TW202223158A - 蝕刻劑及電路基板的製造方法 - Google Patents
蝕刻劑及電路基板的製造方法 Download PDFInfo
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- TW202223158A TW202223158A TW110138564A TW110138564A TW202223158A TW 202223158 A TW202223158 A TW 202223158A TW 110138564 A TW110138564 A TW 110138564A TW 110138564 A TW110138564 A TW 110138564A TW 202223158 A TW202223158 A TW 202223158A
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- Prior art keywords
- copper
- etchant
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- layer
- etching
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- 238000005530 etching Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000010949 copper Substances 0.000 claims abstract description 96
- 229910052802 copper Inorganic materials 0.000 claims abstract description 94
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 halogen ions Chemical class 0.000 claims abstract description 40
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
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- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
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- 239000010931 gold Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000007747 plating Methods 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 13
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- 150000002739 metals Chemical class 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- OQSQRYMTDPLPNY-UHFFFAOYSA-N 1,2-diethylimidazole Chemical compound CCC1=NC=CN1CC OQSQRYMTDPLPNY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 230000009918 complex formation Effects 0.000 description 4
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- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
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- 150000003851 azoles Chemical class 0.000 description 3
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
- C23F1/02—Local etching
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明係一種蝕刻劑,其係選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層,該蝕刻劑包含:銅離子、選自環內具有2個以上氮原子的雜環化合物及碳數8以下的含有胺基的化合物所構成群組中的一種以上的含氮化合物、聚烷二醇、以及鹵離子;前述蝕刻劑含有0.0005重量%以上7重量%以下的聚烷二醇,且含有1ppm以上250ppm以下的鹵離子。
Description
本發明係關於一種蝕刻劑及電路基板的製造方法。
傳統作為形成電路基板的細微電路圖形的方法,已知在絕緣樹脂層的表面藉由無電解電鍍銅,形成種子層,在該種子層上設置電鍍光阻,藉由電解電鍍銅,以形成電路,然後蝕刻除去殘留在電路之間的基板上的種子層之半加成製程(SAP:Semi Additive Process)等。於該半加成製程,構成電路的銅電鍍層的表面,實施了金、銀、鈀等的比銅還貴的金屬(電離傾向小的金屬)的電鍍。因此,蝕刻除去種子層時,需要選擇性地蝕刻種子層的銅(特別是無電解銅電鍍層的銅)的蝕刻劑。
作為在不同種類的金屬共存的基板上選擇銅進行蝕刻的蝕刻劑,例如專利文獻1(日本特開2012-129304號)揭露的蝕刻劑等。
另一方面,與比銅還貴的金屬導通(電連接)的銅與蝕刻劑接觸的情況,可能引發被稱為電偶腐蝕(Galvanic corrosion)的現象。所謂電偶腐蝕係指電離傾向不同的2種金屬放入電解液中時,因兩金屬形成局部電池,電離傾向大的金屬有腐蝕的現象。如上述蝕刻銅與比銅還貴的金屬共存的基板
時,因電偶腐蝕而部分的銅恐會被過度蝕刻。作為抑制如此的電偶腐蝕的蝕刻劑,例如有專利文獻2(WO2019/013160號)揭露的蝕刻劑等。於專利文獻2,記載如此的蝕刻劑對銅的選擇蝕刻性優異,可以確實地抑制電偶腐蝕且蝕刻速度也優異。
但是,專利文獻2記載的蝕刻劑,由於是在pH7.8至11的鹼性蝕刻劑,對製造步驟的應用產生限制。因此,需要在更低的pH下也可以確實地抑制因電偶腐蝕等的部分的過度蝕刻且銅的選擇蝕刻性優異的蝕刻劑。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2012-129304號公報
[專利文獻2]國際公開WO2019/013160號公報
本發明係有鑑於前述的傳統技術的問題點而完成者,以提供在比較低的pH下也可抑制部分的過度蝕刻且銅的選擇蝕刻性優異的蝕刻劑為課題。
而且,以提供在比較低的pH下抑制部分的過度蝕刻且可以選擇性地蝕刻銅的電路基板的製造方法為課題。
關於蝕刻劑的本發明,
其係選擇性地蝕刻被處理物的銅層,該被處理物中,包含比銅還貴的金屬的貴金屬層、與銅層係共存;
該蝕刻劑包含:銅離子;
選自環內具有2個以上氮原子的雜環化合物及碳數8以下的含有胺基的化合物所構成群組中的一種以上的含氮化合物;
聚烷二醇;以及
鹵離子;
前述蝕刻劑含有0.0005重量%以上7重量%以下的聚烷二醇;
且含有1ppm以上250ppm以下的鹵離子。
本發明係前述鹵離子可為選自氯化物離子及溴化物離子所構成群組中的至少一種。
本發明係pH可為6.0以上8.0以下。
本發明可包含0.5重量%以上10.0重量%以下的前述銅離子。
本發明可包含0.1重量%以上30.0重量%以下的前述含氮化合物。
本發明不包含有機酸或者包含超過0重量%未達7重量%的有機酸。
本發明係前述含氮化合物可為咪唑類。
本發明係前述烷二醇可為聚乙二醇。
關於電路基板的製造方法的本發明,其係使用前述任一項記載的蝕刻劑,藉由選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層,以形成電路。
在關於電路基板的製造方法的本發明,前述貴金屬層可為包含
金的層。
根據本發明,可提供在比較低的pH下也可以確實地抑制部分的過度蝕刻且銅的選擇蝕刻性優異的蝕刻劑。
而且,可提供在比較低的pH下也可以確實地抑制部分的過度蝕刻且可以選擇性地蝕刻銅的電路基板的製造方法。
