1. Field of the Invention
The present invention relates to a technique which produces fine wiring and vias on a substrate by means of electroplating.
2. Description of the Related Art
A demand for miniaturization of a wiring pitch of copper wiring to 20 or less μm has strongly increased also in chip-on-films (COF) and semiconductor package substrates due to downsizing of electronic devices. It has been difficult to keep good ion migration resistance according to the progress in the miniaturization of the wiring pitch.
In recent years, as a method for producing fine wiring and via holes (vias) on a substrate, an electroplating method has been used. The electroplating method has advantages such as lower cost, higher throughput and more excellent mass productivity than a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method. Various known methods for producing wiring and vias on a substrate using the electroplating include a Damascene method. In the Damascene method, first of all trenches and vias are formed on a substrate using a suitable method. The trenches and vias, which are concave section, are produced in a shape corresponding to a wiring pattern and via holes, and are formed on a position where a wirings and via holes should be arranged. Next, metal is deposited on the surface of the substrate by electroplating. The deposited metal fills the trenches and the vias. The deposited metal which fills the trench and the vias forms wirings and via holes.
Japanese Patent Application Laid-Open No. 2006-210565
Japanese Patent Application Laid-Open No. 2006-206950
Japanese Patent Application Laid-Open No. 2002-155390
The metal deposited by electroplating, however, covers not only the trenches and the vias on the substrate but also portions other than the trench and the vias After the electroplating is carried out, therefore, a process of removing an unnecessary metal layer is necessary. This metal removing process called chemical mechanical polishing (CMP). CMP process is complicated and high cost because it is difficult to accurately remove this unnecessary metal layer.
It is an object of the present invention to alleviate a work for removing an unnecessary metal layer when wiring and vias are produced on a substrate by electroplating.
According to the present invention, an additive is added to a plating solution to be used for electroplating. The additive has a plating reaction suppressing capability and has a characteristic that the plating reaction suppressing capability is reduced as the plating reaction progresses. As a result, metal can be deposited selectively in a trench and a via formed on the substrate.
According to the present invention, in a polarization curve of the plating solution to be used for the electroplating, when an electric potential shifts a first electric potential E1 to a more negative second electric potential E2 at 1000 rpm of rotational speed, a current density abruptly increases. In a potential region between the first electric potential E1 and the second electric potential E2, the polarization curve at 1000 rpm crosses the polarization curve at the 0 rpm.
According to the present invention, when a wiring and a via are formed on the substrate by a Damascene method, a trench and a via having a predetermined surface roughness are formed on the substrate.
According to the present invention, when the wiring and the via hole are formed on the substrate by electroplating, a work for removing an unnecessary metal layer can be reduced.
An outline of the present invention is described. According to the present invention, an additive is added to a plating solution to be used for electroplating. An acid copper sulfate solution may be used as the plating solution. The acid copper sulfate solution to be used for the electroplating is publicly known, and its details are not described here. When the acid copper sulfate solution is used, wiring and via holes are produced by copper. Wiring and via holes may be produced by metal other than copper. For example, nickel, aluminum and the like can be used. In this case, a metal solution whose metal is a raw material of the wiring and the vias is used as the plating solution. Metal to be used for a conductive layer as a seed layer for the electroplating may be copper, but other metals than copper, such as nickel, cobalt, chromium, tungsten, palladium, titanium and metal alloy containing at least one of these metals may be used.
According to the present invention, the additive has a capability for suppressing plating reaction, but has a characteristic such that the plating reacting suppressing capability is reduced as the plating reaction progresses. Any additive may be used as long as it has such a capability and a characteristic. Inventors of this application find out that cyanine dye and its derivative have such a capability and a characteristic. The cyanine dye is expressed by the following formula, where n is any one of 0, 1, 2 and 3.
As the additive to be used for copper plating, a substance which seppress the plating reaction and loses a plating reaction suppressing effect simultaneously with the progression of the plating reaction is suitable. The effect of the additive for suppressing the plating reaction can be checked by seeing if deposition overpotential of metal becomes higher when the additive is added to the plating solution. The effect that the additive loses the plating reaction suppressing effect simultaneously with the progression of the plating reaction can be checked by the fact that as a flow rate of the plating solution is higher, the deposition overpotential of the metal to be plated becomes higher. This means that as a supply speed of the additive to a first metal layer surface is higher, the plating reaction suppressing effect becomes higher. When the additive loses the plating reaction suppressing effect, the additive is decomposed and is changed into another substance or is reduced so as to be changed into a substance having a different oxidation number.
