TW201908534A - Aqueous composition for depositing a cobalt deposit and method for electrolytically depositing such a deposit - Google Patents

Abstract

The present invention refers to an aqueous composition for depositing a cobalt deposit, the composition comprising (a) a total amount of cobalt (II) ions, (b) at least one first compound of formula (I) wherein independently R1 denotes H, -NR3R4, -OR5, or -CR6R<SP>6'</SP>R7, R2 denotes H, C1 to C4 alkyl, halogen, or OH, n is 1, 2, or 3 wherein independently R3 denotes H, C1 to C4 alkyl, or an alkylene moiety connected to the nitrogen atom in R1 via R4, R4 denotes H, C1 to C4 alkyl, or an alkylene moiety connected to the nitrogen atom in R1 via R3, R5 denotes H or a pair of electrons, or C1 to C4 alkyl, R6 denotes H, C1 to C4 alkyl, or an alkylene moiety connected to the carbon atom in R1 via R7, R<SP>6'</SP> denotes H or C1 to C4 alkyl, R7 denotes H, C1 to C4 alkyl, or an alkylene moiety connected to the carbon atom in R1 via R6, with the proviso that the total amount of said cobalt (II) ions in the composition represents 51 wt.-% to 100 wt.-% of all transition metal cations in the composition, based on the total weight of all transition metal cations in the composition.

Description

用於沉積鈷沉積物之水性組合物及電解沉積該沉積物之方法Aqueous composition for depositing cobalt deposits and method for electrolytically depositing the deposits

本發明係關於用於沉積鈷沉積物之水性組合物及將該鈷沉積物電解沉積於基板上之方法、尤其將該鈷沉積物電解沉積至複數個通孔及/或溝槽中之方法。The present invention relates to an aqueous composition for depositing a cobalt deposit and a method of electrolytically depositing the cobalt deposit on a substrate, in particular a method of electrolytically depositing the cobalt deposit into a plurality of vias and/or trenches.

溝槽及通孔係當前電子裝置之半導體基板上之典型特徵。因幾十年來且直至今天銅始終係具有極低電阻率及極高可靠性之極佳導電材料，故將其沉積至該等特徵中以填充各別通孔及溝槽且形成導電線及互連之圖案。然而，銅作為填充金屬亦具有一些缺點。Trench and via are typical features on semiconductor substrates of current electronic devices. Since copper has been an excellent conductive material with extremely low resistivity and extremely high reliability for decades and until now, it is deposited into these features to fill the respective vias and trenches and form conductive lines and mutual Even the pattern. However, copper also has some disadvantages as a filler metal.

眾所周知，銅具有高遷移及擴散趨勢。端視基板(例如含有氧化矽之基板)，銅容易擴散至基板中，由此引起空隙、電流中斷及甚至電短路。為解決該等關鍵問題，通常將障壁層施加於基板表面上以阻斷或至少顯著阻抑該等遷移及擴散。在許多應用中，障壁層含有鈷。Copper is known to have a high migration and diffusion trend. By looking at the substrate (for example, a substrate containing yttria), copper easily diffuses into the substrate, thereby causing voids, current interruptions, and even electrical shorts. To address these critical issues, a barrier layer is typically applied to the surface of the substrate to block or at least significantly retard such migration and diffusion. In many applications, the barrier layer contains cobalt.

該等障壁層之施加變得愈來愈苛刻，此乃因近年來該等特徵之大小變得愈來愈小，從而亦需要愈薄且愈均勻之障壁層。當前，常用特徵之大小範圍為50 nm至遠小於10 nm。另外，為將銅電解沉積於障壁層上，需要將導電薄晶種層另外沉積於障壁層上。The application of such barrier layers has become more and more demanding, as the size of these features has become smaller and smaller in recent years, requiring thinner and more uniform barrier layers. Currently, common features range in size from 50 nm to much less than 10 nm. In addition, in order to electrolytically deposit copper on the barrier layer, it is necessary to additionally deposit a conductive thin seed layer on the barrier layer.

然而，除該層配置外，含有銅之該等小特徵之無空隙填充變得愈加苛刻及困難。除降低特徵大小及施加薄障壁及晶種層外，因特徵具有高縱橫比而需要額外關注特徵之幾何結構。開口尺寸為(例如) 10 nm且特徵深度為(例如) 100 nm之特徵展現10:1之縱橫比。此縱橫比及類似縱橫比在當前變得愈加重要且預計縱橫比在不久的將來將進一步增加。具有該等高縱橫比之特徵需要複雜填充方法及特定設計之銅沉積浴以避免不完整特徵填充，從而引起通稱為空隙之缺陷。However, in addition to this layer configuration, the void-free filling of these small features containing copper becomes increasingly harsh and difficult. In addition to reducing feature size and applying thin barriers and seed layers, additional features of the geometry are required due to the feature's high aspect ratio. Features with an opening size of, for example, 10 nm and a feature depth of, for example, 100 nm exhibit an aspect ratio of 10:1. This aspect ratio and similar aspect ratios are becoming more important today and the aspect ratio is expected to increase further in the near future. Features having such high aspect ratios require complex filling methods and specially designed copper deposition baths to avoid incomplete feature filling, thereby causing defects known as voids.

降低特徵大小之另一缺點係所得銅電阻率以指數方式增加，尤其在特徵尺寸低於10 nm時。儘管電阻率係金屬固有特性，但銅填充特徵之整體電阻率在很大程度上受環繞銅之金屬及非金屬材料以及電子與該等材料之相互作用方式影響。舉例而言，電子流因穿過(例如) (i)銅與銅中之包埋雜質、(ii)晶粒邊界、(ii)銅與其他層(例如晶種層及障壁層)之間之界面而大受影響。最新探究揭示，其他金屬(例如鈷)不易受該指數式電阻率增加影響且由此表明可藉由鈷代替銅。此結論似乎亦出於另一原因而較為合理。使用可用於雙重或甚至多重目的(作為填充金屬以及障壁及/或晶種層)之金屬可容許導電金屬具有較大體積且由此具有較低整體電阻率。因鈷通常用作銅沉積物之障壁層中之金屬，故鈷填充特徵無需額外障壁層。另外，鈷層亦可用作導電晶種層。因此，可使用鈷代替銅來達成極均質鈷沉積物。Another disadvantage of reducing the size of the features is that the resulting copper resistivity increases exponentially, especially when the feature size is below 10 nm. Although resistivity is an inherent property of a metal, the overall resistivity of a copper-filled feature is largely affected by the manner in which the metal and non-metallic materials surrounding the copper and the interaction of the electrons with the material. For example, electron flow is caused by, for example, (i) embedding impurities in copper and copper, (ii) grain boundaries, (ii) copper and other layers (eg, seed layer and barrier layer). The interface is greatly affected. Recent research has revealed that other metals, such as cobalt, are less susceptible to this exponential increase in resistivity and thus indicate that copper can be replaced by cobalt. This conclusion seems to be more reasonable for another reason. The use of a metal that can be used for dual or even multiple purposes (as a filler metal and a barrier and/or seed layer) can allow the conductive metal to have a larger volume and thus a lower overall resistivity. Since cobalt is commonly used as a metal in the barrier layer of copper deposits, the cobalt fill feature does not require an additional barrier layer. In addition, a cobalt layer can also be used as the conductive seed layer. Therefore, cobalt can be used instead of copper to achieve extremely homogeneous cobalt deposits.

US 2009/0188805 A1係關於使用電沉積利用金屬及合金以實質上無空隙方式來填充基板之凹陷表面特徵，且揭示用於無空隙鈷填充之包括2-巰基-5-苯并咪唑磺酸(MBIS)作為填充添加劑之鈷沉積浴。US 2009/0188805 A1 relates to the use of electrodeposition to fill recessed surface features of a substrate in a substantially void-free manner using metals and alloys, and to disclose 2-mercapto-5-benzimidazole sulfonic acid for use in void-free cobalt filling ( MBIS) as a cobalt deposition bath for filling additives.

CA 1086679 A係關於用於製備含有鈷之電沉積物之製程及組合物。組合物可包括不飽和環碸與炔丙基醇之組合。CA 1086679 A relates to processes and compositions for preparing electrodepositories containing cobalt. The composition may include a combination of an unsaturated cyclic oxime and a propargyl alcohol.

US 6,923,897 B1係關於藉由電解方法提供鈷或鈷合金層之冷軋條帶。電解質浴可包括丁炔二醇及糖精。US 6,923,897 B1 relates to cold rolled strips which provide a cobalt or cobalt alloy layer by electrolytic methods. The electrolyte bath may include butynediol and saccharin.

WO 2017/004424 A1係關於電解沉積化學以及沉積鈷及鈷合金之方法；且更具體而言係關於用於電解電鍍溶液中之添加劑及整體組合物以及互連特徵在半導體基板中基於鈷之金屬化方法。組合物可包括炔丙基醇與雙-(鈉磺基丙基)二硫化物(SPS)之組合。WO 2017/004424 A1 relates to electrolytic deposition chemistry and methods of depositing cobalt and cobalt alloys; and more particularly to additives and overall compositions for use in electrolytic plating solutions and interconnecting features based on cobalt metal in semiconductor substrates Method. The composition may include a combination of propargyl alcohol and bis-(sodium sulfopropyl) disulfide (SPS).

US 3,432,509 A係關於新穎吡啶鎓化合物及其作為主要增亮劑在電沉積鎳中之用途。US 3,432,509 A relates to novel pyridinium compounds and their use as primary brightening agents in electrodepositing nickel.

已利用有機添加劑(例如直鏈炔丙基化合物，例如炔丙基醇)與鈷一起來填充特徵。另外，該等化合物在一些情形下展示可接受之自底向上填充性能，尤其對於具有中等縱橫比之特徵而言。Organic additives such as linear propargyl compounds such as propargyl alcohol have been utilized with the cobalt to fill the features. In addition, the compounds exhibit acceptable bottom-up filling properties in some cases, especially for features having a medium aspect ratio.

特徵縱橫比愈高，則愈需要極佳之自底向上填充性能。若該有機添加劑之總濃度過低，則自底向上填充性能亦不足且通常觀察到空隙。因此，在許多情形下，增加有機添加劑之總濃度以適當填充具有高縱橫比之特徵。然而，若總濃度超過某一限值，則在基板表面上通常出現不可接受之沉積缺陷(例如漏鍍)。在該情形下，鈷在基板表面上之覆蓋不足。理想地，基板之整個表面完全且均勻地經鈷覆蓋，同時基板上之所有特徵經鈷無空隙填充。The higher the feature aspect ratio, the better the bottom-up fill performance is required. If the total concentration of the organic additive is too low, the bottom-up filling performance is also insufficient and voids are usually observed. Therefore, in many cases, the total concentration of the organic additive is increased to properly fill the feature having a high aspect ratio. However, if the total concentration exceeds a certain limit, unacceptable deposition defects (e.g., drain plating) typically occur on the surface of the substrate. In this case, the coverage of cobalt on the surface of the substrate is insufficient. Ideally, the entire surface of the substrate is completely and uniformly covered with cobalt while all features on the substrate are filled with cobalt without voids.

該等直鏈炔丙基化合物(尤其炔丙基醇)之缺點係其毒性。因此，期望分別鑑別替代之毒性較小之有機添加劑及毒性較小之組合物。The disadvantages of such linear propargyl compounds, especially propargyl alcohol, are their toxicity. Therefore, it is desirable to separately identify alternative less toxic organic additives and less toxic compositions.

另外，包括該等直鏈炔丙基化合物之組合物並不高度有效。因此，持續需要鑑別用於沉積鈷沉積物之較有效組合物、較佳地另外具有改良之自底向上填充性能之較有效組合物。Additionally, compositions comprising such linear propargyl compounds are not highly effective. Accordingly, there is a continuing need to identify more effective compositions for depositing cobalt deposits, preferably additionally having improved bottom-up fill properties.

另外，確立電解沉積鈷沉積物之穩健且操作良好之方法極其重要。此主要包含可靠地監測的直鏈炔丙基化合物在各別組合物中之總濃度。通常，該等化合物在組合物中之總濃度通常極低且在實踐中基於組合物之總體積介於10 mg/L與50 mg/L之間。因此，尤其需要可靠監測展現相對較低消光係數之該等直鏈炔丙基化合物。In addition, it is extremely important to establish a robust and well-operated method for electrolytically depositing cobalt deposits. This primarily involves the total concentration of the linear propargyl compounds that are reliably monitored in the individual compositions. Generally, the total concentration of such compounds in the composition is typically very low and in practice is between 10 mg/L and 50 mg/L based on the total volume of the composition. Therefore, it is particularly desirable to reliably monitor such linear propargyl compounds exhibiting a relatively low extinction coefficient.

