CN110643939B - 铜基抗菌pvd涂层 - Google Patents
铜基抗菌pvd涂层 Download PDFInfo
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- CN110643939B CN110643939B CN201910565953.5A CN201910565953A CN110643939B CN 110643939 B CN110643939 B CN 110643939B CN 201910565953 A CN201910565953 A CN 201910565953A CN 110643939 B CN110643939 B CN 110643939B
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- Prior art keywords
- zirconium
- copper alloy
- layer
- base layer
- containing base
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- 239000010949 copper Substances 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title abstract description 16
- 239000011248 coating agent Substances 0.000 title abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 title description 2
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 76
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 90
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000001755 magnetron sputter deposition Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001112 rose gold Inorganic materials 0.000 description 2
- 239000010939 rose gold Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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Abstract
本发明提供了一种涂覆基底，其包括基底、设置在基底上的含锆层以及设置在基底上的一个或多个铜合金层。变化包括涂覆基底具有单一铜合金层、交替铜层或铜合金/含锆层的组合。
Description
相关申请的交叉引用
本申请要求2018年6月27日提交的美国临时申请序列号62/690,781的权益，并且还要求2019年6月20日提交的美国申请序列号16/447,339的优先权，其公开内容在此以其整体通过引用并入本文。
技术领域
在至少一个方面中，本发明涉及抗菌涂层，并且更具体地涉及具有抗菌性能的装饰涂层。
背景技术
以下专利和专利申请公开了包括铜的涂层的变化：美国专利号9107981、8530056和8066854以及美国专利申请号20090162695；20090198343。
发明内容
在至少一个方面，提供了一种多层涂层叠层，该多层涂层叠层包括具有顶部涂层的硬Zr基基层，该顶部涂层具有抗微生物特性的铜合金。含Zr基层可以是与类似于铜合金(其可用的几种色调—白青铜、玫瑰铜和青铜)的颜色相匹配的颜色。有利地，较硬的基层提供两种功能：1)增加耐久性和；2)当软Cu合金磨损时，较硬的层将变得可见，并且如果色差接近，则消费者将不会注意到。变化包括Cu/ZrCN/Cu/ZrCN的多层夹层或存在材料的共沉积的共混层。此外，替代的Cu合金可以使用目前没有提供的不同金属生产，诸如Zr、W、Cr等。这些替代的合金元素可以导致不同的颜色和物理性能。
