TW200305943A - Homogeneous copper-tin alloy plating for enhancement of electro-migration resistance in interconnects - Google Patents
Homogeneous copper-tin alloy plating for enhancement of electro-migration resistance in interconnects Download PDFInfo
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- TW200305943A TW200305943A TW092106694A TW92106694A TW200305943A TW 200305943 A TW200305943 A TW 200305943A TW 092106694 A TW092106694 A TW 092106694A TW 92106694 A TW92106694 A TW 92106694A TW 200305943 A TW200305943 A TW 200305943A
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- Prior art keywords
- copper
- tin
- plating
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- 238000007747 plating Methods 0.000 title claims abstract description 158
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000013508 migration Methods 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 90
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010949 copper Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 claims abstract description 65
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 33
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 26
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000012530 fluid Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims description 39
- 238000009713 electroplating Methods 0.000 claims description 37
- 230000008021 deposition Effects 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000005496 tempering Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 75
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 12
- 239000010408 film Substances 0.000 description 9
- 229910001128 Sn alloy Inorganic materials 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- -1 which is L8 Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 1
- XXONZJKORUUFIZ-UHFFFAOYSA-N 3-sulfanylpyridine-2-sulfonamide Chemical compound NS(=O)(=O)C1=NC=CC=C1S XXONZJKORUUFIZ-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
200305943 玖、發明說明： 【發明所屬之技術領域】 本發明的實施例大致關係於用以沉積一 銅錫合金至半導電基板上之一高深寬比次 特性的方法與設備。 【先前技術】 次四分之一微米大小特性的金屬化係為 代積體電路製程的基礎技術。更明確地說， 積體電路（ULSI)裝置中，即裝置具有超出一 之積體電路者，在這些裝置中心處之多層内 由以導電材料，填充高深寬比内連線特性加 材料係例如鋼或鋁。傳統上，例如化學氣柄 物理氣相沉積（PVD)之沉積技術已經被用以 線特性然而，因為内連線尺寸降低及深寬 經由傳統金屬化技術，而形成無孔隙内連線 更加困難。結果，例如電化學電鍍（E c p)及 鍍技術已經出現作為在積體電路製程中，次 大小兩深寬比内連線特性的無孔隙填充的可 例如，於ECP製程中，形成如一基板 分之一微米大小高深寬比特性可以被有效地 材料，例如銅。ECP電鍍製程大致為兩階甚 一種層係首先形成在該基板的表面特性上， 偏壓被同時施加於基板及定位於電解溶液内 •實質均勻薄膜 〇 · 1 5微米大小 現行及未來世 於例如極大型 百萬個邏輯閘 連線係大致藉 以形成，導電 丨沉積（CVD)及 填充這些内連 比增加，所以 特性填充變得 無電電錄之電 四分之一微米 行製程。 表面内之次四 填充以一導電 製程，其中， 然後，當一電 之陽極間的同 3 200305943 時，基板的諸表面特性係被 溶液大致富有予以電鍍至基 壓的施加造成這些離子予以 然而，有關於ECP銅 内連線之極端小尺寸造成在 增加了形成孔隙的可能性。 於内連線中形成孔隙的可能 遷移阻抗，所以吾人想要產 時，具有想要之電遷移特徵 的方法為將銅與一重金屬作 必可看出增加合金的電阻， 阻特徵。 錫已經被發現為適用以 素。然而，現今沉積技術大 上，然後，回火整個表面， 能有所問題，當回火製程已 性/均質性剖面之銅錫合金 定之導電特徵，而造成孔隙 沉積之銅錫層的沉積已經被 其他更大規格之特性，傳統 積均質銅錫合金至一高深寬 寬比例至少 7，而不會遭遇 銅錫合金電鍍法已經針對於 合金，這對於半導體裝置内 曝露至一電解質溶液。電解質 板表面上之離子，因此，電偏 電鍍至種層上。 沉積製程的一挑戰例如為導電 内連線中，經由電遷移模式， 因為經由電遷移模式，增加了 性係直接相關於銅線的本徵電 生具有最小電阻之導電線，同 。用以改良銅線之電遷移電阻 成合金，而當相較於銅時，不 同時，增加該合金的電遷移電 改良銅的電遷移電阻的合金元 致個別沉積銅及錫層於彼此之 以形成一銅錫合金。此方法可 經被顯示以形成具有變化均勻 ，其可以沿著導電線，產生不 形成。另外，雖然經由電化學 方便地用以產生銲錫凸塊點及 設備及方法已經未能成功地沉 比特性，即一特性，其中深對 填充沉積之孔隙。另外，傳統 具有大百分比錫及小濃度銅之 連線係不想要的，因為富錫合 4 200305943 金的電阻特性係大於銅或富銅合金。例如製 中之多層導電内連線之高深寬比特性的無 U L SI技術的連續成功及連續進行係重要的。 因此，有需要一種方法與設備，以沉積 錫合金薄膜進入一半導體裝置的高深寬比特 【發明内容】 本發明之諸態樣大致提供一電化學電鍍 電鍍一均質銅錫合金至一半導體裝置之高2 微米特性中。於一態樣中，電鍍槽包含一基 有實質平坦下表面架構以嚙合一基板的非產 形絕緣陰極接觸環，具有多數導電偏壓件形 一導電偏壓件係架構以電嚙合一基板的電鍍 樣的實施例中，該電鍍槽更包含一電鍍槽容 持一容積之電化學電鍍溶液，一電源與多數 連並架構以施加一電鍍偏壓至該電鍍面，及 在該電鍍槽容器中的一位置，使得該陽極係 學電鍍溶液中。於浸入該基板時，電鍍溶液系 至約6.5GPM之流率通入電鍍槽中並該電錢 〇·2Μ至約〇·8Μ間之銅離子濃度及約〇.1M 之錫離子的濃度，及電鍍偏壓具有於約 00mA/cm2間之電流密度。 本發明之另一態樣提供一方法，用以電 合金進入半導體基板電鍍面上之高深寬比攻 作半導體裝置 孔隙填充對於 \ 一實質均質鋼 性中。 槽’其架構以 篆寬比次〇. 1 5 板支撐件，具 品側，及一環 成於其中，每 表面。於此態 器，架構以保 導電件電氣相 一陽極，定位 浸入於該電化 έ 以約 0.5GPM 溶液具有於約 至約0.9Μ間 5mA/cm2 至約 錢一均質銅錫 :0.1 5微米特 5 200305943 性中。於一態樣中，該方法提供一電鍍溶液至一電化學電 鍍槽，其中電鍍溶液包含一具有至少一硫酸及磷酸於其中 之酸液；一銅離子源、一錫離子源，具有至少SnS04及SnCl2 之至少之一於其中；及至少一有機電鍍添加劑。於該態樣 之實施例中，該方法更包含曝露一沉積面至電鍍溶液，該 沉積面具有一種層形成於其上；供給一電沉積偏壓至該種 層，其中該沉積偏壓產生於約5mA/cm2至約60mA/cm2之 電流密度於該種層的表面；並以於約 5RPM至約 40RPM 之旋轉速度，旋轉該沉積表面；同時電鍍該錫離子及銅離 子於該基板表面上，以形成一均勻銅錫合金；並以約 200 °C至約40(TC間之溫度回火該銅錫合金，持續於約5分至 約60分之時間。 本發明之實施例更包含提供一方法，用以電鍍一均質 銅錫合金至一半導體基板上。該方法大致包含提供一電鍍 溶液至一電鍍槽，其中該電鍍溶液包含一酸、一銅離子源、 及一錫離子源，該銅離子源包含多至約 9 8 · 5 %之金屬離子 及該錫離子包含多至約1.5 %之金屬離子；提供一電鍍偏 壓至一形成於該半導體基板上之導電層，同時，導電層係 與該電鍍溶液作流體接觸，該電鍍偏壓被架構以重疊銅及 錫之電鍍電位範圍；並同時由該電鍍溶液電鍍銅及錫離子 至導電層上，以在導電層上形成一均質銅錫合金’層。 本發明的實施例更提供一方法，用以電鍍一均質銅錫 合金至一半導體基板上。該方法大致包含提供一電鍍溶液 至一電化學電鍍槽；曝露該基板的一沉積面至該電鍍溶 6 200305943 液，該沉積面具有一種層形成於其中；供給一電沉積偏 至該種層，其中該沉積偏壓產生於約 5mA/cm2至 60mA/cm2之電流密度於種層的表面；同時電鍍錫離子 銅離子至基板表面，以形成一均質銅錫合金。再者，該 鍍溶液大致包含一酸，其包含至少硫酸及磷酸之至少 一，一銅離子源於約0.4至約0.9M之濃度，一錫離子源 該錫離子源包含SnS04及SnCl2之至少之一，該錫離子 於約0.1至0 · 4間之濃度及至少一有機電鍍添加劑。 本發明之諸實施例更提供一方法，用以電鍍一實質 質銅錫合金層於一形成於一半導體基板上之導電種層上 該方法大致包含提供一電鍍溶液，其中具有銅離子及錫 子；曝露該導電種層至電鍍溶液；及施加一電鍍偏壓至 電種層，以電鍍該實質均質銅錫合金層至該導電種層上 其中該電鍍溶液包含於約 0.2M至約 0.5M之銅離子濃 及於約 0.4M至約 0.8M的錫離子濃度，及其中該電鍍 壓包含於約5mA/cm2至約60mA/cm2之電流密度。 本發明之上述特性可以藉由參考附圖中之實施例而 清楚了解。應了解的是，附圖只為本發明之典型實施例 其並不用以限定本發明之範圍，本發明可以採用其他等 之實施例。 【實施方式】 本發明之多數態樣大致提供一方法與設備，用以形 一實質均質銅錫合金至一半導體基板上，更明確地說， 壓 約 及 電 之 源 均 〇 離 導 度 偏 更 效 成 用 7 200305943 以以實質均質銅錫合金填入高深寬比（7或更高）特性中， 該合金具有大濃度之銅（超出約97%)及相當小濃度之錫 (約0.2%至約1.5%) ^銅錫合金大致形成於基板上並經由 一 ECP製程形成内特性中，該銅錫合金提供於半導體裝 置的導電特性中之加強之電遷移阻抗並當高電流通過該内 連線時，防止孔隙形成在界面處。用以沉積銅錫合金之ECP 製程的實施例大致包含將一計算量之錫加入一銅電鍵溶液 中’以及，施加一計算電壓至浸入於電鍍溶液中之基板中。 所計算之加入電鍍溶液中之量及所計算之施加電壓係明確 地加以選擇，以提供實質均質銅錫合金的沉積。另外，本 發明之實施例係被架構以電鍍銅錫合金進入很高深寬比特 性内’即大於10:1 ’對於窄導電基板，即為次〇·1〇微米 寬度特性。銅錫合金的沉積係如下所述地，例如藉由以無 電沉積製程，沉積很薄銅錫合金於一 PVD銅種層上，隨 後電鍍銅錫合金於電鍍溶液中加以完成^ 第1圖例示本發明之例示堰型電鍍機丨〇〇的剖面圖。 電鍵機1〇〇大致包含一電解質容器112，具有一開口頂部 及一蓋/基板爽具114，其係可樞轉地安排於電解質容器 112上。蓋/基板夾具114大致被架構以經由多數凹槽124， 而支撐一基板122於其下表面，諸凹槽係形成在基板夾具 114的下表面。凹槽係與一真空泵（未示出）流體相通，因 此’當一負壓為真空泵所施加至凹槽丨2 4時，基板丨22係 固定在真空吸盤型操作下，被固定至基板夾具114。 一接觸環1 2 0係例如定於蓋組件的下面，並與一電源 200305943 (未示出）電氣連接。因此 U此’接觸環120被架構以電嚙合基 板122/提供一電鑛偏壓至其上。可以在形狀上為環形之 接觸壤120大致包含多叙 夕數導電接觸銷126安排於接觸環 120的圓周部分上。多數接觸銷126大致徑向向内延伸於 土板 W圓周上’以接觸銷126的尖端接觸形成於基板 122上之導電種層。另夕卜，電解質容器m可以包含一分 離薄膜128，定位於一陽極116與基板122之間。薄膜128 可以操作以界定於電解質容ϋ "2中之個別之陽極及陰極 室’即陽極室將包圍陽極及陰極室將鄰近基板的電鍍面。 陽極Π 6被架構以供給離子至被收容於容器i丨2内之電鍍 /合液刀離溥膜係大致為一薄膜，架構以允許施加至容器 之電解/谷液流經其間’同時，限制其他材料的流通， 即〉可染物、銅球等流經該薄膜並接觸該基板丨22。電鍍溶 液被供、”6 g線11 8所供給至該電解質容器11 2，管線係 大致與本技藝所知之一泵及電解質供給系統相通。 再者’有關於陽極Π 6結構及/或架構，應注意的是 錫可以存在於二價及四價的狀態中。因此，由二價轉移至 四價狀態大致發生於一較銅金屬氧化為Cu2+之電位為負 的電位時。這代表於電鍍時之挑戰，因為Sn2+離子將大 致被氧化於陽極表面上，造成Sn〇2的形成，其係為一不 溶解於酸之陶竟。這些固態粒子可能阻塞陽極並需要以施 加一電鑛電壓，最後，造成陽極之完全與電解質阻隔。再 者’ Sn〇2的形成同時也造成溶液變髒並造成過濾器之經 常阻塞並降低於電解溶液中之Sn2+濃度。然而，本發明 9 200305943 之實施例藉由增加陽極表面積至陽極電流密度被限制於小 值（陰極電流岔度可以大至6〇mA/cm2)的範圍，而針對這 些挑戰。這造成於維持陽極電位於很小值，其中Sn2+至s^+ 之氧化反應並不可能。 離子之透射入陽極室可以藉由插入 ： 另外， 丨W雖 子2膜加以防止。這也可以藉由具一陽極室（未含任何 )加以凡成，該陽極室係為一流體可滲透膜加以與 陰極室分離》陽極室相對於陰極室應具有一正|，使得其 中只有-流體流向陰極室的方向…，陽極室的溫度； 以保持高於陰極室，使得對流係朝向該陰極室。 第2圖例示另一例示本發明4電鑛處理# 200的剖面 圖。處理槽200大致包含—頭組件21〇、一處理組件Μ。、 及一電解質收集器240。電解質收集器24〇大致架構以固 定至一電鏡系統的主架。電解質收集器240大致包含—内 壁246、一外壁248、及—底部247，連接相關壁面。