本發明目標 本發明之一目標係提供克服上文所提及問題之用於沉積鈷沉積物之水性組合物。特定目標係鑑別且提供較佳地同時具有以下特徵之組合物：(i)更加有效，(ii)毒性較小，且(iii)容許容易且可靠地尤其藉由UV/VIS量測來監測所利用有機填充添加劑。 OBJECT OF THE INVENTION One object of the present invention is to provide an aqueous composition for depositing cobalt deposits that overcomes the problems mentioned above. A particular target identifies and provides a composition that preferably has at the same time: (i) is more effective, (ii) less toxic, and (iii) allows easy and reliable monitoring of the site, particularly by UV/VIS measurements. Use organic filler additives.

期望該等組合物另外提供極佳漏鍍性能，尤其在相對較高總濃度之該等有機添加劑存在下。It is expected that these compositions additionally provide excellent plating performance, especially in the presence of relatively high total concentrations of such organic additives.

較佳地，該等組合物另外在具有極小開口尺寸、較佳地具有相對較高縱橫比之特徵中提供極佳之自底向上填充性能。Preferably, the compositions additionally provide excellent bottom-up fill performance in features having a very small opening size, preferably a relatively high aspect ratio.

本發明之另一目標係亦提供具有上文所提及優點之電解沉積鈷沉積物之方法。Another object of the invention is also to provide a method of electrolytically depositing cobalt deposits having the advantages mentioned above.

藉由用於沉積鈷沉積物之水性組合物來解決該等目標，該組合物包括 (a) 總量之鈷(II)離子， (b) 至少一種式(I)之第一化合物：(I)， 其中獨立地 R¹ 表示H、-NR³ R⁴ 、-OR⁵ 或-CR⁶ R^6’ R⁷ ， R² 表示H、C1至C4烷基、鹵素或OH， n為1、2或3 其中獨立地 R³ 表示H、C1至C4烷基或經由R⁴ 連結至R¹ 中之氮原子之伸烷基部分， R⁴ 表示H、C1至C4烷基或經由R³ 連結至R¹ 中之氮原子之伸烷基部分， R⁵ 表示H或電子對或C1至C4烷基， R⁶ 表示H、C1至C4烷基或經由R⁷ 連結至R¹ 中之碳原子之伸烷基部分， R^6’ 表示H或C1至C4烷基， R⁷ 表示H、C1至C4烷基或經由R⁶ 連結至R¹ 中之碳原子之伸烷基部分， 條件係基於該組合物中之所有過渡金屬陽離子之總重量，該組合物中該總量之該等鈷(II)離子佔該組合物中之所有過渡金屬陽離子之51 wt.-%至100 wt.-%。These objects are addressed by an aqueous composition for depositing a cobalt deposit comprising (a) a total amount of cobalt (II) ions, (b) at least one first compound of formula (I): (I), wherein independently R ¹ represents H, -NR ³ R ⁴ , -OR ⁵ or -CR ⁶ R ^6' R ⁷ , R ² represents H, C1 to C4 alkyl, halogen or OH, n is 1. 2 or 3 wherein R ³ independently represents H, C1 to C4 alkyl or an alkyl moiety bonded to the nitrogen atom in R ¹ via R ⁴ , R ⁴ represents H, C1 to C4 alkyl or is bonded via R ³ to The alkyl moiety of the nitrogen atom in R ¹ , R ⁵ represents H or an electron pair or a C1 to C4 alkyl group, and R ⁶ represents an extension of H, a C1 to C4 alkyl group or a carbon atom bonded to R ¹ via R ⁷ An alkyl moiety, R ^{6 '} represents H or a C1 to C4 alkyl group, R ⁷ represents H, a C1 to C4 alkyl group or an alkyl moiety bonded to a carbon atom in R ¹ via R ⁶ , the conditions being based on the composition The total weight of all transition metal cations in the composition, the total amount of such cobalt (II) ions in the composition is from 51 wt.-% to 100 wt.-% of all transition metal cations in the composition.

另外，藉由將鈷沉積物電解沉積於基板上之方法來解決其他目標，該方法包括以下步驟： (A) 提供該基板， (B) 提供本發明之水性組合物(如本文之上下文所闡述)， (C) 使該基板與該水性組合物接觸並供應電流，從而將鈷沉積於該基板上以獲得該鈷沉積物。Additionally, other objectives are addressed by a method of electrolytically depositing cobalt deposits on a substrate, the method comprising the steps of: (A) providing the substrate, (B) providing an aqueous composition of the invention (as set forth herein in the context of this document) And (C) contacting the substrate with the aqueous composition and supplying a current to deposit cobalt on the substrate to obtain the cobalt deposit.

本發明組合物係水性組合物，此意指水係主要組分。因此，基於水性組合物之總重量，50 wt.-%以上之組合物係水，較佳地至少70 wt.-%、甚至更佳地至少90 wt.-%、最佳地95 wt.-%或更多之組合物係水。較佳地，水性組合物實質上不含機溶劑；更佳地根本不含機溶劑。另外，該組合物較佳係均質水溶液且由此較佳地不含任何顆粒。The composition of the present invention is an aqueous composition, which means a main component of the water system. Thus, based on the total weight of the aqueous composition, more than 50 wt.-% of the composition is water, preferably at least 70 wt.-%, even more preferably at least 90 wt.-%, optimally 95 wt.- One or more of the compositions are water. Preferably, the aqueous composition is substantially free of organic solvents; more preferably, it is completely free of organic solvents. Additionally, the composition is preferably a homogeneous aqueous solution and is thus preferably free of any particles.

該組合物係用於沉積鈷沉積物、較佳地無硫鈷沉積物。The composition is used to deposit cobalt deposits, preferably sulfur-free cobalt deposits.

較佳者係符合以下條件之本發明組合物：其中該組合物係酸性，較佳地其pH在0.5至6.8範圍內、更佳地在1至6範圍內、甚至更佳地在1.5至5範圍內、最佳地在2.5至4.6範圍內、甚至最佳地在3.5至4.6範圍內。鹼性pH係不期望的，此乃因通常在鹼性pH下觀察到氫氧化鈷沉澱，此通常使得鈷沉積物之表面粗糙度不期望地增加。Preferred are the compositions of the invention wherein the composition is acidic, preferably having a pH in the range of from 0.5 to 6.8, more preferably in the range of from 1 to 6, even more preferably from 1.5 to 5. Within the range, optimally in the range of 2.5 to 4.6, even optimally in the range of 3.5 to 4.6. Alkaline pH is undesirable because cobalt hydroxide precipitation is typically observed at alkaline pH, which typically results in an undesired increase in surface roughness of the cobalt deposit.

除(a)總量之鈷(II)離子外，本發明之水性組合物亦包括(b)至少一種(較佳地一種)式(I)之第一化合物及較佳地另外(c)至少一種(較佳地一種)包括複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物。The aqueous composition of the present invention comprises, in addition to (a) a total amount of cobalt (II) ions, (b) at least one (preferably one) of the first compound of formula (I) and preferably additionally (c) at least One (preferably one) comprises a plurality of polymers each containing a carboxamide moiety of a secondary or tertiary amine nitrogen.

該等本發明組合物之毒性通常小於包括直鏈炔丙基化合物之組合物(例如包括炔丙基醇之組合物)。The compositions of the present invention are generally less toxic than compositions comprising linear propargyl compounds (e.g., compositions comprising propargyl alcohol).

另外，式(I)化合物含有對UV檢測敏感且極佳地可藉助各別分析工具檢測之吡啶部分。此容許可靠地監測式(I)化合物在本發明組合物中之總濃度。典型有機化合物(例如炔丙基醇及炔丙基醇乙氧基化物)在典型UV/VIS光譜內、尤其在250 nm與280 nm之間維持顯著較低之特徵(210 nm至400 nm之間之吸收幾乎維持為零；濃度為0.2 mmol/L)。與之相比，式(I)化合物通常在250 nm與280 nm之間具有強吸收，此可用於監測及甚至量化。舉例而言，式(Ia)化合物(濃度為0.2 mmol/L)在266 nm下展示0.9之最大吸收率。In addition, the compounds of formula (I) contain a pyridine moiety which is sensitive to UV detection and which is excellently detectable by means of separate analytical tools. This allows reliable monitoring of the total concentration of the compound of formula (I) in the compositions of the invention. Typical organic compounds such as propargyl alcohol and propargyl alcohol ethoxylate maintain a significantly lower characteristic (typically between 250 nm and 400 nm) in the typical UV/VIS spectrum, especially between 250 nm and 280 nm. The absorption is almost zero; the concentration is 0.2 mmol/L). In contrast, the compounds of formula (I) typically have strong absorption between 250 nm and 280 nm, which can be used for monitoring and even quantification. For example, a compound of formula (Ia) (concentration 0.2 mmol/L) exhibits a maximum absorption of 0.9 at 266 nm.

自有實驗已展示，本發明組合物之有效性大於包括直鏈炔丙基化合物之組合物(參見下文實例)。此意味著，與代之以包括直鏈炔丙基化合物之組合物(參見下文實例)相比，可在本發明組合物中利用較低工作濃度以達成相同結果。Self-experimental experiments have shown that the compositions of the present invention are more effective than compositions comprising linear propargyl compounds (see examples below). This means that a lower working concentration can be utilized in the compositions of the invention to achieve the same result as compared to a composition comprising a linear propargyl compound (see examples below).

較佳者係符合以下條件之本發明組合物：其中基於組合物之總體積，鈷(II)離子在組合物中之總濃度在0.5 g/L至50 g/L範圍內、較佳地在0.7 g/L至25 g/L範圍內、更佳地在0.9 g/L至15 g/L範圍內、甚至更佳地在1.2 g/L至11 g/L範圍內、最佳地在1.4 g/L至7 g/L範圍內。低於0.5 g/L之濃度通常產生不完全鈷沉積及表面缺陷。若濃度顯著超過50 g/L，則在一些情形下觀察到組合物之不期望沉澱，此亦通常使得鈷沉積物之表面粗糙度不期望地增加。Preferred are compositions of the invention wherein the total concentration of cobalt (II) ions in the composition is in the range of from 0.5 g/L to 50 g/L, preferably based on the total volume of the composition. In the range of 0.7 g/L to 25 g/L, more preferably in the range of 0.9 g/L to 15 g/L, even more preferably in the range of 1.2 g/L to 11 g/L, optimally at 1.4 g/L to 7 g/L. Concentrations below 0.5 g/L typically result in incomplete cobalt deposition and surface defects. If the concentration significantly exceeds 50 g/L, undesired precipitation of the composition is observed in some cases, which also generally causes an undesired increase in the surface roughness of the cobalt deposit.

該等鈷(II)離子之鈷源較佳係至少一種鈷鹽，更佳係至少一種無機鈷鹽及/或至少一種有機鈷鹽。較佳無機鈷鹽係選自由以下組成之群：硝酸鈷、硫酸鈷及鹵化鈷。較佳鹵化鈷係選自由以下組成之群：氟化鈷、氯化鈷及溴化鈷。較佳有機鈷鹽係乙酸鈷。最佳地，至少一種鈷鹽係硫酸鈷、較佳地七水硫酸鈷。The cobalt source of the cobalt (II) ions is preferably at least one cobalt salt, more preferably at least one inorganic cobalt salt and/or at least one organic cobalt salt. Preferably, the inorganic cobalt salt is selected from the group consisting of cobalt nitrate, cobalt sulfate, and cobalt halide. Preferably, the cobalt halide is selected from the group consisting of cobalt fluoride, cobalt chloride and cobalt bromide. A preferred organic cobalt salt is cobalt acetate. Most preferably, at least one cobalt salt is cobalt sulfate, preferably cobalt sulfate heptahydrate.

