TW202305192A - Control of dissolved gas concentration in electroplating baths - Google Patents
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/02—Tanks; Installations therefor
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/02—Tanks; Installations therefor
- C25D17/04—External supporting frames or structures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/04—Removal of gases or vapours ; Gas or pressure control
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
Description
本揭露整體上係關於電鍍浴中溶解氣體濃度的控制。The present disclosure relates generally to the control of dissolved gas concentrations in electroplating baths.
電化學沉積處理在半導體產業中被廣泛用於積體電路製造的金屬化。電化學沉積處理將例如銅、鈷及鎳的金屬或金屬合金沉積至例如在介電質層中預先形成的溝槽及/或通孔中。在此處理中，薄的附著性金屬擴散-阻障物膜係透過使用物理氣相沉積(PVD)或化學氣相沉積(CVD)而預先沉積至該表面上。接著，通常藉由PVD沉積處理將薄的金屬晶種層沉積在阻障物層的頂部上。接著，經由電化學沉積處理將特徵部(通孔及溝槽)以電化學方式填充金屬或金屬合金；在電化學沉積處理期間，金屬或金屬合金陰離子係被電化學還原成金屬，例如銅陰離子係被電化學還原成銅金屬。Electrochemical deposition processes are widely used in the semiconductor industry for metallization in the manufacture of integrated circuits. Electrochemical deposition processes deposit metals or metal alloys such as copper, cobalt, and nickel into pre-formed trenches and/or vias, such as in the dielectric layer. In this process, a thin adherent metal diffusion-barrier film is pre-deposited onto the surface by using physical vapor deposition (PVD) or chemical vapor deposition (CVD). Next, a thin metal seed layer is deposited on top of the barrier layer, typically by a PVD deposition process. Next, the features (vias and trenches) are electrochemically filled with metal or metal alloy through an electrochemical deposition process; during the electrochemical deposition process, metal or metal alloy anions are electrochemically reduced to metals, such as copper anions The system is electrochemically reduced to copper metal.
本說明書中所描述的標的主體的一或更多實行例的細節係闡述於隨附圖式及下方的實施方式中。其他特徵、態樣及優點將從實施方式、圖式及申請專利範圍而顯而易知。下方的非限制性實行例被視為本揭示的一部分；其他實行例從本揭示的整體及隨附圖式將為顯而易知的。Details of one or more implementations of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects and advantages will be apparent from the implementation, drawings and claims. The following non-limiting implementations are considered part of this disclosure; other implementations will be apparent from this disclosure as a whole and from the accompanying drawings.
在下方敘述中，數具體細節係闡述以提供對所呈現實施例的透徹理解。所揭露實施例可在不具一些或所有這些具體細節的情況下實施。在其他實例中，並未詳細描述習知的處理操作以免不必要地模糊所揭露的實施例。雖然所揭露實施例將結合特定實施例進行描述，但將能理解的是這些特定實施例的用意並非在於限制所揭露的實施例。 定義 In the following description, several specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with specific embodiments, it will be understood that these specific embodiments are not intended to limit the disclosed embodiments. definition
下列術語係在本揭示各處間歇使用：The following terms are used intermittently throughout this disclosure:
「基板」-在本申請案中，術語「半導體晶圓」、「晶圓」、「基板」、「晶圓基板」及「部分製造積體電路」可互換使用。本發明所屬技術領域中具有通常知識者將能理解的是，術語「部分製造積體電路」可指的是在上方進行積體電路製造的許多階段的任何者期間的矽晶圓。在半導體裝置工業中使用的晶圓或基板通常具有200 mm、300 mm或450 mm的直徑。此外，術語「電解質」、「電鍍浴」、「鍍浴」、「浴」、「電鍍溶液」及「鍍溶液」可互換使用。工件可為各種形狀、尺寸及材料。除了半導體晶圓之外，可利用所揭露實施例的其他工件包括各種製品，例如印刷電路板、磁性記錄媒體、磁性記錄感測器、鏡體、光學元件、微機械裝置等。"Substrate" - In this application, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate" and "partially fabricated integrated circuit" are used interchangeably. Those of ordinary skill in the art to which the present invention pertains will understand that the term "partially fabricated integrated circuit" may refer to a silicon wafer upon which any of the many stages of integrated circuit fabrication are performed. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm, 300 mm or 450 mm. Furthermore, the terms "electrolyte", "electroplating bath", "plating bath", "bath", "electroplating solution" and "plating solution" are used interchangeably. Workpieces can be of various shapes, sizes and materials. In addition to semiconductor wafers, other workpieces that may utilize disclosed embodiments include various articles such as printed circuit boards, magnetic recording media, magnetic recording sensors, mirrors, optical components, micromechanical devices, and the like.
「電鍍槽」-為一槽體，通常係配置於容納彼此相對設置的陽極及陰極。電鍍(其發生在電鍍槽中的陰極上)指的是使用電流將溶解的金屬陽離子進行還原，使其在電極上形成薄且連貫的金屬塗層的處理。在某些實施例中，電鍍系統具有二個隔間，一個用於容納陽極，而另一者用於容納陰極。在某些實施例中，陽極腔室及陰極腔室由半透膜所分隔，該半透膜准許離子物種的濃度選擇性移動通過該半透膜。該透膜可為離子交換透膜，例如陽離子交換透膜。對於一些實行例而言，Nafion™的版本(例如，Nafion 324)適合使用作為此種透膜。"Electroplating cell"-a cell, usually configured to house an anode and a cathode positioned opposite each other. Electroplating, which occurs at the cathode in an electroplating bath, refers to the process of using an electric current to reduce dissolved metal cations to form a thin, coherent metal coating on the electrode. In certain embodiments, the electroplating system has two compartments, one for anodes and the other for cathodes. In certain embodiments, the anode and cathode chambers are separated by a semipermeable membrane that permits selective movement of concentrations of ionic species across the semipermeable membrane. The membrane may be an ion exchange membrane, such as a cation exchange membrane. For some implementations, versions of Nafion™ (eg, Nafion 324) are suitable for use as such membranes.
「陽極腔室」-位於電鍍槽內且設置用於容納陽極的腔室。該陽極腔室可包含支撐件，用於固持陽極及/或提供對於陽極的一或更多電性連接。陽極腔室可藉由半透膜而與陰極腔室分隔。在陽極腔室中所容納的電解質有時被稱作陽極電解液。"Anode Chamber" - a chamber located within an electroplating bath and configured to contain an anode. The anode chamber may include supports for holding the anode and/or providing one or more electrical connections to the anode. The anode chamber can be separated from the cathode chamber by a semipermeable membrane. The electrolyte contained in the anode compartment is sometimes referred to as the anolyte.
「陰極腔室」-位於電鍍槽內且設置用於容納陰極的腔室。通常，在本揭露的背景中，陰極為具有複數經部分製造的半導體裝置的基板(例如，晶圓(例如，矽晶圓))。在陰極腔室中所容納的電解質有時被稱作陰極電解液。在許多實行例中，陰極係能夠從陰極腔室移除而允許晶圓與該陰極連接；接著可將該陰極重新引進陰極腔室並浸泡在陰極液中。將能理解的是，陽極腔室及陰極腔室也可指同一整體結構(例如，電鍍槽)的不同部分。若是使用透膜，則透膜可做為二腔室之間的分隔件。"Cathode Chamber" - a chamber located within an electroplating bath and configured to contain a cathode. Generally, in the context of the present disclosure, a cathode is a substrate (eg, a wafer (eg, a silicon wafer)) having a plurality of partially fabricated semiconductor devices. The electrolyte contained in the cathode chamber is sometimes referred to as the catholyte. In many implementations, the cathode system can be removed from the cathode chamber allowing wafers to be attached to the cathode; the cathode can then be reintroduced into the cathode chamber and immersed in catholyte. It will be understood that the anode and cathode chambers may also refer to different portions of the same overall structure (eg, an electroplating cell). If a permeable membrane is used, the permeable membrane can be used as a separator between the two chambers.
「電鍍溶液」(或電鍍浴、電鍍電解質、浴、電鍍溶液、溶液或主要電解質)-解離金屬離子的液體，經常是與導電性增強溶劑(例如，酸或鹼)形成溶液。溶解的陽離子及陰離子均勻分散在溶劑各處。在電性上，此種溶液是中性的。若對於此溶液施加電位，該溶液的陽離子會被吸引至具有大量電子的電極，而陰離子會被吸引致缺乏電子的電極。"Plating solution" (or plating bath, plating electrolyte, bath, plating solution, solution, or primary electrolyte) - a liquid that dissociates metal ions, often in solution with a conductivity enhancing solvent (eg, acid or base). Dissolved cations and anions are uniformly dispersed throughout the solvent. Electrically, this solution is neutral. If an electric potential is applied to this solution, the cations of the solution will be attracted to electrodes with a large number of electrons, and the anions will be attracted to electrodes lacking electrons.
「再循環系統」-將電鍍溶液循環回到中央儲存槽而用於後續再次使用的系統。再循環系統可配置以有效地再次使用電鍍溶液，亦依需求控制及/或保持該溶液內的金屬離子的濃度層級。再循環系統可包括管路或其他流體導管，伴隨著幫浦或驅動再循環的其他機構。 導論及背景 "Recirculation system" - A system that circulates the plating solution back to a central storage tank for subsequent reuse. The recirculation system can be configured to efficiently re-use the plating solution and also control and/or maintain the concentration level of metal ions within the solution as desired. The recirculation system may include tubing or other fluid conduits, along with pumps or other mechanisms to drive recirculation. Introduction and Background
半導體裝置的製造通常需要在半導體晶圓上沉積導電材料。舉例來說，導電材料(例如，銅、鎳及鈷)經常是藉由電鍍而沉積在金屬的晶種層上，其中該金屬的晶種層係藉由各種方法(例如，物理氣相沉積(PVD)或化學氣相沉積(CVD))而沉積至晶圓表面上。電鍍通常使用於在鑲嵌及雙重鑲嵌處理期間將金屬沉積至經處理晶圓的通孔及溝槽中。The fabrication of semiconductor devices often requires the deposition of conductive materials on semiconductor wafers. For example, conductive materials such as copper, nickel, and cobalt are often deposited by electroplating on a seed layer of metal deposited by various methods such as physical vapor deposition ( PVD) or chemical vapor deposition (CVD)) and deposited onto the wafer surface. Electroplating is commonly used to deposit metal into vias and trenches of processed wafers during damascene and dual damascene processing.
電鍍通常是在電鍍浴中執行，其中半導體晶圓是浸沒在電鍍溶液中。電鍍溶液(或溶液、電解液、電鍍浴、電鍍電解質或主要電解質)可被視為解離金屬離子的液體，經常是與導電性增強成分(例如，酸或鹼)形成溶液。溶解的陽離子及陰離子均勻分散在溶劑各處。在電性上，此種溶液是中性的。若對於此溶液施加電位，該溶液的陽離子會被吸引至具有大量電子的電極，而陰離子會被吸引致缺乏電子的電極。Electroplating is typically performed in an electroplating bath, where semiconductor wafers are submerged in an electroplating solution. A plating solution (or solution, electrolyte, plating bath, plating electrolyte, or primary electrolyte) can be considered a liquid that dissociates metal ions, often in solution with a conductivity enhancing component such as an acid or base. Dissolved cations and anions are uniformly dispersed throughout the solvent. Electrically, this solution is neutral. If an electric potential is applied to this solution, the cations of the solution will be attracted to electrodes with a large number of electrons, and the anions will be attracted to electrodes lacking electrons.