_ 電解質出口 249係安排經由電解質收集器24〇的底部247 並經由管、軟管、#其他流體傳送連接器被連接至一電解 質補充系、统。頭組件210係大致安裝至-頭組件架252, 其包含一安裝柱254及一 „ 256。安裝柱254係大致安 裂在一主架主體214,及懸臂256大致由安裝柱254之上 部份橫向延伸。一般而t，安裝柱254相對於沿著安裝柱 之垂直轴提供旋轉動作，以允許頭組件21〇之旋轉。鞟臂 ⑸的下端係大致連接至_安裝在安裝柱上之懸臂致 動器257,例如一氣壓缸。懸臂致㈣257提供相對於懸 10 200305943 臂256 m 件致動 升/下降 一基板 具組# 2 5 0 的， 例如為 供足夠 致與― 體，其 能至一 主體係 基板。 座落面 基板。 處理之 基板的 2 0 0 中 積於其 導電層 以在其 於 基板係 及安裝柱254間之接點之懸臂256的樞轉移動。 組件210大致包含一基板夾具組件25〇及一基板組 器25 8。基板組件致動器25 8操作以旋轉及/或上 基板夾具組件2 5 0。基板夾具組件2 5 0大致包含 夾具264及一 一體成型之陰極接觸環266。基板夾 250包含多數真真通道267形成於基板夾具組件 下側。與一真空泵（未示出）相通之真空通道267係 環形定位在基板夾具紐件25〇的下側並被架構以提 真空壓力，以將一基板固定於其上，供處理用。大 電源（未示出）電連接之接觸環266包含一環形主 具有多數導電件，安排於其上，用以由電源供給電 在基板夾具組件250上之基板。接觸環266的環形 大致以一絕緣材料建構，以電絕緣開多數導電件與 接觸環266的主體及導電件大致形成一直徑内基板 ，其於處理時，可以支撐予以為設備2〇〇所處理之 然而，本發明之接觸環被架構以電嚙合及接觸予以 基板，於基板的非產品側，即於基板的背面，使得 產品側不作電氣或機械接觸。因此，處理於電鍍槽 之基板將大致具有一背面導電層，架構以電嚙合沉 上之背面接觸環。另外，可以為一種層延伸之背面 也可以架構以使電源通電至基板的前面或產品面， 上完成電鑛。 操作中，不管所用之電鍍槽架構為何，予以電鍍的 大致被固定至一基板支撐件及基板表面被與一電鍍 11 200305943 觸。於接觸電鑛溶液…，電偏壓係施加至沉積 土的電鍍面上之種層。電偏壓大致為一偏壓架構以將 土反面/種層㈣以一陰極電荷，這使得在電鑛溶液中之 電錢離子被推出溶液外 種層上。 電鍍在被陰極▼電的基板表面/ 於傳統電鍍系統中，電鑛溶液大致包含一水溶液，其 夕s ;丨L 8夂、磷酸、或其衍生物。電鍍溶液可以更包含一或 多數有機添加劑，gp平衡劑、抑制劑、加速劑、及/或其 他本技藝中已知之添加劑，以促成對電鍍製程的控制。添 加劑典型為有機材冑，其係為已知以吸收至予以電鐘的基 表面上例如，有用之抑制劑也可以包含聚酸，例如聚 乙烯、乙二醇，或其他聚合物，例如聚丙烯氧化物，其係 為已知以禁止於基板上之沉積速率。有用之加速劑，可以 例如硫化物或二硫化物，例如雙（3_磺酸丙基）二硫化物， 其影響沉積於基板上之鋼的微結構。有用平衡劑可以包含 胺及聚醯胺，其改良沉積於基板上之鋼的厚度分佈。 因為本發明被架構以沉積一均質銅錫合金於一電化學 電鍍製程中’所以傳統鋼電鍍溶液可以被修改以包含需用 以支援銅錫電鍍的錫離子。然而，沉積於電化電鍍製程中 之銅及錫之數量係主要為兩因素所管理：第一，電鍍操作 進行時之電鍍電位；及第二，於電鍍溶液中之錫離子的濃 度成比例於溶液中之銅離子的濃度。有關於在電鍍溶液中 之錫的濃度’因為錫在鋼中有很低之固溶度，大致係低於 約0.5重量％，大量之錫的加入電鍍溶液中，大致造成金 12 200305943 屬間化合物的形成，這對於半導體裝置的内連線應用係有 害的。因此，吾人想要維持於電鍍合金中之錫百分比低於 1 .5 %以下，當相較於傳統銅内連線時，這提供良好導電 特徵，及良好電遷移特性。另外，電鍍溶液或銅錫合金所 產生之高濃度錫之局部黏聚也造成缺點。因此，本發明之 實施例想出錫的計算濃度，被架構以產生最佳電鍍特徵， 而不會形成金屬間化合物，其中錫的計算濃度係遠小於電 鍍溶液中之銅的濃度，即低於約 1. 5 %之錫對約 9 8.5 %或 更大之銅。 有關於用於電鍍均質銅錫薄膜之電鍍電位，已知特定 電鍍電位範圍造成特定金屬的最佳電鍍。因此，為了銅錫 合金予以由單一電鍍溶液電鍍，於電鍍操作中所施加之電 鍍電位將大致重疊於用於該兩金屬的電鍍電位範圍。因 此，當所施加電鍍電位係在兩金屬的電鍍範圍内時，則可 以同時進行兩金屬的電鍍。然而，應注意的是，用於金屬 的電鍍電位隨著在電鍍溶液中之金屬離子的濃度及其他參 數改變。因此，特定處理參數將隨著處理系統有所不同而 有所改變。然而，為了參考，相對於標準氩電極，用於銅 的標準還原電位係0 · 3 4伏，而相對於標準氫電極，用於 錫之標準還原電位為-0 · 1 3伏。由濃度變動所造成之還原 電位的變化可以以下等式加以計算： E = E0-R.T.ln[M + ] (1) 其中E為金屬的沉積電位，E。代表標準沉積電位，R 代表常數，T代表電鍍溶液的溫度，及Μ代表於電鍍溶 13 200305943 液中之予以電鍍的金屬離子的濃度。因此，因為銅的標準 沉積/還原電位係遠大於錫的標準沉積電位，所以銅的還 原電位可以經由等式（1)中之處理參數的演算，而更接近 錫的還原電位。然而，雖然公式（1)表示銅及錫的還原電 位可以更接近，以促成銅錫合金的均質電鍍，但單單是於 離子濃度的變化並不會造成一金屬的還原電位的大量變 化。另外，傳統銅電鍍系統大致被最佳化，以完成無孔隙 填充之高深寬比特性，因此，吾人並不想要修改於電鍍溶 液中之銅離子的濃度，以完成銅及錫的同時電鍍，因為銅 電鍍特徵可以忍受修改。因此，另一參數被調整以取得有 效及同時電鍍銅及錫的是於電鍍製程中，施加至基板表面 上之電鍍電位或電流密度。 例如，第3圖，顯示用以個別沉積銅及錫之電流對電 壓圖。如於第3圖所示，於電位 V1，並沒有錫沉積及很 少銅沉積發生。然而，當電位由V1增加至V3時，錫沉積 數量增加，銅的沉積數量也增加。相同影響作用至一限定 範圍，並以增加於電鍍溶液中之錫離子（Sn2 + )濃度加以完 成。另外，雖然基於上述理由，傳統電鍍系統並不想要， 但相同作用可以藉由降低於電鍍溶液中之銅離子（Cu2 + )之 濃度加以完成。因此，基於可以修改的參數，以促成同時 銅錫之沉積的觀點，本發明之實施例想到以下處理參數將 允許在電化學電鍍槽中，形成實質均質的銅錫合金薄膜。 一鍍銅溶液可以用以實施本發明的實施例。一如上所 述之傳統鍍銅溶液可以包含例如一銅源、一鹵化素源、及 14 200305943 -或多數有機添加劑，被架構以提 徵的控制要素。銅 又/夺夜之電鍍特200305943 (1) Description of the invention: [Technical field to which the invention belongs] Embodiments of the present invention generally relate to a method and equipment for depositing a copper-tin alloy onto a semi-conductive substrate with a high aspect ratio characteristic. [Previous technology] Metalization systems with sub-quarter-micron size characteristics are the basic technology for the generation of integrated circuit processes. More specifically, in integrated circuit (ULSI) devices, that is, devices with more than one integrated circuit, in multiple layers at the center of these devices are filled with conductive materials, filled with high aspect ratio interconnect characteristics and materials such as steel Or aluminum. Traditionally, deposition techniques such as chemical gas-spinning physical vapor deposition (PVD) have been used for line characteristics. However, because of the reduced size and depth of interconnects, it is more difficult to form void-free interconnects through traditional metallization techniques. As a result, for example, electrochemical plating (E cp) and plating technology have emerged as non-porous filling of the interconnect characteristics of the sub-size to aspect ratio in integrated circuit manufacturing processes. For example, in the ECP process, it is formed as a substrate One micron size high aspect ratio characteristics can be effectively material such as copper. The ECP electroplating process is roughly a two-step process. First, a layer is formed on the surface of the substrate. A bias voltage is applied to the substrate and positioned in the electrolytic solution at the same time. • A substantially uniform thin film. The extremely large one million logic gate lines are roughly formed, and the interconnect ratios of conductive, deposition (CVD) and filling are increased, so the characteristic filling becomes a quarter of a micron line without electricity recording. The surface is then filled with a conductive process, in which, then, when the anodes of an electricity are the same, the surface characteristics of the substrate are substantially rich by the solution and are plated to the application of the base pressure causing these ions to be applied. The extremely small size associated with ECP copper interconnects increases the likelihood of void formation. The possible migration resistance of the pores formed in the interconnects, so when we want to produce, the method that has the desired electromigration characteristics is to use copper and a heavy metal. It must be seen that the resistance and resistance characteristics of the alloy are increased. Tin has been found to be suitable. However, today's deposition technology is great, and then, tempering the entire surface can have some problems. When the tempering process has the conductive characteristics of the copper-tin alloy profile, the deposition of the copper-tin layer that caused the pore deposition has been affected. For other features with larger specifications, the traditional copper-tin alloy with a homogeneous volume to a high aspect ratio is at least 7 without encountering the copper-tin alloy plating method which has been targeted at the alloy, which is exposed to an electrolyte solution in the semiconductor device. The ions on the surface of the electrolyte plate are therefore electroplated to the seed layer. One of the challenges of the deposition process is, for example, in conductive interconnects, via electromigration mode, because via electromigration mode, the conductive lines that have a minimum resistance directly related to the intrinsic electricity of copper wires are added, the same. The alloy used to improve the electromigration resistance of the copper wire, and when compared to copper, the alloy element that increases the electromigration of the alloy and improves the electromigration resistance of the copper at the same