TWI499697B - Wafer pretreatment for copper electroplating - Google Patents
Wafer pretreatment for copper electroplating Download PDFInfo
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- TWI499697B TWI499697B TW099132878A TW99132878A TWI499697B TW I499697 B TWI499697 B TW I499697B TW 099132878 A TW099132878 A TW 099132878A TW 99132878 A TW99132878 A TW 99132878A TW I499697 B TWI499697 B TW I499697B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
Description
本發明係關於一種用於半導體晶圓上之通孔及溝槽特徵之銅電鍍之預處理方法。本發明之方法特別適宜電鍍通孔(包括穿矽通孔)或具有高縱橫比之彼等特徵。This invention relates to a method of pretreating copper plating for through-hole and trench features on a semiconductor wafer. The method of the present invention is particularly suitable for electroplating vias (including through vias) or features having a high aspect ratio.
銅電鍍係用於製造半導體互連之主要方法之一。於銅電鍍期間，有時難以獲得對晶圓上之通孔、溝槽及其他連接結構之理想填充結果。Copper plating is one of the main methods used to fabricate semiconductor interconnects. During copper plating, it is sometimes difficult to obtain ideal fill results for vias, trenches, and other connection structures on the wafer.
除化學調配及鍍液組成之方法以外，預處理方法對於獲得所需填充結果極為重要。預處理之目的係防止氣泡存留於通孔底部。In addition to methods of chemical formulation and bath composition, pretreatment methods are extremely important to achieve the desired fill results. The purpose of the pretreatment is to prevent bubbles from remaining in the bottom of the through hole.
總所周知，利用電解質溶液難以將空氣自通孔底部移除。US 6,562,222教示酸性硫酸銅電解質因包含於電鍍溶液中之硫酸而可輕易溶於銅晶種層。因此，現時工業預處理實務係將晶圓浸沒於表面活性劑溶液或去離子水中，然後實施銅電鍍。例如，JP 2008001963揭示一種含有銨及表面活性劑之預處理溶液。US 6,491,806將去離子水用於晶圓預處理中，將氣泡自通孔中之填充水消除。於電鍍期間，銅離子必須自通孔或溝槽之頂部擴散以鍍覆該通孔或溝槽之底部。然而，有些銅會沉積於通孔或溝槽之頂部側壁，因側壁附近之銅離子濃度較底部高之故。此導致夾斷，形成空隙或接縫。諸如加速劑、抑制劑及均勻劑之添加劑可抑制頂部及頂部側壁沉積之速率以獲得無空隙結果。然而，由於通孔之較高縱橫比，側壁會收窄銅離子通道，弱化銅離子之擴散，及增加避免通孔或溝槽中之空隙或接縫之困難度。因此，需求更穩定之溶液。It is well known that it is difficult to remove air from the bottom of the through hole using an electrolyte solution. US 6,562,222 teaches that an acidic copper sulfate electrolyte is readily soluble in the copper seed layer due to the sulfuric acid contained in the plating solution. Therefore, the current industrial pretreatment practice is to immerse the wafer in a surfactant solution or deionized water and then perform copper plating. For example, JP 2008001963 discloses a pretreatment solution containing ammonium and a surfactant. US 6,491,806 uses deionized water for wafer pretreatment to remove bubbles from the fill water in the vias. During electroplating, copper ions must diffuse from the top of the via or trench to plate the bottom of the via or trench. However, some copper will deposit on the top sidewall of the via or trench because the concentration of copper ions near the sidewall is higher than the bottom. This causes pinching to form voids or seams. Additives such as accelerators, inhibitors, and homogenizers can inhibit the rate of top and top sidewall deposition to achieve void-free results. However, due to the higher aspect ratio of the vias, the sidewalls narrow the copper ion channels, weaken the diffusion of copper ions, and increase the difficulty of avoiding voids or seams in the vias or trenches. Therefore, a more stable solution is required.
US 2007/235343 A1揭示藉由包含含硫有機化合物之溶液之預處理。視需要地，銅離子亦可以0.01至約5.0 g/L之範圍存在於預處理溶液中。US 2007/235343 A1 discloses the pretreatment by a solution comprising a sulfur-containing organic compound. Copper ions may also be present in the pretreatment solution in the range of 0.01 to about 5.0 g/L, as desired.
鑒於所述之問題，本發明提供一種用於晶圓上之通孔及溝槽特徵之銅電鍍以減少空隙及缺陷之預處理方法，其包括以預處理溶液填充該通孔或溝槽特徵，其中該預處理溶液包含10 g/L至300 g/L之銅離子。In view of the problems described, the present invention provides a pretreatment method for copper plating of vias and trench features on a wafer to reduce voids and defects, including filling the via or trench features with a pretreatment solution, Wherein the pretreatment solution contains 10 g/L to 300 g/L of copper ions.
