KR20040051522A - Method of forming and treating a metal film, semiconductor device and wiring board - Google Patents

Abstract

PURPOSE: A treatment method for forming a metal film, a semiconductor device and a wiring board are provided to improve adhesion between the metal film and a surface of a resin member by coating thinly conditioning solutions on the resin member and irradiating UV(UltraViolet) rays thereon. CONSTITUTION: UV rays are irradiated on a surface of a resin member through conditioning solutions(S11). An electroless plating process is performed on the resin member(S5). An electroplating process is then performed on the resultant structure, so that a desired metal film is formed on the resin member(S6).

Description

METHOD OF FORMING AND TREATING A METAL FILM, SEMICONDUCTOR DEVICE AND WIRING BOARD}

The present invention relates to a metal film forming processing method for forming a metal film on a resin substrate, a semiconductor device having a metal film on a resin insulating layer, and a wiring board, and in particular, a metal film formed by plating on the surface of the resin insulating layer. A metal film formation processing method, a semiconductor device, and a wiring board which can improve adhesive force.

In the metal film forming method according to the prior art, for example, a chip size package in which a wiring pattern is formed on a build-up substrate, a wiring board including a semiconductor package using the substrate, or a semiconductor element via a resin insulating layer. It is applied to the semiconductor device called.

For example, when forming a wiring pattern in a semiconductor device, in order to laminate | stack and form a wiring layer between the layers of a resin insulating layer, the base material which has electrical insulation, such as a polyimide and an epoxy resin, shall be made into the base material, and After coating on top or crimping a resin film having electrical insulation to form a resin insulating layer, a conductor layer is formed on the surface of the resin insulating layer by plating or the like. By etching the conductor layer formed on the surface of the resin insulating layer in a predetermined pattern, a wiring pattern can be formed on the surface of the resin insulating layer. Alternatively, after masking in a predetermined pattern on the resin insulating layer in advance, a conductor layer is formed by plating or the like to form a wiring pattern.

By the way, when forming a conductor layer in the surface of a resin insulating layer by plating, in order to improve the adhesiveness of the conductor layer formed by plating and the resin insulating layer, it is disclosed by Unexamined-Japanese-Patent No. 2002-57456, for example. Similarly, after performing the roughening process (desmear process) on the surface of a resin insulating layer previously, plating is conventionally performed. The roughening process is performed by etching the surface of a resin insulating layer using etching liquids, such as potassium permanganate and sodium permanganate.

In this case, the conductor is filled in the recessed part of the surface of the resin insulation layer formed by the roughening process on the surface of the resin insulation layer using the etching liquid, and the conductor of a wiring pattern adheres closely to the resin insulation layer by an anchor action. do. However, when the unevenness of the surface of the resin insulating layer becomes large, when the conductor layer is etched to form the wiring pattern, the unevenness of the surface affects the precision of the pattern formation, so that a very fine wiring pattern cannot be formed accurately. Occurs

When the conductor layer is etched to form a wiring pattern by the magnitude of the surface roughness on the surface of the resin insulating layer, the larger the surface roughness of the resin insulating layer, the larger the amount of immersion, and the smaller the surface roughness, the less the amount of immersion. That is, when the unevenness of the surface of the resin insulating layer is large, when the conductor layer is etched to form the wiring pattern, the etching liquid easily enters the side surface of the wiring pattern from the uneven portion, and the side surface portion of the wiring pattern floats. Becomes For this reason, when surface roughness is large, it becomes difficult to refine | miniaturize a wiring pattern.

In addition, when the surface roughness of the resin insulating layer increases, there is a problem that the transmission loss of the high frequency signal increases. The transmission loss is smaller as the surface roughness is smaller. Moreover, since migration resistance falls when the surface roughness of a resin insulating layer becomes large, it can be said that the surface roughness of the resin insulating layer in which a conductor layer is formed is as small as possible. Therefore, when forming the conductor layer onto the resin insulating layer, it is required to make the surface roughness of the resin insulating layer as small as possible and to improve the adhesion between the resin insulating layer and the conductor layer.

Usually, in a semiconductor device, when forming a conductor layer on a resin insulating layer, a metal film is formed by electroless copper plating and electrolytic copper plating following this, and it is set as a wiring board. However, since copper plating has low adhesiveness with a resin base material compared with nickel plating etc., when forming the metal film which becomes a conductor layer by copper plating, even more reliable adhesiveness of this metal film and a resin base material is calculated | required.

Thus, for example, as disclosed in Japanese Patent Laid-Open No. Hei 6-87964, in order to improve the adhesion, various methods of modifying the surface of the resin substrate and then electroless plating the surface have been proposed. have. For example, there exists a method of irradiating an ultraviolet laser to the surface of the resin base material placed in an amine compound gas or an amide compound gas atmosphere, and performing electroless plating after that.

For example, as a pretreatment for electroless plating on a resin substrate as disclosed in Japanese Patent Application Laid-Open No. Hei 8-253869, ultraviolet rays are irradiated onto the surface of the resin substrate, and then the surface of the resin substrate is electroless. By performing a method of performing plating and contacting with an alkaline solution containing a nonionic surfactant having a polyoxyethylene bond, for example, as disclosed in Japanese Patent Application Laid-Open No. 10-88361. Therefore, a method for improving the adhesion has been proposed.

For example, as disclosed in Japanese Patent Laid-Open No. 10-310873, after surface modification by ultraviolet irradiation on the surface of a resin substrate, a silane coupling agent having an amino-based group is adsorbed, and a tin-palladium-based The method of improving the adhesion of the metal film formed by electroless plating on the resin base material by promoting provision of a catalyst is also proposed.

