TW202200489A - Manufacturing method for metal filled microstructure - Google Patents
Manufacturing method for metal filled microstructure Download PDFInfo
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Abstract
Description
本發明係有關一種使用閥金屬構件之金屬填充微細結構體的製造方法，尤其係有關一種輸送性優異且絕緣性能化良好之金屬填充微細結構體的製造方法。The present invention relates to a method for producing a metal-filled microstructure using a valve metal member, and more particularly, to a method for producing a metal-filled microstructure having excellent transportability and improved insulating performance.
在設置於絕緣性基材之複數個貫通孔中填充金屬等導電性物質而製成之結構體係近年來在奈米技術中亦受關注之領域之一，例如期待作為各向異性導電性構件的用途。 各向異性導電性構件***到半導體元件等電子零件與電路基板之間，僅藉由進行加壓便得到電子零件與電路基板之間的電連接，因此作為半導體元件等電子零件等的電連接構件及進行功能檢查時的檢查用連接器等被廣泛使用。 尤其，半導體元件等電子零件的小型化顯著。在如習知之焊線接合之類的直接連接配線基板之方式、覆晶接合及熱壓接合等中，由於無法充分保證電子零件的電連接的穩定性，因此各向異性導電性構件作為電子連接構件而備受關注。In recent years, one of the fields of nanotechnology has also attracted attention in the field of nanotechnology, for example, it is expected to be used as an anisotropic conductive member. use. The anisotropically conductive member is inserted between electronic components such as semiconductor elements and a circuit board, and electrical connection between the electronic components and the circuit board is obtained only by applying pressure, so it is used as an electrical connection member for electronic components such as semiconductor elements. It is widely used as an inspection connector for functional inspection. In particular, the miniaturization of electronic components such as semiconductor elements is remarkable. In the conventional method of directly connecting the wiring board such as wire bonding, flip chip bonding, thermocompression bonding, etc., since the stability of the electrical connection of electronic components cannot be sufficiently ensured, the anisotropic conductive member is used as the electronic connection. components have attracted much attention.
例如，在專利文獻1中記載有一種微細結構體的製造方法，前述微細結構體由以1000萬個/mm2
以上的密度具有微孔貫通孔之基材組成，一部分微孔貫通孔被除基材的材料以外的物質所填充。在專利文獻1的微細結構體的製造方法中，基材係氧化鋁，在鋁基板上至少依次實施：（A）處理，藉由陽極氧化處理而形成具有微孔之氧化覆膜；（B）處理，從藉由上述（A）處理得到之氧化覆膜去除鋁；（C）處理，使存在於藉由上述（B）處理被去除鋁之氧化覆膜中之微孔的一部分貫通；（D）處理，在藉由上述（C）處理而貫通之微孔內，填充除氧化覆膜以外的物質；及（E）表面平滑化處理，藉由化學機械研磨處理，將上述（D）處理後的氧化覆膜的表面及背面進行平滑化。For example,
[專利文獻1]日本特開2013-167023號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-167023
在上述專利文獻1的微細結構體的製造方法中，能夠得到微孔貫通孔被除基材的材料以外的物質所填充之微細結構體。如上所述，在專利文獻1的微細結構體的製造方法中，實施：（D）處理，在所貫通之微孔內，填充除氧化覆膜以外的物質；及（E）處理，實施藉由化學機械研磨處理將上述（D）處理後的氧化覆膜的表面及背面進行平滑化之表面平滑化，但是亦可不連續進行上述（D）和上述（E）的處理，而在上述（D）之後，例如藉由輸送等在經過既定時間之後實施上述（E）。在該情況下，填充部可能因輸送等而損傷。又，受到製程之間的環境等影響，微細結構體的絕緣性能亦可能劣化。In the manufacturing method of the microstructure of the said
本發明的目的在於提供一種輸送性優異且抑制絕緣性能劣化之金屬填充微細結構體的製造方法。An object of the present invention is to provide a method for producing a metal-filled microstructure which is excellent in transportability and suppresses deterioration of insulating performance.
為了實現上述目的，本發明的一態樣係提供一種金屬填充微細結構體的製造方法，其具有：形成製程，藉由在由配置於閥金屬構件外緣之框部包圍之形成區域中形成具有複數個細孔之氧化膜，得到具有閥金屬構件和氧化膜之結構體；填充製程，對結構體在氧化膜的複數個細孔中填充金屬；及保持製程，將藉由填充製程對結構體在氧化膜的複數個細孔中填充金屬而得到之金屬填充構件，在相對濕度10～30%的環境下暴露24小時以上，複數個細孔的平均直徑為1μm以下。In order to achieve the above-mentioned object, one aspect of the present invention provides a method of manufacturing a metal-filled microstructure, comprising: a forming process by forming a metal-filled microstructure in a forming region surrounded by a frame portion disposed on an outer edge of a valve metal member with a Oxide film with a plurality of pores to obtain a structure with valve metal components and oxide film; filling process, filling metal in the plurality of pores of the oxide film for the structure; and maintaining process, the structure will be filled by the filling process. A metal-filled member obtained by filling a plurality of pores of an oxide film with metal is exposed to an environment with a relative humidity of 10 to 30% for 24 hours or more, and the average diameter of the pores is 1 μm or less.
閥金屬由鋁構成為較佳。 氧化膜係陽極氧化膜為較佳。 陽極氧化膜係Al2 O3 為較佳。 在填充製程中，在氧化膜的複數個細孔中填充之金屬係銅為較佳。 填充製程係藉由在結構體的表面上形成金屬層而將金屬填充於複數個細孔中之製程，填充製程在框部上形成厚度為100μm以下的金屬層為較佳。 在保持製程之後，具有去除形成於結構體的表面上之金屬層之金屬層去除製程為較佳。 在金屬層去除製程之後，具有將氧化膜的表面平滑化之表面進行平滑化處理製程為較佳。 表面平滑化處理製程的平滑化使用化學機械研磨、乾式蝕刻或研削為較佳。 [發明效果]The valve metal is preferably composed of aluminum. The oxide film is preferably an anodic oxide film. The anodic oxide film is preferably Al 2 O 3 . In the filling process, metal-based copper is preferably filled in the plurality of pores of the oxide film. The filling process is a process in which a metal layer is formed on the surface of the structure and the metal is filled in a plurality of pores. The filling process is preferably to form a metal layer with a thickness of 100 μm or less on the frame portion. After the hold process, a metal layer removal process that removes the metal layer formed on the surface of the structure is preferred. After the metal layer removal process, it is preferable to perform a smoothing process on the surface of the oxide film to smoothen the surface. The smoothing of the surface smoothing process is preferably carried out by chemical mechanical polishing, dry etching or grinding. [Inventive effect]
依本發明，能夠獲得輸送性優異且抑制絕緣性能劣化之金屬填充微細結構體的製造方法。According to the present invention, it is possible to obtain a method for producing a metal-filled microstructure which is excellent in transportability and suppresses deterioration of insulation performance.
以下，基於圖式所示較佳實施形態，對本發明的金屬填充微細結構體的製造方法進行詳細說明。 另外，以下進行說明之圖係用於說明本發明中之例示性圖，本發明並不限定於以下所示圖。 另外，以下表示數值範圍之“～”係指包括記載於兩側之數值。例如，εa 為數值αb ～數值βc 係指，εa 的範圍係包括數值αb 和數值βc 之範圍，若用數學記號來表示，則為αb ≤εa ≤βc 。 若無特別記載，則“正交”等角度包括在相應技術領域中通常容許之誤差範圍。又，關於濕度及時間，若無特別記載，則包括在相應技術領域中通常容許之誤差範圍。Hereinafter, the method for producing the metal-filled microstructure of the present invention will be described in detail based on the preferred embodiments shown in the drawings. In addition, the drawings described below are exemplary drawings for explaining the present invention, and the present invention is not limited to the drawings shown below. In addition, "-" which shows a numerical range below means that the numerical value described in both sides is included. For example, when ε a is a numerical value α b to a numerical value β c , it means that the range of ε a includes the numerical value α b and the numerical value β c . If expressed in mathematical notation, α b ≤ ε a ≤ β c . If there is no special description, the "orthogonal" and other angles include the generally allowable error range in the corresponding technical field. In addition, the humidity and time are included in the range of error generally allowable in the corresponding technical field unless otherwise specified.
關於金屬填充微細結構體，具有細孔（貫通孔）之氧化膜的絕緣電阻發生了變動。檢查絕緣電阻的變動，發現了根據保管位置及保管時間而受到影響。發現了如下現象：即使在不進行特別的溫度調節之倉庫內，在寒冷季節絕緣電阻亦良好，或者即使在實施溫度調節之建築物內，絕緣電阻亦不定期劣化等。 經過深入研究之結果，認為具有細孔（貫通孔）之氧化膜中的水分是否造成影響，而不是保管中的溫度，在保管條件中，尤其對濕度檢查與絕緣性能的關係之結果，獲知藉由保持在某一濕度範圍內而得到穩定之絕緣電阻，並完成了本發明。以下，關於金屬填充微細結構體的製造方法進行具體說明。In the metal-filled microstructure, the insulation resistance of the oxide film having pores (through holes) varies. The change in insulation resistance was examined, and it was found that it was affected by the storage location and storage time. It was found that the insulation resistance is good in cold seasons even in a warehouse where special temperature regulation is not performed, or the insulation resistance is not periodically deteriorated even in a building where temperature regulation is performed. As a result of intensive research, it is considered whether the moisture in the oxide film with pores (through holes) has an effect, not the temperature during storage. In the storage conditions, especially the relationship between humidity and insulation performance was examined. Stable insulation resistance is obtained by keeping within a certain humidity range, and the present invention has been completed. Hereinafter, the method for producing the metal-filled microstructure will be specifically described.
[金屬填充微細結構體的製造方法的第1例] 圖1～圖6及圖12～圖19係按製程順序表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一例之示意性剖視圖。圖7係圖5所示結構體的俯視圖，圖8係放大表示圖7所示結構體的區域Q之示意性俯視圖，圖9係放大表示圖7所示結構體的區域Q之示意性剖視圖。又，圖10係關於圖6所示金屬填充構件放大表示相當於圖7所示結構體的區域Q之部分之示意性俯視圖，圖11係關於圖6所示金屬填充構件放大表示相當於圖7所示結構體的區域Q之部分之示意性剖視圖。[The first example of a method for producing a metal-filled microstructure] FIGS. 1 to 6 and FIGS. 12 to 19 are schematic cross-sectional views showing an example of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention in the order of the processes. 7 is a plan view of the structure shown in FIG. 5 , FIG. 8 is an enlarged schematic plan view of a region Q of the structure shown in FIG. 7 , and FIG. 9 is an enlarged schematic cross-sectional view of the region Q of the structure shown in FIG. 7 . 10 is an enlarged schematic plan view showing a portion corresponding to the region Q of the structure shown in FIG. 7 with respect to the metal filling member shown in FIG. 6 , and FIG. 11 is an enlarged view showing the metal filling member shown in FIG. 6 and corresponding to FIG. 7 A schematic cross-sectional view of a portion of region Q of the structure shown.
金屬填充微細結構體係對閥金屬構件的表面實施陽極氧化處理而得到者。金屬填充微細結構體係具有由閥金屬的陽極氧化膜組成之絕緣性基材者。閥金屬係鋁等，但是並不特別限定於鋁，作為絕緣性基材，以鋁的陽極氧化膜為例進行說明。因此，在以下說明中，作為閥金屬構件，以鋁基板為例進行說明。
如圖1所示，作為閥金屬構件11而準備鋁基板。
其次，如圖2所示，僅在閥金屬構件11的表面11a的外緣11b上形成遮罩12。遮罩12若係電絕緣者，則並不受特別的限定，例如能夠使用用於形成半導體元件之公知的阻劑膜。關於遮罩12，例如，在閥金屬構件11的表面11a的整面上形成阻劑膜之後，使用光微影法去除除閥金屬構件11的表面11a的外緣11b以外的阻劑膜，僅在外緣11b上形成遮罩12。除此以外，作為遮罩12，例如可以使用阻劑筆僅在閥金屬構件11的表面11a的外緣11b上形成阻劑膜。此外，亦可將具有耐酸性之黏著性樹脂膠帶黏貼於閥金屬構件11的表面11a的外緣11b上而設為遮罩12。
在閥金屬構件11的表面11a中，由遮罩12包圍之區域11c係陽極氧化膜16（參閱圖5）的形成區域。The metal-filled microstructure system is obtained by anodizing the surface of the valve metal member. The metal-filled microstructure system has an insulating substrate composed of an anodized film of valve metal. Although the valve metal is aluminum or the like, it is not particularly limited to aluminum, and an anodized film of aluminum will be described as an example of the insulating base material. Therefore, in the following description, as the valve metal member, an aluminum substrate is used as an example.
As shown in FIG. 1 , an aluminum substrate is prepared as the
其次，進行陽極氧化膜形成製程，在該製程中實施以閥金屬構件11作為電極之陽極氧化處理，並在閥金屬構件11中的由遮罩12包圍之區域11c中形成陽極氧化膜。另外，陽極氧化膜16（參閱圖5）係絕緣性基材。
在陽極氧化膜形成製程中，以閥金屬構件11作為陽極電極實施陽極氧化處理。藉此，閥金屬構件11被陽極氧化，如圖3所示，在閥金屬構件11的區域11c中形成陽極氧化膜11d。在陽極氧化處理中，例如可以從閥金屬構件11的背面側施加電流，亦可從外緣11b側施加電流。Next, an anodized film forming process is performed, in which an anodization treatment is performed using the
在陽極氧化處理中，如上所述，將閥金屬構件11用作電極，閥金屬構件11的區域11c（參閱圖3）成為陽極氧化膜11d的形成區域，遮罩12下方的閥金屬構件11（參閱圖2）係外緣15b（參閱圖4），並成為框部15d（參閱圖4）。
在上述區域11c中形成陽極氧化膜11d，但是遮罩12下方的閥金屬構件11不被陽極氧化。如此，閥金屬構件11不會全部成為陽極氧化膜11d，而在陽極氧化處理之後亦存在保持閥金屬構件15之區域。藉此，在閥金屬構件15的外緣15b上，配置由閥金屬構件15構成之閥金屬構件15的框部15d。在由框部15d包圍之區域15c中形成陽極氧化膜16（參閱圖4）。
另外，由於閥金屬構件11由鋁構成，因此作為氧化膜而形成陽極氧化膜16，陽極氧化膜16由Al2
O3
膜構成。In the anodizing treatment, as described above, the
陽極氧化膜11d在所形成之時點存在複數個微孔。然而，在複數個微孔中，亦有在厚度方向Dt上未貫通之微孔。又，在微孔的底部存在阻擋層（未圖示）。因此，對圖3所示陽極氧化膜11d去除阻擋層，如圖4所示，在陽極氧化膜16上形成複數個在厚度方向Dt上延伸之貫通孔17。The
藉由以上製程，在由配置於閥金屬構件15的外緣15b之框部15d包圍之區域15c中形成具有複數個細孔（貫通孔17）之氧化膜（陽極氧化膜16），藉此得到具有閥金屬構件15和氧化膜（陽極氧化膜16）之結構體18。例如，如圖7及圖8所示，在閥金屬構件15的表面15a上形成陽極氧化膜16，在陽極氧化膜16的周圍存在框部15d。又，如圖9所示，陽極氧化膜16的表面16a和框部15d的表面大致係同一面。
如上所述，圖3所示陽極氧化膜形成製程和圖4所示之形成複數個在厚度方向Dt上延伸之貫通孔17之製程係，得到結構體18之形成製程。Through the above process, an oxide film (anodic oxide film 16 ) having a plurality of pores (through holes 17 ) is formed in the
[鋁基板] 鋁基板並不受特別的限定，作為其具體例，可舉出：純鋁板；以鋁為主要成分，並包含微量的異質元素之合金板；在低純度鋁（例如回收材料）上蒸鍍有高純度鋁之基板；在矽晶圓、石英、玻璃等表面上，藉由蒸鍍、濺射等方法而被覆有高純度鋁之基板；層合有鋁之樹脂基板；等。[Aluminum plate] The aluminum substrate is not particularly limited, and specific examples thereof include: a pure aluminum plate; an alloy plate mainly composed of aluminum and containing a trace amount of foreign elements; Substrates of high-purity aluminum; substrates coated with high-purity aluminum on the surfaces of silicon wafers, quartz, glass, etc. by methods such as evaporation and sputtering; resin substrates laminated with aluminum; etc.
在鋁基板中，藉由陽極氧化處理形成陽極氧化膜之一側的表面，其鋁純度為99.5質量%以上為較佳，99.9質量%以上為更佳，99.99質量%以上為進一步較佳。若鋁純度在上述範圍內，則微孔排列的規則性變得充分。 鋁基板若能夠形成陽極氧化膜，則並不受特別的限定，例如使用JIS（Japanese Industrial Standards：日本工業標準） 1050材料及1070材料。In the aluminum substrate, on the surface on the side where the anodized film is formed by anodization, the aluminum purity is preferably 99.5 mass % or more, more preferably 99.9 mass % or more, and even more preferably 99.99 mass % or more. When the aluminum purity is within the above range, the regularity of the micropore arrangement becomes sufficient. The aluminum substrate is not particularly limited as long as an anodized film can be formed, and for example, JIS (Japanese Industrial Standards: Japanese Industrial Standards) 1050 material and 1070 material are used.
在鋁基板中被陽極氧化處理之一側的表面預先被實施熱處理、脫脂處理及鏡面精加工處理為較佳。 在此，關於熱處理、脫脂處理及鏡面精加工處理，能夠實施與日本特開2008-270158號公報的[0044]～[0054]段中所記載之各處理相同之處理。 陽極氧化處理之前的鏡面精加工處理例如係電解研磨，在電解研磨中例如使用含有磷酸之電解研磨液。 在此，作為閥金屬，具體而言，例如除了上述鋁以外，還可以舉出鉭、鈮、鈦、鉿、鋯、鋅、鎢、鉍及銻等。It is preferable that a heat treatment, a degreasing treatment, and a mirror finishing treatment are performed in advance on the surface of the anodized side of the aluminum substrate. Here, about the heat treatment, the degreasing treatment, and the mirror finishing treatment, the same treatments as those described in paragraphs [0044] to [0054] of JP-A No. 2008-270158 can be performed. The mirror surface finishing treatment before the anodizing treatment is, for example, electropolishing, and in the electropolishing, for example, an electrolytic polishing liquid containing phosphoric acid is used. Here, specific examples of the valve metal include tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, and the like in addition to the above-mentioned aluminum, for example.
