating solution used in Example 1 to form an electroless nickel-boron plating layer, the same method as in Example 1 was used to obtain a laminate body. This electroless nickel-boron plating layer is equivalent to barrier metal plating layer (E). That is, in Example 3, a laminated body was obtained. The laminated system was laminated on the insulating layer (A) having the groove-formed surface, and the metal particle layer (B), the barrier metal plating layer (E) and Made of metal plating layer (C). As the aforementioned electroless nickel-boron plating solution, "TOP Chem alloy 66-LF" manufactured by Okuno Pharmaceutical Co., Ltd. was used and immersed at 65°C for 2 minutes to form a nickel-boron plating layer with a film thickness of 0.2 μm.

(實施例4) 除了使用前述無電解鎳-硼鍍敷液，代替於實施例2中所使用之無電解銅鍍敷液，形成鎳-硼鍍敷層以外，藉由與實施例2同樣的方法，得到積層體。此鎳-硼鍍敷層，相當於位障金屬鍍敷層(E)。亦即，於實施例4得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)而成。(Example 4) Except that the foregoing electroless nickel-boron plating solution was used instead of the electroless copper plating solution used in Example 2 to form a nickel-boron plating layer, the same method as in Example 2 was used to obtain a laminate . This nickel-boron plating layer is equivalent to barrier metal plating layer (E). That is, in Example 4, a laminate was obtained. The laminate system was laminated on the insulating layer (A) having the groove-formed surface, and the primer layer (D), the metal particle layer (B), and the barrier metal were sequentially laminated. It is formed by plating layer (E) and metal plating layer (C).

(實施例5) 除了使用將金屬粒子層(B)之銀的一部分進行鈀取代後的無電解鎳-磷鍍敷液，代替於實施例4中所使用之無電解鎳-硼鍍敷液，形成鎳-磷鍍敷層以外，藉由與實施例4同樣的方法，得到積層體。此鎳-磷鍍敷層，相當於位障金屬鍍敷層(E)。亦即，實施例5係得到於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)之積層體。(Example 5) In addition to using an electroless nickel-phosphorus plating solution in which part of the silver in the metal particle layer (B) is replaced with palladium, instead of the electroless nickel-boron plating solution used in Example 4, a nickel-phosphorus plating is formed Except for the cladding layer, a laminate was obtained by the same method as in Example 4. This nickel-phosphorus plating layer is equivalent to the barrier metal plating layer (E). That is, in Example 5, a primer layer (D), a metal particle layer (B), and a barrier metal plating layer (E) were sequentially laminated on the insulating layer (A) having the grooved surface. And a laminate of metal plating layer (C).

作為前述鈀取代之方法，於離子交換水80質量份中，溶解氯化鈀3質量份與36質量%之鹽酸17質量份，調製含有鈀離子及酸之水溶液，將其設定為45℃，將絕緣層(A)、底漆層(D)、及金屬粒子層(B)之積層物浸漬於此鈀離子水溶液中，將金屬粒子層(B)之銀的一部分取代成鈀。As the method of palladium substitution, dissolve 3 parts by mass of palladium chloride and 17 parts by mass of 36% by mass hydrochloric acid in 80 parts by mass of ion-exchange water to prepare an aqueous solution containing palladium ions and acid, and set it to 45°C. The laminate of the insulating layer (A), the primer layer (D), and the metal particle layer (B) is immersed in the palladium ion aqueous solution to replace part of the silver in the metal particle layer (B) with palladium.

作為前述無電解鎳-磷鍍敷液，使用JCU股份有限公司製「ELFSEED 　ES-500」，於40℃浸漬10分鐘，形成膜厚0.2μm之鎳-磷鍍敷層。As the aforementioned electroless nickel-phosphorus plating solution, "ELFSEED "ES-500" manufactured by JCU Co., Ltd. was used and immersed at 40°C for 10 minutes to form a nickel-phosphorus plating layer with a thickness of 0.2 μm.

