TWI320062B - Composition for copper electroplating solution - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a composition of a copper plating bath, and more particularly to a composition of a copper plating bath for a dye-free additive. [Prior Art] With the current miniaturization and versatility of electronic products, traditional wafer (Wafer) and integrated circuit (Integrated Circuit; 1C) package substrate (ic

Packaging Substrate) Processes are constantly being updated. Especially after the process of Ball Grid Array (BGA) and Chip Scale Packaging (CSP) became mainstream, the size of the IC substrate became more and more urgent, and the line pitch was also shrinking. To place more electronic components on a smaller area. Holes (vla) and wire trenches for secondary or micro-inner layers in response to current 1C steel process technology and high density internal connections (HDI) for printed circuit boards (PritUed circuit B〇ard, PCB) ) The metal copper material needs to be filled by electroplating. When filling, it must be done by moving up the bottom of the hole (B〇tt〇m Up) or so-called super-filling (Super-FUlmg) to avoid the occurrence of voids (v〇id) or gaps. At present, there are usually two ways to fill the copper wire and the via hole by electroplating. The physical method of using pulse or positive and negative pulse (Pujse with ...1"6) current to achieve the phenomenon of "upward movement of the bottom of the hole." It is a chemical method to add multiple additives in the plating solution, using DC current to reach the hole 1320069.

[95. 6 Filling effect with the bottom up. At present, most of the research and use of the latter is in academic or industrial circles. Therefore, most of the academic copper ore technology is limited to the wafer level electroplating process. Since the difference between the 1C substrate and the wafer is mainly due to the size of the pore size, the basic reaction mechanism should be similar. Furthermore, since the pore size of the 1C substrate is large, there are many factors to be considered (for example, convection, mass transfer), which is more complicated than the wafer electroplating process. Referring to Fig. 1, there is shown a cross-sectional view of a conventional Ic substrate filled with a metal wire. Using a plating fill process, a metal layer 1 〇 5, such as a copper layer, is filled into the micron or submicron openings of the 1C substrate 101, such as in the blind vias 1 〇 3, which causes the filled metal layer 105 to be, for example, non-conformal ( Anti-Conformal), Conformal and Super-Filling are three possible ways to deposit. When depositing in a non-conformal manner, voids are generated on the other hand, and when depositing in a conformal manner, the metal layer 1〇5 is formed in a uniform thickness, so that a slit 113 is finally formed. Therefore, the blind hole 1 〇 3 can be completely filled to the defect-free 11 5 only by the super-filling method, and the cavity 111 and the slit 113 are not generated. The deposition of the former two methods cannot completely fill the blind holes 1 〇 3. The resulting voids and gaps 13 affect the signal transmission rate and reduce the reliability of the wafer. In order to overcome the shortcomings of the prior art, it is taught in U.S. Patent Nos. 3,267, 〇1 与 and 3,288,690, the addition of several additives during the electrowinning process, that is, the copper deposition rate at the bottom of the hole is greater than the surface. The phenomenon of moving up the bottom of the hole to improve the problem of voids and gaps. These two patents use three types of additives, such as Brightener, Suppressor and Leveler, to produce a 1320062 filling effect with the bottom of the hole up, and the above formula has been used until now. In the case of hole-fill plating, conventionally known brighteners or accelerators (Accelerator) Mercapto series of compounds have two kinds, one is bis(3-supply propyl) disulfide (Bis (3) -Sulfopropyl) Disulfide ; SPS)' The other is 3-mercapto-l-Propane Sulfonate (MPS). SPS and MPS will be converted into each other during electroplating, 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 electroplating reaction, and accelerate the deposition of copper. Furthermore, 'SPS and MPS will strongly adsorb on the surface of the electrode during the electroplating reaction, in which SPS will be rapidly reduced to MPS' and MPS will help the divalent copper ions to be reduced to monovalent steel ions and oxidized to sps. The