CN116457494A - 通过PVD由金属靶产生的富Al的AlCrN涂层 - Google Patents
通过PVD由金属靶产生的富Al的AlCrN涂层 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 title description 6
- 239000002184 metal Substances 0.000 title description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 91
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011651 chromium Substances 0.000 claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052729 chemical element Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 50
- 239000013077 target material Substances 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 20
- 238000005240 physical vapour deposition Methods 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000001771 vacuum deposition Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical group [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical group [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
本发明涉及涂层及其生产方法,其中所述涂层包含Al、Cr和N作为主要组分,并具有根据式(AlaCrb)xOyCzNq的关于这些元素的按原子百分比计的化学元素组成,其中a和b分别为铝和铬的原子比浓度,仅考虑Al和Cr以计算所述层中的元素组成,其中a+b=1且0≠a≥0.7且0≠b≥0.2,且其中x为Al的浓度与Cr的浓度之和,且y、z和q分别为氧、碳和氮的原子比浓度,仅考虑Al、Cr、O、C和N以计算所述层中的元素组成,其中x+y+z+q=1且0.45≤x≤0.55,0≤y≤0.25,0≤z≤0.25,并且其中所述涂层表现出90%或更多的fcc立方相,和2.5GPa或更大,优选2.5GPa至6GPa的压缩应力。
Description
本发明涉及通过物理气相沉积(PVD)方法由金属靶产生的富Al的AlCrN涂层(下文也简称为富Al的AlCrN涂层或富Al的AlCrN层或富Al的AlCrN膜)及其生产方法。
本发明还涉及由一个或多个上述本发明的富Al的AlCrN层组成或包括一个或多个上述本发明的富Al的AlCrN层的涂层体系。
根据本发明的富Al的AlCrN涂层应理解为由铝(Al)、铬(Cr)和氮(N)组成的涂层,或者包含铝(Al)、铬(Cr)和氮(N)作为主要组分的涂层。
在本文中,术语富Al的基于AlCrN的层中的“Al、Cr和N作为主要组分”的使用特别是指,如果考虑富Al的基于AlCrN的层中所含的全部化学元素以按原子百分比计确定富Al的基于AlCrN的层的全部化学元素组成,作为原子百分比浓度的富Al的基于AlCrN的层中的Al、Cr和N的含量的总和对应于大于50原子%(即>50原子%至100原子%的值),优选大于75原子%(即>75原子%至100原子%的值),更优选等于或大于80原子%(即80原子%至100原子%的值)。
在本文中,术语“富Al”特别用于表示相应的富Al的基于AlCrN的层中铝(Al)的含量等于或优选大于70原子%,如果仅考虑Al和Cr以确定按原子百分比计的化学元素组成(即Al[原子%]/Cr[原子%]>70/30)。