The reason why plating can be deposited in the concave section (the trench and the via) approximately selectively by carrying out plating using the plating solution containing such an additive is described below. When plating is carried out by using such an additive, the additive loses its effect on the surface of the first metal layer simultaneously with the progression of the plating reaction. As a result, an effective additive concentration relating to the plating reaction is reduced on the surface of the first metal layer. When the concentration of the additive is reduced, the additive is supplied by diffusion from the solution. At this time, the reduction speed of the additive concentration differs between the concave section and the substrate surface. Since unevenness is formed on the first metal layer in the concave section, its surface area is comparatively larger than that of the substrate surface. Therefore, the reduction speed of the additive concentration is high in the concave section. A distance from an bulk plating solution in the concave section is longer than that in the substrate surface. Therefore, the supply of the additive is slow in the concave section, and the increase speed of the additive concentration due to diffusion is low. For this reason, a state that its additive concentration is lower than that in the substrate surface is maintained in the concave section. Since this additive has the plating reaction suppressing effect, the plating reaction in the concave section where the additive concentration is low is not suppressed, and a plating film can be grown selectively in the concave section.
In the plating solution having such a characteristic, it is preferably that a rotating disk electrode has a potential area where a current value at 1000 rpm is 1/100 or less than that at the time of rest in a polarization curve obtained by measurement on the rotating disk electrode. In such a plating solution, as shown in
The plating solution having such a polarization curve enables metal to be deposited selectively in the trench and the via on the substrate.
According to the present invention, wiring and via holes are produced on the substrate by the Damascene method. Surface roughness in the trench and the via formed on the substrate is described together with the Damascene method. As a guidepost of the roughness, arithmetic average roughness Ra defined by JISB0601, and an average length RSm of a roughness curvilinear element defined by JISB0601 are known. According to the Damascene method, a trench and a via are formed on the substrate by a suitable method. The trench is formed in a shape corresponding to a wiring, and the via is formed on a position where the via holes are arranged. According to the present invention, the trench and the via are formed so as to have a predetermined surface roughness. The first metal layer as a seed layer for electroplating is formed on the substrate with the trench and the via formed thereon. A second metal layer is formed on the substrate surface by electroplating.
Before the electroplating is carried out, the surface roughness of the substrate with the first metal layer formed thereon was measured. As a result, the arithmetic average roughness Ra is 0.01 to 4 μm, and preferably 0.01 to 1.0 μm, in the trench and the via. The average length RSm of the rough curvilinear element is 0.005 to 8 μm, and preferably 0.01 to 2.0 μm. The arithmetic average roughness Ra on the area other than the trench and the via, namely, the substrate surface is preferably 0.001 to 0.002 μm. The average length RSm of the roughness curvilinear element is 10 to 50 μm, and preferably 20 to 40 μm.
The arithmetic average roughness Ra in the trench and the concave section is larger than the arithmetic average roughness Ra of the area other than the trench and the concave section, namely, the substrate surface. The arithmetic average roughness Ra in the trench and the via is ten or more times as large as the arithmetic average roughness Ra of the area other than the trench and the via. The average length RSm of the roughness curvilinear element in the trench and the via is smaller than the average length RSm of the roughness curvilinear element on the area other than the trench and the via, namely, the substrate surface. The average length RSm of the roughness curvilinear element in the trench and the via is 1/10 or less of the average length RSm of the roughness curvilinear element on the area other than the trench and the via.
The surface roughness in the trench and the via on the substrate hardly changes before and after the first metal layer is formed. Therefore, by forming the trench and the via having a desired surface roughness on the substrate previously, the trench and the via having a desired surface roughness can be obtained after the first metal layer is formed.
The trench and the via having a desired surface roughness are formed on the substrate, and the first metal layer is formed thereon. Further, the electroplating is carried out by using the plating solution to which the additive is added according to the present invention, so that metal can be precipitated selectively in the trench and the via on the substrate. The metal is not deposited on the area of the substrate other than the trench and the via, namely, the substrate surface. Therefore, the work for removing the metal deposited on the substrate surface can be alleviated. The present invention can be applied to formation of a copper wiring and a through silicon via technology in 3D packages.