〔陽極氧化處理製程〕 陽極氧化處理能夠利用以往公知的方法，但是從提高微孔排列的規則性且確保金屬填充微細結構體的各向異性導電性之觀點考慮，使用自規則化法或恆壓處理為較佳。 在此，關於陽極氧化處理的自規則化法及恆壓處理，能夠實施與日本特開2008-270158號公報的[0056]～[0108]段及[圖3]中所記載之各處理相同之處理。[Anodizing process] Anodizing treatment can be performed by a conventionally known method, but from the viewpoint of improving the regularity of the micropore arrangement and securing the anisotropic conductivity of the metal-filled microstructure, it is preferable to use a self-regularization method or a constant pressure treatment. Here, regarding the self-regularization method and constant-voltage treatment of the anodizing treatment, the same processes as those described in paragraphs [0056] to [0108] and [ FIG. 3 ] of JP-A-2008-270158 can be performed. deal with.
在具有複數個微孔之陽極氧化膜中，如上所述，在微孔的底部存在阻擋層（未圖示）。具有去除該阻擋層之阻擋層去除製程。In an anodized film having a plurality of micropores, as described above, a barrier layer (not shown) is present at the bottom of the micropores. There is a barrier layer removal process for removing the barrier layer.
〔阻擋層去除製程〕 阻擋層去除製程係例如使用包含氫過電壓比鋁高的金屬M1離子之鹼性水溶液來去除陽極氧化膜的阻擋層之製程。 藉由上述阻擋層去除製程，去除阻擋層，並且在微孔的底部形成由金屬M1組成之導電體層。 在此，氫過電壓（hydrogen overvoltage）係指產生氫所需電壓，例如鋁（Al）的氫過電壓為-1.66V（日本化學會雜誌，1982、（8），p1305-1313）。另外，以下示出氫過電壓比鋁高的金屬M1的示例及其氫過電壓值。 ＜金屬M1及氫（1N H2 SO4 ）過電壓＞ ・鉑（Pt）：0.00V ・金（Au）：0.02V ・銀（Ag）：0.08V ・鎳（Ni）：0.21V ・銅（Cu）：0.23V ・錫（Sn）：0.53V ・鋅（Zn）：0.70V[Barrier layer removal process] The barrier layer removal process is, for example, a process of removing the barrier layer of the anodized film using an alkaline aqueous solution containing metal M1 ions having a higher hydrogen overvoltage than aluminum. Through the above-mentioned barrier layer removal process, the barrier layer is removed, and a conductor layer composed of metal M1 is formed at the bottom of the micro-hole. Here, the hydrogen overvoltage refers to the voltage required to generate hydrogen, for example, the hydrogen overvoltage of aluminum (Al) is -1.66V (Journal of the Chemical Society of Japan, 1982, (8), p1305-1313). In addition, an example of the metal M1 whose hydrogen overvoltage is higher than that of aluminum and its hydrogen overvoltage value are shown below. <Overvoltage of metal M1 and hydrogen (1N H 2 SO 4 )> ・Platinum (Pt): 0.00V ・Gold (Au): 0.02V ・Silver (Ag): 0.08V ・Nickel (Ni): 0.21V ・Copper ( Cu): 0.23V ・Tin (Sn): 0.53V ・Zinc (Zn): 0.70V
貫通孔17（細孔）亦可藉由將微孔擴徑並去除阻擋層而形成。在該情況下，在微孔的擴徑中使用擴孔處理。擴孔處理係藉由使陽極氧化膜浸漬於酸性水溶液或鹼性水溶液中而溶解陽極氧化膜並擴大微孔的孔徑之處理，在擴孔處理中，能夠使用硫酸、磷酸、硝酸、鹽酸等無機酸或該等混合物的水溶液、或者氫氧化鈉、氫氧化鉀及氫氧化鋰等的水溶液。 另外，在擴孔處理中亦可去除微孔底部的阻擋層，在擴孔處理中藉由使用氫氧化鈉水溶液，微孔被擴徑且去除阻擋層。 與阻擋層去除製程同樣，擴孔處理無法形成導電體層。因此，在擴孔處理之後，可以重新使用包含氫過電壓比鋁高的金屬M1離子之水溶液來進行處理而形成導電體層，還可以用包含不同金屬之水溶液來實施複數個階段的處理而形成導電體層。The through holes 17 (fine holes) can also be formed by expanding the diameter of the micro holes and removing the barrier layer. In this case, a hole expansion process is used for diameter expansion of the micropores. Pore expansion treatment is a process of dissolving the anodized film and expanding the pore size of the micropores by immersing the anodized film in an acidic aqueous solution or an alkaline aqueous solution. An aqueous solution of an acid or a mixture of these, or an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. In addition, the barrier layer at the bottom of the micropore can also be removed in the hole expansion treatment. In the hole expansion treatment, by using an aqueous sodium hydroxide solution, the diameter of the micropore is enlarged and the barrier layer is removed. Like the barrier removal process, the hole expansion process cannot form a conductor layer. Therefore, after the hole expansion treatment, an aqueous solution containing metal M1 ions having a higher hydrogen overvoltage than aluminum can be used again to form a conductor layer, and an aqueous solution containing different metals can be used for multiple stages of treatment to form a conductive layer. body layer.
其次，從圖4的狀態去除遮罩12（參閱圖5）。然後，實施填充製程，該填充製程對圖5所示結構體18在陽極氧化膜16的複數個貫通孔17中填充金屬。藉由對結構體18在陽極氧化膜16的複數個貫通孔17的內部填充金屬，如圖6所示，形成具有導電性之導通路20，並得到金屬填充構件21。另外，填充金屬之填充製程在後面詳細說明。
在填充製程中，只要在陽極氧化膜16的複數個貫通孔17的內部填充金屬即可，但是如圖5、圖10及圖11所示，亦可藉由在結構體18的表面上，亦即在金屬填充構件21的框部15d上及陽極氧化膜16的表面16a上形成金屬層19，將金屬填充於複數個貫通孔17。在該情況下，在框部15d上，以（圖5及圖11）100μm以下的厚度δ形成金屬層19為較佳。作為金屬層19的厚度δ的下限值，例如為2μm。
若金屬層19的厚度δ為2～100μm，則導通路20得到保護，當輸送金屬填充構件21時，抑制陽極氧化膜16及導通路20等的損傷。另外，金屬層19的厚度δ例如藉由延長鍍覆時間而增大。在填充製程中，藉由超出陽極氧化膜16的表面16a填充金屬，在框部15d上形成金屬層19。
在填充製程中，在貫通孔17內填充金屬直至陽極氧化膜16的表面16a，從而可以設為不設置金屬層19之製程。Next, the
金屬層19的厚度δ係在厚度方向上切斷金屬填充構件21，使用FE-SEM（Field emission-Scanning Electron Microscope：場發射掃描電子顯微鏡）觀察切斷剖面的剖面，並測定10點之平均值。
又，閥金屬構件15的底部15e的厚度並不受特別的限定，但是20μm以上為較佳，30～50μm為進一步較佳。
上述閥金屬構件15的底部15e的厚度係，與上述金屬層19的厚度δ相同，在厚度方向上切斷金屬填充構件21，使用FE-SEM觀察切斷剖面的剖面，並測定10點之平均值。The thickness δ of the
藉由填充上述金屬之填充製程，得到金屬填充構件21。其次，實施保持製程，該製程將金屬填充構件21在相對濕度10～30%的環境下暴露24小時以上。關於保持製程，只要係將金屬填充構件21在相對濕度10～30%的環境下暴露24小時以上之製程，則該製程並不受特別的限定，關於保持製程，後面進行說明。Through the filling process of filling the above-mentioned metal, the
〔填充製程〕
＜被填充之金屬＞
在上述貫通孔17的內部，作為導電性物質被填充之金屬係電阻率為103
Ω・cm以下的材料為較佳，作為其具體例，較佳地例示出金（Au）、銀（Ag）、銅（Cu）、鋁（Al）、鎂（Mg）、鎳（Ni）、鋅（Zn）等。
另外，從導電性的觀點考慮，作為導電性物質，Cu、Au、Al、Ni為較佳，Cu、Au為更佳，Cu為進一步較佳。[Filling process] <Filled metal> The inside of the through
＜填充方法＞ 作為在貫通孔的內部填充金屬之電鍍處理方法，例如，能夠使用電鍍法或無電鍍法。 在此，在著色等中使用之以往公知的電鍍法中，難以選擇性地使金屬在孔中以高縱橫比析出（生長）。可以認為其理由在於，即使析出金屬在孔內被消耗並進行恆定時間以上的電解，鍍層亦不會生長。 因此，在藉由電鍍法填充金屬之情況下，脈衝電解或恆定電位電解時需要設置中止時間。中止時間需要10秒鐘以上，30～60秒鐘為較佳。 又，為了促進電解液的攪拌，亦期望施加超聲波。＜Filling method＞ As a plating treatment method for filling the inside of the through hole with metal, for example, a plating method or an electroless plating method can be used. Here, in a conventionally known electroplating method used for coloring or the like, it is difficult to selectively precipitate (grow) a metal in a hole with a high aspect ratio. The reason for this is considered to be that the plating layer does not grow even if the precipitation metal is consumed in the hole and electrolysis is performed for a predetermined time or longer. Therefore, in the case of filling metal by the electroplating method, it is necessary to set a stop time in the case of pulse electrolysis or constant potential electrolysis. The suspension time needs to be more than 10 seconds, preferably 30 to 60 seconds. In addition, it is also desirable to apply ultrasonic waves in order to promote stirring of the electrolytic solution.
此外，電解電壓通常為20V以下，期望為10V以下，但預先測定所使用之電解液中之目標金屬的析出電位，並在該電位+1V以內進行恆定電位電解為較佳。另外，當進行恆定電位電解時，期望能夠併用循環伏安法者為較佳，能夠使用Solartron公司、BAS Inc.、HOKUTO DENKO CORP.、IVIUM公司等的恆電位儀裝置。 在上述電鍍處理方法中，亦可使用恆定電流電解，但是將電流值設定為使電解時的電壓在與上述電解電壓相同之範圍內為較佳。在該情況下，能夠利用通常的直流電源，例如能夠使用MATSUSADA PRECISION Inc.、TAKASAGO LTD.、KIKUSUI ELECTRONICS CORP.、TEXIO TECHNOLOGY CORPORATION等的公知的裝置。又，在上述電鍍處理方法中，亦可使用在鍍覆處理中通常使用之脈衝電解。In addition, the electrolysis voltage is usually 20V or less, desirably 10V or less, but it is preferable to measure the precipitation potential of the target metal in the electrolyte to be used, and to perform constant-potential electrolysis within +1V of the potential. In addition, when performing constant potential electrolysis, it is desirable to be able to use cyclic voltammetry in combination, and potentiostat devices such as Solartron, BAS Inc., HOKUTO DENKO CORP., IVIUM, etc. can be used. In the above-mentioned electroplating treatment method, constant current electrolysis may be used, but it is preferable to set the current value so that the voltage during electrolysis is within the same range as the above-mentioned electrolysis voltage. In this case, a normal DC power supply can be used, and for example, known devices such as MATSUSADA PRECISION Inc., TAKASAGO LTD., KIKUSUI ELECTRONICS CORP., TEXIO TECHNOLOGY CORPORATION and the like can be used. Moreover, in the said electroplating process method, the pulse electrolysis which is generally used in a plating process can also be used.
鍍液能夠使用以往公知的鍍液。 具體而言，在使銅析出之情況下，通常使用包含硫酸銅之水溶液，但是硫酸銅的濃度，1～300g/L為較佳，100～200g/L為更佳。又，若在電解液中添加鹽酸，則能夠促進析出。在該情況下，鹽酸濃度為10～20g/L為較佳。 又，鍍液可以含有酸，該酸濃度為0.01～1mol/L為較佳。As the plating solution, a conventionally known plating solution can be used. Specifically, in the case of precipitating copper, an aqueous solution containing copper sulfate is usually used, but the concentration of copper sulfate is preferably 1 to 300 g/L, more preferably 100 to 200 g/L. In addition, if hydrochloric acid is added to the electrolytic solution, precipitation can be accelerated. In this case, the concentration of hydrochloric acid is preferably 10 to 20 g/L. In addition, the plating solution may contain an acid, and the acid concentration is preferably 0.01 to 1 mol/L.
電解液可以添加添加劑，作為添加於電解液中之添加劑，例如存在以下所示者。又，藉由添加劑，得到以下所示作用。 作為添加劑，亦可添加被稱為光澤劑、平滑劑之添加成分。在附著抑制作用中，分子或離子單獨吸附或析出，抑制鍍覆反應。糖精、苯并噻唑、硫脲、杰納斯綠B（JGB）、苯并丙酮、鉛、鉍等相當於具有附著抑制作用者。 在界面絡合物形成作用中，吸附於表面之微量絡合物形成離子與金屬離子配位而形成離子橋接或電橋，藉此促進析出反應。認為氯化物離子、CN- 、SCN- 、硫類化合物（硫脲、3,3´-二硫代雙（1-丙烷磺酸）二鈉（SPS）、二巰基噻唑（DMTD）等）、硼酸、草酸、丙二酸等與此對應。 在覆膜形成作用中，界面活性劑或高分子輕度附著於鍍覆表面上而形成覆膜，抑制鍍覆反應。PEG（聚乙二醇）、聚乙二醇單-4-壬基苯基醚（PEGNPE）、聚乙烯醇、明膠等係代表例。 在電解消耗機構中，分子或離子在鍍覆表面上迅速被電解還原，該反應藉由該等分子或離子向表面的擴散輸送而被控制速度。藉此，鍍覆的表面形狀的凹凸變小。不飽和醇（丁炔二醇、炔丙醇、香豆素等）、NO3 - 、Fe3 + 等係代表例。 又，鍍液將表面張力調整為盡可能低亦較佳，作為表面張力，設為比純水低的60mN/m以下為較佳。為了調整表面張力，亦可添加界面活性劑或有機溶劑。 鍍液調整pH（氫離子指數）為較佳，期望pH為1以上。An additive may be added to the electrolytic solution, and as an additive to be added to the electrolytic solution, there are, for example, those shown below. Moreover, by the additive, the following functions are obtained. As an additive, an additive component called a glossing agent and a smoothing agent can also be added. In the adhesion inhibition action, molecules or ions are adsorbed or precipitated alone, and the plating reaction is inhibited. Saccharin, benzothiazole, thiourea, Janus green B (JGB), benzoacetone, lead, bismuth, etc. are equivalent to those with adhesion inhibitory effect. In the formation of interfacial complexes, a small amount of complex-forming ions adsorbed on the surface coordinate with metal ions to form ion bridges or bridges, thereby promoting the precipitation reaction. Think chloride ions, CN - , SCN - , sulfur compounds (thiourea, 3,3´-dithiobis(1-propanesulfonic acid) disodium (SPS), dimercaptothiazole (DMTD), etc.), boric acid , oxalic acid, malonic acid, etc. correspond to this. In the film-forming action, the surfactant or polymer is lightly attached to the plating surface to form a film and suppress the plating reaction. PEG (polyethylene glycol), polyethylene glycol mono-4-nonylphenyl ether (PEGNPE), polyvinyl alcohol, gelatin, etc. are representative examples. In an electrolytic depletion mechanism, molecules or ions are rapidly electrolytically reduced on a plated surface, and the reaction is speed-controlled by diffusive transport of the molecules or ions to the surface. Thereby, the unevenness|corrugation of the surface shape of plating becomes small. Unsaturated alcohols (butynediol, propargyl alcohol, coumarin, etc.), NO 3 − , Fe 3 + and the like are representative examples. In addition, the surface tension of the plating solution is preferably adjusted to be as low as possible, and the surface tension is preferably 60 mN/m or less, which is lower than that of pure water. In order to adjust the surface tension, a surfactant or an organic solvent may also be added. The pH (hydrogen ion index) of the plating solution is preferably adjusted, and the pH is desirably 1 or more.
另外，在使金析出之情況下，期望使用四氯金的硫酸溶液，並藉由交流電解進行鍍覆。 又，在無電鍍法中，由於在由縱橫比高的貫通孔組成之孔中完全填充金屬需要長時間，因此期望利用電鍍法在貫通孔中填充金屬。In addition, in the case of depositing gold, it is desirable to perform plating by alternating current electrolysis using a sulfuric acid solution of gold tetrachloride. In addition, in the electroless plating method, since it takes a long time to completely fill a hole composed of a through hole with a high aspect ratio with a metal, it is desired to fill the through hole with a metal by an electroplating method.
在保持製程之後，如圖12所示，對金屬填充構件21，使用樹脂基材22在陽極氧化膜16的背面16b上設置支撐體24。
樹脂基材22例如使用功能性吸附膜。作為功能性吸附膜，能夠使用Q-chuck（註冊商標）（MARUISHI SANGYO CO.,LTD.製造）等。
支撐體24具有與陽極氧化膜16相同之外形為較佳。支撐體24在後續製程中支撐陽極氧化膜16。藉由安裝支撐體24，操作性提高。After the holding process, as shown in FIG. 12 , the
其次，如圖13所示，例如實施去除金屬填充構件21的金屬層19之金屬層去除製程。在金屬層去除製程中，例如使用黏著帶來剝離金屬層19。複數個貫通孔17的平均直徑為1μm以下而較小，能夠使用黏著帶容易去除金屬層。
另外，金屬層去除製程只要能夠去除金屬層19，則關於其方法並不受特別的限定。Next, as shown in FIG. 13 , for example, a metal layer removal process for removing the
具有表面平滑化處理製程為較佳，該製程在圖13所示之去除金屬層19之狀態下，將陽極氧化膜16的表面16a進行平滑化。表面平滑化處理製程的平滑化能夠使用化學機械研磨（CMP）、乾式蝕刻或研削，又，可以組合化學機械研磨（CMP）、乾式蝕刻及研削進行平滑化。在進行化學機械研磨（CMP）之情況下，可以組合不同磨料進行研磨，在任何方法中，精加工的表面粗糙度（算術平均粗糙度Ra（JIS B 0601：2001）為0.02μm以下亦較佳。
在金屬層去除製程之後，藉由實施表面平滑化處理製程，在表面平滑化處理製程中，能夠減少研磨量等，並能夠容易實施研磨。藉此，能夠縮短表面平滑化處理所需時間，並且容易進行平滑化。
上述金屬層去除製程和表面平滑化處理製程在保持製程之後進行。在上述金屬層去除製程及表面平滑化處理製程中，為了進行輸送等處理，在閥金屬構件15的背面上設置有支撐構件。It is preferable to have a surface smoothing process, which smoothes the
在表面平滑化處理製程之後，如圖14所示，可以以安裝有支撐體24之形態在厚度方向Dt上去除一部分陽極氧化膜16及框部15d，使上述所填充之金屬比陽極氧化膜16的表面16a突出。亦即，亦可使導通路20從陽極氧化膜16的表面16a突出。將導通路20從陽極氧化膜16的表面16a突出之部分稱為突出部20a。將使上述所填充之金屬比陽極氧化膜16的表面16a突出之製程稱為金屬突出製程。After the surface smoothing process, as shown in FIG. 14 , a part of the anodized
〔金屬突出製程〕
去除上述陽極氧化膜16的一部分中，例如使用不溶解構成導通路20之金屬，而溶解陽極氧化膜16亦即氧化鋁（Al2
O3
）之酸性水溶液或鹼性水溶液。藉由使上述酸性水溶液或鹼性水溶液接觸到具有填充有金屬之貫通孔17之陽極氧化膜16，去除一部分陽極氧化膜16。使上述酸性水溶液或鹼性水溶液接觸到陽極氧化膜16之方法並不受特別的限定，例如可舉出浸漬法、噴霧法及旋轉處理法等。其中，從均勻性的觀點考慮，使用旋轉處理器之處理方法為較佳。作為旋轉處理器，能夠使用Mimasu Semiconductor Industry Co.,Ltd.、Hitachi High-Tech Corporation.、SCREEN Holdings Co.,Ltd.、Dainippon Screen Mfg. Co.,Ltd.、ActesKyosan inc.、KANAMEX co.,ltd.等的公知產品。[Metal protrusion process] To remove a part of the
在使用酸性水溶液之情況下，使用硫酸、磷酸、硝酸及鹽酸等無機酸或該等混合物的水溶液為較佳。其中，從安全性優異之方面考慮，不含有鉻酸之水溶液為較佳。酸性水溶液的濃度為1～10質量%為較佳。酸性水溶液的溫度為25～60℃為較佳。 又，在使用鹼性水溶液之情況下，使用選自由氫氧化鈉、氫氧化鉀及氫氧化鋰組成之群組中之至少一種鹼性水溶液為較佳。鹼性水溶液的濃度為0.1～5質量%為較佳。鹼性水溶液的溫度為20～35℃為較佳。 具體而言，例如較佳地使用50g/L、40℃的磷酸性水溶液、0.5g/L、30℃的氫氧化鈉水溶液或0.5g/L、30℃的氫氧化鉀水溶液。In the case of using an acidic aqueous solution, it is preferable to use an aqueous solution of inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, or a mixture thereof. Among them, an aqueous solution containing no chromic acid is preferable from the viewpoint of being excellent in safety. The concentration of the acidic aqueous solution is preferably 1 to 10% by mass. The temperature of the acidic aqueous solution is preferably 25 to 60°C. In addition, in the case of using an alkaline aqueous solution, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 20 to 35°C. Specifically, for example, a phosphoric acid aqueous solution of 50 g/L at 40°C, an aqueous sodium hydroxide solution of 0.5 g/L at 30°C, or an aqueous potassium hydroxide solution of 0.5 g/L at 30°C is preferably used.
