TWI683040B - Co anode and Co plating method using Co anode - Google Patents
Co anode and Co plating method using Co anode Download PDFInfo
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Abstract
本發明提供一種新穎的電鍍之陽極，其代替Cu陽極且能抑制鍍覆不良。該陽極係利用硝酸濃度20質量%之稀硝酸溶解之後，利用液體微粒計數器且根據JIS B 9925所測得的、粒徑為0.5 μm以上之微粒之數量為6000個/g以下之Co陽極。The present invention provides a novel electroplated anode that replaces the Cu anode and can suppress poor plating. This anode is a Co anode having a number of particles having a particle size of 0.5 μm or more and measured in accordance with JIS B 9925 using a liquid particle counter and dissolved in dilute nitric acid having a nitric acid concentration of 20% by mass.
Description
本發明係關於一種Co陽極及使用有Co陽極之Co電鍍方法。The invention relates to a Co anode and a Co plating method using the Co anode.
一般而言，Cu電鍍係用於PWB(印刷配線板)等之Cu配線形成，但最近，亦用於半導體之Cu配線形成。作為用於形成Cu配線之Cu電鍍之陽極，可使用純Cu陽極或含磷Cu陽極。Generally speaking, Cu plating is used for the formation of Cu wiring such as PWB (printed wiring board), but recently, it is also used for the formation of Cu wiring for semiconductors. As an anode for Cu plating for forming Cu wiring, a pure Cu anode or a phosphorus-containing Cu anode can be used.
關於Cu電鍍使用之純Cu陽極或含磷Cu陽極，例如記載於專利文獻1中，記載有：藉由將純度控制於規定範圍、且將雜質之含量控制於規定值以下，能抑制微粒附著於使用該純Cu陽極或含磷Cu陽極所製造之半導體晶圓。The pure Cu anode or phosphorous-containing Cu anode used for Cu plating is described in
而且，作為抑制微粒附著於同樣使用含磷Cu陽極所製造之半導體晶圓的技術，專利文獻2中記載有如下技術：當對半導體晶圓進行Cu電鍍時，預先於含磷Cu陽極之表面形成晶粒徑被控制於規定範圍內之微細結晶層。 [先前技術文獻] [專利文獻]Furthermore, as a technique for suppressing the adhesion of fine particles to a semiconductor wafer that is also manufactured using a phosphorous-containing Cu anode, Patent Document 2 describes a technique in which when a semiconductor wafer is subjected to Cu plating, it is formed in advance on the surface of the phosphorous-containing Cu anode A fine crystal layer whose crystal grain size is controlled within a prescribed range. [Prior Art Literature] [Patent Literature]
[專利文獻1]專利第5066577號公報 [專利文獻2]專利第4076751號公報[Patent Document 1] Patent No. 5066577 [Patent Document 2] Patent No. 4076751
[發明所欲解決之問題][Problems to be solved by the invention]
近年來，逐步要求半導體設備之高性能化、低耗電化，且隨著配線之微細化之進步，影響配線之可靠性之電遷移(EM)之劣化對策或導致信號延遲原因之配線電阻之低電阻化成為課題。專利文獻1或專利文獻2中記載之技術如上所述為可藉由抑制利用Cu電鍍形成Cu配線等時產生之微粒而改善鍍覆不良，以獲得有利於微細配線之Cu配線等之技術，但以往此種使用Cu陽極之電鍍中，於EM耐性或配線電阻之低電阻化方面尚有改善餘地。因此，期待開發出代替Cu陽極、且進而能抑制以往之課題即鍍覆不良的新穎的電鍍之陽極。In recent years, higher performance and lower power consumption of semiconductor devices have been gradually demanded. With the progress of miniaturization of wiring, the countermeasures against deterioration of electromigration (EM) that affect the reliability of wiring or wiring resistance that causes signal delay Reducing resistance becomes a problem. The technique described in
因此，本發明之實施形態以提供一種代替Cu陽極且能抑制鍍覆不良的新穎的電鍍之陽極為課題。 [解決問題之技術手段]Therefore, the embodiment of the present invention aims to provide a novel electroplated anode that can replace a Cu anode and can suppress plating defects. [Technical means to solve the problem]
本發明者等人為了解決上述問題進行了多種研究之結果可知，於形成微細配線之技術領域中，著眼窄配線且配線距離相對較短之最前端局部配線等中自Cu更換為Co配線。得知Co配線相對於Cu配線而言EM耐性良好，且當配線距離依阻障金屬層減薄量而變短時，亦能抑制配線電阻低於Cu配線。The inventors of the present invention conducted various studies to solve the above-mentioned problems, and as a result, in the technical field of forming fine wiring, focusing on narrow wiring and relatively short wiring distance, the front-end local wiring and the like are replaced from Cu to Co wiring. It is understood that Co wiring has better EM resistance than Cu wiring, and when the wiring distance becomes shorter depending on the amount of thinning of the barrier metal layer, the wiring resistance can also be suppressed to be lower than that of Cu wiring.
