WO2024034426A1 - Copper etchant for removing copper seed layer - Google Patents

Copper etchant for removing copper seed layer Download PDF

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Publication number
WO2024034426A1
WO2024034426A1 PCT/JP2023/027679 JP2023027679W WO2024034426A1 WO 2024034426 A1 WO2024034426 A1 WO 2024034426A1 JP 2023027679 W JP2023027679 W JP 2023027679W WO 2024034426 A1 WO2024034426 A1 WO 2024034426A1
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Prior art keywords
copper
seed layer
etching solution
copper seed
hydrogen peroxide
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PCT/JP2023/027679
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French (fr)
Japanese (ja)
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優 清水
秀和 本間
晃治 北
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奥野製薬工業株式会社
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Priority to JP2024540379A priority Critical patent/JPWO2024034426A1/ja
Publication of WO2024034426A1 publication Critical patent/WO2024034426A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a copper etching solution for removing a copper seed layer.
  • a copper etchant is used to remove the copper seed layer that exists between copper interconnects.
  • Such a copper etching solution is required to have sufficient ability to remove the copper seed layer.
  • a sulfuric acid/hydrogen peroxide based etching solution is generally used (for example, Patent Document 1).
  • An object of the present invention is to provide a copper etching solution for removing copper seeds that has sufficient removability of the copper seed layer and suppresses increase in surface roughness of copper wiring or copper electrodes and thinning of the circuit. shall be.
  • the present invention relates to the following copper etching solution for removing a copper seed layer.
  • a copper etching solution for removing a copper seed layer which contains an organic acid and hydrogen peroxide and has a pH of 5.0 to 8.0.
  • 2. The copper etching solution for removing a copper seed layer according to item 1, wherein the organic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and salts thereof. 3.
  • the copper etching solution for removing a copper seed layer according to item 3 wherein the hydrogen peroxide stabilizer is at least one selected from the group consisting of lactams, glycols, and phenolsulfonates. 5. Item 5. The copper etching solution for removing a copper seed layer according to any one of Items 1 to 4, further containing a pH buffer. 6. Item 5. The copper etching solution for removing a copper seed layer according to item 5, wherein the pH buffer is at least one selected from the group consisting of inorganic phosphates and citrates. 7. Item 7. The copper etching solution for removing a copper seed layer according to any one of Items 1 to 6, which does not contain sulfuric acid. 8.
  • a method for manufacturing a circuit board comprising the step of removing a copper seed layer between circuits using the copper etching solution for removing the copper seed layer according to any one of Items 1 to 7. 9.
  • the copper etching solution for removing the copper seed layer of the present invention has sufficient removability of the copper seed layer, and can suppress increase in surface roughness of copper wiring or copper electrodes and circuit thinning.
  • the copper etching solution for removing copper seed layer of the present invention contains an organic acid and hydrogen peroxide, and has a pH of 5. It is characterized by being between 0 and 8.0.
  • the copper etching solution for removing the copper seed layer of the present invention is a copper etching solution containing an organic acid and a hydrogen peroxide solution so that the pH is within a specific range, so it reduces damage to the electrolytic copper plating part and removes the copper wiring or Increase in surface roughness of the copper electrode and thinning of the circuit are suppressed, and the copper seed layer portion between the circuits where copper needs to be removed can be preferentially etched and removed.
  • the copper etching solution for removing a copper seed layer of the present invention hydrogen peroxide acts as an oxidizing agent, and an organic acid acts as a chelating agent or an etching aid.
  • copper is etched by using a combination of an organic acid and hydrogen peroxide, but since the copper seed layer is etched more selectively than electrolytic copper plating, When removing unnecessary copper seed layers between circuits, damage to circuit parts formed of electrolytic copper is suppressed, and increase in surface roughness of copper wiring or copper electrodes and circuit thinning are suppressed. Further, since the copper etching solution for removing the copper seed layer of the present invention has a pH within a specific range, it is possible to suppress an increase in the surface roughness of the copper wiring or the copper electrode and a narrowing of the circuit.
  • the pH of the copper etching solution of the present invention is 5.0 to 8.0. If the pH is less than 5.0, increase in surface roughness of copper wiring or copper electrodes and thinning of the circuit cannot be suppressed. If the pH exceeds 8.0, the copper seed layer cannot be removed sufficiently.
  • the pH of the copper etching solution is preferably 6.0 to 7.0.
  • organic acid is not particularly limited, and organic acids used in copper etching solutions can be used. Such organic acids include dicarboxylic acids, tricarboxylic acids, and salts thereof.
  • dicarboxylic acids examples include oxalic acid, tartaric acid, malic acid, malonic acid, succinic acid, and adipic acid. These dicarboxylic acids may be salts.
  • the dicarboxylic acid salt is not particularly limited, and includes known metal salts, and specifically includes sodium salts, potassium salts, ammonium salts, and the like.
  • tricarboxylic acids examples include citric acid and nitrilotriacetic acid. These tricarboxylic acids may be salts. Tricarboxylic acid salts are not particularly limited, and include known metal salts, and specific examples include sodium salts, potassium salts, ammonium salts, and the like.
  • organic acids may be used alone or in combination of two or more.
  • the copper seed layer between the circuits can be etched in a shorter time.
  • the content of organic acid in the copper etching solution is not particularly limited, and is preferably 10 to 60 g/L, more preferably 20 to 55 g/L, and even more preferably 30 to 40 g/L.
  • the lower limit of the content of the organic acid is within the above range, the removability of the copper seed layer by the copper etching solution is further improved.
  • the upper limit of the content of the organic acid is within the above range, increase in surface roughness of the copper wiring or copper electrode and circuit thinning are further suppressed.
  • Hydrogen peroxide is not particularly limited, and it may be dissolved in water and used as a hydrogen peroxide solution.
  • the content of hydrogen peroxide in the copper etching solution is not particularly limited, and is preferably 15 to 100 g/L, more preferably 25 to 70 g/L, and even more preferably 30 to 50 g/L in terms of hydrogen peroxide.
  • the lower limit of the content of hydrogen peroxide is within the above range, the removability of the copper seed layer by the copper etching solution is further improved.
  • the upper limit of the content of hydrogen peroxide is within the above range, increase in surface roughness of the copper wiring or copper electrode and narrowing of the circuit are further suppressed.
  • the copper etchant of the present invention may contain a hydrogen peroxide stabilizer.
  • the stability of hydrogen peroxide in the copper etchant over time is further improved.
  • the hydrogen peroxide stabilizer is not particularly limited, and those used as hydrogen peroxide stabilizers in aqueous solutions can be used.
  • Such hydrogen peroxide stabilizers include lactams, glycols, phenolsulfonates, and the like.
  • the lactam is not particularly limited and includes, for example, 4-pentanlactam, ⁇ -caprolactam, and the like.
  • Glycols are not particularly limited, and include ethylene glycol, propylene glycol, diethylene glycol, and the like.
  • the phenolsulfonic acid salt is not particularly limited, and examples thereof include sodium p-phenolsulfonate, p-toluenesulfonic acid, and the like. Among these, ⁇ -caprolactam is preferred.
  • the above hydrogen peroxide stabilizers may be used alone or in combination of two or more.