On the other hand, in addition to the method of modifying the surface of the resin substrate by irradiation of ultraviolet rays, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-57456, the surface of the resin substrate is sequentially subjected to plasma treatment and ultraviolet treatment. After carrying out by performing electroless plating, a method of producing a functional group exhibiting adhesion to an electroless copper plated metal film, reducing the surface roughness of the resin substrate and improving the adhesion is proposed.

As mentioned above, when forming the metal film which becomes a conductor layer on the resin base material which is a resin insulation layer used for a semiconductor device etc., there are various methods of improving the adhesiveness of a resin base material and a metal film, and the peeling strength which shows the adhesiveness is practically practical. There is also a method having a sufficient size to improve the adhesion.

However, in each of these methods, the surface of the resin substrate is etched and the roughening treatment is performed. This etching process is generally performed by immersing a resin base material in strong oxidizing etching process liquids, such as a chromic acid and a sulfuric acid liquid mixture, a dichromic acid and a sulfuric acid liquid mixture, a chloric acid, a sulfuric acid, and a perchloric acid liquid mixture. By the way, since this etching process liquid is a chemical liquid with high risk and high pollution, sufficient care is needed about the handling and discharge process, and work load becomes large during the plating process in metal film formation.

In addition, even if the adhesiveness of a resin base material and a metal film can be improved by each said method, not only irradiating an ultraviolet-ray, but also after that irradiation, the processing agent for promoting the modification of the surface of a resin base material is a process liquid in a normal processing process. It is necessary to prepare separately from this, and there is a problem that the number of treatment steps increases, resulting in a treatment cost.

In the case of modifying the surface of the resin substrate, in the case of performing a plasma treatment subsequent to ultraviolet irradiation, a plasma processing apparatus must be provided in addition to the apparatus for ultraviolet irradiation, and the installation of the plasma apparatus increases the equipment cost. It becomes a problem in providing a cheap product.

Therefore, the present invention uses the processing liquid of each processing step in the conventional metal film formation which forms a metal film on the surface of a resin substrate such as a semiconductor device as it is, and the next processing step is performed while the effect of ultraviolet irradiation is continued. To provide a semiconductor film and a circuit wiring device having a metal film forming processing method that can easily improve the adhesion between the resin substrate and the metal film, and a metal film formed by applying the metal film forming processing method on the resin substrate. It is done.

1 is a flowchart for explaining a processing procedure of the metal film formation processing method according to the first embodiment.

FIG. 2 is a view for explaining an example of performing irradiation with radiation during a conditioning treatment step of the metal film formation processing method of the first embodiment; FIG.

3 is a flowchart for explaining a processing procedure of the metal film formation processing method according to the second embodiment.

FIG. 4 is a view for explaining an example of performing radiation irradiation during a conditioning treatment step of the metal film formation processing method of the second embodiment; FIG.

5 is a flowchart for explaining a processing sequence of a metal film formation processing method in which another embodiment is combined;

6 is a flowchart for explaining a processing procedure of the metal film forming method of the present invention.

7A to 7E are diagrams for describing processing steps in the metal film forming method shown in FIG. 6.

8 is a flowchart for explaining a processing procedure of another metal film forming method of the present invention.

In order to solve the above problems, in the present invention, the treatment is performed in accordance with the plating nucleation step and the electroless plating step to form a metal film on the surface of the resin substrate, or after the electroless plating step, the treatment by the electrolytic plating step is performed. In the metal film formation processing method which performs a metal film formation process on the surface of a resin base material, it is supposed to irradiate an ultraviolet-ray to the said surface through the process liquid used before the said electroless plating process.

The treatment liquid may be a conditioning treatment liquid for pretreatment of the surface before the plating nucleation process, or a catalizing treatment liquid applied to the surface in the plating nucleation process. It was carried out in both the case of passing through the conditioning treatment liquid and the case of passing through the catalizing treatment liquid.

Further, the conditioning treatment liquid or the catalyzing treatment liquid was interposed thinly between the glass plate and the surface.

In addition, in this invention, it was set as the semiconductor device which has a metal film formed on the resin insulating layer by the metal film formation processing method mentioned above, and it was set as the wiring board which has a metal film formed on the resin base material by the metal film formation processing method mentioned above. .

Next, embodiment which concerns on the metal film formation method of this invention is described, referring drawings.

Conventionally, the plating method is used for formation of the metal film on the resin base material surface. This plating method is, for example, in the case of forming a copper metal film on the surface of a resin substrate such as polyimide, a pretreatment process such as degreasing of the resin surface, an etching treatment process, a catalizing treatment process, and an accelerating process. ) It is common to become a treatment process, an electroless copper plating process, and an electrolytic copper plating process.

As described above, the plating treatment is performed after various treatment steps without performing plating treatment directly on the surface of the resin substrate, because the resin has hydrophobicity which is hard to get wet with water. If the plating process is performed on the surface of the resin substrate as it is, a metal film cannot be formed on the surface. When performing surface treatment in aqueous solution like plating, the surface of a resin base material must be made hydrophilic which is easy to get wet with water. In order for the surface of the resin substrate and the plating metal to be in close contact with each other, the surface of the resin substrate is made hydrophilic, and then a polar group is formed on the surface of the resin to activate the surface, and roughening is performed with irregularities such as fine pores on the surface of the resin. This process is an etching process.

Further, in order to deposit the plated nuclei, palladium (Pd) activation is required on the resin surface, so that it is immersed in a catalizing treatment liquid containing PdCl ₂ and SnCl ₂ to adsorb the catalyst metal on the resin surface. This process is a catalizing process.

When the catalizing treatment step is performed, the complex salt of Pd and Sn is adsorbed on the surface of the resin substrate, and therefore, in the accelerator treatment step, in the accelerator treatment solution containing HCl or H ₂ SO ₄ , NH ₄ FHF, or the like, The palladium metal which becomes a plating nucleus is deposited on the resin surface.

