201251542 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種印刷配線基板以及選擇印刷配線 基板的方法。 【先前技術】 近年來’隨著電子機器的高功能化等要求，電子零件 的高密度集成化、高密度安裝化等正在推進，該些所&用 的印刷配線基板等亦正推進小型化且高密度化。在此種狀 況下，印刷配線基板中的配線的間隔更狹小化，為了防止 配線間的短路，亦要求配線間的絕緣可靠性進—步提高。 阻礙銅的配線間的絕緣性的要因之一已知有所謂銅離 子的遷移。其為如下現象：若在配線電路間等產生電位差， 則由於水分的存在，構成配線的銅離子化，溶出的銅離子 移動至鄰接的配線。根據上述現象，溶出的銅離子隨著時 間被還原而成為銅化合物，成長為樹枝狀結晶（樹枝狀晶） 狀，結果導致配線間短路。 防止上述遷移的方法提出有形成使用苯并三唑的遷移 抑制層的技術（專利文獻1及專利文獻2)。更具體而言， 該些文獻中，在配線基板上形成用以抑制銅離子遷移的 層，以配線間的絕緣可靠性的提高為目的。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2001-257451號公報 [專利文獻2]日本專利特開平1〇 321994號公報 201251542 4^υιυρίί 如上所述，近年來，配線的微細化急遽推進，對於配 線間的絕緣可靠性要求更進一步的提高。 本發明者等人對專利文獻1及專利文獻2中記載的使 用苯并三唑的遷移抑制層進行研究，結果其遷移抑制效果 無法滿足最近要求的水準，需要進一步的改良。 另外先别技術中，為了評價具備遷移抑制層的印刷 配線基板的配線間的絕緣性，需要對配線間施加長時間的 電壓’因此評價的效率差，$了判斷出哪一種印刷配線基 板顯示較佳結果而需要長時間H不僅必㈣入高價 的評價裝置’而且必需準備具備__評_印刷配線 基板等，因此其評價程序繁雜。 【發明内容】 本發明繁於上述情況’目的在於提供一種銅配線間的 絕緣可靠性優異的印刷配線基板。 另外，本發明的目的在於提供一種藉由更簡便的程序 來選擇銅配線間的絕緣可靠性優異的印刷配線基板的方 法。 本發明者等人進行積極研究，結果發現，與銅離子擴 散抑制層（遷移抑中所含_相互作用的含氮有機 化合物^銅配線表面上的附著量、以及將印刷配線基板浸 潰於規糾㈣水溶液中時的航_侧速㈣不且有 銅離子擴散抑制層的附有銅配線的基板的⑽速率之^， 和銅配線間的絕緣可靠性相關聯’從而完成本發明。 具體而言，發現可藉由以下構成來解決上述課題。 201251542 (1) 一種印刷配線基板，其包括： 附有銅配線的基板，具有基板及配置於基板上的銅配 線；以及 銅離子擴散抑制層，覆蓋銅配線且含有含氮有機化合 物；並且 含氮有機化合物的附著量為5.〇xl〇-9 g/mm2〜ι.〇χΐ〇-6 g/mm2，且 當使上述印刷配線基板浸潰於包含1·8質量％之硫酸 及12質量％之過氧二硫酸鈉的蝕刻水溶液中時的銅配線 的蝕刻速率（Β μπι/min)、與當使不具有銅離子擴散抑制 層的附有銅配線的基板浸潰於飯刻水溶液中時的銅配線的 触刻速率（Αμιη/min)之比（Β/Α)小於1.20。 (2) 如（1)所述之印刷配線基板，其中含氮有機化 合物包含唑化合物。 (3) 如（1)或（2)所述之印刷配線基板，其中含氮 有機化合物包含1，2,3-三唑及/或1，2,4-三唑。 (4 ) 一種選擇印刷配線基板的方法，其是從印刷配線 基板中選擇銅配線間的絕緣性優異的印刷配線基板的方 法’上述印刷配線基板包括：附有銅配線的基板，具有基 板及配置於上述基板上的銅配線；以及銅離子擴散抑制 層，覆蓋銅配線且含有含氮有機化合物；並且 含氮有機化合物的附著量為5.〇xl〇-9 g/mm2〜l.〇xl〇-6 g/mm2，且 當使上述印刷配線基板浸潰於包含1.8質量％之硫酸 201251542 4^UlUpif 及12質量％之過氧二硫酸納的钮刻水溶液中時的銅配線 的蝕刻速率（B μιη/min)、與當使不具有銅離子擴散抑制 層的附有銅配線的基板浸潰於钮刻水溶液中時的銅配線的 I虫刻速率（Αμπι/min)之比（B/A)小於1.2〇。 (5)如（4)所述之選擇印刷配線基板的方法，其中 含氮有機化合物包含唾化合物。 (6 )如（4 )或（5 )所述之選擇印刷配線基板的方法， 其中含氮有機化合物包含1，2,3-三唑及/或l，2,4-三唑。 [發明的效果] 依據本發明，可提供一種銅配線間的絕緣可靠 的印刷配線基板。 ' 另外，依據本發明，亦可提供一種藉由更簡便的程序 來選擇銅配線間的絕緣可靠性優異的印刷配線基板的方 法。 【實施方式】 以下’對本發明的印刷配線基板以及選擇印刷配線基 板的方法的較佳態樣進行詳細說明。 本發明的特徵可列舉如下方面：發現與鋼離子擴散抑 制層中所含的銅相互作用的含氮有機化合物在銅配線上的 附著量、以及當將印刷配線基板浸潰於規定的蝕刻水溶液 中時的銅配線的蝕刻速率與使用不具有銅離子擴散抑制層 的未處理的附有銅配線的基板時的蝕刻速率之比、與銅離 子的遷移抑制功能的關係。 通常’在將以有機皮膜覆蓋的附有銅配線的基板浸潰 201251542 於侧液巾的情況下，為了以有機皮膜錢銅配線，預想 不進行銅配線的蝕刻。另一方面，本發明者等人發現，若 將以遷移抑制功能優異的含有含氮有機化合物的銅離子擴 散抑制層所覆蓋的附有銅配線的基板浸潰於規定的蝕刻液 中，則顯不出固定範圍的銅配線的蝕刻速率。作為在使用 與銅相互作用的含氮有機化合物的情況下產生蝕刻的原 因，認為是由於螯合效應。在印刷配線基板的蝕刻速率、 與不具有銅離子擴散抑制層的附有銅配線的基板的蝕刻速 率之比為規定值以上的情況下，含氮有機化合物對銅的溶 解性變得過強，大量的銅離子包含於銅離子擴散抑制層 中，遷移抑制效果下降。 另外，在與銅離子擴散抑制層（遷移抑制層）的銅配 線上的銅相互作用的含氮有機化合物的附著量在規定範圍 内的情況下，由銅配線產生的銅離子的遷移得到抑制，結 果銅配線間的絕緣可靠性進一步提高。此外，若銅離子擴 散抑制層的附著量小，則捕捉由銅配線產生的銅離子的能 力低，結果無法抑制銅的樹枝狀結晶的產生等，無法擔保 銅配線間的絕緣可靠性。若附著量大，則在印刷配線基板 中阻礙銅配線與絕緣膜的密著，導致銅配線間的絕緣可靠 性惡化。 首先，對本發明的印刷配線基板中的含氮有機化合物 的附著量、以及銅配線的蝕刻速率進行詳細說明，且對其 後使用的印刷配線基板的構成進行詳細說明。 相對於銅配線的總表面積，銅離子擴散抑制層中的含 201251542 42UiUpif 氮有機化合物的附著量為5.〇xl〇-9 g/mm2〜丨〇χ1〇·6 g/mm ’ 較佳為 5.〇xl〇-9 g/mm2〜2.〇xl〇'7 g/mm2，更佳為 ^1〇8 g/mm2〜6.〇xl〇8 g/mm2。若含氮有機化合物的附 著量為上述範圍，則可抑制銅離子的遷移。 此外，附著量可利用公知的方法（例如吸光度測定法） 來測定。具體而言，首先利用水來清洗存在於銅配線間的 銅離子擴散抑制層（利用水的萃取法）。然後，利用有機酸 (例如硫酸）來萃取銅配線上的銅離子擴散抑制層，測定 吸光度，根據液量及塗佈面積來算出附著量。 關於本發明的印刷配線基板，當使該基板浸潰於包含 1.8質量％之硫酸及12質量％之過氧二硫酸鈉的蝕刻水溶 液中時的銅配線的钮刻速率（B pm/min )、與當使不具有 銅離子擴散抑制層的未處理的附有銅配線的基板浸潰於該 敍刻水溶液中時的銅配線的蝕刻速率（A pm/min)之比 (B/A)滿足小於1.2〇。 若上述#刻速率之比為上述範圍，則銅離子擴散抑制 層表現出優異的遷移抑制效果，結果銅配線間的絕緣可靠 性優異。其中’就遷移抑制效果更優異的方面而言，上述 儀刻速率之比較佳為小於丨1〇，更佳為小於i 〇5，尤佳為 小於1.00。此外，就銅離子擴散防止層的皮膜附著量的方 面而言’下限較佳為〇.6〇以上，更佳為〇·65以上。 另一方面，在上述蝕刻速率之比為1·2〇以上的情況 下’在高溫、高濕環境（例如高加速應力試驗（Highly201251542 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a printed wiring board and a method of selecting a printed wiring board. [Prior Art] In recent years, with the demand for higher functionality of electronic devices, high-density integration of electronic components and high-density mounting are progressing, and the printed wiring boards for these applications are being miniaturized. And high density. In such a case, the interval between the wirings in the printed wiring board is further narrowed, and in order to prevent short-circuiting between the wirings, the insulation reliability between the wirings is required to be further improved. One of the factors that hinder the insulation between the wirings of copper is known as the migration of so-called copper ions. In the case where a potential difference occurs between wiring circuits or the like, copper constituting the wiring is ionized by the presence of moisture, and the eluted copper ions move to the adjacent wiring. According to the above phenomenon, the eluted copper ions are reduced with time to become a copper compound, and grow into a dendritic crystal (dendritic crystal), resulting in a short circuit between wirings. A method for preventing the migration described above has been proposed to form a migration inhibiting layer using benzotriazole (Patent Document 1 and Patent Document 2). More specifically, in these documents, a layer for suppressing migration of copper ions is formed on the wiring substrate, and the purpose of improving insulation reliability between wirings is aimed at. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-257451 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. The miniaturization is rushing forward, and the insulation reliability of the wiring closet is further improved. The present inventors have studied the migration inhibiting layer using benzotriazole described in Patent Document 1 and Patent Document 2, and as a result, the migration inhibiting effect cannot satisfy the recently required level, and further improvement is required. In addition, in order to evaluate the insulation between the wirings of the printed wiring board including the migration suppression layer, it is necessary to apply a long-term voltage between the wirings. Therefore, the efficiency of evaluation is poor, and it is determined which type of printed wiring substrate is displayed. A good result requires a long time. H is not only required to enter the high-priced evaluation device, but also requires preparation of a printed wiring board or the like. Therefore, the evaluation procedure is complicated. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. It is an object of the invention to provide a printed wiring board having excellent insulation reliability between copper wirings. Further, an object of the present invention is to provide a method of selecting a printed wiring board having excellent insulation reliability between copper wirings by a simpler program. As a result of active research, the inventors of the present invention found that the amount of adhesion on the surface of the copper ion diffusion suppressing layer (the nitrogen-containing organic compound contained in the migration) and the printed wiring substrate were impregnated on the surface. Correcting (4) the aeronautical_side velocity in the aqueous solution (4) is not related to the (10) rate of the copper wiring diffusion-attached substrate with the copper wiring diffusion layer, and the insulation reliability between the copper wirings. Thus, the present invention has been completed. It is found that the above-mentioned problem can be solved by the following configuration. 201251542 (1) A printed wiring board comprising: a substrate with copper wiring, a substrate, and a copper wiring disposed on the substrate; and a copper ion diffusion suppression layer covering Copper wiring and containing a nitrogen-containing organic compound; and the nitrogen-containing organic compound is attached in an amount of 5. 〇 xl 〇 -9 g / mm 2 〜 〇χΐ〇 -6 g / mm 2 , and when the printed wiring board is immersed in The etching rate (Β μπι/min) of the copper wiring in the etching aqueous solution containing 1.8% by mass of sulfuric acid and 12% by mass of sodium peroxodisulfate, and the attachment of the copper ion diffusion suppressing layer The ratio (Β/Α) of the etch rate (Αμιη/min) of the copper wiring when the substrate of the copper wiring is immersed in the rice-water solution is less than 1.20. (2) The printed wiring board according to (1), which includes (3) The printed wiring board according to (1) or (2), wherein the nitrogen-containing organic compound comprises 1,2,3-triazole and/or 1,2,4-triazole (4) A method of selecting a printed wiring board, which is a method of selecting a printed wiring board having excellent insulation between copper wirings from a printed wiring board. The printed wiring board includes a substrate with copper wiring, and has a substrate and a copper wiring disposed on the substrate; and a copper ion diffusion suppression layer covering the copper wiring and containing a nitrogen-containing organic compound; and the adhesion amount of the nitrogen-containing organic compound is 5. 〇 xl 〇 -9 g / mm 2 〜 l. 