rate of formation of monovalent copper on the surface of the electrode. A composition of an electric forging liquid, wherein the composition of the electroplating solution is used in the composition of the electroplating solution, is disclosed in U.S. Patent Nos. 661,191, 6,350,366, and 6,113,771. The substituted Phthalocyanine compound AlcUn Blue is used as a brightener in copper electroplating, and it needs to be blended with other additives to be suitable for the hole-filling process of semiconductors, and is not suitable for printed circuits. The hole filling electric forging process of the board. The inhibitor or carrier (Carrie® can significantly reduce the copper deposition rate of the electric forging steel reaction) and commonly used inhibitors such as polyethylene glycol (P〇lyethylene Glyco1; PEG) and chloride ions. PEG and chloride ions simultaneously = single = strong: inhibits the deposition of copper ions, but another literature shows that the gas ions will accelerate the reduction of steel ions when they exist alone. 10 1320062 The leveling agent can effectively increase the effective range concentration of the accelerator and reduce the generation of voids. It also has the function of smoothing the surface to be plated. The conventional leveling agent (Leve is an organic nitrogen-containing heterocyclic compound such as a compound of azole compound), and has an N+ uterine energy group, so it is affected by current distribution. It is preferentially adsorbed in the high current density region to suppress the copper deposition rate. The more commonly used leveling agents are, for example, Janus Green B (Jgb) and Benzotriazole (BTA·). Most of the electroplating solution formulations in the academic community and the industry today adopt the above multiple additive formulations. However, the multi-additive formulation has the following disadvantages. First, the above-mentioned commonly used leveling agents all contain dyes. When electroplating, the dye is easily decomposed to produce an insoluble organic substance, and the insoluble organic substance may be stained on the surface of the wafer or the PCB, resulting in pin-point plating resistance (p-heart effect). Second, the accelerator sps The effective concentration of Mps is quite low and the range is very narrow, ranging from about 10,000 parts per million (p_per Mi 〇n; ppm) 〇3 to about 2.0 ppm, making it difficult to control and analyze during production. The conventional electric seam formula is sensitive to fluid mechanics and must be effectively filled and filled in a specific electroplating flow field. In view of the above, it is necessary to propose a composition of a copper electroplating solution to overcome the conventional copper electrowinning. The dye in the liquid causes the needle point to resist the mineral problem, enhances the effective concentration and range of the brightener, and reduces the sensitivity of the copper plating solution to the direction of the flow field. [Invention] Therefore, "one of the objects of the present invention is to provide - The composition of the copper plating solution overcomes the problem of pinpoint resistance caused by the dye 1320062 in the conventional steel plating solution by the dye-free additive, and enhances the brightness of the gloss agent. And reducing the sensitivity of the steel plating solution to the flow field. Another object of the present invention is to provide a method for electroplating copper, which can be carried out by using the copper plating solution of the present invention in the semiconductor copper process and the printed circuit board hole-filling process. Since the additive of the copper plating solution of the present invention does not contain a dye, it not only overcomes the phenomenon of pin-point plating resistance, but also is easier to handle and produce. According to the above object of the present invention, a composition of a copper plating solution comprising at least copper ions is provided; a glossing agent, wherein the brightening agent is a non-simple thiol compound; an inhibitor; and a leveling agent, wherein the leveling agent is a benimidazole derivative (Koimidazole Derivative) 0. According to a preferred embodiment of the present invention, the above non-simple thiol compound The structure is as follows: (X): XS-γ-z (I) wherein 'X can be, for example, the following formula (Π), formula (dish), formula (IV), formula (V), formula (VI), formula (VD) ), (Shan), (IX), or (X) '