對酸性水溶液或鹼性水溶液的浸漬時間，8～120分鐘為較佳，10～90分鐘為更佳，15～60分鐘為進一步較佳。在此，浸漬時間係指在重複進行了短時間的浸漬處理之情況下，各浸漬時間的合計。另外，在各浸漬處理之間，可以實施清洗處理，又可實施中和處理。The immersion time for the acidic aqueous solution or the alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and even more preferably 15 to 60 minutes. Here, the immersion time refers to the total of each immersion time when the immersion treatment for a short time is repeatedly performed. In addition, between each immersion treatment, a cleaning treatment may be performed, and a neutralization treatment may be performed.
又，雖然係使金屬比陽極氧化膜16的表面16a突出之程度，但是當將所製作之金屬填充微細結構體32用作各向異性導電性構件時，根據與配線基板等被接著物的壓接性變得良好之理由，使金屬比陽極氧化膜16的表面16a突出10～1000nm為較佳，突出50～500nm為更佳。亦即，從突出部20a的表面16a的突出量係10nm～1000nm為較佳，更佳為50nm～500nm。In addition, although the metal is protruded beyond the
在嚴格控制導通路20的突出部20a的高度之情況下，在貫通孔17的內部填充金屬之後，將陽極氧化膜16和導通路20的端部加工成同一平面狀，然後選擇性地去除陽極氧化膜為較佳。
又，在填充上述金屬之後，或者在金屬突出製程之後，以減小伴隨填充金屬而產生之導通路20內的應變為目的，能夠實施加熱處理。
從抑制金屬氧化之觀點考慮，加熱處理在還原性環境下實施為較佳，具體而言，在氧濃度為20Pa以下的條件下進行為較佳，在真空下進行為更佳。在此，真空係指氣體密度及氣壓中的至少一方比大氣低的空間的狀態。
又，加熱處理以校正為目的在對陽極氧化膜16施加應力之同時進行為較佳。
又，為了抑制乾燥時由水的表面張力引起之突出部彼此的收斂，實施超臨界乾燥為較佳。在超臨界乾燥中，例如能夠使用超臨界清洗乾燥裝置（SCRD6、Rexxam Co.,Ltd.製）等。In the case of strictly controlling the height of the protruding
藉由在陽極氧化膜16上使用支撐體24，與處理陽極氧化膜16單體相比，能夠抑制陽極氧化膜16的損傷，並容易進行處理。
在此，處理係指保持陽極氧化膜16、以及陽極氧化膜16的運輸、輸送及搬運等使陽極氧化膜16移動的動作。容易處理係指當保持上述陽極氧化膜16時、以及當移動上述陽極氧化膜16時，能夠抑制陽極氧化膜16的損傷等。由於容易處理，因此例如使所填充之金屬比陽極氧化膜16的表面16a突出能夠抑制該金屬的損傷。By using the
如圖14所示，由於所填充之金屬比陽極氧化膜16的表面16a突出，因此保護所突出之金屬亦即導通路20的突出部20a為較佳。因此，如圖15所示，將埋設有導通路20的突出部20a之樹脂層26形成於陽極氧化膜16的表面16a為較佳。將設置樹脂層26之製程稱為樹脂層形成製程。在金屬填充微細結構體的製造方法中，可以包括樹脂層形成製程。As shown in FIG. 14 , since the filled metal protrudes from the
由樹脂層26保護導通路20的突出部20a，能夠進一步提高金屬填充微細結構體的輸送性，更容易進行處理。樹脂層26係具備黏著性者，並且係賦予接著性者。
樹脂層26例如能夠使用以往公知的表面保護膠帶黏貼裝置及層壓機來形成。藉由設置樹脂層26，能夠提高金屬填充微細結構體的輸送性。Protecting the protruding
〔樹脂層形成製程〕
作為構成樹脂層26之樹脂材料，具體而言，能夠舉出例如乙烯類共聚物、聚醯胺樹脂、聚酯樹脂、聚氨酯樹脂、聚烯烴類樹脂、丙烯酸類樹脂及纖維素類樹脂等，但是從輸送性的觀點和容易用作各向異性導電性構件之觀點考慮，上述樹脂層係可剝離之帶黏著層膜為較佳，因加熱處理或紫外線曝光處理而黏著性減弱，並且可剝離之帶黏著層膜為更佳。[Resin layer formation process]
Specific examples of the resin material constituting the
上述帶黏著層膜並不受特別的限定，可舉出熱剝離型樹脂層及紫外線（ultraviolet：UV）剝離型樹脂層等。 在此，熱剝離型樹脂層在常溫下具有黏著力，僅藉由加熱便可以容易剝離者，因此主要多使用發泡性微膠囊等。 又，作為構成黏著層之黏著劑，具體而言，例如可舉出橡膠類黏著劑、丙烯酸類黏著劑、乙烯基烷基醚類黏著劑、聚矽氧類黏著劑、聚酯類黏著劑、聚醯胺類黏著劑、胺酯類黏著劑、苯乙烯-二烯嵌段共聚物類黏著劑等。 又，UV剝離型樹脂層係指，具有UV硬化型接著層者，且藉由硬化而喪失黏著力而可剝離者。The said film with an adhesive layer is not specifically limited, A thermal peeling-type resin layer, an ultraviolet (ultraviolet:UV) peeling-type resin layer, etc. are mentioned. Here, since the heat-peelable resin layer has adhesive force at normal temperature and can be easily peeled off only by heating, foamable microcapsules and the like are mainly used. In addition, as the adhesive constituting the adhesive layer, for example, rubber-based adhesives, acrylic-based adhesives, vinyl alkyl ether-based adhesives, polysiloxane-based adhesives, polyester-based adhesives, Polyamide adhesives, urethane adhesives, styrene-diene block copolymer adhesives, etc. In addition, the UV peeling-type resin layer refers to what has a UV-curable adhesive layer, and can be peeled off by losing the adhesive force by hardening.
作為UV硬化型接著層，可舉出在基礎聚合物中將碳-碳雙鍵導入到聚合物側鏈或主鏈中或主鏈末端之聚合物等。作為具有碳-碳雙鍵之基礎聚合物，將丙烯酸類聚合物作為基本骨架為較佳。 此外，丙烯酸類聚合物為了交聯，根據需要，亦能夠包含多官能性單體等作為共聚用單體成分。 具有碳-碳雙鍵之基礎聚合物能夠單獨使用，但亦能夠配合UV硬化性單體或低聚物。 UV硬化型接著層為了藉由UV照射而硬化，併用光聚合起始劑為較佳。作為光聚合起始劑，可舉出苯偶姻醚類化合物；縮酮類化合物；芳香族磺醯氯類化合物；光敏肟類化合物；二苯甲酮類化合物；噻噸酮類化合物；樟腦醌；鹵代酮；醯基膦氧化物；醯基膦酸酯等。Examples of the UV-curable adhesive layer include polymers in which carbon-carbon double bonds are introduced into the polymer side chain or main chain, or at the end of the main chain in the base polymer. As the base polymer having a carbon-carbon double bond, an acrylic polymer is preferably used as the base skeleton. Moreover, in order to bridge|crosslink, an acrylic polymer can also contain a polyfunctional monomer etc. as a comonomer component as needed. The base polymer having carbon-carbon double bonds can be used alone, but can also be used in combination with UV curable monomers or oligomers. In order to harden the UV-curable adhesive layer by UV irradiation, it is preferable to use a photopolymerization initiator. Examples of photopolymerization initiators include benzoin ether-based compounds; ketal-based compounds; aromatic sulfonic acid chloride-based compounds; photosensitive oxime-based compounds; benzophenone-based compounds; thioxanthone-based compounds; camphorquinone ; Halogenated ketones; Acrylophosphine oxides; Acrylophosphonates, etc.
作為熱剝離型樹脂層的市售品，例如可舉出WS5130C02、WS5130C10等Intellimer〔註冊商標〕膠帶（NITTA Corporation製造）；Somatac〔註冊商標〕TE系列（SOMAR公司製造）；No.3198、No.3198LS、No.3198M、No.3198MS、No.3198H、No.3195、No.3196、No.3195M、No.3195MS、No.3195H、No.3195HS、No.3195V、No.3195VS、No.319Y-4L、No.319Y-4LS、No.319Y-4M、No.319Y-4MS、No.319Y-4H、No.319Y-4HS、No.319Y-4LSC、No.31935MS、No.31935HS、No.3193M、No.3193MS等Riva Alpha〔註冊商標〕系列（NITTO DENKO CORPORATION.製造）；等。Examples of commercially available thermal peelable resin layers include Intellimer (registered trademark) tapes such as WS5130C02 and WS5130C10 (manufactured by NITTA Corporation); Somatac (registered trademark) TE series (manufactured by Somar Corporation); No. 3198, No. 3198LS, No.3198M, No.3198MS, No.3198H, No.3195, No.3196, No.3195M, No.3195MS, No.3195H, No.3195HS, No.3195V, No.3195VS, No.319Y- 4L, No.319Y-4LS, No.319Y-4M, No.319Y-4MS, No.319Y-4H, No.319Y-4HS, No.319Y-4LSC, No.31935MS, No.31935HS, No.3193M, No.3193MS etc. Riva Alpha [registered trademark] series (manufactured by NITTO DENKO CORPORATION.); etc.
作為UV剝離型樹脂層的市售品，能夠利用例如ELP DU-300、ELP DU-2385KS、ELP DU-2187G、ELP NBD-3190K、ELP UE-2091J等ELEPH HOLDER〔註冊商標〕（NITTO DENKO CORPORATION.製造）；Adwill D-210、Adwill D-203、Adwill D-202、Adwill D-175、Adwill D-675（均為Lintec Corporation.製造）；SUMILITE〔註冊商標〕FLS的N8000系列（Sumitomo Bakelite Co.,Ltd.製造）；UC353EP-110（FURUKAWA ELECTRIC CO.,LTD.製造）；等切割膠帶。此外，作為UV剝離型樹脂層的市售品，例如能夠利用ELP RF-7232DB、ELP UB-5133D（均為NITTO DENKO CORPORATION.製造）；SP-575B-150、SP-541B-205、SP-537T-160、SP-537T-230（均為FURUKAWA ELECTRIC CO.,LTD.製造）；等背磨膠帶。 又，上述帶黏著層膜能夠使用以往公知的表面保護膠帶黏貼裝置及層壓機進行黏貼。As commercially available products of the UV peelable resin layer, for example, ELEPH HOLDER [registered trademark] (NITTO DENKO CORPORATION. manufactured); Adwill D-210, Adwill D-203, Adwill D-202, Adwill D-175, Adwill D-675 (all manufactured by Lintec Corporation.); SUMILITE [registered trademark] N8000 series of FLS (Sumitomo Bakelite Co. , Ltd.); UC353EP-110 (manufactured by FURUKAWA ELECTRIC CO., LTD.); and other cutting tapes. Moreover, as a commercial item of a UV peeling type resin layer, for example, ELP RF-7232DB, ELP UB-5133D (both are manufactured by NITTO DENKO CORPORATION.); SP-575B-150, SP-541B-205, SP-537T can be used -160, SP-537T-230 (both are manufactured by FURUKAWA ELECTRIC CO., LTD.); Equal back grinding tape. Moreover, the said film with an adhesive layer can be bonded using the conventionally well-known surface protection tape bonding apparatus and a laminator.
作為樹脂層26的形成方法，除上述方法以外，例如還可以舉出將含有後述抗氧化材料、高分子材料、溶劑（例如甲基乙基酮等）等之樹脂組成物塗佈於陽極氧化膜16的表面及背面和導通路的突出部上並使其乾燥，根據需要進行燒成之方法等。
樹脂組成物的塗佈方法並不受特別的限定，例如能夠使用凹版塗佈法、反轉塗佈法、模塗法、刮刀塗佈法、輥塗法、氣刀塗佈法、絲網塗佈法、棒塗及幕塗法等以往公知的塗覆方法。
又，塗佈後的乾燥方法並不受特別的限定，例如可舉出在大氣下以0℃～100℃的溫度加熱幾秒鐘～幾十分鐘之處理，在減壓下以0℃～80℃的溫度加熱幾分鐘～幾小時之處理等。
又，乾燥後的燒成方法由於根據所使用之高分子材料而不同，因此並不受特別特別的限定，但是在使用聚醯亞胺樹脂之情況下，例如可舉出以160℃～240℃的溫度加熱2分鐘～60分鐘之處理等，在使用環氧樹脂之情況下，例如可舉出以30℃～80℃的溫度加熱2分鐘～60分鐘之處理等。As a method of forming the
其次，從陽極氧化膜16去除圖15所示支撐體24。在該情況下，以樹脂基材22為起點，從陽極氧化膜16去除支撐體24。
其次，如圖16所示，在樹脂層26的表面26a上積層剝離層27。剝離層27係積層有支撐層28和剝離劑29者。剝離劑29接觸於樹脂層26。例如，藉由加熱為預先確定之溫度，剝離劑29的接著力減弱，能夠去除剝離層27。
作為剝離劑29，例如能使用Nitto Denko Corporation製造的REVALPHA（註冊商標）及SOMAR Corporation製造的SOMATAC（註冊商標）等。Next, the
其次，使用雙面黏著劑30，在剝離層27上例如安裝支撐構件31。支撐構件31對向於支撐層28而配置。支撐構件31具有與陽極氧化膜16相同之外形。支撐構件31在後續製程中發揮支撐體的作用。藉由安裝支撐構件31，操作性提高。
雙面黏著劑30只要能夠接著剝離層27的支撐層28與支撐構件31，則其構成並不受特別的限定，例如，能夠使用NITTO DENKO CORPORATION.製造的雙面型REVALPHA（註冊商標）。Next, using the double-
支撐構件31係支撐陽極氧化膜16者，例如由矽基板構成。作為支撐構件31，除矽基板以外，例如還能夠使用SiC、SiN、GaN及氧化鋁（Al2
O3
）等陶瓷基板、玻璃基板、纖維強化塑膠基板及金屬基板。纖維強化塑膠基板中還包括印刷配線基板亦即FR-4（Flame Retardant Type（阻燃型）4）基板等。The
其次，對陽極氧化膜16的背面16b進行研磨。在陽極氧化膜16的背面16b的研磨中，陽極氧化膜16的背面16b和導通路20的端面（未圖示）進行平坦化直至成為同一面之狀態。上述陽極氧化膜16的背面16b的研磨由於與對上述圖13所示陽極氧化膜16的表面16a進行之表面平滑化處理製程相同，因此省略其詳細說明。Next, the
如上所述，在對具有複數個導通路20之陽極氧化膜16的表面16a實施表面平滑化處理製程之後，對具有複數個導通路20之陽極氧化膜16的背面16b實施了表面平滑化處理製程，但是對至少一面實施上述表面平滑化處理製程即可。
例如，可以分別使用感測器（未圖示）對陽極氧化膜16的表面16a及背面16b測量反射率，若反射率值在預先確定之範圍內，則不進行研磨而轉移到下一個製程。As described above, after the surface smoothing process is performed on the
其次，如圖17所示，在厚度方向Dt上去除一部分陽極氧化膜16及框部15d，使上述所填充之金屬比陽極氧化膜16的背面16b突出。亦即，使導通路20從陽極氧化膜16的背面16b突出。將導通路20從陽極氧化膜16的背面16b突出之部分稱為突出部20b。
使上述所填充之金屬比陽極氧化膜16的背面16b突出之製程由於與上述金屬突出製程相同，因此省略其詳細說明。Next, as shown in FIG. 17 , a part of the anodized
其次，如圖18所示，將陽極氧化膜16的背面16b的埋設有導通路20的突出部20b之樹脂層26形成於陽極氧化膜16的背面16b。藉此，能夠得到圖18所示金屬填充微細結構體32。
另外，埋設有導通路20的突出部20b之樹脂層26的形成方法由於與上述樹脂層形成製程相同，因此省略其詳細說明。Next, as shown in FIG. 18 , on the
如圖18所示，在陽極氧化膜16的兩面上形成有樹脂層26之狀態下，在陽極氧化膜16的外緣部上殘留有框部15d。可以利用溶解或研削等物理方法來去除殘留在該外緣部上之框部15d。藉此，如圖19所示，能夠得到陽極氧化膜16單體的金屬填充微細結構體32。另外，若能夠不損壞陽極氧化膜16而去除閥金屬構件15，則並不限定於溶解。將去除鋁基板等閥金屬構件15稱為閥金屬構件去除製程。關於閥金屬構件去除製程，後面進行說明。
若金屬填充微細結構體32的形狀例如為圓板形狀，則在金屬填充微細結構體32的輸送中能夠利用用於輸送半導體晶圓等之裝置，在金屬填充微細結構體32的處理中不需要特別的裝置。As shown in FIG. 18 , in a state where the resin layers 26 are formed on both surfaces of the anodized
〔閥金屬構件去除製程〕
關於溶解閥金屬構件15之處理液，在鋁基板之情況下，鋁基板的溶解中使用不易溶解鋁的陽極氧化膜16且容易溶解鋁之處理液為較佳。對鋁之溶解速度為1μm/分鐘以上為較佳，3μm/分鐘以上為更佳，5μm/分鐘以上為進一步較佳。同樣地，對陽極氧化膜之溶解速度為0.1nm/分鐘以下為較佳，0.05nm/分鐘以下為更佳，0.01nm/分鐘以下為進一步較佳。[Valve metal components removal process]
Regarding the treatment liquid for dissolving the
具體而言，包含至少1種離子化傾向比鋁低的金屬化合物且pH（氫離子指數）為4以下或8以上之處理液為較佳，其pH為3以下或9以上為更佳，2以下或10以上為進一步較佳。 作為該等處理液，將酸或鹼性水溶液為基質，例如為將錳、鋅、鉻、鐵、鎘、鈷、鎳、錫、鉛、銻、鉍、銅、汞、銀、鈀、鉑、金的化合物（例如氯鉑酸）、該等的氟化物、該等的氯化物等配合者為較佳。 其中，酸性水溶液基質為較佳，混合氯化物為較佳。 尤其，從處理範圍的觀點考慮，鹽酸性水溶液中混合氯化汞之處理液（鹽酸/氯化汞）、鹽酸性水溶液中混合氯化銅之處理液（鹽酸/氯化銅）為較佳。 另外，該等處理液的組成並不受特別的限定，例如能夠使用溴/甲醇混合物、溴/乙醇混合物及王水等。Specifically, a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH (hydrogen ion index) of 4 or less or 8 or more is preferable, and its pH is more preferably 3 or less or 9 or more, and 2 Less than or equal to 10 is more preferable. As these treatment liquids, an acid or alkaline aqueous solution is used as a matrix, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, Compounds of gold compounds (eg, chloroplatinic acid), these fluorides, and these chlorides are preferred. Among them, the acid aqueous solution base is preferred, and the mixed chloride is preferred. In particular, from the viewpoint of the treatment range, a treatment liquid (hydrochloric acid/mercuric chloride) mixed with an aqueous hydrochloric acid solution of mercuric chloride, and a treatment liquid (hydrochloric acid/cupric chloride) mixed with an aqueous hydrochloric acid solution of cupric chloride are preferable. In addition, the composition of these treatment liquids is not particularly limited, and for example, a bromine/methanol mixture, a bromine/ethanol mixture, and aqua regia can be used.