藉助本發明組合物，較佳地，獲得主要含有鈷之鈷沉積物。此意指，本發明組合物係較佳的，其中該等鈷(II)離子係用於金屬沉積之主要金屬離子物質。較佳者係符合以下條件之本發明組合物：其中基於組合物中之所有過渡金屬陽離子之總重量，該等鈷(II)離子在組合物中之總量佔組合物中之所有過渡金屬陽離子之80 wt.-%至100 wt.-%、較佳地至少90 wt.-%、更佳地至少95 wt.-%、甚至更佳地至少98 wt.-%、最佳地至少99 wt.-%。By means of the composition of the invention, it is preferred to obtain a cobalt deposit comprising predominantly cobalt. This means that the compositions of the invention are preferred wherein the cobalt (II) ions are used as the primary metal ionic species for metal deposition. Preferred are compositions of the invention wherein the total amount of the cobalt (II) ions in the composition is based on the total weight of all transition metal cations in the composition of all transition metal cations in the composition. 80 wt.-% to 100 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-%, even more preferably at least 98 wt.-%, optimally at least 99 wt .-%.

較佳者係符合以下條件之本發明組合物：其中在組合物中，基於組合物之總體積，除鈷(II)離子外(亦即排除總量之鈷(II)離子)之過渡金屬陽離子之總莫耳量對鈷(II)離子之總莫耳量的莫耳比率在0至0.4範圍內、較佳地在0至0.2範圍內、更佳地在0至0.1範圍內、甚至更佳地在0至0.1範圍內、最佳地在0至0.01範圍內。Preferred are compositions of the invention in which the transition metal cations other than cobalt (II) ions (i.e., the total amount of cobalt (II) ions are excluded) are included in the composition based on the total volume of the composition. The molar ratio of the total molar amount to the total molar amount of cobalt (II) ions is in the range of 0 to 0.4, preferably in the range of 0 to 0.2, more preferably in the range of 0 to 0.1, or even better. The ground is in the range of 0 to 0.1, most preferably in the range of 0 to 0.01.

特定而言，若鎳離子存在於本發明組合物中，則該等鈷(II)離子之總莫耳量至少5倍於鎳陽離子之總莫耳量、較佳地至少10倍。最佳地，本發明組合物實質上不含鎳。In particular, if nickel ions are present in the compositions of the present invention, the total moles of such cobalt (II) ions are at least 5 times the total moles of nickel cations, preferably at least 10 times. Most preferably, the compositions of the invention are substantially free of nickel.

在本發明之上下文中，過渡金屬係週期表第3至12族之元素。In the context of the present invention, transition metals are elements of Groups 3 to 12 of the Periodic Table.

在所有情形中之大部分中，本發明組合物最佳地實質上不含(較佳地不含)合金化金屬陽離子。因此，藉助本發明組合物，最佳地獲得純鈷沉積物。In most of all cases, the compositions of the present invention are most preferably substantially free (preferably free) of alloyed metal cations. Thus, pure cobalt deposits are optimally obtained by means of the compositions of the invention.

在本發明之上下文中，術語「實質上不含」標的物(例如化合物、材料等)表示，該標的物根本不存在或僅以不影響本發明預期目的之極少及非干擾量(程度)存在。舉例而言，該標的物可(例如)以不可避免性雜質形式無意添加或利用。基於本發明組合物之總重量(若針對該組合物來定義)或基於本發明方法中所獲得鈷沉積物之總重量(若針對該沉積物來定義)，「實質上不含」較佳地表示0 (零)至50 ppm、較佳地0 ppm至25 ppm、更佳地0 ppm至10 ppm、甚至更佳地0 ppm至5 ppm、最佳地0 ppm至1 ppm。In the context of the present invention, the term "substantially free" of the subject matter (e.g., compound, material, etc.) indicates that the subject matter does not exist at all or exists only in a minimal and non-interfering amount (degree) that does not affect the intended purpose of the present invention. . For example, the subject matter can be inadvertently added or utilized, for example, in the form of inevitable impurities. "Substantially free" is preferably based on the total weight of the composition of the invention (as defined for the composition) or based on the total weight of the cobalt deposit obtained in the process of the invention (if defined for the deposit) It represents 0 (zero) to 50 ppm, preferably 0 ppm to 25 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, most preferably 0 ppm to 1 ppm.

本發明組合物係較佳的，其中該組合物實質上不含(較佳地不含)鎳離子，較佳地實質上不含(較佳地不含)鎳離子、鐵離子及銅離子，更佳地實質上不含(較佳地不含)鎳離子、鐵離子、銅離子、鋁離子、鉛離子及錫離子。Preferably, the composition of the present invention is substantially free (preferably free) of nickel ions, preferably substantially free (preferably free) of nickel ions, iron ions and copper ions. More preferably, substantially no (preferably free) nickel ions, iron ions, copper ions, aluminum ions, lead ions and tin ions are not contained.

較佳地，本發明組合物實質上不含(較佳地不含)包括二價硫之化合物及/或包括巰基之化合物、更佳地MBIS。Preferably, the compositions of the present invention are substantially free (preferably free) of compounds comprising divalent sulfur and/or compounds comprising mercapto groups, more preferably MBIS.

更佳地，該組合物實質上不含具有氧化數低於+5之硫原子之含硫化合物。最佳地，該組合物不包括該等含硫化合物。此意指，該組合物實質上不含(較佳地不含)廣泛用作其他金屬沉積浴(例如鎳電鍍浴)中之增亮劑之含硫化合物。然而，此情形不排除在本發明組合物中存在硫酸根離子，此乃因硫酸根離子含有氧化數為+6 (但不低於+6)之硫原子。此亦並不排除存在較佳地如下文所闡述具有磺酸部分之陰離子，該等陰離子通常包括氧化數為+5之硫原子。若組合物含有具有氧化數尤其低於+5或更低(例如二價硫)之硫原子之含硫化合物，則在許多情形下，硫納入鈷沉積物中。此係不期望的，此乃因硫負面影響鈷沉積物中之電阻率。其他合金化金屬或元素具有類似觀察。另外，包括大量硫之鈷沉積物負面影響在鈷沉積之後實施之其他處理步驟(例如化學機械拋光(CMP))。More preferably, the composition is substantially free of sulfur-containing compounds having a sulfur atom having an oxidation number below +5. Most preferably, the composition does not include such sulfur-containing compounds. This means that the composition is substantially free (preferably free) of sulfur-containing compounds that are widely used as brighteners in other metal deposition baths, such as nickel plating baths. However, this case does not exclude the presence of sulfate ions in the composition of the present invention because the sulfate ions contain sulfur atoms having an oxidation number of +6 (but not less than +6). This also does not exclude the presence of an anion having a sulfonic acid moiety, preferably as described below, which typically comprises a sulfur atom having an oxidation number of +5. If the composition contains a sulfur-containing compound having a sulfur atom having an oxidation number particularly lower than +5 or lower (e.g., divalent sulfur), sulfur is incorporated into the cobalt deposit in many cases. This is undesirable because sulfur negatively affects the resistivity in cobalt deposits. Other alloying metals or elements have similar observations. In addition, the inclusion of large amounts of sulfur-cobalt deposits negatively affects other processing steps (such as chemical mechanical polishing (CMP)) that are performed after cobalt deposition.

甚至更佳地，該組合物實質上不含具有氧化數低於+6之硫原子之含硫化合物。最佳地，該組合物不包括該等含硫化合物。然而，此不排除在本發明組合物中存在硫酸根離子。Even more preferably, the composition is substantially free of sulfur-containing compounds having a sulfur atom having an oxidation number below +6. Most preferably, the composition does not include such sulfur-containing compounds. However, this does not exclude the presence of sulfate ions in the compositions of the invention.

極佳者係符合以下條件之本發明水性組合物：若水性組合物含有含硫化合物，則含硫化合物僅係硫酸根離子 (SO₄ ^2- )或含有磺酸部分之陰離子(較佳地如下文所闡述)。An aqueous composition of the present invention which is excellent in that if the aqueous composition contains a sulfur-containing compound, the sulfur-containing compound is only a sulfate ion (SO ₄ ^2- ) or an anion having a sulfonic acid moiety (preferably as follows) The article explains).

較佳地，本發明組合物係用於電解沉積以獲得鈷沉積物。因此，該組合物較佳地並不用於無電鈷沉積。因此，本發明組合物係較佳的，其中該組合物不含有效量能夠將鈷(II)離子還原成金屬鈷之還原劑。此情形可包含在組合物中存在微小量之該等還原劑。較佳地，該等微小量藉助標準分析工具無法檢測或至少並不有害於作為電解質之預期應用。較佳者係符合以下條件之本發明組合物：其中基於組合物之總體積，該組合物包括總濃度為0 mg/L至200 mg/L之能夠將鈷(II)離子還原成金屬鈷之還原劑，較佳地，該組合物實質上不含能夠將鈷(II)離子還原成金屬鈷之還原劑。最佳地，本發明組合物不含能夠將鈷(II)離子還原成金屬鈷之還原劑。Preferably, the compositions of the invention are used in electrolytic deposition to obtain cobalt deposits. Therefore, the composition is preferably not used for electroless cobalt deposition. Accordingly, the compositions of the present invention are preferred wherein the composition is free of an effective amount of a reducing agent capable of reducing cobalt (II) ions to metallic cobalt. This situation may involve the presence of minor amounts of such reducing agents in the composition. Preferably, such minor amounts are not detectable by, or at least not detrimental to, the intended application as an electrolyte by means of standard analytical tools. Preferred are compositions of the invention wherein the composition comprises a total concentration of from 0 mg/L to 200 mg/L to reduce cobalt (II) ions to metallic cobalt based on the total volume of the composition. A reducing agent, preferably, the composition is substantially free of a reducing agent capable of reducing cobalt (II) ions to metallic cobalt. Most preferably, the compositions of the present invention are free of reducing agents capable of reducing cobalt (II) ions to metallic cobalt.

本發明組合物係較佳的，其中該組合物實質上不含(較佳地不含)能夠將鈷(II)離子還原成含有磷之金屬鈷之還原劑，甚至更佳地，該組合物實質上不含(較佳地不含)含磷化合物。The composition of the present invention is preferably wherein the composition is substantially free (preferably free) from a reducing agent capable of reducing cobalt (II) ions to a metal cobalt containing phosphorus, and even more preferably, the composition The phosphorus-containing compound is substantially free (preferably free).

在大部分情形下，本發明之水性組合物係較佳的，其中該組合物實質上不含(較佳地不含)不飽和環碸化合物，較佳地實質上不含(較佳地不含)包括硫原子之不飽和環狀化合物。In most cases, aqueous compositions of the invention are preferred, wherein the composition is substantially free (preferably free) of unsaturated cyclic guanidine compounds, preferably substantially free (preferably not Containing an unsaturated cyclic compound including a sulfur atom.

本發明組合物係較佳的，其中該組合物實質上不含(較佳地不含)包括炔系部分但非式(I)化合物之化合物。較佳地，該等化合物之總濃度在0 mg/L至10 mg/L範圍內、更佳地在0 mg/L至2 mg/L範圍內、最佳地在0 mg/L至0.5 mg/L範圍內。換言之，在本發明組合物中，式(I)化合物較佳地僅係具有炔系部分之化合物。Compositions of the invention are preferred wherein the composition is substantially free (preferably free) of a compound comprising an alkyne moiety but not a compound of formula (I). Preferably, the total concentration of the compounds ranges from 0 mg/L to 10 mg/L, more preferably from 0 mg/L to 2 mg/L, optimally from 0 mg/L to 0.5 mg. /L range. In other words, in the composition of the present invention, the compound of the formula (I) is preferably only a compound having an acetylene moiety.

本發明之水性組合物包括(b)至少一種(較佳地一種)不含硫之式(I)之第一化合物(參見上文)。The aqueous composition of the present invention comprises (b) at least one, preferably one, sulfur-free first compound of formula (I) (see above).

在本發明之上下文中，術語「至少一種」通常表示「一種、兩種、三種或三種以上」 (且可與其交換使用)。術語「至少[……]」包含「或大於[……]」。In the context of the present invention, the term "at least one" generally means "one, two, three or more" (and may be used interchangeably with it). The term "at least [...]" contains "or greater than [...]".

不期望受限於理論，若在本發明方法中利用該組合物，則假設第一化合物用作阻抑劑，從而抑制期望減小沉積速率之區域(例如在通孔或溝槽內側之側壁)上之鈷沉積。Without wishing to be bound by theory, if the composition is utilized in the process of the invention, it is assumed that the first compound acts as a repressant, thereby inhibiting regions where it is desired to reduce the deposition rate (eg, sidewalls on the inside of the via or trench) Cobalt deposits on.