Nh2+ I H2N-c (H) (nr) J2 1320062

, 0-N H2C\s/C, s-(five)

N-N HC[ /C, (W)

, SX, s-

N-N HS" /C. (Μ) 'S', S-

N-N , C: two C, 's- αχ)

N-N 'c\ /c\. — ( X ) H 3 C 's' s - 13 1320062 and Y may, for example, be an alkyl group of —(CH 2 ) n — wherein n is an integer between 1 and 5, and Ζ may be, for example, —c〇〇H , one S03Na, one ΟΗ, or one NH2. According to a preferred embodiment of the present invention, the structure of the above benzimidazole derivative may be, for example, the following formula:

-N

(XU

Ri where 'I can be, for example, -S03 Na, _NH2, one SH or one 〇H, R2 can be, for example, -NH -, ~ 0 ~ or one S -, and R3 can be, for example, a CN, a COOH, - S03Na, - 〇 H, -NH2 or -CH3. According to a preferred embodiment of the present invention, the inhibitor comprises at least a polyglycol and an electrolyte, and the polyglycol may be, for example, polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide Oxide, PEO. ) or polyethylene glycol octyl phenyl ether (p〇lyethylene)

Glycol Tert-Octylphenyl Ether; Triton X-405). The electrolyte is a halogen ion. According to a preferred embodiment of the present invention, the above-mentioned steel 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 (CuC〇3), or copper oxide (Cu). 〇). In accordance with a preferred embodiment of the present invention, the composition of the copper plating bath described above further comprises at least an acid, wherein the acid may be, for example, sulfuric acid. According to another object of the present invention, a method of electroplating copper is provided, comprising at least: firstly, providing a substrate having an opening, wherein the opening can be, for example, a micron 1320062 or a submicron opening; then, providing a plating solution, the plating solution At least copper ions, a gloss agent, an inhibitor, and a leveling agent, wherein the gloss agent is a non-simple thiol compound and the leveling agent is a benzimidazole derivative; and the electroplating step is performed by immersing the substrate in the plating solution A current density is applied to deposit copper ions in the openings of the substrate. According to a preferred embodiment of the present invention, the above-mentioned non-simple thiol compound, inhibitor and leveling agent are as described above, and are not described herein again. 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, aqueous copper sulfate, copper carbonate, or copper oxide. According to a preferred embodiment of the present invention, the composition of the above-mentioned steel plating solution further contains at least acid ', wherein the acid may be, for example, sulfuric acid. The additive of the copper plating solution of the invention does not contain the dye, not only overcomes the problem of pin-point plating resistance caused by the dye in the conventional copper plating solution, but also improves the effective concentration and range of the gloss agent, and the copper plating solution of the invention is not sensitive to the flow field direction. Therefore, it is easier to operate and produce. [Embodiment] The present invention discloses a composition of a copper plating solution, which overcomes the problem of needle-point anti-mine caused by dyes in a conventional copper-electric ore by the dye-free additive, and improves the effective concentration of the gloss agent and Range and reduce the sensitivity of the steel plating solution to the flow field. The composition of the steel plating solution of the present invention comprises at least: copper ions; a gloss agent wherein the gloss agent is a non-simple thiol compound; an inhibitor; and a leveling agent wherein the leveling agent is a benzimidazole derivative. 15 1320062 According to a preferred embodiment of the present month, copper ions may be provided by a copper-containing compound and the steel-containing compound may be, for example, anhydrous copper sulfate, aqueous copper sulfate, copper carbonate, or copper oxide, but with copper sulfate pentahydrate (CuS〇4. 5η2〇) is preferred. The concentration of the above a copper compound may be between 5 〇 g/L and 25 〇 g/L, and preferably between 100 g/L and 220 g/L. According to the preferred embodiment of the present invention, the non-simple thiol compound is a dye-free additive, and the structure of the non-simple thiol compound is as follows: (I) X-s-Y-z (I) Wherein X may be, for example, the following formula (Π), formula (m), formula (IV), formula (v), formula (VI), formula w, formula (10), formula (IX), or formula (X),

H2N--2-- (melon)

S

H3c I ":N-C—— (IV) H3C’

S- (V) 16 (VI) 1320062

HS

(νπΐ) h2n

(IX) H3c

s (X) and Y may, for example, be an alkyl group of (CH2)n-, wherein n is an integer between and Z may be, for example, a COOH, a S03Na, or a NH2.

For example, when X in the above formula (I) is, for example, the formula (V), Y 1 to 5 OH, for example, 17 1320062 C5 linear alkyl group, and z is, for example, _s〇3Na, the present invention is not simple. The structure of the thiol compound can be, for example, the following formula (XI):