因此發現，藉由代替先前之Cu陽極而製作Co陽極、且控制該Co陽極中之規定之粒徑以上的微粒之數量，可獲得能抑制鍍覆不良之電鍍之陽極。Therefore, it was found that by making a Co anode instead of the previous Cu anode, and controlling the number of particles above a prescribed particle size in the Co anode, an electroplated anode capable of suppressing poor plating can be obtained.
基於上述見解完成之本發明之實施形態之一態樣係一種Co陽極，其利用硝酸濃度20質量%之稀硝酸進行溶解後，利用液體微粒計數器基於JIS B 9925所測得的、粒徑為0.5 μm以上之微粒之數量為6000個/g以下。One aspect of the embodiment of the present invention completed based on the above findings is a Co anode, which is dissolved in dilute nitric acid with a nitric acid concentration of 20% by mass and measured with a liquid particle counter based on JIS B 9925 and having a particle size of 0.5 The number of particles above μm is 6000/g or less.
又，本發明之實施形態之另一態樣係一種使用本發明之實施形態之Co陽極的Co電鍍方法。 [發明之效果]In addition, another aspect of the embodiment of the present invention is a Co plating method using the Co anode of the embodiment of the present invention. [Effect of invention]
根據本發明之實施形態，可提供一種代替Cu陽極且能抑制鍍覆不良的新穎的電鍍之陽極。According to the embodiment of the present invention, it is possible to provide a novel electroplated anode that can replace a Cu anode and can suppress plating defects.
[Co陽極之構成] 作為本發明之實施形態之Co陽極，其於利用硝酸濃度20質量%之稀硝酸溶解之後，利用液體微粒計數器且根據JIS B 9925所測得的、粒徑為0.5 μm以上之微粒之數量為6000個/g以下。Co陽極相對於Cu陽極而言EM耐性良好，且當配線距離依阻障金屬層減薄量而變短時，配線電阻亦能抑制為低於Cu配線。又，因粒徑為0.5 μm以上之微粒之數量控制為6000個/g以下，故而，當使用Co陽極進行電鍍時，能抑制鍍覆之異常析出之發生，結果能良好地抑制鍍覆不良。[Structure of Co anode] As an embodiment of the present invention, the Co anode is dissolved in dilute nitric acid with a nitric acid concentration of 20% by mass and measured with a liquid particle counter in accordance with JIS B 9925 and having a particle size of 0.5 μm or more. The number of particles is below 6000 particles/g. The Co anode has better EM resistance than the Cu anode, and when the wiring distance becomes shorter depending on the amount of thinning of the barrier metal layer, the wiring resistance can also be suppressed to be lower than that of Cu wiring. In addition, since the number of fine particles having a particle diameter of 0.5 μm or more is controlled to 6000 pieces/g or less, when electroplating is performed using a Co anode, the occurrence of abnormal precipitation of the plating can be suppressed, and as a result, plating defects can be suppressed well.
