TWI298751B - Composition for copper electroplating solution - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the composition of a steel plating bath, and more particularly to a composition of a copper electro-money liquid filled with micron-scale features of a semiconductor wafer and a printed circuit board. [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 volume of Ic substrate became more and more urgent and narrowed down to 1C, so the line width and line spacing were also shrinking. To place more electronic components on a smaller area. In response to current 1C copper process technology and printed circuit board (Printed circuit)

Board; PCB) high density internal connection (8) clock Density

Interneneetion; HDI) Necessary, sub-micron or micro-inner layers of Vias and Trench need to be filled with metal copper by electroplating. Filling must be done with Bottom up (B〇ttom-UP) or so-called P billing to avoid voids (^) or gaps (Seam). At present, there are two methods for filling steel wires and guide holes by electroplating. One is physical method, using pulse or pulse reverse package; L is used to achieve the phenomenon that the bottom of the hole moves up. It is a chemical method, adding multiple additives in the electric liquid 1278951, using DC current electric ore to achieve the filling effect of the bottom of the hole. Whether in academia or industry, the research and use of the latter are mostly, and academic Most of the galvanizing steel technology is limited to the wafer level plating process. Since the difference between the IC substrate and the wafer is mainly due to the size of the aperture, the basic reaction mechanism should be similar. The aperture is large, and there are many factors to consider (such as convection, mass transfer, etc.), which is more complicated than the wafer electroplating process. 4 Referring to Fig. 1, it shows the ic basis of the conventional technique of filling the metal wire. A cross-sectional view of the material. A metal-filled process is used to fill a metal such as copper into a micron-scale feature of the ic substrate 1 〇1, such as a blind via j 〇 3, wherein the filled metal layer 105 produces, for example, a void n丨The gap 丨3, or Defect-Free 115 has three different results, and the cavity lu and the gap 113 affect the signal transmission rate and reduce the reliability of the chip. In order to overcome the shortcomings of the prior art, the US patent in 1966 Bulletin Nos. 3, 267, 〇 1 与 and 3, 288, 690 teach the addition of several additives during the electroplating process, that is, the copper and / / product rate at the bottom of the hole is larger than the surface and the bottom of the hole is moved upward, improving Holes and gaps. These two patents use thiol compounds, polyvinyl alcohols (PEG), chloride ions, and the heterocyclic compound Janus Green B (JGB) to create a hole bottom. The filling effect of the upward movement, and the above formula has been in use until now. The thiol series compound is usually called Accelerator or Brightener in the hole-filling plating, and two kinds are commonly used, one is double (3_sulfonic acid propyl) disulfide (Bis (3e_Sulf〇pr〇pyl) Disulfide; SPS), the other is 3_thiol-propyl-acrylic acid 1289751 (3-Mercapto-l-Propane Sulfonate; MPS) SPS and MPS in the plating process Will convert each other, and the _SH functional group of MPS will form a complex with steel ions, change the reaction mechanism of copper ion reduction, improve the current exchange density of the electroplating reaction, and accelerate the deposition of copper. Furthermore, SPS spot MP S will be strongly adsorbed on the surface of the electrode when the electroplating reaction occurs, and SpS will be rapidly reduced to MPS, and MPS will help the divalent copper ions to be reduced to monovalent copper ions and oxidized to SPS, thus circulating and increasing the surface price of the electrode. The rate of copper formation. The composition of a plating bath in which the composition of the plating solution is replaced by a replacement of the composition of the plating solution is disclosed in U.S. Patent Nos. 661,191, 6,350,366, and Ml. The Phthal〇Cyanine compound Alcian mue is used as a brightener in the copper electroplating process, and it needs to be mixed with other additives to be suitable for the semiconductor hole-filling process, and is not suitable for printed circuits. The hole filling process of the board. Polyvinyl alcohols (PEG) and chloride ions are known as inhibitors (Suppress®) or carriers because they significantly reduce the rate of copper deposition in the reaction of electrical f-copper. When PEG and chloride ions are present at the same time, the deposition of steel ions is very strongly inhibited, but other literatures have shown that chloride ions alone accelerate the reduction of steel ions. In addition, an organic nitrogen-containing heterocyclic compound, such as an Azole Compound, has an N+ functional group, and is preferentially adsorbed in a high current density region due to a current distribution, thereby suppressing a copper deposition rate, and thus organic The nitrogen-containing heterocyclic compound is referred to as a leveler. The more commonly used 11 1298751 leveling agent is, for example, JGB and benzotriazole (Benz〇triaz〇ie · βτΑb leveling agent can effectively increase the effective range