TWI390080B - 藉無電解電鍍形成有銅薄膜之電鍍物 - Google Patents

藉無電解電鍍形成有銅薄膜之電鍍物 Download PDF

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TWI390080B
TWI390080B TW098123864A TW98123864A TWI390080B TW I390080 B TWI390080 B TW I390080B TW 098123864 A TW098123864 A TW 098123864A TW 98123864 A TW98123864 A TW 98123864A TW I390080 B TWI390080 B TW I390080B
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copper
metal
film
electroless
plating
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TW201012967A (en
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Junichi Ito
Atsushi Yabe
Junnosuke Sekiguchi
Toru Imori
Yasuhiro Yamakoshi
Shinichiro Senda
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Nippon Mining Co
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—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
    • 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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
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    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
    • H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12431—Foil or filament smaller than 6 mils
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Description

藉無電解電鍍形成有銅薄膜之電鍍物
本發明係關於一種藉無電解電鍍形成有銅薄膜之電鍍物。尤其是有關於一種作為形成ULSI(ultra-large scale integration，超大規模積體電路)超微細銅配線(鑲嵌(damascene)銅配線)時之晶種(seed)層，而藉無電解電鍍形成有銅薄膜之電鍍物。
以ULSI微細銅配線(鑲嵌銅配線)之銅之成膜方法而言，無電解銅電鍍法係被期待取代現行之濺鍍法、電銅電鍍法。
以往，在如半導體晶圓之鏡面上進行無電解銅電鍍時，難以與所析出之電鍍膜獲得充分之密接性。此外，電鍍之反應性較低，亦難以對整面基板進行均勻之電鍍。以往，例如在氮化鉭等阻障金屬(barrier metal)層上以無電解電鍍法形成銅晶種層時，會有難以均勻地形成電鍍而使密著力不充分之問題。此外，在鎢及鉬等金屬單體上以無電解電鍍法形成銅晶種層作為阻障金屬層時，亦會難以均勻地形成電鍍而有密著力不充分之問題。因此，為了要在氮化鉭等阻障金屬層上以無電解電鍍法均勻地形成銅晶種層，在電鍍前需要賦予觸媒步驟。
本發明人等已發現在無電解銅電鍍液中加入重量平均分子量(Mw)較小之水溶性含氮聚合物作為添加劑，另一方面在電鍍液浸漬前使觸媒金屬附著於被電鍍物之基板，或是將觸媒金屬預先成膜於最表面之後浸漬於電鍍液，而透過氮原子使聚合物吸附於該觸媒金屬上，藉此可抑制電鍍之析出速度，並且使結晶非常微細化而使膜厚15nm以下之均勻薄膜形成於類如晶圓等鏡面上(專利文獻1)。此外，本發明人等亦在前述發明之實施例中，揭示將觸媒金屬預先成膜於最表面之後浸漬於電鍍液，而透過氮原子使聚合物吸附於該觸媒金屬上，藉此可抑制電鍍之析出速度，並且使結晶非常微細化，而使膜厚6nm以下之均勻薄膜形成於類如晶圓等鏡面上。
