TW202045778A - Electrodeposition of a cobalt or copper alloy, and use in microelectronics - Google Patents
Electrodeposition of a cobalt or copper alloy, and use in microelectronics Download PDFInfo
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- TW202045778A TW202045778A TW109103941A TW109103941A TW202045778A TW 202045778 A TW202045778 A TW 202045778A TW 109103941 A TW109103941 A TW 109103941A TW 109103941 A TW109103941 A TW 109103941A TW 202045778 A TW202045778 A TW 202045778A
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- Prior art keywords
- metal
- cobalt
- electrolyte
- acid
- copper
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- 239000010941 cobalt Substances 0.000 title claims abstract description 126
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910000531 Co alloy Inorganic materials 0.000 title description 11
- 229910000881 Cu alloy Inorganic materials 0.000 title description 7
- 238000004070 electrodeposition Methods 0.000 title 1
- 238000004377 microelectronic Methods 0.000 title 1
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 116
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000010949 copper Substances 0.000 claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 239000003792 electrolyte Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000006259 organic additive Substances 0.000 claims abstract description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 90
- 239000002184 metal Substances 0.000 claims description 90
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 42
- 239000011701 zinc Substances 0.000 claims description 42
- 150000002500 ions Chemical class 0.000 claims description 39
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- 238000000151 deposition Methods 0.000 claims description 24
- 238000009713 electroplating Methods 0.000 claims description 24
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- 238000000137 annealing Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
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- 230000010287 polarization Effects 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
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- 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 claims description 8
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960001138 acetylsalicylic acid Drugs 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 17
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 7
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- 230000008569 process Effects 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 2
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- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 4
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- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- XSUMSESCSPMNPN-UHFFFAOYSA-N propane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=NC=C1.CCCS(O)(=O)=O XSUMSESCSPMNPN-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- 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
- H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- 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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- 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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76897—Formation of self-aligned vias or contact plugs, i.e. involving a lithographically uncritical step
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- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
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- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
- H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
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Abstract
Description
本發明係關於一種電解質及其用於在導電表面上電鍍第一金屬及第二金屬之合金的用途,該第一金屬選自鈷、銅及其混合物,該第二金屬選自錳、鋅及其混合物。本發明同樣係關於一種採用此電解質且可用於產生積體電路中之電鈷或銅互連件的製造方法。本發明最後係關於一種包含與第二金屬之層接觸的第一金屬之層的裝置。The present invention relates to an electrolyte and its use for electroplating an alloy of a first metal and a second metal on a conductive surface. The first metal is selected from cobalt, copper and mixtures thereof, and the second metal is selected from manganese, zinc and Its mixture. The present invention also relates to a manufacturing method that uses this electrolyte and can be used to produce electrical cobalt or copper interconnects in integrated circuits. The invention finally relates to a device comprising a layer of a first metal in contact with a layer of a second metal.
用於用鈷填充互連件之習知方法採用含有鈷鹽及眾多有機添加劑之電解質,該等有機添加劑包括具有互補功能之抑制劑及加速劑,以供獲得稱為自下而上填充之物。為獲得良好品質之鈷塊,更特定言之不具有材料空隙,通常需要合併此等添加劑。抑制劑藉由吸收至鈷表面上或藉由與鈷離子錯合來控制鈷在空腔之開口處及在包圍空腔的基板之平坦表面上之沈積。因此,此化合物可為具有高分子質量之分子,諸如不能在空腔內部擴散之聚合物或錯合鈷離子之試劑。就其本身而言,加速劑擴散至空腔之底部,且其之存在在具有較大深度之空腔中為更加必需的。其允許增加鈷在空腔之底部及亦在其壁上的沈積速率。將經由自下而上機制進行之填充方法與稱為「保形(conformal)」或「連續(continuous)」之填充方法進行對比,其中鈷沈積物在中空圖案之底部處及壁上以相同速率生長。The conventional method for filling interconnects with cobalt uses an electrolyte containing cobalt salts and numerous organic additives. The organic additives include inhibitors and accelerators with complementary functions to obtain what is called bottom-up filling . In order to obtain good quality cobalt blocks, more specifically without material voids, it is usually necessary to incorporate these additives. The inhibitor controls the deposition of cobalt at the opening of the cavity and on the flat surface of the substrate surrounding the cavity by absorption on the cobalt surface or by complexing with cobalt ions. Therefore, the compound can be a molecule with high molecular weight, such as a polymer that cannot diffuse inside the cavity or a reagent that complexes cobalt ions. For its part, the accelerator diffuses to the bottom of the cavity, and its presence in a cavity with a greater depth is more necessary. It allows to increase the deposition rate of cobalt at the bottom of the cavity and also on its walls. Comparing the filling method by bottom-up mechanism with the filling method called "conformal" or "continuous", in which the cobalt deposits at the bottom of the hollow pattern and on the wall at the same rate Grow.
此等電鍍浴及其用途具有大量缺陷,該等缺陷最終限制所製造之電子裝置之良好操作且使該等電子裝置對於太昂貴而不能製造。原因在於該等缺陷產生被所需之有機添加劑污染之鈷互連件,從而限制鈷中填充孔之形成。此外,由此等化學品獲得之填充速率太慢且不與工業規模生產相容。These electroplating baths and their uses have numerous defects, which ultimately limit the good operation of the manufactured electronic devices and make them too expensive to manufacture. The reason is that these defects produce cobalt interconnects contaminated by the required organic additives, thereby limiting the formation of filled holes in the cobalt. In addition, the filling rate obtained with such chemicals is too slow and not compatible with industrial scale production.
專利申請案US 2015/0179579描述了出於製造MOSFET電晶體之光柵之目的用於增強在互連件中、更特定言之在經混合鈷/介電基板上的鈷之黏著力的錳之用途。然而,在所描述之方法中,錳及鈷在兩個順次、獨立的材料沈積步驟期間沈積:以氣相化學沈積錳之步驟,隨後為電鍍鈷之步驟。Patent application US 2015/0179579 describes the use of manganese for the purpose of manufacturing gratings of MOSFET transistors for enhancing the adhesion of cobalt in interconnects, more specifically on mixed cobalt/dielectric substrates . However, in the described method, manganese and cobalt are deposited during two sequential, independent material deposition steps: a step of chemical vapor deposition of manganese, followed by a step of electroplating cobalt.
因此仍需要提供電解浴,該等電解浴產生具有經增強效能之鈷沈積物,亦即該等鈷沈積物具有極低雜質含量,該等沈積物之形成速率足夠高以有利的製造電子裝置且/或允許減小基於例如二氧化矽之絕緣基板與鈷之間的諸如氮化鉭的鈷擴散障壁材料層之厚度或甚至避免沈積該鈷擴散障壁材料層。Therefore, it is still necessary to provide electrolytic baths that produce cobalt deposits with enhanced performance, that is, the cobalt deposits have extremely low impurity content, and the formation rate of the deposits is high enough to facilitate the manufacture of electronic devices and /Or it is allowed to reduce the thickness of the cobalt diffusion barrier material layer such as tantalum nitride between the insulating substrate based on, for example, silicon dioxide and the cobalt or even avoid the deposition of the cobalt diffusion barrier material layer.
本發明人已發現,含有鈷II離子及選自錳II離子及鋅II離子之金屬離子的pH在1.8與4.0之間的溶液允許實現此目標。The inventors have found that a solution containing cobalt II ions and metal ions selected from manganese II ions and zinc II ions with a pH between 1.8 and 4.0 allows this goal to be achieved.
從未提議在保形電鍍方法中尤其使用α-羥基羧酸在小於4之pH下沈積鈷合金的可能性,因此使本發明之結果更出人意料。除此之外,從未提出在沈積鈷之前在不需要化學或物理沈積步驟之情況下形成基於錳或基於鋅之薄層的可能性。The possibility of using α-hydroxycarboxylic acid to deposit cobalt alloys at a pH of less than 4 in the conformal electroplating method has never been proposed, thus making the results of the present invention more unexpected. In addition, the possibility of forming a manganese-based or zinc-based thin layer without requiring chemical or physical deposition steps before cobalt deposition has never been proposed.
本發明人已發現,用銅II離子取代鈷II離子達成相同結果,使得本發明能夠產生具有經增強效能之銅沈積物,亦即該等銅沈積物具有極低雜質含量,該等銅沈積物之形成速率足夠高以有利的製造電子裝置及/或允許減小基於例如二氧化矽之絕緣基板與銅之間的諸如氮化鉭的鈷擴散障壁材料層之厚度或甚至避免沈積該鈷擴散障壁材料層。The inventors have found that the substitution of copper II ions for cobalt II ions achieves the same result, so that the present invention can produce copper deposits with enhanced performance, that is, the copper deposits have extremely low impurity content, and the copper deposits The formation rate is high enough to facilitate the manufacture of electronic devices and/or allow to reduce the thickness of the cobalt diffusion barrier material layer such as tantalum nitride between the insulating substrate based on, for example, silicon dioxide and copper or even avoid the deposition of the cobalt diffusion barrier Material layer.