concentration of the accelerator, reduce the generation of voids) Smoothing function. Generally speaking, most of the electroplating formulations in the academic and industrial circles today adopt multi-additive formulations. However, as far as academic research is concerned, there are too many factors to be considered in the multi-additive formulation, including each additive individually affected by the environment. The interaction between shadow molding and two or more additives must be considered, so multiple additives are not conducive to the study of the bottom-up mechanism. For industrial applications, multiple additives often lead to difficulties in analysis and difficult to achieve stability. Product f control. Basin type 'multiple types of additives' analysis and control are not easy, especially when applied to pcb: can only fill blind holes, can not fill through holes. Moreover, most of the through holes filled with pcb or 疋1C substrate are only Plating a thin layer of copper, and then plugging the conductive paste or the tree S. With the improvement of the industry requirements, the plating filling of the through holes is also a future development. Trends 'At present, there are related companies in Japan that use the method of stacking blind holes to complete the filling of via holes. However, due to the above methods, there are quite a few problems that must be overcome, such as alignment problems, connections between copper and copper layers, and the like. Therefore, there is currently no method for using organic additives in the world to make the vias superfilled and all the additive formulations that can be filled on the micron-sized blind holes cannot be applied to the via filling. In view of the above, it is urgent to propose a method. The composition of the copper plating solution is to simplify the composition of the additive in the conventional copper plating solution, and can be simultaneously applied to the plating filled through hole and the blind hole. [Invention] 12 1298751 Therefore, one of the objects of the present invention is to provide a steel. The composition of the plating solution replaces the conventional multiple additive with a single additive formulation, which not only simplifies the composition of the additive in the conventional steel plating solution, but also can be applied to the substrate filled with micron-sized and sub-micron-sized through holes and blind holes. Another object of the present invention is to provide a method of electroplating copper, which can be used in semiconductor steel processes and printed circuits. In the plate filling process, the steel plating solution containing a single additive can be simultaneously applied to the substrate filled with micron-sized and sub-micron-sized through holes and blind holes, and provides better filling ability. The object is to provide a steel plating solution comprising at least: steel ions and a single additive, wherein the steel ions can be provided by a copper-containing compound, and the copper-containing compound can be, for example, anhydrous sulfuric acid steel (CuS〇4), aqueous sulfuric acid steel, carbonic acid steel ( CuC〇3), or copper oxide (Cu〇), as a single additive is a nitrogen-containing heterocyclic compound. According to a preferred embodiment of the present invention, the composition of the copper plating solution further comprises at least an electrolyte and an acid, wherein the electrolyte may be, for example, a halogen ion. And an 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 first providing a substrate having micron and submicron characteristics; and then providing at least a copper tweezers and a single a plating solution for the additive, and a plating step of immersing the substrate in the plating solution and applying at least one current to the substrate The density allows copper ions to be deposited in the micron and submicron features of the substrate. A preferred embodiment of the present invention, wherein the plating solution further comprises at least an electrolyte and an acid, the t electrolyte of which may be, for example, a dentate ion, and the acid may be, for example, sulfuric acid. The invention utilizes a single additive to replace the conventional multiple additive, not only the composition of the additive in the copper plating solution, but also the preferred cake can be applied to the electroplating filling with micron and submicron=system Substrate for sub- and sub-micron vias and blind vias. , for example, micro [embodiment] The present invention discloses a composition of a copper electro-key liquid, a substrate having micro-level and sub-micron-sized through-holes and blind holes, wherein the base is a base of a conductor wafer or a printed circuit board. Material, which contains: copper ions and single-additives, wherein the steel ions can be provided by copper-containing materials, and the concentration of copper-containing compounds can range from 150g/L to 25〇/L, but between 200g/L It is preferably between 25 〇g/L. The steel-containing compound g may be, for example, anhydrous sulfuric acid steel, aqueous copper sulfate, copper carbonate, or copper oxide, and preferably copper sulfate (: 4·5Η_^: PPm to UK) ppm. The additive may be a nitrogen-containing heterocyclic compound, and the structure of the additive is as shown in the following formula (1):

