TWI295696B - Anodes for electroplating operations, and methods of forming materials over semiconductor substrates - Google Patents

Description

1295696 A71295696 A7

技術領域 本發明係關於在半導體基板上電鏡材料的方法。在特定 方面，本發明係關於用於電鍍操作的陽極。於其他方面， 本發明係關於具有至少99·995%純度，並適用於充填浴 中的電解質的金屬。 ' 發明背景 許多應时《用電财法，其巾最好能在基板上形成 -，含金屬的層。圖！中為先前技藝之電鍍裝置1〇的一實例 衣置10包括一容器12，其中包含一液體14(具體而言，為 一電解液）。容器12可包括任何適當材料，包含（例如）一金 屬，在該容器内部表面具有不易純之内襯（未顯示），以保 護該金屬以免和液體14起反應。或者，容器12可包括塑膠 或玻璃。在'某些應用中，可將容器12配置使其能控制該液 體14的溫度，讓該液體14能於電鍍程序中維持在一理想 作溫度。 〜〃 谷态12内包含一陽極16與一基板18。陽極16包括一金脣 ，其最終冑電鑛於基板18的-導電表面上。在所顯示之應 用中，基板18具有一導電表面2〇。其中配置有一電源。與 陽極16和基板18電氣連接，並在該陽極與基板間產生一差 動電壓。該差動電壓導致導電材料自陽極16穿過電解液Μ 遷移到導電表面20處。該導電材料在基板18上橫跨整個表 面20形成一電鍍導電材料層24。 導電材料自陽極16至基板18的遷移，事實上為一系列的 質量轉移事件。具體而言，第一次質量轉移時，導電材料 -5-TECHNICAL FIELD The present invention relates to a method of electron microscopy material on a semiconductor substrate. In a particular aspect, the invention relates to an anode for use in an electroplating operation. In other aspects, the invention relates to metals having an electrolyte of at least 99.995% purity and suitable for use in filling a bath. BACKGROUND OF THE INVENTION Many times, "the use of electricity, the towel is preferably formed on the substrate - a metal-containing layer. Figure! An example of a prior art electroplating apparatus 1A garment 10 includes a container 12 containing a liquid 14 (specifically, an electrolyte). The container 12 can comprise any suitable material, including, for example, a metal having an impervious liner (not shown) on the interior surface of the container to protect the metal from reaction with the liquid 14. Alternatively, container 12 can comprise plastic or glass. In some applications, the container 12 can be configured to control the temperature of the liquid 14 to maintain the liquid 14 at a desired temperature during the plating process. ~ 〃 The valley state 12 contains an anode 16 and a substrate 18. The anode 16 includes a gold lip that eventually is electrowinned on the conductive surface of the substrate 18. In the application shown, the substrate 18 has a conductive surface 2〇. There is a power supply configured therein. It is electrically connected to the anode 16 and the substrate 18, and generates a differential voltage between the anode and the substrate. The differential voltage causes the conductive material to migrate from the anode 16 through the electrolyte Μ to the conductive surface 20. The electrically conductive material forms a layer of electroplated conductive material 24 across the entire surface 20 on the substrate 18. The migration of the conductive material from the anode 16 to the substrate 18 is in fact a series of mass transfer events. Specifically, when the first mass transfer, the conductive material -5-

1295696 . . A71295696 . . A7

本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1295696 五、發明説明（3 ^mic〇nduct〇r subst她）」係定義為指任何包括半導電性材 :结構，包含(但不限於)大塊的半導體材料，例如= B曰圓（單獨的，或於其中包括其他材料的組合）與半導電 層（早獨的，或於其中包括其他材料的組 體=指任何作為支㈣構，包含(但不限於)上 - 日例如）其中具有各種S緣材料與導電材料的 早^^石夕曰曰回。另夕卜，基板5 2亦可包括許多電路元件（未 頌不），共同整合成一積體電路。 關材料54形成於基板52上’並可構成與基板52相 關的電路（未顯示）電性連接的一接線層。導電材料柯括 (例如）鋁及/或銅。 2導電材'料54上形成_絕緣材料56。絕緣材料％係經圖 Π 在其上產生—穿透的開口58。導電材㈣與62形 成於該開口中。導電材料6〇可包括（例如）絡、始、錄、銅 銀和金的至少其中之一，而層膜62則可包括路、錄、銅、 少應用中’層膜60將包括錄 ’而層膜62則將包括金。 在層膜62上有-焊料凸點（s〇lder匕叫⑽。焊料凸點料可 包括（例如）一以錫為基礎的（tin_based)焊料或以鉛為美礎的 焊料’其中的術語「以...為基礎」係指其大部份的二料成 分。焊料凸點64可於最後用作與基板52的外部電路形成一 電性連接，因此即可與層膜54、6〇及62 一起與基板叫目關 聯的電路（未顯示）和基板52的其他外部電路（未顯示）之間形 本紙張尺度適用巾s a家標準(CNS) A4規格(21GX 297公爱） 608 1295696This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1295696 V. The invention description (3 ^mic〇nduct〇r subst her) is defined as any semi-conductive material: structure, including ( But not limited to) a bulk semiconductor material, such as = B circle (alone, or a combination of other materials included therein) and a semiconducting layer (early, or a group including other materials in it = any The branch (four) structure includes, but is not limited to, the upper-day, for example, which has various S-edge materials and conductive materials. In addition, the substrate 52 may also include a plurality of circuit components (not included) which are integrated into an integrated circuit. The closing material 54 is formed on the substrate 52' and may constitute a wiring layer electrically connected to a circuit (not shown) associated with the substrate 52. Conductive materials include, for example, aluminum and/or copper. 2 Conductive material 'material 54 is formed on the material 54. The % of insulating material is through the opening 58 through which the pattern is created. Conductive members (4) and 62 are formed in the opening. The conductive material 6〇 may include, for example, at least one of a network, a precursor, a recording, a copper silver, and a gold, and the layer film 62 may include a road, a recording, a copper, and a lesser application, the layer film 60 will include a recording. Layer film 62 will then comprise gold. There is a solder bump on the layer film 62. The solder bump material may include, for example, a tin-based solder or a lead-based solder. "on a" basis refers to the majority of the two components. The solder bumps 64 can be used to form an electrical connection with the external circuitry of the substrate 52, and thus can be associated with the layers 54 and 6 62 A paper-scale (CNS) A4 specification (21GX 297 public) 608 1295696 is used between the circuit (not shown) associated with the substrate and the other external circuit (not shown) of the substrate 52.