  • the content of the hydrogen peroxide stabilizer in the copper etching solution is not particularly limited, and is preferably 1 to 30 g/L, more preferably 3 to 25 g/L, and even more preferably 5 to 20 g/L.
  • the hydrogen peroxide in the copper etching solution becomes more stable.
  • the upper limit of the content of the hydrogen peroxide stabilizer is above the above range, it is stable, but a dramatic improvement in the effect is unlikely to be observed, so economical efficiency is improved by setting the upper limit to the above range.
  • the copper etching solution of the present invention may contain a pH buffer.
  • the copper etching solution contains a pH buffering agent, the pH of the copper etching solution becomes more stable.
  • the pH buffer is not particularly limited, and those used as pH buffers for copper etching solutions can be used.
  • pH buffering agents include inorganic phosphates, carboxylates, and the like.
  • the inorganic phosphate is not particularly limited and includes, for example, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hypophosphite, sodium phosphate, sodium hydrogen phosphate, and the like.
  • the carboxylic acid salt is not particularly limited, and includes, for example, carboxylic acid sodium salts such as sodium citrate, disodium citrate, trisodium citrate, sodium acetate, and sodium tartrate; potassium citrate, dipotassium citrate, and trisodium citrate.
  • carboxylic acid potassium salts such as potassium, potassium acetate, potassium tartrate, and potassium sodium tartrate
  • carboxylic acid ammonium salts such as diammonium hydrogen citrate, triammonium citrate, ammonium acetate, and ammonium tartrate.
  • the above pH buffering agents may be used alone or in combination of two or more.
  • the content of the pH buffer in the copper etching solution is not particularly limited, and is preferably 5 to 160 g/L, more preferably 7 to 100 g/L, even more preferably 8 to 50 g/L, particularly 10 to 30 g/L. preferable.
  • the pH of the copper etching solution becomes more stable.
  • the upper limit of the content of the pH buffering agent is above the above range, it can be used as a buffer, but it is difficult to see a dramatic improvement in the effect, so economical efficiency is improved by having the upper limit within the above range.
  • the copper etching solution of the present invention may further contain other components.
  • the other components include pH adjusters, antifungal agents, and the like.
  • pH adjuster is not particularly limited, and various pH adjusters used in copper etching solutions can be used.
  • acids such as hydrochloric acid and phosphoric acid
  • alkalis such as sodium hydroxide, potassium hydroxide, and aqueous ammonia
  • pH adjusters can be used alone or in combination of two or more.
  • the content of the pH adjuster in the copper etching solution is not particularly limited, and may be any amount that can adjust the pH of the copper etching solution of the present invention to 5.0 to 8.0.
  • the content of the pH adjuster in the copper etching solution is preferably about 15 to 35 g/L, more preferably about 20 to 30 g/L.
  • the antifungal agent is not particularly limited, and various antifungal agents used in copper etching solutions can be used.
  • the antifungal agent it is preferable to use a copper compound, and specifically, copper acetate, copper chloride, copper nitrate, copper carbonate, copper oxide, etc. can be used.
  • antifungal agents can be used alone or in combination of two or more.
  • the content of the antifungal agent in the copper etching solution is not particularly limited.
  • the content of the antifungal agent in the copper etching solution is preferably about 0.01 to 0.2 g/L, more preferably about 0.05 to 0.15 g/L in terms of copper concentration.
  • each of the above components is preferably contained in a solvent.
  • a known solvent constituting a copper etching solution can be used, and examples thereof include water, alcohols, and the like. Water is preferred because it is easy to handle and safe.
  • the content of the solvent is not particularly limited, and may be the remainder after adding each of the above components.
  • the copper etching solution of the present invention preferably does not contain sulfuric acid. Since the copper etching solution of the present invention does not contain sulfuric acid, increase in surface roughness of copper wiring or copper electrodes and circuit thinning can be further suppressed.
  • the method for producing the copper etching solution of the present invention is not particularly limited, and can be produced by conventionally known methods.
  • Such a production method includes, for example, adding the organic acid and hydrogen peroxide to a solvent such as water, and then adding the hydrogen peroxide stabilizer, pH buffer, and pH adjuster as necessary. It can be manufactured by a manufacturing method in which other components such as antifungal agents are added and stirred.
  • the stirring time is not particularly limited as long as the copper etching solution can be made uniform, and may be about 5 to 10 minutes. Further, the temperature of the copper etching solution during stirring is not particularly limited, and may be preferably 15 to 40°C, more preferably 20 to 35°C.
  • the copper seed layer removal method using the copper etching solution of the present invention is not particularly limited, and the copper seed layer can be removed by a conventionally known method. Examples of such removal methods include, for example, immersing the substrate from which the copper seed layer is to be removed in a copper etching solution and stirring it, and injecting the copper etching solution by spray coating onto the substrate from which the copper seed layer is to be removed. It will be done.
  • the temperature of the copper etching solution when removing the copper seed layer is not particularly limited, and is preferably 20 to 40°C, more preferably 25 to 35°C.
  • the processing time for removing the copper seed layer is not particularly limited as long as the copper seed layer of the substrate can be sufficiently removed.
  • the immersion time may be about 3 to 5 minutes.
  • the injection time may be about 10 seconds to 3 minutes.
  • the pressure during injection is preferably 0.05 to 0.3 MPa, more preferably 0.07 to 0.2 MPa.
  • the method for manufacturing a circuit board of the present invention includes the step of removing a copper seed layer between circuits using the copper etching solution for removing the copper seed layer.
  • the copper etching solution for removing the copper seed layer of the present invention described above is used, the removability of the copper seed layer is sufficient, and the surface roughness of the copper wiring or copper electrode is increased. Also, narrowing of the circuit is suppressed.
  • the circuit board with the copper seed layer between the circuits exposed is removed using the etching solution for removing the copper seed layer.
  • the etching solution for removing the copper seed layer examples include a method of removing the copper seed layer by immersing it in water and performing flash etching, and a method of injecting the etching solution for removing the copper seed layer by spray coating onto the circuit board where the copper seed layer between the circuits is exposed.
  • the temperature (processing temperature) of the copper etching solution for removing the copper seed layer in the above step may be adjusted as appropriate, for example, preferably 20 to 40°C, more preferably 25 to 35°C.
  • the processing time in the above step may be set appropriately depending on the thickness of the copper seed layer. For example, when the circuit board is immersed in the etching solution for removing the copper seed layer, the immersion time is about 3 to 5 minutes. That's fine. Further, when the etching solution for removing the copper seed layer is injected onto the circuit board by spray coating, the injection time may be about 10 seconds to 3 minutes.
  • the copper seed layer between the circuits is removed using the copper etching solution for removing the copper seed layer, and a circuit board is manufactured.
  • a circuit board formed by removing the copper seed layer between the circuits using the copper etching solution for removing the copper seed layer is also part of the present invention.
  • Example and comparative example A copper etching solution of Comparative Example 1 was prepared according to the formulation shown in Table 1. Further, copper etching solutions of Examples 1 to 8 were prepared according to the formulations shown in Table 2. The copper etching solution was prepared by sequentially adding each component shown in Tables 1 and 2 to water.
  • microcircuit board (Characteristics evaluation) The following microcircuit board was prepared as a test piece for characteristic evaluation.
  • Etching was performed on the above-mentioned microcircuit board using the copper etching solutions of Examples and Comparative Examples according to the following etching method.