X (I), formula ( melon), formula (IV), formula (v), wherein x can be, for example, the following formula (Π) Formula (VI) or Formula (W), 14 1298751

(Π)

V, n/n^^ (in)

HO

H3C——CH (IV) \Nj=Y^

r^V^N'N+^N 15 (V) 1298751

Nh2

r^S (VI) H3c

OH

Ch2ch3 (W) and Y may be, for example, -OCH3, -N02, -NH2, -S03Na, -CN, 16 1298751 -COOH, formula (砸), formula αχ) or -CnHm, and wherein n is between The integer ' πι is an integer between 2 and 7.

(Cong) According to West in the Journal of Electrochemistry in 2000 (j〇urnai 〇f

Electrochemical Society, Vol. 147, No. 1, pp. 227-262, in the theory of Filling of High-Aspect Ratio Trenches and Vlas in Presence of Additives As a result of the simulation, it is considered that as long as a single inhibitor 'uses a ratio of its reaction consumption rate to the diffusion rate in the solution =, a concentration gradient is generated between the distance between the pore surface and the bottom of the pore, the super-filling can be achieved. the result of. Although no inhibitor of the fashion can conform to the simulation of this paper, the nitrogen-containing heterocyclic compound disclosed in the present invention is a flat agent, and the nitrogen-containing heterocyclic compound further provides an N+ functional group and can be simultaneously applied to the filling. Through holes and blind holes, examples of which are described in detail later. According to a preferred embodiment of the present invention, the composition of the copper plating solution further comprises at least a <77 Λ 中 电解 电解 可, for example, a halogen ion, and the halogen ion is preferably a chloride ion and the concentration of the chloride ion is between 10 ppm and Between 100 ppm is good. The rat ion can help the nitrogen-containing heterocyclic compound form a coordination with the steel ion 17 1298751 structure to stably adsorb on the copper layer, and the chloride ion can strengthen the nitrogen-containing heterocyclic compound. Adsorption on copper. According to a preferred embodiment of the present invention, 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 is preferably 18 g/L. Please refer to FIG. 2, which is a flow chart of a method for electroplating copper according to a preferred embodiment of the present invention, and together with FIG. 3 to FIG. 4, is a preferred embodiment of the present invention. The method for electroplating copper of the present invention. The method for electroplating copper of the present invention comprises at least: first, as shown in step 2〇1 and in conjunction with FIG. 4, a substrate 401 having micron and submicron characteristics is provided. Material 401 can be, for example, a semiconductor wafer or printed The substrate of the circuit board is 4〇1, and the substrate 401 has been washed by about 3% dilute sulfuric acid pickling and ultrapure water, wherein the micron and submicron features can be, for example, blind holes 403 or through holes 405' The aperture of the blind via 403 or the via 405 is between 20/zm and 500 // m, and the aspect ratio of the blind via 403 is between 1 and $. Then, as in step 203 And in conjunction with Figure 4, a plating solution comprising at least a steel ion and a single additive 410 is provided, wherein the copper ion may be provided by a copper-containing compound, and the steel-containing compound may be, for example, anhydrous copper sulfate, aqueous copper sulfate, carbon-copper or gas. The copper is preferably a copper sulfate pentahydrate. The single addition of mJ 41 0 is a nitrogen-containing heterocyclic compound, wherein the structure of the nitrogen-containing heterocyclic compound is as shown in the above formula (I). Thereafter, as in step 205. As shown in FIG. 4, the electroplating step is performed by immersing the substrate 4〇1 in the plating solution, using the substrate 4〇1 as a cathode, and applying at least one current density to the substrate 40丨 to deposit copper ions on the substrate. MM's micron and submicron features, by micron and submicron 18 1298751 