SS (〇H2^-S03Na (XI) The structure of the stupid imidazole derivative of the present invention may be, for example, the following formula (χ π ): r3 (X π wherein Ri may be, for example, a S03 Na, an NH 2 , a SH or a fluorene H, R2 may, for example, be NH—, _ 〇 _ or —s _, and R 3 may be, for example, _ CN, _ COOH, a S 〇 3Na ' — 〇 H, an NH 2 or _ CH 3 . The organism is a dye-free additive, preferably having a concentration of between 0.1 ppm and (7) Ppm. The inhibitor of the present invention comprises at least a polyglycol and an electrolyte. The polyglycol can be, for example, polyethylene glycol (pEG), Polypropylene glycol (PPG), polyethylene oxide (PEO), or polyethylene glycol octyl phenyl ether (Triton X-405), but polyethylene glycol is preferred 'the molecular weight of polyethylene glycol Between 2000 and 14000. Generally, the concentration of 'polyglycol is between 50 ppm and 200 ppm. The above electrolyte can be, for example, a halogen ion, and the chloride ion is better than 1320062. The concentration is generally between i 〇 ppm and 1 〇〇 ppm, and the concentration is preferably between 50 ppm and 70 ppm. According to the present invention, a preferred embodiment For example, the composition of the copper plating solution further contains at least an acid, wherein the acid may be, for example, sulfuric acid, and the concentration of sulfuric acid may be between i8 and 150 g/L. As described above, the present invention further discloses a method of electroplating copper, The electroplating step can be carried out by using the copper electroplating solution of the invention in the semiconductor copper process and the printed circuit board hole-filling process. Since the additive of the copper electroplating solution of the invention does not contain the dye 2, it not only overcomes the pin-point anti-plating phenomenon, but is easier to operate and The method of electroplating copper of the present invention comprises at least: firstly, providing a substrate having an opening which has been washed with about 3% dilute sulfuric acid pickling and ultrapure water, wherein the opening can be, for example, micron or Submicron-level blind holes, and the aperture of the opening; between 2 and 500 from m, and the aspect ratio between i and 3. Next, a plating solution is provided, wherein the plating solution contains at least Copper ion, gloss agent 'inhibitor and leveling agent' wherein the brightening agent is a non-simple thiol compound, and the leveling agent is a benzimidazole derivative. Thereafter, the electroplating step is performed by immersing the substrate in an electric forging liquid. For the cathode, a current density is applied to the substrate to deposit copper ions in the opening of the substrate, thereby forming a steel layer in the opening. According to a preferred embodiment of the present invention, the method for electroplating copper of the present invention can be used in = For example, please refer to: _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The power supply system 203 and the anode 205 are included in the tank body, wherein the anode and cathode anode materials 207 are electrically connected to the power supply system 2〇3. The anode 19 1320062 205 can be, for example, a soluble anode or an insoluble anode, wherein the soluble anode is, for example, a copper plate, and the insoluble anode is, for example, a titanium sheet or a platinum sheet. The substrate is electrically connected to the power supply system 2〇3 by the cathode material 217, and the substrate 221 and the cathode material 217 can be disposed above the tank by, for example, the bracket 215. When the electroplating step is performed, the substrate 221 is immersed in the plating solution M3, and the substrate 221 is used as a cathode, and a current density is applied to the substrate 22i by the power supply system 203 and the anode 205, wherein the current density is between ampere/ampere/ampere (A/ft2; ASF) to 30ASF, and preferably between 1 octet and 2 october. In addition, during the electroplating process, the bath temperature is maintained between about and about 25 < t, causing copper ions to deposit in the fresh or sub-micrometer-scale openings of the substrate 221. 〆In the electroplating process, the electroplating system 2 can further provide an air pump 23 at the bottom of the tank body 2〇 and agitate the air with air through the vent tube 233, for example, about 2.5 standard liters per minute (N〇rmal Liter per Minute; NL/min) Drives into the bottom of the tank 20 1 to create forced convection in the tank to increase the mass transfer rate of copper ions and additives. It is worth mentioning that the copper electroplating solution of the present invention is insensitive to the flow field direction when the copper electroplating solution of the present invention is used for the electroplating of copper. Therefore, it is easier to handle and produce. The method for electroplating copper of the present invention is further disclosed in the following embodiments in conjunction with the drawings of Figures 3(a) through 6(f), but it is not intended to limit the invention to any familiarity. The skilled person can be used as a slight change and refinement without departing from the spirit of the invention. Embodiment 1 According to a preferred embodiment of the present invention, the method of electroplating copper of the present invention can be carried out under the modified high current density of 95. 9·β. Referring to Figures 3(a) through 3(i), there is shown a copper plating solution of the present invention for depositing copper in micron and submicron openings at different current densities in accordance with a preferred embodiment of the present invention. The metallographic microscope of the layer is enlarged by 200 times. A metallographic microscope, a reflective optical microscope, is mainly used to observe test pieces that cannot be transmitted through light, such as observing the structure of a metal surface. The light beam that is focused by the condensing lens from the light source is reflected by the semi-coated silver mirror and then irradiated on the IC substrate through the objective lens. The area of the surface of the IC substrate perpendicular to the optical axis = the light is reflected into the objective lens, which is the bright area, and the tilt For example, the grain boundary of the engraved or the rough part of the metal surface will reflect the light and behave by the eyepiece, and the microstructure of the metal surface will be revealed. In addition to the brothers, please refer to the figures S3(a) to (3), which show the use of the copper (4) of the present invention at a current density of about 12 asf') at 25 ° C according to the embodiment of the present invention. The metallographic microscope of the copper layer of the aperture 65^, 75 core and 1〇5 core is enlarged and the cross-sectional view is enlarged, and the copper filling effect in the blind hole is good. The composition of *,,..., electricity and liquid contains at least copper sulfate, a sulfuric acid agent and a leveling agent, wherein the alum is made well for 1 71 h, and the concentration of methotrexate copper is 〇g/L; sulfuric acid The degree is 120g/L; the inhibitor A pFn, the eight a county is inferior, the machine is the m agent, the PEG 'molecular weight is 6 〇〇〇 PPm; the gloss agent's snoring helmet is 15 疋 / morning At 40 ppm, its molecular structure is as follows H2N-CS-

fCH 2 ~S〇3Na The structure of the knife is as follows: The concentration of the leveling agent is 5 ppm 21