〇 xl 〇-6 g/mm2, and the etching rate of the copper wiring when the printed wiring board is immersed in a button-shaped aqueous solution containing 1.8% by mass of sulfuric acid 201251542 4^UlUpif and 12% by mass of sodium peroxodisulfate B μιη/min), and when there is no diffusion of copper ions The ratio (B/A) of the I wire engraving rate (Αμπι/min) of the copper wiring when the substrate with the copper wiring is immersed in the button-printing aqueous solution is less than 1.2 〇. (5) As described in (4) A method of selecting a printed wiring substrate, wherein the nitrogen-containing organic compound comprises a saliva compound. (6) A method of selecting a printed wiring substrate according to (4) or (5), wherein the nitrogen-containing organic compound comprises 1, 2, 3 Triazole and/or 1,2,4-triazole. [Effects of the Invention] According to the present invention, it is possible to provide a printed wiring board having a reliable insulation between copper wirings. Further, according to the present invention, it is also possible to provide a A simpler method for selecting a printed wiring board having excellent insulation reliability between copper wirings. [Embodiment] Hereinafter, preferred embodiments of the printed wiring board of the present invention and a method of selecting a printed wiring board will be described in detail. The feature of the present invention is that the amount of the nitrogen-containing organic compound that interacts with the copper contained in the steel ion diffusion suppression layer on the copper wiring is found, and when the printed wiring substrate is immersed in a predetermined etching solution. The ratio of the etching rate of the copper wiring to the etching rate when the untreated copper wiring-attached substrate having no copper ion diffusion suppression layer is used, and the copper ion migration suppression function. In general, when the substrate with the copper wiring covered with the organic film is immersed in the side liquid towel 201251542, it is not expected to etch the copper wiring in order to use the organic film copper wiring. On the other hand, the inventors of the present invention have found that a substrate having a copper wiring covered with a copper ion diffusion suppressing layer containing a nitrogen-containing organic compound excellent in a migration inhibiting function is impregnated into a predetermined etching liquid. The etching rate of the copper wiring of a fixed range is not obtained. The reason for causing etching in the case of using a nitrogen-containing organic compound which interacts with copper is considered to be due to the chelation effect. When the ratio of the etching rate of the printed wiring board to the etching rate of the substrate with the copper wiring having no copper ion diffusion suppression layer is a predetermined value or more, the solubility of the nitrogen-containing organic compound to copper is too strong. A large amount of copper ions are contained in the copper ion diffusion suppression layer, and the migration inhibition effect is lowered. In addition, when the adhesion amount of the nitrogen-containing organic compound that interacts with copper on the copper wiring of the copper ion diffusion suppression layer (migration suppression layer) is within a predetermined range, migration of copper ions by the copper wiring is suppressed. As a result, the insulation reliability between the copper wiring lines is further improved. Further, when the amount of adhesion of the copper ion diffusion suppressing layer is small, the ability to trap copper ions generated by the copper wiring is low, and as a result, the occurrence of dendrites of copper cannot be suppressed, and the insulation reliability between the copper wirings cannot be secured. When the amount of adhesion is large, the adhesion between the copper wiring and the insulating film is inhibited in the printed wiring board, and the insulation reliability between the copper wirings is deteriorated. First, the adhesion amount of the nitrogen-containing organic compound and the etching rate of the copper wiring in the printed wiring board of the present invention will be described in detail, and the configuration of the printed wiring board to be used later will be described in detail. The adhesion amount of the 201251542 42UiUpif nitrogen organic compound in the copper ion diffusion suppression layer is 5. 〇xl 〇 -9 g/mm 2 丨〇χ 1 〇 · 6 g / mm ' with respect to the total surface area of the copper wiring. .〇xl〇-9 g/mm2~2.〇xl〇'7 g/mm2, more preferably ^1〇8 g/mm2~6.〇xl〇8 g/mm2. When the amount of the nitrogen-containing organic compound attached is in the above range, migration of copper ions can be suppressed. Further, the amount of adhesion can be measured by a known method (for example, absorbance measurement method). Specifically, first, the copper ion diffusion suppressing layer (extraction method using water) existing between the copper wirings is washed with water. Then, the copper ion diffusion suppressing layer on the copper wiring is extracted with an organic acid (for example, sulfuric acid), the absorbance is measured, and the amount of adhesion is calculated from the liquid amount and the coated area. In the printed wiring board of the present invention, the button wiring rate (B pm / min ) of the copper wiring when the substrate is immersed in an etching aqueous solution containing 1.8% by mass of sulfuric acid and 12% by mass of sodium peroxodisulfate, The ratio (B/A) of the etching rate (A pm/min) of the copper wiring when the untreated copper wiring-attached substrate having no copper ion diffusion-suppressing layer is immersed in the etched aqueous solution is satisfied to be smaller than 1.2〇. When the ratio of the above-mentioned engraving rate is in the above range, the copper ion diffusion suppressing layer exhibits an excellent migration suppressing effect, and as a result, the insulating reliability between the copper wirings is excellent. Among them, in terms of the more excellent migration inhibition effect, the above-mentioned oscillating rate is preferably less than 丨1〇, more preferably less than i 〇5, and particularly preferably less than 1.00. Further, the lower limit of the coating amount of the copper ion diffusion preventing layer is preferably 〇6〇 or more, more preferably 〇·65 or more. On the other hand, in the case where the ratio of the above etching rates is 1·2 〇 or more, 'in a high-temperature, high-humidity environment (for example, a high-acceleration stress test (Highly)
Accelerated Stress Test ’ HAST)環境下）等中促進銅配線 201251542 中的銅的溶解’結果損及銅配線_絕緣可#心在 速率之比小於0.6㈣情況下，達到阻礙規定触刻液的⑽ 效果的程度的越_量，或成為更疏水的歧，在印刷 配線基板中容易阻礙銅配線與絕緣膜的密著，存在導致銅 配線間的絕緣可靠性惡化的情況。 #刻速率的測定方法可利用公知的方法（例如重量 來測定。更具體而言，重量法是在包含18質量％之硫酸 及12質量％之過氧二硫酸納的叙刻水溶液中，使具有銅離 子擴散抑制層的印刷配線基板浸潰規定時間（9〇秒左 右）’根據浸潰前後的印刷配線基板的重量變化與經過時間 的關係來算出蝕刻速率。 此外三藉由使用附有銅配線的基板代替上述印刷配線 基板’來算出不具有銅離子擴散抑制層的附有銅配線的基 板的銅配線的钮刻速率。 所使用的_水歸巾，相對於水溶液總量而包含！ 8 質量％的硫酸及12質量％的過氧二硫酸鈉。 另外，蝕刻水溶液中的溶劑為水。 上述附著量以及蝕刻速率在規定範圍内的印刷配線基 板的銅配線間的絕緣可靠性優異。 換g之，作為從如下印刷配線基板中選擇銅配線間的 絕緣性優異的印細通基板的方法，上述印刷配線基板包 括具有基板及配置於上述基板上的銅配線的附有銅配線的 基板、以及覆蓋銅配線且含有含氮有機化合物的銅離子擴 散抑制層’可列舉選擇如下印刷配線基板的方法··含氮有 201251542 42UIUpif ，化合物的附著畺為5.〇Χΐ〇·9 g/mm2〜1 〇χι〇_6 ，且 當使上述印刷配線基板浸潰於包含18質量％之硫酸及i2 質量％之過氧二硫酸鈉的#刻水溶液巾時的銅配線的飯刻 速率（Β μπι/min)、與當使不具有銅離子擴散抑制層的附 有銅配線的基板浸潰於餘刻水溶液中時的銅配線的姓刻速 率（Α μιη/min)之比（Β/Α)小於1.2〇。依櫨兮古、土 叮 利用簡易的裝置，依據簡便的程序且在短時間内/選擇銅配 線間的絕緣可靠性優異的印刷配線基板。 以下，圖1中表示本發明的印刷配線基板的一實施形 態。 印刷配線基板10包括：基板12、配置於基板12上的 銅配線14、以及覆蓋銅配線14的銅離子擴散抑制層16。 以下’對構成印刷配線基板〗〇的各構件進行詳細說 明。 (基板） 基板只要是可支持後述銅配線的基板，則並無特別限 制’通常為絕緣基板。絕緣基板例如可使用有機基板、陶 瓷基板、矽基板、玻璃基板等。 有機基板的材料可列舉樹脂，例如較佳為使用熱硬化 性樹脂、熱塑性樹脂、或者將它們混合而成的樹脂。熱硬 化性樹脂可列舉：酚樹脂、脲樹脂、三聚氰胺樹脂、醇酸 樹脂、丙烯酸樹脂、不飽和聚酯樹脂、鄰苯二甲酸二烯丙 酯樹脂、環氧樹脂、矽酮樹脂、呋喃樹脂、酮樹脂、二甲 苯樹脂、苯并環丁烯樹脂等。熱塑性樹脂可列舉：聚醯亞 11 201251542 -----1— 胺樹脂、聚苯醚樹脂、聚苯硫醚樹脂、芳族聚醯胺 . 樹脂、液晶聚合物等。 以1111 此外’有機基板的材料亦可使用玻璃織布、玻璃不織 布、芳族聚醯胺織布、芳族聚酿胺不織布、芳香族聚醯胺 織布或使該些材料中含浸有上述樹脂的材料等。 (銅配線） 基板上的配線包含銅。 基板上的銅配線的形成方法並無特別限制，可採用公 知的方法。代表性而言可列舉：利用蝕刻處理的減成ς (subtractive process )、或利用電解鍍敷的半加成法 (semiadditive process ) 〇 銅配線的寬度並無特別限制，就印刷配線基板的高集 成化的方面而言’較佳為1μηι〜1〇〇〇μιη，更佳為3呵〜 25 μιη ° 銅配線間的間隔並無特別限制，就印刷配線基板的高 集成化的方面而言’較佳為i卿〜誦μιη，更佳為3阿 〜25 μπι 〇 另外，銅配線的圖案形狀並無特別限制，可為任音的 圖案。例如可解直線狀、轉狀、矩形狀、等 銅配線的厚度並無特別限制，就印刷配線基板的高集 《化的方面而5 ’較佳為！帅〜刚❻卿更佳為3叫〜 25 μιη。 銅配線的表面粗輪度 緣膜的密著性的觀點而言In the Accelerated Stress Test 'HAST) environment, etc., the dissolution of copper in the copper wiring 201251542 is promoted. As a result, the copper wiring is _insulated. The ratio of the heart rate is less than 0.6 (four), and the effect of impeding the specified etchant is achieved. In the printed wiring board, the adhesion between the copper wiring and the insulating film is likely to be impeded, and the insulation reliability between the copper wirings may be deteriorated. The method for measuring the engraving rate can be measured by a known method (for example, weight). More specifically, the gravimetric method is carried out in an aqueous solution containing 18% by mass of sulfuric acid and 12% by mass of sodium peroxodisulfate. The printed wiring board of the copper ion diffusion suppression layer is immersed for a predetermined period of time (about 9 sec.). The etching rate is calculated from the relationship between the change in weight of the printed wiring board before and after the immersion and the elapsed time. The substrate is used to calculate the button rate of the copper wiring of the copper wiring-attached substrate having no copper ion diffusion suppression layer instead of the printed wiring board. The water-based towel used is included with respect to the total amount of the aqueous solution! And % of sulfuric acid and 12% by mass of sodium peroxodisulfate. The solvent in the etching aqueous solution is water. The adhesion amount and the etching rate are excellent in insulation reliability between the copper wirings of the printed wiring board within a predetermined range. The printed wiring board package is a method of selecting a printed through substrate having excellent insulation between copper wirings from the following printed wiring boards. A method of printing a wiring board as follows, including a copper wiring substrate having a substrate and a copper wiring disposed on the substrate, and a copper ion diffusion suppression layer containing a nitrogen-containing organic compound; There is 201251542 42UIUpif , and the adhesion of the compound is 5.