TW200532057A - Composition for copper electroplating solution - Google Patents

Abstract

A composition for copper electroplating solution is disclosed. The composition for copper electroplating solution of the present invention utilizes additives without dyes to overcome a pin-hole effect caused by dyes in a prior copper electroplating solution, increases a effective concentration and range of a brighter, and reduces sensitivity of the copper electroplating solution to fluid direction. In addition, a method for electroplating copper is further disclosed. During a copper process of a semiconductor and a via-filling process of a printed circuit board (PCB), the method can perform an electroplating procedure to overcome the pin-hole effect due to additives without dyes, and to be easy in operation and production.

Description

200532057 D. Description of the invention [Technical field to which the invention belongs] The present invention relates to the composition of a copper electroplating solution, and in particular to the composition of a copper electroplating solution containing no dye additives. [Previous Technology] With the continuous miniaturization and multifunctionality of today's electronic products, traditional wafers and integrated circuits (ICs) constitute substrates (ic

The Packaging Substrate) process is also constantly being updated. Especially after the manufacturing process of Ball Grid Array (BGA) and Chip Scale Packaging (CSP) has become mainstream, the volume of IC substrates has shrunk sharply to catch up with 1C ', so the line width and line spacing are also gradually shrinking. To place more electronic components in a smaller area. According to the current 1C steel process technology and high density internal connection (HDI) of Printed Circuit Board (PCB). • Sub-micron or micro-inner layer connection holes (Via) and wire trenches ( Trench) needs to be filled with metallic copper material by electroplating. Filling must be performed by the bottom of the hole (Bottom_Up) or the so-called super fill (Supei * _Filhng) to avoid the occurrence of voids or gaps. There are usually two methods to fill copper wires and vias by electroplating. One is a physical method, which uses pulsed or positive and negative pulse Reverse motors to achieve the phenomenon of "hole bottom moving up." The other is a chemical method. 'Add multiple additives to the electric clock liquid, and use DC current plating to achieve the filling effect of the bottom of the hole 200532057. At present, whether in academia or industry, most of the latter research and use, so most of the academic The electroplated copper technology is limited to the wafer-level electroplating process. Due to the difference between the 1C substrate and the wafer, the main size is the size of the aperture, so the basic reaction mechanism should be similar. Moreover, because the aperture of the 1C substrate is smaller than Large, there are more factors to consider (such as convection, mass transfer), which must be more complicated than the copper plating process of wafers. Please refer to Figure 1, which shows the IC substrate filled with metal wires by conventional techniques. A cross-sectional view of a metal layer 105, such as a copper layer, is filled into a micron- or sub-micron-level opening of a 1C substrate 101, such as a blind hole 103, using the electroplating filling process. Deposition is performed in two possible ways, for example, Anti-Conformal, Conformal, and Super_Filling. When deposited in a non-conformal manner, a void U1 is generated. On the other hand When the deposition is performed in a conformal manner, since the metal layer 105 is formed in a uniform thickness manner, a gap 113 will eventually be generated. Therefore, the blind hole 103 can only be blinded by moonlight. Completely filled up to Defect-Free n5, without generating holes 111 and gaps 113. The former two deposition methods cannot completely fill the blind holes 103, and the resulting holes ui and gaps 13 will Affects the signal transmission rate and reduces the reliability of the wafer. In order to overcome the shortcomings of the conventional technology, 966 US Patent Publication Nos. 3,267,010 and 3,288,690 teach that adding several additives during the plating process can make the bottom of the hole The copper deposition rate is higher than the surface, which causes the bottom of the hole to move up, which improves the problems of voids and gaps. In these two patents, two types of additives are used, such as brighteners and inhibitors. With Leveler, it can produce the filling effect of 200532057 when the bottom of the hole is moved up, and the above formula has been used till now. In the hole-filling electroplating, the commonly used gloss agent or accelerator thiol is commonly known. There are two types of (Mercapto) series compounds, one is Bis (3-Sulfopropyl) Disulfide (SPS) 'and the other is 3-thiol-i-propionic acid (3-Mercapto-1-Propane Sulfonate; MPS). SPS and MPS will convert each other during the electroplating process, and the -SH functional group of MPS will form a complex with copper ions, change the reaction mechanism of copper ion reduction, increase the exchange current density of the electroplating reaction, and accelerate the deposition of copper. In addition, SPS and MPS are strongly adsorbed on the electrode surface when the plating reaction occurs. SPS will quickly reduce to MPS, and MPS will help divalent copper ions to reduce to monovalent copper ions and oxidize to SPS. Rate of formation of monovalent copper on the electrode surface. Landau U. et al. Disclosed the composition of a plating solution in US Patent Publication Nos. 6,610,191, 6,3 50,3 66, and 6,113,771. The use of the substituted Phthalocyanine compound Aiciail Blue as a glossing agent in the copper electroplating process, and other additives need to be blended in order to be suitable for the hole filling plating process of semiconductors, and is not suitable for Process for filling holes in printed circuit boards. The inhibitor, or carrier, can significantly reduce the copper deposition rate of the electroplated copper reaction, and commonly used inhibitors can be, for example, polyethylene glycol (PEG) and gas ions. When pEG and chloride ions coexist, it will strongly inhibit the deposition of steel ions, but other literature shows that chloride ions alone will accelerate the reduction of copper ions. 200532057 The leveling agent can effectively increase the effective range concentration of the accelerator, reduce the generation of voids, and also smooth the surface to be plated. The conventional levelers are mostly organic nitrogen-containing heterocyclic compounds, such as Azole compounds, etc., because they have functional groups, they will be preferentially adsorbed in the high current density area due to the current distribution. , Thereby suppressing the copper deposition rate. Levelling agents used by Veer are, for example, Janus Green β (jgb) and Benzotriazole (BTA). Generally speaking, most of the current electroplating bath formulations in academia and industry adopt the above-mentioned heavy additive formulation, but the multi-additive formulation has the following disadvantages. First of all, the above-mentioned commonly used leveling agents contain dyes, which are easily decomposed during electroplating to generate insoluble organic substances, and this insoluble organic substances will be re-adhered to the surface of the wafer or PCB, resulting in pinpoint anti-plating phenomenon (pin_H 〇ie