背景技术
对具有高于70原子%(相对于Cr)的Al含量的AlCrN涂层(其表现出立方晶体结构和柱状微结构)进行了许多研究并试图尤其在工业PVD室内获得这样的材料,因为预期这些种类的涂层与具有较低Al含量的涂层,例如基于PVD的Al0.7Cr0.3N涂层相比会显示出优异的磨损保护。
因此,还有一些出版物提出了将Al的亚稳态溶解度极限提高到超过70原子%的可能方法。然而,迄今为止所有这些提出的方法都具有一些缺点。
发明目的
本发明的目的是提供富Al的基于AlCrN的涂层及其生产方法,其克服或减轻了现有技术的缺点。
如果富Al的AlCrN涂层被施加到切削工具上,则富Al的基于AlCrN的涂层应优选地呈现立方相、高硬度、适当的压缩应力和涂层微结构,这优选地允许获得高耐磨性和改进的切削性能。
本发明的另一个目的是提供用于产生本发明的富Al的基于AlCrN的涂层的灵活可靠的方法。
发明内容
本发明的目的通过提供如下文所述和要求保护的产生富Al的AlCrN涂层的方法和涂布有由一个或多个这些富Al的AlCrN涂层组成或包括一个或多个这些富Al的AlCrN涂层的涂层体系的基材来实现。
本发明具体涉及一种涂层,其包含Al、Cr和N作为主要组分,并具有根据式(AlaCrb)xOyCzNq的关于这些元素的按原子百分比计的化学元素组成,其中a和b分别为铝和铬的原子比浓度,仅考虑Al和Cr以计算层中的元素组成,其中a+b=1且0≠a>0.7且0≠b≥0.18(更特别地,a为0.7>a≤0.82),且其中x为Al的浓度与Cr的浓度之和,且y、z和q分别为氧、碳和氮的原子比浓度,仅考虑Al、Cr、O、C和N以计算层中的元素组成,其中x+y+z+q=1且0.45≤x≤0.55,0≤y≤0.25,0≤z≤0.25,其中:
●涂层显示:
○90%或更多的fcc立方相,和
○2.5GPa或更大,例如2.5GPa至6GPa的压缩应力。
根据应用,高压缩应力可以更合适,对于这样的情况,例如优选地压缩应力为4至6GPa,如一些应用的涂层或一部分涂层所需要的。
此外,本发明具体涉及根据权利要求1在基材表面上产生涂层的方法,其中:
●在真空涂布室内部,通过使用反应性PVD阴极电弧蒸发技术合成涂层,其中:
-将氮气引入真空涂布室中用作反应性气体,
-使用至少一个电弧蒸发源,其包括作为阴极操作的靶材料以蒸发靶材料,
-靶材料由Al和Cr组成或包含Al和Cr作为主要组分,其中如果仅考虑靶材料中Al和Cr的原子百分比含量,靶材料中Al[原子%]/Cr[原子%]之比大于70/30(即Al[原子%]/Cr[原子%]>70/30),
-该方法包括来自靶材料的铝和铬与引入涂布室中的氮气之间的反应导致的氮化铝铬的反应性沉积,
-如下进行氮化铝铬的反应性沉积
i.在180℃至600℃,优选200℃至500℃的沉积温度下,
ii.在0.1Pa至9Pa,优选0.2Pa至8Pa,更优选0.6Pa至7.5Pa的氮气分压下,
iii.通过使用对应于-250V≤Ub≤-30V的范围内,优选对应于-200V≤Ub≤-40V的范围内的偏压Ub。
因此,优选地,该方法通过使用Krassnitzer在PCT/EP2020/068828(国际公开号WO2021/001536A1)中描述的一种或多种电弧蒸发源进行,该文献在此通过引用并入。以这种方式,可以以如下方式进行反应性PVD涂布方法并产生富A1的AlCrN涂层(如上所述,Al含量高于70原子%):例如200A的电弧电流可以施加到靶,同时获得恒定的放电电压。
本发明人发现,在富Al的AlCrN层中,Al和Cr以上述比率组合(其是指Al[原子%]/Cr[原子%]>70/30,优选82/18≥Al[原子%]/Cr[原子%]>70/30)对改进工具和/或组件的磨损保护有很大贡献。
此外,本发明涉及包括一个或多个本发明的富Al的AlCrN涂层的涂层体系。
上述用于产生上述本发明的富Al的AlCrN涂层的本发明方法也可以通过使用例如另外的靶和/或反应性气流来改变,以便产生与本发明的富Al的AlCrN涂层组合的其它种类的涂层,以便产生不同的涂层体系,例如作为多层和/或梯度涂层体系。