〇Χΐ〇·9 g/mm 2 〜1 〇χι〇_6 , and the printed wiring board is immersed in the peroxygen containing 18% by mass of sulfuric acid and i2% by mass. The copper engraving rate (Β μπι/min) of the copper wiring when the aqueous solution of sodium disulfate is used, and the copper when the substrate with the copper wiring having no copper ion diffusion suppression layer is immersed in the residual aqueous solution The ratio of the surname rate of the wiring (Α μηη/min) (Β/Α) is less than 1.2〇. According to the simple and simple device, the insulation between the copper wiring compartments is selected according to a simple procedure and in a short time. A printed wiring board having excellent reliability. Hereinafter, an embodiment of the printed wiring board of the present invention is shown in Fig. 1. The printed wiring board 10 includes a substrate 12, a copper wiring 14 disposed on the substrate 12, and a covered copper wiring 14. The copper ion diffusion-suppressing layer 16 will be described in detail below. (Substrate) The substrate is not particularly limited as long as it is a substrate that can support a copper wiring to be described later. For example, an organic substrate, a ceramic substrate, a tantalum substrate, a glass substrate, etc. can be used. The material of the organic substrate is, for example, a resin, and a thermosetting resin, a thermoplastic resin, or a resin obtained by mixing them is preferably used. Examples thereof include phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, fluorenone resin, furan resin, ketone resin, and Toluene resin, benzocyclobutene resin, etc. Thermoplastic resin can be exemplified by: Polyamide 11 201251542 -----1 - Amine resin, polyphenylene ether resin, polyphenylene sulfide resin, aromatic polyamine. Resin, Liquid crystal polymer, etc. In addition to 1111, the material of the organic substrate may also be glass woven fabric, glass non-woven fabric, aromatic polyamide woven fabric, aromatic polyamine woven fabric, aromatic polyamide woven fabric or impregnated with these materials. Materials and so on. (Copper wiring) The wiring on the substrate contains copper. The method of forming the copper wiring on the substrate is not particularly limited, and a known method can be employed. Typical examples include a subtractive process by etching treatment or a semi-adhesive process by electrolytic plating. The width of the beryllium copper wiring is not particularly limited, and the printed wiring substrate is highly integrated. In terms of the aspect, it is preferably 1 μηι 1 to 1 μmηη, more preferably 3 ° to 25 μιη °. The interval between the copper wirings is not particularly limited, and in terms of the high integration of the printed wiring substrate,佳为i卿~诵μιη, more preferably 3 〜25 μπι 〇 In addition, the shape of the copper wiring pattern is not particularly limited, and may be a pattern of any tone. For example, the thickness of the copper wiring can be solved in a straight line, a rotating shape, or a rectangular shape. The thickness of the copper wiring is not particularly limited, and it is preferable that the printed wiring board has a high level of "5". Shuai ~ Gang Yuqing is better for 3 calls ~ 25 μιη. The surface roughness of the copper wiring is from the viewpoint of the adhesion of the film.
Rz並無特別限制，就與後述絕 ’較佳為0.001 μιη〜15 μιη，更 201251542 42010pif 佳為 0.3 μηι ^ 3 μπχ。 調整銅配線的表面粗糙度Rz的方法可使用公知的方 法’例如可列舉化學粗糙化處理、拋光研磨處理等。 此外’ Rz是依據jis B 0601 ( 1994年）來測定。 (銅離子擴散抑制層） —如上所述’銅離子擴散抑制層是覆蓋銅配線且含有含 氮有機化合物的層。更具體而言，如圖1所示，銅離子擴 散抑制層16是以覆蓋銅配線14表面的方式配置。藉由形 成該銅離子擴散抑制層16，源自銅配線14表面的銅離子 的遷移得到抑制。 此外’銅離子擴散抑制層16的銅配線14表面上的附 者量如上所述。 如圖1所示，較佳為在基板12上的銅配線14間不設 置銅離子擴散抑制層16。即，較佳為實質上僅在銅配線14 表面上形成有銅離子擴散抑制層16。若在基板12上的銅 配線間存在銅離子擴散抑制層16，則有銅配線間的絕 &可#性&損_慮’並且有後舰賴與基板的密著性 受損的顧慮。 首先’對銅離子擴散抑制層中所含的含氮有機化合物 進行詳細說明。 _含氮有機化合物為至少包含氮原子的化合物 ，經由該 氮，子而吸附於細通上。含氮有機化合物只要是能夠以 規疋里的附著量來形成上賴刻速率之比在規定範圍内的 離子擴散抑㈣的化合物，則並無制㈣卜例如可列 13 201251542 ηζ,νι vpii 舉嗤化合物、胺化合物、氮丙。定（aziridine)化 氰酸醋化合物、胺基甲酸合物、亞胺化合物等。波、異 就銅離子擴散抑制層的娜子的遷移抑佩力展、’ 面而言，較佳為唑化合物。 、的方 唑化合物是環内包含1個以上氮原子的單環式的雜 貝環化合物。例如可列舉：氮原子數為2個的二唑、f 5 子數為3個的三、以及氮原子數為4個的时等。湯原 體而，可列舉：1，2,3-三。坐、1，2,4_三唾、3_胺基_1，2,4_三具 四哇等。其巾’賴離子的遷移抑制效果更優 ^、 言，較佳為三唾，具體而言，較佳為1，2,3-三唾及/或！ 2 7 有醯胺基等取代基 此外’本發明中亦可包含2種以上㈣化合物。 另外’触化合物只要不損及本發_效果，則可具 此外，包含雜5員環的多環式有機化合物不符合唾化 合物。即’作為包含雜5員軸純式㈣族化合物的苯 并二唑不包括在本說明書的唑化合物中。 就可更抑制銅離子遷移的方面而言，銅離子擴散抑制 層中的含氮有機化合物的含量較佳為〇j質量％〜1〇〇質量 %，更佳為20質量％〜100質量％，尤佳為5〇質量％〜9〇 質量％。尤其，銅離子擴散抑制層較佳為實質上含有含氮 有機化合物。若含氮有機化合物的含量過少，則銅離子的 遷移抑制效果降低。 銅離子擴散抑制層中較佳為實質上不含鋼離子或者金 201251542 42UiUpif 屬銅。若銅離子擴散抑制層中包含規定量以上的銅離子或 者金屬銅，則存在本發明的效果差的情況。 [印刷配線基板的製造方法] 一上述印刷配線基板的製造方法並無特別限制，就生產 ! 生尚，谷易去除基板上的銅配線間的銅離子擴散抑制層的 方面而言，較佳為包括後述層形成步驟以及乾燥步驟。 以下，對各步驟進行詳細說明。 (層形成步驟） »亥步驟中’首先，使具有基板及配置於基板上的銅配 線的附有銅配線的基板（芯基板）與含有含氮有機化合物 且pH值顯示5〜9的處理液接觸（接觸步驟）。然後以 溶劑（清洗溶劑）清洗附有銅配線的基板，在銅配線表面 上形成含有含氮有機化合物的銅離子擴散抑制層（清洗步 驟）°藉由該步驟，以覆蓋銅配線的表面的方式形成銅離$ 擴散抑制層，抑制銅的遷移。 首先，對層形成步驟中使用的材料（附有銅配線的義Rz is not particularly limited, and is preferably 0.001 μιη to 15 μιη, and more preferably 201251542 42010 pif is 0.3 μηι ^ 3 μπχ. A known method can be used for the method of adjusting the surface roughness Rz of the copper wiring. For example, a chemical roughening treatment, a buffing treatment, or the like can be mentioned. In addition, 'Rz is measured according to jis B 0601 (1994). (Copper ion diffusion suppressing layer) - As described above, the copper ion diffusion suppressing layer is a layer covering the copper wiring and containing the nitrogen-containing organic compound. More specifically, as shown in Fig. 1, the copper ion diffusion suppression layer 16 is disposed to cover the surface of the copper wiring 14. By forming the copper ion diffusion suppressing layer 16, migration of copper ions derived from the surface of the copper wiring 14 is suppressed. Further, the amount of the attachment on the surface of the copper wiring 14 of the copper ion diffusion suppression layer 16 is as described above. As shown in Fig. 1, it is preferable that the copper ion diffusion suppressing layer 16 is not provided between the copper wirings 14 on the substrate 12. That is, it is preferable that the copper ion diffusion suppression layer 16 is formed substantially only on the surface of the copper wiring 14. When the copper ion diffusion suppressing layer 16 is present between the copper wirings on the substrate 12, there is a concern that the copper wiring has a "smoothness" and a damage to the substrate. . First, the nitrogen-containing organic compound contained in the copper ion diffusion suppression layer will be described in detail. The nitrogen-containing organic compound is a compound containing at least a nitrogen atom, and is adsorbed to the fine passage via the nitrogen. The nitrogen-containing organic compound is not limited to a compound capable of forming an ion diffusion ratio within a predetermined range by the amount of deposition in the gauge, and is not provided as a compound. For example, it can be listed as 13 201251542 ηζ, νι vpii Bismuth compounds, amine compounds, nitrogen and hydrogen. Aziridine Cyanate vinegar compound, amino acid complex, imine compound, and the like. The wave and the difference are preferably an azole compound in terms of the migration inhibition property of the nano-ion of the copper ion diffusion-suppressing layer. The azole compound is a monocyclic heterobe ring compound containing one or more nitrogen atoms in the ring. For example, a diazole having two nitrogen atoms, three having three f 5 subgroups, and four nitrogen atoms are exemplified. As for the original soup, it can be cited as 1, 2, 3 - 3. Sitting, 1, 2, 4_ three saliva, 3_amino group_1, 2, 4_ three four wow and so on. The migration inhibition effect of the towel is better, and it is preferably three saliva. Specifically, it is preferably 1,2,3-three saliva and/or! 2 7 A substituent such as a decylamino group. Further, the present invention may contain two or more (four) compounds. Further, the "touch compound" may have a polycyclic organic compound containing a heterocyclic ring of 5 members as long as it does not impair the effect of the present invention. That is, the benzobisazole which is a compound of the pure (Group) group containing a heterocyclic 5 member is not included in the azole compound of the present specification. The content of the nitrogen-containing organic compound in the copper ion diffusion-suppressing layer is preferably 〇j% by mass to 1% by mass, more preferably 20% by mass to 100% by mass, in terms of suppressing migration of copper ions. More preferably 5 〇 mass% ~ 9 〇 mass%. In particular, the copper ion diffusion inhibiting layer preferably contains substantially a nitrogen-containing organic compound. If the content of the nitrogen-containing organic compound is too small, the effect of inhibiting the migration of copper ions is lowered. Preferably, the copper ion diffusion suppression layer is substantially free of steel ions or gold 201251542 42UiUpif copper. When the copper ion diffusion suppression layer contains a predetermined amount or more of copper ions or metallic copper, the effect of the present invention may be inferior. [Manufacturing Method of Printed Wiring Substrate] The method for producing the printed wiring board is not particularly limited, and it is preferably produced, and it is preferable that the copper ion diffusion suppressing layer between the copper wirings on the substrate is removed. The layer forming step and the drying step described later are included. Hereinafter, each step will be described in detail. (Layer forming step) - First, a substrate (core substrate) having a substrate and a copper wiring disposed on the substrate, and a treatment liquid containing a nitrogen-containing organic compound and having a pH of 5 to 9 are provided. Contact (contact step). Then, the substrate with the copper wiring is washed with a solvent (cleaning solvent), and a copper ion diffusion suppressing layer containing a nitrogen-containing organic compound is formed on the surface of the copper wiring (cleaning step). By this step, the surface of the copper wiring is covered. Forming copper away from the diffusion inhibiting layer inhibits copper migration. First, the material used in the layer formation step (with the meaning of copper wiring)