The steel layer 420 is formed in the blind hole 403 or the through hole 405. According to a preferred embodiment of the present invention, the method for electroplating copper of the present invention can be carried out in an electroplating system for electric ore steel, and It is well known to those skilled in the art, and therefore will not be further described. It is worth mentioning that the method of electroplating copper of the present invention is applied to pre-apply when filling micron and submicron features such as blind via 4〇3 and via 405. In the case of current, a very good filling effect can be obtained. Referring to Figure 3, when a current is applied in advance during the electroplating process, the single additive 41〇 is affected by the current distribution of the cathode substrate 401, and preferentially adsorbs to the substrate. 4表面1 surface 4H and blind hole 403 and through hole 4〇5 hole tip corner corner, and reduce the diffusion speed of single additive 410, intercepting a single additive 41〇 into the bottom surface of the hole to absorb, let the copper surface and blind hole 4〇3 The bottom portion 4丨3 and the bottom portion 415 of the through hole 4〇5 produce a difference in concentration of the single additive 410, resulting in a difference in copper deposition inhibiting ability to achieve a good superfilling effect, and a structure as shown in Fig. 4 is formed. Referring to Figure 5(a), it is a cross-sectional view of an IC substrate that has been polished by a metallographic microscope and magnified 2 times to observe a blind hole of 65". The middle is made by adding 20 melons to 100 ppm. A nitrogen-containing heterocyclic compound is electroplated with a plating solution of (7) Ppm to 1 〇0 ppm of chloride ions at a current density of about 1.5 amps per square inch (A/ft 2 ; ASF) to about 6 (four). The copper filling effect is good. ° Please refer to the 5th, which shows the use of metallographic microscope to enlarge _ test the blind hole aperture lG5"m 1C substrate after filling the cross-sectional view of the grid, ° and add 20 To 100% of the nitrogen-containing heterocyclic compound ;;, 19 1298751 PPm to (10) ppm of chloride ion electro-recording liquid, current density: one time to fill the electric clock, the result of the steel filling effect in the blind hole, the application of the present invention is lower When the concentration of the nitrogen-containing heterocyclic compound is filled in a single dose, the nitrogen-containing heterocyclic compound interacts with the gas ion, and the chloride ion can effectively form the coordination structure of the nitrogen-containing heterocyclic compound with copper. Its =, adsorbed on the steel layer, so adding a certain concentration of chloride ions can Nitrogen-containing: The polarization effect and range of the ruthenium compound are increased. However, the nitrogen-containing heterocyclic compound of the present invention itself contains a part of gas ions, so the nitrogen-containing heterocyclic compound: at a higher concentration, may not be required In addition, when the through hole is filled by the method of galvanizing steel of the present invention, since the plating solution of the conventional multi-additive cannot produce the acceleration in the hole and the surface suppression, the filling effect is very poor, and the center of the through hole is usually A void or a gap is generated. However, since the copper plating solution of the single additive of the present invention does not need to generate intra-hole acceleration, the charge adsorption and the balance of the consumption and the diffusion rate of the electric field are completely relied on, and a concentration gradient is generated between the pore and the pore surface. In addition, the effect of filling is achieved. Furthermore, since the single additive of the present invention first seals the hole at the center of the through hole, that is, the through hole is divided into two symmetrical blind holes, the