An example of the electroplating carried out by the inventors of this application is described below. The inventors of this application conducted experiments of the electroplating in examples 1 to 8 and a comparative example 1. The examples 1 to 8 are electroplating experiments using the plating solution of the present invention to which the additive is added. The comparative example 1 is the electroplating experiment using a conventional plating solution. The plating solution was prepared by adding sulfuric acid with a concentration of 180 g/dm3 to copper sulfate pentahydrate with a concentration of 150 g/dm3. The additive of the present invention was added to this plating solution so that the plating solution of the present invention was prepared.
The arithmetic average roughness Ra defined by JISB0601 and the average length RSm of the roughness curvilinear element defined by JISB0601 are measured values of the surface roughness in the trench and the via on the substrate, which values were measured after the first metal layer being formed.
A production method for the wiring according to the present invention is described with reference to
As shown in
After the surface roughening treatment, the surface roughness on the surface of the substrate 1 was measured by a surface roughness measuring device. As shown in
As shown in
As show in
As shown in
After the first metal layer 3 was formed, the surface roughness in the trenches 3a and the surface roughness of the areas 3c other than the trenches 3a were measured by the surface roughness measuring device. The surface roughness in the trenches 3a were the same as the surface roughness on the surface of the substrate 1 measured after the surface roughening treatment. The arithmetic average roughness Ra defined by JISB0601 was 0.001 μm, and average length RSm of the roughness curvilinear element defined by JISB0601 was 34 μm on the areas 3c other than the trenches 3a.
As shown in
After the electrolytic copper plating, a wiring cross-section was observed. As shown in
As shown in
In the example 1, the surface of the resist film 2, namely, the copper plating film on the areas 3c other than the trenches 3a does not have to be removed, and thus the production of a wiring plate having a copper wiring with a depth of 10 μm and widths of 7 to 100 μm became easy.
The production method for the vias according to the present invention is described with reference to
As shown in
After the surface roughening treatment, the surface roughness of the copper foil 5 was measured by the surface roughness measuring device. As shown in
As shown in
As shown in
As shown in
After the first metal layer 3 was formed, the surface roughness in the concave sections 3b and the surface roughness on the areas 3c other than the concave sections 3b were measured by the surface roughness measuring device. The surface roughness in the concave sections 3b was the same as the surface roughness on the surface of the substrate 1 measured after the surface roughening treatment. The arithmetic average roughness Ra defined by JISB0601 was 0.002 μm and the average length RSm of the roughness curvilinear element defined by JISB0601 was 27 μm on the areas 3c other than the concave section 3b.
As shown in
As show in
In the example 2, the removal of the copper plating film is not necessary on the surface of the resist film 2, namely, the areas 3c other than the concave sections 3b. As a result, the production of the wiring plate having the vias with diameters of 20 to 200 μm became easy.
The production method for the vias according to the present invention is described with reference to
As shown in
As shown in
As shown in
The wiring cross-section was observed after the electrolytic copper plating. As shown in
As shown in
The production method for wiring according to the present invention is described with reference to
As shown in
The surface roughness in the trenches 1a on the substrate 1 was measured by the surface roughness measuring device. As shown in
As shown in
After the first metal layer 3 was formed, the surface roughness in the trenches 3a and the surface roughness on the areas 3c other than the trenches 3a were measured by the surface measuring device. The surface roughness in the trenches 3a was the same as the surface roughness before the first metal layer 3 was formed. On the areas 3c other than the trenches 3a, the arithmetic average roughness Ra defined by JISB0601 was 0.001 μm, and the average length RSm of the roughness curvilinear element defined by JISB0601 was 34 μm.
As shown in
The wiring cross-section was observed after the electrolytic copper plating. In the example 4, the thickness T1 of the copper plating film in the trenches 3a was 7 μm. The thickness T3 of the copper plating film on the areas 3c other than the trenches 3a was not more than 0.001 μm. In the example 4, therefore, it was found that the copper plating film grew selectively in the trenches 3a on the substrate, and that the copper was hardly precipitated on the areas 3c other than the trenches 3a, namely, on the substrate surface.
As shown in
In the example 4, the removal of the copper plating film on the surface of the substrate 1, namely, on the areas 3c other than the trenches 3a was not necessary. As a result, the production for the wiring plate having the copper wiring with a depth of 7 μm and widths of 7 to 100 μm became easy.