本發明亦提供一種關於銅電鍍之方法，一種包含銅離子之銅電鍍預處理溶液及包含10 g/L至300 g/L之銅離子之溶液於銅電鍍前之預處理中之用途。The invention also provides a method for copper electroplating, a copper electroplating pretreatment solution containing copper ions and a solution containing a solution of 10 g/L to 300 g/L of copper ions for pretreatment before copper plating.
由於上述問題及先前技藝中之教示，先前並未考慮將銅電解質及銅離子用於電鍍通孔或溝槽之預處理方法中。然而，出乎意料地，發現於晶圓之通孔或溝槽鍍銅時利用包含充分濃度之銅離子之預處理溶液可有效地避免空隙或接縫發生。於預處理步驟之後，通孔及溝槽填滿預處理溶液。於電鍍期間，銅離子存留於通孔底部，補償受限之銅離子自電鍍溶液向通孔底部之擴散，及立即可用作用於通孔底部表面上之電鍍之銅源。因此，可更輕易地獲得尤其對於具有較大縱橫比或深度之通孔或溝槽之理想及所需填充結果。Due to the above problems and teachings in the prior art, copper electrolytes and copper ions have not previously been considered for use in pretreatment methods for plating through holes or trenches. Unexpectedly, however, it has been found that the use of a pretreatment solution containing a sufficient concentration of copper ions in the through-hole or trench copper plating of the wafer can effectively prevent voids or seams from occurring. After the pretreatment step, the vias and trenches fill the pretreatment solution. During electroplating, copper ions remain in the bottom of the via, compensating for the diffusion of restricted copper ions from the plating solution to the bottom of the via, and can be used immediately as a source of copper for plating on the bottom surface of the via. Therefore, the ideal and desired filling results, especially for through holes or trenches having a large aspect ratio or depth, can be obtained more easily.
由於銅離子存留於通孔或溝槽中，故本發明可減少電鍍所需之時間。亦可獲得較少過電鍍及增加均勻性。電鍍常見之逐步增加電流密度並不需要且可自電鍍方法開始時即使用較高電流密度。此外，於電鍍方法期間可以較大範圍控制電鍍溶液中之添加劑之量而不導致非所欲結果。Since copper ions remain in the vias or trenches, the present invention can reduce the time required for electroplating. Less plating and increased uniformity are also obtained. The gradual increase in current density common in electroplating is not required and a higher current density can be used from the beginning of the electroplating process. In addition, the amount of additive in the plating solution can be controlled over a wide range during the plating process without causing undesirable results.
用於本發明方法中之銅電鍍預處理溶液含有10 g/L至300 g/L之銅離子，較佳，10 g/L至136 g/L之銅離子，更佳，20 g/L至200 g/L，甚至更佳，30 g/L至136 g/L銅離子。且較好，該預處理溶液具有較用於銅電鍍方法中之電解質高之銅濃度。現時用於銅電鍍方法中之電解質一般含有30 g/L至100 g/L之銅離子。The copper plating pretreatment solution used in the method of the present invention contains 10 g/L to 300 g/L of copper ions, preferably 10 g/L to 136 g/L of copper ions, more preferably 20 g/L to 200 g/L, even better, 30 g/L to 136 g/L copper ion. Also preferably, the pretreatment solution has a higher copper concentration than the electrolyte used in the copper plating process. The electrolyte currently used in copper plating processes generally contains 30 g/L to 100 g/L of copper ions.
銅離子可藉由常用於半導體領域中之任何來源獲得，包括，但非限於，硫酸銅、烷磺酸銅、磷酸銅、氟硼酸銅、及氰化銅或類似的銅鹽。較好銅離子可藉由硫酸銅或甲磺酸銅提供。Copper ions can be obtained by any source commonly used in the semiconductor field including, but not limited to, copper sulfate, copper alkane sulfonate, copper phosphate, copper fluoroborate, and copper cyanide or similar copper salts. Preferred copper ions can be provided by copper sulphate or copper methane sulfonate.
諸如加速劑(增亮劑)、抑制劑及均勻劑之添加劑一般係包含於銅電鍍溶液中以藉由改良表面沉積及厚度均勻性及增強化學反應及填充高縱橫比特徵來改良電鍍行為。Additives such as accelerators (brighteners), inhibitors, and homogenizers are typically included in the copper plating solution to improve plating behavior by improving surface deposition and thickness uniformity and enhancing chemical reactions and filling high aspect ratio features.