有利的是，铜基合金可在市场上获得(例如，来自CuVerro)，其可以用于制造本发明的各种产品。在一个变化中，根据这种合金制成的靶材的物理气相沉积(physical vapordeposition，PVD)沉积物可以为不能由合金本身形成的产品提供薄膜。本发明的其他方面涉及改善软铜合金的耐用性和功能性。
附图说明
图1是具有外铜合金层的涂覆基底的示意图。
图2是具有交替的含锆和铜合金层的涂覆基底的示意图。
图3是具有外部混合锆铜合金层的涂覆基底的示意图。
图4提供了可以被使用以用于形成本文所提供的多层涂层的涂层***的示意性图示。
具体实施方式
现在将详细参考本发明目前优选的组合物、实施例和方法，它们构成了发明人目前已知的实践本发明的最佳模式。附图不一定按照比例绘制。然而，应该理解的是，公开的实施例仅仅是本发明的示例，本发明可以以各种和替代的形式实施。因此，本文公开的具体细节不应被解释为限制，而仅仅是作为本发明任何方面的代表性基础和/或作为教导本领域技术人员以各种方式使用本发明的代表性基础。
还应当理解的是，本发明不限于下面描述的具体实施例和方法，因为具体的成份和/或条件当然可以变化。另外，本文使用的术语仅用于描述本发明的特定实施例的目的，并不旨在以任何方式进行限制。
还必须注意的是，如说明书和所附权利要求中所使用的，单数形式“一个”和“该”包括复数指示物，除非上下文另有明确指示。例如，以单数形式引用成份旨在包括多个成份。
术语“包括”与“包括”、“具有”、“包含”或“以……为特征”同义这些术语是包容性和开放性的，不排除附加的、未叙述的元素或方法步骤。
短语“由......组成”排除权利要求中不指定的任何元素、步骤或成分。当这个短语出现在权利要求主体的一个条款中，而不是紧接在序言之后，它仅限制该条款中提出的元素；其他元素不被排除在作为整体的权利要求之外。
短语“基本上由......组成”将权利要求的范围限制于指定的材料或步骤，加上那些不会实质上影响本申请要求保护的主题的基本和新颖(多个)特征的材料或步骤。
关于术语“包括”、“由......组成”和“基本上由......组成”，其中本文使用这三个术语中的一个，本发明公开和要求保护的主题可以包括使用其他两个术语中的任一个。
还应该理解，整数范围明确地包括所有中间整数。例如，整数范围1-10明确地包括1、2、3、4、5、6、7、8、9和10。类似地，范围1至100包括1、2、3、4……97、98、99、100。类似地，当需要任何范围时，介于上限和下限之间的差值除以10的增量可以作为替代的上限或下限。例如，如果范围是1.1至2.1，则可以选择下列数字1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9和2.0作为下限或上限。
在本文叙述的实施例中，浓度、温度和反应条件(例如，压力、pH、流速等)可以用正或负50％的值来实践，该值被四舍五入或截短为示例中提供的值的两个有效数字。在改进方案中，浓度、温度和反应条件(例如，压力、pH、流速等)可以用正或负30％的值来实践，该值被四舍五入或截短为示例中提供的值的两个有效数字。在另一改进方案中，浓度、温度和反应条件(例如，压力)可以用正或负10％的值来实践，该值被四舍五入或截短为实施例中提供的值的两个有效数字。
在整个申请中，在引用出版物的情况下，这些出版物的公开内容通过引用全文并入本申请中，以更全面地描述本发明从属的技术状态。
缩写：
“SCCM”是指标准立方厘米每分钟。
在一个实施例中，提供了包括含铜合金的涂覆基底。涂覆基底包括基底、设置在基底上的含锆基层、以及设置在含锆基层上的一个或多个(即，或多个)铜合金层。含锆基层是碳氮化锆基层或氮化锆基层。在一个变化中，每个铜合金层包括铜和镍。典型地，每个铜合金包括占铜合金层总重量约8重量％至28重量％的镍，铜以占铜合金层总重量约72重量％至92重量％的量存在。在改进方案中，每个铜合金层包括占铜合金层总重量约10重量％至25重量％的镍和占铜合金层总重量约75重量％至90重量％的铜。在一些变化中，每个铜合金层可以独立地包括附加的元素，诸如铁、锆、钨、铬以及其的组合。在改进方案中，这些附加的元素中的每一个独立地以铜合金层总重量的约0.01重量％至约5重量％的量存在。在改进方案中，这些附加的元素中的每一个独立地以铜合金层总重量的约0.01重量％至约5重量％的量存在。铜合金的示例是
白青铜和
玫瑰，其可从位于Louisville，KY的Olin Brass商购获得。
典型地，含锆基层包括锆、碳和氮，其中锆以至少50摩尔％的量存在，碳和氮中的每一个分别以至少0.02摩尔％和0.1摩尔％的量存在。在改进方案中，含锆基层包括具有下式的化合物：
