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1. 发明授权

US06281589B1 System of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides 有权
标题翻译：选择性地清洗铜基板表面的系统，原位去除铜氧化物
公开(公告)号：US06281589B1
公开(公告)日：2001-08-28
申请号：US09270901
申请日：1999-03-15
申请人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： H01L21302
CPC分类号： C23G5/00 , H01L21/02063 , H01L21/02068 , H01L21/31111 , H01L21/31138 , H01L21/32134 , H01L21/76838
摘要： A system and method of selectively etching copper surfaces free of copper oxides in preparation for the deposition of an interconnecting metallic material is provided. The method removes metal oxides with &bgr;-diketones, such as Hhfac. The Hhfac is delivered into the system in vapor form, and reacts almost exclusively to copper oxides. The by-products of the cleaning process are likewise volatile for removal from the system with a vacuum pressure. Since the process is easily adaptable to most IC process systems, it can be conducted in an oxygen-free environment, without the removal of the IC from the process chamber. The in-situ cleaning process permits a minimum amount of copper oxide to reform before the deposition of the overlying interconnection metal. In this manner, a highly conductive electrical interconnection between the copper surface and the interconnecting metal material is formed. An IC having a metal interconnection, in which the underlying copper layer is cleaned of copper oxides, in-situ with Hhfac vapor, is also provided.
摘要翻译：提供了一种选择性地蚀刻不含铜氧化物的铜表面以准备沉积互连金属材料的系统和方法。该方法用β-二酮除去金属氧化物，如Hhfac。 Hhfac以蒸气形式输送到系统中，几乎完全与铜氧化物反应。清洁过程的副产物同样是挥发性的，用于在真空压力下从系统中除去。由于该方法很容易适用于大多数IC工艺系统，所以它可以在无氧环境中进行，而不会从处理室中移除IC。在沉积互连金属之前，原位清洁工艺允许最小量的氧化铜重整。以这种方式，形成铜表面和互连金属材料之间的高导电性电互连。还提供了具有金属互连的IC，其中下面的铜层用Hhfac蒸气原位清除了铜氧化物。

2. 发明授权

US06281377B1 Substituted cycloalkene new copper precursors for chemical vapor deposition of copper metal thin films 有权
标题翻译：用于铜金属薄膜化学气相沉积的取代的环烯烃新铜前体
公开(公告)号：US06281377B1
公开(公告)日：2001-08-28
申请号：US09502425
申请日：2000-02-11
申请人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： C07F108
CPC分类号： C23C16/18 , C07F1/08
摘要： A method of forming a volatile copper precursor for chemical vapor deposition of copper metal thin film includes formation of a volatile liquid having a chemical formula of (n-R-m-cyclohexene)Cu(I)(hfac) or (n-R-m-cyclopentene)Cu(I)(hfac), where n,m=1-6, and where R is a alkyl, such as methyl and ethyl.
摘要翻译：形成铜金属薄膜的化学气相沉积挥发性铜前体的方法包括形成化学式为（nRm-环己烯）Cu（I）（hfac）或（nRm-环戊烯）Cu（I）的挥发性液体，（hfac），其中n，m = 1-6，其中R是烷基，例如甲基和乙基。

