JP2004162098A - Resin-metal laminate structure and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a laminate structure excellent in adhesion between a resin material and a metal layer without performing roughening a resin surface or interlayer formation; and a laminate structure produced thereby. <P>SOLUTION: The method for producing a resin-metal laminate structure comprises step (a) wherein the surface of a substrate with a resin appearing at the surface is exposed to a nitrogen plasma and step (b) wherein a metal layer is formed on the surface of the substrate after the exposure to the nitrogen plasma. In step (a), the nitrogen plasma treatment is conducted under such conditions that the integral strength of a nitrogen peak (N1s) detected after the exposure to the nitrogen plasma is larger than the integral strength of the nitrogen peak (N1s) detected before the exposure. The integral strength is detected by an X-ray photoelectronic spectral analysis of the resin surface of the substrate. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a laminated structure in which a metal layer is laminated on a surface of a resin material and a method of manufacturing the same, and more particularly, to a laminated structure in which adhesion between a resin material and a metal layer is improved and a method of manufacturing the same.
[0002]
[Prior art]
In a printed wiring board in which metal wiring is formed on a resin layer, the surface of the resin layer is subjected to a roughening treatment in order to increase the adhesion between the resin layer and the metal wiring. As the density of metal wiring has been increased, the wiring has become thinner and thinner. When the wiring is thin and thin, irregularities of about several μm due to the roughening treatment of the base surface cannot be ignored.
[0003]
Attempts have also been made to improve the adhesion by modifying the surface of the resin layer (for example, see Patent Documents 1 to 5). For example, Patent Literature 1 proposes a method of forming a copper film on a polyimide resin while introducing nitrogen gas at an initial stage of sputtering film formation. Further, Patent Document 2 proposes a method of performing a plasma treatment in an atmosphere of argon, helium, oxygen, nitrogen, or carbon dioxide before forming a copper film on a polyimide film containing 0.01 to 2 wt% of an inorganic filler of alumina or silica. Have been.
[0004]
In addition, attempts have been made to provide an intermediate layer of chromium, nickel, or the like between the polyimide resin layer and the copper wiring to improve the adhesion (for example, Patent Document 6).
[0005]
[Patent Document 1] JP-A-6-228738 [Patent Document 2] JP-A-2001-151916 [Patent Document 3] JP-A-63-270455 [Patent Document 4] JP-A-2001-73133 [ [Patent Document 5] Japanese Patent Application Laid-Open No. 2000-216534 [Patent Document 6] Japanese Patent Application Laid-Open No. 11-92917 [0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method of manufacturing a laminated structure having high adhesion between a resin material and a metal layer without performing a roughening treatment on a resin surface or forming an intermediate layer, and to provide the laminated structure. It is.
[0007]
[Means for Solving the Problems]
According to one aspect of the present invention, (a) exposing the surface of the substrate having the resin exposed on the surface to nitrogen plasma; and (b) forming a metal on the surface of the substrate after being exposed to the nitrogen plasma. Forming a layer, wherein in the step (a), the integrated intensity of a nitrogen (N1s) peak detected by subjecting the resin surface of the substrate to X-ray photoelectron spectroscopy after exposure to the nitrogen plasma. Is a resin-metal laminate structure that performs a nitrogen plasma treatment under a condition that the integrated intensity of a nitrogen (N1s) peak detected by X-ray photoelectron spectroscopy analysis of the resin surface of the substrate before being exposed to the nitrogen plasma. Is provided.
[0008]
According to another aspect of the present invention, there is provided a substrate having a polyimide resin exposed on the surface, and a laminate having a peel strength of 800 g / cm or more measured by a method specified in JIS standard number C5012, laminated on the polyimide resin surface of the substrate. A resin-metal laminated structure having a copper layer is provided.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
A method for manufacturing the resin-metal laminated structure according to the first embodiment of the present invention will be described. A substrate was prepared in which a resin layer made of a polyimide resin was laminated on both sides of a core substrate made of glass epoxy or the like. The polyimide resin used for the resin layer did not contain a filler such as alumina (Al ₂ O ₃ ) and silica (SiO ₂ ). This substrate was dried in the air at 120 ° C. for 30 minutes.
