TW202337984A - 用於改善聚合物材料至金屬基材之黏著性之單步驟氧化物浴 - Google Patents
用於改善聚合物材料至金屬基材之黏著性之單步驟氧化物浴 Download PDFInfo
- Publication number
- TW202337984A TW202337984A TW111144131A TW111144131A TW202337984A TW 202337984 A TW202337984 A TW 202337984A TW 111144131 A TW111144131 A TW 111144131A TW 111144131 A TW111144131 A TW 111144131A TW 202337984 A TW202337984 A TW 202337984A
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- TW
- Taiwan
- Prior art keywords
- imidazole
- coating composition
- oxide coating
- dichlorobenzotriazole
- dichloroimidazole
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 67
- 239000003112 inhibitor Substances 0.000 claims abstract description 61
- -1 nitrogen heterocyclic compound Chemical class 0.000 claims abstract description 60
- 239000008199 coating composition Substances 0.000 claims abstract description 53
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- 238000005260 corrosion Methods 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 14
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- 229920003002 synthetic resin Polymers 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000002708 enhancing effect Effects 0.000 claims abstract description 5
- 230000003628 erosive effect Effects 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 32
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 claims description 11
- FHZALEJIENDROK-UHFFFAOYSA-N 5-bromo-1h-imidazole Chemical compound BrC1=CN=CN1 FHZALEJIENDROK-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003851 azoles Chemical class 0.000 claims description 8
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 7
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 7
- QAJJXHRQPLATMK-UHFFFAOYSA-N 4,5-dichloro-1h-imidazole Chemical compound ClC=1N=CNC=1Cl QAJJXHRQPLATMK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002367 halogens Chemical group 0.000 claims description 7
- CAXULIMFJKHWDD-UHFFFAOYSA-N 1,4-dichlorobenzotriazole Chemical compound ClC1=CC=CC2=C1N=NN2Cl CAXULIMFJKHWDD-UHFFFAOYSA-N 0.000 claims description 6
- QZWWJMGWDBSBQS-UHFFFAOYSA-N 1,5-dichloroimidazole Chemical compound ClC1=CN=CN1Cl QZWWJMGWDBSBQS-UHFFFAOYSA-N 0.000 claims description 6
- CEWAYAHHRRYAMY-UHFFFAOYSA-N 2,5-dichlorobenzotriazole Chemical compound ClC1=CC=2C(=NN(N2)Cl)C=C1 CEWAYAHHRRYAMY-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000001737 promoting effect Effects 0.000 claims description 6
- CRIAGZDVEWMBRY-UHFFFAOYSA-N 4,5-dichloro-2h-benzotriazole Chemical compound ClC1=CC=C2NN=NC2=C1Cl CRIAGZDVEWMBRY-UHFFFAOYSA-N 0.000 claims description 5
- KJIODOACRIRBPB-UHFFFAOYSA-N 4-bromo-1h-indazole Chemical compound BrC1=CC=CC2=C1C=NN2 KJIODOACRIRBPB-UHFFFAOYSA-N 0.000 claims description 5
- KJBTZMYWBSAZAQ-UHFFFAOYSA-N 2,5-dibromo-1h-imidazole Chemical compound BrC1=CN=C(Br)N1 KJBTZMYWBSAZAQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 150000001565 benzotriazoles Chemical class 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical class C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 claims description 3
- SISLWYYBYOEVFJ-UHFFFAOYSA-N 1,2-dichloroimidazole Chemical compound ClC1=NC=CN1Cl SISLWYYBYOEVFJ-UHFFFAOYSA-N 0.000 claims description 3
- QLQVXSCFCMVRAW-UHFFFAOYSA-N 1,4-dibromoimidazole Chemical compound BrN1C=NC(=C1)Br QLQVXSCFCMVRAW-UHFFFAOYSA-N 0.000 claims description 3
- INOGLHRUEYDAHX-UHFFFAOYSA-N 1-chlorobenzotriazole Chemical compound C1=CC=C2N(Cl)N=NC2=C1 INOGLHRUEYDAHX-UHFFFAOYSA-N 0.000 claims description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 3