因此,本發明係關於一種用於電鍍第一金屬及第二金屬之合金的電解質,該第一金屬選自鈷、銅及其混合物,該第二金屬選自錳、鋅及其混合物,其特徵在於該電解質為水溶液,該水溶液包含: -鈷II離子或銅II離子,其呈1 g/L至5 g/L之質量濃度, -氯離子,其呈1 g/L至10 g/L之質量濃度, -金屬離子,其選自錳II離子及鋅II離子,該等金屬離子呈使得鈷II離子或銅II離子之質量濃度與金屬離子之質量濃度之間的比率為1/10至25/1的質量濃度, -有機酸或無機酸,其呈足以獲得該電解質之pH在1.8與4.0之間的量,及 -僅一種或至多兩種有機添加劑,其不為聚合物,其中該有機添加劑、該兩種有機添加劑中之一者或該兩種有機添加劑在存在於組合物中時可為該有機酸,且其中該有機添加劑之濃度或該兩種有機添加劑之濃度之總和在5 mg/L與200 mg/L之間。Therefore, the present invention relates to an electrolyte for electroplating an alloy of a first metal and a second metal. The first metal is selected from cobalt, copper and their mixtures, and the second metal is selected from manganese, zinc and their mixtures. Because the electrolyte is an aqueous solution, and the aqueous solution contains: -Cobalt II ion or copper II ion, which has a mass concentration of 1 g/L to 5 g/L, -Chloride ion, which has a mass concentration of 1 g/L to 10 g/L, -Metal ions, which are selected from manganese II ions and zinc II ions, these metal ions are such that the ratio between the mass concentration of cobalt II ions or copper II ions and the mass concentration of metal ions is 1/10 to 25/1 Concentration, -Organic acid or inorganic acid, which is in an amount sufficient to obtain the electrolyte with a pH between 1.8 and 4.0, and -Only one or at most two organic additives, which are not polymers, wherein the organic additive, one of the two organic additives, or the two organic additives may be the organic acid when present in the composition, and The concentration of the organic additive or the sum of the concentrations of the two organic additives is between 5 mg/L and 200 mg/L.
鈷II離子(或銅II離子)之質量濃度與金屬離子之質量濃度之間的比率可高於選自由以下組成之群中的值:1/10、1/5、1/3、1/2、1/1、2/1、3/1、5/1、10/1、15/1及20/1。鈷II離子(或銅II離子)之質量濃度與金屬離子之質量濃度之間的比率可低於選自由以下組成之群中的值:1/5、1/3、1/2、1/1、2/1、3/1、5/1、10/1、15/1、20/1及25/1。The ratio between the mass concentration of cobalt II ions (or copper II ions) and the mass concentration of metal ions can be higher than a value selected from the group consisting of: 1/10, 1/5, 1/3, 1/2 , 1/1, 2/1, 3/1, 5/1, 10/1, 15/1 and 20/1. The ratio between the mass concentration of cobalt II ions (or copper II ions) and the mass concentration of metal ions can be lower than a value selected from the group consisting of: 1/5, 1/3, 1/2, 1/1 , 2/1, 3/1, 5/1, 10/1, 15/1, 20/1 and 25/1.
本發明同樣係關於一種用於用鈷或銅填充空腔之方法,該方法包含使用上文電解質保形地沈積合金之第一步驟及使合金退火以得到鈷或銅沈積物之第二步驟。The present invention also relates to a method for filling a cavity with cobalt or copper. The method includes a first step of conformally depositing an alloy using the above electrolyte and a second step of annealing the alloy to obtain a cobalt or copper deposit.
本發明之電解質及方法提供獲得具有高純度之鈷或銅之連續沈積物且在與工業應用相容之製造時間內獲得的途徑。The electrolyte and method of the present invention provide a way to obtain continuous deposits of cobalt or copper with high purity and within a manufacturing time compatible with industrial applications.
鈷或銅沈積物之優點在於其基本上出於三個原因而具有極高純度。The advantage of cobalt or copper deposits is that they are extremely pure for basically three reasons.
在先前技術中實行之目標中之一者為在不穿過導電金屬將填充之中空體的情況下使用特定地在基板之平坦表面上吸收的抑制劑(表面抑制劑)減慢空腔之入口處的金屬沈積。在先前技術中以較大數量使用且需要確保品質填充的此等有機添加劑引起對鈷或銅沈積物之污染。然而,藉助於本發明之電解質所採用之電鍍方法遵循保形且不需要使用此等添加劑的空腔填充方法。One of the goals implemented in the prior art is to use inhibitors (surface inhibitors) that are specifically absorbed on the flat surface of the substrate to slow the entrance of the cavity without passing through the conductive metal to fill the hollow body. Metal deposition. These organic additives, which are used in larger quantities in the prior art and require high-quality filling, cause contamination of cobalt or copper deposits. However, the electroplating method adopted with the electrolyte of the present invention follows a cavity filling method that is conformal and does not require the use of these additives.
因此,本發明之電解質及方法使得能夠藉由限制有機分子之濃度、呈高濃度之緩衝液物質之存在及在電鍍期間氫氧鈷或氫氧化銅之形成而對鈷或銅沈積物之污染有相當多的限制。Therefore, the electrolyte and method of the present invention enable the contamination of cobalt or copper deposits by limiting the concentration of organic molecules, the presence of high-concentration buffer substances, and the formation of cobalt hydroxide or copper hydroxide during electroplating. Quite a lot of restrictions.
此外,本發明之電解質及方法提供獲得具有極低雜質率的具有較佳小於1000 ppm原子同時以較大沈積速率形成之鈷或銅互連件的途徑。In addition, the electrolyte and method of the present invention provide a way to obtain cobalt or copper interconnects with extremely low impurity rates having atoms preferably less than 1000 ppm while being formed at a relatively large deposition rate.
最後,本發明之電解質及方法使得有可能藉由使鈷及錳之合金、鈷及鋅之合金、銅及錳之合金或銅及鋅之合金退火以形成包含錳或鋅之薄層,此合金在單一步驟中藉由電鍍沈積。Finally, the electrolyte and method of the present invention make it possible to form a thin layer containing manganese or zinc by annealing cobalt and manganese alloys, cobalt and zinc alloys, copper and manganese alloys, or copper and zinc alloys. Deposition by electroplating in a single step.
在一個特定實施例中,鈷-錳或銅-錳合金沈積於由金屬材料製成之晶種層之表面上,此層覆蓋絕緣材料。接著對合金進行熱處理,從而允許分離鈷與錳或銅與錳,且一方面產生含有鈷或銅之層,且另一方面產生錳層。在合金之退火期間,分佈於合金內之錳原子遷移至金屬層與絕緣材料之間的界面,以形成插入於金屬層與絕緣材料之間的薄錳層。結果為覆蓋有薄錳層、薄金屬層及鈷或銅之沈積物的絕緣基板之堆疊。退火增強了製造之有利性及包含鈷或銅互連件之電子裝置之可靠性。In a specific embodiment, the cobalt-manganese or copper-manganese alloy is deposited on the surface of a seed layer made of metal material, which layer covers the insulating material. The alloy is then heat treated, allowing the separation of cobalt and manganese or copper and manganese, and on the one hand a layer containing cobalt or copper, and on the other hand a manganese layer. During the annealing of the alloy, the manganese atoms distributed in the alloy migrate to the interface between the metal layer and the insulating material to form a thin manganese layer inserted between the metal layer and the insulating material. The result is a stack of insulating substrates covered with thin manganese layers, thin metal layers, and deposits of cobalt or copper. Annealing enhances the advantages of manufacturing and the reliability of electronic devices containing cobalt or copper interconnects.
最後,在鈷之情況下,本發明之方法允許減小基於二氧化矽之絕緣基板與鈷之間的諸如氮化鉭的鈷擴散障壁材料層之厚度或甚至不沈積該鈷擴散障壁材料層。在銅之情況下獲得相同結果。Finally, in the case of cobalt, the method of the present invention allows to reduce the thickness of the cobalt diffusion barrier material layer such as tantalum nitride between the silicon dioxide-based insulating substrate and the cobalt or even not to deposit the cobalt diffusion barrier material layer. The same result is obtained in the case of copper.
定義 「電解質」係指含有用於電鍍方法中之金屬塗層之前驅物的液體。definition "Electrolyte" refers to a liquid containing a precursor of the metal coating used in the electroplating process.
