EP3768880A1 - Procédé d'électrodéposition de cobalt - Google Patents

Procédé d'électrodéposition de cobalt

Info

Publication number
EP3768880A1
EP3768880A1 EP19710697.4A EP19710697A EP3768880A1 EP 3768880 A1 EP3768880 A1 EP 3768880A1 EP 19710697 A EP19710697 A EP 19710697A EP 3768880 A1 EP3768880 A1 EP 3768880A1
Authority
EP
European Patent Office
Prior art keywords
cobalt
acid
cavities
electrolyte
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19710697.4A
Other languages
German (de)
English (en)
Inventor
Vincent Mevellec
Dominique Suhr
Mikailou Thiam
Louis CAILLARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aveni SA
Original Assignee
Aveni SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR1852386A external-priority patent/FR3079242B1/fr
Application filed by Aveni SA filed Critical Aveni SA
Publication of EP3768880A1 publication Critical patent/EP3768880A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D5/02—Electroplating of selected surface areas
    • 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
    • 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
    • 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
    • H01L21/70—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
    • 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
    • H01L21/70—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
    • H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating

Definitions

  • polymer is intended to mean a compound comprising at least two repeating units in its chemical formula.
  • An electrodeposition process which can be carried out using the electrolyte of the invention follows a conformal filling mode, so that the organic additives used in large amounts in the bottom-up filling processes of the prior art and which generate contaminations are not necessary.
  • continuous filling is intended to mean a mass of cobalt free of voids.
  • holes or voids of material can be observed in a cobalt deposit between the walls of the patterns and the cobalt deposit ("sidewall voids").
  • Voids located at equal distance from the walls of the patterns can also be observed in the form of holes or lines ("seams").
  • These voids can be observed and quantified by transmission or scanning electron microscopy, by making cross sections of the deposits.
  • the continuous deposit of the invention preferably has an average void percentage of less than 10% by volume, preferably less than or equal to 5% by volume.
  • the measurement of the void percentage inside the structures to be filled can be carried out by electron microscopy at a magnification between 50 000 and 350 000.
  • filling is intended to mean a filling mode in which the cobalt deposit grows at the same speed at the bottom and on the walls of the hollow patterns. This filling mode is in contrast to filling from the bottom to the top (termed “bottom-up”) in which the speed of deposition of the cobalt is faster at the bottom of the cavities.
  • Figure 3 is a scanning electron microscopy image of cavities filled according to an electrodeposition process of the prior art (comparative example 3).
  • carboxymethylcellulose nonylphenolpolyglycol ether, polyethylene glycol dimethyl ether, octanediol bis(polyalkylene glycol ether), octanol polyalkylene glycol ether, polyglycolic ester of oleic acid, poly(ethylene glycol- propylene glycol), polyethylene glycol, polyethyleneimine, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polypropylene glycol, polyvinyl alcohol, polyglycolic ester of stearic acid, polyglycolic ether of stearyl alcohol, butyl alcohol/ethylene oxide/propylene oxide copolymers, 2-mercapto-5- benzimidazolesulfonic acid, 2-mercaptobenzimidazole.
  • the electrolyte comprises less than 500 ppm of a buffer compound (having at least 1 pKa) capable of preventing pH variations of the electrolyte during the polarization step of an electrodeposition process.
  • concentration of the buffer compound in the electrolyte is preferably less than 400 ppm, 300 ppm or even 250 ppm.
  • the pH of the electrolyte can be readjusted, if necessary, for isolated additions of an acid, such as hydrochloric acid for example.
  • the invention also relates to an electrochemical process for filling cavities, said process comprising:
  • the process of the invention is a conformal process as opposed to the "bottom-up” or “super conformal” processes of the prior art.
  • the cobalt deposit grows at the same speed at the bottom and on the walls of the hollow patterns to be filled. This filling mode is in contrast to the other processes of the prior art in which the speed of deposition of the cobalt is faster at the bottom of the cavities than on the walls of the cavities.
  • the through-vias and the interconnections can be made according to the Damascene or Dual-Damascene process known to those skilled in the art, comprising a succession of steps comprising: - the etching of the patterns in or through the silicon wafer in a main axis perpendicular to the surface of the wafer in order to obtain patterns with a vertical profile forming hollows; - the depositing of an insulating dielectric layer generally consisting of silicon oxide; - the depositing of a layer of a material that serves to prevent the migration of the cobalt in the silicon; - the optional depositing of a thin metallic layer, called seed layer; - the filling of the patterns by electrodeposition of cobalt; and - the removal of the excess cobalt by polishing.
  • a silicon substrate which has been etched according to the desired patterns and subsequently covered with a layer of silicon oxide and then with a metallic layer which may be a seed layer of a metal, a barrier layer to the diffusion of the cobalt, a liner or a combination of at least two of the above.
  • the metallic layer may have a thickness of between 1 nm and 10 nm, for example between 2 nm and 5 nm, and may comprise for example a single layer or several superimposed layers of various materials.
  • the intensity of the polarization used in the electrical step preferably ranges from 2 mA/cm 2 to 20 mA/cm 2 , whereas it generally ranges from 0.2 mA/cm 2 to 1 mA/cm 2 in the prior art processes in which an alkaline electrolyte is used.
  • the electrical step comprises a first step of polarization of the cathode in ramp mode with a current which goes preferably from 0 mA/cm 2 to 15 mA/cm 2 , preferably from 0 mA/cm 2 to 10 mA/cm 2 , followed by a step in galvanostatic mode by applying a current ranging from 10 mA/cm 2 to 20 mA/cm 2 , preferably ranging from 8 mA/cm 2 to 12 mA/cm 2 .
  • This electrical step can be used in particular when the electrolyte has a pH of between 2.0 and 2.5.
  • the cathode was polarized in galvano-pulsed mode in a current range of from 30 mA (or 3.8 mA/cm 2 ) to 150 mA (or
  • Annealing at 500°C under reducing gas H 2 at 4% in N 2 , called forming gas is carried out for 10 minutes.
  • the equipment is identical to that of example 1.
  • the cathode was polarized in galvanodynamic ramp mode wherein the current changes proportionally with the time from a value greater than or equal to 0 mA to reach a maximum value of 110 mA (or 13.75 mA/cm 2 ).
  • the current changes from 0 mA to 80 mA (or 10 mA/cm 2 ) with a rate of 1.33 mA/sec.
  • This step was performed with a rotation of 50 rpm for 60 seconds.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (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 And Plating Baths Therefor (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'interconnexions de cobalt et un électrolyte qui permet sa mise en oeuvre. L'électrolyte qui a un pH inférieur à 4,0 comprend des ions cobalt, des ions chlorure et au plus deux additifs organiques de faible poids moléculaire. L'un de ces additifs peut être un acide alpha-hydroxy carboxylique ou un composé ayant une valeur pKa allant de 1,8 à 3,5.
EP19710697.4A 2018-03-20 2019-03-15 Procédé d'électrodéposition de cobalt Pending EP3768880A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR1852386A FR3079242B1 (fr) 2018-03-20 2018-03-20 Procede d'electrodeposition de cobalt
FR1855300A FR3079241A1 (fr) 2018-03-20 2018-06-15 Procede d'electrodeposition de cobalt
US201962789554P 2019-01-08 2019-01-08
PCT/EP2019/056593 WO2019179897A1 (fr) 2018-03-20 2019-03-15 Procédé d'électrodéposition de cobalt

