CN100402421C - 高韧性金刚石及其制造方法 - Google Patents

高韧性金刚石及其制造方法 Download PDF

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CN100402421C
CN100402421C CNB2004800201556A CN200480020155A CN100402421C CN 100402421 C CN100402421 C CN 100402421C CN B2004800201556 A CNB2004800201556 A CN B2004800201556A CN 200480020155 A CN200480020155 A CN 200480020155A CN 100402421 C CN100402421 C CN 100402421C
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diamond
crystal diamond
growth
fracture toughness
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CN1823008A (zh
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R·J·赫姆利
H-K·毛
C-S·严
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Carnegie Institution of Washington
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Abstract

一种通过微波等离子体化学气相沉积生长的单晶金刚石的硬度为50-90GPa，断裂韧性为11-20MPa m1/2。用于生长单晶金刚石的方法包括将晶种金刚石置于夹具中；在大约1000℃至大约1100℃的温度下生长单晶金刚石，使得单晶金刚石的断裂韧性为11-20MPa m1/2。

Description

高韧性金刚石及其制造方法
本发明要求2003年7月14日提交的美国临时申请第60/486,435号的优先权，在此引入其内容作为参考。
政府利益声明
本发明是在美国政府的资助下进行的，国家科学基金会基金号EAR-0135626。美国政府拥有本发明的某些权利。
技术领域
本发明涉及金刚石，更具体地，涉及使用微波等离子体化学气相沉积(MPCVD)在沉积室内制造的高韧性金刚石。
背景技术
人造金刚石的大规模制造很久以来一直是研究和工业界的目标。金刚石除了它的宝石性质，它是已知的最硬材料，具有已知的最高热导率，并且对于多种电磁辐射可透过。除了它作为宝石的价值，由于在其许多工业中的广泛应用是有价值的。但是，金刚石的断裂韧性低，这使得它不适于许多应用，例如高抗冲的机床。
至少在最近的20年间，已经可以通过化学气相沉积(CVD)法来制造少量的金刚石。如B.V.Spitsyn等人在“Vapor Growth of Diamond onDiamond and Other Surfaces”，Journal of Crystal Growth，Vol.52，pp.219-226中所报道，该方法涉及使用甲烷或其它简单烃气与氢气的组合在减压和800-1200℃的温度下在基底上进行金刚石的CVD。包括氢气防止了随着金刚石成核和生长而形成石墨。使用这种技术已报道高达1μm/小时的生长速率。
后来的工作，例如Kamo等人在“Diamond Synthesis from Gas Phasein Microwave Plasma”，Journal of Crystal Growth，Vol.62，pp.642-644中所报道的，示范了使用微波等离子体化学气相沉积(MPCVD)在1-8KPa的压力和800-1000℃的温度下用2.45GHz频率下300-700W的微波功率来制造金刚石。Kamo等人的方法中使用了浓度为1-3％的甲烷气体。用这种MPCVD方法已报道最大生长速率为3μm/小时。
