WO2014030779A1 - Procédé de formation de matière de cuivre formée de façon à avoir une structure nano-bicristalline, et matière de cuivre ainsi obtenue - Google Patents

Procédé de formation de matière de cuivre formée de façon à avoir une structure nano-bicristalline, et matière de cuivre ainsi obtenue Download PDF

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Publication number
WO2014030779A1
WO2014030779A1 PCT/KR2012/006678 KR2012006678W WO2014030779A1 WO 2014030779 A1 WO2014030779 A1 WO 2014030779A1 KR 2012006678 W KR2012006678 W KR 2012006678W WO 2014030779 A1 WO2014030779 A1 WO 2014030779A1
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WO
WIPO (PCT)
Prior art keywords
nano
copper
current
copper material
reverse
Prior art date
Application number
PCT/KR2012/006678
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English (en)
Korean (ko)
Inventor
유봉영
서성호
진상현
Original Assignee
한양대학교 에리카산학협력단
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.)
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Application filed by 한양대학교 에리카산학협력단 filed Critical 한양대학교 에리카산학협력단
Priority to PCT/KR2012/006678 priority Critical patent/WO2014030779A1/fr
Publication of WO2014030779A1 publication Critical patent/WO2014030779A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/241—Reinforcing the conductive pattern characterised by the electroplating method; means therefor, e.g. baths or apparatus