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在所有先前技藝有關陽極（諸如圖1中所 ^ ^ 口 所述的陽極16)的問 碭之中’包含在形成陽極時無法確實控制該陽極材料的成 为與物理特性的問.題。本發明所包含之陽極材料，具有相 對於先前技藝之陽極材料較佳的成分與物理特性。 在所有本發明的方法所可控制的成分參數之中，包括純 度和同質性（homogeneity)兩項因素。具體而言，本發明的 方法可由銀、金、鎳、鉻、鈷和銅的至少其中之一^成陽 極’其純度至少可達重量百分比99·99%(即4N的純度，術語 「4N」係指四個「9(nine)」的意思），在特定方面，其純度 至少可達重量百分比99·995%(4Ν5)、99·999%(5Ν)、 99·9999%(6Ν)或至少 99·99999%(7Ν)。 [0022]此類陽極最好包括極少甚至完全不含發射〇1粒子 的材料，因'α粒子會對半導體結構十分不利。因此，理想成 分所含的轴應少於3ppb，所含的钍亦應少於3ppb，最好是 I由加銼的總含量少於3ppb ;轴加钍的總含量少於丨ppb則 更佳；轴加鉉的總含量少於〇 · 5 ppb則最佳。 在進一步的觀點中，本發明的一陽極材料可包括重量百 分比至少99·995%(4Ν5)之銅/磷合金，其磷的濃度最好約為 重量百分比200 ppm至約1000 ppm，例如約為重量百分比 200 ppm至約600 ppm。此銅/磷合金之純度可為5N、6N 甚至超過7N。此種銅/磷合金亦可稱為摻雜磷的銅 (phosphorus-doped copper)。填的加入可助其在陽極表面產 生一黑色氧化物薄膜。此一薄膜可發揮兩項重要功能。首 先，它可作為一過濾器，捕捉薄膜中的雜質、。其次，該薄 -9- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)In all of the prior art relating to the anode (such as the anode 16 described in Figure 1), the problem of the formation and physical properties of the anode material cannot be reliably controlled during the formation of the anode. The anode materials included in the present invention have preferred composition and physical properties relative to prior art anode materials. Among all the component parameters controllable by the method of the present invention are two factors including purity and homogeneity. In particular, the method of the present invention may be made of at least one of silver, gold, nickel, chromium, cobalt and copper as an anode having a purity of at least 99.9% by weight (ie, a purity of 4N, the term "4N"). Refers to the four "9 (nine)"), in a specific aspect, the purity is at least 99.995% (4Ν5), 99.999% (5Ν), 99.9999% (6Ν) or at least 99. ·99999% (7Ν). [0022] Such anodes preferably comprise materials that are little or completely free of particles that emit ruthenium 1 because 'alpha particles are very detrimental to the semiconductor structure. Therefore, the ideal component should contain less than 3 ppb of axis and should contain less than 3 ppb of barium. Preferably, the total content of I is less than 3 ppb. The total amount of axially twisted is less than 丨ppb. The total amount of axial twist is less than 〇·5 ppb. In a further aspect, an anode material of the present invention may comprise a copper/phosphorus alloy having a weight percentage of at least 99.995% (4Ν5), preferably having a phosphorus concentration of from about 200 ppm to about 1000 ppm by weight, for example, about The weight percentage is from 200 ppm to about 600 ppm. The copper/phosphorus alloy may have a purity of 5N, 6N or even more than 7N. Such copper/phosphorus alloys may also be referred to as phosphorous-doped copper. The addition of the filler helps to produce a black oxide film on the surface of the anode. This film has two important functions. First, it acts as a filter to capture impurities in the film. Secondly, the thin -9- paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

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k 1295696 五、發明説明（6 膜可調節銅的溶解速率，從而使溶液中的銅維持在— =里想濃度。另外，碟及/或其他合金成分的加 = 顆粒（grain)的精煉。 了促進 在另帛觀點中，此種陽極可包括重量 99.995%(4N5)的鎳和硫， 比至少 洚-T炎<χτ甘 隹狩疋硯點中，銅/磷組合之純 度可為5Ν、6Ν甚至超過⑼。其中硫的濃度可自重量百分比 :鳩至⑽，而硫的濃度最好為重量百分比約 約請。/。。加入硫的好處在於：.硫可以促進顆粒的精煉。另 外’較之沒有硫的狀況，它可促進陽植更穩定的溶解。再 ί ’加入硫'降低電阻，從而造成電鑛操作時更低的能源 ，耗。另外，右圖2之結構5〇的層膜54包括銅，而層膜μ包 括鎳，則最好於材料60電解沉積時在材料6〇中加入硫，以 改善含鎳材'料60對含銅層膜54的黏附力。 、、在本發明的其他觀點中，一陽極的成分可與一高純度焊 料成刀（諸如重畺百分比至少99.99%純度（4Ν)的焊料成分） 一致，此成分包含一種以上元素選自由錫、銻、鉛、銀、 銅和鉍所組成之群組。在進一步的觀點中，此種焊料的成 分可具有至少5Ν、5Ν5、6Ν、6Ν5或7Ν的純度。範例性 的焊料成分包括至少5Ν純度的鎬、錫/銻、錫/鉛、錫/銀、 錫/銀/銅、銀/祕和錫/銅。 焊料合金中亦可加入磷。若欲加入磷，則其濃度最好少 於1，000 ppm ’例如：漠度由大於〇 ρρ^到500 ppm。 此種嬋料最好為不含鉛者，以減少該成分中發射α粒子材 料的量。具體而言，自然界中存在鉛的同位素之衰變鏈 -10- 1295696 A7k 1295696 V. INSTRUCTIONS (6) The membrane can adjust the dissolution rate of copper so that the copper in the solution is maintained at the concentration of - =. In addition, the addition of the dish and / or other alloy components = grain refining. Promoting another point of view, such an anode may comprise nickel and sulfur in a weight of 99.995% (4N5), and the purity of the copper/phosphorus combination may be 5 比 in the case of at least 洚-T-inflammation. 6Ν even exceeds (9), wherein the concentration of sulfur can be from weight percentage: 鸠 to (10), and the concentration of sulfur is preferably about weight percent. The benefit of adding sulfur is: sulfur can promote the refining of the particles. Compared with the absence of sulfur, it can promote the more stable dissolution of the planting. Then add 'sulfur' to reduce the electrical resistance, resulting in lower energy and consumption during the operation of the electric ore. In addition, the structure of the structure of Figure 5 on the right The film 54 includes copper, and the film μ includes nickel. Preferably, sulfur is added to the material 6 while the material 60 is electrolytically deposited to improve the adhesion of the nickel-containing material 60 to the copper-containing film 54. In other aspects of the invention, an anode component can be combined with a high purity weld A knife (such as a solder composition having a repeat percentage of at least 99.99% purity (4 Å)) is consistent, and the composition contains more than one element selected from the group consisting of tin, antimony, lead, silver, copper, and antimony. In a further view The composition of such solder may have a purity of at least 5 Ν, 5 Ν 5, 6 Ν, 6 Ν 5 or 7 。. Exemplary solder compositions include at least 5 Ν purity of bismuth, tin/bismuth, tin/lead, tin/silver, tin/silver/copper Silver/secret and tin/copper. Phosphorus may also be added to the solder alloy. If phosphorus is to be added, its concentration is preferably less than 1,000 ppm. For example, the degree of infiltration is greater than 〇ρρ^ to 500 ppm. Preferably, the material is lead-free to reduce the amount of alpha-particle material emitted from the component. Specifically, the decay chain of the isotope of lead exists in nature-10-1295696 A7