Effect). Secondly, the effective concentrations of the accelerators sps and Mps are relatively low and the range is very narrow, 'between about parts per MilliI (IlI; ppm) 〇3 to about 2.0 ppm, making it difficult to control and analyze during production . In addition, the conventional plating solution formula is more sensitive to fluid mechanics, and it is necessary to effectively fill the holes in the plating solution under a specific plating solution flow field. Xin stated above that there is a real need to propose a composition of copper plating solution to overcome the problem of anti-plating of the pin point caused by dyes in conventional copper plating solution, improve the effective concentration and range of the gloss agent, and reduce the direction of the convection field of the copper plating solution. Sensitivity. [Summary of the Invention] Therefore, one of the objectives of the present invention is to provide a composition of a copper electroplating solution. The additive does not contain dyes. The problem of plating improves the sensitivity of the copper plating solution to the flow field when the effective concentration of the brightener is low. Another object of the present invention is to provide a method for electroplating copper, which can perform the electric chain step in the copper electroplating solution of the present invention during the process of conducting copper and filling the holes of the printed circuit board. Does not contain dyes, which not only overcomes the phenomenon of pin point resistance to plating, but also facilitates operation and production.

According to the above object of the present invention, a composition of a copper electroplating solution is proposed, including at least: copper ions; a glossing agent, wherein the glossing agent is a non-simple thiol compound; an inhibitor; and a leveling agent, wherein the leveling agent is a benzimidazole derivative (B enzi in ida ζ ο 1 e D erivative) 〇 According to a preferred embodiment of the present invention, the structure of the above non-simple thiol compound is as follows (I): X-S-Y-Z (I) where X For example, the following formula (Π), formula (melon), formula (IV), formula (V), formula (VI), formula (guilty), formula (VI), formula (K), or formula (X),

(Π) nh2 + (Π)

II H2N—C- 12 (IV) 200532057 H3C I N—C H3C ’

(V)

(VI)

HS

N——N

S

(M)

(IX)