在上述方法以及许多更近期报道的方法中，在一些例子中金刚石的断裂韧性优于天然金刚石。尤其是，已经知道仅制造或生长多晶形式的金刚石的高生长速率的方法制造出断裂韧性高于天然金刚石的金刚石。除了某些已经过退火的高压高温(HPHT)人造金刚石，大多数金刚石的断裂韧性小于11MPa m1/2。
发明内容
因此，本发明关注于制造金刚石的装置和方法，其基本上消除了由于相关领域的限制和缺点导致的一个或多个问题。
本发明的目的涉及在微波等离子体化学气相沉积系统中制造断裂韧性提高的金刚石的装置和方法。
本发明另外的特征和优点将在以下描述中阐明，部分从描述中是显而易见的，或者可以通过本发明的实施获悉。本发明的目标和其它优点可以通过书面的描述和本文的权利要求以及附图所特别指出的结构实现和达到。
为了达到这些目的和其它优点并与本发明的目标一致，如所具体化和广泛描述的，通过微波等离子体化学气相沉积生长的单晶金刚石的硬度为50-90GPa，断裂韧性为11-20MPa m1/2。
在另一实施方式中，单晶金刚石的断裂韧性为18-20MPa m1/2。
根据本发明另一实施方式，用于生长单晶金刚石的方法包括将晶种金刚石置于夹具(holder)中，在大约1000℃至约1100℃的温度下生长单晶金刚石，使得单晶金刚石的断裂韧性为11-20MPa m1/2。
应当理解本发明的上述一般性描述和以下的详细描述均是示范性和说明性的，用来提供对所主张的本发明的进一步阐明。
附图说明
附图说明本发明的实施方式，并和说明书一起用来解释本发明，将附图包括在内以提供对本发明的进一步理解，其被结合在本说明书中并构成说明书的一部分。
图1是用于测试金刚石硬度和断裂韧性的压头的图片。
图2是在微波等离子体CVD-生长的单晶金刚石上的压痕的照片。
图3是显示微波等离子体CVD-生长的单晶金刚石与IIa型天然金刚石相比的硬度和韧性的图。
图4是显示不同温度下形成的微波等离子体CVD-生长的单晶金刚石与IIa型天然金刚石相比的硬度和韧性的图。
具体实施方式
现在详细参考本发明优选的实施方式，附图中说明了其结果。
本申请中提到的微波等离子体CVD-生长的单晶金刚石用2002年11月6日提交的题为“Apparatus and Method for Diamond Production(用于制造金刚石的装置和方法)”的美国专利申请第10/288,499号中描述的装置生长，在此引入该专利作为参考。通常，将晶种金刚石置于夹具中，随着金刚石生长，夹具移动晶种金刚石/生长的金刚石。本申请的发明人也是美国专利申请第10/288,499号的发明人。
厚度大于1毫米的微波等离子体CVD-生长的单晶金刚石沉积在Ib{100}型人造金刚石上。为了提高生长速率(50-150μm/h)并促进光滑{100}面的生长，在900-1500℃的温度下和120-220托的总压，N2/CH4＝0.2-5.0％，CH4/H2＝12-20％的气氛中，在CVD室中从微波诱导的等离子体生长单晶金刚石。拉曼光谱显示了在＜950℃和＞1400℃下产生褐色金刚石的少量的氢化无定形碳(a-C:H)4和含氮a-C:H(N:a-C:H)4。光致发光(PL)光谱显示了氮-空位(N-V)杂质。以比传统的多晶CVD生长法高两个数量级的生长速率已制造了厚度高达4.5mm的单晶金刚石。
图1是测试金刚石硬度和断裂韧性的压头的图。用图1所示的压头1在微波等离子体CVD-生长的单晶金刚石上进行维氏硬度和断裂韧性试验。图1中的压头1具有安装在底座3上的冲击材料2。冲击材料2可以是碳化硅、金刚石或者一些其它的坚硬材料。冲击材料的一面具有锥形维氏压头的形状，其中锥形维氏压头形状侧的角度为136°。
压头向试验金刚石2施加点载荷，直至在试验金刚石2中形成压痕或裂纹。为了防止压头的弹性变形，载荷在{100}面上沿试验金刚石的<100>方向在1至3kg之间变化。图2是在微波等离子体CVD-生长的单晶金刚石上产生的压痕的照片。通过光学显微镜测量压痕以及与压痕相关的裂纹的尺寸。
