CN106103792A - 铜基合金溅射靶 - Google Patents
铜基合金溅射靶 Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 43
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052802 copper Inorganic materials 0.000 claims abstract description 61
- 239000011241 protective layer Substances 0.000 claims abstract description 53
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000009413 insulation Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000004411 aluminium Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000011135 tin Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000010408 film Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052718 tin Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 229910000881 Cu alloy Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002310 reflectometry Methods 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
本发明的铜基合金溅射靶含有4质量％～16质量％的锡及4质量％～11质量％的铝，剩余部分包含铜及不可避免的杂质。本发明的靶在将使用该靶而直接形成于玻璃基板上的保护层在退火前的、于室温(25℃)下的体积电阻率设定为R1，将在大气气氛下于350℃对所述保护层进行退火30分钟后的体积电阻率设定为R2时，优选为R1＞R2。
Description
技术领域
本发明涉及一种铜基合金溅射靶。
背景技术
液晶显示器及等离子显示器等平板显示器具有多个薄膜晶体管(TFT)，多在其布线中使用铝。近年来，平板显示器正在大型化及高精细化，起因于此，信号的高速化的要求高涨。为了满足此要求，TFT的布线的进一步低电阻化是必要的。
从布线的低电阻化的观点出发，作为布线材料，正在使用电阻比铝低的金属即铜。铜本身虽然电阻比铝低，但如果暴露于高温的大气下或含氧的气氛下则容易氧化，起因于此而有高电阻化的缺陷。
从防止铜布线氧化的观点出发，提出了在铜布线的表面上设置保护层的方法。例如在专利文献1中，记载了使用含有Cr、Ti、V、Al、Ta、Co、Zr、Nb及Mo，剩余部分为铜及不可避免的杂质的铜合金溅射靶而形成保护层。在专利文献2中，记载了使用含有Ni，进一步含有Al和/或Ti，剩余部分由铜构成的铜合金而形成铜布线保护层。在专利文献3中，记载了使用含有Ni及Mg，剩余部分由铜构成的铜合金而形成铜布线保护层。
在专利文献4中，记载了使用含有Zn、Ni及Mn，剩余部分由铜及不可避免的杂质构成的溅射靶而形成铜布线保护层。在专利文献5中，记载了使用含有Al、Fe、Ni及Mn，剩余部分由铜及不可避免的杂质构成的溅射靶而形成铜布线保护层。
另一方面，还提出了使用Mo基合金形成保护层的方法。例如在专利文献6中，记载了含有Mo、Ni及W，剩余部分由不可避免的杂质构成的保护层即使在350℃的大气中也具有抗氧化性。
现有技术文献
专利文献
专利文献1：日本特开2013-133489号公报
专利文献2：日本特开2014-105362号公报
专利文献3：日本特开2014-129596号公报
专利文献4：日本特开2014-114481号公报
专利文献5：日本特开2014-156621号公报
专利文献6：日本特开2014-199920号公报
发明内容
当使用上述专利文献1～5中所述的材料时，如果是到某程度的温度范围，则能防止铜布线氧化。可是，预想平板显示器等的制造工艺的温度今后进一步提高，在这样的高温区域，例如在超过250℃的高温区域，即使使用上述各专利文献所述的材料，防止铜布线氧化也是困难的。另一方面，如果在保护层中使用Mo基合金，在与Cu布线一起刻蚀该保护层时，一般来讲因两者的刻蚀速度的差异而在锥形部产生阶梯等，有时得不到所希望的图案形状。因此，作为保护层，优选使用刻蚀速度与铜布线的差小的材料。