在本發明組合物中，至少一種第一化合物含有具有連結至羰基碳原子之羰基氧原子之醯基部分。另外，式(I)化合物包括共價連結至環氮之炔系部分。因此，至少第一化合物帶正電。較佳地，炔系部分係炔丙基部分(HC≡C-CH₂ –)。因此，最佳者係R² 係氫之本發明組合物。甚至更佳者係在式(I)中R² 係H且/或n為1之本發明組合物。In the compositions of the present invention, at least one first compound contains a thiol moiety having a carbonyl oxygen atom attached to a carbonyl carbon atom. Additionally, the compound of formula (I) includes an alkyne moiety covalently bonded to the ring nitrogen. Therefore, at least the first compound is positively charged. Preferably, the alkyne moiety is a propargyl moiety (HC≡C-CH ₂ -). Therefore, the most preferred is the composition of the invention in which R ² is hydrogen. Even more preferred are the compositions of the invention wherein R ² is H and/or n is 1 in formula (I).

本發明組合物中之較佳相對陰離子係選自由以下組成之群：鹵素、羧酸殘基陰離子及具有磺酸部分之陰離子。鹵素較佳地係指氯化物及溴化物。較佳羧酸殘基陰離子係甲酸根離子及乙酸根離子。具有磺酸部分之較佳陰離子係選自由以下組成之群：甲苯磺酸根、甲磺酸根、三氟甲磺酸根及全氟丁磺酸根。該等陰離子在碳與硫之間包括共價鍵。較佳者係符合以下條件之本發明組合物：其中該組合物包括上文所提及相對陰離子中之至少一者、較佳地至少溴化物或至少一種具有磺酸部分之陰離子。Preferred relative anions in the compositions of the present invention are selected from the group consisting of halogens, carboxylic acid residue anions, and anions having a sulfonic acid moiety. Halogen preferably refers to chlorides and bromides. Preferred carboxylic acid residue anions are formate ions and acetate ions. Preferred anions having a sulfonic acid moiety are selected from the group consisting of tosylate, mesylate, triflate, and perfluorobutanesulfonate. The anions include a covalent bond between carbon and sulfur. Preferred are compositions of the invention which satisfy the following conditions: wherein the composition comprises at least one of the above mentioned relative anions, preferably at least bromide or at least one anion having a sulfonic acid moiety.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R¹ 表示-NR³ R⁴ 、-OR⁵ 或-CR⁶ R^6’ R⁷ ，更佳地表示-NR³ R⁴ 或-OR⁵ ，最佳地表示-NR³ R⁴ 。Preferred are the compositions of the present invention which satisfy the following conditions: wherein in the formula (I), R ¹ represents -NR ³ R ⁴ , -OR ⁵ or -CR ⁶ R ^6' R ⁷ , more preferably -NR ³ R ⁴ or -OR ⁵ , which best represents -NR ³ R ⁴ .

在本發明組合物中，該至少一種第一化合物係單體，亦即並非聚合物。較佳地，該第一化合物由碳原子、氫原子、氮原子及氧原子組成(亦即在該等情形下，在R² 中不包含鹵素)。因此，較佳者係符合以下條件之本發明組合物：其中在式(I)中，R² 表示H、鹵素或OH，較佳地在一些情形下表示H或鹵素，或在其他情形下較佳地表示H或OH。In the compositions of the invention, the at least one first compound is a monomer, that is, not a polymer. Preferably, the first compound consists of a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom (i.e., in such cases, no halogen is included in R ² ). Accordingly, preferred are compositions of the invention wherein: in formula (I), R ² represents H, halo or OH, preferably in some instances H or halogen, or in other instances Preferably, H or OH is indicated.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，n為1或2、較佳地1。Preferred are the compositions of the present invention which satisfy the following conditions: wherein in the formula (I), n is 1 or 2, preferably 1.

在本發明組合物中，在式(I)中，R³ 及R⁴ 分別包含經由R⁴ 及R³ 連結至R¹ 中之氮原子之伸烷基部分。該伸烷基部分形成包含R¹ 之氮原子之飽和分子內環結構。較佳伸烷基部分包括4至6個碳原子(亦即伸丁基橋、伸戊基橋或伸己基橋)、較佳地4至5個碳原子。In the composition of the present invention, in the formula (I), R ³ and R ⁴ each comprise an alkylene moiety bonded to a nitrogen atom in R ¹ via R ⁴ and R ³ . The alkylene portion is formed comprising a saturated intramolecular structure R ¹ of the nitrogen atoms. Preferably, the alkyl moiety comprises from 4 to 6 carbon atoms (i.e., a butyl bridge, a pentyl bridge or a hexyl bridge), preferably from 4 to 5 carbon atoms.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R³ 表示H或C1至C4烷基，較佳地表示H、甲基或乙基。在該等情形下，R³ 不包括上文所提及之環化。Preferred are the compositions of the invention wherein: in the formula (I), R ³ represents H or a C1 to C4 alkyl group, preferably H, methyl or ethyl. In such cases, R ³ does not include the cyclization mentioned above.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R⁴ 表示H或C1至C4烷基，較佳地表示H、甲基或乙基。在該等情形下，R⁴ 不包括上文所提及之環化。Preferred are the compositions of the invention wherein: in the formula (I), R ⁴ represents H or a C1 to C4 alkyl group, preferably H, methyl or ethyl. In such cases, R ⁴ does not include the cyclization mentioned above.

在一些情形下，極佳地，在式(I)中，R³ 及R⁴ 相同，最佳地，R³ 及R⁴ 不表示該伸烷基部分。最佳地，二者皆係H、甲基或乙基。In some cases, it is preferred that in the formula (I), R ³ and R ^{4 are the} same, and most preferably, R ³ and R ⁴ do not represent the alkylene moiety. Most preferably, both are H, methyl or ethyl.

在本發明組合物中，在式(I)中，R⁵ 表示H或電子對或C1至C4烷基。電子對意指，R¹ 中之氧原子係以解離/去質子化形式存在，從而攜載分佈於式(I)化合物中之整個羧酸基團上之負電荷且產生羧酸根陰離子(–COO^– )。換言之，R¹ 表示H、-NR³ R⁴ 、-OR⁵ 、-O^- 或-CR⁶ R^6’ R⁷ ，其中R⁵ 表示H或C1至C4烷基。關於R² 、R³ 、R⁴ 、R⁶ 、R^6’ 、R⁷ 之定義，分別參見上下文。In the composition of the present invention, in the formula (I), R ⁵ represents H or an electron pair or a C1 to C4 alkyl group. Electron pair means that the oxygen atom in R ^{1 is present} in dissociated/deprotonated form, thereby carrying a negative charge on the entire carboxylic acid group of the compound of formula (I) and producing a carboxylate anion (–COO) ^– ). In other words, R ¹ represents H, -NR ³ R ⁴ , -OR ⁵ , -O ^- or -CR ⁶ R ^6' R ⁷ , wherein R ⁵ represents H or a C1 to C4 alkyl group. For the definitions of R ² , R ³ , R ⁴ , R ⁶ , R ^{6 '} and R ⁷ , refer to the context, respectively.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R⁵ 表示C1至C4烷基，更佳地表示甲基或乙基。Preferred are the compositions of the present invention which satisfy the following conditions: wherein in the formula (I), R ⁵ represents a C1 to C4 alkyl group, more preferably a methyl group or an ethyl group.

在本發明組合物中，在式(I)中，R⁶ 及R⁷ 分別包含經由R⁷ 及R⁶ 連結至R¹ 中之碳原子之伸烷基部分。該伸烷基部分形成包含R¹ 之碳原子之飽和分子內環結構。較佳伸烷基部分包括4至6個碳原子(亦即伸丁基橋、伸戊基橋或伸己基橋)、較佳地4至5個碳原子。In the composition of the present invention, in the formula (I), R ⁶ and R ⁷ each comprise an alkylene moiety bonded to a carbon atom in R ¹ via R ⁷ and R ⁶ . The alkylene moiety forms a saturated intramolecular ring structure comprising a carbon atom of R ¹ . Preferably, the alkyl moiety comprises from 4 to 6 carbon atoms (i.e., a butyl bridge, a pentyl bridge or a hexyl bridge), preferably from 4 to 5 carbon atoms.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R⁶ 表示H或C1至C4烷基，較佳地表示H、甲基或乙基。在該等情形下，R⁶ 不包括上文所提及之環化。Preferred are the compositions of the invention wherein: in the formula (I), R ⁶ represents H or a C1 to C4 alkyl group, preferably H, methyl or ethyl. In such cases, R ⁶ does not include the cyclization mentioned above.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R^6’ 表示H、甲基或乙基，較佳地表示H。Preferred are the compositions of the invention wherein: in the formula (I), R ^{6 '} represents H, methyl or ethyl, preferably H.

較佳者係符合以下條件之本發明組合物：其中在式(I)中，R⁷ 表示H或C1至C4烷基，較佳地表示H、甲基或乙基。在該等情形下，R⁷ 不包括上文所提及之環化。Preferred are the compositions of the invention wherein: in the formula (I), R ⁷ represents H or a C1 to C4 alkyl group, preferably H, methyl or ethyl. In such cases, R ⁷ does not include the cyclization mentioned above.

在一些情形下，極佳地，在式(I)中，R^6’ 係H且R⁶ 及R⁷ 中之一者係H且另一者係H、甲基或乙基。In some cases, it is preferred that in formula (I), R ^{6 '} is H and one of R ⁶ and R ⁷ is H and the other is H, methyl or ethyl.

在本發明之上下文中，C1至C4烷基較佳地表示甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基或第三丁基，更佳地表示甲基或乙基。較佳者係符合以下條件之本發明組合物：其中式(I)之R² 至R⁷ (包含R^6’ )中之C1至C4烷基獨立地係甲基或乙基。In the context of the present invention, C1 to C4 alkyl preferably denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl or t-butyl, more preferably Ground represents methyl or ethyl. Preferred are the compositions of the present invention in which the C1 to C4 alkyl groups in R ² to R ⁷ (including R ^{6 '} ) of the formula (I) are independently methyl or ethyl.

在式(I)化合物中，-(CO)-R¹ 部分位於鄰位、間位或對位。較佳者係符合以下條件之本發明組合物：其中在式(I)中，-(CO)-R¹ 部分位於間位。In the compounds of formula (I), the -(CO)-R ¹ moiety is in the ortho, meta or para position. Preferred are the compositions of the present invention which satisfy the following conditions: wherein in the formula (I), the -(CO)-R ¹ moiety is in the meta position.

最佳者係至少一種式(I)之第一化合物係選自由以下組成之群之本發明組合物：術語「獨立地」表示，式(I)之第一化合物之R¹ 至R⁷ 與相同本發明組合物中之其他式(I)化合物中之R¹ 至R⁷ 獨立選擇。Preferably, at least one of the first compounds of formula (I) is selected from the group consisting of the compositions of the invention consisting of: The term "independently" means that R ¹ to R ⁷ of the first compound of formula (I) are independently selected from R ¹ to R ⁷ of the other compounds of formula (I) in the same composition of the invention.

較佳者係符合以下條件之本發明組合物：其中基於組合物之總體積，至少一種第一化合物在組合物中之總濃度在5 mg/L至250 mg/L範圍內、較佳地在7 mg/L至150 mg/L範圍內、更佳地在9 mg/L至90 mg/L範圍內、甚至更佳地在12 mg/L至70 mg/L範圍內。若濃度顯著低於5 mg/L，則在將各別組合物利用於鈷沉積物方法中以填充特徵時通常觀察不到阻抑效應，從而通常產生複數個空隙。若濃度顯著超過250 mg/L，則通常在鈷沉積物方法中發生重度不可控漏鍍。Preferred are compositions of the invention wherein the total concentration of at least one first compound in the composition is in the range of from 5 mg/L to 250 mg/L, preferably based on the total volume of the composition. It is in the range of 7 mg/L to 150 mg/L, more preferably in the range of 9 mg/L to 90 mg/L, even more preferably in the range of 12 mg/L to 70 mg/L. If the concentration is significantly below 5 mg/L, a repressive effect is generally not observed when the individual compositions are utilized in a cobalt deposit process to fill the features, thereby typically producing a plurality of voids. If the concentration significantly exceeds 250 mg/L, severe uncontrolled plating is typically present in the cobalt deposit process.