微粒係Co陽極之組織中存在之固體形態之夾雜物，係指於後述之液體微粒計數器之實施過程中不會溶解於稀硝酸之物質。作為Co陽極之雜質，亦包含可溶解於稀硝酸之物質(例如，離子化傾向強之金屬)。然而，此類物質即便以粗大組織之形態存在於Co陽極中，於電鍍過程亦會被離子化，故而，會以離子等級之非常微細之形態被攝入鍍覆膜。另一方面，不會溶解於稀硝酸之夾雜物(微粒)電化學上穩定，故而，維持接近於存在於Co陽極中時之形態而被攝入鍍覆膜中。故而，即便為純度相同的Co陽極，雜質中微粒所占之比例較大之一方中被攝入鍍覆膜之雜質的尺寸會變大，而變得容易發生鍍覆不良。本發明中著眼於此方面，提供一種Co陽極，其控制了不溶解於稀硝酸之作為固體形態之夾雜物的微粒之規定粒徑以上者之數量。The particles are solid inclusions present in the structure of the Co anode, and refer to substances that do not dissolve in dilute nitric acid during the implementation of the liquid particle counter described below. The impurities of the Co anode also include substances soluble in dilute nitric acid (for example, metals with strong ionization tendency). However, even if these substances are present in the Co anode in the form of a coarse structure, they will be ionized during the electroplating process, so they will be taken up into the plating film in a very fine form of ion level. On the other hand, inclusions (fine particles) that do not dissolve in dilute nitric acid are electrochemically stable. Therefore, they are absorbed into the plating film while maintaining a state close to that when they exist in the Co anode. Therefore, even if it is a Co anode having the same purity, the size of the impurities that are taken into the plating film in one of the larger proportions of impurities among the impurities becomes larger, and plating defects are more likely to occur. The present invention focuses on this aspect and provides a Co anode that controls the number of particles that are not dissolved in dilute nitric acid as solid-state inclusions or larger than a predetermined particle size.
微粒主要係因Co原料中所含之雜質、或製造工程中混入之雜質或生成物而引起。微粒例如為選自由金屬、金屬氧化物、碳、碳化合物、氯化合物組成之群組中的一種以上。又，微粒亦可為選自由Fe、Mg、Cr、Ni、Si、Al組成之群組中的一種以上之金屬或其氧化物(亦包括鈷氧化物)。The particles are mainly caused by impurities contained in Co raw materials, or impurities or products mixed in the manufacturing process. The fine particles are, for example, one or more selected from the group consisting of metals, metal oxides, carbon, carbon compounds, and chlorine compounds. Furthermore, the fine particles may be one or more metals selected from the group consisting of Fe, Mg, Cr, Ni, Si, and Al, or oxides thereof (including cobalt oxides).
又，本發明者等人尤其發現，因粒徑為0.5 μm以上之微粒不會溶出於電解液而會被攝入鍍覆膜從而變得容易發生鍍覆之異常析出，故而，著眼於此種粒徑之微粒之個數密度，且藉由將該個數密度控制為6000個/g以下，能極其良好地控制通過電鍍製作之鍍覆膜中之微粒之產生，結果發現，能抑制鍍覆之異常析出之產生。又，對於未檢測出作為微粒之雜質之情況、與檢測出作為微粒之雜質之情況進行比較則發現，檢測出微粒之一方對鍍覆工程造成不良影響、尤其是利用Co陽極形成之Co配線多被用作微細配線，此類不良影響變得顯著，從此種觀點出發，亦控制粒徑為0.5 μm以上之微粒之數量。本發明之實施形態之Co陽極較佳為粒徑為0.5 μm以上之微粒的數量為5000個/g以下，更佳為4000個/g以下。In addition, the inventors have found that particles with a particle diameter of 0.5 μm or more do not dissolve in the electrolyte and can be taken into the plating film, so that abnormal precipitation of the plating is likely to occur. The number density of particles with a particle size, and by controlling the number density to 6000 particles/g or less, the generation of particles in a plating film produced by electroplating can be extremely well controlled. As a result, it was found that the plating can be suppressed The occurrence of abnormal precipitation. In addition, comparing the case where impurities as fine particles were not detected with the case where impurities as fine particles were detected, it was found that one of the particles detected had an adverse effect on the plating process, especially the Co wiring formed by the Co anode When used as a fine wiring, such adverse effects become significant. From this point of view, the number of particles with a particle size of 0.5 μm or more is also controlled. In the Co anode according to the embodiment of the present invention, the number of fine particles having a particle diameter of 0.5 μm or more is preferably 5000 particles/g or less, and more preferably 4000 particles/g or less.