  • Etching method (1) Using a single-sided spray device, process a fine circuit board at a spray pressure of 0.1 MPa. (2) The time when the copper seed layer in the solid area visually disappears is the reference (just etching), and the time when the processing time doubles is defined as 100% overetching. (3) The point at which the processing time triples is defined as 200% overetching.
  • the fine circuit board etched using the above etching method was evaluated using the following evaluation method.
  • Example 9 and 10 Copper etching solutions of Examples 9 and 10 were prepared by the same preparation method as Example 1 except that the formulations shown in Table 4 were used. In Examples 9 and 10, assuming a situation in which copper was accumulated due to continuous use of a copper etching solution, a copper compound was added so that the copper concentration was 5 g/L in terms of copper.
  • the hydrogen peroxide concentration of the copper etching solution was measured by the method of redox titration. The measurement was performed by measuring the initial concentration, and the hydrogen peroxide concentration after 3 hours and 24 hours.

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Abstract

The present invention provides a copper etchant which is for removing a copper seed and has sufficient copper seed layer removability and with which an increase in the surface roughness of a copper wiring or a copper electrode and circuit thinning are suppressed.　The present invention provides a copper etchant for removing a copper seed layer, the copper etchant being characterized by containing an organic acid and hydrogen peroxide and having a pH of 5.0-8.0.

Description

銅シード層除去用銅エッチング液Copper etching solution for copper seed layer removal
　本発明は、銅シード層除去用銅エッチング液に関する。 The present invention relates to a copper etching solution for removing a copper seed layer.
　近年、電子機器の小型化、高機能化に伴い、プリント配線板の高密度化が求められている。特に半導体の搭載基板であるサブストレートはより微細な配線パターンが必要とされることから、図１に示すセミアディティブ工法（ＳＡＰ）が用いられる。 In recent years, as electronic devices have become smaller and more sophisticated, there has been a demand for higher density printed wiring boards. In particular, since a substrate, which is a semiconductor mounting board, requires a finer wiring pattern, the semi-additive construction method (SAP) shown in FIG. 1 is used.
　上述のＳＡＰでは、無電解銅または銅スパッタにより基板上に銅シード層を形成後、非回路部分にレジストが残るよう露光現像を行う。次いで、露出した銅シード層に電気銅めっきにより回路パターンを形成し、レジストを剥離し、不要となった回路間の銅シード層をフラッシュエッチング工程によって除去する。 In the above-mentioned SAP, after a copper seed layer is formed on a substrate by electroless copper or copper sputtering, exposure and development is performed so that resist remains in non-circuit areas. Next, a circuit pattern is formed on the exposed copper seed layer by electrolytic copper plating, the resist is peeled off, and the unnecessary copper seed layer between the circuits is removed by a flash etching process.
　フラッシュエッチング工程では銅配線間に存在する銅シード層を除去するため、銅エッチング液が用いられている。このような銅エッチング液には、十分な銅シード層の除去性が要求される。 In the flash etching process, a copper etchant is used to remove the copper seed layer that exists between copper interconnects. Such a copper etching solution is required to have sufficient ability to remove the copper seed layer.
　上述のような銅エッチング液として、一般的に硫酸／過酸化水素系等のエッチング液が用いられている（例えば、特許文献１）。 As the above-mentioned copper etching solution, a sulfuric acid/hydrogen peroxide based etching solution is generally used (for example, Patent Document 1).
　しかしながら、特許文献１のエッチング液を用いた場合、当該エッチング液は銅配線又は銅電極に対してもエッチング作用があり、銅配線又は銅電極の表面粗度が増加するという問題があり、且つ、回路細りが発生するという問題がある。銅配線又は銅電極の表面粗度の増加や回路幅の減少は、伝送損失の上昇や密着性の低下等、回路の信頼性を損ねる。 However, when the etching solution of Patent Document 1 is used, there is a problem that the etching solution also has an etching effect on the copper wiring or the copper electrode, and the surface roughness of the copper wiring or the copper electrode increases. There is a problem that circuit thinning occurs. An increase in the surface roughness or a decrease in the circuit width of copper wiring or copper electrodes impairs circuit reliability, such as an increase in transmission loss and a decrease in adhesion.
　従って、銅シード層の除去性が十分であり、且つ、銅配線又は銅電極の表面粗度の増加、及び、回路細りが抑制される銅シード層除去用銅エッチング液の開発が望まれている。 Therefore, it is desired to develop a copper etching solution for removing the copper seed layer that has sufficient removability of the copper seed layer, and also suppresses the increase in surface roughness of copper wiring or copper electrodes and the thinning of the circuit. .
国際公開第２０１２／０４６８４１号International Publication No. 2012/046841
　本発明は、銅シード層の除去性が十分であり、且つ、銅配線又は銅電極の表面粗度の増加、及び、回路細りが抑制される銅シード除去用銅エッチング液を提供することを目的とする。 An object of the present invention is to provide a copper etching solution for removing copper seeds that has sufficient removability of the copper seed layer and suppresses increase in surface roughness of copper wiring or copper electrodes and thinning of the circuit. shall be.
　本発明者等は、鋭意研究を重ねた結果、有機酸、及び、過酸化水素を含有し、ｐＨが５．０～８．０である銅シード層除去用銅エッチング液によれば、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of extensive research, the present inventors have found that a copper etching solution for removing a copper seed layer containing an organic acid and hydrogen peroxide and having a pH of 5.0 to 8.0 has been found to achieve the above-mentioned objectives. The present inventors have discovered that the following can be achieved, and have completed the present invention.
　即ち、本発明は、下記の銅シード層除去用銅エッチング液に関する。
１．有機酸、及び、過酸化水素を含有し、ｐＨが５．０～８．０であることを特徴とする銅シード層除去用銅エッチング液。
２．前記有機酸は、ジカルボン酸、トリカルボン酸、及び、それらの塩からなる群より選択される少なくとも１種である、項１に記載の銅シード層除去用銅エッチング液。
３．更に、過酸化水素安定剤を含有する、項１又は２に記載の銅シード層除去用銅エッチング液。
４．前記過酸化水素安定剤は、ラクタム、グリコール類、及び、フェノールスルホン酸塩からなる群より選択される少なくとも１種である、項３に記載の銅シード層除去用銅エッチング液。
５．更に、ｐＨ緩衝剤を含有する、項１～４のいずれかに記載の銅シード層除去用銅エッチング液。
６．前記ｐＨ緩衝剤は、無機リン酸塩及びクエン酸塩からなる群より選択される少なくとも１種である、項５に記載の銅シード層除去用銅エッチング液。
７．硫酸を含まない、項１～６のいずれかに記載の銅シード層除去用銅エッチング液。
８．項１～７のいずれかに記載の銅シード層除去用銅エッチング液により、回路間の銅シード層を除去する工程を有する、回路基板の製造方法。
９．項１～７のいずれかに記載の銅シード層除去用銅エッチング液により、回路間の銅シード層を除去してなる、回路基板。 That is, the present invention relates to the following copper etching solution for removing a copper seed layer.
1. A copper etching solution for removing a copper seed layer, which contains an organic acid and hydrogen peroxide and has a pH of 5.0 to 8.0.
2. 2. The copper etching solution for removing a copper seed layer according to item 1, wherein the organic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and salts thereof.
