CN105452543B - 金刚石涂层及沉积该涂层的方法 - Google Patents

金刚石涂层及沉积该涂层的方法 Download PDF

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CN105452543B
CN105452543B CN201480043361.2A CN201480043361A CN105452543B CN 105452543 B CN105452543 B CN 105452543B CN 201480043361 A CN201480043361 A CN 201480043361A CN 105452543 B CN105452543 B CN 105452543B
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diamond
microcrystalline
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CN105452543A (zh
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S·梅尔扎格赫
C·福雷
P·杜博瓦
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Abstract

本发明涉及金刚石涂层，其特征在于它包含至少一个第一纳米晶金刚石层和第二微晶金刚石层的叠层。

Description

金刚石涂层及沉积该涂层的方法
本发明涉及金刚石涂层，特别是具有小于20nm的粗糙度Ra的微晶金刚石涂层(MCD)，其例如用于微观力学领域中的摩擦应用。
本发明还涉及该金刚石涂层的沉积方法，其经济地执行。本发明更具体地涉及应用于微机械零件的这类方法，排列所述微机械零件以与其它零件摩擦接触，微机械零件相对于所述其它零件为运动的。这些微机械零件可同样好地为移动零件，例如旋转零件，或者固定零件，例如轴承。作为非限定性实例，它们可以为用于机械钟表运动的微机械零件。
本发明还涉及包含具有涂有金刚石涂层的功能表面的基质的微机械零件。
现有技术中熟知将基质用微晶金刚石涂层涂覆以提高所述基质的耐磨性以及降低摩擦。
图1为根据现有技术的微晶层的示意性阐述。为产生该单晶金刚石涂层，在待涂覆基质2的表面上产生成核层1。该成核层例如包含由金刚石纳米颗粒形成的晶种，金刚石纳米颗粒以约1010个颗粒/cm2的涂层密度遍布于基质表面上。然后将基质放入热丝或等离子体化学气相沉积(CVD)反应器中，将气体混合物，通常甲烷-氢气混合物注入其中。在测定的压力、温度和气流条件下，金刚石单晶3由晶种以柱状方式生长至所需涂层厚度。微晶通常具有从基质向外扩张的棱锥柱状形状使得晶粒尺寸随着层厚度而提高，如图1所述。
对于摩擦应用和典型的抗磨性，使用具有约0.5-10μm的厚度的金刚石层。以该厚度，表面晶粒尺寸超过200nm且粗糙度(Ra)可达到大于50nm的值，这意味着在许多应用中不能实现满意的摩擦条件。
为克服该缺点，本领域技术人员因此不得不对沉积进行一个或多个随后的抛光操作以降低粗糙度。通常，这些抛光操作机械地或者通过等离子体方法进行。在所有情况下，这些抛光操作为长、困难、昂贵的且不提供对某些应用而言，特别是对涂覆微机械时钟组件如擒纵叉和/或擒纵轮齿而言令人满意的结果。
因此，本发明的目的是通过提供金刚石涂层，特别是具有小于20nm的粗糙度Ra的微晶金刚石涂层克服这些缺点，所述涂层比现有技术涂层更容易得到且更经济地执行。
本发明的目的还有提供具有在其整个厚度上改进的机械性能的微晶金刚石涂层。
本发明的目的还有提供在其可见外表面上具有小于100nm的晶粒尺寸而不管本发明涂层的总厚度的微晶金刚石涂层。
本发明的目的还有提供具有改进美学外观的外表面，尤其是具有改进的反射率且适用于光学领域的微晶金刚石涂层。
为此，本发明涉及金刚石涂层，其特征在于它包含至少一个第一纳米晶金刚石层和第二微晶金刚石层的叠层。
由于这些特征，本发明提供产生厚，即大于1μm，具有比具有相同厚度的微晶金刚石层更小的表面晶粒尺寸和相关粗糙度的微晶金刚石涂层的可能性。这是由于这一事实：单晶微晶生长来自由纳米晶金刚石层形成的成核层，其比由金刚石纳米颗粒形成的常规成核层致密得多。
