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    • 2. 发明授权
    • Process for electrolessly plating copper and plating solution therefor
    • 无电镀铜及其电镀液的方法
    • US4935267A
    • 1990-06-19
    • US190854
    • 1988-05-06
    • Koji KondoKatuhiko MurakawaNobumasa IshidaJunji IshikawaKaoru NomotoFutoshi Ishikawa
    • Koji KondoKatuhiko MurakawaNobumasa IshidaJunji IshikawaKaoru NomotoFutoshi Ishikawa
    • C23C18/40H05K3/18
    • H05K3/181C23C18/40
    • By forming a first copper layer on a substrate by using a complexing agent for copper ion, which has a low copper complex stability constant, a uniform second layer can be stably formed by a second complexing agent for a copper ion, which has a high copper complex stability constant, even if the substrate is composed of a material having a low catalytic activity, such as tungsten, or even if the catalytic activity of the substrate is uneven. A similar effect can also be obtained by adding a small amount of a complexing agent for a copper ion, having a low stability constant, to an electroless copper plating bath containing a complexing agent for a copper ion, having a low stability constant. In this case, an effect of preventing stopping of the reaction of the complexing agent of a copper ion, having a high stability constant, is attained. Most preferably, after formation of a uniform first copper layer by an electroless copper plating solution containing a complexing agent for a copper ion, having a low stability constant, a second copper layer is formed by an electroless copper plating solution containing a complexing agent for a copper ion, having a high stability constant and also in this case, a small amount of a complexing agent for a copper ion, having a low stability constant, is added.
    • 通过使用铜络合物的稳定常数低的铜离子络合剂,在基板上形成第一铜层,可以通过第二铜离子络合剂稳定地形成均匀的第二层,铜离子配位剂 复合稳定性常数即使基材由具有低催化活性的材料如钨构成,或即使基材的催化活性不均匀也是如此。 通过向具有低稳定性常数的含有铜离子络合剂的化学镀铜浴中加入少量用于具有低稳定性常数的铜离子络合剂也可以获得类似的效果。 在这种情况下,可以获得阻止具有高稳定性常数的铜离子络合剂的反应停止的效果。 最优选的是,通过含有铜离子络合剂的化学镀铜溶液形成均匀的第一铜层,具有低稳定性常数,第二铜层由含有络合剂的化学镀铜溶液形成, 铜离子,具有高稳定性常数,并且在这种情况下,加入少量的具有低稳定常数的铜离子络合剂。
    • 5. 发明授权
    • Electroless copper plating solution and process for formation of copper
film
    • 化学镀铜溶液及铜膜形成工艺
    • US5039338A
    • 1991-08-13
    • US456659
    • 1989-12-29
    • Koji KondoSeiji AmakusaKatuhiko MurakawaKatsuaki KojimaNobumasa IshidaJunji IshikawaFutoshi Ishikawa
    • Koji KondoSeiji AmakusaKatuhiko MurakawaKatsuaki KojimaNobumasa IshidaJunji IshikawaFutoshi Ishikawa
    • C23C18/40
    • C23C18/405
    • Disclosed are an electroless copper plating solution comprising a copper ion, a copper ion-complexing agent, a reducing agent and a pH-adjusting agent, the plating solution comprising a trialkanolmonoamine or a salt thereof as a complexing agent and accelerator in an amount giving a higher copper deposition speed than the copper deposition speed obtained when the trialkanolmonoamine or salt thereof is present in an amount sufficient to complex the copper ion but not enough to function as the accelerator, and 1.2.times.10.sup.-4 to 1.2.times.10.sup.-3 mole/l of an iron ion compound as a reaction initiator and/or 1.92.times.10.sup.-4 to 1.92.times.10.sup.-3 mole/l of at least one compound selected from the group consisting of pyridazine, methylpiperidine, 1,2-di-(2-pyridyl)ethylene, 1,2-di-(pyridyl)ethylene, 2,2'-dipyridylamine, 2,2'-bipyridyl, 2,2'-bipyrimidine, 6,6'-dimethyl-2,2'-dipyridyl, di-2-pyridylketone, N,N,N',N'-tetraethylethylenediamine, naphthalene, 1,8-naphthyidine, 1,6-naphthyridine, tetrathiafurvalene, .alpha.,.alpha.,.alpha.-terpyridine, phthalic acid, isophthalic acid and 2,2'-dibenzoic acid as an agent for improving the physical properties of a plating film, and a process for forming an electroless copper deposition film by using this electroless copper plating solution.