1:絕緣樹脂層
2:種子層(銅層)
3:電路
4:貴金屬層
10:電路基板
BW:電解銅電鍍的寬度
TW:鎳/金層的寬度
圖1係表示電路基板的輪廓的部分剖面示意圖。
圖2係表示電路基板的輪廓的部分剖面示意圖。
圖3係用於說明側蝕刻量的測量的示意圖。
以下,說明本發明的蝕刻劑及本發明的電路基板的製造方法(以下也有只稱為製造方法)的實施態樣。
(蝕刻劑)
本實施態樣的蝕刻劑係選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層之蝕刻劑,蝕刻劑包含銅離子、選自環內具有2個以上氮原子的雜環化合物及碳數8以下的含有胺基的化合物所構成群組中的一種以上的含氮化合物、聚烷二醇以及鹵離子,該蝕刻劑含有0.0005重量%以上7重量%以下的聚烷二醇,且含有1ppm以上250ppm以下的鹵離子。
又,本實施態樣所謂「銅」係指純銅及包含90重量%以上的銅合金。而且,本實施態樣所謂「比銅還貴的金屬」係指電離傾向比Cu小的金屬。
[銅離子]
本實施態樣的蝕刻劑包含銅離子。作為銅離子,較佳為二價銅離子(Cu2+)。銅離子係由銅離子源供應到蝕刻劑中。銅離子是作為銅的氧化劑的成分。
作為供給銅離子的銅離子源,例如氫氧化銅、有機酸的銅錯合物、碳酸銅、硫酸銅、氧化銅、氯化銅、溴化銅等的鹵化銅、或者後述含氮化合物的銅錯合物等。
特別從提高蝕刻速度的觀點,係列舉甲酸銅、乙酸銅、氯化銅、溴化銅等。
銅離子源可以單獨使用這些或組合複數種使用。
前述銅離子的含量從提高蝕刻速度的觀點,係列舉例如以銅離子為0.5重量%以上10.0重量%以下或者1.0重量%以上5.重量%以下。
銅離子源的含量可以適當地決定,以成為上述銅離子的含量。
[含氮化合物]
本實施態樣的蝕刻劑包含選自環內具有2個以上氮原子的雜環化合物(以下也有只稱為雜環化合物)及碳數8以下的含有胺基的化合物(以下也有只稱為含胺基化合物)所構成群組中的一種以上的含氮化合物(以下也有只稱為含氮化合物)。含氮化合物係與溶解於蝕刻劑中的銅為錯合物,被調配作為保持在蝕刻劑中的成分。
作為雜環化合物只要是環內具有2個以上的氮原子者,無特別限
制,例如咪唑類、吡唑類、三唑類、四唑類及該等的衍生物等的唑類等。從與溶解的銅的錯合物形成性的觀點,較佳為咪唑、苯并咪唑等的咪唑類或者吡唑等的吡唑類。具體地例如咪唑、2-甲基咪唑、1,2-二乙基咪唑、苯并咪唑、吡唑、三唑、苯并三唑等,特別是咪唑、2-甲基咪唑、1,2-二乙基咪唑、2-乙基-4-甲基咪唑為較佳。
[含胺基化合物]
作為含胺基化合物只要是碳數8以下者,無特別限制,從與溶解的銅的錯合物形成性的觀點,較佳係列舉碳數0以上7以下者,或者0以上5以下者。
作為含胺基化合物,係列舉例如氨;甲基銨、二甲基銨、三甲基銨等的烷基銨;烷醇胺;苯胺等的芳香族胺等。而且,乙二胺等的具有2個以上的胺基的化合物、四甲基銨等的4級胺化合物等。特別是從與溶解的銅的錯合物形成性的觀點,較佳為氨、烷醇胺。
作為烷醇胺的具體例,例如單乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、2-(2-羥基)乙氧基乙醇胺等的單乙醇胺及其衍生物;二乙醇胺、N-甲基二乙醇胺、N-丁基二乙醇胺等的二乙醇胺及其衍生物;三乙醇胺;丙醇胺;異丙醇胺;羥基乙基哌嗪(hydroxyethyl piperazine);及該等的衍生物等。特別是從與溶解的銅的錯合物形成性的觀點,較佳為單乙醇胺、三乙醇胺、N-甲基二乙醇胺。
從與溶解的銅的錯合物形成性的觀點,作為含氮化合物,較佳為咪唑類、吡唑類、氨、烷醇胺,更佳為2-甲基咪唑、咪唑、1,2-二乙基咪唑、2-乙基-4-甲基咪唑、三乙醇胺、單乙醇胺、N-甲基二乙醇胺。
含氮化合物的含量例如為1.0重量%以上30.0重量%以下或5.0重量
%以上25.0重量%以下,或者10.0重量%以上20.0重量%以下。藉由含氮化合物的含量為前述範圍,可提高蝕刻速度,同時可抑制蝕刻劑的黏度的上升。
作為含氮化合物,可以只為雜環化合物及含胺基化合物中的一者,亦可為兩者。
再者,含氮化合物可為前述各成分單獨使用或組合複數種使用。
雜環化合物及含胺基化合物一起使用為較佳。