根据一个优选实施方案，本发明涂层包含一系列的至少两个所述叠层，其中第一叠层的微晶金刚石层与下一叠层的纳米晶金刚石层接触。
由于棱锥柱状生长在形成涂层的各个叠层上再起动，这意味着该系列的本发明叠层以具有给定厚度的单一叠层的晶粒尺寸和粗糙度提供大的涂层厚度。
有利地，纳米晶层的厚度为50nm至1μm，微晶层的厚度为100nm至1μm,，优选纳米晶层的厚度为100-200nm微晶层的厚度为200-500nm。
优选纳米晶金刚石层表面的晶粒尺寸小于50nm，特别是小于30nm，甚至更优选小于10nm。
优选，本发明涂层的可见外表面的晶粒尺寸为约100nm。
本发明还涉及包含具有功能表面的基质的微机械零件，其中功能表面涂有包含至少一个第一纳米晶金刚石层和第二微晶金刚石层的叠层的金刚石涂层，基质的所述功能表面与所述涂层的纳米晶金刚石层接触。
有利地，基质选自包含硅、钛、锆、铪、钒、钽、钼、钨、硼的材料；后面材料的硼化物、碳化物、氮化物和氧化物，和陶瓷的组。
根据优选实施方案，本发明微机械零件可以为齿轮、齿杆、擒纵轮、擒纵叉杆、擒纵叉瓦、发条、主发条、摆轮游丝、心轴和/或枢轴承。
本发明还涉及通过在反应室中化学气相沉积而在基质上沉积金刚石涂层的方法，所述方法包括至少：
a)制备基质的步骤，
b)初始成核步骤，
c)使涂层在基质表面上生长的步骤，所述生长步骤包括至少一系列的2个连续阶段，包括纳米晶金刚石生长形成纳米晶金刚石层的阶段，其后微晶金刚石生长的另一阶段，其中纳米晶金刚石层用作用于微晶金刚石层生长的成核层。
优选，步骤c)重复多次。
有利地，在步骤c)的纳米晶金刚石生长阶段期间，调整沉积参数使得纳米晶金刚石晶粒尺寸不超过50nm，优选30nm，甚至更优选10nm，并设置步骤c)的微晶金刚石生长阶段的持续时间以实现200nm至1μm，优选200-500nm的微晶金刚石厚度。
优选，步骤c)的纳米晶金刚石生长阶段的持续时间使得可得到100-200nm的纳米晶金刚石厚度。
优选，基质选自包含硅、钛、锆、铪、钒、钽、钼、钨、硼的材料；后面材料的硼化物、碳化物、氮化物和氧化物，和陶瓷的组。
有利地，方法在热丝反应器中进行，且步骤c)期间的基质温度为500-1000℃。
根据一个优选实施方案，纳米晶金刚石生长阶段在以下条件下进行：
●持续时间1小时至5小时，
●将CH4/H2/X气体混合物加热，分别直接或间接活化，其中X表示掺杂剂气体，其中相对于总体积，掺杂剂气体的体积百分数为0％至10％，CH4的体积百分数为3％至9％，
●在1巴压力下的氢气流速为20-50升/分钟，优选40升/分钟，
●室中气体混合物的压力为2-6毫巴，
●基质温度为500-1000℃，
且微晶金刚石生长阶段在以下条件下进行：
●持续时间1小时至5小时，
●将CH4/H2/X气体混合物分别直接或间接加热，其中X表示掺杂剂气体，其中相对于总体积，掺杂剂气体的体积百分数为0％至10％，CH4的体积百分数为0,05％至1％，
●在1巴压力下的氢气流速为30-90升/分钟，优选60升/分钟，
●室中气体混合物的压力为0.5-2毫巴，且
●基质温度为500-1000℃。
附图简述
本发明的特征在参考附图阅读对仅作为非限定性实例给出的本发明优选实施方案的描述时更清楚地获悉，其中：
-已经描述的图1显示涂有根据现有技术的微晶金刚石涂层的基质的示意性横截面；
-图2显示涂有包含本发明叠层的微晶金刚石涂层的基质的横截面；
-图3显示涂有包含多个本发明叠层的微晶金刚石涂层的基质的横截面；
-图4a和4b分别为显示涂有根据本发明和根据现有技术的微晶金刚石涂层的基质的顶视图的扫描电子显微镜照片。
参考图1，看出涂有根据常规沉积方法沉积的微晶金刚石涂层3的基质2。应当指出微晶生长由分布于基质2表面上的由金刚石纳米颗粒形成的晶种1引发，并产生由从基质表面向外扩张的具有棱锥柱状几何的晶体形成的层。当层3的厚度提高时，晶体尺寸提高并确保涂层的可见外表面上的晶粒尺寸生长。晶粒尺寸的这一提高导致粗糙度提高，取决于涂层的预期应用，这可能是不理想的。
参考图2，看出涂有根据本发明沉积方法沉积的微晶金刚石涂层5的基质4。
不同于由单一微晶金刚石层3形成的现有技术涂层，单晶金刚石涂层由第一纳米晶金刚石层5a和第二微晶金刚石层5b的叠层形成，如图2所示。