此外,通过使用金属靶并同时将N2气体引入涂布PVD室/装置的反应性PVD涂布方法对于具有复杂涂层结构/设计的硬PVD涂层,如涂层或整个涂层的纳米层和/或多层部分是非常重要的。用于工具和/或组件上的硬涂层的PVD涂布解决方案。优选地,该涂布解决方案应具有所需涂层性质的组合,例如微结构、质地、弹性模量、硬度和应力,厚度不限于仅50nm或更小,以及具有通用(不是非常有限的)涂层性质,例如一个单晶晶粒取向或非常有限的低残余压缩应力。具体而言,该涂布解决方案还应能够改善Al含量为70%的AlCrN的性质,因为这种材料体系在PVD硬涂层中引起了大量关注,并因此改善例如工具在切削过程中的耐磨性。
根据本发明的富Al的AlCrN涂层和/或涂层体系(即包括根据本发明的富Al的AlCrN涂层)显示了优异的机械性质,并且预期具有有益的一组性质来为经受磨损和应力集合(stress collecCrve)的工具和组件提供优异的性能。
上述本发明的(AlaCrb)xNy层显示优选的面心立方结构。重要的是,本发明描述了通过反应性物理气相沉积(PVD)方法产生本发明的富Al的AlCrN涂层的方法,该方法通过电弧放电具有大于70原子%Al的金属AlCr靶,并通过同时将N2气体引入涂布PVD室/装置中。
为了更好地理解本发明,下面将使用一些实例、表格和附图来更详细地描述本发明。然而,这些实例、表格和附图不应被理解为对本发明的限制,而仅应被理解为本发明的具体实例和/或优选实施方案。
如下所述,根据本发明沉积的富Al的AlCrN层的本发明实例通过使用阴极电弧蒸发方法在400℃的工艺温度(在本文中,术语“工艺温度”用于特别指涂层沉积方法过程中的设定温度)和0.2Pa至5Pa的不同值的氮气分压下进行。将以原子%计的元素组成为80Al/20Cr的AlCr靶用作Al和Cr材料源,并通过施加120A至200A,或100A至200A的电弧电流和对于每个实例施加不同的基材偏压和压力,将靶作为阴极操作。
表1中给出了具有详细工艺参数的这样的沉积方法的5个实例。
通过实例1-5中给出的方法获得的富Al的基于AlCrN的涂层的性质在图1-5中给出。
附图说明
图1:(a)根据本发明实例1沉积的富Al的AlCrN涂膜的SEM断裂横截面图像,以及(b)原样沉积膜的谱图。
图2:(a)根据本发明实例2沉积的富Al的AlCrN涂膜的SEM断裂横截面图像,以及(b)原样沉积膜的谱图。
图3:(a)根据本发明实例3沉积的富Al的AlCrN涂膜的SEM断裂横截面图像,以及(b)原样沉积膜的谱图。
图4:(a)根据本发明实例4沉积的富Al的基于AlCrN的涂膜的SEM断裂横截面图像,以及(b)原样沉积膜的谱图。
图5:(a)根据本发明实例5沉积的富Al的基于AlCrN的涂膜的SEM断裂横截面图像,以及(b)原样沉积膜的谱图。
图1(a)、2(a)、3(a)、4(a)和5(a):在具有表1中给出的参数的方法的5个实例中沉积的富Al的基于AlCrN的材料的整体涂层的SEM断裂横截面图像,还包括在沉积膜中测量的杨氏模量(E)、硬度(H)和Al含量。
图1(b)、2(b)、3(b)、4(b)和5(b):由具有表1中给出的参数的方法沉积的富Al的基于AlCrN的涂层的5个实例的原样沉积膜的XRD谱图。
表1
实例 | 靶 | 温度 | 源电流 | N2压力 | 偏压 |
1 | AlCr 80/20 | 400℃ | 200A | 5Pa | -150V |
2 | AlCr 80/20 | 400℃ | 200A | 5Pa | -100V |
3 | AlCr 80/20 | 400℃ | 120A | 0.2Pa | -40V |
4 | AlCr 20/20 | 400℃ | 120A | 3.5Pa | -150V |
5 | AlCr 80/20 | 400℃ | 120A | 3.5Pa | -150V |
使用装备有CuKa辐射源的PANalyCrcal X′Pert Pro MPD衍射仪通过X射线衍射(XRD)进行膜结构分析。以Bragg-Brentano几何学收集衍射图。用FEGSEM Quanta F 200扫描电子显微镜(SEM)获得膜断裂横截面的显微照片。
