WO2020006761A1 - Électrolyte, procédé de préparation d'un cuivre monocristallin par électrodéposition à l'aide d'un électrolyte, et dispositif d'électrodéposition - Google Patents

Électrolyte, procédé de préparation d'un cuivre monocristallin par électrodéposition à l'aide d'un électrolyte, et dispositif d'électrodéposition Download PDF

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WO2020006761A1
WO2020006761A1 PCT/CN2018/094897 CN2018094897W WO2020006761A1 WO 2020006761 A1 WO2020006761 A1 WO 2020006761A1 CN 2018094897 W CN2018094897 W CN 2018094897W WO 2020006761 A1 WO2020006761 A1 WO 2020006761A1
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electrolyte
electrolytic solution
electrodeposition
cathode
ppm
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PCT/CN2018/094897
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English (en)
Chinese (zh)
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窦维平
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力汉科技有限公司
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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
    • C25D3/38—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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk

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  • the invention relates to an electrolytic solution, a method for preparing single-crystal copper by electrodeposition using the electrolytic solution, and an electrodeposition device, and more particularly, to an electrolytic solution, method, and electrodeposition device suitable for preparing super-large-grain single-crystal copper.
  • a copper metal film is deposited on a conductive substrate by electrodeposition.
  • This electrodeposited copper film has a fine copper grain microstructure (average grain size is less than 100 nm).
  • the copper grain size needs to be increased.
  • Traditional methods for increasing the grain size of copper include heat treatment and rolling.
  • Existing electrodeposition copper technology proposes a method for controlling the growth of copper grains.
  • the method includes the steps of: (a) depositing a metal film on a substrate to form a layer A thin film having a fine grain microstructure, and (b) heating the metal film at a temperature range of 70 ° C to 100 ° C for at least 5 minutes, in which the fine grain microstructure is transformed into a stable large grain microstructure ;
  • U.S. Patent Publication No. US20150064496 proposes a method for preparing single crystal copper. The method uses electroplating to grow a nano-twin-crystal copper pillar on the cathode surface of a plating tank.
  • the nano-twin-crystal copper pillar contains a plurality of nano-twin-crystal copper. Grains; the cathode with the nano-twin-crystal copper pillars formed thereon is annealed at a temperature of 350 ° C. to 600 ° C. for 0.5 hour to 3 hours to obtain a single crystal copper, the single crystal copper having [100 ] direction, and the volume of dielectric between 0.1 ⁇ m 3 to 4.0 ⁇ 106 ⁇ m 3; in addition, U.S. Patent Publication No.
  • US2016168746 discloses a copper thin film having a large crystal grains, a plurality of crystal grains of the copper thin film along the [100] crystal axis Direction growth, the average of the multiple grains is large Of 150 ⁇ 700 ⁇ m.
  • the preparation method is to electroplat grow copper foil grains on one surface of a substrate to obtain a [111] nano-twin-copper thin film; and then perform the [111] nano-twin-copper thin film at a temperature between 200 ° C and 500 ° C. Annealing treatment to obtain a copper thin film with large grains.
  • the above various electrodeposition processes require heat treatment before large grain copper can be obtained.
  • heat treatment involves heating equipment and control of heating time and heating temperature.
  • the two processes of electroplating and heat treatment increase the number of processes and man-hours, and the production cost is high, and because The heat treatment diffuses impurities in the copper deposits, which is prone to increase resistance and affect conductivity.
  • the main purpose of the present invention is to solve the problems of the long process time caused by the heat treatment in the existing electrodeposition process and the influence of the quality of copper deposits due to the heat treatment.
  • the present invention provides a method for preparing single crystal copper by electrodeposition without heat treatment, which includes the following steps:
  • Step A Provide an electrolytic solution including a sulfur-containing compound, the sulfur-containing compound is R 1 -SC n H 2n -R 2 , wherein n is between 2 and 10, and R 1 is selected from the following Groups:
  • R 2 is selected from the group consisting of:
  • Step B An anode and a cathode are placed in the electrolyte to perform an electrodeposition.
  • the current density of the electrodeposition is between 1A / dm 2 and 80A / dm 2 , and the cathode is dynamic during the electrodeposition. Placed on the electrolyte to form a potential oscillation interval; and
  • Step C After the electrodeposition, a single crystal copper with a particle size greater than 10 ⁇ m is obtained on the cathode without heat treatment.
  • the present invention also provides an electrolytic solution for preparing single crystal copper by electrodeposition.