—η)導致其發射讀子。另外，此賴同位辛益法 使用習知的精煉方法將其自財移除。適當的無斜成分有 錫/銀、錫/祕、錫/銀/銅、祕/銀和錫/銅。此種組成中的触 遭，最·少於3ppb，而鉉的濃度也最好是少於3响。在 特疋方面本發明之陽極焊料成分的鈾和钍的總量少於 3ppJ)。另外，包括本發明之焊料成分的一較佳陽極之以粒子 數最好係小於或等於G.Hgl/(em2. W，小於Q()2個/㈣2.㈣更 佳，而小於0·0〇2個/(cm2· hr)尤佳。將〇^粒子發射源自焊料移 除的一好處為：α粒子會對效能產生木良影響，主要在所 明「軟錯誤」的區域中。當線路寬度變小時，U粒子可能 會對電路造成永久性的傷害。另一項優點為：消除或減少 鉛含量，將可使電解液沈積程序產生的廢水較乾淨。 一形成包括純度至少5Ν的銅、銀和金的陽極成分的示範 性方法為真空鑄造（vacuum casting)。 幵> 成包括純度至少4N的鎳和鉻的至少其中之一的陽極成 为的示範性方法，包含熱壓（hot pressing)及真空鑄造。 一項形成包括銅/磷並具有至少5N的純度且磷的濃度約 200 ppm到約1〇〇〇 ppm的成分的示範性方法，係採用真空鑄 造及一母合金（mastei: alloy)。銅的精煉可由電解精煉達到 一項形成包括鎳並具有至少4Ν5的鎳/磷純度，且碟的重 量百分率濃度約0.01%到約5%的成分的示範性方法，係採 .· 一 用真空鑄造及一母合金。另一項示範性方法，為結合錄與 硫的粉末，然後將該組合熱壓至一接近理想最終形狀的近 -11 - 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐）- η) causes it to emit a reader. In addition, this acquaintance Xinyi method uses the conventional refining method to remove its self-financing. Suitable non-oblique components are tin/silver, tin/secret, tin/silver/copper, secret/silver and tin/copper. The touch in this composition is less than 3 ppb, and the concentration of strontium is preferably less than 3 volts. In the aspect of the invention, the total amount of uranium and antimony of the anode solder component of the present invention is less than 3 ppJ). Further, the number of particles of a preferred anode including the solder component of the present invention is preferably less than or equal to G.Hgl/(em2.W, less than Q()2/(4)2.(4), and less than 0·0. 〇 2 / (cm2 · hr) is particularly good. One of the benefits of 〇 ^ particle emission from solder removal is that alpha particles will have a good effect on performance, mainly in the area of the "soft error". When the line width becomes small, U particles may cause permanent damage to the circuit. Another advantage is that eliminating or reducing the lead content will make the wastewater generated by the electrolyte deposition process cleaner. One form includes copper with a purity of at least 5 Ν. An exemplary method of the anode composition of silver, gold, and vacuum is vacuum casting. 幵> An exemplary method comprising forming an anode comprising at least one of nickel and chromium having a purity of at least 4N, including hot pressing And vacuum casting. An exemplary method of forming a composition comprising copper/phosphorus and having a purity of at least 5 N and a phosphorus concentration of from about 200 ppm to about 1 〇〇〇 ppm, using vacuum casting and a master alloy (mastei: Alloy). Copper refining can be refined by electrolysis An exemplary method of forming a composition comprising nickel and having a nickel/phosphorus purity of at least 4 Ν5 and a weight percent concentration of the dish of from about 0.01% to about 5%, is a vacuum casting and a mother alloy. An exemplary method is to combine the powder with sulfur and then heat the combination to a near-ideal final shape of approximately -11 - the paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210 X 297 mm)

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線 €12 1295696 A7Line €12 1295696 A7

似網狀。 一項形成-陽極成分，包括至少观度之錫、銻、錯、 銀、銅和!^至少-項，且料料-焊料凸點之電解液 沈積的tf m方法包括將—理想材料的合金進行轉造。 本發明對各種陽極材料的另一項觀點為此類材料的同質 f生“同質性」係用以指涉此類陽極材料，最好在盆 整個陽極中皆能維持_均句成分’且内含物及沈澱物皆均 勻地政佈二其内含物及沈殺物的平均大小最好不超過崎 米。在特定應用中，所有内含物及沈澱物沿著個別内含 及沈殿物的最大尺+ f Α ΑΛ ^ ^+ 寸方向的平均养度將小於或等於1〇微米 ，=於1微米更佳，而所有内含物及沈澱物的平均長度小於 或等於十分之一微米則尤佳。 、It looks like a mesh. A tf m method of forming an anode component comprising at least a portion of the tin, bismuth, erbium, silver, copper, and at least the term, and the material-solder bump deposition comprises an alloy of the desired material Transfer. Another point of view of the present invention for various anode materials is that the homogeneous "homogeneity" of such materials is used to refer to such anode materials, and it is preferred to maintain the _-sentence component in the entire anode of the basin. The inclusions and sediments are evenly distributed. The average size of the inclusions and the sediments is preferably no more than Saki. In a particular application, the average nutrient of all inclusions and precipitates along the maximum radii + f Α ΑΛ ^ ^ + inches of individual inclusions and sediments will be less than or equal to 1 μm, preferably at 1 μm. It is especially preferred that the average length of all inclusions and precipitates is less than or equal to one tenth of a micron. ,

在所有採用本發明的方法生產的陽極成分所可控制的物 理特性之中’包括紋理（texture)和顆粒大小Η以㈣兩項 。具體而言，本發明之陽極的整個平均顆粒大小最好係小 於100微米，小於50微米更隹，而小於10微米則尤佳，且在 特定具體實施例中’則為小於1微米。平均顆粒大小可由相 關技藝的標準方法決定。在本發明的特定方面，一陽極的 顆粒最大尺寸的平均值最好係小於100微米，小於5〇微米更 佳，而小於10微米則尤佳，且在特定具體實施例中，則為 小於1微米。為詮釋本文及隨附之申請專利範圍，指稱一陽 極具有所謂的「平均顆粒大小」，即意謂該陽極的整個所 有顆粒皆具有此一平均顆粒大小，除非特別聲明僅該陽極 之一部份具有所謂的平均顆粒大小。 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1295696 五、發明説明（9 上述之較佳顆粒大小可關係到本發明所包含的任一陽極 成分，包含(例如)基本上含有(或包含)銅 '鎮、銀、金、鉻 、鈷、錫、銻、鉛和鉍的至少其中之一。 術00 V文理」係指結晶方向的分佈，若其方向為具有相 對不規則的分佈，則稱其為具有「弱的㈣」；若__ 具有相對非不規則的方向分佈，則稱其為具有「強的紋理 」本1明的陽極可具有微細構造上的紋理，使不同的金 屬顆粒此以相同速率腐餘。眾所皆知地，纟大多數電解槽 不同的結晶平面會以不同的篷率屬蝕，且利用此一事 實可蝕刻金相顯微照相的樣品，使不同顆粒在光學顯微鏡 檢驗時清晰可見。在陽極微細構造具有紋ί里，以使所有顆 粒顯出相同結晶表面（或近乎相同的表面）的具體實施例中， 可減乂其陽極的差別腐蝕、使其降至最低限或甚至完全消 除。如此可使陽極的腐蝕相對地較均勻。此種均句的腐蝕 可=其他方法造成較均句的電鍍薄膜，以及較長的陽極使 用壽命，和在電鍍浴中較少的微粒。因此，在本發明之陽 極中使用適虽紋理，將可改善該陽極溶解於電鑛浴中的均 勻度，最終將可延長該陽極的使用壽命，並改善該陽極所 形成電鍍薄膜的均勻度。各種陽極皆可要求其具有一均勻 且大體上不規則的紋理，包含基本上由銅、.銅/磷、鎳、; 鎳合金或鎳/硫所構成之陽極，或基本上由鉻或含鉻合金所 構成之陽極，或基本上由銀或含銀合金所構成之陽極，或 基本上包括選自由錫、銻、鉛、銀、銅和鉍所組成群組的 至少其中之一元素的焊料成分所構成之陽極。 本纸張尺度適用中國國家標準((：]^3) Α4規格(210X297公釐） -13- 1295696 A7Among all the physical properties controllable by the anode component produced by the method of the present invention, 'the texture and the particle size are (4). In particular, the anode of the present invention preferably has an overall average particle size of less than 100 microns, less than 50 microns, and more preferably less than 10 microns, and in particular embodiments, less than 1 micron. The average particle size can be determined by standard methods of the relevant art. In a particular aspect of the invention, the average size of the largest dimension of the particles of an anode is preferably less than 100 microns, more preferably less than 5 microns, and more preferably less than 10 microns, and in particular embodiments less than one. Micron. To interpret this article and the accompanying patent application, it is stated that an anode has a so-called "average particle size", which means that all particles of the anode have this average particle size unless specifically stated as only one part of the anode. It has a so-called average particle size. -12- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1295696 V. Description of the invention (9 The preferred particle size described above may be related to any of the anode components included in the present invention, including (for example Basically containing (or containing) at least one of copper 'town, silver, gold, chromium, cobalt, tin, antimony, lead and antimony. 00 V literacy" means the distribution of the crystal direction, if the direction is Relatively irregular distribution, it is said to have "weak (four)"; if __ has a relatively non-irregular direction distribution, it is said to have a "strong texture". The anode of the present invention can have a fine structure. The texture is such that different metal particles are spoiled at the same rate. It is well known that the different crystal planes of most electrolyzers are etched at different rates and the fact that metallographic photomicrographs can be etched To make the different particles clearly visible when examined by optical microscopy. In the specific embodiment where the anode microstructure has a grain so that all particles show the same crystalline surface (or nearly the same surface), the difference in anode can be reduced. Do not corrode, reduce it to a minimum or even eliminate it completely. This can make the corrosion of the anode relatively uniform. Corrosion of this sentence can be compared with other methods to produce a more uniform plating film and a longer anode life. And less particles in the electroplating bath. Therefore, the use of a suitable texture in the anode of the present invention will improve the uniformity of dissolution of the anode in the electric ore bath, which will eventually extend the life of the anode, and Improving the uniformity of the electroplated film formed by the anode. Various anodes may be required to have a uniform and substantially irregular texture, including substantially consisting of copper, copper/phosphorus, nickel, nickel alloy or nickel/sulfur. An anode, or an anode consisting essentially of chromium or a chromium-containing alloy, or an anode consisting essentially of silver or a silver-containing alloy, or consisting essentially of selected from the group consisting of tin, antimony, lead, silver, copper and rhenium The anode of the solder component of at least one of the elements of the group. The paper scale applies to the Chinese national standard ((:]^3) Α4 specification (210X297 mm) -13- 1295696 A7