Next, in the electroless plating process, the copper metal is electroless plated on the resin surface by the catalytic action of the plating nucleus deposited on the resin surface to form a metal film on the entire resin surface. The metal film by electroless plating has a role of a power feeding layer for electrolytic plating, and is about 0.5-2.0 micrometers in thickness normally. Thereafter, the electrolytic copper plating process is performed to electrolytic copper plating until a predetermined thickness that can be used for a wiring pattern or the like is formed to form a metal film.

Although the above-mentioned processing process is a formation method at the time of forming a copper metal film on the surface of a general resin base material, before carrying out this embodiment, the etching process of both high risk and pollution is not performed in this formation method, As a simplification of the treatment step, a metal film formation treatment as shown in Fig. 6 was attempted.

In the formation of the metal film on the surface of the resin substrate shown in Fig. 6, the conditioning treatment step (S1), the pre-dipping step (S2), the catalizing step (S3), the accelerating step (S4), and the electroless copper plating step (S5) And the electrolytic copper plating process S6 is performed in order.

Here, the metal film forming treatment method shown in FIG. 6 is different from the conventional metal film forming method, and the etching treatment step is omitted, and in the conditioning treatment step (S1), pretreatment such as degreasing to the surface of the resin substrate is performed. After that, a predipping treatment (S2) for hydrophilizing and activating the surface of the resin substrate is performed, followed by a catalizing treatment (S4). In the pre-diffusing treatment step (S2), there is also an effect of promoting the adsorption of the complex salt by Pd and Sn as the plating nucleus.

7A to 7E schematically show a metal film forming step in accordance with the procedure by the processing step of the metal film forming method shown in FIG. 6. FIG. 7A corresponds to the conditioning treatment step S1 and shows a state in which the conditioning treatment liquid 2 is brought into contact with the surface of the resin substrate 1 to pretreat the surface of the resin to be plated. have.

FIG. 7B corresponds to the pre-dipping treatment step S2, and shows a state in which the pre-dipping treatment liquid 3 is brought into contact with the surface of the resin substrate 1 to perform the activation treatment of the surface thereof. In addition, in FIG. 7A and FIG. 7B, although the conditioning treatment liquid 2 or the pre-dipping treatment liquid 3 is shown on the surface of the resin base material 1, the resin base material ( It pays attention to the surface treatment of 1), and was represented typically, and the resin base material 1 is immersed in each process liquid and processed in an actual process process.

Next, in FIG. 7C, the surface of the resin substrate 1 is in a state in which Pd activation is completed, that is, a catalizing treatment step S3 and an accelerator treatment step S4 are performed. 4) shows a state of precipitation. Although the plating nucleus 4 is shown by five black rings in the figure, this is enlarged and shown in order to simplify the drawing, and in fact, it is minute and many more nucleus are deposited.

FIG. 7D corresponds to the electroless plating treatment step S5 and shows a state in which the electroless copper plating treatment is performed after the plating nucleus 4 is deposited on the surface of the resin substrate 1. By the catalytic action of Pd, the copper metal 5 is plated on the surface of the plating nucleus 4. In addition, electroless plating further continues, and a continuous copper metal is plated over the entire surface of the resin substrate 1.

7E corresponds to the electrolytic copper plating treatment step S6, wherein the entire surface of the resin substrate 1 is electroless plated with copper metal 5, followed by electrolytic copper plating to form a metal film 6. It shows the state. Thereby, according to the procedure of the metal film formation processing method shown in FIG. 6, the metal film used as a conductor layer on the surface of the resin base material 1 is formed.

By the way, since the etching process process was abbreviate | omitted in this metal film formation processing method, the adhesiveness of a resin base material and a metal film became weak, and sufficient peeling strength value was not obtained. Then, in order to raise the adhesiveness of a resin base material and a metal film by this metal film formation method, improvement which irradiated the ultraviolet-ray to the resin base material surface was performed. The metal film formation method which irradiates an ultraviolet-ray is shown in FIG.

The metal film formation processing method shown in FIG. 8 is equipped with the same processing process (S1-S6) based on each processing process of the method shown in FIG. In the metal film formation processing method of FIG. 8, the ultraviolet treatment step S0 is performed before the conditioning treatment step S1 is performed.

By irradiating the surface of a resin base material with ultraviolet rays, when monochromatic light of 172 nm by a dielectric barrier discharge excimer lamp is used, it is known that the surface of polyimide resin etc. is activated. Although the wavelength of ultraviolet rays is long, the activating effect by irradiation appears, but the shorter the wavelength, the greater the activating effect has been demonstrated (see, for example, Japanese Patent Laid-Open No. 2002-57456). However, this ultraviolet irradiation effect lasted only a short time, and did not continue until Pd activation treatment or electroless copper plating treatment. Therefore, even if there is an activation effect by ultraviolet irradiation, it did not reach to improve the adhesiveness of a resin base material and a metal film.

In the metal film forming treatment method shown in FIG. 8, the ultraviolet irradiation treatment step (S0) is performed alone in front of the conditioning treatment step (S1). Attempts have been made to run simultaneously with the catalysis process. That is, in the state of the conditioning process shown to FIG. 7A, or the state of the catalizing process shown to FIG. 7B, from the upper side of the resin base material 1, the conditioning process liquid 2 or a catalyst The ultraviolet-ray was irradiated to the surface of the resin base material 1 through the rising process liquid 3.

However, ultraviolet rays are irradiated to the surface of the resin substrate 1 through the conditioning treatment liquid 2 or the catalizing treatment liquid 3 from above the resin substrate 1, and the copper metal is placed on the resin substrate 1. When the film 6 was formed, no improvement was observed in the adhesion between the formed copper metal film 6 and the resin substrate 1.

