WO2020006761A1 - Electrolyte, method for preparing single crystal copper by means of electrodeposition using electrolyte, and electrodeposition device - Google Patents

Abstract

Disclosed are an electrolyte, a method for preparing a single crystal copper by means of electrodeposition using the electrolyte, and an electrodeposition device. In the case of excluding existing heat treatment methods, a single crystal copper having ultra-large grains with an average grain size of more than 10 μm can be prepared directly by means of an electrodeposition method, and the single crystal copper having ultra-large grains has low impurity and defect concentrations and thus has the properties of a low electrical resistance, a high electrical conductivity, making it difficult to leave fingerprints on a surface, etc.

Description

Electrolyte, method for preparing single crystal copper by electrodeposition using the electrolyte, and electrodeposition equipment Technical field

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.

Background technique

In the traditional copper foil industry, 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). In different copper foil application fields, based on different requirements such as increasing conductivity and improving the reliability of electronic components, 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, such as US Patent Publication No. US 6,126,761, 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 0.1μm ³ to 4.0 × 106μm ^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 ~ 700μm. 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. However, 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.

Summary of the invention

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.

To achieve the above object, 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:

-H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂

R _{2 is} selected from the group consisting of:

_{^{SO 3 -, PO 4 -,}} COO -;

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 μm is obtained on the cathode without heat treatment.

To achieve the above object, 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:

-H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂

R _{2 is} selected from the group consisting of:

_{^{SO 3 -, PO 4 -,}} COO -.

To achieve the above object, 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:

-H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂

R _{2 is} selected from the group consisting of:

_{^{SO 3 -, PO 4 -,}} COO -;

An electrode group disposed in the electrolyte, including a cathode and an anode disposed opposite the cathode;

A power supply source electrically connected to the electrode group; and

A device is to cause a relative motion between the cathode and the electrolyte to generate a potential oscillation interval.

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.

BRIEF DESCRIPTION OF THE DRAWINGS

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.

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.

detailed description

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 μm.

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 -SC _n H _2n -R ₂ (Equation 1)

Wherein, 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.

In one embodiment, 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.

In one embodiment, 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, OPX], 3-[(amino-iminomethyl) -thio] -1-propanesulfonic acid {3-[(Amino-iminomethyl) thio ] -1-propanesulfonate, UPS}, or sodium polydithiodipropane sulfonate [3,3-Thiobis (1-propanesulfonate), TBPS].

When the electrolytic solution of the present invention is used and applied to the preparation of single-crystal copper by electrodeposition, 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 μm 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.

In the present invention, 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. In one embodiment, 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. Or, 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.

Please refer to FIG. 1, which 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. In this embodiment, 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. In this embodiment, 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.

As shown in FIG. 1, 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.

Please refer to FIG. 2, which is a schematic diagram of an electrodeposition apparatus in another embodiment of the present invention. In this embodiment, the shape of the cathode 1 is a flat plate. According to different electrodeposition methods, 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.

In an example according to the present invention, 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%. In order to calculate the thickness of ultra-large grains (ULG) single crystal copper deposits, it is calculated according to Faraday's law, based on δ = 0.003445 × j × t, where δ is the thickness of the deposit, j is the current density (A / dm ² ) and t is the electrodeposition time (sec). In this example, the size of the copper deposit is 18 cm × 21 cm and the thickness is 30 μm. The copper deposits are all single crystals with super large grains. The copper structure grows, as shown in the following figure.

Please refer to FIG. 3, which is a surface morphology of a copper foil of super large grain single crystal copper in an embodiment of the present invention. As can be seen from the photo of the optical microscope of FIG. Diamond shiny luster due to single crystal total reflection. 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 μm, and the center line average roughness (R _a ) was 4.67 ± 6.14 μm. Because of the high surface roughness, the area in contact with the fingers is small, so fingerprints are not easy to remain.

Please refer to FIG. 4A to FIG. 4C. In an embodiment of the present invention, 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 μm; 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 μm. Please continue to refer to FIG. 9, which 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 μm 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 .

Please continue to refer to Figure 10. For the relationship of potential with time under different current densities and electrode rotation speeds, in this experiment, 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. Further referring to 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. 11 are based on D The copper foil obtained in the electroplating conditions of the figure, in which 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. Among them, the C thumbnail corresponds to the D thumbnail. In the I region, 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 μm can be seen from the small picture of C.

Please continue to refer to FIG. 12A to FIG. 12D, which 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. Finally, the first copper wire 13, the second copper wire 14, the tin-containing body 15, the Ion cross-sectional images of the first intermetallic compound layers 16a and 16b and the second intermetallic compound layers 17a and 17b. Among them, 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, and FIG. FIB picture, 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. It is known that Kirkendall voids will affect the efficiency of electron transfer and lead to an increase in resistance. 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.

The present invention has been described in detail above, but the above is only a preferred embodiment of the present invention, and the scope of implementation of the present invention cannot be limited. That is, all equivalent changes and modifications made according to the scope of the application of the present invention shall still fall within the scope of the patent of the present invention.