time causes the copper and tin layers to be individually deposited on each other. A copper-tin alloy is formed. This method can be shown to form with uniform variation, which can follow conductive lines, resulting in non-formation. In addition, although it is conveniently used to generate solder bump points and equipment and methods through electrochemistry, it has not been able to successfully sink specific characteristics, that is, a characteristic in which the deep pores fill the deposited pores. In addition, the traditional connection system with a large percentage of tin and a small concentration of copper is not desirable because the resistance characteristics of tin-rich alloy 4 200305943 gold are greater than those of copper or copper-rich alloys. For example, the continuous success and continuous operation of the U L SI technology without the high aspect ratio characteristics of the multilayer conductive interconnects in the system are important. Therefore, there is a need for a method and equipment for depositing tin alloy thin films into a semiconductor device with high depth and width. [Summary of the Invention] Aspects of the present invention generally provide an electrochemical plating of a homogeneous copper-tin alloy to the height of a semiconductor device. 2 micron characteristics. In one aspect, the electroplating tank includes a non-producing insulating cathode contact ring having a substantially flat lower surface structure to engage a substrate, and has a plurality of conductive biasing members in the form of a conductive biasing member structure to electrically engage a substrate. In the embodiment of the electroplating sample, the electroplating tank further includes an electroplating tank to hold a volume of electrochemical electroplating solution, a power source connected to the majority to apply a plating bias to the electroplating surface, and in the electroplating tank container. A position such that the anode system is in a plating solution. When immersed in the substrate, the plating solution is passed into the plating bath at a flow rate of about 6.5 GPM and the copper ion concentration of the electricity between 0.2 M and about 0.8 M and the tin ion concentration of about 0.1 M, and The plating bias has a current density between about 00 mA / cm2. Another aspect of the present invention provides a method for attacking a semiconductor device with a high aspect ratio of a galvanic alloy entering a plating surface of a semiconductor substrate. The pore filling is in a substantially homogeneous steel. The groove ’has a structure with a width to width ratio of 0.15 plate support, a product side, and a ring formed in each surface. In this device, the structure is designed to maintain the electrical phase of the conductive part as an anode, and is positioned to be immersed in the electrochemical device. The solution has a 0.5GPM solution with a voltage of about 5mA / cm2 to about 0.9M to about 0.4 a homogeneous copper tin: 0.1 5 microns special 200305943 in sex. In one aspect, the method provides a plating solution to an electrochemical plating tank, wherein the plating solution includes an acid solution having at least one sulfuric acid and phosphoric acid therein; a copper ion source, a tin ion source, having at least SnS04 and At least one of SnCl2; and at least one organic plating additive. In an embodiment of this aspect, the method further includes exposing a deposition surface to a plating solution, the deposition surface having a layer formed thereon; and supplying an electrodeposition bias to the layer, wherein the deposition bias is generated at A current density of about 5 mA / cm2 to about 60 mA / cm2 is on the surface of the layer; and the deposition surface is rotated at a rotation speed of about 5 RPM to about 40 RPM; at the same time, the tin ions and copper ions are electroplated on the surface of the substrate, To form a uniform copper-tin alloy; and tempering the copper-tin alloy at a temperature of about 200 ° C to about 40 ° C for a time of about 5 minutes to about 60 minutes. Embodiments of the present invention further include providing a A method for electroplating a homogeneous copper-tin alloy onto a semiconductor substrate. The method generally includes providing a plating solution to a plating bath, wherein the plating solution includes an acid, a copper ion source, and a tin ion source, the copper The ion source contains up to about 98.5% metal ions and the tin ion contains up to about 1.5% metal ions; a plating bias is provided to a conductive layer formed on the semiconductor substrate, and the conductive layer is With this plating Liquid as fluid contact, the plating bias is structured to overlap the plating potential range of copper and tin; and at the same time copper and tin ions are plated on the conductive layer from the plating solution to form a homogeneous copper-tin alloy layer on the conductive layer An embodiment of the present invention further provides a method for electroplating a homogeneous copper-tin alloy onto a semiconductor substrate. The method generally includes providing a plating solution to an electrochemical plating bath; exposing a deposition surface of the substrate to the electroplating Dissolve 6 200305943 liquid, the deposition surface has a layer formed therein; supplying an electrodeposition biased to the layer, wherein the deposition bias is generated at a current density of about 5 mA / cm2 to 60 mA / cm2 on the surface of the seed layer; Electroplating tin ions and copper ions to the surface of the substrate to form a homogeneous copper-tin alloy. Furthermore, the plating solution generally contains an acid, which contains at least one of sulfuric acid and phosphoric acid, and a copper ion originates from about 0.4 to about 0.9M. Concentration, a tin ion source The tin ion source includes at least one of SnS04 and SnCl2, the tin ion has a concentration between about 0.1 to 0.4, and at least one organic plating additive. The embodiment further provides a method for electroplating a substantially copper-tin alloy layer on a conductive seed layer formed on a semiconductor substrate. The method generally includes providing a plating solution having copper ions and tin particles; exposing the conductive A seed layer to a plating solution; and applying a plating bias to the electric seed layer to electroplate the substantially homogeneous copper-tin alloy layer onto the conductive seed layer, wherein the plating solution contains a copper ion concentration of about 0.2M to about 0.5M and A tin ion concentration of about 0.4M to about 0.8M, and a current density of about 5 mA / cm2 to about 60 mA / cm2 in the plating voltage. The above characteristics