Thus, the cover glass plate is placed on the treatment liquid so that the conditioning treatment liquid 2 or the catalyzing treatment liquid 3 is thin on the surface of the resin substrate 1, for example, about 10 μm. After irradiating the surface of the resin base material 1 with the ultraviolet-ray which has a wavelength of 172 nm through the glass plate, the copper metal film 6 and the resin base material formed as a result of forming the copper metal film 6 on the resin base material 1 ( The adhesion of 1) was greatly improved, and a peel strength value of sufficient size that could be provided for practical use was obtained.

The effect of improving the adhesion is that when the surface of the resin is irradiated with ultraviolet light through a thin treatment liquid, when the resin molecules on the surface are activated and the reactivity becomes high, the resin and the treatment liquid coexist so that the components of the treatment liquid and the resin This is because the molecule is chemically bound strongly and the activation is accelerated and continued.

Therefore, in the metal film formation processing method by this embodiment, in order to improve the adhesiveness of a resin base material and a metal film, the timing of an ultraviolet irradiation is made when a processing liquid exists on the surface of a resin base material, and activation by ultraviolet irradiation is carried out. Was increased so that the metal film was formed while this activation continued.

In FIG. 1, it showed about the processing process of 1st Embodiment of the metal film formation method by this invention. In the metal film forming treatment method of the first embodiment of the same drawing, the ultraviolet irradiation treatment step S0 and the conditioning treatment step S1 shown in FIG. 8 are combined to perform ultraviolet irradiation in the presence of the conditioning treatment liquid. Indicates. Therefore, each treatment process of the metal film formation method of 1st Embodiment is based on the metal film formation treatment method shown in FIG. 8, and attaches the same code | symbol to the same process process.

Therefore, in the metal film forming treatment method of the first embodiment, the ultraviolet irradiation treatment step S0 and the conditioning treatment step S1 of FIG. 8 are replaced with the conditioning and ultraviolet irradiation treatment step S11, but the pre-diffusing treatment is performed. Each step of the step (S2), the catalizing step (S3), the accelerating step (S4), the electroless copper plating step (S5), and the electrolytic copper plating step (S6) is unchanged, and the metal of FIG. Since it is the same as the process of each process in a film formation processing method, description of each process after a process process (S2) is abbreviate | omitted here.

The conditioning and ultraviolet irradiation processing step (S11) characterized by the metal film formation processing method of the first embodiment will be described with reference to FIG. 2. In FIG. 2, it expands typically and partially. For example, the case where a copper metal film is formed on the resin insulating layer laminated | stacked by the semiconductor device is shown.

On the surface of the resin base material 1 which becomes a resin insulating layer, the layer of the conditioning process liquid 2 is formed. When forming this layer, the cover glass plate 7 is placed on the conditioning liquid 2, and the thickness of the conditioning liquid 2 is about 10 micrometers. The cover glass 7 is for forming the layer of the conditioning treatment liquid 2 uniformly and thinly on the resin surface.

Ultraviolet rays are irradiated toward the surface of the resin substrate 1 from above the cover glass plate 7. As ultraviolet light, for example, monochromatic light of 172 nm by a dielectric barrier discharge excimer lamp is used. When the ultraviolet rays are irradiated to the resin surface in the presence of the conditioning treatment liquid 2 on the surface of the polyimide resin or the like, activation of the surface is promoted and strengthened.

In the case of the first embodiment, since activation of the surface of the resin is promoted, the treatment time as the conditioning treatment may be shorter than the treatment time of the conditioning treatment step S1 in the metal film formation treatment method of FIG. 8. In addition, the processing liquid used for the conditioning process here does not need to prepare the processing liquid of a special specification, and the processing liquid used for the conditioning process is normally used as it is.

After the conditioning and ultraviolet irradiation treatment step (S11) shown in FIG. 2 is performed, as shown in FIG. 1, normal Pd activation process, electroless copper plating process, and electrolytic copper plating process are performed in order, and the metal film by copper (6) is formed on the resin base material 1.

Next, FIG. 3 showed the processing process of 2nd Embodiment of the metal film formation method by this invention. In the first embodiment, the ultraviolet irradiation treatment step S0 and the conditioning treatment step S1 shown in FIG. 8 are combined to perform ultraviolet irradiation in the presence of the conditioning treatment liquid. In the metal film forming treatment method, the ultraviolet irradiation treatment step (S0) and the catalizing treatment step (S3) shown in FIG. 8 were combined to allow ultraviolet irradiation to be performed in the presence of the catalyzing treatment liquid.

Therefore, since each processing process of the metal film formation method of 2nd Embodiment is based on the metal film formation processing method shown in FIG. 8, the same code | symbol is attached | subjected to the same process process. Therefore, in the metal film formation processing method of 2nd Embodiment, it replaces the ultraviolet irradiation process (S0) and the catalizing process (S3) of FIG. 8 by the catalizing and ultraviolet irradiation process (S31), and is conditioned The steps of the shoning treatment step (S1), the pre-dipping treatment step (S2), the acceleratoring treatment step (S4), the electroless copper plating treatment step (S5), and the electrolytic copper plating treatment step (S6) remain unchanged. Since each process is the same as the process of each process in the metal film formation treatment method of FIG. 6, description of each process other than a process process S31 is abbreviate | omitted here.

The catalizing ultraviolet irradiation treatment step (S31) characterized by the metal film formation processing method of the second embodiment will be described with reference to FIG. 4. In FIG. 4, similarly to the case of FIG. 2, the diagram is schematically and partially enlarged. For example, the case where a copper metal film is formed on the resin insulating layer laminated | stacked by the semiconductor device is shown.