電鍍溶液的組成係經選擇以優化電鍍的速率及均勻性。在一些銅電鍍處理期間，銅鹽作為銅陽離子的來源，並且還對提供電鍍溶液提供導電性；在某些實施例中，硫酸藉由提供氫離子作為電荷載體而增強電鍍溶液的導電性。此外，有機添加物(通常在本領域中係習知為促進劑，抑制劑或勻平劑)能夠選擇性增強或抑制例如不同表面及晶圓特徵部上的銅(Cu)沉積速率。The composition of the plating solution is selected to optimize the rate and uniformity of plating. During some copper electroplating processes, copper salts serve as a source of copper cations and also provide conductivity to the plating solution; in certain embodiments, sulfuric acid enhances the conductivity of the plating solution by providing hydrogen ions as charge carriers. In addition, organic additives (often known in the art as accelerators, suppressors or levelers) can selectively enhance or suppress, for example, copper (Cu) deposition rates on various surfaces and wafer features.
某些電鍍溶液使用溶解氣體(例如，氧或氮)以控制電鍍溶液中的各種組份，包括添加物及副產物。舉例而言，一些銅電鍍處理會產生一價銅(Cu
1+)作為副產物，而該Cu
1+可能會對電鍍處理及所得到的晶圓性能產生負面影響。在一些實行例中，Cu
1+為高反應性物種，其為陽極電解的產物，且其與電鍍溶液中的一或更多有機添加物反應而形成該一或更多添加物的還原態。某些有機添加物的還原態與氧化態的反應性不同，而這可能會改變電鍍溶液及所得到的電沉積的效能。然而，在電鍍溶液的溶解氣體的存在下，可控制Cu
1+的存在及效應。舉例來說，溶解氧可經由
各種實行例會控制電鍍溶液中的溶解氣體的濃度，原因在於過多或過少的溶解氣體可能會產生不良效果。舉例來說，在電鍍溶液中具有過多溶解氣體可能會產生形成氣泡(例如，微氣泡)，而氣泡可能會導致晶圓缺陷。在一些實行例中，過多的溶解氣體還可能會對電鍍系統的其他層面造成負面影響，例如造成消耗性電極(包括例如銅陽極)的化學腐蝕。另一方面，過少的溶解氣體可能無法充分控制電鍍溶液中的目標組份。舉例而言，在電鍍溶液中具有過少的溶解氧可能無法將Cu 1+減低至所欲層級。因此，需要將電鍍溶液中的溶解氣體濃度控制在溶液中的「次飽和」濃度(大於0)。次飽和濃度是可在該溶液中溶解額外氣體但不產生氣泡的濃度。在一些實施例中，所欲的次飽和濃度係被稱作中間濃度。 Various practices control the concentration of dissolved gas in the plating solution, since too much or too little dissolved gas may have undesirable effects. For example, having too much dissolved gas in the plating solution may result in the formation of air bubbles (eg, microbubbles), which may cause wafer defects. In some implementations, excess dissolved gas may also negatively impact other levels of the plating system, such as causing chemical corrosion of consumable electrodes including, for example, copper anodes. On the other hand, too little dissolved gas may not adequately control the target components in the plating solution. For example, having too little dissolved oxygen in the plating solution may not reduce Cu 1+ to the desired level. Therefore, it is necessary to control the dissolved gas concentration in the electroplating solution to a "sub-saturation" concentration (greater than 0) in the solution. The subsaturation concentration is the concentration at which additional gas can be dissolved in the solution without generating bubbles. In some embodiments, the desired sub-saturation concentration is referred to as an intermediate concentration.
本文中所描述的是用於控制電鍍溶液中溶解氣體濃度的方法、技術、系統及設備。與電鍍系統流體連接的除氣裝置(例如，接觸器)可用於控制電鍍溶液中的溶解氣體濃度。接觸器內的壓力控制著流經該接觸器的電鍍溶液的溶解氣體濃度，且一些實行例可因此藉由控制該接觸器內的壓力來控制及保持所欲的溶解氣體濃度。此控制可依靠來自除氣裝置中的壓力感測器，及/或判斷電鍍溶液中的溶解氣體濃度的氣體感測器的回饋。在一些實施例中，可藉由對該接觸器選擇性施予真空及/或藉由使用壓力調節器來控制接觸器壓力。在一些實施例中，可控制溶解氣體濃度而用於電鍍槽或系統的不同狀態，例如晶圓是否在電鍍槽內或外，以及例如是否正在執行電鍍，或是系統為閒置的。Described herein are methods, techniques, systems, and apparatus for controlling the concentration of dissolved gases in electroplating solutions. A degassing device (eg, a contactor) fluidly connected to the plating system can be used to control the dissolved gas concentration in the plating solution. The pressure within the contactor controls the dissolved gas concentration of the plating solution flowing through the contactor, and some embodiments may therefore control and maintain a desired dissolved gas concentration by controlling the pressure within the contactor. This control may rely on feedback from pressure sensors in the degassing device, and/or gas sensors that determine the concentration of dissolved gases in the plating solution. In some embodiments, the contactor pressure can be controlled by selectively applying a vacuum to the contactor and/or by using a pressure regulator. In some embodiments, the dissolved gas concentration can be controlled for different states of the plating tank or system, such as whether a wafer is in or out of the plating tank, and whether plating is being performed, or the system is idle, for example.
雖然本文所述的一些實施例關注的是銅電鍍系統及銅電鍍溶液中的溶解氧濃度，但所揭露實施例不限於此系統。這些概念通常適用於控制用於電鍍任何金屬的電解質中的任何溶解氣體的濃度，其中溶解氣體的濃度會對於電鍍的一或更多層面造成影響。所揭露的實施例不限於控制氧作為溶解氣體。實施例可延伸至其他溶解氣體，例如氮。While some embodiments described herein focus on copper electroplating systems and dissolved oxygen concentrations in copper electroplating solutions, the disclosed embodiments are not limited to such systems. These concepts are generally applicable to control the concentration of any dissolved gas in the electrolyte used to plate any metal, where the concentration of dissolved gas affects one or more layers of the plating. The disclosed embodiments are not limited to controlling oxygen as a dissolved gas. Embodiments can be extended to other dissolved gases, such as nitrogen.
可使用各種機構以將電解質內的溶解氣體濃度控制在中間或次飽和層級。 電鍍系統 Various mechanisms can be used to control the dissolved gas concentration within the electrolyte at intermediate or sub-saturated levels. Plating system
本文所述的各種系統及設備能夠控制電鍍溶液中的溶解氣體濃度。圖1繪示出示例電鍍系統100，其具有二個電鍍槽102、用於容納電鍍溶液的儲存槽104，以及電鍍槽流動迴路106，配置以在電鍍槽102與儲存槽104之間流動電鍍溶液。雖然電鍍系統100繪示二個電鍍槽，但一些實施例可具有多於二個電鍍槽，或是僅單一電鍍槽；類似地，一些實施例可能不具有儲存槽。該電鍍系統100還包括除氣裝置(其可為接觸器108)，其經由電鍍槽流動迴路106(例如，按照電鍍溶液流動通過的線)而與電鍍系統流體連接。真空源110連接至接觸器108，且配置以對該接觸器108施予真空。Various systems and devices described herein enable the control of dissolved gas concentrations in plating solutions. 1 depicts an
該除氣裝置(包括接觸器108)係配置以將氣體從在裝置內流動的液體移除。接觸器108的一些實行例可具有疏水性氣體-液體分隔透膜，其中氣體可流動通過該疏水性氣體-液體分隔透膜，而液體無法；且藉由對透膜的一側施予真空同時在該透膜的另一側流動液體，該溶液中的溶解氣體被強迫通過透膜孔洞，並且被真空所帶離。該透膜可具有數百或數千中空纖維以產生大的液體-氣體接觸表面積。藉由在透膜的中空纖維的外側或「殼層側」上流動液體，且對於該透膜的中空纖維的內側或「內腔側」施予真空，該液體中的氣體被迫使通過透膜從殼層側移至內腔側，且藉由該真空而從接觸器中抽除。The degassing device, including the
圖2A繪示出示例接觸器的橫截面圖。接觸器208包括外殼212、流體輸入口214及流體輸出口216、真空埠口218及透膜220，其中該外殼212形成接觸器208的外部，且真空線或真空幫浦可與真空埠口218連接以對於接觸器208施予真空。透膜220(以陰影繪示)可具有圍繞著中央圓柱形或管狀通道(有時稱為採集管222)延伸的大致環形。雖然未顯示於圖2A中，但接觸器208的一些實行例可具有一或更多擋板，所述擋板迫使液體徑向朝外進入透膜220中。當液體228流動通過流體輸入口214且在透膜220的殼層側上流動時(如虛線箭頭228所指示)，在真空埠口處且對於透膜220的內腔側施予真空(由箭頭232所指示)時，該接觸器208可對於其中流動的液體228進行除氣。2A depicts a cross-sectional view of an example contactor. The
圖2B繪示圖2A的接觸器的放大橫截面部分。此處，在殼層側224與內腔側226之間可見到透膜220的部分220A。在對內腔側226施予真空(如箭頭232所指示)時，具有溶解氣體230的液體228在殼層側224上流動。疏水性透膜220對於氣體230是可透的，但液體228並不是，從而造成在施予真空時，在液體228中所溶解的氣體230從殼層側224通過該透膜220中的孔洞234流動至內腔側226。FIG. 2B illustrates an enlarged cross-sectional portion of the contactor of FIG. 2A . Here, a
真空源110可為配置以提供真空的真空幫浦，例如一級或二級機械乾式幫浦及/或渦輪分子幫浦，其可將氣體從接觸器抽除。真空源110可配置以將接觸器中的壓力減低至例如0與2 Atm之間，包括0.1 Atm與1 Atm之間。真空源還可為真空幫浦系統，該真空幫浦系統包括第一粗幫浦、第二粗幫浦及渦輪分子幫浦，該渦輪分子幫浦與第一粗幫浦及第二粗幫浦的其中一者或二者流體連通。真空源110亦可為與一或更多真空幫浦(例如，設施真空件)的氣體管線。The
在一些實行例中，粗幫浦(例如，乾式機械幫浦)可用於將接觸器中的壓力抽低。可使用旋轉爪式幫浦、鼓風幫浦及/或增壓幫浦(有時是組合使用)以提供粗幫浦的功能性。在一些實行例中，隨著接觸器中的壓力降低，可卸下粗幫浦，並且可接上高真空幫浦以進一步將接觸器中的壓力抽低。In some implementations, a coarse pump (eg, a dry mechanical pump) can be used to draw down the pressure in the contactor. Rotary claw pumps, blower pumps, and/or booster pumps (sometimes in combination) may be used to provide the functionality of a coarse pump. In some implementations, as the pressure in the contactor decreases, the coarse pump can be removed and the high vacuum pump can be connected to further draw down the pressure in the contactor.
舉例而言，渦輪分子幫浦或渦輪幫浦，可用於抽空在接觸器中存留的分子-流動狀態氣體。渦輪分子幫浦可包括複數同心且堆疊的轉動渦輪葉片，其與同心的固定渦輪葉片交錯。當渦輪葉片轉動時，他們會對行進至渦輪分子幫浦的喉部中的氣體分子產生撞擊，且被迫使通過渦輪葉片堆疊。渦輪分子幫浦可與下游的粗幫浦串接而協助從接觸器抽空氣體。在一些實行例中，可將相同的一或更多粗幫浦使用作為渦輪分子幫浦下游的粗幫浦，以及作為最初的抽低而使用的粗幫浦。在此實行例中，可將粗幫浦的前級管線配置以能夠例如使用閥而在與接觸器直接連接，以及經由渦輪分子幫浦以與接觸器間接連接之間切換。即使在未使用時，仍可將渦輪分子幫浦保持轉動以在接觸器中抽真空，而所使用的閥系統能夠將渦輪分子幫浦與黏性流狀態的氣體隔絕，其中在此狀態下避免對於渦輪分子幫浦的損害。For example, a turbomolecular pump, or turbopump, can be used to evacuate the molecular-flow state gas trapped in the contactor. A turbomolecular pump may comprise a plurality of concentric and stacked rotating turbine blades interleaved with concentric stationary turbine blades. As the turbine blades turn, they impact gas molecules traveling into the throat of the turbomolecular pump and are forced through the turbine blade stack. A turbomolecular pump can be connected in series with a downstream coarse pump to assist in evacuating gas from the contactor. In some implementations, the same one or more coarse pumps may be used as the coarse pump downstream of the turbomolecular pump, as well as the coarse pump used as the initial pump down. In this implementation, the foreline of the rough pump can be configured to be able to switch between a direct connection to the contactor, for example using a valve, and an indirect connection to the contactor via the turbomolecular pump. Even when not in use, the turbomolecular pump can be kept rotating to draw a vacuum in the contactor, and the valve system used can isolate the turbomolecular pump from the gas in the viscous flow state, which avoids Damage to turbomolecular pumps.