of the present invention can be made clear by referring to the embodiments in the accompanying drawings. It should be understood that the drawings are only exemplary embodiments of the present invention and are not intended to limit the scope of the present invention. The present invention may adopt other embodiments. [Embodiments] Most aspects of the present invention generally provide a method and equipment for forming a substantially homogeneous copper-tin alloy onto a semiconductor substrate. More specifically, the source and the source of electricity are more uniform and the ion conductivity is higher. Effectiveness 7 200305943 to fill the characteristics of high aspect ratio (7 or higher) with a substantially homogeneous copper-tin alloy with a high concentration of copper (over about 97%) and a relatively small concentration of tin (about 0.2% to (Approximately 1.5%) ^ A copper-tin alloy is generally formed on a substrate and formed into an internal characteristic through an ECP process. The copper-tin alloy provides an enhanced electromigration resistance in the conductive characteristics of a semiconductor device and when a high current passes through the interconnection At the same time, the formation of pores at the interface is prevented. An embodiment of an ECP process for depositing a copper-tin alloy generally includes adding a calculated amount of tin to a copper electrical bond solution 'and applying a calculated voltage to a substrate immersed in a plating solution. The calculated amount added to the plating solution and the calculated applied voltage are explicitly selected to provide the deposition of a substantially homogeneous copper-tin alloy. In addition, the embodiment of the present invention is structured to plate copper-tin alloy into a high depth and width characteristic, that is, greater than 10: 1. For a narrow conductive substrate, it is a sub-0.10 micron width characteristic. The copper-tin alloy is deposited as described below. For example, by using an electroless deposition process, a very thin copper-tin alloy is deposited on a PVD copper seed layer, and then the copper-tin alloy is plated in a plating solution. An example of the invention is a cross-sectional view of a weir-type plating machine. The key machine 100 generally includes an electrolyte container 112 having an open top and a lid / substrate cooler 114 which is pivotably arranged on the electrolyte container 112. The cover / substrate holder 114 is generally structured to support a substrate 122 on a lower surface thereof through a plurality of grooves 124, and the grooves are formed on the lower surface of the substrate holder 114. The groove is in fluid communication with a vacuum pump (not shown), so 'when a negative pressure is applied to the groove by the vacuum pump, the substrate is fixed to the substrate holder 114 under a vacuum chuck operation. . A contact ring 120 is, for example, positioned under the cover assembly and is electrically connected to a power source 200305943 (not shown). Therefore, the contact ring 120 is configured to electrically engage the substrate 122 / provide a power bias to it. The contact soil 120, which may be annular in shape, generally includes a plurality of conductive contact pins 126 arranged on a circumferential portion of the contact ring 120. Most of the contact pins 126 extend substantially radially inwardly on the circumference of the soil plate W, and the tips of the contact pins 126 contact the conductive seed layer formed on the substrate 122. In addition, the electrolyte container m may include a separation film 128 positioned between an anode 116 and a substrate 122. The thin film 128 can be operated to define individual anode and cathode compartments in the electrolyte container " 2, i.e. the anode compartment will surround the anode and cathode compartments adjacent to the plating surface of the substrate. The anode Π 6 is structured to supply ions to the electroplating / liquid-knife separation membrane system contained in the container i 2 and is generally a thin film. The structure is configured to allow the electrolysis / valley fluid applied to the container to flow therethrough. Circulation of other materials, that is, dyeable materials, copper balls, etc. flow through the film and contact the substrate 22. The plating solution is supplied and the 6 g line 11 8 is supplied to the electrolyte container 11 2. The pipeline is generally connected to one of the pumps and the electrolyte supply system known in the art. Furthermore, there is a structure and / or structure of the anode Π 6 It should be noted that tin can exist in divalent and tetravalent states. Therefore, the transition from divalent to tetravalent state occurs roughly when the potential of a copper metal oxidized to Cu2 + is negative. This is represented by electroplating The challenge is that Sn2 + ions will be roughly oxidized on the surface of the anode, resulting in the formation of Sn02, which is an insoluble ceramic. These solid particles may block the anode and need to apply an electric voltage. Finally, the anode is completely blocked from the electrolyte. In addition, the formation of SnO2 also causes the solution to become dirty and causes the filter to frequently block and reduce the Sn2 + concentration in the electrolytic solution. However, the embodiment of the invention 9 200305943 These challenges are addressed by increasing the anode surface area until the anode current density is limited to a small value (cathode current bifurcation can be as large as 60 mA / cm2). This results in maintaining the anode It is located at a very small value, in which the oxidation reaction of Sn2 + to s ^ + is not possible. The transmission of ions into the anode chamber can be inserted by: In addition, 丨 W is prevented by 2 membranes. This can also be achieved by having an anode chamber ( The anode chamber is a fluid-permeable membrane separated from the cathode chamber. The anode chamber should have a positive | relative to the cathode chamber, so that only-fluid flows in the direction of the cathode chamber ..., anode chamber To maintain the temperature higher than the cathode chamber, so that the convection system faces the cathode chamber. Fig. 2 illustrates another cross-sectional view illustrating another example of the 4 electric mine treatment # 200 of the present invention. The treatment tank 200 generally includes a head assembly 21 and a treatment. Module M, and an electrolyte collector 240. The electrolyte collector 240 is generally structured to be fixed to the main frame of an electron microscope system. The electrolyte collector 240 generally includes-an inner wall 246, an outer wall 248, and a bottom 