On the surface of the resin base material 1 which becomes a resin insulating layer, the layer of the catalizing process liquid 3 is formed. The formation method of this layer was the same as that of FIG. 2, and only the catalizing process liquid 3 was used instead of the conditioning process liquid 2. As shown in FIG. The cover glass plate 7 is placed on the catalyzing liquid 3, and the thickness of the layer of the catalizing liquid 3 is about 10 mu m.

Ultraviolet rays are irradiated toward the surface of the resin substrate 1 from above the cover glass plate 7. As the ultraviolet ray, for example, monochromatic light of 172 nm by a dielectric barrier discharge excimer lamp is used. When this ultraviolet ray is irradiated to the resin surface in the presence of the catalizing treatment liquid 3 on the surface of the polyimide resin or the like, activation of the surface is promoted and strengthened.

In the case of the second embodiment, since activation of the surface of the resin is promoted, the processing time as the catalizing treatment may be shorter than the processing time of the catalizing treatment step (S3) in the metal film forming treatment method of FIG. 8. In addition, here, it is not necessary to prepare the process liquid of a special specification as a process liquid used for a catalizing process, and the catalizing process liquid currently used is used as it is.

After the catalizing and ultraviolet irradiation treatment step (S31) shown in FIG. 4 is performed, as shown in FIG. 3, normal Pd adsorption treatment, electroless copper plating process, and electrolytic copper plating process are performed sequentially, and the metal film by copper (6) is formed on the resin base material 1.

In the metal film formation processing methods of the first and second embodiments described above, ultraviolet rays are irradiated to the surface of the resin in the presence of either the processing liquid of the conditioning treatment liquid or the catalizing treatment liquid. In both the conditioning treatment process (S1) and the catalizing treatment process (S3) in the metal film forming treatment method shown, even if the resin surface is irradiated with ultraviolet rays, the activation of the resin surface is further layered. I can strengthen it.

The processing procedure of the metal film formation processing method of 3rd Embodiment which performed ultraviolet irradiation about each of the processing processes in the metal film formation processing method shown in FIG. 6 was shown in FIG. In the metal film forming treatment method of the third embodiment shown in FIG. 5, the conditioning treatment step (S1) is the conditioning and ultraviolet irradiation treatment step (S11) of the first embodiment, and the catalizing treatment step (S3) is performed. It is substituted by the catalizing and ultraviolet irradiation process process S31 of 2nd Embodiment.

Moreover, in the metal film formation processing method of 3rd Embodiment, ultraviolet irradiation is also performed also in the electroless copper plating process S5 in the metal film formation processing method of FIG. In this electroless copper plating process, the electroless copper plating process itself is divided into two stages, divided into an electroless copper plating process (S51) and (S54), and ultraviolet irradiation is performed even during the electroless copper plating process.

After the plating process by this processing process (S51), the ultraviolet irradiation to the surface of a resin base material exposes the part which the surface of a resin base material exposes by the ultraviolet irradiation process process (S52), and the copper metal film by electroless copper plating is mixed. It is done when By this ultraviolet irradiation, the adhesiveness of the resin surface and the copper metal which precipitates by electroless plating improves.

In addition, even when ultraviolet-ray irradiation is performed on the resin surface in the middle of an electroless copper plating process, when the cover glass plate is placed on the resin surface and the ultraviolet-ray is irradiated to the resin surface through the cover glass plate, the adhesion degree of the copper metal film is improved. I can improve it further.

After the ultraviolet irradiation treatment step S52 is completed, the acid treatment step S53 is performed to clean the surface of the deposited copper metal, and the remaining electroless copper plating treatment is performed in the electroless copper plating treatment step S54. Then, normal electrolytic copper plating process S6 is performed, and a copper metal film is formed on the deposited copper metal. In the case where the copper metal film formed in the processing step S51 is a film thickness capable of becoming a feed layer in the electrolytic copper plating process, the electroless copper plating process in the processing step S54 can be omitted.

By the above, by irradiating the surface with ultraviolet-ray in the presence of the processing liquid on the resin surface, when the resin surface by the ultraviolet irradiation effect was activated and the reactivity became high, the component in a processing liquid and the molecule | numerator of the resin surface became By chemically strong bonding, the copper metal of the electroless copper plating is strongly adhered to the resin surface.

Therefore, according to the metal film formation processing methods of 1st-3rd embodiment, the adhesiveness of the metal film formed on the resin base material surface and the resin base material is in the presence of a process liquid, and is used for strengthening activation of the resin surface by an ultraviolet irradiation effect. Was improved. Moreover, only by studying the timing of ultraviolet irradiation, various process liquids in each process process performed by the method of forming a metal film on the surface of the conventional resin base material can be used as it is, and there is no need to prepare a special process.

In addition, in the metal film formation processing methods of the first to the third embodiments described so far, the metal film is formed on the surface of the resin substrate through the plating nucleation treatment process, the electroless plating treatment process, and the electrolytic plating treatment process. The degree of adhesion between the metal film formed on the surface and the resin substrate is improved in accordance with the strengthening of activation of the resin surface due to the ultraviolet irradiation effect in the presence of the treatment liquid. Therefore, even when the metal film is formed on the resin substrate only by the electroless plating process without performing the electrolytic plating process that is part of the metal film formation, ultraviolet rays can be irradiated in the presence of the respective treatment liquids, and the adhesion degree is Since it improves by irradiation effect, even when forming a metal film only by an electroless-plating process, the metal film formation processing method of this embodiment can be applied.

Moreover, although the polyimide resin was mainly mentioned about the resin base material, the metal film formation treatment method of this embodiment is not limited to polyimide resin, Fluorine-type resins, such as an epoxy resin and polytetrafluoroethylene, acrylonitrile butadiene Applicable to styrene resin, polycarbonate resin and the like. If the resin surface is modified and activated by ultraviolet irradiation, it will not specifically limit about the material, It has the effect of improving the adhesiveness of a metal film. When forming a metal film on these resin substrates, it is natural that the wavelength of the ultraviolet-ray to irradiate is selected optimally according to the material.