Amendment a

NaQ3S

NH; According to an embodiment of the present invention, the composition of the copper plating solution may contain copper sulfate in the range of 100 to 220 g/L. The concentration of sulfuric acid is 20 to 150 g/L. The inhibitor may be PEG and its derivatives, having a molecular weight between 4 〇 0 〇 and ι 5 , and a degree of collapse of 50 to 260 ppm. The concentration of the gloss agent is between 1 〇 and 5 〇, and the molecular structure is X-S-Y-Z, where X is as described above for (h); Y can be one (CH2)n-, n=l~5; Z can be a s〇3Na. The leveling agent is a benzimidazole derivative, and the concentration is preferably between 〇 ppm and 1 〇 ppm. The molecular structure thereof can be referred to the above (χπ) formula. R[ can be -NH2, r2 is -NH-, and R3 can be -s〇3Na. Referring to Figures 3(d) through 3(f), there is shown a copper electroplating solution using a copper electroplating solution having a current density of about 18 asf and a temperature of 65 Å, respectively, in accordance with a preferred embodiment of the present invention. Blind hole of m, 75//m and ι〇5: The metallographic microscope of the deposited steel layer is enlarged by 2〇〇 times, and the results show that the copper filling effect in each blind hole is good. (g) _, 4, Yang Xiao is very similar to the winter invention. The preferred embodiment uses the above copper plating solution at a current density of about Μ A 卯 and 度 listening to 'optical apertures...m, 75//m& 1〇5 A magnified cross-sectional view of the metallographic microscope of the deposited copper layer of the heart results in a good copper filling effect in the pores. Embodiment 2 22 I320Q62 ^ Ά q ^ .95. 9. 6 · According to a preferred embodiment of the present invention, When the method of electroplating copper of the present invention is applied, the 'gloss agent can be carried out in a wide range of effective concentrations and ranges. Please refer to Figures 4(4) to 4(f), which show the use of the present invention in accordance with another preferred embodiment of the present invention. The copper plating solution of the invention has a gloss agent of 1 〇 ppm, a current density of eight orders, and a temperature, respectively, at 65 Mm, 7 〇 " m,... The metallographic microscope of the deposited copper layer in the blind holes of m 85^, 95/zm and l〇5/Zm is magnified _ times. The j-side image shows that the copper filling effect in each blind hole is good. Among them, the copper plating solution The composition comprises at least copper sulfate, sulfuric acid, an inhibitor, a coating agent and a leveling agent, wherein the concentration of copper sulfate is i8〇g/L, the spread of sulfur I is 120g/L; the inhibitor is PEG, and the molecular weight is 4〇〇〇, the concentration is 200 ppm, the concentration of the brightener is 1 〇卯 melon, and its molecular structure is as follows

S——S—(CH2^-S03Na leveling agent is at a concentration of i ppm, and its molecular structure is as follows: h2n

•N Ό

SH According to an embodiment of the present invention, the composition of the steel plating solution may have a concentration of sulfuric acid steel of from 100 to 220 g/L. The concentration of sulfuric acid is from 2 丨 to 丨 50 g/L. It inhibits PEG and its derivatives with a molecular weight between 4 and 15 Å and a temperature of 50 to 250 ppm. The concentration of the gloss agent is 10 ppm, and the molecular structural formula is X~s-Y-Z, wherein X is as described above (Π); Y can be 23 1320062 ΕΓ -(CH2)n-, n=1~ 5; z can be _ s 〇 3Na. The bismuth is a benzoxanthene derivative, and the concentration is preferably between 0.1 ppm and 10 ppm, and the molecular structure thereof can be referred to the above (X Π) formula. Ri can be -NH2, & is two NH-, and R3 can be -s〇3Na. Referring to FIGS. 5(a) to 5(f), there is shown a copper electroplating solution according to still another preferred embodiment of the present invention, the composition comprising at least copper sulfate, sulfuric acid, an inhibitor, and a brightener. And the leveling agent β-copper sulfate concentration g/L; the concentration of sulfuric acid is 12〇g/L; the inhibitor is pEG, the molecular weight is 4〇〇〇, the concentration is 200ppm; the concentration of the brightener is 5〇ppm, the molecule Structural formula