[0010]
The dried substrate was placed in contact with an electrode of a parallel plate type plasma processing apparatus so as to be in contact therewith, and nitrogen plasma processing was performed. The conditions for the nitrogen plasma treatment were a pressure of 10 Pa, a nitrogen flow rate of 100 sccm, a power of 0.8 W / cm ² , and a treatment time of 10 minutes. At this time, a voltage of about -350 V as a DC component with respect to the ground potential and a high frequency having an amplitude of 500 V were generated at the electrode on which the substrate was mounted. It is considered that the nitrogen ions are attracted to the substrate by the action of this voltage, so that the surface of the substrate is efficiently modified.
[0011]
Thereafter, the substrate was transferred to a copper ion plating apparatus, and a seed layer made of copper and having a thickness of 500 nm was formed. The conditions for forming the seed layer are a pressure of 0.01 Pa to 0.1 Pa and a film formation time of 3 minutes to 5 minutes.
[0012]
The substrate was taken out of the ion plating apparatus, and copper was electrolytically plated on the seed layer to form a wiring layer having a thickness of 20 μm.
[0013]
A sample in which the seed layer and the wiring layer were formed after the nitrogen plasma treatment for 10 minutes by the above method and a sample in which the seed layer and the wiring layer were formed without performing the nitrogen plasma treatment were prepared. These samples were subjected to a 90 ° peel test under the conditions of a tensile speed of 50 mm / min and a width of 10 mm by a measurement method specified in JIS standard number C5012.
[0014]
FIG. 1A shows the results of the peel test. It can be seen that the peel strength is greatly increased by the nitrogen plasma treatment for 10 minutes. A polyimide / copper laminated structure having a peel strength of about 1000 g / cm is obtained. As described above, the adhesion of the wiring layer made of copper can be increased without performing the roughening treatment on the surface of the resin layer or the formation of the intermediate layer.
[0015]
Note that FIG. 1A also shows the results of treatment with oxygen plasma, oxygen and CF ₄ plasma, and argon plasma for comparison. Oxygen plasma, there is no oxygen and CF ₄ most effective treatment by plasma. Although some effects are seen in the argon plasma treatment, the adhesion is significantly lower than in the nitrogen plasma treatment.
[0016]
The composition near the surface was analyzed by ESCA (Electron Spectroscopy for Chemical Analysis, X-ray photoelectron spectroscopy) with respect to the two types of samples having different nitrogen plasma treatments shown in FIG. 1A.
[0017]
FIG. 1B shows measurement data of ESCA. The horizontal axis indicates the energy of the bond, and the vertical axis indicates the peak height. The spectrum pi0 is the measurement result without nitrogen plasma treatment, and the spectrum pi10 is the measurement result with nitrogen plasma treatment for 10 minutes.
[0018]
Since the polyimide resin contains nitrogen as a component, a nitrogen (N1s) peak (around 400 eV) corresponding to the single bond CN bond included in the polyimide resin appears in the spectrum pi0. On the other hand, in the spectrum pi10, the width of the peak observed in pi0 is increased and the height is also increased, and the integrated intensity of the peak is increased. Further, another peak is generated on the lower energy side than the above-mentioned peak indicating the CN bond contained in the polyimide resin, which indicates that nitrogen having a different bonding state is introduced.
[0019]
In the first embodiment, the polyimide resin does not contain a filler such as alumina and silica. However, the effect of improving the adhesion by the nitrogen plasma treatment is expected for the polyimide resin containing these fillers. Is done.
[0020]
Further, in the present embodiment, a substrate in which polyimide resin is laminated on both surfaces of a core substrate made of glass epoxy or the like is used, but even when copper is laminated on a normal polyimide film, similar effects can be obtained. .
[0021]
Next, a method for manufacturing the resin-metal laminated structure according to the second embodiment will be described. In this embodiment, a substrate in which the resin layer is a benzocyclobutene (BCB) resin is used instead of the polyimide resin used in the first embodiment. The nitrogen plasma treatment, the step of forming the copper seed layer and the wiring layer, and the like were the same as the steps shown in the first embodiment.
[0022]
Also in the second example, a sample in which the seed layer and the wiring layer were formed after the nitrogen plasma treatment for 10 minutes and a sample in which the seed layer and the wiring layer were formed without performing the nitrogen plasma treatment were produced. These samples were subjected to a 90 ° peel test under the conditions of a tensile speed of 50 mm / min and a width of 10 mm by a measurement method specified in JIS standard number C5012.