金Her:陽極紋理控制的一項好處可解釋為··視--屬物件中的母一顆粒為一曰 相對於4考平面Μ p 、a日格（erystallattlce)係 ，陽朽的2 向。該參考平面可為(例如) 场極的腐姓表面。由於每一顆粒皆為相互獨立，故每_ 顆=的晶格相對於此平面皆有其各自的方向。當顆粒方向 士不規則，而結晶平面相對於一參考平面趨向某種排列 日年’即可稱該材料具有_非不規則的「紋理」。這些紋理 可用標準指數表示，其係界定出相對於結晶平面的方向。 例如：由-具有立方體結晶結構之金屬構成的陽極，諸如 銅’可具有-<100〉或<m>或其他的紋理。同樣地，由一 具有六角形結晶結構之金屬構成的陽極，諸如鈷，可具有 -<000=>的紋理。所發展的實際紋理將取決於金屬的種類 ，以及該陽趣的加工和熱處理的經歷而定。另外，由「0」 圍住的數字指數表示的米勒指數（Miller indices)亦被用來描 述對稱的結晶結構中之平面或方向族群。大多數金屬中皆 可藉改變其熱機械處理程序，以產生不同紋理。 在c. E· Wickersham，Jr發表於1987年七/八月份美國真空 協會（the Amencan Vacuum Society)期刊 j.Vac Sci Techn〇1 A5(4)的一篇名為「磁電管濺鍍時的結晶目標效應 (Crystallographic Target Effects in Magnetron Sputtering), 的文早中，冒描述一濺鍍目標的結晶方向對其濺鍍沈積速 率和薄膜均勻度的影響。作者在此篇文章中指出：可藉控 制目標物件的製造程序，以達成矽晶圓薄膜均勻度的改善 。教導如何控制一濺鍍目標的紋理以在多種應用中獲致最 -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公董) 1295696 A7 -------------^_ · 五、發明説明。"— 佳效能的方法，已有數項美國專利案發佈（例如：請參考美 國專利案號 6302977 、 6238494 、 5993621 、 5809393 、 578075 5、5087297)。然而，這些專利並未表明對紋理的控 制會在用於電解浴中的陽極之形成上有任何應用的機會。 結晶結構可影響一材料的腐蝕或溶解特性，此點在為金 湘檢驗蝕刻一材料時可獲得證明。不同走向的顆粒會受到 不同程度的蝕刻或腐蝕。因此，控制一陽極的顆粒方向之 紋理或均勻度，將有助其均句地溶解，以及均句的薄膜沈 積。對紋理的控制可遵循兩種範例形武：對優勢紋理方向 的控制，以及對紋理強度的控制。 紋理的強度，或具有相同方向性之顆粒的相對比例，對 均勻溶解具有相當重要性。若存在不規則紋理（任何特定紋 理的強度皆，不高，且顆粒方向不規則），則具有較佳方向的 顆粒將腐蝕較快，從而產生一不均勻的表面。可能會有二 弱紋理存在，其中某一方向較常出現或較普遍，但大部份 顆粒仍表現出與此不同的方向。因此，非常強的紋理（大多 數顆粒為相同方向）即可導致更均句的腐蝕。 特殊陽極的特定需求紋理可決定於該陽極的材料和幾何 特徵。例如，對一平坦表面而言，使擁擠的平面對準陽極 表面的紋理較為有利。對屬於HCP金屬的鈷而言，此即 (〇〇1)平面，或一（001)紋理。對諸如銅之類的FCC金屬而言 ’此即（111)紋理，而對諸如鉻之類的BCC金屬而言，此即 為一（110)紋理。在特定方面，本發明包含之陽極具有至少 25%的顆粒、至少5〇%的顆粒、至少乃％的顆粒或總顆粒數 -15-Gold Her: One of the benefits of anode texture control can be explained by the fact that the parent-particle in the object is a 相对 relative to the 4 test plane Μ p , a erstallattlce system, the aging 2 direction. The reference plane can be, for example, the surface of the field of the rot. Since each particle is independent of each other, each of the crystal lattices has its own orientation relative to the plane. When the grain direction is irregular, and the crystal plane tends to be aligned with respect to a reference plane, the material has a _non-irregular "texture". These textures can be represented by a standard index that defines the direction relative to the plane of crystallization. For example, an anode composed of a metal having a cubic crystal structure such as copper ' may have -<100> or <m> or other texture. Similarly, an anode composed of a metal having a hexagonal crystal structure, such as cobalt, may have a texture of -<000 =>. The actual texture developed will depend on the type of metal and the experience of processing and heat treatment. In addition, the Miller indices represented by the numerical index enclosed by "0" are also used to describe the plane or direction group in a symmetrical crystal structure. Most metals can be modified to produce different textures by changing their thermomechanical processing. In c. E. Wickersham, Jr., published in the July/August 1987 issue of the Amencan Vacuum Society, j.Vac Sci Techn〇1 A5(4), entitled "Crystalization of Magnetron Sputtering In the early days of this paper, the effect of the crystal orientation of a sputter target on its sputter deposition rate and film uniformity is described. The author points out in this article that the target can be controlled. The manufacturing process of the object to achieve an improvement in the uniformity of the wafer film. How to control the texture of a sputtering target to achieve the most in a variety of applications - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 Gongdong) 1295696 A7 -------------^_ · V. Invention Description. "- The method of good performance has been published in several US patent cases (for example: please refer to the US patent case) No. 6302977, 6238494, 5993621, 5809393, 578075 5, 5087297). However, these patents do not show that the control of the texture has any chance of application in the formation of the anode used in the electrolytic bath. The corrosion or dissolution characteristics of a material can be demonstrated when etching a material for Jinxiang. The particles of different orientations are etched or etched to varying degrees. Therefore, the texture or uniformity of the grain direction of an anode is controlled. It will help to dissolve it evenly, as well as the film deposition of the uniform sentence. The control of the texture can follow two examples: the control of the dominant texture direction and the control of the texture intensity. The intensity of the texture, or the same The relative proportion of directional particles is of considerable importance for uniform dissolution. If irregular textures are present (the strength of any particular texture is not high and the direction of the particles is irregular), particles with better orientation will corrode faster. , resulting in a non-uniform surface. There may be two weak textures, one of which is more common or more common, but most of the particles still exhibit a different direction. Therefore, very strong texture (large Most particles in the same direction can lead to more uniform corrosion. The specific desired texture of a particular anode can be determined by the material of the anode and For example, for a flat surface, it is advantageous to align the crowded plane with the texture of the anode surface. For cobalt belonging to the HCP metal, this is the (〇〇1) plane, or a (001) texture. For a FCC metal such as copper, this is the (111) texture, and for a BCC metal such as chrome, this is a (110) texture. In a particular aspect, the invention comprises an anode having at least 25% of the particles, at least 5% by weight of the particles, at least the % of the particles or the total number of particles - 15 -

