公开(公告)号：EP0852229B1

公开(公告)日：2003-03-05

申请号：EP97308824.8

申请日：1997-11-04

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki, Yoshihide ,  Charneski, Lawrence Joel ,  Kobayashi, Masato ,  Nguyen, Tue

IPC分类号： C07F7/18 ,  C23C16/18

CPC分类号： C23C16/18 ,  C07F7/1836

公开(公告)号：EP0924754A3

公开(公告)日：1999-09-08

申请号：EP98308687.7

申请日：1998-10-23

申请人： Sharp Kabushiki Kaisha ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Ulrich, Bruce Dale ,  Nguyen, Tue ,  Kobayashi, Masato

IPC分类号： H01L21/3213 ,  C23F1/00

CPC分类号： H01L21/32134 ,  C23F1/18 ,  H01L21/02063 ,  H01L21/02087 ,  H01L21/3212 ,  H01L21/6708

摘要： A method of using diluted nitric acid and an edge bead removal tool to remove copper from the perimeter of a semiconductor wafer is provided. In one method, sensitive areas of the wafer are covered with photoresist, and the wafer perimeter cleared of photoresist, before the acid is applied In another method, sensitive areas of the wafer are protected with water spray as the copper etchant is applied. In a third method, the nitric acid is applied to clear the wafer perimeter of copper before a chemical mechanical polishing (CMP) is performed on the layer of deposited copper. The excess thickness of copper protects copper interconnection structures from reacting with the copper etchant. All these methods permit copper to be removed at a low enough temperature that copper oxides are not formed. A semiconductor wafer cleaned of copper in accordance with the above-described method, and a system for low temperature copper removal is also provided.

摘要翻译： 提供了使用稀释硝酸和边缘珠去除工具从半导体晶片的周边去除铜的方法。 在一种方法中，在施加酸之前，晶片的敏感区域覆盖有光致抗蚀剂，并且晶片周边清除了光致抗蚀剂。在另一种方法中，当施加铜蚀刻剂时，晶片的敏感区域用喷水保护。 在第三种方法中，在对沉积的铜层执行化学机械抛光（CMP）之前，施加硝酸以清除铜的晶圆周边。 铜的多余厚度保护铜互连结构免于与铜蚀刻剂反应。 所有这些方法都允许在足够低的温度下去除铜，以致不会形成铜氧化物。 还提供了根据上述方法清除铜的半导体晶片以及用于低温铜去除的系统。

公开(公告)号：EP0854507A3

公开(公告)日：1999-04-14

申请号：EP97308529.3

申请日：1997-10-24

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki Yoshihide ,  Kobayashi, Masato ,  Charneski Lawrence Joel

IPC分类号： H01L21/768 ,  H01L21/285 ,  H01L21/3205 ,  C23C16/18

CPC分类号： C23C16/18 ,  C07F7/1836 ,  C07F7/184 ,  C07F7/1844

摘要： Copper is applied to integrated circuit substrates for example by chemical vapor deposition using a Cu(hfac) (silylolefin ligand) precursor including combinations of C1-C8 alkyl groups with at least one C2-C8 alkyloxy group. The improved copper complex-ligand bond helps ensure that the ligand separates from the (hfac)Cu complex at consistent temperatures when Cu is to be deposited. Combinations of alkyloxy and alkyl groups allow the molecular weight of the precursor to be manipulated so that the volatility of the precursor is adjustable for specific process scenarios and additional silylolefins, hexafluoroacetylacetone (H-hfac), H-hfac dihydrate and water may be used separately or in combination to enhance deposition rate, conductivity, and precursor stability.

