CN110429018A - 形成钝化层的方法、含钝化层的基底及钝化层去除方法 - Google Patents
形成钝化层的方法、含钝化层的基底及钝化层去除方法 Download PDFInfo
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- CN110429018A CN110429018A CN201910371982.8A CN201910371982A CN110429018A CN 110429018 A CN110429018 A CN 110429018A CN 201910371982 A CN201910371982 A CN 201910371982A CN 110429018 A CN110429018 A CN 110429018A
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Classifications
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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Abstract
本申请提供了一种在基底上形成钝化层的方法。该方法包括以下步骤:a)在处理室中提供基底,所述基底包括金属表面,其中,所述金属表面为铜、锡或银表面,或为包括铜、锡或银中的一种或多种的合金表面;b)通过气相沉积将至少一个有机层沉积到所述金属表面上,由有机前体形成的所述有机层包括:包括氧、氮、磷、硫、硒、碲或硅中的至少一种的第一官能团;和选自羟基(‑OH)或羧基(COOH)的第二官能团;其中,所述第一官能团吸附在所述金属表面上;和c)通过气相沉积将至少一个无机层沉积到所述有机层上,其中所述第二官能团用作无机层的附着位点。本申请还涉及具有所述钝化层的基底及从所述基底去除或降解钝化层的方法。
Description
技术领域
本发明涉及一种在基底上形成钝化层的方法。本发明还涉及包含通过上述方法形成的钝化层的基底。本发明进一步涉及一种从基底去除钝化层的方法。
背景技术
当暴露于或存储在大气条件下时,许多金属易于氧化。金属的氧化导致金属表面上形成金属氧化物。表面金属氧化物的形成对金属的化学、机械、光学和电学性质产生不利影响。基于这些原因,通常在形成电连接之前从金属表面去除金属氧化物。然而,金属氧化物可能生长到超过纳米量级,并且去除金属氧化物困难且耗时。因此,希望防止表面金属氧化物的形成。
用于防止表面金属氧化物形成的已知方法包括形成钝化层。“钝化层”是沉积在基底表面上的保护膜、层或涂层,以抑制或阻止在基底表面发生的化学反应,例如氧化反应。钝化层通常用作氧化阻挡层,该氧化阻挡层阻止下方表面的氧化。在金属表面(例如铜表面)的情况下,钝化层阻止金属表面的氧化,并由此防腐蚀。
有些已知的钝化层是永久性的。例如,已知将氧化铝直接沉积至金属表面上以抑制氧化。然而,去除这种永久钝化层通常需要可能破坏基底的其他组件的侵蚀性的化学蚀刻、机械抛光或其他工艺。
在某些应用中,例如在PCB表面处理或热压接合中,临时性的钝化层是优选的。理想的是能够根据需要来选择性地去除钝化层以为后续处理步骤作准备。例如,在电子器件的制造中,可能需要在形成电连接之前去除钝化层。
当形成电连接时,已知的是在焊接之前,在金属(例如铜)的表面上沉积一层有机保焊剂(organic solderability preservative,OSP)。在焊接之前,OSP层阻止金属表面的氧化并且用作钝化层。