於使用雜環化合物及含胺基化合物兩者作為含氮化合物的情況,係列舉例如組合作為雜環化合物的唑類及作為含胺基化合物的烷醇胺等。具體地,係列舉例如從咪唑、2-甲基咪唑、1,2-二乙基咪唑、2-乙基-4-甲基咪唑中選擇1種或2種以上作為雜環化合物,從三乙醇胺、單乙醇胺、N-甲基二乙醇胺中選擇1種或2種以上作為含胺基化合物等。
於該情況,唑類的含量例如為0.1重量%以上25重量%以下或1.0重量%以上20重量%以下,或者3.0重量%以上10重量%以下,烷醇胺的含量例如為0.1重量%以上25重量%以下或1.0重量%以上20重量%以下,或者2.5重量%以上11重量%以下。
[聚烷二醇]
本實施態樣的蝕刻劑包含聚烷二醇。聚烷二醇為可抑制因電偶腐蝕的過度蝕刻、促進均勻的蝕刻的成分。
作為本實施態樣的聚烷二醇,也包含聚烷二醇及其衍生物。
聚烷二醇無特別限制,惟係列舉例如聚乙二醇、聚丙二醇、聚丁二醇、聚氧乙烯-聚氧丙烯嵌段共聚物等。特別從改進抑制蝕刻不均等的完成結果的觀
點,較佳為聚乙二醇。於使用聚乙二醇的情況,較佳為重量平均分子量為200至20000等的聚乙二醇。
聚烷二醇的含量從抑制過度蝕刻等的觀點,係列舉例如為0.0005重量%以上7重量%以下,或0.001重量%以上5重量%以下。
[鹵離子]
本實施態樣的蝕刻劑包含鹵離子。鹵離子係提高銅的溶解性及溶解安定性且加速蝕刻速度的成分。
作為供應鹵離子到蝕刻劑中的鹵離子源,無特別限制,係列舉例如氯化氫、溴化氫、碘化氫等的無機酸;氯化銅、溴化銅、氯化鐵、氯化鈉、碘化鈉、氯化銨、溴化銨等的無機鹽。
作為供給的鹵離子的種類無特別限制,惟係列舉例如氯、碘、溴等的鹵素。特別從兼具電偶腐蝕的抑制及蝕刻速度的最佳化的觀點,鹵離子係以選自氯化物離子及溴化物離子所構成群組中的至少一種為較佳。
作為鹵離子的含量,從蝕刻速度為適合範圍的觀點,係列舉例如為1ppm以上250ppm以下,或2ppm以上200ppm以下,或者4ppm以上100ppm以下等。
更具體地例如於鹵離子為氯化物離子的情況為50ppm以上200ppm以下,於鹵離子為溴化物離子的情況為2ppm以上40ppm以下等的範圍。
[有機酸]
本實施態樣的蝕刻劑不包含有機酸,或者包含少許為較佳。有機酸雖有提高蝕刻劑中銅的溶解性的作用,由於也有促進因電偶腐蝕的過度蝕刻的作用,
不包含或者即使包含,以超過0重量%未達7重量%,或者1重量%以上6重量%以下為較佳。
於包含有機酸的情況,有機酸的種類無特別限制,惟例如從不妨礙銅的氧化作用且不引起蝕刻劑的黏度上升等的點,係列舉例如脂肪族飽和單羧酸、脂肪族飽和二羧酸、氧羧酸。特別是較佳地列舉甲酸、乙酸、丙酸、丁酸、己酸、草酸、乳酸、蘋果酸、檸檬酸、酒石酸等。
[其他成分]
於本實施態樣的蝕刻劑,在一般的蝕刻劑中可調配的成分只要是不妨礙本實施態樣的蝕刻劑的目的的成分,可以適當地調配。
[pH]
本實施態樣的蝕刻劑的pH調整為6.0以上8.0以下,或6.2以上7.5以下,或6.2以上7.0以下為較佳。
藉由調整為前述pH的範圍,可以容易地抑制因電偶腐蝕的過度蝕刻。
蝕刻劑的pH的調整,藉由調整前述各成分,例如含氮化合物、銅離子源、鹵離子源等的含量進行,藉由調配pH調整劑也可以調整。
本實施態樣的蝕刻劑即使在較低的pH也適合進行蝕刻。藉此,即使需要在pH低的狀態下進行蝕刻的製造步驟,亦可以容易地使用。
本實施態樣的蝕刻劑可藉由將前述各成分溶解於水而調製。作為水,係列舉離子交換水、蒸餾水、純水及超純水等。而且,本實施態樣的蝕刻劑只要調整使前述各成分在使用時成為指定的濃度即可。例如可以先調製濃縮液,在使用前稀釋各成分成為指定的濃度,或者先調整全部成分中的一部分成分混合的複數個溶液,使用時混合各個溶液,使其包含全部的成分。
本實施態樣的蝕刻劑,其對銅的蝕刻速度例如調整為0.3μm/分以上1.0μm/分以下的程度。而且,對銅以外的金屬的蝕刻速度可調整為0.1μm/分以下。只要是該範圍的蝕刻速度,可以確實地抑制對銅的部分過度蝕刻且銅的選擇蝕刻性良好。
(電路基板的製造方法)
接著,說明使用本實施態樣的蝕刻劑的電路基板的製造方法。
本實施態樣的電路基板的製造方法,係使用上述本實施態樣的蝕刻劑,藉由選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層,以形成電路。