problem of voiding can be avoided. Fig. 6 is a cross-sectional view showing the through hole diameter 85 # m of the 1C substrate and the depth of 150 # m after being filled by electroplating by a metallographic microscope. Electroplating is performed by adding a plating solution containing 20 ppm to 100 ppm of a nitrogen-containing heterocyclic compound and a chloride ion of 10 ppm to 1 〇〇 ppm, and as a result, the copper filling effect in the via hole is good. The composition of the copper plating solution of the present invention can be applied to the substrate of the microporous and submicron-sized through-holes and blind vias on the same day, please refer to the figures 7(a) to 7(b). The system shows that a 1C substrate with through holes and blind holes is observed by electroplating with a metallographic microscope. The aperture of the 8C blind hole is 1〇〇"ηι, depth 60/zm, and through hole The pore size is 250 to a depth of 330/zm and is plated with a nitrogen-containing heterocyclic compound of 20 ppm to 100 ppm and a plating solution current density of from 1 ppm to 100 ppm of chloride ions at a pressure of from about 1.5 ASF to about 6 ASF. Filling, the copper filling effect in both the blind hole and the through hole is very good. In summary, the composition of the copper plating bath of the present invention does overcome the conventional problem of not being able to simultaneously fill the through holes and blind holes. It can be seen from the above preferred embodiments of the present invention that the composition of the copper plating solution of the present invention has the advantage of replacing a conventional multiple addition enthalpy with a single additive, which not only simplifies the composition of the additive in the conventional copper electro-mineral liquid, but also simultaneously Suitable for electroplating substrates filled with micron and submicron vias and blind vias. According to the preferred embodiment of the present invention, the method for applying the copper plating of the present invention has the advantages that the semiconductor copper process and the printed circuit board hole-filling process can be applied by using a copper plating solution containing a single-additive. 6 Electroplated to fill substrates with micron and sub-micron vias and blind vias, and provide better fill capability. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection of the present invention is defined by the scope of the patent application. 21 1298751 BRIEF DESCRIPTION OF THE DRAWINGS The following is a brief description of the drawings, which show the maritime examples used in the present invention, wherein: ^ Figure 1 shows the scraping of a 1C substrate filled with metal wires by the prior art. 2 is a flow chart showing a method of electric iron steel according to a preferred embodiment of the present invention; FIG. 3 to FIG. 4 are diagrams showing the process of electric age copper according to a preferred embodiment of the present invention. 5(a) to 5(b) are cross-sectional views showing the blind holes of the 1C substrate of several preferred embodiments of the present invention after electroplating filling using a metallographic microscope; and FIG. A cross-sectional view of a through hole of a 1C substrate of a preferred embodiment of the present invention after electroplating is observed by a metallographic microscope; and FIGS. 7(a) to 7(b) are enlarged by a metallographic microscope. A cross-sectional view of the 1C substrate having through holes and blind holes after electroplating was observed twice. [Simplified Description of Component Symbols] 101: Substrate 103: Blind Hole 105: Metal Layer 111: Cavity 113: Slit 115: No Defect 201 • Provides a substrate 203 having micron and micron-scale characteristics · Providing at least copper ions And single additive plating solution 205: performing plating step 22 1298751 401 405 411 415 substrate 403 : blind via hole 410 : single additive surface 413 : bottom bottom 420 : copper layer 23