所以，本发明的课题在于防止铜布线氧化，更详细地讲，提供一种即使在高温区域也能有效地防止铜布线氧化的铜布线保护层形成用铜基合金溅射靶。
本发明通过提供含有4质量％～16质量％的锡及4质量％～11质量％的铝，剩余部分包含铜及不可避免的杂质的铜布线保护层形成用铜基合金溅射靶而解决所述课题。
具体实施方式
以下，基于本发明的优选实施方式对本发明进行说明。本发明的溅射靶由铜基合金形成。本发明的溅射靶可用于在铜布线上形成保护层。在本发明中，所谓铜布线，是由铜或铜合金形成的电路布线，一般来讲可由用各种薄膜形成方法形成的薄膜层构成。作为构成铜布线的铜合金，可列举出作为合金成分含有选自锰、镁、铋、铟等中的1种或2种以上元素的铜基合金。这些合金成分在铜合金中能以0.01原子％～20原子％的比例含有。在铜布线由铜合金构成时，该铜合金可采用与构成后述的保护层的合金不同种的铜合金。
本发明的溅射靶含有4质量％～16质量％的锡及4质量％～11质量％的铝，剩余部分包含铜及不可避免的杂质。本发明的溅射靶除铜及不可避免的杂质以外，作为构成元素优选只含有锡及铝。可是，也可在不损害本发明的有利的效果的范围内少量含有其它元素。
本发明者的研究结果表明，由于在本发明的溅射靶中组合地含有锡及铝，因而通过采用该溅射靶而形成的保护层可有效地防止铜布线的氧化。详细地讲，通过将含在溅射靶中的锡的比例设定在4质量％以上，且将铝的比例设定在4质量％以上，可充分提高铜布线的起因于保护层的抗氧化性。此外，通过将含在溅射靶中的锡的比例设定在16质量％以下，且将铝的比例设定在11质量％以下，在一起同时刻蚀保护层和铜布线时，能够减小两者的刻蚀速度差，容易通过刻蚀来形成所希望的布线图案。
从使上述的本发明的效果更加显著的观点出发，含在溅射靶中的锡的比例优选为4质量％～10质量％，更优选为5质量％～7质量％。另一方面，含在溅射靶中的铝的比例优选为4质量％～10质量％，更优选为5质量％～9质量％。另外，含在溅射靶中的锡及铝的合计量的比例优选为8质量％～20质量％，更优选为10质量％～16质量％。
从与上述相同的观点出发，铜基合金中的锡和铝的比率按质量比表示，优选Sn/Al的值为0.4～2.5，更优选为0.5～1.4。
本发明的溅射靶具有采用该靶形成的铜布线的保护层的体积电阻率随着该保护层的退火温度的上升而下降的特征。起因于此，当在保护层上形成ITO等透明导电膜时，将产生能够减低相对于透明导电膜的接触电阻的有利效果。所述特征例如可通过使用本发明的溅射靶，直接在基板上形成保护层，测定该保护层的退火前后的体积电阻率来进行评价。详细地讲，首先，使用本发明的溅射靶直接在玻璃基板上形成保护层。然后，测定对所述保护层进行退火前的室温(25℃)时的所述保护层的体积电阻率R1，并测定在350℃下对所述保护层进行了退火后的所述保护层的体积电阻率R2而进行了比较评价。本发明的溅射靶具有如果使用该靶形成保护层则所述体积电阻率R2比所述体积电阻率R1有所降低、即R1＞R2的特征。优选体积电阻率R2相对于体积电阻率R1为85％以下，更优选为80％以下，进一步优选为75％以下。关于保护层的体积电阻率随着该保护层的退火温度的上升而下降的理由，本发明者认为就是因为通过退火而在铜基合金中析出铜和锡的金属间化合物，由此使纯铜成分相对增加。再者，更优选该体积电阻率是随着退火温度的上升而逐渐连续下降的。关于退火，通过在大气气氛下将作为目的的退火温度保持例如30分钟来进行。退火例如可通过从室温缓慢地使温度上升来进行。作为体积电阻率测定中所用的玻璃基板，例如可使用EAGLEXG(コーニング公司/液晶显示器用玻璃，注册商标)等。
本发明的溅射靶可用该技术领域中公知的种种方法来制造。例如将在真空中熔炼的铜、锡及铝进行铸造而使其合金化。接着，采用得到的铸锭制造溅射靶。关于加工成溅射靶的加工方法没有特别的限制，例如可以是热锻造，也可以是冷锻造，或者也可以是热轧。此外，也可以通过线切割进行切制加工来形成板材。通过采用铟等粘结材料将得到的板材贴装在溅射的靶托即背板上，可得到铜基合金溅射靶。再者，在本发明中，所谓铜基合金溅射靶，还包含平面磨削及粘结等溅射靶精加工工序之前的溅射靶材的状态。