在此種方法，亦即在形成鑲嵌銅配線中，己得知於將觸媒金屬成膜之後藉由無電解電鍍設置銅晶種層時，除觸媒金屬層之外另需預先形成用以防止銅擴散之阻障層，因此，由於在將銅晶種層成膜之前要形成阻障層與觸媒金屬層之二層，而在無法增加膜厚之超微細配線中，會有難以應用在實際製程中的問題。
[先行技術文獻] [專利文獻]
[專利文獻1]日本特開2008-223100號公報
本發明之目的為提供一種在以無電解銅電鍍形成晶種層時，於成膜均勻性、及密著性上，相較於在前述之鎢及鉬等單體金屬上進行無電解銅電鍍時更為提升，而且，在銅晶種層成膜之前先要形成前述二個層之繁瑣得以解除，而可形成超微細配線，並以薄且均勻之膜厚形成有晶種層之電鍍物。
經本發明人等不斷努力檢討之結果，終於發現以下內容而完成本發明，亦即藉由採用由可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A所構成之合金薄膜，而且在此合金薄膜上使用pH10以上之無電解銅電鍍液進行無電解銅電鍍時，在成膜均勻性、及密著性方面，相較於在前述之鎢及鉬等單體金屬上進行無電解銅電鍍時更為提升，而且在銅晶種層成膜之前先要形成前述二個層之繁瑣亦可解除。
亦即，本發明係如下所述。
(1)一種電鍍物，其特徵為：在基材上，形成防止銅擴散用阻障合金薄膜，其係由可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A所構成，而該防止銅擴散用阻障合金薄膜係為將前述金屬A設為15原子%以上、35原子%以下之組成，且在此合金薄膜上藉由使用pH10以上之無電解銅電鍍液之無電解電鍍形成銅薄膜。
(2)如前述(1)之電鍍物，其中，前述金屬B係為鎢或鉬，而前述金屬A係為選自鎳、鈷、錫之至少1種金屬。
(3)如前述(1)或(2)之電鍍物，其中，藉由前述無電解電鍍所形成之銅薄膜係為膜厚10nm以下，電阻率10μΩ‧cm以下。
依據本發明，係在基材上形成防止銅擴散用阻障合金薄膜，其係由可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A所構成，且具有特定組成，在此合金薄膜上藉由使用pH10以上之無電解銅電鍍液之無電解電鍍形成銅薄膜時，相較於在鎢及鉬等單體金屬上進行無電解銅電鍍液之情形，可提升銅薄膜之成膜均勻性、密著性。此外，在防止銅擴散用阻障合金薄膜與該合金薄膜上之無電解銅電鍍層之界面中，係可形成實質不含氧之狀態，而可降低銅薄膜之電阻。
再者，前述合金薄膜即使在其上不設置觸媒金屬層，亦可藉由無電解銅電鍍形成成膜均勻性、密著性均優異之銅晶種層，因此形成鑲嵌銅配線時要先形成阻障層與觸媒金屬層二層之繁瑣可得以解除，而可更為薄膜化。
 [發明之實施形態]
本發明係關於一種電鍍物，在基材上形成防止銅擴散用阻障合金薄膜，其係由可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A所構成，且具有特定組成，並在此合金薄膜上藉由使用pH10以上之無電解銅電鍍液之無電解電鍍形成銅薄膜。
以可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B而言，可例舉如鎢與鉬，此等金屬雖可使用其中任一者，惟以鎢為較佳。
使用鎢、鉬作為金屬B時，以在pH10以上之無電解銅電鍍液中之離子化傾向較鎢、鉬為小之金屬A而言，可例舉如有鎳、鈷、錫、鎂、鋁、鋅等，而以鎳、鈷、錫為較佳，鎳、鈷為更佳。鎳、鈷係為相對較高熔點，可與鎢、鉬進行粉末原料之合金化，此外，亦適用作為閘極電極材料。
對鎢或鉬等單體金屬上進行無電解銅電鍍時，首先係開始鎢或鉬與銅之置換電鍍，惟由於置換開始時會不均勻，因此在全面產生置換反應之前，先在置換所析出之銅上進行還原反應，而還原電鍍膜亦會覆蓋於未產生置換電鍍之部分。據推測，係由於在未置換反應部分上形成還原電鍍膜之期間，會產生殘留間隙之形態，而使密著性變差之故。而在形成前述金屬A與金屬B之合金薄膜時，在該合金薄膜上使用pH10以上之無電解銅電鍍液來進行無電解銅電鍍，藉此即易於產生金屬B與銅之置換電鍍，再者金屬B之離子化傾向較金屬A為高，由此而產生局部電池腐蝕，使金屬B進行溶解，又由於該影響而使置換反應進行，未置換反應部分減少，使得密著性及成膜均勻性提升。
可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A之防止銅擴散用阻障合金薄膜之組成，以金屬A之組成比為15原子%以上、35原子%以下為較佳，且以25原子%為更佳。當金屬A較15原子%少時，如前所述，未置換反應部分變多，銅之析出變得不均勻，銅膜之密著性降低。此外，當較35原子%多時，金屬A擴散至銅膜中，電阻會上升。