OSP钝化层必须具有足以抑制下方金属表面的氧化最小厚度(通常为几百纳米),并且会在随后的处理步骤中污染基底。沉积OSP层的已知方法通常导致OSP层在基底表面上具有不均匀的厚度。厚的和/或不均匀的OSP层可能难以完全去除,并且OSP残留物可能在随后的处理步骤中污染基底。
期望减小钝化层的厚度,同时保持钝化层的抗氧化特性。期望钝化层具有改善的厚度均匀性。期望开发一种可以在长时间段内(例如在储存中)抑制或阻止氧化的钝化层,而当需要时可以选择性地从基底上除去该钝化层。期望能够选择性地去除钝化层而无需使用额外的处理步骤,例如侵蚀性的化学蚀刻或机械抛光。
替代的钝化涂层也是已知的,例如公开于R.W.Bonner III等人,Applied PowerElectronics Conference and Exposition(APEC),2012,498-502中的微通道冷却器的钝化涂层。Bonner III等人公开了一种铜基底,其中主要通过在铜基底上镀镍和金层来控制防腐蚀。使用长链烷硫醇以在抛光的金表面上形成自组装单层(SAM),并随后在其上沉积氧化铝层。较长的碳链是优选的,因为与短链的SAM分子相比,SAM分子的链越长组装和组织越好。Bonner的钝化涂层有助于防止腐蚀。
发明内容
在本发明的至少某些实施方式中,本发明旨在解决上述问题、期望和需求中的一部分。在本发明的至少某些实施方式中,本发明提供了一种形成钝化层的方法,该钝化层在长时间段内阻止下方金属表面的氧化,同时减少钝化层的所需厚度。该方法还改善钝化层的均匀性。在本发明的至少某些实施方式中,本发明还提供了一种用于形成钝化层的方法,该钝化层根据使用者的需要至少部分地从表面上选择性地为可降解和/或可去除。
根据本发明的第一方面,提供了一种在基底上形成钝化层的方法,该方法包括以下步骤:
a)在处理室中提供基底,所述基底包括金属表面,其中,所述金属表面为铜、锡或银表面,或为包括铜、锡或银中的一种或多种的合金表面;
b)通过气相沉积将至少一个有机层沉积至所述金属表面上,由有机前体形成的所述有机层包括:
第一官能团,包括氧、氮、磷、硫、硒、碲或硅中的至少一种;和
第二官能团,选自羟基(-OH)或羧基(-COOH);
其中,第一官能团吸附在所述金属表面上;和
c)通过气相沉积将至少一个无机层沉积到所述有机层上,其中所述第二官能团用作所述无机层的附着部位。
钝化层包括有机层和无机层。这种钝化层在室温下在长时间段内抑制或阻止下方金属表面的氧化。然而,钝化层的钝化特性可根据使用者的需要而劣化。在升高的温度下,钝化层可历经状态的变化以使钝化层的钝化特性劣化。例如,在升高的温度下,钝化层可以至少部分地分解、降解或从金属表面解吸。可以在机械应力下至少部分地去除钝化层。钝化层优选在低于焊接或热压接合温度的温度下例如通过降解,解吸或分解历经状态变化。以这种方式,钝化层的钝化特性在焊接过程中劣化,这确保在形成电连接之前不会形成氧化物。然而,如果降解温度太高,则基底的其他组件可能会被破坏。钝化层可在100℃~260℃的温度下至少部分地分解或降解。钝化层可任选地在100℃~150℃、任选地在150℃~200℃以及任选地在200℃~260℃的温度下至少部分地分解或降解。第一官能团可在100℃~260℃的温度下从金属表面解吸。第一官能团可任选地在100℃~150℃、任选地在150℃~200℃以及任选地在200℃~260℃的温度下从金属表面解吸。可以在上述给出的温度范围的任何组合之间的温度下去除钝化层。
包含有机层和无机层的钝化层在室温下提供稳定且有效的气体渗透屏障,由此阻止金属表面的氧化和腐蚀。