Definitions

  • the present invention relates to a method of manufacturing a copper material having a nanotwinned structure, and more particularly, to a method of forming a copper material having a nanotwinned structure using an electrolytic deposition process.
  • conductive metals are widely used in various fields such as electrical connectors of microelectronic devices and electrical conductors of high magnetic fields.
  • copper and its alloys are one of the widely used nonferrous metals because of their high thermal and electrical conductivity and good corrosion resistance, and are essential materials for electronic devices.
  • Grain refinement is a method of improving the mechanical strength by reducing the size of grains and increasing grain boundaries that prevent dislocations during plastic deformation.
  • the electrical conductivity is higher than that of the copper alloy in that no additional alloying element is added, the electrical conductivity is lower than that of pure copper because the grain boundary scatters electrons.
  • Twin refers to a structure in which two grains are symmetrically positioned with respect to the twin plane, and nano twin refers to a microscopic distance between the twin planes.
  • the movement of dislocations is limited to increase the mechanical strength of the material.
  • the twin plane is a matching interface, It does not become a route. Therefore, it is known that copper with nanotwins formed has a maximum ultimate tensile strength of up to 5 times while maintaining excellent electrical conductivity.
  • magnetron sputtering technology has been used as a method for producing a copper thin film having a nanotwinned structure.
  • Magnetron sputtering equipment is widely used in the semiconductor industry.
  • vacuum is an expensive equipment that requires a lot of activity, it is necessary to study a low-cost method for commercialization.
  • This application deviates from the method of supplying a DC current constantly for electrolytic deposition of a copper thin film, on-time (t on ) for applying a DC current and off time without applying a current.
  • on-time t on
  • t oii By repeatedly applying (off-time, t oii ), a nano-twin copper thin film was produced in which the spacing between twins ranged from several nm to 100 nm and the length of twins ranged from 100 nm to 500 nm.
  • the present invention is to solve the above-mentioned problems of the prior art, and provides a method for reducing the time of the electrolytic deposition process for forming copper formed with nano-twin twin, to facilitate the application to the actual industrial process There is this.
  • a method of forming a bath formed copper material comprising: immersing a positive electrode and a negative electrode in a copper sulfate electrolyte solution; And a pulse current step of applying a forward current to the immersed anode and cathode to grow a nucleus and grains including a nanotwinned structure and a reverse current step of dissolving the nucleus and crystal grains except the nanotwinned structure by applying a reverse current.
  • the solution oxidizes the thin film and exhibits a dissolution effect, thereby dissolving the nuclei and grains generated during the on-time during the off-time.
  • the density of the nano-twinned structure can be increased by adjusting the length of the off-time, but there is a limit in reducing the off-time.
  • the inventors considered a method of enhancing the dissolution effect, which is an important phenomenon occurring in off-time, and a method of shortening the dissolution time by applying a reverse current to enhance the dissolution effect.
  • a method of enhancing the dissolution effect which is an important phenomenon occurring in off-time
  • a method of shortening the dissolution time by applying a reverse current to enhance the dissolution effect was developed.
  • ⁇ contained in the electrolyte has a problem of reducing copper ions to copper oxide to reduce the amount of copper ions in the electrolyte, thereby reducing the effect of the overall electrolytic deposition, it is common to use an electrolyte having a ⁇ of 5 or less. .
  • the forward current has a larger current density than the reverse current.
  • the reverse current applied in the reverse pulse step has a current density in the range of 2 to 30 mA / cm 2 , and the time for applying the reverse current is 0.01 seconds or more and 0.1 seconds or less.
  • the reverse current is applied at a current density lower than 2 mA / cm 2 , small growth nuclei and small grains are not sufficiently dissolved, and the ratio of the nano-twinned structure is reduced, and the reverse current is higher than 30 mA / cm 2.
  • there is a problem of dissolving to the nano-twinned structure due to excessive dissolution effect see Fig. 9). If the reverse current is applied for less than 0.01 seconds, the core and crystal grains, which are not twins, cannot be dissolved, resulting in the effect of increasing the density of the twins. .
  • the forward current applied in the step has a current density of 200 mA / cm or more, and the time for applying the forward current is preferably 0.1 seconds or less.
  • the forward current is applied at a current density lower than 200 mA / cm 2 , the nanotwinned structure is difficult to form because the current density is so low that it is difficult to give a sufficient stress to the electro-deposited copper particles.
  • the time for applying the forward current is longer than 0.1 second, too much copper ions are reduced in one forward pilling step, and thus a depletion layer is formed, and this depletion layer prevents electrolytic deposition.
  • Current density upper limit of the forward current-forward pulse step is not particularly limited, if the current density is too high, and so is too high production costs must select the proper current density, and in view of this, carried out at a current density of 1,500 mA / cm 2 or less Good to do.
  • the lower limit of the time to apply the forward current in the forward pulse step is not particularly limited. However, if the forward fill step is too short, an appropriate time must be selected because the deposition slows down and the overall process time increases and the production speed decreases. In consideration of this, it is preferable to apply a forward current of 0.01 seconds or more.
  • the copper material according to the present invention is characterized in that the nano-twinned structure is formed by the electrolytic deposition process of the above method, the copper material has a spacing between the nano-twinned structure is 15 ⁇ 100nm range It is preferable. If the interval between nanotwinned structures is longer than 100nm, the effect of improving the characteristics by nanotwinned is less, and softening phenomenon of less than 15nm occurs, so high strength cannot be realized.
  • the copper material in which the nano-twinned structure is formed has a true ultimate yield strength of 400 MPa or more, a cross-sectional reduction rate of 45% or more, and a specific resistance of 1.9 ⁇ fficm or less.
  • a maximum true tensile strength of 400 MPa or more and cross-sectional area reduction rate of 45% or more it can be seen that there is a significant improvement in physical properties, and it can be used as wiring material for electronic devices when the specific resistance is 1.9 ⁇ or less.