亦可視需要將此等添加劑添加至用於本發明方法中之預處理溶液。These additives may also be added to the pretreatment solution used in the process of the present invention as needed.
使用加速劑(或增亮劑)以加速沉積顆粒之尺寸縮小。加速劑一般係含硫有機化合物且相對地增加其上形成有具有狹窄寬度之溝槽之圖案的銅沉積速率。適宜加速劑之實例係描述於US 6,679,983中，包括N,N-二甲基-二硫代胺基甲酸-(3-磺丙基)酯、3-巰基-丙基磺酸-(3-磺丙基)酯、3-巰基丙基磺酸(鈉鹽)、含3-巰基-1-丙磺酸-(鉀鹽)之甲酸-二硫代-o-乙基酯-s-酯、雙磺丙基二硫化物、3-(苯并噻唑基-s-硫代)丙基磺酸(鈉鹽)、丙磺酸甜菜鹼吡啶鎓鹽、1-鈉-3-巰基丙烷-1-磺酸鹽、二鈉雙(3-磺丙基)二硫化物、或其等混合物。較佳地，加速劑包含二鈉雙(3-磺丙基)二硫化物。本發明之預處理溶液中之加速劑之濃度較佳為0 ml/L至約50 ml/L，更佳0 ml/L至35 ml/L。本發明預處理溶液中之加速劑之活性化合物之濃度較佳為0 ppm至400 ppm。Accelerators (or brighteners) are used to accelerate the size reduction of the deposited particles. Accelerators are generally sulfur-containing organic compounds and relatively increase the rate of copper deposition on which a pattern of trenches having a narrow width is formed. Examples of suitable accelerators are described in US 6,679,983, including N,N-dimethyl-dithiocarbamic acid-(3-sulfopropyl)ester, 3-mercapto-propylsulfonic acid-(3-sulfonate) Propyl)ester, 3-mercaptopropyl sulfonic acid (sodium salt), formic acid-dithio-o-ethyl ester-s-ester containing 3-mercapto-1-propanesulfonic acid-(potassium salt), double Sulfopropyl disulfide, 3-(benzothiazolyl-s-thio)propyl sulfonic acid (sodium salt), propanesulfonic acid betaine pyridinium salt, 1-sodium-3-mercaptopropane-1-sulfonate An acid salt, disodium bis(3-sulfopropyl) disulfide, or a mixture thereof. Preferably, the accelerator comprises disodium bis(3-sulfopropyl) disulfide. The concentration of the accelerator in the pretreatment solution of the present invention is preferably from 0 ml/L to about 50 ml/L, more preferably from 0 ml/L to 35 ml/L. The concentration of the active compound of the accelerator in the pretreatment solution of the present invention is preferably from 0 ppm to 400 ppm.
使用抑制劑以增加用於在較均勻電沉積下沉積鍍覆銅之過電壓。用於銅電鍍之抑制劑一般係含氧高分子量化合物。適宜抑制劑包括，但非限於，羧甲基纖維素、壬基酚聚二醇醚、辛二醇雙(聚伸烷基二醇醚)、辛醇聚伸烷基二醇醚、油酸聚二醇酯、聚乙烯丙二醇、聚乙二醇、聚乙二醇二甲基醚、聚氧基丙二醇、聚丙二醇、聚乙烯醇、硬脂酸聚二醇酯、聚環氧乙烷、硬脂基醇聚二醇醚等。較佳地，抑制劑包含聚(環氧乙烷-環氧丙烷)。本發明預處理溶液中之抑制劑之濃度較佳為0 ml/L至約40 ml/L，更佳0 ml/L至約30 ml/L。本發明預處理溶液中之抑制劑之活性化合物之濃度較佳為0 ppm至600 ppm。Inhibitors are used to increase the overvoltage used to deposit the plated copper under more uniform electrodeposition. Inhibitors for copper electroplating are generally oxygen-containing high molecular weight compounds. Suitable inhibitors include, but are not limited to, carboxymethyl cellulose, nonylphenol polyglycol ether, octanediol bis (polyalkylene glycol ether), octanol polyalkylene glycol ether, oleic acid poly Glycol ester, polyethylene propylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polypropylene glycol, polyvinyl alcohol, polyglycol stearate, polyethylene oxide, stearic acid a base alcohol polyglycol ether or the like. Preferably, the inhibitor comprises poly(ethylene oxide-propylene oxide). The concentration of the inhibitor in the pretreatment solution of the present invention is preferably from 0 ml/L to about 40 ml/L, more preferably from 0 ml/L to about 30 ml/L. The concentration of the active compound of the inhibitor in the pretreatment solution of the present invention is preferably from 0 ppm to 600 ppm.