N—N

S

(X) 13 200532057 and γ can be, for example, an alkyl group of ~ (CH2) n —, where n is an integer between, and Z can be, for example, a COOH, a S03Na, an OH, or an NH2. In a preferred embodiment of the invention, the structure of the above-mentioned benzimidazole derivative can be, for example, the following formula (X Π):

(X π) where, for example, -S03 Na, -NH2, -SH or -OH, R2 can be -NH-, ~ Ο ~ or -s-, and R3 can be -CN, -COOH, -S03Na ,-Oh,-NH2 or -CH3. According to a preferred embodiment of the present invention, the above-mentioned inhibitor includes at least a polyglycol and an electrolyte. The polyglycol may be, for example, polyethylene glycol (PEG), polypropylene glycol (Polypropylene Glycol; PPG), or polyethylene oxide (Polyethylene Oxide). PEO), or polyethylene glycol third octylphenyl ether (p〇lyethylene

Glycol Tert-Octylphenyl Ether; Triton X-405), and the electrolyte is a halogen ion. According to a preferred embodiment of the present invention, the above copper ion is provided by a copper-containing compound, and the copper-containing compound may be, for example, anhydrous copper sulfate (CuS04), aqueous copper sulfate, copper carbonate (CuC03), or copper oxide. (Cu0). According to a preferred embodiment of the present invention, the composition of the above-mentioned copper plating solution further includes an acid, wherein the acid may be, for example, sulfuric acid. According to another object of the present invention, a method for electroplating copper is provided. At least 14 200532057 includes: firstly, providing a substrate having openings, wherein the openings can be, for example, micron or submicron openings; then, providing a plating solution, the plating solution Contains at least copper ions, gloss agents, inhibitors, and leveling agents, where the glossing agent is a non-simple thiolation & leveling agent is a benzimidyl derivative; and a step of electro-mineralization is performed by submerging the substrate into the plating In the liquid, a current density is applied to the substrate, so that copper ions are deposited in the openings of the substrate. According to a preferred embodiment of the present invention, the aforementioned non-simple thiol compounds, inhibitors and leveling agents have been described as above, and will not be repeated here. According to a preferred embodiment of the present invention, the copper ion is provided by a copper-containing compound, and the copper-containing compound may be, for example, anhydrous sulfuric acid steel, hydrous copper sulfate, copper carbonate, or copper oxide. According to a preferred embodiment of the present invention, the composition of the above-mentioned copper plating solution further includes an acid, wherein the acid may be, for example, sulfuric acid. The additive of the copper electroplating solution of the present invention does not contain dyes, which not only overcomes the problem of pinpoint anti-mine caused by the conventional copper electroplating = medium dye, but also improves the effective concentration of the gloss agent and violates the circumstance. Not sensitive and therefore easier to handle and produce. [Embodiment] The present invention discloses the composition of a copper electroplating solution, which overcomes the problem of pinpoint anti-plating caused by dyes in conventional copper electroplating solutions by using dye-free rhenium, and improves the effective concentration and range of the gloss agent. And reduce the sensitivity of the copper electroplating solution to the flow field. The composition of the copper electroplating solution of the present invention includes at least: copper ions; a glossing agent, /, a light / tincture is a non-simple thiol compound; an inhibitor; and a leveling agent, The leveling agent in 15 200532057 is a benzimidazole derivative. According to a preferred embodiment of the present invention, the copper ion may be provided by a copper-containing compound, and the copper-containing compound may be, for example, anhydrous copper sulfate, aqueous copper sulfate, copper carbonate, or copper oxide, and copper sulfate pentahydrate (CuS04 · 5H2 〇) is better. The concentration of the above copper-containing compound may be between 50 g / L and 250 g / L, and more preferably between 100 g / L and 220 g / L. According to a preferred embodiment of the present invention, the above non-simple thiol compound is an additive without dye, and the structure of the non-simple thiol compound is as follows: (I) ·· XS-γ-Z (I) where X may be For example, the following formula (π), formula (Dish), formula (IV), formula (V), formula (^), formula (通) 'formula (Wai), formula (IX), or formula (X),

N

(Π)

nh2 + (m) (IV)

I h2n——c—— s

H3c I N——C—— h3c ’