本發明之水性組合物較佳地另外包括(c)至少一種(較佳地一種)包括複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物。較佳地，該至少一種聚合物不含一級胺氮。在本發明之上下文中，術語「胺氮」係指羧醯胺部分中之氮原子。聚合物通常由單體結構單元組成。The aqueous composition of the present invention preferably further comprises (c) at least one (preferably one) polymer comprising a plurality of carboxyguanamine moieties each containing a secondary or tertiary amine nitrogen. Preferably, the at least one polymer is free of primary amine nitrogen. In the context of the present invention, the term "amine nitrogen" means a nitrogen atom in the carboxyguanamine moiety. The polymer usually consists of monomeric structural units.

較佳者係符合以下條件之本發明組合物：其中至少一種聚合物中所有單體結構單元之50%以上、較佳地70%以上、甚至更佳地85%以上、最佳地95%以上包括至少一個(較佳地一個)該含有二級或三級胺氮之羧醯胺部分。單體結構單元中之羧醯胺部分相同或不同(舉例而言，單體結構單元之一種物質包括含有二級胺氮之羧醯胺部分且另一物質包括含有三級胺氮之羧醯胺部分)。最佳者係其中至少一種聚合物係均聚物之本發明組合物。此意指，每一單體結構單元包括相同之至少一個(較佳地一個)該含有二級或三級胺氮之羧醯胺部分。Preferred are compositions of the invention in which at least 50%, preferably more than 70%, even more preferably more than 85%, most preferably more than 95% of all monomeric structural units in at least one polymer Included is at least one, preferably one, of the carboxyguanamine moiety containing a secondary or tertiary amine nitrogen. The carboxyguanamine moiety in the monomeric structural unit is the same or different (for example, one substance of the monomeric structural unit includes a carboxamide moiety containing a secondary amine nitrogen and the other substance includes a carboxamide containing a tertiary amine nitrogen section). Most preferred are compositions of the invention in which at least one polymer is a homopolymer. This means that each monomer structural unit comprises the same at least one (preferably one) carboxamide moiety containing a secondary or tertiary amine nitrogen.

該等聚合物正面影響基板表面上之漏鍍性能，即使至少一種第一化合物之總濃度相對較高。此正效應發生於寬範圍之分子量內。因此，較佳者係符合以下條件之本發明組合物：其中至少一種聚合物中之每一者之重量平均分子量M_W 在1 200 g/mol至50 000 000 g/mol範圍內、較佳地在2 000 g/mol至20 000 000 g/mol範圍內、更佳地在3 000 g/mol至 8 000 000 g/mol範圍內、甚至更佳地在4 000 g/mol至6 000 000 g/mol範圍內、最佳地在5 000 g/mol至5 000 000 g/mol範圍內(參見下文實例)。These polymers positively affect the plating performance on the surface of the substrate even if the total concentration of at least one of the first compounds is relatively high. This positive effect occurs over a wide range of molecular weights. Accordingly, preferred are compositions of the invention wherein the weight average molecular weight M _W of each of the at least one polymer is in the range of from 1 200 g/mol to 50 000 000 g/mol, preferably In the range from 2 000 g/mol to 20 000 000 g/mol, more preferably in the range from 3 000 g/mol to 8 000 000 g/mol, even more preferably from 4 000 g/mol to 6 000 000 g Within the range of /mol, optimally in the range of 5 000 g/mol to 5 000 000 g/mol (see examples below).

儘管具有相對較高之分子量，但該等聚合物另外改良各別填充實驗中之自底向上填充性能(參見下文實例)。儘管分子量並無特定限制，但似乎此效應主要受限於分子量下限。因此，至少一種或較佳地所有該至少一種聚合物之較佳重量平均分子量M_W 為至少100 000 g/mol。較佳者係符合以下條件之本發明組合物：其中至少一種或較佳地所有該至少一種聚合物之重量平均分子量M_W 在100 000 g/mol至50 000 000 g/mol範圍內、較佳地在200 000 g/mol至10 000 000 g/mol範圍內、最佳地在 500 000 g/mol至5 000 000 g/mol範圍內。利用該等聚合物通常產生改良之漏鍍性能以及(亦即另外)改良之自底向上填充性能(參見下文實例)。因此，該等聚合物在本發明組合物中係最佳的。Despite having a relatively high molecular weight, the polymers additionally improved the bottom-up filling performance in individual filling experiments (see examples below). Although the molecular weight is not particularly limited, it seems that this effect is mainly limited by the lower molecular weight. Thus, at least one or preferably all of the at least one polymer preferably has a weight average molecular weight M _W of at least 100 000 g/mol. Preferred are compositions of the invention wherein at least one or preferably all of the at least one polymer has a weight average molecular weight M _W in the range of from 100 000 g/mol to 50 000 000 g/mol, preferably The ground is in the range of 200 000 g/mol to 10 000 000 g/mol, optimally in the range of 500 000 g/mol to 5 000 000 g/mol. The use of such polymers generally results in improved plating performance and (i.e., improved) bottom-up fill performance (see examples below). Accordingly, such polymers are preferred in the compositions of the present invention.

更佳者係其中羧醯胺部分獨立地由式(II)代表之本發明組合物：(II)， 其中 R⁸ 表示C1至C3烷基或經由R⁹ 連結至式(II)中之該羧醯胺部分之胺氮原子之伸烷基部分， R⁹ 表示氫、C1至C3烷基、該聚合物之主鏈碳原子或經由R⁸ 連結至式(II)中之該羧醯胺部分之羰基碳原子之伸烷基部分，且 R¹⁰ 表示該聚合物之該主鏈之碳原子。More preferably, the composition of the invention wherein the carboxyguanamine moiety is independently represented by formula (II): (II), wherein R ⁸ represents a C1 to C3 alkyl group or an alkyl moiety of an amine nitrogen atom bonded to the carboxamide moiety of the formula (II) via R ⁹ , and R ⁹ represents hydrogen, C1 to C3 alkyl a main chain carbon atom of the polymer or an alkyl moiety bonded to the carbonyl carbon atom of the carboxyguanamine moiety in the formula (II) via R ⁸ , and R ¹⁰ represents a carbon atom of the main chain of the polymer .

由式(II)代表之部分包括連結至R⁹ 及R¹⁰ 之胺氮原子以及連結至R⁸ 之羰基碳原子。The moiety represented by the formula (II) includes an amine nitrogen atom bonded to R ⁹ and R ¹⁰ and a carbonyl carbon atom bonded to R ⁸ .

術語「聚合物之主鏈碳原子」包含以下含義：式(II)中之羧醯胺部分之胺氮原子包含於聚合物之主鏈中(例如在PEOX或PMOX中，參見下文)或包含於聚合物之側鏈中(例如在PNVA或PMVA中，參見下文)。The term "main chain carbon atom of a polymer" encompasses the meaning that the amine nitrogen atom of the carboxyguanamine moiety of formula (II) is contained in the backbone of the polymer (for example in PEOX or PMOX, see below) or In the side chain of the polymer (for example in PNVA or PMVA, see below).

在R⁸ 及R⁹ 中，術語「經由[……]連結之伸烷基部分」分別表示產生包含胺氮原子及羰基碳原子之分子內環結構之橋接伸烷基部分(例如在PVP或PVCL中，參見下文)。較佳伸烷基部分包括3至5個碳原子(亦即伸丙基橋、伸丁基橋或伸戊基橋)、較佳地3個碳原子。In R ⁸ and R ⁹ , the term "alkylene moiety linked via [...]" respectively denotes a bridged alkyl moiety which produces an intramolecular ring structure comprising an amine nitrogen atom and a carbonyl carbon atom (for example, in PVP or PVCL). Medium, see below). Preferably, the alkyl moiety comprises from 3 to 5 carbon atoms (i.e., a propyl bridge, a butyl bridge or a pentyl bridge), preferably 3 carbon atoms.

較佳地，在R⁸ 及R⁹ 中，該C1-C3烷基獨立地選自由以下組成之群：甲基、乙基、正丙基及異丙基，較佳地獨立地選自由甲基及乙基組成之群。Preferably, in R ⁸ and R ⁹ , the C1-C3 alkyl group is independently selected from the group consisting of methyl, ethyl, n-propyl and isopropyl, preferably independently selected from methyl And a group of ethyl groups.

較佳者係其中至少一種聚合物不含硫原子之本發明組合物。Preferred are compositions of the invention wherein at least one of the polymers does not contain a sulfur atom.

更佳者係其中至少一種聚合物中之每一者由碳原子、氫原子、氮原子及氧原子組成之本發明組合物。More preferably, the composition of the invention wherein each of at least one of the polymers consists of a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom.

較佳者係其中至少一種聚合物不含羥基之本發明組合物。Preferred are compositions of the invention wherein at least one of the polymers does not contain a hydroxyl group.

較佳者係其中至少一種聚合物不含炔系部分之本發明組合物。Preferred are compositions of the invention in which at least one polymer does not contain an acetylene moiety.

較佳者係其中至少一種聚合物不含醚氧原子之本發明組合物。Preferred are compositions of the invention in which at least one polymer does not contain an ether oxygen atom.

最佳者係其中至少一種聚合物係選自由以下組成之群之本發明組合物： 最佳者係其中至少一種聚合物係選自由PVP、PEOX及PNVA組成之群之組合物。Preferably, at least one of the polymers is selected from the group consisting of the compositions of the invention consisting of: Most preferably, at least one of the polymers is selected from the group consisting of PVP, PEOX and PNVA.

較佳者係符合以下條件之本發明組合物：其中基於組合物之總體積，至少一種聚合物在組合物中之總濃度在60 mg/L至1000 mg/L範圍內、較佳地在80 mg/L至800 mg/L範圍內、更佳地在100 mg/L至600 mg/L範圍內、甚至更佳地在150 mg/L至500 mg/L範圍內、最佳地在200 mg/L至400 mg/L範圍內。若濃度顯著低於60 mg/L，則在相對較高濃度之第一化合物存在下之不期望漏鍍通常不再得到適當阻抑。若濃度顯著超過1000 mg/L，則沉積製程不期望地受擾。Preferred are compositions of the invention wherein the total concentration of at least one polymer in the composition is in the range of from 60 mg/L to 1000 mg/L, preferably at 80, based on the total volume of the composition. In the range of mg/L to 800 mg/L, more preferably in the range of 100 mg/L to 600 mg/L, even more preferably in the range of 150 mg/L to 500 mg/L, optimally at 200 mg /L to 400 mg/L. If the concentration is significantly below 60 mg/L, undesired leakage plating in the presence of a relatively high concentration of the first compound is generally no longer suitably inhibited. If the concentration significantly exceeds 1000 mg/L, the deposition process is undesirably disturbed.

本發明組合物視情況含有用於穩定pH之緩衝劑且較佳地選自由硼酸及乙酸/乙酸鹽組成之群。最佳者係硼酸。較佳地，基於組合物之總體積，緩衝劑(較佳地硼酸)在組合物中之總濃度在5 g/L至60 g/L範圍內、較佳地在10 g/L至40 g/L範圍內、最佳地在20 g/L至30 g/L範圍內。The compositions of the present invention optionally contain a buffer for stabilizing the pH and are preferably selected from the group consisting of boric acid and acetic acid/acetate. The best is boric acid. Preferably, the total concentration of buffer (preferably boric acid) in the composition is in the range of from 5 g/L to 60 g/L, preferably from 10 g/L to 40 g, based on the total volume of the composition. Within the range of /L, optimally in the range of 20 g/L to 30 g/L.

如上文所提及，本發明亦係關於利用本發明組合物將鈷沉積物電解沉積於基板上之方法。As mentioned above, the present invention is also directed to a method of electrolytically depositing cobalt deposits onto a substrate using the compositions of the present invention.

在本發明方法之步驟(A)中，提供基板。較佳者係其中基板係半導體基底基板之本發明方法。此意指，基板較佳地包括至少一種類金屬及/或鎵、更佳地選自由矽、鍺及鎵組成之群、最佳地矽。In step (A) of the process of the invention, a substrate is provided. Preferred is the method of the invention in which the substrate is a semiconductor base substrate. This means that the substrate preferably comprises at least one metalloid and/or gallium, more preferably selected from the group consisting of ruthenium, osmium and gallium, optimally ruthenium.

用於當前技術裝置之基板通常包括小尺寸特徵。較佳者係其中基板在其至少一個表面上包括複數個通孔及/或溝槽之本發明方法。Substrates for use in current state of the art typically include small size features. Preferably, the method of the invention wherein the substrate comprises a plurality of vias and/or trenches on at least one surface thereof.