3. 发明授权

US5939334A System and method of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides 失效
标题翻译：选择性地清洗铜基板表面的系统和方法，原位去除铜氧化物
公开(公告)号：US5939334A
公开(公告)日：1999-08-17
申请号：US861808
申请日：1997-05-22
申请人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： C23F1/12 , C23G5/00 , H01L21/302 , H01L21/304 , H01L21/306 , H01L21/311 , H01L21/3213 , H01L21/768
CPC分类号： C23G5/00 , H01L21/02063 , H01L21/31111 , H01L21/31138 , H01L21/32134 , H01L21/76838 , H01L21/02068
摘要： A system and method of selectively etching copper surfaces free of copper oxides in preparation for the deposition of an interconnecting metallic material is provided. The method removes metal oxides with .beta.-diketones, such as Hhfac. The Hhfac is delivered into the system in vapor form, and reacts almost exclusively to copper oxides. The by-products of the cleaning process are likewise volatile for removal from the system with a vacuum pressure. Since the process is easily adaptable to most IC process systems, it can be conducted in an oxygen-free environment, without the removal of the IC from the process chamber. The in-situ cleaning process permits a minimum amount of copper oxide to reform before the deposition of the overlying interconnection metal. In this manner, a highly conductive electrical interconnection between the copper surface and the interconnecting metal material is formed. An IC having a metal interconnection, in which the underlying copper layer is cleaned of copper oxides, in-situ with Hhfac vapor, is also provided.
摘要翻译：提供了一种选择性地蚀刻不含铜氧化物的铜表面以准备沉积互连金属材料的系统和方法。该方法用β-二酮如Hhfac除去金属氧化物。 Hhfac以蒸气形式输送到系统中，几乎完全与铜氧化物反应。清洁过程的副产物同样是挥发性的，用于在真空压力下从系统中除去。由于该方法很容易适用于大多数IC工艺系统，所以它可以在无氧环境下进行，而不会从处理室中移除IC。在沉积互连金属之前，原位清洁工艺允许最小量的氧化铜重整。以这种方式，形成铜表面和互连金属材料之间的高导电性电互连。还提供了具有金属互连的IC，其中下面的铜层用Hhfac蒸气原位清除了铜氧化物。

4. 发明授权

US06555916B2 Integrated circuit prepared by selectively cleaning copper substrates, in-situ, to remove copper oxides 失效
公开(公告)号：US06555916B2
公开(公告)日：2003-04-29
申请号：US09941023
申请日：2001-08-27
申请人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： H01L21302
CPC分类号： C23G5/00 , H01L21/02063 , H01L21/02068 , H01L21/31111 , H01L21/31138 , H01L21/32134 , H01L21/76838
摘要： A system and method of selectively etching copper surfaces free of copper oxides in preparation for the deposition of an interconnecting metallic material is provided The method removes metal oxides with &bgr;-diketones, such as Hhfac. The Hhfac is delivered into the system in vapor form, and reacts almost exclusively to copper oxides. The by-products of the cleaning process are likewise volatile for removal from the system with a vacuum pressure. Since the process is easily adaptable to most IC process systems, it can be conducted in an oxygen-free environment, without the removal of the IC from the process chamber. The in-situ cleaning process permits a minimum amount of copper oxide to reform before the deposition of the overlying interconnection metal. In this manner, a highly conductive electrical interconnection between the copper surface and the interconnecting metal material is formed. An IC having a metal interconnection, in which the underlying copper layer is cleaned of copper oxides, in-situ with Hhfac vapor, is also provided.

5. 发明授权

US06669870B2 Substituted phenylethylene precursor synthesis method 失效
标题翻译：取代苯乙烯前体合成方法
公开(公告)号：US06669870B2
公开(公告)日：2003-12-30
申请号：US09820024
申请日：2001-03-28
申请人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： H01B102
CPC分类号： C23C16/18
摘要： A Cu(hfac) precursor with a substituted phenylethylene ligand has been provided. The substituted phenylethylene ligand includes bonds to molecules selected from the group consisting of C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 phenyl, H and C1 to C6 alkoxyl. One variation, the &agr;-methylstyrene ligand precursor has proved to be stable a low temperatures, and sufficiently volatile at higher temperatures. Copper deposited with this precursor has low resistivity and high adhesive characteristics. A synthesis method has been provided which produces a high yield of the above-described precursor.
摘要翻译：已经提供了具有取代的苯基乙炔配体的Cu（hfac）前体。取代的苯基乙炔配体包括与选自C1至C6烷基，C1至C6卤代烷基，C1至C6苯基，H和C1至C6烷氧基的分子的键。已经证明α-甲基苯乙烯配体前体的一个变化是在低温下是稳定的，并且在较高温度下具有足够的挥发性。沉积有该前体的铜具有低电阻率和高粘合特性。已经提供了产生高产率的上述前体的合成方法。

