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21. 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。

22. 发明授权

US06764537B2 Copper metal precursor 失效
标题翻译：铜金属前体
公开(公告)号：US06764537B2
公开(公告)日：2004-07-20
申请号：US10453829
申请日：2003-06-02
申请人： Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： C23C1618
CPC分类号： H01L21/28556 , C23C16/18
摘要： A method for chemical vapor deposition of copper metal thin film on a substrate includes heating a substrate onto which the copper metal thin film is to be deposited in a chemical vapor deposition chamber; vaporizing a precursor containing the copper metal, wherein the precursor is a compound of (&agr;-methylstyrene)Cu(I)(hfac), where hfac is hexafluoroacetylacetonate, and (hfac)Cu(I)L, where L is an alkene; introducing the vaporized precursor into the chemical vapor deposition chamber adjacent the heated substrate; and condensing the vaporized precursor onto the substrate thereby depositing copper metal onto the substrate. A copper metal precursor for use in the chemical vapor deposition of a copper metal thin film is a compound of (&agr;-methylstyrene)Cu(I)(hfac), where hfac is hexafluoroacetylacetonate, and (hfac)Cu(I)L, where L is an alkene taken from the group of alkenes consisting of 1-pentene, 1-hexene and trimethylvinylsilane.
摘要翻译：铜基金属薄膜在基板上进行化学气相沉积的方法包括在化学气相沉积室中加热要沉积铜金属薄膜的基板; 蒸发含有铜金属的前体，其中前体是（α-甲基苯乙烯）Cu（I）（hfac）的化合物，其中hfac是六氟乙酰丙酮化物，和（hfac）Cu（I）L，其中L是烯烃; 将蒸发的前体引入与加热的基底相邻的化学气相沉积室; 并将蒸发的前体冷凝到基底上，从而将铜金属沉积到基底上。用于铜金属薄膜的化学气相沉积的铜金属前体是（α-甲基苯乙烯）Cu（I）（hfac）的化合物，其中hfac是六氟乙酰丙酮化物，和（hfac）Cu（I）L，其中 L是从由1-戊烯，1-己烯和三甲基乙烯基硅烷组成的烯烃族中获得的烯烃。

23. 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.

24. 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。

25. 发明授权

US07696550B2 Bipolar switching PCMO capacitor 有权
标题翻译：双极开关PCMO电容
公开(公告)号：US07696550B2
公开(公告)日：2010-04-13
申请号：US11805177
申请日：2007-05-22
申请人： Tingkai Li , Lawrence J. Charneski , Wei-Wei Zhuang , David R. Evans , Sheng Teng Hsu
发明人： Tingkai Li , Lawrence J. Charneski , Wei-Wei Zhuang , David R. Evans , Sheng Teng Hsu
IPC分类号： H01L29/76
CPC分类号： H01L45/04 , H01L45/1233 , H01L45/147 , H01L45/1616
摘要： A multi-layer PrxCa1-xMnO3 (PCMO) thin film capacitor and associated deposition method are provided for forming a bipolar switching thin film. The method comprises: forming a bottom electrode; depositing a nanocrystalline PCMO layer; depositing a polycrystalline PCMO layer; forming a multi-layer PCMO film with bipolar switching properties; and, forming top electrode overlying the PCMO film. If the polycrystalline layers are deposited overlying the nanocrystalline layers, a high resistance can be written with narrow pulse width, negative voltage pulses. The PCMO film can be reset to a low resistance using a narrow pulse width, positive amplitude pulse. Likewise, if the nanocrystalline layers are deposited overlying the polycrystalline layers, a high resistance can be written with narrow pulse width, positive voltage pulses, and reset to a low resistance using a narrow pulse width, negative amplitude pulse.
摘要翻译：提供多层PrxCa1-xMnO3（PCMO）薄膜电容器和相关的沉积方法用于形成双极开关薄膜。该方法包括：形成底部电极; 沉积纳米晶体PCMO层; 沉积多晶PCMO层; 形成具有双极开关特性的多层PCMO膜; 并且形成覆盖PCMO膜的顶部电极。如果多晶层沉积在纳米晶层之上，则可以用窄脉冲宽度，负电压脉冲写入高电阻。 PCMO膜可以使用窄脉冲宽度，正幅度脉冲复位为低电阻。同样，如果纳米晶层沉积在多晶层上，则可以用窄脉冲宽度，正电压脉冲写入高电阻，并使用窄脉冲宽度，负幅度脉冲将其复位为低电阻。