前述合金薄膜雖可使用形成薄膜之公知之方法來形成，惟以使用包含前述金屬A與金屬B之濺鍍合金靶，在基材上以濺鍍形成為較佳。前述組成之合金薄膜，可藉由包含與所希望之合金薄膜之組成大略相同組成之金屬A與金屬B之濺鍍靶形成。
合金薄膜之膜厚以3至20nm為較佳，尤佳為5至15nm。
本發明中，以形成合金薄膜之基材而言，以半導體晶圓為較佳，藉由實施酸處理、鹼處理、界面活性劑處理、超音波洗淨或將此等處理予以組合之處理，即可謀求基材之清潔、潤濕性提升。
以無電解銅電鍍形成之銅薄膜，反應初期主要係藉由無電解銅電鍍液中所含之銅離子與金屬B之置換反應，而使無電解銅電鍍液中所含之銅離子析出為金屬而形成。
在本發明中，在反應初期藉由置換電鍍形成銅薄膜，藉此將前述合金薄膜表面之氧化物在置換電鍍之過程中去除。此外，藉由上述之作用，將前述合金薄膜與銅薄膜之界面之氧濃度以歐傑電子(Auger electron)分光法(AES)進行分析結果，可設為1原子%以下(檢測極限以下)。界面存在氧時，會有配線之電阻上升，或阻障功能降低等之不良影響。
而且，結果，可將銅薄膜之厚度設在10nm以下且電阻率為10μΩ‧cm以下。藉由將晶種層之膜厚作成較薄，即可應用於線寬數十nm層級之鑲嵌銅配線。
以本發明中使用防止銅擴散用阻障合金薄膜進行無電解銅電鍍時所使用之無電解銅電鍍方法而言，係可使用一般之方法。同樣地所使用之銅電鍍液亦可使用一般之pH10以上之無電解銅電鍍液。
無電解銅電鍍液通常包含銅離子、銅離子之錯合劑、還原劑、及pH調整劑等。
以無電解銅電鍍液之還原劑而言，考慮到甲醛液福馬林(formaline)，對人體及環境之不良影響，以使用乙醛酸(glyoxylic acid)為較佳。
乙醛酸之濃度係以電鍍液中0.005至0.5mol/L為較佳，且以0.01至0.2mol/L為尤佳。濃度未達0.005mol/L時不會產生電鍍反應，超過0.5mol/L時，則電鍍液會不安定而分解。
本發明中，以無電解銅電鍍液之銅離子源而言，係可使用一般所用之所有銅離子源，例如有硫酸銅、氯化銅、硝酸銅等。無電解銅電鍍液中之銅離子源之濃度，係以0.005至0.1mol/L為較佳。此外，以銅離子之錯合劑而言，係可使用一般所用之所有錯合劑，例如乙二胺四乙酸(ethylenediaminetetraacetic acid)、酒石酸等。無電解銅電鍍液中之錯合劑之濃度係以0.02至0.5mol/L為較佳。
以其他添加劑而言，係可使用一般用於電鍍液之添加劑，例如2,2’-雙吡啶(2,2’-bipyridyl)、聚乙二醇(Polyethylene Glycol，PEG)、亞鐵氰化鉀(potassium ferrocyanide)等。
此外，本發明中之無電解銅電鍍液係以在pH10至14使用為較佳，且以在pH12至13使用為尤佳。以pH調整劑而言，雖可使用氫氧化鈉、氫氧化鈣等一般所使用者，惟因半導體用途而欲避免鈉、鉀等鹼金屬時，係可使用氫氧化四甲銨(Tetramethylammonium hydroxide)。
此外，本發明中之無電解銅電鍍液，係以在槽溫40至90℃使用，從浴安定性及銅之析出速度之觀點而言較佳。
在本發明中使用無電解銅電鍍液進行電鍍時，將被電鍍材浸漬於電鍍槽中。被電鍍材係為形成有前述之合金薄膜者。
藉由本發明之無電解電鍍所製作之銅薄膜之厚度係以3至10nm為尤佳。
藉由本發明之無電解電鍍所製作之銅薄膜，係電鍍膜較薄，而膜厚均勻。因此作為鑲嵌銅配線用晶種層使用時，在配線寬度為100nm以下之微細介層孔/溝槽(via/trench)內亦可形成膜厚均勻之薄膜晶種層，結果可獲得不產生孔隙或裂縫(void/seam)等缺陷之半導體晶圓。
本發明之電鍍物，係可在由無電解電鍍所形成之銅薄膜上，進一步藉由電鍍而設置配線部。電鍍係可電鍍或無電解電鍍。
配線部係以銅或以銅為主成分之合金為較佳，且以銅為尤佳。銅電鍍液可為一般用於鑲嵌銅配線埋入用之組成，並未特別限定，惟例如以主成分而言可使用硫酸銅及硫酸、以微量成分而言可使用包含氯、聚乙二醇(polyethylene glycols)、(Disulfide Bis(3-sulfopropyl)disodium)、及耶奴斯綠(Janus green)等之液體。此外，以埋入所使用之無電解銅電鍍液而言，係可使用例如國際公開第2005/038086號公報所記載之銅配線埋入用電鍍液。
本發明之電鍍物係具有形成於基材上之前述特定之合金薄膜，且在該合金薄膜上具有藉由無電解電鍍形成並發揮晶種層作用之銅薄膜。藉由作成前述特定之合金薄膜，如前所述，即可在該合金薄膜上藉由無電解銅電鍍設置成膜均勻性、密著性良好之銅晶種層，因此可作成可進行無電解電鍍且具有阻障功能之單一層，不需形成觸媒金屬層與通常膜厚要數十nm之阻障層等二層。如此，在本發明之電鍍物中，係可藉由作成特定之合金薄膜而可進行無電解電鍍，而作成具有阻障功能之單一層，且可將發揮該晶種層作用之銅薄膜之膜厚設為10nm以下，因此藉由在此銅薄膜上以通常方法進行成為配線部之金屬電鍍，即可作成可應用於線寬數十nm層級之鑲嵌銅配線的半導體元件。再加上，發揮前述晶種層作用之銅薄膜之電阻率可設為10μΩ‧cm以下，而使之後的電鍍初期之均勻成膜變為容易。