又，該等處理液的酸或鹼濃度，0.01～10mol/L為較佳，0.05～5mol/L為更佳。 此外，使用了該等處理液之處理溫度，-10℃～80℃為較佳，0℃～60℃為更佳。In addition, the acid or alkali concentration of these treatment solutions is preferably 0.01 to 10 mol/L, more preferably 0.05 to 5 mol/L. In addition, the treatment temperature using these treatment liquids is preferably -10°C to 80°C, more preferably 0°C to 60°C.
又，上述閥金屬構件15的溶解係，藉由在上述金屬去除製程之後使閥金屬構件15接觸於上述處理液而進行。接觸方法並不受特別的限定，例如可舉出浸漬法及噴霧法。其中，浸漬法為較佳。作為此時的接觸時間，10秒鐘～5小時為較佳，1分鐘～3小時為更佳。In addition, the dissolving system of the
[金屬填充微細結構體的製造方法的第2例] 圖20～圖24係按製程順序表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例之示意性剖視圖。另外，在圖20～圖24中，對與圖6所示構成相同之構成物標註同一符號，並省略其詳細說明。[Second Example of Manufacturing Method of Metal-Filled Microstructure] FIGS. 20 to 24 are schematic cross-sectional views showing a second example of the method for producing the metal-filled microstructure according to the embodiment of the present invention in the order of the processes. In addition, in FIGS. 20-24, the same code|symbol is attached|subjected to the structure which is the same as that shown in FIG. 6, and the detailed description is abbreviate|omitted.
與金屬填充微細結構體的製造方法的第1例相比，金屬填充微細結構體的製造方法的第2例的不同點在於，不僅在閥金屬構件11的表面11a的外緣11b上形成遮罩12（參閱圖4），而且將具有開口13a之遮罩13配置於閥金屬構件11的表面11a的外緣11b上，除此以外，以與金屬填充微細結構體的製造方法的第1例相同之方式，能夠得到圖6所示金屬填充構件21和圖18及圖19所示金屬填充微細結構體32。
如圖20所示，在閥金屬構件11的表面11a上配置具有開口13a之遮罩13。其次，如圖21所示，在閥金屬構件11的表面11a的外緣11b上配置遮罩13。此時，在閥金屬構件11的表面11a上，相當於遮罩13的開口13a之區域11c係陽極氧化膜11d（參閱圖22）的形成區域。
其次，實施陽極氧化膜形成製程，該製程中實施以閥金屬構件11作為電極之陽極氧化處理，並且在閥金屬構件11中在由遮罩13包圍之區域11c中形成陽極氧化膜。陽極氧化膜形成製程與上述金屬填充微細結構體的製造方法的第1例相同，因此省略其詳細說明。在陽極氧化膜形成製程中，在上述區域11c中形成陽極氧化膜11d，但是遮罩13下方的閥金屬構件11不被陽極氧化。Compared with the first example of the method of manufacturing the metal-filled microstructure, the second example of the method of manufacturing the metal-filled microstructure is different in that not only the mask is formed on the
在陽極氧化處理之後，如圖23所示，從閥金屬構件11的表面11a分離遮罩13。其次，對圖23所示陽極氧化膜11d去除阻擋層，如圖24所示，在陽極氧化膜11d中形成複數個在厚度方向Dt上延伸的貫通孔17，得到由陽極氧化膜11d構成之陽極氧化膜16。
其次，實施填充製程，該製程對圖24所示結構體18在陽極氧化膜16的複數個貫通孔17中填充金屬。藉由對結構體18在陽極氧化膜16的複數個貫通孔17的內部超出陽極氧化膜16的表面16a填充金屬，如上述圖6所示形成金屬層19。藉此，形成圖6所示金屬填充構件21。金屬層19的形成方法由於與上述金屬填充微細結構體的製造方法的第1例相同，因此省略其詳細說明。After the anodizing treatment, as shown in FIG. 23 , the
[金屬填充微細結構體的製造方法的第3例] 圖25～圖29係按製程順序表示本發明的實施形態的填充微細結構體的第3例之示意性剖視圖。另外，在圖25～圖29中，對與圖6所示構成相同之構成物標註同一符號，並省略其詳細說明。[The third example of the manufacturing method of the metal-filled microstructure] 25 to 29 are schematic cross-sectional views showing a third example of the filled microstructure according to the embodiment of the present invention in the order of the processes. In addition, in FIGS. 25-29, the same code|symbol is attached|subjected to the structure which is the same as that shown in FIG. 6, and the detailed description is abbreviate|omitted.
與金屬填充微細結構體的製造方法的第1例相比，金屬填充微細結構體的製造方法的第3例的不同點在於，對閥金屬構件的表面11a的整面進行陽極氧化處理、以及去除陽極氧化膜而形成框部，除此以外，以與金屬填充微細結構體的製造方法的第1例相同方式，能夠得到圖6所示金屬填充構件21和圖18及圖19所示金屬填充微細結構體32。
在金屬填充微細結構體的製造方法的第3例中，與金屬填充微細結構體的製造方法的第1例同樣，準備閥金屬構件11（參閱圖1）。其次，對閥金屬構件11的表面11a的整面進行陽極氧化處理，殘留閥金屬構件11的底部11e（參閱圖3）而形成陽極氧化膜11d（參閱圖3）。此外，對陽極氧化膜11d去除阻擋層，如圖25所示，在陽極氧化膜11d上形成複數個在厚度方向Dt上延伸之貫通孔17，得到由陽極氧化膜構成之陽極氧化膜16。在陽極氧化膜16的下方殘留有作為閥金屬構件11（參閱圖3）的一部分之底部11e（參閱圖3），底部11e係閥金屬構件15的底部15e（參閱圖25）。陽極氧化膜16的厚度HA
小於200μm為較佳。若厚度HA
小於200μm，則能夠視為陽極氧化膜16和閥金屬構件15在同一面上。Compared with the first example of the method of manufacturing a metal-filled microstructure, the third example of the method of manufacturing a metal-filled microstructure is different in that the
其次，如圖26所示，在陽極氧化膜16的表面16a上，除陽極氧化膜16的外緣16e以外，還配置遮罩14。在該狀態下，使用陽極氧化膜16溶解且閥金屬構件15不溶解之特性之液體來溶解陽極氧化膜16的外緣16e。藉此，如圖27所示，閥金屬構件15的底部15e露出。
另外，遮罩14若係對具有陽極氧化膜16溶解且閥金屬構件15不溶解之特性之液體不溶解者，則並不受特別的限定，例如使用阻劑膜。遮罩14中使用之阻劑膜係能夠在陽極氧化膜16的表面16a的整面形成阻劑膜之後，利用光微影法去除陽極氧化膜16的外緣16e的阻劑膜而形成。
作為具有上述陽極氧化膜16溶解且閥金屬構件15不溶解之特性之液體，使用溶解氧化鋁（Al2
O3
）之酸性水溶液或鹼性水溶液。具體而言，例如使用包含氯化銅之鹽酸性水溶液。Next, as shown in FIG. 26, on the
其次，如圖28所示，從陽極氧化膜16的表面16a去除遮罩14。藉此，得到具有閥金屬構件15和陽極氧化膜16之結構體18。
陽極氧化膜16的表面16a與框部15d的上表面之差，亦即陽極氧化膜16的厚度HA
小於200μm。因此，陽極氧化膜16的表面16a與框部15d的上表面大致在同一面上。
另外，遮罩14若例如係阻劑膜，則能夠利用灰化而去除。Next, as shown in FIG. 28 , the
其次，實施填充製程，該製程對圖28所示結構體18在陽極氧化膜16的複數個貫通孔17中填充金屬。藉由對結構體18在陽極氧化膜16的複數個貫通孔17的內部超出陽極氧化膜16的表面16a填充金屬，如圖29所示形成金屬層19a。藉此，得到金屬填充構件21。此時，藉由形成金屬層19a而形成具有導電性之導通路20，從而形成金屬填充構件21。金屬層19a的形成方法由於與上述金屬填充微細結構體的製造方法的第1例的金屬層19的形成方法相同，因此省略其詳細說明。
另外，雖然配置遮罩14而溶解了陽極氧化膜16的外緣16e，但是並不限定於此，亦可藉由研削或雷射光等以物理方式來切削陽極氧化膜16的外緣16e。又，例如，亦可利用噴墨法將具有陽極氧化膜溶解且閥金屬構件不溶解之特性之液體噴射於陽極氧化膜16的外緣16e，從而使陽極氧化膜16的外緣16e選擇性地溶解。Next, a filling process is performed, in which the
[金屬填充微細結構體的製造方法的第4例] 圖30～圖34係按製程順序表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例之示意性剖視圖。另外，關於圖30～圖34，對與圖6所示構成相同之構成物標註同一符號，並省略其詳細說明。[The fourth example of the method for producing a metal-filled microstructure] 30 to 34 are schematic cross-sectional views showing a fourth example of the method for producing the metal-filled microstructure according to the embodiment of the present invention in the order of the processes. In addition, regarding FIGS. 30-34, the same code|symbol is attached|subjected to the component with the same structure as shown in FIG. 6, and the detailed description is abbreviate|omitted.
與金屬填充微細結構體的製造方法的第1例相比，金屬填充微細結構體的製造方法的第4例的不同點在於，使用在絕緣支撐體61的表面61a上局部形成有具有導電性之導電層62之電極體60對閥金屬構件11進行陽極氧化處理，除此以外，以與金屬填充微細結構體的製造方法的第1例相同之方式，能夠得到圖6所示金屬填充構件21和圖18及圖19所示金屬填充微細結構體32。Compared with the first example of the method of manufacturing a metal-filled microstructure, the fourth example of the method of manufacturing a metal-filled microstructure is different in that a conductive material is locally formed on the
在金屬填充微細結構體的製造方法的第4例中，如圖30所示，首先準備在矩形絕緣支撐體61的表面61a上局部形成有具有導電性之導電層62之電極體60。電極體60用作陽極氧化處理時的電極。
導電層62在絕緣支撐體61的表面61a上形成阻劑層63，並且例如藉由利用光微影法之圖案化而局部去除阻劑層63。其次，例如在阻劑層63上形成晶種層（未圖示），並藉由鍍覆而形成導電層62。當形成導電層62時，藉由平坦化處理將阻劑層63和導電層62的表面進行平坦化。另外，導電層62藉由鍍覆而形成，但是導電層62的形成方法並不受特別的限定。In the fourth example of the method of manufacturing the metal-filled microstructure, as shown in FIG. 30 , first, an
其次，如圖31所示，設置覆蓋電極體60的導電層62之閥金屬構件11。閥金屬構件11係根據金屬填充構件21的陽極氧化膜16（參閱圖33）亦即陽極氧化膜的厚度、或者根據最終得到之金屬填充微細結構體32（參閱圖34）的陽極氧化膜16的厚度、加工裝置等而適當確定大小及厚度者。閥金屬構件11例如係矩形板材。
作為閥金屬構件11，如上所述，使用鋁基板。
另外，作為閥金屬構件11，例如可以準備鋁基板，但是亦可在電極體60上形成閥金屬構件11。在該情況下，在閥金屬層形成製程中，例如在導電層62的表面62a和阻劑層63的表面63a上，例如藉由蒸鍍法形成鋁基板作為閥金屬構件11。Next, as shown in FIG. 31 , the
其次，進行陽極氧化膜形成製程，該製程中實施以導電層62作為電極之陽極氧化處理，並且在閥金屬構件11中將導電層62上的區域的閥金屬構件11形成為陽極氧化膜。另外，陽極氧化膜係絕緣性基材。藉由對閥金屬構件11進行陽極氧化處理而形成陽極氧化膜11d。
在陽極氧化膜形成製程中，以導電層62作為陰極電極且以閥金屬構件11作為陽極電極實施陽極氧化處理。藉此，導電層62上的閥金屬構件11被陽極氧化，如圖32所示，在閥金屬構件15的區域15c中形成陽極氧化膜11d。在陽極氧化處理中，例如若在導電層62上設置有引出電極，則利用引出電極對導電層62施加直流電流。Next, an anodic oxide film formation process is performed, in which anodization treatment is performed using the
在陽極氧化處理中，如上所述，將電極體60的導電層62用作電極，電極體60的導電層62上的閥金屬構件11（參閱圖31）成為形成陽極氧化膜11d之區域11c（參閱圖31），阻劑層63上的閥金屬構件11（參閱圖31）係閥金屬構件15的外緣15b，並成為框部15d。
在上述區域11c中形成陽極氧化膜11d，但是阻劑層63上的閥金屬構件11不被陽極氧化。如此，閥金屬構件11不會全部成為陽極氧化膜11d，而在陽極氧化處理之後亦存在仍保持閥金屬構件11之區域。藉此，在閥金屬構件15的外緣15b上，配置由閥金屬構件11構成之閥金屬構件15的框部15d。在由框部15d包圍之區域15c中，形成陽極氧化膜11d（參閱圖32）作為陽極氧化膜16。
在陽極氧化處理中，導電層62上的閥金屬構件11全部能夠形成為陽極氧化膜11d，但是藉由調整陽極氧化處理時間等，能夠將導電層62上的閥金屬構件11的一部分形成為陽極氧化膜11d。在圖32中，在導電層62與作為陽極氧化膜之陽極氧化膜16之間，存在閥金屬構件15。
另外，由於閥金屬構件11由鋁構成，因此作為氧化膜而形成陽極氧化膜11d，陽極氧化膜11d由Al2
O3
膜構成。In the anodizing treatment, as described above, the
陽極氧化膜11d在所形成之時點存在複數個微孔。然而，在複數個微孔中，亦有在厚度方向Dt上未貫通之微孔。又，在微孔的底部存在阻擋層（未圖示）。因此，對圖32所示陽極氧化膜11d去除阻擋層，如圖33所示，在陽極氧化膜11d中形成複數個在厚度方向Dt上延伸之貫通孔17，得到由陽極氧化膜11d構成之陽極氧化膜16。The
藉由以上製程，在由配置於閥金屬構件15的外緣15b上之框部15d包圍之區域15c中，形成具有複數個細孔（貫通孔17）之陽極氧化膜16（陽極氧化膜），藉此得到具有閥金屬構件15和陽極氧化膜16（陽極氧化膜）之結構體18。例如，如圖33所示，在閥金屬構件15的表面15a上形成陽極氧化膜16（陽極氧化膜），在陽極氧化膜16的周圍存在框部15d。又，雖然未圖示，但是陽極氧化膜16的表面16a和框部15d的上表面係大致同一面。
如上所述，圖32所示陽極氧化膜形成製程和圖33所示之形成複數個在厚度方向Dt上延伸之貫通孔17之製程係，得到結構體18之形成製程。Through the above process, in the
其次，如圖34所示，實施填充製程，該製程對結構體18在陽極氧化膜16的複數個貫通孔17中填充金屬。對結構體18在陽極氧化膜16的複數個貫通孔17的內部超出陽極氧化膜16的表面16a填充金屬，藉此形成上述金屬層19。藉此，得到金屬填充構件21。此時，藉由形成金屬層19而形成具有導電性之導通路20。金屬層19的形成方法由於與上述金屬填充微細結構體的製造方法的第1例相同，因此省略其詳細說明。
在填充製程中，在陽極氧化膜16的複數個貫通孔17的內部填充金屬，並且如圖34所示，藉由在結構體18的表面上，亦即在金屬填充構件21的框部15d上及陽極氧化膜16的表面16a上形成金屬層19，將金屬填充於複數個貫通孔17中。在該情況下，在金屬層19中，如上所述，將存在於框部15d上之部分的厚度δ（參閱圖2）設為2μm～100μm。
另外，例如藉由延長鍍覆時間，能夠增大金屬層19的厚度δ。在填充製程中，藉由超出陽極氧化膜16的表面16a填充金屬，在框部15d上亦形成金屬層19。
以下，關於金屬填充微細結構體的構成的一例進行說明。Next, as shown in FIG. 34 , a filling process is performed, and the
[金屬填充微細結構體的一例] 圖35係表示本發明的實施形態的金屬填充微細結構體的構成的一例之俯視圖，圖36係表示本發明的實施形態的金屬填充微細結構體的構成的一例之示意性剖視圖。圖36係圖35的剖切線IB-IB剖視圖。[An example of a metal-filled microstructure] 35 is a plan view showing an example of the structure of the metal-filled microstructure according to the embodiment of the present invention, and FIG. 36 is a schematic cross-sectional view showing an example of the structure of the metal-filled microstructure according to the embodiment of the present invention. FIG. 36 is a cross-sectional view taken along the line IB-IB of FIG. 35 .