26. 发明授权

US06972239B1 Low temperature MOCVD processes for fabrication of PrXCa1-xMnO3 thin films 有权
标题翻译：用于制造PrXCa1-xMnO3薄膜的低温MOCVD工艺
公开(公告)号：US06972239B1
公开(公告)日：2005-12-06
申请号：US10923529
申请日：2004-08-20
申请人： Tingkai Li , Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Tingkai Li , Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： C23C16/40 , H01L21/20 , H01L45/00
CPC分类号： H01L45/1616 , C23C16/40 , H01L45/04 , H01L45/1233 , H01L45/147
摘要： A method of fabricating a PCMO thin film at low temperature for use in a RRAM device includes preparing a PCMO precursor; preparing a substrate; placing the substrate into a MOCVD chamber; introducing the PCMO precursor into the MOCVD chamber to deposit a PCMO thin film on the substrate; maintaining a MOCVD vaporizer at between about 240° C. to 280° C. and maintaining the MOCVD chamber at a temperature of between about 300° C. to 400° C.; removing the PCMO thin-film bearing substrate from the MOCVD chamber; and completing the RRAM device.
摘要翻译：在低温下制造用于RRAM器件的PCMO薄膜的方法包括制备PCMO前体; 制备底物; 将基板放置在MOCVD室中; 将PCMO前体引入MOCVD室以在衬底上沉积PCMO薄膜; 将MOCVD蒸发器保持在约240℃至280℃之间并将MOCVD室保持在约300℃至400℃之间的温度下; 从MOCVD室中取出PCMO薄膜轴承衬底; 并完成RRAM设备。

27. 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。

28. 发明授权

US06596344B2 Method of depositing a high-adhesive copper thin film on a metal nitride substrate 失效
公开(公告)号：US06596344B2
公开(公告)日：2003-07-22
申请号：US09820227
申请日：2001-03-27
申请人： Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Lawrence J. Charneski , David R. Evans , Sheng Teng Hsu
IPC分类号： C23C1614
CPC分类号： H01L21/28556 , C23C16/18
摘要： A method for chemical vapor deposition of copper metal thin film on a substrate includes heating a substrate onto which the copper metal thin film is to be deposited in a chemical vapor deposition chamber; vaporizing a precursor containing the copper metal, wherein the precursor is a compound of (&agr;-methylstyrene)Cu(I)(hfac), where hfac is hexafluoroacetylacetonate, and (hfac)Cu(I)L, where L is an alkene; introducing the vaporized precursor into the chemical vapor deposition chamber adjacent the heated substrate; and condensing the vaporized precursor onto the substrate thereby depositing copper metal onto the substrate. A copper metal precursor for use in the chemical vapor deposition of a copper metal thin film is a compound of (&agr;-methylstyrene)Cu(I)(hfac), where hfac is hexafluoroacetylacetonate, and (hfac)Cu(I)L, where L is an alkene taken from the group of alkenes consisting of 1-pentene, 1-hexene and trimethylvinylsilane.

29. 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。

30. 发明授权

US06204176B1 Substituted phenylethylene precursor deposition method 有权
标题翻译：取代苯乙烯前体沉积法
公开(公告)号：US06204176B1
公开(公告)日：2001-03-20
申请号：US09351645
申请日：1999-07-12
申请人： Wei-Wei Zhuang , Lawrence J. Charneski , Sheng Teng Hsu
发明人： Wei-Wei Zhuang , Lawrence J. Charneski , Sheng Teng Hsu
IPC分类号： H01L2144
CPC分类号： C23C16/18
摘要： A method for using a Cu(hfac) precursor with a substituted phenylethylene ligand to form an adhesive seed layer on an IC surface 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, phenyl, H and C1 to C6 alkoxyl. One variation, the &agr;-methylstyrene ligand precursor has proved to be especially adhesive. Copper deposited with this precursor has low resistivity and high adhesive characteristics. The seed layer provides a foundation for subsequent Cu layers deposited through either CVD, PVD, or electroplating. The adhesive seed layer permits the subsequent Cu layer to be deposited through an economical high deposition rate process.
摘要翻译：已经提供了使用Cu（hfac）前体与取代的苯基乙炔配体在IC表面上形成粘合剂种子层的方法。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，苯基，H和C1至C6烷氧基的分子的键。一个变型，α-甲基苯乙烯配体前体已被证明是特别粘合的。沉积有该前体的铜具有低电阻率和高粘合特性。种子层为通过CVD，PVD或电镀沉积的后续Cu层提供了基础。粘合剂种子层允许随后的Cu层通过经济的高沉积速率工艺沉积。

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