3. Item 3. The copper etching solution for removing a copper seed layer according to item 1 or 2, further containing a hydrogen peroxide stabilizer.
4. 4. The copper etching solution for removing a copper seed layer according to item 3, wherein the hydrogen peroxide stabilizer is at least one selected from the group consisting of lactams, glycols, and phenolsulfonates.
5. Item 5. The copper etching solution for removing a copper seed layer according to any one of Items 1 to 4, further containing a pH buffer.
6. Item 5. The copper etching solution for removing a copper seed layer according to item 5, wherein the pH buffer is at least one selected from the group consisting of inorganic phosphates and citrates.
7. Item 7. The copper etching solution for removing a copper seed layer according to any one of Items 1 to 6, which does not contain sulfuric acid.
8. A method for manufacturing a circuit board, comprising the step of removing a copper seed layer between circuits using the copper etching solution for removing the copper seed layer according to any one of Items 1 to 7.
9. A circuit board obtained by removing a copper seed layer between circuits using the copper etching solution for removing a copper seed layer according to any one of Items 1 to 7.
　本発明の銅シード層除去用銅エッチング液は、銅シード層の除去性が十分であり、且つ、銅配線又は銅電極の表面粗度の増加、及び、回路細りを抑制することができる。 The copper etching solution for removing the copper seed layer of the present invention has sufficient removability of the copper seed layer, and can suppress increase in surface roughness of copper wiring or copper electrodes and circuit thinning.
ＳＡＰの処理工程を示す図である。It is a figure which shows the processing process of SAP.
　以下、本発明の銅シード層除去用銅エッチング液について詳細に説明する。 Hereinafter, the copper etching solution for removing the copper seed layer of the present invention will be explained in detail.
１．銅シード層除去用銅エッチング液
　本発明の銅シード層除去用銅エッチング液（以下、単に「銅エッチング液」とも示す。）は、有機酸、及び、過酸化水素を含有し、ｐＨが５．０～８．０であることを特徴とする。本発明の銅シード層除去用銅エッチング液は、ｐＨが特定の範囲となるよう有機酸及び過酸化水素水を含む銅エッチング液であるので、電気銅めっき部分へのダメージを減らし、銅配線又は銅電極の表面粗度の増加、及び、回路細りが抑制され、銅除去の必要な回路間の銅シード層部分を優先的にエッチングして除去することができる。本発明の銅シード層除去用銅エッチング液は、過酸化水素が酸化剤として作用し、有機酸がキレート剤、又は、エッチング補助剤として作用する。本発明の銅シード層除去用銅エッチング液では、有機酸と過酸化水素とを組み合わせて用いることにより銅がエッチングされるが、電気銅めっきよりも銅シード層が選択的にエッチングされるため、回路間の不要な銅シード層を除去する際に、電気銅で形成された回路部へのダメージが抑制され、銅配線又は銅電極の表面粗度の増加、及び、回路細りが抑制される。また、本発明の銅シード層除去用銅エッチング液は、ｐＨが特定の範囲であるので、銅配線又は銅電極の表面粗度の増加、及び、回路細りを抑制することができる。 1. Copper Etching Solution for Removing Copper Seed Layer The copper etching solution for removing copper seed layer of the present invention (hereinafter also simply referred to as "copper etching solution") contains an organic acid and hydrogen peroxide, and has a pH of 5. It is characterized by being between 0 and 8.0. The copper etching solution for removing the copper seed layer of the present invention is a copper etching solution containing an organic acid and a hydrogen peroxide solution so that the pH is within a specific range, so it reduces damage to the electrolytic copper plating part and removes the copper wiring or Increase in surface roughness of the copper electrode and thinning of the circuit are suppressed, and the copper seed layer portion between the circuits where copper needs to be removed can be preferentially etched and removed. In the copper etching solution for removing a copper seed layer of the present invention, hydrogen peroxide acts as an oxidizing agent, and an organic acid acts as a chelating agent or an etching aid. In the copper etching solution for removing the copper seed layer of the present invention, copper is etched by using a combination of an organic acid and hydrogen peroxide, but since the copper seed layer is etched more selectively than electrolytic copper plating, When removing unnecessary copper seed layers between circuits, damage to circuit parts formed of electrolytic copper is suppressed, and increase in surface roughness of copper wiring or copper electrodes and circuit thinning are suppressed. Further, since the copper etching solution for removing the copper seed layer of the present invention has a pH within a specific range, it is possible to suppress an increase in the surface roughness of the copper wiring or the copper electrode and a narrowing of the circuit.
　本発明の銅エッチング液のｐＨは５．０～８．０である。ｐＨが５．０未満であると、銅配線又は銅電極の表面粗度の増加、及び、回路細りを抑制できない。ｐＨが８．０を超えると銅シード層の除去性が十分に発揮できない。銅エッチング液のｐＨは、６．０～７．０が好ましい。 The pH of the copper etching solution of the present invention is 5.0 to 8.0. If the pH is less than 5.0, increase in surface roughness of copper wiring or copper electrodes and thinning of the circuit cannot be suppressed. If the pH exceeds 8.0, the copper seed layer cannot be removed sufficiently. The pH of the copper etching solution is preferably 6.0 to 7.0.
（有機酸）
　有機酸としては特に限定されず、銅エッチング液に用いられる有機酸を用いることができる。このような有機酸としては、ジカルボン酸、トリカルボン酸、又は、それらの塩が挙げられる。 (organic acid)
The organic acid is not particularly limited, and organic acids used in copper etching solutions can be used. Such organic acids include dicarboxylic acids, tricarboxylic acids, and salts thereof.
　ジカルボン酸としては、シュウ酸、酒石酸、リンゴ酸、マロン酸、コハク酸、アジピン酸等が挙げられる。これらのジカルボン酸は、塩であってもよい。ジカルボン酸塩としては特に限定されず、公知の金属塩等が挙げられ、具体的には、ナトリウム塩、カリウム塩、アンモニウム塩等が挙げられる。 Examples of dicarboxylic acids include oxalic acid, tartaric acid, malic acid, malonic acid, succinic acid, and adipic acid. These dicarboxylic acids may be salts. The dicarboxylic acid salt is not particularly limited, and includes known metal salts, and specifically includes sodium salts, potassium salts, ammonium salts, and the like.
　トリカルボン酸としては、クエン酸、ニトリロトリ酢等が挙げられる。これらのトリカルボン酸は、塩であってもよい。トリカルボン酸塩としては特に限定されず、公知の金属塩等が挙げられ、具体的には、ナトリウム塩、カリウム塩、アンモニウム塩等が挙げられる。 Examples of tricarboxylic acids include citric acid and nitrilotriacetic acid. These tricarboxylic acids may be salts. Tricarboxylic acid salts are not particularly limited, and include known metal salts, and specific examples include sodium salts, potassium salts, ammonium salts, and the like.
　上記有機酸は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。特に、有機酸は、２種以上を混合して用いることが好ましい。有機酸を２種以上混合して用いることにより、回路間の銅シード層のエッチングがより短時間で処理可能となる。 The above organic acids may be used alone or in combination of two or more. In particular, it is preferable to use a mixture of two or more organic acids. By using a mixture of two or more organic acids, the copper seed layer between the circuits can be etched in a shorter time.