  • the addition time of applying the reverse current in forming the copper nanostructured copper material by the electrolytic deposition process reduces the formation time compared to the conventional method which did not apply the current. There is an effect that can be greatly shortened.
  • FIG. 1 is a TEM photograph of the surface of the electrolytically deposited copper thin film prepared according to the present embodiment.
  • FIG. 2 is a TEM photograph showing the surface of the electrolytically deposited copper thin film prepared by the method of Comparative Example 1.
  • FIG. 2 is a TEM photograph showing the surface of the electrolytically deposited copper thin film prepared by the method of Comparative Example 1.
  • FIG. 6 is a graph of the time-specific current densities of Examples and Comparative Example 2 for explaining the time reduction mechanism of the Examples.
  • FIG. 7 is a graph comparing deposition rates in the case of forming a copper thin film by three methods.
  • FIG. 8 is a graph showing specific resistance according to reverse pulse current density of a copper thin film manufactured by the manufacturing method of the present embodiment.
  • FIG. 9 is a graph showing the maximum true tensile strength according to the reverse-fill current density of the copper thin film manufactured by the manufacturing method of the present embodiment.
  • a CuS0 4 solution having a pH of 1.0 was prepared as an electrolytic deposition electrolyte.
  • concentrations of Cu 2+ and S0 in the prepared electrolyte were
  • the anode was electrolytically deposited copper
  • the cathode was copper deposited by an evaporator, and immersed in the electrolyte solution so that the distance between the two electrodes was 30 mm.
  • a positive current having a current density of 0.5 A / cm 2 is applied to the positive electrode and the negative electrode immersed in the electrolyte solution.
  • a forward foil step of applying 0.02 seconds and a reverse field step of applying a reverse current having a current density of 4.7 mA / cm 2 for 0.08 seconds were repeatedly performed to electrolytically deposit a copper foil film on the cathode.
  • the electrolyte was continuously stirred and The temperature was kept at 25 ° C.
  • Tensile test results of the electrolytically deposited copper thin film prepared according to the present embodiment showed a maximum ultimate tensile strength of 540 MPa and a cross-sectional area reduction rate of 48%. Indicated.
  • Figure 1 is a ⁇ picture taken of the surface of the electrolytically deposited copper thin film prepared according to the present embodiment, it can be seen that the twin-sized structure of the nano-size is formed.
  • Copper thin films were prepared by electrolytic deposition using a direct current, and mechanical and electrical characteristics were compared.
  • an electrolytic deposition electrolyte was prepared under the same conditions as in Example 1, and the positive electrode and the negative electrode were immersed in the electrolytic solution.
  • the forward current was continuously applied at a current density of 23.8 mA / cm 2 to form a copper thin film, and mechanical and electrical characteristics were measured.
  • the maximum true tensile strength of the copper thin film fabricated by applying only direct current was about 300 MPa, the reduction in cross-sectional area was about 26%, and the specific resistance was about 1.68 ⁇ .
  • Copper thin films were prepared by electrolytic deposition including off-time without direct current, and mechanical and electrical characteristics were compared.
  • an electrolytic deposition electrolyte was prepared under the same conditions as in Example 1, and the positive electrode and the negative electrode were immersed in the electrolyte solution.
  • a copper thin film is formed by repeating a pulse current step of applying a forward current at a current density of 0.5 A / cm 2 for 0.05 seconds and a current off step of not applying a current for 1.0 seconds. The properties were measured.
  • the maximum true tensile strength of the copper thin film prepared by the current off step was about 525 MPa, the cross-sectional area reduction was about 47%, and the specific resistance was about 1.72 ⁇ .
  • Figure 3 is a ⁇ taken the surface of the electrolytically deposited copper thin film prepared by the method of Comparative Example 2 It is a photograph, and it can be seen that a nanosized twinned structure is formed.
  • the copper thin films produced by the three methods are as follows.
  • the time taken to form a copper thin film of the same thickness by the method of the present Example and Comparative Examples 1 and 2 was 2 hours, 3 hours and 6 hours, respectively.
  • the time taken to form the copper thin film by the method of this embodiment is very short, about one third of the time taken to form by the method of Comparative Example 2.
  • the specific resistance of the copper thin film manufactured by the method of Comparative Example 1 is the lowest, and the specific resistance is increased in the order of Example and Comparative Example 2.
  • the specific resistance of the thin film manufactured by the method of this example and Comparative Example 2 can also be used as a wiring material of an electric device. It shows a specific resistance value.
  • the copper thin film formed according to the present embodiment can be used in an electric device.
  • FIG. 5 is a graph showing the maximum true tensile strength of the copper thin film formed by three methods.
  • the maximum true tensile strength was very low.
  • the maximum tensile strength is greatly improved by the nano-twinned structure.
  • the copper thin film formed by the method of the present embodiment compared with the copper thin film formed by the method of Comparative Example 2, although the time required for formation is very short, it can be seen that the maximum true tensile strength is further improved.
  • FIG. 6 is a graph showing the current density by time of Example and Comparative Example 2.
  • FIG. The dissolution effect is shown in the flow time of the reverse pulse current of the embodiment and the off time of Comparative Example 2, as shown in the graph, the time for the dissolution effect is very short in the case of the example can be confirmed that the entire cycle is very fast.
  • 7 is a graph comparing deposition rates in the case of forming a copper thin film by three methods.
  • the deposition rate is faster.
  • the deposition rate is slow because the current density is lower than the current density applied in the forward pulse step of the present embodiment for quality.
  • the deposition rate is the slowest because the current off step is long.
  • the method of the present embodiment can be quickly produced at a low cost of the copper material excellent in physical properties by forming a nano-twinned structure, it can be seen that the process is suitable for mass production.
  • the copper thin film was grown while varying the current density of the reverse fill step.
  • FIG. 9 is a graph showing the maximum true tensile strength according to the reverse-fill current density of the copper thin film manufactured by the manufacturing method of the present embodiment.