The leveling agent has a concentration of 1 ppm and its molecular structure is as follows: -Ν 0' Reuse the same electroplating copper method as described above, at a current density of 18 ASF, and a coverage of 25, respectively, at a pore size of 65 / / m, 70 " m, 75 " m, 8 5 " rxi, 9 5 // m χς ., and the metallographic microscope of the deposited steel layer in the blind hole of l〇5//m is magnified 200 times The results show that the copper filling effect in each blind hole is good. , people 24

1320062-, according to the present invention - a preferred embodiment, the copper ion can be applied at a lower effective concentration when the method of electroplating copper of the present invention is applied. Please refer to FIGS. 6(a) to 6(f) for the use of the present steel plating solution at a current density of 28 ASF and a temperature of 2 rc at a pore diameter of 65_, 7 according to still another preferred embodiment of the present invention. 〇^, 7_, 85_, 95 hearts and 1〇; ^ The metallographic microscope of the copper layer deposited in the blind hole is enlarged by 2〇〇 times, and the result shows that the copper in each blind hole is at the low copper ion concentration. The filling effect is good. . Wherein, the composition of the steel plating solution comprises sulfuric acid steel, sulfuric acid, an inhibitor, a brightener and a leveling agent. The concentration of copper sulfate is just g/L; the old concentration is 1 120g/L, the inhibitor is pEG, the molecular weight is 1〇〇〇〇, the concentration is (9), the concentration of the brightener is I 〇ppm, and its molecular structure The formula is as follows: H+ h2n- -c - S-CH, -S〇3Na leveling agent is 5 ppm, and its molecular structure is as follows - Ν According to an embodiment of the present invention, the composition of the copper plating solution contains sulfuric acid The concentration of copper is 100 g/L. The concentration of sulfuric acid is 20 to 150 g/L. The inhibitor may be PEG and its derivatives having a molecular weight of from 4 to ι 5 浓度 and a concentration of from 50 to 250 PPm. The concentration of the brightener is 1 〇 ppm, and the molecular structural formula is x-s_Y-Z, wherein X is as defined above (π); γ can be -, 25 1320062 n = l~5; Z can be SOsNa. The leveling agent is a benzimidazole derivative, and the concentration is preferably between <1 i·1 ppm i 〇 ppm. The molecular structure thereof can be referred to the Un) formula described above. Rl can be -NH2, R2 is - while _, and R3 can be an S〇3Na. It can be seen from the above preferred embodiments of the present invention that the use of the copper electroplating solution of the present invention has the advantages of overcoming the problem of pin-point plating resistance caused by the dye in the conventional copper electric clock liquid by the dye-free additive. Improve the effective concentration and range of the brightener and reduce the sensitivity of the copper plating solution to the flow field. According to the preferred embodiment of the present invention, the method for applying the copper plating of the present invention has the advantages of performing the electroplating step using the copper electroplating solution of the present invention in the semiconductor copper process and the printed circuit board hole-filling process, due to the copper plating of the present invention. The liquid additive does not contain dyes, which not only overcomes the phenomenon of pin-point plating resistance, but also makes it easier to manufacture and produce. Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS The following is a brief description of the drawings, which show the embodiments of the present invention, wherein: FIG. 1 is a cross-sectional view showing a ic substrate filled with a metal wire by a conventional technique; 2 is a schematic diagram of a 26 l32〇〇62 plating system according to a preferred embodiment of the present invention; FIGS. 3(4) to 3(1) are diagrams showing different copper plating solutions according to the present invention. The current density is magnified 2 times by the metallographic microscope of the micron-level and the second micro- and the opening t-deposited copper layer; FIGS. 4(4) to 4(f) show the use of the copper electro-optic according to the invention according to another example of the present invention. When the luster is about 1 〇ppm, the metallographic microscope of the copper layer deposited in the blind holes of 65^, 7〇/^, 75_, 85^, 95 and 105_ is enlarged by 2 (10) times. Fig. 5(4) to Fig. 5 (Fig. 5 shows a copper electroless ore according to the present invention, preferably in the case where the gloss agent is about ¥, respectively, in the apertures 65"m, 70/zrn, 〇c V 75" m, 85 " m, 95 hearts and 10" section of the metallographic microscope of the deposited copper layer in a blind hole magnified 200 times; and pictures 6 (a) to 6 (f) show another according to the present invention Preferably, the copper plating solution of the present invention has a concentration of about _: s in the copper-containing compound, respectively, in the pore diameters of 65 "m, 7 〇 " m, 75 " m, 85 " m and 1 〇 5 & q Uot; metallographic microscope of deposited steel layer in the blind hole of m. 2〇: face diagram d [Complete description of component symbol] 101: substrate 103: blind hole 105 metal layer 111: cavity 113 200 slit plating system 115 201 : No defect: Tank body 203 Power supply system 205 : Anode 27 1320062 207 : 217 : 223 : 233 : Anode hanging material 215 : Bracket cathode hanging material 221 : Substrate plating solution 231 : Air pump vent pipe