可獨自使用或與其他的高真空幫浦結合使用的高真空幫浦的另一示例為低溫幫浦。低溫幫浦係可被冷卻至非常低溫，以經由冷凝而捕捉氣體及蒸汽的裝置。舉例來說，低溫幫浦可包括藉由使用例如氦或液體氮(或其他合適冷卻機制)而被冷卻的大表面。舉例來說，在腔室中與表面接觸的任何氣體可冷凝在該表面上，接著凍結，據此減低腔室內的自由氣體量(據此減低腔室中的氣體壓力)。低溫幫浦對於捕捉水蒸汽可為特別實用的，雖然低溫幫浦亦可用於捕捉其他氣體。Another example of a high vacuum pump that can be used alone or in combination with other high vacuum pumps is a cryogenic pump. Cryogenic pumps are devices that can be cooled to very low temperatures to capture gases and vapors through condensation. For example, cryopumps may include large surfaces that are cooled using, for example, helium or liquid nitrogen (or other suitable cooling mechanisms). For example, any gas in contact with a surface in the chamber may condense on the surface and then freeze, thereby reducing the amount of free gas in the chamber (and thereby reducing the gas pressure in the chamber). Cryogenic pumps can be particularly useful for capturing water vapor, although cryogenic pumps can also be used to capture other gases.
電鍍系統的額外特徵描述於圖3中，其中圖3繪示圖1的示例系統，伴隨電鍍槽的概略橫截面圖。通常，電鍍系統包括一或更多電鍍槽，而晶圓是在所述電鍍槽進行處理。在圖3中僅顯示一個電鍍槽以保持簡潔。在圖3中，電鍍浴114包含在層面116處顯示的電鍍溶液(其例如具有本文提供的組成)。此容器的陰極液部分適合用於將基板接收在陰極液中。晶圓118係浸泡在電鍍溶液中，並且由安裝在上的「蚌殼式」基板固持件120所固持，其中該可轉動心軸122允許該蚌殼式基板固持件120與該晶圓118一起轉動。Additional features of the electroplating system are depicted in FIG. 3, which depicts the example system of FIG. 1, along with a schematic cross-sectional view of an electroplating tank. Typically, an electroplating system includes one or more electroplating cells in which wafers are processed. Only one plating cell is shown in Figure 3 to keep it simple. In FIG. 3 ,
陽極124係設置在晶圓下方、電鍍浴114內，並藉由電鍍透膜125（較佳為離子選擇透膜）與晶圓區域分隔。舉例來說，可使用Nafion™陽離子交換透膜(CEM)。位於陽極膜下方的區域通常係被稱為「陽極腔室」。離子選擇陽極膜125允許該電鍍槽的陽極區域與陰極區域之間的離子連通，並防止在陽極處產生的微粒進到晶圓的附近而將其汙染。陽極膜還實用於在電鍍處理期間重新分配電流流動，從而改善電鍍均勻性。離子交換透膜(例如，陽離子交換透膜)特別適合用於這些應用。這些膜可由離子聚合性材料所製成，例如含有磺基的全氟化共聚合物（例如，Nafion™）、磺化聚亞胺，以及本發明所屬技術領域中具有通常知識者所習知適合用於陽離子交換的其他材料。合適Nafion™膜的選定示例包括可取得自Dupont de Nemours Co.的N324及N424膜。The
在電鍍期間，來自電鍍溶液的離子沉積於基板上。金屬離子必須擴散通過擴散邊界層，並且進入晶圓的通孔或其他特徵部中。協助擴散的典型方法係透過幫浦126而提供電鍍溶液的對流。另外，可使用振動擾動或音波擾動元件，以及對於均勻電鍍可為有利的晶圓轉動。舉例來說，振動轉換器128可附接至蚌殼式基板固持件120。During electroplating, ions from the electroplating solution are deposited on the substrate. Metal ions must diffuse through the diffusion boundary layer and into vias or other features of the wafer. A typical method of assisting diffusion is to provide convective flow of the plating solution through the
在電鍍期間，電鍍溶液係藉由電鍍槽流動迴路而從儲存槽連續地提供至槽，以及從該槽至該儲存槽，其中該電鍍槽流動迴路可如本文所述地進行操作。如圖3的示例實施例所繪示，電鍍溶液藉由使用幫浦126而從儲存槽104流動至該槽，進入陰極側上的透膜上方的槽，接著朝上流動至晶圓118的中央，並接著徑向朝外流動以遍及晶圓118各處。接著，電鍍溶液溢出電鍍浴114而到達溢流槽132。接著，電鍍溶液流回到儲存槽104，而經由電鍍槽流動迴路106完成電鍍溶液的再循環，而這是由虛線箭頭106而部分表示。During electroplating, electroplating solution is continuously supplied from storage tank to tank, and from the tank to the storage tank, by an electroplating tank flow circuit that can operate as described herein. As shown in the example embodiment of FIG. 3 , the plating solution flows from the
圖3中的電鍍系統100的其他特徵包括參考電極134，該參考電極134位在電鍍浴114的外側上、分離腔室136中，其中該腔室係由來自主電鍍浴114的溢流所補充。或者，在一些實施例中，參考電極的位置盡可能接近基板表面，且該參考電極腔室係透過毛細管或其他方法而連接至晶圓基板的側部，或是直接位於該晶圓基板下方。在一些較佳實施例中，該設備更包括接觸感測引線，該接觸感測引線連接至晶圓周緣，並係配置以感測晶圓周緣處的金屬晶種層的電位，但不承載任何電流至該晶圓。當需要在受控電位下進行電鍍時通常會使用參考電極134。參考電極134可為各種常用類型中的其中一者，例如汞/汞硫酸鹽、銀氯化物、飽和甘汞或銅金屬。除了參考電極之外，在一些實施例中可使用與晶圓118直接接觸的接觸感測引線進行較準確的電位測量（未顯示）。Other features of the
DC電源138可用於控制往晶圓118的電流流動。電源138具有透過一或更多集電環、刷件及接觸件（未顯示）而與晶圓118電性連接的負性輸出引線140；或者，負性輸出引線可與基板固持件120電性連接，而該基板固持件120可因此與該基板連接。電源138的正性輸出引線142係與位在電鍍浴114中的陽極124電性連接。電源138、參考電極134及接觸感測引線（未顯示）可連接至系統控制器144，除其他功能外，該系統控制器144還允許對提供至電鍍槽之元件的電流及電位進行調控。舉例來說，該控制器可允許電位控制狀態及/或電流控制狀態下的電鍍。該控制器可包括程式指令，其中所述程式指令係指定需要施加至電鍍槽的各種元件的電流及電壓位準，以及這些位準需要被改變的時間。當施加順向電流時，電源138將晶圓118進行偏壓使其相對於陽極124具有負電位。這使得電流從陽極124流向晶圓118，並在晶圓表面（陰極）上產生電化學還原反應(例如，
該系統還可包括加熱器152，用於將電鍍溶液的溫度保持在特定層級。電鍍溶液可用於將熱轉移至電鍍浴的其他元件。舉例來說，當將晶圓118輸入電鍍浴中時，可開啟加熱器152及幫浦126使電鍍溶液循環通過電鍍系統100，直到該設備各處的溫度變得實質均勻。在一實施例中，加熱器係連接至系統控制器144。系統控制器144可連接至熱電耦，以接收在該電鍍設備內的電鍍溶液溫度的回饋，並判斷額外加熱的需求。The system may also include a
控制器通常將包括一或更多記憶裝置及一或更多處理器。處理器可包括CPU或電腦、類比及/或數位輸入/輸出連接件、步進馬達控制器板等。在某些實施例中，控制器控制著電鍍設備的所有活動。包含用於根據本實施例而控制處理操作的指令的非瞬態機器可讀媒體可與系統控制器耦接。A controller will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and/or digital input/output connections, a stepper motor controller board, and the like. In some embodiments, a controller controls all activities of the electroplating facility. A non-transitory machine-readable medium containing instructions for controlling processing operations according to the present embodiments may be coupled to the system controller.
通常將存在與控制器144相關的使用者介面。使用者介面可包括顯示螢幕、該設備及/或處理狀態的圖形化軟體顯示器，以及例如指向裝置、鍵盤、顯示螢幕、麥克風等使用者輸入裝置。用於控制電鍍處理的電腦程式編碼可被編寫於任何習知的電腦可讀編程語言中：例如組合語言、C、C++、Pascal、Fortran等。編譯物件編碼或腳本係藉由處理器加以執行，以執行該程式中所認證的任務。可根據本文中的實施例而使用的電鍍設備的一示例為Lam Research Sabre工具。電沉積可在複數構件中進行，而該等構件形成一較大的電沉積設備。Typically there will be a user interface associated with the
圖3的系統100還包括接觸器108及真空源110。該接觸器108流體連接至電鍍系統100，使得電鍍溶液可流動通過接觸器108。這可包括將接觸器的位置設置成沿著電鍍槽流動迴路106(如圖3所繪示)，或是設置成平行於再循環迴路，如描述於下。The
本文所述的電鍍系統得以各種方式實施，以控制電鍍溶液中溶解氣體濃度的。圖4繪示另一電鍍系統400，其包括複數電鍍槽402、儲存槽404、電鍍槽流動迴路406、接觸器408、真空源410及控制器444。這些特徵可與上述圖1及3的電鍍槽102、儲存槽104、電鍍槽流動迴路106、接觸器108、真空源110及控制器144的特徵相同。The electroplating systems described herein can be implemented in various ways to control the concentration of dissolved gases in the electroplating solution. FIG. 4 illustrates another
此處，在系統400中，在接觸器408與真空源410之間包括閥460，且該閥460係配置以控制對於接觸器408的真空施加。在一些實行例中，閥460可配置以完全開啟，從而允許通過該閥的最大流動量；完全關閉，而不允許任何流動通過該閥；或是複數部分開啟配置，以允許通過該閥的不同流動量。閥460還連接至系統控制器444，其中該系統控制器444是配置以控制閥460的操作，例如使其完全開啟、部分開啟，或是關閉。藉由控制閥460的操作，控制器444能夠控制對於接觸器408的真空施加、控制接觸器408的除氣，以及控制電鍍溶液中的溶解氣體濃度。Here, in
系統400還可包括一或更多感測器，所述感測器係連接至控制器444，且用於提供控制接觸器408的操作(例如，閥460的操作，以及對於接觸器408的真空源410施加)所用的回饋。在一些實行例中，系統400可包括一或更多氣體感測器462，配置以偵測及/或判斷電鍍溶液內的氣體的濃度。該等氣體感測器462可位於系統400內的各種位置中，例如在該等電鍍槽402的其中一或更多者(包括該槽的電鍍浴(圖3中的114))中、在儲存槽404中、在溢流槽(圖3中的132)中，及/或在系統400的流動元件(例如，管路、管線或幫浦)內。對於一些電鍍操作及/或狀態，測量電鍍槽及儲存槽二者中的氣體濃度可為有優勢的。這可包括當電鍍槽容積及浴容積是不成比例的及/或若在電鍍槽與浴之間的溶解氣體濃度存在明顯變化。
氣體感測器係配置以偵測電鍍中的一或更多氣體，例如氧或氮。此種氣體感測器一些示例包括與酸可相容的不鏽鋼壓力感測器。如更詳細描述於下，直接偵測及測量電鍍溶液中的氣體濃度能夠控制對接觸器所施加的真空，以及該接觸器所造成的除氣，以控制電鍍溶液中的溶解氣體的濃度。The gas sensor is configured to detect one or more gases, such as oxygen or nitrogen, in the electroplating. Some examples of such gas sensors include acid compatible stainless steel pressure sensors. As described in more detail below, direct detection and measurement of the gas concentration in the plating solution enables control of the vacuum applied to the contactor, and the outgassing caused by the contactor, to control the concentration of dissolved gas in the plating solution.