較佳地，預處理溶液實質上不含任何加速劑，即，不含任何含硫有機化合物。「實質上不含任何含硫有機化合物」意指該溶液包含少於0.1 mg/L，較佳少於0.01 mg/L，最佳少於0.001 mg/L之含硫有機化合物。Preferably, the pretreatment solution is substantially free of any accelerator, i.e., free of any sulfur containing organic compounds. "Substantially free of any sulfur-containing organic compound" means that the solution contains less than 0.1 mg/L, preferably less than 0.01 mg/L, and most preferably less than 0.001 mg/L of sulfur-containing organic compound.
使用均勻劑以降低表面粗糙度。其等與抑制劑類似，係因其等可降低沉積速率。用於銅電鍍之均勻劑一般包含含氮有機化合物。常使用含胺基或經取代之胺基之化合物。此等化合物係揭示於US 4,376,685、US 4,555,315及US 3,770,598中。實例包括1-(2-羥基乙基)-2-咪唑啶硫代酮、4-巰基吡啶、2-巰基噻唑啉、伸乙基硫脲、硫脲、烷基化聚亞烷基亞胺。較佳地，均勻劑係1-(2-羥基乙基)-2-咪唑啶硫代酮。本發明預處理溶液中之均勻劑濃度較佳為0 mL/L至約50 mL/L，更佳0至約40 mL/L。本發明預處理溶液中之均勻劑之活性化合物之濃度為0 ppm至500 ppm。A homogenizer is used to reduce surface roughness. They are similar to inhibitors because they reduce the deposition rate. The homogenizer for copper plating generally comprises a nitrogen-containing organic compound. Compounds containing an amine group or a substituted amine group are often used. Such compounds are disclosed in US 4,376,685, US 4,555,315 and US 3,770,598. Examples include 1-(2-hydroxyethyl)-2-imidazopyridine thioketone, 4-mercaptopyridine, 2-mercaptothiazoline, ethyl thiourea, thiourea, alkylated polyalkyleneimine. Preferably, the homogenizing agent is 1-(2-hydroxyethyl)-2-imidazopyridine thioketone. The concentration of the homogenizing agent in the pretreatment solution of the present invention is preferably from 0 mL/L to about 50 mL/L, more preferably from 0 to about 40 mL/L. The concentration of the active compound of the homogenizing agent in the pretreatment solution of the present invention is from 0 ppm to 500 ppm.
本發明之預處理溶液亦可包含表面活性劑。表面活性劑係用於降低溶液之表面張力。可用的表面活性劑包括高分子量聚合物、經改質之聚丙烯酸系聚合物、經改質之聚矽氧烷，較佳為聚二醇類聚合物及共聚物。預處理溶液中之表面活性劑之濃度可介於0重量%至3重量%之間。The pretreatment solution of the present invention may also comprise a surfactant. Surfactants are used to reduce the surface tension of the solution. Useful surfactants include high molecular weight polymers, modified polyacrylic polymers, modified polyoxyalkylenes, preferably polyglycol based polymers and copolymers. The concentration of the surfactant in the pretreatment solution may be between 0% and 3% by weight.
本發明之預處理溶液亦可包含酸。該酸可選自由硫酸、烷磺酸(諸如甲磺酸、乙磺酸、丙磺酸及三氟甲磺酸)、胺基磺酸、氫氯酸、氫溴酸及氟硼酸及其等混合物組成之群。較佳地，該酸為硫酸、甲磺酸或氫氯酸。該酸之濃度為0 mL/L至約40 mL/L。The pretreatment solution of the present invention may also contain an acid. The acid may be selected from sulfuric acid, alkanesulfonic acid (such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and trifluoromethanesulfonic acid), aminosulfonic acid, hydrochloric acid, hydrobromic acid and fluoroboric acid, and the like. a group of people. Preferably, the acid is sulfuric acid, methanesulfonic acid or hydrochloric acid. The acid concentration is from 0 mL/L to about 40 mL/L.
根據本發明之一態樣，欲鍍覆之通孔或溝槽特徵具有大於2:1，較佳3:1至40:1之縱橫比。根據另一態樣，通孔或溝槽特徵具有大於10微米，較佳10微米至300微米之深度。According to one aspect of the invention, the via or trench features to be plated have an aspect ratio greater than 2:1, preferably 3:1 to 40:1. According to another aspect, the via or trench features have a depth greater than 10 microns, preferably from 10 microns to 300 microns.