- LRDLVPORISMMKL-UHFFFAOYSA-N 2,5-dichloro-1h-imidazole Chemical compound ClC1=CNC(Cl)=N1 LRDLVPORISMMKL-UHFFFAOYSA-N 0.000 claims description 3
- MYYYOBVDIRECDX-UHFFFAOYSA-N 4,5-dibromo-1h-imidazole Chemical compound BrC=1N=CNC=1Br MYYYOBVDIRECDX-UHFFFAOYSA-N 0.000 claims description 3
- GAGULFLHHXEBAG-UHFFFAOYSA-N 4,5-dichloroimidazole-1-carboxylic acid Chemical compound OC(=O)N1C=NC(Cl)=C1Cl GAGULFLHHXEBAG-UHFFFAOYSA-N 0.000 claims description 3
- HHEBHJLYNLALHM-UHFFFAOYSA-N 5,6-dichloro-2h-benzotriazole Chemical compound C1=C(Cl)C(Cl)=CC2=NNN=C21 HHEBHJLYNLALHM-UHFFFAOYSA-N 0.000 claims description 3
- ZLWMWGLWSFVWIW-UHFFFAOYSA-N 5-bromo-1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=C(Br)N1 ZLWMWGLWSFVWIW-UHFFFAOYSA-N 0.000 claims description 3
- STVHMYNPQCLUNJ-UHFFFAOYSA-N 5-bromo-1h-indazole Chemical compound BrC1=CC=C2NN=CC2=C1 STVHMYNPQCLUNJ-UHFFFAOYSA-N 0.000 claims description 3
- WMKDUJVLNZANRN-UHFFFAOYSA-N 6-bromo-1h-indazole Chemical compound BrC1=CC=C2C=NNC2=C1 WMKDUJVLNZANRN-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- JZLZUMYEWXIJDE-UHFFFAOYSA-N ClC1(N=CC=N1)Cl Chemical compound ClC1(N=CC=N1)Cl JZLZUMYEWXIJDE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 150000001556 benzimidazoles Chemical class 0.000 claims description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002780 morpholines Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
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- 150000003536 tetrazoles Chemical class 0.000 claims description 3
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- QYBWIXBVMQYFIL-UHFFFAOYSA-N 2-chlorobenzotriazole Chemical compound C1=CC=CC2=NN(Cl)N=C21 QYBWIXBVMQYFIL-UHFFFAOYSA-N 0.000 claims description 2
- KMHHWCPTROQUFM-UHFFFAOYSA-N 7-bromo-1h-indazole Chemical compound BrC1=CC=CC2=C1NN=C2 KMHHWCPTROQUFM-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000004867 thiadiazoles Chemical class 0.000 claims 2
- NOIXNOMHHWGUTG-UHFFFAOYSA-N 2-[[4-[4-pyridin-4-yl-1-(2,2,2-trifluoroethyl)pyrazol-3-yl]phenoxy]methyl]quinoline Chemical compound C=1C=C(OCC=2N=C3C=CC=CC3=CC=2)C=CC=1C1=NN(CC(F)(F)F)C=C1C1=CC=NC=C1 NOIXNOMHHWGUTG-UHFFFAOYSA-N 0.000 claims 1
- 239000011368 organic material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 55
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 18
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Classifications
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- G—PHYSICS
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- G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/22—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources
- G09G3/30—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels
- G09G3/32—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED]
- G09G3/3208—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED] organic, e.g. using organic light-emitting diodes [OLED]
- G09G3/3225—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED] organic, e.g. using organic light-emitting diodes [OLED] using an active matrix
- G09G3/3233—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters using controlled light sources using electroluminescent panels semiconductive, e.g. using light-emitting diodes [LED] organic, e.g. using organic light-emitting diodes [OLED] using an active matrix with pixel circuitry controlling the current through the light-emitting element
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
- G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
- G09G3/2007—Display of intermediate tones
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
- G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