[0023]
FIG. 2A shows the results of the peel test. It can be seen that even when a BCB-based resin is used, the peel strength is significantly increased by the nitrogen plasma treatment for 10 minutes. A BCB / copper laminated structure having a peel strength of about 600 g / cm is obtained. The adhesion of the wiring layer made of copper can be improved without performing the surface roughening treatment or the formation of the intermediate layer of the resin layer.
[0024]
The composition near the surface was analyzed by ESCA for the two samples having different nitrogen plasma treatments shown in FIG. 2A.
[0025]
FIG. 2B shows measurement data of ESCA. The spectrum bcb0 is the measurement result without nitrogen plasma treatment, and the spectrum bcb10 is the measurement result with nitrogen plasma treatment for 10 minutes.
[0026]
Since the BCB-based resin does not contain nitrogen as a component, a clear peak corresponding to nitrogen is not seen in the spectrum bcb0. On the other hand, in the spectrum bcb10, a clear peak corresponding to the nitrogen (N1s) peak (around 400 eV) appears. That is, it can be seen that the nitrogen plasma treatment introduces a nitrogen-containing functional group into the surface of the BCB-based resin that originally does not contain nitrogen.
[0027]
From the findings shown in the first and second embodiments, the reason for the improvement in the adhesion is understood, for example, as follows. The functional group containing nitrogen introduced to the resin layer surface by the nitrogen plasma treatment includes, for example, those that form a coordination bond between nitrogen and copper, such as a cyano group (a triple bond of a CN bond). It is considered that the coordination bond improves the adhesion between the resin layer and the copper seed layer.
[0028]
From the above findings, among the resins containing nitrogen as a component element, when comparing the ESCA analysis data before and after the nitrogen plasma treatment, the width of the peak corresponding to the binding energy of nitrogen becomes wider or higher after the nitrogen plasma treatment. In the case of a resin that increases the peak intensity and increases the integrated intensity of the peak, improvement in adhesion is expected. For example, the polyimide resin shown in the first embodiment can be understood as a resin in this category.
[0029]
In the case of the polyimide resin of the first example, as shown in FIG. 1B, the integrated intensity of the peak increased about twice before and after the nitrogen plasma treatment. In other resins containing nitrogen as a component element, it may be considered that high adhesiveness can be obtained if the integrated intensity of the peak becomes about twice or more before and after the nitrogen plasma treatment.
[0030]
In addition, even if the resin does not contain nitrogen as a component element, when the ESCA analysis data before and after the nitrogen plasma treatment are compared, a peak corresponding to the binding energy of nitrogen that did not exist before the nitrogen plasma treatment shows a peak corresponding to the nitrogen plasma treatment. It is considered that any resin that appears later has an effect of improving adhesion. For example, the BCB-based resin shown in the second embodiment can be understood as a resin in this category.
[0031]
The metal that can provide high adhesion to the resin layer that has been subjected to the nitrogen plasma treatment is not limited to copper shown in the first and second embodiments. A metal having a strong bonding force with nitrogen, such as nickel or chromium, can be used.
[0032]
In the first and second embodiments, the nitrogen plasma processing time was set to 10 minutes. The effect of improving the adhesion begins to appear in a processing time of 1 minute or more, but is preferably 5 minutes or more.
[0033]
Further, in the first and second embodiments, a sample in which the thickness of the copper wiring layer was set to 20 μm was prepared. However, even when the thickness is other than that, the same effect of improving the adhesion can be obtained by the nitrogen plasma treatment. .
[0034]
Note that there is no particular change in the smoothness of the resin layer surface before and after the nitrogen plasma treatment shown in the first and second embodiments. The surface roughness Rz can be set to about 5 nm before the treatment, and 20 nm or less even after the treatment. Here, the surface roughness Rz is a ten-point average roughness Rz according to the JIS standard, and was determined by measuring a range of 2 μm × 2 μm by AFM (Atomic Force Microscopy).
[0035]
Next, a third embodiment will be described with reference to FIGS. Example 1 In this example, a method for manufacturing a printed wiring board by a subtractive method using the method for manufacturing a resin-metal laminated structure of the present invention will be described.
