CN1853001A - 对单晶化学气相沉积金刚石进行退火 - Google Patents

对单晶化学气相沉积金刚石进行退火 Download PDF

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CN1853001A
CN1853001A CNA2004800201537A CN200480020153A CN1853001A CN 1853001 A CN1853001 A CN 1853001A CN A2004800201537 A CNA2004800201537 A CN A2004800201537A CN 200480020153 A CN200480020153 A CN 200480020153A CN 1853001 A CN1853001 A CN 1853001A
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R·J·赫姆利
H-K·毛
志学颜
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Carnegie Institution of Washington
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Abstract

一种通过使CVD金刚石升高到在金刚石稳定相之外的至少1500℃的设定温度和至少4.0GPa的压力来改进CVD金刚石光学透明度的方法，在这里该CVD金刚石是单晶CVD金刚石。

Description

对单晶化学气相沉积金刚石进行退火
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，其在此并入作为参考。
政府所有权声明
本发明是在美国政府的资助下进行的，隶属美国科学基金会授权号EAR-0135626。美国政府拥有本发明的某些权利。
技术领域
本发明涉及对金刚石进行退火，更具体的说，涉及对单晶CVD金刚石进行退火。
背景技术
通过对含有前体分子的气相碳给予能量来实现金刚石的化学气相沉积生长。例如，可以使用微波能量产生等离子体，该等离子体使碳沉积，从而在晶种金刚石(seed diamond)上形成金刚石。直到最近，用于生长金刚石的所有CVD技术均导致多晶金刚石或者非常薄的单晶金刚石层。本申请的发明人已经开发了一种微波等离子体CVD技术以生长大的单晶CVD，其在2002年11月6日提交的未决专利申请第10/288,499号中被公开，其在此并入作为参考。
本发明人的微波等离子体CVD技术可以在晶种金刚石(例如黄色Ib型HPHT人造金刚石)上以达到每小时150微米的速率生长单晶金刚石。本发明人的微波等离子体CVD技术所生成的金刚石的颜色取决于该金刚石生长的温度。更具体地说，当金刚石在某个取决于等离子体中的气体混合物的温度范围内生长时，可以生成无色的金刚石。但是，在这一范围以外的温度下所生成的金刚石的颜色为黄色或褐色。
发明内容
因此，本发明涉及对单晶CVD金刚石进行退火，其基本上消除了由于相关技术的限制和缺点所导致的一个或多个问题。
本发明的一个目的是减轻或除去单晶CVD金刚石中的颜色。
本发明的另一个目的是消除单晶CVD金刚石中的缺陷。
本发明的另一个目的是提高单晶CVD金刚石的光学特性。
本发明另外的特征和优点的一部分将在以下的说明中阐明，一部分将显而易见地从说明中得出，或者可以通过本发明的实施而获悉。通过所撰写的说明书和权利要求书所特别指出的结构，将可以实现和获得本发明的目的和其它优点。
为了达到这些目的和其它优点并且符合本发明的目标，如所具体表达和广泛说明的，改进单晶CVD金刚石的光学透明度的方法，包括在至少4.0GPa的压力下将CVD金刚石升高到至少1500℃的设定温度。
应当理解到对本发明的上述大体说明和下述详细说明均是示范性和说明性的，意味着为所要求的发明提供进一步的解释。
具体实施方式
现在详细参考本发明的优选实施方式。
本发明人采用了他们的微波等离子体CVD技术来在例如Ib{100}型HPHT人造金刚石的晶种金刚石上生长厚度大于1毫米的单晶金刚石。为了将生长速率提高到大约50-150μm/h并且促进光滑{100}晶面的生长，在900-1500℃的温度下使用120-220托的总压力在N2/CH4＝0.2-5.0％、CH4/H2＝12-20％的气氛中生长单晶CVD金刚石。当金刚石在＜950℃或者＞1400℃下生长时，拉曼光谱显示了少量导致单晶CVD金刚石带有褐色或黄色的氢化无定形碳(a-C:H)4和含氮的a-C:H(N:a-C:H)4。而且，光致发光(PL)光谱显示了氮-空位(N-V)杂质。
CVD单晶金刚石在1400-1500℃的较高温度下生长得更快，但是所得到的金刚石带有褐色。不管颜色如何，通过本发明人的微波等离子体CVD技术所得到的单晶CVD金刚石仍然可以含有杂质。当然，人们需要颜色较浅的金刚石、更透明(more translucent)的金刚石或者无色的金刚石。
I.M.Reinitz等人在Gems&Gemology 36，128-137(2000)中报道了通过高温高压退火使褐色天然金刚石的褐色变浅并且减少杂质。但是，本发明人已经发现，在传统的高温高压装置中，使用反应釜在1800-2900℃的温度和5-7GPa的压力下对黄色或褐色的单晶CVD金刚石进行1-60分钟的退火，以便将部分褐色单晶CVD金刚石转化为透明无色的单晶金刚石。更具体地说，在大约1400-1460℃的温度下在含有比率为4-5％的N2/CH4的气氛中以高生长速率生长的黄色或浅褐色单晶CVD金刚石可以进行退火以变成无色单晶金刚石。而且，这种退火的CVD金刚石的拉曼和PL光谱证实了这种无色单晶金刚石中氢化无定形碳的消失和N-V杂质的显著降低。这些变化看起来与I.M.Reinitz等人通过对褐色天然金刚石进行HPHT退火而提高透明度的报道相似。
反应釜可以是小室(cell)，例如美国专利第3,745,623号或第3,913,280号中所述的小室，该专利在此并入作为参考。使整个小室经受超过4.0GPa的压力，例如5-7GPa，并且将其加热到超过1500℃的温度，例如1800-2900℃，使得小室或反应釜中的压力/温度条件在一段时间内处于石墨稳定相以内或者恰好在金刚石稳定相以内，这段时间可以短到1分钟或者长达1小时。在释放压力之前使小室冷却，以便使得单晶CVD金刚石不会变成石墨。
实施例1
在华盛顿卡内基研究所(Carnegie Institution of Washington)，在大约1500℃的温度下用比率为5％的N2/CH4在黄色Ib型HPHT人造金刚石上生长单晶CVD金刚石。单晶金刚石CVD金刚石的尺寸为1平方厘米，厚度稍大于1毫米。单晶金刚石CVD金刚石的颜色为褐色。然后将Ib型HPHT人造晶种金刚石上的褐色单晶CVD金刚石作为样品放置在反应釜中。
将反应釜放置在传统的HPHT装置中。首先，将压力增加到5.0GPa的压力，然后将温度迅速升高到2200℃。将样品在该退火条件下保持5分钟，然后在释放压力之前用大约1分钟的时间将温度降低至室温。
将样品从反应釜中取出，并且在光学显微镜下检查。褐色单晶CVD金刚石已经变成浅绿色并且保持牢固地结合在黄色Ib型HPHT人造金刚石上。人造Ib型金刚石的黄色变成更浅的黄色或者更透明的黄色。
实施例2
除了将退火条件保持1小时之外，与上述实施例1相同。深褐色的单晶CVD金刚石变成比实施例1中所得到的浅绿色更透明的浅绿色，并且保持牢固地结合在黄色Ib型HPHT人造金刚石上。Ib型HPHT人造金刚石的黄色变成更浅的黄色或者更透明的黄色。
实施例3
在华盛顿卡内基研究所(Carnegie Institution of Washington)，在大约1450℃的温度下用比率为5％的N2/CH4在黄色人造Ib型金刚石上生长单晶CVD金刚石。单晶金刚石CVD金刚石的尺寸为1平方厘米，厚度稍大于1毫米。单晶金刚石CVD金刚石的颜色为浅褐色或黄色。换句话说，不像上述实施例1中的单晶CVD金刚石的褐色那样深的浅褐色。然后将Ib型HPHT人造晶种金刚石上的黄色或浅褐色单晶CVD金刚石作为样品放置在反应釜中。
将反应釜放置在传统的HPHT装置中。将压力增加到大约5.0GPa的压力，然后将温度迅速升高到大约2000℃。将样品在该退火条件下保持5分钟，然后在释放压力之前用大约1分钟的时间将温度降低至室温。
将样品从反应釜中取出，并在光学显微镜下检验。浅褐色或黄色单晶CVD金刚石已经变成无色，并且保持牢固地结合在黄色Ib型HPHT人造金刚石上。Ib型HPHT人造金刚石的黄色也变成更浅的黄色或者更透明的黄色。
实施例4
除了在～1200℃的温度下在N2/CH4＝5％的气氛中对无色的微波等离子体单晶CVD-生长的金刚石进行退火之外，与上述实施例1相同。退火之后，微波等离子体单晶CVD-生长的金刚石是蓝色的。这种蓝色的微波等离子体单晶CVD-生长的金刚石具有＞20MPa m1/2的非常高的韧性。硬度为大约～140GPa。
实施例5
除了在～1200℃的温度下在N2/CH4＝.5％的气氛中对无色的微波等离子体单晶CVD-生长的金刚石进行退火，与上述实施例1相同。微波等离子体单晶CVD-生长的金刚石仍然是无色的。这种无色的微波等离子体单晶CVD-生长的金刚石的硬度为～160GPa，并且韧性为～10MPa m1/2。
由于在不偏离本发明的精神或其实质特征的条件下可以用几种形式具体表达本发明，还应当理解，除非特别指出，上述实施方式并不受任何前述说明的细节所限制，而是应当广泛地认为在如所附权利要求所定义的其精神和范围之内，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，因此均意味着被所附权利要求所包括。