更佳者係符合以下條件之本發明方法：其中基板係晶圓、更佳地在至少一個表面上具有複數個通孔及/或溝槽之晶圓。More preferably, the method of the present invention is characterized in that the substrate is a wafer, more preferably a wafer having a plurality of vias and/or trenches on at least one surface.

本發明方法係較佳的，其中在步驟(C)中，鈷沉積物填充該等通孔及/或溝槽。更佳者係符合以下條件之本發明方法：其中在步驟(C)中，鈷沉積物 -填充該等通孔及/或溝槽且另外 -至少在包括該等經填充通孔及/或溝槽之一側覆蓋整個基板。Preferably, the process of the invention is wherein in step (C), the cobalt deposit fills the vias and/or trenches. More preferably, the method of the invention meets the following conditions: wherein in step (C), the cobalt deposit-fills the vias and/or trenches and additionally - at least includes the filled vias and/or trenches One side of the slot covers the entire substrate.

在沉積鈷沉積物後，本發明方法係較佳的，其中在另一步驟中，較佳地藉由機械及/或化學去除來部分地、水平地去除鈷沉積物。因此，獲得鈷沉積物之極平滑且均勻之表面。The method of the invention is preferred after depositing the cobalt deposit, wherein in another step, the cobalt deposit is partially and horizontally removed, preferably by mechanical and/or chemical removal. Thus, an extremely smooth and uniform surface of the cobalt deposit is obtained.

較佳者係符合以下條件之本發明方法：其中該等通孔及溝槽之最小開口尺寸為100 nm或小於100 nm、較佳地50 nm或小於50 nm、更佳地30 nm或小於30 nm、甚至更佳地20 nm或小於20 nm、最佳地10 nm或小於10 nm。Preferably, the method of the present invention is characterized in that the minimum opening size of the vias and trenches is 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. Nm, even more preferably 20 nm or less than 20 nm, optimally 10 nm or less than 10 nm.

較佳者係符合以下條件之本發明方法：其中該等通孔及溝槽之縱橫比範圍為2:1至50:1、較佳地3:1至40:1、更佳地3:1至30:1、甚至更佳地3:1至20:1、最佳地3:1至15:1。Preferably, the method of the present invention meets the following conditions: wherein the through holes and the grooves have an aspect ratio ranging from 2:1 to 50:1, preferably from 3:1 to 40:1, more preferably 3:1. Up to 30:1, even more preferably 3:1 to 20:1, optimally 3:1 to 15:1.

通常，該基板包括用於電解沉積鈷之導電晶種層。較佳者係其中基板包括鈷晶種層之本發明方法。因此，在步驟(C)中，將鈷沉積物較佳地沉積於鈷晶種層上。此產生晶種層及鈷沉積物之極佳均質層配置。通常，該均質配置展現極期望電阻率。另外，較佳地無需額外障壁層。Typically, the substrate comprises a conductive seed layer for electrolytically depositing cobalt. Preferred are the methods of the invention wherein the substrate comprises a cobalt seed layer. Therefore, in step (C), a cobalt deposit is preferably deposited on the cobalt seed layer. This produces an excellent homogeneous layer configuration of the seed layer and cobalt deposits. Typically, this homogeneous configuration exhibits a very desirable resistivity. In addition, it is preferred that no additional barrier layers are required.

在本發明方法中，基板用作陰極以在步驟(C)中獲得鈷沉積物。In the process of the invention, the substrate is used as a cathode to obtain a cobalt deposit in step (C).

較佳者係符合以下條件之本發明方法：其中電流係直流電流，其中較佳地陰極電流密度在0.01 A/dm² 至2 A/dm² 範圍內，更佳地陰極電流密度在0.03 A/dm² 至1.5 A/dm² 範圍內，最佳地陰極電流密度在0.05 A/dm² 至1.0 A/dm² 範圍內。在一些情形下，較佳地，步驟(C)中之直流電流未由電流脈衝補充。此意指，較佳地，在步驟(C)中，直流電流係唯一電流。Preferably, the method of the present invention is characterized in that the current is a direct current, wherein preferably the cathode current density is in the range of 0.01 A/dm ² to 2 A/dm ² , more preferably the cathode current density is 0.03 A/ In the range of dm ² to 1.5 A/dm ² , the optimum cathode current density is in the range of 0.05 A/dm ² to 1.0 A/dm ² . In some cases, preferably, the direct current in step (C) is not supplemented by current pulses. This means that, preferably, in step (C), the direct current is a unique current.

本發明方法係較佳的，其中在步驟(C)中，實施接觸及電流供應3秒至600秒、較佳地5秒至300秒、最佳地10秒至150秒。若實施接觸顯著小於3秒，則通常獲得不完整鈷沉積物且通常複數個通孔及/或溝槽未填充或至少填充不夠充分。若實施接觸顯著大於600秒，則在大部分情形下，過厚鈷層沉積於整個基板上，此係無需延長之後續處理步驟(例如CMP)所不期望的。The method of the present invention is preferred, wherein in step (C), the contact and current supply is carried out for 3 seconds to 600 seconds, preferably 5 seconds to 300 seconds, and most preferably 10 seconds to 150 seconds. If the contact is effected for significantly less than 3 seconds, then incomplete cobalt deposits are typically obtained and typically a plurality of vias and/or trenches are unfilled or at least insufficiently filled. If the contact is effected for significantly more than 600 seconds, in most cases, an overly thick cobalt layer is deposited over the entire substrate, which is undesirable without the need for extended subsequent processing steps (e.g., CMP).

較佳地，若施加直流電流，則實施沉積序列。因此，本發明方法係較佳的，其中步驟(C)中之接觸包括與第一陰極電流密度之第一接觸時間及隨後與第二陰極電流密度之第二接觸時間，其中第一接觸時間短於第二接觸時間且第一陰極電流密度低於第二陰極電流密度。Preferably, if a direct current is applied, a deposition sequence is performed. Accordingly, the method of the present invention is preferred wherein the contact in step (C) comprises a first contact time with a first cathode current density and a second contact time with a second cathode current density, wherein the first contact time is short At a second contact time and the first cathode current density is lower than the second cathode current density.

較佳地，第一接觸時間在3秒至90秒、更佳地5秒至40秒之範圍內。獨立地，較佳第一陰極電流密度在0.01 A/dm² 至0.5 A/dm² 範圍內、更佳地在0.1 A/dm² 至0.4 A/dm² 範圍內。Preferably, the first contact time is in the range of 3 seconds to 90 seconds, more preferably 5 seconds to 40 seconds. Independently, the preferred first cathode current density is in the range of from 0.01 A/dm ² to 0.5 A/dm ² , more preferably from 0.1 A/dm ² to 0.4 A/dm ² .

較佳地，第二接觸時間在50秒至510秒、更佳地70秒至150秒之範圍內。獨立地，較佳第二陰極電流密度在0.1 A/dm² 至2.0 A/dm² 範圍內、更佳地在0.2 A/dm² 至1.0 A/dm² 範圍內。Preferably, the second contact time is in the range of 50 seconds to 510 seconds, more preferably 70 seconds to 150 seconds. Independently, it is preferred that the second cathode current density is in the range of 0.1 A/dm ² to 2.0 A/dm ² , more preferably 0.2 A/dm ² to 1.0 A/dm ² .

在本發明方法之步驟(C)中，藉助電流將鈷沉積物沉積於基板上(較佳地首先沉積至該等通孔及/或溝槽中且隨後沉積於整個基板上)。較佳者係符合以下條件之本發明方法：基於鈷沉積物之總重量，其中鈷沉積物包括60 wt.-%或更多鈷、較佳地75 wt.-%或更多、更佳地90 wt.-%或更多、甚至更佳地95 wt.-%或更多、極佳地98 wt.-%或更多、最佳地99.9 wt.-%或更多之鈷。包括至少99.9 wt.-%鈷之鈷沉積物通常視為純鈷沉積物。在當前電子裝置中極期望該鈷沉積物。In step (C) of the method of the invention, cobalt deposits are deposited on the substrate by means of an electrical current (preferably first deposited into the vias and/or trenches and subsequently deposited over the entire substrate). Preferably, the method of the invention is based on the total weight of the cobalt deposit, wherein the cobalt deposit comprises 60 wt.-% or more cobalt, preferably 75 wt.-% or more, more preferably 90 wt.-% or more, even more preferably 95 wt.-% or more, very preferably 98 wt.-% or more, optimally 99.9 wt.-% or more of cobalt. Cobalt deposits comprising at least 99.9 wt.-% cobalt are generally considered to be pure cobalt deposits. This cobalt deposit is highly desirable in current electronic devices.

較佳地，鈷沉積物實質上不含(較佳地不包括)由以下組成之群之一種、一種以上或所有元素：鎳、鐵、銅、鋁、鉛及錫。更佳地，鈷沉積物並非鎳鈷合金。Preferably, the cobalt deposit is substantially free (preferably excluding) one, more than one or all of the elements consisting of: nickel, iron, copper, aluminum, lead and tin. More preferably, the cobalt deposit is not a nickel-cobalt alloy.

極佳者係符合以下條件之本發明方法：其中鈷沉積物實際上不含(較佳地不含)磷及/或硫，較佳地實質上不含(較佳地不含)磷及硫。因此，鈷沉積物較佳係無硫及/或無磷鈷沉積物。另外，鈷沉積物較佳地實質上不含(較佳地不含)硼。An excellent method is the process of the invention wherein the cobalt deposit is substantially free (preferably free) of phosphorus and/or sulfur, preferably substantially free (preferably free) of phosphorus and sulfur . Therefore, the cobalt deposit is preferably a sulfur-free and/or phosphorus-free cobalt deposit. Additionally, the cobalt deposit is preferably substantially free (preferably free) of boron.

較佳者係符合以下條件之本發明方法：其中在步驟(C)中，水性組合物之溫度在5℃至90℃範圍內、較佳地在15℃至60℃範圍內、更佳地在20℃至50℃範圍內、最佳地在22℃至30℃範圍內。Preferred is a process of the invention which satisfies the following conditions: wherein in step (C), the temperature of the aqueous composition is in the range of from 5 ° C to 90 ° C, preferably from 15 ° C to 60 ° C, more preferably It is in the range of 20 ° C to 50 ° C, preferably in the range of 22 ° C to 30 ° C.

本發明亦係關於本發明組合物用於沉積鈷沉積物、較佳地用於填充通孔及/或溝槽之用途。上文關於本發明組合物及本發明方法所提及者分別同樣適用於上文所提及之用途。The invention is also directed to the use of the compositions of the invention for depositing cobalt deposits, preferably for filling vias and/or trenches. The above reference to the compositions of the invention and the methods of the invention are equally applicable to the uses mentioned above.

藉由下列非限制性實例來更詳細地闡述本發明。The invention is illustrated in more detail by the following non-limiting examples.

實例 1. 式(I)化合物之合成： 如US 3,432,509 A第5行第68列至第8行第5列中所揭示來合成式(I)化合物、尤其化合物(Ia)至(Ig) (如上文所闡述)。上文提及化合物之合成尤其係基於US’509之實例19至21。 Example 1. Synthesis of a compound of formula (I): The compound of formula (I), especially compounds (Ia) to (Ig), is synthesized as disclosed in column 5, column 68 to column 8, column 5 of US Pat. No. 3,432,509. The article explains). The synthesis of the compounds mentioned above is based in particular on Examples 19 to 21 of US '509.