- G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
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Abstract
一種氧化物塗層組成物及一種使用該氧化物塗層組成物增強金屬導電層與有機材料中或聚合樹脂材料之間的黏著性的程序。該程序包括將氧化物塗層組成物施加至金屬導電層及將無機材料或聚合樹脂材料接合至金屬導電層之步驟。該氧化物塗層組成物包含(a)鹼;(b)氧化劑;(c)酸;及(d)腐蝕抑制劑,其包含氮雜環化合物;
Description
本發明大致上係關於一種氧化物塗層組成物及使用其以在多層電路板之製造中改善金屬表面(諸如銅)至無機材料或聚合樹脂材料之黏著性的方法。
多層電路板尤其包含界定電路圖案之數個金屬層,及其等之間的數個絕緣層。此等各別層可具有各種厚度。例如,其等可係大約僅數微米厚或者更厚。
在多層電路板之典型製造中,首先藉由一程序製備圖案化電路系統內層,其中在所欲電路系統圖案之正影像中用光阻劑對覆銅箔介電基材材料進行圖案化,隨後蝕刻掉暴露之銅。在移除光阻劑後,仍保留所欲的銅電路系統圖案。
任何特定類型或多種類型之電路系統圖案的一或多個電路系統內層,以及可能構成接地平面及電源平面之電路系統內層係藉由在電路系統內層之間插置一或多個部分固化之介電基材材料層(所謂的「預浸漬」層),以形成交替的電路系統內層及介電基材材料之複合物,而組裝成多層電路。接著使該複合物經受熱及壓力以固化該部分固化之基材材料,並達到電路系統內層與其之接合。接著,該固化之複合物具有穿過其中鑽出的數個通孔,接著將其金屬化以提供用於將所有電路系統層導電互連之構件。在通孔金屬化程序的過程中,所欲的電路系統圖案一般係形成在多層複合物之向外層上。
形成多層印刷電路板之替代方法係透過添加劑或表面積層電路系統技術。此等技術以非導電基材開始,電路元件在其上被額外地電鍍。藉由在電路系統上重複施加可成像塗層,並在可成像塗層上電鍍進一步電路元件來達到進一步層。
已知許久的是,在電路系統內層之銅金屬及與其接觸的經固化預浸漬層或其他非導電塗層之間形成的黏著接合強度可能會有問題,結果是經固化之多層複合物或塗層在後續處理及/或使用中易於脫層。基於此,所欲的是增強導電層與絕緣層之間的黏著性,以避免後續製造操作或使用時之脫層。所謂的「黑色氧化物」程序已使用多年以產生牢固黏著之氧化銅層,絕緣層可更好地黏附至該氧化銅層。
經組裝及固化之多層電路複合物具有通孔,該等通孔需要金屬化以作用為電路之電路系統層之導電互連的構件。通孔之金屬化涉及孔表面之樹脂去污、催化活化、無電銅沉積、電解銅沉積、及類似者之步驟。許多此等程序步驟涉及使用介質(諸如酸),其能夠溶解在通孔處或附近暴露的電路系統內層部分上的氧化銅助黏劑塗層。氧化銅之此種局部溶解(其係藉由在通孔周圍形成粉紅圈或暈環來證明(由於藉此暴露的底層銅金屬之粉紅色))可繼而導致多層電路中之局部脫層。
所屬技術領域非常具有此「粉紅圈」現象的知識,並已花費大量努力來尋求達成不易受此類局部脫層影響之多層印刷電路製造程序。
目前使用氧化物替代組成物之主要問題係該程序的整體蝕刻速率。超過0.5至1.5微米(20至60微吋)之蝕刻速率通常會在銅基材上產生太多的形貌。雖然此係有利於內層接合黏著性,但對於印刷電路板(printed circuit board, PCB)市場中的高速應用來說係不可接受的。
已發現,傳統的粗糙銅表面在此等較高頻率下產生顯著的信號損失。此外,隨著向5G技術的發展,市場需要低粗糙度之內層接合應用。
基於此,所欲的是提供一種克服先前技術之缺陷的改善的低粗糙度內層接合程序。
本發明大致上係關於一種奈米氧化物塗層組成物,其展現低粗糙度且藉由在銅表面上產生奈米結晶氧化物結構來促進內層接合。
已建議的其他低粗糙度技術包括錫程序(其商業產品以商品名FlatBond GT購自Uyemura International Corporation)、有機塗層(其商業產品以商品名GLiCAP購自Shikoku Chemicals)、以及氧化物技術(其商業產品以商品名NovaBond購自Atotech)。
然而,此等技術具有一些所欲克服之缺陷。例如,FlatBond GT產品需要新的、昂貴的設備,且錫之成本遠高於本發明中所使用之氧化物。已顯示GLiCAP產品在熱程序之後展現出不良黏著性。最後,NovaBond氧化物在非常高的溫度下操作,且僅可在垂直應用中運行。NovaBond氧化物程序亦需要用於後浸應用之額外程序步驟。
因此,所欲發展改善之新程序,其用於改善無機材料至金屬表面之黏著性,其展現克服先前技術之缺陷的低粗糙度。
本發明之目的係提供一種將無機材料黏著至金屬表面之改善程序。
本發明之另一目的係提供一種不需要一後浸步驟來確保抗酸性之無機材料黏著程序。
本發明之另一目的係提供一種在不蝕刻該金屬基材表面之情況下改善黏著性之程序。
本發明之又另一目的係提供一種在不蝕刻該銅基材之情況下促進內層接合之程序。
本發明之再另一目的係提供一種藉由在銅基材上產生一奈米結晶氧化物結構來促進內層接合之程序。
本發明之又另一目的係提供一種可安裝在現有設備中之改善的一黏著促進程序。
本發明之又另一目的係提供一種可在一較低操作溫度下使用之改善的一黏著促進程序。
為此,在一個實施例中,本發明大致上係關於一種用於在製造一多層電路板期間增強金屬導電層與無機材料或聚合樹脂材料之間的黏著性的程序,該程序包含下列步驟:
a) 可選地,施加預浸至該金屬導電層;
b) 將氧化物塗層組成物施加至該金屬導電層以產生抗酸表面,其中該氧化物塗層組成物包含:
i. 鹼;
ii. 氧化劑;
iii. 酸;及
iv. 腐蝕抑制劑;及
c) 將該無機材料或聚合樹脂材料接合至該金屬導電層。
本發明大致上係關於一種用於改善無機材料及聚合樹脂材料至金屬表面(尤其是銅或銅合金表面)之黏著性的程序。本文所提出之程序在多層印刷電路的生產中特別有用。本文所提出之程序提供金屬與聚合物表面(亦即,電路系統及中間絕緣層)之間的最佳黏著性,且消除及/或實質上最小化粉紅圈。
本發明之發明人已發現一種奈米氧化物程序,其展現低粗糙度且不需要後浸漬步驟來確保抗酸性。本文所描述之新穎的單步驟氧化物浴亦允許將該程序安裝至現有的氧化物替代設備中。
此新穎的奈米氧化物程序不需要後浸步驟來確保抗酸性(亦即,消除及/或最小化「粉紅圈」)。單步驟浴允許將化學品安裝至現有的氧化物替代設備中,包括水平式設備。額外地,該程序得到的較低操作溫度允許在現有設備中實施單步驟浴。
如本文中所使用,「一(a/an)」及「該(the)」係指單數及複數兩種指示對象,除非上下文另有明確規定。
如本文中所使用,用語「約(about)」係指可測量的值,諸如參數、量、時間持續時間、及類似者,且意欲包括具體敘述值之+/-15%或更小的變化、較佳的是+/-10%或更小的變化、更佳的是+/-5%或更小的變化、甚至更佳的是+/-1%或更小的變化、且又更佳的是+/-0.1%或更小的變化,以致此類變化適於在本文所述之本發明中執行。此外,亦應理解的是,修飾語「約(about)」所指的值本身係在本文中明確揭示。
如本文中所使用,諸如「下方(beneath)」、「下面(below)」、「下部(lower)」、「上面(above)」、「上部(upper)」、及類似者的空間相對用語係為了便於描述而用以描述一元件或特徵與另一(或多個)元件或特徵的關係,如圖式中所繪示。進一步應理解的是,用語「前面(front)」及「後面(back)」並非意欲作為限制性的,且係意欲在適當處為可互換的。
如本文中所使用,用語「包含(comprise/comprising)」具體指明所述之特徵、整數、步驟、操作、元件、及/或組件的存在,但不排除一或多個其他特徵、整數、步驟、操作、元件、組件、及/或其群組的存在或添加。
如本文中所使用,若未在本文中針對一特定元件或化合物來另行定義,則用語「實質上無(substantially free)」或「基本上無(essentially free)」意指一給定元件或化合物無法藉由用於浴分析之通常分析手段來偵測到,該等通常分析手段係為金屬電鍍技術領域中具有通常知識者所熟知。此類方法一般包括原子吸收光譜法、滴定、UV-Vis分析、二次離子質譜法、及其他常見可用的分析技術。
除非另有註明,否則所有的量均係重量百分比。除了邏輯上此類數值範圍受限於總計達100%之處,所有數值範圍係包含兩端點數的,且可以任何順序組合。
用語「組成物(composition)」、及「浴(bath)」、及「溶液(solution)」在整個本說明書中可互換使用。