(實施例6) 除了使用無電解鈷鍍敷液，代替於實施例5中所使用之無電解鎳-磷素鍍敷液，形成鈷鍍敷層以外，藉由與實施例5同樣的方法，得到積層體。此鈷鍍敷層，相當於位障金屬鍍敷層(E)。亦即，實施例6係得到於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)之積層體。(Example 6) Except that an electroless cobalt plating solution was used instead of the electroless nickel-phosphorus plating solution used in Example 5 to form a cobalt plating layer, the same method as in Example 5 was used to obtain a laminate. This cobalt plating layer is equivalent to the barrier metal plating layer (E). That is, Example 6 was obtained by sequentially layering the primer layer (D), the metal particle layer (B), and the barrier metal plating layer (E) on the insulating layer (A) having the groove-formed surface. And a laminate of metal plating layer (C).

作為前述無電解鈷鍍敷液，含有硫酸鈷2質量份、檸檬酸6質量份、鎢酸5質量份、二甲基胺硼烷0.3質量份，使用經以氫氧化四甲銨將pH值調整至9.5之液體，於60℃浸漬35分鐘，形成膜厚0.2μm的鈷鍍敷層。As the aforementioned electroless cobalt plating solution, it contains 2 parts by mass of cobalt sulfate, 6 parts by mass of citric acid, 5 parts by mass of tungstic acid, and 0.3 parts by mass of dimethylamine borane. The pH is adjusted with tetramethylammonium hydroxide. Dip the liquid to 9.5 for 35 minutes at 60°C to form a cobalt plating layer with a film thickness of 0.2μm.

(實施例7) 除了使用具有形成線寬5μm、線間隔5μm、線長1,000μm、深度5μm的溝槽的面之脂肪族聚碳酸酯樹脂基材，代替於實施例2中所使用之聚醯亞胺前驅物樹脂及正型感光性之聚醯亞胺前驅物樹脂以外，藉由與實施例2同樣的方法，得到積層體。脂肪族聚碳酸酯樹脂基材係藉由將聚碳酸伸丙酯之二乙二醇單乙基醚乙酸酯溶液於矽晶圓上使用旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)進行塗布，以加熱板於150℃乾燥30分鐘，得到膜厚5μm之絕緣層後，以150℃具備凹凸之模具施加5MPa之壓力進行壓製，而獲得。亦即，於實施例7得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)及金屬鍍敷層(C)而成。(Example 7) In addition to the use of an aliphatic polycarbonate resin substrate having grooves with a line width of 5μm, a line spacing of 5μm, a line length of 1,000μm, and a depth of 5μm, instead of the polyimide precursor resin used in Example 2 Except for the positive photosensitive polyimide precursor resin, the same method as in Example 2 was used to obtain a laminate. The aliphatic polycarbonate resin substrate is made by applying a polypropylene carbonate solution of diethylene glycol monoethyl ether acetate on a silicon wafer using a spin coating device (MIKASA Co., Ltd. "MS-A150" ) Coating, drying on a hot plate at 150°C for 30 minutes to obtain an insulating layer with a film thickness of 5 μm, and then pressing with a mold with unevenness at 150°C under a pressure of 5 MPa. That is, in Example 7, a layered product was obtained. The layered system was formed on the insulating layer (A) having the grooved surface, and the primer layer (D), the metal particle layer (B), and the metal plating were sequentially laminated Layer (C) is formed.

(實施例8) 除了使用前述脂肪族聚碳酸酯樹脂基材，代替於實施例4中所使用之聚醯亞胺前驅物樹脂及正型感光性之聚醯亞胺前驅物樹脂以外，藉由與實施例4同樣的方法，得到積層體。亦即，於實施例8得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)而成。(Example 8) Except that the aforementioned aliphatic polycarbonate resin substrate was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4, the same as in Example 4 The method to obtain a laminate. That is, in Example 8, a laminate was obtained. The laminate system was laminated on the insulating layer (A) having the grooved surface, and the primer layer (D), the metal particle layer (B), and the barrier metal were sequentially laminated. It is formed by plating layer (E) and metal plating layer (C).