1295696 A7 _· '_____B7__ 五、發明説明（14 ) ECAE裝置操作足夠次數（最好是至少四趟，通常是至少六 趟）’同時在各趟之間轉動晶胚150，使該晶胚在各趟之間 產生不同紋理方向，以達成顆粒大小的縮減及紋理的不規 則化。 别文中參考圖3至5說明的方法所生產的材料可用作電解 裝置（諸如參考圖1說明的先前技藝裝置）中的陽極。另外， 可將此種材料切割、壓製或軋製以做成粉末狀、丸狀、軋 條狀或其他可迅速溶解於一適當酸液中以形成一預先填充 電解液的形狀。此種丸狀和粉末狀可稱為該材料的微粒形 式。此種粉末、丸或軋條則可稱岑金屬材料。任何適當的 酸液皆可用來溶解該微粒及/或金屬材料。甲磺酸（methy：u sulfonic acid)可作為一種用來溶解該含焊料成分陽極之金屬 材料的範例，性酸液，而硫酸（sulfuric acid)則可作為溶解含 銅成分陽極的一種範例性酸液。 本發明之一陽極材料可用於一電解沈積程序中，以形成 如圖2中所示之半導體結構5〇中的至少一導電層。具體而言 ，本發明包含一程序，其中提供一半導體基板，並有一佈 線層（如圖2中之佈線層54)形成於該基板之上。可濺鍍沈積 一銅種子層，並接著讓銅電解沈積於該種子層上，以形成 此種佈線層。此種銅可用依據本發明所形成的一陽極沈積 而知，故其純度至少為4N5，且内含物及微粒數量亦已減少 。陽極中最好能避免包含内含物及微粒，因内含物及微粒 會在電解沈積時表現出不同的特性，並會因此導致電化學 沈積材料中的不均勻狀況。在特定具體實施例中，至少某 -18- 本纸張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1295696 A7 - . B7 五、發明説明（15 ) 部份佈線層54係電解沈積自一大體上由銅或銅與磷構成的 才孕 〇 在形成佈線層54之後，再形成遮罩56，然後將後續凸點 下方材料60電化學地沈積於佈線層54上。材料6〇可至少包 括銀、鎳、鉻、鈷和銅的其中之一，並可電化學地沈積自 一含銀純度至少99.995%的陽極；自一含鎳純度至少 99.995%的陽極；或一含錄、絡、姑、銅和銀之中一種以上 純度至少99.995%的陽極。 可利用本發明的方法將各種金屬加入凸點下方金屬中。 例如·鉻常被用來當作石夕晶模上笮路焊塾與構成該倒裝晶 片凸點的焊料之間的凸點下方金屬的一部份。此鉻能強力 黏著於該電路焊墊金屬（通常為A1)，並形成該凸點下方金屬 的其餘部份與該電路之間的一擴散障壁。所採用的鉻係典 型地為一糸列之Cr/Cu層，此一般係使用先前技藝的蒸發方 法所產生。然而，可用依據本發明的方法電鍍Cr和Cu，以 產生這些Cr/Cu層。 在形成凸點下方層膜60之後，第二層凸點下方層膜62可 形成於層膜60之上。在特定具體實施例中，層膜6〇基本上 將為由鎳所構成，或基本上由錄和硫所構成，而層膜62則 基本上將由銀所構成。因此，層膜62可為沈積自一含銀純 度至少4N5的陽極。或者，層膜62可包括，基本上構成自， 或包含除了銀以外（或取代銀）的其他金屬。例如，層膜62可 為沈積自一含銀、鉻和銅之中一種以上，純度至少4N5的陽 極0 -19- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） ΐΙ 12956961295696 A7 _· '_____B7__ V. INSTRUCTIONS (14) The ECAE device is operated a sufficient number of times (preferably at least four turns, usually at least six inches) 'while rotating the crystal embryo 150 between the turns to make the embryo in each Different texture directions are produced between the turns to achieve particle size reduction and texture irregularization. Materials produced by the methods described with reference to Figures 3 through 5 may be used as anodes in electrolytic devices, such as the prior art devices described with reference to Figure 1. Alternatively, the material may be cut, pressed or rolled to form a powder, pellet, strip or other form which is rapidly soluble in a suitable acid to form a pre-filled electrolyte. Such pellets and powders may be referred to as the particulate form of the material. Such powders, pellets or rolled strips can be referred to as metallic materials. Any suitable acid can be used to dissolve the particulates and/or metallic materials. Methion: u sulfonic acid can be used as an example of a metal material for dissolving the anode of the solder-containing component, and sulfuric acid can be used as an exemplary acid for dissolving the anode of the copper-containing component. liquid. One of the anode materials of the present invention can be used in an electrolytic deposition process to form at least one of the conductive layers of the semiconductor structure 5 as shown in FIG. Specifically, the present invention comprises a program in which a semiconductor substrate is provided, and a wiring layer (such as wiring layer 54 in Fig. 2) is formed on the substrate. A copper seed layer can be sputter deposited and then copper deposited onto the seed layer to form such a wiring layer. Such copper can be known by an anode deposition formed in accordance with the present invention, so that it has a purity of at least 4 N5 and the amount of inclusions and particulates has also been reduced. It is preferable to avoid the inclusion of inclusions and particles in the anode, since the inclusions and particles may exhibit different characteristics during electrolytic deposition, and thus may cause unevenness in the electrochemical deposition material. In a specific embodiment, at least a certain -18-paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1295696 A7 - . B7 5. Invention Description (15) Part of the wiring layer 54 is electrolysis Depositing from a portion consisting essentially of copper or copper and phosphorous forms a mask 56 after forming the wiring layer 54, and then depositing the subsequent under bump material 60 onto the wiring layer 54. The material 6 〇 may comprise at least one of silver, nickel, chromium, cobalt and copper, and may be electrochemically deposited from an anode having a purity of at least 99.995% of silver; from an anode having a purity of at least 99.995% of nickel; or One or more anodes of at least 99.995% purity, recorded, complex, copper, and silver. Various metals can be added to the underlying metal of the bumps using the method of the present invention. For example, chromium is often used as part of the underside of the bump between the solder joint between the solder and the solder that forms the bump of the flip chip. This chromium adheres strongly to the circuit pad metal (usually A1) and forms a diffusion barrier between the rest of the metal under the bump and the circuit. The chromium used is typically a stack of Cr/Cu layers, which is typically produced using prior art evaporation methods. However, Cr and Cu can be electroplated by the method according to the invention to produce these Cr/Cu layers. After the formation of the under bump film 60, a second under bump film 62 may be formed over the layer film 60. In a particular embodiment, the film 6 〇 will consist essentially of nickel, or consist essentially of sulphur and sulphur, while the film 62 will consist essentially of silver. Thus, layer film 62 can be deposited from an anode having a silver purity of at least 4N5. Alternatively, layer film 62 may comprise, consist essentially of, or comprise other metals other than silver (or instead of silver). For example, the film 62 may be deposited from one or more of silver, chromium and copper, and the anode having a purity of at least 4N5. 0-19 - The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ΐΙ 1295696