应当指出以相同的微晶金刚石涂层表面厚度，与现有技术涂层相比，涂层的可见外表面上的晶粒尺寸更小，因此粗糙度降低。这是由于这一事实：微晶金刚石层的成核由为密闭层的纳米晶金刚石层产生，这提供比由简单分布在待涂覆基质表面上的金刚石纳米颗粒形成的常规晶种更密且更均匀的生长位数。例如，以约100nm的纳米晶层厚度和约200nm的微晶层厚度，所得晶粒尺寸的降低为约50％，且粗糙度Ra的降低为约30％。这清楚地显示于图4a和4b中。
另外，由于本发明金刚石涂层的层叠性质，以相同的金刚石涂层厚度，本发明涂层的微晶金刚石层比现有技术微晶金刚石涂层更薄。本发明金刚石涂层中微晶金刚石层的这一厚度降低还贡献于涂层外表面的晶粒尺寸和粗糙度Ra的降低。
参考图3，看到本发明涂层7的变化实施方案沉积于其上的基质6。在该变化方案中，涂层包含一系列的两个叠层5，如同参考图2所述的那些。
图4a和4b显示涂有微晶金刚石涂层的基质的顶视图的扫描电子显微镜照片，其中最终微晶金刚石层以相同的条件(一起在相同的反应器中)，根据本发明由纳米晶层(图4a)以及根据现有技术由分布于基质表面的金刚石纳米颗粒沉积。清楚地看出，本发明涂层的晶粒尺寸比现有技术(对于250nm的微晶金刚石层厚度，通常为200nm)小50％(对于250nm的微晶金刚石层厚度，通常为100nm)，且本发明涂层的粗糙度Ra与现有技术相比降低30％。
下文描述本发明微晶金刚石涂层在由包含待涂覆微机械零件的硅片形成的基质上的示例沉积，所述微机械零件通过易碎固定元件保持在晶片上。
涂层5通过在热丝反应室中化学气相沉积(CVD)而沉积在基质4上。
在放入反应室中以前，将基质4在氢氟酸浴中清洗以除去原生氧化物层并增强会用于生长第一纳米晶金刚石层的金刚石纳米颗粒在其表面的附着。
然后将基质4放入包含溶剂，通常异丙醇且金刚石纳米颗粒悬浮的浴中。纳米颗粒的尺寸通常为5-15nm。然后借助超声搅拌该浴以将金刚石纳米颗粒附着在基质表面上。
然后将基质4风干或者在惰性气流，例如氮气流中干燥以完成基质制备步骤。
然后将制备的基质置于反应室中的台上，优选容许气体围绕基质自由流动，然后将室排空，通常以小于1毫巴的真空。
然后将基质借助加热器直接和/或通过由反应器灯丝辐射的热间接加热至沉积温度。通常，沉积温度为500-1000℃，例如约750°的温度。
当达到沉积温度时，将CH4/H2气体混合物注入反应室中。CH4的百分数相对于总体积为3％至9％，优选6％，且在1巴压力下的氢气流速为20-50升/分钟，优选40升/分钟。室中气体混合物的压力则为2-6毫巴，优选4毫巴。这些条件引发成核和由金刚石纳米颗粒的纳米晶金刚石生长步骤并构成初始成核步骤。
然后保持初始成核步骤条件以使纳米晶金刚石层至少在容许形成纳米晶金刚石层的厚度，通常在100nm的厚度上生长。
该厚度当然可取决于待得到的所需最终涂层硬度改变，并且达一微米，尽管已知如果涂层的纳米晶金刚石层具有较大的厚度，则本发明涂层的硬度会是较低的。
纳米晶金刚石生长构成本发明金刚石涂层生长步骤的一个阶段。
当实现所需纳米晶金刚石厚度时，改变反应室中的条件以使微晶金刚石层生长。为此，改进CH4相对于CH4/H2气体混合物总体积的百分数并且变成0.05％至1％，优选0.1％的值，且在1巴压力下的氢气流速变成30-90升/分钟，优选60升/分钟的值。然后使室中气体混合物的压力返回0.5-2毫巴，优选1毫巴的值。在这些沉积条件下，金刚石生长以微晶形式进行，下面纳米晶层的晶粒形成未来微晶层的晶种。
当实现所需厚度时，微晶金刚石层生产阶段中断一次。为得到具有降低的表面晶粒尺寸(通常约100nm)和小于20nm的粗糙度Ra且适用于摩擦应用的微晶金刚石层，微晶金刚石层的厚度应优选不超过500nm。
对于其中需要大于1μm的金刚石涂层厚度的应用，重复纳米晶金刚石和微晶金刚石层的一系列连续沉积直至实现所需厚度。
不言而喻，本发明不限于恰好描述的实施方案且本领域技术人员可不偏离如所附权利要求书所定义的本发明范围而预期各种简单的改进和变化。

Claims (26)

1.包含具有表面的基质的微机械零件，所述表面包含金刚石涂层，其特征在于基质选自材料硅、钛、锆、铪、钒、钽、钼、钨、硼；陶瓷和材料硅、钛、锆、铪、钒、钽、钼或钨的硼化物、碳化物、氮化物或氧化物，金刚石涂层包含至少一个第一纳米晶金刚石层和第二微晶层的叠层，其中第一纳米晶金刚石层在表面具有小于50nm的晶粒尺寸，第二微晶层在表面具有100nm数量级的晶粒尺寸，且特征在于最接近基质的金刚石层为纳米晶的且距离基质最远的金刚石表面为微晶的。