根據本發明之又一態樣，本發明之方法可進一步包含一水沖洗步驟或旋轉乾燥步驟以將預處理溶液自晶圓表面移除。According to still another aspect of the present invention, the method of the present invention may further comprise a water rinsing step or a spin drying step to remove the pretreatment solution from the wafer surface.
將描述本發明之實例及比較例。此等實例僅說明本發明之較佳實施例，且本發明不限制於此等實例。Examples and comparative examples of the invention will be described. These examples are merely illustrative of preferred embodiments of the invention, and the invention is not limited to such examples.
該等實例顯示預處理溶液、電鍍溶液及通孔圖案。於各實例中，所測試晶圓係藉由預處理溶液預處理及隨後浸沒於去離子水(DI水)中約2秒。此處「經預處理」意指，例如，經接觸、潤濕或沖洗。就比較例1及3而言，略去浸沒於DI水中之步驟，係因於此兩例中預處理溶液均為超純水。隨後將晶圓浸沒於用於電鍍之電鍍溶液中。陽極為銅陽極。除實例15及16與比較例5及6之以外，電源提供0.3 ASD(安培/平方分米)之平均電流密度。使電鍍持續約40分鐘。就實例15及比較例5而言，電源提供0.1 ASD之平均電流密度。使電鍍持續約30分鐘。就實例16及比較例6而言，電源提供0.8 ASD之平均電流密度。使電鍍持續約30分鐘。These examples show pretreatment solutions, plating solutions, and via patterns. In each example, the wafers tested were pretreated with a pretreatment solution and subsequently immersed in deionized water (DI water) for about 2 seconds. By "pretreated" herein is meant, for example, contact, wetting or rinsing. For Comparative Examples 1 and 3, the step of immersing in DI water was omitted because the pretreatment solutions in both cases were ultrapure water. The wafer is then immersed in a plating solution for electroplating. The anode is a copper anode. Except for Examples 15 and 16 and Comparative Examples 5 and 6, the power supply provided an average current density of 0.3 ASD (amps per square decimeter). The plating was allowed to last for about 40 minutes. For Example 15 and Comparative Example 5, the power supply provided an average current density of 0.1 ASD. The plating was allowed to continue for about 30 minutes. For Example 16 and Comparative Example 6, the power supply provided an average current density of 0.8 ASD. The plating was allowed to continue for about 30 minutes.
預處理溶液：超純水Pretreatment solution: ultrapure water
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)、CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，來自BASF)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度。電鍍結果顯示於底部存在空隙。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from a diameter of 6 microns and a depth of 50 microns. The plating results showed a void at the bottom.
預處理溶液：具有10 g/L之銅離子濃度之硫酸銅。Pretreatment solution: copper sulfate having a copper ion concentration of 10 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有40 g/L之銅離子濃度之硫酸銅。Pretreatment solution: copper sulfate having a copper ion concentration of 40 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有80 g/L之銅離子濃度之硫酸銅。Pretreatment solution: copper sulfate having a copper ion concentration of 80 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有90 g/L之銅離子濃度之甲磺酸銅。Pretreatment solution: copper methanesulfonate having a copper ion concentration of 90 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有120 g/L之銅離子濃度之甲磺酸銅。Pretreatment solution: copper methanesulfonate having a copper ion concentration of 120 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有136 g/L之銅離子濃度之甲磺酸銅。Pretreatment solution: copper methanesulfonate having a copper ion concentration of 136 g/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：CuPurTM T 5000(0.3%表面活性劑，自BASF獲得)。Pretreatment solution: CuPur TM T 5000 (0.3% surfactant, obtained from BASF).
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有10:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及60微米之深度之開口。電鍍結果顯示於底部出現空隙。The via has a 10:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 6 microns and a depth of 60 microns. The plating results showed a gap at the bottom.
預處理溶液：超純水。Pretreatment solution: ultrapure water.
電鍍溶液：CuPurTM T 1010(甲磺酸銅，銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1010 (copper mesylate, copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as an inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果顯示於底部出現空隙。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results showed a gap at the bottom.
預處理溶液：CuPurTM T 5000(0.3%表面活性劑；自BASF獲得)。Pretreatment solution: CuPur TM T 5000 (0.3% surfactant; obtained from BASF).
電鍍溶液：CuPurTM T 1010(甲磺酸銅，銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1010 (copper mesylate, copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as an inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有10:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及60微米之深度之開口。電鍍結果顯示於底部出現空隙。The via has a 10:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 6 microns and a depth of 60 microns. The plating results showed a gap at the bottom.