「連續填充」係指不含空隙之鈷塊或銅塊。在先前技術中,可在圖案之壁與金屬沈積物之間的鈷或銅沈積物中觀測到材料之孔或空隙(「側壁空隙」)。亦存在可觀測的空隙,該等空隙以孔或線(「縫隙」)形式以距圖案壁之相等距離定位。可藉由傳輸或掃描電子顯微法,藉由製得沈積物之橫截面來觀測及量化此等空隙。本發明之連續沈積物較佳地具有小於10體積%,較佳小於或等於5體積%之平均空隙百分比。可藉由電子顯微術以50 000與350 000之間的放大率或藉由TEM來實現待填充的結構內之空隙百分比之量測。"Continuous filling" refers to cobalt or copper blocks without voids. In the prior art, holes or voids in the material ("sidewall voids") can be observed in the cobalt or copper deposits between the walls of the pattern and the metal deposits. There are also observable voids, which are located at equal distances from the pattern wall in the form of holes or lines ("slits"). These voids can be observed and quantified by transmission or scanning electron microscopy, by making a cross-section of the sediment. The continuous deposit of the present invention preferably has an average void percentage less than 10% by volume, preferably less than or equal to 5% by volume. The measurement of the percentage of voids in the structure to be filled can be achieved by electron microscopy with a magnification between 50 000 and 350,000 or by TEM.
空腔之「平均直徑」或「平均寬度」係指在待填充之空腔之開口處量測的尺寸。空腔例如呈楔形通道或圓柱體形式。The "average diameter" or "average width" of the cavity refers to the size measured at the opening of the cavity to be filled. The cavity is for example in the form of a wedge-shaped channel or a cylinder.
「保形填充(conformal filling)」係指其中鈷及錳之合金、鈷及鋅之合金、銅及錳之合金或銅及鋅之合金之沈積物以相同速率在中空圖案之底部處及壁上生長的填充模式。將此填充模式與底部至頂部之填充(「自下而上」填充)進行對比,其中合金之沈積速率在空腔之底部處較高。"Conformal filling" means that the deposits of cobalt and manganese alloy, cobalt and zinc alloy, copper and manganese alloy, or copper and zinc alloy are deposited at the bottom and on the wall of the hollow pattern at the same rate Growing fill pattern. Compare this filling mode with bottom-to-top filling ("bottom-up" filling), where the deposition rate of the alloy is higher at the bottom of the cavity.
本發明係關於一種用於電鍍第一金屬及第二金屬之合金的電解質,該第一金屬選自鈷、銅及其混合物,該第二金屬選自錳、鋅及其混合物,該合金包含選自錳及鋅之金屬,其特徵在於該電解質為水溶液,該水溶液包含 -鈷II或銅II離子,其呈1 g/L至5 g/L之質量濃度, -氯離子,其呈1 g/L至10 g/L之質量濃度, -金屬離子,其選自錳II離子及鋅II離子,該等金屬離子呈使得鈷II離子或銅II離子之質量濃度與金屬離子之質量濃度之間的比率為1/10至10/1的質量濃度, -有機或無機酸,其呈足以獲得pH在1.8與4.0之間的量,及 -僅一種或至多兩種有機添加劑,其不為聚合物,其中兩種添加劑中之一者可為酸;當此酸為有機酸時,添加劑之濃度或兩種添加劑之濃度之總和在5 mg/L與200 mg/L之間。The present invention relates to an electrolyte for electroplating an alloy of a first metal and a second metal, the first metal is selected from cobalt, copper and mixtures thereof, and the second metal is selected from manganese, zinc and their mixtures, and the alloy contains selected Metal from manganese and zinc, characterized in that the electrolyte is an aqueous solution containing -Cobalt II or Copper II ions, which have a mass concentration of 1 g/L to 5 g/L, -Chloride ion, which has a mass concentration of 1 g/L to 10 g/L, -Metal ions, which are selected from manganese II ions and zinc II ions, the metal ions are such that the ratio of the mass concentration of cobalt II ions or copper II ions to the mass concentration of metal ions is 1/10 to 10/1 Concentration, -Organic or inorganic acid in an amount sufficient to obtain a pH between 1.8 and 4.0, and -Only one or at most two organic additives, which are not polymers, and one of the two additives can be an acid; when the acid is an organic acid, the concentration of the additive or the sum of the concentration of the two additives is 5 mg /L and 200 mg/L.
有機添加劑較佳地為不含硫之添加劑,其中該等有機添加劑中之至少一者或甚至兩者較佳地為α-羥基羧酸。電解質較佳地包含單一有機添加劑。The organic additives are preferably non-sulfur additives, wherein at least one or even both of the organic additives are preferably α-hydroxycarboxylic acids. The electrolyte preferably contains a single organic additive.
一或多種有機添加劑較佳具有小於250 g/mol,較佳小於200 g/mol且大於50 g/mol,更佳大於100 g/mol之分子量。The one or more organic additives preferably have a molecular weight of less than 250 g/mol, preferably less than 200 g/mol and greater than 50 g/mol, more preferably greater than 100 g/mol.
添加劑之濃度或兩種添加劑之濃度之總和較佳地在5 mg/L與200 mg/L之間。在此實施例中,添加劑可各自為不含硫之α-羥基羧酸。The concentration of the additive or the sum of the concentrations of the two additives is preferably between 5 mg/L and 200 mg/L. In this embodiment, the additives may each be a sulfur-free α-hydroxycarboxylic acid.
有機添加劑中之至少一者可選自檸檬酸、酒石酸、蘋果酸、杏仁酸、順丁烯二酸、反丁烯二酸、甘油酸、乳清酸、丙二酸、L-丙胺酸、乙醯水楊酸及水楊酸。At least one of the organic additives can be selected from citric acid, tartaric acid, malic acid, mandelic acid, maleic acid, fumaric acid, glyceric acid, orotic acid, malonic acid, L-alanine, ethyl acetate Salicylic acid and salicylic acid.
鈷II或銅II離子之質量濃度可為1 g/L至5 g/L,例如2 g/L至3 g/L。氯離子之質量濃度可為1 g/L至10 g/L。The mass concentration of cobalt II or copper II ions can be 1 g/L to 5 g/L, for example, 2 g/L to 3 g/L. The mass concentration of chloride ions can range from 1 g/L to 10 g/L.
高酸性pH下之鈷或銅離子之相對高濃度相對於具有鹼性或弱酸性pH及較低鈷或銅離子濃度的先前技術之電解浴具有若干優點。The relatively high concentration of cobalt or copper ions at a highly acidic pH has several advantages over prior art electrolytic baths with alkaline or weakly acidic pH and lower concentrations of cobalt or copper ions.
原因在於本發明人發現不需要在大於4之pH下操作以便限制沈積物中之鈷或銅之腐蝕。藉由增加鈷離子或銅離子之濃度且藉由降低pH之值,似乎有可能藉由實質上增加存在於水溶液中之離子之濃度來使金屬鈷或銅穩定。本發明人因此已觀測到大於先前技術之沈積速率的沈積速率,且亦觀測到在退火步驟之後沈積物中的鈷或銅之晶粒之較大大小,通常地大於20 nm。The reason is that the inventor found that it is not necessary to operate at a pH greater than 4 in order to limit the corrosion of cobalt or copper in the deposit. By increasing the concentration of cobalt ions or copper ions and by lowering the pH value, it seems possible to stabilize metallic cobalt or copper by substantially increasing the concentration of ions present in the aqueous solution. The inventors have therefore observed a deposition rate that is greater than the deposition rate of the prior art, and also observed a larger size of cobalt or copper crystal grains in the deposit after the annealing step, usually greater than 20 nm.
金屬離子選自錳II離子及鋅II離子。其質量濃度使得鈷離子或銅離子之質量濃度與金屬離子之質量濃度之間的比率為1/10至25/1或1/10至10/1。The metal ion is selected from manganese II ion and zinc II ion. Its mass concentration is such that the ratio between the mass concentration of cobalt ion or copper ion and the mass concentration of metal ion is 1/10 to 25/1 or 1/10 to 10/1.
可藉由將i)氯化鈷或氯化銅或其水合物中之一者(諸如氯化鈷六水合物)及ii)氯化錳或氯化鋅溶解於水中來提供氯離子。Chloride ions can be provided by dissolving one of i) cobalt chloride or copper chloride or a hydrate thereof (such as cobalt chloride hexahydrate) and ii) manganese chloride or zinc chloride in water.
組合物較佳地不藉由溶解包含硫酸鹽之鹽來獲得,此引起鈷或銅沈積物之硫污染,為非所需現象。The composition is preferably not obtained by dissolving a salt containing sulfate, which causes sulfur contamination of cobalt or copper deposits, which is an undesirable phenomenon.
一或多種有機添加劑較佳地不含硫,且較佳地選自α-羥基羧酸,諸如化合物檸檬酸、酒石酸、乙醇酸、乳酸、蘋果酸、杏仁酸、順丁烯二酸、草酸及2-羥基丁酸。The one or more organic additives are preferably free of sulfur and are preferably selected from α-hydroxycarboxylic acids such as the compounds citric acid, tartaric acid, glycolic acid, lactic acid, malic acid, mandelic acid, maleic acid, oxalic acid and 2-hydroxybutyric acid.
電解質可包含除α-羥基羧酸以外之有機添加劑,諸如甘胺酸或乙二胺。電解質可屬於任何種類,其限制條件為其不產生自下而上的填充效果。本發明之電解質實際上較佳地不含表面抑制劑聚合物,諸如聚乙二醇、聚丙二醇、聚乙烯吡咯啶酮或聚乙二亞胺。The electrolyte may contain organic additives other than α-hydroxycarboxylic acid, such as glycine or ethylenediamine. The electrolyte can belong to any kind, and its limitation is that it does not produce a bottom-up filling effect. The electrolyte of the present invention preferably does not contain surface inhibitor polymers, such as polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone or polyethylenediimine.
