JP2016211044A - めっき処理方法および記憶媒体 - Google Patents
めっき処理方法および記憶媒体 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000007747 plating Methods 0.000 title claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000007772 electroless plating Methods 0.000 claims abstract description 43
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910000531 Co alloy Inorganic materials 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- 230000010354 integration Effects 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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- 238000001039 wet etching Methods 0.000 description 1
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
【解決手段】めっき処理方法は、表面(例えばTSV(12)の底部表面)にアルミニウムまたはアルミニウム合金からなるAl層(22)が露出している基板(10)を準備する工程と、その後、基板に対してジンケート処理を施し、Al層の表面にジンケート皮膜(30)を形成する工程と、その後、アルカリ性であってかつ錯化剤を含む無電解めっき液(例えばCo系めっき液)を用いて、Al層の表面に第1無電解めっき層(例えばCoバリア層(14a))を形成する第1無電解めっき工程とを備える。
【選択図】図2
Description
まず、アルカリ性洗浄液(NaOHを主成分とするもの)を基板10に供給して、TSV12内に露出しているAl配線層22の表面にある酸化皮膜を除去する。その後、純水(DIW)によるリンス処理を行い、アルカリ性洗浄液および反応副生成物を基板10から除去する。
次に、基板10にスマット除去用の酸性薬液を供給して、酸化皮膜除去工程によりAl配線層22の表面に生じたスマット(Al(OH)3)を除去する。その後、純水によるリンス処理を行い、酸性薬液および反応副生成物を基板10から除去する。
次に、基板にジンケート処理を施し、Al配線層22の表面に亜鉛(Zn)皮膜(ジンケート皮膜)30(図2(b)参照)を形成する。ここでは、ダブルジンケート処理を行うものとする。
ダブルジンケート処理は、
ジンケート処理液を基板10に供給して、Al配線層22の表面にZn粒子を析出させる第1ジンケート工程と、
その後、純水によりジンケート液および反応副生成物を基板10から除去する第1リンス工程と、
その後、硝酸(スマット除去工程で用いたものと同じものでよい)を基板に供給して、第1ジンケート工程で析出せたZn粒子を一旦剥離させるZnストリップ工程と、
その後、純水により硝酸および反応副生成物を基板10から除去する第2リンス工程と、
ジンケート処理液を基板10に供給して、Al配線層22の表面にZn粒子を析出させる第2ジンケート工程と、
その後、純水によりジンケート液および反応副生成物を基板10から除去する第3リンス工程と、
から構成される。
次に、Co系無電解めっき液を基板10に供給して、Al配線層22の表面にCoバリア層14の一部(14a)(図2(c)参照)を形成する。ここでは、例えばタングステン(W)およびホウ素(B)を含むCoWB系のめっきによりCoバリア層14aを形成する。
次に、TSV12内に触媒層32(図2(d)参照)を形成する。触媒層は、例えば、基板10にシランカップリング剤またはチタンカップリング剤等の適当なカップリング剤を供給することによりSAM(自己組織化単分子膜)を形成する工程と、その後、基板10に塩化パラジウム液等の触媒イオン含有液を供給する工程と、その後、DMAB(ジメチルアミンボラン)等の還元剤を基板に供給する工程とを順次実行することにより行うことができる。この触媒層形成工程により、TSV12の内表面(TSV12内に露出しているシリコン基板26およびTEOS層28の表面を含む)を含む基板10の表面全体に触媒層32が形成される。触媒層を形成した後、純水によるリンス処理を行い、最後に使用した薬液(DMAB)および反応副生成物を基板10から除去する。触媒層32の形成方法は、上記のものに限定されるものではなく、公知の任意の方法を採用することができる。触媒層32に含まれる触媒金属は、パラジウムに限定されるものではなく、無電解めっきの還元析出反応の触媒として機能しうる他の金属、例えば金(Au)、白金(Pt)、ルテニウム(Ru)等であってもよい。
次に、Co系無電解めっき液を基板10に供給して、無電解めっき法により、TSV12内にCoバリア層14のうちの別の一部(14b)(図2(e)参照)を形成する。すなわち、TSV12内に露出しているシリコン基板26およびTEOS層28の表面にCoバリア層14bが析出する。なお、このときAl配線層22の表面に既に形成されているCoバリア層14a上にも、さらにCoバリア層14bが析出する。また、基板10の表面全体に触媒層が形成されているため、基板10の表面全体にCoバリア層14bが形成される。Coバリア層14bを形成した後、純水(DIW)によるリンス処理を行い、めっき液および反応副生成物等の残渣を基板10から除去する。
次に、Cu系無電解めっき液を基板10に供給して、Coバリア層14上にシード層としての銅または銅合金(以下、Cuと記す)(図2(f)参照)を析出させる。次いで、電解めっきにより、TSV12内をCuめっきで埋め込んでCu配線層16を形成する。基板10の全表面にCoバリア層14が形成されているため、基板10の全表面にCu配線層16が形成される。なお、穴または凹部(TSV12)のサイズ次第では無電解めっきのみによりCu配線層16を形成してもよい。Cu配線層16を形成した後、純水によるリンス処理を行い、めっき液および反応副生成物等の残渣を基板10から除去する。
12 凹部(TSV)
22 Al層(Al配線層)
30 ジンケート皮膜
14a(14) 第1無電解めっき層(Coバリア層)
14b(14) 第2無電解めっき層(Coバリア層)
16 Cuめっき(Cu配線層)
32 触媒層
100 めっき処理システム
120 制御装置
122 記憶媒体
Claims (6)
- 表面にアルミニウムまたはアルミニウム合金からなるAl層が露出している基板を準備する工程と、
その後、前記基板に対してジンケート処理を施し、前記Al層の表面にジンケート皮膜を形成する工程と、
その後、アルカリ性であってかつ錯化剤を含む無電解めっき液を用いて、前記Al層の前記表面に第1無電解めっき層を形成する第1無電解めっき工程と、
を備えためっき処理方法。 - 前記第1無電解めっき層は、コバルトまたはコバルト合金からなるCoめっき層である、請求項1記載のめっき処理方法。
- 前記基板の前記表面は凹部を有し、前記Al層は前記凹部の底面に露出している表面を有するAl配線層であり、第1無電解めっき工程は、前記凹部の底面に露出している前記Al配線層の表面に前記第1無電解めっき層を形成する、請求項2記載のめっき処理方法。
- 前記第1無電解めっき工程の後に、前記凹部の少なくとも側面に触媒層を形成する工程と、
その後、前記凹部の前記底面および前記側面に、第2無電解めっき層として、コバルトまたはコバルト合金からなるCoめっき層を形成する第2無電解めっき工程と、
をさらに備えた、請求項3記載のめっき処理方法。 - 前記第2無電解めっき工程の後に、前記凹部の内部に銅または銅合金からなるCuめっきを埋め込む工程をさらに備えた、請求項4記載のめっき処理方法。
- めっき処理システムの動作を制御するためのコンピュータにより実行されたときに、前記コンピュータが前記めっき処理システムを制御して請求項1から5のうちのいずれか一項に記載のめっき処理方法を実行させるプログラムが記録された記憶媒体。
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