除非在本說明書中另描述為具有取代基,否則用語「烷基(alkyl)」意指僅由碳及氫組成並具有下列通式的有機化學基:C
nH
2n+1。
用語「平均(average)」等同於樣本之平均值。
在一個實施例中,本發明大致上係關於一種用於增強金屬導電層與無機材料或聚合樹脂材料之間的黏著性的程序,該程序包含下列步驟:
a) 可選地,施加預浸至該金屬導電層;
b) 將氧化物塗層組成物施加至該金屬導電層以產生抗酸表面,其中該氧化物塗層組成物包含:
i. 鹼;
ii. 氧化劑;
iii. 酸;及
iv. 腐蝕抑制劑;及
c) 將該無機材料或聚合樹脂材料接合至該金屬導電層。
在一個實施例中,金屬導電層包含銅或銅合金。
本文所描述之方法能夠處理平滑的銅表面,以在其上產生奈米氧化物結晶氧化物結構,而對表面粗糙度不具有任何可測量的影響。當與各種無機材料及聚合樹脂材料(包括預浸漬材料)使用時,經處理之銅表面之奈米氧化物結晶氧化物結構展現極佳的黏著性及抗熱性。此等無機材料包括例如矽、陶瓷、用作填料之無機材料及玻璃。
聚合樹脂材料之實例包括:丙烯酸酯樹脂、環氧樹脂、聚醯亞胺樹脂、雙馬來醯亞胺樹脂、馬來醯亞胺樹脂、氰酸酯樹脂、聚苯醚樹脂、聚伸苯醚樹脂(polyphenylene oxide resin)、烯烴樹脂、含氟樹脂、聚醚醯亞胺樹脂、聚醚醚酮樹脂、及液晶樹脂,且可係藉由彼此混合或改質之其組合。
例示性聚合樹脂材料包括多官能樹脂系統,其包括經設計以用於需要高熱效能及可靠性之多層印刷線路板應用者。此等樹脂系統之實例包括例如可購自Isola, Megtron Series之370HR環氧樹脂層壓體、可購自Panasonic, Inc.之介電電路板材料(包括例如Megtron M、Megtron 2、Megtron 4、Megtron 6、Megtron 7、及Megtron 7N)、6及Megtron 7N、及可購自Ajinomoto Group之微膜(諸如Ajinomoto Build-up Film (ABF))。
在一個實施例中,在與氧化物塗層組成物接觸之前對銅表面進行處理以預清潔銅表面。一種適合的預清潔劑係酸預清潔劑,其商業產品可以商品名717 Acid Cleaner、MultiBond Acid Cleaner S、及M-Speed Clean購自MacDermid Enthone, Inc。
之後,銅表面經受預浸步驟。大致選擇預浸組成物以與氧化物塗層組成物相容。在一個實施例中,預浸組成物包含與黏著促進組成物相同的鹼及酸,不含有機物組分(亦即,腐蝕抑制劑)或氧化劑。預浸之主要功能係對銅表面種氧化物薄層,使得主要氧化物塗層浴可均勻且更快速地起始氧化物。在一個實施例中,使用本文所述之不同濃度的氧化物塗層組成物執行預浸。
在一個實施例中,金屬導電層與預浸組成物接觸約10至約240秒,更佳地約30至約45秒的期間,然後與氧化物塗層組成物接觸約10至約240秒,更佳地約30至約90秒,更佳地約45至約60秒的期間,以在金屬導電層表面產生奈米氧化物結晶氧化物結構。
與氧化物塗層組成物之接觸可藉由任何習知手段進行,其包括浸沒於氧化物塗層組成物之浴中或其他接觸手段達一段時間期間。
在一替代實施例中,本文所述之方法不需要在黏著促進步驟之前的預浸步驟。亦即,金屬導電層直接與氧化物塗層組成物接觸,而無需首先使金屬導電層與預浸組成物接觸。
已發現,本發明之改善程序不會導致銅表面基材的形貌增加,改善美觀的外觀,且改善對後層壓程序之抗熱性及抗化學性。該方法可併入到印刷電路板製造程序中,以改善高頻應用中使用的內層之間的接合,同時維持極佳的信號完整性。
本文所描述之程序可用於水平及垂直程序組態兩者。所屬技術領域中具有通常知識者將知道水平及垂直程序組態可能需要不同的時間或溫度來達成相同的所欲結果。在一個實施例中,本文所描述之程序可用於現有的水平式設備,其經組態與氧化物替代化學品一起使用,且本文所描述之組成物取代此類氧化物替代化學品。在另一實施例中,本文所描述之程序用於垂直組態。
可用於氧化物塗層組成物之鹼可係氫氧化物,其包括例如氫氧化鈉、氫氧化鉀、或氫氧化銨。在一個實施例中,鹼包含氫氧化鈉。鹼一般以足以將組成物之pH維持在所欲範圍內的量使用。在一較佳實施例中,塗層組成物中之鹼的濃度在約1至50 g/L、更佳的是在約5至約20 g/L之範圍內。
選擇氧化劑是針對其在組成物中之穩定性,且較佳地係亞氯酸鈉。發明人已發現亞氯酸鈉由於其穩定性而提供良好的結果,而其他氧化劑(諸如氯醯基、過氯醯基、次氯酸鹽、氯酸鹽、及過氯酸鹽)大致不是較佳的,因為其等在組成物中不穩定。氧化劑較佳地以在約10至約240 g/L之範圍內,更佳地在約70至180 g/L的範圍內,最佳地在約140至150 g/L之範圍內之濃度使用。
用於本文所描述之組成物中之酸一般係無機酸。在一較佳實施例中,由於其晶粒細化能力,酸包含磷酸。組成物中酸之濃度較佳地在約1至約20 g/L、更佳地在約2至約10 g/L、且最佳地在約2.5至約5.0 g/L之範圍內。
腐蝕抑制劑較佳地係氮雜環化合物。在一個實施例中,氮雜環化合物係5及6員氮雜環化合物,其可選自唑類、吡啶類、嘧啶類、哌啶類、及嗎啉類。在一個實施例中,將氮雜環化合物併入於配方中,以在金屬導電層上形成抗酸性塗層,並減少及/或消除粉紅圈。此氮雜環化合物以足以與氧化物塗層接合以在金屬導電層上產生抗酸性表面之量併入電鍍組成物中。
雖然許多氮雜環化合物賦予金屬導電層某種抗酸性,但較佳的化合物亦導致良好的美觀外觀,且與組成物之其他成分相容。「良好的美觀外觀(good cosmetic appearance)」係指顏色均勻、沒有斑點或變色之表面。
發明人已發現使用較小的抑制劑在抗酸性方面取得更好的成功,部分原因在於其等更容易與氧化物結構調節之能力。基於此,在一個實施例中,腐蝕抑制劑係未經取代或經取代之唑。
在一個實施例中,氮雜環化合物未經取代或經鹵素取代基取代,其中功效大致與鹵素取代基之分子量成反比。
較佳的唑基抑制劑之實例包括經取代或未經取代之吡唑類、咪唑類、三唑類、四唑類、噻唑類、咔唑類、吲唑類、苯并咪唑類、苯并三唑類、苯并噻唑類、苯并噻二唑類、及上述一或多種之組合。在一個實施例中,唑基抑制劑具有包括鹵素取代基之環結構,該鹵素取代基可係例如氯化物或溴化物。在另一實施例中,唑基抑制劑係經硫取代之唑基抑制劑,諸如經硫取代之苯并三唑。
可用於本發明之組成物的合適的唑基抑制劑的實例包括但不限於咪唑、1,4-二氯苯并三唑、4,5-二氯-2H-苯并三唑、1,4-二氯苯并三唑、5,5-二氯苯并三唑、5,6-二氯苯并三唑、2,5-二氯苯并三唑、2,4-二氯苯并三唑、2,6-二氯苯并三唑、2,7-二氯苯并三唑、5-氯苯并三唑、1-氯苯并三唑、2-氯苯并三唑、2-溴-1H-吲唑、4-溴-1H-吲唑、5-溴-1H-吲唑、6-溴-1H-吲唑、7-溴-1H-吲唑、4-溴-1H-咪唑、5-溴-1H-咪唑-2-羧酸、1,2-二溴咪唑-4-羧酸、2,4-二溴-1H-咪唑、4,5-二溴-1H-咪唑、1,4-二溴-1H-咪唑、4,4-二溴-1H-咪唑、苯并咪唑、2-4-二溴咪唑、4,5-二氯咪唑、1,5-二氯咪唑、3,4-二氯咪唑、4,5-二氯咪唑-1-羧酸、1,2-二氯咪唑、4,5-二氯-1H-咪唑、2,2-二氯咪唑、1,4-二氯咪唑、4,4-二氯咪唑、2,5-二氯-1H-咪唑、苯并三唑-5-羧酸、及其他類似化合物、連同上述一或多種之組合。
雖然在先前技術之黏著促進組成物中使用唑基腐蝕抑制劑,例如美國專利第6,554,948號、第6,419,784號、及第6,146,701號中所描述,均關於Ferrier,但此等先前技術之組成物經設計以產生微粗糙化表面。與基於唑類化學品之先前技術組成物相比,本發明之組成物經設計為不提供任何微粗糙化,而是在金屬導電層表面上產生奈米氧化物層,其展現良好的美觀外觀。如此,腐蝕抑制劑之特定類型及使用腐蝕抑制劑之(多個)濃度,連同其他浴成分之濃度係本發明之重要態樣。
發明人已發現本發明之關鍵態樣係氮雜環化合物之大小。出人意料的是,較小的有機結構可產生較大的每單位表面積之剝離強度,並且與金屬導電層表面上氧化物之形成更好地協調。因此,如本文所闡述,單環化合物大致較佳。另一方面,隨著氮雜環化合物之結構大小成長,功效可能減少。
本文所描述之氮雜環化合物一般以在約1 ppb至約5,000 ppm之範圍內的濃度使用,取決於特定抑制劑、附接至環結構之取代基、及氮雜環化合物之分子量,以及其他浴成分之類型及濃度。