　銅エッチング液中の有機酸の含有量は特に限定されず、１０～６０ｇ／Ｌが好ましく、２０～５５ｇ／Ｌがより好ましく、３０～４０ｇ／Ｌが更に好ましい。有機酸の含有量の下限が上記範囲であると、銅エッチング液の銅シード層の除去性がより向上する。有機酸の含有量の上限が上記範囲であると、銅配線又は銅電極の表面粗度の増加、及び、回路細りがより抑制される。 The content of organic acid in the copper etching solution is not particularly limited, and is preferably 10 to 60 g/L, more preferably 20 to 55 g/L, and even more preferably 30 to 40 g/L. When the lower limit of the content of the organic acid is within the above range, the removability of the copper seed layer by the copper etching solution is further improved. When the upper limit of the content of the organic acid is within the above range, increase in surface roughness of the copper wiring or copper electrode and circuit thinning are further suppressed.
（過酸化水素）
　過酸化水素としては特に限定されず、水に溶解させて過酸化水素水として用いてもよい。 (hydrogen peroxide)
Hydrogen peroxide is not particularly limited, and it may be dissolved in water and used as a hydrogen peroxide solution.
　銅エッチング液中の過酸化水素の含有量は特に限定されず、過酸化水素換算で１５～１００ｇ／Ｌが好ましく、２５～７０ｇ／Ｌがより好ましく、３０～５０ｇ／Ｌが更に好ましい。過酸化水素の含有量の下限が上記範囲であると、銅エッチング液の銅シード層の除去性がより向上する。過酸化水素の含有量の上限が上記範囲であると、銅配線又は銅電極の表面粗度の増加、及び、回路細りがより抑制される。 The content of hydrogen peroxide in the copper etching solution is not particularly limited, and is preferably 15 to 100 g/L, more preferably 25 to 70 g/L, and even more preferably 30 to 50 g/L in terms of hydrogen peroxide. When the lower limit of the content of hydrogen peroxide is within the above range, the removability of the copper seed layer by the copper etching solution is further improved. When the upper limit of the content of hydrogen peroxide is within the above range, increase in surface roughness of the copper wiring or copper electrode and narrowing of the circuit are further suppressed.
（過酸化水素安定剤）
　本発明の銅エッチング液は、過酸化水素安定剤を含有していてもよい。銅エッチング液が過酸化水素安定剤を含有することにより、経時的な銅エッチング液中の過酸化水素の安定性がより向上する。 (Hydrogen peroxide stabilizer)
The copper etchant of the present invention may contain a hydrogen peroxide stabilizer. When the copper etchant contains a hydrogen peroxide stabilizer, the stability of hydrogen peroxide in the copper etchant over time is further improved.
　過酸化水素安定剤としては特に限定されず、水溶液中の過酸化水素安定剤として用いられるものを使用することができる。このような過酸化水素安定剤としては、ラクタム、グリコール類、フェノールスルホン酸塩等が挙げられる。ラクタムとしては特に限定されず、例えば、４－ペンタンラクタム、εカプロラクタム等が挙げられる。グリコール類としては特に限定されず、エチレングリコール、プロピレングリコール、ジエチレングリコール等が挙げられる。フェノールスルホン酸塩として特に限定はされず、ｐ－フェノールスルホン酸ナトリウム、ｐ－トルエンスルホン酸等が挙げられる。これらの中でも、εカプロラクタムが好ましい。 The hydrogen peroxide stabilizer is not particularly limited, and those used as hydrogen peroxide stabilizers in aqueous solutions can be used. Such hydrogen peroxide stabilizers include lactams, glycols, phenolsulfonates, and the like. The lactam is not particularly limited and includes, for example, 4-pentanlactam, ε-caprolactam, and the like. Glycols are not particularly limited, and include ethylene glycol, propylene glycol, diethylene glycol, and the like. The phenolsulfonic acid salt is not particularly limited, and examples thereof include sodium p-phenolsulfonate, p-toluenesulfonic acid, and the like. Among these, ε-caprolactam is preferred.
　上記過酸化水素安定剤は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 The above hydrogen peroxide stabilizers may be used alone or in combination of two or more.
　銅エッチング液中の過酸化水素安定剤の含有量は特に限定されず、１～３０ｇ／Ｌが好ましく、３～２５ｇ／Ｌがより好ましく、５～２０ｇ／Ｌが更に好ましい。過酸化水素安定剤の含有量の下限が上記範囲であると、銅エッチング液の過酸化水素がより安定となる。過酸化水素安定剤の含有量の上限が上記以上の場合であっても安定であるが、劇的な効果向上は認められ難いため、上限が上記範囲であることにより経済性が向上する。 The content of the hydrogen peroxide stabilizer in the copper etching solution is not particularly limited, and is preferably 1 to 30 g/L, more preferably 3 to 25 g/L, and even more preferably 5 to 20 g/L. When the lower limit of the content of the hydrogen peroxide stabilizer is within the above range, the hydrogen peroxide in the copper etching solution becomes more stable. Even if the upper limit of the content of the hydrogen peroxide stabilizer is above the above range, it is stable, but a dramatic improvement in the effect is unlikely to be observed, so economical efficiency is improved by setting the upper limit to the above range.
（ｐＨ緩衝剤）
　本発明の銅エッチング液は、ｐＨ緩衝剤を含有していてもよい。銅エッチング液がｐＨ緩衝剤を含有することにより、銅エッチング液のｐＨがより安定する。 (pH buffer)
The copper etching solution of the present invention may contain a pH buffer. When the copper etching solution contains a pH buffering agent, the pH of the copper etching solution becomes more stable.
　ｐＨ緩衝剤としては特に限定されず、銅エッチング液のｐＨ緩衝剤として用いられるものを使用することができる。このようなｐＨ緩衝剤としては、無機リン酸塩、カルボン酸塩等が挙げられる。 The pH buffer is not particularly limited, and those used as pH buffers for copper etching solutions can be used. Examples of such pH buffering agents include inorganic phosphates, carboxylates, and the like.
　無機リン酸塩としては特に限定されず、例えば、リン酸２水素ナトリウム、リン酸水素２ナトリウム、次亜リン酸ナトリウム、リン酸ナトリウム、リン酸水素ナトリウム等が挙げられる。 The inorganic phosphate is not particularly limited and includes, for example, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hypophosphite, sodium phosphate, sodium hydrogen phosphate, and the like.
　カルボン酸塩としては特に限定されず、例えば、クエン酸ナトリウム、クエン酸２ナトリウム、クエン酸３ナトリウム、酢酸ナトリウム、酒石酸ナトリウム等のカルボン酸ナトリウム塩；クエン酸カリウム、クエン酸２カリウム、クエン酸３カリウム、酢酸カリウム、酒石酸カリウム、酒石酸ナトリウムカリウム等のカルボン酸カリウム塩；クエン酸水素２アンモニウム、クエン酸３アンモニウム、酢酸アンモニウム、酒石酸アンモニウム等のカルボン酸アンモニウム塩等が挙げられる。 The carboxylic acid salt is not particularly limited, and includes, for example, carboxylic acid sodium salts such as sodium citrate, disodium citrate, trisodium citrate, sodium acetate, and sodium tartrate; potassium citrate, dipotassium citrate, and trisodium citrate. Examples include carboxylic acid potassium salts such as potassium, potassium acetate, potassium tartrate, and potassium sodium tartrate; and carboxylic acid ammonium salts such as diammonium hydrogen citrate, triammonium citrate, ammonium acetate, and ammonium tartrate.