本发明的钝化层适用于对铜、锡或银表面(或包含铜、锡或银中一种或多种的合金的表面)进行钝化,而不需要额外的金属(例如金)保护层。这有利地省去处理步骤并最小化处理材料的成本。
步骤b)和步骤c)中的气相沉积技术的使用有利地使得在具有高纵横比(例如纵横比为至少10:1,优选至少100:1)的表面上沉积有机层和无机层。可以分别使用分子气相沉积和原子层沉积来在金属表面上沉积具有改善的均匀性的有机层和无机层。
第一官能团可选自:羧基(-COOH)、伯胺(-NH2)、仲胺、叔胺、硫醇(-SH)、二唑、三唑、二硫化物、异氰酸酯、膦酸酯、有机硒、有机碲或有机硅烷。
第一官能团可以是伯、仲或叔官能团。
第一官能团可化学吸附在金属表面上。化学吸附可以在第一官能团和金属表面之间提供临时附着方式。化学吸附可以提供与金属表面足够强的相互作用以在室温下长时间段内提供稳定的钝化层。化学吸附可以提供对温度敏感的钝化层以使得可以在升高的温度下去除该钝化层。化学吸附可以有助于在升高的温度下从金属表面去除钝化层。
有机前体可具有以下形式的结构:
X–R–Y
其中,X是第一官能团;R是取代或未取代的烷基,取代或未取代的环烷基,或取代或未取代的芳基;且Y是第二官能团。R可以是脂族链、脂环族环或芳族环。R可以取代有卤素,例如氟。X可以是伯、仲或叔官能团。Y可以是伯、仲或叔官能团。
R可以具有2~16个碳原子,优选具有2~11个碳原子。R可以具有2~7个碳原子,优选具有6个碳原子。上述碳原子可形成烷基,包括脂族链和脂环族环;或可以是芳基,包括芳族环。包含较少碳原子数的有机前体通常具有较高的蒸气压。这种有机前体优选用于气相沉积工艺。
有机前体可选自包括4-氨基苯酚、6-巯基-1-己醇和11-巯基十一烷酸的组。
所述有机层可以是自组装单层(SAM)。自组装单层可以自发地形成。
所述有机层可以是多层结构。也就是说,有机层可包含多于一层的有机前体。钝化层可包括多个有机层。在有些情况下,较厚的有机层(例如多层)可有助于提供表现出改善的抗氧化性的钝化层。
步骤b)可包括通过分子气相沉积将至少一个有机层沉积到所述金属表面上。
步骤c)可包括通过原子层沉积将至少一个无机层沉积到所述有机层上。
所述无机层可以是陶瓷材料。陶瓷材料可以是金属氧化物。
所述无机层可选自包括以下各项的组:氧化铝(Al2O3);GeO2、ZnO、SiOx、SiO2、Si3N4、TiO2、ZrO2、HfO2、SnO2、In2O3或Ta2O5。无机层可以提供具有低气体渗透率的无机层。无机层可以有效地抑制下方金属表面的氧化。无机层可以是多层结构。在有些情况下,无机多层结构可有助于提供表现出改善的抗氧化性同时使钝化层的总厚度最小化的钝化层。不希望受任何理论或推测的束缚,据信,随后的无机层填充下方无机层中的空隙和/或缺陷以提供具有更低气体渗透速率的层,并因此具有有利的钝化性质。
无机层可以具有0.1nm~10nm的厚度。无机层可包含约1~10个原子层。这种薄膜有利地降低了材料成本、缩短了制造时间,并因此提高了基底产量。此外,这种薄膜可以更容易地去除,并且可以降低后续处理步骤中污染的风险。
该方法还可以包括以下步骤:
aa)在步骤b)之前对金属表面进行还原处理。还原处理可以在步骤b)之前从金属表面去除表面金属氧化物。任何方便的还原处理都是合适的。还原处理可以是含氢等离子体处理。用于含氢等离子体处理的等离子体可以由H2/Ar气体混合物或由纯H2形成。或者,还原处理可包括将金属表面暴露于化学还原剂,例如酸或醇。化学还原剂可以是甲酸或乙醇。