6. 发明授权

US06245261B1 Substituted phenylethylene precursor and synthesis method 有权
标题翻译：取代苯乙烯前体及其合成方法
公开(公告)号：US06245261B1
公开(公告)日：2001-06-12
申请号：US09210099
申请日：1998-12-11
申请人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： H01B102
CPC分类号： C23C16/18
摘要： A Cub(hfac) precursor with a substituted phenylethylene ligand has been provided. The substituted phenylethylene ligand includes bonds to molecules selected from the group consisting of C1 to C6 alkyl, C1 to C6 haloalkyl, C1 to C6 phenyl, H and C1 to C6 alkoxyl. One variation, the &agr;-methylstyrene ligand precursor has proved to be stable a low temperatures, and sufficiently volatile at higher temperatures. Copper deposited with this precursor has low resistivity and high adhesive characteristics. A synthesis method has been provided which produces a high yield of the above-described precursor.
摘要翻译：已经提供了具有取代的苯基乙炔配体的Cub（hfac）前体。取代的苯基乙炔配体包括与选自C1至C6烷基，C1至C6卤代烷基，C1至C6苯基，H和C1至C6烷氧基的分子的键。已经证明α-甲基苯乙烯配体前体的一个变化是在低温下是稳定的，并且在较高温度下具有足够的挥发性。沉积有该前体的铜具有低电阻率和高粘合特性。已经提供了产生高产率的上述前体的合成方法。

7. 发明授权

US5994571A Substituted ethylene precursor and synthesis method 有权
标题翻译：取代乙烯前体及其合成方法
公开(公告)号：US5994571A
公开(公告)日：1999-11-30
申请号：US215921
申请日：1998-12-18
申请人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David Russell Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Tue Nguyen , Lawrence J. Charneski , David Russell Evans , Sheng Teng Hsu
IPC分类号： C07C11/04 , C07F1/08 , C07F1/10 , C07F15/00 , C23C16/18 , H01L21/285 , C23C16/00
CPC分类号： C23C16/18 , C07F1/08
摘要： A Cu(hfac) precursor with a substituted ethylene ligand has been provided. The substituted ethylene ligand includes bonds to molecules selected from the group consisting of C.sub.1 to C.sub.8 alkyl, C.sub.1 to C.sub.8 haloalkyl, H, and C.sub.1 to C.sub.8 alkoxyl. One variation, the 2-methyl-1-butene ligand precursor has proved to be stable at room temperature, and extremely volatile at higher temperatures. Copper deposited with this precursor has low resistivity and high adhesive characteristics. Because of the volatility, the deposition rate of copper deposited with this precursor is very high. A synthesis method has been provided which produces a high yield of the above-described precursor.
摘要翻译：已经提供了具有取代的乙烯配体的Cu（hfac）前体。取代的乙烯配体包括与选自C1至C8烷基，C1至C8卤代烷基，H和C1至C8烷氧基的分子的键。一个变体，2-甲基-1-丁烯配体前体已被证明在室温下是稳定的，并且在较高温度下极易挥发。沉积有该前体的铜具有低电阻率和高粘合特性。由于挥发性，沉积有这种前体的铜的沉积速率非常高。已经提供了产生高产率的上述前体的合成方法。