　上記ｐＨ緩衝剤は、１種単独で用いてもよいし、２種以上を混合して用いてもよい。 The above pH buffering agents may be used alone or in combination of two or more.
　銅エッチング液中のｐＨ緩衝剤の含有量は特に限定されず、５～１６０ｇ／Ｌが好ましく、７～１００ｇ／Ｌがより好ましく、８～５０ｇ／Ｌが更に好ましく、１０～３０ｇ／Ｌが特に好ましい。ｐＨ緩衝剤の含有量の下限が上記範囲であると、銅エッチング液のｐＨがより安定となる。ｐＨ緩衝剤の含有量の上限が上記範囲以上の場合でも緩衝剤として使用可能であるが、劇的な効果向上は認められ難いため、上限が上記範囲であることにより経済性が向上する。 The content of the pH buffer in the copper etching solution is not particularly limited, and is preferably 5 to 160 g/L, more preferably 7 to 100 g/L, even more preferably 8 to 50 g/L, particularly 10 to 30 g/L. preferable. When the lower limit of the content of the pH buffer is within the above range, the pH of the copper etching solution becomes more stable. Even if the upper limit of the content of the pH buffering agent is above the above range, it can be used as a buffer, but it is difficult to see a dramatic improvement in the effect, so economical efficiency is improved by having the upper limit within the above range.
［他の成分］
　本発明の銅エッチング液は、更に、他の成分を含んでいてもよい。当該他の成分としては、ｐＨ調整剤、防カビ剤等が挙げられる。 [Other ingredients]
The copper etching solution of the present invention may further contain other components. Examples of the other components include pH adjusters, antifungal agents, and the like.
（ｐＨ調整剤）
　ｐＨ調整剤としては特に限定されず、銅エッチング液において用いられている各種のｐＨ調整剤を用いることができる。 (pH adjuster)
The pH adjuster is not particularly limited, and various pH adjusters used in copper etching solutions can be used.
　ｐＨ調整剤としては、具体的には、塩酸、リン酸等の酸；水酸化ナトリウム、水酸化カリウム、アンモニア水等のアルカリを用いることができる。 As the pH adjuster, specifically, acids such as hydrochloric acid and phosphoric acid; alkalis such as sodium hydroxide, potassium hydroxide, and aqueous ammonia can be used.
　これらのｐＨ調整剤は、１種単独で又は２種以上を併用して用いることができる。 These pH adjusters can be used alone or in combination of two or more.
　銅エッチング液中のｐＨ調整剤の含有量は特に限定されず、本発明の銅エッチング液のｐＨを５．０～８．０に調整できる量であればよい。例えば、ｐＨ調整剤として水酸化ナトリウムを用いる場合、銅エッチング液中のｐＨ調整剤の含有量は、１５～３５ｇ／Ｌ程度が好ましく、２０～３０ｇ／Ｌ程度がより好ましい。 The content of the pH adjuster in the copper etching solution is not particularly limited, and may be any amount that can adjust the pH of the copper etching solution of the present invention to 5.0 to 8.0. For example, when sodium hydroxide is used as a pH adjuster, the content of the pH adjuster in the copper etching solution is preferably about 15 to 35 g/L, more preferably about 20 to 30 g/L.
（防カビ剤）
　防カビ剤としては特に限定されず、銅エッチング液において用いられている各種の防カビ剤を用いることができる。 (Anti-mold agent)
The antifungal agent is not particularly limited, and various antifungal agents used in copper etching solutions can be used.
　防カビ剤としては、銅化合物を用いることが好ましく、具体的には、酢酸銅、塩化銅、硝酸銅、炭酸銅、酸化銅等を用いることができる。 As the antifungal agent, it is preferable to use a copper compound, and specifically, copper acetate, copper chloride, copper nitrate, copper carbonate, copper oxide, etc. can be used.
　これらの防カビ剤は、１種単独で又は２種以上を併用して用いることができる。 These antifungal agents can be used alone or in combination of two or more.
　銅エッチング液中の防カビ剤の含有量は特に限定されない。銅エッチング液中の防カビ剤の含有量は、銅濃度換算で０．０１～０．２ｇ／Ｌ程度が好ましく、０．０５～０．１５ｇ／Ｌ程度がより好ましい。 The content of the antifungal agent in the copper etching solution is not particularly limited. The content of the antifungal agent in the copper etching solution is preferably about 0.01 to 0.2 g/L, more preferably about 0.05 to 0.15 g/L in terms of copper concentration.
（溶媒）
　本発明の銅エッチング液は、上記各成分が、溶媒に含まれていることが好ましい。 (solvent)
In the copper etching solution of the present invention, each of the above components is preferably contained in a solvent.
　溶媒としては銅エッチング液を構成する公知の溶媒を用いることができ、例えば、水、アルコール類等が挙げられる。取扱が容易で、安全な点で、水が好ましい。 As the solvent, a known solvent constituting a copper etching solution can be used, and examples thereof include water, alcohols, and the like. Water is preferred because it is easy to handle and safe.
　溶媒の含有量は特に限定されず、上記各成分を添加した残部であってよい。 The content of the solvent is not particularly limited, and may be the remainder after adding each of the above components.
　本発明の銅エッチング液は、硫酸を含まないことが好ましい。本発明の銅エッチング液が硫酸を含まないことにより、銅配線又は銅電極の表面粗度の増加、及び、回路細りをより抑制することができる。 The copper etching solution of the present invention preferably does not contain sulfuric acid. Since the copper etching solution of the present invention does not contain sulfuric acid, increase in surface roughness of copper wiring or copper electrodes and circuit thinning can be further suppressed.
２．銅エッチング液の製造方法
　本発明の銅エッチング液の製造方法としては特に限定されず、従来公知の方法により製造することができる。このような製造方法としては、例えば、水等の溶媒に、上記有機酸、及び、過酸化水素を添加し、更に、必要に応じて、上記過酸化水素安定剤、ｐＨ緩衝剤、ｐＨ調整剤、防カビ剤等の他の成分を添加して、撹拌する製造方法により製造することができる。 2. Method for Producing Copper Etching Solution The method for producing the copper etching solution of the present invention is not particularly limited, and can be produced by conventionally known methods. Such a production method includes, for example, adding the organic acid and hydrogen peroxide to a solvent such as water, and then adding the hydrogen peroxide stabilizer, pH buffer, and pH adjuster as necessary. It can be manufactured by a manufacturing method in which other components such as antifungal agents are added and stirred.
　撹拌時間は、銅エッチング液を均一とすることができれば特に限定されず、５～１０分程度とすればよい。また、撹拌の際の銅エッチング液の温度は特に限定されず、好ましくは１５～４０℃、より好ましくは２０～３５℃とすればよい。 The stirring time is not particularly limited as long as the copper etching solution can be made uniform, and may be about 5 to 10 minutes. Further, the temperature of the copper etching solution during stirring is not particularly limited, and may be preferably 15 to 40°C, more preferably 20 to 35°C.