微粒之粒徑可藉由「液體用光散射式自動粒子計數器」(九州RION株式會社製造)測得。該測定法係於液中區分各種尺寸之例子並測定其粒子濃度、粒子數，且係基於JIS B 9925者(本發明中，將該測定稱為「液體微粒計數器」)。 以下，具體說明液體微粒計數器之實施順序，即，採樣1 g，以微粒不溶解之方式利用150 ml之稀硝酸(硝酸濃度20質量%水溶液)緩慢溶解，放置24小時後，進一步對其以純水稀釋為500 ml，並取10 ml，利用上述液體微粒計數器進行測定。例如，當微粒之個數為1000個/ml時，10 ml中測定出0.02 g之樣本，故而微粒為500000個/g。 再者，微粒之個數並不限於利用液體微粒計數器進行測定，只要能測得同樣的個數，亦可使用其他手段測定。The particle diameter of the fine particles can be measured by "light scattering type automatic particle counter for liquid" (manufactured by Kyushu RION Co., Ltd.). This measurement method is an example of distinguishing various sizes in a liquid and measuring the particle concentration and the number of particles, and is based on JIS B 9925 (in the present invention, this measurement is referred to as "liquid particle counter"). The following is a detailed description of the implementation order of the liquid particle counter, that is, sampling 1 g, slowly dissolving with 150 ml of dilute nitric acid (20% by mass nitric acid solution in nitric acid) in such a way that the particles do not dissolve. Dilute with water to 500 ml, and take 10 ml, and use the liquid particle counter to measure. For example, when the number of particles is 1000 particles/ml, a sample of 0.02 g is measured in 10 ml, so the number of particles is 500,000 particles/g. Furthermore, the number of particles is not limited to the measurement using a liquid particle counter, as long as the same number can be measured, it can also be measured by other means.
本發明之實施形態中之Co陽極之純度較佳為3N以上。若Co陽極之純度為3N(純度99.9質量%)以上，則能更良好地抑制藉由使用Co陽極之電鍍而製作之鍍覆膜中的微粒之產生，結果，能更加抑制鍍覆之異常析出之產生。本發明之實施形態之Co陽極之純度更佳為4N(純度99.99質量%)以上，進而更佳為5N(純度99.999質量%)以上。再者，關於本發明中之「純度」，例如純度5N(99.999%)定義為對於溶解後之Co錠利用輝光放電質量分析法(GDMS:Glow Discharge Mass Spectrometry)進行分析，檢測下限以下之元素及Co以外之全部金屬元素、例如Be、Na、Mg、Al、Si、P、S、K、Ca、Ti、V、Cr、Mn、Fe、Ni、Cu、Zn、As、Zr、Mo、Cd、Sn、Sb、Hg、Pb、Bi、Th、U之合計值未達10 ppm。The purity of the Co anode in the embodiment of the present invention is preferably 3N or more. If the purity of the Co anode is 3N (purity 99.9% by mass) or more, the generation of fine particles in the plating film produced by electroplating using the Co anode can be suppressed more, and as a result, abnormal precipitation of plating can be more suppressed Of generation. The purity of the Co anode according to the embodiment of the present invention is more preferably 4N (purity 99.99% by mass) or more, and still more preferably 5N (purity 99.999% by mass) or more. Furthermore, regarding the "purity" in the present invention, for example, the purity of 5N (99.999%) is defined as the analysis of the dissolved Co ingot by glow discharge mass spectrometry (GDMS: Glow Discharge Mass Spectrometry) to detect elements below the lower limit and All metal elements except Co, such as Be, Na, Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Zr, Mo, Cd, The total value of Sn, Sb, Hg, Pb, Bi, Th, U is less than 10 ppm.