本實施態樣的電路基板,係列舉例如印刷電路基板、薄膜觸控感應器的銅電路構件等。於該情況,作為包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物,係列舉例如圖1表示的絕緣樹脂層1的表面藉由無電解電鍍銅,以形成有種子層2(銅層),該種子層2上藉由電解電鍍銅,以形成電路3之電路基板10等。
在電路3的表面藉由電解電鍍或無電解電鍍,形成了金鍍層4(貴金屬層)。又,為了防止金鍍層4與電路3之間的擴散,可形成鎳等所構成的擴散防止層(圖未顯示)。
又,作為形成於電路3的表面之貴金屬層所含有的比銅還貴的金屬,除了金以外,係列舉鈀、汞、銀、鉑等。
本實施態樣的蝕刻劑適合使用於特別是使用包含金的貴金屬層與銅共存的被處理物製造電路基板的情況。
如此的電路基板10例如可藉由半加成製程形成。
首先,在絕緣樹脂層1的表面,藉由無電解電鍍銅,形成種子層2,在該種子層2上,設置電鍍光阻(圖未顯示),藉由電解電鍍銅,以形成電路3。再者,在電路3的表面,藉由電鍍,以形成擴散防止層及金鍍層4。然後,除去電鍍光阻,得到具備如圖1的電路3的構成的電路基板10。
再者,為了蝕刻除去殘留在電路3之間的絕緣樹脂層1上的種子層2,於本實施態樣,使用上述本實施態樣的蝕刻劑進行蝕刻,得到如圖2所示的電路基板10。又,電路3彼此可以藉由內層電路(圖未顯示)等電連接。
蝕刻方法無特別限制,係列舉例如噴塗方法、前述被處理物浸漬於蝕刻劑中的方法等。從有效率地蝕刻電路之間的種子層等狹窄處的金屬的觀點,較佳為噴塗處理。
蝕刻處理時的蝕刻劑的溫度、處理時間等的處理條件無特別限制,惟係列舉例如蝕刻劑的溫度為20℃以上40℃以下,處理時間為20秒以上120秒以下等。
進行如此的蝕刻處理時,由於金鍍層4的金與電路3的銅共同存在,電路彼此也以內層電路電連接存在,其係在容易產生電偶腐蝕的狀態。於該情況,在與如圖3所示電路3的上部的金鍍層4的附近,因電偶腐蝕的過度蝕刻,有如凹陷的狀態,亦即產生側蝕刻。如此的側蝕刻過度進行的話,則電路寬度變窄、電阻變大且可能短路。
於本實施態樣的蝕刻劑,可抑制因電偶腐蝕的側蝕刻且維持蝕刻速度進行均勻的蝕刻。而且,可以選擇性地蝕刻銅,特別是無電解電鍍銅的種子層。因此,也可以抑制電路基板的電路的電阻增加、短路等。
本實施態樣的電路基板的製造方法,也可以在半加成製程的製
造方法實施,在其他製程,選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層的情況也可以實施。
本實施態樣的蝕刻劑及電路基板的製造方法應該被分別獨立解釋。因此,在其他製造方法使用本實施態樣的蝕刻劑,當然藉由組合其他技術,可實施各實施態樣。
關於本實施態樣的蝕刻劑及電路基板的製造方法,雖如以上所述,應該認為此次揭露的實施態樣並不限於例示的全部的點。本發明的範圍係依據請求範圍表示,並非前述的說明,係指包含與請求範圍同等意義及範圍內的全部變更。
[實施例]
以下,顯示實施例更具體地說明本發明,但本發明不限於該等的例。
(蝕刻劑)
使用表1至表3表示的各材料(剩餘為離子交換水)製作實施例及比較例的蝕刻劑。
使用以下作為各原料。
A.鹵離子供應源
氯化鈉(Kishida(岸田)化學公司製、1級)
溴化銨(岸田化學公司製、特級)
碘化鉀(岸田化學公司製、1級)
B.聚烷二醇
聚乙二醇(岸田化學公司製、1級、分子量1000)
C.銅離子源
甲酸銅(富士薄膜和光純藥公司製、1級)
乙酸銅(岸田化學公司製、1級)
D.含胺基化合物
單乙醇胺(富士薄膜和光純藥公司製、1級)
三乙醇胺(岸田化學公司製、1級)
N-甲基二乙醇胺(東京化成工業公司製、1級)
E.雜環化合物
2-甲基咪唑(東京化成工業公司製、1級)
咪唑(岸田化學公司製、特級)
F.有機酸
馬來酸(富士薄膜和光純藥公司製、1級)
蘋果酸(岸田化學公司製、特級)
乳酸(富士薄膜和光純藥公司製、1級)
d-酒石酸(岸田化學公司製、1級)
(pH的測量)
製作的各蝕刻劑的pH係用堀場製作所製pH測量裝置F-71,測量30℃下的pH。結果表示於表2。
(測試基板)
準備如下述的測試基板。
在樹脂層的厚度0.2mm的樹脂基板,使用無電解銅電鍍液(奧野製藥工業公司製、無電解銅電鍍液:ADCOPPER(商品名)),製作厚度0.3μm的銅種