Claims (1)

1298751 Picking up, patent application scope i A composition of a steel plating solution containing at least · copper ions; and a single additive, wherein the single additive is a nitrogen-containing heterocyclic compound 2. As claimed in the patent scope! The composition of the molten steel ore according to the item, wherein the structure of the nitrogen-containing heterocyclic compound is as shown in the formula (1): X Wherein the X system is selected from the group consisting of the formula (H), the formula (m), the formula (IV), the formula (V), the formula (VI), and the formula (νυ), and (Π) 24 V1298751 ΊνΓ (Π) ΗΟ H3C—CH \ [^Ί (IV) 25 (VI)1298751 nh2 OH CH2CH3 (VD) The Y is selected from the group consisting of a CH3, a N02, an NH2, a S03Na, a CN, a COOH, a formula (M), a formula (K) and a CnHm, and wherein The n is an integer between 1 and 3, and the m is an integer between 2 and 7. () c=n+ch3 II OH CH3 26 (IX) 1298751 3. The composition of the copper plating solution according to claim 1, wherein the concentration of the single additive is between 20 ppm and 1 〇〇ppm. between. 4. The composition of the copper plating solution according to claim 1, 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), containing water. A group consisting of copper ruthenate, acid-breaking steel (CuC03) and copper oxide (CuO). 5. The composition of a copper plating solution according to claim 4, wherein the copper-containing compound is copper sulfate pentahydrate (CuSCU · 5H20). 6. The composition of a copper plating solution according to claim 5, wherein the concentration of the copper-containing compound is between 150 g/L and 250 g/L. 7 _ The composition of the copper plating solution as described in claim 5, wherein the concentration of the copper-containing compound is between 2 〇〇 g/L and 250 g/L. 8. The composition of the copper plating solution according to claim 1, further comprising at least one electrolyte, and the electrolyte is a halogen ion. 9. The composition of the copper electroplating solution according to item 8 of the patent application, wherein the halogen ion is chloride ion, and the concentration of the chloride ion is between j 〇 ppm and 100 ppm 〇 27 1298751 ιο· The composition of the copper plating solution described in the first item of the patent scope further comprises at least one acid. 1 1. The composition of the steel plating solution described in item 10 of the scope of the patent application wherein the acid is sulfuric acid and the concentration of the acid is between 18 g/L and 15 g/L. The composition of the steel plating solution comprises at least: a copper ion; and a single additive, wherein the single additive is a nitrogen-containing heterocyclic compound, and the structure of the nitrogen-containing heterocyclic compound is as shown in formula (I) : Wherein, the X system is selected from the group consisting of a formula (Π), a formula (dish), a formula (jy), a formula (V), a formula (W), and a formula (W), and 28 1298751 (Π) HO H3C—CH N, /N 29 (IV) 1298751 N+- (V) nh2r^S (VI) h3c N+ OH CH2CH3 N, (VD) 30 1298751 The γ is selected from the group consisting of ~〇CH3, —N〇2, —NH2, —S03Na, , COOH, (yuj), (han) and cnHm 'and wherein η is an integer between 43 and the 茁 is an integer between 2 and 7. (Μ) (IX) One ~-c=n+ch3 II OH CH3 13 · As in the group of steel plating solutions described in item 12 of the patent application, the concentration of the single additive in the medium is between 20 ppm and 100 Between ppm. 14. The composition of a copper electroplating solution according to claim 12, wherein the steel ion is provided by a copper-containing compound, and the copper-containing compound is selected from the group consisting of anhydrous copper sulfate, aqueous copper sulfate, and copper carbonate. And a group of copper oxides. 15. The composition of the copper plating solution as described in claim 14 wherein the steel-containing compound is steel sulfate pentahydrate (CuS04 · 5H20). [16] The composition of the copper plating solution as described in claim 14 wherein the concentration of the copper-containing compound is between 150 g/L and 250 g/L 31 1298751. 17. The composition of the copper plating solution according to claim 14 wherein the concentration of the copper-containing compound is between 200 g/L and 250 g/L. 18. The composition of the copper plating solution according to claim 12, which further comprises at least one electrolyte, and the electrolyte is a halogen ion. 19. The composition of a copper electroplating bath as described in claim 18, wherein the functional ion is chloride ion and the concentration of the chloride ion is between 10 ppm and 1 〇〇 ppm. 20. The composition of the steel plating solution as described in claim 12, further comprising at least one acid. 21. The composition of a steel plating bath according to claim 20, wherein the acid is sulfuric acid and the acid concentration is between 18 and j 5 〇 g/L. The method of claim 2, comprising: providing a substrate, wherein the substrate has a feature; providing a plating solution, wherein the plating solution comprises at least one steel ion and a single additive; and 32 1298751 In an electroplating step, the substrate is immersed in the plating solution, and at least -Φ, hexafluorene: electrical k-twist is applied to the