(V) 16 (VI) 200532057, S · H2C-N h2c (》 c,

And Y may be, for example, an (CH2) n-alkyl group, where n is an integer between 1 and 5, and Z may be, for example, a COOH, a S03Na, an OH, or an NH2 0. For example, When X in the above formula (I) is, for example, formula (V), Y is, for example, 2005200557a, a linear alkyl group, and z is, for example, -s03Na, the structure of the non-simple thiol compound of the present invention may be, for example, the following formula ( XI):

-NS ^ ~ S—S— (丨 CH2 ^ -S03Na

The structure of the benzimidazole derivative of the present invention may be, for example, the following formula (X n) ·· R3

-N (X Π where R] may be, for example, S03 Na, -NH2, -SH, or -OH, R2 may be, for example, ~ NH ~, -0, or _s, and r3 may be, for example, CN, -COOH,- s〇3Na, mono-OH, mono-NH2 or mono-CH3. The benzo. stilbene derivative of the present invention is a dye-free additive, and its concentration is preferably between 0.1 ppni and 10 ppm. The inhibitor of the invention comprises at least a polyethylene glycol and an electrolyte. The polyethylene glycol may be, for example, polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide (PEO), or polyethylene glycol third octylphenyl ether. (Triton X-405), of course, polyethylene glycol is preferred. 'Where the molecular weight of polyethylene glycol is between 2000 and 14000, generally, the concentration of polyethylene glycol is between 50 ppm to 200 ppm. The above-mentioned electrolyte may be, for example, a halide ion, and a chloride ion is better than 18 200532057. The concentration of the element ion is generally between 10 ppm and 100 ppm, and the concentration is between It is preferably between 50 ppm and 70 ppm. According to a preferred embodiment of the present invention, the composition of the copper electroplating solution further includes at least an acid, wherein the acid may be, for example, sulfuric acid, The concentration of sulfuric acid can be between 18 g / L and 1 50 g / L. According to the above description, the present invention further discloses a method for electroplating copper, which can be used in the process of semiconductor copper and hole-filling electroplating of printed circuit boards. The copper plating solution of the present invention is used for the electroplating step. Since the additives of the copper plating solution of the present invention do not contain dyes, it not only overcomes the phenomenon of pin point resistance to plating, but also is easier to operate and produce. The method of electric copper of the present invention includes at least: Provide a substrate with an opening, and this substrate has been washed with about 3% dilute sulfuric acid and ultrapure water. The opening can be, for example, a micron or submicron blind hole, and the pore diameter of the opening is between 2〇 # m to 500 # m, and the aspect ratio (Aspect Rati) is between 1 and 3. Then 'provide a recording solution, wherein the plating solution contains at least copper ions, gloss agents, inhibitors and A leveling agent, in which the glossing agent is a non-simple thiol compound and the leveling agent is a benzimidazole derivative. After that, a plating step is performed, in which the substrate is immersed in a reference plating solution, and the substrate is used as a cathode. Current density, sinking copper ions In the opening of the substrate, a copper layer is formed in the opening. According to a preferred embodiment of the present invention, the method of electroplating copper of the present invention can be performed in any conventional electroplating system suitable for electroplating copper. For example, Please refer to FIG. 2 and FIG. 2, which are schematic diagrams of a key system according to a preferred embodiment of the present invention. The electroplating system 200 may be, for example, a 1000-liter electroplating tank, including at least a tank body 201 and a power supply system. 