板、處理液等）進行制，然後對層形成步驟的程序^ 說明。 J (附有銅配線的基板） 此外 本步驟中使用的附有銅配線的基板（芯基板）具 板 '及配置於基板上_配線。換言之，附有銅配線二 板只要是至少具有基板及銅配線的積層結構，且在最^ 配置有銅配線即可’可在基板與銅配線之間依如下丄 備其他的金屬配線（配線圖案）以及層間絕緣層、一 15 201251542 其他的金屬配線以及層間絕緣層可在基板與銅配線之間依 此順序交替包含2層以上的各層。即，附有銅配線的基板 可為所謂的多層配線基板、增層基板。 層間絕緣層可使用公知的絕緣材料，例如可列舉：酚 樹脂、萘樹脂、脲樹脂、胺基樹脂、醇酸樹脂、環氧樹脂、 丙烯酸酯樹脂等。 另外，附有銅配線的基板可為所謂的剛性基板（rigid substrate)、可挽性基板（flexible substrate)、剛性撓性基 板（rigid flexible substrate )。 銅配線可僅設置於基板的單面，亦可設置於兩面。即， 附有銅配線的基板可為單面基板，亦可為兩面基板。 附有銅配線的基板中的基板的定義如上所述。另外， 附有銅配線的基板中的配線的定義亦如上所述。 (處理液） 本步驟中使用的處理液含有含氮有機化合物，pH值顯 示5〜9 〇 含氮有機化合物的定義如上所述。此外，該製造方法 中，在使用苯并三唑作為含氮有機化合物的情況下，藉由 後述清洗步驟中利用清洗溶劑進行清洗，大半的苯并三唑 被沖走，結果無法獲得規定附著量的銅離子擴散抑制層。 另外，包含過剩蝕刻劑的含苯并三唑處理液、或包含具有 飯刻能力的咪唑化合物的處理液中，形成於銅配線上的有 機皮膜中包含過剩的銅離子，結果無法獲得規定的銅配線 的蝕刻速率之比。 201251542 ^zuiupif 此外’該製造方法中，在使用三聚硫氰酸（thi〇cyanurie acid)、3-胺基-1，2,4-三唑作為含氮有機化合物的情況下， 亦無法獲得表現出所需特性的印刷配線基板。 處理液中的含氮有機化合物的總含量並無特別限制， 就銅離子擴散抑制層的形成容易度、以及銅離子擴散抑制 層的附著量控制的方面而言，相對於處理液總量，上述含 氮有機化合物的總含量較佳為〇.(Π質量％〜1〇質量％，更 佳為0.1質量％〜5質量0/〇’特佳為〇 25質量％〜5質量〇/0。 若含氮有機化合物的總含量過多，則銅離子擴散抑制層的 堆積量控制變得困難。若含氮有機化合物的總含量過少， 則直至達到所需的銅離子擴散抑制層的堆積量為止花費時 間，生產性差。 處理液中亦可包含溶劑。所使用的溶劑並無特別限 制，例如可列舉：水、醇系溶劑（例如曱醇、乙醇、異丙 醇）、酮系溶劑（例如丙酮、甲基乙基酮、環己酮）、醯胺 系溶劑（例如甲醯胺、二曱基乙醯胺、N_甲基吡咯啶酮）、 腈系溶劑（例如乙腈、丙腈）、酯系溶劑（例如乙酸曱酯、 乙酸乙酯）、碳酸酯系溶劑（例如碳酸二甲酯、碳酸二乙 酯）、醚系溶劑、鹵素系溶劑等。亦可將該些溶劑混合2 種以上來使用。 其中，就印刷配線基板製造中的安全性方面而言，較 佳為水、醇系溶劑。尤其，若使用水作為溶劑，則在使附 有銅配線的基板與處理液接觸時採用浸潰法的情況下，含 氮有機化合物特別容易自我堆積於銅配線表面，因此較佳。 17 201251542 處理液中的溶劑的含量並無特別限制，相對於處理液 總量，上述溶劑的含量較佳為90質量％〜99 99質量〇/， 更佳為95質量％〜99.9質量％ ’特佳為95質量％ 〇 ’ 質量％。 ‘ 另方面，就提尚印刷配線基板中的銅配線間的絕緣 可靠性的方面而言，較佳為處理液中實質上不含銅離子。 若包含過剩量的銅離子’則當形成銅離子擴散抑制層時會 在該層巾包含_子，㈣娜子遷移的絲弱存在 配線間的絕緣可靠性受損的情況。 此外，所謂實質上不含銅離子是指處理液中的銅離子 的含量為1 μιηοΐ/ΐ以下，更佳為〇」陶丨/丨以下。最佳為〇 mo 1/1。 另外，就提高印刷配線基板中的銅配線間的絕緣可靠 =的方面而言，較佳為處理液中實質上不含銅的爛劑。 若處理液巾包含侧劑’财使附有銅喊板與處理 液接觸時’存在娜子糾至處理液巾的情況。因此結果 為，銅離子擴散抑制層中會包含銅離子，抑制銅離子遷移 的效果弱，存在銅配_的絕緣可靠性受損的情況。 作為侧劑，例如可列舉：有機酸（例如硫酸、俩、 鹽酸、乙酸、甲酸、氫氣酸）、氧化劑（例如過氧化氫、濃 硫酸）、螯合劑（例如亞胺基二乙酸、次氮基三乙酸 (mtril〇triacetic acid ))、伸乙基二胺四乙酸伸乙基二胺、 乙醇胺、胺基丙醇）、硫醇化合物#。另外，侧劑亦包含 如味嗤、或咪哇衍生物化合物等那樣自身具有銅的餘刻作 201251542 ^uiupif 用的化合物。 ^此外，所謂實質上不含蝕刻劑，是指相對於處理液總 f，處理液中的蝕刻劑的含量為0.01質量°/〇以下，就更提 局銅配線間的絕緣可靠性的方面而言’更佳為請i質量 %以下。最佳為〇質量0/〇。 處理液的pH值顯示5〜9。其中，就印刷配線基板中 的銅配線間的絕緣可靠性更優異的方面而言，pH值更佳為 6〜8。 若處理液的pH值小於5,則促進銅離子從銅配線中溶 出，銅離子擴散抑制層中大量包含銅離子，結果存在抑制 銅遷移的效果下降的情況。若處理液的pH值超過9,則氫 氧化銅析出，容易氧化溶解，結果存在抑制銅遷移的效果 下降的情況。 此外’ pH值的調整可使用公知的酸（例如鹽酸、硫 、或驗（例如虱氧化鈉）來進行。另外，pH值的測定 可使用公知的測定方法（例如pH計（水溶劑的情況））來 實施。 此外，上述處理液中亦可包含其他添加劑（例如pH 調整劑、界面活性劑、防腐劑、析出防止劑等）。 (溶劑（清洗溶劑）） 清洗附有銅配線的基板的清洗步驟中使用的溶劑（清 洗溶劑）只要能夠去除堆積於基板上的銅配線間的多餘含 氮有機化合物等，則並無特別限制。其中，較佳為溶解含 氮有機化合物的溶劑。藉由使用該溶劑，可更有效率地去 201251542 除堆積於基板上的多餘含氮有機化合物、或配線上的多餘 含氮有機化合物等。 ' 作為溶劑’例如可列舉：水、醇系溶劑（例如甲醇、 乙醇、丙醇）、酮系溶劑（例如丙酿j、曱基乙基酮、環己酮）、 醯胺系溶劑（例如甲醯胺、二甲基乙醯胺、N_甲基吡咯啶 酉同）、腈系溶劑（例如乙腈、丙腈）、酯系溶劑（例如乙酸 甲s曰、乙酸乙酯）、碳酸酯系溶劑（例如碳酸二曱酯、碳酸 —乙酯）、醚系溶劑、鹵素系溶劑等。亦可將該些溶 2種以上來使用。 ° 其中’就對微細配線間的液滲透性方面而言，較佳為 包含選自由水、醇系溶劑及曱基乙基酮所組成組群中的至 少一者的溶劑，更佳為醇系溶劑與水的混合液。 所使用的溶劑的沸點（25t： , i個大氣壓）並無特別 限制，就安全性的觀點而言，較佳為7yc〜1〇(rc，更佳 為 80°C 〜10(TC。 所使用的溶劑的表面張力（25。〇並無特別限制，就 麵1配線間的清洗性更優異、銅配線間的絕緣可靠性更提高 的方面而言’較佳為10mN/m〜80mN/m，更佳為15mN/m 〜6〇 mN/m。 (層形成步驟的程序） 將層形成步驟分成接觸步驟與清洗步驟兩個步驟來進 行說明。 (接觸步驟） 首先，使具有基板及配置於基板上的銅配線的附有銅 201251542 42UlUpif 配線的基板與含有含氮有機化合物且pH值顯示5〜9的處 理液接觸。更具體而言，藉由使圖2 (A)所示的包括基板 12及銅配線14的附有銅配線的基板18與上述處理液接 觸，而如圖2 (B)所示，在附有銅配線的基板18上形成 含有含氮有機化合物的層20。該層20形成於基板12上、 以及銅配線14上。即，換言之，本步驟是使附有銅配線的 基板與處理液接觸，以含氮有機化合物覆蓋基板表面與銅 配線表面的步驟。 含有含氮有機化合物的層中含有含氮有機化合物。該 含氮有機化合物的含量等與上述銅離子擴散抑制層中的含 量的含義相同。另外，該含氮有機化合物的附著量並無特 別限制’較佳為經過後述的清洗步驟，可獲得所需附著量 的銅離子擴散抑制層的附著量。 附有銅配線的基板與上述處理液的接觸方法並無特別 限制，可採用公知的方法。例如可列舉：浸潰浸潰、喷淋 噴霧、喷射塗佈、旋轉塗佈等，就處理的簡便度、處理時 間的調整容易度而言，較佳為浸潰浸潰、喷淋喷霧、喷射 塗佈。 另外，就銅離子擴散抑制層的附著量控制的方面而 s ’接觸時的處理液的液溫較佳為5°C〜60°C的範圍，更 佳為15。〇〜50〇C的範圍，尤佳為20。(：〜40°C的範圍。 另外，就生產性、以及銅離子擴散抑制層的附著量控 制的方面而言，接觸時間較佳為10秒〜3〇分鐘的範圍， 更佳為15秒〜10分鐘的範圍，尤佳為3〇秒〜5分鐘的範 21 201251542 • v A Λ Λ. 圍。 (清洗步驟） 繼而，利用溶劑來清洗附有銅配線的基板，在銅配線 表面上形成含有含氮有機化合物的銅離子擴散抑制層。具 體而言，藉由利用上述清洗溶劑，對圖2 (Β)所得的設置 有含有含氮有機化合物的層20的附有銅配線的基板18進 行清洗，而如圖2 (C)所示，去除銅配線14間的含有含 氮有機化合物的層20，並且去除銅配線μ上的多餘含氮 有機化合物，在銅配線14上形成含有含氮有機化合物的銅 離子擴散抑制層16。即，換言之，本步驟是使用溶劑來清 洗附有銅配線的基板，去除基板表面上的含氮有機化合物 的步驟。 清洗方法並無特別限制，可採用公知的方法。例如可 歹J舉·在附有銅配線的基板上塗佈清洗溶劑的方法、在清 洗溶劑中浸潰附有銅配線的基板的方法等。 另外，就銅離子擴散抑制層的附著量控制的方面而 言’清洗溶劑的液溫較佳為5。(：〜60¾的範圍，更佳為15〇C 〜30°C的範圍。 另外，就生產性、以及銅離子擴散抑制層的附著量控 制的方面而έ，附有銅配線的基板與清洗溶劑的接觸時間 較佳為10秒〜10分鐘的範圍，更佳為15秒〜5分鐘的範 圍。 (乾燥步驟） 該步驟中，對設置有銅離子擴散抑制層的附有銅配線 22 201251542 ^zuiupif 的基板進行加熱乾燥。若附有銅配線的基板上殘存水分， 則有促進娜子遷移的誠，因此較佳域由設置該步驟 來去除水分。 ，抑制銅配線氧化的方面而言，加熱乾燥條件較佳為 f 7〇C〜120°C (較佳為8(TC〜11〇。〇下實施15秒〜10 ^釦（較佳為30秒〜5分鐘）。若乾燥溫度過低、或者乾 燥時，過短’财在水分的擔不充分的航，若乾燥溫 庋過高、或者乾燥時間過長，則有形成氧化銅的顧慮。 乾燥時使用的裝置並無特別限定，可使用恆溫層、加 熱器等公知的加熱裝置。 此外，本步驟為任意的步驟，在層形成步驟中使用的 溶劑為揮發性優異的溶劑的情況等，亦可不實施本步驟。 本發明的印刷配線基板可視需要，以覆蓋銅離子擴散 抑制層的方式具有絕緣膜。更具體而言，如圖2(D)所示， 絕緣膜22是以銅離子擴散抑制層16與設置於表面的銅配 線η接觸的方式設置於附有銅配線的基板18上。即可 獲得如下積層體（附有絕緣膜的印刷配線基板），該積層體 (附有絕緣膜的印刷配線基板）具備基板12、配置於基板 12上的銅配線14、配置於銅配線14上的絕緣膜22，且在 銅配線14與絕緣膜22之間夾有銅離子擴散抑制層16。藉 由設置絕緣膜22，銅配線14間的絕緣可靠性得到進一步 確保。另外，由於基板12與絕緣膜22可直接接觸，故而 絕緣膜22的密著性優異。 首先，對所使用的絕緣膜進行說明，然後對絕緣膜的 23 201251542 形成方法進行說明。 絕緣膜可使用公知的絕緣性材料。例如可使用作 謂的層間絕緣膜來使用的材料，具體而言可列舉：環氧樹 脂、芳族《胺樹脂、結晶性聚馳樹脂、非晶性聚婦炉 樹脂、含氟樹月旨（聚四氟乙烯、全氟化聚醯亞胺、全氣^ 非晶樹脂等）、聚醯亞胺樹脂、聚醚簡脂、聚苯频樹脂、 聚醚醚_樹脂、丙烯酸酯樹脂等。層間絕緣膜例如可列舉 味之素精密技術(Ajinomoto Fine Techno)(股）製造的ABF GX-13 等。 另外，亦可使用所謂的阻焊劑層作為絕緣膜。阻焊劑 可使用市售品，具體而言，例如可列舉：Taiy〇 Ink製造（股） 製造的_00、PSR4000 (商品名），日立化成工業（股) 製造的SR7200G等。 絕緣膜的形成方法並無特別限制，可採用公知的方 法。例如可列舉：將絕緣膜的膜直接層壓於印刷配線基板 上的方法、或將包含構成絕緣膜的成分的絕緣膜形成用組 成物塗佈於印刷配線基板上的方法、或將印刷配線基板浸 潰於該絕緣膜形成用組成物中的方法等。 此外，上述絕緣膜形成用組成物中可視需要包含溶 劑。在使用包含溶劑的絕緣膜形成用組成物的情況下，將 該組成物配置於基板上後’視需要亦可為了去除溶劑而實 施加熱處理。 另外’將絕緣膜設置於印刷配線基板上後，可視需要 對絕緣膜貫施能量賦予（例如曝光或者加熱處理）。 24 201251542 4201〇pif 此外’絕緣膜可設置於印刷配線基板上的整個面上， 亦可設置於-部分上。例如，可以印刷配線基板中的銅配 線的一部分露出的方式，設置成覆蓋銅配線。 所形成的絕緣膜的膜厚並無特別限制，就銅配線間的 絕緣可罪性的觀點而言，較佳為5 〜5〇 μπι，更佳為μ μηι〜40 μπι 〇 另外，亦可將所得的絕緣膜去除一部分，安裝半導體 晶片，來用作印刷電路板。 例如，在使用阻焊劑作為絕緣膜的情況下，將規定圖 案狀的遮罩配置於絕緣膜上，賦予能量而使其硬化，去除 未賦予能量的區域的絕緣膜而使銅配線露出。繼而，利用 公知的方法來清洗（例如使用硫酸或界面活性劑來清洗） 露出的銅配線的表面，然後將半導體晶片安裝於銅配線表 面上。 在使用公知的層間絕緣膜作為絕緣膜的情況下，可藉 由鑽孔加工或雷射加工來去除絕緣膜。 [用途] 本發明的印刷配線基板可對各種用途以及結構來使 用，例如可列舉母板用基板或半導體封裝用基板、模塑互 連元件（Molded Interconnect Device，MID)基板等，可對 剛性基板、可撓性基板、撓性剛性基板、成型電路基板等 來使用。 此外，就絕緣特性更優異的方面而言，本發明的印刷 配線基板的銅配線間產生的樹枝狀結晶的成長速度 25 201251542 (μιη/sec)較佳為 2.9 μιη/sec 以下，更佳為 2.5 μηι/sec 以 下，尤佳為2.0 μπι/sec以下。 [實例] 以下，利用實例，對本發明進一步進行詳細說明，但 本發明並不限定於該些實例。 (實例1) 使用玻璃環氧基板，利用減成法來形成L/S=100 μηι/100μηι的梳型銅配線基板（附有銅配線的基板）。附有 銅配線的基板是利用以下方法來製作。 在覆銅積層板（曰立化成公司製造的MCL-E-679F， 基板：玻璃環氧基板）上，利用真空層壓機，在〇.2 MPa 的壓力下以70°C的條件層壓乾式膜抗蝕劑（DFR，商品 名：RY3315,日立化成工業股份有限公司製造> 層壓後， 利用中心波長為365 nm的曝光機，以70 mJ/cm2的條件對 銅圖案形成部進行遮罩曝光。然後，利用1〇/0碳酸氫納水 溶液進行顯影，進行水洗而獲得減成、触刻用的抗姓劑圖 案。 繼而，在未形成抗蝕劑圖案的非抗蝕劑部的銅被姓刻 之前，對所得的基板喷霧喷射45t的40%氧化銅液。然 後，對所得的基板進行水洗。 繼而，為了剝離抗蝕劑圖案，而將基板在45〇c的 4%NaOH水溶液中浸潰60秒。然後，對所得的基板進行 水洗’在1%硫酸中浸潰30秒。其後，再次水洗。 繼而，利用前處理劑（美克（MEC)公司製造的 26 201251542 Hzuiupif CA-5330)來去除銅配線表面的污垢等，然後利用粗糙化 處理劑（MEC公司製造的CZ-8110)實施銅配線表面的粗 糙化處理，獲得L/S=100 μιη/100 μηι的附有銅配線的基 板°所件銅配線的表面粗链度為rz=1.〇 。 繼而，將所得的附有銅配線的基板在包含1，2,3-三唑 的水溶液（溶劑：水，1，2,3-三唑的含量：相對於水溶液總 量為2.5質量％，液溫：25。〇，ρΗ值：7)中浸潰3〇秒。 然後，使用乙醇來清洗所得的附有銅配線的基板（接觸時 間· 2分鐘，液溫度：25°C )。進而，然後將基板在1〇〇。〇 下進行2分鐘乾燥處理，獲得在附有銅配線的基板上具有 銅離子擴散抑制層的附有銅離子擴散抑制層的銅配線基板 (相當於印刷配線基板）。 藉由進行反射率測定，確認在銅配線上形成包含丨，2,3_ 二唑的銅離子擴散抑制層。另外，藉由上述吸光度測定， °亥二°坐化合物的附著量為3.5 X10·8 g/mm2。 繼而，使所得的附有銅離子擴散抑制層的銅配線基板 /文/貝於包含1.8質量％之硫酸及12質量％之過氧二硫酸納 的勉刻水溶液中，利用上述重量法來測定銅配線的蝕刻速 率（B μιη/min)。蝕刻速率 B 為 0.76 μπι/min » 另外’使用不具有銅離子擴散抑制層的未處理的附有 銅配線的基板’利用與上述相同的方法來測定蝕刻速率。 钮刻速率A為0.75 μιη/min。触刻速率之比（B/A)為1.01。 此外’在附有銅離子擴散抑制層的銅配線基板的銅配 線間的基板表面，藉由利用水的銅配線間萃取液的吸光度 27 201251542 測定’無法確認到銅離子擴散抑制層，確認藉由乙醇清洗 而被去除。 (藉由溶液浸潰試驗的樹枝狀結晶成長速度測定） 使所得的附有銅離子擴散抑制層的銅配線基板浸潰於 pH值為5的鹽酸中，對銅配線間施加1.2 V的電壓，在光 學顯微鏡下（Olympus公司製造的BX-51)測定在銅配線 間產生的樹枝狀結晶的成長速度（μηι/sec)。 將實例1中所得的結果示於表1中。 (藉由HAST試驗的基板壽命測定） 在所得的附有銅離子擴散抑制層的銅配線基板上層壓 絕緣膜（Taiyolnk公司製造的PFR-800)，然後進行曝光、 烘烤，製造附有絕緣膜的印刷配線基板（絕緣膜的膜厚： 35 μιη) ° 使用所得的附有絕緣膜的印刷配線基板，在濕度為 85%、溫度為130度、壓力為1.2 atm、電壓為1〇〇 V的條 件下進行壽命測定（使用裝置：espec公司製造， EHS-221MD)。 評價方法是準備20桿（20個附有絕緣膜的印刷配線 基板）來實施上述試驗。此外，銅配線間的電阻值是以 1x109 Ω為基準電阻值。將自試驗開始起經過12〇小時時 的電阻值顯示為基準電阻值以上的桿設為合格。將實例1 中獲得的結果示於表1中。 此外，依據以下的評價基準進行評價。 「〇」：20桿中，20桿顯示為基準電阻值以上的情況。 28 201251542 ^zuiupif 「△」：20桿中’1〜19桿顯示為基準電阻值以上的情 況。 「X」：20桿中，無顯示為基準電阻值以上者的情況。 (實例2) 除了使用實例1巾使㈣包含丨，2,3_三销水溶液， 使附有銅配線的基板浸漬2分30秒以外，以與實例i相同 的程序，製造附有銅離子擴散抑制層的銅配線基板。將各 種測定結果歸納示於表1中。 (實例3) 除了代替實例1 吏用❾包含H3-三唾的水溶液， 而使用1，2,4-二唾的含量相對於水溶液總量為2 5質量％的 包含1,2,4-三峻的水溶液（溶劑：水，液溫：25。〇，值： 6) ’使附有銅配線的基板浸潰45秒以外，以與實例}相同 的程序，製造附有銅離子擴散抑制層的銅配線基板。將各 種測定結果歸納示於表1中。 (實例4) 除了代替實例1中使用的包含^3-三唑的水溶液， 而使用1，2,4-三唑的含量相對於水溶液總量為2 5質量％的 包含1，2,4-二唾的水溶液（溶劑：水，液溫：25〇c，pH值： 6) ’使附有銅配線的基板浸潰5分鐘以外，以與實例1相 同的程序，製造附有銅離子擴散抑制層的銅配線基板。