３．銅シード層除去方法
　本発明の銅エッチング液を用いた銅シード層除去方法としては特に限定されず、従来公知の方法により銅シード層を除去することができる。このような除去方法としては、例えば、銅シード層を除去する基板を銅エッチング液に浸漬し、撹拌する方法、銅シード層を除去する基板にスプレー塗布により銅エッチング液を射出する方法等が挙げられる。 3. Copper Seed Layer Removal Method The copper seed layer removal method using the copper etching solution of the present invention is not particularly limited, and the copper seed layer can be removed by a conventionally known method. Examples of such removal methods include, for example, immersing the substrate from which the copper seed layer is to be removed in a copper etching solution and stirring it, and injecting the copper etching solution by spray coating onto the substrate from which the copper seed layer is to be removed. It will be done.
　銅シード層を除去する際の銅エッチング液の温度は特に限定されず、２０～４０℃が好ましく、２５～３５℃がより好ましい。 The temperature of the copper etching solution when removing the copper seed layer is not particularly limited, and is preferably 20 to 40°C, more preferably 25 to 35°C.
　銅シード層を除去する際の処理時間は、基板の銅シード層を十分に除去できれば特に限定されない。例えば、銅シード層を除去する基板を銅エッチング液に浸漬する方法による場合、浸漬時間は３～５分程度であればよい。また、銅シード層を除去する基板にスプレー塗布により銅エッチング液を射出する方法による場合、射出時間は１０秒～３分程度であればよい。 The processing time for removing the copper seed layer is not particularly limited as long as the copper seed layer of the substrate can be sufficiently removed. For example, when the substrate from which the copper seed layer is to be removed is immersed in a copper etching solution, the immersion time may be about 3 to 5 minutes. Further, when using a method of injecting the copper etching solution by spray coating onto the substrate from which the copper seed layer is to be removed, the injection time may be about 10 seconds to 3 minutes.
　銅シード層を除去する基板にスプレー塗布により銅エッチング液を射出する方法では、射出の際の圧力は０．０５～０．３ＭＰａが好ましく、０．０７～０．２ＭＰａがより好ましい。 In the method of injecting a copper etching solution by spray coating onto the substrate from which the copper seed layer is to be removed, the pressure during injection is preferably 0.05 to 0.3 MPa, more preferably 0.07 to 0.2 MPa.
４．回路基板の製造方法
　本発明の回路基板の製造方法は、上記銅シード層除去用銅エッチング液により、回路間の銅シード層を除去する工程を有する、回路基板の製造方法である。本発明の製造方法では、上記説明した本発明の銅シード層除去用銅エッチング液を用いるので、銅シード層の除去性が十分であり、且つ、銅配線又は銅電極の表面粗度の増加、及び、回路細りが抑制される。 4. Method for manufacturing a circuit board The method for manufacturing a circuit board of the present invention includes the step of removing a copper seed layer between circuits using the copper etching solution for removing the copper seed layer. In the manufacturing method of the present invention, since the copper etching solution for removing the copper seed layer of the present invention described above is used, the removability of the copper seed layer is sufficient, and the surface roughness of the copper wiring or copper electrode is increased. Also, narrowing of the circuit is suppressed.
　上記工程において、上記銅シード層除去用銅エッチング液により、回路基板の銅シード層を除去する方法としては、例えば、回路間の銅シード層が露出した回路基板を上記銅シード層除去用エッチング液に浸漬し、フラッシュエッチングを行うことにより除去する方法、回路間の銅シード層が露出した回路基板に、上記銅シード層除去用エッチング液をスプレー塗布により射出する方法等が挙げられる。 In the above step, as a method for removing the copper seed layer of the circuit board using the copper etching solution for removing the copper seed layer, for example, the circuit board with the copper seed layer between the circuits exposed is removed using the etching solution for removing the copper seed layer. Examples include a method of removing the copper seed layer by immersing it in water and performing flash etching, and a method of injecting the etching solution for removing the copper seed layer by spray coating onto the circuit board where the copper seed layer between the circuits is exposed.
　上記工程での銅シード層除去用銅エッチング液の液温（処理温度）は適宜調整すればよく、例えば、２０～４０℃が好ましく、２５～３５℃がより好ましい。 The temperature (processing temperature) of the copper etching solution for removing the copper seed layer in the above step may be adjusted as appropriate, for example, preferably 20 to 40°C, more preferably 25 to 35°C.
　上記工程での処理時間は、銅シード層の厚みに応じて適宜設定すればよく、例えば、回路基板を上記銅シード層除去用エッチング液に浸漬する方法による場合、浸漬時間は３～５分程度であればよい。また、回路基板に、上記銅シード層除去用エッチング液をスプレー塗布により射出する方法による場合、射出時間は１０秒～３分程度であればよい。 The processing time in the above step may be set appropriately depending on the thickness of the copper seed layer. For example, when the circuit board is immersed in the etching solution for removing the copper seed layer, the immersion time is about 3 to 5 minutes. That's fine. Further, when the etching solution for removing the copper seed layer is injected onto the circuit board by spray coating, the injection time may be about 10 seconds to 3 minutes.
　上記工程により、上記銅シード層除去用銅エッチング液により、回路間の銅シード層が除去され、回路基板が製造される。このように、上記銅シード層除去用銅エッチング液により、回路間の銅シード層を除去してなる回路基板も本発明の一つである。 Through the above steps, the copper seed layer between the circuits is removed using the copper etching solution for removing the copper seed layer, and a circuit board is manufactured. Thus, a circuit board formed by removing the copper seed layer between the circuits using the copper etching solution for removing the copper seed layer is also part of the present invention.
　以下に実施例及び比較例を示して本発明をより詳しく説明する。但し、本発明は実施例に限定されない。 The present invention will be explained in more detail by showing Examples and Comparative Examples below. However, the present invention is not limited to the examples.
（実施例及び比較例）
　　表１に示す配合により、比較例１の銅エッチング液を調製した。また、表２に示す配合により、実施例１～８の銅エッチング液を調製した。銅エッチング液の調製は、水に、表１及び表２に示す各成分を順次添加することにより行った。 (Example and comparative example)
A copper etching solution of Comparative Example 1 was prepared according to the formulation shown in Table 1. Further, copper etching solutions of Examples 1 to 8 were prepared according to the formulations shown in Table 2. The copper etching solution was prepared by sequentially adding each component shown in Tables 1 and 2 to water.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（特性評価）
　特性評価用の試験片として、下記の微細回路基板を用意した。
微細回路基板
・下地：8インチSiウエハー、ABFラミネート品Ra＝29nm
・スパッタ：チタンスパッタ膜25nm銅スパッタ膜100nm
・レジスト：4～5μm
・硫酸銅めっき：膜厚3μm
・L/S（μm）：順に10/10、7/7、5/5、3/3、2.5/2.5、2/2、2.1/1.8、2.3/1.7、1.8/2.2のL/Sで回路を並べて形成 (Characteristics evaluation)
The following microcircuit board was prepared as a test piece for characteristic evaluation.
Micro circuit board /base: 8 inch Si wafer, ABF laminate product Ra = 29nm
・Sputter: Titanium sputtered film 25nm Copper sputtered film 100nm
・Resist: 4~5μm
・Copper sulfate plating: Film thickness 3μm
・L/S (μm): Circuit with L/S of 10/10, 7/7, 5/5, 3/3, 2.5/2.5, 2/2, 2.1/1.8, 2.3/1.7, 1.8/2.2 in order form by arranging
　上述の微細回路基板に、実施例及び比較例の銅エッチング液を用いて、下記エッチング方法によりエッチングを行った。 Etching was performed on the above-mentioned microcircuit board using the copper etching solutions of Examples and Comparative Examples according to the following etching method.