203 and anode 205, where anode = 205 is electrically connected to the power supply system 203 through the anode hanging material 207. The anode 19 200532057 205 may be, for example, a soluble anode or an insoluble anode, in which a soluble anode is, for example, a phosphor copper plate, and an insoluble anode is, for example, a titanium plate or a platinum plate. The US material 221 is electrically connected to the power supply system 203 through the cathode hanging material 217, and the 1 base material 221 and the cathode hanging material 217 can be arranged above the tank 20 using a bracket 215, for example. During the electroplating step, the substrate 221 is immersed in the plating solution 223, and the substrate 221 is used as the cathode. The power supply system 203 and the anode 205 are used to apply a current density to the substrate 221, where the current density is between amperes per square foot (A / ft2; ASF) to 30 ASF, and more preferably between 10ASF to 20asf. In addition, during the electroplating process, the temperature in the bath is maintained between about 20 ° C. and about 25 ° C., so that copper ions are deposited in the micro-scale or sub-micro-scale openings of the substrate 221. During the electroplating process, the electroplating system 200 can further include an air pump 231 at the bottom of the tank 201, and the air is stirred at a flow rate of air, such as about 2.5 standard liters (Normal Liter Per Minute; NL / min), through the vent pipe 233. Into the bottom of the tank body 20 1, forced convection occurs in the tank to increase the mass transfer speed of copper ions and various additives. It is worth mentioning that, when the copper plating method of the present invention is applied to copper electroplating, the copper plating solution of the present invention is not sensitive to the direction of the flow field, so it is easier to operate and produce. The following is a more detailed disclosure of the copper electroplating method of the present invention by using several embodiments and the diagrams of FIGS. 3 (a) to 6 (f), but it is not intended to limit the present invention. Any familiarity Those skilled in the art should be able to make some modifications and retouching without departing from the spirit of the present invention. Embodiment 1 According to a preferred embodiment of the present invention, the copper electroplating method of the present invention can be performed at a high current density of 20 200532057. Please refer to FIG. 3 (a) to FIG. 3 (i), which show that according to a preferred embodiment of the present invention, the copper plating solution of the present invention is used to deposit copper in the micron and submicron openings at different current densities. Sectional view of 200 times magnification of layer metallographic microscope. Metallographic microscopes are reflective optical microscopes, which are mainly used to observe non-transmissive test pieces, such as observing the structure of metal surfaces. The light beam focused by the condenser from the light source is reflected by the half-coated silver mirror and irradiated on the 1C substrate through the objective lens. The area of the surface of the 1C substrate perpendicular to the optical axis will reflect the light into the objective lens. Inclinations such as etched grain boundaries or rough parts of the metal surface will reflect light away from the objective lens, and finally be imaged by the eyepiece, showing the microstructure characteristics of the metal surface.凊 Referring to FIGS. 3 (a) to 3 (c), it shows that the copper plating solution of the present invention is used at a current density of about i2 A ”according to a preferred embodiment of the present invention. "105 " m" A 200x magnified cross-sectional view of a metallographic microscope with a copper layer deposited in the blind holes. The results show that the steel filling effect in each blind hole is good. 'Referring to Figures 3 (d) to 3 (f), it shows that the copper plating solution of the present invention is used according to a preferred embodiment of the present invention when the current density is about i 8 and eight lamps, respectively at an aperture of 65. // m, 75 / zm, and 10 m " m's beasts, men and women I " L metallographic layer magnified 200 times sectional view of the metallographic microscope, the results show that the blind hole filled with good steel. Referring to Figures 3 (g) to 3 (i), it shows that according to the present invention, the preferred embodiment uses the copper plating solution of the present invention