預處理溶液：具有40 g/L之銅離子濃度之硫酸銅，硫酸10 g/L，及氯離子50 ppm。Pretreatment solution: copper sulfate having a copper ion concentration of 40 g/L, sulfuric acid 10 g/L, and chloride ion 50 ppm.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有40 g/L之銅離子濃度之硫酸銅，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Pretreatment solution: a 40 g / L copper sulfate ion concentrations of copper, CuPur TM T 2000 additive 15 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as an inhibitor, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有90 g/L之銅離子濃度之甲磺酸銅，甲磺酸5 mL/L。Pretreatment solution: copper methanesulfonate having a copper ion concentration of 90 g/L, and methanesulfonic acid 5 mL/L.
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有90 g/L之銅離子濃度之甲磺酸銅，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑2 mL/L(作為抑制劑，自BASF獲得)。Pretreatment solution: a 90 g / methanesulfonic acid L copper ion concentrations of copper, CuPur TM T 2000 additive 15 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 2 mL / L (as inhibition Agent, obtained from BASF).
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有8:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及50微米之深度之開口。電鍍結果為無空隙及無接縫。The via has an aspect ratio (depth: opening diameter) of 8:1 derived from an opening having a diameter of 6 microns and a depth of 50 microns. The plating results were void-free and seamless.
預處理溶液：具有90 g/L之銅離子濃度之甲磺酸銅，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑2 mL/L(作為抑制劑，自BASF獲得)，及表面活性劑(0.2重量%)。Pretreatment solution: a 90 g / methanesulfonic acid L copper ion concentrations of copper, CuPur TM T 2000 additive 12 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 2 mL / L (as inhibition Agent, obtained from BASF), and surfactant (0.2% by weight).
電鍍溶液：甲磺酸銅(銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper methane sulfonate (copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有10:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及60微米之深度之開口。電鍍結果為無空隙及無接縫。The via has a 10:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 6 microns and a depth of 60 microns. The plating results were void-free and seamless.
預處理溶液：具有120 g/L之銅離子濃度之甲磺酸銅，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑2 mL/L(作為抑制劑，自BASF獲得)，及表面活性劑(0.2%)。Pretreatment solution: having 120 g / methanesulfonic acid L copper ion concentrations of copper, CuPur TM T 2000 additive 15 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 2 mL / L (as inhibition Agent, obtained from BASF), and surfactant (0.2%).
電鍍溶液：CuPurTM T 1000(硫酸銅，銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑5 mL/L(作為均勻劑，自BASF獲得)。Plating solution: CuPur TM T 1000 (copper sulfate, copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitors, obtained from BASF), CuPur TM T 4000 additive 5 mL / L (as a leveler, obtained from BASF).
通孔具有10:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及60微米之深度之開口。電鍍結果為無空隙及無接縫。The via has a 10:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 6 microns and a depth of 60 microns. The plating results were void-free and seamless.
預處理溶液：具有120 g/L之銅離子濃度之甲磺酸銅，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑2 mL/L(作為抑制劑，自BASF獲得)，及表面活性劑(0.2%)。Pretreatment solution: having 120 g / methanesulfonic acid L copper ion concentrations of copper, CuPur TM T 2000 additive 15 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 2 mL / L (as inhibition Agent, obtained from BASF), and surfactant (0.2%).
電鍍溶液：甲磺酸銅(銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper methane sulfonate (copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有4:1之縱橫比(深度：開口直徑)，其源自具有30微米直徑及150微米之深度之開口。電鍍結果為無空隙及無接縫。The via has a 4:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 30 microns and a depth of 150 microns. The plating results were void-free and seamless.
預處理溶液：具有180 g/L之銅離子濃度之甲磺酸銅，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑2 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑2 mL/L(作為均勻劑，自BASF獲得)，及表面活性劑(0.2重量%)。Pretreatment solution: having 180 g / methanesulfonic acid L copper ion concentrations of copper, CuPur TM T 2000 additive 15 mL / L (as an accelerator, obtained from BASF), CuPur TM T 3000 additive 2 mL / L (as inhibition agent, obtained from BASF), CuPur TM T 4000 additive 2 mL / L (as a leveler, obtained from BASF), and a surfactant (0.2 wt%).
電鍍溶液：甲磺酸銅(銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper methane sulfonate (copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有10:1之縱橫比(深度：開口直徑)，其源自具有6微米之直徑及60微米之深度之開口。電鍍結果為無空隙及無接縫。The via has a 10:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 6 microns and a depth of 60 microns. The plating results were void-free and seamless.