2.根据权利要求1的微机械零件，其特征在于涂层包含一系列的至少两个所述叠层，其中第一叠层的微晶金刚石层与下一叠层的纳米晶金刚石层接触。
3.根据权利要求1或2的微机械零件，其特征在于纳米晶金刚石层的厚度为50nm至1μm。
4.根据权利要求3的微机械零件，其特征在于纳米晶金刚石层的厚度为100-200nm。
5.根据权利要求1或2的微机械零件，其特征在于微晶金刚石层的厚度为100nm至1μm。
6.根据权利要求5的微机械零件，其特征在于微晶金刚石层的厚度为200-500nm。
7.根据权利要求1或2的微机械零件，其特征在于纳米晶金刚石层表面的晶粒尺寸为小于30nm。
8.根据权利要求1或2的微机械零件，其特征在于纳米晶金刚石层表面的晶粒尺寸为小于10nm。
9.根据权利要求1、2、4和6中任一项的微机械零件，其特征在于零件包括齿轮、齿杆、擒纵轮、擒纵叉杆、擒纵叉瓦、发条、主发条、摆轮游丝、心轴和/或枢轴承。
10.得到根据权利要求1-9中任一项的微机械零件的方法，所述方法包括至少：
a)制备基质的步骤，其中基质选自材料硅、钛、锆、铪、钒、钽、钼、钨、硼；陶瓷和材料硅、钛、锆、铪、钒、钽、钼或钨的硼化物、碳化物、氮化物或氧化物，
b)初始成核步骤，
c)生长步骤，所述生长步骤包括至少一系列的2个连续阶段，包括纳米晶金刚石生长形成纳米晶金刚石层的阶段，其后微晶金刚石生长的另一阶段，其中纳米晶金刚石层用作用于微晶金刚石层生长的成核层。
11.根据权利要求10的方法，其特征在于步骤c)重复多次。
12.根据权利要求10的方法，其特征在于在步骤c)的纳米晶金刚石层生长阶段期间，设置沉积参数使得纳米晶金刚石晶粒尺寸不超过50nm。
13.根据权利要求11的方法，其特征在于在步骤c)的纳米晶金刚石层生长阶段期间，设置沉积参数使得纳米晶金刚石晶粒尺寸不超过50nm。
14.根据权利要求12的方法，其特征在于在步骤c)的纳米晶金刚石层生长阶段期间，设置沉积参数使得纳米晶金刚石晶粒尺寸不超过30nm。
15.根据权利要求12的方法，其特征在于在步骤c)的纳米晶金刚石层生长阶段期间，设置沉积参数使得纳米晶金刚石晶粒尺寸不超过10nm。
16.根据权利要求10-15中任一项的方法，其特征在于步骤c)的微晶金刚石生长阶段的持续时间可产生200nm至1μm的微晶金刚石厚度。
17.根据权利要求16的方法，其特征在于步骤c)的微晶金刚石生长阶段的持续时间可产生200-500nm的微晶金刚石厚度。
18.根据权利要求10-15和17中任一项的方法，其特征在于步骤c)的纳米晶金刚石生长阶段的持续时间可产生100-200nm的纳米晶金刚石厚度。
19.根据权利要求10-15和17中任一项的方法，其特征在于方法在热丝反应器中进行。
20.根据权利要求18的方法，其特征在于方法在热丝反应器中进行。
21.根据权利要求10-15、17和20中任一项的方法，其特征在于步骤c)期间的基质温度为500-1000℃。
22.根据权利要求10-15、17和20中任一项的方法，其特征在于纳米晶金刚石生长阶段在以下条件下进行：
●持续时间1小时至5小时，
●将CH4/H2/X气体混合物加热，分别直接或间接活化，其中X表示掺杂剂气体，其中相对于总体积，掺杂剂气体的体积百分数为0％至10％，CH4的体积百分数为3％至9％，
●在1巴压力下的氢气流速为20-50升/分钟，
●室中气体混合物的压力为2-6毫巴，
●基质温度为500-1000℃。
23.根据权利要求22的方法，其特征在于在1巴压力下的氢气流速为40升/分钟，室中气体混合物的压力为4毫巴。
24.根据权利要求10-15、17、20和23中任一项的方法，其特征在于微晶金刚石生长阶段在以下条件下进行：
●持续时间1小时至5小时，
●将CH4/H2/X气体混合物分别直接或间接加热，其中X表示掺杂剂气体，其中相对于总体积，掺杂剂气体的体积百分数为0％至10％，CH4的体积百分数为0,05％至1％，
●在1巴压力下的氢气流速为30-90升/分钟，
●室中气体混合物的压力为0.5-2毫巴，
●基质温度为500-1000℃。
25.根据权利要求24的方法，其特征在于在1巴压力下的氢气流速为60升/分钟，室中气体混合物的压力为1毫巴。