子層。然後,使用電鍍光阻(日立化成公司製、RD-1225(商品名)),形成光阻,形成電鍍光阻圖形(厚度約25μm、線及間隔L/S=15μm/30μm)。再者,使用電解銅電鍍液(奧野製藥工業公司製、電解銅電鍍液:TOPLUCINA(商品名)),製作厚度15μm、寬度30μm的電解銅電鍍層。然後,使用電解鎳金電鍍液,在電解銅電鍍層上,製作電解鎳金電鍍層。最後,使用除去液(三菱氣體化學公司製、CLEAN ETCH R-100),進行1分鐘處理除去光阻。
(蝕刻)
使用前述測試基板,使用實施例及比較例的各蝕刻劑進行蝕刻,除去在電解銅電鍍層之間露出的種子層。
蝕刻係使用噴嘴(池內公司製、山形扇形噴嘴INVV9030),在噴壓0.1MPa、處理溫度40℃的條件下進行。處理時間係進行到測試基板的電解銅電鍍之間的種子層完全地被除去為止。蝕刻後,進行水洗、乾燥,進行以下表示的評估。
(側蝕刻量的測量)
裁切蝕刻後的各測試基板的一部分,將其埋入熱硬化性樹脂,進行研磨加工,以便可以觀察到電解銅電鍍層的剖面,製作剖面觀察用樣品。電解銅電鍍層的剖面的觀察係使用SEM(掃描電子顯微鏡),拍攝圖像,進行在圖3所示的電解銅電鍍層上的鎳/金層的寬度TW及電解銅電鍍的寬度BW的測量,以(TW-BW)÷2(μm)作為側蝕刻量,表示於表1至表3。
(蝕刻不均的判斷)
將5×5cm的電解銅電鍍板用各實施例及比較例的蝕刻劑,用與蝕刻各測試基板的蝕刻相同的條件,進行蝕刻處理後,用目視觀察銅表面。在處理均勻之情況判斷為沒有不均勻,有陰影之情況判斷為有不均勻。
(蝕刻速度的測量)
準備5×5cm的電解銅電鍍板,測量該重量W1(g)。將各電鍍板用各實施例及比較例的蝕刻劑,進行1分鐘、40℃的處理。測量處理後的重量W2(g),蝕刻速度用以下的式算出,表示於表1至表3。
(W1-W2)×10000÷223(μm/分)
結果表示於表1至表3。
(檢討)
如表1所示,於各實施例,側蝕刻比比較例的量少且也可維持蝕刻速度。而且,沒有產生蝕刻不均。
比較例3及4因產生蝕刻不均,沒有實施測試基板的蝕刻。
而且,如表2所示,即使在pH8.0以下的情況,於各實施例可以抑制側蝕刻。
再者,如表3所示,即使改變含胺基化合物及雜環化合物的種類的情況,於各實施例可以抑制側蝕刻。
1:絕緣樹脂層
2:種子層(銅層)
3:電路
4:貴金屬層
10:電路基板
Claims (10)
- 一種蝕刻劑,其係選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層;該蝕刻劑包含:銅離子;選自環內具有2個以上氮原子的雜環化合物及碳數8以下的含有胺基的化合物所構成群組中的一種以上的含氮化合物;聚烷二醇;以及鹵離子;前述蝕刻劑含有0.0005重量%以上7重量%以下的聚烷二醇,且含有1ppm以上250ppm以下的鹵離子。
- 如請求項1所述之蝕刻劑,其中該鹵離子為選自氯化物離子及溴化物離子所構成群組中的至少一種。
- 如請求項1或2所述之蝕刻劑,其pH為6.0以上8.0以下。
- 如請求項1至3中任一項所述之蝕刻劑,其包含0.5重量%以上10.0重量%以下的前述銅離子。
- 如請求項1至4中任一項所述之蝕刻劑,其包含1.0重量%以上30重量%以下的前述含氮化合物。
- 如請求項1至5中任一項所述之蝕刻劑,其不包含有機酸或者包含超過0重量%未達7重量%的有機酸。
- 如請求項1至6中任一項所述之蝕刻劑,其中前述含氮化合物為咪唑類。
- 如請求項1至7中任一項所述之蝕刻劑,其中前述聚烷二醇為聚乙二醇。
- 一種電路基板的製造方法,其包括下列步驟:使用請求項1至8中任一項所述之蝕刻劑,藉由選擇性地蝕刻包含比銅還貴的金屬的貴金屬層與銅層共存的被處理物的銅層,以形成電路。
- 如請求項9所述之電路基板的製造方法,其中前述貴金屬層為包含金的層。
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JP4606919B2 (ja) * | 2005-03-28 | 2011-01-05 | 朝日化学工業株式会社 | エッチング組成液 |
JP4916455B2 (ja) * | 2008-01-15 | 2012-04-11 | 株式会社Adeka | 銅含有材料用エッチング剤組成物 |
JP4685180B2 (ja) * | 2009-07-09 | 2011-05-18 | 株式会社Adeka | 銅含有材料用エッチング剤組成物及び銅含有材料のエッチング方法 |