再者，如後述之實施例及比較例所示，只要「高純度」則微粒之數量少之關係未必成立，亦存在與純度低之Co陽極相比，純度高之Co陽極中本發明所示之微粒之數量更多的情況。Furthermore, as shown in the examples and comparative examples described later, as long as "high purity", the relationship of the small number of fine particles is not necessarily established, and there are also Co anodes with higher purity compared to Co anodes with lower purity. When the number of particles is larger.
本發明之實施形態之Co陽極較佳為Fe濃度被控制為10 ppm以下。Fe不易溶解於酸性溶液，故而，若Fe混入Co陽極中則變得容易形成微粒。若於同等程度之純度之Co陽極間進行比較，則與Fe濃度超過10 ppm之Co陽極相比，Fe濃度被控制為10 ppm以下之Co陽極一方之鍍覆膜中產生的微粒之數量變得更少，結果，能更加抑制鍍覆之異常析出之產生。本發明之實施形態之Co陽極之Fe濃度被控制為更佳為8 ppm以下，進而更佳為5 ppm以下，進而更佳為3 ppm以下，進而更佳為1 ppm以下，進而更佳為0 ppm。In the Co anode according to the embodiment of the present invention, the Fe concentration is preferably controlled to 10 ppm or less. Fe is not easily dissolved in an acidic solution, so if Fe is mixed into the Co anode, it becomes easy to form fine particles. If the comparison is made between Co anodes of the same degree of purity, the number of particles generated in the plating film of the Co anode with the Fe concentration controlled to 10 ppm or less becomes higher than that of the Co anode with an Fe concentration exceeding 10 ppm. Less, as a result, the occurrence of abnormal precipitation of plating can be more suppressed. The Fe concentration of the Co anode according to the embodiment of the present invention is controlled to be more preferably 8 ppm or less, further preferably 5 ppm or less, still more preferably 3 ppm or less, still more preferably 1 ppm or less, and even more preferably 0 ppm.
[Co陽極之製造方法] 將對本發明之實施形態中之Co陽極之製造方法進行詳細說明。首先，使作為原料之Co於規定容器內熔解。使用之Co原料例如可使用純度3N(純度99.9質量%)以上之Co。 如上文所述，電鍍時成為問題之微粒係Fe、Mg、Cr、Ni、Si、Al等之化合物之粒子，該等粒子是導致鍍覆膜中產生微粒之原因。為了控制該等粒子不會混入Co陽極，亦可控制容器、配管及鑄模中與Co原料接觸之部分之表面粗糙度。又，從該等粒子易浮於熔渣側之見解出發，亦可藉由加長熔液之攪拌時間而使Fe、Mg、Cr、Ni、Si、Al之化合物之粒徑超過0.5 mm的粒子分布到熔渣側。[Manufacturing method of Co anode] The manufacturing method of Co anode in the embodiment of the present invention will be described in detail. First, Co as a raw material is melted in a predetermined container. For the Co raw material used, for example, Co with a purity of 3N (purity of 99.9% by mass) or more can be used. As mentioned above, the particles that are a problem during electroplating are particles of compounds such as Fe, Mg, Cr, Ni, Si, Al, etc. These particles are the cause of particles in the plating film. In order to control that these particles are not mixed into the Co anode, it is also possible to control the surface roughness of the parts in the container, piping and casting mold that are in contact with the Co raw material. In addition, from the view that these particles are easy to float on the slag side, the particle size distribution of the compounds of Fe, Mg, Cr, Ni, Si, and Al can exceed 0.5 mm by increasing the stirring time of the melt To the slag side.
繼而，將已熔解之Co原料供給至鑄模進行鍛造之後，進行軋延、熱處理，進而進行表面切削加工，藉此製作Co陽極。Then, after supplying the melted Co raw material to the casting mold for forging, rolling and heat treatment are performed, and further surface cutting is performed, thereby producing a Co anode.