可以在步骤a)、aa)、b)和/或c)中的一个或多个步骤之前,使用惰性气体吹扫处理室。可以在步骤a)、aa)、b)和/或c)中的一个或多个步骤之后,使用惰性气体吹扫处理室。所述惰性气体可以是氮气(N2)、氩气(Ar)或其他任何惰性气体。惰性气体是元素周期表第18族中的任何气体。用惰性气体吹扫处理室有助于在钝化层完全形成之前使形成表面金属氧化物的风险最小化。
步骤c)可以包括:将第一和第二气态反应物依次引入处理室中以附着到第二官能团或与第二官能团反应,由此形成无机层。第一气态反应物可以是三甲基铝(TMA)。第二气态反应物可以是水。优选地,第一和第二气态反应物非同步地引入处理室。任选地,在将第二气态反应物引入处理室之前,用惰性气体如氮气或氩气吹扫处理室。该任选的吹扫步骤可以去除可能存在于处理室中的副产物气体。
可以在同一处理室中进行步骤b)和步骤c)。在步骤a)、aa)、b)和/或c)期间,基底可以保留在处理室中。
步骤b)和步骤c)可以在这些步骤之间没有真空中断的情况下进行。步骤步骤a)、aa)、b)和/或c)可以在这些步骤之间没有真空中断的情况下进行。
可以重复步骤b)和/或步骤c)。可以重复步骤b)和/或步骤c)以增加有机层和无机层的厚度。可以循环重复步骤b)和步骤c)以形成包含交替的有机层和无机层的钝化层。
根据本发明的第二方面,提供了一种基底,所述基底包括使用本发明第一方面的方法形成的钝化层。
所述基底可以是印刷电路板(PCB)。所述基底可以是热压接合基底、引线接合基底或焊接接合基底。基底可适用于热压接合、引线接合、球形接合、楔形接合、焊接接合或焊接。
根据本发明的第三方面,提供了一种通过使根据第二方面的基底历经100℃~260℃的温度而从所述基底至少部分地去除或降解钝化层的方法。去除或降解钝化层可以包括完全或部分地从基底去除、降解、分解或解吸钝化层。可以在100℃~150℃、任选地在150℃~200℃以及任选地在200℃~260℃的温度下至少部分地去除、降解或分解钝化层。可以在上面提供的温度范围的任何组合之间的温度下去除钝化层。
尽管上面已经描述了本发明,但是本发明可以扩展至上述特征或者在以下描述、附图或权利要求中的任何创造性组合。
附图说明
现在将参考附图描述根据本发明的基底及方法的实施方式,其中:
图1A是具有用根据第一实施方式的方法形成的钝化层的基底的图示;
图1B是仅用有机层改性的基底的图示;
图2是在室温下用第一实施方式的方法形成的基底的氧化铜再生长程度随时间变化的曲线图;
图3是在150℃下使用第一实施方式的方法形成的基底的氧化铜再生长程度随时间变化的曲线图;
图4是适用于根据第一实施方式的方法形成具有钝化层的基底的装置的示意图;和
图5是根据第一实施方式的方法的流程图。
具体实施方式
本发明涉及一种制备具有用钝化层改性的铜、锡、银或合金的区域或表面的基底的方法。具体地,本发明的钝化层在高温和/或机械应力下是可降解的。
图1示出了包括用第一实施方式的方法形成的钝化层的基底100。该基底100包括铜表面102,该铜表面102用钝化层104改性。在其他实施方式中,基底可包括锡或银表面,或包括含铜、锡或银中的一种或多种的合金表面。铜表面102是基底100的暴露的表面。铜表面102可以形成基底100的暴露区域的一部分。铜表面102可以在基底100的表面上形成完整的层。在有些实施方式中,基底100完全由铜形成。
钝化层104包括有机层106和无机层108。钝化层104是具有低气体渗透率的阻挡层,并由此用于阻止铜表面102的氧化。有机层106由双官能或多官能的有机前体形成。多官能的有机分子是具有至少两个官能团的有机分子。通常,所述两个官能团由脂族碳链、脂环族环或芳族环分开。