  • the electrolytic solution includes a sulfur-containing compound, and the sulfur-containing compound is R 1 -SC n H 2n -R 2 , wherein, n is between 2 and 10, and R 1 is selected from the group consisting of:
  • R 2 is selected from the group consisting of:
  • the present invention further provides an electrodeposition device, including:
  • An electrolytic cell includes an electrolytic solution, the electrolytic solution includes a sulfur-containing compound, the sulfur-containing compound is R 1 -SC n H 2n -R 2 , wherein n is between 2 and 10, and R 1 is selected from the following Group of:
  • R 2 is selected from the group consisting of:
  • An electrode group disposed in the electrolyte including a cathode and an anode disposed opposite the cathode;
  • a device is to cause a relative motion between the cathode and the electrolyte to generate a potential oscillation interval.
  • the electrodeposition equipment method and the electrodeposition equipment of the present invention Compared with the prior art, by adopting the electrolytic solution, the electrodeposition equipment method and the electrodeposition equipment of the present invention, super large grain single crystal copper can be prepared without heat treatment, and the single crystal copper has fewer defects and is applicable. In the manufacture of high reliability electronic connection components.
  • FIG. 1 is a schematic diagram of an electrodeposition apparatus according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram of an electrodeposition apparatus in another embodiment of the present invention.
  • FIG. 3 is a surface morphology of a copper foil of super-large-grain single-crystal copper in an embodiment of the present invention.
  • FIG. 4A to FIG. 4C are SEM images of the surface morphology of the copper foil of single-crystal copper with ultra-large grains at different magnifications according to an embodiment of the present invention.
  • FIG. 5 is a comparison diagram of cross-sectional ion images of the surface morphology of a copper foil of super-large-grain single-crystal copper and a conventional double-crystal copper according to an embodiment of the present invention.
  • FIG. 6 is a cross-sectional ion image diagram of the surface morphology of a copper foil of super-large-grain single-crystal copper in an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of obtaining the size of super large-grain single-crystal copper by a truncation method.
  • FIG. 8 is a transmission electron microscope and selective diffraction analysis (TEM & SAD) analysis of the surface morphology of the copper foil of ultra-large grain single crystal copper according to an embodiment of the present invention.
  • TEM & SAD selective diffraction analysis
  • FIG. 9 is a schematic diagram of a connection structure of an electronic component according to an embodiment of the present invention.
  • FIG. 10 shows the change and relationship of the potential with time according to the present invention under different current densities and electrode rotation speeds.
  • FIG. 11 is a microstructure photograph of a copper foil obtained under different plating times in an embodiment of the present invention.
  • FIGS. 12A to 12D are ion cross-sectional image diagrams (FIB images) of an electronic component connection structure made of ultra-large-grain single-crystal copper obtained in accordance with the present invention at a high temperature environment at different times.
  • the invention relates to an electrolytic solution, a method for preparing single crystal copper by electrodeposition using the electrolytic solution, and an electrodeposition device.
  • the electrodeposition referred to in the present invention includes, but is not limited to, electroforming or electroplating, and the electrolysis described in the present invention
  • the liquid, electrodeposition method and electrodeposition equipment are suitable for preparing ultra-large grains (ULG) single-crystal copper without heat treatment.
  • the ultra-large grains referred to in the present invention refer to the grain size Not less than 10 ⁇ m.
  • the electrolytic solution of the present invention is used to prepare single crystal copper by electrodeposition.
  • the essential feature of the electrolytic solution includes a sulfur-containing compound represented by formula (1).
  • R 1 selected from a -H, the group -SC n H 2n -R 2, -C n H 2n -R 2 consisting of; R 2 selected from a SO 3 -, PO 4 -, COO - consisting of And n is between 2 and 10, wherein the sulfur-containing compound is dissolved in deionized water and exists in the electrolyte.
  • the electrolyte further includes chloride ion, wetting agent, sulfuric acid, and copper sulfate pentahydrate.
  • the source of the chloride ion is sodium chloride or hydrochloric acid, and the concentration of the chloride ion with respect to the electrolyte is between 30 ppm and 60 ppm, preferably between 40 ppm and 50 ppm.
  • the wetting agent is selected from polyethylene glycol and has a molecular weight. Between 200 and 2000, preferably between 800 and 1600, the concentration of the wetting agent relative to the electrolyte is between 10 ppm and 200 ppm, and preferably between 50 ppm and 150 ppm.