接着，对采用本发明的溅射靶形成铜布线保护层的方法进行说明。首先，在基板上，采用布线材料即铜或铜基合金，用各种薄膜形成方法成膜铜布线。作为薄膜形成方法，可列举出例如溅射，但也并不局限于此。作为基板，例如可使用玻璃基板等由非导电性材料构成的基板。或者，也可以在表面形成有ITO等透明导电膜的玻璃基板中的该透明导电膜上形成布线材料。铜布线的厚度可根据其具体的用途任意地设定，例如可设定在50nm～500nm。为提高基板和铜布线的密合性，也可以在两者间形成密合层。作为密合层，例如在基板为玻璃基板的情况下，可采用由钛构成的层。
在这样形成的铜布线上形成保护层。关于保护层的形成，可采用本发明的溅射靶，通过溅射来进行。形成的保护层实质上由与溅射靶同组成的铜基合金构成。保护层的厚度可根据其具体的用途任意地设定，例如可设定在20nm～60nm。通过将保护层的厚度设定在20nm以上，能够有效地防止作为保护对象的铜布线的氧化。此外，通过将保护层的厚度设定在60nm以下，能够使保护层的生产率不受损害。
实施例
以下，通过实施例对本发明更详细地进行说明。但是，本发明的范围并不限定于所述实施例。只要不特别说明，“％”就意味着“质量％”。
首先，为调查使用本发明的溅射靶形成的保护层对铜布线的抗氧化效果，进行了以下的评价。
[实施例1～9]
精确地称量铜、锡及铝的各铸锭，使其具有下表1所示的组成。将这些铸锭装入氧化镁制的坩埚中，在真空中通过加热使其熔化。采用得到的熔液进行铸造，得到由铜基合金构成的铸锭。在将得到的铸锭轧制后，通过加工得到直径101.6mm、厚5mm的靶。再者，在表1中，例如“Cu-4Sn-4Al”意味着含在铜基合金中的Sn的比例为4质量％、Al的比例为4质量％。
将玻璃基板安装在DC磁控管溅射装置中，同时安装钛、铜及前述得到的铜基合金的各溅射靶。在此状态下进行溅射，在所述玻璃基板上按以下顺序形成由钛构成的厚15nm的密合层、厚400nm的铜布线及厚50nm的保护层，形成玻璃基板上具有3层的布线基板。溅射条件规定如下。
·溅射方式：DC磁控管溅射
·排气装置：旋转泵+低温泵
·到达真空度：2×10－5Pa以下
·Ar压力：0.5Pa
·基板温度：室温
·溅射功率：250W(功率密度3.2W/cm2)
·使用基板：EAGLE XG(コーニング公司/液晶显示器用玻璃，注册商标)，50mm×50mm×0.7mmt
[比较例1～6]
使用由具有下表1所示的组成的铜基合金构成的靶以取代实施例1～9中使用的靶。除此以外，与实施例1～9同样地形成保护层。
[比较例7]
本比较例为在实施例1～9中没有形成保护层的例子。所以，在本比较例中，呈铜布线露出的状态。
[评价1]
就在实施例及比较例中得到的具有所述3层的布线基板，调查了退火温度和体积电阻率的关系及退火温度和表面反射率的关系。具体地讲，在大气气氛下，对所述布线基板进行加热使其温度上升，在350℃下将该温度保持30分钟，测定该温度下的所述布线基板的从表面侧的体积电阻率及表面反射率。然后，以25℃(即退火前)的体积电阻率及表面反射率为基准，算出该温度下的体积电阻率及表面反射率的比例(％)(退火后的值/退火前的值×100)。下表1中示出了退火温度为350℃下的结果。
关于体积电阻率，通过采用低电阻率计(ロレスターHP/三菱化学分析株式会社制造)和四探针探头，将该探头按压在所述布线基板最表层的保护膜层上来进行测定。此外，关于表面反射率，采用紫外可见分光光度计，测定波长550nm下的值。
表1
从表1所示的结果表明：在按实施例得到的布线基板中，即使在350℃的高温下进行退火时，包含低电阻的铜布线部分的整个3层的体积电阻率的上升及表面反射率的下降都小，最表层的起因于保护层形成的抗氧化效果高。与此相对照，可知在各比较例的布线基板中，如果在350℃的高温下进行退火，则体积电阻率的上升及表面反射率的下降都显著，铜布线发生氧化。
接着，为调查伴随保护层退火温度上升的体积电阻率的变化而进行了以下的评价。
[实施例10～18]
使用具有实施例1～9的组成的靶，在玻璃基板上直接形成保护层。溅射条件与实施例1～9相同，将保护层的厚度规定为400nm。玻璃基板使用EAGLE XG(コーニング公司/液晶显示器用玻璃，注册商标)。
[比较例8～13]
使用具有比较例1～6的组成的靶以代替实施例10～18中使用的靶。除此以外，与实施例10～18同样地在玻璃基板上直接形成保护层。
[评价2]
就在实施例及比较例中得到的具有保护层的基板，按与上述评价1同样的步骤调查了退火温度和体积电阻率的关系。下表2中示出了退火温度为350℃时的结果。
表2
从表2所示的结果表明：在按实施例10～18得到的具有保护层的基板中，与退火前相比，在退火温度为350℃时，体积电阻率下降。与此相对照，在比较例11～13的具有保护层的基板中，与退火前相比，即使在退火温度为350℃时也没有观察到体积电阻率有大的变化。此外，在比较例8～10的具有保护层的基板中，在退火温度为350℃时，发现体积电阻率稍微下降。可是，如从比较例1～3的结果所判明的那样，没有充分得到对铜布线的抗氧化效果。