系統還可包括一或更多壓力感測器464，配置以測量接觸器408內的壓力。該控制器444係連接至該一或更多壓力感測器464，且配置以接收該一或更多壓力感測器464產生的壓力數據。接觸器中的壓力偵測及測量可被使用作為電鍍溶液中的溶解氣體濃度的替代物或替代品，且能夠控制電鍍溶液中的溶解氣體濃度。在一些實行例中，接觸器中的壓力與溶解氣體濃度具有正相關性，使得提高接觸器壓力會使溶解氣體濃度增加，而降低接觸器壓力會使溶解氣體濃度下降。在一些實例中，如圖5所繪示，接觸器壓力及溶解氣體濃度可具有線性或實質線性(例如，在85%線性內)關係，其中圖5繪示所量測的溶解氧對上接觸器壓力的圖表。圖5的數據係在測量電鍍溶液中的接觸器壓力及溶解氧的實驗中加以蒐集。如圖可見，提高接觸器壓力會使溶解氣體濃度增加，而接觸器壓力與溶解氣體濃度之間的關係接近或實質為線性的，並且還遵循正相關性。The system may also include one or
請參照回到圖4，可藉由控制閥460操作來控制接觸器408。舉例來說，藉由關閉該閥460且避免對接觸器408施加真空，或是藉由部分關閉該閥460(其亦可被視為部分開啟狀態)且降低通過該閥460的可允許流動，可提高接觸器408壓力。這可包括將閥460從完全開啟轉變至完全關閉狀態、從完全開啟位置轉變至部分開啟狀態、從一部分開啟狀態轉變至較低的部分開啟狀態，或是從部分開啟狀態轉變至完全關閉。藉由將閥460開啟至完全開啟且對接觸器408施加真空，或是提高通過該閥460的可允許流動並增加對於接觸器408的真空施加，可降低該接觸器408壓力。這可包括將閥460從完全關閉轉變至部分開啟狀態、從一部分開啟狀態轉變至較多的部分開啟狀態、從部分開啟狀態轉變至完全開啟，或是從完全關閉狀態轉變至完全開啟狀態。Referring back to FIG. 4 , the
在一些實行例中，可利用壓力調節器控制接觸器壓力。壓力調節器配置以藉由調整對接觸器施加的真空量，以及使接觸器透膜在殼層側上內的液體與內腔側上的真空之間保持平衡，而保持接觸器內的恆定壓力或實質恆定壓力(例如，15%內)。保持恆定或實質恆定的接觸器壓力導致恆定或實質恆定的流出該接觸器的液體的溶解氣體濃度。舉例來說，請參照回到圖5，將接觸器壓力保持在所列壓力的其中一者(例如，點A)使電鍍溶液中的溶解氧濃度保持在特定的相應值，例如圖5中的點B。由於接觸器在殼層側上內的液體與內腔側之間保持平衡的能力，故上述可保持為真，無論進入該接觸器的液體的溶解氣體濃度超過所欲濃度多高。壓力調節器所固定至的壓力(即，設定壓力)可在執行電鍍之前加以決定及設定。In some implementations, the contactor pressure can be controlled using a pressure regulator. The pressure regulator is configured to maintain a constant pressure within the contactor by adjusting the amount of vacuum applied to the contactor and maintaining a balance between the liquid in the contactor membrane on the shell side and the vacuum on the lumen side Or substantially constant pressure (eg, within 15%). Maintaining a constant or substantially constant contactor pressure results in a constant or substantially constant dissolved gas concentration of the liquid exiting the contactor. For example, referring back to FIG. 5, maintaining the contactor pressure at one of the listed pressures (e.g., point A) maintains the dissolved oxygen concentration in the plating solution at a specific corresponding value, such as Point B. Because of the contactor's ability to maintain equilibrium between the liquid in the shell side and the lumen side, the above holds true no matter how high the dissolved gas concentration of the liquid entering the contactor exceeds the desired concentration. The pressure to which the pressure regulator is fixed (ie, the set pressure) can be decided and set before electroplating is performed.
具有壓力調節器的電鍍系統示例顯示於圖6A及6B中，其各者繪示另一示例電鍍系統600，該電鍍系統600包括複數電鍍槽602、儲存槽604、電鍍槽流動迴路606、接觸器608及真空源610。這些特徵可與上述圖1及3的電鍍槽102、儲存槽104、電鍍槽流動迴路106、接觸器108及真空源110的特徵相同。此處，壓力調節器666係用於控制對於接觸器的真空施加。在圖6A中，離開電鍍槽102的液體在進入儲存槽604之前先通過接觸器108。有時可將此位置稱為「返回」線路的一部分。在圖6B中，離開儲存槽604的液體在進入電鍍槽102之前先進入接觸器108。有時可將此位置稱為「供給」線路的一部分。如上方提供的，使用壓力調節器將接觸器保持恆定或實質恆定壓力會導致恆定或實質恆定的流出該接觸器的液體的溶解氣體濃度。An example of an electroplating system with a pressure regulator is shown in FIGS. 6A and 6B , each of which depicts another
在一些實行例中，可能會將壓力調節器暴露至電鍍溶液，這可能會導致金屬鹽及/或酸堆積在調節器中，而可能使其失靈。這可能會因為其中一些電鍍溶液可能會滲透過該透膜並行進至調節器而發生。許多壓力調節器無法承受對於腐蝕性電鍍溶液的暴露。藉由添加液體捕捉器來保護壓力調節器可避免此暴露；而在一些實例中，這可能需要硬體來感測捕捉層級、排乾捕捉器，以及監測調節器的使用期限。這些特徵部可被包括在使用壓力調節器的一些電鍍系統中。In some implementations, the pressure regulator may be exposed to the plating solution, which may cause metal salts and/or acids to build up in the regulator, possibly causing it to fail. This may occur because some of the plating solution may permeate through the membrane and travel to the regulator. Many pressure regulators cannot withstand exposure to corrosive plating solutions. This exposure can be avoided by adding a liquid trap to protect the pressure regulator; and in some instances, this may require hardware to sense the level of trap, drain the trap, and monitor the age of the regulator. These features may be included in some electroplating systems that use pressure regulators.
另一個電鍍系統的實行例可將接觸器的位置設置在與電鍍槽流動迴路平行，使得流體同時流動通過電鍍槽流動迴路及接觸器二者。在一些如此的實行例中，可對接觸器持續施加真空，使該接觸器的溶解氣體移除速率恆定。通過該接觸器的流率可因此影響被流動通過該接觸器的電鍍溶液的所致溶解氣體濃度。舉例而言，流體越慢流動通過該接觸器伴隨恆定的溶解氣體移除速率，則將會從該流體移除越多的溶解氣體，且電鍍流體的所致溶解氣體濃度越低。相反地，流體越快流動通過該接觸器伴隨恆定的溶解氣體移除速率，則將會從電鍍溶液移除越少的溶解氣體。因此，與低流率的情況期間(例如，在系統閒置期間)相比，在高流率的情況期間(例如，在電鍍期間)可從溶液移除較少的溶解氣體。Another electroplating system implementation may position the contactor parallel to the plating tank flow circuit such that fluid flows through both the plating tank flow circuit and the contactor simultaneously. In some such implementations, vacuum can be continuously applied to the contactor such that the rate of dissolved gas removal from the contactor is constant. The flow rate through the contactor can thus affect the resulting dissolved gas concentration of the plating solution being flowed through the contactor. For example, the slower the fluid flows through the contactor with a constant dissolved gas removal rate, the more dissolved gas will be removed from the fluid and the lower the resulting dissolved gas concentration of the plating fluid. Conversely, the faster the fluid flows through the contactor with a constant dissolved gas removal rate, the less dissolved gas will be removed from the plating solution. Thus, less dissolved gas may be removed from the solution during high flow rate conditions (eg, during electroplating) than during low flow rate conditions (eg, during system idle).
這繪示於圖7A及7B中，其各者繪示又另一示例電鍍系統700，該電鍍系統700包括複數電鍍槽702、儲存槽704、電鍍槽流動迴路706、接觸器708及真空源710。這些特徵部可與上述圖1及3的電鍍槽102、儲存槽104、電鍍槽流動迴路106、接觸器108及真空源110的特徵相同。此處，接觸器708與電鍍槽流動迴路706平行設置，使流體可同時流動通過接觸器708及電鍍槽流動迴路706。在圖7A中，接觸器708的位置與返回線路平行，而在圖7B中，接觸器708的位置與供給線路平行。在一些實行例中，真空源710流體連接至接觸器708，且對於接觸器708的真空源710施加可為恆定的或任選地如上述由控制閥760所控制。圖7C繪示另一示例電鍍系統700，其包括圖7A及7B中顯示的特徵。此處，接觸器708未經由供給線路或返回線路的任一者而直接連接至電鍍槽流動迴路706。反而，接觸器708僅連接至儲存槽704以控制儲存槽704中的氧濃度。換言之，接觸器708的輸入口線及輸出口線均連接至儲存槽704。This is depicted in FIGS. 7A and 7B , each of which depicts yet another
在一些實施例中，得以各種方式控制通過接觸器708的流率，例如利用限流器進行固定或可調控制，其中該限流器可***置及調整，或是利用控制閥761及基於使用上方提供的一或更多感測器(例如，氣體感測器762)所測量的系統700中的溶解氣體濃度的回饋控制而進行主動控制。雖然未顯示於圖7A-7C中，但該回饋控制可由控制器實施，該控制器可接收感測器數據、判斷通過接觸器的經調整流率，以及控制該控制閥761而改變(例如，提高或降低)通過接觸器的流動。舉例而言，若溶解氣體濃度高於所欲值，則該控制器可控制閥使該溶液通過接觸器的流動減慢，從而從該溶液移除較多的溶解氣體。In some embodiments, the flow rate through
接觸器可位於電鍍系統內的各種位置中。這可包括例如插置於圖1及3、4、6A及7A中所示的電鍍槽與儲存槽之間。接觸器還可直接流體連接至圖7C所示的儲存槽、一或更多槽，或是位於電鍍槽流動迴路的不同位置內，例如在圖6B及7B所示的儲存槽後。 控制溶解氣體濃度的技術 Contactors may be located in various locations within the electroplating system. This may include, for example, interposition between the plating tank and the storage tank shown in Figures 1 and 3, 4, 6A and 7A. The contactor can also be directly fluidly connected to the storage tank shown in Figure 7C, one or more tanks, or located in a different location in the plating tank flow circuit, such as after the storage tank shown in Figures 6B and 7B. Techniques for Controlling Dissolved Gas Concentrations
本文所述的各種技術是用於控制及維持電鍍溶液中的溶解氣體濃度，包括依靠回饋的一些技術，而其他不依靠回饋。圖8繪示用於控制電鍍溶液中的溶解氣體濃度的第一技術。此實施例可使用上方提供的系統(包括圖4的系統400)而實施。在第一技術的方格801中，將電鍍溶液流入本文所述的接觸器中。這可包括使用一或更多幫浦(例如，圖3中的幫浦126)以將該溶液推或拉通過接觸器。在一些實例中，該電鍍溶液是從槽流入接觸器；而在使用儲存槽的一些其他實施例中，電鍍溶液可從儲存槽流入接觸器。Various techniques are described herein for controlling and maintaining the dissolved gas concentration in the plating solution, including some that rely on feedback and others that do not. Figure 8 depicts a first technique for controlling the dissolved gas concentration in an electroplating solution. This embodiment may be implemented using the systems provided above, including
在方格803中，控制接觸器中的壓力，使電鍍溶液中的溶解氣體濃度被保持在第一範圍內。在一些實行例中，此壓力控制包括藉由在所欲壓力範圍內將接觸器壓力提高或降低來調整該接觸器壓力，這因此將溶解氣體濃度保持在所欲濃度範圍內。舉例而言，如提供於上方且繪示於圖5中，接觸器內的壓力可與溶解氣體濃度具有正相關性，使得提高接觸器壓力會使溶解氣體濃度增加，而降低接觸器壓力會使溶解氣體濃度減少。方格803的控制可因此包括提高接觸器壓力以增加溶解氣體濃度，以及降低接觸器壓力以減少溶解氣體濃度。在一些其他實行例中，該控制可包括使用壓力調節器來控制接觸器中的壓力，例如利用圖6A及6B中的壓力調節器666。In
如本文提供，可藉由對接觸器施予真空來降低接觸器壓力，以及藉由停止供應真空並持續流動電鍍溶液通過接觸器來提高接觸器壓力。在一些實行例中，可藉由例如打開接觸器與真空源之間的閥(例如，圖4中的系統400的控制閥460)而將真空源連接至接觸器，及/或將與接觸器流體連接的真空源的真空幫浦開啟，從而施予該真空。在一些實例中，所施予的真空可配置以將接觸器中的壓力減低至例如0與2 Atm之間，包括0.2 Atm與1 Atm之間。As provided herein, the contactor pressure can be decreased by applying a vacuum to the contactor, and the contactor pressure can be increased by stopping the supply of vacuum and continuing to flow the plating solution through the contactor. In some implementations, the vacuum source can be connected to the contactor by, for example, opening a valve between the contactor and the vacuum source (e.g.,
在一些實施例中，可重複提高及降低接觸器壓力，以將該接觸器壓力保持在所欲壓力範圍內，並因此將溶解氣體濃度保持在所欲濃度範圍內。舉例而言，在已藉由降低接觸器壓力而減低溶解氣體濃度後，可由於電鍍系統的本質(例如，在該系統中執行的各種操作、晶圓是否位於電鍍槽中，以及電鍍溶液的溶解氣體攝取)而再次提高溶解氣體濃度。該接觸器是用於移除此溶解氣體濃度的其中一些，但這些各種操作及狀態仍然會使氣體被加回到該溶液中。因此，得以一或更多頻率將電鍍溶液的溶解氣體濃度重複或循環提高及降低。In some embodiments, increasing and decreasing the contactor pressure may be repeated to maintain the contactor pressure within a desired pressure range, and thus maintain the dissolved gas concentration within a desired concentration range. For example, after the dissolved gas concentration has been reduced by lowering the contactor pressure, it may be due to the nature of the plating system (e.g., the various operations performed in the system, whether the wafer is in the plating tank, and the dissolution of the plating solution) gas uptake) to increase the dissolved gas concentration again. The contactor is used to remove some of this dissolved gas concentration, but these various operations and conditions still cause gas to be added back into the solution. Thus, the dissolved gas concentration of the plating solution can be increased and decreased repeatedly or cycled at one or more frequencies.