所採用之濃度範圍的差異可歸因於取代基之推電子或拉電子性質。如同推電子氯化物取代,其增加氮鍵結至銅表面之強度,從而使抑制劑變強。而拉電子羧酸基團使抑制劑變弱,導致使用較高濃度。在硫取代之情況下,硫可作用為親核劑且導致非常強的抑制作用。
例如,包括氯苯并三唑之苯并三唑可在約25至300 ppm,更佳地在50至150 ppm,最佳地在70至80 ppm之範圍內的濃度下使用。另一方面,苯并三唑-5-羧酸可在約100至2,000 ppm,更佳地在500至1,500 ppm,最佳地在約900至約1,100 ppm之範圍內的濃度下使用,且經硫取代之苯并三唑可適當地在低至1 ppb的濃度下使用,諸如1與50 ppb之間的濃度。
在一個實施例中,氧化物塗層組成物包含:
i. 1至50 g/L之鹼;
ii. 10至240 g/L之氧化劑;
iii. 1至20 g/L之酸;及
iv. 1 ppb至5,000 ppm之腐蝕抑制劑,其中腐蝕抑制劑包含如本文所述之氮雜環化合物。
在一較佳實施例中,本文所述之組成物中不包括其他組分。在一個實施例中,本發明基本上由鹼、氧化劑、酸、及如本文所述濃度之氮雜環化合物所組成。在另一實施例中,本發明由鹼、氧化劑、酸、及氮雜環化合物所組成,在如本文所闡述之濃度下不存在任何不可避免的污染物。「基本上由……組成(consisting essentially of)」意指組成物不含對氧化物重量、黏著促進、邊緣侵蝕、及抗酸性具有不利影響的任何組分。
本發明之發明人已發現,氧化劑與鹼性之比率對氧化物結構、氧化物顏色等具有影響,且最終可改變氧化物之效能。在一個實施例中,組成物中亞氯酸鹽與氫氧化鈉之比率在約1:1至約20:1,更佳地在約10:1至約19:1,最佳地在約15:1至約18:1之範圍內。
氧化物塗層組成物之pH較佳地在氧化物塗層組成物之整個壽命期間維持在約11至約15,更佳地在約12至約14,更佳地在約12.5至約13.8,最佳地在約13.1至約13.3之間。在一個實施例中,氧化物塗層組成物之pH在氧化物塗層組成物之整個壽命期間維持在約13.2。若需要調整,可添加鹼及/或酸以調整組成物之pH至所欲範圍內。
氧化物塗層組成物之溫度較佳地維持在約40℃與80℃之間,更佳地在約45℃與75℃之間,最佳地在約48℃與約60℃之間。在一個實施例中,氧化物塗層組成物之溫度針對預浸及塗層溶液皆維持在約50℃。在水平及垂直處理兩者期間,可維持氧化物塗層組成物之溫度在此位準。額外地,據信此範圍內的溫度針對水平處理係最佳的。
在使銅表面與氧化物塗層組成物接觸以在銅表面上產生奈米結晶氧化物結構之後,介電非導電層(諸如預浸漬層、聚合物光阻劑、乾膜等)在黏著步驟中係直接相鄰於銅表面放置,以將銅表面結合至介電非導電層,及形成多層印刷電路板。熱及/或壓力可用以起始黏著反應。若干層可在黏著步驟中放置在一起以在單一步驟中層壓若干層。
氧化物重量係浴效能之一項指標,且藉由銅重量增加試樣來評估。所欲的是氧化物重量足夠高以促進極佳的黏著性,同時亦足夠低以提供足夠的抗酸性。氧化物重量較佳地在約0.010與約0.150 mg/cm
2,更佳地在約0.015至約0.035 mg/cm
2之間。低於約0.025 mg/cm
2之氧化物重量,觀察到抗酸性較佳,而高於約0.040 mg/cm
2之氧化物速率,觀察到酸侵蝕更普遍。
現將參照下列非限制性實例描述本發明:
實例:
表1中所闡述之循環用於處理銅箔,以製造所有此等實例中之6層測試面板(Megtron-6預浸體,可購自Panasonic):
表1. 處理測試面板之循環
步驟 | 時間(分鐘) |
MultiBond酸性清潔劑S,43℃ | 3 |
冷水潤洗 | 2 |
MultiBond鹼性清潔劑R,50℃ | 5 |
冷水潤洗 | 2 |
預浸(50℃) | 0.5 |
氧化物塗層組成物,50℃ | 1 |
冷水潤洗 | 1 |
強制風乾 | 0.5 |
MultiBond酸性清潔劑S及MultiBond鹼性清潔劑R皆可購自MacDermid Enthone Inc., Waterbury, CT。
應注意的是,根據表1之步驟垂直地處理所有實例。
評估以下參數:
1) 表面粗糙度,對進入的銅表面之最小變化
2) 均勻的美觀外觀
3) 該程序在所有類型之銅上發揮作用的能力
4) 對各種非導電材料(包括MEG-6、370 HR、及ABF)之黏著性
5) 熱穩定性–至少30次以上的脫層循環及30分鐘以上的T-300。將脫層循環透過回流爐處理,回流曲線在260℃峰值溫度。使用熱機械分析儀(Thermal Mechanical Analyzer, TMA)進行T-300測試,其在300℃等溫下運行60分鐘,以強制測試樣本脫層。
6) 可接受之抗酸性
實例1 :
進行測試以評估各種氧化物塗層組成物之有效性。
製備氧化物塗層組成物,其包含:
6至12 g/L氫氧化鈉
120至180 g/L亞氯酸鈉
2至6 g/L磷酸
腐蝕抑制劑係包括於如下之組成物中:
溶液1:無腐蝕抑制劑
溶液2:75 ppm之苯并三唑(BTA)
溶液3:75 ppm之5-氯苯并三唑(5-Cl-BTA)
溶液4:1000 ppm之苯并三唑-5-羧酸(BTA-5-COOH)
藉由將鹼、氧化劑、及酸連同所列出之腐蝕抑制劑混合在一起製成水溶液,以產生溶液1至4。接著將溶液1至4中之各者施加至銅箔以製造6層測試面板。
將測試箔與水溶液接觸30/60秒循環,其中第一個數字係指在預浸組成物中之停留時間,且第二個數字係指在氧化物塗層組成物中之停留時間。其後,檢驗測試面板。
圖1顯示與不含有任何腐蝕抑制劑之水溶液相比,添加不同腐蝕抑制劑對外觀之影響。如圖1中所見,添加腐蝕抑制劑導致不同氧化物外觀,且亦顯示改善之抗酸性。黏著資料(lbs./in.)係在6X回流之前及之後判定的,且在圖1中描繪。
表2顯示在去污、電鍍通孔處理(plated through-hole processing, PTH)、及在去污及PTH之後的酸性銅及邊緣侵蝕(µm)步驟之後的粉紅圈(µm)結果。如表2中所見,含有本發明腐蝕抑制劑之組成物導致粉紅圈及邊緣侵蝕兩者的量更小,其指示達成更好的抗酸性。
表2. 粉紅圈及邊緣侵蝕之結果
腐蝕抑制劑 | 粉紅圈(µm) | 邊緣侵蝕(µm) |
無 | 81.0 | 90.2 |
BTA | 51.8 | 40.4 |
5-Cl-BTA | 41.4 | 36.7 |
BTA-5-COOH | 42.1 | 23.4 |
圖2描繪包括MEG-6核心及預浸體兩者且循環經過20個循環之6層測試面板的截面。溶液2至4中之各者在20個循環之後皆未觀察到脫層。
圖3描繪包括MEG-6核心及預浸體兩者且已循環30分鐘之6層測試面板的截面。溶液2至4中之各者在30分鐘之後皆未觀察到脫層。
實例2 :
執行時間研究以比較不含有腐蝕抑制劑之測試溶液與含有75 ppm的苯并三唑作為腐蝕抑制劑之溶液,且結果顯示於表3中。在測試溶液中測量不同停留時間之氧化物重量及剝離強度兩者。如表3所示,在30/60秒之停留時間下,含有腐蝕抑制劑之溶液中的氧化物重量較低得多,且在所欲的氧化物重量內。如上文所闡述,第一個數字係指在預浸組成物中之停留時間,且第二個數字係指在氧化物組成物中之停留時間。
如表3中所見,在較長停留時間下之氧化物重量更高,其指示較短的停留時間提供較佳的結果。額外地,在原樣及6X回流之後兩者均測定剝離強度。在不含有機物腐蝕抑制劑之情況下,原樣及在6X回流之後兩者,剝離強度皆更好。在氧化物浴中之腐蝕抑制劑,其在奈米塗層形成期間與氧化物調節,且略微改變結構,產生略微降低的黏著性,但改善抗酸性
表3. 腐蝕抑制劑(苯并三唑)之時間研究
實例3 :
停留時間(秒) | 氧化物重量(mg/cm 2) | 剝離強度(lbs./in.) | ||||
不含有機物 | 75 ppm BTA | 不含有機物 | 75 ppm BTA | |||
原樣 | 6X回流 | 原樣 | 6X回流 | |||
30/60 | 0.0588 | 0.0340 | 4.85 | 5.00 | 4.60 | 4.35 |
60/120 | 0.0665 | 0.0680 | 4.60 | 5.20 | 4.50 | 4.20 |
90/180 | 0.0723 | 0.0932 | 5.10 | 5.40 | 5.00 | 4.85 |
120/240 | 0.0743 | 0.0636 | 4.30 | 5.20 | 4.65 | 4.90 |