    • 公开了包含铜离子,铜离子络合剂,还原剂和pH调节剂的无电镀铜溶液,所述镀溶液包含三烷醇单胺或其盐作为络合剂和促进剂,其量为 当三烷醇单胺或其盐以足以使铜离子复合但不足以起促进剂的量存在时获得的铜沉积速度高的铜沉积速度,以及1.2×10 -4至1.2×10 -3摩尔/升的 作为反应引发剂的铁离子化合物和/或1.92×10 -4至1.92×10 -3摩尔/升的选自哒嗪,甲基哌啶,1,2-二(2-吡啶基)乙烯的至少一种化合物 ,1,2-二(吡啶基)乙烯,2,2'-二吡啶基胺,2,2'-联吡啶基,2,2'-联嘧啶,6,6'-二甲基-2,2'-联吡啶,二-2 吡啶基酮,N,N,N',N'-四乙基乙二胺,萘,1,8-萘啶,1,6-萘啶,四糠醛,α,α ,α-三联吡啶,邻苯二甲酸,间苯二甲酸和2,2'-二苯甲酸作为改善电镀膜的物理性能的试剂,以及使用该化学镀铜溶液形成无电解铜沉积膜的方法。
    • 6. 发明授权
    • Electroless copper plating solution and process for formation of copper
film
    • 化学镀铜溶液及铜膜形成工艺
    • US5965211A
    • 1999-10-12
    • US725767
    • 1991-07-02
    • Koji KondoSeiji AmakusaKatuhiko MurakawaKatsuaki KojimaNobumasa IshidaJunji IshikawaFutoshi Ishikawa
    • Koji KondoSeiji AmakusaKatuhiko MurakawaKatsuaki KojimaNobumasa IshidaJunji IshikawaFutoshi Ishikawa
    • C23C18/40B05D3/04B05D1/18B05D3/10
    • C23C18/405
    • Disclosed are an electroless copper plating solution comprising a copper ion, a copper ion-complexing agent, a reducing agent and a pH-adjusting agent, the plating solution comprising a trialkanolmonoamine or a salt thereof as a complexing agent and accelerator in an amount giving a higher copper deposition speed than the copper deposition speed obtained when the trialkanolmonoamine or salt thereof is present in an amount sufficient to complex the copper ion but not enough to function as the accelerator, and 1.2.times.10.sup.-4 to 1.2.times.10.sup.-3 mole/l of an iron ion compound as a reaction initiator and/or 1.92.times.10.sup.-4 to 1.92.times.10.sup.-3 mole/l of at least one compound selected from the group consisting of pyridazine, methylpiperidine, 1,2-di-(2-pyridyl)ethylene, 1,2-di-(pyridyl)ethylene, 2,2'-dipyridylamine, 2,2'-bipyridyl, 2,2'-bipyrimidine, 6,6'-dimethyl-2,2'-dipyridyl, di-2-pyridylketone, N,N,N',N'-tetraethylethylenediamine, napththalene, 1,8-naphthyridine, 1,6-naphthyridine, tetrathiafurvalene, .alpha.,.alpha.,.alpha.-terpyridine, phthalic acid, isophthalic acid and 2,2'-dibenzoic acid as an agent for improving the physical properties of a plating film, and a process for forming an electroless copper deposition film by using this electroless copper plating solution.
    • 公开了包含铜离子,铜离子络合剂,还原剂和pH调节剂的无电镀铜溶液,所述镀溶液包含三烷醇单胺或其盐作为络合剂和促进剂,其量为 当三烷醇单胺或其盐以足以使铜离子复合但不足以起促进剂的量存在时获得的铜沉积速度高的铜沉积速度,以及1.2×10 -4至1.2×10 -3摩尔/升的 作为反应引发剂的铁离子化合物和/或1.92×10 -4至1.92×10 -3摩尔/升的选自哒嗪,甲基哌啶,1,2-二(2-吡啶基)乙烯的至少一种化合物 ,1,2-二(吡啶基)乙烯,2,2'-二吡啶基胺,2,2'-联吡啶基,2,2'-联嘧啶,6,6'-二甲基-2,2'-联吡啶,二-2 - 吡啶酮,N,N,N',N'-四乙基乙二胺,萘,1,8-萘啶,1,6-萘啶,四硫糠醛,α, ha,α-三联吡啶,邻苯二甲酸,间苯二甲酸和2,2'-二苯甲酸作为改善电镀膜的物理性能的试剂,以及使用该化学镀铜溶液形成无电解铜沉积膜的方法。
    • 8. 发明授权
    • Method and an apparatus for detecting concentration of a chemical
treating solution and an automatic control apparatus thereof
    • 用于检测化学处理溶液浓度的方法和装置及其自动控制装置
    • US5450870A
    • 1995-09-19
    • US162187
    • 1993-12-16
    • Makoto SugaMasashi NiwaFumio KojimaNobumasa IshidaKoji Kondo
    • Makoto SugaMasashi NiwaFumio KojimaNobumasa IshidaKoji Kondo
    • C23C18/16G05D21/02G05D11/08
    • C23C18/1683C23C18/1628G05D21/02Y10T137/0329Y10T137/2509
    • According to the present invention, the changing rate of the predetermined component concentration is determined, based on the difference between the predetermined component concentration in a chemical treating solution (a plating solution) which is analyzed this time and the predetermined component concentration analyzed last time, both measured by an analytical means, and the difference of each sampling time for analysis of each component concentration by the analytical means (140). Subsequently, the correction amount for the analyzed result of this time based on the changing rate obtained above and the elapsed time from the sampling point of time of the plating solution of this time for analysis of the plating solution by the analytical means to the current point of time (150), and then the analyzed result is corrected based on the resulting correction amount to compute or calculate the current concentration (160). As the result, the current concentration can be detected accurately regardless of the analyzing time of the plating solution by the analytical means.
    • PCT No.PCT / JP93 / 00486 Sec。 371日期:1993年12月16日 102(e)日期1993年12月16日PCT提交1993年4月16日PCT公布。 公开号WO93 / 21359 日期为1993年10月28日。根据本发明,基于本次分析的化学处理溶液(电镀液)中的规定成分浓度与本发明的分析浓度之间的差异,确定预定成分浓度的变化率 通过分析手段测量的上次分析的预定组分浓度和通过分析装置(140)分析每种组分浓度的每个采样时间的差异。 随后,根据上述获得的变化率,将该时刻的分析结果的校正量和从该分析手段分析电镀液的时刻的电镀溶液的取样点到当前点的经过时间 的时间(150),然后基于所得到的校正量来校正分析结果,以计算或计算当前浓度(160)。 结果,可以准确地检测电流浓度,而不管分析装置的电镀溶液的分析时间如何。