[Co電鍍方法] 藉由使用本發明之實施形態之Co陽極進行Co電鍍，能極其良好地抑制製作出之鍍覆膜中之微粒之產生，結果，能抑制鍍覆之異常析出之產生。 本發明之實施形態中之Co電鍍方法中，並無特別限制，例如作為鍍覆液，可適量地使用硫酸鈷：10〜30 g/L(Co)、或氯化鈷5〜15 g/L。pH值設為2.5〜3.5。 另外，可設為鍍覆浴溫25〜60℃、陰極電流密度0.5〜10 A/dm 2、陽極電流密度0.5〜10 A/dm 2，但未必需要受限於該等條件。鍍覆浴中亦可包含光澤劑、錯合劑、pH值緩衝劑、界面活性劑等。 [實施例] [Co plating method] By using the Co anode of the embodiment of the present invention for Co plating, the generation of fine particles in the produced plating film can be suppressed extremely well, and as a result, the occurrence of abnormal precipitation of plating can be suppressed. The Co plating method in the embodiment of the present invention is not particularly limited. For example, as the plating solution, an appropriate amount of cobalt sulfate can be used: 10 to 30 g/L (Co), or cobalt chloride 5 to 15 g/L . The pH is set to 2.5~3.5. In addition, the plating bath temperature may be 25 to 60° C., the cathode current density is 0.5 to 10 A/dm 2 , and the anode current density is 0.5 to 10 A/dm 2 , but it is not necessarily limited to these conditions. The plating bath may also contain a gloss agent, a complexing agent, a pH buffer, a surfactant, and the like. [Example]
以下，提供實施例以便更好地理解本發明及其優點，但本發明並不限於該等實施例。In the following, examples are provided to better understand the present invention and its advantages, but the present invention is not limited to these examples.
[Co陽極之製作] 作為實施例1〜5、比較例1，使規定純度之Co原料真空熔解後製成錠並使其熔解。再者，純度為3N之Co原料係使用市售鈷材，純度為4N及5N之Co原料係藉由電解精製而得。 繼而，將已熔解之Co原料供給至鑄模而進行鍛造之後，以30〜50%之軋延率進行軋延，然後以300℃〜600℃進行熱處理，進而進行表面切削加工，藉此製作Co陽極。[Fabrication of Co anode] As Examples 1 to 5 and Comparative Example 1, Co raw materials of predetermined purity were vacuum-melted to make ingots and melted. Furthermore, Co raw materials with a purity of 3N are commercially available cobalt materials, and Co raw materials with a purity of 4N and 5N are obtained by electrolytic purification. Then, after supplying the melted Co raw material to the casting mold and forging, rolling is performed at a rolling rate of 30 to 50%, and then heat treatment is performed at 300 to 600°C, and then surface cutting is performed to produce a Co anode .