Zr1-x-yCxNy。
其中x为0.0至0.3并且y为0.1至0.5。在改进方案中，x为0.0至0.2并且y为0.2至0.3。在另一改进方案中，x至少是以增加的优选顺序0.0、0.02、0.03、0.04、0.05、0.07或0.09，并且至多是以增加的优选顺序0.5、0.4、0.3、0.25、0.2、0.15或0.11。类似地，在这种改进方案中，y至少是以增加的优选顺序0.1、0.15、0.2、0.25、0.27或0.29，并且至多是以增加的优选顺序0.6、0.5、0.40、0.35、0.33或0.31。在进一步改进方案中，含锆基层包括由Zr0.60C0.10N0.30描述的碳氮化锆。
本文使用的基底实际上可以包括任何固体基底。这种基底的示例包括金属基底、塑料基底和玻璃基底。在一个变化中，基底不是玻璃。在一些变化中，基底预先涂覆有金属粘合层。这种金属粘合层包括金属，诸如铬、镍、钨、锆以及其的组合。尽管可以使用粘合层的任何厚度，但是有用的厚度是从100nm至0.2微米。
图1、图2和图3提供了具有上述含锆基层和铜合金层的涂覆基底的不同构型。图1提供了示例，其中一个或多个铜合金层是单一层。在这个示例中，基底10涂覆有含锆基层12，该含锆基层上涂覆有铜合金层14。在改进方案中，可选的金属粘合层18被***在基底10和含锆层12之间。在另一改进方案中，含锆基层12典型地具有约100至800nm的厚度，铜合金层14典型地具有约50至600nm的厚度，并且当金属粘合层18存在时具有约10至200nm的厚度。在又另一改进方案中，含锆基层12典型地具有约200至400nm的厚度，铜合金层14典型地具有约100至300nm的厚度，并且当金属粘合层18存在时具有约20至80nm的厚度。
参考图2，具有交替的铜合金层和含锆层的涂覆基底的示意性图示。在这个示例中，基底20涂覆有含锆基层22，该含锆基层上涂覆有交替的铜合金层24和含锆中间层26。含锆中间层是碳氮化锆中间层或氮化锆中间层。在变化中，涂覆基底包括3至10个铜合金层和3至10个含锆中间层。在改进方案中，可选的金属粘合层28被***在基底20和含锆基层22之间。含锆基层22和含锆中间层26各自典型地具有约40至150nm的厚度，而铜合金层14典型地具有约20至80nm的厚度。当金属粘合层28存在时具有约20至80nm的厚度。在这个变化中，含锆基层22和含锆中间层26各自独立地具有上述含锆的公式。
参考图3，具有共混锆铜合金层的涂覆基底的示意性图示。在这个示例中，基底30涂覆有含锆基层32，其上涂覆有共混锆铜合金层34。在改进方案中，共混锆铜合金层34是共混含锆/铜合金层(即，它包括共混在一起的碳氮化锆和铜合金)。在变化中，缺少含锆基层32。在另一改进方案中，可选的金属粘合层38***在基底30和含锆基层32之间或者共混铜合金层34之间(如果缺少含锆基层32)。当含锆基层32存在时典型地具有约20至300nm的厚度，共混锆铜合金层34典型地具有约50至600nm的厚度。并且当金属粘合层38存在时具有约10至200nm的厚度。在改进方案中，当含锆基层32存在时典型地具有约40至150nm的厚度，共混锆铜合金层34典型地具有约100至300nm的厚度，当金属粘合层38存在时具有约20至80nm的厚度。
参考图4，提供了可以被使用以用于形成上述涂层基底的涂层***的示意性图示。涂层***40包括设置在真空室44内的电弧源42。电弧源42被用于沉积上述金属粘合层和含锆层。涂层***40还包括用于沉积铜合金层的磁控溅射源46和相关联的快门48。挡板48控制磁控溅射源46的可用性，当铜合金层沉积时打开，否则关闭。基底50还设置有典型地围绕电弧源42移动的真空室44。
以下示例示出了本发明的各种实施例。本领域技术人员将认识到在本发明的精神和权利要求的范围内的许多变化。
示例1(双层)
真空薄膜沉积室被抽气至2.0×10-5Torr的压力。然后使用壁装式电阻加热元件将腔室加热至150℃的温度。在腔室内部的转盘上，镀铬黄铜门把手安装在机架上，机架在壁装式磁控溅射阴极和位于中心的圆柱形电弧阴极之间以2轴线行星运动旋转。通过用氩气回填至25.0mTorr的压力并向部件施加-500V的偏置电压来执行离子蚀刻表面制备。通过以400A的电流在电弧阴极上点燃电弧，将锆金属粘合层施加到手柄部件上。用氩将腔室回填至3.0mTorr的压力，并施加-100V的基底偏置。这个步骤持续3分钟，以建立50nm厚的Zr金属层。由碳氮化锆组成的第二涂层通过继续在Zr靶材上运行电弧来施加，但是分别以80sccm和20sccm的流量添加氮气和甲烷气体，以得到大约Zr0.60C0.10N0.30的成分。这个层在25分钟内建立至300nm，此时Zr电弧阴极关闭，并且氮气和甲烷气体关掉，仅留下氩气在3.0mTorr的压力下继续流动。打开壁装式磁控溅射阴极的挡板，露出由C706铜合金材料组成的靶材。阴极通电至10kW水平持续30分钟以产生200nm的层厚度。所得膜的总厚度为550nm。