鈷II或銅II離子以及金屬離子(錳II或鋅II)有利地呈游離形式,意謂其不與一或多種有機添加劑錯合,更特定言之當pH小於3時,不論在不存在極化之情況下或在極化導電表面期間。Cobalt II or copper II ions and metal ions (manganese II or zinc II) are advantageously in free form, meaning that they are not complexed with one or more organic additives, more specifically when the pH is less than 3, regardless of the presence or absence of extremes. In the case of polarization or during polarization of conductive surfaces.
不具有實質數量之鈷或銅錯合物或具有有機分子之其他金屬錯合物存在眾多優點:其使得能夠減少金屬沈積物之有機污染,因為浴液中之有機分子之濃度可能極低;其同樣使得能夠在鈷或銅沈積於結構中的時間段期間避免易於使溶液不穩定之pH的任何不可控變化。此外,鈷或銅離子不藉由錯合物穩定,且可更容易還原,且因此鈷或銅之沈積速率更大。最後,鈷或銅離子之極高濃度保護空腔之導電表面免遭腐蝕。此效果測定基板何時覆蓋有具有極低厚度之層(晶種層),該層在電鍍期間充當導電表面。There are many advantages of cobalt or copper complexes or other metal complexes with organic molecules that do not have a substantial amount: it makes it possible to reduce the organic pollution of metal deposits, because the concentration of organic molecules in the bath may be extremely low; It also makes it possible to avoid any uncontrollable changes in pH that tend to destabilize the solution during the period of time when cobalt or copper is deposited in the structure. In addition, cobalt or copper ions are not stabilized by complex compounds, and can be more easily reduced, and therefore the deposition rate of cobalt or copper is greater. Finally, the extremely high concentration of cobalt or copper ions protects the conductive surface of the cavity from corrosion. This effect determines when the substrate is covered with a layer of very low thickness (seed layer), which acts as a conductive surface during electroplating.
本發明之電解質有利地包含單獨或以組合形式採取的以下特徵中之一者: -其不包含圖案之底部處的鈷或銅生長之加速劑, -電解質不含有能夠藉由特定地在鈷上或在銅上吸收而減慢空腔之開口處的基板之平坦部分上的鈷或銅之生長的有機抑制劑分子,該鈷或該銅在電鍍期間沈積在此位點處, -其不包含產生自下而上填充機制的添加劑之組合,特定言之抑制劑及加速劑之組合,或抑制劑、加速劑及調平劑之組合, -其不包含聚合物,其中聚合物意謂具有至少四個重複單元之分子, -其不包含含硫之化合物。The electrolyte of the present invention advantageously contains one of the following characteristics taken alone or in combination: -It does not contain cobalt or copper growth accelerators at the bottom of the pattern, -The electrolyte does not contain organic inhibitor molecules that can slow down the growth of cobalt or copper on the flat part of the substrate at the opening of the cavity by specifically absorbing it on cobalt or copper. The cobalt or copper is electroplated During the deposition at this site, -It does not contain a combination of additives that produce a bottom-up filling mechanism, specifically a combination of inhibitors and accelerators, or a combination of inhibitors, accelerators and leveling agents, -It does not contain a polymer, where polymer means a molecule with at least four repeating units, -It does not contain sulfur-containing compounds.
表面抑制劑包括以下化合物:羧甲基纖維素、壬基苯酚聚二醇醚、聚乙二醇二甲醚、辛二醇雙(聚伸烷二醇醚)、辛醇聚伸烷二醇醚、油酸之聚二醇酯、聚乙二醇-丙二醇、聚乙二醇、聚乙二亞胺、聚乙二醇二甲醚、聚氧丙二醇、聚丙二醇、聚乙烯醇、硬脂酸之聚二醇酯、十八烷醇之聚二醇醚、丁醇-環氧乙烷-環氧丙烷共聚物、2-巰基-5-苯并咪唑磺酸、2-巰基苯并咪唑。Surface inhibitors include the following compounds: carboxymethyl cellulose, nonylphenol polyglycol ether, polyethylene glycol dimethyl ether, octanediol bis(polyalkylene glycol ether), octanol polyalkylene glycol ether , Polyglycol ester of oleic acid, polyethylene glycol-propylene glycol, polyethylene glycol, polyethylene diimide, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polypropylene glycol, polyvinyl alcohol, stearic acid Polyglycol ester, polyglycol ether of stearyl alcohol, butanol-ethylene oxide-propylene oxide copolymer, 2-mercapto-5-benzimidazole sulfonic acid, 2-mercaptobenzimidazole.
加速劑通常為包含硫原子之化合物,例如N,N-二甲基二硫基胺基甲酸之3-磺丙基酯;3-巰丙基磺酸、3-硫基-1-丙烷磺酸酯之3-磺丙基酯;二硫碳酸鄰乙酯s-酯與3-巰基-1-丙磺酸、雙磺丙基二硫化物之鉀鹽之酯;3-(苯并噻唑基-s-硫基)丙基磺酸、吡啶鎓丙基磺酸甜菜鹼、1-鈉3-巰基丙烷-1-磺酸酯之鈉鹽;N,N-二甲基二硫基胺基甲酸之3-磺乙基酯;3-巰乙基丙基磺酸之3-磺乙基酯;3-巰乙基磺酸、吡啶鎓乙基磺酸甜菜鹼或硫脲之鈉鹽。Accelerators are usually compounds containing sulfur atoms, such as 3-sulfopropyl ester of N,N-dimethyldithiocarbamic acid; 3-mercaptopropyl sulfonic acid, 3-thio-1-propane sulfonic acid 3-sulfopropyl ester of ester; 2-ethyl dithiocarbonate s-ester with 3-mercapto-1-propanesulfonic acid, and the potassium salt of bissulfopropyl disulfide; 3-(benzothiazolyl- s-thio) propyl sulfonic acid, pyridinium propyl sulfonate betaine, sodium salt of 1-sodium 3-mercaptopropane-1-sulfonate; N,N-dimethyldithiocarbamic acid 3-sulfoethyl ester; 3-sulfoethyl ester of 3-mercaptoethyl propyl sulfonic acid; sodium salt of 3-mercaptoethyl sulfonic acid, pyridinium ethyl sulfonate betaine or thiourea.
在第一實施例中,電解質之pH較佳地在1.8與4.0之間。在一個特定實施例中,pH在2.0與3.5之間或在2.0與2.4之間。In the first embodiment, the pH of the electrolyte is preferably between 1.8 and 4.0. In a particular embodiment, the pH is between 2.0 and 3.5 or between 2.0 and 2.4.
組合物之pH可視情況用熟習此項技術者已知之鹼或酸調節。酸可為有機或無機的。較佳考慮使用強無機酸,諸如氫氯酸。The pH of the composition may be adjusted with alkali or acid known to those skilled in the art as appropriate. The acid can be organic or inorganic. It is preferable to consider the use of strong mineral acids, such as hydrochloric acid.
儘管原則上不存在對溶劑之性質的限制(其限制條件為該溶劑充分溶解溶液之活性物種且不干擾電鍍),但該溶劑將較佳為水。根據一個實施例,溶劑主要包含水(按體積計)。Although in principle there is no restriction on the nature of the solvent (the restriction is that the solvent fully dissolves the active species in the solution and does not interfere with electroplating), the solvent will preferably be water. According to one embodiment, the solvent mainly contains water (by volume).
根據一個變型,本發明之電解質具有1.8與4.0之間,例如2.0與4.0之間的pH且在水溶液中包含鈷II或銅II離子、錳II或鋅II之金屬離子、氯離子及5 mg/L與200 mg/L之間的一或多種化合物,該一或多種化合物具有1.8至3.5,較佳2.0至3.5且更佳2.2至3.0之pKa。According to a variant, the electrolyte of the present invention has a pH between 1.8 and 4.0, for example between 2.0 and 4.0, and contains cobalt II or copper II ions, manganese II or zinc II metal ions, chloride ions, and 5 mg/ One or more compounds between L and 200 mg/L, the one or more compounds having a pKa of 1.8 to 3.5, preferably 2.0 to 3.5, and more preferably 2.2 to 3.0.
化合物較佳地具有小於250 g/mol,較佳小於200 g/mol且大於50 g/mol、較佳大於100 g/mol之分子量。The compound preferably has a molecular weight of less than 250 g/mol, preferably less than 200 g/mol and greater than 50 g/mol, preferably greater than 100 g/mol.
在某些情況下,pKa值為1.8至3.5之化合物可與用於第一實施例中的有機添加劑中之至少一者相同。更特定言之,該化合物可選自檸檬酸、酒石酸、蘋果酸、順丁烯二酸及杏仁酸。In some cases, the compound having a pKa value of 1.8 to 3.5 may be the same as at least one of the organic additives used in the first embodiment. More specifically, the compound can be selected from citric acid, tartaric acid, malic acid, maleic acid and mandelic acid.