JP5219304B2 (ja) | 2010-12-14 | 2013-06-26 | メック株式会社 | エッチング剤及びこれを用いたエッチング方法 |
JP5535060B2 (ja) * | 2010-12-28 | 2014-07-02 | 株式会社Adeka | 銅含有材料用エッチング剤組成物及び銅含有材料のエッチング方法 |
JP2014036064A (ja) * | 2012-08-08 | 2014-02-24 | Ube Ind Ltd | プリント配線板の製造方法 |
EP2754732B1 (en) * | 2013-01-15 | 2015-03-11 | ATOTECH Deutschland GmbH | Aqueous composition for etching of copper and copper alloys |
JP6464578B2 (ja) * | 2013-08-01 | 2019-02-06 | 三菱瓦斯化学株式会社 | プリント配線板の製造方法 |
EP3184669B1 (en) * | 2015-12-23 | 2018-07-18 | ATOTECH Deutschland GmbH | Etching solution for copper and copper alloy surfaces |
KR101699798B1 (ko) * | 2016-08-02 | 2017-01-25 | 와이엠티 주식회사 | 구리 에칭 조성물 및 이를 이용한 구리 배선 형성방법 |
KR20180015052A (ko) * | 2017-01-06 | 2018-02-12 | 와이엠티 주식회사 | 구리 에칭 조성물 및 이를 이용한 구리 배선 형성방법 |
JP6949306B2 (ja) | 2017-07-14 | 2021-10-13 | メルテックス株式会社 | 銅エッチング液 |
CN109652804B (zh) * | 2019-01-30 | 2021-01-01 | 湖南互连微电子材料有限公司 | 一种pcb减铜蚀刻液以及制作工艺 |
-
2020
- 2020-11-11 JP JP2020187929A patent/JP7274221B2/ja active Active
-
2021
- 2021-09-30 US US18/036,313 patent/US20230407486A1/en active Pending
- 2021-09-30 CN CN202180086278.3A patent/CN116601331A/zh active Pending
- 2021-09-30 WO PCT/JP2021/036222 patent/WO2022102272A1/ja active Application Filing
- 2021-09-30 KR KR1020237016494A patent/KR20230104628A/ko unknown
- 2021-09-30 EP EP21891519.7A patent/EP4245886A1/en active Pending
- 2021-10-18 TW TW110138564A patent/TW202223158A/zh unknown
Also Published As
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JP2022077193A (ja) | 2022-05-23 |
EP4245886A1 (en) | 2023-09-20 |
JP7274221B2 (ja) | 2023-05-16 |
US20230407486A1 (en) | 2023-12-21 |
KR20230104628A (ko) | 2023-07-10 |
CN116601331A (zh) | 2023-08-15 |
WO2022102272A1 (ja) | 2022-05-19 |
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