26.包含具有表面的基质的微机械零件，所述表面包含金刚石涂层，其特征在于金刚石涂层包含至少一个第一纳米晶金刚石层和第二微晶层的叠层，其中第一纳米晶金刚石层在表面具有小于50nm的晶粒尺寸，第二微晶层在表面具有100nm的数量级的晶粒尺寸，且特征在于最接近基质的金刚石层为纳米晶的且距离基质最远的金刚石表面为微晶的，且特征在于所述零件包括齿轮、齿杆、擒纵轮、擒纵叉杆、擒纵叉瓦、发条、主发条、摆轮游丝、心轴和/或枢轴承。
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CN108604091B (zh) 2015-12-04 2023-07-21 伯克希尔格雷营业股份有限公司 用于动态处理物体的系统和方法
US10049927B2 (en) * 2016-06-10 2018-08-14 Applied Materials, Inc. Seam-healing method upon supra-atmospheric process in diffusion promoting ambient
US10622214B2 (en) 2017-05-25 2020-04-14 Applied Materials, Inc. Tungsten defluorination by high pressure treatment
US10276411B2 (en) 2017-08-18 2019-04-30 Applied Materials, Inc. High pressure and high temperature anneal chamber
WO2019036157A1 (en) 2017-08-18 2019-02-21 Applied Materials, Inc. HIGH PRESSURE AND HIGH TEMPERATURE RECOVERY CHAMBER
CN109750291A (zh) * 2017-11-07 2019-05-14 深圳先进技术研究院 一种硼掺杂金刚石电极及其制备方法
EP4321649A3 (en) 2017-11-11 2024-05-15 Micromaterials LLC Gas delivery system for high pressure processing chamber
CN111432920A (zh) 2017-11-17 2020-07-17 应用材料公司 用于高压处理系统的冷凝器系统
SG11202008256WA (en) 2018-03-09 2020-09-29 Applied Materials Inc High pressure annealing process for metal containing materials
US10950429B2 (en) 2018-05-08 2021-03-16 Applied Materials, Inc. Methods of forming amorphous carbon hard mask layers and hard mask layers formed therefrom
US10748783B2 (en) 2018-07-25 2020-08-18 Applied Materials, Inc. Gas delivery module
US11187040B2 (en) 2018-07-30 2021-11-30 XR Downhole, LLC Downhole drilling tool with a polycrystalline diamond bearing
US11014759B2 (en) 2018-07-30 2021-05-25 XR Downhole, LLC Roller ball assembly with superhard elements
WO2020117462A1 (en) 2018-12-07 2020-06-11 Applied Materials, Inc. Semiconductor processing system
JP2022536052A (ja) * 2019-05-29 2022-08-12 エックスアール ダウンホール リミテッド ライアビリティ カンパニー ダイヤモンド対ダイヤモンド反応材料軸受係合のための材料処理