Claims (9)

1.一种通过将CVD金刚石升高到在金刚石稳定相之外的至少1500℃的设定温度和至少4.0GPa的压力来改进CVD金刚石光学透明度的方法，其中所述的CVD金刚石是单晶CVD金刚石。
2.根据权利要求1所述的方法，其中所述的CVD金刚石是覆盖在另一种材料上的单晶。
3.根据权利要求1所述的方法，其中所述使所述单晶CVD金刚石的温度升高的步骤进一步包括以下步骤：
将所述单晶CVD金刚石升高到大约1800℃至大约2900℃的设定温度。
4.根据权利要求1所述的方法，其中所述使所述单晶CVD金刚石的温度升高的步骤进一步包括以下步骤：
将所述单晶CVD金刚石的温度在所述设定温度下保持少于大约1分钟。
5.根据权利要求1所述的方法，其中所述使所述单晶CVD金刚石的温度升高的步骤进一步包括以下步骤：
经过大约1分钟至5分钟的时间，将所述单晶CVD金刚石的温度升高到至少1500℃。
6.根据权利要求1所述的方法，其中所述使所述单晶CVD金刚石的温度升高的步骤进一步包括以下步骤：
在大约5.0GPa的压力下将所述CVD金刚石的温度升高到大约2200℃。
7.根据权利要求1所述的方法，进一步包括以下步骤：
在达到所述设定温度之后，将所述CVD的温度降低到环境温度，同时保持所述单晶CVD金刚石的压力。
8.根据权利要求1所述的方法，其中所述单晶CVD金刚石最初带有褐色并且变成无色。
9.根据权利要求1所述的方法，进一步包括以下步骤：
在大约1400-1460℃的温度下在含有4-5％的N2/CH4的气氛中生长所述褐色单晶金刚石。
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