247, connected to the relevant wall surface. _ Electrolyte outlet 249 is arranged to be connected to an electrolyte replenishing system and system via the bottom 247 of the electrolyte collector 24 and via pipes, hoses, and other fluid transfer connectors. Head assembly 21 The 0 series is roughly mounted to the head assembly frame 252, which includes a mounting post 254 and a 256. The mounting post 254 is substantially split into a main frame body 214, and the cantilever 256 extends substantially laterally from a portion above the mounting post 254. Generally, the mounting post 254 provides a rotational motion relative to a vertical axis along the mounting post to allow rotation of the head assembly 21o. The lower end of the arm ⑸ is roughly connected to a cantilever actuator 257 mounted on a mounting post, such as a pneumatic cylinder. The cantilever actuator 257 provides 256 m pieces of actuation relative to the cantilever 10 200305943 arm to raise / lower a substrate with a set # 2 50, for example, to provide sufficient flexibility, it can reach a main system substrate. Seating surface Substrate. The conductive substrate of the processed substrate is accumulated on its conductive layer to pivotally move the cantilever 256 at its contact point between the substrate system and the mounting post 254. The assembly 210 generally includes a substrate holder assembly 250 and a substrate assembly 258. The substrate assembly actuator 25 8 operates to rotate and / or mount the substrate holder assembly 250. The substrate holder assembly 250 generally includes a holder 264 and an integrally formed cathode contact ring 266. The substrate holder 250 includes a plurality of true channels 267 formed under the substrate holder assembly. A vacuum channel 267 communicating with a vacuum pump (not shown) is annularly positioned on the lower side of the substrate holder button 25 and is structured to raise vacuum pressure to fix a substrate thereon for processing. A contact ring 266 electrically connected to a large power source (not shown) includes a ring-shaped main body having a plurality of conductive members arranged thereon for supplying power to a substrate on the substrate holder assembly 250 by a power source. The ring shape of the contact ring 266 is generally constructed of an insulating material. Most of the conductive members are electrically insulated from the main body and the conductive members of the contact ring 266 to form a diameter inner substrate. When processed, it can be supported and processed by the equipment 2000. However, the contact ring of the present invention is configured to be electrically engaged and contacted to the substrate, on the non-product side of the substrate, that is, on the back of the substrate, so that the product side does not make electrical or mechanical contact. Therefore, the substrate processed in the plating bath will generally have a back conductive layer, and the structure will electrically engage the back contact ring on the sink. In addition, it can be a layer extended back surface or a structure to enable the power supply to the front surface of the substrate or the product surface to complete the power mining. In operation, regardless of the plating bath structure used, the plated is roughly fixed to a substrate support and the surface of the substrate is contacted with a plating 11 200305943. In contact with the electro-mineral solution ..., an electrical bias is applied to the seed layer on the electroplated surface of the deposited soil. The electrical bias is roughly a biasing structure to charge the opposite side of the soil / seed layer with a cathode charge, which causes the electron ions in the power mineral solution to be pushed out of the seed layer of the solution. Electroplating on the surface of the substrate that is electrically charged by the cathode / In a conventional electroplating system, the electro-mineral solution generally contains an aqueous solution, which is L8, phosphoric acid, or a derivative thereof. The plating solution may further include one or more organic additives, gp balancers, inhibitors, accelerators, and / or other additives known in the art to facilitate control of the plating process. The additive is typically an organic material, which is known to absorb onto the base surface to which the electric clock is applied. For example, useful inhibitors may also include polyacids such as polyethylene, ethylene glycol, or other polymers such as polypropylene. Oxides are known to inhibit deposition rates on substrates. Useful accelerators can be, for example, sulfides or disulfides, such as bis (3-sulfopropyl) disulfide, which affect the microstructure of the steel deposited on the substrate. Useful balancing agents may include amines and polyamides, which improve the thickness distribution of steel deposited on a substrate. Because the present invention is structured to deposit a homogeneous copper-tin alloy in an electrochemical plating process', conventional steel plating solutions can be modified to include tin ions needed to support copper-tin plating. However, the amount of copper and tin deposited in the electrochemical plating process is mainly managed by two factors: first, the plating potential when the plating operation is performed; and second, the concentration of tin ions in the plating solution is proportional to the solution The concentration of copper ions in it. Regarding the concentration of tin in the plating solution 'because tin has a very low solid solubility in steel, which is about less than about 0.5% by weight. A large amount of tin is added to the plating solution, which generally causes gold 12 200305943 intermetallic compounds Formation, which is detrimental to the interconnection of semiconductor devices. Therefore, we want to keep the tin percentage in the electroplated alloy below 1.5%, which provides good conductive characteristics and good electromigration characteristics when compared to traditional copper interconnects. In addition, localized cohesion of high concentrations of tin produced by plating solutions or copper-tin alloys also causes disadvantages. Therefore, the embodiment of the present invention contemplates that the calculated concentration of tin is structured to produce optimal plating characteristics without forming intermetallic compounds. The calculated concentration of tin is much less than the concentration of copper in the plating solution, that is, less than Approximately 1.5% of tin versus approximately 98.5% or greater copper. Regarding the plating potential used to plate a homogeneous copper-tin film, it is known that a specific plating potential range results in optimal plating of a specific