的結構50可用於（例如）倒裝晶片技 依據本發明之方法形成 術’或晶圓級包裝方面。 上述方法為範例性方法，且應明白：除已特y說明者外 本t月亦包含其他具體實施例。例如：本發明包含一項 具體實施例，纟中_陽極材料係用來作為_主要互連電路 之電解沈積。具體而言，本發明包含一方法，其中一半導 體基板上§有溝槽及/或在其上餘刻的通路。接著，以一 PVD或CVD方法沈積一連續障壁層。接著再以PVD、CVD 或無電沉積（electroless dep〇siti〇n)沈積一導電之金屬種子 層1最好為,Cu或Cu的合金。接著再以電化學沈積銅形成整 個半導體特徵。此種銅可用依據本發明所形成的一陽極沈 積而得’故其純度至少為4N5，且内含物及微粒數量亦已減 少〇 本發明在利用高純度陽極與預先填充材料方面相對於先 刖技藝之材料的優勢，包括本發明的材料可改善一電解浴 的電解浴時間壽命；可改善陽極使用壽命；可改善沈積膜 成分、品質和均勻度；並可因此降低相關於電解沈積方法 的成本。 先前已藉由數個示範性方法來說明本發明。然而應明瞭 ’本發明包含之具體實施例具有許多相對於上述示範性方 法的修改及變化。以下將說明數種示範性修改及變化。 -20- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) !295696 五 、發明説明（ 17 ^ 員變化中，可於部份陽極上塗佈一層表面塗料，使 的方、、F在電鍍時不致受電解液腐蝕。一種塗佈此種塗料 的邱々、疋將°亥塗料以火焰喷塗（flame spray)於該陽極需防護 =火噴塗可讓易碎及/或熔點較該陽極成分高很多 -防ΐίί佈於—陽極上。接著，即可用所塗佈材料作為 ^例如，可將一相對較不活潑的金屬（諸如丁⑽ Μ =如氧化鋁）火焰噴塗於一包括Cu的陽極上。在其 乾眭應用中，可將其他材·料火焰噴塗於種類廣泛的陽 護塗料的方ί—Γ易腐姓之表面層。或者，另一種塗佈防 、方法’疋以一聚乙烯塗料實施粉末塗佈。 ^另$變化中，可在一陽極上圖樣化一補償形狀，以 二:腐姓輪靡（en)sicm pn)file)。當陽極溶解在該陽極的 哥命扣持續進行之時，該陽極的表面會逐漸產生一腐 蝕輪廓。腐蝕輪廓係起源於數種陽極特有的特性，以及 錢叹備的*裝和操作。這些特性包含（但不限於）該陽極材質 解槽成何形狀、陽極對陰極比例、電鍍化學作用、電 ^密，、絕緣防護以及電解槽中的流體動態等。兩項因素 、疋陽極的使用哥命。當腐姓輪廓變得越明顯時，它 將會〜響整個晶圓表面上所沈積薄膜的均勻度。一特定使 用者所能容忍的不均勻度將會限制陽極的使用壽命。第二 =因素即該陽極的燒穿（burn-thr()ugh),其中的腐钱實際上 貫穿了該陽極的底部。陽極表面材料的缺乏將可對薄膜的 均句度產生巨大影響。一旦一特定方法發現腐姓輪麻，、即 可發展一補償設計，以將材料加諸直接相關於腐蝕速率的 本纸張尺度適用中國國豕標準(CNS) A4規格(210X297公爱） -21 1295696 A7 B7 五、發明説明（2〇) 易產生問題，因為電解浴會侵蝕到陽極。若未加防護塗 佈，則當陽極腐蝕的時候，電氣連接也會變質。 -24- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)The structure 50 can be used, for example, in flip chip technology to form a wafer or wafer level package in accordance with the method of the present invention. The above method is an exemplary method, and it should be understood that other specific embodiments are included in this month except for those already described. For example, the invention includes a specific embodiment in which the anode material is used for electrolytic deposition of the primary interconnect circuit. In particular, the present invention encompasses a method in which a half of the conductor substrate has § grooves and/or vias remaining thereon. Next, a continuous barrier layer is deposited by a PVD or CVD method. Next, a conductive metal seed layer 1 is deposited by PVD, CVD or electroless deposition (electroless dep〇siti〇n), preferably an alloy of Cu or Cu. The entire semiconductor feature is then formed by electrochemical deposition of copper. Such copper can be obtained by depositing an anode according to the present invention, so that its purity is at least 4N5, and the amount of inclusions and particles has also been reduced. The present invention is relatively advanced in terms of utilizing high purity anodes and prefilled materials. Advantages of the material of the art, including the material of the present invention, can improve the electrolytic bath time life of an electrolytic bath; improve the anode life; improve the composition, quality and uniformity of the deposited film; and thus reduce the cost associated with the electrolytic deposition method . The invention has been previously described by several exemplary methods. It should be understood, however, that the specific embodiments of the present invention are susceptible to many modifications and variations of the exemplary embodiments described above. Several exemplary modifications and variations are described below. -20- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) !295696 V. Invention description (17 ^ member change, can apply a layer of surface coating on some anodes, so that the square , F is not corroded by the electrolyte during electroplating. A coating of such coatings, Qiu Yu, 疋 涂料 coating coating flame spray on the anode to be protected = fire spray can make fragile and / or The melting point is much higher than that of the anode component - it is applied to the anode. Then, the coated material can be used as a flame, for example, a relatively inactive metal such as butyl (10) Μ = alumina can be flame sprayed onto the anode. One includes the anode of Cu. In its dry application, other materials can be flame sprayed on the surface layer of a wide range of masculine coatings. Or another coating protection method '疋Plastic coating with a polyethylene coating. ^ Another variation, can be patterned on an anode to compensate for the shape, two: rot surname (en) sicm pn) file). As the anode dissolves in the anode of the anode, the surface of the anode gradually develops a corroded profile. Corrosion profiles originate from the unique properties of several anodes, as well as the *installation and operation of the money sigh. These characteristics include, but are not limited to, the shape of the anode material, the anode to cathode ratio, the plating chemistry, the electrical insulation, the insulation protection, and the fluid dynamics in the cell. Two factors, the use of the anode of the anode. As the contour of the rot becomes more pronounced, it will rang the uniformity of the film deposited on the entire wafer surface. The unevenness that a particular user can tolerate will limit the useful life of the anode. The second = factor is the burn-thr () ugh of the anode, in which the rot money actually runs through the bottom of the anode. The lack of material on the anode surface can have a large impact on the uniformity of the film. Once a specific method finds a rotten cast, a compensation design can be developed to apply the material to the paper scale directly related to the corrosion rate. The Chinese National Standard (CNS) A4 specification (210X297 public) is used. 1295696 A7 B7 V. INSTRUCTIONS (2〇) It is prone to problems because the electrolytic bath will erode to the anode. If no protective coating is applied, the electrical connections will deteriorate when the anode is corroded. -24- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)

Claims (1)