Claims (26)

A method for preparing single crystal copper by electrodeposition without heat treatment, which comprises 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: -H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂ R _{2 is} selected from the group consisting of: SO _3- , PO _4- , COO-; 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 μm is obtained on the cathode without heat treatment. The method according to claim 1, wherein in step B, a spray is applied to the electrolytic solution to cause a relative movement between the cathode and the electrolytic solution. The method according to claim 2, wherein the velocity of the jet is between 9 cm / s and 45 cm / s. The method of claim 1, wherein in step B, the cathode is rotated in the electrolyte to cause a relative movement between the cathode and the electrolyte. The method of claim 4, wherein the cathode is rotated at a speed between 1000 rpm and 10,000 rpm. The method according to any one of claims 1 to 5, wherein the sulfur-containing compound is an alkylsulfonate sulfide (RSC _n H _2n -SO _3- ). The method according to claim 6, wherein the alkyl sulfonate sulfide compound is selected from the group consisting of 3-mercaptopropanesulfonate (MPS), sodium polydithiodipropane sulfonate [Bis -(3-sulfopropyl) -disulfide, SPS], 3- (benzothiothiazol-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, OPX], 3-[(amino-iminomethyl) -thio] -1-propanesulfonic acid {3-[(Amino-iminomethyl) thio] -1-propanesulfonate, UPS} and sodium polydithiodipropane sulfonate [3,3-Thiobis (1-propanesulfonate), TBPS]. The method according to any one of claims 1 to 5, wherein a concentration of the sulfur-containing compound relative to the electrolyte is between 0.1 ppm and 5 ppm. The method according to any one of claims 1 to 5, wherein the electrolytic solution further comprises copper sulfate, and the concentration of the copper sulfate relative to the electrolytic solution is between 125 g / L and 320 g / L. The method according to any one of claims 1 to 5, wherein the electrolytic solution further comprises sulfuric acid, and the concentration of the sulfuric acid with respect to the electrolytic solution is between 17.6 g / L and 176 g / L. The method according to any one of claims 1 to 5, wherein the electrolyte further comprises chloride ions, and the concentration of the chloride ions relative to the electrolyte is between 30 ppm and 60 ppm. The method according to any one of claims 1 to 5, wherein the electrolyte further comprises a wetting agent, the wetting agent is polyethylene glycol (PEG), and the polyethylene glycol has a The molecular weight is between 200 and 2000, and the concentration relative to the electrolyte is between 10 ppm and 200 ppm. The method according to any one of claims 1 to 5, wherein a distance between the anode and the cathode is between 1 cm and 12 cm. An electrolytic solution for preparing single crystal copper by electrodeposition, characterized in that the electrolytic solution includes at least one sulfur-containing compound, and the sulfur-containing compound is R ₁ -SC _n H _2n -R ₂ , wherein n is between 2 From 10 to 10, R _{1 is} selected from the group consisting of: -H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂ R _{2 is} selected from the group consisting of: SO _3- , PO _4- , COO-. The electrolytic solution according to claim 14, wherein the sulfur-containing compound is an alkylsulfonate sulfide (RSC _n H _2n -SO _3- ). The electrolytic solution according to claim 15, wherein the alkyl sulfonate sulfide compound is selected from the group consisting of 3-mercaptopropanesulfonate, MPS, and 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, OPX], 3-[(amino-iminomethyl) -thio] -1-propanesulfonic acid {3-[(Amino-iminomethyl) thio ] -1-propanesulfonate, UPS} and sodium polydithiodipropane sulfonate [3,3-Thiobis (1-propanesulfonate), TBPS]. The electrolytic solution of claim 14, wherein the concentration of the sulfur-containing compound relative to the electrolytic solution is between 0.1 ppm and 5 ppm. The electrolytic solution according to claim 14, further comprising copper sulfate, the concentration of the copper sulfate relative to the electrolytic solution being between 125 g / L and 320 g / L. The electrolytic solution according to claim 14, further comprising sulfuric acid, and a concentration of the sulfuric acid relative to the electrolytic solution is between 17.6 g / L and 176 g / L. The electrolyte according to claim 14, further comprising chloride ions, the concentration of the chloride ions relative to the electrolyte being between 30 ppm and 60 ppm. The electrolytic solution according to claim 14, further comprising a wetting agent, wherein the wetting agent is polyethylene glycol (PEG), and the polyethylene glycol has a medium between 200 and 2000. Molecular weight, and the concentration of the electrolyte is between 10 ppm and 200 ppm. An electrodeposition equipment includes: 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: -H, -SC _n H _2n -R ₂ , -C _n H _2n -R ₂ R _{2 is} selected from the group consisting of: SO _3- , PO _4- , COO-; An electrode group disposed in the electrolyte, including a cathode and an anode disposed opposite the cathode; A power supply source electrically connected to the electrode group; and A device is to cause a relative movement between the cathode and the electrolyte to generate a potential oscillation interval. The electrodeposition apparatus according to claim 22, wherein the device is a pair of spraying devices for generating a flow rate of the electrolyte between 9 cm / s and 45 cm / s. The electrodeposition apparatus according to claim 22, wherein the device is a rotating device that rotates the cathode at a rotation speed between 1000 rpm and 10000 rpm. The electrodeposition apparatus according to claim 22, wherein the cathode is formed in a disc shape. An electronic component connection structure is characterized in that the electronic component connection structure includes: A bonding pad including 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 μm; A tin-containing body soldered to a surface of the bonding pad; and An intermetallic compound layer is formed between the bonding pad and the tin-containing body.

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