8. 发明授权

US6002176A Differential copper deposition on integrated circuit surfaces 有权
标题翻译：集成电路表面上的差异铜沉积
公开(公告)号：US6002176A
公开(公告)日：1999-12-14
申请号：US135376
申请日：1998-08-17
申请人： Tue Nguyen , Lawrence J. Charneski , Sheng Teng Hsu
发明人： Tue Nguyen , Lawrence J. Charneski , Sheng Teng Hsu
IPC分类号： C23C16/02 , C23C16/04 , H01L21/28 , H01L21/285 , H01L21/3205 , H01L21/768 , H01L23/52 , H01L23/532 , H01L23/48 , H01L29/40
CPC分类号： C23C16/04 , C23C16/0245 , H01L21/28562 , H01L21/76801 , H01L21/76825 , H01L21/76838 , H01L23/53238 , H01L21/28568 , H01L2924/0002 , H01L2924/3011 , Y10S438/906 , Y10S438/974
摘要： A method for selectively applying CVD copper to metallic surfaces, that are co-located with non-metallic surfaces, is provided. The method prepares both the metal and non-metallic surfaces with a low energy ion etch of an inert gas. The etching promotes the growth of copper on the metallic surface, and inhibits the growth on the non-metallic surface. Following an application of CVD copper, the surfaces are etched again to clean any residual copper from the non-metallic surface, and to again prepare the surfaces for another deposition of copper. Through repeated cycles of etching and copper deposition, the copper overlying the metallic surface is accumulated to achieve the desired thickness, while the non-metallic surface remains free of copper. A method is also provided for the selective deposition of copper on metallic surfaces to fill interconnects in damascene IC structures. An IC with a copper layer overlying a metallic surface, co-located with a non-metallic surface, where the copper layer is grown through repeated cycles of ion etching and copper deposition, is also provided.
摘要翻译：提供了一种用于将CVD铜选择性地应用于与非金属表面共位的金属表面的方法。该方法通过惰性气体的低能量离子蚀刻来准备金属和非金属表面。蚀刻促进金属表面上的铜的生长，并且抑制非金属表面上的生长。在应用CVD铜之后，再次蚀刻表面以从非金属表面清除任何残留的铜，并再次准备用于另外沉积铜的表面。通过重复的蚀刻和铜沉积循环，覆盖金属表面的铜被积聚以达到所需的厚度，同时非金属表面保持不含铜。还提供了一种用于在金属表面上选择性沉积铜以填充镶嵌IC结构中的互连的方法。还提供了具有覆盖金属表面的铜层的IC，其与非金属表面共同定位，其中铜层通过重复的离子蚀刻和铜沉积循环而生长。

9. 发明授权

US5851367A Differential copper deposition on integrated circuit surfaces and method for same 失效
标题翻译：集成电路表面上的差分铜沉积及其相同的方法
公开(公告)号：US5851367A
公开(公告)日：1998-12-22
申请号：US731258
申请日：1996-10-11
申请人： Tue Nguyen , Lawrence J. Charneski , Sheng Teng Hsu
发明人： Tue Nguyen , Lawrence J. Charneski , Sheng Teng Hsu
IPC分类号： C23C16/02 , C23C16/04 , H01L21/28 , H01L21/285 , H01L21/3205 , H01L21/768 , H01L23/52 , H01L23/532 , H01L21/302
CPC分类号： C23C16/04 , C23C16/0245 , H01L21/28562 , H01L21/76801 , H01L21/76825 , H01L21/76838 , H01L23/53238 , H01L21/28568 , H01L2924/0002 , H01L2924/3011 , Y10S438/906 , Y10S438/974
摘要： A method for selectively applying CVD copper to metallic surfaces, that are co-located with non-metallic surfaces, is provided. The method prepares both the metal and non-metallic surfaces with a low energy ion etch of an inert gas through the use of an ion gun. The etching promotes the growth of copper on the metallic surface, and inhibits the growth on the non-metallic surface. Following an application of CVD copper, the surfaces are etched again to clean any residual copper from the non-metallic surface, and to again prepare the surfaces for another deposition of copper. Through repeated cycles of etching and copper deposition, the copper overlying the metallic surface is accumulated to achieve the desired thickness, while the non-metallic surface remains free of copper. A method is also provided for the selective deposition of copper on metallic surfaces to fill interconnects in damascene IC structures. An IC with a copper layer overlying a metallic surface, co-located with a non-metallic surface, where the copper layer is grown through repeated cycles of ion etching and copper deposition, is also provided.
摘要翻译：提供了一种用于将CVD铜选择性地应用于与非金属表面共位的金属表面的方法。该方法通过使用离子枪以惰性气体的低能量离子蚀刻来准备金属和非金属表面。蚀刻促进金属表面上的铜的生长，并且抑制非金属表面上的生长。在应用CVD铜之后，再次蚀刻表面以从非金属表面清除任何残留的铜，并再次准备用于另外沉积铜的表面。通过重复的蚀刻和铜沉积循环，覆盖金属表面的铜被积聚以达到所需的厚度，同时非金属表面保持不含铜。还提供了一种用于在金属表面上选择性沉积铜以填充镶嵌IC结构中的互连的方法。还提供了具有覆盖金属表面的铜层的IC，其与非金属表面共同定位，其中铜层通过重复的离子蚀刻和铜沉积循环而生长。