[評價] (微粒之評價) 微粒之粒徑及個數係利用「液體用光散射式自動粒子計數器」(九州RION株式會社製造)測定。具體而言，採樣Co陽極1 g，以微粒不溶解之方式利用150 ml之稀硝酸(硝酸濃度20質量%水溶液)緩慢溶解，放置24小時後，進一步對其以純水稀釋為500 ml，並取10 ml，利用上述液體微粒計數器進行測定。將反覆進行上述操作3次後所得之平均值作為微粒之數量。又，微粒之粒徑係利用SEM像進行評價。圖1(a)中表示實施例5(純度：3N；倍率：300倍)之SEM像，(b)中表示實施例3(純度：4N；倍率：300倍)之SEM像，(c)中表示實施例1(純度：5N；倍率：300倍)之SEM像。又，圖2(a)中表示實施例5(純度：3N；倍率：15000倍)之SEM像，(b)中表示實施例3(純度：4N；倍率：30000倍)之SEM像，(c)中表示實施例1(純度：5N；倍率：15000倍)之SEM像。而且，圖1中，粒徑為0.5 μm以上之微粒(夾雜物)係以線框框起來標示。[Evaluation] (Evaluation of microparticles) The particle size and number of microparticles are measured using "light-scattering automatic particle counter for liquids" (manufactured by Kyushu RION Co., Ltd.). Specifically, 1 g of the Co anode was sampled, and 150 ml of dilute nitric acid (a 20% by mass nitric acid solution in nitric acid) was slowly dissolved in a manner that the particles were not dissolved, and after standing for 24 hours, it was further diluted with pure water to 500 ml, and Take 10 ml and measure with the liquid particle counter above. The average value obtained after repeating the above operation three times was taken as the number of fine particles. In addition, the particle diameter of the fine particles was evaluated by SEM image. Fig. 1 (a) shows the SEM image of Example 5 (purity: 3N; magnification: 300 times), (b) shows the SEM image of Example 3 (purity: 4N; magnification: 300 times), (c) The SEM image of Example 1 (purity: 5N; magnification: 300 times) is shown. 2 (a) shows the SEM image of Example 5 (purity: 3N; magnification: 15000 times), (b) shows the SEM image of Example 3 (purity: 4N; magnification: 30,000 times), (c ) Shows the SEM image of Example 1 (purity: 5N; magnification: 15000 times). In addition, in FIG. 1, particles (inclusions) with a particle size of 0.5 μm or more are marked with a wire frame.
(Fe濃度之評價) Co陽極中所含之Fe濃度係藉由GDMS進行評價。又，對測定微粒之粒徑及個數時殘留於過濾器上之微粒成分使用能量分散型X射線分析(EDX：Energy Dispersive X—ray Spectrometry)進行評價。圖3(a)中表示實施例5之EDX光譜圖，(b)中表示實施例3之EDX光譜圖，(c)中表示實施例1之EDX光譜圖。(Evaluation of Fe concentration) The Fe concentration contained in the Co anode was evaluated by GDMS. In addition, the particle components remaining on the filter when measuring the particle size and number of the particles were evaluated using energy dispersive X-ray analysis (EDX: Energy Dispersive X-ray Spectrometry). FIG. 3 (a) shows the EDX spectrum of Example 5, (b) shows the EDX spectrum of Example 3, and (c) shows the EDX spectrum of Example 1.
(異常電沈積之個數之評價) 於直徑300 mm之晶圓(Wafer)上，使用實施例1〜5及比較例1之Co陽極，分別以相同條件進行Co電鍍，形成厚度為10 nm之Co鍍覆膜，對Co鍍覆膜中產生之缺陷之數量(異常電沈積之個數)進行評價。 將以上之各實施例及比較例之結果示於表1。(Evaluation of the number of abnormal electrodepositions) On the wafer with a diameter of 300 mm (Wafer), the Co anodes of Examples 1 to 5 and Comparative Example 1 were used to perform Co electroplating under the same conditions to form a thickness of 10 nm Co plating film, the number of defects (number of abnormal electrodeposition) generated in the Co plating film is evaluated. The results of the above examples and comparative examples are shown in Table 1.