此概念是利用圖9而繪示，其中圖9繪示在一段時間內的溶解氣體濃度及接觸器壓力的圖表。此處，執行一實驗，在該實驗中測量一段時間週期內的電鍍系統的溶解氧濃度及接觸器壓力。虛線代表接觸器壓力，而實線代表溶解氧濃度。如圖可見，將接觸器壓力控制(或保持)特定壓力範圍內(例如，介於約P1 Atm與約P2 Atm之間)會使溶解氧濃度保持在特定濃度範圍內(例如，介於約C1 ppm與約C2 ppm之間)。當接觸器壓力到達上閾值(即，約為P1 Atm)時，藉由對接觸器施予真空而降低接觸器壓力，直到接觸器壓力到達下閾值(即，約為P2 Atm)，接著在此下閾值時停止對接觸器施予真空以允許接觸器壓力增加，從而將接觸器壓力控制在此範圍內。當接觸器壓力再次達到上限時，可將此步驟重複進行。This concept is illustrated using Figure 9, which shows a graph of dissolved gas concentration and contactor pressure over a period of time. Here, an experiment was performed in which the dissolved oxygen concentration and contactor pressure of the electroplating system were measured over a period of time. The dashed line represents the contactor pressure, while the solid line represents the dissolved oxygen concentration. As can be seen, controlling (or maintaining) the contactor pressure within a specific pressure range (e.g., between about P1 Atm and about P2 Atm) will maintain the dissolved oxygen concentration within a specific concentration range (e.g., between about C1 Atm ppm and about C2 ppm). When the contactor pressure reaches the upper threshold (i.e., approximately P1 Atm), the contactor pressure is reduced by applying a vacuum to the contactor until the contactor pressure reaches the lower threshold (i.e., approximately P2 Atm), then at The contactor pressure is controlled within this range by stopping vacuum to the contactor at the lower threshold to allow the contactor pressure to increase. This step can be repeated when the contactor pressure reaches the upper limit again.
更具體而言，在圖9中，在時間0時並未對接觸器施予真空，因此接觸器壓力能夠隨著流體流動通過接觸器且在電鍍系統內流動而增加。舉例來說，這可藉由將圖4中的控制閥460關閉而實現。在時間t1處，接觸器壓力已到達所欲壓力範圍的上限。因為此原因，在時間t1處對接觸器施予真空，而在時間t2處壓力從約P1 Atm降至約P2 Atm，其可為所欲壓力範圍的下閾值。這種接觸器壓力的減低可藉由將圖4中的控制閥460打開以例如對接觸器408施加真空源410而達成。在到達時間t2及下壓力閾值後，停止施加真空，其可透過關閉控制閥460而完成。在時間t1與t2之間，隨著壓力降低，溶解氧濃度也從約C3 ppm下降至約C4 ppm。在時間t2與t3之間，並未對接觸器施予真空，接觸器壓力可隨著電鍍流體流動通過該接觸器而增加，這也造成電鍍溶液中的溶解氧濃度增加。在時間t3處，壓力再次如時間t1時到達上限，並且對接觸器施予真空源直到時間t4，在時間t4時停止施加真空。這使溶解氧濃度再次降低。圖9繪示藉由將接觸器壓力控制在所欲壓力範圍內，可將溶解氣體濃度保持在所欲濃度範圍內。在此示例中，重複施予真空及停止施予真空保持著該所欲濃度及壓力範圍。More specifically, in FIG. 9, at time 0, no vacuum is applied to the contactor, so the contactor pressure can increase as fluid flows through the contactor and within the plating system. This can be achieved, for example, by closing
藉由重複提高及降低接觸器壓力來控制接觸器壓力係進一步繪示於圖10中，其中圖10繪示用於控制電鍍溶液中的溶解氣體濃度的第二示例技術。方格1001與801相同。方格1003藉由執行方格1003A及1005B來控制接觸器壓力；這三個方格1003、1003A及1003B可共同被視為控制接觸器壓力。在方格1003A中，對接觸器施予真空，這使接觸器壓力降低，並且使溶解氣體濃度降低。如圖9所繪示，舉例來說，當壓力到達上閾值時，可在時間t1處發生此壓力降低，且此壓力降低可持續發生直到該接觸器壓力到達下閾值。該真空得以本文提供的任何方式進行施予，包括圖4實施例的打開控制閥460以對接觸器408施予真空源410。在方格1003B中，停止對接觸器施予真空，而流體可持續流動通過接觸器，從而允許壓力提高並進一步使溶解氣體濃度增加。真空的施加得以本文提供的任何方式來停止，包括圖4實施例的關閉控制閥460或關閉真空源410。Controlling the contactor pressure by repeatedly increasing and decreasing the contactor pressure is further illustrated in FIG. 10 , which illustrates a second example technique for controlling the concentration of dissolved gases in the plating solution. Square 1001 is the same as 801.
在方格1003B後，可再次重複進行方格1003A及1003B。藉由重複對接觸器施予真空以及停止對接觸器施予真空來重複提高及降低接觸器中的壓力，從而將溶解氣體的濃度控制及保持第一範圍內。這可使接觸器壓力在在二壓力之間調整。舉例來說，在第一接觸器壓力時，對接觸器施予真空以將接觸器壓力降低至第二接觸器壓力，而在此時將停止該真空施加，且該接觸器壓力將會再次升至該第一接觸器壓力。此循環可重複進行並且可使溶解氣體濃度在該範圍內提高及降低(考量本文所述的壓力與溶解氣體之間的相關性)。After square 1003B,
可基於各種因素及考量而以不同頻率重複進行方格1003A及1003B。舉例而言，電鍍溶液的溶解氣體濃度可被位在槽內的晶圓所影響，原因在於各個槽在該槽內具有大的電鍍溶液的表面區域，其中該表面區域在晶圓位於槽中時被該晶圓覆蓋，而在晶圓不位於槽中時暴露至環境。暴露至環境的電鍍溶液的表面區域越多，則該電鍍溶液所攝取的氣體就越高且越快速，並造成較高的溶解氣體濃度。相反的，暴露至環境的表面積越少，則發生越少的氣體攝取。由於此原因，與晶圓位於槽中時相比，當晶圓不位於槽中時溶解氣體濃度得以較大速率增加。
本文提供的技術可配置以負責改變氣體攝取速率，包括基於晶圓是否位於電鍍槽中的那些速率。在一些實施例中，施加或不施加真空的頻率當晶圓位於槽中時可為一頻率，而當晶圓不位於槽中時可為不同頻率。在與晶圓位於槽中時相比，當晶圓不位於槽中時的氣體攝取處於較大速率時，在晶圓不位於槽中時執行真空施加及停止真空施加的頻率可高於當該晶圓位於槽中時的頻率。The techniques provided herein can be configured to account for varying gas uptake rates, including those based on whether a wafer is in the plating bath or not. In some embodiments, the frequency at which vacuum is applied or not applied may be one frequency when the wafer is in the slot, and may be a different frequency when the wafer is not in the slot. When the gas uptake is at a greater rate when the wafer is not in the slot than when the wafer is in the slot, the vacuum application can be performed and stopped more frequently when the wafer is not in the slot than when the wafer is in the slot. The frequency when the wafer is in the slot.
圖11繪示溶解氣體濃度隨著時間的圖表。執行在接觸器壓力被控制時對一段時間週期的溶解氧濃度進行測量的實驗。在該圖表中被標示為「晶圓入」的第一部分中，晶圓位於槽中；而在該圖表中被標示為「晶圓出」的第二部分中，晶圓不位於槽中。如圖可見，與晶圓位於槽中時相比，當晶圓在槽外時的溶解氣體濃度以較快的速率上升。與「晶圓出」的頻率相比，「晶圓入」部分中的結果對接觸器施加真空及停止施加真空的頻率較慢。Figure 11 shows a graph of dissolved gas concentration over time. Experiments were performed in which the dissolved oxygen concentration was measured over a period of time while the contactor pressure was controlled. In the first portion of the diagram, labeled "Wafer In," the wafer is in the slot; in the second section of the diagram, labeled "Wafer Out," the wafer is not in the slot. As can be seen, the dissolved gas concentration rises at a faster rate when the wafer is outside the tank than when the wafer is in the tank. The results in the Wafer In section apply vacuum to the contactor and stop applying vacuum at a slower rate than the Wafer Out.
舉例而言，在時間t1時施加真空、在時間t2時停止施加真空、在時間t3時施加真空、在時間t4時停止施加真空，以及在時間t5時再次施加真空。在「晶圓入」部分中，t1與t3之間的時間大於t3與t5之間的「晶圓出」部分，其指出當晶圓在槽外時對接觸器施加真空及停止施加真空的頻率是較大的。在圖11中，「晶圓入」部分在時間t1與t3之間具有第一頻率f1，而「晶圓出」部分在t3與t5之間具有比第一頻率f1大的第二頻率f2。For example, vacuum is applied at time t1, vacuum is stopped at time t2, vacuum is applied at time t3, vacuum is stopped at time t4, and vacuum is reapplied at time t5. In the "Wafer In" section, the time between t1 and t3 is greater than the "Wafer Out" section between t3 and t5, which indicates how often to apply vacuum to the contactor and stop applying vacuum when the wafer is outside the slot is larger. In FIG. 11, the "wafer in" portion has a first frequency f1 between times t1 and t3, and the "wafer out" portion has a second frequency f2 greater than the first frequency f1 between t3 and t5.