(實施例9) 除了使用前述脂肪族聚碳酸酯樹脂基材，代替於實施例6中所使用之聚醯亞胺前驅物樹脂及正型感光性之聚醯亞胺前驅物樹脂以外，藉由與實施例6同樣的方法，得到積層體。亦即，於實施例9得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)而成。(Example 9) Except that the aforementioned aliphatic polycarbonate resin substrate was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 6, the same as in Example 6 The method to obtain a laminate. That is, in Example 9, a laminate was obtained. The laminate system was laminated on the insulating layer (A) having the groove-formed surface, and the primer layer (D), the metal particle layer (B), and the barrier metal were sequentially laminated. It is formed by plating layer (E) and metal plating layer (C).

(實施例10) 使用旋轉塗布裝置(MIKASA股份有限公司製「MS-A150」)，將聚醯亞胺前驅物樹脂(東麗股份有限公司製「SEMICOFINE、SP-341」)於矽晶圓上進行塗布、並乾燥，使乾燥後之膜厚成為10μm。將所得到之塗膜設置於奈米壓印裝置(SCIVAX股份有限公司製「X300」)的下面載台上。將圖案表面經氟系處理之以石英作為材質之模具設置於上述裝置之上表面載台上。使裝置內抽真空後，以1.5氣壓之壓力使模具壓著於前述塗膜上，依序於95℃加熱硬化1分30秒、於125℃加熱硬化1分30秒。接著，將模具剝離，得到線寬5μm、線間隔5μm、線長1000μm、深度5μm之具有經形成溝槽的面之絕緣層(A)。(Example 10) Using a spin coating device (MIKASA Co., Ltd. "MS-A150"), the polyimide precursor resin (Toray Co., Ltd. "SEMICOFINE, SP-341") was coated on the silicon wafer and dried , Make the film thickness after drying 10μm. The obtained coating film was set on the lower stage of a nanoimprinting device ("X300" manufactured by Scivax Co., Ltd.). A mold made of quartz with a fluorine-based treatment on the pattern surface is set on the upper surface of the device. After evacuating the inside of the device, press the mold on the aforementioned coating film under a pressure of 1.5 atmospheres, and heat and cure at 95°C for 1 minute and 30 seconds and at 125°C for 1 minute and 30 seconds. Next, the mold was peeled off to obtain an insulating layer (A) having a grooved surface with a line width of 5 μm, a line interval of 5 μm, a line length of 1000 μm, and a depth of 5 μm.

除了使用前述絕緣層(A)，代替於實施例4中所使用之聚醯亞胺前驅物樹脂及正型感光性之聚醯亞胺前驅物樹脂以外，藉由與實施例4同樣的方法，得到積層體。亦即，實施例10係得到於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)之積層體。Except for using the aforementioned insulating layer (A) instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4, the same method as in Example 4 was used, Obtain a laminate. That is, Example 10 was obtained by sequentially stacking a primer layer (D), a metal particle layer (B), and a barrier metal plating layer (E) on the insulating layer (A) having the groove-formed surface And a laminate of metal plating layer (C).

(實施例11) 將厚度1mm的聚碳酸酯薄膜(旭硝子公司製LEXAN)設置於奈米壓印裝置(SCIVAX股份有限公司製「X300」)的下面載台上。將圖案表面經氟系處理之以石英作為材質之模具設置於上述裝置之上表面載台上。使裝置內抽真空後，於170℃、以2.5氣壓之壓力使模具壓著於前述聚碳酸酯薄膜上30秒。接著，將模具剝離，得到線寬5μm、線間隔5μm、線長1000μm、深度5μm之具有經形成溝槽的面之絕緣層(A)。(Example 11) A polycarbonate film (LEXAN manufactured by Asahi Glass Co., Ltd.) with a thickness of 1 mm was set on the lower stage of the nanoimprinting device ("X300" manufactured by SCIVAX Co., Ltd.). A mold made of quartz with a fluorine-based treatment on the pattern surface is set on the upper surface of the device. After evacuating the device, the mold was pressed against the polycarbonate film at 170°C under a pressure of 2.5 atm for 30 seconds. Next, the mold was peeled off to obtain an insulating layer (A) having a grooved surface with a line width of 5 μm, a line interval of 5 μm, a line length of 1000 μm, and a depth of 5 μm.