2-A. 用於沉積鈷沉積物之水性組合物： 在第一步驟中，製備若干水性組合物(編號C1至C4及E1至E14)。每一組合物含有至少90 wt.-% DI水(基於組合物之總重量)、大約30 g/L硼酸及硫酸鈷(其量應使得每一組合物中之鈷(II)離子總濃度大約為3 g/L) (各自基於組合物之總體積)。表1匯總其他化合物之存在及濃度。每一組合物具有介於4.0與4.5之間之pH且鈷係組合物中之唯一過渡金屬。 表1 *基於組合物之總體積^# 通常表示「分鐘量」之縮寫且係指式(I)化合物之特定分子量 在表1中，X1及X2具有下列含義： X1表示購自BASF之HC≡C-CH₂ -O-(CH₂ )₂ -OH (炔丙基醇乙氧基化物) X2表示雙-(鈉磺基丙基)-二硫化物(SPS)，其並非聚合物；該等實驗係出於對比原因且係基於WO 2017/004424 A1。特定分子量為354 g/mol。2-A. Aqueous composition for depositing cobalt deposits: In the first step, several aqueous compositions (numbers C1 to C4 and E1 to E14) were prepared. Each composition contains at least 90 wt.-% DI water (based on the total weight of the composition), about 30 g/L boric acid, and cobalt sulfate in an amount such that the total cobalt (II) ion concentration in each composition is about It is 3 g/L) (each based on the total volume of the composition). Table 1 summarizes the presence and concentration of other compounds. Each composition has a pH between 4.0 and 4.5 and the only transition metal in the cobalt-based composition. Table 1 *Based on the total volume of the composition ^# is usually an abbreviation of "minute amount" and means that the specific molecular weight of the compound of formula (I) is in Table 1, and X1 and X2 have the following meanings: X1 represents HC≡C-CH available from BASF ₂ -O-(CH ₂ ) ₂ -OH (propargyl alcohol ethoxylate) X 2 represents bis-(sodium sulfopropyl)-disulfide (SPS), which is not a polymer; For comparison reasons and based on WO 2017/004424 A1. The specific molecular weight is 354 g/mol.

聚合物(IIa)係購自Alfa Aesar；M_W 為5 000及500 000之聚合物(IId)分別購自Polyscience及Sigma Aldrich。Polymer (IIa) was purchased from Alfa Aesar; polymers with M _W of 5,000 and 500 000 (IId) were purchased from Polyscience and Sigma Aldrich, respectively.

2-B. 將鈷沉積物電解沉積於基板上之方法(沉積及填充實驗)： 在第二步驟中，實施本發明方法且分別沉積及填充無硫鈷。2-B. Method for Electrodepositing Cobalt Deposits on Substrates (Deposition and Filling Experiment): In the second step, the method of the present invention is carried out and separately deposited and filled with sulfur-free cobalt.

在每一實驗中，使用500 ml在第一步驟中製得之各別水性組合物。為加以對比，表1中所給出之每一數字(編號)係指相應實驗。In each experiment, 500 ml of each of the aqueous compositions prepared in the first step was used. For comparison, each number (number) given in Table 1 refers to the corresponding experiment.

在實驗之前，使用惰性氮氣將每一水性組合物吹掃15分鐘，且隨後針對以下各項進行測試：(I)各別沉積實驗中之漏鍍性能，及(II)各別填充實驗中之填充性能。Prior to the experiment, each aqueous composition was purged with inert nitrogen for 15 minutes and then tested for: (I) plating performance in separate deposition experiments, and (II) in individual filling experiments Fill performance.

2.1 (I)漏鍍性能(沉積實驗)： 為評估(I)漏鍍性能，使用毯覆式晶圓(不含特徵)作為基板且提供用於每一沉積實驗。在其作用側，每一基板配備有3 nm TaN層(藉由PVD沉積)及該層上之10 nm鈷層(藉由CVD沉積，作為導電晶種層)。2.1 (I) Leakage Plating Performance (Deposition Experiment): To evaluate (I) leakage plating performance, a blanket wafer (without features) was used as a substrate and provided for each deposition experiment. On its active side, each substrate is equipped with a 3 nm TaN layer (deposited by PVD) and a 10 nm cobalt layer on the layer (deposited by CVD as a conductive seed layer).

在每一沉積實驗中，供應電流密度為0.6 A/dm² 之電流以電解沉積鈷沉積物，該層之厚度在220 nm至280 nm範圍內。在每一實驗中，在供應電流的同時，使基板與各別水性組合物接觸大約100秒。在實驗期間，每一組合物之溫度約為22℃。In each deposition experiment, a current having a current density of 0.6 A/dm ^{2 was} supplied to electrolytically deposit a cobalt deposit having a thickness in the range of 220 nm to 280 nm. In each experiment, the substrate was contacted with the respective aqueous composition for approximately 100 seconds while the current was being supplied. The temperature of each composition was about 22 ° C during the experiment.

然後，使用DI水沖洗每一基板並藉由氮氣流乾燥，從而獲得乾燥基板。Then, each substrate was rinsed with DI water and dried by a nitrogen stream to obtain a dried substrate.

藉由目測檢查每一乾燥基板之影像來評估每一乾燥基板之漏鍍性能。使用雷射掃描共焦顯微鏡(Olympus Lext OLS4100)實施成像。由受訓專家來實施目測檢查。The plating performance of each of the dried substrates was evaluated by visual inspection of the image of each of the dried substrates. Imaging was performed using a laser scanning confocal microscope (Olympus Lext OLS4100). Visual inspections are carried out by trained experts.

實例E1至E8之漏鍍性能與使用對比實例C1及C2所獲得之性能相同。在C1、E1、E3、E5及E7中僅觀察到極少表面缺陷(亦即較少不含足夠鈷沉積物之斑點)。在對比實例C2以及實例E2、E4、E6及E8中，表面缺陷之數量略大於C1、E1、E3、E5及E7。該等實例展示，在分別顯著增加化合物X1及式(I)之第一化合物之總濃度時，漏鍍性能有所降低。在對比實例C3及C4中，漏鍍性能最差；表面缺陷之數量顯著高於C2、E2、E4、E6及E8。The plating performance of Examples E1 to E8 was the same as that obtained using Comparative Examples C1 and C2. Only very few surface defects (i.e., spots that are less free of sufficient cobalt deposits) were observed in C1, E1, E3, E5, and E7. In Comparative Example C2 and Examples E2, E4, E6, and E8, the number of surface defects was slightly larger than C1, E1, E3, E5, and E7. These examples show that the plating performance is reduced when the total concentration of the compound X1 and the first compound of the formula (I) is significantly increased, respectively. In Comparative Examples C3 and C4, the plating performance was the worst; the number of surface defects was significantly higher than C2, E2, E4, E6 and E8.

然而，藉由分別利用顯著低於對比實例C1及C2之工作濃度(mmol/L)來獲得實例E1至E8中之結果，但總濃度(以mg/L計)相同。在每一各別本發明實例中，第一化合物之有效工作濃度減小30 mol-%至50 mol-%。若使用炔丙基醇(M=56 g/mol)代替化合物X1，則此效應甚至更為顯著(數據未展示)。因此，上文所提及包括式(I)化合物之本發明組合物之有效性大於對比實例C1及C2之組合物以達成相同結果。However, the results in Examples E1 to E8 were obtained by using working concentrations (mmol/L) which were significantly lower than Comparative Examples C1 and C2, respectively, but the total concentrations (in mg/L) were the same. In each of the individual examples of the invention, the effective working concentration of the first compound is reduced by from 30 mol-% to 50 mol-%. This effect was even more pronounced if propargyl alcohol (M = 56 g/mol) was used instead of compound X1 (data not shown). Thus, the compositions of the invention comprising the compounds of formula (I) mentioned above are more effective than the compositions of Comparative Examples C1 and C2 to achieve the same result.

在實例E9至E14中，另外利用包括複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物。在實例E9、E11及E13中，與對比實例C1及實例E1相比(亦與實例E3、E5及E7相比)，漏鍍性能略有改良。改良意指，漏鍍性能極佳且可觀察到並無顯著表面缺陷。在實例E10、E12及E14中，漏鍍性能與如針對實例E9、E11及E13所獲得者同等良好。因此，聚合物之存在可改良漏鍍性能，尤其在第一化合物以較高總濃度(例如50 mg/L)存在時。In Examples E9 to E14, a polymer comprising a plurality of carboxyguanamine moieties each containing a secondary or tertiary amine nitrogen was additionally utilized. In Examples E9, E11 and E13, the plating performance was slightly improved compared to Comparative Example C1 and Example E1 (also compared to Examples E3, E5 and E7). Improved means that the plating performance is excellent and no significant surface defects are observed. In Examples E10, E12 and E14, the plating performance was as good as those obtained for Examples E9, E11 and E13. Thus, the presence of the polymer improves the plating performance, especially when the first compound is present at a higher total concentration (e.g., 50 mg/L).

2.2 (II)填充性能(填充實驗)： 為評估填充性能，使用晶圓(Empire 1 M1, SUNY Polytechnic Institute)作為基板且提供至每一填充實驗中，每一基板具有3 nm TaN層(藉由PVD沉積)及該層上之4 nm鈷晶種層(藉由CVD沉積)。每一基板在其作用表面上配備有複數個開口尺寸為大約100 nm且深度為大約200 nm之溝槽。2.2 (II) Filling performance (filling experiment): To evaluate the filling performance, wafers (Empire 1 M1, SUNY Polytechnic Institute) were used as substrates and supplied to each filling experiment, each substrate having a 3 nm TaN layer (by PVD deposition) and a 4 nm cobalt seed layer on this layer (deposited by CVD). Each substrate is provided on its active surface with a plurality of grooves having an opening size of about 100 nm and a depth of about 200 nm.

在每一填充實驗中，供應電流密度為0.3 A/dm² 之電流以填充該等溝槽。在供應電流的同時，使每一基板與各別水性組合物接觸大約30秒。在實驗期間，每一組合物之溫度約為22℃。In each of the filling experiments, a current having a current density of 0.3 A/dm ^{2 was} supplied to fill the grooves. Each substrate was brought into contact with the respective aqueous composition for about 30 seconds while supplying current. The temperature of each composition was about 22 ° C during the experiment.

然後，亦使用DI水沖洗每一基板並藉由氮氣流乾燥，從而同樣獲得乾燥基板。Then, each substrate was also rinsed with DI water and dried by a nitrogen stream to thereby obtain a dried substrate.

藉由目測檢查在該大約30秒期間以5秒時間間隔(尤其在10、15、20、25及30秒之後)所獲得之該等經填充溝槽之垂直橫截面，評估每一乾燥基板之填充性能。出於此目的，實施FIB-SEM (FEI Helios Nanolab 450S) (參見各圖)。Each dry substrate was evaluated by visual inspection of the vertical cross-section of the filled trenches obtained at 5 second intervals (especially after 10, 15, 20, 25 and 30 seconds) during the approximately 30 seconds. Fill performance. For this purpose, FIB-SEM (FEI Helios Nanolab 450S) was carried out (see respective figures).

實例E1至E8之填充性能與使用對比實例C1及C2所獲得之性能相同。圖1a及1b展示在30秒(對比實例C1)及20秒 (對比實例C2)之後之經完全填充之溝槽。在實例E1及E2中，獲得相同填充性能(實例E1係在30秒之後且參見圖2a；實例E2係在20秒之後且參見圖2b)。The filling performance of Examples E1 to E8 was the same as that obtained using Comparative Examples C1 and C2. Figures 1a and 1b show fully filled trenches after 30 seconds (Comparative Example C1) and 20 seconds (Comparative Example C2). In Examples E1 and E2, the same fill performance was obtained (Example E1 is after 30 seconds and see Figure 2a; Example E2 is after 20 seconds and see Figure 2b).

然而，除相同填充性能外，利用式(I)化合物獲得如上文在2.1項中所闡述之優點。同樣，包括式(I)化合物之本發明組合物在工作濃度方面之有效性大於對比實例C1及C2之組合物。However, in addition to the same filling properties, the advantages of the compounds of formula (I) as set forth above in Section 2.1 are obtained. Likewise, the compositions of the invention comprising a compound of formula (I) are more effective at working concentrations than the compositions of Comparative Examples C1 and C2.

在包括複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物存在下，填充性能得以進一步改良。在實例E9、E10、E13及E14中，不僅填充溝槽，且亦另外可在溝槽內觀察到顯著自底向上填充。此意味著，可觀察到清洗水平沉積平面。在該等實驗中，溝槽填充始於底部且持續至溝槽開口，由此避免形成不期望空隙。圖3展示如在實例E10中於15秒之後獲得之部分填充之溝槽。該水平沉積平面可明確見於溝槽中。此同樣適用於圖4，其代表根據實例E14之填充(亦在15秒之後)。該自底向上填充較為有益且高度期望以填充具有高縱橫比之無空隙溝槽。因此，包括式(I)之第一化合物及另外具有(i)相對較高分子量及(ii)複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物之本發明組合物具有顯著改良的自底向上填充性能。另外，對比實例C3及C4中SPS之存在並不促進自底向上填充。The filling performance is further improved in the presence of a polymer comprising a plurality of carboxyguanamine moieties each containing a secondary or tertiary amine nitrogen. In Examples E9, E10, E13, and E14, not only the trenches were filled, but also significant bottom-up filling was observed in the trenches. This means that the cleaning level deposition plane can be observed. In these experiments, trench filling begins at the bottom and continues until the trench opening, thereby avoiding the formation of undesirable voids. Figure 3 shows a partially filled trench as obtained after 15 seconds in Example E10. This horizontal deposition plane can be clearly seen in the trench. The same applies to Figure 4, which represents the filling according to Example E14 (also after 15 seconds). This bottom-up filling is beneficial and highly desirable to fill void-free trenches with high aspect ratios. Thus, a composition of the invention comprising a first compound of formula (I) and additionally having (i) a relatively high molecular weight and (ii) a plurality of polymers each containing a secondary or tertiary amine nitrogen carboxamide moiety has Significantly improved bottom-up fill performance. In addition, the presence of SPS in Comparative Examples C3 and C4 did not promote bottom-up filling.