When x 芍 approximately 26 ASF, the metallurgical microscope section of 200 times magnification was deposited at the apertures 65 " m, 75 / zm & 105 " ^ 言 7 丨 The microscopic view of the metallurgical layer deposited in the gastric foramen was enlarged. The 21 200532057 copper filling effect in each blind hole is good. Embodiment 2 According to a preferred embodiment of the present invention, when the method of electroplating steel of the present invention is applied, the glossing agent can be performed at a wide range of effective concentrations. Please refer to FIG. 4 (a) to FIG. 4 (f), which show that according to another preferred embodiment of the present invention, the copper plating solution of the present invention is used when the gloss agent is about 10 ppm. ; 200 × magnified cross-section of a metallographic microscope with a copper layer deposited in blind holes in m, 70 // m, 75 / zm, 85 / zm, 95 / zm, and 105 / ztn, the results show the copper filling in each blind hole Works well. Please refer to FIG. 5 (a) to FIG. 5 (f), which show that according to another preferred embodiment of the present invention, the copper plating solution of the present invention is used at a hole diameter of 65/50 when the gloss agent is about 50 ppm. zm, 70 // m, 75 // m, 85 // m, 95 " metallographic microscope magnified 200 times section view of copper layer deposited in blind holes in m and 105 // m 'results show that in each blind hole The copper filling effect is good. Embodiment 3 According to a preferred embodiment of the present invention, when the copper electroplating method of the present invention is applied, copper ions can be performed at a lower effective concentration. Please refer to FIG. 6 (a) to FIG. 6 (f), which show that the concentration of the copper-based mineral liquid using the copper electric ore liquid of the present invention is about 100 g / L according to another preferred embodiment of the present invention. At 200 times, the metallurgical microscope section of the copper deposit layer in the blind holes with apertures of 65μπχ, 70 " m, 75 / zm, 85Am, 95 / zm, and 105 // m were magnified 200 times. The results are shown in When the copper ion concentration is low, the copper filling effect in each blind hole is good. As can be seen from the above-mentioned preferred embodiments of the present invention, the composition of the copper electroplating bath to which the present invention is applied has the advantage of overcoming the problem of pinpoint anti-bonding caused by the dyes in the conventional copper electrolyte 22 200532057 key solution by using dye-free additives , Increase the effective concentration and range of the gloss agent, and reduce the sensitivity of the steel plating solution to the flow field. It can be known from the above-mentioned preferred embodiments of the present invention that the method of applying the electric copper of the present invention has the advantages that the semiconductor copper process and the printed circuit board hole filling and plating process use the copper plating solution of the present invention to perform the plating step. The additives in the plating solution do not contain dyes, which not only overcomes the phenomenon of pin point resistance to plating, but also facilitates operation and production. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make various changes and decorations without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application. [Brief description of the drawing] The following is a brief description of the drawing, which shows an embodiment of the present invention for explanation, wherein: FIG. 1 is a cross-sectional view showing a conventional IC filled metal wire substrate; The drawings are schematic diagrams of a plating system according to a preferred embodiment of the present invention; 'FIGS. 3 (a) to 3 (1) are diagrams showing the use of the copper plating solution of the present invention according to a preferred embodiment of the present invention A cross-sectional view of a metallographic microscope that deposits a copper layer in micron- and sub-micron-sized openings at different current densities is 200 times larger; Figures 4 (a) to 4 (f) show additional A preferred embodiment utilizes the copper electroplating solution of the present invention when the gloss agent is about 10 ounces, and the pores are 65 / zm, 70 / zm, 75 / zm, 85 // m, and 95 / z, respectively. A metallographic microscope with a magnification of 200 times in the hole and / or copper layer ^ m Figures 5 (a) to 5 (f) show a further example according to the present invention using the copper plating solution of the present invention in gloss When the agent is about 5, a preferred implementation * ppm, copper is deposited in blind holes with apertures of 65 // m, 70 / zm, 75 / zm, 85 / zm, 9s, 95, and 105 // m, respectively. A metallographic microscope magnification of 200 times a vertical π π scraped surface; and Figures 6 (a) to 6 (f) show the use of the copper plating solution of the present invention in accordance with yet another preferred embodiment of the present invention. When the concentration of the copper-containing compound is about 100 g / L, the copper layer is deposited in the blind holes with a diameter of 65 // m, 70 0 m, 75 β m, 85 m,% “Cr and 105 μm, respectively. A 200x magnified cross-section view of a metallographic microscope. [Simple description of element representative symbols] 101: substrate 103: blind hole 105: metal layer 111: cavity 113: gap 115: defect-free 200. Electroplating system 201: tank body 203: Power supply system 205: Anode 207 ... Anode hanging material 215: Bracket 217: Cathode hanging material 221 ... Base material 223 ... Electroplating solution 231: Air pump 233: Vent pipe 24

