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    Leveling agent, metal plating composition containing same, preparation method therefor and use thereof
    2.
    发明授权
    Leveling agent, metal plating composition containing same, preparation method therefor and use thereof 有权

    公开(公告)号：US11332471B2

    公开(公告)日：2022-05-17

    申请号：US16462333

    申请日：2017-12-15

    Applicant: SHANGHAI SINYANG SEMICONDUCTOR MATERIALS CO., LTD.

    Inventor： Su Wang ,  Liqi Shi ,  Xuepeng Gao

    IPC: C25D3/38 ,  C07D487/04

    Abstract: Disclosed are a leveling agent, a metal plating composition containing same, and a preparation method therefor and the use thereof. The raw materials of the metal electroplating composition comprise a metal plating solution and a leveling agent; the metal plating solution comprises a copper salt, an acidic electrolyte, a source of halide ions and water; and the leveling agent is a compound of formula I. The metal plating composition can be used in the processes of printed circuit board electroplating and integrated circuit copper interconnection electroplating, can achieve the effects of no voids or defects, low purity in the plating layer, good plating homogeneity, a dense structure and small surface roughness, and has better industrial application value.

    Additive C capable of changing microvia-filling method by TSV copper plating, and electroplating solution containing same
    4.
    发明授权
    Additive C capable of changing microvia-filling method by TSV copper plating, and electroplating solution containing same 有权

    公开(公告)号：US09915005B2

    公开(公告)日：2018-03-13

    申请号：US14908778

    申请日：2013-12-10

    Applicant: SHANGHAI SINYANG SEMICONDUCTOR MATERIALS CO., LTD.

    Inventor： Su Wang ,  Xianxian Yu ,  Li Ma ,  Yanyan Li

    IPC: C25D3/38 ,  C25D7/12 ,  H01L21/288 ,  H01L21/768

    CPC classification number: C25D3/38 ,  C25D7/123 ,  H01L21/2885 ,  H01L21/76898

    Abstract: An additive C capable of changing microvia-filling method by TSV copper plating, and electroplating solution containing same. The additive C contains by mass percentage: 5%-10%, one of polyethylene glycol or polyvinyl alcohol with the molecular weight of 200-100,000, or the mixture with different molecular weight thereof; 0.001%-0.5% isomer of the surfactant which including the alkylphenol polyoxyethylene ether or fatty alcohol-polyoxyethylene ether; and the solvent is water. The electroplating solution containing the additive C could be used for microvia-filling by TSV copper plating, the electroplating current distribution could be adjusted reasonably to realize the smooth transition between the conformal and bottom-up plating, so as to reduce the possibility of the seam or void in the coating, realize the high-speed electroplating, reduce the thickness of the copper layer, reduce the TSV plating duration and the cost of the chemical mechanical polishing (CMP), and significantly improve the production efficiency.

    Additive for reducing voids after annealing of copper plating with through silicon via
    5.
    发明授权
    Additive for reducing voids after annealing of copper plating with through silicon via 有权

    公开(公告)号：US09856572B2

    公开(公告)日：2018-01-02

    申请号：US14909745

    申请日：2013-12-25

    Applicant: Shanghai Sinyang Semiconductor Materials Co., Ltd.

    Inventor： Su Wang ,  Xianxian Yu ,  Li Ma ,  Yanyan Li

    IPC: C08K5/06 ,  C25D3/38 ,  C25D5/50 ,  C25D7/12 ,  H01L21/288 ,  H01L21/768

    CPC classification number: C25D3/38 ,  C25D5/50 ,  C25D7/123 ,  H01L21/2885 ,  H01L21/76898

    Abstract: An additive for reducing voids after annealing of copper plating with through silicon via. The additive contains by weight percent: 0.05-1% of one or more of quaternized polyethylene imine and derivatives thereof having different molecular weights, and 1-10% of polyethylene glycol with an average molecular weight of 200-20000. The additive is used in combination with an electroplating solution of a copper methyl sulfonate system. The electroplating solution of a copper methyl sulfonate system contains 1-5 ml/L of the additive by volume ratio. The electroplating solution of a copper methyl sulfonate system contains by mass volume ratio: 50-110 g/L of copper ions, 5-50 g/L of methanesulfonic acid and 20-80 mg/L of chlorine ions. The electroplating solution also contains by volume ratio: 0.5-5 ml/L of accelerator, 5-20 ml/L of inhibitor and 5-10 ml/L of levelling agent. The additive for reducing voids after annealing of copper plating with through silicon via provided in the present invention can solve the problem of micro-voids between grain boundaries after high temperature annealing of copper plating.

    A METHOD FOR MICROVIA FILLING BY COPPER ELECTROPLATING WITH TSV TECHNOLOGY FOR 3D COPPER INTERCONNECTION AT HIGH ASPECT RATIO
    7.
    发明申请
    A METHOD FOR MICROVIA FILLING BY COPPER ELECTROPLATING WITH TSV TECHNOLOGY FOR 3D COPPER INTERCONNECTION AT HIGH ASPECT RATIO 审中-公开
    通过铜电镀技术在高倍率下进行三维铜相互连接的微电脑填充方法

    公开(公告)号：US20160190007A1

    公开(公告)日：2016-06-30

    申请号：US14909307

    申请日：2013-12-10

    Applicant: SHANGHAI SINYANG SEMICONDUCTOR MATERIALS CO., LTD.