US11901222B2 (en) 2020-02-17 2024-02-13 Applied Materials, Inc. Multi-step process for flowable gap-fill film
US11594416B2 (en) 2020-08-31 2023-02-28 Applied Materials, Inc. Tribological properties of diamond films
US12006973B2 (en) 2020-11-09 2024-06-11 Pi Tech Innovations Llc Diamond surface bearings for sliding engagement with metal surfaces
US11655850B2 (en) 2020-11-09 2023-05-23 Pi Tech Innovations Llc Continuous diamond surface bearings for sliding engagement with metal surfaces
CN112981362B (zh) * 2021-02-08 2023-11-28 上海电气集团股份有限公司 一种金刚石涂层材料及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174875B1 (en) * 1984-09-14 1990-06-06 Konica Corporation Method for converting radiographic image and radiation energy storage panel having stimulable phosphor-containing layer
US5432003A (en) * 1988-10-03 1995-07-11 Crystallume Continuous thin diamond film and method for making same
EP0752293A2 (en) * 1995-07-05 1997-01-08 Ngk Spark Plug Co., Ltd Diamond coated article and process for its production
DE202004014495U1 (de) * 2004-06-02 2005-10-13 Böhlerit Ges.m.b.H. & Co. KG Hartmetallwendeschneidplatte mit Diamantschicht
JP2007277088A (ja) * 2007-06-14 2007-10-25 Kobe Steel Ltd ダイヤモンド被覆非ダイヤモンド炭素部材
CN102059361A (zh) * 2009-11-16 2011-05-18 三菱综合材料株式会社 耐剥离性和耐磨性优异的金刚石包覆工具
CN102421936A (zh) * 2009-05-18 2012-04-18 斯沃奇集团研究及开发有限公司 涂覆用于机械系统的具有高摩擦性能的微机械部件的方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6592839B2 (en) * 1991-11-25 2003-07-15 The University Of Chicago Tailoring nanocrystalline diamond film properties
JP3416967B2 (ja) * 1992-12-10 2003-06-16 日本精工株式会社 人工ダイヤモンド被覆膜及びその形成方法
FR2798397A1 (fr) * 1999-09-03 2001-03-16 Lionel Gerard Vandenbulcke Procede de fabrication d'une piece revetue de diamant nanocristallin de rugosite faible
JP3477162B2 (ja) * 2000-06-29 2003-12-10 オーエスジー株式会社 ダイヤモンド被覆工具およびその製造方法