預處理溶液：具有0.67 g/L(10.6 mmol/L)銅離子濃度之硫酸銅，CuPurTM T 2000添加劑1.06 g/L(3 mmol/L)(作為加速劑，自BASF獲得)。Pretreatment solution: a 0.67 g / L (10.6 mmol / L) concentration of copper ions of copper sulfate, CuPur TM T 2000 additive 1.06 g / L (3 mmol / L) ( as an accelerator, obtained from BASF).
電鍍溶液：甲磺酸銅(銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper methane sulfonate (copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有6:1之縱橫比(深度：開口直徑)，其源自具有10微米之直徑及60微米之深度之開口。特徵之橫截面展現底部空隙。The via has a 6:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 10 microns and a depth of 60 microns. The cross section of the feature reveals a bottom void.
預處理溶液：具有60 g/L之銅離子濃度之硫酸銅。Pretreatment solution: copper sulfate having a copper ion concentration of 60 g/L.
電鍍溶液：甲磺酸銅(銅離子濃度90 g/L)，CuPurTM T 2000添加劑12 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑6 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑16 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper methane sulfonate (copper ion concentration 90 g / L), CuPur TM T 2000 additive 12 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 6 mL / L (as inhibitor, obtained from BASF), CuPur TM T 4000 additive 16 mL / L (as a leveler, obtained from BASF).
通孔具有6:1之縱橫比(深度：開口直徑)，其源自具有10微米之直徑及60微米之深度之開口。特徵之橫截面無空隙及無接縫。The via has a 6:1 aspect ratio (depth: opening diameter) derived from an opening having a diameter of 10 microns and a depth of 60 microns. The cross section of the feature has no gaps and no seams.
預處理溶液：具有0.67 g/L(10.6 mmol/L)之銅離子濃度之硫酸銅，CuPurTM T 2000添加劑1.06 g/L(3 mmol/L)(作為加速劑，自BASF獲得)。Pretreatment solution: copper sulfate having a copper ion concentration of 0.67 g / L (10.6 mmol / L) of, CuPur TM T 2000 additive 1.06 g / L (3 mmol / L) ( as an accelerator, obtained from BASF).
電鍍溶液：硫酸銅(銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑10 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper sulfate (copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitor, from BASF obtained), CuPur TM T 4000 additive 10 mL / L (as a leveler, obtained from BASF).
測試兩溝槽。10微米溝槽具有11:2之縱橫比(深度：寬度)，其源自10微米之寬度及55微米之深度。20微米溝槽具有13:2之縱橫比(深度：寬度)，其源自20微米之寬度及65微米之深度。特徵之橫截面展現底部缺陷。Test both grooves. The 10 micron trench has an aspect ratio (depth: width) of 11:2, which is derived from a width of 10 microns and a depth of 55 microns. The 20 micron trench has an aspect ratio (depth: width) of 13:2, which is derived from a width of 20 microns and a depth of 65 microns. The cross section of the feature exhibits a bottom defect.
預處理溶液：具有60 g/L之銅離子濃度之硫酸銅。Pretreatment solution: copper sulfate having a copper ion concentration of 60 g/L.
電鍍溶液：硫酸銅(銅離子濃度40 g/L)，CuPurTM T 2000添加劑15 mL/L(作為加速劑，自BASF獲得)，CuPurTM T 3000添加劑5 mL/L(作為抑制劑，自BASF獲得)，CuPurTM T 4000添加劑10 mL/L(作為均勻劑，自BASF獲得)。Plating solution: copper sulfate (copper ion concentration 40 g / L), CuPur TM T 2000 additive 15 mL / L (as accelerator, obtained from BASF), CuPur TM T 3000 additive 5 mL / L (as inhibitor, from BASF obtained), CuPur TM T 4000 additive 10 mL / L (as a leveler, obtained from BASF).
測試兩溝槽。10微米溝槽具有11:2之縱橫比(深度：寬度)，其源自10微米之寬度及55微米之深度。20微米溝槽具有13:2之縱橫比(深度：寬度)，其源自20微米之寬度及65微米之深度。特徵之橫截面無缺陷及無接縫。Test both grooves. The 10 micron trench has an aspect ratio (depth: width) of 11:2, which is derived from a width of 10 microns and a depth of 55 microns. The 20 micron trench has an aspect ratio (depth: width) of 13:2, which is derived from a width of 20 microns and a depth of 65 microns. The cross section of the feature is flawless and seamless.