Claims (1)

200532057 Patent application scope 1. Composition of a copper electroplating bath, at least: a copper ion; a brightener, wherein the brightener is a non-simple thiol compound; a suppressor; and a Leveler, wherein the leveler is a benzimidazole derivative (2) The composition of the copper electroplating bath as described in item 1 of the patent application scope, wherein the structure of the non-simple thiol compound is as follows: (I): X- S- Υ- Zn (I) where 5 ×× is selected from formula (Π), formula (melon), formula (IV), formula (V), formula (VI), formula A group consisting of (pass), formula (IX), and formula (X), (Π) ΝΗ〇 + (Π) II Η2N-C— 25 (IV) 200532057 H3C f N—C H3C ’ (V) H2C——N h2c (^ (VI) N——N (VH) (vm) (ix) 26 (X) 200532057 The Y is an (CH2) n-alkyl group, wherein the η is an integer between 1 and 5, and the Z is selected from the group consisting of a COOH, a S03Na, A group consisting of 10Η and 1Η2. 3. The composition of the copper electroplating solution as described in item 1 of the scope of the patent application, wherein the concentration of the gloss agent is between 10 and 100 ppm parts per million (ppm) 0 4 The composition of the copper electroplating solution described in the first item of the scope, wherein the structure of the benzimidazole derivative is as follows (X Π): (X Π) wherein R! Is selected from the group consisting of -S〇3 Na, -NH2, -SH, and -OH, and r2 is selected from the group consisting of _nh-, _〇-and- S — a group consisting of, and the r3 is selected from a group consisting of —cn, —COOH, —S03Na, —oh, —NH2, and —CH3. 5. The composition of the copper electroplating solution as described in item 丨 of the patent application range, wherein the degree of the δ-leveling agent is between 0.1 ppm and 10 ppm. 27 200532057 6. The composition of the copper electroplating solution as described in item 1 of the scope of patent application, wherein the copper ion is provided by a copper-containing compound, and the copper-containing compound is selected from the group consisting of anhydrous copper sulfate (CuS〇4) , A group of hydrous copper sulfate, carbonated steel (CuC03) and copper oxide (CuO). 7. The composition of the copper electroplating solution according to item 6 of the scope of the patent application, wherein the copper-containing compound is copper sulfate pentahydrate (CuS04 · 5H20). 8. The composition of the copper electroplating solution as described in item 6 of the scope of the patent application, wherein the concentration of the copper-containing compound is between 50 grams (g / L) and 250 g / L. 9. The composition of the steel electroplating solution as described in item 6 of the scope of the patent application, wherein the concentration of the copper-containing compound is between 100 g / L and 220 g / L. 10. The composition of the copper plating solution as described in item 1 of the scope of the patent application, wherein the inhibitor comprises at least a polyglycol and an electrolyte. 11. The composition of the copper electroplating bath as described in item 10 of the scope of the patent application, wherein the polyethylene glycol is selected from the group consisting of polyethylene glycol (PEG) and polypropylene glycol (propylene glycol). Glyc0; ppG), 1 ethylene oxide (Polyethylene Oxide; PEO), and polyethylene glycol third octyl phenyl ether (Polyethylene Glycol Tei * t_Octylphenyl Ether; Triton X-405). 28 The group of copper electroplating baths described in 2005200557 is between 2000 and 14000. 12. The group of copper plating solution as described in the item of the patent application No. u 'wherein the molecular weight of polyethylene is between 50 ppm and 200 ppm. 13. If the patent application range is 10%, the concentration of the polyglycol is between 14. As claimed in claim 10, wherein the electrolyte is a halogen ion. Group of copper plating bath 1 5. The composition of the copper electroplating solution as described in item 14 * of the scope of the patent application, wherein the tooth ion is a gas ion. 16. The composition of the copper electroplating solution as described in the scope of the patent application No. 1-4, Le 14, wherein the concentration of the halogen ions is ^ 1 paper / you; 丨 between 10 ppm to 100pprn. The composition of the copper electroplating solution described in item 14 of the scope of the patent application, wherein the concentration of the halide ion is between 50 ppm and 70 ppm. 18 • The composition of the copper plating solution as described in item 1 of the scope of patent application, further comprising at least one acid. 19. The group of copper electroplating baths described in item 18 of the scope of patent application, wherein the acid is sulfuric acid, and the concentration of the acid is between 18 g / L and 50 g / L. 20 · A method for electroplating copper, comprising at least: providing a substrate, wherein the substrate has an opening; providing a plating solution, wherein the plating solution includes at least: a copper ion; a glossing agent, wherein the glossing agent is A non-simple thiol compound; an inhibitor; and a leveling agent, wherein the leveling agent is a benzo miso derivative; performing a plating step, immersing the substrate in the plating solution, and applying the substrate A current density causes the copper ions to be deposited in the opening of the substrate. 