使用装备有Berkovich金刚石尖端的超微压痕系统测定原样沉积样品的硬度和压痕模量。测试程序包括10mN的正常负荷。根据Oliver和Pharr方法评价硬度值。因此,我们确保压痕深度小于涂层厚度的10%以使基材干扰最小化。
图1(a)、2(a)、3(a)、4(a)和5(a)显示了实例1-5的膜的断裂横截面的SEM显微照片和涂层性质:弹性模量、硬度和Al含量。
图1(b)、2(b)、3(b)、4(b)和5(b)显示:实例1-5的原样沉积膜的XRD谱图并且那些XRD谱图表明所有涂层的面心立方晶体结构。
本发明的方法能够产生具有大于70原子%的Al的由立方AlCrN或主要(至少90%)立方AlCrN制成的涂层,其对于Al在涂层内的不同的原子存在,具有整个范围的物理和化学性质,如硬度、弹性模量、质地,但重要的是,所有这些涂层的共同点是完全或至少为90%的立方体,并且同时具有大于70原子%的Al(当仅考虑Al和Cr时)。
本发明人尤其通过以满足以下条件的方式实施本发明的方法,实现产生如此宽范围的具有至少90%立方面的富Al的AlCrN涂层的令人印象深刻的可能性:
-在涂布方法过程中获得并保持高N(氮)电离,意味着到达基材用于涂层形成的N物质的大于50%是双电荷的,同时
-以可获得能量大于或等于200eV的金属离子的高能量的方式,在涂布方法过程中获得并保持金属物质(铝和铬)的高注入。
通过工艺参数的适当组合获得本发明方法中的上述条件,其必须适用于特定的PVD涂布设备以满足上述给出的2个条件。
下面给出了用于获得上述涂布条件的工艺参数组合的实例:
第1组:
对于低偏压(-100V<Ub≤-40V),只有低压(0.1Pa至1Pa)和同时较高温度(350℃至500℃)是合适的,而
第2组:
对于更高的偏压(-200V≤Ub≤-100V),可以使用更高的压力范围(0.8Pa至9Pa)和同时更高的温度范围(200℃至480℃)。
表1给出了通过满足上述条件和工艺参数的特定组合的方法沉积的富A1的基于AlCrN的涂层的具体实例。
在本说明书中给出的实例1至5中,使用Oerlikon Balzers的PVD涂布机。
在表1的实例1和2中,可以观察到,所描述的工艺参数对应于根据上述第2组的涂布参数的适当组合,其中T、源电流和压力的那些参数相同(分别为400℃、200A和5Pa),但仅将偏压从-150V变为-100V。
在图1(a,b)和图2(a,b)中,显示了通过使用表1中所示的涂布参数的组合,通过实例1和2中给出的方法获得的AlCrN涂层的基本性质。也就是说,可以看出,在这两个实例中,获得的涂层是富Al的(涂层分别含有73和75原子%的铝),两个涂层都是立方的,但具有不同的质地、E和H。
另一方面,在表1中给出的实例3中,给出了工艺参数的实例,这些参数对应于根据上述第1组的涂布参数的适当组合,其中对于-40V的非常低的偏压,仅低压力值可能是合适的(例如这里给出的压力仅为0.2Pa),其中这样的低压力可以将碰撞最小化并保持进入物质的更高水平的电离,同时Al物质的高进入通量,如非常高的Al含量(81原子%,见图3(a))所反映的,同时令人惊讶的是仍然获得主要的立方相(见图3(b))。
等离子体性质,特别是氮电离和金属离子的能量可以通过使用Langmuir技术来测量。
为了产生本发明的富Al的基于AlCrN的膜,本发明人在具有大于70原子%Al的金属靶上使用反应性电弧沉积方法,其中基于以下理解选择沉积参数的本发明组合:
a)靶:选择电弧放电电流、磁场分布和强度以形成由Al、Cr和N的单电荷离子和多电荷离子组成的成膜物质的所需等离子体状态
b)一般:选择压力、源电流和偏压的组合以提供非常高能量的物质和因此提高动能,从而提高薄膜生长前沿处的入射离子的淬灭速率。同时,控制那些工艺参数,以抑制在生长表面上的六方相的成核。此外,氮气压力足够高以形成化学计量的AlCrN薄膜。
通过优化电弧沉积的上述工艺水平,在生长表面处抑制了热力学上有利的六方相的成核,从而将c-AlCrN中Al的亚稳态溶解度提高到大于70原子%(例如大于75原子%)的较高浓度。