除了使用前述絕緣層(A)，代替於實施例4中所使用之聚醯亞胺前驅物樹脂及正型感光性之聚醯亞胺前驅物樹脂以外，藉由與實施例4同樣的方法，得到積層體。亦即，實施例11係得到於具有經形成溝槽的面之絕緣層(A)上，依序積層底漆層(D)、金屬粒子層(B)、位障金屬鍍敷層(E)及金屬鍍敷層(C)之積層體。Except for using the aforementioned insulating layer (A) instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4, the same method as in Example 4 was used, Obtain a laminate. That is, in Example 11, a primer layer (D), a metal particle layer (B), and a barrier metal plating layer (E) were sequentially laminated on the insulating layer (A) having the groove-formed surface. And a laminate of metal plating layer (C).

(比較例1) 於將與實施例1同樣製作之具有經形成溝槽的面之絕緣層(A)的表面上，使用徳田製作所製、RF濺鍍裝置，以出力300W、濺鍍壓力為0.5Pa、氬氣流量為40sccm進行反濺鍍之處理5分鐘。接著使用相同裝置，以依到達壓力5×10-4 Pa、濺鍍壓力0.2Pa、氬氣流量20sccm的條件之濺鍍法，於絕緣層(A)上依序形成0.2μm的鈦膜與0.6μm的銅膜。此鈦膜相當於位障層。銅膜係用以電解鍍敷之晶種層。接著，以與實施例1同樣的方法進行電解鍍敷，於溝槽內填充銅後，以CMP去除除了溝槽內所填充的銅以外之銅層。此銅鍍敷層，相當於金屬鍍敷層。 藉由以上方法，得到積層體，該積層體係於具有經形成溝槽的面之絕緣層(A)上，依序積層位障金屬層及金屬鍍敷層而成。(Comparative Example 1) On the surface of the insulating layer (A) with grooves formed in the same manner as in Example 1, an RF sputtering device manufactured by Tokuta Manufacturing Co., Ltd. was used with an output of 300 W and a sputtering pressure of 0.5 Pa, argon flow rate is 40sccm, and the back sputtering process is performed for 5 minutes. Then, using the same device, a 0.2μm titanium film and 0.6 were formed on the insulating layer (A) by the sputtering method under the conditions of reaching pressure of 5×10 -4 Pa, sputtering pressure of 0.2 Pa, and argon flow rate of 20 sccm. μm copper film. This titanium film is equivalent to the barrier layer. The copper film is a seed layer for electrolytic plating. Next, electrolytic plating was performed in the same manner as in Example 1, and after filling the trench with copper, the copper layer other than the copper filled in the trench was removed by CMP. This copper plating layer is equivalent to a metal plating layer. By the above method, a layered body is obtained. The layered system is formed by sequentially stacking barrier metal layers and metal plating layers on the insulating layer (A) having the groove-formed surface.

＜金屬鍍敷層之缺陷評價＞ 針對於實施例1～11及比較例1所得到之積層體，使用掃描型電子顯微鏡(SEM) (日本電子股份有限公司製「JSM-7800F」)，進行剖面觀察，確認金屬鍍敷層之缺陷的有無。剖面觀察係以倍率50000倍進行，隨機觀測10處。根據下述基準，評價金屬鍍敷層之缺陷。 ○：觀測10處，缺陷1個也沒有。 ×：觀測10處，缺陷為1個以上。＜Defect evaluation of metal plating layer＞ For the laminates obtained in Examples 1 to 11 and Comparative Example 1, a scanning electron microscope (SEM) was used ("JSM-7800F" made by JEOL Co., Ltd.), conduct cross-sectional observation to confirm the presence or absence of defects in the metal plating layer. The section observation system was carried out at a magnification of 50,000 times, and 10 locations were randomly observed. According to the following criteria, the defects of the metal plating layer were evaluated. ○: 10 places were observed, and there was no defect at all. ×: 10 places were observed, and there was 1 or more defect.