將 各種測定結果歸納示於表1中。 (實例5 ) 除了代替實例1中使用的包含1,2,3-三唑的水溶液， 29 201251542 而使用包含1，2,3_三唑及l，2,4-三 ，. … °坐的水溶液（溶劑：水， ，溫.25ΐ，pH值：6)以外，以與實例丨相同的程序， 製造附有鋼離子擴散抑制層_配線基板。將定、緒 果歸納示於表1中。 曰此外，處理液中的丨，2,3-三唑的含量相對於處理液總 量為2.5質量％51，2,4•三補含量相對於處 2 5 質量°/〇。 (實例6 ) 除了代替實例1中使用的包含1，2,3-三唑的水溶液， 而使用包含1，2,3-三唑-4-甲酸的水溶液（溶劑：水，液温： 25 C ’ pH值：6，1，2,3-三唑-4-曱酸相對於水溶液總量的 含量：1質量％) ’使附有銅配線的基板浸潰5分鐘以外， 以與貫例1相同的程序，製造附有銅離子擴散抑制層的銅 配線基板。將各種測定結果歸納示於表1中。 (實例7) 除了使用實例1中使用的包含1,2,3-三唾的水溶液， 使附有銅配線的基板浸潰240秒，且代替HAST試驗中使 用的絕緣膜 PFR-800 而使用 ABF GX-13 (Ajinomoto Fine Techno (股）製造）以外，以與實例1相同的程序，製造 附有銅離子擴散抑制層的銅配線基板。將各種測定結果歸 納示於表1中。 (比較例1) 除了代替實例1中使用的包含1，2,3-三唑的水溶液， 而使用包含苯并三唑的水溶液（溶劑：水，液溫：25。(：， 201251542 42UlUpif pH值.6’苯并三唑相對於水溶液總量的含量：丨質量％)， 伽有銅配線的基板浸潰10分鐘以外，以與實例丨相同的 私序，製造附有銅離子擴散抑制層的銅配線基板。將各種 測定結果歸納示於表1中。 (比較例2) 除了代替實例1中使用的包含1，2 3_三唑的水溶液’ 而使用包含二聚硫氰酸的水溶液（溶劑：水，液溫：25。〇， pH值.6 ’二聚硫氰酸相對於水溶液總量的含量：〇〇1質 畺/〇)’使附有銅配線的基板浸潰分鐘以外，以與實例 1相同的程序，製造附有銅離子擴散抑制層的銅配線基 板。將各種測定結果歸納示於表1令。 (比較例3) 除了代替實例1中使用的包含1，2,3-三唑的水溶液， 而使用包含3-胺基-1，2,4-三唑的水溶液（溶劑：水，液溫： 25C ’ pH值.7 ’ 3-胺基-1，2,4-三嗤相對於水溶液總量的 含量：2.5質量％)’使附有銅配線的基板浸潰5分鐘以外， 以與實例1相同的程序，製造附有銅離子擴散抑制層的銅 配線基板。將各種測定結果歸納示於表1中。 (比較例4) 除了使用實例1中使用的包含1，2,3-三唑的水溶液， 使附有銅配線的基板浸潰3秒以外，以與實例1相同的程 序’製造附有銅離子擴散抑制層的銅配線基板。將各種測 定結果歸納示於表1中。 (比較例5) 31 201251542 除了代替實例1中使用的1，2,3-三唑而使用包含1，2,4-三嗤的水溶液，使附有銅配線的基板浸潰12小時以外，以 與實例1相同的程序’製造附有銅離子擴散抑制層的銅配 線基板。將各種測定結果歸納示於表1中。 此外’實例6、比較例2中的各處理液的pH值是使用 氫氧化鈉來調整。另外，pH值的測定時使用PH計 (DKK-TOA公司製造）。表1中的「附著量」是指各實例 以及比較例中的附有銅離子擴散抑制層的銅配線基板的銅 配線上所附著的含氮有機化合物的附著量，其測定是利用 上述吸光度測定法來進行。 32 201251542 JUOStN寸 l< HAST 試驗 〇 〇 〇 〇 〇 <] 〇 X X X X X ^ 〇> ^ ^ ^ <N Ο (N OO cn r-H 寸 (N 〇\ <N 寸 τ-Η (N cn m rn CO Ο cn ρ PQ s T—< UO OO o m oo O m o o m ON 〇 g O l-H CN CN i-H ο 卜 CN i-H 蝕刻速率B (μπι/min ) o oo o o (N o o o o o <N OO o o o On (N to ο 〇\ o 蝕刻速率A (μιη/min ) 卜 o in 〇 〇 o in o to o r> o 〇 to o JO o ΙΟ ο r> d 附著量 (g/mm2) 3.5xl〇-8 5.6xl〇-8 2.1X10'8 4.2xl〇-8 2.5xl0'8 2.1X10·8 l.OxlO·7 1.0x10—9 8.〇xl 0'8 3.5xl0'8 l.oxl Ο'9 2.〇xlO'6 含氮有機化合物 1 _1 1,2,3-三唑 1,2,3-三唑 1,2,4-三唑 1，2,4-三唑 1，2,3-三唑以及1，2,4- 三口坐 1，2,3-三唑-4-甲酸 1，2,3-三唑 苯并三唑 三聚硫氰酸 3-胺基-1,2,4-三唑 1，2,3-三唑 1，2,4-三唑 實例1 實例2 m 冢 IK 實例4 實例5 實例6 實例7 比較例1 比較例2 比較例3 1比較例41 比較例5 201251542 …^上述表1所示，_認：含氮有機化合物的附著量在 規疋範圍θ i與不具有銅離子擴散抑制層的附有銅配線 的基板的綱料之比為規定範圍的本發明的印刷配線基 板，其銅=線間的樹枝狀結晶的成長速度緩慢，銅配線間 的絕，可靠性優異。尤其根據實例1〜實例7的比較，確 認：藉由使用丨，2,3.三唾及/或1，2,4·三峻的情況，高溫高 濕環境下的絕緣特性優異。進而根據實例1〜實例4的比 較’確認：在使用1，2,4-三唑的情況下，樹枝狀結晶的成 長速度更小，絕緣特性優異。 另一方面’不滿足含氮有機化合物的附著量、或者上 述触刻速率之比的至少任一者的比較例1〜比較例5中， 銅配線間的樹枝狀結晶的成長速度快，銅配線間的絕緣可 靠性差。 【圖式簡單說明】 圖1是表示本發明的印刷配線基板的一實施形態的示 意性剖面圖β 圖2是依次表示本發明的附有絕緣膜的印刷配線基板 的製造方法的各步驟的示意性剖面圖。 【主要元件符號說明】 10 :印刷配線基板 12 :基板 14 :銅配線 16 :銅離子擴散抑制層 18 :附有銅配線的基板 34 201251542 42UlUpif 20 :含有含氮有機化合物的層 22 :絕緣膜 35The plate, the treatment liquid, and the like are prepared, and then the procedure of the layer formation step is described. J (substrate with copper wiring) In addition, the substrate (core substrate) with copper wiring used in this step has a board 'and is placed on the board| wiring. In other words, the copper wiring board has a laminated structure including at least a substrate and copper wiring, and the copper wiring is disposed at the most. The other metal wiring (wiring pattern) can be prepared between the substrate and the copper wiring as follows. And the interlayer insulating layer, a 15 201251542 other metal wiring and the interlayer insulating layer may alternately include two or more layers between the substrate and the copper wiring in this order. That is, the substrate to which the copper wiring is attached may be a so-called multilayer wiring substrate or a build-up substrate. A well-known insulating material can be used for the interlayer insulating layer, and examples thereof include a phenol resin, a naphthalene resin, a urea resin, an amine resin, an alkyd resin, an epoxy resin, and an acrylate resin. Further, the substrate to which the copper wiring is attached may be a so-called rigid substrate, a flexible substrate, or a rigid flexible substrate. The copper wiring may be provided only on one side of the substrate or on both sides. That is, the substrate with the copper wiring may be a single-sided substrate or a double-sided substrate. The definition of the substrate in the substrate with the copper wiring is as described above. In addition, the definition of the wiring in the substrate with the copper wiring is also as described above. (Processing liquid) The treatment liquid used in this step contains a nitrogen-containing organic compound, and the pH value is 5 to 9 〇 The definition of the nitrogen-containing organic compound is as described above. Further, in the production method, when benzotriazole is used as the nitrogen-containing organic compound, most of the benzotriazole is washed away by washing with a cleaning solvent in a washing step described later, and as a result, a predetermined amount of adhesion cannot be obtained. The copper ion diffusion suppression layer. Further, in the treatment liquid containing the benzotriazole-containing treatment liquid containing the excess etchant or the imidazole compound having the rice engraving ability, the organic film formed on the copper wiring contains excessive copper ions, and as a result, the predetermined copper cannot be obtained. The ratio of the etch rate of the wiring. 201251542 ^zuiupif In addition, in the production method, when thi〇cyanurie acid or 3-amino-1,2,4-triazole is used as the nitrogen-containing organic compound, performance is not obtained. A printed wiring board having desired characteristics. The total content of the nitrogen-containing organic compound in the treatment liquid is not particularly limited, and the above-described easiness of formation of the copper ion diffusion suppression layer and control of the adhesion amount of the copper ion diffusion suppression layer are the same as the total amount of the treatment liquid. The total content of the nitrogen-containing organic compound is preferably 〇. (Π% by mass% to 1% by mass, more preferably 0.1% by mass to 55% by mass of 0), particularly preferably 〇25% by mass to 55% by mass. When the total content of the nitrogen-containing organic compound is too large, it is difficult to control the deposition amount of the copper ion diffusion suppression layer. If the total content of the nitrogen-containing organic compound is too small, it takes time until the required amount of the copper ion diffusion suppression layer is accumulated. The solvent may be contained in the treatment liquid. The solvent to be used is not particularly limited, and examples thereof include water, an alcohol solvent (for example, decyl alcohol, ethanol, and isopropanol), and a ketone solvent (for example, acetone, A). Base ethyl ketone, cyclohexanone), guanamine solvent (for example, formamide, dimethyl acetamide, N-methylpyrrolidone), nitrile solvent (such as acetonitrile, propionitrile), ester solvent (eg acetic acid) Ester, ethyl acetate), a carbonate-based solvent (for example, dimethyl carbonate or diethyl carbonate), an ether solvent, a halogen solvent, etc. These solvents may be used in combination of two or more kinds. In terms of safety in the production of the wiring board, water or an alcohol-based solvent is preferable. In particular, when water is used as the solvent, when the substrate having the copper wiring is brought into contact with the treatment liquid, the impregnation method is used. The content of the solvent in the treatment liquid is not particularly limited, and the content of the solvent is preferably 90% by mass to 99% by mass based on the total amount of the treatment liquid. 99% 〇 /, more preferably 95% by mass to 99.9% by mass 'Specially 95% by mass 〇 '% by mass. ' On the other hand, in terms of improving the insulation reliability of the copper wiring in the printed wiring board Preferably, the treatment liquid contains substantially no copper ions. If an excessive amount of copper ions is included, when the copper ion diffusion suppression layer is formed, the layer contains _ sub, and (4) the neutron migration is weakly present. In the case where the insulation reliability between the wires is impaired, the content of the copper ions in the treatment liquid is preferably 1 μιηοΐ / ΐ or less, more preferably 〇 丨 丨 / 丨 。. In order to improve the insulation reliability between the copper wirings in the printed wiring board, it is preferable that the processing liquid contains substantially no rot of copper. 