  • the sulfuric acid is relative to the electrolyte
  • the concentration is between 17.6g / L and 176g / L, preferably between 25g / L and 150g / L.
  • the concentration of the copper sulfate pentahydrate relative to the electrolyte is between 125g / L and 320g / L.
  • the concentration of the sulfuric acid with respect to the electrolyte is between 17.6 g / L and 176 g / L, and the preferred range is between 140 g / L and 280 g / L.
  • the sulfur-containing compound is an alkylsulfonate sulfide compound (R, alkanesulfonatesulfide, RSC n H 2n -SO 3- ), and the concentration of the sulfur-containing compound relative to the electrolyte is between 0.1 ppm and 5 ppm. The preferred range is 0.5 ppm to 4 ppm.
  • the alkyl sulfonate sulfide compound includes, but is not limited to, 3-mercaptopropanesulfonate [MPS], sodium polydithiodipropane sulfonate [ Bis- (3-sulfopropyl) -disulfide, SPS], 3- (Benzothiazol-2-mercapto) propanesulfonic acid [3- (2-Benzthiazolylthio) -1-propanesulfonate, ZPS], N, N-dimethyl -Sodium dithioformamide propane sulfonate [3- (N, N-Dimethylthiocarbamoyl) -thiopropanesulfonate, DPS], (O-ethyldithiocarbonate) -S- (3-sulfopropyl) -ester potassium salt [ (O-Ethyldithiocarbonato) -S- (3-sulfopropyl) -ester, OP
  • ultra-large-grain single-crystal copper can be prepared under conditions of no heat treatment, and particularly, ultra-large-grain single-crystal copper having a particle size greater than 10 ⁇ m can be prepared.
  • a method for preparing ultra-large-grained single-crystal copper using the electrolyte will be further described below.
  • the method for preparing single crystal copper by electrodeposition in the present invention includes the following steps:
  • Step A First, an electrolytic solution is provided.
  • the electrolytic solution includes a sulfur-containing compound.
  • the components and concentrations of the electrolytic solution and the sulfur-containing compound can be as described above.
  • Step B An anode and a cathode are placed in the electrolyte to perform an electrodeposition.
  • the current density of the electrodeposition is between 1A / dm 2 and 80A / dm 2 , and the preferred range is 3A / dm 2 to 50A / between dm 2 and the electrode is dynamically placed in the electrolyte during the electrodeposition, so that during the electrodeposition, a potential oscillation interval is formed between the electrodes.
  • Step C After the electrodeposition, an ultra-large grain (ULG) single crystal copper is obtained on the cathode without heat treatment.
  • UMG ultra-large grain
  • the cathode in step B is dynamically placed on the electrolyte, which generally refers to any manner that causes the potential to oscillate by moving the cathode relative to the electrolyte, for example: applying a spray to the electrolyte To cause a relative movement between the cathode and the electrolyte.
  • the velocity of the jet flow is between 9 cm / s and 45 cm / s, and the preferred range is 12 cm / s to 35 cm / s.
  • the cathode is rotated in the electrolyte, and the rotation speed is between 1000 rpm and 10000 rpm, preferably between 3000 rpm and 7000 rpm.
  • the present invention is not limited to this, and any movement manner or device that can form the potential oscillation interval between electrodes can be applied to the present invention.
  • FIG. 1 is a schematic diagram of an electrodeposition apparatus according to an embodiment of the present invention.
  • the electrodeposition apparatus includes a cathode 1, an anode 2, an electrolyte 4, a temperature control device 6, and a power supply source 7.
  • a power supply source 7 is connected to the anode 2 and the cathode 1, respectively, and the anode 2 and the cathode 1 are immersed in the electrolytic solution 4, and the temperature control device 6 contacts the electrolytic solution 4.
  • the electrodeposition device further includes a jet flow device, which may be a stirring device, which stirs the electrolyte 4 to generate a jet flow 5.
  • the stirring device is a rotating magnet M, and in order to make the jet flow 5 disturb the electrolyte 4 near the cathode 1, the anode 2 is provided with an opening 21.
  • the cathode 1 may be a rotatable cylindrical shape, and the shape of the anode 2 is complementary to the shape of the cathode 1 and is half-cylindrical.
  • the anode 2 may be a soluble anode or an insoluble anode.
  • the cathode 1 can be platinum, iridium oxide / titanium, iridium oxide / tantalum pentoxide / titanium, copper, or phosphorous copper.