(實施例)
接著依據實施例說明本發明，惟本發明並不限定於此等實施例。
(實施例1)
使用鎢作為可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B，及使用鎳作為在pH10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A並使用由鎢與鎳所構成之濺鍍合金靶在半導體基板上製作膜厚10nm之合金薄膜，且在合金膜上藉由無電解電鍍法形成銅電鍍薄膜。第1表係表示使用前述濺鍍合金靶所形成之此合金薄膜之組成、及藉由無電解電鍍所形成之銅電鍍薄膜之膜厚。
另外，藉由無電解電鍍之銅膜之形成，係使用以下組成之電鍍液，在pH12.5(調整劑：氫氧化鉀)、50℃×30至40秒之條件下實施。
針對所獲得之銅電鍍薄膜之膜厚、是否有孔徑10nm以上之孔、電阻率、銅是否有擴散至合金薄膜中、銅電鍍薄膜與合金薄膜之界面之氧化狀態(氧量)、銅電鍍薄膜之密著性進行評估。膜厚係藉由剖面TEM觀察來確認。孔之有無係藉由表面SEM觀察來確認。電阻率係從藉由4端針法之薄片電阻測量、及藉由剖面TEM觀察之膜厚測量結果來算出。銅之擴散之有無及界面之氧化狀態，係藉由AES深度分布(depth profiles)測量來判定。銅電鍍薄膜之密著性，係實施使用透明膠帶(cellophane tape)(CT24、Nichiban製)之膠帶剝離實驗，以指腹使膠帶密著於電鍍面之後，將膠帶剝離以確認膜是否剝離。評估係以○表示無電鍍膜之剝離、以×表示有電鍍膜之剝離。結果彙整於第1表。
此外，對於線寬為90nm、縱寬(aspect)比為4之具有溝槽圖案之半導體基板，在進行前述之濺鍍合金薄膜、及無電解銅電鍍薄膜成膜後，以其作為晶種層藉由電銅電鍍進行配線之埋入。
另外，藉由電鍍之配線埋入，係使用以下組成之電鍍液，在25℃×60秒、電流密度1A/dm2 下實施。硫酸銅　0.25mol/L硫酸　1.8mmol/L鹽酸　10mmol/L微量添加劑(聚乙二醇、(Disulfide Bis(3-sulfopropyl)disodium)、及耶奴斯綠(Janus green))
藉由所獲得之銅電鍍膜之剖面TEM觀察，評估線寬90nm凹槽部之埋入性。判定是否有孔隙或裂縫，且以○表示無孔隙或裂縫、以×表示有孔隙或裂縫。
將結果顯示於第1表。
(實施例2至3、比較例1至3)
將實施例1之合金薄膜之組成改變成如第1表所記載以外，其餘均與實施例1相同地製作合金薄膜，並進行無電解電鍍，然後加以評估。
將結果顯示於第1表。

Claims (2)

  1. 一種電鍍物，其特徵為：在基材上形成防止銅擴散用阻障合金薄膜，其係由可與無電解銅電鍍液中所含之銅離子進行置換電鍍且對銅具有阻障性之金屬B、及在pH 10以上之無電解銅電鍍液中之離子化傾向較金屬B小之金屬A所構成，而該防止銅擴散用阻障合金薄膜係為將前述金屬A設為15原子%以上、35原子%以下之組成，且在此合金薄膜上藉由使用pH 10以上之無電解銅電鍍液之無電解電鍍形成銅薄膜，其中，前述金屬B係為鎢或鉬，而前述金屬A係為選自鎳、鈷、錫之至少1種金屬。
  2. 如申請專利範圍第1項之電鍍物，其中，藉由前述無電解電鍍所形成之銅薄膜係為膜厚10nm以下，電阻率10μΩ‧cm以下。
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WO2010016358A1 (ja) 2010-02-11
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EP2309025A1 (en) 2011-04-13
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EP2309025A4 (en) 2011-09-21
EP2309025B1 (en) 2012-09-26
US20110129688A1 (en) 2011-06-02
JPWO2010016358A1 (ja) 2012-01-19
CN102112660B (zh) 2013-07-10
KR101254407B1 (ko) 2013-04-15
US8283051B2 (en) 2012-10-09

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