通过测量压痕的长度D和高度h，可以从以下的方程式(1)确定试验金刚石的硬度Hv：
(1)：Hv＝1.854×p/D2
P是压头上使用的在试验金刚石上形成压痕的最大载荷。D是压头在试验金刚石中形成的最长裂纹的长度，h是在试验金刚石中压痕的深度，如图1所示。
通过在以下的方程式(2)中使用自方程式(1)得到的硬度Hv，可以确定试验金刚石的断裂韧性Kc：
(2)：Kc＝(0.016±0.004)(E/Hv)1/2(P/C3/2)
E是杨氏模量，假定为1000GPa。P是压头上使用的在试验金刚石上形成压痕的最大载荷。d项是试验金刚石中压痕凹槽的平均长度，如图2所示，使d＝(d1+d2)/2。c项是试验金刚石中径向裂纹的平均长度，如图2所示，使c＝(c1+c2)/2。
图3的图片显示了微波等离子体CVD-生长的单晶金刚石与IIa型天然金刚石相比的硬度和韧性。图3所示的微波等离子体CVD-生长的单晶金刚石在大约1300℃的温度下生长，以达到高的生长速率。如图3所示，微波等离子体CVD-生长的单晶金刚石相对于天然IIa金刚石具有高得多的6-18MPa m1/2的断裂韧性。大多数微波等离子体CVD-生长的单晶金刚石的断裂韧性高于IIa型天然金刚石的断裂韧性的报道范围，如图3中的虚线框10所示，并高于多晶CVD金刚石断裂韧性的报道范围，如图3中的虚线框20所示。图3中代表的微波等离子体CVD-生长的单晶金刚石的断裂韧性为11-18MPa m1/2，硬度为50-90GPa。
图3中代表的微波等离子体CVD-生长的单晶金刚石在断裂韧性上的差别多少显得与处理温度有关。因此，本发明人在特定的处理温度范围内生长了另外的微波等离子体CVD-生长的单晶金刚石。换句话说，将晶种金刚石置于夹具中并在特定的处理温度范围内生长单晶金刚石。然后使这些另外的微波等离子体CVD-生长的单晶金刚石经受相同的硬度和断裂韧性测试。
图4的图片显示了不同温度下形成的微波等离子体CVD-生长的单晶金刚石与IIa型天然金刚石相比的硬度和韧性。更具体地，图4显示了分别在1300℃以上、1150℃-1250℃和1000℃-1100℃的温度下形成的微波等离子体CVD-生长的单晶金刚石的硬度和韧性。如图4所示，1000℃-1100℃下生长的微波等离子体CVD-生长的单晶金刚石的断裂韧性为大约18-20MPa m1/2，硬度为60-70GPa。
尽管单晶金刚石的生长速率较慢，但在1000℃-1100℃可以制造断裂韧性为18-20MPa m1/2的单晶金刚石。还没有报道具有这样高的断裂韧性的其它人造或天然的金刚石。而且，在例如1150℃-1350℃的较高温度下生长的金刚石可能未必达到高的断裂韧性，但是趋于有高的硬度，这使得这种金刚石可用于其它用途。
由于不偏离本发明的精神或基本特征可以以若干形式使本发明具体化，应当理解，除非特别指出，上述实施方式并不受任何上文描述的细节所限制，而应当是在如所附权利要求定义的其精神和范围内的广泛解释，因此所有落入权利要求的边界和范围或者这种边界和范围的等同物之内的变化和修改均包含在所附的权利要求中。

Claims (2)

1.一种通过微波等离子体化学气相沉积生长的单晶金刚石，其中在1000℃至1100℃的温度下，在120-220托的总压下在N2/CH4＝0.2-5.0％和CH4/H2＝12-20％的气氛中生长单晶金刚石，所述单晶金刚石的硬度为60-70GPa，断裂韧性为18-20MPam1/2。
2.一种使用微波等离子体化学气相沉积生长单晶金刚石的方法，其包括：
将晶种金刚石置于夹具中；和
在1000℃至1100℃的温度下，在120-220托的总压下在N2/CH4＝0.2-5.0％和CH4/H2＝12-20％的气氛中生长单晶金刚石，使所述单晶金刚石的断裂韧性为18-20MPa m1/2，硬度为60-70GPa。
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