在本发明中,第一官能团111适合于吸附到铜表面102。通常,第一官能团111化学吸附到铜表面102。第一官能团111提供良好的与铜表面102的附着性,以在室温下提供稳定的钝化层。第一官能团111通常包含:硫、氮、硅、氧、磷、碲和/或硒。第一官能团111可以是羧基(-COOH)、伯胺(-NH2)、仲胺、叔胺、硫醇(-SH)、二唑、三唑、二硫化物、异氰酸酯、膦酸酯、有机硒、有机碲或有机硅烷。在第一实施方式中,第一官能团是巯基(-SH)。在基底具有铜表面的情况下,第一官能团优选包含硫,例如巯基(-SH)或二硫化物;或氮,如胺、二唑或三唑。
第二官能团112适于附着至无机层108或与无机层108反应。通常,第二官能团112为随后的薄层(例如无机层108)提供吸附位点。在第一实施方式中,第二官能团是羟基(-OH)。在其他实施方式中,第二官能团是羧基(-COOH)。
通常,第一和第二官能团由脂族碳链、或者由脂环族的或芳族的碳环分开。通常,所述碳链包含2~16个碳原子。
在第一实施方式中,有机层由有机前体6-巯基-1-己醇形成。在替代实施方式中,有机前体是4-氨基苯酚或11-巯基十一烷酸。方便地,有机前体吸附至铜表面102,并形成自组装层110(图1B)。通常,自组装层是自组装单层(SAM),然而,有机层106可以是多层薄层。第一官能团111通常化学吸附到铜表面。第二官能团112通常能够附着于随后添加的任何层,例如无机层108,或与之反应。
无机层108包含陶瓷材料,例如金属氧化物。无机层108沉积在有机层106上。第二官能团112用作无机层108的附着位点。在一些实施方式中,无机层108与第二官能团112反应。在第一实施方式中,无机层108由氧化铝(Al2O3)构成。氧化铝通常形成三维无定型层。在其他实施方式中,无机层可以由GeO2、ZnO、SiOx、SiO2、Si3N4、TiO2、ZrO2、HfO2、SnO2、In2O3或Ta2O5形成。
通过使用包含有机层106和无机层108的混合钝化层104,抑制了铜表面102的氧化。不希望受任何理论或猜想的束缚,无机层108表现为具有低气体渗透速率的阻挡层,其阻止氧气与基底表面相互作用,从而抑制氧化和腐蚀。有机层106使得可以根据使用者的需要(例如在高温或机械应力下)选择性地(至少部分地)去除钝化层104。全部或部分去除有机层104引起钝化层104的钝化特性的劣化。全部或部分去除有机层104包括有机层104的完全或部分地解吸、分解或降解。当在机械应力下时,有机层106的柔软性质有利于无机层108的变形。
用钝化层104改性的基底100适于在室温下的下方铜表面102的抗氧化或防腐蚀。图2示出了在室温下使用第一实施方式的方法制造的基底(曲线202)的氧化铜的再生长程度。还对未改性的铜基底(曲线204)和仅用氧化铝改性的铜基底(曲线206)进行了对比试验。使用椭圆光度法测量氧化铜的厚度。用第一实施方式的方法形成的基底在室温下、在超过3个月的时段内没有显示出氧化物生长的迹象(曲线202)。第一实施方式的基底抑制铜基表面的氧化,并在室温下显示出抗氧化性。仅用氧化铝改性的铜基底(曲线206)在超过3个月的时段内也抑制氧化铜的形成。相反,未改性的铜基底(曲线204)在不到一天的时间内显示出显著的氧化铜再生长。
当使用者需要时,理想的是钝化层104的钝化特性选择性地劣化。本发明人已经意识到,第一实施方式的钝化层104在升高的温度下历经状态(或改性)的改变,从而使得钝化层104的钝化特性劣化。状态的变化可以包括钝化层104从金属表面的完全或部分解吸、分解或降解。