metal. Therefore, for copper-tin alloys to be plated with a single plating solution, the plating potential applied during the plating operation will substantially overlap the range of plating potentials for the two metals. Therefore, when the applied plating potential is within the plating range of the two metals, the plating of both metals can be performed simultaneously. It should be noted, however, that the plating potential for the metal varies with the concentration of metal ions in the plating solution and other parameters. Therefore, specific processing parameters will vary depending on the processing system. For reference, however, the standard reduction potential for copper is 0 · 34 volts relative to a standard argon electrode, and the standard reduction potential for tin is -0.33 volts relative to a standard hydrogen electrode. The change in reduction potential caused by the concentration change can be calculated by the following equation: E = E0-R.T.ln [M +] (1) where E is the deposition potential of the metal, and E. Represents the standard deposition potential, R represents the constant, T represents the temperature of the plating solution, and M represents the concentration of the metal ions to be plated in the plating solution. Therefore, because the standard deposition / reduction potential of copper is much larger than the standard deposition potential of tin, the reduction potential of copper can be closer to the reduction potential of tin through the calculation of the processing parameters in equation (1). However, although formula (1) indicates that the reduction potentials of copper and tin can be closer to promote homogeneous electroplating of copper-tin alloys, changes in the ion concentration alone will not cause a large change in the reduction potential of a metal. In addition, the traditional copper plating system is roughly optimized to complete the high aspect ratio characteristics of non-pore filling. Therefore, we do not want to modify the concentration of copper ions in the plating solution to complete the simultaneous plating of copper and tin, because Copper plating features can tolerate modification. Therefore, another parameter is adjusted to obtain effective and simultaneous electroplating of copper and tin. The electroplating potential or current density applied to the substrate surface during the electroplating process. For example, Figure 3 shows the current vs. voltage graph used to deposit copper and tin individually. As shown in Figure 3, at potential V1, no tin deposition and very little copper deposition occur. However, when the potential was increased from V1 to V3, the amount of tin deposition increased and the amount of copper deposition also increased. The same effect works to a limited range and is accomplished by increasing the tin ion (Sn2 +) concentration in the plating solution. In addition, although the conventional plating system is not desired for the reasons mentioned above, the same effect can be accomplished by reducing the concentration of copper ions (Cu2 +) in the plating solution. Therefore, based on the parameter that can be modified to facilitate the simultaneous deposition of copper and tin, the embodiments of the present invention contemplate that the following processing parameters will allow a substantially homogeneous copper-tin alloy film to be formed in an electrochemical plating bath. A copper plating solution can be used to implement the embodiments of the present invention. The conventional copper plating solution as described above may contain, for example, a copper source, a halogenated source, and most of the organic additives, which are structured to control the elements. Copper
Enth_及液係可以由很多公司購得，例如 y。作為電化學電鍍溶液之鋼$ 硫酸銅，例如，盆 j原可以；a 其具有於約5g/L至約100g/L門^ 乂為Enth_ and liquid systems are available from many companies, such as y. The steel used as the electrochemical plating solution is copper sulfate, for example, the pot j can be used; a it has a gate in the range of about 5g / L to about 100g / L ^ 乂
漢度。電錢溶液可以另包含—酸，其可以例如曰鋼離子 至約2〇〇g/L F4之濃度’再者，電鍍溶液可人約5g/L Γ;Γ氣化物，其可以例如於至約：物 間。可以用於電鍵溶液中之酸包含硫酸、碟酸15⑽之 :丁生物。除了使用硫酸銅作為鋼源外，本及/或其 …鑛溶液可以包含其他銅鹽，例如，…：施例更 糖Si銅、4酸錢鋼、硫酸鋼夂_、葡萄 Λρ.... “、、碟酸鋼、虱化鋼、4、 銅’例如作為銅源。然而 或氰化 數。 I月實施例並不限定這些參 傳統鋼電鍍溶液可以f 用以提供電鑛溶液的電錄特^；；或多數有機添加劑，作 為例如平衡劑、抑制劑、壓控制要素。添加劑可以 ^ A , 制劑、光亮劑、加速劑、+ ::本技藝所知之其他添加劑可以為典型之有機材料或其 吸收至予以電鍍的基材表 科’其 含共聚物-乙烤氧化物、丙二。有用之壓制劑典型包含包 娜乳化物、聚驗，例如聚 醇（PEG)，及/或其他聚合物 '乙二 例如聚乙烯-聚丙烯氧化物 :及收於基板表面上，減緩㈣積於吸收區域中 速劑典型包含硫化物或二访 用加 瓜化物，例如雙（3 -磺酸丙義 硫化物、MPSA、及SPS公2 土’二 刀予，其與壓制劑競爭吸收點 加速鋼沉積於吸收區域中。士 ”、 ’ 有用平衡劑典型包含胺、嘆_ 200305943 唑、咪唑、及其他含有機物之氮。有用抑制劑典型包含苯 曱酸鈉及亞硫酸鈉，其抑制銅沉積於基板上的速率。另外， 對苯二酚可以用作為抑制劑，並可以加入電鍍溶液中，例 如至多約2500ppm之濃度。Hando. The battery solution may further include an acid, which may, for example, be a concentration of steel ions to about 200 g / L F4 '. Furthermore, the plating solution may be about 5 g / L Γ; Γ gaseous, which may be : Between the things. Acids that can be used in the bond solution include sulfuric acid and 15 g of acetic acid. In addition to using copper sulfate as the steel source, the present and / or its ore solution may contain other copper salts, for example,…: Examples are more sugar Si copper, 4 acid steel, sulfuric acid steel 夂 _, grape Λρ ... ",, acid steel, lacquered steel, 4, copper, for example, as a copper source. However, the cyanide number is not limited to these examples. The traditional steel plating solution can be used to provide a record of the electric mining solution. Special additives; or most organic additives, such as balancers, inhibitors, pressure control elements. Additives can be A, formulations, brighteners, accelerators, +: other additives known in the art can be typical organic materials Or it is absorbed into the substrate to be electroplated, which contains copolymers-ethyl oxide, propylene diene. Useful pressure formulations typically include buna emulsions, polyamines, such as polyalcohols (PEG), and / or others Polymer 'ethylene such as polyethylene-polypropylene oxide: and closed on the surface of the substrate to slow down the build-up in the absorption zone. The speed agent typically contains sulfides or quaternary guacuides, such as bis (3-propanesulfonic acid). Sulfide, MPSA, and SPS It competes with the pressure-absorbing agent for the absorption point to accelerate the deposition of steel in the absorption region. "", Useful balance agents typically include amines, 2003-0543 azole, imidazole, and other organic nitrogen. Useful inhibitors typically include sodium benzoate And sodium sulfite, which inhibits the rate of copper deposition on the substrate. In addition, hydroquinone can be used as an inhibitor and can be added to the plating solution, for example, at a concentration of up to about 2500 ppm.