[0036]
As shown in FIG. 3A, an inner copper wiring 2 is formed on a surface of a resin substrate 1 made of glass epoxy or the like. A resin layer 3 made of a polyimide resin or a BCB-based resin is formed on the surface of the resin substrate 1 so as to cover the inner layer copper wiring 2. As the resin layer 3, as described above, a resin having a property of introducing nitrogen by a nitrogen plasma treatment can be used. The thickness of the resin layer 3 is, for example, 40 μm.
[0037]
By irradiating the resin layer 3 with a laser beam, a via hole 4 exposing a part of the inner layer copper wiring 2 is formed. The diameter of the via hole 4 is, for example, 50 μm. For example, an ultraviolet laser can be used as the laser. Residue (smear) 9 after laser processing remains on the bottom surface of via hole 4.
[0038]
The substrate 20 in which the via hole 4 is formed is exposed to plasma of argon, oxygen, or hydrogen, or plasma containing two or more of these elements, and the smear 9 on the bottom surface of the via hole 4 is removed.
[0039]
Next, the substrate from which the smear has been removed is exposed to nitrogen plasma to modify the surface of the substrate, thereby improving the adhesion to a copper seed layer to be formed later. Details of the nitrogen plasma processing step will be described later with reference to FIG.
[0040]
It is preferable that the side wall of the via hole 4 is tapered so that the side wall is easily exposed to nitrogen plasma. In order to form a taper, it is preferable that the laser beam profile has a convex shape such as a Gaussian distribution shape or a trapezoidal shape.
[0041]
As shown in FIG. 3B, a seed layer 6 made of copper is formed on the surface of the resin layer 3 after the surface modification and on the inner surface of the via hole 4 by sputtering or the like. During the process of forming the seed layer 6 from the plasma processing, it is preferable that the substrate 20 be transported in a vacuum and not exposed to the atmosphere.
[0042]
After the formation of the seed layer 6, a wiring layer 7 made of copper is formed on the surface of the seed layer 6 by electrolytic plating or electroless plating. Electroless plating has an advantage that the thickness of the wiring layer 7 can be easily controlled. The plating method may be appropriately selected depending on the purpose. The thickness of the wiring layer is generally 10 to 30 μm.
[0043]
The thickness of the seed layer 6 is preferably 100 nm or more in consideration of dissolution in the plating solution. Further, from the viewpoint of shortening the film formation time and the ease of removal by etching in a later step, the seed layer 6 is preferably 1 μm or less. The thickness of the seed layer 6 is, for example, 300 nm to 1 μm.
[0044]
As shown in FIG. 3C, a resist is applied to the surface of the wiring layer 7, and the resist pattern 8 is formed through exposure and development steps. Using the resist pattern 8 as a mask, the wiring layer 7 and the seed layer 6 are etched using an acidic chemical. After the etching, the resist pattern 8 is removed. In the steps up to this point, a wiring including the seed layer 6 and the wiring layer 7 is formed. This wiring is electrically connected to the inner layer wiring 2 via the inside of the via hole 4.
[0045]
As described above, the subtractive method has been described as an example, but the printed wiring board can also be manufactured by the semi-additive method. In the semi-additive method, after forming the seed layer, a resist is applied on the surface of the seed layer, and a resist pattern is formed through exposure and development steps. Using this resist pattern as a mold, a wiring layer is formed by electrolytic plating. A wiring layer is formed on a portion of the seed layer where no resist pattern exists. After forming the wiring layer, the resist pattern is removed, and unnecessary seed layers below the resist pattern are etched away. In the semi-additive method, etching for forming a wiring layer pattern is not performed. Therefore, there is an advantage that the shoulder of the wiring layer is not rounded during etching.
[0046]
Hereinafter, with reference to FIG. 4, the step of modifying the surface of the resin layer 3 by the nitrogen plasma treatment, the step of removing smear (desmear) in the preceding step, and the step of forming a copper seed layer in the subsequent step will be described in detail.
[0047]
FIG. 4 is a schematic diagram of a metal film forming apparatus used in the method of manufacturing a printed wiring board according to the present embodiment.
[0048]
The plasma processing chamber 10 and the seed layer deposition chamber 12 are connected via a gate valve 15. The plasma processing chamber 10 is connected to a loading load lock chamber (not shown) through a gate valve 13, and the seed layer deposition chamber 12 is loaded through a gate valve 16 to unload a load lock chamber (not shown). It is connected to the. Gas inlets 50 and 54 and exhaust ports 51 and 55 for introducing gases required for processing are connected to the chambers 10 and 12, respectively. The exhaust ports 51 and 55 are connected to a vacuum exhaust device (not shown).