＜金屬鍍敷層之擴散評價＞ 針對於實施例1～11及比較例1所得之積層體，於設定成150℃之恆溫槽內保管168小時後，使用掃描型電子顯微鏡(SEM)(日本電子股份有限公司製「JSM-7800F」)，進行剖面觀察，藉由能量分散式X線(EDS)分析，觀測積層於溝槽內之金屬鍍敷層的金屬擴散至絕緣層的距離。根據下述基準，評價金屬鍍敷層之擴散。 ○：銅之擴散距離小於0.05μm △：銅之擴散距離為0.05μm以上小於0.10μm ×：銅之擴散距離為0.1μm以上＜Diffusion evaluation of metal plating layer＞ The laminates obtained in Examples 1 to 11 and Comparative Example 1 were stored in a thermostat set at 150°C for 168 hours, and then a scanning electron microscope (SEM) (manufactured by JEOL Co., Ltd. "JSM-7800F" was used ), conduct cross-sectional observation, and observe the distance from the metal of the metal plating layer deposited in the trench to the insulating layer by energy dispersive X-ray (EDS) analysis. According to the following criteria, the diffusion of the metal plating layer was evaluated. ○: The diffusion distance of copper is less than 0.05μm △: The diffusion distance of copper is more than 0.05μm and less than 0.10μm ×: The diffusion distance of copper is 0.1μm or more

[表1] 　 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 比較例1 絕緣層之種類 聚醯亞胺 脂肪族聚碳酸酯 聚醯亞胺 聚碳酸酯 聚醯亞胺 溝槽之形成方法 光照射、顯影 奈米壓印 奈米壓印 奈米壓印 光照射、顯影 底漆層之有無 無 有 無 有 有 有 無 金屬取代 無 Pd Pd 無 Pd 無 無 位障金屬鍍敷層之種類 無 無 Ni-B Ni-B Ni-P Co 無 Ni-B Co Ni-B Ni-B Ti 金屬鍍敷層之缺陷評價 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × 金屬鍍敷層之擴散評價 △ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative example 1 Type of insulating layer Polyimide Aliphatic polycarbonate Polyimide Polycarbonate Polyimide Method of forming trench Light irradiation, development Nanoimprint Nanoimprint Nanoimprint Light irradiation, development Presence of primer layer no Have no Have Have Have no Metal substitution no Pd Pd no Pd no no Types of barrier metal plating no no Ni-B Ni-B Ni-P Co no Ni-B Co Ni-B Ni-B Ti Defect evaluation of metal coating ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × Diffusion evaluation of metal coating △ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ×

從表1所示之結果可確認實施例1～10之積層體適宜地形成金屬鍍敷層。此外，確認金屬鍍敷層之擴散受到抑制。 然而，比較例1的積層體，並不形成金屬粒子層，取而代之的是藉由濺鍍形成位障層及晶種層而於此晶種層上形成金屬鍍敷層之實例，而可確認其於金屬鍍敷層上有缺陷，金屬鍍敷層之金屬擴散至絕緣層。在濺鍍的情形，被認為由於溝槽之底面與側壁之位障層及晶種層的厚度變得不均勻，特別是溝槽側壁之膜厚薄，而產生金屬鍍敷層缺陷，金屬鍍敷層的金屬從該缺陷擴散至絕緣層。From the results shown in Table 1, it can be confirmed that the laminates of Examples 1 to 10 suitably form a metal plating layer. In addition, it was confirmed that the diffusion of the metal plating layer was suppressed. However, in the laminate of Comparative Example 1, the metal particle layer is not formed. Instead, a barrier layer and a seed layer are formed by sputtering to form a metal plating layer on the seed layer, which can be confirmed There are defects on the metal plating layer, and the metal of the metal plating layer diffuses to the insulating layer. In the case of sputtering, it is believed that the thickness of the barrier layer and the seed layer on the bottom and sidewalls of the trench has become uneven, especially the thin film thickness of the trench sidewall, resulting in defects in the metal plating layer. The metal of the layer diffuses from the defect to the insulating layer.