使用75 ppm之5-氯苯并三唑執行相同研究,結果顯示於表4中。在測試溶液中測量不同停留時間之氧化物重量及剝離強度兩者。如表4所示,在30/60秒之停留時間下,含有腐蝕抑制劑之溶液中的氧化物重量較低得多,且在所欲的氧化物重量內。然而,在較長停留時間下之氧化物重量更高,其指示較短的停留時間提供較佳的結果。額外地,在原樣及6X回流之後兩者均觀察到剝離強度。
表4. 腐蝕抑制劑(5- 氯苯并三唑)之時間研究
實例4 :
停留時間(秒) | 氧化物重量(mg/cm 2) | 剝離強度(lbs./in.) | ||||
不含有機物 | 75 ppm 5-Cl-BTA | 不含有機物 | 75 ppm 5-Cl-BTA | |||
原樣 | 6X回流 | 原樣 | 6X回流 | |||
30/60 | 0.0607 | 0.0272 | 5.50 | 5.15 | 2.70 | 1.80 |
60/120 | 0.0694 | 0.0626 | 5.30 | 5.25 | 4.30 | 3.20 |
90/180 | 0.0684 | 0.0859 | 5.25 | 4.80 | 5.25 | 3.75 |
120/240 | 0.0767 | 0.0995 | 5.25 | 5.30 | 5.05 | 5.25 |
亦使用1,000 ppm之苯并三唑-5-羧酸執行相同研究,結果顯示於表5中。在測試溶液中測量不同停留時間之氧化物重量及剝離強度兩者。如表5所示,在30/60及60/120秒之停留時間下,含有腐蝕抑制劑之溶液中的氧化物重量較低得多,且在所欲的氧化物重量內。然而,在較長停留時間下之氧化物重量更高,其指示較短的停留時間提供較佳的結果。額外地,在原樣及6X回流之後兩者均觀察到剝離強度。
表5. 腐蝕抑制劑(苯并三唑-5- 羧酸)之時間研究
實例5 :
停留時間(秒) | 氧化物重量(mg/cm 2) | 剝離強度(lbs./in.) | ||||
不含有機物 | 1000 ppm BTA-5-COOH | 不含有機物 | 1000 ppm BTA-5-COOH | |||
原樣 | 6X回流 | 原樣 | 6X回流 | |||
30/60 | 0.0529 | 0.0121 | 5.25 | 4.10 | 0.70 | 0.65 |
60/120 | 0.0631 | 0.0301 | 4.55 | 3.85 | 3.00 | 3.45 |
90/180 | 0.0680 | 0.1019 | 4.70 | 4.15 | 4.60 | 3.35 |
120/240 | 0.0723 | 0.0772 | 5.10 | 4.95 | 4.75 | 4.45 |
執行時間研究以判定若干種不同唑類在各種停留時間下之邊緣侵蝕量。透過奈米氧化物程序處理銅箔,且接著與所欲樹脂系統層壓。在層壓之後,用膠帶黏出一吋的條帶,且將剩餘的銅蝕刻掉,以暴露層壓體。接著透過去污及PTH處理測試樣本,且接著自層壓體拉下黏上的條帶。在高放大率顯微鏡下檢視條帶之邊緣以判定氧化物塗層之侵蝕量。結果顯示於表6中。
所欲的邊緣侵蝕值較佳地小於約100 µm,更佳地小於約50 µm,更佳地小於約40 µm,更佳小於約30 µm,更佳地小於約20 µm,且甚至更佳地小於約15 µm。
表6. 邊緣侵蝕
停留時間(秒) | 邊緣侵蝕(µm) | |||||
不含有機物 | BTA | 不含有機物 | 5-Cl-BTA | 不含有機物 | BTA-5-COOH | |
30/60 | 71.9 | 34.7 | 56.1 | 25.5 | 131 | 26.2 |
60/120 | 155 | 50.6 | 112 | 27.4 | 141 | 46.7 |
90/180 | 126 | 81.5 | 88.7 | 32.8 | 113 | 62.0 |
120/240 | 135 | 126 | 64.3 | 64.6 | 148 | 60.0 |
圖4描繪各種有機添加劑之剝離強度與氧化物速率的散佈圖。如圖4所示,藉由使用本發明之腐蝕抑制劑可達成較低的氧化物重量,且亦觀察到適當的剝離強度。
實例6 :
執行時間研究以比較不含有腐蝕抑制劑之測試溶液與含有75 ppm的苯并三唑作為腐蝕抑制劑之溶液,如表3中所述,但停留時間不同,且結果顯示於表7中。在測試溶液中測量不同停留時間之氧化物重量及剝離強度兩者。如表7所示,在30/60秒及更低之停留時間下,含有腐蝕抑制劑之溶液中的氧化物重量皆較低得多,且在所欲的氧化物重量內。
表7. 腐蝕抑制劑(苯并三唑)之時間研究
停留時間(秒) | 氧化物重量(mg/cm 2) | 剝離強度(lbs./in.) | ||||
不含有機物 | 75 ppm BTA | 不含有機物 | 75 ppm BTA | |||
原樣 | 6X回流 | 原樣 | 6X回流 | |||
15/30 | 0.0262 | 0.0146 | 3.15 | 2.65 | 2.15 | 1.15 |
20/40 | 0.0354 | 0.0194 | 3.80 | 2.20 | 1.85 | 2.20 |
25/50 | 0.0452 | 0.0238 | 4.65 | 3.05 | 2.95 | 2.05 |
30/60 | 0.0544 | 0.0316 | 4.40 | 3.40 | 3.45 | 3.25 |
30/60 (第1次測試) | 0.0588 | 0.0340 | 4.85 | 5.00 | 4.60 | 4.35 |
表8描繪針對苯并三唑腐蝕抑制劑在15/30至120/240之停留時間的邊緣侵蝕資料的時間研究。如表8所示,相較於不含有機物之溶液,邊緣侵蝕在所有停留時間下皆較少,且邊緣侵蝕值在較低停留時間下大致較佳。
表8. 邊緣侵蝕之時間研究
停留時間(秒) | 邊緣侵蝕(µm) | |
不含有機物 | BTA | |
15/30 | 30.8 | 18.4 |
20/40 | 48.8 | 22.3 |
25/50 | 60.1 | 35.0 |
30/60 | 77.1 | 44.0 |
30/60(第1次測試) | 71.9 | 34.7 |
60/120 | 155 | 50.6 |
90/180 | 126 | 81.5 |
120/240 | 135 | 126 |
表9描繪針對苯并三唑腐蝕抑制劑在15/30至30/60之停留時間下氧化物重量及黏著性(剝離強度)的時間研究。
表9. 時間研究– 氧化物重量及黏著性
停留時間(秒) | 氧化物重量(mg/cm 2) | 剝離強度(lbs./in.) | |
原樣 | 6X回流 | ||
15/30 | 0.0369 | 5.00 | 5.00 |
20/40 | 0.0413 | 4.25 | 3.80 |
25/50 | 0.0524 | 4.60 | 4.70 |
30/60(無BTA) | 0.0607 | 4.60 | 4.50 |
30/60 | 0.0597 | 4.60 | 4.85 |
M-Speed HF (30 µin) | 3.30 | 2.90 |
停留時間研究顯示,較高的氧化物重量及厚度導致界面處的更多酸侵蝕。較短的停留時間(亦即,小於30/60秒)展現更好的抗酸性及低至14 µm的邊緣侵蝕。
調整BTA濃度以最佳化剝離強度及美觀均勻性。在一個實施例中,75 ppm之BTA濃度判定為產生良好結果。
本發明顯示,針對各種氮雜環化合物,30/60秒之停留時間提供良好結果。
實例7 :
使用咪唑作為腐蝕抑制劑執行研究,且在下表10中提供各種咪唑濃度之結果。
表10– 咪唑濃度研究:
咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0539 | 74.8 | 4.8 | 4.9 |
50 | 0.0427 | 48.6 | 4.9 | 4.6 |
100 | 0.0315 | 32.9 | 4.1 | 4.1 |
150 | 0.0184 | 13.6 | 3.7 | 3.7 |
M-Speed HF控制 | 0 | 3.3 | 3.2 |
如圖5中所示且如表10中所闡述,氧化物重量、邊緣侵蝕、及剝離強度值在50 ppm及150 ppm之濃度下顯示良好結果。
實例8 :
使用二氯苯并三唑作為腐蝕抑制劑執行研究,且結果在下表11中提供。
表11– 二氯苯并三唑濃度研究:
二氯苯并三唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0563 | 62.1 | 4.2 | 4.7 |