    Inventor： Su WANG ,  Xianxian YU ,  Li MA ,  Yanyan LI

    IPC: H01L21/768 ,  C25D5/48 ,  C25D5/34 ,  C25D7/12 ,  C25D3/38

    CPC classification number: H01L21/76879 ,  C25D3/38 ,  C25D5/34 ,  C25D5/48 ,  C25D7/00 ,  C25D7/12 ,  H01L21/2885 ,  H01L21/76883 ,  H01L21/76898

    Abstract: A method for microvia filling by copper electroplating with a TSV technology for a 3D copper interconnection at a high aspect ratio, which includes: Step 1: formulating an electroplating solution of a copper methyl sulfonate system, Step 2: wetting the microvias of the TSV technology by means of an electroplating pre-treatment, Step 3: charging into the grooves, completing the ultra-low current diffusion, so that the copper ions and the additives are rationally distributed at the surface and the interior of the microvias of the TSV technology, Step 4: connecting the wafer for the TSV technology to the cathode of a power source, fully immersing the electroplating surface of the wafer in the electroplating solution, and electroplating with a step-by-step current method of rotating or stirring the cathode, the current density of the plating conditions is 0.01-10A/dm2 and the temperature is 15-30° C., Step 5: after the electroplating, washing the wafer completely clean with deionized water, and drying it by spinning or blowing. The method for microvia filling by copper electroplating with a TSV technology for a 3D copper interconnection at a high aspect ratio has a high via-filling speed, a thin copper layer on the surface, no risk of creating voids and cracks, and can achieve the complete filling of microvias having an aspect ratio of more than 10:1 which are extremely difficult to fill.

    Abstract translation: 一种利用TSV技术以高宽比进行三维铜互连的铜电镀微孔填充方法，其中包括：步骤1：制备铜甲基磺酸盐体系的电镀溶液，步骤2：润湿TSV技术的微孔 通过电镀预处理，步骤3：充填到槽中，完成超低电流扩散，使得铜离子和添加剂合理分布在TSV技术的微孔的表面和内部， 步骤4：将用于TSV技术的晶片连接到电源的阴极，将晶片的电镀表面完全浸入电镀溶液中，并以逐步电流方式旋转或搅拌阴极进行电镀， 电镀条件的电流密度为0.01-10A / dm 2，温度为15-30℃。步骤5：电镀后，用去离子水清洗晶圆完全清洁 然后通过纺丝或吹干进行干燥。 通过采用TSV技术的铜电镀技术，以高纵横比进行三维铜互连的微电极填充方法具有高的通孔充填速度，表面上的薄铜层，没有产生空隙和裂纹的风险，并且可以实现 完全填充长宽比大于10：1的微孔，这是非常难以填充的。

    Additive for Reducing Voids after Annealing of Copper Plating with Through Silicon Via
    8.
    发明申请
    Additive for Reducing Voids after Annealing of Copper Plating with Through Silicon Via 有权
    通过硅经退火镀铜后减少空隙的添加剂

    公开(公告)号：US20160168738A1

    公开(公告)日：2016-06-16

    申请号：US14909745

    申请日：2013-12-25

    Applicant: SHANGHAI SINYANG SEMICONDUCTOR MATERIALS CO., LTD.

    Inventor： Su Wang ,  Xianxian Yu ,  Li Ma ,  Yanyan Li

    IPC: C25D3/38

    CPC classification number: C25D3/38 ,  C25D5/50 ,  C25D7/123 ,  H01L21/2885 ,  H01L21/76898

    Abstract: An additive for reducing voids after annealing of copper plating with through silicon via. The additive contains by weight percent: 0.05-1% of one or more of quaternized polyethylene imine and derivatives thereof having different molecular weights, and 1-10% of polyethylene glycol with an average molecular weight of 200-20000. The additive is used in combination with an electroplating solution of a copper methyl sulfonate system. The electroplating solution of a copper methyl sulfonate system contains 1-5 ml/L of the additive by volume ratio. The electroplating solution of a copper methyl sulfonate system contains by quality volume ratio: 50-110 g/L of copper ions, 5-50 g/L of methanesulfonic acid and 20-80 mg/L of chlorine ions. The electroplating solution also contains by volume ratio: 0.5-5 ml/L of accelerator, 5-20 ml/L of inhibitor and 5-10 ml/L of levelling agent. The additive for reducing voids after annealing of copper plating with through silicon via provided in the present invention can solve the problem of micro-voids between grain boundaries after high temperature annealing of copper plating.

    Abstract translation: 用于通过硅通孔在铜镀层退火后减少空隙的添加剂。 该添加剂含有重量百分比：0.05-1％的一种或多种季铵化聚乙烯亚胺及其不同分子量的衍生物，和1-10％的平均分子量为200-20000的聚乙二醇。 添加剂与铜甲基磺酸盐系统的电镀溶液组合使用。 铜甲基磺酸盐系统的电镀溶液含有1-5ml / L的体积比的添加剂。 铜甲磺酸铜系电镀液的质量体积比为：50-110g / L铜离子，5-50g / L甲磺酸和20-80mg / L氯离子。 电镀溶液还含有体积比：0.5-5ml / L的促进剂，5-20ml / L的抑制剂和5-10ml / L的流平剂。 通过本发明提供的通过硅通孔的镀铜退火后的空隙添加剂可以解决镀铜高温退火之后的晶界之间的微孔的问题。

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