产业上的可利用性
根据本发明，可提供一种即使在高温区域也可有效地防止铜布线氧化的铜基合金溅射靶。
Claims (7)
1.一种铜布线保护层形成用铜基合金溅射靶，其中，含有4质量％～16质量％的锡及4质量％～11质量％的铝，剩余部分包含铜及不可避免的杂质。
2.根据权利要求1所述的铜基合金溅射靶，其中，使用所述铜基合金溅射靶在玻璃基板上直接形成保护层，当将所述保护层在退火前的、于室温即25℃下的体积电阻率设定为R1，将在大气气氛下于350℃对所述保护层进行退火30分钟后的体积电阻率设定为R2时，为R1＞R2。
3.根据权利要求2所述的铜基合金溅射靶，其中，所述体积电阻率R2为所述体积电阻率R1的85％以下。
4.根据权利要求1～3中任一项所述的铜基合金溅射靶，其中，锡及铝的合计量的比例为8质量％～20质量％。
5.根据权利要求1～4中任一项所述的铜基合金溅射靶，其中，Sn/Al的质量比为0.4～2.5。
6.根据权利要求1～5中任一项所述的铜基合金溅射靶，其中，除铜及不可避免的杂质以外，作为构成元素只含有锡及铝。
7.一种铜布线保护膜，其中，含有4质量％～16质量％的锡及4质量％～11质量％的铝，剩余部分包含铜及不可避免的杂质。
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| WO2003064722A1 (fr) * | 2002-01-30 | 2003-08-07 | Nikko Materials Company, Limited | Cible de pulverisation d'alliage de cuivre et procede de fabrication de cette cible |
| US20050285273A1 (en) * | 2002-11-21 | 2005-12-29 | Nikko Materials Co., Ltd. | Copper alloy sputtering target and semiconductor element wiring |
| CN1839213A (zh) * | 2003-08-21 | 2006-09-27 | 霍尼韦尔国际公司 | 在三元混合物中包含铜的pvd靶和形成含铜pvd靶的方法 |
| JP2011035347A (ja) * | 2009-08-06 | 2011-02-17 | Fujitsu Semiconductor Ltd | 半導体装置の製造方法 |
| JP2014156621A (ja) * | 2013-02-14 | 2014-08-28 | Mitsubishi Materials Corp | 保護膜形成用スパッタリングターゲットおよび積層配線膜 |
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| WO2003064722A1 (fr) * | 2002-01-30 | 2003-08-07 | Nikko Materials Company, Limited | Cible de pulverisation d'alliage de cuivre et procede de fabrication de cette cible |
| US20050285273A1 (en) * | 2002-11-21 | 2005-12-29 | Nikko Materials Co., Ltd. | Copper alloy sputtering target and semiconductor element wiring |
| CN1839213A (zh) * | 2003-08-21 | 2006-09-27 | 霍尼韦尔国际公司 | 在三元混合物中包含铜的pvd靶和形成含铜pvd靶的方法 |
| JP2011035347A (ja) * | 2009-08-06 | 2011-02-17 | Fujitsu Semiconductor Ltd | 半導体装置の製造方法 |
| JP2014156621A (ja) * | 2013-02-14 | 2014-08-28 | Mitsubishi Materials Corp | 保護膜形成用スパッタリングターゲットおよび積層配線膜 |
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