並不展示分別自n = 2且/或R² =甲基及羥基之式(I)化合物獲得之沉積及填充實驗之結果。The results of deposition and packing experiments obtained for compounds of formula (I) from n = 2 and/or R ² = methyl and hydroxy groups, respectively, are not shown.

圖1a係展示在30秒之後自填充實驗C1所獲得溝槽之橫截面之影像(對比實例)。 圖1b係展示在20秒之後自填充實驗C2所獲得溝槽之橫截面之影像(對比實例)。 圖2a係展示在30秒之後自填充實驗E1所獲得溝槽之橫截面之影像(根據本發明)。 圖2b係展示在20秒之後自填充實驗E2所獲得溝槽之橫截面之影像(根據本發明)。 圖3係展示在15秒之後自填充實驗E10所獲得溝槽之橫截面之影像(根據本發明)。 圖4係展示在15秒之後自填充實驗E14所獲得溝槽之橫截面之影像(根據本發明)。Figure 1a shows an image of a cross section of a trench obtained from Filling Experiment C1 after 30 seconds (comparative example). Figure 1b shows an image of a cross section of a trench obtained from Filling Experiment C2 after 20 seconds (comparative example). Figure 2a shows an image of a cross section of a trench obtained from Filling Experiment E1 after 30 seconds (according to the invention). Figure 2b shows an image of a cross section of a trench obtained from Filling Experiment E2 after 20 seconds (according to the invention). Figure 3 is an image showing the cross section of the trench obtained from Filling Experiment E10 after 15 seconds (according to the present invention). Figure 4 is an image showing the cross section of the trench obtained from Filling Experiment E14 after 15 seconds (according to the present invention).

Claims (16)

一種用於沉積鈷沉積物之水性組合物，該組合物包括 (a) 總量之鈷(II)離子， (b) 至少一種式(I)之第一化合物：(I)， 其中獨立地 R¹ 表示H、-NR³ R⁴ 、-OR⁵ 或-CR⁶ R^6’ R⁷ ， R² 表示H、C1至C4烷基、鹵素或OH， n為1、2或3 其中獨立地 R³ 表示H、C1至C4烷基或經由R⁴ 連結至R¹ 中之氮原子之伸烷基部分， R⁴ 表示H、C1至C4烷基或經由R³ 連結至R¹ 中之氮原子之伸烷基部分， R⁵ 表示H或電子對或C1至C4烷基， R⁶ 表示H、C1至C4烷基或經由R⁷ 連結至R¹ 中之碳原子之伸烷基部分， R^6’ 表示H或C1至C4烷基， R⁷ 表示H、C1至C4烷基或經由R⁶ 連結至R¹ 中之碳原子之伸烷基部分， 條件係基於該組合物中之所有過渡金屬陽離子之總重量，該組合物中該總量之該等鈷(II)離子佔該組合物中之所有過渡金屬陽離子之51 wt.-%至100 wt.-%。An aqueous composition for depositing a cobalt deposit, the composition comprising (a) a total amount of cobalt (II) ions, (b) at least one first compound of formula (I): (I), wherein independently R ¹ represents H, -NR ³ R ⁴ , -OR ⁵ or -CR ⁶ R ^6' R ⁷ , R ² represents H, C1 to C4 alkyl, halogen or OH, n is 1. 2 or 3 wherein R ³ independently represents H, C1 to C4 alkyl or an alkyl moiety bonded to the nitrogen atom in R ¹ via R ⁴ , R ⁴ represents H, C1 to C4 alkyl or is bonded via R ³ to The alkyl moiety of the nitrogen atom in R ¹ , R ⁵ represents H or an electron pair or a C1 to C4 alkyl group, and R ⁶ represents an extension of H, a C1 to C4 alkyl group or a carbon atom bonded to R ¹ via R ⁷ An alkyl moiety, R ^{6 '} represents H or a C1 to C4 alkyl group, R ⁷ represents H, a C1 to C4 alkyl group or an alkyl moiety bonded to a carbon atom in R ¹ via R ⁶ , the conditions being based on the composition The total weight of all transition metal cations in the composition, the total amount of such cobalt (II) ions in the composition is from 51 wt.-% to 100 wt.-% of all transition metal cations in the composition. 如請求項1之組合物，其中基於該組合物中之所有過渡金屬陽離子之總重量，該組合物中該等鈷(II)離子之總量佔該組合物中之所有過渡金屬陽離子之80 wt.-%至100 wt.-%、較佳地至少90 wt.-%、更佳地至少95 wt.-%、甚至更佳地至少98 wt.-%、最佳地至少99 wt.-%。The composition of claim 1, wherein the total amount of the cobalt (II) ions in the composition is 80 wt% of all transition metal cations in the composition based on the total weight of all transition metal cations in the composition. .-% to 100 wt.-%, preferably at least 90 wt.-%, more preferably at least 95 wt.-%, even more preferably at least 98 wt.-%, optimally at least 99 wt.-% . 如請求項1或2之組合物，其中該組合物另外包括 (c) 至少一種包括複數個各自含有二級或三級胺氮之羧醯胺部分之聚合物。The composition of claim 1 or 2, wherein the composition additionally comprises (c) at least one polymer comprising a plurality of carboxyguanamine moieties each containing a secondary or tertiary amine nitrogen. 如請求項1或2之組合物，其中在式(I)中，R² 係H且/或n為1。The composition of claim 1 or 2, wherein in formula (I), R ² is H and/or n is 1. 如請求項1或2之組合物，其中式(I)之R² 至R⁷ 中之C1至C4烷基獨立地係甲基或乙基。The composition of claim 1 or 2, wherein the C1 to C4 alkyl groups in R ² to R ⁷ of the formula (I) are independently methyl or ethyl. 如請求項1或2之組合物，其中在式(I)中，該-(CO)-R¹ 部分位於間位。The composition of claim 1 or 2, wherein in the formula (I), the -(CO)-R ¹ moiety is in the meta position. 如請求項1或2之組合物，其中該至少一種式(I)之第一化合物係選自由以下組成之群： The composition of claim 1 or 2, wherein the at least one first compound of formula (I) is selected from the group consisting of: 如請求項1或2之組合物，其中基於該組合物之總體積，該至少一種第一化合物在該組合物中之總濃度在5 mg/L至250 mg/L範圍內、較佳地在7 mg/L至150 mg/L範圍內、更佳地在9 mg/L至90 mg/L範圍內、甚至更佳地在12 mg/L至70 mg/L範圍內。The composition of claim 1 or 2, wherein the total concentration of the at least one first compound in the composition is in the range of 5 mg/L to 250 mg/L, based on the total volume of the composition, preferably It is in the range of 7 mg/L to 150 mg/L, more preferably in the range of 9 mg/L to 90 mg/L, even more preferably in the range of 12 mg/L to 70 mg/L. 如請求項1或2之組合物，其中該至少一種聚合物中之每一者之重量平均分子量M_W 在1 200 g/mol至50 000 000 g/mol範圍內、較佳地在2 000 g/mol至20 000 000 g/mol範圍內、更佳地在3 000 g/mol至8 000 000 g/mol範圍內、甚至更佳地在4 000 g/mol至6 000 000 g/mol範圍內、最佳地在5 000 g/mol至5 000 000 g/mol範圍內。The composition of claim 1 or 2, wherein each of the at least one polymer has a weight average molecular weight M _W in the range of from 1 200 g/mol to 50 000 000 g/mol, preferably 2 000 g In the range from /mol to 20 000 000 g/mol, more preferably in the range from 3 000 g/mol to 8 000 000 g/mol, even more preferably in the range from 4 000 g/mol to 6 000 000 g/mol , preferably in the range of 5 000 g/mol to 5 000 000 g/mol. 如請求項1或2之組合物，其中該等羧醯胺部分獨立地由式(II)代表：(II)， 其中 R⁸ 表示C1至C3烷基或經由R⁹ 連結至式(II)中之該羧醯胺部分之胺氮原子之伸烷基部分， R⁹ 表示氫、C1至C3烷基、該聚合物之主鏈碳原子或經由R⁸ 連結至式(II)中之該羧醯胺部分之羰基碳原子之伸烷基部分，且 R¹⁰ 表示該聚合物之該主鏈之碳原子。The composition of claim 1 or 2, wherein the carboxyguanamine moiety is independently represented by formula (II): (II), wherein R ⁸ represents a C1 to C3 alkyl group or an alkyl moiety of an amine nitrogen atom bonded to the carboxamide moiety of the formula (II) via R ⁹ , and R ⁹ represents hydrogen, C1 to C3 alkyl a main chain carbon atom of the polymer or an alkyl moiety bonded to the carbonyl carbon atom of the carboxyguanamine moiety in the formula (II) via R ⁸ , and R ¹⁰ represents a carbon atom of the main chain of the polymer . 如請求項1或2之組合物，其中該至少一種聚合物係選自由以下組成之群： (IIa) 聚乙烯基吡咯啶酮； (IIb) 聚乙烯基己內醯胺； (IIc) 聚(2-甲基-2-噁唑啉)； (IId) 聚(2-乙基-2-噁唑啉)； (IIe) 聚(N-乙烯基-乙醯胺)；及 (IIf) 聚(N-甲基-N-乙烯基-乙醯胺)。The composition of claim 1 or 2, wherein the at least one polymer is selected from the group consisting of: (IIa) polyvinylpyrrolidone; (IIb) polyvinyl caprolactam; (IIc) poly( 2-methyl-2-oxazoline); (IId) poly(2-ethyl-2-oxazoline); (IIe) poly(N-vinyl-acetamide); and (IIf) poly( N-methyl-N-vinyl-acetamide). 如請求項1或2之組合物，其中基於該組合物之總體積，該至少一種聚合物在該組合物中之總濃度在60 mg/L至1000 mg/L範圍內、較佳地在80 mg/L至800 mg/L範圍內、更佳地在100 mg/L至600 mg/L範圍內、甚至更佳地在150 mg/L至500 mg/L範圍內、最佳地在200 mg/L至400 mg/L範圍內。The composition of claim 1 or 2, wherein the total concentration of the at least one polymer in the composition is in the range of 60 mg/L to 1000 mg/L, preferably 80, based on the total volume of the composition. In the range of mg/L to 800 mg/L, more preferably in the range of 100 mg/L to 600 mg/L, even more preferably in the range of 150 mg/L to 500 mg/L, optimally at 200 mg /L to 400 mg/L. 一種將鈷沉積物電解沉積於基板上之方法，該方法包括以下步驟： (A) 提供該基板， (B) 提供如請求項1至12中任一項之水性組合物， (C) 使該基板與該水性組合物接觸並供應電流，從而將鈷沉積於該基板上以形成該鈷沉積物。A method of electrolytically depositing a cobalt deposit on a substrate, the method comprising the steps of: (A) providing the substrate, (B) providing the aqueous composition according to any one of claims 1 to 12, (C) A substrate is contacted with the aqueous composition and supplied with an electric current to deposit cobalt on the substrate to form the cobalt deposit. 如請求項13之方法，其中該基板在其表面中之至少一者上包括複數個通孔及/或溝槽。The method of claim 13, wherein the substrate comprises a plurality of vias and/or trenches on at least one of its surfaces. 如請求項14之方法，其中在步驟(C)中，該鈷沉積物填充該等通孔及/或溝槽。The method of claim 14, wherein in step (C), the cobalt deposit fills the vias and/or trenches. 一種如請求項1至12中任一項之組合物之用途，其用於沉積鈷沉積物、較佳地用於填充通孔及/或溝槽。Use of a composition according to any one of claims 1 to 12 for depositing cobalt deposits, preferably for filling vias and/or trenches.