該化合物亦可選自化合物反丁烯二酸(pKa = 3.03)、甘油酸(pKa = 3.52)、乳清酸(pKa = 2.83)、丙二酸(pKa = 2.85)、L-丙胺酸(pKa = 2.34)、磷酸(pKa = 2.15)、乙醯水楊酸(pKa = 3.5)及水楊酸(pKa = 2.98)。The compound can also be selected from the compounds fumaric acid (pKa = 3.03), glyceric acid (pKa = 3.52), orotic acid (pKa = 2.83), malonic acid (pKa = 2.85), L-alanine (pKa = 2.34), phosphoric acid (pKa = 2.15), acetylsalicylic acid (pKa = 3.5) and salicylic acid (pKa = 2.98).
在施加極低電流密度及對具有鈷具有特異性之抑制劑化合物時,鈷填充之先前技術方法採用鹼性電解質,例如pH大於4,且因此溝槽內部之pH在整個填充步驟中保持大於4,因此引起在所得鈷沈積物中大量形成氫氧化鈷,其中該氫氧化鈷減小鈷互連件之導電性且降低積體電路的效能位準。When applying a very low current density and an inhibitor compound specific for cobalt, the prior art method of cobalt filling uses alkaline electrolyte, for example, the pH is greater than 4, and therefore the pH inside the trench remains greater than 4 throughout the filling step , Thus causing a large amount of cobalt hydroxide to be formed in the resulting cobalt deposit, wherein the cobalt hydroxide reduces the conductivity of the cobalt interconnect and lowers the performance level of the integrated circuit.
本發明之電解質及本發明之方法特定地旨在藉由顯著限制氫氧化鈷之形成以使得其僅以痕量存在於已沈積之鈷中來解決此問題。此問題之解決方案涉及使用pH在1.8與4.0之間(例如在2.0與4.0之間)的電解質,向該電解質添加添加劑,該添加劑較佳地展現諸如以下之特徵中之至少一者或甚至全部: -在其表面上的溝槽內之局部緩衝能力,其允許在整個基板極化時間中將電解質之pH維持處於大於1.8或2.0且小於3.5且較佳小於2.5的值處, -低分子量,使得添加劑能夠擴散至在開口處具有低平均直徑或具有低平均寬度之結構中,及 -在電解質中之極低濃度,使得在極化開始之前存在於電解質中的添加劑之量幾乎全部擴散至結構之空腔中,且使得添加劑具有局部緩衝能力。The electrolyte of the present invention and the method of the present invention specifically aim to solve this problem by significantly limiting the formation of cobalt hydroxide so that it exists only in trace amounts in the deposited cobalt. The solution to this problem involves using an electrolyte with a pH between 1.8 and 4.0 (for example, between 2.0 and 4.0), and adding an additive to the electrolyte, which preferably exhibits at least one or even all of the following characteristics: : -Local buffering capacity in the grooves on its surface, which allows the pH of the electrolyte to be maintained at a value greater than 1.8 or 2.0 and less than 3.5 and preferably less than 2.5 throughout the substrate polarization time, -Low molecular weight, which enables additives to diffuse into structures with low average diameter or low average width at the opening, and -Very low concentration in the electrolyte, so that almost all the amount of additives present in the electrolyte before polarization starts to diffuse into the cavity of the structure, and make the additives have a local buffering capacity.
包含此類型之添加劑的電解質能夠例如僅僅在結構之空腔中且不在基板之平坦表面處將pH之增加選擇性限制至小於4.0,較佳小於3.0之值且更佳地選擇性限制至2.0與2.5之間的值。因此添加劑能夠藉由局部發揮其效果(亦即僅僅在空腔中)來有利地滿足緩衝液之功能。有機添加劑或pKa為1.8至3.5或2.0至3.5之化合物能夠充當局部緩衝液,僅在空腔中觀測到其效果。An electrolyte containing this type of additive can, for example, only in the cavity of the structure and not at the flat surface of the substrate, restrict the increase in pH to less than 4.0, preferably less than 3.0 and more preferably to 2.0 and Value between 2.5. Therefore, the additive can advantageously fulfill the function of the buffer by exerting its effect locally (that is, only in the cavity). Organic additives or compounds with a pKa of 1.8 to 3.5 or 2.0 to 3.5 can act as a local buffer, and their effect is only observed in the cavity.
根據第一實施例,第一金屬為鈷且第二金屬為錳。根據第二實施例,第一金屬為鈷且第二金屬為鋅。根據第三實施例,第一金屬為銅且第二金屬為錳。根據第四實施例,第一金屬為銅且第二金屬為鋅。According to the first embodiment, the first metal is cobalt and the second metal is manganese. According to the second embodiment, the first metal is cobalt and the second metal is zinc. According to the third embodiment, the first metal is copper and the second metal is manganese. According to the fourth embodiment, the first metal is copper and the second metal is zinc.
舉例而言,電解質為水溶液,該水溶液包含: -鈷II離子,其呈1 g/L至5 g/L之質量濃度, -氯離子,其呈1 g/L至5 g/L之質量濃度, -鋅II離子,其呈使得鈷II離子之質量濃度與鋅II離子之質量濃度之間的比率為15/1至20/1的質量濃度, -無機酸,其呈足以獲得pH在2.0與2.4之間的量,及 -僅一種有機添加劑,該有機添加劑之濃度在10 mg/L與20 mg/L之間。For example, the electrolyte is an aqueous solution, and the aqueous solution includes: -Cobalt II ion, which has a mass concentration of 1 g/L to 5 g/L, -Chloride ion, which has a mass concentration of 1 g/L to 5 g/L, -Zinc II ion, which has a mass concentration such that the ratio between the mass concentration of cobalt II ion and the mass concentration of zinc II ion is 15/1 to 20/1, -Inorganic acid in an amount sufficient to obtain a pH between 2.0 and 2.4, and -Only one organic additive, the concentration of the organic additive is between 10 mg/L and 20 mg/L.
在此實例中,有機添加劑可為酒石酸。In this example, the organic additive may be tartaric acid.
本發明同樣係關於一種用於填充空腔之電化學方法,該等空腔在開口處具有15 nm與100 nm之間的平均寬度或平均直徑及50 nm與250 nm之間的深度,該方法包含: -使該等空腔之導電表面與如上文描述之電解質接觸的步驟, -使該導電表面極化持續足以藉由沈積第一金屬及第二金屬之合金進行該等空腔之保形及完全填充之一段時間的步驟,該第一金屬選自鈷、銅及其混合物,該第二金屬選自錳、鋅及其混合物,及 -使在極化步驟結束時所獲得的合金之沈積物退火的步驟,該退火在允許金屬遷移以形成第一層及第二層之溫度下進行,該第一層主要含有金屬,該層具有0.5 nm與2 nm之間的厚度,該第二層基本上含有鈷或銅。The present invention also relates to an electrochemical method for filling cavities, the cavities having an average width or diameter between 15 nm and 100 nm and a depth between 50 nm and 250 nm at the opening. contain: -The step of bringing the conductive surfaces of the cavities into contact with the electrolyte as described above, -The step of making the conductive surface polarized for a period of time sufficient to perform conformal and complete filling of the cavities by depositing an alloy of the first metal and the second metal, the first metal being selected from cobalt, copper and mixtures thereof , The second metal is selected from manganese, zinc and mixtures thereof, and -A step of annealing the deposit of the alloy obtained at the end of the polarization step, the annealing is performed at a temperature that allows the migration of the metal to form the first layer and the second layer, the first layer mainly containing metal, and the layer having With a thickness between 0.5 nm and 2 nm, the second layer essentially contains cobalt or copper.
退火步驟亦能夠改良鈷或銅之結晶度且抑制沈積物中之任何材料空隙。The annealing step can also improve the crystallinity of cobalt or copper and suppress any material voids in the deposit.
在一個特定實施例中,導電表面為厚度為1至10奈米之金屬晶種層之第一表面,該晶種層具有與包含二氧化矽之介電材料接觸的第二表面。金屬晶種層可包含選自由以下組成之群的金屬:鈷、銅、鎢、鈦、鉭、釕、鎳、氮化鈦及氮化鉭。In a specific embodiment, the conductive surface is a first surface of a metal seed layer with a thickness of 1 to 10 nanometers, and the seed layer has a second surface in contact with a dielectric material containing silicon dioxide. The metal seed layer may include a metal selected from the group consisting of cobalt, copper, tungsten, titanium, tantalum, ruthenium, nickel, titanium nitride, and tantalum nitride.