圖35及圖36所示金屬填充微細結構體32具有如上所述作為絕緣性基材之陽極氧化膜16、在陽極氧化膜16的厚度方向Dt上貫通之貫通孔17、由填充於貫通孔17的內部之金屬構成之複數個導通路20。複數個導通路20以彼此電絕緣之狀態設置。此外，例如具備設置於陽極氧化膜16的表面16a及背面16b之樹脂層26。
在此，“彼此電絕緣之狀態”係指，存在於陽極氧化膜16的內部之各導通路20彼此在陽極氧化膜16的內部導通性足夠低的狀態。
金屬填充微細結構體32係如下構件：導通路20彼此電絕緣，在與陽極氧化膜16的厚度方向Dt正交之方向x上導電性足夠低，在厚度方向Dt上具有導電性，並顯示出各向異性導電性。金屬填充微細結構體32配置成使厚度方向Dt與例如後述電子元件的積層方向一致。
如圖35及圖36所示，導通路20以彼此電絕緣之狀態在厚度方向Dt上貫通設置有陽極氧化膜16。The metal-filled
金屬填充微細結構體32的厚度h例如為40μm以下。又，金屬填充微細結構體32的TTV（Total Thickness Variation：總厚度變化）為10μm以下為較佳。陽極氧化膜16由於表面16a和背面16b被研磨，因此作為厚度，比金屬填充微細結構體32的厚度h厚，例如超過60μm，從脆性的觀點考慮，40μm程度為較佳。The thickness h of the metal-filled
在此，金屬填充微細結構體32的厚度h及陽極氧化膜16的厚度係，由聚焦離子束（Focused Ion Beam：FIB）分別相對於厚度方向對金屬填充微細結構體32及陽極氧化膜16進行切削加工，由電解發射型掃描電子顯微鏡以20萬倍的倍率觀察其剖面，分別獲取金屬填充微細結構體32及陽極氧化膜16的輪廓形狀，並關於相當於厚度h之區域測定10點之平均值。
又，金屬填充微細結構體32的TTV（Total Thickness Variation：總厚度變化）係，藉由切塊機將金屬填充微細結構體32連同支撐構件31一起進行切斷，並觀察金屬填充微細結構體32的剖面形狀而求出之值。Here, the thickness h of the metal-filled
金屬填充微細結構體32例如能夠用作顯示出各向異性導電性之各向異性導電性構件。在該情況下，將半導體元件和半導體元件經由金屬填充微細結構體32進行接合，從而能夠得到將半導體元件和半導體元件電連接之電子元件。在電子元件中，金屬填充微細結構體32發揮TSV（Through Silicon Via：總厚度變化）的功能。
除此以外，亦可作為使用金屬填充微細結構體32將3個以上半導體元件電連接之電子元件。藉由使用金屬填充微細結構體32，可以進行三維安裝。另外，接合半導體元件之數量並不受特別的限定，係根據電子元件的功能及對電子元件要求之性能而適當確定者。
與電子元件的接合，能夠使用熱加壓接合。若在還原性環境下進行接合，則以250℃以下的溫度容易接合金屬電極和突出部，因此能夠減小對器件的熱影響。The metal-filled
藉由使用金屬填充微細結構體32，能夠減小電子元件的大小，並能夠減小安裝面積。又，藉由縮小金屬填充微細結構體32的厚度，能夠縮小半導體元件之間的配線長度，並能夠抑制訊號的延遲且提高電子元件的處理速度。藉由縮小半導體元件之間的配線長度，亦可抑制消耗電力。
如上所述，金屬填充微細結構體32由於研磨成陽極氧化膜16和導通路20在陽極氧化膜16的表面16a上成為同一面的狀態，因此形狀精度高，又，如上所述，由於能夠嚴格控制導通路20的突出部20a的高度，因此半導體元件與半導體元件的電連接的可靠性優異。
又，金屬填充微細結構體32由於緻密地填充有金屬，因此與樹脂材料相比，導熱性高。不僅所連接之電極之間、半導體元件之間的上下方向的導熱大，而且平面方向的熱擴散亦大，因此對需要散熱之構件尤其有用。金屬填充微細結構體32除上述半導體元件以外，還可以使用於金屬基底基板的散熱等，在散熱片的連接中亦有效。又，在具有由多層連接引起之保熱問題之記憶體等的接合中，非常有效。By filling the
作為半導體元件，例如可舉出ASIC（Application Specific Integrated Circuit：特殊應用積體電路）、FPGA（Field Programmable Gate Array：場域可程式閘陣列）、ASSP（Application Specific Standard Product：應用特定標準產品）等邏輯積體電路。又，例如可舉出CPU（Central Processing Unit：中央處理單元）、GPU（Graphics Processing Unit：圖案處理單元）等微處理器。又，例如可舉出DRAM（Dynamic Random Access Memory：動態隨機存取記憶體）、HMC（Hybrid Memory Cube：混合記憶體立方體）、MRAM（Magnetoresistive Random Access Memory：磁記憶體）、PCM（Phase-Change Memory：相變化記憶體）、ReRAM（Resistance Random Access Memory：可變電阻式記憶體）、FeRAM（Ferroelectric Random Access Memory：鐵電隨機存取記憶體）、快閃記憶體等記憶體。又，例如可舉出LED（Light Emitting Diode：發光二極體）、功率器件、DC（Direct Current：直流電）-DC（Direct Current：直流電）轉換器、絕緣閘雙極電晶體（Insulated Gate Bipolar Transistor：IGBT）等模擬積體電路。又，例如可舉出加速度感測器、壓力感測器、振子、陀螺儀感測器等MEMS（Micro Electro Mechanical Systems：微機電系統）。又，例如可舉出GPS（Global Positioning System：全球定位系統）、FM（Frequency Modulation：調頻）、NFC（Near field communication：近場通訊）、RFEM（RF Expansion Module：射頻擴展模組）、MMIC（MonolithicMicrowaveIntegratedCircuit：毫米波積體電路）、WLAN（WirelessLocalAreaNetwork：無線區域網路）等無線元件、離散元件、CMOS（Complementary Metal Oxide Semiconductor：互補式金屬氧化物半導體）、CMOS圖像感測器、相機模組、Passive（被動）器件、SAW（Surface Acoustic Wave：表面聲波）濾波器、RF（Radio Frequency：射頻）濾波器、IPD（Integrated Passive Devices：整合式被動元件）等。Examples of semiconductor elements include ASIC (Application Specific Integrated Circuit), FPGA (Field Programmable Gate Array), ASSP (Application Specific Standard Product), and the like. logic integrated circuits. Moreover, for example, microprocessors, such as a CPU (Central Processing Unit: Central Processing Unit) and a GPU (Graphics Processing Unit: Pattern Processing Unit), are mentioned. Moreover, for example, DRAM (Dynamic Random Access Memory), HMC (Hybrid Memory Cube: hybrid memory cube), MRAM (Magnetoresistive Random Access Memory: magnetic memory), PCM (Phase-Change Memory) can be mentioned Memory: phase change memory), ReRAM (Resistance Random Access Memory: variable resistance memory), FeRAM (Ferroelectric Random Access Memory: ferroelectric random access memory), flash memory and other memories. Also, for example, LEDs (Light Emitting Diodes), power devices, DC (Direct Current: direct current)-DC (Direct Current: direct current) converters, insulated gate bipolar transistors (Insulated Gate Bipolar Transistor) can be mentioned. : IGBT) and other analog integrated circuits. Moreover, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems), such as an acceleration sensor, a pressure sensor, a vibrator, and a gyroscope sensor, are mentioned, for example. Moreover, for example, GPS (Global Positioning System: Global Positioning System), FM (Frequency Modulation: Frequency Modulation), NFC (Near field communication: Near Field Communication), RFEM (RF Expansion Module: Radio Frequency Expansion Module), MMIC ( Monolithic Microwave Integrated Circuit: millimeter wave integrated circuit), wireless components such as WLAN (Wireless Local Area Network: wireless local area network), discrete components, CMOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CMOS image sensor, camera module , Passive (passive) devices, SAW (Surface Acoustic Wave: surface acoustic wave) filters, RF (Radio Frequency: radio frequency) filters, IPD (Integrated Passive Devices: integrated passive components) and so on.
又，半導體元件可以係具有元件區域者。元件區域係形成有用於作為電子元件發揮功能之各種元件構成電路等之區域。在元件區域中，例如有形成有如快閃記憶體等之類之記憶體電路、微處理器及FPGA（field-programmable gate array：場域可程式閘陣列）等之類的邏輯電路之區域；及形成有無線標籤等通信模組和配線之區域。在元件區域中，除此以外，還可以形成有MEMS（Micro Electro Mechanical Systems：微機電系統）。MEMS例如係感測器、致動器及天線等。在感測器中，例如包括加速度感測器、聲音感測器、光感測器等各種感測器。光感測器若能夠檢測光，則並不受特別的限定，例如使用CCD（Charge Coupled Device：電荷耦合元件）圖像感測器或CMOS（Complementary Metal Oxide Semiconductor：互補金屬氧化物半導體）圖像感測器。In addition, the semiconductor element may have an element region. The element region is a region in which various elements functioning as electronic elements constitute circuits and the like. In the device area, for example, there is an area where a memory circuit such as a flash memory, a microprocessor, and a logic circuit such as an FPGA (field-programmable gate array) are formed; and An area where communication modules such as wireless tags and wiring are formed. In the element region, in addition to this, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems) may be formed. MEMS are, for example, sensors, actuators, and antennas. The sensors include, for example, various sensors such as an acceleration sensor, a sound sensor, and a light sensor. The light sensor is not particularly limited as long as it can detect light. For example, a CCD (Charge Coupled Device: Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor) image sensor is used. sensor.
根據在電子元件中實現之功能，適當選擇半導體元件。例如，在電子元件中，能夠設為具有邏輯電路之半導體元件與具有記憶體電路之半導體元件的組合。又，作為電子元件中之半導體元件的組合，可以係感測器、致動器及天線等與記憶體電路和邏輯電路的組合。
半導體元件例如由矽構成，但是並不限定於此，亦可以係碳化矽、鍺、砷化鎵或氮化鎵等。
又，除半導體元件以外，還可以使用金屬填充微細結構體32來電連接兩個配線層。The semiconductor element is appropriately selected according to the function implemented in the electronic element. For example, in the electronic device, a combination of a semiconductor device having a logic circuit and a semiconductor device having a memory circuit can be used. In addition, as a combination of a semiconductor element among electronic components, a combination of a sensor, an actuator, an antenna, etc., a memory circuit, and a logic circuit may be used.
The semiconductor element is made of, for example, silicon, but is not limited to this, and may be made of silicon carbide, germanium, gallium arsenide, gallium nitride, or the like.
In addition to the semiconductor element, the metal-filled
以下，關於金屬填充微細結構體32的構成，進行更具體說明。
[陽極氧化膜]
陽極氧化膜16係作為絕緣性基材發揮功能者。陽極氧化膜16中之各貫通孔的間隔係5nm～800nm為較佳，10nm～200nm為更佳，20nm～60nm為進一步較佳。若陽極氧化膜16中之各貫通孔的間隔在該範圍內，則陽極氧化膜16作為絕緣性隔壁充分發揮功能。
在此，各導通路的間隔係指相鄰之導通路之間的寬度w，並且係指由電場發射型掃描電子顯微鏡以20萬倍的倍率觀察金屬填充微細結構體32的剖面，並在10個點上測定出相鄰之導通路之間的寬度之平均值。Hereinafter, the structure of the metal-filled
＜細孔的平均直徑＞
細孔的平均直徑，亦即貫通孔17的平均直徑d（參閱圖35、圖36）係1μm以下，5～500nm為較佳，20～400nm為更佳，40～200nm為進一步較佳，50～100nm為最佳。貫通孔17的平均直徑d若為1μm以下且在上述範圍內，則當電氣訊號通過所得到之導通路20時能夠得到充分的響應，因此能夠更佳地用作電子零件的檢查用連接器。又，若貫通孔17的平均直徑d為1μm以下，則能夠容易去除金屬層19（參閱圖6）。
貫通孔17的平均直徑d係，使用掃描電子顯微鏡從正上方以100～10000倍的倍率拍攝陽極氧化膜16的表面而得到攝影圖像。在攝影圖像中至少提取20個周圍呈環狀相連之貫通孔，測定其直徑並設為開口直徑，將該等開口直徑的平均值作為貫通孔的平均直徑而計算。
另外，倍率能夠適當選擇上述範圍的倍率，以使得到能夠提取20個以上貫通孔之攝影圖像。又，開口直徑測定為貫通孔部分的端部之間的距離的最大值。亦即，由於貫通孔的開口部的形狀並不限定於大致圓形，因此在開口部的形狀為非圓形之情況下，將貫通孔部分的端部之間的距離的最大值設為開口直徑。從而，例如在2個以上的貫通孔一體化形狀的貫通孔之情況下，亦將其視為1個貫通孔，並將貫通孔部分的端部之間的距離的最大值設為開口直徑。<Average diameter of pores>
The average diameter of the pores, that is, the average diameter d of the through holes 17 (see Fig. 35 and Fig. 36 ) is 1 μm or less, preferably 5 to 500 nm, more preferably 20 to 400 nm, more preferably 40 to 200 nm, and 50 ~100nm is the best. When the average diameter d of the through-
〔導通路〕
如上所述，複數個導通路20在陽極氧化膜16的厚度方向Dt上貫通，並以彼此電絕緣之狀態設置且呈柱狀。導通路20由金屬構成。導通路20可以具有從陽極氧化膜16的表面及背面突出之突出部，並且各導通路的突出部埋設於樹脂層中。
作為構成導通路之金屬的具體例，較佳地例示出金（Au）、銀（Ag）、銅（Cu）、鋁（Al）、鎂（Mg）及鎳（Ni）等。從導電性的觀點考慮，銅、金、鋁及鎳為較佳，銅及金為更佳。[conduction path]
As described above, the plurality of
＜突出部＞
導通路20的突出部20a、20b係導通路20從陽極氧化膜16的表面16a及背面16b突出之部分，由樹脂層26保護為較佳。
在將金屬填充微細結構體32用作各向異性導電性構件之情況下，當藉由壓接等方法將各向異性導電性構件與電極電連接或物理接合時，根據能夠充分確保突出部壓扁時的平面方向的絕緣性之理由，導通路的突出部的縱橫比（突出部的高度/突出部的直徑）為0.5以上且小於50為較佳，0.8～20為更佳，1～10為進一步較佳。<Projection>
The protruding
又，從追隨連接對象的半導體元件或半導體晶圓的表面形狀之觀點考慮，導通路的突出部的高度，20nm以上為較佳，100nm～500nm為更佳。 導通路的突出部的高度係指，由電解發射型掃描電子顯微鏡以2萬倍的倍率觀察各向異性導電性構件的剖面，並在10點上測定出導通路的突出部的高度之平均值。 導通路的突出部的直徑係指，由電解發射型掃描電子顯微鏡觀察各向異性導電性構件的剖面，並在10點上測定出導通路的突出部的直徑之平均值。In addition, from the viewpoint of following the surface shape of the semiconductor element or semiconductor wafer to be connected, the height of the protruding portion of the conduction path is preferably 20 nm or more, and more preferably 100 nm to 500 nm. The height of the protruding portion of the conducting path is the average value of the height of the protruding portion of the conducting path measured at 10 points by observing the cross section of the anisotropic conductive member with an electrolytic emission scanning electron microscope at a magnification of 20,000 times. . The diameter of the protruding portion of the conduction path means the average value of the diameter of the protruding portion of the conduction path measured at 10 points of the cross section of the anisotropically conductive member observed with an electrolytic emission scanning electron microscope.
＜其他形狀＞
如上所述，導通路20的密度係2萬個/mm2
以上為較佳，200萬個/mm2
以上為更佳，1000萬個/mm2
以上為進一步較佳，5000萬個/mm2
以上為特佳，1億個/mm2
以上為最佳。
此外，相鄰之各導通路20的中心間距p（參閱圖35及圖36）係20nm～500nm為較佳，40nm～200nm為更佳，50nm～140nm為進一步較佳。<Other shapes> As described above, the density of the
〔樹脂層〕
如上所述，樹脂層26設置於陽極氧化膜16的表面16a和背面16b，如上所述，係埋設導通路20的突出部20a、20b者。亦即，樹脂層26被覆從陽極氧化膜16突出之導通路20的端部，並保護突出部20a、20b。
樹脂層26係藉由上述樹脂層形成製程而形成者。樹脂層26係對連接對象賦予接著性者。樹脂層26例如在50℃～200℃的溫度範圍內顯示出流動性，在200℃以上之溫度下硬化者為較佳。
樹脂層26係藉由上述樹脂層形成製程而形成者，但是亦能夠使用以下所示之樹脂層的組成。以下，關於樹脂層的組成進行說明。例如，樹脂層係含有高分子材料者，亦可含有抗氧化材料。[Resin layer]
As described above, the
＜高分子材料＞ 作為樹脂層中所包含之高分子材料並不受特別的限定，但是根據能夠有效地填埋半導體元件或半導體晶圓與各向異性導電性構件的間隙，並進一步提高與半導體元件或半導體晶圓的密接性之理由，熱硬化性樹脂為較佳。 作為熱硬化性樹脂，具體而言，例如可舉出環氧樹脂、酚樹脂、聚醯亞胺樹脂、聚酯樹脂、聚氨酯樹脂、雙馬來醯亞胺樹脂、三聚氰胺樹脂、異氰酸酯類樹脂等。 其中，根據進一步提高絕緣可靠性且耐化學性優異之理由，使用聚醯亞胺樹脂及/或環氧樹脂為較佳。＜Polymer material＞ The polymer material contained in the resin layer is not particularly limited, but it can effectively fill the gap between the semiconductor element or semiconductor wafer and the anisotropic conductive member, and further enhance the connection with the semiconductor element or semiconductor wafer. For the reasons of adhesion, thermosetting resins are preferred. Specific examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, polyurethane resins, bismaleimide resins, melamine resins, and isocyanate-based resins. Among them, it is preferable to use polyimide resin and/or epoxy resin for the reasons of further improving insulation reliability and excellent chemical resistance.