图3示出了在150℃下,对于用本发明第一实施方式的方法制造的基底(曲线302)以及仅用氧化铝改性的铜基底(曲线306)的铜基底的氧化铜的再生长程度。已知氧化铝在直接沉积在金属表面上时形成永久钝化层。在150℃下,覆有氧化铝的基底抑制铜基底的氧化(曲线306)。相反,在150℃下,本发明的改性基底(曲线302)在10分钟后显示出显著的氧化铜再生长。
不希望受任何理论或猜想的束缚,据信在升高的温度下,钝化层经历状态变化,由此钝化层的钝化特性劣化。状态的变化可包括有机层完全或部分降解、分解或从铜表面的解吸。在其他金属表面(包括锡和银表面以及含铜、锡和银的合金表面)上也观察到这种效果。在钝化层104的状态改变之后,基底的表面不再受保护并且能够发生金属表面的氧化。
温度敏感的钝化层104有利地使得层104的钝化特性根据使用者的需要而劣化。通常,在形成电连接之前或同时去除钝化层104。钝化层104的温度敏感性质使得在焊接过程中能够至少部分地选择性地去除层104。这有利地减少了去除钝化层所需的处理步骤的数量,并且还有助于最小化在去除钝化层104的步骤和随后的处理步骤(例如形成电连接)之间发生氧化物再生长的风险。
钝化层104的解吸、分解或降解在更高的温度下更容易发生。然而,使基底经受过高的温度可能会破坏基底上的其他组件。优选避免这种严酷的处理条件。优选地,钝化层104的状态变化,例如解吸过程,在低于用于焊接和/或热压接合的温度的温度下发生。通常,焊接温度约为260℃,然而可以约为200℃。在第一实施方式中,在约150℃的温度下和在高于150℃的温度下发生解吸过程(图3)。解吸温度足够低以使得钝化层104的钝化特性劣化而不破坏基底的其他组件。
可以使用描述于专利文献US 9,725,805B2(其全部内容通过引用并入本文)中的装置来沉积本发明的钝化层。用于沉积钝化层的装置可购自英国纽波特的SPTSTechnologies Limited(前身为加利福尼亚州圣何塞的Applied Microstructures,Inc.)。图4中示意性示出的装置401适合于进行根据本发明的方法。就每个单独的工艺步骤提供给处理室的反应物的量而言,以及就可提供给所述反应的这些反应物的时间和顺序而言,该装置进行了专门设计以用于对此提供高度控制。
图5是表示根据第一实施方式的沉积钝化层的方法的流程图。通常,该过程包括清洁处理502、有机层沉积步骤504和无机层沉积步骤506。可以根据需要重复或循环沉积步骤504和506。所有步骤502、504和506可以方便地在同一处理室中进行。这有利地最小化污染的风险,并且不再需要转移步骤,例如在处理模块之间转移基底。因此,该方法在保证高质量的同时提高了制造基底的产量。
将具有金属表面402的基底400装载到处理室410中。在一个实施方式中,金属表面是铜表面。在其他实施方式中,金属表面可以是锡或银表面,或是含铜、锡或银中的一种或多种的合金表面。铜表面402朝上并且搁置在基底支撑件412上。首先对基底进行清洁处理502,以从铜表面402去除污染物和金属氧化物。通常,清洁处理502是氢等离子体处理。可以使用微波、DC或感应RF电源或其组合来产生等离子体。或者,清洁处理可包括使铜表面402暴露于化学还原剂,例如酸或醇。化学还原剂可以是甲酸或乙醇。
在预清洁步骤502完成之后,由有机前体414形成的有机层通过分子气相沉积工艺504沉积到基底400上。在本发明的第一实施方式中,有机前体是6-巯基-1-己醇。有机前体414保持在储存容器416中,该储存容器416可以按需通过加热器418来加热。有机前体蒸汽经由传输管线420和膨胀室422引入处理室410。在有机层沉积步骤502期间,处理室410中的压力通常为0.02托~2托,优选地为约0.2托。通常,处理室410保持在20℃~150℃的温度。