Publications (1)

Publication Number Publication Date
EP3768880A1 true EP3768880A1 (fr) 2021-01-27

Family

ID=65763472

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19710697.4A Pending EP3768880A1 (fr) 2018-03-20 2019-03-15 Procédé d'électrodéposition de cobalt

Country Status (4)

Country Link
EP (1) EP3768880A1 (fr)
CN (1) CN111771016B (fr)
TW (1) TWI804593B (fr)
WO (1) WO2019179897A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11230778B2 (en) 2019-12-13 2022-01-25 Macdermid Enthone Inc. Cobalt chemistry for smooth topology
FR3119848A1 (fr) 2021-02-18 2022-08-19 Aveni Electrolyte et Procédé d’électrodéposition de cobalt
CN115058741A (zh) * 2022-06-30 2022-09-16 金川集团股份有限公司 一种电积钴生产用添加剂

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905776A (en) * 1973-07-05 1975-09-16 Nico Magnetics Inc Method of making a thin, ferro-magnetic memory layer and article made thereby
JPS60190588A (ja) * 1984-03-12 1985-09-28 Toyo Kohan Co Ltd 亜鉛または亜鉛合金めつき鋼板の黒色処理方法
JPS62109991A (ja) * 1985-07-29 1987-05-21 C Uyemura & Co Ltd 電気めつき液
US4904353A (en) * 1988-08-31 1990-02-27 Martin Marietta Corporation Optically black cobalt surface
JP5558675B2 (ja) * 2007-04-03 2014-07-23 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． 金属メッキ組成物
US20110253545A1 (en) * 2010-04-19 2011-10-20 International Business Machines Corporation Method of direct electrodeposition on semiconductors
US9496145B2 (en) * 2014-03-19 2016-11-15 Applied Materials, Inc. Electrochemical plating methods
US9828687B2 (en) * 2014-05-30 2017-11-28 Applied Materials, Inc. Method for electrochemically depositing metal on a reactive metal film
US9758896B2 (en) * 2015-02-12 2017-09-12 Applied Materials, Inc. Forming cobalt interconnections on a substrate
US9777386B2 (en) * 2015-03-19 2017-10-03 Lam Research Corporation Chemistry additives and process for cobalt film electrodeposition
EP3885475A1 (fr) * 2016-07-18 2021-09-29 Basf Se Composition pour dépôt de cobalt comprenant un additif pour remplissage d'éléments submicroniques sans vide

Also Published As

Publication number Publication date
CN111771016B (zh) 2023-05-23
WO2019179897A1 (fr) 2019-09-26
CN111771016A (zh) 2020-10-13
TW201940746A (zh) 2019-10-16
TWI804593B (zh) 2023-06-11

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