於電鍍時，添加劑係大致消耗於基板表面。因此，電 鍍系統大致包含一補充機制，架構以補充消耗於電鍍製程 中之添加劑，使得一相當恒定濃度之添加劑可以維持於電 鐘溶液中。然而，已知於各種添加劑之擴散速率的差可能 造成相較於特性之底部，在高深寬比特性的頂部，有一變 化的特定添加劑的濃度，藉以在特性的頂部對特性的底 部，設立不同之電鍍速率。例如，抑制劑可以具較大分子， 其可以較加速劑擴散為慢，因此，相較於加速劑，有較少 之抑制劑被吸收至高深寬比特性的底面上。因此，特性的 底部可以較特性的頂部有一較快的電鍍速率，因此，增加 特性的填充速率。因此，想要於電鍍溶液中有適當組成之 添加劑，以完成高深寬比特性的無孔隙填充。During electroplating, additives are generally consumed on the substrate surface. Therefore, the electroplating system roughly includes a supplement mechanism, which is structured to supplement the additives consumed in the electroplating process, so that a fairly constant concentration of the additives can be maintained in the clock solution. However, it is known that the difference in the diffusion rate of various additives may result in a change in the concentration of a specific additive at the top of a high aspect ratio characteristic compared to the bottom of the characteristic, thereby establishing a difference between the top of the characteristic and the bottom of the characteristic. Plating rate. For example, inhibitors can have larger molecules, which can diffuse more slowly than accelerators. Therefore, less inhibitors are absorbed onto the bottom surface of high aspect ratio characteristics than accelerators. Therefore, the bottom of the feature can have a faster plating rate than the top of the feature, and therefore, the fill rate of the feature is increased. Therefore, it is desirable to have additives with appropriate composition in the plating solution to complete the non-void filling with high aspect ratio characteristics.
C 為了同時電鍍銅及錫，本發明之實施例想出加入錫離 子至上述銅電鍍溶液中。錫離子的來源包含例如 SnS04、 SnCl2、或其他含錫化合物，其可接受一銅電化學電鍍溶 液者。於電鍍溶液中之錫離子的濃度係於約 0.1M至約 0.9M之間，而於電鍍溶液中之銅離子的濃度係於約0.2Μ 至約0 · 8Μ之間。於本發明之另一態樣中，於電鍍溶液中 之銅濃度可以於0.4Μ至約0.8Μ之間。使用銅錫溶液， 以於銅錫電鍍製程中，施加至基板的電鍍電流密度係於約 16 200305943 5mA/cm2至約6〇mA/cm2之間，例如，於一定電流密度。C In order to electroplate copper and tin simultaneously, an embodiment of the present invention contemplates adding tin ions to the above-mentioned copper electroplating solution. The source of tin ions includes, for example, SnS04, SnCl2, or other tin-containing compounds, which can accept a copper electrochemical plating solution. The concentration of tin ions in the plating solution is between about 0.1M to about 0.9M, and the concentration of copper ions in the plating solution is between about 0.2M to about 0.8M. In another aspect of the present invention, the copper concentration in the plating solution may be between 0.4M and about 0.8M. Using a copper-tin solution, the current density of the plating current applied to the substrate during the copper-tin electroplating process is between about 16 200305943 5 mA / cm2 to about 60 mA / cm2, for example, at a certain current density.
或者，電鐘電流密度也可以於整個銅錫沉積製程中加 以變化，即於電鍍製程中，電流密度步階上升或下降，或 交替於高及低電流密度之間。例如，電流密度係被計算以 在填充一特性的啟始階段中，促成銅錫沉積，然後，當特 性被界面處，略墊以銅錫合金時，電流密度被改變以促成 更多銅大沉積。另外，於銅錫電沉積製程中’支撐基板 的基板支撐件係以約5RPM至約40RPM轉速旋轉，同時， 銅錫電鍛 >谷液流入電鏟槽中之流量係例如於約〇 · 5 G P Μ至 約6.5 GPM之間。本發明之實施例想出電鍍槽能提供大致 怪定流體動力，使得於基板的電鍍表面之電鍍溶液的流速 恆定。此作用以維持銅及錫離子的新鮮供應於電鍍表面， 這對於同時電鍍操作係重要的，因為一離子可以大致較另 一離子為快栝蝎，並造成於合金層中之不均勻（空間非均 質合金）。Alternatively, the clock current density can be changed throughout the copper-tin deposition process, that is, during the electroplating process, the current density step increases or decreases, or alternates between high and low current densities. For example, the current density is calculated to promote copper-tin deposition during the initial stage of filling a characteristic, and then, when the characteristic is interfaced with a copper-tin alloy, the current density is changed to promote more large copper deposition. . In addition, the substrate supporting member that supports the substrate in the copper-tin electrodeposition process is rotated at a rotation speed of about 5 RPM to about 40 RPM, and at the same time, the flow rate of the copper-tin electro-forging > valley liquid flowing into the shovel tank is, for example, about 0.5 GP M to about 6.5 GPM. An embodiment of the present invention contemplates that the plating bath can provide approximately strange fluid power so that the flow rate of the plating solution on the plating surface of the substrate is constant. This action is to maintain the fresh supply of copper and tin ions to the electroplated surface, which is important for simultaneous electroplating operations, because one ion can be roughly faster than the other ion and cause unevenness in the alloy layer (non-spatial Homogeneous alloy).