[0049]
The substrate 20 after the formation of the via hole 4 shown in FIG. 3A is carried into the plasma processing chamber 10 through the gate valve 13 shown in FIG. The electrode 19 is one electrode of the parallel plate type plasma generator. The substrate 20 is set so as to be in contact with the electrode 19. Part of the gas inlet 50 and the plasma processing chamber 10 function as the other electrode. The plasma processing chamber 10 and the gas inlet 50 are grounded.
[0050]
A high frequency voltage is applied between the electrode 19 and the gas inlet 50 by the high frequency power supply 17. A matching box 18 is inserted between the electrode 19 and the high frequency power supply 17. In the plasma processing chamber 10, a nitrogen plasma process for improving adhesion and a desmear process as a preceding process are performed.
[0051]
First, smear is removed. The inside of the plasma processing chamber 10 is evacuated. Oxygen gas or argon gas is introduced, and then a high-frequency voltage is applied to generate plasma. Smear 9 remaining on the bottom surface of via hole 4 is removed, and the surface of resin layer 3 and the inner surface of via hole 4 are cleaned. The time required for the desmear treatment depends on the composition of the resin layer 3, but 1 to 5 minutes is sufficient.
[0052]
Next, the surface of the resin layer 3 is modified by nitrogen plasma treatment. The introduction of oxygen gas or argon gas is stopped, the processing chamber is evacuated, and then nitrogen gas is introduced. Next, a high-frequency voltage is applied to generate plasma.
[0053]
The conditions for the nitrogen plasma treatment may be a pressure of 1 Pa to 20 Pa, an input power of 0.1 W / cm ^{2 to} 5.0 W / cm ² , and a treatment time of 1 minute or more. Preferably, the pressure is greater than 5 Pa and equal to or less than 20 Pa, and the treatment time is 5 minutes to 10 minutes. The input power is, for example, 0.8 W / cm ² , and the nitrogen flow rate is, for example, 100 sccm.
[0054]
In order to maintain the surface smoothness after the plasma treatment, the input power density is preferably 5.0 W / cm ² or less. Further, in order to obtain the effect of improving the adhesion, it is preferable that it is at least 0.1 W / cm ² or more.
[0055]
It is considered that this nitrogen plasma treatment forms a nitrogen-containing functional group that promotes chemical bonding with a metal such as copper on the surface of the resin layer 3. Adhesion with the seed layer 6 formed in the next step is improved.
[0056]
The substrate 20 that has been subjected to the nitrogen plasma processing passes through the gate valve 15 and is carried into the seed layer deposition chamber 12 that is a DC magnetron sputtering apparatus. A copper target 60 as a film material is installed in the seed layer deposition chamber 12.
[0057]
As shown in FIG. 3B, a seed layer 6 made of copper on the resin layer 3 is formed in the seed layer forming chamber 12. Regarding temperature conditions, it is desirable that the substrate temperature during film formation does not exceed the glass transition temperature of the resin layer 3.
[0058]
The seed layer film forming chamber 12 is not limited to a DC magnetron sputtering apparatus, but may be any other apparatus that can use a vapor phase growth method such as an RF magnetron sputtering apparatus, an ion plating apparatus, a vacuum deposition apparatus, and a chemical vapor deposition apparatus. What is necessary is just a film-forming chamber. By employing a vacuum film forming method, a metal film can be formed with high reproducibility in a fine via hole as compared with a case of employing a wet film forming method.
[0059]
After the nitrogen plasma treatment, it is desirable to continuously form a copper seed layer in a vacuum in order to prevent dust and dust in the air from adhering to the substrate, but it is not always necessary to form the copper seed layer continuously. Absent. After the nitrogen plasma treatment, for a short period of time, the film may be stored in an environment such as a desiccator that can prevent re-adsorption of moisture, and then returned to the seed layer deposition chamber 12 to form a film.
[0060]
The substrate 20 on which the seed layer 6 is formed is transferred to the unloading load lock chamber through the gate valve 15. After unloading, copper is electrolytically or electrolessly plated on the surface of the seed layer 6 to form the wiring layer 7.