與圖11類似的接觸器壓力的控制不限於「晶圓入」及「晶圓出」實施例，而是適用於不同溶解氣體濃度的任何實行例。在一些如此實施例中，與在相對較低速率及/或量進行氣體攝取時相比，在較大速率及/或量進行氣體攝取時重複進行真空施加及停止真空施加的二個操作的頻率(例如，參照回到圖10，重複進行方格1003A及1003B的頻率)可為較高頻率。舉例而言，與電鍍系統執行電鍍操作時相比，當電鍍系統閒置時，電鍍溶液的氣體攝取及電鍍溶液的溶解氣體濃度可能是較少的。在此示例中，參照回到圖10，重複進行方格1003A及1003B的頻率在閒置期間可為一頻率，而在電鍍操作期間可為較高頻率。Control of contactor pressure similar to that of FIG. 11 is not limited to "wafer-in" and "wafer-out" embodiments, but is applicable to any implementation with different dissolved gas concentrations. In some such embodiments, the frequency with which the two operations of applying vacuum and stopping vacuum application are repeated when the gas uptake is performed at a greater rate and/or amount compared to when the gas uptake is performed at a relatively lower rate and/or amount (eg, referring back to FIG. 10, the frequency at which
如上所述，一些實施例可使用來自一或更多感測器的回饋以控制接觸器壓力。這可包括基於壓力偵測來偵測接觸器壓力及控制接觸器壓力，及/或基於此濃度偵測來偵測溶解氣體濃度及控制接觸器壓力。圖12繪示用於控制電鍍溶液中的溶解氣體濃度的第三示例技術。此處，基於該偵測來偵測及控制(例如，提高或降低)接觸器壓力，以將溶解氣體濃度保持在所欲範圍內。在方格1201中，如同方格801，將具有濃度的電鍍溶液流動通過接觸器。在方格1205中，透過上方提供的任何壓力感測器(例如，圖4的壓力感測器464)來偵測接觸器壓力。可連續偵測或判斷接觸器壓力。基於此偵測，在方格1203、1203A及1203B中控制接觸器壓力。As noted above, some embodiments may use feedback from one or more sensors to control contactor pressure. This may include detecting the contactor pressure and controlling the contactor pressure based on the pressure detection, and/or detecting the dissolved gas concentration and controlling the contactor pressure based on the concentration detection. 12 depicts a third example technique for controlling the concentration of dissolved gases in an electroplating solution. Here, the contactor pressure is detected and controlled (eg, increased or decreased) based on the detection to maintain the dissolved gas concentration within a desired range. In square 1201, like
若是偵測或判斷到接觸器壓力已到達第一接觸器壓力(例如，上閾值)，則可藉由執行方格1203A及如本文所述(例如，上方的方格1003A)對於接觸器施予真空來降低接觸器壓力。參照回到圖9，例如，若偵測到接觸器壓力到達時間t1或t3時的約為P1 Atm的上閾值，則可執行方格1203A。若是偵測或判斷到接觸器壓力已到達比第一接觸器壓力更低的第二接觸器壓力(例如，下閾值)，則可藉由執行方格1203B及如本文所述(例如，上方的方格1003B)停止對於接觸器施予真空來提高接觸器壓力。再次參照回到圖9，例如，若偵測到接觸器壓力到達時間t2時的約為P2 Atm的下閾值，則例如可執行方格1203B且持續執行，直到例如在時間t3時接觸器壓力再次達到上限。在一些實施例中，可將壓力偵測為測量值或類比信號；然而，在一些其他實施例中，該壓力可為從壓力感測器接收信號的控制器或其他邏輯裝置所判斷、計算及/或解譯的數值。在這些實施例的任何者中，壓力感測器所產生的數據是用於控制接觸器壓力。If it is detected or determined that the contactor pressure has reached a first contactor pressure (e.g., an upper threshold), then the contactor pressure may be applied by executing
類似於上述，也可基於所偵測的接觸器壓力而以各種頻率重複進行方格1203A及1203B。舉例而言，參照回到圖11，可與圖11所示類似的方法，基於晶圓是否在電鍍槽中而以不同頻率控制接觸器壓力。Similar to the above,
在一些基於回饋的實施例中，接觸器壓力控制可基於偵測溶解氣體濃度，及基於此濃度偵測控制接觸器壓力。圖13繪示用於控制電鍍溶液中的溶解氣體濃度的第四示例技術。此處，基於該偵測而直接測量氣體濃度，且控制(例如，提高或降低)接觸器壓力，以將溶解氣體濃度保持在所欲範圍內。在方格1301中，如同方格801，將具有濃度的電鍍溶液流動通過接觸器。在方格1305中，藉由位於上述系統內的一或更多位置中的上方提供氣體感測器的任何者(例如，圖4的氣體感測器462)來測量氣體濃度。基於此偵測，在方格1303、1303A及1303B中控制接觸器壓力。In some feedback-based embodiments, contactor pressure control may be based on detecting a dissolved gas concentration, and controlling the contactor pressure based on this concentration detection. 13 depicts a fourth example technique for controlling dissolved gas concentration in an electroplating solution. Here, the gas concentration is directly measured based on this detection, and the contactor pressure is controlled (eg, increased or decreased) to maintain the dissolved gas concentration within a desired range. In
若是偵測或判斷到溶解氣體濃度到達第一濃度層級(例如，上閾值)，則可藉由執行方格1303A及如本文所述(例如，方格1003A)對於接觸器施予真空來降低接觸器壓力。舉例而言，參照回到圖9，若偵測到濃度層級約到達時間t1時的約為C3 ppm的上閾值，則可執行方格1303A以降低接觸器壓力。若是偵測或判斷到溶解氣體濃度已到達比第一濃度層級更低的第二濃度層級(例如，下閾值)，則可藉由執行方格1303B及如本文所述(例如，方格1003B)停止對於接觸器施予真空來提高接觸器壓力。再次參照回到圖9，例如，若偵測到溶解氣體濃度到達約為C4 ppm的下閾值，則可執行方格1303B且持續執行直到時間t3。在一些實施例中，可將氣體濃度偵測為測量值或類比信號；然而，在一些其他實施例中，該濃度可為從氣體感測器接收信號的控制器或其他邏輯裝置所判斷、計算及/或解譯的數值。在這些實施例的任何者中，氣體感測器所產生的數據是用於控制接觸器壓力。在一些實施例中，該溶解氣體可為溶解氧，而一或更多氣體感測器可為氧感測器。If the dissolved gas concentration is detected or determined to reach a first concentration level (e.g., an upper threshold), exposure can be reduced by performing
在一些實施例中，接觸器壓力可基於所偵測的接觸器壓力及所測量的溶解氣體濃度二者而加以控制。In some embodiments, the contactor pressure can be controlled based on both the detected contactor pressure and the measured dissolved gas concentration.
在一些實行例中，基於電鍍系統的不同狀態(例如，在電鍍期間、閒置時、晶圓進及/或晶圓出)而具有不同溶解氣體濃度可為有優勢的。舉例而言，可將該接觸器壓力進行控制，使得在槽中具有晶圓時產生第一溶解氣體濃度，而當槽中不具有晶圓時產生不同的第二溶解氣體濃度。在另一示例中，可將該接觸器壓力進行控制，在進行電鍍時產生第一溶解氣體濃度，而在不進行電鍍時產生不同的第二溶解氣體濃度。類似地，可將該接觸器壓力進行控制，以在電鍍處理的不同階段期間產生不同的溶解氣體濃度。這可有利於用於在不同處理期間調整不同副產物層級，及/或在電鍍期間產生不同浴及沉積材料性質。In some implementations, it may be advantageous to have different dissolved gas concentrations based on different states of the plating system (eg, during plating, while idle, wafer in and/or wafer out). For example, the contactor pressure may be controlled such that a first dissolved gas concentration results when the tank has a wafer in it, and a different second dissolved gas concentration results when the tank does not have a wafer in it. In another example, the contactor pressure can be controlled to produce a first dissolved gas concentration when electroplating is in progress and a different second dissolved gas concentration when electroplating is not in progress. Similarly, the contactor pressure can be controlled to produce different dissolved gas concentrations during different stages of the electroplating process. This can be advantageously used to tune different by-product levels during different processes, and/or create different bath and deposited material properties during electroplating.
如上方提供，電鍍系統可包括與上述圖6A及6B中的接觸器連接的壓力調節器。在這些實施例的其中一些中，該壓力調節器被設定在特定值，且控制接觸器壓力及真空施加，以將接觸器保持在特定數值，並因此將溶解氣體濃度保持在設定數值。圖14繪示用於控制電鍍溶液中的溶解氣體濃度的另一示例技術。此處，接觸器所用的壓力調節器是被設定在設定壓力。如圖6A及6B中所示，壓力調節器可被流體插置在真空源與接觸器之間；該調節器是配置以保持該接觸器中的設定壓力。在方格1403中，將電鍍溶液流動經過接觸器，如本文所述；而在方格1405中，經由調節器對該接觸器施予真空，其中該接觸器調整該真空施加，並且保持該接觸器中的設定壓力。如方格1407所述，保持設定壓力使溶液中的溶解氣體濃度被保持在第一值內、落在設定值上，或是實質落在設定值上(例如，該數值的15%內)。As provided above, the electroplating system may include a pressure regulator connected to the contactors in FIGS. 6A and 6B described above. In some of these embodiments, the pressure regulator is set at a specific value, and the contactor pressure and vacuum application are controlled to maintain the contactor at a specific value, and thus maintain the dissolved gas concentration at the set value. 14 depicts another example technique for controlling the dissolved gas concentration in an electroplating solution. Here, the pressure regulator used for the contactor is set at the set pressure. As shown in Figures 6A and 6B, a pressure regulator can be fluidly interposed between the vacuum source and the contactor; the regulator is configured to maintain a set pressure in the contactor. In
在一些實施例中，該電鍍系統可包括與電鍍流動迴路平行的接觸器，上方圖7A及7B中所述及顯示。在一些如此實施例中，該真空可被恆定施加至接觸器，以產生恆定或實質恆定(例如，數值的10%內)的氣體濃度移除速率。圖15繪示用於控制電鍍溶液中的溶解氣體濃度的又另一示例技術。在方格1501中，電鍍流體同時流動通過電鍍流動迴路(例如，迴路706)，以及與該迴路706平行的接觸器708。在方格1503中，對接觸器施予真空，使得流動通過該接觸器的電鍍溶液的氣體濃度移除速率為實質恆定的。In some embodiments, the electroplating system may include a contactor parallel to the electroplating flow loop, described and shown above in FIGS. 7A and 7B . In some such embodiments, the vacuum can be constantly applied to the contactor to produce a constant or substantially constant (eg, within 10% of value) gas concentration removal rate. 15 depicts yet another example technique for controlling dissolved gas concentration in an electroplating solution. In
如上所述，通過接觸器的流體的流率會影響從該流體移除的實際氣體量。舉例來說，流率越快，所移除的實際氣體越低。因此，在一些實施例中，圖15的技術還可包括任選步驟，用於調整通過接觸器的流體的流率，從而提高、降低氣體濃度，或是將氣體濃度保持在範圍內或設定層級上。在一些實施例中，此流率可基於氣體感測器(例如，圖7A、7B及7C中的感測器762)的判斷而加以調整。舉例而言，若氣體感測器判斷氣體濃度處於或高於所欲的氣體濃度層級，可透過接觸器降低該流率以從該液體移除較多的溶解氣體，從而降低該溶液的總氣體濃度層級。As noted above, the flow rate of a fluid through a contactor can affect the actual amount of gas removed from that fluid. For example, the faster the flow rate, the lower the actual gas removed. Thus, in some embodiments, the technique of FIG. 15 may also include an optional step for adjusting the flow rate of the fluid through the contactor to increase, decrease, or maintain the gas concentration within a range or set level superior. In some embodiments, this flow rate can be adjusted based on the determination of a gas sensor (eg,
如上方提供，一些技術是用於電鍍槽或系統的不同狀態。這些狀態可包括晶圓是否位於浴/溶液中，或是在浴溶液外。在一些如此實施例中，當晶圓位於浴中時，溶解氣體濃度(例如，溶解氧濃度)可為相對低濃度；而晶圓在浴之外時，溶解氣體濃度可為相對高濃度。這些狀態還可包括晶圓在槽中進行電鍍時及未進行電鍍時。此外，在這些狀態的其中一者期間的溶解氣體濃度比起其他者可為較高的，而這些技術可控制接觸器壓力以用於這些狀態。As provided above, some techniques are used in different states of plating cells or systems. These states may include whether the wafer is in the bath/solution, or out of the bath solution. In some such embodiments, the dissolved gas concentration (eg, dissolved oxygen concentration) may be relatively low when the wafer is in the bath, and the dissolved gas concentration may be relatively high when the wafer is outside the bath. These states may also include when the wafer is being plated in the bath and when it is not being plated. Furthermore, the dissolved gas concentration during one of these states may be higher than the other, and these techniques may control the contactor pressure for these states.