10. 发明授权

US5744192A Method of using water vapor to increase the conductivity of cooper desposited with cu(hfac)TMVS 失效
标题翻译：使用水蒸气增加铜（hfac）TMVS沉积铜的电导率的方法
公开(公告)号：US5744192A
公开(公告)日：1998-04-28
申请号：US745562
申请日：1996-11-08
申请人： Tue Nguyen , Yoshihide Senzaki , Masato Kobayashi , Lawrence J. Charneski , Sheng Teng Hsu
发明人： Tue Nguyen , Yoshihide Senzaki , Masato Kobayashi , Lawrence J. Charneski , Sheng Teng Hsu
IPC分类号： C01G3/00 , C23C16/18 , C23C16/448 , C23C16/52 , H01L21/28 , H01L21/285 , H01L21/60 , B05D5/12 , C23C16/04
CPC分类号： C23C16/4481 , C23C16/18 , H01L2924/0002
摘要： A method of blending water vapor with volatile Cu(hfac)TMVS (copper hexafluoroacetylacetonate trimethylvinylsilane) is provided which improves the deposition rate of Cu, without degrading the resistivity of the Cu deposited upon an integrated circuit surface. The method of the present invention uses a relatively small amount of water vapor, approximately 0.3 to 3% of the total pressure of the system in which chemical vapor deposition (CVD) Cu is applied. The method specifies the flow rates of the liquid precursor, carrier gas, and liquid water. The method also specifies the pressures of the vaporized precursor, vaporized precursor blend including carrier gas and water vapor. In addition, the temperatures of the vaporizers, chamber walls, and IC surfaces are disclosed. A Cu precursor blend is also provided comprising vaporized Cu(hfac)TMVS and water vapor. The ratio of water vapor pressure to vaporized precursor is approximately 0.5 to 5%. Further, an IC surface covered with Cu applied with a Cu precursor blend including vaporized Cu(hfac)TMVS and water vapor, with the above mentioned ratio of water vapor pressure to volatile Cu(hfac)TMVS pressure, is provided.
摘要翻译：提供了将水蒸汽与挥发性Cu（hfac）TMVS（六氟乙酰丙酮酸铜三甲基乙烯基硅烷）共混的方法，其改善了Cu的沉积速率，而不降低沉积在集成电路表面上的Cu的电阻率。本发明的方法使用相对少量的水蒸气，其中施加化学气相沉积（CVD）Cu的系统的总压力的大约0.3至3％。该方法规定了液体前体，载气和液态水的流量。该方法还规定了蒸发的前体，蒸发的前体共混物包括载气和水蒸气的压力。此外，公开了蒸发器，室壁和IC表面的温度。还提供了包含蒸发的Cu（hfac）TMVS和水蒸气的Cu前体共混物。水蒸气压与汽化前体的比率约为0.5〜5％。此外，提供了用Cu涂覆Cu包含蒸发的Cu（hfac）TMVS和水蒸气的Cu前体共混物的IC表面，具有上述的水蒸气压与挥发性Cu（hfac）TMVS压力的比率。

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