In addition, although the metal film formation processing method of this embodiment demonstrated the case where a copper metal film is formed on the resin insulating layer laminated | stacked in the semiconductor device as an example, it is not limited to a semiconductor device about an application object, It is based on resin The present invention is also applied to the formation of a metal film in a semiconductor package using a circuit wiring apparatus or a build-up wiring substrate using a substrate or a flexible sheet.

In addition, other metals such as nickel and chromium may be used for the metal film formed on the surface of the resin substrate, for example, instead of copper as the metal for electroplating, as in the case where corrosion resistance is required.

Below, the specific example of the metal formation processing method by this embodiment is demonstrated. In this description, a case of forming a copper metal film on a resin insulating layer made of a polyimide resin laminated in a semiconductor device is shown. And before demonstrating an Example, the comparative example as a reference was shown in order to show the effect accompanying the metal film formation processing method of this embodiment.

[Comparative Example l]

Formation of the metal film by the comparative example 1 was performed according to each processing process of the metal film formation processing method shown in FIG.

In the conditioning treatment step (S1), the polyether was treated at 45 ° C for 5 minutes using a conditioning treatment liquid (containing 30 mL of the stock solution in 1 L of the treatment liquid) manufactured by Atotech Co., Ltd. The surface of the mid resin was cleaned. In the next pre-dipping treatment step (S2), a pre-dipping treatment solution (containing 200 mL of the stock solution in 1 L of the treatment solution) of the brand name cataprep 404 manufactured by Shiprey Co., Ltd. containing sodium chloride (NaCl) and sodium hydrogen sulfate (NaHSO ₄ ). In addition, the treatment for plating nuclei adsorption on the surface of the polyimide resin was performed in one minute of treatment time.

Subsequently, in the catalizing treatment step (S3), as catalyst, the above-mentioned cataprep 404 manufactured by Shiprey Co., Ltd. (containing 250 mL of the stock solution in 1 L of the treating solution), palladium chloride (PdCl) and stannous chloride (SnCl). ₂ ) Catalizing treatment was carried out at 45 ° C. for 5 minutes using a mixed treatment solution of trade name cataposit 44 (containing 33 mL of the stock solution in 1 L of the treatment solution) containing the same product to adsorb the complex salt of Pd and Sn. I was. Thereafter, in the accelerator treatment step (S4), an accelerator treatment for 8 minutes of treatment time was performed by Shipley's trade name accelerator 19E (containing 40 mL of the stock solution in 1 L of the treatment solution) containing hydrofluoric acid (HBF ₄ ). Pd was deposited as a plating nucleus on the surface of the polyimide resin.

In the electroless copper plating treatment step (S5), electroless copper plating was carried out for 8 minutes by electrolytic copper plating under the trade name Cupposit 328 manufactured by Shiprey Co., Ltd., using Pd as a catalyst. Precipitated. Here, the cupposit 328 is cupposit 328A containing copper sulfate (CuSO ₄ · 5H ₂ O) (120 mL in 1 L of the treatment solution), rossel salt (C ₄ H ₄ O ₆ K · Na), and sodium hydroxide ( It consists of 328L of cupposite (100 mL in 1 L of treatment liquid) containing NaOH) and cupposit 328C (15 mL of 1 L of treatment liquid) containing formaldehyde (HCHO).

Subsequently, in the electrolytic copper plating treatment step (S6), 40 minutes of electrolytic copper plating was carried out using an electric current of ^{2 A} / dm ² , using a trade name KappaPix 125 manufactured by Maltex Co., Ltd. Formed.

As mentioned above, the metal film by copper was formed on the insulating layer based on polyimide resin. In addition, as a result of measuring the adhesion between the polyimide resin and the metal film, a peel strength of about 100 gf / cm was obtained.

Comparative Example 2

Formation of the metal film concerning the comparative example 2 was performed according to each processing process of the metal film formation processing method shown in FIG. In the metal film forming treatment method of FIG. 8, the ultraviolet irradiation treatment step S0 is added before the execution of each treatment step in the metal film forming treatment method of FIG. 6.

Therefore, the treatment steps (S1) to (S6) shown in FIG. 8 are completely the same as the treatments in the treatment steps (S1) to (S6) shown in Comparative Example 1, and thus the description thereof is omitted, but the ultraviolet irradiation treatment In the step (S0), ultraviolet rays having a wavelength of 172 nm were irradiated on the surface of the polyimide resin at an illuminance of 13.44 mW / cm ² for 120 seconds. About this ultraviolet-ray irradiated resin base material, the process in each processing process (S1)-(S6) was performed sequentially.

As mentioned above, the metal film by copper was formed on the insulating layer based on polyimide resin. Moreover, as a result of measuring the adhesiveness of a polyimide resin and a metal film, the peeling strength about 122 gf / cm was obtained.

Example 1

Example 1 is a case where the metal film by copper was formed on the insulating layer based on polyimide resin according to the metal film formation processing method shown in FIG. The metal film formation processing method of FIG. 1 replaces the conditioning process S1 with the conditioning and ultraviolet irradiation process S11 based on the metal film formation method of FIG. Therefore, the processing process of forming a copper metal film on the surface of a polyimide resin base material was performed based on the processing process in the comparative example 1.