U 9. 2 V 129%96)7959號專利申請案 中文申請專利範圍替換本(94年U 9. 2 V 129% 96) Patent Application No. 7959 Replacement of Chinese Patent Application (94 years) 申清專利範園 一種用於電鍍浴的陽極，包括一顆粒總數，其中該顆粒 總數中的至少25%具有一互相共同的結晶紋理，以及其 中該共同的結晶紋理為（〇〇丨）。 /、 如申請專利範‘圍第1項之陽極，其中該顆粒總數中的至 少50%具有互相共同的結晶紋理。 如申明專利範圍第1項之陽極，其中該顆粒總數中的至 少75%具有互相共同的結晶紋理。 如申睛專利範圍第1項之陽極，其中該顆粒總數中的至 少90%具有互相共同的結晶紋理。 如申明專利範圍第1項之陽極，其包括一 Hcp金屬' 如申請專利範圍第丨項之陽極，其包括鈷。 一種用於電鍍浴的陽極，其包括一小於1〇〇微米的平均 顆粒大小。 如申請專利範圍第7項之陽極，其包括一小於5〇微米的 平均顆粒大小。 如申請專利範圍第7項之陽極，其包括一小於1〇微米的 平均顆粒大小。 1〇·如申請專利範圍第7項之陽極，其包括一小於1微米的平 均顆粒大小。 1. 2. 3. 4. 5.6. 8. 9. 11·如申請專利範圍第7項之陽極，其重量百分率主要包括 銀、金、鎳、鈷和鉻的至少其中之一。 12· —種用於電鍍浴的陽極，其包括重量百分率至少99·99〇/〇 的銀、金、鎳、鉻或鈷。 13.如申請專利範圍第12項之陽極，其包括至少99·99%的銀。 77952-940919.doc 裝 訂 I295696 A8 B8 C8 ^—-----D8 〜申範圍 ~ - 如申请專利範圍第12項之陽極，其包括至少99.990/0的金。 15 ^ 如申睛專利範圍第12項之陽極，其包括至少99.99%的絡。 .如申請專利範圍第12項之陽極，其包括至少99·99%的鈷。 .如申請專利範圍第12項之陽極，其包括至少99·99%的鎳。 •如申請專利範圍第12項之陽極，其包括一小於ι〇〇微米 的平均顆粒大小。 19 vL· .申請專利範圍第12項之陽極，其包括一小於5〇微米的 平均顆粒大小。 〇·如申請專利範圍第12項之陽極，其包括一小於1〇微米的 平均顆粒大小。 21·如申請專利範圍第12項之陽極，其包括一小於^微米的 平均顆粒大小。 22.如申睛專利範圍第I]項之陽極，其包括重量百分率至少 99.995% 的鎳。 23·如申請專利範圍第22項之陽極，其包括一小於1〇〇微米 的平均顆粒大小。 24·如申請專利範圍第22項之陽極，其包括一小於5〇微米的 平均顆粒大小。 25·如申請專利範圍第22項之陽極，其包括一小於1〇微米的 平均顆粒大小。 26. 如申請專利範圍第22項之陽極，其包括一小於1微米的 千均顆粒大小。 27. 如申請專利範圍第22項之陽極，其包括至少99.9995%的 鎳。 77952-940919.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1295696An anode for an electroplating bath comprising a total number of particles wherein at least 25% of the total number of particles have a mutually common crystalline texture, and wherein the common crystalline texture is (〇〇丨). /, as in the patent application, the anode of the first item, wherein at least 50% of the total number of particles have a mutually common crystal texture. An anode according to claim 1, wherein at least 75% of the total number of particles have a crystal texture in common with each other. The anode of claim 1, wherein at least 90% of the total number of particles has a crystal texture in common with each other. An anode according to claim 1 of the patent scope, which comprises an Hcp metal, such as the anode of the scope of the patent application, which comprises cobalt. An anode for an electroplating bath comprising an average particle size of less than 1 〇〇 micron. An anode according to claim 7 of the patent application, which comprises an average particle size of less than 5 Å. An anode according to claim 7 of the patent application, which comprises an average particle size of less than 1 〇 micrometer. 1A. The anode of claim 7, which comprises an average particle size of less than 1 micron. 1. 2. 3. 4. 5.6. 8. 9. 11. The anode of the scope of claim 7 is mainly composed of at least one of silver, gold, nickel, cobalt and chromium. 12. An anode for an electroplating bath comprising silver, gold, nickel, chromium or cobalt in a weight percentage of at least 99.99 Å/〇. 13. The anode of claim 12, which comprises at least 99.99% silver. 77952-940919.doc Binding I295696 A8 B8 C8 ^—-----D8 ~ Application scope ~ - As in the anode of claim 12, it includes at least 99.990/0 gold. 15 ^ The anode of claim 12, which includes at least 99.99% of the anode. An anode according to claim 12, which comprises at least 99.99% cobalt. An anode according to claim 12, which comprises at least 99.99% nickel. • An anode as claimed in claim 12, which comprises an average particle size of less than 1 μm. 19 vL. The anode of claim 12, which comprises an average particle size of less than 5 microns. 〇 An anode according to claim 12, which comprises an average particle size of less than 1 〇 micrometer. 21. The anode of claim 12, which comprises an average particle size of less than <RTIgt; 22. The anode of claim 1, wherein the anode comprises at least 99.995% by weight nickel. 23. The anode of claim 22, which comprises an average particle size of less than 1 micron. 24. The anode of claim 22, which comprises an average particle size of less than 5 microns. 25. The anode of claim 22, which comprises an average particle size of less than 1 micron. 26. The anode of claim 22, which comprises a thousand mean particle size of less than 1 micron. 27. The anode of claim 22, which comprises at least 99.9995% nickel. 77952-940919.doc This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1295696 28. —種用於電鍍浴的陽極，其包括重量百分率至少 99.999%的銅。 29·如申請專利範圍第28項之陽極，其包括至少99 9995〇/〇的 銅〇 30·如申請專利範圍第28項之陽極，其包括一小於1〇〇微米 的平均顆粒大小。 31·如申請專利範圍第28項之陽極，其包括一小於咒微米的 平均顆粒大小。 32_如申請專利範圍第28項之陽極，其包括一小於⑺微米的 平均顆粒大小。 3 3 ·如申凊專利範圍第2 8項之陽極，其包括一小於}微米的 平均顆粒大小。 34·如申請專利範圍第28項之陽極，其包括少於十億分之3 的轴，並進一步包括少於十億分之3的钍。 35· —種陽極，其包括重量百分率至少Μ;%。/❶的銅/磷合金。 36·如申請專利範圍第35項之陽極，其中該磷之濃度為自重 量百分率約200 ppm至約1〇〇〇 ppm。 37·如申請專利範圍第35項之陽極，其包括一小於1〇〇微米 的平均顆粒大小。 38·如申請專利範圍第35項之陽極，其包括一小於5〇微米的 平均顆粒大小。 39·如申請專利範圍第35項之陽極，其包括一小於1〇微米的 平均顆粒大小。 40·如申請專利範圍第35項之陽極，其包括一小於1微米的 77952-940919.doc -3- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐）- A8 B8 C8 1295696 申請專利範園 平均顆粒大小。 41· 一種用.於電鍍浴的陽極，其包括重量百分率至少 99.995%的錄和硫。 42·如申請專利範圍第41項之陽極，其包栝重量百分率約 〇·〇1%至約5%的硫。 43.如申請專利範圍第41項之陽極，其必栝一小於ι〇〇微米 的干均顆粒大小。. 44·如申請專利範圍第41項之陽極，其忽抟一小於50微米的 平均顆粒大小。 45.如申請專利範圍第41項之陽極，其包抟〆小於1〇微米的 平均顆粒大小。 46·如申請專利範圍第4丨項之陽極，其包栝一小於1微米的 平均顆粒大小。 47· —種用於電鍍浴的陽極，其包括重量百分率至少 99·999%純度的一焊料成分，該焊料成分包括選自由錫 、銻、鉛、銀、鋼和级所構成群組的至少直中之一。 认如申請專利範圍第47項之陽極，其包括_，小於％微米的 平均顆粒火小。 49.如申請專利範圍第47項之陽極，其包括—小於顺米的 平均顆粒大小。 5〇·如申請專利範圍第47項之陽極，直白红 ,^ 只< iw往，具包括一小於5微米的 平均顆粒大小。 51·如申請專利範圍第47項之陽極，其包括—小w微米的 平均顆粒大小。 77952-940919.doc28. An anode for an electroplating bath comprising at least 99.999% by weight copper. 29. The anode of claim 28, which comprises at least 99 9995 Å/inch of copper bismuth. 30. The anode of claim 28, which comprises an average particle size of less than 1 〇〇 microns. 31. The anode of claim 28, which comprises an average particle size less than the curse micron. 32. The anode of claim 28, which comprises an average particle size of less than (7) microns. 3 3 . The anode of claim 28, which comprises an average particle size of less than > 34. The anode of claim 28, which comprises less than 3 parts per billion, and further comprises less than 3 parts per billion. 