在一個特定實施例中,晶種層為鈷晶種層。本發明之方法可藉由上文所描述之電解質中之一者實施,該等電解質包含一或兩種非聚合有機添加劑或包含pKa為1.8至3.5,較佳2.0至3.5且更佳2.2至3.0的5 mg/L與200 mg/L之間的一或多種化合物。In a specific embodiment, the seed layer is a cobalt seed layer. The method of the present invention can be implemented by one of the electrolytes described above, which electrolytes contain one or two non-polymeric organic additives or contain a pKa of 1.8 to 3.5, preferably 2.0 to 3.5 and more preferably 2.2 to 3.0 One or more compounds between 5 mg/L and 200 mg/L.
在實施本發明之方法之填充步驟期間的整個時間中,視所使用之電解質類型而定,空腔內部之pH有利地保持小於3.5或甚至小於3.0。During the entire time during the filling step of the method of the present invention, depending on the type of electrolyte used, the pH inside the cavity is advantageously kept less than 3.5 or even less than 3.0.
可在實施金屬鑲嵌法或雙金屬鑲嵌法之情形中設計空腔。可尤其藉由實施以下步驟來獲得空腔: -將結構蝕刻至矽基板中的步驟, -在結構之矽表面上形成氧化矽層以得到氧化矽表面的步驟, -在該氧化矽層上沈積金屬層以便得到空腔導電表面的步驟。The cavity can be designed in the case of implementing the damascene method or the dual damascene method. The cavity can be obtained especially by implementing the following steps: -The step of etching the structure into the silicon substrate, -The step of forming a silicon oxide layer on the silicon surface of the structure to obtain a silicon oxide surface, -A step of depositing a metal layer on the silicon oxide layer to obtain a conductive surface of the cavity.
金屬層較佳為厚度在1 nm與10 nm之間的金屬晶種層。金屬層較佳地沈積於氧化矽層上,該氧化矽層與矽接觸。金屬可包含至少一種選自由以下組成之群的化合物:鈷、銅、鎢、鈦、鉭、釕、鎳、氮化鈦及氮化鉭。金屬層較佳地包含鈷層。在第一實施例中,金屬層由鈷層構成。在第二實施例中,金屬層包含鈷層及具有鈷擴散障壁特性之材料層。金屬層可藉由熟習此項技術者已知之任何適當方法沈積。The metal layer is preferably a metal seed layer with a thickness between 1 nm and 10 nm. The metal layer is preferably deposited on the silicon oxide layer, which is in contact with the silicon. The metal may include at least one compound selected from the group consisting of cobalt, copper, tungsten, titanium, tantalum, ruthenium, nickel, titanium nitride, and tantalum nitride. The metal layer preferably includes a cobalt layer. In the first embodiment, the metal layer is composed of a cobalt layer. In the second embodiment, the metal layer includes a cobalt layer and a material layer with cobalt diffusion barrier characteristics. The metal layer can be deposited by any suitable method known to those skilled in the art.
相較於先前技術之「自下而上」或「超級保形(super-conformal)」方法,本發明之方法為「保形」方法。在本發明之保形填充方法中,鈷合金或銅合金沈積物在待填充之中空圖案之底部處及壁上以相同速率生長。將此填充模式與先前技術之其他方法進行對比,其中鈷合金之沈積速率在空腔之底部處比在空腔之壁上更高。Compared with the prior art "bottom-up" or "super-conformal" method, the method of the present invention is a "conformal" method. In the conformal filling method of the present invention, the cobalt alloy or copper alloy deposits grow at the same rate at the bottom and on the walls of the hollow pattern to be filled. This filling mode is compared with other methods of the prior art, in which the deposition rate of the cobalt alloy is higher at the bottom of the cavity than on the wall of the cavity.
在電鍍步驟結束時沈積的合金之錳含量或鋅含量較佳地在0.5原子%與10原子%之間,例如在1.0原子%與5.0原子%之間或在1.5原子%與2.5原子%之間。The manganese content or zinc content of the alloy deposited at the end of the electroplating step is preferably between 0.5 atomic% and 10 atomic %, for example between 1.0 atomic% and 5.0 atomic% or between 1.5 atomic% and 2.5 atomic% .
用於電步驟中的極化強度較佳為2 mA/cm2 至50 mA/cm2 ,而極化強度在使用鹼性電解質之先前技術方法中通常為0.2 mA/cm2 至1 mA/cm2 。The polarization intensity used in the electrical step is preferably 2 mA/cm 2 to 50 mA/cm 2 , and the polarization intensity is usually 0.2 mA/cm 2 to 1 mA/cm in the prior art method using alkaline electrolyte 2 .
本發明之方法之電步驟可包含僅一個或若干個極化步驟,其中熟習此項技術者將知道如何基於其常識選擇變量。The electrical steps of the method of the present invention may include only one or several polarization steps, wherein those familiar with the art will know how to select variables based on their common sense.
電步驟可使用至少一個選自由以下組成之群的極化模式進行:斜升模式(ramp mode)、恆電流模式(galvano-static mode)及脈衝電流模式(galvano-pulsed mode)。The electrical step can be performed using at least one polarization mode selected from the group consisting of: ramp mode, galvano-static mode, and galvano-pulsed mode.
電步驟可因此包含在脈衝電流模式中進行電鍍的至少一個步驟及在恆電流模式中進行電鍍的至少一個步驟,在恆電流模式中進行之電鍍步驟較佳地於在脈衝電流模式中進行之電鍍步驟之後。The electrical step may therefore include at least one step of electroplating in the pulse current mode and at least one step of electroplating in the constant current mode. The electroplating step performed in the constant current mode is preferably better than the electroplating performed in the pulse current mode After the steps.
舉例而言,電步驟包含在脈衝電流模式中極化陰極的第一步驟,從而使電流自3 mA/cm2 至20 mA/cm2 、例如自12 mA/cm2 至16 mA/cm2 交流較佳地介於5 ms與50 ms之間的一段時間(Ton )且零極化較佳地介於50 ms與150 ms之間的一段時間(Toff )。For example, the electrical step includes the first step of polarizing the cathode in the pulse current mode, so that the current is from 3 mA/cm 2 to 20 mA/cm 2 , such as from 12 mA/cm 2 to 16 mA/cm 2 AC It is preferably a period of time between 5 ms and 50 ms (T on ) and the zero polarization is preferably a period of time between 50 ms and 150 ms (T off ).
在此第一步驟中,基板可在極化之前或在極化之後與電解質接觸。與空腔接觸較佳地在施加電壓之前執行,以便限制對與電解質接觸之金屬層的腐蝕。In this first step, the substrate may be in contact with the electrolyte before polarization or after polarization. The contact with the cavity is preferably performed before the voltage is applied in order to limit corrosion of the metal layer in contact with the electrolyte.
在第二步驟中,陰極可在恆電流模式中極化,其中電流的範圍介於3 mA/cm2 至50 mA/cm2 。兩個步驟較佳地具有實質上相同的持續時間。In the second step, the cathode can be polarized in a constant current mode, where the current range is from 3 mA/cm 2 to 50 mA/cm 2 . The two steps preferably have substantially the same duration.
恆電流模式中之第二步驟自身可包含兩個步驟:第一步驟,其中電流之強度為3 mA/cm2 至8 mA/cm2 ,及第二步驟,其中施加強度為9 mA/cm2 至50 mA/cm2 之電流。The second step in the constant current mode itself can include two steps: the first step, in which the intensity of the current is 3 mA/cm 2 to 8 mA/cm 2 , and the second step, in which the applied intensity is 9 mA/cm 2 Up to 50 mA/cm 2 current.
此電步驟可尤其在電解質之pH在2.5與3.5之間時使用。This electrical step can be used especially when the pH of the electrolyte is between 2.5 and 3.5.
在另一實例中,電步驟包含在斜升模式中極化陰極之第一步驟,其中其之電流較佳為0 mA/cm2 至15 mA/cm2 ,較佳0 mA/cm2 至10 mA/cm2 ,隨後為在恆電流模式中之步驟,其中施加10 mA/cm2 至50 mA/cm2 ,較佳8 mA/cm2 至20 mA/cm2 之電流。此電步驟可尤其在電解質之pH在2.0與2.5之間時使用。In another example, the electrical step includes the first step of polarizing the cathode in the ramp-up mode, where the current is preferably 0 mA/cm 2 to 15 mA/cm 2 , preferably 0 mA/cm 2 to 10 mA/cm 2 , followed by a step in the constant current mode, in which a current of 10 mA/cm 2 to 50 mA/cm 2 , preferably 8 mA/cm 2 to 20 mA/cm 2 is applied. This electrical step can be used especially when the pH of the electrolyte is between 2.0 and 2.5.
電鍍步驟通常在合金沈積物覆蓋基板之平坦表面時停止:在此情況下,沈積物包含空腔內部之材料及覆蓋其中空腔已經挖空的基板之表面的材料。覆蓋表面之合金層之厚度可在50 nm與400 nm之間,且可例如在125 nm與200 nm之間。The electroplating step usually stops when the alloy deposit covers the flat surface of the substrate: in this case, the deposit includes the material inside the cavity and the material covering the surface of the substrate in which the cavity has been hollowed out. The thickness of the alloy layer covering the surface can be between 50 nm and 400 nm, and can be, for example, between 125 nm and 200 nm.