實例及比較例之最終填充特徵係藉由剖斷橫截面光學顯微圖或掃描式電子顯微圖(SEM)檢測及於有些例中係藉由利用聚焦離子束(FIB)以用於觀察結果之雙重確認，且結果顯示於表1中。結果顯示本發明對避免填充結果中出現空隙及接縫具有優異作用。The final filling characteristics of the examples and comparative examples were determined by cutting cross-section optical micrographs or scanning electron micrographs (SEM) and in some cases by using focused ion beams (FIB) for observation. Double confirmation, and the results are shown in Table 1. The results show that the present invention has an excellent effect on avoiding voids and seams in the filling result.
維持其他參數不變，表2顯示關於預處理溶液中之不同銅離子濃度之填充結果。結果清楚顯示包含任何所測試的銅離子濃度之本發明預處理溶液可避免空隙或接縫之出現。於比較例5及6中，使用如US 2007/235343之實例1中所使用之相同銅離子及加速劑濃度。分別重複實例15及16之該等實驗，然而，不含添加劑及使用更高銅濃度。Maintaining other parameters unchanged, Table 2 shows the results of the filling of different copper ion concentrations in the pretreatment solution. The results clearly show that the pretreatment solution of the present invention comprising any of the tested copper ion concentrations avoids the appearance of voids or seams. In Comparative Examples 5 and 6, the same copper ion and accelerator concentration as used in Example 1 of US 2007/235343 was used. The experiments of Examples 15 and 16 were repeated, respectively, however, without additives and using higher copper concentrations.
本發明並非由僅作為實例提出之上述實施例所限制，且可於藉由後附申請專利範圍所界定之保護範圍內以各種方法修改。The present invention is not limited by the above-described embodiments, which are presented by way of example only, and may be modified in various ways within the scope of the protection defined by the scope of the appended claims.
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| US10214826B2 (en) * | 2013-01-29 | 2019-02-26 | Novellus Systems, Inc. | Low copper electroplating solutions for fill and defect control |
| US9598787B2 (en) * | 2013-03-14 | 2017-03-21 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes |
| US20140299476A1 (en) * | 2013-04-09 | 2014-10-09 | Ebara Corporation | Electroplating method |
| CN104762643A (en) * | 2014-12-17 | 2015-07-08 | 安捷利电子科技（苏州）有限公司 | Copper plating solution capable of realizing co-plating of through hole, blind hole and circuit |
| US10512174B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| US10508357B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| CN114507886A (en) * | 2022-03-29 | 2022-05-17 | 四会富仕电子科技股份有限公司 | Hole-filling electroplating method |
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| US6562222B1 (en) * | 2000-01-20 | 2003-05-13 | Nikko Materials Company, Limited | Copper electroplating liquid, pretreatment liquid for copper electroplating and method of copper electroplating |
| US20090020434A1 (en) * | 2007-07-02 | 2009-01-22 | Akira Susaki | Substrate processing method and substrate processing apparatus |
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| US3770598A (en) | 1972-01-21 | 1973-11-06 | Oxy Metal Finishing Corp | Electrodeposition of copper from acid baths |
| US4376685A (en) | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4555315A (en) | 1984-05-29 | 1985-11-26 | Omi International Corporation | High speed copper electroplating process and bath therefor |
| US5058799A (en) * | 1986-07-24 | 1991-10-22 | Zsamboky Kalman F | Metallized ceramic substrate and method therefor |
| US5340947A (en) * | 1992-06-22 | 1994-08-23 | Cirqon Technologies Corporation | Ceramic substrates with highly conductive metal vias |
| US6491806B1 (en) | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| US6679983B2 (en) | 2000-10-13 | 2004-01-20 | Shipley Company, L.L.C. | Method of electrodepositing copper |
| WO2004107422A2 (en) * | 2003-05-27 | 2004-12-09 | Ebara Corporation | Plating apparatus and plating method |
| US7064068B2 (en) * | 2004-01-23 | 2006-06-20 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method to improve planarity of electroplated copper |
| WO2007112768A1 (en) * | 2006-03-30 | 2007-10-11 | Freescale Semiconductor, Inc. | Process for filling recessed features in a dielectric substrate |
| US7575666B2 (en) * | 2006-04-05 | 2009-08-18 | James Watkowski | Process for electrolytically plating copper |
| JP4822519B2 (en) | 2006-06-26 | 2011-11-24 | Ｊｘ日鉱日石金属株式会社 | Semiconductor wafer pretreatment agent and pretreatment method |
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| US6562222B1 (en) * | 2000-01-20 | 2003-05-13 | Nikko Materials Company, Limited | Copper electroplating liquid, pretreatment liquid for copper electroplating and method of copper electroplating |
| US20090020434A1 (en) * | 2007-07-02 | 2009-01-22 | Akira Susaki | Substrate processing method and substrate processing apparatus |
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