＜抗氧化材料＞ 作為樹脂層中所包含之抗氧化材料，具體而言，例如可舉出1,2,3,4-四唑、5-胺基-1,2,3,4-四唑、5-甲基-1,2,3,4-四唑、1H-四唑-5-乙酸、1H-四唑-5-琥珀酸、1,2,3-***、4-胺基-1,2,3-***、4,5-二胺基-1,2,3-***、4-羧基-1H-1,2,3-***、4,5-二羧基-1H-1,2,3-***、1H-1,2,3-***-4-乙酸、4-羧基-5-羧甲基-1H-1,2,3-***、1,2,4-***、3-胺基-1,2,4-***、3,5-二胺基-1,2,4-***、3-羧基-1,2,4-***、3,5-二羧基-1,2,4-***、1,2,4-***-3-乙酸、1H-苯并***、1H-苯并***-5-羧酸、苯并呋喃、2,1,3-苯并噻唑、鄰苯二胺、間苯二胺、兒茶酚、鄰胺基酚、2-巰基苯并噻唑、2-巰基苯并咪唑、2-巰基苯并噁唑、三聚氰胺及該等衍生物。 其中，苯并***及其衍生物為較佳。 作為苯并***衍生物，可舉出在苯并***的苯環上具有羥基、烷氧基（例如甲氧基、乙氧基等）、胺基、硝基、烷基（例如甲基、乙基及丁基等）、鹵素原子（例如氟、氯、溴及碘等）等之取代苯并***。又，與萘***、萘雙***同樣地，亦能夠舉出被取代之取代萘***、取代萘雙***等。＜Antioxidant material＞ Specific examples of the antioxidant material contained in the resin layer include 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, and 5-methyl tetrazole. -1,2,3,4-tetrazole, 1H-tetrazole-5-acetic acid, 1H-tetrazole-5-succinic acid, 1,2,3-triazole, 4-amino-1,2,3 -triazole, 4,5-diamino-1,2,3-triazole, 4-carboxy-1H-1,2,3-triazole, 4,5-dicarboxy-1H-1,2,3 - Triazole, 1H-1,2,3-triazole-4-acetic acid, 4-carboxy-5-carboxymethyl-1H-1,2,3-triazole, 1,2,4-triazole, 3 -Amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-carboxy-1,2,4-triazole, 3,5-dicarboxy- 1,2,4-triazole, 1,2,4-triazole-3-acetic acid, 1H-benzotriazole, 1H-benzotriazole-5-carboxylic acid, benzofuran, 2,1,3 - Benzothiazole, o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, melamine and the like derivative. Among them, benzotriazole and its derivatives are preferred. Examples of benzotriazole derivatives include those having a hydroxyl group, an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), an amino group, a nitro group, an alkyl group (for example, a methyl group) on the benzene ring of the benzotriazole. , ethyl and butyl, etc.), halogen atoms (such as fluorine, chlorine, bromine and iodine, etc.) substituted benzotriazoles. Moreover, similarly to naphthalene triazole and naphthalene bistriazole, a substituted substituted naphthalene triazole, a substituted naphthalene bistriazole, etc. can be mentioned.
又，作為樹脂層中所包含之抗氧化材料的其他例，可舉出通常之抗氧化劑，亦即，高級脂肪酸、高級脂肪酸銅、酚化合物、烷醇胺、氫醌類、銅螯合劑、有機胺及有機銨鹽等。Moreover, as another example of the antioxidant material contained in the resin layer, the usual antioxidants, that is, higher fatty acids, higher fatty acid copper, phenolic compounds, alkanolamines, hydroquinones, copper chelating agents, organic Amines and organic ammonium salts, etc.
樹脂層中所包含之抗氧化材料的含量並不受特別的限定，但是從防腐效果的觀點考慮，相對於樹脂層的總質量，0.0001質量%以上為較佳，0.001質量%以上為更佳。又，根據在正式接合步驟中得到適當之電阻之理由，5.0質量%以下為較佳，2.5質量%以下為更佳。The content of the antioxidant material contained in the resin layer is not particularly limited, but from the viewpoint of the anti-corrosion effect, 0.0001 mass % or more is preferable, and 0.001 mass % or more is more preferable with respect to the total mass of the resin layer. Moreover, 5.0 mass % or less is preferable, and 2.5 mass % or less is more preferable for the reason of obtaining an appropriate resistance in a main joining process.
＜遷移防止材料＞ 根據藉由捕獲可包含於樹脂層中之金屬離子、鹵素離子和源自半導體元件及半導體晶圓之金屬離子而進一步提高絕緣可靠性之理由，樹脂層含有遷移防止材料為較佳。<Migration prevention material> For the reason of further improving insulation reliability by trapping metal ions, halogen ions, and metal ions derived from semiconductor elements and semiconductor wafers that can be contained in the resin layer, it is preferable that the resin layer contains a migration preventing material.
作為遷移防止材料，例如能夠僅使用離子交換體，具體而言，陽離子交換體與陰離子交換體的混合物或陽離子交換體。 在此，陽離子交換體及陰離子交換體例如分別能夠從後述無機離子交換體及有機離子交換體中適當進行選擇。As the migration preventing material, for example, only an ion exchanger, specifically, a mixture of a cation exchanger and an anion exchanger, or a cation exchanger can be used. Here, the cation exchanger and the anion exchanger can be appropriately selected from, for example, an inorganic ion exchanger and an organic ion exchanger to be described later, respectively.
（無機離子交換體） 作為無機離子交換體，例如可舉出以含氫氧化鋯為代表之金屬的含氫氧化物。 作為金屬的種類，例如除鋯以外，還已知有鐵、鋁、錫、鈦、銻、鎂、鈹、銦、鉻及鉍等。 其中，鋯類金屬具有陽離子Cu2+ 、Al3+ 的交換能力。又，鐵類金屬亦具有Ag+ 、Cu2+ 的交換能力。同樣地，錫類、鈦類及銻類金屬係陽離子交換體。 另一方面，鉍類金屬具有陰離子Cl- 的交換能力。 又，鋯類金屬根據條件顯示出陰離子的交換能力。鋁類及錫類金屬亦相同。 作為除此以外的無機離子交換體，已知有以磷酸鋯為代表之多價金屬的酸性鹽、以鉬磷酸銨為代表之雜多酸鹽、不溶性亞鐵氰化等合成物。 該等無機離子交換體的一部分已市售，例如已知有TOAGOSEI CO.,LTD.的商品名稱“IXE”的各種等級。 另外，除合成品以外，還能夠使用如天然產品的沸石或蒙脫石之類的無機離子交換體粉末。(Inorganic ion exchanger) As an inorganic ion exchanger, the metal containing hydroxide represented by zirconium hydroxide is mentioned, for example. As types of metals, iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, bismuth, and the like are known, for example, in addition to zirconium. Among them, the zirconium-based metal has the exchange capacity of cations Cu 2+ and Al 3+ . In addition, iron-based metals also have exchange capacity for Ag + and Cu 2+ . Similarly, tin-based, titanium-based and antimony-based metal-based cation exchangers. On the other hand, the bismuth-type metal has the exchange ability of the anion Cl- . In addition, the zirconium-based metal exhibits anion exchange ability depending on the conditions. The same applies to aluminum-based and tin-based metals. As other inorganic ion exchangers, compounds such as acid salts of polyvalent metals represented by zirconium phosphate, heteropoly acid salts represented by ammonium molybdenum phosphate, and insoluble ferrocyanide are known. Some of these inorganic ion exchangers are commercially available, for example, various grades are known under the trade name "IXE" of TOAGOSEI CO., LTD. In addition, in addition to synthetic products, inorganic ion exchanger powders such as zeolite or montmorillonite, which are natural products, can also be used.
（有機離子交換體） 作為有機離子交換體，可舉出作為陽離子交換體而具有磺酸基之交聯聚苯乙烯，此外，還可舉出具有羧酸基、膦酸基或次膦酸基者。 又，可舉出作為陰離子交換體而具有季銨基、季鏻基或叔鋶基之交聯聚苯乙烯。(Organic ion exchanger) As an organic ion exchanger, the crosslinked polystyrene which has a sulfonic acid group as a cation exchanger is mentioned, and what has a carboxylic acid group, a phosphonic acid group, or a phosphinic acid group is also mentioned. Moreover, the crosslinked polystyrene which has a quaternary ammonium group, a quaternary phosphonium group, or a tertiary perylene group as an anion exchanger is mentioned.
該等無機離子交換體及有機離子交換體只要考慮慾捕捉之陽離子、陰離子的種類、關於前述離子的交換容量適當選擇即可。當然，亦可將無機離子交換體和有機離子交換體進行混合而使用。 電子元件的製造製程中包括進行加熱之步驟，因此無機離子交換體為較佳。These inorganic ion exchangers and organic ion exchangers may be appropriately selected in consideration of the types of cations and anions to be captured, and the exchange capacity of the ions. Of course, an inorganic ion exchanger and an organic ion exchanger may be mixed and used. The manufacturing process of electronic components includes the step of heating, so inorganic ion exchangers are preferred.
又，例如從機械強度的觀點考慮，關於防止材料與上述高分子材料的混合比，將遷移防止材料設為10質量%以下為較佳，將遷移防止材料設為5質量%以下為更佳，此外，將遷移防止材料設為2.5質量%以下為進一步較佳。又，從抑制接合半導體元件或半導體晶圓與各向異性導電性構件時的遷移之觀點考慮，將遷移防止材料設為0.01質量%以上為較佳。In addition, for example, from the viewpoint of mechanical strength, the mixing ratio of the preventing material and the above-mentioned polymer material is preferably 10 mass % or less of the migration preventing material, and more preferably 5 mass % or less of the migration preventing material. Moreover, it is more preferable to make a migration prevention material 2.5 mass % or less. Moreover, from the viewpoint of suppressing migration at the time of bonding a semiconductor element or a semiconductor wafer and an anisotropically conductive member, it is preferable to make the migration preventing material 0.01 mass % or more.
＜無機填充劑＞ 樹脂層可以含有無機填充劑。 作為無機填充劑並不受特別的限制，能夠從公知者中適當選擇，例如可舉出高嶺土、硫酸鋇、鈦酸鋇、氧化矽粉末、微粉狀氧化矽、氣相法二氧化矽、無定形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母、氮化鋁、氧化鋯、氧化釔、碳化矽及氮化矽等。＜Inorganic fillers＞ The resin layer may contain an inorganic filler. The inorganic filler is not particularly limited and can be appropriately selected from known ones, and examples thereof include kaolin, barium sulfate, barium titanate, silicon oxide powder, fine powdered silicon oxide, fumed silicon dioxide, Shaped silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica, aluminum nitride, zirconia, yttrium oxide , silicon carbide and silicon nitride, etc.
根據防止無機填充劑進入導通路之間且進一步提高導通可靠性之理由，無機填充劑的平均粒徑大於各導通路的間隔為較佳。 無機填充劑的平均粒徑，30nm～10μm為較佳，80nm～1μm為更佳。 在此，關於平均粒徑，將藉由雷射衍射散射式粒徑測定裝置（NIKKISO CO.,LTD.製造的Microtrac MT3300）測定之一次粒徑設為平均粒徑。For the reasons of preventing the inorganic filler from entering between the conduction paths and further improving the conduction reliability, the average particle size of the inorganic filler is preferably larger than the interval between the conduction paths. The average particle size of the inorganic filler is preferably 30 nm to 10 μm, and more preferably 80 nm to 1 μm. Here, about the average particle size, the primary particle size measured by a laser diffraction scattering particle size measuring apparatus (Microtrac MT3300 manufactured by NIKKISO CO., LTD.) is referred to as an average particle size.
＜硬化劑＞ 樹脂層可以含有硬化劑。 在含有硬化劑之情況下，從抑制與連接對象的半導體元件或半導體晶圓的表面形狀的接合不良之觀點考慮，不使用常溫下為固體的硬化劑，而含有常溫下為液體的硬化劑為更佳。 在此，“常溫下為固體”係指在25℃下為固體，例如熔點高於25℃之溫度之物質。＜Hardener＞ The resin layer may contain a hardener. In the case of containing a curing agent, from the viewpoint of suppressing poor bonding with the surface shape of the semiconductor element or semiconductor wafer to be connected, a curing agent that is solid at room temperature is not used, and a curing agent that is liquid at room temperature is included: better. Here, "solid at normal temperature" refers to a solid at 25°C, for example, a substance whose melting point is higher than 25°C.
作為硬化劑，具體而言，例如可舉出如二胺基二苯甲烷、二胺基二苯碸之類的芳香族胺、脂肪族胺、4-甲基咪唑等咪唑衍生物、雙氰胺、四甲基胍、硫脲加成胺、甲基六氫鄰苯二甲酸酐等羧酸酐、羧酸醯肼、羧酸醯胺、多酚化合物、酚醛清漆樹脂及聚硫醇等，能夠從該等硬化劑中適當選擇在25℃下為液體者。另外，硬化劑可單獨使用1種，亦可併用2種以上。Specific examples of the curing agent include aromatic amines such as diaminodiphenylmethane and diaminodiphenylene, aliphatic amines, imidazole derivatives such as 4-methylimidazole, and dicyandiamide. , tetramethylguanidine, thiourea addition amine, methylhexahydrophthalic anhydride and other carboxylic anhydrides, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins and polythiols, etc., can be obtained from Among these hardeners, those that are liquid at 25°C are appropriately selected. Moreover, a hardening agent may be used individually by 1 type, and may use 2 or more types together.
在樹脂層中，在不損害其特性之範圍內，可以含有各種添加劑，例如通常廣泛添加到半導體封裝的樹脂絕緣膜中之分散劑、緩衝劑、黏度調整劑等。The resin layer may contain various additives, such as dispersants, buffers, viscosity modifiers, etc., which are generally widely added to resin insulating films of semiconductor encapsulation, within the range not impairing the properties thereof.
＜形狀＞
根據保護金屬填充微細結構體32導通路20之理由，樹脂層的厚度大於導通路20的突出部20a、20b的高度，1μm～5μm為較佳。＜Shape＞
The thickness of the resin layer is larger than the heights of the protruding
其次，關於保持製程進行說明。 〔保持製程〕 圖37係表示在本發明的實施形態的保持製程中使用之容器的一例之示意性立體圖，圖38係表示本發明的實施形態的保持製程的收納容器的一例之示意性剖視圖。 在保持製程中，保持係指還包括靜置狀態及輸送等移動，而並不限定於靜置狀態。Next, the holding process will be described. [Maintain process] 37 is a schematic perspective view showing an example of a container used in the holding process according to the embodiment of the present invention, and FIG. 38 is a schematic cross-sectional view showing an example of a storage container in the holding process according to the embodiment of the present invention. In the holding process, holding refers to a stationary state and movement such as conveying, and is not limited to a stationary state.
如上所述，保持製程係將藉由填充製程在結構體18（參閱圖5）的複數個貫通孔17（細孔）中填充金屬而得到之金屬填充構件21（參閱圖6），在相對濕度10～30%的環境下暴露24小時以上之製程。藉由上述保持製程，在具有貫通孔（細孔）之氧化膜（陽極氧化膜16）中得到穩定之絕緣電阻。若相對濕度超過40%，則絕緣電阻發生變動，無法得到穩定之絕緣電阻。 另一方面，將相對濕度維持在小於10%需要專用設備等，難以管理濕度。 又，關於保持時間，若小於24小時，則絕緣電阻發生變動，無法得到穩定之絕緣電阻。As described above, the holding process is a metal-filled member 21 (see FIG. 6 ) obtained by filling the plurality of through holes 17 (pores) of the structure 18 (see FIG. 5 ) with metal by the filling process, and the relative humidity The process of exposure for more than 24 hours under the environment of 10-30%. By the above-mentioned holding process, stable insulation resistance is obtained in the oxide film (anodized film 16 ) having through holes (pores). If the relative humidity exceeds 40%, the insulation resistance will fluctuate and a stable insulation resistance cannot be obtained. On the other hand, maintaining the relative humidity to less than 10% requires dedicated equipment and the like, and it is difficult to manage the humidity. In addition, about the holding time, if it is less than 24 hours, the insulation resistance will fluctuate, and a stable insulation resistance cannot be obtained.