substrate to deposit the copper ions in the feature of the substrate. The method of claim 2, wherein the single additive is a nitrogen-containing heterocyclic compound, and the structure of the nitrogen-containing hybrid is as shown in formula (I): (V) wherein the X is selected from the group consisting of formula (Π), formula (gu), formula (jy), gas, formula (VI), and formula (VB), and X 33 1298751 (m) HO I H3C—CH N+: (IV) (V) 34 (VI)1298751 nh2 H3C N+< OH (W) the Y is selected from the group consisting of an OCH3, a N02, an NH2, a S03Na, a CN, a COOH, a formula (M), a formula (K), and a CnHmK, wherein the n is An integer between 1 and 3, and m is an integer between 2 and 7. ...........IJ (VBI) (IX) C=N+CH3 II OH CH3 24. The method of electroplating copper according to claim 22, 35 1298751 wherein the single additive The concentration range is between 20 ppm and 100 ppm. The method of electroplating copper according to claim 22, wherein the steel ion is provided by a copper-containing compound, and the copper-containing compound is selected from the group consisting of anhydrous copper sulfate, aqueous copper sulfate, copper carbonate, and A group of copper oxides. The method of electroplating copper according to claim 25, wherein the copper-containing compound is copper sulfate pentahydrate (CuS04 · 5H20). The method of electroplating copper according to claim 25, wherein the concentration of the copper-containing compound is between 150 g/L and 250 g/L. 28. The method of electroplating copper according to claim 25, wherein the concentration of the copper-containing compound is between 200 g/L and 250 g/L. 29. The method of electroplating copper according to claim 22, wherein the electroplating solution further comprises at least one electrolyte, and the electrolyte is a halogen ion. The method of electroplating copper according to claim 29 Wherein the _ elementary ion is chloride ion and the concentration of the chloride ion is between 10 ppm and 100 ppm. The method of electroplating copper according to claim 22, wherein the liquid crystal liquid further comprises at least one acid. 2. The method of claim 4, wherein the acid is sulfuric acid and the concentration of the acid is between 18 g/L and 150 g/L. 33. The method of electroplating copper according to claim 22, wherein the feature is selected from the group consisting of a -micron-level blind via, a sub-micron-level blind via, a micro-level via, and a micro-micron via. And a combination of the above and a combination thereof. The method for pen iron ore comprises at least: providing a substrate, wherein the substrate has a through hole and a blind hole; providing a plating solution, wherein the plating solution comprises at least one copper ion and a single additive; and the step of plating And immersing the substrate in the plating solution, and applying at least a current density to the substrate, and depositing the steel ions in the through hole and the potting method of claiming the copper plating described in the patent scope No. 34 , 1: Λ: the additive is a nitrogen-containing heterocyclic compound ' and the nitrogen-containing heterocyclic a substance has the structure shown by the formula (I): 37 1298751 Wherein the x is selected from the group consisting of the formula (π), the formula (m), the formula (ιν), the formula (V), the formula (VI), and the formula (w), and \ (瓜) 38 1298751 39 1298751 OH (VH) 5H Y series, selected from one of OCH3, one N〇2, ~NH2, one SC^Na, ~CN, ~C00H, formula (Μ), formula (K) and one CnHm a population, and wherein the η is an integer between 1 and 3, and the m is an integer between 2 and 7. -N 〇(Μ) -c=n+ch3 II (IX) OH CH3 36. The method of electroplating copper according to claim 34, wherein the concentration of the single additive is between 20 ppm and 1 〇〇 Between ppm. 37. The method of electroplating copper according to claim 34, 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, aqueous copper sulfate, copper carbonate, and Copper oxide is a group of people. The method of claim 4, wherein the copper-containing compound is steel sulfate pentahydrate (CuS〇4·5H2〇). 39. The method of electroplating copper according to claim 37, wherein the concentration of the copper-containing compound is between 15 〇 g / Li 25 〇 g / L. 40. The method of electroplating copper according to claim 37, wherein the concentration of the copper-containing compound is between 2 〇〇g/L and 25 〇g/L. 4. The method of electroplating copper according to item 34 of the patent application, wherein the money liquid further comprises at least an electrolyte, and (4) the electrolyte is a _ element ion. The method of %, electrospin, wherein the halogen ion is chloride ion, and the concentration of the chloride ion is between W ppm and 1 〇〇 ppm. 43. The method according to claim 34, wherein the plating solution further comprises at least one acid. 44. The galvanized steel of claim 43, wherein the acid is sulfuric acid and the concentration of the acid is between ', % 18 g/L to 15 。. The method of electroplating copper according to claim 34, wherein the through hole is selected from the group consisting of a one-micron-sized through-hole and a one-micron-sized through-hole. Method of galvanizing steel of MW 级 级 目 目 目 目 目 目 目 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 46 42