公开(公告)号：EP0854507B1

公开(公告)日：2006-06-07

申请号：EP97308529.3

申请日：1997-10-24

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki Yoshihide ,  Kobayashi, Masato ,  Charneski Lawrence Joel

IPC分类号： H01L21/285 ,  C23C16/18 ,  C07F7/18

CPC分类号： C23C16/18 ,  C07F7/1836 ,  C07F7/184 ,  C07F7/1844

公开(公告)号：EP0852229A3

公开(公告)日：1999-07-07

申请号：EP97308824.8

申请日：1997-11-04

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki, Yoshihide ,  Charneski, Lawrence Joel ,  Kobayashi, Masato ,  Nguyen, Tue

IPC分类号： C07F7/18 ,  C23C16/18

CPC分类号： C23C16/18 ,  C07F7/1836

摘要： Copper is applied to integrated circuit substrates, for example, by chemical vapor deposition using a copper precursor of a dimethoxymethylvinylsilane (dmomvs), or a methoxydimethylvinylsilane (modmvs) silylolefin ligand bonded to (hfac)Cu. The improved copper complex-ligand bond helps ensure that the ligand separates from the (hfac)Cu complex at consistent temperatures when Cu is to be deposited. Water vapor may be added to the precursor to improve the conductivity of the deposited Cu, and additional silylolefins, hexafluoroacetylacetone (H-hfac), and water may be used separately or in combination to enhance deposition rate, conductivity, and precursor stability.

摘要翻译： 例如，通过使用二甲氧基甲基乙烯基硅烷（dmomvs）的铜前体或与（hfac）Cu键合的甲氧基二甲基乙烯基硅烷（modmvs）甲硅烷基烯烃配体的化学气相沉积，将铜施加到集成电路基板。 改进的铜配合物 - 配体键有助于确保配位体在需要沉积Cu时在恒定温度下与（hfac）Cu配合物分离。 可以将水蒸气添加到前体中以改善沉积的Cu的电导率，并且可以单独或组合使用额外的甲硅烷烃，六氟乙酰丙酮（H-hfac）和水以提高沉积速率，电导率和前体稳定性。

公开(公告)号：EP0924754A2

公开(公告)日：1999-06-23

申请号：EP98308687.7

申请日：1998-10-23

申请人： Sharp Kabushiki Kaisha ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Ulrich, Bruce Dale ,  Nguyen, Tue ,  Kobayashi, Masato

IPC分类号： H01L21/3213 ,  C23F1/00

CPC分类号： H01L21/32134 ,  C23F1/18 ,  H01L21/02063 ,  H01L21/02087 ,  H01L21/3212 ,  H01L21/6708

摘要： A method of using diluted nitric acid and an edge bead removal tool to remove copper from the perimeter of a semiconductor wafer is provided. In one method, sensitive areas of the wafer are covered with photoresist, and the wafer perimeter cleared of photoresist, before the acid is applied In another method, sensitive areas of the wafer are protected with water spray as the copper etchant is applied. In a third method, the nitric acid is applied to clear the wafer perimeter of copper before a chemical mechanical polishing (CMP) is performed on the layer of deposited copper. The excess thickness of copper protects copper interconnection structures from reacting with the copper etchant. All these methods permit copper to be removed at a low enough temperature that copper oxides are not formed. A semiconductor wafer cleaned of copper in accordance with the above-described method, and a system for low temperature copper removal is also provided.

摘要翻译： 在半导体晶片的制造中，从晶片上去除铜的方法包括在包括铜互连的晶片顶表面上的选定区域上形成一层保护涂层。 蚀刻保护涂层以将其从晶片的顶表面和侧面的边缘移除，而不是从顶部表面铜互连。 稀释铜蚀刻剂溶液 在室温下使用 以从未被保护涂层覆盖的部分去除铜。 晶片包括至少一个直的顶表面边缘和侧面，并且保护涂层是沉积在晶片顶表面上的光致抗蚀剂。 沿着直的顶边缘表面的光致抗蚀剂的选定区域通过靠近晶片的荫罩曝光，以化学改变曝光的光致抗蚀剂。 光致抗蚀剂被显影以沿着顶表面的直边缘去除它，随后从顶表面直边蚀刻铜。 用去离子水冲洗将晶片清除铜蚀刻剂化合物，并将蚀刻的保护涂层从晶片上完全除去。 在替代实施例中：（i）当应用铜蚀刻剂时，晶片的敏感区域可以用喷水器保护; （ii）在对沉积的铜层进行化学机械抛光之前，施加铜蚀刻剂以清除铜的晶片周边，其中Coper的过剩厚度保护铜互连结构不与铜蚀刻剂反应。 另一种保护涂层是旋涂玻璃。