鈷合金或銅合金之沈積速率在0.1 nm/s與3.0 nm/s之間,較佳在1.0 nm/s與3.0 nm/s之間,且更佳在1 nm/s與2.5 nm/s之間。The deposition rate of cobalt alloy or copper alloy is between 0.1 nm/s and 3.0 nm/s, preferably between 1.0 nm/s and 3.0 nm/s, and more preferably between 1 nm/s and 2.5 nm/s between.
本發明之方法包含使如上文所描述之在填充結束時所獲得的合金沈積物退火的步驟。The method of the present invention comprises the step of annealing the alloy deposit obtained at the end of the filling as described above.
此退火熱處理可在50℃與550℃之間的溫度下,較佳在諸如於N2 中呈4%之H2 的還原氣體下執行。This annealing heat treatment can be performed at a temperature between 50°C and 550°C, preferably under a reducing gas such as 4% H 2 in N 2 .
低雜質含量以及極低百分比之空隙的組合提供獲取具有較低電阻率之鈷沈積物或銅沈積物的途徑。The combination of low impurity content and very low percentage of voids provides a way to obtain cobalt deposits or copper deposits with lower resistivity.
在退火步驟期間,存在於合金中之錳或鋅原子朝向導電基板之表面遷移,因此引起兩個層之形成:第一層,其基本上包含鈷或銅;及第二層,其基本上包含錳或鋅。「基本上」包含鈷之層可為包含至多100%鈷及最少量之選自由以下組成之群之鈷的層:95%、96%、97%、98%、99%、99.5%、99.8%及99.9%。「基本上」包含銅之層可為包含至多100%銅及最少量之選自由以下組成之群之銅的層:95%、96%、97%、98%、99%、99.5%、99.8%及99.9%。「基本上」包含錳之層可為包含至多100%錳及最少量之選自由以下組成之群之錳的層:95%、96%、97%、98%、99%、99.5%、99.8%及99.9%。「基本上」包含鋅之層可為包含至多100%鋅及最少量之選自由以下組成之群之鋅的層:95%、96%、97%、98%、99%、99.5%、99.8%及99.9%。此等百分比為原子%,且可藉由熟習此項技術者已知之任何方法來量測。During the annealing step, the manganese or zinc atoms present in the alloy migrate towards the surface of the conductive substrate, thus causing the formation of two layers: the first layer, which essentially contains cobalt or copper; and the second layer, which essentially contains Manganese or zinc. The "substantially" cobalt-containing layer may be a layer containing up to 100% cobalt and a minimum amount of cobalt selected from the group consisting of 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8% And 99.9%. The "substantially" copper-containing layer may be a layer containing up to 100% copper and a minimum amount of copper selected from the group consisting of: 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8% And 99.9%. The "substantially" manganese-containing layer may be a layer containing up to 100% manganese and a minimum amount of manganese selected from the group consisting of 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8% And 99.9%. The "substantially" zinc-containing layer may be a layer containing up to 100% zinc and a minimum amount of zinc selected from the group consisting of 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8% And 99.9%. These percentages are atomic% and can be measured by any method known to those skilled in the art.
在一個實施例中,導電表面為鈷晶種層之表面,該層覆蓋包含二氧化矽之絕緣基板。在此實施例中,錳或鋅原子在退火步驟期間遷移穿過鈷晶種層以到達第一晶種層與包含二氧化矽之絕緣基板之間的界面。In one embodiment, the conductive surface is the surface of a cobalt seed layer, which covers an insulating substrate containing silicon dioxide. In this embodiment, manganese or zinc atoms migrate through the cobalt seed layer during the annealing step to reach the interface between the first seed layer and the insulating substrate containing silicon dioxide.
藉由本發明之電鍍及退火方法獲得之鈷沈積物或銅沈積物之總雜質含量小於1000 ppm原子,不將錳或鋅視為雜質。雜質主要包括氧,隨後包括碳及氮。總碳及氮含量小於300 ppm。鈷或銅沈積物為有利地連續的。鈷或銅沈積物較佳地具有小於10體積%或表面積%,較佳小於或等於5體積%或表面積%的平均空隙百分比。鈷或銅沈積物之空隙百分比可藉由利用電子顯微術進行觀測來量測,該電子顯微術為熟習此項技術者所已知,該等熟習此項技術者將選擇對於其而言似乎最適當的方法。此等方法中之一者可為使用50 000與350 000之間的放大率之掃描電子顯微法(scanning electron microscopy;SEM)或穿透電子顯微術(transmission electron microscopy;TEM)。可藉由量測在包含經填充空腔之基板之一或多個橫截面上觀測到的空隙表面積來評估空隙體積。當在兩個或更多個橫截面上量測兩個或更多個表面積時,將計算此等表面積之平均值以便評估空隙體積。The total impurity content of the cobalt deposit or the copper deposit obtained by the electroplating and annealing method of the present invention is less than 1000 ppm atoms, and manganese or zinc is not considered as an impurity. Impurities mainly include oxygen, followed by carbon and nitrogen. The total carbon and nitrogen content is less than 300 ppm. The cobalt or copper deposits are advantageously continuous. The cobalt or copper deposit preferably has an average void percentage less than 10% by volume or surface area%, preferably less than or equal to 5% by volume or surface area%. The percentage of voids in cobalt or copper deposits can be measured by observation using electron microscopy. The electron microscopy is known to those familiar with the technology, and those familiar with the technology will choose to It seems the most appropriate method. One of these methods can be scanning electron microscopy (SEM) or transmission electron microscopy (TEM) using magnification between 50 000 and 350,000. The void volume can be evaluated by measuring the void surface area observed on one or more cross-sections of the substrate containing the filled cavity. When two or more surface areas are measured on two or more cross sections, the average value of these surface areas will be calculated in order to estimate the void volume.
基本上包含錳或鋅之層較佳為平均厚度為0.5 nm至2 nm之連續層。「連續」意謂層覆蓋介電基板之整個表面而後者沒有傳透。相對於平均厚度,層之厚度較佳地變化+/- 10%。The layer substantially containing manganese or zinc is preferably a continuous layer with an average thickness of 0.5 nm to 2 nm. "Continuous" means that the layer covers the entire surface of the dielectric substrate without the latter being transparent. Relative to the average thickness, the thickness of the layer preferably varies by +/- 10%.
方法可包含藉由還原電漿進行處理之基本步驟,以便還原存在於基板之表面處的天然金屬氧化物。電漿亦作用於溝槽之表面上,由此能夠改善導電表面與合金之間的界面之品質。後續電鍍步驟較佳地緊接在電漿處理之後進行,以便最小化自然氧化物之再形成。The method may include the basic step of treatment by reducing plasma in order to reduce the natural metal oxide present at the surface of the substrate. The plasma also acts on the surface of the trench, thereby improving the quality of the interface between the conductive surface and the alloy. The subsequent electroplating step is preferably performed immediately after the plasma treatment in order to minimize the reformation of natural oxides.
本發明之方法發現特定言之在半導體裝置之製造中、在生產諸如沿表面延伸的溝槽或連接不同整合位準之通孔的導電金屬互連件期間的應用。The method of the present invention finds application particularly in the manufacture of semiconductor devices, during the production of conductive metal interconnects such as trenches extending along the surface or connecting vias of different integration levels.
最後,本發明係關於一種配備有金屬互連件的半導體裝置,該金屬互連件包含介電材料層,該介電材料層由基本上包含錳或鋅之層覆蓋且與該層接觸,該層由鈷或銅層覆蓋。Finally, the present invention relates to a semiconductor device equipped with a metal interconnection, the metal interconnection comprising a layer of dielectric material covered by a layer substantially containing manganese or zinc and in contact with the layer, the The layer is covered by a cobalt or copper layer.
可將金屬晶種層插入於基本上包含錳或鋅之層與鈷或銅層之間,且可與此兩個層中之每一者接觸。A metal seed layer can be inserted between the layer substantially comprising manganese or zinc and the cobalt or copper layer, and can be in contact with each of these two layers.
互連件基本上由鈷或銅構成且可藉由上文所描述之方法獲得。在此情況下,該等互連件對應於填充空腔之鈷或銅沈積物。互連件可具有15 nm與100 nm之間的平均寬度及50 nm與250 nm之間的平均深度。The interconnects are basically composed of cobalt or copper and can be obtained by the methods described above. In this case, the interconnects correspond to cobalt or copper deposits filling the cavity. The interconnect may have an average width between 15 nm and 100 nm and an average depth between 50 nm and 250 nm.
基本上包含錳或鋅之層有利地具有0.5 nm與2 nm之間的厚度且與諸如二氧化矽之介電材料接觸。The layer substantially comprising manganese or zinc advantageously has a thickness between 0.5 nm and 2 nm and is in contact with a dielectric material such as silicon dioxide.