  • the cathode 1 can be any conductor, including various metals, carbon materials, and the like.
  • the electrodeposition 3 on the surface of the cathode 1 is taken away from the cathode 1 by a take-up roller 8. In this embodiment, the distance between the cathode 1 and the anode 2 is between 1 cm and 12 cm, and preferably between 2 cm and 10 cm.
  • FIG. 2 is a schematic diagram of an electrodeposition apparatus in another embodiment of the present invention.
  • the shape of the cathode 1 is a flat plate.
  • the electrodeposition 3 may be Bonded to the surface of the cathode 1, or the electrodeposition 3 and the cathode 2 may be in a separable bonding relationship.
  • the power supply source 7 is a DC power supply.
  • the maximum output current / voltage of the power supply is 100A / 10V, and the current density of the electrodeposition is between 1A / dm 2 and 80A / dm. Between 2 , the preferred range is between 3 A / dm 2 and 50 A / dm 2 , and the current efficiency is 94%.
  • USG ultra-large grains
  • it is calculated according to Faraday's law, based on ⁇ 0.003445 ⁇ j ⁇ t, where ⁇ is the thickness of the deposit, j is the current density (A / dm 2 ) and t is the electrodeposition time (sec).
  • the size of the copper deposit is 18 cm ⁇ 21 cm and the thickness is 30 ⁇ m.
  • the copper deposits are all single crystals with super large grains. The copper structure grows, as shown in the following figure.
  • FIG. 3 is a surface morphology of a copper foil of super large grain single crystal copper in an embodiment of the present invention.
  • the surface roughness was analyzed by a SURFCOM 130A surface roughness measuring instrument. According to the measurement results, the ten-point average roughness (R z ) was 29.40 ⁇ 8.40 ⁇ m, and the center line average roughness (R a ) was 4.67 ⁇ 6.14 ⁇ m. Because of the high surface roughness, the area in contact with the fingers is small, so fingerprints are not easy to remain.
  • FIG. 4A to FIG. 4C an electron scanning microscope image of the surface morphology of super-large-grain single-crystal copper foil at different magnifications is shown in FIG. 4A at a magnification of 100x, showing a copper crystal surface. It presents a concavo-convex shape like a valley shape, and the depth of the concavity between the ridges is extremely deep.
  • the magnifications of Fig. 4B and Fig. 4C are 500x and 3000x, respectively. It can be seen that the surface of the copper crystal has many edges and angles.
  • FIG. 5 is a comparison diagram of cross-section ion images of the copper foil surface morphology of the ultra-large grain single crystal copper and the existing twin crystal copper according to an embodiment of the present invention.
  • ions (beam image, FIB image), on the right is an existing cross-sectional ion image diagram containing a large amount of double crystal copper, both of which have a magnification of 5000x.
  • the comparison results show that the grain size of the large single crystal copper obtained according to the present invention is about 10 to 50 times the right.
  • Fig. 6 is a cross-sectional ion image of a super-large-grain single-crystal copper according to the present invention, with a magnification of 1400x, showing a consistent microstructure in a cross-section of 100 ⁇ m; Schematic diagram of linear intercept method of grain intercept.
  • Figure 8 is a transmission electron microscope and selected diffraction analysis diagram of the surface morphology of the copper foil of large single crystal copper according to an embodiment of the present invention. (TEM & SAD Analysis).
  • the invention further discloses an electronic component connection structure.
  • the electronic component connection structure includes a bonding pad, a tin-containing body soldered to a surface of the bonding pad, and a bonding pad formed on the bonding pad and the tin-containing body.
  • the intermetallic compound layer, the bonding pad includes at least one super-large grain single crystal copper, and the grain size of the super large grain single crystal copper is not less than 10 ⁇ m.
  • FIG. 9, is a schematic diagram of an electronic component connection structure according to an embodiment of the present invention.
  • the electronic component connection structure includes: a first dielectric layer 11, a second dielectric layer 12, a first copper wire 13, A second copper wire 14, a tin-containing body 15, and a first interposer metal compound layer 16a, a first interposer metal compound layer 16b, a second interposer metal compound layer 17a, and a second interposer metal compound Layer 17b, the copper wires 13, 14 are disposed on opposite surfaces of the first dielectric layer 11 and the second dielectric layer 12, and the first copper wire 13 and the second copper wire 14 are ultra-large grains larger than 10 ⁇ m Single crystal copper is prepared by the method disclosed above.