[0061]
A case has been described in which one plasma processing chamber is commonly used for oxygen or argon plasma processing for desmearing and nitrogen plasma processing for improving adhesion, but the productivity is improved by installing dedicated processing equipment for each. Can do things.
[0062]
The processing of a printed wiring board having via holes has been described as an example. However, when processing a substrate that has not been subjected to via processing, desmear processing using oxygen gas or argon gas can be omitted. Only the surface modification step using nitrogen plasma and the seed layer formation step are performed.
[0063]
Now, as shown in FIG. 3B, the seed layer 6 needs to be continuously coated up to the inner surface of the via hole 4 having a fine diameter of about 50 μm. An ion plating apparatus using a pressure gradient plasma gun is suitable for forming a film that continuously covers the inside of the fine via hole 4. As described below, a film can be formed well on the side wall of the via hole 4. An ion plating apparatus using a pressure gradient plasma gun is described in, for example, JP-A-2002-30423.
[0064]
FIG. 5 shows a schematic diagram of this ion plating apparatus. A vacuum evacuation device 41 and a pressure gradient type plasma gun 31 are attached to a vacuum chamber 30 which is a film forming chamber. The detailed structure of the pressure gradient plasma gun 31 is described in, for example, Japanese Patent Application Laid-Open No. 7-138743. The pressure gradient plasma gun 31 causes the argon plasma beam PB to enter the vacuum chamber 30. A steering coil 33 and the like disposed at a connection between the plasma gun 31 and the vacuum vessel 30 control the intensity of the argon plasma beam PB and the distribution of argon ions.
[0065]
An anode member 32 is arranged at the bottom inside the vacuum vessel 30. The anode member 32 includes a hearth 34 serving as a main anode and an annular auxiliary anode 35 disposed around the hearth 34. The auxiliary anode 35 is configured to include a ring-shaped container arranged around and concentric with the hearth 34. An annular container houses an annular permanent magnet 38 made of ferrite or the like and a coil 39 laminated concentrically with the permanent magnet 38.
[0066]
The permanent magnet 38 and the coil 39 form a cusp-shaped magnetic field immediately above the hearth 34. The cusp-shaped magnetic field corrects the direction and the like of the plasma beam PB incident on the hearth 34. By controlling the current flowing through the coil 39, the direction of the plasma beam PB can be finely adjusted.
[0067]
The hearth 34 is formed of a conductive material, and is supported by a grounded vacuum vessel 30 via an insulator. The potential of the hearth 34 is controlled to be positive, and the hearth 34 sucks the plasma beam PB downward. Note that a copper target 36 which is a film material to be formed on the hearth 34 is loaded. The target 36 is heated by the collision of electrons flowing from the argon plasma beam PB, and is melted and evaporated.
[0068]
The transport mechanism 40 is connected to the upper surface of the vacuum container 30. The transport mechanism 40 holds the target substrate 20 on which the film is to be formed so that the surface on which the film is to be formed faces the hearth 34, and transports the substrate appropriately.
[0069]
When the electrons flowing from the argon plasma beam PB emitted from the pressure gradient plasma gun 31 collide, a part of the target 36 is heated and melted and evaporated. The evaporated copper atoms are ionized in the argon plasma and collide with the surface of the substrate 20 with high energy.
[0070]
Since the copper ions colliding with the substrate 20 have high energy, a resputtering phenomenon occurs in the via holes. Copper on the bottom of the via hole is sputtered and adheres to the side wall. It is also expected that copper ions incident on the bottom surface of the via hole are reflected and adhere to the side wall. As described above, the seed layer having a sufficient thickness can be formed also on the side wall of the via hole by the ion plating apparatus using the pressure gradient plasma gun.
[0071]
Here, the acceleration energy of the copper ions is desirably 50 eV or more at which recoil starts to frequently occur and 300 eV or less at which damage to the resin can be prevented.
[0072]
Although the present invention has been described with reference to the embodiments, the present invention is not limited thereto. For example, it will be apparent to those skilled in the art that various modifications, improvements, combinations, and the like can be made.
[0073]
【The invention's effect】
As described above, according to the present invention, the surface of the resin member is exposed to nitrogen plasma, and then the metal wiring layer is formed on the resin member, so that the resin surface is roughened or the intermediate layer is formed. In addition, the adhesion between the resin member and the metal wiring layer can be improved.