本說明書亦涉及一種形成金屬互連結構的方法,該金屬互連結構包含一種黏著層材料及金屬填充材料,該黏著層材料為錳或鋅,且該金屬填充材料為鈷或銅,其中黏著層由至多兩個步驟形成:無電極沈積包含金屬填充材料及黏著層材料之合金的第一步驟,及使造成黏著層材料與金屬填充材料分離以形成兩個分離區域(黏著層及金屬填充物層)之合金沈積物熱退火的第二步驟。此方法包含:在基板中之介電層中形成開口的步驟,其中開口暴露導電表面;用包含第一金屬及第二金屬之合金無電極填充開口的步驟,該第一金屬為鈷或銅,該第二金屬為錳或鋅;及使合金熱退火的步驟。根據此實施例,方法不包含在用合金無電極填充開口之前形成包含錳之黏著層的步驟。This specification also relates to a method for forming a metal interconnection structure. The metal interconnection structure includes an adhesion layer material and a metal filling material, the adhesion layer material is manganese or zinc, and the metal filling material is cobalt or copper, and the adhesion layer It is formed by at most two steps: the first step of electrodeless deposition of an alloy containing a metal filler material and an adhesive layer material, and separates the adhesive layer material from the metal filler material to form two separate regions (adhesive layer and metal filler layer) ) The second step of thermal annealing of alloy deposits. This method includes: forming an opening in a dielectric layer in a substrate, wherein the opening exposes a conductive surface; and a step of filling the opening with an alloy including a first metal and a second metal, the first metal being cobalt or copper, The second metal is manganese or zinc; and the step of thermally annealing the alloy. According to this embodiment, the method does not include the step of forming an adhesive layer containing manganese before filling the opening with an alloy electrodelessly.
與電解質及方法有關且上文所描述的特徵可在適當時應用於本發明之半導體裝置。The features described above related to the electrolyte and method can be applied to the semiconductor device of the present invention when appropriate.
實例 1 : 在包含鈷晶種層之基板上電鍍來自 pH=2.2 之溶液的鈷及鋅之合金 將鈷及鋅之合金電鍍於包含鈷晶種層之平坦基板上。在存在酒石酸之情況下藉助於含有鈷(II)離子之含氯鹽及鋅(II)離子之含氯鹽的組合物(pH 2.2)進行沈積。 Example 1 : Electroplating an alloy of cobalt and zinc from a solution of pH=2.2 on a substrate containing a cobalt seed layer The alloy of cobalt and zinc was electroplated on a flat substrate containing a cobalt seed layer. In the presence of tartaric acid, the deposition is carried out by means of a composition (pH 2.2) containing a chloride salt of cobalt (II) ion and a chloride salt of zinc (II) ion.
A.- 材料及裝備 : 基板 : 用於此實例中之基板由4×4 cm矽試片組成。矽覆蓋有與3 nm厚之鉭層接觸的氧化矽,該鉭層自身由3 nm厚之鈷層覆蓋且由CVD沈積。基板之經量測電阻率為約168歐姆/平方。 A.- Materials and Equipment: a substrate: a substrate for this example of 4 × 4 cm from the test piece composed of silicon. The silicon is covered with silicon oxide in contact with a 3 nm thick tantalum layer, which is itself covered by a 3 nm thick cobalt layer and deposited by CVD. The measured resistivity of the substrate is about 168 ohm/square.
電鍍溶液 : 此溶液中之Co2+ 濃度為2.35 g/L,獲自CoCl2 (H2 O)6 。Zn2+ 濃度為0.136 g/L,獲自ZnCl2 。酒石酸以15 mg/L存在。藉助於添加氫氯酸將溶液之pH調節至pH=2.2。 Electroplating solution : The Co 2+ concentration in this solution is 2.35 g/L, obtained from CoCl 2 (H 2 O) 6 . The Zn 2+ concentration is 0.136 g/L, obtained from ZnCl 2 . Tartaric acid is present at 15 mg/L. The pH of the solution was adjusted to pH=2.2 by adding hydrochloric acid.
裝備 : 在此實例中,所使用之電解沈積裝備由兩個部分構成:用於容納電鍍溶液之電池,其配備有流體再循環系統以便控制系統之流體動力學;及旋轉電極,其配備有適用於所使用的試片之大小(4 cm × 4 cm)的試樣夾。電解沈積電池由兩個電極構成: -鈷陽極 -矽試片塗佈有上文所描述之層,其構成陰極,參考連接至陽極。 Equipment : In this example, the electrolytic deposition equipment used consists of two parts: a battery for holding the electroplating solution, which is equipped with a fluid recirculation system to control the fluid dynamics of the system; and a rotating electrode, which is equipped with suitable Specimen holder with the size of the specimen used (4 cm × 4 cm). The electrolytic deposition battery consists of two electrodes:-Cobalt anode-The silicon test piece is coated with the layer described above, which constitutes the cathode, which is connected to the anode for reference.
連接件使得能夠與電極電接觸,該等電極藉由電線連接至供應至多20 V或2 A之穩壓器。The connector makes it possible to make electrical contact with the electrodes, which are connected by wires to a potentiostat supplying up to 20 V or 2 A.
B.- 實驗方案 : 基本步驟 : 由於具有高齡或已經不佳地儲存之晶圓,基板通常僅在天然氧化鈷層太大量時需要特殊處理。此儲存通常在氮氣下發生。在此情況下,有必要產生含有氫氣之電漿,其為純氫氣或於氮氣中含有4%氫氣之混合氣體。 B.- Experimental program : Basic steps : Because of the wafers that are old or poorly stored, the substrate usually only needs special treatment when the natural cobalt oxide layer is too large. This storage usually takes place under nitrogen. In this case, it is necessary to generate a plasma containing hydrogen, which is pure hydrogen or a mixed gas containing 4% hydrogen in nitrogen.
電氣方法 : 方法如下執行:在連續電流模式中在50 mA (或11 mA/cm2 )至120 mA (或26 mA/cm2 ) (例如,100 mA (或22.1 mA/cm2 )之電流範圍內極化陰極。使此步驟在60 rpm之旋轉之情況下進行1小時。使電解質在施加電壓之前與基板接觸5秒之時間。合金之沈積速率為3.3 nm/s。在另一實施例中,在脈衝電流模式中在80 mA (或17.6 mA/cm2 )至160 mA (或35.2 mA/cm2 ) (例如,130 mA (或28.6 mA/cm2 ))之電流範圍內極化陰極,其中脈衝持續時間在陰極極化時為5 ms至1000 ms且在兩個陰極脈衝之間的零極化中為5 ms至1000 ms。 Electrical method : The method is performed as follows: in continuous current mode at 50 mA (or 11 mA/cm2 ) To 120 mA (or 26 mA/cm2 ) (E.g. 100 mA (or 22.1 mA/cm2 ) Polarize the cathode within the current range. Allow this step to be performed for 1 hour while rotating at 60 rpm. The electrolyte is brought into contact with the substrate for a period of 5 seconds before applying voltage. The deposition rate of the alloy is 3.3 nm/s. In another embodiment, in the pulse current mode at 80 mA (or 17.6 mA/cm2 ) To 160 mA (or 35.2 mA/cm2 ) (E.g. 130 mA (or 28.6 mA/cm2 )) Polarize the cathode in the current range, where the pulse duration is 5 ms to 1000 ms in cathodic polarization and 5 ms to 1000 ms in zero polarization between two cathode pulses.
退火 : 退火在400℃之溫度下在含氫氛圍(4%氫氣於氮氣中)下進行30分鐘,以便使鋅遷移至SiO2 與鈷之間的界面。 annealing : Annealing is carried out for 30 minutes in a hydrogen-containing atmosphere (4% hydrogen in nitrogen) at a temperature of 400°C to allow the zinc to migrate to SiO2 The interface with cobalt.
C.- 所獲得之結果 : 藉由掃描電子顯微法進行之概況分析展示接近於200 nm之合金厚度。此厚度在退火之後略微減少至190 nm。退火之前的XPS分析展示合金中存在約2原子%之鋅。在一方面,在退火之後,此相同形式之分析展示鋅朝向SiO2 -鈷界面及朝向最外表面兩者的遷移。在另一方面,氧、碳及氮之總污染不超過600 ppm原子。 C.- Results obtained : The profile analysis by scanning electron microscopy showed an alloy thickness close to 200 nm. This thickness is slightly reduced to 190 nm after annealing. XPS analysis before annealing revealed the presence of approximately 2 atomic% zinc in the alloy. In one aspect, after annealing, this analysis shows the same form of zinc toward 2 SiO - migration of both cobalt and the interface toward the outermost surface. On the other hand, the total pollution of oxygen, carbon and nitrogen does not exceed 600 ppm atoms.
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FR1901264A FR3092589A1 (en) | 2019-02-08 | 2019-02-08 | Electroplating of a cobalt alloy and use in microelectronics |
FR1901264 | 2019-02-08 | ||
FR2000297A FR3092590A1 (en) | 2019-02-08 | 2020-01-14 | Electroplating of a cobalt or copper alloy, and use in microelectronics |
FR2000297 | 2020-01-14 |
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TW202045778A true TW202045778A (en) | 2020-12-16 |
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