舉例來說，當這些狀態的其中一者期間的濃度比起另一狀態處於相對高濃度時，可如上述以較高頻率將接觸器壓力增加及降低。當這些狀態的其中一者期間的濃度較高時，接觸器壓力所保持的範圍亦可為較高的。請參照圖10，例如，當濃度較高時，重複進行方格1003A及1003B的頻率可為較高的。此外，當濃度較低時，方格1003A及1003B的壓力範圍可處於較高範圍。
電解質參數 For example, when the concentration during one of these states is at a relatively high concentration compared to the other state, the contactor pressure may be increased and decreased at a higher frequency as described above. When the concentration during one of these states is higher, the range over which the contactor pressure is maintained may also be higher. Referring to FIG. 10 , for example, when the density is high, the frequency of repeating
在各種實施例中，溶解氣體可為溶解氧，而銅電鍍溶液中的此溶解氧濃度可被保持在約1 ppm與10 ppm之間，或約2 ppm與約8 ppm之間。在一些實施例中，銅電鍍溶液中的溶解氧濃度被保持在約3 ppm與6 ppm之間。在進一步實施例中，銅電鍍溶液中的溶解氧濃度被保持在約4.5 ppm與6 ppm之間。In various embodiments, the dissolved gas may be dissolved oxygen, and this dissolved oxygen concentration in the copper electroplating solution may be maintained between about 1 ppm and 10 ppm, or between about 2 ppm and about 8 ppm. In some embodiments, the dissolved oxygen concentration in the copper electroplating solution is maintained between about 3 ppm and 6 ppm. In a further embodiment, the dissolved oxygen concentration in the copper electroplating solution is maintained between about 4.5 ppm and 6 ppm.
在各種實施例中，用於控制溶解氧濃度的接觸器壓力介於約0.2Atm與2Atm之間。在某些實施例中，用於控制溶解氧濃度的接觸器壓力介於約0.2Atm與約1Atm之間，約0.3與約0.7Atm之間。在進一步實施例中，用於控制溶解氧濃度的接觸器壓力介於約0.4Atm與約0.6Atm之間。在某些實行例中，接觸器壓力是施加以在達成電鍍溶液中的溶解氧的平衡濃度的條件下流動或靜止電鍍溶液。In various embodiments, the contactor pressure for controlling the dissolved oxygen concentration is between about 0.2 Atm and 2 Atm. In certain embodiments, the contactor pressure for controlling the dissolved oxygen concentration is between about 0.2 Atm and about 1 Atm, between about 0.3 and about 0.7 Atm. In a further embodiment, the contactor pressure for controlling the dissolved oxygen concentration is between about 0.4 Atm and about 0.6 Atm. In certain implementations, the contactor pressure is applied to flow or stand still the plating solution under conditions to achieve an equilibrium concentration of dissolved oxygen in the plating solution.
雖然控制電鍍溶液中的溶解氧濃度可為某些所揭示實施例的目標，但各種其他參數可影響溶解氧濃度。這些其他參數可包括電鍍溶液的溫度及/或電解質的組成。While controlling the dissolved oxygen concentration in the plating solution may be a goal of certain disclosed embodiments, various other parameters may affect the dissolved oxygen concentration. These other parameters may include the temperature of the plating solution and/or the composition of the electrolyte.
本文提供的系統係配置以執行本文所述的任何技術。這可包括用於控制本文所述的電鍍系統的處理條件及硬體狀態的系統控制器，例如包括控制器144及444。系統控制器可包括一或更多記憶裝置、一或更多大量儲存裝置及一或更多處理器。處理器可包括CPU或電腦、類比及/或數位輸入/輸出連接件、步進器馬達控制器板等。The systems provided herein are configured to perform any of the techniques described herein. This may include system controllers, such as
在一些實行例中，控制器為系統的一部份且該系統可為上述示例的一部分。此系統可包括半導體處理設備，而該半導體處理設備包括一或更多處理工具、一或更多腔室、一或更多處理平台及/或特定處理構件（晶圓基座、氣體流動系統等）。可將這些系統與電子元件進行整合以在處理半導體晶圓或基板之前、期間及之後控制它們的操作。所述電子元件可被稱為「控制器」，其可控制一或更多系統的各種構件或子部件。取決於處理需求及/或系統類型，可將控制器進行編程以控制本文所揭露的任何處理，包括處理氣體及流體的輸送、真空源、幫浦、電鍍、溫度設定（例如，加熱及/或冷卻）、壓力設定、真空設定、功率設定、流率設定、流體輸送設定、定位及操作設定、與特定系統連接或接合的一工具及其他傳輸工具及/或負載鎖室的晶圓傳輸進出。In some implementations, the controller is part of a system and the system can be part of the examples described above. Such systems may include semiconductor processing equipment including one or more processing tools, one or more chambers, one or more processing platforms, and/or specific processing components (wafer susceptors, gas flow systems, etc. ). These systems can be integrated with electronic components to control the operation of semiconductor wafers or substrates before, during and after processing them. The electronic components may be referred to as "controllers," which may control various components or subcomponents of one or more systems. Depending on the process requirements and/or system type, the controller can be programmed to control any of the processes disclosed herein, including delivery of process gases and fluids, vacuum sources, pumps, plating, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, flow rate settings, fluid delivery settings, positioning and operation settings, a tool and other transfer tools and/or load lock chambers for wafer transfer in and out of connection or engagement with a particular system.
廣義來說，可將控制器義成具有各種積體電路、邏輯、記憶體及/或軟體的電子元件，以接收指令、發送指令、控制操作、啟用清潔操作、啟用端點測量等。所述積體電路可包括以韌體形式儲存程式指令的晶片、數位信號處理器(DSP)、定義為特殊應用積體電路（ASIC）的晶片及/或執行程式指令（例如，軟體）的一或更多微處理器或微控制器。程式指令得為以各種獨立設定（或程式檔案）形式而被傳送至控制器的指令，而定義出用於在半導體晶圓上、或針對半導體晶圓、或對系統執行特定步驟的操作參數。在一些實施例中，操作參數可為製程工程師所定義之配方的一部分，以在將一或更多層、材料、金屬、氧化物、矽、二氧化矽、表面、電路、及/或晶圓的晶粒的製造期間完成一或更多的處理步驟。Broadly speaking, a controller can be defined as an electronic component having various integrated circuits, logic, memory, and/or software to receive commands, send commands, control operations, enable cleaning operations, enable endpoint measurements, and so on. The integrated circuit may include a chip storing program instructions in the form of firmware, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and/or a chip that executes program instructions (eg, software). or more microprocessors or microcontrollers. Program instructions may be instructions transmitted to the controller in the form of various individual settings (or program files) defining operating parameters for performing specific steps on or for the semiconductor wafer or for the system. In some embodiments, the operating parameters may be part of a recipe defined by a process engineer to process one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or wafers One or more processing steps are performed during the fabrication of the die.
在一些實行例中，控制器可為電腦的一部分或耦接至電腦，所述電腦係整合並耦接至所述系統，或以其他方式與所述系統網路連接，或是其組合。例如，控制器可位於「雲端」、或FAB主電腦系統的全部或一部分中而可允許基板處理的遠端存取。電腦可使對系統的遠端存取能夠監控加工操作的當前進程、檢視過去加工操作的歷史、檢視來自複數加工操作的趨勢或性能度量、變更當前處理的參數、設定當前處理之後的處理步驟，或是開始新的處理。在一些示例中，遠端電腦（例如，伺服器）可透過網路向系統提供處理配方，其中該網路可包括區域網路或網際網路。遠端電腦可包括使用者介面，而能夠對參數及/或設定進行輸入或編程，所述參數及/或設定則接著從遠端電腦傳送至系統。在一些示例中，控制器接收數據形式的指令，其中所述指令係指明一或更多操作期間待執行之各處理步驟所用的參數。應當理解的是，所述參數可特定於待執行的步驟類型，及控制器所配置以連接或控制的工具類型。因此，如上所述，控制器可例如藉由包括一或更多離散控制器而進行分佈，其中所述離散控制器係彼此以網路連接且朝向共同的目的（例如本文所述的步驟與控制）而運作。為此目的所分佈的控制器之示例將係位於腔室上的一或更多積體電路，其與遠端設置（例如，位於平台層或作為遠端電腦的一部分）且結合以控制腔室上之處理的一或更多積體電路連通。In some implementations, the controller can be part of or coupled to a computer that is integrated and coupled to the system, or otherwise networked with the system, or a combination thereof. For example, the controller can reside in the "cloud," or in all or part of the FAB's main computer system, allowing remote access for substrate processing. The computer enables remote access to the system to monitor the current progress of the machining operation, view the history of past machining operations, view trends or performance metrics from multiple machining operations, change the parameters of the current process, set the processing steps after the current process, Or start a new process. In some examples, a remote computer (eg, a server) may provide processing recipes to the system over a network, which may include a local area network or the Internet. The remote computer may include a user interface to enable input or programming of parameters and/or settings which are then transmitted from the remote computer to the system. In some examples, the controller receives instructions in the form of data specifying parameters for various processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of step to be performed, and the type of implement the controller is configured to connect to or control. Thus, as noted above, the controllers may be distributed, for example, by including one or more discrete controllers networked with each other and directed toward a common purpose (such as the steps and controls described herein) ) while operating. An example of a controller distributed for this purpose would be one or more integrated circuits located on the chamber that are located remotely (e.g. at the platform level or as part of a remote computer) and combined to control the chamber One or more integrated circuits for the above processing are connected.
不具限制地，示例性系統可包括沉積腔室或模組、旋轉-淋洗腔室或模組、金屬電鍍腔室或模組、清潔腔室或模組、晶邊蝕刻腔室或模組、物理氣相沉積（PVD）腔室或模組、化學氣相沉積（CVD）腔室或模組、原子層沉積（ALD）腔室或模組、原子層蝕刻（ALE）腔室或模組、離子植入腔室或模組、軌道腔室或模組，以及可能有關於或使用於半導體晶圓之加工及/或製造中的任何其他半導體處理系統。Without limitation, exemplary systems may include deposition chambers or modules, spin-rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, edge etch chambers or modules, Physical vapor deposition (PVD) chamber or module, chemical vapor deposition (CVD) chamber or module, atomic layer deposition (ALD) chamber or module, atomic layer etching (ALE) chamber or module, Ion implantation chambers or modules, orbital chambers or modules, and any other semiconductor processing systems that may be related to or used in the processing and/or fabrication of semiconductor wafers.