有机前体的第一官能团111自发地吸附到铜表面402以形成自组装层,例如自组装单层(SAM)。形成SAM确保有机层在基底表面上具有均匀的厚度。然而,在一些实施方式中,有机层是多层薄层。通常,吸附是化学吸附。在第一实施方式中,6-巯基-1-己醇前体的巯基官能团化学吸附到基底的铜表面102上以形成SAM。通常,第一官能团111优先于第二官能团112吸附到铜表面。在一些实施方式中,第二官能团112不吸附至铜表面。其结果,有机前体被定向使得第二官能团112远离铜表面402,从而为随后的处理步骤提供吸附或反应位点。在第一实施方式中,6-巯基-1-己醇的羟基提供了用于附着到无机层的反应位点。
随后,在无机层沉积步骤506期间将无机层沉积在有机层上。无机层沉积步骤506是进一步的气相沉积工艺,例如,原子层沉积或化学气相沉积。可以使用任何方便类型的气相沉积。通常,无机层沉积步骤506是原子层沉积工艺。原子层沉积步骤方便地允许沉积无机材料的单个的层,这提供了跨基底表面的优异的均匀性。
无机沉积处理506通常包括将第一气态反应物424引入处理室(步骤506a)和将第二反应物426引入处理室(步骤506b)的子步骤。可以根据需要重复多次子步骤以获得所需的无机层厚度。通常,子步骤506a和506b重复1~10次。在第一实施方式中,第一和第二气态反应物分别是三甲基铝(TMA)和水(H2O)。通常,在每个子步骤506a和506b之间,用惰性气体如N2或Ar吹扫处理室410。
子步骤506a包括将第一气态反应物引入处理室410。第一气态反应物424保持在储存容器428中,该储存容器428可以按需通过加热器430来加热。第一气态反应物经由传输管线432和膨胀室434引入处理室410。第一反应物与有机层的可用的第二官能团112(例如羟基和羧基)反应,直到不再发生进一步反应。以这种方式,仅沉积单原子层。在第一实施方式中,TMA与有机层上可用的羟基(或羧基)反应以形成铝基中间体物质(未示出)。
子步骤506b包括将第二气态反应物426引入处理室410。第二气态反应物426保持在储存容器436中,该储存容器436可以按需通过加热器438来加热。第二气态反应物经由传输管线440和膨胀室442引入处理室410。第二反应物与第一反应物反应以形成无机层。通常,无机层是陶瓷层和/或金属氧化物层。可以使用具有低气体渗透速率的其他方便的无机层。无机层可以由Al2O3、GeO2、ZnO、SiOx、SiO2、Si3N4、TiO2、ZrO2、HfO2、SnO2、In2O3或Ta2O5组成。在第一实施方式中,水与铝基中间体物质反应形成无定形氧化铝(Al2O3)层。该氧化铝层形成所述无机层。
通常,子步骤506a和506b的温度保持在35℃~250℃的温度下。通常,子步骤506a,506b期间处理室的压力约为0.05Torr。
子步骤506a和506b的每个循环将单个原子层沉积到基底上。通常,子步骤506a和506b的每个循环沉积厚度为(即0.05nm~0.40nm)的层。通常重复子步骤506a和506b,直到达到所需的无机层厚度。通常,无机层的厚度约为0.1nm~10nm。本发明人发现,沉积在有机层106上的0.1nm~10nm厚的无机层108可以令人满意地抑制铜、锡、银或合金表面102的氧化。
Claims (25)
1.一种在基底上形成钝化层的方法,所述方法包括以下步骤:
a)在处理室中提供基底,所述基底包括金属表面,其中,所述金属表面为铜、锡或银表面,或为包括铜、锡或银中的一种或多种的合金表面;
b)通过气相沉积将至少一个有机层沉积到所述金属表面上,由有机前体形成的所述有机层包括:
第一官能团,包括氧、氮、磷、硫、硒、碲或硅中的至少一种;和
第二官能团,选自羟基(-OH)或羧基(-COOH);
其中,所述第一官能团吸附在所述金属表面上;
和
c)通过气相沉积将至少一个无机层沉积到所述有机层上,其中所述第二官能团用作无机层的附着位点。
2.根据权利要求1所述的方法,其中,所述第一官能团选自以下基团:羧基(-COOH)、伯胺(-NH2)、仲胺、叔胺、硫醇(-SH)、二唑、三唑、二硫化物、异氰酸酯、膦酸酯、有机硒、有机碲或有机硅烷。
3.根据权利要求1或2所述的方法,其中,所述第一官能团化学吸附在所述金属表面上。
4.根据前述权利要求中任一项所述的方法,其中,所述有机前体具有以下形式的结构:
X–R–Y
其中,X是所述第一官能团;R是取代或未取代的烷基,取代或未取代的环烷基,或取代或未取代的芳基;和Y是所述第二官能团。
5.根据权利要求4所述的方法,其中,R具有2~16个碳原子,优选具有2~11个碳原子。
6.根据权利要求5所述的方法,其中,R具有2~7个碳原子,优选具有6个碳原子。
7.根据前述权利要求中任一项所述的方法,其中,所述有机前体选自包括4-氨基苯酚、6-巯基-1-己醇和11-巯基十一烷酸的组。
8.根据前述权利要求中任一项所述的方法,其中,所述有机层是自组装单层(SAM)。
9.根据权利要求1~7中任一项所述的方法,其中,所述有机层是多层结构。
10.根据前述权利要求中任一项所述的方法,其中,步骤b)包括通过分子气相沉积将至少一个有机层沉积到所述金属表面上。
11.根据前述权利要求中任一项所述的方法,其中,步骤c)包括通过原子层沉积将至少一个无机层沉积到有机层上。
12.根据前述权利要求中任一项所述的方法,其中,所述无机层是陶瓷材料。
13.根据前述权利要求中任一项所述的方法,其中,所述无机层选自包括以下各项的组:氧化铝(Al2O3)、GeO2、ZnO、SiOx、SiO2、Si3N4、TiO2、ZrO2、HfO2、SnO2、In2O3或Ta2O5。
14.根据前述权利要求中任一项所述的方法,其中,所述无机层是多层结构。
15.根据前述权利要求中任一项所述的方法,其中,所述无机层具有0.1nm~10nm的厚度。
16.根据前述权利要求中任一项所述的方法,所述方法还包括以下步骤:
aa)在步骤b)之前对所述金属表面进行还原处理。
17.根据权利要求16的所述的方法,其中,所述还原处理是含氢等离子体处理。
18.根据前述权利要求中任一项所述的方法,在步骤a)、aa)、b)和/或c)中的一个或多个步骤之前,使用惰性气体吹扫所述处理室。
19.根据前述权利要求中任一项所述的方法,其中,步骤c)包括:
将第一和第二气态反应物依次引入所述处理室中以附着到第二官能团或与第二官能团反应,由此形成所述无机层。
20.根据前述权利要求中任一项所述的方法,其中,步骤b)和步骤c)在同一处理室中进行。
21.根据权利要求20所述的方法,其中,步骤b)和c)在所述步骤之间在没有真空中断的情况下进行。
22.根据前述权利要求中任一项所述的方法,其中,重复步骤b)和或步骤c)。
23.一种基底,所述基底包括用权利要求1所述的方法形成的钝化层。
24.根据权利要求23所述的基底,其中,所述基底是印刷电路板(PCB)、热压接合基底、引线接合基底或焊接接合基底。
25.一种从根据权利要求23所述的基底至少部分地去除或降解钝化层的方法,所述方法通过使所述的基底经历100℃~260℃的温度来进行。
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