公开(公告)号：EP0854507A2

公开(公告)日：1998-07-22

申请号：EP97308529.3

申请日：1997-10-24

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki Yoshihide ,  Kobayashi, Masato ,  Charneski Lawrence Joel

IPC分类号： H01L21/768 ,  H01L21/285 ,  H01L21/3205 ,  C23C16/18

CPC分类号： C23C16/18 ,  C07F7/1836 ,  C07F7/184 ,  C07F7/1844

摘要： Copper is applied to integrated circuit substrates for example by chemical vapor deposition using a Cu(hfac) (silylolefin ligand) precursor including combinations of C1-C8 alkyl groups with at least one C2-C8 alkyloxy group. The improved copper complex-ligand bond helps ensure that the ligand separates from the (hfac)Cu complex at consistent temperatures when Cu is to be deposited. Combinations of alkyloxy and alkyl groups allow the molecular weight of the precursor to be manipulated so that the volatility of the precursor is adjustable for specific process scenarios and additional silylolefins, hexafluoroacetylacetone (H-hfac), H-hfac dihydrate and water may be used separately or in combination to enhance deposition rate, conductivity, and precursor stability.

摘要翻译： 用于铜（CU）到选定表面的化学气相沉积（CVD）的挥发性铜（Cu）前体化合物。 前体化合物包括：（i）Cu + 1（六氟乙酰丙酮化物）; 和（ii）包含至少一个具有至少两个与硅原子键合的C原子的烷氧基的硅单元配体。 当化合物被加热至汽化温度时，烷氧基硅单体烯配体中的氧的电子供体能力提供了Cu和烷氧基 - 硅单体烯配体之间的牢固结合。 还要求保护的是前体共混物，其中在包含水蒸汽的化合物中包含添加剂，该水蒸汽具有真空分压，其中水蒸气与前体共混，使得水蒸汽的分压为前体分压的0.5-5％ 并且向前体添加水蒸汽增加了Cu沉积的速率。

公开(公告)号：EP0852229A2

公开(公告)日：1998-07-08

申请号：EP97308824.8

申请日：1997-11-04

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki, Yoshihide ,  Charneski, Lawrence Joel ,  Kobayashi, Masato ,  Nguyen, Tue

IPC分类号： C07F7/18 ,  C23C16/18

CPC分类号： C23C16/18 ,  C07F7/1836

摘要： Copper is applied to integrated circuit substrates, for example, by chemical vapor deposition using a copper precursor of a dimethoxymethylvinylsilane (dmomvs), or a methoxydimethylvinylsilane (modmvs) silylolefin ligand bonded to (hfac)Cu. The improved copper complex-ligand bond helps ensure that the ligand separates from the (hfac)Cu complex at consistent temperatures when Cu is to be deposited. Water vapor may be added to the precursor to improve the conductivity of the deposited Cu, and additional silylolefins, hexafluoroacetylacetone (H-hfac), and water may be used separately or in combination to enhance deposition rate, conductivity, and precursor stability.

摘要翻译： 例如通过使用二甲氧基甲基乙烯基硅烷（dmomvs）的铜前体或与（hfac）Cu键合的甲氧基二甲基乙烯基硅烷（modmvs）silylolefin配体的化学气相沉积将铜应用于集成电路基板。 当Cu沉积时，改进的铜络合物 - 配体键有助于确保配体在恒定温度下与（hfac）Cu络合物分离。 可以向前体中加入水蒸汽以改善沉积的Cu的导电性，并且可以单独或组合使用另外的水溶性六氟乙酰丙酮（H-hfac）和水，以增强沉积速率，导电性和前体稳定性。