如上所述，取決於工具所待執行的一或更多處理步驟，控制器可連通至一或更多其他工具電路或模組、其他工具組件、群集式工具、其他工具介面、相鄰工具、鄰近工具、遍布於工廠的工具、主電腦、另一控制器，或材料輸送中所使用的工具，而將基板的容器帶進及帶出半導體製造工廠的工具位置及/或裝載埠口。As noted above, depending on one or more processing steps to be performed by the tool, the controller may communicate to one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, A tool location and/or a load port adjacent to a tool, a tool throughout the fab, a host computer, another controller, or a tool used in material handling to bring containers of substrates into and out of a semiconductor fabrication facility.
應理解，序數指標的使用，例如 (a)、(b)、(c)、……，僅用於組織目的，並不旨在傳達任何對於與各序數指標相關的項目的特定順序或重要性。例如，"(a)獲得有關速度的資訊及(b)獲得有關位置的資訊"將包括在獲得有關速度的資訊之前獲得有關位置的資訊、在獲得有關位置的資訊之前獲得有關速度的資訊，以及同時獲得有關位置的資訊及獲得有關速度的資訊。然而，在某些情況下，與序數指標相關的某些項目可能固有地需要特定的順序，例如，"(a)獲得有關速度的資訊、(b) 基於有關速度的資訊確定第一加速度，以及(c)獲得有關位置的資訊"；在本例中，要執行(b)將需要(a)，因為 (b) 依賴於 (a) 中獲得的資訊；但是，(c)可在 (a) 或 (b) 之前或之後執行。It should be understood that the use of ordinal indicators, such as (a), (b), (c), ..., is for organizational purposes only and is not intended to convey any particular order or importance of the items associated with each ordinal indicator . For example, "(a) obtaining information about velocity and (b) obtaining information about location" would include obtaining information about location before obtaining information about velocity, obtaining information about velocity before obtaining information about location, and At the same time get information about position and get information about speed. In some cases, however, certain items related to ordinal indicators may inherently require a specific order, for example, "(a) obtain information about velocity, (b) determine a first acceleration based on information about velocity, and (c) obtain information about the location"; in this example, (a) would be required to perform (b) because (b) relies on the information obtained in (a); however, (c) can be found in (a) or before or after (b).
對本揭示中描述的實行例的各種修改對於本領域中的通常知識者來說是顯而易見的，並且在不脫離本揭示的精神或範圍的情況下，本文定義的一般原理可以應用於其他實行例。因此，申請專利範圍不旨在限於本文中所示的實行例，而是要被賦予與本揭示、本文所揭示原理及新穎特徵一致的最寬範圍。Various modifications to the implementations described in this disclosure will be readily apparent to those of ordinary skill in the art, and the generic principles defined herein may be applied to other implementations without departing from the spirit or scope of this disclosure. Thus, the claims are not intended to be limited to the implementations shown herein but are to be accorded the widest scope consistent with this disclosure, the principles and novel features disclosed herein.
本說明書中在個別實行例的上下文中描述的某些特徵也可以在單一實行例中組合實現。相反，在單一實行例的上下文中描述的各種特徵也可以在多個實現中單獨或以任何合適的子組合來實現。此外，儘管特徵可以在上面描述為在某些組合中起作用並且甚至最初以此請求保護，但是在某些情況下可以從所請保護的組合中去除一或多個特徵，並且所請保護的組合可以針對子組合或子組合的變體。類似地，雖然在圖式中以特定順序描繪操作，但這不應被理解為要求這些操作以所示的特定順序或按順序執行，或者所有所示的操作都被執行以獲得期望的結果。此外，圖式得以流程圖的形式示意性地描繪另一個示例過程。然而，未描繪的其他操作可以併入示意性說明的示例過程中。例如，一個或多個附加操作可以在任何所示操作之前、之後、同時或之間執行。在某些情況下，多任務和並行處理可為有利的。此外，上述實行例中各種系統構件的分離不應理解為在所有實行例中都需要這種分離；應當理解，所描述的程序構件和系統通常可以一起整合在單個軟體產品中或打包成多種軟體產品。此外，其他實行例落在所附申請專利範圍的範圍內。在某些情況下，申請專利範圍中所述的動作得以不同的順序執行，並且仍能達到期望的結果。Certain features that are described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Furthermore, although features may be described above as functioning in certain combinations and were even originally claimed as such, in some cases one or more features may be removed from the claimed combination and the claimed Combinations can be for subcombinations or variations of subcombinations. Similarly, while operations are depicted in the drawings in a particular order, this should not be construed as requiring that those operations be performed in the particular order shown or sequentially, or that all illustrated operations be performed, to achieve desirable results. In addition, the drawings schematically depict another example process in flowchart form. However, other operations not depicted may be incorporated into the schematically illustrated example processes. For example, one or more additional operations may be performed before, after, concurrently with, or between any illustrated operations. In certain circumstances, multitasking and parallel processing may be advantageous. Furthermore, the separation of various system components in the above-described implementations should not be understood as requiring such separation in all implementations; it should be understood that the described program components and systems can often be integrated together in a single software product or packaged as multiple software products. product. Additionally, other implementations are within the scope of the appended claims. In some cases, the actions described in the claims can be performed in a different order and still achieve desirable results.
100:電鍍系統 102:電鍍槽 104:儲存槽 106:電鍍槽流動迴路 108:接觸器 110:真空源 114:電鍍浴 116:層面 118:晶圓 120:基板固持件 122:可轉動心軸 124:陽極 125:透膜 126:幫浦 128:振動轉換器 132:溢流槽 134:參考電極 136:分離腔室 138:DC電源 140:負性輸出引線 142:正性輸出引線 144:系統控制器 152:加熱器 208:接觸器 212:外殼 214:流體輸入口 216:流體輸出口 218:真空埠口 220:透膜 220A:部分 222:採集管 224:殼層側 226:內腔側 228:液體/箭頭 230:溶解氣體 232:箭頭 234:孔洞 400:電鍍系統 402:電鍍槽 404:儲存槽 406:電鍍槽流動迴路 408:接觸器 410:真空源 444:控制器 460:閥 462:氣體感測器 464:壓力感測器 600:電鍍系統 602:電鍍槽 604:儲存槽 606:電鍍槽流動迴路 608:接觸器 610:真空源 666:壓力調節器 700:電鍍系統 702:電鍍槽 704:儲存槽 706:電鍍槽流動迴路 708:接觸器 710:真空源 760,761:控制閥 762:氣體感測器 801,803:方格 1001,1003,1003A,1003B:方格 1201,1203,1203A,1203B,1205:方格 1301,1303,1303A,1303B,1305:方格 1401,1403,1405,1407:方格 1501,1503,1505:方格 100: Electroplating system 102: Electroplating tank 104: storage tank 106: Electroplating tank flow circuit 108: Contactor 110: vacuum source 114: electroplating bath 116: level 118: Wafer 120: substrate holder 122: rotatable mandrel 124: anode 125: permeable membrane 126: pump 128: Vibration converter 132: overflow tank 134: Reference electrode 136: separation chamber 138:DC power supply 140: Negative output lead 142: Positive output lead 144: System controller 152: heater 208: Contactor 212: shell 214: Fluid input port 216: Fluid outlet 218: Vacuum port 220: permeable membrane 220A: part 222: collection tube 224: shell side 226: Lumen side 228:Liquid/Arrow 230: Dissolved gas 232: Arrow 234: hole 400: Electroplating system 402: Plating tank 404: storage tank 406: Electroplating tank flow circuit 408: contactor 410: vacuum source 444: controller 460: valve 462: Gas sensor 464:Pressure sensor 600: Electroplating system 602: Plating tank 604: storage tank 606: Electroplating tank flow circuit 608: contactor 610: vacuum source 666: Pressure Regulator 700: Electroplating system 702: Plating tank 704: storage tank 706: Electroplating tank flow circuit 708: contactor 710: vacuum source 760,761: Control valves 762: Gas sensor 801,803: grid 1001, 1003, 1003A, 1003B: grid 1201, 1203, 1203A, 1203B, 1205: grid 1301, 1303, 1303A, 1303B, 1305: grid 1401, 1403, 1405, 1407: grid 1501, 1503, 1505: grid
本文所揭示的各種實行例係以示例而非限制方式繪示於隨附圖式的圖中，其中類似元件符號指的是類似元件。The various implementations disclosed herein are depicted in the figures of the accompanying drawings by way of illustration and not limitation, wherein like reference numerals refer to like elements.
圖1繪示出示例性電鍍系統。Figure 1 depicts an exemplary electroplating system.
圖2A繪示出示例性接觸器的橫截面圖。2A depicts a cross-sectional view of an exemplary contactor.
圖2B繪示圖2A的接觸器的放大橫截面部分。FIG. 2B illustrates an enlarged cross-sectional portion of the contactor of FIG. 2A .
圖3繪示圖1的示例系統，伴隨電鍍槽的概略橫截面圖。Figure 3 depicts the example system of Figure 1, along with a schematic cross-sectional view of an electroplating tank.
圖4繪示另一電鍍系統。FIG. 4 illustrates another electroplating system.
圖5繪示所量測的溶解氧對上接觸器壓力的圖表。Figure 5 depicts a graph of measured dissolved oxygen versus upper contactor pressure.
圖6A繪示另一示例電鍍系統。FIG. 6A illustrates another example electroplating system.
圖6B繪示另一示例電鍍系統。FIG. 6B illustrates another example electroplating system.
圖7A繪示又另一示例電鍍系統。Figure 7A illustrates yet another example electroplating system.
圖7B繪示又另一示例電鍍系統。7B illustrates yet another example electroplating system.
圖7C繪示又另一示例電鍍系統。7C illustrates yet another example electroplating system.
圖8繪示用於控制電鍍溶液中的溶解氣體濃度的第一技術。Figure 8 depicts a first technique for controlling the dissolved gas concentration in an electroplating solution.
圖9繪示在一段時間內的溶解氣體濃度及接觸器壓力的圖表。Figure 9 shows a graph of dissolved gas concentration and contactor pressure over a period of time.
圖10繪示用於控制電鍍溶液中的溶解氣體濃度的第二示例技術。10 depicts a second example technique for controlling the concentration of dissolved gases in an electroplating solution.
圖11繪示溶解氣體濃度隨著時間的圖表。Figure 11 shows a graph of dissolved gas concentration over time.
圖12繪示用於控制電鍍溶液中的溶解氣體濃度的第三示例技術。12 depicts a third example technique for controlling the concentration of dissolved gases in an electroplating solution.
圖13繪示用於控制電鍍溶液中的溶解氣體濃度的第四示例技術。13 depicts a fourth example technique for controlling dissolved gas concentration in an electroplating solution.
圖14繪示用於控制電鍍溶液中的溶解氣體濃度的另一示例技術。14 depicts another example technique for controlling the dissolved gas concentration in an electroplating solution.
圖15繪示用於控制電鍍溶液中的溶解氣體濃度的又另一示例技術。15 depicts yet another example technique for controlling dissolved gas concentration in an electroplating solution.
100:電鍍系統 100: Electroplating system
102:電鍍槽 102: Electroplating tank
104:儲存槽 104: storage tank
106:電鍍槽流動迴路 106: Electroplating tank flow circuit
108:接觸器 108: Contactor
110:真空源 110: vacuum source
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2022
- 2022-04-14 TW TW111114203A patent/TW202305192A/en unknown
- 2022-04-14 CN CN202280005335.5A patent/CN115867696A/en active Pending
- 2022-04-14 WO PCT/US2022/024762 patent/WO2022221498A1/en active Application Filing
- 2022-04-14 KR KR1020227044417A patent/KR20230169826A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN115867696A (en) | 2023-03-28 |
| WO2022221498A1 (en) | 2022-10-20 |
| KR20230169826A (en) | 2023-12-18 |
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