28

Claims (1)

1320062-_ Amendment 1-------MI.J 拾.,.Shen Lianquan Wei. Turn: I A composition of copper electro-mineral liquid, comprising at least: a copper-containing compound with a concentration of between liters per liter 50 grams (g / L) to 250 g / L; a brightener (Brightener), the concentration is between parts per million (Parts Per Million; ppm) i 〇 to 1 〇〇 ppm, where the gloss The agent is a non-simple thiol compound having the following formula (I): XSYZ (I) wherein the X is selected from the group consisting of formula (Π), formula (gu), formula (IV), formula (V), a group consisting of formula (VI), formula (W), formula (νπΐ), formula (IX), and formula (X); 29 1320062 N (V) , S, S- H2C I/C' (VI) , sx 'S- NN HCC /C. , s- (W) (M) HS, , S- (ix) h2n "S — NN (X) , s- the Y is an alkyl group of (CH 2 ) n — wherein n is an integer between 1 and 5, and 30 1320062. The Z series is selected from —c〇〇 h, a group consisting of s〇3Na, OH, and -NH2; a suppressor (Suppressor) with a concentration between 5〇ppm and 200ppm; and a leveler (Leveler) Between 1 ppm and 10 ppm, wherein the leveling agent is a Benzimidazole Derivative having a structure of the following formula (χ)Ι: Rs (X Π ) Ri wherein 'the Ri is selected from a group consisting of -S03 Na, a NH2, a SH and an OH' is selected from a group consisting of a NH ~, a Ο - and - s - and the R3 is selected from It consists of a group of CN, -COOH, a S03Na, ~ 〇H, a NH2 and a CH3. 2. The composition of a copper electroplating bath according to claim 1, wherein the copper-containing compound is selected from the group consisting of anhydrous copper sulfate (CuS04), aqueous copper sulfate, copper carbonate (CuC03), and copper oxide (CuO). ) is a group of people. 3. The composition of the copper plating solution according to claim 2, wherein the copper-containing compound is copper sulfate pentahydrate (CuS04. 5H20). 31 1320062 4. The composition of the copper electricity liquid according to claim 2, wherein the concentration of the copper-containing compound is between 1 〇〇g/L and 220 g/L. The composition of the copper bell liquid of the first aspect of the invention, wherein the inhibitor comprises at least a polyglycol and an electrolyte. 6. The composition of the copper plating solution according to claim 5, wherein the polyglycol is selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), poly A group consisting of ethylene oxide (PEO) and polyethylene glycol octyl phenyl ether (Polyethylene Glycol Tert-Octylphenyl Ether; Triton X-405). 7. The composition of the copper electroplating bath of claim 6, wherein the polyethylene glycol has a molecular weight of between 2,000 and 14,000. 8. The composition of a copper electroplating bath as claimed in claim 10, wherein the electrolyte is a halogen ion. 9. The composition of a copper electroplating bath as described in claim 8 wherein the dentate ion is a chloride ion. 32 1320062 ίο. The composition of the copper electroplating solution of claim 8, wherein the concentration of the halogen ion is between 10 ppm and 1 Torr. Π The composition of the steel plating solution as described in claim 8 of the patent application, wherein the concentration of the dentate ion is between 50 ppm and 70 ppm. 12. The composition of a copper electroplating bath as described in the scope of claim 2, further comprising at least one acid. 13. The composition of the copper electroplating bath as described in claim 12, wherein the acid is sulfuric acid and the concentration of the acid is between 18 g/L and 15 g/L. 14. A method of electro-recording steel, comprising: providing a substrate 'wherein the substrate has an opening; providing a plating solution' wherein the plating solution comprises at least: a copper-containing compound having a concentration of 50 g/L to Between 250 g/L; a glossing agent, the concentration is between 10 ppm and 100 ppm, wherein the brightening agent is a non-simple sterol compound having the structure of the following formula (I) ·· XSYZ (I) 33 1320062 The X is selected from the group consisting of formula (Π), formula (dish), formula (IV), formula (V), formula (VI), formula (VII), formula (er), formula (IX), and formula ( X) a group of constituents; Ηη2+ I η2ν——c— (Π ) (Π) (IV) H3C I —C H3cx (V) H2C——N H2c{ 3C' (VI) s' , s- (VH) 34 1320062 HS N-N (Μ) h2n (ix) h3c (X) The Y is an alkyl group of (CH2)n-, wherein the n is between 1 and 5, and the Z is selected from the group consisting of a COOH, a S03Na, an OH, And a group consisting of -NH2; an inhibitor with a concentration between 50 ppm and 200 ppm; and a leveling agent at a concentration between 0. 