エッチング方法
（１）片面スプレー装置を使用して、スプレー圧0.1Mpaの条件で微細回路基板を処理する。
（２）目視にてベタ部の銅シード層が消失した時間を基準（ジャストエッチング）とし、処理時間が2倍となった時点をオーバーエッチング100％とする。
（３）処理時間が3倍となった時点をオーバーエッチング200％とする。 Etching method (1) Using a single-sided spray device, process a fine circuit board at a spray pressure of 0.1 MPa.
(2) The time when the copper seed layer in the solid area visually disappears is the reference (just etching), and the time when the processing time doubles is defined as 100% overetching.
(3) The point at which the processing time triples is defined as 200% overetching.
　上記エッチング方法によりエッチングを行った微細回路基板について、下記評価方法により評価した。 The fine circuit board etched using the above etching method was evaluated using the following evaluation method.
（スパッタ膜の除去性）
　ジャストエッチングの時点でのスプレーエッチング後のベタ部及びL/S＝10/10の箇所におけるスパッタ銅残渣をFE-SEM（10000倍）にて確認し、下記評価基準に従って評価した。
○：回路間の銅シード層が除去された状態である
×：回路間の銅シード層が残留している状態である (Removability of sputtered film)
The sputtered copper residue in the solid area after spray etching at the time of just etching and the location where L/S = 10/10 was confirmed using FE-SEM (10000x magnification) and evaluated according to the following evaluation criteria.
○: The copper seed layer between the circuits has been removed. ×: The copper seed layer between the circuits remains.
（銅配線の表面粗度）
　エッチング前後（オーバーエッチング200％）の表面粗度(Ra)を、形状解析レーザー顕微鏡を用いて拡大倍率1500倍の条件で測定した。 (Surface roughness of copper wiring)
The surface roughness (Ra) before and after etching (over-etching 200%) was measured using a shape analysis laser microscope at a magnification of 1500 times.
（銅配線の減膜量）
　エッチング前後（オーバーエッチング100％）前後の銅配線減膜量をFE-SEMを用いて測定した。 (Amount of copper wiring thinning)
The amount of copper interconnect thinning before and after etching (100% over-etching) was measured using FE-SEM.
　結果を表３に示す。 The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（実施例９及び１０）
　表４に示す配合とした以外は実施例１と同様の調製方法により、実施例９及び１０の銅エッチング液を調製した。なお、実施例９及び１０では、銅エッチング液の連続使用により銅が蓄積した状況を想定し、銅濃度が銅換算で5g/Lとなるよう銅化合物を添加した。 (Examples 9 and 10)
Copper etching solutions of Examples 9 and 10 were prepared by the same preparation method as Example 1 except that the formulations shown in Table 4 were used. In Examples 9 and 10, assuming a situation in which copper was accumulated due to continuous use of a copper etching solution, a copper compound was added so that the copper concentration was 5 g/L in terms of copper.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例９及び１０の銅エッチング液を用いて、下記方法により浴安定性を評価した。 Using the copper etching solutions of Examples 9 and 10, bath stability was evaluated by the following method.
（浴安定性）
　酸化還元滴定の方法により銅エッチング液の過酸化水素濃度を測定した。測定は初期濃度、３時間後、２４時間後の過酸化水素濃度を測定することにより行った。 (bath stability)
The hydrogen peroxide concentration of the copper etching solution was measured by the method of redox titration. The measurement was performed by measuring the initial concentration, and the hydrogen peroxide concentration after 3 hours and 24 hours.
　結果を表５に示す。 The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (9)

  1. 　有機酸、及び、過酸化水素を含有し、ｐＨが５．０～８．０であることを特徴とする銅シード層除去用銅エッチング液。 A copper etching solution for removing a copper seed layer, which contains an organic acid and hydrogen peroxide and has a pH of 5.0 to 8.0.
  2. 　前記有機酸は、ジカルボン酸、トリカルボン酸、及び、それらの塩からなる群より選択される少なくとも１種である、請求項１に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 1, wherein the organic acid is at least one selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and salts thereof.
  3. 　更に、過酸化水素安定剤を含有する、請求項１又は２に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 1 or 2, further comprising a hydrogen peroxide stabilizer.
  4. 　前記過酸化水素安定剤は、ラクタム、グリコール類、及び、フェノールスルホン酸塩からなる群より選択される少なくとも１種である、請求項３に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 3, wherein the hydrogen peroxide stabilizer is at least one selected from the group consisting of lactams, glycols, and phenolsulfonates.
  5. 　更に、ｐＨ緩衝剤を含有する、請求項１又は２に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 1 or 2, further comprising a pH buffer.
  6. 　前記ｐＨ緩衝剤は、無機リン酸塩及びクエン酸塩からなる群より選択される少なくとも１種である、請求項５に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 5, wherein the pH buffer is at least one selected from the group consisting of inorganic phosphates and citrates.
  7. 　硫酸を含まない、請求項１又は２に記載の銅シード層除去用銅エッチング液。 The copper etching solution for removing a copper seed layer according to claim 1 or 2, which does not contain sulfuric acid.
  8. 　請求項１に記載の銅シード層除去用銅エッチング液により、回路間の銅シード層を除去する工程を有する、回路基板の製造方法。 A method for manufacturing a circuit board, comprising the step of removing the copper seed layer between the circuits using the copper etching solution for removing the copper seed layer according to claim 1.
  9. 　請求項１に記載の銅シード層除去用銅エッチング液により、回路間の銅シード層を除去してなる、回路基板。 A circuit board obtained by removing a copper seed layer between circuits using the copper etching solution for removing a copper seed layer according to claim 1.
PCT/JP2023/027679 2022-08-08 2023-07-28 Copper etchant for removing copper seed layer WO2024034426A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010265524A (en) * 2009-05-15 2010-11-25 Kanto Chem Co Inc Etchant for copper-containing stacked film
JP2013076119A (en) * 2011-09-30 2013-04-25 Advanced Technology Materials Inc Etchant for copper or cooper alloy
JP2017031502A (en) * 2015-08-03 2017-02-09 三菱瓦斯化学株式会社 Etching solution for etching multilayer thin film comprising copper layer and titanium layer and etching method using the same, and substrate obtained by using the etching method
JP2022052909A (en) * 2020-09-24 2022-04-05 パナソニックＩｐマネジメント株式会社 Etchant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010265524A (en) * 2009-05-15 2010-11-25 Kanto Chem Co Inc Etchant for copper-containing stacked film
JP2013076119A (en) * 2011-09-30 2013-04-25 Advanced Technology Materials Inc Etchant for copper or cooper alloy
JP2017031502A (en) * 2015-08-03 2017-02-09 三菱瓦斯化学株式会社 Etching solution for etching multilayer thin film comprising copper layer and titanium layer and etching method using the same, and substrate obtained by using the etching method
JP2022052909A (en) * 2020-09-24 2022-04-05 パナソニックＩｐマネジメント株式会社 Etchant

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