'When the financial support is attached to the copper plate and the treatment liquid, there is a case where the child is neglected to handle the liquid towel. Therefore, the copper ion diffusion suppression layer contains copper ions, and the effect of suppressing copper ion migration is weak, and copper exists. When the insulation reliability of the distribution is impaired, examples of the side agent include organic acids (for example, sulfuric acid, two, hydrochloric acid, acetic acid, formic acid, hydrogen acid), oxidizing agents (for example, hydrogen peroxide, concentrated sulfuric acid), and chelating agents. (eg, iminodiacetic acid, mtril〇triacetic acid, ethyldiaminetetraacetic acid ethyldiamine, ethanolamine, aminopropanol), thiol compound #. Further, the side agent also contains a compound having a copper itself such as miso, or a imiline derivative compound as 201251542 ^uiupif. In addition, the term "substantially no etchant" means that the content of the etchant in the treatment liquid is 0.01 mass%/〇 or less with respect to the total f of the treatment liquid, and the insulation reliability between the copper wirings is further improved. Say 'better for i please be below mass%. The best is 〇 quality 0 / 〇. The pH of the treatment liquid showed 5 to 9. Among them, the pH is more preferably 6 to 8 in terms of the insulation reliability between the copper wirings in the printed wiring board. When the pH of the treatment liquid is less than 5, copper ions are promoted to be eluted from the copper wiring, and a large amount of copper ions are contained in the copper ion diffusion suppression layer. As a result, the effect of suppressing migration of copper may be lowered. When the pH of the treatment liquid exceeds 9, the copper hydroxide precipitates and is easily oxidized and dissolved, and as a result, the effect of suppressing the migration of copper may be lowered. Further, the adjustment of the pH can be carried out by using a known acid (for example, hydrochloric acid, sulfur, or a test (for example, sodium ruthenium oxide). Further, a known measurement method can be used for the measurement of the pH (for example, a pH meter (in the case of a water solvent) Further, the treatment liquid may contain other additives (for example, a pH adjuster, a surfactant, a preservative, a precipitation inhibitor, etc.). (Solvent (cleaning solvent)) Cleaning of the substrate with copper wiring is cleaned. The solvent (cleaning solvent) used in the step is not particularly limited as long as it can remove excess nitrogen-containing organic compound or the like between the copper wirings deposited on the substrate. Among them, a solvent for dissolving the nitrogen-containing organic compound is preferably used. This solvent can more efficiently go to 201251542 except for excess nitrogen-containing organic compounds deposited on the substrate, or excess nitrogen-containing organic compounds on the wiring, etc. 'As a solvent', for example, water, an alcohol-based solvent (for example, methanol, Ethanol, propanol), ketone solvents (eg, propyl, decyl ketone, cyclohexanone), guanamine solvents (eg, formazan, dimethyl Amidoxime, N-methylpyrrolidinium), a nitrile solvent (for example, acetonitrile, propionitrile), an ester solvent (for example, methyl acetate, ethyl acetate), a carbonate solvent (for example, dinonyl carbonate, Carbonic acid-ethyl ester), an ether solvent, a halogen solvent, etc. may be used in combination of two or more kinds. Among them, in terms of liquid permeability between the fine wirings, it is preferable to contain water selected from water. The solvent of at least one of the group consisting of the alcohol solvent and the mercaptoethyl ketone is more preferably a mixture of an alcohol solvent and water. The boiling point of the solvent used (25t: , i atmospheres) is not In particular, from the viewpoint of safety, it is preferably 7 yc to 1 Torr (rc, more preferably 80 ° C to 10 (TC). The surface tension of the solvent to be used (25. 〇 is not particularly limited, just face 1 The cleaning property between the wirings is more excellent, and the insulation reliability between the copper wirings is improved. It is preferably 10 mN/m to 80 mN/m, more preferably 15 mN/m to 6 〇 mN/m. Procedure of the step) The layer forming step is divided into two steps of a contact step and a washing step. First, the substrate with the copper 201251542 42UlUpif wiring having the substrate and the copper wiring disposed on the substrate is brought into contact with a treatment liquid containing a nitrogen-containing organic compound and having a pH value of 5 to 9. More specifically, The substrate 18 with the copper wiring including the substrate 12 and the copper wiring 14 shown in FIG. 2(A) is in contact with the processing liquid, and as shown in FIG. 2(B), is formed on the substrate 18 with the copper wiring. a layer 20 containing a nitrogen-containing organic compound. The layer 20 is formed on the substrate 12 and on the copper wiring 14. That is, in other words, this step is to bring the substrate with the copper wiring into contact with the treatment liquid, and cover the surface of the substrate with a nitrogen-containing organic compound. The step of the surface of the copper wiring. The layer containing the nitrogen-containing organic compound contains a nitrogen-containing organic compound. The content and the like of the nitrogen-containing organic compound have the same meanings as those in the above-mentioned copper ion diffusion-suppressing layer. Further, the amount of the nitrogen-containing organic compound to be attached is not particularly limited. It is preferred to obtain a deposition amount of the copper ion diffusion-suppressing layer having a desired adhesion amount by a washing step to be described later. The method of contacting the substrate with the copper wiring and the treatment liquid is not particularly limited, and a known method can be employed. For example, the impregnation dipping, the spray spray, the spray coating, the spin coating, and the like are preferable, and the ease of the treatment and the ease of adjustment of the treatment time are preferably impregnation, spray, and spray. Spray coating. Further, the liquid temperature of the treatment liquid at the time of contact with respect to the adhesion amount of the copper ion diffusion suppression layer is preferably in the range of 5 ° C to 60 ° C, more preferably 15. 〇~50〇C range, especially good for 20. In the range of the production property and the adhesion amount of the copper ion diffusion suppression layer, the contact time is preferably in the range of 10 seconds to 3 minutes, more preferably 15 seconds. The range of 10 minutes, especially the range of 3 sec to 5 minutes, 2012 21 521 • v A Λ Λ. (cleaning step) Then, the solvent is used to clean the substrate with the copper wiring, and the surface of the copper wiring is formed. A copper ion diffusion-suppressing layer containing a nitrogen-containing organic compound. Specifically, the copper wiring-attached substrate 18 provided with the layer 20 containing the nitrogen-containing organic compound obtained in Fig. 2 is cleaned by using the above-mentioned cleaning solvent. As shown in FIG. 2(C), the layer 20 containing the nitrogen-containing organic compound between the copper wirings 14 is removed, and the excess nitrogen-containing organic compound on the copper wiring μ is removed, and the nitrogen-containing organic compound is formed on the copper wiring 14. The copper ion diffusion suppression layer 16. That is, in other words, this step is a step of removing the nitrogen-containing organic compound on the surface of the substrate by using a solvent to clean the substrate with the copper wiring. The cleaning method is not particularly limited and may be employed. For example, a method of applying a cleaning solvent to a substrate having a copper wiring, a method of impregnating a substrate having a copper wiring in a cleaning solvent, and the like can be used. In terms of the amount of adhesion control, the liquid temperature of the cleaning solvent is preferably 5. (: ～ 603⁄4, more preferably 15 〇 C to 30 ° C. In addition, productivity, and copper ion diffusion suppression layer In terms of the adhesion amount control, the contact time of the substrate with the copper wiring and the cleaning solvent is preferably in the range of 10 seconds to 10 minutes, more preferably in the range of 15 seconds to 5 minutes. (Drying step) In this step The substrate with the copper wiring 22201251542 ^zuiupif provided with the copper ion diffusion suppression layer is heated and dried. If moisture remains on the substrate with the copper wiring, there is a sincerity to promote the migration of the nano, so it is preferable to set the substrate. In order to suppress the oxidation of the copper wiring, the heating and drying conditions are preferably f 7 〇 C to 120 ° C (preferably 8 (TC 〜 11 〇. 