10:積層體 12:基材 14:絕緣層 16:底漆層 18:金屬粒子層 20:位障金屬鍍敷層 22:金屬鍍敷層10: Laminated body 12: Substrate 14: Insulation layer 16: Primer layer 18: Metal particle layer 20: Barrier metal plating layer 22: Metal plating layer

[圖1] 為本發明之一實施態樣的積層體之剖面模式圖。 [圖2] 為用以說明本實施態樣的積層體之製造方法之剖面模式圖。 [圖3] 為用以說明本實施態樣的積層體之製造方法之剖面模式圖。 [圖4] 為用以說明本實施態樣的積層體之製造方法之剖面模式圖。 [圖5] 為用以說明本實施態樣的積層體之製造方法之剖面模式圖。[Figure 1] is a schematic cross-sectional view of a laminate in one embodiment of the present invention. [Fig. 2] is a schematic cross-sectional view for explaining the manufacturing method of the laminated body of this embodiment. [Fig. 3] is a schematic cross-sectional view for explaining the manufacturing method of the laminated body of this embodiment. [Fig. 4] is a schematic cross-sectional view for explaining the manufacturing method of the laminated body of this embodiment. [Fig. 5] is a schematic cross-sectional view for explaining the manufacturing method of the laminated body of this embodiment.

無。no.

Claims (6)

一種積層體，其特徵在於具有： 具有經形成溝槽的面之絕緣層(A)、 積層於前述溝槽之金屬粒子層(B)、及 積層於前述溝槽內且前述金屬粒子層(B)上之金屬鍍敷層(C)。A layered body characterized by: The insulating layer (A) with the grooved surface, The metal particle layer (B) laminated on the aforementioned groove, and The metal plating layer (C) laminated in the groove and on the metal particle layer (B). 如請求項1之積層體，其係於前述金屬粒子層(B)與前述金屬鍍敷層(C)之間，具有位障金屬鍍敷層(E)。The laminate of claim 1, which is between the metal particle layer (B) and the metal plating layer (C), and has a barrier metal plating layer (E). 如請求項1或2之積層體，其係於前述絕緣層(A)與前述金屬粒子層(B)之間，具有底漆層(D)。The laminate of claim 1 or 2, which is between the aforementioned insulating layer (A) and the aforementioned metal particle layer (B), and has a primer layer (D). 一種積層體之製造方法，其特徵在於具有： 準備具有經形成溝槽的面之絕緣層(A)之步驟(1)； 於前述溝槽塗布含有金屬粒子之分散液(b)，形成金屬粒子層(B)之步驟(2)及 進行鍍敷處理，於前述溝槽內且前述金屬粒子層(B)上形成金屬鍍敷層(C)之步驟(3)。A method for manufacturing a laminate, which is characterized by having: Step (1) of preparing an insulating layer (A) having a surface on which grooves are formed; Coating the dispersion liquid (b) containing metal particles on the aforementioned groove to form a metal particle layer (B) (2) and Perform a plating process to form a metal plating layer (C) in the groove and on the metal particle layer (B) (3). 如請求項4之積層體之製造方法，其係 於前述步驟(2)之後，具有於前述金屬粒子層(B)進行位障金屬鍍敷處理，而形成位障金屬鍍敷層(E)之步驟(2-1)， 於前述步驟(2-1)之後，進行前述步驟(3)。Such as the manufacturing method of the laminated body of claim 4, which is After the aforementioned step (2), there is a step (2-1) of performing barrier metal plating treatment on the aforementioned metal particle layer (B) to form a barrier metal plating layer (E), After the aforementioned step (2-1), the aforementioned step (3) is performed. 如請求項4或5之積層體之製造方法，其係 於前述步驟(1)之後，具有於前述絕緣層(A)塗布底漆組成物(d)，而形成底漆層(D)之步驟(1-1)， 於前述步驟(1-1)之後，進行前述步驟(2)。Such as the manufacturing method of the laminated body of claim 4 or 5, which is After the aforementioned step (1), there is a step (1-1) of coating the aforementioned insulating layer (A) with the primer composition (d) to form the primer layer (D), After the aforementioned step (1-1), the aforementioned step (2) is performed.
TW108137396A 2018-10-22 2019-10-17 Layered body, and layered body manufacturing method TW202031935A (en)

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