示例2(多层)
真空薄膜沉积室被抽气至2.0×10-5Torr的压力。然后使用壁装式电阻加热元件将腔室加热至150℃的温度。在腔室内部的转盘上，不锈钢面板安装在机架上，机架在壁装式磁控溅射阴极和位于中心的圆柱形电弧阴极之间以2轴线行星运动旋转。通过用氩气回填至25.0mTorr的压力并向部件施加-500V的偏置电压来执行离子蚀刻表面制备。通过在电弧阴极上以400A的电流点燃电弧，将锆金属粘合层施加到面板上。用氩将腔室回填至3.0mTorr的压力，并施加-100V的基底偏置。这个步骤持续3分钟，以建立50nm厚的Zr金属层。由碳氮化锆组成的第二涂层通过继续在Zr靶材上运行电弧来施加，但是分别以80sccm和20sccm的流量添加氮气和甲烷气体，以得到大约Zr0.60C0.10N0.30的成分。这个层在5分钟内建立至60nm，此时Zr电弧阴极关闭，并且氮气和甲烷气体关掉，仅留下氩气在3.0mTorr的压力下继续流动。打开壁装式磁控溅射阴极的挡板，露出由C706铜合金材料组成的靶材。将阴极通电至10kW的水平持续6分钟的持续时间以产生40nm的层厚度。最后两层重复四次，最多建立至10个总交替层。所得膜的总厚度为550nm。
示例3(共混)
真空薄膜沉积室被抽气至2.0×10-5Torr的压力。在室温下操作反应室。在腔室内部的转盘上，镀铬ABS塑料装饰部件安装在机架上，机架在壁装式磁控溅射阴极和位于中心的圆柱形电弧阴极之间以2轴线行星运动旋转。通过用氩气回填至25.0mTorr的压力并向部件施加-500V的偏置电压来执行离子蚀刻表面制备。通过在电弧阴极上以300A的电流点燃电弧，将锆金属粘合层施加到面板上。用氩气将腔室回填至3.0mTorr的压力，并施加-50V的基底偏置。这个步骤持续3分钟，以建立40nm厚的Zr金属层。由铜合金和碳氮化锆的混合物组成的第二涂层通过继续在Zr靶材上运行电弧来施加，但是分别以80sccm和20sccm的流量添加氮气和甲烷气体，以得到大约Zr0.60C0.10N0.30的成分。打开壁装式磁控溅射阴极的挡板，露出由C706铜合金材料组成的靶材。阴极被供电至10kW的水平。Zr电弧靶材和Cu合金溅射靶都运行10分钟以产生160nm的涂层厚度。所得膜厚度为200nm。
表1提供了使用Minolta分光光度计进行的颜色测量，该分光光度计使用CIELAB颜色空间，具有D65光源和10度观察角，用于基于铜合金和ZrCN的涂覆基底。上述涂覆基底的变化具有表1中值的正或负10％的颜色坐标。
表1涂覆样本的颜色坐标
| L* | a* | b* | |
| C706铜合金(玫瑰金) | 76.3 | 7.46 | 20.8 |
| C710(白青铜) | 80.3 | 2.50 | 10.4 |
| ZrCN(玫瑰金) | 69.7 | 9.26 | 21.3 |
| ZrCN(白青铜) | 75.2 | 2.23 | 10.0 |
虽然上面描述了示例性实施例，但这些实施例并不旨在描述本发明的所有可能形式。相反，在说明书中使用的词语是描述性的词语而不是限制性的词语，并且应当理解的是，在没有脱离本发明的精神和范围的情况下，可以进行各种改变。附加地，各种实施的实施例的特征可以被组合以形成本发明的进一步实施例。
Claims (16)
1.一种涂覆基底，包括：
基底；
金属粘合层，所述金属粘合层设置在所述基底上并且与所述基底接触，所述金属粘合层具有20至80 nm的厚度；
含锆基层，所述含锆基层设置在所述金属粘合层上并且与所述金属粘合层接触，所述含锆基层是碳氮化锆基层或氮化锆基层，其中，所述含锆基层包括具有下式的化合物：
Zr1-x-yCxNy，其中x为0.0至0.3并且y为0.1至0.5；以及
一个或多个铜合金层，所述一个或多个铜合金层设置在所述含锆基层上并且与所述含锆基层接触，其中所述一个或多个铜合金层与所述含锆基层颜色相匹配，所述铜合金层与所述含锆基层色差接近，当铜合金层磨损时，含锆基层变得可见并且被磨损的铜合金层也不会被注意到。