公开(公告)号：EP1670051A1

公开(公告)日：2006-06-14

申请号：EP06075568.3

申请日：1998-10-23

申请人： SHARP KABUSHIKI KAISHA ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Ulrich, Bruce Dale ,  Nguyen, Tue ,  Kobayashi, Masato

IPC分类号： H01L21/3213 ,  C23F1/00

CPC分类号： H01L21/32134 ,  C23F1/18 ,  H01L21/02063 ,  H01L21/02087 ,  H01L21/3212 ,  H01L21/6708

摘要： An apparatus for removing copper from semiconductor wafer disk having top and bottom surfaces, with top surface edges and sides along the top surface edge around the perimeter of the wafer surfaces comprises: an enclosed chamber; a spin-chuck to rotate the mounted wafer; a first solution application nozzle having at least one position approximately above the wafer edge to spray diluted copper etchant solution at room temperature towards the sides and perimeter edge of the wafer, to remove copper from the sides and perimeter edge of the wafer; a second nozzle having at least one position approximately above the wafer perimeter to spray a protective coating etchant upon the edge of the wafer top surface along the perimeter, whereby protective coating, masking copper interconnection structures on the wafer top surface, is removed on the edge of the top surface and the wafer side before copper etchant is applied; and a third solution application nozzle having at least one position approximately above the center of the wafer to spray de-ionized water on the wafer, whereby the water is used to remove etchants and etchant compounds from the wafer.

摘要翻译： 一种用于从具有顶表面和底表面的半导体晶片盘中去除铜的装置，具有围绕晶片表面的周边的顶表面边缘的顶表面边缘和侧边包括：封闭室; 用于旋转安装的晶片的旋转卡盘; 第一溶液施加喷嘴，其具有大约在晶片边缘上方的至少一个位置，以在室温下朝向晶片的侧面和周边边缘喷射稀释的铜蚀刻剂溶液，以从晶片的侧面和周边边缘移除铜; 第二喷嘴具有大约在晶片周边上方的至少一个位置，以沿着周边在晶片顶表面的边缘上喷射保护性涂层蚀刻剂，由此在晶片顶表面上的保护涂层，掩模铜互连结构在边缘上被去除 在施加铜蚀刻剂之前的顶表面和晶片侧; 以及第三溶液施加喷嘴，其具有大约高于晶片中心的至少一个位置以在晶片上喷射去离子水，由此使用水从晶片去除蚀刻剂和蚀刻剂化合物。

公开(公告)号：EP0987346A1

公开(公告)日：2000-03-22

申请号：EP99302806.7

申请日：1999-04-12

申请人： Sharp Kabushiki Kaisha ,  SHARP MICROELECTRONICS TECHNOLOGY, INC.

发明人： Senzaki, Yoshihide ,  Kobayashi, Masato ,  Charneski, Lawrence J. ,  Nguyen, Tue

IPC分类号： C23C16/18 ,  C07F7/18

CPC分类号： C23C16/18

摘要： Chemical vapor deposition (CVD) of copper (Cu) to integrated circuit substrates uses as Cu precursor a Cu(hfac)(ligand) including a silylolefin ligand including combinations of C1-C8 alkyl groups with at least one C2-C8 alkyloxy group, combinations of ethyl and ethoxy groups being preferred. The alkyloxy oxygens and the long carbon chains of the alkyl and alkyloxy groups increase precursor stability by contributing electrons to the Cu(hfac) complex to assist ligand separation from the complex at consistent temperatures. Selection of alkyloxy and alkyl groups enables precursor volatility to be adjusted to specific process scenarios.

摘要翻译： 铜（Cu）到集成电路基板的化学气相沉积（CVD）用作Cu前体Cu（hfac）（配体），其包括含有C 1 -C 8烷基与至少一个C 2 -C 8烷氧基的组合的硅单元配体配体，组合 的乙基和乙氧基是优选的。 烷基和烷氧基的烷氧基氧和长碳链通过向Cu（hfac）络合物贡献电子来增加前体的稳定性，以辅助配体在一致的温度下与络合物分离。 选择烷氧基和烷基可使前体挥发性调整到具体的工艺情况。