DE10149588B4 (de) * 2001-10-08 2017-09-07 Oerlikon Trading Ag, Trübbach Verfahren zur Diamantbeschichtung von Substraten
EP2431503A1 (en) * 2004-05-27 2012-03-21 Toppan Printing Co., Ltd. Method of manufacturing an organic electroluminescent device or an organic photoelectric receiving device using a nano-crystalline diamond film
DE602006004055D1 (de) * 2005-06-28 2009-01-15 Eta Sa Mft Horlogere Suisse Verstärktes mikromechanisches teil
US20100209665A1 (en) * 2005-09-29 2010-08-19 Konovalov Valeriy V Ultra smooth nanostructured diamond films and compositions and methods for producing same
JP5648171B2 (ja) * 2009-01-21 2015-01-07 セイコーインスツル株式会社 機械部品の製造方法
EP2453038A1 (en) * 2010-11-16 2012-05-16 The Swatch Group Research and Development Ltd. Method for coating micromechanical parts with dual diamond coating
US9958830B2 (en) * 2011-07-21 2018-05-01 The Swatch Group Research And Development Ltd Functional micromechanical assembly

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174875B1 (en) * 1984-09-14 1990-06-06 Konica Corporation Method for converting radiographic image and radiation energy storage panel having stimulable phosphor-containing layer
US5432003A (en) * 1988-10-03 1995-07-11 Crystallume Continuous thin diamond film and method for making same
EP0752293A2 (en) * 1995-07-05 1997-01-08 Ngk Spark Plug Co., Ltd Diamond coated article and process for its production
DE202004014495U1 (de) * 2004-06-02 2005-10-13 Böhlerit Ges.m.b.H. & Co. KG Hartmetallwendeschneidplatte mit Diamantschicht
JP2007277088A (ja) * 2007-06-14 2007-10-25 Kobe Steel Ltd ダイヤモンド被覆非ダイヤモンド炭素部材
CN102421936A (zh) * 2009-05-18 2012-04-18 斯沃奇集团研究及开发有限公司 涂覆用于机械系统的具有高摩擦性能的微机械部件的方法
CN102059361A (zh) * 2009-11-16 2011-05-18 三菱综合材料株式会社 耐剥离性和耐磨性优异的金刚石包覆工具

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