25 | 0.0524 | 67.2 | 4.7 | 4.3 |
50 | 0.0383 | 47.2 | 4.4 | 4.5 |
75 | 0.0252 | 39.6 | 3.5 | 3.3 |
100 | 0.0180 | 35.4 | 2.5 | 3.0 |
M-Speed HF控制 | 0 | 3.2 | 3.2 |
如圖6中所示且如表11中所闡述,氧化物重量、邊緣侵蝕、及剝離強度值在25 ppm及50 ppm之濃度下顯示良好結果,但在75 ppm及100 ppm之二氯苯并三唑之濃度下,氧化物重量減少,且剝離強度亦減損。
實例9 : 表12– 4- 溴-1H- 吲唑濃度研究:
4- 溴-1H- 吲唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0558 | 89.1 | 4.1 | 3.7 |
2 | 0.0495 | 69.0 | 4.1 | 2.9 |
4 | 0.0417 | 64.9 | 3.6 | 2.5 |
6 | 0.0257 | 50.4 | 3.1 | 1.6 |
M-Speed HF控制 | 0 | 3.1 | 3.4 |
如表12中所闡述,4-溴-1H-吲唑以比上述其他唑類更低的濃度使用。然而,在2至6 ppm之範圍內的濃度下,氧化物重量、邊緣侵蝕、及剝離強度值顯示良好結果,雖然氧化物重量及剝離強度在6 ppm之較高濃度下降低。然而,邊緣侵蝕值高於所測試之其他唑類腐蝕抑制劑的一些者。
實例10 : 表13– 苯并咪唑濃度研究:
苯并咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0524 | 65.7 | 4.7 | 4.6 |
25 | 0.0481 | 52.9 | 4.2 | 4.2 |
50 | 0.0515 | 63.0 | 1.6 | 1.9 |
75 | 0.0461 | 86.2 | 0.5 | 0.6 |
100 | 0.0417 | 79.6 | <0.5 | <0.5 |
M-Speed HF控制 | 0 | 2.4 | 2.4 |
如表13中所見,該浴僅在較低濃度的苯并咪唑下最穩定。雖然保持可接受的氧化物速率,但剝離強度在高於約25 ppm未顯示良好結果,且邊緣侵蝕值在整個範圍內皆係高的。因此,雖然苯并咪唑可用作唑類腐蝕抑制劑,但必須小心控制苯并咪唑之濃度及其他參數以產生可接受的結果。
實例11 : 表14– 咪唑濃度研究:
咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0544 | 83.1 | 4.5 | 4.8 |
100 | 0.0330 | 28.4 | 4.5 | 4.3 |
200 | 0.0146 | 8.02 | 2.7 | 2.8 |
400 | 0.0078 | 21.0 | <0.5 | <0.5 |
M-Speed HF控制 | 0 | 3.2 | 3.3 |
如表14中所見,該浴在400 ppm咪唑之濃度下停止。由於非常低的氧化物重量及不良的氧化物發展,此濃度下之剝離強度小於0.5 lbs./in.。然而,邊緣侵蝕值在濃度範圍內非常良好。
實例12 : 表15– 4- 溴- 咪唑濃度研究:
4- 溴- 咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0510 | 65.8 | 4.5 | 5.0 |
10 | 0.0495 | 55.8 | 4.8 | 5.0 |
25 | 0.0476 | 70.2 | 4.7 | 5.1 |
50 | 0.0417 | 64.0 | 4.7 | 4.7 |
75 | 0.0393 | 55.4 | 4.7 | 4.7 |
100 | 0.0354 | 50.6 | 4.7 | 4.6 |
125 | 0.0320 | 47.4 | 4.7 | 4.9 |
150 | 0.0315 | 54.9 | 4.5 | 4.9 |
M-Speed HF控制 | 0 | 3.3 | 3.2 |
如表15中所闡述,該浴在至多150 ppm的4-溴咪唑下未停止。氧化物重量逐漸降低,但維持極佳的剝離強度。邊緣侵蝕性能保持穩定且可接受但不是很好。
在較寬的濃度範圍內執行4-溴-咪唑之進一步研究,且結果顯示於表16中。
表16– 至多400 ppm 的4- 溴- 咪唑濃度研究:
4- 溴- 咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0582 | 60.4 | 4.8 | 5.0 |
50 | 0.0417 | 46.9 | 4.8 | 4.6 |
100 | 0.0311 | 46.7 | 4.7 | 4.4 |
200 | 0.0248 | 33.1 | 4.8 | 4.6 |
300 | 0.0194 | 30.3 | 4.4 | 4.1 |
400 | 0.0180 | 20.6 | 4.5 | 4.1 |
M-Speed HF控制 | 0 | 3.3 | 3.6 |
如表16中所見,即使4-溴-咪唑在400 ppm之濃度下,該浴並未停止。隨著濃度增加,氧化物重量持續下降,但剝離強度仍保持極佳。在較高濃度下,邊緣侵蝕有顯著改善,但觀察到美觀外觀展現些微非均勻性。
實例13 : 表17–2,4- 二溴- 咪唑濃度研究:
2,4- 二溴- 咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0451 | 70.2 | 4.9 | 4.9 |
10 | 0.0539 | 56.8 | 4.9 | 5.0 |
25 | 0.0694 | 80.8 | 4.7 | 4.8 |
50 | 0.0544 | 85.5 | 4.8 | 4.9 |
100 | 0.0524 | 75.6 | 5.0 | 5.0 |
200 | 0.0500 | 73.0 | 4.5 | 4.8 |
300 | 0.0476 | 74.4 | 4.9 | 4.9 |
400 | 0.0456 | 64.3 | 4.6 | 4.3 |
500 | 0.0476 | 90.9 | 4.6 | 4.5 |
M-Speed HF控制 | 0 | 2.4 | 2.6 |
如表17中所見,即使在500 ppm下,該浴並未停止。在濃度範圍內,在氧化物重量增加、美觀、邊緣侵蝕、及剝離強度方面未觀察到效能的顯著變化。然而,邊緣侵蝕效能在濃度範圍內相對較差。
實例14 : 表18 – 4,5- 二氯- 咪唑濃度研究:
4,5- 二氯- 咪唑(ppm) | 氧化物重量(mg/cm 2) | 邊緣侵蝕(µm) | 剝離強度(lbs./in.) | |
原樣 | 6X 回流 | |||
0 | 0.0471 | 58.4 | 5.0 | 5.3 |
25 | 0.0466 | 82.9 | 4.9 | 5.1 |
50 | 0.0558 | 59.0 | 4.7 | 5.0 |
75 | 0.0544 | 59.0 | 4.9 | 5.1 |
100 | 0.0507 | 65.2 | 4.8 | 5.1 |
200 | 0.0485 | 67.8 | 4.9 | 5.1 |
400 | 0.0447 | 69.9 | 4.9 | 4.8 |
800 | 0.0126 | 37.7 | 3.2 | 1.6 |
M-Speed HF控制 | 0 | 2.9 | 3.0 |
如表18中所見,即使在800 ppm之濃度下,該浴並未停止。然而,在此濃度下之美觀外觀係不可接受的,且氧化物重量及剝離強度顯著降低。在整個至多400 ppm之濃度範圍內,氧化物重量及剝離強度保持穩定。與其他唑類相比,邊緣侵蝕效能不良。
該等實例顯示氮雜環化合物之類型及濃度連同停留時間係使用本文所述之程序增強金屬導電層與無機材料之間的黏著性的重要因素,且此等因素之平衡係必要的,以達到最佳結果。
所欲的是,氮雜環化合物在能夠達成以下所欲性質之濃度下用於浴中:
a. 氧化物重量增加在約0.010至約0.080,更佳地在約0.015至約0.070,更佳地在約0.015至約0.035 mg/cm
2之範圍內,以提供良好的黏著性及抗酸性;及/或
b. 邊緣侵蝕小於小於約100 µm,更佳地小於約50 µm,更佳地小於約40 µm,更佳小於約30 µm,更佳地小於約20 µm,且甚至更佳地小於約15 µm;及/或