The production method for the wiring and the vias according to the present invention is described with reference to
As shown in
After the nanoimprint treatment, the surface roughness of the trench 7 and the concave section 8 was measured by the surface roughness measuring device. As shown in
As shown in
After the surface roughening treatment, the surface roughness of the exposed copper foil 5 was measured by the surface roughness measuring device. As shown in
As shown in
After the first metal layer 3 was formed, the surface roughness in the concave section 3a and the trench section 3b and on the other areas 3c was measured by the surface roughness measuring device. The surface roughness of the copper foil in the trench section 3b and the concave section 3a was the same as the surface roughness measured before the first metal layer 3 was formed. On the areas 3c other than the trench section and the concave section, namely, the substrate surface, the arithmetic average roughness defined by JISB0601 was 0.001 μm, and the average length RSm of the roughness curvilinear element defined by JISB0601 was 30 μm.
As shown in
The wiring cross-section was observed after the electrolytic copper plating. In the example 5, the thickness T1 of the copper plating film in the trench 3a was 5 μm, the thickness T2 of the copper plating film in the concave section was 10 μm. The thickness T3 of the copper plating film on the areas which were not subject to the nanoimprint treatment, namely, the substrate surface was not more than 0.001 μm. Therefore, in the example 5, it was found that the copper plating film grew selectively in the trench 3a on the substrate, and that the copper is hardly precipitated on the areas 3c other than the trench 3a, namely, the substrate surface.
As shown in
In the example 5, the removal of the copper plating film was not necessary on the surface of the substrate 1, namely, the areas 3c other than the trench 3a. As a result, the production of the wiring plate collectively having the copper wiring with a depth of 5 μm and widths of 5 to 100 μm and the vias with a diameter of 5 μm became easy.
The production method for wiring according to the present invention is described again with reference to
As shown in
After the surface roughening treatment, the surface roughness on the surface of the substrate 1 was measured by the surface roughness measuring device. As shown in
As shown in
As show in
As shown in
After the first metal layer 3 was formed, the surface roughness in the trenches 3a and the surface roughness on the areas 3c other than the trenches 3a were measured by the surface roughness measuring device. The surface roughness in the trenches 3a was the same as the surface roughness on the surface of the substrate 1 measured after the surface roughening treatment. On the areas 3c other than the trenches 3a, the arithmetic average roughness Ra defined by JISB0601 was 0.001 μm, and the average length RSm of the roughness curvilinear element defined by JISB0601 was 31 μm.
As shown in
The wiring cross-section was observed after the electrolytic copper plating. In the example 6, the thickness T1 of the copper plating film in the trenches 3a was 10 μm. The thickness T3 of the copper plating film on the areas 3c other than the trenches 3a was not more than 0.001 μm. In the example 6, therefore, it was found that the copper plating film grew selectively in the trenches 3a on the substrate, and that the copper was hardly precipitated on the areas 3c other than the trenches 3a, namely on the substrate surface.
As shown in
In the example 6, the removal of the copper plating film was not necessary on the surface of the resist film 2, namely, the areas 3c other than the trenches 3a. As a result, the production of the wiring plate having copper wiring with a depth of 10 μm and widths of 5 to 100 μm became easy.
The production method for wiring according to the present invention is described with reference to
The wiring cross-section was observed after the electrolytic copper plating. In the examples 7 and 8, the thickness T1 of the copper plating film in the trenches 3a was 10 m. The thickness T3 of the copper plating film on the areas 3c other than the trenches 3a was not more than 0.001 μm. In the examples 7 and 8, therefore, it was found that the copper plating film grew selectively in the trenches 3a on the substrate, and that the copper was hardly precipitated on the areas 3c other than the trenches 3a, namely, the substrate surface.
In the examples 7 and 8, the removal of the copper plating film was not necessary on the surface of the resist film 2, namely, on the areas 3c other than the trenches 3a. As a result, the production for the wiring plate having copper wiring with a depth of 10 μm and widths of 7 to 100 μm became easy.
Comparative example 1 is similar to the example 1 except that the plating solution does not contain an additive. The plating conditions are as shown in
In the comparative example, the removal of the copper plating film on the surface of the resist film 2, namely, on the areas 3c other than the trenches 3a was necessary. As a result, the production for the wiring plate having copper wiring with a depth of 10 μm and widths of 7 to 100 μm became difficult.
The examples of the present invention were described, but the present invention is not limited to the above examples, and various modifications within the scope of the present invention described in claims can be easily understood by those skilled in the art.
Number | Date | Country | Kind |
---|---|---|---|
2007-223617 | Aug 2007 | JP | national |