具体地,本发明涉及生产经涂布的基材的方法,其包括在基材表面上沉积至少一个涂层,其中:
●所述至少一个涂层通过使用反应性PVD阴极电弧蒸发技术在真空涂布室的内部合成,其中:
-将氮气引入真空涂布室中用作反应性气体,
-使用至少一个包括作为阴极操作的靶材料的电弧蒸发源以蒸发靶材料,
-靶材料由Al和Cr组成或包含Al和Cr作为主要组分,其中如果仅考虑靶材料中的Al和Cr的原子百分比含量,则靶材料中的Al[原子%]/Cr[原子%]之比大于70/30,优选70/30<Al[原子%]/Cr[原子%]≤90/10,
-该方法包括来自靶材料的铝和铬与涂布室中包含的氮气之间的反应导致的氮化铝铬的反应性沉积,
-氮化铝铬的反应性沉积如下进行
i.在180℃至600℃,优选200℃至500℃的沉积温度下,
ii.在0.1Pa至9Pa、优选0.2Pa至8Pa、更优选0.6Pa至7.5Pa的氮气分压下,
iii.通过使用对应于-250V≤Ub≤-30V的范围内,优选对应于
-200V≤Ub≤-40V的范围内的偏压Ub,
iv.所形成的涂层:
a.包含Al、Cr和N作为仅有组分或作为主要组分,并具有根据式(AlaCrb)xOyCzNq的关于这些元素的按原子百分比计的化学元素组成,其中a和b分别为铝和铬的原子比浓度,仅考虑Al和Cr以计算层中的元素组成,其中a+b=1且82≥a≥>0.7且0≠b≥0.18,且其中x为Al的浓度与Cr的浓度之和,且y、z和q分别为氧、碳和氮的原子比浓度,仅考虑Al、Cr、O、C和N以计算层中的元素组成,其中x+y+z+q=1且0.45≤x≤0.55,0≤y≤0.25,0≤z≤0.25,
b.表现出90%或更多的fcc立方相,和
c.2.5GPa或更大,优选2.5GPa至6GPa的压缩应力。
如上所述的方法,其中:
-选择涂布参数,使得:
i.在至少一个涂层的沉积过程中获得并保持高氮电离,使得到达基材的氮物质的大于50%是双电荷的,
ii.通过获得对应于等于或大于200eV的值的铝和铬的金属离子的高能量,能够实现金属铝和铬物质的高注入。
如上所述的方法,其中:
-选择的涂布参数是同时在以下范围内的涂布参数的组合:
i.在-100V<Ub≤-40V的低偏压范围内的偏压Ub,
ii.在0.1Pa至1Pa的低压力范围内的氮气分压,和
iii.在350℃至500℃的温度范围内的工艺温度。
或者
-选择的涂布参数是同时在以下范围内的涂布参数的组合:
i.在-200V≤Ub≤-100V的高偏压范围内的偏压Ub,
ii.在0.8Pa至9Pa的高压力范围内的氮气分压,和
iii.在200℃至480℃的温度范围内的工艺温度。
如上所述的方法,其中电弧蒸发源电流为120A至200A。
包括涂层体系的经涂布的基材,该涂层体系包括根据上述任何本发明方法产生的至少一个涂层,其中所述涂层表现出高于30GPa,例如30GPa至50GPa的硬度,高于330GPa,例如330GPa至400GPa的杨氏模量,和72原子%至82原子%,即0.72≤a≤0.82的铝含量。
其它杂项
通常来说,意图在于,任选要求保护-当时间可能已经到来时-独立于或附加于最初存在的权利要求,保护根据下文的一个或多个(组合的)段落的层和/或方法:
一种涂层,其包含Al、Cr和N作为主要组分,并具有根据式(AlaCrb)xOyCzNq的关于这些元素的按原子百分比计的化学元素组成,其中a和b分别为铝和铬的原子比浓度,仅考虑Al和Cr以计算层中的元素组成,其中a+b=1且0≠a≥0.7且0≠b≥0.2,且其中x为Al的浓度与Cr的浓度之和,且y、z和q分别为氧、碳和氮的原子比浓度,仅考虑Al、Cr、O、C和N以计算层中的元素组成,其中x+y+z+q=1且0.45≤x≤0.55,0≤y≤0.25,0≤z≤0.25,其特征在于:涂层显示:90%或更多的fcc立方相,和2.5GPa或更大,优选2.5GPa至6GPa的压缩应力。