[表1]
(評價結果) 實施例1〜5中，可製作出粒徑為0.5 μm以上之微粒數為6000個/g以下的Co陽極。另一方面，比較例1中，則為粒徑為0.5 μm以上之微粒數超過6000個/g之Co陽極。 又，實施例1與實施例2、實施例3與實施例4、實施例5與比較例1分別使用相同純度之Co陽極，但因Fe濃度不同，故而粒徑為0.5 μm以上之微粒數存在差異。從該結果可知，若純度相同，則Fe濃度小之一方能更加減少粒徑為0.5 μm以上之微粒數。 再者，與純度3N之實施例5相比，純度4N之實施例4之粒徑為0.5 μm以上之微粒數更多。如此，只要「高純度」則微粒之數量少之關係未必成立，亦存在與純度低之Co陽極相比，純度高之Co陽極之一方中本發明所示之微粒之數量更多的情況。 又，使用實施例1〜5之Co陽極形成之Co鍍覆膜，其異常電沈積之個數為0，良好地抑制了鍍覆不良。比較例1之使用Co陽極形成之Co鍍覆膜中發現有異常電沈積，產生鍍覆不良。(Evaluation Results) In Examples 1 to 5, Co anodes with a particle size of 0.5 μm or more and a number of particles of 6000 particles/g or less can be produced. On the other hand, in Comparative Example 1, it is a Co anode having a particle size of 0.5 μm or more and the number of particles exceeding 6000 particles/g. In addition, in Examples 1 and 2, Example 3 and Example 4, Example 5 and Comparative Example 1, Co anodes of the same purity were used, but because the Fe concentration was different, the number of particles with a particle size of 0.5 μm or more existed difference. From this result, it can be seen that if the purity is the same, the smaller the Fe concentration, the smaller the number of fine particles having a particle diameter of 0.5 μm or more. Furthermore, compared with Example 5 with a purity of 3N, Example 4 with a purity of 4N has a larger number of particles with a particle size of 0.5 μm or more. In this way, as long as "high purity", the relationship of a small number of particles may not be established, and there are cases where the number of particles shown in the present invention is greater in one of the high-purity Co anodes than the low-purity Co anodes. Furthermore, the Co plating film formed using the Co anode of Examples 1 to 5 has an abnormal electrodeposition number of 0, which suppresses poor plating well. In the Co plating film formed using the Co anode of Comparative Example 1, abnormal electrodeposition was found, resulting in poor plating.
無no
圖1(a)係實施例5(純度：3N ；倍率：300倍)之SEM像、(b)係實施例3(純度：4N；倍率：300倍)之SEM像，(c)係實施例1(純度：5N；倍率：300倍)之SEM像。 圖2(a)係實施例5(純度：3N；倍率：15000倍)之SEM像，(b)係實施例3(純度：4N；倍率：30000倍)之SEM像，(c)係實施例1(純度：5N；倍率：15000倍)之SEM像。 圖3(a)係實施例5之EDX光譜圖，(b)係實施例3之EDX光譜圖，(c)係實施例1之EDX光譜圖。 Fig. 1 (a) is an SEM image of Example 5 (purity: 3N ; magnification: 300 times), (b) is an SEM image of Example 3 (purity: 4N; magnification: 300 times), (c) is an example 1 (purity: 5N; magnification: 300 times) SEM image. Fig. 2 (a) is an SEM image of Example 5 (purity: 3N; magnification: 15000 times), (b) is an SEM image of Example 3 (purity: 4N; magnification: 30,000 times), (c) is an example 1 (purity: 5N; magnification: 15000 times) SEM image. 3 (a) is the EDX spectrum of Example 5, (b) is the EDX spectrum of Example 3, and (c) is the EDX spectrum of Example 1. FIG.
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| CN103966627A (en) * | 2014-04-30 | 2014-08-06 | 金川集团股份有限公司 | Method for reducing content of impurity Fe in high-purity cobalt |
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| DE19609439A1 (en) * | 1995-03-14 | 1996-09-19 | Japan Energy Corp | Prodn. of pure cobalt@ for sputtering targets for electronics use |
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| DE60142831D1 (en) * | 2000-05-22 | 2010-09-30 | Nippon Mining Co | METHOD FOR PRODUCING METAL OF HIGHER PURITY |
| JP4076751B2 (en) | 2001-10-22 | 2008-04-16 | 日鉱金属株式会社 | Electro-copper plating method, phosphor-containing copper anode for electrolytic copper plating, and semiconductor wafer plated with these and having less particle adhesion |
| AU2002241512A1 (en) * | 2001-11-16 | 2003-06-10 | Honeywell International Inc. | Anodes for electroplating operations, and methods of forming materials over semiconductor substrates |
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| KR101766607B1 (en) * | 2013-12-02 | 2017-08-08 | 제이엑스금속주식회사 | High purity cobalt chloride and manufacturing method therefor |
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