35. An anode comprising a weight percentage of at least Μ; %. /❶ Copper/phosphorus alloy. 36. The anode of claim 35, wherein the phosphorus concentration is from about 200 ppm to about 1 ppm by weight. 37. The anode of claim 35, which comprises an average particle size of less than 1 micron. 38. The anode of claim 35, which comprises an average particle size of less than 5 microns. 39. The anode of claim 35, which comprises an average particle size of less than 1 micron. 40. For the anode of patent application No. 35, which includes a 77952-940919.doc of less than 1 micron. -3- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) - A8 B8 C8 1295696 The average particle size of the patent application garden. 41. An anode for use in an electroplating bath comprising at least 99.995% by weight of sulfur and sulfur. 42. The anode of claim 41, having a weight percentage of from about 1% to about 5% by weight of the anode. 43. The anode of claim 41, which must have a dry average particle size of less than 1 micron. 44. The anode of claim 41, which ignores an average particle size of less than 50 microns. 45. The anode of claim 41, which has an average particle size of less than 1 micron. 46. The anode of claim 4, wherein the envelope has an average particle size of less than 1 micron. 47. An anode for an electroplating bath comprising a solder component having a purity of at least 99.999% by weight, the solder composition comprising at least one selected from the group consisting of tin, antimony, lead, silver, steel, and grades One of them. The anode of the patent application category 47, which includes _, has an average particle fire of less than % micron. 49. The anode of claim 47, which comprises - an average particle size less than cis. 5〇·The anode of the patent application range 47, straight white red, ^ only < iw, with an average particle size of less than 5 microns. 51. The anode of claim 47, which comprises an average particle size of - small w microns. 77952-940919.doc 12956961295696 52.如申請專利範圍第47項之陽極，其包括至少的別㈣的 焊料。 53·如申請專利範圍第47項之陽極，其包括少於十億分之3 的抽，·並進一步包括少於十億分之3的鉦。 54.如申請專利範圍第47項之陽極，其包括至少99 999%的 錫。 55•如中請專利範圍第47項之陽極，其中該焊料成分包㈣ 和銻。 56·如申請專利範圍第47項之陽極，其中該焊料成分包括錫 和船。 57.如申請專利範圍第47項之陽極，其中該焊料成分包括錫 和銀。 5 8·如申請專利範圍第47項之陽極，其中該焊料成分包括锡 、銀和銅。 59.如申請專利範圍第47項之陽極，其中該焊料成分包括银 和秘。 60·如申請專利範圍第47項之陽極，其中該焊料成分包括锡 和銅。 61· —種形成材料於一半導體基板上的方法，該方法包括下 列步驟： 提供一半導體基板，其上具有佈線層； 於該佈線層上電解沈積銀和鎳的至少其中之一；所有 銀皆係沈積自一含銀量至少99.995%純度的陽極；而戶斤 有鎳則皆係沈積自一含鎳量至少99.995%純度，或係、、尤 77952-940919.doc -5- 1295696 A8 B8 C8 D8 六、申請專利範園 積自一含鎳及硫量至少99·995%純度的陽極，其中硫的 濃度為重量百分率自約001%至約5% ;以及 在該銀和鎳的至少其中之一上形成一焊料。 62·如申請專利範圍第61項之方法，其中該佈線層包括銅， 且係利用一陽極電解沈積形成，該陽極係含有至少重量 百分率99.999°/。的銅，或含有至少重量百分率99 995%的 銅/填合金，其含磷濃度為重量百分率自約2〇〇 ρριη至約 1000 ppm ° 63·如申請專利範圍第61項之方法，其中該焊料係利用一陽 極電解沈積形成，該陽極包括重量百分率純度至少 99.999%的焊料成分，該焊料成分包括選自由錫、銻、 錯、銀、銅和叙所構成元素群組的至少其中之一。 64·如申清專利範圍第61項之方法，其中該電解沈積在該佈 線層上形成鎳，該電解沈積係在一電解浴中發生，且該 電解浴最初係填充以金屬材料，該金屬材料係具有至少 99.995%純度的鎳，或具有至少99.995%純度的鎳及硫， 其中硫的濃度為重量百分率自約0.01 %至約5%。 65·如申請專利範圍第61項之方法，其中該電解沈積在該佈 線層上形成銀，該電解沈積係在一電解浴中發生，且該 電解浴最初係填充以微粒，該微粒係具有至少99.995% 純度的銀。 -6- 77952-940919.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)52. The anode of claim 47, which comprises at least the other (four) solder. 53. The anode of claim 47, which includes less than 3 parts per billion, and further includes less than 3 parts per billion. 54. The anode of claim 47, which comprises at least 99 999% tin. 55• The anode of the 47th patent range, in which the solder component is packaged with (4) and bismuth. 56. The anode of claim 47, wherein the solder composition comprises tin and a boat. 57. The anode of claim 47, wherein the solder composition comprises tin and silver. 5 8. The anode of claim 47, wherein the solder composition comprises tin, silver and copper. 59. The anode of claim 47, wherein the solder composition comprises silver and secret. 60. The anode of claim 47, wherein the solder composition comprises tin and copper. a method of forming a material on a semiconductor substrate, the method comprising the steps of: providing a semiconductor substrate having a wiring layer thereon; electrolytically depositing at least one of silver and nickel on the wiring layer; all silver It is deposited from an anode containing at least 99.995% purity of silver; and nickel is deposited from a nickel content of at least 99.995% purity, or system, especially 77952-940919.doc -5 - 1295696 A8 B8 C8 D8 6. Applying for a patent to an anode comprising nickel and a purity of at least 99.995%, wherein the concentration of sulfur is from about 001% to about 5% by weight; and at least in the silver and nickel A solder is formed on one. 62. The method of claim 61, wherein the wiring layer comprises copper and is formed by electrolytic deposition of an anode comprising at least 99.999 °/weight percent. Copper, or a copper/filled alloy containing at least 99 995% by weight, having a phosphorus concentration of from about 2 〇〇ρριη to about 1000 ppm ° 63. The method of claim 61, wherein the solder The electrode is formed by an anodic electrodeposition comprising a solder component having a weight percent purity of at least 99.999%, the solder component comprising at least one selected from the group consisting of tin, antimony, erbium, silver, copper, and arsenic. 64. The method of claim 61, wherein the electrolytic deposition forms nickel on the wiring layer, the electrolytic deposition occurs in an electrolytic bath, and the electrolytic bath is initially filled with a metal material, the metal material Nickel and sulfur having a purity of at least 99.995%, or nickel and sulfur having a purity of at least 99.995%, wherein the concentration of sulfur is from about 0.01% to about 5% by weight. 65. The method of claim 61, wherein the electrolytic deposition forms silver on the wiring layer, the electrolytic deposition occurs in an electrolytic bath, and the electrolytic bath is initially filled with particles having at least 99.995% purity silver. -6- 77952-940919.doc This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)