2.如权利要求1所述的涂覆基底，其中，所述含锆基层包括至少50摩尔%的锆的量、至少0.02摩尔%的碳的量、以及至少0.02摩尔%的氮的量。
3.如权利要求1所述的涂覆基底，其中，所述含锆基层包括具有下式的化合物：
Zr1-x-yCxNy ，其中x为0.0至0.2并且y为0.2至0.3。
4.如权利要求1所述的涂覆基底，其中，所述含锆基层包括具有式Zr0.60C0.10N0.30的碳氮化锆。
5.如权利要求1所述的涂覆基底，其中，每个铜合金层包括铜和镍。
6.如权利要求5所述的涂覆基底，其中，镍以每个铜合金层的总重量的10重量%至25重量%的量存在，铜以每个铜合金层的总重量的75重量%至90重量%的量存在。
7.如权利要求1所述的涂覆基底，其中，每个铜合金层包括选自铁、锆、钨、铬以及其所组成的组中附加的元素。
8.如权利要求7所述的涂覆基底，其中，所述附加的元素中的每一个以所述铜合金层的总重量的0.01重量%至5重量%的量独立地存在。
9.如权利要求1所述的涂覆基底，其中，单一铜合金层设置在所述含锆基层上。
10.如权利要求1所述的涂覆基底，其中，所述含锆基层具有100至800 nm的厚度，并且单一铜合金层具有50至 600 nm的厚度。
11.如权利要求1所述的涂覆基底，其中，所述涂覆基底具有交替铜合金层和设置在所述含锆基层上的含锆中间层，所述含锆中间层是碳氮化锆中间层或氮化锆中间层。
12.如权利要求11所述的涂覆基底，其中，所述含锆基层和所述含锆中间层各自独立地具有20至300 nm的厚度，并且每个铜合金层具有10至200 nm的厚度。
13.如权利要求1所述的涂覆基底，其中，所述涂覆基底具有3至10层铜合金层和3至10层含锆中间层。
14.一种涂覆基底，包括：
基底；
金属粘合层，所述金属粘合层设置在所述基底上并且与所述基底接触，所述金属粘合层具有20至80 nm的厚度；
含锆基层，所述含锆基层设置在所述金属粘合层上并且与所述金属粘合层接触，所述含锆基层是碳氮化锆基层或氮化锆基层，其中，所述含锆基层包括具有下式的化合物：
Zr1-x-yCxNy，其中x为0.0至0.3并且y为0.1至0.5；以及
共混锆铜合金层，所述共混锆铜合金层设置在所述含锆基层上并且与所述含锆基层接触，其中，所述共混锆铜合金层与所述含锆基层颜色相匹配，所述共混锆铜合金层与所述含锆基层色差接近，当共混锆铜合金层磨损时，含锆基层变得可见并且被磨损的共混锆铜合金层也不会被注意到。
15.如权利要求14所述的涂覆基底，其中，共混锆铜合金层是共混含锆/铜合金层。
16.如权利要求14所述的涂覆基底，其中，共混锆铜合金层具有50至600 nm的厚度。
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| US11821075B2 (en) * | 2020-06-15 | 2023-11-21 | Vapor Technologies, Inc. | Anti-microbial coating physical vapor deposition such as cathodic arc evaporation |
| KR102454450B1 (ko) * | 2020-10-16 | 2022-10-14 | 주식회사 티에스컴퍼니 | 무기 항균제 및 그것의 제조방법 |
| US20220174946A1 (en) * | 2020-12-07 | 2022-06-09 | Vapor Technologies, Inc. | Copper-based antimicrobial pvd coatings with wear indicator |
| CN113230462B (zh) * | 2021-04-08 | 2022-11-29 | 上海微创医疗器械（集团）有限公司 | 医用器件 |
| CN115233157A (zh) * | 2022-06-14 | 2022-10-25 | 沈阳大学 | 一种锌及锌合金表面磁控溅射制备铜薄膜方法 |
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| CN110643939A (zh) | 2020-01-03 |
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| EP4306679A3 (en) | 2024-04-03 |
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