2 1 · The method of electroplating copper as described in item 20 of the scope of patent application, wherein the structure of the non-simple thiol compound is as follows: (I) XS-Υ-z (I) where X is selected from the group consisting of A group of formula (π), formula (m), formula (ιν), formula (V), formula (VI), formula (w), formula (view), formula (K), and formula (X), 30 200532057 (Π) NH〇 + I H2 | sj-c- (Π) H3C I N—C H3C ’(IV) (V), person S (VI) (VH) 31 200532057 αχ) (X) 4 Υ is an alkyl group of (CH2) n—, where η is an integer between j and 5, and -0H, and -NH2. Z is selected from -c. 〇H, ~ S03Na, a group of groups. 22. The method of electroplating copper as described in item 20 of the scope of patent application, wherein the concentration of the gloss agent is between 10 ppms and 100 ppm. 23. The method of electroplating copper as described in item 20 of the scope of the patent application, wherein the structure of the benzoimide derivative is as follows (X Mutual): r3 wherein R! is selected from the group consisting of S03 Na, NH2, ~ SH, and -OH, and r2 is selected from the group consisting of nh-Q-and S A group, and the r3 is selected from the group consisting of -CN, -C00H, -S03Na, -OH, -NH2, and -CH3. 24. The method of electroplating copper according to item 20 of the scope of patent application, wherein the concentration of the leveling agent is between 0.1 ppm and 10 ppm. 25. The method for electroplating copper as described in item 20 of the scope of the patent application, wherein the copper ion is provided by a copper-containing compound, and the copper-containing compound is selected from the group consisting of anhydrous copper sulfate, copper hydroxide and copper carbonate. And a group of copper oxides. 26. The method of electroplating copper according to item 25 of the scope of application for a patent, wherein the copper-containing compound is copper sulfate pentahydrate. 27. The method of electro-mineral copper as described in item 25 of the Shenyan patent, wherein the concentration of the copper-containing compound is between 50 g / L and 250 g / L. 28. The method of electroplating copper as described in item 25 of the scope of patent application, wherein the concentration of the copper-containing compound is between 100 g / L and 220 g / L ·. As described in the method of claim 20 for patenting the scope of the patent for the electro-mineral copper, the '4 inhibitor includes at least a polyglycol and an electrolyte. 30. According to the method of electroplating copper described in item 29 of the scope of patent application, Yazhongzhong polyglycol is selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol 33 200532057 (PPG), and polyethylene oxide (PEO ), And a group consisting of polyethylene glycol third octylphenyl ether (Triton X-405). 3 1. The method of electroplating copper as described in item 29 of the scope of patent application, wherein the molecular weight of the polyethylene glycol is between 2000 and 14,000. 32. The method of electroplating copper as described in item 29 of the scope of patent application, wherein the concentration of the polyglycol is between 50 ppm and 200 ppm. 33. The method of electroplating copper as described in item 29 of the scope of patent application, wherein the electrolyte is a halogen ion. 34. The method of electroplating copper as described in item 33 of the application for a kiss kiss patent, wherein the halide ion is a gas ion. The method of electroplating copper according to item 33 is between 10 ppm and 100 ppm. 3 5 · As claimed in the patent scope of $, where the concentration of i element ions is between 3 6 The method of electroplating copper described in item 33 is between 50 ppm and 70 ppm. The method of electroplating copper described in item 20, 37. As described in the scope of patent application No. 2 (where the electroplating solution at least contains-@ 200532057 3 8 · The method of electroplating copper described in item 37 of the scope of patent application, where the The acid is sulfuric acid, and the concentration of the acid is between 18 g / L and 1 50 g / L ° 39. The method of electroplating copper as described in item 20 of the Shenyan patent scope, wherein the The current density ranges from 10 amperes per square foot (A / ft2; ASF) to 30 ASF 〇40. The method of electro-mineral copper described in item 20 of the patent application scope, wherein the current density ranges from 10 ASF to 20 ASF. 41. The method of electric copper according to item 2G of the patent scope, wherein the opening is selected from a group consisting of one micron-sized blind hole and one micron-level blind hole. 35