在保持製程中，若將金屬填充構件21在相對濕度10～30%的環境下暴露24小時以上，則保管位置等並不受特別的限定。例如，在保持製程中，金屬填充構件21收納於圖37所示容器40中而保管。容器40具有容器主體42和蓋44。在容器40中，用蓋44封閉容器主體42的開口42a，容器主體42被密封。
保持製程中之溫度為25℃以上即可，40℃～50℃為較佳。In the holding process, if the
在容器內部42b，雖然未圖示，但是例如設置有擱板，複數個金屬填充構件21一個個隔開間隔地收納於擱板中。若金屬填充構件21接觸並積層，則因金屬填充構件21振動等而金屬填充構件21彼此摩擦時，金屬填充構件21可能會損傷，因此金屬填充構件21如上所述隔開間隔地收納為較佳。若能夠一個個隔開間隔地收納，則並不限定於擱板，亦可以係間隔件來代替擱板。
另外，金屬填充構件21如上所述呈矩形，作為容器40，能夠使用收納矩形基板之各種容器。
金屬填充構件21與通常的半導體晶圓的形狀相同，在圓形之情況下，作為容器40，能夠使用收納半導體晶圓之各種容器。作為容器40，能夠使用半導體晶圓的輸送容器，例如，能夠使用前端開口片盒（FOUP）及前端開口運輸盒（FOSB）等。In the container interior 42b, although not shown, for example, a shelf is provided, and the plurality of
在保持製程中，例如，如圖38所示，使用收納容器50和調整收納容器50的內部50a的溫度及濕度之調整部52。
在收納容器50中設置有記錄內部50a的溫度變化及濕度變化之感測器53，根據來自感測器53的溫度資訊及濕度資訊，調整部52至少調整收納容器50的內部50a的濕度。在由調整部52調整收納容器50的內部50a的溫度及濕度中，例如使用基於來自感測器53的溫度資訊及濕度資訊之反饋控制。In the holding process, for example, as shown in FIG. 38, the
調整部52例如若能夠調整濕度，則並不受特別的限定。可以利用公知的空調設備。又，調整部52與收納容器50可以係一體或分體。
在保持製程中，由於在相對濕度10～30%的環境下暴露24小時以上即可，因此調整部52具有至少能夠調整溫度之功能即可，亦可以係對收納容器50的內部50a進行換氣之葉片。
另外，關於濕度，可以藉由將吸濕劑設置於收納容器50的內部50a進行調整，亦可將吸濕劑設置於容器40內，並由調整部52僅調整溫度。
感測器53若在保管期間能夠測量溫度及濕度，則並不受特別的限定，但是溫度資訊及濕度資訊係與時刻一同按時序記錄者，亦即，能夠以時間履歷記錄為較佳。又，感測器53可以係有線式或無線式。The
在保持製程中，在收納容器50的內部50a收納複數個容器40，在收納之狀態下，使調整部52進行動作，從而將收納容器50的內部50a中的容器40的金屬填充構件21的相對濕度保持在10～40%。In the holding process, a plurality of
又，由調整部52將收納容器50的內部50a調整成為在溫度25℃下的絕對濕度為50%以下的含水量（g/cm3
）的環境為較佳。另外，溫度25℃下的絕對濕度為50%以下的含水量（g/cm3
）為11.52（g/cm3
）。藉由降低收納容器50的內部50a的濕度，能夠減少收納容器50的內部50a的含水量。
在該情況下，例如將溫度與濕度及絕對濕度的關係存儲於調整部52中，並根據來自感測器53的溫度資訊和濕度資訊來求出收納容器50的內部50a的含水量。根據所求出之含水量，可以由調整部52來調整溫度和濕度。
如上所述，收納容器50的內部50a的上述含水量能夠使用吸濕劑進行調整。Moreover, it is preferable to adjust the inside 50a of the
又，在壓力比大氣壓低的減壓下，保管金屬填充構件21亦較佳。藉此，收納容器50的內部50a的絕對濕度降低。藉此，能夠抑制金屬填充構件21的絕緣電阻的變動，進而能夠抑制金屬填充微細結構體的性能劣化。又，如上所述，藉由在減壓下保管金屬填充構件21，亦可抑制導通路20的突出部20a、20b的氧化等，藉此能夠提高與金屬填充構件21的接合對象例如半導體元件及半導體晶圓的接合強度，並能夠獲得與接合對象的接合電阻的降低的效果。Moreover, it is also preferable to store the
上述減壓下係例如藉由排出收納容器50的內部50a的空氣而實現，例如藉由在調整部52中設置旋轉泵等真空泵，進而設置測量收納容器50的內部50a的壓力之壓力計或壓力感測器而實現。作為壓力計及壓力感測器，若係測定比大氣壓低的壓力者，則並不受特別的限定，在通常之真空容器中適當利用用於測量壓力者。
上述減壓下係指壓力為0.01～0.1Pa程度。
又，雖然構成為在收納容器50的內部50a設置複數個，但是並不限定於此，亦可為一個。The above-mentioned decompression is realized by, for example, discharging the air in the interior 50a of the
如此，能夠保管金屬填充構件21，並能夠在保管於收納容器50中之狀態下運輸金屬填充構件21。藉此，能夠管理保管狀態，並運輸至運輸目的地。In this way, the
容器40並不限定於收納容器50，例如，如圖39所示，亦可收納於收納袋54中。收納袋54例如由具有阻氣性之膜構成。具有阻氣性之膜例如係水蒸氣透過性低者，能夠使用用於包裝電子零件之公知的膜，或者在有機EL（Electro Luminescence：電致發光）、電子紙或太陽能電池等中使用之阻氣膜。
阻氣性由水蒸氣透過性來評價，水蒸氣透過性藉由MOCON法等而測定。The
在將容器40收納於收納袋54中之情況下，收納袋54的水蒸氣透過性低，由於從外部難以調整內部的濕度，因此在收納袋54的內部設置吸濕劑55為較佳。關於吸濕劑55的量，根據所使用之收納袋54的水蒸氣透過性、容器40的大小及保管期間等預先求出，並將預先求出之量的吸濕劑55設置於收納袋54的內部。將收納於收納袋54中之容器40配置於收納容器50的內部50a，如上所述，進行保管。在該情況下，由調整部52調整收納容器50的內部50a的溫度，金屬填充構件21的相對溫度設為10～40%，並保管金屬填充構件21。即使在將容器40收納於收納袋54中之情況下，如上所述，亦可將收納容器50的內部50a的壓力設為比大氣壓低的壓力，並在減壓下保管金屬填充構件21。When the
又，如圖40所示，可以在容器40中設置上述調整部52和感測器53。即使在該情況下，亦能夠以與在上述收納容器50的內部50a配置容器40時相同之方式保管金屬填充構件21。如上所述，亦能夠將收納容器50的內部50a的壓力設為比大氣壓低的壓力，並在減壓下保管金屬填充構件21。In addition, as shown in FIG. 40 , the above-mentioned
如圖39所示，在使用收納袋54之情況下，不需要圖37所示容器40，例如，如圖41所示，可以在金屬填充構件21的金屬層19上配置間隔件56，積層複數個金屬填充構件21並收納於收納袋54中。在該情況下，為了將相對溫度設為10～40%，如圖39所示，在收納袋54的內部配置吸濕劑55亦較佳。
作為間隔件56，能夠使用紙、樹脂膜等。另外，作為間隔件56，至少覆蓋金屬填充構件21的金屬層19者即可。As shown in FIG. 39, when the
本發明係基本上如上所述構成者。以上，關於本發明的金屬填充微細結構體的製造方法進行了詳細說明，但是本發明並不限定於上述實施形態，在不脫離本發明的主旨之範圍內，當然，可以進行各種改進或變更。 [實施例]The present invention is basically constituted as described above. As mentioned above, although the manufacturing method of the metal-filled microstructure of the present invention has been described in detail, the present invention is not limited to the above-described embodiment, and various improvements and changes can of course be made without departing from the gist of the present invention. [Example]
以下，舉出實施例，對本發明的特徵進行更具體的說明。以下實施例所示材料、試劑、物質量其比例及操作等，只要不脫離本發明的主旨，就能夠適當地變更。從而，本發明的範圍並不限定於以下實施例。 在本實施例中，製作出實施例1～實施例9及比較例1～比較例3的金屬填充構件。關於實施例1～實施例9及比較例1～比較例3的金屬填充構件，評價了輸送性。關於實施例1～實施例9及比較例1～比較例3的金屬填充構件，在確保各向異性導電性之後，評價了絕緣電阻。以下，關於輸送性及絕緣電阻的各評價項目進行說明。Hereinafter, an Example is given and the characteristic of this invention is demonstrated more concretely. The materials, reagents, substance amounts, ratios, operations, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following examples. In this example, the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3 were produced. Regarding the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3, the transportability was evaluated. Regarding the metal-filled members of Examples 1 to 9 and Comparative Examples 1 to 3, after securing anisotropic conductivity, the insulation resistance was evaluated. Hereinafter, each evaluation item of transportability and insulation resistance will be described.
關於輸送性的評價進行說明。
＜輸送性的評價＞
使用金屬填充構件，如下所示評價了輸送性。
關於輸送性，根據JIS Z0200：2013包裝貨物-性能試驗方法的一般規則，在JIS Z0232：2004的包裝貨物-振動試驗方法中記載的隨機振動試驗中假定為1級，並實施輸送振動試驗及彈跳振動試驗而進行了評價。
包裝形態係，一邊夾持合紙，一邊將各金屬填充構件積層10片並封入到氯乙烯製盒（155mm×155mm×35mm、苯乙烯方形盒19型AS ONE Corporation.製造）中。將厚度為1cm的發泡苯乙烯製緩衝材料配置於積層後之金屬填充構件的上方和下方。在盒子上蓋上蓋，對每個盒進行層合封裝，並設為測試材料。合紙使用了AP清潔紙II A4粉色（72g/m2
）。The evaluation of transportability will be described. <Evaluation of Transportability> Using the metal filling member, the transportability was evaluated as follows. Regarding transportability, according to the general rules of JIS Z0200:2013 Packaged Goods - Performance Test Methods, the random vibration test described in JIS Z0232:2004's Packaged Goods - Vibration Test Method is assumed to be
輸送性試驗中之溫度和濕度條件係提供於如下試驗：根據JIS Z 0203：2000的表1（預處理的溫度和濕度條件）的G（+23℃，濕度為50%RH（相對濕度））對測試材料進行180分鐘的隨機振動試驗，接著對相同之測試材料進行30分鐘的彈跳試驗。
在上述試驗之後，肉眼確認從盒中取出之金屬填充構件，在金屬填充部中，將輸送複數片者中的評價級別最差者的結果設為整體評價。
根據以下評價基準，評價了對金屬填充部損傷。將輸送性的評價結果示於下述表1中。The temperature and humidity conditions in the transportability test are provided in the following test: G (+23°C,
評價基準 在金屬填充構件中，將作為金屬填充部之金屬層中無刮痕之情況設為A。 在金屬填充構件中，將作為金屬填充部之金屬層中有刮痕但未到達陽極氧化膜之情況設為B。 在金屬填充構件中，將作為金屬填充部之金屬層中有刮痕且到達陽極氧化膜之情況設為C。Evaluation benchmark In the metal-filled member, the case where there is no scratch in the metal layer serving as the metal-filled portion is referred to as A. In the metal-filled member, the case where there is a scratch in the metal layer serving as the metal-filled portion but does not reach the anodic oxide film is defined as B. In the metal-filled member, the case where there is a scratch in the metal layer as the metal-filled portion and reaches the anodic oxide film is set as C.
關於絕緣電阻的評價進行說明。 ＜絕緣電阻的評價＞ 關於所製造之金屬填充構件，在去除金屬層之後，去除構成閥金屬構件之鋁基板，並設為陽極氧化膜單體。其次，藉由化學機械研磨（CMP）來研磨陽極氧化膜的表面而進行了平滑化。藉此，確保了各向異性導電性。在該狀態下，在陽極氧化膜的表面上，當離開20mm設置端子時，使用絕緣電阻計測定出電阻值。 另外，關於直至金屬填充構件確保各向異性導電性之製程，後面進行詳細說明。 基於電阻值的數值，藉由下述評價基準評價了絕緣電阻。將絕緣電阻的評價結果示於下述表1中。 評價基準 A：電阻R＞10MΩ B：10MΩ≥電阻R＞1MΩ C：1MΩ≥電阻R＞10kΩ D：10kΩ≥電阻R＞1kΩ E：1kΩ≥電阻RThe evaluation of insulation resistance will be described. <Evaluation of Insulation Resistance> With regard to the fabricated metal-filled member, after removing the metal layer, the aluminum substrate constituting the valve metal member was removed, and was used as an anodic oxide film alone. Next, the surface of the anodized film was smoothed by chemical mechanical polishing (CMP). Thereby, anisotropic conductivity is ensured. In this state, on the surface of the anodized film, when the terminal was installed at a distance of 20 mm, the resistance value was measured using an insulation resistance meter. In addition, the process until anisotropic conductivity is ensured to the metal-filled member will be described in detail later. Based on the numerical value of the resistance value, the insulation resistance was evaluated by the following evaluation criteria. The evaluation results of the insulation resistance are shown in Table 1 below. Evaluation benchmark A: Resistance R＞10MΩ B: 10MΩ≥resistance R＞1MΩ C: 1MΩ≥resistance R>10kΩ D: 10kΩ≥resistance R＞1kΩ E: 1kΩ≥resistance R
以下，關於實施例1～實施例9及比較例1～比較例3進行說明。Hereinafter, Examples 1 to 9 and Comparative Examples 1 to 3 will be described.
（實施例1）
關於實施例1的金屬填充構件進行說明。
［金屬填充構件］
＜鋁基板＞
使用了純度為99.999質量%的鋁基板。將鋁基板的厚度設為120μm。
關於鋁基板，在修整為15cm見方尺寸之基礎上，以在周圍產生5mm寬度的框之方式黏貼了高黏著帶。框內部的陽極氧化膜16部分的尺寸設為14cm見方。高黏著帶使用了NITTO DENKO CS SYSTEM CORPORATION製造的DANPALON（註冊商標）膠帶No.375（寬度25mm×長度50m）。(Example 1)
The metal-filled member of Example 1 will be described.
[Metal filling member]
＜Aluminum substrate＞
An aluminum substrate with a purity of 99.999 mass % was used. The thickness of the aluminum substrate was set to 120 μm.
The aluminum substrate was trimmed to a size of 15cm square, and then a high-adhesion tape was attached so that a frame with a width of 5mm was formed around it. The size of the portion of the anodized
＜電解研磨處理＞ 使用以下組成的電解研磨液，在電壓10V、液體溫度65℃、液體流速3.0m/分鐘的條件下，對上述鋁基板實施了電解研磨處理。另外，電解處理的處理面積設為0.12m2 。 陰極設為碳電極，電源使用了GP0110-30R（TAKASAGO LTD.製造）。又，使用旋漩渦式流量監測器FLM22-10PCW（AS ONE Corporation.製造）測量電解液的流速。 （電解研磨液組成） ・85質量%磷酸（Wako Pure Chemical,Ltd.試劑） 660mL ・純水 160mL ・硫酸 150mL ・乙二醇 30mL<Electrolytic polishing treatment> The above-mentioned aluminum substrate was subjected to an electrolytic polishing treatment under the conditions of a voltage of 10 V, a liquid temperature of 65° C., and a liquid flow rate of 3.0 m/min using an electrolytic polishing liquid of the following composition. In addition, the treatment area of the electrolytic treatment was set to 0.12 m 2 . The cathode was a carbon electrode, and the power source used GP0110-30R (manufactured by TAKASAGO LTD.). Also, the flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation). (Composition of electrolytic polishing liquid) ・85% by mass phosphoric acid (Wako Pure Chemical, Ltd. reagent) 660mL ・Pure water 160mL ・Sulfuric acid 150mL ・Ethylene glycol 30mL
＜陽極氧化處理製程＞ 其次，按照日本特開2007-204802號公報中記載的順序，藉由自規則化法對電解研磨處理之後的鋁基板實施了陽極氧化處理。 用0.50mol/L的草酸電解液，在電壓45V、液體溫度16℃、液體流速3.0m/分鐘的條件下，對電解研磨處理之後的鋁基板實施了1小時的預陽極氧化處理。 然後，實施了使預陽極氧化處理後的鋁基板在0.6mol/L磷酸的水溶液（液體溫度：40℃）中浸漬0.5小時之脫膜處理。 然後，用0.50mol/L草酸的電解液，在電壓45V、液體溫度16℃、液體流速3.0m/分鐘的條件下再次實施陽極氧化處理，使鋁基板的表面局部陽極氧化，從而形成厚度為50μm的陽極氧化膜。 藉此，得到結構體，該結構體具有在外緣上具備5mm寬度的框部之鋁基板和設置於鋁基板的框部內之陽極氧化膜。 另外，預陽極氧化處理及再陽極氧化處理均在用高黏著帶來掩蓋鋁基板之狀態下進行。另外，在預陽極氧化處理及再陽極氧化處理中，陰極均為鈦電極，電源使用了PAM320-12（KIKUSUI ELECTRONICS CORPORATION製造）。又，冷卻裝置使用了NeoCool BD36（Yamato Scientific Co.,Ltd.製造），攪拌加溫裝置使用了對攪拌器PS-100（EYELATOKYO RIKAKIKAI CO,LTD.製造）。此外，使用漩渦式流量監測器FLM22-10PCW（AS ONE Corporation.製造）測量了電解液的流速。＜Anodizing process＞ Next, according to the procedure described in Japanese Patent Laid-Open No. 2007-204802, the aluminum substrate after the electrolytic polishing treatment was subjected to anodization treatment by the self-regulating method. Using 0.50 mol/L oxalic acid electrolyte, under the conditions of a voltage of 45 V, a liquid temperature of 16° C., and a liquid flow rate of 3.0 m/min, the aluminum substrate after the electropolishing treatment was subjected to a pre-anodizing treatment for 1 hour. Then, a film release treatment in which the pre-anodized aluminum substrate was immersed in an aqueous solution of 0.6 mol/L phosphoric acid (liquid temperature: 40° C.) for 0.5 hours was performed. Then, anodizing treatment was performed again with an electrolyte of 0.50mol/L oxalic acid under the conditions of a voltage of 45V, a liquid temperature of 16°C, and a liquid flow rate of 3.0m/min to partially anodize the surface of the aluminum substrate to form a thickness of 50μm. anodic oxide film. In this way, a structure having an aluminum substrate having a frame portion having a width of 5 mm on the outer edge and an anodized film provided in the frame portion of the aluminum substrate was obtained. In addition, both the pre-anodizing treatment and the re-anodizing treatment were performed in a state where the aluminum substrate was covered with a high-adhesion tape. In addition, in the pre-anodizing treatment and the re-anodizing treatment, both the cathodes were titanium electrodes, and PAM320-12 (manufactured by KIKUSUI ELECTRONICS CORPORATION) was used for the power supply. In addition, NeoCool BD36 (manufactured by Yamato Scientific Co., Ltd.) was used as a cooling device, and a pair of stirrer PS-100 (manufactured by EYELATOKYO RIKAKIKAI CO, LTD.) was used as a stirring and heating device. Furthermore, the flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation.).
＜阻擋層去除製程＞ 其次，在與上述陽極氧化處理相同的處理液及處理條件下，一邊使電壓從40V至0V以電壓下降速度0.2V/sec連續下降，一邊實施了電解處理（電解去除處理）。在電解處理中，作為直流電源而使用了PK45-9（模型名稱、MATSUSADA PRECISION Inc.製造）。 陽極氧化處理後的基材在用流水充分清洗之後，用低溫風在幾分鐘內進行了乾燥。經過陽極氧化處理之基板在包含離子交換水（50℃）及界面活性劑之溶液（45℃）中交替各浸漬3分鐘之後，倒入離子交換水，然後以濕潤狀態提供於阻擋層去除處理。另外，包含界面活性劑之溶液使用了將ROHM AND HAAS ELECTRONIC MATERIALS K.K.製造的預處理液“NeutraClean68”以1：4的比例與離子交換水稀釋之溶液。 實施在保持為溫度25℃之過飽和狀態的包含金屬鋅之氫氧化鈉溶液中浸漬2分鐘之蝕刻處理（阻擋層去除處理），然後藉由進行水洗而去除存在於陽極氧化膜底部之阻擋層，在經由微孔露出之鋁基板表面上形成了鋅導電層。包含金屬鋅之氫氧化鈉溶液使用了在氫氧化鈉水溶液（NaOH=52g/L）中溶解了2000ppm氧化鋅之溶液。<Barrier removal process> Next, electrolytic treatment (electrolytic removal treatment) was performed while continuously decreasing the voltage from 40 V to 0 V at a voltage decrease rate of 0.2 V/sec under the same treatment solution and treatment conditions as the above-mentioned anodizing treatment. In the electrolytic treatment, PK45-9 (model name, manufactured by MATSUSADA PRECISION Inc.) was used as a DC power source. After the anodized substrate was sufficiently washed with running water, it was dried with low-temperature air within a few minutes. After the anodized substrate was immersed alternately in a solution containing ion-exchanged water (50°C) and a surfactant (45°C) for 3 minutes, ion-exchanged water was poured, and then the substrate was provided in a wet state for barrier removal treatment. In addition, as the solution containing the surfactant, a solution obtained by diluting the pretreatment liquid "NeutraClean68" manufactured by ROHM AND HAAS ELECTRONIC MATERIALS K.K. with ion-exchanged water at a ratio of 1:4 was used. Etching treatment (barrier layer removal treatment) by immersion in a sodium hydroxide solution containing metallic zinc maintained in a supersaturated state at a temperature of 25°C for 2 minutes, followed by water washing to remove the barrier layer existing at the bottom of the anodized film, A zinc conductive layer is formed on the surface of the aluminum substrate exposed through the micropores. As the sodium hydroxide solution containing metallic zinc, a solution in which 2000 ppm of zinc oxide was dissolved in an aqueous sodium hydroxide solution (NaOH=52 g/L) was used.