〇 under the implementation of 15 seconds ~ 10 ^ buckle ( Preferably 30 seconds to 5 minutes). When the temperature is too low, or when it is dry, it is too short for the water to be insufficient. If the drying temperature is too high or the drying time is too long, there is a concern that copper oxide is formed. A known heating device such as a constant temperature layer or a heater can be used. In addition, this step is an arbitrary step, and the solvent used in the layer forming step is a solvent having excellent volatility, and the like. The printed wiring board may have an insulating film so as to cover the copper ion diffusion suppressing layer as needed. More specifically, as shown in FIG. 2(D), the insulating film 22 is a copper ion diffusion suppressing layer 16 and is disposed on the surface. The copper wiring η is placed in contact with the substrate 18 to which the copper wiring is attached. The laminated body (printed wiring board with an insulating film) having the substrate 12, the copper wiring 14 disposed on the substrate 12, and the copper wiring 14 can be obtained. The insulating film 22 has a copper ion diffusion suppressing layer 16 interposed between the copper wiring 14 and the insulating film 22. By providing the insulating film 22, the insulation reliability between the copper wirings 14 is further ensured. Further, since the substrate 12 and the insulating film 22 can be in direct contact with each other, the insulating film 22 is excellent in adhesion. First, the insulating film to be used will be described, and then a method of forming the insulating film 23 201251542 will be described. As the insulating film, a known insulating material can be used. For example, a material which can be used as an interlayer insulating film is specifically exemplified by an epoxy resin, an aromatic "amine resin, a crystalline polylocene resin, an amorphous polybut furnace resin, and a fluorine-containing tree." Polytetrafluoroethylene, perfluoropolyimine, total gas, amorphous resin, etc., polyimine resin, polyether simple fat, polyphenylene resin, polyether ether resin, acrylate resin, and the like. Examples of the interlayer insulating film include ABF GX-13 manufactured by Ajinomoto Fine Techno Co., Ltd., and the like. Further, a so-called solder resist layer can also be used as the insulating film. For the solder resist, a commercially available product can be used, and, for example, _00, PSR4000 (trade name) manufactured by Taiyin Ink Co., Ltd., and SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like can be used. The method of forming the insulating film is not particularly limited, and a known method can be employed. For example, a method of directly laminating a film of an insulating film on a printed wiring board, or a method of applying a composition for forming an insulating film containing a component constituting the insulating film onto a printed wiring board, or a printed wiring board A method of immersing in the composition for forming an insulating film or the like. Further, the above-mentioned composition for forming an insulating film may optionally contain a solvent. In the case of using a composition for forming an insulating film containing a solvent, after the composition is placed on a substrate, heat treatment may be applied as needed to remove the solvent. Further, after the insulating film is provided on the printed wiring board, energy can be applied to the insulating film (e.g., exposure or heat treatment) as needed. 24 201251542 4201〇pif Further, the 'insulating film may be provided on the entire surface of the printed wiring board, or may be provided on the - portion. For example, a part of the copper wiring in the printed wiring board may be exposed so as to cover the copper wiring. The film thickness of the insulating film to be formed is not particularly limited, and is preferably 5 to 5 μm μm, more preferably μ μηι to 40 μπι, from the viewpoint of insulation sin in the copper wiring. The obtained insulating film was partially removed, and a semiconductor wafer was mounted for use as a printed circuit board. For example, when a solder resist is used as the insulating film, a mask having a predetermined pattern is placed on the insulating film, energized and hardened, and an insulating film in a region where no energy is applied is removed to expose the copper wiring. Then, the surface of the exposed copper wiring is cleaned (for example, by using sulfuric acid or a surfactant) by a known method, and then the semiconductor wafer is mounted on the surface of the copper wiring. In the case where a known interlayer insulating film is used as the insulating film, the insulating film can be removed by drilling or laser processing. [Application] The printed wiring board of the present invention can be used for various applications and structures, and examples thereof include a mother board substrate, a semiconductor package board, a molded interconnect device (MID) board, and the like, and a rigid board. A flexible substrate, a flexible rigid substrate, a molded circuit board, or the like is used. In addition, the growth rate of dendritic crystals generated between the copper wirings of the printed wiring board of the present invention is preferably 2.9 μm/sec or less, more preferably 2.9 μm/sec or less, and more preferably 2.5. Below μηι/sec, it is preferably 2.0 μπι/sec or less. [Examples] Hereinafter, the present invention will be further described in detail by way of examples, but the invention is not limited to the examples. (Example 1) A comb-shaped copper wiring substrate (a substrate with a copper wiring) of L/S = 100 μm / 100 μm was formed by a subtractive method using a glass epoxy substrate. A substrate with copper wiring was produced by the following method. On a copper clad laminate (MCL-E-679F manufactured by Kelly Chemical Co., Ltd., substrate: glass epoxy substrate), a dry laminator was laminated at 70 ° C under a pressure of 2 2 MPa using a vacuum laminator. Film resist (DFR, trade name: RY3315, manufactured by Hitachi Chemical Co., Ltd.) After lamination, the copper pattern forming portion was masked at 70 mJ/cm2 using an exposure machine having a center wavelength of 365 nm. Then, it was developed with a 1 〇/0 aqueous solution of sodium hydrogencarbonate, and washed with water to obtain a pattern of anti-surname for subtraction and etch. Then, the copper of the non-resist portion in which the resist pattern was not formed was obtained. Before the last name, the obtained substrate was spray-sprayed with 45 t of 40% copper oxide liquid. Then, the obtained substrate was washed with water. Then, in order to peel off the resist pattern, the substrate was placed in a 45 〇c 4% NaOH aqueous solution. The resulting substrate was washed with water and then immersed in 1% sulfuric acid for 30 seconds. Thereafter, it was washed again. Then, a pretreatment agent (26 201251542 Hzuiupif CA-manufactured by MEC) was used. 5330) to remove dirt and the like on the surface of the copper wiring, Then, the roughening treatment of the surface of the copper wiring is performed by using a roughening treatment agent (CZ-8110 manufactured by MEC Co., Ltd.) to obtain a surface of the copper wiring with a copper wiring of L/S=100 μm/100 μηι. The degree is rz=1.〇. Then, the obtained copper wiring-attached substrate is in an aqueous solution containing 1,2,3-triazole (solvent: water, 1,2,3-triazole content: relative to aqueous solution) The total amount is 2.5% by mass, the liquid temperature is 25. The 〇, ρ Η value: 7) is immersed for 3 sec. Then, the obtained copper wiring-attached substrate is washed with ethanol (contact time · 2 minutes, liquid temperature: 25 ° C. Further, the substrate was dried under a crucible for 2 minutes to obtain a copper wiring substrate with a copper ion diffusion suppression layer having a copper ion diffusion suppression layer on a substrate with a copper wiring. (corresponding to a printed wiring board). By performing reflectance measurement, it was confirmed that a copper ion diffusion suppressing layer containing cerium, 2,3-oxadiazole was formed on the copper wiring. Further, by the above-mentioned absorbance measurement, the compound was measured by the absorbance. The amount of adhesion is 3.5 X10·8 g/mm2. A copper wiring board with a copper ion diffusion-suppressing layer/in a etched aqueous solution containing 1.8% by mass of sulfuric acid and 12% by mass of sodium peroxodisulfate, the etching rate of the copper wiring was measured by the above gravimetric method ( B μιη/min). Etching rate B was 0.76 μm/min » Further 'Using an untreated copper wiring-attached substrate having no copper ion diffusion suppression layer' was measured by the same method as described above. A is 0.75 μηη/min. The ratio of etch rate (B/A) is 1.01. In addition, 'the surface of the substrate between the copper wirings of the copper wiring board with the copper ion diffusion-suppressing layer is measured by the absorbance of the copper wiring between the waters 27 201251542, and the copper ion diffusion suppression layer cannot be confirmed. It was removed by ethanol washing. (Measurement of dendritic growth rate by solution impregnation test) The obtained copper wiring substrate with a copper ion diffusion suppression layer was immersed in hydrochloric acid having a pH of 5, and a voltage of 1.2 V was applied between the copper wirings. The growth rate (μηι/sec) of dendritic crystals generated between the copper wirings was measured under an optical microscope (BX-51, manufactured by Olympus Co., Ltd.). The results obtained in Example 1 are shown in Table 1. (Measurement of substrate life by HAST test) An insulating film (PFR-800 manufactured by Taiyolnk Co., Ltd.) was laminated on the obtained copper wiring substrate with a copper ion diffusion suppression layer, and then exposed and baked to produce an insulating film. Printed wiring board (film thickness of insulating film: 35 μm) ° Using the obtained printed wiring board with an insulating film, the humidity is 85%, the temperature is 130 degrees, the pressure is 1.2 atm, and the voltage is 1 〇〇V. Life measurement was carried out under conditions (using device: manufactured by espec, EHS-221MD). The evaluation method was carried out by preparing 20 rods (20 printed wiring boards with an insulating film) to carry out the above test. In addition, the resistance value between the copper wirings is based on 1x109 Ω. A rod whose resistance value after 12 hours from the start of the test was