In Comparative Example 1, at a temperature of 45 ° C. in a conditioning treatment step (S1), a conditioning treatment solution (containing 30 mL of the stock solution in 1 L of the treatment solution) manufactured by Atotech Co., Ltd. Although the surface of the polyimide resin was cleaned for 5 minutes, in Example 1, as shown in FIG. 2, the conditioning treatment liquid 2 of the brand name Conditioner Neo Pact U made from the same Atotech Co., Ltd. was covered with the cover glass plate 7. The treatment was performed for 120 seconds while interposing a resin having a thickness of 10 µm between the resins 1 and irradiating an ultraviolet ray having a wavelength of 172 nm from the upper side with an illuminance of 13.44 mW / cm ² .

After the activation process of the resin surface by processing process (S11) was complete | finished, each processing process by the metal film formation processing method of the comparative example 1 was performed.

As mentioned above, the metal film by copper was formed on the insulating layer based on polyimide resin. And as a result of measuring the adhesiveness of a polyimide resin and a metal film, the peel strength value of 570 gf / cm or more which can be provided practically was obtained.

Example 2

Example 2 is a case where the metal film by copper was formed on the insulating layer based on polyimide resin according to the metal film formation processing method shown in FIG. Although the metal film formation processing method of FIG. 3 is based on the metal film formation method of FIG. 6, the catalizing process S3 is substituted by the catalizing and ultraviolet irradiation process S31. Therefore, an Example The treatment process of forming a copper metal film on the surface of the polyimide resin base material in 2 was performed similarly based on the treatment process in Comparative Example 1.

In Comparative Example 1, in the catalizing treatment step (S3), the cataprep 404 (prepared with 250 mL of the stock solution in 1 L of the treating solution), palladium chloride (PdCl ₂ ), and stannous chloride (manufactured by Shipley) were used as the catalyst. Catalizing treatment was carried out at 45 ° C. for 5 minutes using a mixed treatment solution of cataposit 44 (containing 33 mL of the stock solution in 1 L of the treatment solution) manufactured by the same company containing SnCl ₂ ) to form a complex salt of Pd and Sn. Although adsorbed, in Example 2, the mixed liquid of the same brand name cataprep 404 and the brand name cataposit 44 made by Shipley Co. is used as the catalyst, and this catalyst is shown in FIG. 4, and the cover glass plate 7 and the resin ( 1), it interposed in the layer of thickness 10micrometer, and the process was performed for 120 second, irradiating the ultraviolet-ray which has a wavelength of 172nm from upper direction with illuminance 13.44mW / cm <^2> .

As mentioned above, the metal film by copper was formed on the insulating layer based on polyimide resin. And as a result of measuring the adhesiveness of a polyimide resin and a metal film, the peel strength value of 700 gf / cm or more which can be provided practically was obtained.

Example 3

Example 3 is a case where the metal film by copper was formed on the insulating layer based on polyimide resin according to the metal film formation processing method by 3rd Embodiment shown in FIG. Although the metal film formation processing method of FIG. 5 is based on the metal film formation method of FIG. 6, it combines the 1st and 2nd embodiment, and the conditioning and ultraviolet irradiation process process (S11) is carried out in the conditioning process process (S1). ), And the catalizing treatment step (S3) is replaced by the catalizing and ultraviolet irradiation treatment step (S31).

Therefore, in the conditioning and ultraviolet irradiation processing process (S11), the conditioning treatment liquid 2 of the above-mentioned Atotech Co., Ltd. brand name Conditiona NeoPact U is 10 micrometers in thickness between the cover glass plate 7 and resin 1 120 seconds of irradiation with ultraviolet rays having a wavelength of 172 nm, and irradiated from above with an illuminance of 13.44 mW / cm ^2, and in the catalizing and ultraviolet irradiation treatment step (S31), the catalyst was prepared by Name ka tarp rep 404 and trade name Kata opposite to bit 44 using a cover glass plate (7) and the resin (1) with the interposed layer having a thickness 10㎛, ultraviolet light having a wavelength of 172nm is also roughness 13.44mW / cm ² between the The treatment was performed for 120 seconds while irradiating from above.

Moreover, in the metal film formation processing method of 3rd Embodiment, the ultraviolet-ray irradiation to the resin surface is performed also in the middle of an electroless copper plating process. In Comparative Example 1, the electroless copper plating treatment was performed for 8 minutes using the above-mentioned brand name Cuposite 328 manufactured by Shipley, but the electroless copper plating treatment was carried out in two stages. Ultraviolet irradiation was performed in the middle of the electroless plating process in which the portion exposed by the surface of the resin substrate and the copper metal film by electroless copper plating were mixed. Thereby, the adhesiveness of the resin base material and the copper metal by electroless copper plating was able to be improved.

In electroless copper plating process (S51), using Pd as a catalyst, it was immersed in the electroless copper plating process liquid by the above brand name cupid 328 by Shipley, and electroless copper plating was performed for 2 minutes of processing time. At this point, the plated copper metal was 0.025 µm thick in terms of the film thickness on the resin surface. And the to-be-processed object was removed from this electroless copper plating process liquid, and the ultraviolet-ray which has a wavelength of 172nm was irradiated to the surface of the said to-be-processed object for 120 second at roughness 13.44mW / cm <^2> in an ultraviolet-ray processing process (S52). .

Thereafter, in an acid treatment step (S53), an acid treatment was performed for 10 seconds using a treatment solution with 10% sulfuric acid to clean the surface of the copper metal attached with the plating nuclei of Pd as a catalyst. In addition, in order to perform further electroless copper plating in the electroless copper plating treatment step (S54), the treated object irradiated with ultraviolet rays is again immersed in the electroless copper plating treatment liquid described above and subjected to electroless copper plating treatment for 6 minutes, A copper metal film of 0.075 탆 was obtained.

In addition, similarly to the case of Comparative Example 1, in the electrolytic copper plating treatment step (S6), electrolytic copper plating was performed for 40 minutes at an electric current of ^{2 A} / dm ² using the tradename Kappaglim 125 manufactured by Maltex Co., Ltd. A micron copper metal film was formed.