c. 在原樣及6X回流之後兩者,剝離強度均大於約2.0 lbs./in.,更佳地大於約3.0 lbs./in.,更佳地大於約4.0 lbs./in.,更佳地大於約4.5 lbs./in.,且大致較佳的是剝離強度及6X回流後相對一致。
為了最佳結果,較佳的是符合所有此等性質。如藉由實例所證明,組成物中之氮雜環化合物之濃度可取決於所使用之特定抑制劑而廣泛變化。
最後,亦應理解的是,下列申請專利範圍意欲涵蓋本文所述之本發明的所有通用及特定特徵,以及就語言方面可落在其間的本發明之範疇的所有陳述。
無
現將參照下列圖式描述本發明,其中:
〔圖1〕描繪根據實例1所製備之若干不同氧化物塗層組成物處理之測試樣本的美觀及剝離強度的結果。
〔圖2〕描繪判定根據實例1之若干不同氧化物塗層組成物處理之測試樣本的脫層循環數目的研究結果。
〔圖3〕描繪根據實例1之若干不同氧化物塗層組成物處理之測試樣本的脫層測試結果。
〔圖4〕描繪藉由實例1之氧化物塗層組成物之浴構成的邊緣侵蝕(edge attack)與氧化物重量的散佈圖。
〔圖5〕描繪根據實例7之氧化物塗層組成物中處理之測試樣本的邊緣侵蝕的停留時間研究結果。
〔圖6〕描繪根據實例8之氧化物塗層組成物中處理之測試樣本的邊緣侵蝕的停留時間研究結果。
Claims (27)
- 一種用於增強金屬導電層與無機材料或聚合樹脂材料之間的黏著性的程序,該程序包含下列步驟: a) 施加預浸至該金屬導電層; b) 將氧化物塗層組成物施加至該金屬導電層以產生抗酸表面,其中該氧化物塗層組成物包含: i. 鹼; ii. 氧化劑; iii. 酸;及 iv. 腐蝕抑制劑,其中該腐蝕抑制劑包含氮雜環化合物;及 c) 將該無機材料或聚合樹脂材料接合至該金屬導電層。
- 如請求項1之程序,其中該金屬導電層包含銅或銅合金。
- 如請求項1之程序,其中該黏著性促進組成物之該鹼係選自由氫氧化鈉、氫氧化鉀、氫氧化銨、及上述一或多種之組合所組成之群組的氫氧化物。
- 如請求項1之程序,其中該氧化物塗層組成物之該氧化劑包含亞氯酸鈉。
- 如請求項1之程序,其中該氧化物塗層組成物之該酸包含磷酸。
- 如請求項5之程序,其中該酸由磷酸組成。
- 如請求項1之程序,其中該氮雜環化合物係選自由下列所組成之群組:唑類、吡啶類、嘧啶類、哌啶類、嗎啉類、及上述一或多種之組合。
- 如請求項7之程序,其中該氮雜環化合物包含唑基腐蝕抑制劑,該唑基腐蝕抑制劑選自由下列所組成之群組:未經取代或經取代之吡唑類、咪唑類、三唑類、四唑類、噻唑類、噻二唑類、咔唑類、吲唑類、苯并咪唑類、苯并三唑類、苯并噻唑類、苯并噻二唑類、及上述一或多種之組合。
- 如請求項8之程序,其中該唑基腐蝕抑制劑具有包括鹵素取代基之環結構。
- 如請求項8之程序,其中該鹵素成分係氯化物及溴化物中之至少一者。
- 如請求項1之程序,其中該氮雜環化合物係經取代或未經取代之單環化合物。
- 如請求項8之程序,其中該唑基腐蝕抑制劑係選自由下列所組成之群組:咪唑、1,4-二氯苯并三唑、4,5-二氯-2H-苯并三唑、1,4-二氯苯并三唑、5,5-二氯苯并三唑、5,6-二氯苯并三唑、2,5-二氯苯并三唑、2,4-二氯苯并三唑、2,6-二氯苯并三唑、2,7-二氯苯并三唑、5-氯苯并三唑、1-氯苯并三唑、2-氯苯并三唑、2-溴-1H-吲唑、4-溴-1H-吲唑、5-溴-1H-吲唑、6-溴-1H-吲唑、7-溴-1H-吲唑、4-溴-1H-咪唑、5-溴-1H-咪唑-2-羧酸、1,2-二溴咪唑-4-羧酸、2,4-二溴-1H-咪唑、4,5-二溴-1H-咪唑、1,4-二溴-1H-咪唑、4,4-二溴-1H-咪唑、苯并咪唑、2-4-二溴咪唑、4,5-二氯咪唑、1,5-二氯咪唑、3,4-二氯咪唑、4,5-二氯咪唑-1-羧酸、1,2-二氯咪唑、4,5-二氯-1H-咪唑、2,2-二氯咪唑、1,4-二氯咪唑、4,4-二氯咪唑、2,5-二氯-1H-咪唑、苯并三唑-5-羧酸、及上述一或多種之組合。
- 如請求項1之程序,其中該氧化物塗層組成物維持在約12與約14之間的pH。
- 如請求項1之程序,其中該氧化物塗層組成物維持在約40℃與約80℃之間的溫度下。
- 如請求項1之方法,其中該基材係與該組成物接觸15至240秒的期間。
- 如請求項1之方法,其中氧化劑與鹼之比率在約1:1至約20:1之範圍內。
- 如請求項1之方法,其中該金屬導電層上之氧化物速率係在約0.010與約0.080 mg/cm 2之間。
- 一種多層線路板,其藉由如請求項1之程序製備。
- 如請求項18之多層線路板,其中該多層線路板展現以下性質: a. 該金屬導電層上之氧化物速率係在約0.020與約0.080 mg/cm 2之間;及/或 b. 邊緣侵蝕小於約75 µm;及/或 c. 在原樣及6X回流後,剝離強度大於約2.0 lbs./in。
- 一種氧化物塗層組成物,其包含: i. 1至150 g/L之鹼; ii. 10至240 g/L之氧化劑; iii. 1至20 g/L之酸;及 iv. 1 ppb至5,000 ppm之腐蝕抑制劑,其中該腐蝕抑制劑包含氮雜環化合物。
- 如請求項20之氧化物塗層組成物,其中該氮雜環化合物係選自由下列所組成之群組:唑類、吡啶類、嘧啶類、哌啶類、嗎啉類、及上述一或多種之組合。
- 如請求項21之氧化物塗層組成物,其中該氮雜環化合物包含唑基腐蝕抑制劑,該唑基腐蝕抑制劑選自由下列所組成之群組:未經取代或經取代之吡唑類、咪唑類、三唑類、四唑類、噻唑類、噻二唑類、咔唑類、吲唑類、苯并咪唑類、苯并三唑類、苯并噻唑類、苯并噻二唑類、及上述一或多種之組合。
- 如請求項20之氧化物塗層組成物,其中該氮雜環化合物具有包括鹵素取代基之環結構。
- 如請求項23之氧化物塗層組成物,其中該鹵素成分係氯化物及溴化物中之至少一者。
- 如請求項22之氧化物塗層組成物,其中該唑基腐蝕抑制劑係選自由下列所組成之群組:咪唑、1,4-二氯苯并三唑、4,5-二氯-2H-苯并三唑、1,4-二氯苯并三唑、5,5-二氯苯并三唑、5,6-二氯苯并三唑、2,5-二氯苯并三唑、2,4-二氯苯并三唑、2,6-二氯苯并三唑、2,7-二氯苯并三唑、5-氯苯并三唑、1-氯苯并三唑、2-氯苯并三唑、2-溴-1H-吲唑、4-溴-1H-吲唑、5-溴-1H-吲唑、6-溴-1H-吲唑、7-溴-1H-吲唑、4-溴-1H-咪唑、5-溴-1H-咪唑-2-羧酸、1,2-二溴咪唑-4-羧酸、2,4-二溴-1H-咪唑、4,5-二溴-1H-咪唑、1,4-二溴-1H-咪唑、4,4-二溴-1H-咪唑、苯并咪唑、2-4-二溴咪唑、4,5-二氯咪唑、1,5-二氯咪唑、3,4-二氯咪唑、4,5-二氯咪唑-1-羧酸、1,2-二氯咪唑、4,5-二氯-1H-咪唑、2,2-二氯咪唑、1,4-二氯咪唑、4,4-二氯咪唑、2,5-二氯-1H-咪唑、苯并三唑-5-羧酸、及上述一或多種之組合。
- 如請求項20之氧化物塗層組成物,其中該氧化物塗層組成物之pH係在約12與約14之間。
- 如請求項20之氧化物塗層組成物,其中氧化劑與鹼之比率係在約1:1至約20:1之範圍內。
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2022
- 2022-11-18 TW TW111144131A patent/TW202337984A/zh unknown
- 2022-12-16 US US18/082,701 patent/US20230119587A1/en not_active Abandoned
- 2022-12-16 WO PCT/US2022/081797 patent/WO2023122498A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
JP2022099497A (ja) | 2022-07-05 |
US20220199021A1 (en) | 2022-06-23 |
US11562695B2 (en) | 2023-01-24 |
WO2023122498A1 (en) | 2023-06-29 |
US20230199972A1 (en) | 2023-06-22 |
US20230119587A1 (en) | 2023-04-20 |
CN114664248B (zh) | 2023-06-27 |
CN114664248A (zh) | 2022-06-24 |
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