  • the tin-containing body 15 includes pure tin solder, tin / silver / copper alloy, tin / silver alloy, or other lead-free tin solder; the first interposer metal compound layer 16a and the second interposer metal compound layer 17a are disposed on the Between the first copper wire 13 and the tin-containing body 15, the first lower intermetal compound layer 16b and the second lower metal compound layer 17b are disposed between the second copper wire 14 and the tin-containing body 15, The composition of the first intermetallic compound layers 16a and 16b is Cu 3 Sn, and the composition of the second intermetallic compound layers 17a and 17b is Cu 6 Sn 5 .
  • the cathode used is a rotating disk electrode, which is designed to be placed in electrolysis
  • the liquid rotates relative to the electrolyte, and at a specific speed, current density, and elapsed time, a potential oscillation interval can be generated.
  • FIG. 11 according to an embodiment of the method and the electrolyte disclosed in the present invention, microstructure photographs of copper foil obtained at different plating times, the small panels A to C in FIG.
  • the small picture A shows an optical microscope photo of the entire copper foil, no difference in grain structure can be seen
  • the small picture B is an SEM picture of the copper foil
  • the small picture C is A FIB photograph of a portion of the copper foil, which was mined from the area pointed by the arrow in the small panel B.
  • the C thumbnail corresponds to the D thumbnail.
  • the potential has not yet oscillated, so the grains of the C thumbnail have a polycrystalline structure; in the II region, the potential begins to oscillate slightly, which can be seen from the C thumbnail The microstructure has gradually shown large grains; in the III region, the potential fluctuates significantly, and the ultra-large grain single-crystal copper with a size greater than 10 ⁇ m can be seen from the small picture of C.
  • FIG. 12A to FIG. 12D are FIB photographs of an electronic component connection structure made of ultra-large-grain single-crystal copper obtained according to an embodiment of the method and the electrolyte disclosed in the present invention, in a high-temperature environment at different times.
  • the electronic component connection structure of FIG. 9 is heat-treated at 200 ° C. at different times, and cut by ion cutting.
  • FIG. 12A to FIG. 12D are FIB photographs of an electronic component connection structure made of ultra-large-grain single-crystal copper obtained according to an embodiment of the method and the electrolyte disclosed in the present invention, in a high-temperature environment at different times.
  • the electronic component connection structure of FIG. 9 is heat-treated at 200 ° C. at different times, and cut by ion cutting.
  • FIG. 12A is a FIB photograph after being left in a high-temperature environment at 200 ° C for 72 hours
  • FIG. 12B is a FIB photograph after being placed in a high-temperature environment at 200 ° C for 144 hours
  • FIG. 12D is a FIB picture after being left for 1000 hours in a high-temperature environment of 200 ° C. From these pictures, it can be seen that the ultra-large grain single crystals obtained according to the method disclosed in the present invention and the electrolyte formulation are found to have undergone high Over a long period of experiments, the intermetallic compound layer does not generate Kirkendall voids and any undesirable voids.
  • the electronic component connection structure of the present invention has no Kirkendall voids, and the ultra-large grain copper contains very few impurities and has extremely low resistance. Low, therefore, the electronic connection component using the ultra-large grain single crystal copper of the present invention has high reliability.

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Abstract

L'invention concerne un électrolyte, un procédé de préparation d'un cuivre monocristallin par électrodéposition à l'aide de l'électrolyte, et un dispositif d'électrodéposition. Dans le cas de l'exclusion de procédés de traitement thermique existants, un cuivre monocristallin présentant de très gros grains dotés d'une taille de grain moyenne supérieure à 10 µm peut être préparé directement par un procédé d'électrodéposition, et le cuivre monocristallin présentant de très gros grains présente de faibles concentrations d'impuretés et de défauts et présente ainsi les propriétés d'une faible résistance électrique, d'une conductivité électrique élevée, ce qui permet d'éviter de laisser des empreintes sur une surface, etc.
PCT/CN2018/094897 2018-07-06 2018-07-06 Électrolyte, procédé de préparation d'un cuivre monocristallin par électrodéposition à l'aide d'un électrolyte, et dispositif d'électrodéposition WO2020006761A1 (fr)

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CN106480479A (zh) * 2016-10-12 2017-03-08 东莞华威铜箔科技有限公司 挠性电解铜箔用添加剂的制备方法、制品及其应用
CN107217282A (zh) * 2017-07-24 2017-09-29 苏州天承化工有限公司 一种高tp值软板电镀液及电镀方法

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