expressed as a reference resistance value or more was set as a pass. The results obtained in Example 1 are shown in Table 1. In addition, evaluation was performed based on the following evaluation criteria. "〇": Among the 20 shots, 20 shots are displayed as the reference resistance value or more. 28 201251542 ^zuiupif "△": The "1 to 19" of 20 shots is displayed as the reference resistance value or more. "X": Among the 20 shots, there is no case where the display is equal to or higher than the reference resistance value. (Example 2) Copper ion diffusion was carried out in the same procedure as in Example i except that the crucible, the 2, 3_ three-pin aqueous solution was used, and the substrate with the copper wiring was immersed for 2 minutes and 30 seconds. A copper wiring substrate of a suppression layer. The results of various measurements are summarized in Table 1. (Example 3) In addition to the example 1, an aqueous solution containing H3-trisin was used, and the content of 1,2,4-disal was used to contain 1,2,4-three with respect to the total amount of the aqueous solution of 25 mass%. Aqueous aqueous solution (solvent: water, liquid temperature: 25 〇, value: 6) 'The substrate with the copper wiring was immersed for 45 seconds, and the same procedure as in the example} was used to produce a copper ion diffusion suppression layer. Copper wiring board. The results of various measurements are summarized in Table 1. (Example 4) In addition to the aqueous solution containing ^3-triazole used in Example 1, the content of 1,2,4-triazole was used in an amount of 25% by mass based on the total amount of the aqueous solution, including 1,2,4- An aqueous solution of disazone (solvent: water, liquid temperature: 25 〇c, pH: 6) 'The copper ion diffusion suppression was produced by the same procedure as in Example 1 except that the substrate with the copper wiring was immersed for 5 minutes. A layer of copper wiring substrate. The results of various measurements are summarized in Table 1. (Example 5) In addition to the aqueous solution containing 1,2,3-triazole used in Example 1, 29 201251542, and the use of 1,2,3-triazole and 1,2,4-tri,. A steel ion diffusion suppression layer-wiring substrate was produced in the same procedure as in Example 以外 except for an aqueous solution (solvent: water, temperature: 25 Torr, pH: 6). The definitions and results are summarized in Table 1. Further, the content of ruthenium, 2,3-triazole in the treatment liquid is 2.5% by mass relative to the total amount of the treatment liquid, and the content of 2,4•3 is relative to the mass of 25 mass/〇. (Example 6) An aqueous solution containing 1,2,3-triazole-4-carboxylic acid (solvent: water, liquid temperature: 25 C) was used instead of the aqueous solution containing 1,2,3-triazole used in Example 1. 'pH value: content of 6,1,2,3-triazole-4-decanoic acid relative to the total amount of the aqueous solution: 1% by mass) 'The substrate with the copper wiring was immersed for 5 minutes, and the example 1 was In the same procedure, a copper wiring substrate with a copper ion diffusion suppression layer was fabricated. The results of various measurements are summarized in Table 1. (Example 7) ABF was used, and the substrate with the copper wiring was dipped for 240 seconds, and the ABF was used instead of the insulating film PFR-800 used in the HAST test, except that the aqueous solution containing 1,2,3-three saliva used in Example 1 was used. A copper wiring board with a copper ion diffusion suppression layer was produced in the same procedure as in Example 1 except for GX-13 (manufactured by Ajinomoto Fine Techno Co., Ltd.). The results of various measurements are summarized in Table 1. (Comparative Example 1) An aqueous solution containing benzotriazole (solvent: water, liquid temperature: 25 was used instead of the aqueous solution containing 1,2,3-triazole used in Example 1 (:, 201251542 42UlUpif pH value) .6' content of benzotriazole relative to the total amount of the aqueous solution: 丨 mass%), and the substrate having the copper wiring was immersed for 10 minutes, and the copper ion diffusion suppression layer was produced in the same private order as the example 丨. Copper wiring board. Various measurement results are summarized in Table 1. (Comparative Example 2) An aqueous solution containing a dimerized thiocyanate (solvent was used instead of the aqueous solution containing 1,2 3 -triazole used in Example 1) : water, liquid temperature: 25. 〇, pH value. 6 'content of dimer thiocyanate relative to the total amount of aqueous solution: 〇〇1 mass 畺 / 〇) 'so that the substrate with copper wiring is immersed for minutes, A copper wiring board with a copper ion diffusion suppression layer was produced in the same procedure as in Example 1. The results of various measurements are summarized in Table 1. (Comparative Example 3) In addition to the use of 1, 2, 3 in place of Example 1. An aqueous solution of triazole, using an aqueous solution containing 3-amino-1,2,4-triazole (dissolved : water, liquid temperature: 25C 'pH value. 7 ' 3-amino-1,2,4-triazole relative to the total amount of aqueous solution: 2.5% by mass) 'Immerse the substrate with copper wiring for 5 minutes A copper wiring board with a copper ion diffusion suppression layer was produced in the same manner as in Example 1. The results of various measurements are summarized in Table 1. (Comparative Example 4) In addition to the use of 1, 2 contained in Example 1, A copper wiring board with a copper ion diffusion suppression layer was produced in the same procedure as in Example 1 except that the substrate with the copper wiring was immersed for 3 seconds. The measurement results are summarized in the table. (Comparative Example 5) 31 201251542 In addition to the 1,2,3-triazole used in Example 1, an aqueous solution containing 1,2,4-triazole was used, and the substrate with the copper wiring was immersed for 12 hours. A copper wiring board with a copper ion diffusion suppression layer was produced in the same procedure as in Example 1. The various measurement results are summarized in Table 1. Further, the pH values of the respective treatment liquids in Example 6 and Comparative Example 2 were also shown. It is adjusted with sodium hydroxide. In addition, the pH is measured using a pH meter (DKK-TOA) The "adhesive amount" in Table 1 refers to the adhesion amount of the nitrogen-containing organic compound adhered to the copper wiring of the copper wiring board with the copper ion diffusion suppression layer in each of the examples and the comparative examples, and the measurement is performed. The above absorbance measurement method is carried out. 32 201251542 JUOStN inch l< HAST test file<] 〇XXXXX ^ 〇> ^ ^ ^ <N Ο (N OO cn rH inch (N 〇\ <N inch) τ-Η (N cn m rn CO Ο cn ρ PQ s T-< UO OO om oo O moom ON 〇g O lH CN CN iH ο 卜 CN iH Etching rate B (μπι/min) o oo oo (N ooooo <N OO ooo On (N to ο 〇\ o etch rate A (μιη/min) 卜o in 〇〇o in o to o r> o 〇to o JO o ΙΟ ο r> d adhesion amount (g/mm2 ) 3.5xl〇-8 5.6xl〇-8 2.1X10'8 4.2xl〇-8 2.5xl0'8 2.1X10·8 l.OxlO·7 1.0x10—9 8.〇xl 0'8 3.5xl0'8 l. Oxl Ο'9 2.〇xlO'6 Nitrogen-containing organic compound 1 _1 1,2,3-triazole 1,2,3-triazole 1,2,4-triazole 1,2,4-triazole 1, 2,3-triazole and 1,2,4-trisole 1,2,3-triazole-4-carboxylic acid 1,2,3-triazole benzotriazole tripolysulfide Acid 3-Amino-1,2,4-triazole 1,2,3-triazole 1,2,4-triazole Example 1 Example 2 m 冢IK Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 1 Comparative Example 41 Comparative Example 5 201251542 As shown in Table 1, the adhesion amount of the nitrogen-containing organic compound is in the range θ i and the copper wiring with no copper ion diffusion suppression layer In the printed wiring board of the present invention in which the ratio of the substrate is in a predetermined range, the growth rate of the dendrites between the copper and the lines is slow, and the reliability between the copper wirings is excellent. In particular, according to the comparison of Examples 1 to 7, it was confirmed that the insulating property in a high-temperature and high-humidity environment was excellent by using yttrium, 2, 3. trisodium and/or 1,2,4·sanjun. Further, according to the comparison of Examples 1 to 4, it was confirmed that in the case of using 1,2,4-triazole, the dendrite has a smaller growth rate and is excellent in insulating properties. On the other hand, in Comparative Example 1 to Comparative Example 5, which did not satisfy at least one of the adhesion amount of the nitrogen-containing organic compound or the above-described etch rate, the dendrite growth rate between the copper wiring lines was fast, and the copper wiring was fast. Poor insulation reliability. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an embodiment of a printed wiring board according to the present invention. FIG. 2 is a schematic view showing steps of a method for manufacturing a printed wiring board with an insulating film according to the present invention in order. Sexual profile. [Description of main component symbols] 10 : Printed wiring substrate 12 : Substrate 14 : Copper wiring 16 : Copper ion diffusion suppression layer 18 : Substrate with copper wiring 34 201251542 42UlUpif 20 : Layer containing nitrogen-containing organic compound 22 : Insulating film 35