Abstract

La présente invention concerne un procédé de formation d'une matière de cuivre formée de façon à avoir une structure nano-bicristalline par l'utilisation de dépôt électrolytique, le procédé comprenant les étapes de : immersion d'une anode et d'une cathode dans une solution électrolytique de sulfate de cuivre ; et dépôt de façon électrolytique de cuivre sur la surface de l'anode par réalisation de façon répétée d'une étape de courant de pulsation dans laquelle un courant direct est appliqué à l'anode et à la cathode immergées de façon à faire croître des grains cristallins et des noyaux comprenant une structure nano-bicristalline et une étape de courant inverse dans laquelle un courant inverse est appliqué de façon à dissoudre les grains cristallins et les noyaux à l'exception de la structure nano-bicristalline, et, ici, la densité de la structure nano-bicristalline est améliorée dans l'étape de pulsation inverse. Lors de la formation d'une matière de cuivre formée de façon à avoir une structure nano-bicristalline au moyen d'un procédé de dépôt électrolytique, la présente invention a l'effet avantageux de rendre possible de réduire sensiblement le temps de formation par comparaison avec les procédés existants. De plus, il y a également l'effet avantageux que la matière de cuivre formée de façon à avoir la structure nano-bicristalline peut être rapidement obtenue en volume par l'utilisation d'un procédé de dépôt électrolytique à faible coût. Finalement, il y a l'effet avantageux que le cuivre de structure nano-bicristalline, formé en volume par le procédé de dépôt électrolytique, peut être utilisé comme matière de câblage pour divers éléments électroniques de telle sorte que la performance des éléments électroniques est améliorée.
PCT/KR2012/006678 2012-08-22 2012-08-22 Procédé de formation de matière de cuivre formée de façon à avoir une structure nano-bicristalline, et matière de cuivre ainsi obtenue WO2014030779A1 (fr)

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PCT/KR2012/006678 WO2014030779A1 (fr) 2012-08-22 2012-08-22 Procédé de formation de matière de cuivre formée de façon à avoir une structure nano-bicristalline, et matière de cuivre ainsi obtenue

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PCT/KR2012/006678 WO2014030779A1 (fr) 2012-08-22 2012-08-22 Procédé de formation de matière de cuivre formée de façon à avoir une structure nano-bicristalline, et matière de cuivre ainsi obtenue

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110073485A (zh) * 2016-12-15 2019-07-30 应用材料公司 无空隙间隙填充的电化学沉积方法
CN112921370A (zh) * 2019-12-06 2021-06-08 添鸿科技股份有限公司 纳米双晶铜金属层及其制备方法及包含其的基板
CN113046796A (zh) * 2019-12-27 2021-06-29 铂识科技股份有限公司 一种纳米双晶层的制备方法和一种纳米双晶层

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KR20020012118A (ko) * 2000-08-04 2002-02-15 미야무라 심뻬이 전착 동박 및 전착 동박의 제조 방법
KR20020093584A (ko) * 2001-06-07 2002-12-16 쉬플리 캄파니, 엘.엘.씨. 전해 구리 도금법
JP2005344208A (ja) * 2004-05-06 2005-12-15 Okuno Chem Ind Co Ltd 無電解ニッケルめっき液の処理方法
JP2006505101A (ja) * 2002-11-01 2006-02-09 中国科学院金属研究所 超高強度及び導電率を有するナノ結晶銅材料ならびにその製造方法

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Publication number Priority date Publication date Assignee Title
KR20020012118A (ko) * 2000-08-04 2002-02-15 미야무라 심뻬이 전착 동박 및 전착 동박의 제조 방법
KR20020093584A (ko) * 2001-06-07 2002-12-16 쉬플리 캄파니, 엘.엘.씨. 전해 구리 도금법
JP2006505101A (ja) * 2002-11-01 2006-02-09 中国科学院金属研究所 超高強度及び導電率を有するナノ結晶銅材料ならびにその製造方法
JP2005344208A (ja) * 2004-05-06 2005-12-15 Okuno Chem Ind Co Ltd 無電解ニッケルめっき液の処理方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110073485A (zh) * 2016-12-15 2019-07-30 应用材料公司 无空隙间隙填充的电化学沉积方法
CN110073485B (zh) * 2016-12-15 2023-07-28 应用材料公司 无空隙间隙填充的电化学沉积方法
CN112921370A (zh) * 2019-12-06 2021-06-08 添鸿科技股份有限公司 纳米双晶铜金属层及其制备方法及包含其的基板
CN112921370B (zh) * 2019-12-06 2024-04-19 添鸿科技股份有限公司 纳米双晶铜金属层及其制备方法及包含其的基板
CN113046796A (zh) * 2019-12-27 2021-06-29 铂识科技股份有限公司 一种纳米双晶层的制备方法和一种纳米双晶层

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