在此，存在於阻擋層去除製程後的陽極氧化膜中之微孔（細孔）的平均直徑為60nm。另外，平均直徑係由FE-SEM（Field emission - Scanning Electron Microscope：場發射掃描電子顯微鏡）拍攝表面照片（50000倍的倍率），並作為測定50點之平均值而計算出。 又，阻擋層去除製程後的陽極氧化膜的平均厚度為40μm。亦即，氧化膜的平均厚度為40μm。另外，陽極氧化膜的平均厚度係由FIB（Focused Ion Beam:聚焦離子束）相對於厚度方向對陽極氧化膜進行切削加工，由FE-SEM對其剖面拍攝表面照片（50000倍的倍率），並作為測定10點之平均值而計算出。 存在於陽極氧化膜中之微孔的密度約為1億個/mm2 。另外，微孔的密度藉由在日本特開2008-270158號公報的＜0168＞及＜0169＞段中記載之方法來測定並計算。 又，存在於陽極氧化膜中之微孔的規則度為92%。另外，規則度藉由由FE-SEM拍攝表面照片（20000倍的倍率），並藉由在日本特開2008-270158號公報的[0024]～[0027]段中記載之方法來測定計算。Here, the average diameter of micropores (fine pores) existing in the anodized film after the barrier layer removal process was 60 nm. In addition, the average diameter was calculated by taking a surface photograph (50,000-fold magnification) by FE-SEM (Field Emission-Scanning Electron Microscope), and calculating it as an average value of 50 measurement points. In addition, the average thickness of the anodized film after the barrier layer removal process was 40 μm. That is, the average thickness of the oxide film was 40 μm. In addition, the average thickness of the anodized film was processed by FIB (Focused Ion Beam: Focused Ion Beam) with respect to the thickness direction. Calculated as an average value of 10 measurement points. The density of micropores present in the anodized film is about 100 million/mm 2 . In addition, the density of micropores is measured and calculated by the method described in the paragraphs <0168> and <0169> of JP-A No. 2008-270158. Moreover, the regularity of the micropores existing in the anodized film was 92%. In addition, the regularity is calculated by taking a surface photograph (20000 times magnification) by FE-SEM, and measuring and calculating by the method described in paragraphs [0024] to [0027] of Japanese Patent Laid-Open No. 2008-270158.
＜金屬填充製程＞
其次，將鋁基板設為陰極且將銅設為正極而實施了電鍍處理。
具體而言，藉由使用以下所示組成的銅鍍液實施恆定電流電解，得到在微孔的內部填充銅且在框部上亦形成有由銅構成之金屬層之金屬填充構件。框部上的金屬層的厚度δ（參閱圖6）為50μm。
在此，恆定電流電解係使用PAS20-36（KIKUSUI ELECTRONICS CORP.製造）作為電源，使用Novell,Inc.製造的鍍覆裝置，並使用HOKUTO DENKO CORPORATION製造的電源（HZ-3000），在鍍液中進行循環伏安法而確認析出電位之後，在以下所示條件實施了處理。
（銅鍍液組成及條件）
・硫酸銅 100g/L
・硫酸 1g/L
・鹽酸 15g/L
・SPS（3,3´-二硫代雙（1-丙烷磺酸）二鈉）8.5ppm
・PEG（聚乙二醇）5ppm
・溫度 30℃
・電流密度 10A/dm2 <Metal Filling Process> Next, an aluminum substrate was used as a cathode and copper was used as a positive electrode, and electroplating was performed. Specifically, by performing constant-current electrolysis using a copper plating solution of the composition shown below, a metal-filled member in which copper is filled in the micropores and a metal layer made of copper is also formed on the frame portion is obtained. The thickness δ (see FIG. 6 ) of the metal layer on the frame portion was 50 μm. Here, the constant current electrolysis system used PAS20-36 (manufactured by KIKUSUI ELECTRONICS CORP.) as a power source, a plating apparatus manufactured by Novell, Inc., and a power source (HZ-3000) manufactured by HOKUTO DENKO CORPORATION were used in the plating solution. After cyclic voltammetry was performed to confirm the precipitation potential, the treatment was performed under the conditions shown below. (Copper plating solution composition and conditions) ・Copper sulfate 100g/L ・Sulfuric acid 1g/L ・Hydrochloric acid 15g/L ・SPS (3,3´-dithiobis(1-propanesulfonic acid) disodium) 8.5ppm ・PEG (Polyethylene glycol) 5ppm ・
為了評價上述絕緣電阻，在積層10片所製造之金屬填充構件並收納於氯乙烯製盒中蓋上蓋之狀態下，保管於低濕度型低溫恆溫恆濕器（PDL-4J（型號）ESPEC CORP.製造）內。將低濕度型低溫恆溫恆濕器內部設為40℃的溫度且相對濕度為20%的環境，在暴露25小時之後實施了以下製程。 ＜阻擋層去除製程＞ 對金屬填充構件，使用黏著帶去除了金屬層。黏著帶使用了DANPALON膠帶No.375（NITTO DENKO CORPORATION.製造）。 ＜基板去除製程＞ 其次，藉由在20質量%氯化汞水溶液（升汞）中在20℃下浸漬3小時而溶解並去除鋁基板，藉此設為陽極氧化膜單體。In order to evaluate the above-mentioned insulation resistance, 10 pieces of the fabricated metal filling member were laminated and stored in a low-humidity type cryostat (PDL-4J (model) ESPEC CORP. manufacture). The inside of the low-humidity type cryostat was set to an environment with a temperature of 40°C and a relative humidity of 20%, and the following process was implemented after exposure for 25 hours. <Barrier removal process> For metal-filled components, the metal layer was removed using adhesive tape. The adhesive tape used DANPALON Tape No.375 (manufactured by NITTO DENKO CORPORATION.). <Substrate removal process> Next, the aluminum substrate was dissolved and removed by being immersed in a 20 mass % mercuric chloride aqueous solution (mercuric chloride) at 20° C. for 3 hours, thereby being used as an anodic oxide film alone.
＜平滑化製程＞ 藉此，對陽極氧化膜的表面實施CMP（Chemical Mechanical Polishing：化學機械拋光）處理，並且對表面進行研磨，藉此使表面平滑化。藉由平滑化製程而確保各向異性導電性。在該狀態下，測定出上述絕緣電阻。 在平滑化製程中，使用MAT公司製造的研磨裝置（BC-15CN（商品名稱）），用包含氧化鋁之研磨劑（將WA＃8000（FF）Kemet Japan Co.,Ltd.製造用純水稀釋成4倍之溶液）對陽極氧化膜的表面進行一次研磨，用包含二氧化矽之研磨劑（S-A1-1-0 Kemet Japan Co.,Ltd.製造）進行二次研磨，將研磨後的精加工的算術平均粗糙度（JIS B0601：2001）設為0.005μm。＜Smoothing process＞ Thereby, CMP (Chemical Mechanical Polishing) treatment is performed on the surface of the anodized film, and the surface is polished, thereby smoothing the surface. Anisotropic conductivity is ensured by smoothing the process. In this state, the above-mentioned insulation resistance was measured. In the smoothing process, a grinding device (BC-15CN (trade name)) manufactured by MAT Corporation was used, and an abrasive containing alumina (WA#8000 (FF) manufactured by Kemet Japan Co., Ltd. was diluted with pure water) 4 times the solution), the surface of the anodized film was polished once, and a second polishing was performed with an abrasive containing silicon dioxide (S-A1-1-0, manufactured by Kemet Japan Co., Ltd.), and the polished The arithmetic mean roughness (JIS B0601:2001) of finishing was set to 0.005 μm.
（實施例2） 與實施例1相比，實施例2的不同點在於保持時間為30小時，除此以外，與實施例1相同。 （實施例3） 與實施例1相比，實施例3的不同點在於保持時間為40小時，除此以外，與實施例1相同。 （實施例4） 與實施例2相比，實施例4的不同點在於框部的寬度為3mm，除此以外，與實施例1相同。在實施例4中，以在周圍產生3mm寬度的框之方式黏貼了高黏著帶。 （實施例5） 與實施例3相比，實施例5的不同點在於框部的厚度為240μm，除此以外，與實施例1相同。在實施例5中，使用了厚度為240μm的鋁基板。(Example 2) Compared with Example 1, Example 2 is the same as Example 1 except that the holding time is 30 hours. (Example 3) Compared with Example 1, Example 3 was the same as Example 1 except that the holding time was 40 hours. (Example 4) Compared with Example 2, Example 4 is the same as Example 1 except that the width of the frame portion is 3 mm. In Example 4, the high-adhesion tape was pasted so as to create a frame with a width of 3 mm around it. (Example 5) Compared with Example 3, Example 5 is the same as Example 1 except that the thickness of the frame portion is 240 μm. In Example 5, an aluminum substrate having a thickness of 240 μm was used.
（實施例6） 與實施例2相比，實施例6的不同點在於相對濕度為10%，除此以外，與實施例1相同。 （實施例7） 與實施例3相比，實施例7的不同點在於相對濕度為30%，除此以外，與實施例1相同。 （實施例8） 與實施例3相比，實施例8的不同點在於平均直徑為40nm，除此以外，與實施例1相同。在實施例8中，在15%的硫酸性水溶液中，在25V的電壓下，將液體溫度設定為3℃而實施陽極氧化處理，並將平均直徑設為40nm。 （實施例9） 與實施例3相比，實施例9的不同點在於平均直徑為200nm，除此以外，與實施例1相同。在實施例9中，在195V的電壓下，將液體溫度設定為3℃，用0.1M磷酸性水溶液實施陽極氧化處理，並將平均直徑設為200nm。(Example 6) Compared with Example 2, Example 6 is the same as Example 1 except that the relative humidity is 10%. (Example 7) Compared with Example 3, Example 7 is the same as Example 1 except that the relative humidity is 30%. (Example 8) Compared with Example 3, Example 8 is the same as Example 1 except that the average diameter is 40 nm. In Example 8, in a 15% sulfuric acid aqueous solution, at a voltage of 25V, the liquid temperature was set to 3° C. to perform anodization treatment, and the average diameter was set to 40 nm. (Example 9) Compared with Example 3, Example 9 is the same as Example 1 except that the average diameter is 200 nm. In Example 9, at a voltage of 195 V, the liquid temperature was set to 3° C., anodization treatment was performed with a 0.1 M phosphoric acid aqueous solution, and the average diameter was set to 200 nm.
（比較例1） 與實施例1相比，比較例1的不同點在於保持時間為20小時，除此以外，與實施例1相同。 （比較例2） 與實施例1相比，比較例2的不同點在於構成為沒有框部，除此以外，與實施例1相同。在比較例2中，在閥金屬構件的表面的整個區域形成陽極氧化膜，從而製作出金屬填充構件。 （比較例3） 與實施例1相比，比較例3的不同點在於相對濕度為40%，除此以外，與實施例1相同。(Comparative Example 1) Compared with Example 1, Comparative Example 1 is the same as Example 1 except that the holding time is 20 hours. (Comparative Example 2) Compared with Example 1, Comparative Example 2 is the same as Example 1 except that it has no frame portion. In Comparative Example 2, an anodized film was formed on the entire surface of the valve metal member to produce a metal filled member. (Comparative Example 3) Compared with Example 1, Comparative Example 3 is the same as Example 1 except that the relative humidity is 40%.
[表1]
如表1所示，與比較例1～比較例3相比，在實施例1～實施例9中，關於輸送性及絕緣電阻獲得良好之結果。 在比較例1中，保持時間短，絕緣電阻的結果差。在比較例3中，沒有框部，輸送性的結果差。在比較例5中，相對濕度高，絕緣電阻的結果差。As shown in Table 1, as compared with Comparative Examples 1 to 3, in Examples 1 to 9, favorable results were obtained regarding transportability and insulation resistance. In Comparative Example 1, the holding time was short, and the results of insulation resistance were poor. In Comparative Example 3, there was no frame portion, and the result of transportability was poor. In Comparative Example 5, the relative humidity was high and the results of insulation resistance were poor.
11、15:閥金屬構件
11a、15a、16a、26a、61a、62a、63a:表面
11b、16e:外緣
11c、15c:區域
11d:陽極氧化膜
11e:底部
12、13、14:遮罩
13a:開口
15b:外緣
15d:框部
15e:底部
16:陽極氧化膜
16b:背面
17:貫通孔
18:結構體
19:金屬層
19a:金屬層
20:導通路
20a、20b:突出部
21:金屬填充構件
22:樹脂基材
24:支撐體
26:樹脂層
27:剝離層
28:支撐層
29:剝離劑
30:雙面黏著劑
31:支撐構件
32:金屬填充微細結構體
40:容器
42:容器主體
42a:開口
42b:容器內部
44:蓋
50:收納容器
50a:內部
52:調整部
53:感測器
54:收納袋
55:吸濕劑
56:間隔件
60:電極體
61:絕緣支撐體
62:導電層
63:阻劑層
d:平均直徑
Dt:厚度方向
h:厚度
HA
:厚度
p:中心間距
Q:區域
w:寬度
x:方向
δ:厚度11, 15:
圖1係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖2係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖3係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖4係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖5係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖6係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖7係表示圖5之結構體的俯視圖。 圖8係放大表示圖7所示之結構體的區域Q之示意性俯視圖。 圖9係放大表示圖7所示之結構體的區域Q之示意性剖視圖。 圖10係關於圖6所示之金屬填充構件放大表示相當於圖7所示之結構體的區域Q之部分之示意性俯視圖。 圖11係關於圖6所示之金屬填充構件放大表示相當於圖7所示之結構體的區域Q之部分之示意性剖視圖。 圖12係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖13係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖14係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖15係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖16係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖17係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖18係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖19係表示本發明的實施形態的金屬填充微細結構體的製造方法的第1例的一製程之示意性剖視圖。 圖20係表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例的一製程之示意性剖視圖。 圖21係表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例的一製程之示意性剖視圖。 圖22係表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例的一製程之示意性剖視圖。 圖23係表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例的一製程之示意性剖視圖。 圖24係表示本發明的實施形態的金屬填充微細結構體的製造方法的第2例的一製程之示意性剖視圖。 圖25係表示本發明的實施形態的金屬填充微細結構體的製造方法的第3例的一製程之示意性剖視圖。 圖26係表示本發明的實施形態的金屬填充微細結構體的製造方法的第3例的一製程之示意性剖視圖。 圖27係表示本發明的實施形態的金屬填充微細結構體的製造方法的第3例的一製程之示意性剖視圖。 圖28係表示本發明的實施形態的金屬填充微細結構體的製造方法的第3例的一製程之示意性剖視圖。 圖29係表示本發明的實施形態的金屬填充微細結構體的製造方法的第3例的一製程之示意性剖視圖。 圖30係表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例的一製程之示意性剖視圖。 圖31係表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例的一製程之示意性剖視圖。 圖32係表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例的一製程之示意性剖視圖。 圖33係表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例的一製程之示意性剖視圖。 圖34係表示本發明的實施形態的金屬填充微細結構體的製造方法的第4例的一製程之示意性剖視圖。 圖35係表示本發明的實施形態的金屬填充微細結構體的構成的一例之俯視圖。 圖36係表示本發明的實施形態的金屬填充微細結構體的構成的一例之示意性剖視圖。 圖37係表示在本發明的實施形態的保持製程中使用之容器的一例之示意性立體圖。 圖38係表示在本發明的實施形態的保持工序中使用之收納容器的一例之示意性剖視圖。 圖39係表示在本發明的實施形態的保持製程中使用之收納袋的一例之示意性立體圖。 圖40係表示在本發明的實施形態的保持製程中使用之容器的另一例之示意圖。 圖41係表示在本發明的實施形態的保持製程中使用之收納形態的一例之示意性立體圖。FIG. 1 is a schematic cross-sectional view showing a process of a first example of a method for producing a metal-filled microstructure according to an embodiment of the present invention. 2 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 3 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 4 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 5 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 6 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. FIG. 7 is a plan view showing the structure of FIG. 5 . FIG. 8 is an enlarged schematic plan view showing a region Q of the structure shown in FIG. 7 . FIG. 9 is an enlarged schematic cross-sectional view showing a region Q of the structure shown in FIG. 7 . FIG. 10 is an enlarged schematic plan view showing a portion corresponding to the region Q of the structure shown in FIG. 7 with respect to the metal filling member shown in FIG. 6 . FIG. 11 is a schematic cross-sectional view showing, in an enlarged manner, a portion corresponding to the region Q of the structure shown in FIG. 7 with respect to the metal filling member shown in FIG. 6 . 12 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 13 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 14 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 15 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 16 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 17 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 18 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 19 is a schematic cross-sectional view showing a process of the first example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 20 is a schematic cross-sectional view showing a process of the second example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 21 is a schematic cross-sectional view showing a process of a second example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 22 is a schematic cross-sectional view showing a process of a second example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 23 is a schematic cross-sectional view showing a process of a second example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 24 is a schematic cross-sectional view showing a process of the second example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 25 is a schematic cross-sectional view showing a process of a third example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 26 is a schematic cross-sectional view showing a process of a third example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 27 is a schematic cross-sectional view showing a process of a third example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 28 is a schematic cross-sectional view showing a process of a third example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 29 is a schematic cross-sectional view showing a process of a third example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 30 is a schematic cross-sectional view showing a process of a fourth example of the method for producing the metal-filled microstructure according to the embodiment of the present invention. 31 is a schematic cross-sectional view showing a process of a fourth example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 32 is a schematic cross-sectional view showing a process of a fourth example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 33 is a schematic cross-sectional view showing a process of a fourth example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 34 is a schematic cross-sectional view showing a process of a fourth example of the method for producing a metal-filled microstructure according to the embodiment of the present invention. 35 is a plan view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention. 36 is a schematic cross-sectional view showing an example of the configuration of the metal-filled microstructure according to the embodiment of the present invention. 37 is a schematic perspective view showing an example of a container used in the holding process according to the embodiment of the present invention. 38 is a schematic cross-sectional view showing an example of a storage container used in the holding step of the embodiment of the present invention. 39 is a schematic perspective view showing an example of a storage bag used in the holding process according to the embodiment of the present invention. FIG. 40 is a schematic diagram showing another example of the container used in the holding process according to the embodiment of the present invention. FIG. 41 is a schematic perspective view showing an example of the storage form used in the holding process according to the embodiment of the present invention.
15:閥金屬構件 15: Valve metal components
15b:外緣 15b: Outer edge
15c:區域 15c: Area
15d:框部 15d: Frame
15e:底部 15e: Bottom
16:陽極氧化膜 16: Anodized film
16a:表面 16a: Surface
17:貫通孔 17: Through hole
18:結構體 18: Structure
19:金屬層 19: Metal layer
20:導通路 20: Conduction Path
21:金屬填充構件 21: Metal Filled Components
Dt:厚度方向 Dt: thickness direction
δ:厚度 δ: thickness
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