As mentioned above, the metal film by copper was formed on the insulating layer based on polyimide resin. Moreover, as a result of measuring the adhesiveness of a polyimide resin and a metal film, the peel strength value 1050gf / cm or more higher than the peel strength value obtained in Example 1 or 2 was obtained.

As described above, according to the metal film forming treatment method according to the embodiment described above, since ultraviolet irradiation to the surface of the resin substrate is performed in the presence of the treatment liquid, the copper metal of the electroless plating of the electroless plating is continued while the surface activation is continued. It was found that adhesion to the surface was performed, and the adhesion thereof became strong, and the adhesion between the resin surface and the metal film could be improved, as compared with the case of the metal film formation of Comparative Examples 1 and 2.

As described above, in the metal film forming treatment method according to the present invention, ultraviolet treatment to the resin surface is performed in the presence of a treatment liquid used in each treatment step, so that activation by ultraviolet irradiation of the resin surface is promoted, and the effect thereof is improved. Electroless plating becomes possible while it is being continued, and the adhesiveness of the resin surface and precipitation metal by the ultraviolet irradiation effect can be improved, and a metal film is used for practical use, even without performing the etching process with respect to the conventionally performed resin surface. The degree of adhesion that can be provided was obtained.

In addition, since the etching treatment liquid is not used, it is easy to cope with danger and pollution, and the handling and discharge treatment are reduced, and the work load is reduced.

In addition, in the metal film forming treatment method according to the present invention, the timing of ultraviolet irradiation is studied to be performed when the treatment liquid used in each treatment step is present, and thus the adhesion between the resin substrate and the metal film is improved. It is not necessary to prepare a treatment agent for promoting surface modification separately from the treatment liquid in a normal treatment step, and thus the usual treatment liquid can be used as it is. do.

In addition, for the modification of the surface of the resin substrate, it is not necessary to provide a special treatment device other than the device for ultraviolet irradiation, and each treatment liquid used in the past can be used as it is. Can provide.

The method of forming a metal film on the surface of the resin substrate according to the present invention can be applied to the formation of a metal film on a laminated insulating layer in a semiconductor device, and the metal film can also be easily formed on a resin substrate or a flexible sheet. Inexpensive products can be provided.

Claims (24)

As a method of forming and processing a metal film on the surface of a resin substrate by treating in accordance with a plating nucleation process and an electroless plating process, A metal film forming treatment method of irradiating ultraviolet rays to the surface through a treatment liquid used before the electroless plating process. The method of claim 1, The metal film formation processing method in which the process by an electrolytic plating process is performed after the said electroless plating process. The method according to claim 1 or 2, And the treatment liquid is a conditioning treatment liquid for pretreating the surface before the plating nucleation step. The method of claim 3, The irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid and in the case of passing through the catalizing treatment liquid applied to the surface in the plating nucleation step. The method of claim 4, wherein The conditioning treatment liquid or the catalyzing treatment liquid is a thin film interposed between the glass plate and the surface in a thin layer formation method. The method according to claim 1 or 2, And the treatment liquid is a catalizing treatment liquid applied to the surface in the plating nucleation step. The method of claim 6, The irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid for pretreating the surface before the plating nucleation step and in the case of passing through the catalizing treatment liquid. The method of claim 7, wherein The conditioning treatment liquid or the catalyzing treatment liquid is a thin film interposed between the glass plate and the surface in a thin layer formation method. A semiconductor device having a metal film formed by plating on a resin insulating layer, And the metal film is formed on the surface of the resin substrate by a plating nucleation process and an electroless plating process including irradiating ultraviolet rays to the surface through a processing liquid used. The method of claim 9, The semiconductor device after the said electroless plating process is performed by the electrolytic plating process. The method of claim 9 or 10, And the treatment liquid is a conditioning treatment liquid for pretreating the surface before the plating nucleation step. The method of claim 11, The irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid and in the case of passing through the catalizing treatment liquid applied to the surface in the plating nucleation step. The method of claim 12, And the conditioning treatment liquid or the catalyzing treatment liquid is interposed in a thin layer between the glass plate and the surface. The method of claim 9 or 10, And the treatment liquid is a catalizing treatment liquid applied to the surface in the plating nucleation process. The method of claim 14, The irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid for pretreating the surface before the plating nucleation step and in the case of passing through the catalizing treatment liquid. The method of claim 15, The conditioning device or the catalyzing solution is a semiconductor device in which a thin layer is interposed between a glass plate and the surface. As a wiring board which has a metal film formed by plating on a resin insulating layer, And the metal film is formed on the surface of the resin substrate by a plating nucleation process and an electroless plating process including irradiating ultraviolet rays to the surface through a processing liquid used. The method of claim 17, After the electroless plating process, the wiring board is processed by the electrolytic plating process. The method of claim 17 or 18, And said processing liquid is a conditioning treatment liquid for pretreating said surface before said plating nucleation process. The method of claim 19, Irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid and in the case of passing through the catalizing treatment liquid applied to the surface in the plating nucleation step. The method of claim 20, And the conditioning treatment liquid or the catalizing treatment liquid is interposed thinly between the glass plate and the surface in a layered manner. The method of claim 17 or 18, And the processing liquid is a catalizing treatment liquid applied to the surface in the plating nucleation process. The method of claim 22, Irradiation of the ultraviolet rays is carried out both in the case of passing through the conditioning treatment liquid for pretreating the surface before the plating nucleation step and in the case of passing through the catalizing treatment liquid. The method of claim 23, wherein And the conditioning treatment liquid or the catalizing treatment liquid is interposed thinly between the glass plate and the surface in a layered manner.