[Brief description of the drawings]
FIG. 1 is a table showing the peel strength of a wiring layer formed on a polyimide resin member and an ESCA analysis spectrum of the polyimide resin member.
FIG. 2 is a table showing the peel strength of a wiring layer formed on a BCB-based resin member and an ESCA analysis spectrum of the BCB-based resin member.
FIG. 3 is a cross-sectional view of a substrate for describing a method of manufacturing a printed wiring board.
FIG. 4 is a schematic view of a film forming apparatus used in a method for manufacturing a resin-metal laminated structure according to an embodiment.
FIG. 5 is a schematic diagram of an ion plating apparatus.
[Explanation of symbols]
REFERENCE SIGNS LIST 1 resin substrate 2 inner wiring 3 resin layer 4 via hole 6 seed layer 7 wiring layer 8 resist pattern 9 smear 10 plasma processing chamber 12 seed layer deposition chambers 13, 15, 16 gate valve 17 high frequency power supply 18 matching box 19 electrode 20 substrate 50 , 54 Gas inlet 51, 55 Exhaust 60 Target

Claims (11)

(A) exposing the surface of the substrate having the resin exposed on the surface to nitrogen plasma;
(B) forming a metal layer on the surface of the substrate after being exposed to the nitrogen plasma;
In the step (a), after the exposure to the nitrogen plasma, the integrated intensity of the nitrogen (N1s) peak detected by performing X-ray photoelectron spectroscopy analysis on the resin surface of the substrate before the exposure to the nitrogen plasma. A method for producing a resin-metal laminated structure, wherein a nitrogen plasma treatment is performed under a condition where the integrated intensity of a nitrogen (N1s) peak detected by performing X-ray photoelectron spectroscopy analysis on the resin surface of the substrate. (C) exposing the surface of the substrate having the resin exposed on the surface to nitrogen plasma;
(D) forming a metal layer on the surface of the substrate after being exposed to the nitrogen plasma;
Before exposing the resin surface of the substrate to the nitrogen plasma, the nitrogen (N1s) peak is not detected by X-ray photoelectron spectroscopy analysis of the resin surface of the substrate, and in the step (c), the nitrogen plasma is exposed to the nitrogen plasma. A method for producing a resin-metal laminated structure, wherein a nitrogen plasma treatment is performed under the condition that a nitrogen (N1s) peak is detected by X-ray photoelectron spectroscopy analysis of the resin surface of the substrate after the exposure. Exposing the surface of the substrate having the resin exposed on the surface to nitrogen plasma by setting the pressure in the plasma chamber to more than 5 Pa and less than 20 Pa;
Forming a metal layer on the surface of the substrate after being exposed to the nitrogen plasma. Exposing the surface of the substrate where the polyimide resin containing no filler is exposed to the surface to nitrogen plasma,
Forming a metal layer on the surface of the substrate after being exposed to the nitrogen plasma. Exposing the surface of the substrate having the benzocyclobutene-based resin exposed to nitrogen plasma,
Forming a metal layer on the surface of the substrate after being exposed to the nitrogen plasma. The method for manufacturing a resin-metal laminated structure according to any one of claims 1 to 5, wherein the metal forming the metal layer is at least one of copper, nickel, and chromium. The method for producing a resin-metal laminate structure according to any one of claims 1 to 6, wherein the metal layer is formed by an ion plating apparatus having a pressure gradient plasma gun. A substrate with a polyimide resin exposed on the surface,
A copper layer laminated on the polyimide resin surface of the substrate and having a peel strength of 800 g / cm or more as measured by a method specified in JIS standard number C5012;
A resin-metal laminated structure having: A substrate with a benzocyclobutene-based resin exposed on the surface,
A copper layer laminated on the benzocyclobutene-based resin surface of the substrate and having a peel strength of 500 g / cm or more as measured by a method specified in JIS standard number C5012;
A resin-metal laminated structure having: A substrate on which a resin is exposed on the surface and a functional group containing nitrogen is present on the surface,
A copper layer containing copper which is stacked on the surface of the substrate and forms a coordination bond with nitrogen contained in the functional group,
A resin-metal laminated structure having: The resin-metal laminate structure according to any one of claims 8 to 10, wherein the surface of the substrate has a ten-point average roughness Rz defined by JIS standards of 20 nm or less.

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