C 一旦沉積岣質鋼錫合金層，該層可以被回火。回火製 程可肖b促成晶粒大小決定、於合金中之晶粒分佈、及合金 之結晶結構。本發明之實施例想出一回火處理，其可以實 施以回火均質鋼錫合金膜，其中，回火製程包含將膜曝露 至例如於約2〇0°C至約400°C間之溫度。銅錫膜的曝光/回 火時間可以於約5分至約1小時，這係取決於想要結構及 製程可用之熱預算而定。所得實質均質銅錫層將大致具有 至多約2重量％的錫濃度。更明確地說，本發明之均質銅 錫合金將具有〇·2重量％至約1重量％間之錫濃度，或例 17 200305943 如於約0.2重量％至於0 · 6重量°/〇之錫濃度。 第4、5 a及5b圖大致例示於電鍍操作 電鍍時，施加至基板的電流密度及於電鍍操 速間之關係例示圖。第4圖更明確地說，例 錫合金沉積圖，其中，於電鍍溶液中之基板 保持為 20RPM，於電鍍溶液中之銅濃度變 及約44g/L之間，及於電鍍溶液中之錫濃度 變至約20g/L，其係被計算以產生具有低於 合金。第5a及5b圖例示本發明之電鍍製程 用於電鍍溶液中之錫及銅之變化濃度及對於 樣品濃度架構，增加之基板旋轉速度。於第 示之每一濃度區域包含一銅濃度，其係遠高 之錫濃度。第6、7及8圖例示本發明實施4 /面積）對電流密度之例示圖表。第6圖為針 段。第 7圖例示幾個例示應用至電鍍製程 度，即錫及銅濃度，於基板旋轉速表示。然 示，用於溶液之銅及錫濃度係被設立以使 中，銅遠大於錫，即由於電鍍溶液中之金屬 於沉積合金中，只有約0.5 %至約1 · 5 °/。錫。 電鍍製程中，於施加至基板的電流密度及基 電阻間之關係，其中，關係係只示出幾個例示 第9圖例示本發明實施例中，於錫濃度及進 電鍍溶液之流率間之關係。第1 0圖例示銅 結晶結構成為於電鍍時之基板轉速之函數。 中，錫濃度與 作時之基板轉 示本發明之銅 的旋轉速度被 化於約 28g/L .被由5g/L改 1. 5 %錫之銅錫 的例示圖，使 溶液中之每一 5a及5b圖所 於電鍍溶液中 之Rs(m歐姆 對一回火後階 之電鍍溶液濃 而，如先前例 得於所得合金 濃度的結果’ 第8圖例示於 板每單位面積 錫及銅濃度。 入電鍍槽中之 及銅錫合金之 然而，應注意 18 200305943 的是，於第4至10圖所示之資料代表用於本發明實施例 之實驗資料。 雖然前述針對本發明之實施例，但本發明之其他實施 例可以在不脫離由隨附申請專利範圍所界定之本案基本範 圍下加以想出。 【圖式簡單說明】C Once a hafnium steel tin alloy layer is deposited, this layer can be tempered. The tempering process can contribute to grain size determination, grain distribution in the alloy, and crystal structure of the alloy. An embodiment of the present invention contemplates a tempering process that can be implemented by tempering a homogeneous steel-tin alloy film, wherein the tempering process includes exposing the film to a temperature between, for example, about 200 ° C to about 400 ° C. . The exposure / tempering time of the copper-tin film can be from about 5 minutes to about 1 hour, depending on the desired structure and the available thermal budget of the process. The resulting substantially homogeneous copper-tin layer will have a tin concentration of up to about 2% by weight. More specifically, the homogeneous copper-tin alloy of the present invention will have a tin concentration between 0.2% and about 1% by weight, or Example 17 200305943 as a tin concentration between about 0.2% by weight and 0.6% by weight. . Figures 4, 5a, and 5b are roughly illustrative examples of the relationship between the current density applied to the substrate and the plating speed during plating. FIG. 4 is more specific. For example, the tin alloy deposition map, in which the substrate in the plating solution is maintained at 20 RPM, the copper concentration in the plating solution changes to about 44 g / L, and the tin concentration in the plating solution Changed to about 20 g / L, which was calculated to produce a lower-than-alloy. Figures 5a and 5b illustrate the plating process of the present invention for varying concentrations of tin and copper in a plating solution and, for a sample concentration framework, an increased substrate rotation speed. Each concentration region shown includes a copper concentration, which is a much higher tin concentration. Figures 6, 7 and 8 illustrate exemplary graphs of the current implementation (4 / area) versus current density. Figure 6 shows the needle segment. Fig. 7 illustrates several examples of application to the plating process, namely the concentration of tin and copper, expressed at the substrate rotation speed. However, the concentration of copper and tin used in the solution is set so that copper is much larger than tin, that is, because the metal in the plating solution is only about 0.5% to about 1.5 ° / in the deposited alloy. tin. In the electroplating process, the relationship between the current density applied to the substrate and the base resistance is shown. Among them, only a few examples are shown. Figure 9 illustrates the relationship between the tin concentration and the flow rate into the plating solution in the embodiment of the present invention. relationship. Figure 10 illustrates the copper crystal structure as a function of the substrate rotation speed during electroplating. In the tin concentration and substrate, the rotation speed of the copper of the present invention is reduced to about 28g / L. An example of copper tin that was changed from 5g / L to 1.5% tin, so that each of the solutions Figure 5a and 5b show the concentration of Rs in the plating solution (m ohm vs. the concentration of the plating solution after the tempering step, and the results obtained from the alloy concentration obtained in the previous example). Figure 8 illustrates the tin and copper concentration per unit area of the board. However, it should be noted that 18 200305943, the data shown in Figures 4 to 10 represent the experimental data used in the embodiment of the present invention. Although the foregoing is directed to the embodiment of the present invention, However, other embodiments of the present invention can be conceived without departing from the basic scope of the present invention, which is defined by the scope of the accompanying patent application.
第1圖為本發明之例示堰型電鍍槽。 第2圖為本發明之面朝下型電鍍槽。 第3圖為用以個別沉積銅及錫之電流對電壓圖表。 第4圖為用於本發明實施例之濃度對電流密度圖表。 第5 a及5b圖為用於本發明實施例之電鍍溶液中之濃度對 基板旋轉速率圖表。 第6圖為本發明實施例之Rs對電流密度之圖表。 第7圖為用於本發明之實施例之Rs對電鍍溶液中之基板 的旋轉速率圖表。FIG. 1 is an exemplary weir-type plating bath of the present invention. Fig. 2 is a face-down type plating tank of the present invention. Figure 3 is a current versus voltage chart used to deposit copper and tin individually. Figure 4 is a graph of concentration versus current density used in the examples of the present invention. Figures 5a and 5b are graphs of concentration versus substrate rotation rate in the plating solution used in the examples of the present invention. FIG. 6 is a graph of Rs versus current density according to an embodiment of the present invention. Fig. 7 is a graph of the rotation rate of Rs against the substrate in the plating solution used in the embodiment of the present invention.
C 第8圖為本發明實施例之Rs對電流密度之圖表。 第9圖為本發明實施例之錫百分比對流入電鍍槽中之電鍍 溶液流速之圖表。 第10圖為均質膜之角方向對計數的圖表。 【元件代表符號簡單說明】 100 電鍍機 112 容器 114 夾具 116 陽極 19 管線 120 接觸環 基板 124 凹槽 銷 128 薄膜 槽 210 頭組件 主體 220 處理組件 收集器 246 内壁 底部 248 外壁 出口 250 夾具組件 頭組件架 254 安裝柱 懸臂 257 - 25 8 致動 基板夾具 266 接觸環 真空環C FIG. 8 is a graph of Rs versus current density according to an embodiment of the present invention. Fig. 9 is a graph of the percentage of tin versus the flow rate of the plating solution flowing into the plating tank according to the embodiment of the present invention. Figure 10 is a graph of the angular direction of the homogeneous film versus counting. [Simple description of component representative symbols] 100 plating machine 112 container 114 fixture 116 anode 19 pipeline 120 contact ring substrate 124 groove pin 128 film slot 210 head assembly main body 220 processing assembly collector 246 inner wall bottom 248 outer wall outlet 250 clamp assembly head assembly rack 254 Mounting column cantilever 257-25 8 Actuating the substrate holder 266 Contact ring Vacuum ring
Γ 20Γ 20
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| US37051202P | 2002-04-03 | 2002-04-03 |
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| TW092106694A TW200305943A (en) | 2002-04-03 | 2003-03-25 | Homogeneous copper-tin alloy plating for enhancement of electro-migration resistance in interconnects |
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| US (1) | US20030188974A1 (en) |
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| WO (1) | WO2003085713A1 (en) |
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| TWI382479B (en) * | 2008-10-24 | 2013-01-11 | Wei Hua Lu | Manufacturing method and structure of copper-tin core shell conductive particles |
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- 2003-01-24 WO PCT/US2003/002224 patent/WO2003085713A1/en not_active Application Discontinuation
- 2003-01-24 US US10/351,227 patent/US20030188974A1/en not_active Abandoned
- 2003-03-25 TW TW092106694A patent/TW200305943A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI382479B (en) * | 2008-10-24 | 2013-01-11 | Wei Hua Lu | Manufacturing method and structure of copper-tin core shell conductive particles |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030188974A1 (en) | 2003-10-09 |
| WO2003085713A1 (en) | 2003-10-16 |
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