1 ppm and 10 ppm, wherein the leveling agent A A benzimidazole derivative having the structure of the following formula (X JJ ): r3 Λ (X Π Ri wherein the Ri is selected from the group consisting of -S〇3 Na, a NH2'-SH and 35 1320062-OH a group, the & is selected from a group consisting of -nh-, _〇-, and an S-, and the r3 is selected from _cN, -C00H, -S03Na, -〇H, -NH2 And a group consisting of -CH3; performing an electroplating step of immersing the substrate in the plating solution, applying a current density to the substrate, and depositing the copper ions in the opening of the substrate. The method of electroplating copper according to claim 14, wherein the copper-containing compound is selected from the group consisting of anhydrous copper sulfate, aqueous copper sulfate, copper carbonate and copper oxide. 16. The method of electroplating copper according to claim 4, wherein the aqueous copper sulfate is copper sulfate pentahydrate. 17_The method of electroplating copper according to claim 14 The method of the copper-containing compound is between 100 g/L and 220 g/L. 18. The method of electroplating copper according to claim 14, wherein the inhibitor comprises at least a polyglycol and a 19. The method of electroplating copper according to claim 18, wherein the polyglycol is selected from the group consisting of polyethylene glycol (peg), polypropylene glycol (PPG), and polyethylene oxide (PEO). And a group consisting of polyethylene glycol tert-octylphenyl ether (Triton X-405). 36 1320062 20 · Method for electrowinning copper as described in claim ip. The molecular weight of the alcohol is between 200 and 14,000. The method of electroplating copper according to claim 18, wherein the concentration of the polyglycol is between 50 ppm and 200 ppm. The method of electroplating copper according to claim 18, wherein the electrolyte is halogen 23. The method of electroplating copper according to claim 22, wherein the dentate ion is a gas ion. 24. The method of electroplating copper according to claim 22, wherein the tooth is The concentration of the cation ion is between 1 〇叩 and 1 〇〇 ppm. 25. The method of the electric bell copper according to the 22nd item of the Shenjing patent range, wherein the concentration of the sinosin ion is between 50 Between ppm and 70 ppm. 26. The method of claim 4, wherein the electrocalyptus further comprises at least one acid. 27. The method of claim 4, wherein the acid is sulfuric acid and the concentration of the acid is between 18 g/L and 15 g/L 37 1320062. 28. The method of electroplating copper according to claim 14, wherein the current density is between 10 amps per square foot (A/ft 2 ; ASF) to 30 ASF. 29. The method of electroplating copper according to claim 14, wherein the current density is between 10 ASF and 20 ASF. 30. The method of electroplating copper according to claim 14, wherein the opening is selected from the group consisting of a one-micron blind hole and a one-micron blind hole. 38 132006 柒, (1), the designated representative figure of this case is: __2.——图(二), the representative symbol of the representative figure is a simple description: 201: tank 205: anode 215: bracket 221: substrate 231: Air Pump 2 00: Electroplating System 203: Power Supply System 207: Anode Hanging Material 2 1 7 : Cathode Hanging Material 223: Electric Shovel 233: Snorkeling Pipe, Shame of the Case: Miscellaneous: :,:; Prayer: Ningde ^ -- ... * - · XS-γ-Ζ ( I ) where X can be, for example, the following formula (Π ), formula (dish), formula (IV), formula (V), formula (VI) , formula (W), formula (Μ), formula (IX), or formula (X) ' sIH2+ (Π) (m) h2n-c—— (IV)1320062 (V) (VI) (W) (Vffl) (IX) (X) is a radical between 1 and 5 and may be, for example, a (CH2)n, wherein the integer ' and Z may be, for example, a COOH, a S03Na, an OH, or a NH2. 1320062 -N (X Π ) Ri wherein r2 can be, for example, -COOH, Ri can be, for example, a SO3 Na, an NH2'-SH or an OH'-NH-, a 〇- or an S-, and R3 can be, for example, a CN , —S〇3Na, an OH ' —NH 2 or a CH 3 .