一种用于在基材表面上产生根据前述段落的涂层的方法,其特征在于,所述涂层通过使用反应性PVD阴极电弧蒸发技术在真空涂布室的内部合成,其中:将氮气引入真空涂布室中用作反应性气体,使用至少一个电弧蒸发源,其包括作为阴极操作的靶材料以蒸发靶材料,靶材料由Al和Cr组成或包含Al和Cr作为主要组分,其中如果仅考虑靶材料中的Al和Cr的原子百分比含量,靶材料中Al[原子%]/Cr[原子%]之比大于70/30,所述方法包括来自靶材料的铝和铬与涂布室中包含的氮气之间的反应导致的氮化铝铬的反应性沉积,氮化铝铬的反应性沉积在180℃至600℃,优选200℃至500℃的沉积温度下,在0.1Pa至9Pa、优选0.2Pa至8Pa、更优选0.6Pa至7.5Pa的氮气分压下,通过使用对应于-250V≤Ub≤-30V的范围内,优选对应于-200V≤Ub≤-40V的范围内的偏压Ub进行。
Claims (6)
1.用于生产经涂布的基材的方法,其包括在基材表面上沉积至少一个涂层,其特征在于:
●在真空涂布室内部,通过使用反应性PVD阴极电弧蒸发技术合成所述至少一个涂层,其中:
-将氮气引入真空涂布室中用作反应性气体,
-使用至少一个电弧蒸发源,其包括作为阴极操作的靶材料以蒸发靶材料,
-靶材料由Al和Cr组成或包含Al和Cr作为主要组分,其中如果仅考虑靶材料中的Al和Cr的原子百分比含量,靶材料中Al[原子%]/Cr[原子%]之比大于70/30,优选70/30>Al[原子%]/Cr[原子%]≥90/10,
-所述方法包括来自靶材料的铝和铬与涂布室中包含的氮气之间的反应导致的氮化铝铬的反应性沉积,
-如下进行氮化铝铬的反应性沉积
i.在180℃至600℃,优选200℃至500℃的沉积温度下,
ii.在0.1Pa至9Pa、优选0.2Pa至8Pa、更优选0.6Pa至7.5Pa的氮气分压下,
iii.通过使用对应于-250V≤Ub≤-30V的范围内,优选对应于-200V≤Ub≤-40V的范围内的偏压Ub,
iv.所形成的涂层:
a.包含Al、Cr和N作为仅有组分或作为主要组分,并具有根据式(AlaCrb)xOyCzNq的关于这些元素的按原子百分比计的化学元素组成,其中a和b分别为铝和铬的原子比浓度,仅考虑Al和Cr以计算所述层中的元素组成,其中a+b=1且82≥a≥>0.7且0≠b≥0.18,且其中x为Al的浓度与Cr的浓度之和,且y、z和q分别为氧、碳和氮的原子比浓度,仅考虑Al、Cr、O、C和N以计算所述层中的元素组成,其中x+y+z+q=1且0.45≤x≤0.55,0≤y≤0.25,0≤z≤0.25,
b.表现出90%或更多的fcc立方相,和
c.2.5GPa或更大,优选2.5GPa至6GPa的压缩应力。
2.根据权利要求1所述的方法,其特征在于:
-选择涂布参数,使得:
i.在至少一个涂层的沉积过程中获得并保持高氮电离,使得到达基材的氮物质的大于50%是双电荷的,
ii.通过获得对应于等于或大于200eV的值的铝和铬的金属离子的高能量,能够实现金属铝和铬物质的高注入。
3.根据权利要求2所述的方法,其特征在于:
-选择的涂布参数是同时在以下范围内的涂布参数的组合:
i.在-100V<Ub≤-40V的低偏压范围内的偏压Ub,
ii.在0.1Pa至1Pa的低压力范围内的氮气分压,和
iii.在350℃至500℃的温度范围内的工艺温度。
4.根据权利要求2所述的方法,其特征在于:
-选择的涂布参数是同时在以下范围内的涂布参数的组合:
i.在-200V≤Ub≤-100V的高偏压范围内的偏压Ub,
ii.在0.8Pa至9Pa的高压力范围内的氮气分压,和
iii.在200℃至480℃的温度范围内的工艺温度。
5.根据前述权利要求任一项所述的方法,其特征在于电弧蒸发源电流为100A至200A。
6.包括涂层体系的经涂布的基材,所述涂层体系包括根据前述权利要求任一项产生的至少一个涂层,其中所述涂层表现出高于30GPa,例如30GPa至50GPa的硬度,高于330GPa,优选330GPa至490GPa的杨氏模量,和70原子%至82原子%,即0.70≤a≤0.82,优选72原子%至82原子%,即0.72≤a≤0.82的铝含量。
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